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

Four new one-dimensional coordination polymers containing the dimetal cluster Cu-2(OAc)(4) have been synthesized by reacting Cu(OAC)(2). H2O with two different N, N'-bidentate ligands. Reaction of the flexible ligand, 1,2-bis(4-pyridyl)ethane (L-1), with the copper starting material produced two, co-crystallizing coordination polymers: catena-Poly[CU2(OAc)(4)(L-1)](.)2H(2)O (1) and catena-Poly[Cu-2(OAc)(4)(L-1)]. In the solid state, 1 (monoclinic, C2/c, a = 24.9471(17) angstrom, b = 13.3539(9) angstrom, c = 8.8050(6) angstrom,beta = 93.6480(10)degrees, V = 2927.4(3) angstrom(3), Z = 4) 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, a = 7.6263(6) angstrom, b = 8.5283(6) angstrom, c = 9.8633(6) angstrom, alpha = 74.1070(10)degrees, beta = 68.2160(10)degrees, gamma = 74.0090(10)degrees, V = 561.96(7) angstrom(3), Z = 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 (L-2), with the copper starting material also afforded two co-crystallizing coordination polymers: catena-Poly[Cu-2(OAC)(4)(L-2)] (3) and catena-Poly [Cu-2) (OAC)(4) (L-2)] (.) solvents (4). 3 (monoclinic, P2(1)/m, a = 9.8065(9) angstrom, b = 12.3793(11) angstrom, c = 9.9408(g) angstrom,beta = 107.6009(17)degrees, V 1150.29(18) angstrom(3), Z = 2), like 2, features linear chains and contains no significant solvent accessible void space. 4 (monoclinic, C2/c, a 28.9810(16) angstrom, b = 12.9301(7) angstrom, c = 8.6954(5) angstrom,beta = 98.8010(10)degrees, V = 3220.0(3) angstrom(3), Z = 4) 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 I 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. (c) 2005 Elsevier SAS. All rights reserved.