Poly[diimidazole-μ4-oxalato-μ2-oxalato-dicopper(II)]

Jin, Z.-N.; Lin, H.

doi:10.1107/S1600536811015777

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m680

doi:10.1107/S1600536811015777

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Poly[diimidazole-μ₄-oxalato-μ₂-oxalato-dicopper(II)]

Zhu-Nian Jin ^a and Hong Lin ^a ^*

^aJinhua Professional Technical College, No. 1188 Wuzhou Street, Jinhua, Zhejiang 321007, People's Republic of China
^*Correspondence e-mail: jh_ll@126.com

(Received 29 March 2011; accepted 26 April 2011; online 7 May 2011)

The title compound, [Cu₂(C₂O₄)₂(C₃H₄N₂)₂]_n, was obtained as an unexpected product under hydrothermal conditions. The Cu^II atom is in a Jahn–Teller-distorted octahedral environment formed by one imidazole N atom and five O atoms from three oxalate anions. The two independent oxalate anions are situated on centres of inversion and coordinate to the Cu^II atom in two different modes, viz. bidentate and monodentate. The bidentate anions bridge two Cu^II atoms, whereas the monodentate anions bridge four Cu^II atoms, leading to a layered arrangement parallel to (100). These layers are further linked into a final three-dimensional network structure via intermolecular N—H⋯O hydrogen bonds. The title compound is isotypic with the Zn analogue.

Related literature

For background to oxalates, see: Ghosh et al. (2004 ); Ye & Lin (2010 ). For the isotypic Zn analogue, see: Lu et al. (2005 ).

Experimental

Crystal data

[Cu₂(C₂O₄)₂(C₃H₄N₂)₂]
M_r = 439.28
Monoclinic, P 2₁ /c
a = 8.3367 (4) Å
b = 9.3131 (5) Å
c = 8.4838 (5) Å
β = 92.352 (3)°
V = 658.13 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.29 mm⁻¹
T = 296 K
0.28 × 0.18 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.497, T_max = 0.821
10313 measured reflections
1511 independent reflections
1362 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.062
S = 1.09
1511 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.9624 (18)
Cu1—O3	1.9713 (13)
Cu1—O2ⁱ	1.9960 (14)
Cu1—O1	2.0016 (13)
Cu1—O4	2.3536 (14)
Cu1—O4ⁱⁱ	2.512 (1)
Symmetry codes: (i) -x-2, -y, -z; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2ⁱⁱⁱ	0.86	2.00	2.841 (2)	167
Symmetry code: (iii) -x-1, -y, -z.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811015777/wm2473sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015777/wm2473Isup2.hkl

checkCIF report

Comment top

Oxalates can represent one of the end-products of the degradation of some organic ligands, under both oxidative and non-oxidative conditions (Ghosh et al., 2004). For example, we reported an oxalate compound with a three-dimensional structure, which was constructed by decomposition of 2-carboxymethylsulfanyl nicotinic acid (Ye et al., 2010). Herein, we report a new polymeric oxalate compound, Cu₂(C₂O₄)₂(C₃N₂H₄)₂, (I), which is isotypic with Zn₂(C₂O₄)₂(C₃N₂H₄)₂ (Lu et al., 2005).

A view on the molecular structure of compound (I) is given in Fig. 1. The Cu^II atoms are each in a Jahn-Teller distorted coordination by one nitrogen atom from imidazole and five oxygen atoms from three oxalate groups. The oxalate anions adopt two different coordination modes: one adopts a chelate bis-bidentate linkage, the other adopts a chelate and bridging bis-bidentate linkage (Fig. 1). As shown in Fig. 2, the oxalate anions connect the Cu^II atoms into a two dimensional layer along the bc plane, and are further linked into a three-dimensional network structure by N—H···O hydrogen bonds (Fig. 3).

Related literature top

For background to oxalates, see: Ghosh et al. (2004); Ye et al. (2010). For the isotypic Zn analogue, see: Lu et al. (2005).

Experimental top

A mixture of 2-carboxymethylsulfanyl nicotinic acid (0.086 g, 0.40 mmol), CuCl₂^.2H₂O (0.068 g, 0.40 mmol), and imidazole (0.054 g, 0.80 mmol) in CH₃CH₂OH (2 ml)/H₂O (16 ml) was placed in a 25 ml Teflon-lined stainless steel reactor and heated at 383 K for 24 h, and then cooled to room temperature over a period of 24 h. Green crystals suitable for X-ray analysis were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the structure of Cu₂(C₂O₄)₂(C₃N₂H₄)₂. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two-dimensional layer constructed by bridging oxalate anions. Imidazole ligands are omitted for clarity.
	Fig. 3. The three-dimensional network in Cu₂(C₂O₄)₂(C₃N₂H₄)₂. The N—H···O hydrogen bond interactions are depicted by dashed lines.

Poly[diimidazole-µ₄-oxalato-µ₂-oxalato-dicopper(II)] top

Crystal data top

[Cu₂(C₂O₄)₂(C₃H₄N₂)₂]	F(000) = 436
M_r = 439.28	D_x = 2.217 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4365 reflections
a = 8.3367 (4) Å	θ = 2.5–27.6°
b = 9.3131 (5) Å	µ = 3.29 mm⁻¹
c = 8.4838 (5) Å	T = 296 K
β = 92.352 (3)°	Block, green
V = 658.13 (6) Å³	0.28 × 0.18 × 0.06 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1511 independent reflections
Radiation source: fine-focus sealed tube	1362 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.6°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
T_min = 0.497, T_max = 0.821	k = −12→12
10313 measured reflections	l = −11→10

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0335P)² + 0.3353P] where P = (F_o² + 2F_c²)/3
1511 reflections	(Δ/σ)_max = 0.001
109 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu₂(C₂O₄)₂(C₃H₄N₂)₂]	V = 658.13 (6) Å³
M_r = 439.28	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3367 (4) Å	µ = 3.29 mm⁻¹
b = 9.3131 (5) Å	T = 296 K
c = 8.4838 (5) Å	0.28 × 0.18 × 0.06 mm
β = 92.352 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1511 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1362 reflections with I > 2σ(I)
T_min = 0.497, T_max = 0.821	R_int = 0.028
10313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.062	H-atom parameters constrained
S = 1.09	Δρ_max = 0.49 e Å⁻³
1511 reflections	Δρ_min = −0.42 e Å⁻³
109 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	−0.87721 (3)	0.23821 (2)	−0.10302 (3)	0.02435 (10)
O1	−0.80090 (16)	0.04677 (14)	−0.02324 (17)	0.0263 (3)
O2	−0.90639 (16)	−0.15701 (14)	0.06412 (17)	0.0265 (3)
O3	−0.97708 (18)	0.41685 (14)	−0.18398 (16)	0.0277 (3)
O4	−0.91189 (18)	0.37282 (15)	0.12789 (17)	0.0296 (3)
N1	−0.6552 (2)	0.30160 (19)	−0.1281 (2)	0.0294 (4)
N2	−0.3925 (2)	0.2996 (3)	−0.1154 (3)	0.0450 (5)
H2A	−0.2956	0.2704	−0.0975	0.054*
C1	−0.9154 (2)	−0.03131 (19)	0.0114 (2)	0.0214 (4)
C2	−1.0193 (2)	0.51365 (19)	−0.0895 (2)	0.0225 (4)
C3	−0.5993 (3)	0.4276 (3)	−0.1902 (3)	0.0411 (5)
H3A	−0.6631	0.5019	−0.2305	0.049*
C4	−0.4374 (3)	0.4264 (3)	−0.1836 (3)	0.0483 (6)
H4A	−0.3699	0.4981	−0.2186	0.058*
C5	−0.5252 (3)	0.2292 (2)	−0.0814 (3)	0.0400 (6)
H5A	−0.5266	0.1404	−0.0313	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02007 (15)	0.01856 (14)	0.03460 (17)	0.00096 (8)	0.00343 (10)	0.00411 (9)
O1	0.0212 (7)	0.0228 (6)	0.0351 (8)	−0.0002 (5)	0.0017 (6)	0.0042 (6)
O2	0.0215 (7)	0.0203 (6)	0.0377 (8)	0.0020 (5)	0.0023 (6)	0.0040 (5)
O3	0.0356 (8)	0.0206 (6)	0.0269 (7)	0.0042 (5)	0.0015 (6)	0.0004 (5)
O4	0.0369 (8)	0.0235 (7)	0.0284 (7)	0.0072 (6)	0.0001 (6)	0.0016 (5)
N1	0.0244 (8)	0.0261 (8)	0.0379 (10)	−0.0009 (7)	0.0034 (7)	0.0014 (7)
N2	0.0216 (10)	0.0462 (12)	0.0670 (15)	0.0008 (8)	0.0001 (9)	0.0017 (10)
C1	0.0204 (9)	0.0217 (8)	0.0222 (9)	0.0022 (7)	0.0013 (7)	−0.0013 (7)
C2	0.0224 (9)	0.0214 (8)	0.0238 (10)	−0.0019 (7)	0.0008 (7)	0.0019 (7)
C3	0.0339 (12)	0.0401 (12)	0.0490 (14)	−0.0052 (10)	−0.0025 (10)	0.0143 (10)
C4	0.0334 (12)	0.0551 (15)	0.0561 (16)	−0.0138 (11)	−0.0001 (11)	0.0164 (13)
C5	0.0272 (12)	0.0303 (11)	0.0624 (16)	0.0021 (8)	0.0015 (11)	0.0043 (10)

Geometric parameters (Å, º) top

Cu1—N1	1.9624 (18)	N1—C3	1.375 (3)
Cu1—O3	1.9713 (13)	N2—C5	1.328 (3)
Cu1—O2ⁱ	1.9960 (14)	N2—C4	1.361 (3)
Cu1—O1	2.0016 (13)	N2—H2A	0.8600
Cu1—O4	2.3536 (14)	C1—C1ⁱ	1.532 (4)
Cu1—O4ⁱⁱ	2.512 (1)	C2—O4ⁱⁱⁱ	1.240 (2)
O1—C1	1.245 (2)	C2—C2ⁱⁱⁱ	1.560 (4)
O2—C1	1.254 (2)	C3—C4	1.348 (3)
O2—Cu1ⁱ	1.9960 (14)	C3—H3A	0.9300
O3—C2	1.266 (2)	C4—H4A	0.9300
O4—C2ⁱⁱⁱ	1.240 (2)	C5—H5A	0.9300
N1—C5	1.323 (3)

N1—Cu1—O3	95.45 (7)	C3—N1—Cu1	129.37 (16)
N1—Cu1—O2ⁱ	174.07 (6)	C5—N2—C4	107.7 (2)
O3—Cu1—O2ⁱ	90.33 (6)	C5—N2—H2A	126.2
N1—Cu1—O1	90.95 (6)	C4—N2—H2A	126.2
O3—Cu1—O1	173.43 (6)	O1—C1—O2	126.46 (17)
O2ⁱ—Cu1—O1	83.31 (5)	O1—C1—C1ⁱ	117.3 (2)
N1—Cu1—O4	94.51 (7)	O2—C1—C1ⁱ	116.2 (2)
O3—Cu1—O4	77.05 (5)	O4ⁱⁱⁱ—C2—O3	125.35 (17)
O2ⁱ—Cu1—O4	85.50 (6)	O4ⁱⁱⁱ—C2—C2ⁱⁱⁱ	118.0 (2)
O1—Cu1—O4	103.96 (5)	O3—C2—C2ⁱⁱⁱ	116.7 (2)
O1—Cu1—O4ⁱⁱ	87.92 (5)	C4—C3—N1	109.4 (2)
O4—Cu1—O4ⁱⁱ	164.20 (6)	C4—C3—H3A	125.3
O3—Cu1—O4ⁱⁱ	89.98 (5)	N1—C3—H3A	125.3
N1—Cu1—O4ⁱⁱ	95.69 (6)	C3—C4—N2	106.4 (2)
C1—O1—Cu1	111.35 (12)	C3—C4—H4A	126.8
C1—O2—Cu1ⁱ	111.80 (12)	N2—C4—H4A	126.8
C2—O3—Cu1	120.32 (12)	N1—C5—N2	111.3 (2)
C2ⁱⁱⁱ—O4—Cu1	107.87 (12)	N1—C5—H5A	124.4
C5—N1—C3	105.23 (19)	N2—C5—H5A	124.4
C5—N1—Cu1	125.38 (16)

N1—Cu1—O1—C1	178.87 (13)	O2ⁱ—Cu1—N1—C3	−170.1 (6)
O3—Cu1—O1—C1	−14.0 (6)	O1—Cu1—N1—C3	175.6 (2)
O2ⁱ—Cu1—O1—C1	0.34 (13)	O4—Cu1—N1—C3	−80.3 (2)
O4—Cu1—O1—C1	83.99 (13)	Cu1—O1—C1—O2	179.88 (16)
N1—Cu1—O3—C2	−96.29 (15)	Cu1—O1—C1—C1ⁱ	−0.4 (3)
O2ⁱ—Cu1—O3—C2	82.40 (15)	Cu1ⁱ—O2—C1—O1	179.67 (16)
O1—Cu1—O3—C2	96.7 (5)	Cu1ⁱ—O2—C1—C1ⁱ	0.0 (2)
O4—Cu1—O3—C2	−2.90 (14)	Cu1—O3—C2—O4ⁱⁱⁱ	−177.21 (15)
N1—Cu1—O4—C2ⁱⁱⁱ	97.23 (13)	Cu1—O3—C2—C2ⁱⁱⁱ	2.8 (3)
O3—Cu1—O4—C2ⁱⁱⁱ	2.66 (13)	C5—N1—C3—C4	1.7 (3)
O2ⁱ—Cu1—O4—C2ⁱⁱⁱ	−88.72 (13)	Cu1—N1—C3—C4	179.68 (18)
O1—Cu1—O4—C2ⁱⁱⁱ	−170.67 (12)	N1—C3—C4—N2	−0.6 (3)
O3—Cu1—N1—C5	174.7 (2)	C5—N2—C4—C3	−0.7 (3)
O2ⁱ—Cu1—N1—C5	7.6 (8)	C3—N1—C5—N2	−2.1 (3)
O1—Cu1—N1—C5	−6.7 (2)	Cu1—N1—C5—N2	179.75 (17)
O4—Cu1—N1—C5	97.3 (2)	C4—N2—C5—N1	1.8 (3)
O3—Cu1—N1—C3	−2.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^iv	0.86	2.00	2.841 (2)	167

Symmetry code: (iv) −x−1, −y, −z.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂O₄)₂(C₃H₄N₂)₂]
M_r	439.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.3367 (4), 9.3131 (5), 8.4838 (5)
β (°)	92.352 (3)
V (Å³)	658.13 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.29
Crystal size (mm)	0.28 × 0.18 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.497, 0.821
No. of measured, independent and observed [I > 2σ(I)] reflections	10313, 1511, 1362
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.062, 1.09
No. of reflections	1511
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.42

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	1.9624 (18)	Cu1—O1	2.0016 (13)
Cu1—O3	1.9713 (13)	Cu1—O4	2.3536 (14)
Cu1—O2ⁱ	1.9960 (14)	Cu1—O4ⁱⁱ	2.512 (1)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2ⁱⁱⁱ	0.86	2.00	2.841 (2)	167

Symmetry code: (iii) −x−1, −y, −z.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Ghosh, S. K., Savitha, G. & Bharadwaj, P. K. (2004). Inorg. Chem. 43, 5495–5497. Web of Science CSD CrossRef PubMed CAS Google Scholar
Lu, J., Zhao, K., Fang, Q. R., Xu, J. Q., Yu, J. H., Zhang, X., Bie, H. Y. & Wang, T. G. (2005). Cryst. Growth Des. 5, 1091–1098. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, S.-F. & Lin, H. (2010). Acta Cryst. E66, m901–m902. Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m680

doi:10.1107/S1600536811015777

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