Syntheses, characterization and crystal structures of new organogermanium complexes with 2,5-dimercapto-4-phenyl-1,3,4-thiodiazole

Article abstract of DOI:10.1016/S0277-5387(03)00401-7

A series of organogermanium(IV) complexes with 2,5-dimercapto-4-phenyl-1,3,4-thiodiazole of the type, R₁₁ Ge[S(C₈H₅N₂S₂)]_4-n (n = 3, R = CH₃, 1; C₂H₅, 2; C₄H ₉, 3; C₆H₅, 4; n = 2, R = CH₃, 5; C₂H₅, 6; C₄H₉, 7; C ₆H₅, 8) have been synthesized. All the complexes 1-8 have been characterized by elemental, IR and ¹H NMR analyses. Among them complexes 4 and 8 have also been characterized by X-ray crystallography diffraction analyses, which revealed that the structure of complex 4 is a tetrahedron while the germanium environment of complex 8 is a distorted octahedron. Furthermore, an intermolecular non-bonded sulfur-sulfur interaction was recognized in complex 8. The IR and ¹H NMR spectral data indicate such an inclination that those structures of trialkylgermanium derivatives are apt to be four-coordinated and those of dialkylgermanium derivatives are likely to be six-coordinated.

Full text of DOI:10.1016/S0277-5387(03)00401-7

Polyhedron 22 (2003) 2767ꢂ2772
/
www.elsevier.com/locate/poly
Syntheses, characterization and crystal structures of new
organogermanium complexes with 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole
Chunlin Ma a,b,*, Qin Jiang a, Junhong Zhang a, Rufen Zhang a
a Department of Chemistry, Liaocheng University, Liaocheng 252059, China
b Department of Chemistry, Taishan University, Taian 271021, China
Received 31 March 2003; accepted 27 May 2003
Abstract
A series of organogermanium(IV) complexes with 2,5-dimercapto-4-phenyl-1,3,4-thiodiazole of the type, RnGe[S(C8H5N2S2)]4ꢀn
(nꢁ3, RꢁCH3, 1; C2H5, 2; C4H9, 3; C6H5, 4; nꢁ2, RꢁCH3, 5; C2H5, 6; C4H9, 7; C6H5, 8) have been synthesized. All the
complexes 1ꢂ8 have been characterized by elemental, IR and H NMR analyses. Among them complexes 4 and 8 have also been
characterized by X-ray crystallography diffraction analyses, which revealed that the structure of complex 4 is a tetrahedron while the
germanium environment of complex 8 is a distorted octahedron. Furthermore, an intermolecular non-bonded sulfurꢂsulfur
/
/
/
/
1
/
/
1
interaction was recognized in complex 8. The IR and H NMR spectral data indicate such an inclination that those structures of
trialkylgermanium derivatives are apt to be four-coordinated and those of dialkylgermanium derivatives are likely to be six-
coordinated.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: 2,5-Dimercapto-4-phenyl-1,3,4-thiodiazole; Organogermanium(IV); Non-bonded interaction; Crystal structures; X-ray crystallography
diffraction
1. Introduction
to do an initial probe in the coordination chemistry of
germanium complexes so that we report some details of
the syntheses of a series of organogermanium complexes
The complexes of Group 14 elements (silicon, tin and
germanium(IV)) can be obtained by using their tetra-
halides with appropriate ligands [1]. Recently this field
has attracted much attention in order to investigate the
influences of the functional groups on the coordination
modes and properties of these complexes [2,3]. However,
until now most of the studies have been focused on the
organotin and organosilicon compounds for either the
diversity of their commercial application or the richness
of the type RnGe[S(C8H5N2S2)]4ꢀn (nꢁ
/
3, Rꢁ
/
CH3, 1;
C2H5, 2; C4H9, 3; C6H5, 4; nꢁ2, RꢁCH3, 5; C2H5, 6;
/
/
C4H9, 7; C6H5, 8) and characterize them by elemental,
1
IR, H NMR analyses. X-ray crystallography analyses
of the complexes 4 and 8 have also been given in the
present paper.
of their structural chemistry [4ꢂ8]. In our previous
/
2. Experimental
work, we have synthesized and characterized a variety
of penta- or hexa-coordinate organotin complexes where
in most cases the donor is nitrogen or sulfur [9,10].
From a theoretical point of view, we think it necessary
2.1. Materials and measurements
All reagents and solvents were purchased commer-
cially and used without further purification unless
otherwise noted. The melting points were obtained
with Kofler micro melting point apparatus and were
uncorrected. Infrared-spectra were recorded on a Nico-
* Corresponding author. Tel.: ꢃ
823-8274.
E-mail address: macl@lctu.edu.cn (C. Ma).
/
86-635-823-8121; fax: ꢃ86-635-
/
0277-5387/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0277-5387(03)00401-7

2768
C. Ma et al. / Polyhedron 22 (2003) 2767ꢂ2772
/
let-460 spectrophotometer using KBr discs and sodium
1
chloride optics. H NMR spectra were recorded on a
2.2.4. Ph3Ge[S(C8H5N2S2)] (4)
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.264 g, 1 mmol) and triphenylgermanium
chloride (0.339 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. Yellow
crystal complex 4 was obtained from n-hexane. Yield:
JEOL-FX-90Q spectrometer using TMS as internal
standard and CDCl3 as solvent. The chemical shifts
were reported in ppm. Elemental analyses were per-
formed with a PE-2400II apparatus.
89%. M.p. 166ꢂ
/
168 8C. Anal. Found: C, 59.04; H, 3.73;
N, 5.37; S, 18.30; Calc. for C26H20GeN2S3: C, 59.03; H,
2.2. Syntheses of the complexes 1ꢂ8
/
1
3.81; N, 5.29; S, 18.15%. H NMR (CDCl3): 7.34ꢂ
(m, 15H, PhÃH), 7.19ꢂ7.34 (m, 5H, C6H5ÃN). IR (KBr,
cmꢀ1): n(PhÃ
H), 3026; n(GeÃC), 1098; n(GeÃS), 458
cmꢀ1; n(CÄ
N), 1610; n(CÃS), 973; n(CÄS), 1257.
/7.67
/
/
/
2.2.1. (CH3)3Ge[S(C8H5N2S2)] (1)
/
/
/
The reaction was carried out under nitrogen atmo-
sphere. The potassium salt of 2,5-dimercapto-4-phenyl-
1,3,4-thiodiazole (0.264 g, 1 mmol) and trimethylgerma-
nium chloride (0.153 g, 1 mmol) were added to the
solution of absolute benzene (20 ml) in a Schlenk flask,
stirred for 12 h at 40 8C and then filtrated. The filtered
solution was gradually reduced by evaporation under
vacuum until a solid product was obtained. The solid
was then recrystallized from ether. White crystal com-
/
/
/
2.2.5. (CH3)2Ge[S(C8H5N2S2)]2 (5)
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.528 g, 2 mmol) and dimethylgermanium
dichloride (0.173 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. White crystal
complex 5 was obtained from ether. Yield: 90%. M.p.
128ꢂ
S, 34.82; Calc. for C18H16GeN4S6: C, 39.10; H, 2.92; N,
10.13; S, 34.73%. 1H NMR (CDCl3): 7.20ꢂ
7.32 (m, 5H,
NC6H5), 1.78 (s, 6H, GeÃ
CH3). IR (KBr, cmꢀ1): n(PhÃ
H), 3048; n(CÃH), 2964, 2872; n(GeÁ Á ÁN), 632; n(GeÃ
C), 589; n(GeÃS), 453; n(CÄN), 1626; n(CÃS), 990;
n(CÄS), 1256.
/
130 8C. Anal. Found: C, 39.22; H, 2.71; N, 10.30;
plex 1 was formed. Yield: 91%. M.p. 138ꢂ140 8C. Anal.
Found: C, 37.89; H, 4.01; N, 8.29; S, 28.21; Calc. for
C11H14GeN2S3: C, 37.87; H, 4.12; N, 8.17; S, 28.00%.
/
/
/
/
1H NMR (CDCl3): 7.20ꢂ
9H, GeÃ
H), 2985, 2870; n(GeÃ
1595; n(CÃS), 981; n(CÄ
/
7.33 (m, 5H, C6H5Ã
CH3). IR (KBr, cmꢀ1): n(PhÃ
H), 3028; n(CÃ
C), 585; n(GeÃS), 446; n(CÄN),
S), 1256.
/
N), 1.71 (s,
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.2.6. (C2H5)2Ge[S(C8H5N2S2)]2 (6)
2.2.2. (C2H5)3Ge[S(C8H5N2S2)] (2)
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.528 g, 2 mmol) and diethylgermanium
dichloride (0.202 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. Colorless
crystal complex 6 was obtained from ether-dichloro-
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.264 g, 1 mmol) and triethylgermanium
chloride (0.195 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. After
removing the solvent, the solid was redissolved in n-
hexane. Colorless crystal complex 2 was formed. Yield:
methane. Yield: 92%. M.p. 112ꢂ114 8C. Anal. Found:
/
C, 41.44; H, 3.29; N, 9.88; S, 33.17; Calc. for
C20H20GeN4S6: C, 41.35; H, 3.47; N, 9.64; S, 33.05%.
87%. M.p. 124ꢂ
/
126 8C. Anal. Found: C, 43.89; H, 5.66;
N, 5.35; S, 25.17; Calc. for C14H20GeN2S3: C, 43.85; H,
1H NMR (CDCl3): 7.22ꢂ
(q, 4H, GeÃ
n(PhÃH), 3055; n(CÃ
n(GeÃC), 586; n(GeÃ
982; n(CÄS), 1257.
/
7.35 (m, 5H, C6H5Ã
CH2), 0.94 (t, 6H, CH3). IR (KBr, cmꢀ1):
H), 2957, 2856; n(Ge N), 636;
Á Á Á
S), 461; n(CÄN), 1628; n(CÃS),
/
N), 1.75
1
5.78; N, 5.24; S, 24.94%. H NMR (CDCl3): 7.22ꢂ
(m, 5H, C6H5ÃN), 1.76 (q, 6H, GeÃCH2), 0.88 (t, 9H,
CH3). IR (KBr, cmꢀ1): n(PhÃ
H), 3024; n(CÃH), 2979,
2865; n(GeÃC), 579; n(GeÃS), 457; n(CÄN), 1607; n(CÃ
S), 977; n(CÄS), 1256.
/
7.35
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
2.2.7. (n-C4H9)2Ge[S(C8H5N2S2)]2 (7)
2.2.3. (n-C4H9)3Ge[S(C8H5N2S2)] (3)
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.528 g, 2 mmol) and dibutylgermanium
dichloride (0.258 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. Yellow
crystal complex 7 was obtained from n-hexane. Yield:
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.264 g, 1 mmol) and tributylgermanium
chloride (0.279 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. Yellow
crystal complex 3 was obtained from benzene. Yield:
88%. M.p. 74ꢂ
/
76 8C. Anal. Found: C, 45.37; H, 2.99; N,
8.91; S, 30.25; Calc. for C24H28GeN4S6: C, 45.25; H,
89%. M.p. 58ꢂ
/
60 8C. Anal. Found: C, 51.25; H, 6.73; N,
6.12; S, 20.61; Calc. for C20H32GeN2S3: C, 51.21; H,
1
3.16; N, 8.79; S, 30.14%. H NMR (CDCl3): 7.22ꢂ
(m, 5H, PhÃH), 1.73 (t, 4H, GeÃCH2), 1.12ꢂ1.50 (m,
8H, CH2), 0.91 (t, 6H, CH3). IR (KBr, cmꢀ1): n(PhÃ
H),
3047; n(CÃH), 2978, 2868; n(GeÁ Á ÁN), 628; n(GeÃC),
578; n(GeÃS), 459; n(CÄN), 1624; n(CÃS), 974; n(CÄS),
1257.
/
7.34
1
6.88; N, 5.97; S, 20.47%. H NMR (CDCl3): 7.15ꢂ
(m, 5H, PhÃH), 1.79 (t, 6H, GeÃCH2), 1.13ꢂ1.50 (m,
12H, CH2), 0.86 (t, 9H, CH3). IR (KBr, cmꢀ1): n(PhÃ
H), 3020; n(CÃH), 2978, 2868; n(GeÃC), 588; n(GeÃS),
461; n(CÄN), 1603; n(CÃS), 973; n(CÄS), 1257.
/
7.32
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

C. Ma et al. / Polyhedron 22 (2003) 2767ꢂ
/2772
2769
2.2.8. Ph2Ge[S(C8H5N2S2)]2 (8)
complexes 1ꢂ
/
8. Together with the absorption region
The potassium salt of 2,5-dimercapto-4-phenyl-1,3,4-
thiodiazole (0.528 g, 2 mmol) and diphenylgermanium
dichloride (0.298 g, 1 mmol) in benzene (20 ml) were
stirred for 12 h at 40 8C and then filtrated. The filtered
solution was gradually removed until solid product was
obtained. The solid was then recrystallized from ether.
Yellow crystal complex 8 was formed. Yield: 92%. M.p.
ranging from 973 to 990 cmꢀ1 attributed to the
vibration of nCÃS, all above messages indicate the
coordination of the ligand to germanium by sulfur
atom in all complexes 1ꢂ
that complexes 1ꢂ4 are four-coordinated with a sulfur
atom and three alkyl (or phenyl) groups substituted to
the central germanium atom. The geometry at the
germanium atom can be described as Scheme 2a. The
conclusion well coincides with the following X-ray
crystallographic analysis of complex 4.
/8. So it can be concluded
/
118ꢂ
28.44; Calc. for C28H20GeN4S6: C, 53.03; H, 2.98; N,
8.27; S, 28.36%. 1H NMR (CDCl3): 7.35ꢂ
7.64 (m, 10H,
PhÃH), 7.21ꢂ7.35 (m, 5H, C6H5Ã
N). IR (KBr, cmꢀ1):
n(PhÃH), 3061; n(GeÃC), 1096; n(GeÁ Á ÁN), 633; n(GeÃ
S), 453; n(CÄN), 1626; n(CÃS), 986; n(CÄS), 1257.
/
120 8C. Anal. Found: C, 53.13; H, 2.80; N, 8.36; S,
/
/
/
/
It is worthy to note that besides the absorption region
/
/
/
/
/
belonging to GeÃ
another weak bands at about 630 cmꢀ1 which can be
attributed to Ge N vibration [12]. Furthermore, the
Á Á Á
absorption band belonging to CÄN in complexes 5ꢂ8 all
shift about 20 cmꢀ1 towards high-frequency compared
with those of complexes 1ꢂ4, which also prove that
there exist the weak coordination from nitrogen atom of
the ligand to germanium atom in complexes 5ꢂ8. As a
result, the probable geometry for complexes 5ꢂ8 can be
/
S, all spectra of complexes 5ꢂ
/
8 have
/
/
/
/
/
/
/
2.3. X-ray crystallographic studies of complexes 4 and 8
/
All X-ray crystallographic data were collected on a
Bruker SMART CCD 1000 diffractometer. Criterion of
observability was used for the solution and refinement.
The structure was solved by direct methods and refined
by a full-matrix least-squares procedure based on F2
using the SHELXL-97 program system. All data were
/
/
described as distorted octahedron, see Scheme 2b. The
following crystal structure of complex 8 well supports
such a conclusion.
collected at 298(2) K using graphite-monochromated
˚
0.71073 A) and corrected for
Mo Ka radiation (lꢁ
/
Lorentz and polarization effects but not for absorption.
All non-H atoms were included in the model at their
calculated positions. The positions of hydrogen atoms
were calculated, and their contributions in structural
factor calculations were included.
3.3. NMR data of the complexes 1ꢂ
/
8
The 1H NMR spectra show that the chemical shifts of
the phenyl group (GeÃC6H6) in complexes 4 and 8,
7.34ꢂ7.67 ppm, and those of methylene connected
directly with germanium in complexes 1ꢂ3 and com-
plexes 5ꢂ7, 1.72ꢂ1.79 ppm, upfield shift as compared
/
/
/
/
/
3. Results and discussion
with those of their corresponding precursors. All these
data are similar to those cases appear in literature [13],
indicating there may exist novel coordination of the
ligand to germanium atom for all the eight complexes
3.1. Syntheses of the complexes 1ꢂ
The synthesis procedure is given in Scheme 1.
3.2. IR spectroscopic studies of the complexes 1ꢂ
/
8
1ꢂ
connected with nitrogen atom (NÃ
7.35 ppm for all complexes 1ꢂ8.
/8. In addition, the resonance of the phenyl group
/
Ph) appears at 7.15ꢂ
/
/
/
8
The assignment of IR bands of these complexes has
been made by comparison with the IR spectra of their
related precursors. A new absorption band, appearing at
3.4. Crystal structures of complexes 4 and 8
The crystal structures and unit cells or crystal packing
of complexes 4 and 8 in crystal are shown in Figs. 1ꢂ4,
about 450 cmꢀ1 for all eight complexes 1ꢂ
/8, can be
/
attributed to the vibrations of GeÃ
/
S bond according to
the literature [11]. The strong peaks at about 1255 cmꢀ1
respectively. All H atoms have been omitted for the
purpose of clarity. Table 1 list the crystal data and
structure refinement parameters for complexes 4 and 8.
have been attributed to the vibration of nCÄS in all
Scheme 1.

2770
C. Ma et al. / Polyhedron 22 (2003) 2767ꢂ2772
/
Scheme 2.
Fig. 1. Molecular structure of complex 4.
Fig. 4. Unit cell of complex 8.
to the sulfur atom. Thus, complex 4 displays an almost
perfect tetrahedral coordination sphere with four angles
ranging from 108.91(8) to 111.79(10)8. The GeÃ
/
C bond
lengths (1.927(2) to 1.937(3) A) are in the normal range
˚
˚
(1.93 A for GeÃ
/
Cp) [2]. The GeÃ
/
S bond lengths
(2.2798(9) A) is a little longer than that reported in
˚
˚
dichloro-(ferrocene-1,1?-dithiolato)-germane (2.19 A)
[2].
For complex 8, the six-coordinate metal center dis-
plays a slightly distorted octahedral geometry with two
carbons and two sulfur atoms covalently linked to the
germanium atom. The valence extension is performed
via the nitrogen atoms. The two chelating nitrogen
Fig. 2. Unit cell of complex 4.
atoms occupy trans positions (N(1)Ã
148.65(10)8), while the cases for the sulfur bonding
vary and they occupy cis positions (S(2)ÃGe(1)ÃS(4),
93.15(5)8). Besides, the S and N equatorial ligating
atoms belong to the same moiety (S(5)ÃGe(1)ÃN(3):
59.74(8)8, S(2)ÃGe(1)ÃN(1): 59.53(8)8), so their posi-
tions are fixed and the SÃGeÃN angles can only admit
/
Ge(1)Ã
/
N(3),
/
/
/
/
/
/
/
/
very little deformation. The sum of angles between the
germanium atom and the equatorial ligating atoms (i.e.
two N and two S in each case) is 360.08, typical for the
ideal octahedral value of 3608. The GeÃ
/
C bond lengths
Fig. 3. Molecular structure of complex 8.
˚
(1.922(4) and 1.924(4) A) are quite close to the ones in
the literature [2]. It is worthy to note that in complex 8
Tables 2 and 3 lists the selected bond lengths and angles
of complexes 4 and 8.
For complex 4, the central germanium atom forms
four primary bonds: three to the phenyl groups and one
both GeÃ
/
N bond lengths are markedly elongated
˚
(2.984(3) and 3.005(4) A) compared to those reported
in GeCl4(bipy) and GeCl(bipy)(hcit) with values ranging
˚
from 2.000(3) to 2.068(4) A [14], so it is obvious that the

C. Ma et al. / Polyhedron 22 (2003) 2767ꢂ
/2772
2771
Table 1
Crystal data and structure refinement parameters for complexes 4 and
Table 3
˚
Selected bond lengths (A) and angles (8) for complex 8
8
Bond lengths
Complex 4
26H20GeN2S3
Complex 8
Ge(1)Ã
Ge(1)Ã
Ge(1)Ã
S(5)
Á Á Á
/
C(23)
1.922(4)
Ge(1)Ã
/
C(17)
S(5)
N(3)
1.924(4)
Empirical formula
Formula weight
Crystal system
C
529.21
C28H20GeN4S6
677.43
triclinic
/S(2)
2.2588(15) Ge(1)Ã
2.984(3)
3.61
/
2.2786(14)
3.005(4)
3.72
/N(1)
Ge(1)Ã
/
triclinic
¯
/
/
S(2)#
S(2)
/
Á Á Á
/
S(2)#
¯
P1
Space group
P/1
/
Bond angles
C(23)ÃGe(1)Ã
C(17)ÃGe(1)Ã
C(17)ÃGe(1)Ã
C(23)ÃGe(1)Ã
S(2)ÃGe(1)Ã
C(23)Ã
S(2)ÃGe(1)Ã
N(1)Ã
Unit cell dimensions
˚
/
/
C(17) 119.34(19) C(23)Ã
/
Ge(1)Ã
/
S(2)
S(5)
110.32(13)
113.13(12)
93.15(5)
a (A)
˚
9.194(2)
9.595(2)
14.648(4)
85.277(4)
72.303(3)
79.430(4)
1209.2(5)
2
9.956(6)
10.700(6)
15.026(8)
97.225(9)
91.511(9)
111.855(7)
1469.2(14)
2
/
/
S(2)
S(5)
N(1)
111.18(13) C(23)Ã
106.61(14) S(2)ÃGe(1)Ã
81.89(13) C(17)Ã
59.53(8) Ge(1)Ã
S(5)Ã
/
Ge(1)Ã
/
b (A)
˚
c (A)
/
/
/
/S(5)
/
/
/
Ge(1)Ã
/
N(1)
83.12(14)
152.53(8)
81.59(13)
58.74(8)
a (8)
b (8)
g (8)
/
/
N(1)
/
/N(1)
/
Ge(1)Ã
/N(3)
82.04(14) C(17)Ã
/
Ge(1)Ã
/
N(3)
/
/
N(3)
151.82(8)
148.65(10)
S(5)Ã
/
Ge(1)Ã
/N(3)
3
˚
V (A )
/
Ge(1)Ã
/
N(3)
Z
Dcalc (g cmꢀ3
)
1.453
1.531
Crystal size (mm)
F(0 0 0)
0.40ꢄ
540
/0.40ꢄ/0.30
0.30ꢄ
688
/
0.20ꢄ0.09
/
Total reflections
Independent reflections
Data/restraints/para-
meters
7091
4855
8731
5909
bonded S/
Á Á Á
/
S interaction [18,19] and what we recognized
4855/0/369
5909/0/432
in complex 8 can be regarded as a supplement to that
kind of contact.
Final R indices [I ꢀ
/
R1ꢁ
0.0667
R1ꢁ0.0550, wR2ꢁ
/
0.0360, wR2ꢁ
/
R1ꢁ
0.0784
R1ꢁ
/
0.0397, wR2ꢁ
/
2s(I)]
R indices (all data)
/
/
/0.0842, wR2ꢁ
/
0.0724
0.909
0.1075
0.825
4. Conclusions
Goodness-of-fit
u Range for data collec- 1.46ꢂ
/
26.42
1.37ꢂ
1.495
0.344 and ꢀ
/
26.37
A series of germanium complexes based on the 2,5-
dimercapto-4-phenyl-1,3,4-thiodiazole ligand containing
two functional heterocyclic pendants have been synthe-
sized and characterized. Detail studies on the structures
and spectra of these complexes indicate that there exist
such an inclination that the structures of those trialk-
tion (8)
Absorption coefficient
1.543
0.445 and ꢀ
(mmꢀ1
)
Largest difference peak
ꢀ3
/0.358
/
0.425
˚
and hole (e A
)
GeÃ
/
N coordination is very weak. Concerning the GeÃ
/
S
ylgermanium complexes 1ꢂ
geometry and those dialkylgermanium complexes 5ꢂ
are likely to construct octahedral geometry.
/
4 are apt to be of tetrahedral
8
˚
A
/
bond lengths (2.2588(15)
for Ge(1)Ã
/
S(2) and
˚
2.2786(14) A for Ge(1)Ã
are similar to those in complex 4.
Besides, intermolecular non-bonded S
/S(5)), we may note that they
/
Á Á Á
/
S interactions
were recognized in the crystallographic analysis of
complex 8, which help the construction of the dimer of
5. Supplementary material
˚
complex 8. The non-bond S
/
Á Á Á
S(2)# and 3.72 A for S(2)
those reported in literature [15,16] but close to the sum
/
S distance (3.61 A for S(5)
/
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Center, CCDC Nos. 206691 and 206692 for
complexes 4 and 8, respectively. Copies of this informa-
tion may be obtained free of charge from the Director,
˚
Á Á Á
/
/
Á Á Á
/
S(2)#) is longer than
˚
(3.70 A) of the van der Waals radii (S and S) [17]. There
have been several papers that have discussed the non-
Table 2
˚
Selected bond lengths (A) and angles (8) for complex 4
Bond lengths
Ge(1)Ã
Ge(1)Ã
/
C(21)
1.927(2)
1.937(3)
Ge(1)Ã
Ge(1)Ã
/
C(15)
S(2)
1.934(2)
2.2798(9)
/C(9)
/
Bond angles
C(21)ÃGe(1)Ã
C(15)ÃGe(1)Ã
C(15)ÃGe(1)Ã
/
/
C(15)
C(9)
S(2)
111.50(10)
111.79(10)
99.15(8)
C(21)Ã
C(21)Ã
C(9)ÃGe(1)Ã
/
Ge(1)Ã
/
C(9)
S(2)
113.59(11)
110.95(8)
108.91(8)
/
/
/
Ge(1)Ã
/
/
/
/
/
S(2)

2772
C. Ma et al. / Polyhedron 22 (2003) 2767ꢂ2772
/
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[6] J. Li, Y. Ma, R. Liu, J. Li, Appl. Organomet. Chem. 15 (2001)
227.
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: ꢃ44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk
/
or www: http://www.ccdc.cam.ac.uk).
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Acknowledgements
We thank the National Natural Foundation, P.R.
China (20271025), the Key Teachers Foundation from
the State Education Ministry of China and the National
Natural Foundation of Shandong Province, P.R. China
for financial support of this work.
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