Uhrinová Anna, Kuchár Juraj, Cernák Juraj
Department of Inorganic Chemistry, Institute of Chemistry, P. J. Šafárik University in Košice, Moyzesova 11, 041 54 Košice, Slovakia.
Acta Crystallogr Sect E Struct Rep Online. 2012 Feb 1;68(Pt 2):m92-3. doi: 10.1107/S1600536811054614. Epub 2012 Jan 7.
Using modified solvothermal conditions (longer cooling time), beside previously characterized dark-green crystals of [Ni(C(4)H(2)O(4))(C(12)H(8)N(2))] (main product), a few light-green crystals of the polymeric title compound, catena-poly[[aqua-(1,10-phenanthroline-κ(2)N,N')nickel(II)]-μ-fumarato-κ(2)O:O'-[aqua-(1,10-phenanthroline-κ(2)N,N')nickel(II)]-μ-fumarato-κ(4)O,O':O'',O'''], Ni(C(4)H(2)O(4))(C(12)H(8)N(2))(H(2)O) were isolated. Its crystal structure is made up from zigzag chains, propagating in [001], in which the Ni(2+) ions are linked alternatively by μ(2)-fumarato and bis-chelating fumarato bridging ligands. The Ni(2+) ion is coordinated in a deformed octa-hedral geometry by one chelating 1,10-phenanthroline ligand, one aqua ligand in a cis position with regard to both N-donor atoms and by two different fumarato ligands, each residing with its central C=C bond on an inversion centre, occupying the remaining coordination sites in a fac fashion. The chains thus formed are linked by O-H⋯O hydrogen bonds and π-π inter-actions between the aromatic rings of the phenanthroline ligands with a shortest ring centroid separation of 3.4787 (10) Å.
使用改进的溶剂热条件（更长的冷却时间），除了之前已表征的深绿色晶体[Ni(C₄H₂O₄)(C₁₂H₈N₂)]（主要产物）外，还分离出了一些聚合物标题化合物链状聚[[水合-(1,10-菲咯啉-κ²N,N')镍(II)]-μ-富马酸根-κ²O:O'-[水合-(1,10-菲咯啉-κ²N,N')镍(II)]-μ-富马酸根-κ⁴O,O':O'',O''']，[Ni(C₄H₂O₄)(C₁₂H₈N₂)(H₂O)]ₙ的浅绿色晶体。其晶体结构由沿[001]方向延伸的锯齿链组成，其中Ni²⁺离子通过μ₂-富马酸根和双螯合富马酸根桥联配体交替连接。Ni²⁺离子通过一个螯合的1,10-菲咯啉配体、一个相对于两个氮供体原子处于顺式位置的水合配体以及两个不同的富马酸根配体以变形八面体几何构型配位，每个富马酸根配体的中心C = C键位于一个倒转中心上，以面式方式占据其余配位位点。由此形成的链通过O-H⋯O氢键和菲咯啉配体芳环之间的π-π相互作用相连，最短的环心间距为3.4787 (10) Å。
