Bond-length distributions for ions bonded to oxygen: Results for the non-metals and discussion of lone-pair stereoactivity and the polymerization of PO4: Results

Abstract

Bond-length distributions are examined for three configurations of the H+ ion, 16 configurations of the group 14-16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen, for 223 coordination polyhedra and 452 bond distances for the H+ ion, 5957 coordination polyhedra and 22 784 bond distances for the group 14-16 non-metal ions, and 248 coordination polyhedra and 1394 bond distances for the group 17 non-metal ions. H..O and O-H + H..O distances correlate with O..O distance (R2 = 0.94 and 0.96): H..O = 1.273 × O..O-1.717Å; O-H + H..O = 1.068 × O..O-0.170Å. These equations may be used to locate the hydrogen atom more accurately in a structure refined by X-ray diffraction. For non-metal elements that occur with lone-pair electrons, the most observed state between the nversusn+2 oxidation state is that of highest oxidation state for period 3 cations, and lowest oxidation state for period 4 and 5 cations when bonded to O2-. Observed O-X-O bond angles indicate that the period 3 non-metal ions P3+, S4+, Cl3+ and Cl5+ are lone-pair seteroactive when bonded to O2-, even though they do not form secondary bonds. There is no strong correlation between the degree of lone-pair stereoactivity and coordination number when including secondary bonds. There is no correlation between lone-pair stereoactivity and bond-valence sum at the central cation. In synthetic compounds, PO4 polymerizes via one or two bridging oxygen atoms, but not by three. Partitioning our PO4 dataset shows that multi-modality in the distribution of bond lengths is caused by the different bond-valence constraints that arise for Obr = 0, 1 and 2. For strongly bonded cations, i.e. oxyanions, the most probable cause of mean bond length variation is the effect of structure type, i.e. stress induced by the inability of a structure to follow its a priori bond lengths. For ions with stereoactive lone-pair electrons, the most probable cause of variation is bond-length distortion.Bond-length distributions are examined for three configurations of the H+ ion, 16 configurations of the group 14-16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen. Lone-pair stereoactivity for ions bonded to O2- is discussed, as well as the polymerization of the PO4 group.