Hydrogen bonding and π-π stacking interaction in the coordination of sulfur and nitrogen donor heterocycle to organotin(IV): Syntheses and crystal structures of di- and triorganotin(IV) derivatives with 1-(4-hydroxyphenyl)-1H- tetrazole-5-thiol

Article abstract of DOI:10.1016/j.poly.2004.03.003

A series of organotin(IV) complexes with 1-(4-hydroxyphenyl)-1H-tetrazole- 5-thiol of the type, R_nSn[S(C₇H₅N ₄O)]_4-n·L (n=3, L=0: R=Me (1), n-Bu (2), Ph (3); n=3, L=0.5C₂H₅OH·0.5H₂O, R=PhCH ₂ (4); n=2, L=H₂O, R=Me (5); n=2, L=0: R=n-Bu (6), Ph (7), PhCH₂ (8)) have been synthesized. All the complexes 1-8 have been characterized by elemental, IR and ¹H NMR analyses. Among them complexes 3, 4, 5 and 6 have also been characterized by X-ray crystallography diffraction analyses, which revealed the 1D ribbons of complexes 3 and 5 and the 2D network of complex 6 due to the versatile intermolecular hydrogen bonds O-H?X (X=O, N, S) in the crystallographic structures. Moreover, strong π-π stacking interactions are found in complexes 4 and 5.

Full text of DOI:10.1016/j.poly.2004.03.003

Polyhedron 23 (2004) 1547–1555
www.elsevier.com/locate/poly
Hydrogen bonding and p–p stacking interaction
in the coordination of sulfur and nitrogen donor heterocycle
to organotin(IV): syntheses and crystal structures
of di- and triorganotin(IV) derivatives
with 1-(4-hydroxyphenyl)-1H-tetrazole-5-thiol
a,b,
a
Chunlin Ma
*, Jiafeng Sun
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Taishan University, Taian 271021, PR China
Received 11 February 2004; accepted 10 March 2004
Available online 9 April 2004
Abstract
A series of organotin(IV) complexes with 1-(4-hydroxyphenyl)-1H-tetrazole-5-thiol of the type, RnSn[S(C7H5N4O)]4 ꢀ n ꢁ L (n ¼ 3,
L ¼ 0: R ¼ Me (1), n-Bu (2), Ph (3); n ¼ 3, L ¼ 0.5C2H5OH ꢁ 0.5H2O, R ¼ PhCH2 (4); n ¼ 2, L ¼ H2O, R ¼ Me (5); n ¼ 2, L ¼ 0:
1
R ¼ n-Bu (6), Ph (7), PhCH2 (8)) have been synthesized. All the complexes 1–8 have been characterized by elemental, IR and H
NMR analyses. Among them complexes 3, 4, 5 and 6 have also been characterized by X-ray crystallography diffraction analyses,
which revealed the 1D ribbons of complexes 3 and 5 and the 2D network of complex 6 due to the versatile intermolecular hydrogen
bonds O–Hꢁ ꢁ ꢁX (X ¼ O, N, S) in the crystallographic structures. Moreover, strong p–p stacking interactions are found in complexes
4 and 5.
Ó 2004 Elsevier Ltd. All rights reserved.
Keywords: 1-(4-Hydroxyphenyl)-1H-tetrazole-5-thiol; Organotin(IV); Hydrogen bonding; p–p stacking interaction; Crystal structures; X-ray
crystallography
1. Introduction
group (N–C–S)ꢀ, respectively. The X-ray analyses re-
vealed that the former act as thiol form but the primary
bond of the latter to the tin atom varies dramatically
according to distinct R of the precursor RnSnCl4 ꢀ n
[5,6]. These results indicate there are several factors can
influence the topologies of the organotin derivatives
from heterocyclic thionates such as the special geome-
tries of ligand, the spacial resistant from R, etc. To
continue our studies in this field, we choose another
fascinating heterocyclic thionate: 1-(4-Hydroxyphenyl)-
1H-tetrazole-5-thiol, which possesses one –SH and one –
OH group, through which primary bonds to tin atoms
are likely formed. Moreover, the three potential coor-
dination nitrogen atoms of tetrazole make the ligand
act as a fulcrum about which lattice construction is
orchestrated in one or more dimensions.
Increasing investigation of organotin(IV) complexes
has been focused on acquiring well-defined solid-state
structures to learn the nature of their versatile coordi-
nation chemistry [1], especially that of some organo-
tin(IV) derivatives from heterocyclic thionates
containing a nitrogen atom (or more) and an adjacent,
exocyclic thioketo group [2–4]. In our previous work, we
studied the coordination chemistry of two ligands of
such kind: 2-mercaptonicotinic acid (Hmnc) and 2,5-
dimercapto-1,3,4-thiodiazole (bismuthiol-I), which pos-
sess one and two deprotonated heterocyclic thioamide
* Corresponding author. Tel.: +866358238121; fax: +866358238274.
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.2004.03.003

1548
C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
In this paper, we report some details of the syntheses
cmꢀ1): m(C@N) 1600, m(Sn–C)as 536, m(Sn–C)s 504,
m(Sn–S) 312.
and characterizations of a series of organotin(IV) com-
plexes with the ligand of the type RnSn[S(C7-
H5N4O)]4 ꢀ n ꢁ L (n ¼ 3, L ¼ 0: R ¼ Me (1), n-Bu (2), Ph
(3); n ¼ 3, L ¼ 0.5C2H5OH ꢁ 0.5H2O, R ¼ PhCH2 (4);
n ¼ 2, L ¼ H2O, R ¼ Me (5); n ¼ 2, L ¼ 0: R ¼ n-Bu (6),
Ph (7), PhCH2 (8)). X-ray crystallography of complexes
3, 4, 5 and 6 show that all the complexes contain the
thiol form of the ligand, i.e. the ligand is linked to the
organometal moiety primarily through sulfur, resem-
bling as Hmnc and 1-phenyl-1H-tetrazole-5-thiol [5,7].
Interestingly, the versatile hydrogen bonding, O–Hꢁ ꢁ ꢁX
(X ¼ O, N, S), and strong p–p stacking interactions are
found.
2.2.2. (n-Bu)3Sn[S(C7H5N4O)] (2)
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.194 g, 1 mmol),
sodium ethoxide (0.068 g, 1 mmol) and (n-Bu)3SnCl
(0.326 g, 1 mmol), reaction time 12 h, temperature 45
°C. Recrystallized from ether–petroleum. White crystal
was formed. Yield, 74%. m.p. 67–69 °C. Anal. Calc. for
C19H32N4OSSn: C, 47.22; H, 6.67; N, 11.59. Found: C,
47.26; H, 6.57; N, 11.70%. 1H NMR (90 MHz, CDCl3):
d 7.25–7.38 (m, 4H,C6H4–N), 0.84–1.71 (m, 27H, Sn–
C4H9) ppm. IR (KBr, cmꢀ1): m(C@N) 1601, m(Sn–C)as
445, m(Sn–C)s 425, m(Sn–S) 309.
2.2.3. Ph3Sn[S(C7H5N4O)] (3)
2. Experimental
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.194 g, 1 mmol),
sodium ethoxide (0.068 g, 1 mmol) and Ph3SnCl (0.385
g, 1 mmol), reaction time 12 h, temperature 45 °C. Re-
crystallized from hexane-dichloromethane. White crys-
tal was formed. Yield, 72%. m.p. 184–186 °C. Anal.
Calc. for C25H20N4OSSn: C, 55.27; H, 3.71; N, 10.31.
Found: C, 55.31; H, 3.76; N, 10.32%. 1H NMR (90
MHz, CDCl3): d 7.18–7.37 (m, 4H,C6H4–N), 7.46–7.79
(m, 15H, Sn–C6H5) ppm. IR (KBr, cmꢀ1): m(C@N)
1599, m(Sn–C)as 444, m(Sn–C)s 409, m(Sn–S) 310.
2.1. Materials and measurements
Trimethyltin chloride, tri-n-butyltin chloride, triphe-
nyltin chloride, dimethyltin dichloride, di-n-butyltin
dichloride, diphenyltin dichloride and 1-(4-hydroxy-
phenyl)-1H-tetrazole-5-thiol were commercially avail-
able, and they were used without further purification.
Tribenzyltin chloride and dibenzyltin chloride were
prepared by a standard method reported in the literature
[8]. The melting points were obtained with Kofler micro
melting point apparatus and are uncorrected. Infrared-
spectra were recorded on a Nicolet-460 spectropho-
tometer using KBr disks and sodium chloride optics. 1H
NMR spectra were obtained on a JEOL-FX-90Q spec-
trometer, chemical shifts were given in ppm relative
to Me4Si in CDCl3 solvent. Elemental analyses were
performed with a PE-2400II apparatus.
2.2.4. (PhCH2)3Sn[S(C7H5N4O)] ꢁ 0.5C2H5OH ꢁ 0.5H2O
(4)
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.194 g, 1 mmol),
sodium ethoxide (0.068 g, 1 mmol) and (PhCH2)3SnCl
(0.427 g, 1 mmol), reaction time 12 h, temperature 45
°C. Recrystallized from dichloromethane. White crystal
was formed. The crystal suitable for X-ray diffraction
was grown from ethanol (95%). Yield, 78%. m.p. 124–
126 °C. Anal. Calc. for C29H30N4O2SSn: C, 56.42; H,
2.2. Syntheses of the complexes 1–8
1
4.90; N, 9.08. Found: C, 56.47; H, 4.86; N, 9.14%. H
2.2.1. Me3Sn[S(C7H5N4O)] (1)
NMR (90 MHz, CDCl3): d 7.30 (m, 4H,C6H4–N), 6.88–
7.15 (m, 15H, Sn–CH2C6H5), 3.74 (m, 1H, CH3CH2-
OH), 2.78 (s, 6H, Sn–CH2C6H5), 1.25 (t, 1.5H, CH3CH2
OH) ppm. IR (KBr, cmꢀ1): m(C@N) 1599, m(Sn–C)as
450, m(Sn–C)s 427, m(Sn–S) 309.
The reaction was carried out under nitrogen atmo-
sphere. The 1-(4-hydroxyphenyl)-1H-tetrazole-5-thiol
(0.194 g, 1 mmol) was added to the solution of ethanol
20 ml with sodium ethoxide (0.068 g, 1 mmol), and the
mixture was stirred for 10 min, then add Me3SnCl (0.199
g, 1 mmol) to the mixture, continuing the reaction for 12
h at 45 °C. After cooling down to the room temperature,
the solution was filtered. The solvent of the filtrate was
gradually removed by evaporation under vacuum until
solid product was obtained. The solid was then recrys-
tallized from ether. White crystal was formed. Yield,
65%. m.p. 118–120 °C. Anal. Calc. for C10H14N4OSSn:
C, 33.64; H, 3.95; N, 15.69. Found: C, 33.68; H, 3.95; N,
2.2.5. Me2Sn[S(C7H5N4O)]2 ꢁ H2O (5)
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.388 g, 2 mmol),
sodium ethoxide (0.136 g, 2 mmol) and Me2SnCl2 (0.220
g, 1 mmol), reaction time 12 h, temperature 45 °C. Re-
crystallized from ether–petroleum. White crystal was
formed. The crystal suitable for X-ray diffraction was
grown from ethanol (95%). Yield, 70%. m.p. 126–128
°C. Anal. Calc. for C16H18N8O3S2Sn: C, 34.74; H, 3.28;
N, 20.26. Found: C, 34.84; H, 3.23; N, 20.07%. 1H
1
15.70%. H NMR (90 MHz, CDCl3): d 7.23–7.38 (m,
4H,C6H4–N), 0.75 (s, 9H, Sn–CH3) ppm. IR (KBr,

C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
1549
NMR (90 MHz, CDCl3): d 7.26–7.40 (m, 8H,C6H4–N),
1.42 (s, 6H, Sn–CH3) ppm. IR (KBr, cmꢀ1): m(C@N)
1600, m(Sn–C)as 476, m(Sn–C)s 450, m(Sn–S) 310.
2.2.8. (PhCH2)2Sn[S(C7H5N4O)]2 (8)
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.388 g, 2 mmol),
sodium ethoxide (0.136 g, 2 mmol) and (PhCH2)2SnCl2
(0.372 g, 1 mmol), reaction time 12 h, temperature 45
°C. Recrystallized from ether–petroleum. White crystal
was formed. Yield, 79%. m.p. 112–114 °C. Anal. Calc.
for C28H24N8O2S2Sn: C, 48.92; H, 3.52; N, 16.30.
Found: C, 49.02; H, 3.59; N, 16.39%. 1H NMR (90
MHz, CDCl3): d 7.17–7.42 (m, 8H, C6H4–N), 6.82–7.05
(m, 10H, Sn–CH2C6H5), 3.52 (s, 4H, Sn–CH2C6H5)
ppm. IR (KBr, cmꢀ1): m(C@N) 1600, m(Sn–C)as 440,
m(Sn–C)s 421, m(Sn–S) 310.
2.2.6. (n-Bu)2Sn[S(C7H5N4O)]2 (6)
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.388 g, 2 mmol),
sodium ethoxide (0.136 g, 2 mmol) and (n-Bu)2SnCl2
(0.304 g, 1 mmol), reaction time 12 h, temperature 45
°C. Recrystallized from ether–petroleum. White crystal
was formed. Yield, 76%. m.p. 128–130 °C. Anal. Calc.
for C22H28N8O2S2Sn: C, 42.66; H, 4.56; N, 18.09.
Found: C, 42.75; H, 4.49; N, 18.20%. 1H NMR (90
MHz, CDCl3): d 7.20–7.37 (m, 8H,C6H4–N), 0.86–2.12
(m, 18H, Sn–C4H9) ppm. IR (KBr, cmꢀ1): m(C@N)
1600, m(Sn–C)as 441, m(Sn–C)s 425, m(Sn–S) 315.
2.3. X-ray crystallographic studies of complexes 3, 4, 5
and 6
2.2.7. Ph2Sn[S(C7H5N4O)]2 (7)
The synthesis procedure was the same as 1. 1-(4-
Hydroxyphenyl)-1H-tetrazole-5-thiol (0.388 g, 2 mmol),
sodium ethoxide (0.136 g, 2 mmol) and Ph2SnCl2 (0.344
g, 1 mmol), reaction time 12 h, temperature 50 °C. Re-
crystallized from ether–petroleum. White crystal was
formed. Yield, 67%. m.p. 168–170 °C. Anal. Calc. for
C26H20N8O2S2Sn: C, 47.36; H, 3.06; N, 17.00. Found:
C, 47.48; H, 2.91; N, 17.12%. 1H NMR (90 MHz,
CDCl3): d 7.20–7.33 (m, 8H,C6H4–N), 7.46–7.79 (m,
10H, Sn–C6H5) ppm. IR (KBr, cmꢀ1): m(C@N) 1601,
m(Sn–C)as 444, m(Sn–C)s 415, m(Sn–S) 309.
Crystals were mounted in Lindemann capillaries un-
der nitrogen. All X-ray crystallographic data were col-
lected on a Bruker SMART CCD 1000 diffractometer
with graphite monochromated Mo Ka radiation
ꢀ
(k ¼ 0:71073 A) at 298(2) K. A semi-empirical absorp-
tion correction was applied to the data. The structure
was solved by direct methods using SHELXL-97 and re-
fined against F2 by full-matrix least-squares using
SHELXL-97. Hydrogen atoms were placed in calculated
positions. Crystal data and experimental details of the
structure determinations are listed in Table 1.
Table 1
Crystal data and structure refinement parameters for complex 3, 4, 5 and 6
Complexes
3
4
5
6
Empirical formula
Formula weight
Crystal system
C
543.20
25H20N4OSSn
C29H30N4O2SSn
617.32
triclinic
C16H18N8O3S2Sn
553.19
C22H28N8O2S2Sn
619.33
triclinic
ꢁ
orthorhombic
Pnma
monoclinic
P21=n
ꢁ
Space group
Unit cell dimensions
P1a
P1
ꢀ
a (A)
9.517(5)
10.533(5)
12.313(6)
24.147(11)
86.956(6)
88.200(7)
71.827(6)
2971(2)
7.223(13)
22.09(4)
16.76(3)
90
14.964(12)
9.548(8)
ꢀ
b (A)
14.348(8)
18.953(11)
107.796(8)
100.726(8)
102.442(8)
2316(2)
ꢀ
c (A)
20.233(16)
90
a (°)
b (°)
c (°)
90
90
111.703(9)
90
2686(4)
3
ꢀ
V (A )
2674(8)
4
1.374
Z
4
1.558
4
1.380
4
1.532
Dc (Mg mꢀ3
)
Absorption coefficient (mmꢀ1
F ð000Þ
)
1.218
1088
0.961
1256
1.140
1104
1.142
1256
Crystal size (mm)
0.32 ꢂ 0.15 ꢂ 0.11
1.56–25.03
8093 (Rint ¼ 0:0281)
8093/0/577
0.925
0.55 ꢂ 0.33 ꢂ 0.25
1.69–25.03
10345 (Rint ¼ 0:0254)
10345/5/675
1.063
0.29 ꢂ 0.23 ꢂ 0.16
1.84–25.02
2323 (Rint ¼ 0:1932)
2323/3/147
0.904
0.41 ꢂ 0.35 ꢂ 0.09
2.39–25.02
4652 (Rint ¼ 0:0462)
4652/0/316
0.956
h range (°)
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F 2
Final R indices [I > 2rðIÞ]
R1 ¼ 0:0408,
wR2 ¼ 0:0937
R1 ¼ 0:0704,
wR2 ¼ 0:1143
R1 ¼ 0:0413,
wR2 ¼ 0:0981
R1 ¼ 0:0662,
wR2 ¼ 0:1139
R1 ¼ 0:0706,
wR2 ¼ 0:1319
R1 ¼ 0:1526,
wR2 ¼ 0:1563
R1 ¼ 0:0537,
wR2 ¼ 0:1317
R1 ¼ 0:0838,
wR2 ¼ 0:1492
R indices (all data)

1550
C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
N
to literatures [12,13], which suggested the coordinates of
free ligand to these complexes is through sulfur atoms
via thiol form.
EtONa
N
N
RnSnCl4-n
+
N
OH
RnSn[S(C7H5N4O)]4-n.L
SH
(n = 3, L = 0: R = Me 1, n-Bu 2, Ph 3; n = 3, L = 0.5C2H5OH 0.5H2O, R =PhCH2 4;
n = 2, L = H2O, R = Me 5; n = 2, L = 0: R = n-Bu 6, Ph 7, PhCH2 8)
1
3.3. H NMR data of the complexes 1–8
Scheme 1.
1H NMR data showed that the signal of the –SH
proton in the spectrum of the ligand is absent in all of
the complexes, indicating the removal of the –SH proton
and the formation of Sn–S bonds. The formation ac-
cords well with what the IR data have revealed. More-
over, the 1H NMR spectra show that the chemical shifts
of the phenyl group (Sn–C6H5) in complexes 3 and 7,
7.46–7.79 ppm, and those of methylene connected di-
rectly with tin in complexes 2, 4, 6 and 8, 1.71–3.52 ppm,
upfield shift as compared with those of their corre-
sponding precursors. All these data are similar to those
cases appear in literature [14], indicating there may exist
novel coordination of the ligand to tin atom for all the
eight complexes 1–8. In addition, the resonance of the
phenyl group connected with nitrogen atom and hy-
droxyl group (N–C6H4–OH) appears at 7.17–7.42 ppm
for all complexes 1–8.
3. Results and discussion
3.1. Syntheses of the complexes 1–8
The synthesis procedure is given in Scheme 1.
3.2. IR spectroscopic studies of the complexes 1–8
The explicit feature in the IR spectra of the eight
complexes 1–8 is the absence of the band in the region
2550–2430 cmꢀ1, which appears in the free ligand as the
m(S–H) vibration, thus indicating metal–ligand bond
formation through this site. In the far-IR spectra, the
absorption about 310 cmꢀ1 region for all complexes 1–8,
which is absent in the spectrum of the ligand, is assigned
to the Sn–S stretching mode of the vibration and all the
values are located within the range for Sn–S vibration
observed in common organotin derivatives of thiolate
(300–400 cmꢀ1) [9,10]. In organotin compounds, the IR
spectra can provide useful information concerning the
geometry of the SnCn moiety [11]. In the case of our
compounds, for both di- and triorganotin(IV) deriva-
tives, two bands were assigned to asymmetric and
symmetric Sn–C vibrations. Thus suggesting nonlinear
SnC2 units for diorganotins and non-planar SnC3 frag-
ments for triorganotins, respectively. The middle inten-
sity bands observed at about 1600 cmꢀ1 in the spectra of
all complexes have been assignable to m(C@N) according
3.4. Crystal structures of complexes 3, 4, 5 and 6
3.4.1. Ph3Sn[S(C7H5N4O)] (3)
For complex 3, the asymmetric unit contains two
monomers A and B (Fig. 1), which are crystallographi-
cally nonequivalent. The conformations of the two in-
dependent molecules A and B are almost the same, with
only small differences in bond lengths and bond angles
(see Table 2). The compound is formed by discrete
molecules in which the tin atom is indeed bound to the
sulfur atom of the tetrazolate, which together with the
phenyl groups defines a distorted tetrahedron around
Fig. 1. Molecular structure of the complex 3.

C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
1551
Table 2
Selected bond lengths (A) and bond angles (°) for complex 3
ꢀ
Molecule A
Molecule B
Bond lengths
Sn(1)–C(8)
Sn(1)–C(20)
Sn(1)–C(14)
Sn(1)–S(1)
Sn(1)ꢁ ꢁ ꢁN(4)
N(4)–C(1)
2.128(6) Sn(2)–C(39)
2.136(6) Sn(2)–C(45)
2.152(5) Sn(2)–C(33)
2.4760(17) Sn(2)–S(2)
3.330(6) Sn(2)ꢁ ꢁ ꢁN(8)
1.313(7) N(8)–C(26)
1.740(5) S(2)–C(26)
2.122(6)
2.129(5)
2.138(6)
2.4726(17)
3.487(6)
1.315(7)
1.727(6)
S(1)–C(1)
Fig. 2. perspective view showing the 1D ribbon of the complex 3.
Bond angles
C(8)–Sn(1)–C(20) 112.4(2)
C(8)–Sn(1)–C(14) 110.1(2)
C(20)–Sn(1)–C(14) 111.9(2)
C(39)–Sn(2)–C(45) 112.1(2)
C(45)–Sn(2)–C(33) 110.3(2)
C(39)–Sn(2)–C(33) 111.2(2)
119.28(15) C(39)–Sn(2)–S(2) 119.55(15)
might be the result of packing effects in the crystal.
The molecular structure of complex 4 is shown in
Fig. 3. Selected bond lengths and angels are listed in
Table 3.
In the monomeric units the tetrazolethiolato ligand is
primarily coordinated through the sulfur atom: Sn(1)–
C(8)–Sn(1)–S(1)
C(20)–Sn(1)–S(1) 104.81(15) C(33)–Sn(2)–S(2)
108.24(16)
94.07(14)
105.8(2)
C(14)–Sn(1)–S(1)
C(1)–S(1)–Sn(1)
N(4)–C(1)–S(1)
97.31(15) C(45)–Sn(2)–S(2)
99.83(18) C(26)-S(2)–Sn(2)
126.9(4)
N(8)–C(26)–S(2)
126.9(4)
ꢀ
ꢀ
S(1) 2.5812(14) A, Sn(2)–S(2) 2.6260(15) A. They are
slightly longer than the sum of the covalent radii (2.42
the tin atom. There is also an intramolecular tin–nitro-
ꢀ
ꢀ
A) [18]. This is consistent with the thiol form of the li-
gen short contact (Sn(1)ꢁ ꢁ ꢁN(4) 3.330(6) A for A and
ꢀ
Sn(2)ꢁ ꢁ ꢁN(8) 3.487(6) A for B), shorter than the sum of
gand in the previously reported molecular structure of
Bz3SnSCN4Ph [7c], and in contrast to the primary co-
ordination suggested on the basis of IR data. It is similar
to the complex 3, there are also secondary intramolec-
ular tin–nitrogen short contacts (Sn(1)ꢁ ꢁ ꢁN(4) 3.289(4)
ꢀ
the van der Waals radii (3.75 A) [15]. The C–Sn–C bond
angles are close to the theoretical tetrahedral angle but
the C–Sn–S bond angles more acute or obtuse than it,
largest deviations occurring in C(8)–Sn(1)–S(1)
119.28(15)° for A and C(39)–Sn(2)–S(2) 119.55(15)° for
B; C(14)–Sn(1)–S(1) 97.31(15)° for A and C(45)–Sn(2)–
S(2) 94.07(14)° for B. This is possibly due to the sec-
ondary interaction (Sn(1)ꢁ ꢁ ꢁN(4) for A and Sn(2)ꢁ ꢁ ꢁN(8)
ꢀ
ꢀ
A and Sn(2)ꢁ ꢁ ꢁN(8) 3.311(4) A), shorter than the sum of
ꢀ
the van der Waals radii (3.75 A) [15]. In the crystal, the
molecules of complex 3 associated in polymeric chains
through intermolecular, dative tin–nitrogen bonds
ꢀ
ꢀ
ꢀ
for B). The Sn–S bond length (Sn(1)–S(1) 2.4760(17) A
(Sn(1)–N(7A) 2.604(4) A and Sn(2)–N(3) 2.557(4) A).
This leads to an increase in the tin coordination number
to 5. The coordination polyhedron around the central
tin atom can be described as distorted trigonal bipyra-
midal. The methylene carbons are in equatorial posi-
tions and the axial ones are occupied by the sulfur atom
of the ligand and a nitrogen atom of a neighboring
molecule, respectively.
ꢀ
for A and Sn(2)–S(2) 2.4726(17) A for B) lies toward the
middle of the range reported for triphenyltin heteroa-
ꢀ
renethiolates (2.405–2.481 A) [16,17] and approach the
ꢀ
sum of the covalent radii of tin and sulfur (2.42 A) [18].
In the tetrazolate, the C–S bond distance (C(1)–S(1)
ꢀ
1.740(5) A for A and C(26)–S(2) 1.727(6) A for B) lies
ꢀ
between the average value for the double C@S bond in
ꢀ
thioureas (1.681 A) and the single C–S bond in the C–S–
The component (PhCH2)3Sn[S(C7H5N4O)] crystal-
lizes with 0.5 molecules of ethanol and 0.5 molecules of
water while the water molecule shows no short contacts,
the ethanol is involved in two hydrogen bonds, both as a
ꢀ
Me fragment (1.789 A) [19], suggesting that the C–S
bond has some double-bond character in the deproto-
nated tetrazole.
ꢀ
Moreover, the discrete molecules of complex 3 asso-
ciate in a 1D ribbon by hydrogen bonds (O(1)–
donor (O(3)–H(3A)ꢁ ꢁ ꢁO(2) 2.735 A, O(3)–H(3A)–O(2)
169.33°) and as an acceptor (O(2)–H(33)ꢁ ꢁ ꢁO(3) 2.735
ꢀ
ꢀ
H(1)ꢁ ꢁ ꢁN(3) 2.911 A, O(1)–H(1)–N(3) 157.88° for A;
A, O(2)–H(33)–O(3) 168.41°). Moreover, the polymeric
chain in the unit cell associates in a dimeric form with
ꢀ
O(2)–H(2)ꢁ ꢁ ꢁN(7) 2.857 A, O(1)–H(1)–N(3) 148.77° for
B). A view of the extended ribbon is shown in Fig. 2.
another chain through the O(1)–H(5)ꢁ ꢁ ꢁS(1) (O(1)ꢁ ꢁ ꢁ
ꢀ
S(1) 3.338 A, O(1)–H(5)–S(1) 155.93°) hydrogen bond.
3.4.2. (PhCH2)3Sn[S(C7H5N4O)] ꢁ 0.5C2H5OH ꢁ 0.5H2O
(4)
The crystal structure of 4 shows ring-stacking interac-
tions, each hydroxyphenyl group involved O–Hꢁ ꢁ ꢁS
hydrogen bond is arrange face-to-face at a distance of
The X-ray diffraction investigation of complex 4 has
shown two independent molecules in the unit cell, which
are alternatively associated in a polymeric chain through
intermolecular dative N ! Sn bonds. The differences in
the bond lengths and angles within the two molecules
ꢀ
3.744 A and shows significant p–p stacking interactions,
as reported in the literatures [20]. A view of the unit cell
of 4 showing hydrogen bonds and p–p stacking inter-
actions is given in Fig. 4.

1552
C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
Fig. 3. Molecular structure of the complex 4.
Table 3
ꢀ
Selected bond lengths (A) and bond angles (°) for complex 4
Intramolecular
Bond lengths
Sn(1)–C(8)
Sn(1)–C(15)
Sn(1)–C(22)
Sn(1)–S(1)
Sn(1)ꢁ ꢁ ꢁN(4)
N(4)–C(1)
S(1)–C(1)
2.144(5)
2.149(4)
2.166(5)
2.5812(14)
3.289(4)
1.326(5)
1.729(4)
Sn(2)–C(36)
Sn(2)–C(43)
Sn(2)–C(50)
Sn(2)–S(2)
2.154(5)
2.159(5)
2.163(5)
2.6260(15)
3.311(4)
1.327(6)
1.706(5)
Sn(2)ꢁ ꢁ ꢁN(8)
N(8)–C(29)
S(2)–C(29)
Bond angles
C(8)–Sn(1)–C(15)
C(8)–Sn(1)–C(22)
C(15)–Sn(1)–C(22)
C(8)–Sn(1)–S(1)
C(15)–Sn(1)–S(1)
C(22)–Sn(1)–S(1)
C(1)–S(1)–Sn(1)
N(4)–C(1)–S(1)
116.3(2)
124.16(19)
114.9(2)
C(36)–Sn(2)–C(43)
C(36)–Sn(2)–C(50)
C(43)–Sn(2)–C(50)
C(36)–Sn(2)–S(2)
C(43)–Sn(2)–S(2)
C(50)–Sn(2)–S(2)
C(29)–S(2)–Sn(2)
N(8)–C(29)–S(2)
127.6(2)
116.0(2)
115.2(2)
96.32(15)
95.73(14)
99.43(14)
98.41(15)
128.0(3)
94.09(14)
97.19(15)
89.04(14)
100.00(16)
126.1(4)
Intermolecular
Bond lengths
Sn(1)–N(7A)
2.604(4)
Sn(2)–N(3)
2.557(4)
Bond angles
N(7A)–Sn(1)–C(8)
N(7A)–Sn(1)–C(15)
N(7A)–Sn(1)–C(22)
N(7A)–Sn(1)–S(1)
85.04(18)
80.05(17)
83.06(17)
175.73(10)
N(3)–Sn(2)–C(36)
N(3)–Sn(2)–C(43)
N(3)–Sn(2)–C(50)
N(3)–Sn(2)–S(2)
87.85(17)
83.69(17)
87.72(16)
176.71(9)
3.4.3. Me2Sn[S(C7H5N4O)]2 ꢁ H2O (5) and (n-Bu)2Sn-
[S(C7H5N4O)]2 (6)
atoms, apart from the two methyl or methylene carbons,
and interacts intramolecularly with the unsubstituted
nitrogen atoms of the ring thioamide moiety (N(4),
N(4A) for 5 and N(4), N(8) for 6). The Sn–C bond
Selected bond lengths and bond angles for 5 and 6 are
given in Tables 4 and 5, respectively. The molecular
structures of 5 and 6 are shown in Figs. 5 and 6. In
contrast with the triorganotin derivatives mentioned
above, the coordination of diorganotin derivatives is
different. In both complexes 5 and 6, the tin atom es-
tablishes covalent bonds with the two heterocyclic sulfur
ꢀ
lengths (2.050(15) and 2.111(14) A in 5; 2.134(6) and
ꢀ
2.150(7) A in 6) are quite close to those previously de-
scribed in the literature [6]. The Sn–S bond distances
ꢀ
(2.505(4) A in 5; 2.4740(19) and 2.4716(19) A in 6) are
ꢀ
very close to the sum of the corresponding covalent radii

C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
1553
Table 5
ꢀ
Selected bond lengths (A) and bond angles (°) for complex 6
Bond lengths
Sn(1)–C(15)
Sn(1)–C(19)
Sn(1)–S(2)
Sn(1)–S(1)
Sn(1)–N(4)
2.134(6)
2.150(7)
Sn(1)–N(8)
N(4)–C(1)
3.175(5)
1.324(6)
1.318(6)
1.732(5)
1.743(5)
2.4716(19) N(8)–C(8)
2.4740(19) S(1)–C(1)
3.154(5)
S(2)–C(8)
Bond angles
C(15)–Sn(1)–C(19) 129.2(3)
C(19)–Sn(1)–N(8)
S(2)–Sn(1)–N(8)
S(1)–Sn(1)–N(8)
N(4)–Sn(1)–N(8)
C(1)–N(4)–Sn(1)
C(8)–N(8)–Sn(1)
N(4)–C(1)–S(1)
C(8)–S(2)–Sn(1)
N(4)–C(1)–S(1)
N(8)–C(8)–S(2)
92.63(17)
56.27(9)
140.61(8)
161.87(11)
79.3(3)
C(15)–Sn(1)–S(2)
C(19)–Sn(1)–S(2)
C(15)–Sn(1)–S(1)
C(19)–Sn(1)–S(1)
S(2)–Sn(1)–S(1)
C(15)–Sn(1)–N(4)
C(19)–Sn(1)–N(4)
S(2)–Sn(1)–N(4)
S(1)–Sn(1)–N(4)
C(15)–Sn(1)–N(8)
108.55(17)
109.64(17)
107.78(18)
107.83(17)
84.87(8)
79.7(3)
86.88(17)
83.52(17)
141.56(8)
56.73(9)
96.92(17)
97.88(17)
126.9(4)
126.0(4)
Fig. 4. Packing diagram of complex 4, showing hydrogen bonds and
p–p stacking interactions.
81.85(17)
Table 4
ꢀ
Selected bond lengths (A) and bond angles (°) for complex 5
Bond lengths
Sn(1)–C(9)
Sn(1)–C(8)
Sn(1)–S(1)
2.050(15) Sn(1)–N(4)
2.111(14) N(4)–C(1)
2.704(8)
1.287(10)
1.724(9)
2.505(4)
S(1)–C(1)
Bond angles
C(9)–Sn(1)–C(8)
C(9)–Sn(1)–S(1)
C(8)–Sn(1)–S(1)
S(1A)–Sn(1)–S(1)
C(9)–Sn(1)–N(4)
C(8)–Sn(1)–N(4)
134.8(6)
S(1A)–Sn(1)–N(4) 151.95(16)
103.6(3)
107.5(3)
91.50(17)
87.0(2)
S(1)–Sn(1)–N(4)
C(1)–N(4)–Sn(1)
C(1)–S(1)–Sn(1)
N(4)–C(1)–S(1)
60.59(18)
89.9(5)
88.1(3)
121.3(6)
80.72(19)
Fig. 5. Molecular structure of the complex 5.
ꢀ
(2.42 A) [18], and is similar to the distances found in
other Sn(IV) complexes of the terazolethiolato with
is worth noting that in complex 5 the Sn–N bond length
ꢀ
is shorten (2.704(8) A) than those reported in analogous
diorganotin derivatives of 1-phenyl-1H-tetrazole-5-
ꢀ
metal–sulfur primary bonds, viz. 2.474(3)–2.614(5) A. It
Fig. 6. Molecular structure of the complex 6.

1554
C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
Fig. 7. perspective view showing the 2D network of the complex 5.
ꢀ
thilato (2.975(5) [7a] and 2.947(4) A [7b]). But in com-
ꢀ
plex 6 the Sn–N bond lengths are longer (3.154(5) A and
ꢀ
3.175(5) A), although they all lie within the sum of their
ꢀ
respective van der Walls radii (3.75 A).
the 2D network of 5 (see Fig. 7). It is worthy noting
that no short contacts have been found though the
main component Me2Sn[S(C7H5N4O)]2 crystallizes
with one water molecule. Moreover, ring-stacking in-
teractions are shown in the complex 5. The orientation
is such that the phenyl ring substituents ‘face’ other
phenyl ring on neighboring layer at a distance of
The establishment of such intramolecular tin–ni-
trogen interactions brings the present structure rather
far from a regular tetrahedron, i.e. despite the fact
that the complexes’ core angles (S(1)–Sn(1)–C(9)
103.6(3)° and S(1)–Sn(1)–C(8) 107.5(3)° for 5; S(1)–
Sn(1)–C(15) 107.78(18)°, S(1)–Sn(1)–C(19) 107.83(17)°,
S(2)–Sn(1)–C(15) 108.55(17)° and S(2)–Sn(1)–C(19)
109.64(17)° for 6) are close the expected tetrahedral
value, the C–Sn–C angle (134.8(6)° for 5 and 129.2(3)°
for 6) is more obtuse due to the occurrence of the Sn–
N secondary interactions in a plane bisecting it, with
the concomitant decrease of the S–Sn–S angle
(91.50(17)° for 5 and 84.87(8)° for 6). The geometry
around the metal may thus be viewed, alternatively, as
ꢀ
3.677 A and show significant p–p stacking interactions
[20]. A view of the crystal packing along the a axis is
shown in Fig. 8. As for 6, the hydrogen bonds are
ꢀ
also found (O(1)–H(1)ꢁ ꢁ ꢁN(3) 2.892 A, O(1)–H(1)–
ꢀ
N(3) 138.73° and O(2)–H(2)ꢁ ꢁ ꢁN(7) 2.886 A, O(1)–
H(1)–N(3) 139.08°) and its discrete molecules are
a
distorted trapezoidal bipyramid, with the two
methyl or methylene carbons in bent axial positions
and the trapezoidal plane being defined by the two
Sn–S covalent bonds and the two Sn–N secondary
interactions.
In the complex 5, the hydrogen bonding between
the hydroxyl of ligand and nitrogen atom adjacent
ꢀ
molecule (O(1)–H(1)ꢁ ꢁ ꢁN(3) 2.750 A, O(1)–H(1)–N(3)
Fig. 8. Packing diagram of complex 5, showing p–p stacking
interactions.
167.89°) is recognized, which contributes to construct

C. Ma, J. Sun / Polyhedron 23 (2004) 1547–1555
1555
Acknowledgements
We thank the National Natural Science Foundation
of China (20271025) and the Natural Science Founda-
tion of Shandong Province for financial support.
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Crystallographic data (excluding structure factors)
for the structure reported in this paper have been de-
posited with the Cambridge Crystallographic Data
Center as Supplementary Publication Nos. CCDC-
220182, 222015, 222017, 220175. Copies of the data can
be obtained free of charge on application to the Direc-
tor, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk
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