Bis[4-(dimethyl­amino)pyridinium] tetra­bromidodiphenyl­stannate(IV)

Yap, Q.L.; Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536808010830

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m696

doi:10.1107/S1600536808010830

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Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylstannate(IV)

Quai Ling Yap,^a 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 7 April 2008; accepted 18 April 2008; online 23 April 2008)

The Sn^IV atom of the stannate anion in the title salt, (C₇H₁₁N₂)₂[SnBr₄(C₆H₅)₂], lies on a center of inversion in a tetragonally compressed octahedron. The two independent Br atoms in the anion are hydrogen-bond acceptors for the same cation.

Related literature

For the structure of dipyridinium tetrabromidostannate(II), see: Tuleda & Khan (1991 ).

Experimental

Crystal data

(C₇H₁₁N₂)₂[SnBr₄(C₆H₅)₂]
M_r = 838.89
Monoclinic, P 2₁ /n
a = 10.7803 (2) Å
b = 9.3847 (2) Å
c = 14.4068 (4) Å
β = 94.126 (2)°
V = 1453.76 (6) Å³
Z = 2
Mo Kα radiation
μ = 6.40 mm⁻¹
T = 100 (2) K
0.24 × 0.18 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.386, T_max = 0.514 (expected range = 0.348–0.464)
11853 measured reflections
3334 independent reflections
2688 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.051
S = 0.99
3334 reflections
166 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Sn1—C1	2.143 (3)
Sn1—Br1	2.7395 (2)
Sn1—Br2	2.7470 (3)

C1—Sn1—Br1	90.53 (7)
C1—Sn1—Br1ⁱ	89.47 (7)
C1—Sn1—Br2	89.64 (7)
C1—Sn1—Br2ⁱ	90.36 (7)
Br1—Sn1—Br2	88.981 (8)
Br1—Sn1—Br2ⁱ	91.019 (8)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯Br1	0.88 (1)	2.79 (3)	3.385 (3)	126 (3)
N2—H2N⋯Br2	0.88 (1)	2.81 (3)	3.485 (3)	135 (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, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010830/tk2264sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010830/tk2264Isup2.hkl

checkCIF report

Comment top

Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylstannate(IV), (I) (Fig. 1 and Table 1) was the product of the cleavage of the mixed alkyl/triarylstannate, cyclopentyltriphenyltin, by 4-dimethylaminopyridine hydrobromide perbromide. The stannate has the tin atom in a tetragonally compressed octahedral Br₄C₂ environment. The anion has also been reported as the centrosymmetric pyridinium salt: Sn–Br = 2.7592 (3), 2.7737 (3) and Sn–C 2.158 (3) Å (Tuleda & Khan, 1991). Connections between ions are of the type N-H···Br (Table 2) so that each independent pair of bromide atoms are linked to the same cation.

Related literature top

For the structure of dipyridinium tetrabromidostannate, see: Tuleda & Khan (1991).

Experimental top

Cyclopentyltriphenyltin (1.36 g, 3 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (1.1 g, 3 mmol) were heated in chloroform (100 ml) for 3 h. The filtered solution when allowed to evaporate yielded large yellow crystals, m.p. 470–473 K.

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

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) plot of [C₇H₁₁N]₂ [SnBr₄(C₆H₅)₂] at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

Bis[4-(dimethylamino)pyridinium] tetrabromidodiphenylstannate(IV) top

Crystal data top

(C₇H₁₁N₂)₂[SnBr₄(C₆H₅)₂]	F(000) = 812
M_r = 838.89	D_x = 1.916 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3449 reflections
a = 10.7803 (2) Å	θ = 2.3–28.3°
b = 9.3847 (2) Å	µ = 6.40 mm⁻¹
c = 14.4068 (4) Å	T = 100 K
β = 94.126 (2)°	Block, colorless
V = 1453.76 (6) Å³	0.24 × 0.18 × 0.12 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	3334 independent reflections
Radiation source: fine-focus sealed tube	2688 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.386, T_max = 0.514	k = −12→12
11853 measured reflections	l = −18→14

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0228P)²] where P = (F_o² + 2F_c²)/3
3334 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.47 e Å⁻³
1 restraint	Δρ_min = −0.42 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[SnBr₄(C₆H₅)₂]	V = 1453.76 (6) Å³
M_r = 838.89	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.7803 (2) Å	µ = 6.40 mm⁻¹
b = 9.3847 (2) Å	T = 100 K
c = 14.4068 (4) Å	0.24 × 0.18 × 0.12 mm
β = 94.126 (2)°

Data collection top

Bruker SMART APEX diffractometer	3334 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2688 reflections with I > 2σ(I)
T_min = 0.386, T_max = 0.514	R_int = 0.035
11853 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	1 restraint
wR(F²) = 0.051	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.47 e Å⁻³
3334 reflections	Δρ_min = −0.42 e Å⁻³
166 parameters

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

	x	y	z	U_iso*/U_eq
Sn1	0.5000	0.5000	0.5000	0.01159 (7)
Br1	0.25635 (2)	0.50711 (3)	0.43147 (2)	0.01591 (7)
Br2	0.55014 (2)	0.71661 (3)	0.38004 (2)	0.01549 (7)
N1	0.05057 (19)	1.2090 (2)	0.45413 (16)	0.0168 (5)
N2	0.2527 (2)	0.8608 (3)	0.3851 (2)	0.0309 (7)
H2N	0.296 (3)	0.785 (2)	0.372 (3)	0.057 (12)*
C1	0.4622 (2)	0.6546 (3)	0.60374 (19)	0.0130 (6)
C2	0.5344 (2)	0.7784 (3)	0.6151 (2)	0.0185 (6)
H2	0.6043	0.7916	0.5794	0.022*
C3	0.5038 (3)	0.8816 (3)	0.6784 (2)	0.0232 (7)
H3	0.5529	0.9654	0.6862	0.028*
C4	0.4025 (3)	0.8631 (3)	0.7301 (2)	0.0248 (7)
H4	0.3807	0.9354	0.7722	0.030*
C5	0.3325 (3)	0.7406 (3)	0.7212 (2)	0.0219 (7)
H5	0.2639	0.7277	0.7582	0.026*
C6	0.3615 (2)	0.6360 (3)	0.65865 (19)	0.0172 (6)
H6	0.3131	0.5515	0.6530	0.021*
C7	−0.0284 (3)	1.2845 (3)	0.3844 (2)	0.0260 (7)
H7A	0.0236	1.3368	0.3429	0.039*
H7B	−0.0816	1.3517	0.4153	0.039*
H7C	−0.0804	1.2160	0.3481	0.039*
C8	0.0588 (3)	1.2631 (3)	0.5493 (2)	0.0209 (6)
H8A	0.0386	1.1866	0.5920	0.031*
H8B	−0.0001	1.3418	0.5541	0.031*
H8C	0.1435	1.2972	0.5657	0.031*
C9	0.1188 (2)	1.0979 (3)	0.4305 (2)	0.0141 (6)
C10	0.1155 (2)	1.0461 (3)	0.3381 (2)	0.0182 (6)
H10	0.0668	1.0937	0.2900	0.022*
C11	0.1821 (3)	0.9282 (3)	0.3182 (2)	0.0254 (7)
H11	0.1786	0.8932	0.2562	0.031*
C12	0.2617 (3)	0.9093 (3)	0.4731 (2)	0.0280 (8)
H12	0.3141	0.8609	0.5186	0.034*
C13	0.1979 (2)	1.0250 (3)	0.4982 (2)	0.0201 (7)
H13	0.2058	1.0577	0.5607	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01150 (12)	0.01286 (14)	0.01055 (14)	0.00047 (10)	0.00166 (10)	0.00068 (11)
Br1	0.01193 (13)	0.01943 (15)	0.01628 (15)	0.00059 (10)	0.00046 (10)	0.00031 (12)
Br2	0.01807 (13)	0.01534 (14)	0.01326 (14)	−0.00163 (11)	0.00254 (10)	0.00332 (13)
N1	0.0165 (11)	0.0180 (12)	0.0155 (13)	0.0016 (10)	−0.0018 (9)	0.0031 (11)
N2	0.0372 (15)	0.0258 (16)	0.0305 (17)	0.0166 (13)	0.0093 (13)	0.0049 (14)
C1	0.0147 (13)	0.0135 (14)	0.0109 (15)	0.0026 (11)	0.0011 (11)	−0.0007 (12)
C2	0.0209 (14)	0.0194 (15)	0.0155 (15)	−0.0009 (12)	0.0027 (12)	0.0045 (13)
C3	0.0308 (16)	0.0152 (16)	0.0227 (17)	−0.0012 (12)	−0.0039 (13)	−0.0025 (13)
C4	0.0339 (17)	0.0243 (17)	0.0158 (16)	0.0109 (14)	−0.0004 (13)	−0.0078 (14)
C5	0.0193 (14)	0.0345 (19)	0.0120 (15)	0.0065 (12)	0.0012 (12)	−0.0018 (14)
C6	0.0139 (13)	0.0235 (16)	0.0138 (15)	0.0001 (11)	−0.0015 (11)	−0.0003 (13)
C7	0.0217 (15)	0.0307 (18)	0.0244 (17)	0.0081 (13)	−0.0072 (13)	−0.0020 (15)
C8	0.0233 (14)	0.0217 (16)	0.0178 (16)	−0.0016 (12)	0.0018 (12)	−0.0022 (13)
C9	0.0132 (12)	0.0147 (14)	0.0147 (15)	−0.0048 (10)	0.0016 (11)	0.0038 (12)
C10	0.0184 (14)	0.0163 (15)	0.0197 (16)	0.0006 (11)	0.0000 (12)	0.0056 (13)
C11	0.0345 (17)	0.0237 (17)	0.0188 (17)	0.0052 (14)	0.0073 (14)	0.0021 (15)
C12	0.0271 (16)	0.0303 (19)	0.0261 (19)	0.0057 (14)	−0.0014 (14)	0.0102 (16)
C13	0.0192 (13)	0.0234 (17)	0.0175 (16)	−0.0012 (12)	0.0010 (12)	0.0045 (13)

Geometric parameters (Å, º) top

Sn1—C1	2.143 (3)	C4—H4	0.9500
Sn1—C1ⁱ	2.143 (3)	C5—C6	1.384 (4)
Sn1—Br1	2.7395 (2)	C5—H5	0.9500
Sn1—Br1ⁱ	2.7395 (2)	C6—H6	0.9500
Sn1—Br2	2.7470 (3)	C7—H7A	0.9800
Sn1—Br2ⁱ	2.7470 (3)	C7—H7B	0.9800
N1—C9	1.334 (3)	C7—H7C	0.9800
N1—C7	1.454 (3)	C8—H8A	0.9800
N1—C8	1.459 (4)	C8—H8B	0.9800
N2—C12	1.344 (4)	C8—H8C	0.9800
N2—C11	1.342 (4)	C9—C10	1.415 (4)
N2—H2N	0.879 (10)	C9—C13	1.424 (4)
C1—C6	1.399 (4)	C10—C11	1.361 (4)
C1—C2	1.402 (4)	C10—H10	0.9500
C2—C3	1.387 (4)	C11—H11	0.9500
C2—H2	0.9500	C12—C13	1.349 (4)
C3—C4	1.376 (4)	C12—H12	0.9500
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.376 (4)

C1—Sn1—C1ⁱ	180.0	C6—C5—C4	120.3 (3)
C1—Sn1—Br1	90.53 (7)	C6—C5—H5	119.8
C1—Sn1—Br1ⁱ	89.47 (7)	C4—C5—H5	119.8
C1—Sn1—Br2	89.64 (7)	C5—C6—C1	120.1 (3)
C1—Sn1—Br2ⁱ	90.36 (7)	C5—C6—H6	120.0
C1ⁱ—Sn1—Br1	89.47 (7)	C1—C6—H6	120.0
C1ⁱ—Sn1—Br1ⁱ	90.53 (7)	N1—C7—H7A	109.5
C1ⁱ—Sn1—Br2	90.36 (7)	N1—C7—H7B	109.5
C1ⁱ—Sn1—Br2ⁱ	89.64 (7)	H7A—C7—H7B	109.5
Br1—Sn1—Br1ⁱ	180.0	N1—C7—H7C	109.5
Br1—Sn1—Br2	88.981 (8)	H7A—C7—H7C	109.5
Br1—Sn1—Br2ⁱ	91.019 (8)	H7B—C7—H7C	109.5
Br1ⁱ—Sn1—Br2ⁱ	88.981 (8)	N1—C8—H8A	109.5
Br1ⁱ—Sn1—Br2	91.019 (8)	N1—C8—H8B	109.5
Br2—Sn1—Br2ⁱ	180.0	H8A—C8—H8B	109.5
C9—N1—C7	120.7 (2)	N1—C8—H8C	109.5
C9—N1—C8	121.0 (2)	H8A—C8—H8C	109.5
C7—N1—C8	118.2 (2)	H8B—C8—H8C	109.5
C12—N2—C11	121.0 (3)	N1—C9—C10	122.1 (2)
C12—N2—H2N	118 (3)	N1—C9—C13	121.0 (3)
C11—N2—H2N	120 (3)	C10—C9—C13	116.9 (2)
C6—C1—C2	118.9 (3)	C11—C10—C9	120.0 (3)
C6—C1—Sn1	120.3 (2)	C11—C10—H10	120.0
C2—C1—Sn1	120.71 (19)	C9—C10—H10	120.0
C3—C2—C1	120.0 (3)	N2—C11—C10	120.8 (3)
C3—C2—H2	120.0	N2—C11—H11	119.6
C1—C2—H2	120.0	C10—C11—H11	119.6
C4—C3—C2	120.2 (3)	N2—C12—C13	121.5 (3)
C4—C3—H3	119.9	N2—C12—H12	119.3
C2—C3—H3	119.9	C13—C12—H12	119.3
C3—C4—C5	120.4 (3)	C12—C13—C9	119.7 (3)
C3—C4—H4	119.8	C12—C13—H13	120.1
C5—C4—H4	119.8	C9—C13—H13	120.1

Br1ⁱ—Sn1—C1—C6	−130.5 (2)	C2—C1—C6—C5	1.7 (4)
Br1—Sn1—C1—C6	49.5 (2)	Sn1—C1—C6—C5	−175.7 (2)
Br2ⁱ—Sn1—C1—C6	−41.5 (2)	C7—N1—C9—C10	−1.6 (4)
Br2—Sn1—C1—C6	138.5 (2)	C8—N1—C9—C10	−178.0 (2)
Br1ⁱ—Sn1—C1—C2	52.2 (2)	C7—N1—C9—C13	178.9 (2)
Br1—Sn1—C1—C2	−127.8 (2)	C8—N1—C9—C13	2.6 (4)
Br2ⁱ—Sn1—C1—C2	141.2 (2)	N1—C9—C10—C11	−176.8 (3)
Br2—Sn1—C1—C2	−38.8 (2)	C13—C9—C10—C11	2.6 (4)
C6—C1—C2—C3	−1.5 (4)	C12—N2—C11—C10	−1.4 (5)
Sn1—C1—C2—C3	175.9 (2)	C9—C10—C11—N2	−0.9 (4)
C1—C2—C3—C4	−0.2 (4)	C11—N2—C12—C13	1.7 (5)
C2—C3—C4—C5	1.7 (4)	N2—C12—C13—C9	0.2 (5)
C3—C4—C5—C6	−1.5 (4)	N1—C9—C13—C12	177.1 (3)
C4—C5—C6—C1	−0.2 (4)	C10—C9—C13—C12	−2.3 (4)

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
N2—H2N···Br1	0.88 (1)	2.79 (3)	3.385 (3)	126 (3)
N2—H2N···Br2	0.88 (1)	2.81 (3)	3.485 (3)	135 (3)

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[SnBr₄(C₆H₅)₂]
M_r	838.89
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.7803 (2), 9.3847 (2), 14.4068 (4)
β (°)	94.126 (2)
V (Å³)	1453.76 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.40
Crystal size (mm)	0.24 × 0.18 × 0.12

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.386, 0.514
No. of measured, independent and observed [I > 2σ(I)] reflections	11853, 3334, 2688
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.051, 0.99
No. of reflections	3334
No. of parameters	166
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.42

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

Selected geometric parameters (Å, º) top

Sn1—C1	2.143 (3)	Sn1—Br2	2.7470 (3)
Sn1—Br1	2.7395 (2)

C1—Sn1—Br1	90.53 (7)	C1—Sn1—Br2ⁱ	90.36 (7)
C1—Sn1—Br1ⁱ	89.47 (7)	Br1—Sn1—Br2	88.981 (8)
C1—Sn1—Br2	89.64 (7)	Br1—Sn1—Br2ⁱ	91.019 (8)

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
N2—H2N···Br1	0.88 (1)	2.79 (3)	3.385 (3)	126 (3)
N2—H2N···Br2	0.88 (1)	2.81 (3)	3.485 (3)	135 (3)

Acknowledgements

We thank the University of Malaya for funding this study (SF022155/2007 A) and also for the purchase of the diffractometer.

References

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