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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): m715.
Published online 2009 June 6. doi:  10.1107/S1600536809019734
PMCID: PMC2969252

Bis[4-(dimethyl­amino)pyridinium] hexa­kis[bromido/chlorido(0.78/0.22)]stannate(IV)

Abstract

The Sn atom in the title salt, (C7H11N2)2[SnBr4.67Cl1.33], lies on a center of symmetry within an octa­hedron of disordered halogen atoms. The three independent halogen atoms are each a mixture of bromine and chlorine atoms [with site occupancies for bromine of 0.614 (1), 0.831 (1) and 0.888 (1)]. An N—H(...) hydrogen bond is present.

Related literature

For the isostructural tribromidotrichloridostannate, see: Lo & Ng (2008 [triangle]); for the isostructural penta­bromido­chlorido­stannate, see: Jang et al. (2009 [triangle]).

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Object name is e-65-0m715-scheme1.jpg

Experimental

Crystal data

  • (C7H11N2)2[SnBr4.67Cl1.33]
  • M r = 785.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m715-efi1.jpg
  • a = 8.4530 (2) Å
  • b = 11.9036 (2) Å
  • c = 11.9093 (2) Å
  • β = 107.109 (1)°
  • V = 1145.30 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 9.42 mm−1
  • T = 100 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.504, T max = 0.746 (expected range = 0.103–0.152)
  • 10319 measured reflections
  • 2622 independent reflections
  • 2240 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.060
  • S = 0.99
  • 2622 reflections
  • 127 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.80 e Å−3
  • Δρmin = −0.87 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, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019734/tk2458sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019734/tk2458Isup2.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 1 hour. Colorless crystals separated from the cool solution after a day. The benzyl groups on tin has been cleaved in the reaction. In the previous study, a heating time of 3 hours gave the pentabromidochloridostannate (Jang et al., 2009).

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.95–0.98, N–H 0.88 Å) and were treated as riding on their parent atoms, with U(H) set to 1.2–1.5 times Ueq(C,N).

The three halogen atoms in the stannate are disordered. The sum of the occupancies of the three bromide atoms refined to nearly 2.33Br and 0.67Cl atoms; the total occupancy of the disordered bromide atoms was then fixed as exactly 2.333. The occupancy of the disordered chloride atoms was similarly set to be 0.667. The anisotropic displacement parameters of each pair of Br/Cl atoms were restrained to be identical.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of 2[C7H11N2]+ [SnBr4.67Cl1.33]2- at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The bromine atoms are disordered with respect to the chlorine atoms.

Crystal data

(C7H11N2)2[SnBr4.67Cl1.33]F(000) = 740
Mr = 785.15Dx = 2.277 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4263 reflections
a = 8.4530 (2) Åθ = 2.5–28.3°
b = 11.9036 (2) ŵ = 9.42 mm1
c = 11.9093 (2) ÅT = 100 K
β = 107.109 (1)°Irregular block, colorless
V = 1145.30 (4) Å30.30 × 0.25 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer2622 independent reflections
Radiation source: fine-focus sealed tube2240 reflections with I > 2σ(I)
graphiteRint = 0.033
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.504, Tmax = 0.746k = −15→15
10319 measured reflectionsl = −14→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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060H atoms treated by a mixture of independent and constrained refinement
S = 0.99w = 1/[σ2(Fo2) + (0.0343P)2 + 0.6005P] where P = (Fo2 + 2Fc2)/3
2622 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.80 e Å3
6 restraintsΔρmin = −0.87 e Å3

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

xyzUiso*/UeqOcc. (<1)
Sn10.50000.50000.50000.01384 (8)
Br10.50914 (5)0.63592 (3)0.66901 (3)0.02247 (12)0.6143 (14)
Br20.58481 (5)0.33875 (3)0.64866 (3)0.02405 (12)0.8309 (9)
Br30.80683 (4)0.53911 (3)0.52227 (3)0.02760 (12)0.8878 (10)
Cl10.50914 (5)0.63592 (3)0.66901 (3)0.02247 (12)0.3858 (14)
Cl20.58481 (5)0.33875 (3)0.64866 (3)0.02405 (12)0.1122 (10)
Cl30.80683 (4)0.53911 (3)0.52227 (3)0.02760 (12)0.1691 (9)
N10.6521 (4)0.8743 (2)0.5886 (3)0.0309 (7)
H10.598 (5)0.812 (2)0.593 (4)0.061 (14)*
N20.9135 (3)1.1561 (2)0.5550 (2)0.0231 (6)
C10.7281 (4)0.9350 (3)0.6844 (3)0.0304 (8)
H1A0.72120.91160.75900.036*
C20.8143 (4)1.0288 (3)0.6765 (3)0.0259 (7)
H20.86831.06960.74570.031*
C30.8251 (4)1.0670 (3)0.5661 (3)0.0190 (6)
C40.7363 (4)1.0019 (3)0.4663 (3)0.0228 (7)
H40.73451.02490.38960.027*
C50.6553 (4)0.9080 (3)0.4810 (3)0.0297 (8)
H50.59940.86450.41420.036*
C61.0103 (4)1.2201 (3)0.6573 (3)0.0349 (8)
H6A0.93561.26520.68830.052*
H6B1.08761.26970.63400.052*
H6C1.07251.16800.71820.052*
C70.9124 (4)1.1989 (3)0.4397 (3)0.0293 (7)
H7A0.95771.14180.39850.044*
H7B0.98021.26700.44960.044*
H7C0.79851.21660.39370.044*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Sn10.01350 (14)0.01560 (14)0.01208 (14)−0.00189 (10)0.00326 (11)−0.00020 (11)
Br10.0329 (2)0.0187 (2)0.0178 (2)−0.00322 (16)0.01055 (17)−0.00423 (15)
Br20.0329 (2)0.01902 (19)0.01671 (19)−0.00065 (14)0.00180 (15)0.00479 (13)
Br30.01394 (18)0.0409 (2)0.0279 (2)−0.00705 (13)0.00609 (14)−0.00114 (15)
Cl10.0329 (2)0.0187 (2)0.0178 (2)−0.00322 (16)0.01055 (17)−0.00423 (15)
Cl20.0329 (2)0.01902 (19)0.01671 (19)−0.00065 (14)0.00180 (15)0.00479 (13)
Cl30.01394 (18)0.0409 (2)0.0279 (2)−0.00705 (13)0.00609 (14)−0.00114 (15)
N10.0277 (16)0.0246 (15)0.0427 (19)0.0002 (12)0.0141 (14)0.0088 (14)
N20.0235 (14)0.0244 (14)0.0195 (14)−0.0029 (11)0.0032 (11)−0.0017 (11)
C10.0298 (19)0.037 (2)0.0273 (18)0.0121 (15)0.0138 (15)0.0114 (16)
C20.0256 (17)0.0335 (18)0.0190 (17)0.0045 (14)0.0071 (14)0.0010 (13)
C30.0157 (14)0.0217 (15)0.0185 (15)0.0046 (11)0.0036 (12)0.0009 (12)
C40.0214 (15)0.0252 (16)0.0198 (16)−0.0003 (13)0.0030 (13)−0.0026 (13)
C50.0238 (17)0.0282 (18)0.033 (2)−0.0001 (13)0.0021 (15)−0.0037 (15)
C60.033 (2)0.035 (2)0.033 (2)−0.0101 (15)0.0035 (16)−0.0085 (16)
C70.0300 (18)0.0285 (18)0.0270 (18)−0.0048 (14)0.0045 (14)0.0082 (14)

Geometric parameters (Å, °)

Sn1—Br12.5658 (4)C1—C21.351 (5)
Sn1—Cl1i2.5658 (4)C1—H1A0.9500
Sn1—Br1i2.5658 (4)C2—C31.419 (4)
Sn1—Br22.5663 (3)C2—H20.9500
Sn1—Cl2i2.5663 (3)C3—C41.433 (4)
Sn1—Br2i2.5663 (3)C4—C51.349 (5)
Sn1—Cl3i2.5709 (3)C4—H40.9500
Sn1—Br3i2.5709 (3)C5—H50.9500
Sn1—Br32.5709 (3)C6—H6A0.9800
N1—C11.343 (5)C6—H6B0.9800
N1—C51.351 (5)C6—H6C0.9800
N1—H10.882 (10)C7—H7A0.9800
N2—C31.327 (4)C7—H7B0.9800
N2—C61.466 (4)C7—H7C0.9800
N2—C71.462 (4)
Br1—Sn1—Cl1i180.0Br3i—Sn1—Br3180.000 (17)
Br1—Sn1—Br1i180.0C1—N1—C5120.5 (3)
Cl1i—Sn1—Br1i0.000 (14)C1—N1—H1122 (3)
Br1—Sn1—Br289.576 (13)C5—N1—H1118 (3)
Cl1i—Sn1—Br290.424 (13)C3—N2—C6121.7 (3)
Br1i—Sn1—Br290.424 (13)C3—N2—C7121.6 (3)
Br1—Sn1—Cl2i90.424 (13)C6—N2—C7116.6 (3)
Cl1i—Sn1—Cl2i89.576 (12)N1—C1—C2121.2 (3)
Br1i—Sn1—Cl2i89.576 (12)N1—C1—H1A119.4
Br2—Sn1—Cl2i180.0C2—C1—H1A119.4
Br1—Sn1—Br2i90.424 (13)C1—C2—C3120.8 (3)
Cl1i—Sn1—Br2i89.576 (12)C1—C2—H2119.6
Br1i—Sn1—Br2i89.576 (12)C3—C2—H2119.6
Br2—Sn1—Br2i180.0N2—C3—C2122.7 (3)
Cl2i—Sn1—Br2i0.00 (2)N2—C3—C4121.5 (3)
Br1—Sn1—Cl3i89.529 (12)C2—C3—C4115.7 (3)
Cl1i—Sn1—Cl3i90.471 (12)C5—C4—C3120.2 (3)
Br1i—Sn1—Cl3i90.471 (12)C5—C4—H4119.9
Br2—Sn1—Cl3i90.248 (12)C3—C4—H4119.9
Cl2i—Sn1—Cl3i89.752 (12)C4—C5—N1121.4 (3)
Br2i—Sn1—Cl3i89.752 (12)C4—C5—H5119.3
Br1—Sn1—Br3i89.529 (12)N1—C5—H5119.3
Cl1i—Sn1—Br3i90.471 (12)N2—C6—H6A109.5
Br1i—Sn1—Br3i90.471 (12)N2—C6—H6B109.5
Br2—Sn1—Br3i90.248 (12)H6A—C6—H6B109.5
Cl2i—Sn1—Br3i89.752 (12)N2—C6—H6C109.5
Br2i—Sn1—Br3i89.752 (12)H6A—C6—H6C109.5
Cl3i—Sn1—Br3i0.00 (2)H6B—C6—H6C109.5
Br1—Sn1—Br390.471 (12)N2—C7—H7A109.5
Cl1i—Sn1—Br389.529 (12)N2—C7—H7B109.5
Br1i—Sn1—Br389.529 (12)H7A—C7—H7B109.5
Br2—Sn1—Br389.752 (12)N2—C7—H7C109.5
Cl2i—Sn1—Br390.248 (12)H7A—C7—H7C109.5
Br2i—Sn1—Br390.248 (12)H7B—C7—H7C109.5
Cl3i—Sn1—Br3180.000 (17)
C5—N1—C1—C2−2.3 (5)C1—C2—C3—N2−177.4 (3)
N1—C1—C2—C30.9 (5)C1—C2—C3—C41.5 (5)
C6—N2—C3—C21.6 (5)N2—C3—C4—C5176.1 (3)
C7—N2—C3—C2−175.2 (3)C2—C3—C4—C5−2.8 (5)
C6—N2—C3—C4−177.3 (3)C3—C4—C5—N11.6 (5)
C7—N2—C3—C45.9 (5)C1—N1—C5—C41.0 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.88 (1)2.48 (2)3.334 (3)162 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2458).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Jang, Y., Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, m645. [PMC free article] [PubMed]
  • Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m834. [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.

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