organic compounds
N,N′-Dibenzyl-N′′-(2-chloro-2,2-difluoroacetyl)phosphoric triamide
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
In the title molecule, C16H17ClF2N3O2P, the N—H unit of the C(=O)NHP(=O) fragment adopts a syn orientation with respect to the P=O group. The two F atoms and the Cl atom of the ClF2C group are disordered over two sets of sites with refined occupancies of 0.605 (6) and 0.395 (6). In the crystal, molecules are linked via N—H⋯O=C hydrogen bonds and the (N—H⋯)(N—H⋯)O=P group into chains along [010].
Related literature
For related structures with a P(=O)[NHC(=O)CClF2] fragment, and for reference values of P=O, C=O and P—N bond lengths and P—N—C bond angles, see: Pourayoubi et al. (2011); Raissi Shabari et al. (2011); Pourayoubi & Saneei (2011). For the double hydrogen-bond acceptor capability of the phosphoryl O atom in phosphoramidates, see: Pourayoubi et al. (2012). For the synthesis of the starting material, CClF2C(=O)NHP(=O)Cl2, see: Iriarte et al. (2008).
Experimental
Crystal data
|
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
https://doi.org/10.1107/S1600536812039712/lh5506sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039712/lh5506Isup2.hkl
ClF2CC(O)NHP(O)Cl2 was prepared according to the literature method reported by Iriarte et al. (2008).
To a solution of ClF2CC(O)NHP(O)Cl2 (0.473 g, 1.92 mmol) in dry chloroform (25 ml), a solution of benzylamine (0.823 g, 7.68 mmol) in the same solvent (5 ml) was added at 273 K. After 6 h stirring, the solvent was removed and the product was washed with distilled water and recrystallized from CH3CN at room temperature.
H atoms H1N, H2N and H3N were located in a difference Fourier map and were refined with Uiso(H) = 1.2Ueq(N), giving N—H distances of 0.88 (2) or 0.86 (2) Å. The other H atoms were placed in calculated positions with 0.95 Å for CH, 0.99 Å for CH2 and with Uiso(H) = 1.2Ueq(C). F atoms F1 and F2 and chlorine Cl1 are disordered over two sets of sites with occupancies of 0.605 (6) and 0.395 (6).
In the previous studies, the structures of some compounds with a P(O)[NHC(O)CClF2] fragment have been investigated; for example, [4-CH3-C6H4NH]2P(O)[NHC(O)CClF2] (Pourayoubi, Tarahhomi et al., 2011), [(C6H5CH2)(CH3)N]2P(O)[NHC(O)CClF2] (Raissi Shabari et al., 2011) and [(CH3)2CHNH]2P(O)[NHC(O)CClF2] (Pourayoubi & Saneei, 2011). Here, the
of the title compound (Fig. 1) is reported.Atoms F1, F2 and Cl1 were refined as disordered over two sets of sites with occupancies of 0.605 (6) and 0.395 (6). The N—H unit of the C(O)NHP(O) fragment adopts a syn orientation with respect to the phosphoryl group. The P atom is bonded in a distorted tetrahedral environment as has been noted for other phosphoric triamides. The P═O, C═O and P—N bond lengths and P—N—C bond angles are within the expected values (Pourayoubi, Tarahhomi et al., 2011; Raissi Shabari et al., 2011; Pourayoubi & Saneei, 2011).
In the crystal, the O atom of P═O group acts as a double-hydrogen bond acceptor (Pourayoubi et al., 2012) and molecules are linked by N—H···O═C hydrogen bonds and (N—H···)2O═P group, into a linear arrangement along the b axis (Fig. 2).
For related structures with a P(═O)[NHC(═O)CClF2] fragment, and for reference values of P═O, C═O and P—N bond lengths and P—N—C bond angles, see: Pourayoubi et al. (2011); Raissi Shabari et al. (2011); Pourayoubi & Saneei (2011). For the double hydrogen-bond acceptor capability of the phosphoryl O atom in phosphoramidates, see: Pourayoubi et al. (2012). For the synthesis of the starting material, CClF2C(═ O)NHP(═O)Cl2, see: Iriarte et al. (2008).
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).C16H17ClF2N3O2P | F(000) = 400 |
Mr = 387.75 | Dx = 1.453 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3176 reflections |
a = 12.9734 (5) Å | θ = 3.3–32.2° |
b = 4.9900 (2) Å | µ = 0.34 mm−1 |
c = 13.7750 (4) Å | T = 173 K |
β = 96.482 (3)° | Block, colourless |
V = 886.06 (6) Å3 | 0.35 × 0.22 × 0.12 mm |
Z = 2 |
Oxford Xcalibur (Eos, Gemini) diffractometer | 5460 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 4909 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 16.1500 pixels mm-1 | θmax = 32.2°, θmin = 3.3° |
ω scans | h = −18→19 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | k = −7→6 |
Tmin = 0.890, Tmax = 0.960 | l = −9→20 |
9633 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.3968P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
5460 reflections | Δρmax = 0.55 e Å−3 |
263 parameters | Δρmin = −0.71 e Å−3 |
18 restraints | Absolute structure: Flack (1983), with 2216 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.06 (11) |
C16H17ClF2N3O2P | V = 886.06 (6) Å3 |
Mr = 387.75 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 12.9734 (5) Å | µ = 0.34 mm−1 |
b = 4.9900 (2) Å | T = 173 K |
c = 13.7750 (4) Å | 0.35 × 0.22 × 0.12 mm |
β = 96.482 (3)° |
Oxford Xcalibur (Eos, Gemini) diffractometer | 5460 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | 4909 reflections with I > 2σ(I) |
Tmin = 0.890, Tmax = 0.960 | Rint = 0.025 |
9633 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.122 | Δρmax = 0.55 e Å−3 |
S = 1.09 | Δρmin = −0.71 e Å−3 |
5460 reflections | Absolute structure: Flack (1983), with 2216 Friedel pairs |
263 parameters | Absolute structure parameter: 0.06 (11) |
18 restraints |
Experimental. IR (KBr, ν, cm-1): 3253, 1718, 1457, 1419, 1282, 1215, 1139, 1073, 977, 873, 735 and 688. |
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 | 0.51645 (5) | 0.70594 (13) | 0.19236 (4) | 0.01939 (13) | |
Cl1 | 0.2161 (2) | 0.5360 (8) | 0.3959 (2) | 0.0795 (10) | 0.605 (6) |
F1 | 0.3784 (5) | 0.5030 (15) | 0.4995 (4) | 0.086 (2) | 0.605 (6) |
F2 | 0.3555 (5) | 0.8763 (7) | 0.4479 (3) | 0.073 (2) | 0.605 (6) |
Cl1A | 0.3973 (4) | 0.6102 (13) | 0.5203 (3) | 0.0829 (18) | 0.395 (6) |
F1A | 0.2518 (6) | 0.4471 (17) | 0.4089 (7) | 0.066 (3) | 0.395 (6) |
F2A | 0.2775 (5) | 0.8461 (12) | 0.3861 (5) | 0.058 (2) | 0.395 (6) |
O1 | 0.54403 (15) | 0.9827 (4) | 0.16821 (14) | 0.0261 (4) | |
O2 | 0.4173 (2) | 0.3092 (5) | 0.3189 (2) | 0.0528 (8) | |
N1 | 0.45241 (18) | 0.5364 (5) | 0.10546 (18) | 0.0266 (5) | |
H1N | 0.460 (3) | 0.362 (5) | 0.106 (3) | 0.032* | |
N2 | 0.61194 (18) | 0.5089 (5) | 0.22963 (16) | 0.0241 (4) | |
H2N | 0.601 (3) | 0.340 (5) | 0.226 (2) | 0.029* | |
N3 | 0.4401 (2) | 0.7487 (5) | 0.28612 (18) | 0.0288 (5) | |
H3N | 0.428 (3) | 0.909 (5) | 0.305 (2) | 0.035* | |
C1 | 0.3635 (2) | 0.6492 (6) | 0.0436 (2) | 0.0294 (6) | |
H1B | 0.3792 | 0.6516 | −0.0251 | 0.035* | |
H1A | 0.3527 | 0.8367 | 0.0637 | 0.035* | |
C2 | 0.2652 (2) | 0.4925 (6) | 0.04980 (19) | 0.0270 (5) | |
C3 | 0.2351 (2) | 0.2941 (6) | −0.0179 (2) | 0.0309 (6) | |
H3A | 0.2759 | 0.2598 | −0.0696 | 0.037* | |
C4 | 0.1463 (3) | 0.1456 (7) | −0.0111 (3) | 0.0391 (7) | |
H4A | 0.1267 | 0.0093 | −0.0577 | 0.047* | |
C5 | 0.0860 (2) | 0.1951 (9) | 0.0635 (2) | 0.0432 (7) | |
H5A | 0.0247 | 0.0937 | 0.0679 | 0.052* | |
C6 | 0.1150 (3) | 0.3920 (9) | 0.1315 (3) | 0.0457 (9) | |
H6A | 0.0742 | 0.4238 | 0.1835 | 0.055* | |
C7 | 0.2035 (2) | 0.5440 (8) | 0.1241 (2) | 0.0364 (7) | |
H7A | 0.2219 | 0.6832 | 0.1698 | 0.044* | |
C8 | 0.6884 (2) | 0.5876 (6) | 0.3112 (2) | 0.0286 (6) | |
H8A | 0.6577 | 0.5637 | 0.3733 | 0.034* | |
H8B | 0.7050 | 0.7800 | 0.3048 | 0.034* | |
C9 | 0.7871 (2) | 0.4274 (6) | 0.31541 (19) | 0.0263 (5) | |
C10 | 0.8070 (2) | 0.2410 (7) | 0.2450 (2) | 0.0303 (6) | |
H10A | 0.7574 | 0.2120 | 0.1899 | 0.036* | |
C11 | 0.8993 (3) | 0.0966 (8) | 0.2550 (3) | 0.0401 (7) | |
H11A | 0.9121 | −0.0311 | 0.2067 | 0.048* | |
C12 | 0.9720 (3) | 0.1367 (8) | 0.3341 (3) | 0.0453 (9) | |
H12A | 1.0345 | 0.0358 | 0.3409 | 0.054* | |
C13 | 0.9537 (3) | 0.3244 (9) | 0.4035 (3) | 0.0505 (10) | |
H13A | 1.0045 | 0.3561 | 0.4575 | 0.061* | |
C14 | 0.8624 (3) | 0.4658 (8) | 0.3949 (2) | 0.0403 (7) | |
H14A | 0.8502 | 0.5920 | 0.4439 | 0.048* | |
C15 | 0.4032 (3) | 0.5428 (6) | 0.3344 (3) | 0.0405 (8) | |
C16 | 0.3359 (2) | 0.6241 (6) | 0.4143 (2) | 0.0490 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0211 (3) | 0.0136 (2) | 0.0242 (3) | −0.0009 (3) | 0.00582 (19) | −0.0014 (2) |
Cl1 | 0.0438 (12) | 0.139 (3) | 0.0597 (12) | 0.0070 (14) | 0.0255 (10) | −0.0081 (14) |
F1 | 0.076 (4) | 0.169 (7) | 0.0121 (19) | −0.017 (4) | 0.0062 (19) | −0.016 (3) |
F2 | 0.139 (5) | 0.036 (2) | 0.056 (3) | −0.013 (3) | 0.066 (3) | −0.0126 (18) |
Cl1A | 0.076 (3) | 0.148 (5) | 0.0257 (15) | 0.005 (3) | 0.0091 (13) | −0.0213 (17) |
F1A | 0.028 (3) | 0.079 (6) | 0.098 (6) | −0.017 (4) | 0.036 (4) | 0.007 (5) |
F2A | 0.081 (5) | 0.043 (3) | 0.060 (4) | 0.032 (3) | 0.047 (4) | 0.012 (3) |
O1 | 0.0319 (10) | 0.0160 (9) | 0.0322 (9) | −0.0018 (7) | 0.0107 (7) | 0.0004 (7) |
O2 | 0.0767 (19) | 0.0144 (10) | 0.0769 (18) | 0.0017 (12) | 0.0504 (16) | 0.0025 (11) |
N1 | 0.0229 (10) | 0.0199 (11) | 0.0361 (11) | 0.0025 (9) | −0.0006 (8) | −0.0079 (9) |
N2 | 0.0240 (10) | 0.0158 (10) | 0.0316 (11) | −0.0011 (8) | −0.0008 (8) | −0.0015 (9) |
N3 | 0.0405 (13) | 0.0129 (12) | 0.0366 (11) | 0.0009 (9) | 0.0198 (10) | −0.0012 (8) |
C1 | 0.0263 (12) | 0.0335 (18) | 0.0281 (12) | −0.0024 (10) | 0.0009 (9) | 0.0050 (10) |
C2 | 0.0218 (12) | 0.0308 (14) | 0.0281 (12) | 0.0024 (10) | 0.0014 (9) | 0.0067 (10) |
C3 | 0.0275 (13) | 0.0332 (16) | 0.0321 (13) | 0.0026 (11) | 0.0033 (11) | 0.0008 (11) |
C4 | 0.0366 (16) | 0.0320 (19) | 0.0477 (17) | −0.0011 (12) | 0.0000 (13) | −0.0013 (12) |
C5 | 0.0271 (13) | 0.0458 (19) | 0.0568 (18) | −0.0050 (17) | 0.0047 (12) | 0.008 (2) |
C6 | 0.0327 (17) | 0.064 (3) | 0.0427 (17) | −0.0004 (17) | 0.0129 (13) | 0.0049 (17) |
C7 | 0.0287 (14) | 0.049 (2) | 0.0314 (13) | −0.0020 (14) | 0.0042 (11) | −0.0040 (13) |
C8 | 0.0296 (13) | 0.0269 (14) | 0.0284 (12) | 0.0019 (11) | −0.0006 (10) | −0.0036 (10) |
C9 | 0.0252 (12) | 0.0265 (13) | 0.0270 (12) | −0.0032 (10) | 0.0025 (9) | 0.0035 (10) |
C10 | 0.0260 (12) | 0.0340 (17) | 0.0309 (12) | −0.0004 (12) | 0.0030 (9) | −0.0017 (11) |
C11 | 0.0298 (15) | 0.0427 (19) | 0.0494 (18) | 0.0062 (14) | 0.0113 (13) | −0.0021 (15) |
C12 | 0.0297 (15) | 0.052 (2) | 0.0533 (19) | 0.0088 (14) | 0.0011 (13) | 0.0121 (16) |
C13 | 0.0378 (19) | 0.062 (3) | 0.0474 (19) | 0.0040 (17) | −0.0156 (15) | 0.0013 (18) |
C14 | 0.0393 (17) | 0.0429 (19) | 0.0356 (15) | 0.0020 (15) | −0.0096 (12) | −0.0027 (14) |
C15 | 0.060 (2) | 0.0165 (13) | 0.0516 (18) | 0.0013 (13) | 0.0366 (16) | 0.0015 (12) |
C16 | 0.0641 (16) | 0.0245 (15) | 0.066 (2) | −0.0012 (15) | 0.0394 (15) | 0.0048 (15) |
P1—O1 | 1.474 (2) | C3—H3A | 0.9500 |
P1—N1 | 1.617 (2) | C4—C5 | 1.382 (5) |
P1—N2 | 1.619 (2) | C4—H4A | 0.9500 |
P1—N3 | 1.728 (2) | C5—C6 | 1.381 (6) |
Cl1—C16 | 1.607 (3) | C5—H5A | 0.9500 |
F1—C16 | 1.379 (5) | C6—C7 | 1.390 (5) |
F2—C16 | 1.355 (4) | C6—H6A | 0.9500 |
Cl1A—C16 | 1.585 (4) | C7—H7A | 0.9500 |
F1A—C16 | 1.399 (5) | C8—C9 | 1.505 (4) |
F2A—C16 | 1.373 (4) | C8—H8A | 0.9900 |
O2—C15 | 1.203 (4) | C8—H8B | 0.9900 |
N1—C1 | 1.467 (4) | C9—C10 | 1.388 (4) |
N1—H1N | 0.88 (2) | C9—C14 | 1.396 (4) |
N2—C8 | 1.466 (3) | C10—C11 | 1.391 (4) |
N2—H2N | 0.86 (2) | C10—H10A | 0.9500 |
N3—C15 | 1.341 (4) | C11—C12 | 1.373 (5) |
N3—H3N | 0.86 (2) | C11—H11A | 0.9500 |
C1—C2 | 1.507 (4) | C12—C13 | 1.378 (6) |
C1—H1B | 0.9900 | C12—H12A | 0.9500 |
C1—H1A | 0.9900 | C13—C14 | 1.373 (5) |
C2—C3 | 1.386 (4) | C13—H13A | 0.9500 |
C2—C7 | 1.393 (4) | C14—H14A | 0.9500 |
C3—C4 | 1.382 (4) | C15—C16 | 1.534 (4) |
O1—P1—N1 | 116.13 (13) | C9—C8—H8B | 109.0 |
O1—P1—N2 | 116.36 (12) | H8A—C8—H8B | 107.8 |
N1—P1—N2 | 103.17 (12) | C10—C9—C14 | 118.1 (3) |
O1—P1—N3 | 103.15 (11) | C10—C9—C8 | 123.6 (2) |
N1—P1—N3 | 109.14 (13) | C14—C9—C8 | 118.3 (3) |
N2—P1—N3 | 108.72 (12) | C9—C10—C11 | 120.2 (3) |
C1—N1—P1 | 122.3 (2) | C9—C10—H10A | 119.9 |
C1—N1—H1N | 118 (2) | C11—C10—H10A | 119.9 |
P1—N1—H1N | 117 (2) | C12—C11—C10 | 120.7 (3) |
C8—N2—P1 | 120.50 (19) | C12—C11—H11A | 119.7 |
C8—N2—H2N | 114 (2) | C10—C11—H11A | 119.7 |
P1—N2—H2N | 118 (2) | C11—C12—C13 | 119.5 (3) |
C15—N3—P1 | 122.91 (19) | C11—C12—H12A | 120.2 |
C15—N3—H3N | 119 (2) | C13—C12—H12A | 120.2 |
P1—N3—H3N | 118 (2) | C14—C13—C12 | 120.3 (3) |
N1—C1—C2 | 112.5 (2) | C14—C13—H13A | 119.9 |
N1—C1—H1B | 109.1 | C12—C13—H13A | 119.9 |
C2—C1—H1B | 109.1 | C13—C14—C9 | 121.2 (3) |
N1—C1—H1A | 109.1 | C13—C14—H14A | 119.4 |
C2—C1—H1A | 109.1 | C9—C14—H14A | 119.4 |
H1B—C1—H1A | 107.8 | O2—C15—N3 | 125.7 (3) |
C3—C2—C7 | 118.9 (3) | O2—C15—C16 | 119.6 (3) |
C3—C2—C1 | 120.6 (2) | N3—C15—C16 | 114.6 (2) |
C7—C2—C1 | 120.5 (3) | F2—C16—F2A | 54.8 (4) |
C4—C3—C2 | 120.8 (3) | F2—C16—F1 | 94.3 (4) |
C4—C3—H3A | 119.6 | F2A—C16—F1 | 138.5 (4) |
C2—C3—H3A | 119.6 | F2—C16—F1A | 136.0 (5) |
C5—C4—C3 | 120.1 (3) | F2A—C16—F1A | 95.3 (5) |
C5—C4—H4A | 120.0 | F1—C16—F1A | 90.2 (5) |
C3—C4—H4A | 120.0 | F2—C16—C15 | 113.0 (3) |
C6—C5—C4 | 119.9 (3) | F2A—C16—C15 | 110.6 (3) |
C6—C5—H5A | 120.1 | F1—C16—C15 | 106.8 (4) |
C4—C5—H5A | 120.1 | F1A—C16—C15 | 107.3 (5) |
C5—C6—C7 | 120.2 (3) | F2—C16—Cl1A | 70.7 (4) |
C5—C6—H6A | 119.9 | F2A—C16—Cl1A | 120.0 (4) |
C7—C6—H6A | 119.9 | F1A—C16—Cl1A | 109.2 (5) |
C6—C7—C2 | 120.1 (3) | C15—C16—Cl1A | 112.5 (3) |
C6—C7—H7A | 119.9 | F2—C16—Cl1 | 116.7 (4) |
C2—C7—H7A | 119.9 | F2A—C16—Cl1 | 71.6 (4) |
N2—C8—C9 | 112.7 (2) | F1—C16—Cl1 | 107.5 (4) |
N2—C8—H8A | 109.0 | C15—C16—Cl1 | 115.7 (3) |
C9—C8—H8A | 109.0 | Cl1A—C16—Cl1 | 120.6 (3) |
N2—C8—H8B | 109.0 | ||
O1—P1—N1—C1 | −45.6 (3) | C14—C9—C10—C11 | 0.6 (5) |
N2—P1—N1—C1 | −174.1 (2) | C8—C9—C10—C11 | −178.7 (3) |
N3—P1—N1—C1 | 70.4 (2) | C9—C10—C11—C12 | −0.3 (5) |
O1—P1—N2—C8 | 53.1 (2) | C10—C11—C12—C13 | −0.8 (6) |
N1—P1—N2—C8 | −178.5 (2) | C11—C12—C13—C14 | 1.5 (6) |
N3—P1—N2—C8 | −62.8 (2) | C12—C13—C14—C9 | −1.2 (6) |
O1—P1—N3—C15 | −175.7 (3) | C10—C9—C14—C13 | 0.2 (5) |
N1—P1—N3—C15 | 60.2 (3) | C8—C9—C14—C13 | 179.5 (3) |
N2—P1—N3—C15 | −51.6 (3) | P1—N3—C15—O2 | −0.6 (6) |
P1—N1—C1—C2 | −120.2 (2) | P1—N3—C15—C16 | −179.3 (2) |
N1—C1—C2—C3 | −94.8 (3) | O2—C15—C16—F2 | 157.9 (5) |
N1—C1—C2—C7 | 84.9 (3) | N3—C15—C16—F2 | −23.3 (5) |
C7—C2—C3—C4 | −1.2 (4) | O2—C15—C16—F2A | −142.8 (5) |
C1—C2—C3—C4 | 178.4 (3) | N3—C15—C16—F2A | 36.0 (6) |
C2—C3—C4—C5 | 0.4 (5) | O2—C15—C16—F1 | 55.6 (6) |
C3—C4—C5—C6 | −0.4 (5) | N3—C15—C16—F1 | −125.6 (4) |
C4—C5—C6—C7 | 1.2 (6) | O2—C15—C16—F1A | −40.0 (6) |
C5—C6—C7—C2 | −2.0 (6) | N3—C15—C16—F1A | 138.8 (5) |
C3—C2—C7—C6 | 2.0 (5) | O2—C15—C16—Cl1A | 80.1 (5) |
C1—C2—C7—C6 | −177.6 (3) | N3—C15—C16—Cl1A | −101.1 (4) |
P1—N2—C8—C9 | −162.00 (19) | O2—C15—C16—Cl1 | −64.0 (5) |
N2—C8—C9—C10 | 5.0 (4) | N3—C15—C16—Cl1 | 114.8 (4) |
N2—C8—C9—C14 | −174.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.88 (2) | 2.30 (3) | 3.092 (3) | 151 (3) |
N2—H2N···O1i | 0.86 (2) | 2.05 (2) | 2.867 (3) | 158 (3) |
N3—H3N···O2ii | 0.86 (2) | 2.01 (2) | 2.854 (3) | 166 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C16H17ClF2N3O2P |
Mr | 387.75 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 173 |
a, b, c (Å) | 12.9734 (5), 4.9900 (2), 13.7750 (4) |
β (°) | 96.482 (3) |
V (Å3) | 886.06 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.35 × 0.22 × 0.12 |
Data collection | |
Diffractometer | Oxford Xcalibur (Eos, Gemini) |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.890, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9633, 5460, 4909 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.751 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.122, 1.09 |
No. of reflections | 5460 |
No. of parameters | 263 |
No. of restraints | 18 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.71 |
Absolute structure | Flack (1983), with 2216 Friedel pairs |
Absolute structure parameter | 0.06 (11) |
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 | 0.88 (2) | 2.30 (3) | 3.092 (3) | 151 (3) |
N2—H2N···O1i | 0.86 (2) | 2.05 (2) | 2.867 (3) | 158 (3) |
N3—H3N···O2ii | 0.86 (2) | 2.01 (2) | 2.854 (3) | 166 (3) |
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z. |
Acknowledgements
MP thanks Ferdowsi University of Mashhad for a Research University Grant (No. 15144/2). 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 CSD CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Iriarte, A. G., Erben, M. F., Gholivand, K., Jios, J. L., Ulic, S. E. & Védova, C. O. D. (2008). J. Mol. Struct. 886, 66–71. Web of Science CrossRef CAS Google Scholar
Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Pourayoubi, M., Nečas, M. & Negari, M. (2012). Acta Cryst. C68, o51–o56. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Pourayoubi, M. & Saneei, A. (2011). Acta Cryst. E67, o665. 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
Raissi Shabari, A., Pourayoubi, M. & Saneei, A. (2011). Acta Cryst. E67, o663–o664. Web of Science CSD CrossRef 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.
In the previous studies, the structures of some compounds with a P(O)[NHC(O)CClF2] fragment have been investigated; for example, [4-CH3-C6H4NH]2P(O)[NHC(O)CClF2] (Pourayoubi, Tarahhomi et al., 2011), [(C6H5CH2)(CH3)N]2P(O)[NHC(O)CClF2] (Raissi Shabari et al., 2011) and [(CH3)2CHNH]2P(O)[NHC(O)CClF2] (Pourayoubi & Saneei, 2011). Here, the structure determination of the title compound (Fig. 1) is reported.
Atoms F1, F2 and Cl1 were refined as disordered over two sets of sites with occupancies of 0.605 (6) and 0.395 (6). The N—H unit of the C(O)NHP(O) fragment adopts a syn orientation with respect to the phosphoryl group. The P atom is bonded in a distorted tetrahedral environment as has been noted for other phosphoric triamides. The P═O, C═O and P—N bond lengths and P—N—C bond angles are within the expected values (Pourayoubi, Tarahhomi et al., 2011; Raissi Shabari et al., 2011; Pourayoubi & Saneei, 2011).
In the crystal, the O atom of P═O group acts as a double-hydrogen bond acceptor (Pourayoubi et al., 2012) and molecules are linked by N—H···O═C hydrogen bonds and (N—H···)2O═P group, into a linear arrangement along the b axis (Fig. 2).