Highly fluorinated naphthalenes and bifurcated C-H⋯F-C hydrogen bonding

TY - JOUR

T1 - Highly fluorinated naphthalenes and bifurcated C-H⋯F-C hydrogen bonding

AU - Loader, Jason R.

AU - Libri, Stefano

AU - Meijer, Anthony J. H. M.

AU - Perutz, Robin N.

AU - Brammer, Lee

PY - 2014/11/7

Y1 - 2014/11/7

N2 - The synthesis and crystal structures of 1,2,4,5,6,8-hexafluoronaphthalene and 1,2,4,6,8-pentafluoronaphthalene are reported. Intermolecular interactions are dominated by offset stacking and by C-H⋯F-C hydrogen bonds. For hexafluoronaphthalene, molecules are linked in layers with (4,4) network topology via R12(6) C-H⋯(F-C)2supramolecular synthons that are rationalised by consideration of the calculated electrostatic potential of the molecule. Such an arrangement is prevented by the additional hydrogen atom in pentafluoronaphthalene and molecules instead form tapes via an R12(8) (C-H⋯F)2synthon. The geometric characteristics of C-H⋯(F-C)2bifurcated hydrogen bonds have been analysed for crystal structures in the Cambridge Structural Database (6416 crystal structures; 9534 C-H⋯(F-C)2bifurcated hydrogen bonds). A geometric analysis of these hydrogen bonds has enabled the extent of asymmetry of these hydrogen bonds to be assessed and indicates a preference for symmetrically bifurcated interactions.

AB - The synthesis and crystal structures of 1,2,4,5,6,8-hexafluoronaphthalene and 1,2,4,6,8-pentafluoronaphthalene are reported. Intermolecular interactions are dominated by offset stacking and by C-H⋯F-C hydrogen bonds. For hexafluoronaphthalene, molecules are linked in layers with (4,4) network topology via R12(6) C-H⋯(F-C)2supramolecular synthons that are rationalised by consideration of the calculated electrostatic potential of the molecule. Such an arrangement is prevented by the additional hydrogen atom in pentafluoronaphthalene and molecules instead form tapes via an R12(8) (C-H⋯F)2synthon. The geometric characteristics of C-H⋯(F-C)2bifurcated hydrogen bonds have been analysed for crystal structures in the Cambridge Structural Database (6416 crystal structures; 9534 C-H⋯(F-C)2bifurcated hydrogen bonds). A geometric analysis of these hydrogen bonds has enabled the extent of asymmetry of these hydrogen bonds to be assessed and indicates a preference for symmetrically bifurcated interactions.

UR - http://www.scopus.com/inward/record.url?scp=84907482490&partnerID=8YFLogxK

U2 - 10.1039/c4ce01322k

DO - 10.1039/c4ce01322k

M3 - Article

AN - SCOPUS:84907482490

SN - 1466-8033

VL - 16

SP - 9711

EP - 9720

JO - CrystEngComm

JF - CrystEngComm

IS - 41

ER -