Triorganotin(IV) complexes of Schiff base derived from 6-amino-2-mercaptobenzothiazole: Synthesis, characterization and X-ray crystal structures

Article abstract of DOI:10.1016/j.ica.2006.12.017

Nine triorganotin(IV) complexes of the type R₃SnL (L = L1 R = Me 1, Ph 2, PhCH₂ 3; L = L2 R = Me 4, Ph 5, PhCH₂ 6; L = L2 R = Me 7, Ph 8, PhCH₂ 9) have been obtained by reaction of new Schiff base HL1, HL2 or HL3 with triorganotin(IV) chloride in the presence of sodium ethoxide. All the complexes 1-9 were characterized by elemental, IR and NMR spectra analyses. Except for complexes 3, 4, 6, 9, the others were also characterized by X-ray crystallography diffraction analyses, which revealed that complexes 1, 2, 5, 7, 8 were four coordinated and displayed a capped tetrahedron.

Full text of DOI:10.1016/j.ica.2006.12.017

Inorganica Chimica Acta 360 (2007) 2439–2446
www.elsevier.com/locate/ica
Triorganotin(IV) complexes of Schiff base derived from
6-amino-2-mercaptobenzothiazole: Synthesis, characterization
and X-ray crystal structures
a,b,
a
a
Chunlin Ma
*, Yawen Han , Rufen Zhang
a
Department of Chemistry, Liaocheng University, Liaocheng 252059, PR China
b
Department of Chemistry, Taishan University, Taian 271021, PR China
Received 19 November 2006; received in revised form 6 December 2006; accepted 6 December 2006
Available online 16 December 2006
Abstract
Nine triorganotin(IV) complexes of the type R3SnL (L = L1 R = Me 1, Ph 2, PhCH2 3; L = L2 R = Me 4, Ph 5, PhCH2 6; L = L2
R = Me 7, Ph 8, PhCH2 9) have been obtained by reaction of new Schiff base HL1, HL2 or HL3 with triorganotin(IV) chloride in the
presence of sodium ethoxide. All the complexes 1–9 were characterized by elemental, IR and NMR spectra analyses. Except for com-
plexes 3, 4, 6, 9, the others were also characterized by X-ray crystallography diffraction analyses, which revealed that complexes 1, 2,
5, 7, 8 were four coordinated and displayed a capped tetrahedron.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Triorganotin(IV); Schiffbase; 6-Amino-2-mercaptobenzothiazole; Crystal structure
1. Introduction
that has been reported so far involves complexes of these
ligands with transition metal ions. Complexes of non-tran-
sition metal ions such as tin have received less attention.
Since organotin(IV) Schiff base ligands have potential
applications in organic synthesis, catalysis, medicinal
chemistry and biotechnology [17–20] and very little work
has been done on organotin(IV) complexes of Schiff base
derived from heterocyclic thiones. As an extension of this
research program and in connection with our current inter-
est in the coordination chemistry of organotin(IV) com-
plexes with heterocyclic thionates, and combined with the
development of organotin(IV) Schiff base chemistry, we
select the ligand: 6-amino-2-mercaptobenzothiazole as
raw material, synthesis the Schiff base HL1, HL2, HL3
and nine new organotin(IV) complexes 1–9 of the Schiff
base. The HL1, HL2 and HL3 have been characterized
In recent years, organotin(IV) complexes have received
much attention both in academic and applied research
because of the ability tin to afford stable bonds with carbon
as well as with other hetero atoms. Heterocyclic thiones
that contain at least one deprotonated heterocyclic thioam-
ide group (N–C–S)ꢀ has been subject for their versatile
coordination modes and effective biological activities.
Recently, some organotin(IV) derivatives from heterocyclic
thionates have been reported [1–5]. Our research group has
been focused on this area for many years and reported
many interesting structures [3,4,6–12]. Schiff base derived
from various heterocycles were reported to possess cyto-
toxic, anticonvulsant, antiproliferative, anticancer and
antifungal actives [13–16]. However, the majority of work
1
by the elemental, IR and H NMR spectra analyses. All
the complexes 1–9 have been characterized by the elemen-
tal, IR, 1H, 13C and 119Sn NMR spectra analyses. The com-
plexes 1, 2, 5, 7 and 8 were also characterized by X-ray
crystallography.
*
Corresponding author. Address: Department of Chemistry, Liaocheng
University, Liaocheng 252059, PR China. Tel.: +86 635 8230660; fax: +86
538 6715521.
E-mail address: macl@lcu.edu.cn (C. Ma).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.12.017

2440
C. Ma et al. / Inorganica Chimica Acta 360 (2007) 2439–2446
2. Experimental
2730, m (C@N) 1650, m (S–C@N) 1584, (C–S) 962. 1H
NMR (CDCl3, ppm): d 8.91 (CH@N), 2.52 (S–H).
2.1. Materials and measurements
2.2.3. Synthesis of HL3
All reagents were commercially available, and were used
without further purification. The melting points were
obtained with Kofler micro melting point apparatus and
are uncorrected. Infrared-spectra were recorded on a Nico-
let-460 spectrophotometer using KBr discs and sodium
chloride optics. 1H, 13C and 119Sn NMR spectra were
obtained on a Varian Mercury Plus 400 spectrometer oper-
ating at 400, 101 and 149.2 MHz, respectively. The chemi-
cal shifts were given in ppm with respect to the references
The produce was the same as the HL1, The 6-amino-2-
mercaptobenzothiazole (0.550 g, 3 mmol) and salicylalde-
hyde (0.430 g, 3.5 mmol) added to ethanol 30 ml, refluxing
6 h. The yellow precipitate was collected by filtration,
washed with ether-petroleum, and dried at the nitrogen
atmosphere. M.p. >200 ꢁC. Yield: 0.545 g, 70%. Anal.
Calc. for C15H11NOS2: C, 63.13; H, 3.89; N, 4.91. Found:
C, 63.41; H, 3.48; N, 4.66%. IR (KBr, cmꢀ1): m (S–H) 2727,
m (C@N) 1650, m (S–C@N) 1571, (C–S) 963. 1H NMR
(CDCl3, ppm): d 9.23 (CH@N), 2.61 (S–H).
1
and were stated relative to Me4Si for H and 13C NMR,
and to neat Me4Sn for 119Sn NMR. Elemental analyses
were performed with a PE-2400II apparatus. The synthetic
experiments of new Schiff base HL1, HL2, HL3 were
shown in Scheme 1.
2.3. Synthesis of complexes 1–4
2.3.1. Synthesis of [Me3SnL1] (1)
The reaction was carried out under nitrogen atmo-
sphere. The HL1 (0.276 g, 1 mmol) was added to the solu-
tion of absolute benzene (20 ml) with sodium ethoxide
(0.068 g, 1 mmol), and the mixture was stirred for 15 min,
then added trimethyltin chloride (0.199 g, 1 mmol) to the
mixture, continuing the reaction for 12 h at 40 ꢁC. After
cooling down to room temperature filtered it. The solvent
of the filtrate was gradually removed by evaporation under
vacuum until solid product was obtained. The solid was
then recrystallized from ether. Yellow crystal was formed.
Yield: 72%. M.p.: 100–102 ꢁC. Anal. Calc. for C15H16-
N2S3Sn: C, 41.02; H, 3.67; N, 6.38. Found: C, 41.14; H,
3.59; N, 6.21%. IR (KBr, cmꢀ1): m (C@N) 1609, m (S–
C@N) 1578, (C–S) 973, (Sn–S) 318. 1H NMR (CDCl3,
ppm): d 8.63 (CH@N), 7.14–7.72 (Ar–H), 1.23 (Sn–CH3).
13C NMR (CDCl3, ppm): d 167.4 (C–S–Sn) 152.1, 151.9,
147.6, 142.8, 138.4, 132.4, 130.5, 127.9, 120.9, 119.9,
112.8, 11.3. 119Sn NMR (CDCl3, ppm): 108.2.
2.2. Synthesis of new Schiff base HL1, HL2 and HL3
2.2.1. Synthesis of HL1
The reaction was carried out under nitrogen atmosphere
with use of standard Schlenk technique. The 6-amino-2-
mercaptobenzothiazole (0.550 g, 3 mmol) was added to
the solution of ethanol 30 ml, and then added thiophene-
2-carboxaldehyde (0.400 g, 3.5 mmol) to the solution,
continuing the reaction for 6 h at refluxing. The yellow pre-
cipitate was collected by filtration, washed with ether-
petroleum, and dried at the nitrogen atmosphere. M.p.
>200 ꢁC. Yield: 0.514 g, 72%. Anal. Calc. for C13H9NS3:
C, 56.69; H, 3.29; N, 5.09. Found: C, 57.01; H, 3.41; N,
4.89%. IR (KBr, cmꢀ1): m (S–H) 2734, m (C@N) 1653, m
(S–C@N) 1583 (C–S) 972. 1H NMR (CDCl3, ppm): d
8.85 (CH@N), 7.72–7.99 (Ar–H), 2.41 (S–H).
2.2.2. Synthesis of HL2
The produce was the same as the HL1, The 6-amino-2-
mercaptobenzothiazole (0.550 g, 3 mmol) and 2-furalde-
hyde (0.336 g, 3.5 mmol) added to ethanol 30 ml, refluxing
6 h. The yellow precipitate was collected by filtration,
washed with ether-petroleum, and dried at the nitrogen
atmosphere. M.p. >200 ꢁC. Yield: 0.515 g, 68%. Anal.
Calc. for C13H9NOS2: C, 60.20; H, 3.50; N, 5.40. Found:
C, 59.92; H, 3.22; N, 5.13%. IR (KBr, cmꢀ1): m (S–H)
2.3.2. Synthesis of [Ph3SnL1] (2)
The procedure is similar to that of complex 1. The HL1
(0.276 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
Ph3SnCl (0.385 g, 1 mmol) were added to the solution of
benzene (20 ml), continuing the reaction for 12 h at 40 ꢁC.
The solid was recrystallized from ether-petroleum, and yel-
low crystals were formed. M.p.: 176–178 ꢁC. Anal. Calc. for
C30H22N2S3Sn: C, 57.62; H, 3.55; N, 4.48. Found: C, 57.60;
H, 3.38; N, 4.52%. IR (KBr, cmꢀ1): m (C@N) 1611, m (S–
C@N) 1582, (C–S) 996, (Sn–S) 338. 1H NMR (CDCl3,
ppm): d 8.62 (CH@N), 7.25–7.76 (Ar–H). 13C NMR
(CDCl3, ppm): d 167.2 (C–S–Sn) 151.8, 147.1, 137.3,
136.4, 136.2, 136.0, 130.6, 129.5, 129.2, 128.9, 120.1, 119.7,
119.1, 117.5, 113.4. 119Sn NMR (CDCl3, ppm): ꢀ117.2.
N
EtOH
N
SH
R-CHO
SH
R CH N
S
Refluxing
NH2
S
S
R=
HL1
O
R=
R=
2.3.3. Synthesis of [(PhCH2)3SnL1] (3)
HL2
HL3
The procedure is similar to that of complex 1. The HL1
(0.276 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
(PhCH2)3SnCl (0.427 g, 1 mmol) were added to the solu-
tion of benzene (20 ml), continuing the reaction for 12 h
OH
Scheme 1.

C. Ma et al. / Inorganica Chimica Acta 360 (2007) 2439–2446
2441
at 40 ꢁC. The solid was recrystallized from ether-petro-
leum, and yellow crystals were formed. M.p.: 165–167 ꢁC.
Anal. Calc. for C33H28N2S3Sn: C, 59.38; H, 4.23; N, 4.19.
Found: C, 59.05; H, 4.38; N, 4.49%. IR (KBr, cmꢀ1): m
2.3.7. Synthesis of [Me3SnL3] (7)
The procedure is similar to that of complex 1. The HL3
(0.287 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
Me3SnCl (0.199 g, 1 mmol) were added to the solution of
benzene (20 ml), continuing the reaction for 12 h at
40 ꢁC. The solid was recrystallized from ether-petroleum,
and yellow crystals were formed. M.p.: 106–108 ꢁC. Anal.
Calc. for C17H18N2OS2Sn: C, 45.46; H, 4.04; N, 6.23.
Found: C, 45.32; H, 3.97; N, 6.18%. IR (KBr, cmꢀ1): m
1
(C@N) 1610, m (S–C@N) 1579, (C–S) 995, (Sn–S) 332. H
NMR (CDCl3, ppm): d 8.62 (CH@N), 7.25–7.76 (Ar–H).
13C NMR (CDCl3, ppm): d 167.9 (C–S–Sn) 152.4, 147.9,
137.1, 136.1, 135.8, 135.6, 130.2, 129.3, 129.0, 128.7,
120.0, 119.5, 118.7, 117.1, 113.0, 38.4 (CH2–Ph). 119Sn
NMR (CDCl3, ppm): ꢀ98.5.
1
(C@N) 1612, m (S–C@N) 1568, (C–S) 978, (Sn–S) 325. H
NMR (CDCl3, ppm): d 13.22 (–OH), 8.68 (CH@N),
6.98–7.84 (Ar–H) 0.98 (Sn–CH3). 13C NMR (CDCl3,
ppm): d 168.3 (C–S–Sn), 162.1, 161.1, 152.4, 144.6, 138.6,
132.3, 121.1, 119.8, 119.3, 119.2, 117.3, 113.1, 14.2. 119Sn
NMR (CDCl3, ppm): 111.3.
2.3.4. Synthesis of [Me3SnL2] (4)
The procedure is similar to that of complex 1. The HL2
(0.260 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
Me3SnCl (0.199 g, 1 mmol) were added to the solution of
benzene (20 ml), continuing the reaction for 12 h at
40 ꢁC. The solid was recrystallized from ether-petroleum,
and yellow crystals were formed. M.p.: 104–106 ꢁC. Anal.
Calc. for C62H50N4O3S4Sn2: C, 58.88; H, 3.98; N, 4.43.
Found: C, 58.56; H, 3.77; N, 4.68%. IR (KBr, cmꢀ1): m
2.3.8. Synthesis of [Ph3SnL3] (8)
The procedure is similar to that of complex 1. The HL3
(0.287 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
Ph3SnCl (0.385 g, 1 mmol) were added to the solution of
benzene (20 ml), continuing the reaction for 12 h at
40 ꢁC. The solid was recrystallized from ether-petroleum,
and yellow crystals were formed. M.p.: 142–144 ꢁC. Anal.
Calc. for C32H24N2OS2Sn: C, 60.49; H, 3.81; N, 4.41.
Found: C, 60.40; H, 3.90; N, 4.25%. IR (KBr, cmꢀ1): m
(C@N) 1615, m (S–C@N) 1570, m (C–S) 997, (Sn–S) 342.
1H NMR (CDCl3, ppm): d 13.22 (–OH), 8.67 (CH@N),
6.95–7.74 (Ar–H). 13C NMR (CDCl3, ppm): d 167.3 (C–
S–Sn), 162.4, 161.1, 151.7, 144.8, 139.3, 138.8, 137.1,
136.8, 136.6, 133.3, 132.3, 129.9, 129.7, 129.2, 128.9,
128.8, 128.6, 120.7, 120.1, 119.3, 117.3, 113.2. 119Sn
NMR (CDCl3, ppm): ꢀ108.2.
1
(C@N) 1606, m (S–C@N) 1579, (C–S) 970, (Sn–S) 320. H
NMR (CDCl3, ppm): d 8.64 (CH@N), 7.16–7.78 (Ar–H),
1.25 (Sn–CH3). 13C NMR (CDCl3, ppm): d167.0 (C–S–
Sn) 152.0, 151.6, 147.3, 142.7, 138.3, 132.1, 130.2, 127.7,
120.6, 119.8, 112.7, 11.2. 119Sn NMR (CDCl3, ppm): 106.5.
2.3.5. Synthesis of [Ph3SnL2] (5)
The procedure is similar to that of complex 1. The HL2
(0.260 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
Ph3SnCl (0.385 g, 1 mmol) were added to the solution of
benzene (20 ml), continuing the reaction for 12 h at
40 ꢁC. The solid was recrystallized from ether-petroleum,
and yellow crystals were formed. M.p.: 150–152 ꢁC. Anal.
Calc. for C30H22N2OS2Sn: C, 59.13; H, 3.64; N, 4.60.
Found: C, 59.40; H, 3.89; N, 4.33%. IR (KBr, cmꢀ1): m
(C@N) 1611, m (S–C@N) 1583, m (C–S) 998, (Sn–S) 340.
1H NMR (CDCl3, ppm): d 8.62 (CH@N), 7.24–7.75 (Ar–
H). 13C NMR (CDCl3, ppm): d167.1 (C–S–Sn) 151.7,
147.2, 137.1, 136.3, 136.1, 135.9, 130.5, 129.3, 129.1,
128.7, 120.0, 119.6, 119.0, 117.3, 113.2. 119Sn NMR
(CDCl3, ppm): ꢀ118.1.
2.3.9. Synthesis of [(PhCH2)3SnL3] (9)
The procedure is similar to that of complex 1. The HL2
(0.287 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
(PhCH2)3SnCl (0.427 g, 1 mmol) were added to the solu-
tion of benzene (20 ml), continuing the reaction for 12 h
at 40 ꢁC. The solid was recrystallized from ether-petro-
leum, and yellow crystals were formed. M.p.: 150–152 ꢁC.
Anal. Calc. for C35H30N2OS2Sn: C, 62.61; H, 3.60; N,
4.17. Found: C, 62.33; H, 3.87; N, 4.35%. IR (KBr,
cmꢀ1): m (C@N) 1614, m (S–C@N) 1569, m (C–S) 996,
2.3.6. Synthesis of [(PhCH2)3SnL2] (6)
The procedure is similar to that of complex 1. The HL1
(0.276 g, 1 mmol), sodium ethoxide (0.068 g, 1 mmol) and
(PhCH2)3SnCl (0.427 g, 1 mmol) were added to the solu-
tion of benzene (20 ml), continuing the reaction for 12 h
at 40 ꢁC. The solid was recrystallized from ether-petro-
leum, and yellow crystals were formed. M.p.: 148–150 ꢁC.
Anal. Calc. for C33H26N2OS2Sn: C, 61.03; H, 3.41; N,
4.31. Found: C, 61.33; H, 3.65; N, 4.63%. IR (KBr,
cmꢀ1): m (C@N) 1607, m (S–C@N) 1581, (C–S) 997, (Sn–
1
(Sn–S) 336. H NMR (CDCl3, ppm): d 13.18 (–OH), 8.73
(CH@N), 7.05–7.86 (Ar–H), 3.26 (CH2–Ph). 13C NMR
(CDCl3, ppm): d 172.8 (C–S–Sn), 168.5, 164.2, 156.7,
148.2, 140.3, 138.5, 137.6, 136.8, 135.4, 134.1, 132.8,
130.5, 129.8, 129.0, 128.7, 128.1, 121.3, 120.7, 119.8,
118.1, 113.9, 37.5 (CH2–Ph). 119Sn NMR (CDCl3, ppm):
ꢀ95.7.
1
3. Result and discussion
S) 330. H NMR (CDCl3, ppm): d 8.62 (CH@N), 7.25–
7.76 (Ar–H). 13C NMR (CDCl3, ppm): d 167.9 (C–S–Sn)
152.3, 147.7, 137.0, 136.0, 135.5, 135.3, 130.0, 129.1,
129.0, 128.5, 119.8, 119.5, 118.6, 116.9, 112.9, 38.3 (CH2–
Ph). 119Sn NMR (CDCl3, ppm): ꢀ97.2.
3.1. Synthesis of complexes 1–9
The synthesis procedure was shown in Scheme 2.

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C. Ma et al. / Inorganica Chimica Acta 360 (2007) 2439–2446
3.4. Description of crystal structures of 1, 2, 5, 7 and 8
R'
Sn R'
R'
N
S
S
R'3SnCl
HL
EtONa
S
R CH N
Selected bond lengths and bond angles for 1, 2, 5, 7 and
8 are given in Tables 1–3, respectively, and their crystal
molecular structures are given in Figs. 1–5, respectively.
From the structures we can see that there exist four pri-
mary bonds to the central tin atom in complexes 1, 2, 5, 7
and 8, three carbons from the methyl (for complexes 1 and
7), phenyl groups (for complexes 2, 5 and 8), and one S
from the HL1, HL2 or HL3. Thus, the complexes 1, 2, 5,
7 and 8 are all display tetrahedral coordination sphere with
six angles ranging from 95.30(18)ꢁ to 118.1(2)ꢁ. The Sn–S
R=
HL=HL1
R'=Me 1, Ph 2, PhCH2 3
R'=Me 4, Ph 5, PhCH2 6
R'=Me 7, Ph 8, PhCH2 9
O
HL2
HL3
R=
R=
OH
Scheme 2.
˚
bond lengths [between 2.4281(14) and 2.4877(14) A] are a
3.2. IR
little longer than the covalent radii of tin and sulfur atoms
The stretching frequencies of interest are those associ-
ated with the SnAS and SAC@N groups. The spectra of
all the complexes 1–9 show some common characters. The
explicit features in the infrared spectra of all complexes 1–
9, strong absorption appearing in the range of 318–
342 cmꢀ1 in respective of the complexes, which are absent
in the free ligands, are assigned to the Sn–S stretching mode
of vibration. All these values are consistent with that
detected in a number of organotin(IV)-sulfur derivative
[21]. Thꢀe1 m (SAC@N), occurring at 1578 cmꢀ1 for 1,
1582 cm for 2, 1580 cmꢀ1 3, 1579 cmꢀ1 4, 1583 cmꢀ1 5,
1581 cmꢀ1 6, 1568 cmꢀ1 for 7, 1570 cmꢀ1 for 8, 1569 cmꢀ1
for 9 is shift a littler lower frequencies compare with that
of the HL1 (1583 cmꢀ1), HL2 (1584 cmꢀ1) and HL3
(1571 cmꢀ1), confirming the very weak coordination of
the heterocyclic N to the tin. This can be further confirmed
by the X-ray crystallography.
Table 1
˚
Selected bond lengths (A) and bond angles (ꢁ) of complex 1 and 2
Complex 1
Complex 2
Bond lengths
Sn(1)–C(15)
Sn(1)–C(13)
Sn(1)–C(14)
Sn(1)–S(2)
Bond lengths
Sn(1)–C(13)
Sn(1)–C(25)
Sn(1)–C(19)
Sn(1)–S(2)
2.101(15)
2.131(14)
2.143(13)
2.455(4)
3.005
2.120(5)
2.124(5)
2.130(5)
2.4281(14)
3.381
Sn(1)–N(1)
Sn(1)–N(1)
Bond angles
Bond angles
C(15)–Sn(1)–C(13)
C(15)–Sn(1)–C(14)
C(13)–Sn(1)–C(14)
C(15)–Sn(1)–S(2)
C(13)–Sn(1)–S(2)
C(14)–Sn(1)–S(2)
111.5(8)
C(13)–Sn(1)–C(25)
C(13)–Sn(1)–C(19)
C(25)–Sn(1)–C(19)
C(13)–Sn(1)–S(2)
C(25)–Sn(1)–S(2)
C(19)–Sn(1)–S(2)
110.07(19)
114.39(19)
108.73(18)
110.27(13)
96.69(14)
115.9(7)
111.8(7)
107.4(5)
100.4(5)
108.5(5)
115.21(14)
Table 2
˚
Selected bond lengths (A) and bond angles (ꢁ) of complex 5
3.3. NMR
Bond lengths
Sn(1)–C(13)
Sn(1)–C(19)
In the 1H NMR spectrums of the complexes 1–9, the 1H
NMR spectra show the expected integration and peak mul-
tiplicities. In the spectra of the HL1, HL2 and HL3 ligands,
the resonances observed at 2.41, 2.52 and 2.61 ppm, which
are absent in the spectra of the complexes, indicate removal
of the SH protons and formation of Sn–S bonds. This con-
2.129(7)
2.135(6)
Sn(1)–C(25)
Sn(1)–S(2)
2.133(7)
2.460(2)
Bond angles
C(13)–Sn(1)–C(25)
C(25)–Sn(1)–C(19)
C(25)–Sn(1)–S(2)
112.7(2)
109.5(3)
113.45(17)
C(13)–Sn(1)–C(19)
C(13)–Sn(1)–S(2)
C(19)–Sn(1)–S(2)
112.6(2)
112.1(2)
95.30(18)
1
clusion accords well with the IR data. Moreover, the H
NMR spectroscopic data show that the chemical shifts of
the phenyl groups in complexes 2, 5, 8, the methyl groups
in complexes 1, 4, and 7, and the methyl groups in com-
plexes 3, 6 and 9 undergo an up field shift relative to those
of their precursors.
Table 3
˚
Selected bond lengths (A) and bond angles (ꢁ) of complex 7 and 8
Complex 7
Complex 8
Bond lengths
Sn(1)–C(16)
Sn(1)–C(17)
Sn(1)–C(15)
Sn(1)–S(2)
Bond lengths
Sn(1)–C(27)
Sn(1)–C(21)
Sn(1)–C(15)
Sn(1)–S(2)
2.110(4)
2.132(5)
2.139(4)
2.4877(14)
3.073(3)
2.127(5)
2.143(4)
2.143(4)
2.447(3)
3.049
The 13C NMR spectra of all complexes 1–9 show a sig-
nificant downfield shift of all carbon resonances compared
with the free ligand (HL1, HL2 and HL3) because of an
electron-density transfer from the ligand to the metal atom.
The 119Sn NMR spectroscopic data shown only one signals
for complexes 1–9 (d = 108.2 ppm for 1, ꢀ117.2 ppm for 2,
ꢀ98.5 ppm for 3, 106.5 ppm for 4, ꢀ118.1 ppm for 5,
ꢀ97.2 ppm for 6, 111.3 ppm for 7, ꢀ108.2 ppm for 8,
ꢀ95.7 ppm for 9) are in the normal range for four-coordi-
nate tin complexes [22].
Sn(1)–N(1)
Sn(1)–N(1)
Bond angles
Bond angles
C(16)–Sn(1)–C(17)
C(16)–Sn(1)–C(15)
C(17)–Sn(1)–C(15)
C(16)–Sn(1)–S(2)
C(17)–Sn(1)–S(2)
C(15)–Sn(1)–S(2)
118.1(2)
114.99(18)
112.5(2)
105.42(14)
103.56(15)
99.26(14)
C(27)–Sn(1)–C(21)
C(27)–Sn(1)–C(15)
C(21)–Sn(1)–C(15)
C(27)–Sn(1)–S(2)
C(21)–Sn(1)–S(2)
C(15)–Sn(1)–S(2)
116.54(16)
108.90(17)
110.21(17)
111.52(12)
111.27(11)
96.56(13)

C. Ma et al. / Inorganica Chimica Acta 360 (2007) 2439–2446
2443
Fig. 1. The molecular structure of complex 1.
Fig. 5. The molecular structure of complex 8.
˚
3.049 A 8, respectively], they are all longer than the sum
˚
of the covalent radii of tin and nitrogen atoms (2.15 A),
but still lie within the sum of the van der Walls radii of
˚
the two atoms (3.74 A) [23]. As the N atoms of the hetero-
cycle are involved in a weak coordinative interaction with
tin along one of the tetrahedral faces, the structure distor-
tion for the tin atom in 1, 2, 5, 7 and 8 is best described as a
capped tetrahedron. For complexes 7 and 8 there is differ-
ent from 1, 2 and 5 is that an intramolecular hydrogen
bonds between the oxygen of the hydrogen and nitrogen
of the CH@N was identified as can be seen from the Figs.
4 and 5 and the values are list in Table 4.
Fig. 2. The molecular structure of complex 2.
Further analysis of the supramolecular structure of the
complexes 1, 2, 5, 7 and 8, only find the complexes 1 and
7 have more important intermolecular interactions. The
supramolecular structure of 1 is dominated by 1D chain
linked by intermolecular C(8)–H(8)ꢁ ꢁ ꢁS(3) [H(8)ꢁ ꢁ ꢁS(3)
˚
˚
2.961 A, C(8)ꢁ ꢁ ꢁS(3) 3.857 A, C(8)–H(8)ꢁ ꢁ ꢁS(3) 162.35ꢁ] as
can be seen from the Fig. 6. The H(8)ꢁ ꢁ ꢁS(3) distance is
much close to the literature report for the H and S weak
˚
interaction (2.959 A) [25].
The supramolecular structure of complex 7 is dominated
by intermolecular Snꢁ ꢁ ꢁO, C–Hꢁ ꢁ ꢁp and C–Hꢁ ꢁ ꢁS interac-
tions. An important Snꢁ ꢁ ꢁO interaction along the b axis
was found from the crystal packing of complex 7
(Fig. 7), and link the discrete molecular into a 1D chain.
Fig. 3. The molecular structure of complex 5.
˚
Though the Snꢁ ꢁ ꢁO distance (Sn(1)ꢁ ꢁ ꢁO(1) = 3.296 A) is
considerably longer than the normal Sn–O covalent bond,
they are much shorter than the van der Waals radii of Sn
˚
and O (3.68 A). The C–Hꢁ ꢁ ꢁp interaction has identified
between the C7A and the ring of benzothiazole. This can
be considered as a pair of bifurcated intermolecular C–
Hꢁ ꢁ ꢁp interaction [C(7)–H(7 A)ꢁ ꢁ ꢁCg1 (Cg1 cent of the
Fig. 4. The molecular structure of complex 7.
˚
˚
C2–C7, H(7A)ꢁ ꢁ ꢁCg1 2.783 A, 3.671 A, 160.18ꢁ) and
C(7)–H(7A)ꢁ ꢁ ꢁCg2 (Cg2 cent of the C(1)–N(1)–C(2)–
˚
˚
˚
˚
(2.42 A) [23] and within the range from 2.41 to 2.48 A on
the whole that reported in triphenyltin(IV) heteroarenethi-
olates [24]. The Sn–C bond lengths fall in a narrow range
C(3)–S(1) 3.169 A, 3.790 A, 125.98ꢁ)] as shown in Fig. 8,
all these distances are reasonable as an intermolecular
action according to the literature reported [26]. The pair
of C–Hꢁ ꢁ ꢁp interactions further reinforces the 1D chain
as can be seen from the Fig. 9. In the direction of a axis
˚
from 2.101(15) to 2.143(13) A for complexes 1, 2, 5, 7
and 8, typical for organotin(IV) derivatives. Five com-
plexes are different distinctly from each other with regards
to their weak intramolecular Snꢁ ꢁ ꢁN interactions [Sn(1)–
˚
an intermolecular C–Hꢁ ꢁ ꢁS (C12–H12ꢁ ꢁ ꢁS2 2.862 A,
˚
3.635 A, 141.26 ꢁ) interaction link these 1D chain together
˚
˚
˚
˚
N(1): 3.005 A 1, 3.381 A 2, 2.992 A 5, 3.073(3) A 7,
and 2D network was formed in the bc plane (Fig. 9).

2444
C. Ma et al. / Inorganica Chimica Acta 360 (2007) 2439–2446
Table 4
Hydrogen bonds and C–Hꢁ ꢁ ꢁp interaction for the complexes 7 and 8
˚
˚
˚
D–Hꢁ ꢁ ꢁA
d(D–H) (A)
d(H. . .A) (A)
d(D. . .A) (A)
\DHA (ꢁ)
Complex 7
Complex 8
O1–H1ꢁ ꢁ ꢁN2
0.820
0.820
0.820
1.887
1.861
1.973
2.617
2.618
2.762
C–Hꢁ ꢁ ꢁCg
160.18
125.98
147.68
152.98
161.21
O1–H1_aꢁ ꢁ ꢁN2_a
O10–H10_bꢁ ꢁ ꢁN20_b
C–Hꢁ ꢁ ꢁp
˚
˚
Hꢁ ꢁ ꢁCg (A)
Cꢁ ꢁ ꢁCg (A)
C(7)–H(7A)ꢁ ꢁ ꢁCg(1)
C(7)–H(7A)ꢁ ꢁ ꢁCg(2)
2.783
3.671
3.790
3.169
Cg(1) and Cg(2) are referred to the centroids of C(2)–C(3)–C(4)–C(5)–C(6)–C(7), C(1)–N(1)–C(2)–C(3)–S(1).
Fig. 6. 1D chain was connected by intermolecular C–Hꢁ ꢁ ꢁS interaction of
complex 1.
Fig. 8. The 1D chain linked by intermolecular Snꢁ ꢁ ꢁO and C–Hꢁ ꢁ ꢁp
interaction of complex 7.
4. X-ray crystallography
Crystals were mounted in Lindemann capillaries under
nitrogen. All X-ray crystallographic data were collected
on a Bruker SMART CCD 1000 diffractometer with
graphite monochromated Mo Ka radiation (k =
˚
0.71073 A) at 298(2) K. A semi-empirical absorption cor-
rection was applied to the data. The structure was solved
by direct methods using SHELXS-97 and refined against F2
by full-matrix least squares using SHELXL-97. Hydrogen
Fig. 7. The crystal packing of complex 7.
Fig. 9. The 2D network connected by intermolecular Snꢁ ꢁ ꢁO, C–Hꢁ ꢁ ꢁp and C–Hꢁ ꢁ ꢁS interaction of complex 7. The non-interaction hydrogen atoms and
the methyl group have been omitted for clarity.

C. Ma et al. / Inorganica Chimica Acta 360 (2007) 2439–2446
2445
Table 5
Crystal data and structure refinement parameters for complexes 1, 2, 5, 7 and 8
Complex
1
2
5
7
8
Empirical formula
Formula weight
Wavelength (A)
C15H16N2S3Sn
439.17
0.71073
C120H88N8S12Sn4
2501.46
0.71073
C62H50N4O3S4Sn2
1264.68
0.71073
C17H18N2OS2Sn
449.14
0.71073
C32H24N2OS2Sn
635.34
0.71073
˚
Crystal system
orthorhombic
Pccn
monoclinic
P2(1)/n
9.5234(16)
29.597(5)
10.1657(17)
90
107.927(2)
90
2726.2(8)
1
1.524
1256
1.189
0.53 · 0.49 · 0.48
1.38–25.01
ꢀ10 6 h 6 11,
ꢀ32 6 k 6 35,
ꢀ11 6 l 6 12
14089
triclinic
monoclinic
P2(1)/c
11.755(5)
7.337(3)
21.838(10)
90
93.108(6)
90
1880.6(15)
4
1.586
896
1.585
0.38 · 0.27 · 0.21
1.73–25.01
ꢀ11 6 h 6 13,
ꢀ8 6 k 6 8,
ꢀ25 6 l 6 22
9413
triclinic
ꢀ
ꢀ
Space group
P1
P1
˚
a (A)
44.779(2)
10.786(3)
7.502(3)
90
90
9.685(2)
9.547(9)
˚
b (A)
13.204(3)
13.323(3)
68.117(4)
76.261(4)
75.145(4)
1508.8(6)
1
1.392
638
1.012
0.21 · 0.16 · 0.11
1.94–25.01
ꢀ11 6 h 6 11,
ꢀ15 6 k 6 15,
ꢀ15 6 l 6 8
8021
11.792(13)
14.644(16)
113.141(14)
94.362(16)
101.25(2)
1465(3)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
3
˚
V (A )
3623.4(18)
8
1.610
1744
1.750
0.42 · 0.39 · 0.16
1.82–25.01
ꢀ53 6 h 6 47,
ꢀ12 6 k 6 12,
ꢀ6 6 l 6 8
16673
Z
2
Dcalc (Mg mꢀ3
F(000)
)
1.440
640
1.041
0.57 · 0.51 · 0.48
1.90–25.01
ꢀ10 6 h 6 11,
ꢀ12 6 k 6 14
ꢀ17 6 l 6 17
7580
Absorption coefficient (mmꢀ1
Crystal size (mm)
)
h Range for data collection (ꢁ)
Index ranges
Reflections collected
Unique reflections
3105
4794
8021
3312
5072
Maximum/minimum transmission
Data/restraints/parameters
Goodness of fit on F2
0.7671/0.5268
3105/0/190
1.009
0.5991/0.5714
4794/0/325
1.000
0.8968/0.8156
5267/39/353
1.001
0.7319/0.5842
3312/0/208
1.000
0.6349/0.5883
5072/11/371
1.003
Final R indices [I > 2r(I)]
R1 = 0.0756,
wR2 = 0.1969
R1 = 0.1087,
wR2 = 0.2246
R1 = 0.0447,
wR2 = 0.1094
R1 = 0.0631,
wR2 = 0.1200
R1 = 0.0525,
wR2 = 0.1282
R1 = 0.0960,
wR2 = 0.1572
R1 = 0.0323,
wR2 = 0.0728
R1 = 0.0498,
wR2 = 0.0848
R1 = 0.0346,
wR2 = 0.0870
R1 = 0.0501,
wR2 = 0.1001
R indices (all data)
[3] C.L. Ma, Q. Jiang, R.F. Zhang, J. Organomet. Chem. 678 (2003) 148.
atoms were placed in calculated positions. Crystal data and
experimental details of the structure determinations are list
in Table 5.
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5. Supplementary material
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[8] C.L. Ma, Q. Jiang, R.F. Zhang, Can. J. Chem. 81 (2003) 825.
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(2005) 1560.
CCDC 627615, 627613, 627616 and 627614 contain the
supplementary crystallographic data for 1, 2, 7 and 8.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk.
[11] C.L. Ma, J.H. Zhang, G.R. Tian, R.F. Zhang, J. Organomet. Chem.
690 (2005) 519.
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Acknowledgement
We thank the National Natural Science Foundation of
China (20271025) for financial support.
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