Acta Cryst. (2008). E64, i80 [ doi:10.1107/S1600536808035435 ]
In comparison with the previous refinement of tetrapotassium di-![[mu]](/logos/entities/mu_rmgif.gif)
-chlorido-bis[tetrachloridobismuthate(III)] tetrahydrate [Volkova, Udovenko, Levin & Shevchenko (1983). Koord. Khim. 9, 356-360], the current redetermination reveals anisotropic displacement parameters for all non-H atoms, localization of the H atoms, and higher precision of lattice parameters and interatomic distances. The crystal structure is built up of edge-sharing [Bi2Cl10]4- double octahedra with the bridging Cl atoms situated on a mirror plane, three K+ counter-cations (two of which are on mirror planes), and two water molecules that are solely coordinated to the K+ cations. These building units are linked into a three-dimensional network structure. Additional O-H
Cl hydrogen bonds between the water molecules and the complex anions stabilize this arrangement.
(BiO)2CO3 was dissolved in concentrated hydrochloric acid in order to prepare a BiCl3 solution. The latter was then added to an aqueous KCl solution in a molar ratio of 1:2. The resulting solution has been kept under stirring for 1 h and was allowed to stand at room temperature for some days. After this time colourless crystals of the title compound were obtained and isolated from the acid solution by filtration.
The H atom positions were located from difference Fourier maps and were refined freely.
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003) and publCif (Westrip, 2008).
![[Figure 1]](./wm2201fig1thm.gif)
| Fig. 1. Part of the crystal structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius. [Symmetry codes: (i) x, y, z + 1; (ii) -x, -1/2 - y, z + 1.] |
![[Figure 2]](./wm2201fig2thm.gif)
| Fig. 2. Projection of the K4[Bi2Cl10].4H2O structure along the a axis, showing the pairs of edge-sharing [BiCl6] octahedra. |
| K4[Bi2Cl10]·4H2O | F(000) = 1808 |
| Mr = 1000.94 | Dx = 2.945 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 4596 reflections |
| a = 8.4310 (1) Å | θ = 1.9–34.2° |
| b = 21.8444 (3) Å | µ = 17.49 mm−1 |
| c = 12.2561 (2) Å | T = 295 K |
| V = 2257.21 (6) Å3 | Prism, colourless |
| Z = 4 | 0.28 × 0.12 × 0.08 mm |
| Bruker APEXII CCD diffractometer | 2801 reflections with I > 3.0σ(I) |
| graphite | Rint = 0.034 |
| ω scans | θmax = 34.2°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2006) | h = −10→12 |
| Tmin = 0.067, Tmax = 0.247 | k = −22→33 |
| 26961 measured reflections | l = −19→17 |
| 4596 independent reflections |
| Refinement on F | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.017 | All H-atom parameters refined |
| wR(F2) = 0.017 | Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)
[weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.260 0.753E-01 0.968E-01 |
| S = 1.08 | (Δ/σ)max = 0.002 |
| 2801 reflections | Δρmax = 1.01 e Å−3 |
| 114 parameters | Δρmin = −0.82 e Å−3 |
| 0 restraints | Extinction correction: Larson (1970), Equation 22 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 33.8 (8) |
| K4[Bi2Cl10]·4H2O | V = 2257.21 (6) Å3 |
| Mr = 1000.94 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 8.4310 (1) Å | µ = 17.49 mm−1 |
| b = 21.8444 (3) Å | T = 295 K |
| c = 12.2561 (2) Å | 0.28 × 0.12 × 0.08 mm |
| Bruker APEXII CCD diffractometer | 4596 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2006) | 2801 reflections with I > 3.0σ(I) |
| Tmin = 0.067, Tmax = 0.247 | Rint = 0.034 |
| 26961 measured reflections | θmax = 34.2° |
| R[F2 > 2σ(F2)] = 0.017 | All H-atom parameters refined |
| wR(F2) = 0.017 | Δρmax = 1.01 e Å−3 |
| S = 1.08 | Δρmin = −0.82 e Å−3 |
| 2801 reflections | Absolute structure: ? |
| 114 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Bi1 | 0.367812 (10) | −0.349919 (4) | 0.996881 (8) | 0.0204 | |
| Cl2 | 0.49635 (11) | −0.35057 (4) | 0.79938 (7) | 0.0394 | |
| Cl3 | 0.17101 (13) | −0.2500 | 0.92700 (9) | 0.0308 | |
| Cl4 | 0.15802 (11) | −0.43464 (4) | 0.95182 (7) | 0.0360 | |
| Cl5 | 0.56356 (13) | −0.2500 | 0.06223 (10) | 0.0308 | |
| Cl6 | 0.24213 (9) | −0.34605 (4) | 0.20120 (6) | 0.0302 | |
| Cl7 | 0.57912 (10) | −0.42888 (4) | 0.05937 (7) | 0.0331 | |
| K8 | 0.44796 (13) | −0.2500 | 0.34052 (9) | 0.0349 | |
| K9 | 0.28965 (14) | −0.2500 | 0.66630 (9) | 0.0379 | |
| K10 | 0.02601 (12) | −0.54772 (5) | 0.80949 (8) | 0.0506 | |
| O11 | 0.3695 (3) | −0.16188 (16) | 0.5001 (3) | 0.0504 | |
| O12 | 0.2459 (5) | −0.47915 (15) | 0.6858 (3) | 0.0552 | |
| H13 | 0.278 (9) | −0.140 (3) | 0.487 (5) | 0.10 (2)* | |
| H8 | 0.205 (8) | −0.481 (3) | 0.629 (5) | 0.09 (2)* | |
| H14 | 0.428 (8) | −0.142 (3) | 0.535 (5) | 0.09 (2)* | |
| H15 | 0.223 (5) | −0.445 (8) | 0.707 (6) | 0.08 (3)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Bi1 | 0.02127 (5) | 0.01939 (4) | 0.02050 (4) | 0.00016 (3) | 0.00160 (4) | −0.00009 (4) |
| Cl2 | 0.0440 (4) | 0.0469 (5) | 0.0272 (3) | 0.0084 (4) | 0.0102 (3) | 0.0035 (3) |
| Cl3 | 0.0218 (5) | 0.0365 (6) | 0.0342 (5) | 0.0000 | −0.0043 (4) | 0.0000 |
| Cl4 | 0.0351 (4) | 0.0338 (4) | 0.0392 (4) | −0.0049 (3) | −0.0057 (3) | −0.0086 (3) |
| Cl5 | 0.0228 (5) | 0.0305 (5) | 0.0390 (5) | 0.0000 | −0.0037 (4) | 0.0000 |
| Cl6 | 0.0316 (3) | 0.0338 (4) | 0.0252 (3) | −0.0039 (3) | 0.0044 (3) | −0.0028 (3) |
| Cl7 | 0.0338 (4) | 0.0302 (4) | 0.0354 (4) | 0.0042 (3) | −0.0028 (3) | 0.0025 (3) |
| K8 | 0.0329 (5) | 0.0334 (5) | 0.0383 (5) | 0.0000 | −0.0061 (4) | 0.0000 |
| K9 | 0.0370 (6) | 0.0432 (6) | 0.0335 (5) | 0.0000 | −0.0037 (4) | 0.0000 |
| K10 | 0.0460 (5) | 0.0586 (5) | 0.0472 (5) | −0.0134 (4) | 0.0086 (4) | −0.0190 (4) |
| O11 | 0.0291 (13) | 0.0507 (16) | 0.071 (2) | −0.0020 (11) | −0.0121 (15) | −0.0093 (17) |
| O12 | 0.076 (2) | 0.0449 (17) | 0.0446 (17) | 0.0092 (17) | 0.0009 (17) | −0.0044 (14) |
| Bi1—Cl7i | 2.5954 (8) | Bi1—Cl3 | 2.8724 (7) |
| Bi1—Cl4 | 2.6190 (8) | O11—H13 | 0.92 (7) |
| Bi1—Cl2 | 2.6522 (8) | O11—H14 | 0.78 (7) |
| Bi1—Cl6i | 2.7205 (7) | O12—H8 | 0.79 (6) |
| Bi1—Cl5ii | 2.8512 (7) | O12—H15 | 0.81 (12) |
| Cl6i—Bi1—Cl7i | 90.94 (3) | Cl6i—Bi1—Cl4 | 87.31 (3) |
| Cl6i—Bi1—Cl5ii | 86.74 (3) | Cl7i—Bi1—Cl4 | 93.22 (3) |
| Cl7i—Bi1—Cl5ii | 91.64 (2) | Cl5ii—Bi1—Cl4 | 172.37 (3) |
| Cl6i—Bi1—Cl2 | 178.11 (3) | Cl2—Bi1—Cl4 | 94.57 (3) |
| Cl7i—Bi1—Cl2 | 89.16 (3) | Cl3—Bi1—Cl4 | 94.82 (3) |
| Cl5ii—Bi1—Cl2 | 91.37 (3) | Bi1iii—Cl3—Bi1 | 98.91 (3) |
| Cl6i—Bi1—Cl3 | 91.48 (3) | Bi1iv—Cl5—Bi1v | 99.91 (3) |
| Cl7i—Bi1—Cl3 | 171.71 (3) | H13—O11—H14 | 110 (6) |
| Cl5ii—Bi1—Cl3 | 80.58 (2) | H8—O12—H15 | 103 (7) |
| Cl2—Bi1—Cl3 | 88.16 (3) |
| Symmetry codes: (i) x, y, z+1; (ii) x, −y−1/2, z+1; (iii) x, −y−1/2, z; (iv) x, y, z−1; (v) x, −y−1/2, z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O11—H13···Cl7vi | 0.92 (7) | 2.32 (7) | 3.234 (4) | 169 (7) |
| O11—H14···Cl4vii | 0.78 (7) | 2.56 (8) | 3.273 (3) | 150 (9) |
| O12—H8···Cl7viii | 0.79 (6) | 2.78 (7) | 3.497 (4) | 152 (7) |
| O12—H15···Cl2ix | 0.81 (17) | 2.81 (8) | 3.514 (3) | 145 (9) |
| Symmetry codes: (vi) x−1/2, −y−1/2, −z+1/2; (vii) x+1/2, −y−1/2, −z+3/2; (viii) x−1/2, y, −z+1/2; (ix) x−1/2, y, −z+3/2. |
| Bi1—Cl7i | 2.5954 (8) | Bi1—Cl6i | 2.7205 (7) |
| Bi1—Cl4 | 2.6190 (8) | Bi1—Cl5ii | 2.8512 (7) |
| Bi1—Cl2 | 2.6522 (8) | Bi1—Cl3 | 2.8724 (7) |
| Symmetry codes: (i) x, y, z+1; (ii) x, −y−1/2, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O11—H13···Cl7iii | 0.92 (7) | 2.32 (7) | 3.234 (4) | 169 (7) |
| O11—H14···Cl4iv | 0.78 (7) | 2.56 (8) | 3.273 (3) | 150 (9) |
| O12—H8···Cl7v | 0.79 (6) | 2.78 (7) | 3.497 (4) | 152 (7) |
| O12—H15···Cl2vi | 0.81 (17) | 2.81 (8) | 3.514 (3) | 145 (9) |
| Symmetry codes: (iii) x−1/2, −y−1/2, −z+1/2; (iv) x+1/2, −y−1/2, −z+3/2; (v) x−1/2, y, −z+1/2; (vi) x−1/2, y, −z+3/2. |
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Some bismuth-containing compounds (Belkyal et al., 1997; Benachenhou et al., 1986) exhibit phase transitions and have interesting physical properties which make them the object of an intensive research due to their potential application in catalysis.
Under investigation of a series of these materials, we have selected the K4[Bi2Cl10].4H2O compound and redetermined its structure. For the previous crystallographic study on this compound, see: Volkova et al. (1983). The isotypic Br compound was reported by Lazarini (1977).
The structure of the title compound can be described by [Bi2Cl10]4- pairs of octahedra, K+ cations and water molecules (Fig. 1), forming a three-dimensional network (Fig. 2). The [Bi2Cl10]4- anions are formed by pairs of distorted [BiCl6] octahedra sharing an edge. The mean Bi—Cl distances range from 2.5954 (8) to 2.8724 (7) Å with the Cl—Bi—Cl angles varying between 80.58 (2) and 94.82 (3)°, likewise showing the distortions of the BiCl6 octahedra. Compared to the previous study, the distortion of the [BiCl6] octahedra is relatively lower. The structure is additionally stabilized by the presence of hydrogen bonds of the type O—H···Cl between water molecules and the binuclear complex anions. For the polyhedra around the K+ cations the coordinations are similar. Whereas two K+ cations (K8 and K9) are located at the 4c sites (m symmetry), the third cation (K10) is on a general position. However, all K+ cations are surrounded by two water O atoms and seven Cl atoms, leading to irregular [KO2Cl7] polyhedra.