Ethyl 1-[3-(1H-imidazol-1-yl)prop-yl]-2-(4-chloro-phen-yl)-1H-benzo[d]imidazole-5-carboxyl-ate dihydrate.

In the title compound, C(22)H(21)ClN(4)O(2)·2H(2)O, the almost-planar benzimidazole ring system [maximum deviation 0.014 (1) Å] is inclined at angles of 36.32 (5) and 74.75 (7)° with respect to the phenyl and imidazole rings, respectively. In the crystal structure, the water mol-ecules are linked to the organic mol-ecules to form a three-dimensional network via O-H⋯N and O-H⋯O hydrogen bonds. The packing is further consolidated by a pair of bifurcated C-H⋯O bonds, generating R(1) (2)(6) loops. C-H⋯π inter-actions are also observed.

Related literature

For related structures and background to benzimidazoles, see: Eltayeb et al. (2009 ▶, 2011 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C22H21ClN4O2·2H2O

M = 444.91

Monoclinic,

a = 9.0611 (1) Å

b = 13.8393 (2) Å

c = 18.0470 (3) Å

β = 92.386 (1)°

V = 2261.12 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 100 K

0.40 × 0.30 × 0.27 mm

Data collection

Bruker SMART APEX II CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.922, T max = 0.947

31604 measured reflections

8235 independent reflections

6221 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.136

S = 1.05

8235 reflections

296 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.40 e Å−3

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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811033654/hb6369sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033654/hb6369Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811033654/hb6369Isup3.cml

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

C22H21ClN4O2·2H2O	F(000) = 936
Mr = 444.91	Dx = 1.307 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9994 reflections
a = 9.0611 (1) Å	θ = 2.3–32.3°
b = 13.8393 (2) Å	µ = 0.20 mm−1
c = 18.0470 (3) Å	T = 100 K
β = 92.386 (1)°	Block, bronze
V = 2261.12 (6) Å3	0.40 × 0.30 × 0.27 mm
Z = 4

Bruker SMART APEX II CCD diffractometer	8235 independent reflections
Radiation source: fine-focus sealed tube	6221 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 32.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→12
Tmin = 0.922, Tmax = 0.947	k = −15→20
31604 measured reflections	l = −27→27

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) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.067P)2 + 0.584P] where P = (Fo2 + 2Fc2)/3
8235 reflections	(Δ/σ)max = 0.001
296 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
Cl1	0.00707 (4)	1.20793 (2)	1.108564 (19)	0.03204 (9)
O1	0.79039 (11)	0.47315 (7)	0.97069 (5)	0.0284 (2)
O2	0.71434 (12)	0.49126 (7)	1.08701 (6)	0.0345 (2)
N1	0.39801 (11)	0.80622 (7)	1.05570 (5)	0.02072 (19)
N2	0.39541 (11)	0.84567 (7)	0.93472 (5)	0.01967 (19)
N3	0.31059 (13)	1.05497 (9)	0.76026 (6)	0.0275 (2)
N4	0.07811 (15)	1.10407 (11)	0.74881 (7)	0.0405 (3)
C1	0.47996 (13)	0.73886 (9)	1.01809 (6)	0.0201 (2)
C2	0.55633 (14)	0.65815 (9)	1.04496 (6)	0.0223 (2)
H2A	0.5563	0.6408	1.0959	0.027*
C3	0.63268 (14)	0.60382 (9)	0.99427 (7)	0.0228 (2)
C4	0.63171 (14)	0.62896 (9)	0.91822 (7)	0.0246 (2)
H4A	0.6859	0.5905	0.8852	0.030*
C5	0.55404 (14)	0.70792 (9)	0.89077 (6)	0.0237 (2)
H5A	0.5516	0.7241	0.8396	0.028*
C6	0.47921 (13)	0.76287 (9)	0.94225 (6)	0.0201 (2)
C7	0.34981 (13)	0.86860 (9)	1.00442 (6)	0.0194 (2)
C8	0.25981 (13)	0.95260 (8)	1.02341 (6)	0.0192 (2)
C9	0.27664 (13)	1.04393 (9)	0.99159 (6)	0.0214 (2)
H9A	0.3421	1.0521	0.9523	0.026*
C10	0.19832 (14)	1.12307 (9)	1.01704 (7)	0.0228 (2)
H10A	0.2098	1.1850	0.9953	0.027*
C11	0.10321 (14)	1.11010 (9)	1.07454 (7)	0.0235 (2)
C12	0.08425 (14)	1.01997 (9)	1.10666 (7)	0.0253 (2)
H12A	0.0183	1.0121	1.1458	0.030*
C13	0.16240 (14)	0.94177 (9)	1.08108 (6)	0.0229 (2)
H13A	0.1498	0.8800	1.1029	0.027*
C14	0.71494 (14)	0.51778 (9)	1.02296 (7)	0.0255 (2)
C15	0.87442 (16)	0.38867 (10)	0.99498 (8)	0.0303 (3)
H15A	0.8083	0.3398	1.0160	0.036*
H15B	0.9503	0.4068	1.0335	0.036*
C16	0.94627 (18)	0.34885 (11)	0.92785 (9)	0.0379 (3)
H16A	1.0040	0.2914	0.9419	0.057*
H16B	1.0116	0.3979	0.9077	0.057*
H16C	0.8700	0.3314	0.8901	0.057*
C17	0.35549 (14)	0.89102 (9)	0.86335 (6)	0.0219 (2)
H17A	0.2697	0.9342	0.8694	0.026*
H17B	0.3256	0.8402	0.8271	0.026*
C18	0.48274 (14)	0.94958 (10)	0.83277 (6)	0.0260 (2)
H18A	0.5095	1.0027	0.8675	0.031*
H18B	0.5703	0.9074	0.8286	0.031*
C19	0.43969 (16)	0.99175 (11)	0.75674 (7)	0.0293 (3)
H19A	0.5238	1.0290	0.7382	0.035*
H19B	0.4175	0.9385	0.7214	0.035*
C20	0.17101 (17)	1.03385 (12)	0.73574 (7)	0.0339 (3)
H20A	0.1435	0.9750	0.7118	0.041*
C21	0.16200 (19)	1.17397 (13)	0.78406 (9)	0.0414 (4)
H21A	0.1252	1.2341	0.8007	0.050*
C22	0.30538 (18)	1.14512 (11)	0.79179 (8)	0.0349 (3)
H22A	0.3854	1.1802	0.8144	0.042*
O1W	0.35783 (15)	0.73706 (9)	0.20403 (6)	0.0449 (3)
O2W	0.78478 (15)	0.35533 (11)	0.20142 (7)	0.0478 (3)
H1W1	0.354 (3)	0.7653 (18)	0.1566 (14)	0.067 (7)*
H2W1	0.307 (2)	0.7811 (16)	0.2306 (12)	0.052 (6)*
H1W2	0.870 (2)	0.3758 (15)	0.2149 (12)	0.045 (5)*
H2W2	0.757 (3)	0.3993 (16)	0.1690 (14)	0.057 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.03324 (18)	0.02542 (16)	0.03796 (17)	0.00757 (13)	0.00755 (13)	−0.00212 (12)
O1	0.0276 (5)	0.0222 (4)	0.0355 (5)	0.0066 (4)	0.0011 (4)	0.0004 (4)
O2	0.0391 (6)	0.0306 (5)	0.0336 (5)	0.0089 (4)	0.0012 (4)	0.0078 (4)
N1	0.0233 (5)	0.0215 (5)	0.0175 (4)	0.0019 (4)	0.0022 (3)	0.0011 (3)
N2	0.0222 (5)	0.0213 (4)	0.0156 (4)	0.0017 (4)	0.0010 (3)	0.0011 (3)
N3	0.0310 (6)	0.0312 (6)	0.0202 (4)	−0.0011 (5)	−0.0003 (4)	0.0056 (4)
N4	0.0324 (6)	0.0539 (8)	0.0351 (6)	0.0007 (6)	0.0024 (5)	0.0165 (6)
C1	0.0211 (5)	0.0217 (5)	0.0174 (4)	−0.0001 (4)	0.0020 (4)	0.0005 (4)
C2	0.0239 (6)	0.0225 (5)	0.0204 (5)	0.0009 (4)	0.0013 (4)	0.0020 (4)
C3	0.0232 (6)	0.0201 (5)	0.0250 (5)	0.0017 (4)	0.0003 (4)	0.0001 (4)
C4	0.0264 (6)	0.0249 (6)	0.0227 (5)	0.0037 (5)	0.0025 (4)	−0.0032 (4)
C5	0.0270 (6)	0.0261 (6)	0.0180 (5)	0.0023 (5)	0.0019 (4)	−0.0015 (4)
C6	0.0209 (5)	0.0217 (5)	0.0176 (4)	0.0010 (4)	0.0006 (4)	0.0003 (4)
C7	0.0201 (5)	0.0213 (5)	0.0168 (4)	−0.0007 (4)	0.0017 (4)	0.0002 (4)
C8	0.0199 (5)	0.0205 (5)	0.0173 (4)	0.0003 (4)	0.0000 (4)	−0.0003 (4)
C9	0.0209 (5)	0.0237 (5)	0.0196 (4)	−0.0008 (4)	0.0004 (4)	0.0021 (4)
C10	0.0231 (5)	0.0200 (5)	0.0251 (5)	0.0004 (4)	−0.0009 (4)	0.0026 (4)
C11	0.0217 (5)	0.0232 (5)	0.0255 (5)	0.0028 (4)	0.0000 (4)	−0.0020 (4)
C12	0.0256 (6)	0.0259 (6)	0.0246 (5)	0.0012 (5)	0.0055 (4)	−0.0002 (4)
C13	0.0246 (6)	0.0219 (5)	0.0225 (5)	0.0005 (4)	0.0041 (4)	0.0017 (4)
C14	0.0237 (6)	0.0209 (5)	0.0317 (6)	0.0011 (5)	−0.0005 (4)	0.0008 (4)
C15	0.0276 (6)	0.0217 (6)	0.0413 (7)	0.0049 (5)	−0.0009 (5)	0.0011 (5)
C16	0.0360 (8)	0.0301 (7)	0.0473 (8)	0.0094 (6)	0.0010 (6)	−0.0014 (6)
C17	0.0240 (5)	0.0268 (6)	0.0149 (4)	0.0021 (5)	−0.0005 (4)	0.0023 (4)
C18	0.0244 (6)	0.0324 (6)	0.0212 (5)	0.0008 (5)	0.0021 (4)	0.0051 (5)
C19	0.0338 (7)	0.0342 (7)	0.0203 (5)	0.0022 (5)	0.0054 (5)	0.0052 (5)
C20	0.0344 (7)	0.0438 (8)	0.0232 (5)	−0.0083 (6)	−0.0025 (5)	0.0084 (5)
C21	0.0451 (9)	0.0374 (8)	0.0421 (8)	0.0076 (7)	0.0070 (7)	0.0098 (6)
C22	0.0406 (8)	0.0317 (7)	0.0323 (6)	−0.0015 (6)	0.0010 (6)	0.0033 (5)
O1W	0.0663 (8)	0.0436 (6)	0.0255 (5)	0.0184 (6)	0.0094 (5)	0.0097 (5)
O2W	0.0364 (6)	0.0639 (8)	0.0424 (6)	−0.0085 (6)	−0.0064 (5)	0.0247 (6)

Cl1—C11	1.7358 (13)	C10—C11	1.3880 (17)
O1—C14	1.3387 (16)	C10—H10A	0.9500
O1—C15	1.4529 (16)	C11—C12	1.3892 (18)
O2—C14	1.2131 (16)	C12—C13	1.3831 (17)
N1—C7	1.3261 (15)	C12—H12A	0.9500
N1—C1	1.3868 (15)	C13—H13A	0.9500
N2—C7	1.3773 (14)	C15—C16	1.504 (2)
N2—C6	1.3782 (15)	C15—H15A	0.9900
N2—C17	1.4646 (14)	C15—H15B	0.9900
N3—C20	1.3544 (18)	C16—H16A	0.9800
N3—C22	1.3729 (19)	C16—H16B	0.9800
N3—C19	1.4642 (18)	C16—H16C	0.9800
N4—C20	1.313 (2)	C17—C18	1.5310 (18)
N4—C21	1.370 (2)	C17—H17A	0.9900
C1—C2	1.3906 (17)	C17—H17B	0.9900
C1—C6	1.4081 (15)	C18—C19	1.5268 (17)
C2—C3	1.3906 (17)	C18—H18A	0.9900
C2—H2A	0.9500	C18—H18B	0.9900
C3—C4	1.4154 (17)	C19—H19A	0.9900
C3—C14	1.4864 (17)	C19—H19B	0.9900
C4—C5	1.3805 (17)	C20—H20A	0.9500
C4—H4A	0.9500	C21—C22	1.361 (2)
C5—C6	1.3979 (16)	C21—H21A	0.9500
C5—H5A	0.9500	C22—H22A	0.9500
C7—C8	1.4687 (16)	O1W—H1W1	0.94 (3)
C8—C9	1.3993 (16)	O1W—H2W1	0.91 (2)
C8—C13	1.4004 (16)	O2W—H1W2	0.85 (2)
C9—C10	1.3933 (17)	O2W—H2W2	0.87 (2)
C9—H9A	0.9500
C14—O1—C15	115.80 (10)	C12—C13—H13A	119.6
C7—N1—C1	105.28 (9)	C8—C13—H13A	119.6
C7—N2—C6	106.64 (9)	O2—C14—O1	123.67 (12)
C7—N2—C17	129.20 (10)	O2—C14—C3	123.52 (12)
C6—N2—C17	123.91 (9)	O1—C14—C3	112.80 (11)
C20—N3—C22	106.48 (13)	O1—C15—C16	106.91 (11)
C20—N3—C19	126.43 (13)	O1—C15—H15A	110.3
C22—N3—C19	127.03 (12)	C16—C15—H15A	110.3
C20—N4—C21	104.98 (13)	O1—C15—H15B	110.3
N1—C1—C2	129.64 (10)	C16—C15—H15B	110.3
N1—C1—C6	109.64 (10)	H15A—C15—H15B	108.6
C2—C1—C6	120.72 (10)	C15—C16—H16A	109.5
C1—C2—C3	117.31 (10)	C15—C16—H16B	109.5
C1—C2—H2A	121.3	H16A—C16—H16B	109.5
C3—C2—H2A	121.3	C15—C16—H16C	109.5
C2—C3—C4	121.46 (11)	H16A—C16—H16C	109.5
C2—C3—C14	117.39 (11)	H16B—C16—H16C	109.5
C4—C3—C14	121.16 (11)	N2—C17—C18	112.44 (10)
C5—C4—C3	121.67 (11)	N2—C17—H17A	109.1
C5—C4—H4A	119.2	C18—C17—H17A	109.1
C3—C4—H4A	119.2	N2—C17—H17B	109.1
C4—C5—C6	116.50 (11)	C18—C17—H17B	109.1
C4—C5—H5A	121.7	H17A—C17—H17B	107.8
C6—C5—H5A	121.7	C19—C18—C17	110.99 (10)
N2—C6—C5	131.86 (10)	C19—C18—H18A	109.4
N2—C6—C1	105.81 (10)	C17—C18—H18A	109.4
C5—C6—C1	122.33 (11)	C19—C18—H18B	109.4
N1—C7—N2	112.63 (10)	C17—C18—H18B	109.4
N1—C7—C8	121.49 (10)	H18A—C18—H18B	108.0
N2—C7—C8	125.88 (10)	N3—C19—C18	111.35 (10)
C9—C8—C13	118.98 (11)	N3—C19—H19A	109.4
C9—C8—C7	123.24 (10)	C18—C19—H19A	109.4
C13—C8—C7	117.52 (10)	N3—C19—H19B	109.4
C10—C9—C8	120.61 (11)	C18—C19—H19B	109.4
C10—C9—H9A	119.7	H19A—C19—H19B	108.0
C8—C9—H9A	119.7	N4—C20—N3	112.24 (14)
C11—C10—C9	119.04 (11)	N4—C20—H20A	123.9
C11—C10—H10A	120.5	N3—C20—H20A	123.9
C9—C10—H10A	120.5	C22—C21—N4	110.43 (15)
C10—C11—C12	121.30 (11)	C22—C21—H21A	124.8
C10—C11—Cl1	120.00 (10)	N4—C21—H21A	124.8
C12—C11—Cl1	118.70 (9)	C21—C22—N3	105.87 (14)
C13—C12—C11	119.30 (11)	C21—C22—H22A	127.1
C13—C12—H12A	120.3	N3—C22—H22A	127.1
C11—C12—H12A	120.3	H1W1—O1W—H2W1	101.6 (19)
C12—C13—C8	120.77 (11)	H1W2—O2W—H2W2	101 (2)
C7—N1—C1—C2	179.48 (12)	C7—C8—C9—C10	−173.62 (11)
C7—N1—C1—C6	−0.08 (13)	C8—C9—C10—C11	0.05 (17)
N1—C1—C2—C3	−178.60 (12)	C9—C10—C11—C12	−0.39 (18)
C6—C1—C2—C3	0.91 (18)	C9—C10—C11—Cl1	178.71 (9)
C1—C2—C3—C4	−0.60 (18)	C10—C11—C12—C13	0.39 (19)
C1—C2—C3—C14	179.73 (11)	Cl1—C11—C12—C13	−178.73 (10)
C2—C3—C4—C5	−0.6 (2)	C11—C12—C13—C8	−0.04 (19)
C14—C3—C4—C5	179.08 (12)	C9—C8—C13—C12	−0.30 (18)
C3—C4—C5—C6	1.37 (19)	C7—C8—C13—C12	173.96 (11)
C7—N2—C6—C5	−179.35 (13)	C15—O1—C14—O2	−0.03 (19)
C17—N2—C6—C5	5.9 (2)	C15—O1—C14—C3	179.57 (10)
C7—N2—C6—C1	0.18 (13)	C2—C3—C14—O2	2.6 (2)
C17—N2—C6—C1	−174.58 (11)	C4—C3—C14—O2	−177.04 (13)
C4—C5—C6—N2	178.41 (12)	C2—C3—C14—O1	−176.97 (11)
C4—C5—C6—C1	−1.06 (19)	C4—C3—C14—O1	3.36 (17)
N1—C1—C6—N2	−0.07 (13)	C14—O1—C15—C16	178.52 (12)
C2—C1—C6—N2	−179.67 (11)	C7—N2—C17—C18	108.32 (14)
N1—C1—C6—C5	179.52 (11)	C6—N2—C17—C18	−78.16 (14)
C2—C1—C6—C5	−0.08 (19)	N2—C17—C18—C19	177.29 (10)
C1—N1—C7—N2	0.20 (14)	C20—N3—C19—C18	−105.09 (14)
C1—N1—C7—C8	−178.91 (10)	C22—N3—C19—C18	71.78 (17)
C6—N2—C7—N1	−0.24 (14)	C17—C18—C19—N3	59.23 (15)
C17—N2—C7—N1	174.15 (11)	C21—N4—C20—N3	−0.39 (16)
C6—N2—C7—C8	178.82 (11)	C22—N3—C20—N4	0.51 (15)
C17—N2—C7—C8	−6.79 (19)	C19—N3—C20—N4	177.91 (11)
N1—C7—C8—C9	140.42 (12)	C20—N4—C21—C22	0.12 (17)
N2—C7—C8—C9	−38.57 (18)	N4—C21—C22—N3	0.19 (17)
N1—C7—C8—C13	−33.57 (16)	C20—N3—C22—C21	−0.41 (15)
N2—C7—C8—C13	147.44 (12)	C19—N3—C22—C21	−177.78 (12)
C13—C8—C9—C10	0.29 (17)

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···N1i	0.94 (3)	1.96 (3)	2.8802 (14)	164 (2)
O1W—H2W1···O2Wii	0.91 (2)	1.83 (2)	2.7284 (18)	169 (2)
O2W—H1W2···N4iii	0.849 (19)	1.978 (19)	2.8147 (19)	169 (2)
O2W—H2W2···O2i	0.87 (2)	1.98 (2)	2.8460 (17)	172 (2)
C17—H17B···O1Wiv	0.99	2.49	3.3785 (16)	149
C19—H19B···O1Wiv	0.99	2.51	3.3799 (19)	147
C10—H10A···Cg1v	0.95	2.86	3.4875 (14)	125

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯N1i	0.94 (3)	1.96 (3)	2.8802 (14)	164 (2)
O1W—H2W1⋯O2Wii	0.91 (2)	1.83 (2)	2.7284 (18)	169 (2)
O2W—H1W2⋯N4iii	0.849 (19)	1.978 (19)	2.8147 (19)	169 (2)
O2W—H2W2⋯O2i	0.87 (2)	1.98 (2)	2.8460 (17)	172 (2)
C17—H17B⋯O1Wiv	0.99	2.49	3.3785 (16)	149
C19—H19B⋯O1Wiv	0.99	2.51	3.3799 (19)	147
C10—H10A⋯Cg1v	0.95	2.86	3.4875 (14)	125

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .