The influence of the miscellaneous crown ethers (CE) composition and structure on peculiarities of formation, as well as stoichiometry, molecular and crystalline structure of CE complexes (adducts) with the amidosulfuric acid zwitterion (+NH3SO3 ¯), hydroxonium (Н3О+), water and molecules containing groups H2N-, HN< and HC<, generating hydrogen bonds with CE cavity is discussed. Under the +NH3SO3 ¯ interaction with 15 distal and proximal dibenzo-СЕ (DBCE), in contrast to aliphatic, cycloaliphatic and benzo-СЕ (BCE), only in the case of [2.4]− and [1.5]DB18C6 as well as biphenyl-20-crown-6 (BP20C6) was a success to separate the stable complexes (1:1) in which the zwitterion, at the expense of N–H….O bonds, forms practically ideal «tripod» structure with alternative oxygen atoms of СЕ. The similar situation realizes in cations of complexes [(H3O·BP20C6)]MF6 (М = Nb and Та), while in complexes [(H2O·[1.5]DB18C6)2(Н3О)]MF6 supramolecular cations are associated by two СЕs centered by Н7О3 + «bridge» via Н-bonds. It was revealed that the polymeric chains in crystal of complex SbF3 with [1.5]DB-thia-18C6 (1:1) are formed via expanded of C–H….F hydrogen bonds. The role of transannular C-H…O interactions in stabilization of DBCE conformations and a character of macrocycle form change as a consequence of complexation with various «guests» are considered. The peculiarities and possible mechanism of 5-substituted BCE and 5,5/-disubstituted DBCE interaction with the hydrated surface of non-porous aerosil (AS), γ-aminopropyl-AS and its protonated form are discussed. The results of X-ray analysis of more than 30 complexes of СЕ with halogenochromates MCrO3X (M = Li, Na, K, H4N+; X = F, Cl, Br) including complexes containing as “extra-ligands” water molecules, determinant different variants of coordination and association of the last ones with the СЕ complex cations and neutral ligand, are systematized. Interrelationships of structural factors determining a reactivity of studied complexes were revealed. For instance, the rate of benzyl alcohol oxidation by these complexes is cymbate to a distance of metal cation from the mean plane of n oxygen atoms of CE.