1-(4-Carb­oxy­phen­yl)-1H-imidazol-3-ium chloride dihydrate

Yu, Z.-P.; Geng, W.-Q.; Kong, L.; Zhou, H.-P.

doi:10.1107/S1600536811001838

organic compounds

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Volume 67| Part 2| February 2011| Page o452

doi:10.1107/S1600536811001838

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1-(4-Carboxyphenyl)-1H-imidazol-3-ium chloride dihydrate

Zhi-Peng Yu,^a Wen-Qian Geng,^a Lin Kong ^a and Hong-Ping Zhou ^a ^*

^aDepartment of Chemistry, Anhui University, Key Laboratory of Functional Inorganic Materials Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: zhpzhp@263.net

(Received 30 December 2010; accepted 12 January 2011; online 22 January 2011)

In the crystal structure of the title compound, C₁₀H₉N₂O₂⁺·Cl⁻·2H₂O, the components are linked by O—H⋯O, N—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds. In the cation, the imidazole ring is oriented at a dihedral angle of 13.67 (17)° with respect to the benzene ring. In the crystal, π–π stacking occurs between nearly parallel benzene rings, which are oriented at a dihedral angle of 3.4 (1)°, the centroid–centroid distance being 3.798 (3) Å.

Related literature

For related imidazole-containing compounds, see: Nyamori & Bala (2008 ); Nie et al. (2009 ).

Experimental

Crystal data

C₁₀H₉N₂O₂⁺·Cl⁻·2H₂O
M_r = 260.67
Orthorhombic, P b c a
a = 7.427 (5) Å
b = 17.708 (5) Å
c = 18.748 (5) Å
V = 2465.7 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.912, T_max = 0.940
14555 measured reflections
2165 independent reflections
1515 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.146
S = 0.96
2165 reflections
175 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.21	2.822 (3)	128
N2—H2⋯Cl1ⁱⁱ	0.86	2.62	3.231 (2)	129
O2—H7⋯O4ⁱⁱⁱ	0.82	1.77	2.594 (3)	177
O3—H10⋯Cl1^iv	0.83 (4)	2.36 (4)	3.150 (3)	159 (3)
O3—H11⋯Cl1^v	0.94 (5)	2.22 (5)	3.141 (3)	168 (3)
O4—H12⋯O3	0.76 (4)	1.99 (4)	2.718 (4)	162 (4)
O4—H13⋯Cl1	0.86 (4)	2.22 (4)	3.066 (4)	172 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (v) x-1, y, z.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001838/xu5134sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001838/xu5134Isup2.hkl

checkCIF report

Comment top

Imidazol - based materials had been investigated for their electrical and optical properties. Beside, the introduction about the structure of its complex has been reported (Nie et al., 2009). The title molecule that we has designed and synthesized is a good intermediate and penetratingly investigated. In the title molecule(I) (Fig.1), the bond lengths and angles show normal values. The imidazole ring is twisted out of the plane of the center benzene ring at a dihedral angle of 13.67 (17)°. In the title molecule (I) (Fig.2), the neighboring molecules connect through O—H···O, N—H···O, O—H···Cl and N—H···Cl hydrogen bonds (Table 1). π–π stacking is observed between nearly parallel benzene rings, the centroids distance being 3.798 (3) Å.

Related literature top

For related imidazole-containing compounds, see: Nyamori & Bala (2008); Nie et al. (2009).

Experimental top

A 150 ml round-bottom flask was charged with a magnetic stirrer and a reflux condenser, iminazole (44 mmol), K₂CO₃ (6.00 g, 43 mmol), 30 ml DMSO and a little Aliquat 336 were added. 4-Fluorobenzaldehyde (4.5 ml, 42 mmol) was added dropwise to the mixture at 363 K and stirred for 15 min. Then the reaction mixture was refluxed for 24 h at 353 K, cooled to room temperature, poured into 150 ml ice-water and filtered. The primrose yellow crude product was obtained, washed with distilled water, and dried in vacuo at room temperature, then purified by recrystallization with ethyl acetate to give the desired analytical pure intermediate products. Intermediate product (12.5 mmol) and 15 ml 20% (wt) NaOH (aq) were added to a round-bottom flask equipped with a magnetic stirrer and a reflux condenser at 333 K for 30 min. Then AgNO₃ (4.00 g, 24 mmol) was added to the mixture group by group. The reaction mixture was refluxed for 24 h at 333 K, cooled to room temperature and filtered. Excessive HCl (1 M) was added to the filtrate and adjust pH to 2, a great deal of sediments were obtained and then filtered. The crude product was recrystallized from ethanol-water solution.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 the title molecule(I) showing 30% probability displacement ellipsoids.
	Fig. 2. The H-bond and weak π–π interaction diagram of the title molecule(I).

1-(4-Carboxyphenyl)-1H-imidazol-3-ium chloride dihydrate top

Crystal data top

C₁₀H₉N₂O₂⁺·Cl⁻·2H₂O	F(000) = 1088
M_r = 260.67	D_x = 1.404 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3445 reflections
a = 7.427 (5) Å	θ = 2.3–21.7°
b = 17.708 (5) Å	µ = 0.32 mm⁻¹
c = 18.748 (5) Å	T = 298 K
V = 2465.7 (19) Å³	Block, yellow
Z = 8	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2165 independent reflections
Radiation source: fine-focus sealed tube	1515 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→7
T_min = 0.912, T_max = 0.940	k = −21→16
14555 measured reflections	l = −17→22

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ²(F_o²) + (0.1P)² + 0.3P] where P = (F_o² + 2F_c²)/3
2165 reflections	(Δ/σ)_max < 0.001
175 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₀H₉N₂O₂⁺·Cl⁻·2H₂O	V = 2465.7 (19) Å³
M_r = 260.67	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.427 (5) Å	µ = 0.32 mm⁻¹
b = 17.708 (5) Å	T = 298 K
c = 18.748 (5) Å	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2165 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1515 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.940	R_int = 0.033
14555 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.20 e Å⁻³
2165 reflections	Δρ_min = −0.32 e Å⁻³
175 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
Cl1	0.99581 (9)	0.35765 (4)	0.14987 (4)	0.0637 (3)
O3	0.4071 (3)	0.34344 (12)	0.18640 (13)	0.0661 (6)
N1	0.6552 (3)	0.13527 (10)	0.12446 (10)	0.0467 (5)
C4	0.6689 (3)	0.11991 (13)	0.19963 (12)	0.0423 (6)
O4	0.6325 (4)	0.41591 (12)	0.09501 (10)	0.0628 (6)
O2	0.6026 (3)	0.11860 (11)	0.46109 (9)	0.0678 (6)
H7	0.6154	0.1068	0.5031	0.102*
O1	0.7751 (3)	0.01818 (11)	0.44419 (10)	0.0717 (6)
C10	0.6934 (3)	0.07130 (14)	0.42051 (13)	0.0484 (6)
C6	0.7468 (3)	0.03739 (12)	0.29454 (12)	0.0473 (6)
H6	0.7936	−0.0083	0.3105	0.057*
C7	0.6859 (3)	0.09017 (12)	0.34359 (12)	0.0436 (6)
C5	0.7388 (3)	0.05180 (13)	0.22262 (12)	0.0481 (6)
H5	0.7798	0.0163	0.1899	0.058*
C8	0.6198 (3)	0.15821 (13)	0.31931 (13)	0.0483 (6)
H8	0.5805	0.1941	0.3520	0.058*
C9	0.6110 (3)	0.17379 (12)	0.24755 (13)	0.0469 (6)
H9	0.5667	0.2199	0.2316	0.056*
N2	0.6424 (3)	0.12032 (12)	0.01107 (11)	0.0572 (6)
H2	0.6454	0.0992	−0.0302	0.069*
C3	0.6691 (3)	0.08596 (14)	0.07173 (13)	0.0532 (7)
H3	0.6941	0.0348	0.0771	0.064*
C2	0.6095 (6)	0.19392 (17)	0.02329 (16)	0.0848 (11)
C1	0.6184 (6)	0.20415 (17)	0.09362 (16)	0.0934 (12)
H1	0.6026	0.2496	0.1176	0.112*
H12	0.554 (5)	0.402 (2)	0.117 (2)	0.079 (13)*
H13	0.734 (5)	0.3965 (18)	0.1065 (16)	0.076 (11)*
H11	0.283 (6)	0.341 (2)	0.179 (2)	0.118 (15)*
H10	0.421 (6)	0.359 (2)	0.228 (2)	0.112 (15)*
H4	0.597 (5)	0.230 (2)	−0.017 (2)	0.112 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0640 (5)	0.0782 (5)	0.0489 (5)	−0.0013 (3)	0.0008 (3)	−0.0005 (3)
O3	0.0661 (15)	0.0778 (14)	0.0545 (14)	0.0097 (11)	0.0031 (11)	−0.0011 (11)
N1	0.0583 (12)	0.0435 (11)	0.0383 (11)	−0.0004 (9)	−0.0028 (9)	−0.0008 (9)
C4	0.0480 (13)	0.0421 (12)	0.0370 (13)	−0.0030 (10)	−0.0038 (10)	−0.0021 (10)
O4	0.0735 (15)	0.0696 (13)	0.0452 (12)	0.0004 (13)	0.0000 (12)	0.0038 (9)
O2	0.0905 (15)	0.0737 (12)	0.0393 (10)	0.0220 (11)	0.0038 (10)	0.0017 (10)
O1	0.0959 (15)	0.0695 (12)	0.0497 (11)	0.0272 (12)	−0.0011 (10)	0.0107 (9)
C10	0.0514 (14)	0.0493 (13)	0.0444 (14)	0.0007 (12)	−0.0044 (12)	−0.0011 (12)
C6	0.0571 (14)	0.0351 (11)	0.0497 (14)	0.0043 (11)	−0.0047 (12)	0.0016 (11)
C7	0.0460 (13)	0.0431 (13)	0.0416 (13)	−0.0026 (10)	−0.0050 (10)	0.0009 (10)
C5	0.0623 (15)	0.0406 (13)	0.0413 (13)	0.0032 (11)	0.0000 (12)	−0.0057 (11)
C8	0.0602 (16)	0.0449 (13)	0.0397 (14)	0.0045 (11)	−0.0018 (11)	−0.0059 (10)
C9	0.0583 (15)	0.0374 (11)	0.0450 (14)	0.0064 (11)	−0.0015 (11)	0.0012 (11)
N2	0.0716 (15)	0.0631 (14)	0.0369 (12)	−0.0002 (11)	−0.0019 (10)	−0.0056 (10)
C3	0.0677 (17)	0.0500 (14)	0.0420 (14)	0.0050 (12)	−0.0007 (12)	−0.0075 (12)
C2	0.152 (3)	0.0592 (19)	0.0428 (17)	0.011 (2)	−0.0073 (19)	0.0062 (14)
C1	0.186 (4)	0.0480 (16)	0.0467 (17)	0.017 (2)	−0.010 (2)	0.0026 (13)

Geometric parameters (Å, º) top

O3—H11	0.94 (5)	C6—C7	1.387 (3)
O3—H10	0.83 (4)	C6—H6	0.9300
N1—C3	1.323 (3)	C7—C8	1.379 (3)
N1—C1	1.377 (3)	C5—H5	0.9300
N1—C4	1.439 (3)	C8—C9	1.375 (3)
C4—C9	1.379 (3)	C8—H8	0.9300
C4—C5	1.382 (3)	C9—H9	0.9300
O4—H12	0.76 (4)	N2—C3	1.305 (3)
O4—H13	0.86 (3)	N2—C2	1.346 (4)
O2—C10	1.317 (3)	N2—H2	0.8600
O2—H7	0.8200	C3—H3	0.9300
O1—C10	1.204 (3)	C2—C1	1.333 (4)
C10—C7	1.481 (3)	C2—H4	0.99 (4)
C6—C5	1.373 (3)	C1—H1	0.9300

H11—O3—H10	106 (4)	C4—C5—H5	120.5
C3—N1—C1	106.6 (2)	C9—C8—C7	121.0 (2)
C3—N1—C4	127.0 (2)	C9—C8—H8	119.5
C1—N1—C4	126.3 (2)	C7—C8—H8	119.5
C9—C4—C5	121.2 (2)	C8—C9—C4	118.9 (2)
C9—C4—N1	119.0 (2)	C8—C9—H9	120.5
C5—C4—N1	119.8 (2)	C4—C9—H9	120.5
H12—O4—H13	115 (3)	C3—N2—C2	109.3 (2)
C10—O2—H7	109.5	C3—N2—H2	125.3
O1—C10—O2	122.8 (2)	C2—N2—H2	125.3
O1—C10—C7	123.6 (2)	N2—C3—N1	109.4 (2)
O2—C10—C7	113.6 (2)	N2—C3—H3	125.3
C5—C6—C7	120.8 (2)	N1—C3—H3	125.3
C5—C6—H6	119.6	C1—C2—N2	106.9 (3)
C7—C6—H6	119.6	C1—C2—H4	132 (2)
C8—C7—C6	119.1 (2)	N2—C2—H4	121 (2)
C8—C7—C10	122.1 (2)	C2—C1—N1	107.8 (3)
C6—C7—C10	118.8 (2)	C2—C1—H1	126.1
C6—C5—C4	119.0 (2)	N1—C1—H1	126.1
C6—C5—H5	120.5

C3—N1—C4—C9	−165.3 (2)	C6—C7—C8—C9	1.0 (4)
C1—N1—C4—C9	12.2 (4)	C10—C7—C8—C9	−178.7 (2)
C3—N1—C4—C5	14.4 (4)	C7—C8—C9—C4	0.3 (4)
C1—N1—C4—C5	−168.1 (3)	C5—C4—C9—C8	−1.5 (4)
C5—C6—C7—C8	−1.1 (4)	N1—C4—C9—C8	178.3 (2)
C5—C6—C7—C10	178.6 (2)	C2—N2—C3—N1	−0.2 (3)
O1—C10—C7—C8	−167.9 (3)	C1—N1—C3—N2	−0.3 (3)
O2—C10—C7—C8	11.7 (3)	C4—N1—C3—N2	177.6 (2)
O1—C10—C7—C6	12.4 (4)	C3—N2—C2—C1	0.6 (4)
O2—C10—C7—C6	−168.0 (2)	N2—C2—C1—N1	−0.7 (4)
C7—C6—C5—C4	0.0 (4)	C3—N1—C1—C2	0.6 (4)
C9—C4—C5—C6	1.4 (4)	C4—N1—C1—C2	−177.3 (3)
N1—C4—C5—C6	−178.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.21	2.822 (3)	128
N2—H2···Cl1ⁱⁱ	0.86	2.62	3.231 (2)	129
O2—H7···O4ⁱⁱⁱ	0.82	1.77	2.594 (3)	177
O3—H10···Cl1^iv	0.83 (4)	2.36 (4)	3.150 (3)	159 (3)
O3—H11···Cl1^v	0.94 (5)	2.22 (5)	3.141 (3)	168 (3)
O4—H12···O3	0.76 (4)	1.99 (4)	2.718 (4)	162 (4)
O4—H13···Cl1	0.86 (4)	2.22 (4)	3.066 (4)	172 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉N₂O₂⁺·Cl⁻·2H₂O
M_r	260.67
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	7.427 (5), 17.708 (5), 18.748 (5)
V (Å³)	2465.7 (19)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.912, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	14555, 2165, 1515
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.146, 0.96
No. of reflections	2165
No. of parameters	175
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.32

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.21	2.822 (3)	128
N2—H2···Cl1ⁱⁱ	0.86	2.62	3.231 (2)	129
O2—H7···O4ⁱⁱⁱ	0.82	1.77	2.594 (3)	177
O3—H10···Cl1^iv	0.83 (4)	2.36 (4)	3.150 (3)	159 (3)
O3—H11···Cl1^v	0.94 (5)	2.22 (5)	3.141 (3)	168 (3)
O4—H12···O3	0.76 (4)	1.99 (4)	2.718 (4)	162 (4)
O4—H13···Cl1	0.86 (4)	2.22 (4)	3.066 (4)	172 (3)

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

Acknowledgements

This work was supported by grants from the National Natural Science Foundation of China (21071001), the Education Committee of Anhui Province (KJ2009A52, KJ2010A30), the Team for Scientific Innovation Foundation of Anhui Province (2006 K J007TD), the Ministry of Education Person with Ability Foundation of Anhui University, the Science and Technological Fund of Anhui Province for Outstanding Youth (10040606Y22), and the 211 Project of Anhui University.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SAMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Nie, J.-J., Li, J.-H. & Xu, D.-J. (2009). Acta Cryst. E65, m822–m823. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nyamori, V. O. & Bala, M. D. (2008). Acta Cryst. E64, m1451. 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