Monofluorophosphates—New Examples and a Survey of the PO3F2? Anion

During a systematic study of monofluorophosphates, i.e., compounds comprising the tetrahedral anion PO3F2?, twelve, for most part new, were obtained from aqueous solutions. Crystal structure refinements based on single crystal X-ray diffraction data revealed previously unknown structures CdPO3F(H2O)2, Cr2(PO3F)3(H2O)18.8, Pb2(PO3F)Cl2(H2O), (NH4)2M(PO3F)2(H2O)2 (M = Mg, Mn, Co), NH4Cr(PO3F)2(H2O)6, NH4Cu2(H3O2)(PO3F)2, (NH4)2Zn(PO3F)2(H2O)0.2, and (NH4)2Zn3(PO3F)4(H2O), as well redeterminations ZnPO3F(H2O)2.5 (NH4)2Ni(PO3F)2(H2O)6. From structures, CdPO3F(H2O)2 (space group P1¯), Cr2(PO3F)3(H2O)18.8 (P1¯), Pb2(PO3F)Cl2(H2O) (Pnma), NH4Cr(PO3F)2(H2O)6 (R3¯m), (NH4)2Zn(PO3F)2(H2O)0.2 (C2/c), (NH4)2Zn3(PO3F)4(H2O) (I4¯3d) each crystallizes in an unique structure, whereas Co) crystallize (NH4)2Cu(PO3F)2(H2O)2 type (C2/m) (NH4)2Mn(PO3F)2(H2O)2 subgroup thereof (P21/n, with klassengleiche relationship index 2), NH4Cu2(H3O2)(PO3F)2 isotypically natrochalcite-type KCu2(H3O2)(SO4)2. A survey PO3F2? anion, including database entries all inorganic this group, mean bond lengths P–O 1.506(13) Å, P–F 1.578(20) angles O–P–O 113.7(1.7)° O–P–F 104.8(1.7)°, using dataset 88 independent anions or entities. For those monofluorophosphates where hydrogen bonding is present, vast majority cases, bonds D–H···F–P (D O, N) are not developed.