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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1335.
Published online 2009 May 20. doi:  10.1107/S1600536809018182
PMCID: PMC2969668

Bis(5,6-dicarboxy­benzimidazolium) sulfate monohydrate

Abstract

In the title compound, 2C9H7N2O4 +·SO4 2−·H2O, the sulfate S atom and the water O atom reside on a crystallographic twofold axis. In the crystal, the component species are linked by N—H(...)O, O—H(...)O and C—H(...)O hydrogen bonds, forming a three-dimensional network structure. An intramol­ecular O—H(...)O link is seen in the cation.

Related literature

For a related structure that contains a benzimidazole mol­ecule, see: Gao et al. (2008 [triangle]). For the pharmacokinetics of an anti­allergic benzimidazole derivative, see: Sakai et al. (1989 [triangle]). For the synthesis and chemoluminescence of an amino drivative, see: White & Matsuo (1967 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1335-scheme1.jpg

Experimental

Crystal data

  • 2C9H7N2O4 +·SO4 2−·H2O
  • M r = 528.41
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1335-efi2.jpg
  • a = 14.691 (3) Å
  • b = 7.7968 (17) Å
  • c = 17.983 (4) Å
  • V = 2059.8 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.24 mm−1
  • T = 296 K
  • 0.12 × 0.11 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.971, T max = 0.976
  • 11525 measured reflections
  • 2413 independent reflections
  • 1994 reflections with I > 2σ(I)
  • R int = 0.060

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.138
  • S = 1.00
  • 2413 reflections
  • 168 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018182/si2172sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018182/si2172Isup2.hkl

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

Acknowledgments

This work was supported by the Beijing Municipal Natural Science Foundation (No. 2082004) and the Seventh Technology Fund for Postgraduates of Beijing University of Technology.

supplementary crystallographic information

Comment

Benzimidazole and related heterocyclic compounds have been extensively investigated because of their pharmacological activities (Sakai et al., 1989) and the application as intermediate for the synthesis of chemiluminescent compound (White & Matsuo, 1967). Otherwise, this kind of compounds is one of the most prevalent ligands in the field of coordination chemistry (Gao et al., 2008). Herein, we report the crystal structure of the title compound (Fig. 1), Bis(1H-benzimidazolium-5,6-dicarboxyl) sulfate monohydrate.

The title compound consists of two 1H-benzimidazole-5,6-dicarboxylic acid cations, one sulfate dianion and one water molecule. The sulfate S atom and the water O atom reside on crystallographic twofold axis. As one imine N atom on the benzimidazolium ring is protonated, there exsist positive charge in the ring (Scheme 1). The cations, dianions and water molecules are linked through a combination of intermolecular N—H···O, O—H···O and C—H···O hydrogen bonds (Table 1) to form a three-dimensional network structure.

Experimental

A solution containing a 2:1 molar ratio of ZnSO4 and 1H-benzoimidazole-5,6-dicarboxylate in water was sealed in a 25 ml teflon reactor and kept at 393K for 3 days. Then the mixture was filtered and the filtrate was allowed to stand at room temperature. Colorless block crystals suitable for the X-ray investigation were collected.

Refinement

The water H atoms were located in a difference Fourier map and freely refined. The N-bound H atoms were located in a difference Fourier map and fixed during the refinement with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
A view of the molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-hydrogen atoms. Symmetry related atoms labelled A have the symmetry code A = -x, y, 1/2 - z.

Crystal data

2C9H7N2O4+·SO42·H2OF(000) = 1088
Mr = 528.41Dx = 1.704 Mg m3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 2413 reflections
a = 14.691 (3) Åθ = 2.3–25.0°
b = 7.7968 (17) ŵ = 0.24 mm1
c = 17.983 (4) ÅT = 296 K
V = 2059.8 (8) Å3Block, colorless
Z = 40.12 × 0.11 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer2413 independent reflections
Radiation source: fine-focus sealed tube1994 reflections with I > 2σ(I)
graphiteRint = 0.060
[var phi] and ω scansθmax = 27.8°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −17→16
Tmin = 0.971, Tmax = 0.976k = −9→9
11525 measured reflectionsl = −21→17

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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0847P)2 + 0.8915P] where P = (Fo2 + 2Fc2)/3
2413 reflections(Δ/σ)max < 0.001
168 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.40 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
O10.35417 (10)0.1890 (2)0.09502 (8)0.0418 (4)
H280.36850.19030.14080.050*
O20.22201 (11)0.2483 (3)0.15019 (8)0.0553 (5)
O30.00994 (12)0.3035 (2)0.08983 (10)0.0586 (5)
O40.08286 (11)0.05673 (19)0.07644 (9)0.0474 (4)
H210.04650.01720.10890.057*
N10.29633 (11)0.4817 (2)−0.16017 (8)0.0344 (4)
H250.35350.4982−0.17180.041*
N20.15053 (11)0.5073 (2)−0.17520 (9)0.0358 (4)
H220.09690.5355−0.19620.043*
C10.26786 (14)0.2354 (2)0.09487 (10)0.0339 (4)
C20.23266 (12)0.2806 (2)0.01950 (9)0.0280 (4)
C30.29283 (11)0.3365 (2)−0.03408 (10)0.0293 (4)
H3A0.35540.3271−0.02760.035*
C40.25595 (12)0.4077 (2)−0.09819 (9)0.0282 (4)
C50.23151 (14)0.5390 (3)−0.20452 (11)0.0381 (4)
H5A0.24130.5936−0.24980.046*
C60.16218 (12)0.4236 (2)−0.10814 (10)0.0295 (4)
C70.10081 (12)0.3636 (2)−0.05544 (10)0.0316 (4)
H7A0.03830.3721−0.06260.038*
C80.13689 (12)0.2909 (2)0.00784 (10)0.0301 (4)
C90.07088 (12)0.2201 (3)0.06351 (11)0.0345 (4)
S10.0000−0.14201 (8)0.25000.0295 (2)
O90.07896 (13)−0.2429 (2)0.22937 (9)0.0630 (6)
O11−0.02520 (10)−0.0310 (2)0.18688 (9)0.0533 (5)
O1W0.00000.3439 (3)0.25000.0540 (6)
H1WA−0.024 (5)0.266 (8)0.286 (3)0.20 (3)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0398 (8)0.0540 (9)0.0318 (7)0.0075 (6)−0.0091 (6)0.0022 (6)
O20.0509 (9)0.0893 (13)0.0258 (7)0.0019 (9)0.0010 (6)−0.0032 (7)
O30.0511 (10)0.0602 (10)0.0645 (11)0.0225 (8)0.0302 (8)0.0198 (9)
O40.0501 (9)0.0412 (8)0.0510 (9)0.0022 (7)0.0229 (7)0.0079 (7)
N10.0301 (8)0.0445 (9)0.0285 (8)−0.0057 (7)0.0029 (6)0.0030 (6)
N20.0331 (8)0.0436 (9)0.0306 (8)−0.0038 (7)−0.0061 (6)0.0050 (7)
C10.0392 (10)0.0365 (10)0.0260 (9)−0.0010 (8)−0.0034 (7)−0.0017 (7)
C20.0283 (8)0.0305 (9)0.0253 (8)0.0027 (7)−0.0014 (6)−0.0028 (6)
C30.0239 (8)0.0355 (10)0.0284 (8)−0.0007 (7)−0.0010 (6)−0.0025 (7)
C40.0264 (8)0.0330 (9)0.0252 (8)−0.0035 (7)0.0010 (6)−0.0035 (7)
C50.0404 (10)0.0445 (11)0.0295 (9)−0.0061 (9)−0.0012 (8)0.0035 (8)
C60.0281 (8)0.0328 (9)0.0275 (8)−0.0020 (7)−0.0039 (6)−0.0003 (7)
C70.0222 (8)0.0381 (10)0.0345 (9)−0.0011 (7)0.0002 (7)0.0012 (7)
C80.0292 (8)0.0321 (9)0.0291 (9)0.0009 (7)0.0040 (7)−0.0014 (7)
C90.0287 (9)0.0426 (11)0.0323 (9)0.0032 (7)0.0055 (7)0.0038 (8)
S10.0309 (3)0.0334 (4)0.0243 (3)0.0000.0043 (2)0.000
O90.0814 (13)0.0702 (12)0.0374 (8)0.0449 (10)0.0205 (8)0.0090 (8)
O110.0300 (7)0.0781 (11)0.0517 (9)0.0056 (8)0.0054 (6)0.0308 (8)
O1W0.0597 (16)0.0487 (14)0.0538 (15)0.000−0.0195 (11)0.000

Geometric parameters (Å, °)

O1—C11.319 (2)C2—C81.425 (2)
O1—H280.8499C3—C41.389 (3)
O2—C11.205 (2)C3—H3A0.9300
O3—C91.204 (2)C4—C61.395 (3)
O4—C91.306 (3)C5—H5A0.9300
O4—H210.8496C6—C71.389 (3)
N1—C51.320 (3)C7—C81.377 (3)
N1—C41.388 (2)C7—H7A0.9300
N1—H250.8747C8—C91.499 (2)
N2—C51.325 (3)S1—O9i1.4498 (16)
N2—C61.382 (2)S1—O91.4498 (16)
N2—H220.9011S1—O11i1.4745 (15)
C1—C21.493 (2)S1—O111.4745 (15)
C2—C31.379 (2)O1W—H1WA0.95 (6)
C1—O1—H28103.7N1—C5—H5A124.9
C9—O4—H21113.0N2—C5—H5A124.9
C5—N1—C4108.51 (16)N2—C6—C7132.38 (17)
C5—N1—H25119.9N2—C6—C4106.03 (15)
C4—N1—H25131.5C7—C6—C4121.58 (17)
C5—N2—C6108.92 (16)C8—C7—C6116.90 (17)
C5—N2—H22124.9C8—C7—H7A121.6
C6—N2—H22126.1C6—C7—H7A121.6
O2—C1—O1123.95 (17)C7—C8—C2121.67 (16)
O2—C1—C2122.41 (18)C7—C8—C9117.03 (16)
O1—C1—C2113.55 (16)C2—C8—C9121.30 (16)
C3—C2—C8120.82 (16)O3—C9—O4123.86 (18)
C3—C2—C1119.15 (16)O3—C9—C8122.97 (18)
C8—C2—C1119.28 (16)O4—C9—C8113.02 (16)
C2—C3—C4117.14 (16)O9i—S1—O9114.29 (17)
C2—C3—H3A121.4O9i—S1—O11i108.80 (9)
C4—C3—H3A121.4O9—S1—O11i108.33 (10)
N1—C4—C3131.72 (17)O9i—S1—O11108.33 (10)
N1—C4—C6106.39 (15)O9—S1—O11108.80 (9)
C3—C4—C6121.81 (16)O11i—S1—O11108.15 (16)
N1—C5—N2110.14 (17)

Symmetry codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O3i0.96 (6)2.26 (5)2.9012 (11)123.6
O1W—H1WA···O11i0.96 (6)2.47 (6)3.1575 (16)128.4
O4—H21···O110.851.792.6330 (11)169
N2—H22···O1Wii0.901.962.8365 (10)163
N1—H25···O11iii0.881.822.6931 (12)175
O1—H28···O9iv0.851.842.6616 (11)161
C5—H5A···O2v0.932.203.098 (3)162

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2172).

References

  • Bruker (1998). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Gao, Q., Gao, W.-H., Zhang, C.-Y. & Xie, Y.-B. (2008). Acta Cryst. E64, m928. [PMC free article] [PubMed]
  • Sakai, T., Hamada, T., Awata, N. & Watanabe, J. (1989). J. Pharmacobio-Dynam.12, 530–536. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • White, E. H. & Matsuo, K. (1967). J. Org. Chem.32, 1921–1926.

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