N,N,N',N'-Tetra-ethyl-N''-(2-fluoro-benzo-yl)phospho-ric triamide.

In the title compound, C(15)H(25)FN(3)O(2)P, the phosphoryl group is in an anti and syn orientation to the C=O and N-H groups, respectively. The P atom is in a distorted tetra-hedral environment. One of the ethyl groups is disordered over two sets of sites with refined occupancies of 0.755 (6) and 0.245 (6). In addition, the F atom was refined as disordered with occupancies fixed at 0.9 and 0.1. This disorder corresponds to a rotation of approximately 180° of the fluoro-benzene ring about its connecting C-C bond. In the crystal, pairs of inter-molecular N-H⋯O(=P) hydrogen bonds form centrosymmetric dimers.

Related literature

For background to phospho­ric triamide compounds containing a C(=O)NHP(=O) skeleton, see: Pourayoubi et al. (2011a ▶,b ▶); Tarahhomi et al. (2011 ▶). For the synthesis of the starting material 2-F—C6H4C(=O)NHP(=O)Cl2, see: Pourayoubi et al. (2011a ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C15H25FN3O2P

M = 329.35

Monoclinic,

a = 10.9296 (9) Å

b = 12.2221 (10) Å

c = 12.3423 (10) Å

β = 91.443 (1)°

V = 1648.2 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 100 K

0.45 × 0.40 × 0.35 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.920, T max = 0.937

11336 measured reflections

3741 independent reflections

3056 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.122

S = 1.08

3741 reflections

236 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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 and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811036944/lh5308sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036944/lh5308Isup2.hkl

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

C15H25FN3O2P	F(000) = 704
Mr = 329.35	Dx = 1.327 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6938 reflections
a = 10.9296 (9) Å	θ = 2.5–27.9°
b = 12.2221 (10) Å	µ = 0.19 mm−1
c = 12.3423 (10) Å	T = 100 K
β = 91.443 (1)°	Block, colourless
V = 1648.2 (2) Å3	0.45 × 0.40 × 0.35 mm
Z = 4

Bruker APEXII CCD diffractometer	3741 independent reflections
Radiation source: fine-focus sealed tube	3056 reflections with I > 2σ(I)
graphite	Rint = 0.051
φ and ω scans	θmax = 28.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→7
Tmin = 0.920, Tmax = 0.937	k = −16→14
11336 measured reflections	l = −15→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0487P)2 + 0.7763P] where P = (Fo2 + 2Fc2)/3
3741 reflections	(Δ/σ)max < 0.001
236 parameters	Δρmax = 0.55 e Å−3
6 restraints	Δρmin = −0.42 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	Occ. (<1)
P1	0.62104 (4)	0.64819 (4)	0.52994 (4)	0.01901 (14)
F1	0.88953 (13)	0.41423 (11)	0.83105 (10)	0.0338 (3)	0.90
F1A	0.7449 (9)	0.3460 (7)	0.4748 (4)	0.019 (2)	0.10
O1	0.83305 (12)	0.57884 (11)	0.68306 (10)	0.0259 (3)
O2	0.52742 (11)	0.62160 (11)	0.44464 (10)	0.0230 (3)
N1	0.66071 (13)	0.52777 (13)	0.58794 (12)	0.0199 (3)
H1N	0.6116 (17)	0.4741 (15)	0.5750 (16)	0.024*
N2	0.57927 (14)	0.72748 (13)	0.62914 (12)	0.0260 (4)
N3	0.73894 (13)	0.70810 (12)	0.47587 (11)	0.0201 (3)
C1	0.86735 (17)	0.34892 (16)	0.74688 (15)	0.0254 (4)
H1A	0.8811	0.3968	0.8066	0.030*	0.10
C2	0.91255 (17)	0.24343 (17)	0.75327 (17)	0.0303 (5)
H2	0.9557	0.2194	0.8167	0.036*
C3	0.89453 (18)	0.17367 (17)	0.66716 (17)	0.0300 (4)
H3	0.9265	0.1014	0.6704	0.036*
C4	0.82999 (18)	0.20843 (16)	0.57575 (16)	0.0289 (4)
H4	0.8176	0.1603	0.5161	0.035*
C5	0.78342 (17)	0.31405 (16)	0.57156 (15)	0.0243 (4)
H5A	0.7374	0.3366	0.5092	0.029*	0.90
C6	0.80224 (15)	0.38782 (15)	0.65610 (14)	0.0200 (4)
C7	0.76718 (16)	0.50656 (15)	0.64574 (13)	0.0203 (4)
C8	0.5579 (3)	0.8451 (2)	0.6092 (2)	0.0279 (7)	0.755 (6)
H8A	0.5829	0.8629	0.5347	0.034*	0.755 (6)
H8B	0.6103	0.8880	0.6601	0.034*	0.755 (6)
C9	0.4260 (3)	0.8792 (3)	0.6222 (3)	0.0463 (10)	0.755 (6)
H9A	0.4164	0.9562	0.6016	0.069*	0.755 (6)
H9B	0.4033	0.8698	0.6980	0.069*	0.755 (6)
H9C	0.3728	0.8338	0.5756	0.069*	0.755 (6)
C8A	0.4916 (9)	0.8158 (7)	0.5807 (7)	0.032 (2)	0.245 (6)
H8AA	0.5086	0.8280	0.5032	0.038*	0.245 (6)
H8AB	0.4054	0.7922	0.5867	0.038*	0.245 (6)
C9A	0.5141 (8)	0.9196 (7)	0.6449 (7)	0.033 (3)	0.245 (6)
H9AA	0.4629	0.9785	0.6147	0.049*	0.245 (6)
H9AB	0.6005	0.9403	0.6409	0.049*	0.245 (6)
H9AC	0.4935	0.9073	0.7208	0.049*	0.245 (6)
C10	0.54246 (19)	0.68425 (18)	0.73515 (15)	0.0297 (4)
H10A	0.5370	0.7459	0.7868	0.036*
H10B	0.6071	0.6341	0.7629	0.036*
C11	0.4206 (2)	0.6232 (2)	0.7324 (2)	0.0485 (6)
H11A	0.3562	0.6713	0.7029	0.073*
H11B	0.4002	0.6010	0.8061	0.073*
H11C	0.4271	0.5582	0.6865	0.073*
C12	0.78030 (17)	0.66718 (17)	0.37025 (15)	0.0260 (4)
H12A	0.8211	0.7276	0.3318	0.031*
H12B	0.7077	0.6450	0.3259	0.031*
C13	0.86787 (19)	0.57083 (18)	0.37903 (18)	0.0358 (5)
H13A	0.9365	0.5897	0.4281	0.054*
H13B	0.8989	0.5536	0.3072	0.054*
H13C	0.8247	0.5071	0.4074	0.054*
C14	0.82939 (17)	0.77616 (15)	0.53521 (15)	0.0241 (4)
H14A	0.9105	0.7403	0.5329	0.029*
H14B	0.8062	0.7812	0.6121	0.029*
C15	0.8391 (2)	0.89111 (17)	0.48869 (18)	0.0343 (5)
H15A	0.8554	0.8867	0.4111	0.051*
H15B	0.9060	0.9304	0.5259	0.051*
H15C	0.7620	0.9303	0.4991	0.051*

	U11	U22	U33	U12	U13	U23
P1	0.0162 (2)	0.0221 (3)	0.0187 (2)	0.00183 (17)	0.00024 (16)	0.00116 (17)
F1	0.0485 (8)	0.0294 (7)	0.0229 (6)	0.0034 (6)	−0.0118 (6)	−0.0017 (5)
F1A	0.025 (5)	0.014 (5)	0.018 (5)	0.003 (4)	−0.003 (4)	0.003 (4)
O1	0.0268 (7)	0.0235 (7)	0.0271 (7)	−0.0039 (6)	−0.0082 (5)	0.0007 (5)
O2	0.0172 (6)	0.0280 (7)	0.0236 (6)	−0.0007 (5)	−0.0028 (5)	0.0052 (5)
N1	0.0158 (7)	0.0218 (8)	0.0220 (7)	−0.0009 (6)	−0.0011 (5)	0.0005 (6)
N2	0.0284 (8)	0.0253 (8)	0.0245 (8)	0.0068 (7)	0.0064 (6)	0.0005 (6)
N3	0.0192 (7)	0.0224 (8)	0.0186 (7)	−0.0011 (6)	−0.0006 (5)	−0.0006 (6)
C1	0.0255 (9)	0.0283 (10)	0.0221 (9)	−0.0044 (8)	−0.0043 (7)	0.0018 (7)
C2	0.0247 (9)	0.0319 (11)	0.0338 (11)	0.0001 (8)	−0.0069 (8)	0.0140 (9)
C3	0.0236 (10)	0.0250 (10)	0.0414 (12)	0.0022 (8)	0.0037 (8)	0.0071 (9)
C4	0.0309 (10)	0.0237 (10)	0.0323 (10)	−0.0007 (8)	0.0043 (8)	−0.0004 (8)
C5	0.0254 (9)	0.0253 (10)	0.0222 (9)	0.0001 (8)	−0.0007 (7)	0.0025 (7)
C6	0.0152 (8)	0.0223 (9)	0.0223 (9)	−0.0007 (7)	0.0006 (6)	0.0043 (7)
C7	0.0198 (8)	0.0241 (9)	0.0170 (8)	−0.0002 (7)	0.0011 (6)	0.0021 (7)
C8	0.0256 (16)	0.0286 (15)	0.0294 (15)	0.0069 (12)	−0.0018 (12)	−0.0034 (11)
C9	0.0295 (17)	0.0396 (19)	0.069 (2)	0.0107 (14)	−0.0061 (14)	−0.0157 (16)
C8A	0.036 (5)	0.033 (5)	0.026 (4)	0.020 (4)	−0.017 (4)	−0.011 (4)
C9A	0.038 (5)	0.029 (5)	0.031 (4)	0.013 (4)	−0.003 (4)	−0.007 (4)
C10	0.0339 (11)	0.0328 (11)	0.0229 (10)	−0.0025 (9)	0.0099 (8)	−0.0048 (8)
C11	0.0439 (14)	0.0531 (16)	0.0498 (14)	−0.0144 (12)	0.0241 (11)	−0.0154 (12)
C12	0.0223 (9)	0.0356 (11)	0.0203 (9)	−0.0060 (8)	0.0034 (7)	−0.0037 (8)
C13	0.0316 (11)	0.0344 (12)	0.0420 (12)	−0.0005 (9)	0.0155 (9)	−0.0062 (9)
C14	0.0246 (9)	0.0221 (9)	0.0255 (9)	−0.0045 (8)	−0.0025 (7)	−0.0002 (7)
C15	0.0424 (12)	0.0231 (10)	0.0375 (11)	−0.0042 (9)	0.0012 (9)	0.0017 (9)

P1—O2	1.4855 (13)	C9—H9A	0.9800
P1—N2	1.6354 (16)	C9—H9B	0.9800
P1—N3	1.6387 (15)	C9—H9C	0.9800
P1—N1	1.6885 (16)	C8A—C9A	1.513 (11)
O1—C7	1.222 (2)	C8A—H8AA	0.9900
N1—C7	1.374 (2)	C8A—H8AB	0.9900
N1—H1N	0.860 (15)	C9A—H9AA	0.9800
N2—C8	1.476 (3)	C9A—H9AB	0.9800
N2—C10	1.476 (2)	C9A—H9AC	0.9800
N2—C8A	1.553 (7)	C10—C11	1.526 (3)
N3—C14	1.473 (2)	C10—H10A	0.9900
N3—C12	1.478 (2)	C10—H10B	0.9900
C1—C2	1.382 (3)	C11—H11A	0.9800
C1—C6	1.396 (2)	C11—H11B	0.9800
C1—H1A	0.9500	C11—H11C	0.9800
C2—C3	1.373 (3)	C12—C13	1.520 (3)
C2—H2	0.9500	C12—H12A	0.9900
C3—C4	1.382 (3)	C12—H12B	0.9900
C3—H3	0.9500	C13—H13A	0.9800
C4—C5	1.388 (3)	C13—H13B	0.9800
C4—H4	0.9500	C13—H13C	0.9800
C5—C6	1.390 (3)	C14—C15	1.522 (3)
C5—H5A	0.9500	C14—H14A	0.9900
C6—C7	1.506 (3)	C14—H14B	0.9900
C8—C9	1.514 (4)	C15—H15A	0.9800
C8—H8A	0.9900	C15—H15B	0.9800
C8—H8B	0.9900	C15—H15C	0.9800
O2—P1—N2	117.38 (8)	N2—C8A—H8AA	110.3
O2—P1—N3	110.11 (7)	C9A—C8A—H8AB	110.3
N2—P1—N3	106.10 (8)	N2—C8A—H8AB	110.3
O2—P1—N1	105.95 (8)	H8AA—C8A—H8AB	108.6
N2—P1—N1	105.82 (8)	C8A—C9A—H9AA	109.5
N3—P1—N1	111.47 (8)	C8A—C9A—H9AB	109.5
C7—N1—P1	126.13 (13)	H9AA—C9A—H9AB	109.5
C7—N1—H1N	118.0 (14)	C8A—C9A—H9AC	109.5
P1—N1—H1N	115.7 (14)	H9AA—C9A—H9AC	109.5
C8—N2—C10	116.79 (17)	H9AB—C9A—H9AC	109.5
C8—N2—C8A	33.4 (4)	N2—C10—C11	114.35 (18)
C10—N2—C8A	114.2 (4)	N2—C10—H10A	108.7
C8—N2—P1	119.88 (15)	C11—C10—H10A	108.7
C10—N2—P1	122.61 (14)	N2—C10—H10B	108.7
C8A—N2—P1	107.7 (3)	C11—C10—H10B	108.7
C14—N3—C12	114.42 (14)	H10A—C10—H10B	107.6
C14—N3—P1	125.08 (12)	C10—C11—H11A	109.5
C12—N3—P1	117.98 (12)	C10—C11—H11B	109.5
C2—C1—C6	122.54 (18)	H11A—C11—H11B	109.5
C2—C1—H1A	118.7	C10—C11—H11C	109.5
C6—C1—H1A	118.7	H11A—C11—H11C	109.5
C3—C2—C1	119.41 (18)	H11B—C11—H11C	109.5
C3—C2—H2	120.3	N3—C12—C13	113.92 (16)
C1—C2—H2	120.3	N3—C12—H12A	108.8
C2—C3—C4	120.08 (19)	C13—C12—H12A	108.8
C2—C3—H3	120.0	N3—C12—H12B	108.8
C4—C3—H3	120.0	C13—C12—H12B	108.8
C3—C4—C5	119.69 (19)	H12A—C12—H12B	107.7
C3—C4—H4	120.2	C12—C13—H13A	109.5
C5—C4—H4	120.2	C12—C13—H13B	109.5
C4—C5—C6	121.87 (17)	H13A—C13—H13B	109.5
C4—C5—H5A	119.1	C12—C13—H13C	109.5
C6—C5—H5A	119.1	H13A—C13—H13C	109.5
C5—C6—C1	116.39 (17)	H13B—C13—H13C	109.5
C5—C6—C7	121.92 (15)	N3—C14—C15	112.69 (16)
C1—C6—C7	121.34 (16)	N3—C14—H14A	109.1
O1—C7—N1	122.84 (17)	C15—C14—H14A	109.1
O1—C7—C6	121.22 (15)	N3—C14—H14B	109.1
N1—C7—C6	115.87 (15)	C15—C14—H14B	109.1
N2—C8—C9	113.5 (2)	H14A—C14—H14B	107.8
N2—C8—H8A	108.9	C14—C15—H15A	109.5
C9—C8—H8A	108.9	C14—C15—H15B	109.5
N2—C8—H8B	108.9	H15A—C15—H15B	109.5
C9—C8—H8B	108.9	C14—C15—H15C	109.5
H8A—C8—H8B	107.7	H15A—C15—H15C	109.5
C9A—C8A—N2	106.9 (6)	H15B—C15—H15C	109.5
C9A—C8A—H8AA	110.3
O2—P1—N1—C7	158.75 (14)	C4—C5—C6—C7	171.39 (17)
N2—P1—N1—C7	−75.93 (16)	C2—C1—C6—C5	0.7 (3)
N3—P1—N1—C7	38.97 (17)	C2—C1—C6—C7	−172.59 (17)
O2—P1—N2—C8	−72.0 (2)	P1—N1—C7—O1	17.5 (3)
N3—P1—N2—C8	51.5 (2)	P1—N1—C7—C6	−159.56 (12)
N1—P1—N2—C8	170.05 (18)	C5—C6—C7—O1	−139.50 (18)
O2—P1—N2—C10	97.97 (16)	C1—C6—C7—O1	33.4 (3)
N3—P1—N2—C10	−138.49 (15)	C5—C6—C7—N1	37.6 (2)
N1—P1—N2—C10	−19.96 (17)	C1—C6—C7—N1	−149.49 (17)
O2—P1—N2—C8A	−37.8 (5)	C10—N2—C8—C9	−56.1 (3)
N3—P1—N2—C8A	85.7 (5)	C8A—N2—C8—C9	37.9 (6)
N1—P1—N2—C8A	−155.7 (5)	P1—N2—C8—C9	114.5 (2)
O2—P1—N3—C14	159.56 (14)	C8—N2—C8A—C9A	−28.3 (5)
N2—P1—N3—C14	31.58 (16)	C10—N2—C8A—C9A	74.1 (8)
N1—P1—N3—C14	−83.15 (16)	P1—N2—C8A—C9A	−146.0 (6)
O2—P1—N3—C12	−39.48 (15)	C8—N2—C10—C11	100.8 (2)
N2—P1—N3—C12	−167.46 (13)	C8A—N2—C10—C11	63.7 (5)
N1—P1—N3—C12	77.81 (15)	P1—N2—C10—C11	−69.5 (2)
C6—C1—C2—C3	0.7 (3)	C14—N3—C12—C13	77.6 (2)
C1—C2—C3—C4	−1.0 (3)	P1—N3—C12—C13	−85.37 (18)
C2—C3—C4—C5	−0.1 (3)	C12—N3—C14—C15	75.8 (2)
C3—C4—C5—C6	1.6 (3)	P1—N3—C14—C15	−122.62 (16)
C4—C5—C6—C1	−1.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2i	0.86 (2)	1.93 (2)	2.7714 (19)	167 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2i	0.86 (2)	1.93 (2)	2.7714 (19)	167 (2)

Symmetry code: (i) .