N,N'-Dibenzyl-N''-(2,4-difluoro-benzo-yl)-N,N'-dimethyl-phospho-ric triamide.

In the title mol-ecule, C(23)H(24)F(2)N(3)O(2)P, the P atom is in a distorted tetra-hedral P(=O)(N)(N)(2) environment, with the bond angles around the P atom in the range 106.78 (11)-114.10 (13)°. The phosphoryl and carbonyl groups, which are separated by an N atom, adopt an anti orientation relative to each other. In the C(=O)NHP(=O) fragment, the P-N bond is longer [1.683 (2) Å] and the O-P-N angle is smaller [106.78 (11)°] than the other P-N bonds [1.613 (2) and 1.632 (2) Å] and O-P-N bond angles [114.10 (13) and 110.83 (12)°], respectively. The N atoms have sp(2) character. In the crystal, pairs of P=O⋯H-N hydrogen bonds form inversion dimers with R(2) (2)(8) ring motifs.

Related literature

For hydrogen-bond patterns in compounds with formula RC(O)NHP(O)[NR 1 R 2]2 and RC(O)NHP(O)[NHR 1]2 and for the discussion of different C(=O) versus P(=O) orientations in the C(O)NHP(O) fragment, see: Toghraee et al. (2011 ▶). For hydrogen-bond strengths in cyclic hydrogen-bond motifs and for bond lengths and angles, see: Pourayoubi et al. (2011 ▶). For graph-set analysis of hydrogen-bonds motifs, see: Bernstein et al. (1995 ▶). For the synthesis of the starting phospho­rous–chlorine compound, see: Pourayoubi et al. (2010 ▶).

Experimental

Crystal data

C23H24F2N3O2P

M = 443.42

Triclinic,

a = 10.3619 (6) Å

b = 10.7721 (10) Å

c = 11.6433 (8) Å

α = 70.523 (7)°

β = 72.495 (5)°

γ = 70.197 (7)°

V = 1126.65 (15) Å3

Z = 2

Cu Kα radiation

μ = 1.44 mm−1

T = 300 K

0.17 × 0.14 × 0.03 mm

Data collection

Agilent Xcalibur Gemini R diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.954, T max = 1.000

10022 measured reflections

4209 independent reflections

2758 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.141

S = 1.01

4209 reflections

268 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811055115/fy2035sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055115/fy2035Isup2.hkl

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

C23H24F2N3O2P	Z = 2
Mr = 443.42	F(000) = 464
Triclinic, P1	Dx = 1.307 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 10.3619 (6) Å	Cell parameters from 2755 reflections
b = 10.7721 (10) Å	θ = 4.1–70.6°
c = 11.6433 (8) Å	µ = 1.44 mm−1
α = 70.523 (7)°	T = 300 K
β = 72.495 (5)°	Plate, colorless
γ = 70.197 (7)°	0.17 × 0.14 × 0.03 mm
V = 1126.65 (15) Å3

Agilent Xcalibur Gemini R diffractometer	4209 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2758 reflections with I > 2σ(I)
graphite	Rint = 0.044
Detector resolution: 10.2673 pixels mm-1	θmax = 70.7°, θmin = 4.1°
ω scans	h = −8→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→13
Tmin = 0.954, Tmax = 1.000	l = −14→14
10022 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0585P)2] where P = (Fo2 + 2Fc2)/3
4209 reflections	(Δ/σ)max < 0.001
268 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
P1	0.58022 (6)	0.27216 (7)	0.57829 (7)	0.0460 (2)
N2	0.4103 (2)	0.3411 (2)	0.5698 (2)	0.0484 (5)
H2	0.3866	0.4255	0.5297	0.058*
N3	0.6579 (2)	0.1967 (3)	0.4676 (2)	0.0586 (6)
N4	0.5904 (2)	0.1570 (2)	0.7108 (2)	0.0528 (6)
O5	0.63610 (18)	0.38484 (19)	0.5704 (2)	0.0595 (5)
O6	0.3324 (2)	0.1512 (2)	0.6516 (2)	0.0684 (6)
F7	0.0748 (2)	0.2082 (2)	0.5985 (2)	0.0946 (7)
F8	−0.24562 (18)	0.6018 (2)	0.6907 (2)	0.0991 (7)
C9	0.1600 (3)	0.3630 (3)	0.6399 (3)	0.0503 (7)
C10	0.1264 (3)	0.4859 (3)	0.6711 (3)	0.0594 (7)
H10	0.1977	0.5144	0.6792	0.071*
C11	−0.0098 (3)	0.5667 (4)	0.6902 (3)	0.0681 (6)
H11	−0.0315	0.6484	0.7115	0.082*
C12	−0.1121 (3)	0.5211 (4)	0.6763 (3)	0.0681 (6)
C13	−0.0871 (3)	0.4028 (3)	0.6477 (3)	0.0604 (5)
H13	−0.1592	0.3749	0.6400	0.072*
C14	0.0492 (3)	0.3252 (3)	0.6305 (3)	0.0604 (5)
C15	0.6261 (3)	0.2312 (3)	0.2566 (3)	0.0548 (7)
C16	0.5939 (3)	0.3719 (3)	0.2161 (3)	0.0689 (9)
H16	0.5505	0.4238	0.2739	0.083*
C17	0.6249 (4)	0.4357 (4)	0.0925 (4)	0.0835 (11)
H17	0.6024	0.5305	0.0666	0.100*
C18	0.6890 (4)	0.3607 (5)	0.0060 (4)	0.0868 (12)
H18	0.7097	0.4047	−0.0783	0.104*
C19	0.7225 (3)	0.2209 (4)	0.0442 (3)	0.0767 (10)
H19	0.7663	0.1699	−0.0142	0.092*
C20	0.6910 (3)	0.1556 (3)	0.1697 (3)	0.0586 (7)
H20	0.7135	0.0607	0.1954	0.070*
C21	0.7259 (3)	−0.0736 (3)	0.8050 (3)	0.0553 (7)
C22	0.7176 (3)	−0.2009 (3)	0.8816 (3)	0.0663 (8)
H22	0.6435	−0.2339	0.8862	0.080*
C23	0.8165 (4)	−0.2796 (4)	0.9508 (4)	0.0905 (12)
H23	0.8101	−0.3658	1.0010	0.109*
C24	0.9252 (4)	−0.2314 (5)	0.9463 (4)	0.1019 (14)
H24	0.9920	−0.2843	0.9940	0.122*
C25	0.9347 (4)	−0.1054 (5)	0.8716 (4)	0.0970 (13)
H25	1.0080	−0.0723	0.8690	0.116*
C26	0.8370 (3)	−0.0268 (4)	0.8002 (4)	0.0770 (10)
H26	0.8456	0.0582	0.7484	0.092*
C27	0.3063 (3)	0.2749 (3)	0.6210 (3)	0.0512 (7)
C28	0.5913 (3)	0.1608 (3)	0.3930 (3)	0.0622 (8)
H28A	0.4903	0.1859	0.4229	0.075*
H28B	0.6220	0.0627	0.4037	0.075*
C29	0.6160 (3)	0.0108 (3)	0.7288 (3)	0.0600 (8)
H29A	0.6461	−0.0092	0.6481	0.072*
H29B	0.5289	−0.0148	0.7704	0.072*
C30	0.8121 (3)	0.1484 (4)	0.4424 (4)	0.0864 (12)
H30A	0.8473	0.1766	0.4943	0.130*
H30B	0.8494	0.1865	0.3563	0.130*
H30C	0.8401	0.0505	0.4600	0.130*
C31	0.5236 (4)	0.2029 (4)	0.8241 (3)	0.0922 (13)
H31A	0.5110	0.2996	0.8052	0.138*
H31B	0.5819	0.1564	0.8842	0.138*
H31C	0.4340	0.1831	0.8575	0.138*

	U11	U22	U33	U12	U13	U23
P1	0.0399 (3)	0.0435 (4)	0.0562 (4)	−0.0113 (3)	−0.0114 (3)	−0.0136 (3)
N2	0.0407 (10)	0.0409 (12)	0.0630 (15)	−0.0116 (9)	−0.0131 (10)	−0.0100 (10)
N3	0.0524 (12)	0.0660 (16)	0.0568 (15)	−0.0061 (11)	−0.0139 (11)	−0.0230 (12)
N4	0.0536 (12)	0.0533 (14)	0.0517 (14)	−0.0087 (10)	−0.0142 (11)	−0.0167 (11)
O5	0.0465 (9)	0.0476 (11)	0.0894 (15)	−0.0148 (8)	−0.0206 (10)	−0.0161 (10)
O6	0.0572 (11)	0.0446 (12)	0.1014 (18)	−0.0157 (9)	−0.0223 (11)	−0.0092 (11)
F7	0.0756 (12)	0.0788 (14)	0.150 (2)	−0.0270 (10)	−0.0354 (13)	−0.0388 (14)
F8	0.0412 (9)	0.1202 (18)	0.1219 (19)	−0.0012 (10)	−0.0078 (10)	−0.0427 (15)
C9	0.0430 (13)	0.0523 (16)	0.0551 (17)	−0.0172 (12)	−0.0112 (12)	−0.0079 (13)
C10	0.0503 (15)	0.0680 (19)	0.065 (2)	−0.0196 (14)	−0.0077 (13)	−0.0238 (16)
C11	0.0461 (10)	0.0789 (16)	0.0738 (16)	−0.0124 (10)	−0.0027 (10)	−0.0261 (13)
C12	0.0461 (10)	0.0789 (16)	0.0738 (16)	−0.0124 (10)	−0.0027 (10)	−0.0261 (13)
C13	0.0479 (9)	0.0677 (13)	0.0672 (14)	−0.0239 (9)	−0.0129 (9)	−0.0101 (11)
C14	0.0479 (9)	0.0677 (13)	0.0672 (14)	−0.0239 (9)	−0.0129 (9)	−0.0101 (11)
C15	0.0556 (15)	0.0624 (18)	0.0538 (18)	−0.0246 (13)	−0.0113 (13)	−0.0154 (14)
C16	0.076 (2)	0.063 (2)	0.067 (2)	−0.0164 (16)	−0.0143 (17)	−0.0183 (17)
C17	0.088 (2)	0.077 (2)	0.070 (2)	−0.018 (2)	−0.022 (2)	0.002 (2)
C18	0.081 (2)	0.110 (3)	0.056 (2)	−0.025 (2)	−0.0169 (18)	−0.002 (2)
C19	0.0647 (19)	0.109 (3)	0.062 (2)	−0.0185 (19)	−0.0110 (16)	−0.036 (2)
C20	0.0537 (15)	0.071 (2)	0.0576 (19)	−0.0199 (14)	−0.0103 (14)	−0.0230 (16)
C21	0.0517 (15)	0.0591 (17)	0.0504 (17)	−0.0104 (13)	−0.0117 (13)	−0.0117 (14)
C22	0.0624 (17)	0.0610 (19)	0.064 (2)	−0.0105 (15)	−0.0121 (15)	−0.0088 (16)
C23	0.085 (3)	0.079 (3)	0.079 (3)	−0.004 (2)	−0.024 (2)	0.003 (2)
C24	0.072 (2)	0.113 (4)	0.095 (3)	0.013 (2)	−0.038 (2)	−0.014 (3)
C25	0.0576 (19)	0.119 (4)	0.112 (3)	−0.012 (2)	−0.036 (2)	−0.022 (3)
C26	0.0608 (18)	0.082 (2)	0.084 (3)	−0.0206 (17)	−0.0262 (17)	−0.005 (2)
C27	0.0479 (14)	0.0464 (16)	0.0629 (18)	−0.0154 (12)	−0.0173 (13)	−0.0107 (13)
C28	0.0791 (19)	0.0574 (18)	0.0570 (19)	−0.0301 (15)	−0.0025 (15)	−0.0216 (15)
C29	0.0641 (17)	0.0502 (17)	0.068 (2)	−0.0211 (14)	−0.0254 (15)	−0.0026 (15)
C30	0.0557 (18)	0.109 (3)	0.083 (3)	0.0049 (18)	−0.0099 (17)	−0.042 (2)
C31	0.098 (3)	0.105 (3)	0.059 (2)	0.006 (2)	−0.019 (2)	−0.034 (2)

P1—O5	1.4787 (19)	C17—H17	0.9300
P1—N3	1.613 (2)	C18—C19	1.371 (5)
P1—N4	1.632 (2)	C18—H18	0.9300
P1—N2	1.683 (2)	C19—C20	1.386 (5)
N2—C27	1.370 (3)	C19—H19	0.9300
N2—H2	0.8600	C20—H20	0.9300
N3—C28	1.465 (4)	C21—C22	1.379 (4)
N3—C30	1.472 (4)	C21—C26	1.385 (4)
N4—C31	1.455 (4)	C21—C29	1.510 (4)
N4—C29	1.458 (4)	C22—C23	1.367 (5)
O6—C27	1.213 (3)	C22—H22	0.9300
F7—C14	1.351 (4)	C23—C24	1.372 (6)
F8—C12	1.357 (3)	C23—H23	0.9300
C9—C14	1.385 (4)	C24—C25	1.364 (6)
C9—C10	1.392 (4)	C24—H24	0.9300
C9—C27	1.487 (4)	C25—C26	1.375 (5)
C10—C11	1.381 (4)	C25—H25	0.9300
C10—H10	0.9300	C26—H26	0.9300
C11—C12	1.379 (5)	C28—H28A	0.9700
C11—H11	0.9300	C28—H28B	0.9700
C12—C13	1.345 (4)	C29—H29A	0.9700
C13—C14	1.370 (4)	C29—H29B	0.9700
C13—H13	0.9300	C30—H30A	0.9600
C15—C16	1.381 (4)	C30—H30B	0.9600
C15—C20	1.382 (4)	C30—H30C	0.9600
C15—C28	1.504 (4)	C31—H31A	0.9600
C16—C17	1.363 (5)	C31—H31B	0.9600
C16—H16	0.9300	C31—H31C	0.9600
C17—C18	1.373 (6)
O5—P1—N3	114.10 (13)	C15—C20—C19	120.1 (3)
O5—P1—N4	110.83 (12)	C15—C20—H20	120.0
N3—P1—N4	108.04 (13)	C19—C20—H20	120.0
O5—P1—N2	106.78 (11)	C22—C21—C26	118.3 (3)
N3—P1—N2	108.02 (12)	C22—C21—C29	120.1 (3)
N4—P1—N2	108.93 (12)	C26—C21—C29	121.7 (3)
C27—N2—P1	125.86 (19)	C23—C22—C21	121.1 (3)
C27—N2—H2	117.1	C23—C22—H22	119.4
P1—N2—H2	117.1	C21—C22—H22	119.4
C28—N3—C30	114.7 (2)	C22—C23—C24	120.1 (4)
C28—N3—P1	127.0 (2)	C22—C23—H23	120.0
C30—N3—P1	118.1 (2)	C24—C23—H23	120.0
C31—N4—C29	114.2 (3)	C25—C24—C23	119.7 (4)
C31—N4—P1	117.2 (2)	C25—C24—H24	120.2
C29—N4—P1	125.2 (2)	C23—C24—H24	120.2
C14—C9—C10	116.4 (3)	C24—C25—C26	120.5 (4)
C14—C9—C27	121.6 (3)	C24—C25—H25	119.7
C10—C9—C27	122.0 (2)	C26—C25—H25	119.7
C11—C10—C9	121.9 (3)	C25—C26—C21	120.4 (4)
C11—C10—H10	119.1	C25—C26—H26	119.8
C9—C10—H10	119.1	C21—C26—H26	119.8
C12—C11—C10	117.2 (3)	O6—C27—N2	121.8 (2)
C12—C11—H11	121.4	O6—C27—C9	122.0 (2)
C10—C11—H11	121.4	N2—C27—C9	116.2 (2)
C13—C12—F8	118.3 (3)	N3—C28—C15	112.2 (2)
C13—C12—C11	124.0 (3)	N3—C28—H28A	109.2
F8—C12—C11	117.7 (3)	C15—C28—H28A	109.2
C12—C13—C14	117.0 (3)	N3—C28—H28B	109.2
C12—C13—H13	121.5	C15—C28—H28B	109.2
C14—C13—H13	121.5	H28A—C28—H28B	107.9
F7—C14—C13	117.0 (3)	N4—C29—C21	112.5 (2)
F7—C14—C9	119.4 (3)	N4—C29—H29A	109.1
C13—C14—C9	123.6 (3)	C21—C29—H29A	109.1
C16—C15—C20	118.9 (3)	N4—C29—H29B	109.1
C16—C15—C28	120.8 (3)	C21—C29—H29B	109.1
C20—C15—C28	120.3 (3)	H29A—C29—H29B	107.8
C17—C16—C15	120.8 (3)	N3—C30—H30A	109.5
C17—C16—H16	119.6	N3—C30—H30B	109.5
C15—C16—H16	119.6	H30A—C30—H30B	109.5
C16—C17—C18	120.4 (4)	N3—C30—H30C	109.5
C16—C17—H17	119.8	H30A—C30—H30C	109.5
C18—C17—H17	119.8	H30B—C30—H30C	109.5
C19—C18—C17	119.8 (4)	N4—C31—H31A	109.5
C19—C18—H18	120.1	N4—C31—H31B	109.5
C17—C18—H18	120.1	H31A—C31—H31B	109.5
C18—C19—C20	120.0 (3)	N4—C31—H31C	109.5
C18—C19—H19	120.0	H31A—C31—H31C	109.5
C20—C19—H19	120.0	H31B—C31—H31C	109.5
O5—P1—N2—C27	−152.1 (2)	C28—C15—C16—C17	−179.7 (3)
N3—P1—N2—C27	84.8 (3)	C15—C16—C17—C18	−0.1 (6)
N4—P1—N2—C27	−32.3 (3)	C16—C17—C18—C19	−0.2 (6)
O5—P1—N3—C28	−133.5 (2)	C17—C18—C19—C20	0.3 (6)
N4—P1—N3—C28	102.7 (3)	C16—C15—C20—C19	−0.1 (4)
N2—P1—N3—C28	−15.0 (3)	C28—C15—C20—C19	179.8 (3)
O5—P1—N3—C30	51.3 (3)	C18—C19—C20—C15	−0.2 (5)
N4—P1—N3—C30	−72.4 (3)	C26—C21—C22—C23	−0.2 (5)
N2—P1—N3—C30	169.9 (2)	C29—C21—C22—C23	179.6 (3)
O5—P1—N4—C31	55.7 (3)	C21—C22—C23—C24	1.0 (6)
N3—P1—N4—C31	−178.6 (2)	C22—C23—C24—C25	−0.7 (7)
N2—P1—N4—C31	−61.5 (3)	C23—C24—C25—C26	−0.5 (7)
O5—P1—N4—C29	−146.5 (2)	C24—C25—C26—C21	1.2 (6)
N3—P1—N4—C29	−20.8 (3)	C22—C21—C26—C25	−0.9 (5)
N2—P1—N4—C29	96.3 (2)	C29—C21—C26—C25	179.3 (3)
C14—C9—C10—C11	−0.7 (5)	P1—N2—C27—O6	−18.5 (4)
C27—C9—C10—C11	−179.1 (3)	P1—N2—C27—C9	159.9 (2)
C9—C10—C11—C12	−0.4 (5)	C14—C9—C27—O6	−34.0 (5)
C10—C11—C12—C13	1.2 (6)	C10—C9—C27—O6	144.4 (3)
C10—C11—C12—F8	−177.8 (3)	C14—C9—C27—N2	147.6 (3)
F8—C12—C13—C14	178.3 (3)	C10—C9—C27—N2	−34.1 (4)
C11—C12—C13—C14	−0.7 (5)	C30—N3—C28—C15	−66.2 (4)
C12—C13—C14—F7	−178.3 (3)	P1—N3—C28—C15	118.5 (3)
C12—C13—C14—C9	−0.6 (5)	C16—C15—C28—N3	−58.5 (4)
C10—C9—C14—F7	178.9 (3)	C20—C15—C28—N3	121.6 (3)
C27—C9—C14—F7	−2.7 (5)	C31—N4—C29—C21	−68.0 (3)
C10—C9—C14—C13	1.2 (5)	P1—N4—C29—C21	133.6 (2)
C27—C9—C14—C13	179.7 (3)	C22—C21—C29—N4	148.0 (3)
C20—C15—C16—C17	0.2 (5)	C26—C21—C29—N4	−32.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5i	0.86	1.96	2.812 (3)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O5i	0.86	1.96	2.812 (3)	171

Symmetry code: (i) .