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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1353.
Published online 2010 October 2. doi:  10.1107/S1600536810038705
PMCID: PMC3009011

Chloridodimeth­yl(thio­semi­carbazide)tin(IV) chloride

Abstract

In the title salt, [Sn(CH3)2Cl(CH4N3S)]Cl, the SnIV 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 D 3 3(10) link cations and anions.

Related literature

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

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Object name is e-66-m1353-scheme1.jpg

Experimental

Crystal data

  • [Sn(CH3)2Cl(CH4N3S)]Cl
  • M r = 309.79
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1353-efi1.jpg
  • a = 13.4980 (12) Å
  • b = 6.2470 (5) Å
  • c = 12.7160 (13) Å
  • β = 108.871 (10)°
  • V = 1014.60 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.19 mm−1
  • T = 293 K
  • 0.13 × 0.10 × 0.09 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SORTAV; Blessing, 1995 [triangle]) T min = 0.613, T max = 0.809
  • 4452 measured reflections
  • 2915 independent reflections
  • 2475 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.103
  • S = 1.14
  • 2915 reflections
  • 91 parameters
  • H-atom parameters constrained
  • Δρmax = 1.04 e Å−3
  • Δρmin = −1.52 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038705/bx2306sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038705/bx2306Isup2.hkl

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

Acknowledgments

The authors are grateful to Richard Welter for the X-ray analysis.

supplementary crystallographic information

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.

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.

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 Uiso(H) = 1.5Ueq(C) and 1.2Ueq(N)

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.

Crystal data

[Sn(CH3)2Cl(CH4N3S)]ClF(000) = 596
Mr = 309.79Dx = 2.028 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 1915 reflections
a = 13.4980 (12) Åθ = 1.0–30.0°
b = 6.2470 (5) ŵ = 3.19 mm1
c = 12.7160 (13) ÅT = 293 K
β = 108.871 (10)°Prism, colorless
V = 1014.60 (16) Å30.13 × 0.10 × 0.09 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer2915 independent reflections
Radiation source: fine-focus sealed tube2475 reflections with I > 2σ(I)
graphiteRint = 0.020
π scansθmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)h = −18→18
Tmin = 0.613, Tmax = 0.809k = −7→8
4452 measured reflectionsl = −17→17

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.14w = 1/[σ2(Fo2) + (0.0482P)2 + 1.1794P] where P = (Fo2 + 2Fc2)/3
2915 reflections(Δ/σ)max = 0.001
91 parametersΔρmax = 1.04 e Å3
0 restraintsΔρmin = −1.52 e Å3

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 (Å2)

xyzUiso*/Ueq
Sn0.18008 (2)0.64590 (4)0.54686 (2)0.03327 (10)
Cl10.10951 (9)0.27486 (19)0.52290 (13)0.0570 (3)
Cl20.37205 (8)0.89418 (16)0.34229 (9)0.0384 (2)
S0.34762 (8)0.45496 (15)0.57559 (10)0.0394 (2)
N10.4153 (3)0.8592 (5)0.6156 (3)0.0304 (6)
H10.46470.95080.64200.036*
N20.3105 (2)0.9290 (5)0.5800 (3)0.0348 (7)
H20.29371.06210.57070.042*
N30.5392 (3)0.6073 (5)0.6316 (3)0.0371 (7)
H3AN0.58590.70630.64940.045*
H3BN0.55750.47620.62820.045*
C10.4390 (3)0.6566 (6)0.6093 (3)0.0291 (7)
C20.1509 (4)0.7230 (10)0.6955 (4)0.0548 (12)
H2A0.15480.87530.70600.082*
H2B0.20220.65490.75690.082*
H2C0.08230.67380.69130.082*
C30.1119 (4)0.7551 (9)0.3820 (4)0.0471 (10)
H3A0.06400.86950.38060.071*
H3B0.07490.63960.33620.071*
H3C0.16580.80600.35420.071*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn0.03237 (15)0.03147 (15)0.03651 (16)−0.00300 (10)0.01187 (11)−0.00248 (10)
Cl10.0403 (5)0.0344 (5)0.0951 (9)−0.0086 (5)0.0201 (6)−0.0063 (6)
Cl20.0369 (5)0.0377 (5)0.0413 (5)−0.0039 (4)0.0138 (4)0.0036 (4)
S0.0352 (5)0.0245 (4)0.0595 (6)−0.0027 (4)0.0168 (4)−0.0017 (4)
N10.0299 (15)0.0266 (14)0.0342 (15)−0.0046 (12)0.0097 (12)−0.0039 (12)
N20.0285 (15)0.0259 (14)0.0494 (19)0.0002 (13)0.0117 (13)0.0017 (14)
N30.0316 (16)0.0367 (17)0.0444 (19)−0.0017 (14)0.0141 (14)−0.0064 (14)
C10.0322 (18)0.0308 (17)0.0262 (15)0.0006 (14)0.0121 (13)0.0015 (13)
C20.062 (3)0.067 (3)0.046 (3)−0.017 (3)0.031 (2)−0.010 (2)
C30.042 (2)0.057 (3)0.038 (2)−0.002 (2)0.0072 (17)0.002 (2)

Geometric parameters (Å, °)

Sn—C22.107 (4)N3—C11.325 (5)
Sn—C32.112 (4)N3—H3AN0.8600
Sn—N22.434 (3)N3—H3BN0.8600
Sn—S2.4771 (11)C2—H2A0.9600
Sn—Cl12.4870 (12)C2—H2B0.9600
S—C11.718 (4)C2—H2C0.9600
N1—C11.315 (5)C3—H3A0.9600
N1—N21.408 (4)C3—H3B0.9600
N1—H10.8600C3—H3C0.9600
N2—H20.8600
C2—Sn—C3132.0 (2)C1—N3—H3BN120.0
C2—Sn—N290.75 (17)H3AN—N3—H3BN120.0
C3—Sn—N289.75 (16)N1—C1—N3117.6 (3)
C2—Sn—S113.85 (17)N1—C1—S123.5 (3)
C3—Sn—S112.70 (14)N3—C1—S118.9 (3)
N2—Sn—S75.51 (8)Sn—C2—H2A109.5
C2—Sn—Cl198.48 (16)Sn—C2—H2B109.5
C3—Sn—Cl198.80 (15)H2A—C2—H2B109.5
N2—Sn—Cl1157.72 (8)Sn—C2—H2C109.5
S—Sn—Cl182.21 (4)H2A—C2—H2C109.5
C1—S—Sn103.38 (13)H2B—C2—H2C109.5
C1—N1—N2121.2 (3)Sn—C3—H3A109.5
C1—N1—H1119.4Sn—C3—H3B109.5
N2—N1—H1119.4H3A—C3—H3B109.5
N1—N2—Sn115.2 (2)Sn—C3—H3C109.5
N1—N2—H2122.4H3A—C3—H3C109.5
Sn—N2—H2122.4H3B—C3—H3C109.5
C1—N3—H3AN120.0
C2—Sn—S—C1−79.8 (2)S—Sn—N2—N1−9.3 (2)
C3—Sn—S—C188.0 (2)Cl1—Sn—N2—N1−9.7 (4)
N2—Sn—S—C14.48 (15)N2—N1—C1—N3172.0 (3)
Cl1—Sn—S—C1−175.69 (14)N2—N1—C1—S−8.9 (5)
C1—N1—N2—Sn13.1 (4)Sn—S—C1—N10.0 (4)
C2—Sn—N2—N1105.2 (3)Sn—S—C1—N3179.2 (3)
C3—Sn—N2—N1−122.9 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Cl2i0.862.35553.147 (4)153.17
N2—H2···Sii0.862.55493.327 (3)149.90

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2306).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Davies, A. G. & Smith, P. G. (1982). Comprehensive Organometallic Chemistry, edited by G. Wilkinson, F. Gordon, A. Stone & E.W. Abel, pp. 519–616. New York: Pergamon Press.
  • Delgado, D. J. A., Okio, C. K. Y. A. & Welter, R. (2009). Acta Cryst. E65, m426. [PMC free article] [PubMed]
  • Nonius (1998). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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