N-[Bis(benzylamino)phosphoryl]-2,2,2-trichloroacetamide

Vladimir A Ovchynnikov

doi:10.1107/S1600536810017873

. 2010 May 22;66(Pt 6):o1425. doi: 10.1107/S1600536810017873

N-[Bis(benzylamino)phosphoryl]-2,2,2-trichloroacetamide

Vladimir A Ovchynnikov ^a,^*

PMCID: PMC2979604 PMID: 21579501

Abstract

In the title compound, C₁₆H₁₇Cl₃N₃O₂P, the P atom has a slightly distorted tetrahedral configuration. The conformations of the carbonyl and phosphoryl groups are anti to each other. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into infinite chains parallel to the b axis.

Related literature

For the use of carbacylamidophosphates as potential new ligands, see: Skopenko et al. (1996 ▶); Ovchynnikov et al. (1998 ▶); Znovjak et al. (2009 ▶); Gubina et al. (2009 ▶); Gowda et al. (2010 ▶); Amirkhanov et al. (1997a ▶); Safin et al. (2009 ▶). For their biological activity, see: Amirkhanov et al. (1996 ▶); Rebrova et al. (1982 ▶). For P=O bond lengths, see: Amirkhanov et al. (1997b ▶). For the synthesis of the title compound, see: Kirsanov & Derkach (1956 ▶).

Experimental

Crystal data

C₁₆H₁₇Cl₃N₃O₂P
M _r = 420.65
Triclinic,
a = 9.116 Å
b = 10.3586 (2) Å
c = 11.7713 (2) Å
α = 68.320 (1)°
β = 67.762 (1)°
γ = 86.469 (1)°
V = 952.13 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.893, T _max = 0.893
4976 measured reflections
3286 independent reflections
3069 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.103
S = 1.05
3286 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017873/dn2554sup1.cif

e-66-o1425-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017873/dn2554Isup2.hkl

e-66-o1425-Isup2.hkl^{(157.9KB, 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
N1—H1⋯O1ⁱ	0.86	1.95	2.790 (2)	167
N2—H2⋯O2ⁱⁱ	0.86	2.23	3.055 (2)	161

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

Acknowledgments

The author thanks Professor Joachim Sieler for his help with the data collection.

supplementary crystallographic information

Comment

Carbacylamidophosphates of the general formula RC(O)NHP(O)R₂ are potential new ligands for metal ions (Skopenko et al., 1996; Ovchynnikov et al., 1998; Znovjak et al., 2009; Gubina et al., 2009; Amirkhanov et al., 1997a; Gowda et al., 2010; Safin et al., 2009). Many of these compounds also show biological activity, including anticancer activity (Amirkhanov et al., 1996; Rebrova et al., 1982). This work reports the structure of N,N'-dibenzyl-N"-trichloroacetylphosphortriamide (HDBA).

In the title compound, the phosphorus atom has a slightly distorted tetrahedral configuration (Fig.1). The average values of the angles OPN in the molecule are larger than tetrahedral, while the N – P – N angles are smaller, with the exception O1 – P1– N1 106.85 (7) ° and N(1) – P1– N(2) 112.32 (7) °, which can be rationalized by the influence of the hydrogen bonds. The environment of the nitrogen atoms is practically planar with only slight deviations from the mean planes.

The bond length P ═O (1.479 (1) Å is longer than in the compounds with alkyl amide substituents (the range of bond length d_(P_═_O) 1.475 - 1.478 Å) (Amirkhanov et al., 1997b). In the structure the carbonyl and phosphoryl groups are anti to each other as in most carbacylamidophosphates.

The fragment including the atoms O(2), N(1), C(1), C(2) is virtually planar, with only slight deviations from the mean plane. The phosphorus and oxygen atom of the phosphoryl group do not fit into this plane. Close enough to this plane lie the hydrogen H(1 N) and one of the chlorine atoms Cl(3). The carbonyl oxygen-phosphorus distance 3.023 (1) Å is considerably shorter than the sum of Van der Waals radii (3.3 Å).

Molecules are linked by hydrogen bonds of the phosphorylic oxygen atoms and the hydrogen atoms of the C(O)N(H)P(O) groups of neighboring molecules. The N—H···O intermolecular hydrogen bonds pack the molecules into infinite chains parallel to the b axis (Table 1, Fig.2).

Experimental

The solution of benzylamine (26.8 g, 0.25 mol) in 30 ml of chloroform was cooled to 10 °C and a solution of the dichloride of trichloroacetylamidophosphoric acid (14 g, 0.047 mol) in 150 ml of chloroform was added slowly with stirring. The temperature was not allowed to rise above 15 °C. Stirring was continued for about 40 min. The resulting mixture, containing HL, H₂NCH₂C₆H₅*HCl and excess dibenzylamine, was filtered from the precipitate (H₂NCH₂C₆H₅*HCl). Then the solution was evaporated and the residue was treated with aqueous HCl; the product precipitated as a yellow crystalline powder (90 % yield) (Kirsanov & Derkach, 1956). A colourless crystalline compound was obtained after recristallization from acetone. The compound is air stable, soluble in alcohols and hot acetone, insoluble in non-polar aprotic solvents and water, M.p. = 144 °C. Anal. Calc.: C 45.68,H 4.07, N 9.99; Found: C 45.73, H 3.95, N 9.85. IR (KBr pellet, cm^-1): 1709 (s, CO) and 1250 (s, PO).