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Acta Cryst. (2008). E64, m696    [ doi:10.1107/S1600536808010830 ]

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

Q. L. Yap, K. M. Lo and S. W. Ng

Abstract top

The SnIV atom of the stannate anion in the title salt, (C7H11N2)2[SnBr4(C6H5)2], lies on a center of inversion in a tetragonally compressed octahedron. The two independent Br atoms in the anion are hydrogen-bond acceptors for the same cation.

Comment top

Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylstannate(IV), (I) (Fig. 1 and Table 1) was the product of the cleavage of the mixed alkyl/triarylstannate, cyclopentyltriphenyltin, by 4-dimethylaminopyridine hydrobromide perbromide. The stannate has the tin atom in a tetragonally compressed octahedral Br4C2 environment. The anion has also been reported as the centrosymmetric pyridinium salt: Sn–Br = 2.7592 (3), 2.7737 (3) and Sn–C 2.158 (3) Å (Tuleda & Khan, 1991). Connections between ions are of the type N-H···Br (Table 2) so that each independent pair of bromide atoms are linked to the same cation.

Related literature top

For the structure of dipyridinium tetrabromidostannate, see: Tuleda & Khan (1991).

Experimental top

Cyclopentyltriphenyltin (1.36 g, 3 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (1.1 g, 3 mmol) were heated in chloroform (100 ml) for 3 h. The filtered solution when allowed to evaporate yielded large yellow crystals, m.p. 470–473 K.

Refinement top

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 refined with a distance restraint of N–H 0.88±0.01 Å; its displacement parameter was freely refined.

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
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of [C7H11N]2 [SnBr4(C6H5)2] at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylstannate(IV) top
Crystal data top
(C7H11N2)2[SnBr4(C6H5)2]F000 = 812
Mr = 838.89Dx = 1.916 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3449 reflections
a = 10.7803 (2) Åθ = 2.3–28.3º
b = 9.3847 (2) ŵ = 6.40 mm−1
c = 14.4068 (4) ÅT = 100 (2) K
β = 94.126 (2)ºBlock, colorless
V = 1453.76 (6) Å30.24 × 0.18 × 0.12 mm
Z = 2
Data collection top
Bruker SMART APEX
diffractometer		3334 independent reflections
Radiation source: fine-focus sealed tube2688 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 100(2) Kθmax = 27.5º
ω scansθmin = 2.3º
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		h = −14→14
Tmin = 0.386, Tmax = 0.514k = −12→12
11853 measured reflectionsl = −18→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.051  w = 1/[σ2(Fo2) + (0.0228P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3334 reflectionsΔρmax = 0.47 e Å−3
166 parametersΔρmin = −0.42 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C7H11N2)2[SnBr4(C6H5)2]V = 1453.76 (6) Å3
Mr = 838.89Z = 2
Monoclinic, P21/nMo Kα
a = 10.7803 (2) ŵ = 6.40 mm−1
b = 9.3847 (2) ÅT = 100 (2) K
c = 14.4068 (4) Å0.24 × 0.18 × 0.12 mm
β = 94.126 (2)º
Data collection top
Bruker SMART APEX
diffractometer		3334 independent reflections
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		2688 reflections with I > 2σ(I)
Tmin = 0.386, Tmax = 0.514Rint = 0.035
11853 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0241 restraint
wR(F2) = 0.051H atoms treated by a mixture of
independent and constrained refinement
S = 0.99Δρmax = 0.47 e Å−3
3334 reflectionsΔρmin = −0.42 e Å−3
166 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.50000.50000.50000.01159 (7)
Br10.25635 (2)0.50711 (3)0.43147 (2)0.01591 (7)
Br20.55014 (2)0.71661 (3)0.38004 (2)0.01549 (7)
N10.05057 (19)1.2090 (2)0.45413 (16)0.0168 (5)
N20.2527 (2)0.8608 (3)0.3851 (2)0.0309 (7)
H2N0.296 (3)0.785 (2)0.372 (3)0.057 (12)*
C10.4622 (2)0.6546 (3)0.60374 (19)0.0130 (6)
C20.5344 (2)0.7784 (3)0.6151 (2)0.0185 (6)
H20.60430.79160.57940.022*
C30.5038 (3)0.8816 (3)0.6784 (2)0.0232 (7)
H30.55290.96540.68620.028*
C40.4025 (3)0.8631 (3)0.7301 (2)0.0248 (7)
H40.38070.93540.77220.030*
C50.3325 (3)0.7406 (3)0.7212 (2)0.0219 (7)
H50.26390.72770.75820.026*
C60.3615 (2)0.6360 (3)0.65865 (19)0.0172 (6)
H60.31310.55150.65300.021*
C7−0.0284 (3)1.2845 (3)0.3844 (2)0.0260 (7)
H7A0.02361.33680.34290.039*
H7B−0.08161.35170.41530.039*
H7C−0.08041.21600.34810.039*
C80.0588 (3)1.2631 (3)0.5493 (2)0.0209 (6)
H8A0.03861.18660.59200.031*
H8B−0.00011.34180.55410.031*
H8C0.14351.29720.56570.031*
C90.1188 (2)1.0979 (3)0.4305 (2)0.0141 (6)
C100.1155 (2)1.0461 (3)0.3381 (2)0.0182 (6)
H100.06681.09370.29000.022*
C110.1821 (3)0.9282 (3)0.3182 (2)0.0254 (7)
H110.17860.89320.25620.031*
C120.2617 (3)0.9093 (3)0.4731 (2)0.0280 (8)
H120.31410.86090.51860.034*
C130.1979 (2)1.0250 (3)0.4982 (2)0.0201 (7)
H130.20581.05770.56070.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.01150 (12)0.01286 (14)0.01055 (14)0.00047 (10)0.00166 (10)0.00068 (11)
Br10.01193 (13)0.01943 (15)0.01628 (15)0.00059 (10)0.00046 (10)0.00031 (12)
Br20.01807 (13)0.01534 (14)0.01326 (14)−0.00163 (11)0.00254 (10)0.00332 (13)
N10.0165 (11)0.0180 (12)0.0155 (13)0.0016 (10)−0.0018 (9)0.0031 (11)
N20.0372 (15)0.0258 (16)0.0305 (17)0.0166 (13)0.0093 (13)0.0049 (14)
C10.0147 (13)0.0135 (14)0.0109 (15)0.0026 (11)0.0011 (11)−0.0007 (12)
C20.0209 (14)0.0194 (15)0.0155 (15)−0.0009 (12)0.0027 (12)0.0045 (13)
C30.0308 (16)0.0152 (16)0.0227 (17)−0.0012 (12)−0.0039 (13)−0.0025 (13)
C40.0339 (17)0.0243 (17)0.0158 (16)0.0109 (14)−0.0004 (13)−0.0078 (14)
C50.0193 (14)0.0345 (19)0.0120 (15)0.0065 (12)0.0012 (12)−0.0018 (14)
C60.0139 (13)0.0235 (16)0.0138 (15)0.0001 (11)−0.0015 (11)−0.0003 (13)
C70.0217 (15)0.0307 (18)0.0244 (17)0.0081 (13)−0.0072 (13)−0.0020 (15)
C80.0233 (14)0.0217 (16)0.0178 (16)−0.0016 (12)0.0018 (12)−0.0022 (13)
C90.0132 (12)0.0147 (14)0.0147 (15)−0.0048 (10)0.0016 (11)0.0038 (12)
C100.0184 (14)0.0163 (15)0.0197 (16)0.0006 (11)0.0000 (12)0.0056 (13)
C110.0345 (17)0.0237 (17)0.0188 (17)0.0052 (14)0.0073 (14)0.0021 (15)
C120.0271 (16)0.0303 (19)0.0261 (19)0.0057 (14)−0.0014 (14)0.0102 (16)
C130.0192 (13)0.0234 (17)0.0175 (16)−0.0012 (12)0.0010 (12)0.0045 (13)
Geometric parameters (Å, °) top
Sn1—C12.143 (3)C4—H40.9500
Sn1—C1i2.143 (3)C5—C61.384 (4)
Sn1—Br12.7395 (2)C5—H50.9500
Sn1—Br1i2.7395 (2)C6—H60.9500
Sn1—Br22.7470 (3)C7—H7A0.9800
Sn1—Br2i2.7470 (3)C7—H7B0.9800
N1—C91.334 (3)C7—H7C0.9800
N1—C71.454 (3)C8—H8A0.9800
N1—C81.459 (4)C8—H8B0.9800
N2—C121.344 (4)C8—H8C0.9800
N2—C111.342 (4)C9—C101.415 (4)
N2—H2N0.879 (10)C9—C131.424 (4)
C1—C61.399 (4)C10—C111.361 (4)
C1—C21.402 (4)C10—H100.9500
C2—C31.387 (4)C11—H110.9500
C2—H20.9500C12—C131.349 (4)
C3—C41.376 (4)C12—H120.9500
C3—H30.9500C13—H130.9500
C4—C51.376 (4)
C1—Sn1—C1i180.0C6—C5—C4120.3 (3)
C1—Sn1—Br190.53 (7)C6—C5—H5119.8
C1—Sn1—Br1i89.47 (7)C4—C5—H5119.8
C1—Sn1—Br289.64 (7)C5—C6—C1120.1 (3)
C1—Sn1—Br2i90.36 (7)C5—C6—H6120.0
C1i—Sn1—Br189.47 (7)C1—C6—H6120.0
C1i—Sn1—Br1i90.53 (7)N1—C7—H7A109.5
C1i—Sn1—Br290.36 (7)N1—C7—H7B109.5
C1i—Sn1—Br2i89.64 (7)H7A—C7—H7B109.5
Br1—Sn1—Br1i180.0N1—C7—H7C109.5
Br1—Sn1—Br288.981 (8)H7A—C7—H7C109.5
Br1—Sn1—Br2i91.019 (8)H7B—C7—H7C109.5
Br1i—Sn1—Br2i88.981 (8)N1—C8—H8A109.5
Br1i—Sn1—Br291.019 (8)N1—C8—H8B109.5
Br2—Sn1—Br2i180.0H8A—C8—H8B109.5
C9—N1—C7120.7 (2)N1—C8—H8C109.5
C9—N1—C8121.0 (2)H8A—C8—H8C109.5
C7—N1—C8118.2 (2)H8B—C8—H8C109.5
C12—N2—C11121.0 (3)N1—C9—C10122.1 (2)
C12—N2—H2N118 (3)N1—C9—C13121.0 (3)
C11—N2—H2N120 (3)C10—C9—C13116.9 (2)
C6—C1—C2118.9 (3)C11—C10—C9120.0 (3)
C6—C1—Sn1120.3 (2)C11—C10—H10120.0
C2—C1—Sn1120.71 (19)C9—C10—H10120.0
C3—C2—C1120.0 (3)N2—C11—C10120.8 (3)
C3—C2—H2120.0N2—C11—H11119.6
C1—C2—H2120.0C10—C11—H11119.6
C4—C3—C2120.2 (3)N2—C12—C13121.5 (3)
C4—C3—H3119.9N2—C12—H12119.3
C2—C3—H3119.9C13—C12—H12119.3
C3—C4—C5120.4 (3)C12—C13—C9119.7 (3)
C3—C4—H4119.8C12—C13—H13120.1
C5—C4—H4119.8C9—C13—H13120.1
Br1i—Sn1—C1—C6−130.5 (2)C2—C1—C6—C51.7 (4)
Br1—Sn1—C1—C649.5 (2)Sn1—C1—C6—C5−175.7 (2)
Br2i—Sn1—C1—C6−41.5 (2)C7—N1—C9—C10−1.6 (4)
Br2—Sn1—C1—C6138.5 (2)C8—N1—C9—C10−178.0 (2)
Br1i—Sn1—C1—C252.2 (2)C7—N1—C9—C13178.9 (2)
Br1—Sn1—C1—C2−127.8 (2)C8—N1—C9—C132.6 (4)
Br2i—Sn1—C1—C2141.2 (2)N1—C9—C10—C11−176.8 (3)
Br2—Sn1—C1—C2−38.8 (2)C13—C9—C10—C112.6 (4)
C6—C1—C2—C3−1.5 (4)C12—N2—C11—C10−1.4 (5)
Sn1—C1—C2—C3175.9 (2)C9—C10—C11—N2−0.9 (4)
C1—C2—C3—C4−0.2 (4)C11—N2—C12—C131.7 (5)
C2—C3—C4—C51.7 (4)N2—C12—C13—C90.2 (5)
C3—C4—C5—C6−1.5 (4)N1—C9—C13—C12177.1 (3)
C4—C5—C6—C1−0.2 (4)C10—C9—C13—C12−2.3 (4)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Br10.88 (1)2.79 (3)3.385 (3)126 (3)
N2—H2N···Br20.88 (1)2.81 (3)3.485 (3)135 (3)
Table 1
Selected geometric parameters (Å, °) top
Sn1—C12.143 (3)Sn1—Br22.7470 (3)
Sn1—Br12.7395 (2)
C1—Sn1—Br190.53 (7)C1—Sn1—Br2i90.36 (7)
C1—Sn1—Br1i89.47 (7)Br1—Sn1—Br288.981 (8)
C1—Sn1—Br289.64 (7)Br1—Sn1—Br2i91.019 (8)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2N···Br10.88 (1)2.79 (3)3.385 (3)126 (3)
N2—H2N···Br20.88 (1)2.81 (3)3.485 (3)135 (3)
Acknowledgements top

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

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT . Bruker AXS Inc., Madison, Wisconsin, USA. APEX2software is only applicable to APEXII diffractometer; please correct either diffractometer name or software reference.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tuleda, D. & Khan, M. A. (1991). J. Chem. Soc. Dalton Trans. pp. 1003–1005.

Westrip, S. P. (2008). publCIF. In preparation.