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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1102.
Published online 2010 April 17. doi:  10.1107/S1600536810013589
PMCID: PMC2979112

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

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

An external file that holds a picture, illustration, etc.
Object name is e-66-o1102-scheme1.jpg

Experimental

Crystal data

  • C6H13Cl3N3O2P
  • M r = 296.51
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1102-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.40 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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(PNamine)), 867 (ν(PNamide)), 676 (ν(CCl)).

Refinement

Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Figures

Fig. 1.
Structural representation of 1 with atom numbering scheme and 50% probability thermal ellipsoid. The hydrogen atoms are omitted for clarity.
Fig. 2.
A projection of packing diagram of the title compound along the y direction. Hydrogen bonds are indicated by dashed lines. H and Cl atoms are omitted for clarity.

Crystal data

C6H13Cl3N3O2PF(000) = 1216
Mr = 296.51Dx = 1.619 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 35140 reflections
a = 15.794 (3) Åθ = 3.6–36.1°
b = 15.820 (3) ŵ = 0.87 mm1
c = 9.739 (2) ÅT = 100 K
V = 2433.4 (8) Å3Block, white
Z = 80.60 × 0.40 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer5631 independent reflections
Radiation source: Enhance (Mo) X-ray Source4869 reflections with I > 2σ(I)
graphiteRint = 0.032
Detector resolution: 8.3359 pixels mm-1θmax = 36.1°, θmin = 3.6°
ω scansh = −26→26
Absorption correction: gaussian Coppens et al. (1965)k = −25→25
Tmin = 0.624, Tmax = 0.845l = −12→15
35140 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 1.15w = 1/[σ2(Fo2) + (0.0336P)2 + 0.5268P] where P = (Fo2 + 2Fc2)/3
5631 reflections(Δ/σ)max = 0.001
144 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
P10.285320 (15)0.522358 (14)0.42665 (2)0.00982 (5)
C10.14518 (6)0.60952 (6)0.48883 (9)0.01181 (14)
C20.06928 (6)0.62610 (5)0.58869 (9)0.01177 (15)
Cl10.033556 (15)0.534225 (14)0.67522 (3)0.01615 (5)
Cl20.104133 (16)0.701650 (14)0.71094 (2)0.01672 (5)
Cl3−0.015884 (16)0.668869 (15)0.49346 (3)0.01985 (6)
O10.26191 (5)0.51406 (5)0.28033 (7)0.01480 (12)
O20.15469 (5)0.65692 (5)0.39188 (8)0.02050 (15)
N10.19672 (5)0.54418 (5)0.52192 (8)0.01086 (13)
N20.35444 (5)0.59761 (5)0.45503 (8)0.01341 (14)
N30.32000 (5)0.43758 (5)0.50197 (9)0.01413 (14)
C30.36307 (7)0.63290 (7)0.59326 (10)0.01877 (18)
H3A0.34490.59080.66100.028*
H3B0.32770.68350.60140.028*
H3C0.42240.64790.60990.028*
C40.37770 (7)0.65551 (6)0.34435 (11)0.01709 (17)
H4A0.34340.70700.35100.026*
H4B0.36750.62820.25560.026*
H4C0.43780.67020.35230.026*
C50.40306 (6)0.42489 (7)0.56243 (11)0.01898 (18)
H5A0.43710.47620.55070.028*
H5B0.43130.37740.51690.028*
H5C0.39690.41260.66050.028*
C60.26438 (7)0.36368 (6)0.51134 (12)0.01950 (19)
H6A0.29060.31580.46360.029*
H6B0.20980.37670.46860.029*
H6C0.25560.34910.60810.029*
H1N0.1961 (10)0.5241 (9)0.6005 (17)0.023 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.01062 (9)0.01090 (9)0.00794 (9)0.00005 (7)0.00106 (7)−0.00067 (7)
C10.0138 (4)0.0121 (3)0.0095 (3)0.0019 (3)−0.0007 (3)−0.0001 (3)
C20.0123 (3)0.0113 (3)0.0117 (4)0.0021 (3)−0.0013 (3)−0.0018 (3)
Cl10.01546 (10)0.01469 (9)0.01831 (11)−0.00068 (7)0.00464 (8)0.00048 (7)
Cl20.02070 (10)0.01642 (10)0.01304 (10)−0.00216 (7)−0.00055 (8)−0.00503 (7)
Cl30.01663 (10)0.01936 (10)0.02357 (12)0.00705 (8)−0.00704 (9)−0.00265 (8)
O10.0174 (3)0.0188 (3)0.0082 (3)−0.0010 (2)0.0010 (2)−0.0026 (2)
O20.0275 (4)0.0196 (3)0.0144 (3)0.0069 (3)0.0044 (3)0.0073 (3)
N10.0119 (3)0.0131 (3)0.0076 (3)0.0026 (2)0.0013 (2)0.0018 (2)
N20.0165 (3)0.0145 (3)0.0092 (3)−0.0034 (3)0.0001 (3)−0.0002 (2)
N30.0116 (3)0.0120 (3)0.0188 (4)0.0006 (2)−0.0001 (3)0.0027 (3)
C30.0226 (5)0.0203 (4)0.0134 (4)−0.0056 (3)−0.0021 (3)−0.0032 (3)
C40.0195 (4)0.0157 (4)0.0160 (4)−0.0041 (3)0.0007 (3)0.0031 (3)
C50.0147 (4)0.0214 (4)0.0208 (5)0.0021 (3)−0.0032 (4)0.0047 (4)
C60.0177 (4)0.0124 (4)0.0284 (5)−0.0003 (3)0.0031 (4)0.0013 (3)

Geometric parameters (Å, °)

P1—O11.4780 (8)N3—C61.4652 (13)
P1—N31.6239 (8)C3—H3A0.9800
P1—N21.6388 (8)C3—H3B0.9800
P1—N11.7141 (8)C3—H3C0.9800
C1—O21.2151 (11)C4—H4A0.9800
C1—N11.3546 (12)C4—H4B0.9800
C1—C21.5658 (13)C4—H4C0.9800
C2—Cl31.7684 (9)C5—H5A0.9800
C2—Cl11.7723 (10)C5—H5B0.9800
C2—Cl21.7745 (9)C5—H5C0.9800
N1—H1N0.828 (16)C6—H6A0.9800
N2—C41.4614 (13)C6—H6B0.9800
N2—C31.4637 (13)C6—H6C0.9800
N3—C51.4518 (13)
O1—P1—N3116.53 (4)N2—C3—H3A109.5
O1—P1—N2113.19 (4)N2—C3—H3B109.5
N3—P1—N2107.40 (4)H3A—C3—H3B109.5
O1—P1—N1109.61 (4)N2—C3—H3C109.5
N3—P1—N1101.37 (4)H3A—C3—H3C109.5
N2—P1—N1107.83 (4)H3B—C3—H3C109.5
O2—C1—N1125.55 (9)N2—C4—H4A109.5
O2—C1—C2118.29 (8)N2—C4—H4B109.5
N1—C1—C2116.12 (8)H4A—C4—H4B109.5
C1—C2—Cl3108.70 (6)N2—C4—H4C109.5
C1—C2—Cl1113.68 (6)H4A—C4—H4C109.5
Cl3—C2—Cl1108.72 (5)H4B—C4—H4C109.5
C1—C2—Cl2106.98 (6)N3—C5—H5A109.5
Cl3—C2—Cl2109.28 (5)N3—C5—H5B109.5
Cl1—C2—Cl2109.40 (5)H5A—C5—H5B109.5
C1—N1—P1121.03 (7)N3—C5—H5C109.5
C1—N1—H1N120.3 (11)H5A—C5—H5C109.5
P1—N1—H1N115.7 (11)H5B—C5—H5C109.5
C4—N2—C3114.58 (8)N3—C6—H6A109.5
C4—N2—P1119.89 (7)N3—C6—H6B109.5
C3—N2—P1119.62 (7)H6A—C6—H6B109.5
C5—N3—C6113.97 (8)N3—C6—H6C109.5
C5—N3—P1127.02 (7)H6A—C6—H6C109.5
C6—N3—P1119.00 (7)H6B—C6—H6C109.5
O2—C1—C2—Cl332.74 (11)N3—P1—N2—C4138.23 (8)
N1—C1—C2—Cl3−149.48 (7)N1—P1—N2—C4−113.24 (8)
O2—C1—C2—Cl1153.97 (8)O1—P1—N2—C3159.66 (7)
N1—C1—C2—Cl1−28.25 (10)N3—P1—N2—C3−70.29 (8)
O2—C1—C2—Cl2−85.16 (10)N1—P1—N2—C338.24 (9)
N1—C1—C2—Cl292.62 (8)O1—P1—N3—C5118.05 (9)
O2—C1—N1—P11.02 (14)N2—P1—N3—C5−10.10 (10)
C2—C1—N1—P1−176.58 (6)N1—P1—N3—C5−123.08 (9)
O1—P1—N1—C1−53.07 (8)O1—P1—N3—C6−61.17 (9)
N3—P1—N1—C1−176.80 (7)N2—P1—N3—C6170.68 (7)
N2—P1—N1—C170.54 (8)N1—P1—N3—C657.70 (8)
O1—P1—N2—C48.18 (9)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.828 (16)1.968 (16)2.7586 (11)159.3 (16)

Symmetry codes: (i) −x+1/2, −y+1, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: JH2144).

References

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