Bis[4-(dimethyl­amino)pyridinium] tribromidochloridodimethyl­stannate(IV)

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536808014669

metal-organic compounds

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Volume 64| Part 6| June 2008| Page m834

doi:10.1107/S1600536808014669

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Bis[4-(dimethylamino)pyridinium] tribromidochloridodimethylstannate(IV)

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 14 May 2008; accepted 15 May 2008; online 21 May 2008)

The Sn^IV atom in the title salt, (C₇H₁₁N₂)₂[SnBr₃(CH₃)₂Cl], lies on a center of inversion in a tetragonally compressed octahedron; two independent Br atoms share the same site as two independent chlorine atoms so that the anion effectively has one Cl and three Br atoms. The occupancies of the Br atoms are 0.721 (1) and 0.779 (1), and those of the Cl atoms are 0.279 (1) and 0.221 (1). The crystal structure involves N—H⋯halogen hydrogen bonds.

Related literature

For the isostructural bis(4-dimethylaminopyridinium) dibromidodichlorodimethylstannate(IV), see: Lo & Ng (2008 ).

Experimental

Crystal data

(C₇H₁₁N₂)₂[SnBr₃(CH₃)₂Cl]
M_r = 670.29
Triclinic, $[P \overline 1]$
a = 7.3692 (2) Å
b = 8.6303 (1) Å
c = 9.5686 (2) Å
α = 96.902 (1)°
β = 106.546 (1)°
γ = 91.628 (1)°
V = 577.87 (2) Å³
Z = 1
Mo Kα radiation
μ = 6.42 mm⁻¹
T = 100 (2) K
0.35 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.212, T_max = 0.566 (expected range = 0.197–0.527)
7041 measured reflections
2623 independent reflections
2344 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.061
S = 1.07
2623 reflections
122 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Sn1—C1	2.131 (3)
Sn1—Br1	2.7240 (3)
Sn1—Br2	2.7234 (3)

C1—Sn1—Br1	89.74 (7)
C1—Sn1—Br1ⁱ	90.26 (7)
Br1—Sn1—Br2	88.54 (1)
Br1—Sn1—Br2ⁱ	91.47 (1)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯X1	0.88	2.61	3.325 (2)	139
N1—H1⋯X2	0.88	2.83	3.475 (2)	132
Symmetry codes: .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808014669/sj2501sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808014669/sj2501Isup2.hkl

checkCIF report

Comment top

We have been investigating the reaction of organotin compounds with 4-dimethylpyridinium hydrobromide perbromide. In the previous study, this compound was reacted with dimethyltin dichloride to afford bis(4-dimethylpyridinium) dibromidodichloridodimethylstannate (Lo & Ng, 2008), whose. The halogens are in the expected 2:2 molar ratio. The bromine atoms are disordered with respect to the chlorine atoms. In the present study, the organotin reactant, chlorodimethyltin dimethyldithiocarbamate contains only one chlorine atom. The resulting stannate (Scheme I, Fig. 1) is the expected tribromidochloridodimethylstannate; the two salts are isostructural. N1—H1···X hydrogen bonds (X is a disordered mixture of Cl and Br; symmetry code: x, y, z) link the anions and cations, Fig 1, Table 2.

Related literature top

For the isostructural bis(4-dimethylaminopyridinium) dibromidodichlorodimethylstannate(IV), see: Lo & Ng (2008).

Experimental top

Chlorodimethyltin dimethyldithiocarbamate (1.54 g, 0.005 mol) and 4-dimethylpyridinium hydrobromide perbromide (1.81 g, 0.005 mol) were dissolved in a mixture of ethanol and chloroform (1:1) and the resulting mixture was refluxed for 15 minutes. Colorless crystals separated from the cool solution after several days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 2008).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of [C₇H₁₁N₂]₂ [SnBr₃Cl₂(CH₃)₂] at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The Sn atom lies on a center-of-inversion such that the two independent Br atoms are disordered with respect to the two independent Cl atoms. Symmetry code: i = 1 – x, 1 – y, 1 – z. Dashed lines denote hydrogen bonds.

Bis[4-(dimethylamino)pyridinium] tribromidochloridodimethylstannate(IV) top

Crystal data top

(C₇H₁₁N₂)₂[SnBr₃(CH₃)₂Cl]	Z = 1
M_r = 670.29	F(000) = 324
Triclinic, P1	D_x = 1.926 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3692 (2) Å	Cell parameters from 3862 reflections
b = 8.6303 (1) Å	θ = 2.4–28.3°
c = 9.5686 (2) Å	µ = 6.42 mm⁻¹
α = 96.902 (1)°	T = 100 K
β = 106.546 (1)°	Prism, colorless
γ = 91.628 (1)°	0.35 × 0.15 × 0.10 mm
V = 577.87 (2) Å³

Data collection top

Bruker SMART APEX diffractometer	2623 independent reflections
Radiation source: fine-focus sealed tube	2344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.212, T_max = 0.566	k = −11→11
7041 measured reflections	l = −12→12

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0363P)²] where P = (F_o² + 2F_c²)/3
2623 reflections	(Δ/σ)_max = 0.001
122 parameters	Δρ_max = 0.89 e Å⁻³
4 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[SnBr₃(CH₃)₂Cl]	γ = 91.628 (1)°
M_r = 670.29	V = 577.87 (2) Å³
Triclinic, P1	Z = 1
a = 7.3692 (2) Å	Mo Kα radiation
b = 8.6303 (1) Å	µ = 6.42 mm⁻¹
c = 9.5686 (2) Å	T = 100 K
α = 96.902 (1)°	0.35 × 0.15 × 0.10 mm
β = 106.546 (1)°

Data collection top

Bruker SMART APEX diffractometer	2623 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2344 reflections with I > 2σ(I)
T_min = 0.212, T_max = 0.566	R_int = 0.022
7041 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	4 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.07	Δρ_max = 0.89 e Å⁻³
2623 reflections	Δρ_min = −0.63 e Å⁻³
122 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sn1	0.5000	0.5000	0.5000	0.01608 (8)
Br1	0.50013 (5)	0.49555 (4)	0.78420 (3)	0.02259 (11)	0.7207 (11)
Br2	0.64681 (5)	0.21397 (3)	0.50475 (3)	0.02106 (10)	0.7793 (11)
Cl1	0.50013 (5)	0.49555 (4)	0.78420 (3)	0.02259 (11)	0.2793 (11)
Cl2	0.64681 (5)	0.21397 (3)	0.50475 (3)	0.02106 (10)	0.2207 (11)
N1	0.6543 (3)	0.1474 (3)	0.8573 (2)	0.0201 (5)
H1	0.6158	0.2122	0.7921	0.024*
N2	0.8485 (3)	−0.1517 (3)	1.1630 (2)	0.0221 (5)
C1	0.2173 (4)	0.3966 (3)	0.4268 (3)	0.0218 (6)
H1A	0.1467	0.4384	0.4941	0.033*
H1B	0.2201	0.2829	0.4250	0.033*
H1C	0.1550	0.4209	0.3276	0.033*
C2	0.6702 (4)	0.1943 (3)	1.0009 (3)	0.0228 (6)
H2	0.6368	0.2962	1.0297	0.027*
C3	0.7329 (4)	0.0981 (3)	1.1038 (3)	0.0207 (5)
H3	0.7430	0.1331	1.2039	0.025*
C4	0.7837 (4)	−0.0549 (3)	1.0634 (3)	0.0169 (5)
C5	0.7598 (4)	−0.0989 (3)	0.9112 (3)	0.0191 (5)
H5	0.7883	−0.2008	0.8774	0.023*
C6	0.6970 (4)	0.0029 (3)	0.8136 (3)	0.0215 (6)
H6	0.6828	−0.0286	0.7123	0.026*
C7	0.8693 (5)	−0.1024 (4)	1.3185 (3)	0.0307 (7)
H7A	0.9483	−0.0041	1.3512	0.046*
H7B	0.9297	−0.1832	1.3764	0.046*
H7C	0.7440	−0.0869	1.3323	0.046*
C8	0.9004 (4)	−0.3085 (3)	1.1218 (3)	0.0282 (6)
H8A	0.9901	−0.3028	1.0639	0.042*
H8B	0.7864	−0.3730	1.0631	0.042*
H8C	0.9597	−0.3554	1.2108	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01588 (14)	0.01489 (13)	0.01660 (13)	0.00076 (9)	0.00352 (10)	0.00175 (9)
Br1	0.0347 (2)	0.01817 (17)	0.01694 (16)	0.00364 (13)	0.01007 (14)	0.00342 (12)
Br2	0.02735 (19)	0.01599 (15)	0.01872 (16)	0.00594 (12)	0.00403 (13)	0.00333 (11)
Cl1	0.0347 (2)	0.01817 (17)	0.01694 (16)	0.00364 (13)	0.01007 (14)	0.00342 (12)
Cl2	0.02735 (19)	0.01599 (15)	0.01872 (16)	0.00594 (12)	0.00403 (13)	0.00333 (11)
N1	0.0196 (12)	0.0193 (11)	0.0212 (11)	0.0008 (9)	0.0039 (9)	0.0067 (9)
N2	0.0207 (13)	0.0257 (12)	0.0189 (11)	0.0001 (10)	0.0034 (9)	0.0049 (9)
C1	0.0208 (14)	0.0214 (13)	0.0237 (13)	0.0021 (11)	0.0068 (11)	0.0044 (11)
C2	0.0200 (14)	0.0206 (13)	0.0273 (14)	0.0007 (11)	0.0074 (12)	−0.0001 (11)
C3	0.0172 (14)	0.0259 (14)	0.0184 (12)	−0.0033 (11)	0.0060 (11)	−0.0008 (10)
C4	0.0112 (12)	0.0215 (13)	0.0183 (12)	−0.0013 (10)	0.0036 (10)	0.0055 (10)
C5	0.0176 (14)	0.0169 (12)	0.0214 (13)	−0.0027 (10)	0.0044 (11)	0.0010 (10)
C6	0.0204 (15)	0.0257 (14)	0.0182 (12)	−0.0034 (11)	0.0063 (11)	0.0010 (10)
C7	0.0287 (17)	0.0428 (18)	0.0203 (13)	0.0058 (14)	0.0037 (12)	0.0110 (13)
C8	0.0267 (16)	0.0253 (15)	0.0320 (15)	0.0027 (12)	0.0053 (13)	0.0095 (12)

Geometric parameters (Å, º) top

Sn1—C1	2.131 (3)	C1—H1A	0.9800
Sn1—Br1	2.7240 (3)	C1—H1B	0.9800
Sn1—Br2	2.7234 (3)	C1—H1C	0.9800
N1—C6	1.342 (3)	C2—H2	0.9500
N1—C2	1.356 (3)	C3—H3	0.9500
N2—C4	1.338 (3)	C5—H5	0.9500
N2—C8	1.456 (4)	C6—H6	0.9500
N2—C7	1.460 (3)	C7—H7A	0.9800
C2—C3	1.354 (4)	C7—H7B	0.9800
C3—C4	1.421 (4)	C7—H7C	0.9800
C4—C5	1.419 (3)	C8—H8A	0.9800
C5—C6	1.353 (4)	C8—H8B	0.9800
N1—H1	0.8800	C8—H8C	0.9800

C1—Sn1—C1ⁱ	180.0	Sn1—C1—H1C	109.5
C1—Sn1—Br1	89.74 (7)	H1A—C1—H1C	109.5
C1—Sn1—Br1ⁱ	90.26 (7)	H1B—C1—H1C	109.5
Br1—Sn1—Br1ⁱ	180.0	C3—C2—H2	119.5
Br1—Sn1—Br2	88.54 (1)	N1—C2—H2	119.5
Br1—Sn1—Br2ⁱ	91.47 (1)	C2—C3—H3	119.7
Br2—Sn1—Br2ⁱ	180.0	C4—C3—H3	119.7
C6—N1—C2	120.5 (2)	C6—C5—H5	119.7
C4—N2—C8	121.9 (2)	C4—C5—H5	119.7
C4—N2—C7	120.5 (2)	N1—C6—H6	119.4
C8—N2—C7	117.6 (2)	C5—C6—H6	119.4
C3—C2—N1	120.9 (2)	N2—C7—H7A	109.5
C2—C3—C4	120.6 (2)	N2—C7—H7B	109.5
N2—C4—C5	122.2 (2)	H7A—C7—H7B	109.5
N2—C4—C3	121.8 (2)	N2—C7—H7C	109.5
C5—C4—C3	116.0 (2)	H7A—C7—H7C	109.5
C6—C5—C4	120.6 (2)	H7B—C7—H7C	109.5
N1—C6—C5	121.3 (2)	N2—C8—H8A	109.5
C6—N1—H1	119.7	N2—C8—H8B	109.5
C2—N1—H1	119.7	H8A—C8—H8B	109.5
Sn1—C1—H1A	109.5	N2—C8—H8C	109.5
Sn1—C1—H1B	109.5	H8A—C8—H8C	109.5
H1A—C1—H1B	109.5	H8B—C8—H8C	109.5

C6—N1—C2—C3	1.4 (4)	C2—C3—C4—N2	179.1 (3)
N1—C2—C3—C4	0.0 (4)	C2—C3—C4—C5	−1.5 (4)
C8—N2—C4—C5	0.5 (4)	N2—C4—C5—C6	−178.8 (3)
C7—N2—C4—C5	−179.4 (3)	C3—C4—C5—C6	1.7 (4)
C8—N2—C4—C3	179.9 (2)	C2—N1—C6—C5	−1.2 (4)
C7—N2—C4—C3	0.0 (4)	C4—C5—C6—N1	−0.4 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···X1	0.88	2.61	3.325 (2)	139
N1—H1···X2	0.88	2.83	3.475 (2)	132

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[SnBr₃(CH₃)₂Cl]
M_r	670.29
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.3692 (2), 8.6303 (1), 9.5686 (2)
α, β, γ (°)	96.902 (1), 106.546 (1), 91.628 (1)
V (Å³)	577.87 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	6.42
Crystal size (mm)	0.35 × 0.15 × 0.10

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.212, 0.566
No. of measured, independent and observed [I > 2σ(I)] reflections	7041, 2623, 2344
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.061, 1.07
No. of reflections	2623
No. of parameters	122
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.63

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Selected geometric parameters (Å, º) top

Sn1—C1	2.131 (3)	Sn1—Br2	2.7234 (3)
Sn1—Br1	2.7240 (3)

C1—Sn1—Br1	89.74 (7)	Br1—Sn1—Br2	88.54 (1)
C1—Sn1—Br1ⁱ	90.26 (7)	Br1—Sn1—Br2ⁱ	91.47 (1)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···X1	0.88	2.61	3.325 (2)	139
N1—H1···X2	0.88	2.83	3.475 (2)	132

Acknowledgements

We thank the University of Malaya for funding this study (SF022155/2007 A) and also for the purchase of the diffractometer.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m800. Web of Science CSD CrossRef IUCr Journals 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
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar