The Limited Predictive Power of the Pauling Rules

George, Janine; Waroquiers, David; Stefano, Davide Di; Petretto, Guido; Rignanese, Gian‐Marco; Hautier, Geoffroy

doi:10.1002/anie.202000829

Cited by 62 publications

(37 citation statements)

References 42 publications

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“…The agreement of the observed coordination (color of the data point) with the predicted region is relatively good for smaller cations with the observed coordination number within 2-4. For larger cations, the predictive power of the first Pauling rule is very poor, which is in agreement with the recent analysis of Pauling rules validity for oxides [28]. For example, we observe the tetragonal coordination in the region where the octahedral coordination should exist.…”

Section: Preferred Cation Sitessupporting

confidence: 86%

The Crystal Chemistry of Inorganic Hydroborates

2020

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The crystal structures of inorganic hydroborates (salts and coordination compounds with anions containing hydrogen bonded to boron) except for the simplest anion, borohydride BH4−, are analyzed regarding their structural prototypes found in the inorganic databases such as Pearson’s Crystal Data [Villars and Cenzual (2015), Pearson’s Crystal Data. Crystal Structure Database for Inorganic Compounds, Release 2019/2020, ASM International, Materials Park, Ohio, USA]. Only the compounds with hydroborate as the only type of anion are reviewed, although including compounds gathering more than one different hydroborate (mixed anion). Carbaborane anions and partly halogenated hydroborates are included. Hydroborates containing anions other than hydroborate or neutral molecules such as NH3 are not discussed. The coordination polyhedra around the cations, including complex cations, and the hydroborate anions are determined and constitute the basis of the structural systematics underlying hydroborates chemistry in various variants of anionic packing. The latter is determined from anion–anion coordination with the help of topology analysis using the program TOPOS [Blatov (2006), IUCr CompComm. Newsl. 7, 4–38]. The Pauling rules for ionic crystals apply only to smaller cations with the observed coordination number within 2–4. For bigger cations, the predictive power of the first Pauling rule is very poor. All non-molecular hydroborate crystal structures can be derived by simple deformation of the close-packed anionic lattices, i.e., cubic close packing (ccp) and hexagonal close packing (hcp), or body-centered cubic (bcc), by filling tetrahedral or octahedral sites. This review on the crystal chemistry of hydroborates is a contribution that should serve as a roadmap for materials engineers to design new materials, synthetic chemists in their search for promising compounds to be prepared, and materials scientists in understanding the properties of novel materials.

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Section: Preferred Cation Sitessupporting

confidence: 86%

The Crystal Chemistry of Inorganic Hydroborates

2020

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“…It is interesting to note that all nitrogen atoms are connected to phosphorus atoms as well as to zinc atoms, with the nitrogen on 4a being connected to two P 5+ and two Zn 2+ and the one on 8b to one P 5+ and three Zn 2+ . Therefore, both positions do not strictly fulfil the octet rule as discussed previously, but only approximate Pauling's rules (George et al, 2020) with bond strengths of +3.5 and +2.75, respectively.…”

Section: The Na 2 Sio 3 Typementioning

confidence: 80%

Symmetry relations in wurtzite nitrides and oxide nitrides and the curious case of Pmc2₁

Breternitz

Schorr

2021

Acta Cryst Sect A

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Binary III–V nitrides such as AlN, GaN and InN in the wurtzite-type structure have long been considered as potent semiconducting materials because of their optoelectronic properties, amongst others. With rising concerns over the utilization of scarce elements, a replacement of the trivalent cations by others in ternary and multinary nitrides has led to the development of different variants of nitrides and oxide nitrides crystallizing in lower-symmetry variants of wurtzite. This work presents the symmetry relationships between these structural types specific to nitrides and oxide nitrides and updates some prior work on this matter. The non-existence of compounds crystallizing in Pmc21, formally the highest subgroup of the wurtzite type fulfilling Pauling's rules for 1:1:2 stoichiometries, has been puzzling scientists for a while; a rationalization is given, from a crystallographic basis, of why this space group is unlikely to be adopted.

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“…Darüber hinaus hat auch die erste Regel, die Radien-Verhältnis-Regel, viele Ausnahmen: Sie gilt nur für 66 % der getesteten Koordinationsumgebungen. 44) Schnick und Dubrovinsky realisierten einen von ihnen schon vor Jahren theoretisch vorhergesagten ultrainkompressiblen Hartstoff, ein neues Beispiel für die oft untersuchten Nitridspinelle. 45) BB…”

Section: Neue Verbindungenunclassified