metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

(3-Anilino-1-phenyl­imino­thio­ureato)chloridodi­methyl­tin(IV)

aDepartamento de Quimíca, Universidad Nacional de Colombia, Sede Bogotá, Bogotá, Colombia, and bLaboratoire DECOMET, UMR–CNRS 7177, Université Louis Pasteur, 4 rue Blaise Pascal, 67000 Strasbourg, France
*Correspondence e-mail: kaokio@unal.edu.co

(Received 10 March 2009; accepted 17 March 2009; online 25 March 2009)

In the title compound, [Sn(CH3)2(C13H11N4S)Cl], the Sn 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 the Cl atom occupying the apical positions.

Related literature

For related structures, see: Labib et al. (1996[Labib, L., Khalil, T. E., Iskander, M. F. & Refaar, L. S. (1996). Polyhedron, 15, 349-357.]). For the biological and pharmaceutical applications of organotin derivatives, see: Davies & Smith (1982[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.]); Diop et al. (2003[Diop, L., Mahieu, B., Mahon, M. F., Molloy, K. C. & Okio, K. Y. A. (2003). Appl. Organomet. Chem. 17, 881-882.]); Okio et al. (2003[Okio, K. Y. A., Diop, L., Barry, A. H., Jouini, T. & Ortega, S. H. (2003). Appl. Organomet. Chem. 17, 317-318.]).

[Scheme 1]

Experimental

Crystal data
  • [Sn(CH3)2(C13H11N4S)Cl]

  • Mr = 439.53

  • Orthorhombic, P b n a

  • a = 11.6850 (2) Å

  • b = 14.8920 (5) Å

  • c = 20.6790 (7) Å

  • V = 3598.42 (18) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 1.69 mm−1

  • T = 173 K

  • 0.10 × 0.10 × 0.10 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: none

  • 25644 measured reflections

  • 4130 independent reflections

  • 2731 reflections with I > 2σ(I)

  • Rint = 0.115

Refinement
  • R[F2 > 2σ(F2)] = 0.044

  • wR(F2) = 0.137

  • S = 1.09

  • 4130 reflections

  • 199 parameters

  • H-atom parameters constrained

  • Δρmax = 1.13 e Å−3

  • Δρmin = −1.84 e Å−3

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[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.]); data reduction: DENZO (Otwinowski & Minor, 1997[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.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The interest in the synthesis of new organotin derivatives is related to the diversity of structures that such compounds can form, and on the other side, to their biological and pharmaceutical applications (Davies & Smith, 1982,Okio et al., 2003; Diop et al., 2003). We report here the crystal structure of the title compound (I). The structure consists of discrete molecules (Fig.1).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 N1 and Cl atom occupying the apical positions. The Sn—Cl and Sn—S bond distances are shorter than the values of 2.672 (1) Å and 2.478 (2) Å found in dimethylmonochloro[(N-(2-pyridinylmethylene) hydrazinecarbothioamidato)NS(– 1)]tin(IV) hemihydrate ( Labib et al.,1996), while the Sn—N and Sn—C bonds are longer than the corresponding ones reported for the same previous compound, (2.359 (4) Å, 2.108 (7) Å and 2.105 (7) Å), as representative example.

Related literature top

For related structures, see: Labib et al. (1996). For the biological and pharmaceutical applications of organotin derivatives, see: Davies & Smith (1982); Diop et al. (2003); Okio et al. (2003).

Experimental top

Compound (I) was obtained by reacting dimethyltin (IV) dichloride (220 mg, 1 mmol) with 1,5 diphenylthiocarbazone (128 mg, 0.5 mmol) in dichloromethane under reflux for 3 h. Dark red crystals suitable for X-ray analysis were grown by slow solvent evaporation.

Refinement top

H atoms were positioned geometrically, with C—H distances in the range 0.95 - 0.98 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2-1.5Ueq(C). H atom bonded to N4 was found in difference maps and positioned geometrically (N4-H = 0.88 Å) and was refined with a riding model, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (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 top
[Figure 1] 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.
(3-Anilino-1-phenyliminothioureato)chloridodimethyltin(IV) top
Crystal data top
[Sn(CH3)2(C13H11N4S)Cl]F(000) = 1744
Mr = 439.53Dx = 1.623 Mg m3
Orthorhombic, PbnaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2bCell parameters from 14356 reflections
a = 11.6850 (2) Åθ = 1.0–27.5°
b = 14.8920 (5) ŵ = 1.69 mm1
c = 20.6790 (7) ÅT = 173 K
V = 3598.42 (18) Å3Prism, dark red
Z = 80.10 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
2731 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.115
Graphite monochromatorθmax = 27.5°, θmin = 2.0°
π scansh = 1515
25644 measured reflectionsk = 1819
4130 independent reflectionsl = 2622
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.07P)2]
where P = (Fo2 + 2Fc2)/3
4130 reflections(Δ/σ)max = 0.002
199 parametersΔρmax = 1.13 e Å3
0 restraintsΔρmin = 1.84 e Å3
Crystal data top
[Sn(CH3)2(C13H11N4S)Cl]V = 3598.42 (18) Å3
Mr = 439.53Z = 8
Orthorhombic, PbnaMo Kα radiation
a = 11.6850 (2) ŵ = 1.69 mm1
b = 14.8920 (5) ÅT = 173 K
c = 20.6790 (7) Å0.10 × 0.10 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
2731 reflections with I > 2σ(I)
25644 measured reflectionsRint = 0.115
4130 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.09Δρmax = 1.13 e Å3
4130 reflectionsΔρmin = 1.84 e Å3
199 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
xyzUiso*/Ueq
Sn0.18590 (3)0.56103 (2)0.509606 (17)0.03083 (14)
Cl0.03058 (11)0.57242 (10)0.59081 (6)0.0489 (4)
S0.30578 (10)0.64147 (10)0.58678 (6)0.0440 (4)
N10.3690 (3)0.5795 (2)0.45454 (18)0.0308 (9)
N20.4565 (3)0.6110 (3)0.48494 (17)0.0325 (9)
N30.5342 (3)0.6667 (2)0.57432 (18)0.0343 (9)
N40.5270 (3)0.6917 (2)0.63558 (19)0.0364 (9)
H4N0.46060.68890.65560.044*
C10.3037 (4)0.5110 (3)0.3553 (2)0.0368 (11)
H10.23160.50110.37540.044*
C20.3220 (4)0.4841 (3)0.2918 (3)0.0444 (13)
H20.26200.45590.26830.053*
C30.4263 (5)0.4979 (3)0.2626 (2)0.0516 (14)
H30.43800.47970.21910.062*
C40.5137 (5)0.5383 (4)0.2966 (3)0.0484 (14)
H40.58560.54740.27610.058*
C50.4985 (4)0.5659 (3)0.3598 (2)0.0364 (11)
H50.55950.59340.38290.044*
C60.3923 (4)0.5527 (3)0.3896 (2)0.0316 (10)
C70.6144 (4)0.7333 (3)0.7357 (2)0.0423 (13)
H70.54510.71880.75730.051*
C80.7073 (5)0.7652 (3)0.7698 (3)0.0474 (14)
H80.70110.77350.81520.057*
C90.8086 (4)0.7852 (4)0.7392 (3)0.0503 (14)
H90.87180.80750.76330.060*
C100.8178 (4)0.7729 (4)0.6738 (3)0.0518 (15)
H100.88840.78560.65290.062*
C110.7263 (5)0.7424 (3)0.6376 (3)0.0425 (13)
H110.73300.73510.59210.051*
C120.6243 (4)0.7226 (3)0.6692 (2)0.0342 (11)
C130.4384 (4)0.6391 (3)0.5470 (2)0.0329 (10)
C140.2130 (5)0.4204 (4)0.5157 (3)0.0438 (14)
H14A0.15170.38900.49260.066*
H14B0.21290.40190.56120.066*
H14C0.28690.40530.49610.066*
C150.1051 (3)0.6462 (3)0.4410 (2)0.0374 (11)
H15A0.08600.61150.40220.056*
H15B0.15720.69520.42930.056*
H15C0.03500.67120.45980.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.0292 (2)0.0351 (2)0.0282 (2)0.00016 (13)0.00196 (12)0.00342 (13)
Cl0.0390 (7)0.0750 (10)0.0326 (7)0.0030 (6)0.0051 (5)0.0065 (6)
S0.0344 (6)0.0634 (9)0.0342 (8)0.0036 (6)0.0021 (5)0.0164 (6)
N10.033 (2)0.029 (2)0.031 (2)0.0025 (16)0.0031 (17)0.0010 (16)
N20.035 (2)0.030 (2)0.032 (2)0.0017 (18)0.0044 (17)0.0016 (17)
N30.037 (2)0.033 (2)0.033 (2)0.0034 (16)0.0054 (17)0.0021 (18)
N40.039 (2)0.037 (2)0.034 (2)0.0020 (18)0.0062 (17)0.0077 (18)
C10.044 (3)0.035 (3)0.032 (3)0.002 (2)0.007 (2)0.001 (2)
C20.069 (4)0.031 (3)0.033 (3)0.008 (3)0.017 (3)0.006 (2)
C30.082 (4)0.042 (3)0.031 (3)0.013 (3)0.000 (3)0.001 (2)
C40.066 (3)0.043 (3)0.036 (3)0.011 (3)0.018 (3)0.006 (2)
C50.043 (3)0.033 (3)0.033 (3)0.002 (2)0.005 (2)0.002 (2)
C60.040 (2)0.027 (3)0.028 (3)0.0068 (19)0.002 (2)0.0025 (19)
C70.045 (3)0.046 (3)0.036 (3)0.012 (2)0.007 (2)0.009 (2)
C80.061 (3)0.041 (3)0.040 (3)0.019 (2)0.021 (3)0.012 (2)
C90.050 (3)0.041 (3)0.060 (4)0.001 (3)0.024 (3)0.007 (3)
C100.048 (3)0.048 (3)0.060 (4)0.018 (2)0.013 (3)0.006 (3)
C110.049 (3)0.038 (3)0.040 (3)0.007 (2)0.012 (2)0.005 (2)
C120.037 (3)0.025 (2)0.040 (3)0.004 (2)0.010 (2)0.004 (2)
C130.035 (2)0.032 (3)0.032 (3)0.000 (2)0.004 (2)0.004 (2)
C140.042 (3)0.037 (3)0.052 (4)0.003 (2)0.002 (2)0.010 (2)
C150.036 (2)0.038 (3)0.038 (3)0.000 (2)0.003 (2)0.006 (2)
Geometric parameters (Å, º) top
Sn—C142.122 (5)C4—H40.9500
Sn—C152.125 (5)C5—C61.399 (6)
Sn—S2.4380 (13)C5—H50.9500
Sn—N12.439 (4)C7—C81.379 (7)
Sn—Cl2.4784 (13)C7—C121.388 (7)
S—C131.755 (4)C7—H70.9500
N1—N21.289 (5)C8—C91.375 (8)
N1—C61.428 (6)C8—H80.9500
N2—C131.366 (6)C9—C101.370 (8)
N3—C131.320 (5)C9—H90.9500
N3—N41.323 (5)C10—C111.382 (7)
N4—C121.410 (6)C10—H100.9500
N4—H4N0.8800C11—C121.392 (7)
C1—C21.390 (7)C11—H110.9500
C1—C61.400 (6)C14—H14A0.9800
C1—H10.9500C14—H14B0.9800
C2—C31.375 (7)C14—H14C0.9800
C2—H20.9500C15—H15A0.9800
C3—C41.377 (7)C15—H15B0.9800
C3—H30.9500C15—H15C0.9800
C4—C51.383 (7)
C14—Sn—C15134.0 (2)C5—C6—N1122.9 (4)
C14—Sn—S111.14 (15)C1—C6—N1117.3 (4)
C15—Sn—S113.52 (14)C8—C7—C12118.8 (5)
C14—Sn—N190.45 (17)C8—C7—H7120.6
C15—Sn—N190.60 (14)C12—C7—H7120.6
S—Sn—N175.30 (9)C9—C8—C7121.1 (5)
C14—Sn—Cl97.86 (15)C9—C8—H8119.4
C15—Sn—Cl94.95 (13)C7—C8—H8119.4
S—Sn—Cl86.77 (4)C10—C9—C8119.5 (5)
N1—Sn—Cl161.98 (9)C10—C9—H9120.2
C13—S—Sn100.99 (16)C8—C9—H9120.2
N2—N1—C6114.2 (4)C9—C10—C11121.3 (5)
N2—N1—Sn120.6 (3)C9—C10—H10119.4
C6—N1—Sn125.1 (3)C11—C10—H10119.4
N1—N2—C13116.6 (4)C10—C11—C12118.5 (5)
C13—N3—N4116.3 (4)C10—C11—H11120.7
N3—N4—C12120.8 (4)C12—C11—H11120.7
N3—N4—H4N119.6C7—C12—C11120.8 (4)
C12—N4—H4N119.6C7—C12—N4117.3 (4)
C2—C1—C6119.5 (4)C11—C12—N4121.9 (4)
C2—C1—H1120.3N3—C13—N2111.5 (4)
C6—C1—H1120.3N3—C13—S122.8 (4)
C3—C2—C1120.5 (5)N2—C13—S125.7 (3)
C3—C2—H2119.7Sn—C14—H14A109.5
C1—C2—H2119.7Sn—C14—H14B109.5
C2—C3—C4120.0 (5)H14A—C14—H14B109.5
C2—C3—H3120.0Sn—C14—H14C109.5
C4—C3—H3120.0H14A—C14—H14C109.5
C3—C4—C5121.1 (5)H14B—C14—H14C109.5
C3—C4—H4119.4Sn—C15—H15A109.5
C5—C4—H4119.4Sn—C15—H15B109.5
C4—C5—C6119.2 (5)H15A—C15—H15B109.5
C4—C5—H5120.4Sn—C15—H15C109.5
C6—C5—H5120.4H15A—C15—H15C109.5
C5—C6—C1119.8 (4)H15B—C15—H15C109.5
C14—Sn—S—C1377.8 (2)C2—C1—C6—N1179.6 (4)
C15—Sn—S—C1391.0 (2)N2—N1—C6—C54.7 (6)
N1—Sn—S—C136.86 (18)Sn—N1—C6—C5179.1 (3)
Cl—Sn—S—C13175.02 (17)N2—N1—C6—C1174.9 (4)
C14—Sn—N1—N2104.0 (3)Sn—N1—C6—C11.3 (5)
C15—Sn—N1—N2121.9 (3)C12—C7—C8—C90.8 (7)
S—Sn—N1—N27.7 (3)C7—C8—C9—C100.3 (8)
Cl—Sn—N1—N213.8 (5)C8—C9—C10—C111.3 (9)
C14—Sn—N1—C671.9 (3)C9—C10—C11—C121.2 (8)
C15—Sn—N1—C662.1 (3)C8—C7—C12—C111.0 (7)
S—Sn—N1—C6176.3 (3)C8—C7—C12—N4178.6 (4)
Cl—Sn—N1—C6170.2 (2)C10—C11—C12—C70.0 (7)
C6—N1—N2—C13179.0 (4)C10—C11—C12—N4179.6 (5)
Sn—N1—N2—C134.6 (5)N3—N4—C12—C7169.6 (4)
C13—N3—N4—C12179.8 (4)N3—N4—C12—C1110.9 (7)
C6—C1—C2—C30.2 (7)N4—N3—C13—N2177.1 (4)
C1—C2—C3—C40.3 (8)N4—N3—C13—S4.1 (6)
C2—C3—C4—C50.3 (8)N1—N2—C13—N3177.5 (4)
C3—C4—C5—C60.3 (7)N1—N2—C13—S3.8 (6)
C4—C5—C6—C10.8 (7)Sn—S—C13—N3172.3 (4)
C4—C5—C6—N1179.6 (4)Sn—S—C13—N29.1 (4)
C2—C1—C6—C50.8 (7)

Experimental details

Crystal data
Chemical formula[Sn(CH3)2(C13H11N4S)Cl]
Mr439.53
Crystal system, space groupOrthorhombic, Pbna
Temperature (K)173
a, b, c (Å)11.6850 (2), 14.8920 (5), 20.6790 (7)
V3)3598.42 (18)
Z8
Radiation typeMo Kα
µ (mm1)1.69
Crystal size (mm)0.10 × 0.10 × 0.10
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
25644, 4130, 2731
Rint0.115
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.137, 1.09
No. of reflections4130
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.13, 1.84

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

 

References

First citationDavies, 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.  Google Scholar
First citationDiop, L., Mahieu, B., Mahon, M. F., Molloy, K. C. & Okio, K. Y. A. (2003). Appl. Organomet. Chem. 17, 881-882.  Web of Science CSD CrossRef CAS Google Scholar
First citationLabib, L., Khalil, T. E., Iskander, M. F. & Refaar, L. S. (1996). Polyhedron, 15, 349-357.  CSD CrossRef CAS Web of Science Google Scholar
First citationNonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOkio, K. Y. A., Diop, L., Barry, A. H., Jouini, T. & Ortega, S. H. (2003). Appl. Organomet. Chem. 17, 317-318.  Web of Science CSD CrossRef CAS Google Scholar
First citationOtwinowski, 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.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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