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Acta Cryst. (2007). E63, m1748-m1749    [ doi:10.1107/S1600536807023628 ]

catena-Poly[[[bis(2-methyl-1H-imidazole)copper(II)]-[mu]-1,4-cyclohexanedicarboxylato-[kappa]2O,O'] monohydrate]

G. De

Abstract top

In the title compound, {[Cu(1,4-chdc)(L)2]·H2O}n, where 1,4-chdc is the 1,4-cyclohexanedicarboxylate dianion, C8H10O42-, and L is 2-methyl-1H-imidazole, C4H6N2, each CuII atom is four-coordinated by two N atoms from two L ligands and two O atoms from two 1,4-chdc anions in a distorted tetrahedral geometry. Each 1,4-chdc ligand bridges two neighbouring CuII atoms in a bidentate mode, forming a unique helical chain. These chains are decorated with L ligands alternately on the two sides. O-H...O and N-H...O hydrogen bonds complete the structure.

Comment top

Rigid spacer ligands such as benzenedi- and tri-carboxylates have successfully produced various extended structures with metal cations (Li et al., 2002). However, the studies on the structures composed of flexible carboxylate ligands still remains undeveloped probably because the low symmetry and the flexibility of the ligand make it difficult to control the final structure. We selected 1,4-cyclohexanedicarboxylic acid (1,4-chdcH2) as a bridging ligand and 2-methyl-1H-imidazole (L) as a secondary ligand, generating a new helical chain coordination polymer, [Cu(1,4-chdc)(L)2].H2O, (I), which is reported here.

Selected bond lengths and angles for (I) are given in Table 1. In compound (I), each Cu(II) atom is four-coordinated by two N atoms from two L ligands, and two O atoms from two 1,4-chdc molecules in a distorted tetrahedral geometry (Fig. 1). The Cu1—O2 and Cu1—O3i distances are 1.9951 (16) and 1.9627 (14) Å, respectively (Table 1). The Cu1—N1 and Cu1—N3 distances are 1.9692 (17) and 1.9976 (18) Å, respectively (Table 1). Each 1,4-chdc ligand bridges two neighboring Cu(II) atoms in a bidentate mode, forming a unique helical chain (Fig. 2). These chains are decorated with L ligands alternately at two sides. In addition, the O—H···O and N—H···O hydrogen bonds complete structure of (I) (Table 2).

Related literature top

The related compound, [Zn(1,4-chdc)(phen)(H2O)]n (1,4-chdc = 1,4-cyclohexanedicarboxylate and phen = 1,10-phenanthroline), also has a chain structure. The central ZnII cation is coordinated by four water and carboxylate O atoms and two N atoms from the phen ligand. Each 1,4-chdc ligand links two ZnII cations in chelating and monodentate modes, forming an infinite helical chain-like structure with 21 helices (Bi et al., 2004).

For related literature, see: Li et al. (2002).

Experimental top

A mixture of CuCl2.2H2O (0.5 mmol), 1,4-chdc acid (0.5 mmol), and L (0.5 mmol) was adjusted to pH=6 by addition of aqueous NaOH solution. The resulting solution was filtered, the filtrate was allowed to stand in air at room temperature for two weeks, and the blue crystals of (I) were obtained (yield 31% based on Cu).

Refinement top

All H atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93–0.98 Å) and refined as riding, with Uiso(H)=1.2Ueq(carrier). The water H-atoms were located in a difference Fourier map, and were refined with distance restraints of O–H = 0.85 Å; their temperature factors were tied to those of parent atoms by a factor of 1.2.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; 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.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (i) x - 1/2, y + 1/2, z.
[Figure 2] Fig. 2. View of the chain structure in (I).
catena-Poly[[[bis(2-methyl-1H-imidazole)copper(II)] -µ-1,4-cyclohexanedicarboxylato-κ2O,O'] monohydrate] top
Crystal data top
[Cu(C8H10O4)(C4H6N2)2]·H2OF(000) = 868
Mr = 415.93Dx = 1.439 Mg m−3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 8581 reflections
a = 13.179 (3) Åθ = 3.2–27.5°
b = 11.897 (2) ŵ = 1.17 mm−1
c = 12.314 (3) ÅT = 293 K
β = 96.03 (3)°Block, blue
V = 1920.1 (7) Å30.28 × 0.27 × 0.24 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3853 independent reflections
Radiation source: rotating anode3592 reflections with I > 2σ(I)
graphiteRint = 0.019
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scanh = −17→17
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −15→15
Tmin = 0.713, Tmax = 0.758l = −15→15
9070 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)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059 w = 1/[σ2(Fo2) + (0.0309P)2 + 0.0676P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
3853 reflectionsΔρmax = 0.22 e Å−3
245 parametersΔρmin = −0.21 e Å−3
5 restraintsAbsolute structure: Flack (1983), 1655 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.011 (10)
Crystal data top
[Cu(C8H10O4)(C4H6N2)2]·H2OV = 1920.1 (7) Å3
Mr = 415.93Z = 4
Monoclinic, CcMo Kα radiation
a = 13.179 (3) ŵ = 1.17 mm−1
b = 11.897 (2) ÅT = 293 K
c = 12.314 (3) Å0.28 × 0.27 × 0.24 mm
β = 96.03 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3853 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3592 reflections with I > 2σ(I)
Tmin = 0.713, Tmax = 0.758Rint = 0.019
9070 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059Δρmax = 0.22 e Å−3
S = 1.09Δρmin = −0.21 e Å−3
3853 reflectionsAbsolute structure: Flack (1983), 1655 Friedel pairs
245 parametersFlack parameter: 0.011 (10)
5 restraints
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
C10.19772 (16)0.23174 (15)0.28646 (19)0.0282 (4)
C20.30024 (17)0.25386 (14)0.2433 (2)0.0329 (5)
H2A0.29420.32610.20500.039*
C30.38580 (18)0.26687 (17)0.3369 (2)0.0396 (5)
H3A0.36370.31820.39090.047*
H3B0.44530.29930.30860.047*
C40.41519 (17)0.15402 (17)0.39159 (18)0.0373 (5)
H4A0.47150.16510.44790.045*
H4B0.35780.12470.42600.045*
C50.44610 (15)0.06954 (15)0.30770 (16)0.0278 (4)
H50.50510.10110.27620.033*
C60.36148 (17)0.05469 (16)0.21444 (17)0.0326 (4)
H6A0.30290.01970.24220.039*
H6B0.38500.00520.15980.039*
C70.32944 (18)0.16732 (18)0.16160 (17)0.0370 (5)
H7A0.38530.19660.12460.044*
H7B0.27180.15520.10710.044*
C80.47826 (14)−0.04401 (15)0.35574 (16)0.0281 (4)
C90.10618 (19)0.22595 (19)0.6122 (2)0.0377 (5)
H90.10560.30370.62010.045*
C100.1344 (2)0.1525 (2)0.69177 (18)0.0445 (6)
H100.15690.16910.76410.053*
C110.09062 (17)0.06032 (17)0.54026 (17)0.0346 (4)
C120.0745 (3)−0.0340 (2)0.4619 (2)0.0602 (8)
H12A0.0586−0.10100.50020.090*
H12B0.1354−0.04580.42700.090*
H12C0.0190−0.01620.40780.090*
C13−0.15859 (19)0.1245 (2)0.43684 (19)0.0414 (5)
H13−0.14260.13380.51170.050*
C14−0.23970 (19)0.0679 (2)0.3894 (2)0.0466 (6)
H14−0.28960.03170.42460.056*
C15−0.15176 (16)0.13368 (17)0.26216 (17)0.0337 (4)
C16−0.1217 (2)0.1605 (3)0.15148 (18)0.0561 (7)
H16A−0.16820.12480.09690.084*
H16B−0.05380.13360.14590.084*
H16C−0.12380.24040.14050.084*
N10.07791 (14)0.16816 (14)0.51644 (14)0.0318 (4)
N20.12344 (16)0.04764 (15)0.64560 (15)0.0392 (4)
H20.1356−0.01530.67880.047*
N3−0.10236 (13)0.16677 (14)0.35673 (14)0.0316 (4)
N4−0.23445 (14)0.07396 (16)0.28022 (16)0.0395 (4)
H4−0.27720.04440.23080.047*
O10.13847 (12)0.15720 (12)0.24666 (14)0.0410 (4)
O20.17380 (11)0.29511 (12)0.36217 (13)0.0352 (3)
O1W0.61751 (13)0.03906 (15)0.63232 (14)0.0424 (4)
O30.48379 (11)−0.12457 (11)0.28814 (11)0.0329 (3)
O40.49861 (13)−0.05853 (13)0.45594 (12)0.0434 (4)
Cu10.03143 (3)0.246810 (16)0.37949 (3)0.02601 (6)
HW110.5812 (18)0.015 (2)0.5807 (15)0.034 (6)*
HW120.5816 (18)0.0736 (19)0.6717 (17)0.038 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0256 (10)0.0215 (8)0.0373 (11)0.0054 (7)0.0011 (8)0.0044 (8)
C20.0296 (11)0.0242 (9)0.0456 (12)0.0057 (7)0.0081 (9)0.0061 (8)
C30.0290 (11)0.0260 (9)0.0640 (16)−0.0004 (8)0.0063 (10)−0.0086 (10)
C40.0340 (12)0.0330 (10)0.0428 (12)0.0073 (8)−0.0061 (9)−0.0122 (9)
C50.0235 (10)0.0260 (8)0.0335 (10)0.0018 (7)0.0009 (8)−0.0001 (8)
C60.0350 (11)0.0295 (9)0.0321 (10)0.0095 (8)−0.0021 (8)−0.0033 (8)
C70.0375 (12)0.0393 (11)0.0344 (10)0.0117 (9)0.0052 (9)0.0064 (9)
C80.0213 (10)0.0298 (9)0.0323 (10)0.0017 (7)−0.0013 (8)0.0020 (8)
C90.0404 (13)0.0341 (9)0.0370 (12)−0.0006 (9)−0.0032 (9)−0.0015 (9)
C100.0533 (15)0.0444 (12)0.0335 (11)0.0018 (10)−0.0062 (10)0.0007 (10)
C110.0345 (12)0.0303 (10)0.0377 (11)−0.0027 (8)−0.0016 (9)0.0052 (9)
C120.087 (2)0.0346 (12)0.0555 (16)−0.0004 (13)−0.0105 (15)−0.0039 (12)
C130.0446 (14)0.0477 (12)0.0329 (10)−0.0109 (10)0.0085 (9)0.0005 (10)
C140.0381 (13)0.0501 (13)0.0522 (14)−0.0147 (10)0.0077 (11)0.0042 (12)
C150.0295 (11)0.0382 (10)0.0323 (10)0.0006 (8)−0.0028 (8)−0.0032 (9)
C160.0512 (16)0.086 (2)0.0310 (11)−0.0052 (14)0.0015 (11)−0.0031 (13)
N10.0335 (9)0.0281 (8)0.0325 (8)−0.0024 (7)−0.0029 (7)0.0039 (7)
N20.0431 (11)0.0339 (9)0.0389 (10)0.0014 (8)−0.0041 (8)0.0122 (8)
N30.0285 (9)0.0347 (8)0.0311 (9)−0.0054 (7)0.0004 (7)0.0009 (7)
N40.0316 (10)0.0413 (9)0.0435 (10)−0.0056 (7)−0.0062 (8)−0.0044 (9)
O10.0329 (8)0.0346 (7)0.0563 (10)−0.0038 (6)0.0080 (7)−0.0166 (7)
O20.0315 (8)0.0306 (7)0.0444 (9)−0.0022 (6)0.0088 (6)−0.0087 (7)
O1W0.0373 (9)0.0517 (9)0.0370 (9)0.0068 (8)−0.0016 (7)−0.0061 (8)
O30.0413 (9)0.0244 (6)0.0320 (7)0.0060 (6)−0.0015 (6)0.0018 (6)
O40.0574 (11)0.0431 (8)0.0283 (7)0.0119 (7)−0.0022 (7)−0.0007 (7)
Cu10.02640 (10)0.02329 (9)0.02761 (10)−0.00107 (9)−0.00064 (7)0.00362 (9)
Geometric parameters (Å, °) top
C1—O11.247 (2)C10—H100.9300
C1—O21.264 (3)C11—N11.323 (3)
C1—C21.526 (3)C11—N21.332 (3)
C2—C71.517 (3)C11—C121.480 (3)
C2—C31.533 (4)C12—H12A0.9600
C2—H2A0.9800C12—H12B0.9600
C3—C41.534 (3)C12—H12C0.9600
C3—H3A0.9700C13—C141.344 (3)
C3—H3B0.9700C13—N31.389 (3)
C4—C51.527 (3)C13—H130.9300
C4—H4A0.9700C14—N41.356 (3)
C4—H4B0.9700C14—H140.9300
C5—C81.517 (3)C15—N31.333 (3)
C5—C61.525 (3)C15—N41.339 (3)
C5—H50.9800C15—C161.493 (3)
C6—C71.530 (3)C16—H16A0.9600
C6—H6A0.9700C16—H16B0.9600
C6—H6B0.9700C16—H16C0.9600
C7—H7A0.9700Cu1—N11.9692 (17)
C7—H7B0.9700N2—H20.8600
C8—O41.247 (2)Cu1—N31.9976 (18)
C8—O31.277 (2)N4—H40.8600
C9—C101.336 (3)Cu1—O21.9951 (16)
C9—N11.382 (3)O1W—HW110.807 (16)
C9—H90.9300O1W—HW120.822 (16)
C10—N21.372 (3)Cu1—O3i1.9627 (14)
O1—C1—O2121.3 (2)N2—C10—H10126.8
O1—C1—C2121.78 (19)N1—C11—N2110.27 (19)
O2—C1—C2116.89 (18)N1—C11—C12125.7 (2)
C7—C2—C1114.17 (18)N2—C11—C12124.0 (2)
C7—C2—C3110.44 (18)C11—C12—H12A109.5
C1—C2—C3111.4 (2)C11—C12—H12B109.5
C7—C2—H2A106.8H12A—C12—H12B109.5
C1—C2—H2A106.8C11—C12—H12C109.5
C3—C2—H2A106.8H12A—C12—H12C109.5
C2—C3—C4111.95 (17)H12B—C12—H12C109.5
C2—C3—H3A109.2C14—C13—N3109.4 (2)
C4—C3—H3A109.2C14—C13—H13125.3
C2—C3—H3B109.2N3—C13—H13125.3
C4—C3—H3B109.2C13—C14—N4106.5 (2)
H3A—C3—H3B107.9C13—C14—H14126.8
C5—C4—C3110.6 (2)N4—C14—H14126.8
C5—C4—H4A109.5N3—C15—N4110.06 (19)
C3—C4—H4A109.5N3—C15—C16125.6 (2)
C5—C4—H4B109.5N4—C15—C16124.31 (19)
C3—C4—H4B109.5C15—C16—H16A109.5
H4A—C4—H4B108.1C15—C16—H16B109.5
C8—C5—C6110.05 (15)H16A—C16—H16B109.5
C8—C5—C4113.94 (17)C15—C16—H16C109.5
C6—C5—C4111.09 (16)H16A—C16—H16C109.5
C8—C5—H5107.1H16B—C16—H16C109.5
C6—C5—H5107.1C11—N1—C9106.06 (17)
C4—C5—H5107.1C11—N1—Cu1132.18 (14)
C5—C6—C7111.49 (17)C9—N1—Cu1121.75 (14)
C5—C6—H6A109.3C11—N2—C10108.04 (18)
C7—C6—H6A109.3C11—N2—H2126.0
C5—C6—H6B109.3C10—N2—H2126.0
C7—C6—H6B109.3C15—N3—C13105.40 (18)
H6A—C6—H6B108.0C15—N3—Cu1127.33 (15)
C2—C7—C6112.96 (17)C13—N3—Cu1127.01 (14)
C2—C7—H7A109.0C15—N4—C14108.68 (18)
C6—C7—H7A109.0C15—N4—H4125.7
C2—C7—H7B109.0C14—N4—H4125.7
C6—C7—H7B109.0C1—O2—Cu1102.54 (13)
H7A—C7—H7B107.8HW11—O1W—HW12108 (2)
O4—C8—O3121.34 (17)C8—O3—Cu1ii104.38 (12)
O4—C8—C5122.11 (17)O3i—Cu1—N1155.96 (6)
O3—C8—C5116.55 (16)O3i—Cu1—O287.82 (7)
C10—C9—N1109.24 (19)N1—Cu1—O290.97 (8)
C10—C9—H9125.4O3i—Cu1—N393.83 (7)
N1—C9—H9125.4N1—Cu1—N394.84 (7)
C9—C10—N2106.37 (19)O2—Cu1—N3161.53 (7)
C9—C10—H10126.8
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) x+1/2, y−1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O40.81 (2)1.99 (2)2.794 (2)174 (2)
O1W—HW12···O3iii0.82 (2)2.12 (2)2.921 (2)167 (2)
N2—H2···O1iii0.861.882.734 (2)170
N4—H4···O1Wiv0.862.012.861 (2)172
Symmetry codes: (iii) x, −y, z+1/2; (iv) x−1, −y, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N11.9692 (17)Cu1—O21.9951 (16)
Cu1—N31.9976 (18)Cu1—O3i1.9627 (14)
O3i—Cu1—N1155.96 (6)O3i—Cu1—N393.83 (7)
O3i—Cu1—O287.82 (7)N1—Cu1—N394.84 (7)
N1—Cu1—O290.97 (8)O2—Cu1—N3161.53 (7)
Symmetry codes: (i) x−1/2, y+1/2, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O40.81 (2)1.99 (2)2.794 (2)174 (2)
O1W—HW12···O3ii0.82 (2)2.12 (2)2.921 (2)167 (2)
N2—H2···O1ii0.861.882.734 (2)170
N4—H4···O1Wiii0.862.012.861 (2)172
Symmetry codes: (ii) x, −y, z+1/2; (iii) x−1, −y, z−1/2.
Acknowledgements top

The author thanks the Inner Mongolia Normal University for supporting this work.

references
References top

Bi, W.-H., Sun, D.-F., Cao, R. & Wang, Y.-Q. (2004). Acta Cryst. E60, m711–m712.

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Li, Y. G., Zhang, H., Wang, E., Hao, N., Hu, C., Yu, Y. & Hall, D. (2002). New J. Chem. 26, 1619–1623.

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 Góttingen, Germany.