metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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[Nie, X.-L., Wen, H.-L., Wu, Z.-S., Liu, D.-B. & Liu, C.-B. (2007). Acta Cryst. E63, m753-m755.]); Liang et al. (2002[Liang, Y. C., Cao, R. & Hong, M. C. (2002). Inorg. Chem. Commun. 5, 366-368.]); Net et al. (1989[Net, G., Bayon, J. C., Butler, W. M. & Rasmussen, P. (1989). J. Chem. Soc. Chem. Commun. pp. 1022-1023.]); Zeng et al. (2008[Zeng, J.-Z., Yi, X.-G., Lin, J.-Y., Ying, S.-M. & Huang, G.-S. (2008). Acta Cryst. E64, m476.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C6H5N2O4)2]

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.638, Tmax = 0.727

  • 5198 measured reflections

  • 1609 independent reflections

  • 1472 reflections with I > 2σ(I)

  • Rint = 0.019

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.084

  • S = 1.07

  • 1609 reflections

  • 116 parameters

  • H-atom parameters constrained

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.66 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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⋯O1iv 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL/PC (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL/PC.

Supporting information


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 CuCl2 with 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).

Refinement top

The hydroxyl H atom was located from a difference Fourier map but not refined [Uiso(H)=1.5Ueq(O)]. All other H atoms were placed at calculated positions and refined as riding, with C—H = 0.96 Å, N—H = 0.86 Å, and with Uiso(H)=1.5Ueq(C) and Uiso(H)=1.2Ueq(N)

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
[Figure 1] 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).
[Figure 2] 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
Mr = 401.78Dx = 1.893 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2111 reflections
a = 7.3780 (17) Åθ = 3.1–27.5°
b = 7.575 (2) ŵ = 1.61 mm1
c = 12.863 (3) ÅT = 292 K
β = 101.287 (13)°Prism, blue
V = 705.0 (3) Å30.30 × 0.25 × 0.20 mm
Z = 2
Data collection top
Rigaku SCXmini
diffractometer
1609 independent reflections
Radiation source: fine-focus sealed tube1472 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = 99
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 98
Tmin = 0.638, Tmax = 0.727l = 1616
5198 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0506P)2 + 0.3299P]
where P = (Fo2 + 2Fc2)/3
1609 reflections(Δ/σ)max < 0.001
116 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.66 e Å3
Crystal data top
[Cu(C6H5N2O4)2]V = 705.0 (3) Å3
Mr = 401.78Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.3780 (17) ŵ = 1.61 mm1
b = 7.575 (2) ÅT = 292 K
c = 12.863 (3) Å0.30 × 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)
Tmin = 0.638, Tmax = 0.727Rint = 0.019
5198 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.084H-atom parameters constrained
S = 1.07Δρmax = 0.28 e Å3
1609 reflectionsΔρmin = 0.66 e Å3
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
xyzUiso*/Ueq
Cu10.00000.50000.00000.02591 (14)
C10.3363 (3)0.5580 (3)0.26068 (15)0.0322 (4)
H1A0.42010.65620.27250.048*
H1B0.35750.48280.32190.048*
H1C0.21140.60050.24820.048*
C20.3672 (2)0.4571 (3)0.16737 (14)0.0222 (4)
C30.3316 (2)0.3269 (2)0.01393 (13)0.0211 (3)
C40.5089 (2)0.2949 (2)0.06414 (13)0.0221 (4)
C50.6677 (3)0.2144 (3)0.02784 (15)0.0267 (4)
C60.2221 (2)0.2795 (3)0.09127 (14)0.0241 (4)
N10.24525 (19)0.4288 (2)0.07763 (11)0.0216 (3)
N20.5278 (2)0.3781 (2)0.16036 (11)0.0226 (3)
H2A0.62660.37960.20860.027*
O10.06229 (18)0.3460 (2)0.11265 (10)0.0328 (3)
O20.29058 (19)0.1816 (2)0.15194 (10)0.0325 (3)
O30.6306 (2)0.1289 (2)0.06309 (11)0.0362 (4)
H3A0.51020.13580.09720.054*
O40.8232 (2)0.2331 (2)0.07777 (12)0.0396 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01512 (18)0.0374 (2)0.02196 (19)0.00490 (12)0.00433 (12)0.00595 (12)
C10.0263 (10)0.0449 (12)0.0231 (9)0.0015 (9)0.0008 (7)0.0072 (8)
C20.0190 (8)0.0268 (9)0.0190 (8)0.0015 (7)0.0004 (6)0.0029 (7)
C30.0172 (8)0.0242 (9)0.0205 (8)0.0010 (6)0.0000 (6)0.0001 (6)
C40.0189 (8)0.0240 (9)0.0217 (8)0.0008 (7)0.0001 (6)0.0029 (7)
C50.0210 (8)0.0291 (10)0.0294 (9)0.0036 (7)0.0034 (7)0.0054 (7)
C60.0201 (8)0.0304 (10)0.0196 (8)0.0010 (7)0.0013 (6)0.0023 (7)
N10.0165 (7)0.0275 (8)0.0190 (7)0.0003 (6)0.0013 (5)0.0017 (6)
N20.0172 (7)0.0294 (8)0.0184 (7)0.0003 (6)0.0038 (5)0.0025 (6)
O10.0206 (7)0.0470 (9)0.0263 (7)0.0062 (6)0.0065 (5)0.0103 (6)
O20.0252 (7)0.0441 (8)0.0256 (7)0.0036 (6)0.0010 (5)0.0113 (6)
O30.0273 (7)0.0465 (9)0.0342 (8)0.0079 (6)0.0047 (6)0.0077 (6)
O40.0196 (7)0.0569 (10)0.0390 (8)0.0073 (7)0.0025 (6)0.0007 (7)
Geometric parameters (Å, º) top
Cu1—N11.9633 (15)C3—N11.370 (2)
Cu1—N1i1.9633 (15)C3—C61.478 (2)
Cu1—O11.9830 (14)C4—N21.372 (2)
Cu1—O1i1.9830 (14)C4—C51.475 (3)
C1—C21.478 (3)C5—O41.208 (2)
C1—H1A0.9600C5—O31.318 (2)
C1—H1B0.9600C6—O21.252 (2)
C1—H1C0.9600C6—O11.262 (2)
C2—N11.335 (2)N2—H2A0.8600
C2—N21.346 (2)O3—H3A0.9117
C3—C41.363 (2)
N1—Cu1—N1i180.0C3—C4—N2105.31 (15)
N1—Cu1—O183.56 (6)C3—C4—C5132.21 (17)
N1i—Cu1—O196.44 (6)N2—C4—C5121.95 (16)
N1—Cu1—O1i96.44 (6)O4—C5—O3122.69 (18)
N1i—Cu1—O1i83.56 (6)O4—C5—C4120.88 (18)
O1—Cu1—O1i180.00 (5)O3—C5—C4116.37 (16)
C2—C1—H1A109.5O2—C6—O1125.06 (16)
C2—C1—H1B109.5O2—C6—C3119.96 (16)
H1A—C1—H1B109.5O1—C6—C3114.98 (16)
C2—C1—H1C109.5C2—N1—C3107.11 (14)
H1A—C1—H1C109.5C2—N1—Cu1142.56 (13)
H1B—C1—H1C109.5C3—N1—Cu1109.91 (11)
N1—C2—N2108.89 (16)C2—N2—C4109.26 (14)
N1—C2—C1126.93 (17)C2—N2—H2A125.4
N2—C2—C1124.18 (16)C4—N2—H2A125.4
C4—C3—N1109.42 (15)C6—O1—Cu1114.58 (11)
C4—C3—C6133.84 (17)C5—O3—H3A114.3
N1—C3—C6116.72 (15)
N1—C3—C4—N20.6 (2)C4—C3—N1—C21.1 (2)
C6—C3—C4—N2178.80 (19)C6—C3—N1—C2179.58 (16)
N1—C3—C4—C5170.85 (19)C4—C3—N1—Cu1173.21 (12)
C6—C3—C4—C57.3 (4)C6—C3—N1—Cu15.3 (2)
C3—C4—C5—O4163.5 (2)O1—Cu1—N1—C2175.3 (2)
N2—C4—C5—O46.8 (3)O1i—Cu1—N1—C24.7 (2)
C3—C4—C5—O313.6 (3)O1—Cu1—N1—C34.36 (12)
N2—C4—C5—O3176.04 (17)O1i—Cu1—N1—C3175.64 (12)
C4—C3—C6—O24.4 (3)N1—C2—N2—C40.7 (2)
N1—C3—C6—O2177.58 (17)C1—C2—N2—C4179.41 (18)
C4—C3—C6—O1174.8 (2)C3—C4—N2—C20.0 (2)
N1—C3—C6—O13.2 (3)C5—C4—N2—C2172.59 (17)
N2—C2—N1—C31.1 (2)O2—C6—O1—Cu1178.45 (16)
C1—C2—N1—C3179.04 (19)C3—C6—O1—Cu10.7 (2)
N2—C2—N1—Cu1170.06 (15)N1—Cu1—O1—C62.89 (14)
C1—C2—N1—Cu19.8 (4)N1i—Cu1—O1—C6177.11 (14)
Symmetry code: (i) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O2ii0.862.012.822 (2)157
C1—H1A···O4iii0.962.493.217 (2)132
C1—H1B···O3iv0.962.583.285 (3)130
C1—H1C···O1i0.962.433.258 (3)144
O3—H3A···O20.911.672.576 (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) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu(C6H5N2O4)2]
Mr401.78
Crystal system, space groupMonoclinic, P21/n
Temperature (K)292
a, b, c (Å)7.3780 (17), 7.575 (2), 12.863 (3)
β (°) 101.287 (13)
V3)705.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)1.61
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.638, 0.727
No. of measured, independent and
observed [I > 2σ(I)] reflections
5198, 1609, 1472
Rint0.019
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.084, 1.07
No. of reflections1609
No. of parameters116
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···O2i0.862.012.822 (2)156.5
C1—H1A···O4ii0.962.493.217 (2)132.2
C1—H1B···O3iii0.962.583.285 (3)130.1
C1—H1C···O1iv0.962.433.258 (3)144.3
O3—H3A···O20.911.672.576 (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) x1/2, 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

First citationLiang, Y. C., Cao, R. & Hong, M. C. (2002). Inorg. Chem. Commun. 5, 366–368.  Web of Science CSD CrossRef CAS Google Scholar
First citationNet, G., Bayon, J. C., Butler, W. M. & Rasmussen, P. (1989). J. Chem. Soc. Chem. Commun. pp. 1022–1023.  CrossRef Web of Science Google Scholar
First citationNie, X.-L., Wen, H.-L., Wu, Z.-S., Liu, D.-B. & Liu, C.-B. (2007). Acta Cryst. E63, m753–m755.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZeng, J.-Z., Yi, X.-G., Lin, J.-Y., Ying, S.-M. & Huang, G.-S. (2008). Acta Cryst. E64, m476.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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