Diphenyl (benzyl­amido)phosphate

Mehrdad Pourayoubi; Hossein Eshtiagh-Hosseini; Poorya Zargaran; Vladimir Divjakovic

doi:10.1107/S1600536809053744

. 2009 Dec 19;66(Pt 1):o204. doi: 10.1107/S1600536809053744

Diphenyl (benzylamido)phosphate

Mehrdad Pourayoubi ^a,^*, Hossein Eshtiagh-Hosseini ^a, Poorya Zargaran ^a, Vladimir Divjakovic ^b

PMCID: PMC2980091 PMID: 21580089

Abstract

The title compound, C₁₉H₁₈NO₃P, was prepared by the reaction of diphenyl phosphorochloridate and benzylamine. In the crystal structure, molecules are linked via N—H⋯O=P hydrogen bonds into extended chains parallel to the c axis.

Related literature

For related structures, see: Bao & Wulff (1993 ▶); Gholivand et al. (2005 ▶); Karolak-Wojciechowska et al. (1979 ▶).

Experimental

Crystal data

C₁₉H₁₈NO₃P
M _r = 339.31
Monoclinic,
a = 10.0226 (5) Å
b = 19.2450 (8) Å
c = 10.2273 (5) Å
β = 115.375 (6)°
V = 1782.38 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 295 K
0.43 × 0.28 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire3 (Gemini Mo) detector
Absorption correction: multi-scan CrysAlis PRO (Oxford Diffraction, 2009 ▶) T _min = 0.977, T _max = 1.000
8248 measured reflections
4105 independent reflections
2568 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.102
S = 0.91
4105 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809053744/lh2963sup1.cif

e-66-0o204-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053744/lh2963Isup2.hkl

e-66-0o204-Isup2.hkl^{(197.1KB, 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
N—H⋯O3ⁱ	0.86	1.97	2.8241 (15)	175

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Symmetry code: (i) Inline graphic .

Acknowledgments

Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged.

supplementary crystallographic information

Comment

In previous work, the synthesis and X-ray structures of some amidophosphoric acid ester compounds, such as [(C₆H₅)(CH₃)CH—NH]P(O)(p—OC₆H₄CH₃)₂ (Gholivand et al., 2005) and P(O)[OC₆H₅]₂[N(CH₂C₆H₅)(C(S)NHCH₂C₆H₅)] (Karolak-Wojciechowska et al., 1979) have been investigated. We report here on the synthesis and crystal structure of a new amido bis(phosphoric acid ester) compound, [C₆H₅—CH₂—NH]P(O)[O—C₆H₅]₂. The title compound was synthesized from the reaction of diphenyl phosphorochloridate with an excess amount of benzylamine. The P—O3 bond length of 1.4567 (10) Å and the P—N bond length of 1.5952 (14) Å are standard for this type of compound [for example for two crystallographically different [(C₆H₅)(CH₃)CH—NH]P(O)(p—OC₆H₄CH₃)₂ molecules (Gholivand et al., 2005), P═O = 1.462 (3) Å and 1.469 (3) Å and P—N = 1.610 (5) Å and 1.614 (5) Å and for the heterocyclic phosphorus compound obtained from sequential treatment of (+)2,2'-diphenyl-3,3'-biphenanthrol with phosphorus oxychloride and (S)-(-)-α-methylbenzylamine (Bao & Wulff, 1993) P═O = 1.456 (6) Å, P—N = 1.612 (7)]. In the title copmound, the P—O1 and P—O2 bond lengths are slightly different (1.5844 (12) Å and 1.5880 (12) Å) and the P atom has a distorted tetrahedral configuration (Fig. 1); the bond angles around the P atom are in the range of 98.80 (6)° [for the O1—P—O2 angle] to 114.84 (7)° [for the O3—P—O1 angle]. Molecules are linked via N—H···O═P hydrogen bonds (N···O3 = 2.8241 (15) Å) into extended chains parallel to the c axis (Fig. 2).

Experimental

To a solution of diphenyl phosphorochloridate (0.572 g, 2.13 mmol) in chloroform (15 ml), a solution of benzylamine (0.456 g, 4.26 mmol) in chloroform (30 ml) was added at 273K. After 4 h of stirring, the solvent was evaporated in vacuum. The solid was washed with distilled water. Single crystals were obtained from a solution of the title compound in chloroform and n-heptane (4:1) after slow evaporation at room temperature. IR (KBr, cm^-1): 3165 s, 2891 m, 2680 w, 2221 w, 1952 w, 1592 m, 1475 s, 1242 vs, 1198 vs, 1116 s, 1004 m, 931 vs, 759 s, 687 s.