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Acta Cryst. (2007). E63, m2612    [ doi:10.1107/S1600536807046879 ]

catena-Poly[[bis(1-ethyl-1H-imidazole-[kappa]N3)copper(II)]-[mu]-benzene-1,4-dicarboxylato]

G.-B. Che, Y. Liu, L. Lu, J. Sun and J. Wang

Abstract top

In the title compound, [Cu(C8H4O4)(C5H8N2)2]n, each CuII atom is four-coordinated by two carboxylate O atoms from two different benzene-1,4-dicarboxylate (1,4-BDC) ligands and two N atoms from two 1-ethyl-1H-imidazole (EI) ligands in a slightly distorted square-planar coordination environment. There are two Cu atoms, both with site symmetry \overline{1}. Each 1,4-BDC acts as a bis-monodentate ligand that binds two CuII atoms, thus forming two unique chains. The EI ligands are attached on both sides of the chains.

Comment top

Chain structures have received much attention in coordination chemistry and materials chemistry (Lehn, 1990). An appropriate flexible bidentate organic acid bridge could be useful in the formation of chains in the presence of secondary ligands, such as 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) (Qi et al., 2003). The N atoms from the secondary ligand may occupy two coordination positions of metal ions; the rest of the coordination positions are available for other carboxylate ligands to allow the formation of chain. We selected 1,4-benzenedicarboxylic acid (1,4-H2BDC) as a bridging ligand and 1-ethyl-1H-imidazole (EI) as a secondary ligand, generating the title compound, a new chain coordination polymer, [Cu(1,4-BDC)(EI)2], (I), which is reported here.

In compound (I), there exist two unique CuII atoms, both with site symmetry 1. Each CuII atom is four-coordinated by two carboxylate O atoms from two different 1,4-BDC ligands, and two N atoms from two EI ligands in a square-planar coordination environment (Fig. 1). The Cu—O and Cu—N distances are within their normal ranges (Table 1). As shown in Fig. 2, each 1,4-BDC acts as a bis-modentate ligand that binds two CuII atoms, forming two unique chains, both propagating in [010]. The EI ligands are attached to both sides of the chains.

Related literature top

For related literature, see: Lehn (1990); Qi et al. (2003); De (2007).

Experimental top

A mixture of CuCl2·2H2O (0.5 mmol), 1,4-H2BDC (0.5 mmol), EI (0.5 mmol), and H2O (500 mmol) was adjusted to pH = 5.5 by addition of aqueous NaOH solution, and heated in a sealed vessel at 463 K for 2 days. After the mixture was slowly cooled to room temperature, blue blocks of (I) were yielded (21% yield).

Refinement top

The H atoms were positioned geometrically (C—H = 0.93–0.97 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level. (H atoms have been omitted). Symmetry codes: (i) 2 − x, −y, 2 − z; (ii) 2 − x, 1 − y, 2 − z; (iii) 2 − x, 1 − y, 3 − z; (iv) 2 − x, −y, 3 − z.
[Figure 2] Fig. 2. View of the chain structure of (I).
catena-Poly[[bis(1-ethyl-1H-imidazole-κN3)copper(II)]-µ- benzene-1,4-dicarboxylato] top
Crystal data top
[Cu(C8H4O4)(C5H8N2)2]Z = 2
Mr = 419.92F000 = 434
Triclinic, P1Dx = 1.518 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 7.6864 (15) ÅCell parameters from 7742 reflections
b = 10.948 (2) Åθ = 3.0–27.5º
c = 11.372 (2) ŵ = 1.22 mm−1
α = 93.14 (3)ºT = 293 (2) K
β = 92.61 (3)ºBlock, blue
γ = 105.54 (3)º0.33 × 0.27 × 0.21 mm
V = 918.8 (3) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4136 independent reflections
Radiation source: rotating anode3397 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
Detector resolution: 10.0 pixels mm-1θmax = 27.5º
T = 293(2) Kθmin = 3.2º
ω scansh = −9→9
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −13→14
Tmin = 0.661, Tmax = 0.775l = −14→14
8970 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.111  w = 1/[σ2(Fo2) + (0.0729P)2 + 0.0254P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
4136 reflectionsΔρmax = 0.32 e Å−3
249 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu(C8H4O4)(C5H8N2)2]γ = 105.54 (3)º
Mr = 419.92V = 918.8 (3) Å3
Triclinic, P1Z = 2
a = 7.6864 (15) ÅMo Kα
b = 10.948 (2) ŵ = 1.22 mm−1
c = 11.372 (2) ÅT = 293 (2) K
α = 93.14 (3)º0.33 × 0.27 × 0.21 mm
β = 92.61 (3)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4136 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3397 reflections with I > 2σ(I)
Tmin = 0.661, Tmax = 0.775Rint = 0.018
8970 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032249 parameters
wR(F2) = 0.111H-atom parameters constrained
S = 1.15Δρmax = 0.32 e Å−3
4136 reflectionsΔρmin = −0.49 e Å−3
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
Cu21.00000.50001.50000.02771 (12)
Cu11.00000.00001.00000.02926 (12)
O30.9107 (2)0.27569 (14)1.36307 (14)0.0467 (4)
O20.93649 (19)0.17782 (13)0.86458 (14)0.0439 (4)
O11.04795 (19)0.18231 (12)1.04847 (13)0.0374 (3)
C90.6494 (3)0.3343 (2)1.5848 (3)0.0571 (7)
H90.67430.25851.56090.069*
O41.03966 (18)0.33904 (12)1.54287 (13)0.0360 (3)
N20.5345 (3)−0.0014 (2)1.16622 (18)0.0484 (5)
N10.7624 (2)−0.03149 (17)1.07038 (15)0.0361 (4)
N40.5146 (2)0.4683 (2)1.65828 (17)0.0414 (4)
N30.7593 (2)0.45316 (18)1.57218 (16)0.0369 (4)
C81.0313 (3)−0.03193 (18)1.61379 (18)0.0352 (4)
H81.0523−0.05341.69010.042*
C130.4459 (4)0.5512 (4)1.8516 (3)0.0774 (11)
H13A0.43270.47171.88670.116*
H13B0.37070.59701.88900.116*
H13C0.57000.60061.86170.116*
C180.4524 (5)0.0567 (5)1.3606 (3)0.0932 (14)
H18A0.4053−0.02961.38020.140*
H18B0.39250.11011.40310.140*
H18C0.58000.08441.38170.140*
C20.9975 (2)0.37248 (17)0.98204 (17)0.0290 (4)
C140.6978 (3)0.0531 (2)1.1280 (2)0.0426 (5)
H140.75760.13911.14050.051*
C41.0389 (3)0.56046 (18)1.11242 (18)0.0333 (4)
H41.06500.60091.18770.040*
C31.0364 (2)0.43359 (18)1.09464 (18)0.0337 (4)
H31.06070.38921.15800.040*
C150.6332 (3)−0.1453 (2)1.0739 (2)0.0469 (5)
H150.6414−0.22291.04060.056*
C10.9929 (2)0.23451 (17)0.96117 (18)0.0315 (4)
C60.9910 (2)0.12260 (17)1.48043 (18)0.0297 (4)
C50.9782 (2)0.25449 (17)1.45794 (19)0.0327 (4)
C71.0223 (3)0.09013 (18)1.59434 (18)0.0332 (4)
H71.03710.15031.65760.040*
C110.3898 (3)0.5266 (3)1.7217 (2)0.0558 (7)
H11A0.26810.47051.71140.067*
H11B0.38890.60611.68830.067*
C160.4928 (3)−0.1277 (3)1.1329 (2)0.0507 (6)
H160.3884−0.18951.14790.061*
C120.6734 (3)0.5318 (2)1.6179 (2)0.0410 (5)
H120.71680.61991.62180.049*
C100.4989 (3)0.3439 (3)1.6375 (3)0.0605 (7)
H100.40290.27711.65590.073*
C170.4214 (4)0.0649 (3)1.2339 (3)0.0689 (8)
H17A0.45080.15341.21590.083*
H17B0.29460.02651.21060.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu20.03678 (19)0.01434 (17)0.03383 (19)0.00974 (12)0.00320 (13)0.00240 (12)
Cu10.04075 (19)0.01696 (18)0.0337 (2)0.01396 (13)0.00339 (13)0.00183 (12)
O30.0661 (9)0.0273 (8)0.0518 (10)0.0207 (7)−0.0015 (7)0.0100 (7)
O20.0558 (8)0.0276 (7)0.0504 (9)0.0172 (6)−0.0004 (7)−0.0067 (7)
O10.0536 (8)0.0189 (7)0.0444 (8)0.0174 (6)0.0061 (7)0.0024 (6)
C90.0574 (14)0.0260 (11)0.089 (2)0.0094 (10)0.0257 (13)0.0077 (12)
O40.0467 (7)0.0146 (6)0.0489 (9)0.0117 (5)0.0022 (6)0.0033 (6)
N20.0481 (10)0.0546 (13)0.0476 (11)0.0225 (9)0.0078 (9)0.0009 (9)
N10.0440 (9)0.0300 (9)0.0383 (9)0.0169 (7)0.0027 (7)0.0027 (7)
N40.0402 (9)0.0469 (12)0.0382 (9)0.0138 (8)0.0032 (7)0.0009 (8)
N30.0418 (9)0.0288 (9)0.0419 (10)0.0119 (7)0.0060 (7)0.0048 (7)
C80.0490 (10)0.0235 (10)0.0356 (10)0.0136 (8)0.0025 (8)0.0045 (8)
C130.0614 (17)0.121 (3)0.0501 (16)0.0303 (18)0.0069 (13)−0.0189 (18)
C180.0693 (19)0.144 (4)0.065 (2)0.032 (2)0.0096 (16)−0.024 (2)
C20.0308 (8)0.0195 (9)0.0394 (10)0.0107 (6)0.0058 (7)0.0022 (7)
C140.0492 (12)0.0372 (12)0.0456 (12)0.0186 (9)0.0076 (10)0.0005 (9)
C40.0433 (10)0.0224 (9)0.0356 (10)0.0122 (7)0.0021 (8)−0.0008 (7)
C30.0416 (10)0.0236 (10)0.0387 (11)0.0131 (7)0.0018 (8)0.0041 (8)
C150.0462 (12)0.0357 (12)0.0586 (14)0.0107 (9)0.0049 (10)0.0016 (10)
C10.0332 (9)0.0202 (9)0.0433 (11)0.0101 (6)0.0089 (8)0.0002 (8)
C60.0324 (8)0.0185 (9)0.0402 (11)0.0098 (6)0.0048 (7)0.0025 (7)
C50.0358 (9)0.0202 (9)0.0461 (11)0.0121 (7)0.0093 (8)0.0082 (8)
C70.0442 (10)0.0201 (9)0.0369 (10)0.0122 (7)0.0036 (8)−0.0018 (7)
C110.0443 (12)0.0768 (19)0.0492 (14)0.0231 (12)0.0070 (10)−0.0056 (13)
C160.0445 (12)0.0464 (15)0.0614 (15)0.0116 (10)0.0042 (11)0.0084 (12)
C120.0422 (11)0.0358 (12)0.0470 (12)0.0129 (8)0.0094 (9)0.0016 (9)
C100.0479 (13)0.0483 (15)0.084 (2)0.0063 (11)0.0212 (13)0.0156 (13)
C170.0745 (18)0.072 (2)0.0684 (18)0.0332 (15)0.0221 (15)−0.0047 (15)
Geometric parameters (Å, °) top
Cu1—O11.9725 (14)C13—H13A0.9600
Cu1—O1i1.9725 (14)C13—H13B0.9600
Cu1—N1i1.9797 (17)C13—H13C0.9600
Cu1—N11.9797 (18)C18—C171.461 (5)
Cu2—O4ii1.9505 (13)C18—H18A0.9600
Cu2—O41.9505 (13)C18—H18B0.9600
Cu2—N3ii2.0088 (18)C18—H18C0.9600
Cu2—N32.0088 (18)C2—C4iv1.393 (3)
C1—O11.283 (3)C2—C31.393 (3)
C1—O21.232 (3)C2—C11.507 (2)
C5—O31.236 (3)C14—H140.9300
C5—O41.280 (3)C4—C31.388 (3)
C9—C101.353 (4)C4—C2iv1.393 (3)
C9—N31.368 (3)C4—H40.9300
C9—H90.9300C3—H30.9300
N2—C141.341 (3)C15—C161.347 (3)
N2—C161.361 (3)C15—H150.9300
N2—C171.487 (3)C6—C71.389 (3)
N1—C141.321 (3)C6—C8iii1.392 (3)
N1—C151.373 (3)C6—C51.508 (2)
N4—C101.342 (3)C7—H70.9300
N4—C121.347 (3)C11—H11A0.9700
N4—C111.479 (3)C11—H11B0.9700
N3—C121.318 (3)C16—H160.9300
C8—C71.386 (3)C12—H120.9300
C8—C6iii1.392 (3)C10—H100.9300
C8—H80.9300C17—H17A0.9700
C13—C111.509 (4)C17—H17B0.9700
O1—Cu1—O1i180.0C3—C2—C1120.90 (18)
O1—Cu1—N1i90.68 (7)N1—C14—N2111.0 (2)
O1i—Cu1—N1i89.32 (7)N1—C14—H14124.5
O1—Cu1—N189.32 (7)N2—C14—H14124.5
O1i—Cu1—N190.68 (7)C3—C4—C2iv120.28 (19)
N1i—Cu1—N1180.0C3—C4—H4119.9
O4ii—Cu2—O4180.0C2iv—C4—H4119.9
O4ii—Cu2—N3ii89.55 (7)C4—C3—C2120.14 (19)
O4—Cu2—N3ii90.45 (7)C4—C3—H3119.9
O4ii—Cu2—N390.45 (7)C2—C3—H3119.9
O4—Cu2—N389.55 (7)C16—C15—N1109.8 (2)
N3ii—Cu2—N3180.0C16—C15—H15125.1
C1—O1—Cu1106.68 (13)N1—C15—H15125.1
C10—C9—N3109.6 (2)O2—C1—O1123.63 (18)
C10—C9—H9125.2O2—C1—C2119.96 (19)
N3—C9—H9125.2O1—C1—C2116.40 (18)
C5—O4—Cu2109.27 (13)C7—C6—C8iii119.66 (18)
C14—N2—C16107.6 (2)C7—C6—C5120.69 (18)
C14—N2—C17125.8 (2)C8iii—C6—C5119.64 (18)
C16—N2—C17126.6 (2)O3—C5—O4123.98 (18)
C14—N1—C15105.37 (18)O3—C5—C6120.52 (19)
C14—N1—Cu1126.74 (16)O4—C5—C6115.50 (18)
C15—N1—Cu1127.86 (15)C8—C7—C6120.03 (19)
C10—N4—C12107.14 (19)C8—C7—H7120.0
C10—N4—C11127.1 (2)C6—C7—H7120.0
C12—N4—C11125.6 (2)N4—C11—C13111.2 (2)
C12—N3—C9105.09 (18)N4—C11—H11A109.4
C12—N3—Cu2126.86 (15)C13—C11—H11A109.4
C9—N3—Cu2128.05 (16)N4—C11—H11B109.4
C7—C8—C6iii120.31 (19)C13—C11—H11B109.4
C7—C8—H8119.8H11A—C11—H11B108.0
C6iii—C8—H8119.8C15—C16—N2106.2 (2)
C11—C13—H13A109.5C15—C16—H16126.9
C11—C13—H13B109.5N2—C16—H16126.9
H13A—C13—H13B109.5N3—C12—N4111.3 (2)
C11—C13—H13C109.5N3—C12—H12124.3
H13A—C13—H13C109.5N4—C12—H12124.3
H13B—C13—H13C109.5N4—C10—C9106.9 (2)
C17—C18—H18A109.5N4—C10—H10126.6
C17—C18—H18B109.5C9—C10—H10126.6
H18A—C18—H18B109.5C18—C17—N2110.6 (3)
C17—C18—H18C109.5C18—C17—H17A109.5
H18A—C18—H18C109.5N2—C17—H17A109.5
H18B—C18—H18C109.5C18—C17—H17B109.5
C4iv—C2—C3119.57 (17)N2—C17—H17B109.5
C4iv—C2—C1119.52 (18)H17A—C17—H17B108.1
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, −y+1, −z+3; (iii) −x+2, −y, −z+3; (iv) −x+2, −y+1, −z+2.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.9725 (14)Cu2—O41.9505 (13)
Cu1—N11.9797 (18)Cu2—N32.0088 (18)
Acknowledgements top

The authors thank the Natural Science Foundation of Jilin Province (grant No. 20060516), the Doctoral Foundation of Jilin Normal University (grant No. 2006006), the Science and Technology Institute Foundation of Siping City (grant No. 2005016) and the Subject and Base Construction Foundation of Jilin Normal University (grant No. 2006041).

references
References top

De, G. (2007). Acta Cryst. E63, m1748–m1749.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Lehn, J. M. (1990). Angew. Chem. Int. Ed. Engl. 29, 1304–1305.

Qi, Y., Wang, Y., Hu, C., Cao, M., Mao, L. & Wang, E. (2003). Inorg. Chem. 42, 8519–8523. [Please check year - originally 2002 in both citations, but 2003 here]

Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (1990). SHELXTL-Plus. Siemens Analytical X-Ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.