trans-Bis(5-carb­oxy-2-methyl-1H-imidazole-4-carboxyl­ato-κ2N3,O4)copper(II)

Guo, X.; Li, Y.L.; Wang, J.X.; Wang, Y.C.

doi:10.1107/S1600536809016791

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m637

doi:10.1107/S1600536809016791

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trans-Bis(5-carboxy-2-methyl-1H-imidazole-4-carboxylato-κ²N³,O⁴)copper(II)

Xin Guo,^a Yi Liang Li,^a Ju Xian Wang ^a and Yu Cheng Wang ^a ^*

^aInstitute of Medicinal Biotechnology, Chinese Academy of Medical Sciences, and Peking Union Medical College, Beijing 100050, People's Republic of China
^*Correspondence e-mail: hongzhaoupr@yahoo.com

(Received 25 April 2009; accepted 5 May 2009; online 14 May 2009)

In the title compound, [Cu(C₆H₅N₂O₄)₂], the copper(II) atom lies on an inversion centre and is in an N₂O₂ four-coordinate environment with a nearly regular square-planar geometry. An extended network of intramolecular O—H⋯O and intermolecular N—H⋯O and C—H⋯O hydrogen bonds stabilizes the crystal structure.

Related literature

For the synthesis and crystal structure of metal complexes with N-heterocyclic carboxylic acids, see: Nie et al. (2007 ); Liang et al. (2002 ); Net et al. (1989 ); Zeng et al. (2008 ).

Experimental

Crystal data

[Cu(C₆H₅N₂O₄)₂]
M_r = 401.78
Monoclinic, P 2₁ /n
a = 7.3780 (17) Å
b = 7.575 (2) Å
c = 12.863 (3) Å
β = 101.287 (13)°
V = 705.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 292 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.638, T_max = 0.727
5198 measured reflections
1609 independent reflections
1472 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.084
S = 1.07
1609 reflections
116 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱ	0.86	2.01	2.822 (2)	157
C1—H1A⋯O4ⁱⁱ	0.96	2.49	3.217 (2)	132
C1—H1B⋯O3ⁱⁱⁱ	0.96	2.58	3.285 (3)	130
C1—H1C⋯O1^iv	0.96	2.43	3.258 (3)	144
O3—H3A⋯O2	0.91	1.67	2.576 (2)	171
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809016791/rz2318sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016791/rz2318Isup2.hkl

checkCIF report

Comment top

The study of metal complexes with N-heterocyclic carboxylic acids has been given considerable attention ((Nie et al., 2007; Liang et al., 2002; Net et al., 1989; Zeng et al., 2008). In this paper, we report on the synthesis and structure of the title compound, which was obtained by the hydrothermal reaction of CuCl₂with 2-methyl-1H-imidazole-4,5-dicarboxylic acid.

Figure 1 shows the monomeric complex molecule along with the atom-labelling scheme. The copper(II) metal lies on an inversion centre and is in an N₂O₂ four-coordinate environment with a regular square-planar geometry. The Cu—O distance is 1.9633 (15) Å and the Cu—N distance is 1.9830 (14) Å. The five-membered chelating ring assumes an approximately planar conformation (maximum deviation -0.033 (1) Å for atom N1). The crystal structure is stabilized by an intramolecular O—H···O hydrogen bond, and by intermolecular N—H···O and C—H···O hydrogen interactions (Table 1), forming an extended three-dimensional network (Fig. 2).

Related literature top

For the synthesis and crystal structure of metal complexes with N-heterocyclic carboxylic acids, see: Nie et al. (2007); Liang et al. (2002); Net et al. (1989); Zeng et al. (2008).

Experimental top

Blue single crystals of title compound were obtained by hydrothermal treatment of CuCl₂ (1 mmol), 2-methyl-1H-imidazole-4,5-dicarboxylic acid (1 mmol) and water (5 ml) over 2 days at 388 K. Yield: 61% (based on CuCl₂).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with suffix A are generated by the symmetry operation (-x,1 - y,-z).
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Intermolecular hydrogen bonds are shown as dashed lines.

trans-Bis(5-carboxy-2-methyl-1H-imidazole-4-carboxylato-κ²N³,O⁴)copper(II) top

Crystal data top

[Cu(C₆H₅N₂O₄)₂]	F(000) = 406
M_r = 401.78	D_x = 1.893 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2111 reflections
a = 7.3780 (17) Å	θ = 3.1–27.5°
b = 7.575 (2) Å	µ = 1.61 mm⁻¹
c = 12.863 (3) Å	T = 292 K
β = 101.287 (13)°	Prism, blue
V = 705.0 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	1609 independent reflections
Radiation source: fine-focus sealed tube	1472 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→8
T_min = 0.638, T_max = 0.727	l = −16→16
5198 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0506P)² + 0.3299P] where P = (F_o² + 2F_c²)/3
1609 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Cu(C₆H₅N₂O₄)₂]	V = 705.0 (3) Å³
M_r = 401.78	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.3780 (17) Å	µ = 1.61 mm⁻¹
b = 7.575 (2) Å	T = 292 K
c = 12.863 (3) Å	0.30 × 0.25 × 0.20 mm
β = 101.287 (13)°

Data collection top

Rigaku SCXmini diffractometer	1609 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1472 reflections with I > 2σ(I)
T_min = 0.638, T_max = 0.727	R_int = 0.019
5198 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.07	Δρ_max = 0.28 e Å⁻³
1609 reflections	Δρ_min = −0.66 e Å⁻³
116 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
Cu1	0.0000	0.5000	0.0000	0.02591 (14)
C1	0.3363 (3)	0.5580 (3)	0.26068 (15)	0.0322 (4)
H1A	0.4201	0.6562	0.2725	0.048*
H1B	0.3575	0.4828	0.3219	0.048*
H1C	0.2114	0.6005	0.2482	0.048*
C2	0.3672 (2)	0.4571 (3)	0.16737 (14)	0.0222 (4)
C3	0.3316 (2)	0.3269 (2)	0.01393 (13)	0.0211 (3)
C4	0.5089 (2)	0.2949 (2)	0.06414 (13)	0.0221 (4)
C5	0.6677 (3)	0.2144 (3)	0.02784 (15)	0.0267 (4)
C6	0.2221 (2)	0.2795 (3)	−0.09127 (14)	0.0241 (4)
N1	0.24525 (19)	0.4288 (2)	0.07763 (11)	0.0216 (3)
N2	0.5278 (2)	0.3781 (2)	0.16036 (11)	0.0226 (3)
H2A	0.6266	0.3796	0.2086	0.027*
O1	0.06229 (18)	0.3460 (2)	−0.11265 (10)	0.0328 (3)
O2	0.29058 (19)	0.1816 (2)	−0.15194 (10)	0.0325 (3)
O3	0.6306 (2)	0.1289 (2)	−0.06309 (11)	0.0362 (4)
H3A	0.5102	0.1358	−0.0972	0.054*
O4	0.8232 (2)	0.2331 (2)	0.07777 (12)	0.0396 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01512 (18)	0.0374 (2)	0.02196 (19)	0.00490 (12)	−0.00433 (12)	−0.00595 (12)
C1	0.0263 (10)	0.0449 (12)	0.0231 (9)	0.0015 (9)	−0.0008 (7)	−0.0072 (8)
C2	0.0190 (8)	0.0268 (9)	0.0190 (8)	−0.0015 (7)	−0.0004 (6)	0.0029 (7)
C3	0.0172 (8)	0.0242 (9)	0.0205 (8)	−0.0010 (6)	0.0000 (6)	0.0001 (6)
C4	0.0189 (8)	0.0240 (9)	0.0217 (8)	0.0008 (7)	−0.0001 (6)	0.0029 (7)
C5	0.0210 (8)	0.0291 (10)	0.0294 (9)	0.0036 (7)	0.0034 (7)	0.0054 (7)
C6	0.0201 (8)	0.0304 (10)	0.0196 (8)	−0.0010 (7)	−0.0013 (6)	−0.0023 (7)
N1	0.0165 (7)	0.0275 (8)	0.0190 (7)	0.0003 (6)	−0.0013 (5)	−0.0017 (6)
N2	0.0172 (7)	0.0294 (8)	0.0184 (7)	0.0003 (6)	−0.0038 (5)	0.0025 (6)
O1	0.0206 (7)	0.0470 (9)	0.0263 (7)	0.0062 (6)	−0.0065 (5)	−0.0103 (6)
O2	0.0252 (7)	0.0441 (8)	0.0256 (7)	0.0036 (6)	−0.0010 (5)	−0.0113 (6)
O3	0.0273 (7)	0.0465 (9)	0.0342 (8)	0.0079 (6)	0.0047 (6)	−0.0077 (6)
O4	0.0196 (7)	0.0569 (10)	0.0390 (8)	0.0073 (7)	−0.0025 (6)	0.0007 (7)

Geometric parameters (Å, º) top

Cu1—N1	1.9633 (15)	C3—N1	1.370 (2)
Cu1—N1ⁱ	1.9633 (15)	C3—C6	1.478 (2)
Cu1—O1	1.9830 (14)	C4—N2	1.372 (2)
Cu1—O1ⁱ	1.9830 (14)	C4—C5	1.475 (3)
C1—C2	1.478 (3)	C5—O4	1.208 (2)
C1—H1A	0.9600	C5—O3	1.318 (2)
C1—H1B	0.9600	C6—O2	1.252 (2)
C1—H1C	0.9600	C6—O1	1.262 (2)
C2—N1	1.335 (2)	N2—H2A	0.8600
C2—N2	1.346 (2)	O3—H3A	0.9117
C3—C4	1.363 (2)

N1—Cu1—N1ⁱ	180.0	C3—C4—N2	105.31 (15)
N1—Cu1—O1	83.56 (6)	C3—C4—C5	132.21 (17)
N1ⁱ—Cu1—O1	96.44 (6)	N2—C4—C5	121.95 (16)
N1—Cu1—O1ⁱ	96.44 (6)	O4—C5—O3	122.69 (18)
N1ⁱ—Cu1—O1ⁱ	83.56 (6)	O4—C5—C4	120.88 (18)
O1—Cu1—O1ⁱ	180.00 (5)	O3—C5—C4	116.37 (16)
C2—C1—H1A	109.5	O2—C6—O1	125.06 (16)
C2—C1—H1B	109.5	O2—C6—C3	119.96 (16)
H1A—C1—H1B	109.5	O1—C6—C3	114.98 (16)
C2—C1—H1C	109.5	C2—N1—C3	107.11 (14)
H1A—C1—H1C	109.5	C2—N1—Cu1	142.56 (13)
H1B—C1—H1C	109.5	C3—N1—Cu1	109.91 (11)
N1—C2—N2	108.89 (16)	C2—N2—C4	109.26 (14)
N1—C2—C1	126.93 (17)	C2—N2—H2A	125.4
N2—C2—C1	124.18 (16)	C4—N2—H2A	125.4
C4—C3—N1	109.42 (15)	C6—O1—Cu1	114.58 (11)
C4—C3—C6	133.84 (17)	C5—O3—H3A	114.3
N1—C3—C6	116.72 (15)

N1—C3—C4—N2	0.6 (2)	C4—C3—N1—C2	−1.1 (2)
C6—C3—C4—N2	178.80 (19)	C6—C3—N1—C2	−179.58 (16)
N1—C3—C4—C5	−170.85 (19)	C4—C3—N1—Cu1	173.21 (12)
C6—C3—C4—C5	7.3 (4)	C6—C3—N1—Cu1	−5.3 (2)
C3—C4—C5—O4	163.5 (2)	O1—Cu1—N1—C2	175.3 (2)
N2—C4—C5—O4	−6.8 (3)	O1ⁱ—Cu1—N1—C2	−4.7 (2)
C3—C4—C5—O3	−13.6 (3)	O1—Cu1—N1—C3	4.36 (12)
N2—C4—C5—O3	176.04 (17)	O1ⁱ—Cu1—N1—C3	−175.64 (12)
C4—C3—C6—O2	4.4 (3)	N1—C2—N2—C4	−0.7 (2)
N1—C3—C6—O2	−177.58 (17)	C1—C2—N2—C4	179.41 (18)
C4—C3—C6—O1	−174.8 (2)	C3—C4—N2—C2	0.0 (2)
N1—C3—C6—O1	3.2 (3)	C5—C4—N2—C2	172.59 (17)
N2—C2—N1—C3	1.1 (2)	O2—C6—O1—Cu1	−178.45 (16)
C1—C2—N1—C3	−179.04 (19)	C3—C6—O1—Cu1	0.7 (2)
N2—C2—N1—Cu1	−170.06 (15)	N1—Cu1—O1—C6	−2.89 (14)
C1—C2—N1—Cu1	9.8 (4)	N1ⁱ—Cu1—O1—C6	177.11 (14)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱⁱ	0.86	2.01	2.822 (2)	157
C1—H1A···O4ⁱⁱⁱ	0.96	2.49	3.217 (2)	132
C1—H1B···O3^iv	0.96	2.58	3.285 (3)	130
C1—H1C···O1ⁱ	0.96	2.43	3.258 (3)	144
O3—H3A···O2	0.91	1.67	2.576 (2)	171

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

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₅N₂O₄)₂]
M_r	401.78
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	292
a, b, c (Å)	7.3780 (17), 7.575 (2), 12.863 (3)
β (°)	101.287 (13)
V (Å³)	705.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.61
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.638, 0.727
No. of measured, independent and observed [I > 2σ(I)] reflections	5198, 1609, 1472
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.07
No. of reflections	1609
No. of parameters	116
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.66

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱ	0.86	2.01	2.822 (2)	156.5
C1—H1A···O4ⁱⁱ	0.96	2.49	3.217 (2)	132.2
C1—H1B···O3ⁱⁱⁱ	0.96	2.58	3.285 (3)	130.1
C1—H1C···O1^iv	0.96	2.43	3.258 (3)	144.3
O3—H3A···O2	0.91	1.67	2.576 (2)	170.7

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

Acknowledgements

The work was supported by the National Basic Public Welfare Research Program of China (IMBF-20060403).

References

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