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

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

doi:10.1107/S1600536809019734

metal-organic compounds

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doi:10.1107/S1600536809019734

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Bis[4-(dimethylamino)pyridinium] hexakis[bromido/chlorido(0.78/0.22)]stannate(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 19 May 2009; accepted 25 May 2009; online 6 June 2009)

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, P 2₁ /c
a = 8.4530 (2) Å
b = 11.9036 (2) Å
c = 11.9093 (2) Å
β = 107.109 (1)°
V = 1145.30 (4) Å³
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[F² > 2σ(F²)] = 0.023
wR(F²) = 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

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)

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019734/tk2458sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019734/tk2458Isup2.hkl

checkCIF report

Related literature top

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

Experimental top

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).

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: pubCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 2[C₇H₁₁N₂]⁺ [SnBr_4.67Cl_1.33]^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.

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

Crystal data top

(C₇H₁₁N₂)₂[SnBr_4.67Cl_1.33]	F(000) = 740
M_r = 785.15	D_x = 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 top

Bruker SMART APEX diffractometer	2622 independent reflections
Radiation source: fine-focus sealed tube	2240 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.504, T_max = 0.746	k = −15→15
10319 measured reflections	l = −14→15

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)] = 0.023	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(F_o²) + (0.0343P)² + 0.6005P] where P = (F_o² + 2F_c²)/3
2622 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.80 e Å⁻³
6 restraints	Δρ_min = −0.87 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[SnBr_4.67Cl_1.33]	V = 1145.30 (4) Å³
M_r = 785.15	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4530 (2) Å	µ = 9.42 mm⁻¹
b = 11.9036 (2) Å	T = 100 K
c = 11.9093 (2) Å	0.30 × 0.25 × 0.20 mm
β = 107.109 (1)°

Data collection top

Bruker SMART APEX diffractometer	2622 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2240 reflections with I > 2σ(I)
T_min = 0.504, T_max = 0.746	R_int = 0.033
10319 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	6 restraints
wR(F²) = 0.060	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.80 e Å⁻³
2622 reflections	Δρ_min = −0.87 e Å⁻³
127 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	0.01384 (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 (Å²) top

	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, º) top

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 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 (1)	2.48 (2)	3.334 (3)	162 (4)

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[SnBr_4.67Cl_1.33]
M_r	785.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.4530 (2), 11.9036 (2), 11.9093 (2)
β (°)	107.109 (1)
V (Å³)	1145.30 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	9.42
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.504, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	10319, 2622, 2240
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.060, 0.99
No. of reflections	2622
No. of parameters	127
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.87

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), pubCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

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)

Acknowledgements

We thank the University of Malaya (RG020/09AFR) for supporting this study.

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
Jang, Y., Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, m645. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m834. 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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m715

doi:10.1107/S1600536809019734

Open

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Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

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

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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