To a stirred solution of Co(O2CCH3)2·4H2O (2.04 mmol, 0.508 g) in 20 ml of DMF was added a solution of 1,10-phenanthroline (1.36 mmol, 0.27 g) in 10 ml of DMF. The resulting solution was allowed to stir for 10 min. and then pink solid began to precipitate. After stirring for further 10 min, the reaction mixture was filtered off and washed with several aliquots of DMF, followed by several aliquots of acetone, and then diethyl ether. The solid was dried in vacuo. Data for (1): Yield 0.38 g (62%). mp=297 ℃ (dec.). λM (mmho cm2 mol-1, in DMSO at 25 ℃): 28. Anal. Calc. for C36H34N4 O12Co3: C, 48.50; H, 3.84; N, 6.28; Co, 20.95. Found: C, 48.07; H, 3.86; N, 6.39; Co, 20.60. FAB-MS, m/z: [M+2H]+, 893; [M-OAc+H]+, 833; [M-phen+ 2H]+, 713. FT-IR (KBr, cm-1): 3069, 2923, 1592 (vasym. COO-), 1515, 1419 (vsym. COO-), 1339, 1018, 849, 728, 669.
Pink crystals of (1) suitable for X-ray diffraction study were grown by diffusive mixing of DMF solutions of 1,10-phenanthroline and Co(O2CCH3)2·4H2O.
Crystal Structure Determination of 1. X-ray quality crystals were obtained as described above. A crystal size 0.50×0.25×0.13 mm was used for data collection on a STOE STAD14 four-circlediffractometer11 with graphite-monochromatized Mo- Kα radiation (λ=0.71069 Å) at room temperature. Cell parameters and orientation matrix for data collection were determined by least-squares refinement, using 34 reflections in the range of 9.5°<θ< 10.5°. Data were collected using the ω-2θ scan technique. Three standard reflections monitored every 1h and decayed 4.4% over the course of the data collection. The intensity data were corrected for Lorentz and polarization effects. The structure was solved by direct method12 and refined by fullmatrix least-squares methods.13 All non-hydrogen atoms were refined anisotropically. The positions of hydrogen atoms were idealized (d(C-H)=0.93 or 0.96 Å) and included in the calculations of the structure factors as fixed contributions. Each hydrogen atom was assigned an isotropic thermal parameter of 1.2 times that of attached atom. The data collection and structure solution parameters are listed in Table 1, together with standard discrepancy discrepancy indicies R and wR.
Table 1.aw= 1/[σ2(Fo2)+(0.0451P)2+17.2917P] where P=(Fo2+2Fc2)/3|
Table 2.Symmetry transformations of i: 1-x, y, -z+1/2
This work was partially supported by the 2003 research fund of Catholic University of Daegu, Korea.
Supporting information available. Crystallographic data for the structure reported here have been deposited with the Cambridge Crystallographic Data Centre (Deposition No. CCDC-216817). The data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033; e-mail: email@example.com).