rac-Phenyl (benzylamido)(p-tolyl­amido)­phosphinate

Mehrdad Pourayoubi; Fatemeh Karimi Ahmadabad; Marek Nečas

doi:10.1107/S1600536811034465

. 2011 Aug 31;67(Pt 9):o2523. doi: 10.1107/S1600536811034465

rac-Phenyl (benzylamido)(p-tolylamido)phosphinate

Mehrdad Pourayoubi ^a,^*, Fatemeh Karimi Ahmadabad ^a, Marek Nečas ^b

PMCID: PMC3200931 PMID: 22059060

Abstract

The title compound, C₂₀H₂₁N₂O₂P, was synthesized from (RS)-(C₆H₅O)P(O)Cl(NHC₆H₄-p-CH₃) and benzylamine. The product crystallizes as a racemate in a polar space group. The phosphorus atom has a distorted tetrahedral configuration: the bond angles at the P atom are in the range 103.2 (1)–118.4 (1)°. The P—N(benzylamido) bond [1.615 (2) Å] is slightly shorter than the P—N(p-tolylamido) bond [1.630 (2) Å]. Both N—H groups adopt an anti orientation relative to the phosphoryl group. In the crystal, the adjacent molecules are linked via N—H⋯O hydrogen bonds, forming R ₂ ²(8) rings, into a one-dimensional arrangement parallel to the x axis.

Related literature

For a related mixed-amido phosphinate derivative and its molecular geometry, see: Sabbaghi et al. (2011 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₀H₂₁N₂O₂P
M _r = 352.36
Orthorhombic,
a = 9.6986 (5) Å
b = 13.0751 (6) Å
c = 14.3446 (5) Å
V = 1819.04 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 120 K
0.30 × 0.30 × 0.10 mm

Data collection

Xcalibur, Sapphire2, large Be window diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.785, T _max = 1.000
20413 measured reflections
3200 independent reflections
2823 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.099
S = 1.00
3200 reflections
233 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ▶), 1526 Friedel pairs
Flack parameter: 0.01 (10)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811034465/ld2023sup1.cif

e-67-o2523-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034465/ld2023Isup2.hkl

e-67-o2523-Isup2.hkl^{(157KB, 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⋯O1ⁱ	0.76 (3)	2.43 (3)	3.127 (3)	153 (3)
N2—H2N⋯O2ⁱ	0.86 (3)	1.91 (3)	2.761 (3)	176 (3)

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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 continuation of the previous works on synthesis and structure determination of mixed-amido phosphinates with common formula (RO)(NR¹R²)(NR³R⁴)P(O) (Sabbaghi et al., 2011; and the related reference cited therein), the structure of the title molecule, [C₆H₅O][4-CH₃C₆H₄NH][C₆H₅CH₂NH]PO (Fig. 1), is reported here.

Single crystals were obtained from CHCl₃/CH₃CN at room temperature.

The P═O (1.4679 (17) Å), P—O (1.6250 (17) Å), P—N (1.615 (2) Å & 1.630 (2) Å) and C—O (1.400 (3) Å) bond lengths and the P—N—C (120.54 (18)° & 125.18 (18)°) and P—O—C (120.90 (14)°) bond angles are within the expected values (Sabbaghi et al., 2011).

The phosphorus atom has a distorted tetrahedral P(═O)(O)(N)(N) environment. The bond angles at the P atom are in the range from 103.17 (9)° [for the O2—P1—O1 angle] to 118.39 (11)° [for the O2—P1—N2 angle].

In the crystal structure, neighbouring molecules are H-bonded via N—H···O(P) hydrogen bonds, building R₂²(8) rings (Bernstein et al., 1995), in a linear arrangement parallel to [100], Table 1, Fig. 2.

Experimental

To a solution of (C₆H₅O)(4-CH₃C₆H₄NH)P(O)Cl (2.286 mmol) in chloroform, a solution of benzylamine (4.572 mmol) in chloroform was added at 273 K. After stirring for 5 h, the solvent was removed and the obtained solid was washed with distilled water. Single crystals were obtained from a solution of the title compound in CH₃CN/CHCl₃ after slow evaporation at room temperature.