Bond-length distributions for ions bonded to oxygen: metalloids and post-transition metals

Abstract

Bond-length distributions have been examined for 33 configurations of the metalloid ions and 56 configurations of the post-transition metal ions bonded to oxygen, for 5279 coordination polyhedra and 21 761 bond distances for the metalloid ions, and 1821 coordination polyhedra and 10 723 bond distances for the post-transition metal ions. For the metalloid and post-transition elements with lone-pair electrons, the more common oxidation state between n versus n+2 is n for Sn, Te, Tl, Pb and Bi and n+2 for As and Sb. There is no correlation between bond-valence sum and coordination number for cations with stereoactive lone-pair electrons when including secondary bonds, and both intermediate states of lone-pair stereoactivity and inert lone pairs may occur for any coordination number > [4]. Variations in mean bond length are $ 0.06-0.09 Å for strongly bonded oxyanions of metalloid and post-transition metal ions, and $ 0.1-0.3 Å for ions showing lone-pair stereoactivity. Bond-length distortion is confirmed to be a leading cause of variation in mean bond lengths for ions with stereoactive lone-pair electrons. For strongly bonded cations (i.e. oxyanions), the causes of mean bond-length variation are unclear; the most plausible cause of mean bond-length variation for these ions is the effect of structure type, i.e. stress resulting from the inability of a structure to adopt its characteristic a priori bond lengths.

Phase Formation Studies of Lead(II) Copper(II) Oxotellurates: The Crystal Structures of Dimorphic PbCuTeO5, PbCuTe2O6, and [Pb2Cu2(Te4O11)](NO3)2

“…According to a recent classification of the structural architecture of tellurium oxocompounds, this type of tellurium‐oxygen chain belongs to ino oxotellurates and is composed of corner‐sharing achter ‐chains which makes it the most complex type of an oxotellurate(VI) chain reported so far. The average Te–O bond length in the chain (1.928 Å) conforms perfectly with the value of 1.923 Å derived from 864 Te–O bonds with hexavalent tellurium in octahedral coordination . The spatial arrangement of the copper‐ and tellurium‐oxygen chains leaves space for the four Pb II cations that are irregularly surrounded by oxygen atoms.…”

β‐Mannosylation through O‐Alkylation of Anomeric Cesium Alkoxides: Mechanistic Studies and Synthesis of the Hexasaccharide Core of Complex Fucosylated N‐Linked Glycans

“…The 1 C 4 conformer of 7‐Cs is 6.4 kcal/mol less stable (see SI for details). Strong chelation of the cesium ion with four oxygen atoms, O1, O2, O6, and O5 (the endocyclic oxygen), was observed . The lower stability of anomeric cesium alkoxides 9‐Cs and 11‐Cs is attributed to the lack of O2 and O6 substituents, respectively, which diminished the chelating Cs–O interactions.…”

On the Crystal Chemistry of Inorganic Nitrides: Crystal-Chemical Parameters, Bonding Behavior, and Opportunities in the Exploration of Their Compositional Space

“…In this work, we use the method of Gagné & Hawthorne 59 to derive new bondvalence parameters for nitrides, provide a scale of Lewis acidity for nitrides, and further outline a baseline statistical knowledge of bond lengths for cations bonded to N 3-as a contribution to our gradual effort toward modernizing Shannon's set of ionic radii 60 (see refs. 50,[61][62][63][64] for bondlength statistics of cations bonded to O 2-; in prep for cations bonded to S 2-, Se 2-and/or Te 2-). Later in this work, we explore new and interesting venues for the exploratory synthesis of functional inorganic nitrides from a crystal-chemical perspective.…”

“…Gagné & Hawthorne state that deviations from such shape are the result of bond-topological, electronic and/or crystal-structure effects, 50 which they go on to describe for all cations of the periodic table observed bonding to O 2-in inorganic structures. 50,[61][62][63][64] Notable examples of anomalous bond-length distributions include a tri-modal distribution for [4] P 5+ -O 2bonds, 62 caused by varying bond-valence requirements as a function of the degree of polymerization of the [PO4] 3-oxyanion (i.e. bond-topological effects), a tri-modal distribution for [6] Mo 6+ -O 2-bonds, 50 arising from a combination of pseudo Jahn-Teller and bond-topological effects, and anomalously long tails at longer bond lengths for penta-coordinated ion configurations of Cr 2+ , Co 2+ and Cu 2+ , also caused by pseudo Jahn-Teller and bond-topological effects.…”

“…In light of the recent extensive review of the crystal chemistry of oxides and oxysalts by Gagné & Hawthorne,50,[61][62][63][64] we investigate our dataset of inorganic nitride structures for the occurrence of bond topological, electronic and/or crystal-structure effects, placing emphasis on the functional properties resulting from these effects. Compositional and structural divergences are expected between the compounds making up these two datasets.…”