PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m852.
Published online 2009 July 1. doi:  10.1107/S1600536809024568
PMCID: PMC2977254

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

Abstract

In the title compound, (C12H11N3)[BiCl5]·H2O, the BiIII 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 [triangle]); Goforth et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m852-scheme1.jpg

Experimental

Crystal data

  • (C12H11N3)[BiCl5]·H2O
  • M r = 601.48
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m852-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.116
  • S = 1.15
  • 4049 reflections
  • 199 parameters
  • H-atom parameters constrained
  • Δρmax = 1.28 e Å−3
  • Δρmin = −2.37 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically with O-H = 0.85 Å (for H2O), N-H = 0.86 Å (for NH) and C-H = 0.93 Å for aromatic H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N,O).

Figures

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.

Crystal data

(C12H11N3)[BiCl5]·H2OF(000) = 1128
Mr = 601.48Dx = 2.256 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1647 reflections
a = 9.3297 (19) Åθ = 3.0–27.6°
b = 13.391 (3) ŵ = 10.72 mm1
c = 14.476 (3) ÅT = 294 K
β = 101.78 (3)°Prism, colorless
V = 1770.6 (6) Å30.25 × 0.20 × 0.16 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer4049 independent reflections
Radiation source: fine-focus sealed tube2822 reflections with I > 2σ(I)
graphiteRint = 0.115
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −17→17
Tmin = 0.090, Tmax = 0.180l = −18→18
17812 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.15w = 1/[σ2(Fo2) + (0.0236P)2] where P = (Fo2 + 2Fc2)/3
4049 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 1.28 e Å3
0 restraintsΔρmin = −2.37 e Å3

Special details

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)

xyzUiso*/Ueq
Bi10.50077 (4)0.91031 (3)0.12159 (2)0.03242 (14)
Cl10.4928 (3)0.7336 (2)0.1799 (2)0.0538 (8)
Cl20.7784 (3)0.8830 (2)0.1188 (2)0.0516 (8)
Cl30.4576 (3)0.8682 (2)−0.07062 (17)0.0432 (6)
Cl40.1991 (3)0.8994 (2)0.09655 (18)0.0461 (7)
Cl50.5648 (3)0.9799 (2)0.29758 (18)0.0474 (7)
O1W0.6526 (7)0.8372 (5)0.4766 (5)0.060 (2)
H1WA0.64700.77470.48540.072*
H1WB0.65940.82340.42040.072*
N10.1677 (8)0.8703 (6)0.6102 (6)0.041 (2)
H1A0.24660.87200.65290.049*
N2−0.0597 (8)0.8600 (6)0.5442 (5)0.0296 (18)
H2A−0.15320.85410.53710.036*
N30.0630 (10)0.8739 (7)0.8836 (6)0.046 (2)
H3B0.13050.88130.93330.055*
C10.0159 (10)0.8685 (8)0.4712 (7)0.034 (2)
C20.1627 (10)0.8756 (8)0.5147 (7)0.039 (3)
C30.2710 (12)0.8833 (10)0.4600 (8)0.066 (4)
H3A0.37000.88580.48800.079*
C40.2242 (12)0.8869 (9)0.3637 (9)0.061 (4)
H4A0.29240.89380.32530.073*
C50.0769 (12)0.8804 (8)0.3231 (7)0.049 (3)
H5A0.04940.88270.25770.058*
C6−0.0300 (11)0.8709 (8)0.3738 (7)0.041 (3)
H6A−0.12840.86620.34480.049*
C70.0345 (9)0.8625 (7)0.6271 (7)0.030 (2)
C8−0.0055 (10)0.8596 (7)0.7183 (7)0.030 (2)
C90.1021 (11)0.8701 (8)0.8005 (7)0.042 (3)
H9A0.20030.87450.79700.051*
C10−0.0742 (12)0.8670 (8)0.8940 (7)0.041 (3)
H10A−0.09560.87020.95390.050*
C11−0.1834 (11)0.8552 (8)0.8174 (7)0.041 (3)
H11A−0.28000.84910.82430.049*
C12−0.1504 (10)0.8524 (7)0.7299 (7)0.032 (2)
H12A−0.22550.84570.67710.039*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Bi10.0332 (2)0.0371 (2)0.0254 (2)−0.00200 (18)0.00251 (15)0.00118 (18)
Cl10.0385 (15)0.0486 (19)0.068 (2)−0.0013 (13)−0.0025 (14)0.0145 (15)
Cl20.0353 (15)0.071 (2)0.0482 (18)−0.0031 (13)0.0091 (13)0.0045 (15)
Cl30.0503 (16)0.0478 (17)0.0285 (14)0.0024 (13)0.0014 (12)−0.0016 (12)
Cl40.0344 (14)0.072 (2)0.0317 (14)0.0069 (13)0.0062 (11)−0.0009 (14)
Cl50.0567 (17)0.0524 (19)0.0308 (15)−0.0069 (14)0.0031 (12)−0.0090 (13)
O1W0.057 (5)0.044 (5)0.074 (6)−0.010 (4)−0.001 (4)0.022 (4)
N10.033 (5)0.051 (6)0.034 (5)0.001 (4)−0.004 (4)0.002 (4)
N20.022 (4)0.036 (5)0.029 (5)0.005 (3)0.001 (4)−0.001 (4)
N30.050 (6)0.053 (6)0.031 (5)−0.002 (5)−0.003 (4)0.001 (4)
C10.032 (6)0.035 (6)0.033 (6)−0.001 (4)0.002 (5)0.002 (5)
C20.033 (6)0.049 (7)0.035 (6)0.001 (5)0.007 (5)−0.002 (5)
C30.031 (7)0.114 (12)0.052 (8)−0.002 (6)0.008 (6)0.020 (8)
C40.043 (7)0.097 (11)0.050 (8)0.005 (6)0.023 (6)0.020 (7)
C50.052 (7)0.070 (9)0.024 (6)0.003 (6)0.007 (5)0.009 (5)
C60.039 (6)0.047 (7)0.037 (6)−0.001 (5)0.009 (5)0.011 (5)
C70.024 (5)0.028 (6)0.037 (6)−0.001 (4)0.001 (5)−0.004 (5)
C80.043 (6)0.016 (5)0.026 (5)−0.006 (4)0.000 (4)0.000 (4)
C90.044 (6)0.048 (7)0.028 (6)−0.002 (5)−0.009 (5)−0.002 (5)
C100.063 (7)0.032 (6)0.029 (6)−0.001 (6)0.008 (5)−0.006 (5)
C110.050 (7)0.029 (7)0.045 (7)0.001 (5)0.010 (5)−0.008 (5)
C120.032 (6)0.024 (6)0.037 (6)0.000 (4)−0.001 (5)0.003 (5)

Geometric parameters (Å, °)

Bi1—Cl12.519 (3)C4—H4A0.9300
Bi1—Cl22.624 (3)C5—C61.359 (13)
Bi1—Cl32.787 (3)C5—H5A0.9300
Bi1—Cl42.767 (3)C6—H6A0.9300
Bi1—Cl52.664 (3)C7—N11.319 (11)
O1W—H1WA0.8500C7—N21.335 (10)
O1W—H1WB0.8500C7—C81.443 (12)
N1—H1A0.8600C8—C91.399 (12)
N2—H2A0.8600C8—C121.400 (12)
N3—H3B0.8600C9—N31.327 (12)
C1—C61.389 (13)C9—H9A0.9300
C1—C21.389 (12)C10—N31.322 (13)
C1—N21.390 (11)C10—C111.354 (13)
C2—N11.376 (12)C10—H10A0.9300
C2—C31.409 (14)C11—C121.363 (13)
C3—C41.375 (15)C11—H11A0.9300
C3—H3A0.9300C12—H12A0.9300
C4—C51.383 (14)
Cl1—Bi1—Cl288.33 (9)C2—C3—H3A121.4
Cl1—Bi1—Cl397.85 (9)C3—C4—C5120.7 (10)
Cl1—Bi1—Cl483.99 (8)C3—C4—H4A119.6
Cl1—Bi1—Cl591.41 (10)C5—C4—H4A119.6
Cl2—Bi1—Cl384.18 (9)C6—C5—C4123.5 (10)
Cl2—Bi1—Cl4166.23 (9)C6—C5—H5A118.2
Cl2—Bi1—Cl591.96 (9)C4—C5—H5A118.2
Cl4—Bi1—Cl385.56 (8)C5—C6—C1116.2 (10)
Cl5—Bi1—Cl3169.84 (8)C5—C6—H6A121.9
Cl5—Bi1—Cl499.63 (8)C1—C6—H6A121.9
H1WA—O1W—H1WB87.0N1—C7—N2107.9 (8)
C2—N1—H1A124.7N1—C7—C8126.9 (9)
C7—N1—C2110.5 (8)N2—C7—C8125.1 (8)
C7—N1—H1A124.7C9—C8—C12116.6 (9)
C1—N2—H2A125.1C9—C8—C7120.1 (9)
C7—N2—C1109.7 (8)C12—C8—C7123.3 (8)
C7—N2—H2A125.1N3—C9—C8119.5 (10)
C9—N3—H3B118.2N3—C9—H9A120.2
C10—N3—C9123.5 (10)C8—C9—H9A120.2
C10—N3—H3B118.2N3—C10—C11120.0 (10)
C6—C1—C2122.0 (9)N3—C10—H10A120.0
C6—C1—N2132.4 (9)C11—C10—H10A120.0
C2—C1—N2105.5 (8)C10—C11—C12119.3 (10)
N1—C2—C1106.2 (9)C10—C11—H11A120.4
N1—C2—C3133.4 (10)C12—C11—H11A120.4
C1—C2—C3120.3 (10)C11—C12—C8121.1 (9)
C4—C3—C2117.2 (10)C11—C12—H12A119.4
C4—C3—H3A121.4C8—C12—H12A119.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl5i0.862.653.267 (8)130
N1—H1A···Cl1ii0.862.663.302 (8)133
N2—H2A···O1Wiii0.861.862.680 (9)159
N3—H3B···Cl4iv0.862.333.104 (9)150
O1W—H1WA···Cl3ii0.852.623.292 (7)137
O1W—H1WB···Cl50.852.773.190 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2717).

References

  • Goforth, A. M., Smith, M. D., Peterson, L. Jr & zur Loye, H.-C. (2004). Inorg. Chem 43, 7042–7049. [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Turel, I., Golič, L., Bukovec, P. & Gubina, M. (1998). Inorg. Biochem.71, 53–60. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography