Date Available


Year of Publication


Degree Name

Doctor of Philosophy (PhD)

Document Type



Arts and Sciences



First Advisor

Dr. Carolyn P. Brock


The series of compounds [M(H2O)2(15-crown-5)](NO3)2, M = Mg, Mn, Co, Cu and Zn, has been extended to include two new phases for M = Fe and two new phases for M = Ni. The system [M(H2O)2(15-crown-5)](NO3)2 is remarkable for having many high-Z’ phases (Z’ > 1) with similar packing and for having solid-solid phase transitions through which there is no significant loss of crystallinity. The synthesis of the analogous Ni complex was carried out. Single-crystal X-ray diffraction showed that the coordination of the Ni2+ ion is different from that of the other six M2+ ions in the system [M(H2O)2(15-crown- 5)](NO3)2.

High temperature phases with high Z’ (8) were isolated for M = Mg, Fe and Zn. The refinements of such phases are challenging because of the lack of information in the diffraction patterns. Full details of the refinements for these three phases are discussed.

Six other Ni(II) complexes consisting of Ni2+, NO3-, 15-crown-5 and different solvents were found when efforts were made to synthesize the compound [Ni(H2O)2(15-crown- 5)](NO3)2. In these chemically different environments, the Ni2+ ions are not coordinated by the 15-crown-5 molecules; rather, one-dimensional H-bonded chains are formed from uncomplexed 15-crown-5 molecules and the Ni(II) complexes.

Among these six Ni(II) complexes, the compounds [Ni(H2O)6](NO3)2·(15-crown-5)·H2O, [Ni(H2O)6](NO3)2·(15-crown-5)·2H2O and [Ni(H2O)2(MeCN)(NO3)2]·(15-crown- 5)·MeCN were found to have reversible solid-solid phase transitions between structurally related phases. In all of these transitions, no significant crystal damage was detectable. The two latter systems are unusual because their phase sequences include three transitions and four phases between 90 and 295 K and because of the existence of high-Z’ phases. These high-Z’ phases are best depicted as being intermediate to low- and hightemperature phases. A method based on thermal analyses and X-ray diffraction has been developed for studying such sets of phase transitions.

Included in

Chemistry Commons



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