Corfield Peter W R, Goedken Virgil L
Department of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA.
Department of Chemistry, The Ohio State University, Columbus, OH 43210, USA.
Acta Crystallogr E Crystallogr Commun. 2019 Feb 8;75(Pt 3):332-337. doi: 10.1107/S2056989019002056. eCollection 2019 Mar 1.
The crystal structure of the Ni-14 macrocycle salt, (5,7,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)nickel(II) bis-(perchlorate) hemihydrate, Ni(CHN)·HO, contains two different diasteriomeric macrocyclic cations in the asymmetric unit, one with two NH protons on each side of the cation (), and the other with all four NH protons on the same side (). The crystal structure of the bromide trihydrate salt of the same Ni-14 macrocyclic cation, namely (5,7,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)nickel(II) dibromide trihydrate, [Ni(CHN)]Br·3HO (), contains only the same diastereomer as , with the four N-H bonds on the same side. The geometry around the Ni atom differs slightly between the two diastereomeric cations, as the mean Ni-N distance in is 1.952 (2) Å, while that for and is 1.928 (2) Å. The hexa-methyl substitution in all three macrocyclic cations has the two dimethyl-substituted C atoms to one another, different from the 5,5,7,12,12,14-hexa-methyl Ni-14 cations found in all but one of the many published crystal structures of hexa-methyl Ni-14 macrocycles. In each of the two crystal structures, the anions, water mol-ecules, and N-H protons of the macrocyclic cations form extensive hydrogen-bonded zigzag chains propagating along [001] in and [010] in .
镍 - 14大环盐（5,7,7,12,12,14 - 六甲基 - 1,4,8,11 - 四氮杂环十四烷）镍（II）双（高氯酸盐）半水合物，Ni(CHN)·HO的晶体结构在不对称单元中包含两种不同的非对映异构大环阳离子，一种在阳离子两侧各有两个NH质子（ ），另一种的所有四个NH质子在同一侧（ ）。相同镍 - 14大环阳离子的溴化三水合物盐，即（5,7,7,12,12,14 - 六甲基 - 1,4,8,11 - 四氮杂环十四烷）镍（II）二溴化三水合物，[Ni(CHN)]Br·3HO（ ）的晶体结构仅包含与 相同的非对映异构体，四个N - H键在同一侧。两种非对映异构阳离子周围镍原子的几何形状略有不同，因为 中的平均Ni - N距离为1.952 (2) Å，而 和 中的为1.928 (2) Å。所有三种大环阳离子中的六甲基取代使得两个二甲基取代的C原子彼此（ ），这与在许多已发表的六甲基镍 - 14大环晶体结构中除一个之外的所有结构中发现的5,5,7,12,12,14 - 六甲基镍 - 14阳离子不同。在这两种晶体结构中，大环阳离子的阴离子、水分子和N - H质子形成了广泛的氢键锯齿链，在 中沿[001]方向传播，在 中沿[010]方向传播。
