Bis(piperazine-1,4-diium) hexa­chlorido­bismuthate(III) chloride monohydrate

Yu-Hua Gao; Xiao-Jia Liu; Lei Sun; Wen-Jun Le

doi:10.1107/S1600536811045594

. 2011 Nov 5;67(Pt 12):m1688. doi: 10.1107/S1600536811045594

Bis(piperazine-1,4-diium) hexachloridobismuthate(III) chloride monohydrate

Yu-Hua Gao ^a,^*, Xiao-Jia Liu ^a, Lei Sun ^a, Wen-Jun Le ^a

PMCID: PMC3238614 PMID: 22199505

Abstract

The crystal structure of the title compound, (C₄H₁₂N₂)₂[BiCl₆]Cl·H₂O, consists of piperazinediium cations, [BiCl₆]³⁻ anions, Cl⁻ anions and uncoordinated water molecules. The Bi^III cation is coordinated by six Cl⁻ anions in a slightly distorted octahedral geometry. The diprotonated piperazine ring adopts a chair conformation. In the crystal, extensive intermolecular N—H⋯Cl, N—H⋯O and O—H⋯Cl hydrogen bonds occur.

Related literature

For related structures, see: Wu et al. (2005 ▶); Fu et al. (2005 ▶)

Experimental

Crystal data

(C₄H₁₂N₂)₂[BiCl₆]Cl·H₂O
M _r = 651.46
Monoclinic,
a = 11.085 (3) Å
b = 16.642 (4) Å
c = 11.862 (3) Å
β = 98.997 (3)°
V = 2161.3 (10) Å³
Z = 4
Mo Kα radiation
μ = 9.03 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.266, T _max = 0.266
12000 measured reflections
4108 independent reflections
3341 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.061
S = 1.03
4108 reflections
197 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811045594/xu5366sup1.cif

e-67-m1688-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045594/xu5366Isup2.hkl

e-67-m1688-Isup2.hkl^{(201.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H9A⋯Cl2ⁱ	0.84 (4)	2.67 (6)	3.390 (7)	144 (6)
O1—H9B⋯Cl5ⁱⁱ	0.85 (6)	2.39 (6)	3.201 (6)	162 (5)
N1—H1A⋯Cl4ⁱⁱⁱ	0.90	2.40	3.181 (5)	145
N1—H1D⋯Cl4	0.90	2.57	3.284 (5)	137
N1—H1D⋯Cl5	0.90	2.75	3.455 (5)	136
N2—H2A⋯O1	0.90	1.82	2.705 (7)	167
N2—H2D⋯Cl7^iv	0.90	2.26	3.149 (5)	169
N3—H3C⋯Cl6	0.90	2.36	3.208 (5)	158
N3—H3D⋯Cl7^v	0.90	2.21	3.069 (5)	159
N4—H4C⋯Cl1^vi	0.90	2.37	3.228 (5)	158
N4—H4D⋯Cl4^vii	0.90	2.43	3.155 (5)	138

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

Acknowledgments

This work was supported by Jiangsu University of Science and Technology, China

supplementary crystallographic information

Comment

Recently, the crystal structure of compounds closely related to the title molecule, e.g., bis(piperazinium) bis(µ₂-chloro)-octachloro-di-bismuth(iii) trihydrate (Wu et al., 2005) and bis(N-Methylpiperazinium) bis((µ₂-chloro)-tetrachlorobismuthate(iii))- dihydrate (Fu et al., 2005) have been synthesized..We reported here thenew member of this family compounds.

The asymmetric unit of the title compound, 2C₄H₁₂N₂²⁺.BiCl₆^3-.Cl^-.H₂O(Fig.1), consists of two piperazine cation, one [BiCl₆]^3-one Cl^-anions and one water molecule. The Bi(III) ion exhibits a slightly distorted octahedral coordination environment. The diprotonated piperazine ring adopts a chair conformation. In the crystal structure, cations and anions are linked by intermolecular N—H···Cl, N—H···O and O—H···Cl hydrogen bonds into a three-dimensional network viewed along the a-axis (Fig.2).

Experimental

piperazine (10 mmol, 0.86 g) BiCl₃ (6.8 mmol, 2.15 g)and 35% aqueous HCl (3 ml) were mixed and dissolved in 30 ml water by heating to 353 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, block crystals of the title compound were formed after fifteen days.