5-Carb­oxy-2-isopropyl-1H-imidazol-3-ium-4-carboxyl­ate monohydrate

Du, C.-J.; Shi, Z.-H.; Wang, L.-S.; Du, C.-L.

doi:10.1107/S1600536811024767

organic compounds

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Volume 67| Part 7| July 2011| Page o1837

doi:10.1107/S1600536811024767

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5-Carboxy-2-isopropyl-1H-imidazol-3-ium-4-carboxylate monohydrate

Chao-Jun Du,^a,^b ^* Zheng-Hai Shi,^a Li-Sheng Wang ^b and Chao-Ling Du ^c

^aDepartment of Chemical and Biochemical Engineering, Nanyang Institute of Technology, 473004 Nanyang, Henan, People's Republic of China, ^bSchool of Chemical Engineering and Environment, Beijing Institute of Technology, 100081 Beijing, People's Republic of China, and ^cCollege of Science, Nanjing University of Aeronautics and Astronautics, Nanjing 211100, People's Republic of China
^*Correspondence e-mail: chjdu@yahoo.com.cn

(Received 1 June 2011; accepted 23 June 2011; online 30 June 2011)

In the title compound, C₈H₁₀N₂O₄·H₂O, the imidazole N atom is protonated and one of the carboxylate groups is deprotoned, forming a zwitterion. An intramolecular O—H⋯O hydrogen bond occurs. The crystal structure is stabilized by intermolecular N—H⋯O and O—H⋯O hydrogen bonds. In addition, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the molecules into two-dimensional networks parallel to (10 $[\overline{2}]$ ).

Related literature

For the use of related imidazoledicarboxylic acid structures in coordination chemistry, see: Sun et al. (2006 ); Merchan & Stoeckli-Evans (2007 ); Guo (2009 ); Wang & Qin (2010 ); Wang et al. (2010 ); Feng et al. (2010 ); Li et al. (2010 ). For the synthesis of the title compound, see: Alcalde et al. (1992 ).

Experimental

Crystal data

C₈H₁₀N₂O₄·H₂O
M_r = 216.20
Monoclinic, P 2₁ /c
a = 7.828 (2) Å
b = 14.308 (4) Å
c = 8.930 (2) Å
β = 93.590 (3)°
V = 998.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 298 K
0.40 × 0.32 × 0.28 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.953, T_max = 0.967
4874 measured reflections
2147 independent reflections
1599 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.06
2147 reflections
140 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.64	2.4576 (19)	175
N1—H1⋯O5	0.86	1.83	2.6879 (19)	171
N2—H2⋯O1ⁱ	0.86	1.93	2.7619 (19)	162
O5—H5B⋯O3ⁱⁱ	0.85	2.03	2.8684 (19)	171
O5—H5A⋯O4ⁱⁱⁱ	0.85	1.94	2.7857 (19)	173
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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 global, I. DOI: 10.1107/S1600536811024767/lr2015sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024767/lr2015Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811024767/lr2015Isup3.cml

checkCIF report

Comment top

In the past the construction of metal complexes based on N-heterocyclic carboxylic acids has attracted much attention due to their intriguing topologies as well as their potential applications in many fields. Particular attention has been paid to the 1H-imidazole-4,5-dicarboxylic acid ligand and its analogs: (Sun et al., 2006) have synthesized the 4-carboxy-2-(pyridinium-4-yl)-1H-imidazole-5-carboxylate monohydrate; Merchan et al. (2007) have prepared the dimethylammonium 4-carboxy-1H-imidazole-5-carboxylate; (Guo, 2009) have reported the 4-carboxy-2-methyl-1H-imidazole-5-carboxylate monohydrate and (Wang & Qin, 2010) have reported the dimethylammonium 4-carboxy-2-n-propyl-1H-imidazole-5-carboxylate. All of these 1H-imidazole-4,5-dicarboxylic acid and their analogs have been used as ligands to design metal complexes and most of them are proved ideal ligands (Wang et al., 2010; Feng et al., 2010; Li et al., 2010). However, the crystal structure of 4-carboxy-2-isopropyl-1H-imidazole-5-carboxylate has not been yet determined. Keeping that in mind, we report here the preparation and crystal structure of the title compound. The crystal structure (Fig.2, Table1) is stabilized by two intramolecular and three intermolecular N—H···O and O—H···O hydrogen bonds which link the molecules into two-dimensional networks parallel to the (102) planes.

Related literature top

For the use of related imidazoledicarboxylic acid structures in coordination chemistry, see: Sun et al. (2006); Merchan & Stoeckli-Evans (2007); Guo (2009); Wang & Qin (2010); Wang et al. (2010); Feng et al. (2010); Li et al. (2010). For the synthesis of the title compound, see: Alcalde et al. (1992).

Experimental top

The title compound was synthesized according to the method reported in the literature (Alcalde et al., 1992). Colourless single crystals suitable for X-ray diffraction were obtained by slow evaporation of a water solution of the compound.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the crystal structure. The H-atoms not included in hydrogen bonding have been omitted for clarity.

5-Carboxy-2-isopropyl-1H-imidazol-3-ium-4-carboxylate monohydrate top

Crystal data top

C₈H₁₀N₂O₄·H₂O	F(000) = 456
M_r = 216.20	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1379 reflections
a = 7.828 (2) Å	θ = 2.7–25.1°
b = 14.308 (4) Å	µ = 0.12 mm⁻¹
c = 8.930 (2) Å	T = 298 K
β = 93.590 (3)°	Block, colourless
V = 998.2 (4) Å³	0.40 × 0.32 × 0.28 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2147 independent reflections
Radiation source: fine-focus sealed tube	1599 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.953, T_max = 0.967	k = −17→18
4874 measured reflections	l = −11→7

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.059P)² + 0.133P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2147 reflections	Δρ_max = 0.32 e Å⁻³
140 parameters	Δρ_min = −0.19 e Å⁻³
3 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (3)

Crystal data top

C₈H₁₀N₂O₄·H₂O	V = 998.2 (4) Å³
M_r = 216.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.828 (2) Å	µ = 0.12 mm⁻¹
b = 14.308 (4) Å	T = 298 K
c = 8.930 (2) Å	0.40 × 0.32 × 0.28 mm
β = 93.590 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2147 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1599 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.967	R_int = 0.028
4874 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	3 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.06	Δρ_max = 0.32 e Å⁻³
2147 reflections	Δρ_min = −0.19 e Å⁻³
140 parameters

Special details top

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 ofF² > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C4	1.2174 (2)	0.88114 (12)	0.4485 (2)	0.0397 (4)
C2	1.0189 (2)	0.76673 (11)	0.29253 (18)	0.0346 (4)
C3	1.0710 (2)	0.85223 (11)	0.34578 (19)	0.0350 (4)
C6	0.6833 (2)	0.91545 (12)	0.1177 (2)	0.0413 (4)
H6	0.6971	0.9835	0.1205	0.050*
C1	1.0889 (2)	0.67085 (11)	0.3136 (2)	0.0391 (4)
C5	0.8360 (2)	0.87217 (11)	0.19793 (19)	0.0366 (4)
C7	0.5240 (2)	0.89011 (17)	0.1978 (2)	0.0593 (6)
H7A	0.5139	0.8233	0.2031	0.089*
H7B	0.4249	0.9154	0.1435	0.089*
H7C	0.5328	0.9156	0.2975	0.089*
C8	0.6644 (3)	0.88445 (16)	−0.0461 (2)	0.0622 (6)
H8A	0.7620	0.9051	−0.0971	0.093*
H8B	0.5624	0.9113	−0.0934	0.093*
H8C	0.6571	0.8175	−0.0507	0.093*
O2	1.21461 (18)	0.66102 (9)	0.41079 (17)	0.0588 (4)
O4	1.24232 (16)	0.96417 (9)	0.47291 (15)	0.0527 (4)
O3	1.31065 (17)	0.81470 (9)	0.50578 (16)	0.0521 (4)
H3	1.2783	0.7647	0.4692	0.078*
O1	1.02199 (16)	0.60794 (8)	0.23815 (16)	0.0494 (4)
N1	0.87377 (17)	0.78132 (9)	0.20091 (15)	0.0368 (3)
H1	0.8162	0.7384	0.1529	0.044*
N2	0.95551 (16)	0.91583 (9)	0.28360 (16)	0.0372 (4)
H2	0.9601	0.9752	0.2981	0.045*
O5	0.66848 (18)	0.65027 (9)	0.07026 (18)	0.0638 (5)
H5B	0.5604	0.6549	0.0562	0.096*
H5A	0.6938	0.5927	0.0646	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C4	0.0340 (9)	0.0334 (10)	0.0514 (10)	0.0000 (7)	0.0003 (7)	−0.0017 (8)
C2	0.0306 (8)	0.0264 (8)	0.0464 (9)	0.0013 (6)	−0.0014 (7)	0.0008 (7)
C3	0.0308 (8)	0.0258 (8)	0.0483 (10)	0.0020 (6)	0.0007 (7)	0.0004 (6)
C6	0.0366 (9)	0.0297 (9)	0.0565 (11)	0.0066 (7)	−0.0047 (7)	0.0023 (7)
C1	0.0346 (9)	0.0256 (9)	0.0566 (10)	0.0024 (7)	−0.0013 (7)	0.0012 (7)
C5	0.0336 (9)	0.0260 (8)	0.0499 (10)	0.0017 (7)	−0.0005 (7)	0.0001 (7)
C7	0.0405 (11)	0.0786 (16)	0.0581 (12)	0.0123 (10)	−0.0015 (9)	0.0096 (11)
C8	0.0637 (13)	0.0724 (16)	0.0502 (12)	0.0243 (12)	0.0007 (10)	0.0104 (10)
O2	0.0564 (9)	0.0348 (8)	0.0813 (10)	0.0108 (6)	−0.0258 (7)	0.0023 (6)
O4	0.0521 (8)	0.0331 (7)	0.0711 (9)	−0.0084 (6)	−0.0102 (6)	−0.0041 (6)
O3	0.0438 (8)	0.0372 (7)	0.0725 (9)	0.0015 (6)	−0.0178 (6)	−0.0031 (6)
O1	0.0450 (7)	0.0245 (6)	0.0775 (9)	0.0024 (5)	−0.0040 (6)	−0.0058 (6)
N1	0.0336 (7)	0.0242 (7)	0.0514 (8)	0.0017 (6)	−0.0070 (6)	−0.0022 (6)
N2	0.0334 (8)	0.0205 (7)	0.0570 (9)	0.0013 (5)	−0.0028 (6)	−0.0026 (6)
O5	0.0516 (8)	0.0357 (8)	0.0994 (11)	0.0046 (6)	−0.0323 (8)	−0.0154 (7)

Geometric parameters (Å, º) top

C4—O4	1.221 (2)	C5—N2	1.327 (2)
C4—O3	1.285 (2)	C5—N1	1.333 (2)
C4—C3	1.481 (2)	C7—H7A	0.9600
C2—C3	1.366 (2)	C7—H7B	0.9600
C2—N1	1.374 (2)	C7—H7C	0.9600
C2—C1	1.485 (2)	C8—H8A	0.9600
C3—N2	1.375 (2)	C8—H8B	0.9600
C6—C5	1.489 (2)	C8—H8C	0.9600
C6—C7	1.520 (3)	O3—H3	0.8200
C6—C8	1.526 (3)	N1—H1	0.8600
C6—H6	0.9800	N2—H2	0.8600
C1—O1	1.222 (2)	O5—H5B	0.8500
C1—O2	1.279 (2)	O5—H5A	0.8501

O4—C4—O3	124.60 (17)	C6—C7—H7A	109.5
O4—C4—C3	119.41 (16)	C6—C7—H7B	109.5
O3—C4—C3	115.99 (15)	H7A—C7—H7B	109.5
C3—C2—N1	106.79 (14)	C6—C7—H7C	109.5
C3—C2—C1	133.16 (16)	H7A—C7—H7C	109.5
N1—C2—C1	120.04 (15)	H7B—C7—H7C	109.5
C2—C3—N2	106.13 (14)	C6—C8—H8A	109.5
C2—C3—C4	131.93 (15)	C6—C8—H8B	109.5
N2—C3—C4	121.93 (14)	H8A—C8—H8B	109.5
C5—C6—C7	109.35 (15)	C6—C8—H8C	109.5
C5—C6—C8	111.52 (14)	H8A—C8—H8C	109.5
C7—C6—C8	110.41 (17)	H8B—C8—H8C	109.5
C5—C6—H6	108.5	C4—O3—H3	109.5
C7—C6—H6	108.5	C5—N1—C2	109.54 (14)
C8—C6—H6	108.5	C5—N1—H1	125.2
O1—C1—O2	125.32 (16)	C2—N1—H1	125.2
O1—C1—C2	117.95 (16)	C5—N2—C3	110.08 (14)
O2—C1—C2	116.73 (15)	C5—N2—H2	125.0
N2—C5—N1	107.44 (14)	C3—N2—H2	125.0
N2—C5—C6	126.67 (15)	H5B—O5—H5A	107.5
N1—C5—C6	125.84 (15)

N1—C2—C3—N2	−0.31 (17)	C7—C6—C5—N2	−106.3 (2)
C1—C2—C3—N2	178.46 (17)	C8—C6—C5—N2	131.29 (19)
N1—C2—C3—C4	179.79 (16)	C7—C6—C5—N1	71.0 (2)
C1—C2—C3—C4	−1.4 (3)	C8—C6—C5—N1	−51.3 (2)
O4—C4—C3—C2	175.88 (18)	N2—C5—N1—C2	1.04 (18)
O3—C4—C3—C2	−3.9 (3)	C6—C5—N1—C2	−176.75 (15)
O4—C4—C3—N2	−4.0 (2)	C3—C2—N1—C5	−0.44 (18)
O3—C4—C3—N2	176.25 (16)	C1—C2—N1—C5	−179.40 (15)
C3—C2—C1—O1	−172.81 (18)	N1—C5—N2—C3	−1.24 (18)
N1—C2—C1—O1	5.8 (2)	C6—C5—N2—C3	176.52 (16)
C3—C2—C1—O2	7.7 (3)	C2—C3—N2—C5	0.97 (18)
N1—C2—C1—O2	−173.71 (15)	C4—C3—N2—C5	−179.12 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.64	2.4576 (19)	175
N1—H1···O5	0.86	1.83	2.6879 (19)	171
N2—H2···O1ⁱ	0.86	1.93	2.7619 (19)	162
O5—H5B···O3ⁱⁱ	0.85	2.03	2.8684 (19)	171
O5—H5A···O4ⁱⁱⁱ	0.85	1.94	2.7857 (19)	173

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

Experimental details

Crystal data
Chemical formula	C₈H₁₀N₂O₄·H₂O
M_r	216.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.828 (2), 14.308 (4), 8.930 (2)
β (°)	93.590 (3)
V (Å³)	998.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.40 × 0.32 × 0.28

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.953, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	4874, 2147, 1599
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.06
No. of reflections	2147
No. of parameters	140
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.19

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.64	2.4576 (19)	175
N1—H1···O5	0.86	1.83	2.6879 (19)	171
N2—H2···O1ⁱ	0.86	1.93	2.7619 (19)	162
O5—H5B···O3ⁱⁱ	0.85	2.03	2.8684 (19)	171
O5—H5A···O4ⁱⁱⁱ	0.85	1.94	2.7857 (19)	173

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

Acknowledgements

This work was supported financially by the National Natural Science Foundation of China (No. 1011104).

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