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The functional group approach for crystal structure design and prediction is not entirely viable. Recent investigations have shown that the simultaneous operation of weaker interactions and strong and directional O-H⋯O hydrogen bonds leads to departure from the expectations based on molecular association via strong interactions alone, see Desiraju, G. R.; Steiner, T. The Weak Hydrogen Bond in Structural Chemistry and Biology; Oxford University Press: Oxford, U. K., 1999.
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We have preferred to term "C-H⋯X" as an interaction to a "hydrogen bond". The question of whether the C-H⋯X interaction involving formyl hydrogens can be called a hydrogen bond will be addressed elsewhere.
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0141545387
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The C=O⋯Br distance of 3.44 Å in the case of triclinic modification, i.e., 2T, is larger than the sum of van der Waals radii. This is presumably due to crystal packing forces. The directionality as reflected from the C-X⋯O=C angle leaves no doubt as to the anisotropic interaction. Indeed, the assessment of the strength of an interaction based on distance criterion alone can be misleading. It has been shown that the position of minimum in the intermolecular potential is ca. 0.4 Å larger than the van der Waals distance, see Dance, I. New J. Chem. 2003, 27, 22.
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A similar isostructurality in the crystal structures of 2,5-dichloro- and 2,5-dibromo-1,4-benzoquinones has been attributed to the effectiveness of C=O⋯X interactions, see ref 27. For discussion on the crystal packing of a variety of halogen-substituted benzoquinones, see ref 22.
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31
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0141545384
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note
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C-Br⋯O = 168.7°). The absence of the dimeric motif 1 in the remaining compounds is found to be due to the presence of other functional groups such as Br, OH, COOH, etc., which are capable of stabilizing the crystal lattice through interactions of their own. The alternative and equally or better-stabilizing interactions appear to obviate the adoption of dimeric motif 1 in all these cases.
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