原位产生的SO42-配位的二维无机钴配合物K2[Co3(OH)2(SO4)3(H2O)2]的水热合成及晶体结构

相同的水热反应条件下4-氨基-二(2-吡啶基)-1,2,4-三氮唑(abpt)、KSCN与钴盐(CoCl2·6H2O)反应合成了2种新的钴配合物:零维的单核配合物CoSCN(abpt)](1α)和二维的无机层状配合物K2Co3(OH)2(SO4)3(H2O)2](1β),并通过元素分析和红外光谱对其进行了表征.配合物1α的晶体属于单斜晶系,P21/c空间群.配合物1β晶体属于正交晶系,Cmc21空间群.在配合物1α中,abpt和SCN-配体都参与配位与Co(Ⅱ)离子形成了2个不同的单核单元,这些单核单元又通过S原子和N原子之间的氢键作用连成了三维超分子结构;在配合物1β中,abpt配体没有参与配位,而SCN-配体则被氧化成了SO42-离子并与Co(Ⅱ)离子配位形成了二维配位层状结构,相邻层之间进一步通过氢键作用形成了沿c轴方向有孔道的三维超分子网络,这些孔道里面填充着反离子K+.

Hydrothermal Synthesis and Crystal Structure of 2D K2[Co3(OH)2(SO4)3(H2O)2] Coordination Polymer with the In-Situ Formation of SO42-

Reaction of CoCl2·6H2O, 4-amino-3,5-di(2-pyridyl)-4H-1,2,4-triazole (abpt), KSCN results in formation of two new complexes, OD mononuclear complex named CoSCN (abpt)] (1α) and 2D inorganic coordination framework K2Co3(OH)2(SO4)3(H2O)2] (1β), in the same hydrothermal reaction system and were characterized by elemental analysis and IR. X-ray diffraction crystal structure analysis shows that 1α crystallizes in monoclinic system, space group P21/c with a=1.073 91(11) nm, b=1.589 59(16) nm, c=1.74041(18) nm,β=106.720(2)°, V=2.845 4(5) nm3, Z=4; and 1β crystallizes in orthorhombic system, space group Cmc21 with a=1.794 24(17) nm, b=0.755 83(7) nm, c=0.976 05(10) nm, V=1.323 7(2) nm3, Z=4. In complex 1α, both abpt and SCN- ligands are coordinated to Co (Ⅱ) to form two different mononuclear units and further generate a 3D supramolecular architecture by the hydrogen bonds between the S atoms and uncoordinated N atoms of the abpt ligand. While in 1β, the abpt ligand is uncoordinated and the SCN- anion is changed to SO42- anion coordinated to Co(Ⅱ) atoms to result in a 2D coordination layer. Adjacent layers are linked to each other by hydrogen bonds to generate a 3D porous supramolecular architecture with 1D channels running along the c-axis, which are occupied by the counter K+ ions. CCDC: 658233, 1α; CSD: 418495, 1β.