Acta Cryst. (2008). E64, m356 [ doi:10.1107/S1600536808000597 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
N3)bis[2-(oxaloamino)benzoato(3-)]dicopper(II)barium(II)] dihydrate]In the title coordination polymer, {[BaCu2(C9H4NO5)2(C3H4N2)2(H2O)4]·2H2O}n, the Ba2+ cation is decacoordinate, ligated by four aqua ligands and four [Cu(C9H4O5N)(C3H4N2)] `complex ligands'. The CuII-containing complex-ligands are bridged by the Ba2+ cations, resulting in a one-dimensional polymeric chain structure. The crystal structure is maintained via N-H
O and O-HO hydrogen bonds. There is one disordered solvent water molecule in the asymmetric unit, with occupancies of 0.44 (2) and 0.56 (2).
0.232 g (1 mmol) oxamato-N-benzoic acid (Zang et al., 2003) and 0.12 g (3 mmol) were dissolved in 20 ml water. To this solution, 0.17 g (1 mmol) CuCl2.2H2O and 0.068 g (1 mmol) imidazole were added. After stirring for an hour, 0.208 g (1 mmol) BaCl2 was added. The solution was filtered after stirring for another hour. Evaporation of the filtrate gave red single crystals of the title compound in one week.
The structure was solved by direct methods. All the H atoms were fixed geometrically and constrained with a riding model. d(C—H) = 0.93 Å, Uiso = 1.2Ueq (C) for aromatic H atoms; 0.85 Å, Uiso = 1.5Ueq (O) for H2O hydrogen atoms.
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: publCIF (Westrip, 2008).
![[Figure 1]](./pk2076fig1thm.gif)
| Fig. 1. Asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary size. A disordered solvent water (O10) molecule has been omitted for clarity. Symmetry-equivalent O atoms generated about the Ba1 atom are at (1 - x, y, 1.5 - z), (1 - x, 2 - y, 2 - z) and (x, 2 - y, z - 1/2). |
![[Figure 2]](./pk2076fig2thm.gif)
| Fig. 2. The one-dimensional polymeric chain viewed along the c axis. H atoms, aqueous ligands and solvent water molecules are omitted for clarity. |
| [BaCu2(C9H4NO5)2(C3H4N2)2(H2O)4]·2H2O | F000 = 912 |
| Mr = 920.94 | Dx = 1.981 Mg m−3 |
| Monoclinic, P2/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yc | Cell parameters from 857 reflections |
| a = 10.662 (3) Å | θ = 3.0–27.3º |
| b = 6.9165 (18) Å | µ = 2.71 mm−1 |
| c = 21.335 (5) Å | T = 293 (2) K |
| β = 101.146 (4)º | Block, red |
| V = 1543.6 (7) Å3 | 0.3 × 0.2 × 0.2 mm |
| Z = 2 |
| Bruker SMART CCD area-detector diffractometer | 2713 independent reflections |
| Radiation source: fine-focus sealed tube | 2398 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.084 |
| T = 293(2) K | θmax = 25.0º |
| φ and ω scans | θmin = 2.5º |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −12→12 |
| Tmin = 0.525, Tmax = 0.583 | k = −8→8 |
| 7263 measured reflections | l = −25→15 |
| 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)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 2713 reflections | Δρmax = 0.86 e Å−3 |
| 226 parameters | Δρmin = −0.64 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [BaCu2(C9H4NO5)2(C3H4N2)2(H2O)4]·2H2O | V = 1543.6 (7) Å3 |
| Mr = 920.94 | Z = 2 |
| Monoclinic, P2/c | Mo Kα |
| a = 10.662 (3) Å | µ = 2.71 mm−1 |
| b = 6.9165 (18) Å | T = 293 (2) K |
| c = 21.335 (5) Å | 0.3 × 0.2 × 0.2 mm |
| β = 101.146 (4)º |
| Bruker SMART CCD area-detector diffractometer | 2713 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2398 reflections with I > 2σ(I) |
| Tmin = 0.525, Tmax = 0.583 | Rint = 0.084 |
| 7263 measured reflections |
| R[F2 > 2σ(F2)] = 0.035 | 226 parameters |
| wR(F2) = 0.089 | H-atom parameters constrained |
| S = 1.01 | Δρmax = 0.86 e Å−3 |
| 2713 reflections | Δρmin = −0.64 e Å−3 |
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 > 2σ(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 | Occ. (<1) | |
| Ba1 | 0.5000 | 0.90568 (5) | 0.7500 | 0.03268 (14) | |
| Cu2 | 0.70008 (4) | 0.79877 (8) | 1.03715 (2) | 0.03358 (16) | |
| C1 | 0.4210 (4) | 0.7210 (6) | 0.9961 (2) | 0.0308 (9) | |
| C2 | 0.3109 (4) | 0.6829 (7) | 0.9499 (2) | 0.0413 (10) | |
| H2 | 0.3156 | 0.6890 | 0.9069 | 0.050* | |
| C3 | 0.1959 (4) | 0.6366 (7) | 0.9667 (2) | 0.0459 (12) | |
| H3 | 0.1245 | 0.6136 | 0.9350 | 0.055* | |
| C4 | 0.1856 (4) | 0.6243 (7) | 1.0289 (2) | 0.0460 (12) | |
| H4 | 0.1082 | 0.5917 | 1.0401 | 0.055* | |
| C5 | 0.2922 (4) | 0.6609 (7) | 1.0754 (2) | 0.0415 (10) | |
| H5 | 0.2856 | 0.6533 | 1.1182 | 0.050* | |
| C6 | 0.4103 (4) | 0.7096 (6) | 1.0598 (2) | 0.0334 (9) | |
| C7 | 0.5146 (4) | 0.7449 (7) | 1.1180 (2) | 0.0362 (10) | |
| C8 | 1.0359 (4) | 0.7848 (9) | 1.1711 (2) | 0.0550 (14) | |
| H8 | 1.0897 | 0.7403 | 1.2078 | 0.066* | |
| C9 | 0.9614 (4) | 0.9421 (7) | 1.0840 (2) | 0.0464 (12) | |
| H9 | 0.9563 | 1.0274 | 1.0499 | 0.056* | |
| C10 | 0.9169 (4) | 0.7209 (8) | 1.1470 (2) | 0.0479 (12) | |
| H10 | 0.8736 | 0.6250 | 1.1648 | 0.058* | |
| C12 | 0.5519 (4) | 0.7837 (6) | 0.91832 (19) | 0.0345 (10) | |
| C13 | 0.6890 (4) | 0.8380 (7) | 0.91134 (19) | 0.0339 (9) | |
| N1 | 0.5387 (3) | 0.7682 (5) | 0.97887 (15) | 0.0301 (7) | |
| N2 | 0.8704 (3) | 0.8215 (6) | 1.09186 (17) | 0.0390 (8) | |
| N3 | 1.0623 (3) | 0.9254 (6) | 1.13173 (18) | 0.0484 (10) | |
| H3A | 1.1315 | 0.9922 | 1.1365 | 0.058* | |
| O1 | 0.7097 (3) | 0.8641 (5) | 0.85734 (13) | 0.0460 (8) | |
| O2 | 0.4736 (3) | 0.7653 (6) | 0.86823 (14) | 0.0549 (10) | |
| O3 | 0.7724 (2) | 0.8539 (5) | 0.96263 (13) | 0.0412 (7) | |
| O4 | 0.6293 (3) | 0.7678 (5) | 1.11137 (13) | 0.0466 (8) | |
| O5 | 0.7323 (3) | 1.0322 (6) | 0.72527 (16) | 0.0648 (10) | |
| H5B | 0.7114 | 1.0964 | 0.6909 | 0.097* | |
| H5C | 0.7768 | 0.9304 | 0.7246 | 0.097* | |
| O8 | 0.4863 (3) | 0.7515 (5) | 1.17116 (14) | 0.0462 (8) | |
| O9 | 0.3581 (4) | 0.5293 (6) | 0.7463 (2) | 0.0893 (13) | |
| H9C | 0.2794 | 0.5576 | 0.7421 | 0.134* | |
| H9A | 0.3773 | 0.4384 | 0.7804 | 0.134* | |
| O10 | 0.874 (3) | 0.681 (4) | 0.7671 (15) | 0.143 (6) | 0.44 (2) |
| O10' | 0.8713 (19) | 0.711 (3) | 0.7229 (13) | 0.143 (6) | 0.56 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ba1 | 0.0323 (2) | 0.0479 (2) | 0.01666 (19) | 0.000 | 0.00160 (13) | 0.000 |
| Cu2 | 0.0342 (3) | 0.0463 (4) | 0.0181 (3) | 0.0002 (2) | −0.0003 (2) | −0.0013 (2) |
| C1 | 0.035 (2) | 0.028 (2) | 0.029 (2) | 0.0008 (17) | 0.0056 (17) | −0.0027 (18) |
| C2 | 0.044 (2) | 0.048 (3) | 0.032 (2) | −0.002 (2) | 0.0073 (19) | −0.003 (2) |
| C3 | 0.037 (2) | 0.054 (3) | 0.044 (3) | −0.003 (2) | 0.000 (2) | −0.006 (3) |
| C4 | 0.039 (2) | 0.045 (3) | 0.056 (3) | −0.006 (2) | 0.013 (2) | −0.006 (2) |
| C5 | 0.045 (2) | 0.044 (3) | 0.037 (2) | −0.001 (2) | 0.013 (2) | 0.004 (2) |
| C6 | 0.037 (2) | 0.028 (2) | 0.034 (2) | 0.0018 (17) | 0.0045 (18) | −0.0012 (19) |
| C7 | 0.041 (2) | 0.040 (3) | 0.026 (2) | 0.0017 (19) | 0.0055 (18) | −0.001 (2) |
| C8 | 0.040 (2) | 0.090 (4) | 0.031 (2) | 0.007 (3) | −0.004 (2) | 0.005 (3) |
| C9 | 0.044 (2) | 0.063 (3) | 0.032 (2) | 0.002 (2) | 0.007 (2) | 0.004 (2) |
| C10 | 0.048 (2) | 0.066 (3) | 0.029 (2) | −0.006 (2) | 0.003 (2) | 0.007 (2) |
| C12 | 0.043 (2) | 0.036 (3) | 0.023 (2) | 0.0002 (19) | 0.0032 (18) | 0.0035 (19) |
| C13 | 0.040 (2) | 0.038 (2) | 0.022 (2) | −0.0004 (19) | 0.0019 (17) | 0.000 (2) |
| N1 | 0.0336 (16) | 0.0324 (19) | 0.0228 (17) | 0.0026 (14) | 0.0013 (13) | 0.0009 (15) |
| N2 | 0.0354 (18) | 0.054 (2) | 0.0247 (18) | −0.0018 (17) | −0.0015 (15) | −0.0008 (18) |
| N3 | 0.0347 (18) | 0.070 (3) | 0.039 (2) | −0.0095 (19) | 0.0035 (16) | −0.005 (2) |
| O1 | 0.0424 (16) | 0.074 (2) | 0.0213 (15) | −0.0110 (16) | 0.0058 (13) | 0.0047 (16) |
| O2 | 0.0451 (16) | 0.095 (3) | 0.0201 (16) | −0.0169 (18) | −0.0047 (14) | 0.0107 (18) |
| O3 | 0.0361 (14) | 0.063 (2) | 0.0225 (14) | −0.0028 (14) | 0.0000 (12) | 0.0063 (16) |
| O4 | 0.0384 (16) | 0.082 (3) | 0.0182 (14) | −0.0026 (15) | 0.0034 (12) | −0.0059 (16) |
| O5 | 0.0491 (18) | 0.099 (3) | 0.0427 (19) | −0.0122 (19) | −0.0002 (15) | 0.023 (2) |
| O8 | 0.0517 (17) | 0.068 (2) | 0.0209 (16) | −0.0074 (16) | 0.0120 (13) | −0.0011 (15) |
| O9 | 0.126 (3) | 0.073 (3) | 0.059 (3) | 0.002 (3) | −0.008 (3) | 0.003 (2) |
| O10 | 0.115 (5) | 0.122 (8) | 0.198 (18) | 0.027 (5) | 0.045 (14) | −0.028 (15) |
| O10' | 0.115 (5) | 0.122 (8) | 0.198 (18) | 0.027 (5) | 0.045 (14) | −0.028 (15) |
| Ba1—O2i | 2.767 (3) | C5—H5 | 0.9300 |
| Ba1—O2 | 2.767 (3) | C6—C7 | 1.518 (6) |
| Ba1—O5 | 2.772 (3) | C7—O8 | 1.230 (5) |
| Ba1—O5i | 2.772 (3) | C7—O4 | 1.268 (5) |
| Ba1—O1i | 2.889 (3) | C8—C10 | 1.347 (6) |
| Ba1—O1 | 2.889 (3) | C8—N3 | 1.349 (6) |
| Ba1—O8ii | 2.894 (3) | C8—H8 | 0.9300 |
| Ba1—O8iii | 2.894 (3) | C9—N2 | 1.314 (6) |
| Ba1—O9 | 3.004 (5) | C9—N3 | 1.335 (6) |
| Ba1—O9i | 3.004 (4) | C9—H9 | 0.9300 |
| Cu2—O4 | 1.894 (3) | C10—N2 | 1.375 (6) |
| Cu2—N1 | 1.930 (3) | C10—H10 | 0.9300 |
| Cu2—O3 | 1.934 (3) | C12—O2 | 1.229 (5) |
| Cu2—N2 | 1.966 (3) | C12—N1 | 1.331 (5) |
| C1—C6 | 1.389 (6) | C12—C13 | 1.544 (5) |
| C1—C2 | 1.404 (6) | C13—O1 | 1.228 (5) |
| C1—N1 | 1.412 (5) | C13—O3 | 1.274 (5) |
| C2—C3 | 1.380 (6) | N3—H3A | 0.8600 |
| C2—H2 | 0.9300 | O5—H5B | 0.8502 |
| C3—C4 | 1.355 (7) | O5—H5C | 0.8500 |
| C3—H3 | 0.9300 | O8—Ba1ii | 2.894 (3) |
| C4—C5 | 1.379 (6) | O9—H9C | 0.8498 |
| C4—H4 | 0.9300 | O9—H9A | 0.9530 |
| C5—C6 | 1.404 (5) | ||
| O2i—Ba1—O2 | 138.93 (16) | C6—C1—C2 | 117.4 (3) |
| O2i—Ba1—O5 | 71.64 (10) | C6—C1—N1 | 120.9 (4) |
| O2—Ba1—O5 | 122.44 (9) | C2—C1—N1 | 121.7 (4) |
| O2i—Ba1—O5i | 122.44 (9) | C3—C2—C1 | 121.7 (4) |
| O2—Ba1—O5i | 71.64 (10) | C3—C2—H2 | 119.1 |
| O5—Ba1—O5i | 143.21 (18) | C1—C2—H2 | 119.1 |
| O2i—Ba1—O1i | 56.10 (8) | C4—C3—C2 | 120.9 (4) |
| O2—Ba1—O1i | 119.20 (9) | C4—C3—H3 | 119.6 |
| O5—Ba1—O1i | 117.63 (9) | C2—C3—H3 | 119.6 |
| O5i—Ba1—O1i | 66.37 (9) | C3—C4—C5 | 118.7 (4) |
| O2i—Ba1—O1 | 119.20 (9) | C3—C4—H4 | 120.6 |
| O2—Ba1—O1 | 56.10 (8) | C5—C4—H4 | 120.6 |
| O5—Ba1—O1 | 66.37 (9) | C4—C5—C6 | 121.7 (4) |
| O5i—Ba1—O1 | 117.63 (9) | C4—C5—H5 | 119.1 |
| O1i—Ba1—O1 | 168.57 (15) | C6—C5—H5 | 119.1 |
| O2i—Ba1—O8ii | 144.53 (10) | C1—C6—C5 | 119.5 (4) |
| O2—Ba1—O8ii | 76.13 (10) | C1—C6—C7 | 127.3 (3) |
| O5—Ba1—O8ii | 84.57 (10) | C5—C6—C7 | 113.2 (4) |
| O5i—Ba1—O8ii | 65.01 (10) | O8—C7—O4 | 120.8 (4) |
| O1i—Ba1—O8ii | 119.12 (9) | O8—C7—C6 | 119.3 (3) |
| O1—Ba1—O8ii | 71.12 (10) | O4—C7—C6 | 119.9 (3) |
| O2i—Ba1—O8iii | 76.13 (10) | C10—C8—N3 | 107.1 (4) |
| O2—Ba1—O8iii | 144.53 (10) | C10—C8—H8 | 126.5 |
| O5—Ba1—O8iii | 65.01 (10) | N3—C8—H8 | 126.5 |
| O5i—Ba1—O8iii | 84.57 (10) | N2—C9—N3 | 110.7 (4) |
| O1i—Ba1—O8iii | 71.12 (10) | N2—C9—H9 | 124.6 |
| O1—Ba1—O8iii | 119.12 (9) | N3—C9—H9 | 124.6 |
| O8ii—Ba1—O8iii | 69.99 (12) | C8—C10—N2 | 108.5 (4) |
| O2i—Ba1—O9 | 79.15 (11) | C8—C10—H10 | 125.8 |
| O2—Ba1—O9 | 65.19 (11) | N2—C10—H10 | 125.8 |
| O5—Ba1—O9 | 137.09 (13) | O2—C12—N1 | 130.9 (4) |
| O5i—Ba1—O9 | 79.31 (13) | O2—C12—C13 | 116.0 (3) |
| O1i—Ba1—O9 | 65.44 (11) | N1—C12—C13 | 113.1 (3) |
| O1—Ba1—O9 | 104.07 (11) | O1—C13—O3 | 124.8 (4) |
| O8ii—Ba1—O9 | 133.93 (10) | O1—C13—C12 | 118.2 (3) |
| O8iii—Ba1—O9 | 136.55 (10) | O3—C13—C12 | 117.0 (3) |
| O2i—Ba1—O9i | 65.19 (11) | C12—N1—C1 | 122.5 (3) |
| O2—Ba1—O9i | 79.15 (11) | C12—N1—Cu2 | 111.6 (3) |
| O5—Ba1—O9i | 79.31 (13) | C1—N1—Cu2 | 125.8 (3) |
| O5i—Ba1—O9i | 137.09 (13) | C9—N2—C10 | 106.1 (4) |
| O1i—Ba1—O9i | 104.07 (11) | C9—N2—Cu2 | 126.5 (3) |
| O1—Ba1—O9i | 65.44 (11) | C10—N2—Cu2 | 127.3 (3) |
| O8ii—Ba1—O9i | 136.55 (10) | C9—N3—C8 | 107.6 (4) |
| O8iii—Ba1—O9i | 133.93 (10) | C9—N3—H3A | 126.2 |
| O9—Ba1—O9i | 59.89 (18) | C8—N3—H3A | 126.2 |
| O4—Cu2—N1 | 94.38 (13) | C13—O1—Ba1 | 120.4 (2) |
| O4—Cu2—O3 | 175.12 (15) | C12—O2—Ba1 | 125.8 (3) |
| N1—Cu2—O3 | 86.53 (13) | C13—O3—Cu2 | 111.5 (2) |
| O4—Cu2—N2 | 89.12 (13) | C7—O4—Cu2 | 131.0 (3) |
| N1—Cu2—N2 | 175.91 (14) | C7—O8—Ba1ii | 124.9 (3) |
| O3—Cu2—N2 | 90.17 (13) |
| Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+2, −z+2; (iii) x, −y+2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···O1iv | 0.86 | 1.95 | 2.804 (5) | 177 |
| O5—H5B···O4iii | 0.85 | 1.99 | 2.827 (5) | 169 |
| O5—H5B···O8iii | 0.85 | 2.58 | 3.047 (5) | 116 |
| O9—H9A···O8v | 0.95 | 2.08 | 2.915 (5) | 145 |
| Symmetry codes: (iv) −x+2, −y+2, −z+2; (iii) x, −y+2, z−1/2; (v) −x+1, −y+1, −z+2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···O1i | 0.86 | 1.95 | 2.804 (5) | 177 |
| O5—H5B···O4ii | 0.85 | 1.99 | 2.827 (5) | 169 |
| O5—H5B···O8ii | 0.85 | 2.58 | 3.047 (5) | 116 |
| O9—H9A···O8iii | 0.95 | 2.08 | 2.915 (5) | 145 |
| Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) x, −y+2, z−1/2; (iii) −x+1, −y+1, −z+2. |
The authors express their thanks to the Natural Science Foundation of Henan Province for financial support.
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Designing metal-containing building blocks to spontaneously assembly infinite molecular architectures is of considerable interest recently as a result of the peculiar magnetic exchange interactions between metal ions through bridging ligands (Kahn, 1993). Among many other methods, the "complex as ligand" approach, i.e. using metal cations to link reactively stable coordination compounds that contain potential bridging blocks, is particularly suitable for designing heteropolymetallic compounds, ranging from discrete entities to three-dimensional architectures. (Gao et al., 2001)
In the title compound, CuII adopts a square planar geometry, coordinating to O3, O4 and N1 from the oxamato-N-benzoate and N2 from the imidazole ligand to afford a Cu-containing "ligand". BaII, lying on the 2-fold axis, is decacoordinate and bridges these Cu-ligands to form one-dimensional chains along the c axis.