Acta Cryst. (2008). E64, m637-m638 [ doi:10.1107/S160053680800901X ]
The asymmetric unit of the title compound, (C5H5BrN)2[SnCl6], contains one cation and one half-anion. The [SnCl6]2- anion is located on an inversion center and forms a quasi-regular octahedral arrangement. Hydrogen-bonding interactions of two kinds, viz. N-H
Cl-Sn and C-HCl-Sn, along with ClBr interactions [3.4393 (15) Å], connect the ions in the crystal structure into two-dimensional supramolecular arrays. These supramolecular arrays are arranged in layers approximately parallel to (110) built up from anions interacting with six symmetry-related surrounding cations.
Warm solution of SnCl4 (1.0 mmol) dissolved in absolute ethanol (10 ml) and concentrated HCl (1 ml), was added dropwise to a stirred hot solution of 2-bromopyridine (1 mmol) dissolved in ethanol (10 ml). The mixture was treated with another 2 ml of concentrated HCl and refluxed for 2 h, then cooled, filtered off, and allowed to stand undisturbed at room temperature. The salt crystallized over 1 d as nice yellow block crystals (yield: 89.6%).
H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bh2165fig1thm.gif)
| Fig. 1. A view of the asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./bh2165fig2thm.gif)
| Fig. 2. A packing diagram of (I). Hydrogen bonds and Cl···Br interactions are shown as dashed lines. |
![[Figure 3]](./bh2165fig3thm.gif)
| Fig. 3. Part of the cell contents of (I), showing Cl···Br and (C,N)—H···Cl intermolecular interactions (dashed lines) for one (SnCl6)2- anion and six surrounding cations. |
| (C5H5BrN)2[SnCl6] | F000 = 612 |
| Mr = 649.41 | Dx = 2.222 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 90 reflections |
| a = 9.0843 (14) Å | θ = 1.6–27.4º |
| b = 10.6827 (9) Å | µ = 6.25 mm−1 |
| c = 10.6345 (17) Å | T = 296 (2) K |
| β = 109.843 (11)º | Block, yellow |
| V = 970.8 (2) Å3 | 0.20 × 0.15 × 0.10 mm |
| Z = 2 |
| Siemens P4 diffractometer | 1791 independent reflections |
| Radiation source: fine-focus sealed tube | 1343 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.048 |
| Detector resolution: 3 pixels mm-1 | θmax = 25.5º |
| T = 296(2) K | θmin = 2.8º |
| ω scans | h = −1→11 |
| Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −12→1 |
| Tmin = 0.340, Tmax = 0.535 | l = −12→12 |
| 2385 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0417P)2 + 0.8983P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.097 | (Δ/σ)max < 0.001 |
| S = 1.05 | Δρmax = 0.61 e Å−3 |
| 1791 reflections | Δρmin = −0.73 e Å−3 |
| 98 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0145 (10) |
| Secondary atom site location: difference Fourier map |
| (C5H5BrN)2[SnCl6] | V = 970.8 (2) Å3 |
| Mr = 649.41 | Z = 2 |
| Monoclinic, P21/n | Mo Kα |
| a = 9.0843 (14) Å | µ = 6.25 mm−1 |
| b = 10.6827 (9) Å | T = 296 (2) K |
| c = 10.6345 (17) Å | 0.20 × 0.15 × 0.10 mm |
| β = 109.843 (11)º |
| Siemens P4 diffractometer | 1791 independent reflections |
| Absorption correction: ψ scan (XSCANS; Siemens, 1996) | 1343 reflections with I > 2σ(I) |
| Tmin = 0.340, Tmax = 0.535 | Rint = 0.048 |
| 2385 measured reflections |
| R[F2 > 2σ(F2)] = 0.040 | 98 parameters |
| wR(F2) = 0.097 | H-atom parameters constrained |
| S = 1.05 | Δρmax = 0.61 e Å−3 |
| 1791 reflections | Δρmin = −0.73 e Å−3 |
| x | y | z | Uiso*/Ueq | ||
| Sn1 | 0.0000 | 0.0000 | 0.5000 | 0.0271 (2) | |
| Br2 | 0.68293 (9) | 0.00098 (6) | 0.92745 (7) | 0.0595 (3) | |
| Cl1 | 0.15178 (16) | 0.07315 (13) | 0.36630 (13) | 0.0376 (4) | |
| Cl2 | 0.24265 (16) | −0.03276 (15) | 0.68883 (14) | 0.0474 (4) | |
| Cl3 | 0.01440 (19) | −0.21235 (13) | 0.42546 (16) | 0.0500 (4) | |
| N1 | 0.8532 (5) | 0.1873 (5) | 1.0891 (4) | 0.0410 (11) | |
| H1 | 0.7983 | 0.1643 | 1.1369 | 0.049* | |
| C6 | 0.9552 (7) | 0.2804 (5) | 1.1327 (6) | 0.0485 (15) | |
| H6 | 0.9655 | 0.3203 | 1.2130 | 0.058* | |
| C5 | 1.0445 (8) | 0.3170 (7) | 1.0591 (7) | 0.0612 (19) | |
| H5 | 1.1162 | 0.3820 | 1.0881 | 0.073* | |
| C2 | 0.8330 (6) | 0.1285 (5) | 0.9736 (5) | 0.0368 (12) | |
| C4 | 1.0264 (8) | 0.2556 (7) | 0.9409 (7) | 0.0621 (19) | |
| H4 | 1.0880 | 0.2782 | 0.8904 | 0.075* | |
| C3 | 0.9181 (7) | 0.1612 (6) | 0.8968 (6) | 0.0518 (16) | |
| H3 | 0.9039 | 0.1210 | 0.8160 | 0.062* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Sn1 | 0.0278 (3) | 0.0278 (3) | 0.0285 (3) | 0.0023 (2) | 0.0134 (2) | 0.0006 (2) |
| Br2 | 0.0574 (5) | 0.0572 (4) | 0.0634 (5) | −0.0230 (3) | 0.0197 (3) | −0.0074 (3) |
| Cl1 | 0.0379 (7) | 0.0438 (7) | 0.0379 (7) | −0.0022 (6) | 0.0216 (6) | 0.0021 (6) |
| Cl2 | 0.0334 (7) | 0.0680 (9) | 0.0382 (8) | −0.0004 (7) | 0.0088 (6) | 0.0147 (7) |
| Cl3 | 0.0604 (10) | 0.0319 (7) | 0.0698 (10) | 0.0009 (7) | 0.0378 (8) | −0.0086 (7) |
| N1 | 0.040 (3) | 0.050 (3) | 0.035 (2) | −0.003 (2) | 0.016 (2) | 0.001 (2) |
| C6 | 0.042 (3) | 0.045 (3) | 0.051 (4) | 0.000 (3) | 0.005 (3) | −0.010 (3) |
| C5 | 0.046 (4) | 0.050 (4) | 0.076 (5) | −0.010 (3) | 0.005 (3) | 0.007 (4) |
| C2 | 0.031 (3) | 0.036 (3) | 0.041 (3) | −0.002 (2) | 0.009 (2) | 0.001 (2) |
| C4 | 0.050 (4) | 0.076 (5) | 0.069 (5) | −0.013 (4) | 0.033 (3) | 0.002 (4) |
| C3 | 0.054 (4) | 0.062 (4) | 0.050 (4) | −0.009 (3) | 0.031 (3) | −0.011 (3) |
| Sn1—Cl1 | 2.4216 (13) | N1—H1 | 0.8600 |
| Sn1—Cl2 | 2.4513 (14) | C6—C5 | 1.362 (9) |
| Sn1—Cl3 | 2.4212 (13) | C6—H6 | 0.9300 |
| Sn1—Cl1i | 2.4216 (13) | C5—C4 | 1.378 (10) |
| Sn1—Cl2i | 2.4513 (14) | C5—H5 | 0.9300 |
| Sn1—Cl3i | 2.4212 (13) | C2—C3 | 1.347 (8) |
| Br2—C2 | 1.871 (5) | C4—C3 | 1.375 (9) |
| N1—C6 | 1.331 (8) | C4—H4 | 0.9300 |
| N1—C2 | 1.336 (7) | C3—H3 | 0.9300 |
| Cl1—Sn1—Cl2 | 89.67 (5) | C2—N1—H1 | 118.9 |
| Cl3—Sn1—Cl1i | 89.70 (5) | N1—C6—C5 | 119.6 (6) |
| Cl3—Sn1—Cl1 | 90.30 (5) | N1—C6—H6 | 120.2 |
| Cl3—Sn1—Cl2 | 90.06 (6) | C5—C6—H6 | 120.2 |
| Cl3—Sn1—Cl2i | 89.94 (6) | C6—C5—C4 | 118.6 (6) |
| Cl1—Sn1—Cl2i | 90.33 (5) | C6—C5—H5 | 120.7 |
| Cl3i—Sn1—Cl3 | 180.0 | C4—C5—H5 | 120.7 |
| Cl3i—Sn1—Cl1i | 90.30 (5) | N1—C2—C3 | 120.5 (5) |
| Cl3i—Sn1—Cl1 | 89.70 (5) | N1—C2—Br2 | 116.4 (4) |
| Cl1i—Sn1—Cl1 | 180.0 | C3—C2—Br2 | 123.1 (5) |
| Cl3i—Sn1—Cl2i | 90.06 (6) | C3—C4—C5 | 120.7 (7) |
| Cl1i—Sn1—Cl2i | 89.67 (5) | C3—C4—H4 | 119.6 |
| Cl3i—Sn1—Cl2 | 89.94 (6) | C5—C4—H4 | 119.6 |
| Cl1i—Sn1—Cl2 | 90.33 (5) | C2—C3—C4 | 118.4 (6) |
| Cl2i—Sn1—Cl2 | 180.0 | C2—C3—H3 | 120.8 |
| C6—N1—C2 | 122.3 (5) | C4—C3—H3 | 120.8 |
| C6—N1—H1 | 118.9 | ||
| C2—N1—C6—C5 | −0.9 (9) | C6—C5—C4—C3 | 1.4 (11) |
| N1—C6—C5—C4 | −0.1 (10) | N1—C2—C3—C4 | 0.6 (9) |
| C6—N1—C2—C3 | 0.7 (9) | Br2—C2—C3—C4 | −179.4 (5) |
| C6—N1—C2—Br2 | −179.4 (4) | C5—C4—C3—C2 | −1.6 (11) |
| Symmetry codes: (i) −x, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl2ii | 0.86 | 2.45 | 3.234 (5) | 151 |
| C3—H3···Cl1iii | 0.93 | 2.77 | 3.646 (6) | 158 |
| C5—H5···Cl1iv | 0.93 | 2.86 | 3.774 (7) | 170 |
| Symmetry codes: (ii) −x+1, −y, −z+2; (iii) −x+1, −y, −z+1; (iv) −x+3/2, y+1/2, −z+3/2. |
| Sn1—Cl1 | 2.4216 (13) | Sn1—Cl3 | 2.4212 (13) |
| Sn1—Cl2 | 2.4513 (14) | ||
| Cl1—Sn1—Cl2 | 89.67 (5) | Cl3—Sn1—Cl2 | 90.06 (6) |
| Cl3—Sn1—Cl1i | 89.70 (5) | Cl3—Sn1—Cl2i | 89.94 (6) |
| Cl3—Sn1—Cl1 | 90.30 (5) |
| Symmetry codes: (i) −x, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···Cl2ii | 0.86 | 2.45 | 3.234 (5) | 151 |
| C3—H3···Cl1iii | 0.93 | 2.77 | 3.646 (6) | 158 |
| C5—H5···Cl1iv | 0.93 | 2.86 | 3.774 (7) | 170 |
| Symmetry codes: (ii) −x+1, −y, −z+2; (iii) −x+1, −y, −z+1; (iv) −x+3/2, y+1/2, −z+3/2. |
Al al-Bayt University and Al-Balqa'a Applied University are thanked for supporting this work
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Noncovalent interactions play an important role in organizing structural units in both natural and artificial systems. Hybrid organic-inorganic compounds are of great interest owing to their ionic, electrical, magnetic and optical properties (Hill, 1998; Kagan et al., 1999; Raptopoulou et al., 2002). Tin metal-halo based hybrids are of particular interest as being materials with interesting optical and magnetic properties (Aruta et al., 2005; Knutson et al., 2005; Mitzi et al., 2001; Kagan et al., 1999). We are currently carrying out studies about lattice including different types of intermolecular interactions. Our strategy is to use aromatic compounds to encourage aryl···aryl packing arrangements of various types, using substituted pyridinium in order to facilitates associations, and halo salts that can involve in X···X interactions as well as X···aryl and X···H interactions. Within our research of hybrid compounds containing tin metal (Al-Far & Ali 2007; Ali, Al-Far & Al-Sou'od, 2007; Ali & Al-Far, 2007; Ali, Al-Far & Ng, 2007), the crystal structure of the title salt, (I), has been investigated.
The asymmetric unit of (I) contains one cation and one-half anion (Fig. 1). The (SnCl6)2- anion lies on an inversion center, in a quasi-octahedral geometry (Table 1). The Sn—Cl bond lengths are almost invariant, but Sn—Cl2 is longer than the others (involved in the shortest hydrogen bonds). These lengths fall within the range of tin-chloride distances reported previously for compounds containing (SnCl6)2- anions (Bouacida et al., 2007; Ellis & Macdonald, 2006; Li et al., 2005; Willett & Haddad, 2000). Bond lengths and angles within the cation are as expected (Allen et al., 1987).
The packing of the structure (Fig. 2) can be described as layers of alternating anions (zigzag orientation) along the face parallel to b-axis and diagonal to ac plane. Each (SnCl6)2- anion is surrounded by six cations via four equatorial (C,N)—H···Cl interactions (Table 2) and two axial Cl···Br interactions [Cl3···Br2i = 3.4393 (15) Å; symmetry code: (i) -1/2 + x, -1/2 - y, -1/2 + z; Fig. 3). This arrangement of molecules appears as layers approximately parallel to [110]. It is noteworthy that structural and theoretical results (Awwadi et al., 2007; and references therein), show the significance of linear C—Y···X- (in this case C—Cl···Br) synthons in influencing structures of crystalline materials and in use as potential building blocks in crystal engineering via supramolecular synthesis.
The intermolecular hydrogen bonds (Table 2) and Cl···Br interactions would therefore add some lattice stability. This is evident in the isostructurality with the reported Te analogue (Fernandes et al., 2004).