Solvent control of dimensionality in titanium aryloxide coordination polymers prepared from 4,4′-bis(hydroxyphenyl)sulfide

X-ray crystal structures of three titanium (IV) coordination polymers with 4,4′-bis(phenoxy)sulfide bridging ligands. Strongly coordinating pyridine results in a one-dimensional chain, weakly coordinating tetrahydrofuran leads to a two-dimensional sheet, and non-coordinating benzene yields a three-dimensional network. [Display omitted] •Three new titanium (IV) coordination polymers were prepared with 4,4′-bis(hydroxyphenyl)sulfide as the ligand precursor.•The X-ray crystal structures feature octahedral and trigonal bipyramidal titanium (IV).•The dimensionality of the polymers is impacted by the coordinating ability of the solvent used in the synthesis. The crystal and molecular structures of three covalent metal–organic network (CMON) materials synthesized from titanium (IV) isopropoxide and the Bisphenol-A analog 4,4′-bis(hydroxyphenyl)sulfide in three different solvents have been determined. The structures of the one-dimensional chain coordination polymer [trans-Ti(μ-O:O’-OC6H4SC6H4O)2(C5H5N)2]n (1) obtained from pyridine and the two-dimensional sheet coordination polymer {[Ti2(μ-O:O’-OC6H4SC6H4O)2(μ2O:κO’-OC6H4SC6H4O)2(C4H8O)2]∙(C4H8O)y}n (2) from tetrahydrofuran both contain octahedral titanium (IV) coordination geometries, whereas the doubly interpenetrated three-dimensional coordination network [Ti2(μ-O:O’-OC6H4SC6H4O)2(μ2O:κO′-OC6H4SC6H4O)2]n (3) synthesized from benzene contains trigonal bipyramidal titanium (IV). Each material has been characterized by single crystal and powder X-ray diffraction, elemental analysis, and by 1H NMR quench when it contains more than one organic component.