Single-crystal X-ray and neutron structure refinements carried out on neptunite (KNa2Li(Fe, Mg, Mn)2Ti2Si8O24) from San Benito, California at various temperatures (neutrons: 15 K and 293 K; X-rays: 110 K, 293 K and 493 K) indicate that this mineral crystallizes in the acentric space group Cc (T=293K: a=16.427 A, b=12.478 A, c=9.975 A, β= 115.56°, Z=4, V=1844.53 A3) due to ordering of octahedrally coordinated metals (Ti, Fe, Mn, Mg). In the neptunite structure, Ti and (Fe, Mn, Mg) octahedra share edges to form chains that run along [110] and [110]. These chains are, in turn, linked through shared corners along [001]. The resulting octahedral framework is interwoven by a similar [Si8O22] tetrahedral framework. Li, Na and K occupy 6-, 8- and 10- coordinated sites within the framework. The metal-containing polyhedra show strong distortions at all temperatures. In particular, Ti exhibits a strong off-center displacement (≈0.25 A) within its octahedron, leading to four Ti-O distances of 2.0 A, one of 2.2 A and one of 1.7 A. The displaced Ti position is in good agreement with a position that minimizes differences between ionic bond strengths and is interpreted as an energy minimum in an ionic potential model. Mossbauer spectra collected at 77 K, 293 K and 400 K indicate all Fe to be present as octahedral Fe2+. Although two distinct Fe positions were found in the structure, 77 K and 293 K spectra display only one quadrupole doublet. Two Fe sites can only be resolved in the 400 K spectrum. It is suggested that the temperature dependence of octahedral edge distortions is responsible for the separation of the Mossbauer doublets.