The double H-atom acceptability of the P=O group in new XP(O)(NHCH₂C₆H₄-2-Cl)₂ phosphor­amidates [X = C₆H₅O- and CF₃C(O)NH-]: a database analysis of compounds having a P(O)(NHR) group

In the hydrogen-bond patterns of phenyl bis­(2-chloro­benzyl­amido)phosphinate, C₂₀H₁₉Cl₂N₂O₂P, (I), and N,N'-bis­(2-chloro­benzyl)-N''-(2,2,2-trifluoro­acetyl)phosphoric triamide, C₁₆H₁₅Cl₂F₃N₃O₂P, (II), the O atoms of the related phosphoryl groups act as double H-atom acceptors, so that the P=O...(H-N)₂ hydrogen bond in (I) and the P=O...(H-N_amide)₂ and C=O...H-N_C(O)NHP(O) hydrogen bonds in (II) are responsible for the aggregation of the mol­ecules in the crystal packing. The presence of a double H-atom acceptor centre is a result of the involvement of a greater number of H-atom donor sites with a smaller number of H-atom acceptor sites in the hydrogen-bonding inter­actions. This article also reviews structures having a P(O)NH group, with the aim of finding similar three-centre hydrogen bonds in the packing of phospho­ramidate compounds. This analysis shows that the factors affecting the preference of the above-mentioned O atom to act as a double H-atom acceptor are: (i) a higher number of H-atom donor sites relative to H-atom acceptor centres in mol­ecules with P(=O)(NH)₃, (N)P(=O)(NH)₂, C(=O)NHP(=O)(NH)₂ and (NH)₂P(=O)OP(=O)(NH)₂ groups, and (ii) the remarkable H-atom acceptability of this atom relative to the other acceptor centre(s) in mol­ecules containing an OP(=O)(NH)₂ group, with the explanation that the N atom bound to the P atom in almost all of the structures found does not take part in hydrogen bonding as an acceptor. Moreover, the differences in the H-atom acceptability of the phosphoryl O atom relative to the O atom of the alk­oxy or phen­oxy groups in amido­phospho­ric acid esters may be illustrated by considering the mol­ecular packing of com­pounds having (O)₂P(=O)(NH) and (O)P(=O)(NH)(N)groups, in which the unique N-H unit in the above-mentioned mol­ecules almost always selects the phosphoryl O atom as a partner in forming hydrogen-bond inter­actions. The P atoms in (I) and (II) are in tetra­hedral coordination environments, and the phosphoryl and carbonyl groups in (II) are anti with respect to each other (the P and C groups are separated by one N atom). In the crystal structures of (I) and (II), adjacent mol­ecules are linked via the above-mentioned hydrogen bonds into a linear arrangement parallel to [100] in both cases, in (I) by forming R₂²(8) rings and in (II) through a combination of R₂²(10) and R₂¹(6) rings.

S1. Comment

A three-centred (D—H)₂···A hydrogen bond is formed when two H-atom donor sites both interact with a single acceptor which is called a double H-atom acceptor (Steiner, 2002). The term `bifurcated' is commonly used to describe another type of three-centred hydrogen bond, viz. D—H···(A)₂ (Steiner, 2002). To predict the hydrogen-bond pattern of a molecule with more H-atom donor sites than H-atom acceptor sites, one would anticipate that some H-atom acceptors would be suitable to act as double H-atom acceptors. Of course, the positions of the H-atom acceptors and H-atom donors and their relative directionalities are important too. Moreover, if the H-atom acceptabilities of the two H-atom acceptor centres in a molecule are very different, the better H-atom acceptor may act as a double H-atom acceptor. In such cases, the competing hydrogen bonds involved in the three-centred hydrogen bond may reduce the strength of each other.

In this paper, the syntheses and crystal structures of phenyl bis(2-chlorobenzylamido)phosphinate, C₆H₅OP(O)(NHCH₂C₆H₄-2-Cl)₂, (I), and N,N'-bis(2-chlorobenzyl)-N''-(2,2,2-trifluoroacetyl)phosphoric triamide, CF₃C(O)NHP(O)(NHCH₂C₆H₄-2-Cl)₂, (II), are reported. Their molecular structures are shown in Figs. 1 and 2, respectively. Additionally, we have attempted to analyse the three-centred hydrogen bonds in (I) and (II) and in analogous phosphorus compounds of the formula XP(O)(NHR)₂ with CIFs deposited in the Cambridge Structural Database (CSD, Version 5.32, May 2011 update; Allen, 2002) and papers published recently in IUCr journals. Either X is OR' (R' ≠ H) or NR¹R², i.e. these are compounds having a P(O)(NH)₃, (N)P(O)(NH)₂ or OP(O)(NH)₂ skeleton, or X is a group containing both H-atom donor and acceptor sites such as R'C(O)NH or (NHR)₂P(O)O in compounds with a C(O)NHP(O)(NH)₂ or (NH)₂P(O)OP(O)(NH)₂ fragment.

Usually in phosphoramidates, no N atom bonded to phosphorus takes part in any hydrogen bond as an acceptor, showing its low Lewis base character. A search of the CSD revealed one phosphoramidate molecular packing (belonging to the diazaphosphorinane family) containing a very weak N—H···N—P hydrogen bond (CSD refcode HESCEO; Gholivand et al., 2006). In most cases, the N atom has a nearly planar environment (Toghraee et al., 2011). Of course, the N-atom environment of some substituents, such as aziridine, for example in NH₂P(O)[NCH₂C(CH₃)₂]₂ (GOMDOB; Hempel et al., 1999), shows some deviation from planarity, but such an N atom does not cooperate in hydrogen-bonding interactions as an acceptor. Moreover, the O atom of the phenoxy and alkoxy groups in the 49 structures with an (O)P(═O)(NH)(N) skeleton [for example, (4-CH₃–C₆H₄O)P(O)(NHC₆H₄-4-CH₃)₂; GUDGIW; Ghadimi et al., 2009) does not cooperate in hydrogen-bond interactions, as it cannot compete with the phosphoryl O atom to accept an H atom from the unique H-atom donor site in the molecule.

Focusing on the (O)(O)P(═O)(NH) skeleton in the 104 related deposited structures, only the structure of (CH₃O)₂P(O)[NHCH{CH(CH₃)[OC(O)CH₃]}{C(O)[C(NN)(COOC₂H₅]}] (IJUMAB; Sa et al., 2003) shows N—H···O(CH₃) and not N—H···O(P) hydrogen bonding. Thus, this skeleton almost always has one H-atom acceptor (the O atom of the phosphorylgroup ) and one H-atom donor site, both in the P(O)NH group. In this study, there were a few structures that were not included because their CIFs were unavailable; hydrated (or solvated with a protic solvent) molecules were also excluded.

The O atom of the OR group in some examples of compounds with a higher number of H-atom donor sites, such as compounds containing an (O)P(═O) (NH)(NH) skeleton, has a lower H-atom acceptability than the phosphoryl O atom, enforcing involvement in the hydrogen-bond interaction (MUBPIJ; Pourayoubi et al., 2009) (Fig. 3).

In some cases, the better H-atom acceptability of the O atom of P═O relative to the RO group, e.g. (NHC₆H₁₁)(NHC₆H₄-4-CH₃) (ERUFIH; Sabbaghi, Pourayoubi, Karimi Ahmadabad & Parvez, 2011), leads it to act as a double H-atom acceptor (Fig. 4), similar to what is observed in the crystal packing of (I) (Fig. 5). For example, in the molecular packing of (C₆H₅O)P(O)(NHC₆H₁₁)₂.CH₃OH (HIVLOO; Gholivand et al., 2008), a linear arrangement is formed through a P(O)(···H—O)(H—N) group, where the P(O) group acts as a double H-atom acceptor and the OH unit belongs to the methanol solvent molecule. In the two-dimensional hydrogen-bonded arrangement of diazaphosphorinanes 4-CH₃C₆H₄OP(O)X (X is NHCH₂CH₂CH₂NH; KIVXIX; [Reference?]) and C₆H₅OP(O)Y [Y is NHCH₂C(CH₃)₂CH₂NH; KIVXOD; Gholivand, Shariatinia et al., 2007], the P(O) functions as a double H-atom acceptor (Gholivand, Shariatinia et al., 2007).

In other cases, both O atoms are involved in hydrogen-bond interactions with the two N—H units [or the other H-atom donor site(s) in the molecule or in the crystal structure], forming hydrogen bonds with different strengths in which the P(O) cooperates in a stronger hydrogen bond. For example, in the crystal packing of (4-CH₃-C₆H₄O)P(O)(NHC₆H₄-4-CH₃)₂ (MUBPIJ), N···O(P) = 2.805 (2) and N···O(C₆H₅) = 3.068 (2) Å, while in C₆H₅OP(O)(NHC₆H₄-4-CH₃)(NHCH₂C₆H₅) [Pourayoubi, Karimi Ahmadabad & Nečas (2011)], these distances are 2.761 (3) and 3.127 (3) Å, respectively.

In the crystal packing of compounds with the general formula (R¹O)P(O)(NHR²)₂, both linear and two-dimensional hydrogen-bonded arrangements are observed; for example, C₆H₅OP(O)(NHC₆H₁₁)₂.CH₃OH (HIVLOO; Gholivand et al., 2008), 4-CH₃-C₆H₄OP(O)(NHC₆H₄-4-CH₃)₂ (MUBPIJ; Pourayoubi et al., 2009), 4-CH₃-C₆H₄OP(O)(NHC₆H₄-2-CH₃)₂ (YUPVEL; Sabbaghi et al., 2010) and 4-CH₃-C₆H₄OP(O)X [X is NHCH₂C(CH₃)₂CH₂NH; NIBNOC; Gholivand, Pourayoubi & Shariatinia, 2007] exist as linear hydrogen-bonded arrangements, whereas a two-dimensional array is found, for instance, in 4-CH₃-C₆H₄OP(O)X (X is NHCH₂CH₂CH₂NH; KIVXIX; [Reference?]), C₆H₅OP(O)X [X is NHCH₂C(CH₃)₂CH₂NH; KIVXOD), (C₆H₅O)P(O)(NH₂)₂ (PPOSAM; Bullen & Dann, 1973) and C₆H₅OP(O)X [X is NHNHP(O)(OC₆H₅)NHNH; FIMVUS; Engelhardt & Franzmann, 1987].

For (I), single crystals were obtained at room temperature from a mixture of CH₃OH and CH₃CN. The P atom exhibits a distorted tetrahedral environment, as has been noted for other amidophosphoric acid esters (Sabbaghi et al., 2010). This distortion is illustrated by the bond angles at the P atom [in the range 97.42 (7)–119.79 (7)°] and the bond lengths in the P(═ O)(O)(N)₂ skeleton (Table 1). The C—O bond length and the P—N—C and P—O—C angles are within the expected values (Sabbaghi, Pourayoubi, Karimi Ahmadabad & Parvez, 2011).

The molecules of (I) are linked by two intermolecular N—H···OP hydrogen bonds (Table 2) into a one-dimensional arrangement in the direction of the a axis, in which the O atom of the P═O group acts as a double H-atom acceptor (Steiner, 2002) (Fig. 5). From this arrangement, R₂²(8) rings are formed (Bernstein et al., 1995).

Similar cases are observed in compounds containing an (N)P(═O)(NH)(NH) moiety [MIFYIJ (Gholivand et al., 2002) and IKASAP (Sabbaghi, Pourayoubi, Karimi Ahmadabad, Azarkamanzad et al., 2011)], where `one H-atom acceptor and two H-atom donor' sites exist in the molecules (the N atoms are not involved in hydrogen bonding as H-atom acceptors). In [N(CH₃)(C₆H₁₁)]P(O)(NHC₅H₄-2-N)₂ (HIVLII; Gholivand et al., 2008), the pyridine N atom is involved in one of the N—H units in an intramolecular hydrogen bond, whereas the other N—H unit cooperates in the P(O)···H—N hydrogen bond.

Compound (II) (Fig. 2) is an example of a compound containing two H-atom acceptor and three H-atom donor sites; all of these sites exist in the C(O)NHP(O)(NH)₂ skeleton of the molecule. Single crystals were obtained at room temperature from a mixture of C₂H₅OH and CH₃CN. As has been noted in a recently published paper by Toghraee et al. (2011), and similar to the amidophosphoric acid esters, the N atoms are not involved as H-atom acceptors in hydrogen-bond interactions. Similar to all reported acyclic phosphoric triamides containing a C(O)NHP(O)(NH)₂ skeleton, the C(O) adopts an anti orientation with respect to P(O) (although the P and C groups are separated by an N atom). Of course, in the diazaphosphorinanes containing a similar skeleton, a gauche position was observed (Toghraee et al., 2011).

The tetrahedral P(═O)(N)(N)₂ environment is distorted, and the P═O, C═O and P—N bond lengths and C—N—P angles are within the expected ranges (Pourayoubi, Karimi Ahmadabad & Nečas, 2011 or Pourayoubi, Padělková et al., 2011 or Pourayoubi, Tarahhomi et al., 2011 ?; Tarahhomi et al., 2011). The O—P—N—C torsion angle in the C(O)NHP(O) group is within the expected range for analogous compounds having an anti orientation of P(O) with respect to C(O). As expected, the P—N bonds in the P(O)(NH-CH₂C₆H₄-2-Cl)₂ group are shorter than the P—N bond in the C(═O)NHP(═O) fragment (Table 3).

In the crystal packing of (II), adjacent molecules are linked via N_C(O)NHP(O)—H···O(C) hydrogen bonds and also through two different N_amide—H···O(P) hydrogen bonds involving the same pair of molecules (Table 4), building R₂²(10) rings combined with R₂¹(6) rings (Fig. 6) in a linear arrangement parallel to [100]. This means that, in this structure, the phosphoryl group acts as a double hydrogen-bond acceptor to form a P═O(···H—N_amide)₂ group.

For compounds of the formula RC(O)NHP(O)(NHR')₂, the two H-atom donors [H—N_C(O)NHP(O) and one of the H—NR'] participate with the two O atoms in the intermolecular hydrogen bonding; the other H—NR' may make one of three choices: (i) cooperation in an additional hydrogen bond with P(O) as in the above-mentioned three-centred hydrogen bond; (ii) involvement in an intramolecular hydrogen bond with C(O); or (iii) no cooperation in any hydrogen bond.

With an (NH)₂P(O)OP(O)(NH)₂ skeleton, the structure of one neutral molecule has been reported [OXPOTU (Cameron et al., 1978) and OXPOTU01 (Pourayoubi, Padělková et al., 2011) [Text missing?] atom acceptor to form one inter- and one intramolecular N—H···O hydrogen bond.

In summary, the CIF files of all published compounds with the (N)P(═ O)(NH)₂, (O)P(═O)(NH)₂, (O)₂P(═O)(NH), (O)P(═O)(NH)(N), C(═O)NHP(═O)(NH)₂, P(═O)(NH)₃ and P(═O)NHP(═O)(NH)₂ skeletons (belonging to phosphoramidate compounds) were investigated and the following `empirical rules' were obtained. (i) In virtually none of the reported structures does the N atom cooperate in a hydrogen-bond interaction as an acceptor. There is only one example of a hydrogen bond of the type N—H···N—P (N···N distance more than 3.2 Å). (ii) In almost all compounds having the (O)₂P(═O)(NH) and (O)P(═O)(NH)(N) skeletons, the O atom of the phenoxy group does not cooperate in a hydrogen bond interaction, as it cannot compete with the phosphoryl O atom as an H-atom acceptor from the single H-atom donor site in the molecule. There is only one example of a hydrogen bond of the type N—H···O(R)—P in this family of compounds in one compound containing some H-atom acceptor centres in addition to one phosphoryl group. (iii) The O atom of the OR group in some examples of compounds with higher numbers of H-atom donor sites than H-atom acceptor centres, such as compounds containing an (O)P(═O)(NH)₂ skeleton, even though it has a lower H-atom acceptability than the phosphoryl O atom, is forced to be involved in a hydrogen-bond interaction. (iv) In compounds having an (O)P(═O)(NH)₂ skeleton, the better H-atom acceptability of the phosphoryl O atom compared with the RO group leads it to act in some cases as a double H-atom acceptor. (v) In compounds having a C(═O)NHP(═ O)(NH)₂ skeleton containing two H-atom acceptor and three H-atom donor centres, two H-atom donors [H—N_C(O)NHP(O) and one of the H—NR'] participate with the two O atoms in intermolecular hydrogen bonds, while the other H—NR' may act in one of the three following ways: (a) involved in an additional hydrogen bond with P(O), (b) cooperating in an intramolecular hydrogen bond with C(O), and (c) not cooperating in any hydrogen bond. (vi) In the crystal packing of (II), the C(═ O)···H—N_C(O)NHP(O) hydrogen bond and a P(═O)···(H—N_amide)₂ group are responsible for the aggregation of the molecules. This type of aggregation, a combination of R₂²(10) and R₂¹(6) rings, has been observed for a few structures having a C(O)NHP(O)(NH)₂ skeleton. The other hydrogen-bond pattern is alternating R₂²(8) and R₂²(12) motifs [formed through pairs of P(═ O)···(H—N_C(O)NHP(O) and pairs of C(═O)···H—N_amide hydrogen bonds, respectively]. The R₂²(12) loop may also be accompanied by R₂¹(6) or S₆ rings.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Bullen & Dann (1973); Cameron et al. (1978); Engelhardt & Franzmann (1987); Ghadimi et al. (2009); Gholivand et al. (2002, 2006, 2008); Gholivand, Pourayoubi & Shariatinia (2007); Gholivand, Shariatinia, Mahzouni & Amiri (2007); Hempel et al. (1999); Narula et al. (1999); Pourayoubi et al. (2009); Pourayoubi, Karimi Ahmadabad & Nečas (2011); Pourayoubi, Padělková, Rostami Chaijan & Růžička (2011); Sa et al. (2003); Sabbaghi et al. (2010); Sabbaghi, Pourayoubi, Karimi Ahmadabad & Parvez (2011); Sabbaghi, Pourayoubi, Karimi Ahmadabad, Azarkamanzad & Ebrahimi Valmoozi (2011); Steiner (2002); Tarahhomi et al. (2011); Toghraee et al. (2011).

S2. Experimental

CF₃C(O)NHP(O)Cl₂ was prepared according to the procedure reported by Narula et al. (1999). Compound (I) was synthesized from the reaction of phenyl dichlorophosphate (2.507 mmol) and 2-chlorobenzylamine (10.028 mmol) in chloroform (30 ml). After stirring for 4 h at 273 K, the solvent was evaporated in a vacuum and the solid obtained was washed with distilled water. Single crystals of (I) suitable for X-ray crystallography were obtained from a mixture of CH₃OH and CH₃CN [Solvent ratio?] by slow evaporation at room temperature. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3262, 3176, 2915, 1581, 1486, 1201, 1115, 1030, 916, 745, 683. Compound (II) was synthesized by a similar method to that for (I), but using CF₃C(O)NHP(O)Cl₂ instead of C₆H₅OP(O)Cl₂. Single crystals of (II) suitable for X-ray crystallography were obtained from a mixture of C₂H₅OH and CH₃CN [Solvent ratio?] by slow evaporation at room temperature. Spectroscopic analysis: IR (KBr, ν, cm^-1): 3257, 2904, 1725, 1482, 1410, 1315, 1205, 1162, 1076, 1043, 900, 790, 761, 690.

S3. Refinement

For (I) and (II), carbon-bound H atoms were placed at calculated positions and refined as riding, with C—H = 0.95–0.99 Å [Please confirm added text] and with U_iso = 1.2U_eq(C). Nitrogen-bound H atoms were located in difference Fourier maps and refined isotropically, with N—H restrained to 0.88 (1) Å and with U_iso = 1.2U_eq(N).

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The molecular structure and atom-labelling scheme for (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure and atom-labelling scheme for (II). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Cooperation of the O atoms of both P(═O) and RO groups in the hydrogen-bond pattern.
	Fig. 4. The role of the P(═O) O atom as a double H-atom acceptor.
	Fig. 5. The phosphoryl O atom as a double H-atom acceptor in the hydrogen-bond pattern of (I). C-bound H atoms have been omitted for clarity.
	Fig. 6. Part of the crystal packing of (II), with the hydrogen bonds shown as dotted lines. C-bound H atoms have been omitted for clarity.

(I) phenyl bis(2-chlorobenzylamido)phosphinate

Crystal data

C20H19Cl2N2O2P	Z = 2
Mr = 421.24	F(000) = 436
Triclinic, P1	Dx = 1.434 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4673 (4) Å	Cell parameters from 4268 reflections
b = 10.4338 (5) Å	θ = 3.1–27.7°
c = 12.9911 (6) Å	µ = 0.43 mm^−1
α = 86.215 (4)°	T = 120 K
β = 79.611 (4)°	Block, colourless
γ = 78.588 (4)°	0.50 × 0.40 × 0.40 mm
V = 975.41 (8) Å^3

Data collection

Oxford Xcalibur Sapphire2 (large Be window) diffractometer	3429 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2750 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 8.4353 pixels mm^-1	θmax = 25.0°, θmin = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −12→11
Tmin = 0.952, Tmax = 1.000	l = −15→15
6980 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0385P)^2] where P = (Fo^2 + 2Fc^2)/3
3429 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.25 e Å^−3
2 restraints	Δρmin = −0.35 e Å^−3

Special details

Experimental. The planes for (I)

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 2.8116 (0.0133) x - 1.6988 (0.0147) y + 10.8576 (0.0110) z = 4.6736 (0.0072) * 0.0000 (0.0000) P1 * 0.0000 (0.0000) N1 * 0.0000 (0.0000) C7 - 0.3007 (0.0175) H1N Rms deviation of fitted atoms = 0.0000

3.2283 (0.0114) x + 10.0787 (0.0056) y + 2.3930 (0.0213) z = 2.9534 (0.0122) A ngle to previous plane (with approximate e.s.d.) = 80.20 (0.13) * 0.0000 (0.0000) P1 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) C14 - 0.5190 (0.0149) H2N Rms deviation of fitted atoms = 0.0000

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	0.23555 (7)	0.60643 (4)	0.61964 (4)	0.03232 (15)
Cl2	−0.00509 (7)	0.12839 (5)	0.91439 (4)	0.02975 (14)
P1	0.20680 (6)	0.10787 (4)	0.50088 (4)	0.01715 (13)
O1	0.28331 (15)	−0.03432 (10)	0.49310 (9)	0.0196 (3)
O2	0.16562 (15)	0.17136 (11)	0.38923 (9)	0.0204 (3)
N1	0.34604 (19)	0.17932 (14)	0.54811 (12)	0.0195 (3)
H1N	0.4553 (15)	0.1345 (15)	0.5417 (14)	0.023*
N2	0.00087 (19)	0.15788 (14)	0.56807 (11)	0.0184 (3)
H2N	−0.0865 (18)	0.1405 (16)	0.5425 (13)	0.022*
C1	0.2927 (2)	0.14886 (15)	0.29585 (14)	0.0183 (4)
C2	0.4826 (2)	0.13689 (16)	0.29153 (14)	0.0224 (4)
H2	0.5328	0.1395	0.3534	0.027*
C3	0.5971 (3)	0.12107 (17)	0.19450 (15)	0.0264 (5)
H3	0.7273	0.1127	0.1901	0.032*
C4	0.5251 (3)	0.11725 (18)	0.10446 (15)	0.0292 (5)
H4	0.6052	0.1065	0.0387	0.035*
C5	0.3353 (3)	0.12917 (18)	0.11041 (15)	0.0291 (5)
H5	0.2849	0.1265	0.0486	0.035*
C6	0.2193 (3)	0.14503 (16)	0.20657 (14)	0.0231 (4)
H6	0.0892	0.1533	0.2108	0.028*
C7	0.3207 (2)	0.31962 (16)	0.56349 (13)	0.0191 (4)
H7A	0.1934	0.3618	0.5543	0.023*
H7B	0.4086	0.3574	0.5094	0.023*
C8	0.3512 (2)	0.34955 (17)	0.67069 (14)	0.0181 (4)
C9	0.3161 (2)	0.47862 (17)	0.70343 (14)	0.0227 (4)
C10	0.3404 (3)	0.5090 (2)	0.80175 (16)	0.0307 (5)
H10	0.3139	0.5974	0.8224	0.037*
C11	0.4034 (3)	0.4094 (2)	0.86929 (16)	0.0339 (5)
H11	0.4209	0.4291	0.9367	0.041*
C12	0.4409 (3)	0.2810 (2)	0.83888 (15)	0.0292 (5)
H12	0.4849	0.2125	0.8852	0.035*
C13	0.4144 (2)	0.25213 (18)	0.74060 (14)	0.0229 (4)
H13	0.4401	0.1635	0.7207	0.027*
C14	−0.0319 (2)	0.14117 (16)	0.68261 (13)	0.0216 (4)
H14A	0.0815	0.0891	0.7048	0.026*
H14B	−0.1330	0.0912	0.7040	0.026*
C15	−0.0831 (2)	0.26951 (16)	0.73846 (14)	0.0177 (4)
C16	−0.0718 (2)	0.27424 (17)	0.84390 (14)	0.0208 (4)
C17	−0.1108 (3)	0.38998 (18)	0.89709 (15)	0.0286 (5)
H17	−0.0984	0.3897	0.9686	0.034*
C18	−0.1682 (3)	0.50596 (19)	0.84416 (16)	0.0318 (5)
H18	−0.1950	0.5865	0.8791	0.038*
C19	−0.1864 (3)	0.50437 (18)	0.73992 (15)	0.0278 (5)
H19	−0.2278	0.5838	0.7038	0.033*
C20	−0.1444 (2)	0.38733 (16)	0.68813 (14)	0.0220 (4)
H20	−0.1579	0.3878	0.6168	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0335 (3)	0.0200 (3)	0.0421 (3)	−0.0040 (2)	−0.0043 (2)	0.0000 (2)
Cl2	0.0312 (3)	0.0325 (3)	0.0236 (3)	−0.0028 (2)	−0.0053 (2)	0.0053 (2)
P1	0.0155 (3)	0.0181 (3)	0.0179 (3)	−0.00132 (19)	−0.00420 (19)	−0.00271 (19)
O1	0.0167 (7)	0.0171 (7)	0.0254 (7)	−0.0010 (5)	−0.0061 (5)	−0.0035 (5)
O2	0.0170 (7)	0.0245 (7)	0.0179 (7)	0.0012 (5)	−0.0040 (5)	−0.0005 (5)
N1	0.0133 (8)	0.0183 (8)	0.0268 (9)	0.0013 (6)	−0.0053 (7)	−0.0067 (7)
N2	0.0135 (8)	0.0231 (8)	0.0197 (8)	−0.0029 (6)	−0.0047 (6)	−0.0053 (6)
C1	0.0219 (10)	0.0130 (9)	0.0189 (10)	−0.0019 (7)	−0.0018 (8)	−0.0008 (7)
C2	0.0217 (11)	0.0240 (10)	0.0214 (10)	−0.0013 (8)	−0.0061 (8)	−0.0018 (8)
C3	0.0196 (10)	0.0266 (11)	0.0304 (12)	−0.0011 (8)	−0.0018 (9)	0.0005 (9)
C4	0.0333 (12)	0.0300 (11)	0.0208 (11)	−0.0029 (9)	0.0017 (9)	−0.0012 (9)
C5	0.0370 (13)	0.0318 (11)	0.0214 (11)	−0.0093 (9)	−0.0095 (9)	−0.0004 (9)
C6	0.0221 (10)	0.0227 (10)	0.0259 (11)	−0.0058 (8)	−0.0069 (8)	0.0012 (8)
C7	0.0168 (10)	0.0203 (10)	0.0205 (10)	−0.0046 (8)	−0.0027 (8)	−0.0012 (8)
C8	0.0120 (9)	0.0215 (10)	0.0215 (10)	−0.0064 (7)	−0.0002 (8)	−0.0033 (8)
C9	0.0168 (10)	0.0236 (10)	0.0268 (11)	−0.0051 (8)	0.0006 (8)	−0.0023 (8)
C10	0.0274 (11)	0.0340 (12)	0.0321 (12)	−0.0104 (9)	0.0012 (9)	−0.0150 (10)
C11	0.0269 (12)	0.0562 (14)	0.0213 (11)	−0.0132 (10)	−0.0009 (9)	−0.0138 (10)
C12	0.0229 (11)	0.0428 (13)	0.0227 (11)	−0.0088 (9)	−0.0044 (9)	0.0031 (9)
C13	0.0196 (10)	0.0253 (10)	0.0244 (11)	−0.0065 (8)	−0.0028 (8)	−0.0009 (8)
C14	0.0213 (10)	0.0214 (10)	0.0207 (10)	−0.0036 (8)	−0.0007 (8)	0.0015 (8)
C15	0.0100 (9)	0.0197 (10)	0.0221 (10)	−0.0037 (7)	0.0016 (7)	−0.0014 (8)
C16	0.0154 (10)	0.0225 (10)	0.0237 (10)	−0.0044 (8)	−0.0012 (8)	0.0021 (8)
C17	0.0270 (11)	0.0350 (12)	0.0236 (11)	−0.0084 (9)	0.0014 (9)	−0.0084 (9)
C18	0.0337 (12)	0.0247 (11)	0.0352 (13)	−0.0071 (9)	0.0048 (10)	−0.0115 (9)
C19	0.0261 (11)	0.0187 (10)	0.0341 (12)	−0.0010 (8)	0.0024 (9)	0.0009 (9)
C20	0.0171 (10)	0.0234 (10)	0.0230 (10)	−0.0021 (8)	0.0012 (8)	−0.0005 (8)

Geometric parameters (Å, º)

Cl1—C9	1.7470 (19)	C7—H7B	0.9900
Cl2—C16	1.7560 (18)	C8—C13	1.387 (2)
P1—O1	1.4837 (11)	C8—C9	1.400 (2)
P1—O2	1.6095 (12)	C9—C10	1.387 (3)
P1—N1	1.6157 (15)	C10—C11	1.381 (3)
P1—N2	1.6302 (15)	C10—H10	0.9500
O2—C1	1.4003 (19)	C11—C12	1.383 (3)
N1—C7	1.461 (2)	C11—H11	0.9500
N1—H1N	0.849 (9)	C12—C13	1.388 (2)
N2—C14	1.468 (2)	C12—H12	0.9500
N2—H2N	0.838 (9)	C13—H13	0.9500
C1—C6	1.375 (2)	C14—C15	1.514 (2)
C1—C2	1.390 (2)	C14—H14A	0.9900
C2—C3	1.390 (2)	C14—H14B	0.9900
C2—H2	0.9500	C15—C20	1.388 (2)
C3—C4	1.378 (3)	C15—C16	1.392 (2)
C3—H3	0.9500	C16—C17	1.385 (2)
C4—C5	1.387 (3)	C17—C18	1.383 (3)
C4—H4	0.9500	C17—H17	0.9500
C5—C6	1.385 (2)	C18—C19	1.387 (3)
C5—H5	0.9500	C18—H18	0.9500
C6—H6	0.9500	C19—C20	1.387 (2)
C7—C8	1.513 (2)	C19—H19	0.9500
C7—H7A	0.9900	C20—H20	0.9500
O1—P1—O2	110.93 (7)	C10—C9—C8	122.07 (17)
O1—P1—N1	109.90 (7)	C10—C9—Cl1	118.35 (14)
O2—P1—N1	112.03 (7)	C8—C9—Cl1	119.58 (14)
O1—P1—N2	119.79 (7)	C11—C10—C9	119.27 (18)
O2—P1—N2	97.42 (7)	C11—C10—H10	120.4
N1—P1—N2	106.23 (8)	C9—C10—H10	120.4
C1—O2—P1	123.36 (10)	C10—C11—C12	120.05 (18)
C7—N1—P1	125.65 (12)	C10—C11—H11	120.0
C7—N1—H1N	118.1 (12)	C12—C11—H11	120.0
P1—N1—H1N	112.5 (12)	C11—C12—C13	119.95 (19)
C14—N2—P1	120.13 (12)	C11—C12—H12	120.0
C14—N2—H2N	111.3 (12)	C13—C12—H12	120.0
P1—N2—H2N	114.9 (12)	C8—C13—C12	121.63 (17)
C6—C1—C2	121.04 (17)	C8—C13—H13	119.2
C6—C1—O2	116.43 (15)	C12—C13—H13	119.2
C2—C1—O2	122.46 (16)	N2—C14—C15	113.23 (13)
C3—C2—C1	118.36 (17)	N2—C14—H14A	108.9
C3—C2—H2	120.8	C15—C14—H14A	108.9
C1—C2—H2	120.8	N2—C14—H14B	108.9
C4—C3—C2	121.10 (18)	C15—C14—H14B	108.9
C4—C3—H3	119.4	H14A—C14—H14B	107.7
C2—C3—H3	119.4	C20—C15—C16	116.80 (16)
C3—C4—C5	119.68 (18)	C20—C15—C14	122.17 (16)
C3—C4—H4	120.2	C16—C15—C14	121.03 (15)
C5—C4—H4	120.2	C17—C16—C15	122.95 (17)
C6—C5—C4	119.88 (18)	C17—C16—Cl2	117.57 (14)
C6—C5—H5	120.1	C15—C16—Cl2	119.48 (13)
C4—C5—H5	120.1	C18—C17—C16	118.77 (18)
C1—C6—C5	119.93 (18)	C18—C17—H17	120.6
C1—C6—H6	120.0	C16—C17—H17	120.6
C5—C6—H6	120.0	C17—C18—C19	119.78 (18)
N1—C7—C8	112.50 (14)	C17—C18—H18	120.1
N1—C7—H7A	109.1	C19—C18—H18	120.1
C8—C7—H7A	109.1	C18—C19—C20	120.31 (18)
N1—C7—H7B	109.1	C18—C19—H19	119.8
C8—C7—H7B	109.1	C20—C19—H19	119.8
H7A—C7—H7B	107.8	C19—C20—C15	121.34 (17)
C13—C8—C9	117.03 (16)	C19—C20—H20	119.3
C13—C8—C7	122.24 (15)	C15—C20—H20	119.3
C9—C8—C7	120.73 (16)
O1—P1—O2—C1	−47.55 (13)	C13—C8—C9—Cl1	−179.81 (13)
N1—P1—O2—C1	75.67 (13)	C7—C8—C9—Cl1	0.2 (2)
N2—P1—O2—C1	−173.43 (12)	C8—C9—C10—C11	0.9 (3)
O1—P1—N1—C7	177.62 (13)	Cl1—C9—C10—C11	179.80 (14)
O2—P1—N1—C7	53.82 (16)	C9—C10—C11—C12	−0.2 (3)
N2—P1—N1—C7	−51.42 (16)	C10—C11—C12—C13	−0.3 (3)
O1—P1—N2—C14	69.33 (14)	C9—C8—C13—C12	0.3 (3)
O2—P1—N2—C14	−171.36 (12)	C7—C8—C13—C12	−179.70 (15)
N1—P1—N2—C14	−55.77 (14)	C11—C12—C13—C8	0.3 (3)
P1—O2—C1—C6	146.10 (13)	P1—N2—C14—C15	114.90 (14)
P1—O2—C1—C2	−36.8 (2)	N2—C14—C15—C20	17.4 (2)
C6—C1—C2—C3	0.1 (2)	N2—C14—C15—C16	−163.04 (15)
O2—C1—C2—C3	−176.88 (15)	C20—C15—C16—C17	−2.8 (3)
C1—C2—C3—C4	0.0 (3)	C14—C15—C16—C17	177.59 (16)
C2—C3—C4—C5	−0.1 (3)	C20—C15—C16—Cl2	177.26 (12)
C3—C4—C5—C6	0.1 (3)	C14—C15—C16—Cl2	−2.3 (2)
C2—C1—C6—C5	−0.1 (3)	C15—C16—C17—C18	1.7 (3)
O2—C1—C6—C5	177.07 (14)	Cl2—C16—C17—C18	−178.41 (13)
C4—C5—C6—C1	0.0 (3)	C16—C17—C18—C19	0.3 (3)
P1—N1—C7—C8	132.69 (14)	C17—C18—C19—C20	−1.1 (3)
N1—C7—C8—C13	6.0 (2)	C18—C19—C20—C15	−0.2 (3)
N1—C7—C8—C9	−173.97 (14)	C16—C15—C20—C19	2.0 (2)
C13—C8—C9—C10	−0.9 (3)	C14—C15—C20—C19	−178.40 (16)
C7—C8—C9—C10	179.11 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.85 (1)	2.01 (1)	2.8551 (17)	173 (2)
N2—H2N···O1^ii	0.84 (1)	2.13 (1)	2.9365 (17)	160 (2)

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

(II) N,N'-bis(2-chlorobenzyl)-N''-(2,2,2- trifluoroacetyl)phosphoric triamide

Crystal data

C16H15Cl2F3N3O2P	Z = 2
Mr = 440.18	F(000) = 448
Triclinic, P1	Dx = 1.614 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.8860 (8) Å	Cell parameters from 1283 reflections
b = 12.192 (2) Å	θ = 3.4–27.7°
c = 15.838 (3) Å	µ = 0.49 mm^−1
α = 103.714 (17)°	T = 120 K
β = 94.636 (15)°	Block, colourless
γ = 96.099 (15)°	0.30 × 0.20 × 0.20 mm
V = 905.9 (3) Å^3

Data collection

Oxford Xcalibur Sapphire2 (large Be window) diffractometer	3179 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1971 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 8.4353 pixels mm^-1	θmax = 25.0°, θmin = 3.5°
ω scans	h = −5→5
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −14→12
Tmin = 0.652, Tmax = 1.000	l = −18→18
5706 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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 0.81	w = 1/[σ^2(Fo^2) + (0.0371P)^2] where P = (Fo^2 + 2Fc^2)/3
3179 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.32 e Å^−3
3 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental. The planes for (II)

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 1.0086 (0.0178) x + 10.8000 (0.0069) y - 10.0179 (0.0287) z = 3.4649 (0.0091) * 0.0000 (0.0000) P1 * 0.0000 (0.0000) N1 * 0.0000 (0.0000) C10 0.1585 (0.0281) H1N Rms deviation of fitted atoms = 0.0000

- 1.8431 (0.0168) x + 10.7920 (0.0181) y - 8.4692 (0.0126) z = 3.1673 (0.0264) A ngle to previous plane (with approximate e.s.d.) = 10.93 (0.29) * 0.0000 (0.0000) P1 * 0.0000 (0.0000) N2 * 0.0000 (0.0000) C3 0.2422 (0.0277) H2N Rms deviation of fitted atoms = 0.0000

0.0777 (0.0204) x + 3.9759 (0.0103) y + 13.1262 (0.0121) z = 6.4288 (0.0148) A ngle to previous plane (with approximate e.s.d.) = 85.81 (0.12) * 0.0000 (0.0000) P1 * 0.0000 (0.0000) N3 * 0.0000 (0.0000) C1 0.0434 (0.0285) H3N Rms deviation of fitted atoms = 0.0000

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	0.83804 (16)	0.34887 (7)	−0.02978 (5)	0.0296 (2)
Cl2	1.32673 (19)	0.92801 (7)	0.57998 (5)	0.0415 (2)
P1	0.87561 (16)	0.66520 (7)	0.28310 (5)	0.01974 (19)
F1	1.1107 (3)	1.02222 (14)	0.26270 (11)	0.0343 (5)
F2	1.0648 (3)	0.92382 (14)	0.12911 (10)	0.0338 (5)
F3	0.7407 (4)	1.01882 (14)	0.17822 (11)	0.0359 (5)
O1	1.1408 (4)	0.62114 (16)	0.29464 (12)	0.0240 (5)
O2	0.5430 (4)	0.83835 (16)	0.22847 (12)	0.0270 (5)
N1	0.6401 (5)	0.5798 (2)	0.21478 (15)	0.0206 (6)
H1N	0.472 (3)	0.588 (2)	0.2249 (17)	0.025*
N2	0.7187 (5)	0.7056 (2)	0.36873 (15)	0.0222 (6)
H2N	0.539 (2)	0.693 (2)	0.3629 (17)	0.027*
N3	0.9690 (5)	0.7839 (2)	0.24659 (15)	0.0211 (6)
H3N	1.145 (2)	0.802 (2)	0.2435 (17)	0.025*
C1	0.7923 (6)	0.8529 (2)	0.22675 (17)	0.0201 (7)
C2	0.9270 (6)	0.9562 (3)	0.19904 (19)	0.0243 (7)
C3	0.8579 (7)	0.7901 (3)	0.44614 (18)	0.0294 (8)
H3B	0.7311	0.8466	0.4667	0.035*
H3C	1.0229	0.8310	0.4295	0.035*
C4	0.9474 (6)	0.7394 (2)	0.52056 (17)	0.0228 (7)
C5	1.1626 (7)	0.7954 (3)	0.58438 (19)	0.0290 (8)
C6	1.2496 (7)	0.7497 (3)	0.65209 (19)	0.0322 (8)
H6A	1.3986	0.7891	0.6943	0.039*
C7	1.1197 (7)	0.6472 (3)	0.65797 (19)	0.0340 (8)
H7A	1.1798	0.6149	0.7042	0.041*
C8	0.9026 (7)	0.5907 (3)	0.59730 (19)	0.0348 (8)
H8A	0.8097	0.5205	0.6024	0.042*
C9	0.8197 (7)	0.6362 (3)	0.52894 (19)	0.0325 (8)
H9A	0.6718	0.5958	0.4867	0.039*
C10	0.6992 (6)	0.5083 (2)	0.13171 (17)	0.0235 (7)
H10A	0.9011	0.5050	0.1336	0.028*
H10B	0.6447	0.5439	0.0839	0.028*
C11	0.5504 (6)	0.3889 (2)	0.11159 (17)	0.0190 (7)
C12	0.6017 (6)	0.3086 (3)	0.03814 (18)	0.0223 (7)
C13	0.4759 (6)	0.1976 (3)	0.01682 (19)	0.0275 (7)
H13A	0.5186	0.1445	−0.0332	0.033*
C14	0.2861 (7)	0.1647 (3)	0.06939 (19)	0.0319 (8)
H14A	0.1957	0.0887	0.0553	0.038*
C15	0.2288 (6)	0.2428 (3)	0.14223 (19)	0.0305 (8)
H15A	0.0984	0.2202	0.1782	0.037*
C16	0.3586 (6)	0.3528 (3)	0.16320 (18)	0.0232 (7)
H16A	0.3170	0.4053	0.2137	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0319 (5)	0.0344 (5)	0.0223 (4)	0.0011 (4)	0.0102 (4)	0.0058 (4)
Cl2	0.0486 (6)	0.0362 (5)	0.0349 (5)	−0.0090 (4)	−0.0024 (4)	0.0078 (4)
P1	0.0191 (4)	0.0236 (5)	0.0176 (4)	0.0018 (3)	0.0031 (3)	0.0074 (3)
F1	0.0342 (11)	0.0292 (10)	0.0354 (10)	−0.0078 (8)	−0.0032 (9)	0.0073 (9)
F2	0.0409 (11)	0.0370 (11)	0.0300 (10)	0.0071 (9)	0.0158 (9)	0.0163 (9)
F3	0.0333 (11)	0.0317 (11)	0.0486 (11)	0.0073 (9)	0.0042 (9)	0.0205 (9)
O1	0.0194 (11)	0.0296 (12)	0.0256 (11)	0.0036 (9)	0.0047 (9)	0.0110 (10)
O2	0.0170 (12)	0.0334 (13)	0.0340 (12)	0.0028 (10)	0.0049 (10)	0.0143 (10)
N1	0.0143 (13)	0.0244 (14)	0.0216 (13)	0.0011 (11)	0.0056 (12)	0.0022 (11)
N2	0.0158 (13)	0.0332 (15)	0.0174 (13)	0.0022 (12)	0.0024 (12)	0.0061 (12)
N3	0.0140 (13)	0.0275 (15)	0.0236 (14)	0.0016 (12)	0.0049 (12)	0.0097 (12)
C1	0.0219 (18)	0.0240 (17)	0.0150 (15)	0.0022 (14)	0.0040 (13)	0.0056 (13)
C2	0.0224 (17)	0.0257 (18)	0.0265 (18)	0.0053 (14)	0.0036 (15)	0.0087 (15)
C3	0.041 (2)	0.0284 (19)	0.0201 (16)	0.0048 (15)	0.0049 (15)	0.0071 (15)
C4	0.0280 (18)	0.0267 (18)	0.0141 (15)	0.0066 (14)	0.0048 (14)	0.0036 (14)
C5	0.035 (2)	0.0283 (19)	0.0241 (17)	0.0055 (15)	0.0102 (16)	0.0032 (15)
C6	0.032 (2)	0.042 (2)	0.0195 (17)	0.0065 (16)	−0.0027 (15)	0.0030 (16)
C7	0.043 (2)	0.041 (2)	0.0223 (18)	0.0120 (18)	0.0038 (17)	0.0140 (17)
C8	0.043 (2)	0.033 (2)	0.0315 (19)	0.0011 (17)	0.0042 (17)	0.0163 (17)
C9	0.039 (2)	0.033 (2)	0.0259 (18)	−0.0020 (16)	−0.0016 (16)	0.0111 (16)
C10	0.0254 (18)	0.0274 (18)	0.0186 (16)	0.0027 (14)	0.0051 (14)	0.0067 (14)
C11	0.0158 (16)	0.0238 (17)	0.0178 (15)	0.0016 (13)	−0.0013 (13)	0.0075 (14)
C12	0.0208 (17)	0.0308 (19)	0.0173 (16)	0.0034 (14)	0.0039 (13)	0.0093 (15)
C13	0.0341 (19)	0.0261 (19)	0.0195 (16)	0.0026 (15)	0.0019 (15)	0.0010 (14)
C14	0.038 (2)	0.0236 (18)	0.0299 (19)	−0.0068 (15)	0.0000 (16)	0.0050 (16)
C15	0.036 (2)	0.033 (2)	0.0226 (18)	−0.0042 (16)	0.0036 (15)	0.0108 (16)
C16	0.0217 (17)	0.0314 (19)	0.0162 (15)	0.0030 (14)	0.0024 (13)	0.0057 (14)

Geometric parameters (Å, º)

Cl1—C12	1.750 (3)	C5—C6	1.379 (4)
Cl2—C5	1.746 (3)	C6—C7	1.367 (4)
P1—O1	1.469 (2)	C6—H6A	0.9500
P1—N1	1.609 (2)	C7—C8	1.374 (4)
P1—N2	1.613 (2)	C7—H7A	0.9500
P1—N3	1.714 (2)	C8—C9	1.381 (4)
F1—C2	1.336 (3)	C8—H8A	0.9500
F2—C2	1.344 (3)	C9—H9A	0.9500
F3—C2	1.318 (3)	C10—C11	1.506 (4)
O2—C1	1.216 (3)	C10—H10A	0.9900
N1—C10	1.465 (3)	C10—H10B	0.9900
N1—H1N	0.863 (10)	C11—C12	1.390 (4)
N2—C3	1.464 (4)	C11—C16	1.395 (4)
N2—H2N	0.868 (10)	C12—C13	1.377 (4)
N3—C1	1.337 (3)	C13—C14	1.385 (4)
N3—H3N	0.871 (10)	C13—H13A	0.9500
C1—C2	1.531 (4)	C14—C15	1.379 (4)
C3—C4	1.511 (4)	C14—H14A	0.9500
C3—H3B	0.9900	C15—C16	1.374 (4)
C3—H3C	0.9900	C15—H15A	0.9500
C4—C9	1.384 (4)	C16—H16A	0.9500
C4—C5	1.394 (4)
O1—P1—N1	115.42 (12)	C7—C6—C5	119.5 (3)
O1—P1—N2	117.70 (12)	C7—C6—H6A	120.3
N1—P1—N2	103.43 (13)	C5—C6—H6A	120.3
O1—P1—N3	102.57 (11)	C6—C7—C8	120.2 (3)
N1—P1—N3	110.46 (12)	C6—C7—H7A	119.9
N2—P1—N3	107.06 (12)	C8—C7—H7A	119.9
C10—N1—P1	122.87 (19)	C7—C8—C9	119.9 (3)
C10—N1—H1N	120.6 (18)	C7—C8—H8A	120.0
P1—N1—H1N	115.5 (18)	C9—C8—H8A	120.0
C3—N2—P1	121.2 (2)	C8—C9—C4	121.5 (3)
C3—N2—H2N	118.3 (19)	C8—C9—H9A	119.3
P1—N2—H2N	117.9 (19)	C4—C9—H9A	119.3
C1—N3—P1	124.3 (2)	N1—C10—C11	113.1 (2)
C1—N3—H3N	118.7 (18)	N1—C10—H10A	109.0
P1—N3—H3N	116.9 (18)	C11—C10—H10A	109.0
O2—C1—N3	125.3 (3)	N1—C10—H10B	109.0
O2—C1—C2	120.1 (3)	C11—C10—H10B	109.0
N3—C1—C2	114.6 (2)	H10A—C10—H10B	107.8
F3—C2—F1	108.2 (2)	C12—C11—C16	116.9 (3)
F3—C2—F2	107.6 (2)	C12—C11—C10	119.7 (2)
F1—C2—F2	106.8 (2)	C16—C11—C10	123.3 (3)
F3—C2—C1	111.5 (2)	C13—C12—C11	122.6 (3)
F1—C2—C1	111.4 (2)	C13—C12—Cl1	118.2 (2)
F2—C2—C1	111.1 (2)	C11—C12—Cl1	119.1 (2)
N2—C3—C4	113.6 (2)	C12—C13—C14	119.0 (3)
N2—C3—H3B	108.8	C12—C13—H13A	120.5
C4—C3—H3B	108.8	C14—C13—H13A	120.5
N2—C3—H3C	108.8	C15—C14—C13	119.7 (3)
C4—C3—H3C	108.8	C15—C14—H14A	120.1
H3B—C3—H3C	107.7	C13—C14—H14A	120.1
C9—C4—C5	117.0 (3)	C16—C15—C14	120.6 (3)
C9—C4—C3	121.9 (3)	C16—C15—H15A	119.7
C5—C4—C3	121.1 (3)	C14—C15—H15A	119.7
C6—C5—C4	121.9 (3)	C15—C16—C11	121.2 (3)
C6—C5—Cl2	118.5 (3)	C15—C16—H16A	119.4
C4—C5—Cl2	119.6 (2)	C11—C16—H16A	119.4
O1—P1—N1—C10	−40.4 (3)	C3—C4—C5—Cl2	1.6 (4)
N2—P1—N1—C10	−170.3 (2)	C4—C5—C6—C7	−0.9 (5)
N3—P1—N1—C10	75.4 (2)	Cl2—C5—C6—C7	178.5 (3)
O1—P1—N2—C3	54.8 (3)	C5—C6—C7—C8	−0.6 (5)
N1—P1—N2—C3	−176.7 (2)	C6—C7—C8—C9	1.6 (5)
N3—P1—N2—C3	−60.0 (2)	C7—C8—C9—C4	−1.2 (5)
O1—P1—N3—C1	179.9 (2)	C5—C4—C9—C8	−0.2 (5)
N1—P1—N3—C1	56.3 (3)	C3—C4—C9—C8	−179.9 (3)
N2—P1—N3—C1	−55.6 (3)	P1—N1—C10—C11	137.4 (2)
P1—N3—C1—O2	−3.2 (4)	N1—C10—C11—C12	−175.3 (2)
P1—N3—C1—C2	177.63 (19)	N1—C10—C11—C16	4.9 (4)
O2—C1—C2—F3	−0.9 (4)	C16—C11—C12—C13	−1.2 (4)
N3—C1—C2—F3	178.3 (2)	C10—C11—C12—C13	179.0 (3)
O2—C1—C2—F1	120.1 (3)	C16—C11—C12—Cl1	179.48 (19)
N3—C1—C2—F1	−60.6 (3)	C10—C11—C12—Cl1	−0.3 (4)
O2—C1—C2—F2	−121.0 (3)	C11—C12—C13—C14	1.4 (4)
N3—C1—C2—F2	58.3 (3)	Cl1—C12—C13—C14	−179.3 (2)
P1—N2—C3—C4	−104.1 (3)	C12—C13—C14—C15	−0.7 (4)
N2—C3—C4—C9	−24.1 (4)	C13—C14—C15—C16	−0.1 (4)
N2—C3—C4—C5	156.3 (3)	C14—C15—C16—C11	0.2 (4)
C9—C4—C5—C6	1.3 (4)	C12—C11—C16—C15	0.4 (4)
C3—C4—C5—C6	−179.1 (3)	C10—C11—C16—C15	−179.8 (3)
C9—C4—C5—Cl2	−178.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.86 (1)	2.05 (1)	2.875 (3)	159 (2)
N2—H2N···O1^i	0.87 (1)	2.14 (2)	2.947 (3)	155 (3)
N3—H3N···O2^ii	0.87 (1)	2.00 (1)	2.866 (3)	176 (3)

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