Bis(5,6-dicarboxy­benzimidazolium) sulfate monohydrate

Cui, Y.; Gao, Q.; Zhang, C.-Y.; Xie, Y.-B.

doi:10.1107/S1600536809018182

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1335

doi:10.1107/S1600536809018182

Open

access

Bis(5,6-dicarboxybenzimidazolium) sulfate monohydrate

Yue Cui,^a Qian Gao,^a Chao-Yan Zhang ^a and Ya-Bo Xie ^a ^*

^aCollege of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: xieyabo@bjut.edu.cn

(Received 29 April 2009; accepted 14 May 2009; online 20 May 2009)

In the title compound, 2C₉H₇N₂O₄⁺·SO₄²⁻·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 ). For the pharmacokinetics of an antiallergic benzimidazole derivative, see: Sakai et al. (1989 ). For the synthesis and chemoluminescence of an amino drivative, see: White & Matsuo (1967 ).

Experimental

Crystal data

2C₉H₇N₂O₄⁺·SO₄²⁻·H₂O
M_r = 528.41
Orthorhombic, P b c n
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 ) 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[F² > 2σ(F²)] = 0.048
wR(F²) = 0.138
S = 1.00
2413 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H22⋯O1Wⁱⁱ	0.90	1.96	2.8365 (10)	163
N1—H25⋯O11ⁱⁱⁱ	0.88	1.82	2.6931 (12)	175
C5—H5A⋯O2^v	0.93	2.20	3.098 (3)	162
O1—H28⋯O9^iv	0.85	1.84	2.6616 (11)	161
O4—H21⋯O11	0.85	1.79	2.6330 (11)	169
O1W—H1WA⋯O3ⁱ	0.96 (6)	2.26 (5)	2.9012 (11)	123.6
O1W—H1WA⋯O11ⁱ	0.96 (6)	2.47 (6)	3.1575 (16)	128.4
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) $[x, -y+1, z-{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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: SHELXTL (Sheldrick, 2008).

Figures top

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.

Bis(5,6-dicarboxybenzimidazolium) sulfate monohydrate top

Crystal data top

2C₉H₇N₂O₄⁺·SO₄²⁻·H₂O	F(000) = 1088
M_r = 528.41	D_x = 1.704 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2413 reflections
a = 14.691 (3) Å	θ = 2.3–25.0°
b = 7.7968 (17) Å	µ = 0.24 mm⁻¹
c = 17.983 (4) Å	T = 296 K
V = 2059.8 (8) Å³	Block, colorless
Z = 4	0.12 × 0.11 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2413 independent reflections
Radiation source: fine-focus sealed tube	1994 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ and ω scans	θ_max = 27.8°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −17→16
T_min = 0.971, T_max = 0.976	k = −9→9
11525 measured reflections	l = −21→17

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0847P)² + 0.8915P] where P = (F_o² + 2F_c²)/3
2413 reflections	(Δ/σ)_max < 0.001
168 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

2C₉H₇N₂O₄⁺·SO₄²⁻·H₂O	V = 2059.8 (8) Å³
M_r = 528.41	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.691 (3) Å	µ = 0.24 mm⁻¹
b = 7.7968 (17) Å	T = 296 K
c = 17.983 (4) Å	0.12 × 0.11 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2413 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1994 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.976	R_int = 0.060
11525 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.46 e Å⁻³
2413 reflections	Δρ_min = −0.40 e Å⁻³
168 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
O1	0.35417 (10)	0.1890 (2)	0.09502 (8)	0.0418 (4)
H28	0.3685	0.1903	0.1408	0.050*
O2	0.22201 (11)	0.2483 (3)	0.15019 (8)	0.0553 (5)
O3	0.00994 (12)	0.3035 (2)	0.08983 (10)	0.0586 (5)
O4	0.08286 (11)	0.05673 (19)	0.07644 (9)	0.0474 (4)
H21	0.0465	0.0172	0.1089	0.057*
N1	0.29633 (11)	0.4817 (2)	−0.16017 (8)	0.0344 (4)
H25	0.3535	0.4982	−0.1718	0.041*
N2	0.15053 (11)	0.5073 (2)	−0.17520 (9)	0.0358 (4)
H22	0.0969	0.5355	−0.1962	0.043*
C1	0.26786 (14)	0.2354 (2)	0.09487 (10)	0.0339 (4)
C2	0.23266 (12)	0.2806 (2)	0.01950 (9)	0.0280 (4)
C3	0.29283 (11)	0.3365 (2)	−0.03408 (10)	0.0293 (4)
H3A	0.3554	0.3271	−0.0276	0.035*
C4	0.25595 (12)	0.4077 (2)	−0.09819 (9)	0.0282 (4)
C5	0.23151 (14)	0.5390 (3)	−0.20452 (11)	0.0381 (4)
H5A	0.2413	0.5936	−0.2498	0.046*
C6	0.16218 (12)	0.4236 (2)	−0.10814 (10)	0.0295 (4)
C7	0.10081 (12)	0.3636 (2)	−0.05544 (10)	0.0316 (4)
H7A	0.0383	0.3721	−0.0626	0.038*
C8	0.13689 (12)	0.2909 (2)	0.00784 (10)	0.0301 (4)
C9	0.07088 (12)	0.2201 (3)	0.06351 (11)	0.0345 (4)
S1	0.0000	−0.14201 (8)	0.2500	0.0295 (2)
O9	0.07896 (13)	−0.2429 (2)	0.22937 (9)	0.0630 (6)
O11	−0.02520 (10)	−0.0310 (2)	0.18688 (9)	0.0533 (5)
O1W	0.0000	0.3439 (3)	0.2500	0.0540 (6)
H1WA	−0.024 (5)	0.266 (8)	0.286 (3)	0.20 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0398 (8)	0.0540 (9)	0.0318 (7)	0.0075 (6)	−0.0091 (6)	0.0022 (6)
O2	0.0509 (9)	0.0893 (13)	0.0258 (7)	0.0019 (9)	0.0010 (6)	−0.0032 (7)
O3	0.0511 (10)	0.0602 (10)	0.0645 (11)	0.0225 (8)	0.0302 (8)	0.0198 (9)
O4	0.0501 (9)	0.0412 (8)	0.0510 (9)	0.0022 (7)	0.0229 (7)	0.0079 (7)
N1	0.0301 (8)	0.0445 (9)	0.0285 (8)	−0.0057 (7)	0.0029 (6)	0.0030 (6)
N2	0.0331 (8)	0.0436 (9)	0.0306 (8)	−0.0038 (7)	−0.0061 (6)	0.0050 (7)
C1	0.0392 (10)	0.0365 (10)	0.0260 (9)	−0.0010 (8)	−0.0034 (7)	−0.0017 (7)
C2	0.0283 (8)	0.0305 (9)	0.0253 (8)	0.0027 (7)	−0.0014 (6)	−0.0028 (6)
C3	0.0239 (8)	0.0355 (10)	0.0284 (8)	−0.0007 (7)	−0.0010 (6)	−0.0025 (7)
C4	0.0264 (8)	0.0330 (9)	0.0252 (8)	−0.0035 (7)	0.0010 (6)	−0.0035 (7)
C5	0.0404 (10)	0.0445 (11)	0.0295 (9)	−0.0061 (9)	−0.0012 (8)	0.0035 (8)
C6	0.0281 (8)	0.0328 (9)	0.0275 (8)	−0.0020 (7)	−0.0039 (6)	−0.0003 (7)
C7	0.0222 (8)	0.0381 (10)	0.0345 (9)	−0.0011 (7)	0.0002 (7)	0.0012 (7)
C8	0.0292 (8)	0.0321 (9)	0.0291 (9)	0.0009 (7)	0.0040 (7)	−0.0014 (7)
C9	0.0287 (9)	0.0426 (11)	0.0323 (9)	0.0032 (7)	0.0055 (7)	0.0038 (8)
S1	0.0309 (3)	0.0334 (4)	0.0243 (3)	0.000	0.0043 (2)	0.000
O9	0.0814 (13)	0.0702 (12)	0.0374 (8)	0.0449 (10)	0.0205 (8)	0.0090 (8)
O11	0.0300 (7)	0.0781 (11)	0.0517 (9)	0.0056 (8)	0.0054 (6)	0.0308 (8)
O1W	0.0597 (16)	0.0487 (14)	0.0538 (15)	0.000	−0.0195 (11)	0.000

Geometric parameters (Å, º) top

O1—C1	1.319 (2)	C2—C8	1.425 (2)
O1—H28	0.8499	C3—C4	1.389 (3)
O2—C1	1.205 (2)	C3—H3A	0.9300
O3—C9	1.204 (2)	C4—C6	1.395 (3)
O4—C9	1.306 (3)	C5—H5A	0.9300
O4—H21	0.8496	C6—C7	1.389 (3)
N1—C5	1.320 (3)	C7—C8	1.377 (3)
N1—C4	1.388 (2)	C7—H7A	0.9300
N1—H25	0.8747	C8—C9	1.499 (2)
N2—C5	1.325 (3)	S1—O9ⁱ	1.4498 (16)
N2—C6	1.382 (2)	S1—O9	1.4498 (16)
N2—H22	0.9011	S1—O11ⁱ	1.4745 (15)
C1—C2	1.493 (2)	S1—O11	1.4745 (15)
C2—C3	1.379 (2)	O1W—H1WA	0.95 (6)

C1—O1—H28	103.7	N1—C5—H5A	124.9
C9—O4—H21	113.0	N2—C5—H5A	124.9
C5—N1—C4	108.51 (16)	N2—C6—C7	132.38 (17)
C5—N1—H25	119.9	N2—C6—C4	106.03 (15)
C4—N1—H25	131.5	C7—C6—C4	121.58 (17)
C5—N2—C6	108.92 (16)	C8—C7—C6	116.90 (17)
C5—N2—H22	124.9	C8—C7—H7A	121.6
C6—N2—H22	126.1	C6—C7—H7A	121.6
O2—C1—O1	123.95 (17)	C7—C8—C2	121.67 (16)
O2—C1—C2	122.41 (18)	C7—C8—C9	117.03 (16)
O1—C1—C2	113.55 (16)	C2—C8—C9	121.30 (16)
C3—C2—C8	120.82 (16)	O3—C9—O4	123.86 (18)
C3—C2—C1	119.15 (16)	O3—C9—C8	122.97 (18)
C8—C2—C1	119.28 (16)	O4—C9—C8	113.02 (16)
C2—C3—C4	117.14 (16)	O9ⁱ—S1—O9	114.29 (17)
C2—C3—H3A	121.4	O9ⁱ—S1—O11ⁱ	108.80 (9)
C4—C3—H3A	121.4	O9—S1—O11ⁱ	108.33 (10)
N1—C4—C3	131.72 (17)	O9ⁱ—S1—O11	108.33 (10)
N1—C4—C6	106.39 (15)	O9—S1—O11	108.80 (9)
C3—C4—C6	121.81 (16)	O11ⁱ—S1—O11	108.15 (16)
N1—C5—N2	110.14 (17)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3ⁱ	0.96 (6)	2.26 (5)	2.9012 (11)	123.6
O1W—H1WA···O11ⁱ	0.96 (6)	2.47 (6)	3.1575 (16)	128.4
O4—H21···O11	0.85	1.79	2.6330 (11)	169
N2—H22···O1Wⁱⁱ	0.90	1.96	2.8365 (10)	163
N1—H25···O11ⁱⁱⁱ	0.88	1.82	2.6931 (12)	175
O1—H28···O9^iv	0.85	1.84	2.6616 (11)	161
C5—H5A···O2^v	0.93	2.20	3.098 (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.

Experimental details

Crystal data
Chemical formula	2C₉H₇N₂O₄⁺·SO₄²⁻·H₂O
M_r	528.41
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	296
a, b, c (Å)	14.691 (3), 7.7968 (17), 17.983 (4)
V (Å³)	2059.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.12 × 0.11 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.971, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	11525, 2413, 1994
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.656

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.138, 1.00
No. of reflections	2413
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.40

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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
O1W—H1WA···O3ⁱ	0.96 (6)	2.26 (5)	2.9012 (11)	123.6
O1W—H1WA···O11ⁱ	0.96 (6)	2.47 (6)	3.1575 (16)	128.4
O4—H21···O11	0.85	1.79	2.6330 (11)	169.4
N2—H22···O1Wⁱⁱ	0.90	1.96	2.8365 (10)	163.4
N1—H25···O11ⁱⁱⁱ	0.88	1.82	2.6931 (12)	174.7
O1—H28···O9^iv	0.85	1.84	2.6616 (11)	160.6
C5—H5A···O2^v	0.93	2.20	3.098 (3)	162.4

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.

Acknowledgements

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.

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gao, Q., Gao, W.-H., Zhang, C.-Y. & Xie, Y.-B. (2008). Acta Cryst. E64, m928. Web of Science CrossRef IUCr Journals Google Scholar
Sakai, T., Hamada, T., Awata, N. & Watanabe, J. (1989). J. Pharmacobio-Dynam. 12, 530–536. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
White, E. H. & Matsuo, K. (1967). J. Org. Chem. 32, 1921–1926. CrossRef CAS Web of Science Google Scholar