Acta Cryst. (2009). E65, m645 [ doi:10.1107/S160053680901705X ]
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.
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.
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.
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).
![[Figure 1]](./hb2965fig1thm.gif)
| Fig. 1. The molecular structure of (I) viewed at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. |
| (C7H11N2)2[SnBr5Cl] | F000 = 752 |
| Mr = 800.05 | Dx = 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 = 2.5–28.3º |
| b = 11.8821 (2) Å | µ = 10.01 mm−1 |
| c = 11.8868 (2) Å | T = 100 K |
| β = 107.123 (1)º | Block, colourless |
| V = 1139.55 (3) Å3 | 0.30 × 0.10 × 0.10 mm |
| Z = 2 |
| Bruker SMART APEX CCD diffractometer | 2613 independent reflections |
| Radiation source: fine-focus sealed tube | 2408 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.022 |
| T = 100 K | θmax = 27.5º |
| ω scans | θmin = 2.5º |
| Absorption correction: Multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
| Tmin = 0.152, Tmax = 0.434 | k = −15→15 |
| 9261 measured reflections | l = −15→15 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.021 | H-atom parameters constrained |
| wR(F2) = 0.053 | w = 1/[σ2(Fo2) + (0.0276P)2 + 1.7721P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 2613 reflections | Δρmax = 0.91 e Å−3 |
| 121 parameters | Δρmin = −0.95 e Å−3 |
| 4 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| (C7H11N2)2[SnBr5Cl] | V = 1139.55 (3) Å3 |
| Mr = 800.05 | Z = 2 |
| Monoclinic, P21/c | Mo Kα |
| 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)º |
| 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 = 0.434 | Rint = 0.022 |
| 9261 measured reflections |
| R[F2 > 2σ(F2)] = 0.021 | 4 restraints |
| wR(F2) = 0.053 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.91 e Å−3 |
| 2613 reflections | Δρmin = −0.95 e Å−3 |
| 121 parameters |
| x | y | z | Uiso*/Ueq | 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* |
| 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) |
| 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 codes: (i) −x+1, −y+1, −z+1. |
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Westrip, S. P. (2009). publCIF. In preparation.
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