Channel-containing structures generated from linear coordination polymer chains containing -bidentate ligands and Cu–Cu dimetal units

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Four new one-dimensional coordination polymers containing the dimetal cluster Cu2(OAc)4 have been synthesized by reacting Cu(OAc)2 ⋅ H2O with two different -bidentate ligands. Reaction of the flexible ligand, 1,2-bis(4-pyridyl)ethane (L1), with the copper starting material produced two, co-crystallizing coordination polymers: catena-Poly[Cu2(OAc)4(L1)] ⋅ 2H2O (1) and catena-Poly[Cu2(OAc)4(L1)]. In the solid state, 1 (monoclinic, C2/c ) features linear chains which are organized into layers. These layers stack along the crystallographic c-axis forming small hexagonal channels occupied by the solvent of crystallization. Compound 2 (triclinic, P-1) also features linear chains of the coordination polymer, but differs from 1 in that the chains are packed so as to leave no significant channels. Reaction of the rigid ligand, 1,4-bis(4-pyridyl)buta-1,3-diyne (L2), with the copper starting material also afforded two co-crystallizing coordination polymers: catena-Poly[Cu2(OAc)4(L2)] (3) and catena-Poly[Cu2(OAc)4(L2)] ⋅ solvents (4). 3 (monoclinic, P21/m, ), like 2, features linear chains and contains no significant solvent accessible void space. 4 (monoclinic, C2/c, ) also consists of linear chains of the coordination polymer. However, the overall topology of 4 is identical to that of 1, with the generated hexagonal channels containing crystallographically unidentifiable solvents of crystallization. Compounds 1 and 2 and compounds 3 and 4 are pairs of polymorphic coordination polymers neglecting the solvents of crystallization in 1 and 4. The compounds, which represent four new examples of coordination polymers containing dimetal units, have been characterized by IR, elemental analysis, and thermogravimetric analysis in addition to X-ray crystallography.