Acta Cryst. (2007). E63, m2411 [ doi:10.1107/S1600536807040901 ]
The title compound, (C2H7O)2[SbCl5], contains one-half of an [SbCl5]2- anion lying on a mirror plane and one C2H7O+ cation in the asymmetric unit. The ion pairs are linked togather by strong O-H
Cl hydrogen bonds. The [SbCl5]2- anions are also linked through coordinated Sb-Cl bonds to form parallel chains.
The title compound was prepared by dissolving 1.5 g antimony trichloride in 10 ml absolute acetone, then adding 5 ml hydrochloride acid and 2 ml dimethylether to the solution. The solution was stirred and heated till turned clear. The reaction system was cooled slowly to room temperature. Crystals of (I) were formed by gradual evaporation of the solvents over a period of three weeks at 300 K. 1H NMR (DMSO-d6 / TMS): 2.55 (s, 6H, CH3), 3.60 (s, 1H, OH).
Two voids with volume 67 Å3 were indicated by the program PLATON (Spek, 2003) which were ignored. H atom attached to O atom was deduced from a difference Fourier map, and incorporated in refinement freely. Others were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.97 Å, with Uiso(H) = 1.5 Ueq(C). The final difference map showed a residual electron density of 1.26 e Å−3 lying 1.75 Å from Sb1 and was deemed meaningless.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
![[Figure 1]](./pv2024fig1thm.gif)
| Fig. 1. The molecular structure of (I) plotted with 30% probability displacement ellipsoids; the symmetry related atoms are labeled with A. The hydrogn bonds are illustrated as dashed line. |
![[Figure 2]](./pv2024fig2thm.gif)
| Fig. 2. The packing diagram of (I) viewed down the b axis. Hydrogen bonds are illustrated by dashed lines. |
| (C2H7O)2[SbCl5] | F000 = 760.0 |
| Mr = 393.16 | Dx = 1.724 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation λ = 0.71070 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 5451 reflections |
| a = 8.5731 (15) Å | θ = 3.2–25.3º |
| b = 11.858 (2) Å | µ = 2.68 mm−1 |
| c = 14.899 (3) Å | T = 223 (2) K |
| V = 1514.6 (5) Å3 | Block, colourless |
| Z = 4 | 0.50 × 0.30 × 0.30 mm |
| Bruker APEX area-detector diffractometer | 1462 independent reflections |
| Radiation source: fine-focus sealed tube | 1408 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| T = 223(2) K | θmax = 25.4º |
| φ and ω scans | θmin = 3.2º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −10→10 |
| Tmin = 0.397, Tmax = 0.448 | k = −14→12 |
| 13634 measured reflections | l = −16→17 |
| 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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0272P)2 + 1.5075P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.18 | (Δ/σ)max = 0.001 |
| 1462 reflections | Δρmax = 1.26 e Å−3 |
| 67 parameters | Δρmin = −0.48 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| (C2H7O)2[SbCl5] | V = 1514.6 (5) Å3 |
| Mr = 393.16 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα |
| a = 8.5731 (15) Å | µ = 2.68 mm−1 |
| b = 11.858 (2) Å | T = 223 (2) K |
| c = 14.899 (3) Å | 0.50 × 0.30 × 0.30 mm |
| Bruker APEX area-detector diffractometer | 1462 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1408 reflections with I > 2σ(I) |
| Tmin = 0.397, Tmax = 0.448 | Rint = 0.034 |
| 13634 measured reflections |
| R[F2 > 2σ(F2)] = 0.029 | 67 parameters |
| wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.18 | Δρmax = 1.26 e Å−3 |
| 1462 reflections | Δρmin = −0.48 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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 | ||
| Sb1 | 0.80313 (3) | 0.7500 | 0.602413 (18) | 0.03087 (12) | |
| Cl1 | 0.81044 (10) | 0.53013 (7) | 0.59403 (6) | 0.0446 (2) | |
| Cl2 | 0.60634 (14) | 0.7500 | 0.48064 (8) | 0.0487 (3) | |
| Cl3 | 1.00870 (13) | 0.7500 | 0.49238 (7) | 0.0419 (3) | |
| Cl4 | 1.06504 (14) | 0.7500 | 0.72397 (8) | 0.0437 (3) | |
| O1 | 0.8051 (3) | 0.4769 (3) | 0.3795 (2) | 0.0707 (9) | |
| C1 | 0.6423 (5) | 0.4401 (4) | 0.3866 (3) | 0.0746 (14) | |
| H1C | 0.6068 | 0.4128 | 0.3288 | 0.112* | |
| H1D | 0.5779 | 0.5031 | 0.4053 | 0.112* | |
| H1E | 0.6346 | 0.3800 | 0.4306 | 0.112* | |
| C2 | 0.8291 (5) | 0.5704 (4) | 0.3151 (3) | 0.0618 (11) | |
| H2A | 0.7672 | 0.6349 | 0.3333 | 0.093* | |
| H2B | 0.7974 | 0.5463 | 0.2556 | 0.093* | |
| H2C | 0.9386 | 0.5911 | 0.3142 | 0.093* | |
| H1 | 0.848 (5) | 0.500 (3) | 0.441 (3) | 0.074* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Sb1 | 0.03218 (19) | 0.03316 (19) | 0.02726 (19) | 0.000 | 0.00403 (11) | 0.000 |
| Cl1 | 0.0512 (5) | 0.0344 (5) | 0.0483 (5) | −0.0028 (3) | 0.0036 (4) | 0.0002 (4) |
| Cl2 | 0.0398 (6) | 0.0594 (7) | 0.0470 (7) | 0.000 | −0.0087 (5) | 0.000 |
| Cl3 | 0.0392 (6) | 0.0542 (7) | 0.0323 (6) | 0.000 | 0.0098 (5) | 0.000 |
| Cl4 | 0.0496 (7) | 0.0451 (7) | 0.0363 (6) | 0.000 | −0.0014 (5) | 0.000 |
| O1 | 0.0618 (19) | 0.086 (2) | 0.0644 (19) | −0.0030 (15) | −0.0056 (14) | −0.0033 (18) |
| C1 | 0.052 (2) | 0.084 (3) | 0.088 (3) | −0.019 (2) | 0.006 (2) | −0.035 (3) |
| C2 | 0.081 (3) | 0.063 (3) | 0.042 (2) | 0.007 (2) | −0.003 (2) | −0.0039 (19) |
| Sb1—Cl3 | 2.4070 (11) | O1—H1 | 1.03 (5) |
| Sb1—Cl2 | 2.4775 (12) | C1—H1C | 0.9700 |
| Sb1—Cl1 | 2.6110 (10) | C1—H1D | 0.9700 |
| Sb1—Cl1i | 2.6110 (10) | C1—H1E | 0.9700 |
| Sb1—Cl4 | 2.8847 (12) | C2—H2A | 0.9700 |
| O1—C1 | 1.466 (5) | C2—H2B | 0.9700 |
| O1—C2 | 1.480 (5) | C2—H2C | 0.9700 |
| Cl3—Sb1—Cl2 | 89.99 (4) | O1—C1—H1C | 109.5 |
| Cl3—Sb1—Cl1 | 87.126 (19) | O1—C1—H1D | 109.5 |
| Cl2—Sb1—Cl1 | 88.93 (2) | H1C—C1—H1D | 109.5 |
| Cl3—Sb1—Cl1i | 87.126 (19) | O1—C1—H1E | 109.5 |
| Cl2—Sb1—Cl1i | 88.930 (19) | H1C—C1—H1E | 109.5 |
| Cl1—Sb1—Cl1i | 173.87 (4) | H1D—C1—H1E | 109.5 |
| Cl3—Sb1—Cl4 | 81.82 (4) | O1—C2—H2A | 109.5 |
| Cl2—Sb1—Cl4 | 171.81 (4) | O1—C2—H2B | 109.5 |
| Cl1—Sb1—Cl4 | 90.65 (2) | H2A—C2—H2B | 109.5 |
| Cl1i—Sb1—Cl4 | 90.65 (2) | O1—C2—H2C | 109.5 |
| C1—O1—C2 | 113.8 (3) | H2A—C2—H2C | 109.5 |
| C1—O1—H1 | 111 (2) | H2B—C2—H2C | 109.5 |
| C2—O1—H1 | 109 (2) |
| Symmetry codes: (i) x, −y+3/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···Cl1 | 1.03 (5) | 2.32 (5) | 3.258 (4) | 150 (3) |
| Sb1—Cl3 | 2.4070 (11) | Sb1—Cl4 | 2.8847 (12) |
| Sb1—Cl2 | 2.4775 (12) | O1—C1 | 1.466 (5) |
| Sb1—Cl1 | 2.6110 (10) | O1—C2 | 1.480 (5) |
| Cl3—Sb1—Cl2 | 89.99 (4) | Cl2—Sb1—Cl4 | 171.81 (4) |
| Cl3—Sb1—Cl1 | 87.126 (19) | Cl1—Sb1—Cl4 | 90.65 (2) |
| Cl2—Sb1—Cl1 | 88.93 (2) | C1—O1—C2 | 113.8 (3) |
| Cl3—Sb1—Cl4 | 81.82 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···Cl1 | 1.03 (5) | 2.32 (5) | 3.258 (4) | 150 (3) |
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Dimethyl ether (DME) can be used as a fuel with higher quality of heat in place of diesel oil, whereas its pollution is much lesser than the latter (Cai et al., 1995; Wang et al., 2006). It is also an important intermediate in fine chemical synthesis and is employed as aerosol, vesicant and low pressure refrigerant in many industries (Cheng & Niu, 1995; Zhou, 2005; Wegman, 1994; Shikada et al., 1983; Bagno & Bukala, 1990). Several crystalline compounds containing DME have already been reported (Vojinovic et al., 2006; Blake et al., 1990; Astruc et al., 1990; Ponikiewski & Rothenberger, 2005; Rietz et al., 1978). Now we present here the structure of the title compound, (I).
An asymmetric unit of the title compound consists of a dimethyl ether oxonium (HDME) cation and a half [SbCl5]2− anion lying on a mirror plane (Fig. 1); atoms Sb1/Cl2/Cl3/Cl4 lie in the plane. The HDME cations link to the [SbCl5]2− anion by an O—H1···Cl1 hydrogen bond. The geometry of [SbCl5]2− anion is distorted bipyramid. The geometrical arrangement of [SbCl5]2− anion in general is like that of [SbCl5]2− anion reported by Bujak (Bujak & Zaleski, 1998). The crystals of (I) and that reported by Bujak are allomers, which are similar in the crystalline structure of substances of different chemical composition. Furthermore, the coordinated Sb—Cl bond is worthy of note. A survey of some structures containing antimony and chlorine reveals that normal Sb—Cl bond lengths generally lie between 2.3 and 2.4 Å (Einstein & Jones, 1973) and those involved in bridging range from 2.8 and 3.0 Å (Hall & Sowerby, 1979; Feng et al., 2007). It is noted that the upper limit for a Sb—Cl bond distance has been extended beyond 2.4 Å out and away, to 2.8847 (12) Å in the case of Sb1—Cl4 in (I).
In the crystal structure, the [SbCl5]2− anions link to their neighbouring ones through coordinated bonds Sb1—Cl4 [3.295 (10) Å] forming chains and the [SbCl5]2− chains are associated with HDME cations by O1—H1···Cl to strengthen the crystal structure (Fig. 2).