Abstract
In crystal structures of flexible molecules the total energy is a summation of the molecular conformer and crystal lattice energy contribution. These two energy factors are of comparable magnitude in organic solids because bond torsions and intermolecular interactions have similar energies, worth a few kcal mol-1. The two contributions may be additive or cancel one another. Polymorphism is likely in molecular systems wherein molecular conformer and crystal lattice energy effects compensate each other, i.e. a metastable conformer resides in a stable packing arrangement or a stable rotamer is assembled in a metastable crystal environment. Consequently, conformational polymorph energy differences occur in a small window of <3 kcal mol-1. Several organic conformational polymorph clusters that highlight this principle are discussed in this chapter
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References
W. C. McCrone, in Physics and Chemistry of the Organic Solid State, Vol. 2, D. Fox, M. M. Labes and A. Weissberger (Eds.), Wiley Interscience: New York, 1965, pp. 725–767.
J. Bernstein, Polymorphism in Molecular Crystals, Clarendon, Oxford, 2002.
a) A. Kálmán, L. Fábián, G. Argay, G. BernPth and Z. Gyarmati, J. Am. Chem. Soc., 125 (2003) 34; b) I. Weissbuch, V. Y. Torbeev, L. Leiserowitz and M. Lahav, Angew. Chem. Int. Ed., 44 (2005) 3226; c) M. Morimoto, S. Kobatake and M. Irie, Chem. Eur. J., 9 (2003) 621; d) P. Raiteri, R. Martoňák and M. Parrinello, Angew. Chem. Int. Ed., 44 (2005) 3769; e) P. K. Thallapally, R. K. R. Jetti, A. K. Katz, H. L. Carrell, K. Singh, K. Lahiri, S. Kotha, R. Boese and G. R. Desiraju, Angew. Chem. Int. Ed., 43 (2004) 1149; f) H. Chow, P. A. W. Dean, D. C. Craig, N. T. Lucas, M. L. Scudder and I. G. Dance, New J. Chem., 27 (2003) 704; g) R. G. Gonnade, M. M. Bhadbhade and M. S. Shashidhar, Chem. Commun., (2004) 2530; h) C. Guo, M. B. Hickey, E. R. Guggenheim, V. Enkelmann and B. M. Foxman, Chem. Commun., (2005) 2220; i) W. I. F. David, K. Shankland, C. R. Pulham, N. Bladgen, R. J. Davey and M. Song, Angew. Chem. Int. Ed., 44 (2005) 7032.
a) R. J. Davey, Chem. Commun. (2003) 1463; b) N. Blagden and R. J. Davey, Cryst. Growth Des., 3 (2003) 873; c) P. Erk, H. Hengelsberg, M. F. Haddow and R. van Gelder, CrystEngComm, 6 (2004) 474; d) J. Bernstein, Chem. Commun., (2005) 5007; e) L. Yu, J. Am. Chem. Soc., 125 (2003) 6380; f) P. Vishweshwar, J. A. McMahon, M. Oliveira, M. L. Peterson and M. J. Zaworotko, J. Am. Chem. Soc., 127 (2005) 16802; g) C. P. Price, A. L. Grzesiak and A. J. Matzger, J. Am. Chem. Soc., 127 (2005) 5512; h) R. J. Davey, G. Dent, R. K. Mughal and S. Praveen, Cryst. Growth Des., 6 (2006) 1788.
a) S. R. Bryn, R. R. Pfeiffer and J. G. Stowell, Solid-State Chemistry of Drugs, SSCI, West Lafayette, IN, 1999; b) R. Hilfiker, F. Blatter and M. von Raumer, in Polymorphism in the Pharmaceutical Industry, R. Hilfiker (Ed.), Wiley–VCH, Weinheim, 2006, 1–19.
J. van de Streek and S. Motherwell, Acta Crystallogr., B61 (2005) 504.
J. Chisholm, E. Pidcock, J. van de Streek, L. Infantes, S. Motherwell and F. H. Allen, CrystEngComm, 8 (2006) 11.
S. Chen, I. A. Guzei and L. Yu, J. Am. Chem. Soc., 127 (2005) 9881.
a) C. P. Brock and L. L. Duncan, Chem. Mater., 6 (1994) 1307; b) J. W. Steed, CrystEngComm, 5 (2003) 169; c) S. Aitipamula and A. Nangia, Chem. Eur. J., 11 (2005) 6727; d) X. Hao, J. Chen, A. Cammers, S. Perkin and C. P. Brock, Acta Crystallogr., B61 (2005) 218; e) D. Das, R. Banerjee, R. Mondal, J. A. K. Howard, R. Boese and G. R. Desiraju, Chem. Commun., (2006) 555; f) K. M. Anderson, A. E. Goeta, K. S. B. Hancock and J. W. Steed, Chem. Commun., (2006) 2138; g) N. J. Babu and A. Nangia, Cryst. Growth Des., 6 (2006) 1995.
A. Nangia, Cryst. Growth Des., 6 (2006) 2.
G. R. Desiraju and T. Steiner, The Weak Hydrogen Bond in Structural Chemistry and Biology, IUCR Monograph, Oxford University Press, Oxford, 1999.
J. Bernstein, in Organic Solid State Chemistry, G. R. Desiraju (Ed.), Elsevier: Amsterdam, 1987, pp. 471–518.
Gaussian 03: www.gaussian.com; Spartan 04: www.wavefun.com; Cerius2: www.accelrys.com.
V. S. S. Kumar, A. Addlagatta, A. Nangia, W. T. Robinson, C. K. Broder, R. Mondal, I. R. Evans, J. A. K. Howard and F. H. Allen, Angew. Chem. Int. Ed., 41 (2002) 3848.
S. Roy, R. Banerjee, A. Nangia and G. J. Kruger, Chem. Eur. J., 12 (2006) 3777.
N. Krauss and G. Nolze, Federal Institute for Materials Research and Testing, Berlin, Germany, 2000.
S. K. Chandran and A. Nangia, CrystEngComm, 8 (2006) 581.
G. S. Nichol and W. Clegg, Cryst. Growth Des., 6 (2006) 451.
X. Hao, M. A. Siegler, S. Parkin and C. P. Brock, Cryst. Growth Des., 5 (2005) 2225.
B. Sarma, S. Roy and A. Nangia, Chem. Commun., (2006) 4918.
E. Weber, K. Skobridis, A. Wierig, L. R. Nassimbeni and L. Johnson, J. Chem. Soc., Perkin Trans 2, (1992) 2123.
a) T. W. Lewis, I. C. Paul and D. Y. Curtin, Acta Crystallogr., B36 (1980) 70; b) E. N. Duesler, T. W. Lewis, I. C. Paul and D. Y. Curtin, Acta Crystallogr., B36 (1980) 166.
S. K. Chandran, S. Roy and A. Nangia, unpublished results.
S. Roy and A. Nangia, unpublished results.
J. D. Dunitz and A. Gavezzotti, Cryst. Growth Des., 5 (2005) 2180.
a) B. RodrÃguez-Spong, C. P. Price, A. Jayashankar, A. J. Matzger and N. RodrÃguez-Hornendo, Adv. Drug. Del. Rev., 56 (2004) 241; b) C. R. Gardner, C. T. Walsh and Ö. Almarsson, Nature Reviews, 3 (2004) 926; c) J. Bernstein, Chem. Commun., (2005) 5007; d) A.V. Trask and W. Jones, Top. Curr. Chem., 254 (2005) 41.
S. Aitipamula and A. Nangia, Chem. Commun., (2005) 3159.
T. C. W. Mak and C.-K. Lam, in Encyclopedia of Supramolecular Chemistry, Vol. 1, J. L. Atwood and J. W. Steed (Eds.), Marcel Dekker, 2004, pp. 679–685.
S. Roy, P. M. Bhatt, A. Nangia and G. J. Kruger, Cryst. Growth Des., 7 (2007) 476.
S. Roy, S. Aitipamula and A. Nangia, Cryst. Growth Des., 5 (2005) 2268.
G. R. Desiraju, CrystEngComm, 9 (2007) 91.
K. M. Anderson and J. W. Steed, CrystEngComm, 9 (2007) 328.
M. Rafilovich and J. Bernstein, J. Am. Chem. Soc., 128 (2006) 12189.
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Nangia, A. (2008). Molecular Conformation and Crystal Lattice Energy Factors in Conformational Polymorphs. In: Boeyens, J.C., Ogilvie, J. (eds) Models, Mysteries and Magic of Molecules. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-5941-4_3
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DOI: https://doi.org/10.1007/978-1-4020-5941-4_3
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