Different cyclic motifs in phospho­ric triamides containing a C(O)NHP(O)(NH)₂ skeleton and an R₂²(10) graph set in three new compounds: a database analysis of hydrogen-bond strengths based on motifs

In the crystal networks of N,N'-bis­(2-chloro­benzyl)-N''-(2,6-difluoro­benzo­yl)phosphor­ic triamide, C₂₁H₁₈Cl₂F₂N₃O₂P, (I), N-(2,6-difluoro­benzo­yl)-N',N''-bis­(4-meth­oxy­benzyl)phosphor­ic triamide, C₂₃H₂₄F₂N₃O₄P, (II), and N-(2-chloro-2,2-difluoro­acetyl)-N',N''-bis­(4-methyl­phenyl)phosphor­ic tri­amide, C₁₆H₁₇ClF₂N₃O₂P, (III), C=O...H-N_C(O)NHP(O) and P=O...H-N_amide hydrogen bonds are responsible for the aggregation of the mol­ecules. This is the opposite result from that commonly observed for carbacyl­amido­phosphates, which show a tendency for the phosphoryl group, rather than the carbonyl counterpart, to form hydrogen bonds with the NH group of the C(O)NHP(O) skeleton. This hydrogen-bond pattern leads to cyclic R₂²(10) motifs in (I)-(III), different from those found for all previously reported compounds of the general formula RC(O)NHP(O)[NR¹R²]₂ with the syn orientation of P=O versus NH [R₂²(8)], and also from those commonly observed for RC(O)NHP(O)[NHR¹]₂ [a sequence of alternate R₂²(8) and R₂²(12) motifs]. In these cases, the R₂²(8) and R₂²(12) graph sets are formed through similar kinds of hydrogen bond, i.e. a pair of P=O...H-N_C(O)NHP(O) hydrogen bonds for the former and two C=O...H-N_amide hydrogen bonds for the latter. This article also reviews 102 similar structures deposited in the Cambridge Structural Database and with the Inter­national Union of Crystallography, with the aim of comparing hydrogen-bond strengths in the above-mentioned cyclic motifs. This analysis shows that the strongest N-H...O hydrogen bonds exist in the R₂²(8) rings of some mol­ecules. The phosphoryl and carbonyl groups in each of compounds (I)-(III) are anti with respect to each other and the P atoms are in a tetra­hedral coordination environment. In the crystal structures, adjacent mol­ecules are linked via the above-mentioned hydrogen bonds in a linear arrangement, parallel to [010] for (I) and (III) and parallel to [100] for (II). Formation of the N_C(O)NHP(O)-H...O=C instead of the N_C(O)NHP(O)-H...O=P hydrogen bond is reflected in the higher N_C(O)NHP(O)-H vibrational frequencies for these mol­ecules compared with previously reported analogous compounds.

S1. Comment

In a recently published paper by Toghraee et al. (2011), the patterns of hydrogen bonds were studied in the crystal packing of phosphoric triamides (PTAs) containing a C(O)NHP(O) skeleton. The authors classified this category of phosphoramide compounds into different subclasses with C(O)NHP(O)(N)₂ and C(O)NHP(O)(NH)₂ moieties, named as subclasses A and B, respectively. It was found that the phosphoryl group has a better donor ability than the carbonyl counterpart, so that, in all deposited CIF files in the Cambridge Structural Database (CSD, Version 5.32, November 2010 update; Allen, 2002) belonging to subclass A, only the PO···H—N hydrogen bond was observed in the crystal packing. When the P═O group and N—H unit are syn with respect to one another, this type of hydrogen bond forms a hydrogen-bonded dimer [R₂²(8) ring; for graph-set notation, see Bernstein et al. (1995)] (Fig. 1). Moreover, for most cases of compounds in subclass B, the NH group of C(O)NHP(O) moiety is hydrogen-bonded to P(O), whereas the H atom of the NHR' unit is involved in a hydrogen-bond interaction with C(O). These interactions usually produce two different kinds of centrosymmetric cyclic motifs, viz. R₂²(8) and R₂²(12), which are altered [Alternate?] in a linear arrangement. The R₂²(8) motif is formed through a pair of N_C(O)NHP(O)—H···O═P hydrogen bonds, while the R₂²(12) ring is built via two C═O···H—N_amide hydrogen bonds (Fig. 2). Among the published structures, the C═O···H—N_C(O)NHP(O) interaction was found for only two examples: C₆H₅C(O)NHP(O)[NHCH₂C₆H₅]₂ (Gholivand et al., 2006) and C₆H₅C(O)NHP(O)[NHC₆H₁₁]₂ (Pourayoubi, Rostami Chaijan et al., 2011a). However, the existence of the PO···HNR' interaction has been observed for four compounds as a PO[···.HN_C(O)NHP(O)][···HNR'] (Gubina et al., 2009; Gholivand, Shariatinia, Mashhadi et al., 2009) and a PO[···HNR']₂ hydrogen bond (Gholivand et al., 2006; Pourayoubi, Rostami Chaijan et al., 2011a), where the O atoms act as double hydrogen-bond acceptors (Steiner, 2002).

We present here the three new compounds N,N'-bis(2-chlorobenzyl)-N''-(2,6-difluorobenzoyl)phosphoric triamide, (I), N-(2,6-difluorobenzoyl)-N',N''-bis(4-methoxybenzyl)phosphoric triamide, (II), and N-(2-chloro-2,2-difluoroacetyl)-N',N''-bis(4-µethylphenyl)phosphoric triamide, (III), which show relatively rare C═ O···H—N_C(O)NHP(O) and P═O···H—N_amide hydrogen bonds. In addition, we attempted to analyse the strength of the hydrogen-bonds based on their motifs, and also to find a relationship between the N—H stretching frequency and the hydrogen-bond pattern.

For compounds (I)–(III), single crystals were obtained at roonm temperature from a 1:2 mixture of CH₃OH/CHCl₃ for (I) and (II), and a 1:4 mixture of CH₃CN/CH₃OH for (III). Their molecular structures are shown in Figs. 3, 4 and 5, respectively. The P atoms exhibit a distorted tetrahedral environment, as has been noted for other phosphoric triamides and their chalco-derivatives (Rudd et al., 1996). For example, in (I), the bond angles at the P atom vary in the range 102.33 (13)–116.04 (12)°, while the P—N bond distances range from 1.616 (2) to 1.707 (2) Å (Table 1). The phosphoryl and carbonyl groups adopt an anti position in these structures, which is in agreement with all previously reported acyclic phosphoramidate compounds (Gholivand & Pourayoubi, 2004; Gholivand, Shariatinia, Mashhadi et al., 2009) containing a C(O)NHP(O)(N'H)₂ skeleton. This conformation is the opposite of the orientation of P(O) and C(O) in the diazaphosphorinanes CCl₃C(O)NHP(O)X (X = NHC₁₀H₆NH; Gholivand, Shariatinia, Ansar et al., 2009), 4-F-C₆H₅C(O)NHP(O)X [X = NHCH₂C(CH₃)₂CH₂NH; Tarahhomi et al., 2011] and CCl₂HC(O)NHP(O)X [X = NHCH₂C(CH₃)₂CH₂NH; Toghraee et al., 2011] and a few examples of compounds with the formula RC(O)NHP(O)[NR¹R²]₂, which show a gauche orientation of P═O versus C═O (Toghraee et al., 2011).

The P═O bond lengths are standard in (I) [1.475 (2) Å], (II) [1.4804 (12) Å] and (III) [1.473 (3) Å]. As expected, the P—N_amide distances in both [All three?] compounds were found to be significantly shorter than the related P—N_C(O)NHP(O) (Tables 1, 3 and 5).

In (I) and (II), the chemical natures of the N atoms in both compounds are different, so that the N atom of one benzylamide moiety exhibits a slight deviation from planarity, while the N atom of the other benzylamide group has a practically planar environment [Please check rephrasing]. In (III), the environments of all three N atoms are nearly planar. None of these N atoms acts in any hydrogen bond as an acceptor, thus exhibiting low Lewis base character. As expected, the C—N_C(O)NHP(O) bonds for these structures are shorter than the other C—N_amide bonds.

In the structures (I)–(III), adjacent molecules are linked via N_C(O)NHP(O)—H···O═C hydrogen bonds [(I): N1—H1N···O1(x, y + 1, z); (II): N1—H1N···O1(x + 1, y, z); (III): N1—H1N···O2(x, y + 1, z)] and also through two different N_amide—H···O═P hydrogen bonds [(I): N2—H2N···O2(x, y - 1, z) and N3—H3N···O2(x, y - 1, z); (II) N2—H2N···O2(x - 1, y, z) and N3—H3N···O2(x - 1, y, z); (III): N2—H2N···O1(x, y - 1, z) and N3—H3A···O1(x, y - 1, z)], building R₂²(10) rings (Fig. 6) in a linear arrangement, parallel to [010] for (I) and (III) [for example, see Fig. 7 for compound (I)] and [parallel to?] [100] for (II) (Fig. 8). This means that, in each of these structures, the phosphoryl group acts as a double-hydrogen acceptor to form a P═O[···H—N_amide]₂ hydrogen bond.

This hydrogen-bond pattern is the opposite of that commonly observed for carbacylamidophosphates, which show a tendency for the phosphoryl group, rather than the carbonyl counterpart, to form hydrogen bonds with the more acidic NH group of the C(O)NHP(O) skeleton, whereas the NH group of the NHR' unit is hydrogen-bonded to C(O).

Exceptions to this bonding selectivity in these structures may be attributed to kinetic factors controlling the crystal growth (MacDonald & Whitesides, 1994).

A search of the CSD and recently published papers (Pourayoubi, Tarahhomi et al., 2010a,b, 2011; Pourayoubi, Rostami Chaijan et al., 2011a,b; Pourayoubi & Saneei, 2011; Pourayoubi, Toghraee & Divjakovic, 2011; Raissi Shabari et al., 2011; Tarahhomi et al., 2011; Toghraee et al., 2011) shows that the strongest N—H···O hydrogen bonds are found for P═O···H—N_C(O)NHP(O) hydrogen bonds, especially in the R₂²(8) rings of some molecules [in the case of a syn orientation of P═O versus N—H which allows the building of the cyclic motif through a pair of P═O···H—N_C(O)NHP(O) hydrogen bonds]. A histogram of the N···O distances in these N—H···O hydrogen bonds is given in Fig. 9. The strongest (three columns on the left) and weakest (three columns on the right) hydrogen bonds are shown for N···O distances in the ranges 2.70–2.85 Å [for N_C(O)NHP(O)–H···O(P) hydrogen bonds] and 2.95–3.10 Å [for N_amide–H···O(C) hydrogen bonds], while in the range 2.85–2.95 Å for donor–acceptor distances both cases of hydrogen bonds are found.

In (I), besides cooperation in the N—H···O hydrogen bond, the benzamide N—H group is involved in an intramolecular N1—H1N···F1 hydrogen bond (Table 2). Further stabilization of (I) is produced via a weak C11—H11A···F2ⁱⁱⁱ hydrogen bond [C11···F2ⁱⁱⁱ = 3.354 (3) Å; symmetry code: (iii) -x + 1, y - 1/2, -z + 3/2] and C7═ O1···F1ⁱ [O1···F1ⁱ = 2.876 (3) Å; symmetry code: (i) x, y + 1, z] and Cl2···Cl2^iv [3.258 (1) Å; symmetry code: (iv) -x, -y + 2, -z + 1] intermolecular interactions.

The hydrogen-bond pattern in (II) is complicated. A pair of C15_methoxy—H15A···F1ⁱⁱⁱ [C15···F1ⁱⁱⁱ = 3.155 (2) Å; symmetry code: (iii) -x, -y + 1, -z + 1] hydrogen bonds make an R₂²(30) ring, whereas a combination of one C13—H13A···O3_methoxy^iv [C13···O3^iv = 3.390 (2) Å; symmetry code: (iv) -x, -y + 2, -z + 1], one C_methoxy—H···F and one C3—H3B···(O2)P1^v [C3···O2^v = 3.293 (2) Å; symmetry code: (v) x, y + 1, z] hydrogen bonds forms R₃³(16) rings. Moreover, the cyclic dimer and trimer motifs are composed, respectively, via a pair of intermolecular C—H···O_methoxy hydrogen bonds to form a centrosymmetric R₂²(8) ring (Fig. 10). Also, an R₃³(27) ring (Fig. 10) is formed through a combination of intermolecular C16—H16B···O4_methoxy [C16···O4^vi = 3.581 (2) Å; symmetry code: (vi) -x + 1/2, y + 1/2, -z + 3/2] and C—H···(O)P hydrogen bonds. These hydrogen bonds expand the crystal structure of (II) into a three-dimensional arrangement. A weak C7═O1···F1ⁱ [O1···F1ⁱ = 2.986 (2) Å; symmetry code: (i) x + 1, y, z] interaction is also found in the crystal packing. The crystal packing of (III) does not show any C—H···X (X = O, F or Cl) interactions.

In a previously reported paper by Tarahhomi et al. (2011), the effect of lowering the N_C(O)NHP(O)—H vibrational frequency by strong N_C(O)NHP(O)—H···O═P hydrogen bonds was discussed, so a that compound with a stronger N—H···O hydrogen bond showed a lower N—H vibrational frequency. Moreover, the N_C(O)NHP(O)—H stretching mode appeared at a lower frequency than that of the N_amide—H.

The differences in the N—H regions in the IR spectroscopic data of (I)–(III) from those of the previously reported analogous compounds may be a result of these different hydrogen-bond patterns. For example, in the compounds 2-NO₂–C₆H₄C(O)NHP(O)[N(C₂H₅)₂]₂ (Gholivand et al., 2010) and Cl₃CC(O)NHP(O)[NHC(CH₃)₃]₂ (Gholivand & Pourayoubi, 2004), the N_C(O)NHP(O)—H stretching frequencies, which are involved in the N_C(O)NHP(O)—H···O(P) hydrogen bond, appear at 3030 and 3045 cm^-1, respectively, while no absorption bands are observed below 3180 cm^-1 in any of (I)–(III). For example in (I), three absorption bands are revealed at 3204, 3262 and 3345 cm^-1, while for (II), with hydrogen bonds with relatively similar strengths, the N—H stretching modes overlap and only one absorption band appears at 3263 cm^-1. For (III), the absorption bands at 3260 and 3183 cm^-1 are assigned to the N—H stretching modes.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Gholivand & Pourayoubi (2004); Gholivand et al. (2006, 2010); Gholivand, Shariatinia, Ansar, Mashhadi & Daeepour (2009); Gholivand, Shariatinia, Mashhadi, Daeepour, Farshidnasab, Mahzouni, Taheri, Amiri & Ansar (2009); Gubina et al. (2009); Iriarte et al. (2008); MacDonald & Whitesides (1994); Pourayoubi & Saneei (2011); Pourayoubi et al. (2010a, 2010b, 2011a, 2011b); Pourayoubi, Tarahhomi, Rheingold & Golen (2011); Pourayoubi, Toghraee & Divjakovic (2011); Raissi Shabari, Pourayoubi & Saneei (2011); Rudd et al. (1996); Steiner (2002); Tarahhomi et al. (2011); Toghraee et al. (2011).

S2. Experimental

2,6-F₂–C₆H₃C(O)NHP(O)Cl₂ and CClF₂C(O)NHP(O)Cl₂ were prepared according to the literature methods reported by Pourayoubi, Tarahhomi et al. (2010a) and Iriarte et al. (2008), respectively.

Compound (I) was synthesized from the reaction of 2,6-F₂–C₆H₃C(O)NHP(O)Cl₂ (0.35 g, 1.28 mmol) and 2-chlorobenzylamine (0.725 g, 5.12 mmol) in dry chloroform (30 ml). The amine was added dropwise to a solution of initial phosphorus-chlorine at 273 K. After stirring for 6 h, the solvent was evaporated, and the product was washed with distilled water and recrystallized from a 1:2 (v/v) mixture of methanol–chloroform at room temperature. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3345 (NH), 3262 (NH), 3204 (NH), 2925, 1668 (C═O), 1623, 1470, 1426, 1287, 1236, 1205, 1127, 1090, 1049, 1041, 1011, 902, 817, 769, 753, 694, 584, 510, 578.

Compound (II) was synthesized in a similar procedure to (I) but by using 4-methoxybenzylamine (0.598 g, 4.36 mmol) instead of 2-chlorobenzylamine [2,6-F₂–C₆H₃C(O)NHP(O)Cl₂: 0.30 g, 1.09 mmol]. Single crystals suitable for X-ray crystallography were obtained after recrystallization from a 1:2 (v/v) mixture of methanol–chloroform at room temperature. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3263 (NH), 3003, 2958, 1668 (C═O), 1623, 1589, 1515, 1466, 1441, 1303, 1253, 1197, 1078, 1042, 1007, 923, 813, 788, 764, 698, 588, 523, 478.

Compound (III) was synthesized from the reaction of CClF₂C(O)NHP(O)Cl₂ (0.40 g, 1.6 mmol) in dry CHCl₃ and a solution of para-toluidine (0.343 g, 3.2 mmol) and triethylamine (0.324 g, 3.2 mmol) in dry CHCl₃ at 273 K. After stirring for 4 h, the solvent was evaporated at room temperature. The solid product was washed with H₂O. Single crystals suitable for X-ray crystallography were recrystallized from a 4:1 (v/v) mixture of methanol–acetonitrile by slow evaporation at room temperature. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3260 (NH), 3183 (NH), 2927, 1717 (C═O), 1620, 1517, 1466, 1383, 1281, 1225, 1163, 1133, 963, 863, 813, 697.

S3. Refinement

For (I), (II) and (III), H atoms on N1, N2, and N3 were found in difference Fourier maps and allowed to refine with an N—H bond-length restraint of 0.85 (2) Å and with U_iso(H) = 1.2U_eq(N). The positions of H atoms bound to C atoms were calculated and refined as isotropic using an appropriate riding model; for compounds (I) and (II), bond distances were 0.95, 0.99 and 0.98 Å for CH, CH₂ and CH₃ groups, respectively, with riding constraints of 1.2U_eq(C) for CH and CH₂ groups, and 1.5U_eq(C) for CH₃ groups. For compound (III), the distance values were 0.93 and 0.96 Å for CH and CH₃ groups, with U_iso(H) = 1.2 and 1.5U_eq(C), respectively.

Computing details

Data collection: APEX2 (Bruker, 2005) for (I), (II); SMART (Bruker, 1998) for (III). Cell refinement: SAINT (Bruker, 2005) for (I), (II); SAINT-Plus (Bruker, 1998) for (III). Data reduction: SAINT (Bruker, 2005) for (I), (II); SAINT-Plus (Bruker, 1998) for (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The R2^2(8) graph set in compounds containing a C(O)NHP(O)(N)2 skeleton and a syn orientation of P═O versus NH.
	Fig. 2. A view of the R2^2(8) and R2^2(12) motifs in compounds containing a C(O)NHP(O)(NH)2 skeleton.
	Fig. 3. The molecular structure and atom-labelling scheme for (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The molecular structure and atom-labelling scheme for (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 5. The molecular structure and atom-labelling scheme for (III). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 6. A view of the R2^2(10) graph set in compounds containing a C(O)NHP(O)(NH)2 skeleton.
	Fig. 7. A crystal packing diagram for (I). H atoms bound to C atoms have been omitted for clarity. The P═O···H—Namide (marked a), C═ O···H—NC(O)NHP(O) (marked b) and F···H—NC(O)NHP(O) (marked c) hydrogen bonds are shown. [Colour key for the electronic version of the paper: red, black and violet dashed lines, respectively. Additionally, O atoms are red, amide N atoms are dark blue, NC(O)NHP(O) atoms are light blue, F atoms are green–yellow and H atoms are light grey.]
	Fig. 8. A crystal packing diagram for (II). H atoms bound to C atoms have been omitted for clarity. The P═O···H—Namide (marked a) and C═ O···H—NC(O)NHP(O) (marked b) hydrogen bonds are shown. (Colour key for the electronic version of the paper: red and black dashed lines, respectively; the atomic colour scheme is the same as for Fig. 7.)
	Fig. 9. A histogram of N···O distances in N—H···O hydrogen bonds for phosphoric triamides with a C(O)NHP(O) skeleton. The data shown in the first two and last two columns (brown and red, respectively, in the electronic version of the paper) were observed for NC(O)NHP(O)—H···O and Namide—H···O hydrogen bonds, respectively. Both types of hydrogen bond were observed in the range 2.80–3.00 Å (central four columns). Only one Namide—H···O, and one NC(O)NHP(O)—H···O hydrogen bond is respectively found in the range 2.80-2.85 and 2.95–3.00 Å.
	Fig. 10. A partial crystal packing diagram for (II), viewed parallel to the bc plane, formed via intermolecular C—H···F and C—H···O hydrogen bonds (the N—H···O hydrogen bonds are along the a axis). H atoms involved in contacts are shown as light grey and the other H atoms have been omitted for clarity. The C15methoxy—H15A···F1^iii [marked a; C15···F1^iii = 3.155 (2) Å], C13—H13A···O3methoxy^iv [marked b; C13···O3^iv = 3.390 (2) Å], C3—H3B···(O2)P1^v [marked c; C3···O2^v = 3.293 (2) Å] and C16—H16B···O4methoxy [marked d; C16···O4^vi = 3.581 (2) Å] hydrogen bonds are shown (colour key for the electronic version of the paper: black, orange, purple and blue dashed lines, respectively). [Symmetry codes: (iii) -x, -y + 1, -z + 1; (iv) -x, -y + 2, -z + 1; (v) x, y + 1, z; (vi) -x + 1/2, y + 1/2, -z + 3/2.]

(I) N,N'-bis(2-chlorobenzyl)-N''-(2,6- difluorobenzoyl)phosphoric triamide

Crystal data

C21H18Cl2F2N3O2P	F(000) = 992
Mr = 484.25	Dx = 1.563 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.643 (3) Å	Cell parameters from 7966 reflections
b = 4.9874 (6) Å	θ = 3.4–27.8°
c = 21.482 (3) Å	µ = 0.44 mm^−1
β = 102.056 (2)°	T = 100 K
V = 2058.2 (4) Å^3	Block, colourless
Z = 4	0.25 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	4821 independent reflections
Radiation source: fine-focus sealed tube	3463 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
ϕ and ω scans	θmax = 27.9°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −25→25
Tmin = 0.899, Tmax = 0.958	k = −6→6
25048 measured reflections	l = −28→27

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0446P)^2 + 2.5057P] where P = (Fo^2 + 2Fc^2)/3
4821 reflections	(Δ/σ)max = 0.002
289 parameters	Δρmax = 0.65 e Å^−3
3 restraints	Δρmin = −0.48 e Å^−3

Special details

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
Cl1	0.56322 (4)	0.82496 (15)	0.57320 (3)	0.02548 (18)
Cl2	−0.01375 (4)	0.77969 (15)	0.44276 (3)	0.02530 (18)
P1	0.27115 (4)	0.74413 (14)	0.50981 (3)	0.01593 (17)
F1	0.15953 (8)	0.9940 (3)	0.65322 (7)	0.0252 (4)
F2	0.32417 (9)	0.3325 (4)	0.73647 (8)	0.0287 (4)
O1	0.25395 (10)	0.3553 (4)	0.60992 (9)	0.0214 (4)
O2	0.27054 (10)	1.0164 (4)	0.48287 (9)	0.0201 (4)
N1	0.26151 (12)	0.7935 (5)	0.58611 (10)	0.0175 (5)
H1N	0.2581 (16)	0.949 (4)	0.6011 (13)	0.021*
N2	0.34085 (12)	0.5706 (5)	0.51076 (11)	0.0184 (5)
H2N	0.3346 (16)	0.411 (4)	0.4998 (14)	0.022*
N3	0.20998 (12)	0.5420 (5)	0.47405 (11)	0.0190 (5)
H3N	0.2201 (16)	0.383 (4)	0.4815 (14)	0.023*
C1	0.19795 (15)	0.8613 (6)	0.70344 (13)	0.0205 (6)
C2	0.18783 (15)	0.9231 (6)	0.76331 (14)	0.0252 (7)
H2A	0.1558	1.0587	0.7692	0.030*
C3	0.22578 (16)	0.7818 (6)	0.81506 (13)	0.0262 (7)
H3A	0.2205	0.8238	0.8569	0.031*
C4	0.27096 (16)	0.5812 (7)	0.80576 (13)	0.0266 (7)
H4A	0.2963	0.4823	0.8408	0.032*
C5	0.27869 (15)	0.5265 (6)	0.74460 (13)	0.0222 (6)
C6	0.24330 (14)	0.6648 (6)	0.69125 (12)	0.0184 (6)
C7	0.25292 (14)	0.5913 (6)	0.62590 (12)	0.0184 (6)
C8	0.41113 (14)	0.6730 (6)	0.53326 (12)	0.0198 (6)
H8A	0.4082	0.8641	0.5449	0.024*
H8B	0.4362	0.6641	0.4979	0.024*
C9	0.45316 (15)	0.5247 (6)	0.58983 (12)	0.0193 (6)
C10	0.52358 (15)	0.5791 (6)	0.61148 (13)	0.0200 (6)
C11	0.56409 (16)	0.4456 (6)	0.66265 (13)	0.0248 (7)
H11A	0.6120	0.4879	0.6764	0.030*
C12	0.53366 (17)	0.2495 (6)	0.69349 (13)	0.0272 (7)
H12A	0.5609	0.1542	0.7282	0.033*
C13	0.46341 (16)	0.1924 (6)	0.67365 (13)	0.0250 (7)
H13A	0.4424	0.0599	0.6953	0.030*
C14	0.42361 (15)	0.3286 (6)	0.62220 (13)	0.0217 (6)
H14A	0.3755	0.2875	0.6089	0.026*
C15	0.13673 (14)	0.6099 (6)	0.47053 (12)	0.0204 (6)
H15A	0.1306	0.8062	0.4654	0.024*
H15B	0.1234	0.5578	0.5108	0.024*
C16	0.08956 (14)	0.4695 (6)	0.41556 (12)	0.0194 (6)
C17	0.01876 (15)	0.5362 (6)	0.39907 (13)	0.0210 (6)
C18	−0.02593 (15)	0.4159 (6)	0.34858 (13)	0.0244 (7)
H18A	−0.0734	0.4693	0.3377	0.029*
C19	−0.00137 (16)	0.2176 (6)	0.31399 (13)	0.0248 (7)
H19A	−0.0319	0.1332	0.2794	0.030*
C20	0.06798 (15)	0.1425 (6)	0.32998 (13)	0.0230 (6)
H20A	0.0849	0.0052	0.3066	0.028*
C21	0.11285 (15)	0.2674 (6)	0.38021 (12)	0.0198 (6)
H21A	0.1603	0.2142	0.3907	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0220 (4)	0.0238 (4)	0.0314 (4)	−0.0035 (3)	0.0075 (3)	−0.0043 (3)
Cl2	0.0224 (4)	0.0254 (4)	0.0287 (4)	0.0044 (3)	0.0067 (3)	0.0006 (3)
P1	0.0173 (4)	0.0149 (4)	0.0156 (3)	0.0005 (3)	0.0034 (3)	0.0001 (3)
F1	0.0242 (9)	0.0243 (9)	0.0278 (9)	0.0048 (7)	0.0073 (7)	0.0030 (7)
F2	0.0291 (10)	0.0288 (10)	0.0281 (9)	0.0104 (8)	0.0059 (7)	0.0044 (8)
O1	0.0271 (11)	0.0144 (10)	0.0230 (10)	−0.0008 (9)	0.0060 (8)	−0.0017 (8)
O2	0.0232 (11)	0.0159 (10)	0.0214 (9)	0.0007 (8)	0.0048 (8)	0.0002 (8)
N1	0.0234 (13)	0.0118 (12)	0.0180 (11)	0.0011 (10)	0.0055 (9)	−0.0026 (9)
N2	0.0192 (13)	0.0122 (12)	0.0232 (12)	−0.0004 (10)	0.0027 (9)	−0.0036 (9)
N3	0.0179 (13)	0.0161 (12)	0.0219 (12)	0.0008 (10)	0.0012 (9)	0.0001 (10)
C1	0.0194 (15)	0.0175 (15)	0.0250 (14)	−0.0014 (12)	0.0055 (11)	0.0000 (12)
C2	0.0197 (15)	0.0270 (17)	0.0305 (15)	−0.0028 (13)	0.0086 (12)	−0.0068 (13)
C3	0.0281 (16)	0.0341 (18)	0.0182 (13)	−0.0066 (14)	0.0088 (12)	−0.0065 (13)
C4	0.0277 (17)	0.0320 (18)	0.0196 (14)	−0.0019 (14)	0.0037 (12)	0.0022 (12)
C5	0.0205 (15)	0.0209 (15)	0.0252 (14)	0.0008 (12)	0.0049 (11)	0.0003 (12)
C6	0.0180 (14)	0.0179 (15)	0.0196 (13)	−0.0046 (11)	0.0047 (10)	−0.0010 (11)
C7	0.0136 (14)	0.0200 (15)	0.0207 (13)	−0.0021 (11)	0.0019 (10)	0.0012 (11)
C8	0.0194 (15)	0.0197 (15)	0.0207 (13)	0.0000 (12)	0.0054 (11)	−0.0022 (11)
C9	0.0212 (15)	0.0194 (15)	0.0177 (13)	0.0017 (12)	0.0049 (11)	−0.0045 (11)
C10	0.0232 (15)	0.0167 (15)	0.0214 (13)	−0.0007 (12)	0.0076 (11)	−0.0051 (11)
C11	0.0211 (16)	0.0252 (17)	0.0255 (15)	0.0045 (13)	−0.0011 (11)	−0.0070 (12)
C12	0.0327 (18)	0.0260 (17)	0.0210 (14)	0.0096 (14)	0.0010 (12)	−0.0029 (12)
C13	0.0313 (17)	0.0235 (16)	0.0210 (14)	0.0035 (13)	0.0072 (12)	0.0021 (12)
C14	0.0210 (15)	0.0218 (16)	0.0221 (14)	0.0003 (12)	0.0041 (11)	−0.0011 (12)
C15	0.0187 (15)	0.0231 (16)	0.0191 (13)	−0.0004 (12)	0.0033 (11)	−0.0004 (12)
C16	0.0203 (15)	0.0195 (15)	0.0186 (13)	−0.0027 (12)	0.0045 (11)	0.0036 (11)
C17	0.0216 (15)	0.0181 (15)	0.0240 (14)	0.0002 (12)	0.0065 (11)	0.0025 (12)
C18	0.0165 (15)	0.0272 (17)	0.0281 (15)	−0.0010 (13)	0.0011 (11)	0.0052 (13)
C19	0.0266 (16)	0.0251 (17)	0.0208 (14)	−0.0057 (13)	0.0004 (11)	0.0026 (12)
C20	0.0275 (17)	0.0210 (15)	0.0204 (13)	−0.0020 (13)	0.0050 (11)	−0.0001 (12)
C21	0.0204 (14)	0.0200 (15)	0.0196 (13)	−0.0013 (12)	0.0052 (11)	0.0045 (11)

Geometric parameters (Å, º)

Cl1—C10	1.747 (3)	C8—H8A	0.9900
Cl2—C17	1.736 (3)	C8—H8B	0.9900
P1—O2	1.475 (2)	C9—C10	1.391 (4)
P1—N2	1.616 (2)	C9—C14	1.395 (4)
P1—N3	1.632 (2)	C10—C11	1.385 (4)
P1—N1	1.707 (2)	C11—C12	1.385 (4)
F1—C1	1.353 (3)	C11—H11A	0.9500
F2—C5	1.353 (3)	C12—C13	1.386 (4)
O1—C7	1.227 (3)	C12—H12A	0.9500
N1—C7	1.355 (4)	C13—C14	1.390 (4)
N1—H1N	0.850 (18)	C13—H13A	0.9500
N2—C8	1.457 (4)	C14—H14A	0.9500
N2—H2N	0.833 (18)	C15—C16	1.512 (4)
N3—C15	1.465 (4)	C15—H15A	0.9900
N3—H3N	0.826 (18)	C15—H15B	0.9900
C1—C2	1.377 (4)	C16—C21	1.395 (4)
C1—C6	1.386 (4)	C16—C17	1.402 (4)
C2—C3	1.394 (4)	C17—C18	1.382 (4)
C2—H2A	0.9500	C18—C19	1.383 (4)
C3—C4	1.379 (4)	C18—H18A	0.9500
C3—H3A	0.9500	C19—C20	1.385 (4)
C4—C5	1.381 (4)	C19—H19A	0.9500
C4—H4A	0.9500	C20—C21	1.390 (4)
C5—C6	1.393 (4)	C20—H20A	0.9500
C6—C7	1.501 (4)	C21—H21A	0.9500
C8—C9	1.512 (4)
O2—P1—N2	115.79 (12)	C10—C9—C14	117.3 (3)
O2—P1—N3	116.04 (12)	C10—C9—C8	120.7 (3)
N2—P1—N3	102.33 (13)	C14—C9—C8	122.0 (3)
O2—P1—N1	104.51 (11)	C11—C10—C9	122.5 (3)
N2—P1—N1	109.20 (12)	C11—C10—Cl1	118.2 (2)
N3—P1—N1	108.83 (12)	C9—C10—Cl1	119.3 (2)
C7—N1—P1	123.5 (2)	C12—C11—C10	119.0 (3)
C7—N1—H1N	114 (2)	C12—C11—H11A	120.5
P1—N1—H1N	122 (2)	C10—C11—H11A	120.5
C8—N2—P1	123.93 (19)	C11—C12—C13	120.0 (3)
C8—N2—H2N	120 (2)	C11—C12—H12A	120.0
P1—N2—H2N	116 (2)	C13—C12—H12A	120.0
C15—N3—P1	120.01 (19)	C12—C13—C14	120.2 (3)
C15—N3—H3N	115 (2)	C12—C13—H13A	119.9
P1—N3—H3N	112 (2)	C14—C13—H13A	119.9
F1—C1—C2	118.0 (3)	C13—C14—C9	121.0 (3)
F1—C1—C6	117.9 (2)	C13—C14—H14A	119.5
C2—C1—C6	124.0 (3)	C9—C14—H14A	119.5
C1—C2—C3	118.3 (3)	N3—C15—C16	111.6 (2)
C1—C2—H2A	120.8	N3—C15—H15A	109.3
C3—C2—H2A	120.8	C16—C15—H15A	109.3
C4—C3—C2	120.3 (3)	N3—C15—H15B	109.3
C4—C3—H3A	119.9	C16—C15—H15B	109.3
C2—C3—H3A	119.9	H15A—C15—H15B	108.0
C3—C4—C5	118.9 (3)	C21—C16—C17	117.0 (3)
C3—C4—H4A	120.6	C21—C16—C15	122.8 (3)
C5—C4—H4A	120.6	C17—C16—C15	120.1 (3)
F2—C5—C4	118.1 (3)	C18—C17—C16	122.0 (3)
F2—C5—C6	118.5 (2)	C18—C17—Cl2	118.9 (2)
C4—C5—C6	123.4 (3)	C16—C17—Cl2	119.1 (2)
C1—C6—C5	115.1 (2)	C17—C18—C19	119.8 (3)
C1—C6—C7	124.1 (2)	C17—C18—H18A	120.1
C5—C6—C7	120.7 (3)	C19—C18—H18A	120.1
O1—C7—N1	121.7 (2)	C18—C19—C20	119.7 (3)
O1—C7—C6	120.6 (2)	C18—C19—H19A	120.1
N1—C7—C6	117.7 (2)	C20—C19—H19A	120.1
N2—C8—C9	114.6 (2)	C19—C20—C21	120.2 (3)
N2—C8—H8A	108.6	C19—C20—H20A	119.9
C9—C8—H8A	108.6	C21—C20—H20A	119.9
N2—C8—H8B	108.6	C20—C21—C16	121.3 (3)
C9—C8—H8B	108.6	C20—C21—H21A	119.4
H8A—C8—H8B	107.6	C16—C21—H21A	119.4
O2—P1—N1—C7	173.6 (2)	P1—N2—C8—C9	118.4 (2)
N2—P1—N1—C7	−61.9 (3)	N2—C8—C9—C10	172.1 (2)
N3—P1—N1—C7	49.1 (3)	N2—C8—C9—C14	−7.6 (4)
O2—P1—N2—C8	47.4 (2)	C14—C9—C10—C11	0.5 (4)
N3—P1—N2—C8	174.6 (2)	C8—C9—C10—C11	−179.2 (3)
N1—P1—N2—C8	−70.2 (2)	C14—C9—C10—Cl1	−179.4 (2)
O2—P1—N3—C15	−60.8 (2)	C8—C9—C10—Cl1	0.8 (4)
N2—P1—N3—C15	172.2 (2)	C9—C10—C11—C12	0.2 (4)
N1—P1—N3—C15	56.7 (2)	Cl1—C10—C11—C12	−179.8 (2)
F1—C1—C2—C3	178.2 (3)	C10—C11—C12—C13	−1.0 (4)
C6—C1—C2—C3	0.6 (5)	C11—C12—C13—C14	1.0 (4)
C1—C2—C3—C4	−1.5 (4)	C12—C13—C14—C9	−0.2 (4)
C2—C3—C4—C5	1.1 (5)	C10—C9—C14—C13	−0.5 (4)
C3—C4—C5—F2	178.8 (3)	C8—C9—C14—C13	179.2 (3)
C3—C4—C5—C6	0.3 (5)	P1—N3—C15—C16	156.82 (19)
F1—C1—C6—C5	−176.9 (2)	N3—C15—C16—C21	10.1 (4)
C2—C1—C6—C5	0.7 (4)	N3—C15—C16—C17	−171.5 (2)
F1—C1—C6—C7	0.5 (4)	C21—C16—C17—C18	−2.5 (4)
C2—C1—C6—C7	178.1 (3)	C15—C16—C17—C18	179.0 (3)
F2—C5—C6—C1	−179.7 (2)	C21—C16—C17—Cl2	178.2 (2)
C4—C5—C6—C1	−1.1 (4)	C15—C16—C17—Cl2	−0.3 (4)
F2—C5—C6—C7	2.8 (4)	C16—C17—C18—C19	2.0 (4)
C4—C5—C6—C7	−178.7 (3)	Cl2—C17—C18—C19	−178.7 (2)
P1—N1—C7—O1	2.6 (4)	C17—C18—C19—C20	−0.5 (4)
P1—N1—C7—C6	−178.51 (19)	C18—C19—C20—C21	−0.6 (4)
C1—C6—C7—O1	−133.9 (3)	C19—C20—C21—C16	0.1 (4)
C5—C6—C7—O1	43.4 (4)	C17—C16—C21—C20	1.4 (4)
C1—C6—C7—N1	47.1 (4)	C15—C16—C21—C20	179.9 (3)
C5—C6—C7—N1	−135.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.85 (2)	2.04 (2)	2.858 (3)	162 (3)
N1—H1N···F1	0.85 (2)	2.44 (3)	2.881 (3)	113 (2)
N2—H2N···O2^ii	0.83 (2)	2.32 (2)	3.092 (3)	154 (3)
N3—H3N···O2^ii	0.83 (2)	2.08 (2)	2.869 (3)	161 (3)

Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z.

(II) N-(2,6-difluorobenzoyl)-N',N''-bis(4- methoxybenzyl)phosphoric triamide

Crystal data

C23H24F2N3O4P	F(000) = 992
Mr = 475.42	Dx = 1.404 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.8252 (6) Å	Cell parameters from 6676 reflections
b = 10.3456 (12) Å	θ = 2.4–27.9°
c = 45.068 (5) Å	µ = 0.17 mm^−1
β = 90.530 (2)°	T = 100 K
V = 2249.7 (5) Å^3	Block, colourless
Z = 4	0.22 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5131 independent reflections
Radiation source: fine-focus sealed tube	4200 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ϕ and ω scans	θmax = 28.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −6→6
Tmin = 0.963, Tmax = 0.983	k = −13→13
18537 measured reflections	l = −59→44

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) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0353P)^2 + 1.3104P] where P = (Fo^2 + 2Fc^2)/3
5131 reflections	(Δ/σ)max = 0.020
309 parameters	Δρmax = 0.41 e Å^−3
3 restraints	Δρmin = −0.34 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.52732 (8)	0.59705 (4)	0.636114 (9)	0.01463 (11)
F1	0.8051 (2)	0.28742 (10)	0.58288 (2)	0.0261 (2)
F2	0.3388 (2)	0.11618 (10)	0.66522 (3)	0.0357 (3)
O1	0.1869 (2)	0.34953 (11)	0.63342 (3)	0.0229 (3)
O2	0.7990 (2)	0.66351 (11)	0.63678 (3)	0.0197 (3)
O3	−0.2604 (3)	0.85524 (15)	0.49307 (3)	0.0393 (4)
O4	−0.3356 (3)	0.88688 (13)	0.76831 (3)	0.0330 (3)
N1	0.6175 (3)	0.43798 (13)	0.63298 (3)	0.0162 (3)
H1N	0.787 (3)	0.4217 (18)	0.6320 (4)	0.019*
N2	0.3179 (3)	0.62877 (13)	0.60858 (3)	0.0179 (3)
H2N	0.153 (3)	0.6385 (19)	0.6132 (4)	0.022*
N3	0.3392 (3)	0.62370 (14)	0.66491 (3)	0.0183 (3)
H3N	0.168 (3)	0.6222 (18)	0.6620 (4)	0.022*
C1	0.7468 (4)	0.18689 (16)	0.60109 (4)	0.0202 (3)
C2	0.8624 (4)	0.06833 (17)	0.59493 (4)	0.0275 (4)
H2C	0.9829	0.0577	0.5786	0.033*
C3	0.7987 (4)	−0.03528 (17)	0.61318 (5)	0.0308 (4)
H3B	0.8774	−0.1177	0.6094	0.037*
C4	0.6221 (4)	−0.01976 (17)	0.63685 (5)	0.0308 (4)
H4A	0.5796	−0.0906	0.6494	0.037*
C5	0.5089 (4)	0.10008 (17)	0.64185 (4)	0.0242 (4)
C6	0.5667 (3)	0.20797 (15)	0.62449 (4)	0.0177 (3)
C7	0.4380 (3)	0.33775 (15)	0.63064 (4)	0.0170 (3)
C8	0.3647 (4)	0.57684 (19)	0.57880 (4)	0.0286 (4)
H8A	0.3137	0.4842	0.5784	0.034*
H8B	0.5638	0.5841	0.5739	0.034*
C9	0.1949 (4)	0.64924 (18)	0.55601 (4)	0.0236 (4)
C10	0.0055 (4)	0.58474 (18)	0.53816 (4)	0.0262 (4)
H10A	−0.0180	0.4942	0.5406	0.031*
C11	−0.1517 (4)	0.64953 (19)	0.51673 (4)	0.0278 (4)
H11A	−0.2800	0.6035	0.5046	0.033*
C12	−0.1193 (4)	0.78076 (19)	0.51333 (4)	0.0283 (4)
C13	0.0704 (4)	0.84769 (19)	0.53114 (4)	0.0318 (4)
H13A	0.0933	0.9383	0.5288	0.038*
C14	0.2247 (4)	0.78212 (19)	0.55220 (4)	0.0286 (4)
H14A	0.3532	0.8283	0.5643	0.034*
C15	−0.4459 (5)	0.7911 (2)	0.47313 (5)	0.0454 (6)
H15A	−0.5379	0.8551	0.4604	0.068*
H15B	−0.5853	0.7438	0.4845	0.068*
H15C	−0.3418	0.7303	0.4608	0.068*
C16	0.4485 (4)	0.6366 (2)	0.69512 (4)	0.0279 (4)
H16A	0.6223	0.6874	0.6948	0.033*
H16B	0.4916	0.5499	0.7032	0.033*
C17	0.2409 (3)	0.70291 (17)	0.71476 (4)	0.0211 (4)
C18	0.1213 (4)	0.82083 (17)	0.70690 (4)	0.0248 (4)
H18A	0.1721	0.8614	0.6888	0.030*
C19	−0.0710 (4)	0.87936 (17)	0.72517 (4)	0.0265 (4)
H19A	−0.1527	0.9593	0.7195	0.032*
C20	−0.1448 (4)	0.82127 (17)	0.75181 (4)	0.0240 (4)
C21	−0.0263 (4)	0.70515 (18)	0.75996 (4)	0.0249 (4)
H21A	−0.0741	0.6655	0.7782	0.030*
C22	0.1636 (4)	0.64649 (18)	0.74125 (4)	0.0256 (4)
H22A	0.2422	0.5657	0.7468	0.031*
C23	−0.4128 (4)	0.8321 (2)	0.79597 (4)	0.0377 (5)
H23A	−0.5467	0.8888	0.8057	0.056*
H23B	−0.2479	0.8226	0.8087	0.056*
H23C	−0.4968	0.7470	0.7926	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0107 (2)	0.01413 (19)	0.0191 (2)	0.00178 (15)	0.00027 (15)	−0.00148 (16)
F1	0.0333 (6)	0.0211 (5)	0.0239 (5)	0.0009 (4)	0.0051 (4)	0.0015 (4)
F2	0.0435 (7)	0.0242 (6)	0.0397 (7)	−0.0008 (5)	0.0191 (5)	0.0033 (5)
O1	0.0118 (6)	0.0218 (6)	0.0351 (7)	0.0009 (5)	−0.0001 (5)	−0.0011 (5)
O2	0.0124 (6)	0.0162 (5)	0.0303 (7)	0.0003 (5)	0.0012 (5)	−0.0013 (5)
O3	0.0443 (9)	0.0435 (8)	0.0298 (7)	0.0067 (7)	−0.0138 (6)	0.0067 (6)
O4	0.0346 (8)	0.0340 (7)	0.0305 (7)	0.0041 (6)	0.0107 (6)	−0.0108 (6)
N1	0.0106 (6)	0.0142 (6)	0.0238 (7)	0.0032 (5)	−0.0002 (5)	−0.0016 (5)
N2	0.0129 (7)	0.0219 (7)	0.0190 (7)	0.0054 (6)	0.0020 (5)	−0.0012 (5)
N3	0.0102 (7)	0.0240 (7)	0.0206 (7)	0.0022 (6)	−0.0012 (5)	−0.0051 (6)
C1	0.0203 (8)	0.0175 (8)	0.0226 (8)	−0.0016 (7)	−0.0030 (7)	−0.0004 (7)
C2	0.0270 (10)	0.0227 (9)	0.0328 (10)	0.0026 (7)	0.0034 (8)	−0.0066 (8)
C3	0.0338 (11)	0.0163 (8)	0.0424 (11)	0.0059 (8)	0.0006 (9)	−0.0053 (8)
C4	0.0357 (11)	0.0169 (9)	0.0398 (11)	0.0005 (8)	0.0030 (9)	0.0039 (8)
C5	0.0244 (9)	0.0212 (8)	0.0270 (9)	−0.0017 (7)	0.0028 (7)	0.0001 (7)
C6	0.0149 (8)	0.0158 (8)	0.0223 (8)	0.0015 (6)	−0.0036 (6)	−0.0024 (6)
C7	0.0160 (8)	0.0161 (7)	0.0188 (8)	0.0005 (6)	−0.0008 (6)	−0.0002 (6)
C8	0.0319 (10)	0.0351 (10)	0.0188 (9)	0.0149 (8)	0.0005 (7)	−0.0015 (7)
C9	0.0230 (9)	0.0309 (9)	0.0168 (8)	0.0090 (8)	0.0026 (7)	−0.0008 (7)
C10	0.0285 (10)	0.0278 (9)	0.0224 (9)	0.0019 (8)	0.0056 (7)	0.0003 (7)
C11	0.0244 (9)	0.0374 (10)	0.0217 (9)	−0.0014 (8)	−0.0003 (7)	−0.0016 (8)
C12	0.0280 (10)	0.0365 (11)	0.0204 (9)	0.0071 (8)	−0.0022 (7)	0.0029 (8)
C13	0.0406 (12)	0.0261 (9)	0.0287 (10)	0.0030 (9)	−0.0041 (8)	0.0003 (8)
C14	0.0288 (10)	0.0323 (10)	0.0247 (9)	0.0019 (8)	−0.0046 (8)	−0.0038 (8)
C15	0.0402 (13)	0.0649 (15)	0.0309 (11)	0.0104 (11)	−0.0167 (10)	−0.0003 (11)
C16	0.0194 (9)	0.0427 (11)	0.0215 (9)	0.0091 (8)	−0.0046 (7)	−0.0068 (8)
C17	0.0156 (8)	0.0280 (9)	0.0195 (8)	0.0000 (7)	−0.0033 (6)	−0.0066 (7)
C18	0.0268 (10)	0.0257 (9)	0.0220 (9)	−0.0027 (7)	0.0027 (7)	−0.0020 (7)
C19	0.0314 (10)	0.0179 (8)	0.0301 (10)	0.0012 (7)	0.0017 (8)	−0.0038 (7)
C20	0.0223 (9)	0.0246 (9)	0.0251 (9)	−0.0032 (7)	0.0031 (7)	−0.0112 (7)
C21	0.0252 (9)	0.0293 (9)	0.0202 (9)	−0.0045 (8)	0.0005 (7)	−0.0011 (7)
C22	0.0253 (9)	0.0264 (9)	0.0249 (9)	0.0026 (8)	−0.0038 (7)	−0.0011 (7)
C23	0.0332 (11)	0.0540 (13)	0.0259 (10)	−0.0040 (10)	0.0099 (8)	−0.0123 (9)

Geometric parameters (Å, º)

P1—O2	1.4804 (12)	C9—C10	1.383 (3)
P1—N3	1.6141 (14)	C9—C14	1.393 (3)
P1—N2	1.6263 (14)	C10—C11	1.394 (3)
P1—N1	1.7084 (14)	C10—H10A	0.9500
F1—C1	1.3558 (19)	C11—C12	1.375 (3)
F2—C5	1.352 (2)	C11—H11A	0.9500
O1—C7	1.225 (2)	C12—C13	1.396 (3)
O3—C12	1.371 (2)	C13—C14	1.379 (3)
O3—C15	1.426 (3)	C13—H13A	0.9500
O4—C20	1.369 (2)	C14—H14A	0.9500
O4—C23	1.422 (2)	C15—H15A	0.9800
N1—C7	1.355 (2)	C15—H15B	0.9800
N1—H1N	0.835 (14)	C15—H15C	0.9800
N2—C8	1.465 (2)	C16—C17	1.508 (2)
N2—H2N	0.832 (15)	C16—H16A	0.9900
N3—C16	1.461 (2)	C16—H16B	0.9900
N3—H3N	0.833 (15)	C17—C22	1.383 (3)
C1—C2	1.377 (2)	C17—C18	1.394 (2)
C1—C6	1.390 (2)	C18—C19	1.386 (2)
C2—C3	1.387 (3)	C18—H18A	0.9500
C2—H2C	0.9500	C19—C20	1.392 (3)
C3—C4	1.381 (3)	C19—H19A	0.9500
C3—H3B	0.9500	C20—C21	1.379 (3)
C4—C5	1.374 (3)	C21—C22	1.391 (3)
C4—H4A	0.9500	C21—H21A	0.9500
C5—C6	1.393 (2)	C22—H22A	0.9500
C6—C7	1.506 (2)	C23—H23A	0.9800
C8—C9	1.507 (2)	C23—H23B	0.9800
C8—H8A	0.9900	C23—H23C	0.9800
C8—H8B	0.9900
O2—P1—N3	114.12 (7)	C11—C10—H10A	119.2
O2—P1—N2	117.74 (7)	C12—C11—C10	119.32 (18)
N3—P1—N2	103.24 (7)	C12—C11—H11A	120.3
O2—P1—N1	102.89 (7)	C10—C11—H11A	120.3
N3—P1—N1	112.12 (7)	O3—C12—C11	124.92 (18)
N2—P1—N1	106.75 (7)	O3—C12—C13	115.04 (18)
C12—O3—C15	117.58 (17)	C11—C12—C13	120.04 (18)
C20—O4—C23	117.47 (16)	C14—C13—C12	119.91 (18)
C7—N1—P1	125.50 (11)	C14—C13—H13A	120.0
C7—N1—H1N	117.8 (13)	C12—C13—H13A	120.0
P1—N1—H1N	116.7 (14)	C13—C14—C9	120.98 (18)
C8—N2—P1	121.68 (12)	C13—C14—H14A	119.5
C8—N2—H2N	115.6 (14)	C9—C14—H14A	119.5
P1—N2—H2N	114.9 (13)	O3—C15—H15A	109.5
C16—N3—P1	124.33 (12)	O3—C15—H15B	109.5
C16—N3—H3N	119.7 (13)	H15A—C15—H15B	109.5
P1—N3—H3N	115.6 (13)	O3—C15—H15C	109.5
F1—C1—C2	118.34 (15)	H15A—C15—H15C	109.5
F1—C1—C6	118.26 (14)	H15B—C15—H15C	109.5
C2—C1—C6	123.37 (16)	N3—C16—C17	110.66 (14)
C1—C2—C3	118.45 (17)	N3—C16—H16A	109.5
C1—C2—H2C	120.8	C17—C16—H16A	109.5
C3—C2—H2C	120.8	N3—C16—H16B	109.5
C4—C3—C2	120.66 (17)	C17—C16—H16B	109.5
C4—C3—H3B	119.7	H16A—C16—H16B	108.1
C2—C3—H3B	119.7	C22—C17—C18	118.31 (16)
C5—C4—C3	118.72 (17)	C22—C17—C16	120.04 (16)
C5—C4—H4A	120.6	C18—C17—C16	121.65 (16)
C3—C4—H4A	120.6	C19—C18—C17	120.63 (17)
F2—C5—C4	118.95 (16)	C19—C18—H18A	119.7
F2—C5—C6	117.72 (15)	C17—C18—H18A	119.7
C4—C5—C6	123.30 (17)	C18—C19—C20	120.12 (17)
C1—C6—C5	115.48 (15)	C18—C19—H19A	119.9
C1—C6—C7	122.78 (15)	C20—C19—H19A	119.9
C5—C6—C7	121.74 (15)	O4—C20—C21	124.50 (17)
O1—C7—N1	123.24 (15)	O4—C20—C19	115.66 (16)
O1—C7—C6	121.16 (15)	C21—C20—C19	119.83 (16)
N1—C7—C6	115.60 (14)	C20—C21—C22	119.52 (17)
N2—C8—C9	110.78 (14)	C20—C21—H21A	120.2
N2—C8—H8A	109.5	C22—C21—H21A	120.2
C9—C8—H8A	109.5	C17—C22—C21	121.57 (17)
N2—C8—H8B	109.5	C17—C22—H22A	119.2
C9—C8—H8B	109.5	C21—C22—H22A	119.2
H8A—C8—H8B	108.1	O4—C23—H23A	109.5
C10—C9—C14	118.20 (17)	O4—C23—H23B	109.5
C10—C9—C8	120.57 (17)	H23A—C23—H23B	109.5
C14—C9—C8	121.22 (17)	O4—C23—H23C	109.5
C9—C10—C11	121.55 (18)	H23A—C23—H23C	109.5
C9—C10—H10A	119.2	H23B—C23—H23C	109.5
O2—P1—N1—C7	−178.00 (13)	N2—C8—C9—C10	−121.66 (18)
N3—P1—N1—C7	58.94 (15)	N2—C8—C9—C14	58.7 (2)
N2—P1—N1—C7	−53.42 (15)	C14—C9—C10—C11	0.3 (3)
O2—P1—N2—C8	74.65 (16)	C8—C9—C10—C11	−179.35 (16)
N3—P1—N2—C8	−158.61 (14)	C9—C10—C11—C12	−0.4 (3)
N1—P1—N2—C8	−40.27 (16)	C15—O3—C12—C11	−2.9 (3)
O2—P1—N3—C16	−36.82 (17)	C15—O3—C12—C13	176.60 (18)
N2—P1—N3—C16	−165.81 (15)	C10—C11—C12—O3	179.77 (17)
N1—P1—N3—C16	79.65 (16)	C10—C11—C12—C13	0.3 (3)
F1—C1—C2—C3	−178.75 (16)	O3—C12—C13—C14	−179.71 (18)
C6—C1—C2—C3	−0.8 (3)	C11—C12—C13—C14	−0.2 (3)
C1—C2—C3—C4	0.4 (3)	C12—C13—C14—C9	0.1 (3)
C2—C3—C4—C5	0.5 (3)	C10—C9—C14—C13	−0.2 (3)
C3—C4—C5—F2	−179.12 (17)	C8—C9—C14—C13	179.46 (18)
C3—C4—C5—C6	−1.1 (3)	P1—N3—C16—C17	161.36 (13)
F1—C1—C6—C5	178.20 (15)	N3—C16—C17—C22	127.33 (18)
C2—C1—C6—C5	0.2 (3)	N3—C16—C17—C18	−52.3 (2)
F1—C1—C6—C7	−0.9 (2)	C22—C17—C18—C19	−0.3 (3)
C2—C1—C6—C7	−178.90 (16)	C16—C17—C18—C19	179.36 (16)
F2—C5—C6—C1	178.79 (15)	C17—C18—C19—C20	0.6 (3)
C4—C5—C6—C1	0.7 (3)	C23—O4—C20—C21	1.1 (3)
F2—C5—C6—C7	−2.1 (2)	C23—O4—C20—C19	−178.82 (17)
C4—C5—C6—C7	179.86 (17)	C18—C19—C20—O4	179.80 (16)
P1—N1—C7—O1	−7.4 (2)	C18—C19—C20—C21	−0.1 (3)
P1—N1—C7—C6	173.02 (11)	O4—C20—C21—C22	179.35 (17)
C1—C6—C7—O1	127.57 (18)	C19—C20—C21—C22	−0.7 (3)
C5—C6—C7—O1	−51.5 (2)	C18—C17—C22—C21	−0.6 (3)
C1—C6—C7—N1	−52.8 (2)	C16—C17—C22—C21	179.76 (16)
C5—C6—C7—N1	128.14 (17)	C20—C21—C22—C17	1.1 (3)
P1—N2—C8—C9	−163.75 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.84 (1)	2.07 (2)	2.8958 (18)	169 (2)
N2—H2N···O2^ii	0.83 (2)	2.04 (2)	2.8414 (18)	163 (2)
N3—H3N···O2^ii	0.83 (2)	2.15 (2)	2.9173 (18)	153 (2)
C15—H15A···F1^iii	0.98	2.76	3.156 (2)	105
C13—H13A···O3^iv	0.95	2.49	3.390 (3)	158
C3—H3B···O2^v	0.95	2.61	3.293 (2)	129
C16—H16B···O4^vi	0.99	2.68	3.581 (2)	151

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1; (v) x, y−1, z; (vi) −x+1/2, y−1/2, −z+3/2.

(III) N-(2-chloro-2,2-difluoroacetyl)-N',N''-bis(4- methylphenyl)phosphoric triamide

Crystal data

C16H17ClF2N3O2P	F(000) = 1600
Mr = 387.75	Dx = 1.453 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 924 reflections
a = 21.164 (5) Å	θ = 2.5–24.3°
b = 5.0011 (12) Å	µ = 0.34 mm^−1
c = 33.635 (8) Å	T = 120 K
β = 95.149 (5)°	Plate, colourless
V = 3545.7 (15) Å^3	0.40 × 0.25 × 0.15 mm
Z = 8

Data collection

Bruker SMART 1000 CCD area detector diffractometer	3058 independent reflections
Radiation source: fine-focus sealed tube	1614 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.111
phi and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −24→24
Tmin = 0.903, Tmax = 0.950	k = −5→5
16802 measured reflections	l = −39→39

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.197	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0901P)^2] where P = (Fo^2 + 2Fc^2)/3
3058 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.54 e Å^−3
3 restraints	Δρmin = −0.44 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cl1	1.07693 (9)	0.1339 (5)	0.50628 (5)	0.0667 (7)
P1	1.11556 (7)	0.1608 (3)	0.64991 (4)	0.0193 (4)
F1	1.17528 (16)	0.4191 (6)	0.51375 (9)	0.0340 (9)
F2	1.1879 (2)	0.0143 (7)	0.53346 (11)	0.0533 (12)
O1	1.13291 (19)	0.5481 (7)	0.58314 (11)	0.0304 (10)
O2	1.11008 (17)	−0.1113 (6)	0.66623 (10)	0.0211 (9)
N1	1.1313 (2)	0.1096 (8)	0.60159 (13)	0.0255 (11)
H1	1.128 (3)	−0.047 (6)	0.5915 (15)	0.031*
N2	1.1705 (2)	0.3488 (9)	0.67132 (14)	0.0252 (11)
H2	1.155 (2)	0.498 (7)	0.6769 (16)	0.030*
N3	1.0536 (2)	0.3520 (8)	0.64951 (13)	0.0195 (10)
H3	1.057 (3)	0.517 (4)	0.6529 (15)	0.023*
C1	1.1362 (3)	0.3080 (11)	0.57531 (16)	0.0250 (13)
C2	1.1476 (3)	0.2237 (11)	0.53266 (16)	0.0259 (14)
C3	1.2329 (2)	0.2702 (10)	0.68457 (15)	0.0202 (13)
C4	1.2661 (3)	0.4174 (12)	0.71479 (16)	0.0292 (14)
H4	1.2468	0.5632	0.7258	0.035*
C5	1.3272 (3)	0.3502 (14)	0.72854 (18)	0.0395 (16)
H5	1.3489	0.4564	0.7479	0.047*
C6	1.3573 (3)	0.1284 (14)	0.71425 (18)	0.0365 (16)
C7	1.3234 (3)	−0.0177 (13)	0.68427 (18)	0.0363 (16)
H7	1.3424	−0.1670	0.6739	0.044*
C8	1.2631 (3)	0.0502 (11)	0.66942 (17)	0.0303 (15)
H8	1.2423	−0.0513	0.6491	0.036*
C9	1.4224 (3)	0.0471 (16)	0.7311 (2)	0.058 (2)
H9A	1.4515	0.1916	0.7282	0.087*
H9B	1.4358	−0.1070	0.7171	0.087*
H9C	1.4216	0.0045	0.7589	0.087*
C10	0.9932 (2)	0.2677 (10)	0.63021 (16)	0.0200 (13)
C11	0.9670 (3)	0.4022 (11)	0.59698 (17)	0.0288 (14)
H11	0.9888	0.5430	0.5864	0.035*
C12	0.9081 (3)	0.3269 (14)	0.57938 (17)	0.0384 (16)
H12	0.8901	0.4218	0.5574	0.046*
C13	0.8753 (3)	0.1132 (13)	0.59379 (18)	0.0367 (16)
C14	0.9029 (3)	−0.0193 (12)	0.62645 (19)	0.0348 (16)
H14	0.8816	−0.1633	0.6365	0.042*
C15	0.9619 (3)	0.0533 (12)	0.64529 (17)	0.0287 (14)
H15	0.9796	−0.0404	0.6674	0.034*
C16	0.8104 (3)	0.0371 (15)	0.5755 (2)	0.0493 (19)
H16A	0.8099	−0.1495	0.5687	0.074*
H16B	0.8002	0.1411	0.5518	0.074*
H16C	0.7797	0.0709	0.5942	0.074*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0572 (13)	0.1051 (18)	0.0372 (10)	−0.0479 (12)	0.0011 (9)	−0.0163 (11)
P1	0.0193 (8)	0.0126 (7)	0.0254 (8)	−0.0012 (6)	−0.0004 (6)	0.0007 (7)
F1	0.045 (2)	0.0230 (19)	0.0357 (19)	−0.0062 (16)	0.0125 (16)	0.0041 (15)
F2	0.091 (3)	0.031 (2)	0.042 (2)	0.024 (2)	0.027 (2)	0.0010 (18)
O1	0.045 (3)	0.007 (2)	0.039 (3)	−0.0011 (18)	0.0058 (19)	−0.0035 (18)
O2	0.033 (2)	0.0052 (19)	0.026 (2)	0.0001 (15)	0.0058 (16)	0.0044 (15)
N1	0.039 (3)	0.009 (2)	0.029 (3)	−0.001 (2)	0.003 (2)	0.003 (2)
N2	0.023 (3)	0.014 (2)	0.038 (3)	−0.005 (2)	−0.001 (2)	−0.005 (2)
N3	0.021 (3)	0.007 (2)	0.030 (3)	0.000 (2)	−0.0009 (19)	−0.002 (2)
C1	0.026 (3)	0.021 (3)	0.028 (3)	−0.002 (3)	0.004 (2)	0.004 (3)
C2	0.032 (4)	0.015 (3)	0.032 (3)	−0.010 (3)	0.009 (3)	−0.001 (3)
C3	0.013 (3)	0.023 (3)	0.025 (3)	0.003 (2)	0.003 (2)	0.008 (2)
C4	0.026 (4)	0.029 (4)	0.032 (3)	0.000 (3)	−0.001 (3)	−0.001 (3)
C5	0.033 (4)	0.052 (4)	0.033 (4)	−0.014 (3)	0.003 (3)	−0.003 (3)
C6	0.019 (3)	0.055 (5)	0.035 (4)	−0.004 (3)	0.000 (3)	0.013 (3)
C7	0.029 (4)	0.036 (4)	0.044 (4)	0.006 (3)	0.009 (3)	0.010 (3)
C8	0.026 (4)	0.026 (3)	0.039 (4)	0.002 (3)	0.004 (3)	−0.007 (3)
C9	0.030 (4)	0.079 (6)	0.064 (5)	0.003 (4)	−0.003 (4)	0.026 (4)
C10	0.017 (3)	0.012 (3)	0.031 (3)	0.003 (2)	0.002 (2)	−0.001 (2)
C11	0.025 (3)	0.022 (3)	0.039 (4)	0.001 (3)	0.005 (3)	0.009 (3)
C12	0.032 (4)	0.050 (4)	0.031 (3)	0.001 (3)	−0.005 (3)	0.007 (3)
C13	0.029 (4)	0.044 (4)	0.038 (4)	−0.003 (3)	0.009 (3)	−0.010 (3)
C14	0.022 (4)	0.036 (4)	0.048 (4)	−0.008 (3)	0.008 (3)	−0.003 (3)
C15	0.027 (4)	0.031 (3)	0.029 (3)	−0.002 (3)	0.008 (3)	0.002 (3)
C16	0.024 (4)	0.067 (5)	0.058 (5)	−0.006 (3)	0.007 (3)	−0.017 (4)

Geometric parameters (Å, º)

Cl1—C2	1.729 (6)	C6—C9	1.498 (8)
P1—O2	1.475 (4)	C7—C8	1.370 (8)
P1—N2	1.615 (5)	C7—H7	0.9300
P1—N3	1.622 (4)	C8—H8	0.9300
P1—N1	1.707 (5)	C9—H9A	0.9600
F1—C2	1.330 (6)	C9—H9B	0.9600
F2—C2	1.350 (6)	C9—H9C	0.9600
O1—C1	1.233 (6)	C10—C15	1.381 (7)
N1—C1	1.339 (7)	C10—C11	1.377 (7)
N1—H1	0.86 (2)	C11—C12	1.384 (8)
N2—C3	1.410 (7)	C11—H11	0.9300
N2—H2	0.85 (2)	C12—C13	1.385 (9)
N3—C10	1.443 (7)	C12—H12	0.9300
N3—H3	0.84 (2)	C13—C14	1.368 (8)
C1—C2	1.535 (8)	C13—C16	1.503 (8)
C3—C8	1.392 (7)	C14—C15	1.396 (8)
C3—C4	1.394 (7)	C14—H14	0.9300
C4—C5	1.374 (8)	C15—H15	0.9300
C4—H4	0.9300	C16—H16A	0.9600
C5—C6	1.387 (9)	C16—H16B	0.9600
C5—H5	0.9300	C16—H16C	0.9600
C6—C7	1.391 (8)
O2—P1—N2	116.7 (2)	C8—C7—C6	122.4 (6)
O2—P1—N3	117.1 (2)	C8—C7—H7	118.8
N2—P1—N3	102.1 (2)	C6—C7—H7	118.8
O2—P1—N1	104.2 (2)	C7—C8—C3	120.4 (6)
N2—P1—N1	108.5 (2)	C7—C8—H8	119.8
N3—P1—N1	107.9 (2)	C3—C8—H8	119.8
C1—N1—P1	123.4 (4)	C6—C9—H9A	109.5
C1—N1—H1	115 (4)	C6—C9—H9B	109.5
P1—N1—H1	120 (4)	H9A—C9—H9B	109.5
C3—N2—P1	126.5 (4)	C6—C9—H9C	109.5
C3—N2—H2	123 (4)	H9A—C9—H9C	109.5
P1—N2—H2	109 (4)	H9B—C9—H9C	109.5
C10—N3—P1	120.9 (3)	C15—C10—C11	120.4 (5)
C10—N3—H3	114 (4)	C15—C10—N3	119.8 (5)
P1—N3—H3	122 (4)	C11—C10—N3	119.9 (5)
O1—C1—N1	124.8 (5)	C10—C11—C12	119.7 (5)
O1—C1—C2	118.9 (5)	C10—C11—H11	120.1
N1—C1—C2	116.2 (5)	C12—C11—H11	120.1
F1—C2—F2	106.0 (4)	C13—C12—C11	121.4 (6)
F1—C2—C1	111.0 (4)	C13—C12—H12	119.3
F2—C2—C1	110.3 (5)	C11—C12—H12	119.3
F1—C2—Cl1	110.1 (4)	C14—C13—C12	117.6 (6)
F2—C2—Cl1	109.0 (4)	C14—C13—C16	121.0 (6)
C1—C2—Cl1	110.5 (4)	C12—C13—C16	121.3 (6)
C8—C3—C4	117.7 (5)	C13—C14—C15	122.6 (6)
C8—C3—N2	123.6 (5)	C13—C14—H14	118.7
C4—C3—N2	118.7 (5)	C15—C14—H14	118.7
C5—C4—C3	121.0 (6)	C10—C15—C14	118.3 (5)
C5—C4—H4	119.5	C10—C15—H15	120.8
C3—C4—H4	119.5	C14—C15—H15	120.8
C4—C5—C6	121.8 (6)	C13—C16—H16A	109.5
C4—C5—H5	119.1	C13—C16—H16B	109.5
C6—C5—H5	119.1	H16A—C16—H16B	109.5
C5—C6—C7	116.6 (6)	C13—C16—H16C	109.5
C5—C6—C9	121.4 (6)	H16A—C16—H16C	109.5
C7—C6—C9	121.9 (7)	H16B—C16—H16C	109.5
O2—P1—N1—C1	176.1 (4)	C3—C4—C5—C6	−2.7 (9)
N2—P1—N1—C1	−58.9 (5)	C4—C5—C6—C7	2.2 (9)
N3—P1—N1—C1	51.0 (5)	C4—C5—C6—C9	−176.3 (6)
O2—P1—N2—C3	41.3 (5)	C5—C6—C7—C8	−0.4 (9)
N3—P1—N2—C3	170.4 (4)	C9—C6—C7—C8	178.0 (6)
N1—P1—N2—C3	−75.8 (5)	C6—C7—C8—C3	−0.9 (9)
O2—P1—N3—C10	−55.5 (5)	C4—C3—C8—C7	0.5 (8)
N2—P1—N3—C10	175.7 (4)	N2—C3—C8—C7	−178.7 (5)
N1—P1—N3—C10	61.5 (4)	P1—N3—C10—C15	66.1 (6)
P1—N1—C1—O1	3.3 (8)	P1—N3—C10—C11	−114.2 (5)
P1—N1—C1—C2	−177.4 (4)	C15—C10—C11—C12	2.0 (8)
O1—C1—C2—F1	23.3 (7)	N3—C10—C11—C12	−177.7 (5)
N1—C1—C2—F1	−156.1 (5)	C10—C11—C12—C13	−1.8 (9)
O1—C1—C2—F2	140.4 (5)	C11—C12—C13—C14	0.8 (9)
N1—C1—C2—F2	−39.0 (7)	C11—C12—C13—C16	178.0 (6)
O1—C1—C2—Cl1	−99.1 (5)	C12—C13—C14—C15	0.0 (9)
N1—C1—C2—Cl1	81.5 (5)	C16—C13—C14—C15	−177.1 (6)
P1—N2—C3—C8	23.2 (8)	C11—C10—C15—C14	−1.1 (8)
P1—N2—C3—C4	−156.0 (4)	N3—C10—C15—C14	178.6 (5)
C8—C3—C4—C5	1.3 (8)	C13—C14—C15—C10	0.1 (9)
N2—C3—C4—C5	−179.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86 (2)	2.05 (3)	2.877 (6)	163 (5)
N2—H2···O2^ii	0.85 (2)	2.19 (3)	2.986 (6)	158 (5)
N3—H3···O2^ii	0.84 (2)	2.20 (3)	2.972 (5)	153 (5)

Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z.