Specifics of Molecular Structures of (565)Macrotricyclic 3d-
Metal Chelates in the Ternary Systems M(II)
Hydrazinecarbothioamide2,4-Pentanedione According to DFT
Calculations

D. V. Chachkov^a, O. V. Mikhailov^b, and T. F. Shamsutdinov^c

^a Joint Supercomputer Center, Kazan Branch, Russian Academy of Sciences,
ul. Lobachevskogo 2/31, Kazan, Tatarstan, 420111 Russia

^b Kazan National Research Technological University, ul. K. Marksa 68, Kazan, Tatarstan, 420015 Russia

^c Kazan State University of Architecture and Civil Engineering, ul. Zelenaya 1, Kazan, Tatarstan, 420043 Russia

Received April 17, 2012

Abstract—The geometric parameters of the molecular structures and thermodynamic parameters of formation
of macrotricyclic M(II) complexes (M = Mn, Fe, Co, Ni, Cu, and Zn) with the MN₂S₂ coordination core formed
by the reactions of corresponding hexacyanoferrates(II) with hydrazinecarbothioamide H₂N–HN–C(=S)–NH₂
and 2,4-pentanedione H₃C–C(=O)–CH₂–C(=O)–CH₃ in gelatin-immobilized matrix implants have been calcu-
lated by the B3LYP hybrid density functional theory method with the use of the 6-31G(d) basis set and the
Gaussian 09 program package. The bond lengths and bond and torsion angles in these chelates have been
reported. It has been shown that the Fe(II) and Ni(II) complexes are strictly planar, whereas the Mn(II), Co(II),
and Cu(II) complexes are quasi-planar with a rather small deviation of the MN₂S₂ chelate core from coplanarity,
and only the Zn(II) complex is pseudotetrahedral. The additional six-membered chelate rings resulting from the
above processes are almost planar in all chelates.

DOI: 10.1134/S0036023613050045

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