TY - JOUR
T1 - Centrosymmetric Nickel(II) Complexes Derived from Bis-(Dithiocarbamato)piperazine with 1,1′-Bis-(Diphenylphosphino)ferrocene and 1,2-Bis-(Diphenylphosphino)ethane as Ancillary Ligands
T2 - Syntheses, Crystal Structure and Computational Studies
AU - Srivastava, Devyani
AU - Prakash, Om
AU - Kociok-Köhn, Gabriele
AU - Kumar, Abhinav
AU - Alarifi, Abdullah
AU - Abduh, Naaser A.Y.
AU - Afzal, Mohd
AU - Muddassir, Mohd
N1 - Funding Information:
The authors extend their appreciation to the Deputyship for Research & Innovation, Ministry of Education in Saudi Arabia, for funding this research work through the project number IFKSURG-2-1503.
PY - 2023/2/17
Y1 - 2023/2/17
N2 - Two Ni(II) complexes with the formula [{Ni(dppf)}2{(L1)2}](PF6)2 (Ni-I) and [{Ni(dppe)}2{(L1)2}](PF6)2 (Ni-II) were prepared by reacting [Ni(dppf)Cl2] and [Ni(dppe)Cl2] (dppf = 1,1′-Bis-(diphenylphosphino)ferrocene; dppe = 1,2-Bis-(diphenylphosphino)ethane) with secondary amine piperazine derived ligand disodium bis-(dithiocarbamate)piperazine ((piper(dtc)2 = L1) and counter anion PF6−. These complexes were characterized by elemental analyses, FT-IR, 1H, 13C and 31P NMR, UV-Vis. spectroscopy and single crystal X-ray diffraction. The X-ray analyses reveal centrosymmetric structures where each Ni(II) centre adopts distorted square planar geometry defined by two sulfur centres of dithiocarbamate ligand and two phosphorus centres of dppf and dppe ligands in Ni-I and Ni-II, respectively. The supramolecular framework of both Ni-I and Ni-II are sustained by C-H⋯π and C-H⋯F interactions, and they also display interesting intramolecular C-H⋯Ni anagostic interactions. Further, the nature of these interactions are studied using Hirshfeld surface analyses, DFT and quantum theory of atoms in molecules (QTAIM) calculations. Additionally, non-covalent interaction (NCI) plot analyses were conducted to gain additional insight into these non-covalent interactions. This work is vital in a new approach towards the rational designing of the centrosymmetric molecules with interesting architectures.
AB - Two Ni(II) complexes with the formula [{Ni(dppf)}2{(L1)2}](PF6)2 (Ni-I) and [{Ni(dppe)}2{(L1)2}](PF6)2 (Ni-II) were prepared by reacting [Ni(dppf)Cl2] and [Ni(dppe)Cl2] (dppf = 1,1′-Bis-(diphenylphosphino)ferrocene; dppe = 1,2-Bis-(diphenylphosphino)ethane) with secondary amine piperazine derived ligand disodium bis-(dithiocarbamate)piperazine ((piper(dtc)2 = L1) and counter anion PF6−. These complexes were characterized by elemental analyses, FT-IR, 1H, 13C and 31P NMR, UV-Vis. spectroscopy and single crystal X-ray diffraction. The X-ray analyses reveal centrosymmetric structures where each Ni(II) centre adopts distorted square planar geometry defined by two sulfur centres of dithiocarbamate ligand and two phosphorus centres of dppf and dppe ligands in Ni-I and Ni-II, respectively. The supramolecular framework of both Ni-I and Ni-II are sustained by C-H⋯π and C-H⋯F interactions, and they also display interesting intramolecular C-H⋯Ni anagostic interactions. Further, the nature of these interactions are studied using Hirshfeld surface analyses, DFT and quantum theory of atoms in molecules (QTAIM) calculations. Additionally, non-covalent interaction (NCI) plot analyses were conducted to gain additional insight into these non-covalent interactions. This work is vital in a new approach towards the rational designing of the centrosymmetric molecules with interesting architectures.
KW - metal ions
KW - NCI
KW - reduced schiff-base
KW - X-ray crystallography
UR - http://www.scopus.com/inward/record.url?scp=85149218373&partnerID=8YFLogxK
U2 - 10.3390/cryst13020343
DO - 10.3390/cryst13020343
M3 - Article
AN - SCOPUS:85149218373
SN - 2073-4352
VL - 13
JO - Crystals
JF - Crystals
IS - 2
M1 - 343
ER -