Unusual asymmetry in halobenzenes, a solid-state, gas-phase and theoretical investigation

S.L. Masters, I.D. MacKie, D.A. Wann, H.E. Robertson, D.W.H. Rankin, S. Parsons

Research output: Contribution to journalArticlepeer-review

Abstract

The molecular structures of 1-Br-4-F-C 6H 4 and 1-Cl-4-F-C 6H 4 have been studied in the gas phase using gas electron diffraction (GED) and ab initio methods. The structure of 1-Cl,4-F-C 6H 4 in the crystalline phase has also been studied, but whilst the gaseous structures were found to possess C 2v symmetry, the solid-state structure was found to be quite distorted, with three molecules in the asymmetric unit. These fragments only possess C s symmetry in the plane of the molecules, as opposed to the C 2v symmetry observed in the gas phase. The bonding motifs within the solid-state structure are very unusual and unexpected, with quite different C-F bond lengths for the three moieties, and are a result of weak hydrogen-halogen interactions within the structure. © 2010 Springer Science+Business Media, LLC.
Original languageEnglish
Pages (from-to)279-285
JournalStructural Chemistry
Volume22
Issue number2
DOIs
Publication statusPublished - Apr 2011

Bibliographical note

Cited By (since 1996):1

Export Date: 1 October 2013

Source: Scopus

CODEN: STCHE

doi: 10.1007/s11224-010-9700-0

Language of Original Document: English

Correspondence Address: Masters, S. L.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, United Kingdom; email: s.masters@ed.ac.uk

References: Thalladi, V.R., Weiss, H.-C., Blaser, D., Boese, R., Nangia, A., Desiraju, G.R., C-H···F interactions in the crystal structures of some fluorobenzenes (1998) Journal of the American Chemical Society, 120 (34), pp. 8702-8710. , DOI 10.1021/ja981198e; Wann, D.A., Masters, S.L., Robertson, H.E., Rankin, D.W.H., Additivity of ring distortions in halogen-substituted aromatics: A gas-phase electron diffraction and computational study (2007) Journal of Physical Chemistry A, 111 (32), pp. 7882-7887. , DOI 10.1021/jp073581o; Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Pople, J.A., (1998) Gaussian 98, Revision A.7, , Gaussian, Inc. Pittsburgh, PA; Binkley, J.S., Pople, J.A., Hehre, W.J., (1980) J Am Chem Soc, 102, p. 939. , 10.1021/ja00523a008 1:CAS:528:DyaL3cXpvFylsA%3D%3D; Gordon, M.S., Binkley, J.S., Pople, J.A., Pietro, W.J., Hehre, W.J., (1982) J Am Chem Soc, 104, p. 2797. , 10.1021/ja00374a017 1:CAS:528:DyaL38XhvVOnsb0%3D; Pietro, W.J., Francl, M.M., Hehre, W.J., Defrees, D.J., Pople, J.A., Binkley, J.S., (1982) J Am Chem Soc, 104, p. 5039. , 10.1021/ja00383a007 1:CAS:528:DyaL38XltFGnu7w%3D; Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J Chem Phys, 56, p. 2257. , 10.1063/1.1677527 1:CAS:528:DyaE38XptVemsw%3D%3D; Hariharan, P.C., Pople, J.A., (1973) Theor Chim Acta, 28, p. 213. , 10.1007/BF00533485 1:CAS:528:DyaE3sXhtFGnsL4%3D; Gordon, M.S., (1980) Chem Phys Lett, 76, p. 163. , 10.1016/0009-2614(80)80628-2 1:CAS:528:DyaL3MXmsV2lsg%3D%3D; McLean, A.D., Chandler, G.S., (1980) J Chem Phys, 72, p. 5639. , 10.1063/1.438980 1:CAS:528:DyaL3cXksFCnu7c%3D; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J Chem Phys, 72, p. 650. , 10.1063/1.438955 1:CAS:528:DyaL3cXpvFyitA%3D%3D; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J Chem Soc Dalton Trans, p. 954; Lewis, J.R., Brain, P.T., Rankin, D.W.H., (1997) Spectrum, 15, p. 7; Hinchley, S.L., Robertson, H.E., Borisenko, K.B., Turner, A.R., Johnston, B.F., Rankin, D.W.H., Ahmadian, M., Cowley, A.H., (2004) Dalton Trans, p. 2469; Ross, A.W., Fink, M., Hilderbrandt, R., (1992) International Tables for Crystallography, 100, p. 245. , Wilson AJC (ed) Kluwer Academic Publishers, Dordrecht, Boston and London; Cosier, J., Glazer, A.M., (1986) J Appl Crystallogr, 19, p. 105. , 10.1107/S0021889886089835 1:CAS:528:DyaL28XhsF2qurY%3D; Boese, R., Nussbaumer, M., (1994) Correlations, Transformations and Interactions in Organic Crystal Chemistry, 7, pp. 20-37. , Jones DW, Katrusiak A (eds) IUCr crystallographic symposia. Oxford University Press, Oxford; Sheldrick, G.M., (2008) SADABS Version 2008/1, , University of Göttingen Germany; Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Completion and refinement of crystal structures with SIR92 (1993) Journal of Applied Crystallography, 26 (PART 3), pp. 343-350. , DOI 10.1107/S0021889892010331; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J., (2003) J Appl Crystallogr, 36, p. 1487. , 10.1107/S0021889803021800 1:CAS:528:DC%2BD3sXptFekt78%3D; Moran, D., Simmonett, A.C., Leach III, F.E., Allen, W.D., Schleyer, P.V.R., Schaefer III, H.F., Popular theoretical methods predict benzene and arenes to be nonplanar (2006) Journal of the American Chemical Society, 128 (29), pp. 9342-9343. , DOI 10.1021/ja0630285; Sipachev, V.A., (1985) J Mol Struct (THEOCHEM), 121, p. 143. , 10.1016/0166-1280(85)80054-3; Sipachev, V.A., Local centrifugal distortions caused by internal motions of molecules (2001) Journal of Molecular Structure, 567-568, pp. 67-72. , DOI 10.1016/S0022-2860(01)00534-8, PII S0022286001005348; Blake, A.J., Brain, P.T., McNab, H., Miller, J., Morrison, C.A., Parsons, S., Rankin, D.W.H., Smart, B.A., (1996) J Phys Chem, 100, p. 12280. , 10.1021/jp960084r 1:CAS:528:DyaK28XjvFCisLY%3D; Brain, P.T., Morrison, C.A., Parsons, S., Rankin, D.W.H., (1996) J Chem Soc Dalton Trans, p. 4589; Mitzel, N.W., Rankin, D.W.H., (2003) Dalton Trans, p. 3650

Keywords

  • Ab initio methods
  • Gas electron diffraction
  • Halobenzenes

Cite this