Synthesis and Structural Characterization of Substituted Salicylate Titanocene Complexes: Three Supramolecular Frameworks Determined by Weak Interactions

摘要

Based on the reaction between Cp2TiCl2 and substituted salicylic acids in the presence of b-cyclodextrin polymer (b-CDP), three four-coordinated titanocene complexes [(eta(5)-C5H5)(2)Ti(S,O')(OCC6H4)center dot(C6H6)(0.5)] (1), [(eta(5)-C5H5)(2)Ti{(O,O')(3,5-Cl-2-OCC6H2)}] (2) and [(eta(5)-C5H5)(2)Ti{(O,O')(3,5-(NO2)(2)-OCC6H2)}] (3) were synthesized in high yields and their crystal structures have been determined by single-crystal X-ray diffraction. The structure of 1 has a Monoclinic space group P2(1)/c with a = 8.313(3) angstrom, b = 9.960(4) angstrom, c = 22.330(8) angstrom, beta = 111.856(11)degrees and Z = 4. The structure of 2 has a Monoclinic space group P2(1)/c with a = 8.0577(13) angstrom, b = 8.9022(14) angstrom, c = 21.977(4) angstrom, beta = 96.298(3)degrees and Z = 4. The structure of 3 has a Triclinic space group P-1 with a = 8.1687(11) angstrom, b = 8.3027(11) angstrom, c = 12.7164(17) angstrom, alpha = 102.930(2)degrees, beta = 100.479(2)degrees, gamma = 95.458(2)degrees and Z = 2. Each of the complexes exhibits a three-dimensional framework constructed through weak interactions, which are hydrogen bonding, pi-pi stacking and C-H center dot center dot center dot pi interactions. It was found that the variation of the substituted salicylate ligands affect the weak interactions as well as the specific framework structure that forms.