Acta Crystallographica Section B

Structural Science

Volume 63, Part 2 (April 2007)


research papers



Acta Cryst. (2007). B63, 277-284    [ doi:10.1107/S0108768106052463 ]

Optimal partitioning of molecular properties into additive contributions: the case of crystal volumes

S. Beaucamp, D. Mathieu and V. Agafonov

Abstract: A systematic scheme to split the volume of molecular crystals into additive increments is discussed. In contrast to earlier procedures, it relies on the definition of atom types on the basis of their geometrical rather than chemical environment. In addition, the role of the relevant structural features of the compounds is explicitly taken into account. This approach provides insight into the relative influence of chemical bonds, hydrogen bonds and rings on the volume of organic crystals. Compared with group-contribution techniques, it yields very similar results with many fewer empirical parameters. Applied to estimate the densities of 42 880 crystals containing elements up to chlorine and measured at different temperatures, an average absolute deviation from experiment close to 2% is obtained.

Keywords: partitioning; additive contributions; hydrogen bonds.

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