Di-tert-butyl­bis(N-isopropyl-N-methyl­dithio­carbamato-κ2S,S′)tin(IV)

Muthalib, A.F.; Baba, I.; Samsudin, M.W.; Ng, S.W.

doi:10.1107/S1600536810007439

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page m356

doi:10.1107/S1600536810007439

Open

access

Di-tert-butylbis(N-isopropyl-N-methyldithiocarbamato-κ²S,S′)tin(IV)

Amirah Faizah Muthalib,^a Ibrahim Baba,^a Mohd Wahid Samsudin ^a and Seik Weng Ng ^b ^*

^aSchool of Chemical Sciences, Universiti Kebangbaan Malaysia, 43600 Bangi, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 21 February 2010; accepted 26 February 2010; online 3 March 2010)

The dithiocarbamate anions in the title compound, [Sn(C₄H₉)₂(C₅H₁₀NS₂)₂], chelate to the Sn^IV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The molecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1).

Related literature

For the crystal structure of di(tert-butyl)bis(N,N-dimethyldithiocarbamato)tin(IV), see: Kim et al. (1987 ). For a discussion of the geometry of tin in diorganotin bischelates, see: Ng et al. (1987 ). For the treatment of non-merohedral twinning, see: Spek (2009 ).

Experimental

Crystal data

[Sn(C₄H₉)₂(C₅H₁₀NS₂)₂]
M_r = 529.43
Monoclinic, P 2/n
a = 11.2934 (11) Å
b = 7.0175 (7) Å
c = 15.6894 (15) Å
β = 95.016 (1)°
V = 1238.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.37 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.610, T_max = 0.875
7346 measured reflections
2838 independent reflections
2199 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.186
S = 1.09
2838 reflections
121 parameters
H-atom parameters constrained
Δρ_max = 1.76 e Å⁻³
Δρ_min = −1.58 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Sn1—C1	2.233 (7)
Sn1—S1	2.5444 (18)
Sn1—S2	2.9911 (17)

C1ⁱ—Sn1—C1	142.5 (4)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007439/ci5041sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007439/ci5041Isup2.hkl

checkCIF report

Related literature top

For the crystal structure of di(tert-butyl)bis(N,N-dimethyldithiocarbamato)tin(IV), see: Kim et al. (1987). For a discussion of the geometry of tin in diorganotin bischelates, see: Ng et al. (1987). For the treatment of non-merohedral twinning, see: Spek (2009).

Experimental top

Di-t-butyltin dichloride (10 mmol), isopropylmethylamine (10 mmol) and carbon disulfide (10 mmol) were reacted in ethanol (50 ml) at 277 K to produce a white solid. The mixture was stirred for 1 h. The solid was collected and recrystallized from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of [Sn(C₆H₅)₂(C₅H₁₁NS₂)₂] at 50% probability level. H atoms are drawn as spheres of arbitrary radii. Unlabelled atoms are related to labelled atoms by the symmetry operation (3/2 - x, y, 3/2 - z).

Di-tert-butylbis(N-isopropyl-N-methyldithiocarbamato- κ²S,S')tin(IV) top

Crystal data top

[Sn(C₄H₉)₂(C₅H₁₀NS₂)₂]	F(000) = 548
M_r = 529.43	D_x = 1.420 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 4020 reflections
a = 11.2934 (11) Å	θ = 2.6–28.1°
b = 7.0175 (7) Å	µ = 1.37 mm⁻¹
c = 15.6894 (15) Å	T = 293 K
β = 95.016 (1)°	Block, colourless
V = 1238.6 (2) Å³	0.40 × 0.20 × 0.10 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	2838 independent reflections
Radiation source: fine-focus sealed tube	2199 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.610, T_max = 0.875	k = −8→9
7346 measured reflections	l = −11→20

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0968P)² + 1.7978P] where P = (F_o² + 2F_c²)/3
2838 reflections	(Δ/σ)_max = 0.001
121 parameters	Δρ_max = 1.76 e Å⁻³
0 restraints	Δρ_min = −1.58 e Å⁻³

Crystal data top

[Sn(C₄H₉)₂(C₅H₁₀NS₂)₂]	V = 1238.6 (2) Å³
M_r = 529.43	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 11.2934 (11) Å	µ = 1.37 mm⁻¹
b = 7.0175 (7) Å	T = 293 K
c = 15.6894 (15) Å	0.40 × 0.20 × 0.10 mm
β = 95.016 (1)°

Data collection top

Bruker SMART APEX diffractometer	2838 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2199 reflections with I > 2σ(I)
T_min = 0.610, T_max = 0.875	R_int = 0.065
7346 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.09	Δρ_max = 1.76 e Å⁻³
2838 reflections	Δρ_min = −1.58 e Å⁻³
121 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.7500	0.42189 (9)	0.7500	0.0369 (2)
S1	0.77107 (19)	0.1454 (3)	0.64749 (11)	0.0514 (5)
S2	0.82366 (17)	0.5223 (3)	0.57705 (11)	0.0469 (4)
N1	0.8073 (5)	0.2052 (8)	0.4857 (3)	0.0402 (12)
C1	0.5675 (6)	0.5241 (11)	0.7062 (4)	0.0426 (15)
C2	0.4811 (7)	0.3967 (12)	0.7504 (5)	0.059 (2)
H2A	0.4021	0.4474	0.7409	0.089*
H2B	0.5043	0.3925	0.8107	0.089*
H2C	0.4828	0.2702	0.7271	0.089*
C3	0.5406 (8)	0.5079 (17)	0.6112 (5)	0.070 (2)
H3A	0.4581	0.5351	0.5963	0.105*
H3B	0.5580	0.3809	0.5932	0.105*
H3C	0.5886	0.5972	0.5831	0.105*
C4	0.5556 (7)	0.7310 (12)	0.7355 (6)	0.060 (2)
H4A	0.4789	0.7793	0.7148	0.090*
H4B	0.6164	0.8071	0.7131	0.090*
H4C	0.5642	0.7362	0.7968	0.090*
C5	0.8030 (5)	0.2889 (9)	0.5620 (4)	0.0373 (13)
C6	0.8255 (8)	0.3238 (13)	0.4121 (5)	0.059 (2)
H6A	0.7772	0.4361	0.4134	0.089*
H6B	0.8038	0.2539	0.3605	0.089*
H6C	0.9077	0.3598	0.4138	0.089*
C7	0.7887 (7)	0.0018 (11)	0.4715 (5)	0.0501 (17)
H7A	0.8045	−0.0620	0.5269	0.060*
C8	0.6609 (11)	−0.0364 (16)	0.4406 (10)	0.102 (4)
H8A	0.6102	0.0090	0.4822	0.153*
H8B	0.6494	−0.1710	0.4325	0.153*
H8C	0.6418	0.0283	0.3872	0.153*
C9	0.8748 (12)	−0.0792 (14)	0.4117 (7)	0.097 (4)
H9A	0.9505	−0.0174	0.4222	0.145*
H9B	0.8442	−0.0579	0.3534	0.145*
H9C	0.8841	−0.2136	0.4216	0.145*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0481 (4)	0.0382 (4)	0.0266 (3)	0.000	0.0163 (2)	0.000
S1	0.0883 (13)	0.0388 (9)	0.0311 (8)	−0.0034 (9)	0.0284 (8)	0.0010 (7)
S2	0.0678 (11)	0.0352 (9)	0.0400 (9)	−0.0041 (8)	0.0169 (8)	0.0007 (7)
N1	0.053 (3)	0.040 (3)	0.029 (3)	0.000 (2)	0.017 (2)	−0.001 (2)
C1	0.041 (3)	0.051 (4)	0.038 (3)	−0.004 (3)	0.010 (3)	0.004 (3)
C2	0.053 (4)	0.076 (6)	0.051 (4)	−0.014 (4)	0.015 (3)	0.001 (4)
C3	0.059 (5)	0.110 (8)	0.041 (4)	0.007 (5)	0.003 (4)	0.000 (5)
C4	0.064 (5)	0.052 (5)	0.064 (5)	0.009 (4)	0.005 (4)	0.004 (4)
C5	0.046 (3)	0.038 (3)	0.030 (3)	0.004 (3)	0.015 (2)	0.005 (3)
C6	0.087 (5)	0.060 (5)	0.033 (3)	−0.007 (4)	0.020 (4)	0.006 (3)
C7	0.080 (5)	0.037 (4)	0.035 (3)	−0.001 (4)	0.014 (3)	−0.003 (3)
C8	0.095 (8)	0.071 (7)	0.134 (12)	−0.026 (6)	−0.018 (8)	−0.007 (7)
C9	0.159 (12)	0.064 (7)	0.075 (7)	0.013 (6)	0.062 (7)	−0.014 (5)

Geometric parameters (Å, º) top

Sn1—C1ⁱ	2.233 (7)	C3—H3B	0.96
Sn1—C1	2.233 (7)	C3—H3C	0.96
Sn1—S1	2.5444 (18)	C4—H4A	0.96
Sn1—S1ⁱ	2.5444 (18)	C4—H4B	0.96
Sn1—S2ⁱ	2.9911 (17)	C4—H4C	0.96
Sn1—S2	2.9911 (17)	C6—H6A	0.96
S1—C5	1.739 (6)	C6—H6B	0.96
S2—C5	1.669 (7)	C6—H6C	0.96
N1—C5	1.338 (8)	C7—C8	1.506 (13)
N1—C6	1.453 (9)	C7—C9	1.520 (12)
N1—C7	1.457 (10)	C7—H7A	0.98
C1—C3	1.500 (10)	C8—H8A	0.96
C1—C2	1.533 (10)	C8—H8B	0.96
C1—C4	1.532 (11)	C8—H8C	0.96
C2—H2A	0.96	C9—H9A	0.96
C2—H2B	0.96	C9—H9B	0.96
C2—H2C	0.96	C9—H9C	0.96
C3—H3A	0.96

C1ⁱ—Sn1—C1	142.5 (4)	H3A—C3—H3C	109.5
C1ⁱ—Sn1—S1	107.74 (18)	H3B—C3—H3C	109.5
C1—Sn1—S1	100.7 (2)	C1—C4—H4A	109.5
C1ⁱ—Sn1—S1ⁱ	100.7 (2)	C1—C4—H4B	109.5
C1—Sn1—S1ⁱ	107.74 (19)	H4A—C4—H4B	109.5
S1—Sn1—S1ⁱ	80.64 (8)	C1—C4—H4C	109.5
S1—Sn1—S2	63.73 (6)	H4A—C4—H4C	109.5
S1—Sn1—S2ⁱ	143.31 (6)	H4B—C4—H4C	109.5
C1—Sn1—S2	88.14 (17)	N1—C5—S2	122.8 (5)
C1ⁱ—Sn1—S2ⁱ	88.14 (17)	N1—C5—S1	117.5 (5)
S1ⁱ—Sn1—S2	143.31 (6)	S2—C5—S1	119.7 (4)
S2ⁱ—Sn1—S2	152.75 (6)	N1—C6—H6A	109.5
C1—Sn1—S2ⁱ	83.17 (17)	N1—C6—H6B	109.5
C1ⁱ—Sn1—S2	83.17 (17)	H6A—C6—H6B	109.5
S1ⁱ—Sn1—S2ⁱ	63.73 (6)	N1—C6—H6C	109.5
C5—S1—Sn1	94.8 (2)	H6A—C6—H6C	109.5
C5—N1—C6	118.6 (6)	H6B—C6—H6C	109.5
C5—N1—C7	123.4 (5)	N1—C7—C8	110.2 (7)
C6—N1—C7	117.9 (6)	N1—C7—C9	111.7 (7)
C3—C1—C2	108.9 (7)	C8—C7—C9	112.4 (9)
C3—C1—C4	110.8 (7)	N1—C7—H7A	107.4
C2—C1—C4	110.0 (6)	C8—C7—H7A	107.4
C3—C1—Sn1	112.5 (5)	C9—C7—H7A	107.4
C2—C1—Sn1	106.3 (5)	C7—C8—H8A	109.5
C4—C1—Sn1	108.3 (5)	C7—C8—H8B	109.5
C1—C2—H2A	109.5	H8A—C8—H8B	109.5
C1—C2—H2B	109.5	C7—C8—H8C	109.5
H2A—C2—H2B	109.5	H8A—C8—H8C	109.5
C1—C2—H2C	109.5	H8B—C8—H8C	109.5
H2A—C2—H2C	109.5	C7—C9—H9A	109.5
H2B—C2—H2C	109.5	C7—C9—H9B	109.5
C1—C3—H3A	109.5	H9A—C9—H9B	109.5
C1—C3—H3B	109.5	C7—C9—H9C	109.5
H3A—C3—H3B	109.5	H9A—C9—H9C	109.5
C1—C3—H3C	109.5	H9B—C9—H9C	109.5

C1ⁱ—Sn1—S1—C5	−76.5 (3)	S1ⁱ—Sn1—C1—C4	117.8 (5)
C1—Sn1—S1—C5	78.8 (3)	C6—N1—C5—S2	−2.8 (9)
S1ⁱ—Sn1—S1—C5	−174.8 (2)	C7—N1—C5—S2	−179.6 (5)
C1ⁱ—Sn1—C1—C3	103.1 (6)	C6—N1—C5—S1	175.8 (5)
S1—Sn1—C1—C3	−35.9 (6)	C7—N1—C5—S1	−1.0 (8)
S1ⁱ—Sn1—C1—C3	−119.4 (6)	Sn1—S1—C5—N1	−171.6 (5)
C1ⁱ—Sn1—C1—C2	−137.8 (5)	Sn1—S1—C5—S2	7.0 (4)
S1—Sn1—C1—C2	83.1 (5)	C5—N1—C7—C8	95.0 (9)
S1ⁱ—Sn1—C1—C2	−0.3 (5)	C6—N1—C7—C8	−81.9 (9)
C1ⁱ—Sn1—C1—C4	−19.7 (4)	C5—N1—C7—C9	−139.4 (8)
S1—Sn1—C1—C4	−158.7 (5)	C6—N1—C7—C9	43.8 (10)

Symmetry code: (i) −x+3/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Sn(C₄H₉)₂(C₅H₁₀NS₂)₂]
M_r	529.43
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	293
a, b, c (Å)	11.2934 (11), 7.0175 (7), 15.6894 (15)
β (°)	95.016 (1)
V (Å³)	1238.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.37
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.610, 0.875
No. of measured, independent and observed [I > 2σ(I)] reflections	7346, 2838, 2199
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.186, 1.09
No. of reflections	2838
No. of parameters	121
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.76, −1.58

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top

Sn1—C1	2.233 (7)	Sn1—S2	2.9911 (17)
Sn1—S1	2.5444 (18)

C1ⁱ—Sn1—C1	142.5 (4)

Symmetry code: (i) −x+3/2, y, −z+3/2.

Acknowledgements

The authors thank Universiti Kebangsaan Malaysia (UKM-GUP-NBT-08-27-111 and 06-01-02-SF0539) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kim, K., Ibers, J. A., Jung, O.-S. & Sohn, Y. S. (1987). Acta Cryst. C43, 2317–2319. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ng, S. W., Chen, W., Kumar Das, V. G. & Mak, T. C. W. (1987). J. Organomet. Chem. 334, 295–305. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar