N-(3-Fluoro­benzo­yl)-N′,N′′-bis­(4-methyl­phen­yl)phospho­ric triamide

Mehrdad Pourayoubi; Samad Shoghpour; Giuseppe Bruno; Hadi Amiri Rudbari

doi:10.1107/S1600536811045314

. 2011 Oct 29;67(Pt 11):o3034. doi: 10.1107/S1600536811045314

N-(3-Fluorobenzoyl)-N′,N′′-bis(4-methylphenyl)phosphoric triamide

Mehrdad Pourayoubi ^a,^*, Samad Shoghpour ^a, Giuseppe Bruno ^b, Hadi Amiri Rudbari ^b

PMCID: PMC3247428 PMID: 22220046

Abstract

In the title compound, C₂₁H₂₁FN₃O₂P, the NH and P(=O) groups of the C(=O)NHP(=O) fragment are in a syn arrangement with respect to each other, as are the two amide H atoms of the two CH₃–4-C₆H₄–NH moieties. In the crystal, molecules are linked through N—H⋯O(=P) and N—H⋯O(=C) hydrogen bonds, forming R ₂ ²(8) and R ₂ ²(12) rings, which are arranged in chains parallel to [010].

Related literature

For hydrogen-bond patterns in phosphoric triamides of the formula RC(O)NHP(O)[NR ¹ R ²]₂ and RC(O)NHP(O)[NHR ¹]₂, see: Toghraee et al. (2011 ▶). For different cyclic hydrogen-bond motifs, see: Pourayoubi et al. (2011 ▶).

Experimental

Crystal data

C₂₁H₂₁FN₃O₂P
M _r = 397.38
Monoclinic,
a = 10.2132 (5) Å
b = 9.8588 (4) Å
c = 20.2711 (9) Å
β = 93.621 (2)°
V = 2037.02 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.662, T _max = 0.745
20105 measured reflections
3844 independent reflections
3061 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.109
S = 1.04
3844 reflections
255 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX (Dolomanov et al., 2003 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811045314/lh5349sup1.cif

e-67-o3034-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045314/lh5349Isup2.hkl

e-67-o3034-Isup2.hkl^{(184.6KB, 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—H1⋯O2ⁱ	0.86	1.97	2.7835 (18)	157
N3—H3⋯O1ⁱⁱ	0.86	2.06	2.8972 (18)	165

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

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

supplementary crystallographic information

Comment

The possible hydrogen bond patterns in crystal structure of phosphoric triamides of the general formula RC(O)NHP(O)[NR¹R²]₂ and RC(O)NHP(O)[NHR¹]₂ have been analyzed recently (Toghraee et al., 2011) and the hydrogen bonds strengths in these systems were discussed based on cyclic hydrogen bond motifs (Pourayoubi et al., 2011). It was concluded that the R₂²(8) ring motif is generated by a pair of P(═O)···H–N_C(O)NHP(O) hydrogen bonds between two neighboring molecules in the crystal packing of phosphoric triamides of the formula RC(O)NHP(O)[NR¹R²]₂ which contain a syn orientation of P(═O) versus N—H. In the case of phosphoric triamides of the formula RC(O)NHP(O)[NHR¹]₂, crystal structure is usually composed of a chain of R₂²(8) and R₂²(12) ring motifs which alternately connected to each other. However, a few other hydrogen bond patterns were also found. The R₂²(8) motif is formed by two P(═O)···H–N_C(O)NHP(O) hydrogen bonds and the R₂²(12) motif by two C(═O)···H–N_amide hydrogen bonds. In this work, the synthesis and crystal structure of a new phosphoric triamide, P(O)[NHC(O)C₆H₄(3-F)][NH–C₆H₄–4–CH₃]₂, is reported. This investigation was carried out as part of a comprehensive study on the hydrogen bonds pattern in phosphoric triamides with formula RC(O)NHP(O)[NHR¹]₂. The phosphorus atom has a distorted tetrahedral environment (Fig. 1). Comparison of the O–P–N angles indicates that the O–P–N1 angle is smaller than ideal tetrahedral (107.02 (7)°) and the O–P–N2 and O–P–N3 angles (113.75 (7)° and 116.29 (7)°, respectively) display larger than ideal values. This probably arises due to steric repulsion involving the P(═O) group. Moreover, there is no π···π interaction between the two para-methyl phenyl groups. The C(═O) and P(═O) groups of the C(═O)NHP(═O) moiety are in anti positions relative to each other, contrary to the syn orientation of P(═O) and NH groups. The P(═O), C(═O) and P–N bond lengths and P–N–C bond angles are in the range of the expected values. In the crystal structure, molecules are linked through P(═O)···H–N_C(O)NHP(O) and C(═ O)···H–N_amide hydrogen bonds (Table 1), to give a linear chain running along the b axis.

Experimental

Synthesis of 3-F–C₆H₄C(O)NHP(O)Cl₂ A mixture of phosphorus pentachloride (3.773 g, 18.12 mmol) and 3-fluorobenzamide (2.521 g, 18.12 mmol) were refluxed in CCl₄ for 8 h, and then the resulting solution was cooled to the room temperature. Formic acid (0.834 g, 18.12 mmol) was syringed dropwise into the stirring solution in 20 min and stirred for 6 h to yield the white precipitate that was filtered and dried in vacuum.

Synthesis of the title molecule To a solution of 3-F–C₆H₄C(O)NHP(O)Cl₂ (0.256 g, 1 mmol) in CHCl₃ (20 ml), a mixture of p-toluidine (0.214 g, 2 mmol) and triethylamine (0.202 g, 2 mmol) in CHCl₃ (5 ml) was added dropwise at 273 K. After 4 h stirring, the solvent was evaporated in vacuum and then the resulting solid was washed with distilled water. Single crystals of title compound were obtained from a mixture of CH₃OH, CH₃CN and n-C₆H₁₄ after slow evaporation at room temperature. IR (KBr, cm^-1): 3355 (NH), 3313 (NH), 3081 (NH), 2921, 1651 (C═O), 1615, 1588, 1513, 1440, 1386, 1267, 1235, 1210, 961, 870, 861, 817, 751.