TY - JOUR

T1 - Isomorphous Series of PdII-Containing Halogen-Bond Donors Exhibiting Cl/Br/I Triple Halogen Isostructural Exchange

AU - Buldakov, Alexander V.

AU - Kinzhalov, Mikhail A.

AU - Kryukova, Mariya A.

AU - Ivanov, Daniil M.

AU - Novikov, Alexander S.

AU - Smirnov, Andrey S.

AU - Starova, Galina L.

AU - Bokach, Nadezhda A.

AU - Kukushkin, Vadim Yu.

PY - 2020/3/4

Y1 - 2020/3/4

N2 - Two isomorphous series including the adducts trans-[PdI2(CNC6H4-4-X)2]·2I2 [(1-3)·2I2; X = Cl 1, Br 2, I 3] and the complexes cis-[PdCl2(CNC6H4-4-X)(PPh3)] (4-6; X = Cl 4, Br 5, I 6) were characterized by X-ray crystallography. Inspection of the X-ray diffraction data allowed the identification of halogen-bonding C-X···I-I in (1-3)·2I2 and C-X···Cl-[Pd] in 4-6 thus providing a rare example of the triple Cl/Br/I exchange of σ-hole donating halogens. In accord with the conducted theoretical considerations, the strength of these XBs are in the range of 0.9-2.8 kcal/mol, and these contacts are of a noncovalent nature. The calculated maximum electrostatic potentials on the σ-hole donating X centers of CNC6H4-4-X on the 0.001 au molecular surfaces for both (1-3)·2I2 and 4-6 series are increased along with the decrease of relative XB lengths. These data are consistent with Politzer and co-workers conclusions that are based exclusively on theoretical ground.

AB - Two isomorphous series including the adducts trans-[PdI2(CNC6H4-4-X)2]·2I2 [(1-3)·2I2; X = Cl 1, Br 2, I 3] and the complexes cis-[PdCl2(CNC6H4-4-X)(PPh3)] (4-6; X = Cl 4, Br 5, I 6) were characterized by X-ray crystallography. Inspection of the X-ray diffraction data allowed the identification of halogen-bonding C-X···I-I in (1-3)·2I2 and C-X···Cl-[Pd] in 4-6 thus providing a rare example of the triple Cl/Br/I exchange of σ-hole donating halogens. In accord with the conducted theoretical considerations, the strength of these XBs are in the range of 0.9-2.8 kcal/mol, and these contacts are of a noncovalent nature. The calculated maximum electrostatic potentials on the σ-hole donating X centers of CNC6H4-4-X on the 0.001 au molecular surfaces for both (1-3)·2I2 and 4-6 series are increased along with the decrease of relative XB lengths. These data are consistent with Politzer and co-workers conclusions that are based exclusively on theoretical ground.

KW - ZETA BASIS-SETS

KW - CRYSTAL-STRUCTURES

KW - THERMAL-EXPANSION

KW - CO-CRYSTALS

KW - TEMPERATURE

KW - VAN

KW - STRENGTHS

KW - PHOSPHORESCENCE

KW - THERMODYNAMICS

KW - POLYMORPHISM

UR - http://www.scopus.com/inward/record.url?scp=85081121438&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/81656cdf-4c04-367f-a675-20778ea13eb9/

U2 - 10.1021/acs.cgd.9b01631

DO - 10.1021/acs.cgd.9b01631

M3 - Article

AN - SCOPUS:85081121438

VL - 20

SP - 1975

EP - 1984

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 3

ER -