Acta Cryst. (2008). E64, m573 [ doi:10.1107/S1600536808007368 ]
The crystal structure of the title compound, (C6H14N)2[SnCl6], is built of 4-methylpiperidinium cations, occupying special positions on the mirror plane, and hexachloridostannate(IV) anions on a special position of 2/m symmetry. The ions are linked via N-H
Cl hydrogen bonds into chains running along the b axis.
The 4-methyl-1-piperidine carbodithioic acid (3.0 g, 17.1 mmol) and tin tetrachloride pentahydrate (5.99 g, 17.1 mmol) were added to 100 ml of dry methanol in round bottom flask and stirred for 6 h. The resulting clear solution was evaporated at room temperature. Colourless crystals of the title compound were obtained after recrystallization in chlorofom and n-hexane (1:1). Yield: 64%. m.p. 228°C.
H atoms bonded to C1—C3 were included in riding motion approximation in calculated positions with C—H distances of 0.99 Å and Uiso 1.2 times those of the parent atoms; those bonded to C4 and N1 were located in a difference Fourier map and refined isotropically with Uiso 1.2 times those of the parent atoms (C4 - H distances 0.93 (2) and 0.95 (3) Å and N1 - H 0.84 (3) and 0.88 (3) Å).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ya2069fig1thm.gif)
| Fig. 1. Structure of (I) with displacement ellipsoids drawn at the 50% probability level. The unlabelled atoms of the 4-methylpiperidinium cation are symmetry related (symmetry code x, y, -z). The unlabelled Cl atoms are symmetry related to Cl1 (symmetry code -x, 2 - y, -z) and Cl2 (symmetry codes -x, 2 - y, -z; -x, 2 - y, z; x, y, -z). |
![[Figure 2]](./ya2069fig2thm.gif)
| Fig. 2. Fragment of the crystal packing of (I) showing chain along the b axis, viewed approximately along the diagonal of the bc-plane; H-bonds are shown as dashed lines. |
| (C6H14N)2[SnCl6] | F000 = 532 |
| Mr = 531.75 | Dx = 1.660 Mg m−3 |
| Orthorhombic, Pnnm | Mo Kα radiation λ = 0.71069 Å |
| Hall symbol: -P22n | Cell parameters from 3718 reflections |
| a = 13.123 (5) Å | θ = 2.5–26.3º |
| b = 7.722 (5) Å | µ = 1.95 mm−1 |
| c = 10.500 (5) Å | T = 100 (2) K |
| V = 1064.0 (9) Å3 | Pyramidal, colourless |
| Z = 2 | 0.25 × 0.25 × 0.25 mm |
| Bruker APEX CCD area-detector diffractometer | 1055 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.050 |
| Monochromator: graphite | θmax = 26.3º |
| T = 100(2) K | θmin = 2.5º |
| φ and ω scans | h = −16→16 |
| Absorption correction: none | k = −9→9 |
| 7975 measured reflections | l = −13→13 |
| 1153 independent reflections |
| 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)] = 0.018 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.040 | w = 1/[σ2(Fo2) + (0.0164P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 1153 reflections | Δρmax = 0.78 e Å−3 |
| 65 parameters | Δρmin = −0.29 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| (C6H14N)2[SnCl6] | V = 1064.0 (9) Å3 |
| Mr = 531.75 | Z = 2 |
| Orthorhombic, Pnnm | Mo Kα |
| a = 13.123 (5) Å | µ = 1.95 mm−1 |
| b = 7.722 (5) Å | T = 100 (2) K |
| c = 10.500 (5) Å | 0.25 × 0.25 × 0.25 mm |
| Bruker APEX CCD area-detector diffractometer | 1153 independent reflections |
| Absorption correction: none | 1055 reflections with I > 2σ(I) |
| 7975 measured reflections | Rint = 0.050 |
| R[F2 > 2σ(F2)] = 0.018 | 65 parameters |
| wR(F2) = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.78 e Å−3 |
| 1153 reflections | Δρmin = −0.29 e Å−3 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Sn1 | 0.0000 | 1.0000 | 0.0000 | 0.01428 (9) | |
| Cl1 | 0.18119 (5) | 0.94377 (8) | 0.0000 | 0.02127 (15) | |
| Cl2 | −0.02412 (3) | 0.77582 (6) | 0.15973 (4) | 0.02279 (12) | |
| N1 | 0.16716 (17) | 0.5226 (3) | 0.0000 | 0.0187 (5) | |
| H1N | 0.128 (2) | 0.615 (4) | 0.0000 | 0.022* | |
| H2N | 0.130 (2) | 0.434 (4) | 0.0000 | 0.022* | |
| C1 | 0.23016 (14) | 0.5228 (2) | 0.11919 (17) | 0.0202 (4) | |
| H1C | 0.1850 | 0.5171 | 0.1946 | 0.024* | |
| H1D | 0.2701 | 0.6313 | 0.1242 | 0.024* | |
| C2 | 0.30167 (13) | 0.3686 (2) | 0.11902 (17) | 0.0194 (4) | |
| H2A | 0.2611 | 0.2607 | 0.1235 | 0.023* | |
| H2B | 0.3456 | 0.3736 | 0.1956 | 0.023* | |
| C3 | 0.36885 (19) | 0.3640 (3) | 0.0000 | 0.0194 (6) | |
| H3 | 0.4130 | 0.4696 | 0.0000 | 0.023* | |
| C4 | 0.4374 (2) | 0.2055 (4) | 0.0000 | 0.0271 (7) | |
| H4A | 0.4780 (15) | 0.200 (3) | −0.0726 (19) | 0.032* | |
| H4B | 0.399 (2) | 0.102 (4) | 0.0000 | 0.032* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Sn1 | 0.01250 (13) | 0.01126 (13) | 0.01907 (14) | −0.00031 (9) | 0.000 | 0.000 |
| Cl1 | 0.0136 (3) | 0.0153 (3) | 0.0349 (4) | 0.0005 (2) | 0.000 | 0.000 |
| Cl2 | 0.0214 (2) | 0.0228 (2) | 0.0242 (3) | −0.00568 (18) | −0.00453 (18) | 0.00756 (19) |
| N1 | 0.0165 (11) | 0.0122 (12) | 0.0274 (13) | 0.0012 (9) | 0.000 | 0.000 |
| C1 | 0.0205 (10) | 0.0199 (10) | 0.0203 (10) | −0.0007 (8) | −0.0011 (7) | −0.0040 (8) |
| C2 | 0.0189 (10) | 0.0200 (10) | 0.0192 (10) | 0.0010 (8) | −0.0028 (8) | −0.0011 (8) |
| C3 | 0.0151 (13) | 0.0189 (14) | 0.0241 (15) | 0.0003 (10) | 0.000 | 0.000 |
| C4 | 0.0239 (16) | 0.0321 (18) | 0.0252 (17) | 0.0102 (13) | 0.000 | 0.000 |
| Sn1—Cl1 | 2.4170 (11) | C1—H1C | 0.9900 |
| Sn1—Cl1i | 2.4170 (11) | C1—H1D | 0.9900 |
| Sn1—Cl2ii | 2.4310 (11) | C2—C3 | 1.530 (2) |
| Sn1—Cl2iii | 2.4310 (11) | C2—H2A | 0.9900 |
| Sn1—Cl2i | 2.4310 (11) | C2—H2B | 0.9900 |
| Sn1—Cl2 | 2.4310 (11) | C3—C4 | 1.519 (4) |
| N1—C1iii | 1.500 (2) | C3—C2iii | 1.530 (2) |
| N1—C1 | 1.500 (2) | C3—H3 | 1.0000 |
| N1—H1N | 0.88 (3) | C4—H4A | 0.931 (19) |
| N1—H2N | 0.84 (3) | C4—H4B | 0.95 (3) |
| C1—C2 | 1.516 (2) | ||
| Cl1—Sn1—Cl1i | 180.000 (5) | N1—C1—C2 | 109.83 (15) |
| Cl1—Sn1—Cl2ii | 89.990 (19) | N1—C1—H1C | 109.7 |
| Cl1i—Sn1—Cl2ii | 90.010 (19) | C2—C1—H1C | 109.7 |
| Cl1—Sn1—Cl2iii | 90.010 (19) | N1—C1—H1D | 109.7 |
| Cl1i—Sn1—Cl2iii | 89.990 (19) | C2—C1—H1D | 109.7 |
| Cl2ii—Sn1—Cl2iii | 180.0 | H1C—C1—H1D | 108.2 |
| Cl1—Sn1—Cl2i | 89.990 (19) | C1—C2—C3 | 112.08 (16) |
| Cl1i—Sn1—Cl2i | 90.010 (19) | C1—C2—H2A | 109.2 |
| Cl2ii—Sn1—Cl2i | 87.24 (5) | C3—C2—H2A | 109.2 |
| Cl2iii—Sn1—Cl2i | 92.76 (5) | C1—C2—H2B | 109.2 |
| Cl1—Sn1—Cl2 | 90.010 (19) | C3—C2—H2B | 109.2 |
| Cl1i—Sn1—Cl2 | 89.990 (19) | H2A—C2—H2B | 107.9 |
| Cl2ii—Sn1—Cl2 | 92.76 (5) | C4—C3—C2iii | 111.10 (15) |
| Cl2iii—Sn1—Cl2 | 87.24 (5) | C4—C3—C2 | 111.10 (15) |
| Cl2i—Sn1—Cl2 | 180.0 | C2iii—C3—C2 | 109.6 (2) |
| C1iii—N1—C1 | 113.1 (2) | C4—C3—H3 | 108.3 |
| C1iii—N1—H1N | 108.7 (8) | C2iii—C3—H3 | 108.3 |
| C1—N1—H1N | 108.7 (8) | C2—C3—H3 | 108.3 |
| C1iii—N1—H2N | 108.6 (10) | C3—C4—H4A | 112.1 (14) |
| C1—N1—H2N | 108.6 (10) | C3—C4—H4B | 111.2 (18) |
| H1N—N1—H2N | 109 (3) | H4A—C4—H4B | 105.6 (17) |
| C1iii—N1—C1—C2 | −56.8 (2) | C1—C2—C3—C4 | −178.20 (18) |
| N1—C1—C2—C3 | 55.7 (2) | C1—C2—C3—C2iii | −55.1 (2) |
| Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+2, z; (iii) x, y, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···Cl1 | 0.88 (3) | 2.63 (3) | 3.258 (3) | 129 (2) |
| N1—H2N···Cl2iv | 0.84 (3) | 2.72 (2) | 3.413 (2) | 141.6 (5) |
| N1—H2N···Cl2v | 0.84 (3) | 2.72 (2) | 3.413 (2) | 141.6 (5) |
| Symmetry codes: (iv) −x, −y+1, −z; (v) −x, −y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···Cl1 | 0.88 (3) | 2.63 (3) | 3.258 (3) | 129 (2) |
| N1—H2N···Cl2i | 0.84 (3) | 2.72 (2) | 3.413 (2) | 141.6 (5) |
| N1—H2N···Cl2ii | 0.84 (3) | 2.72 (2) | 3.413 (2) | 141.6 (5) |
| Symmetry codes: (i) −x, −y+1, −z; (ii) −x, −y+1, z. |
SA is thankful to Quaid-i-Azam University, Islamabad, Pakistan, for financial support.
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2002). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Shahzadi, S., Ali, S., Bhatti, M. H., Fettouhi, M. & Athar, M. (2006). J. Organomet. Chem. 691, 1797–1802.
Shahzadi, S., Ali, S. & Fettouhi, M. (2006). Acta Cryst. E62, m1178–m1180.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
We report here the crystal structure of the title compound (I) as shown in Fig. 1. The Sn1—Cl distances span the range of 2.417 (1)–2.431 (1) Å; the N1—C1 bond is 1.500 (2) Å. The N—H···Cl bonds link the ions into chains along the b axis (Table 1, Fig. 2).