Acta Cryst. (2009). E65, m556 [ doi:10.1107/S1600536809013889 ]
![[mu]](/logos/entities/mu_rmgif.gif)
3-pyridine-3,5-dicarboxylato-![[kappa]](/logos/entities/kappa_rmgif.gif)
3N:O3:O5)copper(II)]The title complex, [Cu(C7H3NO4)(H2O)2]n, was prepared under hydrothermal reaction conditions. In the crystal structure, the CuII cation is located on a twofold rotation axis and is coordinated by two carboxylate O atoms and one N atom from three pyridine-3,5-dicarboxylate (PDA) anions and two water molecules with a distorted trigonal-bipyramidal geometry. The tridentate PDA anion is also located on the twofold rotation axis and bridges the CuII cations to form a two-dimensional polymeric layer. O-H
O hydrogen bonding between layers links the two-dimensional layers into a three-dimensional supramolecular framework.
The compound was synthesized by heating a mixture of Cu(CH3COO)2 (0.25 mmol, 0.05 g), 3,5-pyridinedicarboxylic acid (0.25 mmol, 0.0418 g), CH3OH (5 ml) and H2O (5 ml) in a Teflon-lined autoclave (25 ml) at 150 °C for 3 d. Green crystals of the title compound appeared after cooling to room temperature.
The water H atoms were placed in chemically sensible positions on the basis of hydrogen bonding, and were refined with distance restraint O—H = 0.85 Å. Other H atoms were placed in calculated positions and were refined in riding mode with C—H = 0.93 Å. Uiso(H) = 1.2Ueq(C,O).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./xu2500fig1thm.gif)
| Fig. 1. The molecular structure of the title complex with displacement ellipsoids drawn at the 30% probability level [symmetry code: (A) -x + 2, y, 1/2 - z]. |
![[Figure 2]](./xu2500fig2thm.gif)
| Fig. 2. The crystal packing diagram of the title compound, viewed along the c axis. |
| [Cu(C7H3NO4)(H2O)2] | F(000) = 532 |
| Mr = 264.68 | Dx = 2.018 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2266 reflections |
| a = 10.1285 (16) Å | θ = 2.7–28.3° |
| b = 12.0669 (19) Å | µ = 2.52 mm−1 |
| c = 7.2770 (11) Å | T = 298 K |
| β = 101.584 (2)° | Block, green |
| V = 871.3 (2) Å3 | 0.23 × 0.18 × 0.07 mm |
| Z = 4 |
| Bruker APEXII 1000 CCD area-detector diffractometer | 1003 independent reflections |
| Radiation source: fine-focus sealed tube | 892 reflections with I > 2σ(I) |
| graphite | Rint = 0.024 |
| φ and ω scans | θmax = 28.3°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −13→12 |
| Tmin = 0.588, Tmax = 0.840 | k = −15→12 |
| 2751 measured reflections | l = −9→9 |
| 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.148 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.108P)2 + 2.2514P] where P = (Fo2 + 2Fc2)/3 |
| 1003 reflections | (Δ/σ)max < 0.001 |
| 70 parameters | Δρmax = 1.31 e Å−3 |
| 0 restraints | Δρmin = −0.48 e Å−3 |
| [Cu(C7H3NO4)(H2O)2] | V = 871.3 (2) Å3 |
| Mr = 264.68 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 10.1285 (16) Å | µ = 2.52 mm−1 |
| b = 12.0669 (19) Å | T = 298 K |
| c = 7.2770 (11) Å | 0.23 × 0.18 × 0.07 mm |
| β = 101.584 (2)° |
| Bruker APEXII 1000 CCD area-detector diffractometer | 1003 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 892 reflections with I > 2σ(I) |
| Tmin = 0.588, Tmax = 0.840 | Rint = 0.024 |
| 2751 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
| wR(F2) = 0.148 | Δρmax = 1.31 e Å−3 |
| S = 1.00 | Δρmin = −0.48 e Å−3 |
| 1003 reflections | Absolute structure: ? |
| 70 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Cu1 | 0.5000 | 0.16047 (5) | 0.2500 | 0.0252 (3) | |
| O1W | 0.4771 (4) | 0.1611 (2) | −0.0245 (5) | 0.0387 (8) | |
| H1WA | 0.5216 | 0.1161 | −0.0782 | 0.046* | |
| H1WB | 0.4226 | 0.2065 | −0.0896 | 0.046* | |
| O1 | 0.6503 (3) | 0.0232 (3) | 0.2667 (5) | 0.0387 (8) | |
| O2 | 0.7647 (4) | 0.1761 (3) | 0.2777 (7) | 0.0573 (12) | |
| C1 | 0.7562 (4) | 0.0748 (4) | 0.2691 (6) | 0.0289 (9) | |
| C2 | 0.8837 (3) | 0.0104 (3) | 0.2610 (5) | 0.0214 (7) | |
| C3 | 1.0000 | 0.0672 (4) | 0.2500 | 0.0227 (10) | |
| H3A | 1.0000 | 0.1443 | 0.2500 | 0.027* | |
| C4 | 0.8885 (3) | −0.1037 (3) | 0.2620 (5) | 0.0227 (8) | |
| H4A | 0.8109 | −0.1426 | 0.2713 | 0.027* | |
| N1 | 1.0000 | −0.1614 (3) | 0.2500 | 0.0215 (9) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0257 (4) | 0.0176 (4) | 0.0328 (4) | 0.000 | 0.0073 (3) | 0.000 |
| O1W | 0.049 (2) | 0.0299 (18) | 0.0370 (17) | 0.0036 (12) | 0.0074 (15) | −0.0021 (12) |
| O1 | 0.0211 (15) | 0.0452 (19) | 0.0507 (19) | 0.0075 (12) | 0.0097 (13) | −0.0097 (15) |
| O2 | 0.040 (2) | 0.0264 (19) | 0.101 (4) | 0.0149 (14) | 0.005 (2) | −0.0080 (18) |
| C1 | 0.0189 (19) | 0.029 (2) | 0.036 (2) | 0.0121 (15) | −0.0006 (15) | −0.0074 (16) |
| C2 | 0.0162 (16) | 0.0185 (17) | 0.0293 (17) | 0.0049 (12) | 0.0043 (14) | −0.0009 (14) |
| C3 | 0.022 (3) | 0.013 (2) | 0.032 (3) | 0.000 | 0.001 (2) | 0.000 |
| C4 | 0.0135 (16) | 0.0187 (18) | 0.0352 (19) | −0.0015 (12) | 0.0033 (14) | −0.0009 (14) |
| N1 | 0.017 (2) | 0.013 (2) | 0.035 (2) | 0.000 | 0.0062 (18) | 0.000 |
| Cu1—O1Wi | 1.964 (4) | C1—C2 | 1.518 (5) |
| Cu1—O1W | 1.964 (4) | C2—C4 | 1.378 (5) |
| Cu1—N1ii | 2.149 (4) | C2—C3 | 1.379 (4) |
| Cu1—O1i | 2.236 (3) | C3—C2iii | 1.379 (4) |
| Cu1—O1 | 2.236 (3) | C3—H3A | 0.9300 |
| O1W—H1WA | 0.8500 | C4—N1 | 1.344 (4) |
| O1W—H1WB | 0.8500 | C4—H4A | 0.9300 |
| O1—C1 | 1.238 (5) | N1—C4iii | 1.344 (4) |
| O2—C1 | 1.226 (5) | N1—Cu1iv | 2.149 (4) |
| O1Wi—Cu1—O1W | 179.54 (17) | O2—C1—C2 | 117.5 (4) |
| O1Wi—Cu1—N1ii | 89.77 (8) | O1—C1—C2 | 118.9 (4) |
| O1W—Cu1—N1ii | 89.77 (8) | C4—C2—C3 | 117.8 (3) |
| O1Wi—Cu1—O1i | 89.90 (13) | C4—C2—C1 | 122.8 (3) |
| O1W—Cu1—O1i | 90.44 (13) | C3—C2—C1 | 119.4 (4) |
| N1ii—Cu1—O1i | 137.80 (9) | C2—C3—C2iii | 120.4 (5) |
| O1Wi—Cu1—O1 | 90.44 (13) | C2—C3—H3A | 119.8 |
| O1W—Cu1—O1 | 89.90 (13) | C2iii—C3—H3A | 119.8 |
| N1ii—Cu1—O1 | 137.80 (9) | N1—C4—C2 | 123.2 (3) |
| O1i—Cu1—O1 | 84.40 (18) | N1—C4—H4A | 118.4 |
| Cu1—O1W—H1WA | 120.0 | C2—C4—H4A | 118.4 |
| Cu1—O1W—H1WB | 120.0 | C4iii—N1—C4 | 117.6 (4) |
| H1WA—O1W—H1WB | 120.0 | C4iii—N1—Cu1iv | 121.2 (2) |
| C1—O1—Cu1 | 101.9 (3) | C4—N1—Cu1iv | 121.2 (2) |
| O2—C1—O1 | 123.7 (4) |
| Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x−1/2, y+1/2, z; (iii) −x+2, y, −z+1/2; (iv) x+1/2, y−1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···O1v | 0.85 | 2.53 | 3.377 (5) | 178 |
| O1W—H1WB···O2vi | 0.85 | 2.21 | 3.052 (5) | 171 |
| Symmetry codes: (v) x, −y, z−1/2; (vi) x−1/2, −y+1/2, z−1/2. |
| Cu1—O1W | 1.964 (4) | Cu1—O1 | 2.236 (3) |
| Cu1—N1i | 2.149 (4) | ||
| O1Wii—Cu1—O1W | 179.54 (17) | O1Wii—Cu1—O1 | 90.44 (13) |
| O1W—Cu1—N1i | 89.77 (8) | O1W—Cu1—O1 | 89.90 (13) |
| O1W—Cu1—O1ii | 90.44 (13) | O1ii—Cu1—O1 | 84.40 (18) |
| N1i—Cu1—O1ii | 137.80 (9) |
| Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+1, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···O1iii | 0.85 | 2.53 | 3.377 (5) | 178 |
| O1W—H1WB···O2iv | 0.85 | 2.21 | 3.052 (5) | 171 |
| Symmetry codes: (iii) x, −y, z−1/2; (iv) x−1/2, −y+1/2, z−1/2. |
The authors acknowledge the National Natural Science Foundation of China for financial support.
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Chang, F., Wang, Z.-M., Sun, H.-L., Gao, S., Wen, G.-H. & Zhang, X.-X. (2005). Dalton Trans. pp. 2976–2978.
Hou, H.-W., Xie, L.-X., Li, G., Ge, T.-Z., Fan, Y.-T. & Zhu, Y. (2004). New J. Chem. 28, 191–199.
Plater, M. J., Roberts, J. A. & Howie, R. A. (1998). J. Chem. Res. pp. 240–241.
Sheldrick, G. M. (2004). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Whitfield, T., Zheng, L.-M., Wang, X.-Q. & Jacobson, A. J. (2001). Solid State Sci. 3, 829–835.
Over the past few years, much progress has been made toward the building of supramolecular structures with metal–organic compounds (Hou et al., 2004). To get designed their intriguing frameworks and properties, an enormous amount of research is being focused in using versatile organic ligands and functional metal ions to construct the novel polymers (Chang et al., 2005). The role of organic carboxylic acid ligand in synthesis such materials are of great interest. Here we report the hydrothermal synthesis and structure characterization of the title compound which is the isomorphism with CoII complex reported in the previous literature (Whitfield et al., 2001; Plater et al., 1998).
The title compound crystallizes in space group C2/c. As illustrated in Fig. 1, in the asymmetric unit of it there is only one crystalographically distinct CuII ions which is coordinated by four O atoms and one N atom with the bond distance Cu—O 2.236 (3) and 2.236 (3) Å and Cu—N 2.149 (4) Å. The 3,5-PDA ligand acts as a tridentate ligand and bridges three equivalent Cu atoms with the Cu···Cu 7.877 Å. The O2 atom of each carboxylate group is terminal and oriented to the Cu1 atom with the Cu1···O2 distance 2.655 Å which are slightly larger than the CoII isomorphism (Co···OT 2.433 Å). A two-dimensional layer structure is thus constructed in the ab plane with openings along the c direction (Fig. 2). Hydrogen bonds are formed between coordinated water molecules and the carboxylate O atoms of adjacent layers (O1W···O1 3.377 (5) Å, O1W···O2 3.052 (5) Å) which furtherly connect the two-dimensional layers to a three-dimensional architecture. The shortes distance between Cu ions in the layers is 5.314 (2) Å.