A new polymorph of white phospho­rus at ambient conditions

Dedicated to Professor George Sheldrick on the occasion of his 80th birthday. Phospho­rus exists in several different allotropes: white, red, violet and black. For industrial and academic applications, white phospho­rus is the most important. So far, three polymorphs of white phospho­rus, all consis...

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Bibliographic Details
Published in:IUCrJ 2023-11, Vol.10 (6), p.766-771
Main Authors: Herbst-Irmer, Regine, Wang, Xiaobai, Haberstock, Laura, Köhne, Ingo, Oswald, Rainer, Behler, Jörg, Stalke, Dietmar
Format: Article
Language:English
Subjects:
Allotropy
Cubic lattice
Energy levels
Lattice parameters
Phosphorus
Research Papers
Tetrahedra
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Summary:Dedicated to Professor George Sheldrick on the occasion of his 80th birthday. Phospho­rus exists in several different allotropes: white, red, violet and black. For industrial and academic applications, white phospho­rus is the most important. So far, three polymorphs of white phospho­rus, all consisting of P4 tetrahedra, have been described. Among these, β-P4 crystallizes in the space group P 1 and γ-P4 in the space group C2/m. α-P4 forms soft plastic crystals with a proposed structure in the cubic space group I 43m with the lattice constant a = 18.51 (3) Å, consisting of 58 rotationally disordered tetrahedra and thus is similar to the structure of α-Mn. Here we present a new polymorph, δ-P4. It crystallizes as a sixfold twin with the cell dimensions a = 18.302 (2), b = 18.302 (2), c = 36.441 (3) Å in the space group P212121 with 29 P4 tetrahedra in the asymmetric unit. The arrangement resembles the structure of α-Mn, but δ-P4 differs from α-P4. DFT calculations show δ-P4 to be metastable at a similar energy level to that of γ-P4.
ISSN:2052-2525
DOI:10.1107/S2052252523009247