Wang Hui Ting
College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China.
Acta Crystallogr C Struct Chem. 2015 Oct;71(Pt 10):850-5. doi: 10.1107/S2053229615015818. Epub 2015 Sep 18.
In order to explore new metal coordination polymers and to search for new types of ferroelectrics among hybrid coordination polymers, two manganese dicyanamide complexes, poly[tetramethylammonium [di-μ3-dicyanamido-κ(6)N(1):N(3):N(5)-tri-μ2-dicyanamido-κ(6)N(1):N(5)-dimanganese(II)]], {[(CH3)4N][Mn2(NCNCN)5]}n, (I), and catena-poly[bis(butyltriphenylphosphonium) [[(dicyanamido-κN(1))manganese(II)]-di-μ2-dicyanamido-κ(4)N(1):N(5)]], {[(C4H9)(C6H5)3P]2[Mn(NCNCN)4]}n, (II), were synthesized in aqueous solution. In (I), one Mn(II) cation is octahedrally coordinated by six nitrile N atoms from six anionic dicyanamide (dca) ligands, while the second Mn(II) cation is coordinated by four nitrile N atoms and two amide N atoms from six anionic dca ligands. Neighbouring Mn(II) cations are linked together by μ-1,5- and μ-1,3,5-bridging dca anions to form a three-dimensional polymeric structure. The anionic framework exhibits a solvent-accessible void of 289.8 Å(3), amounting to 28.0% of the total unit-cell volume. Each of the cavities in the network is occupied by only one tetramethylammonium cation. In (II), each Mn(II) cation is octahedrally coordinated by six nitrile N atoms from six dca ligands. Neighbouring Mn(II) cations are linked together by double dca bridges to form a one-dimensional polymeric chain, and C-H...N hydrogen-bonding interactions are involved in the formation of the one-dimensional layer structure.
为了探索新型金属配位聚合物，并在杂化配位聚合物中寻找新型铁电体，在水溶液中合成了两种二氰胺锰配合物，聚[四甲基铵[二-μ3-二氰胺基-κ(6)N(1):N(3):N(5)-三-μ2-二氰胺基-κ(6)N(1):N(5)-二锰(II)]]，{[(CH3)4N][Mn2(NCNCN)5]}n，(I)，和链状聚[双(丁基三苯基膦鎓)[[(二氰胺基-κN(1))锰(II)]-二-μ2-二氰胺基-κ(4)N(1):N(5)]]，{[(C4H9)(C6H5)3P]2[Mn(NCNCN)4]}n，(II)。在(I)中，一个Mn(II)阳离子由来自六个阴离子二氰胺(dca)配体的六个腈N原子八面体配位，而第二个Mn(II)阳离子由来自六个阴离子dca配体的四个腈N原子和两个酰胺N原子配位。相邻的Mn(II)阳离子通过μ-1,5-和μ-1,3,5-桥连dca阴离子连接在一起，形成三维聚合物结构。阴离子骨架显示出289.8 Å(3)的溶剂可及空隙，占总晶胞体积的28.0%。网络中的每个空腔仅被一个四甲基铵阳离子占据。在(II)中，每个Mn(II)阳离子由来自六个dca配体的六个腈N原子八面体配位。相邻的Mn(II)阳离子通过双dca桥连接在一起，形成一维聚合物链，并且C-H...N氢键相互作用参与一维层状结构的形成。
