Dipyridinium tribromidochloridobis(4-chloro­phen­yl)stannate(IV)

Abstract

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,

• a = 11.5130 (2) Å

• b = 11.7139 (2) Å

• c = 18.7748 (3) Å

• β = 93.230 (1)°

• V = 2527.99 (7) ų

• 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[F ² > 2σ(F ²)] = 0.018

• wR(F ²) = 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

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

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

supplementary crystallographic information

Experimental

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.

Refinement

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).

Each of the two independent tin-bound halogen atoms is a mixture of chlorine and bromine; as the total occupancy of chlorine refined to nearly 0.5 and that of bromine to nearly 1.5, these values were fixed as 0.5 and 1.5. Furthermore, the different halogen atoms sharing the same site were constrained to have the same coordinates and the same anisotropic displacement parameters. The final difference Fourier map did not have large peaks/deep holes near the disordered atoms.

Figures

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.

Crystal data

(C5H6N)2[SnBr3(C6H4Cl)2Cl]	F(000) = 1488
Mr = 777.17	Dx = 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

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

Refinement

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(Fo2) + (0.0246P)2 + 3.4843P] where P = (Fo2 + 2Fc2)/3
2903 reflections	(Δ/σ)max = 0.001
146 parameters	Δρmax = 0.39 e Å−3
4 restraints	Δρmin = −0.83 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

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