3-(4-Carb­oxy-5-carboxyl­ato-1H-imidazol-2-yl)pyridin-1-ium monohydrate

Abstract

In the zwitterionic mol­ecule of the title compound, C₁₀H₇N₃O₄·H₂O, one carboxyl group is deprotonated and the pyridine N atom is protonated. The pyridinium and imidazole rings form a dihedral angle of 5.23 (1)°. An intramolecular O—H⋯O hydrogen bond occurs. In the crystal, inter­molecular N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds link the zwitterions and water mol­ecules into sheets parallel to (102).

Related literature

For the use of 4,5-imidazole­dicarb­oxy­lic acid in coordination chemistry and for related structures, see: Sun et al. (2006 ▶); Chen (2008 ▶); Liu et al. (2009 ▶). For the synthesis of the title compound, see: Lebedev et al. (2007 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₁₀H₇N₃O₄·H₂O

• M _r = 251.20

• Monoclinic,

• a = 3.7342 (18) Å

• b = 16.354 (8) Å

• c = 16.634 (8) Å

• β = 97.019 (10)°

• V = 1008.2 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.14 mm⁻¹

• T = 298 K

• 0.32 × 0.28 × 0.25 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.958, T _max = 0.967

• 5038 measured reflections

• 1777 independent reflections

• 1314 reflections with I > 2σ(I)

• R _int = 0.028

Refinement

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.119

• S = 1.14

• 1777 reflections

• 179 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.18 e Å⁻³

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.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4i	0.98 (2)	1.87 (2)	2.824 (3)	164.8 (16)
N3—H3⋯O1Wii	0.99 (3)	1.66 (3)	2.625 (3)	163 (2)
O1W—H1A⋯O3iii	0.94 (4)	1.84 (4)	2.782 (3)	176 (4)
O1W—H1B⋯O1	0.95 (4)	2.50 (4)	3.032 (3)	115 (3)
O1W—H1B⋯N2	0.95 (4)	1.90 (4)	2.839 (2)	166 (3)
O2—H2⋯O3	0.82	1.67	2.493 (2)	179

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

supplementary crystallographic information

Comment

Imidazole-4,5-dicarboxylic acid derivatives are recognized as efficient N,O-donors exhibiting diverse modes of coordination (Sun et al., 2006; Chen, 2008; Liu et al., 2009). In order to search for new derivatives of imidazole-4,5-dicarboxylic acid, the title compound (I) was synthesized and its crystal structure is reported here.

In (I) (Fig. 1), all bond lengths and angles are normal (Allen et al., 1987). The C4-containing carboxyl group is deprotonated and forms an intramolecular hydrogen bond with the neighboring C1-containing carboxyl group. The dihedral angle formed by imidazole ring and pyridinium ring is 5.23 (1) °. In the crystal structure, intermolecular N—H···O, O—H···N and O—H···O hydrogen bonds (Table 1) link the molecules into sheets parallel to (102) plane (Fig. 2). The short axis a of 3.7342 (18) Å suggests a presence of π-π interactions between the rings from the neighbouring sheets, which consolidate further the crystal packing.

Experimental

The title compound was synthesized according to the method reported in the literature (Lebedev et al., 2007). Yellow single crystals suitable for X-ray diffraction were obtained by slow evaporation of an acetonitrile solution of the compound.

Refinement

H atoms bonded to N and O atoms were located in a difference Fourier map and refined isotropically. C-bound H atoms were placed in calculated positions with C—H = 0.93 Å, and refined as riding, with U_iso(H) = 1.2U_iso(C).

Figures

Fig. 1.

View of (I) showing the atomic numbering and 30% probabilty displacement ellipsoids.

Fig. 2.

Portion of the crystal packing showing the sheet of hydrogen-bonded (dashed lines) molecules.

Crystal data

C10H7N3O4·H2O	F(000) = 520
Mr = 251.20	Dx = 1.655 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1155 reflections
a = 3.7342 (18) Å	θ = 2.5–21.9°
b = 16.354 (8) Å	µ = 0.14 mm−1
c = 16.634 (8) Å	T = 298 K
β = 97.019 (10)°	Block, yellow
V = 1008.2 (8) Å3	0.32 × 0.28 × 0.25 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1777 independent reflections
Radiation source: fine-focus sealed tube	1314 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 25.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −4→4
Tmin = 0.958, Tmax = 0.967	k = −18→19
5038 measured reflections	l = −19→15

Refinement

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0612P)2] where P = (Fo2 + 2Fc2)/3
1777 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.5287 (5)	0.93482 (10)	0.16289 (9)	0.0556 (5)
O2	0.7858 (5)	1.05235 (10)	0.19683 (9)	0.0573 (5)
H2	0.9129	1.0721	0.2357	0.086*
O3	1.1698 (5)	1.11399 (9)	0.31442 (9)	0.0576 (5)
O4	1.4072 (5)	1.07667 (9)	0.43806 (9)	0.0525 (5)
N1	1.1259 (5)	0.92199 (10)	0.41497 (10)	0.0348 (4)
N2	0.7955 (5)	0.86368 (10)	0.31150 (9)	0.0356 (4)
N3	1.0972 (6)	0.70365 (11)	0.55425 (11)	0.0455 (5)
C1	0.7137 (6)	0.97627 (13)	0.21234 (13)	0.0415 (6)
C2	0.8660 (6)	0.94325 (12)	0.29214 (11)	0.0347 (5)
C3	1.0711 (5)	0.98027 (11)	0.35661 (11)	0.0335 (5)
C4	1.2301 (6)	1.06322 (12)	0.37174 (12)	0.0391 (5)
C5	0.9577 (6)	0.85300 (11)	0.38601 (11)	0.0329 (5)
C6	0.9521 (6)	0.77649 (12)	0.43184 (12)	0.0338 (5)
C7	1.1011 (6)	0.77284 (13)	0.51242 (12)	0.0396 (5)
H7	1.2050	0.8194	0.5375	0.047*
C8	0.7973 (6)	0.70592 (13)	0.39780 (13)	0.0424 (6)
H8	0.6916	0.7062	0.3442	0.051*
C9	0.7986 (7)	0.63518 (13)	0.44279 (13)	0.0466 (6)
H9	0.6945	0.5877	0.4197	0.056*
C10	0.9544 (7)	0.63514 (14)	0.52181 (13)	0.0478 (6)
H10	0.9599	0.5875	0.5524	0.057*
O1W	0.4229 (6)	0.75493 (12)	0.19730 (11)	0.0711 (6)
H1	1.271 (5)	0.9320 (11)	0.4672 (12)	0.032 (5)*
H3	1.211 (8)	0.7089 (16)	0.6111 (18)	0.080 (9)*
H1B	0.556 (12)	0.797 (2)	0.228 (2)	0.143 (15)*
H1A	0.570 (11)	0.709 (2)	0.193 (2)	0.122 (13)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0640 (12)	0.0629 (10)	0.0351 (9)	−0.0017 (9)	−0.0135 (8)	−0.0030 (7)
O2	0.0700 (13)	0.0532 (10)	0.0441 (9)	−0.0053 (9)	−0.0114 (8)	0.0136 (7)
O3	0.0715 (13)	0.0442 (9)	0.0524 (10)	−0.0060 (8)	−0.0111 (9)	0.0120 (8)
O4	0.0650 (12)	0.0457 (9)	0.0419 (9)	−0.0067 (8)	−0.0127 (8)	−0.0030 (7)
N1	0.0393 (11)	0.0355 (9)	0.0286 (9)	−0.0006 (8)	0.0004 (8)	−0.0026 (7)
N2	0.0354 (11)	0.0405 (10)	0.0298 (9)	0.0014 (8)	−0.0001 (8)	−0.0026 (7)
N3	0.0547 (14)	0.0490 (11)	0.0312 (10)	0.0002 (9)	−0.0017 (9)	0.0036 (9)
C1	0.0408 (14)	0.0468 (13)	0.0363 (12)	0.0044 (11)	0.0021 (10)	−0.0003 (10)
C2	0.0340 (13)	0.0389 (11)	0.0313 (11)	0.0053 (9)	0.0048 (9)	0.0008 (9)
C3	0.0330 (12)	0.0355 (11)	0.0314 (10)	0.0047 (9)	0.0018 (9)	−0.0015 (9)
C4	0.0400 (14)	0.0394 (12)	0.0373 (12)	0.0049 (10)	0.0021 (10)	0.0019 (10)
C5	0.0331 (12)	0.0358 (11)	0.0292 (10)	0.0027 (9)	0.0013 (9)	−0.0044 (8)
C6	0.0296 (12)	0.0385 (11)	0.0331 (11)	0.0028 (9)	0.0027 (9)	−0.0015 (9)
C7	0.0409 (14)	0.0401 (12)	0.0366 (12)	−0.0007 (10)	0.0005 (10)	−0.0009 (9)
C8	0.0451 (15)	0.0466 (12)	0.0337 (12)	−0.0034 (10)	−0.0027 (10)	−0.0026 (10)
C9	0.0492 (15)	0.0401 (12)	0.0501 (14)	−0.0070 (11)	0.0045 (11)	−0.0059 (10)
C10	0.0524 (16)	0.0460 (13)	0.0447 (14)	−0.0051 (11)	0.0044 (12)	0.0052 (10)
O1W	0.1032 (17)	0.0470 (11)	0.0534 (11)	0.0091 (11)	−0.0304 (11)	−0.0099 (8)

Geometric parameters (Å, °)

O1—C1	1.214 (2)	C2—C3	1.379 (3)
O2—C1	1.305 (3)	C3—C4	1.490 (3)
O2—H2	0.8201	C5—C6	1.467 (3)
O3—C4	1.264 (2)	C6—C8	1.381 (3)
O4—C4	1.235 (2)	C6—C7	1.388 (3)
N1—C5	1.351 (2)	C7—H7	0.9300
N1—C3	1.358 (3)	C8—C9	1.377 (3)
N1—H1	0.98 (2)	C8—H8	0.9300
N2—C5	1.323 (2)	C9—C10	1.371 (3)
N2—C2	1.374 (3)	C9—H9	0.9300
N3—C10	1.327 (3)	C10—H10	0.9300
N3—C7	1.329 (3)	O1W—H1B	0.95 (4)
N3—H3	0.99 (3)	O1W—H1A	0.94 (4)
C1—C2	1.481 (3)
C1—O2—H2	109.5	N2—C5—N1	111.31 (17)
C5—N1—C3	107.96 (17)	N2—C5—C6	124.45 (18)
C5—N1—H1	129.6 (10)	N1—C5—C6	124.24 (17)
C3—N1—H1	122.4 (11)	C8—C6—C7	117.27 (19)
C5—N2—C2	105.42 (16)	C8—C6—C5	122.13 (18)
C10—N3—C7	122.4 (2)	C7—C6—C5	120.60 (18)
C10—N3—H3	124.4 (16)	N3—C7—C6	120.88 (19)
C7—N3—H3	113.2 (16)	N3—C7—H7	119.6
O1—C1—O2	120.8 (2)	C6—C7—H7	119.6
O1—C1—C2	121.9 (2)	C9—C8—C6	120.4 (2)
O2—C1—C2	117.32 (19)	C9—C8—H8	119.8
N2—C2—C3	109.74 (17)	C6—C8—H8	119.8
N2—C2—C1	119.47 (18)	C10—C9—C8	119.6 (2)
C3—C2—C1	130.76 (19)	C10—C9—H9	120.2
N1—C3—C2	105.58 (17)	C8—C9—H9	120.2
N1—C3—C4	119.74 (17)	N3—C10—C9	119.5 (2)
C2—C3—C4	134.67 (18)	N3—C10—H10	120.3
O4—C4—O3	125.7 (2)	C9—C10—H10	120.3
O4—C4—C3	118.17 (18)	H1B—O1W—H1A	110 (4)
O3—C4—C3	116.11 (18)
C5—N2—C2—C3	−0.5 (2)	C2—N2—C5—N1	0.3 (2)
C5—N2—C2—C1	−178.48 (19)	C2—N2—C5—C6	179.57 (19)
O1—C1—C2—N2	−0.4 (3)	C3—N1—C5—N2	−0.1 (2)
O2—C1—C2—N2	179.53 (19)	C3—N1—C5—C6	−179.32 (19)
O1—C1—C2—C3	−178.0 (2)	N2—C5—C6—C8	5.3 (3)
O2—C1—C2—C3	2.0 (4)	N1—C5—C6—C8	−175.5 (2)
C5—N1—C3—C2	−0.2 (2)	N2—C5—C6—C7	−174.0 (2)
C5—N1—C3—C4	−179.47 (18)	N1—C5—C6—C7	5.2 (3)
N2—C2—C3—N1	0.4 (2)	C10—N3—C7—C6	0.3 (3)
C1—C2—C3—N1	178.2 (2)	C8—C6—C7—N3	0.8 (3)
N2—C2—C3—C4	179.5 (2)	C5—C6—C7—N3	−179.91 (19)
C1—C2—C3—C4	−2.8 (4)	C7—C6—C8—C9	−0.9 (3)
N1—C3—C4—O4	−0.5 (3)	C5—C6—C8—C9	179.8 (2)
C2—C3—C4—O4	−179.5 (2)	C6—C8—C9—C10	0.1 (3)
N1—C3—C4—O3	179.49 (19)	C7—N3—C10—C9	−1.2 (4)
C2—C3—C4—O3	0.5 (4)	C8—C9—C10—N3	1.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4i	0.98 (2)	1.87 (2)	2.824 (3)	164.8 (16)
N3—H3···O1Wii	0.99 (3)	1.66 (3)	2.625 (3)	163 (2)
O1W—H1A···O3iii	0.94 (4)	1.84 (4)	2.782 (3)	176 (4)
O1W—H1B···O1	0.95 (4)	2.50 (4)	3.032 (3)	115 (3)
O1W—H1B···N2	0.95 (4)	1.90 (4)	2.839 (2)	166 (3)
O2—H2···O3	0.82	1.67	2.493 (2)	179

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