Benzimidazolium 2-(2,4-dichloro­phen­oxy)acetate monohydrate

Liu, H.-L.; Wang, Q.-Z.; Jian, F.-F.

doi:10.1107/S1600536809045899

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3043

doi:10.1107/S1600536809045899

Open

access

Benzimidazolium 2-(2,4-dichlorophenoxy)acetate monohydrate

Hui-Lian Liu,^a Qing-Zhong Wang ^a and Fang-Fang Jian ^b ^*

^aMicroscale Science Institute, Biology Department, Weifang University, Weifang 261061, People's Republic of China, and ^bMicrosale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 29 October 2009; accepted 2 November 2009; online 11 November 2009)

In the crystal of the title hydrated molecular salt, C₇H₇N₂⁺·C₈H₅Cl₂O₃·H₂O, the components interact by way of N—H⋯O and O—H⋯O hydrogen bonds, leading to chains propagating in [100].

Related literature

For background to 2,4-dichlorophenoxyacetic acid, see: Lv (1998 ).

Experimental

Crystal data

C₇H₇N₂⁺·C₈H₅Cl₂O₃⁻·H₂O
M_r = 357.18
Orthorhombic, P n a 2₁
a = 4.9322 (10) Å
b = 23.808 (5) Å
c = 13.931 (3) Å
V = 1635.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
13995 measured reflections
3746 independent reflections
3083 reflections with I > 2σ(I)
R_int = 0.069

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.102
S = 0.98
3746 reflections
216 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ), 1784 Friedel pairs
Flack parameter: 0.04 (5)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	1.78	2.636 (3)	179
N2—H2A⋯O3	0.86	1.81	2.667 (3)	172
O1W—H1WA⋯O3	0.74 (5)	2.11 (5)	2.822 (4)	160 (5)
O1W—H1WB⋯O1Wⁱⁱ	0.81 (4)	1.95 (4)	2.751 (4)	173 (4)
Symmetry codes: (i) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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/S1600536809045899/hb5201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045899/hb5201Isup2.hkl

checkCIF report

Related literature top

For background to 2,4-dichlorophenoxyacetic acid, see: Lv (1998).

Experimental top

A mixture of 2,4-Dichlorophenoxyacetic acid 4.42 g (0.02 mol) and benzimidazole 2.4 g (0.02 mol) was stirred with ethanol (50 ml) at 367 K for 3 h. Colourless bars of (I) were obtained by recrystallization from acetone and ethanol (1:1) at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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. The molecular structure of (I) showing 30% probability displacement ellipsoids.

Benzimidazolium 2-(2,4-dichlorophenoxy)acetate monohydrate top

Crystal data top

C₇H₇N₂⁺·C₈H₅Cl₂O₃⁻·H₂O	F(000) = 736
M_r = 357.18	D_x = 1.450 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2216 reflections
a = 4.9322 (10) Å	θ = 3.4–27.5°
b = 23.808 (5) Å	µ = 0.42 mm⁻¹
c = 13.931 (3) Å	T = 293 K
V = 1635.9 (6) Å³	Bar, colorless
Z = 4	0.20 × 0.15 × 0.11 mm

Data collection top

Bruker SMART CCD diffractometer	3083 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.069
Graphite monochromator	θ_max = 27.5°, θ_min = 3.4°
ω scans	h = −6→6
13995 measured reflections	k = −30→30
3746 independent reflections	l = −18→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0468P)²] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
3746 reflections	Δρ_max = 0.32 e Å⁻³
216 parameters	Δρ_min = −0.34 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1784 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (5)

Crystal data top

C₇H₇N₂⁺·C₈H₅Cl₂O₃⁻·H₂O	V = 1635.9 (6) Å³
M_r = 357.18	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 4.9322 (10) Å	µ = 0.42 mm⁻¹
b = 23.808 (5) Å	T = 293 K
c = 13.931 (3) Å	0.20 × 0.15 × 0.11 mm

Data collection top

Bruker SMART CCD diffractometer	3083 reflections with I > 2σ(I)
13995 measured reflections	R_int = 0.069
3746 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.102	Δρ_max = 0.32 e Å⁻³
S = 0.98	Δρ_min = −0.34 e Å⁻³
3746 reflections	Absolute structure: Flack (1983), 1784 Friedel pairs
216 parameters	Absolute structure parameter: 0.04 (5)
1 restraint

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
Cl1	0.90454 (14)	0.52904 (3)	0.19850 (5)	0.05295 (18)
Cl2	0.18254 (15)	0.69703 (3)	0.23025 (7)	0.0655 (2)
O1	0.9973 (3)	0.57283 (7)	0.00727 (12)	0.0399 (4)
N2	0.5521 (4)	0.57806 (9)	−0.38610 (16)	0.0433 (5)
H2A	0.6477	0.5848	−0.3358	0.052*
O3	0.8577 (4)	0.60800 (8)	−0.23670 (12)	0.0495 (5)
N1	0.3939 (4)	0.53553 (8)	−0.51242 (16)	0.0424 (5)
H1A	0.3716	0.5105	−0.5563	0.051*
O2	0.6808 (3)	0.53999 (7)	−0.14827 (13)	0.0419 (4)
C10	0.5471 (5)	0.61429 (10)	0.2019 (2)	0.0429 (5)
H10A	0.5020	0.6018	0.2631	0.051*
C15	0.8470 (4)	0.57845 (8)	−0.16206 (16)	0.0316 (4)
C13	0.6758 (5)	0.65057 (10)	0.01831 (19)	0.0392 (5)
H13A	0.7166	0.6629	−0.0433	0.047*
C1	0.3528 (5)	0.61244 (10)	−0.42408 (17)	0.0378 (5)
C8	0.8059 (4)	0.60339 (9)	0.05484 (16)	0.0345 (5)
C14	1.0646 (5)	0.59077 (11)	−0.08771 (18)	0.0387 (5)
H14A	1.2313	0.5724	−0.1072	0.046*
H14B	1.0983	0.6309	−0.0867	0.046*
C7	0.5692 (5)	0.53288 (10)	−0.4412 (2)	0.0446 (6)
H7A	0.6888	0.5033	−0.4310	0.054*
C11	0.4222 (5)	0.66116 (11)	0.1635 (2)	0.0437 (6)
C12	0.4859 (5)	0.67944 (11)	0.0727 (2)	0.0450 (6)
H12A	0.4016	0.7112	0.0477	0.054*
C6	0.2510 (5)	0.58563 (10)	−0.50448 (18)	0.0360 (5)
C9	0.7402 (5)	0.58614 (10)	0.14810 (17)	0.0366 (5)
C2	0.2556 (6)	0.66476 (10)	−0.3953 (2)	0.0517 (7)
H2B	0.3238	0.6831	−0.3415	0.062*
C4	−0.0475 (6)	0.66061 (14)	−0.5315 (3)	0.0641 (8)
H4A	−0.1831	0.6780	−0.5671	0.077*
C5	0.0468 (6)	0.60888 (13)	−0.5602 (2)	0.0511 (7)
H5A	−0.0224	0.5906	−0.6139	0.061*
C3	0.0547 (7)	0.68769 (13)	−0.4503 (3)	0.0673 (9)
H3A	−0.0161	0.7225	−0.4331	0.081*
O1W	0.8508 (6)	0.72439 (12)	−0.1984 (3)	0.0798 (9)
H1WA	0.831 (9)	0.696 (2)	−0.219 (4)	0.111 (19)*
H1WB	0.995 (8)	0.7405 (17)	−0.194 (3)	0.088 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0616 (4)	0.0589 (4)	0.0383 (3)	0.0105 (3)	−0.0035 (3)	0.0137 (3)
Cl2	0.0578 (4)	0.0584 (4)	0.0802 (6)	0.0021 (3)	0.0287 (4)	−0.0082 (4)
O1	0.0435 (9)	0.0492 (9)	0.0271 (8)	0.0090 (7)	−0.0022 (7)	0.0020 (7)
N2	0.0522 (12)	0.0432 (11)	0.0344 (11)	−0.0106 (10)	−0.0063 (9)	0.0002 (9)
O3	0.0647 (12)	0.0488 (10)	0.0350 (9)	−0.0190 (8)	−0.0114 (8)	0.0130 (7)
N1	0.0489 (11)	0.0373 (10)	0.0410 (12)	−0.0052 (9)	−0.0017 (10)	−0.0081 (9)
O2	0.0464 (10)	0.0415 (9)	0.0378 (9)	−0.0093 (7)	−0.0024 (8)	0.0054 (7)
C10	0.0419 (12)	0.0494 (13)	0.0373 (12)	−0.0089 (10)	0.0023 (12)	−0.0011 (11)
C15	0.0352 (10)	0.0321 (10)	0.0274 (11)	0.0031 (8)	0.0026 (9)	−0.0011 (8)
C13	0.0471 (12)	0.0393 (11)	0.0313 (12)	−0.0005 (10)	−0.0020 (10)	0.0019 (10)
C1	0.0457 (12)	0.0354 (11)	0.0321 (12)	−0.0084 (10)	0.0051 (10)	0.0021 (9)
C8	0.0356 (11)	0.0380 (11)	0.0300 (11)	−0.0005 (9)	−0.0054 (10)	−0.0027 (9)
C14	0.0354 (12)	0.0497 (13)	0.0310 (11)	0.0018 (10)	−0.0023 (10)	0.0029 (10)
C7	0.0502 (14)	0.0363 (12)	0.0474 (15)	−0.0031 (10)	−0.0030 (12)	−0.0002 (11)
C11	0.0376 (12)	0.0434 (13)	0.0501 (15)	−0.0058 (10)	0.0041 (11)	−0.0061 (11)
C12	0.0462 (13)	0.0397 (12)	0.0491 (16)	0.0029 (10)	−0.0018 (12)	0.0007 (11)
C6	0.0377 (12)	0.0382 (11)	0.0322 (12)	−0.0057 (9)	0.0012 (9)	0.0008 (9)
C9	0.0391 (11)	0.0419 (12)	0.0288 (12)	−0.0036 (10)	−0.0022 (10)	0.0019 (9)
C2	0.0674 (17)	0.0394 (14)	0.0482 (16)	−0.0074 (13)	0.0174 (14)	−0.0081 (12)
C4	0.0554 (16)	0.0667 (19)	0.070 (2)	0.0127 (14)	0.0073 (16)	0.0225 (17)
C5	0.0493 (14)	0.0633 (18)	0.0409 (15)	−0.0074 (13)	−0.0075 (13)	0.0076 (13)
C3	0.078 (2)	0.0415 (15)	0.083 (3)	0.0100 (14)	0.023 (2)	0.0027 (16)
O1W	0.0654 (16)	0.0463 (13)	0.128 (3)	0.0020 (12)	0.0147 (17)	0.0039 (14)

Geometric parameters (Å, º) top

Cl1—C9	1.731 (2)	C1—C6	1.384 (3)
Cl2—C11	1.729 (3)	C1—C2	1.394 (3)
O1—C8	1.364 (3)	C8—C9	1.401 (3)
O1—C14	1.429 (3)	C14—H14A	0.9700
N2—C7	1.324 (3)	C14—H14B	0.9700
N2—C1	1.384 (3)	C7—H7A	0.9300
N2—H2A	0.8600	C11—C12	1.375 (4)
O3—C15	1.257 (3)	C12—H12A	0.9300
N1—C7	1.318 (3)	C6—C5	1.387 (4)
N1—C6	1.390 (3)	C2—C3	1.366 (4)
N1—H1A	0.8600	C2—H2B	0.9300
O2—C15	1.244 (3)	C4—C5	1.376 (4)
C10—C11	1.383 (4)	C4—C3	1.396 (5)
C10—C9	1.385 (3)	C4—H4A	0.9300
C10—H10A	0.9300	C5—H5A	0.9300
C15—C14	1.520 (3)	C3—H3A	0.9300
C13—C12	1.387 (3)	O1W—H1WA	0.73 (5)
C13—C8	1.390 (3)	O1W—H1WB	0.81 (4)
C13—H13A	0.9300

C8—O1—C14	116.82 (18)	N1—C7—N2	110.9 (2)
C7—N2—C1	107.7 (2)	N1—C7—H7A	124.6
C7—N2—H2A	126.2	N2—C7—H7A	124.6
C1—N2—H2A	126.2	C12—C11—C10	120.7 (3)
C7—N1—C6	108.3 (2)	C12—C11—Cl2	119.7 (2)
C7—N1—H1A	125.9	C10—C11—Cl2	119.7 (2)
C6—N1—H1A	125.9	C11—C12—C13	120.0 (2)
C11—C10—C9	119.2 (3)	C11—C12—H12A	120.0
C11—C10—H10A	120.4	C13—C12—H12A	120.0
C9—C10—H10A	120.4	C1—C6—C5	122.2 (2)
O2—C15—O3	124.6 (2)	C1—C6—N1	106.0 (2)
O2—C15—C14	120.1 (2)	C5—C6—N1	131.8 (2)
O3—C15—C14	115.25 (19)	C10—C9—C8	121.3 (2)
C12—C13—C8	120.8 (2)	C10—C9—Cl1	118.83 (19)
C12—C13—H13A	119.6	C8—C9—Cl1	119.89 (18)
C8—C13—H13A	119.6	C3—C2—C1	116.4 (3)
N2—C1—C6	107.1 (2)	C3—C2—H2B	121.8
N2—C1—C2	131.5 (2)	C1—C2—H2B	121.8
C6—C1—C2	121.4 (2)	C5—C4—C3	121.8 (3)
O1—C8—C13	124.9 (2)	C5—C4—H4A	119.1
O1—C8—C9	117.0 (2)	C3—C4—H4A	119.1
C13—C8—C9	118.0 (2)	C4—C5—C6	116.1 (3)
O1—C14—C15	114.17 (19)	C4—C5—H5A	122.0
O1—C14—H14A	108.7	C6—C5—H5A	122.0
C15—C14—H14A	108.7	C2—C3—C4	122.1 (3)
O1—C14—H14B	108.7	C2—C3—H3A	118.9
C15—C14—H14B	108.7	C4—C3—H3A	118.9
H14A—C14—H14B	107.6	H1WA—O1W—H1WB	126 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	1.78	2.636 (3)	179
N2—H2A···O3	0.86	1.81	2.667 (3)	172
O1W—H1WA···O3	0.74 (5)	2.11 (5)	2.822 (4)	160 (5)
O1W—H1WB···O1Wⁱⁱ	0.81 (4)	1.95 (4)	2.751 (4)	173 (4)

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

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·C₈H₅Cl₂O₃⁻·H₂O
M_r	357.18
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	4.9322 (10), 23.808 (5), 13.931 (3)
V (Å³)	1635.9 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.20 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13995, 3746, 3083
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.102, 0.98
No. of reflections	3746
No. of parameters	216
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.34
Absolute structure	Flack (1983), 1784 Friedel pairs
Absolute structure parameter	0.04 (5)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
N1—H1A···O2ⁱ	0.86	1.78	2.636 (3)	179
N2—H2A···O3	0.86	1.81	2.667 (3)	172
O1W—H1WA···O3	0.74 (5)	2.11 (5)	2.822 (4)	160 (5)
O1W—H1WB···O1Wⁱⁱ	0.81 (4)	1.95 (4)	2.751 (4)	173 (4)

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

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lv, F. T. (1998). Chem. Agent. 20, 179. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3043

doi:10.1107/S1600536809045899

Open

access