Chloridodimeth­yl(thio­semi­carbazide)tin(IV) chloride

In the title salt, [Sn(CH₃)₂Cl(CH₄N₃S)]Cl, the Sn^IV atom is five-coordinated in a distorted trigonal-bipyramidal geometry with two methyl groups and one S atom in the equatorial plane, and one N atom and one Cl atom occupying the apical positions. In the crystal, mol­ecules are linked by inter­molecular N—H...S hydrogen bonds with set graph-motif C(4) along [010]. N—H... Cl hydrogen bonds with graph-set motif D(2) and D₃³(10) link cations and anions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](N-C) = 0.005 Å
• R factor = 0.037
• wR factor = 0.103
• Data-to-parameter ratio = 32.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         23
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         16

Alert level G
PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 =          3
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Organotin(IV) complexes have been extensively studied due to the diversity of structures that such compounds can form and to their potential biological activities as well as their wide industrial and agricultural applications (Davies & Smith, 1982). In the framework of our research for new organotin(IV) compounds (Delgado et al., 2009), we report here the crystal structure of the title compound (I). The asymmetric unit is formed by one cation and one anion. The Sn atom is five-coordinate in a distorted trigonal–bipyramidal geometry. The distorted trigonal-bipyramidal coordination polyhedron has two methyl groups and one S atom in the equatorial plane, the N2 and Cl1 atom occupying the apical positions. In the crystal, molecules are linked by intermolecular N—H···S hydrogen bonds with set graph-motif C(4) along [010]. N—H··· Cl hydrogen bond linking cations and anions with set graph-motif D(2) and D₃³(10) , Table 1 and Fig.2. The C1-S and C1-N1 bond distances are quite shorter than the ones reported for C-S and C-N single bonds (1.755 (4), 1.366 (6)) (Delgado et al., 2009), suggesting the delocalization of the C=S double bond on the SCN moiety.

Related literature

For a related structure, see: Delgado et al. (2009). For set-graph-motifs, see: Bernstein, et al. (1995). For the biological activity of organotin(IV) complexes, see: Davies & Smith 1982.

S2. Experimental

Compound (I) was obtained by reacting dimethyltin (IV) dichloride (220 mg, 1 mmol) with thiosemicarbazide (68 mg, 0.75 mmol) in methanol under reflux for 3 h. Colourless crystals suitable for X-ray analysis were grown by slow solvent evaporation.

S3. Refinement

H atoms were positioned geometrically, with C—H, N—H distances of 0.96 and 0.86Å respectively, and constrained to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C) and 1.2U_eq(N)

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted.
	Fig. 2. Unit-cell packing diagram for (I). Hydrogen bonds are shown as dashed lines.

Chloridodimethyl(thiosemicarbazide)tin(IV) chloride

Crystal data

[Sn(CH3)2Cl(CH4N3S)]Cl	F(000) = 596
Mr = 309.79	Dx = 2.028 Mg m^−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 1915 reflections
a = 13.4980 (12) Å	θ = 1.0–30.0°
b = 6.2470 (5) Å	µ = 3.19 mm^−1
c = 12.7160 (13) Å	T = 293 K
β = 108.871 (10)°	Prism, colorless
V = 1014.60 (16) Å^3	0.13 × 0.10 × 0.09 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2915 independent reflections
Radiation source: fine-focus sealed tube	2475 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
π scans	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −18→18
Tmin = 0.613, Tmax = 0.809	k = −7→8
4452 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 1.1794P] where P = (Fo^2 + 2Fc^2)/3
2915 reflections	(Δ/σ)max = 0.001
91 parameters	Δρmax = 1.04 e Å^−3
0 restraints	Δρmin = −1.52 e Å^−3

Special details

Experimental. Absorption correction: multi-scan from symmetry-related measurements (SORTAV; Blessing, 1995)

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
Sn	0.18008 (2)	0.64590 (4)	0.54686 (2)	0.03327 (10)
Cl1	0.10951 (9)	0.27486 (19)	0.52290 (13)	0.0570 (3)
Cl2	0.37205 (8)	0.89418 (16)	0.34229 (9)	0.0384 (2)
S	0.34762 (8)	0.45496 (15)	0.57559 (10)	0.0394 (2)
N1	0.4153 (3)	0.8592 (5)	0.6156 (3)	0.0304 (6)
H1	0.4647	0.9508	0.6420	0.036*
N2	0.3105 (2)	0.9290 (5)	0.5800 (3)	0.0348 (7)
H2	0.2937	1.0621	0.5707	0.042*
N3	0.5392 (3)	0.6073 (5)	0.6316 (3)	0.0371 (7)
H3AN	0.5859	0.7063	0.6494	0.045*
H3BN	0.5575	0.4762	0.6282	0.045*
C1	0.4390 (3)	0.6566 (6)	0.6093 (3)	0.0291 (7)
C2	0.1509 (4)	0.7230 (10)	0.6955 (4)	0.0548 (12)
H2A	0.1548	0.8753	0.7060	0.082*
H2B	0.2022	0.6549	0.7569	0.082*
H2C	0.0823	0.6738	0.6913	0.082*
C3	0.1119 (4)	0.7551 (9)	0.3820 (4)	0.0471 (10)
H3A	0.0640	0.8695	0.3806	0.071*
H3B	0.0749	0.6396	0.3362	0.071*
H3C	0.1658	0.8060	0.3542	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn	0.03237 (15)	0.03147 (15)	0.03651 (16)	−0.00300 (10)	0.01187 (11)	−0.00248 (10)
Cl1	0.0403 (5)	0.0344 (5)	0.0951 (9)	−0.0086 (5)	0.0201 (6)	−0.0063 (6)
Cl2	0.0369 (5)	0.0377 (5)	0.0413 (5)	−0.0039 (4)	0.0138 (4)	0.0036 (4)
S	0.0352 (5)	0.0245 (4)	0.0595 (6)	−0.0027 (4)	0.0168 (4)	−0.0017 (4)
N1	0.0299 (15)	0.0266 (14)	0.0342 (15)	−0.0046 (12)	0.0097 (12)	−0.0039 (12)
N2	0.0285 (15)	0.0259 (14)	0.0494 (19)	0.0002 (13)	0.0117 (13)	0.0017 (14)
N3	0.0316 (16)	0.0367 (17)	0.0444 (19)	−0.0017 (14)	0.0141 (14)	−0.0064 (14)
C1	0.0322 (18)	0.0308 (17)	0.0262 (15)	0.0006 (14)	0.0121 (13)	0.0015 (13)
C2	0.062 (3)	0.067 (3)	0.046 (3)	−0.017 (3)	0.031 (2)	−0.010 (2)
C3	0.042 (2)	0.057 (3)	0.038 (2)	−0.002 (2)	0.0072 (17)	0.002 (2)

Geometric parameters (Å, º)

Sn—C2	2.107 (4)	N3—C1	1.325 (5)
Sn—C3	2.112 (4)	N3—H3AN	0.8600
Sn—N2	2.434 (3)	N3—H3BN	0.8600
Sn—S	2.4771 (11)	C2—H2A	0.9600
Sn—Cl1	2.4870 (12)	C2—H2B	0.9600
S—C1	1.718 (4)	C2—H2C	0.9600
N1—C1	1.315 (5)	C3—H3A	0.9600
N1—N2	1.408 (4)	C3—H3B	0.9600
N1—H1	0.8600	C3—H3C	0.9600
N2—H2	0.8600
C2—Sn—C3	132.0 (2)	C1—N3—H3BN	120.0
C2—Sn—N2	90.75 (17)	H3AN—N3—H3BN	120.0
C3—Sn—N2	89.75 (16)	N1—C1—N3	117.6 (3)
C2—Sn—S	113.85 (17)	N1—C1—S	123.5 (3)
C3—Sn—S	112.70 (14)	N3—C1—S	118.9 (3)
N2—Sn—S	75.51 (8)	Sn—C2—H2A	109.5
C2—Sn—Cl1	98.48 (16)	Sn—C2—H2B	109.5
C3—Sn—Cl1	98.80 (15)	H2A—C2—H2B	109.5
N2—Sn—Cl1	157.72 (8)	Sn—C2—H2C	109.5
S—Sn—Cl1	82.21 (4)	H2A—C2—H2C	109.5
C1—S—Sn	103.38 (13)	H2B—C2—H2C	109.5
C1—N1—N2	121.2 (3)	Sn—C3—H3A	109.5
C1—N1—H1	119.4	Sn—C3—H3B	109.5
N2—N1—H1	119.4	H3A—C3—H3B	109.5
N1—N2—Sn	115.2 (2)	Sn—C3—H3C	109.5
N1—N2—H2	122.4	H3A—C3—H3C	109.5
Sn—N2—H2	122.4	H3B—C3—H3C	109.5
C1—N3—H3AN	120.0
C2—Sn—S—C1	−79.8 (2)	S—Sn—N2—N1	−9.3 (2)
C3—Sn—S—C1	88.0 (2)	Cl1—Sn—N2—N1	−9.7 (4)
N2—Sn—S—C1	4.48 (15)	N2—N1—C1—N3	172.0 (3)
Cl1—Sn—S—C1	−175.69 (14)	N2—N1—C1—S	−8.9 (5)
C1—N1—N2—Sn	13.1 (4)	Sn—S—C1—N1	0.0 (4)
C2—Sn—N2—N1	105.2 (3)	Sn—S—C1—N3	179.2 (3)
C3—Sn—N2—N1	−122.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2^i	0.86	2.3555	3.147 (4)	153.17
N2—H2···S^ii	0.86	2.5549	3.327 (3)	149.90

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