O,O′-2-Iodo-1,3-phenyl­ene bis­(diphenyl­phosphinothio­ate)

Jun-long Niu; Xia Wang; Biao Gao; Mao-ping Song

doi:10.1107/S1600536811033629

. 2011 Aug 27;67(Pt 9):o2499. doi: 10.1107/S1600536811033629

O,O′-2-Iodo-1,3-phenylene bis(diphenylphosphinothioate)

Jun-long Niu ^a, Xia Wang ^b, Biao Gao ^a, Mao-ping Song ^a,^*

PMCID: PMC3200686 PMID: 22064275

Abstract

The title compound, C₃₀H₂₃IO₂P₂S₂, was synthesized by the reaction of 2-iodobenzene-1,3-diol, chlorodiphenylphosphine, Et₃N and sulfur. The P=S bonds project to opposite sides of the central aromatic ring. The O—P—S and C—P—S bond angles are significantly larger than the O—P—C and C—P—C bond angles, indicating significant distortion of the tetrahedral geometries of the P atoms. The P=S bond lengths of 1.9311 (13) and 1.9302 (12) Å in the title compound are shorter than that found in Ph₃P=S [1.950 (3) Å] because the replacement of one C atom attached the P atom by an O atom increases the effective electronegativity of the P atom.

Related literature

For related compounds, see: Eisler & Puddephatt (2006 ▶); Aleksanyan et al. (2011 ▶); Mague et al. (2007 ▶).

Experimental

Crystal data

C₃₀H₂₃IO₂P₂S₂
M _r = 668.44
Monoclinic,
a = 12.5467 (11) Å
b = 13.4389 (9) Å
c = 18.0010 (13) Å
β = 108.299 (8)°
V = 2881.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.39 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.739, T _max = 1.000
13529 measured reflections
5949 independent reflections
4846 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.086
S = 1.08
5949 reflections
335 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811033629/hb6374sup1.cif

e-67-o2499-sup1.cif^{(24.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033629/hb6374Isup2.hkl

e-67-o2499-Isup2.hkl^{(291.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank Professor Yu Zhu of Zhengzhou University for help.

supplementary crystallographic information

Comment

Phosphinothioates play significant roles in coordination chemistry and transition-metal catalysis (Eisler & Puddephatt, 2006). Furthermore, the ability of thiophosphinoyl moieties to act as bridging ligands has prompted the development of the pincer-type chemistry (Aleksanyan et al., 2011). In this work, through a facile one-pot phosphorylation/oxidiation procedure, we obtained the title compound, which is reported here. The title compound, C₃₀H₂₃IO₂P₂S₂, was synthesized by the reaction of 2-iodobenzene-1,3-diol, chlorodiphenylphosphine, Et₃N with sulfur. The compound exhibits distorted tetrahedral geometry about the P1 and P2 atoms (Fig. 1), and the O—P—S, C—P—S bond angles are significantly larger than the O—P—C, C—P—C bond angles. The P=S bonds of 1.9311 (13) and 1.9302 (12) Å are shorter than that found in Ph₃P=S [1.950 (3) Å] because the replacement of one carbon on phosphorus by oxygen increases the effective electronegativity of the P atom.

Experimental

A mixture of 2-iodobenzene-1,3-diol (118 mg, 0.5 mmol), Et₃N (0.2 ml, 1.5 mmol) and chlorodiphenylphosphine (0.14 ml, 0.75 mmol) in toluene (5 ml) was heated to reflux for 3 h. Then sulfur (48 mg, 1.5 mmol) was added and the mixture was heated to 90\ %C for 30 min. The product was isolated and recrystallized from dicholomethane/hexane, colorless crystals of the title compound was obtained.