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organic compounds
N,N,N′,N′-Tetraethyl-N′′-(2-fluorobenzoyl)phosphoric triamide
aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad 91779, Iran, and bDepartment of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
*Correspondence e-mail: mehrdad_pourayoubi@yahoo.com
In the title compound, C15H25FN3O2P, 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 tetrahedral 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 fluorobenzene ring about its connecting C—C bond. In the crystal, pairs of intermolecular 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
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2005); cell 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
).
Supporting information
https://doi.org/10.1107/S1600536811036944/lh5308sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036944/lh5308Isup2.hkl
2-F—C6H4C(O)NHP(O)Cl2 was prepared according to the literature method reported by Pourayoubi et al. (2011a).
The title compound was synthesized from the reaction of 0.40 g (1.56 mmol) 2-F—C6H4C(O)NHP(O)Cl2 with 0.456 g (6.24 mmol) of diethyl amine in dry chloroform (30 ml). The amine was added dropwise to a solution of 2-F—C6H4C(O)NHP(O)Cl2 at 273 K, with continuous stirring. After 17 h, the solvent was evaporated; the obtained solid was washed with distilled water and dissolved in a mixture of CH3OH/DMF [4:1 (v/v)]. Single crystals were obtained from this solution after a few days at room temperature. IR (KBr, ν, cm-1): 3061 (NH), 2970, 2886, 1675 (C═O), 1457, 1196, 1048, 946, 766.
Atoms C8 and C9 are disordered over two sets of sites with refined occupancies of 0.755 (6) and 0.245 (6). The fluorine atom is disordered over two positions and refined with the occupancy F1 and F1A fixed at 0.9 and 0.1 and the corresponding hydrogen atoms H1A and H5A were also treated as disordered. Hydrogen H1N was found in a Fourier difference map and refined with a N1—H1N distance was set at 0.87 (0.02) Å and allowed to refine with Uiso at 1.2 of parent N atom. All other hydrogen atoms were placed in calculated positions with C—H distances for CH2 of 0.99 Å, CH3 of 0.98 Å and C(Ar)H of 0.95 Å and with Uiso of 1.20 (or 1.5 for methyl H atoms) that of the parent C atom.
Following our previous work on phosphoric triamides containing an XC(O)NHP(O) moiety, X = 2-F—C6H4 (Pourayoubi et al., 2011a), 4-F—C6H4 (Tarahhomi et al., 2011) and 2,6-F2—C6H3 (Pourayoubi et al., 2011b), herein, we report the synthesis and
of the title compound, P(O)[2-F—C6H4C(O)NH][N(C2H5)2]2 (Fig. 1).One of the —CH2CH3 groups in the diethylamido substituent N2 is disordered over two sets of sites with refined occupancies of 0.755 (6) and 0.245 (6). The fluorine atom of the aromatic ring is disordered over two sets of sites with occupancies of 0.9 and 0.1.
In the C(═O)NHP(═O) skeleton of the title phosphoric triamide, the phosphoryl group adopts the anti orientation with respect to the carbonyl group; whereas it is in a syn position relative to the N—H unit. The tetrahedral environment at the P atom is distorted as has been noted for the other phosphoric triamides. The P═O, C═O and P—N bond lengths are within the expected values (Pourayoubi et al. (2011b) and Tarahhomi et al. (2011)).
In the crystal, pairs of intermolecular N—H···O(P) hydrogen bonds form a hydrogen-bonded dimer with R22(8) graph-set notation (Bernstein et al., 1995).
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).
Data collection: APEX2 (Bruker, 2005); cell
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).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 monochromator | 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 |
C15H25FN3O2P | V = 1648.2 (2) Å3 |
Mr = 329.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.9296 (9) Å | µ = 0.19 mm−1 |
b = 12.2221 (10) Å | T = 100 K |
c = 12.3423 (10) Å | 0.45 × 0.40 × 0.35 mm |
β = 91.443 (1)° |
Bruker APEXII CCD diffractometer | 3741 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3056 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.937 | Rint = 0.051 |
11336 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 6 restraints |
wR(F2) = 0.122 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.55 e Å−3 |
3741 reflections | Δρmin = −0.42 e Å−3 |
236 parameters |
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) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H25FN3O2P |
Mr | 329.35 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.9296 (9), 12.2221 (10), 12.3423 (10) |
β (°) | 91.443 (1) |
V (Å3) | 1648.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.45 × 0.40 × 0.35 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.920, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11336, 3741, 3056 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.122, 1.08 |
No. of reflections | 3741 |
No. of parameters | 236 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.42 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.860 (15) | 1.928 (16) | 2.7714 (19) | 167 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Following our previous work on phosphoric triamides containing an XC(O)NHP(O) moiety, X = 2-F—C6H4 (Pourayoubi et al., 2011a), 4-F—C6H4 (Tarahhomi et al., 2011) and 2,6-F2—C6H3 (Pourayoubi et al., 2011b), herein, we report the synthesis and crystal structure of the title compound, P(O)[2-F—C6H4C(O)NH][N(C2H5)2]2 (Fig. 1).
One of the —CH2CH3 groups in the diethylamido substituent N2 is disordered over two sets of sites with refined occupancies of 0.755 (6) and 0.245 (6). The fluorine atom of the aromatic ring is disordered over two sets of sites with occupancies of 0.9 and 0.1.
In the C(═O)NHP(═O) skeleton of the title phosphoric triamide, the phosphoryl group adopts the anti orientation with respect to the carbonyl group; whereas it is in a syn position relative to the N—H unit. The tetrahedral environment at the P atom is distorted as has been noted for the other phosphoric triamides. The P═O, C═O and P—N bond lengths are within the expected values (Pourayoubi et al. (2011b) and Tarahhomi et al. (2011)).
In the crystal, pairs of intermolecular N—H···O(P) hydrogen bonds form a hydrogen-bonded dimer with R22(8) graph-set notation (Bernstein et al., 1995).