Po&/tedrun Vol. 16, No. 2, pp. 321 325.

lYY7
Copyright ,c 1996 Elsev~er Science Ltd
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Synthesis and crystal structure of the cryptate

complex [Gd(L)(DMF)I
KSCN CH$N
3H20
(L is a deprotonated phenol-based Ns03
cryptand)
??

??

??

Shu-Yan Yu, Quan-Ming Wang, Biao Wu, Xin-Tao WU,~* Huai-Ming Hu.
Liu-Fang Wang and An-Xin Wu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure
Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China
hState Key Laboratory
Department

of Coordination
of Chemistry,

(Received

Chemistry,
Lanzhou

23 February

Nanjing

University,

University,
Lanzhou

1996 ; accepted

Nanjing

of Matter,

210093, P.R. China

730000, P.R. China

I May 1996)

Abstract-The
cryptate complex [Gd(L)(DMF)]
* KSCN - CH,CN - 3H,O has been synthesized by the reaction
of gadolinium isothiocyanate
and potassium thiocyanate with cryptate [Na(H,L)], which was prepared by a
(2 + 3) Schiff-base condensation
of tris(2-aminoethyl)amine
and 2,6-diformyl-4-methoxyphenol
in the presence
of NaOH. The Gd atom is encapsulated
in the cryptand with an unsymmetric eight-coordinate
environment.
Copyright $> 1996 Elsevier Science Ltd
Kepord.~:

gadolinium

; cryptate ; complex ; cryptand

; synthesis ; structure.

Much current attention has been devoted to the design

and synthesis of lanthanide complexes of macrocyclic
ligands [l]. Their studies are extensively correlated
with many emerging fields of application,
such as
supramolecular
devices [24], luminescent labels and
fluorescent probes in biological and medical applications [5], magnetic resonance imaging [6] and catalytic cleavage of RNA [7], etc. The lanthanide
complexes of phenol-based
two-dimensional
macrocyclic ligands have been extensively studied up to
1995. Drew [8] reported several kinetically stable lanthanide complexes of phenol-based
protonated
cryptands
(three-dimensional
macrobicyclic
ligands).
Recently, we synthesized a series of lanthanide cryptates with deprotonated
analogous cryptands. Herein
we describe the synthesis and crystal structure of
[Gd(L)(DMF)]
* KSCN *CH,CN - 3Hz0. Owing to
the compartment
coordination,
the cryptate possesses
an unsymmetrical
mononuclear eight-coordinate
conformation.

*Author to whom correspondence

EXPERIMENTAL
Gadolinium isothiocyanate
was prepared from the
reaction of gadolinium chloride (99.9%, China) and
potassium thiocyanate. Tris(2-aminoethyl)amine
and
2,6-diformyl-4-methoxyphenol
were prepared by the
modified methods according to Kimura [9] and Hu
[lo], respectively. Elemental analysis was carried out
by the analytical division of the State Key Laboratory
of Structural Chemistry. NMR, IR and UV-vis spectra were recorded on Varian Unity 500, Perkin-Elmer
577 and Shimadzu UV-3000 instruments, respectively.

Synthesl:c qf[Na(H,L)]
To a stirred suspension
of NaOH (0.060 g, 1.5
mmol) and 2,6-diformyl-4-methoxyphenol
(0.270 g,
1.5 mmol) in anhydrous methanol (50 cm3) was added
dropwise an anhydrous methanol solution (50 cm) of
tren (0.146 g, 1 mmol) at room temperature over 1 h.
The resulting orange precipitate was filtered off and
recrystalized from chloroform, yield 7 1%. Found : C.

should be addressed.

321

322

Shu-Yan

62.6 ; H, 6.5 ; N, 15.2. Calc. for C3aH4rNs06Na:

62.7,

N, 15.0%.

H NMR

(d,-DMSO,

TMS)

C,

*KSCN*CH3CN*3H,0

A mixture of [Na(H,L)]
(0.149 g, 0.2 mmol) in
acetonitrile
(20 cm3) and aqueous gadolinium
isothiocyanate
(0.176 g, 0.4 mmol) and potassium thiocyanate (0.02 g, 0.2 mmol) in ethanol (30 cm) was
stirred and heated for 0.5 h. The reaction solution
was filtered and the yellow filtrate stood for several
minutes, yellow microcrystals were isolated. The crude
product is redissolved into DMF by slow diffusion of
ether over a week, yellow crystals suitable for X-ray
structure determination
were obtained,
yield 75%.
Found:
C, 47.4; H, 5.1 ; N, 13.7. Calc. for
C,,H,,N,,O,,SGdK:
C, 47.2; H, 5.4; N, 13.5%. IR
(cm-, KBr disc.): 3420~ (uon), 2056s (us&, 1652s
(u,=,), 1636sh, 1604, 1545, 1470, 1345, 1295, 1220,
1037, 796. UV-vis
spectrum
(CH,CN):
260 (E,,,
14300), 475 nm (11800).

crystal
structure
X-ray
[Gd(L)(DMF)]
* KSCN CH,CN

Table

1.

data
for
[Gd(L)(DMF)] *KSCN.
CH,CN. 3H20

Crystal

: 6 13.78

(s(br), 2H, ph-OH), 8.45 (s(br), 6H, imino-CH), 6.94

(s(br), 6H, ph-H), 3.67 (s, 9H, OCHJ, 3.59, 3.55 (d,
12H, H2C-N
(imino)), 2.81 (s(br), 12H, H2C-N
(bridgehead)).
IR (cm-, KBr disc.): 3543~ (uon),
3411,3244,3012,2995,2939,2906,2842,2810,
1643s
(uc&
1597, 1460, 1317, 1259, 1155, 1051, 960, 815,
754. UV-vis spectrum (CH,CH) : 258 (E,,, 14900 dm3
cm- mall), 370 nm (10000).

Synthesis of[Gd(L)(DMF)]

Yu et al.

determination

of

* 3H20

A yellow block crystal encapsulated

with gel possessing approximate
dimensions
0.35 x 0.25 x 0.25
mm was mounted on a glass fibre in a random orientation. The unit cell parameters were determined from
least-squares
refinement
of the
setting
angle
(12 < 6 < 14) for 19 reflections. Intensity data were
recorded on an Enraf-Nonius
CAD4 diffractometer
at 23C, using graphite-monochromated
MO-K, radiation (1 = 0.71073 A). A total of 9640 reflections were
measured, of which 9207 were unique and 5963 with
1 > 3.0 u (1) were used in the refinement (w-20 scan
type, 2Q,,, = 50, scan rate 1-7 min- in o). Three
representative
reflections were measured every 120
mins, no significant decay was observed.
Lorentzpolarization
and empirical
absorption
corrections
were applied. Intensities of equivalent reflections were
averaged.
The structure
was solved by Patterson
heavy-atom
method
using MolEN
[l I] program,
which revealed the coordinates
of the Gd atom. The
remaining non-hydrogen
atoms were located in succeeding difference Fourier syntheses. Hydrogen atoms
were located theoretically and not refined. The K atom
is disordered.
All calculations
were performed
on a
COMPAQ PL4/50 computer. See details in Table 1.

Formula

G&N,

F.W.

1144.47
1174
0.35 x 0.25 x 0.25 mm
MO-Ka(l = 0.71073 A)
23
triclinic
P-l
13.354(3)
13.674(5)
15.777(2)
89.04(2)
93.51(l)
114.20(3)
2622(l)
2
1.45
14.5
w-20
l-7
50.0
G-15, - 1616, - 18-18
9640 total, 9207 unique
0.053
0.998, 0.845
1.0 if F, < 56.5
(56.5/F,J2 if F. > 56.5
5963 with 1z 3.0 Q (I)
561
0.073
0.086
1.04
0.05
1.93, -0.19

F(OO0)
Crystal dimensions
Radiation
Temperature
(C)
Crystal system
Space group
a (A)
b (A)
c (A
a ()
B ()
Y ()
v (A)
Z
&, (g cm-)
p (cm-)
Scan type
Scan rate ( min
Maximum 20 ()
Range of h, k, I
Refl. measured
R I,
T,,, and T,,,
Least-squares
Reflections
Parameters
R

in 0)

weights

included
refined

RW
Goodness-of-fit
Largest shift
High and Low peak in final

,%SGdK

map (e A)

RESULTS AND DISCUSSION

Cryptate
[Na(H2L)] was synthesized
by a facile
sodium template reaction as shown in Scheme 1.
Only one phenolic proton was replaced by NaOH
in the formation of the cryptand, resulting in a mono
sodium cryptate. This template effect is different from
the sodium template synthesis of phenol-based
twodimensional
macrocycles
[12]. The cavity size plays
an important role in synthesis of the sodium cryptate.
The IR spectra show no bands with the characteristic
stretching frequency of the carbonyl groups and the
primary amine groups. However, the cryptate possesses a very strong absorption
band at 1643 cm-,
assigned to the imino stretching mode, supporting the
Schiff-base linkage. There are some broad peaks in
its H NMR spectra, perhaps resulting from a rapid
conformational
exchange. At room temperature,
distinguishable
NMR splitting similar to the unsymmetric sodium mononuclear
cryptates described by
Nelson et al. [13-141 was not observed.

Synthesis

and crystal structure

of the cryptate

323

complex

NaOH

QCH 3

i)CH3
Scheme

GdtSCN) 3

KSCN

1.

[Na (H,L)

CH3CN - E tOH

DMF

Scheme 2

The complex
[Gd(L)(DMF)]
* KSCN* CH,CN *
3Hz0 was synthesized as shown in Scheme 2.
The crude product isolated from CH,CN-EtOH
is difficult to dissolve in normal solvents. Thus the
pure thiocyanate
coordinate
cryptate failed to be
obtained.
When redissolved
in DMF, the crystals
composed
of a Gd cryptate [Gd(L)(DMF)]
and a
KSCN were obtained.
In the IR spectra, the very
strong vibration absorption
of SCN is observed at
2056 cm- . The crystal structure of [Gd(L)(DMF)]
is
illustrated as Fig. 1.
The Gd ion is linked to one bridgehead nitrogen
(Nl) and three imino-nitrogen
atoms (N(l l), N(21)
and N(31)) as well as three phenol-oxygen
atoms
(O(l), O(2) and O(3)), forming a N4(0-)? coordination inside the cryptand. DMF acts as another 0

donor to the Gd atom. The other nitrogen donors of

the cryptand (N(2), N(12), N(22) and N(32)) are not
bonded to the Gd atom. The cryptand gives three
coordinated
imino N donors (N(1 I), N(21). N(31))
at one side, and three uncoordinated
imino N atoms
(N(12), N(22), N(32)) at another side. Thus. the metal
ion is eight-coordinate
and is unsymmetrically
encapsulated in the cryptand. The coordination
geometry
about the Gd atom can be considered as a distorted
dodecahedron,
being isostructural with the complexes
of the neutral cryptand [8]. This unsymmetric
conformation
was also observed in mononuclear
Na .
Zn2, Pb+ and Cd+ complexes of neutral phenolbased cryptands [I 3, 141. Selected bond lengths (A)
and angles ( ) are shown in Table 2.
The average Gd-0
(phenol) distance is 2.3 16 A.

324

Shu-Yan

Yu et al.

C(33)
Cf32d

YxiP

OW)

~(27)

Fig.

1. Structure

Table 2. Selected bond lengths

Gd-0
Gd-O(l)
Gd-O(2)
Gd-O(3)
Gd-N(
1)
Gd-N(l1)
Gd-N(21)
Gd-N(3
1)
N(ll)-C(13)
0-Gd-0(
1)
O-Gd-O(2)
O-Gd-O(3)
0-Gd-N(
1)
0-Gd-N(
11)
0-Gd-N(2I)
0-Gd-N(3
1)
O(l)-Gd-O(2)
O(l)-Gd-O(3)
O(l)-Gd-N(1)
0( I)-Gd-N(
11)
O(l)-Gd-N(21)
0( I)-Gd-N(3
1)
O(2)-Gd-O(3)

of cryptate

[Gd(L)(DMF)].

(A) and angles () with e.s.d.s in parentheses

N(21)-C(23)
N(31)-C(33)
N(12)-C(14)
H(22)-C(24)
N(32)-C(34)
Gd
N(2)
Gd...N(12)
Gd . N(22)
Gd
N(32)

2.354(9)
2.311(8)
2.376(9)
2.260(8)
2.64(l)
2.50(l)
2.497(9)
2.59(2)
1.28(2)
143.0(3)
72.3(3)
98.1(3)
81.4(4)
145.3(4)
84.2(3)
70.6(4)
70.7(3)
78.6(3)
126.7(3)
71.0(3)
85.6(3)
138.9(2)
86.5(3)

1.27(2)
1.26(2)
I .32(2)
1.29(l)
I .34(2)
5.74(l)
4.47( 1)
4.52(l)
4.45( 1)

O(2)-Gd-N(1)
O(2)-Gd-N(l1)
O(2)--Cd-N(21)
O(2)--Cd-N(3
1)
O(3)-Gd-N(
1)
O(3)-Gd-N(I
1)
O(3)-Gd-N(21)
O(3)-Gd-N(31)
N(l)-Gd-N(I
1)
N(l)-Gd-N(21)
N(l)-Gd-N(31)
N(1 I)-Gd-N(2I)
N(l I)-Gd-N(31)
N(21)-Gd-N(31)

133.9(3)
140.4(3)
71.7(3)
133.4(3)
135.1(3)
95.6(4)
156.4(4)
71.9(3)
66.6(3)
68.4(3)
65.6(3)
95.6(3)
83.8(3)
130.0(3)

Synthesis

and crystal structure

consistent with the range in the complexes of phenolbased cryptands [8] and macrocyclic
[15] as well as
tripodal
hemi-cage
ligands
[ 16,171. The average
Gd-N
(imino) bond distance is 2.529 A, being shorter by 0.1 A than that in the normal macrocyclic
complexes [ 11. Comparing the bond lengths of C=N,
we can see that the average distance of coordinated
imino groups is shorter by 0.05 i\ than that of uncoordinated ones, showing that coordination
caused x
electron of bis(iminopheno1)
moieties of the cryptand
to be transferred
to the metal ion. The distances of
Gd
N (uncoordinated)
are in the range of 4.45( l)5.74( I ) A. This size may be expected to provide coordination to a second metal ion, but the second lanthanide or sodium ion failed to be encapsulated
possibly owing to their high coordination
numbers or
large radii. In other words, this compartment
cryptand only recognizes selectively one lanthanide(l1)
ion
or sodium ion.

of the cryptate

4.
5.

6.

7.
8.

9.

10.

I. V. Alexander, Chrm. Ret?. 1995, 95, 273.

2. J.-M. Lehn, Angew. Chem., Int. Ed. Engl.
27, 89.
3. V. Balzani

13.

14.

16.
1988,
17.

and

F.

Scandola,

Supramolecular

Horwood.
Chichester,
U.K.
(1991).
N. Sabbatini and M. Guardigli,
Mater. Chml.
Phys. 1992, 31, 13.
J.-C. G. Bunzli. in Lanthanide
pro/w
in Lif>,
Medical and Environment
Sciences (Edited by G.
R. Choppin and J.-C. G. Bunzli), chap. 7. Elsevier, Amsterdam, The Netherlands
(1989).
K. Kumar and M. F. Tweedle, Purt, Appl. Clam.
1993, 65, 515.
R. Breslow and D.-L. Hunang, Pro<,. NutI Acau.
Sci. U.S.A. 1991. 88, 4080.
M. G. B. Drew, 0. W. Howarth, C. J Harding,
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E. Kimura. S. Young and J. P. Collman. Inorg.
Chem. 1990,9. 1183.
Y. Hu and H. Hu, Chem. J. Chin. I/nil,. 1986. 7.
132.

Il.

15.

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325

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Ac,kno~~lr,d~enzpn/r-~We thank the State Key Laboratories
of Structural
Chemistry
and Coordination
Chemistry
of
China
as well as the Chinese
Postdoctoral
Science
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