New complexes with a sterically hindered thiourea: Syntheses and crystal structures of [Co(dchtu)2Cl2], [Zn(dchtu) 2(NCS)2] and [Pb(dchtu)6](SCN)2 · 2C2H5OH (dchtu = N,N′-dicyclohexy!thiourea)

Article abstract of DOI:10.1002/zaac.200700137

New complexes of a sterically hindered thiourea, [M(dchtu) ₂Cl₂] (M = Co 1, Ni 2), [Zn(dchtu)₂(NCS) ₂] (3) and [Pb(dchtu)₆](SCN)₂·2C ₂H₅OH (4) (dchtu = N.N·-dicyclohexylthiourea), have been synthesized and characterized. The single crystal structures of 1, 3 and 4 have been determined by single crystal Xray diffraction analyses. Co ^II, Ni^II and Zn form 1: 2 compounds with dchtu even if molar excesses of dchtu is used, while Pb forms 1:6 compound under the same conditions. The dchtu acts as a monodenate S-donor ligand in all the complexes. Co^II and Zn^II atoms are tetrahedrally coordinated with two dchtu ligands, and two chloride or isothiocyanate ions, respectively. The Pb^II ion in 4 forms an octahedral coordination sphere with six dchtu ligands. The structures of the complexes are stabilized by a system of intermolecular H-bonding.

Full text of DOI:10.1002/zaac.200700137

DOI: 10.1002/zaac.200700137
New Complexes with a Sterically Hindered Thiourea: Syntheses and Crystal
Structures of [Co(dchtu)2Cl2], [Zn(dchtu)2(NCS)2] and
[Pb(dchtu)6](SCN)2 ·2C2H5OH (dchtu ؍ N,NЈ-dicyclohexylthiourea)
Ding-Xian Jia*, Ai-Mei Zhu, Jie Deng, and Yong Zhang
Suzhou / P. R. China, Suzhou University, College of Chemistry and Chemical Engineering
Received March 20th, 2007.
Abstract. New complexes of
a
sterically hindered thiourea,
are tetrahedrally coordinated with two dchtu ligands, and two chlo-
ride or isothiocyanate ions, respectively. The PbII ion in 4 forms an
octahedral coordination sphere with six dchtu ligands. The struc-
tures of the complexes are stabilized by a system of intermolecular
H-bonding.
[M(dchtu)2Cl2] (M ϭ Co 1, Ni 2), [Zn(dchtu)2(NCS)2] (3) and
[Pb(dchtu)6](SCN)2 ·2C2H5OH (4) (dchtu ϭ N,NЈ-dicyclohexylthi-
ourea), have been synthesized and characterized. The single crystal
structures of 1, 3 and 4 have been determined by single crystal X-
ray diffraction analyses. CoII, NiII, and ZnII form 1: 2 compounds
with dchtu even if molar excesses of dchtu is used, while PbII forms
1:6 compound under the same conditions. The dchtu acts as a mon-
odenate S-donor ligand in all the complexes. CoII and ZnII atoms
Keywords: Cobalt; Zinc; Lead; N,NЈ-dicyclohexylthiourea; Crystal
structures
Introduction
N,NЈ-dicyclohexylthiourea (dchtu) is an important sym-
metrically substituted thiourea derivative. Toshimi et. al.
found that the sterically bulky N,NЈ-dicyclohexylthiourea
mixed with copper acetylacetonate is capable of absorbing
near IR-rays and provides superior optical materials for
shielding sunlight thermic rays [17]. However, the interac-
tions of dchtu with metal atoms still remain unexplored ex-
cept the only example of a tellurium(II) complex, [Te(dcht-
u)2Cl]Cl [18]. To the best of our knowledge there are no
examples of transition metal complexes containing dchtu.
Now we investigate the reactions of dchtu with CoII, NiII,
ZnII, and PbII metal ions and obtained the new complexes
[M(dchtu)2Cl2] (M ϭ Co 1, Ni 2), [Zn(dchtu)2(NCS)2] (3)
and [Pb(dchtu)6](SCN)2 ·2C2H5OH (4). The present contri-
bution reports the synthesis and characterization of the
new complexes.
Thioureas are potentially very versatile ligands in coordi-
nation chemistry being able to coordinate to metal atoms
via either sulfur or nitrogen atoms. Their soft sulfur and
hard nitrogen donor atoms provide a multitude of bonding
possibilities, therefore exhibiting coordination diversity in
metal complexes. In addition, thioureas are able to coordi-
nate to a range of metal atoms either as neutral ligands,
as monoanions, or as dianions [1Ϫ3]. Furthermore, their
physical and chemical properties are modified by the sub-
stituents on nitrogen. Now, the chemistry of substituted
thiourea derivatives has attracted increasing attention be-
cause of their potential use as reagents for the separation
or recognition of metal ions [4, 5] and in biological appli-
cations [6Ϫ8]. There have been many studies on N-alkyl or
aryl and N,NЈ-dialkyl or diaryl substituted thioureas and
related ligands coordinated to a series of metals [9Ϫ14]. The
properties of metal complexes with substituted thiourea de-
rivatives are influenced by the substituents on the nitrogen
atoms. For example, the sterically bulky N,NЈ-disubstituted
thiourea-Pd complexes are air- and moisture-stable, and
highly active catalysts for palladium-catalyzed Heck reac-
tion of aryl iodides and bromides with olefins [15, 16].
Results and Discussion
Synthesis and IR Spectral Studies
The dchtu ligand reacts with CoII, NiII, and ZnII salts in
C2H5OH to form exclusively the 1:2 stoichiometric coordi-
nation compounds 1, 2 and 3, respectively. Using three-fold
molar excesses of dchtu in the reactions also give rise to the
formation of these 1:2 compounds of dchtu. In contrast,
these metal thiourea-type complexes form 1:4 compounds,
[M(tu)4](NO3)2 (M ϭ Co, Zn) [19, 20], [Ni(tu)4]S2O3 ·H2O
[21] (tu ϭ thiourea) under similar conditions. The sterically
hindered nature of dchtu is the most likely explanation for
the limited degree of substitution in the valence shell of
the metal atoms despite the molar excess ligand. However,
lead(II) produced a 1:6 compound with dchtu under the
* Dr. Dingxian Jia
College of Chemistry and Chemical Engineering
Suzhou University (Dushu Lake Campus)
No.1 Renai Road
Suzhou, 215123/ P. R. China
Fax: ϩ 86-512-65880089
e-mail: jiadingxian@suda.edu.cn
Z. Anorg. Allg. Chem. 2007, 633, 2059Ϫ2063
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2059

D.-X. Jia, A.-M. Zhu, J. Deng, Y. Zhang
˚
Table 1 Selected bond distances /A and angles /° for 1, 3, and 4
Table 2 List of hydrogen bonds in the crystal structures of com-
plexes 1, 3, and 4
[Co(dchtu)2Cl2] (1)
DϪH
A
d(D···A)
<(DHA)
Co(1)ϪS(1)
2.2970(11)
Co(1)ϪCl(1)
2.2595(9)
Cl(1)ϪCo(1)ϪS(1)
111.63(4)
118.99(5)
S(1)ϪCo(1)ϪS(1)a
114.50(7)
100.40(4)
1
Cl(1)ϪCo(1)ϪCl(1)a
Cl(1)ϪCo(1)ϪS(1)a
N(1)ϪH(1)
N(2)ϪH(2)
Cl(1)
3.486(3)
3.290(3)
166(4)
161(3)
Cl(1)a
[Zn(dchtu)2(NCS)2] (3)
3
Zn(1)ϪS(1)
2.3311(12)
Zn(1)ϪN(3)
1.995(4)
N(1)ϪH(1)
S(2)a
3.721(4)
161(4)
S(1)ϪZn(1)ϪN(3)
N(3)ϪZn(1)ϪN(3)a
106.91(12)
113.0(2)
S(1)ϪZn(1)ϪS(1)a
112.57(7)
108.77(13)
S(1)ϪZn(1)ϪN(3)a
4
N(1)ϪH(1)
N(2)ϪH(2)
N(3)ϪH(3)
N(4)ϪH(4)
N(5)ϪH(5)
N(6)ϪH(6)
S(3)a
S(4)
3.581(3)
3.588(3)
3.746(3)
3.494(3)
3.602(3)
3.004(4)
155(3)
163(3)
161(3)
148(3)
159(3)
161(3)
[Pb(dchtu)6](SCN)2·2C2H5OH (4)
S(1)a
S(4)b
S(1)a
N(7)c
Pb(1)ϪS(1)
Pb(1)ϪS(3)
2.9636(7)
2.9625(8)
Pb(1)ϪS(2)
2.9610(7)
S(1)ϪPb(1)ϪS(2)
S(1)ϪPb(1)ϪS(3)
S(1)ϪPb(1)ϪS(3)a
S(2)ϪPb(1)ϪS(3)
S(2)ϪPb(1)ϪS(3)a
82.66(2)
87.91(2)
92.09(2)
74.10(2)
105.90(2)
S(1)ϪPb(1)ϪS(1)a
S(1)ϪPb(1)ϪS(2)a
S(2)ϪPb(1)ϪS(2)a
S(3)ϪPb(1)ϪS(3)a
S(3)ϪPb(1)ϪS(1)a
180.0
97.34(2)
180.0
180.0
92.09(2)
Symmetry transformations used to generate equivalent atoms: For 1:
a Ϫxϩ1/2, yϪ1/2, Ϫzϩ3/2. For 3: a x, yϩ1, z. For 4: a Ϫxϩ1, Ϫyϩ1, Ϫzϩ1;
b x, yϪ1, z; c x, y, zϪ1.
a Symmetry transformations used to generate equivalent atoms: For 1 and 3:
Ϫxϩ1, y, Ϫzϩ3/2. For 4: Ϫxϩ1, Ϫyϩ1, Ϫzϩ1.
same conditions, even when less dchtu is used. With thio-
urea, lead(II) also forms the 1:6 compound [Pb(tu)6](ClO4)2
[22]. The effects of sterically hindered substituents on the
nitrogen atoms of thiourea decrease with the increase of
metal radius.
The IR spectra of the complexes showed characteristic
bands due to N,NЈ-dicyclohexylthiourea and some import-
ant ones are listed in section 2. The presence of a ν (NϪH)
signal in the region 3072-3125 cmϪ1 as a weak band in the
complexes shows that the ligand is not deprotonated in the
complexes. The feature of the broad bands with low inten-
sity is evident that could arise from hydrogen-bonded NH
group. A strong ν (CϭS) band at 1153 cmϪ1 in the free
ligand shifts to the lower range, 1147-1152 cmϪ1. This
shows that the ligand coordinates to the metal atom via its
sulfur donor atom and the magnitude of the coordination
shift is similar to that reported in literatures [23Ϫ25].
Figure 1 Crystal structure of 1 with the labelling scheme (40 %
probability ellipsoids). Hydrogen atoms of CϪH are omitted for
clarity.
[27]. In complex 1, N,NЈ-dicyclohexylthiourea exhibits
cisϪtrans conformation (Fig. 1). As evidenced by the crys-
tal structures below, N,NЈ-dicyclohexylthiourea in 3 and 4
is also in cisϪtrans conformation. This difference might be
related with the steric hinderance of the cyclohexyl substitu-
ents and the H-bonding in the complexes. In 1, the hydro-
gen bonding interaction is between thioamide (>NϪH)
groups and ClϪ ions. Each of the [Co(dchtu)2Cl2] molecules
forms four NϪH···Cl hydrogen bonds with four neighbor
molecules forming a layered hydrogen bonding network
perpendicular to the c-axis of unit cell (Fig. 2). Since the
two ligands are symmetry equivalent, the unique N···Cl dis-
Crystal Structures
The structures of compounds 1, 3, and 4 are depicted in
Figures 1Ϫ6. Selected bond distances and angles are listed
in Tables 1 and 2. As show in Figure 1, the Co2ϩ ion is
coordinated by two S atoms from two N,NЈ-dicyclohexylthi-
ourea ligands and two chlorine atoms. The N,NЈ-dicyclohe-
xylthiourea ligand coordinates to the CoII atom through its
sulfur atom. The CoII atom forms a tetrahedral structure,
as evidenced by bond angles around the CoII atom ranging
from 100.40(4) to 118.99(5)°. Two CoϪS bonds are chemi-
˚
cally equivalent and the CoϪS distance is 2.2970(11) A.
The distance of CoϪCl bond is 2.2595(9) A (Table 1).
˚
˚
tances are 3.486(3) and 3.290(3) A, and NϪH···Cl angles
The CoϪS bond distances are similar to those observed in
the CoII complexes of thiourea [19, 26]. The N,NЈ-dialkyl
substituted thiourea, with the coplanar N2CS skeletal
atoms, can take transϪtrans, cisϪtrans, and cisϪcis three
possible conformations. N,NЈ-dimethylthiourea and N,NЈ-
diethylthiourea were transϪtrans isomers in the solid state
are 166(4) and 161(3)° (Table 2).
The molecular structure of 3 is depicted in Figure 3. The
Zn2ϩ ion is also in a tetrahedral coordination, involving
two S atoms of two N,NЈ-dicyclohexylthiourea ligands and
two N atoms of two NCSϪ anions (Fig. 3). The thiocyanate
anion coordinates to the Zn2ϩ ion through its N atom. The
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New Complexes with a Sterically Hindered Thiourea
Figure 4 View of the packing of [Zn(dchtu)2(NSC)2] molecules
showing the hydrogen bond interactions viewed along c axis.
Hydrogen atoms of CϪH are omitted for clarity.
Figure 2 View of the packing of [Co(dchtu)2Cl2] molecules sho-
wing the hydrogen bond interactions viewed along c axis. Hydrogen
atoms of CϪH are omitted for clarity.
Figure 3 Crystal structure of 3 with the labelling scheme (40 %
probability ellipsoids). Hydrogen atoms are omitted for clarity.
Figure 5 Crystal structure of 4 with the labelling scheme (30 %
probability ellipsoids). Hydrogen atoms are omitted for clarity.
˚
bond angles at the metal atom vary from 106.91(12) to
113.0(2)° (Table 1). Due to the sterical bulk of the cyclo-
hexyl rings, the SϪZnϪS angle (112.57(7)°) is much larger
than the corresponding angle observed in Zinc(II) complex
with thiourea, [Zn(tu)2Cl2] (SϪZnϪS: 98.40(3)°) [28]. The
3.587 A] forming a layer along (011) plane of the unit cell
(Fig. 4).
Compound 4 crystallizes in the monoclinic space group
P1 (no.2) with one formula unit in the unit cell. The Pb
2ϩ
¯
ion is coordinated by six N,NЈ-dicyclohexylthiourea ligands
forming a distorted octahedron (Fig. 5). The SϪPbϪS
bond angles at equatorial positions vary from 74.10(2) to
105.90(2)°. Three PbϪS bond distances are almost equiva-
˚
˚
ZnϪS (2.3311(12) A) and ZnϪN (1.995(4) A) bond dis-
tances are consistent with those observed in literatures for
similar zinc(II) thiourea complexes [20, 28, 29]. In 3, the
sulfur atoms of isothiocyanate ions acts as hydrogen bond-
ing acceptors, forming two equivalent NϪH···S weak hy-
drogen bonds with neighbor molecules [N(1)···S(2) ϭ
˚
lent and vary in a narrow range [2.9610(7)Ϫ2.9636(7) A]
(Table 1), which is in consistence with those of lead com-
plexes with thiourea [22, 30]. Although the thiocyanate ions
have no influence on coordination, they have significant in-
fluence on the crystal packing of the [Pb(dchtu)6]2ϩ cations
in 4. The thiocyanate ion forms three hydrogen bonds with
˚
3.721(4) A] (Table 2). The [Zn(dchtu)2(NSC)2] molecules
are arranged in a chain via this hydrogen bonding (Fig. 4).
The chains are extended via weak S···S interaction [S···S ϭ
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D.-X. Jia, A.-M. Zhu, J. Deng, Y. Zhang
Synthesis of [Co(dchtu)2Cl2] (1): A solution of dchtu (0.197 g,
0.82 mmol) in C2H5OH (8 ml) was added to a solution of
CoCl2 ·6H2O (0.100 g, 0.42 mmol) in C2H5OH (5 ml) followed by
stirring for 30 min when a clear blue solution was formed. The slow
evaporation of the solution at room temperature formed blue block
crystals of 1 in 85 % yield. Anal. Calc. for C26H48N4S2Cl2Co (%):
C, 51.14; H, 7.92; N, 9.17. Found: C, 50.98; H, 7.83; N, 9.07. IR
data (KBr pellets, cmϪ1): 3125w (νNϪH), 1147s (νCϭS), 1524vs
(νCϪN).
Synthesis of [Ni(dchtu)2Cl2] (2): A solution of dchtu (0.197 g,
0.82 mmol) in C2H5OH (8 ml) was added to a solution of
NiCl2 ·6H2O (0.100 g, 0.42 mmol) in C2H5OH (5 ml) followed by
stirring for 30 min when a light yellow solution was formed. The
slow evaporation of the solution at room temperature formed yel-
low precipitate of 2 in 78 % yield. No single crystals of the complex
is obtained, even after several attempts. Anal. Calc. for
C26H48N4S2Cl2Ni (%): C, 51.16; H, 7.93; N, 9.18. Found: C, 12.22;
H, 2.11; N, 9.34. IR data (KBr pellets, cmϪ1): 3095w (νNϪH),
1149s (νCϭS), 1521vs (νCϪN).
Figure 6 View of the packing of [Pb(dchtu)6](SCN)2 molecules
showing the hydrogen bond interactions viewed along a axis. The
cyclohexyl rings are omitted for clarity.
Synthesis of [Zn(dchtu)2(NCS)2] (3): A solution of dchtu (0.182 g,
0.76 mmol) in C2H5OH (8 ml) was added to Zn(SCN)2 (0.070 g,
0.38 mmol) suspended in C2H5OH (5 ml) and the mixture was
stirred for 2 h. The solution formed was filtered. The slow evapor-
ation of the resulted solution at room temperature formed colorless
block crystals of 3 in 65 % yield. Anal. Calc. for C28H48N6S4Zn
(%): C, 50.78; H, 7.30; N, 12.69. Found: C, 50.71; H, 7.21; N, 12.54.
IR (KBr pellets, cmϪ1): 3072w (νNϪH), 1152s (νCϭS), 1526s
(νCϪN).
thioamide (>NϪH) groups of dchtu ligand via its nitrogen
and sulfur atoms [N(6)···N(7) ϭ 3.004(4), N(2)···S(4) ϭ
˚
3.588(3), N(4)···S(4) ϭ 3.494(3) A] (Table 2). In the crystal
structure, each [Pb(dchtu)6]2ϩ cation is surrounded by six
cations, which form a planar hexagon. The central cation
interacts with its six neighbors by hydrogen bonding
through six thiocyanate ions (Fig. 6). By the connection
of thiocyanate ions, the [Pb(dchtu)6]2ϩ cations form a two-
dimensional network parallel to the (100) face of unit cell.
The effects of monodenate thione-sulfur coordination are
reflected in the thioamide dimensions of the ligand. An av-
erage lengthening of the CϪS distance and an average
shortening of the NϪC(ϭS) one are observed in the com-
plexes. The carbon-sulfur (thione) distance is increased
Synthesis of [Pb(dchtu)6](SCN)2 ·2C2H5OH (4): A solution of dchtu
(0.223 g, 0.93 mmol) in C2H5OH (10 ml) was added to Pb(SCN)2
(0.100 g, 0.31 mmol) suspended in C2H5OH (5 ml) and the mixture
was stirred for 2 h. The clear colorless solution formed was filtered.
The slow evaporation of the solution at room temperature formed
light yellow block crystals of 4 in 45 % yield (based on dchtu).
Reaction of dchtu and Pb(SCN)2 in C2H5OH in a 4:1 mole ratio
also produce 4 but with a higher yield (70 %). Anal. Calc. for
C84H156N14S8O2Pb (%): C, 54.30; H, 8.46; N, 10.55. Found: C,
54.22; H, 8.36; N, 10.41. IR (KBr pellets, cmϪ1): 3105w (νNϪH),
1151s (νCϭS), 1523s (νCϪN).
˚
˚
from 1.7013(15) A [31] in the free ligand, to 1.724(3) A,
˚
˚
1.734(4) A, and 1.716(3)Ϫ1.729(3) A for the coordinated li-
gands in 1, 3, and 4, respectively. On average, the thioamide
carbonϪnitrogen distance is correspondingly decreased
Crystal Structure Determination
˚
˚
from 1.338(2) A [31], in the free ligand to 1.329(4) A,
Data were collected on a Rigaku Mercury CCD diffractometer at
˚
˚
1.332(3) A, and 1.329(4) A in the coordinated ligand. The
carbonϪsulfur and carbonϪnitrogen bonds lie in inter-
mediate bond lengths between single and double bond,
which is attributed to the delocalization of the electrons in
the amide bond. This extent of the dimensional changes is
consistent with monodenate thione-sulfur coordination of
substituted thiourea ligands [10Ϫ12].
193(2) K using graphite-monochromated Mo-Kα radiation (λ ϭ
˚
0.71073 A) with a ω-scaning mode in the range 6.14 Յ 2θ Յ 50.68
for 1, 6.22 Յ 2θ Յ 50.68 for 3, and 6.24 Յ 2θ Յ 50.70 for 4. The
crystals of size 0.30 ϫ 0.20 ϫ 0.12 mm3, 0.26 ϫ 0.20 ϫ 0.18 mm3,
and 0.50 ϫ 0.23 ϫ 0.23 mm3 were used for data collection for 1, 3
and 4, respectively. An absorption correction was applied for all
data with multi-scan. The structures were solved with direct meth-
ods using SHELXS-97 [32] and structure refinements were done
against F2 with SHELXL-97 [33]. All non-hydrogen atoms were
refined with anisotropic displacement parameters. The hydrogen
atoms were positioned with idealised geometry and refined with
fixed isotropic displacement parameters using a riding model. The
atom of C(12) in 4 is disordered and the occupancies of disordered
C/CЈ are assigned as 65 % and 35 %. Technical details of data ac-
quisition and selected refinement results are summarized in Table 3.
Crystallographic data for the structural analyses have been de-
Experimental Section
Materials and Physical measurements: All chemicals were commer-
cial materials of analytical grade and used without further purifi-
cation. FT-IR spectra were recorded on a Nicolet Magna-IR 550
spectrometer in dry KBr pellets. C, H and N analysis was measured
on a MOD 1106 elemental analyzer.
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New Complexes with a Sterically Hindered Thiourea
Table 3 Crystal data and structure refinement details for complexes 1, 3, and 4
1
3
4
Formula
C26H48N4S2Cl2Co
610.63
C28H48N6S4Zn
662.33
C84H156N14S8O2Pb
1857.90
Formula weight
Crystal system
Space group
monoclinic
C2/c (no.15)
11.405(2)
14.592(3)
19.419(4)
90.00
91.130(5)
90.00
3231.2(11)
4
monoclinic
C2/c (no.15)
24.046(4)
8.9058(14)
19.038(4)
90.00
125.748(4)
90.00
3308.9(11)
4
triclinic
¯
P1 (no.2)
˚
a / A
12.4692(11)
14.9151(9)
14.9843(11)
60.813(3)
87.599(6)
79.837(5)
2391.6(3)
1
˚
b / A
˚
c / A
Ͱ / °
β / °
γ / °
3
˚
V /A
Z
T / K
193(2)
1.255
1300
0.846
6.14 Յ 2θ Յ 50.68
Ϫ13 Յ h Յ 12
Ϫ17 Յ k Յ 17
Ϫ21 Յ l Յ 23
15813
2951 [Rint ϭ 0.0539]
2535
193(2)
1.330
1408
1.022
6.22 Յ 2θ Յ 50.68
Ϫ27 Յ h Յ 28
Ϫ9 Յ k Յ 10
Ϫ22 Յ l Յ 22
15953
3038 [Rint ϭ 0.0458]
2605
153(2)
1.290
984
1.989
6.24 Յ 2θ Յ 50.70
Ϫ15 Յ h Յ 15
Ϫ17 Յ k Յ 17
Ϫ18 Յ l Յ 16
23378
8675 [Rint ϭ 0.0233]
8631
Dcalc. / g·cmϪ3
F(000)
µ / mmϪ1
Scane range / °
Index range
Collected reflections
Independent reflections
Reflections with (I > 2σ(I))
Parameters
168
186
519
R1 (I > 2σ(I))
wR2 (I > 2σ(I))
∆ρmax, ∆ρmin /e A
Goodness-of-fit
0.0591
0.0722
Ϫ0.360/0.385
1.138
0.0624
0.1405
Ϫ0.504/0.646
1.149
0.0263
0.0682
Ϫ0.910 / 1.089
1.064
Ϫ3
˚
posited with the Cambridge Crystallographic Data Centre, CCDC
Nos. 635441-635443. These data can be obtained free of charge
via www.ccdc.cam.ac.uk.
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