N,N′-Dibenzyl-N,N′-dimethyl-N′′-(4-nitro­benzo­yl)phospho­ric triamide

Mehrdad Pourayoubi; Mahnaz Rostami Chaijan; Laura Torre-Fernández; Santiago García-Granda

doi:10.1107/S1600536811011275

. 2011 Apr 7;67(Pt 5):o1031. doi: 10.1107/S1600536811011275

N,N′-Dibenzyl-N,N′-dimethyl-N′′-(4-nitrobenzoyl)phosphoric triamide

Mehrdad Pourayoubi ^a, Mahnaz Rostami Chaijan ^a, Laura Torre-Fernández ^b, Santiago García-Granda ^b,^*

PMCID: PMC3089276 PMID: 21754361

Abstract

The P atom in the title compound, C₂₃H₂₅N₄O₄P, is in a slightly distorted tetrahedral coordination environment and the N atoms show sp ² character. The phosphoryl group and the NH unit are syn with respect to each other. In the crystal, pairs of intermolecular N—H⋯O(P) hydrogen bonds form centrosymmetric dimers.

Related literature

For phosphorus compounds with general formula XP(O)[N(CH₃)(CH₂C₆H₅)]₂, see: Gholivand et al. (2005 ▶). For bond lengths in a related structure, see: Sabbaghi et al. (2010 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₃H₂₅N₄O₄P
M _r = 452.44
Triclinic,
a = 8.3526 (5) Å
b = 11.8150 (5) Å
c = 12.2668 (4) Å
α = 77.184 (3)°
β = 81.289 (4)°
γ = 71.928 (4)°
V = 1117.70 (9) Å³
Z = 2
Cu Kα radiation
μ = 1.41 mm⁻¹
T = 297 K
0.24 × 0.14 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.941, T _max = 1.000
8669 measured reflections
4203 independent reflections
3779 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.093
S = 1.05
4203 reflections
390 parameters
All H-atom parameters refined
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011275/ng5139sup1.cif

e-67-o1031-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011275/ng5139Isup2.hkl

e-67-o1031-Isup2.hkl^{(205.9KB, 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
N8—H8⋯O2ⁱ	0.85 (2)	2.07 (2)	2.909 (2)	169 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Spanish Ministerio de Educacion y Ciencia (MAT2006–01997, MAT2010–15094 and the ‘Factoría de Cristalización’ Consolider Ingenio 2010) and FEDER funding is acknowledged.

supplementary crystallographic information

Comment

Some phosphoric triamide compounds of the general formula XP(O)[N(CH₃)(CH₂C₆H₅)]₂ [X = Cl, C₆H₅C(O)NH & CCl₃C(O)NH (Gholivand et al., 2005) have been structurally investigated. Here, we report on the synthesis and crystal structure of title compound (where X = 4-NO₂C₆H₄C(O)NH).

The asymmetric unit consists of a single molecule, shown in Fig. 1, of the title compound with no unusual bonding features. The P═O and P—N bond lengths are comparable to those in similar compounds like for example in P(O)[NHC(O)C₆H₄(4-NO₂)][NHC₆H₁₁]₂ (Sabbaghi et al., 2010). As can be expected, the N8—C26 bond length is shorter than the other N—C bonds in the molecule.

The phosphorus atom has a slightly distorted tetrahedral configuration, the bond angles around the P atom are in the range of 103.85 (6)° [N6—P1—N7] to 118.67 (6)° [O2—P1—N7]. The average of surrounding angles around the tertiary nitrogen atom N6 (119.7°) shows that it is bonded in an essentially planar geometry; whereas, the environment of N7 is slightly deviated from planarity (average of bond angles around N7 atom is equal to 117.3°). Furthermore, the angle C26—N8—P1 is 124.98 (10)°.

The oxygen atom of P═O group is a better H-acceptor than that of the C═ O counterpart; so, the hydrogen atom of the C(O)NHP(O) moiety is involving in an intermolecular –P═O···H—N– hydrogen bond (see Table 1) to form a centrosymmetric dimer [graph set: R₂²(8) (Etter et al., 1990; Bernstein et al., 1995)].

Experimental

4-NO₂—C₆H₄C(O)NHP(O)Cl₂ was prepared according to the procedure of literature (Sabbaghi et al., 2010). To a solution of (2 mmol) 4-NO₂C₆H₄C(O)NHP(O)Cl₂ in CH₃CN (20 ml), a solution of N-methylbenzyl amine (8 mmol) in CH₃CN (5 ml) was added dropwise at 273 K. After 4 h stirring, the solvent was removed in vacuum. Single crystals were obtained from a solution of title compound in C₂H₅OH after slow evaporation at room temperature. IR (KBr, cm^-1): 3141, 2881, 1680, 1604, 1522, 1452, 1342, 1273, 1186, 1104, 1005, 949, 853, 793, 708.