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

Abstract

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,

• a = 13.721 (9) Å

• b = 16.383 (10) Å

• c = 16.282 (10) Å

• V = 3660 (4) ų

• 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[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 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.

Supplementary Material

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

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H = 0.96 Å, and with U_iso(H) = 1.5U_eq(C)].

Figures

Fig. 1.

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

Crystal data

[Sn(CH3)2(C3H3N2S3)2]	F(000) = 1872
Mr = 475.27	Dx = 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

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

Refinement

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(Fo2) + (0.0351P)2 + 5.554P] where P = (Fo2 + 2Fc2)/3
3368 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.72 e Å−3
0 restraints	Δρmin = −0.58 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

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.