organic compounds
N,N,N′,N′-Tetrabenzyl-N′′-(2,6-difluorobenzoyl)phosphoric triamide
aFaculty of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran, bDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, Iran, and cDepartment of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
*Correspondence e-mail: a.raissi_shabari@yahoo.com
In the C(O)NHP(O) fragment of the title compound, C35H32F2N3O2P, the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and O—P—N angles. The P atom adopts a distorted tetrahedral environment and the phosphoryl and carbonyl groups are anti with respect to each other. The two tertiary N atoms of the dibenzylamido groups show sp2 character with a slight deviation from planarity. In the crystal, pairs of N—H⋯O(P) hydrogen bonds form inversion dimers.
Related literature
For related structures with a [C(O)NH]P(O)[N]2 configuration, see: Sabbaghi et al. (2010); Pourayoubi et al. (2010). For the geometries of the tertiary N atoms in phosphoric triamides with a C(O)NHP(O)[N]2 core, see: Pourayoubi et al. (2012).
Experimental
Crystal data
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Refinement
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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
10.1107/S1600536812042481/sj5269sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042481/sj5269Isup2.hkl
2,6-F2—C6H3C(O)NHP(O)Cl2 was prepared according to a procedure reported by Pourayoubi et al. (2010).
To a solution of 2,6-F2—C6H3C(O)NHP(O)Cl2 (1.5 mmol) in chloroform (25 ml), a solution of dibenzylamine (6 mmol) in chloroform (5 ml) was added at 273 K. After 4 h stirring, the solvent was removed and the product was washed with distilled water and recrystallized from a mixture of CH3OH/CHCl3 (4:1 v/v) at room temperature.
The hydrogen atom H1N was found in a Fourier difference map and was allowed to refine isotropically with the N—H distance constrained to 0.87 (2) Å and Uiso(H) = 1.2 Ueq(N). All other hydrogen atoms were placed in calculated positions with appropriate riding parameters.
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); enCIFer (Allen et al., 2004).Fig. 1. An ORTEP-style plot and atom labeling scheme for the title compound. Displacement ellipsoids are given at 50% probability level and H atoms are drawn as small spheres with arbitrary radii. |
C35H32F2N3O2P | F(000) = 1248 |
Mr = 595.61 | Dx = 1.313 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3822 reflections |
a = 12.3079 (7) Å | θ = 2.7–25.0° |
b = 19.5089 (12) Å | µ = 0.14 mm−1 |
c = 13.0131 (6) Å | T = 100 K |
β = 105.430 (3)° | Block, colourless |
V = 3012.0 (3) Å3 | 0.18 × 0.12 × 0.10 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 6199 independent reflections |
Radiation source: fine-focus sealed tube | 4332 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ϕ and ω scans | θmax = 26.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −15→15 |
Tmin = 0.975, Tmax = 0.986 | k = −24→24 |
23928 measured reflections | l = −10→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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.6985P] where P = (Fo2 + 2Fc2)/3 |
6199 reflections | (Δ/σ)max = 0.001 |
391 parameters | Δρmax = 0.28 e Å−3 |
1 restraint | Δρmin = −0.39 e Å−3 |
C35H32F2N3O2P | V = 3012.0 (3) Å3 |
Mr = 595.61 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.3079 (7) Å | µ = 0.14 mm−1 |
b = 19.5089 (12) Å | T = 100 K |
c = 13.0131 (6) Å | 0.18 × 0.12 × 0.10 mm |
β = 105.430 (3)° |
Bruker APEXII CCD diffractometer | 6199 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 4332 reflections with I > 2σ(I) |
Tmin = 0.975, Tmax = 0.986 | Rint = 0.062 |
23928 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 1 restraint |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.28 e Å−3 |
6199 reflections | Δρmin = −0.39 e Å−3 |
391 parameters |
Experimental. IR (KBr, ν, cm-1): 3052, 2885, 1699, 1609, 1471, 1353, 1277, 1186, 1115, 1077, 1011, 930, 854, 802, 745. |
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 | 0.59266 (4) | 0.54027 (3) | 0.16718 (4) | 0.01441 (13) | |
F1 | 0.85267 (11) | 0.58682 (6) | −0.04221 (9) | 0.0281 (3) | |
F2 | 0.78767 (12) | 0.36483 (7) | 0.05916 (11) | 0.0416 (4) | |
O1 | 0.84569 (11) | 0.52129 (7) | 0.18588 (11) | 0.0207 (3) | |
O2 | 0.47271 (11) | 0.53813 (7) | 0.10611 (10) | 0.0172 (3) | |
N1 | 0.66497 (13) | 0.50969 (8) | 0.08388 (13) | 0.0156 (4) | |
H1N | 0.6240 (16) | 0.4957 (10) | 0.0232 (13) | 0.019* | |
N2 | 0.62881 (13) | 0.61912 (8) | 0.20347 (12) | 0.0155 (4) | |
N3 | 0.63429 (13) | 0.49405 (8) | 0.27580 (12) | 0.0149 (4) | |
C1 | 0.85840 (17) | 0.51846 (10) | −0.05653 (16) | 0.0185 (4) | |
C2 | 0.90366 (17) | 0.49400 (11) | −0.13495 (16) | 0.0226 (5) | |
H2A | 0.9310 | 0.5245 | −0.1792 | 0.027* | |
C3 | 0.90846 (17) | 0.42409 (12) | −0.14784 (16) | 0.0244 (5) | |
H3A | 0.9400 | 0.4062 | −0.2014 | 0.029* | |
C4 | 0.86834 (19) | 0.37989 (12) | −0.08434 (18) | 0.0288 (5) | |
H4A | 0.8703 | 0.3317 | −0.0941 | 0.035* | |
C5 | 0.82520 (18) | 0.40748 (11) | −0.00619 (17) | 0.0238 (5) | |
C6 | 0.81866 (16) | 0.47654 (10) | 0.01110 (15) | 0.0157 (4) | |
C7 | 0.77876 (17) | 0.50491 (10) | 0.10290 (16) | 0.0166 (4) | |
C8 | 0.72603 (16) | 0.63857 (10) | 0.29096 (15) | 0.0173 (4) | |
H8A | 0.7710 | 0.5970 | 0.3171 | 0.021* | |
H8B | 0.6984 | 0.6567 | 0.3504 | 0.021* | |
C9 | 0.80209 (16) | 0.69147 (10) | 0.26126 (16) | 0.0171 (4) | |
C10 | 0.84585 (16) | 0.74433 (10) | 0.33157 (16) | 0.0202 (5) | |
H10A | 0.8213 | 0.7496 | 0.3944 | 0.024* | |
C11 | 0.92460 (18) | 0.78945 (11) | 0.31167 (18) | 0.0253 (5) | |
H11A | 0.9546 | 0.8247 | 0.3614 | 0.030* | |
C12 | 0.95970 (18) | 0.78337 (11) | 0.21971 (18) | 0.0266 (5) | |
H12A | 1.0141 | 0.8141 | 0.2061 | 0.032* | |
C13 | 0.91462 (17) | 0.73200 (11) | 0.14762 (17) | 0.0238 (5) | |
H13A | 0.9376 | 0.7279 | 0.0837 | 0.029* | |
C14 | 0.83644 (17) | 0.68657 (10) | 0.16778 (16) | 0.0200 (5) | |
H14A | 0.8059 | 0.6517 | 0.1174 | 0.024* | |
C15 | 0.55331 (17) | 0.67630 (10) | 0.15645 (15) | 0.0173 (4) | |
H15A | 0.4978 | 0.6601 | 0.0912 | 0.021* | |
H15B | 0.5982 | 0.7133 | 0.1356 | 0.021* | |
C16 | 0.49147 (17) | 0.70473 (10) | 0.23293 (15) | 0.0187 (4) | |
C17 | 0.39712 (17) | 0.67077 (11) | 0.24741 (16) | 0.0233 (5) | |
H17A | 0.3712 | 0.6300 | 0.2086 | 0.028* | |
C18 | 0.34077 (19) | 0.69638 (12) | 0.31862 (17) | 0.0289 (5) | |
H18A | 0.2757 | 0.6735 | 0.3275 | 0.035* | |
C19 | 0.3792 (2) | 0.75492 (12) | 0.37635 (17) | 0.0314 (6) | |
H19A | 0.3412 | 0.7719 | 0.4258 | 0.038* | |
C20 | 0.4724 (2) | 0.78869 (12) | 0.36247 (17) | 0.0298 (6) | |
H20A | 0.4986 | 0.8290 | 0.4024 | 0.036* | |
C21 | 0.52835 (19) | 0.76405 (10) | 0.29027 (16) | 0.0227 (5) | |
H21A | 0.5920 | 0.7879 | 0.2802 | 0.027* | |
C22 | 0.67520 (17) | 0.42326 (10) | 0.27705 (16) | 0.0190 (4) | |
H22A | 0.7078 | 0.4168 | 0.2159 | 0.023* | |
H22B | 0.6104 | 0.3916 | 0.2675 | 0.023* | |
C23 | 0.76288 (17) | 0.40440 (10) | 0.37836 (16) | 0.0191 (5) | |
C24 | 0.77030 (18) | 0.33680 (11) | 0.41232 (16) | 0.0231 (5) | |
H24A | 0.7203 | 0.3035 | 0.3721 | 0.028* | |
C25 | 0.84993 (19) | 0.31741 (11) | 0.50427 (17) | 0.0263 (5) | |
H25A | 0.8552 | 0.2707 | 0.5258 | 0.032* | |
C26 | 0.92163 (18) | 0.36505 (12) | 0.56484 (18) | 0.0284 (5) | |
H26A | 0.9759 | 0.3514 | 0.6281 | 0.034* | |
C27 | 0.91417 (19) | 0.43264 (12) | 0.53319 (19) | 0.0330 (6) | |
H27A | 0.9623 | 0.4660 | 0.5754 | 0.040* | |
C28 | 0.83611 (18) | 0.45199 (11) | 0.43947 (18) | 0.0297 (5) | |
H28A | 0.8328 | 0.4984 | 0.4169 | 0.036* | |
C29 | 0.57861 (17) | 0.50956 (10) | 0.36177 (15) | 0.0169 (4) | |
H29A | 0.5423 | 0.5551 | 0.3480 | 0.020* | |
H29B | 0.6370 | 0.5121 | 0.4307 | 0.020* | |
C30 | 0.49109 (16) | 0.45744 (10) | 0.37099 (15) | 0.0162 (4) | |
C31 | 0.38563 (18) | 0.45573 (11) | 0.29768 (17) | 0.0235 (5) | |
H31A | 0.3682 | 0.4874 | 0.2402 | 0.028* | |
C32 | 0.30626 (18) | 0.40808 (11) | 0.30833 (18) | 0.0265 (5) | |
H32A | 0.2345 | 0.4073 | 0.2579 | 0.032* | |
C33 | 0.33008 (18) | 0.36155 (11) | 0.39148 (16) | 0.0215 (5) | |
H33A | 0.2748 | 0.3293 | 0.3987 | 0.026* | |
C34 | 0.43417 (17) | 0.36235 (10) | 0.46344 (16) | 0.0193 (4) | |
H34A | 0.4515 | 0.3303 | 0.5204 | 0.023* | |
C35 | 0.51438 (17) | 0.41011 (10) | 0.45299 (15) | 0.0184 (4) | |
H35A | 0.5864 | 0.4102 | 0.5030 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0122 (3) | 0.0172 (3) | 0.0140 (3) | 0.0008 (2) | 0.0036 (2) | −0.0007 (2) |
F1 | 0.0412 (8) | 0.0198 (6) | 0.0268 (7) | 0.0001 (6) | 0.0154 (6) | 0.0029 (5) |
F2 | 0.0616 (10) | 0.0199 (7) | 0.0603 (9) | −0.0026 (6) | 0.0459 (8) | 0.0008 (6) |
O1 | 0.0142 (7) | 0.0271 (8) | 0.0198 (8) | −0.0020 (6) | 0.0027 (6) | −0.0038 (6) |
O2 | 0.0133 (7) | 0.0224 (7) | 0.0157 (7) | 0.0004 (6) | 0.0034 (6) | −0.0037 (6) |
N1 | 0.0120 (9) | 0.0202 (9) | 0.0142 (9) | 0.0008 (7) | 0.0028 (7) | −0.0015 (7) |
N2 | 0.0139 (9) | 0.0181 (9) | 0.0135 (8) | 0.0035 (7) | 0.0018 (7) | 0.0007 (7) |
N3 | 0.0147 (9) | 0.0157 (8) | 0.0154 (9) | 0.0019 (7) | 0.0060 (7) | −0.0011 (7) |
C1 | 0.0162 (11) | 0.0189 (11) | 0.0192 (11) | 0.0005 (8) | 0.0025 (9) | 0.0006 (8) |
C2 | 0.0170 (11) | 0.0335 (13) | 0.0169 (11) | 0.0037 (9) | 0.0039 (9) | 0.0060 (9) |
C3 | 0.0177 (11) | 0.0370 (13) | 0.0204 (11) | 0.0052 (10) | 0.0083 (9) | −0.0036 (10) |
C4 | 0.0289 (13) | 0.0242 (12) | 0.0370 (13) | 0.0029 (10) | 0.0152 (11) | −0.0055 (10) |
C5 | 0.0222 (12) | 0.0226 (12) | 0.0314 (13) | −0.0013 (9) | 0.0157 (10) | 0.0010 (9) |
C6 | 0.0098 (10) | 0.0202 (11) | 0.0170 (10) | 0.0014 (8) | 0.0033 (8) | −0.0012 (8) |
C7 | 0.0162 (10) | 0.0148 (10) | 0.0201 (11) | 0.0005 (8) | 0.0072 (9) | 0.0030 (8) |
C8 | 0.0189 (11) | 0.0177 (10) | 0.0131 (10) | 0.0012 (8) | 0.0002 (8) | −0.0017 (8) |
C9 | 0.0134 (10) | 0.0158 (10) | 0.0202 (11) | 0.0049 (8) | 0.0011 (8) | 0.0005 (8) |
C10 | 0.0177 (11) | 0.0188 (11) | 0.0219 (11) | 0.0050 (8) | 0.0014 (9) | −0.0027 (8) |
C11 | 0.0205 (12) | 0.0184 (11) | 0.0322 (13) | 0.0002 (9) | −0.0014 (10) | −0.0043 (9) |
C12 | 0.0164 (11) | 0.0210 (11) | 0.0418 (14) | −0.0001 (9) | 0.0066 (10) | 0.0042 (10) |
C13 | 0.0200 (11) | 0.0235 (12) | 0.0290 (12) | 0.0066 (9) | 0.0086 (10) | 0.0033 (9) |
C14 | 0.0209 (11) | 0.0172 (10) | 0.0213 (11) | 0.0026 (9) | 0.0043 (9) | −0.0004 (8) |
C15 | 0.0180 (11) | 0.0176 (10) | 0.0161 (10) | 0.0042 (8) | 0.0042 (8) | 0.0027 (8) |
C16 | 0.0194 (11) | 0.0202 (11) | 0.0153 (11) | 0.0084 (8) | 0.0026 (9) | 0.0062 (8) |
C17 | 0.0210 (12) | 0.0259 (12) | 0.0224 (12) | 0.0069 (9) | 0.0051 (9) | 0.0043 (9) |
C18 | 0.0230 (12) | 0.0399 (14) | 0.0265 (13) | 0.0113 (10) | 0.0115 (10) | 0.0094 (10) |
C19 | 0.0372 (14) | 0.0391 (14) | 0.0216 (12) | 0.0224 (12) | 0.0141 (11) | 0.0070 (10) |
C20 | 0.0453 (15) | 0.0234 (12) | 0.0193 (12) | 0.0135 (11) | 0.0063 (11) | 0.0026 (9) |
C21 | 0.0293 (12) | 0.0200 (11) | 0.0189 (11) | 0.0078 (9) | 0.0065 (9) | 0.0046 (9) |
C22 | 0.0185 (11) | 0.0183 (10) | 0.0220 (11) | 0.0013 (8) | 0.0085 (9) | 0.0002 (9) |
C23 | 0.0158 (11) | 0.0216 (11) | 0.0223 (11) | 0.0031 (8) | 0.0093 (9) | 0.0028 (8) |
C24 | 0.0275 (12) | 0.0204 (11) | 0.0235 (12) | 0.0035 (9) | 0.0104 (10) | −0.0012 (9) |
C25 | 0.0343 (13) | 0.0200 (11) | 0.0268 (12) | 0.0101 (10) | 0.0118 (10) | 0.0066 (9) |
C26 | 0.0221 (12) | 0.0338 (13) | 0.0289 (13) | 0.0105 (10) | 0.0060 (10) | 0.0104 (10) |
C27 | 0.0229 (13) | 0.0334 (13) | 0.0374 (14) | −0.0028 (10) | −0.0009 (11) | 0.0072 (11) |
C28 | 0.0225 (12) | 0.0242 (12) | 0.0383 (14) | −0.0030 (9) | 0.0009 (10) | 0.0122 (10) |
C29 | 0.0196 (11) | 0.0174 (10) | 0.0143 (10) | 0.0002 (8) | 0.0057 (8) | −0.0004 (8) |
C30 | 0.0175 (11) | 0.0174 (10) | 0.0151 (10) | 0.0003 (8) | 0.0068 (8) | −0.0030 (8) |
C31 | 0.0225 (12) | 0.0221 (11) | 0.0235 (11) | −0.0005 (9) | 0.0016 (9) | 0.0083 (9) |
C32 | 0.0187 (11) | 0.0280 (12) | 0.0290 (12) | −0.0033 (9) | −0.0003 (10) | 0.0050 (10) |
C33 | 0.0222 (11) | 0.0184 (11) | 0.0261 (12) | −0.0045 (9) | 0.0101 (9) | −0.0004 (9) |
C34 | 0.0239 (12) | 0.0180 (10) | 0.0184 (11) | 0.0030 (9) | 0.0097 (9) | 0.0035 (8) |
C35 | 0.0196 (11) | 0.0218 (11) | 0.0140 (10) | 0.0022 (8) | 0.0051 (8) | −0.0003 (8) |
P1—O2 | 1.4794 (14) | C16—C21 | 1.386 (3) |
P1—N2 | 1.6358 (17) | C16—C17 | 1.393 (3) |
P1—N3 | 1.6395 (16) | C17—C18 | 1.390 (3) |
P1—N1 | 1.6841 (17) | C17—H17A | 0.9500 |
F1—C1 | 1.351 (2) | C18—C19 | 1.380 (3) |
F2—C5 | 1.356 (2) | C18—H18A | 0.9500 |
O1—C7 | 1.214 (2) | C19—C20 | 1.376 (3) |
N1—C7 | 1.359 (2) | C19—H19A | 0.9500 |
N1—H1N | 0.860 (15) | C20—C21 | 1.390 (3) |
N2—C8 | 1.465 (2) | C20—H20A | 0.9500 |
N2—C15 | 1.476 (2) | C21—H21A | 0.9500 |
N3—C22 | 1.469 (2) | C22—C23 | 1.510 (3) |
N3—C29 | 1.490 (2) | C22—H22A | 0.9900 |
C1—C2 | 1.372 (3) | C22—H22B | 0.9900 |
C1—C6 | 1.383 (3) | C23—C24 | 1.386 (3) |
C2—C3 | 1.377 (3) | C23—C28 | 1.387 (3) |
C2—H2A | 0.9500 | C24—C25 | 1.382 (3) |
C3—C4 | 1.374 (3) | C24—H24A | 0.9500 |
C3—H3A | 0.9500 | C25—C26 | 1.376 (3) |
C4—C5 | 1.376 (3) | C25—H25A | 0.9500 |
C4—H4A | 0.9500 | C26—C27 | 1.377 (3) |
C5—C6 | 1.372 (3) | C26—H26A | 0.9500 |
C6—C7 | 1.512 (3) | C27—C28 | 1.389 (3) |
C8—C9 | 1.511 (3) | C27—H27A | 0.9500 |
C8—H8A | 0.9900 | C28—H28A | 0.9500 |
C8—H8B | 0.9900 | C29—C30 | 1.509 (3) |
C9—C10 | 1.389 (3) | C29—H29A | 0.9900 |
C9—C14 | 1.393 (3) | C29—H29B | 0.9900 |
C10—C11 | 1.384 (3) | C30—C35 | 1.382 (3) |
C10—H10A | 0.9500 | C30—C31 | 1.392 (3) |
C11—C12 | 1.381 (3) | C31—C32 | 1.382 (3) |
C11—H11A | 0.9500 | C31—H31A | 0.9500 |
C12—C13 | 1.384 (3) | C32—C33 | 1.383 (3) |
C12—H12A | 0.9500 | C32—H32A | 0.9500 |
C13—C14 | 1.384 (3) | C33—C34 | 1.371 (3) |
C13—H13A | 0.9500 | C33—H33A | 0.9500 |
C14—H14A | 0.9500 | C34—C35 | 1.390 (3) |
C15—C16 | 1.510 (3) | C34—H34A | 0.9500 |
C15—H15A | 0.9900 | C35—H35A | 0.9500 |
C15—H15B | 0.9900 | ||
O2—P1—N2 | 109.73 (8) | C21—C16—C17 | 119.32 (19) |
O2—P1—N3 | 119.07 (8) | C21—C16—C15 | 120.73 (19) |
N2—P1—N3 | 105.64 (8) | C17—C16—C15 | 119.94 (18) |
O2—P1—N1 | 105.49 (8) | C18—C17—C16 | 120.1 (2) |
N2—P1—N1 | 111.66 (8) | C18—C17—H17A | 120.0 |
N3—P1—N1 | 105.23 (8) | C16—C17—H17A | 120.0 |
C7—N1—P1 | 127.05 (14) | C19—C18—C17 | 120.1 (2) |
C7—N1—H1N | 118.0 (14) | C19—C18—H18A | 120.0 |
P1—N1—H1N | 115.0 (14) | C17—C18—H18A | 120.0 |
C8—N2—C15 | 114.85 (15) | C20—C19—C18 | 120.1 (2) |
C8—N2—P1 | 124.82 (13) | C20—C19—H19A | 119.9 |
C15—N2—P1 | 119.87 (13) | C18—C19—H19A | 119.9 |
C22—N3—C29 | 114.04 (15) | C19—C20—C21 | 120.2 (2) |
C22—N3—P1 | 123.66 (13) | C19—C20—H20A | 119.9 |
C29—N3—P1 | 115.78 (12) | C21—C20—H20A | 119.9 |
F1—C1—C2 | 119.50 (18) | C16—C21—C20 | 120.1 (2) |
F1—C1—C6 | 117.12 (17) | C16—C21—H21A | 119.9 |
C2—C1—C6 | 123.38 (19) | C20—C21—H21A | 119.9 |
C1—C2—C3 | 118.3 (2) | N3—C22—C23 | 113.71 (16) |
C1—C2—H2A | 120.8 | N3—C22—H22A | 108.8 |
C3—C2—H2A | 120.8 | C23—C22—H22A | 108.8 |
C4—C3—C2 | 121.0 (2) | N3—C22—H22B | 108.8 |
C4—C3—H3A | 119.5 | C23—C22—H22B | 108.8 |
C2—C3—H3A | 119.5 | H22A—C22—H22B | 107.7 |
C3—C4—C5 | 118.0 (2) | C24—C23—C28 | 118.44 (19) |
C3—C4—H4A | 121.0 | C24—C23—C22 | 118.76 (18) |
C5—C4—H4A | 121.0 | C28—C23—C22 | 122.79 (18) |
F2—C5—C6 | 117.08 (18) | C25—C24—C23 | 120.5 (2) |
F2—C5—C4 | 119.10 (19) | C25—C24—H24A | 119.8 |
C6—C5—C4 | 123.8 (2) | C23—C24—H24A | 119.8 |
C5—C6—C1 | 115.49 (18) | C26—C25—C24 | 120.7 (2) |
C5—C6—C7 | 122.33 (18) | C26—C25—H25A | 119.7 |
C1—C6—C7 | 122.03 (18) | C24—C25—H25A | 119.7 |
O1—C7—N1 | 124.51 (18) | C25—C26—C27 | 119.6 (2) |
O1—C7—C6 | 120.86 (17) | C25—C26—H26A | 120.2 |
N1—C7—C6 | 114.63 (17) | C27—C26—H26A | 120.2 |
N2—C8—C9 | 114.30 (16) | C26—C27—C28 | 119.9 (2) |
N2—C8—H8A | 108.7 | C26—C27—H27A | 120.1 |
C9—C8—H8A | 108.7 | C28—C27—H27A | 120.1 |
N2—C8—H8B | 108.7 | C23—C28—C27 | 120.9 (2) |
C9—C8—H8B | 108.7 | C23—C28—H28A | 119.5 |
H8A—C8—H8B | 107.6 | C27—C28—H28A | 119.5 |
C10—C9—C14 | 118.14 (19) | N3—C29—C30 | 113.79 (15) |
C10—C9—C8 | 119.78 (18) | N3—C29—H29A | 108.8 |
C14—C9—C8 | 121.94 (17) | C30—C29—H29A | 108.8 |
C11—C10—C9 | 121.1 (2) | N3—C29—H29B | 108.8 |
C11—C10—H10A | 119.4 | C30—C29—H29B | 108.8 |
C9—C10—H10A | 119.4 | H29A—C29—H29B | 107.7 |
C12—C11—C10 | 120.2 (2) | C35—C30—C31 | 118.50 (19) |
C12—C11—H11A | 119.9 | C35—C30—C29 | 120.37 (18) |
C10—C11—H11A | 119.9 | C31—C30—C29 | 121.12 (18) |
C11—C12—C13 | 119.2 (2) | C32—C31—C30 | 120.18 (19) |
C11—C12—H12A | 120.4 | C32—C31—H31A | 119.9 |
C13—C12—H12A | 120.4 | C30—C31—H31A | 119.9 |
C14—C13—C12 | 120.6 (2) | C31—C32—C33 | 120.8 (2) |
C14—C13—H13A | 119.7 | C31—C32—H32A | 119.6 |
C12—C13—H13A | 119.7 | C33—C32—H32A | 119.6 |
C13—C14—C9 | 120.63 (19) | C34—C33—C32 | 119.5 (2) |
C13—C14—H14A | 119.7 | C34—C33—H33A | 120.3 |
C9—C14—H14A | 119.7 | C32—C33—H33A | 120.3 |
N2—C15—C16 | 112.12 (15) | C33—C34—C35 | 119.98 (19) |
N2—C15—H15A | 109.2 | C33—C34—H34A | 120.0 |
C16—C15—H15A | 109.2 | C35—C34—H34A | 120.0 |
N2—C15—H15B | 109.2 | C30—C35—C34 | 121.09 (19) |
C16—C15—H15B | 109.2 | C30—C35—H35A | 119.5 |
H15A—C15—H15B | 107.9 | C34—C35—H35A | 119.5 |
O2—P1—N1—C7 | 176.64 (16) | C10—C11—C12—C13 | 0.4 (3) |
N2—P1—N1—C7 | 57.50 (19) | C11—C12—C13—C14 | −0.9 (3) |
N3—P1—N1—C7 | −56.63 (18) | C12—C13—C14—C9 | −0.3 (3) |
O2—P1—N2—C8 | 159.51 (15) | C10—C9—C14—C13 | 2.0 (3) |
N3—P1—N2—C8 | 29.97 (18) | C8—C9—C14—C13 | −173.73 (19) |
N1—P1—N2—C8 | −83.90 (17) | C8—N2—C15—C16 | −68.0 (2) |
O2—P1—N2—C15 | −12.28 (17) | P1—N2—C15—C16 | 104.57 (17) |
N3—P1—N2—C15 | −141.81 (14) | N2—C15—C16—C21 | 99.8 (2) |
N1—P1—N2—C15 | 104.31 (15) | N2—C15—C16—C17 | −79.4 (2) |
O2—P1—N3—C22 | 90.02 (16) | C21—C16—C17—C18 | 0.1 (3) |
N2—P1—N3—C22 | −146.14 (15) | C15—C16—C17—C18 | 179.28 (18) |
N1—P1—N3—C22 | −27.88 (17) | C16—C17—C18—C19 | −1.0 (3) |
O2—P1—N3—C29 | −59.88 (15) | C17—C18—C19—C20 | 1.0 (3) |
N2—P1—N3—C29 | 63.95 (15) | C18—C19—C20—C21 | 0.0 (3) |
N1—P1—N3—C29 | −177.79 (13) | C17—C16—C21—C20 | 0.9 (3) |
F1—C1—C2—C3 | −179.99 (17) | C15—C16—C21—C20 | −178.33 (18) |
C6—C1—C2—C3 | 0.8 (3) | C19—C20—C21—C16 | −0.9 (3) |
C1—C2—C3—C4 | 0.4 (3) | C29—N3—C22—C23 | −61.0 (2) |
C2—C3—C4—C5 | −1.2 (3) | P1—N3—C22—C23 | 148.61 (14) |
C3—C4—C5—F2 | −178.4 (2) | N3—C22—C23—C24 | 150.43 (18) |
C3—C4—C5—C6 | 0.8 (3) | N3—C22—C23—C28 | −29.2 (3) |
F2—C5—C6—C1 | 179.56 (18) | C28—C23—C24—C25 | −0.8 (3) |
C4—C5—C6—C1 | 0.3 (3) | C22—C23—C24—C25 | 179.58 (18) |
F2—C5—C6—C7 | 3.9 (3) | C23—C24—C25—C26 | 1.3 (3) |
C4—C5—C6—C7 | −175.3 (2) | C24—C25—C26—C27 | −0.3 (3) |
F1—C1—C6—C5 | 179.63 (17) | C25—C26—C27—C28 | −1.3 (4) |
C2—C1—C6—C5 | −1.2 (3) | C24—C23—C28—C27 | −0.8 (3) |
F1—C1—C6—C7 | −4.7 (3) | C22—C23—C28—C27 | 178.8 (2) |
C2—C1—C6—C7 | 174.50 (18) | C26—C27—C28—C23 | 1.8 (4) |
P1—N1—C7—O1 | 1.6 (3) | C22—N3—C29—C30 | −48.9 (2) |
P1—N1—C7—C6 | −178.72 (14) | P1—N3—C29—C30 | 103.88 (17) |
C5—C6—C7—O1 | 95.9 (2) | N3—C29—C30—C35 | 104.5 (2) |
C1—C6—C7—O1 | −79.5 (3) | N3—C29—C30—C31 | −75.5 (2) |
C5—C6—C7—N1 | −83.8 (2) | C35—C30—C31—C32 | 0.8 (3) |
C1—C6—C7—N1 | 100.8 (2) | C29—C30—C31—C32 | −179.23 (19) |
C15—N2—C8—C9 | −58.6 (2) | C30—C31—C32—C33 | 0.0 (3) |
P1—N2—C8—C9 | 129.21 (16) | C31—C32—C33—C34 | −0.7 (3) |
N2—C8—C9—C10 | 138.58 (18) | C32—C33—C34—C35 | 0.6 (3) |
N2—C8—C9—C14 | −45.8 (2) | C31—C30—C35—C34 | −0.9 (3) |
C14—C9—C10—C11 | −2.4 (3) | C29—C30—C35—C34 | 179.13 (18) |
C8—C9—C10—C11 | 173.37 (18) | C33—C34—C35—C30 | 0.2 (3) |
C9—C10—C11—C12 | 1.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.86 (2) | 1.90 (2) | 2.761 (2) | 176 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C35H32F2N3O2P |
Mr | 595.61 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 12.3079 (7), 19.5089 (12), 13.0131 (6) |
β (°) | 105.430 (3) |
V (Å3) | 3012.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.18 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.975, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23928, 6199, 4332 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.111, 1.01 |
No. of reflections | 6199 |
No. of parameters | 391 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.39 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008); enCIFer (Allen et al., 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.860 (15) | 1.902 (15) | 2.761 (2) | 176 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
Acknowledgements
Support of this investigation by the North Tehran Branch, Islamic Azad University, is gratefully acknowledged.
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
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Pourayoubi, M., Jasinski, J. P., Shoghpour Bayraq, S., Eshghi, H., Keeley, A. C., Bruno, G. & Amiri Rudbari, H. (2012). Acta Cryst. C68, o399–o404. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Pourayoubi, M., Tarahhomi, A., Rheingold, A. L. & Golen, J. A. (2010). Acta Cryst. E66, o2524. Web of Science CSD CrossRef IUCr Journals Google Scholar
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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.
The structure determination of the title compound, [2,6-F2—C6H3C(O)NH]P(O)[N(CH2C6H5)2]2 (Fig. 1), was performed as part of a project on the synthesis of new phosphoric triamides with a [C(O)NH]P(O)[N]2 skeleton, where '[N]2' denotes two tertiary N atoms belonging to an amide group.
The phosphoryl and carbonyl groups, which are separated by an N atom, have a relative anti disposition. In the C(O)NHP(O) fragment, the P1—N1 bond is longer and the O2—P1—N1 angle is contracted compared with the other two P—N bonds and O—P—N angles, similar to what is found for related phosphoramide derivatives (Sabbaghi et al., 2010; Pourayoubi et al., 2010).
The two tertiary N atoms show sp2 character with a slight deviation from planarity, wherein one of the two dibenzylamido N atoms shows a slightly greater deviation than the other [viz N3 with the sum of the surrounding bond angles = 353.48 (2)°]. The tertiary N3 atom is more pyramidal than N2 and is oriented so that the lone pair of electrons is anti with respect to the P═O group (Pourayoubi et al., 2012).
In the crystal, the hydrogen atom of the C(O)NHP(O) moiety is involved in an intermolecular N—H···O(P) hydrogen bond (see Table 1) to form an inversion dimer.