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The addition of tert-butyl hydro­peroxide (tBuOOH) to two MnII complexes, differing by a small synthetic alteration from an ethyl to a propyl linker in the ligand scaffold, results in the formation of the high-valent bis-oxo complexes, {[MnIV{N4(6-Me-DPEN)}]2(μ-O)2}2+ (1) and {[MnIV{N4(6-Me-DPPN)}]2(μ-O)2}2+ (2).

The crystal structures of caesium di­hydrogen arsenate(V) bis­[tri­hydrogen arsen­ate(V)], Cs(H2AsO4)(H3AsO4)2, ammonium di­hydrogen arsenate(V) tri­hydrogen arsenate(V), NH4(H2AsO4)(H3AsO4), and dilithium bis­(di­hydrogen phosphate), Li2(H2PO4)2, were solved from single-crystal X-ray diffraction data. NH4(H2AsO4)(H3AsO4), which was hydro­thermally synthesized (T = 493 K), is homeotypic with Rb(H2AsO4)(H3AsO4), while Cs(H2AsO4)(H3AsO4)2 crystallizes in a novel structure type and Li2(H2PO4)2 represents a new polymorph of this composition. The Cs and Li compounds grew at room temperature from highly acidic aqueous solutions. Li2(H2PO4)2 forms a three-dimensional (3D) framework of PO4 tetra­hedra sharing corners with Li2O6 dimers built of edge-sharing LiO4 groups, which is reinforced by hydrogen bonds. The two arsenate compounds are characterized by a 3D network of AsO4 groups that are connected solely via multiple strong hydrogen bonds. A statistical evaluation of the As—O bond lengths in singly, doubly and triply protonated AsO4 groups gave average values of 1.70 (2) Å for 199 As—OH bonds, 1.728 (19) Å for As—OH bonds in HAsO4 groups, 1.714 (12) Å for As—OH bonds in H2AsO4 groups and 1.694 (16) Å for As—OH bonds in H3AsO4 groups, and a grand mean value of 1.667 (18) Å for As—O bonds to nonprotonated O atoms.