Redetermination of K4[Bi2Cl10]·4H2O

Khelifi, M.; Zouari, R.; Ben Salah, A.

doi:10.1107/S1600536808035435

inorganic compounds

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Volume 64| Part 12| December 2008| Page i80

doi:10.1107/S1600536808035435

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Redetermination of K₄[Bi₂Cl₁₀]·4H₂O

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

^aFaculté des Sciences de Sfax, Laboratoire de Sciences des Matériaux et d'Environnement, BP 115 Sfax 3052, Tunisia
^*Correspondence e-mail: mabrouk.khelifi@fss.rnu.tn

(Received 18 October 2008; accepted 29 October 2008; online 8 November 2008)

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, P n m a
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[F² > 2σ(F²)] = 0.017
wR(F²) = 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

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)
Symmetry codes: (i) x, y, z+1; (ii) $[x, -y-{\script{1\over 2}}, z+1]$ .

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)
Symmetry codes: (iii) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

(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.

Computing details top

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).

Figures top

	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.]
	Fig. 2. Projection of the K₄[Bi₂Cl₁₀].4H₂O structure along the a axis, showing the pairs of edge-sharing [BiCl₆] octahedra.

tetrapotassium di-µ-chlorido-bis[tetrachloridomuthate(III)] tetrahydrate top

Crystal data top

K₄[Bi₂Cl₁₀]·4H₂O	F(000) = 1808
M_r = 1000.94	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2801 reflections with I > 3.0σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 34.2°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→12
T_min = 0.067, T_max = 0.247	k = −22→33
26961 measured reflections	l = −19→17
4596 independent reflections

Refinement top

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/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 0.260 0.753E-01 0.968E-01
S = 1.08	(Δ/σ)_max = 0.002
2801 reflections	Δρ_max = 1.01 e Å⁻³
114 parameters	Δρ_min = −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)

Crystal data top

K₄[Bi₂Cl₁₀]·4H₂O	V = 2257.21 (6) Å³
M_r = 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

Data collection top

Bruker APEXII CCD diffractometer	4596 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	2801 reflections with I > 3.0σ(I)
T_min = 0.067, T_max = 0.247	R_int = 0.034
26961 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.017	All H-atom parameters refined
S = 1.08	Δρ_max = 1.01 e Å⁻³
2801 reflections	Δρ_min = −0.82 e Å⁻³
114 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)	Bi1^iv—Cl5—Bi1^v	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H13···Cl7^vi	0.92 (7)	2.32 (7)	3.234 (4)	169 (7)
O11—H14···Cl4^vii	0.78 (7)	2.56 (8)	3.273 (3)	150 (9)
O12—H8···Cl7^viii	0.79 (6)	2.78 (7)	3.497 (4)	152 (7)
O12—H15···Cl2^ix	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.

Experimental details

Crystal data
Chemical formula	K₄[Bi₂Cl₁₀]·4H₂O
M_r	1000.94
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	295
a, b, c (Å)	8.4310 (1), 21.8444 (3), 12.2561 (2)
V (Å³)	2257.21 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	17.49
Crystal size (mm)	0.28 × 0.12 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.067, 0.247
No. of measured, independent and observed [I > 3.0σ(I)] reflections	26961, 4596, 2801
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.790

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.017, 0.017, 1.08
No. of reflections	2801
No. of parameters	114
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	1.01, −0.82

Computer programs: APEX2 (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and CRYSTALS (Betteridge et al., 2003), DIAMOND (Brandenburg, 2001), CRYSTALS (Betteridge et al., 2003) and publCIF (Westrip, 2008).

Selected bond lengths (Å) top

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.

Hydrogen-bond geometry (Å, º) top

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)

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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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page i80

doi:10.1107/S1600536808035435

Open

access