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Crystals of Picric acid, C 6 H 3 N 3 O 7  are orthorhombic, space group  Pca 2 1 , and cell dimensions  a  = 9.262(1),  b  = 19.137(1),  c  = 9.714(1) Å with  D m   = 1.78 g· cm −3  and  D x   = 1.768 g · cm −3 . There are eight molecules in the unit cell. The crystal structure was solved by a combination of multisolution technique and “dummy atom” method with three-dimensional data collected (to the limit of 2θ ∼ 165° for Cu Kα ) by the stationary crystal-stationary counter technique on a GE XRD-6 diffractometer. The crystal structure was refined by least-squares method with block diagonal approximation to a final  R  value of 0.058. The two molecules in the asymmetric unit have different orientations of the nitro groups. In molecule I, the nitro groups are inclined by 17.0, 0.4, 7.7° whereas the corresponding values in molecule II are 2.7, 5.2 and 20.3° respectively. In both the molecules, there is an internal hydrogen bond from the OH group to the proximal oxygen of an adjacent nitro group (O–H… O 2.572, 2.619 Å). There appears to be no correlation between the C —N bond distance and the twist of the nitro groups from the mean phenyl plane. There is a wealth of internal short contacts between the various substituents of the phenyl ring.

Orientation and intramolecular hydrogen bonding of nitro groups in the crystal structure of picric acid, C 6 H 3 N 3 O 7 *