PMID- 37686131
OWN - NLM
STAT- MEDLINE
DCOM- 20230911
LR  - 20230911
IS  - 1422-0067 (Electronic)
IS  - 1422-0067 (Linking)
VI  - 24
IP  - 17
DP  - 2023 Aug 28
TI  - Halogen Bonding Involving Isomeric Isocyanide/Nitrile Groups.
LID - 10.3390/ijms241713324 [doi]
LID - 13324
AB  - 2,3,5,6-Tetramethyl-1,4-diisocyanobenzene (1), 1,4-diisocyanobenzene (2), and 
      1,4-dicyanobenzene (3) were co-crystallized with 1,3,5-triiodotrifluorobenzene 
      (1,3,5-FIB) to give three cocrystals, 1.1,3,5-FIB, 2.2(1,3,5-FIB), and 
      3.2(1,3,5-FIB), which were studied by X-ray diffraction. A common feature of the 
      three structures is the presence of I...C(isocyanide) or I...N(nitrile) halogen 
      bonds (HaBs), which occurs between an iodine sigma-hole and the isocyanide C-(or the 
      nitrile N-) atom. The diisocyanide and dinitrile cocrystals 2.2(1,3,5-FIB) and 
      3.2(1,3,5-FIB) are isostructural, thus providing a basis for accurate comparison 
      of the two types of noncovalent linkages of C identical withN/N identical withC groups in the composition of 
      structurally similar entities and in one crystal environment. The bonding 
      situation was studied by a set of theoretical methods. Diisocyanides are more 
      nucleophilic than the dinitrile and they exhibit stronger binding to 1,3,5-FIB. 
      In all structures, the HaBs are mostly determined by the electrostatic 
      interactions, but the dispersion and induction components also provide a 
      noticeable contribution and make the HaBs attractive. Charge transfer has a small 
      contribution (<5%) to the HaB and it is higher for the diisocyanide than for the 
      dinitrile systems. At the same time, diisocyanide and dinitrile structures 
      exhibit typical electron-donor and pi-acceptor properties in relation to the HaB 
      donor.
FAU - Smirnov, Andrey S
AU  - Smirnov AS
AD  - Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 
      7/9, 199034 Saint Petersburg, Russia.
FAU - Katlenok, Eugene A
AU  - Katlenok EA
AUID- ORCID: 0000-0002-4485-7247
AD  - Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 
      7/9, 199034 Saint Petersburg, Russia.
FAU - Mikherdov, Alexander S
AU  - Mikherdov AS
AUID- ORCID: 0000-0002-6471-5158
AD  - Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 
      7/9, 199034 Saint Petersburg, Russia.
FAU - Kryukova, Mariya A
AU  - Kryukova MA
AD  - Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 
      7/9, 199034 Saint Petersburg, Russia.
FAU - Bokach, Nadezhda A
AU  - Bokach NA
AUID- ORCID: 0000-0001-8692-9627
AD  - Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 
      7/9, 199034 Saint Petersburg, Russia.
FAU - Kukushkin, Vadim Yu
AU  - Kukushkin VY
AUID- ORCID: 0000-0002-2253-085X
AD  - Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 
      7/9, 199034 Saint Petersburg, Russia.
AD  - Laboratory of Crystal Engineering of Functional Materials, South Ural State 
      University, 76, Lenin Av., 454080 Chelyabinsk, Russia.
LA  - eng
GR  - 22-23-00307/Russian Science Foundation/
PT  - Journal Article
DEP - 20230828
PL  - Switzerland
TA  - Int J Mol Sci
JT  - International journal of molecular sciences
JID - 101092791
RN  - 0 (1,4-diisocyanobenzene)
RN  - 0 (Cyanides)
RN  - 0 (Halogens)
RN  - 0 (Nitriles)
RN  - 9679TC07X4 (Iodine)
SB  - IM
MH  - *Cyanides
MH  - Halogens
MH  - Nitriles
MH  - *Iodine
PMC - PMC10487382
OTO - NOTNLM
OT  - NBO analysis
OT  - QTAIM
OT  - SAPT
OT  - halogen bond
OT  - isocyanides
OT  - nitriles
COIS- The authors declare no conflict of interest.
EDAT- 2023/09/09 11:45
MHDA- 2023/09/11 06:42
PMCR- 2023/08/28
CRDT- 2023/09/09 01:12
PHST- 2023/07/26 00:00 [received]
PHST- 2023/08/24 00:00 [revised]
PHST- 2023/08/25 00:00 [accepted]
PHST- 2023/09/11 06:42 [medline]
PHST- 2023/09/09 11:45 [pubmed]
PHST- 2023/09/09 01:12 [entrez]
PHST- 2023/08/28 00:00 [pmc-release]
AID - ijms241713324 [pii]
AID - ijms-24-13324 [pii]
AID - 10.3390/ijms241713324 [doi]
PST - epublish
SO  - Int J Mol Sci. 2023 Aug 28;24(17):13324. doi: 10.3390/ijms241713324.