TY - JOUR

T1 - Recognition of S center dot center dot center dot CI Chalcogen Bonding in Metal-Bound Alkylthiocyanates

AU - Yandanova, Ekaterina S.

AU - Ivanov, Daniil M.

AU - Kuznetsov, Maxim L.

AU - Starikov, Andrey G.

AU - Starova, Galina L.

AU - Kukushkin, Vadim Yu.

PY - 2016/5

Y1 - 2016/5

N2 - Reaction of K-2[PtCl4] with excess AIkSCN in water gives the alkylthiocyanate complexes trans-[PtCl2-(AlkSCN)(2)] (Alk = Et 1, Pr-n 2; 80-85%). These species were studied, in particular, by X-ray crystallography. In the solid state, both 1 and 2 exhibit the previously unreported S center dot center dot center dot Cl chalcogen bonding, which consolidates the complexes into networks and leads to layered structures. Theoretical density functional theory calculations and Bader's atoms in molecules analysis demonstrated two types of intermolecular interactions in tetramer (1)(4), viz. the S center dot center dot center dot Cl chalcogen and the H center dot center dot center dot Cl hydrogen bonds. Despite that each particular S center dot center dot center dot Cl or H center dot center dot center dot Cl bonding is weak -with the estimated energy of 1-2 kcal/mol, altogether they play a crucial role in the stabilization of the S2Cl2 fragment in (1)(4), the basis set of superposition error corrected interaction energy being -12.8 kcal/mol per monomer complex molecule. The chalcogen bonding and the rhomboidal structure of the S2Cl2 fragment can be interpreted in terms of electrostatic arguments as a result of the interaction between the belt of negative electrostatic potential around the Cl atoms and the sulfur (Tholes. The natural bond orbital analysis revealed that both LP(S) -> LP*(Pt)/sigma*(Pt-N)/sigma*(Pt-Cl) and LP(Cl) -> sigma o*(S-C) types of hyperconjugative charge transfers are important in the chalcogen bonding.

AB - Reaction of K-2[PtCl4] with excess AIkSCN in water gives the alkylthiocyanate complexes trans-[PtCl2-(AlkSCN)(2)] (Alk = Et 1, Pr-n 2; 80-85%). These species were studied, in particular, by X-ray crystallography. In the solid state, both 1 and 2 exhibit the previously unreported S center dot center dot center dot Cl chalcogen bonding, which consolidates the complexes into networks and leads to layered structures. Theoretical density functional theory calculations and Bader's atoms in molecules analysis demonstrated two types of intermolecular interactions in tetramer (1)(4), viz. the S center dot center dot center dot Cl chalcogen and the H center dot center dot center dot Cl hydrogen bonds. Despite that each particular S center dot center dot center dot Cl or H center dot center dot center dot Cl bonding is weak -with the estimated energy of 1-2 kcal/mol, altogether they play a crucial role in the stabilization of the S2Cl2 fragment in (1)(4), the basis set of superposition error corrected interaction energy being -12.8 kcal/mol per monomer complex molecule. The chalcogen bonding and the rhomboidal structure of the S2Cl2 fragment can be interpreted in terms of electrostatic arguments as a result of the interaction between the belt of negative electrostatic potential around the Cl atoms and the sulfur (Tholes. The natural bond orbital analysis revealed that both LP(S) -> LP*(Pt)/sigma*(Pt-N)/sigma*(Pt-Cl) and LP(Cl) -> sigma o*(S-C) types of hyperconjugative charge transfers are important in the chalcogen bonding.

KW - CRYSTAL-STRUCTURES

KW - HALOGEN BOND

KW - INTERMOLECULAR INTERACTIONS

KW - MOLECULAR-STRUCTURE

KW - COMPLEXES

KW - DENSITY

KW - ANION

KW - THERMOCHEMISTRY

KW - DITHIOCYANATE

KW - THIOCYANATE

U2 - 10.1021/acs.cgd.6b00346

DO - 10.1021/acs.cgd.6b00346

M3 - статья

VL - 16

SP - 2979

EP - 2987

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 5

ER -