Vivianite specimens from various world localities yield X-ray powder patterns of two types: one corresponds with that shown by synthetic Fe3(PO4)2 · 8H2O and is not readily distinguished from that of barićite; the second shows reflections of monoclinic vivianite and triclinic metavivianite along with reflections of a bobierrite-type phase. The triclinic phase occurs as two twin-related lattices with twin plane 110 being the structural equivalent of 010 in the monoclinic phase. The relationship of the bobierrite-type lattice to the other two has not been established. The ternary pattern is produced by some coarse-grained vivianites on natural oxidation. Finer grained vivianites oxidise to an X-ray amorphous state without passing through a triclinic intermediate.

Metavivianite has been shown to be not dimorphous with vivianite. Assuming the homogeneity and uniformity of the original type samples, it is a triclinic hydrated ferri-ferrous hydroxy phosphate whose formula may be given as Fe2+3-xFe3+x(po4)2(OH)x(8-x)H2O where x > 1.4. The precise oxidation limits between which the triclinic lattice is stable are not known but the structure persists close to total oxidation of all iron. The structure of metavivianite was established using a fragment of kerchenite whose formula as originally given is covered by the general metavivianite formula. Assuming the homogeneity of the original (1907) samples, kerchenite and metavivianite appear to be identical.

The composition, structure, X-ray powder diffraction pattern, optical properties, density, infrared, Raman and Mössbauer spectra, and thermal properties of a homogeneous sample of metavivianite from the Boa Vista pegmatite, near Galiléia, Minas Gerais, Brazil are reported for the first time. Metavivianite is biaxial (+) with α = 1.600(3), β = 1.640(3), γ = 1.685(3) and 2Vmeas = 85(5)°. The measured and calculated densities are Dmeas = 2.56(2) and Dcalc = 2.579 g cm–3. The chemical composition, based on electronmicroprobe analyses, Mössbauer spectroscopy (to determine the Fe2+:Fe3+ ratio) and gas chromatography (to determine H2O) is MgO 0.70, MnO 0.92, FeO 17.98, Fe2O3 26.60, P2O5 28.62, H2O 26.5; total 101.32 wt.%. The empirical formula is (Fe3+1.64Fe2+1.23Mg0.085Mn0.06)Σ3.015(PO4)1.98(OH)1.72·6.36H2O. Metavivianite is triclinic, P, a = 7.989(1), b = 9.321(2), c = 4.629(1) Å, α = 97.34(1), β = 95.96(1), γ = 108.59(2)°, V = 320.18(11) Å3 and Z = 1. The crystal structure was solved using a single-crystal techniques to an agreement index R = 6.0%. The dominant cations in the independent sites are Fe2+ and Fe3+, with multiplicities of 1 and 2, respectively. The simplified crystal-chemical formula for metavivianite is Fe2+ (Fe3+, Fe2+)2(PO4)2(OH,H2O)2·6H2O; the endmember formula is Fe2+Fe3+2(PO4)2(OH)2·6H2O, which is dimorphous with ferrostrunzite.