Dichloridobis(pyridine-2-thiol-ato-κ²N,S)tin(IV): a new polymorph.

The title compound, [SnCl₂(C₅H₄NS)₂], is the product of reaction of 2,2'-dipyridyl disulfide with tin tetra-chloride. The Sn(IV) atom adopts a distorted octa-hedral geometry, with the two bidentate pyridine-2-thiol-ate ligands forming two planar four-membered chelate rings. The two Sn-Cl, two Sn-N and two Sn-S bonds are in cis, cis and trans configurations, respectively. The crystal grown from acetonitrile represents a new monoclinic polymorph in space group C2/c with the mol-ecule having twofold rotational symmetry, the Sn(IV) atom lying on the twofold axis. The mol-ecular structure of the monoclinic polymorph is very close to that of the triclinic polymorph studied previously in space group P-1, the mol-ecule occupying a general position [Masaki & Matsunami (1976 ▶). Bull. Chem. Soc. Jpn, 49, 3274-3279; Masaki et al. (1978 ▶). Bull. Chem. Soc. Jpn, 51, 3298-3301]. Apparently, the formation of the two polymorphs is determined by the different systems of inter-molecular inter-actions. In the crystal of the monoclinic polymorph, mol-ecules are bound into ribbons along the c axis by C-H⋯Cl hydrogen bonds, whereas in the crystal of the triclinic polymorph, mol-ecules form chains along the a axis by attractive S⋯S inter-actions. The crystal studied was a pseudo-merohedral twin; the refined BASF value is 0.221 (1).

Related literature

For metal complexes with 2,2′-dipyridyl dichalcogenides, see: Kadooka et al. (1976a ▶,b ▶); Cheng et al. (1996 ▶); Kienitz et al. (1996 ▶); Bell et al. (2000 ▶); Kita et al. (2001 ▶); Kedarnath et al. (2009 ▶). For the triclinic polymorph, see: Masaki & Matsunami (1976 ▶); Masaki et al. (1978 ▶).

Experimental

Crystal data

[SnCl2(C5H4NS)2]

M = 409.93

Monoclinic,

a = 6.3240 (7) Å

b = 12.9391 (14) Å

c = 16.4240 (18) Å

β = 100.922 (2)°

V = 1319.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.63 mm−1

T = 100 K

0.16 × 0.14 × 0.10 mm

Data collection

Bruker SMART 1K CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T min = 0.678, T max = 0.779

6681 measured reflections

1584 independent reflections

1562 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.050

S = 1.00

1584 reflections

79 parameters

H-atom parameters constrained

Δρmax = 0.81 e Å−3

Δρmin = −0.53 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812024026/rk2356sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024026/rk2356Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[SnCl2(C5H4NS)2]	F(000) = 792
Mr = 409.93	Dx = 2.063 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6340 reflections
a = 6.3240 (7) Å	θ = 2.5–30.0°
b = 12.9391 (14) Å	µ = 2.63 mm−1
c = 16.4240 (18) Å	T = 100 K
β = 100.922 (2)°	Prism, colourless
V = 1319.6 (3) Å3	0.16 × 0.14 × 0.10 mm
Z = 4

Bruker SMART 1K CCD diffractometer	1584 independent reflections
Radiation source: fine-focus sealed tube	1562 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ– and ω–scans	θmax = 28.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −8→8
Tmin = 0.678, Tmax = 0.779	k = −16→16
6681 measured reflections	l = −21→21

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.050	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.014P)2 + 7.75P] where P = (Fo2 + 2Fc2)/3
1584 reflections	(Δ/σ)max < 0.001
79 parameters	Δρmax = 0.81 e Å−3
0 restraints	Δρmin = −0.53 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Sn1	0.5000	0.38034 (2)	0.2500	0.01554 (7)
Cl1	0.68565 (13)	0.25722 (5)	0.18092 (4)	0.02082 (15)
S1	0.17981 (13)	0.41891 (5)	0.14189 (4)	0.01907 (14)
N1	0.5510 (4)	0.50833 (19)	0.16215 (15)	0.0166 (5)
C1	0.3563 (5)	0.5095 (2)	0.11252 (18)	0.0170 (6)
C2	0.3100 (5)	0.5780 (2)	0.04557 (18)	0.0201 (6)
H2	0.1720	0.5786	0.0105	0.024*
C3	0.4699 (6)	0.6444 (2)	0.0318 (2)	0.0229 (7)
H3	0.4425	0.6915	−0.0134	0.028*
C4	0.6725 (6)	0.6430 (2)	0.08400 (17)	0.0209 (6)
H4	0.7836	0.6884	0.0749	0.025*
C5	0.7064 (5)	0.5737 (2)	0.14906 (17)	0.0190 (5)
H5	0.8425	0.5722	0.1854	0.023*

	U11	U22	U33	U12	U13	U23
Sn1	0.01793 (13)	0.01560 (12)	0.01225 (12)	0.0000	0.00070 (12)	0.0000
Cl1	0.0251 (4)	0.0200 (3)	0.0175 (3)	0.0044 (3)	0.0042 (3)	−0.0017 (2)
S1	0.0182 (3)	0.0197 (3)	0.0179 (3)	−0.0009 (3)	−0.0002 (3)	0.0007 (2)
N1	0.0196 (12)	0.0165 (12)	0.0131 (11)	0.0011 (9)	0.0018 (9)	−0.0001 (9)
C1	0.0209 (14)	0.0153 (13)	0.0152 (13)	0.0005 (10)	0.0041 (11)	−0.0020 (10)
C2	0.0236 (15)	0.0208 (14)	0.0150 (13)	0.0043 (12)	0.0013 (11)	−0.0019 (11)
C3	0.0334 (18)	0.0190 (14)	0.0164 (14)	0.0036 (12)	0.0046 (13)	0.0014 (11)
C4	0.0250 (15)	0.0190 (14)	0.0191 (13)	−0.0032 (13)	0.0053 (14)	−0.0012 (10)
C5	0.0213 (14)	0.0195 (13)	0.0161 (12)	−0.0007 (12)	0.0031 (12)	−0.0028 (10)

Sn1—N1	2.259 (2)	C2—C3	1.379 (5)
Sn1—Cl1	2.3892 (8)	C2—H2	0.9500
Sn1—S1	2.4779 (8)	C3—C4	1.400 (5)
S1—C1	1.748 (3)	C3—H3	0.9500
N1—C1	1.342 (4)	C4—C5	1.380 (4)
N1—C5	1.345 (4)	C4—H4	0.9500
C1—C2	1.399 (4)	C5—H5	0.9500
N1i—Sn1—N1	85.72 (12)	N1—C1—S1	112.7 (2)
N1i—Sn1—Cl1	159.13 (7)	C2—C1—S1	126.3 (2)
N1—Sn1—Cl1	92.47 (7)	C3—C2—C1	118.3 (3)
Cl1i—Sn1—Cl1	96.36 (4)	C3—C2—H2	120.9
N1i—Sn1—S1	96.54 (7)	C1—C2—H2	120.9
N1—Sn1—S1	65.85 (7)	C2—C3—C4	120.4 (3)
Cl1i—Sn1—S1	93.80 (3)	C2—C3—H3	119.8
Cl1—Sn1—S1	101.68 (3)	C4—C3—H3	119.8
S1i—Sn1—S1	156.76 (4)	C5—C4—C3	118.2 (3)
C1—S1—Sn1	81.67 (10)	C5—C4—H4	120.9
C1—N1—C5	120.7 (3)	C3—C4—H4	120.9
C1—N1—Sn1	99.82 (18)	N1—C5—C4	121.4 (3)
C5—N1—Sn1	139.5 (2)	N1—C5—H5	119.3
N1—C1—C2	121.0 (3)	C4—C5—H5	119.3
N1i—Sn1—S1—C1	82.81 (12)	S1—Sn1—N1—C5	179.8 (3)
N1—Sn1—S1—C1	0.49 (12)	C5—N1—C1—C2	0.5 (4)
Cl1i—Sn1—S1—C1	175.74 (10)	Sn1—N1—C1—C2	−179.2 (2)
Cl1—Sn1—S1—C1	−86.96 (10)	C5—N1—C1—S1	−179.4 (2)
S1i—Sn1—S1—C1	43.78 (10)	Sn1—N1—C1—S1	0.9 (2)
N1i—Sn1—N1—C1	−99.78 (19)	Sn1—S1—C1—N1	−0.82 (19)
Cl1i—Sn1—N1—C1	−14.1 (3)	Sn1—S1—C1—C2	179.3 (3)
Cl1—Sn1—N1—C1	101.05 (17)	N1—C1—C2—C3	0.0 (4)
S1i—Sn1—N1—C1	−164.84 (16)	S1—C1—C2—C3	179.9 (2)
S1—Sn1—N1—C1	−0.64 (15)	C1—C2—C3—C4	−0.2 (5)
N1i—Sn1—N1—C5	80.6 (3)	C2—C3—C4—C5	−0.1 (5)
Cl1i—Sn1—N1—C5	166.3 (2)	C1—N1—C5—C4	−0.8 (4)
Cl1—Sn1—N1—C5	−78.5 (3)	Sn1—N1—C5—C4	178.7 (2)
S1i—Sn1—N1—C5	15.6 (3)	C3—C4—C5—N1	0.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ii	0.95	2.80	3.673 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1i	0.95	2.80	3.673 (3)	154

Symmetry code: (i) .