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

Lee, S.M.; Lo, K.M.; Mohd Ali, H.; Robinson, W.T.

doi:10.1107/S1600536809030323

metal-organic compounds

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Volume 65| Part 9| September 2009| Page m1040

doi:10.1107/S1600536809030323

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

See Mun Lee,^a Kong Mun Lo,^a ^* Hapipah Mohd Ali ^a and Ward T. Robinson ^a

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

(Received 8 June 2009; accepted 30 July 2009; online 8 August 2009)

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, P 2₁ /n
a = 10.2178 (3) Å
b = 10.4808 (3) Å
c = 14.5833 (3) Å
β = 95.063 (1)°
V = 1555.64 (7) Å³
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[F² > 2σ(F²)] = 0.018
wR(F²) = 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

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) x-1, y+1, z.

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030323/lh2842sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030323/lh2842Isup2.hkl

checkCIF report

Comment top

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

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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).

Figures top

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).

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

Crystal data top

(C₇H₁₁N₂)₂[SnBr₄(C₇H₇)₂]	F(000) = 844
M_r = 866.94	D_x = 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 top

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

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) = 0.045	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0246P)² + 0.5727P] where P = (F_o² + 2F_c²)/3
3569 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[SnBr₄(C₇H₇)₂]	V = 1555.64 (7) Å³
M_r = 866.94	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.2178 (3) Å	µ = 5.98 mm⁻¹
b = 10.4808 (3) Å	T = 100 K
c = 14.5833 (3) Å	0.35 × 0.30 × 0.22 mm
β = 95.063 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3569 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3225 reflections with I > 2σ(I)
T_min = 0.229, T_max = 0.353	R_int = 0.019
11555 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	0 restraints
wR(F²) = 0.045	H-atom parameters constrained
S = 1.05	Δρ_max = 0.44 e Å⁻³
3569 reflections	Δρ_min = −0.45 e Å⁻³
172 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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	2.7652 (2)	C7—H7B	0.9800
Sn1—Br1ⁱ	2.7652 (2)	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 code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

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 code: (ii) x−1, y+1, z.

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[SnBr₄(C₇H₇)₂]
M_r	866.94
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.2178 (3), 10.4808 (3), 14.5833 (3)
β (°)	95.063 (1)
V (Å³)	1555.64 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.98
Crystal size (mm)	0.35 × 0.30 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.229, 0.353
No. of measured, independent and observed [I > 2σ(I)] reflections	11555, 3569, 3225
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.045, 1.05
No. of reflections	3569
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.45

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

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) x−1, y+1, z.

Acknowledgements

We thank the University of Malaya (grant No. PS072/2007C and PS320/2008C) for supporting this study.

References

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Koon, Y. C., Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, m663. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, m630. 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

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Volume 65| Part 9| September 2009| Page m1040

doi:10.1107/S1600536809030323

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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