organic compounds
Bis(pyrrolidin-1-yl)phosphinic (2,4-difluorobenzoyl)amide
aDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran, and bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
*Correspondence e-mail: pourayoubi@um.ac.ir
The P atom in the title molecule, C15H20F2N3O2P, is in a distorted tetrahedral P(O)(N)(N)2 environment. The phosphoryl group and the NH unit adopt a syn orientation with respect to each other. An F atom at position 2 and an H atom at position 6 are found to occupy similar sites in a 0.70:0.30 ratio and were refined with fixed occupancies. The pyrrolidin-1-yl rings are disordered over two sets of sites, with site occupancies of 0.566 (6) and 0.434 (6), and were refined using a two-part model. In the crystal, hydrogen-bonded dimers linked by pairs of N—H⋯O(P) hydrogen bonds generate an R22(8) ring motif.
Related literature
For background and related crystal structures, see: Pourayoubi et al. (2011, 2012). For the preparation of the starting compound, see: Pourayoubi et al. (2012). For graph-set motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
|
Refinement
|
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010); 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
10.1107/S1600536812034733/pv2575sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812034733/pv2575Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812034733/pv2575Isup3.cml
2,4-F2—C6H3C(O)NHP(O)Cl2 was prepared according to the literature method (Pourayoubi et al., 2012). To a solution of 2,4-F2–C6H3C(O)NHP(O)Cl2 (2 mmol) in CHCl3 (20 ml), a solution of pyrrolidine (8 mmol) in CHCl3 (10 ml) was added dropwise at 273 K. After 4 h of stirring, the solvent was evaporated at room temperature and the solid was washed with distilled water. Single crystals of the title compound were obtained from a mixture of methanol/acetonitrile (1:1) after slow evaporation at room temperature.
Fluorine atom F1 and hydrogen atom H1A (and F1A and H1) were found to occupy similar sites in the ratio of 70/30 and were refined with fixed occupancies. Rings N2, C8—C11 and N3, C12—C15 were disordered and were refined using a two part model. Hydrogen atom H1N was found from a Fourier difference map and was refined with N—H distance of 0.87 Å and 1.20 × Ueq of N atom. All other hydrogen atoms were placed in calculated positions, CH2 0.99 Å, C(Ar)—H 0.95 Å with 1.20 Ueq of the parent carbon atoms.
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); 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).C15H20F2N3O2P | F(000) = 720 |
Mr = 343.31 | Dx = 1.359 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7108 reflections |
a = 9.1028 (3) Å | θ = 3.3–32.3° |
b = 9.9477 (2) Å | µ = 0.20 mm−1 |
c = 18.5465 (5) Å | T = 173 K |
β = 92.268 (3)° | Block, colorless |
V = 1678.11 (8) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 4 |
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 4339 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3828 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 16.1500 pixels mm-1 | θmax = 28.7°, θmin = 3.3° |
ω scans | h = −12→7 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | k = −12→13 |
Tmin = 0.926, Tmax = 0.962 | l = −24→25 |
17134 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0515P)2 + 0.7979P] where P = (Fo2 + 2Fc2)/3 |
4339 reflections | (Δ/σ)max = 0.001 |
300 parameters | Δρmax = 0.38 e Å−3 |
25 restraints | Δρmin = −0.30 e Å−3 |
C15H20F2N3O2P | V = 1678.11 (8) Å3 |
Mr = 343.31 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.1028 (3) Å | µ = 0.20 mm−1 |
b = 9.9477 (2) Å | T = 173 K |
c = 18.5465 (5) Å | 0.40 × 0.30 × 0.20 mm |
β = 92.268 (3)° |
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 4339 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | 3828 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.962 | Rint = 0.017 |
17134 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 25 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.38 e Å−3 |
4339 reflections | Δρmin = −0.30 e Å−3 |
300 parameters |
Experimental. IR (KBr, ν, cm-1): 3067, 2973, 2892, 1685, 1623, 1457, 1258, 1220, 1177, 1129, 1087, 1011, 968, 859, 811. 1H NMR (400.22 MHz, DMSO-d6, 293.9 K, TMS): 1.57 (m, 8H), 3.14 (m, 8H), 7.19 (t, 1H, Ar—H), 7.36 (t, 3J[(H,H),(H,F)] = 10.0 Hz, 1H, Ar—H), 7.66 (m, 1H, Ar—H), 9.26 p.p.m. (s, 1H, N—H). 13C NMR (100.64 MHz, DMSO-d6, 293.9 K, TMS): 26.38 (d, 3J(C,P) = 9.1 Hz, 4C), 46.34 (d, 2J(C,P) = 5.0 Hz, 4C), 105.03 (t, 2J(C,F) = 26.2 Hz, 1C, Ar—C), 112.16 (dd, 2J(C,F) = 21.6 Hz, 4J(C,F) = 3.5 Hz, 1C, Ar—C), 121.61 (m, 1C, Ar—C), 132.22 (dd, 3J(C,F) = 4.0 Hz and 11.1 Hz, 1C, Ar—C), 160.29 (d, 3J(C,F) = 13.6, 1J(C,F) = 252.1 Hz, 1C, Ar—C), 164.06 (d, 3J(C,F) = 12.1, 1J(C,F) = 251.1 Hz, 1C, Ar—C), 165.37 p.p.m. (s, 1C, C(O)). 31P{1H} NMR (162.01 MHz, DMSO-d6, 293.9 K, 85% H3PO4): 5.66 p.p.m. (s). |
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 | 0.59836 (4) | 0.47159 (3) | 0.114620 (16) | 0.02308 (10) | |
F1 | 0.59877 (19) | 1.01499 (17) | 0.13543 (9) | 0.0434 (4) | 0.70 |
F1A | 0.2448 (4) | 0.6940 (3) | 0.0502 (2) | 0.0405 (8) | 0.30 |
F2 | 0.17516 (14) | 1.14989 (11) | 0.00596 (7) | 0.0617 (3) | |
O1 | 0.53714 (12) | 0.37387 (9) | 0.06124 (5) | 0.0316 (2) | |
O3 | 0.57983 (14) | 0.75048 (11) | 0.18642 (6) | 0.0425 (3) | |
N1 | 0.53996 (13) | 0.62346 (11) | 0.08554 (6) | 0.0264 (2) | |
H1N | 0.5064 (18) | 0.6275 (17) | 0.0427 (7) | 0.032* | |
N2 | 0.54212 (13) | 0.44054 (13) | 0.19479 (6) | 0.0317 (3) | |
N3 | 0.77636 (14) | 0.47924 (12) | 0.12213 (7) | 0.0326 (3) | |
C1 | 0.47337 (16) | 0.98082 (14) | 0.09944 (7) | 0.0289 (3) | |
H1A | 0.571 (4) | 1.003 (9) | 0.117 (4) | 0.035* | 0.30 |
C2 | 0.38927 (18) | 1.08460 (14) | 0.07115 (8) | 0.0351 (3) | |
H2A | 0.4184 | 1.1758 | 0.0770 | 0.042* | |
C3 | 0.26117 (18) | 1.05011 (15) | 0.03401 (9) | 0.0365 (3) | |
C4 | 0.21545 (16) | 0.91998 (16) | 0.02352 (8) | 0.0354 (3) | |
H4A | 0.1260 | 0.9000 | −0.0024 | 0.042* | |
C5 | 0.30424 (15) | 0.81899 (14) | 0.05208 (7) | 0.0285 (3) | |
H1 | 0.278 (4) | 0.7283 (15) | 0.0411 (18) | 0.034* | 0.70 |
C6 | 0.43458 (14) | 0.84645 (12) | 0.09091 (6) | 0.0239 (2) | |
C7 | 0.52591 (15) | 0.73730 (13) | 0.12577 (7) | 0.0264 (3) | |
C8 | 0.6225 (6) | 0.4742 (8) | 0.2636 (3) | 0.0272 (17) | 0.566 (6) |
H8A | 0.6806 | 0.5577 | 0.2591 | 0.033* | 0.566 (6) |
H8B | 0.6888 | 0.4002 | 0.2796 | 0.033* | 0.566 (6) |
C9 | 0.4996 (10) | 0.4928 (11) | 0.3144 (4) | 0.065 (2) | 0.566 (6) |
H9A | 0.4666 | 0.5877 | 0.3146 | 0.078* | 0.566 (6) |
H9B | 0.5314 | 0.4667 | 0.3641 | 0.078* | 0.566 (6) |
C10 | 0.3769 (6) | 0.4013 (8) | 0.2855 (2) | 0.0748 (16) | 0.566 (6) |
H10A | 0.2804 | 0.4304 | 0.3028 | 0.090* | 0.566 (6) |
H10B | 0.3948 | 0.3069 | 0.3003 | 0.090* | 0.566 (6) |
C11 | 0.3829 (8) | 0.4168 (11) | 0.2035 (4) | 0.0489 (19) | 0.566 (6) |
H11A | 0.3491 | 0.3341 | 0.1781 | 0.059* | 0.566 (6) |
H11B | 0.3231 | 0.4940 | 0.1858 | 0.059* | 0.566 (6) |
C8A | 0.6167 (14) | 0.4736 (16) | 0.2641 (6) | 0.063 (5) | 0.434 (6) |
H8AA | 0.6565 | 0.5662 | 0.2632 | 0.076* | 0.434 (6) |
H8AB | 0.6987 | 0.4103 | 0.2747 | 0.076* | 0.434 (6) |
C9A | 0.5017 (15) | 0.4612 (18) | 0.3196 (8) | 0.085 (5) | 0.434 (6) |
H9AA | 0.5180 | 0.5274 | 0.3589 | 0.102* | 0.434 (6) |
H9AB | 0.5003 | 0.3696 | 0.3404 | 0.102* | 0.434 (6) |
C10A | 0.3614 (6) | 0.4907 (8) | 0.2760 (3) | 0.0644 (17) | 0.434 (6) |
H10C | 0.3506 | 0.5875 | 0.2646 | 0.077* | 0.434 (6) |
H10D | 0.2731 | 0.4583 | 0.3003 | 0.077* | 0.434 (6) |
C11A | 0.3941 (13) | 0.4072 (19) | 0.2095 (7) | 0.079 (5) | 0.434 (6) |
H11C | 0.3842 | 0.3099 | 0.2196 | 0.095* | 0.434 (6) |
H11D | 0.3267 | 0.4313 | 0.1683 | 0.095* | 0.434 (6) |
C12 | 0.8722 (3) | 0.5949 (3) | 0.1329 (3) | 0.0476 (10) | 0.566 (6) |
H12A | 0.8306 | 0.6592 | 0.1673 | 0.057* | 0.566 (6) |
H12B | 0.8873 | 0.6417 | 0.0866 | 0.057* | 0.566 (6) |
C13 | 1.0112 (5) | 0.5376 (5) | 0.1622 (6) | 0.118 (3) | 0.566 (6) |
H13A | 1.0949 | 0.5834 | 0.1402 | 0.142* | 0.566 (6) |
H13B | 1.0191 | 0.5532 | 0.2150 | 0.142* | 0.566 (6) |
C14 | 1.0185 (4) | 0.3994 (5) | 0.1484 (3) | 0.0579 (11) | 0.566 (6) |
H14A | 1.0650 | 0.3506 | 0.1898 | 0.069* | 0.566 (6) |
H14B | 1.0740 | 0.3810 | 0.1047 | 0.069* | 0.566 (6) |
C15 | 0.8656 (9) | 0.3626 (9) | 0.1378 (6) | 0.065 (3) | 0.566 (6) |
H15A | 0.8549 | 0.2979 | 0.0973 | 0.078* | 0.566 (6) |
H15B | 0.8314 | 0.3181 | 0.1818 | 0.078* | 0.566 (6) |
C12A | 0.8614 (5) | 0.5743 (6) | 0.0805 (4) | 0.0635 (17) | 0.434 (6) |
H12C | 0.8512 | 0.6670 | 0.0991 | 0.076* | 0.434 (6) |
H12D | 0.8299 | 0.5725 | 0.0288 | 0.076* | 0.434 (6) |
C13A | 1.0174 (6) | 0.5242 (7) | 0.0916 (6) | 0.081 (2) | 0.434 (6) |
H13C | 1.0757 | 0.5418 | 0.0487 | 0.098* | 0.434 (6) |
H13D | 1.0668 | 0.5667 | 0.1343 | 0.098* | 0.434 (6) |
C14A | 0.9971 (6) | 0.3782 (7) | 0.1029 (6) | 0.082 (2) | 0.434 (6) |
H14C | 1.0803 | 0.3433 | 0.1335 | 0.099* | 0.434 (6) |
H14D | 0.9982 | 0.3316 | 0.0558 | 0.099* | 0.434 (6) |
C15A | 0.8561 (9) | 0.3470 (9) | 0.1381 (4) | 0.0336 (18) | 0.434 (6) |
H15C | 0.8710 | 0.3310 | 0.1906 | 0.040* | 0.434 (6) |
H15D | 0.8046 | 0.2694 | 0.1153 | 0.040* | 0.434 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.02981 (18) | 0.02096 (16) | 0.01801 (16) | 0.00199 (12) | −0.00475 (11) | 0.00008 (11) |
F1 | 0.0477 (8) | 0.0307 (7) | 0.0504 (10) | −0.0092 (6) | −0.0175 (6) | −0.0046 (6) |
F1A | 0.0350 (18) | 0.0305 (16) | 0.055 (2) | −0.0053 (12) | −0.0065 (14) | −0.0031 (14) |
F2 | 0.0686 (7) | 0.0373 (6) | 0.0781 (8) | 0.0235 (5) | −0.0103 (6) | 0.0113 (5) |
O1 | 0.0503 (6) | 0.0211 (4) | 0.0227 (4) | 0.0007 (4) | −0.0091 (4) | −0.0013 (3) |
O3 | 0.0668 (8) | 0.0314 (5) | 0.0276 (5) | 0.0033 (5) | −0.0184 (5) | −0.0070 (4) |
N1 | 0.0376 (6) | 0.0214 (5) | 0.0193 (5) | 0.0052 (4) | −0.0090 (4) | −0.0025 (4) |
N2 | 0.0337 (6) | 0.0406 (7) | 0.0205 (5) | −0.0028 (5) | −0.0027 (4) | 0.0009 (5) |
N3 | 0.0317 (6) | 0.0307 (6) | 0.0349 (6) | 0.0038 (5) | −0.0034 (5) | 0.0060 (5) |
C1 | 0.0343 (7) | 0.0247 (6) | 0.0277 (6) | −0.0036 (5) | 0.0024 (5) | −0.0037 (5) |
C2 | 0.0492 (9) | 0.0203 (6) | 0.0365 (7) | −0.0001 (6) | 0.0090 (6) | 0.0004 (5) |
C3 | 0.0420 (8) | 0.0285 (7) | 0.0393 (8) | 0.0126 (6) | 0.0042 (6) | 0.0053 (6) |
C4 | 0.0319 (7) | 0.0350 (7) | 0.0388 (8) | 0.0057 (6) | −0.0031 (6) | 0.0000 (6) |
C5 | 0.0308 (7) | 0.0235 (6) | 0.0310 (6) | 0.0001 (5) | −0.0001 (5) | −0.0020 (5) |
C6 | 0.0300 (6) | 0.0206 (6) | 0.0213 (5) | 0.0015 (5) | 0.0021 (5) | −0.0020 (4) |
C7 | 0.0334 (7) | 0.0222 (6) | 0.0232 (6) | 0.0002 (5) | −0.0038 (5) | −0.0023 (5) |
C8 | 0.031 (2) | 0.040 (5) | 0.011 (3) | 0.004 (2) | −0.002 (2) | 0.001 (3) |
C9 | 0.073 (5) | 0.094 (4) | 0.029 (3) | −0.020 (3) | 0.015 (3) | −0.026 (3) |
C10 | 0.073 (3) | 0.108 (5) | 0.045 (2) | −0.016 (3) | 0.023 (2) | 0.007 (3) |
C11 | 0.027 (2) | 0.085 (5) | 0.035 (3) | −0.010 (2) | 0.014 (2) | 0.001 (3) |
C8A | 0.096 (8) | 0.054 (9) | 0.038 (7) | −0.004 (6) | −0.025 (6) | 0.005 (6) |
C9A | 0.073 (7) | 0.150 (12) | 0.033 (4) | 0.011 (6) | 0.008 (4) | 0.025 (6) |
C10A | 0.057 (3) | 0.091 (5) | 0.047 (3) | 0.014 (3) | 0.020 (2) | 0.007 (3) |
C11A | 0.065 (6) | 0.134 (12) | 0.037 (4) | −0.022 (6) | −0.017 (4) | −0.003 (5) |
C12 | 0.0330 (15) | 0.0340 (15) | 0.076 (3) | −0.0070 (11) | −0.0001 (15) | 0.0075 (16) |
C13 | 0.038 (2) | 0.063 (3) | 0.249 (10) | −0.003 (2) | −0.038 (4) | −0.015 (4) |
C14 | 0.0310 (16) | 0.061 (2) | 0.080 (3) | 0.0046 (15) | −0.0115 (18) | 0.014 (2) |
C15 | 0.048 (4) | 0.052 (4) | 0.095 (5) | 0.010 (3) | 0.002 (3) | 0.036 (3) |
C12A | 0.043 (2) | 0.053 (3) | 0.095 (5) | −0.009 (2) | 0.004 (3) | 0.019 (3) |
C13A | 0.031 (2) | 0.074 (4) | 0.139 (7) | −0.005 (2) | 0.009 (3) | 0.024 (4) |
C14A | 0.030 (2) | 0.069 (4) | 0.148 (8) | 0.013 (2) | 0.000 (4) | −0.003 (5) |
C15A | 0.029 (3) | 0.033 (3) | 0.037 (3) | 0.015 (2) | −0.014 (2) | −0.009 (3) |
P1—O1 | 1.4805 (10) | C10—H10A | 0.9900 |
P1—N2 | 1.6213 (12) | C10—H10B | 0.9900 |
P1—N3 | 1.6226 (13) | C11—H11A | 0.9900 |
P1—N1 | 1.6832 (11) | C11—H11B | 0.9900 |
F1—C1 | 1.3431 (19) | C8A—C9A | 1.502 (14) |
F1—H1A | 0.43 (5) | C8A—H8AA | 0.9900 |
F1A—C5 | 1.356 (3) | C8A—H8AB | 0.9900 |
F1A—H1 | 0.49 (2) | C9A—C10A | 1.513 (14) |
F2—C3 | 1.3552 (17) | C9A—H9AA | 0.9900 |
O3—C7 | 1.2165 (16) | C9A—H9AB | 0.9900 |
N1—C7 | 1.3649 (16) | C10A—C11A | 1.526 (13) |
N1—H1N | 0.841 (13) | C10A—H10C | 0.9900 |
N2—C11A | 1.425 (11) | C10A—H10D | 0.9900 |
N2—C8A | 1.467 (11) | C11A—H11C | 0.9900 |
N2—C11 | 1.484 (6) | C11A—H11D | 0.9900 |
N2—C8 | 1.484 (6) | C12—C13 | 1.472 (5) |
N3—C15 | 1.440 (9) | C12—H12A | 0.9900 |
N3—C12 | 1.453 (3) | C12—H12B | 0.9900 |
N3—C12A | 1.462 (5) | C13—C14 | 1.400 (7) |
N3—C15A | 1.526 (8) | C13—H13A | 0.9900 |
C1—C2 | 1.377 (2) | C13—H13B | 0.9900 |
C1—C6 | 1.3900 (18) | C14—C15 | 1.445 (9) |
C1—H1A | 0.957 (10) | C14—H14A | 0.9900 |
C2—C3 | 1.374 (2) | C14—H14B | 0.9900 |
C2—H2A | 0.9500 | C15—H15A | 0.9900 |
C3—C4 | 1.371 (2) | C15—H15B | 0.9900 |
C4—C5 | 1.3817 (19) | C12A—C13A | 1.512 (7) |
C4—H4A | 0.9500 | C12A—H12C | 0.9900 |
C5—C6 | 1.3905 (18) | C12A—H12D | 0.9900 |
C5—H1 | 0.953 (10) | C13A—C14A | 1.480 (8) |
C6—C7 | 1.4985 (17) | C13A—H13C | 0.9900 |
C8—C9 | 1.503 (8) | C13A—H13D | 0.9900 |
C8—H8A | 0.9900 | C14A—C15A | 1.495 (10) |
C8—H8B | 0.9900 | C14A—H14C | 0.9900 |
C9—C10 | 1.521 (9) | C14A—H14D | 0.9900 |
C9—H9A | 0.9900 | C15A—H15C | 0.9900 |
C9—H9B | 0.9900 | C15A—H15D | 0.9900 |
C10—C11 | 1.532 (9) | ||
O1—P1—N2 | 111.35 (6) | H11A—C11—H11B | 109.3 |
O1—P1—N3 | 115.87 (7) | N2—C8A—C9A | 105.7 (10) |
N2—P1—N3 | 106.30 (6) | N2—C8A—H8AA | 110.6 |
O1—P1—N1 | 105.63 (5) | C9A—C8A—H8AA | 110.6 |
N2—P1—N1 | 110.96 (6) | N2—C8A—H8AB | 110.6 |
N3—P1—N1 | 106.68 (6) | C9A—C8A—H8AB | 110.6 |
C7—N1—P1 | 127.22 (9) | H8AA—C8A—H8AB | 108.7 |
C7—N1—H1N | 116.0 (12) | C8A—C9A—C10A | 102.4 (10) |
P1—N1—H1N | 116.3 (12) | C8A—C9A—H9AA | 111.3 |
C11A—N2—C8A | 107.0 (7) | C10A—C9A—H9AA | 111.3 |
C8A—N2—C11 | 111.2 (6) | C8A—C9A—H9AB | 111.3 |
C11A—N2—C8 | 109.0 (6) | C10A—C9A—H9AB | 111.3 |
C11—N2—C8 | 113.1 (4) | H9AA—C9A—H9AB | 109.2 |
C11A—N2—P1 | 123.8 (6) | C9A—C10A—C11A | 98.0 (9) |
C8A—N2—P1 | 127.5 (5) | C9A—C10A—H10C | 112.2 |
C11—N2—P1 | 118.4 (3) | C11A—C10A—H10C | 112.2 |
C8—N2—P1 | 125.6 (2) | C9A—C10A—H10D | 112.2 |
C15—N3—C12 | 106.2 (4) | C11A—C10A—H10D | 112.2 |
C15—N3—C12A | 108.8 (4) | H10C—C10A—H10D | 109.8 |
C12—N3—C15A | 112.2 (3) | N2—C11A—C10A | 104.1 (9) |
C12A—N3—C15A | 113.7 (4) | N2—C11A—H11C | 110.9 |
C15—N3—P1 | 122.2 (4) | C10A—C11A—H11C | 110.9 |
C12—N3—P1 | 129.90 (15) | N2—C11A—H11D | 110.9 |
C12A—N3—P1 | 122.2 (2) | C10A—C11A—H11D | 110.9 |
C15A—N3—P1 | 116.2 (3) | H11C—C11A—H11D | 108.9 |
F1—C1—C2 | 116.64 (14) | N3—C12—C13 | 104.3 (3) |
F1—C1—C6 | 120.47 (14) | N3—C12—H12A | 110.9 |
C2—C1—C6 | 122.88 (13) | C13—C12—H12A | 110.9 |
C2—C1—H1A | 117 (5) | N3—C12—H12B | 110.9 |
C6—C1—H1A | 119 (5) | C13—C12—H12B | 110.9 |
C3—C2—C1 | 116.86 (13) | H12A—C12—H12B | 108.9 |
C3—C2—H2A | 121.6 | C14—C13—C12 | 111.0 (4) |
C1—C2—H2A | 121.6 | C14—C13—H13A | 109.4 |
F2—C3—C4 | 118.00 (15) | C12—C13—H13A | 109.4 |
F2—C3—C2 | 118.39 (14) | C14—C13—H13B | 109.4 |
C4—C3—C2 | 123.62 (13) | C12—C13—H13B | 109.4 |
C3—C4—C5 | 117.54 (14) | H13A—C13—H13B | 108.0 |
C3—C4—H4A | 121.2 | C13—C14—C15 | 102.8 (5) |
C5—C4—H4A | 121.2 | C13—C14—H14A | 111.2 |
F1A—C5—C4 | 115.48 (19) | C15—C14—H14A | 111.2 |
F1A—C5—C6 | 121.66 (19) | C13—C14—H14B | 111.2 |
C4—C5—C6 | 122.00 (13) | C15—C14—H14B | 111.2 |
C4—C5—H1 | 118 (2) | H14A—C14—H14B | 109.1 |
C6—C5—H1 | 120 (2) | N3—C15—C14 | 110.8 (6) |
C1—C6—C5 | 117.10 (12) | N3—C15—H15A | 109.5 |
C1—C6—C7 | 120.90 (12) | C14—C15—H15A | 109.5 |
C5—C6—C7 | 121.91 (11) | N3—C15—H15B | 109.5 |
O3—C7—N1 | 123.49 (12) | C14—C15—H15B | 109.5 |
O3—C7—C6 | 121.16 (12) | H15A—C15—H15B | 108.1 |
N1—C7—C6 | 115.32 (11) | N3—C12A—C13A | 103.2 (4) |
N2—C8—C9 | 102.3 (5) | N3—C12A—H12C | 111.1 |
N2—C8—H8A | 111.3 | C13A—C12A—H12C | 111.1 |
C9—C8—H8A | 111.3 | N3—C12A—H12D | 111.1 |
N2—C8—H8B | 111.3 | C13A—C12A—H12D | 111.1 |
C9—C8—H8B | 111.3 | H12C—C12A—H12D | 109.1 |
H8A—C8—H8B | 109.2 | C14A—C13A—C12A | 102.8 (4) |
C8—C9—C10 | 105.1 (6) | C14A—C13A—H13C | 111.2 |
C8—C9—H9A | 110.7 | C12A—C13A—H13C | 111.2 |
C10—C9—H9A | 110.7 | C14A—C13A—H13D | 111.2 |
C8—C9—H9B | 110.7 | C12A—C13A—H13D | 111.2 |
C10—C9—H9B | 110.7 | H13C—C13A—H13D | 109.1 |
H9A—C9—H9B | 108.8 | C13A—C14A—C15A | 112.3 (5) |
C9—C10—C11 | 103.6 (5) | C13A—C14A—H14C | 109.1 |
C9—C10—H10A | 111.0 | C15A—C14A—H14C | 109.1 |
C11—C10—H10A | 111.0 | C13A—C14A—H14D | 109.1 |
C9—C10—H10B | 111.0 | C15A—C14A—H14D | 109.1 |
C11—C10—H10B | 111.0 | H14C—C14A—H14D | 107.9 |
H10A—C10—H10B | 109.0 | C14A—C15A—N3 | 98.4 (6) |
N2—C11—C10 | 101.4 (6) | C14A—C15A—H15C | 112.1 |
N2—C11—H11A | 111.5 | N3—C15A—H15C | 112.1 |
C10—C11—H11A | 111.5 | C14A—C15A—H15D | 112.1 |
N2—C11—H11B | 111.5 | N3—C15A—H15D | 112.1 |
C10—C11—H11B | 111.5 | H15C—C15A—H15D | 109.7 |
O1—P1—N1—C7 | 157.09 (12) | C5—C6—C7—O3 | −137.01 (15) |
N2—P1—N1—C7 | 36.30 (14) | C1—C6—C7—N1 | −142.04 (13) |
N3—P1—N1—C7 | −79.07 (13) | C5—C6—C7—N1 | 41.38 (18) |
O1—P1—N2—C11A | −43.6 (9) | C11A—N2—C8—C9 | −14.5 (11) |
N3—P1—N2—C11A | −170.6 (9) | C8A—N2—C8—C9 | −8 (27) |
N1—P1—N2—C11A | 73.7 (9) | C11—N2—C8—C9 | −9.0 (9) |
O1—P1—N2—C8A | 153.3 (8) | P1—N2—C8—C9 | 151.5 (5) |
N3—P1—N2—C8A | 26.3 (8) | N2—C8—C9—C10 | 29.3 (9) |
N1—P1—N2—C8A | −89.3 (8) | C8—C9—C10—C11 | −39.2 (10) |
O1—P1—N2—C11 | −48.0 (5) | C11A—N2—C11—C10 | 37 (7) |
N3—P1—N2—C11 | −175.0 (5) | C8A—N2—C11—C10 | −14.5 (10) |
N1—P1—N2—C11 | 69.4 (5) | C8—N2—C11—C10 | −14.4 (8) |
O1—P1—N2—C8 | 152.4 (4) | P1—N2—C11—C10 | −176.5 (4) |
N3—P1—N2—C8 | 25.4 (4) | C9—C10—C11—N2 | 31.8 (9) |
N1—P1—N2—C8 | −90.2 (4) | C11A—N2—C8A—C9A | −1.6 (15) |
O1—P1—N3—C15 | −55.4 (5) | C11—N2—C8A—C9A | 3.8 (13) |
N2—P1—N3—C15 | 68.9 (5) | C8—N2—C8A—C9A | −175 (28) |
N1—P1—N3—C15 | −172.6 (5) | P1—N2—C8A—C9A | 163.7 (8) |
O1—P1—N3—C12 | 141.4 (3) | N2—C8A—C9A—C10A | −27.4 (14) |
N2—P1—N3—C12 | −94.3 (3) | C8A—C9A—C10A—C11A | 43.4 (14) |
N1—P1—N3—C12 | 24.2 (3) | C8A—N2—C11A—C10A | 30.0 (14) |
O1—P1—N3—C12A | 92.4 (4) | C11—N2—C11A—C10A | −100 (8) |
N2—P1—N3—C12A | −143.3 (4) | C8—N2—C11A—C10A | 30.2 (13) |
N1—P1—N3—C12A | −24.8 (4) | P1—N2—C11A—C10A | −136.0 (7) |
O1—P1—N3—C15A | −54.8 (3) | C9A—C10A—C11A—N2 | −45.7 (14) |
N2—P1—N3—C15A | 69.5 (3) | C15—N3—C12—C13 | −5.9 (7) |
N1—P1—N3—C15A | −172.0 (3) | C12A—N3—C12—C13 | −105.9 (6) |
F1—C1—C2—C3 | 179.74 (15) | C15A—N3—C12—C13 | −5.0 (6) |
C6—C1—C2—C3 | 0.9 (2) | P1—N3—C12—C13 | 159.3 (5) |
C1—C2—C3—F2 | 179.47 (13) | N3—C12—C13—C14 | 18.5 (8) |
C1—C2—C3—C4 | −0.7 (2) | C12—C13—C14—C15 | −22.6 (9) |
F2—C3—C4—C5 | 179.73 (14) | C12—N3—C15—C14 | −7.8 (8) |
C2—C3—C4—C5 | −0.1 (2) | C12A—N3—C15—C14 | 34.0 (8) |
C3—C4—C5—F1A | 170.3 (2) | P1—N3—C15—C14 | −174.4 (4) |
C3—C4—C5—C6 | 0.8 (2) | C13—C14—C15—N3 | 18.6 (9) |
F1—C1—C6—C5 | −179.07 (14) | C15—N3—C12A—C13A | −15.8 (7) |
C2—C1—C6—C5 | −0.2 (2) | C12—N3—C12A—C13A | 77.2 (6) |
F1—C1—C6—C7 | 4.2 (2) | C15A—N3—C12A—C13A | −19.4 (7) |
C2—C1—C6—C7 | −176.98 (13) | P1—N3—C12A—C13A | −167.4 (4) |
F1A—C5—C6—C1 | −169.5 (2) | N3—C12A—C13A—C14A | 28.8 (8) |
C4—C5—C6—C1 | −0.6 (2) | C12A—C13A—C14A—C15A | −30.9 (10) |
F1A—C5—C6—C7 | 7.2 (3) | C13A—C14A—C15A—N3 | 18.5 (8) |
C4—C5—C6—C7 | 176.09 (13) | C15—N3—C15A—C14A | −33 (6) |
P1—N1—C7—O3 | 14.1 (2) | C12—N3—C15A—C14A | −42.0 (5) |
P1—N1—C7—C6 | −164.21 (10) | C12A—N3—C15A—C14A | 1.4 (6) |
C1—C6—C7—O3 | 39.6 (2) | P1—N3—C15A—C14A | 151.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.84 (1) | 1.95 (1) | 2.7845 (14) | 170 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H20F2N3O2P |
Mr | 343.31 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 9.1028 (3), 9.9477 (2), 18.5465 (5) |
β (°) | 92.268 (3) |
V (Å3) | 1678.11 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Eos Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.926, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17134, 4339, 3828 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.676 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.108, 1.03 |
No. of reflections | 4339 |
No. of parameters | 300 |
No. of restraints | 25 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.30 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), 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···O1i | 0.841 (13) | 1.953 (14) | 2.7845 (14) | 169.9 (16) |
Symmetry code: (i) −x+1, −y+1, −z. |
Acknowledgements
Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.
References
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Pourayoubi, M., Shoghpour, S., Torre-Fernández, L. & García-Granda, S. (2012). Acta Cryst. E68, o270–o271. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pourayoubi, M., Tarahhomi, A., Saneei, A., Rheingold, A. L. & Golen, J. A. (2011). Acta Cryst. C67, o265–o272. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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 the previous work in our research group on phosphoric triamides (Pourayoubi et al., 2011; 2012), herein, we report the synthesis and crystal structure of the title compound.
In the C(O)NHP(O) skeleton of the title phosphoric triamide (Fig. 1), the phosphoryl group adopts an anti orientation with respect to the carbonyl group; whereas it is in a syn position relative to the N—H unit. The phosphorus atom has a distorted tetrahedral configuration and the P—N bonds in the P(O)[NC4H8]2 fragment are shorter than the other P—N bond in the molecule. The P═O and C═O bond lengths, and P—N—C bond angles are within the expected values (Pourayoubi et al., 2012). The atoms F1/H1A and F1A/H1 are found to occupy similar sites in the ratio of 70/30 and are refined with fixed occupancies. Both pyrrolidine substituents (rings N2, C8—C11 and N3, C12—C15) are disordered over two sets of sites, with site occupancies of 0.566 (6) and 0.434 (6) and are refined using a two part model.
In the crystal structure, pairs of intermolecular P═O···H—N hydrogen bonds (Table 1 and Fig. 2) form hydrogen-bonded dimers as R22(8) ring (Bernstein et al., 1995).