Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
In the phospho­ric triamides N,N,N′,N′-tetra­benzyl-N′′-(2-chloro-2,2-difluoro­acet­yl)phospho­ric triamide, C30H29ClF2N3O2P, (I), N,N,N′,N′-tetra­benzyl-N′′-(3-fluoro­benzo­yl)phospho­ric triamide, C35H33FN3O2P, (II), and N,N,N′,N′-tetra­benzyl-N′′-(3,5-difluoro­benzo­yl)phospho­ric triamide, C35H32F2N3O2P, (III), the tertiary N atoms of the dibenzyl­amido groups have sp2 character with minimal deviation from planarity. The sums of the three bond angles about the N atoms in (I)–(III) deviate by less than 8° from the planar value of 360°. The geometries of the tertiary N atoms in all phospho­ric triamides with C(O)NHP(O)[N]2 skeletons deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380–388] have been examined and the bond-angle sums at the two tertiary N atoms (SUM1 and SUM2) and the parameter ΔSUM (= SUM1 − SUM2) considered. It was found that in compounds with a considerable ΔSUM value, the more pyramidal N atoms are usually oriented so that the corresponding lone electron pair is anti with respect to the P=O group. In (I), (II) and (III), the phosphoryl and carbonyl groups, separated by an N atom, are anti with respect to each other. In the C(O)NHP(O) fragment of (I)–(III), the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and the O—P—N angles in the mol­ecules. These effects are also seen in analogous compounds deposited in the CSD. Compounds with [C(O)NH]P(O)[N]X (X ≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been considered here. Also, com­pounds with a [C(O)NH]2P(O)[N] fragment have not been reported to date. In the crystal structures of all three title compounds, adjacent mol­ecules are linked via pairs of P=O...H—N hydrogen bonds, forming dimers with Ci symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112036396/fa3282sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112036396/fa3282Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112036396/fa3282IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112036396/fa3282IIIsup4.hkl
Contains datablock III

CCDC references: 906577; 906578; 906579

Comment top

The N—PO group is the basic skeleton of a large family of compounds called phosphoramides. The environment of the N atom bonded to the P atom in these compounds tends toward planarity (Pourayoubi et al., 2011), similar to N atoms bonded to C atoms in organic amides (Döring et al., 2012), unless the N atom is in an environment with an inherent distortion (Rebrova et al., 1992).

We present here three new phosphoric triamides with a C(O)NHP(O)[N]2 skeleton, where `[N]2' denotes two tertiary N atoms belonging to an amido group; these compounds are N,N,N',N'-tetrabenzyl-N''-(2-chloro-2,2-difluoroacetyl)phosphoric triamide, (I), N,N,N',N'-tetrabenzyl-N''-(3-fluorobenzoyl)phosphoric triamide, (II), and N,N,N',N'-tetrabenzyl-N''-(3,5-difluorobenzoyl)phosphoric triamide, (III). The geometries of the tertiary N atoms in these compounds are analyzed and compared with those of analogous structures deposited in the Cambridge Structural Database (CSD, Version 5.32, May 2011 update; Allen, 2002; for each example, the CSD refcode is given in capitals followed by the primary reference). All three N atoms in the C(O)NHP(O)[N]2 core are amido N atoms. For clarity, the N atom in the C(O)NHP(O) fragment is designated as NC(O)NHP(O), whereas the other two N atoms are designated as Namido atoms.

In (I), (II) and (III), the asymmetric unit contains one molecule, with the C(O)NHP(O)[N]2 skeleton (Figa. 1, 2 and 3). The P atom exhibits a distorted tetrahedral environment, which is reflected in the bond lengths and angles in the [N]P(O)[N]2 fragment (Tables 1, 3 and 5), similar to that observed for related phosphoramide derivatives (Pourayoubi et al., 2011). The P O and P—N bond lengths, as well as the bond angles at the P atom, are comparable to those in similar compounds (Pourayoubi et al., 2011). In (I)–(III), the widest angle about the P atom is observed in one of the two O—P—Namido angles, whereas the narrowest angle for (I) and (III) is O—P—NC(O)NHP(O) and for (II) is an Namido—P—NC(O)NHP(O) angle.

In the C(O)NHP(O) fragment of (I), (II) and (III), the P—N bond is longer and the O—P—N angle is contracted compared with the other two P—N bonds and the other two O—P—N angles in each molecule. The bond distance trend is seen in a histogram of P—Namide and P—NC(O)NHP(O) distances (Fig. 4). This histogram covers the P—N bond lengths in all phosphoric triamides with C(O)NHP(O)[N]2 and C(O)NHP(O)[NH]2 fragments found in the CSD. In the range 1.60–1.66 Å, only P—Namide bonds are found; and in the range 1.68–1.74 Å only P—NC(O)NHP(O) bonds are found, while in the range 1.66–1.68 Å, both types of P—N bonds are observed. The number of P—Namide bond entries is twice the number of P—NC(O)NHP(O) bonds found in the CSD for phosphoramides with C(O)NHP(O) fragments. Compounds with [C(O)NH]P(O)[N]X (X ≠ N), such as compounds with a [C(O)NH]P(O)[N][O] skeleton, have not been reported. Also, compounds with a [C(O)NH]2P(O)[N] fragment have not been reported to date.

The two tertiary N atoms in each of (I), (II) and (III) show sp2 character with a slight deviation from planarity, wherein one of the two benzylamido N atoms shows a slightly higher deviation than the other. The sum of the surrounding bond angles (2 × P—N—C + C—N—C) at N2 and N3 in (I) are 359.6 (2) and 355.2 (2)°, respectively. In (II) and (III), the higher values are 359.71 (15) and 357.45 (15)°, respectively, while the lower values are 352.39 (15) and 355.14 (14)°, respectively. Thus, the differences in these bond-angle sums are small. The more pyramidal of the tertiary N atoms in these molecules [i.e. N3 in (I) and (III), and N2 in (II)] are oriented so that the lone electron pair (LEP) is anti with respect to the P O group.

Fig. 5 shows the slight pyramidality of one of the N atoms in compound (I) with the LEP anti relative to PO.

The bond-angle sums for phosphoric triamides with C(O)NHP(O)[N]2 skeletons found in the CSD were also examined (`[N]' denotes a tertiary N atom). Compounds with three-membered cyclic amido substituents were excluded from consideration, as ring strain affects the sum of the surrounding bond angles at the tertiary N atoms, which can deviate significantly from 360° (in the range 292.3–311.8°). Compounds with disorder in the N or surrounding atoms were also excluded.

Fig. 6 shows the sum of surrounding bond angles around the two tertiary N atoms (as different colors) in 60 compounds with C(O)NHP(O)[N]2 fragments; the bond-angle sum varies in the range 339.1–360°. The entries are arranged from smallest difference (leftmost) to largest (rightmost). The greatest difference is found for C6H5C(O)NHP(O)[NC3H6]2 (LAYMII; Gholivand et al., 2005), with values of 357.96 and 340.49°, respectively. In this example, similar to compounds (I), (II) and (III), the LEP of the N atom adopts an anti orientation relative to the PO group (entry 60; Fig. 6). This situation is also observed for entries 59 (LARTII01; Marsh, 2009), 58 (WIYTUT; Gubina et al., 2000), 57 (VEHTAE; Gholivand, Alizadehgan et al., 2006), 56 (VEFLUO; Gholivand, Mojahed et al., 2006), 55 (LIVWAP; Dehghanpour et al., 2008), 54 (KEBPUD; Gholivand, Shariatinia & Pourayoubi, 2006), 53 (BUVJOS; Dehghanpour et al., 2010), 52 and 51 (SIRXIB and SIRXEX; Gholivand et al., 2007), 50 (BUVJIM; Dehghanpour et al., 2010) and 49 (VEHTAE; Gholivand, Alizadehgan et al., 2006), with ΔSUM (= SUM1 - SUM2) ranging from 14.3 to 5.9°, where the LEP of the more pyramidal N atom is anti relative to PO.

Of the three angles at the tertiary N atoms, the C—N—C angles in all the studied structures have a significantly lower value than those of the two P—N—C angles.

For each of (I), (II) and (III), the phosphoryl and carbonyl groups, which are separated by an N atom, have a relative anti disposition. The O/P/N/C torsion angles in (I), (II) and (III) are 169.65 (12), -177.83 (10) and -174.13 (10)°, respectively. Similar relative orientations have been observed for a majority of the compounds with C(O)NHP(O)[N]2 skeletons (Toghraee et al., 2011).

In (I), (II) and (III), adjacent molecules are linked via pairs of P O···H—N hydrogen bonds forming dimers with Ci symmetry (Tables 2, 4 and 6). For structures (II) and (III), phosphoryl atom O2 receives a second hydrogen bond (C—H···O) from the inversion-related molecule. A view of the packing in the crystal structure of compound (III) is shown in Fig. 7. Another C—H···O interaction is also observed in structure (II) (Table 5) involving carbonyl atom O1 as acceptor.

In summary, three new [XC(O)NH]P(O)[N(CH2C6H5)2]2 phosphoric triamides (X = CClF2, 3-F-C6H4 and 3,5-F2-C6H3) were studied by X-ray crystallography and compared with analogous compounds deposited in the CSD. In the C(O)NHP(O) fragment of these compounds, the P—N bond is longer and the O—P—N angle is contracted compared with the two remaining P—N bonds and O—P—N angles. For compounds having a C(O)NHP(O)[N]2 fragment, the geometry of the tertiary N atoms was also examined. Among the three angles around these atoms, the C—N—C angles in all reported structures have significantly lower values than do the two P—N—C angles. The sums of the bond angles at the tertiary N atoms have been used to evaluate their pyramidality. An anti orientation of the lone electron pair of the more pyramidal N atom relative to PO is observed for compounds with ΔSUM (= SUM1 - SUM2) ranging from 14.3 to 5.9°.

Related literature top

For related literature, see: Allen (2002); Döring et al. (2012); Dehghanpour et al. (2008, 2010); Gholivand et al. (2005, 2007); Gholivand, Alizadehgan, Arshadi & Firooz (2006); Gholivand, Mojahed, Salehi & Alizadehgan (2006); Gholivand, Shariatinia & Pourayoubi (2006); Gubina et al. (2000); Marsh (2009); Pourayoubi et al. (2011); Rebrova et al. (1992); Toghraee et al. (2011).

Experimental top

Three starting materials with the general formula XC(O)NHP(O)Cl2 (X = CClF2, 3-F-C6H4 and 3,5-F2-C6H3) were synthesized from the reaction between phosphorus pentachloride (16.7 mmol) and the corresponding XC(O)NH2 amide (16.7 mmol) in dry CCl4 at 358 K (about 3 h) followed by treatment with formic acid (16.7 mmol) at ice-bath temperature.

For the preparation of (I), a solution of dibenzylamine (4 mmol) in dry CHCl3 (5 ml) was added to a solution of CClF2C(O)NHP(O)Cl2 (1 mmol) in the same solvent (10 ml) at 273 K. After stirring for 5 h, the solvent was removed and the product was washed with distilled water. Single crystals were obtained from a solution of (I) in CH3OH–CHCl3 [ratio? volume?] by slow evaporation at 273 K.

For the preparation of (II), a solution of dibenzylamine (4 mmol) in dry CHCl3 (5 ml) was added to a solution of 3-F-C6H4C(O)NHP(O)Cl2 (1 mmol) in the same solvent (20 ml) and the resulting solution stirred at 273 K for 4 h. The solvent was the evaporated in vacuo and the product washed with distilled water. Colorless single crystals were obtained from a CH3CN solution by slow evaporation at room temperature.

For the preparation of (III), a solution of dibenzylamine (4 mmol) in dry CHCl3 was added to a solution of 3,5-F2-C6H3C(O)NHP(O)Cl2 (1 mmol) in the same solvent (20 ml). After stirring at 273 K for 4 h, the solvent was evaporated in vacuo and the product was washed with distilled water. Colorless single crystals were obtained from a CH3CN solution by slow evaporation at room temperature.

Refinement top

For compounds (I), (II) and (III), atom H1N was located in a difference map and refined isotropically. All of the remaining H atoms were placed at calculated positions and refined using a riding model, with C—H bond lengths of 0.93 (CH) or 0.97 Å (CH2). The isotropic displacement parameters for these H atoms were set at 1.2 times Ueq of their respective parent atoms. The largest difference peak and hole for (II) were 1.117 (3.01 Å from H15A) and -0.322 e Å-3 , with the positive peak in a small void of 57 Å3. This and a second difference peak in the void appeared to represent occupation by a diffuse source of electron density. Platon SQUEEZE estimated a total of 4 electrons per cell in the void, and no further action was taken. The results reported for this structure have not had SQUEEZE applied.

Computing details top

Data collection: APEX2 (Bruker, 2007) for (I); CrysAlis PRO (Oxford Diffraction, 2010) for (II), (III). Cell refinement: SAINT (Bruker, 2007) for (I); CrysAlis PRO (Oxford Diffraction, 2010) for (II), (III). Data reduction: SAINT (Bruker, 2007) for (I); CrysAlis RED (Oxford Diffraction, 2010) for (II), (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: XPW (Siemens, 1996) and Mercury (Macrae et al., 2008) for (I); SHELXTL (Sheldrick, 2008) for (II), (III). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004) for (I); SHELXTL (Sheldrick, 2008) for (II), (III).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot (50% probability) and atom-numbering scheme for (I). H atoms are drawn as circles of arbitrary radii.
[Figure 2] Fig. 2. Displacement ellipsoid plot (50% probability) and atom-numbering scheme for (II). H atoms are drawn as circles of arbitrary radii.
[Figure 3] Fig. 3. Displacement ellipsoid plot (50% probability) and atom-numbering scheme for (III). H atoms are drawn as circles of arbitrary radii.
[Figure 4] Fig. 4. Histogram of P—Namide (blue in the electronic version of the paper) and P—NC(O)NHP(O) (brown) bond distances in phosphoric triamides with C(O)NHP(O)[N]2 and C(O)NHP(O)[NH]2 fragments. The numbers of data found in each region are given above the column.
[Figure 5] Fig. 5. The anti orientation of the N3 lone electron pair (LEP) relative to PO in compound (I). For the C6H5CH2 moieties, only the ipso C atoms are shown for clarity. (Colour key: Cl green, F yellow–green and C dark grey.)
[Figure 6] Fig. 6. Sum of the surrounding bond angles (2 × P—N—C + C—N—C) at two tertiary N atoms (as different colors) from 60 data base entries.
[Figure 7] Fig. 7. Part of the crystal structure of compound (III). H atoms not involved in hydrogen bonding are not shown.
(I) N,N,N',N'-Tetrabenzyl-N''-(2-chloro- 2,2-difluoroacetyl)phosphoric triamide top
Crystal data top
C30H29ClF2N3O2PF(000) = 1184
Mr = 567.98Dx = 1.317 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9995 reflections
a = 10.8298 (3) Åθ = 2.6–29.0°
b = 9.9164 (3) ŵ = 0.23 mm1
c = 26.6740 (8) ÅT = 296 K
β = 91.539 (1)°Irregular, colorless
V = 2863.56 (15) Å30.56 × 0.51 × 0.48 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
6905 independent reflections
Radiation source: fine-focus sealed tube5873 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 28.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1414
Tmin = 0.694, Tmax = 0.746k = 1313
31854 measured reflectionsl = 3522
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0663P)2 + 1.1866P]
where P = (Fo2 + 2Fc2)/3
6905 reflections(Δ/σ)max = 0.001
356 parametersΔρmax = 0.78 e Å3
0 restraintsΔρmin = 0.68 e Å3
Crystal data top
C30H29ClF2N3O2PV = 2863.56 (15) Å3
Mr = 567.98Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.8298 (3) ŵ = 0.23 mm1
b = 9.9164 (3) ÅT = 296 K
c = 26.6740 (8) Å0.56 × 0.51 × 0.48 mm
β = 91.539 (1)°
Data collection top
Bruker APEXII CCD
diffractometer
6905 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
5873 reflections with I > 2σ(I)
Tmin = 0.694, Tmax = 0.746Rint = 0.019
31854 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.78 e Å3
6905 reflectionsΔρmin = 0.68 e Å3
356 parameters
Special details top

Experimental. IR (KBr, ν, cm-1): 3064, 3036, 2901, 2868, 2758, 1736, 1602, 1586, 1494, 1454, 1372, 1360, 1347, 1301, 1285, 1213, 1185, 1173, 1137, 1124, 1103, 1068, 1026, 977, 954, 944, 921, 905, 858, 833, 820, 808, 747, 725, 699, 671, 622, 609, 599, 581, 543, 520, 486, 465, 437, 416.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.34696 (6)0.83086 (7)1.01897 (2)0.0761 (2)
P10.01521 (3)0.88010 (4)0.925175 (13)0.03216 (11)
O10.25772 (12)0.85020 (15)0.89093 (5)0.0507 (3)
F20.33710 (12)1.06452 (13)0.98342 (5)0.0678 (3)
O20.10455 (10)0.92420 (13)0.96253 (4)0.0423 (3)
F30.45045 (11)0.9261 (2)0.94339 (6)0.0911 (5)
C30.21381 (19)0.5602 (2)0.94220 (7)0.0526 (4)
H30.19840.63440.96240.063*
N20.01394 (12)0.71619 (14)0.91926 (5)0.0366 (3)
N30.02763 (13)0.94120 (13)0.86824 (5)0.0359 (3)
C50.3281 (2)0.3594 (3)0.92671 (13)0.0817 (8)
H50.39090.29940.93570.098*
C40.3070 (2)0.4708 (3)0.95599 (10)0.0676 (6)
H40.35500.48610.98490.081*
C20.14316 (17)0.54042 (17)0.89859 (7)0.0435 (4)
C10.04933 (16)0.64269 (17)0.87983 (6)0.0406 (3)
H1A0.09070.70740.85880.049*
H1B0.01220.59660.85900.049*
C150.11343 (17)0.87955 (18)0.83075 (6)0.0431 (4)
H15A0.13870.79210.84320.052*
H15B0.06900.86440.80020.052*
C160.22776 (18)0.96065 (18)0.81805 (6)0.0464 (4)
C170.3107 (2)0.9971 (2)0.85393 (9)0.0591 (5)
H170.29450.97470.88730.071*
C180.4180 (2)1.0668 (3)0.84101 (13)0.0811 (8)
H180.47341.08990.86560.097*
C190.4422 (3)1.1013 (3)0.79216 (17)0.0992 (11)
H190.51381.14860.78350.119*
C120.4023 (3)0.4794 (4)0.86672 (11)0.0975 (11)
H120.46910.44730.84760.117*
C110.2996 (3)0.4016 (3)0.87355 (12)0.0941 (10)
H110.29680.31630.85910.113*
C100.1990 (2)0.4484 (2)0.90186 (10)0.0679 (6)
H100.12990.39390.90680.081*
C90.20186 (17)0.57579 (19)0.92262 (7)0.0464 (4)
C140.3073 (2)0.6534 (3)0.91567 (9)0.0618 (5)
H140.31080.73910.92980.074*
C130.4071 (2)0.6045 (4)0.88796 (11)0.0859 (9)
H130.47780.65700.88370.103*
C80.09195 (17)0.63158 (19)0.95136 (6)0.0450 (4)
H8A0.12020.68510.97920.054*
H8B0.04290.55760.96500.054*
C220.00184 (18)1.08433 (17)0.85889 (6)0.0428 (4)
H22A0.06031.11550.88450.051*
H22B0.07281.13760.86150.051*
C230.05588 (17)1.10691 (18)0.80788 (6)0.0450 (4)
C240.0088 (2)1.2072 (2)0.77678 (8)0.0567 (5)
H240.05811.25830.78690.068*
C250.0605 (3)1.2321 (3)0.73065 (9)0.0738 (7)
H250.02871.30040.71020.089*
C260.1577 (3)1.1569 (3)0.71521 (9)0.0805 (8)
H260.19211.17360.68420.097*
C270.2046 (3)1.0564 (3)0.74549 (9)0.0818 (8)
H270.27051.00450.73490.098*
C280.1544 (2)1.0320 (3)0.79184 (8)0.0635 (6)
H280.18750.96440.81230.076*
C200.3615 (4)1.0664 (3)0.75625 (13)0.1020 (12)
H200.37861.08970.72300.122*
C210.2532 (3)0.9960 (3)0.76855 (8)0.0723 (7)
H210.19850.97290.74370.087*
N10.12407 (12)0.93551 (15)0.94785 (5)0.0365 (3)
C290.23604 (15)0.90400 (17)0.93035 (6)0.0388 (3)
C300.34493 (16)0.9375 (2)0.96680 (7)0.0486 (4)
C60.2570 (3)0.3369 (2)0.88443 (13)0.0815 (8)
H60.27090.26070.86500.098*
C70.1647 (2)0.4263 (2)0.87036 (9)0.0608 (5)
H70.11650.40960.84160.073*
H1N0.1250 (19)0.973 (2)0.9743 (8)0.045 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0827 (4)0.0806 (4)0.0631 (3)0.0111 (3)0.0368 (3)0.0119 (3)
P10.03187 (19)0.0408 (2)0.02364 (17)0.00448 (15)0.00330 (13)0.00506 (14)
O10.0456 (7)0.0691 (9)0.0377 (6)0.0010 (6)0.0033 (5)0.0091 (6)
F20.0607 (7)0.0626 (8)0.0790 (8)0.0172 (6)0.0199 (6)0.0090 (6)
O20.0358 (6)0.0590 (7)0.0321 (5)0.0039 (5)0.0005 (4)0.0121 (5)
F30.0335 (6)0.1605 (16)0.0793 (9)0.0125 (8)0.0032 (6)0.0236 (10)
C30.0542 (11)0.0543 (11)0.0492 (10)0.0010 (8)0.0022 (8)0.0084 (8)
N20.0418 (7)0.0402 (7)0.0278 (6)0.0057 (5)0.0005 (5)0.0005 (5)
N30.0429 (7)0.0371 (7)0.0271 (6)0.0051 (5)0.0071 (5)0.0019 (5)
C50.0554 (13)0.0619 (14)0.129 (2)0.0098 (11)0.0169 (15)0.0348 (16)
C40.0511 (12)0.0753 (15)0.0761 (15)0.0016 (10)0.0018 (10)0.0312 (12)
C20.0454 (9)0.0393 (8)0.0459 (9)0.0060 (7)0.0042 (7)0.0017 (7)
C10.0495 (9)0.0419 (8)0.0302 (7)0.0039 (7)0.0020 (6)0.0049 (6)
C150.0546 (10)0.0459 (9)0.0282 (7)0.0052 (7)0.0117 (6)0.0049 (6)
C160.0542 (10)0.0432 (9)0.0406 (8)0.0112 (8)0.0184 (7)0.0063 (7)
C170.0599 (12)0.0556 (11)0.0613 (12)0.0002 (9)0.0104 (9)0.0066 (9)
C180.0569 (13)0.0632 (14)0.122 (2)0.0019 (11)0.0191 (14)0.0033 (15)
C190.0776 (19)0.0694 (17)0.147 (3)0.0003 (14)0.059 (2)0.0147 (19)
C120.0754 (19)0.140 (3)0.0764 (17)0.058 (2)0.0095 (14)0.0003 (18)
C110.102 (2)0.087 (2)0.094 (2)0.0529 (18)0.0100 (17)0.0222 (16)
C100.0686 (14)0.0563 (12)0.0788 (15)0.0201 (10)0.0070 (11)0.0052 (11)
C90.0500 (10)0.0484 (9)0.0408 (8)0.0145 (8)0.0015 (7)0.0089 (7)
C140.0556 (12)0.0673 (13)0.0624 (12)0.0083 (10)0.0022 (9)0.0120 (10)
C130.0547 (13)0.121 (3)0.0815 (18)0.0183 (15)0.0113 (12)0.0195 (17)
C80.0509 (9)0.0496 (10)0.0345 (8)0.0097 (8)0.0010 (7)0.0089 (7)
C220.0543 (10)0.0360 (8)0.0380 (8)0.0042 (7)0.0024 (7)0.0016 (6)
C230.0512 (10)0.0451 (9)0.0384 (8)0.0095 (7)0.0054 (7)0.0040 (7)
C240.0730 (13)0.0460 (10)0.0506 (10)0.0031 (9)0.0087 (9)0.0065 (8)
C250.103 (2)0.0638 (14)0.0536 (12)0.0141 (13)0.0128 (12)0.0232 (11)
C260.0878 (18)0.104 (2)0.0501 (12)0.0216 (16)0.0092 (12)0.0218 (13)
C270.0684 (15)0.120 (2)0.0577 (13)0.0108 (15)0.0155 (11)0.0137 (14)
C280.0617 (12)0.0823 (15)0.0467 (10)0.0117 (11)0.0044 (9)0.0156 (10)
C200.120 (3)0.094 (2)0.089 (2)0.0125 (19)0.066 (2)0.0334 (17)
C210.0889 (16)0.0790 (15)0.0471 (11)0.0152 (13)0.0307 (11)0.0169 (10)
N10.0337 (6)0.0485 (8)0.0271 (6)0.0058 (5)0.0035 (5)0.0085 (5)
C290.0350 (8)0.0483 (9)0.0330 (7)0.0056 (6)0.0024 (6)0.0012 (6)
C300.0346 (8)0.0640 (12)0.0470 (9)0.0062 (8)0.0048 (7)0.0033 (8)
C60.0720 (16)0.0443 (11)0.129 (2)0.0051 (11)0.0243 (17)0.0049 (14)
C70.0618 (12)0.0457 (10)0.0753 (14)0.0061 (9)0.0092 (10)0.0103 (10)
Geometric parameters (Å, º) top
P1—N11.7011 (13)C12—H120.9300
P1—N21.6331 (14)C11—C101.388 (4)
P1—N31.6373 (13)C11—H110.9300
P1—O21.4739 (11)C10—C91.380 (3)
Cl1—C301.748 (2)C10—H100.9300
O1—C291.208 (2)C9—C141.385 (3)
F2—C301.338 (2)C9—C81.504 (2)
F3—C301.322 (2)C14—C131.381 (3)
C3—C41.385 (3)C14—H140.9300
C3—C21.389 (3)C13—H130.9300
C3—H30.9300C8—H8A0.9700
N2—C11.465 (2)C8—H8B0.9700
N2—C81.480 (2)C22—C231.512 (2)
N3—C221.477 (2)C22—H22A0.9700
N3—C151.4788 (19)C22—H22B0.9700
C5—C61.367 (4)C23—C281.378 (3)
C5—C41.375 (4)C23—C241.383 (3)
C5—H50.9300C24—C251.388 (3)
C4—H40.9300C24—H240.9300
C2—C71.383 (3)C25—C261.363 (4)
C2—C11.511 (2)C25—H250.9300
C1—H1A0.9700C26—C271.372 (4)
C1—H1B0.9700C26—H260.9300
C15—C161.507 (3)C27—C281.385 (3)
C15—H15A0.9700C27—H270.9300
C15—H15B0.9700C28—H280.9300
C16—C171.378 (3)C20—C211.396 (4)
C16—C211.387 (2)C20—H200.9300
C17—C181.387 (3)C21—H210.9300
C17—H170.9300N1—C291.348 (2)
C18—C191.366 (5)N1—H1N0.80 (2)
C18—H180.9300C29—C301.544 (2)
C19—C201.359 (5)C6—C71.381 (4)
C19—H190.9300C6—H60.9300
C12—C111.362 (5)C7—H70.9300
C12—C131.366 (5)
O2—P1—N1104.82 (7)C13—C14—C9120.5 (3)
O2—P1—N2111.59 (7)C13—C14—H14119.8
O2—P1—N3118.57 (7)C9—C14—H14119.8
N1—P1—N2110.25 (7)C12—C13—C14120.2 (3)
N1—P1—N3105.08 (7)C12—C13—H13119.9
N2—P1—N3106.23 (7)C14—C13—H13119.9
C4—C3—C2120.9 (2)N2—C8—C9111.72 (13)
C4—C3—H3119.6N2—C8—H8A109.3
C2—C3—H3119.6C9—C8—H8A109.3
C1—N2—C8114.75 (14)N2—C8—H8B109.3
C1—N2—P1124.74 (11)C9—C8—H8B109.3
C8—N2—P1120.13 (11)H8A—C8—H8B107.9
C22—N3—C15114.69 (13)N3—C22—C23112.63 (14)
C15—N3—P1120.57 (11)N3—C22—H22A109.1
C22—N3—P1119.96 (10)C23—C22—H22A109.1
C6—C5—C4120.1 (2)N3—C22—H22B109.1
C6—C5—H5120.0C23—C22—H22B109.1
C4—C5—H5120.0H22A—C22—H22B107.8
C5—C4—C3119.6 (2)C28—C23—C24118.53 (18)
C5—C4—H4120.2C28—C23—C22121.41 (17)
C3—C4—H4120.2C24—C23—C22120.04 (18)
C7—C2—C3118.32 (19)C23—C24—C25120.6 (2)
C7—C2—C1119.39 (17)C23—C24—H24119.7
C3—C2—C1122.20 (16)C25—C24—H24119.7
N2—C1—C2114.80 (13)C26—C25—C24120.3 (2)
N2—C1—H1A108.6C26—C25—H25119.9
C2—C1—H1A108.6C24—C25—H25119.9
N2—C1—H1B108.6C25—C26—C27119.8 (2)
C2—C1—H1B108.6C25—C26—H26120.1
H1A—C1—H1B107.5C27—C26—H26120.1
N3—C15—C16115.39 (14)C26—C27—C28120.3 (3)
N3—C15—H15A108.4C26—C27—H27119.9
C16—C15—H15A108.4C28—C27—H27119.9
N3—C15—H15B108.4C23—C28—C27120.6 (2)
C16—C15—H15B108.4C23—C28—H28119.7
H15A—C15—H15B107.5C27—C28—H28119.7
C17—C16—C21118.6 (2)C19—C20—C21120.9 (3)
C17—C16—C15122.06 (16)C19—C20—H20119.5
C21—C16—C15119.3 (2)C21—C20—H20119.5
C16—C17—C18121.0 (2)C16—C21—C20119.6 (3)
C16—C17—H17119.5C16—C21—H21120.2
C18—C17—H17119.5C20—C21—H21120.2
C19—C18—C17120.0 (3)C29—N1—P1126.83 (11)
C19—C18—H18120.0C29—N1—H1N115.1 (15)
C17—C18—H18120.0P1—N1—H1N117.1 (15)
C20—C19—C18119.8 (3)O1—C29—N1126.99 (15)
C20—C19—H19120.1O1—C29—C30118.70 (15)
C18—C19—H19120.1N1—C29—C30114.27 (14)
C11—C12—C13120.0 (3)F3—C30—F2107.49 (17)
C11—C12—H12120.0F3—C30—C29109.84 (15)
C13—C12—H12120.0F2—C30—C29110.93 (16)
C12—C11—C10120.6 (3)F3—C30—Cl1109.36 (15)
C12—C11—H11119.7F2—C30—Cl1107.76 (13)
C10—C11—H11119.7C29—C30—Cl1111.35 (13)
C9—C10—C11119.9 (3)C5—C6—C7120.5 (2)
C9—C10—H10120.0C5—C6—H6119.8
C11—C10—H10120.0C7—C6—H6119.8
C10—C9—C14118.8 (2)C6—C7—C2120.6 (2)
C10—C9—C8121.0 (2)C6—C7—H7119.7
C14—C9—C8120.13 (19)C2—C7—H7119.7
O2—P1—N2—C1169.65 (12)C1—N2—C8—C967.4 (2)
N3—P1—N2—C139.05 (15)P1—N2—C8—C9105.97 (16)
N1—P1—N2—C174.29 (14)C10—C9—C8—N295.6 (2)
O2—P1—N2—C82.96 (14)C14—C9—C8—N283.1 (2)
N3—P1—N2—C8133.56 (12)C15—N3—C22—C2357.0 (2)
N1—P1—N2—C8113.09 (12)P1—N3—C22—C23147.32 (13)
O2—P1—N3—C2269.94 (15)N3—C22—C23—C2851.2 (2)
N2—P1—N3—C22163.55 (13)N3—C22—C23—C24130.71 (18)
N1—P1—N3—C2246.70 (14)C28—C23—C24—C250.5 (3)
O2—P1—N3—C1584.28 (14)C22—C23—C24—C25177.64 (19)
N2—P1—N3—C1542.23 (14)C23—C24—C25—C260.7 (4)
N1—P1—N3—C15159.09 (13)C24—C25—C26—C270.2 (4)
C6—C5—C4—C30.4 (4)C25—C26—C27—C280.6 (5)
C2—C3—C4—C51.4 (3)C24—C23—C28—C270.3 (4)
C4—C3—C2—C72.7 (3)C22—C23—C28—C27178.4 (2)
C4—C3—C2—C1173.96 (18)C26—C27—C28—C230.8 (4)
C8—N2—C1—C264.23 (18)C18—C19—C20—C210.4 (5)
P1—N2—C1—C2122.80 (14)C17—C16—C21—C200.3 (3)
C7—C2—C1—N2149.48 (17)C15—C16—C21—C20177.4 (2)
C3—C2—C1—N233.9 (2)C19—C20—C21—C160.3 (4)
C22—N3—C15—C1648.0 (2)O2—P1—N1—C29170.32 (14)
P1—N3—C15—C16107.54 (15)N2—P1—N1—C2950.10 (16)
N3—C15—C16—C1758.8 (2)N3—P1—N1—C2963.97 (16)
N3—C15—C16—C21123.49 (19)P1—N1—C29—O113.5 (3)
C21—C16—C17—C180.5 (3)P1—N1—C29—C30164.11 (13)
C15—C16—C17—C18177.19 (19)O1—C29—C30—F313.3 (3)
C16—C17—C18—C190.6 (4)N1—C29—C30—F3168.88 (17)
C17—C18—C19—C200.5 (4)O1—C29—C30—F2131.99 (18)
C13—C12—C11—C100.2 (5)N1—C29—C30—F250.2 (2)
C12—C11—C10—C91.2 (4)O1—C29—C30—Cl1108.00 (17)
C11—C10—C9—C141.6 (3)N1—C29—C30—Cl169.82 (19)
C11—C10—C9—C8177.0 (2)C4—C5—C6—C70.9 (4)
C10—C9—C14—C130.7 (3)C5—C6—C7—C20.4 (4)
C8—C9—C14—C13177.9 (2)C3—C2—C7—C62.2 (3)
C11—C12—C13—C141.1 (4)C1—C2—C7—C6174.6 (2)
C9—C14—C13—C120.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.80 (2)1.98 (2)2.7788 (17)172 (2)
Symmetry code: (i) x, y+2, z+2.
(II) N,N,N',N'-Tetrabenzyl-N''-(3- fluorobenzoyl)phosphoric triamide top
Crystal data top
C35H33FN3O2PZ = 2
Mr = 577.61F(000) = 608
Triclinic, P1Dx = 1.263 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.0173 (10) ÅCell parameters from 6536 reflections
b = 11.2362 (8) Åθ = 3.3–32.3°
c = 14.5992 (12) ŵ = 0.13 mm1
α = 99.351 (6)°T = 173 K
β = 109.960 (8)°Chunk, colorless
γ = 91.135 (7)°0.48 × 0.40 × 0.36 mm
V = 1519.0 (2) Å3
Data collection top
Xcalibur, Eos, Gemini
diffractometer
9840 independent reflections
Radiation source: Enhance (Mo) X-ray Source8118 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
Detector resolution: 16.1500 pixels mm-1θmax = 32.3°, θmin = 3.3°
ω scansh = 1414
Absorption correction: multi-scan
CrysAlis PRO, Oxford Diffraction, 2010.
k = 1516
Tmin = 0.943, Tmax = 1.000l = 2121
17423 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0785P)2 + 0.4137P]
where P = (Fo2 + 2Fc2)/3
9840 reflections(Δ/σ)max = 0.001
383 parametersΔρmax = 1.12 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C35H33FN3O2Pγ = 91.135 (7)°
Mr = 577.61V = 1519.0 (2) Å3
Triclinic, P1Z = 2
a = 10.0173 (10) ÅMo Kα radiation
b = 11.2362 (8) ŵ = 0.13 mm1
c = 14.5992 (12) ÅT = 173 K
α = 99.351 (6)°0.48 × 0.40 × 0.36 mm
β = 109.960 (8)°
Data collection top
Xcalibur, Eos, Gemini
diffractometer
9840 independent reflections
Absorption correction: multi-scan
CrysAlis PRO, Oxford Diffraction, 2010.
8118 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 1.000Rint = 0.021
17423 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 1.12 e Å3
9840 reflectionsΔρmin = 0.32 e Å3
383 parameters
Special details top

Experimental. IR (KBr, ν, cm-1): 3080, 3064, 3031, 2888, 2864, 1681, 1588, 1495, 1455, 1365, 1356, 1316, 1285, 1279, 1209, 1190, 1099, 1064, 1029, 1004, 951, 936, 916, 902, 887, 884, 802, 748, 700, 675, 604, 596, 585, 557, 527, 485, 462, 432.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.61224 (3)0.52499 (3)0.17147 (2)0.01907 (8)
F10.09542 (14)0.11276 (10)0.14885 (8)0.0595 (3)
O10.43362 (11)0.37517 (10)0.25151 (7)0.0341 (2)
O20.64579 (9)0.56565 (8)0.08984 (6)0.02406 (18)
N10.46767 (11)0.42457 (9)0.11608 (7)0.02139 (19)
H1N0.4313 (18)0.4221 (15)0.0549 (13)0.029 (4)*
N20.56350 (11)0.62438 (9)0.24783 (7)0.02175 (19)
N30.75016 (11)0.46451 (10)0.24019 (7)0.02328 (19)
C10.26260 (13)0.28721 (11)0.09631 (9)0.0248 (2)
C20.24014 (15)0.23735 (12)0.00175 (10)0.0301 (3)
H20.30690.25170.03080.036*
C30.11489 (18)0.16555 (13)0.05481 (11)0.0378 (3)
C40.01102 (18)0.14373 (15)0.01578 (15)0.0471 (4)
H40.07350.09770.05450.057*
C50.03640 (18)0.19228 (17)0.08265 (16)0.0509 (4)
H50.03110.17770.11110.061*
C60.16203 (16)0.26254 (14)0.13908 (13)0.0380 (3)
H60.17940.29330.20560.046*
C70.39457 (13)0.36511 (11)0.16160 (9)0.0233 (2)
C80.76361 (13)0.43097 (12)0.33578 (8)0.0248 (2)
H8A0.67370.43970.34660.030*
H8B0.83550.48610.38830.030*
C90.80392 (14)0.30247 (12)0.34142 (9)0.0265 (2)
C100.71824 (16)0.20475 (13)0.27461 (11)0.0347 (3)
H100.63360.21850.22690.042*
C110.75667 (19)0.08760 (15)0.27790 (14)0.0442 (4)
H110.69900.02350.23190.053*
C120.8805 (2)0.06598 (16)0.34936 (16)0.0492 (4)
H120.90720.01260.35130.059*
C130.96441 (19)0.16098 (18)0.41774 (15)0.0514 (4)
H131.04690.14620.46700.062*
C140.92681 (16)0.27899 (15)0.41383 (12)0.0392 (3)
H140.98470.34270.46020.047*
C150.87940 (14)0.45173 (13)0.21260 (9)0.0277 (2)
H15A0.85550.46060.14400.033*
H15B0.91010.37110.21820.033*
C161.00150 (13)0.54409 (12)0.27702 (10)0.0272 (2)
C171.11964 (15)0.51077 (14)0.34877 (11)0.0326 (3)
H171.12490.43050.35720.039*
C181.23005 (16)0.59669 (16)0.40806 (12)0.0391 (3)
H181.30850.57340.45570.047*
C191.22389 (17)0.71609 (16)0.39659 (13)0.0402 (3)
H191.29720.77350.43690.048*
C201.10789 (17)0.74988 (15)0.32468 (14)0.0415 (3)
H201.10360.83010.31610.050*
C210.99754 (16)0.66420 (14)0.26510 (12)0.0365 (3)
H210.92010.68770.21670.044*
C220.67207 (13)0.71875 (11)0.31683 (8)0.0241 (2)
H22A0.67100.78870.28550.029*
H22B0.76550.68830.33040.029*
C230.64753 (13)0.75728 (11)0.41343 (8)0.0241 (2)
C240.61737 (16)0.67221 (13)0.46430 (10)0.0312 (3)
H240.60600.59050.43650.037*
C250.60394 (18)0.70759 (16)0.55601 (10)0.0375 (3)
H250.58480.64970.58970.045*
C260.61904 (19)0.82884 (18)0.59725 (11)0.0450 (4)
H260.61100.85270.65910.054*
C270.6460 (2)0.91451 (16)0.54692 (13)0.0471 (4)
H270.65470.99630.57430.057*
C280.66030 (16)0.87901 (13)0.45523 (11)0.0342 (3)
H280.67860.93730.42160.041*
C290.41673 (13)0.66476 (12)0.21893 (9)0.0250 (2)
H29A0.39620.69480.27850.030*
H29B0.34960.59560.18230.030*
C300.39415 (13)0.76240 (12)0.15641 (9)0.0253 (2)
C310.39678 (17)0.88282 (13)0.19750 (11)0.0367 (3)
H310.40970.90410.26440.044*
C320.38032 (19)0.97234 (15)0.13996 (15)0.0476 (4)
H320.38211.05300.16830.057*
C330.36147 (18)0.94131 (17)0.04103 (16)0.0482 (4)
H330.35241.00110.00260.058*
C340.3560 (2)0.82113 (18)0.00112 (13)0.0480 (4)
H340.34170.80010.06830.058*
C350.37159 (18)0.73209 (15)0.05590 (10)0.0369 (3)
H350.36700.65140.02680.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.02207 (14)0.02263 (14)0.01297 (12)0.00043 (10)0.00599 (10)0.00493 (10)
F10.0821 (8)0.0427 (6)0.0359 (5)0.0171 (5)0.0037 (5)0.0028 (4)
O10.0346 (5)0.0483 (6)0.0208 (4)0.0061 (4)0.0085 (4)0.0136 (4)
O20.0274 (4)0.0299 (4)0.0163 (3)0.0020 (3)0.0084 (3)0.0070 (3)
N10.0246 (5)0.0254 (5)0.0139 (4)0.0018 (3)0.0059 (3)0.0054 (3)
N20.0239 (5)0.0245 (5)0.0159 (4)0.0023 (3)0.0056 (3)0.0038 (3)
N30.0242 (5)0.0304 (5)0.0169 (4)0.0048 (4)0.0079 (4)0.0072 (4)
C10.0259 (5)0.0213 (5)0.0276 (6)0.0018 (4)0.0084 (4)0.0076 (4)
C20.0378 (7)0.0233 (6)0.0279 (6)0.0022 (5)0.0086 (5)0.0075 (5)
C30.0462 (8)0.0236 (6)0.0334 (7)0.0032 (5)0.0017 (6)0.0045 (5)
C40.0340 (8)0.0339 (8)0.0615 (11)0.0078 (6)0.0049 (7)0.0027 (7)
C50.0346 (8)0.0483 (10)0.0705 (12)0.0095 (7)0.0257 (8)0.0017 (9)
C60.0339 (7)0.0377 (7)0.0447 (8)0.0047 (6)0.0204 (6)0.0002 (6)
C70.0242 (5)0.0261 (5)0.0215 (5)0.0016 (4)0.0083 (4)0.0084 (4)
C80.0289 (6)0.0293 (6)0.0155 (5)0.0047 (4)0.0056 (4)0.0064 (4)
C90.0274 (6)0.0309 (6)0.0227 (5)0.0060 (4)0.0080 (4)0.0101 (5)
C100.0352 (7)0.0324 (7)0.0322 (7)0.0044 (5)0.0052 (5)0.0084 (5)
C110.0485 (9)0.0311 (7)0.0523 (9)0.0040 (6)0.0159 (7)0.0089 (7)
C120.0491 (9)0.0391 (8)0.0676 (12)0.0176 (7)0.0238 (9)0.0229 (8)
C130.0391 (9)0.0531 (10)0.0589 (11)0.0186 (7)0.0051 (8)0.0264 (9)
C140.0321 (7)0.0436 (8)0.0351 (7)0.0076 (6)0.0003 (6)0.0127 (6)
C150.0275 (6)0.0338 (6)0.0238 (5)0.0064 (5)0.0114 (5)0.0053 (5)
C160.0243 (5)0.0338 (6)0.0269 (6)0.0053 (4)0.0121 (5)0.0080 (5)
C170.0283 (6)0.0377 (7)0.0337 (7)0.0060 (5)0.0103 (5)0.0121 (6)
C180.0280 (7)0.0510 (9)0.0367 (7)0.0013 (6)0.0064 (6)0.0144 (7)
C190.0329 (7)0.0449 (8)0.0420 (8)0.0046 (6)0.0134 (6)0.0062 (7)
C200.0355 (7)0.0357 (7)0.0568 (10)0.0021 (6)0.0177 (7)0.0145 (7)
C210.0288 (6)0.0397 (8)0.0433 (8)0.0055 (5)0.0109 (6)0.0176 (6)
C220.0294 (6)0.0246 (5)0.0181 (5)0.0011 (4)0.0083 (4)0.0034 (4)
C230.0261 (5)0.0273 (6)0.0164 (5)0.0039 (4)0.0050 (4)0.0025 (4)
C240.0441 (7)0.0310 (6)0.0218 (5)0.0070 (5)0.0143 (5)0.0069 (5)
C250.0466 (8)0.0493 (9)0.0214 (6)0.0119 (6)0.0151 (6)0.0117 (6)
C260.0524 (9)0.0598 (10)0.0223 (6)0.0142 (8)0.0154 (6)0.0007 (6)
C270.0596 (10)0.0396 (8)0.0371 (8)0.0067 (7)0.0179 (7)0.0096 (6)
C280.0404 (7)0.0289 (6)0.0313 (6)0.0033 (5)0.0123 (6)0.0004 (5)
C290.0266 (5)0.0289 (6)0.0212 (5)0.0053 (4)0.0091 (4)0.0072 (4)
C300.0268 (5)0.0276 (6)0.0228 (5)0.0075 (4)0.0089 (4)0.0071 (4)
C310.0397 (7)0.0306 (7)0.0321 (7)0.0088 (5)0.0038 (6)0.0025 (5)
C320.0430 (9)0.0289 (7)0.0616 (11)0.0060 (6)0.0039 (8)0.0132 (7)
C330.0367 (8)0.0540 (10)0.0666 (11)0.0153 (7)0.0202 (8)0.0404 (9)
C340.0572 (10)0.0644 (11)0.0406 (8)0.0331 (9)0.0283 (8)0.0321 (8)
C350.0504 (8)0.0398 (8)0.0252 (6)0.0202 (6)0.0156 (6)0.0120 (5)
Geometric parameters (Å, º) top
P1—N11.6922 (10)C16—C211.388 (2)
P1—N21.6484 (11)C16—C171.3916 (18)
P1—N31.6400 (11)C17—C181.392 (2)
P1—O21.4786 (9)C17—H170.9300
F1—C31.3500 (19)C18—C191.379 (2)
O1—C71.2200 (15)C18—H180.9300
N1—C71.3716 (15)C19—C201.382 (2)
N1—H1N0.837 (18)C19—H190.9300
N2—C221.4768 (15)C20—C211.391 (2)
N2—C291.4868 (16)C20—H200.9300
N3—C81.4672 (15)C21—H210.9300
N3—C151.4844 (16)C22—C231.5096 (17)
C1—C21.3886 (18)C22—H22A0.9700
C1—C61.3987 (19)C22—H22B0.9700
C1—C71.4984 (17)C23—C281.3886 (19)
C2—C31.3851 (19)C23—C241.3888 (18)
C2—H20.9300C24—C251.3860 (19)
C3—C41.381 (3)C24—H240.9300
C4—C51.385 (3)C25—C261.380 (2)
C4—H40.9300C25—H250.9300
C5—C61.388 (2)C26—C271.376 (3)
C5—H50.9300C26—H260.9300
C6—H60.9300C27—C281.390 (2)
C8—C91.5144 (18)C27—H270.9300
C8—H8A0.9700C28—H280.9300
C8—H8B0.9700C29—C301.5107 (17)
C9—C141.3847 (18)C29—H29A0.9700
C9—C101.3917 (19)C29—H29B0.9700
C10—C111.382 (2)C30—C311.3839 (19)
C10—H100.9300C30—C351.3887 (18)
C11—C121.377 (3)C31—C321.390 (2)
C11—H110.9300C31—H310.9300
C12—C131.374 (3)C32—C331.375 (3)
C12—H120.9300C32—H320.9300
C13—C141.390 (2)C33—C341.382 (3)
C13—H130.9300C33—H330.9300
C14—H140.9300C34—C351.381 (2)
C15—C161.5181 (19)C34—H340.9300
C15—H15A0.9700C35—H350.9300
C15—H15B0.9700
N1—P1—N2103.81 (5)C21—C16—C17118.52 (13)
N1—P1—N3112.50 (5)C21—C16—C15120.36 (12)
N2—P1—N3106.54 (5)C17—C16—C15121.13 (12)
O2—P1—N1105.60 (5)C16—C17—C18120.50 (14)
O2—P1—N2118.92 (5)C16—C17—H17119.8
O2—P1—N3109.48 (5)C18—C17—H17119.8
C7—N1—P1127.16 (8)C19—C18—C17120.46 (14)
C7—N1—H1N118.5 (12)C19—C18—H18119.8
P1—N1—H1N113.4 (12)C17—C18—H18119.8
C22—N2—C29113.09 (10)C18—C19—C20119.51 (15)
C22—N2—P1117.96 (8)C18—C19—H19120.2
C29—N2—P1121.34 (8)C20—C19—H19120.2
C8—N3—C15114.81 (10)C19—C20—C21120.18 (15)
C8—N3—P1124.58 (8)C19—C20—H20119.9
C15—N3—P1120.32 (8)C21—C20—H20119.9
C2—C1—C6120.18 (13)C16—C21—C20120.82 (14)
C2—C1—C7122.70 (12)C16—C21—H21119.6
C6—C1—C7117.09 (12)C20—C21—H21119.6
C3—C2—C1117.73 (14)N2—C22—C23112.56 (10)
C3—C2—H2121.1N2—C22—H22A109.1
C1—C2—H2121.1C23—C22—H22A109.1
F1—C3—C4118.74 (14)N2—C22—H22B109.1
F1—C3—C2117.89 (15)C23—C22—H22B109.1
C4—C3—C2123.36 (15)H22A—C22—H22B107.8
C3—C4—C5118.09 (14)C28—C23—C24118.56 (12)
C3—C4—H4121.0C28—C23—C22120.38 (12)
C5—C4—H4121.0C24—C23—C22121.01 (11)
C4—C5—C6120.33 (16)C25—C24—C23120.85 (14)
C4—C5—H5119.8C25—C24—H24119.6
C6—C5—H5119.8C23—C24—H24119.6
C5—C6—C1120.23 (15)C26—C25—C24119.88 (15)
C5—C6—H6119.9C26—C25—H25120.1
C1—C6—H6119.9C24—C25—H25120.1
O1—C7—N1122.00 (11)C27—C26—C25120.03 (14)
O1—C7—C1120.72 (11)C27—C26—H26120.0
N1—C7—C1117.28 (10)C25—C26—H26120.0
N3—C8—C9112.68 (10)C26—C27—C28120.08 (15)
N3—C8—H8A109.1C26—C27—H27120.0
C9—C8—H8A109.1C28—C27—H27120.0
N3—C8—H8B109.1C23—C28—C27120.58 (15)
C9—C8—H8B109.1C23—C28—H28119.7
H8A—C8—H8B107.8C27—C28—H28119.7
C14—C9—C10118.16 (13)N2—C29—C30113.65 (10)
C14—C9—C8120.79 (12)N2—C29—H29A108.8
C10—C9—C8121.05 (11)C30—C29—H29A108.8
C11—C10—C9121.19 (14)N2—C29—H29B108.8
C11—C10—H10119.4C30—C29—H29B108.8
C9—C10—H10119.4H29A—C29—H29B107.7
C12—C11—C10119.90 (16)C31—C30—C35118.79 (13)
C12—C11—H11120.1C31—C30—C29121.26 (12)
C10—C11—H11120.1C35—C30—C29119.95 (12)
C13—C12—C11119.76 (16)C30—C31—C32120.80 (15)
C13—C12—H12120.1C30—C31—H31119.6
C11—C12—H12120.1C32—C31—H31119.6
C12—C13—C14120.42 (15)C33—C32—C31119.79 (16)
C12—C13—H13119.8C33—C32—H32120.1
C14—C13—H13119.8C31—C32—H32120.1
C9—C14—C13120.55 (16)C32—C33—C34119.86 (15)
C9—C14—H14119.7C32—C33—H33120.1
C13—C14—H14119.7C34—C33—H33120.1
N3—C15—C16112.84 (10)C35—C34—C33120.36 (16)
N3—C15—H15A109.0C35—C34—H34119.8
C16—C15—H15A109.0C33—C34—H34119.8
N3—C15—H15B109.0C34—C35—C30120.37 (15)
C16—C15—H15B109.0C34—C35—H35119.8
H15A—C15—H15B107.8C30—C35—H35119.8
O2—P1—N1—C7177.83 (10)C10—C9—C14—C131.4 (2)
N3—P1—N1—C762.80 (12)C8—C9—C14—C13179.03 (15)
N2—P1—N1—C751.98 (12)C12—C13—C14—C90.4 (3)
O2—P1—N2—C2269.72 (10)C8—N3—C15—C1669.52 (14)
N3—P1—N2—C2254.45 (9)P1—N3—C15—C16104.64 (11)
N1—P1—N2—C22173.40 (8)N3—C15—C16—C2173.76 (16)
O2—P1—N2—C2977.75 (10)N3—C15—C16—C17106.47 (14)
N3—P1—N2—C29158.08 (9)C21—C16—C17—C181.0 (2)
N1—P1—N2—C2939.13 (10)C15—C16—C17—C18179.27 (13)
O2—P1—N3—C8170.38 (10)C16—C17—C18—C190.1 (2)
N2—P1—N3—C840.57 (11)C17—C18—C19—C200.9 (2)
N1—P1—N3—C872.54 (11)C18—C19—C20—C210.7 (3)
O2—P1—N3—C153.18 (11)C17—C16—C21—C201.1 (2)
N2—P1—N3—C15132.99 (10)C15—C16—C21—C20179.08 (14)
N1—P1—N3—C15113.90 (10)C19—C20—C21—C160.3 (2)
C6—C1—C2—C31.3 (2)C29—N2—C22—C2361.38 (13)
C7—C1—C2—C3179.24 (12)P1—N2—C22—C23148.57 (9)
C1—C2—C3—F1177.25 (13)N2—C22—C23—C28135.97 (12)
C1—C2—C3—C41.5 (2)N2—C22—C23—C2446.59 (16)
F1—C3—C4—C5176.03 (16)C28—C23—C24—C251.7 (2)
C2—C3—C4—C52.7 (3)C22—C23—C24—C25175.83 (13)
C3—C4—C5—C61.2 (3)C23—C24—C25—C260.7 (2)
C4—C5—C6—C11.5 (3)C24—C25—C26—C270.6 (3)
C2—C1—C6—C52.7 (2)C25—C26—C27—C281.0 (3)
C7—C1—C6—C5179.17 (15)C24—C23—C28—C271.3 (2)
P1—N1—C7—O13.97 (19)C22—C23—C28—C27176.22 (14)
P1—N1—C7—C1175.47 (9)C26—C27—C28—C230.0 (3)
C2—C1—C7—O1156.09 (13)C22—N2—C29—C3067.33 (13)
C6—C1—C7—O121.96 (19)P1—N2—C29—C3081.59 (12)
C2—C1—C7—N124.46 (18)N2—C29—C30—C31100.23 (15)
C6—C1—C7—N1157.50 (13)N2—C29—C30—C3579.14 (15)
C15—N3—C8—C957.00 (14)C35—C30—C31—C321.4 (2)
P1—N3—C8—C9129.12 (10)C29—C30—C31—C32177.98 (14)
N3—C8—C9—C14121.40 (14)C30—C31—C32—C330.1 (3)
N3—C8—C9—C1059.07 (17)C31—C32—C33—C341.4 (3)
C14—C9—C10—C112.2 (2)C32—C33—C34—C351.0 (3)
C8—C9—C10—C11178.24 (15)C33—C34—C35—C300.5 (3)
C9—C10—C11—C121.2 (3)C31—C30—C35—C341.7 (2)
C10—C11—C12—C130.7 (3)C29—C30—C35—C34177.66 (14)
C11—C12—C13—C141.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.932.453.1124 (16)128
C25—H25···O1ii0.932.453.2342 (17)142
N1—H1N···O2i0.837 (18)2.017 (18)2.8497 (13)173.7 (17)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.
(III) N,N,N',N'-Tetrabenzyl-N''-(3,5- difluorobenzoyl)phosphoric triamide top
Crystal data top
C35H32F2N3O2PZ = 2
Mr = 595.61F(000) = 624
Triclinic, P1Dx = 1.341 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 11.9526 (11) ÅCell parameters from 6783 reflections
b = 12.2897 (10) Åθ = 3.2–32.3°
c = 12.7463 (12) ŵ = 0.14 mm1
α = 102.074 (7)°T = 173 K
β = 104.462 (8)°Chunk, colorless
γ = 118.262 (9)°0.32 × 0.28 × 0.16 mm
V = 1474.5 (2) Å3
Data collection top
Oxford Diffraction Xcalibur (Eos, Gemini)
diffractometer
9523 independent reflections
Radiation source: Enhance (Mo) X-ray Source7763 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Detector resolution: 16.1500 pixels mm-1θmax = 32.4°, θmin = 3.2°
ω scansh = 1717
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
k = 1718
Tmin = 0.992, Tmax = 1.000l = 1818
17265 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0513P)2 + 0.4759P]
where P = (Fo2 + 2Fc2)/3
9523 reflections(Δ/σ)max < 0.001
392 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
C35H32F2N3O2Pγ = 118.262 (9)°
Mr = 595.61V = 1474.5 (2) Å3
Triclinic, P1Z = 2
a = 11.9526 (11) ÅMo Kα radiation
b = 12.2897 (10) ŵ = 0.14 mm1
c = 12.7463 (12) ÅT = 173 K
α = 102.074 (7)°0.32 × 0.28 × 0.16 mm
β = 104.462 (8)°
Data collection top
Oxford Diffraction Xcalibur (Eos, Gemini)
diffractometer
9523 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
7763 reflections with I > 2σ(I)
Tmin = 0.992, Tmax = 1.000Rint = 0.019
17265 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.41 e Å3
9523 reflectionsΔρmin = 0.37 e Å3
392 parameters
Special details top

Experimental. IR (KBr, ν, cm-1): 3089, 3076, 3032, 2921, 2860, 1675, 1623, 1599, 1494, 1447, 1355, 1321, 1224, 1190, 1124, 1101, 1068, 1057, 1030, 987, 949, 913, 902, 871, 807, 796, 773, 749, 743, 697, 665, 614, 600, 571, 542, 523, 516, 476, 465, 410.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.43740 (3)0.02169 (3)0.30322 (2)0.01984 (7)
F10.49638 (11)0.40250 (9)0.77758 (7)0.0432 (2)
F20.26919 (12)0.48796 (10)0.48246 (9)0.0500 (3)
O10.32602 (10)0.14761 (9)0.26412 (8)0.02789 (19)
O20.48794 (10)0.08185 (9)0.37548 (7)0.02689 (18)
N10.42791 (11)0.09006 (10)0.39671 (9)0.02233 (19)
H1N0.4533 (18)0.0941 (18)0.4664 (17)0.039 (5)*
N20.28600 (11)0.14105 (10)0.19524 (9)0.02231 (19)
N30.53297 (10)0.06323 (10)0.24067 (8)0.02067 (18)
C10.38081 (11)0.26075 (11)0.46306 (10)0.01907 (19)
C20.32275 (12)0.32957 (12)0.42896 (11)0.0239 (2)
H20.28370.31460.35030.029*
C30.32482 (14)0.42044 (13)0.51513 (13)0.0295 (3)
C40.38077 (15)0.44723 (13)0.63302 (12)0.0311 (3)
H40.37940.50800.68920.037*
C50.43884 (14)0.37847 (12)0.66256 (11)0.0272 (2)
C60.44136 (13)0.28633 (11)0.58150 (10)0.0233 (2)
H60.48230.24260.60530.028*
C70.37487 (12)0.16138 (11)0.36620 (10)0.0203 (2)
C80.63319 (12)0.20891 (12)0.29033 (10)0.0242 (2)
H8A0.72570.22870.32740.029*
H8B0.61290.24890.35080.029*
C90.63249 (12)0.27303 (11)0.20105 (11)0.0240 (2)
C100.51002 (13)0.24232 (12)0.11758 (11)0.0259 (2)
H100.42470.17580.11210.031*
C110.51447 (15)0.31028 (14)0.04249 (12)0.0319 (3)
H110.43230.28840.01330.038*
C120.64137 (18)0.41068 (15)0.05066 (15)0.0413 (3)
H120.64440.45690.00120.050*
C130.76264 (17)0.44130 (16)0.13250 (17)0.0451 (4)
H130.84780.50850.13820.054*
C140.75871 (14)0.37255 (14)0.20666 (14)0.0355 (3)
H140.84140.39320.26070.043*
C150.56485 (12)0.01043 (12)0.15817 (10)0.0237 (2)
H15A0.56310.01880.09310.028*
H15B0.49230.10500.12670.028*
C160.70388 (13)0.00782 (12)0.21205 (10)0.0244 (2)
C170.81851 (14)0.09705 (15)0.19713 (12)0.0314 (3)
H170.81060.14780.15450.038*
C180.94557 (15)0.11212 (17)0.24496 (14)0.0387 (3)
H181.02190.17270.23440.046*
C190.95815 (16)0.03721 (18)0.30793 (15)0.0415 (3)
H191.04280.04690.34010.050*
C200.84434 (19)0.0522 (2)0.32287 (19)0.0516 (5)
H200.85240.10280.36560.062*
C210.71770 (16)0.06731 (17)0.27473 (16)0.0418 (4)
H210.64140.12870.28480.050*
C220.23433 (12)0.13973 (12)0.07795 (10)0.0230 (2)
H22A0.25310.19130.02500.028*
H22B0.28580.04830.08300.028*
C230.08095 (12)0.19524 (12)0.02627 (10)0.0226 (2)
C240.03004 (14)0.12016 (13)0.06257 (12)0.0300 (3)
H240.09070.03540.12200.036*
C250.11001 (15)0.16988 (14)0.01136 (13)0.0354 (3)
H250.14260.11860.03690.042*
C260.20173 (14)0.29556 (14)0.07766 (13)0.0340 (3)
H260.29550.32830.11250.041*
C270.15325 (14)0.37201 (14)0.11446 (13)0.0350 (3)
H270.21460.45700.17350.042*
C280.01251 (13)0.32199 (13)0.06331 (12)0.0298 (3)
H280.01960.37360.08910.036*
C290.21642 (14)0.27347 (12)0.20305 (11)0.0271 (2)
H29A0.28250.29880.21940.033*
H29B0.14130.33870.12740.033*
C300.15810 (13)0.27986 (12)0.29566 (11)0.0240 (2)
C310.10079 (17)0.20779 (16)0.32146 (14)0.0372 (3)
H310.10020.15150.28290.045*
C320.04429 (18)0.21939 (18)0.40456 (16)0.0436 (4)
H320.00780.16940.42240.052*
C330.04182 (15)0.30452 (16)0.46101 (13)0.0364 (3)
H330.00200.31340.51530.044*
C340.09897 (13)0.37615 (13)0.43611 (12)0.0294 (3)
H340.09820.43320.47410.035*
C350.15751 (13)0.36316 (12)0.35458 (11)0.0254 (2)
H350.19690.41090.33910.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.02944 (15)0.02422 (14)0.01462 (12)0.02134 (12)0.00770 (10)0.00797 (10)
F10.0675 (6)0.0436 (5)0.0207 (4)0.0381 (5)0.0116 (4)0.0057 (3)
F20.0756 (7)0.0585 (6)0.0564 (6)0.0610 (6)0.0298 (5)0.0292 (5)
O10.0383 (5)0.0348 (5)0.0193 (4)0.0276 (4)0.0084 (4)0.0110 (3)
O20.0434 (5)0.0341 (4)0.0190 (4)0.0323 (4)0.0113 (4)0.0124 (3)
N10.0343 (5)0.0279 (5)0.0164 (4)0.0251 (4)0.0100 (4)0.0092 (4)
N20.0303 (5)0.0216 (4)0.0181 (4)0.0161 (4)0.0084 (4)0.0101 (3)
N30.0250 (4)0.0229 (4)0.0165 (4)0.0169 (4)0.0066 (3)0.0048 (3)
C10.0211 (5)0.0196 (5)0.0214 (5)0.0141 (4)0.0091 (4)0.0087 (4)
C20.0274 (5)0.0265 (5)0.0274 (6)0.0204 (5)0.0114 (5)0.0130 (4)
C30.0355 (6)0.0294 (6)0.0397 (7)0.0266 (5)0.0178 (6)0.0165 (5)
C40.0425 (7)0.0266 (6)0.0353 (7)0.0253 (6)0.0202 (6)0.0103 (5)
C50.0357 (6)0.0243 (5)0.0222 (5)0.0190 (5)0.0102 (5)0.0062 (4)
C60.0300 (6)0.0227 (5)0.0224 (5)0.0193 (5)0.0089 (4)0.0081 (4)
C70.0249 (5)0.0230 (5)0.0192 (5)0.0176 (4)0.0086 (4)0.0089 (4)
C80.0231 (5)0.0237 (5)0.0194 (5)0.0137 (4)0.0032 (4)0.0021 (4)
C90.0251 (5)0.0203 (5)0.0233 (5)0.0130 (4)0.0084 (4)0.0033 (4)
C100.0269 (6)0.0234 (5)0.0258 (6)0.0136 (5)0.0097 (5)0.0088 (4)
C110.0409 (7)0.0317 (6)0.0287 (6)0.0231 (6)0.0146 (5)0.0132 (5)
C120.0548 (9)0.0356 (7)0.0455 (9)0.0259 (7)0.0296 (8)0.0232 (7)
C130.0396 (8)0.0341 (7)0.0617 (11)0.0148 (6)0.0293 (8)0.0223 (7)
C140.0263 (6)0.0294 (6)0.0427 (8)0.0126 (5)0.0123 (6)0.0090 (6)
C150.0269 (5)0.0276 (5)0.0187 (5)0.0190 (5)0.0078 (4)0.0046 (4)
C160.0282 (6)0.0287 (6)0.0224 (5)0.0208 (5)0.0103 (4)0.0077 (4)
C170.0334 (6)0.0418 (7)0.0294 (6)0.0249 (6)0.0162 (5)0.0173 (5)
C180.0300 (7)0.0484 (8)0.0422 (8)0.0234 (6)0.0175 (6)0.0177 (7)
C190.0343 (7)0.0560 (9)0.0454 (9)0.0341 (7)0.0150 (6)0.0176 (7)
C200.0513 (9)0.0695 (12)0.0746 (13)0.0495 (9)0.0330 (9)0.0491 (10)
C210.0387 (8)0.0498 (9)0.0652 (11)0.0341 (7)0.0283 (7)0.0384 (8)
C220.0251 (5)0.0266 (5)0.0181 (5)0.0148 (5)0.0078 (4)0.0101 (4)
C230.0249 (5)0.0235 (5)0.0207 (5)0.0137 (4)0.0090 (4)0.0105 (4)
C240.0311 (6)0.0267 (6)0.0283 (6)0.0183 (5)0.0056 (5)0.0056 (5)
C250.0342 (7)0.0346 (7)0.0386 (7)0.0249 (6)0.0098 (6)0.0072 (6)
C260.0252 (6)0.0332 (7)0.0394 (7)0.0164 (5)0.0100 (5)0.0098 (6)
C270.0259 (6)0.0259 (6)0.0393 (7)0.0109 (5)0.0088 (5)0.0023 (5)
C280.0272 (6)0.0257 (6)0.0336 (7)0.0151 (5)0.0120 (5)0.0057 (5)
C290.0402 (7)0.0232 (5)0.0245 (6)0.0203 (5)0.0147 (5)0.0118 (4)
C300.0276 (5)0.0239 (5)0.0228 (5)0.0158 (5)0.0088 (4)0.0107 (4)
C310.0520 (9)0.0453 (8)0.0418 (8)0.0385 (7)0.0261 (7)0.0272 (7)
C320.0541 (9)0.0610 (10)0.0491 (9)0.0468 (9)0.0313 (8)0.0296 (8)
C330.0352 (7)0.0484 (8)0.0352 (7)0.0253 (6)0.0199 (6)0.0205 (6)
C340.0290 (6)0.0312 (6)0.0270 (6)0.0146 (5)0.0104 (5)0.0154 (5)
C350.0296 (6)0.0253 (5)0.0250 (6)0.0172 (5)0.0102 (5)0.0122 (4)
Geometric parameters (Å, º) top
P1—N11.6880 (10)C16—C211.3804 (18)
P1—N21.6488 (11)C16—C171.3822 (18)
P1—N31.6443 (11)C17—C181.3915 (19)
P1—O21.4798 (9)C17—H170.9300
F1—C51.3537 (15)C18—C191.376 (2)
F2—C31.3538 (14)C18—H180.9300
O1—C71.2236 (14)C19—C201.377 (2)
N1—C71.3664 (14)C19—H190.9300
N1—H1N0.847 (19)C20—C211.387 (2)
N2—C221.4748 (14)C20—H200.9300
N2—C291.4756 (15)C21—H210.9300
N3—C81.4687 (15)C22—C231.5115 (16)
N3—C151.4829 (14)C22—H22A0.9700
C1—C61.3936 (16)C22—H22B0.9700
C1—C21.3945 (15)C23—C241.3891 (17)
C1—C71.5047 (15)C23—C281.3961 (17)
C2—C31.3789 (17)C24—C251.3858 (19)
C2—H20.9300C24—H240.9300
C3—C41.377 (2)C25—C261.385 (2)
C4—C51.3768 (18)C25—H250.9300
C4—H40.9300C26—C271.3805 (19)
C5—C61.3816 (16)C26—H260.9300
C6—H60.9300C27—C281.3921 (19)
C8—C91.5141 (18)C27—H270.9300
C8—H8A0.9700C28—H280.9300
C8—H8B0.9700C29—C301.5111 (17)
C9—C141.3925 (18)C29—H29A0.9700
C9—C101.3959 (17)C29—H29B0.9700
C10—C111.3908 (18)C30—C311.3882 (18)
C10—H100.9300C30—C351.3890 (16)
C11—C121.389 (2)C31—C321.388 (2)
C11—H110.9300C31—H310.9300
C12—C131.377 (3)C32—C331.382 (2)
C12—H120.9300C32—H320.9300
C13—C141.389 (2)C33—C341.380 (2)
C13—H130.9300C33—H330.9300
C14—H140.9300C34—C351.3863 (18)
C15—C161.5151 (16)C34—H340.9300
C15—H15A0.9700C35—H350.9300
C15—H15B0.9700
N1—P1—N2113.07 (5)C21—C16—C17118.49 (12)
N1—P1—N3105.18 (5)C21—C16—C15120.46 (12)
N2—P1—N3105.51 (5)C17—C16—C15121.02 (11)
O2—P1—N1105.15 (5)C16—C17—C18121.00 (13)
O2—P1—N2109.06 (5)C16—C17—H17119.5
O2—P1—N3119.05 (5)C18—C17—H17119.5
C7—N1—P1125.60 (8)C19—C18—C17119.91 (14)
C7—N1—H1N120.9 (12)C19—C18—H18120.0
P1—N1—H1N113.3 (12)C17—C18—H18120.0
C22—N2—C29115.46 (10)C18—C19—C20119.44 (13)
C22—N2—P1125.00 (8)C18—C19—H19120.3
C29—N2—P1116.99 (8)C20—C19—H19120.3
C8—N3—C15113.59 (9)C19—C20—C21120.50 (15)
C8—N3—P1125.14 (8)C19—C20—H20119.7
C15—N3—P1116.41 (8)C21—C20—H20119.7
C6—C1—C2120.19 (10)C16—C21—C20120.65 (14)
C6—C1—C7123.37 (10)C16—C21—H21119.7
C2—C1—C7116.44 (10)C20—C21—H21119.7
C3—C2—C1118.15 (11)N2—C22—C23114.47 (9)
C3—C2—H2120.9N2—C22—H22A108.6
C1—C2—H2120.9C23—C22—H22A108.6
F2—C3—C4117.80 (12)N2—C22—H22B108.6
F2—C3—C2118.35 (12)C23—C22—H22B108.6
C4—C3—C2123.85 (11)H22A—C22—H22B107.6
C5—C4—C3115.88 (11)C24—C23—C28118.32 (11)
C5—C4—H4122.1C24—C23—C22121.29 (11)
C3—C4—H4122.1C28—C23—C22120.33 (11)
F1—C5—C4118.00 (11)C25—C24—C23120.87 (12)
F1—C5—C6118.29 (11)C25—C24—H24119.6
C4—C5—C6123.71 (12)C23—C24—H24119.6
C5—C6—C1118.19 (11)C26—C25—C24120.34 (13)
C5—C6—H6120.9C26—C25—H25119.8
C1—C6—H6120.9C24—C25—H25119.8
O1—C7—N1121.81 (10)C27—C26—C25119.65 (13)
O1—C7—C1120.41 (10)C27—C26—H26120.2
N1—C7—C1117.77 (10)C25—C26—H26120.2
N3—C8—C9113.99 (9)C26—C27—C28120.05 (13)
N3—C8—H8A108.8C26—C27—H27120.0
C9—C8—H8A108.8C28—C27—H27120.0
N3—C8—H8B108.8C27—C28—C23120.78 (12)
C9—C8—H8B108.8C27—C28—H28119.6
H8A—C8—H8B107.6C23—C28—H28119.6
C14—C9—C10118.38 (12)N2—C29—C30114.45 (10)
C14—C9—C8118.93 (12)N2—C29—H29A108.6
C10—C9—C8122.56 (11)C30—C29—H29A108.6
C11—C10—C9120.60 (12)N2—C29—H29B108.6
C11—C10—H10119.7C30—C29—H29B108.6
C9—C10—H10119.7H29A—C29—H29B107.6
C12—C11—C10120.16 (14)C31—C30—C35118.62 (12)
C12—C11—H11119.9C31—C30—C29121.91 (11)
C10—C11—H11119.9C35—C30—C29119.44 (11)
C13—C12—C11119.60 (14)C30—C31—C32120.28 (13)
C13—C12—H12120.2C30—C31—H31119.9
C11—C12—H12120.2C32—C31—H31119.9
C12—C13—C14120.43 (14)C33—C32—C31120.62 (14)
C12—C13—H13119.8C33—C32—H32119.7
C14—C13—H13119.8C31—C32—H32119.7
C13—C14—C9120.81 (14)C34—C33—C32119.42 (13)
C13—C14—H14119.6C34—C33—H33120.3
C9—C14—H14119.6C32—C33—H33120.3
N3—C15—C16114.46 (9)C33—C34—C35120.11 (12)
N3—C15—H15A108.6C33—C34—H34119.9
C16—C15—H15A108.6C35—C34—H34119.9
N3—C15—H15B108.6C34—C35—C30120.93 (12)
C16—C15—H15B108.6C34—C35—H35119.5
H15A—C15—H15B107.6C30—C35—H35119.5
O2—P1—N1—C7174.13 (10)C11—C12—C13—C140.0 (2)
N3—P1—N1—C759.38 (11)C12—C13—C14—C91.0 (2)
N2—P1—N1—C755.24 (12)C10—C9—C14—C131.2 (2)
O2—P1—N2—C22148.50 (9)C8—C9—C14—C13174.90 (13)
N3—P1—N2—C2219.53 (11)C8—N3—C15—C1660.84 (13)
N1—P1—N2—C2294.90 (10)P1—N3—C15—C1695.82 (11)
O2—P1—N2—C2912.48 (10)N3—C15—C16—C2182.20 (16)
N3—P1—N2—C29141.45 (9)N3—C15—C16—C1799.52 (14)
N1—P1—N2—C29104.12 (9)C21—C16—C17—C180.6 (2)
O2—P1—N3—C894.45 (10)C15—C16—C17—C18178.90 (13)
N2—P1—N3—C8142.75 (9)C16—C17—C18—C190.2 (2)
N1—P1—N3—C822.97 (10)C17—C18—C19—C200.0 (3)
O2—P1—N3—C1559.19 (10)C18—C19—C20—C210.2 (3)
N2—P1—N3—C1563.61 (9)C17—C16—C21—C200.8 (2)
N1—P1—N3—C15176.61 (8)C15—C16—C21—C20179.14 (16)
C6—C1—C2—C31.29 (18)C19—C20—C21—C160.6 (3)
C7—C1—C2—C3179.30 (11)C29—N2—C22—C2357.53 (14)
C1—C2—C3—F2179.68 (11)P1—N2—C22—C23141.23 (9)
C1—C2—C3—C40.1 (2)N2—C22—C23—C2477.82 (14)
F2—C3—C4—C5178.67 (12)N2—C22—C23—C28104.96 (13)
C2—C3—C4—C51.1 (2)C28—C23—C24—C250.1 (2)
C3—C4—C5—F1179.37 (12)C22—C23—C24—C25177.40 (12)
C3—C4—C5—C60.8 (2)C23—C24—C25—C260.3 (2)
F1—C5—C6—C1179.36 (11)C24—C25—C26—C270.7 (2)
C4—C5—C6—C10.5 (2)C25—C26—C27—C280.9 (2)
C2—C1—C6—C51.55 (18)C26—C27—C28—C230.7 (2)
C7—C1—C6—C5179.08 (11)C24—C23—C28—C270.3 (2)
P1—N1—C7—O11.24 (18)C22—C23—C28—C27177.62 (13)
P1—N1—C7—C1177.54 (8)C22—N2—C29—C30125.48 (11)
C6—C1—C7—O1176.63 (11)P1—N2—C29—C3071.71 (13)
C2—C1—C7—O12.76 (16)N2—C29—C30—C3135.58 (18)
C6—C1—C7—N12.16 (17)N2—C29—C30—C35146.45 (12)
C2—C1—C7—N1178.45 (10)C35—C30—C31—C320.0 (2)
C15—N3—C8—C966.04 (12)C29—C30—C31—C32177.99 (14)
P1—N3—C8—C9139.68 (9)C30—C31—C32—C331.3 (3)
N3—C8—C9—C14138.17 (12)C31—C32—C33—C341.4 (3)
N3—C8—C9—C1045.92 (15)C32—C33—C34—C350.4 (2)
C14—C9—C10—C110.36 (18)C33—C34—C35—C300.9 (2)
C8—C9—C10—C11175.57 (11)C31—C30—C35—C341.06 (19)
C9—C10—C11—C120.6 (2)C29—C30—C35—C34176.98 (12)
C10—C11—C12—C130.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.223.1123 (14)162
N1—H1N···O2i0.847 (19)2.024 (19)2.8659 (13)172.8 (17)
Symmetry code: (i) x+1, y, z+1.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC30H29ClF2N3O2PC35H33FN3O2PC35H32F2N3O2P
Mr567.98577.61595.61
Crystal system, space groupMonoclinic, P21/nTriclinic, P1Triclinic, P1
Temperature (K)296173173
a, b, c (Å)10.8298 (3), 9.9164 (3), 26.6740 (8)10.0173 (10), 11.2362 (8), 14.5992 (12)11.9526 (11), 12.2897 (10), 12.7463 (12)
α, β, γ (°)90, 91.539 (1), 9099.351 (6), 109.960 (8), 91.135 (7)102.074 (7), 104.462 (8), 118.262 (9)
V3)2863.56 (15)1519.0 (2)1474.5 (2)
Z422
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.230.130.14
Crystal size (mm)0.56 × 0.51 × 0.480.48 × 0.40 × 0.360.32 × 0.28 × 0.16
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Xcalibur, Eos, Gemini
diffractometer
Oxford Diffraction Xcalibur (Eos, Gemini)
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Multi-scan
CrysAlis PRO, Oxford Diffraction, 2010.
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2010)
Tmin, Tmax0.694, 0.7460.943, 1.0000.992, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
31854, 6905, 5873 17423, 9840, 8118 17265, 9523, 7763
Rint0.0190.0210.019
(sin θ/λ)max1)0.6600.7530.753
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.134, 1.05 0.048, 0.143, 1.04 0.042, 0.116, 1.05
No. of reflections690598409523
No. of parameters356383392
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.78, 0.681.12, 0.320.41, 0.37

Computer programs: APEX2 (Bruker, 2007), CrysAlis PRO (Oxford Diffraction, 2010), SAINT (Bruker, 2007), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XPW (Siemens, 1996) and Mercury (Macrae et al., 2008), SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Selected geometric parameters (Å, º) for (I) top
P1—N11.7011 (13)F3—C301.322 (2)
P1—N21.6331 (14)N2—C11.465 (2)
P1—N31.6373 (13)N2—C81.480 (2)
P1—O21.4739 (11)N3—C221.477 (2)
Cl1—C301.748 (2)N3—C151.4788 (19)
O1—C291.208 (2)N1—C291.348 (2)
F2—C301.338 (2)
O2—P1—N1104.82 (7)C8—N2—P1120.13 (11)
O2—P1—N2111.59 (7)C22—N3—C15114.69 (13)
O2—P1—N3118.57 (7)C15—N3—P1120.57 (11)
N1—P1—N2110.25 (7)C22—N3—P1119.96 (10)
N1—P1—N3105.08 (7)C29—N1—P1126.83 (11)
N2—P1—N3106.23 (7)O1—C29—N1126.99 (15)
C1—N2—C8114.75 (14)F3—C30—F2107.49 (17)
C1—N2—P1124.74 (11)F3—C30—Cl1109.36 (15)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.80 (2)1.98 (2)2.7788 (17)172 (2)
Symmetry code: (i) x, y+2, z+2.
Selected geometric parameters (Å, º) for (II) top
P1—N11.6922 (10)N1—C71.3716 (15)
P1—N21.6484 (11)N2—C221.4768 (15)
P1—N31.6400 (11)N2—C291.4868 (16)
P1—O21.4786 (9)N3—C81.4672 (15)
F1—C31.3500 (19)N3—C151.4844 (16)
O1—C71.2200 (15)
N1—P1—N2103.81 (5)C22—N2—C29113.09 (10)
N1—P1—N3112.50 (5)C22—N2—P1117.96 (8)
N2—P1—N3106.54 (5)C29—N2—P1121.34 (8)
O2—P1—N1105.60 (5)C8—N3—C15114.81 (10)
O2—P1—N2118.92 (5)C8—N3—P1124.58 (8)
O2—P1—N3109.48 (5)C15—N3—P1120.32 (8)
C7—N1—P1127.16 (8)O1—C7—N1122.00 (11)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.932.453.1124 (16)128.4
C25—H25···O1ii0.932.453.2342 (17)142.4
N1—H1N···O2i0.837 (18)2.017 (18)2.8497 (13)173.7 (17)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.
Selected geometric parameters (Å, º) for (III) top
P1—N11.6880 (10)O1—C71.2236 (14)
P1—N21.6488 (11)N1—C71.3664 (14)
P1—N31.6443 (11)N2—C221.4748 (14)
P1—O21.4798 (9)N2—C291.4756 (15)
F1—C51.3537 (15)N3—C81.4687 (15)
F2—C31.3538 (14)N3—C151.4829 (14)
N1—P1—N2113.07 (5)C22—N2—C29115.46 (10)
N1—P1—N3105.18 (5)C22—N2—P1125.00 (8)
N2—P1—N3105.51 (5)C29—N2—P1116.99 (8)
O2—P1—N1105.15 (5)C8—N3—C15113.59 (9)
O2—P1—N2109.06 (5)C8—N3—P1125.14 (8)
O2—P1—N3119.05 (5)C15—N3—P1116.41 (8)
C7—N1—P1125.60 (8)O1—C7—N1121.81 (10)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O2i0.932.223.1123 (14)161.6
N1—H1N···O2i0.847 (19)2.024 (19)2.8659 (13)172.8 (17)
Symmetry code: (i) x+1, y, z+1.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds