TY - JOUR
T1 - Spectroscopic and DFT studies of zinc(II) complexes of diamines and thiocyanate; crystal structure of (cis-1,2-diaminocyclohexane)bis(thiocyanato-κN)zinc(II)
AU - Akhtar, Muhammad
AU - Alotaibi, Mshari A.
AU - Alharthi, Abdulrahman I.
AU - Zierkiewicz, Wiktor
AU - Tahir, Muhammad Nawaz
AU - Mazhar, Muhammad
AU - Isab, Anvarhusein A.
AU - Monim-ul-Mehboob, Muhammad
AU - Ahmad, Saeed
N1 - Publisher Copyright:
© 2016 Elsevier B.V.
PY - 2017/1/15
Y1 - 2017/1/15
N2 - Zinc(II) complexes of diamines, cis-1,2-diaminocyclohexane (Dach) and N,N,N,N-tetramethylethylenediamine (Tmen), [Zn(Dach)(NCS)2] (1) and [Zn(Tmen)(NCS)2] (2) have been prepared and characterized by elemental analysis, IR, 1H & 13C NMR spectroscopy. The crystal structure of [Zn(Dach)(NCS)2] (1) was determined by X-ray crystallography. In 1, the Zn(II) atom is bound to one 1,2-diaminocyclohexane molecule and to two terminal thiocyanate ions via the nitrogen atoms adopting a slightly distorted tetrahedral geometry. In the crystal structure, molecules are linked through intermolecular N[sbnd]H⋯S hydrogen bonds, forming chains running along the a axis. The structures of 1 and 2 as well as of [Zn(En)(NCS)2] (3) (En = 1,2-diaminoethane) were predicted using theoretical (DFT) method. The interaction energies (ΔE) for NCS anions obtained by B3LYP-D3 method are about −140 kcal mol−1, while the calculated ΔE values for neutral organic ligands are about twice smaller. The atomic charges and second-order interaction energies between orbitals were calculated with natural bond orbital (NBO) analysis.
AB - Zinc(II) complexes of diamines, cis-1,2-diaminocyclohexane (Dach) and N,N,N,N-tetramethylethylenediamine (Tmen), [Zn(Dach)(NCS)2] (1) and [Zn(Tmen)(NCS)2] (2) have been prepared and characterized by elemental analysis, IR, 1H & 13C NMR spectroscopy. The crystal structure of [Zn(Dach)(NCS)2] (1) was determined by X-ray crystallography. In 1, the Zn(II) atom is bound to one 1,2-diaminocyclohexane molecule and to two terminal thiocyanate ions via the nitrogen atoms adopting a slightly distorted tetrahedral geometry. In the crystal structure, molecules are linked through intermolecular N[sbnd]H⋯S hydrogen bonds, forming chains running along the a axis. The structures of 1 and 2 as well as of [Zn(En)(NCS)2] (3) (En = 1,2-diaminoethane) were predicted using theoretical (DFT) method. The interaction energies (ΔE) for NCS anions obtained by B3LYP-D3 method are about −140 kcal mol−1, while the calculated ΔE values for neutral organic ligands are about twice smaller. The atomic charges and second-order interaction energies between orbitals were calculated with natural bond orbital (NBO) analysis.
KW - DFT calculations
KW - Diamines
KW - Thiocyanate
KW - X-ray structure
KW - Zinc(II)
UR - http://www.scopus.com/inward/record.url?scp=84987834906&partnerID=8YFLogxK
U2 - 10.1016/j.molstruc.2016.09.015
DO - 10.1016/j.molstruc.2016.09.015
M3 - Article
AN - SCOPUS:84987834906
SN - 0022-2860
VL - 1128
SP - 455
EP - 461
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
ER -