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

Abstract

The Sn atom in the title salt, (C₇H₁₁N₂)₂[SnBr_4.67Cl_1.33], 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

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

Experimental

Crystal data

• (C₇H₁₁N₂)₂[SnBr_4.67Cl_1.33]

• M _r = 785.15

• Monoclinic,

• a = 8.4530 (2) Å

• b = 11.9036 (2) Å

• c = 11.9093 (2) Å

• β = 107.109 (1)°

• V = 1145.30 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 9.42 mm⁻¹

• T = 100 K

• 0.30 × 0.25 × 0.20 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.504, T _max = 0.746 (expected range = 0.103–0.152)

• 10319 measured reflections

• 2622 independent reflections

• 2240 reflections with I > 2σ(I)

• R _int = 0.033

Refinement

• R[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 0.060

• S = 0.99

• 2622 reflections

• 127 parameters

• 6 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.80 e Å⁻³

• Δρ_min = −0.87 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. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.88 (1)	2.484 (18)	3.334 (3)	162 (4)

supplementary crystallographic information

Experimental

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

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 U_eq(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.

Figures

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.

Crystal data

(C7H11N2)2[SnBr4.67Cl1.33]	F(000) = 740
Mr = 785.15	Dx = 2.277 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4263 reflections
a = 8.4530 (2) Å	θ = 2.5–28.3°
b = 11.9036 (2) Å	µ = 9.42 mm−1
c = 11.9093 (2) Å	T = 100 K
β = 107.109 (1)°	Irregular block, colorless
V = 1145.30 (4) Å3	0.30 × 0.25 × 0.20 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	2622 independent reflections
Radiation source: fine-focus sealed tube	2240 reflections with I > 2σ(I)
graphite	Rint = 0.033
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.504, Tmax = 0.746	k = −15→15
10319 measured reflections	l = −14→15

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.060	H 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 parameters	Δρmax = 0.80 e Å−3
6 restraints	Δρmin = −0.87 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	0.01384 (8)
Br1	0.50914 (5)	0.63592 (3)	0.66901 (3)	0.02247 (12)	0.6143 (14)
Br2	0.58481 (5)	0.33875 (3)	0.64866 (3)	0.02405 (12)	0.8309 (9)
Br3	0.80683 (4)	0.53911 (3)	0.52227 (3)	0.02760 (12)	0.8878 (10)
Cl1	0.50914 (5)	0.63592 (3)	0.66901 (3)	0.02247 (12)	0.3858 (14)
Cl2	0.58481 (5)	0.33875 (3)	0.64866 (3)	0.02405 (12)	0.1122 (10)
Cl3	0.80683 (4)	0.53911 (3)	0.52227 (3)	0.02760 (12)	0.1691 (9)
N1	0.6521 (4)	0.8743 (2)	0.5886 (3)	0.0309 (7)
H1	0.598 (5)	0.812 (2)	0.593 (4)	0.061 (14)*
N2	0.9135 (3)	1.1561 (2)	0.5550 (2)	0.0231 (6)
C1	0.7281 (4)	0.9350 (3)	0.6844 (3)	0.0304 (8)
H1A	0.7212	0.9116	0.7590	0.036*
C2	0.8143 (4)	1.0288 (3)	0.6765 (3)	0.0259 (7)
H2	0.8683	1.0696	0.7457	0.031*
C3	0.8251 (4)	1.0670 (3)	0.5661 (3)	0.0190 (6)
C4	0.7363 (4)	1.0019 (3)	0.4663 (3)	0.0228 (7)
H4	0.7345	1.0249	0.3896	0.027*
C5	0.6553 (4)	0.9080 (3)	0.4810 (3)	0.0297 (8)
H5	0.5994	0.8645	0.4142	0.036*
C6	1.0103 (4)	1.2201 (3)	0.6573 (3)	0.0349 (8)
H6A	0.9356	1.2652	0.6883	0.052*
H6B	1.0876	1.2697	0.6340	0.052*
H6C	1.0725	1.1680	0.7182	0.052*
C7	0.9124 (4)	1.1989 (3)	0.4397 (3)	0.0293 (7)
H7A	0.9577	1.1418	0.3985	0.044*
H7B	0.9802	1.2670	0.4496	0.044*
H7C	0.7985	1.2166	0.3937	0.044*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Sn1	0.01350 (14)	0.01560 (14)	0.01208 (14)	−0.00189 (10)	0.00326 (11)	−0.00020 (11)
Br1	0.0329 (2)	0.0187 (2)	0.0178 (2)	−0.00322 (16)	0.01055 (17)	−0.00423 (15)
Br2	0.0329 (2)	0.01902 (19)	0.01671 (19)	−0.00065 (14)	0.00180 (15)	0.00479 (13)
Br3	0.01394 (18)	0.0409 (2)	0.0279 (2)	−0.00705 (13)	0.00609 (14)	−0.00114 (15)
Cl1	0.0329 (2)	0.0187 (2)	0.0178 (2)	−0.00322 (16)	0.01055 (17)	−0.00423 (15)
Cl2	0.0329 (2)	0.01902 (19)	0.01671 (19)	−0.00065 (14)	0.00180 (15)	0.00479 (13)
Cl3	0.01394 (18)	0.0409 (2)	0.0279 (2)	−0.00705 (13)	0.00609 (14)	−0.00114 (15)
N1	0.0277 (16)	0.0246 (15)	0.0427 (19)	0.0002 (12)	0.0141 (14)	0.0088 (14)
N2	0.0235 (14)	0.0244 (14)	0.0195 (14)	−0.0029 (11)	0.0032 (11)	−0.0017 (11)
C1	0.0298 (19)	0.037 (2)	0.0273 (18)	0.0121 (15)	0.0138 (15)	0.0114 (16)
C2	0.0256 (17)	0.0335 (18)	0.0190 (17)	0.0045 (14)	0.0071 (14)	0.0010 (13)
C3	0.0157 (14)	0.0217 (15)	0.0185 (15)	0.0046 (11)	0.0036 (12)	0.0009 (12)
C4	0.0214 (15)	0.0252 (16)	0.0198 (16)	−0.0003 (13)	0.0030 (13)	−0.0026 (13)
C5	0.0238 (17)	0.0282 (18)	0.033 (2)	−0.0001 (13)	0.0021 (15)	−0.0037 (15)
C6	0.033 (2)	0.035 (2)	0.033 (2)	−0.0101 (15)	0.0035 (16)	−0.0085 (16)
C7	0.0300 (18)	0.0285 (18)	0.0270 (18)	−0.0048 (14)	0.0045 (14)	0.0082 (14)

Geometric parameters (Å, °)

Sn1—Br1	2.5658 (4)	C1—C2	1.351 (5)
Sn1—Cl1i	2.5658 (4)	C1—H1A	0.9500
Sn1—Br1i	2.5658 (4)	C2—C3	1.419 (4)
Sn1—Br2	2.5663 (3)	C2—H2	0.9500
Sn1—Cl2i	2.5663 (3)	C3—C4	1.433 (4)
Sn1—Br2i	2.5663 (3)	C4—C5	1.349 (5)
Sn1—Cl3i	2.5709 (3)	C4—H4	0.9500
Sn1—Br3i	2.5709 (3)	C5—H5	0.9500
Sn1—Br3	2.5709 (3)	C6—H6A	0.9800
N1—C1	1.343 (5)	C6—H6B	0.9800
N1—C5	1.351 (5)	C6—H6C	0.9800
N1—H1	0.882 (10)	C7—H7A	0.9800
N2—C3	1.327 (4)	C7—H7B	0.9800
N2—C6	1.466 (4)	C7—H7C	0.9800
N2—C7	1.462 (4)
Br1—Sn1—Cl1i	180.0	Br3i—Sn1—Br3	180.000 (17)
Br1—Sn1—Br1i	180.0	C1—N1—C5	120.5 (3)
Cl1i—Sn1—Br1i	0.000 (14)	C1—N1—H1	122 (3)
Br1—Sn1—Br2	89.576 (13)	C5—N1—H1	118 (3)
Cl1i—Sn1—Br2	90.424 (13)	C3—N2—C6	121.7 (3)
Br1i—Sn1—Br2	90.424 (13)	C3—N2—C7	121.6 (3)
Br1—Sn1—Cl2i	90.424 (13)	C6—N2—C7	116.6 (3)
Cl1i—Sn1—Cl2i	89.576 (12)	N1—C1—C2	121.2 (3)
Br1i—Sn1—Cl2i	89.576 (12)	N1—C1—H1A	119.4
Br2—Sn1—Cl2i	180.0	C2—C1—H1A	119.4
Br1—Sn1—Br2i	90.424 (13)	C1—C2—C3	120.8 (3)
Cl1i—Sn1—Br2i	89.576 (12)	C1—C2—H2	119.6
Br1i—Sn1—Br2i	89.576 (12)	C3—C2—H2	119.6
Br2—Sn1—Br2i	180.0	N2—C3—C2	122.7 (3)
Cl2i—Sn1—Br2i	0.00 (2)	N2—C3—C4	121.5 (3)
Br1—Sn1—Cl3i	89.529 (12)	C2—C3—C4	115.7 (3)
Cl1i—Sn1—Cl3i	90.471 (12)	C5—C4—C3	120.2 (3)
Br1i—Sn1—Cl3i	90.471 (12)	C5—C4—H4	119.9
Br2—Sn1—Cl3i	90.248 (12)	C3—C4—H4	119.9
Cl2i—Sn1—Cl3i	89.752 (12)	C4—C5—N1	121.4 (3)
Br2i—Sn1—Cl3i	89.752 (12)	C4—C5—H5	119.3
Br1—Sn1—Br3i	89.529 (12)	N1—C5—H5	119.3
Cl1i—Sn1—Br3i	90.471 (12)	N2—C6—H6A	109.5
Br1i—Sn1—Br3i	90.471 (12)	N2—C6—H6B	109.5
Br2—Sn1—Br3i	90.248 (12)	H6A—C6—H6B	109.5
Cl2i—Sn1—Br3i	89.752 (12)	N2—C6—H6C	109.5
Br2i—Sn1—Br3i	89.752 (12)	H6A—C6—H6C	109.5
Cl3i—Sn1—Br3i	0.00 (2)	H6B—C6—H6C	109.5
Br1—Sn1—Br3	90.471 (12)	N2—C7—H7A	109.5
Cl1i—Sn1—Br3	89.529 (12)	N2—C7—H7B	109.5
Br1i—Sn1—Br3	89.529 (12)	H7A—C7—H7B	109.5
Br2—Sn1—Br3	89.752 (12)	N2—C7—H7C	109.5
Cl2i—Sn1—Br3	90.248 (12)	H7A—C7—H7C	109.5
Br2i—Sn1—Br3	90.248 (12)	H7B—C7—H7C	109.5
Cl3i—Sn1—Br3	180.000 (17)
C5—N1—C1—C2	−2.3 (5)	C1—C2—C3—N2	−177.4 (3)
N1—C1—C2—C3	0.9 (5)	C1—C2—C3—C4	1.5 (5)
C6—N2—C3—C2	1.6 (5)	N2—C3—C4—C5	176.1 (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—N1	1.6 (5)
C7—N2—C3—C4	5.9 (5)	C1—N1—C5—C4	1.0 (5)

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 (1)	2.48 (2)	3.334 (3)	162 (4)