Experimental and Theoretical Study of Halogen-Bonded Complexes of DMAP with Di- and Triiodofluorobenzenes. A Complex with a Very Short N center dot center dot center dot I Halogen Bond

TY - JOUR

T1 - Experimental and Theoretical Study of Halogen-Bonded Complexes of DMAP with Di- and Triiodofluorobenzenes. A Complex with a Very Short N center dot center dot center dot I Halogen Bond

AU - Roper, Laila C.

AU - Prasang, Carsten

AU - Kozhevnikov, Valery N.

AU - Whitwood, Adrian C.

AU - Karadakov, Peter B.

AU - Bruce, Duncan W.

PY - 2010/8/4

Y1 - 2010/8/4

N2 - X-ray single crystal structures are reported for 2:1 halogen-bonded complexes of 4-(N,N-dimethylamino)pyridine (DMAP) with 1,4- and 1,3-diiodotetrafluorobenzene and 1,3-diiodo-4,5,6-trifluorobenzene and for a 3:1 complex of DMAP with 1,3,5-triiodotrifluorobenzene. The complex between DMAP and 1,4-diiodotetrafluorobenzene shows the shortest halogen bond recorded for fluorinated iodoarenes. Model systems based on complexes between the same iodofluorobenzenes and ammonia are investigated by Hartree-Fock and DFT calculations to gain insights into the features of halogen bonding in di- and triiodo systems. The calculations reveal a weak charge-transfer component to the halogen bond and account for the lengthening of the C-I bond on complexation in terms of the C-I antibonding character observed within the localized molecular orbital describing the N center dot center dot center dot I bond.

AB - X-ray single crystal structures are reported for 2:1 halogen-bonded complexes of 4-(N,N-dimethylamino)pyridine (DMAP) with 1,4- and 1,3-diiodotetrafluorobenzene and 1,3-diiodo-4,5,6-trifluorobenzene and for a 3:1 complex of DMAP with 1,3,5-triiodotrifluorobenzene. The complex between DMAP and 1,4-diiodotetrafluorobenzene shows the shortest halogen bond recorded for fluorinated iodoarenes. Model systems based on complexes between the same iodofluorobenzenes and ammonia are investigated by Hartree-Fock and DFT calculations to gain insights into the features of halogen bonding in di- and triiodo systems. The calculations reveal a weak charge-transfer component to the halogen bond and account for the lengthening of the C-I bond on complexation in terms of the C-I antibonding character observed within the localized molecular orbital describing the N center dot center dot center dot I bond.

KW - LIQUID-CRYSTALS

KW - HYDROGEN-BONDS

KW - LEWIS-BASES

KW - SIGMA-HOLE

KW - AB-INITIO

KW - DERIVATIVES

KW - SOLIDS

KW - DONORS

KW - PHASE

KW - COCRYSTALLIZATION

UR - http://www.scopus.com/inward/record.url?scp=77955325649&partnerID=8YFLogxK

U2 - 10.1021/cg100549u

DO - 10.1021/cg100549u

M3 - Article

SN - 1528-7483

VL - 10

SP - 3710

EP - 3720

JO - CRYSTAL GROWTH DESIGN

JF - CRYSTAL GROWTH DESIGN

IS - 8

ER -