2,4,8,10,13-Penta­methyl-6-phenyl-13,14-dihydro-12H-6λ5-dibenzo[d,i][1,3,7,2]dioxaza­phosphecin-6-thione

M Krishnaiah; VHH Surendra Babu; A Uma Ravi Sankar; C Naga Raju; Rajni Kant

doi:10.1107/S1600536809052180

. 2009 Dec 12;66(Pt 1):o120. doi: 10.1107/S1600536809052180

2,4,8,10,13-Pentamethyl-6-phenyl-13,14-dihydro-12H-6λ⁵-dibenzo[d,i][1,3,7,2]dioxazaphosphecin-6-thione

M Krishnaiah ^a,^*, VHH Surendra Babu ^a, A Uma Ravi Sankar ^b, C Naga Raju ^c, Rajni Kant ^d

PMCID: PMC2980263 PMID: 21580010

Abstract

In the title compound, C₂₅H₂₈NO₂PS, the cyclodecene ring exhibits a crown conformation. The two dimethylbenzene rings which are fused symmetrically on either side of the ten-membered ring, make dihedral angles of 20.2 (1) and 18.0 (1)°. The phenyl ring substituted at P is perpendicular to the heterocyclic ring, making a dihedral angle of 88.4 (1)°. The crystal structure is stabilized by very weak intramolecular C—H⋯O hydrogen bonding.

Related literature

For applications of phosphorus containing macrocycles, see: Lehn (1988 ▶); Cram (1988 ▶). For their biological activity, see: Sankar et al. (2009 ▶). For P=S bond lengths in related structures, see: Dutasta et al. (1979 ▶).

Experimental

Crystal data

C₂₅H₂₈NO₂PS
M _r = 437.52
Monoclinic,
a = 8.7117 (9) Å
b = 16.3225 (16) Å
c = 16.9021 (16) Å
β = 99.525 (10)°
V = 2370.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.30 × 0.24 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
21854 measured reflections
7063 independent reflections
3672 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.161
S = 1.03
7063 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CryAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CryAlis PRO; data reduction: CryAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ZORTEPII (Zsolnai, 1997 ▶); software used to prepare material for publication: PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052180/pb2015sup1.cif

e-66-0o120-sup1.cif^{(24KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052180/pb2015Isup2.hkl

e-66-0o120-Isup2.hkl^{(333.3KB, hkl)}

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
C23—H23A⋯O3	0.96	2.39	2.848 (3)	109

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Acknowledgments

MK thanks the University Grants Commission, New Delhi, for sanctioning the major research project for this work.

supplementary crystallographic information

Comment

Phosphorus containing macrocycles are interesting molecules with potential applications in supramolecular and synthetic organic chemistry. The molecules found numerous industrial (Lehn, 1988) and biological (Cram, 1988) applications and also function as good hosts in the host–guest chemistry. The present title compound possesses antimicrobial activity against gram positive Staphylococcus aureus, gram negative Escherichia coli and antifungal activity against Aspergillus niger, Helminthosporium oryzae. It also exhibits equal antimicrobial and antifungal activities when compared with that of standard Penicillin and Griseofulvin (Sankar et al., 2009).

The P=S bond length, 1.913Å is in good agreement with the related structure (Dutasta et al., 1979). The crown conformation makes P—N bond length[3.133 Å] smaller than the Van der Waal's radii[3.35 Å] in such a way, which is favourable for P—N coordination. It is interesting to mention that the geometrical parameters between the two fragments from P to N of the ten membered heterocyclic ring are equal within the experimental limitations. The sulfur substituted at P and the methyl substituted at N are almost orthogonally oriented to the mean plane of cyclodecene. The bond angles O(3)—P(1)=S(2) and O(4)—P(1)=S(2) are identical to each other and same is the case with the bond angles O(3)—P(1)—C(25), O(4)—P(1)—C(25)and C(14)—N(5)—C(15),C(16)—N(5)—C(15). The crystal structure is stabilized by intra molecular C—H···O hydrogen bonding. The packing of the molecules is along [110] plane (figure 2).

Experimental

A solution of phenyl dichlorophosphine (300 mg, 2 mmol) in 25 ml of dry toluene was added dropwise over a period of 20 minutes to a stirred solution of bis(2,4-dimethyl-2-hydroxybenzyl)methylamine (600 mg, 2 mmol) and triethyl amine (404 mg, 4 mmol) in 25 ml of dry toluene at 0°C under N₂ atmosphere. After the addition, the temperature of the reaction mixture was raised to room temperature and stirred for 3 h, later the reaction mixture was stirred at 30°C for another 3 h. The triethylamine hydrochloride was removed by filtration. The intermediate obtained was dissolved in dry toluene (30 ml) and sulfur was added at room temperature. The reaction mixture was brought to reflux and kept with stirring for 2 h for the completion of reaction was indicated by TLC analysis. The solvent was removed in a rota-evaporator. The resulting crude product was crystallized by 2-propanol, rectangular shaped single crystals are obtained for diffraction studies.