O-Phenyl (tert-butyl­amido)(p-tolyl­amido)­phosphinate

Mehrdad Pourayoubi; Arnold L Rheingold; Chao Chen; Fatemeh Karimi Ahmadabad; Atekeh Tarahhomi

doi:10.1107/S1600536811048537

. 2011 Nov 23;67(Pt 12):o3405–o3406. doi: 10.1107/S1600536811048537

O-Phenyl (tert-butylamido)(p-tolylamido)phosphinate

Mehrdad Pourayoubi ^a,^*, Arnold L Rheingold ^b, Chao Chen ^b, Fatemeh Karimi Ahmadabad ^a, Atekeh Tarahhomi ^a

PMCID: PMC3239044 PMID: 22199892

Abstract

In the title molecule, C₁₇H₂₃N₂O₂P, the P atom has a distorted tetrahedral environment. The P—N bond to the tolylamido fragment is 1.642 (4) Å while that to the butylamido fragment is 1.629 (3) Å. The dihedral angle between the two benzene rings is 82.3 (2)°. In the crystal, adjacent molecules are linked via weak N—H⋯(O)P and N—H⋯N hydrogen-bonding interactions into an extended chain parallel to the b axis. The three methyl groups of the tert-butylamido substituent are disordered over two sets of sites with equal occupancies. The crystal studied was found to be a non-merohedral twin with the minor twin component = 23.1 (1)%.

Related literature

For background to mixed-amido phosphinates, see: Pourayoubi et al. (2011a ▶); Sabbaghi et al. (2011 ▶). For the sp ² character of the nitrogen atom of the P(=O)N unit and also for its low Lewis-base character in acting as a hydrogen-bond acceptor, see: Toghraee et al. (2011 ▶); Pourayoubi et al. (2011b ▶,c ▶). For a description of the Cambridge Structure Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₇H₂₃N₂O₂P
M _r = 318.34
Monoclinic,
a = 11.412 (5) Å
b = 9.519 (4) Å
c = 15.768 (6) Å
β = 104.332 (5)°
V = 1659.5 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100 K
0.20 × 0.18 × 0.15 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008a ▶) T _min = 0.966, T _max = 0.974
18075 measured reflections
3860 independent reflections
2497 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.089
wR(F ²) = 0.203
S = 1.08
3860 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: CELL_NOW (Sheldrick, 2008a ▶) and SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b ▶) and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811048537/wm2550sup1.cif

e-67-o3405-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048537/wm2550Isup2.hkl

e-67-o3405-Isup2.hkl^{(189.2KB, 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⋯N2ⁱ	0.88	2.32	3.175 (5)	163
N2—H2⋯O1ⁱⁱ	0.88	2.40	3.275 (5)	170

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

Acknowledgments

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

supplementary crystallographic information

Comment

Following our previous work on the synthesis of mixed-amido phosphinates containing a P(O)(O)(NH)(NH) skeleton (Pourayoubi et al., 2011a), we report here on the synthesis and crystal structure of the title compound, P(O)[OC₆H₅][NHC₆H₄(4-CH₃)][NHC(CH₃)₃] (Fig. 1).

The P═O, P—O and P—N bond lengths and P—O—C and P—N—C bond angles are within the expected values (Sabbaghi et al., 2011). The P atom has a distorted tetrahedral conformation with the bond angles in the range of 96.76 (17)° [O2–P1–N2] to 117.03 (17)° [O1–P1–N2]. The P1—N1 bond (with length of 1.642 (4) Å) is slightly longer than the P1—N2 bond (1.629 (3) Å). The dihedral angle between the phenyl rings of the OC₆H₅ and NHC₆H₄(4-CH₃) moieties is 82.3 (2)°.

In the crystal structure, the molecules are linked by weak N—H···(O)P and N—H···N hydrogen bonding interactions (Table 1) into an extended chain along [010] (Fig. 2). As illustrated for phosphoramidates by Toghraee et al. (2011) and Pourayoubi et al. (2011b,c) by examining all deposited phosphoramidates in the Cambridge Structural Database (CSD, Version 5.32, May 2011 update; Allen, 2002), the N atom of the P(═O)N unit usually adopts an sp² character (which is reflected in the bond angles at the N atom) and usually does not act as an acceptor in hydrogen bonding interactions. Therefore, the N—H···N—P contact in the crystal packing may rather be attributed to the assembly of the molecules with respect to one another.

Experimental

To a solution of (C₆H₅O)(4-CH₃C₆H₄NH)P(O)Cl (1.714 mmol) in chloroform, a solution of tert-butylamine (3.428 mmol) in chloroform was added at 273 K. After 5 h stirring, the solvent was removed in vacuum and the solid product was washed with distilled water. Single crystals were obtained from a mixture of CH₃CN/CHCl₃ at room temperature.