Three new [XC(O)NH]P(O)[N(CH₂C₆H₅)₂]₂ phospho­ric triamides (X = CClF₂, 3-F-C₆H₄ and 3,5-F₂-C₆H₃): a database analysis of tertiary N-atom geometry in compounds with a C(O)NHP(O)[N]₂ core

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 C_i symmetry.

S1. Comment

The N—P═O 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 N_C(O)NHP(O), whereas the other two N atoms are designated as N_amido 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—N_amido angles, whereas the narrowest angle for (I) and (III) is O—P—N_C(O)NHP(O) and for (II) is an N_amido—P—N_C(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—N_amide and P—N_C(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—N_amide bonds are found; and in the range 1.68–1.74 Å only P—N_C(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—N_amide bond entries is twice the number of P—N_C(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 P═O.

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 P═O 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 P═O.

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 C_i 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 P═O is observed for compounds with ΔSUM (= SUM1 - SUM2) ranging from 14.3 to 5.9°.

Related literature

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).

S2. Experimental

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.

S3. Refinement

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 U_eq 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 ų. 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

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

	Fig. 1. Displacement ellipsoid plot (50% probability) and atom-numbering scheme for (I). H atoms are drawn as circles of arbitrary radii.
	Fig. 2. Displacement ellipsoid plot (50% probability) and atom-numbering scheme for (II). H atoms are drawn as circles of arbitrary radii.
	Fig. 3. Displacement ellipsoid plot (50% probability) and atom-numbering scheme for (III). H atoms are drawn as circles of arbitrary radii.
	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.
	Fig. 5. The anti orientation of the N3 lone electron pair (LEP) relative to P═O 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.)
	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.
	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

Crystal data

C30H29ClF2N3O2P	F(000) = 1184
Mr = 567.98	Dx = 1.317 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9995 reflections
a = 10.8298 (3) Å	θ = 2.6–29.0°
b = 9.9164 (3) Å	µ = 0.23 mm^−1
c = 26.6740 (8) Å	T = 296 K
β = 91.539 (1)°	Irregular, colorless
V = 2863.56 (15) Å^3	0.56 × 0.51 × 0.48 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	6905 independent reflections
Radiation source: fine-focus sealed tube	5873 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 28.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.694, Tmax = 0.746	k = −13→13
31854 measured reflections	l = −35→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0663P)^2 + 1.1866P] where P = (Fo^2 + 2Fc^2)/3
6905 reflections	(Δ/σ)max = 0.001
356 parameters	Δρmax = 0.78 e Å^−3
0 restraints	Δρmin = −0.68 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.34696 (6)	0.83086 (7)	1.01897 (2)	0.0761 (2)
P1	−0.01521 (3)	0.88010 (4)	0.925175 (13)	0.03216 (11)
O1	0.25772 (12)	0.85020 (15)	0.89093 (5)	0.0507 (3)
F2	0.33710 (12)	1.06452 (13)	0.98342 (5)	0.0678 (3)
O2	−0.10455 (10)	0.92420 (13)	0.96253 (4)	0.0423 (3)
F3	0.45045 (11)	0.9261 (2)	0.94339 (6)	0.0911 (5)
C3	0.21381 (19)	0.5602 (2)	0.94220 (7)	0.0526 (4)
H3	0.1984	0.6344	0.9624	0.063*
N2	−0.01394 (12)	0.71619 (14)	0.91926 (5)	0.0366 (3)
N3	−0.02763 (13)	0.94120 (13)	0.86824 (5)	0.0359 (3)
C5	0.3281 (2)	0.3594 (3)	0.92671 (13)	0.0817 (8)
H5	0.3909	0.2994	0.9357	0.098*
C4	0.3070 (2)	0.4708 (3)	0.95599 (10)	0.0676 (6)
H4	0.3550	0.4861	0.9849	0.081*
C2	0.14316 (17)	0.54042 (17)	0.89859 (7)	0.0435 (4)
C1	0.04933 (16)	0.64269 (17)	0.87983 (6)	0.0406 (3)
H1A	0.0907	0.7074	0.8588	0.049*
H1B	−0.0122	0.5966	0.8590	0.049*
C15	−0.11343 (17)	0.87955 (18)	0.83075 (6)	0.0431 (4)
H15A	−0.1387	0.7921	0.8432	0.052*
H15B	−0.0690	0.8644	0.8002	0.052*
C16	−0.22776 (18)	0.96065 (18)	0.81805 (6)	0.0464 (4)
C17	−0.3107 (2)	0.9971 (2)	0.85393 (9)	0.0591 (5)
H17	−0.2945	0.9747	0.8873	0.071*
C18	−0.4180 (2)	1.0668 (3)	0.84101 (13)	0.0811 (8)
H18	−0.4734	1.0899	0.8656	0.097*
C19	−0.4422 (3)	1.1013 (3)	0.79216 (17)	0.0992 (11)
H19	−0.5138	1.1486	0.7835	0.119*
C12	−0.4023 (3)	0.4794 (4)	0.86672 (11)	0.0975 (11)
H12	−0.4691	0.4473	0.8476	0.117*
C11	−0.2996 (3)	0.4016 (3)	0.87355 (12)	0.0941 (10)
H11	−0.2968	0.3163	0.8591	0.113*
C10	−0.1990 (2)	0.4484 (2)	0.90186 (10)	0.0679 (6)
H10	−0.1299	0.3939	0.9068	0.081*
C9	−0.20186 (17)	0.57579 (19)	0.92262 (7)	0.0464 (4)
C14	−0.3073 (2)	0.6534 (3)	0.91567 (9)	0.0618 (5)
H14	−0.3108	0.7391	0.9298	0.074*
C13	−0.4071 (2)	0.6045 (4)	0.88796 (11)	0.0859 (9)
H13	−0.4778	0.6570	0.8837	0.103*
C8	−0.09195 (17)	0.63158 (19)	0.95136 (6)	0.0450 (4)
H8A	−0.1202	0.6851	0.9792	0.054*
H8B	−0.0429	0.5576	0.9650	0.054*
C22	0.00184 (18)	1.08433 (17)	0.85889 (6)	0.0428 (4)
H22A	0.0603	1.1155	0.8845	0.051*
H22B	−0.0728	1.1376	0.8615	0.051*
C23	0.05588 (17)	1.10691 (18)	0.80788 (6)	0.0450 (4)
C24	0.0088 (2)	1.2072 (2)	0.77678 (8)	0.0567 (5)
H24	−0.0581	1.2583	0.7869	0.068*
C25	0.0605 (3)	1.2321 (3)	0.73065 (9)	0.0738 (7)
H25	0.0287	1.3004	0.7102	0.089*
C26	0.1577 (3)	1.1569 (3)	0.71521 (9)	0.0805 (8)
H26	0.1921	1.1736	0.6842	0.097*
C27	0.2046 (3)	1.0564 (3)	0.74549 (9)	0.0818 (8)
H27	0.2705	1.0045	0.7349	0.098*
C28	0.1544 (2)	1.0320 (3)	0.79184 (8)	0.0635 (6)
H28	0.1875	0.9644	0.8123	0.076*
C20	−0.3615 (4)	1.0664 (3)	0.75625 (13)	0.1020 (12)
H20	−0.3786	1.0897	0.7230	0.122*
C21	−0.2532 (3)	0.9960 (3)	0.76855 (8)	0.0723 (7)
H21	−0.1985	0.9729	0.7437	0.087*
N1	0.12407 (12)	0.93551 (15)	0.94785 (5)	0.0365 (3)
C29	0.23604 (15)	0.90400 (17)	0.93035 (6)	0.0388 (3)
C30	0.34493 (16)	0.9375 (2)	0.96680 (7)	0.0486 (4)
C6	0.2570 (3)	0.3369 (2)	0.88443 (13)	0.0815 (8)
H6	0.2709	0.2607	0.8650	0.098*
C7	0.1647 (2)	0.4263 (2)	0.87036 (9)	0.0608 (5)
H7	0.1165	0.4096	0.8416	0.073*
H1N	0.1250 (19)	0.973 (2)	0.9743 (8)	0.045 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0827 (4)	0.0806 (4)	0.0631 (3)	−0.0111 (3)	−0.0368 (3)	0.0119 (3)
P1	0.03187 (19)	0.0408 (2)	0.02364 (17)	−0.00448 (15)	−0.00330 (13)	−0.00506 (14)
O1	0.0456 (7)	0.0691 (9)	0.0377 (6)	0.0010 (6)	0.0033 (5)	−0.0091 (6)
F2	0.0607 (7)	0.0626 (8)	0.0790 (8)	−0.0172 (6)	−0.0199 (6)	−0.0090 (6)
O2	0.0358 (6)	0.0590 (7)	0.0321 (5)	−0.0039 (5)	0.0005 (4)	−0.0121 (5)
F3	0.0335 (6)	0.1605 (16)	0.0793 (9)	−0.0125 (8)	0.0032 (6)	−0.0236 (10)
C3	0.0542 (11)	0.0543 (11)	0.0492 (10)	−0.0010 (8)	−0.0022 (8)	0.0084 (8)
N2	0.0418 (7)	0.0402 (7)	0.0278 (6)	−0.0057 (5)	0.0005 (5)	−0.0005 (5)
N3	0.0429 (7)	0.0371 (7)	0.0271 (6)	−0.0051 (5)	−0.0071 (5)	−0.0019 (5)
C5	0.0554 (13)	0.0619 (14)	0.129 (2)	0.0098 (11)	0.0169 (15)	0.0348 (16)
C4	0.0511 (12)	0.0753 (15)	0.0761 (15)	−0.0016 (10)	−0.0018 (10)	0.0312 (12)
C2	0.0454 (9)	0.0393 (8)	0.0459 (9)	−0.0060 (7)	0.0042 (7)	0.0017 (7)
C1	0.0495 (9)	0.0419 (8)	0.0302 (7)	−0.0039 (7)	−0.0020 (6)	−0.0049 (6)
C15	0.0546 (10)	0.0459 (9)	0.0282 (7)	−0.0052 (7)	−0.0117 (6)	−0.0049 (6)
C16	0.0542 (10)	0.0432 (9)	0.0406 (8)	−0.0112 (8)	−0.0184 (7)	0.0063 (7)
C17	0.0599 (12)	0.0556 (11)	0.0613 (12)	−0.0002 (9)	−0.0104 (9)	0.0066 (9)
C18	0.0569 (13)	0.0632 (14)	0.122 (2)	0.0019 (11)	−0.0191 (14)	0.0033 (15)
C19	0.0776 (19)	0.0694 (17)	0.147 (3)	−0.0003 (14)	−0.059 (2)	0.0147 (19)
C12	0.0754 (19)	0.140 (3)	0.0764 (17)	−0.058 (2)	−0.0095 (14)	−0.0003 (18)
C11	0.102 (2)	0.087 (2)	0.094 (2)	−0.0529 (18)	0.0100 (17)	−0.0222 (16)
C10	0.0686 (14)	0.0563 (12)	0.0788 (15)	−0.0201 (10)	0.0070 (11)	−0.0052 (11)
C9	0.0500 (10)	0.0484 (9)	0.0408 (8)	−0.0145 (8)	0.0015 (7)	0.0089 (7)
C14	0.0556 (12)	0.0673 (13)	0.0624 (12)	−0.0083 (10)	−0.0022 (9)	0.0120 (10)
C13	0.0547 (13)	0.121 (3)	0.0815 (18)	−0.0183 (15)	−0.0113 (12)	0.0195 (17)
C8	0.0509 (9)	0.0496 (10)	0.0345 (8)	−0.0097 (8)	−0.0010 (7)	0.0089 (7)
C22	0.0543 (10)	0.0360 (8)	0.0380 (8)	−0.0042 (7)	−0.0024 (7)	−0.0016 (6)
C23	0.0512 (10)	0.0451 (9)	0.0384 (8)	−0.0095 (7)	−0.0054 (7)	0.0040 (7)
C24	0.0730 (13)	0.0460 (10)	0.0506 (10)	−0.0031 (9)	−0.0087 (9)	0.0065 (8)
C25	0.103 (2)	0.0638 (14)	0.0536 (12)	−0.0141 (13)	−0.0128 (12)	0.0232 (11)
C26	0.0878 (18)	0.104 (2)	0.0501 (12)	−0.0216 (16)	0.0092 (12)	0.0218 (13)
C27	0.0684 (15)	0.120 (2)	0.0577 (13)	0.0108 (15)	0.0155 (11)	0.0137 (14)
C28	0.0617 (12)	0.0823 (15)	0.0467 (10)	0.0117 (11)	0.0044 (9)	0.0156 (10)
C20	0.120 (3)	0.094 (2)	0.089 (2)	−0.0125 (19)	−0.066 (2)	0.0334 (17)
C21	0.0889 (16)	0.0790 (15)	0.0471 (11)	−0.0152 (13)	−0.0307 (11)	0.0169 (10)
N1	0.0337 (6)	0.0485 (8)	0.0271 (6)	−0.0058 (5)	−0.0035 (5)	−0.0085 (5)
C29	0.0350 (8)	0.0483 (9)	0.0330 (7)	−0.0056 (6)	−0.0024 (6)	0.0012 (6)
C30	0.0346 (8)	0.0640 (12)	0.0470 (9)	−0.0062 (8)	−0.0048 (7)	−0.0033 (8)
C6	0.0720 (16)	0.0443 (11)	0.129 (2)	0.0051 (11)	0.0243 (17)	−0.0049 (14)
C7	0.0618 (12)	0.0457 (10)	0.0753 (14)	−0.0061 (9)	0.0092 (10)	−0.0103 (10)

Geometric parameters (Å, º)

P1—N1	1.7011 (13)	C12—H12	0.9300
P1—N2	1.6331 (14)	C11—C10	1.388 (4)
P1—N3	1.6373 (13)	C11—H11	0.9300
P1—O2	1.4739 (11)	C10—C9	1.380 (3)
Cl1—C30	1.748 (2)	C10—H10	0.9300
O1—C29	1.208 (2)	C9—C14	1.385 (3)
F2—C30	1.338 (2)	C9—C8	1.504 (2)
F3—C30	1.322 (2)	C14—C13	1.381 (3)
C3—C4	1.385 (3)	C14—H14	0.9300
C3—C2	1.389 (3)	C13—H13	0.9300
C3—H3	0.9300	C8—H8A	0.9700
N2—C1	1.465 (2)	C8—H8B	0.9700
N2—C8	1.480 (2)	C22—C23	1.512 (2)
N3—C22	1.477 (2)	C22—H22A	0.9700
N3—C15	1.4788 (19)	C22—H22B	0.9700
C5—C6	1.367 (4)	C23—C28	1.378 (3)
C5—C4	1.375 (4)	C23—C24	1.383 (3)
C5—H5	0.9300	C24—C25	1.388 (3)
C4—H4	0.9300	C24—H24	0.9300
C2—C7	1.383 (3)	C25—C26	1.363 (4)
C2—C1	1.511 (2)	C25—H25	0.9300
C1—H1A	0.9700	C26—C27	1.372 (4)
C1—H1B	0.9700	C26—H26	0.9300
C15—C16	1.507 (3)	C27—C28	1.385 (3)
C15—H15A	0.9700	C27—H27	0.9300
C15—H15B	0.9700	C28—H28	0.9300
C16—C17	1.378 (3)	C20—C21	1.396 (4)
C16—C21	1.387 (2)	C20—H20	0.9300
C17—C18	1.387 (3)	C21—H21	0.9300
C17—H17	0.9300	N1—C29	1.348 (2)
C18—C19	1.366 (5)	N1—H1N	0.80 (2)
C18—H18	0.9300	C29—C30	1.544 (2)
C19—C20	1.359 (5)	C6—C7	1.381 (4)
C19—H19	0.9300	C6—H6	0.9300
C12—C11	1.362 (5)	C7—H7	0.9300
C12—C13	1.366 (5)
O2—P1—N1	104.82 (7)	C13—C14—C9	120.5 (3)
O2—P1—N2	111.59 (7)	C13—C14—H14	119.8
O2—P1—N3	118.57 (7)	C9—C14—H14	119.8
N1—P1—N2	110.25 (7)	C12—C13—C14	120.2 (3)
N1—P1—N3	105.08 (7)	C12—C13—H13	119.9
N2—P1—N3	106.23 (7)	C14—C13—H13	119.9
C4—C3—C2	120.9 (2)	N2—C8—C9	111.72 (13)
C4—C3—H3	119.6	N2—C8—H8A	109.3
C2—C3—H3	119.6	C9—C8—H8A	109.3
C1—N2—C8	114.75 (14)	N2—C8—H8B	109.3
C1—N2—P1	124.74 (11)	C9—C8—H8B	109.3
C8—N2—P1	120.13 (11)	H8A—C8—H8B	107.9
C22—N3—C15	114.69 (13)	N3—C22—C23	112.63 (14)
C15—N3—P1	120.57 (11)	N3—C22—H22A	109.1
C22—N3—P1	119.96 (10)	C23—C22—H22A	109.1
C6—C5—C4	120.1 (2)	N3—C22—H22B	109.1
C6—C5—H5	120.0	C23—C22—H22B	109.1
C4—C5—H5	120.0	H22A—C22—H22B	107.8
C5—C4—C3	119.6 (2)	C28—C23—C24	118.53 (18)
C5—C4—H4	120.2	C28—C23—C22	121.41 (17)
C3—C4—H4	120.2	C24—C23—C22	120.04 (18)
C7—C2—C3	118.32 (19)	C23—C24—C25	120.6 (2)
C7—C2—C1	119.39 (17)	C23—C24—H24	119.7
C3—C2—C1	122.20 (16)	C25—C24—H24	119.7
N2—C1—C2	114.80 (13)	C26—C25—C24	120.3 (2)
N2—C1—H1A	108.6	C26—C25—H25	119.9
C2—C1—H1A	108.6	C24—C25—H25	119.9
N2—C1—H1B	108.6	C25—C26—C27	119.8 (2)
C2—C1—H1B	108.6	C25—C26—H26	120.1
H1A—C1—H1B	107.5	C27—C26—H26	120.1
N3—C15—C16	115.39 (14)	C26—C27—C28	120.3 (3)
N3—C15—H15A	108.4	C26—C27—H27	119.9
C16—C15—H15A	108.4	C28—C27—H27	119.9
N3—C15—H15B	108.4	C23—C28—C27	120.6 (2)
C16—C15—H15B	108.4	C23—C28—H28	119.7
H15A—C15—H15B	107.5	C27—C28—H28	119.7
C17—C16—C21	118.6 (2)	C19—C20—C21	120.9 (3)
C17—C16—C15	122.06 (16)	C19—C20—H20	119.5
C21—C16—C15	119.3 (2)	C21—C20—H20	119.5
C16—C17—C18	121.0 (2)	C16—C21—C20	119.6 (3)
C16—C17—H17	119.5	C16—C21—H21	120.2
C18—C17—H17	119.5	C20—C21—H21	120.2
C19—C18—C17	120.0 (3)	C29—N1—P1	126.83 (11)
C19—C18—H18	120.0	C29—N1—H1N	115.1 (15)
C17—C18—H18	120.0	P1—N1—H1N	117.1 (15)
C20—C19—C18	119.8 (3)	O1—C29—N1	126.99 (15)
C20—C19—H19	120.1	O1—C29—C30	118.70 (15)
C18—C19—H19	120.1	N1—C29—C30	114.27 (14)
C11—C12—C13	120.0 (3)	F3—C30—F2	107.49 (17)
C11—C12—H12	120.0	F3—C30—C29	109.84 (15)
C13—C12—H12	120.0	F2—C30—C29	110.93 (16)
C12—C11—C10	120.6 (3)	F3—C30—Cl1	109.36 (15)
C12—C11—H11	119.7	F2—C30—Cl1	107.76 (13)
C10—C11—H11	119.7	C29—C30—Cl1	111.35 (13)
C9—C10—C11	119.9 (3)	C5—C6—C7	120.5 (2)
C9—C10—H10	120.0	C5—C6—H6	119.8
C11—C10—H10	120.0	C7—C6—H6	119.8
C10—C9—C14	118.8 (2)	C6—C7—C2	120.6 (2)
C10—C9—C8	121.0 (2)	C6—C7—H7	119.7
C14—C9—C8	120.13 (19)	C2—C7—H7	119.7
O2—P1—N2—C1	169.65 (12)	C1—N2—C8—C9	−67.4 (2)
N3—P1—N2—C1	39.05 (15)	P1—N2—C8—C9	105.97 (16)
N1—P1—N2—C1	−74.29 (14)	C10—C9—C8—N2	95.6 (2)
O2—P1—N2—C8	−2.96 (14)	C14—C9—C8—N2	−83.1 (2)
N3—P1—N2—C8	−133.56 (12)	C15—N3—C22—C23	−57.0 (2)
N1—P1—N2—C8	113.09 (12)	P1—N3—C22—C23	147.32 (13)
O2—P1—N3—C22	69.94 (15)	N3—C22—C23—C28	−51.2 (2)
N2—P1—N3—C22	−163.55 (13)	N3—C22—C23—C24	130.71 (18)
N1—P1—N3—C22	−46.70 (14)	C28—C23—C24—C25	−0.5 (3)
O2—P1—N3—C15	−84.28 (14)	C22—C23—C24—C25	177.64 (19)
N2—P1—N3—C15	42.23 (14)	C23—C24—C25—C26	0.7 (4)
N1—P1—N3—C15	159.09 (13)	C24—C25—C26—C27	−0.2 (4)
C6—C5—C4—C3	−0.4 (4)	C25—C26—C27—C28	−0.6 (5)
C2—C3—C4—C5	−1.4 (3)	C24—C23—C28—C27	−0.3 (4)
C4—C3—C2—C7	2.7 (3)	C22—C23—C28—C27	−178.4 (2)
C4—C3—C2—C1	−173.96 (18)	C26—C27—C28—C23	0.8 (4)
C8—N2—C1—C2	−64.23 (18)	C18—C19—C20—C21	−0.4 (5)
P1—N2—C1—C2	122.80 (14)	C17—C16—C21—C20	−0.3 (3)
C7—C2—C1—N2	149.48 (17)	C15—C16—C21—C20	177.4 (2)
C3—C2—C1—N2	−33.9 (2)	C19—C20—C21—C16	0.3 (4)
C22—N3—C15—C16	−48.0 (2)	O2—P1—N1—C29	170.32 (14)
P1—N3—C15—C16	107.54 (15)	N2—P1—N1—C29	50.10 (16)
N3—C15—C16—C17	−58.8 (2)	N3—P1—N1—C29	−63.97 (16)
N3—C15—C16—C21	123.49 (19)	P1—N1—C29—O1	13.5 (3)
C21—C16—C17—C18	0.5 (3)	P1—N1—C29—C30	−164.11 (13)
C15—C16—C17—C18	−177.19 (19)	O1—C29—C30—F3	13.3 (3)
C16—C17—C18—C19	−0.6 (4)	N1—C29—C30—F3	−168.88 (17)
C17—C18—C19—C20	0.5 (4)	O1—C29—C30—F2	131.99 (18)
C13—C12—C11—C10	−0.2 (5)	N1—C29—C30—F2	−50.2 (2)
C12—C11—C10—C9	−1.2 (4)	O1—C29—C30—Cl1	−108.00 (17)
C11—C10—C9—C14	1.6 (3)	N1—C29—C30—Cl1	69.82 (19)
C11—C10—C9—C8	−177.0 (2)	C4—C5—C6—C7	0.9 (4)
C10—C9—C14—C13	−0.7 (3)	C5—C6—C7—C2	0.4 (4)
C8—C9—C14—C13	177.9 (2)	C3—C2—C7—C6	−2.2 (3)
C11—C12—C13—C14	1.1 (4)	C1—C2—C7—C6	174.6 (2)
C9—C14—C13—C12	−0.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.80 (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

Crystal data

C35H33FN3O2P	Z = 2
Mr = 577.61	F(000) = 608
Triclinic, P1	Dx = 1.263 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0173 (10) Å	Cell parameters from 6536 reflections
b = 11.2362 (8) Å	θ = 3.3–32.3°
c = 14.5992 (12) Å	µ = 0.13 mm^−1
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) Å^3

Data collection

Xcalibur, Eos, Gemini diffractometer	9840 independent reflections
Radiation source: Enhance (Mo) X-ray Source	8118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 16.1500 pixels mm^-1	θmax = 32.3°, θmin = 3.3°
ω scans	h = −14→14
Absorption correction: multi-scan CrysAlis PRO, Oxford Diffraction, 2010.	k = −15→16
Tmin = 0.943, Tmax = 1.000	l = −21→21
17423 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0785P)^2 + 0.4137P] where P = (Fo^2 + 2Fc^2)/3
9840 reflections	(Δ/σ)max = 0.001
383 parameters	Δρmax = 1.12 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.61224 (3)	0.52499 (3)	0.17147 (2)	0.01907 (8)
F1	0.09542 (14)	0.11276 (10)	−0.14885 (8)	0.0595 (3)
O1	0.43362 (11)	0.37517 (10)	0.25151 (7)	0.0341 (2)
O2	0.64579 (9)	0.56565 (8)	0.08984 (6)	0.02406 (18)
N1	0.46767 (11)	0.42457 (9)	0.11608 (7)	0.02139 (19)
H1N	0.4313 (18)	0.4221 (15)	0.0549 (13)	0.029 (4)*
N2	0.56350 (11)	0.62438 (9)	0.24783 (7)	0.02175 (19)
N3	0.75016 (11)	0.46451 (10)	0.24019 (7)	0.02328 (19)
C1	0.26260 (13)	0.28721 (11)	0.09631 (9)	0.0248 (2)
C2	0.24014 (15)	0.23735 (12)	−0.00175 (10)	0.0301 (3)
H2	0.3069	0.2517	−0.0308	0.036*
C3	0.11489 (18)	0.16555 (13)	−0.05481 (11)	0.0378 (3)
C4	0.01102 (18)	0.14373 (15)	−0.01578 (15)	0.0471 (4)
H4	−0.0735	0.0977	−0.0545	0.057*
C5	0.03640 (18)	0.19228 (17)	0.08265 (16)	0.0509 (4)
H5	−0.0311	0.1777	0.1111	0.061*
C6	0.16203 (16)	0.26254 (14)	0.13908 (13)	0.0380 (3)
H6	0.1794	0.2933	0.2056	0.046*
C7	0.39457 (13)	0.36511 (11)	0.16160 (9)	0.0233 (2)
C8	0.76361 (13)	0.43097 (12)	0.33578 (8)	0.0248 (2)
H8A	0.6737	0.4397	0.3466	0.030*
H8B	0.8355	0.4861	0.3883	0.030*
C9	0.80392 (14)	0.30247 (12)	0.34142 (9)	0.0265 (2)
C10	0.71824 (16)	0.20475 (13)	0.27461 (11)	0.0347 (3)
H10	0.6336	0.2185	0.2269	0.042*
C11	0.75667 (19)	0.08760 (15)	0.27790 (14)	0.0442 (4)
H11	0.6990	0.0235	0.2319	0.053*
C12	0.8805 (2)	0.06598 (16)	0.34936 (16)	0.0492 (4)
H12	0.9072	−0.0126	0.3513	0.059*
C13	0.96441 (19)	0.16098 (18)	0.41774 (15)	0.0514 (4)
H13	1.0469	0.1462	0.4670	0.062*
C14	0.92681 (16)	0.27899 (15)	0.41383 (12)	0.0392 (3)
H14	0.9847	0.3427	0.4602	0.047*
C15	0.87940 (14)	0.45173 (13)	0.21260 (9)	0.0277 (2)
H15A	0.8555	0.4606	0.1440	0.033*
H15B	0.9101	0.3711	0.2182	0.033*
C16	1.00150 (13)	0.54409 (12)	0.27702 (10)	0.0272 (2)
C17	1.11964 (15)	0.51077 (14)	0.34877 (11)	0.0326 (3)
H17	1.1249	0.4305	0.3572	0.039*
C18	1.23005 (16)	0.59669 (16)	0.40806 (12)	0.0391 (3)
H18	1.3085	0.5734	0.4557	0.047*
C19	1.22389 (17)	0.71609 (16)	0.39659 (13)	0.0402 (3)
H19	1.2972	0.7735	0.4369	0.048*
C20	1.10789 (17)	0.74988 (15)	0.32468 (14)	0.0415 (3)
H20	1.1036	0.8301	0.3161	0.050*
C21	0.99754 (16)	0.66420 (14)	0.26510 (12)	0.0365 (3)
H21	0.9201	0.6877	0.2167	0.044*
C22	0.67207 (13)	0.71875 (11)	0.31683 (8)	0.0241 (2)
H22A	0.6710	0.7887	0.2855	0.029*
H22B	0.7655	0.6883	0.3304	0.029*
C23	0.64753 (13)	0.75728 (11)	0.41343 (8)	0.0241 (2)
C24	0.61737 (16)	0.67221 (13)	0.46430 (10)	0.0312 (3)
H24	0.6060	0.5905	0.4365	0.037*
C25	0.60394 (18)	0.70759 (16)	0.55601 (10)	0.0375 (3)
H25	0.5848	0.6497	0.5897	0.045*
C26	0.61904 (19)	0.82884 (18)	0.59725 (11)	0.0450 (4)
H26	0.6110	0.8527	0.6591	0.054*
C27	0.6460 (2)	0.91451 (16)	0.54692 (13)	0.0471 (4)
H27	0.6547	0.9963	0.5743	0.057*
C28	0.66030 (16)	0.87901 (13)	0.45523 (11)	0.0342 (3)
H28	0.6786	0.9373	0.4216	0.041*
C29	0.41673 (13)	0.66476 (12)	0.21893 (9)	0.0250 (2)
H29A	0.3962	0.6948	0.2785	0.030*
H29B	0.3496	0.5956	0.1823	0.030*
C30	0.39415 (13)	0.76240 (12)	0.15641 (9)	0.0253 (2)
C31	0.39678 (17)	0.88282 (13)	0.19750 (11)	0.0367 (3)
H31	0.4097	0.9041	0.2644	0.044*
C32	0.38032 (19)	0.97234 (15)	0.13996 (15)	0.0476 (4)
H32	0.3821	1.0530	0.1683	0.057*
C33	0.36147 (18)	0.94131 (17)	0.04103 (16)	0.0482 (4)
H33	0.3524	1.0011	0.0026	0.058*
C34	0.3560 (2)	0.82113 (18)	−0.00112 (13)	0.0480 (4)
H34	0.3417	0.8001	−0.0683	0.058*
C35	0.37159 (18)	0.73209 (15)	0.05590 (10)	0.0369 (3)
H35	0.3670	0.6514	0.0268	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.02207 (14)	0.02263 (14)	0.01297 (12)	0.00043 (10)	0.00599 (10)	0.00493 (10)
F1	0.0821 (8)	0.0427 (6)	0.0359 (5)	−0.0171 (5)	0.0037 (5)	−0.0028 (4)
O1	0.0346 (5)	0.0483 (6)	0.0208 (4)	−0.0061 (4)	0.0085 (4)	0.0136 (4)
O2	0.0274 (4)	0.0299 (4)	0.0163 (3)	−0.0020 (3)	0.0084 (3)	0.0070 (3)
N1	0.0246 (5)	0.0254 (5)	0.0139 (4)	−0.0018 (3)	0.0059 (3)	0.0054 (3)
N2	0.0239 (5)	0.0245 (5)	0.0159 (4)	0.0023 (3)	0.0056 (3)	0.0038 (3)
N3	0.0242 (5)	0.0304 (5)	0.0169 (4)	0.0048 (4)	0.0079 (4)	0.0072 (4)
C1	0.0259 (5)	0.0213 (5)	0.0276 (6)	0.0018 (4)	0.0084 (4)	0.0076 (4)
C2	0.0378 (7)	0.0233 (6)	0.0279 (6)	−0.0022 (5)	0.0086 (5)	0.0075 (5)
C3	0.0462 (8)	0.0236 (6)	0.0334 (7)	−0.0032 (5)	0.0017 (6)	0.0045 (5)
C4	0.0340 (8)	0.0339 (8)	0.0615 (11)	−0.0078 (6)	0.0049 (7)	0.0027 (7)
C5	0.0346 (8)	0.0483 (10)	0.0705 (12)	−0.0095 (7)	0.0257 (8)	−0.0017 (9)
C6	0.0339 (7)	0.0377 (7)	0.0447 (8)	−0.0047 (6)	0.0204 (6)	−0.0002 (6)
C7	0.0242 (5)	0.0261 (5)	0.0215 (5)	0.0016 (4)	0.0083 (4)	0.0084 (4)
C8	0.0289 (6)	0.0293 (6)	0.0155 (5)	0.0047 (4)	0.0056 (4)	0.0064 (4)
C9	0.0274 (6)	0.0309 (6)	0.0227 (5)	0.0060 (4)	0.0080 (4)	0.0101 (5)
C10	0.0352 (7)	0.0324 (7)	0.0322 (7)	0.0044 (5)	0.0052 (5)	0.0084 (5)
C11	0.0485 (9)	0.0311 (7)	0.0523 (9)	0.0040 (6)	0.0159 (7)	0.0089 (7)
C12	0.0491 (9)	0.0391 (8)	0.0676 (12)	0.0176 (7)	0.0238 (9)	0.0229 (8)
C13	0.0391 (9)	0.0531 (10)	0.0589 (11)	0.0186 (7)	0.0051 (8)	0.0264 (9)
C14	0.0321 (7)	0.0436 (8)	0.0351 (7)	0.0076 (6)	0.0003 (6)	0.0127 (6)
C15	0.0275 (6)	0.0338 (6)	0.0238 (5)	0.0064 (5)	0.0114 (5)	0.0053 (5)
C16	0.0243 (5)	0.0338 (6)	0.0269 (6)	0.0053 (4)	0.0121 (5)	0.0080 (5)
C17	0.0283 (6)	0.0377 (7)	0.0337 (7)	0.0060 (5)	0.0103 (5)	0.0121 (6)
C18	0.0280 (7)	0.0510 (9)	0.0367 (7)	0.0013 (6)	0.0064 (6)	0.0144 (7)
C19	0.0329 (7)	0.0449 (8)	0.0420 (8)	−0.0046 (6)	0.0134 (6)	0.0062 (7)
C20	0.0355 (7)	0.0357 (7)	0.0568 (10)	0.0021 (6)	0.0177 (7)	0.0145 (7)
C21	0.0288 (6)	0.0397 (8)	0.0433 (8)	0.0055 (5)	0.0109 (6)	0.0176 (6)
C22	0.0294 (6)	0.0246 (5)	0.0181 (5)	−0.0011 (4)	0.0083 (4)	0.0034 (4)
C23	0.0261 (5)	0.0273 (6)	0.0164 (5)	0.0039 (4)	0.0050 (4)	0.0025 (4)
C24	0.0441 (7)	0.0310 (6)	0.0218 (5)	0.0070 (5)	0.0143 (5)	0.0069 (5)
C25	0.0466 (8)	0.0493 (9)	0.0214 (6)	0.0119 (6)	0.0151 (6)	0.0117 (6)
C26	0.0524 (9)	0.0598 (10)	0.0223 (6)	0.0142 (8)	0.0154 (6)	−0.0007 (6)
C27	0.0596 (10)	0.0396 (8)	0.0371 (8)	0.0067 (7)	0.0179 (7)	−0.0096 (6)
C28	0.0404 (7)	0.0289 (6)	0.0313 (6)	0.0033 (5)	0.0123 (6)	0.0004 (5)
C29	0.0266 (5)	0.0289 (6)	0.0212 (5)	0.0053 (4)	0.0091 (4)	0.0072 (4)
C30	0.0268 (5)	0.0276 (6)	0.0228 (5)	0.0075 (4)	0.0089 (4)	0.0071 (4)
C31	0.0397 (7)	0.0306 (7)	0.0321 (7)	0.0088 (5)	0.0038 (6)	0.0025 (5)
C32	0.0430 (9)	0.0289 (7)	0.0616 (11)	0.0060 (6)	0.0039 (8)	0.0132 (7)
C33	0.0367 (8)	0.0540 (10)	0.0666 (11)	0.0153 (7)	0.0202 (8)	0.0404 (9)
C34	0.0572 (10)	0.0644 (11)	0.0406 (8)	0.0331 (9)	0.0283 (8)	0.0321 (8)
C35	0.0504 (8)	0.0398 (8)	0.0252 (6)	0.0202 (6)	0.0156 (6)	0.0120 (5)

Geometric parameters (Å, º)

P1—N1	1.6922 (10)	C16—C21	1.388 (2)
P1—N2	1.6484 (11)	C16—C17	1.3916 (18)
P1—N3	1.6400 (11)	C17—C18	1.392 (2)
P1—O2	1.4786 (9)	C17—H17	0.9300
F1—C3	1.3500 (19)	C18—C19	1.379 (2)
O1—C7	1.2200 (15)	C18—H18	0.9300
N1—C7	1.3716 (15)	C19—C20	1.382 (2)
N1—H1N	0.837 (18)	C19—H19	0.9300
N2—C22	1.4768 (15)	C20—C21	1.391 (2)
N2—C29	1.4868 (16)	C20—H20	0.9300
N3—C8	1.4672 (15)	C21—H21	0.9300
N3—C15	1.4844 (16)	C22—C23	1.5096 (17)
C1—C2	1.3886 (18)	C22—H22A	0.9700
C1—C6	1.3987 (19)	C22—H22B	0.9700
C1—C7	1.4984 (17)	C23—C28	1.3886 (19)
C2—C3	1.3851 (19)	C23—C24	1.3888 (18)
C2—H2	0.9300	C24—C25	1.3860 (19)
C3—C4	1.381 (3)	C24—H24	0.9300
C4—C5	1.385 (3)	C25—C26	1.380 (2)
C4—H4	0.9300	C25—H25	0.9300
C5—C6	1.388 (2)	C26—C27	1.376 (3)
C5—H5	0.9300	C26—H26	0.9300
C6—H6	0.9300	C27—C28	1.390 (2)
C8—C9	1.5144 (18)	C27—H27	0.9300
C8—H8A	0.9700	C28—H28	0.9300
C8—H8B	0.9700	C29—C30	1.5107 (17)
C9—C14	1.3847 (18)	C29—H29A	0.9700
C9—C10	1.3917 (19)	C29—H29B	0.9700
C10—C11	1.382 (2)	C30—C31	1.3839 (19)
C10—H10	0.9300	C30—C35	1.3887 (18)
C11—C12	1.377 (3)	C31—C32	1.390 (2)
C11—H11	0.9300	C31—H31	0.9300
C12—C13	1.374 (3)	C32—C33	1.375 (3)
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.390 (2)	C33—C34	1.382 (3)
C13—H13	0.9300	C33—H33	0.9300
C14—H14	0.9300	C34—C35	1.381 (2)
C15—C16	1.5181 (19)	C34—H34	0.9300
C15—H15A	0.9700	C35—H35	0.9300
C15—H15B	0.9700
N1—P1—N2	103.81 (5)	C21—C16—C17	118.52 (13)
N1—P1—N3	112.50 (5)	C21—C16—C15	120.36 (12)
N2—P1—N3	106.54 (5)	C17—C16—C15	121.13 (12)
O2—P1—N1	105.60 (5)	C16—C17—C18	120.50 (14)
O2—P1—N2	118.92 (5)	C16—C17—H17	119.8
O2—P1—N3	109.48 (5)	C18—C17—H17	119.8
C7—N1—P1	127.16 (8)	C19—C18—C17	120.46 (14)
C7—N1—H1N	118.5 (12)	C19—C18—H18	119.8
P1—N1—H1N	113.4 (12)	C17—C18—H18	119.8
C22—N2—C29	113.09 (10)	C18—C19—C20	119.51 (15)
C22—N2—P1	117.96 (8)	C18—C19—H19	120.2
C29—N2—P1	121.34 (8)	C20—C19—H19	120.2
C8—N3—C15	114.81 (10)	C19—C20—C21	120.18 (15)
C8—N3—P1	124.58 (8)	C19—C20—H20	119.9
C15—N3—P1	120.32 (8)	C21—C20—H20	119.9
C2—C1—C6	120.18 (13)	C16—C21—C20	120.82 (14)
C2—C1—C7	122.70 (12)	C16—C21—H21	119.6
C6—C1—C7	117.09 (12)	C20—C21—H21	119.6
C3—C2—C1	117.73 (14)	N2—C22—C23	112.56 (10)
C3—C2—H2	121.1	N2—C22—H22A	109.1
C1—C2—H2	121.1	C23—C22—H22A	109.1
F1—C3—C4	118.74 (14)	N2—C22—H22B	109.1
F1—C3—C2	117.89 (15)	C23—C22—H22B	109.1
C4—C3—C2	123.36 (15)	H22A—C22—H22B	107.8
C3—C4—C5	118.09 (14)	C28—C23—C24	118.56 (12)
C3—C4—H4	121.0	C28—C23—C22	120.38 (12)
C5—C4—H4	121.0	C24—C23—C22	121.01 (11)
C4—C5—C6	120.33 (16)	C25—C24—C23	120.85 (14)
C4—C5—H5	119.8	C25—C24—H24	119.6
C6—C5—H5	119.8	C23—C24—H24	119.6
C5—C6—C1	120.23 (15)	C26—C25—C24	119.88 (15)
C5—C6—H6	119.9	C26—C25—H25	120.1
C1—C6—H6	119.9	C24—C25—H25	120.1
O1—C7—N1	122.00 (11)	C27—C26—C25	120.03 (14)
O1—C7—C1	120.72 (11)	C27—C26—H26	120.0
N1—C7—C1	117.28 (10)	C25—C26—H26	120.0
N3—C8—C9	112.68 (10)	C26—C27—C28	120.08 (15)
N3—C8—H8A	109.1	C26—C27—H27	120.0
C9—C8—H8A	109.1	C28—C27—H27	120.0
N3—C8—H8B	109.1	C23—C28—C27	120.58 (15)
C9—C8—H8B	109.1	C23—C28—H28	119.7
H8A—C8—H8B	107.8	C27—C28—H28	119.7
C14—C9—C10	118.16 (13)	N2—C29—C30	113.65 (10)
C14—C9—C8	120.79 (12)	N2—C29—H29A	108.8
C10—C9—C8	121.05 (11)	C30—C29—H29A	108.8
C11—C10—C9	121.19 (14)	N2—C29—H29B	108.8
C11—C10—H10	119.4	C30—C29—H29B	108.8
C9—C10—H10	119.4	H29A—C29—H29B	107.7
C12—C11—C10	119.90 (16)	C31—C30—C35	118.79 (13)
C12—C11—H11	120.1	C31—C30—C29	121.26 (12)
C10—C11—H11	120.1	C35—C30—C29	119.95 (12)
C13—C12—C11	119.76 (16)	C30—C31—C32	120.80 (15)
C13—C12—H12	120.1	C30—C31—H31	119.6
C11—C12—H12	120.1	C32—C31—H31	119.6
C12—C13—C14	120.42 (15)	C33—C32—C31	119.79 (16)
C12—C13—H13	119.8	C33—C32—H32	120.1
C14—C13—H13	119.8	C31—C32—H32	120.1
C9—C14—C13	120.55 (16)	C32—C33—C34	119.86 (15)
C9—C14—H14	119.7	C32—C33—H33	120.1
C13—C14—H14	119.7	C34—C33—H33	120.1
N3—C15—C16	112.84 (10)	C35—C34—C33	120.36 (16)
N3—C15—H15A	109.0	C35—C34—H34	119.8
C16—C15—H15A	109.0	C33—C34—H34	119.8
N3—C15—H15B	109.0	C34—C35—C30	120.37 (15)
C16—C15—H15B	109.0	C34—C35—H35	119.8
H15A—C15—H15B	107.8	C30—C35—H35	119.8
O2—P1—N1—C7	−177.83 (10)	C10—C9—C14—C13	1.4 (2)
N3—P1—N1—C7	62.80 (12)	C8—C9—C14—C13	−179.03 (15)
N2—P1—N1—C7	−51.98 (12)	C12—C13—C14—C9	0.4 (3)
O2—P1—N2—C22	−69.72 (10)	C8—N3—C15—C16	−69.52 (14)
N3—P1—N2—C22	54.45 (9)	P1—N3—C15—C16	104.64 (11)
N1—P1—N2—C22	173.40 (8)	N3—C15—C16—C21	−73.76 (16)
O2—P1—N2—C29	77.75 (10)	N3—C15—C16—C17	106.47 (14)
N3—P1—N2—C29	−158.08 (9)	C21—C16—C17—C18	1.0 (2)
N1—P1—N2—C29	−39.13 (10)	C15—C16—C17—C18	−179.27 (13)
O2—P1—N3—C8	170.38 (10)	C16—C17—C18—C19	0.1 (2)
N2—P1—N3—C8	40.57 (11)	C17—C18—C19—C20	−0.9 (2)
N1—P1—N3—C8	−72.54 (11)	C18—C19—C20—C21	0.7 (3)
O2—P1—N3—C15	−3.18 (11)	C17—C16—C21—C20	−1.1 (2)
N2—P1—N3—C15	−132.99 (10)	C15—C16—C21—C20	179.08 (14)
N1—P1—N3—C15	113.90 (10)	C19—C20—C21—C16	0.3 (2)
C6—C1—C2—C3	1.3 (2)	C29—N2—C22—C23	61.38 (13)
C7—C1—C2—C3	179.24 (12)	P1—N2—C22—C23	−148.57 (9)
C1—C2—C3—F1	−177.25 (13)	N2—C22—C23—C28	−135.97 (12)
C1—C2—C3—C4	1.5 (2)	N2—C22—C23—C24	46.59 (16)
F1—C3—C4—C5	176.03 (16)	C28—C23—C24—C25	−1.7 (2)
C2—C3—C4—C5	−2.7 (3)	C22—C23—C24—C25	175.83 (13)
C3—C4—C5—C6	1.2 (3)	C23—C24—C25—C26	0.7 (2)
C4—C5—C6—C1	1.5 (3)	C24—C25—C26—C27	0.6 (3)
C2—C1—C6—C5	−2.7 (2)	C25—C26—C27—C28	−1.0 (3)
C7—C1—C6—C5	179.17 (15)	C24—C23—C28—C27	1.3 (2)
P1—N1—C7—O1	−3.97 (19)	C22—C23—C28—C27	−176.22 (14)
P1—N1—C7—C1	175.47 (9)	C26—C27—C28—C23	0.0 (3)
C2—C1—C7—O1	−156.09 (13)	C22—N2—C29—C30	67.33 (13)
C6—C1—C7—O1	21.96 (19)	P1—N2—C29—C30	−81.59 (12)
C2—C1—C7—N1	24.46 (18)	N2—C29—C30—C31	−100.23 (15)
C6—C1—C7—N1	−157.50 (13)	N2—C29—C30—C35	79.14 (15)
C15—N3—C8—C9	−57.00 (14)	C35—C30—C31—C32	−1.4 (2)
P1—N3—C8—C9	129.12 (10)	C29—C30—C31—C32	177.98 (14)
N3—C8—C9—C14	121.40 (14)	C30—C31—C32—C33	−0.1 (3)
N3—C8—C9—C10	−59.07 (17)	C31—C32—C33—C34	1.4 (3)
C14—C9—C10—C11	−2.2 (2)	C32—C33—C34—C35	−1.0 (3)
C8—C9—C10—C11	178.24 (15)	C33—C34—C35—C30	−0.5 (3)
C9—C10—C11—C12	1.2 (3)	C31—C30—C35—C34	1.7 (2)
C10—C11—C12—C13	0.7 (3)	C29—C30—C35—C34	−177.66 (14)
C11—C12—C13—C14	−1.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2^i	0.93	2.45	3.1124 (16)	128
C25—H25···O1^ii	0.93	2.45	3.2342 (17)	142
N1—H1N···O2^i	0.837 (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

Crystal data

C35H32F2N3O2P	Z = 2
Mr = 595.61	F(000) = 624
Triclinic, P1	Dx = 1.341 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.9526 (11) Å	Cell parameters from 6783 reflections
b = 12.2897 (10) Å	θ = 3.2–32.3°
c = 12.7463 (12) Å	µ = 0.14 mm^−1
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) Å^3

Data collection

Oxford Diffraction Xcalibur (Eos, Gemini) diffractometer	9523 independent reflections
Radiation source: Enhance (Mo) X-ray Source	7763 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 16.1500 pixels mm^-1	θmax = 32.4°, θmin = 3.2°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→18
Tmin = 0.992, Tmax = 1.000	l = −18→18
17265 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0513P)^2 + 0.4759P] where P = (Fo^2 + 2Fc^2)/3
9523 reflections	(Δ/σ)max < 0.001
392 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.43740 (3)	−0.02169 (3)	0.30322 (2)	0.01984 (7)
F1	0.49638 (11)	0.40250 (9)	0.77758 (7)	0.0432 (2)
F2	0.26919 (12)	0.48796 (10)	0.48246 (9)	0.0500 (3)
O1	0.32602 (10)	0.14761 (9)	0.26412 (8)	0.02789 (19)
O2	0.48794 (10)	−0.08185 (9)	0.37548 (7)	0.02689 (18)
N1	0.42791 (11)	0.09006 (10)	0.39671 (9)	0.02233 (19)
H1N	0.4533 (18)	0.0941 (18)	0.4664 (17)	0.039 (5)*
N2	0.28600 (11)	−0.14105 (10)	0.19524 (9)	0.02231 (19)
N3	0.53297 (10)	0.06323 (10)	0.24067 (8)	0.02067 (18)
C1	0.38081 (11)	0.26075 (11)	0.46306 (10)	0.01907 (19)
C2	0.32275 (12)	0.32957 (12)	0.42896 (11)	0.0239 (2)
H2	0.2837	0.3146	0.3503	0.029*
C3	0.32482 (14)	0.42044 (13)	0.51513 (13)	0.0295 (3)
C4	0.38077 (15)	0.44723 (13)	0.63302 (12)	0.0311 (3)
H4	0.3794	0.5080	0.6892	0.037*
C5	0.43884 (14)	0.37847 (12)	0.66256 (11)	0.0272 (2)
C6	0.44136 (13)	0.28633 (11)	0.58150 (10)	0.0233 (2)
H6	0.4823	0.2426	0.6053	0.028*
C7	0.37487 (12)	0.16138 (11)	0.36620 (10)	0.0203 (2)
C8	0.63319 (12)	0.20891 (12)	0.29033 (10)	0.0242 (2)
H8A	0.7257	0.2287	0.3274	0.029*
H8B	0.6129	0.2489	0.3508	0.029*
C9	0.63249 (12)	0.27303 (11)	0.20105 (11)	0.0240 (2)
C10	0.51002 (13)	0.24232 (12)	0.11758 (11)	0.0259 (2)
H10	0.4247	0.1758	0.1121	0.031*
C11	0.51447 (15)	0.31028 (14)	0.04249 (12)	0.0319 (3)
H11	0.4323	0.2884	−0.0133	0.038*
C12	0.64137 (18)	0.41068 (15)	0.05066 (15)	0.0413 (3)
H12	0.6444	0.4569	0.0012	0.050*
C13	0.76264 (17)	0.44130 (16)	0.13250 (17)	0.0451 (4)
H13	0.8478	0.5085	0.1382	0.054*
C14	0.75871 (14)	0.37255 (14)	0.20666 (14)	0.0355 (3)
H14	0.8414	0.3932	0.2607	0.043*
C15	0.56485 (12)	−0.01043 (12)	0.15817 (10)	0.0237 (2)
H15A	0.5631	0.0188	0.0931	0.028*
H15B	0.4923	−0.1050	0.1267	0.028*
C16	0.70388 (13)	0.00782 (12)	0.21205 (10)	0.0244 (2)
C17	0.81851 (14)	0.09705 (15)	0.19713 (12)	0.0314 (3)
H17	0.8106	0.1478	0.1545	0.038*
C18	0.94557 (15)	0.11212 (17)	0.24496 (14)	0.0387 (3)
H18	1.0219	0.1727	0.2344	0.046*
C19	0.95815 (16)	0.03721 (18)	0.30793 (15)	0.0415 (3)
H19	1.0428	0.0469	0.3401	0.050*
C20	0.84434 (19)	−0.0522 (2)	0.32287 (19)	0.0516 (5)
H20	0.8524	−0.1028	0.3656	0.062*
C21	0.71770 (16)	−0.06731 (17)	0.27473 (16)	0.0418 (4)
H21	0.6414	−0.1287	0.2848	0.050*
C22	0.23433 (12)	−0.13973 (12)	0.07795 (10)	0.0230 (2)
H22A	0.2531	−0.1913	0.0250	0.028*
H22B	0.2858	−0.0483	0.0830	0.028*
C23	0.08095 (12)	−0.19524 (12)	0.02627 (10)	0.0226 (2)
C24	0.03004 (14)	−0.12016 (13)	0.06257 (12)	0.0300 (3)
H24	0.0907	−0.0354	0.1220	0.036*
C25	−0.11001 (15)	−0.16988 (14)	0.01136 (13)	0.0354 (3)
H25	−0.1426	−0.1186	0.0369	0.042*
C26	−0.20173 (14)	−0.29556 (14)	−0.07766 (13)	0.0340 (3)
H26	−0.2955	−0.3283	−0.1125	0.041*
C27	−0.15325 (14)	−0.37201 (14)	−0.11446 (13)	0.0350 (3)
H27	−0.2146	−0.4570	−0.1735	0.042*
C28	−0.01251 (13)	−0.32199 (13)	−0.06331 (12)	0.0298 (3)
H28	0.0196	−0.3736	−0.0891	0.036*
C29	0.21642 (14)	−0.27347 (12)	0.20305 (11)	0.0271 (2)
H29A	0.2825	−0.2988	0.2194	0.033*
H29B	0.1413	−0.3387	0.1274	0.033*
C30	0.15810 (13)	−0.27986 (12)	0.29566 (11)	0.0240 (2)
C31	0.10079 (17)	−0.20779 (16)	0.32146 (14)	0.0372 (3)
H31	0.1002	−0.1515	0.2829	0.045*
C32	0.04429 (18)	−0.21939 (18)	0.40456 (16)	0.0436 (4)
H32	0.0078	−0.1694	0.4224	0.052*
C33	0.04182 (15)	−0.30452 (16)	0.46101 (13)	0.0364 (3)
H33	0.0020	−0.3134	0.5153	0.044*
C34	0.09897 (13)	−0.37615 (13)	0.43611 (12)	0.0294 (3)
H34	0.0982	−0.4332	0.4741	0.035*
C35	0.15751 (13)	−0.36316 (12)	0.35458 (11)	0.0254 (2)
H35	0.1969	−0.4109	0.3391	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.02944 (15)	0.02422 (14)	0.01462 (12)	0.02134 (12)	0.00770 (10)	0.00797 (10)
F1	0.0675 (6)	0.0436 (5)	0.0207 (4)	0.0381 (5)	0.0116 (4)	0.0057 (3)
F2	0.0756 (7)	0.0585 (6)	0.0564 (6)	0.0610 (6)	0.0298 (5)	0.0292 (5)
O1	0.0383 (5)	0.0348 (5)	0.0193 (4)	0.0276 (4)	0.0084 (4)	0.0110 (3)
O2	0.0434 (5)	0.0341 (4)	0.0190 (4)	0.0323 (4)	0.0113 (4)	0.0124 (3)
N1	0.0343 (5)	0.0279 (5)	0.0164 (4)	0.0251 (4)	0.0100 (4)	0.0092 (4)
N2	0.0303 (5)	0.0216 (4)	0.0181 (4)	0.0161 (4)	0.0084 (4)	0.0101 (3)
N3	0.0250 (4)	0.0229 (4)	0.0165 (4)	0.0169 (4)	0.0066 (3)	0.0048 (3)
C1	0.0211 (5)	0.0196 (5)	0.0214 (5)	0.0141 (4)	0.0091 (4)	0.0087 (4)
C2	0.0274 (5)	0.0265 (5)	0.0274 (6)	0.0204 (5)	0.0114 (5)	0.0130 (4)
C3	0.0355 (6)	0.0294 (6)	0.0397 (7)	0.0266 (5)	0.0178 (6)	0.0165 (5)
C4	0.0425 (7)	0.0266 (6)	0.0353 (7)	0.0253 (6)	0.0202 (6)	0.0103 (5)
C5	0.0357 (6)	0.0243 (5)	0.0222 (5)	0.0190 (5)	0.0102 (5)	0.0062 (4)
C6	0.0300 (6)	0.0227 (5)	0.0224 (5)	0.0193 (5)	0.0089 (4)	0.0081 (4)
C7	0.0249 (5)	0.0230 (5)	0.0192 (5)	0.0176 (4)	0.0086 (4)	0.0089 (4)
C8	0.0231 (5)	0.0237 (5)	0.0194 (5)	0.0137 (4)	0.0032 (4)	0.0021 (4)
C9	0.0251 (5)	0.0203 (5)	0.0233 (5)	0.0130 (4)	0.0084 (4)	0.0033 (4)
C10	0.0269 (6)	0.0234 (5)	0.0258 (6)	0.0136 (5)	0.0097 (5)	0.0088 (4)
C11	0.0409 (7)	0.0317 (6)	0.0287 (6)	0.0231 (6)	0.0146 (5)	0.0132 (5)
C12	0.0548 (9)	0.0356 (7)	0.0455 (9)	0.0259 (7)	0.0296 (8)	0.0232 (7)
C13	0.0396 (8)	0.0341 (7)	0.0617 (11)	0.0148 (6)	0.0293 (8)	0.0223 (7)
C14	0.0263 (6)	0.0294 (6)	0.0427 (8)	0.0126 (5)	0.0123 (6)	0.0090 (6)
C15	0.0269 (5)	0.0276 (5)	0.0187 (5)	0.0190 (5)	0.0078 (4)	0.0046 (4)
C16	0.0282 (6)	0.0287 (6)	0.0224 (5)	0.0208 (5)	0.0103 (4)	0.0077 (4)
C17	0.0334 (6)	0.0418 (7)	0.0294 (6)	0.0249 (6)	0.0162 (5)	0.0173 (5)
C18	0.0300 (7)	0.0484 (8)	0.0422 (8)	0.0234 (6)	0.0175 (6)	0.0177 (7)
C19	0.0343 (7)	0.0560 (9)	0.0454 (9)	0.0341 (7)	0.0150 (6)	0.0176 (7)
C20	0.0513 (9)	0.0695 (12)	0.0746 (13)	0.0495 (9)	0.0330 (9)	0.0491 (10)
C21	0.0387 (8)	0.0498 (9)	0.0652 (11)	0.0341 (7)	0.0283 (7)	0.0384 (8)
C22	0.0251 (5)	0.0266 (5)	0.0181 (5)	0.0148 (5)	0.0078 (4)	0.0101 (4)
C23	0.0249 (5)	0.0235 (5)	0.0207 (5)	0.0137 (4)	0.0090 (4)	0.0105 (4)
C24	0.0311 (6)	0.0267 (6)	0.0283 (6)	0.0183 (5)	0.0056 (5)	0.0056 (5)
C25	0.0342 (7)	0.0346 (7)	0.0386 (7)	0.0249 (6)	0.0098 (6)	0.0072 (6)
C26	0.0252 (6)	0.0332 (7)	0.0394 (7)	0.0164 (5)	0.0100 (5)	0.0098 (6)
C27	0.0259 (6)	0.0259 (6)	0.0393 (7)	0.0109 (5)	0.0088 (5)	0.0023 (5)
C28	0.0272 (6)	0.0257 (6)	0.0336 (7)	0.0151 (5)	0.0120 (5)	0.0057 (5)
C29	0.0402 (7)	0.0232 (5)	0.0245 (6)	0.0203 (5)	0.0147 (5)	0.0118 (4)
C30	0.0276 (5)	0.0239 (5)	0.0228 (5)	0.0158 (5)	0.0088 (4)	0.0107 (4)
C31	0.0520 (9)	0.0453 (8)	0.0418 (8)	0.0385 (7)	0.0261 (7)	0.0272 (7)
C32	0.0541 (9)	0.0610 (10)	0.0491 (9)	0.0468 (9)	0.0313 (8)	0.0296 (8)
C33	0.0352 (7)	0.0484 (8)	0.0352 (7)	0.0253 (6)	0.0199 (6)	0.0205 (6)
C34	0.0290 (6)	0.0312 (6)	0.0270 (6)	0.0146 (5)	0.0104 (5)	0.0154 (5)
C35	0.0296 (6)	0.0253 (5)	0.0250 (6)	0.0172 (5)	0.0102 (5)	0.0122 (4)

Geometric parameters (Å, º)

P1—N1	1.6880 (10)	C16—C21	1.3804 (18)
P1—N2	1.6488 (11)	C16—C17	1.3822 (18)
P1—N3	1.6443 (11)	C17—C18	1.3915 (19)
P1—O2	1.4798 (9)	C17—H17	0.9300
F1—C5	1.3537 (15)	C18—C19	1.376 (2)
F2—C3	1.3538 (14)	C18—H18	0.9300
O1—C7	1.2236 (14)	C19—C20	1.377 (2)
N1—C7	1.3664 (14)	C19—H19	0.9300
N1—H1N	0.847 (19)	C20—C21	1.387 (2)
N2—C22	1.4748 (14)	C20—H20	0.9300
N2—C29	1.4756 (15)	C21—H21	0.9300
N3—C8	1.4687 (15)	C22—C23	1.5115 (16)
N3—C15	1.4829 (14)	C22—H22A	0.9700
C1—C6	1.3936 (16)	C22—H22B	0.9700
C1—C2	1.3945 (15)	C23—C24	1.3891 (17)
C1—C7	1.5047 (15)	C23—C28	1.3961 (17)
C2—C3	1.3789 (17)	C24—C25	1.3858 (19)
C2—H2	0.9300	C24—H24	0.9300
C3—C4	1.377 (2)	C25—C26	1.385 (2)
C4—C5	1.3768 (18)	C25—H25	0.9300
C4—H4	0.9300	C26—C27	1.3805 (19)
C5—C6	1.3816 (16)	C26—H26	0.9300
C6—H6	0.9300	C27—C28	1.3921 (19)
C8—C9	1.5141 (18)	C27—H27	0.9300
C8—H8A	0.9700	C28—H28	0.9300
C8—H8B	0.9700	C29—C30	1.5111 (17)
C9—C14	1.3925 (18)	C29—H29A	0.9700
C9—C10	1.3959 (17)	C29—H29B	0.9700
C10—C11	1.3908 (18)	C30—C31	1.3882 (18)
C10—H10	0.9300	C30—C35	1.3890 (16)
C11—C12	1.389 (2)	C31—C32	1.388 (2)
C11—H11	0.9300	C31—H31	0.9300
C12—C13	1.377 (3)	C32—C33	1.382 (2)
C12—H12	0.9300	C32—H32	0.9300
C13—C14	1.389 (2)	C33—C34	1.380 (2)
C13—H13	0.9300	C33—H33	0.9300
C14—H14	0.9300	C34—C35	1.3863 (18)
C15—C16	1.5151 (16)	C34—H34	0.9300
C15—H15A	0.9700	C35—H35	0.9300
C15—H15B	0.9700
N1—P1—N2	113.07 (5)	C21—C16—C17	118.49 (12)
N1—P1—N3	105.18 (5)	C21—C16—C15	120.46 (12)
N2—P1—N3	105.51 (5)	C17—C16—C15	121.02 (11)
O2—P1—N1	105.15 (5)	C16—C17—C18	121.00 (13)
O2—P1—N2	109.06 (5)	C16—C17—H17	119.5
O2—P1—N3	119.05 (5)	C18—C17—H17	119.5
C7—N1—P1	125.60 (8)	C19—C18—C17	119.91 (14)
C7—N1—H1N	120.9 (12)	C19—C18—H18	120.0
P1—N1—H1N	113.3 (12)	C17—C18—H18	120.0
C22—N2—C29	115.46 (10)	C18—C19—C20	119.44 (13)
C22—N2—P1	125.00 (8)	C18—C19—H19	120.3
C29—N2—P1	116.99 (8)	C20—C19—H19	120.3
C8—N3—C15	113.59 (9)	C19—C20—C21	120.50 (15)
C8—N3—P1	125.14 (8)	C19—C20—H20	119.7
C15—N3—P1	116.41 (8)	C21—C20—H20	119.7
C6—C1—C2	120.19 (10)	C16—C21—C20	120.65 (14)
C6—C1—C7	123.37 (10)	C16—C21—H21	119.7
C2—C1—C7	116.44 (10)	C20—C21—H21	119.7
C3—C2—C1	118.15 (11)	N2—C22—C23	114.47 (9)
C3—C2—H2	120.9	N2—C22—H22A	108.6
C1—C2—H2	120.9	C23—C22—H22A	108.6
F2—C3—C4	117.80 (12)	N2—C22—H22B	108.6
F2—C3—C2	118.35 (12)	C23—C22—H22B	108.6
C4—C3—C2	123.85 (11)	H22A—C22—H22B	107.6
C5—C4—C3	115.88 (11)	C24—C23—C28	118.32 (11)
C5—C4—H4	122.1	C24—C23—C22	121.29 (11)
C3—C4—H4	122.1	C28—C23—C22	120.33 (11)
F1—C5—C4	118.00 (11)	C25—C24—C23	120.87 (12)
F1—C5—C6	118.29 (11)	C25—C24—H24	119.6
C4—C5—C6	123.71 (12)	C23—C24—H24	119.6
C5—C6—C1	118.19 (11)	C26—C25—C24	120.34 (13)
C5—C6—H6	120.9	C26—C25—H25	119.8
C1—C6—H6	120.9	C24—C25—H25	119.8
O1—C7—N1	121.81 (10)	C27—C26—C25	119.65 (13)
O1—C7—C1	120.41 (10)	C27—C26—H26	120.2
N1—C7—C1	117.77 (10)	C25—C26—H26	120.2
N3—C8—C9	113.99 (9)	C26—C27—C28	120.05 (13)
N3—C8—H8A	108.8	C26—C27—H27	120.0
C9—C8—H8A	108.8	C28—C27—H27	120.0
N3—C8—H8B	108.8	C27—C28—C23	120.78 (12)
C9—C8—H8B	108.8	C27—C28—H28	119.6
H8A—C8—H8B	107.6	C23—C28—H28	119.6
C14—C9—C10	118.38 (12)	N2—C29—C30	114.45 (10)
C14—C9—C8	118.93 (12)	N2—C29—H29A	108.6
C10—C9—C8	122.56 (11)	C30—C29—H29A	108.6
C11—C10—C9	120.60 (12)	N2—C29—H29B	108.6
C11—C10—H10	119.7	C30—C29—H29B	108.6
C9—C10—H10	119.7	H29A—C29—H29B	107.6
C12—C11—C10	120.16 (14)	C31—C30—C35	118.62 (12)
C12—C11—H11	119.9	C31—C30—C29	121.91 (11)
C10—C11—H11	119.9	C35—C30—C29	119.44 (11)
C13—C12—C11	119.60 (14)	C30—C31—C32	120.28 (13)
C13—C12—H12	120.2	C30—C31—H31	119.9
C11—C12—H12	120.2	C32—C31—H31	119.9
C12—C13—C14	120.43 (14)	C33—C32—C31	120.62 (14)
C12—C13—H13	119.8	C33—C32—H32	119.7
C14—C13—H13	119.8	C31—C32—H32	119.7
C13—C14—C9	120.81 (14)	C34—C33—C32	119.42 (13)
C13—C14—H14	119.6	C34—C33—H33	120.3
C9—C14—H14	119.6	C32—C33—H33	120.3
N3—C15—C16	114.46 (9)	C33—C34—C35	120.11 (12)
N3—C15—H15A	108.6	C33—C34—H34	119.9
C16—C15—H15A	108.6	C35—C34—H34	119.9
N3—C15—H15B	108.6	C34—C35—C30	120.93 (12)
C16—C15—H15B	108.6	C34—C35—H35	119.5
H15A—C15—H15B	107.6	C30—C35—H35	119.5
O2—P1—N1—C7	−174.13 (10)	C11—C12—C13—C14	0.0 (2)
N3—P1—N1—C7	59.38 (11)	C12—C13—C14—C9	−1.0 (2)
N2—P1—N1—C7	−55.24 (12)	C10—C9—C14—C13	1.2 (2)
O2—P1—N2—C22	−148.50 (9)	C8—C9—C14—C13	−174.90 (13)
N3—P1—N2—C22	−19.53 (11)	C8—N3—C15—C16	60.84 (13)
N1—P1—N2—C22	94.90 (10)	P1—N3—C15—C16	−95.82 (11)
O2—P1—N2—C29	12.48 (10)	N3—C15—C16—C21	82.20 (16)
N3—P1—N2—C29	141.45 (9)	N3—C15—C16—C17	−99.52 (14)
N1—P1—N2—C29	−104.12 (9)	C21—C16—C17—C18	−0.6 (2)
O2—P1—N3—C8	−94.45 (10)	C15—C16—C17—C18	−178.90 (13)
N2—P1—N3—C8	142.75 (9)	C16—C17—C18—C19	0.2 (2)
N1—P1—N3—C8	22.97 (10)	C17—C18—C19—C20	0.0 (3)
O2—P1—N3—C15	59.19 (10)	C18—C19—C20—C21	0.2 (3)
N2—P1—N3—C15	−63.61 (9)	C17—C16—C21—C20	0.8 (2)
N1—P1—N3—C15	176.61 (8)	C15—C16—C21—C20	179.14 (16)
C6—C1—C2—C3	−1.29 (18)	C19—C20—C21—C16	−0.6 (3)
C7—C1—C2—C3	179.30 (11)	C29—N2—C22—C23	57.53 (14)
C1—C2—C3—F2	179.68 (11)	P1—N2—C22—C23	−141.23 (9)
C1—C2—C3—C4	−0.1 (2)	N2—C22—C23—C24	77.82 (14)
F2—C3—C4—C5	−178.67 (12)	N2—C22—C23—C28	−104.96 (13)
C2—C3—C4—C5	1.1 (2)	C28—C23—C24—C25	0.1 (2)
C3—C4—C5—F1	179.37 (12)	C22—C23—C24—C25	177.40 (12)
C3—C4—C5—C6	−0.8 (2)	C23—C24—C25—C26	−0.3 (2)
F1—C5—C6—C1	179.36 (11)	C24—C25—C26—C27	0.7 (2)
C4—C5—C6—C1	−0.5 (2)	C25—C26—C27—C28	−0.9 (2)
C2—C1—C6—C5	1.55 (18)	C26—C27—C28—C23	0.7 (2)
C7—C1—C6—C5	−179.08 (11)	C24—C23—C28—C27	−0.3 (2)
P1—N1—C7—O1	1.24 (18)	C22—C23—C28—C27	−177.62 (13)
P1—N1—C7—C1	−177.54 (8)	C22—N2—C29—C30	−125.48 (11)
C6—C1—C7—O1	−176.63 (11)	P1—N2—C29—C30	71.71 (13)
C2—C1—C7—O1	2.76 (16)	N2—C29—C30—C31	35.58 (18)
C6—C1—C7—N1	2.16 (17)	N2—C29—C30—C35	−146.45 (12)
C2—C1—C7—N1	−178.45 (10)	C35—C30—C31—C32	0.0 (2)
C15—N3—C8—C9	66.04 (12)	C29—C30—C31—C32	177.99 (14)
P1—N3—C8—C9	−139.68 (9)	C30—C31—C32—C33	−1.3 (3)
N3—C8—C9—C14	−138.17 (12)	C31—C32—C33—C34	1.4 (3)
N3—C8—C9—C10	45.92 (15)	C32—C33—C34—C35	−0.4 (2)
C14—C9—C10—C11	−0.36 (18)	C33—C34—C35—C30	−0.9 (2)
C8—C9—C10—C11	175.57 (11)	C31—C30—C35—C34	1.06 (19)
C9—C10—C11—C12	−0.6 (2)	C29—C30—C35—C34	−176.98 (12)
C10—C11—C12—C13	0.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2^i	0.93	2.22	3.1123 (14)	162
N1—H1N···O2^i	0.847 (19)	2.024 (19)	2.8659 (13)	172.8 (17)

Symmetry code: (i) −x+1, −y, −z+1.