Four related diethyl [(aryl­amino)­(4-ethynylphen­yl)meth­yl]phosphon­ates

Crystal structures are reported for four related diethyl [(aryl­amino)­(4-ethynyl­phenyl)lmethyl]phosphon­ate derivatives, namely diethyl [(4-bromo­anilino)(4-ethynyl­phenyl)methyl]phosphon­ate, C₁₉H₂₁BrNO₃P, (I), diethyl ((4-chloro-2-methylanilino){4-[2-(tri­methyl­silyl)ethynyl]phenyl}methyl)phosphon­ate, C₂₃H₃₁ClNO₃PSi, (II), diethyl ((4-fluoroanilino){4-[2-(tri­methyl­silyl)ethynyl]phenyl}methyl)phosphonate, C₂₂H₂₉FNO₃PSi, (III), and diethyl [(4-ethynyl­phenyl)(naphthalen-2-yl­amino)­methyl]phosphon­ate, C₂₃H₂₄NO₃P, (IV). The conformation of the anilino­benzyl group is very similar in all four compounds. The P—C bond has an approximately staggered conformation, with the aniline and ethynylphenyl groups in gauche positions with respect to the P=O double bond. The two six-membered rings are almost perpendicular. The sums of the valence angles about the N atoms vary from 344 (2) to 351 (2)°. In the crystal structures, mol­ecules of (I), (III) and (IV) are arranged as centro­symmetric or pseudo­centro­symmetric dimers connected by two N—H...O=P hydrogen bonds. The mol­ecules of (II) are arranged as centro­symmetric dimers connected by C_meth­yl—H...O=P hydrogen bonds. The N—H bond of (II) is not involved in hydrogen bonding.

S1. Introduction

α-Amino­phospho­nates are structural analogues of natural amino acids. They have been the subject of considerable attention due to their potential biological activities. They may be applied as enzyme inhibitors (Maier & Spörri, 1991), anti­bacterial agents (Atherton et al., 1986), anti­tumour agents (Lavielle et al., 1991) or anti­viral agents (Huang & Chen, 2000; Xu et al., 2006). α-Amino­phospho­nates can be synthesized via the Kabachnik–Fields reaction (Cherkasov & Galkin, 1998) by the coupling of a carbonyl, an amine and a di­alkyl­phosphite unit. We report here the syntheses and crystal structures of four di­ethyl aryl­amino­(4-ethynyl­phenyl)­methyl­phospho­nate derivatives, namely di­ethyl [(4-bromo­anilino)(4-ethynyl­phenyl)­methyl]­phospho­nate, (I), di­ethyl ((4-chloro-2-methyl­anilino){4-[2-(tri­methyl­silyl)ethynyl]phenyl}­methyl)­phospho­nate, (II), di­ethyl ((4-fluoro­anilino){4-[2-(tri­methyl­silyl)ethynyl]phenyl}­methyl)­phospho­nate, (III), and di­ethyl [(4-ethynyl­phenyl)(naphthalen-2-yl­amino)­methyl]­phospho­nate, (IV).

S2. Experimental

S2.1. Synthesis and crystallization

Compounds (I)–(IV) were prepared via a three-component reaction of an aldehyde, an amine and di­ethyl phosphite, as described by Wu et al. (2006). Thus, 4-(tri­methyl­silylethynyl)benzaldehyde (1 mmol) was reacted at room temperature with 4-bromo­aniline (1.2 mmol) and di­ethyl phosphite (1.2 mmol) in aceto­nitrile (2.5 ml) using molecular iodine (0.2 mmol) as catalyst. Next, the tri­methyl­silyl group was removed by reacting the product with tetra­butyl­ammonium fluoride (1 equivalent) in tetra­hydro­furane (2.5 ml). Compound (I) was obtained in a yield of 83%. The crude product was purified by chromatography through a column filled with silica gel, using ethyl acetate/n-hexane (7:3 v/v) as solvent. Recrystallization from ethyl acetate resulted in pale-brown blocks of (I).

4-(Tri­methyl­silylethynyl)benzaldehyde (1 mmol) was reacted at room temperature with 4-chloro-2-methyl­aniline (1.2 mmol) and di­ethyl phosphite (1.2 mmol) in aceto­nitrile (2.5 ml) using molecular iodine (0.2 mmol) as catalyst, resulting in (II) in a yield of 87%. The solvent was removed and the residue purified through a silica-gel column using ethyl acetate/n-hexane (7:3 v/v) as solvent. Recrystallization from ethyl acetate/n-hexane (7:3 v/v) resulted in pale-brown blocks of (II).

4-(Tri­methyl­silylethynyl)benzaldehyde (1 mmol) was reacted at room temperature with 4-fluoro­aniline (1.2 mmol) and di­ethyl­phosphite (1.2 mmol) in aceto­nitrile (2.5 ml) using molecular iodine (0.2 mmol) as catalyst, resulting in (III) in a yield of 77%. The solvent was removed and the residue purified through a silica-gel column using ethyl acetate/n-hexane (7:3 v/v) as solvent. Recrystallization from ethyl acetate/n-hexane (7:3 v/v) resulted in pale-brown blocks of (III).

4-(Tri­methyl­silylethynyl)benzaldehyde (1 mmol) was reacted at room temperature with β-naphthyl­amine (1.2 mmol) and di­ethyl­phosphite (1.2 mmol) in aceto­nitrile (2.5 ml) using molecular iodine (0.2 mmol) as catalyst. Next, the tri­methyl­silyl group was removed by reacting the product with tetra­butyl­ammonium fluoride (1 equivalent) in tetra­hydro­furan (2.5 ml). Compound (IV) was obtained in a yield of 93%. The crude product was purified by chromatography through a column filled with silica gel using di­chloro­methane as solvent. Recrystallization from ethyl acetate/n-hexane (7:3 v/v) resulted in pale-brown blocks of (IV).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically and treated as riding, with C—H = 0.95–1.00 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) for other H atoms. N-bound H atoms were located from difference Fourier syntheses; their coordinates and isotropic displacement parameters were refined. Some ethyl groups in (I) and (II) were found to be disordered over two orientations and were refined with split atoms. The occupancy factors refined to 0.881 (9) for C17, 0.877 (7) for C18 and C19, 0.119 (9) for C17', 0.123 (7) for C18' and C19' of (I), and 0.516 (11) for C18 and C19 and 0.484 (11) for C18' and C19' of (II). The crystal structure of (II) was refined in the nonstandard space group I2/a rather than in C2/c, to avoid a large monoclinic angle of β = 130.698 (1)°.

S3. Results and discussion

The conformation of the anilino­benzyl fragment of (I) (Fig. 1) is very similar to that observed in the crystal structure of unsubstituted di­ethyl anilino­benzyl­phospho­nate (Rużić-Toroš et al., 1978). The P1—C1 bond has a staggered conformation, with the C1—H bond in a trans position with respect to the P═O double bond. The two benzene rings are almost perpendicular [angle between planes = 87.34 (7)°]. The ethynyl group shows a small deviation from the plane of the C2–C7 benzene ring [atoms C8 and C9 deviate by 0.037 (3) and 0.079 (4) Å, respectively, from the benzene plane]. The N atom shows a small deviation from planarity; the sum of the three valence angles about the N atom is 345 (1)°. The molecules are connected by inter­molecular N—H···O═P hydrogen bonds to form centrosymmetric dimers (Fig. 2, Table 2). The dimers are also stabilized by two inter­molecular C—H···O═P contacts, with H···O distances of 2.55 and 2.59 Å. Neighbouring dimers are connected by a weak inter­molecular C_ethynyl—H···N contact, an additional C—H···O contact, two very weak C—H···Br contacts and a C_methyl—H···π_benzene contact.

The conformation of the anilino­benzyl fragment of (II) (Fig. 3) is very similar to that observed for (I). The angle between the planes of the benzene rings is 82.49 (14)°. The N atom again shows a small deviation from planarity; the sum of the three valence angles about the N atom is 346 (3)°. The N—H bond is not involved in hydrogen bonding. The crystal packing of (II) is shown in Fig. 4. The molecules are connected by inter­molecular C—H···O═P contacts, with H···O distances of 2.49 and 2.60 Å, to form centrosymmetric dimers (Table 3). The shorter of these contacts involves the methyl group attached to the aniline group. The presence of this methyl group near the N—H bond may prevent the amino group from being involved in the hydrogen-bonding system. A similar situation is found in the crystal structure of di­ethyl [(2-chloro­phenyl­amino)(2-hy­droxy­phenyl)­methyl]­phospho­nate (Wang et al., 2012). There, a Cl substituent is positioned next to the N—H bond and again the amino group is not involved in inter­molecular hydrogen bonding. The dimers of (II) are connected by an additional C—H···O contact, with an H···O distance of 2.54 Å.

The molecular structure of (III) (Fig. 5) is rather similar to the structures of (I) and (II). The sum of the three valence angles about the N atom is 344 (2)°. The angle between the benzene planes is 87.96 (8)°. The crystal packing of (III) is shown in Fig. 6. The molecules are arranged to form centrosymmetric dimers connected by two symmetry-related N—H···O═P hydrogen bonds (Table 4). The dimers are also stabilized by two C—H···O═ P contacts, with H···O distances of 2.44 and 2.71 Å. Neigbouring dimers are connected by two very weak inter­molecular C_methyl—H···π_benzene inter­actions and two weak inter­molecular C_benzene—H···F contacts, with H···F distances of 2.67 and 2.76 Å, respectively.

Crystals of (IV) undergo a phase transition on cooling from room temperature to 180 K, accompanied by a doubling of the unit-cell volume. The cell constants at room temperature are a = 10.0601 (15), b = 11.452 (2) and c = 11.506 (3) Å, and α = 111.314 (14), β = 114.179 (12) and γ = 96.888 (11)°. The low-temperature unit cell is related to the room-temperature unit cell by the transformations a_lt = -b_rt, b_lt = a_rt + c_rt and c_lt = -a_rt + c_rt. Consequently, the asymmetric unit of (IV) at 180 K contains two independent molecules (A and B; Fig. 7), which are approximately related by pseudo-translation [0 1/2 1/2]. The conformations of molecules A and B differ mainly in the relative orientations of the eth­oxy groups attached to the P atoms. The angle between the naphthyl and benzene planes is 86.05 (9)° for molecule A and 85.92 (8)° for molecule B. The ethynyl group shows a considerable deviation from the plane of the benzene ring for molecule B [atoms C31 and C32 deviate by 0.175 (5) and 0.391 (6) Å, respectively, from the benzene plane]. A smaller deviation is observed for the ethynyl group of molecule A [atoms C8 And C9 deviate by 0.061 (5) and 0.141 (6) Å, respectively, from the benzene plane]. The sum of the three valence angles about the N atom is 351 (2)° for N1 and 349 (2)° for N2. The crystal packing of (IV) is shown in Fig. 8. In the crystal structure, molecules are connected to form pseudocentrosymmetric dimers. Each dimer consists of a molecule A and a molecule B, which are connected by two N—H···O═P hydrogen bonds, and by two C—H···O═P contacts with H···O distances of 2.48 and 2.56 Å, respectively (Table 5). Neigbouring dimers are connected by an inter­molecular C_ethynyl—H···O contact with an H···O distance of 2.44 Å. The latter contact is rather short and may be responsible for the nonplanarity of the ethynyl­phenyl group of molecule B. There are also a number of weak inter­molecular C—H···π_benzene and C—H···π_naphthyl inter­actions and an additional C—H···O contact, with an H···O distance of 2.63 Å (Table 5).

The conformation of the anilino­benzyl group is very similar in all four compounds. Selected torsion angles in (I)–(IV) are reported in Table 6 and compared with the corresponding torsion angles in other anilino–phenyl­methyl phospho­nate structures with no substituents at the ortho positions of the benzene rings. The six-membered ring of the anilino group is almost coplanar with the amino group in all compounds. The P—C bond has an approximately staggered conformation in all structures, with the C1—N1 and C1—C2 bonds in gauche positions and the C1—H bond in a trans position with respect to the P═O double bond. For the C2—C1—N1—C10 torsion angle, two possible orientations are found: in 17 structures the torsion angle has a value of -69 (5)°, while in four structures values between -114 and -147° are found. The intra­molecular N—H···O═P contact is shorter in the former case (H···O distances 2.64–2.91 Å), which may therefore correspond to the preferred conformation. For the C3—C2—C1—N1 torsion angle, a value near -47 (10)° is found in all structures. This corresponds to the conformation where the benzyl plane is almost parallel to the C1—H bond. In the crystal structures, the anilino­benzyl­phospho­nate units of all molecules listed in Table 6 are connected to form centrosymmetric or pseudo-centrosymmetric dimers. In each dimer, except in (II), the molecules are connected by two N—H···O═P hydrogen bonds. In (II), where the amino N—H bond is shielded by a methyl substituent in the ortho-position of the aniline ring, no N—H···O hydrogen bond is found. Here, C_methyl—H···O═P hydrogen bonds connect the molecules to form centrosymmetric dimers.

Related literature

For related literature, see: Atherton et al. (1986); Cherkasov & Galkin (1998); Huang & Chen (2000); Lavielle et al. (1991); Maier & Spörri (1991); Rużić-Toroš, Kojić-Prodić & Šljukic (1978); Wang et al. (2012); Wu et al. (2006); Xu et al. (2006).

Computing details

For all compounds, data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only the major orientation of the disordered ethyl groups is shown.
	Fig. 2. The crystal packing of (I), viewed down [001]. C-bound H atoms have been omitted for clarity. N—H···O hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x + 2, -y + 1, -z + 1.]
	Fig. 3. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Only the major orientation of the disordered ethyl group is shown.
	Fig. 4. The crystal packing of (II), viewed down [010]. C-bound H atoms have been omitted for clarity. The Cmethyl···O and Cbenzene···O contacts, which connect the molecules into dimers, are shown as dashed lines. [Symmetry code: (i) -x + 1/2, -y + 3/2, -z + 1/2.]
	Fig. 5. The molecular structure of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 6. The crystal packing of (III), viewed down [100]. C-bound H atoms have been omitted for clarity. N—H···O hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x + 1, -y + 2, -z + 1.]
	Fig. 7. The molecular structure of (a) molecule A and (b) molecule B of (IV), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 8. The crystal packing of (IV), viewed down [010]. C-bound H atoms have been omitted for clarity. N—H···O hydrogen bonds are shown as dashed lines. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]

(I) Diethyl [(4-bromoanilino)(4-ethynylphenyl)methyl]phosphonate

Crystal data

C19H21BrNO3P	F(000) = 864
Mr = 422.25	Dx = 1.438 Mg m^−3
Monoclinic, P21/n	Melting point: 416(1) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.9339 (7) Å	Cell parameters from 7719 reflections
b = 16.5179 (11) Å	θ = 3–27°
c = 11.1325 (7) Å	µ = 2.21 mm^−1
β = 104.114 (1)°	T = 186 K
V = 1949.9 (2) Å^3	Block, pale brown
Z = 4	0.60 × 0.60 × 0.50 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	4762 independent reflections
Radiation source: normal-focus sealed tube	4104 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω scans	θmax = 28.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −14→14
Tmin = 0.284, Tmax = 0.332	k = −21→21
22735 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.025P)^2 + 1.3P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4762 reflections	Δρmax = 0.47 e Å^−3
245 parameters	Δρmin = −0.43 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0039 (4)

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 > 2sigma(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)
Br1	0.44620 (2)	0.162990 (14)	0.40970 (2)	0.04550 (9)
P1	0.84365 (4)	0.62113 (3)	0.49540 (4)	0.02480 (12)
O1	0.97550 (12)	0.60700 (9)	0.49191 (14)	0.0343 (3)
O2	0.77945 (13)	0.69708 (9)	0.42188 (14)	0.0343 (3)
O3	0.82091 (13)	0.63275 (9)	0.62817 (13)	0.0339 (3)
N1	0.77465 (15)	0.46582 (10)	0.50665 (15)	0.0258 (3)
H1B	0.849 (2)	0.4551 (14)	0.517 (2)	0.037 (6)*
C1	0.73722 (16)	0.53871 (11)	0.43243 (17)	0.0247 (4)
H1A	0.6508	0.5542	0.4395	0.030*
C2	0.73341 (17)	0.53028 (11)	0.29485 (17)	0.0254 (4)
C3	0.83644 (19)	0.49747 (13)	0.25893 (18)	0.0338 (5)
H3A	0.9071	0.4786	0.3202	0.041*
C4	0.8369 (2)	0.49211 (14)	0.13498 (19)	0.0368 (5)
H4A	0.9083	0.4702	0.1120	0.044*
C5	0.7334 (2)	0.51861 (12)	0.04342 (18)	0.0306 (4)
C6	0.6311 (2)	0.55212 (12)	0.07949 (19)	0.0346 (5)
H6A	0.5606	0.5714	0.0184	0.041*
C7	0.63142 (18)	0.55764 (12)	0.20376 (18)	0.0306 (4)
H7A	0.5608	0.5805	0.2269	0.037*
C8	0.7344 (2)	0.51049 (13)	−0.0856 (2)	0.0376 (5)
C9	0.7375 (2)	0.50198 (15)	−0.1907 (2)	0.0454 (6)
H9A	0.7399	0.4952	−0.2748	0.055*
C10	0.69665 (17)	0.39730 (11)	0.48211 (16)	0.0245 (4)
C11	0.56698 (18)	0.40216 (12)	0.42991 (19)	0.0301 (4)
H11A	0.5291	0.4535	0.4075	0.036*
C12	0.49261 (19)	0.33260 (13)	0.4104 (2)	0.0334 (4)
H12A	0.4044	0.3366	0.3757	0.040*
C13	0.54771 (19)	0.25799 (12)	0.44163 (19)	0.0319 (4)
C14	0.6760 (2)	0.25156 (13)	0.4943 (2)	0.0336 (4)
H14A	0.7134	0.2000	0.5162	0.040*
C15	0.74927 (19)	0.32088 (12)	0.51483 (19)	0.0305 (4)
H15A	0.8370	0.3165	0.5519	0.037*
C16	0.8259 (3)	0.73571 (15)	0.3239 (2)	0.0473 (6)	0.877 (11)
H16A	0.7540	0.7491	0.2535	0.057*	0.877 (11)
H16B	0.8821	0.6979	0.2938	0.057*	0.877 (11)
C16'	0.8259 (3)	0.73571 (15)	0.3239 (2)	0.0473 (6)	0.123 (11)
H16C	0.9149	0.7207	0.3304	0.057*	0.123 (11)
H16D	0.7747	0.7191	0.2415	0.057*	0.123 (11)
C17	0.8959 (6)	0.81067 (19)	0.3710 (3)	0.0601 (15)	0.877 (11)
H17A	0.9267	0.8361	0.3045	0.090*	0.877 (11)
H17B	0.9676	0.7972	0.4400	0.090*	0.877 (11)
H17C	0.8398	0.8483	0.3997	0.090*	0.877 (11)
C17'	0.815 (3)	0.8204 (11)	0.3414 (19)	0.037 (6)*	0.123 (11)
H17D	0.7265	0.8368	0.3106	0.056*	0.123 (11)
H17E	0.8671	0.8496	0.2957	0.056*	0.123 (11)
H17F	0.8430	0.8333	0.4297	0.056*	0.123 (11)
C18	0.9149 (3)	0.66885 (18)	0.7308 (2)	0.0408 (8)	0.877 (7)
H18A	0.9987	0.6455	0.7321	0.049*	0.877 (7)
H18B	0.8941	0.6543	0.8098	0.049*	0.877 (7)
C18'	0.861 (2)	0.7080 (13)	0.696 (2)	0.042 (6)*	0.123 (7)
H18C	0.8275	0.7546	0.6420	0.050*	0.123 (7)
H18D	0.8233	0.7103	0.7688	0.050*	0.123 (7)
C19	0.9224 (4)	0.7579 (2)	0.7227 (3)	0.0581 (11)	0.877 (7)
H19A	0.9867	0.7784	0.7936	0.087*	0.877 (7)
H19B	0.8404	0.7816	0.7235	0.087*	0.877 (7)
H19C	0.9450	0.7729	0.6457	0.087*	0.877 (7)
C19'	0.996 (2)	0.7154 (13)	0.7383 (19)	0.044 (6)*	0.123 (7)
H19D	1.0172	0.7666	0.7832	0.066*	0.123 (7)
H19E	1.0335	0.7145	0.6668	0.066*	0.123 (7)
H19F	1.0294	0.6701	0.7935	0.066*	0.123 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.04488 (14)	0.03430 (13)	0.05704 (17)	−0.01325 (10)	0.01189 (11)	−0.00322 (10)
P1	0.0230 (2)	0.0267 (2)	0.0258 (2)	−0.00257 (18)	0.00832 (18)	−0.00322 (19)
O1	0.0244 (7)	0.0365 (8)	0.0436 (8)	−0.0035 (6)	0.0113 (6)	−0.0050 (6)
O2	0.0369 (8)	0.0291 (7)	0.0380 (8)	0.0010 (6)	0.0114 (6)	0.0006 (6)
O3	0.0349 (7)	0.0402 (8)	0.0280 (7)	−0.0097 (6)	0.0105 (6)	−0.0086 (6)
N1	0.0214 (8)	0.0287 (8)	0.0276 (8)	−0.0013 (6)	0.0064 (6)	−0.0011 (6)
C1	0.0213 (8)	0.0268 (9)	0.0267 (9)	−0.0009 (7)	0.0073 (7)	−0.0036 (7)
C2	0.0265 (9)	0.0247 (9)	0.0248 (9)	−0.0021 (7)	0.0056 (7)	−0.0022 (7)
C3	0.0289 (10)	0.0454 (12)	0.0257 (10)	0.0097 (9)	0.0041 (8)	−0.0014 (9)
C4	0.0373 (11)	0.0449 (12)	0.0296 (11)	0.0086 (9)	0.0107 (9)	−0.0001 (9)
C5	0.0399 (11)	0.0253 (10)	0.0251 (10)	−0.0028 (8)	0.0048 (8)	0.0015 (8)
C6	0.0344 (11)	0.0321 (11)	0.0318 (11)	0.0032 (8)	−0.0023 (8)	0.0040 (8)
C7	0.0275 (9)	0.0293 (10)	0.0336 (11)	0.0035 (8)	0.0051 (8)	−0.0018 (8)
C8	0.0464 (13)	0.0325 (11)	0.0317 (11)	−0.0003 (9)	0.0052 (9)	0.0049 (9)
C9	0.0584 (15)	0.0486 (14)	0.0286 (12)	0.0021 (11)	0.0092 (10)	0.0044 (10)
C10	0.0253 (9)	0.0301 (10)	0.0213 (9)	−0.0028 (7)	0.0114 (7)	−0.0037 (7)
C11	0.0271 (9)	0.0286 (10)	0.0359 (11)	0.0014 (7)	0.0103 (8)	−0.0033 (8)
C12	0.0242 (9)	0.0385 (11)	0.0385 (11)	−0.0036 (8)	0.0097 (8)	−0.0060 (9)
C13	0.0325 (10)	0.0300 (10)	0.0365 (11)	−0.0093 (8)	0.0148 (9)	−0.0049 (8)
C14	0.0365 (11)	0.0302 (10)	0.0364 (11)	0.0007 (8)	0.0137 (9)	0.0035 (8)
C15	0.0250 (9)	0.0357 (11)	0.0315 (10)	0.0011 (8)	0.0083 (8)	0.0029 (8)
C16	0.0695 (17)	0.0417 (13)	0.0329 (12)	0.0004 (12)	0.0166 (11)	0.0068 (10)
C16'	0.0695 (17)	0.0417 (13)	0.0329 (12)	0.0004 (12)	0.0166 (11)	0.0068 (10)
C17	0.094 (4)	0.0383 (16)	0.055 (2)	−0.0152 (18)	0.032 (2)	0.0043 (14)
C18	0.0464 (16)	0.0446 (17)	0.0277 (13)	−0.0039 (13)	0.0021 (11)	−0.0075 (11)
C19	0.084 (3)	0.0471 (19)	0.0406 (16)	−0.0257 (17)	0.0088 (16)	−0.0057 (13)

Geometric parameters (Å, º)

Br1—C13	1.9048 (19)	C11—H11A	0.9500
P1—O1	1.4702 (14)	C12—C13	1.379 (3)
P1—O2	1.5672 (15)	C12—H12A	0.9500
P1—O3	1.5693 (14)	C13—C14	1.387 (3)
P1—C1	1.8170 (18)	C14—C15	1.384 (3)
O2—C16	1.457 (3)	C14—H14A	0.9500
O3—C18	1.465 (3)	C15—H15A	0.9500
O3—C18'	1.47 (2)	C16—C17	1.483 (4)
N1—C10	1.403 (2)	C16—H16A	0.9900
N1—C1	1.461 (2)	C16—H16B	0.9900
N1—H1B	0.81 (2)	C17—H17A	0.9800
C1—C2	1.528 (3)	C17—H17B	0.9800
C1—H1A	1.0000	C17—H17C	0.9800
C2—C7	1.387 (3)	C17'—H17D	0.9800
C2—C3	1.394 (3)	C17'—H17E	0.9800
C3—C4	1.384 (3)	C17'—H17F	0.9800
C3—H3A	0.9500	C18—C19	1.478 (4)
C4—C5	1.396 (3)	C18—H18A	0.9900
C4—H4A	0.9500	C18—H18B	0.9900
C5—C6	1.392 (3)	C18'—C19'	1.45 (3)
C5—C8	1.445 (3)	C18'—H18C	0.9900
C6—C7	1.386 (3)	C18'—H18D	0.9900
C6—H6A	0.9500	C19—H19A	0.9800
C7—H7A	0.9500	C19—H19B	0.9800
C8—C9	1.187 (3)	C19—H19C	0.9800
C9—H9A	0.9500	C19'—H19D	0.9800
C10—C11	1.397 (3)	C19'—H19E	0.9800
C10—C15	1.398 (3)	C19'—H19F	0.9800
C11—C12	1.394 (3)
O1—P1—O2	115.50 (8)	C12—C13—Br1	119.37 (15)
O1—P1—O3	115.20 (9)	C14—C13—Br1	119.95 (16)
O2—P1—O3	103.91 (8)	C15—C14—C13	119.44 (19)
O1—P1—C1	114.24 (8)	C15—C14—H14A	120.3
O2—P1—C1	103.61 (8)	C13—C14—H14A	120.3
O3—P1—C1	102.79 (8)	C14—C15—C10	121.28 (18)
C16—O2—P1	123.23 (15)	C14—C15—H15A	119.4
C18—O3—P1	122.84 (15)	C10—C15—H15A	119.4
C18'—O3—P1	119.7 (8)	O2—C16—C17	110.2 (2)
C10—N1—C1	118.78 (15)	O2—C16—H16A	109.6
C10—N1—H1B	112.9 (17)	C17—C16—H16A	109.6
C1—N1—H1B	113.0 (17)	O2—C16—H16B	109.6
N1—C1—C2	115.29 (15)	C17—C16—H16B	109.6
N1—C1—P1	109.55 (12)	H16A—C16—H16B	108.1
C2—C1—P1	108.26 (12)	C16—C17—H17A	109.5
N1—C1—H1A	107.8	C16—C17—H17B	109.5
C2—C1—H1A	107.8	H17A—C17—H17B	109.5
P1—C1—H1A	107.8	C16—C17—H17C	109.5
C7—C2—C3	118.61 (18)	H17A—C17—H17C	109.5
C7—C2—C1	121.57 (17)	H17B—C17—H17C	109.5
C3—C2—C1	119.77 (16)	H17D—C17'—H17E	109.5
C4—C3—C2	120.71 (19)	H17D—C17'—H17F	109.5
C4—C3—H3A	119.6	H17E—C17'—H17F	109.5
C2—C3—H3A	119.6	O3—C18—C19	113.4 (2)
C3—C4—C5	120.59 (19)	O3—C18—H18A	108.9
C3—C4—H4A	119.7	C19—C18—H18A	108.9
C5—C4—H4A	119.7	O3—C18—H18B	108.9
C6—C5—C4	118.63 (18)	C19—C18—H18B	108.9
C6—C5—C8	121.66 (19)	H18A—C18—H18B	107.7
C4—C5—C8	119.7 (2)	C19'—C18'—O3	113.0 (18)
C7—C6—C5	120.52 (18)	C19'—C18'—H18C	109.0
C7—C6—H6A	119.7	O3—C18'—H18C	109.0
C5—C6—H6A	119.7	C19'—C18'—H18D	109.0
C6—C7—C2	120.93 (18)	O3—C18'—H18D	109.0
C6—C7—H7A	119.5	H18C—C18'—H18D	107.8
C2—C7—H7A	119.5	C18—C19—H19A	109.5
C9—C8—C5	178.1 (3)	C18—C19—H19B	109.5
C8—C9—H9A	180.0	H19A—C19—H19B	109.5
C11—C10—C15	118.14 (17)	C18—C19—H19C	109.5
C11—C10—N1	122.78 (17)	H19A—C19—H19C	109.5
C15—C10—N1	119.04 (17)	H19B—C19—H19C	109.5
C12—C11—C10	120.77 (19)	C18'—C19'—H19D	109.5
C12—C11—H11A	119.6	C18'—C19'—H19E	109.5
C10—C11—H11A	119.6	H19D—C19'—H19E	109.5
C13—C12—C11	119.68 (19)	C18'—C19'—H19F	109.5
C13—C12—H12A	120.2	H19D—C19'—H19F	109.5
C11—C12—H12A	120.2	H19E—C19'—H19F	109.5
C12—C13—C14	120.67 (18)
O1—P1—O2—C16	20.18 (19)	C2—C3—C4—C5	−0.8 (3)
O3—P1—O2—C16	147.35 (16)	C3—C4—C5—C6	1.4 (3)
C1—P1—O2—C16	−105.52 (17)	C3—C4—C5—C8	−178.4 (2)
O1—P1—O3—C18	30.9 (2)	C4—C5—C6—C7	−1.1 (3)
O2—P1—O3—C18	−96.40 (19)	C8—C5—C6—C7	178.61 (19)
C1—P1—O3—C18	155.86 (19)	C5—C6—C7—C2	0.2 (3)
O1—P1—O3—C18'	72.9 (11)	C3—C2—C7—C6	0.4 (3)
O2—P1—O3—C18'	−54.5 (11)	C1—C2—C7—C6	177.76 (18)
C1—P1—O3—C18'	−162.2 (11)	C1—N1—C10—C11	−26.6 (3)
C10—N1—C1—C2	−64.5 (2)	C1—N1—C10—C15	155.68 (17)
C10—N1—C1—P1	173.11 (13)	C15—C10—C11—C12	−0.4 (3)
O1—P1—C1—N1	62.67 (15)	N1—C10—C11—C12	−178.19 (18)
O2—P1—C1—N1	−170.84 (12)	C10—C11—C12—C13	−0.7 (3)
O3—P1—C1—N1	−62.87 (14)	C11—C12—C13—C14	1.2 (3)
O1—P1—C1—C2	−63.81 (15)	C11—C12—C13—Br1	−178.00 (15)
O2—P1—C1—C2	62.69 (13)	C12—C13—C14—C15	−0.4 (3)
O3—P1—C1—C2	170.66 (12)	Br1—C13—C14—C15	178.72 (15)
N1—C1—C2—C7	132.71 (18)	C13—C14—C15—C10	−0.7 (3)
P1—C1—C2—C7	−104.23 (18)	C11—C10—C15—C14	1.2 (3)
N1—C1—C2—C3	−50.0 (2)	N1—C10—C15—C14	179.01 (18)
P1—C1—C2—C3	73.1 (2)	P1—O2—C16—C17	−102.3 (3)
C7—C2—C3—C4	−0.1 (3)	P1—O3—C18—C19	76.9 (3)
C1—C2—C3—C4	−177.55 (19)	P1—O3—C18'—C19'	−70.8 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1^i	0.81 (2)	2.20 (2)	2.981 (2)	162 (2)
C3—H3A···O1^i	0.95	2.59	3.481 (3)	156
C15—H15A···O1^i	0.95	2.55	3.254 (2)	131
C9—H9A···N1^ii	0.95	2.60	3.542 (3)	172
C12—H12A···O3^iii	0.95	2.50	3.398 (2)	157
C4—H4A···Br1^iv	0.95	3.25	3.968 (2)	134
C18—H18B···Br1^v	0.99	3.19	3.920 (3)	132
C17—H17A···C11^vi	0.98	2.84	3.786 (4)	161
C17—H17A···C12^vi	0.98	2.74	3.646 (4)	153

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

(II) Diethyl ((4-chloro-2-methylanilino){4-[2-(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate

Crystal data

C23H31ClNO3PSi	F(000) = 1968
Mr = 464.00	Dx = 1.204 Mg m^−3
Monoclinic, I2/a	Melting point: 371(1) K
Hall symbol: -I 2ya	Mo Kα radiation, λ = 0.71073 Å
a = 17.3791 (16) Å	Cell parameters from 5632 reflections
b = 14.7131 (13) Å	θ = 3–25°
c = 20.019 (3) Å	µ = 0.28 mm^−1
β = 90.464 (1)°	T = 183 K
V = 5118.6 (10) Å^3	Block, pale brown
Z = 8	0.38 × 0.36 × 0.34 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	5021 independent reflections
Radiation source: normal-focus sealed tube	3655 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ω scans	θmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −21→21
Tmin = 0.790, Tmax = 0.909	k = −18→18
24553 measured reflections	l = −24→24

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)] = 0.101	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.04P)^2 + 12P] where P = (Fo^2 + 2Fc^2)/3
5021 reflections	(Δ/σ)max = 0.001
297 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.27 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 > 2sigma(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)
Cl1	0.68735 (6)	0.76247 (11)	0.43042 (7)	0.0803 (5)
P1	0.20317 (6)	0.73870 (8)	0.38093 (6)	0.0451 (3)
Si1	0.39549 (7)	0.13406 (9)	0.32089 (7)	0.0559 (4)
O1	0.18631 (16)	0.7528 (2)	0.30989 (16)	0.0634 (10)
O2	0.15600 (14)	0.66097 (19)	0.41600 (13)	0.0419 (7)
O3	0.18498 (19)	0.8192 (2)	0.42940 (19)	0.0726 (11)
N1	0.35325 (19)	0.7771 (2)	0.36837 (19)	0.0448 (9)
H1B	0.341 (3)	0.785 (3)	0.329 (2)	0.054*
C1	0.3027 (2)	0.7113 (3)	0.4000 (2)	0.0387 (10)
H1A	0.3095	0.7189	0.4493	0.046*
C2	0.3207 (2)	0.6124 (3)	0.38435 (19)	0.0362 (9)
C3	0.3332 (2)	0.5839 (3)	0.3192 (2)	0.0426 (10)
H3A	0.3311	0.6267	0.2837	0.051*
C4	0.3487 (2)	0.4940 (3)	0.3056 (2)	0.0449 (11)
H4A	0.3581	0.4755	0.2609	0.054*
C5	0.3505 (2)	0.4296 (3)	0.3572 (2)	0.0408 (10)
C6	0.3375 (2)	0.4582 (3)	0.4220 (2)	0.0432 (10)
H6A	0.3382	0.4154	0.4575	0.052*
C7	0.3234 (2)	0.5486 (3)	0.4353 (2)	0.0394 (10)
H7A	0.3154	0.5675	0.4801	0.047*
C8	0.3667 (2)	0.3345 (3)	0.3442 (2)	0.0481 (11)
C9	0.3810 (2)	0.2562 (3)	0.3345 (2)	0.0540 (12)
C10	0.4323 (2)	0.7740 (3)	0.3838 (2)	0.0374 (9)
C11	0.4596 (2)	0.7372 (3)	0.4436 (2)	0.0509 (11)
H11A	0.4240	0.7129	0.4746	0.061*
C12	0.5372 (2)	0.7353 (3)	0.4586 (2)	0.0530 (12)
H12A	0.5547	0.7108	0.5000	0.064*
C13	0.5888 (2)	0.7687 (3)	0.4137 (2)	0.0485 (11)
C14	0.5630 (2)	0.8072 (3)	0.3547 (2)	0.0457 (11)
H14A	0.5992	0.8316	0.3243	0.055*
C15	0.4853 (2)	0.8109 (3)	0.33909 (19)	0.0363 (9)
C16	0.1316 (3)	0.5798 (3)	0.3817 (2)	0.0613 (13)
H16A	0.1675	0.5294	0.3923	0.074*
H16B	0.1325	0.5901	0.3329	0.074*
C17	0.0535 (3)	0.5549 (4)	0.4023 (3)	0.0814 (18)
H17A	0.0376	0.4993	0.3790	0.122*
H17B	0.0179	0.6043	0.3909	0.122*
H17C	0.0528	0.5445	0.4506	0.122*
C18	0.1974 (7)	0.9058 (7)	0.4043 (6)	0.082 (4)	0.518 (12)
H18A	0.1774	0.9121	0.3580	0.099*	0.518 (12)
H18B	0.2527	0.9222	0.4054	0.099*	0.518 (12)
C18'	0.1246 (6)	0.8825 (7)	0.4340 (6)	0.063 (4)	0.482 (12)
H18C	0.1091	0.8871	0.4813	0.076*	0.482 (12)
H18D	0.0799	0.8590	0.4084	0.076*	0.482 (12)
C19	0.1513 (13)	0.9624 (13)	0.4532 (11)	0.126 (8)	0.518 (12)
H19A	0.1549	1.0268	0.4410	0.189*	0.518 (12)
H19B	0.1721	0.9538	0.4985	0.189*	0.518 (12)
H19C	0.0974	0.9432	0.4518	0.189*	0.518 (12)
C19'	0.1424 (13)	0.9720 (12)	0.4100 (10)	0.095 (6)	0.482 (12)
H19D	0.0966	1.0107	0.4132	0.142*	0.482 (12)
H19E	0.1587	0.9684	0.3634	0.142*	0.482 (12)
H19F	0.1840	0.9981	0.4372	0.142*	0.482 (12)
C20	0.4579 (2)	0.8533 (3)	0.2746 (2)	0.0470 (11)
H20A	0.4305	0.8076	0.2478	0.070*
H20B	0.5022	0.8759	0.2495	0.070*
H20C	0.4231	0.9039	0.2844	0.070*
C21	0.3942 (4)	0.0769 (4)	0.4033 (3)	0.108 (2)
H21A	0.3456	0.0903	0.4257	0.161*
H21B	0.4372	0.0992	0.4307	0.161*
H21C	0.3992	0.0112	0.3971	0.161*
C22	0.3139 (4)	0.0938 (5)	0.2698 (4)	0.126 (3)
H22A	0.3191	0.1167	0.2241	0.190*
H22B	0.2657	0.1161	0.2889	0.190*
H22C	0.3136	0.0272	0.2693	0.190*
C23	0.4876 (3)	0.1160 (4)	0.2790 (3)	0.092 (2)
H23A	0.4848	0.1410	0.2336	0.137*
H23B	0.4985	0.0508	0.2768	0.137*
H23C	0.5286	0.1467	0.3041	0.137*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0325 (6)	0.1103 (12)	0.0978 (11)	−0.0059 (7)	−0.0187 (6)	0.0263 (9)
P1	0.0269 (5)	0.0496 (7)	0.0589 (8)	0.0088 (5)	0.0064 (5)	0.0228 (6)
Si1	0.0431 (7)	0.0488 (8)	0.0757 (10)	0.0008 (6)	0.0029 (6)	−0.0147 (7)
O1	0.0370 (16)	0.080 (2)	0.073 (2)	−0.0011 (15)	−0.0036 (15)	0.0449 (19)
O2	0.0318 (14)	0.0486 (17)	0.0453 (17)	0.0014 (13)	0.0049 (12)	0.0122 (14)
O3	0.061 (2)	0.051 (2)	0.106 (3)	0.0261 (17)	0.029 (2)	0.0185 (19)
N1	0.0302 (18)	0.051 (2)	0.053 (2)	0.0038 (15)	−0.0017 (17)	0.0214 (19)
C1	0.031 (2)	0.047 (2)	0.039 (2)	0.0053 (18)	0.0004 (17)	0.0114 (19)
C2	0.0226 (18)	0.047 (2)	0.039 (2)	0.0024 (17)	0.0031 (16)	0.0053 (19)
C3	0.033 (2)	0.053 (3)	0.041 (3)	−0.0004 (19)	0.0035 (18)	0.010 (2)
C4	0.039 (2)	0.062 (3)	0.033 (2)	−0.001 (2)	0.0050 (18)	−0.003 (2)
C5	0.030 (2)	0.050 (3)	0.042 (3)	0.0058 (18)	0.0013 (18)	−0.005 (2)
C6	0.041 (2)	0.049 (3)	0.040 (3)	0.012 (2)	0.0011 (19)	0.010 (2)
C7	0.040 (2)	0.048 (3)	0.030 (2)	0.0107 (19)	0.0013 (17)	0.0029 (19)
C8	0.037 (2)	0.057 (3)	0.051 (3)	−0.001 (2)	0.004 (2)	−0.006 (2)
C9	0.042 (2)	0.052 (3)	0.068 (3)	0.001 (2)	0.006 (2)	−0.011 (2)
C10	0.030 (2)	0.036 (2)	0.046 (2)	0.0043 (17)	−0.0022 (17)	0.0056 (18)
C11	0.037 (2)	0.066 (3)	0.050 (3)	0.005 (2)	0.005 (2)	0.017 (2)
C12	0.040 (2)	0.069 (3)	0.050 (3)	0.006 (2)	−0.009 (2)	0.011 (2)
C13	0.028 (2)	0.058 (3)	0.059 (3)	−0.001 (2)	−0.008 (2)	0.004 (2)
C14	0.032 (2)	0.053 (3)	0.052 (3)	−0.0050 (19)	0.003 (2)	0.006 (2)
C15	0.033 (2)	0.033 (2)	0.042 (2)	0.0000 (17)	−0.0007 (18)	0.0012 (18)
C16	0.063 (3)	0.072 (3)	0.049 (3)	−0.005 (3)	0.000 (2)	0.011 (3)
C17	0.051 (3)	0.123 (5)	0.070 (4)	−0.022 (3)	−0.001 (3)	0.001 (3)
C18	0.087 (9)	0.054 (7)	0.106 (9)	−0.007 (6)	0.007 (7)	−0.013 (6)
C18'	0.046 (6)	0.054 (7)	0.090 (8)	0.024 (5)	−0.014 (5)	−0.014 (6)
C19	0.158 (16)	0.069 (12)	0.150 (19)	0.040 (10)	−0.038 (17)	−0.038 (13)
C19'	0.115 (13)	0.051 (8)	0.118 (15)	0.025 (8)	−0.011 (13)	0.019 (11)
C20	0.043 (2)	0.053 (3)	0.045 (3)	−0.005 (2)	−0.0019 (19)	0.010 (2)
C21	0.139 (6)	0.079 (4)	0.106 (5)	−0.003 (4)	0.030 (5)	−0.002 (4)
C22	0.087 (5)	0.094 (5)	0.197 (8)	0.010 (4)	−0.051 (5)	−0.066 (5)
C23	0.071 (4)	0.061 (4)	0.144 (6)	0.007 (3)	0.036 (4)	−0.003 (4)

Geometric parameters (Å, º)

Cl1—C13	1.745 (4)	C13—C14	1.382 (6)
P1—O1	1.464 (3)	C14—C15	1.384 (5)
P1—O3	1.565 (4)	C14—H14A	0.9500
P1—O2	1.575 (3)	C15—C20	1.508 (5)
P1—C1	1.814 (4)	C16—C17	1.469 (6)
Si1—C23	1.832 (5)	C16—H16A	0.9900
Si1—C9	1.835 (5)	C16—H16B	0.9900
Si1—C22	1.839 (6)	C17—H17A	0.9800
Si1—C21	1.852 (6)	C17—H17B	0.9800
O2—C16	1.440 (5)	C17—H17C	0.9800
O3—C18	1.388 (11)	C18—C19	1.52 (2)
O3—C18'	1.406 (9)	C18—H18A	0.9900
N1—C10	1.407 (5)	C18—H18B	0.9900
N1—C1	1.456 (5)	C18'—C19'	1.44 (2)
N1—H1B	0.81 (4)	C18'—H18C	0.9900
C1—C2	1.521 (5)	C18'—H18D	0.9900
C1—H1A	1.0000	C19—H19A	0.9800
C2—C7	1.387 (5)	C19—H19B	0.9800
C2—C3	1.389 (5)	C19—H19C	0.9800
C3—C4	1.377 (6)	C19'—H19D	0.9800
C3—H3A	0.9500	C19'—H19E	0.9800
C4—C5	1.403 (6)	C19'—H19F	0.9800
C4—H4A	0.9500	C20—H20A	0.9800
C5—C6	1.385 (6)	C20—H20B	0.9800
C5—C8	1.451 (6)	C20—H20C	0.9800
C6—C7	1.378 (5)	C21—H21A	0.9800
C6—H6A	0.9500	C21—H21B	0.9800
C7—H7A	0.9500	C21—H21C	0.9800
C8—C9	1.194 (6)	C22—H22A	0.9800
C10—C11	1.393 (6)	C22—H22B	0.9800
C10—C15	1.399 (5)	C22—H22C	0.9800
C11—C12	1.381 (6)	C23—H23A	0.9800
C11—H11A	0.9500	C23—H23B	0.9800
C12—C13	1.366 (6)	C23—H23C	0.9800
C12—H12A	0.9500
O1—P1—O3	117.06 (19)	C10—C15—C20	120.2 (3)
O1—P1—O2	115.77 (17)	O2—C16—C17	110.0 (4)
O3—P1—O2	99.49 (17)	O2—C16—H16A	109.7
O1—P1—C1	114.77 (18)	C17—C16—H16A	109.7
O3—P1—C1	103.59 (19)	O2—C16—H16B	109.7
O2—P1—C1	104.08 (16)	C17—C16—H16B	109.7
C23—Si1—C9	109.4 (2)	H16A—C16—H16B	108.2
C23—Si1—C22	111.8 (3)	C16—C17—H17A	109.5
C9—Si1—C22	106.9 (3)	C16—C17—H17B	109.5
C23—Si1—C21	111.0 (3)	H17A—C17—H17B	109.5
C9—Si1—C21	108.0 (3)	C16—C17—H17C	109.5
C22—Si1—C21	109.6 (4)	H17A—C17—H17C	109.5
C16—O2—P1	122.8 (3)	H17B—C17—H17C	109.5
C18—O3—P1	115.9 (5)	O3—C18—C19	100.6 (12)
C18'—O3—P1	134.1 (5)	O3—C18—H18A	111.6
C10—N1—C1	118.4 (3)	C19—C18—H18A	111.6
C10—N1—H1B	117 (3)	O3—C18—H18B	111.6
C1—N1—H1B	111 (3)	C19—C18—H18B	111.6
N1—C1—C2	114.9 (3)	H18A—C18—H18B	109.4
N1—C1—P1	109.8 (3)	O3—C18'—C19'	115.0 (12)
C2—C1—P1	111.5 (3)	O3—C18'—H18C	108.5
N1—C1—H1A	106.7	C19'—C18'—H18C	108.5
C2—C1—H1A	106.7	O3—C18'—H18D	108.5
P1—C1—H1A	106.7	C19'—C18'—H18D	108.5
C7—C2—C3	118.8 (4)	H18C—C18'—H18D	107.5
C7—C2—C1	120.1 (4)	C18—C19—H19A	109.5
C3—C2—C1	121.1 (4)	C18—C19—H19B	109.5
C4—C3—C2	120.5 (4)	H19A—C19—H19B	109.5
C4—C3—H3A	119.7	C18—C19—H19C	109.5
C2—C3—H3A	119.7	H19A—C19—H19C	109.5
C3—C4—C5	120.5 (4)	H19B—C19—H19C	109.5
C3—C4—H4A	119.8	C18'—C19'—H19D	109.5
C5—C4—H4A	119.8	C18'—C19'—H19E	109.5
C6—C5—C4	118.8 (4)	H19D—C19'—H19E	109.5
C6—C5—C8	119.7 (4)	C18'—C19'—H19F	109.5
C4—C5—C8	121.6 (4)	H19D—C19'—H19F	109.5
C7—C6—C5	120.3 (4)	H19E—C19'—H19F	109.5
C7—C6—H6A	119.8	C15—C20—H20A	109.5
C5—C6—H6A	119.8	C15—C20—H20B	109.5
C6—C7—C2	121.1 (4)	H20A—C20—H20B	109.5
C6—C7—H7A	119.5	C15—C20—H20C	109.5
C2—C7—H7A	119.5	H20A—C20—H20C	109.5
C9—C8—C5	178.9 (5)	H20B—C20—H20C	109.5
C8—C9—Si1	175.8 (4)	Si1—C21—H21A	109.5
C11—C10—C15	118.7 (4)	Si1—C21—H21B	109.5
C11—C10—N1	121.7 (4)	H21A—C21—H21B	109.5
C15—C10—N1	119.6 (3)	Si1—C21—H21C	109.5
C12—C11—C10	121.3 (4)	H21A—C21—H21C	109.5
C12—C11—H11A	119.3	H21B—C21—H21C	109.5
C10—C11—H11A	119.3	Si1—C22—H22A	109.5
C13—C12—C11	119.6 (4)	Si1—C22—H22B	109.5
C13—C12—H12A	120.2	H22A—C22—H22B	109.5
C11—C12—H12A	120.2	Si1—C22—H22C	109.5
C12—C13—C14	120.0 (4)	H22A—C22—H22C	109.5
C12—C13—Cl1	120.2 (3)	H22B—C22—H22C	109.5
C14—C13—Cl1	119.8 (3)	Si1—C23—H23A	109.5
C13—C14—C15	121.2 (4)	Si1—C23—H23B	109.5
C13—C14—H14A	119.4	H23A—C23—H23B	109.5
C15—C14—H14A	119.4	Si1—C23—H23C	109.5
C14—C15—C10	119.1 (4)	H23A—C23—H23C	109.5
C14—C15—C20	120.7 (4)	H23B—C23—H23C	109.5
O1—P1—O2—C16	32.7 (4)	C3—C4—C5—C8	−180.0 (4)
O3—P1—O2—C16	159.1 (3)	C4—C5—C6—C7	−0.4 (6)
C1—P1—O2—C16	−94.2 (3)	C8—C5—C6—C7	178.8 (4)
O1—P1—O3—C18	−35.7 (7)	C5—C6—C7—C2	1.1 (6)
O2—P1—O3—C18	−161.1 (6)	C3—C2—C7—C6	−0.6 (6)
C1—P1—O3—C18	91.8 (6)	C1—C2—C7—C6	178.2 (3)
O1—P1—O3—C18'	39.9 (8)	C1—N1—C10—C11	−24.6 (6)
O2—P1—O3—C18'	−85.6 (8)	C1—N1—C10—C15	157.0 (4)
C1—P1—O3—C18'	167.3 (7)	C15—C10—C11—C12	−1.0 (7)
C10—N1—C1—C2	−61.0 (5)	N1—C10—C11—C12	−179.4 (4)
C10—N1—C1—P1	172.4 (3)	C10—C11—C12—C13	−1.1 (7)
O1—P1—C1—N1	50.7 (4)	C11—C12—C13—C14	2.4 (7)
O3—P1—C1—N1	−78.2 (3)	C11—C12—C13—Cl1	−177.3 (4)
O2—P1—C1—N1	178.2 (3)	C12—C13—C14—C15	−1.6 (7)
O1—P1—C1—C2	−77.8 (3)	Cl1—C13—C14—C15	178.2 (3)
O3—P1—C1—C2	153.4 (3)	C13—C14—C15—C10	−0.6 (6)
O2—P1—C1—C2	49.8 (3)	C13—C14—C15—C20	179.9 (4)
N1—C1—C2—C7	133.7 (4)	C11—C10—C15—C14	1.8 (6)
P1—C1—C2—C7	−100.6 (4)	N1—C10—C15—C14	−179.7 (4)
N1—C1—C2—C3	−47.5 (5)	C11—C10—C15—C20	−178.7 (4)
P1—C1—C2—C3	78.2 (4)	N1—C10—C15—C20	−0.2 (6)
C7—C2—C3—C4	−0.5 (6)	P1—O2—C16—C17	−140.1 (3)
C1—C2—C3—C4	−179.3 (3)	P1—O3—C18—C19	162.8 (9)
C2—C3—C4—C5	1.2 (6)	P1—O3—C18'—C19'	−103.2 (12)
C3—C4—C5—C6	−0.8 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1^i	0.95	2.60	3.543 (5)	175
C7—H7A···O2^ii	0.95	2.54	3.421 (5)	155
C20—H20A···O1^i	0.98	2.49	3.392 (5)	153

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

(III) Diethyl ((4-fluoroanilino){4-[2-(trimethylsilyl)ethynyl]phenyl}methyl)phosphonate

Crystal data

C22H29FNO3PSi	Z = 2
Mr = 433.52	F(000) = 460
Triclinic, P1	Dx = 1.257 Mg m^−3
Hall symbol: -P 1	Melting point: 420(1) K
a = 8.9633 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.1726 (9) Å	Cell parameters from 7350 reflections
c = 12.6997 (10) Å	θ = 3–25°
α = 69.980 (1)°	µ = 0.20 mm^−1
β = 87.263 (1)°	T = 184 K
γ = 73.667 (1)°	Block, pale brown
V = 1145.06 (16) Å^3	0.40 × 0.40 × 0.30 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	4782 independent reflections
Radiation source: normal-focus sealed tube	3504 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ω scans	θmax = 27.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −11→11
Tmin = 0.852, Tmax = 0.941	k = −14→14
12221 measured reflections	l = −16→15

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.067P)^2] where P = (Fo^2 + 2Fc^2)/3
4782 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.39 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	0.44796 (8)	0.79898 (7)	0.44261 (5)	0.02109 (19)
Si1	1.32304 (9)	0.26686 (7)	0.97006 (6)	0.0252 (2)
F1	0.0799 (2)	0.83978 (18)	1.02839 (14)	0.0449 (5)
O1	0.4981 (2)	0.92061 (17)	0.40445 (15)	0.0279 (4)
O2	0.5577 (2)	0.67519 (17)	0.41834 (15)	0.0266 (4)
O3	0.2932 (2)	0.80477 (18)	0.38553 (15)	0.0297 (5)
N1	0.3440 (3)	0.8614 (2)	0.62068 (18)	0.0231 (5)
H1B	0.392 (4)	0.924 (3)	0.601 (2)	0.039 (9)*
C1	0.4263 (3)	0.7429 (2)	0.5946 (2)	0.0220 (6)
H1A	0.3572	0.6830	0.6117	0.026*
C2	0.5820 (3)	0.6633 (2)	0.6590 (2)	0.0207 (6)
C3	0.6891 (3)	0.7256 (3)	0.6739 (2)	0.0257 (6)
H3A	0.6633	0.8198	0.6468	0.031*
C4	0.8337 (3)	0.6516 (3)	0.7280 (2)	0.0275 (6)
H4A	0.9065	0.6956	0.7364	0.033*
C5	0.8732 (3)	0.5129 (3)	0.7701 (2)	0.0263 (6)
C6	0.7656 (3)	0.4501 (3)	0.7548 (2)	0.0291 (6)
H6A	0.7906	0.3559	0.7824	0.035*
C7	0.6220 (3)	0.5252 (3)	0.6992 (2)	0.0272 (6)
H7A	0.5500	0.4816	0.6885	0.033*
C8	1.0212 (3)	0.4358 (3)	0.8306 (2)	0.0287 (6)
C9	1.1429 (3)	0.3699 (3)	0.8824 (2)	0.0306 (7)
C10	0.2815 (3)	0.8494 (3)	0.7272 (2)	0.0218 (6)
C11	0.2295 (3)	0.7412 (3)	0.7907 (2)	0.0257 (6)
H11A	0.2413	0.6689	0.7648	0.031*
C12	0.1603 (3)	0.7380 (3)	0.8920 (2)	0.0305 (7)
H12A	0.1242	0.6646	0.9350	0.037*
C13	0.1454 (3)	0.8426 (3)	0.9282 (2)	0.0292 (6)
C14	0.1952 (3)	0.9512 (3)	0.8674 (2)	0.0312 (7)
H14A	0.1821	1.0232	0.8939	0.037*
C15	0.2643 (3)	0.9540 (3)	0.7673 (2)	0.0276 (6)
H15A	0.3005	1.0278	0.7254	0.033*
C16	0.7250 (3)	0.6572 (3)	0.4094 (2)	0.0301 (6)
H16A	0.7659	0.6827	0.4671	0.036*
H16B	0.7465	0.7137	0.3345	0.036*
C17	0.8015 (3)	0.5135 (3)	0.4264 (3)	0.0415 (8)
H17A	0.9148	0.4975	0.4258	0.062*
H17B	0.7656	0.4909	0.3659	0.062*
H17C	0.7741	0.4583	0.4988	0.062*
C18	0.1491 (3)	0.9122 (3)	0.3746 (3)	0.0368 (7)
H18A	0.1057	0.9493	0.2961	0.044*
H18B	0.1719	0.9843	0.3937	0.044*
C19	0.0330 (4)	0.8595 (3)	0.4517 (3)	0.0454 (8)
H19A	−0.0655	0.9297	0.4403	0.068*
H19B	0.0728	0.8295	0.5297	0.068*
H19C	0.0155	0.7846	0.4355	0.068*
C20	1.4639 (3)	0.1870 (3)	0.8846 (2)	0.0366 (7)
H20A	1.4831	0.2556	0.8172	0.055*
H20B	1.4206	0.1271	0.8626	0.055*
H20C	1.5620	0.1363	0.9290	0.055*
C21	1.4063 (3)	0.3772 (3)	1.0138 (3)	0.0355 (7)
H21A	1.4389	0.4390	0.9477	0.053*
H21B	1.4966	0.3237	1.0661	0.053*
H21C	1.3276	0.4274	1.0509	0.053*
C22	1.2707 (3)	0.1406 (3)	1.0937 (2)	0.0324 (7)
H22A	1.1849	0.1847	1.1303	0.049*
H22B	1.3612	0.0934	1.1469	0.049*
H22C	1.2384	0.0771	1.0690	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0179 (4)	0.0225 (4)	0.0216 (4)	−0.0044 (3)	0.0003 (3)	−0.0070 (3)
Si1	0.0197 (4)	0.0242 (4)	0.0281 (4)	−0.0011 (3)	−0.0042 (3)	−0.0082 (3)
F1	0.0490 (11)	0.0537 (12)	0.0304 (10)	−0.0142 (9)	0.0181 (8)	−0.0147 (8)
O1	0.0299 (11)	0.0254 (10)	0.0279 (10)	−0.0090 (8)	0.0053 (8)	−0.0081 (8)
O2	0.0215 (10)	0.0292 (10)	0.0329 (11)	−0.0071 (8)	0.0036 (8)	−0.0157 (9)
O3	0.0212 (10)	0.0345 (11)	0.0316 (11)	−0.0035 (9)	−0.0048 (8)	−0.0117 (9)
N1	0.0213 (12)	0.0211 (12)	0.0242 (12)	−0.0041 (10)	0.0017 (9)	−0.0059 (10)
C1	0.0206 (14)	0.0200 (13)	0.0246 (14)	−0.0051 (11)	0.0012 (11)	−0.0070 (11)
C2	0.0186 (13)	0.0240 (14)	0.0165 (13)	−0.0005 (11)	0.0023 (10)	−0.0076 (11)
C3	0.0256 (15)	0.0234 (14)	0.0260 (14)	−0.0040 (12)	−0.0009 (11)	−0.0078 (12)
C4	0.0219 (15)	0.0320 (16)	0.0292 (15)	−0.0065 (12)	−0.0011 (11)	−0.0119 (12)
C5	0.0208 (14)	0.0293 (15)	0.0238 (14)	0.0004 (12)	−0.0010 (11)	−0.0088 (12)
C6	0.0265 (15)	0.0214 (14)	0.0307 (15)	−0.0013 (12)	−0.0025 (12)	−0.0023 (12)
C7	0.0222 (14)	0.0258 (15)	0.0310 (15)	−0.0059 (12)	−0.0036 (11)	−0.0066 (12)
C8	0.0245 (15)	0.0314 (16)	0.0280 (15)	−0.0048 (12)	0.0021 (12)	−0.0101 (13)
C9	0.0254 (15)	0.0293 (16)	0.0330 (16)	−0.0042 (13)	−0.0010 (12)	−0.0080 (13)
C10	0.0124 (13)	0.0252 (14)	0.0217 (13)	−0.0007 (11)	−0.0011 (10)	−0.0042 (11)
C11	0.0210 (14)	0.0233 (14)	0.0321 (16)	−0.0047 (11)	0.0026 (12)	−0.0101 (12)
C12	0.0256 (15)	0.0280 (15)	0.0320 (16)	−0.0076 (12)	0.0052 (12)	−0.0036 (13)
C13	0.0207 (15)	0.0412 (17)	0.0233 (14)	−0.0068 (13)	0.0081 (11)	−0.0104 (13)
C14	0.0308 (16)	0.0340 (16)	0.0324 (16)	−0.0079 (13)	0.0038 (13)	−0.0172 (13)
C15	0.0246 (15)	0.0290 (15)	0.0295 (15)	−0.0096 (12)	0.0055 (12)	−0.0096 (12)
C16	0.0184 (14)	0.0389 (17)	0.0373 (16)	−0.0079 (13)	0.0067 (12)	−0.0194 (14)
C17	0.0296 (18)	0.0385 (18)	0.048 (2)	−0.0007 (14)	0.0110 (14)	−0.0129 (15)
C18	0.0272 (16)	0.0338 (17)	0.0372 (17)	0.0007 (13)	−0.0084 (13)	−0.0033 (14)
C19	0.0255 (17)	0.045 (2)	0.055 (2)	−0.0029 (15)	0.0000 (15)	−0.0094 (16)
C20	0.0290 (16)	0.0401 (18)	0.0371 (17)	−0.0010 (14)	0.0019 (13)	−0.0159 (14)
C21	0.0315 (16)	0.0340 (17)	0.0401 (18)	−0.0062 (13)	−0.0037 (13)	−0.0135 (14)
C22	0.0311 (16)	0.0292 (15)	0.0328 (16)	−0.0039 (13)	0.0005 (13)	−0.0092 (13)

Geometric parameters (Å, º)

P1—O1	1.4679 (19)	C11—C12	1.395 (4)
P1—O3	1.5710 (18)	C11—H11A	0.9500
P1—O2	1.5725 (18)	C12—C13	1.367 (4)
P1—C1	1.833 (3)	C12—H12A	0.9500
Si1—C21	1.847 (3)	C13—C14	1.377 (4)
Si1—C9	1.849 (3)	C14—C15	1.382 (4)
Si1—C22	1.861 (3)	C14—H14A	0.9500
Si1—C20	1.862 (3)	C15—H15A	0.9500
F1—C13	1.369 (3)	C16—C17	1.501 (4)
O2—C16	1.460 (3)	C16—H16A	0.9900
O3—C18	1.469 (3)	C16—H16B	0.9900
N1—C10	1.417 (3)	C17—H17A	0.9800
N1—C1	1.461 (3)	C17—H17B	0.9800
N1—H1B	0.88 (3)	C17—H17C	0.9800
C1—C2	1.523 (3)	C18—C19	1.498 (4)
C1—H1A	1.0000	C18—H18A	0.9900
C2—C3	1.388 (4)	C18—H18B	0.9900
C2—C7	1.392 (4)	C19—H19A	0.9800
C3—C4	1.388 (4)	C19—H19B	0.9800
C3—H3A	0.9500	C19—H19C	0.9800
C4—C5	1.398 (4)	C20—H20A	0.9800
C4—H4A	0.9500	C20—H20B	0.9800
C5—C6	1.398 (4)	C20—H20C	0.9800
C5—C8	1.447 (4)	C21—H21A	0.9800
C6—C7	1.390 (4)	C21—H21B	0.9800
C6—H6A	0.9500	C21—H21C	0.9800
C7—H7A	0.9500	C22—H22A	0.9800
C8—C9	1.205 (4)	C22—H22B	0.9800
C10—C11	1.394 (4)	C22—H22C	0.9800
C10—C15	1.395 (4)
O1—P1—O3	116.73 (11)	C12—C13—F1	119.3 (2)
O1—P1—O2	116.52 (11)	C12—C13—C14	122.1 (3)
O3—P1—O2	98.15 (10)	F1—C13—C14	118.6 (2)
O1—P1—C1	111.35 (11)	C13—C14—C15	119.1 (2)
O3—P1—C1	107.21 (11)	C13—C14—H14A	120.5
O2—P1—C1	105.52 (11)	C15—C14—H14A	120.5
C21—Si1—C9	107.99 (13)	C14—C15—C10	120.7 (3)
C21—Si1—C22	111.10 (14)	C14—C15—H15A	119.7
C9—Si1—C22	108.04 (13)	C10—C15—H15A	119.7
C21—Si1—C20	109.43 (14)	O2—C16—C17	107.8 (2)
C9—Si1—C20	108.90 (13)	O2—C16—H16A	110.2
C22—Si1—C20	111.28 (14)	C17—C16—H16A	110.2
C16—O2—P1	121.38 (16)	O2—C16—H16B	110.2
C18—O3—P1	122.23 (17)	C17—C16—H16B	110.2
C10—N1—C1	120.3 (2)	H16A—C16—H16B	108.5
C10—N1—H1B	110.3 (19)	C16—C17—H17A	109.5
C1—N1—H1B	114 (2)	C16—C17—H17B	109.5
N1—C1—C2	115.8 (2)	H17A—C17—H17B	109.5
N1—C1—P1	106.11 (16)	C16—C17—H17C	109.5
C2—C1—P1	111.53 (17)	H17A—C17—H17C	109.5
N1—C1—H1A	107.7	H17B—C17—H17C	109.5
C2—C1—H1A	107.7	O3—C18—C19	109.7 (2)
P1—C1—H1A	107.7	O3—C18—H18A	109.7
C3—C2—C7	118.8 (2)	C19—C18—H18A	109.7
C3—C2—C1	121.3 (2)	O3—C18—H18B	109.7
C7—C2—C1	119.9 (2)	C19—C18—H18B	109.7
C2—C3—C4	120.7 (2)	H18A—C18—H18B	108.2
C2—C3—H3A	119.7	C18—C19—H19A	109.5
C4—C3—H3A	119.7	C18—C19—H19B	109.5
C3—C4—C5	120.7 (2)	H19A—C19—H19B	109.5
C3—C4—H4A	119.7	C18—C19—H19C	109.5
C5—C4—H4A	119.7	H19A—C19—H19C	109.5
C6—C5—C4	118.7 (2)	H19B—C19—H19C	109.5
C6—C5—C8	120.5 (2)	Si1—C20—H20A	109.5
C4—C5—C8	120.7 (2)	Si1—C20—H20B	109.5
C7—C6—C5	120.1 (3)	H20A—C20—H20B	109.5
C7—C6—H6A	119.9	Si1—C20—H20C	109.5
C5—C6—H6A	119.9	H20A—C20—H20C	109.5
C6—C7—C2	121.0 (2)	H20B—C20—H20C	109.5
C6—C7—H7A	119.5	Si1—C21—H21A	109.5
C2—C7—H7A	119.5	Si1—C21—H21B	109.5
C9—C8—C5	178.7 (3)	H21A—C21—H21B	109.5
C8—C9—Si1	176.4 (3)	Si1—C21—H21C	109.5
C11—C10—C15	118.8 (2)	H21A—C21—H21C	109.5
C11—C10—N1	122.9 (2)	H21B—C21—H21C	109.5
C15—C10—N1	118.2 (2)	Si1—C22—H22A	109.5
C10—C11—C12	120.6 (2)	Si1—C22—H22B	109.5
C10—C11—H11A	119.7	H22A—C22—H22B	109.5
C12—C11—H11A	119.7	Si1—C22—H22C	109.5
C13—C12—C11	118.8 (3)	H22A—C22—H22C	109.5
C13—C12—H12A	120.6	H22B—C22—H22C	109.5
C11—C12—H12A	120.6
O1—P1—O2—C16	28.0 (2)	C3—C4—C5—C6	1.2 (4)
O3—P1—O2—C16	153.42 (19)	C3—C4—C5—C8	−177.4 (2)
C1—P1—O2—C16	−96.1 (2)	C4—C5—C6—C7	−0.4 (4)
O1—P1—O3—C18	−49.5 (2)	C8—C5—C6—C7	178.2 (3)
O2—P1—O3—C18	−174.78 (19)	C5—C6—C7—C2	−0.7 (4)
C1—P1—O3—C18	76.1 (2)	C3—C2—C7—C6	0.9 (4)
C10—N1—C1—C2	−68.2 (3)	C1—C2—C7—C6	177.7 (2)
C10—N1—C1—P1	167.48 (18)	C1—N1—C10—C11	−29.9 (3)
O1—P1—C1—N1	44.5 (2)	C1—N1—C10—C15	153.3 (2)
O3—P1—C1—N1	−84.28 (18)	C15—C10—C11—C12	0.6 (4)
O2—P1—C1—N1	171.83 (15)	N1—C10—C11—C12	−176.1 (2)
O1—P1—C1—C2	−82.44 (19)	C10—C11—C12—C13	−0.5 (4)
O3—P1—C1—C2	148.76 (17)	C11—C12—C13—F1	−179.0 (2)
O2—P1—C1—C2	44.87 (19)	C11—C12—C13—C14	0.6 (4)
N1—C1—C2—C3	−44.1 (3)	C12—C13—C14—C15	−0.9 (4)
P1—C1—C2—C3	77.4 (3)	F1—C13—C14—C15	178.7 (2)
N1—C1—C2—C7	139.1 (2)	C13—C14—C15—C10	1.0 (4)
P1—C1—C2—C7	−99.4 (2)	C11—C10—C15—C14	−0.9 (4)
C7—C2—C3—C4	0.0 (4)	N1—C10—C15—C14	176.0 (2)
C1—C2—C3—C4	−176.8 (2)	P1—O2—C16—C17	160.59 (18)
C2—C3—C4—C5	−1.1 (4)	P1—O3—C18—C19	−109.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O1^i	0.88 (3)	2.21 (3)	3.066 (3)	165 (3)
C15—H15A···O1^i	0.95	2.44	3.225 (3)	140
C3—H3A···O1^i	0.95	2.71	3.629 (3)	162
C6—H6A···F1^ii	0.95	2.67	3.424 (3)	136
C14—H14A···F1^iii	0.95	2.76	3.442 (3)	129
C21—H21B···Cg(C10–C15)^iv	0.98	2.83	3.785 (3)	166
C21—H21C···Cg(C2–C7)^iv	0.98	2.95	3.713 (4)	135

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

(IV) Diethyl [(4-ethynylphenyl)(naphthalen-2-ylamino)methyl]phosphonate

Crystal data

C23H24NO3P	Z = 4
Mr = 393.40	F(000) = 832
Triclinic, P1	Dx = 1.266 Mg m^−3
Hall symbol: -P 1	Melting point: 418(1) K
a = 11.3104 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5194 (10) Å	Cell parameters from 5680 reflections
c = 17.8485 (16) Å	θ = 3–25°
α = 82.703 (1)°	µ = 0.16 mm^−1
β = 81.943 (1)°	T = 180 K
γ = 64.035 (1)°	Block, pale brown
V = 2064.5 (3) Å^3	0.60 × 0.44 × 0.30 mm

Data collection

Siemens SMART 1K CCD area-detector diffractometer	8309 independent reflections
Radiation source: normal-focus sealed tube	5727 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 26.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −14→14
Tmin = 0.860, Tmax = 0.954	k = −14→14
21384 measured reflections	l = −22→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.156	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ^2(Fo^2) + (0.04P)^2 + 1.2P] where P = (Fo^2 + 2Fc^2)/3
8309 reflections	(Δ/σ)max = 0.001
517 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.40 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	0.29431 (8)	0.30458 (7)	0.20746 (4)	0.0265 (2)
P2	0.26297 (8)	0.79002 (7)	0.69386 (4)	0.0266 (2)
O1	0.43502 (19)	0.22269 (19)	0.18740 (11)	0.0306 (5)
O2	0.19745 (19)	0.27793 (19)	0.16445 (11)	0.0333 (5)
O3	0.2481 (2)	0.45388 (19)	0.19394 (12)	0.0426 (6)
O4	0.40598 (19)	0.73817 (19)	0.67199 (11)	0.0338 (5)
O5	0.1851 (2)	0.7330 (2)	0.65543 (11)	0.0351 (5)
O6	0.18668 (19)	0.94065 (18)	0.67641 (11)	0.0315 (5)
N1	0.3144 (3)	0.3220 (2)	0.35297 (13)	0.0293 (6)
H1B	0.396 (3)	0.296 (3)	0.3398 (16)	0.026 (8)*
N2	0.2838 (3)	0.8086 (2)	0.83689 (13)	0.0282 (6)
H2A	0.366 (3)	0.787 (2)	0.8232 (15)	0.014 (7)*
C1	0.2430 (3)	0.2836 (3)	0.30765 (15)	0.0265 (7)
H1A	0.1470	0.3425	0.3166	0.032*
C2	0.2592 (3)	0.1437 (3)	0.32391 (15)	0.0265 (7)
C3	0.3808 (3)	0.0455 (3)	0.33859 (19)	0.0413 (8)
H3A	0.4523	0.0662	0.3424	0.050*
C4	0.4004 (3)	−0.0824 (3)	0.3479 (2)	0.0465 (9)
H4A	0.4850	−0.1485	0.3578	0.056*
C5	0.2972 (3)	−0.1151 (3)	0.34285 (17)	0.0366 (8)
C6	0.1738 (3)	−0.0153 (3)	0.33018 (17)	0.0356 (8)
H6A	0.1011	−0.0350	0.3285	0.043*
C7	0.1559 (3)	0.1114 (3)	0.32006 (16)	0.0309 (7)
H7A	0.0713	0.1779	0.3103	0.037*
C8	0.3179 (4)	−0.2489 (3)	0.3500 (2)	0.0464 (9)
C9	0.3353 (4)	−0.3579 (4)	0.3536 (2)	0.0611 (11)
H9A	0.3493	−0.4459	0.3565	0.073*
C10	0.2795 (3)	0.3323 (3)	0.43102 (15)	0.0259 (6)
C11	0.1623 (3)	0.3339 (3)	0.46709 (15)	0.0273 (7)
H11A	0.1041	0.3212	0.4389	0.033*
C12	0.1277 (3)	0.3541 (3)	0.54528 (15)	0.0266 (7)
C13	0.2143 (3)	0.3734 (3)	0.58760 (16)	0.0277 (7)
C14	0.3351 (3)	0.3692 (3)	0.54937 (17)	0.0318 (7)
H14A	0.3948	0.3809	0.5768	0.038*
C15	0.3667 (3)	0.3488 (3)	0.47421 (16)	0.0293 (7)
H15A	0.4485	0.3455	0.4502	0.035*
C16	0.2390 (3)	0.1607 (3)	0.12558 (18)	0.0430 (8)
H16A	0.1648	0.1359	0.1293	0.052*
H16B	0.3128	0.0891	0.1503	0.052*
C17	0.2825 (4)	0.1814 (4)	0.0436 (2)	0.0644 (12)
H17A	0.3021	0.1044	0.0172	0.097*
H17B	0.3619	0.1966	0.0398	0.097*
H17C	0.2118	0.2567	0.0201	0.097*
C18	0.2302 (5)	0.5244 (4)	0.1202 (2)	0.0677 (13)
H18A	0.1666	0.5063	0.0964	0.081*
H18B	0.1879	0.6179	0.1284	0.081*
C19	0.3414 (5)	0.5017 (4)	0.0670 (3)	0.0851 (16)
H19A	0.3132	0.5543	0.0197	0.128*
H19B	0.3848	0.4098	0.0571	0.128*
H19C	0.4034	0.5251	0.0874	0.128*
C20	0.0085 (3)	0.3557 (3)	0.58369 (16)	0.0317 (7)
H20A	−0.0506	0.3426	0.5565	0.038*
C21	−0.0228 (3)	0.3760 (3)	0.65947 (17)	0.0352 (8)
H21A	−0.1030	0.3763	0.6842	0.042*
C22	0.0623 (3)	0.3961 (3)	0.70062 (17)	0.0389 (8)
H22A	0.0395	0.4102	0.7530	0.047*
C23	0.1778 (3)	0.3956 (3)	0.66576 (17)	0.0363 (8)
H23A	0.2345	0.4102	0.6941	0.044*
C24	0.2218 (3)	0.7548 (3)	0.79392 (15)	0.0260 (6)
H24A	0.1239	0.8019	0.8052	0.031*
C25	0.2608 (3)	0.6102 (3)	0.81254 (15)	0.0267 (7)
C26	0.3922 (3)	0.5224 (3)	0.80202 (18)	0.0361 (8)
H26A	0.4575	0.5534	0.7856	0.043*
C27	0.4301 (3)	0.3907 (3)	0.81496 (18)	0.0403 (8)
H27A	0.5206	0.3323	0.8067	0.048*
C28	0.3360 (3)	0.3430 (3)	0.84007 (16)	0.0336 (7)
C29	0.2049 (3)	0.4309 (3)	0.85428 (16)	0.0343 (7)
H29A	0.1403	0.4004	0.8742	0.041*
C30	0.1675 (3)	0.5631 (3)	0.83956 (16)	0.0305 (7)
H30A	0.0772	0.6220	0.8481	0.037*
C31	0.3754 (3)	0.2050 (3)	0.84541 (18)	0.0401 (8)
C32	0.4093 (4)	0.0920 (4)	0.8444 (2)	0.0509 (10)
H32A	0.4364	0.0016	0.8436	0.061*
C33	0.2505 (3)	0.8181 (3)	0.91559 (15)	0.0253 (6)
C34	0.1325 (3)	0.8228 (3)	0.95176 (16)	0.0275 (7)
H34A	0.0719	0.8140	0.9236	0.033*
C35	0.1003 (3)	0.8405 (3)	1.03078 (16)	0.0278 (7)
C36	0.1910 (3)	0.8517 (3)	1.07301 (16)	0.0292 (7)
C37	0.3123 (3)	0.8446 (3)	1.03464 (16)	0.0316 (7)
H37A	0.3747	0.8513	1.0622	0.038*
C38	0.3409 (3)	0.8283 (3)	0.95844 (16)	0.0298 (7)
H38A	0.4229	0.8237	0.9341	0.036*
C39	0.2062 (4)	0.7183 (4)	0.57355 (19)	0.0502 (10)
H39A	0.1963	0.6404	0.5639	0.060*
H39B	0.2975	0.7054	0.5549	0.060*
C40	0.1117 (4)	0.8328 (4)	0.53111 (19)	0.0555 (11)
H40A	0.1303	0.8202	0.4767	0.083*
H40B	0.1209	0.9102	0.5407	0.083*
H40C	0.0214	0.8437	0.5479	0.083*
C41	0.2558 (3)	1.0239 (3)	0.65979 (19)	0.0385 (8)
H41A	0.3288	0.9936	0.6927	0.046*
H41B	0.1939	1.1135	0.6715	0.046*
C42	0.3110 (4)	1.0236 (3)	0.57795 (19)	0.0455 (9)
H42A	0.3509	1.0849	0.5680	0.068*
H42B	0.2396	1.0491	0.5452	0.068*
H42C	0.3782	0.9365	0.5674	0.068*
C43	−0.0209 (3)	0.8466 (3)	1.06854 (17)	0.0321 (7)
H43A	−0.0830	0.8400	1.0406	0.039*
C44	−0.0497 (3)	0.8619 (3)	1.14493 (18)	0.0366 (8)
H44A	−0.1312	0.8652	1.1694	0.044*
C45	0.0402 (3)	0.8727 (3)	1.18718 (18)	0.0393 (8)
H45A	0.0194	0.8832	1.2401	0.047*
C46	0.1581 (3)	0.8681 (3)	1.15238 (17)	0.0356 (8)
H46A	0.2183	0.8760	1.1813	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0297 (4)	0.0276 (4)	0.0190 (4)	−0.0109 (3)	0.0033 (3)	−0.0014 (3)
P2	0.0252 (4)	0.0309 (4)	0.0195 (4)	−0.0093 (3)	−0.0003 (3)	0.0005 (3)
O1	0.0302 (12)	0.0368 (12)	0.0249 (11)	−0.0159 (10)	0.0050 (9)	−0.0055 (9)
O2	0.0295 (12)	0.0405 (12)	0.0257 (11)	−0.0115 (10)	−0.0023 (9)	−0.0011 (9)
O3	0.0610 (16)	0.0293 (12)	0.0277 (12)	−0.0143 (11)	0.0085 (11)	−0.0008 (9)
O4	0.0274 (12)	0.0421 (12)	0.0260 (11)	−0.0110 (10)	0.0013 (9)	−0.0005 (9)
O5	0.0405 (13)	0.0422 (13)	0.0260 (11)	−0.0205 (11)	−0.0080 (10)	0.0016 (9)
O6	0.0285 (12)	0.0333 (11)	0.0290 (11)	−0.0117 (10)	0.0025 (9)	−0.0002 (9)
N1	0.0269 (15)	0.0406 (15)	0.0209 (13)	−0.0166 (13)	0.0059 (11)	−0.0048 (11)
N2	0.0246 (15)	0.0374 (15)	0.0214 (13)	−0.0141 (12)	0.0045 (11)	−0.0027 (11)
C1	0.0266 (16)	0.0303 (16)	0.0184 (14)	−0.0092 (13)	0.0022 (12)	−0.0031 (12)
C2	0.0267 (16)	0.0340 (16)	0.0161 (14)	−0.0125 (14)	0.0043 (12)	−0.0016 (12)
C3	0.0302 (19)	0.041 (2)	0.054 (2)	−0.0187 (16)	−0.0088 (16)	0.0081 (16)
C4	0.0326 (19)	0.0380 (19)	0.061 (2)	−0.0108 (16)	−0.0095 (17)	0.0125 (17)
C5	0.048 (2)	0.0372 (18)	0.0255 (16)	−0.0217 (17)	0.0013 (15)	0.0029 (14)
C6	0.0358 (19)	0.046 (2)	0.0297 (17)	−0.0237 (16)	0.0013 (14)	−0.0030 (14)
C7	0.0280 (17)	0.0372 (18)	0.0254 (16)	−0.0130 (14)	0.0002 (13)	−0.0025 (13)
C8	0.053 (2)	0.046 (2)	0.041 (2)	−0.0255 (19)	0.0042 (17)	0.0014 (16)
C9	0.074 (3)	0.043 (2)	0.065 (3)	−0.027 (2)	0.002 (2)	0.000 (2)
C10	0.0285 (16)	0.0235 (15)	0.0217 (15)	−0.0086 (13)	0.0007 (13)	−0.0009 (11)
C11	0.0320 (17)	0.0298 (16)	0.0211 (15)	−0.0142 (14)	−0.0010 (13)	−0.0033 (12)
C12	0.0286 (16)	0.0241 (15)	0.0225 (15)	−0.0084 (13)	0.0027 (13)	−0.0017 (12)
C13	0.0319 (17)	0.0228 (15)	0.0242 (15)	−0.0087 (13)	−0.0029 (13)	0.0011 (12)
C14	0.0319 (18)	0.0334 (17)	0.0302 (17)	−0.0131 (14)	−0.0077 (14)	0.0000 (13)
C15	0.0284 (17)	0.0317 (16)	0.0272 (16)	−0.0135 (14)	0.0005 (13)	−0.0005 (13)
C16	0.043 (2)	0.055 (2)	0.0374 (19)	−0.0249 (18)	−0.0068 (16)	−0.0075 (16)
C17	0.082 (3)	0.093 (3)	0.040 (2)	−0.056 (3)	0.004 (2)	−0.025 (2)
C18	0.096 (3)	0.038 (2)	0.048 (2)	−0.019 (2)	0.011 (2)	0.0138 (18)
C19	0.108 (4)	0.052 (3)	0.061 (3)	−0.017 (3)	0.029 (3)	0.009 (2)
C20	0.0342 (18)	0.0345 (17)	0.0260 (16)	−0.0150 (14)	0.0002 (14)	−0.0033 (13)
C21	0.0372 (19)	0.0385 (18)	0.0253 (16)	−0.0155 (15)	0.0083 (14)	−0.0019 (13)
C22	0.045 (2)	0.045 (2)	0.0201 (16)	−0.0138 (17)	0.0030 (15)	−0.0049 (14)
C23	0.042 (2)	0.0417 (19)	0.0230 (16)	−0.0151 (16)	−0.0053 (14)	−0.0028 (14)
C24	0.0236 (16)	0.0339 (16)	0.0190 (14)	−0.0120 (13)	0.0015 (12)	−0.0018 (12)
C25	0.0283 (17)	0.0343 (16)	0.0172 (14)	−0.0128 (14)	−0.0043 (12)	−0.0005 (12)
C26	0.0275 (17)	0.0385 (18)	0.0398 (19)	−0.0146 (15)	−0.0011 (14)	0.0056 (15)
C27	0.0327 (19)	0.0366 (19)	0.042 (2)	−0.0072 (15)	−0.0047 (15)	0.0043 (15)
C28	0.041 (2)	0.0361 (18)	0.0221 (16)	−0.0149 (16)	−0.0061 (14)	−0.0004 (13)
C29	0.040 (2)	0.0438 (19)	0.0256 (16)	−0.0243 (16)	−0.0025 (14)	−0.0023 (14)
C30	0.0309 (17)	0.0376 (18)	0.0212 (15)	−0.0136 (14)	0.0010 (13)	−0.0040 (13)
C31	0.049 (2)	0.040 (2)	0.0297 (17)	−0.0185 (17)	−0.0054 (15)	0.0011 (15)
C32	0.064 (3)	0.037 (2)	0.052 (2)	−0.0228 (19)	−0.0063 (19)	0.0014 (17)
C33	0.0292 (16)	0.0220 (15)	0.0215 (14)	−0.0093 (13)	0.0003 (12)	0.0001 (11)
C34	0.0278 (16)	0.0296 (16)	0.0235 (15)	−0.0115 (13)	−0.0009 (13)	−0.0012 (12)
C35	0.0292 (17)	0.0232 (15)	0.0266 (16)	−0.0087 (13)	0.0018 (13)	−0.0010 (12)
C36	0.0362 (18)	0.0260 (16)	0.0231 (15)	−0.0123 (14)	0.0020 (13)	−0.0030 (12)
C37	0.0323 (18)	0.0405 (18)	0.0272 (16)	−0.0202 (15)	−0.0023 (14)	−0.0039 (14)
C38	0.0271 (17)	0.0341 (17)	0.0262 (16)	−0.0131 (14)	0.0022 (13)	−0.0007 (13)
C39	0.048 (2)	0.061 (2)	0.039 (2)	−0.0152 (19)	−0.0048 (17)	−0.0259 (18)
C40	0.090 (3)	0.062 (2)	0.0254 (18)	−0.042 (2)	−0.0118 (19)	0.0013 (17)
C41	0.0383 (19)	0.0316 (17)	0.048 (2)	−0.0176 (15)	−0.0020 (16)	−0.0039 (15)
C42	0.052 (2)	0.0384 (19)	0.044 (2)	−0.0219 (17)	0.0037 (17)	0.0043 (16)
C43	0.0297 (17)	0.0334 (17)	0.0292 (17)	−0.0113 (14)	0.0032 (13)	−0.0036 (13)
C44	0.0328 (18)	0.0375 (18)	0.0341 (18)	−0.0134 (15)	0.0099 (15)	−0.0047 (14)
C45	0.048 (2)	0.0404 (19)	0.0248 (16)	−0.0174 (17)	0.0092 (15)	−0.0073 (14)
C46	0.046 (2)	0.0398 (18)	0.0245 (16)	−0.0206 (16)	−0.0028 (15)	−0.0052 (14)

Geometric parameters (Å, º)

P1—O1	1.471 (2)	C19—H19B	0.9800
P1—O3	1.559 (2)	C19—H19C	0.9800
P1—O2	1.573 (2)	C20—C21	1.372 (4)
P1—C1	1.821 (3)	C20—H20A	0.9500
P2—O4	1.470 (2)	C21—C22	1.399 (4)
P2—O5	1.571 (2)	C21—H21A	0.9500
P2—O6	1.575 (2)	C22—C23	1.364 (4)
P2—C24	1.822 (3)	C22—H22A	0.9500
O2—C16	1.455 (4)	C23—H23A	0.9500
O3—C18	1.447 (4)	C24—C25	1.528 (4)
O5—C39	1.467 (4)	C24—H24A	1.0000
O6—C41	1.463 (4)	C25—C26	1.385 (4)
N1—C10	1.399 (3)	C25—C30	1.390 (4)
N1—C1	1.445 (4)	C26—C27	1.381 (4)
N1—H1B	0.85 (3)	C26—H26A	0.9500
N2—C33	1.408 (3)	C27—C28	1.398 (4)
N2—C24	1.455 (4)	C27—H27A	0.9500
N2—H2A	0.86 (3)	C28—C29	1.391 (4)
C1—C2	1.534 (4)	C28—C31	1.444 (4)
C1—H1A	1.0000	C29—C30	1.390 (4)
C2—C3	1.380 (4)	C29—H29A	0.9500
C2—C7	1.385 (4)	C30—H30A	0.9500
C3—C4	1.382 (4)	C31—C32	1.187 (4)
C3—H3A	0.9500	C32—H32A	0.9500
C4—C5	1.391 (5)	C33—C34	1.380 (4)
C4—H4A	0.9500	C33—C38	1.411 (4)
C5—C6	1.392 (4)	C34—C35	1.424 (4)
C5—C8	1.446 (5)	C34—H34A	0.9500
C6—C7	1.374 (4)	C35—C36	1.412 (4)
C6—H6A	0.9500	C35—C43	1.416 (4)
C7—H7A	0.9500	C36—C37	1.418 (4)
C8—C9	1.178 (5)	C36—C46	1.428 (4)
C9—H9A	0.9500	C37—C38	1.371 (4)
C10—C11	1.384 (4)	C37—H37A	0.9500
C10—C15	1.420 (4)	C38—H38A	0.9500
C11—C12	1.416 (4)	C39—C40	1.481 (5)
C11—H11A	0.9500	C39—H39A	0.9900
C12—C20	1.418 (4)	C39—H39B	0.9900
C12—C13	1.421 (4)	C40—H40A	0.9800
C13—C23	1.421 (4)	C40—H40B	0.9800
C13—C14	1.423 (4)	C40—H40C	0.9800
C14—C15	1.362 (4)	C41—C42	1.505 (4)
C14—H14A	0.9500	C41—H41A	0.9900
C15—H15A	0.9500	C41—H41B	0.9900
C16—C17	1.501 (5)	C42—H42A	0.9800
C16—H16A	0.9900	C42—H42B	0.9800
C16—H16B	0.9900	C42—H42C	0.9800
C17—H17A	0.9800	C43—C44	1.372 (4)
C17—H17B	0.9800	C43—H43A	0.9500
C17—H17C	0.9800	C44—C45	1.403 (5)
C18—C19	1.410 (5)	C44—H44A	0.9500
C18—H18A	0.9900	C45—C46	1.372 (4)
C18—H18B	0.9900	C45—H45A	0.9500
C19—H19A	0.9800	C46—H46A	0.9500
O1—P1—O3	116.72 (12)	C21—C20—H20A	119.5
O1—P1—O2	114.27 (11)	C12—C20—H20A	119.5
O3—P1—O2	103.90 (12)	C20—C21—C22	120.6 (3)
O1—P1—C1	112.85 (13)	C20—C21—H21A	119.7
O3—P1—C1	103.00 (12)	C22—C21—H21A	119.7
O2—P1—C1	104.72 (12)	C23—C22—C21	120.2 (3)
O4—P2—O5	116.27 (12)	C23—C22—H22A	119.9
O4—P2—O6	114.01 (12)	C21—C22—H22A	119.9
O5—P2—O6	103.82 (11)	C22—C23—C13	120.8 (3)
O4—P2—C24	113.29 (13)	C22—C23—H23A	119.6
O5—P2—C24	101.00 (12)	C13—C23—H23A	119.6
O6—P2—C24	107.13 (12)	N2—C24—C25	114.3 (2)
C16—O2—P1	122.56 (19)	N2—C24—P2	106.79 (18)
C18—O3—P1	124.4 (2)	C25—C24—P2	111.47 (19)
C39—O5—P2	121.2 (2)	N2—C24—H24A	108.0
C41—O6—P2	121.75 (19)	C25—C24—H24A	108.0
C10—N1—C1	120.6 (2)	P2—C24—H24A	108.0
C10—N1—H1B	115 (2)	C26—C25—C30	118.4 (3)
C1—N1—H1B	116 (2)	C26—C25—C24	119.8 (3)
C33—N2—C24	120.2 (2)	C30—C25—C24	121.7 (3)
C33—N2—H2A	113.8 (18)	C27—C26—C25	121.3 (3)
C24—N2—H2A	114.6 (18)	C27—C26—H26A	119.4
N1—C1—C2	115.7 (2)	C25—C26—H26A	119.4
N1—C1—P1	109.68 (19)	C26—C27—C28	120.4 (3)
C2—C1—P1	107.49 (18)	C26—C27—H27A	119.8
N1—C1—H1A	107.9	C28—C27—H27A	119.8
C2—C1—H1A	107.9	C29—C28—C27	118.5 (3)
P1—C1—H1A	107.9	C29—C28—C31	121.9 (3)
C3—C2—C7	118.4 (3)	C27—C28—C31	119.4 (3)
C3—C2—C1	119.9 (3)	C30—C29—C28	120.5 (3)
C7—C2—C1	121.5 (3)	C30—C29—H29A	119.7
C2—C3—C4	121.1 (3)	C28—C29—H29A	119.7
C2—C3—H3A	119.5	C25—C30—C29	120.8 (3)
C4—C3—H3A	119.5	C25—C30—H30A	119.6
C3—C4—C5	120.5 (3)	C29—C30—H30A	119.6
C3—C4—H4A	119.7	C32—C31—C28	175.4 (4)
C5—C4—H4A	119.7	C31—C32—H32A	180.0
C4—C5—C6	118.1 (3)	C34—C33—N2	123.2 (3)
C4—C5—C8	120.9 (3)	C34—C33—C38	119.0 (3)
C6—C5—C8	121.1 (3)	N2—C33—C38	117.7 (3)
C7—C6—C5	120.9 (3)	C33—C34—C35	120.9 (3)
C7—C6—H6A	119.6	C33—C34—H34A	119.6
C5—C6—H6A	119.6	C35—C34—H34A	119.6
C6—C7—C2	121.0 (3)	C36—C35—C43	118.8 (3)
C6—C7—H7A	119.5	C36—C35—C34	119.6 (3)
C2—C7—H7A	119.5	C43—C35—C34	121.5 (3)
C9—C8—C5	178.0 (4)	C35—C36—C37	118.3 (3)
C8—C9—H9A	180.0	C35—C36—C46	119.1 (3)
C11—C10—N1	123.5 (3)	C37—C36—C46	122.6 (3)
C11—C10—C15	118.8 (3)	C38—C37—C36	121.1 (3)
N1—C10—C15	117.6 (3)	C38—C37—H37A	119.4
C10—C11—C12	121.1 (3)	C36—C37—H37A	119.4
C10—C11—H11A	119.5	C37—C38—C33	121.1 (3)
C12—C11—H11A	119.5	C37—C38—H38A	119.5
C11—C12—C20	122.2 (3)	C33—C38—H38A	119.5
C11—C12—C13	119.7 (3)	O5—C39—C40	111.9 (3)
C20—C12—C13	118.1 (3)	O5—C39—H39A	109.2
C23—C13—C12	119.3 (3)	C40—C39—H39A	109.2
C23—C13—C14	122.6 (3)	O5—C39—H39B	109.2
C12—C13—C14	118.1 (3)	C40—C39—H39B	109.2
C15—C14—C13	121.2 (3)	H39A—C39—H39B	107.9
C15—C14—H14A	119.4	C39—C40—H40A	109.5
C13—C14—H14A	119.4	C39—C40—H40B	109.5
C14—C15—C10	121.2 (3)	H40A—C40—H40B	109.5
C14—C15—H15A	119.4	C39—C40—H40C	109.5
C10—C15—H15A	119.4	H40A—C40—H40C	109.5
O2—C16—C17	110.6 (3)	H40B—C40—H40C	109.5
O2—C16—H16A	109.5	O6—C41—C42	111.7 (3)
C17—C16—H16A	109.5	O6—C41—H41A	109.3
O2—C16—H16B	109.5	C42—C41—H41A	109.3
C17—C16—H16B	109.5	O6—C41—H41B	109.3
H16A—C16—H16B	108.1	C42—C41—H41B	109.3
C16—C17—H17A	109.5	H41A—C41—H41B	107.9
C16—C17—H17B	109.5	C41—C42—H42A	109.5
H17A—C17—H17B	109.5	C41—C42—H42B	109.5
C16—C17—H17C	109.5	H42A—C42—H42B	109.5
H17A—C17—H17C	109.5	C41—C42—H42C	109.5
H17B—C17—H17C	109.5	H42A—C42—H42C	109.5
C19—C18—O3	119.1 (4)	H42B—C42—H42C	109.5
C19—C18—H18A	107.5	C44—C43—C35	120.9 (3)
O3—C18—H18A	107.5	C44—C43—H43A	119.6
C19—C18—H18B	107.5	C35—C43—H43A	119.6
O3—C18—H18B	107.5	C43—C44—C45	120.5 (3)
H18A—C18—H18B	107.0	C43—C44—H44A	119.7
C18—C19—H19A	109.5	C45—C44—H44A	119.7
C18—C19—H19B	109.5	C46—C45—C44	120.2 (3)
H19A—C19—H19B	109.5	C46—C45—H45A	119.9
C18—C19—H19C	109.5	C44—C45—H45A	119.9
H19A—C19—H19C	109.5	C45—C46—C36	120.5 (3)
H19B—C19—H19C	109.5	C45—C46—H46A	119.8
C21—C20—C12	121.0 (3)	C36—C46—H46A	119.8
O1—P1—O2—C16	16.7 (3)	C13—C12—C20—C21	0.3 (4)
O3—P1—O2—C16	145.0 (2)	C12—C20—C21—C22	0.3 (5)
C1—P1—O2—C16	−107.3 (2)	C20—C21—C22—C23	−0.1 (5)
O1—P1—O3—C18	74.8 (3)	C21—C22—C23—C13	−0.6 (5)
O2—P1—O3—C18	−51.9 (3)	C12—C13—C23—C22	1.2 (4)
C1—P1—O3—C18	−161.0 (3)	C14—C13—C23—C22	−178.6 (3)
O4—P2—O5—C39	−46.2 (3)	C33—N2—C24—C25	−67.9 (3)
O6—P2—O5—C39	79.9 (2)	C33—N2—C24—P2	168.3 (2)
C24—P2—O5—C39	−169.2 (2)	O4—P2—C24—N2	57.5 (2)
O4—P2—O6—C41	−15.7 (3)	O5—P2—C24—N2	−177.47 (18)
O5—P2—O6—C41	−143.2 (2)	O6—P2—C24—N2	−69.1 (2)
C24—P2—O6—C41	110.5 (2)	O4—P2—C24—C25	−68.0 (2)
C10—N1—C1—C2	−67.3 (3)	O5—P2—C24—C25	57.0 (2)
C10—N1—C1—P1	170.9 (2)	O6—P2—C24—C25	165.37 (19)
O1—P1—C1—N1	62.4 (2)	N2—C24—C25—C26	−59.7 (3)
O3—P1—C1—N1	−64.3 (2)	P2—C24—C25—C26	61.6 (3)
O2—P1—C1—N1	−172.68 (19)	N2—C24—C25—C30	120.8 (3)
O1—P1—C1—C2	−64.1 (2)	P2—C24—C25—C30	−118.0 (3)
O3—P1—C1—C2	169.18 (19)	C30—C25—C26—C27	2.6 (4)
O2—P1—C1—C2	60.8 (2)	C24—C25—C26—C27	−177.0 (3)
N1—C1—C2—C3	−39.3 (4)	C25—C26—C27—C28	−0.8 (5)
P1—C1—C2—C3	83.6 (3)	C26—C27—C28—C29	−2.3 (5)
N1—C1—C2—C7	144.4 (3)	C26—C27—C28—C31	173.4 (3)
P1—C1—C2—C7	−92.7 (3)	C27—C28—C29—C30	3.7 (4)
C7—C2—C3—C4	1.2 (5)	C31—C28—C29—C30	−171.9 (3)
C1—C2—C3—C4	−175.2 (3)	C26—C25—C30—C29	−1.2 (4)
C2—C3—C4—C5	−0.2 (5)	C24—C25—C30—C29	178.3 (3)
C3—C4—C5—C6	−1.6 (5)	C28—C29—C30—C25	−1.9 (4)
C3—C4—C5—C8	177.9 (3)	C24—N2—C33—C34	−23.5 (4)
C4—C5—C6—C7	2.5 (5)	C24—N2—C33—C38	159.0 (3)
C8—C5—C6—C7	−177.1 (3)	N2—C33—C34—C35	−176.1 (2)
C5—C6—C7—C2	−1.5 (5)	C38—C33—C34—C35	1.4 (4)
C3—C2—C7—C6	−0.3 (4)	C33—C34—C35—C36	−0.9 (4)
C1—C2—C7—C6	176.0 (3)	C33—C34—C35—C43	179.4 (3)
C1—N1—C10—C11	−13.9 (4)	C43—C35—C36—C37	179.6 (3)
C1—N1—C10—C15	169.6 (2)	C34—C35—C36—C37	−0.1 (4)
N1—C10—C11—C12	−175.3 (3)	C43—C35—C36—C46	0.3 (4)
C15—C10—C11—C12	1.2 (4)	C34—C35—C36—C46	−179.4 (3)
C10—C11—C12—C20	−179.8 (3)	C35—C36—C37—C38	0.4 (4)
C10—C11—C12—C13	0.2 (4)	C46—C36—C37—C38	179.7 (3)
C11—C12—C13—C23	179.0 (3)	C36—C37—C38—C33	0.1 (5)
C20—C12—C13—C23	−1.0 (4)	C34—C33—C38—C37	−1.1 (4)
C11—C12—C13—C14	−1.1 (4)	N2—C33—C38—C37	176.6 (3)
C20—C12—C13—C14	178.8 (3)	P2—O5—C39—C40	−92.7 (3)
C23—C13—C14—C15	−179.5 (3)	P2—O6—C41—C42	82.4 (3)
C12—C13—C14—C15	0.7 (4)	C36—C35—C43—C44	−0.6 (4)
C13—C14—C15—C10	0.7 (4)	C34—C35—C43—C44	179.1 (3)
C11—C10—C15—C14	−1.7 (4)	C35—C43—C44—C45	0.4 (5)
N1—C10—C15—C14	175.0 (3)	C43—C44—C45—C46	0.0 (5)
P1—O2—C16—C17	−92.8 (3)	C44—C45—C46—C36	−0.3 (5)
P1—O3—C18—C19	−65.9 (5)	C35—C36—C46—C45	0.2 (4)
C11—C12—C20—C21	−179.8 (3)	C37—C36—C46—C45	−179.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4^i	0.85 (3)	2.08 (3)	2.906 (3)	166 (3)
N2—H2A···O1^i	0.86 (3)	2.19 (3)	3.013 (3)	162 (2)
C15—H15A···O4^i	0.95	2.56	3.309 (3)	136
C32—H32A···O1^ii	0.95	2.44	3.349 (4)	161
C38—H38A···O1^i	0.95	2.48	3.283 (3)	143
C7—H7A···O5^iii	0.95	2.63	3.457 (4)	146
C18—H18B···Cg(C35/C36/C43–C46)^iv	0.99	2.48	3.439 (4)	163
C19—H19A···Cg(C33–C38)^iv	0.98	2.92	3.591 (5)	127
C23—H23A···Cg(C25–C30)	0.95	2.86	3.735 (4)	153
C41—H41B···Cg(C12/C13/C20–C23)^v	0.99	2.78	3.649 (3)	147
C42—H42A···Cg(C10–C15)^v	0.98	2.88	3.609 (3)	132

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