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Acta Cryst. (2011). E67, o934    [ doi:10.1107/S1600536811009640 ]

N-(2-Fluorobenzoyl)-N',N''-bis(4-methylphenyl)phosphoric triamide

M. Pourayoubi, A. Tarahhomi, A. L. Rheingold and J. A. Golen

Abstract top

The P atom in the title compound, C21H21FN3O2P, is in a tetrahedral coordination environment and the environment of each N atom is essentially planar (sums of angles = 359.7, 359.9 and 358.4°). The phosphoryl and carbonyl groups adopt anti orientations with respect to each other. In the crystal, adjacent molecules are linked via N-H...O=P and two N-H...O=C hydrogen bonds into an extended chain parallel to the a axis.

Comment top

Carbacylamidophosphates with a C(O)NHP(O) skeleton have attracted attention because of their roles as the O,O'-donor ligands for metal complexation (Gholivand et al., 2010). Following the previous works about carbacylamidophosphates such as P(O)[NHC(O)C6H3(2,6-F2)][N(CH3)(CH2C6H5)]2 (Pourayoubi et al., 2010), here, we report on the synthesis and crystal structure of the title compound, P(O)[NHC(O)C6H4(2-F)][NH—C6H4-4-CH3]2.

In the crystal structure of the title compound the phosphoryl and carbonyl groups adopt anti positions to each other. The P atom has a slightly distorted tetrahedral configuration (Fig. 1). The bond angles around the P atom are in the range of 101.09 (8)° to 116.67 (8)°. The P1—N2 and P1—N3 bonds (1.6361 (15) Å and 1.6291 (17) Å) are shorter than the P1—N1 bond (1.6872 (15) Å). The environment of the nitrogen atoms is essentially planar. The P═O bond length of 1.4723 (13) Å is comparable to those in similar compounds e.g. in P(O)[NHC(O)C6H4(4-NO2)][NHC6H11]2 (Sabbaghi et al., 2010).

In the crystal structure, adjacent molecules are linked via NC(O)NHP(O)—H···O ═P and two Namide—H···O ═C hydrogen bonds (see Table 1), into an extended chain parallel to the a axis.

Related literature top

For a phosphorus ligand having a C(O)NHP(O) skeleton, see: Gholivand et al. (2010). For a related structure, see: Pourayoubi et al. (2010). For bond lengths in related structures, see: Sabbaghi et al. (2010) and references cited therein.

Experimental top

2-F—C6H4C(O)NHP(O)Cl2 has been synthesized from the reaction between phosphorus pentachloride (4.0 g, 19.2 mmol) and 2-fluorobenzamide (2.671 g, 19.2 mmol) in dry CCl4 at 358 K (3 h) and then the treatment of formic acid (0.884 g, 19.2 mmol) at ice bath temperature. To a solution of 2-F—C6H4C(O)NHP(O)Cl2 (0.3 g, 1.17 mmol) in dry chloroform (30 ml), a mixture of p-toluidine (0.251 g, 2.34 mmol) and triethylamine (0.237 g, 2.34 mmol) in dry chloroform (10 ml) was added at 273 k. After 4 h stirring, the solvent was removed and the product was washed with distilled water and recrystallized from methanol/chloroform at room temperature. IR (KBr, cm-1): 3308 (NH), 3030 (NH), 2896, 2627, 1639 (C═O), 1457, 1220, 1061, 944, 795.

Refinement top

Hydrogen atoms H1N, H2N, and H3N were located in Fourier difference map and were refined with DFIX 0.88 (0.01) for the N–H bond lengths and isotropic displacement parameter of 1.2 times Ueq of the parent N atoms. All other hydrogen atoms were placed in their calculated positions with atom–H lengths of 0.95 Å (CH) and 0.98 Å (CH3) and isotropic displacement parameters for these atoms were set to 1.20 times (CH) and 1.50 times (CH3) Ueq of the parent C atom.

Computing details top

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

Figures top
[Figure 1] Fig. 1. An ORTEP-style plot of title compound with labeling. Displacement ellipsoids are drawn at the 50% probability level.
N-{bis[(4-methylphenyl)amino]phosphoryl}-2-fluorobenzamide top
Crystal data top
C21H21FN3O2PF(000) = 832
Mr = 397.38Dx = 1.315 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.7697 (9) ÅCell parameters from 5744 reflections
b = 10.2197 (9) Åθ = 2.2–27.5°
c = 20.2404 (18) ŵ = 0.17 mm−1
β = 96.605 (1)°T = 100 K
V = 2007.5 (3) Å3Block, colourless
Z = 40.25 × 0.15 × 0.15 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		4551 independent reflections
Radiation source: fine-focus sealed tube3411 reflections with I > 2σ(I)
graphiteRint = 0.035
φ and ω scansθmax = 27.9°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −12→12
Tmin = 0.959, Tmax = 0.975k = −11→13
15865 measured reflectionsl = −25→25
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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0669P)2 + 0.498P]
where P = (Fo2 + 2Fc2)/3
4551 reflections(Δ/σ)max = 0.007
264 parametersΔρmax = 0.41 e Å−3
3 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C21H21FN3O2PV = 2007.5 (3) Å3
Mr = 397.38Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.7697 (9) ŵ = 0.17 mm−1
b = 10.2197 (9) ÅT = 100 K
c = 20.2404 (18) Å0.25 × 0.15 × 0.15 mm
β = 96.605 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		4551 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		3411 reflections with I > 2σ(I)
Tmin = 0.959, Tmax = 0.975Rint = 0.035
15865 measured reflectionsθmax = 27.9°
Refinement top
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127Δρmax = 0.41 e Å−3
S = 1.05Δρmin = −0.26 e Å−3
4551 reflectionsAbsolute structure: ?
264 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
P10.72255 (5)0.92119 (4)0.50855 (2)0.02136 (14)
F10.92737 (14)1.40039 (12)0.55287 (6)0.0441 (3)
O10.91560 (13)1.14443 (13)0.50431 (6)0.0293 (3)
O20.58757 (12)0.86140 (12)0.51487 (6)0.0250 (3)
N10.69300 (16)1.08365 (14)0.50258 (7)0.0210 (3)
H1N0.6074 (11)1.1095 (19)0.4983 (9)0.025*
N20.79772 (16)0.87866 (15)0.44363 (8)0.0240 (3)
H2N0.8811 (12)0.8507 (19)0.4525 (10)0.029*
N30.84260 (16)0.88686 (16)0.56874 (8)0.0267 (4)
H3N0.9270 (12)0.905 (2)0.5636 (10)0.032*
C10.8139 (2)1.41838 (19)0.50898 (9)0.0296 (4)
C20.7701 (2)1.5451 (2)0.49516 (11)0.0381 (5)
H2C0.81941.61730.51570.046*
C30.6533 (2)1.5647 (2)0.45090 (11)0.0379 (5)
H3B0.62191.65110.44080.045*
C40.5822 (2)1.4596 (2)0.42132 (11)0.0344 (5)
H4A0.50291.47370.39030.041*
C50.6265 (2)1.33331 (19)0.43680 (9)0.0278 (4)
H5A0.57651.26120.41660.033*
C60.74372 (19)1.31052 (17)0.48164 (9)0.0230 (4)
C70.79305 (18)1.17460 (18)0.49728 (8)0.0220 (4)
C80.7441 (2)0.89104 (17)0.37612 (9)0.0244 (4)
C90.6203 (2)0.9545 (2)0.35614 (10)0.0319 (5)
H9A0.56850.99140.38840.038*
C100.5725 (2)0.9640 (2)0.28921 (10)0.0360 (5)
H10A0.48861.00890.27620.043*
C110.6439 (2)0.9096 (2)0.24070 (10)0.0404 (5)
C120.7657 (2)0.8443 (2)0.26118 (10)0.0419 (6)
H12A0.81570.80510.22880.050*
C130.8164 (2)0.8347 (2)0.32801 (10)0.0341 (5)
H13A0.90040.78980.34090.041*
C140.5884 (3)0.9202 (3)0.16774 (11)0.0561 (7)
H14A0.60980.83980.14460.084*
H14B0.63130.99500.14790.084*
H14C0.48840.93260.16360.084*
C150.8269 (2)0.85706 (18)0.63606 (9)0.0260 (4)
C160.7217 (2)0.7756 (2)0.65213 (10)0.0406 (5)
H16A0.65700.74080.61800.049*
C170.7115 (2)0.7452 (3)0.71817 (11)0.0506 (7)
H17A0.63670.69290.72880.061*
C180.8072 (3)0.7891 (2)0.76906 (10)0.0435 (6)
C190.9162 (3)0.8633 (2)0.75138 (11)0.0507 (7)
H19A0.98620.89090.78500.061*
C200.9253 (3)0.8980 (2)0.68584 (11)0.0427 (6)
H20A1.00000.95040.67520.051*
C210.7964 (3)0.7510 (3)0.84055 (11)0.0657 (8)
H21A0.87910.78010.86870.099*
H21B0.78790.65570.84370.099*
H21C0.71500.79260.85560.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0143 (3)0.0263 (2)0.0236 (2)0.00103 (18)0.00229 (18)0.00314 (18)
F10.0442 (8)0.0440 (7)0.0404 (7)−0.0137 (6)−0.0116 (6)−0.0023 (5)
O10.0150 (7)0.0379 (8)0.0351 (8)−0.0004 (6)0.0030 (6)0.0005 (6)
O20.0142 (7)0.0278 (7)0.0330 (7)−0.0001 (5)0.0025 (5)0.0038 (5)
N10.0143 (8)0.0244 (8)0.0245 (8)0.0002 (6)0.0038 (6)0.0007 (6)
N20.0158 (8)0.0297 (8)0.0262 (8)0.0048 (6)0.0015 (6)−0.0003 (6)
N30.0133 (8)0.0388 (9)0.0279 (9)0.0000 (7)0.0018 (7)0.0086 (6)
C10.0288 (11)0.0346 (11)0.0252 (10)−0.0079 (9)0.0024 (8)−0.0004 (8)
C20.0497 (15)0.0292 (10)0.0368 (12)−0.0104 (10)0.0106 (10)−0.0051 (9)
C30.0433 (14)0.0280 (11)0.0443 (12)0.0005 (9)0.0135 (11)0.0062 (9)
C40.0271 (11)0.0353 (11)0.0411 (12)0.0002 (9)0.0058 (9)0.0084 (9)
C50.0231 (10)0.0292 (10)0.0317 (10)−0.0033 (8)0.0057 (8)0.0011 (8)
C60.0202 (10)0.0273 (9)0.0227 (9)−0.0035 (7)0.0073 (7)−0.0015 (7)
C70.0167 (10)0.0303 (9)0.0192 (9)−0.0013 (7)0.0033 (7)−0.0019 (7)
C80.0212 (10)0.0274 (9)0.0247 (9)−0.0034 (8)0.0032 (8)0.0010 (7)
C90.0270 (11)0.0404 (11)0.0278 (10)0.0020 (9)0.0019 (8)−0.0030 (8)
C100.0290 (12)0.0461 (12)0.0313 (11)0.0001 (10)−0.0038 (9)0.0029 (9)
C110.0345 (13)0.0601 (15)0.0262 (11)−0.0110 (11)0.0015 (9)0.0024 (9)
C120.0351 (13)0.0624 (15)0.0300 (12)−0.0047 (11)0.0109 (10)−0.0062 (10)
C130.0254 (11)0.0452 (12)0.0324 (11)0.0013 (9)0.0060 (9)−0.0017 (9)
C140.0465 (16)0.095 (2)0.0262 (12)−0.0108 (14)0.0008 (11)0.0069 (12)
C150.0234 (10)0.0299 (10)0.0248 (10)0.0057 (8)0.0040 (8)0.0025 (7)
C160.0266 (12)0.0627 (15)0.0318 (11)−0.0063 (10)0.0001 (9)0.0129 (10)
C170.0322 (13)0.0782 (18)0.0421 (14)−0.0019 (12)0.0075 (11)0.0229 (12)
C180.0496 (15)0.0558 (14)0.0263 (11)0.0136 (12)0.0098 (10)0.0039 (9)
C190.0709 (19)0.0504 (14)0.0284 (12)−0.0100 (13)−0.0048 (12)−0.0038 (10)
C200.0499 (15)0.0433 (13)0.0336 (12)−0.0166 (11)−0.0006 (10)0.0005 (9)
C210.074 (2)0.095 (2)0.0310 (13)0.0190 (17)0.0163 (13)0.0111 (13)
Geometric parameters (Å, °) top
P1—O21.4723 (13)C9—H9A0.9500
P1—N31.6291 (17)C10—C111.385 (3)
P1—N21.6361 (15)C10—H10A0.9500
P1—N11.6872 (15)C11—C121.386 (3)
F1—C11.351 (2)C11—C141.517 (3)
O1—C71.229 (2)C12—C131.389 (3)
N1—C71.362 (2)C12—H12A0.9500
N1—H1N0.872 (9)C13—H13A0.9500
N2—C81.412 (2)C14—H14A0.9800
N2—H2N0.862 (9)C14—H14B0.9800
N3—C151.422 (2)C14—H14C0.9800
N3—H3N0.863 (9)C15—C201.375 (3)
C1—C61.380 (3)C15—C161.390 (3)
C1—C21.382 (3)C16—C171.387 (3)
C2—C31.382 (3)C16—H16A0.9500
C2—H2C0.9500C17—C181.384 (3)
C3—C41.378 (3)C17—H17A0.9500
C3—H3B0.9500C18—C191.387 (3)
C4—C51.385 (3)C18—C211.514 (3)
C4—H4A0.9500C19—C201.386 (3)
C5—C61.396 (3)C19—H19A0.9500
C5—H5A0.9500C20—H20A0.9500
C6—C71.492 (3)C21—H21A0.9800
C8—C91.391 (3)C21—H21B0.9800
C8—C131.392 (3)C21—H21C0.9800
C9—C101.384 (3)
O2—P1—N3114.88 (8)C9—C10—C11121.7 (2)
O2—P1—N2116.67 (8)C9—C10—H10A119.2
N3—P1—N2101.09 (8)C11—C10—H10A119.2
O2—P1—N1105.49 (8)C10—C11—C12117.8 (2)
N3—P1—N1111.59 (8)C10—C11—C14120.6 (2)
N2—P1—N1107.03 (8)C12—C11—C14121.6 (2)
C7—N1—P1123.97 (13)C11—C12—C13121.5 (2)
C7—N1—H1N118.3 (13)C11—C12—H12A119.2
P1—N1—H1N117.4 (13)C13—C12—H12A119.2
C8—N2—P1127.06 (13)C12—C13—C8120.0 (2)
C8—N2—H2N117.9 (13)C12—C13—H13A120.0
P1—N2—H2N114.9 (13)C8—C13—H13A120.0
C15—N3—P1127.97 (13)C11—C14—H14A109.5
C15—N3—H3N111.7 (14)C11—C14—H14B109.5
P1—N3—H3N118.7 (14)H14A—C14—H14B109.5
F1—C1—C6119.15 (18)C11—C14—H14C109.5
F1—C1—C2118.14 (18)H14A—C14—H14C109.5
C6—C1—C2122.7 (2)H14B—C14—H14C109.5
C3—C2—C1118.7 (2)C20—C15—C16118.94 (18)
C3—C2—H2C120.7C20—C15—N3119.60 (18)
C1—C2—H2C120.7C16—C15—N3121.11 (18)
C4—C3—C2120.4 (2)C17—C16—C15119.8 (2)
C4—C3—H3B119.8C17—C16—H16A120.1
C2—C3—H3B119.8C15—C16—H16A120.1
C3—C4—C5119.9 (2)C18—C17—C16121.8 (2)
C3—C4—H4A120.0C18—C17—H17A119.1
C5—C4—H4A120.0C16—C17—H17A119.1
C4—C5—C6120.93 (19)C17—C18—C19117.3 (2)
C4—C5—H5A119.5C17—C18—C21120.8 (2)
C6—C5—H5A119.5C19—C18—C21121.8 (2)
C1—C6—C5117.37 (18)C20—C19—C18121.5 (2)
C1—C6—C7121.68 (18)C20—C19—H19A119.2
C5—C6—C7120.92 (16)C18—C19—H19A119.2
O1—C7—N1121.22 (17)C15—C20—C19120.5 (2)
O1—C7—C6123.01 (16)C15—C20—H20A119.8
N1—C7—C6115.77 (15)C19—C20—H20A119.8
C9—C8—C13118.93 (18)C18—C21—H21A109.5
C9—C8—N2122.47 (16)C18—C21—H21B109.5
C13—C8—N2118.58 (17)H21A—C21—H21B109.5
C10—C9—C8120.08 (18)C18—C21—H21C109.5
C10—C9—H9A120.0H21A—C21—H21C109.5
C8—C9—H9A120.0H21B—C21—H21C109.5
O2—P1—N1—C7178.66 (14)C5—C6—C7—N1−39.0 (2)
N3—P1—N1—C753.27 (16)P1—N2—C8—C96.1 (3)
N2—P1—N1—C7−56.46 (16)P1—N2—C8—C13−172.26 (15)
O2—P1—N2—C857.27 (18)C13—C8—C9—C10−1.7 (3)
N3—P1—N2—C8−177.42 (15)N2—C8—C9—C10179.93 (18)
N1—P1—N2—C8−60.53 (17)C8—C9—C10—C111.1 (3)
O2—P1—N3—C15−28.7 (2)C9—C10—C11—C120.3 (3)
N2—P1—N3—C15−155.21 (16)C9—C10—C11—C14179.3 (2)
N1—P1—N3—C1591.30 (17)C10—C11—C12—C13−0.9 (3)
F1—C1—C2—C3−179.31 (17)C14—C11—C12—C13180.0 (2)
C6—C1—C2—C3−1.7 (3)C11—C12—C13—C80.3 (3)
C1—C2—C3—C40.1 (3)C9—C8—C13—C121.0 (3)
C2—C3—C4—C51.1 (3)N2—C8—C13—C12179.47 (19)
C3—C4—C5—C6−0.7 (3)P1—N3—C15—C20−144.91 (18)
F1—C1—C6—C5179.64 (15)P1—N3—C15—C1641.9 (3)
C2—C1—C6—C52.0 (3)C20—C15—C16—C174.9 (3)
F1—C1—C6—C7−2.4 (3)N3—C15—C16—C17178.1 (2)
C2—C1—C6—C7179.95 (17)C15—C16—C17—C18−3.0 (4)
C4—C5—C6—C1−0.8 (3)C16—C17—C18—C19−1.2 (4)
C4—C5—C6—C7−178.77 (17)C16—C17—C18—C21−178.0 (2)
P1—N1—C7—O1−8.6 (2)C17—C18—C19—C203.3 (4)
P1—N1—C7—C6170.55 (12)C21—C18—C19—C20−179.9 (2)
C1—C6—C7—O1−37.7 (3)C16—C15—C20—C19−2.8 (3)
C5—C6—C7—O1140.17 (18)N3—C15—C20—C19−176.1 (2)
C1—C6—C7—N1143.13 (17)C18—C19—C20—C15−1.4 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.87 (1)1.92 (1)2.780 (2)171 (2)
N2—H2N···O1ii0.86 (1)2.08 (1)2.886 (2)156 (2)
N3—H3N···O1ii0.86 (1)2.24 (2)2.945 (2)139 (2)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.87 (1)1.92 (1)2.780 (2)171 (2)
N2—H2N···O1ii0.86 (1)2.08 (1)2.886 (2)156 (2)
N3—H3N···O1ii0.86 (1)2.24 (2)2.945 (2)139 (2)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+2, −z+1.
Acknowledgements top

Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged. The authors wish to thank Bruker AXS Inc. or the use of one of their SMART X2S benchtop instruments.

references
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