2-(3-Pyridinio)benzimidazolium penta­chloridobismuthate(III) monohydrate

Cui, L.-J.; Xu, H.-J.; Pang, Y.-J.

doi:10.1107/S1600536809024568

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m852

doi:10.1107/S1600536809024568

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2-(3-Pyridinio)benzimidazolium pentachloridobismuthate(III) monohydrate

Li-Jing Cui,^a Hai-Jun Xu ^a ^* and Yi-Jie Pang ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xuhj@seu.edu.cn

(Received 19 June 2009; accepted 26 June 2009; online 1 July 2009)

In the title compound, (C₁₂H₁₁N₃)[BiCl₅]·H₂O, the Bi^III atom is coordinated by five chloride anions in a distorted square-pyramidal geometry. The planar imidazole ring system [maximum deviation = 0.012 (3) Å] is oriented at a dihedral angle of 6.08 (5)° with respect to the protonated pyridine ring. An O—H⋯Cl interaction links the water molecule to the dianion. In the crystal structure, intermolecular O—H⋯Cl, N—H⋯O and N—H⋯Cl interactions link the molecules into a three-dimensional network.

Related literature

For the properties of bismuthate(III) compounds, see: Turel et al. (1998 ); Goforth et al. (2004 ).

Experimental

Crystal data

(C₁₂H₁₁N₃)[BiCl₅]·H₂O
M_r = 601.48
Monoclinic, P 2₁ /c
a = 9.3297 (19) Å
b = 13.391 (3) Å
c = 14.476 (3) Å
β = 101.78 (3)°
V = 1770.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 10.72 mm⁻¹
T = 294 K
0.25 × 0.20 × 0.16 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.090, T_max = 0.180
17812 measured reflections
4049 independent reflections
2822 reflections with I > 2σ(I)
R_int = 0.115

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.116
S = 1.15
4049 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 1.28 e Å⁻³
Δρ_min = −2.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl5ⁱ	0.86	2.65	3.267 (8)	130
N1—H1A⋯Cl1ⁱⁱ	0.86	2.66	3.302 (8)	133
N2—H2A⋯O1Wⁱⁱⁱ	0.86	1.86	2.680 (9)	159
N3—H3B⋯Cl4^iv	0.86	2.33	3.104 (9)	150
O1W—H1WA⋯Cl3ⁱⁱ	0.85	2.62	3.292 (7)	137
O1W—H1WB⋯Cl5	0.85	2.77	3.190 (7)	112
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x-1, y, z; (iv) x, y, z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024568/hk2717sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024568/hk2717Isup2.hkl

checkCIF report

Comment top

Bismuthate(III) compounds have received great attention owing to their anti-ulcer activity (Turel et al., 1998) and their unique optical and electronic properties, including nonlinear optical activity, luminescence and semiconductivity (Goforth et al., 2004). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains a 2-(3'-pyridinio)benzimidazolium dication, a pentachlorobismuthate dianion and a water molecule. In the dianion, the bismuth (III) atom is coordinated by five chloride anions in a distorted square-pyramidal geometry. The Bi-Cl distances are in the range of 2.519 (3)-2.787 (3) Å. In the dication, the planar imidazole ring system [with maximum deviation of 0.012 (3) Å for atom C3] is oriented with respect to the pyridine ring at a dihedral angle of 6.08 (5)°. Intramolecular O-H···Cl interaction links the water molecule to the dianion (Table 1).

In the crystal structure, intramolecular O-H···Cl and intermolecular N-H···O and N-H···Cl interactions (Table 1) link the molecules into a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For the properties of the bismuthate(III) compounds, see: Turel et al. (1998); Goforth et al. (2004).

Experimental top

For the preparation of the title compound, concentrated hydrochloric acid (12 M) was added dropwise to a mixture of 2-(3-pyridinio)benzimidazole (0.1 mmol) and water (7 ml), until complete dissolution of the solid phase. Concentrated hydrochloric acid was similarly added dropwise to dissolve the solid phase persisting in a mixture of bismuth chloride (0.3 mmol) and water (5 ml). The two solutions were then mixed and stirred for 20 min. The resulting precipitate was filtered off and dissolved in hydrochloric acid. Colorless crystals suitable for X-ray analysis were obtained after several weeks by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level
	Fig. 2. A partial packing diagram.

2-(3-Pyridinio)benzimidazolium pentachloridobismuthate(III) monohydrate top

Crystal data top

(C₁₂H₁₁N₃)[BiCl₅]·H₂O	F(000) = 1128
M_r = 601.48	D_x = 2.256 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1647 reflections
a = 9.3297 (19) Å	θ = 3.0–27.6°
b = 13.391 (3) Å	µ = 10.72 mm⁻¹
c = 14.476 (3) Å	T = 294 K
β = 101.78 (3)°	Prism, colorless
V = 1770.6 (6) Å³	0.25 × 0.20 × 0.16 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	4049 independent reflections
Radiation source: fine-focus sealed tube	2822 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.115
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −17→17
T_min = 0.090, T_max = 0.180	l = −18→18
17812 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0236P)²] where P = (F_o² + 2F_c²)/3
4049 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 1.28 e Å⁻³
0 restraints	Δρ_min = −2.37 e Å⁻³

Crystal data top

(C₁₂H₁₁N₃)[BiCl₅]·H₂O	V = 1770.6 (6) Å³
M_r = 601.48	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3297 (19) Å	µ = 10.72 mm⁻¹
b = 13.391 (3) Å	T = 294 K
c = 14.476 (3) Å	0.25 × 0.20 × 0.16 mm
β = 101.78 (3)°

Data collection top

Rigaku SCXmini diffractometer	4049 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2822 reflections with I > 2σ(I)
T_min = 0.090, T_max = 0.180	R_int = 0.115
17812 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.15	Δρ_max = 1.28 e Å⁻³
4049 reflections	Δρ_min = −2.37 e Å⁻³
199 parameters

Special details top

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 > σ(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.

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

	x	y	z	U_iso*/U_eq
Bi1	0.50077 (4)	0.91031 (3)	0.12159 (2)	0.03242 (14)
Cl1	0.4928 (3)	0.7336 (2)	0.1799 (2)	0.0538 (8)
Cl2	0.7784 (3)	0.8830 (2)	0.1188 (2)	0.0516 (8)
Cl3	0.4576 (3)	0.8682 (2)	−0.07062 (17)	0.0432 (6)
Cl4	0.1991 (3)	0.8994 (2)	0.09655 (18)	0.0461 (7)
Cl5	0.5648 (3)	0.9799 (2)	0.29758 (18)	0.0474 (7)
O1W	0.6526 (7)	0.8372 (5)	0.4766 (5)	0.060 (2)
H1WA	0.6470	0.7747	0.4854	0.072*
H1WB	0.6594	0.8234	0.4204	0.072*
N1	0.1677 (8)	0.8703 (6)	0.6102 (6)	0.041 (2)
H1A	0.2466	0.8720	0.6529	0.049*
N2	−0.0597 (8)	0.8600 (6)	0.5442 (5)	0.0296 (18)
H2A	−0.1532	0.8541	0.5371	0.036*
N3	0.0630 (10)	0.8739 (7)	0.8836 (6)	0.046 (2)
H3B	0.1305	0.8813	0.9333	0.055*
C1	0.0159 (10)	0.8685 (8)	0.4712 (7)	0.034 (2)
C2	0.1627 (10)	0.8756 (8)	0.5147 (7)	0.039 (3)
C3	0.2710 (12)	0.8833 (10)	0.4600 (8)	0.066 (4)
H3A	0.3700	0.8858	0.4880	0.079*
C4	0.2242 (12)	0.8869 (9)	0.3637 (9)	0.061 (4)
H4A	0.2924	0.8938	0.3253	0.073*
C5	0.0769 (12)	0.8804 (8)	0.3231 (7)	0.049 (3)
H5A	0.0494	0.8827	0.2577	0.058*
C6	−0.0300 (11)	0.8709 (8)	0.3738 (7)	0.041 (3)
H6A	−0.1284	0.8662	0.3448	0.049*
C7	0.0345 (9)	0.8625 (7)	0.6271 (7)	0.030 (2)
C8	−0.0055 (10)	0.8596 (7)	0.7183 (7)	0.030 (2)
C9	0.1021 (11)	0.8701 (8)	0.8005 (7)	0.042 (3)
H9A	0.2003	0.8745	0.7970	0.051*
C10	−0.0742 (12)	0.8670 (8)	0.8940 (7)	0.041 (3)
H10A	−0.0956	0.8702	0.9539	0.050*
C11	−0.1834 (11)	0.8552 (8)	0.8174 (7)	0.041 (3)
H11A	−0.2800	0.8491	0.8243	0.049*
C12	−0.1504 (10)	0.8524 (7)	0.7299 (7)	0.032 (2)
H12A	−0.2255	0.8457	0.6771	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Bi1	0.0332 (2)	0.0371 (2)	0.0254 (2)	−0.00200 (18)	0.00251 (15)	0.00118 (18)
Cl1	0.0385 (15)	0.0486 (19)	0.068 (2)	−0.0013 (13)	−0.0025 (14)	0.0145 (15)
Cl2	0.0353 (15)	0.071 (2)	0.0482 (18)	−0.0031 (13)	0.0091 (13)	0.0045 (15)
Cl3	0.0503 (16)	0.0478 (17)	0.0285 (14)	0.0024 (13)	0.0014 (12)	−0.0016 (12)
Cl4	0.0344 (14)	0.072 (2)	0.0317 (14)	0.0069 (13)	0.0062 (11)	−0.0009 (14)
Cl5	0.0567 (17)	0.0524 (19)	0.0308 (15)	−0.0069 (14)	0.0031 (12)	−0.0090 (13)
O1W	0.057 (5)	0.044 (5)	0.074 (6)	−0.010 (4)	−0.001 (4)	0.022 (4)
N1	0.033 (5)	0.051 (6)	0.034 (5)	0.001 (4)	−0.004 (4)	0.002 (4)
N2	0.022 (4)	0.036 (5)	0.029 (5)	0.005 (3)	0.001 (4)	−0.001 (4)
N3	0.050 (6)	0.053 (6)	0.031 (5)	−0.002 (5)	−0.003 (4)	0.001 (4)
C1	0.032 (6)	0.035 (6)	0.033 (6)	−0.001 (4)	0.002 (5)	0.002 (5)
C2	0.033 (6)	0.049 (7)	0.035 (6)	0.001 (5)	0.007 (5)	−0.002 (5)
C3	0.031 (7)	0.114 (12)	0.052 (8)	−0.002 (6)	0.008 (6)	0.020 (8)
C4	0.043 (7)	0.097 (11)	0.050 (8)	0.005 (6)	0.023 (6)	0.020 (7)
C5	0.052 (7)	0.070 (9)	0.024 (6)	0.003 (6)	0.007 (5)	0.009 (5)
C6	0.039 (6)	0.047 (7)	0.037 (6)	−0.001 (5)	0.009 (5)	0.011 (5)
C7	0.024 (5)	0.028 (6)	0.037 (6)	−0.001 (4)	0.001 (5)	−0.004 (5)
C8	0.043 (6)	0.016 (5)	0.026 (5)	−0.006 (4)	0.000 (4)	0.000 (4)
C9	0.044 (6)	0.048 (7)	0.028 (6)	−0.002 (5)	−0.009 (5)	−0.002 (5)
C10	0.063 (7)	0.032 (6)	0.029 (6)	−0.001 (6)	0.008 (5)	−0.006 (5)
C11	0.050 (7)	0.029 (7)	0.045 (7)	0.001 (5)	0.010 (5)	−0.008 (5)
C12	0.032 (6)	0.024 (6)	0.037 (6)	0.000 (4)	−0.001 (5)	0.003 (5)

Geometric parameters (Å, º) top

Bi1—Cl1	2.519 (3)	C4—H4A	0.9300
Bi1—Cl2	2.624 (3)	C5—C6	1.359 (13)
Bi1—Cl3	2.787 (3)	C5—H5A	0.9300
Bi1—Cl4	2.767 (3)	C6—H6A	0.9300
Bi1—Cl5	2.664 (3)	C7—N1	1.319 (11)
O1W—H1WA	0.8500	C7—N2	1.335 (10)
O1W—H1WB	0.8500	C7—C8	1.443 (12)
N1—H1A	0.8600	C8—C9	1.399 (12)
N2—H2A	0.8600	C8—C12	1.400 (12)
N3—H3B	0.8600	C9—N3	1.327 (12)
C1—C6	1.389 (13)	C9—H9A	0.9300
C1—C2	1.389 (12)	C10—N3	1.322 (13)
C1—N2	1.390 (11)	C10—C11	1.354 (13)
C2—N1	1.376 (12)	C10—H10A	0.9300
C2—C3	1.409 (14)	C11—C12	1.363 (13)
C3—C4	1.375 (15)	C11—H11A	0.9300
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.383 (14)

Cl1—Bi1—Cl2	88.33 (9)	C2—C3—H3A	121.4
Cl1—Bi1—Cl3	97.85 (9)	C3—C4—C5	120.7 (10)
Cl1—Bi1—Cl4	83.99 (8)	C3—C4—H4A	119.6
Cl1—Bi1—Cl5	91.41 (10)	C5—C4—H4A	119.6
Cl2—Bi1—Cl3	84.18 (9)	C6—C5—C4	123.5 (10)
Cl2—Bi1—Cl4	166.23 (9)	C6—C5—H5A	118.2
Cl2—Bi1—Cl5	91.96 (9)	C4—C5—H5A	118.2
Cl4—Bi1—Cl3	85.56 (8)	C5—C6—C1	116.2 (10)
Cl5—Bi1—Cl3	169.84 (8)	C5—C6—H6A	121.9
Cl5—Bi1—Cl4	99.63 (8)	C1—C6—H6A	121.9
H1WA—O1W—H1WB	87.0	N1—C7—N2	107.9 (8)
C2—N1—H1A	124.7	N1—C7—C8	126.9 (9)
C7—N1—C2	110.5 (8)	N2—C7—C8	125.1 (8)
C7—N1—H1A	124.7	C9—C8—C12	116.6 (9)
C1—N2—H2A	125.1	C9—C8—C7	120.1 (9)
C7—N2—C1	109.7 (8)	C12—C8—C7	123.3 (8)
C7—N2—H2A	125.1	N3—C9—C8	119.5 (10)
C9—N3—H3B	118.2	N3—C9—H9A	120.2
C10—N3—C9	123.5 (10)	C8—C9—H9A	120.2
C10—N3—H3B	118.2	N3—C10—C11	120.0 (10)
C6—C1—C2	122.0 (9)	N3—C10—H10A	120.0
C6—C1—N2	132.4 (9)	C11—C10—H10A	120.0
C2—C1—N2	105.5 (8)	C10—C11—C12	119.3 (10)
N1—C2—C1	106.2 (9)	C10—C11—H11A	120.4
N1—C2—C3	133.4 (10)	C12—C11—H11A	120.4
C1—C2—C3	120.3 (10)	C11—C12—C8	121.1 (9)
C4—C3—C2	117.2 (10)	C11—C12—H12A	119.4
C4—C3—H3A	121.4	C8—C12—H12A	119.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl5ⁱ	0.86	2.65	3.267 (8)	130
N1—H1A···Cl1ⁱⁱ	0.86	2.66	3.302 (8)	133
N2—H2A···O1Wⁱⁱⁱ	0.86	1.86	2.680 (9)	159
N3—H3B···Cl4^iv	0.86	2.33	3.104 (9)	150
O1W—H1WA···Cl3ⁱⁱ	0.85	2.62	3.292 (7)	137
O1W—H1WB···Cl5	0.85	2.77	3.190 (7)	112

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x−1, y, z; (iv) x, y, z+1.

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₁N₃)[BiCl₅]·H₂O
M_r	601.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	9.3297 (19), 13.391 (3), 14.476 (3)
β (°)	101.78 (3)
V (Å³)	1770.6 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.72
Crystal size (mm)	0.25 × 0.20 × 0.16

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.090, 0.180
No. of measured, independent and observed [I > 2σ(I)] reflections	17812, 4049, 2822
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.116, 1.15
No. of reflections	4049
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.28, −2.37

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl5ⁱ	0.86	2.65	3.267 (8)	129.6
N1—H1A···Cl1ⁱⁱ	0.86	2.66	3.302 (8)	132.8
N2—H2A···O1Wⁱⁱⁱ	0.86	1.86	2.680 (9)	159.2
N3—H3B···Cl4^iv	0.86	2.33	3.104 (9)	149.7
O1W—H1WA···Cl3ⁱⁱ	0.85	2.62	3.292 (7)	137.0
O1W—H1WB···Cl5	0.85	2.77	3.190 (7)	111.9

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x−1, y, z; (iv) x, y, z+1.

References

Goforth, A. M., Smith, M. D., Peterson, L. Jr & zur Loye, H.-C. (2004). Inorg. Chem. 43, 7042–7049. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Turel, I., Golič, L., Bukovec, P. & Gubina, M. (1998). Inorg. Biochem. 71, 53–60. Web of Science CrossRef CAS Google Scholar

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doi:10.1107/S1600536809024568

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