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

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

doi:10.1107/S160053680901705X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m645

doi:10.1107/S160053680901705X

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

Yong Jang,^a 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 4 May 2009; accepted 6 May 2009; online 14 May 2009)

In the title compound, (C₇H₁₁N₂)₂[SnBr₅Cl], there is Br/Cl disorder in 0.6561 (12):0.3439 (12) and 0.8438 (12):0.1561 (12) ratios over two of three halide sites in the centrosymmetric anion, such that an overall formulation of [SnBr₅Cl]²⁻ arises. In the crystal, associations of two cations and one anion linked by N—H⋯Br hydrogen bonds occur.

Related literature

For related 4-dimethylaminopyridinium halogenoorganostannates, see: Lo & Ng (2008 ); Norhafiza et al. (2008 ); Yau et al. (2008 ).

Experimental

Crystal data

(C₇H₁₁N₂)₂[SnBr₅Cl]
M_r = 800.05
Monoclinic, P 2₁ /c
a = 8.4424 (1) Å
b = 11.8821 (2) Å
c = 11.8868 (2) Å
β = 107.123 (1)°
V = 1139.55 (3) Å³
Z = 2
Mo Kα radiation
μ = 10.01 mm⁻¹
T = 100 K
0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.152, T_max = 0.434 (expected range = 0.129–0.367)
9261 measured reflections
2613 independent reflections
2408 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.053
S = 1.01
2613 reflections
121 parameters
4 restraints
H-atom parameters constrained
Δρ_max = 0.91 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Table 1
Selected bond lengths (Å). X = (Br, Cl)

Sn1—X1	2.5608 (3)
Sn1—X2	2.5618 (3)
Sn1—X3	2.5687 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br1	0.88	2.47	3.327 (2)	165

Data collection: APEX2 software (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/S160053680901705X/hb2965sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901705X/hb2965Isup2.hkl

checkCIF report

Related literature top

For related 4-dimethylaminopyridinium halogenoorganostannates, see: Lo & Ng (2008); Norhafiza et al. (2008); Yau et al. (2008).

Experimental top

Dibenzyltin dichloride (0.37 g, 1 mmol) and 4-dimethylaminopyridine hydrobromide perbromide (0.73 g, 2 mmol) were heated in chloroform for 3 hours. Colourless blocks of (I) separated from the cool solution after a day. The crystal structure showed that the benzyl groups on tin had been cleaved in the reaction.

Computing details top

Data collection: APEX2 software (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. The molecular structure of (I) viewed at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

(C₇H₁₁N₂)₂[SnBr₅Cl]	F(000) = 752
M_r = 800.05	D_x = 2.332 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5777 reflections
a = 8.4424 (1) Å	θ = 2.5–28.3°
b = 11.8821 (2) Å	µ = 10.01 mm⁻¹
c = 11.8868 (2) Å	T = 100 K
β = 107.123 (1)°	Block, colourless
V = 1139.55 (3) Å³	0.30 × 0.10 × 0.10 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	2613 independent reflections
Radiation source: fine-focus sealed tube	2408 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.152, T_max = 0.434	k = −15→15
9261 measured reflections	l = −15→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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.053	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0276P)² + 1.7721P] where P = (F_o² + 2F_c²)/3
2613 reflections	(Δ/σ)_max = 0.001
121 parameters	Δρ_max = 0.91 e Å⁻³
4 restraints	Δρ_min = −0.95 e Å⁻³

Crystal data top

(C₇H₁₁N₂)₂[SnBr₅Cl]	V = 1139.55 (3) Å³
M_r = 800.05	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4424 (1) Å	µ = 10.01 mm⁻¹
b = 11.8821 (2) Å	T = 100 K
c = 11.8868 (2) Å	0.30 × 0.10 × 0.10 mm
β = 107.123 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2613 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2408 reflections with I > 2σ(I)
T_min = 0.152, T_max = 0.434	R_int = 0.022
9261 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	4 restraints
wR(F²) = 0.053	H-atom parameters constrained
S = 1.01	Δρ_max = 0.91 e Å⁻³
2613 reflections	Δρ_min = −0.95 e Å⁻³
121 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	0.01035 (7)
Br1	0.50979 (5)	0.63602 (3)	0.66902 (3)	0.02104 (10)	0.6561 (12)
Br2	0.58402 (4)	0.33881 (2)	0.64884 (3)	0.02209 (9)	0.8438 (12)
Br3	0.80725 (3)	0.53820 (3)	0.52248 (3)	0.02568 (8)
Cl1	0.50979 (5)	0.63602 (3)	0.66902 (3)	0.02104 (10)	0.3439 (12)
Cl2	0.58402 (4)	0.33881 (2)	0.64884 (3)	0.02209 (9)	0.1561 (12)
N1	0.6520 (3)	0.8746 (2)	0.5886 (3)	0.0271 (6)
H1	0.5999	0.8123	0.5962	0.032*
N2	0.9139 (3)	1.15682 (19)	0.5545 (2)	0.0186 (5)
C1	0.8253 (3)	1.0669 (2)	0.5659 (2)	0.0154 (5)
C2	0.7373 (4)	1.0025 (2)	0.4666 (3)	0.0194 (5)
H2	0.7358	1.0257	0.3898	0.023*
C3	0.6551 (4)	0.9077 (2)	0.4809 (3)	0.0245 (6)
H3	0.5991	0.8642	0.4139	0.029*
C4	0.7277 (4)	0.9358 (3)	0.6848 (3)	0.0251 (6)
H4	0.7203	0.9125	0.7595	0.030*
C5	0.8137 (4)	1.0296 (2)	0.6768 (3)	0.0211 (6)
H5	0.8670	1.0711	0.7459	0.025*
C6	0.9127 (4)	1.1990 (3)	0.4393 (3)	0.0249 (6)
H6A	0.9488	1.1393	0.3955	0.037*
H6B	0.9883	1.2633	0.4490	0.037*
H6C	0.8002	1.2229	0.3958	0.037*
C7	1.0105 (4)	1.2208 (3)	0.6571 (3)	0.0291 (7)
H7A	0.9353	1.2650	0.6887	0.044*
H7B	1.0866	1.2715	0.6336	0.044*
H7C	1.0740	1.1687	0.7175	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.00978 (11)	0.01195 (11)	0.00936 (12)	−0.00163 (8)	0.00287 (9)	−0.00006 (8)
Br1	0.0306 (2)	0.01735 (16)	0.01761 (19)	−0.00301 (13)	0.01094 (15)	−0.00399 (12)
Br2	0.03025 (18)	0.01759 (15)	0.01582 (17)	−0.00058 (12)	0.00271 (13)	0.00430 (11)
Br3	0.01302 (14)	0.03789 (17)	0.02652 (17)	−0.00656 (11)	0.00643 (12)	−0.00107 (12)
Cl1	0.0306 (2)	0.01735 (16)	0.01761 (19)	−0.00301 (13)	0.01094 (15)	−0.00399 (12)
Cl2	0.03025 (18)	0.01759 (15)	0.01582 (17)	−0.00058 (12)	0.00271 (13)	0.00430 (11)
N1	0.0210 (12)	0.0210 (12)	0.0407 (17)	−0.0003 (10)	0.0115 (11)	0.0092 (11)
N2	0.0175 (11)	0.0195 (11)	0.0167 (12)	−0.0033 (9)	0.0019 (9)	−0.0018 (9)
C1	0.0123 (12)	0.0183 (12)	0.0145 (13)	0.0038 (9)	0.0025 (10)	0.0005 (10)
C2	0.0183 (13)	0.0212 (13)	0.0170 (14)	0.0007 (10)	0.0024 (11)	−0.0009 (11)
C3	0.0208 (14)	0.0230 (14)	0.0265 (16)	−0.0016 (11)	0.0019 (12)	−0.0023 (12)
C4	0.0214 (14)	0.0320 (15)	0.0256 (16)	0.0108 (12)	0.0130 (12)	0.0122 (13)
C5	0.0207 (14)	0.0283 (14)	0.0141 (14)	0.0061 (11)	0.0049 (11)	0.0018 (11)
C6	0.0240 (14)	0.0240 (14)	0.0251 (16)	−0.0053 (11)	0.0047 (12)	0.0069 (12)
C7	0.0290 (16)	0.0304 (16)	0.0233 (17)	−0.0097 (12)	0.0007 (13)	−0.0110 (13)

Geometric parameters (Å, º) top

Sn1—Br1	2.5608 (3)	C1—C2	1.419 (4)
Sn1—Cl1ⁱ	2.5608 (3)	C1—C5	1.421 (4)
Sn1—Br1ⁱ	2.5608 (3)	C2—C3	1.360 (4)
Sn1—Br2	2.5618 (3)	C2—H2	0.9500
Sn1—Cl2ⁱ	2.5618 (3)	C3—H3	0.9500
Sn1—Br2ⁱ	2.5618 (3)	C4—C5	1.348 (4)
Sn1—Br3ⁱ	2.5687 (3)	C4—H4	0.9500
Sn1—Br3	2.5687 (3)	C5—H5	0.9500
N1—C4	1.347 (4)	C6—H6A	0.9800
N1—C3	1.347 (4)	C6—H6B	0.9800
N1—H1	0.8800	C6—H6C	0.9800
N2—C1	1.334 (3)	C7—H7A	0.9800
N2—C6	1.456 (4)	C7—H7B	0.9800
N2—C7	1.464 (4)	C7—H7C	0.9800

Br1—Sn1—Cl1ⁱ	180.0	C1—N2—C6	121.5 (2)
Br1—Sn1—Br1ⁱ	180.0	C1—N2—C7	121.6 (2)
Cl1ⁱ—Sn1—Br1ⁱ	0.000 (11)	C6—N2—C7	116.9 (2)
Br1—Sn1—Br2	89.520 (11)	N2—C1—C2	121.3 (3)
Cl1ⁱ—Sn1—Br2	90.480 (11)	N2—C1—C5	122.5 (3)
Br1ⁱ—Sn1—Br2	90.480 (11)	C2—C1—C5	116.2 (3)
Br1—Sn1—Cl2ⁱ	90.480 (11)	C3—C2—C1	120.3 (3)
Cl1ⁱ—Sn1—Cl2ⁱ	89.520 (11)	C3—C2—H2	119.8
Br1ⁱ—Sn1—Cl2ⁱ	89.520 (11)	C1—C2—H2	119.8
Br2—Sn1—Cl2ⁱ	180.000 (12)	N1—C3—C2	120.9 (3)
Br1—Sn1—Br2ⁱ	90.480 (11)	N1—C3—H3	119.6
Cl1ⁱ—Sn1—Br2ⁱ	89.520 (11)	C2—C3—H3	119.6
Br1ⁱ—Sn1—Br2ⁱ	89.520 (11)	N1—C4—C5	121.1 (3)
Br2—Sn1—Br2ⁱ	180.000 (12)	N1—C4—H4	119.4
Cl2ⁱ—Sn1—Br2ⁱ	0.00 (2)	C5—C4—H4	119.4
Br1—Sn1—Br3ⁱ	89.512 (11)	C4—C5—C1	120.6 (3)
Cl1ⁱ—Sn1—Br3ⁱ	90.488 (11)	C4—C5—H5	119.7
Br1ⁱ—Sn1—Br3ⁱ	90.488 (11)	C1—C5—H5	119.7
Br2—Sn1—Br3ⁱ	90.316 (10)	N2—C6—H6A	109.5
Cl2ⁱ—Sn1—Br3ⁱ	89.684 (10)	N2—C6—H6B	109.5
Br2ⁱ—Sn1—Br3ⁱ	89.684 (10)	H6A—C6—H6B	109.5
Br1—Sn1—Br3	90.488 (11)	N2—C6—H6C	109.5
Cl1ⁱ—Sn1—Br3	89.512 (11)	H6A—C6—H6C	109.5
Br1ⁱ—Sn1—Br3	89.512 (11)	H6B—C6—H6C	109.5
Br2—Sn1—Br3	89.684 (10)	N2—C7—H7A	109.5
Cl2ⁱ—Sn1—Br3	90.316 (10)	N2—C7—H7B	109.5
Br2ⁱ—Sn1—Br3	90.316 (10)	H7A—C7—H7B	109.5
Br3ⁱ—Sn1—Br3	180.0	N2—C7—H7C	109.5
C4—N1—C3	120.8 (3)	H7A—C7—H7C	109.5
C4—N1—H1	119.6	H7B—C7—H7C	109.5
C3—N1—H1	119.6

C6—N2—C1—C2	5.6 (4)	C4—N1—C3—C2	1.3 (4)
C7—N2—C1—C2	−177.4 (3)	C1—C2—C3—N1	1.7 (4)
C6—N2—C1—C5	−174.8 (3)	C3—N1—C4—C5	−2.4 (4)
C7—N2—C1—C5	2.2 (4)	N1—C4—C5—C1	0.6 (4)
N2—C1—C2—C3	176.4 (3)	N2—C1—C5—C4	−177.5 (3)
C5—C1—C2—C3	−3.3 (4)	C2—C1—C5—C4	2.2 (4)

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	2.47	3.327 (2)	165

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)₂[SnBr₅Cl]
M_r	800.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.4424 (1), 11.8821 (2), 11.8868 (2)
β (°)	107.123 (1)
V (Å³)	1139.55 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	10.01
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.152, 0.434
No. of measured, independent and observed [I > 2σ(I)] reflections	9261, 2613, 2408
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.053, 1.01
No. of reflections	2613
No. of parameters	121
No. of restraints	4
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.91, −0.95

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

Selected bond lengths (Å) top

Sn1—Br1	2.5608 (3)	Sn1—Br3	2.5687 (3)
Sn1—Br2	2.5618 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.88	2.47	3.327 (2)	165

Acknowledgements

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

References

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