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Acta Cryst. (2009). E65, m715    [ doi:10.1107/S1600536809019734 ]

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

K. M. Lo and S. W. Ng

Abstract top

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 top

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

Experimental top

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 top

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.

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: pubCIF (Westrip, 2009).

Figures top
[Figure 1] 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.
Bis[4-(dimethylamino)pyridinium] hexakis[bromido/chlorido(0.78/0.22)]stannate(IV) top
Crystal data top
(C7H11N2)2[SnBr4.67Cl1.33]F(000) = 740
Mr = 785.15Dx = 2.277 Mg m−3
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 mm−1
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 top
Bruker SMART APEX
diffractometer		2622 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 top
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 = 0.99 w = 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 Å−3
6 restraintsΔρmin = −0.87 e Å−3
Crystal data top
(C7H11N2)2[SnBr4.67Cl1.33]V = 1145.30 (4) Å3
Mr = 785.15Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.4530 (2) ŵ = 9.42 mm−1
b = 11.9036 (2) ÅT = 100 K
c = 11.9093 (2) Å0.30 × 0.25 × 0.20 mm
β = 107.109 (1)°
Data collection top
Bruker SMART APEX
diffractometer		2622 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2240 reflections with I > 2σ(I)
Tmin = 0.504, Tmax = 0.746Rint = 0.033
10319 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.060Δρmax = 0.80 e Å−3
S = 0.99Δρmin = −0.87 e Å−3
2622 reflectionsAbsolute structure: ?
127 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.88 (1)2.48 (2)3.334 (3)162 (4)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.88 (1)2.48 (2)3.334 (3)162 (4)
Acknowledgements top

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

references
References top

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.

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

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

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

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