(CuI)₂P₁₄: ein neues Phosphorpolymer in einer Kupferhalogenid-Matrix /(CuI)₂P₁₄: a Novel Phosphorus Polymer in a Copper Halide Matrix

Abstract

Phosphorus, Copper Compounds, Crystal Structure (CuI)2Pi4 is a new adduct of copper iodide to a neutral phosphorus polymer. It is obtained by reaction of Cul and Pred at 400 °C. The compound crystallizes monoclinically, space group P2,/c (No. 14), a = 9.919 (2), b = 9.718(2), c = 16.478(3) Ä, ß = 105.71(1)°, V = 1529.0(7) A3, with Z = 4. The crystal structure was refined to R\ = 0.029 for 2680 reflections and 173 parameters. It contains a new polymeric phosphorus allotrope with the translational unit P^° consisting of experimentally unknown [PI2] groups which are linked by [P2] fragments. The phosphorus rods consist of five-and six-membered rings, and are coordinated only by copper atoms. Einleitung

Icosahedral and Ring‐Shaped Allotropes of Phosphorus

“…[24,25,38] The experimental band gap for the orthorhombic black phosphorus is 0.33 eV. [39] Ring-shaped allotropes of phosphorus: The C 2v -symmetric P 18 and P 28 have been reported by Häser et al [11,13] as stable clusters of red phosphorus. They are also short chains, where P 8 and P 2 structural units are sequentially repeated.…”

“…, [17] and [P2- [18] were fully optimized for reference purposes. The periodic calculations were carried out with the CRYSTAL software (versions 2003 and 06).…”

“…Bçcker and Häser also devised a naming convention for the description of the red phosphorus structures using structural rules derived from the Baudlers rules for covalently bound phosphorus compounds. [14] Bçcker and Häser studied several tubular chains of red phosphorus, three of which have been obtained embedded in a copper halide matrix: [15] The chain denoted as ]P4 (4)[P8] [16] was known earlier; ]P2A C H T U N G T R E N N U N G [P10] [17] and [P2A C H T U N G T R E N N U N G [P12(4)] [18] were found soon after the predictions. Recently, the ]P4(4)[P8] and ]P2-A C H T U N G T R E N N U N G [P10] chains were isolated from the copper halide matrix, resulting in phosphorus nanorods.…”

Van der Waals interactions in selected allotropes of phosphorus

“…Lately, pair-wise tubes were discovered and obtained in crystalline form with parallel orientation (Ruck's fibrous P [10]) -in contrast to a perpendicular arrangement in Hittorf's violet P [11]. The discovery of different kinds of P nanorods [12][13][14][15] extended the variety of P structures but left some open questions concerning their crystal structures and their place in the stability order of the P allotropes.…”

Phosphorus Nanorods—Two Allotropic Modifications of a Long‐Known Element

“…[6][7][8][9][10][11] Furthermore, polymeric phosphorus strands are readily formed as their copper iodide adducts by treating stoichiometric mixtures of CuX (X = Br, I) with elemental P. Compounds of this kind include two different 1 1 [P 12 ] polymers in (CuI) 8 P 12 [12] and in (CuI) 3 P 12 , [13] respectively, and a 1 1 [P 14 ] polymer in (CuI) 2 P 14 . [14] The separation of the pure phosphorus strands from the copper halide matrix represents an intriguing chemical challenge and should help to verify the theoretical investigations. Herein, we report the isolation and characterization of the Figure 1)-by a low-temperature route.…”