1H-Benzo[d]imidazol-3-ium (Z)-3-carboxyprop-2-enoate

Amudha, M.; Gunasekaran, B.; Kumar, P.P.; Chakkaravarthi, G.

doi:10.1107/S2414314616010257

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161025

https://doi.org/10.1107/S2414314616010257

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access

1H-Benzo[d]imidazol-3-ium (Z)-3-carboxyprop-2-enoate

M. Amudha,^a B. Gunasekaran,^b P. Praveen Kumar ^a ^* and G. Chakkaravarthi ^c ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, ^bDepartment of Physics & Nano Technology, SRM University, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203 Tamil Nadu, India, and ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: ppkpresidency@gmail.com, chakkaravarthi_2005@yahoo.com

Edited by J. Simpson, University of Otago, New Zealand (Received 22 June 2016; accepted 24 June 2016; online 12 July 2016)

In the anion of the title molecular salt, C₇H₇N₂⁺.C₄H₃O₄⁻, an O—H⋯O hydrogen bond generates an S(7) graph-set motif while a pair of intermolecular N—H⋯O and C—H⋯O hydrogen bonds generate an R₄⁴(10) ring-motif. Adjacent anions and cations are further connected through N—H⋯O hydrogen bonds into infinite chains along [101] and these chains are linked by C—H⋯O hydrogen bonds, forming a three-dimensional network.

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1488139

Structure description

Benzimidazole derivatives exhibit various biological effects including antidiabetic (Subudhi et al., 2007 ) and antimicrobial (El-masry et al., 2000 ) activity. Herewith we report the synthesis and crystal structure of the title compound whose geometric parameters are comparable to those found in similar structures (Amudha et al., 2015 ; Krishnamurthy et al., 2015 ).

The asymmetric unit, Fig. 1, contains a 1H-benzo[d]imidazol-3-ium cation, protonated at the benzoimidazole N2 atom, and a (Z)-carboxyprop-2-enoate anion with the OH group of one carboxylic acid deprotonated. The benzoimidazole ring system is almost planar [r.m.s. deviation = 0.016 (2) Å from the best-fit mean plane]. In the anion, an O4—H4A⋯O2 hydrogen bond (Table 1), generates an S(7) graph-set motif, Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O2	0.86 (2)	1.54 (2)	2.395 (2)	173 (2)
N1—H1⋯O3ⁱ	0.87 (1)	1.85 (1)	2.716 (2)	170 (2)
N1—H1⋯O4ⁱ	0.87 (1)	2.59 (2)	3.2215 (19)	130 (2)
N2—H2A⋯O1ⁱⁱ	0.87 (1)	1.89 (1)	2.761 (2)	173 (2)
N2—H2A⋯O2ⁱⁱ	0.87 (1)	2.58 (2)	3.2157 (19)	130 (2)
C7—H7⋯O1ⁱⁱⁱ	0.93	2.29	3.193 (2)	164
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) -x+2, -y+1, -z+1.

Figure 1
The structure of the title salt, showing the atom labelling and 30% probability displacement ellipsoids.

Figure 2
A partial view of the crystal packing of the title compound, showing the ring-set motifs.

In the crystal, a pair of N2—H2A⋯O1 and C7—H7⋯O1 hydrogen bonds generate an R₄⁴(10) ring motif. Atom N2 acts as a bifurcated N—H⋯(O,O) donor, forming a very long N2—H2A⋯O2 hydrogen bond enclosing an R₁²(4) ring, Fig. 2 and Table 1. In the crystal, adjacent anions and cations are connected through N—H⋯O hydrogen bonds (Table 1) into infinite chains along [101]. These chains are further linked by C—H⋯O hydrogen bonds, forming a three-dimensional network, Fig. 3.

Figure 3
The crystal packing of the title molecular salt viewed along the b axis. The hydrogen bonds are shown as dashed lines (see Table 1

). With the exception of H7, C-bound H atoms have been omitted for clarity.

Synthesis and crystallization

Benzimidazole (6 g m) and maleic acid (5.88 g m) were taken in an equimolar ratio (1:1) and dissolved in water at room temperature. The resulting solution was stirred well for about six h using a magnetic stirrer and then the solution was filtered and allowed to evaporate at room temperature. Slow evaporation of the solvent yielded crystals suitable for X-ray diffraction analysis over 15 days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·C₄H₃O₄⁻
M_r	234.21
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	12.8062 (18), 5.4759 (8), 15.840 (2)
β (°)	92.709 (4)
V (Å³)	1109.5 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.968, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	14385, 2814, 1758
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.118, 1.01
No. of reflections	2814
No. of parameters	165
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1488139

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616010257/sj4052sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010257/sj4052Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010257/sj4052Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

1H-Benzo[d]imidazol-3-ium (Z)-3-carboxyprop-2-enoate top

Crystal data top

C₇H₇N₂⁺·C₄H₃O₄⁻	F(000) = 488
M_r = 234.21	D_x = 1.402 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2814 reflections
a = 12.8062 (18) Å	θ = 2.6–28.4°
b = 5.4759 (8) Å	µ = 0.11 mm⁻¹
c = 15.840 (2) Å	T = 295 K
β = 92.709 (4)°	Block, colourless
V = 1109.5 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2814 independent reflections
Radiation source: fine-focus sealed tube	1758 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and φ scans	θ_max = 28.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −17→17
T_min = 0.968, T_max = 0.979	k = −7→7
14385 measured reflections	l = −21→21

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0452P)² + 0.3092P] where P = (F_o² + 2F_c²)/3
2814 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.18 e Å⁻³
3 restraints	Δρ_min = −0.16 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.80286 (14)	0.4571 (3)	0.63117 (10)	0.0408 (4)
C2	0.74325 (18)	0.2787 (4)	0.66778 (12)	0.0577 (5)
H2	0.7736	0.1541	0.7005	0.069*
C3	0.63754 (19)	0.2955 (4)	0.65332 (14)	0.0698 (6)
H3	0.5946	0.1791	0.6767	0.084*
C4	0.59243 (16)	0.4824 (4)	0.60453 (15)	0.0678 (6)
H4	0.5201	0.4862	0.5956	0.081*
C5	0.65108 (14)	0.6604 (4)	0.56929 (12)	0.0539 (5)
H5	0.6205	0.7862	0.5374	0.065*
C6	0.75809 (12)	0.6443 (3)	0.58345 (10)	0.0386 (4)
C7	0.92803 (14)	0.6872 (4)	0.58628 (11)	0.0495 (5)
H7	0.9943	0.7480	0.5768	0.059*
C8	0.75802 (13)	0.2061 (3)	0.41264 (10)	0.0407 (4)
C9	0.73360 (13)	0.4304 (3)	0.36290 (10)	0.0404 (4)
H9	0.7734	0.5666	0.3785	0.048*
C10	0.66372 (13)	0.4662 (3)	0.29959 (11)	0.0418 (4)
H10	0.6611	0.6247	0.2785	0.050*
C11	0.58908 (13)	0.2933 (3)	0.25709 (11)	0.0427 (4)
N1	0.90930 (12)	0.4909 (3)	0.63094 (9)	0.0487 (4)
N2	0.83986 (11)	0.7854 (3)	0.55688 (9)	0.0446 (4)
O1	0.83660 (9)	0.2067 (2)	0.46103 (8)	0.0498 (3)
O2	0.69760 (11)	0.0217 (2)	0.40536 (9)	0.0652 (4)
O3	0.54288 (11)	0.3592 (3)	0.19178 (9)	0.0649 (4)
O4	0.57443 (10)	0.0823 (2)	0.28870 (9)	0.0587 (4)
H1	0.9574 (13)	0.392 (3)	0.6511 (14)	0.081 (7)*
H2A	0.8352 (15)	0.913 (3)	0.5238 (11)	0.063 (6)*
H4A	0.6146 (17)	0.056 (5)	0.3328 (11)	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0504 (10)	0.0373 (9)	0.0346 (9)	−0.0001 (8)	0.0026 (7)	−0.0051 (7)
C2	0.0855 (15)	0.0431 (11)	0.0456 (10)	−0.0063 (10)	0.0129 (10)	0.0011 (8)
C3	0.0801 (16)	0.0646 (14)	0.0670 (14)	−0.0266 (12)	0.0281 (12)	−0.0085 (11)
C4	0.0453 (11)	0.0846 (17)	0.0745 (15)	−0.0131 (12)	0.0149 (10)	−0.0164 (13)
C5	0.0436 (10)	0.0602 (13)	0.0578 (11)	0.0035 (9)	0.0019 (8)	−0.0036 (10)
C6	0.0414 (9)	0.0356 (9)	0.0388 (9)	−0.0016 (7)	0.0017 (7)	−0.0042 (7)
C7	0.0417 (10)	0.0541 (12)	0.0519 (11)	−0.0044 (8)	−0.0062 (8)	−0.0003 (9)
C8	0.0468 (10)	0.0352 (9)	0.0399 (9)	−0.0012 (8)	0.0016 (7)	−0.0030 (7)
C9	0.0476 (10)	0.0280 (8)	0.0454 (9)	−0.0105 (7)	0.0011 (8)	−0.0021 (7)
C10	0.0491 (10)	0.0271 (8)	0.0491 (10)	−0.0059 (7)	0.0011 (8)	0.0024 (7)
C11	0.0416 (9)	0.0373 (9)	0.0488 (10)	−0.0016 (7)	−0.0016 (8)	−0.0027 (8)
N1	0.0494 (10)	0.0488 (9)	0.0466 (9)	0.0067 (8)	−0.0104 (7)	0.0028 (7)
N2	0.0439 (8)	0.0397 (8)	0.0495 (9)	−0.0034 (7)	−0.0041 (7)	0.0066 (7)
O1	0.0499 (7)	0.0509 (8)	0.0478 (7)	0.0009 (6)	−0.0066 (6)	0.0001 (6)
O2	0.0779 (10)	0.0358 (7)	0.0795 (10)	−0.0180 (7)	−0.0221 (8)	0.0195 (7)
O3	0.0719 (9)	0.0587 (9)	0.0617 (9)	−0.0106 (7)	−0.0233 (7)	0.0066 (7)
O4	0.0590 (9)	0.0393 (7)	0.0759 (10)	−0.0154 (6)	−0.0191 (7)	0.0058 (7)

Geometric parameters (Å, º) top

C1—N1	1.376 (2)	C7—H7	0.9300
C1—C6	1.382 (2)	C8—O1	1.2359 (19)
C1—C2	1.384 (3)	C8—O2	1.274 (2)
C2—C3	1.365 (3)	C8—C9	1.485 (2)
C2—H2	0.9300	C9—C10	1.327 (2)
C3—C4	1.392 (3)	C9—H9	0.9300
C3—H3	0.9300	C10—C11	1.484 (2)
C4—C5	1.366 (3)	C10—H10	0.9300
C4—H4	0.9300	C11—O3	1.222 (2)
C5—C6	1.381 (2)	C11—O4	1.277 (2)
C5—H5	0.9300	N1—H1	0.871 (9)
C6—N2	1.383 (2)	N2—H2A	0.873 (9)
C7—N1	1.315 (2)	O4—H4A	0.860 (10)
C7—N2	1.316 (2)

N1—C1—C6	106.51 (15)	N2—C7—H7	124.8
N1—C1—C2	131.48 (17)	O1—C8—O2	122.11 (16)
C6—C1—C2	122.01 (17)	O1—C8—C9	118.15 (15)
C3—C2—C1	116.38 (19)	O2—C8—C9	119.73 (15)
C3—C2—H2	121.8	C10—C9—C8	129.87 (15)
C1—C2—H2	121.8	C10—C9—H9	115.1
C2—C3—C4	121.7 (2)	C8—C9—H9	115.1
C2—C3—H3	119.2	C9—C10—C11	130.20 (15)
C4—C3—H3	119.2	C9—C10—H10	114.9
C5—C4—C3	122.0 (2)	C11—C10—H10	114.9
C5—C4—H4	119.0	O3—C11—O4	121.68 (16)
C3—C4—H4	119.0	O3—C11—C10	118.12 (16)
C4—C5—C6	116.65 (19)	O4—C11—C10	120.19 (15)
C4—C5—H5	121.7	C7—N1—C1	108.51 (14)
C6—C5—H5	121.7	C7—N1—H1	124.3 (15)
C5—C6—C1	121.27 (17)	C1—N1—H1	126.8 (15)
C5—C6—N2	132.43 (17)	C7—N2—C6	108.26 (15)
C1—C6—N2	106.29 (14)	C7—N2—H2A	124.9 (13)
N1—C7—N2	110.43 (16)	C6—N2—H2A	126.7 (13)
N1—C7—H7	124.8	C11—O4—H4A	112.0 (17)

N1—C1—C2—C3	−178.05 (18)	O1—C8—C9—C10	169.98 (18)
C6—C1—C2—C3	0.8 (3)	O2—C8—C9—C10	−11.0 (3)
C1—C2—C3—C4	−0.1 (3)	C8—C9—C10—C11	−1.3 (3)
C2—C3—C4—C5	−0.7 (3)	C9—C10—C11—O3	−169.26 (18)
C3—C4—C5—C6	0.9 (3)	C9—C10—C11—O4	10.8 (3)
C4—C5—C6—C1	−0.2 (3)	N2—C7—N1—C1	0.0 (2)
C4—C5—C6—N2	178.47 (18)	C6—C1—N1—C7	0.34 (19)
N1—C1—C6—C5	178.42 (16)	C2—C1—N1—C7	179.36 (18)
C2—C1—C6—C5	−0.7 (3)	N1—C7—N2—C6	−0.3 (2)
N1—C1—C6—N2	−0.53 (18)	C5—C6—N2—C7	−178.24 (19)
C2—C1—C6—N2	−179.66 (16)	C1—C6—N2—C7	0.54 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O2	0.86 (2)	1.54 (2)	2.395 (2)	173 (2)
N1—H1···O3ⁱ	0.87 (1)	1.85 (1)	2.716 (2)	170 (2)
N1—H1···O4ⁱ	0.87 (1)	2.59 (2)	3.2215 (19)	130 (2)
N2—H2A···O1ⁱⁱ	0.87 (1)	1.89 (1)	2.761 (2)	173 (2)
N2—H2A···O2ⁱⁱ	0.87 (1)	2.58 (2)	3.2157 (19)	130 (2)
C7—H7···O1ⁱⁱⁱ	0.93	2.29	3.193 (2)	164

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

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras, for the data collection.

References

Amudha, M., Kumar, P. P. & Chakkaravarthi, G. (2015). Acta Cryst. E71, o794–o795. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
El-masry, A. H., Fahmy, H. H. & Ali Abdelwahed, S. H. (2000). Molecules, 5, 1429–1438. CAS Google Scholar
Krishnamurthy, M. S. & Begum, N. S. (2015). Acta Cryst. E71, o387–o388. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Subudhi, B. B., Panda, P. K., Kundu, T., Sahoo, S. & Pradhan, D. (2007). J. Pharm. Res. 6, 114–118. CAS Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1H-Benzo[d]imidazol-3-ium (Z)-3-carboxyprop-2-enoate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds