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Acta Cryst. (2007). E63, m1735-m1736    [ doi:10.1107/S1600536807024063 ]

catena-Poly[[[bis(2-methyl-1H-imidazole)cobalt(II)]-[mu]-cyclohexane-1,4-dicarboxylato] monohydrate]

Y.-M. Zhang, G. Xin, Dong-Yan Hou and T.-C. Li

Abstract top

In the title compound, {[Co(1,4-chdc)(L)2]·H2O}n, where 1,4-chdc is the cyclohexane-1,4-dicarboxylate dianion, C8H10O42-, and L is 2-methyl-1H-imidazole, C4H6N2, each CoII atom is four-coordinated by two O atoms from two 1,4-chdc ligands and two N atoms from two L molecules in a distorted tetrahedral geometry. Each 1,4-chdc anion acts as a bidentate ligand that links two CoII atoms, thus generating a helical chain. These chains are decorated with L ligands alternately on the two sides. In addition, O-H...O and N-H...O hydrogen bonds complete the structure of (I).

Comment top

Helical structures have received much attention in coordination chemistry (Chen & Liu, 2002). The flexible bidentate organic acid may be useful in the generation of helical chains in the presence of secondary ligands (Zhang et al., 2007). The N atoms from the secondary ligand may occupy one or two coordination positions of metal ions. The rest of the coordination positions are available for other carboxylate ligands to allow the formation of a helical structure. Here, we selected cyclohexane-1,4-dicarboxylic acid (1,4-chdcH2) as a organic acid ligand and 2-methyl-1H-imidazole (L) as a secondary ligand, resulting in a new helical chain structure, [Co(1,4-chdc)(L)2].H2O, (I), which is reported.

Selected bond lengths and angles for (I) are given in Table 1. In compound (I), each Co(II) atom is four-coordinated by two O atoms from two 1,4-chdc ligands, and two N atoms from two L molecules in a distorted tetrahedral geometry (Fig. 1). The Co1—O1 and Co1—O3i distances are 1.955 (2) and 2.0042 (16) Å, respectively (Table 1). The Co1—N1 and Co1—N4 distances are 2.0460 (19) and 2.024 (2) Å, respectively (Table 1). Each 1,4-chdc ligand links two neighboring Co(II) atoms in a bidentate mode, generating a unique helical chain (Fig. 2). These chains are decorated with L ligands alternately at two sides. Finally, the O—H···O and N—H···O hydrogen bonds complete the structure of (I).

Related literature top

Two isomorphous structures (Qi et al., 2003) of coordination polymers with cyclohexane-1,4-dicarboxylate (1,4-chdc) have been reported, viz. [Co2(phen)2(1,4-chdc)2(H2O)2]n and [Ni2(phen)2(1,4-chdc)2(H2O)2]n (phen is 1,10-phenanthroline). The striking feature of the two compounds is that they both exhibit an infinite helical chain-like structure with 21 helices.

For related literature, see: Chen & Liu (2002); Zhang et al. (2007).

Experimental top

A mixture of CoCl2.2H2O (0.5 mmol), 1,4-chdc acid (0.5 mmol), and L (0.5 mmol) was adjusted to pH=6.5 by addition of aqueous NaOH solution. The resulting solution was filtered, the filtrate was allowed to stand in air at room temperature for one week, and the pink crystals of (I) were obtained (yield 39% based on Co).

Refinement top

All H atoms on C and N atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.93 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.

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) 1 - x, y - 1/2, 1.5 - z.
[Figure 2] Fig. 2. View of the helical chain structure of (I).
catena-Poly[[[bis(2-methyl-1H-imidazole)cobalt(II)] -µ-cyclohexane-1,4-dicarboxylato] monohydrate] top
Crystal data top
[Co(C8H10O4)(C4H6N2)2]·H2OF(000) = 860
Mr = 411.32Dx = 1.450 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 11934 reflections
a = 13.300 (3) Åθ = 3.2–27.5°
b = 11.075 (2) ŵ = 0.95 mm−1
c = 14.334 (3) ÅT = 293 K
β = 116.82 (3)°Block, pink
V = 1884.2 (8) Å30.29 × 0.27 × 0.24 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4295 independent reflections
Radiation source: rotating anode3311 reflections with I > 2σ(I)
graphiteRint = 0.046
Detector resolution: 10.0 pixels mm-1θmax = 27.5°, θmin = 3.2°
ω scanh = −15→17
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −14→14
Tmin = 0.752, Tmax = 0.798l = −18→16
15286 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.039P)2 + 0.6548P]
where P = (Fo2 + 2Fc2)/3
4295 reflections(Δ/σ)max = 0.001
245 parametersΔρmax = 0.37 e Å−3
3 restraintsΔρmin = −0.25 e Å−3
Crystal data top
[Co(C8H10O4)(C4H6N2)2]·H2OV = 1884.2 (8) Å3
Mr = 411.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.300 (3) ŵ = 0.95 mm−1
b = 11.075 (2) ÅT = 293 K
c = 14.334 (3) Å0.29 × 0.27 × 0.24 mm
β = 116.82 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		4295 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3311 reflections with I > 2σ(I)
Tmin = 0.752, Tmax = 0.798Rint = 0.046
15286 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094Δρmax = 0.37 e Å−3
S = 1.06Δρmin = −0.25 e Å−3
4295 reflectionsAbsolute structure: ?
245 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
C10.4008 (2)0.2780 (2)0.71383 (18)0.0401 (6)
C20.4978 (2)0.2657 (2)0.68613 (18)0.0360 (5)
H2A0.48890.18730.65160.043*
C30.6113 (2)0.2625 (2)0.78389 (18)0.0410 (6)
H3A0.62280.33820.82140.049*
H3B0.61090.19810.82950.049*
C40.7079 (2)0.2425 (2)0.7561 (2)0.0432 (6)
H4A0.70220.16170.72800.052*
H4B0.77880.24790.81920.052*
C50.7085 (2)0.3338 (2)0.67631 (17)0.0327 (5)
H50.76320.30540.65290.039*
C60.5928 (2)0.3373 (2)0.58001 (17)0.0386 (6)
H6A0.59280.40030.53300.046*
H6B0.57960.26090.54330.046*
C70.4978 (2)0.3608 (2)0.60950 (17)0.0374 (5)
H7A0.50720.44020.64090.045*
H7B0.42610.35930.54710.045*
C80.74491 (19)0.4602 (2)0.72160 (17)0.0319 (5)
C90.3517 (2)0.4190 (2)0.92264 (19)0.0464 (6)
H90.40150.43460.89480.056*
C100.3467 (3)0.4798 (3)1.0017 (2)0.0540 (8)
H100.39190.54451.03830.065*
C110.2184 (2)0.3384 (2)0.94879 (17)0.0397 (6)
C120.1208 (3)0.2644 (3)0.9383 (3)0.0629 (8)
H12A0.06130.31660.93420.094*
H12B0.14340.21230.99790.094*
H12C0.09460.21650.87590.094*
C130.0093 (2)0.1407 (2)0.6170 (2)0.0453 (6)
H130.02390.05830.62690.054*
C14−0.0897 (2)0.1900 (3)0.5501 (2)0.0553 (7)
H14−0.15490.14910.50560.066*
C150.0311 (2)0.3347 (2)0.63310 (17)0.0347 (5)
C160.0767 (2)0.4585 (2)0.6651 (2)0.0508 (7)
H16A0.03270.51470.61100.076*
H16B0.15350.46090.67660.076*
H16C0.07320.48000.72850.076*
N10.27049 (17)0.32969 (17)0.88959 (14)0.0362 (5)
N20.2633 (2)0.42856 (19)1.01784 (15)0.0485 (6)
H20.24270.45011.06430.058*
N30.08621 (16)0.23135 (16)0.66915 (14)0.0338 (4)
N4−0.07494 (17)0.3123 (2)0.56069 (16)0.0445 (5)
H4−0.12500.36580.52680.053*
O10.3881 (2)0.19246 (18)0.76549 (19)0.0648 (6)
O20.33529 (19)0.3642 (2)0.68658 (16)0.0742 (7)
O1W−0.23698 (18)0.48020 (19)0.47705 (16)0.0562 (5)
O30.74594 (15)0.54197 (14)0.65811 (12)0.0387 (4)
O40.77284 (16)0.48266 (16)0.81481 (13)0.0480 (5)
Co10.24756 (3)0.20400 (3)0.77712 (2)0.03035 (10)
HW12−0.249 (2)0.503 (2)0.5266 (16)0.054 (9)*
HW11−0.271 (3)0.521 (3)0.4237 (16)0.077 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0397 (14)0.0493 (15)0.0358 (12)−0.0085 (12)0.0209 (11)−0.0083 (11)
C20.0381 (13)0.0353 (12)0.0393 (12)−0.0057 (10)0.0216 (10)−0.0058 (10)
C30.0417 (14)0.0449 (14)0.0376 (13)0.0004 (11)0.0190 (11)0.0097 (11)
C40.0386 (14)0.0353 (12)0.0543 (15)0.0063 (11)0.0198 (12)0.0078 (11)
C50.0336 (12)0.0315 (11)0.0394 (12)−0.0013 (9)0.0221 (10)−0.0063 (9)
C60.0436 (15)0.0450 (13)0.0310 (11)−0.0108 (11)0.0203 (11)−0.0070 (10)
C70.0322 (13)0.0462 (14)0.0306 (11)−0.0018 (11)0.0112 (10)0.0010 (10)
C80.0304 (12)0.0341 (12)0.0344 (11)−0.0029 (10)0.0175 (9)−0.0047 (9)
C90.0522 (17)0.0449 (15)0.0409 (13)−0.0072 (12)0.0201 (12)−0.0042 (11)
C100.069 (2)0.0444 (15)0.0386 (14)−0.0037 (14)0.0160 (13)−0.0106 (11)
C110.0526 (16)0.0381 (13)0.0303 (11)0.0099 (11)0.0205 (11)0.0046 (10)
C120.077 (2)0.066 (2)0.0678 (19)−0.0042 (17)0.0528 (18)−0.0046 (15)
C130.0416 (15)0.0364 (14)0.0538 (15)−0.0033 (11)0.0178 (12)0.0026 (11)
C140.0375 (15)0.0544 (18)0.0625 (17)−0.0095 (13)0.0125 (13)−0.0024 (14)
C150.0363 (13)0.0384 (12)0.0335 (11)0.0039 (10)0.0195 (10)0.0020 (9)
C160.0540 (17)0.0361 (14)0.0571 (16)0.0071 (12)0.0206 (13)0.0013 (12)
N10.0447 (12)0.0351 (10)0.0295 (10)0.0014 (9)0.0174 (9)−0.0018 (8)
N20.0738 (17)0.0435 (12)0.0314 (10)0.0133 (12)0.0264 (11)−0.0012 (9)
N30.0343 (10)0.0319 (10)0.0345 (10)0.0025 (8)0.0149 (8)0.0012 (8)
N40.0337 (11)0.0502 (13)0.0471 (12)0.0109 (10)0.0160 (9)0.0083 (10)
O10.0752 (15)0.0534 (12)0.0987 (16)−0.0031 (11)0.0682 (14)0.0062 (11)
O20.0662 (14)0.1131 (19)0.0603 (12)0.0437 (14)0.0436 (11)0.0330 (13)
O1W0.0605 (13)0.0701 (14)0.0449 (11)0.0277 (11)0.0298 (10)0.0136 (10)
O30.0531 (11)0.0310 (8)0.0398 (9)−0.0039 (7)0.0279 (8)−0.0035 (7)
O40.0548 (12)0.0573 (11)0.0340 (9)−0.0179 (9)0.0219 (8)−0.0143 (8)
Co10.03402 (18)0.03078 (16)0.02738 (16)0.00234 (13)0.01485 (12)0.00074 (12)
Geometric parameters (Å, °) top
C1—O21.231 (3)C10—H100.9300
C1—O11.260 (3)C11—N11.319 (3)
C1—C21.518 (4)C11—N21.342 (3)
C2—C71.521 (3)C11—C121.484 (4)
C2—C31.528 (3)C12—H12A0.9600
C2—H2A0.9800C12—H12B0.9600
C3—C41.523 (4)C12—H12C0.9600
C3—H3A0.9700C13—C141.346 (4)
C3—H3B0.9700C13—N31.387 (3)
C4—C51.530 (3)C13—H130.9300
C4—H4A0.9700C14—N41.367 (3)
C4—H4B0.9700C14—H140.9300
C5—C81.526 (3)C15—N31.332 (3)
C5—C61.536 (3)C15—N41.344 (3)
C5—H50.9800C15—C161.486 (3)
C6—C71.524 (3)C16—H16A0.9600
C6—H6A0.9700C16—H16B0.9600
C6—H6B0.9700C16—H16C0.9600
C7—H7A0.9700Co1—N12.0460 (19)
C7—H7B0.9700N2—H20.8600
C8—O41.240 (3)Co1—N32.024 (2)
C8—O31.289 (3)N4—H40.8600
C9—C101.346 (4)Co1—O11.955 (2)
C9—N11.382 (3)O1W—HW120.837 (16)
C9—H90.9300O1W—HW110.826 (17)
C10—N21.356 (4)Co1—O3i2.0042 (16)
O2—C1—O1120.4 (3)N2—C10—H10126.6
O2—C1—C2123.4 (2)N1—C11—N2110.0 (2)
O1—C1—C2116.2 (2)N1—C11—C12125.7 (2)
C1—C2—C7113.8 (2)N2—C11—C12124.3 (2)
C1—C2—C3111.52 (19)C11—C12—H12A109.5
C7—C2—C3110.88 (19)C11—C12—H12B109.5
C1—C2—H2A106.7H12A—C12—H12B109.5
C7—C2—H2A106.7C11—C12—H12C109.5
C3—C2—H2A106.7H12A—C12—H12C109.5
C4—C3—C2111.4 (2)H12B—C12—H12C109.5
C4—C3—H3A109.4C14—C13—N3109.7 (2)
C2—C3—H3A109.4C14—C13—H13125.2
C4—C3—H3B109.4N3—C13—H13125.2
C2—C3—H3B109.4C13—C14—N4106.1 (2)
H3A—C3—H3B108.0C13—C14—H14126.9
C3—C4—C5112.9 (2)N4—C14—H14126.9
C3—C4—H4A109.0N3—C15—N4110.0 (2)
C5—C4—H4A109.0N3—C15—C16126.6 (2)
C3—C4—H4B109.0N4—C15—C16123.3 (2)
C5—C4—H4B109.0C15—C16—H16A109.5
H4A—C4—H4B107.8C15—C16—H16B109.5
C8—C5—C4113.31 (19)H16A—C16—H16B109.5
C8—C5—C6110.85 (19)C15—C16—H16C109.5
C4—C5—C6110.3 (2)H16A—C16—H16C109.5
C8—C5—H5107.4H16B—C16—H16C109.5
C4—C5—H5107.4C11—N1—C9106.5 (2)
C6—C5—H5107.4C11—N1—Co1128.45 (18)
C7—C6—C5112.02 (18)C9—N1—Co1124.96 (18)
C7—C6—H6A109.2C11—N2—C10108.2 (2)
C5—C6—H6A109.2C11—N2—H2125.9
C7—C6—H6B109.2C10—N2—H2125.9
C5—C6—H6B109.2C15—N3—C13105.7 (2)
H6A—C6—H6B107.9C15—N3—Co1129.33 (16)
C2—C7—C6110.6 (2)C13—N3—Co1125.00 (16)
C2—C7—H7A109.5C15—N4—C14108.5 (2)
C6—C7—H7A109.5C15—N4—H4125.8
C2—C7—H7B109.5C14—N4—H4125.8
C6—C7—H7B109.5C1—O1—Co1112.82 (19)
H7A—C7—H7B108.1HW12—O1W—HW11113 (2)
O4—C8—O3121.7 (2)C8—O3—Co1ii108.32 (14)
O4—C8—C5121.7 (2)O1—Co1—O3i97.93 (8)
O3—C8—C5116.51 (18)O1—Co1—N3132.04 (9)
C10—C9—N1108.6 (3)O3i—Co1—N3107.31 (8)
C10—C9—H9125.7O1—Co1—N1107.66 (9)
N1—C9—H9125.7O3i—Co1—N1106.51 (7)
C9—C10—N2106.8 (2)N3—Co1—N1103.32 (8)
C9—C10—H10126.6
O2—C1—C2—C7−7.7 (3)N4—C15—N3—C13−0.9 (3)
O1—C1—C2—C7170.7 (2)C16—C15—N3—C13179.6 (3)
O2—C1—C2—C3118.6 (3)N4—C15—N3—Co1179.31 (16)
O1—C1—C2—C3−63.0 (3)C16—C15—N3—Co1−0.2 (4)
C1—C2—C3—C4176.5 (2)C14—C13—N3—C150.7 (3)
C7—C2—C3—C4−55.5 (3)C14—C13—N3—Co1−179.42 (19)
C2—C3—C4—C553.8 (3)N3—C15—N4—C140.7 (3)
C3—C4—C5—C872.4 (3)C16—C15—N4—C14−179.8 (3)
C3—C4—C5—C6−52.6 (3)C13—C14—N4—C15−0.2 (3)
C8—C5—C6—C7−72.2 (2)O2—C1—O1—Co18.0 (3)
C4—C5—C6—C754.1 (3)C2—C1—O1—Co1−170.51 (16)
C1—C2—C7—C6−176.17 (19)O4—C8—O3—Co1ii−16.5 (3)
C3—C2—C7—C657.1 (3)C5—C8—O3—Co1ii164.01 (15)
C5—C6—C7—C2−57.0 (3)C1—O1—Co1—O3i171.49 (18)
C4—C5—C8—O41.4 (3)C1—O1—Co1—N349.5 (2)
C6—C5—C8—O4126.1 (2)C1—O1—Co1—N1−78.3 (2)
C4—C5—C8—O3−179.2 (2)C15—N3—Co1—O1−87.9 (2)
C6—C5—C8—O3−54.5 (3)C13—N3—Co1—O192.3 (2)
N1—C9—C10—N20.1 (3)C15—N3—Co1—O3i153.67 (19)
N3—C13—C14—N4−0.3 (3)C13—N3—Co1—O3i−26.1 (2)
N2—C11—N1—C9−0.3 (3)C15—N3—Co1—N141.4 (2)
C12—C11—N1—C9176.8 (3)C13—N3—Co1—N1−138.4 (2)
N2—C11—N1—Co1175.74 (15)C11—N1—Co1—O1−154.1 (2)
C12—C11—N1—Co1−7.1 (4)C9—N1—Co1—O121.3 (2)
C10—C9—N1—C110.1 (3)C11—N1—Co1—O3i−49.9 (2)
C10—C9—N1—Co1−176.08 (18)C9—N1—Co1—O3i125.47 (19)
N1—C11—N2—C100.3 (3)C11—N1—Co1—N363.0 (2)
C12—C11—N2—C10−176.8 (3)C9—N1—Co1—N3−121.63 (19)
C9—C10—N2—C11−0.3 (3)
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O2iii0.83 (2)1.90 (2)2.723 (3)171 (3)
O1W—HW12···O3iv0.84 (2)1.96 (2)2.790 (3)170 (3)
N2—H2···O4v0.861.982.827 (3)168
N4—H4···O1W0.861.842.685 (3)169
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) x−1, y, z; (v) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Co1—N12.0460 (19)Co1—O11.955 (2)
Co1—N32.024 (2)Co1—O3i2.0042 (16)
O1—Co1—O3i97.93 (8)O1—Co1—N1107.66 (9)
O1—Co1—N3132.04 (9)O3i—Co1—N1106.51 (7)
O3i—Co1—N3107.31 (8)N3—Co1—N1103.32 (8)
Symmetry codes: (i) −x+1, y−1/2, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O2ii0.83 (2)1.90 (2)2.723 (3)171 (3)
O1W—HW12···O3iii0.84 (2)1.96 (2)2.790 (3)170 (3)
N2—H2···O4iv0.861.982.827 (3)168
N4—H4···O1W0.861.842.685 (3)169
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+2.
Acknowledgements top

The authors thank Anshan Normal University for supporting this work.

references
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