Bis[4-(dimethyl­amino)pyridinium] tetra­bromidobis(4-methyl­phen­yl)stannate(IV)

Abstract

In the title compound, (C₇H₁₁N₂)₂[SnBr₄(C₇H₇)₂], the tetra­bromidobis(4-methyl­phen­yl)stannate(IV) anion possesses a centre of inversion located at the Sn^IV atom. In the crystal structure, two inversion-related cations are linked to the anion via weak N—H⋯Br hydrogen bonds.

Related literature

For related crystal structures, see Lo & Ng (2009 ▶); Koon et al. (2009 ▶); Yap et al. (2008 ▶).

Experimental

Crystal data

• (C₇H₁₁N₂)₂[SnBr₄(C₇H₇)₂]

• M _r = 866.94

• Monoclinic,

• a = 10.2178 (3) Å

• b = 10.4808 (3) Å

• c = 14.5833 (3) Å

• β = 95.063 (1)°

• V = 1555.64 (7) ų

• Z = 2

• Mo Kα radiation

• μ = 5.98 mm⁻¹

• T = 100 K

• 0.35 × 0.30 × 0.22 mm

Data collection

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.229, T _max = 0.353 (expected range = 0.174–0.268)

• 11555 measured reflections

• 3569 independent reflections

• 3225 reflections with I > 2σ(I)

• R _int = 0.019

Refinement

• R[F ² > 2σ(F ²)] = 0.018

• wR(F ²) = 0.045

• S = 1.05

• 3569 reflections

• 172 parameters

• H-atom parameters constrained

• Δρ_max = 0.44 e Å⁻³

• Δρ_min = −0.45 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); 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⋯Br1i	0.88	2.75	3.448 (2)	138
N1—H1⋯Br2i	0.88	2.94	3.517 (2)	125

Symmetry code: (i) .

supplementary crystallographic information

Comment

The molecular structure of the title compound is shown in Fig. 1.

Experimental

Tetra(4-methylphenyl)tin (0.49 g, 1 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (0.40 g, 1 mmol) were dissolved in absolute ethanol (25 ml) and refluxed for six hours. The solution was filtered and colourless crystals were isolated upon cooling to room temperature.

Refinement

Hydrogen atoms were placed at calculated positions (C–H 0.95 to 0.98 Å) and were treated as riding on their parent carbon atoms, with U(H) set to 1.2–1.5 times U(C,N). N—H was refined and placed in the calculated position of N—H 0.88 ± 0.01 Å.

Figures

Fig. 1.

The molecular structure of the title compound with 50% probability displacement ellipsoids and the atom numbering. Hydrogen atoms are drawn as spheres of arbitrary radius and dashed lines indicate hydrogen bonds (symmetry codes: (A) 1+x, -1+y, z and (B) 2-x, -y, -z).

Crystal data

(C7H11N2)2[SnBr4(C7H7)2]	F(000) = 844
Mr = 866.94	Dx = 1.851 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6698 reflections
a = 10.2178 (3) Å	θ = 2.3–30.5°
b = 10.4808 (3) Å	µ = 5.98 mm−1
c = 14.5833 (3) Å	T = 100 K
β = 95.063 (1)°	Block, colourless
V = 1555.64 (7) Å3	0.35 × 0.30 × 0.22 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	3569 independent reflections
Radiation source: fine-focus sealed tube	3225 reflections with I > 2σ(I)
graphite	Rint = 0.019
ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→10
Tmin = 0.229, Tmax = 0.353	k = −13→8
11555 measured reflections	l = −18→18

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) = 0.045	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0246P)2 + 0.5727P] where P = (Fo2 + 2Fc2)/3
3569 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Sn1	1.0000	0.0000	0.0000	0.01042 (5)
Br1	0.951470 (19)	−0.180492 (17)	0.131083 (12)	0.01383 (5)
Br2	1.261950 (18)	−0.018292 (18)	0.055861 (14)	0.01597 (6)
N1	0.24150 (18)	0.65685 (17)	0.11335 (13)	0.0237 (4)
H1	0.2028	0.7281	0.1280	0.028*
N2	0.43055 (16)	0.33066 (16)	0.04249 (11)	0.0166 (3)
C1	0.98097 (18)	0.15055 (17)	0.09731 (12)	0.0106 (3)
C2	1.06827 (19)	0.25260 (18)	0.10370 (13)	0.0140 (4)
H2	1.1417	0.2527	0.0680	0.017*
C3	1.04872 (19)	0.35431 (19)	0.16189 (13)	0.0158 (4)
H3	1.1089	0.4236	0.1651	0.019*
C4	0.94235 (19)	0.35675 (19)	0.21573 (13)	0.0148 (4)
C5	0.85693 (19)	0.25278 (19)	0.21028 (13)	0.0142 (4)
H5	0.7847	0.2514	0.2471	0.017*
C6	0.87603 (18)	0.15088 (18)	0.15165 (12)	0.0136 (4)
H6	0.8167	0.0809	0.1488	0.016*
C7	0.9200 (2)	0.46954 (19)	0.27623 (15)	0.0204 (4)
H7A	0.8970	0.5443	0.2377	0.031*
H7B	1.0004	0.4873	0.3160	0.031*
H7C	0.8482	0.4506	0.3144	0.031*
C8	0.2184 (2)	0.6093 (2)	0.02768 (15)	0.0249 (5)
H8	0.1593	0.6526	−0.0157	0.030*
C9	0.2777 (2)	0.5010 (2)	0.00204 (15)	0.0201 (4)
H9	0.2596	0.4687	−0.0586	0.024*
C10	0.36716 (18)	0.43551 (18)	0.06587 (13)	0.0131 (4)
C11	0.3857 (2)	0.48772 (18)	0.15624 (14)	0.0171 (4)
H11	0.4421	0.4461	0.2022	0.021*
C12	0.3229 (2)	0.5969 (2)	0.17697 (14)	0.0202 (4)
H12	0.3367	0.6314	0.2373	0.024*
C13	0.4097 (2)	0.2765 (2)	−0.05001 (14)	0.0208 (4)
H13A	0.3200	0.2431	−0.0599	0.031*
H13B	0.4726	0.2072	−0.0565	0.031*
H13C	0.4225	0.3430	−0.0956	0.031*
C14	0.5171 (2)	0.2619 (2)	0.11039 (15)	0.0249 (5)
H14A	0.5837	0.3204	0.1387	0.037*
H14B	0.5603	0.1920	0.0801	0.037*
H14C	0.4653	0.2270	0.1580	0.037*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Sn1	0.01059 (9)	0.00929 (9)	0.01105 (9)	0.00024 (6)	−0.00081 (6)	−0.00130 (6)
Br1	0.01585 (10)	0.01282 (10)	0.01285 (9)	−0.00079 (7)	0.00140 (7)	0.00179 (7)
Br2	0.01007 (10)	0.01519 (10)	0.02186 (11)	0.00061 (7)	−0.00312 (7)	−0.00193 (7)
N1	0.0260 (10)	0.0161 (9)	0.0291 (10)	0.0075 (7)	0.0021 (8)	0.0008 (7)
N2	0.0155 (8)	0.0160 (8)	0.0179 (8)	0.0010 (7)	−0.0002 (6)	0.0011 (7)
C1	0.0124 (9)	0.0099 (8)	0.0091 (8)	0.0006 (7)	−0.0018 (7)	−0.0002 (7)
C2	0.0120 (9)	0.0134 (9)	0.0165 (9)	−0.0010 (7)	0.0013 (7)	−0.0003 (7)
C3	0.0139 (9)	0.0119 (9)	0.0210 (10)	−0.0036 (7)	−0.0009 (7)	−0.0015 (7)
C4	0.0157 (9)	0.0137 (9)	0.0143 (9)	0.0041 (8)	−0.0027 (7)	−0.0022 (7)
C5	0.0119 (9)	0.0185 (10)	0.0124 (9)	0.0022 (7)	0.0024 (7)	0.0002 (7)
C6	0.0126 (9)	0.0143 (9)	0.0136 (9)	−0.0019 (7)	−0.0006 (7)	0.0005 (7)
C7	0.0218 (11)	0.0158 (10)	0.0232 (10)	0.0042 (8)	0.0005 (8)	−0.0068 (8)
C8	0.0252 (11)	0.0265 (12)	0.0225 (11)	0.0073 (9)	−0.0016 (9)	0.0083 (9)
C9	0.0193 (11)	0.0246 (11)	0.0157 (10)	0.0023 (8)	−0.0021 (8)	0.0035 (8)
C10	0.0110 (9)	0.0119 (9)	0.0165 (9)	−0.0037 (7)	0.0011 (7)	0.0020 (7)
C11	0.0153 (10)	0.0175 (10)	0.0177 (10)	−0.0019 (8)	−0.0035 (8)	0.0019 (8)
C12	0.0208 (11)	0.0179 (10)	0.0214 (10)	−0.0019 (8)	−0.0012 (8)	−0.0016 (8)
C13	0.0203 (11)	0.0228 (11)	0.0194 (10)	−0.0016 (9)	0.0025 (8)	−0.0038 (8)
C14	0.0275 (12)	0.0205 (11)	0.0259 (11)	0.0108 (9)	−0.0016 (9)	0.0030 (9)

Geometric parameters (Å, °)

Sn1—C1i	2.1424 (18)	C5—C6	1.393 (3)
Sn1—C1	2.1424 (18)	C5—H5	0.9500
Sn1—Br2i	2.7349 (2)	C6—H6	0.9500
Sn1—Br2	2.7349 (2)	C7—H7A	0.9800
Sn1—Br1	2.76515 (18)	C7—H7B	0.9800
Sn1—Br1i	2.76515 (18)	C7—H7C	0.9800
N1—C12	1.346 (3)	C8—C9	1.356 (3)
N1—C8	1.346 (3)	C8—H8	0.9500
N1—H1	0.8800	C9—C10	1.422 (3)
N2—C10	1.335 (2)	C9—H9	0.9500
N2—C14	1.459 (3)	C10—C11	1.424 (3)
N2—C13	1.462 (3)	C11—C12	1.359 (3)
C1—C6	1.388 (3)	C11—H11	0.9500
C1—C2	1.391 (3)	C12—H12	0.9500
C2—C3	1.388 (3)	C13—H13A	0.9800
C2—H2	0.9500	C13—H13B	0.9800
C3—C4	1.396 (3)	C13—H13C	0.9800
C3—H3	0.9500	C14—H14A	0.9800
C4—C5	1.394 (3)	C14—H14B	0.9800
C4—C7	1.504 (3)	C14—H14C	0.9800
C1i—Sn1—C1	180.00 (13)	C1—C6—C5	120.63 (18)
C1i—Sn1—Br2i	89.88 (5)	C1—C6—H6	119.7
C1—Sn1—Br2i	90.12 (5)	C5—C6—H6	119.7
C1i—Sn1—Br2	90.12 (5)	C4—C7—H7A	109.5
C1—Sn1—Br2	89.88 (5)	C4—C7—H7B	109.5
Br2i—Sn1—Br2	180.000 (12)	H7A—C7—H7B	109.5
C1i—Sn1—Br1	89.22 (5)	C4—C7—H7C	109.5
C1—Sn1—Br1	90.78 (5)	H7A—C7—H7C	109.5
Br2i—Sn1—Br1	91.340 (6)	H7B—C7—H7C	109.5
Br2—Sn1—Br1	88.660 (6)	N1—C8—C9	121.3 (2)
C1i—Sn1—Br1i	90.78 (5)	N1—C8—H8	119.3
C1—Sn1—Br1i	89.22 (5)	C9—C8—H8	119.3
Br2i—Sn1—Br1i	88.660 (6)	C8—C9—C10	120.1 (2)
Br2—Sn1—Br1i	91.340 (6)	C8—C9—H9	120.0
Br1—Sn1—Br1i	180.000 (10)	C10—C9—H9	120.0
C12—N1—C8	120.94 (19)	N2—C10—C9	121.88 (18)
C12—N1—H1	119.5	N2—C10—C11	121.65 (18)
C8—N1—H1	119.5	C9—C10—C11	116.47 (18)
C10—N2—C14	120.81 (17)	C12—C11—C10	120.16 (19)
C10—N2—C13	121.38 (17)	C12—C11—H11	119.9
C14—N2—C13	117.71 (17)	C10—C11—H11	119.9
C6—C1—C2	118.88 (17)	N1—C12—C11	121.0 (2)
C6—C1—Sn1	119.98 (13)	N1—C12—H12	119.5
C2—C1—Sn1	121.04 (13)	C11—C12—H12	119.5
C3—C2—C1	120.37 (17)	N2—C13—H13A	109.5
C3—C2—H2	119.8	N2—C13—H13B	109.5
C1—C2—H2	119.8	H13A—C13—H13B	109.5
C2—C3—C4	121.28 (18)	N2—C13—H13C	109.5
C2—C3—H3	119.4	H13A—C13—H13C	109.5
C4—C3—H3	119.4	H13B—C13—H13C	109.5
C5—C4—C3	117.91 (17)	N2—C14—H14A	109.5
C5—C4—C7	121.42 (17)	N2—C14—H14B	109.5
C3—C4—C7	120.66 (18)	H14A—C14—H14B	109.5
C6—C5—C4	120.90 (17)	N2—C14—H14C	109.5
C6—C5—H5	119.5	H14A—C14—H14C	109.5
C4—C5—H5	119.5	H14B—C14—H14C	109.5
C1i—Sn1—C1—C6	0.00 (18)	C7—C4—C5—C6	177.77 (18)
Br2i—Sn1—C1—C6	44.67 (14)	C2—C1—C6—C5	1.2 (3)
Br2—Sn1—C1—C6	−135.33 (14)	Sn1—C1—C6—C5	−175.23 (14)
Br1—Sn1—C1—C6	−46.67 (14)	C4—C5—C6—C1	0.1 (3)
Br1i—Sn1—C1—C6	133.33 (14)	C12—N1—C8—C9	−1.1 (3)
C1i—Sn1—C1—C2	0.00 (7)	N1—C8—C9—C10	−0.4 (3)
Br2i—Sn1—C1—C2	−131.72 (15)	C14—N2—C10—C9	−177.10 (19)
Br2—Sn1—C1—C2	48.28 (15)	C13—N2—C10—C9	−0.9 (3)
Br1—Sn1—C1—C2	136.94 (15)	C14—N2—C10—C11	2.9 (3)
Br1i—Sn1—C1—C2	−43.06 (15)	C13—N2—C10—C11	179.12 (18)
C6—C1—C2—C3	−1.5 (3)	C8—C9—C10—N2	−178.0 (2)
Sn1—C1—C2—C3	174.92 (14)	C8—C9—C10—C11	2.0 (3)
C1—C2—C3—C4	0.5 (3)	N2—C10—C11—C12	177.86 (18)
C2—C3—C4—C5	0.9 (3)	C9—C10—C11—C12	−2.1 (3)
C2—C3—C4—C7	−178.05 (19)	C8—N1—C12—C11	1.0 (3)
C3—C4—C5—C6	−1.1 (3)	C10—C11—C12—N1	0.7 (3)

Symmetry codes: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1ii	0.88	2.75	3.448 (2)	138
N1—H1···Br2ii	0.88	2.94	3.517 (2)	125

Symmetry codes: (ii) x−1, y+1, z.