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]

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-Ni_1/4-)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.