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ISSN: 2056-9890

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

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[Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m834.]); Norhafiza et al. (2008[Norhafiza, I., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m720.]); Yau et al. (2008[Yau, C. K., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m1391.]).

[Scheme 1]

Experimental

Crystal data
  • (C7H11N2)2[SnBr5Cl]

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.152, Tmax = 0.434 (expected range = 0.129–0.367)

  • 9261 measured reflections

  • 2613 independent reflections

  • 2408 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.91 e Å−3

  • Δρmin = −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 DA D—H⋯A
N1—H1⋯Br1 0.88 2.47 3.327 (2) 165

Data collection: APEX2 software (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


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.

Refinement top

Hydrogen atoms were placed at calculated positions (C–H 0.95, N–H 0.88 Å) and were treated as riding on their parent atoms, with U(H) set to 1.2 times Ueq(C,N).

Two of the three halogen atoms in the stannate are disordered. The pair of Br1/Cl1 and Br2/Cl2 atoms initially refined to nearly 1.5Br and 0.5Cl atoms; the total occupancy of the disordered bromine atoms was then fixed as exactly 1.5. The occupancy of the disordered chlorine atoms was similarly set to be exactly 0.5.

The Uij values of the Br1 and Cl1 atoms were restrained to be identical, as were those of the Br2 and Cl2 atoms.

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
[Figure 1] 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
Mr = 800.05Dx = 2.332 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5777 reflections
a = 8.4424 (1) Åθ = 2.5–28.3°
b = 11.8821 (2) ŵ = 10.01 mm1
c = 11.8868 (2) ÅT = 100 K
β = 107.123 (1)°Block, colourless
V = 1139.55 (3) Å30.30 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer
2613 independent reflections
Radiation source: fine-focus sealed tube2408 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1010
Tmin = 0.152, Tmax = 0.434k = 1515
9261 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.021Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0276P)2 + 1.7721P]
where P = (Fo2 + 2Fc2)/3
2613 reflections(Δ/σ)max = 0.001
121 parametersΔρmax = 0.91 e Å3
4 restraintsΔρmin = 0.95 e Å3
Crystal data top
(C7H11N2)2[SnBr5Cl]V = 1139.55 (3) Å3
Mr = 800.05Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.4424 (1) ŵ = 10.01 mm1
b = 11.8821 (2) ÅT = 100 K
c = 11.8868 (2) Å0.30 × 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)
Tmin = 0.152, Tmax = 0.434Rint = 0.022
9261 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0214 restraints
wR(F2) = 0.053H-atom parameters constrained
S = 1.01Δρmax = 0.91 e Å3
2613 reflectionsΔρmin = 0.95 e Å3
121 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sn10.50000.50000.50000.01035 (7)
Br10.50979 (5)0.63602 (3)0.66902 (3)0.02104 (10)0.6561 (12)
Br20.58402 (4)0.33881 (2)0.64884 (3)0.02209 (9)0.8438 (12)
Br30.80725 (3)0.53820 (3)0.52248 (3)0.02568 (8)
Cl10.50979 (5)0.63602 (3)0.66902 (3)0.02104 (10)0.3439 (12)
Cl20.58402 (4)0.33881 (2)0.64884 (3)0.02209 (9)0.1561 (12)
N10.6520 (3)0.8746 (2)0.5886 (3)0.0271 (6)
H10.59990.81230.59620.032*
N20.9139 (3)1.15682 (19)0.5545 (2)0.0186 (5)
C10.8253 (3)1.0669 (2)0.5659 (2)0.0154 (5)
C20.7373 (4)1.0025 (2)0.4666 (3)0.0194 (5)
H20.73581.02570.38980.023*
C30.6551 (4)0.9077 (2)0.4809 (3)0.0245 (6)
H30.59910.86420.41390.029*
C40.7277 (4)0.9358 (3)0.6848 (3)0.0251 (6)
H40.72030.91250.75950.030*
C50.8137 (4)1.0296 (2)0.6768 (3)0.0211 (6)
H50.86701.07110.74590.025*
C60.9127 (4)1.1990 (3)0.4393 (3)0.0249 (6)
H6A0.94881.13930.39550.037*
H6B0.98831.26330.44900.037*
H6C0.80021.22290.39580.037*
C71.0105 (4)1.2208 (3)0.6571 (3)0.0291 (7)
H7A0.93531.26500.68870.044*
H7B1.08661.27150.63360.044*
H7C1.07401.16870.71750.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.00978 (11)0.01195 (11)0.00936 (12)0.00163 (8)0.00287 (9)0.00006 (8)
Br10.0306 (2)0.01735 (16)0.01761 (19)0.00301 (13)0.01094 (15)0.00399 (12)
Br20.03025 (18)0.01759 (15)0.01582 (17)0.00058 (12)0.00271 (13)0.00430 (11)
Br30.01302 (14)0.03789 (17)0.02652 (17)0.00656 (11)0.00643 (12)0.00107 (12)
Cl10.0306 (2)0.01735 (16)0.01761 (19)0.00301 (13)0.01094 (15)0.00399 (12)
Cl20.03025 (18)0.01759 (15)0.01582 (17)0.00058 (12)0.00271 (13)0.00430 (11)
N10.0210 (12)0.0210 (12)0.0407 (17)0.0003 (10)0.0115 (11)0.0092 (11)
N20.0175 (11)0.0195 (11)0.0167 (12)0.0033 (9)0.0019 (9)0.0018 (9)
C10.0123 (12)0.0183 (12)0.0145 (13)0.0038 (9)0.0025 (10)0.0005 (10)
C20.0183 (13)0.0212 (13)0.0170 (14)0.0007 (10)0.0024 (11)0.0009 (11)
C30.0208 (14)0.0230 (14)0.0265 (16)0.0016 (11)0.0019 (12)0.0023 (12)
C40.0214 (14)0.0320 (15)0.0256 (16)0.0108 (12)0.0130 (12)0.0122 (13)
C50.0207 (14)0.0283 (14)0.0141 (14)0.0061 (11)0.0049 (11)0.0018 (11)
C60.0240 (14)0.0240 (14)0.0251 (16)0.0053 (11)0.0047 (12)0.0069 (12)
C70.0290 (16)0.0304 (16)0.0233 (17)0.0097 (12)0.0007 (13)0.0110 (13)
Geometric parameters (Å, º) top
Sn1—Br12.5608 (3)C1—C21.419 (4)
Sn1—Cl1i2.5608 (3)C1—C51.421 (4)
Sn1—Br1i2.5608 (3)C2—C31.360 (4)
Sn1—Br22.5618 (3)C2—H20.9500
Sn1—Cl2i2.5618 (3)C3—H30.9500
Sn1—Br2i2.5618 (3)C4—C51.348 (4)
Sn1—Br3i2.5687 (3)C4—H40.9500
Sn1—Br32.5687 (3)C5—H50.9500
N1—C41.347 (4)C6—H6A0.9800
N1—C31.347 (4)C6—H6B0.9800
N1—H10.8800C6—H6C0.9800
N2—C11.334 (3)C7—H7A0.9800
N2—C61.456 (4)C7—H7B0.9800
N2—C71.464 (4)C7—H7C0.9800
Br1—Sn1—Cl1i180.0C1—N2—C6121.5 (2)
Br1—Sn1—Br1i180.0C1—N2—C7121.6 (2)
Cl1i—Sn1—Br1i0.000 (11)C6—N2—C7116.9 (2)
Br1—Sn1—Br289.520 (11)N2—C1—C2121.3 (3)
Cl1i—Sn1—Br290.480 (11)N2—C1—C5122.5 (3)
Br1i—Sn1—Br290.480 (11)C2—C1—C5116.2 (3)
Br1—Sn1—Cl2i90.480 (11)C3—C2—C1120.3 (3)
Cl1i—Sn1—Cl2i89.520 (11)C3—C2—H2119.8
Br1i—Sn1—Cl2i89.520 (11)C1—C2—H2119.8
Br2—Sn1—Cl2i180.000 (12)N1—C3—C2120.9 (3)
Br1—Sn1—Br2i90.480 (11)N1—C3—H3119.6
Cl1i—Sn1—Br2i89.520 (11)C2—C3—H3119.6
Br1i—Sn1—Br2i89.520 (11)N1—C4—C5121.1 (3)
Br2—Sn1—Br2i180.000 (12)N1—C4—H4119.4
Cl2i—Sn1—Br2i0.00 (2)C5—C4—H4119.4
Br1—Sn1—Br3i89.512 (11)C4—C5—C1120.6 (3)
Cl1i—Sn1—Br3i90.488 (11)C4—C5—H5119.7
Br1i—Sn1—Br3i90.488 (11)C1—C5—H5119.7
Br2—Sn1—Br3i90.316 (10)N2—C6—H6A109.5
Cl2i—Sn1—Br3i89.684 (10)N2—C6—H6B109.5
Br2i—Sn1—Br3i89.684 (10)H6A—C6—H6B109.5
Br1—Sn1—Br390.488 (11)N2—C6—H6C109.5
Cl1i—Sn1—Br389.512 (11)H6A—C6—H6C109.5
Br1i—Sn1—Br389.512 (11)H6B—C6—H6C109.5
Br2—Sn1—Br389.684 (10)N2—C7—H7A109.5
Cl2i—Sn1—Br390.316 (10)N2—C7—H7B109.5
Br2i—Sn1—Br390.316 (10)H7A—C7—H7B109.5
Br3i—Sn1—Br3180.0N2—C7—H7C109.5
C4—N1—C3120.8 (3)H7A—C7—H7C109.5
C4—N1—H1119.6H7B—C7—H7C109.5
C3—N1—H1119.6
C6—N2—C1—C25.6 (4)C4—N1—C3—C21.3 (4)
C7—N2—C1—C2177.4 (3)C1—C2—C3—N11.7 (4)
C6—N2—C1—C5174.8 (3)C3—N1—C4—C52.4 (4)
C7—N2—C1—C52.2 (4)N1—C4—C5—C10.6 (4)
N2—C1—C2—C3176.4 (3)N2—C1—C5—C4177.5 (3)
C5—C1—C2—C33.3 (4)C2—C1—C5—C42.2 (4)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.473.327 (2)165

Experimental details

Crystal data
Chemical formula(C7H11N2)2[SnBr5Cl]
Mr800.05
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)8.4424 (1), 11.8821 (2), 11.8868 (2)
β (°) 107.123 (1)
V3)1139.55 (3)
Z2
Radiation typeMo Kα
µ (mm1)10.01
Crystal size (mm)0.30 × 0.10 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.152, 0.434
No. of measured, independent and
observed [I > 2σ(I)] reflections
9261, 2613, 2408
Rint0.022
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.021, 0.053, 1.01
No. of reflections2613
No. of parameters121
No. of restraints4
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—Br12.5608 (3)Sn1—Br32.5687 (3)
Sn1—Br22.5618 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Br10.882.473.327 (2)165
 

Acknowledgements

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

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationLo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m834.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationNorhafiza, I., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m720.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar
First citationYau, C. K., Lo, K. M. & Ng, S. W. (2008). Acta Cryst. E64, m1391.  Web of Science CrossRef IUCr Journals Google Scholar

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