RESUMO
A method for the visualization of noncovalent interactions using examples of the conformational polymorphs of four organic compounds: 2-(phenylamino)nicotinic, 2-(3-chloro-2-methylphenylamino)nicotinic, N-(3-chloro-2-methylphenyl)anthranilic and 2-(methylphenylamino)nicotinic acids is examined. The changes in noncovalent contacts are plotted against the angle between the planes of aromatic rings allowing a visual representation of conformational adjustment of molecules as well as packing features of crystal structures. According to the k-Φ criterion, the studied structures represent conformational polymorphs. Different types of hydrogen bonding are discussed within the framework of the method of visualization and molecular Voronoi-Dirichlet polyhedra. Good correlations are found between calculated and experimental data for several cases, such as the agreement between π stacking and polymorphic transition temperatures as well as between the area of a contact and the energy of conjugation. Also, an attempt has been made to assess the relative contributions of conformational and packing polymorphism in the formation of polymorphs.
RESUMO
Synthesis, FTIR spectral study, and X-ray diffraction analysis of single crystals of (CH3)4N[UO2(mba)3] (I), (CH3)4N[NpO2(mba)2(NO3)] (II), (CH3)4N[PuO2(mba)2(NO3)] (III), and (CH3)4N[NpO2(mba)(NO3)2] (IV), where mba is a monobromoacetate ion (CH2BrCOO-), were conducted. The main structural units of crystals I-IV are mononuclear anionic complexes of the [AnO2(mba)3]-, [AnO2(mba)2(NO3)]-, or [AnO2(mba)(NO3)2]- composition. All these complex units are characterized with the same crystal-chemical formula AB 01 3 (A = AnO2 2+ and B 01 = CH2BrCOO- or NO3 -). Using the method of molecular Voronoi-Dirichlet polyhedra, the contributions of various types of noncovalent interactions into the formation of supramolecular structures of the obtained complexes were characterized. The analysis of coordination modes of all monobromoacetate-containing compounds from the Cambridge Structural Database was accomplished. Actinide contraction in the studied compounds is discussed.
RESUMO
The structures of the single crystals of compounds K2UO2(tca)4(tcaH)2 (I), K4NpO2(tca)6(tcaH)(H2O)3 (II), Rb4UO2(tca)6(tcaH)(H2O)3 (III), and Cs3UO2(tca)5(tcaH)2·H2O (IV), where tca is the trichloroacetate ion, were established by X-ray diffraction analysis. The crystals of II-IV have a framework structure, whereas in the layered crystals of I, neighboring layers are connected to each other via halogen bonds. In this regard, the crystals of I possess perfect cleavage along the (001) plane: the crystals are easily cut into stacks of very thin layers. Halogen bonds in the structures of all title compounds were characterized using the method of molecular Voronoi-Dirichlet polyhedra. The donor-acceptor halogen bond synthon, where the same halogen atom is both the donor towards one halogen atom and the acceptor from the second halogen atom, is recognized for its usefulness in the crystal design. The description of the ligand coordination modes and crystal chemical formulae of complexes is adapted for cases when ligands have chemically non-equivalent and unobvious donor atoms (for example, oxygen and halogen atoms in halogen-substituted carboxylate anions).
