TY - JOUR

T1 - Bifurcated mu(2)-I center dot center dot center dot(N,O) Halogen Bonding

T2 - The Case of (Nitrosoguanidinate)Ni-II Cocrystals with lodine(I)-Based sigma-Hole Donors

AU - Efimenko, Zarina M.

AU - Eliseeva, Anastasiya A.

AU - Ivanov, Daniil M.

AU - Galmés, Bartomeu

AU - Frontera, Antonio

AU - Bokach, Nadezhda A.

AU - Kukushkin, Vadim Yu

N1 - Funding Information: This work was supported by the Russian Science Foundation (project 19-13-00013). The authors are grateful to the Center for X-ray Diffraction Studies, Magnetic Resonance Research Center, and Center for Chemical Analysis and Materials Research (all belonging to Saint Petersburg State University) for the physicochemical studies. A.A.E. is much obliged to Saint Petersburg State University for a postdoctoral fellowship. V.Y.K. thanks South Ural State University (Act 211 Government of the Russian Federation, contract No 02.A03.21.0011) for putting facilities at the author’s disposal. B.G. and A.F. conducted the theoretical calculations and thank the MICIU/AEI from Spain for financial support (Project CTQ2017-85821-R, Feder funds). Publisher Copyright: © Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2021/1/6

Y1 - 2021/1/6

N2 - Cocrystallization of the nitrosoguanidinate complexes [Ni{NH═C(NR2)NN(O)}2] (R2 = Me2 (1), Me/Ph (2), C5H10 (3)) with 1,2-diiodotetrafluorobenzene (1,2-FIB), 1,4-diiodotetrafluorobenzene (1,4-FIB), 1,3,5-triiodotrifluorobenzene (1,3,5-FIB), and tetraiodoethylene (C2I4) gave new cocrystals (1-3)·2(1,2-FIB), 2·(1,4-FIB), 3·2(1,3,5-FIB), 1·C2I4, and 2·2C2I4; all of these solids were studied by single-crystal X-ray diffraction. Each structure exhibits the asymmetric bifurcated halogen bond μ2-I···(N,O) as a characteristic feature and a structure-directing contact. DFT calculations were used to evaluate the energetic features of the bifurcated halogen bonds that range from -6.7 to -8.3 kcal/mol; in general, the I···O contact is stronger that the I···N contact. Molecular electrostatic potential (MEP) surfaces along with the quantum theory of "atoms in molecules"(QTAIM) and the noncovalent interaction plot index (NCIPlot) computational tools were used to characterize the bifurcated halogen bonds in the cocrystals of 1-3. Various types of bifurcated halogen bonds involving nonmetal atoms as halogen-bond-accepting centers were systematized and categorized.

AB - Cocrystallization of the nitrosoguanidinate complexes [Ni{NH═C(NR2)NN(O)}2] (R2 = Me2 (1), Me/Ph (2), C5H10 (3)) with 1,2-diiodotetrafluorobenzene (1,2-FIB), 1,4-diiodotetrafluorobenzene (1,4-FIB), 1,3,5-triiodotrifluorobenzene (1,3,5-FIB), and tetraiodoethylene (C2I4) gave new cocrystals (1-3)·2(1,2-FIB), 2·(1,4-FIB), 3·2(1,3,5-FIB), 1·C2I4, and 2·2C2I4; all of these solids were studied by single-crystal X-ray diffraction. Each structure exhibits the asymmetric bifurcated halogen bond μ2-I···(N,O) as a characteristic feature and a structure-directing contact. DFT calculations were used to evaluate the energetic features of the bifurcated halogen bonds that range from -6.7 to -8.3 kcal/mol; in general, the I···O contact is stronger that the I···N contact. Molecular electrostatic potential (MEP) surfaces along with the quantum theory of "atoms in molecules"(QTAIM) and the noncovalent interaction plot index (NCIPlot) computational tools were used to characterize the bifurcated halogen bonds in the cocrystals of 1-3. Various types of bifurcated halogen bonds involving nonmetal atoms as halogen-bond-accepting centers were systematized and categorized.

KW - CENTER-DOT-N

KW - INTERMOLECULAR INTERACTIONS

KW - NONCOVALENT INTERACTIONS

KW - PROGRAM

UR - http://www.scopus.com/inward/record.url?scp=85096611912&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/f470a704-033a-3ae5-aaa5-b188771e52db/

U2 - 10.1021/acs.cgd.0c01408

DO - 10.1021/acs.cgd.0c01408

M3 - Article

AN - SCOPUS:85096611912

VL - 21

SP - 588

EP - 596

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 1

ER -