7-[(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)­oxy]-4-methyl-2H-chromen-2-one

Yan-Ru Zhao; Xu-Feng Hou; Zhi-Hong Xu

doi:10.1107/S1600536812023513

. 2012 May 31;68(Pt 6):o1924. doi: 10.1107/S1600536812023513

7-[(5,5-Dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)oxy]-4-methyl-2H-chromen-2-one

Yan-Ru Zhao ^a,^*, Xu-Feng Hou ^a, Zhi-Hong Xu ^a

PMCID: PMC3379479 PMID: 22719677

Abstract

The title compound, C₁₅H₁₇O₆P, was obtained from a reaction of 4-methyl-7-hydroxycoumarin and 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide. There are two molecules in the asymmetric unit in which the benzopyran ring system is almost planar [r.m.s. deviation for each molecule = 0.003 Å]. In the crystal, C—H⋯O hydrogen bonds and π–π stacking interactions [with centroid–centroid distances of 3.743 (3) and 3.727 (3) Å] link the two molecules. The dioxaphosphorinane ring adopts a chair conformation in both asymmetric molecules.

Related literature

For the application of 4-methyl-7-hydroxycoumarin and 2-oxido-1,3,2-dioxaphosphinan derivatives, see: Babu et al.(2008 ▶); Li et al. (2002 ▶, 2006 ▶); Raghu & Reddy (1996 ▶); Sierosławski et al. (2006 ▶); Zhou et al. (2006 ▶). graphic file with name e-68-o1924-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₇O₆P
M _r = 324.26
Monoclinic,
a = 7.309 (4) Å
b = 17.010 (9) Å
c = 25.507 (13) Å
β = 102.596 (17)°
V = 3095 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 293 K
0.22 × 0.17 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.957, T _max = 0.970
16892 measured reflections
6065 independent reflections
2926 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.134
S = 1.00
6065 reflections
398 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812023513/ez2291sup1.cif

e-68-o1924-sup1.cif^{(27.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023513/ez2291Isup2.hkl

e-68-o1924-Isup2.hkl^{(296.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812023513/ez2291Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O2ⁱ	0.93	2.36	3.223 (5)	155
C13—H13B⋯O11ⁱⁱ	0.97	2.48	3.250 (5)	136

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Natural Science Foundation of Henan Province Education Department, China (grant No. 2011 A150027).

supplementary crystallographic information

Comment

2-oxido-1,3,2-dioxaphosphinan and its derivatives exhibit high flame-retardance (Li et al., 2002; Li et al., 2006) as well as biological and pharmaceutical activity (Babu et al., 2008). Coumarin and its derivatives have a wide range of biological activities, and for years have received significant attention regarding natural and synthetic sources (Sierosławski et al., 2006; Zhou et al., 2006). Few crystal sructures containing both of these groups have been characterized. We report here the crystal structure of a new 2-chloro-1,3,2-dioxaphosphinane derivative containing the 7-oxy-4-methyl-2H-chromen-2-one group.

In the title compound, C₁₅H₁₇O₆P, bond distances and angles in (I) are as expected, and the dioxaphosphinan ring adopts a chair conformation (Fig. 1). π-π stacking interactions and C—H···O hydrogen bonds link the molecules. (Table 1, Fig. 2)

Experimental

The title compound was prepared according to the procedure of Raghu & Reddy (1996). The 4-methyl-7-hydroxycoumarin (0.95 g, 6.2 mmol), dry dichloromethane (10 ml) and triethylamine (0.61 g, 6 mmol) were placed in a 100 ml three-necked flask and a solution of 2-chloro-5,5-dimethyl- [1,3,2]dioxaphosphinane 2-oxide (1.12 g, 6.1 mmol) in dry dichloromethane (5 ml) was added dropwise over a period of 1 h at room temperature (298 K). The reaction temperature was raised to 308 K and stirring was continued for 8 h. The solvent was removed under reduced pressure and the residual mixture was washed with anhydrous ether (25 ml), dried and recrystallized from ethanol to give compound (I). Suitable crystals were obtained from a anhydrous methanol at room temperature (m.p. 440 K).