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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): m645.
Published online 2009 May 14. doi:  10.1107/S160053680901705X
PMCID: PMC2969538

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

Abstract

In the title compound, (C7H11N2)2[SnBr5Cl], there is Br/Cl disorder in 0.6561 (12):0.3439 (12) and 0.8438 (12):0.1561 (12) ratios over two of three halide sites in the centrosymmetric anion, such that an overall formulation of [SnBr5Cl]2− arises. In the crystal, associations of two cations and one anion linked by N—H(...)Br hydrogen bonds occur.

Related literature

For related 4-dimethyl­amino­pyridinium halogenoorgano­stannates, see: Lo & Ng (2008 [triangle]); Norhafiza et al. (2008 [triangle]); Yau et al. (2008 [triangle]).

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Object name is e-65-0m645-scheme1.jpg

Experimental

Crystal data

  • (C7H11N2)2[SnBr5Cl]
  • M r = 800.05
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m645-efi1.jpg
  • a = 8.4424 (1) Å
  • b = 11.8821 (2) Å
  • c = 11.8868 (2) Å
  • β = 107.123 (1)°
  • V = 1139.55 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 10.01 mm−1
  • T = 100 K
  • 0.30 × 0.10 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.152, T max = 0.434 (expected range = 0.129–0.367)
  • 9261 measured reflections
  • 2613 independent reflections
  • 2408 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.053
  • S = 1.01
  • 2613 reflections
  • 121 parameters
  • 4 restraints
  • H-atom parameters constrained
  • Δρmax = 0.91 e Å−3
  • Δρmin = −0.95 e Å−3

Data collection: APEX2 software (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, 2009 [triangle]).

Table 1
Selected bond lengths (Å). X = (Br, Cl)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901705X/hb2965sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901705X/hb2965Isup2.hkl

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

Acknowledgments

We thank the University of Malaya (RG020/09AFR) for supporting this study.

supplementary crystallographic information

Experimental

Dibenzyltin dichloride (0.37 g, 1 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (0.73 g, 2 mmol) were heated in chloroform for 3 hours. Colourless blocks of (I) separated from the cool solution after a day. The crystal structure showed that the benzyl groups on tin had been cleaved in the reaction.

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.95, N–H 0.88 Å) and were treated as riding on their parent atoms, with U(H) set to 1.2 times Ueq(C,N).

Two of the three halogen atoms in the stannate are disordered. The pair of Br1/Cl1 and Br2/Cl2 atoms initially refined to nearly 1.5Br and 0.5Cl atoms; the total occupancy of the disordered bromine atoms was then fixed as exactly 1.5. The occupancy of the disordered chlorine atoms was similarly set to be exactly 0.5.

The Uij values of the Br1 and Cl1 atoms were restrained to be identical, as were those of the Br2 and Cl2 atoms.

Figures

Fig. 1.
The molecular structure of (I) viewed at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

(C7H11N2)2[SnBr5Cl]F(000) = 752
Mr = 800.05Dx = 2.332 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5777 reflections
a = 8.4424 (1) Åθ = 2.5–28.3°
b = 11.8821 (2) ŵ = 10.01 mm1
c = 11.8868 (2) ÅT = 100 K
β = 107.123 (1)°Block, colourless
V = 1139.55 (3) Å30.30 × 0.10 × 0.10 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer2613 independent reflections
Radiation source: fine-focus sealed tube2408 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.152, Tmax = 0.434k = −15→15
9261 measured reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0276P)2 + 1.7721P] where P = (Fo2 + 2Fc2)/3
2613 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.91 e Å3
4 restraintsΔρmin = −0.95 e Å3

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

xyzUiso*/UeqOcc. (<1)
Sn10.50000.50000.50000.01035 (7)
Br10.50979 (5)0.63602 (3)0.66902 (3)0.02104 (10)0.6561 (12)
Br20.58402 (4)0.33881 (2)0.64884 (3)0.02209 (9)0.8438 (12)
Br30.80725 (3)0.53820 (3)0.52248 (3)0.02568 (8)
Cl10.50979 (5)0.63602 (3)0.66902 (3)0.02104 (10)0.3439 (12)
Cl20.58402 (4)0.33881 (2)0.64884 (3)0.02209 (9)0.1561 (12)
N10.6520 (3)0.8746 (2)0.5886 (3)0.0271 (6)
H10.59990.81230.59620.032*
N20.9139 (3)1.15682 (19)0.5545 (2)0.0186 (5)
C10.8253 (3)1.0669 (2)0.5659 (2)0.0154 (5)
C20.7373 (4)1.0025 (2)0.4666 (3)0.0194 (5)
H20.73581.02570.38980.023*
C30.6551 (4)0.9077 (2)0.4809 (3)0.0245 (6)
H30.59910.86420.41390.029*
C40.7277 (4)0.9358 (3)0.6848 (3)0.0251 (6)
H40.72030.91250.75950.030*
C50.8137 (4)1.0296 (2)0.6768 (3)0.0211 (6)
H50.86701.07110.74590.025*
C60.9127 (4)1.1990 (3)0.4393 (3)0.0249 (6)
H6A0.94881.13930.39550.037*
H6B0.98831.26330.44900.037*
H6C0.80021.22290.39580.037*
C71.0105 (4)1.2208 (3)0.6571 (3)0.0291 (7)
H7A0.93531.26500.68870.044*
H7B1.08661.27150.63360.044*
H7C1.07401.16870.71750.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn10.00978 (11)0.01195 (11)0.00936 (12)−0.00163 (8)0.00287 (9)−0.00006 (8)
Br10.0306 (2)0.01735 (16)0.01761 (19)−0.00301 (13)0.01094 (15)−0.00399 (12)
Br20.03025 (18)0.01759 (15)0.01582 (17)−0.00058 (12)0.00271 (13)0.00430 (11)
Br30.01302 (14)0.03789 (17)0.02652 (17)−0.00656 (11)0.00643 (12)−0.00107 (12)
Cl10.0306 (2)0.01735 (16)0.01761 (19)−0.00301 (13)0.01094 (15)−0.00399 (12)
Cl20.03025 (18)0.01759 (15)0.01582 (17)−0.00058 (12)0.00271 (13)0.00430 (11)
N10.0210 (12)0.0210 (12)0.0407 (17)−0.0003 (10)0.0115 (11)0.0092 (11)
N20.0175 (11)0.0195 (11)0.0167 (12)−0.0033 (9)0.0019 (9)−0.0018 (9)
C10.0123 (12)0.0183 (12)0.0145 (13)0.0038 (9)0.0025 (10)0.0005 (10)
C20.0183 (13)0.0212 (13)0.0170 (14)0.0007 (10)0.0024 (11)−0.0009 (11)
C30.0208 (14)0.0230 (14)0.0265 (16)−0.0016 (11)0.0019 (12)−0.0023 (12)
C40.0214 (14)0.0320 (15)0.0256 (16)0.0108 (12)0.0130 (12)0.0122 (13)
C50.0207 (14)0.0283 (14)0.0141 (14)0.0061 (11)0.0049 (11)0.0018 (11)
C60.0240 (14)0.0240 (14)0.0251 (16)−0.0053 (11)0.0047 (12)0.0069 (12)
C70.0290 (16)0.0304 (16)0.0233 (17)−0.0097 (12)0.0007 (13)−0.0110 (13)

Geometric parameters (Å, °)

Sn1—Br12.5608 (3)C1—C21.419 (4)
Sn1—Cl1i2.5608 (3)C1—C51.421 (4)
Sn1—Br1i2.5608 (3)C2—C31.360 (4)
Sn1—Br22.5618 (3)C2—H20.9500
Sn1—Cl2i2.5618 (3)C3—H30.9500
Sn1—Br2i2.5618 (3)C4—C51.348 (4)
Sn1—Br3i2.5687 (3)C4—H40.9500
Sn1—Br32.5687 (3)C5—H50.9500
N1—C41.347 (4)C6—H6A0.9800
N1—C31.347 (4)C6—H6B0.9800
N1—H10.8800C6—H6C0.9800
N2—C11.334 (3)C7—H7A0.9800
N2—C61.456 (4)C7—H7B0.9800
N2—C71.464 (4)C7—H7C0.9800
Br1—Sn1—Cl1i180.0C1—N2—C6121.5 (2)
Br1—Sn1—Br1i180.0C1—N2—C7121.6 (2)
Cl1i—Sn1—Br1i0.000 (11)C6—N2—C7116.9 (2)
Br1—Sn1—Br289.520 (11)N2—C1—C2121.3 (3)
Cl1i—Sn1—Br290.480 (11)N2—C1—C5122.5 (3)
Br1i—Sn1—Br290.480 (11)C2—C1—C5116.2 (3)
Br1—Sn1—Cl2i90.480 (11)C3—C2—C1120.3 (3)
Cl1i—Sn1—Cl2i89.520 (11)C3—C2—H2119.8
Br1i—Sn1—Cl2i89.520 (11)C1—C2—H2119.8
Br2—Sn1—Cl2i180.000 (12)N1—C3—C2120.9 (3)
Br1—Sn1—Br2i90.480 (11)N1—C3—H3119.6
Cl1i—Sn1—Br2i89.520 (11)C2—C3—H3119.6
Br1i—Sn1—Br2i89.520 (11)N1—C4—C5121.1 (3)
Br2—Sn1—Br2i180.000 (12)N1—C4—H4119.4
Cl2i—Sn1—Br2i0.00 (2)C5—C4—H4119.4
Br1—Sn1—Br3i89.512 (11)C4—C5—C1120.6 (3)
Cl1i—Sn1—Br3i90.488 (11)C4—C5—H5119.7
Br1i—Sn1—Br3i90.488 (11)C1—C5—H5119.7
Br2—Sn1—Br3i90.316 (10)N2—C6—H6A109.5
Cl2i—Sn1—Br3i89.684 (10)N2—C6—H6B109.5
Br2i—Sn1—Br3i89.684 (10)H6A—C6—H6B109.5
Br1—Sn1—Br390.488 (11)N2—C6—H6C109.5
Cl1i—Sn1—Br389.512 (11)H6A—C6—H6C109.5
Br1i—Sn1—Br389.512 (11)H6B—C6—H6C109.5
Br2—Sn1—Br389.684 (10)N2—C7—H7A109.5
Cl2i—Sn1—Br390.316 (10)N2—C7—H7B109.5
Br2i—Sn1—Br390.316 (10)H7A—C7—H7B109.5
Br3i—Sn1—Br3180.0N2—C7—H7C109.5
C4—N1—C3120.8 (3)H7A—C7—H7C109.5
C4—N1—H1119.6H7B—C7—H7C109.5
C3—N1—H1119.6
C6—N2—C1—C25.6 (4)C4—N1—C3—C21.3 (4)
C7—N2—C1—C2−177.4 (3)C1—C2—C3—N11.7 (4)
C6—N2—C1—C5−174.8 (3)C3—N1—C4—C5−2.4 (4)
C7—N2—C1—C52.2 (4)N1—C4—C5—C10.6 (4)
N2—C1—C2—C3176.4 (3)N2—C1—C5—C4−177.5 (3)
C5—C1—C2—C3−3.3 (4)C2—C1—C5—C42.2 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.473.327 (2)165

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2965).

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, m834. [PMC free article] [PubMed]
  • Norhafiza, I., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m720. [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. (2009). publCIF In preparation.
  • Yau, C. K., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m1391. [PMC free article] [PubMed]

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