(S)-2-(2-Pyrrolidinio)-1H-benzimidazol-3-ium dichloride monohydrate.

In the title compound, C(11)H(15)N(3) (2+)·2Cl(-)·H(2)O, one N atom of the imidazole ring and the N atom of the pyrrolidine ring are protonated. The crystal structure is stabilized by aromatic π-π inter-actions between the benzene rings of neighbouring benzimidazole systems [centroid-centroid duistance = 3.712 (2) Å]. The crystal structure is further stabilized by inter-molecular N-H⋯Cl, O-H⋯Cl and N-H⋯O hydrogen bonds.

Related literature

For proline derivatives, see: Fu et al. (2007 ▶); Aminabhavi et al. (1986 ▶). For related structures, see: Dai & Fu (2008a ▶,b ▶); Fu & Ye (2007 ▶).

Experimental

Crystal data

C11H15N3 2+·2Cl−·H2O

M = 278.18

Triclinic,

a = 7.493 (2) Å

b = 9.739 (2) Å

c = 9.937 (2) Å

α = 99.23 (3)°

β = 95.73 (3)°

γ = 106.27 (3)°

V = 679.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.47 mm−1

T = 293 K

0.35 × 0.30 × 0.15 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.959, T max = 0.982 (expected range = 0.911–0.932)

7119 measured reflections

3108 independent reflections

2310 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.120

S = 1.08

3108 reflections

162 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.24 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019084/lx2100sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019084/lx2100Isup2.hkl

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

C11H15N32+·2Cl−·H2O	Z = 2
Mr = 278.18	F(000) = 292
Triclinic, P1	Dx = 1.361 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.493 (2) Å	Cell parameters from 3108 reflections
b = 9.739 (2) Å	θ = 3.1–27.5°
c = 9.937 (2) Å	µ = 0.47 mm−1
α = 99.23 (3)°	T = 293 K
β = 95.73 (3)°	Block, colorless
γ = 106.27 (3)°	0.35 × 0.30 × 0.15 mm
V = 679.0 (3) Å3

Rigaku Mercury2 diffractometer	3108 independent reflections
Radiation source: fine-focus sealed tube	2310 reflections with I > 2σ(I)
graphite	Rint = 0.037
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
CCD profile fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.959, Tmax = 0.982	l = −12→12
7119 measured reflections

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0354P)2 + 0.3615P] where P = (Fo2 + 2Fc2)/3
3108 reflections	(Δ/σ)max < 0.001
162 parameters	Δρmax = 0.28 e Å−3
2 restraints	Δρmin = −0.24 e Å−3

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	0.81735 (10)	0.00616 (8)	0.30163 (7)	0.0600 (2)
Cl2	0.79242 (9)	0.58762 (8)	0.97152 (7)	0.0597 (2)
N1	0.2136 (3)	0.5855 (2)	0.31035 (18)	0.0390 (4)
H1	0.2058	0.5445	0.2257	0.047*
N2	0.2230 (3)	0.7465 (2)	0.48963 (18)	0.0414 (5)
H2A	0.2224	0.8269	0.5400	0.050*
N3	0.1820 (3)	0.7775 (2)	0.11964 (19)	0.0425 (5)
H3A	0.0823	0.7024	0.0759	0.051*
H3B	0.2875	0.7518	0.1123	0.051*
C1	0.2450 (3)	0.6267 (3)	0.5381 (2)	0.0405 (5)
C2	0.2697 (4)	0.5979 (3)	0.6704 (3)	0.0573 (7)
H2	0.2738	0.6666	0.7483	0.069*
C3	0.2877 (4)	0.4640 (4)	0.6804 (3)	0.0662 (8)
H3	0.3058	0.4419	0.7674	0.079*
C4	0.2798 (4)	0.3597 (3)	0.5650 (3)	0.0628 (8)
H4	0.2919	0.2697	0.5766	0.075*
C5	0.2546 (4)	0.3866 (3)	0.4338 (3)	0.0537 (6)
H5	0.2481	0.3169	0.3562	0.064*
C6	0.2394 (3)	0.5228 (2)	0.4234 (2)	0.0379 (5)
C7	0.2029 (3)	0.7186 (2)	0.3528 (2)	0.0364 (5)
C8	0.1637 (3)	0.8211 (3)	0.2668 (2)	0.0409 (5)
H8	0.0341	0.8225	0.2709	0.049*
C9	0.2916 (4)	0.9767 (3)	0.3080 (3)	0.0529 (6)
H9A	0.4185	0.9793	0.3426	0.063*
H9B	0.2454	1.0327	0.3786	0.063*
C10	0.2868 (6)	1.0359 (3)	0.1762 (3)	0.0755 (9)
H10A	0.2191	1.1077	0.1822	0.091*
H10B	0.4137	1.0822	0.1609	0.091*
C11	0.1905 (5)	0.9111 (3)	0.0618 (3)	0.0666 (8)
H11A	0.2606	0.9135	−0.0152	0.080*
H11B	0.0648	0.9134	0.0302	0.080*
O1W	0.5254 (3)	0.7671 (3)	0.0856 (3)	0.0863 (8)
H1A	0.613 (4)	0.832 (3)	0.142 (3)	0.117 (16)*
H1B	0.572 (5)	0.707 (3)	0.043 (3)	0.102 (13)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0704 (5)	0.0589 (4)	0.0530 (4)	0.0339 (4)	0.0092 (3)	−0.0076 (3)
Cl2	0.0536 (4)	0.0722 (5)	0.0447 (4)	0.0234 (3)	0.0033 (3)	−0.0186 (3)
N1	0.0487 (11)	0.0378 (10)	0.0303 (9)	0.0166 (9)	0.0067 (8)	−0.0010 (7)
N2	0.0501 (11)	0.0408 (11)	0.0331 (10)	0.0182 (9)	0.0101 (8)	−0.0037 (8)
N3	0.0439 (11)	0.0448 (11)	0.0382 (10)	0.0161 (9)	0.0007 (8)	0.0050 (8)
C1	0.0378 (12)	0.0459 (13)	0.0378 (12)	0.0124 (10)	0.0106 (9)	0.0056 (10)
C2	0.0588 (16)	0.0740 (19)	0.0380 (13)	0.0176 (14)	0.0137 (12)	0.0085 (13)
C3	0.0662 (19)	0.086 (2)	0.0546 (17)	0.0220 (17)	0.0159 (14)	0.0355 (16)
C4	0.0642 (18)	0.0557 (17)	0.077 (2)	0.0197 (14)	0.0146 (15)	0.0316 (15)
C5	0.0593 (16)	0.0436 (14)	0.0600 (17)	0.0172 (12)	0.0119 (13)	0.0104 (12)
C6	0.0380 (12)	0.0374 (12)	0.0381 (12)	0.0111 (10)	0.0082 (9)	0.0052 (9)
C7	0.0357 (11)	0.0376 (12)	0.0350 (11)	0.0123 (9)	0.0076 (9)	0.0010 (9)
C8	0.0392 (12)	0.0445 (13)	0.0420 (13)	0.0197 (10)	0.0086 (10)	0.0031 (10)
C9	0.0599 (16)	0.0413 (14)	0.0550 (16)	0.0156 (12)	0.0086 (13)	0.0021 (11)
C10	0.110 (3)	0.0456 (16)	0.069 (2)	0.0160 (17)	0.0164 (18)	0.0150 (14)
C11	0.092 (2)	0.0606 (18)	0.0564 (18)	0.0338 (17)	0.0045 (16)	0.0239 (14)
O1W	0.0539 (13)	0.0682 (15)	0.125 (2)	0.0221 (12)	0.0145 (14)	−0.0227 (14)

N1—C7	1.324 (3)	C4—H4	0.9300
N1—C6	1.384 (3)	C5—C6	1.381 (3)
N1—H1	0.8600	C5—H5	0.9300
N2—C7	1.327 (3)	C7—C8	1.484 (3)
N2—C1	1.376 (3)	C8—C9	1.514 (3)
N2—H2A	0.8600	C8—H8	0.9800
N3—C8	1.487 (3)	C9—C10	1.514 (4)
N3—C11	1.492 (3)	C9—H9A	0.9700
N3—H3A	0.9000	C9—H9B	0.9700
N3—H3B	0.9000	C10—C11	1.481 (4)
C1—C6	1.386 (3)	C10—H10A	0.9700
C1—C2	1.393 (3)	C10—H10B	0.9700
C2—C3	1.366 (4)	C11—H11A	0.9700
C2—H2	0.9300	C11—H11B	0.9700
C3—C4	1.389 (4)	O1W—H1A	0.85 (3)
C3—H3	0.9300	O1W—H1B	0.84 (3)
C4—C5	1.375 (4)
C7—N1—C6	109.38 (18)	N1—C6—C1	105.90 (19)
C7—N1—H1	125.3	N1—C7—N2	108.91 (19)
C6—N1—H1	125.3	N1—C7—C8	127.69 (19)
C7—N2—C1	109.25 (18)	N2—C7—C8	123.30 (19)
C7—N2—H2A	125.4	C7—C8—N3	112.88 (18)
C1—N2—H2A	125.4	C7—C8—C9	115.7 (2)
C8—N3—C11	104.06 (19)	N3—C8—C9	103.78 (19)
C8—N3—H3A	110.9	C7—C8—H8	108.1
C11—N3—H3A	110.9	N3—C8—H8	108.1
C8—N3—H3B	110.9	C9—C8—H8	108.1
C11—N3—H3B	110.9	C8—C9—C10	104.4 (2)
H3A—N3—H3B	109.0	C8—C9—H9A	110.9
N2—C1—C6	106.55 (19)	C10—C9—H9A	110.9
N2—C1—C2	132.8 (2)	C8—C9—H9B	110.9
C6—C1—C2	120.7 (2)	C10—C9—H9B	110.9
C3—C2—C1	116.9 (3)	H9A—C9—H9B	108.9
C3—C2—H2	121.6	C11—C10—C9	107.4 (2)
C1—C2—H2	121.6	C11—C10—H10A	110.2
C2—C3—C4	122.2 (3)	C9—C10—H10A	110.2
C2—C3—H3	118.9	C11—C10—H10B	110.2
C4—C3—H3	118.9	C9—C10—H10B	110.2
C5—C4—C3	121.5 (3)	H10A—C10—H10B	108.5
C5—C4—H4	119.3	C10—C11—N3	105.7 (2)
C3—C4—H4	119.3	C10—C11—H11A	110.6
C4—C5—C6	116.5 (3)	N3—C11—H11A	110.6
C4—C5—H5	121.8	C10—C11—H11B	110.6
C6—C5—H5	121.8	N3—C11—H11B	110.6
C5—C6—N1	131.8 (2)	H11A—C11—H11B	108.7
C5—C6—C1	122.3 (2)	H1A—O1W—H1B	109 (4)
C7—N2—C1—C6	0.6 (2)	C6—N1—C7—N2	0.8 (2)
C7—N2—C1—C2	−179.6 (3)	C6—N1—C7—C8	−175.7 (2)
N2—C1—C2—C3	−179.8 (3)	C1—N2—C7—N1	−0.9 (3)
C6—C1—C2—C3	0.0 (4)	C1—N2—C7—C8	175.8 (2)
C1—C2—C3—C4	−0.7 (4)	N1—C7—C8—N3	−14.5 (3)
C2—C3—C4—C5	0.4 (5)	N2—C7—C8—N3	169.4 (2)
C3—C4—C5—C6	0.6 (4)	N1—C7—C8—C9	−133.8 (2)
C4—C5—C6—N1	−180.0 (2)	N2—C7—C8—C9	50.1 (3)
C4—C5—C6—C1	−1.3 (4)	C11—N3—C8—C7	−164.9 (2)
C7—N1—C6—C5	178.4 (3)	C11—N3—C8—C9	−38.9 (2)
C7—N1—C6—C1	−0.4 (2)	C7—C8—C9—C10	154.4 (2)
N2—C1—C6—C5	−179.1 (2)	N3—C8—C9—C10	30.1 (3)
C2—C1—C6—C5	1.1 (4)	C8—C9—C10—C11	−10.2 (3)
N2—C1—C6—N1	−0.1 (2)	C9—C10—C11—N3	−13.5 (4)
C2—C1—C6—N1	−180.0 (2)	C8—N3—C11—C10	32.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2i	0.86	2.17	3.018 (2)	169
N2—H2A···Cl1i	0.86	2.18	3.021 (2)	166
N3—H3A···Cl2ii	0.90	2.20	3.058 (2)	158
N3—H3B···O1W	0.90	1.80	2.656 (3)	159
O1W—H1A···Cl1iii	0.85 (3)	2.22 (3)	3.069 (3)	174 (4)
O1W—H1B···Cl2iv	0.84 (3)	2.37 (4)	3.181 (2)	161 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2i	0.86	2.17	3.018 (2)	169
N2—H2A⋯Cl1i	0.86	2.18	3.021 (2)	166
N3—H3A⋯Cl2ii	0.90	2.20	3.058 (2)	158
N3—H3B⋯O1W	0.90	1.80	2.656 (3)	159
O1W—H1A⋯Cl1iii	0.85 (3)	2.22 (3)	3.069 (3)	174 (4)
O1W—H1B⋯Cl2iv	0.84 (3)	2.37 (4)	3.181 (2)	161 (4)

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