TY - JOUR

T1 - Diiodomethane as a halogen bond donor toward metal-bound halides

AU - Novikov, A.S.

AU - Ivanov, D.M.

AU - Avdontceva, M.S.

AU - Kukushkin, V.Y.

N1 - cited By 4

PY - 2017/5/14

Y1 - 2017/5/14

N2 - A 1,3,5,7,9-pentaazanona-1,3,6,8-tetraenate (PANT) chloride platinum.II) complex (1) was obtained via the metal-mediated double coupling of 2,3-diphenylmaleimidine with both nitrile ligands in trans[PtCl2.NCtBu)(2)]. Compound 1 was then co-crystallized with diiodomethane forming solvate 1.1/2CH(2)I(2). The XRD experiment reveals that this solvate displays the halogen bonds H2C(I)-I...Cl-Pt and hydrogen bonds I2C(H)-H. Cl-Pt, which join two complex and one CH2I2 molecules in a heterotrimeric supramolecular cluster. Inspection of the CCDC database reveals only one example of the halogen bond H2C(I)-I...I-Pt between the CH2I2 molecule and metal-coordinated halide in the structure of VEMWOA. In VEMWOA, CH2I2 serves solely as a halogen bond donor with no hydrogen bond contribution. Results of the Hirshfeld surface analysis and DFT calculations (M06/DZP-DKH level of theory) followed by topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) for both .1/2CH(2)I(2) and VEMWOA confirmed the formation of these weak interactions. The evaluated energies of halogen bonds involving CH2I2 are in the 2.2-2.8 kcal mol(-1) range.

AB - A 1,3,5,7,9-pentaazanona-1,3,6,8-tetraenate (PANT) chloride platinum.II) complex (1) was obtained via the metal-mediated double coupling of 2,3-diphenylmaleimidine with both nitrile ligands in trans[PtCl2.NCtBu)(2)]. Compound 1 was then co-crystallized with diiodomethane forming solvate 1.1/2CH(2)I(2). The XRD experiment reveals that this solvate displays the halogen bonds H2C(I)-I...Cl-Pt and hydrogen bonds I2C(H)-H. Cl-Pt, which join two complex and one CH2I2 molecules in a heterotrimeric supramolecular cluster. Inspection of the CCDC database reveals only one example of the halogen bond H2C(I)-I...I-Pt between the CH2I2 molecule and metal-coordinated halide in the structure of VEMWOA. In VEMWOA, CH2I2 serves solely as a halogen bond donor with no hydrogen bond contribution. Results of the Hirshfeld surface analysis and DFT calculations (M06/DZP-DKH level of theory) followed by topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) for both .1/2CH(2)I(2) and VEMWOA confirmed the formation of these weak interactions. The evaluated energies of halogen bonds involving CH2I2 are in the 2.2-2.8 kcal mol(-1) range.

KW - ZETA BASIS-SETS

KW - HYDROGEN-BOND

KW - SOLID-STATE

KW - CARBON TETRABROMIDE

KW - COMPLEXES

KW - MOLECULES

KW - CLUSTERS

KW - SYSTEMS

KW - ANIONS

KW - ATOMS

U2 - 10.1039/c7ce00346c

DO - 10.1039/c7ce00346c

M3 - Article

VL - 19

SP - 2517

EP - 2525

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 18

ER -