Dimethyl­ammonium 5-carb­oxy-2-(1-oxo-1λ⁵-pyridin-2-yl)-1H-imidazole-4-car­box­yl­ate

Abstract

In the title salt, C₂H₈N⁺·C₁₀H₆N₃O₅ ⁻, the imidazole­carboxyl­ate anion is essentially planar [maximum deviation from the least-squares plane = 0.046 (5) Å], with a dihedral angle between the rings of 2.7 (2)°. This conformation is maintained by the presence of both intra­molecular carb­oxy–carboxyl­ate O—H⋯O and imidazole–oxide N—H⋯O hydrogen bonds. Iin the crystal, cation–carboxyl­ate N—H⋯O and cation–imidazole N—H⋯N hydrogen bonds result in chains along the b axis.

Related literature  

For the structures of compounds with similar ligands, see: Chen (2008 ▶; Chen et al. (2011 ▶); Sun et al. (2005 ▶). For the synthesis of the ligand, see: Sun et al. (2006 ▶).

Experimental  

Crystal data  

• C₂H₈N⁺·C₁₀H₆N₃O₅ ⁻

• M _r = 294.27

• Monoclinic,

• a = 10.9690 (18) Å

• b = 17.305 (3) Å

• c = 8.0160 (13) Å

• β = 120.901 (2)°

• V = 1305.6 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 298 K

• 0.32 × 0.28 × 0.26 mm

Data collection  

• Bruker APEXII area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.963, T _max = 0.970

• 3782 measured reflections

• 1419 independent reflections

• 1204 reflections with I > 2σ(I)

• R _int = 0.025

Refinement  

• R[F ² > 2σ(F ²)] = 0.036

• wR(F ²) = 0.085

• S = 1.05

• 1419 reflections

• 193 parameters

• 2 restraints

• H-atom parameters constrained

• Δρ_max = 0.14 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812033557/zs2224Isup3.mol

Supplementary material file. DOI: 10.1107/S1600536812033557/zs2224Isup4.cml

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
N4—H4B⋯N1i	0.90	2.49	3.166 (3)	132
N4—H4B⋯O1i	0.90	2.11	2.933 (3)	151
N4—H4A⋯O1ii	0.90	1.95	2.806 (3)	159
O3—H3⋯O2	0.82	1.64	2.455 (3)	170
N2—H2⋯O5	0.86	2.06	2.603 (3)	120

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Imidazole-4,5-dicarboxylic acid and its derivatives have a variety of coordination modes as ligands in the formation of metal complexes (Chen, 2008; Sun et al., 2005), which include those with the lanthanide metals (Chen et al., 2011). In the title salt, C₂ H₈N⁺ C₁₀H₆N₃O₅^-, (Fig. 1), which consists of a dimethylammonium cation and a 5-carboxy-2-(2-pyridyl-N-oxide)-1H-imidazole-4-carboxylate anion, the anion is essentially planar [maximum deviation from the l.s. plane = 0.046 (5) Å], with the dihedral angle between the rings of 2.7 (2)Å. This conformation is maintained by the presence of both intramolecular carboxyl O—H···O and imidazole N—H···O_oxide hydrogen bonds while intermolecular cation N—H···O_carboxyl and N—H···N_imidazole hydrogen bonds (Table 1) give a one-dimensional chain structure.

Experimental

The ligand,(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide was prepared by the method reported in the literature (Sun et al., 2006). A diluted dimethylamine aqueous solution was added dropwise to an ethanolic solution of the ligand until the pH reached 7.4. Crystals of the title compound suitable for X-ray analysis were obtained after a few days of slow evaporation of the solvent.

Refinement

Hydrogen atoms were placed at calculated positions (C—H = 0.95–0.99 Å, N—H = 0.90 Å and O—H = 0.82 Å) and were treated as riding on their parent atoms, with U_iso(H) = 1.2–1.5U_eq(C, N, O). In the absence of a suitable heavy atom, Friedel pairs were averaged in the refinement.

Figures

Fig. 1.

Molecular conformation and atom-numbering scheme for the title compound, with displacement ellipsoids drawn at the 50% probability level.

Crystal data

C2H8N+·C10H6N3O5−	F(000) = 616
Mr = 294.27	Dx = 1.497 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3600 reflections
a = 10.9690 (18) Å	θ = 1.3–28.0°
b = 17.305 (3) Å	µ = 0.12 mm−1
c = 8.0160 (13) Å	T = 298 K
β = 120.901 (2)°	Block, colourless
V = 1305.6 (4) Å3	0.32 × 0.28 × 0.26 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	1419 independent reflections
Radiation source: fine-focus sealed tube	1204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→12
Tmin = 0.963, Tmax = 0.970	k = −19→21
3782 measured reflections	l = −8→10

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0423P)2P] where P = (Fo2 + 2Fc2)/3
1419 reflections	(Δ/σ)max < 0.001
193 parameters	Δρmax = 0.14 e Å−3
2 restraints	Δρmin = −0.19 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
C1	0.8048 (3)	0.88560 (14)	0.6235 (4)	0.0435 (6)
C2	0.6875 (3)	0.92371 (14)	0.4485 (4)	0.0399 (6)
C3	0.6630 (3)	1.00178 (15)	0.4067 (4)	0.0405 (6)
C4	0.7352 (3)	1.07430 (16)	0.5114 (4)	0.0462 (7)
C5	0.4999 (3)	0.93154 (13)	0.1662 (4)	0.0392 (6)
C6	0.3776 (3)	0.90945 (15)	−0.0207 (4)	0.0408 (6)
C7	0.3453 (3)	0.83297 (16)	−0.0743 (4)	0.0504 (7)
H7	0.4041	0.7945	0.0095	0.060*
C8	0.2281 (4)	0.81248 (17)	−0.2486 (5)	0.0581 (8)
H8	0.2074	0.7607	−0.2825	0.070*
C9	0.1414 (3)	0.86974 (19)	−0.3729 (4)	0.0578 (8)
H9	0.0610	0.8570	−0.4910	0.069*
C10	0.1752 (4)	0.94533 (19)	−0.3202 (5)	0.0584 (8)
H10	0.1173	0.9838	−0.4047	0.070*
C11	0.1058 (4)	0.83037 (18)	0.1270 (5)	0.0663 (9)
H11A	0.0357	0.8668	0.1150	0.099*
H11B	0.1698	0.8554	0.0960	0.099*
H11C	0.1580	0.8113	0.2580	0.099*
C12	−0.0512 (4)	0.71875 (19)	0.0443 (6)	0.0688 (9)
H12A	0.0075	0.6984	0.1731	0.103*
H12B	−0.0929	0.6769	−0.0464	0.103*
H12C	−0.1250	0.7501	0.0399	0.103*
N1	0.5853 (3)	0.88073 (11)	0.2989 (4)	0.0414 (5)
N2	0.5433 (2)	1.00487 (12)	0.2268 (3)	0.0418 (5)
H2	0.5024	1.0462	0.1629	0.050*
N3	0.2913 (2)	0.96589 (13)	−0.1477 (3)	0.0468 (6)
N4	0.0354 (3)	0.76580 (12)	−0.0071 (4)	0.0483 (5)
H4A	−0.0202	0.7846	−0.1280	0.058*
H4B	0.1019	0.7356	−0.0080	0.058*
O1	0.8070 (2)	0.81390 (9)	0.6329 (3)	0.0522 (5)
O2	0.8994 (2)	0.92884 (11)	0.7573 (3)	0.0584 (6)
O3	0.8499 (2)	1.06669 (12)	0.6792 (3)	0.0583 (6)
H3	0.8722	1.0209	0.6990	0.087*
O4	0.6859 (3)	1.13664 (11)	0.4385 (4)	0.0669 (6)
O5	0.3198 (3)	1.03909 (11)	−0.1066 (3)	0.0666 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0445 (15)	0.0422 (14)	0.0441 (15)	0.0006 (13)	0.0229 (13)	0.0027 (13)
C2	0.0444 (15)	0.0369 (13)	0.0429 (15)	0.0007 (13)	0.0256 (13)	0.0014 (13)
C3	0.0437 (16)	0.0379 (13)	0.0433 (16)	−0.0040 (11)	0.0249 (14)	−0.0003 (11)
C4	0.0520 (19)	0.0372 (16)	0.0480 (18)	−0.0081 (12)	0.0248 (16)	−0.0012 (12)
C5	0.0427 (16)	0.0351 (14)	0.0415 (16)	−0.0004 (11)	0.0227 (14)	0.0032 (12)
C6	0.0405 (15)	0.0405 (13)	0.0404 (15)	−0.0010 (12)	0.0199 (13)	0.0046 (12)
C7	0.0578 (19)	0.0426 (14)	0.0482 (18)	−0.0033 (13)	0.0253 (17)	0.0002 (13)
C8	0.067 (2)	0.0522 (18)	0.0520 (18)	−0.0110 (16)	0.0279 (17)	−0.0071 (15)
C9	0.053 (2)	0.067 (2)	0.0443 (18)	−0.0098 (16)	0.0188 (16)	−0.0052 (15)
C10	0.0516 (19)	0.065 (2)	0.0466 (17)	0.0030 (16)	0.0167 (15)	0.0110 (15)
C11	0.0513 (19)	0.0587 (19)	0.067 (2)	0.0029 (15)	0.0145 (17)	−0.0142 (17)
C12	0.057 (2)	0.059 (2)	0.078 (2)	0.0050 (15)	0.0259 (19)	0.0192 (17)
N1	0.0419 (12)	0.0355 (11)	0.0410 (12)	−0.0004 (9)	0.0170 (10)	0.0029 (10)
N2	0.0450 (13)	0.0328 (11)	0.0447 (13)	0.0004 (9)	0.0211 (11)	0.0060 (9)
N3	0.0454 (14)	0.0442 (13)	0.0453 (14)	0.0005 (11)	0.0194 (13)	0.0065 (11)
N4	0.0450 (13)	0.0410 (12)	0.0476 (12)	0.0066 (10)	0.0157 (11)	0.0004 (11)
O1	0.0579 (12)	0.0383 (10)	0.0505 (12)	0.0056 (10)	0.0208 (11)	0.0057 (9)
O2	0.0515 (14)	0.0500 (13)	0.0542 (14)	−0.0042 (10)	0.0131 (12)	0.0017 (10)
O3	0.0610 (14)	0.0452 (12)	0.0562 (13)	−0.0110 (10)	0.0212 (12)	−0.0028 (10)
O4	0.0746 (16)	0.0372 (10)	0.0702 (15)	−0.0051 (12)	0.0238 (13)	0.0021 (11)
O5	0.0696 (15)	0.0361 (11)	0.0670 (15)	0.0016 (10)	0.0157 (13)	0.0075 (10)

Geometric parameters (Å, º)

C1—O1	1.243 (3)	C9—C10	1.366 (4)
C1—O2	1.282 (3)	C9—H9	0.9300
C1—C2	1.485 (4)	C10—N3	1.361 (4)
C2—N1	1.367 (4)	C10—H10	0.9300
C2—C3	1.385 (4)	C11—N4	1.465 (4)
C3—N2	1.364 (3)	C11—H11A	0.9600
C3—C4	1.491 (4)	C11—H11B	0.9600
C4—O4	1.214 (3)	C11—H11C	0.9600
C4—O3	1.293 (4)	C12—N4	1.462 (4)
C5—N1	1.326 (3)	C12—H12A	0.9600
C5—N2	1.355 (3)	C12—H12B	0.9600
C5—C6	1.458 (4)	C12—H12C	0.9600
C6—N3	1.377 (3)	N2—H2	0.8600
C6—C7	1.380 (4)	N3—O5	1.306 (3)
C7—C8	1.373 (5)	N4—H4A	0.9000
C7—H7	0.9300	N4—H4B	0.9000
C8—C9	1.380 (4)	O3—H3	0.8200
C8—H8	0.9300
O1—C1—O2	123.4 (3)	N3—C10—H10	119.1
O1—C1—C2	118.8 (3)	C9—C10—H10	119.1
O2—C1—C2	117.9 (2)	N4—C11—H11A	109.5
N1—C2—C3	110.4 (3)	N4—C11—H11B	109.5
N1—C2—C1	120.7 (2)	H11A—C11—H11B	109.5
C3—C2—C1	128.9 (3)	N4—C11—H11C	109.5
N2—C3—C2	104.8 (2)	H11A—C11—H11C	109.5
N2—C3—C4	120.4 (2)	H11B—C11—H11C	109.5
C2—C3—C4	134.7 (3)	N4—C12—H12A	109.5
O4—C4—O3	123.1 (3)	N4—C12—H12B	109.5
O4—C4—C3	120.0 (3)	H12A—C12—H12B	109.5
O3—C4—C3	116.8 (3)	N4—C12—H12C	109.5
N1—C5—N2	111.1 (2)	H12A—C12—H12C	109.5
N1—C5—C6	123.3 (2)	H12B—C12—H12C	109.5
N2—C5—C6	125.6 (2)	C5—N1—C2	105.44 (19)
N3—C6—C7	118.8 (3)	C5—N2—C3	108.2 (2)
N3—C6—C5	119.6 (2)	C5—N2—H2	125.9
C7—C6—C5	121.6 (3)	C3—N2—H2	125.9
C8—C7—C6	121.4 (3)	O5—N3—C10	119.2 (2)
C8—C7—H7	119.3	O5—N3—C6	121.1 (2)
C6—C7—H7	119.3	C10—N3—C6	119.7 (2)
C7—C8—C9	119.1 (3)	C12—N4—C11	113.1 (3)
C7—C8—H8	120.4	C12—N4—H4A	109.0
C9—C8—H8	120.4	C11—N4—H4A	109.0
C10—C9—C8	119.2 (3)	C12—N4—H4B	109.0
C10—C9—H9	120.4	C11—N4—H4B	109.0
C8—C9—H9	120.4	H4A—N4—H4B	107.8
N3—C10—C9	121.9 (3)	C4—O3—H3	109.5
O1—C1—C2—N1	−1.3 (4)	C6—C7—C8—C9	0.3 (4)
O2—C1—C2—N1	178.4 (2)	C7—C8—C9—C10	0.7 (5)
O1—C1—C2—C3	179.8 (3)	C8—C9—C10—N3	−0.6 (5)
O2—C1—C2—C3	−0.6 (4)	N2—C5—N1—C2	−0.6 (3)
N1—C2—C3—N2	−0.3 (3)	C6—C5—N1—C2	178.4 (2)
C1—C2—C3—N2	178.8 (2)	C3—C2—N1—C5	0.6 (3)
N1—C2—C3—C4	179.4 (3)	C1—C2—N1—C5	−178.6 (2)
C1—C2—C3—C4	−1.5 (5)	N1—C5—N2—C3	0.5 (3)
N2—C3—C4—O4	1.6 (4)	C6—C5—N2—C3	−178.6 (2)
C2—C3—C4—O4	−178.0 (3)	C2—C3—N2—C5	−0.1 (2)
N2—C3—C4—O3	−178.4 (2)	C4—C3—N2—C5	−179.8 (2)
C2—C3—C4—O3	2.0 (4)	C9—C10—N3—O5	178.8 (3)
N1—C5—C6—N3	177.7 (2)	C9—C10—N3—C6	−0.4 (4)
N2—C5—C6—N3	−3.4 (4)	C7—C6—N3—O5	−177.8 (2)
N1—C5—C6—C7	−2.2 (4)	C5—C6—N3—O5	2.3 (3)
N2—C5—C6—C7	176.7 (3)	C7—C6—N3—C10	1.4 (4)
N3—C6—C7—C8	−1.4 (4)	C5—C6—N3—C10	−178.5 (2)
C5—C6—C7—C8	178.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N1i	0.90	2.49	3.166 (3)	132
N4—H4B···O1i	0.90	2.11	2.933 (3)	151
N4—H4A···O1ii	0.90	1.95	2.806 (3)	159
O3—H3···O2	0.82	1.64	2.455 (3)	170
N2—H2···O5	0.86	2.06	2.603 (3)	120

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