Hydrogen bis[tris(4-fluorophenyl)phosphane oxide] triiodide

Abstract

In the title compound, C(36)H(25)F(6)O(2)P(2)(+)·I(3)(-), hydrogen-bonded [{(p-FC(6)H(4))(3)PO}(2)H](+) dimers assemble along the crystallographic c axis to form channels that house extended chains of triiodide anions. Although the I-I bond lengths of 2.9452 (14) and 2.9023 (15) Å are typical, the inter-ion I...I distance of 3.5774 (10) Å is unusually short. A posteriori modelling of nonmerohedral twinning about (100) has been only partially successful, achieving a reduction in the maximum residual electron density from 5.28 to 3.24 e Å(-3). The inclusion of two low-occupancy I-atom sites (total 1.7%), which can be interpreted as translational disorder of the triiodide anions along the channels, reduced the maximum residual electron density to 2.03 e Å(-3). The minor fractional contribution volume of the nonmerohedral twin domains refined to 0.24 and simultaneous refinement of the inversion twin domains showed the crystal to be a 0.5:0.5 inversion twin.

Anionic phosph(in)ito (“phosphoryl”) ligands: Non-classical “actor” phosphane-type ligands in coordination chemistry

“…Phosphane oxides have been investigated in strong intermolecular hydrogen bonding with proton H + or Hbonded water molecule that link intermolecularly pairs of P + −O -entities [159][160][161][162][163][164][165][166][167][168]. Triphenylphosphane oxide A c c e p t e d M a n u s c r i p t (TPPO) has been widely exploited [169][170][171] in crystal engineering [172], particularly with regard to the design of hydrogen-bonded co-crystals.…”

Evidence of the unprecedented conversion of intermolecular proton to water bridging of two phosphoryl ruthenium complexes

“…Many studies have emphasized that the PQO unit, better described with the highly polar canonical structure P + -O À , creates the possibility to interact with protons. It has been confirmed by Pietschnig and co-workers for Me 3 PO and HCl 6 and demonstrated for example by the structurally characterized discrete [(R 3 PO) 2 H] + type cations (R = Me, 7 Et, 8 iPr, 9 Ph, 10 p-FC 6 H 4 , 11 ) which have been shown to involve a strong hydrogen bond with H + that links intermolecularly pairs of phosphane oxide R 3 PQO entities. Surprisingly and to the best of our knowledge, hydrogen-bonded dimers of P-metallated phosphoryl complexes [{[L n M](R 2 PQO) 2 }H] + have not yet been described in the literature.…”

“…The presence of a strong hydrogen bonding interaction between the two metallic fragments was indicated by the short OÁ Á ÁO separation [O1-O 0 1 2.409 Å]. [6][7][8][9][10][11] The P-O bond of 1.559( 5) is significantly longer than typical double PQO bonds of, for example, 1.487(3) Å in (C 6 H 5 ) 3 PQO 19 and 1.467(2) Å in (C 6 F 5 ) 3 PQO. 20 However, they are shorter than the single P-O bonds of 1.581(4), 1.579(4) and 1.553(3) Å in triphenylphosphane oxyl derivatives, 21 which average 1.571 Å.…”

Absolute-structure reports

“…Due to the overlap of Friedel opposites in a powder diffraction experiment, it is not possible to produce 2AD and selected D plots from these; there were four such cases. The intensity data of eg3082 (Haghjoo et al, 2012) had a data manipulation or software error. The data had clearly been merged and averaged in point group 2 rather than the m appropriate to its space group, Cc.…”