The reaction system consisting of copper, saccharinate, and the auxiliary ligands H2O, PPh3, and NH3 produces a sequence of compounds in which saccharinate is coordinated to copper in four distinct manners. The complex trans-[Cu(sacch)(2)(H2O)(4)] (2) (produced by thermal dehydration of trans- [Cu(sacch)(2)(H2O)(4)]. 2H(2)O (1)) reacts with triphenylphosphine in CH2Cl2 to produce any or all of three Cu(I) complexes, depending upon conditions. The three Cu(I) compounds are Cu(sacch)(PPh3)(3) (3), in which saccharinate binds to copper through the carbonyl group of the ligand, Cu(sacch)(PPh3)(2) (4), in which sacch binds to Cu through its charge-bearing nitrogen atom; and [Cu(sacch)(PPh3)](2) (5), a dinuclear complex in which saccharinate bridges two Cu centers through its imidate nitrogen and carbonyl oxygen atoms. Complexes 3-5 can be isolated individually, although in solution they exist in a complex equilibrium which has been examined by NMR spectroscopy. Each of the three Cu(1) products reacts with NH3 in CH2Cl2 solution to produce trans-[Cu(sacch)(2)(NH3)(4)] (6), an unstable Cu(H) complex that exhibits misdirected valence at the Cu-N(sacch) bond. Complex 6 evolves spontaneously to [Cu(sacch)(NH3)(4)](sacch).H2O (7), which in the solid state is dominated by a supramolecular aggregate of two formula units, linked by hydrogen bonding in which the water molecule plays a central role. Alternative pathways exist to several of the products. The X-ray crystal structure analyses of 3-7 are reported and establish the coordination modes of saccharinate, the misdirected valence in 6, and the supramolecular aggregation in 7. The structure analysis of 7 by single-crystal neutron diffraction is reported and together with the previously reported neutron structure analysis of 1 establishes the substitution of the auxiliary ligand H2O by NH3 in the Cu(II) products.