Syntheses, characterizations and crystal structures of new triorgano-tin or -germanium complexes with 1H-5-mercapto-1,2,3-triazolato

Article abstract of DOI:10.1016/j.poly.2004.05.005

A series of triorganotin and triorganogermanium(IV) complexes with 1H-5-mercapto-1,2,3-triazolato, of the type R₃MSC₂H ₂N₃ (M=Sn, R=CH₃, (1); C₂H ₅, (2); n-C₄H₉, (3); C₆H ₅, (4); M=Ge, R=CH₃, (5); C₂H₅, (6); n-C₄H₉, (7); C₆H₅, (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 Sn and Ge atom environments are distorted tetrahedral coordination polyhedrons, coordinated to three phenyl groups and to one sulfur atom of the ligand. The packing of complexes 4 and 8 is stabilized into a one-dimensional infinite chain by intermolecular N-H?N hydrogen bonds.

Full text of DOI:10.1016/j.poly.2004.05.005

Polyhedron 23 (2004) 1981–1986
www.elsevier.com/locate/poly
Syntheses, characterizations and crystal structures of new
triorgano-tin or -germanium complexes with
1H-5-mercapto-1,2,3-triazolato
a,b,
a
a
Chunlin Ma
*, Junhong Zhang , Rufen Zhang
a
Department of Chemistry, Liaocheng University, 34 Wenhua Road, Liaocheng 252059, China
b
Department of Chemistry, Taishan University, Taian 271021, China
Received 15 March 2004; accepted 4 May 2004
Available online
Abstract
A series of triorganotin and triorganogermanium(IV) complexes with 1H-5-mercapto-1,2,3-triazolato, of the type R3MSC2H2N3
(M ¼ Sn, R ¼ CH3, (1); C2H5, (2); n-C4H9, (3); C6H5, (4); M ¼ Ge, R ¼ CH3, (5); C2H5, (6); n-C4H9, (7); C6H5, (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 Sn and Ge atom environments
are distorted tetrahedral coordination polyhedrons, coordinated to three phenyl groups and to one sulfur atom of the ligand. The
packing of complexes 4 and 8 is stabilized into a one-dimensional infinite chain by intermolecular N–Hꢀ ꢀ ꢀN hydrogen bonds.
Ó 2004 Elsevier Ltd. All rights reserved.
Keywords: 1H-5-mercapto-1,2,3-triazolato; Organotin; Organogermanium(IV); Crystal structure; X-ray crystallography
1. Introduction
of a series of organotin and organogermanium com-
plexes R3MSC2H2N3 (M ¼ Sn, R ¼ CH3, (1); C2H5, (2);
n-C4H9, (3); C6H5, 4; M ¼ Ge, R ¼ CH3, (5); C2H5, (6);
C4H9, (7); C6H5, (8)) and their characterization by ele-
mental, IR and H NMR analyses. X-ray crystallogra-
phy analyses of the complexes 4 and 8 have also been
given in the present paper.
Metal thiolato complexes have been extensively
studied because of their ability to adopt various nucle-
arities and their relevance in biology, since they form the
inorganic part of the biologically active centers of some
metalloproteins and enzymes [1–3]. Recently, attention
has been paid to the coordination chemistry of hetero-
cyclic thiol/thione donors, which can give potential ac-
cess to new compounds with unusual structures and
reactivities [4]. For example, triazyl- and tetrazole-thiol
organometallic derivatives have been reported. A related
class of such compounds is thiosemicarbazones in which
the structure unit HS–C–N–N or S@C–N–N can bond
to metal ions through S or N or both atoms [5–8].
As a result of our continuing interest in the coordi-
nation of main group metals with polydentate S, N li-
gands [9–11], here we report the studies on the syntheses
1
2. Experimental
2.1. Materials and measurements
All reagents and the sodium salt of the ligand (1H-5-
mercapto-1,2,3-triazole) were purchased commercially
and used without further purification unless otherwise
noted. The melting points were obtained with a Kofler
micro-melting point apparatus and were uncorrected.
Infrared-spectra were recorded on a Nicolet-460 spec-
trophotometer using KBr discs and sodium chloride
optics. 1H NMR spectra were recorded on a JEOL-FX-
90Q spectrometer using TMS as internal standard and
* Corresponding author. Tel.: +86-635-8238121; fax: +86-635-
8238274/86-538-671-5521.
E-mail address: macl@lctu.edu.cn (C. Ma).
0277-5387/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2004.05.005

1982
C. Ma et al. / Polyhedron 23 (2004) 1981–1986
CDCl3 as solvent. The chemical shifts are reported in
ppm. Elemental analyses were performed with a PE-
2400II apparatus.
triazole (0.123 g, 1 mmol), triphenyltin chloride (0.385 g,
1 mmol) and benzene (30 ml). The yellow crystal com-
plex 4 was obtained from hexane–dichloromethane.
Yield, 89%. M.p.: 128–130 °C. Anal. Calc. for
C20H17N3SSn: C, 53.37; H, 3.81; N, 9.33; S, 7.12.
Found: C, 53.24; H, 3.76; N, 9.28; S, 6.97%. IR (KBr,
cmꢁ1): 3250 (br, N–H), 3050 (w, C–H), 1605 (m, C@C),
1595 (C–N), 1443 (m, N@N), 1152, 1076 (m, C–S), 561,
533 (m, Sn–C), 317 (m, Sn–S). 1H NMR (CDCl3): d 11.0
(br, 1H, N–H), 7.31–7.96 (m, 15H, Ph–H), 7.28 (s, 1H,
@CH).
2.2. Syntheses of the complexes 1–8
2.2.1. (CH3)3Sn(SC2H2N3) (1)
The reaction was carried out under nitrogen atmo-
sphere. The sodium salt of 1H-5-mercapto-1,2,3-triazole
(0.123 g, 1 mmol) and trimethyltin chloride (0.199 g, 1
mmol) were added to a solution of absolute benzene (20
ml) in a Schlenk flask, stirred for 12 h at 40 °C and then
filtered. The filtered solution was gradually reduced by
evaporation under vacuum until a solid product was
obtained. The solid was then recrystallized from ether.
The white crystal complex 1 was formed. Yield, 89%.
M.p.: 121–123 °C. Anal. Calc. for C5H11N3SSn: C,
22.76; H, 4.20; N, 15.93. Found: C, 22.72; H, 4.18; N,
15.96%. IR (KBr, cmꢁ1): 3251 (br, N–H), 3052 (w, C–
H), 1605 (m, C@C), 1596 (C–N), 1442 (m, N@N), 1156,
2.2.5. (CH3)3Ge(SC2H2N3) (5)
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
triazole (0.123 g, 1 mmol), trimethylgermanium chlo-
ride (0.153 g, 1 mmol) and benzene (20 ml). The yellow
crystal complex 5 was obtained from hexane–dichlo-
romethane. Yield, 78%. M.p.: 120–122 °C. Anal. Calc.
for C5H11N3SGe: C, 27.57; H, 5.02; N, 19.29. Found:
C, 27.40; H, 5.06; N, 19.05%. IR (KBr, cmꢁ1): 3251
(br, N–H), 3120 (w, C–H), 1608 (m, C@C), 1595 (C–
N), 1445 (m, N@N), 1160, 1073 (m, C–S), 587, 505 (m,
Ge–C), 455 (m, Ge–S). 1H NMR (CDCl3): d 10.8
(br, 1H, N–H), 1.71 (s, 9H, Ge–CH3), 7.29 (s, 1H,
@CH).
1
1078 (m, C–S), 560, 535 (m, Sn–C), 319 (m, Sn–S). H
NMR (CDCl3): d 10.9 (br, 1H, N-H), 1.53 (m, 9H,
CH3), 7.30 (s, 1H, @CH).
2.2.2. (C2H5)3Sn(SC2H2N3) (2)
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
triazole (0.123 g, 1 mmol), triethyltin chloride (0.241 g, 1
mmol) and benzene (20 ml). The colorless crystal com-
plex 2 was obtained from n-hexane. Yield: 82%. M.p.:
124–126 °C. Anal. Calc. for C8H17N3SSn: C, 31.41; H,
5.60; N, 13.74. Found: C, 31.38; H, 5.46; N, 13.79%. IR
(KBr, cmꢁ1): 3250 (br, N–H), 3050 (w, C–H), 1605 (m,
C@C), 1595 (C–N), 1443 (m, N@N), 1152, 1076 (m, C–
S), 561, 524 (m, Sn–C), 317 (m, Sn–S). 1H NMR
(CDCl3): d 10.5 (br, 1H, N–H), 1.76 (q, 6H, –CH2), 0.88
(t, 9H, CH3), 7.28 (s, 1H, @CH).
2.2.6. (C2H5)3Ge(SC2H2N3) (6)
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
triazole (0.123 g, 1 mmol), triethylgermanium chloride
(0.195 g, 1 mmol) and benzene (20 ml). The yellow
crystal complex 6 was obtained from hexane–dichlo-
romethane. Yield, 79%. M.p.: 119–121 °C. Anal. Calc.
for C8H17N3SGe: C, 36.97; H, 6.60; N, 16.17. Found: C,
36.94; H, 6.57; N, 16.19%. IR (KBr, cmꢁ1): 3252 (br, N–
H), 3121 (w, C–H), 1608 (m, C@C), 1596 (C–N), 1443
(m, N@N), 1161, 1073 (m, C–S), 579, 516 (s, Ge–C), 457
1
2.2.3. (n-C4H9)3Sn(SC2H2N3) (3)
(m, Ge–S). H NMR (90 MHz, CDCl3): d 10.8 (br, 1H,
N–H), 1.76 (q, 6H, Ge–CH2), 0.88 (t, 9H, CH3), 7.30 (s,
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
triazole (0.123 g, 1 mmol), tributyltin chloride (0.325 g,
1 mmol) and benzene (20 ml). The colourless crystal
complex 3 was obtained from benzene. Yield: 80%.
M.p.: 58–60 °C. Anal. Calc. for C14H29N3SSn: C, 43.11;
H, 7.50; N, 10.78. Found: C, 43.14; H, 7.53; N, 10.76%.
IR (KBr, cmꢁ1): 3249 (br, N–H), 3050 (w, C–H), 1605
(m, C@C), 1595 (C–N), 1443 (m, N@N), 1152, 1076 (m,
C–S), 565, 540 (m, Sn–C), 316 (m, Sn–S). 1H NMR
(CDCl3): d 10.6 (br, 1H, N–H), 1.79 (t, 6H, –CH2),
1.13–1.50 (m, 12H, CH2), 0.86 (t, 9H, CH3), 7.28 (s, 1H,
@CH).
1H, @CH).
2.2.7. (n-C4H9)3Ge(SC2H2N3) (7)
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
triazole (0.123 g, 1 mmol), triphenylgermanium chloride
(0.279 g, 1 mmol) and benzene (20 ml). The yellow
crystal complex 7 was obtained from hexane–dichlo-
romethane. Yield, 71%. M.p.: 49–51 °C. Anal. Calc. for
C14H29N3SGe: C, 48.89; H, 8.50; N, 12.21. Found: C,
48.87; H, 8.53; N, 12.19%. IR (KBr, cmꢁ1): 3250 (br, N–
H), 3120 (w, C–H), 1605 (m, C@C), 1592(C–N), 1442
(m, N@N), 1162, 1073 (m, C–S), 585, 531 (m, Ge–C),
1
2.2.4. Ph3Sn(SC2H2N3) (4)
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
461 (m, Ge–S). H NMR (CDCl3): d 10.7 (br, 1H, N–
H), 1.79 (t, 6H, Ge–CH2), 1.13–1.50 (m, 12H, CH2),
0.86 (t, 9H, CH3), 7.30 (s, 1H, @CH).

C. Ma et al. / Polyhedron 23 (2004) 1981–1986
1983
2.2.8. Ph3Ge(SC2H2N3) (8)
spectra of related organotin(IV) and organogerma-
nium(IV) compounds. A new absorption band that ap-
pears at about 309–316 cmꢁ1 for complexes 1–4 can be
attributed to the vibration of the Sn–S bond, which is
consistent with that detected for a number of organo-
tin(IV)–sulfur derivatives [12], and the absorption band
that appears at 453–461 cmꢁ1 for complexes 5–8 can be
attributed to the vibrations of the Ge–S bond according
to the literature [13].
The synthesis procedure was the same as in Section
2.2.1, using the sodium salt of 1H-5-mercapto-1,2,3-
triazole (0.123 g, 1 mmol), triphenylgermanium chloride
(0.339 g, 1 mmol) and benzene (25 ml). The yellow
crystal complex 8 was obtained from hexane–dichlo-
romethane. Yield, 73%. M.p.: 130–132 °C. Anal. Calc.
for C20H17N3SGe: C, 59.46; H, 4.24; N, 10.40. Found:
C, 59.40; H, 4.19; N, 10.36%. IR (KBr, cmꢁ1): 3250 (br,
N–H), 3120 (w, C–H), 1608 (m, C@C), 1595 (C–N),
1445 (m, N@N), 1160, 1073 (m, C–S), 591, 535 (m, Ge–
In complexes 1–4, two strong or medium absorptions
are observed at 560–565 and 524–540 cmꢁ1. They are
due to masym and msym Sn–C stretching vibrations, re-
spectively. In complexes 5–8, masym and msym Ge–C
1
C), 453 (m, Ge–S). H NMR (CDCl3): d 11.2 (br, 1H,
N–H), 7.33–7.74 (m, 15H, Ph–H), 7.30 (s, 1H, @CH).
stretching vibrations are at 579–591 and 505–535 cmꢁ1
,
2.3. X-ray crystallographic studies of complexes 4 and 8
respectively. This suggests that there are no-planar SnC3
fragments for all the complexes 1–8.
All X-ray crystallographic data were collected on a
Bruker SMART CCD 1000 diffractometer. The u=x,
scan technique was employed. Corrections were applied
for Lorentz and polarization effects but not for ab-
sorption, satisfying I P rðIÞ. Criterion of observability
was used for the solution and refinement. The structure
was solved by direct methods and refined by a full-ma-
trix least-squares procedure based on F 2 using the
SHELXL-97 program system. All data were collected at
298(2) K using graphite-monochromated Mo Ka radi-
The middle intensity bands observed at 1592–1596
cmꢁ1 in the spectra of all the complexes 1–8 have been
assigned to m(C–N), according to the literature [14], to-
gether with the absorption region ranging from 1442 to
1445 cmꢁ1 attributed to the vibration of m(N@N), which
are all consistent with the free ligand. In the 2800–
2600 cmꢁ1 region the ligands exhibit a broad band
typical of N–H stretching. In the organotin(IV) and
organogermanium(IV) adducts this shifts to 3250 cmꢁ1
.
The position and character of the broadened N–H
stretching band are consistent with the presence of a
NHꢀ ꢀ ꢀN intermolecular hydrogen bond, as reported in
the literature [15].
All the above data indicate the coordination of the
ligand to tin or germanium only by the sulfur atom in all
the complexes 1–8. So it can be concluded that com-
plexes 1–8 are four-coordinate, with a sulfur atom and
three alkyl (or phenyl) groups bonded to the central
metal atom. The conclusion well coincides with the
following X-ray crystallographic analysis of complexes 4
and 8.
ꢀ
ation (k ¼ 0:71073 A) and corrected for 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 cal-
culated, and their contributions in structural factor
calculations were included.
3. Results and discussion
3.1. Syntheses of the complexes 1–8
1
The synthesis procedure was as in the following
Scheme 1:
3.3. H NMR data of the complexes 1–8
The 1HNMR spectra show that the chemical shifts of
the proton on the phenyl group (Sn–C6H6) 7.31–7.96
ppm for 4 and (Ge–C6H6) 7.30–7.74 ppm for 8 and
those of the methylene connected directly with tin in
complexes 1–3 and with germanium in complexes 5–7,
3.2. IR spectroscopic studies of the complexes 1–8
The assignment of the IR bands of all the complexes
1–8 have been made by a comparison with the IR
N
R
N
R
Benzene
R
N
S
M
R
Cl
+
NaS
M
N
N
N
H
H
R
R
M=Sn, R=CH3, 1; C2H5, 2; n-C4H9, 3; C6H5, 4; M=Ge, R=CH3, 5; C2H5, 6; C4H9, 7; C6H5, 8
Scheme 1.

1984
C. Ma et al. / Polyhedron 23 (2004) 1981–1986
1.53–1.79 ppm, upfield shift when compared with those
of their corresponding precursors. All these data are
similar to those cases that appear in the literature [16],
indicating there may exist coordination of the ligand to
the metal atom for all the complexes. In addition, the
broad resonance of the (N–H) proton appears at 10.5–
11.2 ppm for all the complexes 1–8.
3.4. Crystal structures of complexes 4 and 8
The structure details of complexes 4 and 8 are shown
in Figs. 1 and 2, respectively. The intermolecular hy-
drogen-bond packing of complexes 4 and 8 are similar,
one of which is displayed in Fig. 3. Single crystal X-ray
diffraction study details are shown in Table 1, and se-
lected bond lengths and angles are listed in Table 2. The
complexes 4 and 8 exhibit the tin(IV) and the germa-
nium(IV) in a distorted tetrahedral geometry defined by
three phenyl groups and one sulfur atom, which exists as
a bridge between the tin or the germanium atom and the
triazole ring.
Fig. 2. SHELX view of complex 8 (30% probability thermal ellipsoids).
0
ꢀ
dichloro-(ferrocene-1,1 -dithiolato)-germanium (2.19 A)
[20], and is consistent with that in complex 4-
For complex 4, Sn–C bond lengths (2.121(5) to
ꢀ
2.135(5) A) are comparable with the complex: triphe-
ꢀ
CH3C6H5CS2GePh3 (2.2526(8) A) [21]. The angles
nyl(5-mercapto-1-phen-1,2,3,4-tetralato)tin
ꢀ
(2.120–
2.127 A) [17]. The Sn–S distance is 2.4354(15) A, which
ꢀ
around the center Ge element range from 103.00° to
113.40°, which all depart from the theoretical tetrahe-
dral angle.
Furthermore, the salient feature of the superamolec-
ular structure of complexes 4 and 8 is that of a one-di-
mensional hydrogen-bonded polymer, as shown in
Fig. 3, in which N(3) of the triazole bonds to N(1) of a
ꢀ
is consistent with the sum of the covalent radii (2.42 A)
t
[18] and the complex [Cy2NeophylSnS2P(OC6H4 Bu-
ꢀ
4)2] (2.477(3) A) [19], and this distance is much shorter
ꢀ
than the sum of the van der Waals’ radii (4.0 A) [18].
The S–Sn–C bond angles are more acute and the C–Sn–
C bond angles are larger than the theoretical tetrahedral
angle, the largest deviations occurring in S(1)–Sn(1)–
C(15) [101.32(14)°] and C(15)–Sn(1)–C(9) [116.12(17)°].
For complex 8, the germanium atom environment is
similar to that of the tin atom in complex 4. The Ge–C
neighboring triazole through
i
a
hydrogen bond
i
ꢀ
[H(1)ꢀ ꢀ ꢀN(1) 1.966 A, N(3)–H(1)ꢀ ꢀ ꢀN(1) 173.93° for 4);
i
i
ꢀ
H(1)ꢀ ꢀ ꢀN(1) 1.880 A, N(3)–H(1)ꢀ ꢀ ꢀN(1) 165.56° for 8,
(i) X þ 1=2, ꢁY þ 1=2, ꢁZ], the parameters of which are
ꢀ
ꢀ
consistent with that reported, H(1)ꢀ ꢀ ꢀN(1) 1.92(3) A, for
bond lengths (1.925(2)–1.929(3) A) are in the normal
ꢀ
the complex [(C6H5)3SnSCNH2@N–N@C(CH3)(C6H4-
2–OH)] [22].
range (1.93 A for Ge–Cp) [20]. The Ge–S bond length
ꢀ
(2.2406(11) A) is a little longer than that reported in
Fig. 1. SHELX view of complex 4 (30% probability thermal ellipsoids).

C. Ma et al. / Polyhedron 23 (2004) 1981–1986
1985
Fig. 3. A drawing showing the intermolecular hydrogen-bonds in complex 8 (the intermolecular hydrogen-bonds in complex 4 are similar to complex 8).
Table 1
Crystal data and refinement details for complexes 4 and 8
Data and details
4
8
Empirical formula
Formula weight
Temperature (K)
Wavelength (nm)
Crystal system
C20H17N3SSn
450.12
298(2)
C20H17N3SGe
404.02
298(2)
0.71073
monoclinic
P21=c
0.71073
orthorhombic
P2ð1Þ2ð1Þ2ð1Þ
Space group
Unit cell dimensions
ꢀ
a (A)
9.539(2)
21.892 (5)
9.184(4)
9.657(4)
ꢀ
b (A)
ꢀ
c (A)
9.441(2)
93.846 (4)
1967.1(8)
21.283(8)
90
1887.7(12)
b (°)
V (A )
3
ꢀ
Z
4
1.520
4
1.422
Dcalc (Mg/m3)
Absorption coefficient (mmꢁ1
)
1.412
0.8162 and 0.6768
1.740
0.7803 and 0.6059
Maximum and minimum transmission factors
F ð000Þ
896
0.30 ꢂ 0.20 ꢂ 0.15
824
0.32 ꢂ 0.18 ꢂ 0.15
Crystal size (mm)
h Data collection (°)
Index ranges
1.86–26.44
ꢁ11 6 h 6 11, ꢁ15 6 k 6 27,
1.91–26.37
ꢁ10 6 h 6 11, ꢁ12 6 k 6 11,
ꢁ11 6 l 6 11
ꢁ21 6 l 6 26
Reflections collected
Independent reflections
Rint
11458
4034
0.0543
10994
3842
0.0382
Completeness to h ¼ 26:37
Refinement method
Absorption correction
Number of parameters
Goodness-of-fit on F2
Final R indices [I > 2:0rðIÞ]
R indices (all data)
99.7%
99.5%
full-matrix least-squares on F2
semi-empirical from equivalents
294
full-matrix least-squares on F2
semi-empirical from equivalents
294
0.903
0.857
R1 ¼ 0.0409, wR2 ¼ 0.0726
R1 ¼ 0.0881, wR2 ¼ 0.0859
0.584 and )0.724
R1 ¼ 0.0293, wR2 ¼ 0.0467
R1 ¼ 0.0455, wR2 ¼ 0.0495
0.289 and )0.223
ꢁ3
ꢀ
Largest difference peak and hole (e A
)
4. Supplementary material
posited with the Cambridge Crystallographic Data
Center as supplementary publication Nos. CCDC-
192514 and CCDC-207060. Copies of the data can be
obtained free of charge on application to the Director,
Crystallographic data (excluding structure factors)
for the structures reported in this paper have been de-

1986
C. Ma et al. / Polyhedron 23 (2004) 1981–1986
Table 2
ꢀ
Selected bond lengths (A) and angles (°) for complexes 4 and 8
4
8
Bond lengths
Sn(1)–S(1)
Sn(1)–C(8)
Sn(1)–C(9)
Sn(1)–C(15)
S(1)–C(2)
N(1)–N(2)
N(2)–N(3)
N(1)–C(2)
N(3)–C(1)
N(3)–H(1)
N(1)iꢀ ꢀ ꢀH
2.4354(15)
2.121(5)
2.135(5)
2.133(4)
1.746(4)
1.316(5)
1.329(5)
1.348(5)
1.317(6)
0.858
Ge(1)–S(1)
Ge(1)–C(3)
Ge(1)–C(9)
Ge(1)–C(15)
S(1)–C(2)
2.2406(11)
1.926(2)
1.925(3)
1.929(3)
1.743(3)
1.314(3)
1.321(3)
1.347(3)
1.316(4)
0.985
N(1)–N(2)
N(2)–N(3)
N(1)–C(2)
N(3)–C(1)
N(3)–H(1)
N(1)iꢀ ꢀ ꢀH
1.966
1.880
Bond angles
C(8)–Sn(1)–S(1)
C(9)–Sn(1)–S(1)
C(15)–Sn(1)–S(1)
C(8)–Sn(1)–C(15)
C(8)–Sn(1)–C(9)
C(9)–Sn(1)–C(15)
N(3)–H(1)ꢀ ꢀ ꢀN(1)I
C(1)–S(1)–Sn(1)
N(2)–N(1)–C(2)
N(1)–N(2)–N(3)
C(1)–N(3)–N(2)
N(1)–C(1)–S(1)
C(1)–C(2)–S(1)
N(3)–C(1)–C(2)
N(1)–C(2)–C(1)
110.20(13)
107.11(15)
101.32(14)
113.45(19)
108.2(2)
116.12(17)
173.93
C(3)–Ge(1)–S(1)
C(9)–Ge(1)–S(1)
C(15)–Ge(1)–S(1)
C(3)–Ge(1)–C(9)
C(15)–Ge(1)–C(9)
C(3)–Ge(1)–C(15)
N(3)–H(1)ꢀ ꢀ ꢀN(1)i
C(1)–S(1)–Sn(1)
N(2)–N(1)–C(1)
N(1)–N(2)–N(3)
C(2)–N(3)–N(2)
N(1)–C(1)–S(1)
C(2)–C(1)–S(1)
N(3)–C(2)–C(1)
N(1)–C(1)–C(2)
109.00(8)
110.08(11)
103.00(10)
108.70(13)
112.49(14)
113.40(11)
165.56
98.83(16)
109.7(4)
105.7(4)
112.0(4)
122.2(3)
130.6(4)
105.4(5)
107.2(4)
99.79(10)
108.8(2)
106.4(2)
111.4(3)
122.3(2)
129.8(2)
105.8(3)
107.6(3)
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CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk
or www: http://www.ccdc.cam.ac.ck).
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This work was supported by the Natural Science
Foundation of Shandong Province, and the Key
Teachers Foundation from the State Education Minis-
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