TY - JOUR

T1 - Noncovalent Interactions Involving lodofluorobenzenes

T2 - The Interplay of Halogen Bonding and Weak Ip(O)center dot center dot center dot pi-Hole(arene) Interactions

AU - Novikov, Alexander S.

AU - Ivanov, Daniil M.

AU - Bikbaeva, Zarina M.

AU - Bokach, Nadezhda A.

AU - Kukushkin, Vadim Yu.

N1 - doi: 10.1021/acs.cgd.8b01457

PY - 2018/12/5

Y1 - 2018/12/5

N2 - Fluorinated iodoarenes such as 1,4-diiodotetrafluorobenzene (1,4-FIB) and 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) were cocrystallized with the nitrosoguanidinate-nickel(II) species [Ni{NHC(NRR')NN(O)} 2] (RR' = Me 2 1, RR' = MePh 2, RR' = (CH 2) 5 3) and structures of three adducts were studied by X-ray crystallography. The Hirshfeld surface analysis for the X-ray structures of 1·(1,4-FIB), 2·2(1,3,5-FIB), and 3·2(1,4-FIB) revealed that crystal packing is determined primarily by intermolecular contacts involving hydrogen and halogen atoms. In addition, FIBs are linked to the O atom of the nitroso-group via π-hole of the arene cores thus representing an unreported noncovalent bonding pattern for iodofluorobenzenes; it belongs to lone pair(O)-π hole interactions, lp(O)-πh. Results of DFT calculations followed by QTAIM analysis at the M06/DZP-DKH level of theory revealed that estimated energies of the lp(O)-πh interactions are 1.3-2.2 kcal/mol (in experimental X-ray geometries of model supramolecular adducts) or 0.9-2.4 kcal/mol (in equilibrium optimized geometries of model supramolecular adducts). The geometry optimization procedure for model adducts does not change significantly the structural motifs of these systems indicating that lp(O)-πh contacts are not determined exclusively by crystal packing effects, but also exist in the isolated "gas phase" form. Our processing of the CCDC database and the theoretical calculations for TAXZAW01, featuring the shortest O···arene distance, revealed five additional structures with overlooked lp(O)-πh contacts involving iodofluoroarene cores.

AB - Fluorinated iodoarenes such as 1,4-diiodotetrafluorobenzene (1,4-FIB) and 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) were cocrystallized with the nitrosoguanidinate-nickel(II) species [Ni{NHC(NRR')NN(O)} 2] (RR' = Me 2 1, RR' = MePh 2, RR' = (CH 2) 5 3) and structures of three adducts were studied by X-ray crystallography. The Hirshfeld surface analysis for the X-ray structures of 1·(1,4-FIB), 2·2(1,3,5-FIB), and 3·2(1,4-FIB) revealed that crystal packing is determined primarily by intermolecular contacts involving hydrogen and halogen atoms. In addition, FIBs are linked to the O atom of the nitroso-group via π-hole of the arene cores thus representing an unreported noncovalent bonding pattern for iodofluorobenzenes; it belongs to lone pair(O)-π hole interactions, lp(O)-πh. Results of DFT calculations followed by QTAIM analysis at the M06/DZP-DKH level of theory revealed that estimated energies of the lp(O)-πh interactions are 1.3-2.2 kcal/mol (in experimental X-ray geometries of model supramolecular adducts) or 0.9-2.4 kcal/mol (in equilibrium optimized geometries of model supramolecular adducts). The geometry optimization procedure for model adducts does not change significantly the structural motifs of these systems indicating that lp(O)-πh contacts are not determined exclusively by crystal packing effects, but also exist in the isolated "gas phase" form. Our processing of the CCDC database and the theoretical calculations for TAXZAW01, featuring the shortest O···arene distance, revealed five additional structures with overlooked lp(O)-πh contacts involving iodofluoroarene cores.

KW - CENTER-DOT-PI

KW - CHARGE-TRANSFER

KW - CO-CRYSTALS

KW - CRYSTAL-STRUCTURES

KW - DESIGN

KW - SIGMA-HOLE

KW - SOLID-STATE

KW - STRUCTURAL COMPETITION

KW - VAN

KW - ZETA BASIS-SETS

UR - http://www.scopus.com/inward/record.url?scp=85057031394&partnerID=8YFLogxK

UR - http://pubs.acs.org/doi/10.1021/acs.cgd.8b01457

UR - http://www.mendeley.com/research/noncovalent-interactions-involving-iodofluorobenzenes-interplay-halogen-bonding-weak-lpo%CF%80hole-subare

U2 - 10.1021/acs.cgd.8b01457

DO - 10.1021/acs.cgd.8b01457

M3 - Article

VL - 18

SP - 7641

EP - 7654

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 12

ER -