N-[Bis(dimethyl­amino)phosphinoyl]-2,2,2-trichloro­acetamide

Oleksiy V Amirkhanov; Olesia V Moroz; Kateryna O Znovjyak; Elizaveta A Trush; Tetyana Yu Sliva

doi:10.1107/S1600536810013589

. 2010 Apr 17;66(Pt 5):o1102. doi: 10.1107/S1600536810013589

N-[Bis(dimethylamino)phosphinoyl]-2,2,2-trichloroacetamide

Oleksiy V Amirkhanov ^a,^*, Olesia V Moroz ^a, Kateryna O Znovjyak ^a, Elizaveta A Trush ^a, Tetyana Yu Sliva ^a

PMCID: PMC2979112 PMID: 21579154

Abstract

In the title compound, C₆H₁₃Cl₃N₃O₂P or CCl₃C(O)NHP(O)(N(CH₃)₂), the phosphinoyl group is synclinal to the carbonyl group and acts as an acceptor for an intermolecular N—H⋯O hydrogen bond from the amide group as the donor.

Related literature

For the biological and pharmacological properties of carbacylamidophosphate derivatives, see: Adams et al. (2002 ▶); Grimes et al. (2008 ▶). For structural and conformation studies of related molecules, see: Gholivand et al. (2008a ▶,b ▶); Skopenko et al. (2004 ▶); Znovjyak et al. (2009a ▶,b ▶). For details of the synthesis, see: Kirsanov & Derkach (1956 ▶). For P—O bond lengths in compounds with amide substituents close to phosphorus atoms, see: Rebrova et al. (1982 ▶).

Experimental

Crystal data

C₆H₁₃Cl₃N₃O₂P
M _r = 296.51
Orthorhombic,
a = 15.794 (3) Å
b = 15.820 (3) Å
c = 9.739 (2) Å
V = 2433.4 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 100 K
0.60 × 0.40 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer
Absorption correction: Gaussian (Coppens et al., 1965 ▶) T _min = 0.624, T _max = 0.845
35140 measured reflections
5631 independent reflections
4869 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.072
S = 1.15
5631 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013589/jh2144sup1.cif

e-66-o1102-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013589/jh2144Isup2.hkl

e-66-o1102-Isup2.hkl^{(270.2KB, 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—H1N⋯O1ⁱ	0.828 (16)	1.968 (16)	2.7586 (11)	159.3 (16)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful to Dr Yu. S. Moroz for his kind assistance in the preparation of the manuscript.

supplementary crystallographic information

Comment

P, N-substituted analogues of β-diketones – carbacylamidophosphates (CAPh), which comprise C(O)NHP(O) structural fragment, have attracted attention because of their using in pharmacology, as insecticides, pesticides and ureas inhibitor (Adams et al., 2002; Grimes et al., 2008). A variety of new coordination compounds with s-, p-, d- and f-metals based on the CAPh have been synthesized and characterized up to date (Skopenko et al., 2004; Znovjyak et al., 2009a). Thus, the syntheses and structure analysis of CAPh have been of increased interest (Gholivand et al., 2008a). In this paper we report the crystal structure of a new CAPh – N-[bis(dimethylamino)phosphinoyl]-2,2,2-trichloroacetamide (1).

In the crystal packing molecules of 1 are linked to each other by intermolecular hydrogen bonds (N–H···O), where amide nitrogen atom of one molecule acts as donor and oxygen atom of phosphinoyl group of neighboring molecule acts as acceptor (Fig. 2). The bond distance P(1)—O(1) (1.478 (1) Å) is typical for compounds with amide substituents close to phosphorus atoms (Rebrova et al., 1982) and CAPh (Znovjyak et al., 2009b). The values of C(1)—O(2) and C(1)—N(1) are 1.215 (1) Å and 1.355 (1) Å, respectively and close to the corresponding values of the CAPh (Gholivand et al., 2008b). The P(1)—N(1) (1.714 (1) Å) distance in 1 is longer on average by 0.08 Å than P—N bond distances between amide substituents and phosphorus atoms (P(1)—N(2), P(1)—N(3)). The geometry around the phosphorus atom in 1 can be described as a distorted tetrahedron and which is similar to early reported CAPh. The O(1)—P(1)—N(1) angle value is close to near tetrahedral one (109.61 (4)°), while other O—P—N angels have values 113.19 (4)° and 116.53 (4)°, that may be explained by the repulsion between amide substituents and PO group. Fragment O(2)—C(1)—N(1)—P(1) is close to planarity (the torsion angle is -176.6°).

Experimental

The dichloranhydride of trichloroacetylamidophosphoric acid (CCl₃C(O)NHP(O)Cl₂) was prepared according to the method reported by Kirsanov (Kirsanov et al., 1956).

The dioxane solution (200 ml) of CCl₃C(O)NHP(O)Cl₂ (27.9 g, 0.1 mol) was placed in a three-neck round-bottomed flask and cooled by ice to 268 K. Then the dry dimethylamine (18.03 g, 0.4 mol) was bubbled through the dioxane solution of CCl₃C(O)NHP(O)Cl₂ under stirring until the solution became alkaline. The temperature was not allowed to rise above 278 K. The stirring was continued for 1 h and the solution was left under ambient conditions. HN(CH₃)₂^.HCl was filtered off after 12 h and the filtrate was evaporated. The oily precipitate of 1 was isolated and recrystallized from 2-propanol which led to formation of white crystalline powder (yield 80%). White needle-shaped crystals suitable for X-ray analysis were formed over a period of 5 days from the 2-propanol/hexane solution. IR (KBr pellet, cm^-1): 3070 (ν(NH)), 1715 (ν(CO)), 1205 (ν(PO)), 1000 (ν(PN_amine)), 867 (ν(PN_amide)), 676 (ν(CCl)).