Additivity of ring geometry distortion effects in unsaturated five-membered heterocyclic rings

J.T. Schirlin; D.A. Wann; S.F. Bone; H.E. Robertson; D.W.H. Rankin

doi:10.1016/j.molstruc.2009.01.032

Additivity of ring geometry distortion effects in unsaturated five-membered heterocyclic rings

J.T. Schirlin, D.A. Wann, S.F. Bone, H.E. Robertson, D.W.H. Rankin

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Empirical rules for the prediction of structures are valuable, providing aids to understanding and prediction that complement sophisticated computational methods. In this work, the structures of unsaturated five-membered rings have been predicted using sets of parameters describing distortions caused by substitutions in benzene and other rings. Effects on the structures of unsaturated five-membered rings due to both ring-member and substituent changes are found to be additive. Moreover, distortions caused by chlorine substitution observed for aromatic six-membered rings can be directly transferred to unsaturated five-membered rings with satisfying accuracy. The analysis has made use of data obtained by study of the structures of 2,5-dichlorothiophene and 3,4-dichloro-1,2,5-thiadiazole by gas-phase electron diffraction and computational chemistry methods. © 2009 Elsevier B.V. All rights reserved.

Original language	English
Pages (from-to)	103-108
Journal	JOURNAL OF MOLECULAR STRUCTURE
Volume	922
Issue number	1-3
DOIs	https://doi.org/10.1016/j.molstruc.2009.01.032
Publication status	Published - 30 Mar 2009

Bibliographical note

Cited By (since 1996):1

Export Date: 1 October 2013

Source: Scopus

CODEN: JMOSB

doi: 10.1016/j.molstruc.2009.01.032

Language of Original Document: English

Correspondence Address: Rankin, D.W.H.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected]

References: Momany, F.A., Bonham, R.A., (1961) J. Am. Chem. Soc., 83, p. 4475; Momany, F.A., Bonham, R.A., (1964) J. Am. Chem. Soc., 86, p. 162; Bonham, R.A., Momany, F.A., (1963) J. Phys. Chem., 67, p. 2474; Dobyns, V., Pierce, L., (1963) J. Am. Chem. Soc., 85, p. 3553; Kochikov, I.V., Tarasov, Yu.I., Spiridonov, V.P., Kuramshina, G.M., Rankin, D.W.H., Saakjan, A.S., Yagola, A.G., (2001) J. Mol. Struct., 568, p. 29; Glossman-Mitnik, D., Márquez-Lucero, A., (2001) J. Mol. Struct., 548, p. 153; Glossman-Mitnik, D., (2003) J. Mol. Struct. (THEOCHEM), 634, p. 77; Trofimov, A.B., Schirmer, J., Holland, D.M.P., Karlsson, L., Maripuu, R., Siegbahn, K., Potts, A.W., (2001) Chem. Phys., 263, p. 167; Potts, A.W., Trofimov, A.B., Schirmer, J., Holland, D.M.P., Karlsson, L., (2001) Chem. Phys., 271, p. 337; Baker, A.D., Betteridge, D., Kemp, N.R., Kirby, R.E., (1970) Anal. Chem., 42, p. 1064; Domenicano, A., (1998) Stereochemical Applications of Gas-phase Electron Diffraction Part B, , Hargittai I., and Hargittai M. (Eds), VCH Publishers, Weinheim, Germany and references therein; M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. GoBastiansen, O., Trætteberg, M., (1960) Acta Crystallogr., 13, p. 1108; Morino, Y., Cyvin, S.J., Kuchitsu, K., Iijima, T., (1962) J. Chem. Phys., 36, p. 1109; Stølevik, R., Seip, H.M., Cyvin, S.J., (1972) Chem. Phys. Lett., 15, p. 263; Binkley, J.S., Pople, J.A., Hehre, W.J., (1980) J. Am. Chem. Soc., 102, p. 939; Gordon, M.S., Binkley, J.S., Pople, J.A., Pietro, W.J., Hehre, W.J., (1982) J. Am. Chem. Soc., 104, p. 2797; 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; Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257; Hariharan, P.C., Pople, J.A., (1973) Theor. Chim. Acta, 28, p. 213; Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618; Krishnan, R., Pople, J.A., (1978) Int. J. Quant. Chem., 14, p. 91; Pople, J.A., Seeger, R., Krishnan, R., (1977) Int. J. Quant. Chem, 11, p. 149; Krishnan, R., Schlegel, H.B., Pople, J.A., (1980) J. Chem. Phys., 72, p. 4654; Raghavachari, K., Pople, J.A., (1981) Int. J. Quant. Chem., 20, p. 167; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B Condens. Matter, 37, p. 785; Miehlich, B., Savin, A., Stoll, H., Preuss, H., (1989) Chem. Phys. Lett., 157, p. 200; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Cradock, S., Koprowski, J., Rankin, D.W.H., (1981) J. Mol. Struct., 71, p. 217; 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, C, p. 245. , Wilson A.J.C. (Ed), Kluwer Academic Publishers, Dordrecht, The Netherlands; Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; 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; 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; Eon, C., Pommier, C., Guiochon, G., (1971) J. Phys. Chem., 75, p. 2632; Anderson, D.G., Cradock, S., Liescheski, P.B., Rankin, D.W.H., (1990) J. Mol. Struct., 216, p. 181

Keywords

Ab initio calculations
Additivity
Gas electron diffraction
Ring distortion
Unsaturated five-membered heterocycles
Benzene
Chlorine
Electron diffraction

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10.1016/j.molstruc.2009.01.032

http://www.scopus.com/inward/record.url?eid=2-s2.0-61849114652&partnerID=40&md5=1025a3e78a537dde86e3fc10b8744087

Cite this

@article{0d087614d10e43f4884b8d6629074638,

title = "Additivity of ring geometry distortion effects in unsaturated five-membered heterocyclic rings",

abstract = "Empirical rules for the prediction of structures are valuable, providing aids to understanding and prediction that complement sophisticated computational methods. In this work, the structures of unsaturated five-membered rings have been predicted using sets of parameters describing distortions caused by substitutions in benzene and other rings. Effects on the structures of unsaturated five-membered rings due to both ring-member and substituent changes are found to be additive. Moreover, distortions caused by chlorine substitution observed for aromatic six-membered rings can be directly transferred to unsaturated five-membered rings with satisfying accuracy. The analysis has made use of data obtained by study of the structures of 2,5-dichlorothiophene and 3,4-dichloro-1,2,5-thiadiazole by gas-phase electron diffraction and computational chemistry methods. {\textcopyright} 2009 Elsevier B.V. All rights reserved.",

keywords = "Ab initio calculations, Additivity, Gas electron diffraction, Ring distortion, Unsaturated five-membered heterocycles, Benzene, Chlorine, Electron diffraction",

author = "J.T. Schirlin and D.A. Wann and S.F. Bone and H.E. Robertson and D.W.H. Rankin",

note = "Cited By (since 1996):1 Export Date: 1 October 2013 Source: Scopus CODEN: JMOSB doi: 10.1016/j.molstruc.2009.01.032 Language of Original Document: English Correspondence Address: Rankin, D.W.H.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected] References: Momany, F.A., Bonham, R.A., (1961) J. Am. Chem. Soc., 83, p. 4475; Momany, F.A., Bonham, R.A., (1964) J. Am. Chem. Soc., 86, p. 162; Bonham, R.A., Momany, F.A., (1963) J. Phys. Chem., 67, p. 2474; Dobyns, V., Pierce, L., (1963) J. Am. Chem. Soc., 85, p. 3553; Kochikov, I.V., Tarasov, Yu.I., Spiridonov, V.P., Kuramshina, G.M., Rankin, D.W.H., Saakjan, A.S., Yagola, A.G., (2001) J. Mol. Struct., 568, p. 29; Glossman-Mitnik, D., M{\'a}rquez-Lucero, A., (2001) J. Mol. Struct., 548, p. 153; Glossman-Mitnik, D., (2003) J. Mol. Struct. (THEOCHEM), 634, p. 77; Trofimov, A.B., Schirmer, J., Holland, D.M.P., Karlsson, L., Maripuu, R., Siegbahn, K., Potts, A.W., (2001) Chem. Phys., 263, p. 167; Potts, A.W., Trofimov, A.B., Schirmer, J., Holland, D.M.P., Karlsson, L., (2001) Chem. Phys., 271, p. 337; Baker, A.D., Betteridge, D., Kemp, N.R., Kirby, R.E., (1970) Anal. Chem., 42, p. 1064; Domenicano, A., (1998) Stereochemical Applications of Gas-phase Electron Diffraction Part B, , Hargittai I., and Hargittai M. (Eds), VCH Publishers, Weinheim, Germany and references therein; M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. GoBastiansen, O., Tr{\ae}tteberg, M., (1960) Acta Crystallogr., 13, p. 1108; Morino, Y., Cyvin, S.J., Kuchitsu, K., Iijima, T., (1962) J. Chem. Phys., 36, p. 1109; St{\o}levik, R., Seip, H.M., Cyvin, S.J., (1972) Chem. Phys. Lett., 15, p. 263; Binkley, J.S., Pople, J.A., Hehre, W.J., (1980) J. Am. Chem. Soc., 102, p. 939; Gordon, M.S., Binkley, J.S., Pople, J.A., Pietro, W.J., Hehre, W.J., (1982) J. Am. Chem. Soc., 104, p. 2797; 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; Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257; Hariharan, P.C., Pople, J.A., (1973) Theor. Chim. Acta, 28, p. 213; Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; M{\o}ller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618; Krishnan, R., Pople, J.A., (1978) Int. J. Quant. Chem., 14, p. 91; Pople, J.A., Seeger, R., Krishnan, R., (1977) Int. J. Quant. Chem, 11, p. 149; Krishnan, R., Schlegel, H.B., Pople, J.A., (1980) J. Chem. Phys., 72, p. 4654; Raghavachari, K., Pople, J.A., (1981) Int. J. Quant. Chem., 20, p. 167; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B Condens. Matter, 37, p. 785; Miehlich, B., Savin, A., Stoll, H., Preuss, H., (1989) Chem. Phys. Lett., 157, p. 200; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Cradock, S., Koprowski, J., Rankin, D.W.H., (1981) J. Mol. Struct., 71, p. 217; 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, C, p. 245. , Wilson A.J.C. (Ed), Kluwer Academic Publishers, Dordrecht, The Netherlands; Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; 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; 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; Eon, C., Pommier, C., Guiochon, G., (1971) J. Phys. Chem., 75, p. 2632; Anderson, D.G., Cradock, S., Liescheski, P.B., Rankin, D.W.H., (1990) J. Mol. Struct., 216, p. 181",

year = "2009",

month = mar,

day = "30",

doi = "10.1016/j.molstruc.2009.01.032",

language = "English",

volume = "922",

pages = "103--108",

journal = "JOURNAL OF MOLECULAR STRUCTURE",

issn = "0022-2860",

publisher = "Elsevier",

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TY - JOUR

T1 - Additivity of ring geometry distortion effects in unsaturated five-membered heterocyclic rings

AU - Schirlin, J.T.

AU - Wann, D.A.

AU - Bone, S.F.

AU - Robertson, H.E.

AU - Rankin, D.W.H.

N1 - Cited By (since 1996):1 Export Date: 1 October 2013 Source: Scopus CODEN: JMOSB doi: 10.1016/j.molstruc.2009.01.032 Language of Original Document: English Correspondence Address: Rankin, D.W.H.; School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom; email: [email protected] References: Momany, F.A., Bonham, R.A., (1961) J. Am. Chem. Soc., 83, p. 4475; Momany, F.A., Bonham, R.A., (1964) J. Am. Chem. Soc., 86, p. 162; Bonham, R.A., Momany, F.A., (1963) J. Phys. Chem., 67, p. 2474; Dobyns, V., Pierce, L., (1963) J. Am. Chem. Soc., 85, p. 3553; Kochikov, I.V., Tarasov, Yu.I., Spiridonov, V.P., Kuramshina, G.M., Rankin, D.W.H., Saakjan, A.S., Yagola, A.G., (2001) J. Mol. Struct., 568, p. 29; Glossman-Mitnik, D., Márquez-Lucero, A., (2001) J. Mol. Struct., 548, p. 153; Glossman-Mitnik, D., (2003) J. Mol. Struct. (THEOCHEM), 634, p. 77; Trofimov, A.B., Schirmer, J., Holland, D.M.P., Karlsson, L., Maripuu, R., Siegbahn, K., Potts, A.W., (2001) Chem. Phys., 263, p. 167; Potts, A.W., Trofimov, A.B., Schirmer, J., Holland, D.M.P., Karlsson, L., (2001) Chem. Phys., 271, p. 337; Baker, A.D., Betteridge, D., Kemp, N.R., Kirby, R.E., (1970) Anal. Chem., 42, p. 1064; Domenicano, A., (1998) Stereochemical Applications of Gas-phase Electron Diffraction Part B, , Hargittai I., and Hargittai M. (Eds), VCH Publishers, Weinheim, Germany and references therein; M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, Jr, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. GoBastiansen, O., Trætteberg, M., (1960) Acta Crystallogr., 13, p. 1108; Morino, Y., Cyvin, S.J., Kuchitsu, K., Iijima, T., (1962) J. Chem. Phys., 36, p. 1109; Stølevik, R., Seip, H.M., Cyvin, S.J., (1972) Chem. Phys. Lett., 15, p. 263; Binkley, J.S., Pople, J.A., Hehre, W.J., (1980) J. Am. Chem. Soc., 102, p. 939; Gordon, M.S., Binkley, J.S., Pople, J.A., Pietro, W.J., Hehre, W.J., (1982) J. Am. Chem. Soc., 104, p. 2797; 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; Hehre, W.J., Ditchfield, R., Pople, J.A., (1972) J. Chem. Phys., 56, p. 2257; Hariharan, P.C., Pople, J.A., (1973) Theor. Chim. Acta, 28, p. 213; Gordon, M.S., (1980) Chem. Phys. Lett., 76, p. 163; Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., (1980) J. Chem. Phys., 72, p. 650; McLean, A.D., Chandler, G.S., (1980) J. Chem. Phys., 72, p. 5639; Møller, C., Plesset, M.S., (1934) Phys. Rev., 46, p. 618; Krishnan, R., Pople, J.A., (1978) Int. J. Quant. Chem., 14, p. 91; Pople, J.A., Seeger, R., Krishnan, R., (1977) Int. J. Quant. Chem, 11, p. 149; Krishnan, R., Schlegel, H.B., Pople, J.A., (1980) J. Chem. Phys., 72, p. 4654; Raghavachari, K., Pople, J.A., (1981) Int. J. Quant. Chem., 20, p. 167; Becke, A.D., (1993) J. Chem. Phys., 98, p. 5648; Lee, C., Yang, W., Parr, R.G., (1992) Phys. Rev. B Condens. Matter, 37, p. 785; Miehlich, B., Savin, A., Stoll, H., Preuss, H., (1989) Chem. Phys. Lett., 157, p. 200; Huntley, C.M., Laurenson, G.S., Rankin, D.W.H., (1980) J. Chem. Soc., Dalton Trans., p. 954; Cradock, S., Koprowski, J., Rankin, D.W.H., (1981) J. Mol. Struct., 71, p. 217; 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, C, p. 245. , Wilson A.J.C. (Ed), Kluwer Academic Publishers, Dordrecht, The Netherlands; Sipachev, V.A., (1985) J. Mol. Struct. (THEOCHEM), 121, p. 143; Sipachev, V.A., (2001) J. Mol. Struct., 567, p. 67; 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; 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; Eon, C., Pommier, C., Guiochon, G., (1971) J. Phys. Chem., 75, p. 2632; Anderson, D.G., Cradock, S., Liescheski, P.B., Rankin, D.W.H., (1990) J. Mol. Struct., 216, p. 181

PY - 2009/3/30

Y1 - 2009/3/30

N2 - Empirical rules for the prediction of structures are valuable, providing aids to understanding and prediction that complement sophisticated computational methods. In this work, the structures of unsaturated five-membered rings have been predicted using sets of parameters describing distortions caused by substitutions in benzene and other rings. Effects on the structures of unsaturated five-membered rings due to both ring-member and substituent changes are found to be additive. Moreover, distortions caused by chlorine substitution observed for aromatic six-membered rings can be directly transferred to unsaturated five-membered rings with satisfying accuracy. The analysis has made use of data obtained by study of the structures of 2,5-dichlorothiophene and 3,4-dichloro-1,2,5-thiadiazole by gas-phase electron diffraction and computational chemistry methods. © 2009 Elsevier B.V. All rights reserved.

AB - Empirical rules for the prediction of structures are valuable, providing aids to understanding and prediction that complement sophisticated computational methods. In this work, the structures of unsaturated five-membered rings have been predicted using sets of parameters describing distortions caused by substitutions in benzene and other rings. Effects on the structures of unsaturated five-membered rings due to both ring-member and substituent changes are found to be additive. Moreover, distortions caused by chlorine substitution observed for aromatic six-membered rings can be directly transferred to unsaturated five-membered rings with satisfying accuracy. The analysis has made use of data obtained by study of the structures of 2,5-dichlorothiophene and 3,4-dichloro-1,2,5-thiadiazole by gas-phase electron diffraction and computational chemistry methods. © 2009 Elsevier B.V. All rights reserved.

KW - Ab initio calculations

KW - Additivity

KW - Gas electron diffraction

KW - Ring distortion

KW - Unsaturated five-membered heterocycles

KW - Benzene

KW - Chlorine

KW - Electron diffraction

U2 - 10.1016/j.molstruc.2009.01.032

DO - 10.1016/j.molstruc.2009.01.032

M3 - Article

SN - 0022-2860

VL - 922

SP - 103

EP - 108

JO - JOURNAL OF MOLECULAR STRUCTURE

JF - JOURNAL OF MOLECULAR STRUCTURE

IS - 1-3

ER -