Acta Cryst. (2009). E65, m494 [ doi:10.1107/S1600536809012422 ]
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O)bis(pyridine-N)copper(II)In the crystal structure of the title complex, [Cu(C4H5O2)2(C5H5N)2(H2O)], the CuII cation is located on a twofold rotation axis and coordinated by two methylacrylate anions, two pyridine ligands and one water molecule in a distorted square-pyramidal geometry. The coordinated water molecule is also located on the twofold axis. In the crystal structure O-H
O hydrogen bonds link the molecules, forming chains along the c axis.
HL, CH2C(CH3)COOH, (0.5 ml, 6.0 mmol) and Cu(NO3)2.3H2O (240 mg, 1.0 mmol) were dissolved in 60 ml H2O, and the pH adjusted to 4.0 using 0.5 M NaOH. Two mililiters of 1.0 M pyridine solution were added into the mixed solution with stirring. After filtration, the filtrate was allowed to stand at room temperature and single crystals were obtained after one week.
Methyl H atoms were constrained to an ideal geometry with C—H distances of 0.96 Å and Uiso(H) = 1.5Ueq(C), but each group was allowed to rotate freely about its C—C bond. The methylene H atoms and aromatic H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008; program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./xu2491fig1thm.gif)
| Fig. 1. The molecular structure of the title molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms. |
| [Cu(C4H5O2)2(C5H5N)2(H2O)] | F(000) = 1704 |
| Mr = 409.92 | Dx = 1.432 Mg m−3 |
| Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71069 Å |
| Hall symbol: F 2 -2d | Cell parameters from 8692 reflections |
| a = 15.619 (3) Å | θ = 3.0–27.5° |
| b = 40.200 (8) Å | µ = 1.18 mm−1 |
| c = 6.0576 (12) Å | T = 293 K |
| V = 3803.4 (13) Å3 | Platelet, blue |
| Z = 8 | 0.50 × 0.36 × 0.08 mm |
| Rigaku R-AXIS RAPID IP diffractometer | 1808 independent reflections |
| Radiation source: fine-focus sealed tube | 1740 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 25.8°, θmin = 3.3° |
| ω scans | h = −18→18 |
| Absorption correction: multi-scan ABSCOR (Higashi, 1995) | k = −48→48 |
| Tmin = 0.612, Tmax = 0.913 | l = −7→7 |
| 7925 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.055 | w = 1/[σ2(Fo2) + (0.0325P)2 + 0.6515P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.09 | (Δ/σ)max < 0.001 |
| 1808 reflections | Δρmax = 0.15 e Å−3 |
| 124 parameters | Δρmin = −0.19 e Å−3 |
| 1 restraint | Absolute structure: Flack (1983), 797 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.006 (13) |
| [Cu(C4H5O2)2(C5H5N)2(H2O)] | V = 3803.4 (13) Å3 |
| Mr = 409.92 | Z = 8 |
| Orthorhombic, Fdd2 | Mo Kα radiation |
| a = 15.619 (3) Å | µ = 1.18 mm−1 |
| b = 40.200 (8) Å | T = 293 K |
| c = 6.0576 (12) Å | 0.50 × 0.36 × 0.08 mm |
| Rigaku R-AXIS RAPID IP diffractometer | 1808 independent reflections |
| Absorption correction: multi-scan ABSCOR (Higashi, 1995) | 1740 reflections with I > 2σ(I) |
| Tmin = 0.612, Tmax = 0.913 | Rint = 0.027 |
| 7925 measured reflections | θmax = 25.8° |
| R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.055 | Δρmax = 0.15 e Å−3 |
| S = 1.09 | Δρmin = −0.19 e Å−3 |
| 1808 reflections | Absolute structure: Flack (1983), 797 Friedel pairs |
| 124 parameters | Flack parameter: 0.006 (13) |
| 1 restraint |
Experimental. Analysis: calculated C 52.74, H 5.41, N 6.83%; found C 52.61, H 5.22, N 6.69%. Spectroscopic analysis: IR (KBr, ν cm-1): 700, 832, 936, 1036, 1214, 1243, 1368, 1417, 1599, 1642. |
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. |
| x | y | z | Uiso*/Ueq | ||
| Cu | 1.0000 | 0.0000 | 0.11357 (7) | 0.03375 (10) | |
| O1 | 1.0000 | 0.0000 | 0.4901 (4) | 0.0450 (5) | |
| O2 | 1.05574 (8) | 0.04310 (3) | 0.1163 (3) | 0.0442 (3) | |
| O3 | 1.03022 (11) | 0.05452 (4) | −0.2378 (3) | 0.0529 (4) | |
| N1 | 0.88531 (9) | 0.02292 (3) | 0.0789 (3) | 0.0361 (3) | |
| C1 | 1.05091 (11) | 0.06268 (5) | −0.0494 (3) | 0.0371 (4) | |
| C2 | 1.07255 (14) | 0.09857 (5) | −0.0019 (4) | 0.0460 (5) | |
| C3 | 1.0791 (3) | 0.10857 (7) | 0.2115 (5) | 0.0967 (13) | |
| H3A | 1.0922 | 0.1306 | 0.2439 | 0.116* | |
| H3B | 1.0705 | 0.0934 | 0.3252 | 0.116* | |
| C4 | 1.0850 (2) | 0.12071 (5) | −0.1829 (5) | 0.0694 (7) | |
| H4A | 1.1000 | 0.1423 | −0.1281 | 0.104* | |
| H4B | 1.0331 | 0.1222 | −0.2672 | 0.104* | |
| H4C | 1.1302 | 0.1125 | −0.2752 | 0.104* | |
| C5 | 0.83858 (12) | 0.01819 (5) | −0.1017 (3) | 0.0431 (5) | |
| H5 | 0.8607 | 0.0050 | −0.2143 | 0.052* | |
| C6 | 0.75841 (12) | 0.03207 (5) | −0.1284 (8) | 0.0485 (4) | |
| H6 | 0.7275 | 0.0286 | −0.2576 | 0.058* | |
| C7 | 0.72506 (13) | 0.05110 (5) | 0.0387 (4) | 0.0493 (5) | |
| H7 | 0.6705 | 0.0602 | 0.0262 | 0.059* | |
| C8 | 0.77349 (15) | 0.05649 (5) | 0.2250 (5) | 0.0523 (6) | |
| H8 | 0.7525 | 0.0695 | 0.3397 | 0.063* | |
| C9 | 0.85367 (14) | 0.04220 (4) | 0.2390 (4) | 0.0443 (4) | |
| H9 | 0.8868 | 0.0461 | 0.3640 | 0.053* | |
| H1 | 1.0098 (15) | 0.0163 (6) | 0.569 (6) | 0.052 (8)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu | 0.02640 (14) | 0.04033 (15) | 0.03451 (15) | 0.00130 (13) | 0.000 | 0.000 |
| O1 | 0.0619 (14) | 0.0422 (12) | 0.0309 (11) | −0.0041 (9) | 0.000 | 0.000 |
| O2 | 0.0355 (6) | 0.0454 (6) | 0.0516 (8) | −0.0031 (5) | −0.0055 (7) | 0.0079 (7) |
| O3 | 0.0684 (10) | 0.0493 (7) | 0.0410 (8) | −0.0091 (7) | 0.0044 (8) | −0.0081 (7) |
| N1 | 0.0290 (7) | 0.0405 (7) | 0.0389 (9) | 0.0003 (6) | 0.0015 (7) | 0.0002 (7) |
| C1 | 0.0287 (9) | 0.0394 (9) | 0.0432 (10) | 0.0040 (7) | 0.0049 (8) | −0.0027 (8) |
| C2 | 0.0534 (12) | 0.0379 (9) | 0.0468 (11) | 0.0101 (8) | −0.0090 (10) | −0.0030 (9) |
| C3 | 0.185 (4) | 0.0516 (14) | 0.0534 (16) | 0.0172 (18) | −0.027 (2) | −0.0070 (12) |
| C4 | 0.109 (2) | 0.0436 (10) | 0.0552 (16) | −0.0013 (12) | −0.0059 (15) | 0.0058 (11) |
| C5 | 0.0357 (9) | 0.0541 (10) | 0.0394 (12) | 0.0002 (8) | −0.0002 (8) | −0.0046 (8) |
| C6 | 0.0362 (9) | 0.0556 (10) | 0.0538 (11) | −0.0010 (8) | −0.0128 (11) | 0.0031 (17) |
| C7 | 0.0319 (9) | 0.0450 (10) | 0.0711 (15) | 0.0064 (8) | −0.0002 (10) | 0.0046 (10) |
| C8 | 0.0475 (12) | 0.0461 (11) | 0.0634 (14) | 0.0101 (9) | 0.0061 (11) | −0.0088 (11) |
| C9 | 0.0419 (11) | 0.0457 (9) | 0.0453 (11) | 0.0022 (8) | −0.0027 (9) | −0.0038 (9) |
| Cu—O1 | 2.281 (2) | C3—H3B | 0.9300 |
| Cu—O2 | 1.9389 (12) | C4—H4A | 0.9600 |
| Cu—O2i | 1.9391 (12) | C4—H4B | 0.9600 |
| Cu—N1 | 2.0254 (14) | C4—H4C | 0.9600 |
| Cu—N1i | 2.0254 (14) | C5—C6 | 1.380 (3) |
| O1—H1 | 0.82 (3) | C5—H5 | 0.9300 |
| O2—C1 | 1.278 (2) | C6—C7 | 1.371 (5) |
| O3—C1 | 1.230 (3) | C6—H6 | 0.9300 |
| N1—C5 | 1.329 (3) | C7—C8 | 1.376 (4) |
| N1—C9 | 1.336 (3) | C7—H7 | 0.9300 |
| C1—C2 | 1.510 (3) | C8—C9 | 1.380 (3) |
| C2—C3 | 1.357 (4) | C8—H8 | 0.9300 |
| C2—C4 | 1.425 (3) | C9—H9 | 0.9300 |
| C3—H3A | 0.9300 | ||
| O2—Cu—O2i | 179.03 (10) | H3A—C3—H3B | 120.0 |
| O2—Cu—N1 | 89.51 (5) | C2—C4—H4A | 109.5 |
| O2i—Cu—N1 | 90.59 (5) | C2—C4—H4B | 109.5 |
| O2—Cu—N1i | 90.59 (5) | H4A—C4—H4B | 109.5 |
| O2i—Cu—N1i | 89.51 (5) | C2—C4—H4C | 109.5 |
| N1—Cu—N1i | 168.08 (10) | H4A—C4—H4C | 109.5 |
| O2—Cu—O1 | 89.51 (5) | H4B—C4—H4C | 109.5 |
| O2i—Cu—O1 | 89.51 (5) | N1—C5—C6 | 122.5 (3) |
| N1—Cu—O1 | 95.96 (5) | N1—C5—H5 | 118.8 |
| N1i—Cu—O1 | 95.96 (5) | C6—C5—H5 | 118.8 |
| Cu—O1—H1 | 126 (2) | C7—C6—C5 | 118.9 (3) |
| C1—O2—Cu | 121.15 (13) | C7—C6—H6 | 120.5 |
| C5—N1—C9 | 118.52 (16) | C5—C6—H6 | 120.5 |
| C5—N1—Cu | 120.41 (13) | C6—C7—C8 | 119.0 (2) |
| C9—N1—Cu | 121.03 (14) | C6—C7—H7 | 120.5 |
| O3—C1—O2 | 125.43 (17) | C8—C7—H7 | 120.5 |
| O3—C1—C2 | 119.36 (18) | C7—C8—C9 | 118.9 (2) |
| O2—C1—C2 | 115.21 (18) | C7—C8—H8 | 120.5 |
| C3—C2—C4 | 122.5 (2) | C9—C8—H8 | 120.5 |
| C3—C2—C1 | 118.8 (2) | N1—C9—C8 | 122.1 (2) |
| C4—C2—C1 | 118.7 (2) | N1—C9—H9 | 118.9 |
| C2—C3—H3A | 120.0 | C8—C9—H9 | 118.9 |
| C2—C3—H3B | 120.0 |
| Symmetry codes: (i) −x+2, −y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O3ii | 0.83 (3) | 1.96 (3) | 2.783 (2) | 178 (2) |
| Symmetry codes: (ii) x, y, z+1. |
| Cu—O1 | 2.281 (2) | O2—C1 | 1.278 (2) |
| Cu—O2 | 1.9389 (12) | O3—C1 | 1.230 (3) |
| Cu—N1 | 2.0254 (14) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O3i | 0.83 (3) | 1.96 (3) | 2.783 (2) | 178 (2) |
| Symmetry codes: (i) x, y, z+1. |
This work was supported by the Natural Science Foundation of Zhejiang Province, China (M203105).
Du, M., Cai, H. & Zhao, X.-J. (2004). Acta Cryst. E60, m1139–m1141.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Hu, R.-Z., Liu, Z.-D., Tan, M.-Y. & Zhu, H.-L. (2004). Acta Cryst. E60, m946–m947.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wu, B. & Wang, G. (2004). Acta Cryst. E60, m1764–m1765.
Zhu, X.-F., Zhao, L.-M., Hou, G.-F. & Gao, J.-S. (2007). Acta Cryst. E63, m1809.
Copper complexes with organic acids and other donor ligands exist extensively in living things, playing an important role in a vast range of chemical and biochemical catalytic systems. A series of copper-carboxylate complexes has been reported (Du et al., 2004; Hu et al., 2004; Zhu et al., 2007).
The molecular structure is shown in Fig. 1. The Cu atom is located on a twofold axis and coordinated with two methylacrylate, two pyridine ligands and one coordinated water molecule in a distorted square-pyramidal geometry (Table 1).
The compound is an infinite one-dimensional network structure connected by hydrogen bonds. It forms hydrogen bonds between coordination waters and carboxy group (Table 2).
The corresponding complex with one pyridine ligand has binuclear cage structural unit, two Cu atoms are bridged by four µ2–O,O'α-methacrylate groups, forming a cage structure (Wu et al., 2004).