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

Delgado D., J.A.; Okio, C.K.Y.A.; Welter, R.

doi:10.1107/S160053680900988X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m426

doi:10.1107/S160053680900988X

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

Jorge A. Delgado D.,^a Coco K. Y. A. Okio ^a ^* and Richard Welter ^b

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

Experimental

Crystal data

[Sn(CH₃)₂(C₁₃H₁₁N₄S)Cl]
M_r = 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)
R_int = 0.115

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.137
S = 1.09
4130 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 1.13 e Å⁻³
Δρ_min = −1.84 e Å⁻³

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900988X/bx2197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680900988X/bx2197Isup2.hkl

checkCIF report

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.

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

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
M_r = 439.53	D_x = 1.623 Mg m⁻³
Orthorhombic, Pbna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2b	Cell parameters from 14356 reflections
a = 11.6850 (2) Å	θ = 1.0–27.5°
b = 14.8920 (5) Å	µ = 1.69 mm⁻¹
c = 20.6790 (7) Å	T = 173 K
V = 3598.42 (18) Å³	Prism, dark red
Z = 8	0.10 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	2731 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.115
Graphite monochromator	θ_max = 27.5°, θ_min = 2.0°
π scans	h = −15→15
25644 measured reflections	k = −18→19
4130 independent reflections	l = −26→22

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.07P)²] where P = (F_o² + 2F_c²)/3
4130 reflections	(Δ/σ)_max = 0.002
199 parameters	Δρ_max = 1.13 e Å⁻³
0 restraints	Δρ_min = −1.84 e Å⁻³

Crystal data top

[Sn(CH₃)₂(C₁₃H₁₁N₄S)Cl]	V = 3598.42 (18) Å³
M_r = 439.53	Z = 8
Orthorhombic, Pbna	Mo Kα radiation
a = 11.6850 (2) Å	µ = 1.69 mm⁻¹
b = 14.8920 (5) Å	T = 173 K
c = 20.6790 (7) Å	0.10 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	2731 reflections with I > 2σ(I)
25644 measured reflections	R_int = 0.115
4130 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.137	H-atom parameters constrained
S = 1.09	Δρ_max = 1.13 e Å⁻³
4130 reflections	Δρ_min = −1.84 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Sn	0.18590 (3)	0.56103 (2)	0.509606 (17)	0.03083 (14)
Cl	0.03058 (11)	0.57242 (10)	0.59081 (6)	0.0489 (4)
S	0.30578 (10)	0.64147 (10)	0.58678 (6)	0.0440 (4)
N1	0.3690 (3)	0.5795 (2)	0.45454 (18)	0.0308 (9)
N2	0.4565 (3)	0.6110 (3)	0.48494 (17)	0.0325 (9)
N3	0.5342 (3)	0.6667 (2)	0.57432 (18)	0.0343 (9)
N4	0.5270 (3)	0.6917 (2)	0.63558 (19)	0.0364 (9)
H4N	0.4606	0.6889	0.6556	0.044*
C1	0.3037 (4)	0.5110 (3)	0.3553 (2)	0.0368 (11)
H1	0.2316	0.5011	0.3754	0.044*
C2	0.3220 (4)	0.4841 (3)	0.2918 (3)	0.0444 (13)
H2	0.2620	0.4559	0.2683	0.053*
C3	0.4263 (5)	0.4979 (3)	0.2626 (2)	0.0516 (14)
H3	0.4380	0.4797	0.2191	0.062*
C4	0.5137 (5)	0.5383 (4)	0.2966 (3)	0.0484 (14)
H4	0.5856	0.5474	0.2761	0.058*
C5	0.4985 (4)	0.5659 (3)	0.3598 (2)	0.0364 (11)
H5	0.5595	0.5934	0.3829	0.044*
C6	0.3923 (4)	0.5527 (3)	0.3896 (2)	0.0316 (10)
C7	0.6144 (4)	0.7333 (3)	0.7357 (2)	0.0423 (13)
H7	0.5451	0.7188	0.7573	0.051*
C8	0.7073 (5)	0.7652 (3)	0.7698 (3)	0.0474 (14)
H8	0.7011	0.7735	0.8152	0.057*
C9	0.8086 (4)	0.7852 (4)	0.7392 (3)	0.0503 (14)
H9	0.8718	0.8075	0.7633	0.060*
C10	0.8178 (4)	0.7729 (4)	0.6738 (3)	0.0518 (15)
H10	0.8884	0.7856	0.6529	0.062*
C11	0.7263 (5)	0.7424 (3)	0.6376 (3)	0.0425 (13)
H11	0.7330	0.7351	0.5921	0.051*
C12	0.6243 (4)	0.7226 (3)	0.6692 (2)	0.0342 (11)
C13	0.4384 (4)	0.6391 (3)	0.5470 (2)	0.0329 (10)
C14	0.2130 (5)	0.4204 (4)	0.5157 (3)	0.0438 (14)
H14A	0.1517	0.3890	0.4926	0.066*
H14B	0.2129	0.4019	0.5612	0.066*
H14C	0.2869	0.4053	0.4961	0.066*
C15	0.1051 (3)	0.6462 (3)	0.4410 (2)	0.0374 (11)
H15A	0.0860	0.6115	0.4022	0.056*
H15B	0.1572	0.6952	0.4293	0.056*
H15C	0.0350	0.6712	0.4598	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.0292 (2)	0.0351 (2)	0.0282 (2)	0.00016 (13)	−0.00196 (12)	0.00342 (13)
Cl	0.0390 (7)	0.0750 (10)	0.0326 (7)	0.0030 (6)	0.0051 (5)	0.0065 (6)
S	0.0344 (6)	0.0634 (9)	0.0342 (8)	0.0036 (6)	−0.0021 (5)	−0.0164 (6)
N1	0.033 (2)	0.029 (2)	0.031 (2)	−0.0025 (16)	−0.0031 (17)	0.0010 (16)
N2	0.035 (2)	0.030 (2)	0.032 (2)	−0.0017 (18)	−0.0044 (17)	−0.0016 (17)
N3	0.037 (2)	0.033 (2)	0.033 (2)	−0.0034 (16)	−0.0054 (17)	−0.0021 (18)
N4	0.039 (2)	0.037 (2)	0.034 (2)	0.0020 (18)	−0.0062 (17)	−0.0077 (18)
C1	0.044 (3)	0.035 (3)	0.032 (3)	0.002 (2)	−0.007 (2)	−0.001 (2)
C2	0.069 (4)	0.031 (3)	0.033 (3)	0.008 (3)	−0.017 (3)	−0.006 (2)
C3	0.082 (4)	0.042 (3)	0.031 (3)	0.013 (3)	0.000 (3)	−0.001 (2)
C4	0.066 (3)	0.043 (3)	0.036 (3)	0.011 (3)	0.018 (3)	0.006 (2)
C5	0.043 (3)	0.033 (3)	0.033 (3)	0.002 (2)	0.005 (2)	0.002 (2)
C6	0.040 (2)	0.027 (3)	0.028 (3)	0.0068 (19)	−0.002 (2)	0.0025 (19)
C7	0.045 (3)	0.046 (3)	0.036 (3)	0.012 (2)	−0.007 (2)	−0.009 (2)
C8	0.061 (3)	0.041 (3)	0.040 (3)	0.019 (2)	−0.021 (3)	−0.012 (2)
C9	0.050 (3)	0.041 (3)	0.060 (4)	−0.001 (3)	−0.024 (3)	−0.007 (3)
C10	0.048 (3)	0.048 (3)	0.060 (4)	−0.018 (2)	−0.013 (3)	0.006 (3)
C11	0.049 (3)	0.038 (3)	0.040 (3)	−0.007 (2)	−0.012 (2)	0.005 (2)
C12	0.037 (3)	0.025 (2)	0.040 (3)	0.004 (2)	−0.010 (2)	−0.004 (2)
C13	0.035 (2)	0.032 (3)	0.032 (3)	0.000 (2)	−0.004 (2)	−0.004 (2)
C14	0.042 (3)	0.037 (3)	0.052 (4)	0.003 (2)	−0.002 (2)	0.010 (2)
C15	0.036 (2)	0.038 (3)	0.038 (3)	0.000 (2)	−0.003 (2)	0.006 (2)

Geometric parameters (Å, º) top

Sn—C14	2.122 (5)	C4—H4	0.9500
Sn—C15	2.125 (5)	C5—C6	1.399 (6)
Sn—S	2.4380 (13)	C5—H5	0.9500
Sn—N1	2.439 (4)	C7—C8	1.379 (7)
Sn—Cl	2.4784 (13)	C7—C12	1.388 (7)
S—C13	1.755 (4)	C7—H7	0.9500
N1—N2	1.289 (5)	C8—C9	1.375 (8)
N1—C6	1.428 (6)	C8—H8	0.9500
N2—C13	1.366 (6)	C9—C10	1.370 (8)
N3—C13	1.320 (5)	C9—H9	0.9500
N3—N4	1.323 (5)	C10—C11	1.382 (7)
N4—C12	1.410 (6)	C10—H10	0.9500
N4—H4N	0.8800	C11—C12	1.392 (7)
C1—C2	1.390 (7)	C11—H11	0.9500
C1—C6	1.400 (6)	C14—H14A	0.9800
C1—H1	0.9500	C14—H14B	0.9800
C2—C3	1.375 (7)	C14—H14C	0.9800
C2—H2	0.9500	C15—H15A	0.9800
C3—C4	1.377 (7)	C15—H15B	0.9800
C3—H3	0.9500	C15—H15C	0.9800
C4—C5	1.383 (7)

C14—Sn—C15	134.0 (2)	C5—C6—N1	122.9 (4)
C14—Sn—S	111.14 (15)	C1—C6—N1	117.3 (4)
C15—Sn—S	113.52 (14)	C8—C7—C12	118.8 (5)
C14—Sn—N1	90.45 (17)	C8—C7—H7	120.6
C15—Sn—N1	90.60 (14)	C12—C7—H7	120.6
S—Sn—N1	75.30 (9)	C9—C8—C7	121.1 (5)
C14—Sn—Cl	97.86 (15)	C9—C8—H8	119.4
C15—Sn—Cl	94.95 (13)	C7—C8—H8	119.4
S—Sn—Cl	86.77 (4)	C10—C9—C8	119.5 (5)
N1—Sn—Cl	161.98 (9)	C10—C9—H9	120.2
C13—S—Sn	100.99 (16)	C8—C9—H9	120.2
N2—N1—C6	114.2 (4)	C9—C10—C11	121.3 (5)
N2—N1—Sn	120.6 (3)	C9—C10—H10	119.4
C6—N1—Sn	125.1 (3)	C11—C10—H10	119.4
N1—N2—C13	116.6 (4)	C10—C11—C12	118.5 (5)
C13—N3—N4	116.3 (4)	C10—C11—H11	120.7
N3—N4—C12	120.8 (4)	C12—C11—H11	120.7
N3—N4—H4N	119.6	C7—C12—C11	120.8 (4)
C12—N4—H4N	119.6	C7—C12—N4	117.3 (4)
C2—C1—C6	119.5 (4)	C11—C12—N4	121.9 (4)
C2—C1—H1	120.3	N3—C13—N2	111.5 (4)
C6—C1—H1	120.3	N3—C13—S	122.8 (4)
C3—C2—C1	120.5 (5)	N2—C13—S	125.7 (3)
C3—C2—H2	119.7	Sn—C14—H14A	109.5
C1—C2—H2	119.7	Sn—C14—H14B	109.5
C2—C3—C4	120.0 (5)	H14A—C14—H14B	109.5
C2—C3—H3	120.0	Sn—C14—H14C	109.5
C4—C3—H3	120.0	H14A—C14—H14C	109.5
C3—C4—C5	121.1 (5)	H14B—C14—H14C	109.5
C3—C4—H4	119.4	Sn—C15—H15A	109.5
C5—C4—H4	119.4	Sn—C15—H15B	109.5
C4—C5—C6	119.2 (5)	H15A—C15—H15B	109.5
C4—C5—H5	120.4	Sn—C15—H15C	109.5
C6—C5—H5	120.4	H15A—C15—H15C	109.5
C5—C6—C1	119.8 (4)	H15B—C15—H15C	109.5

C14—Sn—S—C13	77.8 (2)	C2—C1—C6—N1	179.6 (4)
C15—Sn—S—C13	−91.0 (2)	N2—N1—C6—C5	−4.7 (6)
N1—Sn—S—C13	−6.86 (18)	Sn—N1—C6—C5	179.1 (3)
Cl—Sn—S—C13	175.02 (17)	N2—N1—C6—C1	174.9 (4)
C14—Sn—N1—N2	−104.0 (3)	Sn—N1—C6—C1	−1.3 (5)
C15—Sn—N1—N2	121.9 (3)	C12—C7—C8—C9	−0.8 (7)
S—Sn—N1—N2	7.7 (3)	C7—C8—C9—C10	−0.3 (8)
Cl—Sn—N1—N2	13.8 (5)	C8—C9—C10—C11	1.3 (9)
C14—Sn—N1—C6	71.9 (3)	C9—C10—C11—C12	−1.2 (8)
C15—Sn—N1—C6	−62.1 (3)	C8—C7—C12—C11	1.0 (7)
S—Sn—N1—C6	−176.3 (3)	C8—C7—C12—N4	−178.6 (4)
Cl—Sn—N1—C6	−170.2 (2)	C10—C11—C12—C7	0.0 (7)
C6—N1—N2—C13	179.0 (4)	C10—C11—C12—N4	179.6 (5)
Sn—N1—N2—C13	−4.6 (5)	N3—N4—C12—C7	−169.6 (4)
C13—N3—N4—C12	−179.8 (4)	N3—N4—C12—C11	10.9 (7)
C6—C1—C2—C3	0.2 (7)	N4—N3—C13—N2	−177.1 (4)
C1—C2—C3—C4	0.3 (8)	N4—N3—C13—S	4.1 (6)
C2—C3—C4—C5	−0.3 (8)	N1—N2—C13—N3	177.5 (4)
C3—C4—C5—C6	−0.3 (7)	N1—N2—C13—S	−3.8 (6)
C4—C5—C6—C1	0.8 (7)	Sn—S—C13—N3	−172.3 (4)
C4—C5—C6—N1	−179.6 (4)	Sn—S—C13—N2	9.1 (4)
C2—C1—C6—C5	−0.8 (7)

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₂(C₁₃H₁₁N₄S)Cl]
M_r	439.53
Crystal system, space group	Orthorhombic, Pbna
Temperature (K)	173
a, b, c (Å)	11.6850 (2), 14.8920 (5), 20.6790 (7)
V (Å³)	3598.42 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.69
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	25644, 4130, 2731
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.137, 1.09
No. of reflections	4130
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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