Bond‐length distributions for ions bonded to oxygen: results for the non‐metals and discussion of lone‐pair stereoactivity and the polymerization of PO4. Issue 1 (16th January 2018)

• Record Type: Journal Article
• Authors: Gagné, Olivier Charles; Hawthorne, Frank Christopher
• Is Part Of: Acta crystallographica. Volume 74:Issue 1(2018:Feb.)
• Page Start: 79
• Page End: 96
• Publication Date: 2018-01-16
• Subjects: bond lengths -- non‐metals -- lone‐pair stereoactivity -- hydrogen -- phosphate -- polymerization -- oxides -- oxysalts
• DOI: 10.1107/S2052520617017541
• Languages: English
• ISSNs: 2052-5206

Abstract

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. Lone‐pair stereoactivity for ions bonded to O 2− is discussed, as well as the polymerization of the PO4 group. 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 ( R 2 = 0.94 and 0.96): H…O = 1.273 × O…O – 1.717 Å; O—H + H…O = 1.068 × O…O – 0.170 Å. 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 n versus n +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 O 2− . Observed O— X —O bond angles indicate that the period 3 non‐metal ions P 3+, S 4+, Cl 3+ and Cl 5+ are lone‐pair seteroactive when bonded to O 2−, 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.