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On the polymorphism of pharmaceuticals and other molecular crystals. II

Über die Polymorphie von Arzneistoffen und anderen Molekülkristallen. II

Applicability of thermodynamic rules

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Summary

The heat-of-transition rule, heat-of-fusion rule, infrared rule and density rule, which concern the relative stability of polymorphic molecular crystals, have been checked experimentally. Among the 228 transitions examined, there are only few exceptions, and these mainly concern the infrared and density rules. The heat-of-transition and heat-of-fusion rules, however, give the right result in more than 99% of cases. If certain restrictions are observed, the other rules are also fairly reliable. By their means the stability relations in polymorphic systems can easily be clarified. Data are given for 113 polymorphic substances.

Zusammenfassung

Die früher formulierte Umwandlungswärmeregel, Schmelzwärmeregel, IR-Regel und Dichteregel, die sich mit der relativen Stabilität polymorpher Molekülkristalle befassen, wurden nun experimentellen Ergebnissen gegenübergestellt. Unter den 228 überprüften Umwandlungen befinden sich nur wenige Ausnahmen, die hauptsächlich die IR- und Dichteregel betreffen. Die Umwandlungs- und Schmelzwärmeregel hingegen ergeben in mehr als 99% der Fälle das richtige Resultat. Mit einigen Einschränkungen sind auch die beiden anderen Regeln recht zuverlässig. Damit kann man nun die Stabilitätsverhältnisse in polymorphen Systemen leichter klären. Daten für 113 polymorphe Substanzen sind angegeben.

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References

  1. A. Burger and R. Ramberger, Mikrochim. Acta [Wien]1979 II, 259.

    Google Scholar 

  2. Landolt-Börnstein, Zahlenwerte und Funktionen, Vol. II, Part 4, Berlin: Springer-Verlag. 1961.

    Google Scholar 

  3. L. Deffet, Repertoire des composées organiques polymorphes, Liège: Desoer. 1942.

    Google Scholar 

  4. Selected Values of Properties of Hydrocarbons and Related Compounds, edited by American Petroleum Institute, College Station, Texas: Texas A & M Research Foundation.

  5. Selected Values of Properties of Chemical Compounds, edited by Thermodynamics Research Center, College Station, Texas: Texas A & M Research Foundation.

  6. J. F. Westrum Jr. and J. P. McCullough, in Physics and Chemistry of the Organic Solid State, Vol. I, edited by D. Fox, M. M. Labes and A. Weissberger, New York: Interscience. 1963. pp. 1–178.

    Google Scholar 

  7. A. Burger, K. Schulte, and R. Ramberger, to be published.

  8. A. Burger and R. Ramberger, to be published.

  9. A. Burger, R. Ramberger, and K. Schulte, to be published.

  10. L. Kofler, A. Kofler, and M. Brandstätter, Thermomikromethoden, Weinheim: Verlag Chemie. 1954.

    Google Scholar 

  11. M. Kuhnert-Brandstätter, Thermomicroscopy in the Analysis of Pharmaceuticals, Oxford: Pergamon Press. 1971.

    Google Scholar 

  12. A. Burger, Sci. pharm.41, 290 (1973).

    Google Scholar 

  13. A. Burger, Sci. pharm.43, 152 (1975).

    Google Scholar 

  14. A. Burger, Sci. pharm.41, 303 (1973).

    Google Scholar 

  15. A. Burger, Sci. pharm.46, 207 (1978).

    Google Scholar 

  16. W. Hückel, Theoretische Grundlagen der organischen Chemie, Leipzig: Akadem. Verlag. 1941. p. 266.

    Google Scholar 

  17. J. K. Haleblian, R. T. Koda, and J. A. Biles, J. Pharm. Sci.60, 1485 (1971).

    Google Scholar 

  18. S. Amelinckx, Acta Cryst.8, 530 (1955);9, 16 (1956);9, 217 (1956).

    Google Scholar 

  19. D. Precht, Fette-Scifen-Anstr.78, 145 (1976).

    Google Scholar 

  20. The Merck Index, 9th Ed., Rahway, N. J.: Merck. 1976.

  21. R. Müller, Z. physik. Chem. (Leipzig)86, 177 (1914).

    Google Scholar 

  22. CRC Handbook of Chemistry and Physics, 56th Ed., Cleveland, Ohio: CRC Press. 1975.

  23. P. R. Arnold and F. Jones, Mol. Cryst. Liq. Cryst.19, 133 (1972).

    Google Scholar 

  24. W. C. McCrone, I. Corvin, and J. Whitney, Analyt. Chemistry21, 1016 (1949).

    Google Scholar 

  25. A. Théorêt, Spectrochim. Acta27 A, 11 (1971).

    Google Scholar 

  26. R. F. Deese Jr., J. Amer. Chem. Soc.53, 3673 (1931).

    Google Scholar 

  27. W. O. Baker and C. P. Smyth, J. Amer. Chem. Soc.61, 1695 (1939).

    Google Scholar 

  28. E. L. Skau and R. McCullough, J. Amer. Chem. Soc.57, 2439 (1935).

    Google Scholar 

  29. H. Tschamler, E. Richter, and F. Wettig, Mh. Chem.80, 856 (1949).

    Google Scholar 

  30. L. M. Kushner, R. W. Crowe, and C. P. Smyth, J. Amer. Chem. Soc.72, 1091 (1950).

    Google Scholar 

  31. R. Bouché, M. Draguet-Brughmans, and C. De Ranter, Mikrochim. Acta [Wien]1977 I, 511.

    Google Scholar 

  32. L. Bata, V. L. Broude, V. G. Fedotov, N. Kroo, L. Rosta, J. Szabon, L. M. Umarov, and I. Vizi, Mol. Cryst. Liq. Cryst.44, 71 (1978).

    Google Scholar 

  33. M. Brandstätter-Kuhnert and M. Aepkers, Mikrochim. Acta [Wien]1962, 1055.

  34. M. Kuhnert-Brandstätter and F. Bachleitner-Hofmann, Arch. Pharm.304, 580 (1971).

    Google Scholar 

  35. B. M. Craven, E. A. Vizzini, and M. M. Rodrigues, Acta Cryst.B 25, 1978 (1969).

    Google Scholar 

  36. A. Burger, Acta Pharm. Technol., Suppl.7, 107 (1979).

    Google Scholar 

  37. A. Kofler, Mikrochem.33, 4 (1948).

    Google Scholar 

  38. Beilsteins Handbuch der organischen Chemie, Vol. 9 (3. Erg.), Berlin: Springer-Verlag. 1970.

  39. M. Kuhnert-Brandstätter, A. Kofier, and H. C. Rhi, Sci. pharm.32, 308 (1964).

    Google Scholar 

  40. G. Bertholon, M. F. Vincent-Falquet, E. Collange, and M. Perrin, Journées de Calorimetrie et d'Analysé Thermique, Mai 9–10, 1974, Rennes (France), 3/33.

  41. M. Perrin, P. Michel, and R. Perrin, J. chim. phys.72, 851 (1975).

    Google Scholar 

  42. F. L. Oetting, J. Phys. Chem.67, 2757 (1963).

    Google Scholar 

  43. J. F. Martin, Chem. Thermodynamics1, 133 (1973).

    Google Scholar 

  44. M. Davies and B. Kybett, Trans. Faraday Soc.61, 2646 (1965).

    Google Scholar 

  45. C. Mosselman, J. Mourik, and H. Dekker, J. Chem. Thermodyn.6, 477 (1974).

    Google Scholar 

  46. A. Burger, Sci. pharm.45, 269 (1977).

    Google Scholar 

  47. Y. Eguchi and Y. Itaka, Acta Cryst.B 30, 2781 (1974).

    Google Scholar 

  48. A. Burger, to be published. In parts reported at: 22. Jahreskongreß der Arbeitsgem. f. Pharm. Verfahrenstechnik, März 1976, Berlin.

  49. A. Burger, Pharm. Ind.38, 306 (1976).

    Google Scholar 

  50. W. T. Berg, D. W. Scott, W. N. Hubbard, S. S. Todd, J. F. Messerly, I. A. Hossenlopp, A. Osborn, D. R. Douslin, and J. P. McCullough, J. Phys. Chem.65, 1425 (1961).

    Google Scholar 

  51. J. F. Messerly, H. L. Finke, and S. S. Todd, J. Chem. Thermodyn.6, 635 (1974).

    Google Scholar 

  52. M. Kuhnert-Brandstätter and L. Bösch, Mikrochim. Acta [Wien]1977 II, 55.

    Google Scholar 

  53. G. L. Wheeler and S. D. Colson, J. Chem. Phys.65, 1227 (1976).

    Google Scholar 

  54. P. Figuiere and H. Szwarc, Mol. Cryst. Liq. Cryst.27, 305 (1974).

    Google Scholar 

  55. M. Brandstätter, Mh. Chem.80, 1 (1949).

    Google Scholar 

  56. M. Kuhnert-Brandstätter and E. Junger, Spectrochim. Acta23 A, 1453 (1967).

    Google Scholar 

  57. H. G. Carlson and E. F. Westrum Jr., J. Phys. Chem.69, 1524 (1965).

    Google Scholar 

  58. S. R. Gunning, M. Freeman, and J. A. Stead, J. Pharm. Pharmac.28, 758 (1976).

    Google Scholar 

  59. K. S. Markley, Fatty Acids, New York: Interscience. 1947.

    Google Scholar 

  60. A. M. King and W. E. Garner, J. Chem. Soc.1934, 1449.

  61. M. Kuhnert-Brandstätter and A. Martinek, Mikrochim. Acta [Wien]1965, 909.

  62. M. E. Gross, G. D. Oliver, and H. M. Huffman, J. Amer. Chem. Soc.75, 2801 (1953).

    Google Scholar 

  63. M. Kuhnert-Brandstätter, E. Junger, and A. Kofler, Microchem. J.9, 105 (1965).

    Google Scholar 

  64. M. Kuhnert-Brandstätter, L. Borka, and G. Friedrich-Sander, Arch. Pharm.307, 845 (1974).

    Google Scholar 

  65. J. Krc Jr., Microscope25, 31 (1977).

    Google Scholar 

  66. A. Cingolani and G. Berchiesi, J. Therm. Anal.6, 87 (1974).

    Google Scholar 

  67. G. H. Charbonnet and W. S. Singleton, J. Am. Oil Chemists Soc.24, 140 (1947).

    Google Scholar 

  68. D. Precht and E. Frede, Kieler Milchw. Forschber.29, 265, 287 (1977).

    Google Scholar 

  69. R. W. Crowe and C. P. Smyth, J. Amer. Chem. Soc.72, 1098 (1950).

    Google Scholar 

  70. S. Mössmer, Diplomarbeit, Univ. Innsbruck. 1979.

  71. W. E. Garner and A. M. King, J. Chem. Soc.1929, 1849.

  72. A. J. Aguiar and J. E. Zelmer, J. Pharm. Sci.58, 983 (1969).

    Google Scholar 

  73. A. Burger and K. Schulte, to be published.

  74. J. A. Clements and D. Stanski, Can. J. Pharm. Sci.6, 9 (1971).

    Google Scholar 

  75. A. Burger, K. Schulte, and R. Ramberger, to be published.

  76. A. Burger, Sci. pharm.47, 16 (1979).

    Google Scholar 

  77. M. C. Etter, J. Amer. Chem. Soc.98, 5326 (1976).

    Google Scholar 

  78. G. R. Desiraju, I. C. Paul, and D. Y. Curtin, J. Amer. Chem. Soc.99, 1594 (1977).

    Google Scholar 

  79. G. Pelizza, M. Nebuloni, P. Ferrari, G. G. Gallo, G. Pelizzi, and P. Tarasconi, Farmaco (Ed. Sci.)33, 3 (1978).

    Google Scholar 

  80. J. K. Guillory, J. Pharm. Sci.56, 72 (1967).

    Google Scholar 

  81. W. I. Higuchi, P. K. Lau, T. Higuchi, and J. W. Shell, J. Pharm. Sci.52, 150 (1963).

    Google Scholar 

  82. M. Kuhnert-Brandstätter and A. Burger, Mikrochim. Acta [Wien]1975 I, 549.

    Google Scholar 

  83. A. Burger, Arzneimittelforsch.25, 24 (1975).

    Google Scholar 

  84. H. Bonadeo, E. D'Alessio, E. Halac, and E. Burgos, J. Chem. Phys.68, 4714 (1978).

    Google Scholar 

  85. R. Cameroni, G. Gamberini, V. Ferioli, and M. T. Bernabei, Farmaco (Ed. Pr.)32, 125 (1977).

    Google Scholar 

  86. M. Kuhnert-Brandstätter and I. Moser, Mikrochim. Acta [Wien]1978 II, 255.

    Google Scholar 

  87. A. Kofler and J. Kolsek, Mikrochim. Acta [Wien]1971, 848.

  88. M. Hashimoto, J. Magnetic Res.30, 431 (1978).

    Google Scholar 

  89. N. Nakamura and A. Watanabe, Yukagaku27, 441 (1978).

    Google Scholar 

  90. J. T. Pearson and G. Varney, J. Pharm. Pharmac.25, 62 P (1973).

    Google Scholar 

  91. W. E. Garner and F. C. Randall, J. Chem. Soc.125, 881 (1924).

    Google Scholar 

  92. P. P. Williams, Acta Cryst.B 29, 1572 (1973).

    Google Scholar 

  93. B. W. Müller (Groningen, Netherlands), private communication.

  94. M. Kuhnert-Brandstätter, Pharm. Ind.39, 377 (1977).

    Google Scholar 

  95. M. T. Bernabei, G. Gamberini, and R. Cameroni, Farmaco (Ed. Pr.)29, 184 (1974).

    Google Scholar 

  96. H. Campsteyn, Dissertation, Univ. Liège. 1974/75.

  97. M. Kuhnert-Brandstätter and L. Bösch, Arch. Pharm.311, 757 (1978).

    Google Scholar 

  98. L. Bösch, unpublished data.

  99. M. Kuhnert-Brandstätter and A. Burger, Pharm. Ind.34, 496 (1972).

    Google Scholar 

  100. J. M. Robertson and A. R. Ubbelohde, Proc. Roy. Soc. (London)A 167, 122 (1938).

    Google Scholar 

  101. A. Burger, unpublished data.

  102. M. F. Dupré La Tour, Ann. physique18, 201 (1932).

    Google Scholar 

  103. M. Kuhnert-Brandstätter and F. Bachleitner-Hofmann, Sci. pharm.39, 15 (1971).

    Google Scholar 

  104. S. S. Yang and J. K. Guillory, J. Pharm. Sci.61, 26 (1972).

    Google Scholar 

  105. S. Alberola, J. Rambaud, and F. Sabon, Bull. soc. chim. France1977, 181.

  106. M. Kuhnert-Brandstätter and F. Bachleitner-Hofmann, Spectrochim. Acta27 A, 191 (1971).

    Google Scholar 

  107. M. Kuhnert-Brandstätter and S. Wunsch, Mikrochim. Acta [Wien]1969, 1297.

  108. G. P. Bettinetti, F. Giordano, A. La Manna, and G. Giuseppetti, Farmaco (Ed. Pr.)29, 493 (1974).

    Google Scholar 

  109. A. Burger, Dissertation, Univ. Innsbruck. 1971.

  110. A. Burger, Pharm. Ind.35, 626 (1973).

    Google Scholar 

  111. M. Alleaume and J. Decap, Acta Cryst.18, 731 (1965) and19, 934 (1965).

    Google Scholar 

  112. B. H. O'Connor and E. N. Maslen, Acta Cryst.18, 363 (1965).

    Google Scholar 

  113. G. Milosovich, J. Pharm. Sci.53, 484 (1964).

    Google Scholar 

  114. G. J. Kruger and G. Gafner, Acta Cryst.B 27, 326 (1971);B 28, 272 (1972).

    Google Scholar 

  115. R. J. Mesley, J. Pharm. Pharmac.23, 687 (1971).

    Google Scholar 

  116. W. I. Higuchi, P. D. Bernardo, and S. C. Mehta, J. Pharm. Sci.56, 200 (1967).

    Google Scholar 

  117. M. Kuhnert-Brandstätter and A. Burger, Pharm. Ind.34, 353 (1972).

    Google Scholar 

  118. H. Doser, Arch. Pharm.281, 251 (1943).

    Google Scholar 

  119. A. Wickstrøm. J. Pharm. Pharmac.5, 158 (1953)

    Google Scholar 

  120. J. G. Aston, R. M. Kennedy, and G. H. Messerly, J. Amer. Chem. Soc.63, 2343 (1941).

    Google Scholar 

  121. A. Burger, Sci. pharm.43, 161 (1975).

    Google Scholar 

  122. V. P. Kolesov, V. N. Vorob'ev, E. A. Sarzhina, Yu. A. Pentin, and Yu. D. Timoshenkova, J. Chem. Thermodyn.6, 613 (1974).

    Google Scholar 

  123. M. Kuhnert-Brandstätter and R. Ulmer, Sci. pharm.41, 203 (1973).

    Google Scholar 

  124. A. Kofier, Mikrochem.34, 15 (1948).

    Google Scholar 

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Burger, A., Ramberger, R. On the polymorphism of pharmaceuticals and other molecular crystals. II. Mikrochim Acta 72, 273–316 (1979). https://doi.org/10.1007/BF01197380

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