Diphenyl (isopropyl­amido)­phosphate

Fahimeh Sabbaghi; Mehrdad Pourayoubi; Marek Nečas; Michal Babiak

doi:10.1107/S1600536812047940

. 2012 Nov 28;68(Pt 12):o3459. doi: 10.1107/S1600536812047940

Diphenyl (isopropylamido)phosphate

Fahimeh Sabbaghi ^a,^*, Mehrdad Pourayoubi ^b, Marek Nečas ^c, Michal Babiak ^c

PMCID: PMC3589035 PMID: 23476271

Abstract

The P atom in the title compound, C₁₅H₁₈NO₃P, is in a distorted tetrahedral P(O)(O)₂N environment; the bond angles at P are in the range 98.16 (6)–115.82 (6)°. In the crystal, adjacent molecules are linked via N—H⋯O=P hydrogen bonds into a chain running parallel to the b axis. The methyl groups are disordered over two sets of sites in a 0.677 (14):0.323 (14) ratio. The crystal studied was a non-merohedral twin with a refined minor component of 22.31 (4)%.

Related literature

For bond lengths and angles in a related structure, see: Sabbaghi et al. (2011 ▶).

Experimental

Crystal data

C₁₅H₁₈NO₃P
M _r = 291.27
Monoclinic,
a = 8.4432 (5) Å
b = 5.3030 (4) Å
c = 16.3443 (11) Å
β = 90.453 (6)°
V = 731.78 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 120 K
0.45 × 0.42 × 0.40 mm

Data collection

Oxford Diffraction Xcalibur (Sapphire2) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.918, T _max = 0.926
6226 measured reflections
6226 independent reflections
6040 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.081
S = 1.06
6226 reflections
208 parameters
28 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 1229 Friedel pairs
Flack parameter: 0.05 (6)

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Click here for additional data file.^{(25.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812047940/ff2090sup1.cif

e-68-o3459-sup1.cif^{(25.3KB, cif)}

Click here for additional data file.^{(304.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047940/ff2090Isup2.hkl

e-68-o3459-Isup2.hkl^{(304.7KB, 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
N1—H1N⋯O3ⁱ	0.81 (1)	2.23 (1)	3.0065 (17)	161 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Support of this investigation by Zanjan Branch, Islamic Azad University, is gratefully acknowledged.

supplementary crystallographic information

Comment

This work is a continuation of our studies of phosphoramidate compounds, during which the structures of various diphenyl amido phosphates, for example [C₆H₅O]₂P(O)[NHCH(C₂H₅)(C₆H₅)] (Sabbaghi et al., 2011) were reported. Here, we report the synthesis and crystal structure determination of the title compound, [C₆H₅O]₂P(O)[NHCH(CH₃)₂].

The P═O (1.4602 (11) Å), P—O (1.5858 (11) and 1.5896 (11) Å) and P—N (1.6043 (14) Å) bond lengths are within the expected values (Sabbaghi et al., 2011).

The P atom adopts a distorted tetrahedral configuration (Fig. 1). The bond angles at the P atom vary in the range 98.16 (6) [O1—P1—O2] to 115.82 (6)° [O3—P1—O2].

The C—O—P bond angles (124.07 (10) [C1—O1—P1] and 121.74 (10)° [C7—O2—P1]) and the C13A—N1—P1 (124.19 (11)°) bond angle are standard for this category of phosphoramidate compounds (Sabbaghi et al., 2011).

In the crystal structure, molecules are linked via N—H···O═P hydrogen bonds into extended chains running parallel to the b axis (Table 1).

Experimental

To a solution of [C₆H₅O]₂P(O)Cl (2 mmol) in dry CH₃CN (30 ml), a solution of isopropylamine (4 mmol) in the same solvent (5 ml) was added at ice bath temperature under stirring. After 4 h, the solvent was removed and the product was washed with distilled water and recrystallized from CH₃CN/n-C₆H₁₄ (4:1) at room temperature. The single crystals suitable for X-ray analysis were obtained from this solution after a few days at room temperature.