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Acta Cryst. (2009). E65, m663    [ doi:10.1107/S1600536809017590 ]

Bis[4-(dimethylamino)pyridinium] tetrabromidobis(3,4-dichlorophenyl)stannate(IV)-1-bromo-3,4-dichlorobenzene (1/1)

Y. C. Koon, K. M. Lo and S. W. Ng

Abstract top

The Sn atom in the title substituted pyridinium stannate bromo-3,4-dichlorobenzene solvate, (C7H11N2)2[SnBr4(C6H3Cl2)2]·C6H3BrCl2, lies on a twofold axis within an octahedral C2Br4 donor set. Each cation forms an N-H...Br hydrogen bond to one of the Br atoms of the anion. The solvent molecule is disordered about the twofold rotation axis with equal occupancy. The crystal under investigation was non-merohedrally twinned, with a twin component ratio of 0.76:0.24.

Related literature top

For bis(4-dimethylaminopyridinium) tetrahalidodiorganostannates, see: Lo & Ng (2008a,b); Yap et al. (2008). For deconvolution of the diffraction data, see: Spek (2009).

Experimental top

Tetrakis(3,4-dichlorophenyl)tin (0.70 g, 1 mol) and 4-dimethylaminopyridine hydrobromide perbromide (0.73 g, 2 mmol) were heated in ethanol/chloroform (1:1 v/v, 100 ml) for 3 h. Crystals separated from the cool solution after a day.

The presence of bromo-3,4-dichlorobenzene in the crystal structure probably arose from contamination of the tetrakis(3,4-dichlorophenyl)tin reactant, which itself was synthesized in a Grignard reaction with bromo-3,4-dichlorobenzene as the starting halogen-bearing compound.

Refinement top

The structure initially refined to 7.7%. PLATON (Spek, 2009) gave the twin law as (1 0 0.746, 0 - 1 0, 0 0 - 1); a new hkl file was generated by using the detwinning tool in the program.

The aromatic and pyridyl rings were refined as rigid hexagons of 1.39 Å sides. For the lattice solvent molecule, which is situated about a 2-fold axis, the C–Cl distance was restrained to 1.74±0.01 Å and the C–Br distance to 1.90±0.01 Å. The molecule was allowed to refine off the 2-fold rotation axis. The anisotropic displacement factors of the carbon atoms were restrained to be nearly isotropic.

SHELXL-97 suggested an unusually large values for a and b in the weighting scheme, and so the suggested scheme was not used. Instead, an arbitrary value of a = 0.15 was used which gave a statisfactory Goodness-of-Fit of about 1.5.

Hydrogen atoms were placed in calculated positions (C—H 0.95, N–H 0.88 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C,N). The torsion angles of the methyl groups were refined.

The final difference Fourier map had a large peak at 1.3 Å from H7 and a deep hole at 1.5 Å from H15.

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, 2009).

Figures top
[Figure 1] Fig. 1. 70% Probability thermal ellipsoid plot of the ion-pair (C7H11N2)2 [SnBr4(C6H3Cl2)2].C6H3BrCl2. Unlabelled atoms are related by a 2-fold axis. Hydrogen atoms are drawn as spheres of arbitrary radius.
Bis[4-(dimethylamino)pyridinium] tetrabromidobis(3,4-dichlorophenyl)stannate(IV)–1-bromo-3,4-dichlorobenzene (1/1) top
Crystal data top
(C7H11N2)2[SnBr4(C6H3Cl2)2]·C6H3BrCl2F000 = 2312
Mr = 1202.55Dx = 2.022 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9914 reflections
a = 19.2308 (2) Åθ = 2.2–28.4º
b = 13.8983 (2) ŵ = 6.14 mm−1
c = 15.4961 (2) ÅT = 100 K
β = 107.491 (1)ºBlock, colorless
V = 3950.23 (9) Å30.25 × 0.20 × 0.15 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		4495 independent reflections
Radiation source: fine-focus sealed tube4061 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 100 Kθmax = 27.5º
ω scansθmin = 1.8º
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		h = −24→24
Tmin = 0.309, Tmax = 0.459k = −18→18
17636 measured reflectionsl = −20→20
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)] = 0.050H-atom parameters constrained
wR(F2) = 0.243  w = 1/[σ2(Fo2) + (0.15P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.47(Δ/σ)max = 0.001
4495 reflectionsΔρmax = 2.01 e Å−3
225 parametersΔρmin = −1.80 e Å−3
39 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C7H11N2)2[SnBr4(C6H3Cl2)2]·C6H3BrCl2V = 3950.23 (9) Å3
Mr = 1202.55Z = 4
Monoclinic, C2/cMo Kα
a = 19.2308 (2) ŵ = 6.14 mm−1
b = 13.8983 (2) ÅT = 100 K
c = 15.4961 (2) Å0.25 × 0.20 × 0.15 mm
β = 107.491 (1)º
Data collection top
Bruker SMART APEX
diffractometer		4495 independent reflections
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		4061 reflections with I > 2σ(I)
Tmin = 0.309, Tmax = 0.459Rint = 0.030
17636 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05039 restraints
wR(F2) = 0.243H-atom parameters constrained
S = 1.47Δρmax = 2.01 e Å−3
4495 reflectionsΔρmin = −1.80 e Å−3
225 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.50000.61725 (3)0.75000.0092 (2)
Br20.44267 (3)0.48127 (5)0.62311 (4)0.0174 (2)
Br10.44630 (3)0.75638 (5)0.62507 (4)0.0186 (2)
Cl10.81264 (8)0.62573 (10)0.85386 (12)0.0179 (4)
Cl20.81408 (10)0.62116 (11)0.65044 (13)0.0243 (4)
N20.2115 (3)0.6236 (4)0.1836 (4)0.0196 (12)
C10.60066 (16)0.6174 (2)0.7153 (3)0.0102 (11)
C20.6660 (2)0.6216 (2)0.7850 (2)0.0102 (11)
H20.66570.62380.84610.012*
C30.73187 (16)0.6224 (2)0.7651 (2)0.0138 (12)
C40.73233 (17)0.6191 (3)0.6756 (3)0.0155 (13)
C50.6670 (2)0.6150 (3)0.6060 (2)0.0151 (13)
H50.66730.61280.54490.018*
C60.60113 (17)0.6142 (2)0.6259 (2)0.0175 (13)
H60.55640.61130.57830.021*
N10.3539 (2)0.6345 (3)0.4428 (2)0.0293 (14)
H10.38420.63710.49810.035*
C70.38080 (17)0.6245 (3)0.3695 (3)0.0244 (16)
H70.43190.62050.37900.029*
C80.3330 (2)0.6204 (3)0.2822 (3)0.0185 (14)
H80.35140.61350.23200.022*
C90.2582 (2)0.6262 (3)0.2682 (2)0.0144 (12)
C100.23132 (17)0.6362 (3)0.3415 (3)0.0185 (13)
H100.18020.64010.33200.022*
C110.2791 (2)0.6403 (3)0.4288 (2)0.0239 (14)
H110.26080.64710.47900.029*
C120.2386 (5)0.6177 (5)0.1057 (5)0.0273 (17)
H12A0.26950.67370.10500.041*
H12B0.19740.61680.05010.041*
H12C0.26720.55870.10950.041*
C130.1323 (4)0.6238 (5)0.1685 (6)0.0268 (17)
H13A0.11960.57270.20470.040*
H13B0.10710.61260.10430.040*
H13C0.11750.68620.18660.040*
Br30.5258 (5)0.7963 (5)0.4343 (4)0.0355 (11)0.50
Cl30.4624 (2)0.9970 (3)0.0505 (2)0.0351 (9)0.50
Cl40.4620 (14)0.7751 (14)0.0633 (11)0.038 (3)0.50
C140.5139 (16)0.8551 (8)0.3234 (8)0.027 (4)0.50
C150.501 (2)0.7983 (4)0.2464 (11)0.027 (3)0.50
H150.50330.73020.25170.032*0.50
C160.4852 (16)0.8411 (7)0.1616 (9)0.025 (4)0.50
C170.4820 (8)0.9408 (8)0.1538 (4)0.023 (4)0.50
C180.4948 (9)0.9976 (4)0.2309 (6)0.023 (4)0.50
H180.49261.06570.22550.028*0.50
C190.5107 (8)0.9548 (8)0.3156 (4)0.021 (3)0.50
H190.51940.99360.36830.025*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0068 (4)0.0113 (4)0.0099 (3)0.0000.0031 (2)0.000
Br20.0141 (4)0.0186 (4)0.0195 (4)−0.0016 (2)0.0048 (3)−0.0054 (2)
Br10.0175 (4)0.0215 (4)0.0169 (4)0.0013 (2)0.0050 (3)0.0030 (2)
Cl10.0082 (7)0.0195 (8)0.0236 (8)0.0003 (5)0.0010 (6)−0.0001 (5)
Cl20.0133 (8)0.0351 (10)0.0291 (9)−0.0020 (5)0.0132 (7)−0.0020 (6)
N20.019 (3)0.019 (3)0.018 (3)0.0001 (18)0.001 (2)0.0001 (19)
C10.011 (3)0.009 (3)0.011 (3)0.0016 (17)0.003 (2)0.0001 (17)
C20.007 (3)0.014 (3)0.010 (3)0.0001 (17)0.003 (2)−0.0007 (18)
C30.008 (3)0.014 (3)0.019 (3)−0.0021 (18)0.004 (2)−0.001 (2)
C40.008 (3)0.015 (3)0.026 (4)−0.0011 (18)0.008 (3)0.000 (2)
C50.016 (3)0.017 (3)0.014 (3)−0.003 (2)0.007 (2)−0.002 (2)
C60.018 (3)0.019 (3)0.016 (3)−0.002 (2)0.006 (3)−0.002 (2)
N10.027 (4)0.033 (3)0.018 (3)0.008 (2)−0.007 (3)−0.007 (2)
C70.016 (3)0.018 (3)0.033 (4)0.003 (2)−0.002 (3)−0.006 (3)
C80.016 (3)0.016 (3)0.023 (3)0.001 (2)0.007 (3)−0.002 (2)
C90.017 (3)0.012 (3)0.014 (3)−0.002 (2)0.003 (2)−0.0018 (19)
C100.015 (3)0.013 (3)0.027 (3)0.000 (2)0.006 (3)0.001 (2)
C110.033 (4)0.026 (3)0.012 (3)0.008 (3)0.007 (3)−0.002 (3)
C120.036 (5)0.031 (4)0.011 (3)0.001 (3)0.001 (3)0.001 (2)
C130.013 (4)0.032 (4)0.030 (4)0.001 (2)−0.002 (3)−0.004 (3)
Br30.050 (3)0.036 (3)0.0186 (11)−0.0140 (19)0.0077 (13)−0.0007 (11)
Cl30.049 (2)0.0289 (19)0.0208 (16)−0.0123 (16)−0.0002 (15)0.0031 (14)
Cl40.047 (7)0.039 (8)0.026 (3)0.008 (4)0.009 (3)−0.003 (3)
C140.030 (8)0.036 (7)0.017 (6)−0.012 (7)0.012 (6)0.003 (6)
C150.028 (5)0.024 (5)0.032 (5)0.003 (9)0.014 (4)−0.008 (9)
C160.018 (7)0.039 (8)0.027 (6)0.014 (6)0.018 (6)0.001 (6)
C170.024 (6)0.028 (7)0.020 (7)−0.007 (5)0.012 (5)−0.009 (6)
C180.026 (6)0.025 (5)0.019 (9)0.003 (5)0.007 (7)0.000 (4)
C190.022 (6)0.022 (6)0.023 (7)−0.007 (5)0.015 (6)0.000 (6)
Geometric parameters (Å, °) top
Sn1—C1i2.159 (3)C8—C91.3900
Sn1—C12.159 (3)C8—H80.9500
Sn1—Br22.7111 (7)C9—C101.3900
Sn1—Br2i2.7111 (7)C10—C111.3900
Sn1—Br1i2.7114 (7)C10—H100.9500
Sn1—Br12.7114 (7)C11—H110.9500
Cl1—C31.739 (3)C12—H12A0.9800
Cl2—C41.730 (3)C12—H12B0.9800
N2—C91.349 (7)C12—H12C0.9800
N2—C121.454 (10)C13—H13A0.9800
N2—C131.468 (10)C13—H13B0.9800
C1—C21.3900C13—H13C0.9800
C1—C61.3900Br3—C141.855 (6)
C2—C31.3900Cl3—C171.719 (7)
C2—H20.9500Cl4—C161.718 (9)
C3—C41.3900C14—C151.3900
C4—C51.3900C14—C191.3900
C5—C61.3900C15—C161.3900
C5—H50.9500C15—H150.9500
C6—H60.9500C16—C171.3900
N1—C71.3900C17—C181.3900
N1—C111.3900C18—C191.3900
N1—H10.8800C18—H180.9500
C7—C81.3900C19—H190.9500
C7—H70.9500
C1i—Sn1—C1179.87 (18)C7—C8—C9120.0
C1i—Sn1—Br288.95 (10)C7—C8—H8120.0
C1—Sn1—Br291.15 (10)C9—C8—H8120.0
C1i—Sn1—Br2i91.15 (10)N2—C9—C8120.4 (4)
C1—Sn1—Br2i88.95 (10)N2—C9—C10119.6 (4)
Br2—Sn1—Br2i91.62 (3)C8—C9—C10120.0
C1i—Sn1—Br1i89.95 (10)C11—C10—C9120.0
C1—Sn1—Br1i89.95 (10)C11—C10—H10120.0
Br2—Sn1—Br1i178.301 (19)C9—C10—H10120.0
Br2i—Sn1—Br1i89.70 (2)C10—C11—N1120.0
C1i—Sn1—Br189.95 (10)C10—C11—H11120.0
C1—Sn1—Br189.95 (10)N1—C11—H11120.0
Br2—Sn1—Br189.70 (2)N2—C12—H12A109.5
Br2i—Sn1—Br1178.301 (19)N2—C12—H12B109.5
Br1i—Sn1—Br189.01 (3)H12A—C12—H12B109.5
C9—N2—C12120.5 (6)N2—C12—H12C109.5
C9—N2—C13120.7 (6)H12A—C12—H12C109.5
C12—N2—C13118.8 (6)H12B—C12—H12C109.5
C2—C1—C6120.0N2—C13—H13A109.5
C2—C1—Sn1118.5 (2)N2—C13—H13B109.5
C6—C1—Sn1121.5 (2)H13A—C13—H13B109.5
C3—C2—C1120.0N2—C13—H13C109.5
C3—C2—H2120.0H13A—C13—H13C109.5
C1—C2—H2120.0H13B—C13—H13C109.5
C2—C3—C4120.0C15—C14—C19120.0
C2—C3—Cl1118.8 (2)C15—C14—Br3119.1 (9)
C4—C3—Cl1121.2 (2)C19—C14—Br3120.6 (9)
C5—C4—C3120.0C16—C15—C14120.0
C5—C4—Cl2119.8 (2)C16—C15—H15120.0
C3—C4—Cl2120.2 (2)C14—C15—H15120.0
C4—C5—C6120.0C15—C16—C17120.0
C4—C5—H5120.0C15—C16—Cl4122.3 (11)
C6—C5—H5120.0C17—C16—Cl4117.6 (11)
C5—C6—C1120.0C18—C17—C16120.0
C5—C6—H6120.0C18—C17—Cl3118.3 (8)
C1—C6—H6120.0C16—C17—Cl3121.7 (8)
C7—N1—C11120.0C17—C18—C19120.0
C7—N1—H1120.0C17—C18—H18120.0
C11—N1—H1120.0C19—C18—H18120.0
C8—C7—N1120.0C18—C19—C14120.0
C8—C7—H7120.0C18—C19—H19120.0
N1—C7—H7120.0C14—C19—H19120.0
Br2—Sn1—C1—C2−138.45 (15)C12—N2—C9—C8−1.9 (6)
Br2i—Sn1—C1—C2−46.86 (16)C13—N2—C9—C8176.2 (4)
Br1i—Sn1—C1—C242.84 (16)C12—N2—C9—C10177.2 (4)
Br1—Sn1—C1—C2131.85 (16)C13—N2—C9—C10−4.7 (6)
Br2—Sn1—C1—C641.96 (17)C7—C8—C9—N2179.0 (4)
Br2i—Sn1—C1—C6133.56 (17)C7—C8—C9—C100.0
Br1i—Sn1—C1—C6−136.74 (17)N2—C9—C10—C11−179.0 (4)
Br1—Sn1—C1—C6−47.73 (17)C8—C9—C10—C110.0
C6—C1—C2—C30.0C9—C10—C11—N10.0
Sn1—C1—C2—C3−179.6 (2)C7—N1—C11—C100.0
C1—C2—C3—C40.0C19—C14—C15—C160.0
C1—C2—C3—Cl1−179.0 (2)Br3—C14—C15—C16173.9 (18)
C2—C3—C4—C50.0C14—C15—C16—C170.0
Cl1—C3—C4—C5179.0 (3)C14—C15—C16—Cl4−175 (2)
C2—C3—C4—Cl2179.5 (3)C15—C16—C17—C180.0
Cl1—C3—C4—Cl2−1.5 (3)Cl4—C16—C17—C18175.1 (19)
C3—C4—C5—C60.0C15—C16—C17—Cl3−179.9 (11)
Cl2—C4—C5—C6−179.5 (3)Cl4—C16—C17—Cl3−5(2)
C4—C5—C6—C10.0C16—C17—C18—C190.0
C2—C1—C6—C50.0Cl3—C17—C18—C19179.9 (10)
Sn1—C1—C6—C5179.6 (2)C17—C18—C19—C140.0
C11—N1—C7—C80.0C15—C14—C19—C180.0
N1—C7—C8—C90.0Br3—C14—C19—C18−173.8 (18)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.583.315 (3)142
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.583.315 (3)142
Acknowledgements top

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

references
References top

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Lo, K. M. & Ng, S. W. (2008b). Acta Cryst. E64, m834.

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

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Westrip, S. P. (2009). publCIF. In preparation.

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