Dipyridinium tribromidochloridobis(4-chloro­phen­yl)stannate(IV)

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536809016687

metal-organic compounds

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Volume 65| Part 6| June 2009| Page m630

doi:10.1107/S1600536809016687

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Dipyridinium tribromidochloridobis(4-chlorophenyl)stannate(IV)

Kong Mun Lo ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 4 May 2009; accepted 4 May 2009; online 14 May 2009)

The tin atom in the substituted ammonium stannate(IV), (C₅H₆N)₂[SnBr₃(C₆H₄Cl)₂Cl], lies on a center of symmetry in a distorted octahedral coordination geometry. Each independent halogen site is occupied by bromine and chlorine anions in an approximate 3:1 ratio. The pyridinium cation forms a hydrogen bond to only one of the halogen atoms.

Related literature

For bis(4-dimethylaminopyridinium) tetrahalidodiorganostannates, see: Lo & Ng (2008a ,b ); Yap et al. (2008 ).

Experimental

Crystal data

(C₅H₆N)₂[SnBr₃(C₆H₄Cl)₂Cl]
M_r = 777.17
Monoclinic, C 2/c
a = 11.5130 (2) Å
b = 11.7139 (2) Å
c = 18.7748 (3) Å
β = 93.230 (1)°
V = 2527.99 (7) Å³
Z = 4
Mo Kα radiation
μ = 6.08 mm⁻¹
T = 100 K
0.27 × 0.19 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.327, T_max = 0.529 (expected range = 0.298–0.482)
11728 measured reflections
2903 independent reflections
2668 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.018
wR(F²) = 0.047
S = 1.02
2903 reflections
146 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Table 1
Selected bond lengths (Å) (X = Br, Cl)

Sn1—C1	2.149 (2)
Sn1—X1	2.7166 (2)
Sn1—X2	2.7060 (2)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016687/bt2945sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016687/bt2945Isup2.hkl

checkCIF report

Related literature top

For bis(4-dimethylaminopyridinium) tetrahalidodiorganostannates, see: Lo & Ng (2008a,b); Yap et al. (2008).

Experimental top

Bis(4-chlorophenyl)tin dichloride (0.40 g, 1 mol) and pyridine hydrobromide perbromide (0.64 g, 2 mmol) were heated in chloroform for 3 h. Crystals separated from the cool solution after a day.

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

Fig. 1. 70% Probability anisotropic displacement ellipsoid plot of the ion-pair 2(C₅H₆ N) [SnBr₃Cl(C₆H₄Cl)₂]. Hydrogen atoms are drawn as spheres of arbitrary radius. Dashed lines denote hydrogen bonds. The tin-bound halogen atoms are disordered.

Dipyridinium tribromidochloridobis(4-chlorophenyl)stannate(IV) top

Crystal data top

(C₅H₆N)₂[SnBr₃(C₆H₄Cl)₂Cl]	F(000) = 1488
M_r = 777.17	D_x = 2.042 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6664 reflections
a = 11.5130 (2) Å	θ = 2.5–28.3°
b = 11.7139 (2) Å	µ = 6.08 mm⁻¹
c = 18.7748 (3) Å	T = 100 K
β = 93.230 (1)°	Prism, brown
V = 2527.99 (7) Å³	0.27 × 0.19 × 0.12 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	2903 independent reflections
Radiation source: fine-focus sealed tube	2668 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.327, T_max = 0.529	k = −15→15
11728 measured reflections	l = −23→24

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.047	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0246P)² + 3.4843P] where P = (F_o² + 2F_c²)/3
2903 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.39 e Å⁻³
4 restraints	Δρ_min = −0.84 e Å⁻³

Crystal data top

(C₅H₆N)₂[SnBr₃(C₆H₄Cl)₂Cl]	V = 2527.99 (7) Å³
M_r = 777.17	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 11.5130 (2) Å	µ = 6.08 mm⁻¹
b = 11.7139 (2) Å	T = 100 K
c = 18.7748 (3) Å	0.27 × 0.19 × 0.12 mm
β = 93.230 (1)°

Data collection top

Bruker SMART APEX diffractometer	2903 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2668 reflections with I > 2σ(I)
T_min = 0.327, T_max = 0.529	R_int = 0.022
11728 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	4 restraints
wR(F²) = 0.047	H-atom parameters constrained
S = 1.02	Δρ_max = 0.39 e Å⁻³
2903 reflections	Δρ_min = −0.84 e Å⁻³
146 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sn1	0.5000	0.5000	0.5000	0.01196 (6)
Br1	0.308690 (19)	0.509165 (19)	0.578153 (12)	0.01383 (8)	0.7365 (11)
Br2	0.551744 (19)	0.288797 (18)	0.550827 (12)	0.01450 (7)	0.7635 (11)
Cl1'	0.308690 (19)	0.509165 (19)	0.578153 (12)	0.01383 (8)	0.2635 (11)
Cl2'	0.551744 (19)	0.288797 (18)	0.550827 (12)	0.01450 (7)	0.2365 (11)
Cl1	0.83429 (5)	0.71755 (5)	0.76748 (3)	0.02688 (12)
N1	0.15868 (16)	0.59124 (16)	0.43101 (10)	0.0217 (4)
H1	0.2206	0.5891	0.4607	0.026*
C1	0.60325 (16)	0.57206 (16)	0.58772 (10)	0.0129 (4)
C2	0.60187 (18)	0.52532 (17)	0.65598 (11)	0.0165 (4)
H2	0.5522	0.4626	0.6644	0.020*
C3	0.67258 (18)	0.56972 (18)	0.71184 (11)	0.0188 (4)
H3	0.6716	0.5379	0.7584	0.023*
C4	0.74442 (17)	0.66121 (18)	0.69830 (11)	0.0182 (4)
C5	0.74654 (17)	0.70998 (17)	0.63157 (11)	0.0171 (4)
H5	0.7961	0.7729	0.6234	0.021*
C6	0.67469 (17)	0.66515 (17)	0.57641 (11)	0.0155 (4)
H6	0.6745	0.6987	0.5303	0.019*
C7	0.0884 (2)	0.50083 (18)	0.42776 (13)	0.0225 (5)
H7	0.1048	0.4366	0.4575	0.027*
C8	−0.0077 (2)	0.50100 (18)	0.38125 (13)	0.0235 (5)
H8	−0.0579	0.4366	0.3777	0.028*
C9	−0.03042 (19)	0.5968 (2)	0.33953 (12)	0.0238 (5)
H9	−0.0971	0.5988	0.3074	0.029*
C10	0.0440 (2)	0.68937 (19)	0.34465 (12)	0.0231 (5)
H10	0.0290	0.7552	0.3161	0.028*
C11	0.13982 (19)	0.68517 (19)	0.39135 (12)	0.0224 (5)
H11	0.1920	0.7479	0.3955	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01296 (10)	0.01329 (10)	0.00948 (10)	−0.00098 (6)	−0.00070 (7)	0.00034 (7)
Br1	0.01297 (12)	0.01610 (12)	0.01249 (13)	−0.00044 (8)	0.00142 (9)	0.00093 (8)
Br2	0.01749 (12)	0.01242 (11)	0.01334 (12)	0.00098 (8)	−0.00136 (8)	0.00188 (8)
Cl1'	0.01297 (12)	0.01610 (12)	0.01249 (13)	−0.00044 (8)	0.00142 (9)	0.00093 (8)
Cl2'	0.01749 (12)	0.01242 (11)	0.01334 (12)	0.00098 (8)	−0.00136 (8)	0.00188 (8)
Cl1	0.0254 (3)	0.0349 (3)	0.0193 (3)	−0.0073 (2)	−0.0073 (2)	−0.0056 (2)
N1	0.0177 (9)	0.0277 (10)	0.0190 (9)	0.0050 (7)	−0.0038 (7)	−0.0047 (8)
C1	0.0126 (9)	0.0155 (9)	0.0103 (9)	0.0020 (7)	−0.0011 (7)	−0.0014 (7)
C2	0.0160 (9)	0.0177 (9)	0.0156 (10)	−0.0017 (7)	0.0004 (8)	−0.0001 (8)
C3	0.0221 (10)	0.0222 (10)	0.0119 (9)	0.0010 (8)	−0.0016 (8)	0.0022 (8)
C4	0.0153 (10)	0.0237 (10)	0.0150 (10)	0.0002 (8)	−0.0041 (8)	−0.0054 (8)
C5	0.0155 (9)	0.0170 (9)	0.0188 (10)	−0.0028 (7)	0.0002 (8)	−0.0013 (8)
C6	0.0154 (9)	0.0170 (9)	0.0142 (10)	0.0012 (7)	0.0018 (7)	0.0010 (8)
C7	0.0251 (12)	0.0223 (11)	0.0204 (12)	0.0064 (8)	0.0055 (9)	0.0023 (9)
C8	0.0194 (11)	0.0239 (11)	0.0276 (13)	−0.0015 (8)	0.0062 (9)	−0.0024 (9)
C9	0.0173 (10)	0.0332 (12)	0.0204 (11)	0.0049 (9)	−0.0028 (8)	−0.0028 (9)
C10	0.0280 (11)	0.0214 (10)	0.0201 (11)	0.0058 (9)	0.0029 (9)	0.0019 (9)
C11	0.0251 (11)	0.0196 (10)	0.0225 (11)	−0.0018 (8)	0.0034 (9)	−0.0048 (9)

Geometric parameters (Å, º) top

Sn1—C1ⁱ	2.149 (2)	C3—C4	1.386 (3)
Sn1—C1	2.149 (2)	C3—H3	0.9500
Sn1—Br1	2.7166 (2)	C4—C5	1.378 (3)
Sn1—Cl2'ⁱ	2.7060 (2)	C5—C6	1.391 (3)
Sn1—Br2ⁱ	2.7060 (2)	C5—H5	0.9500
Sn1—Br2	2.7060 (2)	C6—H6	0.9500
Sn1—Cl1'ⁱ	2.7166 (2)	C7—C8	1.370 (3)
Sn1—Br1ⁱ	2.7166 (2)	C7—H7	0.9500
Cl1—C4	1.744 (2)	C8—C9	1.384 (3)
N1—C7	1.332 (3)	C8—H8	0.9500
N1—C11	1.339 (3)	C9—C10	1.383 (3)
N1—H1	0.8800	C9—H9	0.9500
C1—C6	1.389 (3)	C10—C11	1.371 (3)
C1—C2	1.394 (3)	C10—H10	0.9500
C2—C3	1.392 (3)	C11—H11	0.9500
C2—H2	0.9500

C1ⁱ—Sn1—C1	180.000 (1)	C6—C1—Sn1	119.86 (14)
C1ⁱ—Sn1—Cl2'ⁱ	89.29 (5)	C2—C1—Sn1	121.05 (14)
C1—Sn1—Cl2'ⁱ	90.71 (5)	C3—C2—C1	120.63 (19)
C1ⁱ—Sn1—Br2ⁱ	89.29 (5)	C3—C2—H2	119.7
C1—Sn1—Br2ⁱ	90.71 (5)	C1—C2—H2	119.7
Cl2'ⁱ—Sn1—Br2ⁱ	0.000 (13)	C4—C3—C2	118.71 (19)
C1ⁱ—Sn1—Br2	90.71 (5)	C4—C3—H3	120.6
C1—Sn1—Br2	89.29 (5)	C2—C3—H3	120.6
Cl2'ⁱ—Sn1—Br2	180.0	C5—C4—C3	121.90 (19)
Br2ⁱ—Sn1—Br2	180.0	C5—C4—Cl1	118.68 (16)
C1ⁱ—Sn1—Cl1'ⁱ	90.05 (5)	C3—C4—Cl1	119.41 (17)
C1—Sn1—Cl1'ⁱ	89.95 (5)	C4—C5—C6	118.67 (19)
Cl2'ⁱ—Sn1—Cl1'ⁱ	90.845 (7)	C4—C5—H5	120.7
Br2ⁱ—Sn1—Cl1'ⁱ	90.845 (7)	C6—C5—H5	120.7
Br2—Sn1—Cl1'ⁱ	89.155 (7)	C5—C6—C1	120.98 (19)
C1ⁱ—Sn1—Br1ⁱ	90.05 (5)	C5—C6—H6	119.5
C1—Sn1—Br1ⁱ	89.95 (5)	C1—C6—H6	119.5
Cl2'ⁱ—Sn1—Br1ⁱ	90.845 (7)	N1—C7—C8	119.7 (2)
Br2ⁱ—Sn1—Br1ⁱ	90.845 (7)	N1—C7—H7	120.2
Br2—Sn1—Br1ⁱ	89.155 (7)	C8—C7—H7	120.2
Cl1'ⁱ—Sn1—Br1ⁱ	0.000 (8)	C7—C8—C9	118.8 (2)
C1ⁱ—Sn1—Br1	89.95 (5)	C7—C8—H8	120.6
C1—Sn1—Br1	90.05 (5)	C9—C8—H8	120.6
Cl2'ⁱ—Sn1—Br1	89.155 (7)	C8—C9—C10	120.0 (2)
Br2ⁱ—Sn1—Br1	89.155 (7)	C8—C9—H9	120.0
Br2—Sn1—Br1	90.845 (7)	C10—C9—H9	120.0
Cl1'ⁱ—Sn1—Br1	180.0	C11—C10—C9	119.3 (2)
Br1ⁱ—Sn1—Br1	180.0	C11—C10—H10	120.3
C7—N1—C11	123.26 (19)	C9—C10—H10	120.3
C7—N1—H1	118.4	N1—C11—C10	119.0 (2)
C11—N1—H1	118.4	N1—C11—H11	120.5
C6—C1—C2	119.08 (18)	C10—C11—H11	120.5

Cl2'ⁱ—Sn1—C1—C6	−40.72 (15)	C1—C2—C3—C4	−0.1 (3)
Br2ⁱ—Sn1—C1—C6	−40.72 (15)	C2—C3—C4—C5	0.9 (3)
Br2—Sn1—C1—C6	139.28 (15)	C2—C3—C4—Cl1	−179.64 (16)
Cl1'ⁱ—Sn1—C1—C6	50.12 (15)	C3—C4—C5—C6	−0.4 (3)
Br1ⁱ—Sn1—C1—C6	50.12 (15)	Cl1—C4—C5—C6	−179.89 (15)
Br1—Sn1—C1—C6	−129.88 (15)	C4—C5—C6—C1	−0.9 (3)
Cl2'ⁱ—Sn1—C1—C2	140.70 (15)	C2—C1—C6—C5	1.7 (3)
Br2ⁱ—Sn1—C1—C2	140.70 (15)	Sn1—C1—C6—C5	−176.91 (15)
Br2—Sn1—C1—C2	−39.30 (15)	C11—N1—C7—C8	1.0 (3)
Cl1'ⁱ—Sn1—C1—C2	−128.46 (15)	N1—C7—C8—C9	−1.2 (3)
Br1ⁱ—Sn1—C1—C2	−128.46 (15)	C7—C8—C9—C10	0.8 (3)
Br1—Sn1—C1—C2	51.54 (15)	C8—C9—C10—C11	−0.1 (3)
C6—C1—C2—C3	−1.2 (3)	C7—N1—C11—C10	−0.3 (3)
Sn1—C1—C2—C3	177.39 (15)	C9—C10—C11—N1	−0.1 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.88	2.55	3.317 (2)	146

Experimental details

Crystal data
Chemical formula	(C₅H₆N)₂[SnBr₃(C₆H₄Cl)₂Cl]
M_r	777.17
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	11.5130 (2), 11.7139 (2), 18.7748 (3)
β (°)	93.230 (1)
V (Å³)	2527.99 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.08
Crystal size (mm)	0.27 × 0.19 × 0.12

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.327, 0.529
No. of measured, independent and observed [I > 2σ(I)] reflections	11728, 2903, 2668
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.047, 1.02
No. of reflections	2903
No. of parameters	146
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.84

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Selected bond lengths (Å) top

Sn1—C1	2.149 (2)	Sn1—Br2	2.7060 (2)
Sn1—Br1	2.7166 (2)

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lo, K. M. & Ng, S. W. (2008a). Acta Cryst. E64, m800. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lo, K. M. & Ng, S. W. (2008b). Acta Cryst. E64, m834. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Yap, Q. L., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m696. Web of Science CSD CrossRef IUCr Journals Google Scholar