A New Look at the Chemical Bonding in S2N2 and S4N4

Tetrasulfur tetranitride is the earliest known sulfurnitrogen compound , having

been first prepared in 1835 . Disulfur dinitride was discovered as an unstable
intermediate in 1910 during the purification of a sample of S4N4 by vacuum
sublimation ; it spontaneously polymerized to a golden , metallic material ,
poly(sulfur nitride) , having the formula (SN)x . These three compounds are the
tetramer , dimer , and polymer respectively of the thiazyl radical , SN .
The unusual formulas of these sulfurnitrogen compounds have been both puzzling
and intriguing . The sulfur valence S is normal for sulfur(II) compounds , such
as in hydrogen sulfide , mercaptans (thiols) , sulfides (thioethers) , disulfides , and
in elemental octosulfur S8 . The sulfur atoms in these substances all have
a tetrahedral coordination , in which the six valence electrons (3s2 3p4) have a
sp3 configuration . Two electrons are shared in two sigma covalent bonds with
neighbouring atoms , and four electrons are in two nonbonding lone pairs . The
S atoms in S2N2 , S4N4 , and (SN)x seem to be ordinary divalent sulfur , and have
a similar tetrahedral sp3 configuration .
The problem arises with the peculiar electronic state of the nitrogen atoms in these
compounds . The N type of valence implies trigonal planar nitrogen , sp2 + pz ,
such as is found in the nitrogen atom of the pyridine molecule , for example . Two
of the five nitrogen valence electrons , 2s2 2p3 , are shared in sigma covalent bonds
with neighbouring carbon atoms , two are in a nonbonding lone pair in the x-y
plane , and the fifth valence electron is in an axial native (unhybridized) 2pz orbital
. In pyridine this latter orbital with its singlet electron can overlap with the five
carbon 2pz1 orbitals to form a hexagonal ring in which the six 2pz electrons have a
stabilizing aromatic resonance .
A similar resonance has been proposed in various electronic structures for
S2N2 and S4N4 [the references are presented at the end of the text , below] . The
nitrogen atoms are trigonal , while half of the sulfur atoms are divalent S and the
other half are tetravalent =S= . These two sulfur valences are reproportionated into
trigonal S= by resonance with the nitrogens : SN=S=N -----> S=NS=N .
This works well for the nitrogens , but a problem arises with the sulfurs in that they
have six valence electrons , but only five can be accomodated in the pi resonance
system . Where does the sixth one go ? Some of these resonance schemes become
quite complicated as they attempt to provide rational Lewis covalent bond
structures for the compounds .
The objective of this essay is to describe the chemical bonds in S2N2 and S4N4 in a
simple , elementary manner . Several guidelines have been followed in this study :

* The sulfur atoms have a tetrahedral sp3 configuration , and are electronically
inert linking atoms ;
* The nitrogen atoms have a trigonal planar sp2 + pz configuration , and are the
electronically active components of S2N2 and S4N4 ; and ,
* There is no transfer or resonance of valence electrons between the sulfur and
nitrogen atoms in S2N2 and S4N4 . An unusual sort of resonance will be proposed
for the nitrogen 2pz1valence electrons in tetrasulfur tetranitride .
The electronic structure of poly(sulfur nitride) is discussed in another web page ,
Three Models of the Metallic Bond in Poly(sulfur nitride) [Underlined blue
hyperlinks can be clicked when online to download the PDF or HTML file , which
will open in a new window] . As with S2N2 and S4N4 , the sulfur atoms in (SN)x are
again considered to have the electronically inert tetrahedral configuration .
However , instead of being trigonal planar sp2 + pz , the nitrogen atoms are
considered to have the trigonal pyramid s + p3 configuration . The s orbital in this
case is the 2s1 native (unhybridized) orbital , which can overlap continuously in the
polymer chains to form the metallic bond in them .
The consequences of the sp2 + pz configuration of the nitrogens , and how the
electronic state of the chemical bonds in S2N2 and S4N4 are correlated with their
known physical and chemical properties , are discussed in the following sections of
this web page .

Disulfur Dinitride , S2N2

Brauer (pp. 409-410) describes S2N2 as ...........

Well-formed , colorless crystals ; very volatile ; unpleasant iodine-like odor ;
stable only at low temperatures ; becomes dark after a short exposure to 20 C ;
sublimes at 10-2 mm even at room temperature ; polymerizes readily to (SN)x ; in
the presence of moisture , about 67% of the S2N2 polymerizes to (SN)x , while 33%
dimerizes to S4N4 ........ The addition of even trace amounts of various salts
(NaOH , KCN , Na2CO3) to S2N2 causes instantaneous and complete
dimerization. To purify the S2N2 it can be sublimed at room temperature in high
vacuum . Beautiful , large , colorless crystals are obtained. The material
detonates violently at 30 C , or when under high mechanical pressure.
S2N2 is diamagnetic ; as it polymerizes to (SN)x it darkens and becomes
paramagnetic :

As polymerization proceeds the colorless diamagnetic S2N2 crystals turn intense

blue-black and become paramagnetic giving a weak free radical signal at g = 2.005
. As the blue-black color fades , the crystals become a metallic golden color and
the free radical signal gradually decreases to zero (Mikulski and co-workers , p.
6361) . They also note ,
It should be stressed that S2N2 , which is a slightly volatile colorless solid , has
been reported to be extremely explosive and sensitive to slight mechanical shock
(p. 6360) .
Mikulski et al. determined the molecular structure and physical constants of
S2N2 by X-ray diffraction . They found it had a nearly perfect square , flat shape :

Sulfur(II)sulfur(IV) resonance was thought to average the SN bond lengths in

S2N2 to 1.654 :

........ suggesting a bond order of approximately 1.5 for all of the equivalent SN
bonds . The SN single bond length is expected to be approximately 1.74 and
that for the SN double bond is approximately 1.54 . Their average , 1.64 ,
expected for a bond order of ca. 1.5 , is remarkably close to that found
experimentally (1.654 ) [Mikulski et al. , p. 6361 ; Gritsan and co-workers] .
This resonance structure of S2N2 is sketched as follows :

It certainly is an attractive model in many ways . The almost perfectly square ,

planar shape of the S2N2 molecule is explained . There is an aromatic type

of bonding over the sigma bonds , consisting of six electrons in the four
pz orbitals , which would stabilize the molecule . Resonance of the two singlet
nitrogen electrons in this pi cloud would result in diamagnetism in S2N2 , which is
observed . The nitrogen atoms unquestionably have a trigonal planar configuration
; this is shown in the stable , crystalline adduct S2N2(SbCl5)2 , whichX-ray
diffraction demonstrates has a linear shape :

In this compound the nucleophilic nitrogen sp2 lone pairs form coordinate covalent
bonds with the electrophilic antimony atoms of the SbCl5 .
As attractive as it is , there are three problems with the resonance-stabilized model
of S2N2 . First , there probably isn't any aromatic stabilzation in the molecule , as
it is well known to be very unstable , exploding at only a few degrees above room
temperature . Second , the six electrons resonating in the four bonds would result
in a total bond order in the molecule of 2.5 [1.0 SN sigma + 1.5 SN pi] . This 2.5
bond order would result in a much shorter SN bond length , possibly ~ 1.5 ,
than is actually observed in S2N2 (1.654 ) .
Third , the 90 bond angles are much too small for the usual trigonal planar
coordination , whose ideal bond angle is 120 . The well-known Valence
Bond octahedral hybrid orbital has 90 angles , but would be inapplicable to the
nitrogen atoms in all molecules , and to the sulfur atoms in S2N2 . The composite
hybrid orbital [comprised of two simpler hybrids] sp+p2would have 90 angles . If
all four atoms in S2N2 had such a sp+p2 hybridization , a perfectly square molecule
could be constructed from their combination :

However , this model is unsatifactory , as the sp lobes of the nitrogen atoms are
pointing in the wrong direction with respect to forming coordinate covalent bonds
with electrophilic acceptor molecules such as SbCl5 . The nitrogens must have a
standard trigonal planar sp2 + pz configuration , but with a non-standard type
of orbital overlap with the sulfur atoms .
One possibility is that the nitrogen and sulfur bonds could have a bent banana
orbital overlap , thereby forming slightly curved sigma covalent bonds . To
examine this idea more closely I constructed a model of S2N2 using the Framework
Molecular Model kit (Prentice-Hall , Englewood Cliffs , NJ) from my college
chemistry days back in the mid 1960s . The kit is equipped with three types of
small metal jacks with tetrahedral (109) , trigonal bipyramid (120 , equatorial)
and octahedral (90/180) angles . It also has many thin plastic tubes in various
colors , for constructing the interatomic bonds .
I tried making the model directly with trigonal jacks for the nitrogens and
tetrahedral ones for the sulfurs , but ring closure was impossible . Then I tried a
bent banana orbital overlap , which was more successful , but there was still
considerable ring strain when any sort of jack was used to connect the overlap .
Finally , I used adhesive tape to join the ends of the tubes together , and this
provided the required flexibility for the banana orbital overlap , whose
connection angle is comfortably between trigonal and linear (probably ~ 160) :

The resulting S2N2 molecule , while rather crude , was approximately square . A
similar result was obtained when using trigonal planar jacks for the sulfur atoms .
However , a tetrahedral sp3 sulfur configuration is more realistic , occurring in a
great majority of organosulfur molecules . Trigonal planar sulfur is found in some
heterocyclic compounds , the best known of which is undoubtedly thiophene . A
possible reason for the minority of trigonal planar sulfur compounds compared to
tetrahedral sulfur ones is that the former configuration is probably less
energetically stable than the latter when completely filled with six electrons (as in
thiophene's sulfur) . There is more steric repulsion between the two lone pairs (one
axial , the other equatorial , 90) than in tetrahedral sulfur , in which the two lone
pairs are more widely spaced apart (109) [see the model above] . In the case of
thiophene , the aromatic stabilization energy it gains when its sulfur atom is
trigonal exceeds the energy stabilization it would have with a tetrahedral
configuration compared to being trigonal .
In the above model the singlet electrons in the nitrogen 2pz1 orbitals are shown
with opposite spins . This could result in an overall zero magnetic moment for
S2N2 , thereby making the compound diamagnetic , which is observed
experimentally .
The slightly curved SN banana bonds in the above model are weaker than
conventional sigma covalent bonds ; these attenuated bonds would cause S2N2 to
be thermally unstable , which is very much the case .

The concise overview by Evans and co-workers (2011) of various models of the
electronic structure of S2N2 deserves to be quoted at some length :
There is ........ the question of the bonding in S2N2 . It was first described with four
localized -bonds and six delocalized -electrons , in accordance with the Hckel
4n+2 rule . Numerous theoretical studies seeking to elucidate the structure have
found difficulty , however , in arriving at a clear consensus . Thus , the aromaticity
implicit in the earliest models has been countered by the resemblance of the
primary Lewis-type valence bond (VB) structure to a spin-paired diradical with a
long transannular NN bond . Yet , while favoring a singlet diradical description ,
spin-coupled VB theory calculations lend weight to the contrary view that the
diradical character is associated solely with two coupled -electrons , one from
each of the S atoms . More recently , though , various ab initio and DFT
calculations have been used to re-establish the case for aromaticity . In common
with the currently unknown analogues Se2N2 and SeSN2 , S2N2 should now be
described , according to the most recent analysis , as a 2-electron aromatic with
minor singlet diradical character of 68% that can be attributed solely to the N
atoms . High-level quantum chemical calculations have then been used to
reproduce molecular properties for the S2N2 molecule close to those determined
experimentally for the crystalline solid (p. 5127) .
Evans et al. refer to a long transannular NN bond ; a simple trigonometric
calculation (sketch of the physical structure of S2N2 , above) shows that the NN
distance in the molecule is 2.33 . The NN bond length in hydrazine , H2N
NH2 , is 1.45 ; in the nitrogen molecule , it's 1.0976 . The N=N double bond
length is approximately the average of the hydrazine single bond and nitrogen
triple bond lengths , i.e. 1.27 . The hypothetical N=N bond in S2N2 would
therefore have to be almost double that , which is very doubtful . Similarly , a
2.33 long S=S bond , as hypothesized by Gerratt and McNicholas (mentioned by
Evans et al.) , would be equally dubious .
It's also puzzling as to why sulfur atoms would transfer a valence electron to the
nitrogens , so as to have 3pz1 for the bond . Given that the Pauling
electronegativities of sulfur and nitrogen are 2.58 and 3.04 respectively , the SN
bond shouldn't even be very polar . The nearly similar electronegativities of sulfur
and nitrogen don't support the concept of electron transfer from S to N , or vice
versa . Of course , they don't rule out a pi bond , but given the 2.33 NN (or S
S) distance , that scenario seems unrealistic in S2N2 .
The overlapping of empty , higher energy level sulfur 4pz0 orbitals with the
nitrogen 2pz1 orbitals could form a pi MO cloud over the SN sigma bond
framework :

Two-electron resonance over the four atoms would produce a pseudo-aromatic pi

MO in the S2N2 molecule . It would result in diamagnetism in the compound , and
would add half a bond order to the single SN bond order . The 1.5 bond order
would result in a contraction of the SN bond length to the observed 1.654 , as
noted above by Mikulski and co-workers . The question must be posed , though :
how realistic is the use of the relatively high energy sulfur 4pz orbitals in the pi MO
?
It would be interesting to experimentally confirm the configuration of the sulfur
atoms : are they tetrahedral (my model) or trigonal planar (resonance model) ? If a
sulfur-selective electrophile could be found to complex with S2N2 as SbCl5 did
with its nitrogens , an X-ray analysis of the adduct's crystal structure could shed
some light on this question . For example , iron is known to bond strongly with
sulfur but weakly to nitrogen in forming coordinate covalent compounds .
Possibly iron pentacarbonyl would selectively bond to the sulfur atoms in S2N2 ,
forming an adduct somewhat similar to the known compound S2N2(SbCl5)2 :

In the above sketch the S2N2 has combined with two equivalents of Fe(CO)5 ,
displacing a CO ligand from each one to form the hypothetical compound
S2N2[Fe(CO)4]2 . The iron(0) atoms have a trigonal bipyramid coordination , as in
the Fe(CO)5 reagent . The adduct is shown with a non-linear (chair) structure ,
which might be observed if the sulfur atoms had a tetrahedral configuration , and
retained it in the formation of the adduct .
Update (added February 10th , 2012) : a revised electronic structure for
S2N2 combines features from both the resonance model with the 6 electrons
resonating in the four atom ring , and from the sp + p2 model discussed (and
rejected) above . In this latest version both the sulfur and nitrogen atoms have a s +
p2 + pz electronic configuration , as shown in the following sketch :

In this picture the sulfur 3pz lone pairs don't participate in the resonance ; rather ,
the nitrogen 2pz1 singlet electrons use their 3pz orbitals as a conduit to complete the
electrical circuit, so to speak , around the ring . As mentioned above , the SN
bond order is 1.5 , with the 4 SN covalent bonds providing a single order , and
the two resonating nitrogen singlet electrons in the MO providing the 0.5 bond
order . If the sulfur 3pz lone pairs participated in the MO , an additional full bond
order would have to be added to the structure , shortening the SN bond lengths to
~ 1.5 , which isn't observed in S2N2 . The nitrogen singlet electrons are thus only
piggybacking over the sulfur 3pz orbitals , which are energetically accessible and
have the correct shape , symmetry , and orientation for MO formation with the
nitrogen 2pz orbitals .
Positive attributes of this model are a rationalization of the square , flat structure of
the S2N2 molecule , of its diamagnetism , of the bond angles and bond lengths /
bond order , and of the possible pseudoaromatic 2 electron resonance . A negative
aspect of the model is the somewhat nondirectional nature of the sulfur and
nitrogen 3s2 and 2s2 lone pairs , respectively . The linear structure of the
S2N2(SbCl5)2 coordinate covalent adduct is difficult to reconcile with the spherical
shape of the the nitrogen 2s orbitals that would have to be used in forming the N
Sb bonds . Synthesis of a well-defined sulfur-selective SX coordinate covalent
complex of S2N2 , and the determination of its molecular structure by X-ray
crystallography , might provide some clues in the resolution of this question .

Tetrasulfur Tetranitride , S4N4

Brauer (pp. 406-408) describes S4N4 as a ..........

light yellow-orange solid at ordinary temperatures ; becomes light yellow at 30
C ; on heating to 100 C , orange-red ...... m.p. 178 C , b.p. ~ 185 C ; explodes at
> 185 C ....... readily soluble in benzene , CS2 , dioxane ; insoluble in water.
The Wikipedia article on S4N4 describes it as a vivid orange or golden-poppy
colored solid which melts at 187 C (this latter melting point is more applicable to
highly purified material) . Tetrasulfur tetranitride is thermally unstable , exploding
at its melting point , and is also mechanically unstable ; highly pure S4N4 crystals
are shock sensitive and will detonate if ground in a mortar . It's an insulator with an
electrical conductivity of RT = 10-14 ohm-1-cm-1 (Labes , Love , and Nichols , p. 2)
. It's also diamagnetic , with a magnetic susceptibility of mol = 102 x 10-6 cgsu
(Allen , Table 1 , p. 38) . S4N4 has an asymmetrical shape and a small dipole
moment ofp = 0.52 D resulting from its relatively nonpolar SN bonds .
Because of its unstable , explosive nature S4N4 isn't offered commercially , but
must be prepared by the researcher following a published synthesis procedure . The
preparations generally involve the reaction of sulfur monochloride or dichloride
with ammonia or ammonium chloride .
Tetrasulfur tetranitride has an remarkable folded molecular structure , usually
described as a cradle conformation :

This sketch was adapted from Fig. 1 , Bond Distances and Angles, by Sharma
and Donohue (p. 894) . My thanks to the copyright holder .
The NSN bond angles of 105 indicate that the sulfur atoms in S4N4 are
tetrahedral sp3, and are therefore electronically inert linking atoms in the molecule
. The SNS bond angles , at 113, are suggestive of a compressed trigonal planar
configuration for the nitrogen atoms . The arithmetic average of the eight SN
bond lengths in Sharma and Donohue's sketch is 1.616 .
The S4N4 molecule seems to be curled up, so to speak . In its hydrogen-reduced
analogue , tetrasulfur tetraimide [S4(NH)4] , the NSN bond angles = 109 , the
SNS bond angles = 123 , and the SN bond length averages ~ 1.673 . While
still somewhat puckered , the S4(NH)4 ring is flatter than the more rounded , folded
shape of S4N4 . Clearly , hydrogenation of the latter's nitrogens has broken some
bonds and has permitted a relaxation in the curled-up S4N4 form . The tetrahedral
and trigonal planar configurations of the sulfur and nitrogen atoms , respectively ,
are now very obvious in S4(NH)4 , and imply they are the same in S4N4 , while
being somewhat compressed in it because of its cradle shape .
As with S2N2 , I once again deployed my Framework Molecular Model kit and
began making various models of S4N4 . Despite the simplicity of these little models
or maybe becauseof it I was able to study the nitrogen atoms' 2pz orbital
overlap in various molecular configurations , with revealing results . In the first
model , the sulfurs are tetrahedral and the nitrogens are trigonal planar :

A top view of the molecule shows the neat symmetry of the banana bonds and
the square shape of the SN ring :

When the nitrogens are trigonal planar , their 2pz orbitals with the singlet fifth
electrons can overlap in a rather odd manner . The positive and negative symmetry
lobes can overlap tip-to-tip with corresponding orbital lobes on adjacent nitrogen
atoms , but in an alternating pattern above and below the molecular equator .
This 2pz orbital overlap should thus produce NN banana bonds around the
periphery of the molecule . There are four nitrogen 2pz valence electrons
resonating in the four sigma bonds ; therefore they could be considered asoneelectron bonds . These peculiar NN resonating one-electron bonds could have five
effects on the S4N4 molecule :
First , while they are expected to be very weak , they could nevertheless add a
small stabilizing secondary 0.5 bond order to it (the normal SN sigma covalent
bonds being the primary 1.0 bond order) . Note that while the nitrogen
2pz1 orbitals' overlap is sigma and not pi in nature , the continuous NNNN
daisy-chain nature of of the overlap would permit a delocalization of the four
2pz1 electrons around the perimeter of the molecule . This resonance could provide
some stabilization to S4N4 , if only of a partial bond order .
Second , this secondary bond order to S4N4 would result in a contraction of the
observed SN bond length from that in S4(NH)4 [1.673 , considered to be a
single SN bond] to that in S4N4 [1.616 , considered to be of a 1.5 SN bond
order ; see comments by Mikulski et al. , quoted above in the S2N2 section below
the S(II)S(IV) resonance sketch , and in theGritsan and co-workers reference
below] .

Third , the resonance would pair up the nitrogen atoms' singlet fifth electrons ,
thus resulting in diamagnetism in the compound , which has been observed
experimentally .
Fourth , these weak NN one-electron bonds would freeze the molecule into its
characteristic cradle shape . They could therefore be responsible for the peculiar
folded conformation of S4N4 ; and ,
Fifth , they might also be responsible for the observed thermochromism in the
material [as described by Brauer , quoted above] . Because the 2pz orbitals are
overlapping tip-to-tip , the resulting molecular orbital is sigma and will have nodes
around the nitrogen kernels . These nodal sigma MOs will impose a thermal
dependence on the electron resonance in them . An analogous situation occurs in
the semiconductors , whose electrical conductivity is similarly temperature
dependent , and which also have nodal metallic bonds . As S4N4 is cooled down ,
the 2pz1 electrons become more and more localized between the nitrogen kernels .
The color fades to a pale yellow . As it is heated , more and more of the energetic
electrons are able to tunnel through the nodes , and their resonance around the ring
increases . As the electron resonance strengthens , the solid's color intensifies to a
deep red at 100 C . As is well known in organic compounds , the stronger the
electron resonance is in the molecule , the more intense is its color . For example ,
such an increase in color is noted in the series of aromatic compounds , from
benzene and napthalene (colorless) through to tetracene (orange)
and pentacene (purple) . An extreme example of this phenomenon is provided by
polyacetylene , which has a bright silvery appearance and a metallic luster .
The addition of hydrogen atoms to S4N4 to form S4(NH)4 breaks these NN bonds
and permits the molecule to unfold into a flatter , if still puckered , eight-atom ring
. Pritchina and co-workers found evidence of a transitory cyclic eight-atom
compound corresponding to an unfolded form of S4N4 when its solution in hexane
is irradiated with UV light . S4N4 strongly absorbs the energetic UV energy at 254
nm , apparently resulting in a cleavage of the NN bonds .
Gopinathan and Whitehead [cited in various electronic structures] noted the
existence of a diamagnetic ring current in S4N4 , but attributed it to a SN pp resonance :
The diamagnetic ring current in S4N4 suggests electron delocalization around the
SN ring . From the LMOs the diamagnetic ring current is obviously due to the porbital lone pair electrons on nitrogen delocalizing into the p-orbitals on the sulfur
atoms to which it is directly bonded (p. 1347) .
In my model of S4N4 the diamagnetic ring current , originally observed by Mason ,
would be produced by the NN one-electron bonds resonating around the
molecule's perimeter . In the proposed model of the electronic structure

of poly(sulfur nitride) , there are similarly NN resonating one-electron bonds , but

the nitrogen fifth valence electrons are delocalizedthroughout the polymer chains
; the material is metallic as a result . In this model of S4N4 the NN one-electron
bonds are localized around its circumference , so tetrasulfur tetranitride is an
electrical insulator . A comparison can be made to benzene [insulator] , with
resonating but localized bonds , and graphite [metallic solid] , with resonating
and delocalized bonds .
In a second model of tetrasulfur tetranitride both the sulfur and nitrogen atoms
have a tetrahedral sp3 configuration :

The dihedral angle made by the NSN peaks relative to the square plane of the
four nitrogen atoms is exactly 90 (unfortunately this structural feature isn't shown
above in Sharma and Donohue's sketch of S4N4) . Thus , in this second model the
nitrogen axial sigma orbitals are precisely parallel in each of the two sets . If
each orbital has the fifth nitrogen singlet electron (the lone pairs are in the less
sterically-hindered equatorial lobes) , it might be possible for these two sets of
parallel lobes to overlap to form a type of molecular orbital .
Using the trigonometric formula a2 = b2 + c2 2bc cos A , with a = the NN
distance across the sulfur atom , b = c = 1.616 , and A = NSN = 105 , the
value for a = 2.5459 . As mentioned above , a typical NN single bond length

(as in hydrazine) would be ~ 1.45 , so the hypothetical NN sigma bond would

seem to be ruled out . If there actually were such bonds between the two sets of
nitrogens , they would be very diffuse and weak . Also , in this second model the
two NN bonds would be spatially isolated , and no diamagnetic ring current
would be observed in S4N4 .
There are at least five possible conformations for eight-atom rings :

This sketch was adapted from Fig. 3 , Some Configurations of the Eight Ring,
by Lu and Donohue (p. 821) . My thanks to the copyright holder .
I built Framework Molecular Models for all five of the S4N4 configurations , first
with trigonal planar nitrogens , and then again with tetrahedral nitrogen atoms in
the ring . The puckered X8 ring was the most interesting , because it's the usual
conformation of octosulfur S8 , which comprises the common and familiar
flowers of sulfur :

This image was copied from the Wikipedia web page , Sulfur. I thank the author
of this sketch , and Wikipedia , for implied permission to reproduce it on this web
page .
In a sense , S4N4 can be thought of as a derivative of S8 , with four sulfur atoms
replaced by four nitrogens . The molecular model clearly shows that no
overlapping of the nitrogens' 2pz orbitals with their singlet electrons are possible
when S4N4 is in this conformation :

A top view of the puckered conformation of S4N4 shows the symmetrical ring and
the nitrogen 2pz orbitals :

The tub and chair conformations of S4N4 were equally unsuccessful with respect to
any possible overlapping of the nitrogen 2pz orbitals . The butterfly conformation
permitted a possible overlap of either the + or lobes of the 2pz orbitals separately
, but not both simultaneously .
The curled-up cradle conformation is the only one having the essential four coplanar nitrogen atoms and the correct orientation of those nitrogens so that a
complete and proper (if somewhat unusual) overlap of the nitrogen 2pz orbitals is
possible . It could be that in the formation of S4N4 the ring undergoes the various
conformations examined ; when it curls into the cradle conformation the NN
2pz12pz1 one-electron bonds form and the molecule is locked into that
configuration .
Sharma and Donohue sketched two models that were then (1963) considered as
reasonable candidates for the molecular structure of S4N4 :

This sketch was adapted from the illustration on p. 891 in the article by Sharma
and Donohue . My thanks to the copyright holder .
The co-planar sulfur atoms model was appealing because both the sulfurs and the
nitrogens had the correct valences , the latter with the familiar three covalent bonds
. In the co-planar nitrogen atoms model the sulfurs had the conventional divalent
sulfur , but also required the strange and perplexing N . Sharma and Donohue's
painstakingly careful X-ray analysis of S4N4 (see their sketch above) validated
beyond any doubt the co-planar nitrogens model .
Ten years earlier (in 1953) , Lippincott and Tobin had carried out a meticulous
infrared and Raman spectroscopic analysis of S4N4 . They assigned the 925 cm-1 IR
absorption band , and the 888 and 934 cm-1 Raman bands , to the NN bond
stretching frequency , by analogy with that in hydrazine (at 893 cm-1, Raman) :

This sketch was adapted from Fig. 3B , p. 1560 in the article by Lippincott and
Tobin . My thanks to the copyright holder .
The absorption bands assigned to the NN bond stretching frequency in S4N4 were
entirely absent in the IR and Raman spectra of a co-analysed sample of S4(NH)4 .
They remarked ,

We are now in a position to see why the reduction products of nitrogen

tetrasulfide never contain NN bonds . The fact that the infrared spectrum of
nitrogen hydrogen sulfide very closely resembles that of nitrogen tetrasulfide in the
region 250-1000 cm-1 makes it appear probable that the skeleton is intact and that
the NN bonds of nitrogen tetrasulfide were broken to form NH bonds . In other
words , the NN bonds were attacked more readily than the NS bonds (p. 1563) .
A decade after Lippincott and Tobin's report Sharma and Donohue conclusively
solved the molecular structure of S4N4 and thereby completely discredited the coplanar sulfur atoms model , which contained the NN bonds . Thereafter , any
subsequent studies of tetrasulfur tetranitride either didn't mention the possibility of
NN bonds in the compound , or even specifically refuted the concept . For
example , Bragin and Evans (1969) studied the Raman and infrared spectra of both
S4N4 and S2N2 ; their IR spectrum of S4N4 was quite similar to that of Lippincott
and Tobin . While they detected the strong 925 cm-1 band in the solid [Nujol mull]
IR spectrum first observed by Lippincott and Tobin , they didn't provide an
assignment for it . The the nearby 938 cm-1 band (dioxane solution) was assigned
to a SN stretching mode . Bragin and Evans made no mention at all of NN bonds
in S4N4 . They did suggest the possibility of a non-bonded SS interaction in the
molecule :
....for the nonbonded SS interaction a repulsive force constant in the range 1.131.36 was obtained . This value is comparable to that of the main force constants
of the molecule and supports the view that the nonbonded SS repulsion plays a
significant role in the molecular potential field of S4N4 (pp. 274-275) .
Touzin (1981) also carried out a Raman and infrared spectroscopic analysis of
S4N4 ; he reported a band at 937 cm-1 , but assigned it to a ring vibration . He also
found absorption bands at 180 and 213 cm-1 , and assigned them to SS bond
stretching . No mention was made of the 925 cm-1 band observed by previous
researchers .
SS bonds in S4N4 , if only weak and of thin density , are now considered almost
conventional . Modern-day sketches of the compound often have a dashed line
connecting the opposite pairs of sulfur atoms in the illustrations . As pointed out
earlier , the NSN bond angles in both S4N4 and its relaxed , unfolded analogue
, S4(NH)4 , are strongly indicative of a tetrahedral configuration of the sulfur atoms
in these compounds . Tetrahedral means sp3 ; sp3 means two covalent SN bonds
plus two lone pairs ; and that means the sulfur atoms are just electronically inert
linking atoms in S4N4 and S4(NH)4 . If anything the sulfur lone pairs should
produce some repulsion , not bonding (cf. Bragin and Evans' comment above) ,
between the two opposed pairs of sulfur atoms in the ring .
Unfortunately , when the co-planar sulfur atoms model of S4N4 was discredited by
Sharma and Donohue in 1963 , the idea of NN bonds in the compound was also

discarded . Perhaps the concept might be revisited , but within the framework of
the correct molecular structure of tetrasulfur tetranitride . The model having NN
2pz12pz1 resonating one-electron bonds with the unusual banana type of overlap
could be a good starting point for a renewed investigation of the chemical bonds in
tetrasulfur tetranitride :

It might be quite difficult , though , to experimentally verify the existence of the

four NN one-electron bonds . They are undoubtedly thin and feeble , and would
contribute only half of a bond order to the molecule . Their IR absorption might be
minor (or nil) , and could easily be masked by the overwhelming SN bond
frequencies and ring flexing and bending . There is also the unresolved question of
the 925 cm-1 band in the IR absorption spectrum of S4N4 . Is it genuine , i.e.
reproducible , and can it really be attributed to the NN bond stretching frequency
? And are there really SS bonds in the compound ?
In the companion web page to this one , Three Models of the Metallic Bond in
Poly(sulfur nitride), the instrumental technique of ARPES/ARPUS (angleresolved photoelectron/ultraviolet spectroscopy) was suggested as a possible
method of determining the nature of the metallic bond orbitals in (SN) x . ARPES
might also be used to detect the hypothetical NN resonating one-electron bonds in
tetrasulfur tetranitride . They are expected to be at a higher energy level , and
physically outside , the stronger SN sigma covalent bonds .

Would the somewhat fragile NN bonds survive in the ARPES/ARPUS

experimental environment ? Recall Pritchina and co-workers' photolysis
experiments with S4N4 , in which the molecule strongly absorbed the UV light and
unfolded into an unstable , puckered eight-atom ring . This transient intermediate
in turn rearranged into a six-atom ring with a SN attachment : a SN analogue of
styrene . The ARPES/ARPUS energy input into the S4N4 test sample might well
overstress its delicate chemical stability .
The essence of the scientific method is the experimental testing of models . Those
of the chemical bonding in S2N2 and S4N4 discussed above provide a simple , fresh
, new approach to understanding the electronic structures of these two compounds .
I hope this essay with its admittedly unorthodox ideas will be thought-provoking ,
and will stimulate more experimental study of S2N2 and S4N4 in the ongoing effort
of resolving the long-standing puzzle of their chemical bonding .

References , Notes , and Comments

various electronic structures : A brief summary of various theoretical studies of the

electronic structure of S4N4 is provided by W.R. Salaneck et al. , Direct
Determination of the Electronic Structure of S4N4 by X-ray and Ultraviolet
Photoemission, Phys. Rev. B 13 (10) , pp. 4517-4528 (1976) ; p. 4524 . These
researchers observed a transfer of electron density from the sulfurs to the nitrogens
:
The X-ray photoemission spectra of the N(1s) and S(2p) core levels , when
compared with those of charge neutral atoms in N2 and S8 molecules , respectively
, indicate an effective charge transfer of about one-half of an electronic charge
from the sulfur atoms to the nitrogen atoms (p. 4526) ;
A.G. Turner and F.S. Mortimer , On the Electronic Structure of Tetranitrogen
Tetrasulfide, Inorg. Chem. , 5 (5) , pp. 906-910 (1966) . They emphatically
declared :
Lippincott and Tobin assigned the coplanar sulfur structure on the basis of the
occurrence of a Raman line at 888 cm-1 corresponding to an NN bond (to be
compared with a line at 893 cm-1 for N2H4) .The molecular orbital calculations ,
SCCMO , show absolutely no tendency for bonding between nitrogen atoms since
the calculated overlap population between nitrogen atoms is negative or zero under
all parametizations . Hence , both experiment and theory argue against a structure
containing a NN bond (p. 907) ;

M.S. Gopinathan and M.A. Whitehead , The Electronic Structure and Localized
Molecular Orbitals in S4N4 by the CNDO/BW Theory, Can. J. Chem. 53 (9) , pp.
1343-1347 (1975) [PDF , 328 KB . Note : this file can be opened only with Adobe
Acrobat Reader v. 6 or later . If desired , this application can be downloaded for
free from Oldversion.com] . They concluded ,
S4N4 has a molecular structure with coplanar nitrogen atoms . The electronic
formula for the molecule is the polar Lewis structure B [on p. 1344] . There is no sp hybridization at nitrogen or sulfur . The NS and SS bonds are bent single
bonds involving pure p-orbitals . There is no NN bond . Electron delocalization
occurs by delocalization of the p-electrons in a nitrogen lone pair to the p-orbitals
on the sulfur atoms to which the nitrogen is bonded (p. 1347) ;
D.R. Salahub and R.P. Messmer , A Study of the Electronic Structures of SN ,
S2N2 , S4N4 , NO , and N2O2 and Their Implications for (SN)x, J. Chem.
Phys. 64 (5) , pp. 2039-2047 (1976) ;
R.H. Findlay et al. , Electronic Structure of the Sulfur Nitrides . Ab Initio
Calculations and Photoelectron Spectra, Inorg. Chem. 19 (5) , pp. 1307-1314
(1980) . These authors concluded that the localized molecular orbitals i.e.
roughly corresponding to a Valence Bond description in S4N4 consists of 8 SN
bonds , 2 SS bonds , 4 lone pairs on the sulfurs (one pair each) , and 8 lone pairs
on the nitrogens (2 pairs each) ; see Table VII , p. 1314 . Their figure 8 on p. 1314
shows an ionic S4N4 molecule , with full positive charges on the sulfurs and full
negative charges on the nitrogens . Such a structure would be strongly polar and
would have a large dipole moment . However , Rogers and Gross (dipole moment ,
below) found that S4N4 was relatively nonpolar , with a dipole moment of p = 0.52
D , as mentioned above . Water and many polar organic solvents have dipole
moments several times that . The solubility of S4N4 in relatively non-polar solvents
such as benzene , dioxane , and CS2 , and its insolubility in water , are consistent
with a non-polar , un-ionized molecular structure . These observed polarity
properties of S4N4 suggest that resonance structures involving charge transfer from
sulfur to nitrogen or vice versa , resulting in partial or full ionic charges on the
atoms , are unlikely .
R.D. Harcourt , T.M. Klaptke , A. Schulz , and P. Wolynec , On the Singlet
Diradical Character of S2N2, J. Phys. Chem. A , 102 (10) , pp. 1850-1853 (1998)
. Resonance structures for S2N2 .
Brauer : G. Brauer (ed.) , Handbook of Preparative Inorganic Chemistry ,
2nd edition , vol. 1 , Academic Press , New York , 1963 ; S2N2 , pp. 409-410 ;
S4N4 , pp. 406-408 .

Mikulski and co-workers : C.M. Mikulski et al. , Synthesis and Structure of

Metallic Polymeric Sulfur Nitride , (SN)x , and Its Precursor , Disulfur Dinitride ,
S2N2, J. Amer. Chem. Soc. 97 (22) , pp. 6358-6363 (1975) .
Gritsan and co-workers : N.P. Gritsan et al. , Matrix Isolation and Computational
Study of the Photochemistry of 1,3,2,4-Benzodithiadiazine, J. Phys. Chem.
A 111 (5) , pp. 817-824 (2007) [PDF , 300 KB] . These researchers calculated SN
and S=N bond lengths of 1.71 and 1.56 , respectively , in the title compound
(Figure 8 , p. 823) :

X-ray diffraction demonstrates : R.L. Patton and K.N. Raymond , The Crystal and
Molecular Structure of S2N2(SbCl5)2, Inorg. Chem. 8 (11) , pp. 2426-2431 (1969)
.
Evans and co-workers : R. Evans , A.J. Downs , R. Kppe , and S.C. Peake
, Vibrational Properties of the Disulfur Dinitride Molecule , S2N2 : IR and Raman
Spectra of the Matrix-Isolated Molecule, J. Phys. Chem. A 115 (20) , pp. 51275137 (2011) .
iron pentacarbonyl : S2N2 could conceivably form a dithiolene type of adduct with
iron pentacarbonyl :

Perhaps more effective sulfur-selective candidate electrophiles for preparing

S2N2 coordinate covalent adducts might be heavy metal cations such as silver(I)
[5s0] and mercury(II) [6s0] . These two cations in particular are well-known for
having especially strong affinities for sulfur , certainly much more so than for
nitrogen . Both silver(I) perchlorate , AgClO4 , and mercury(II) chloride , HgCl2 ,
are soluble in various organic solvents (MeOH , EtOH , benzene , and acetone ;
possibly also in ethyl ether and THF) . S2N2 is soluble in ethyl ether and maybe it
dissolves in the other organic solvents mentioned without reaction or
decomposition . Insoluble coordination compounds might precipitate from the
combination of Ag1+ and Hg2+ with S2N2 in a suitable anhydrous organic solvent .
mechanically unstable : A.F. Cotton , G. Wilkinson , C.A. Murillo , and M.
Bochmann , Advanced Inorganic Chemistry , 6th edition , John Wiley , New York ,
1999 :
The compound [S4N4] must be handled with care , since grinding , percussion ,
friction , or rapid heating can cause it to explode (p. 509) . S4N4 is discussed on
pp. 509-511 .

Labes , Love , and Nichols : M.M. Labes , P. Love , and L.F. Nichols , Polysulfur
Nitride A Metallic , Superconducting Polymer, Chem. Rev. 79 (1) , pp. 1-15
(1979) .
Allen : C.W. Allen , The Chemistry of Tetrasulfur Tetranitride, J. Chem.
Educ. 44 (1) , pp. 38-44 (1967) .
dipole moment : M.T. Rogers and K.J. Gross , The Electric Moments of Some
Sulfur and Selenium Compounds, J. Amer. Chem. Soc. 74 (21) , pp. 5294-5296
(1952) .
synthesis procedure : M. Becke-Goehring , Sulfur Nitrides, Inorg. Synth. 6 , pp.
123-128 , E.G. Rochow et al. (eds.) , McGraw-Hill , New York , 1960 ; M.
Villena-Blanco and W.L. Jolly , Tetrasulfur Tetranitride, Inorg. Synth. 9 , pp.
98-102 , L.F. Audrieth et al. (eds.) , McGraw-Hill , New York , 1967 ; W.L. Jolly
, Synthetic Inorganic Chemistry , Prentice-Hall , Englewood Cliffs (NJ) , 1960 ;
pp. 166-168 ; idem. , The Synthesis and Characterization of Inorganic
Compounds , Prentice-Hall , Englewood Cliffs (NJ) , 1970 ; pp. 500-502 . The
actual sulfur precursor for S4N4 is sulfur dichloride , SCl2 , a corrosive ,
lachrymatory , viscous , red liquid , b.p. 60 C . It's somewhat unstable and is
difficult to obtain pure , so in practice the sulfur source usually employed in
S4N4 syntheses is the stable sulfur monochloride [disulfur dichloride] , S2Cl2 . This
latter chemical is a yellow-red , oily liquid , b.p. 137 C , and is also corrosive and
lachrymatory like SCl2 . Sulfur monochloride is chlorinated in situ to SCl2 in the
initial stages of the S4N4 preparation . S2Cl2 (98% reagent grade) is offered
commercially , eg. by the Aldrich Chemical Company .
Sharma and Donohue : B.D. Sharma and J. Donohue , The Crystal and Molecular
Structure of Sulfur Nitride , S4N4, Acta. Cryst. 16 (9) , pp. 891-897 (1963) .
tetrasulfur tetraimide : D. Gregson , G. Klebe , and H. Fuess , Charge Density
Distribution in Tetrasulfur Tetraimide (S4(NH)4), J. Amer. Chem. Soc. 110 (25) ,
pp. 8488-8893 (1988) . See esp. Figure 5 , p. 8492 for a sketch of S4(NH)4 showing
its bond lengths and angles .
one electron bonds : L. Pauling , The Nature of the Chemical Bond and the
Structure of Molecules and Crystals , 3rd ed. , Cornell University Press , Ithaca
(NY) , 1960 ; p. 340 ; A. Holden , The Nature of Solids , Dover Publications , New
York , 1992 [reprint of the Columbia University Press textbook , 1965] ; p. 91 .
Pritchina and co-workers : E.A. Pritchina , N.P. Gritsan , A.V. Zibarev , and T.
Bally , Photochemical Study on the Reactivity of Tetrasulfur Tetranitride ,
S4N4, Inorg. Chem. 48 (9) , pp. 4075-4082 (2009) [PDF , 404 KB] .

Mason : J.B. Mason , Electronic Structure of Tetrasulphur Tetranitride , S4N4, J.

Chem. Soc. A 1969 , pp. 1567-1570 . I've only read the abstract of this paper , and
unfortunately have been unable to access its full text .
Lu and Donohue : C-S. Lu and J. Donohue , An Electron Diffraction Investigation
of Sulfur Nitride , Arsenic Disulfide (Realgar) , Arsenic Trisulfide (Orpiment) and
Sulfur, J. Amer. Chem. Soc. 66 (5) , pp. 818-827 (1944) .
various conformations : The SN compounds may be fluxional to a certain extent .
One of the best known examples of a fluxional molecule is that of iron
pentacarbonyl , mentioned above . Fe(CO)5 flip-flops to and from the trigonal
bipyramid and square pyramid structures . In Valence Bond terms these structures
correspond respectively to the sp3dz2 and the sp3dx2-y2 hybrid orbitals on the iron
atom . Since the iron 3dz2 and 3dx2-y2 orbitals are at the virtually same energy level
in the molecule , the hybrid orbitals can readily change to and from sp 3dz2 and
sp3dx2-y2 . As they change back and forth , the iron pentacarbonyl structure
correspondingly flips back and forth (the flip-flopping has the technical name of
the Berry mechanism) .
S2N2 , S4N4 , and (SN)x may behave in somewhat the same way , at least in their
formative stages . The sulfur atoms are most thermodynamically stable in their
tetrahedral sp3configuration , as mentioned above . The nitrogen atoms may try out
several different configurations : sp3 , sp2 + pz , s + p3 , and so on . S4N4 may also
try out the various ring conformations , as discussed above . Finally , when the
most stable electronic configurations and structural conformations have been
achieved , the molecule is frozen into its familar form . When S4N4 folds into its
cradle shape , the NN bonds form and the molecule locks up . When the
nitrogens in (SN)x try out the s + p3 configuration , the metallic bond forms along
the polymer spines and it's frozenas a metallic solid .
Lippincott and Tobin : E.R. Lippincott and M.C. Tobin , The Vibrational Spectra
and Structure of Nitrogen Tetrasulfide, J. Chem. Phys. 21 (9) , pp. 1559-1565
(1953) .
with that in hydrazine : P.A. Gigure and I.D. Liu , On the Infrared Spectrum of
Hydrazine, J. Chem. Phys. 20 (1) , pp. 136-140 (1952) . These researchers stated ,
Finally the NN fundamental vibration 5 is expected to be weak in infrared since
it involves an essentially nonpolar bond . In addition , it falls in a region of strong
absorption from the NH wagging modes . No definite evidence of it was observed
in the spectrum of the vapor , but in the liquid a remarkably strong maximum at
873 cm-1 corresponds to a Raman line of moderate intensity at 876 cm-1 . This
frequency seems a little low compared to the OO vibration in hydrogen peroxide
(877 cm-1) and the CN vibration in methylamine (1045 cm-1) . From electron
diffraction and x-ray data the NN bond length in hydrazine is known to be 1.46

; application of Badger's rule yields about 960 cm-1 for the corresponding
frequency . Values of 816 and 801 cm-1, respectively , have been found for it in
methylhydrazine and sym-dimethylhydrazine , the gradual decrease in frequency
being caused by an increase in the reduced mass of the vibrating groups (p. 140) .
J.C. Decius and D.P. Pearson , The Infrared Absorption of Crystalline and Liquid
Hydrazine Monochloride and Monobromide, J. Amer. Chem. Soc. 75 (10) , pp.
2436-2439 (1953) . These authors found a somewhat higher value for the NN
bond stretch absorption in hydrazine hydrochloride :
For N2H5Cl , this region may be expected to include the NN stretch , a torsional
vibration and the lattice modes . In agreement with Edsall and Scheinberg , we
assign 973 cm-1(which shifts only to 940 cm-1 in N2D5Cl) as the NN stretch (p.
2438) .
Bragin and Evans : J. Bragin and M.V. Evans , Vibrational Spectra and Structure
of S4N4 and S2N2, J. Chem. Phys. 51 (1) , pp. 268-277 (1969) ; see esp. Table I ,
p. 270 .
Touzin : J. Touzin , Vibration Spectra of Sulfur Tetranitride, Coll. Czech. Chem.
Commun. 46 (11) , pp. 2613-2619 (1981) ; see esp. Table 1 , p. 2615 .
SS bond stretching : R.M. Silverstein , F.X. Webster , and D.J. Kiemle
, Spectrometric Identification of Organic Compounds , 7th edition , John Wiley ,
New York , 2005 :
Disulfides : The SS stretching vibration is very weak and falls between 500 and
400 cm-1 (p. 106) .
N.B. Colthup , L.H. Daly , and S.E. Wiberly , Introduction to Infrared and Raman
Spectroscopy , 3rd edition , Academic Press , Boston (MA) , 1990 . In organic
disulfides the SSstretching frequency exhibits a weak band at 500 cm-1 (p. 371) .
On the web page , Infrared Spectroscopy , the SS absorption is listed as having a
weak band in the 500-540 cm-1 range in the Other Functional Groups tabulation .
No mention of NN IR frequencies was made in these three references , nor in any
other IR spectroscopy reference I consulted (eg. in the CRC Handbook of
Chemistry and Physics) .
tetrahedral configuration : Salaneck and co-workers [various electronic
structures above] noted :
From the chemical perspective , sulfur in S4N4 corresponds to sp3 hybridization .
The NSN bond angle is about 105, and thus a small amount of S(3d) mixing is
necessary to account for the geometry (p. 4521) . I don't agree with this ; the

slight (4)compression of the NSN bond angles can be accounted for by the
steric compression of the two lone pairs on the sulfurs , and by the curled ,
compressed geometry of the S4N4 molecule in general . The 3d orbitals in sulfur
are rarely , if ever , used in chemical bonding . See my discussion of this in another
Chemexplore web page .
In a Valence Bond analysis the sulfur atoms in S4N4 simply have a tetrahedral
sp3 configuration . The trigonal planar hybrid orbital is less energetically favorable
for sulfur than the tetrahedral one unless it is involved in an aromatic resonance (as
in thiophene) , which doesn't occur in S4N4 . Other hybrid orbitals , such as the
trigonal bipyramid sp3d hybrid , are also unsatisfactory for the sulfur atoms .
The concept of SS bonding in S4N4 is derived from the Molecular Orbital Theory
. In MO analyses the sulfur atoms have higher energy orbitals which can overlap to
form weak SS bonds :
Perhaps the most significant feature of the frontier orbitals is the effect of the
weak SS interaction on the wave functions and the corresponding orbital energies
. The weak SS (4b2) bonding orbital has the lowest ionization potential of any
filled orbital . In particular , this highest occupied MO contains almost 70% of its
charge density in the SS bonding portion of the wave function . The lowest
unoccupied MO , on the other hand , contains over 80% of its charge density in the
corresponding SS antibonding portion of the wave function(Salaneck et al. , p.
4524) .

Three Models of the Metallic Bond in Poly(sulfur nitride)

[ Index Page ] [ Contact ]

Composition of Stars and Planets

Composition of the Crust

Eight elements make up 99 per cent of the crust. Note how rare many industrial
metals are.

Minerals are the Chemicals that make up the Earth

NATURALLY-OCCURRING
INORGANIC
CHEMICAL COMPOUNDS
ABOUT 3000 KNOWN
200 COMMON
20 ROCK-FORMING
MINERALOIDS
Term for mineral-like materials that don't quite fit the full definition of minerals,
including:

Non-crystalline materials (opal, some hydrocarbons)

Organic rock materials
Substances that are mixtures of several minerals on a microscopic scale (limonite,
bauxite)

Atomic Bonding
1. IONS

Normal Configurations: Sodium: 11 p+, e-; Chlorine: 17 p+, eYou may have heard that the pictures above are not really accurate. If you want
to know more, you can visit
What Do Atoms Really "Look Like?" (optional)

ELECTRON SHELL STRUCTURE

Most stable arrangement: 8 e- in outermost shell

Noble gases (Ar, Ne, etc.) have that arrangement naturally and rarely combine
with anything else.
Sodium: Loses electron, has 11p+, 10e-, charge +1: becomes a cation
Chlorine: Gains electron, has 17p+, 18e-, charge -1: becomes an anion
Many elements would have to gain or lose too many electrons and settle for
other electron structures instead.
2. ELECTRICAL NEUTRALITY
(+) and (-) Cancel Out
3. BONDING (SATISFY 1 & 2)

Ionic (NaCl)
Covalent (O2)

Metallic (Cu, Al, Fe)

Hydrogen (in water)
Ionic and Covalent Bonding

o
o
o
o
o

o
o

Ionic Bonding
Some atoms gain electrons to become anions
Others lose electrons to become cations
Ions are attracted by their opposing charges
Electrical Neutrality Maintained
Most Important Bonding in Rocks and Minerals
Covalent Bonding
Electrons share electrons to fill incomplete shells
Most Important Bonding in Organic Materials (and Organisms)
Metallic Bonding

A. Outermost electrons wander freely through metal. Metal consists of cations

held together by negatively-charged electron "glue."
B. Free electrons can move rapidly in response to electric fields, hence metals are
a good conductor of electricity.
C. Free electrons can transmit kinetic energy rapidly, hence metals are good
conductors of heat.
D. The layers of atoms in metal are hard to pull apart because of the electrons
holding them together, hence metals are tough. But individual atoms are not held
to any other specific atoms, hence atoms slip easily past one another. Thus metals
are ductile. Metallic Bonding is the basis of our industrial civilization.
Hydrogen Bonding

Hydrogen Bonding is Geologically Important

A. Water molecules are asymmetrical. The positively-charged portions of one are

attracted to the negatively-charged parts of another. It takes a lot of energy to
pull them apart. Hence:

Water melts and boils at unusually high temperatures for such a light molecule.
Water has a high heat capacity.
It takes a lot of energy to melt ice and vaporize water.
Thus water is the principal heat reservoir on the Earth.
B. The asymmetrical charge distribution on a water molecule makes it very
effective in dissolving ionically-bonded materials. However, it is not an effective
solvent of covalently bonded materials (oil and water don't mix). Hence:

Water is very effective at weathering rocks and minerals. It is the closest thing to
a universal solvent.
Water is very effective at transporting ions and dissolved nutrients in the human
body.
Water is not an effective solvent of organic molecules. Thus we do not dissolve in
our own cell fluids. Nifty feature.
C. When water freezes, it assumes a very open structure and actually
expands. Most materials shrink when they freeze and sink in their liquid phases.
Implications:

If ice sank like most frozen solids, it would accumulate at the bottoms of frozen
lakes and seas. Most of the world's water would be ice.
Expansion of ice in rocks is a powerful weathering agent.

Summary of Bonding

Ionic bonding holds rocks and minerals together

Covalent bonding holds people and other organisms together
Metallic bonding holds civilization together
Hydrogen bonding gives water its heat-retaining and solvent properties
4. LATTICE
Usually anions are bigger (They form framework and cations fill in spaces
between). Thus it is often possible to remove one cation and replace it with
another. Below, both halite (NaCl) and sylvite (KCl) have identical atomic
structures and similar physical properties. They can be distinguished by their taste
- sylvite is very bitter, somewhat like licking a belt sander. Those of you who have
used so-called "light salt" know.
At right, a rubidium atom has substituted for potassium. Some elements, like
rubidium, have no minerals of their own and occur in nature almost entirely by
substituting for more common elements. In many minerals, this substitution
occurs to such an extent that the mineral can be considered to consist of mixture
of two or more ideal compounds. Such mixtures are called solid solutions.

5. RADICALS

Radicals are groups of atoms that behave

as single units. Three of the most
common are shown at left.

NAMING MINERALS
COLOR

Albite (Latin: Albus = White)

Rhodonite (Greek: Rhodon = Rose)
Glauconite (Greek: Glaucos = Blue-green)
Azurite
OTHER PROPERTIES, USES

Magnetite
Orthoclase (Straight + Break)
Microcline (Small + Angle)
Pyrophyllite (Fire + Leaf)
Fluorite (Latin: Fluere - to Flow)
Graphite (Greek: Graphos - Writing)
COMPONENTS

Magnesite
Chromite
Cuprite
Siderite (Greek: Sideros - Iron)
Calcite
PLACES

Aragonite
Muscovite (Moscow)
Turquoise (Turkey)

Andalusite
Labradorite
PEOPLE

Scheelite
Sillimanite
Biotite
Cordierite
Wollastonite

CHEMICALS (AND MINERALS) ARE CLASSIFIED BY THEIR

ANIONS
For Example: Iron Compounds Have Little in Common

Fe: Gray, Metallic

FeCl2: Light Green, Water Soluble
FeSO4: Light Green, Water Soluble
FeCO3: Brown, Fizzes in Acid
FeS2: Dense, Brittle, Metallic, Cubic Crystals
On the Other Hand, Sulfides have Many Properties in Common

FeS2
CuS2
PbS2
ZnS2
All are Dense, Brittle, Metallic, have Cubic Crystals

IDENTIFYING MINERALS

o
o

COLOR -Sometimes Distinctive

Often Unreliable
Affected By
Chemical Impurities
Surface Coating
Grain Size
Weathering


o
o

o
o

o
o
o

o
o
o
o
o

o
o
o

o
o
o
o

o
o

o
o
o

HARDNESS
Resistance to Scratching
Directly related to relative strength of atomic bonds
DENSITY
Directly related to masses of component atoms and their spacing
Usually very consistent
LUSTER
Metallic or Nonmetallic is the most important distinction.
Resinous, waxy, silky, etc. are self-explanatory.
Vitreous is often used for glassy luster.
CLEAVAGE
Tendency to split along smooth planes between atoms in crystal
Thus directly related to atomic structure
Related to Crystal Form
Every cleavage face is a possible crystal face
Not every crystal face is a cleavage face. Quartz commonly forms crystals but
lacks cleavage.
CRYSTAL FORM
Takes Luck & Practice
Well-formed crystals are uncommon
Crystal Classification is somewhat subtle
FRACTURE
GEOLOGIC SETTING
Some minerals occur in all geologic settings: quartz, feldspar, pyrite
Some minerals occur mostly in sedimentary settings: calcite, dolomite
Some minerals occur mostly in igneous settings: olivine
Some minerals occur mostly in metamorphic settings: garnet, kyanite
SPECIAL PROPERTIES
Taste, Magnetism, Etc.
Don't try on every mineral, but will quickly identify or rule out specific minerals.
EXPERIENCE AND READING
PROFESSIONAL METHODS
Chemical Analysis
X-Ray Studies
Thin Section

HARDNESS

Scratch Test (MOHS)

Indentation Test (KNOOP) - a more accurate scale used by metallurgists and

engineers
Common Errors due to

Weathering, Chalk' marks

Breaking vs. Scratching
MOHS vs. KNOOP Scales

1. Talc: very small

2. Gypsum, Fingernail: 30
3. Calcite, Penny: 135
4. Fluorite: 163
5. Apatite: 430
6. Feldspar, Glass: 560
7. Quartz: 820
8. Topaz: 1340
9. Corundum: 2100
10. Diamond: 7000

DENSITY - gm/cm3
weight relative to water
Air: 0.001
Wood - Balsa: 0.1, Pine: 0.5, Oak: 0.6-0.9
Gasoline: 0.7, Motor Oil: 0.9
Ice: 0.92
Water: 1.00
Sugar: 1.59
Halite: 2.18
Quartz: 2.65
Most Major Minerals: 2.6-3.0
Aluminum: 2.7
Pyrite, Hematite, Magnetite: 5.0
Galena: 7.5
Iron: 7.9
Copper: 9
Lead: 11.4
Mercury: 13.6

Uranium: 19
Gold: 19.3
Platinum: 21.4
Iridium: 22.4 (densest material on Earth)

MAJOR MINERAL SUITES

ELEMENTS

Metallic:Au, Ag, Cu
Not Al, Pb, Zn, Fe, etc.
Nonmetallic: C - Diamond, Graphite
Sulfur
SULFIDES
Dense, Usually Metallic
Many Major Ores

Pyrite FeS2
Chalcopyrite CuFeS2
Galena PbS2
Sphalerite ZnS2
Molybdenite MoS2
HALIDES
Usually Soft, Often Soluble

Halite NaCl
Fluorite CaF2
SULFATES
Soft, Light Color

Gypsum CaSO4
Barite BaSO4
OXIDES
Often Variable, Some Ores

Hematite Fe2O3
Bauxite Al (OH)3 (a hydroxide)
Corundum Al2O3 (Ruby, Sapphire)
CARBONATES
Fizz in Acid, Give off CO2

Calcite CaCO3
Dolomite CaMg (CO3)2

MOST IMPORTANT MINERAL SUITE:

The Silicate Minerals

Si + O = 75% of Crust
Silicates make up 95% + of all Rocks
SiO4: -4 charge
Link Corner-To-Corner by Sharing Oxygen atoms
Nesosilicates - Isolated Tetrahedra
In the sketches, the O's represent oxygen atoms. The tetrahedra are viewed from
above, and the Si atom would be below the central O atom. These are schematic
only, the actual three-dimensional arrangement is more complex.
Red circles denote other cations between the
tetrahedra. The silica unit behaves like any
other radical. The clue to a nesosilicate is
SiO4 in the chemical formula.
Representatives:

Sorosilicates - Paired Tetrahedra

Olivine
Garnet
Kyanite

Epidote is the most

common mineral of this
type. The pair of
tetrahedra has the
formula Si2O7

Cyclosilicates - Rings
Minerals with three, four,
and six-sided rings are
known. Examples of the
rare three- and four-sided
rings are at top. Six-sided
rings are most common.
The ring unit has the
formula Si(x)O(3x) where
x is the number of
tetrahedra in the ring. Six
sided rings thus have the
formula Si6O18. The most
common are:

Inosilicates - Chains
Single Chains

Beryl (Emerald - bottom

left)
Tourmaline (bottom
right)

The ratio of silicon

to oxygen is 1:3, so
these minerals
have formulas with
SiO3 or some
multiple.
Pyroxenes have
this structure.
Related minerals,
called pyroxenoids,
have single, but
twisted, chains

Double Chains

These minerals, the

amphiboles, have
Si4O11 in their
formula. A few triplechain minerals are also
known.

Phyllosilicates - Sheets

These minerals have Si2O5 in

their formulas. The silica sheets
are sandwiched with layers of
magnesium and aluminum
hydroxide, water, and other
cations. There are many
possible structures formed by
the various layering possibilities
but the main groups are:

Micas
Clay minerals
Serpentine (asbestos) minerals

Tectosilicates - Three-Dimensional Networks

These include Quartz and the Feldspars

One of the simplest tectosilicate structures:

tridymite, a high-temperature form of silica.

Quartz has a more complex structure, with

spiral chains of tetrahedra. In this diagram
they are colored differently to distinguish
neighboring chains.

The structure of the feldspars. The red atoms

are potassium, sodium, or calcium. Since
these atoms are cations, some of the
tetrahedra contain aluminum (+3) instead of
silicon (+4) to maintain charge balance.

The Problem of Crystals

Unit Cells
Repeating patterns, whether flowers on wallpaper, or atoms in a crystal, can all
be described in terms ofUnit Cells. A unit cell is an imaginary box that contains
the basic pattern. Repeating the unit cells recreates the whole pattern. There are
FIVE basic unit cells for two-dimensional patterns:

Parallelogram (green)
Rectangle (purple)
Rhombus (yellow)
Square (blue)
Hexagonal (red)

Note that the rhombus pattern can be considered either as made up of

rhombuses or as a rectangle with an extra point in the center. Crystallographers
prefer the latter, because it makes the rectangular nature of the pattern clearer.
Bricks in a wall have this pattern.
The hexagonal pattern can be described by rhombuses oriented in one of three
ways. Two are in red and the third is outlined but not colored. The three unit cells
lead to identical descriptions of the pattern.

Unit Cells in Three Dimensions

We can modify a cube by shaving off the edges, as shown in the top row. If we
shave away the faces completely, the end result is a shape called
a dodecahedron (Greek dodeka = twelve, hedron = side). The bottom left shows
how cubic cells can be stacked to create this shape. The lower right shows the
dodecahedron. In an actual crystal, the unit cells are so tiny the faces appear
perfectly smooth.

We can modify a cube by shaving off the corners, as shown in the top row. If we
shave away the corners completely, the end result is a shape called
an octahedron (Greek okta = eight, hedron = side). The bottom left shows how
cubic cells can be stacked to create this shape. The lower right shows the
octahedron.
Below, we see some of the forms that can be made just from combining the three
simple ways of stacking cubes above. Clearly, memorizing all the possible shapes
is out of the question.

Animation showing how the forms below are related

Symmetry
What crystallographers look for is the rules
behind the shapes, called symmetry. All the
shapes above can be cut in half in many ways to
make mirror-image halves. This is
called reflection symmetry.
They can also be rotated in various ways to
positions where they look the same as their
original orientation. This is called rotational
symmetry.
All together, there are 32 kinds of symmetry
crystals can have, grouped into six classes
according to the shapes of the unit cells in the
crystal.

Animation of Symmetry
Upper Left: several possible ways of cutting the
crystal into mirror-image halves are shown.
There are numerous others not shown.
Upper Right: Note that the crystal looks the
same four times during a complete rotation. We
refer to this rotation axis as a four-fold
symmetry axis.
Lower Left: The crystal looks the same three
times during a complete rotation. We refer to
this rotation axis as a three-fold symmetry axis.
Lower Right: The crystal looks the same twice
during a complete rotation. We refer to this
rotation axis as a two-fold symmetry axis.

Note (for the passionately interested only) that something irregular with no
symmetry will only look the same once during a 360-degree rotation. Thus
crystallographers say something with no symmetry has one-fold symmetry. It
sounds convoluted, but all the mathematical formulas (yes, there is math in
geology!) that are used to describe symmetry work perfectly.

The Crystal Classes

Just as plane patterns can be described in terms of five unit cells, three
dimensional patterns can be thought of as belonging to one of six classes. Just as
there are two kinds of rectangular plane patterns, there are several types of
three-dimensional pattern for each of the six crystal classes

ISOMETRIC or CUBIC
All edges equal, all angles 90 degrees
Halite, Fluorite, Pyrite
Galena, Garnet, Magnetite
Gold, Copper, Diamond

TETRAGONAL
Two edges equal, all angles 90 degrees. Square
cross-section but different third dimension.
Zircon
Chalcopyrite

ORTHORHOMBIC
No edges equal, all angles 90 degrees. Like the
shape of a cereal carton.
Olivine, Andalusite, Sillimanite
Some Amphiboles and Pyroxenes
Topaz, Sulfur
MONOCLINIC
No edges equal, two angles 90 degrees. The
shape obtained by knocking the ends out of a
carton and skewing it.
Some Amphiboles and Pyroxenes
Micas
Gypsum, Epidote
Sugar also belongs to this crystal class.
TRICLINIC
No edges equal, no angles 90 degrees
Most Feldspars
Kyanite
Clay Minerals
What if you have one 90 degree angle, or two
equal edges? It turns out that these contribute
no extra symmetry and the crystal is still
triclinic.
HEXAGONAL
Angles of 60, 90, and 120 degrees.
Ice (snowflakes)
Quartz, Beryl
Corundum, Hematite
Calcite, Dolomite

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Created 8 February, 1997

Last Update 23 January, 2001
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