Synthesis and synchrotron X-ray characterization of two 2D Hoffman related compounds [Ni(p-Xylylenediamine)nNi(CN)4] and [Ni(p-tetrafluoroxylylenediamine)nNi(CN)4]

• Published in: Solid state sciences Vol. 81; no. C; pp. 12 - 18
• Main Authors: Wong-Ng, W., Culp, J.T., Siderius, D.W., Chen, Y.S.
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier Masson SAS 01-07-2018; Elsevier
• Subjects: 2D Hofmann-related structures; CO2 mitigation; Ni(p-xylyenediamine)nNi(CN)4; Ni(tetra-fluoro- p-xylyenediamine)nNi(CN)4; Synchrotron X-ray; Synthesis; CO2 mitigation; 2D Hofmann-related structures; Ni(p-xylyenediamine)nNi(CN)4; Synthesis; Ni(tetra-fluoro- p-xylyenediamine)nNi(CN)4; Synchrotron X-ray
• ISSN: 1293-2558; 1873-3085
• DOI: 10.1016/j.solidstatesciences.2018.04.009

Synchrotron X-ray single crystal structure determination of two 2D Hofmann-related compounds, [Ni(p-Xylyenediamine)n-tetracyanonickelate] (abbreviated as Ni-pXdam) and [Ni(tetrafluoro-p-Xylyenediamine)n-tetracyanonickelate] (abbreviated as Ni-pXdamF4), have been conducted. Both the pXdam and pXdamF4 ligands contain two short chains of -CH2NH2 at the para-positions of a phenyl ring. These flexible chains link the 6-fold coordinated Ni2 sites throughout the network. In Ni-pXdam, the closed-2D network of [Ni-(CN-Ni1/4-)4]∞ is broken into 1D chains, leaving the C≡N groups at the trans-positions of the Ni(CN)4 moiety unbridged. The resulting 1D chains [(trans-)-NC-Ni(CN)2-CN-Ni-]∞ runs along the [010] direction of the unit cell. The pXdam ligands bridge in pair between the Ni atoms of the adjacent chains. The catenation structure of [Ni{(pXdam)}]∞ could be referred to as double -1D. In Ni-pXdamF4, the -CH2NH2 ligands connect the neighboring chains via the 6-fold Ni2 site. Surrounding the 4-fold Ni1 site, the two trans terminal C≡N groups were replaced by the Lewis base NH3 during the synthesis process, therefore preventing the propagation of the 2D net to form a 3D network. Computed pore volume of both compounds indicated that there is not sufficient space in the structure to accommodate gas molecules. In both compounds, hydrogen bonds were found, and solvent of crystallization was absent due to the limited free space in the structure.
[Display omitted]
•Structure of two Hofmann related compounds, Ni(L)[Ni(CN)4] (L = ligands), determined.•Both compounds have 2D layered structure instead of the expected 3D structure.•Blocking ligands NH3 replace -C≡N groups, preventing chain propagation.•Hydrogen bonds further stabilized both the 2D structures.