| Abstract | The long, rigid ligands 1,4-bis[(3-pyridyl)ethynyl]benzene (L1) and 1,4-bis[(4-pyridyl)ethynyl]benzene (L2) were used in the synthesis of 10 new organic-inorganic coordination frameworks, each of them adopting different structural motifs. Synthesis, single-crystal X-ray structure determination, and spectroscopic and thermogravimetric analyses are presented. The reactions between M(NO3)2?xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2?H2O [hfac = bis(hexafluoroacetylacetonato)] with L1 afforded the following one-dimensional zigzag chain structures: [Cd(C20H12N2)0.5(NO3)(CH3OH)]n (1, monoclinic, C2/c; a = 7.586(1) ?, b = 23.222(1) ?, c = 13.572(1) ?, = 92.824(1), Z = 4); [{Cu(C20H12N2)(NO3)2(CH3OH)}?CH3OH]n (2, orthorhombic, P212121; a = 8.589(1) ?, b = 15.766(1) ?, c = 17.501(1) ?, Z = 4); [Co(C20H12N2)2(NO3)2(H2O)2] (5, triclinic, P1; a = 7.493(1) ?, b = 8.948(1) ?, c = 14.854(1) ?, = 100.427(1), = 97.324(1), = 110.901(1), Z = 1); [Cu(C20H12N2)(hfac)2]n (4, monoclinic, C2/c, a = 18.828(1) ?, b = 14.671(1) ?, c = 13.427(1) ?, = 90.447(1), Z = 4). Moreover, the minority phase compound formed from Cu(NO3)2?3H2O and L1 yielded a metallocyclic chain structure, [Cu(C20H12N2)(NO3)]n (3, triclinic, P; a = 8.728(1) ?, b = 10.018(1) ?, c = 11.893(1) ?, = 109.991(1), = 97.109(1), = 115.542(1), Z = 1). In addition to the dinuclear coordination complex 5, all other polymeric structures (1-4) from L1 are composed of interpenetrating 2D and 3D cross-linked zigzag chains via hydrogen-bonding interactions. The reactions between M(NO3)2?xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2?H2O [hfac = bis(hexafluoroacetylacetonato)] and L2 were dependent on the nature of the metal center and resulted in the formation of four different interpenetrating and noninterpenetrating compounds (6-10): [Co(C20H12N2)1.5(NO3)2]n (6, triclinic, P; a = 14.172(1) ?, b = 15.795(1) ?, c = 18.072(1) ?, = 115.380(1), = 101.319(1), = 93.427(2), Z = 4), which consists of T-shaped building blocks assembled into three-dimensional interpenetrating polycatenated ladders; [Cd(C20H12N2)2(NO3)2]n (7, monoclinic, I2/a; a = 11.371(1) ?, b = 20.311(2) ?, c = 15.240(2) ?, = 100.201(2), Z = 4), which adopts a two-dimensional noninterpenetrating square-grid motif; [Cu(C20H12N2)(hfac)2]n (8, monoclinic, I2/a; a = 11.371(1) ?, b = 20.311(2) ?, c = 15.240(2) ?, = 100.201(2), Z = 4), composed of three sets of distinct one-dimensional linear chains; [Cu(C20H12N2)(EtOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2]?2EtOH (9, triclinic, P; a = 12.248(2) ?, b = 13.711(3) ?, c = 18.257(4) ?, = 108.078(4), = 97.890(4), = 103.139(5), Z = 2) and [Cu(C20H12N2)(MeOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2]?2MeOH (10, triclinic, P; a = 12.136(1) ?, b = 13.738(2) ?, c = 17.563(3) ?, = 107.663(3), = 94.805(4), = 104.021(4), Z = 2). Both 9 and 10 stack into infinite interpenetrating ladders through bundles of infinite chains and are described in our preliminary communication. |
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