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Acta Cryst. (2008). E64, m720    [ doi:10.1107/S1600536808011094 ]

4-(Dimethylamino)pyridinium dibromidotriphenylstannate(IV)

I. Norhafiza, K. M. Lo and S. W. Ng

Abstract top

The anion in the title salt, (C7H11N2)[SnBr2(C6H5)3], lies on a twofold rotation axis that passes through the metal atom as well as the Cipso-Cpara atoms of one of the aromatic rings. The metal center is five-coordinate in a trans-Br2SnC3 trigonal bipyramidal geometry. The cation is disordered about a center of inversion.

Comment top

The aqueous solubility of biocidal triorganotin halides can be improved by converting them to their ionic salts through treatment with an ammonium halide. A small number of ammonium dihalogenotriorganostannates are known; tetraethylammonium dibromidotriphenylstannate, who crystal structure is known, is synthesized in this manner (Wharf & Simard, 1991).

The present synthesis uses the mild brominating agent, 4-dimethylaminopyridine hydrobromide perbromide, which cleaves one of the four tin-carbon bonds of tetraphenyltin to yield the bromidotriphenylstannate anion. In the title compound (I), the anion lies about a twofold rotation axis that passes through the metal atom as well as the Cipso–Cpara atoms of one of the aromatic rings. The metal center is five-coordinate in a trans-C3SnBr2 trigonal bipyramidal geometry. The cation and anion exist as two non-interacting species (Fig. 1).

Related literature top

For the crystal structures of dibromidotriorganostannates, see: Aslanov et al. (1977); Spek et al. (2004); Wharf & Simard (1991).

Experimental top

Tetraphenyltin (2 g, 4.7 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (1.7 g, 4.6 mmol) were heated in chloroform (100 ml) for 6 h. The solution was filtered and the solvent allow to evaporate to give yellow crystals (m.p. 455–457 K, 80% yield).

Refinement top

The cation is disordered over a center-of-inversion, and was allowed to refine over this symmetry element as a half-occupancy cation. For the aromatic ring, 1,2-related distances were restrained to 1.39±0.01 Å and 1,3-related ones to 2.78±0.01 Å. For the dimethylamino group, the N–C distances were restrained to 1.50±0.01 Å. Anisotropic temperature factors of the carbon and nitrogen atoms were restrained to be nearly isotropic.

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The ammonium H-atom was similarly treated (N–H 0.86 Å; U(H) = 1.2U(B).

The final difference Fourier map had a large peak at 1 Å from Br1.

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 of the title compound.
4-(Dimethylamino)pyridinium dibromidotriphenylstannate(IV) top
Crystal data top
(C7H11N2)[SnBr2(C6H5)3]F000 = 1240
Mr = 632.99Dx = 1.706 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 7191 reflections
a = 15.5955 (2) Åθ = 2.3–24.8º
b = 10.6897 (1) ŵ = 4.29 mm−1
c = 14.8204 (2) ÅT = 100 K
β = 93.924 (1)ºBlock, yellow
V = 2464.93 (5) Å30.3 × 0.2 × 0.1 mm
Z = 4
Data collection top
Bruker SMART APEXII
diffractometer		2840 independent reflections
Radiation source: fine-focus sealed tube2328 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 100 Kθmax = 27.5º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −20→20
Tmin = 0.368, Tmax = 0.651k = −13→13
24740 measured reflectionsl = −19→19
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)] = 0.026H-atom parameters constrained
wR(F2) = 0.069  w = 1/[σ2(Fo2) + (0.0352P)2 + 2.1489P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2840 reflectionsΔρmax = 0.34 e Å−3
180 parametersΔρmin = −1.16 e Å−3
69 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C7H11N2)[SnBr2(C6H5)3]V = 2464.93 (5) Å3
Mr = 632.99Z = 4
Monoclinic, C2/cMo Kα
a = 15.5955 (2) ŵ = 4.29 mm−1
b = 10.6897 (1) ÅT = 100 K
c = 14.8204 (2) Å0.3 × 0.2 × 0.1 mm
β = 93.924 (1)º
Data collection top
Bruker SMART APEXII
diffractometer		2840 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2328 reflections with I > 2σ(I)
Tmin = 0.368, Tmax = 0.651Rint = 0.033
24740 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02669 restraints
wR(F2) = 0.069H-atom parameters constrained
S = 1.06Δρmax = 0.34 e Å−3
2840 reflectionsΔρmin = −1.16 e Å−3
180 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.50000.76516 (2)0.75000.03975 (9)
Br10.56766 (2)0.76825 (3)0.928473 (19)0.05538 (10)
C10.60873 (15)0.8708 (2)0.71394 (16)0.0377 (5)
C20.69169 (17)0.8273 (3)0.73324 (19)0.0504 (6)
H20.70040.75120.76290.061*
C30.76163 (18)0.8960 (3)0.7087 (2)0.0613 (8)
H30.81690.86470.72060.074*
C40.7501 (2)1.0094 (3)0.6672 (2)0.0647 (9)
H40.79741.05570.65150.078*
C50.6686 (2)1.0548 (3)0.6489 (2)0.0648 (8)
H50.66031.13220.62100.078*
C60.59864 (18)0.9851 (3)0.6720 (2)0.0518 (7)
H60.54351.01620.65880.062*
C70.50000.5641 (3)0.75000.0372 (7)
C80.51067 (16)0.4971 (3)0.67160 (19)0.0461 (6)
H80.51730.53990.61790.055*
C90.51168 (18)0.3672 (3)0.6717 (2)0.0557 (7)
H90.52030.32390.61870.067*
C100.50000.3029 (4)0.75000.0595 (11)
H100.50000.21590.75000.071*
N10.3033 (4)0.9766 (5)1.0723 (4)0.0750 (16)0.50
H10.32071.04681.09500.090*0.50
C110.3619 (5)0.8914 (9)1.0461 (4)0.065 (4)0.50
H110.42030.91011.05300.078*0.50
C120.3361 (4)0.7792 (6)1.0100 (4)0.0548 (14)0.50
H120.37570.72090.99200.066*0.50
C130.2490 (6)0.7552 (8)1.0011 (6)0.0454 (9)0.50
C140.1886 (3)0.8397 (5)1.0268 (4)0.0547 (14)0.50
H140.13020.82151.01990.066*0.50
C150.2171 (6)0.9515 (9)1.0628 (6)0.091 (9)0.50
H150.17781.01041.08080.109*0.50
N20.2210 (3)0.6420 (4)0.9598 (3)0.0512 (11)0.50
C160.2813 (5)0.5487 (7)0.9338 (7)0.059 (6)0.50
H16A0.31260.58030.88500.089*0.50
H16B0.25080.47440.91450.089*0.50
H16C0.32080.52950.98440.089*0.50
C170.1314 (6)0.6173 (12)0.9365 (9)0.077 (4)0.50
H17A0.09980.62390.98970.116*0.50
H17B0.12500.53450.91190.116*0.50
H17C0.10960.67720.89240.116*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.03660 (13)0.03341 (14)0.04972 (15)0.0000.00641 (10)0.000
Br10.05950 (19)0.0641 (2)0.04166 (16)−0.00651 (13)−0.00302 (13)−0.00418 (12)
C10.0366 (12)0.0376 (13)0.0393 (12)−0.0018 (10)0.0044 (10)−0.0026 (10)
C20.0446 (14)0.0523 (17)0.0544 (16)0.0075 (12)0.0036 (12)0.0014 (13)
C30.0356 (14)0.085 (2)0.0640 (19)−0.0006 (14)0.0056 (13)−0.0193 (17)
C40.0598 (19)0.073 (2)0.0630 (19)−0.0290 (17)0.0163 (15)−0.0189 (17)
C50.078 (2)0.0459 (17)0.070 (2)−0.0193 (15)0.0078 (17)0.0074 (15)
C60.0485 (15)0.0409 (15)0.0651 (18)−0.0002 (12)−0.0021 (13)0.0052 (13)
C70.0311 (16)0.0348 (17)0.0456 (19)0.0000.0023 (14)0.000
C80.0429 (14)0.0454 (14)0.0503 (15)−0.0012 (11)0.0056 (11)−0.0031 (12)
C90.0529 (16)0.0472 (16)0.0668 (19)0.0020 (13)0.0029 (14)−0.0157 (14)
C100.055 (2)0.038 (2)0.085 (3)0.000−0.001 (2)0.000
N10.080 (4)0.075 (4)0.070 (3)−0.024 (3)0.002 (3)−0.017 (3)
C110.057 (5)0.077 (7)0.061 (5)−0.010 (5)−0.003 (4)−0.002 (4)
C120.050 (3)0.066 (4)0.049 (3)0.000 (3)0.003 (2)0.004 (3)
C130.051 (2)0.050 (2)0.0354 (18)−0.0006 (18)0.0071 (16)0.0045 (17)
C140.050 (3)0.058 (3)0.057 (3)−0.004 (3)0.009 (3)−0.007 (3)
C150.096 (12)0.091 (12)0.088 (12)−0.004 (8)0.017 (8)−0.006 (8)
N20.061 (3)0.046 (2)0.047 (3)−0.002 (2)0.003 (2)−0.001 (2)
C160.068 (8)0.049 (7)0.061 (8)0.005 (5)0.014 (5)−0.018 (5)
C170.073 (7)0.068 (6)0.088 (6)−0.018 (5)−0.005 (5)−0.006 (5)
Geometric parameters (Å, °) top
Sn1—C12.135 (2)C10—C9i1.372 (4)
Sn1—C1i2.135 (2)C10—H100.9300
Sn1—C72.149 (3)N1—C111.366 (9)
Sn1—Br1i2.7801 (3)N1—C151.369 (9)
Sn1—Br12.7801 (3)N1—H10.8600
C1—C61.375 (4)C11—C121.363 (9)
C1—C21.386 (3)C11—H110.9300
C2—C31.384 (4)C12—C131.379 (9)
C2—H20.9300C12—H120.9300
C3—C41.365 (5)C13—C141.378 (9)
C3—H30.9300C13—N21.412 (8)
C4—C51.371 (5)C14—C151.370 (9)
C4—H40.9300C14—H140.9300
C5—C61.383 (4)C15—H150.9300
C5—H50.9300N2—C161.441 (7)
C6—H60.9300N2—C171.441 (8)
C7—C81.384 (3)C16—H16A0.9600
C7—C8i1.384 (3)C16—H16B0.9600
C8—C91.389 (4)C16—H16C0.9600
C8—H80.9300C17—H17A0.9600
C9—C101.372 (4)C17—H17B0.9600
C9—H90.9300C17—H17C0.9600
C1—Sn1—C1i116.17 (13)C9—C8—C7121.2 (3)
C1—Sn1—C7121.92 (6)C9—C8—H8119.4
C1i—Sn1—C7121.92 (6)C7—C8—H8119.4
C1—Sn1—Br188.61 (6)C10—C9—C8120.0 (3)
C1—Sn1—Br1i90.68 (6)C10—C9—H9120.0
C1i—Sn1—Br1i88.61 (6)C8—C9—H9120.0
C7—Sn1—Br190.68 (1)C9—C10—C9i119.8 (4)
C7—Sn1—Br1i90.68 (1)C9—C10—H10120.1
C1i—Sn1—Br190.68 (6)C9i—C10—H10120.1
Br1—Sn1—Br1i178.64 (2)C11—N1—C15120.8 (7)
C6—C1—C2117.9 (2)C11—N1—H1119.6
C6—C1—Sn1120.98 (18)C15—N1—H1119.6
C2—C1—Sn1121.13 (19)C12—C11—N1120.8 (7)
C3—C2—C1120.6 (3)C12—C11—H11119.6
C3—C2—H2119.7N1—C11—H11119.6
C1—C2—H2119.7C11—C12—C13117.7 (6)
C4—C3—C2120.5 (3)C11—C12—H12121.2
C4—C3—H3119.7C13—C12—H12121.2
C2—C3—H3119.7C14—C13—C12122.6 (7)
C3—C4—C5119.7 (3)C14—C13—N2119.0 (7)
C3—C4—H4120.2C12—C13—N2118.3 (7)
C5—C4—H4120.2C15—C14—C13118.0 (7)
C4—C5—C6119.8 (3)C15—C14—H14121.0
C4—C5—H5120.1C13—C14—H14121.0
C6—C5—H5120.1C14—C15—N1120.1 (7)
C1—C6—C5121.5 (3)C14—C15—H15120.0
C1—C6—H6119.2N1—C15—H15120.0
C5—C6—H6119.2C13—N2—C16121.4 (6)
C8—C7—C8i117.7 (3)C13—N2—C17121.8 (7)
C8—C7—Sn1121.13 (17)C16—N2—C17116.7 (7)
C8i—C7—Sn1121.13 (17)
C1i—Sn1—C1—C6−32.12 (19)C1—Sn1—C7—C8i119.08 (14)
C7—Sn1—C1—C6147.88 (19)C1i—Sn1—C7—C8i−60.92 (14)
Br1i—Sn1—C1—C656.7 (2)Br1i—Sn1—C7—C8i−149.70 (12)
Br1—Sn1—C1—C6−122.2 (2)Br1—Sn1—C7—C8i30.30 (12)
C1i—Sn1—C1—C2146.9 (2)C8i—C7—C8—C9−0.75 (19)
C7—Sn1—C1—C2−33.1 (2)Sn1—C7—C8—C9179.25 (19)
Br1i—Sn1—C1—C2−124.3 (2)C7—C8—C9—C101.5 (4)
Br1—Sn1—C1—C256.9 (2)C8—C9—C10—C9i−0.74 (18)
C6—C1—C2—C3−1.6 (4)C15—N1—C11—C12−0.1 (3)
Sn1—C1—C2—C3179.4 (2)N1—C11—C12—C13−0.1 (3)
C1—C2—C3—C41.8 (5)C11—C12—C13—C140.2 (7)
C2—C3—C4—C5−0.7 (5)C11—C12—C13—N2177.0 (7)
C3—C4—C5—C6−0.4 (5)C12—C13—C14—C15−0.2 (10)
C2—C1—C6—C50.4 (4)N2—C13—C14—C15−177.0 (7)
Sn1—C1—C6—C5179.5 (2)C13—C14—C15—N10.1 (9)
C4—C5—C6—C10.6 (5)C11—N1—C15—C140.1 (7)
C1—Sn1—C7—C8−60.92 (14)C14—C13—N2—C16−178.4 (7)
C1i—Sn1—C7—C8119.08 (14)C12—C13—N2—C164.7 (11)
Br1i—Sn1—C7—C830.30 (12)C14—C13—N2—C175.7 (12)
Br1—Sn1—C7—C8−149.70 (12)C12—C13—N2—C17−171.2 (9)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 1
Selected geometric parameters (Å, °) top
Sn1—C12.135 (2)Sn1—Br12.7801 (3)
Sn1—C72.149 (3)
C1—Sn1—C1i116.17 (13)C1—Sn1—Br1i90.68 (6)
C1—Sn1—C7121.92 (6)C7—Sn1—Br190.68 (1)
C1—Sn1—Br188.61 (6)Br1—Sn1—Br1i178.64 (2)
Symmetry codes: (i) −x+1, y, −z+3/2.
Acknowledgements top

We thank the University of Malaya for funding this study (FR155/2007 A) and also for the purchase of the diffractometer.

references
References top

Aslanov, L. A., Attiya, V. M., Ionov, V. M., Permin, A. B. & Petrosyan, V. S. (1977). Zh. Strukt. Khim. 18, 1113–1118 (in Russian).

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.

Spek, A. L., Wijkens, P. & van Koten, G. (2004). Private communication (refcode CSIGOC). CCDC, Cambridge, England.

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

Wharf, I. & Simard, M. G. (1991). Acta Cryst. C47, 1605–1609.