Potočňák Ivan, Burčák Milan, Dušek Michal
Department of Inorganic Chemistry, Faculty of Science, P. J. Šafárik University, Moyzesova 11, SK-041 54 Košice, Slovakia.
Acta Crystallogr C. 2013 Nov;69(Pt 11):1357-61. doi: 10.1107/S0108270113027091. Epub 2013 Oct 12.
(Dicyanamido-κN(1))bis(5,5'-dimethyl-2,2'-bipyridine-κ(2)N,N')copper(II) tetrafluoroborate, [Cu{N(CN)2}(C12H12N2)2]BF4, (I), and (dicyanamido-κN(1))bis(5,5'-dimethyl-2,2'-bipyridine-κ(2)N,N')copper(II) perchlorate, [Cu{N(CN)2}(C12H12N2)2]ClO4, (II), are isomorphous and consist of Cu{N(CN)2}(mbpy)2 cations (mbpy is 5,5'-dimethyl-2,2'-bipyridine) and BF4(-) or ClO4(-) anions, respectively. The Cu(II) cations in both structures are five-coordinated in distorted trigonal bipyramidal environments by four N atoms of two mbpy ligands and one N atom of the dicyanamide anion, which is coordinated in a monodentate manner in the equatorial plane, with Cu-N distances of 1.980 (3) and 1.977 (2) Å in (I) and (II), respectively. The two axial Cu-Nmbpy bonds have very similar values [1.986 (1) Å on average] and are shorter than the other two equatorial Cu-Nmbpy bonds. These have different values in the individual compounds but nevertheless form two pairs of similar bonds in (I) and (II) [2.066 (8) and 2.112 (2) Å, respectively, on average]. Besides the ionic forces in both structures, the structures are stabilized by C-H...N and C-H...X hydrogen bonds (X = F and O, respectively), and by π-π interactions between the pyridine rings of neighbouring mbpy molecules.
四氟硼酸(二氰胺基 - κN(1))双(5,5'-二甲基 - 2,2'-联吡啶 - κ(2)N,N')铜(II),[Cu{N(CN)₂}(C₁₂H₁₂N₂)₂]BF₄,(I),和高氯酸(二氰胺基 - κN(1))双(5,5'-二甲基 - 2,2'-联吡啶 - κ(2)N,N')铜(II),[Cu{N(CN)₂}(C₁₂H₁₂N₂)₂]ClO₄,(II),是同晶型的,分别由Cu{N(CN)₂}(mbpy)₂阳离子(mbpy是5,5'-二甲基 - 2,2'-联吡啶)和BF₄(-)或ClO₄(-)阴离子组成。两种结构中的Cu(II)阳离子在扭曲的三角双锥环境中通过两个mbpy配体的四个N原子和二氰胺阴离子的一个N原子进行五配位,二氰胺阴离子在赤道平面以单齿方式配位,在(I)和(II)中Cu - N距离分别为1.980 (3)和1.977 (2) Å。两条轴向Cu - Nmbpy键的值非常相似[平均为1.986 (1) Å],并且比另外两条赤道面的Cu - Nmbpy键短。它们在各个化合物中的值不同,但在(I)和(II)中仍分别形成两对相似的键[平均分别为2.066 (8)和2.112 (2) Å]。除了两种结构中的离子力外,结构还通过C - H...N和C - H...X氢键(X分别为F和O)以及相邻mbpy分子吡啶环之间的π - π相互作用得以稳定。