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New guidelines for the design of structurally equivalent molecular crystals were derived from structural analyses of new cocrystals and polymorphs of saccharin and thiosaccharin, aided by a computational study. The study shows that isostructural crystals may be obtained through an exchange of >C═O with >C═S in the molecular components of the solids, but only if the exchanged atom is not involved in hydrogen bonding.

Are Oxygen and Sulfur Atoms Structurally Equivalent in Organic Crystals?