Sodium tetraperoxidochromate(V), Na3Cr(O2)4·14H2O, was prepared and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. It crystallizes in the triclinic space group P1 with a = 7.5349(6)Å, b = 8.6378(7)Å, c = 8.9921(7)Å, α = 64.087(1), β = 81.565(1), γ = 69.348(1)°, V = 492.56(7)Å3, Dx = 1.690 g/cm3, and Z = 1. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0277 and 0.0722, respectively, for all 2310 independent reflections. The chromium ion is coordinated by four peroxido ligands in a distorted dodecahedral geometry, whereas each sodium ion is coordinated by six water molecules to form an octahedral Na(H2O)6 unit, which is connected by two bridging water molecules to form zigzag [cis-{Na(H2O)2(μ-H2O)4}-trans-{Na(H2O)2(μ-H2O)4}]n chain molecules in the crystal.
