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

doi:10.1007/s11224-010-9700-0

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

Chemistry

Research output: Contribution to journal › Article › peer-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 language	English
Pages (from-to)	279-285
Journal	Structural Chemistry
Volume	22
Issue number	2
DOIs	https://doi.org/10.1007/s11224-010-9700-0
Publication status	Published - 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: [email protected]

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

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10.1007/s11224-010-9700-0

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Cite this

@article{c27d153f5f5c469cae51d856763d0d71,

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

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. {\textcopyright} 2010 Springer Science+Business Media, LLC.",

keywords = "Ab initio methods, Gas electron diffraction, Halobenzenes",

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

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: [email protected] 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 G{\"o}ttingen 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",

year = "2011",

month = apr,

doi = "10.1007/s11224-010-9700-0",

language = "English",

volume = "22",

pages = "279--285",

journal = "Structural Chemistry",

issn = "1040-0400",

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TY - JOUR

T1 - Unusual asymmetry in halobenzenes, a solid-state, gas-phase and theoretical investigation

AU - Masters, S.L.

AU - MacKie, I.D.

AU - Wann, D.A.

AU - Robertson, H.E.

AU - Rankin, D.W.H.

AU - Parsons, S.

N1 - 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: [email protected] 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

PY - 2011/4

Y1 - 2011/4

N2 - 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.

AB - 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.

KW - Ab initio methods

KW - Gas electron diffraction

KW - Halobenzenes

U2 - 10.1007/s11224-010-9700-0

DO - 10.1007/s11224-010-9700-0

M3 - Article

SN - 1040-0400

VL - 22

SP - 279

EP - 285

JO - Structural Chemistry

JF - Structural Chemistry

IS - 2

ER -