ic034999d_si_001.cif (99.02 kB)

Coordination Polymers Assembled from Angular Dipyridyl Ligands and CuII, CdII, CoII Salts:  Crystal Structures and Properties

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posted on 09.02.2004, 00:00 by Zheng Huang, Hai-Bin Song, Miao Du, Shen-Tan Chen, Xian-He Bu, Joan Ribas
Six new metal-organic coordination networks based on linking unit 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (L1) or 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L3) and inorganic CuII, CdII, and CoII salts have been prepared and structurally characterized by single-crystal X-ray analysis. Using L1 to react with three different CuII salts, Cu(OAc)2·H2O, Cu(NO3)2·3H2O, and CuSO4·5H2O, respectively, two different one-dimensional (1-D) coordination polymers, {[Cu2L1(μ-OAc)4](CHCl3)2}n (1) [triclinic, space group P1̄, a = 7.416(3) Å, b = 8.207(3) Å, c = 14.137(5) Å, α = 100.333(7)°, β = 105.013(6)°, γ = 94.547(6)°, Z = 1] and {[CuL1(NO3)2](CHCl3)0.5}n (2) [monoclinic, space group C2/c, a = 28.070(8) Å, b = 9.289(3) Å, c = 15.235(4) Å, β = 113.537(5)°, Z = 8], and a chiral 3-D open framework, {[CuL1(H2O)(SO4)](H2O)2}n (3) [orthorhombic, space group P212121, a = 5.509(2) Å, b = 10.545(4) Å, c = 29.399(11) Å, Z = 4], were obtained. Reaction of L1 and Cd(ClO4)2·6H2O or Co(ClO4)2·6H2O, in the presence of NH4SCN, yielded another 3-D open framework, {[CdL1(NCS)2](CH3OH)1.5}n (4) [monoclinic, space group C2/c, a = 28.408(10) Å, b = 9.997(5) Å, c = 7.358(4) Å, β = 99.013(8)°, Z = 4], or a 2-D network, {[Co(L1)2(NCS)2](H2O)2.5}n (5) [orthorhombic, space group Pnna, a = 22.210(5) Å, b = 12.899(3) Å, c = 20.232(4) Å, Z = 4]. When L1 was replaced by L3 to react with Co(ClO4)2·6H2O and NH4SCN, another 2-D coordination polymer, [Co(L3)2(NCS)2]n (6) [monoclinic, space group P21/c, a = 8.120(3) Å, b = 9.829(4) Å, c = 17.453(6) Å, β = 103.307(6)°, Z = 2], was constructed. These results indicate that the nature of the ligands, metal centers, or counteranions plays the critical role in construction of these novel coordination polymers. The interesting porous natures of two 3-D open frameworks 3 and 4 were investigated by TGA and XPRD techniques, and the magnetic properties of the CuII and CoII complexes were studied by variable-temperature magnetic susceptibility and magnetization measurements.

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