Acta Cryst. (2008). E64, m691 [ doi:10.1107/S1600536808010593 ]
In the title mononuclear complex, [Cu(C9H9O3)2(H2O)2], the CuII ion, located on an inversion center, is hexacoordinated by four O atoms from two benzyloxyacetate ligands [Cu-O = 1.9420 (14) and 2.2922 (14) Å] and two water molecules [Cu-O = 2.0157 (15) Å] in a distorted octahedral geometry. In the crystal structure, intermolecular O-H
O hydrogen bonds link the molecules into layers parallel to the bc plane.
The ligand, benzyloxyacetic acid was commercially available and used without further purification. The title complex was prepared by the addition of Cu(Ac)2.H2O (4.00 g, 20 mmol) to a hot aqueous solution of benzyloxyacetic acid (1.66 g, 10 mmol); the pH was adjusted to 6 with 0.1M sodium hydroxide. The solution was allowed to evaporate at room temperature. Blue prismatic crystals were separated from the filtered solution after several days. C&H analysis. Calc. for C18H22CuO8: C 50.28, H 5.16%. Found: C 50.26, H 5.17%.
The C-bound H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å, and were refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(C). The H atoms of the water molecule were located in a difference Fourier map and refined with bond restrint O—H = 0.84 (2) Å in the riding-model approximation, with Uiso(H) = 1.5Ueq(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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./cv2398fig1thm.gif)
| Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids [symmetry code: (i) -x+1, -y, -z+1]. |
| [Cu(C9H9O3)2(H2O)2] | F000 = 446 |
| Mr = 429.91 | Dx = 1.536 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 7991 reflections |
| a = 11.8847 (4) Å | θ = 1.8–27.6º |
| b = 7.1509 (2) Å | µ = 1.22 mm−1 |
| c = 11.6564 (5) Å | T = 296 (2) K |
| β = 110.283 (3)º | Prism, blue |
| V = 929.21 (6) Å3 | 0.32 × 0.24 × 0.18 mm |
| Z = 2 |
| Bruker P4 diffractometer | 2144 independent reflections |
| Radiation source: fine-focus sealed tube | 1606 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.035 |
| Detector resolution: 10.000 pixels mm-1 | θmax = 27.6º |
| T = 296(2) K | θmin = 1.8º |
| ω scans | h = −15→15 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→8 |
| Tmin = 0.711, Tmax = 0.803 | l = −15→10 |
| 7991 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)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0429P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 2144 reflections | Δρmax = 0.40 e Å−3 |
| 130 parameters | Δρmin = −0.57 e Å−3 |
| 3 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Cu(C9H9O3)2(H2O)2] | V = 929.21 (6) Å3 |
| Mr = 429.91 | Z = 2 |
| Monoclinic, P21/c | Mo Kα |
| a = 11.8847 (4) Å | µ = 1.22 mm−1 |
| b = 7.1509 (2) Å | T = 296 (2) K |
| c = 11.6564 (5) Å | 0.32 × 0.24 × 0.18 mm |
| β = 110.283 (3)º |
| Bruker P4 diffractometer | 2144 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1606 reflections with I > 2σ(I) |
| Tmin = 0.711, Tmax = 0.803 | Rint = 0.035 |
| 7991 measured reflections |
| R[F2 > 2σ(F2)] = 0.034 | 3 restraints |
| wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | Δρmax = 0.40 e Å−3 |
| 2144 reflections | Δρmin = −0.57 e Å−3 |
| 130 parameters |
| x | y | z | Uiso*/Ueq | ||
| Cu1 | 0.5000 | 0.0000 | 0.5000 | 0.02860 (13) | |
| O1 | 0.47417 (14) | 0.2249 (2) | 0.58090 (13) | 0.0345 (4) | |
| O2 | 0.53762 (17) | 0.4957 (2) | 0.67150 (14) | 0.0417 (4) | |
| O3 | 0.66880 (13) | 0.1742 (2) | 0.52517 (14) | 0.0407 (4) | |
| O1W | 0.42562 (15) | 0.1187 (2) | 0.33393 (14) | 0.0374 (4) | |
| C1 | 0.5503 (2) | 0.3554 (3) | 0.61482 (17) | 0.0325 (5) | |
| C2 | 0.6644 (2) | 0.3444 (3) | 0.5852 (2) | 0.0376 (5) | |
| C3 | 0.7506 (2) | 0.1723 (4) | 0.4603 (2) | 0.0442 (6) | |
| C4 | 0.8798 (2) | 0.1745 (3) | 0.54208 (19) | 0.0341 (5) | |
| C5 | 0.9166 (2) | 0.0908 (4) | 0.6556 (2) | 0.0427 (6) | |
| C6 | 1.0355 (3) | 0.0908 (4) | 0.7283 (2) | 0.0510 (7) | |
| C7 | 1.1196 (2) | 0.1751 (4) | 0.6891 (2) | 0.0513 (7) | |
| C8 | 1.0844 (2) | 0.2568 (4) | 0.5758 (3) | 0.0507 (7) | |
| C9 | 0.9650 (2) | 0.2583 (4) | 0.5025 (2) | 0.0430 (6) | |
| H1W1 | 0.425 (2) | 0.2360 (13) | 0.335 (2) | 0.056* | |
| H1W2 | 0.457 (2) | 0.075 (3) | 0.286 (2) | 0.056* | |
| H2A | 0.6675 | 0.4486 | 0.5331 | 0.045* | |
| H2B | 0.7333 | 0.3530 | 0.6601 | 0.045* | |
| H3A | 0.7352 | 0.2803 | 0.4067 | 0.053* | |
| H3B | 0.7361 | 0.0612 | 0.4094 | 0.053* | |
| H5A | 0.8604 | 0.0339 | 0.6833 | 0.051* | |
| H6A | 1.0593 | 0.0333 | 0.8045 | 0.061* | |
| H7A | 1.1998 | 0.1768 | 0.7392 | 0.062* | |
| H8A | 1.1414 | 0.3115 | 0.5482 | 0.061* | |
| H9A | 0.9416 | 0.3157 | 0.4262 | 0.052* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cu1 | 0.0348 (2) | 0.0229 (2) | 0.03073 (19) | −0.00185 (16) | 0.01464 (16) | −0.00319 (15) |
| O1 | 0.0435 (9) | 0.0261 (8) | 0.0393 (8) | −0.0028 (7) | 0.0212 (7) | −0.0052 (7) |
| O2 | 0.0643 (11) | 0.0267 (9) | 0.0400 (8) | −0.0002 (8) | 0.0254 (8) | −0.0066 (7) |
| O1W | 0.0465 (10) | 0.0316 (9) | 0.0357 (8) | 0.0020 (8) | 0.0160 (7) | 0.0004 (7) |
| C1 | 0.0444 (13) | 0.0287 (12) | 0.0245 (9) | 0.0028 (10) | 0.0122 (10) | 0.0021 (9) |
| C2 | 0.0400 (13) | 0.0300 (13) | 0.0423 (12) | −0.0057 (10) | 0.0136 (11) | −0.0086 (10) |
| O3 | 0.0369 (9) | 0.0375 (9) | 0.0537 (9) | −0.0061 (7) | 0.0234 (8) | −0.0147 (8) |
| C3 | 0.0414 (14) | 0.0559 (17) | 0.0389 (12) | −0.0013 (12) | 0.0188 (11) | −0.0086 (11) |
| C4 | 0.0382 (12) | 0.0335 (12) | 0.0347 (11) | 0.0017 (10) | 0.0178 (10) | −0.0028 (9) |
| C5 | 0.0493 (16) | 0.0419 (14) | 0.0427 (12) | 0.0061 (12) | 0.0233 (12) | 0.0054 (11) |
| C6 | 0.0590 (18) | 0.0537 (17) | 0.0393 (13) | 0.0205 (14) | 0.0158 (13) | 0.0053 (12) |
| C7 | 0.0400 (14) | 0.0482 (17) | 0.0584 (15) | 0.0070 (13) | 0.0077 (13) | −0.0118 (13) |
| C8 | 0.0413 (15) | 0.0456 (16) | 0.0726 (18) | −0.0036 (12) | 0.0289 (14) | −0.0005 (14) |
| C9 | 0.0453 (14) | 0.0432 (15) | 0.0459 (13) | 0.0038 (11) | 0.0225 (12) | 0.0055 (11) |
| Cu1—O1 | 1.9420 (14) | C3—C4 | 1.500 (3) |
| Cu1—O3 | 2.2922 (14) | C3—H3A | 0.9700 |
| Cu1—O1W | 2.0157 (15) | C3—H3B | 0.9700 |
| O1—C1 | 1.264 (3) | C4—C5 | 1.379 (3) |
| O2—C1 | 1.239 (2) | C4—C9 | 1.386 (3) |
| Cu1—O1i | 1.9420 (14) | C5—C6 | 1.372 (4) |
| Cu1—O3i | 2.2922 (14) | C5—H5A | 0.9300 |
| Cu1—O1Wi | 2.0157 (15) | C6—C7 | 1.374 (4) |
| O3—C3 | 1.424 (2) | C6—H6A | 0.9300 |
| O1W—H1W1 | 0.839 (9) | C7—C8 | 1.370 (4) |
| O1W—H1W2 | 0.83 (2) | C7—H7A | 0.9300 |
| C1—C2 | 1.512 (3) | C8—C9 | 1.380 (4) |
| C2—O3 | 1.414 (2) | C8—H8A | 0.9300 |
| C2—H2A | 0.9700 | C9—H9A | 0.9300 |
| C2—H2B | 0.9700 | ||
| O1i—Cu1—O1 | 180.00 (7) | C1—C2—H2B | 109.6 |
| O1i—Cu1—O3 | 103.51 (6) | C2—O3—C3 | 114.88 (17) |
| O1—Cu1—O3 | 76.49 (6) | C2—O3—Cu1 | 110.48 (12) |
| O1i—Cu1—O1W | 88.45 (6) | C3—O3—Cu1 | 130.94 (13) |
| O1—Cu1—O1W | 91.55 (6) | C4—C3—H3A | 108.9 |
| O3—Cu1—O3i | 180.0 | C4—C3—H3B | 108.9 |
| O1W—Cu1—O3 | 88.11 (6) | C4—C5—H5A | 119.7 |
| O1Wi—Cu1—O3 | 91.89 (6) | C4—C9—H9A | 119.9 |
| O1W—Cu1—O1Wi | 180.0 | C5—C4—C9 | 118.8 (2) |
| Cu1—O1W—H1W1 | 114.0 (18) | C5—C4—C3 | 121.3 (2) |
| Cu1—O1W—H1W2 | 109.5 (18) | C5—C6—C7 | 120.4 (2) |
| O1i—Cu1—O3i | 76.49 (6) | C5—C6—H6A | 119.8 |
| O1—Cu1—O3i | 103.51 (6) | C6—C5—C4 | 120.6 (2) |
| O1i—Cu1—O1Wi | 91.55 (6) | C6—C5—H5A | 119.7 |
| O1—Cu1—O1Wi | 88.45 (6) | C6—C7—H7A | 120.2 |
| O1—C1—C2 | 119.44 (18) | C7—C6—H6A | 119.8 |
| O2—C1—O1 | 123.9 (2) | C7—C8—C9 | 120.3 (2) |
| O2—C1—C2 | 116.6 (2) | C7—C8—H8A | 119.9 |
| O3—C2—C1 | 110.35 (18) | C8—C7—C6 | 119.6 (2) |
| O3—C2—H2A | 109.6 | C8—C7—H7A | 120.2 |
| O3—C2—H2B | 109.6 | C8—C9—C4 | 120.3 (2) |
| O3—C3—C4 | 113.51 (18) | C8—C9—H9A | 119.9 |
| O3—C3—H3A | 108.9 | C9—C8—H8A | 119.9 |
| O3—C3—H3B | 108.9 | C9—C4—C3 | 119.9 (2) |
| O1W—Cu1—O3i | 91.89 (6) | H1W1—O1W—H1W2 | 113.6 (15) |
| O1Wi—Cu1—O3i | 88.11 (6) | H2A—C2—H2B | 108.1 |
| C1—O1—Cu1 | 123.14 (13) | H3A—C3—H3B | 107.7 |
| C1—C2—H2A | 109.6 | ||
| Cu1—O1—C1—O2 | −176.53 (15) | O1W—Cu1—O3—C2 | 92.76 (14) |
| Cu1—O1—C1—C2 | 3.9 (3) | O1Wi—Cu1—O3—C2 | −87.24 (14) |
| Cu1—O3—C3—C4 | −134.22 (17) | O1W—Cu1—O3—C3 | −63.95 (19) |
| O1i—Cu1—O3—C2 | −179.29 (13) | O1Wi—Cu1—O3—C3 | 116.05 (19) |
| O1—Cu1—O3—C2 | 0.71 (13) | C1—C2—O3—C3 | 161.48 (18) |
| O1i—Cu1—O3—C3 | 24.0 (2) | C1—C2—O3—Cu1 | 0.7 (2) |
| O1—Cu1—O3—C3 | −156.0 (2) | C2—O3—C3—C4 | 69.9 (3) |
| O1—C1—C2—O3 | −2.8 (3) | C3—C4—C5—C6 | 178.6 (2) |
| O2—C1—C2—O3 | 177.60 (17) | C3—C4—C9—C8 | −178.3 (2) |
| O3—Cu1—O1—C1 | −2.51 (15) | C4—C5—C6—C7 | 0.3 (4) |
| O3i—Cu1—O1—C1 | 177.49 (15) | C5—C4—C9—C8 | 0.2 (3) |
| O3—C3—C4—C5 | 31.9 (3) | C5—C6—C7—C8 | −1.2 (4) |
| O3—C3—C4—C9 | −149.7 (2) | C6—C7—C8—C9 | 1.5 (4) |
| O1W—Cu1—O1—C1 | −90.19 (16) | C7—C8—C9—C4 | −1.0 (4) |
| O1Wi—Cu1—O1—C1 | 89.81 (16) | C9—C4—C5—C6 | 0.1 (3) |
| Symmetry codes: (i) −x+1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W1···O2ii | 0.839 (9) | 1.978 (12) | 2.796 (2) | 165 (2) |
| O1W—H1W2···O2iii | 0.83 (2) | 1.964 (10) | 2.788 (2) | 173 (2) |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W1···O2i | 0.839 (9) | 1.978 (12) | 2.796 (2) | 165 (2) |
| O1W—H1W2···O2ii | 0.83 (2) | 1.964 (10) | 2.788 (2) | 173 (2) |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z−1/2. |
This work was supported by Guangdong Ocean University (Project Nos. 0612178 and 0612179) and Zhanjiang City Technology Tender (Project No. 0810014).
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Eddaoudi, M., Chen, B., O'Keeffe, M. & Yaghi, O. M. (2005). J. Am. Chem. Soc. 127, 1504–1510.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Current interests in supramolecular chemistry are rapidly expanding for their intriguing architectures and potential applications (Eddaoudi et al., 2005). The organic aromatic carboxylate ligand, benzyloxyacetate, has various coordination modes and can link metal centres through carboxylate groups or/and benzyloxy group into different extended architectures. Therefore, benzyloxyacetate can be considered as a good candidate to construct various metal-organic complexes. Herein we report the crystal structure of the title mononuclear complex of benzyloxyacetate, [Cu(C9H9O3)2(H2O)2], (I).
As illustrated in Fig. 1, the CuII ion lies on an inversion center and displays an octahedral geometry defined by four carboxylate O atoms from two different benzyloxyacetate ligands and two water molecules. The Cu—O and Cu—Ow bond lengths are 1.942 (1), 2.292 (1) and 2.016 (2) Å, respectively. The characteristic C—O(carboxylate) bond lengths suggest electron localization of the carboxylate groups of the anionic ligands. In the crystal structure, intermolecular hydrogen bonds (Table 1) give rise to a supramolecular structure.