The Crystal Structure of Rochelle Salt (Sodium Potassium Tartrate Tetrahydrate NaKC4H4

O6. 4H2O)
Author(s): C. A. Beevers and W. Hughes
Source: Proceedings of the Royal Society of London. Series A, Mathematical and Physical
Sciences, Vol. 177, No. 969 (Jan. 10, 1941), pp. 251-259
Published by: Royal Society
Stable URL: https://www.jstor.org/stable/97552
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The crystal structure of Rochelle salt (sodium potassium
tartrate tetrahydrate NaKC4H4O6* 4H20)

BY C. A. BEEVERS AND W. HUGHES

(Communicated by W. L. Bragg, F.R.S.-Received 1 August 1940)

The complete crystal structure of Rochelle salt (sodium potassium

tartrate tetrahydrate) has been determined by Fourier and Patterson
methods. Some of the difficulties in the application of these methods are
discussed.
The tartrate molecule is found to lie approximately in three planes, the
planes of each half of the molecule being inclined at 600 to the plane of the
carbon atoms. The tartrate molecules are bonded to sodium and potassium
atoms both directly and through the medium of water molecules. If the
water molecules are to preserve their customary tetrahedral 'bonding' it is
necessary to suppose that one of the carboxyl groups of the molecule is also
a dipole. A reversal of the continuous chain of carboxyl-water-water
dipoles is a possible explanation of the peculiar dielectric properties of the
salt.

INTRODUCTION

This work was undertaken primarily as a development of previous work

on crystalline hydrates, and as an exercise in the X-ray analysis of a
complex structure. As will be seen later the structure requires the deter-
mination of forty-seven parameters, has no centre of symmetry, and no
features which permit any simplification of the direct methods of analysis
which are now available. These methods are, however, so powerful, that
in the authors' opinion they extend very greatly the complexity of
structures which can be solved by X-ray analysis.
Rochelle salt is also of great interest as being optically active, and
because of its somewhat remarkable electric properties. The potassium
sodium salt has abnormally large values of the dielectric constant parallel
to the a-axis between the temperatures -10 and + 25? C. This property
has attracted much attention, a recent summary of the theoretical work
being by Mueller (I940), but it seems clear that the theoretical work
requires guidance by an accurate and complete X-ray analysis.
The present work also provides the first measurements on the con-
figuration and size of the tartrate molecule.

[ 251 ]

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 252 C. A. Beevers and W. Hughes

DESCRIPTION AND DISCUSSION OF THE STRUCTURE

Rochelle salt crystallizes in the orthorhombic bisphenoidal class and

has been shown by many previous workers to possess the space group

P 212.2, having the absences (hOO) when h is odd, and (OkO) when
We have verified this assignment of space group, and by measurements
on high-order planes have deduced the following values of the cell edges
for Rochelle salt itself, and for other members of the isomorphous series
to which this salt belongs:
ao b() co
A A A

Potassium-sodium salt 11-93 14-30 6.17*

Ammonium-sodium salt 12 15 14 40 6-18*
Rubidium-sodium salt 12-05 14 40 6.21*

* By layer-line measurement only.

According to Groth the density of Rochelle salt is 1F790, and this

requires four molecules of KNaC4H406. 4H20 in the unit cell.
The general positions of the space group P 21212 are the points

(XyZ) GTYZ) ( 2 + X 12- y Z) (lf- x 12 + yZ)

while the special positions (on the twofold axes) are

(a) (OOz) (j 1); (b) (1Oz) (OZ).

The different salts studied appear to be strictly isomorphous, but we
have obtained accurate parameters only of the potassium salt. These
parameters are probably very close to the true values for the other salts
also.
The potassium atoms occupy the two sets of two-fold positions as shown
in table 1, with z parameters of 0 05 and 0d15 respectively. The sodium
atoms occupy the general positions (0-23, 0 01, 0.52), and (as shown in
figure 1) this gives an arrangement of positive ions lying rather closely
together in sheets perpendicular to the b-axis. The remaining atomic
positions are listed in table 1, and the projection of the complete unit
cell on the (001) plane is shown in figure 1. In this figure the atoms are
numbered to correspond to table 1 and the z co-ordinates are given along-
side the circles representing the atoms.
The sodium atom has around it a co-ordination group of six, two oxygens
and one hydroxyl from the tartrate groups, and three water molecules.
The sodium-oxygen distances are given in figure 2, and average 2*39 A,
which is sufficiently close to the accepted values. (Sum of Na and 0 radii

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 The crystal structure of Rochelle salt 253

tO5, ( ( 5) (42)* N

(0- 37) 1~)1 \ / 0 08) 0 OorOH

(0 021120
18 (O X0 l . e |
(052) 82O ) (003)

0 1 2 3 4 0 5 6 7 8 9 10
FIGURE 1. Projection on (001) plane, of the structure of Rochelle salt. The arrow
heads on the bonds are drawn in a direction from positive atoms to negative atoms.
The bonds inv7olv7ed in the 1-2-9-10 chains are drawn thick, so that the chains
canSbe picked out.

TABLE 1

2 K on (a) (0.00 000 0.05)

2 K on (b) (0.00 0 $0 0.15)
4 Na on (0*23 0 99 0.52)
4 0 on (1) (0.12 010 0H37)
4 0 on (2) (0*22 0*20 0.12)
4 0 on (3) (0*23 0 40 0.82)
4 0 on (4) (0P06 0 37 0 085)
4 OH on (5) (0a16 036 0.32)
4 OH on (6) (0229 024 0.63)
4 H20 on (7) (0.40 0 (08 050)
4 H20 on (8) (025 005 0 87)
4 H20 on (9) (0p44 0 30 0 05)
4 H20 on (10) (0 42 0*40 0 45)
4 C on (e 1i 0i18 0 28)
42C on (0-12 028 0.42)
4 C on (0.17 0*27 0*65)
4Con (025 035 080)

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254 C. A. Beevers and W. Hughes

from Internationale Tabellen, 2, 611, is 2*32 A.) The potassium atom on

(0, 0, 0.05) has a four-co-ordination group consisting of two oxygens from
tartrate groups and two waters, while the other potassium atom touches
two oxygens and two hydroxyls from tartrate groups, and four water
molecules, thus having a co-ordination of eight. The interatomic distances
in these groups are shown in figure 2.

.1 ~~~~~~~~~~~~~~~~~~~~-7
2 88 2-5

FIGURE 2. Final Fourier synthesis of one-quarter of the complete unit cell pro-
jected on (001), giving the positions chosen for the atoms and the interatomic dis-
tances in Angstrom units.

The potassium atom at (0, 0.05) has distances of 279 A to the two
oxygens, and 3*01 to the two waters. Possibly it is also bonded to water
molecule 8 (at 3*29 A) which would increase its co-ordination to six. If
there are also residual forces to water molecule 10 (3.52 A) the co-ordina-
tion would go up to ten. These bonds above 3a2 A have not been included
in figure 1, as they must be considerably weaker than the shorter bonds,
but their possible existence suggests that the large K ion is readily polar-
izable, and has a somewhat indefinite co-ordination.

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 The crystal structure of Rochelle salt

The tartrate molecule has its chain of carbon atoms almost exactly in
a plane. Figure 3 is a perspective drawing of the molecule the carbon
atoms being in the plane of the paper. The C(OH)-COOH groups con-
stituting each half of the molecule are also practically plane groups
inclined at 600 + 2 to the plane of the carbon atoms. The C-C distances
found are 1-58, 1*53 and 1-52 A, while the C-O distances are 1-36, 1-32,
1-22 and 1*15 A. The C-OH distances seem to be rather longer, viz. 1-40
1-51 A. It must be stressed that all the final atomic positions have been
chosen from the Fourier maps without manipulation with a view to
obtaining good interatomic distances, so that the values may be taken as
independent determinations. They are not regarded as being very accurate,
but the mean of 1-54 A is good supporting evidence for the usually
accepted separation of single bonded carbon atoms.

10

129/ 1150

FIGuRE 3. The tartrate molecule in parallel perspective viewed in a direction

perpendicular to the plane of the carbon atoms, showing the angles between the
various bonds. Each half of the molecule lies in a plane inclined at 60? to the plane
of the carbon atoms.

The water molecule 7 (see figure 1) is 2 75 A from a potassium atom,

2-39 A from a sodium atom, 2-73 A from a hydroxyl group, and 2-96 A
from an oxygen atom, and apart from neighbouring atoms in the same
co-ordination group it makes no other close approaches. The four bonds
described have an approximately tetrahedral distribution in agreement
with the Bernal-Fowler model for the water molecule.
Water molecule 8 can also be given four bonds, although these are not
so regular as in the previous case. These bonds are, to a potassium atom
3'07 A, to a sodium atom 2-34 A, to an oxygen atom 2-67 A, and to a

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256 C. A. Beevers and W. Hughes

hydroxyl group 3 14 A. If the latter distance be disregarded the water

molecule may be regarded as of the planar type described by Beevers and
Lipson (934). It should be pointed out that this water molecule is not
resolved from other atoms in any of the three Fourier projections con-
sidered, so that it is probably the least accurately located atom in the
structure.
Water molecule 9 has a distance of 3-01 A to a potassium atom and
distances of 2-83 and 3 07 A to oxygen atoms 4 and 2 respectively. It is
distant 2-86 A from water molecule 10 and 3-20 A from the hydroxyl
group 6 (in the unit cell co removed). This final distance must be negle
if the molecule is to be fitted into the tetrahedral theory, and the bond
between 10 and 9, regarded as a line of electrostatic force, may be taken as
being directed from 10 to 9. The water molecule 10 has, in addition to the
outgoing bond to 9, bonds to the sodium atom (2-31 A), to the oxygen
atom 1 (2.56 A), and to the hydroxyl group 6 (2.99 A). The sodium bond
must be regarded as incoming, so that one of the bonds to the tartrate
molecule must also be regarded as incoming. If the bond from oxygen 1
be taken as incoming we obtain at once a simple explanation of the
dielectric properties of Rochelle salt.
Oxygen 1 is behaving as a positive atom to water molecule 10, but as
a negative atom to the potassium and sodium atoms with which it is also
in contact. That is to say, the oxygen atom 1 in association with its carbon
atom is strongly polarized perhaps because of a hydrogen nucleus from
another part of the molecule. The positive direction of the bonds is thus
1 to 10, 10 to 9, 9 to 2. However, if the polarization of oxygen 1 can be
transferred to oxygen 2 within the same molecule the positive bond direc-
tion may now go 2 to 9, 9 to 10, 10 to 1. Such a change requires the water
molecules 9 and 10 to interchange a positive and negative bond, i.e. in
each case one of the hydrogen nuclei within the molecule shifts to one of
the tetrahedral negative areas. This chain of atoms 1-2-9-10-1-2-9-10,
etc., extends along the direction of the a-axis, the direction in which the
anomalies are observed. Thus, if a field is impressed on the crystal in this
direction the chain of molecules will arrange themselves so that the direc-
tion of the bonds is the same as the direction of the field. This will involve,
as has been pointed out by Jaff6 (I937), a lowering of the symmetry to
monoclinic, but since only the positions of hydrogen nuclei are involved
the lowering of the symmetry will not be detectable by change in the
X-ray intensities.
The facts that the anomaly disappears gradually as potassium is sub-
stituted by ammonium or rubidium or thallium and as the temperature is

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 The crystal structure of Rochelle salt 257

raised above 25' C are probably to be accounted for by an expansion of

the structure so that some of the contacts 2-9, 9-10, 10-1, are broken.
The bond 2-9 is already 3 07 A long and this is probably near the limit.
There is also to be considered the possibility of the rotations of molecules
or of chains of molecules above 25 C, by analogy with the change from
ferro to paramagnetism. The lower Curie point might correspond to para-
meter changes which result in bonds being broken or made, or to the
'freezing' of the subatomic changes. Further accurate intensity work
on Rochelle salt at different temperatures and with the potassium atoms
substituted would enable these ideas to be tested rigorously. We think,
however, that three-dimensional Fourier methods would be the best to
adopt. We hope at some more favourable time to use a Fourier machine to
do this work (Beevers 1939).

METHOD OF ANALYSIS

Fourier and Patterson methods were used -to supplement each other in
the elucidation of the structure. The Fourier method used is a general one
applicable whenever the crystal is a member of an isomorphous series.
In the present case the ammonium, potassium, rubidium and thallium
sodium tartrates were studied, Weissenberg photographs being taken abou
the a-, b-, and c-axes. From a knowledge of the position of the replaceable
atoms in the lattice and observation of the changes of intensity between
the different salts, the signs of the F's can be obtained.
In the case of the thallium compound the position of the thallium atoms
can be readily deduced, since to a first approximation the intensities
depend only on these atoms. This deduction in the case of Rochelle salt
was first made by Dr R. C. Evans, to whom we are indebted for access to
his unpublished work. If we next assume that atoms replacing thallium
occupy the same positions, the sign of each F may be taken to be the same
as the sign of the thallium structure factor if there is an increase in the
intensity as an atom is replaced by a heavier one. If there is a decrease in
the intensity then the sign is opposite to the sign of the thallium con-
tribution. In the actual carrying out of this process there are two diffi-
culties, the first being due to the effect of the varying absorption coeffi-
cients on the intensities, which makes it impossible to compare photographs
of different crystals directly. In this work crystals were used which had
been ground to accurate cylinders parallel to the axis of rotation, thus
enabling the absorption to be calculated (Bradley I935). The substitution
of potassium by rubidium is particularly useful since the copper Kcx

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258 C. A. Beevers and W. Hughes

radiation used has an absorption edge between this pair of alkali metals,
and the change of absorption coefficient is not therefore so marked.
The second difficulty in the change of intensity method arises from the
fact that many of the structure factors are small, and in the particular case
of Rochelle salt rather a high proportion are actually zero. For example,
in the (hOt) set all planes with 1 = 5 have a thallium or potassium structure
factor which happens to be zero. When the structure factor is small valu-
able information as to sign can be got by inspection of the thallium in-
tensities, but when it is zero, of course, the sign cannot be derived by the
method of substitution at all. In spite of these difficulties the projections
obtained down the a- and b-axes were substantially correct and the three-
dimensional structure could have been derived from them immediately
had it not been for the fact that in each projection two molecules are super-
imposed. The resolving power is thus very low, and it was felt that more
accurate positions were desirable. The lack of resolving power obtainable
by Fourier methods is even more marked down the c-axis. The projection
in this direction has a unit cell, as far as the potassium atoms are con-
cerned, of one quarter of the true unit. This means that only the planes
with h and k both even have a, potassium contribution. Only these planes
can therefore be used in a Fourier synthesis, and the resulting summation
is a superposition of the four quarters of the unit cell.
The Patterson syntheses used in the work were:
(1) Sections at z=0, x = and y = I of the three-dimensional synthesis
of the ammonium salt.
(2) Patterson synthesis of the (hk0) planes excluding those having h
and k both even.
The general intensities required for (1) were obtained mainly from layer-
line Weissenberg photographs of the ammonium salt about the a-, b-, and
c-axes. The use of the Weissenberg method rather than oscillation photo-
graphs requires a much greater total exposure time, but this is counter-
balanced by the perfect resolution obtained, and the ease of analysis of
the photographs. The experimental work throughout was performed on a
Weissenberg camera of special design (having a vertical travel of 0*74 mm.
per degree rotation of the crystal, and a radius of 5 cm.) and mounted
alongside a Metropolitan-Vickers crystallographic X-ray set. The Weissen-
berg photographs gave all the intensities obtainable with Cu K radiation
except those within cusps having axes parallel to [111] in the reciprocal
space. These remaining intensities were obtained from a set of oscillation
photographs with [110] as rotation axis. In this case the layer-lines are
so close together as to make the oscillation photograph the most advan-
tageous method.

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 The crystal str'ucture of Rochelle salt 259

The derivation of the structure from the three sections of the general
Patterson synthesis alone is not easy, and the Fourier syntheses pre-
viously described were found to be of great assistance in this work. The
general Patterson synthesis is more symmetrical than the structure (it has
the symmetry P 2/rn 2/rn 2/rn with a unit cell one-eighth of the unit of
the structure) and provides a correspondingly large number of alternative
atomic positions corresponding to each peak. A further difficulty in the
interpretation is that in the section at x = 1, for example, we obtain not
only each peak due to a vector between corresponding atoms (related by
the screw axis parallel to a) but also peaks of double weight due to different
atoms having by chance the same value of X. In a structure as complex
as Rochelle salt, with fifteen unique atoms in general positions within a
!ao distance of 6 A there is almost certain to be a number of such
cidences, and they give rise to two pairs of atoms with the same inter-
atomic vectors having x components of 1ao. Similar considerations apply
to the y and z = 0 sections. There is no doubt that if the complete
three-dimensional synthesis were available it would simplify a great deal
the derivation of a complex structure. However, the labour of calculating
the three-dimensional series with this size of unit cell is rather great.
The interpretation of the general Patterson sections and the Fourier
projections together, enables rather accurate atomic sites to be found, the
only remaining alternative being that a position may be (xyz) or x-x
W-yz), i.e. there is left a centre of symmetry at ({, , w). If the first atom
to be inserted is placed on one of these alternatives the Patterson synthesis
of the (hkO) planes (which is the projection parallel to the c-axis of the
general Patterson) shows which alternatives are to be chosen for the other
atomic positions. In this way two structures can be built up, related to
each other by a centre of symmetry at (4, -, 1) and these correspond to
and d- and i-forms of the optically active compound. The X-ray evidence
cannot of course distinguish between them.
Note. The calculated and observed intensities and other details of this
work are to be deposited in the archives of the Royal Society.

REFERENCES

Beevers 1939 Proc. Phys. Soc. 51, 660.

Beevers and Lipson 1934 Proc. Roy. Soc. A, 146, 570.
Bradley 1935 Proc. Phys. Soc. 47, 879.
Groth I906 Chem. Krist. 3, 332.
Jaff6 I937 Phys. Rev. 51, 43.
Mueller 1940 Phys. Rev. 57, 829.

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