Dimethyl­bis(3-methylsulfanyl-1,2,4-thia­diazole-5-thiol­ato)tin(IV)

Zhang, J.; Zhang, R.; Ma, C.; Wang, H.; Wang, D.

doi:10.1107/S1600536809030062

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1030

doi:10.1107/S1600536809030062

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Dimethylbis(3-methylsulfanyl-1,2,4-thiadiazole-5-thiolato)tin(IV)

Junhong Zhang,^a Rufen Zhang,^b ^* Chunlin Ma,^b Haizeng Wang ^a and Daqi Wang ^b

^aCollege of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, Shandong, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: zhangjunhong@lcu.edu.cn

(Received 20 July 2009; accepted 29 July 2009; online 8 August 2009)

In the title compound, [Sn(CH₃)₂(C₃H₃N₂S₃)₂], the Sn^IV atom is coordinated within a C₂N₂S₂ donor set that defines a skew-trapezoidal bipyramidal geometry in which the methyl groups lie over the weakly coordinated N atoms. Two independent molecules comprise the asymmetric unit, each of which lies on a mirror plane that passes through the C₂Sn unit.

Related literature

For related structures, see: Ma et al. (2005 ).

Experimental

Crystal data

[Sn(CH₃)₂(C₃H₃N₂S₃)₂]
M_r = 475.27
Orthorhombic, P n m a
a = 13.721 (9) Å
b = 16.383 (10) Å
c = 16.282 (10) Å
V = 3660 (4) Å³
Z = 8
Mo Kα radiation
μ = 2.07 mm⁻¹
T = 293 K
0.48 × 0.37 × 0.25 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.436, T_max = 0.625
18306 measured reflections
3368 independent reflections
2269 reflections with I > 2σ(I)
R_int = 0.086

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.09
3368 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030062/tk2508sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030062/tk2508Isup2.hkl

checkCIF report

Comment top

Two independent molecules of (CH₃)₂Sn(C₃H₃S₃N₂)₂ (I) comprise the asymmetric unit, each of which has mirror symmetry so that the C₂Sn units lie on a plane (Fig. 1). The molecules have essentially equivalent bond distances and angles. Each tin atoms exists within a C₂N₂S₂ donor set that defines a skew-trapezoidal bipyramidal geometry where the methyl groups lie over the weakly coordinated N atoms. The structure of (I) resembles closely those reported for a series of diorganotin(IV) 2-mercapto-4-methylpyrimidine derivatives (Ma et al., 2005).

Related literature top

For related structures, see: Ma et al. (2005).

Experimental top

3-Methylmercapto-5-mercapto-1,2,4-thiadiazole (2 mmol) was added to a solution of ethanol (20 ml) containing sodium ethoxide (2 mmol). The mixture was stirred for 30 minutes after which dimethyltin dichloride (1 mmol) was added. Stirring continued for 12 h at 318 K. After cooling to room temperature, the solution was filtered. The solvent was gradually removed by evaporation under vacuum until a solid product was obtained. The solid was then recrystallized from ether-dichloromethane to yield coulorless crystals; m. p. 356 K. Analysis, calculated for C₈H₁₂N₄S₆Sn: C 20.22, H 2.54, N 11.79; Found: C 20.16, H 2.49, N 11.83%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SaINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and atom labelling.

Dimethylbis(3-methylsulfanyl-1,2,4-thiadiazole-5-thiolato)tin(IV) top

Crystal data top

[Sn(CH₃)₂(C₃H₃N₂S₃)₂]	F(000) = 1872
M_r = 475.27	D_x = 1.725 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 5224 reflections
a = 13.721 (9) Å	θ = 3.0–24.2°
b = 16.383 (10) Å	µ = 2.07 mm⁻¹
c = 16.282 (10) Å	T = 293 K
V = 3660 (4) Å³	Block, colourless
Z = 8	0.48 × 0.37 × 0.25 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	3368 independent reflections
Radiation source: fine-focus sealed tube	2269 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.086
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→16
T_min = 0.436, T_max = 0.625	k = −19→19
18306 measured reflections	l = −17→19

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0351P)² + 5.554P] where P = (F_o² + 2F_c²)/3
3368 reflections	(Δ/σ)_max < 0.001
181 parameters	Δρ_max = 0.72 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Sn(CH₃)₂(C₃H₃N₂S₃)₂]	V = 3660 (4) Å³
M_r = 475.27	Z = 8
Orthorhombic, Pnma	Mo Kα radiation
a = 13.721 (9) Å	µ = 2.07 mm⁻¹
b = 16.383 (10) Å	T = 293 K
c = 16.282 (10) Å	0.48 × 0.37 × 0.25 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	3368 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2269 reflections with I > 2σ(I)
T_min = 0.436, T_max = 0.625	R_int = 0.086
18306 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.09	Δρ_max = 0.72 e Å⁻³
3368 reflections	Δρ_min = −0.58 e Å⁻³
181 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sn1	0.82279 (4)	0.2500	0.19604 (3)	0.04949 (19)
Sn2	0.43193 (4)	0.7500	0.09775 (3)	0.04987 (19)
N1	0.8651 (4)	0.4226 (3)	0.1828 (3)	0.0512 (12)
N2	0.8588 (4)	0.5637 (3)	0.1905 (3)	0.0652 (15)
N3	0.3945 (4)	0.5731 (3)	0.0784 (3)	0.0523 (12)
N4	0.4114 (4)	0.4321 (3)	0.0854 (3)	0.0636 (14)
S1	0.75305 (13)	0.53359 (10)	0.23249 (11)	0.0635 (5)
S2	0.70308 (12)	0.35277 (9)	0.24329 (11)	0.0622 (5)
S3	1.02182 (15)	0.49793 (12)	0.12428 (12)	0.0799 (6)
S4	0.51099 (13)	0.46584 (10)	0.13109 (10)	0.0637 (5)
S5	0.54857 (14)	0.64762 (10)	0.14981 (11)	0.0685 (5)
S6	0.25017 (14)	0.49009 (14)	0.00916 (12)	0.0833 (6)
C1	0.7797 (4)	0.4321 (3)	0.2172 (3)	0.0487 (14)
C2	0.9065 (5)	0.4983 (4)	0.1694 (4)	0.0568 (16)
C3	1.0417 (6)	0.6055 (5)	0.1120 (5)	0.093 (3)
H3A	1.1042	0.6144	0.0871	0.140*
H3B	1.0398	0.6316	0.1647	0.140*
H3C	0.9917	0.6279	0.0775	0.140*
C4	0.8323 (8)	0.2500	0.0646 (5)	0.079 (3)
H4A	0.7678	0.2500	0.0416	0.119*
H4B	0.8666	0.2022	0.0467	0.119*	0.50
H4C	0.8666	0.2978	0.0467	0.119*	0.50
C5	0.9452 (7)	0.2500	0.2736 (6)	0.072 (3)
H5A	0.9242	0.2500	0.3299	0.108*
H5B	0.9837	0.2978	0.2632	0.108*	0.50
H5C	0.9837	0.2022	0.2632	0.108*	0.50
C6	0.4790 (4)	0.5664 (3)	0.1173 (3)	0.0486 (14)
C7	0.3603 (5)	0.4953 (4)	0.0620 (3)	0.0525 (15)
C8	0.2309 (6)	0.3820 (5)	0.0082 (5)	0.096 (3)
H8A	0.1711	0.3700	−0.0198	0.144*
H8B	0.2272	0.3623	0.0637	0.144*
H8C	0.2841	0.3559	−0.0196	0.144*
C9	0.4396 (8)	0.7500	−0.0320 (5)	0.066 (3)
H9A	0.5066	0.7500	−0.0488	0.099*
H9B	0.4078	0.7978	−0.0530	0.099*	0.50
H9C	0.4078	0.7022	−0.0530	0.099*	0.50
C10	0.3045 (7)	0.7500	0.1705 (6)	0.072 (3)
H10A	0.3222	0.7500	0.2276	0.108*
H10B	0.2667	0.7022	0.1586	0.108*	0.50
H10C	0.2667	0.7978	0.1586	0.108*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0439 (3)	0.0543 (3)	0.0502 (3)	0.000	−0.0037 (3)	0.000
Sn2	0.0534 (4)	0.0459 (3)	0.0503 (3)	0.000	−0.0019 (3)	0.000
N1	0.051 (3)	0.048 (3)	0.054 (3)	0.008 (2)	−0.004 (3)	0.006 (2)
N2	0.080 (4)	0.048 (3)	0.067 (3)	−0.010 (3)	−0.015 (3)	0.009 (3)
N3	0.058 (3)	0.049 (3)	0.050 (3)	0.010 (2)	0.000 (3)	0.002 (2)
N4	0.077 (4)	0.054 (3)	0.060 (3)	−0.001 (3)	0.001 (3)	0.003 (2)
S1	0.0649 (11)	0.0480 (9)	0.0776 (11)	0.0094 (8)	−0.0071 (9)	−0.0073 (8)
S2	0.0522 (10)	0.0504 (9)	0.0841 (12)	0.0054 (8)	0.0027 (9)	0.0019 (8)
S3	0.0784 (13)	0.0800 (13)	0.0814 (13)	−0.0037 (11)	0.0119 (11)	0.0128 (10)
S4	0.0728 (11)	0.0481 (9)	0.0703 (10)	0.0163 (9)	−0.0074 (9)	0.0044 (8)
S5	0.0706 (12)	0.0535 (10)	0.0813 (12)	0.0090 (9)	−0.0135 (10)	0.0023 (8)
S6	0.0677 (12)	0.1003 (15)	0.0819 (13)	−0.0007 (11)	−0.0121 (11)	0.0127 (11)
C1	0.048 (4)	0.044 (3)	0.054 (3)	0.004 (3)	−0.014 (3)	0.003 (3)
C2	0.066 (4)	0.056 (4)	0.048 (3)	−0.001 (3)	−0.009 (3)	0.001 (3)
C3	0.086 (6)	0.091 (6)	0.102 (6)	−0.019 (5)	0.005 (5)	0.031 (5)
C4	0.086 (8)	0.110 (8)	0.043 (5)	0.000	0.011 (5)	0.000
C5	0.061 (6)	0.061 (6)	0.094 (7)	0.000	−0.032 (6)	0.000
C6	0.053 (4)	0.050 (3)	0.043 (3)	0.009 (3)	0.010 (3)	0.004 (3)
C7	0.059 (4)	0.066 (4)	0.033 (3)	−0.001 (3)	0.010 (3)	0.006 (3)
C8	0.092 (6)	0.108 (6)	0.088 (5)	−0.025 (5)	−0.009 (5)	0.006 (5)
C9	0.089 (7)	0.061 (6)	0.047 (5)	0.000	−0.004 (5)	0.000
C10	0.078 (7)	0.059 (6)	0.080 (6)	0.000	0.022 (6)	0.000

Geometric parameters (Å, º) top

Sn1—C5	2.102 (9)	S5—C6	1.721 (6)
Sn1—C4	2.144 (8)	S6—C7	1.741 (7)
Sn1—S2ⁱ	2.475 (2)	S6—C8	1.790 (8)
Sn1—S2	2.475 (2)	C3—H3A	0.9600
Sn1—N1	2.894 (5)	C3—H3B	0.9600
Sn2—C10	2.112 (9)	C3—H3C	0.9600
Sn2—C9	2.115 (8)	C4—H4A	0.9600
Sn2—S5ⁱⁱ	2.468 (2)	C4—H4B	0.9600
Sn2—S5	2.468 (2)	C4—H4C	0.9600
N1—C1	1.308 (7)	C5—H5A	0.9600
N1—C2	1.382 (7)	C5—H5B	0.9600
N2—C2	1.301 (8)	C5—H5C	0.9600
N2—S1	1.678 (6)	C8—H8A	0.9600
N3—C6	1.325 (7)	C8—H8B	0.9600
N3—C7	1.384 (7)	C8—H8C	0.9600
N4—C7	1.306 (7)	C9—H9A	0.9600
N4—S4	1.651 (6)	C9—H9B	0.9600
S1—C1	1.721 (6)	C9—H9C	0.9600
S2—C1	1.725 (6)	C10—H10A	0.9600
S3—C2	1.744 (7)	C10—H10B	0.9600
S3—C3	1.794 (8)	C10—H10C	0.9600
S4—C6	1.719 (6)

C5—Sn1—C4	123.5 (4)	H3A—C3—H3C	109.5
C5—Sn1—S2ⁱ	110.1 (2)	H3B—C3—H3C	109.5
C4—Sn1—S2ⁱ	110.5 (2)	Sn1—C4—H4A	109.5
C5—Sn1—S2	110.1 (2)	Sn1—C4—H4B	109.5
C4—Sn1—S2	110.5 (2)	H4A—C4—H4B	109.5
S2ⁱ—Sn1—S2	85.74 (9)	Sn1—C4—H4C	109.5
C5—Sn1—N1	83.37 (11)	H4A—C4—H4C	109.5
C4—Sn1—N1	85.03 (11)	H4B—C4—H4C	109.5
S2ⁱ—Sn1—N1	145.17 (11)	Sn1—C5—H5A	109.5
S2—Sn1—N1	59.45 (11)	Sn1—C5—H5B	109.5
C10—Sn2—C9	127.0 (4)	H5A—C5—H5B	109.5
C10—Sn2—S5ⁱⁱ	110.1 (2)	Sn1—C5—H5C	109.5
C9—Sn2—S5ⁱⁱ	108.1 (2)	H5A—C5—H5C	109.5
C10—Sn2—S5	110.1 (2)	H5B—C5—H5C	109.5
C9—Sn2—S5	108.1 (2)	N3—C6—S4	111.4 (4)
S5ⁱⁱ—Sn2—S5	85.61 (10)	N3—C6—S5	124.6 (4)
C1—N1—C2	109.2 (5)	S4—C6—S5	124.0 (4)
C1—N1—Sn1	84.5 (3)	N4—C7—N3	119.4 (6)
C2—N1—Sn1	166.2 (4)	N4—C7—S6	124.8 (5)
C2—N2—S1	107.5 (4)	N3—C7—S6	115.8 (5)
C6—N3—C7	108.2 (5)	S6—C8—H8A	109.5
C7—N4—S4	108.1 (4)	S6—C8—H8B	109.5
N2—S1—C1	92.3 (3)	H8A—C8—H8B	109.5
C1—S2—Sn1	91.8 (2)	S6—C8—H8C	109.5
C2—S3—C3	100.4 (4)	H8A—C8—H8C	109.5
N4—S4—C6	92.9 (3)	H8B—C8—H8C	109.5
C6—S5—Sn2	93.5 (2)	Sn2—C9—H9A	109.5
C7—S6—C8	100.4 (4)	Sn2—C9—H9B	109.5
N1—C1—S1	111.6 (4)	H9A—C9—H9B	109.5
N1—C1—S2	124.2 (4)	Sn2—C9—H9C	109.5
S1—C1—S2	124.2 (4)	H9A—C9—H9C	109.5
N2—C2—N1	119.4 (6)	H9B—C9—H9C	109.5
N2—C2—S3	124.8 (5)	Sn2—C10—H10A	109.5
N1—C2—S3	115.9 (5)	Sn2—C10—H10B	109.5
S3—C3—H3A	109.5	H10A—C10—H10B	109.5
S3—C3—H3B	109.5	Sn2—C10—H10C	109.5
H3A—C3—H3B	109.5	H10A—C10—H10C	109.5
S3—C3—H3C	109.5	H10B—C10—H10C	109.5

Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₂(C₃H₃N₂S₃)₂]
M_r	475.27
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	13.721 (9), 16.383 (10), 16.282 (10)
V (Å³)	3660 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.07
Crystal size (mm)	0.48 × 0.37 × 0.25

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.436, 0.625
No. of measured, independent and observed [I > 2σ(I)] reflections	18306, 3368, 2269
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.09
No. of reflections	3368
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.58

Computer programs: SMART (Siemens, 1996), SaINT (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the National Natural Science Foundation of China (20741008) and the State Key Laboratory of Crystalline Materials, Liaocheng University, People's Republic of China.

References

Ma, C.-L., Zhang, J.-H., Tian, G.-R. & Zhang, R.-F. (2005). J. Organomet. Chem. 690, 519–533. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar