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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m834.
Published online 2008 May 21. doi:  10.1107/S1600536808014669
PMCID: PMC2961353

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

Abstract

The SnIV 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 [triangle]).

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Object name is e-64-0m834-scheme1.jpg

Experimental

Crystal data

  • (C7H11N2)2[SnBr3(CH3)2Cl]
  • M r = 670.29
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m834-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.061
  • S = 1.07
  • 2623 reflections
  • 122 parameters
  • 4 restraints
  • H-atom parameters constrained
  • Δρmax = 0.89 e Å−3
  • Δρmin = −0.63 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5Ueq(C). The ammonium H atom was similarly treated (N–H 0.88 Å).

The two indepedent chlorine atoms are disordered with respect to the bromine atoms, so that each halogen site is occupied by both a chlorine and a bromine. Restraints were applied so that at each site; the atoms were restrained to have the same anisotropic temperature factors. Without occupancy restraints, occupancies of the chlorine atoms refined to nearly 0.5 and the total number of bromine atoms to approximately 1.5. The sum of the occupancies were then restrained to these values and, in the final refinement, occupancies refined to Br1 0.721 (1), Br2 0.779 (1), Cl1 0.279 (1) and Cl2 0.221 (1). The final difference Fourier map was featureless.

Figures

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 ...

Crystal data

(C7H11N2)2[SnBr3(CH3)2Cl]Z = 1
Mr = 670.29F000 = 324
Triclinic, P1Dx = 1.926 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.3692 (2) ÅCell parameters from 3862 reflections
b = 8.6303 (1) Åθ = 2.4–28.3º
c = 9.5686 (2) ŵ = 6.42 mm1
α = 96.902 (1)ºT = 100 (2) K
β = 106.546 (1)ºPrism, colorless
γ = 91.628 (1)º0.35 × 0.15 × 0.10 mm
V = 577.87 (2) Å3

Data collection

Bruker SMART APEX diffractometer2623 independent reflections
Radiation source: fine-focus sealed tube2344 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.022
T = 100(2) Kθmax = 27.5º
ω scansθmin = 2.2º
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)h = −9→8
Tmin = 0.212, Tmax = 0.566k = −11→11
7041 measured reflectionsl = −12→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.061  w = 1/[σ2(Fo2) + (0.0363P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2623 reflectionsΔρmax = 0.89 e Å3
122 parametersΔρmin = −0.63 e Å3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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

xyzUiso*/UeqOcc. (<1)
Sn10.50000.50000.50000.01608 (8)
Br10.50013 (5)0.49555 (4)0.78420 (3)0.02259 (11)0.7207 (11)
Br20.64681 (5)0.21397 (3)0.50475 (3)0.02106 (10)0.7793 (11)
Cl10.50013 (5)0.49555 (4)0.78420 (3)0.02259 (11)0.2793 (11)
Cl20.64681 (5)0.21397 (3)0.50475 (3)0.02106 (10)0.2207 (11)
N10.6543 (3)0.1474 (3)0.8573 (2)0.0201 (5)
H10.61580.21220.79210.024*
N20.8485 (3)−0.1517 (3)1.1630 (2)0.0221 (5)
C10.2173 (4)0.3966 (3)0.4268 (3)0.0218 (6)
H1A0.14670.43840.49410.033*
H1B0.22010.28290.42500.033*
H1C0.15500.42090.32760.033*
C20.6702 (4)0.1943 (3)1.0009 (3)0.0228 (6)
H20.63680.29621.02970.027*
C30.7329 (4)0.0981 (3)1.1038 (3)0.0207 (5)
H30.74300.13311.20390.025*
C40.7837 (4)−0.0549 (3)1.0634 (3)0.0169 (5)
C50.7598 (4)−0.0989 (3)0.9112 (3)0.0191 (5)
H50.7883−0.20080.87740.023*
C60.6970 (4)0.0029 (3)0.8136 (3)0.0215 (6)
H60.6828−0.02860.71230.026*
C70.8693 (5)−0.1024 (4)1.3185 (3)0.0307 (7)
H7A0.9483−0.00411.35120.046*
H7B0.9297−0.18321.37640.046*
H7C0.7440−0.08691.33230.046*
C80.9004 (4)−0.3085 (3)1.1218 (3)0.0282 (6)
H8A0.9901−0.30281.06390.042*
H8B0.7864−0.37301.06310.042*
H8C0.9597−0.35541.21080.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn10.01588 (14)0.01489 (13)0.01660 (13)0.00076 (9)0.00352 (10)0.00175 (9)
Br10.0347 (2)0.01817 (17)0.01694 (16)0.00364 (13)0.01007 (14)0.00342 (12)
Br20.02735 (19)0.01599 (15)0.01872 (16)0.00594 (12)0.00403 (13)0.00333 (11)
Cl10.0347 (2)0.01817 (17)0.01694 (16)0.00364 (13)0.01007 (14)0.00342 (12)
Cl20.02735 (19)0.01599 (15)0.01872 (16)0.00594 (12)0.00403 (13)0.00333 (11)
N10.0196 (12)0.0193 (11)0.0212 (11)0.0008 (9)0.0039 (9)0.0067 (9)
N20.0207 (13)0.0257 (12)0.0189 (11)0.0001 (10)0.0034 (9)0.0049 (9)
C10.0208 (14)0.0214 (13)0.0237 (13)0.0021 (11)0.0068 (11)0.0044 (11)
C20.0200 (14)0.0206 (13)0.0273 (14)0.0007 (11)0.0074 (12)−0.0001 (11)
C30.0172 (14)0.0259 (14)0.0184 (12)−0.0033 (11)0.0060 (11)−0.0008 (10)
C40.0112 (12)0.0215 (13)0.0183 (12)−0.0013 (10)0.0036 (10)0.0055 (10)
C50.0176 (14)0.0169 (12)0.0214 (13)−0.0027 (10)0.0044 (11)0.0010 (10)
C60.0204 (15)0.0257 (14)0.0182 (12)−0.0034 (11)0.0063 (11)0.0010 (10)
C70.0287 (17)0.0428 (18)0.0203 (13)0.0058 (14)0.0037 (12)0.0110 (13)
C80.0267 (16)0.0253 (15)0.0320 (15)0.0027 (12)0.0053 (13)0.0095 (12)

Geometric parameters (Å, °)

Sn1—C12.131 (3)C1—H1A0.9800
Sn1—Br12.7240 (3)C1—H1B0.9800
Sn1—Br22.7234 (3)C1—H1C0.9800
N1—C61.342 (3)C2—H20.9500
N1—C21.356 (3)C3—H30.9500
N2—C41.338 (3)C5—H50.9500
N2—C81.456 (4)C6—H60.9500
N2—C71.460 (3)C7—H7A0.9800
C2—C31.354 (4)C7—H7B0.9800
C3—C41.421 (4)C7—H7C0.9800
C4—C51.419 (3)C8—H8A0.9800
C5—C61.353 (4)C8—H8B0.9800
N1—H10.8800C8—H8C0.9800
C1—Sn1—C1i180.0Sn1—C1—H1C109.5
C1—Sn1—Br189.74 (7)H1A—C1—H1C109.5
C1—Sn1—Br1i90.26 (7)H1B—C1—H1C109.5
Br1—Sn1—Br1i180.0C3—C2—H2119.5
Br1—Sn1—Br288.54 (1)N1—C2—H2119.5
Br1—Sn1—Br2i91.47 (1)C2—C3—H3119.7
Br2—Sn1—Br2i180.0C4—C3—H3119.7
C6—N1—C2120.5 (2)C6—C5—H5119.7
C4—N2—C8121.9 (2)C4—C5—H5119.7
C4—N2—C7120.5 (2)N1—C6—H6119.4
C8—N2—C7117.6 (2)C5—C6—H6119.4
C3—C2—N1120.9 (2)N2—C7—H7A109.5
C2—C3—C4120.6 (2)N2—C7—H7B109.5
N2—C4—C5122.2 (2)H7A—C7—H7B109.5
N2—C4—C3121.8 (2)N2—C7—H7C109.5
C5—C4—C3116.0 (2)H7A—C7—H7C109.5
C6—C5—C4120.6 (2)H7B—C7—H7C109.5
N1—C6—C5121.3 (2)N2—C8—H8A109.5
C6—N1—H1119.7N2—C8—H8B109.5
C2—N1—H1119.7H8A—C8—H8B109.5
Sn1—C1—H1A109.5N2—C8—H8C109.5
Sn1—C1—H1B109.5H8A—C8—H8C109.5
H1A—C1—H1B109.5H8B—C8—H8C109.5
C6—N1—C2—C31.4 (4)C2—C3—C4—N2179.1 (3)
N1—C2—C3—C40.0 (4)C2—C3—C4—C5−1.5 (4)
C8—N2—C4—C50.5 (4)N2—C4—C5—C6−178.8 (3)
C7—N2—C4—C5−179.4 (3)C3—C4—C5—C61.7 (4)
C8—N2—C4—C3179.9 (2)C2—N1—C6—C5−1.2 (4)
C7—N2—C4—C30.0 (4)C4—C5—C6—N1−0.4 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···X10.882.613.325 (2)139
N1—H1···X20.882.833.475 (2)132

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2501).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m800. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography