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

Lo, K.M.; Ng, S.W.

doi:10.1107/S1600536808013561

metal-organic compounds

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Volume 64| Part 6| June 2008| Page m800

doi:10.1107/S1600536808013561

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

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 6 May 2008; accepted 7 May 2008; online 10 May 2008)

The tin(IV) atom in the salt, (C₇H₁₁N₂)₂[SnBr₂(CH₃)₂Cl₂], lies on a center of inversion in a tetragonally compressed octahedron; the bromine atoms are disordered with the chlorine atoms, so that they appear to share the same site. The crystal structure is stabilized by N—H⋯Br hydrogen bonds.

Related literature

For the structure of bis(4-dimethylaminopyridinium) tetrabromidodiphenylstannate(IV), see: Yap et al. (2008 ).

Experimental

Crystal data

(C₇H₁₁N₂)₂[SnBr₂(CH₃)₂Cl₂]
M_r = 625.83
Triclinic, $[P \overline 1]$
a = 7.3573 (3) Å
b = 8.7717 (3) Å
c = 9.6644 (4) Å
α = 97.183 (3)°
β = 107.990 (3)°
γ = 90.052 (2)°
V = 588.04 (4) Å³
Z = 1
Mo Kα radiation
μ = 4.72 mm⁻¹
T = 100 (2) K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS;Sheldrick, 1996 ) T_min = 0.385, T_max = 0.538 (expected range = 0.353–0.493)
4965 measured reflections
2756 independent reflections
1656 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.123
S = 1.04
2756 reflections
122 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—C1	2.225 (5)
Sn1—X1	2.690 (1)
Sn1—X2	2.6926 (8)
X is a disordered mixture of Cl and Br.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯X1	0.88	2.60	3.316 (5)	139
N1—H1⋯X2ⁱ	0.88	2.81	3.458 (6)	132
X is a disordered mixture of Cl and Br. Symmetry code: (i) -x+1, -y+1, -z+1.

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/S1600536808013561/bt2709sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013561/bt2709Isup2.hkl

checkCIF report

Comment top

Bis(4-methylaminopyridinium) tetrabromidodiphenylstannate is produced from the cleavage of the mixed alkyl/triarylstannate, cyclopentyltriphenyltin, by 4-dimethylaminopyridine hydrobromide perbromide (Yap et al., 2008). In principle, the salt can be synthesized from the reaction of 4-dimethylaminopyridine hydrobromide perbromide and diphenyltin dibromide. The possibility is borne out by reacting the organic reagent with dimethyltin dichloride to yield the title salt (Scheme I, Fig. 1). The Sn^IV atom of the stannate lies on a center-of-inversion in tetragonally compressed octahedron; the two indepedent bromine atom share the sames site as the two independent chlorine atoms.

Related literature top

For the structure of bis(4-dimethylaminopyridinium) tetrabromidodiphenylstannate, see: Yap et al. (2008).

Experimental top

Dimethyltin dichoride (2.20 g, 1 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (3.62 g, 1 mmol) were heated in ethanol in an attempt to synthesize the bromodichloridodimethylstannate salt. Colorless crystals separated from it after a few days.

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 [SnBr₂Cl₂(CH₃)₂] at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The disorder is not shown.

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

Crystal data top

(C₇H₁₁N₂)₂[SnBr₂(CH₃)₂Cl₂]	Z = 1
M_r = 625.83	F(000) = 306
Triclinic, P1	D_x = 1.767 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3573 (3) Å	Cell parameters from 1302 reflections
b = 8.7717 (3) Å	θ = 2.3–23.1°
c = 9.6644 (4) Å	µ = 4.72 mm⁻¹
α = 97.183 (3)°	T = 100 K
β = 107.990 (3)°	Prism, colorless
γ = 90.052 (2)°	0.25 × 0.20 × 0.15 mm
V = 588.04 (4) Å³

Data collection top

Bruker SMART APEX diffractometer	2756 independent reflections
Radiation source: fine-focus sealed tube	1656 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS;Sheldrick, 1996)	h = −9→9
T_min = 0.385, T_max = 0.538	k = −11→11
4965 measured reflections	l = −10→12

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.051P)²] where P = (F_o² + 2F_c²)/3
2756 reflections	(Δ/σ)_max = 0.001
122 parameters	Δρ_max = 0.82 e Å⁻³
4 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[SnBr₂(CH₃)₂Cl₂]	γ = 90.052 (2)°
M_r = 625.83	V = 588.04 (4) Å³
Triclinic, P1	Z = 1
a = 7.3573 (3) Å	Mo Kα radiation
b = 8.7717 (3) Å	µ = 4.72 mm⁻¹
c = 9.6644 (4) Å	T = 100 K
α = 97.183 (3)°	0.25 × 0.20 × 0.15 mm
β = 107.990 (3)°

Data collection top

Bruker SMART APEX diffractometer	2756 independent reflections
Absorption correction: multi-scan (SADABS;Sheldrick, 1996)	1656 reflections with I > 2σ(I)
T_min = 0.385, T_max = 0.538	R_int = 0.045
4965 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	4 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.04	Δρ_max = 0.82 e Å⁻³
2756 reflections	Δρ_min = −1.14 e Å⁻³
122 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Sn1	0.5000	0.5000	0.5000	0.0414 (2)
Br1	0.50474 (16)	0.50403 (11)	0.77987 (11)	0.0610 (3)	0.4551 (15)
Br2	0.36593 (14)	0.78543 (10)	0.49452 (10)	0.0588 (3)	0.5449 (15)
Cl1	0.50474 (16)	0.50403 (11)	0.77987 (11)	0.0610 (3)	0.5449 (15)
Cl2	0.36593 (14)	0.78543 (10)	0.49452 (10)	0.0588 (3)	0.4551 (15)
N1	0.6576 (7)	0.1602 (6)	0.8588 (6)	0.0552 (14)
H1	0.6205	0.2248	0.7938	0.066*
N2	0.8414 (7)	−0.1391 (6)	1.1635 (6)	0.0557 (14)
C1	0.2014 (7)	0.4016 (6)	0.4157 (6)	0.0344 (12)
H1A	0.2023	0.2904	0.4192	0.052*
H1B	0.1432	0.4214	0.3142	0.052*
H1C	0.1271	0.4495	0.4767	0.052*
C2	0.6816 (9)	0.2092 (8)	1.0006 (8)	0.0581 (18)
H2	0.6571	0.3128	1.0290	0.070*
C3	0.7413 (9)	0.1116 (7)	1.1061 (7)	0.0545 (16)
H3	0.7570	0.1480	1.2060	0.065*
C4	0.7793 (8)	−0.0433 (7)	1.0650 (7)	0.0443 (15)
C5	0.7486 (8)	−0.0875 (7)	0.9140 (7)	0.0488 (15)
H5	0.7698	−0.1904	0.8805	0.059*
C6	0.6890 (9)	0.0144 (8)	0.8144 (7)	0.0536 (16)
H6	0.6698	−0.0183	0.7132	0.064*
C7	0.8687 (11)	−0.0920 (10)	1.3200 (8)	0.084 (3)
H7A	0.9886	−0.0305	1.3639	0.127*
H7B	0.8740	−0.1836	1.3695	0.127*
H7C	0.7616	−0.0305	1.3310	0.127*
C8	0.8809 (10)	−0.2972 (8)	1.1236 (9)	0.071 (2)
H8A	0.7602	−0.3560	1.0736	0.106*
H8B	0.9498	−0.3417	1.2124	0.106*
H8C	0.9594	−0.3008	1.0579	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0437 (4)	0.0408 (3)	0.0388 (4)	0.0028 (3)	0.0122 (3)	0.0040 (3)
Br1	0.0938 (9)	0.0501 (6)	0.0460 (6)	0.0082 (5)	0.0319 (6)	0.0062 (5)
Br2	0.0809 (7)	0.0458 (5)	0.0461 (6)	0.0187 (5)	0.0144 (5)	0.0062 (4)
Cl1	0.0938 (9)	0.0501 (6)	0.0460 (6)	0.0082 (5)	0.0319 (6)	0.0062 (5)
Cl2	0.0809 (7)	0.0458 (5)	0.0461 (6)	0.0187 (5)	0.0144 (5)	0.0062 (4)
N1	0.050 (3)	0.064 (4)	0.052 (4)	0.001 (3)	0.012 (3)	0.020 (3)
N2	0.048 (3)	0.070 (4)	0.050 (3)	0.004 (3)	0.012 (3)	0.017 (3)
C1	0.032 (3)	0.039 (3)	0.040 (3)	0.009 (2)	0.019 (3)	0.012 (3)
C2	0.050 (4)	0.058 (4)	0.064 (5)	0.007 (3)	0.016 (4)	0.004 (4)
C3	0.048 (4)	0.065 (4)	0.048 (4)	0.001 (3)	0.016 (3)	−0.006 (3)
C4	0.031 (3)	0.063 (4)	0.037 (3)	−0.005 (3)	0.008 (3)	0.009 (3)
C5	0.047 (4)	0.050 (3)	0.047 (4)	−0.003 (3)	0.013 (3)	0.002 (3)
C6	0.054 (4)	0.064 (4)	0.042 (4)	−0.013 (3)	0.016 (3)	0.001 (3)
C7	0.075 (5)	0.136 (7)	0.043 (4)	0.025 (5)	0.013 (4)	0.028 (5)
C8	0.071 (5)	0.063 (5)	0.079 (6)	0.002 (4)	0.016 (4)	0.026 (4)

Geometric parameters (Å, º) top

Sn1—C1ⁱ	2.225 (5)	C1—H1C	0.9800
Sn1—C1	2.225 (5)	C2—C3	1.381 (8)
Sn1—Br1	2.690 (1)	C2—H2	0.9500
Sn1—Cl1ⁱ	2.690 (1)	C3—C4	1.420 (9)
Sn1—Br1ⁱ	2.690 (1)	C3—H3	0.9500
Sn1—Br2ⁱ	2.6926 (8)	C4—C5	1.409 (9)
Sn1—Br2	2.6926 (8)	C5—C6	1.369 (8)
Sn1—Cl2ⁱ	2.6926 (8)	C5—H5	0.9500
N1—C2	1.341 (9)	C6—H6	0.9500
N1—C6	1.341 (9)	C7—H7A	0.9800
N1—H1	0.8800	C7—H7B	0.9800
N2—C4	1.324 (7)	C7—H7C	0.9800
N2—C8	1.446 (9)	C8—H8A	0.9800
N2—C7	1.467 (9)	C8—H8B	0.9800
C1—H1A	0.9800	C8—H8C	0.9800
C1—H1B	0.9800

C1ⁱ—Sn1—C1	180.0	Sn1—C1—H1A	109.5
C1ⁱ—Sn1—Br1	88.38 (14)	Sn1—C1—H1B	109.5
C1—Sn1—Br1	91.62 (14)	H1A—C1—H1B	109.5
C1ⁱ—Sn1—Cl1ⁱ	91.62 (14)	Sn1—C1—H1C	109.5
C1—Sn1—Cl1ⁱ	88.38 (14)	H1A—C1—H1C	109.5
Br1—Sn1—Cl1ⁱ	180.0	H1B—C1—H1C	109.5
C1ⁱ—Sn1—Br1ⁱ	91.62 (14)	N1—C2—C3	121.1 (6)
C1—Sn1—Br1ⁱ	88.38 (14)	N1—C2—H2	119.5
Br1—Sn1—Br1ⁱ	180.0	C3—C2—H2	119.5
Cl1ⁱ—Sn1—Br1ⁱ	0.0	C2—C3—C4	120.0 (6)
C1ⁱ—Sn1—Br2ⁱ	89.83 (13)	C2—C3—H3	120.0
C1—Sn1—Br2ⁱ	90.17 (13)	C4—C3—H3	120.0
Br1—Sn1—Br2ⁱ	89.12 (3)	N2—C4—C5	122.5 (6)
Cl1ⁱ—Sn1—Br2ⁱ	90.88 (3)	N2—C4—C3	121.6 (6)
Br1ⁱ—Sn1—Br2ⁱ	90.88 (3)	C5—C4—C3	115.9 (6)
C1ⁱ—Sn1—Br2	90.17 (13)	C6—C5—C4	121.5 (6)
C1—Sn1—Br2	89.83 (13)	C6—C5—H5	119.2
Br1—Sn1—Br2	90.88 (3)	C4—C5—H5	119.2
Cl1ⁱ—Sn1—Br2	89.12 (3)	N1—C6—C5	120.4 (6)
Br1ⁱ—Sn1—Br2	89.12 (3)	N1—C6—H6	119.8
Br2ⁱ—Sn1—Br2	180.0	C5—C6—H6	119.8
C1ⁱ—Sn1—Cl2ⁱ	89.83 (13)	N2—C7—H7A	109.5
C1—Sn1—Cl2ⁱ	90.17 (13)	N2—C7—H7B	109.5
Br1—Sn1—Cl2ⁱ	89.12 (3)	H7A—C7—H7B	109.5
Cl1ⁱ—Sn1—Cl2ⁱ	90.88 (3)	N2—C7—H7C	109.5
Br1ⁱ—Sn1—Cl2ⁱ	90.88 (3)	H7A—C7—H7C	109.5
Br2ⁱ—Sn1—Cl2ⁱ	0.000 (13)	H7B—C7—H7C	109.5
Br2—Sn1—Cl2ⁱ	180.0	N2—C8—H8A	109.5
C2—N1—C6	121.1 (6)	N2—C8—H8B	109.5
C2—N1—H1	119.4	H8A—C8—H8B	109.5
C6—N1—H1	119.4	N2—C8—H8C	109.5
C4—N2—C8	122.3 (6)	H8A—C8—H8C	109.5
C4—N2—C7	121.8 (6)	H8B—C8—H8C	109.5
C8—N2—C7	115.9 (6)

C6—N1—C2—C3	0.6 (9)	C2—C3—C4—N2	178.3 (5)
N1—C2—C3—C4	0.3 (10)	C2—C3—C4—C5	−1.1 (8)
C8—N2—C4—C5	−0.6 (9)	N2—C4—C5—C6	−178.3 (6)
C7—N2—C4—C5	−178.7 (6)	C3—C4—C5—C6	1.1 (9)
C8—N2—C4—C3	−180.0 (5)	C2—N1—C6—C5	−0.7 (9)
C7—N2—C4—C3	1.9 (9)	C4—C5—C6—N1	−0.2 (9)

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
N1—H1···Br1	0.88	2.60	3.316 (5)	139
N1—H1···Br2ⁱ	0.88	2.81	3.458 (6)	132

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[SnBr₂(CH₃)₂Cl₂]
M_r	625.83
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.3573 (3), 8.7717 (3), 9.6644 (4)
α, β, γ (°)	97.183 (3), 107.990 (3), 90.052 (2)
V (Å³)	588.04 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	4.72
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS;Sheldrick, 1996)
T_min, T_max	0.385, 0.538
No. of measured, independent and observed [I > 2σ(I)] reflections	4965, 2756, 1656
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.123, 1.04
No. of reflections	2756
No. of parameters	122
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −1.14

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

Selected bond lengths (Å) top

Sn1—C1	2.225 (5)	Sn1—Br2	2.6926 (8)
Sn1—Br1	2.690 (1)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.88	2.60	3.316 (5)	139
N1—H1···Br2ⁱ	0.88	2.81	3.458 (6)	132

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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. (2008). 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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m800

doi:10.1107/S1600536808013561

Open

access