Three new phospho­ric tri­amides with a [C(O)NH]P(O)[N(C)(C)]₂ skeleton: a database analysis of C—N—C and P—N—C bond angles

In N,N,N′,N′-tetra­ethyl-N′′-(4-fluoro­benzo­yl)phospho­ric tri­amide, C₁₅H₂₅FN₃O₂P, (I), and N-(2,6-di­fluoro­benzo­yl)-N′,N′′-bis­(4-methyl­piperidin-1-yl)phospho­ric tri­amide, C₁₉H₂₈F₂N₃O₂P, (II), the C—N—C angle at each tertiary N atom is significantly smaller than the two P—N—C angles. For the other new structure, N,N′-di­cyclo­hexyl-N′′-(2-fluoro­benzo­yl)-N,N′-dimethylphospho­ric tri­amide, C₂₁H₃₃FN₃O₂P, (III), one C—N—C angle [117.08 (12)°] has a greater value than the related P—N—C angle [115.59 (9)°] at the same N atom. Furthermore, for most of the analogous structures with a [C(=O)NH]P(=O)[N(C)(C)]₂ skeleton deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B58, 380–388], the C—N—C angle is significantly smaller than the two P—N—C angles; exceptions were found for four structures with the N-methyl­cyclo­hexyl­amide substituent, similar to (III), one structure with the seven-membered cyclic amide azepan-1-yl substituent and one structure with an N-methyl­benzyl­amide substituent. The asymmetric units of (I), (II) and (III) contain one mol­ecule, and in the crystal structures, adjacent mol­ecules are linked via pairs of N—H...O=P hydrogen bonds to form dimers.

S1. Introduction

The P—N bond and the geometry at the N atom in phospho­ric tri­amides are salient structural features for this family of compounds. The theoretical concepts of bond order are difficult to study in P—N bonds because of the complex characteristics of d orbitals. In 1973, Norman and Arthur Camerman reported their studies of the π-bond character of the P—N bond in phospho­ric tri­amides by a comparison with P—N single-bond compounds and they attributed 30% of the π-bond character to a P—N distance of 1.66 Å (Camerman & Camerman, 1973). Moreover, an analysis of the bond-angle sums at the two tertiary N atoms in phospho­ric tri­amides containing a C(═ O)NHP(═O)[N(C)(C)]₂ skeleton (Pourayoubi et al., 2012), it was found that, in a compound with a considerable Δ SUM (= SUM1 - SUM2) value [where SUM1 and SUM2 are the bond-angle sums at the two tertiary N atoms], the more pyramidal N atom is oriented so that the position of the lone electron pair (LEP) is anti with respect to the P═O group.

Here, we explore the structures of three new phospho­ric tri­amides with a [C(═O)NH]P(═O)[N(C)(C)]₂ skeleton: 4-F—C₆H₄C(═O)NHP(═ O)[N(C₂H₅)₂]₂, (I), 2,6-F₂—C₆H₃C(═O)NHP(═ O)[NC₅H₉(4-CH₃)]₂, (II), and 2-F—C₆H₄C(═O)NHP(═ O)[N(CH₃)(C₆H₁₁)]₂, (III). The NRR' group attached to the P═ O group is named an amide group. The amide group is obtained by the loss of one H⁺ cation from the initial NHRR' amine used in the reaction, so that, in the synthesis of the phospho­ramide, the Cl^- substituent in the related initial phospho­rus-chlorine compound is replaced by the [NRR']^- amide group.

The C—N—C and two P—N—C bond angles at the N atoms are examined in these three new structures and compared with analogous structures deposited in the Cambridge Structural Database (CSD, Version 5.35, Feb 2014 update; Allen, 2002); for each example, the CSD refcode is given in capitals followed by the primary reference).

S2. Experimental

S2.1. Synthesis and crystallization

The three starting materials 4-F—C₆H₄C(═O)NHP(═O)Cl₂, 2,6-F₂—C₆H₃C(═O)NHP(═O)Cl₂ and 2-F—C₆H₄C(═O)NHP(═ O)Cl₂ were synthesized according to the literature methods reported by Tarahhomi et al. (2011), Pourayoubi, Tarahhomi, Saneei et al. (2011) and Pourayoubi et al. (2011a), respectively.

For the preparation of (I), a solution of di­ethyl­amine (4 mmol) in dry CH₃CN (5 ml) was added to a solution of 4-F—C₆H₄C(═O)NHP(═O)Cl₂ (1 mmol) in the same solvent (20 ml) and stirred at 273 K. After stirring for 4 h, the solvent was evaporated and the solid obtained was washed with distilled water. IR (KBr, ν, cm^-1): 3096, 2975, 2875, 1668, 1601, 1457, 1380, 1274, 1221, 1106, 1024, 952, 846, 793, 756.

Compounds (II) and (III) were obtained in a similar procedure to (I) by using the relevant amine and initial phospho­rous-chlorine compound: 4-methyl­piperidine and 2,6-F₂—C₆H₃C(═O)NHP(═O)Cl₂ for (II), and N-methyl­cyclo­hexyl­amine and 2-F—C₆H₄C(═O)NHP(═O)Cl₂ for (III). IR (KBr, ν, cm^-1) for (II): 3069, 2934, 2873, 1690, 1609, 1457, 1372, 1277, 1192, 1063, 939, 802, 726; for (III): 3053, 2922, 2863, 1690, 1604, 1457, 1272, 1243, 1172, 996, 868, 840, 745.

Colourless single crystals were formed from solutions of (I), (II) and (III), separately, in CH₃OH/di­methyl­formamide (5:1 v/v) after slow evaporation at room temperature.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystal data, data collection and structure refinement details are summarized in Table 1. Atom H1N was found from a Fourier difference map and allowed to refine isotropically, with N—H = 0.87 (2) Å for (I) and (II) or 0.87 (1) Å for (III), and with U_iso(H) = 1.2U_eq(N). All [Other?] H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95 (CH, Ar), 0.99 (CH₂) or 0.98 Å (CH₃) for all compounds and 1.00 Å (CH) for the cyclo­hexyl groups in (III), and with U_iso(H) = 1.2U_eq(C) (CH, CH₂) or 1.5U_eq(C) (CH₃). In (III), the C1–C6 phenyl ring and attached F atom were disordered over two positions and refined using a two-part disorder model with an occupancy of 0.6439/0.3561. The C1B—C7 distance was restrained to 1.50 (1) Å.

S3. Results and discussion

The molecular structures of (I)–(III) are shown in Figs. 1–3, respectively. The asymmetric unit of all three structures contains one molecule. The P atom exhibits a distorted tetra­hedral environment, which is reflected in the bond lengths and angles in the [N]P(═O)[N]₂ fragment (Tables 2, 4 and 6). The characteristic bond lengths and angles are within the expected values (Tarahhomi et al., 2013). As expected, in each molecule the P—N_CP bond is longer than the other two P—N bonds [the N-atom separator of the phospho­ryl and carbonyl groups is designated as N_CP] and the O—P—N_CP angle is reduced compared with the other two O—P—N angles (Tables 2, 4 and 6). For example, in (III), P—N_CP = 1.6856 (11) Å and P—N = 1.6353 (11) and 1.6371 (12) Å; O—P—N_CP = 105.47 (5)° and O—P—N = 110.71 (5) and 117.00 (6)°. In all three structures, the anti orientation of P═O with respect to C═O is reflected in the O—P—N—C torsion angles: -164.80 (11)° in (I), -162.48 (12)° in (II) and 166.02 (12)° in (III).

In the crystal structures of (I)–(III), adjacent molecules are linked via pairs of N—H···O═P hydrogen bonds to form dimers (Tables 3, 5 and 7). For example, part of the crystal structure of (I) is shown in Fig. 4.

In (I) and (II), with a [C(═O)NH]P(═O)[N(C)(C)]₂ skeleton, the C—N—C angles are significantly smaller than two related P—N—C angles. In contrast, for (III), having the N-methyl­cyclo­hexyl­amide fragments, the C—N—C angle at one of the tertiary N atoms is larger than one of the P—N—C angles at the same N atom.

The C—N—C, P—N—C and P—N—C bond angles at the tertiary N atoms in phospho­ric tri­amides with a [C(═O)NH]P(═O)[N(C)(C)]₂ skeleton found in the CSD were also examined. Compounds with disorder in the N or surrounding atoms were excluded from consideration. Compounds with three- and four-membered cyclic amide substituents were not included, as ring strain has an effect on the surrounding angles at the tertiary N atoms and naturally reduces the C—N—C angles. Four structures with unusual bond angles were also excluded.

Fig. 5 shows the values of the C—N—C and two P—N—C angles at the two tertiary N atoms for 84 phospho­ric tri­amides with a [C(═O)NH]P(═ O)[N(C)(C)]₂ skeleton; the bond angles vary in the range 107.9–129.2°. The hits related to the C—N—C angles are distinguished from the P—N—C angles as red squares [Circles?]. The data clearly show that, for most of the studied structures, the C—N—C angles are significantly smaller than the P—N—C angles at the same N atom. This can be attributed to the different natures of P—N and C—N bonds and the differing structural hindrance of the substituted groups on the N atoms (and also on the P atom). Thus, partial multiple-bond character is found in the P—N bond, due to a resonance inter­action with the P═O group (Goldwhite, 1981). This leads to an increase in the repulsion between P—N and C—N bonds compared with C—N and C—N bonds. Moreover, in the P—N bond, the P atom is connected to three other groups, while apart from the P atom two other groups are attached to the N atom. Therefore the atomic volume of the P atom and the steric hindrance around it are also important, which may not be easily predicted. It is noted that the N-atom hybridization changes from almost sp³ in amine (R¹R²NH) to almost sp² in the related phospho­ramide [with an R¹R²NP(═O) fragment].

Six structures were observed with a C—N—C angle slightly larger than the P—N—C angles, at least for one of two tertiary N atoms: entry 3 in Fig. 5 [2,4-Cl₂—C₆H₃C(═O)NHP(═O)[NC₆H₁₂]₂, LUPGAF; Gholivand et al., 2010], entry 5 [2,6-F₂—C₆H₃C(═O)NHP(═ O)[N(CH₃)(C₆H₁₁)]₂, YAJGUN; Pourayoubi et al., 2011b], entry 7 [3-F—C₆H₄C(═O)NHP(═ O)[N(CH₃)(C₆H₁₁)]₂, YAHGOF; Pourayoubi, Shoghpour, Bruno & Amiri Rudbari, 2011], entry 26 [4-NO₂—C₆H₄C(═O)NHPδb O)[N(CH₃)(C₆H₁₁)]₂, YUPVAH; Sabbaghi et al., 2010], entry 31 [C₆H₅C(═O)NHP(═ O)[N(CH₃)(C₆H₁₁)]₂, SEYPES; Gholivand & Shariatinia, 2007] and entry 67 [C₆H₅CH₂C(═O)NHP(═O)[N(CH₃)(CH₂C₆H₅)]₂, OCAYIC; Pourayoubi, Shoghpour, Torre-Fernández & García-Granda, 2011].

Inter­estingly, most of these structures contain the N-methyl­cyclo­hexyl­amide substituent similar to (III), except for entry 3 (LUPGAF), where the structure contains a seven-membered cyclic amide substituent, and entry 67 (OCAYIC), where the structure contains an N-methyl­benzyl­amide substituent. These exceptions can be attributed to an increase in steric congestion between the substituent groups located on the N atoms, for example methyl/cyclo­hexyl groups in entry 5 and (III).

Related literature

For related literature, see: Allen (2002); Camerman & Camerman (1973); Gholivand & Shariatinia (2007); Gholivand et al. (2010); Goldwhite (1981); Pourayoubi et al. (2011a, 2011b, 2012); Pourayoubi, Shoghpour, Bruno & Amiri Rudbari (2011); Pourayoubi, Shoghpour, Torre-Fernández & García-Granda (2011); Pourayoubi, Tarahhomi, Saneei, Rheingold & Golen (2011); Sabbaghi et al. (2010); Tarahhomi et al. (2011, 2013).

Computing details

For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Putz, 2005) for (I); SHELXTL (Sheldrick, 2008) for (II), (III). For all compounds, software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and enCIFer (Allen et al., 2004).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity, except for atom H1N, which is shown as a small sphere of arbitrary radius. Disordered atoms are labelled with the suffices A and B. [Dashed lines indicate the minor occupancy component?]
	Fig. 4. Part of the crystal structure of (I), showing the N—HO═P hydrogen bonds (dotted lines).
	Fig. 5. The values of C—N—C and P—N—C bond angles at the two tertiary N atoms from 84 hits with a [C(═O)NH]P(═O)[N(C)(C)]2 skeleton. Red squares denote the C—N—C bond angles. [No red squares visible - they are all circles. Please clarify.]

(I) N,N,N',N'-tetraethyl-N''-(4-fluorobenzoyl)phosphoric triamide

Crystal data

C15H25FN3O2P	Z = 2
Mr = 329.35	F(000) = 352
Triclinic, P1	Dx = 1.317 Mg m^−3
a = 8.8477 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7545 (6) Å	Cell parameters from 9991 reflections
c = 10.0198 (7) Å	θ = 2.4–26.4°
α = 79.993 (2)°	µ = 0.19 mm^−1
β = 77.973 (2)°	T = 90 K
γ = 83.658 (2)°	Block, colourless
V = 830.43 (10) Å^3	0.20 × 0.20 × 0.12 mm

Data collection

Bruker D8 Quest CMOS area-detector diffractometer	3036 independent reflections
Radiation source: fine-focus sealed tube	2773 reflections with I > 2σ(I)
Doubly curved mirror monochromator	Rint = 0.049
φ and ω scans	θmax = 25.4°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
Tmin = 0.964, Tmax = 0.978	k = −11→11
16977 measured reflections	l = −12→12

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 0.4677P] where P = (Fo^2 + 2Fc^2)/3
3036 reflections	(Δ/σ)max = 0.001
206 parameters	Δρmax = 0.34 e Å^−3
1 restraint	Δρmin = −0.37 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
P1	0.33324 (4)	0.02186 (3)	0.34653 (3)	0.01179 (12)
F1	0.95876 (10)	0.59701 (9)	0.20166 (9)	0.0242 (2)
O1	0.41953 (11)	0.26842 (10)	0.12140 (10)	0.0182 (2)
O2	0.32711 (10)	−0.05119 (10)	0.49006 (9)	0.0148 (2)
N1	0.47013 (13)	0.13710 (12)	0.32044 (12)	0.0129 (2)
H1N	0.5313 (17)	0.1195 (17)	0.3780 (15)	0.015*
N2	0.16274 (13)	0.09852 (12)	0.32886 (11)	0.0134 (3)
N6	0.38792 (13)	−0.07024 (12)	0.22089 (12)	0.0144 (3)
C1	0.66466 (16)	0.35279 (14)	0.33794 (14)	0.0162 (3)
H1A	0.6209	0.2995	0.4232	0.019*
C2	0.77961 (16)	0.44066 (15)	0.33328 (15)	0.0180 (3)
H2A	0.8142	0.4496	0.4148	0.022*
C3	0.84207 (16)	0.51451 (14)	0.20736 (16)	0.0174 (3)
C4	0.79169 (17)	0.50976 (15)	0.08756 (15)	0.0199 (3)
H4A	0.8352	0.5641	0.0028	0.024*
C5	0.67544 (16)	0.42328 (15)	0.09420 (14)	0.0168 (3)
H5A	0.6376	0.4191	0.0131	0.020*
C6	0.61338 (15)	0.34253 (14)	0.21805 (14)	0.0135 (3)
C7	0.49251 (15)	0.24755 (14)	0.21520 (14)	0.0135 (3)
C8	0.11485 (16)	0.15042 (15)	0.19562 (14)	0.0168 (3)
H8A	0.1993	0.1255	0.1200	0.020*
H8B	0.0989	0.2535	0.1841	0.020*
C9	−0.03327 (17)	0.09156 (17)	0.18336 (16)	0.0217 (3)
H9A	−0.0651	0.1365	0.0971	0.033*
H9B	−0.1155	0.1096	0.2619	0.033*
H9C	−0.0146	−0.0093	0.1832	0.033*
C10	0.07037 (16)	0.16120 (14)	0.44727 (14)	0.0158 (3)
H10A	0.0799	0.0970	0.5337	0.019*
H10B	−0.0401	0.1712	0.4394	0.019*
C11	0.11976 (17)	0.30341 (16)	0.45679 (16)	0.0210 (3)
H11A	0.0475	0.3437	0.5308	0.032*
H11B	0.1190	0.3655	0.3688	0.032*
H11C	0.2245	0.2925	0.4770	0.032*
C12	0.55196 (16)	−0.08724 (15)	0.15168 (14)	0.0173 (3)
H12A	0.5876	0.0062	0.1105	0.021*
H12B	0.5588	−0.1411	0.0752	0.021*
C13	0.66150 (17)	−0.16023 (16)	0.24512 (17)	0.0225 (3)
H13A	0.7661	−0.1723	0.1901	0.034*
H13B	0.6256	−0.2518	0.2890	0.034*
H13C	0.6633	−0.1035	0.3164	0.034*
C14	0.28695 (16)	−0.17513 (15)	0.20629 (15)	0.0179 (3)
H14A	0.2814	−0.1668	0.1075	0.021*
H14B	0.1811	−0.1531	0.2574	0.021*
C15	0.33795 (18)	−0.32526 (15)	0.25750 (16)	0.0220 (3)
H15A	0.2624	−0.3870	0.2470	0.033*
H15B	0.3447	−0.3351	0.3551	0.033*
H15C	0.4398	−0.3507	0.2034	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01254 (19)	0.01165 (19)	0.0112 (2)	−0.00223 (13)	−0.00314 (13)	−0.00005 (13)
F1	0.0198 (4)	0.0217 (5)	0.0327 (5)	−0.0103 (4)	−0.0046 (4)	−0.0034 (4)
O1	0.0215 (5)	0.0190 (5)	0.0152 (5)	−0.0050 (4)	−0.0077 (4)	0.0014 (4)
O2	0.0155 (5)	0.0150 (5)	0.0139 (5)	−0.0029 (4)	−0.0047 (4)	0.0009 (4)
N1	0.0138 (6)	0.0133 (6)	0.0124 (6)	−0.0030 (4)	−0.0055 (4)	0.0007 (5)
N2	0.0139 (6)	0.0148 (6)	0.0112 (6)	−0.0007 (4)	−0.0028 (4)	−0.0012 (4)
N6	0.0137 (6)	0.0146 (6)	0.0158 (6)	−0.0029 (4)	−0.0026 (4)	−0.0034 (5)
C1	0.0197 (7)	0.0126 (7)	0.0159 (7)	−0.0016 (5)	−0.0042 (6)	0.0004 (5)
C2	0.0216 (7)	0.0146 (7)	0.0198 (7)	−0.0006 (6)	−0.0089 (6)	−0.0025 (6)
C3	0.0130 (7)	0.0120 (7)	0.0274 (8)	−0.0022 (5)	−0.0035 (6)	−0.0033 (6)
C4	0.0207 (7)	0.0174 (7)	0.0189 (7)	−0.0049 (6)	0.0011 (6)	0.0005 (6)
C5	0.0188 (7)	0.0166 (7)	0.0148 (7)	−0.0010 (5)	−0.0041 (5)	−0.0015 (5)
C6	0.0139 (6)	0.0103 (6)	0.0153 (7)	0.0011 (5)	−0.0021 (5)	−0.0015 (5)
C7	0.0148 (6)	0.0128 (7)	0.0126 (7)	0.0004 (5)	−0.0020 (5)	−0.0026 (5)
C8	0.0164 (7)	0.0199 (7)	0.0131 (7)	−0.0006 (5)	−0.0047 (5)	0.0015 (5)
C9	0.0182 (7)	0.0281 (8)	0.0205 (8)	−0.0007 (6)	−0.0082 (6)	−0.0037 (6)
C10	0.0159 (7)	0.0169 (7)	0.0139 (7)	−0.0005 (5)	−0.0015 (5)	−0.0027 (5)
C11	0.0210 (7)	0.0197 (8)	0.0244 (8)	0.0004 (6)	−0.0065 (6)	−0.0075 (6)
C12	0.0163 (7)	0.0184 (7)	0.0165 (7)	−0.0022 (5)	0.0007 (5)	−0.0047 (6)
C13	0.0174 (7)	0.0209 (8)	0.0310 (8)	0.0014 (6)	−0.0071 (6)	−0.0078 (6)
C14	0.0182 (7)	0.0186 (7)	0.0194 (7)	−0.0038 (6)	−0.0054 (6)	−0.0065 (6)
C15	0.0294 (8)	0.0179 (7)	0.0204 (7)	−0.0067 (6)	−0.0063 (6)	−0.0028 (6)

Geometric parameters (Å, º)

P1—O2	1.4828 (10)	C8—H8A	0.9900
P1—N6	1.6337 (12)	C8—H8B	0.9900
P1—N2	1.6378 (11)	C9—H9A	0.9800
P1—N1	1.6928 (11)	C9—H9B	0.9800
F1—C3	1.3637 (15)	C9—H9C	0.9800
O1—C7	1.2244 (17)	C10—C11	1.524 (2)
N1—C7	1.3702 (18)	C10—H10A	0.9900
N1—H1N	0.854 (13)	C10—H10B	0.9900
N2—C8	1.4736 (17)	C11—H11A	0.9800
N2—C10	1.4788 (17)	C11—H11B	0.9800
N6—C14	1.4747 (17)	C11—H11C	0.9800
N6—C12	1.4773 (17)	C12—C13	1.522 (2)
C1—C2	1.389 (2)	C12—H12A	0.9900
C1—C6	1.392 (2)	C12—H12B	0.9900
C1—H1A	0.9500	C13—H13A	0.9800
C2—C3	1.378 (2)	C13—H13B	0.9800
C2—H2A	0.9500	C13—H13C	0.9800
C3—C4	1.374 (2)	C14—C15	1.517 (2)
C4—C5	1.385 (2)	C14—H14A	0.9900
C4—H4A	0.9500	C14—H14B	0.9900
C5—C6	1.3906 (19)	C15—H15A	0.9800
C5—H5A	0.9500	C15—H15B	0.9800
C6—C7	1.4979 (18)	C15—H15C	0.9800
C8—C9	1.5233 (19)
O2—P1—N6	118.04 (6)	C8—C9—H9A	109.5
O2—P1—N2	110.05 (6)	C8—C9—H9B	109.5
N6—P1—N2	106.21 (6)	H9A—C9—H9B	109.5
O2—P1—N1	105.37 (6)	C8—C9—H9C	109.5
N6—P1—N1	104.75 (6)	H9A—C9—H9C	109.5
N2—P1—N1	112.45 (6)	H9B—C9—H9C	109.5
C7—N1—P1	126.01 (10)	N2—C10—C11	113.44 (11)
C7—N1—H1N	119.7 (11)	N2—C10—H10A	108.9
P1—N1—H1N	114.2 (11)	C11—C10—H10A	108.9
C8—N2—C10	114.89 (11)	N2—C10—H10B	108.9
C8—N2—P1	124.90 (9)	C11—C10—H10B	108.9
C10—N2—P1	117.09 (9)	H10A—C10—H10B	107.7
C14—N6—C12	116.17 (11)	C10—C11—H11A	109.5
C14—N6—P1	119.09 (9)	C10—C11—H11B	109.5
C12—N6—P1	121.62 (9)	H11A—C11—H11B	109.5
C2—C1—C6	120.22 (13)	C10—C11—H11C	109.5
C2—C1—H1A	119.9	H11A—C11—H11C	109.5
C6—C1—H1A	119.9	H11B—C11—H11C	109.5
C3—C2—C1	118.23 (13)	N6—C12—C13	114.86 (12)
C3—C2—H2A	120.9	N6—C12—H12A	108.6
C1—C2—H2A	120.9	C13—C12—H12A	108.6
F1—C3—C4	118.50 (13)	N6—C12—H12B	108.6
F1—C3—C2	118.35 (13)	C13—C12—H12B	108.6
C4—C3—C2	123.15 (13)	H12A—C12—H12B	107.5
C3—C4—C5	117.92 (13)	C12—C13—H13A	109.5
C3—C4—H4A	121.0	C12—C13—H13B	109.5
C5—C4—H4A	121.0	H13A—C13—H13B	109.5
C4—C5—C6	120.86 (13)	C12—C13—H13C	109.5
C4—C5—H5A	119.6	H13A—C13—H13C	109.5
C6—C5—H5A	119.6	H13B—C13—H13C	109.5
C1—C6—C5	119.54 (13)	N6—C14—C15	115.14 (12)
C1—C6—C7	122.97 (12)	N6—C14—H14A	108.5
C5—C6—C7	117.50 (12)	C15—C14—H14A	108.5
O1—C7—N1	122.44 (12)	N6—C14—H14B	108.5
O1—C7—C6	120.63 (12)	C15—C14—H14B	108.5
N1—C7—C6	116.92 (12)	H14A—C14—H14B	107.5
N2—C8—C9	113.08 (11)	C14—C15—H15A	109.5
N2—C8—H8A	109.0	C14—C15—H15B	109.5
C9—C8—H8A	109.0	H15A—C15—H15B	109.5
N2—C8—H8B	109.0	C14—C15—H15C	109.5
C9—C8—H8B	109.0	H15A—C15—H15C	109.5
H8A—C8—H8B	107.8	H15B—C15—H15C	109.5
O2—P1—N1—C7	−164.80 (11)	C3—C4—C5—C6	−0.8 (2)
N6—P1—N1—C7	70.00 (12)	C2—C1—C6—C5	−1.5 (2)
N2—P1—N1—C7	−44.91 (13)	C2—C1—C6—C7	178.60 (12)
O2—P1—N2—C8	−164.07 (10)	C4—C5—C6—C1	2.5 (2)
N6—P1—N2—C8	−35.22 (12)	C4—C5—C6—C7	−177.62 (12)
N1—P1—N2—C8	78.79 (12)	P1—N1—C7—O1	−5.2 (2)
O2—P1—N2—C10	36.95 (11)	P1—N1—C7—C6	175.61 (9)
N6—P1—N2—C10	165.79 (9)	C1—C6—C7—O1	159.21 (13)
N1—P1—N2—C10	−80.19 (10)	C5—C6—C7—O1	−20.70 (19)
O2—P1—N6—C14	67.71 (11)	C1—C6—C7—N1	−21.62 (19)
N2—P1—N6—C14	−56.30 (11)	C5—C6—C7—N1	158.46 (12)
N1—P1—N6—C14	−175.49 (10)	C10—N2—C8—C9	−75.37 (15)
O2—P1—N6—C12	−91.54 (11)	P1—N2—C8—C9	125.24 (12)
N2—P1—N6—C12	144.45 (11)	C8—N2—C10—C11	−81.32 (14)
N1—P1—N6—C12	25.26 (12)	P1—N2—C10—C11	79.76 (13)
C6—C1—C2—C3	−1.1 (2)	C14—N6—C12—C13	−97.85 (14)
C1—C2—C3—F1	−177.70 (12)	P1—N6—C12—C13	61.98 (15)
C1—C2—C3—C4	2.8 (2)	C12—N6—C14—C15	57.79 (16)
F1—C3—C4—C5	178.64 (12)	P1—N6—C14—C15	−102.57 (13)
C2—C3—C4—C5	−1.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.85 (1)	1.99 (1)	2.8390 (15)	172 (2)

Symmetry code: (i) −x+1, −y, −z+1.

(II) N-(2,6-difluorobenzoyl)-N',N''-bis(4-methylpiperidin-1-yl)phosphoric triamide

Crystal data

C19H28F2N3O2P	Z = 2
Mr = 399.41	F(000) = 424
Triclinic, P1	Dx = 1.315 Mg m^−3
a = 9.6501 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0580 (13) Å	Cell parameters from 4849 reflections
c = 10.9947 (15) Å	θ = 2.6–26.4°
α = 75.392 (3)°	µ = 0.17 mm^−1
β = 77.744 (4)°	T = 90 K
γ = 88.084 (4)°	Block, colourless
V = 1008.9 (2) Å^3	0.25 × 0.22 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3952 independent reflections
Radiation source: fine-focus sealed tube	3370 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→12
Tmin = 0.958, Tmax = 0.983	k = −9→12
9054 measured reflections	l = −12→13

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.4226P] where P = (Fo^2 + 2Fc^2)/3
3952 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.31 e Å^−3
1 restraint	Δρmin = −0.36 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
P1	0.51614 (4)	0.38074 (4)	0.69930 (3)	0.01150 (10)
F1	0.44221 (10)	0.85378 (9)	0.75579 (9)	0.0280 (2)
F2	0.85888 (10)	0.70839 (10)	0.52388 (9)	0.0274 (2)
O1	0.62555 (12)	0.59114 (11)	0.82726 (10)	0.0221 (3)
O2	0.52053 (11)	0.33666 (10)	0.57979 (9)	0.0147 (2)
N1	0.56551 (13)	0.54963 (12)	0.64944 (12)	0.0128 (3)
H1N	0.5505 (17)	0.5919 (16)	0.5760 (14)	0.015*
N2	0.35810 (12)	0.35880 (12)	0.79196 (12)	0.0140 (3)
N3	0.62586 (12)	0.30814 (12)	0.78784 (11)	0.0143 (3)
C1	0.56440 (17)	0.88440 (16)	0.66585 (15)	0.0195 (3)
C2	0.5968 (2)	1.01962 (16)	0.60307 (16)	0.0261 (4)
H2B	0.5357	1.0909	0.6223	0.031*
C3	0.7214 (2)	1.04863 (17)	0.51091 (16)	0.0293 (4)
H3A	0.7460	1.1414	0.4661	0.035*
C4	0.81098 (19)	0.94496 (18)	0.48282 (16)	0.0281 (4)
H4A	0.8968	0.9653	0.4199	0.034*
C5	0.77203 (17)	0.81166 (16)	0.54872 (15)	0.0208 (3)
C6	0.64865 (16)	0.77592 (15)	0.64142 (14)	0.0159 (3)
C7	0.61155 (15)	0.62938 (15)	0.71690 (14)	0.0145 (3)
C8	0.32035 (16)	0.41758 (16)	0.90464 (14)	0.0177 (3)
H8A	0.4082	0.4395	0.9293	0.021*
H8B	0.2647	0.3485	0.9780	0.021*
C9	0.23452 (16)	0.54700 (16)	0.87722 (15)	0.0192 (3)
H9A	0.2962	0.6213	0.8149	0.023*
H9B	0.2019	0.5766	0.9578	0.023*
C10	0.10571 (16)	0.52607 (15)	0.82302 (15)	0.0183 (3)
H10A	0.0414	0.4557	0.8899	0.022*
C11	0.15441 (16)	0.46872 (15)	0.70523 (15)	0.0175 (3)
H11A	0.0709	0.4501	0.6725	0.021*
H11B	0.2164	0.5374	0.6364	0.021*
C12	0.23517 (15)	0.33648 (15)	0.73969 (15)	0.0168 (3)
H12A	0.1708	0.2659	0.8041	0.020*
H12B	0.2679	0.3018	0.6619	0.020*
C13	0.02303 (18)	0.65775 (17)	0.79406 (17)	0.0264 (4)
H13A	−0.0038	0.6917	0.8717	0.040*
H13B	−0.0626	0.6391	0.7661	0.040*
H13C	0.0823	0.7273	0.7257	0.040*
C14	0.77889 (15)	0.33638 (15)	0.74004 (15)	0.0179 (3)
H14A	0.8137	0.3892	0.7927	0.021*
H14B	0.7966	0.3926	0.6500	0.021*
C15	0.85850 (16)	0.20273 (15)	0.74646 (15)	0.0176 (3)
H15A	0.9616	0.2235	0.7184	0.021*
H15B	0.8306	0.1549	0.6866	0.021*
C16	0.82804 (16)	0.10832 (15)	0.88181 (15)	0.0186 (3)
H16A	0.8655	0.1540	0.9395	0.022*
C17	0.66810 (16)	0.08714 (15)	0.93067 (15)	0.0193 (3)
H17A	0.6314	0.0324	0.8806	0.023*
H17B	0.6487	0.0342	1.0218	0.023*
C18	0.58979 (16)	0.22228 (15)	0.91992 (14)	0.0158 (3)
H18A	0.4862	0.2034	0.9451	0.019*
H18B	0.6160	0.2718	0.9793	0.019*
C19	0.90183 (19)	−0.02812 (17)	0.88444 (18)	0.0289 (4)
H19A	1.0044	−0.0116	0.8543	0.043*
H19B	0.8665	−0.0743	0.8281	0.043*
H19C	0.8821	−0.0863	0.9725	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01361 (19)	0.01000 (18)	0.01153 (19)	0.00098 (14)	−0.00459 (14)	−0.00237 (14)
F1	0.0304 (5)	0.0215 (5)	0.0296 (6)	0.0040 (4)	0.0005 (4)	−0.0081 (4)
F2	0.0252 (5)	0.0301 (5)	0.0259 (5)	0.0012 (4)	−0.0002 (4)	−0.0100 (4)
O1	0.0341 (7)	0.0197 (6)	0.0148 (6)	−0.0017 (5)	−0.0099 (5)	−0.0041 (4)
O2	0.0204 (5)	0.0108 (5)	0.0145 (5)	0.0021 (4)	−0.0063 (4)	−0.0039 (4)
N1	0.0184 (6)	0.0104 (6)	0.0105 (6)	0.0013 (5)	−0.0069 (5)	−0.0011 (5)
N2	0.0129 (6)	0.0166 (6)	0.0149 (6)	0.0009 (5)	−0.0058 (5)	−0.0063 (5)
N3	0.0128 (6)	0.0154 (6)	0.0128 (6)	−0.0003 (5)	−0.0041 (5)	0.0012 (5)
C1	0.0262 (8)	0.0174 (8)	0.0167 (8)	−0.0018 (6)	−0.0065 (6)	−0.0058 (6)
C2	0.0418 (10)	0.0147 (8)	0.0272 (9)	0.0013 (7)	−0.0163 (8)	−0.0078 (7)
C3	0.0495 (11)	0.0164 (8)	0.0238 (9)	−0.0130 (8)	−0.0153 (8)	−0.0001 (7)
C4	0.0329 (10)	0.0289 (9)	0.0215 (9)	−0.0141 (8)	−0.0034 (7)	−0.0043 (7)
C5	0.0250 (8)	0.0215 (8)	0.0190 (8)	−0.0021 (7)	−0.0065 (6)	−0.0088 (6)
C6	0.0234 (8)	0.0141 (7)	0.0134 (7)	−0.0017 (6)	−0.0088 (6)	−0.0046 (6)
C7	0.0155 (7)	0.0139 (7)	0.0151 (8)	0.0009 (6)	−0.0040 (6)	−0.0048 (6)
C8	0.0150 (7)	0.0253 (8)	0.0139 (7)	0.0002 (6)	−0.0024 (6)	−0.0077 (6)
C9	0.0170 (8)	0.0216 (8)	0.0208 (8)	−0.0007 (6)	−0.0007 (6)	−0.0108 (6)
C10	0.0148 (7)	0.0177 (7)	0.0206 (8)	0.0002 (6)	−0.0024 (6)	−0.0026 (6)
C11	0.0137 (7)	0.0189 (8)	0.0201 (8)	−0.0001 (6)	−0.0068 (6)	−0.0026 (6)
C12	0.0142 (7)	0.0180 (7)	0.0199 (8)	−0.0022 (6)	−0.0065 (6)	−0.0052 (6)
C13	0.0217 (8)	0.0221 (8)	0.0327 (10)	0.0050 (7)	−0.0031 (7)	−0.0049 (7)
C14	0.0138 (7)	0.0156 (7)	0.0214 (8)	−0.0011 (6)	−0.0047 (6)	0.0014 (6)
C15	0.0142 (7)	0.0188 (8)	0.0206 (8)	0.0012 (6)	−0.0056 (6)	−0.0046 (6)
C16	0.0206 (8)	0.0160 (7)	0.0217 (8)	0.0038 (6)	−0.0107 (6)	−0.0043 (6)
C17	0.0218 (8)	0.0162 (7)	0.0177 (8)	0.0008 (6)	−0.0060 (6)	0.0014 (6)
C18	0.0184 (7)	0.0166 (7)	0.0114 (7)	0.0001 (6)	−0.0051 (6)	0.0000 (6)
C19	0.0282 (9)	0.0197 (8)	0.0373 (10)	0.0076 (7)	−0.0091 (8)	−0.0037 (7)

Geometric parameters (Å, º)

P1—O2	1.4812 (10)	C10—C13	1.522 (2)
P1—N3	1.6215 (12)	C10—C11	1.527 (2)
P1—N2	1.6315 (12)	C10—H10A	1.0000
P1—N1	1.6989 (12)	C11—C12	1.524 (2)
F1—C1	1.3560 (18)	C11—H11A	0.9900
F2—C5	1.3578 (18)	C11—H11B	0.9900
O1—C7	1.2121 (18)	C12—H12A	0.9900
N1—C7	1.3619 (18)	C12—H12B	0.9900
N1—H1N	0.852 (13)	C13—H13A	0.9800
N2—C12	1.4699 (18)	C13—H13B	0.9800
N2—C8	1.4766 (18)	C13—H13C	0.9800
N3—C18	1.4659 (18)	C14—C15	1.519 (2)
N3—C14	1.4700 (18)	C14—H14A	0.9900
C1—C2	1.374 (2)	C14—H14B	0.9900
C1—C6	1.386 (2)	C15—C16	1.524 (2)
C2—C3	1.384 (3)	C15—H15A	0.9900
C2—H2B	0.9500	C15—H15B	0.9900
C3—C4	1.385 (3)	C16—C19	1.521 (2)
C3—H3A	0.9500	C16—C17	1.526 (2)
C4—C5	1.375 (2)	C16—H16A	1.0000
C4—H4A	0.9500	C17—C18	1.523 (2)
C5—C6	1.384 (2)	C17—H17A	0.9900
C6—C7	1.510 (2)	C17—H17B	0.9900
C8—C9	1.519 (2)	C18—H18A	0.9900
C8—H8A	0.9900	C18—H18B	0.9900
C8—H8B	0.9900	C19—H19A	0.9800
C9—C10	1.530 (2)	C19—H19B	0.9800
C9—H9A	0.9900	C19—H19C	0.9800
C9—H9B	0.9900
O2—P1—N3	116.74 (6)	C12—C11—C10	110.37 (12)
O2—P1—N2	111.60 (6)	C12—C11—H11A	109.6
N3—P1—N2	106.71 (6)	C10—C11—H11A	109.6
O2—P1—N1	105.13 (6)	C12—C11—H11B	109.6
N3—P1—N1	105.32 (6)	C10—C11—H11B	109.6
N2—P1—N1	111.20 (6)	H11A—C11—H11B	108.1
C7—N1—P1	128.36 (10)	N2—C12—C11	111.36 (12)
C7—N1—H1N	115.7 (11)	N2—C12—H12A	109.4
P1—N1—H1N	115.6 (11)	C11—C12—H12A	109.4
C12—N2—C8	113.25 (11)	N2—C12—H12B	109.4
C12—N2—P1	119.95 (10)	C11—C12—H12B	109.4
C8—N2—P1	121.62 (10)	H12A—C12—H12B	108.0
C18—N3—C14	113.40 (11)	C10—C13—H13A	109.5
C18—N3—P1	126.95 (10)	C10—C13—H13B	109.5
C14—N3—P1	119.46 (10)	H13A—C13—H13B	109.5
F1—C1—C2	118.75 (14)	C10—C13—H13C	109.5
F1—C1—C6	117.48 (14)	H13A—C13—H13C	109.5
C2—C1—C6	123.76 (15)	H13B—C13—H13C	109.5
C1—C2—C3	117.86 (16)	N3—C14—C15	110.33 (12)
C1—C2—H2B	121.1	N3—C14—H14A	109.6
C3—C2—H2B	121.1	C15—C14—H14A	109.6
C2—C3—C4	121.22 (16)	N3—C14—H14B	109.6
C2—C3—H3A	119.4	C15—C14—H14B	109.6
C4—C3—H3A	119.4	H14A—C14—H14B	108.1
C5—C4—C3	118.02 (16)	C14—C15—C16	111.84 (12)
C5—C4—H4A	121.0	C14—C15—H15A	109.2
C3—C4—H4A	121.0	C16—C15—H15A	109.2
F2—C5—C4	119.11 (15)	C14—C15—H15B	109.2
F2—C5—C6	117.36 (14)	C16—C15—H15B	109.2
C4—C5—C6	123.53 (15)	H15A—C15—H15B	107.9
C5—C6—C1	115.60 (14)	C19—C16—C15	110.95 (13)
C5—C6—C7	122.53 (13)	C19—C16—C17	111.25 (13)
C1—C6—C7	121.78 (14)	C15—C16—C17	109.51 (12)
O1—C7—N1	125.50 (13)	C19—C16—H16A	108.3
O1—C7—C6	120.29 (12)	C15—C16—H16A	108.3
N1—C7—C6	114.20 (12)	C17—C16—H16A	108.3
N2—C8—C9	111.80 (12)	C18—C17—C16	112.56 (12)
N2—C8—H8A	109.3	C18—C17—H17A	109.1
C9—C8—H8A	109.3	C16—C17—H17A	109.1
N2—C8—H8B	109.3	C18—C17—H17B	109.1
C9—C8—H8B	109.3	C16—C17—H17B	109.1
H8A—C8—H8B	107.9	H17A—C17—H17B	107.8
C8—C9—C10	112.57 (12)	N3—C18—C17	110.36 (12)
C8—C9—H9A	109.1	N3—C18—H18A	109.6
C10—C9—H9A	109.1	C17—C18—H18A	109.6
C8—C9—H9B	109.1	N3—C18—H18B	109.6
C10—C9—H9B	109.1	C17—C18—H18B	109.6
H9A—C9—H9B	107.8	H18A—C18—H18B	108.1
C13—C10—C11	112.49 (13)	C16—C19—H19A	109.5
C13—C10—C9	111.58 (13)	C16—C19—H19B	109.5
C11—C10—C9	109.18 (12)	H19A—C19—H19B	109.5
C13—C10—H10A	107.8	C16—C19—H19C	109.5
C11—C10—H10A	107.8	H19A—C19—H19C	109.5
C9—C10—H10A	107.8	H19B—C19—H19C	109.5
O2—P1—N1—C7	−162.48 (12)	C2—C1—C6—C7	177.41 (14)
N3—P1—N1—C7	−38.61 (14)	P1—N1—C7—O1	0.2 (2)
N2—P1—N1—C7	76.60 (14)	P1—N1—C7—C6	179.18 (10)
O2—P1—N2—C12	−15.99 (13)	C5—C6—C7—O1	103.58 (18)
N3—P1—N2—C12	−144.59 (11)	C1—C6—C7—O1	−72.8 (2)
N1—P1—N2—C12	101.06 (11)	C5—C6—C7—N1	−75.44 (18)
O2—P1—N2—C8	−168.81 (11)	C1—C6—C7—N1	108.16 (16)
N3—P1—N2—C8	62.58 (13)	C12—N2—C8—C9	−52.83 (16)
N1—P1—N2—C8	−51.77 (13)	P1—N2—C8—C9	101.65 (13)
O2—P1—N3—C18	−117.48 (12)	N2—C8—C9—C10	52.12 (17)
N2—P1—N3—C18	8.08 (13)	C8—C9—C10—C13	−178.96 (13)
N1—P1—N3—C18	126.35 (12)	C8—C9—C10—C11	−53.99 (17)
O2—P1—N3—C14	67.96 (12)	C13—C10—C11—C12	−179.43 (12)
N2—P1—N3—C14	−166.49 (11)	C9—C10—C11—C12	56.13 (16)
N1—P1—N3—C14	−48.21 (12)	C8—N2—C12—C11	56.01 (16)
F1—C1—C2—C3	−179.49 (14)	P1—N2—C12—C11	−98.95 (13)
C6—C1—C2—C3	−0.5 (2)	C10—C11—C12—N2	−57.73 (16)
C1—C2—C3—C4	−0.1 (2)	C18—N3—C14—C15	57.82 (16)
C2—C3—C4—C5	0.4 (3)	P1—N3—C14—C15	−126.92 (11)
C3—C4—C5—F2	−179.27 (14)	N3—C14—C15—C16	−55.89 (16)
C3—C4—C5—C6	−0.1 (2)	C14—C15—C16—C19	176.66 (13)
F2—C5—C6—C1	178.70 (13)	C14—C15—C16—C17	53.47 (16)
C4—C5—C6—C1	−0.4 (2)	C19—C16—C17—C18	−175.72 (13)
F2—C5—C6—C7	2.1 (2)	C15—C16—C17—C18	−52.71 (16)
C4—C5—C6—C7	−177.05 (14)	C14—N3—C18—C17	−56.67 (16)
F1—C1—C6—C5	179.78 (13)	P1—N3—C18—C17	128.49 (12)
C2—C1—C6—C5	0.8 (2)	C16—C17—C18—N3	54.07 (17)
F1—C1—C6—C7	−3.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.85 (1)	1.94 (1)	2.7786 (16)	168 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

(III) N,N'-dicyclohexyl-N''-(2-fluorobenzoyl)-N,N'-dimethylphosphoric triamide

Crystal data

C21H33FN3O2P	Z = 2
Mr = 409.47	F(000) = 440
Triclinic, P1	Dx = 1.228 Mg m^−3
a = 10.3245 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.5131 (2) Å	Cell parameters from 8116 reflections
c = 11.3253 (2) Å	θ = 4.3–68.2°
α = 67.915 (1)°	µ = 1.34 mm^−1
β = 77.902 (1)°	T = 90 K
γ = 79.978 (1)°	Block, colourless
V = 1107.61 (4) Å^3	0.15 × 0.15 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3824 independent reflections
Radiation source: fine-focus sealed tube	3710 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 68.2°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −12→12
Tmin = 0.824, Tmax = 0.878	k = −11→12
10794 measured reflections	l = −13→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0581P)^2 + 0.4562P] where P = (Fo^2 + 2Fc^2)/3
3824 reflections	(Δ/σ)max = 0.001
292 parameters	Δρmax = 0.33 e Å^−3
2 restraints	Δρmin = −0.43 e Å^−3

Special details

Experimental. Colorless crystal of AT18 was mounted on a Cryoloop with Paratone-N oil and data collected on at 90 K using a Bruker APEXII CCD detector and Cu K alpha radiation generated from a rotating anode. Data corrected for absorption with SADABS and structure solved by direct methods. Phenyl ring C1–C6 and fluorine atom were disordered over two positions and refined using a two-part disorder model with occupancy of 64.39/35.61. Distance between carbon atom C1B—C7 restained to 1.50(0.01) angstroms. All non-hydrogen atoms were refined anisotropically by full matrix least squares on F2. Hydrogen atom H1N was found from a Fourier difference map and was allowed to refine isotropically with a distance of 0.87(0.01) angstroms with 1.20U_eq of parent N atom. All other hydrogen atoms were placed in calculated positions with C—H distances of 0.950 for CH(aromatic), 1.000 for CH, 0.990 for CH2, 0.980 for CH3 with U_eq values of 1.20 and 1.50 of parent C atoms.

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	Occ. (<1)
P1	0.42479 (3)	0.43096 (3)	0.20706 (3)	0.01861 (12)
O1	0.65592 (10)	0.41228 (13)	0.34616 (10)	0.0344 (3)
O2	0.35132 (9)	0.49988 (10)	0.09619 (9)	0.0228 (2)
N1	0.57694 (11)	0.48747 (12)	0.15539 (11)	0.0205 (3)
H1N	0.6021 (16)	0.5136 (17)	0.0729 (9)	0.025*
N2	0.34610 (11)	0.46790 (12)	0.33325 (10)	0.0204 (3)
N3	0.44984 (12)	0.26222 (12)	0.25788 (12)	0.0260 (3)
C7	0.67042 (13)	0.47474 (16)	0.23001 (13)	0.0243 (3)
F1A	0.93376 (15)	0.3704 (2)	0.27751 (16)	0.0495 (6)	0.644 (4)
C1A	0.7894 (4)	0.5529 (7)	0.1528 (6)	0.0239 (13)	0.644 (4)
C2A	0.9190 (3)	0.4988 (5)	0.1831 (4)	0.0288 (8)	0.644 (4)
C3A	1.0324 (2)	0.5616 (6)	0.1187 (4)	0.0313 (7)	0.644 (4)
H3A	1.1171	0.5205	0.1424	0.038*	0.644 (4)
C4A	1.0197 (3)	0.6860 (5)	0.0188 (4)	0.0378 (8)	0.644 (4)
H4A	1.0966	0.7317	−0.0271	0.045*	0.644 (4)
C5A	0.8955 (4)	0.7452 (4)	−0.0155 (4)	0.0360 (7)	0.644 (4)
H5A	0.8869	0.8311	−0.0842	0.043*	0.644 (4)
C6A	0.7862 (6)	0.6782 (6)	0.0508 (6)	0.0283 (12)	0.644 (4)
H6A	0.7023	0.7199	0.0255	0.034*	0.644 (4)
F1B	0.6933 (3)	0.7324 (3)	0.0201 (3)	0.0346 (9)	0.356 (4)
C1B	0.8032 (9)	0.5289 (12)	0.1680 (11)	0.023 (3)*	0.356 (4)
C2B	0.8019 (15)	0.6499 (14)	0.0701 (14)	0.032 (3)*	0.356 (4)
C3B	0.9283 (9)	0.7065 (7)	0.0119 (6)	0.0302 (17)*	0.356 (4)
H3B	0.9336	0.7930	−0.0569	0.036*	0.356 (4)
C4B	1.0385 (7)	0.6309 (8)	0.0598 (8)	0.0260 (16)*	0.356 (4)
H4B	1.1223	0.6654	0.0216	0.031*	0.356 (4)
C5B	1.0349 (6)	0.5069 (6)	0.1606 (6)	0.0258 (15)*	0.356 (4)
H5B	1.1142	0.4571	0.1919	0.031*	0.356 (4)
C6B	0.9124 (7)	0.4562 (7)	0.2155 (7)	0.0217 (18)*	0.356 (4)
H6B	0.9062	0.3710	0.2858	0.026*	0.356 (4)
C8	0.27088 (13)	0.60618 (14)	0.31331 (13)	0.0212 (3)
H8A	0.2491	0.6433	0.2237	0.025*
C9	0.35276 (15)	0.70709 (16)	0.32442 (15)	0.0300 (3)
H9A	0.4346	0.7167	0.2594	0.036*
H9B	0.3796	0.6709	0.4110	0.036*
C10	0.2724 (2)	0.84849 (18)	0.30331 (18)	0.0447 (5)
H10A	0.3253	0.9108	0.3163	0.054*
H10B	0.2544	0.8891	0.2133	0.054*
C11	0.1409 (2)	0.83783 (18)	0.39551 (18)	0.0455 (5)
H11A	0.1587	0.8066	0.4852	0.055*
H11B	0.0893	0.9300	0.3760	0.055*
C12	0.06011 (17)	0.73717 (18)	0.38358 (18)	0.0393 (4)
H12A	0.0351	0.7729	0.2963	0.047*
H12B	−0.0228	0.7286	0.4472	0.047*
C13	0.13923 (14)	0.59522 (16)	0.40678 (15)	0.0274 (3)
H13A	0.0860	0.5325	0.3948	0.033*
H13B	0.1575	0.5557	0.4967	0.033*
C14	0.36563 (14)	0.38265 (16)	0.46596 (13)	0.0268 (3)
H14A	0.3909	0.4397	0.5071	0.040*
H14B	0.4364	0.3076	0.4647	0.040*
H14C	0.2826	0.3438	0.5147	0.040*
C15	0.57431 (14)	0.18274 (15)	0.22067 (14)	0.0269 (3)
H15A	0.6429	0.2493	0.1778	0.032*
C16	0.62556 (17)	0.07397 (18)	0.34002 (15)	0.0364 (4)
H16A	0.5592	0.0071	0.3867	0.044*
H16B	0.6378	0.1192	0.3988	0.044*
C17	0.75812 (19)	−0.00234 (19)	0.30104 (17)	0.0434 (4)
H17A	0.8263	0.0635	0.2605	0.052*
H17B	0.7884	−0.0743	0.3790	0.052*
C18	0.7439 (2)	−0.06916 (19)	0.20670 (17)	0.0443 (5)
H18A	0.6812	−0.1405	0.2496	0.053*
H18B	0.8314	−0.1150	0.1805	0.053*
C19	0.69255 (17)	0.03868 (17)	0.08707 (16)	0.0364 (4)
H19A	0.6789	−0.0078	0.0298	0.044*
H19B	0.7601	0.1039	0.0390	0.044*
C20	0.56113 (16)	0.11894 (16)	0.12340 (15)	0.0315 (3)
H20A	0.5347	0.1929	0.0447	0.038*
H20B	0.4904	0.0559	0.1609	0.038*
C21	0.32908 (15)	0.18998 (16)	0.30808 (15)	0.0309 (3)
H21A	0.3470	0.1031	0.3786	0.046*
H21B	0.3029	0.1704	0.2388	0.046*
H21C	0.2568	0.2483	0.3403	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01483 (18)	0.0215 (2)	0.02007 (19)	−0.00204 (13)	−0.00211 (13)	−0.00817 (14)
O1	0.0238 (5)	0.0568 (7)	0.0235 (5)	0.0006 (5)	−0.0065 (4)	−0.0160 (5)
O2	0.0162 (5)	0.0314 (5)	0.0229 (5)	−0.0026 (4)	−0.0020 (4)	−0.0124 (4)
N1	0.0166 (5)	0.0267 (6)	0.0189 (5)	−0.0031 (4)	−0.0023 (4)	−0.0088 (5)
N2	0.0191 (5)	0.0209 (6)	0.0197 (6)	−0.0001 (4)	−0.0032 (4)	−0.0064 (4)
N3	0.0210 (6)	0.0222 (6)	0.0328 (7)	−0.0019 (5)	0.0019 (5)	−0.0109 (5)
C7	0.0173 (6)	0.0335 (8)	0.0267 (7)	0.0017 (6)	−0.0052 (5)	−0.0167 (6)
F1A	0.0250 (8)	0.0795 (15)	0.0417 (10)	0.0101 (8)	−0.0117 (6)	−0.0223 (10)
C1A	0.0099 (15)	0.042 (3)	0.031 (3)	0.0050 (17)	−0.0085 (14)	−0.026 (2)
C2A	0.0194 (15)	0.041 (2)	0.0303 (18)	−0.0020 (15)	−0.0071 (12)	−0.0168 (17)
C3A	0.0162 (13)	0.049 (2)	0.0371 (19)	−0.0017 (13)	−0.0069 (12)	−0.024 (2)
C4A	0.0237 (17)	0.056 (2)	0.045 (2)	−0.0200 (16)	0.0094 (14)	−0.031 (2)
C5A	0.0313 (19)	0.0385 (18)	0.0416 (17)	−0.0121 (15)	0.0025 (15)	−0.0184 (16)
C6A	0.028 (3)	0.028 (3)	0.031 (3)	−0.009 (2)	0.0014 (19)	−0.013 (2)
F1B	0.0277 (17)	0.0334 (15)	0.0424 (16)	−0.0083 (12)	−0.0069 (11)	−0.0099 (12)
C8	0.0205 (7)	0.0213 (7)	0.0219 (6)	0.0002 (5)	−0.0041 (5)	−0.0083 (5)
C9	0.0314 (8)	0.0298 (8)	0.0312 (8)	−0.0100 (6)	0.0016 (6)	−0.0140 (6)
C10	0.0621 (12)	0.0252 (8)	0.0460 (10)	−0.0108 (8)	0.0059 (9)	−0.0164 (7)
C11	0.0579 (12)	0.0293 (9)	0.0454 (10)	0.0058 (8)	0.0019 (8)	−0.0185 (8)
C12	0.0310 (8)	0.0384 (9)	0.0441 (9)	0.0105 (7)	−0.0027 (7)	−0.0174 (7)
C13	0.0204 (7)	0.0287 (8)	0.0332 (8)	−0.0004 (6)	−0.0016 (6)	−0.0134 (6)
C14	0.0257 (7)	0.0300 (8)	0.0198 (7)	0.0024 (6)	−0.0028 (5)	−0.0059 (6)
C15	0.0245 (7)	0.0248 (7)	0.0284 (7)	0.0018 (6)	0.0004 (6)	−0.0106 (6)
C16	0.0403 (9)	0.0360 (9)	0.0282 (8)	0.0088 (7)	−0.0046 (7)	−0.0120 (7)
C17	0.0446 (10)	0.0419 (10)	0.0358 (9)	0.0176 (8)	−0.0100 (7)	−0.0126 (7)
C18	0.0499 (11)	0.0341 (9)	0.0405 (9)	0.0145 (8)	−0.0027 (8)	−0.0143 (7)
C19	0.0421 (9)	0.0317 (8)	0.0327 (8)	0.0038 (7)	0.0005 (7)	−0.0151 (7)
C20	0.0347 (8)	0.0280 (8)	0.0299 (8)	0.0008 (6)	−0.0019 (6)	−0.0115 (6)
C21	0.0282 (8)	0.0247 (7)	0.0371 (8)	−0.0055 (6)	0.0038 (6)	−0.0114 (6)

Geometric parameters (Å, º)

P1—O2	1.4836 (10)	C9—C10	1.531 (2)
P1—N2	1.6353 (11)	C9—H9A	0.9900
P1—N3	1.6371 (12)	C9—H9B	0.9900
P1—N1	1.6856 (11)	C10—C11	1.521 (3)
O1—C7	1.2190 (18)	C10—H10A	0.9900
N1—C7	1.3694 (17)	C10—H10B	0.9900
N1—H1N	0.863 (9)	C11—C12	1.516 (3)
N2—C14	1.4677 (17)	C11—H11A	0.9900
N2—C8	1.4836 (17)	C11—H11B	0.9900
N3—C21	1.4705 (18)	C12—C13	1.528 (2)
N3—C15	1.4803 (17)	C12—H12A	0.9900
C7—C1B	1.505 (8)	C12—H12B	0.9900
C7—C1A	1.520 (5)	C13—H13A	0.9900
F1A—C2A	1.379 (5)	C13—H13B	0.9900
C1A—C6A	1.388 (10)	C14—H14A	0.9800
C1A—C2A	1.419 (6)	C14—H14B	0.9800
C2A—C3A	1.374 (5)	C14—H14C	0.9800
C3A—C4A	1.377 (5)	C15—C20	1.527 (2)
C3A—H3A	0.9500	C15—C16	1.530 (2)
C4A—C5A	1.391 (5)	C15—H15A	1.0000
C4A—H4A	0.9500	C16—C17	1.530 (2)
C5A—C6A	1.362 (7)	C16—H16A	0.9900
C5A—H5A	0.9500	C16—H16B	0.9900
C6A—H6A	0.9500	C17—C18	1.524 (3)
F1B—C2B	1.375 (12)	C17—H17A	0.9900
C1B—C2B	1.337 (17)	C17—H17B	0.9900
C1B—C6B	1.338 (14)	C18—C19	1.529 (2)
C2B—C3B	1.451 (19)	C18—H18A	0.9900
C3B—C4B	1.357 (9)	C18—H18B	0.9900
C3B—H3B	0.9500	C19—C20	1.533 (2)
C4B—C5B	1.372 (8)	C19—H19A	0.9900
C4B—H4B	0.9500	C19—H19B	0.9900
C5B—C6B	1.387 (9)	C20—H20A	0.9900
C5B—H5B	0.9500	C20—H20B	0.9900
C6B—H6B	0.9500	C21—H21A	0.9800
C8—C9	1.521 (2)	C21—H21B	0.9800
C8—C13	1.5300 (19)	C21—H21C	0.9800
C8—H8A	1.0000
O2—P1—N2	110.71 (5)	C9—C10—H10A	109.3
O2—P1—N3	117.00 (6)	C11—C10—H10B	109.3
N2—P1—N3	105.12 (6)	C9—C10—H10B	109.3
O2—P1—N1	105.47 (5)	H10A—C10—H10B	108.0
N2—P1—N1	112.52 (6)	C12—C11—C10	110.89 (15)
N3—P1—N1	106.11 (6)	C12—C11—H11A	109.5
C7—N1—P1	126.82 (10)	C10—C11—H11A	109.5
C7—N1—H1N	117.4 (11)	C12—C11—H11B	109.5
P1—N1—H1N	114.9 (11)	C10—C11—H11B	109.5
C14—N2—C8	116.85 (11)	H11A—C11—H11B	108.0
C14—N2—P1	123.33 (9)	C11—C12—C13	111.01 (14)
C8—N2—P1	118.80 (9)	C11—C12—H12A	109.4
C21—N3—C15	117.08 (12)	C13—C12—H12A	109.4
C21—N3—P1	115.59 (9)	C11—C12—H12B	109.4
C15—N3—P1	124.43 (10)	C13—C12—H12B	109.4
O1—C7—N1	123.16 (13)	H12A—C12—H12B	108.0
O1—C7—C1B	116.5 (5)	C12—C13—C8	110.61 (13)
N1—C7—C1B	120.1 (5)	C12—C13—H13A	109.5
O1—C7—C1A	124.4 (3)	C8—C13—H13A	109.5
N1—C7—C1A	112.3 (3)	C12—C13—H13B	109.5
C1B—C7—C1A	10.7 (6)	C8—C13—H13B	109.5
C6A—C1A—C2A	113.6 (4)	H13A—C13—H13B	108.1
C6A—C1A—C7	126.3 (4)	N2—C14—H14A	109.5
C2A—C1A—C7	120.1 (5)	N2—C14—H14B	109.5
C3A—C2A—F1A	117.5 (3)	H14A—C14—H14B	109.5
C3A—C2A—C1A	124.3 (4)	N2—C14—H14C	109.5
F1A—C2A—C1A	118.0 (4)	H14A—C14—H14C	109.5
C2A—C3A—C4A	118.0 (3)	H14B—C14—H14C	109.5
C2A—C3A—H3A	121.0	N3—C15—C20	113.11 (12)
C4A—C3A—H3A	121.0	N3—C15—C16	110.87 (12)
C3A—C4A—C5A	120.6 (3)	C20—C15—C16	111.50 (13)
C3A—C4A—H4A	119.7	N3—C15—H15A	107.0
C5A—C4A—H4A	119.7	C20—C15—H15A	107.0
C6A—C5A—C4A	119.1 (5)	C16—C15—H15A	107.0
C6A—C5A—H5A	120.5	C15—C16—C17	110.48 (13)
C4A—C5A—H5A	120.5	C15—C16—H16A	109.6
C5A—C6A—C1A	124.4 (6)	C17—C16—H16A	109.6
C5A—C6A—H6A	117.8	C15—C16—H16B	109.6
C1A—C6A—H6A	117.8	C17—C16—H16B	109.6
C2B—C1B—C6B	124.7 (9)	H16A—C16—H16B	108.1
C2B—C1B—C7	116.5 (11)	C18—C17—C16	110.94 (15)
C6B—C1B—C7	118.8 (8)	C18—C17—H17A	109.5
C1B—C2B—F1B	127.8 (13)	C16—C17—H17A	109.5
C1B—C2B—C3B	117.4 (11)	C18—C17—H17B	109.5
F1B—C2B—C3B	114.7 (11)	C16—C17—H17B	109.5
C4B—C3B—C2B	117.2 (8)	H17A—C17—H17B	108.0
C4B—C3B—H3B	121.4	C17—C18—C19	110.80 (14)
C2B—C3B—H3B	121.4	C17—C18—H18A	109.5
C3B—C4B—C5B	123.3 (7)	C19—C18—H18A	109.5
C3B—C4B—H4B	118.4	C17—C18—H18B	109.5
C5B—C4B—H4B	118.4	C19—C18—H18B	109.5
C4B—C5B—C6B	118.2 (7)	H18A—C18—H18B	108.1
C4B—C5B—H5B	120.9	C18—C19—C20	111.47 (13)
C6B—C5B—H5B	120.9	C18—C19—H19A	109.3
C1B—C6B—C5B	119.1 (7)	C20—C19—H19A	109.3
C1B—C6B—H6B	120.4	C18—C19—H19B	109.3
C5B—C6B—H6B	120.4	C20—C19—H19B	109.3
N2—C8—C9	112.02 (11)	H19A—C19—H19B	108.0
N2—C8—C13	110.67 (11)	C15—C20—C19	111.23 (13)
C9—C8—C13	111.09 (12)	C15—C20—H20A	109.4
N2—C8—H8A	107.6	C19—C20—H20A	109.4
C9—C8—H8A	107.6	C15—C20—H20B	109.4
C13—C8—H8A	107.6	C19—C20—H20B	109.4
C8—C9—C10	110.66 (14)	H20A—C20—H20B	108.0
C8—C9—H9A	109.5	N3—C21—H21A	109.5
C10—C9—H9A	109.5	N3—C21—H21B	109.5
C8—C9—H9B	109.5	H21A—C21—H21B	109.5
C10—C9—H9B	109.5	N3—C21—H21C	109.5
H9A—C9—H9B	108.1	H21A—C21—H21C	109.5
C11—C10—C9	111.55 (14)	H21B—C21—H21C	109.5
C11—C10—H10A	109.3
O2—P1—N1—C7	166.02 (12)	O1—C7—C1B—C6B	33.6 (12)
N2—P1—N1—C7	45.22 (14)	N1—C7—C1B—C6B	−141.5 (8)
N3—P1—N1—C7	−69.21 (13)	C1A—C7—C1B—C6B	174 (5)
O2—P1—N2—C14	158.40 (11)	C6B—C1B—C2B—F1B	−177.2 (10)
N3—P1—N2—C14	31.17 (13)	C7—C1B—C2B—F1B	1 (2)
N1—P1—N2—C14	−83.86 (12)	C6B—C1B—C2B—C3B	0 (2)
O2—P1—N2—C8	−33.54 (12)	C7—C1B—C2B—C3B	177.8 (8)
N3—P1—N2—C8	−160.77 (10)	C1B—C2B—C3B—C4B	1.2 (16)
N1—P1—N2—C8	84.20 (11)	F1B—C2B—C3B—C4B	178.4 (7)
O2—P1—N3—C21	−62.72 (12)	C2B—C3B—C4B—C5B	−1.3 (11)
N2—P1—N3—C21	60.56 (12)	C3B—C4B—C5B—C6B	0.5 (10)
N1—P1—N3—C21	179.97 (10)	C2B—C1B—C6B—C5B	−0.5 (19)
O2—P1—N3—C15	97.35 (12)	C7—C1B—C6B—C5B	−178.6 (7)
N2—P1—N3—C15	−139.37 (12)	C4B—C5B—C6B—C1B	0.5 (11)
N1—P1—N3—C15	−19.96 (14)	C14—N2—C8—C9	73.62 (15)
P1—N1—C7—O1	4.1 (2)	P1—N2—C8—C9	−95.21 (12)
P1—N1—C7—C1B	178.8 (6)	C14—N2—C8—C13	−50.95 (16)
P1—N1—C7—C1A	−173.0 (3)	P1—N2—C8—C13	140.22 (10)
O1—C7—C1A—C6A	−141.5 (5)	N2—C8—C9—C10	179.97 (12)
N1—C7—C1A—C6A	35.6 (6)	C13—C8—C9—C10	−55.69 (16)
C1B—C7—C1A—C6A	174 (4)	C8—C9—C10—C11	55.5 (2)
O1—C7—C1A—C2A	38.2 (6)	C9—C10—C11—C12	−55.9 (2)
N1—C7—C1A—C2A	−144.7 (4)	C10—C11—C12—C13	56.5 (2)
C1B—C7—C1A—C2A	−6 (3)	C11—C12—C13—C8	−56.75 (18)
C6A—C1A—C2A—C3A	−0.5 (7)	N2—C8—C13—C12	−178.41 (12)
C7—C1A—C2A—C3A	179.8 (3)	C9—C8—C13—C12	56.50 (16)
C6A—C1A—C2A—F1A	−175.9 (4)	C21—N3—C15—C20	54.79 (17)
C7—C1A—C2A—F1A	4.4 (6)	P1—N3—C15—C20	−105.01 (14)
F1A—C2A—C3A—C4A	176.0 (3)	C21—N3—C15—C16	−71.31 (17)
C1A—C2A—C3A—C4A	0.6 (5)	P1—N3—C15—C16	128.89 (13)
C2A—C3A—C4A—C5A	−0.2 (4)	N3—C15—C16—C17	−176.95 (14)
C3A—C4A—C5A—C6A	−0.2 (5)	C20—C15—C16—C17	56.06 (19)
C4A—C5A—C6A—C1A	0.4 (7)	C15—C16—C17—C18	−57.3 (2)
C2A—C1A—C6A—C5A	−0.1 (8)	C16—C17—C18—C19	57.1 (2)
C7—C1A—C6A—C5A	179.6 (4)	C17—C18—C19—C20	−55.6 (2)
O1—C7—C1B—C2B	−144.7 (10)	N3—C15—C20—C19	179.58 (12)
N1—C7—C1B—C2B	40.3 (14)	C16—C15—C20—C19	−54.65 (17)
C1A—C7—C1B—C2B	−5 (3)	C18—C19—C20—C15	54.31 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.86 (1)	1.93 (1)	2.7476 (14)	158 (2)

Symmetry code: (i) −x+1, −y+1, −z.