Redetermination of K4[Bi2Cl10]·4H2O

Mabrouk Khelifi; Ridha Zouari; Abdelhamid Ben Salah

doi:10.1107/S1600536808035435

. 2008 Nov 8;64(Pt 12):i80. doi: 10.1107/S1600536808035435

Redetermination of K₄[Bi₂Cl₁₀]·4H₂O

Mabrouk Khelifi ^a,^*, Ridha Zouari ^a, Abdelhamid Ben Salah ^a

PMCID: PMC2960101 PMID: 21581105

Abstract

In comparison with the previous refinement of tetrapotassium di-μ-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.

Related literature

The isotypic Br compound was reported by Lazarini (1977 ▶). For related structures, see: Belkyal et al. (1997 ▶); Benachenhou et al. (1986 ▶). For general background, see: Larson (1970 ▶); Prince (1982 ▶); Watkin (1994 ▶).

Experimental

Crystal data

K₄[Bi₂Cl₁₀]·4H₂O
M _r = 1000.94
Orthorhombic,
a = 8.4310 (1) Å
b = 21.8444 (3) Å
c = 12.2561 (2) Å
V = 2257.21 (6) Å³
Z = 4
Mo Kα radiation
μ = 17.49 mm⁻¹
T = 295 (2) K
0.28 × 0.12 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.067, T _max = 0.247
26961 measured reflections
4596 independent reflections
2801 reflections with I > 3.0σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.017
wR(F ²) = 0.017
S = 1.08
2801 reflections
114 parameters
All H-atom parameters refined
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: APEX2; 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 and publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035435/wm2201sup1.cif

e-64-00i80-sup1.cif^{(12.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035435/wm2201Isup2.hkl

e-64-00i80-Isup2.hkl^{(220.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Bi1—Cl7ⁱ	2.5954 (8)
Bi1—Cl4	2.6190 (8)
Bi1—Cl2	2.6522 (8)
Bi1—Cl6ⁱ	2.7205 (7)
Bi1—Cl5ⁱⁱ	2.8512 (7)
Bi1—Cl3	2.8724 (7)

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Symmetry codes: (i) Inline graphic ; (ii) .

Table 2. Hydrogen-bond geometry (Å, °).

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⋯Cl4^iv	0.78 (7)	2.56 (8)	3.273 (3)	150 (9)
O12—H8⋯Cl7^v	0.79 (6)	2.78 (7)	3.497 (4)	152 (7)
O12—H15⋯Cl2^vi	0.81 (17)	2.81 (8)	3.514 (3)	145 (9)

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Symmetry codes: (iii) Inline graphic ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

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.

Experimental

(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.