TY - JOUR
T1 - Synthesis, crystal structure and DFT calculations of a cyanido-bridged dinuclear zinc(II) complex of cis-1,2-diaminocyclohexane (Dach) containing a dinuclear cyanidozincate(II) anion, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH
AU - Monim-ul-Mehboob, Muhammad
AU - Rüffer, Tobias
AU - Lang, Heinrich
AU - Zierkiewicz, Wiktor
AU - Rauf, Abdul
AU - Amin, Muhammad
AU - Isab, Anvarhusein A.
AU - Ajouyed, Omar
AU - Ahmad, Saeed
N1 - Publisher Copyright:
© 2018 Elsevier B.V.
PY - 2018/10/5
Y1 - 2018/10/5
N2 - A zinc(II)-cyanide complex of cis-1,2-diaminocyclohexane (Dach) containing two dinuclear units, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH (1) was prepared and characterized by IR and NMR spectroscopy as well as by single crystal X-ray crystallography. Complex 1 is composed of two dinuclear ionic units, cationic [Zn2(Dach)4(CN)]3+ and anionic [Zn2(CN)7]3- and two non-coordinating molecules of methanol. The Zn atoms in [Zn2(Dach)4(CN)]3+ cation adopt a square-pyramidal environment with CN ligand occupying the apical position, while the Zn atoms in [Zn2(CN)7]3- anion exhibit a tetrahedral geometry. The dinuclear units are associated to each other through hydrogen bonding interactions to form a three dimensional network in the solid state. The presence of, a band around 2200 cm−1 in IR spectrum and a resonance at 140 ppm in 13C NMR indicated the presence of cyanide in the complex. The structures of 1 and two of its analogues, [Zn(Dach)(CN)2]4 (2) and {[Zn(Dach)2][Zn(CN)4]}2 (3) were predicted using theoretical (DFT) method. The DFT calculated values of the Gibbs free energies of the model complexes reveal that 1 is more stable than the analogous predicted complexes, 2 and 3 by 5.16 and 3.47 kcal mol−1, respectively.
AB - A zinc(II)-cyanide complex of cis-1,2-diaminocyclohexane (Dach) containing two dinuclear units, [Zn2(Dach)4(CN)][Zn2(CN)7]·2CH3OH (1) was prepared and characterized by IR and NMR spectroscopy as well as by single crystal X-ray crystallography. Complex 1 is composed of two dinuclear ionic units, cationic [Zn2(Dach)4(CN)]3+ and anionic [Zn2(CN)7]3- and two non-coordinating molecules of methanol. The Zn atoms in [Zn2(Dach)4(CN)]3+ cation adopt a square-pyramidal environment with CN ligand occupying the apical position, while the Zn atoms in [Zn2(CN)7]3- anion exhibit a tetrahedral geometry. The dinuclear units are associated to each other through hydrogen bonding interactions to form a three dimensional network in the solid state. The presence of, a band around 2200 cm−1 in IR spectrum and a resonance at 140 ppm in 13C NMR indicated the presence of cyanide in the complex. The structures of 1 and two of its analogues, [Zn(Dach)(CN)2]4 (2) and {[Zn(Dach)2][Zn(CN)4]}2 (3) were predicted using theoretical (DFT) method. The DFT calculated values of the Gibbs free energies of the model complexes reveal that 1 is more stable than the analogous predicted complexes, 2 and 3 by 5.16 and 3.47 kcal mol−1, respectively.
KW - Cyanide
KW - DFT calculations
KW - X-ray structure
KW - Zinc(II)
KW - cis-1,2-Diaminocyclohexane
UR - https://www.scopus.com/pages/publications/85047269191
U2 - 10.1016/j.molstruc.2018.05.049
DO - 10.1016/j.molstruc.2018.05.049
M3 - Article
AN - SCOPUS:85047269191
SN - 0022-2860
VL - 1169
SP - 110
EP - 118
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
ER -