The thesis is devoted to synthesis and structural investigation of H-bonded and coordination polymers of 4,4'-bipyrazolyls, a new class of tectons in the field of crystal engineering. Known modes of the pyrazole self-assembly was used for rational design of quite regular three-connected network via inheritance of them in the structures of 4,4'-bipyrazolyls and their analogs. The original design of the tecton, represented as a flexible joint of two three-connected vertices, allows the self-assembly process to reproduce regular networks including the noncentrosymmetric (10,3)-a,c ones. A range of 3,3',5,5'-tetramethyl-4,4'-bipyrazolyl adducts were obtained in order to investigate the influence of H-bond donor/acceptor inclusion on the pyrazole self-assemby modes. The formation of helical patterns attributed to the nonplanarity of the tecton were found for a range of hydrates and the inheritance of pyrazole-like catameric paterns were stated for some new pyrazole-phenol adducts. Also, the structural roleof newly observed (Pz)H---pi(Ph)OH and PhOH---pi(Pz), Pz = pyrazole, interactions were established for adducts with meta- phenols. The potential of pyrazolium cation for crystal engineering by strong H-bonds was tested through structural investigation of 4,4'-bipyrazolium salts. The formation of chain-based structures were rationalized on the basis that pyrazolium-anion interaction patterns follow a few well-defined cyclic {(Hpz)(AX2)1/2}, {(Hpz)2A2} modes, depending on the anion's shape and charge. The established modes are supramolecular synthon candidates, and can be used for anion dependent "chain-engineering" in the structures of pyrazolium salts. The original skew geometry of the 4,4?-bipyrazolyl as a bidentate ligand, limited flexibility of the tetramethyl substituted 4,4'-bipyrazolyl, the presence of NH group near the ligand's N-donor atoms substantiate the interest towards the coordination bonded crystal engineering of the proposed tectons. 1D, 2D, 3D coordination polymers of 4,4'-bipyrazolyls and Co(II), Cu(II), Zn(II), Ag(I), Cd(II) were synthesized as a crystalline solids under different conditions, including the use of different counter anions and the type of guest molecules; their structures were proven by single crystal X-ray diffraction analysis. Typical 1D and 2D coordination polymers manifest tecton caused "flexibility", which results in such a nontypical structure organization like chiral double helices, or porous, H-bonded stacking of corrugated (4,4) networks, formation of which is principally influenced by NH---A- interactions. It was clearly shown that variable angularity of the tecton could result in fundamental and rationally conditioned changes in the network topology, namely the observed cases (4,4) net " diamond net and (4,4) net " 3(2)6(2) net (porous) isomerism, or reproduce a new, porous 4·4·8(8)·8(8)·8(4)·8(4) network almost in the most regular form, which is impossible for the 4,4'-bipyridyl spacer tecton.84 crystalline crystalline phases of H-bonded and coordination compounds ofnew tecton class, the 4,4'-bipyrazolyls were investigated by means of X-ray single crystal structure determination. Possible areas of application of 4,4'-bipyrazolyls were shown and new promising directions of investigation in particular towards rational design of noncentrosymmetric and porous crystalline structure were targeted.
