Shao Ze-Huai, Luo Jun, Cai Rui-Fang, Zhou Xi-Geng, Weng Lin-Hong, Chen Zhen-Xia
Department of Chemistry, Fudan University, Shanghai 200433, People's Republic of China.
Acta Crystallogr C. 2004 Jun;60(Pt 6):m250-3. doi: 10.1107/S0108270104008406. Epub 2004 May 11.
Two new one-dimensional coordination polymers, viz. the title compounds, CoC(CN)(3)(C(6)H(5)N(3))(2), (I), and MnC(CN)(3)(C(5)H(8)N(2))(2), (II), have been synthesized and characterized by X-ray diffraction. Both complexes consist of linear chains with double 1,5-tricyanomethanide bridges between neighbouring divalent metal ions. The Co and Mn atoms are located on centres of inversion. In (I), the coordination environment of the Co(II) atom is that of an elongated octahedron. The Co(II) atom is coordinated in the equatorial plane by four nitrile N atoms of four bridging tricyanomethanide ions, with Co-N distances of 2.106 (2) and 2.110 (2) A, and in the apical positions by two N atoms from the benzotriazole ligands, with a Co-N distance of 2.149 (2) A. The [CoC(CN)(3)(C(6)H(5)N(3))(2)] units form infinite chains extending along the a axis. These chains are crosslinked via a hydrogen bond between the uncoordinated nitrile N atom of a tricyanomethanide anion and the H atom on the uncoordinated N atom of a benzotriazole ligand from an adjacent chain, thus forming a three-dimensional network structure. In (II), the Mn(II) atom also adopts a slightly distorted octahedral geometry, with four nitrile N atoms of tricyanomethanide ligands [Mn-N = 2.226 (2) and 2.227 (2) A] in equatorial positions and two N atoms of the monodentate 3,5-dimethylpyrazole ligands [Mn-N = 2.231 (2) A] in the axial sites. In (II), one-dimensional polymeric chains extending along the b axis are formed, with tricyanomethanide anions acting as bidentate bridging ligands. A hydrogen bond between the uncoordinated nitrile N atom of the tricyanomethanide ligand and the H atom on the uncoordinated N atom of a 3,5-dimethylpyrazole group from a neighbouring chain links the molecule into a two-dimensional layered structure.
两种新型一维配位聚合物,即标题化合物CoC(CN)(3)(C(6)H(5)N(3))(2),(I),和MnC(CN)(3)(C(5)H(8)N(2))(2),(II),已经通过X射线衍射进行了合成和表征。两种配合物均由线性链组成,相邻二价金属离子之间有双1,5 - 三氰基甲烷桥。Co和Mn原子位于对称中心。在(I)中,Co(II)原子的配位环境为拉长的八面体。Co(II)原子在赤道平面上由四个桥连三氰基甲烷离子的腈N原子配位,Co - N距离为2.106(2)和2.110(2) Å,在顶端位置由来自苯并三唑配体的两个N原子配位,Co - N距离为2.149(2) Å。[CoC(CN)(3)(C(6)H(5)N(3))(2)]单元形成沿a轴延伸的无限链。这些链通过三氰基甲烷阴离子的未配位腈N原子与相邻链的苯并三唑配体的未配位N原子上的H原子之间的氢键交联,从而形成三维网络结构。在(II)中,Mn(II)原子也采用略微扭曲的八面体几何构型,赤道位置有三氰基甲烷配体的四个腈N原子[Mn - N = 2.226(2)和2.227(2) Å],轴向位置有单齿3,5 - 二甲基吡唑配体的两个N原子[Mn - N = 2.231(2) Å]。在(II)中,形成了沿b轴延伸的一维聚合物链,三氰基甲烷阴离子作为双齿桥连配体。三氰基甲烷配体的未配位腈N原子与相邻链的3,5 - 二甲基吡唑基团的未配位N原子上的H原子之间的氢键将分子连接成二维层状结构。