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Acta Cryst. (2011). E67, o2792    [ doi:10.1107/S1600536811039511 ]

N,N'-Bis(2-methylphenyl)-N''-(2,2,2-trichloroacetyl)phosphoric triamide

M. Pourayoubi, M. Keikha and M. Parvez

Abstract top

In the title compound, C16H17Cl3N3O2P, the P-N bonds in the P(O)[NH(2-CH3)C6H4]2 unit [1.623 (4) and 1.637 (3) Å] are shorter than the P-N bond in the C(O)NHP(O) fragment [1.704 (3) Å]. The phosphoryl and carbonyl groups are anti with respect to each other and the P atom has a distorted tetrahedral configuration. In the crystal, adjacent molecules are linked via N-H...O(P) and N-H...O(C) hydrogen bonds into an extended chain parallel to [101].

Comment top

The structure determination of the title compound, P(O)[NHC(O)CCl3][NHC6H4(2-CH3)]2 (Fig. 1), was performed in continuing of works on the synthesis and structural investigation of new phosphoramidate compounds having a C(O)NHP(O) skeleton (Toghraee et al., 2011; Pourayoubi, Tarahhomi et al., 2011).

The phosphoryl and the carbonyl groups adopt the anti positions with respect to each other. The P atom has a distorted tetrahedral conformation. The bond angles around the P atom are in the range of 102.06 (17)° to 117.28 (17)°. As expected, the P1—N2 (1.623 (4) Å) and P1—N3 (1.637 (3) Å) bonds are shorter than the P1—N1 (1.704 (3) Å) bond. The P═O and C═O bond lengths and the P—N—C bond angles are standard for this category of compounds (Pourayoubi, Fadaei & Parvez, 2011).

In the crystal structure, adjacent molecules are linked via NC(O)NHP(O)—H···O(P) and N—H···O(C) hydrogen bonds, into an extended chain parallel to [101], Table 1 and Fig. 2.

Related literature top

For background to compounds having a C(O)NHP(O) skeleton, see: Toghraee et al. (2011); Pourayoubi, Tarahhomi et al. (2011). For bond lengths and angles in a related structure, see: Pourayoubi, Fadaei & Parvez (2011).

Experimental top

CCl3C(O)NHP(O)Cl2 was synthesized from the reaction between phosphorus pentachloride (16.7 mmol) and 2,2,2-trichloroacetamide (16.7 mmol) in dry CCl4 at 358 K (3 h) and then the treatment of formic acid 85% (16.7 mmol) at ice bath temperature. To a solution of CCl3C(O)NHP(O)Cl2 (1.79 mmol) in CHCl3, a solution of o-toluidine (7.16 mmol) in CHCl3 was added dropwise at 273 K. After 4 h of stirring, the solvent was evaporated at room temperature. The solid was washed with distilled water. Single crystals were obtained from a mixture of CH3OH/CH3CN after slow evaporation at room temperature.

Refinement top

H-atoms were included in geometrically idealized positions with N—H = 0.98 Å and C—H = 0.95 and 0.98Å for aryl and methyl type H-atoms, respectively, and were included in the refinement with Uiso(H) = 1.2Ueq(C/N).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with ellipsoids shown at the 50% probability level. [Colour key: P atom is violet, O atoms are red, N atoms are blue, Cl atoms are green and C and H atoms are light grey.]
[Figure 2] Fig. 2. Part of the crystal structure of the title compound with N—H···O hydrogen bonds shown as dotted lines (the hydrogen atoms of the C—H units are omitted for clarity). [Symmetry codes: (i)-x+1, y, -z+1.5; (ii) -x+0.5, -y+0.5, -z+1]
N,N'-Bis(2-methylphenyl)-N''-(2,2,2- trichloroacetyl)phosphoric triamide top
Crystal data top
C16H17Cl3N3O2PF(000) = 1728
Mr = 420.65Dx = 1.471 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4137 reflections
a = 14.2030 (5) Åθ = 2.5–27.5°
b = 16.1935 (6) ŵ = 0.58 mm−1
c = 16.9107 (6) ÅT = 173 K
β = 102.3720 (19)°Prism, colorless
V = 3799.1 (2) Å30.10 × 0.09 × 0.08 mm
Z = 8
Data collection top
Nonius KappaCCD
diffractometer with APEXII CCD		4296 independent reflections
Radiation source: fine-focus sealed tube3031 reflections with I > 2σ(I)
graphiteRint = 0.055
ω and φ scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SORTAV; Blessing, 1997)		h = −18→18
Tmin = 0.944, Tmax = 0.955k = −20→21
8110 measured reflectionsl = −21→21
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.071Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.P)2 + 26.070P]
where P = (Fo2 + 2Fc2)/3
4296 reflections(Δ/σ)max < 0.001
228 parametersΔρmax = 0.48 e Å−3
0 restraintsΔρmin = −0.38 e Å−3
Crystal data top
C16H17Cl3N3O2PV = 3799.1 (2) Å3
Mr = 420.65Z = 8
Monoclinic, C2/cMo Kα radiation
a = 14.2030 (5) ŵ = 0.58 mm−1
b = 16.1935 (6) ÅT = 173 K
c = 16.9107 (6) Å0.10 × 0.09 × 0.08 mm
β = 102.3720 (19)°
Data collection top
Nonius KappaCCD
diffractometer with APEXII CCD		4296 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1997)		3031 reflections with I > 2σ(I)
Tmin = 0.944, Tmax = 0.955Rint = 0.055
8110 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.071 w = 1/[σ2(Fo2) + (0.P)2 + 26.070P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.141Δρmax = 0.48 e Å−3
S = 1.11Δρmin = −0.38 e Å−3
4296 reflectionsAbsolute structure: ?
228 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
Special details top

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

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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.23160 (9)0.15298 (9)0.78649 (8)0.0533 (4)
Cl20.09485 (7)0.26270 (8)0.68962 (7)0.0474 (3)
Cl30.27140 (8)0.32851 (9)0.78607 (8)0.0513 (3)
P10.44011 (7)0.21369 (7)0.61189 (6)0.0253 (2)
O10.2270 (2)0.2435 (2)0.58675 (16)0.0383 (7)
O20.53687 (18)0.20089 (18)0.66214 (15)0.0312 (6)
N10.3656 (2)0.2181 (2)0.67847 (18)0.0264 (7)
H10.39040.20940.73010.032*
N20.4268 (2)0.2961 (2)0.5559 (2)0.0350 (8)
H20.38410.29500.50980.042*
N30.3973 (2)0.1417 (2)0.54605 (19)0.0288 (7)
H30.37500.15810.49590.035*
C10.2710 (3)0.2342 (2)0.6560 (2)0.0274 (8)
C20.2186 (3)0.2441 (3)0.7272 (2)0.0349 (10)
C30.4812 (3)0.3707 (3)0.5776 (3)0.0379 (10)
C40.5651 (3)0.3852 (3)0.5521 (3)0.0430 (11)
C50.6135 (4)0.4609 (3)0.5734 (3)0.0556 (15)
H50.67200.47220.55700.067*
C60.5758 (5)0.5179 (4)0.6178 (4)0.0661 (17)
H60.60820.56910.63060.079*
C70.4923 (6)0.5032 (4)0.6446 (4)0.0733 (19)
H70.46820.54320.67620.088*
C80.4446 (4)0.4301 (3)0.6250 (3)0.0565 (14)
H80.38690.41910.64310.068*
C90.6031 (4)0.3245 (3)0.5022 (3)0.0573 (14)
H9A0.65920.34780.48500.069*
H9B0.55310.31080.45440.069*
H9C0.62230.27430.53400.069*
C100.3923 (3)0.0558 (3)0.5609 (2)0.0284 (9)
C110.3738 (3)0.0013 (3)0.4949 (3)0.0319 (9)
C120.3716 (3)−0.0828 (3)0.5109 (3)0.0384 (10)
H120.3599−0.12070.46700.046*
C130.3860 (3)−0.1126 (3)0.5889 (3)0.0426 (11)
H130.3840−0.17030.59830.051*
C140.4031 (3)−0.0585 (3)0.6528 (3)0.0391 (10)
H140.4121−0.07900.70650.047*
C150.4074 (3)0.0250 (3)0.6399 (3)0.0345 (10)
H150.42060.06190.68460.041*
C160.3589 (3)0.0325 (3)0.4097 (3)0.0421 (11)
H16A0.3531−0.01430.37230.051*
H16B0.41410.06670.40400.051*
H16C0.29990.06570.39700.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0420 (6)0.0706 (9)0.0466 (7)−0.0022 (6)0.0080 (5)0.0227 (6)
Cl20.0251 (5)0.0693 (9)0.0452 (7)0.0064 (5)0.0018 (5)−0.0046 (6)
Cl30.0384 (6)0.0659 (8)0.0473 (7)0.0042 (6)0.0041 (5)−0.0278 (6)
P10.0242 (5)0.0315 (6)0.0181 (5)−0.0012 (4)0.0003 (4)0.0003 (4)
O10.0291 (15)0.057 (2)0.0239 (15)0.0055 (14)−0.0050 (12)0.0003 (14)
O20.0252 (14)0.0454 (18)0.0206 (14)0.0009 (13)−0.0009 (11)−0.0016 (13)
N10.0251 (16)0.0362 (19)0.0149 (15)0.0026 (14)−0.0026 (12)−0.0019 (14)
N20.0348 (19)0.038 (2)0.0263 (18)−0.0065 (16)−0.0060 (15)0.0049 (16)
N30.0327 (18)0.0355 (19)0.0160 (16)0.0003 (15)0.0004 (13)0.0005 (14)
C10.0258 (19)0.030 (2)0.0238 (19)−0.0002 (16)−0.0010 (15)−0.0006 (16)
C20.024 (2)0.049 (3)0.029 (2)0.0001 (19)0.0010 (17)−0.004 (2)
C30.044 (3)0.035 (2)0.030 (2)−0.004 (2)−0.0019 (19)0.0095 (19)
C40.043 (3)0.039 (3)0.041 (3)−0.005 (2)−0.003 (2)0.010 (2)
C50.062 (3)0.044 (3)0.048 (3)−0.013 (3)−0.018 (3)0.015 (3)
C60.092 (5)0.042 (3)0.054 (4)−0.012 (3)−0.008 (3)0.007 (3)
C70.120 (6)0.052 (4)0.046 (3)0.007 (4)0.012 (4)−0.008 (3)
C80.074 (4)0.049 (3)0.042 (3)0.001 (3)0.003 (3)−0.003 (3)
C90.057 (3)0.054 (3)0.060 (4)0.002 (3)0.013 (3)0.004 (3)
C100.0262 (19)0.031 (2)0.028 (2)−0.0005 (17)0.0059 (16)−0.0030 (17)
C110.025 (2)0.041 (2)0.030 (2)−0.0028 (18)0.0072 (17)−0.0067 (19)
C120.037 (2)0.038 (3)0.041 (3)−0.005 (2)0.009 (2)−0.010 (2)
C130.045 (3)0.033 (2)0.051 (3)−0.004 (2)0.012 (2)0.001 (2)
C140.038 (2)0.042 (3)0.038 (3)0.000 (2)0.010 (2)0.004 (2)
C150.038 (2)0.037 (2)0.027 (2)−0.0035 (19)0.0045 (18)0.0002 (19)
C160.049 (3)0.046 (3)0.031 (2)−0.009 (2)0.010 (2)−0.009 (2)
Geometric parameters (Å, °) top
Cl1—C21.771 (5)C6—H60.9500
Cl2—C21.762 (4)C7—C81.369 (8)
Cl3—C21.762 (4)C7—H70.9500
P1—O21.468 (3)C8—H80.9500
P1—N21.623 (4)C9—H9A0.9800
P1—N31.637 (3)C9—H9B0.9800
P1—N11.704 (3)C9—H9C0.9800
O1—C11.213 (4)C10—C151.397 (6)
N1—C11.341 (5)C10—C111.404 (5)
N1—H10.8800C11—C121.390 (6)
N2—C31.439 (5)C11—C161.499 (6)
N2—H20.8800C12—C131.377 (6)
N3—C101.419 (5)C12—H120.9500
N3—H30.8800C13—C141.372 (6)
C1—C21.554 (6)C13—H130.9500
C3—C41.371 (6)C14—C151.373 (6)
C3—C81.420 (7)C14—H140.9500
C4—C51.413 (7)C15—H150.9500
C4—C91.472 (7)C16—H16A0.9800
C5—C61.369 (8)C16—H16B0.9800
C5—H50.9500C16—H16C0.9800
C6—C71.377 (9)
O2—P1—N2115.54 (18)C8—C7—C6119.1 (6)
O2—P1—N3117.28 (17)C8—C7—H7120.4
N2—P1—N3102.06 (17)C6—C7—H7120.4
O2—P1—N1105.08 (15)C7—C8—C3120.0 (6)
N2—P1—N1109.89 (18)C7—C8—H8120.0
N3—P1—N1106.68 (16)C3—C8—H8120.0
C1—N1—P1123.1 (3)C4—C9—H9A109.5
C1—N1—H1118.4C4—C9—H9B109.5
P1—N1—H1118.4H9A—C9—H9B109.5
C3—N2—P1123.6 (3)C4—C9—H9C109.5
C3—N2—H2118.2H9A—C9—H9C109.5
P1—N2—H2118.2H9B—C9—H9C109.5
C10—N3—P1127.1 (3)C15—C10—C11120.0 (4)
C10—N3—H3116.4C15—C10—N3121.0 (4)
P1—N3—H3116.4C11—C10—N3118.9 (4)
O1—C1—N1125.2 (4)C12—C11—C10118.0 (4)
O1—C1—C2120.1 (3)C12—C11—C16120.9 (4)
N1—C1—C2114.7 (3)C10—C11—C16121.1 (4)
C1—C2—Cl2110.2 (3)C13—C12—C11121.7 (4)
C1—C2—Cl3107.5 (3)C13—C12—H12119.2
Cl2—C2—Cl3110.0 (2)C11—C12—H12119.2
C1—C2—Cl1110.1 (3)C14—C13—C12119.7 (4)
Cl2—C2—Cl1108.8 (2)C14—C13—H13120.2
Cl3—C2—Cl1110.3 (2)C12—C13—H13120.2
C4—C3—C8120.6 (5)C13—C14—C15120.7 (4)
C4—C3—N2121.2 (4)C13—C14—H14119.7
C8—C3—N2118.1 (4)C15—C14—H14119.7
C3—C4—C5118.4 (5)C14—C15—C10120.0 (4)
C3—C4—C9121.0 (4)C14—C15—H15120.0
C5—C4—C9120.5 (5)C10—C15—H15120.0
C6—C5—C4119.9 (6)C11—C16—H16A109.5
C6—C5—H5120.0C11—C16—H16B109.5
C4—C5—H5120.0H16A—C16—H16B109.5
C5—C6—C7121.9 (6)C11—C16—H16C109.5
C5—C6—H6119.0H16A—C16—H16C109.5
C7—C6—H6119.0H16B—C16—H16C109.5
O2—P1—N1—C1176.0 (3)N2—C3—C4—C9−0.6 (7)
N2—P1—N1—C151.1 (4)C3—C4—C5—C6−0.6 (7)
N3—P1—N1—C1−58.9 (4)C9—C4—C5—C6178.1 (5)
O2—P1—N2—C3−29.9 (4)C4—C5—C6—C71.6 (8)
N3—P1—N2—C3−158.3 (4)C5—C6—C7—C8−1.2 (9)
N1—P1—N2—C388.8 (4)C6—C7—C8—C3−0.1 (8)
O2—P1—N3—C1051.5 (4)C4—C3—C8—C71.0 (8)
N2—P1—N3—C10178.8 (3)N2—C3—C8—C7−177.7 (5)
N1—P1—N3—C10−65.9 (4)P1—N3—C10—C1512.9 (6)
P1—N1—C1—O13.5 (6)P1—N3—C10—C11−165.8 (3)
P1—N1—C1—C2−174.1 (3)C15—C10—C11—C12−0.3 (6)
O1—C1—C2—Cl23.5 (5)N3—C10—C11—C12178.4 (4)
N1—C1—C2—Cl2−178.7 (3)C15—C10—C11—C16−179.1 (4)
O1—C1—C2—Cl3−116.4 (4)N3—C10—C11—C16−0.3 (6)
N1—C1—C2—Cl361.4 (4)C10—C11—C12—C130.7 (6)
O1—C1—C2—Cl1123.5 (4)C16—C11—C12—C13179.4 (4)
N1—C1—C2—Cl1−58.8 (4)C11—C12—C13—C14−0.1 (7)
P1—N2—C3—C493.0 (5)C12—C13—C14—C15−0.8 (7)
P1—N2—C3—C8−88.3 (5)C13—C14—C15—C101.2 (7)
C8—C3—C4—C5−0.6 (7)C11—C10—C15—C14−0.6 (6)
N2—C3—C4—C5178.1 (4)N3—C10—C15—C14−179.4 (4)
C8—C3—C4—C9−179.3 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.881.902.768 (4)170.
N2—H2···O1ii0.882.112.957 (4)162.
N3—H3···O1ii0.882.393.149 (4)144.
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.881.902.768 (4)170.
N2—H2···O1ii0.882.112.957 (4)162.
N3—H3···O1ii0.882.393.149 (4)144.
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1.
Acknowledgements top

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

references
References top

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