Modelling polymorphs of metal–organic frameworks: a systematic study of diamondoid zinc imidazolates

The energetic landscape of Zn(imidazolate)2 networks with diamond topology is explored in detail. 30 different conformations are derived and compared on the basis of density-functional theory total energy calculations. The most stable conformations for both single and two-fold interpenetrated structures have been identified (space groups I2d and I41cd, respectively). H⋯H interactions are shown to be one of the factors governing the stability of the frameworks.