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Acta Cryst. (2008). E64, m800    [ doi:10.1107/S1600536808013561 ]

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

K. M. Lo and S. W. Ng

Abstract top

The tin(IV) atom in the salt, (C7H11N2)2[SnBr2(CH3)2Cl2], lies on a center of inversion in a tetragonally compressed octahedron; the bromine atoms are disordered with the chlorine atoms, so that they appear to share the same site. The crystal structure is stabilized by N-H...Br hydrogen bonds.

Comment top

Bis(4-methylaminopyridinium) tetrabromidodiphenylstannate is produced from the cleavage of the mixed alkyl/triarylstannate, cyclopentyltriphenyltin, by 4-dimethylaminopyridine hydrobromide perbromide (Yap et al., 2008). In principle, the salt can be synthesized from the reaction of 4-dimethylaminopyridine hydrobromide perbromide and diphenyltin dibromide. The possibility is borne out by reacting the organic reagent with dimethyltin dichloride to yield the title salt (Scheme I, Fig. 1). The SnIV atom of the stannate lies on a center-of-inversion in tetragonally compressed octahedron; the two indepedent bromine atom share the sames site as the two independent chlorine atoms.

Related literature top

For the structure of bis(4-dimethylaminopyridinium) tetrabromidodiphenylstannate, see: Yap et al. (2008).

Experimental top

Dimethyltin dichoride (2.20 g, 1 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (3.62 g, 1 mmol) were heated in ethanol in an attempt to synthesize the bromodichloridodimethylstannate salt. Colorless crystals separated from it after a few days.

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 similarly treated (N–H 0.88 Å; U(H) = 1.2 Ueq(N)).

The chlorine atoms are disordered with respect to the bromine atoms, so that the halogen site is occupied by both a chlorine and a bromine. Constraints were applied so that at each site, the atoms had the same coordinates and the same anisotropic displacement parameters. The occupancies refined to 0.4551 (15) for the Br1/Cl2 pair, and to 0.5449 (15) for the Br2/Cl1 pair. The final difference Fourier map had a large peak at 1 Å from Sn1.

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 [SnBr2Cl2(CH3)2] at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The disorder is not shown.
Bis[4-(dimethylamino)pyridinium] dibromidodichloridodimethylstannate(IV) top
Crystal data top
(C7H11N2)2[SnBr2(CH3)2Cl2]Z = 1
Mr = 625.83F000 = 306
Triclinic, P1Dx = 1.767 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.3573 (3) ÅCell parameters from 1302 reflections
b = 8.7717 (3) Åθ = 2.3–23.1º
c = 9.6644 (4) ŵ = 4.72 mm−1
α = 97.183 (3)ºT = 100 (2) K
β = 107.990 (3)ºPrism, colorless
γ = 90.052 (2)º0.25 × 0.20 × 0.15 mm
V = 588.04 (4) Å3
Data collection top
Bruker SMART APEX
diffractometer		2756 independent reflections
Radiation source: fine-focus sealed tube1656 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
T = 100(2) Kθmax = 27.5º
ω scansθmin = 2.3º
Absorption correction: Multi-scan
(SADABS;Sheldrick, 1996)		h = −9→9
Tmin = 0.385, Tmax = 0.538k = −11→11
4965 measured reflectionsl = −10→12
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)] = 0.046H-atom parameters constrained
wR(F2) = 0.123  w = 1/[σ2(Fo2) + (0.051P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2756 reflectionsΔρmax = 0.82 e Å−3
122 parametersΔρmin = −1.14 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C7H11N2)2[SnBr2(CH3)2Cl2]γ = 90.052 (2)º
Mr = 625.83V = 588.04 (4) Å3
Triclinic, P1Z = 1
a = 7.3573 (3) ÅMo Kα
b = 8.7717 (3) ŵ = 4.72 mm−1
c = 9.6644 (4) ÅT = 100 (2) K
α = 97.183 (3)º0.25 × 0.20 × 0.15 mm
β = 107.990 (3)º
Data collection top
Bruker SMART APEX
diffractometer		2756 independent reflections
Absorption correction: Multi-scan
(SADABS;Sheldrick, 1996)		1656 reflections with I > 2σ(I)
Tmin = 0.385, Tmax = 0.538Rint = 0.045
4965 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0464 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.04Δρmax = 0.82 e Å−3
2756 reflectionsΔρmin = −1.14 e Å−3
122 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.50000.50000.50000.0414 (2)
Br10.50474 (16)0.50403 (11)0.77987 (11)0.0610 (3)0.4551 (15)
Br20.36593 (14)0.78543 (10)0.49452 (10)0.0588 (3)0.5449 (15)
Cl10.50474 (16)0.50403 (11)0.77987 (11)0.0610 (3)0.5449 (15)
Cl20.36593 (14)0.78543 (10)0.49452 (10)0.0588 (3)0.4551 (15)
N10.6576 (7)0.1602 (6)0.8588 (6)0.0552 (14)
H10.62050.22480.79380.066*
N20.8414 (7)−0.1391 (6)1.1635 (6)0.0557 (14)
C10.2014 (7)0.4016 (6)0.4157 (6)0.0344 (12)
H1A0.20230.29040.41920.052*
H1B0.14320.42140.31420.052*
H1C0.12710.44950.47670.052*
C20.6816 (9)0.2092 (8)1.0006 (8)0.0581 (18)
H20.65710.31281.02900.070*
C30.7413 (9)0.1116 (7)1.1061 (7)0.0545 (16)
H30.75700.14801.20600.065*
C40.7793 (8)−0.0433 (7)1.0650 (7)0.0443 (15)
C50.7486 (8)−0.0875 (7)0.9140 (7)0.0488 (15)
H50.7698−0.19040.88050.059*
C60.6890 (9)0.0144 (8)0.8144 (7)0.0536 (16)
H60.6698−0.01830.71320.064*
C70.8687 (11)−0.0920 (10)1.3200 (8)0.084 (3)
H7A0.9886−0.03051.36390.127*
H7B0.8740−0.18361.36950.127*
H7C0.7616−0.03051.33100.127*
C80.8809 (10)−0.2972 (8)1.1236 (9)0.071 (2)
H8A0.7602−0.35601.07360.106*
H8B0.9498−0.34171.21240.106*
H8C0.9594−0.30081.05790.106*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0437 (4)0.0408 (3)0.0388 (4)0.0028 (3)0.0122 (3)0.0040 (3)
Br10.0938 (9)0.0501 (6)0.0460 (6)0.0082 (5)0.0319 (6)0.0062 (5)
Br20.0809 (7)0.0458 (5)0.0461 (6)0.0187 (5)0.0144 (5)0.0062 (4)
Cl10.0938 (9)0.0501 (6)0.0460 (6)0.0082 (5)0.0319 (6)0.0062 (5)
Cl20.0809 (7)0.0458 (5)0.0461 (6)0.0187 (5)0.0144 (5)0.0062 (4)
N10.050 (3)0.064 (4)0.052 (4)0.001 (3)0.012 (3)0.020 (3)
N20.048 (3)0.070 (4)0.050 (3)0.004 (3)0.012 (3)0.017 (3)
C10.032 (3)0.039 (3)0.040 (3)0.009 (2)0.019 (3)0.012 (3)
C20.050 (4)0.058 (4)0.064 (5)0.007 (3)0.016 (4)0.004 (4)
C30.048 (4)0.065 (4)0.048 (4)0.001 (3)0.016 (3)−0.006 (3)
C40.031 (3)0.063 (4)0.037 (3)−0.005 (3)0.008 (3)0.009 (3)
C50.047 (4)0.050 (3)0.047 (4)−0.003 (3)0.013 (3)0.002 (3)
C60.054 (4)0.064 (4)0.042 (4)−0.013 (3)0.016 (3)0.001 (3)
C70.075 (5)0.136 (7)0.043 (4)0.025 (5)0.013 (4)0.028 (5)
C80.071 (5)0.063 (5)0.079 (6)0.002 (4)0.016 (4)0.026 (4)
Geometric parameters (Å, °) top
Sn1—C1i2.225 (5)C1—H1C0.9800
Sn1—C12.225 (5)C2—C31.381 (8)
Sn1—Br12.690 (1)C2—H20.9500
Sn1—Cl1i2.690 (1)C3—C41.420 (9)
Sn1—Br1i2.690 (1)C3—H30.9500
Sn1—Br2i2.6926 (8)C4—C51.409 (9)
Sn1—Br22.6926 (8)C5—C61.369 (8)
Sn1—Cl2i2.6926 (8)C5—H50.9500
N1—C21.341 (9)C6—H60.9500
N1—C61.341 (9)C7—H7A0.9800
N1—H10.8800C7—H7B0.9800
N2—C41.324 (7)C7—H7C0.9800
N2—C81.446 (9)C8—H8A0.9800
N2—C71.467 (9)C8—H8B0.9800
C1—H1A0.9800C8—H8C0.9800
C1—H1B0.9800
C1i—Sn1—C1180.0Sn1—C1—H1A109.5
C1i—Sn1—Br188.38 (14)Sn1—C1—H1B109.5
C1—Sn1—Br191.62 (14)H1A—C1—H1B109.5
C1i—Sn1—Cl1i91.62 (14)Sn1—C1—H1C109.5
C1—Sn1—Cl1i88.38 (14)H1A—C1—H1C109.5
Br1—Sn1—Cl1i180.0H1B—C1—H1C109.5
C1i—Sn1—Br1i91.62 (14)N1—C2—C3121.1 (6)
C1—Sn1—Br1i88.38 (14)N1—C2—H2119.5
Br1—Sn1—Br1i180.0C3—C2—H2119.5
Cl1i—Sn1—Br1i0.0C2—C3—C4120.0 (6)
C1i—Sn1—Br2i89.83 (13)C2—C3—H3120.0
C1—Sn1—Br2i90.17 (13)C4—C3—H3120.0
Br1—Sn1—Br2i89.12 (3)N2—C4—C5122.5 (6)
Cl1i—Sn1—Br2i90.88 (3)N2—C4—C3121.6 (6)
Br1i—Sn1—Br2i90.88 (3)C5—C4—C3115.9 (6)
C1i—Sn1—Br290.17 (13)C6—C5—C4121.5 (6)
C1—Sn1—Br289.83 (13)C6—C5—H5119.2
Br1—Sn1—Br290.88 (3)C4—C5—H5119.2
Cl1i—Sn1—Br289.12 (3)N1—C6—C5120.4 (6)
Br1i—Sn1—Br289.12 (3)N1—C6—H6119.8
Br2i—Sn1—Br2180.0C5—C6—H6119.8
C1i—Sn1—Cl2i89.83 (13)N2—C7—H7A109.5
C1—Sn1—Cl2i90.17 (13)N2—C7—H7B109.5
Br1—Sn1—Cl2i89.12 (3)H7A—C7—H7B109.5
Cl1i—Sn1—Cl2i90.88 (3)N2—C7—H7C109.5
Br1i—Sn1—Cl2i90.88 (3)H7A—C7—H7C109.5
Br2i—Sn1—Cl2i0.000 (13)H7B—C7—H7C109.5
Br2—Sn1—Cl2i180.0N2—C8—H8A109.5
C2—N1—C6121.1 (6)N2—C8—H8B109.5
C2—N1—H1119.4H8A—C8—H8B109.5
C6—N1—H1119.4N2—C8—H8C109.5
C4—N2—C8122.3 (6)H8A—C8—H8C109.5
C4—N2—C7121.8 (6)H8B—C8—H8C109.5
C8—N2—C7115.9 (6)
C6—N1—C2—C30.6 (9)C2—C3—C4—N2178.3 (5)
N1—C2—C3—C40.3 (10)C2—C3—C4—C5−1.1 (8)
C8—N2—C4—C5−0.6 (9)N2—C4—C5—C6−178.3 (6)
C7—N2—C4—C5−178.7 (6)C3—C4—C5—C61.1 (9)
C8—N2—C4—C3−180.0 (5)C2—N1—C6—C5−0.7 (9)
C7—N2—C4—C31.9 (9)C4—C5—C6—N1−0.2 (9)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.603.316 (5)139
N1—H1···Br2i0.882.813.458 (6)132
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
Sn1—C12.225 (5)Sn1—Br22.6926 (8)
Sn1—Br12.690 (1)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.603.316 (5)139
N1—H1···Br2i0.882.813.458 (6)132
Symmetry codes: (i) −x+1, −y+1, −z+1.
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.

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

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

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

Yap, Q. L., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m696.