2-Thio­ureido-1H-benzimidazol-3-ium chloride monohydrate

Sundaresan, C.N.; Singh, D.K.; Nanubolu, J.B.

doi:10.1107/S1600536814006837

organic compounds

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Volume 70| Part 5| May 2014| Page o553

doi:10.1107/S1600536814006837

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2-Thioureido-1H-benzimidazol-3-ium chloride monohydrate

C. N. Sundaresan,^a ^* Dheeraj Kumar Singh ^a and Jagadeesh Babu Nanubolu ^b

^aDepartment of Chemistry, Sri Sathya Sai Institute of Higher Learning, Brindavan Campus, Kadugodi, Bangalore 560 067, India, and ^bX-ray Crystallography Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
^*Correspondence e-mail: cnsundaresan@sssihl.edu.in

(Received 20 March 2014; accepted 27 March 2014; online 16 April 2014)

In the title compound, C₈H₉N₄S⁺·Cl⁻·H₂O, the cation is approximately planar, with a dihedral angle of 7.71 (8)° between the mean planes of the benzoimidazole ring system and the thiourea unit. In the crystal, cations, anions and water molecules of crystallization are linked by O—H⋯Cl, N—H⋯O, N—H⋯Cl and N—H⋯S hydrogen bonds into a three-dimensional network. π–π stacking is observed between the benzene and imidazole rings of neighbouring molecules, the centroid–centroid distance being 3.5774 (11) Å.

CCDC reference: 994075

Related literature

For the synthesis and biological activity of benzimidazoles, see: Siva & Subhash (2011 ); Sharghi et al. (2008 ); Refaat (2010 ); Puratchikody et al. (2008 ); Achar et al. (2010 ); Starcevic et al. (2007 ). For hydrogen-bond classification, see: Jeffrey et al. (1985 ).

Experimental

Crystal data

C₈H₉N₄S⁺·Cl⁺·H₂O
M_r = 246.72
Monoclinic, P 2₁ /c
a = 9.3027 (6) Å
b = 8.7038 (5) Å
c = 14.5503 (8) Å
β = 109.143 (3)°
V = 1112.97 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.33 × 0.19 × 0.14 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.850, T_max = 0.932
10318 measured reflections
1958 independent reflections
1818 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.083
S = 1.07
1958 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯Cl1ⁱ	0.81	2.29	3.0991 (15)	179
O1—H2O⋯Cl1	0.87	2.30	3.1443 (14)	165
N1—H1N⋯O1	0.86	2.32	3.064 (2)	145
N1—H2N⋯O1ⁱⁱ	0.86	2.14	3.000 (2)	174
N2—H2⋯O1	0.86	2.03	2.8667 (19)	165
N3—H3N⋯S1	0.80	2.43	3.0146 (14)	131
N4—H4N⋯Cl1	0.83	2.28	3.1055 (15)	175
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 994075

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814006837/xu5781sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814006837/xu5781Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814006837/xu5781Isup3.cml

checkCIF report

Comment top

In recent years, Benzimidazole moiety has gained increased interest in drug industry worldwide, as an important pharmocophore exhibiting a wide spectrum of biological and pharmaceutical activities. They act as anti-HIV agents, anti cancer agents (Refaat, 2010), anti-tumor agents (Starcevic et al., 2007), anti-microbial agents (Puratchikody et al., 2008) analgesic and anti-inflammatory agents (Achar et al., 2010).

The title compound (Fig. 1), C₈H₁₁ClN₄OS, crystallized in monoclinic P2₁/c space group with Z=4 (Fig. 2). Two chloride anions and two water molecules are acting as a bridge to connect four molecules of the title compound which resulted in infinite layered type supramolecular architecture. The title compound is mainly stabilized by N—H···O, N—H···Cl, O—H···Cl intermolecular hydrogen bonding which resulted in generating of ring motifs R²₂ (8) and R¹₂ (6). The intramolecular ring motif S¹₁ (6) is also generated due to intramolecular N—H···S hydrogen bonding.

Related literature top

For the synthesis and biological activity of benzimidazoles, see: Siva & Subhash (2011); Sharghi et al. (2008); Refaat (2010); Puratchikody et al. (2008); Achar et al. (2010); Starcevic et al. (2007). For hydrogen-bond classification, see: Jeffrey et al. (1985).

Experimental top

A mixture of 5-amino-3H-1, 2, 4-dithiazole-3-thione (1.5 g, 0.01 mol) and o-phenylenediamine (1.08 g, 0.01 mol) in absolute ethanol (25 ml) was refluxed for 24 h. The solvent was removed under reduced pressure and the residue was treated with aqueous sodium hydroxide (1 N, 3 × 20 ml) and then filtered after an hour. The filtrate was adjusted to pH 5 by addition of aqueous hydrochloric acid (1 N) and left in a refrigerator overnight. The precipitate (1.8 g, 74%) was collected, washed with water and dried. The title compound was recrystallized from formic acid-propanol mixture to yield small crystals. The melting point was recorded as 248–251°C.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP diagram of 1-(1H-benzo[d]imidazol-2-yl)thiourea salt hydrate (Thermal ellipsoids are drawn at 30% probability level).
	Fig. 2. Crystal packing diagram of the title compound (I).
	Fig. 3. Synthetic scheme of the title compound (I).

2-Thioureido-1H-benzimidazol-3-ium chloride monohydrate top

Crystal data top

C₈H₉N₄S⁺·Cl⁺·H₂O	F(000) = 512
M_r = 246.72	D_x = 1.472 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 5220 reflections
a = 9.3027 (6) Å	θ = 2.3–27.9°
b = 8.7038 (5) Å	µ = 0.51 mm⁻¹
c = 14.5503 (8) Å	T = 293 K
β = 109.143 (3)°	Block, yellow
V = 1112.97 (11) Å³	0.33 × 0.19 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1958 independent reflections
Radiation source: fine-focus sealed tube	1818 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.850, T_max = 0.932	k = −10→10
10318 measured reflections	l = −17→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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.041P)² + 0.391P] where P = (F_o² + 2F_c²)/3
1958 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₈H₉N₄S⁺·Cl⁺·H₂O	V = 1112.97 (11) Å³
M_r = 246.72	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3027 (6) Å	µ = 0.51 mm⁻¹
b = 8.7038 (5) Å	T = 293 K
c = 14.5503 (8) Å	0.33 × 0.19 × 0.14 mm
β = 109.143 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1958 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1818 reflections with I > 2σ(I)
T_min = 0.850, T_max = 0.932	R_int = 0.021
10318 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.07	Δρ_max = 0.25 e Å⁻³
1958 reflections	Δρ_min = −0.20 e Å⁻³
136 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
S1	0.37873 (6)	−0.13735 (5)	0.83964 (4)	0.05278 (17)
N1	0.45104 (18)	0.12730 (17)	0.77931 (11)	0.0483 (4)
H1N	0.4545	0.2261	0.7785	0.058*
H2N	0.4887	0.0771	0.7417	0.058*
N2	0.33167 (17)	0.15159 (16)	0.89088 (10)	0.0415 (3)
H2	0.3490	0.2470	0.8830	0.050*
N3	0.25238 (15)	−0.02567 (16)	0.99381 (10)	0.0372 (3)
H3N	0.2705	−0.1020	0.9695	0.045*
N4	0.22253 (15)	0.22080 (16)	1.00973 (10)	0.0394 (3)
H4N	0.2267	0.3140	0.9987	0.047*
C1	0.38850 (19)	0.0537 (2)	0.83586 (12)	0.0383 (4)
C2	0.27105 (19)	0.11420 (19)	0.96112 (12)	0.0366 (4)
C3	0.19110 (17)	−0.00866 (19)	1.06892 (11)	0.0348 (4)
C4	0.1550 (2)	−0.1157 (2)	1.12841 (13)	0.0421 (4)
H4	0.1668	−0.2207	1.1213	0.051*
C5	0.1006 (2)	−0.0573 (2)	1.19897 (14)	0.0475 (4)
H5	0.0780	−0.1248	1.2418	0.057*
C6	0.0785 (2)	0.1001 (2)	1.20790 (14)	0.0487 (4)
H6	0.0397	0.1343	1.2556	0.058*
C7	0.11296 (19)	0.2059 (2)	1.14772 (13)	0.0445 (4)
H7	0.0972	0.3106	1.1531	0.053*
C8	0.17212 (18)	0.14874 (18)	1.07901 (12)	0.0360 (4)
O1	0.44295 (16)	0.44905 (15)	0.86287 (10)	0.0522 (3)
H1O	0.5262	0.4440	0.9042	0.078*
H2O	0.3841	0.4980	0.8881	0.078*
Cl1	0.23786 (6)	0.57314 (5)	0.98063 (4)	0.05321 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0756 (4)	0.0303 (3)	0.0653 (3)	−0.0048 (2)	0.0406 (3)	−0.0053 (2)
N1	0.0621 (10)	0.0372 (8)	0.0539 (9)	−0.0004 (7)	0.0303 (8)	0.0037 (7)
N2	0.0569 (9)	0.0264 (7)	0.0446 (8)	−0.0004 (6)	0.0210 (7)	0.0028 (6)
N3	0.0462 (8)	0.0258 (7)	0.0404 (7)	0.0011 (6)	0.0152 (6)	−0.0025 (6)
N4	0.0479 (8)	0.0243 (7)	0.0456 (8)	0.0015 (6)	0.0150 (6)	0.0010 (6)
C1	0.0400 (9)	0.0361 (9)	0.0372 (8)	−0.0004 (7)	0.0104 (7)	0.0009 (7)
C2	0.0411 (9)	0.0288 (8)	0.0372 (8)	0.0000 (7)	0.0092 (7)	0.0006 (7)
C3	0.0347 (8)	0.0307 (8)	0.0371 (8)	0.0004 (6)	0.0094 (7)	−0.0016 (7)
C4	0.0455 (9)	0.0320 (9)	0.0489 (10)	0.0001 (7)	0.0156 (8)	0.0012 (7)
C5	0.0490 (10)	0.0459 (10)	0.0513 (11)	−0.0029 (8)	0.0214 (9)	0.0050 (8)
C6	0.0484 (10)	0.0511 (11)	0.0529 (11)	0.0017 (8)	0.0248 (9)	−0.0047 (9)
C7	0.0445 (10)	0.0356 (9)	0.0531 (10)	0.0049 (7)	0.0156 (8)	−0.0057 (8)
C8	0.0358 (8)	0.0313 (9)	0.0389 (9)	0.0001 (6)	0.0096 (7)	0.0001 (7)
O1	0.0616 (8)	0.0418 (7)	0.0558 (8)	0.0010 (6)	0.0227 (6)	−0.0045 (6)
Cl1	0.0654 (3)	0.0333 (3)	0.0646 (3)	0.0053 (2)	0.0264 (2)	0.0047 (2)

Geometric parameters (Å, º) top

S1—C1	1.6673 (18)	C3—C4	1.386 (2)
N1—C1	1.319 (2)	C3—C8	1.395 (2)
N1—H1N	0.8607	C4—C5	1.382 (3)
N1—H2N	0.8592	C4—H4	0.9300
N2—C2	1.359 (2)	C5—C6	1.397 (3)
N2—C1	1.387 (2)	C5—H5	0.9300
N2—H2	0.8606	C6—C7	1.379 (3)
N3—C2	1.339 (2)	C6—H6	0.9300
N3—C3	1.396 (2)	C7—C8	1.382 (2)
N3—H3N	0.7964	C7—H7	0.9300
N4—C2	1.332 (2)	O1—H1O	0.8112
N4—C8	1.393 (2)	O1—H2O	0.8651
N4—H4N	0.8304

C1—N1—H1N	121.3	C4—C3—N3	131.46 (15)
C1—N1—H2N	120.4	C8—C3—N3	106.54 (14)
H1N—N1—H2N	118.4	C5—C4—C3	116.06 (16)
C2—N2—C1	128.15 (14)	C5—C4—H4	122.0
C2—N2—H2	118.3	C3—C4—H4	122.0
C1—N2—H2	113.1	C4—C5—C6	122.05 (18)
C2—N3—C3	108.39 (14)	C4—C5—H5	119.0
C2—N3—H3N	122.0	C6—C5—H5	119.0
C3—N3—H3N	129.5	C7—C6—C5	121.59 (17)
C2—N4—C8	108.90 (13)	C7—C6—H6	119.2
C2—N4—H4N	122.2	C5—C6—H6	119.2
C8—N4—H4N	128.9	C6—C7—C8	116.69 (17)
N1—C1—N2	113.04 (15)	C6—C7—H7	121.7
N1—C1—S1	123.02 (14)	C8—C7—H7	121.7
N2—C1—S1	123.94 (13)	C7—C8—N4	132.05 (15)
N4—C2—N3	109.79 (15)	C7—C8—C3	121.58 (16)
N4—C2—N2	121.94 (15)	N4—C8—C3	106.37 (14)
N3—C2—N2	128.26 (15)	H1O—O1—H2O	107.1
C4—C3—C8	121.98 (16)

C2—N2—C1—N1	−174.63 (16)	C3—C4—C5—C6	2.0 (3)
C2—N2—C1—S1	5.7 (3)	C4—C5—C6—C7	−1.3 (3)
C8—N4—C2—N3	1.18 (19)	C5—C6—C7—C8	−0.8 (3)
C8—N4—C2—N2	−177.76 (15)	C6—C7—C8—N4	−177.98 (17)
C3—N3—C2—N4	−1.16 (18)	C6—C7—C8—C3	2.1 (2)
C3—N3—C2—N2	177.68 (16)	C2—N4—C8—C7	179.38 (17)
C1—N2—C2—N4	178.93 (15)	C2—N4—C8—C3	−0.71 (18)
C1—N2—C2—N3	0.2 (3)	C4—C3—C8—C7	−1.5 (3)
C2—N3—C3—C4	−177.73 (17)	N3—C3—C8—C7	179.93 (15)
C2—N3—C3—C8	0.69 (18)	C4—C3—C8—N4	178.62 (15)
C8—C3—C4—C5	−0.6 (2)	N3—C3—C8—N4	0.01 (17)
N3—C3—C4—C5	177.59 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Cl1ⁱ	0.81	2.29	3.0991 (15)	179
O1—H2O···Cl1	0.87	2.30	3.1443 (14)	165
N1—H1N···O1	0.86	2.32	3.064 (2)	145
N1—H2N···O1ⁱⁱ	0.86	2.14	3.000 (2)	174
N2—H2···O1	0.86	2.03	2.8667 (19)	165
N3—H3N···S1	0.80	2.43	3.0146 (14)	131
N4—H4N···Cl1	0.83	2.28	3.1055 (15)	175

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···Cl1ⁱ	0.81	2.29	3.0991 (15)	179.1
O1—H2O···Cl1	0.87	2.30	3.1443 (14)	165.2
N1—H1N···O1	0.86	2.32	3.064 (2)	145.2
N1—H2N···O1ⁱⁱ	0.86	2.14	3.000 (2)	173.6
N2—H2···O1	0.86	2.03	2.8667 (19)	164.7
N3—H3N···S1	0.80	2.43	3.0146 (14)	130.7
N4—H4N···Cl1	0.83	2.28	3.1055 (15)	175.4

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

Acknowledgements

We thank the Director, IICT, Hyderabad, India, for the XRD data and Dr Anand Solomon for his guidance.

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