Investigations on benz­[1,2]­oxaphos­phinane derivatives

The structures of two compounds, 3-[1-(2-hydroxy­ethyl­amino)­ethyl­idene]-2-methoxy-3,4-di­hydro-1,2λ⁵-benz­oxa­phosphinane-2,4-dione, C₁₃H₁₆NO₅P, and 3-[1-(2-hydr­oxy-­ethyl­amino)­ethyl­idene]-2-methoxy-6-methyl-3,4-di­hydro-1,2λ⁵-benz­oxaphosphinane-2,4-dione, C₁₄H₁₈NO₅P, have been studied and compared. The oxophosphinane rings have a half-chair conformation and extra six- and five-membered rings are formed by intramolecular N—H...O hydrogen bonds. An intermolecular O—H...O hydrogen bond is also observed.

S1. Comment

The aminophosphonic acids are the synthetic analogues of the natural amino acids in which the carboxylic acid group is replaced by phosphonic acid group. The aminophosphonic acids, their esters and salts have very attractive significant attention owing to their synthetic and biological value both as agrochemical (herbicides, pesticides, growth regulator in plants) and medical (antibiotics, antivirals, enzyme inhibitors) products with broad applications (Kalir & Kalir, 1996; Hudson & Pianka, 1996; Kukhar & Hudson, 1999).

In our previous work we described the reaction of the 2-methyl-4-oxo-4H-chromen-3-yl-phosphonate, (Ia), and 2,6-dimethyl-4-oxo-4H-chromen-3-yl-phosphonate, (IIa), with 2-hydroxyethylamine (Budzisz et al., 2001). In this reaction we obtained cyclic 2-aminophosphonic analogues of chromone of 2-methoxy-3-[1(2-hydroxyethylamine)ethylidene]-2,3-dihydro-2,4-dioxo-2λ⁵– benzo[e][1,2]oxaphosphinane, (I), and 2-methoxy-6-methyl-3-[1(2-hydroxyethyl amine)ethylidene]-2,3-dihydro-2,4-dioxo-2λ⁵-benzo[e][1,2]oxaphosphinane, (II) general structure (Budzisz & Pastuszko, 1999; Budzisz et al., 2001). The obtained compounds exhibited alkylation properties in the NBS-test (Preussman et al., 1969). \sch

In the series of IR spectra determined in chloroform, the derivatives of benzo[1,2]oxaphosphinane in various concentrations (1 mM to 100 mM) confirm the presence of a strong intramolecular hydrogen bond exhibiting a broad band at ν 3430–3450 cm^-1.

The X-ray structural investigation on two derivatives of benzo[1,2]oxaphosphinane has been carried out in continuation of our studies (Budzisz et al., 2001). The titled structures consist of a benzene ring fused with an oxaphosphinane ring. The hydroxyethylamine ethylidyne group is attached at position 3 in both molecules. In (II), the benzene ring is substituted by a methyl group at position 6.

The oxaphosphinane rings have half-chair conformation. The puckering parameters (Cremer & Pople, 1975) are Q_T = 0.383 (3) Å, ϕ₂ = 32.1 (8)°, θ₂ = 67.1 (7)° in (I) and Q_T = 0.360 (2) Å, ϕ₂ = 38.7 (5)°, θ₂ = 65.8 (7)° in (II), corresponding to the O1—P2—C3—C4—C10—C9 atom sequence, with twofold pseudo-axis passing through the midpoints of P2—O1 and C4—C10 bonds; asymmetry parameters (Nardelli, 1983) Δ₂ = 0.009 (2) for (I) and Δ₂ = 0.025 (1) for (II).

An intramolecular hydrogen bond, N32—H32···O4 and N32—H32···O35, is observed in both molecules which closes the extra six- and five-membered rings, respectively. The six-membered rings are planar, whereas conformation of the five-membered rings is C34 deformed envelope (I) and N32 twist (II) [asymmetry parameters (Nardelli, 1983a) Δ_s = 0.04 (1) for (I), and Δ₂ = 0.05 (1) for (II). The puckering parameters (Cremer & Pople, 1975) are: q₂ = 0.42 (1) Å, ϕ₂ = -137 (5)°, in (I) and q₂ = 0.49 (1) Å, ϕ₂ = -130 (3)°, in (II), corresponding to C33—C34—O35—H32—N32 sequence.

The P atom has a slightly distorted tetrahedral geometry towards trigonal pyramidal with an elongated C3—P2 apical bond.

Bond distances and angles in both molecules are in a good agreement with expected values (Allen et al., 1987). The ORTEP drawings of molecules (I) and (II) with the atomic numbering scheme are given in Figs. 1–2

Related literature

For related literature, see: Allen et al. (1987); Budzisz & Pastuszko (1999); Budzisz et al. (2001); Cremer & Pople (1975); Hudson & Pianka (1996); Kalir & Kalir (1996); Kukhar & Hudson (1999); Nardelli (1983); Preussman et al. (1969).

S2. Experimental

To the mixture of the compounds 2-methyl-4-oxo-4H-chromen-3-yl-phosphonate (for I) or 2,6-dimethyl-4-oxo-4H-chromen-3-yl-phosphonate (for II) in methanol was added ethanylamine in methanol. The mixture was left overnight at room temperature. The solvent was removed in vacuo and crude products of (I), and (II) were purified by crystallization. The colourless crystals were obtained by slow evaporation from methanol at room temperature (Budzisz & Pastuszko, 1999; Budzisz et al., 2001). The reaction was carried out at room temperature in anhydrous methanol.

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (1989b); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEX (Mc Ardle, 1995) for (I); ORTEX (McArdle, 1995) for (II). For both compounds, software used to prepare material for publication: PARST97 (Nardelli, 1996).

Figures

	Fig. 1. The perspective view of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Symmetry codes are as given in Table 2.
	Fig. 2. The perspective view of (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Symmetry codes are as given in Table 4.

(I) 2-methoxy-3-[1(2-hydroxyethylamine)ethylidene]-2,3-dihydro-2,4-dioxo- 2λ⁵-benzo[e][1,2]oxaphosphinane

Crystal data

C13H16NO5P	Dx = 1.403 Mg m^−3
Mr = 297.24	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 9.325 (1) Å	θ = 26.9–30.5°
b = 9.662 (1) Å	µ = 1.92 mm^−1
c = 15.619 (2) Å	T = 293 K
V = 1407.4 (1) Å^3	Prism, colourless
Z = 4	0.2 × 0.1 × 0.1 mm
F(000) = 624

Data collection

AFC5S Rigaku diffractometer	1664 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 66.0°, θmin = 5.5°
ω scan	h = −11→11
Absorption correction: analytical (De Meulenar & Tompa, 1965)	k = −11→9
Tmin = 0.712, Tmax = 0.841	l = −18→18
8498 measured reflections	3 standard reflections every 150 min
2402 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.064	w = [1.00000exp(3.00(sinθ/λ)^2)]/ [σ^2(Fo^2) + (0.1052P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.157	(Δ/σ)max = 0.051
S = 1.23	Δρmax = 0.42 e Å^−3
2402 reflections	Δρmin = −0.62 e Å^−3
224 parameters	Absolute structure: (Flack, 1983)
0 restraints	Absolute structure parameter: 0.00 (5)
Primary atom site location: structure-invariant direct methods

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. All H-atoms from methyl groups constrained to their parent atoms as a rigid body SHELXL97 (Sheldrick, 1997). U(H231)=1.1 U_eqof its parent atom. U(H232)=1.1 U_eqof its parent atom. U(H233)=1.1 U_eqof its parent atom. U(H342)=1.1 U_eqof its parent atom. U(H5)=1.1 U_eqof its parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0085 (4)	0.6457 (3)	0.47913 (18)	0.0567 (8)
P2	0.99166 (15)	0.52449 (13)	0.41005 (7)	0.0513 (3)
O21	0.9628 (5)	0.3971 (4)	0.4561 (2)	0.0714 (11)
O22	1.1366 (4)	0.5232 (5)	0.3601 (2)	0.0696 (11)
C23	1.2650 (7)	0.4675 (9)	0.4012 (5)	0.101 (2)
H231	1.3069	0.5371	0.4372	0.111*
H232	1.3329	0.4404	0.3581	0.111*
H233	1.2396	0.3885	0.4352	0.111*
C3	0.8643 (5)	0.5872 (5)	0.3370 (3)	0.0480 (10)
C4	0.8479 (5)	0.7341 (5)	0.3302 (3)	0.0493 (11)
O4	0.7573 (4)	0.7897 (4)	0.2813 (2)	0.0639 (10)
C5	0.9452 (5)	0.9682 (6)	0.3623 (3)	0.0533 (12)
H5	0.890 (6)	0.993 (6)	0.324 (3)	0.059*
C6	1.0258 (6)	1.0587 (6)	0.4111 (4)	0.0665 (14)
H6	1.025 (6)	1.154 (6)	0.402 (4)	0.066 (16)*
C7	1.0992 (6)	1.0096 (6)	0.4823 (4)	0.0682 (16)
H7	1.154 (6)	1.067 (5)	0.509 (3)	0.055 (14)*
C8	1.0935 (6)	0.8733 (6)	0.5026 (4)	0.0619 (13)
H8	1.155 (7)	0.814 (7)	0.555 (4)	0.09 (2)*
C9	1.0141 (5)	0.7822 (5)	0.4541 (3)	0.0522 (11)
C10	0.9371 (5)	0.8295 (5)	0.3819 (3)	0.0454 (10)
C31	0.7798 (5)	0.4932 (5)	0.2876 (3)	0.0508 (11)
C311	0.8019 (6)	0.3403 (6)	0.2894 (4)	0.0624 (13)
H311	0.8980	0.3204	0.3077	0.057 (15)*
H312	0.7869	0.3032	0.2331	0.12 (3)*
H313	0.7351	0.2991	0.3285	0.11 (2)*
N32	0.6769 (4)	0.5415 (5)	0.2383 (3)	0.0568 (11)
H32	0.679 (6)	0.642 (7)	0.235 (4)	0.068 (17)*
C33	0.5784 (6)	0.4641 (7)	0.1846 (4)	0.0642 (14)
H331	0.541 (7)	0.374 (7)	0.214 (4)	0.10 (2)*
H332	0.640 (5)	0.445 (5)	0.139 (3)	0.043 (12)*
C34	0.4537 (6)	0.5512 (6)	0.1608 (4)	0.0617 (14)
H341	0.384 (5)	0.495 (5)	0.118 (3)	0.047 (12)*
H342	0.394 (6)	0.571 (5)	0.207 (3)	0.052*
O35	0.4923 (5)	0.6801 (4)	0.1261 (3)	0.0689 (10)
H35	0.541 (7)	0.665 (7)	0.095 (4)	0.07 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.067 (2)	0.0493 (19)	0.0534 (14)	0.0048 (19)	−0.0097 (18)	−0.0007 (13)
P2	0.0526 (7)	0.0488 (6)	0.0523 (5)	0.0043 (6)	−0.0049 (6)	−0.0009 (5)
O21	0.087 (3)	0.054 (2)	0.073 (2)	0.0046 (19)	−0.021 (2)	−0.0007 (17)
O22	0.057 (2)	0.093 (3)	0.0588 (18)	0.014 (2)	−0.0113 (16)	−0.0076 (19)
C23	0.059 (4)	0.153 (7)	0.090 (4)	0.031 (4)	−0.018 (4)	−0.013 (5)
C3	0.041 (2)	0.053 (3)	0.050 (2)	−0.0034 (19)	0.005 (2)	−0.004 (2)
C4	0.038 (2)	0.064 (3)	0.046 (2)	0.000 (2)	0.0026 (19)	−0.001 (2)
O4	0.064 (2)	0.057 (2)	0.070 (2)	0.0018 (18)	−0.0280 (19)	0.0023 (18)
C5	0.038 (2)	0.060 (3)	0.062 (2)	0.002 (2)	−0.007 (2)	−0.002 (2)
C6	0.058 (3)	0.054 (4)	0.087 (3)	−0.005 (2)	−0.004 (3)	−0.004 (3)
C7	0.059 (3)	0.060 (4)	0.086 (3)	−0.003 (3)	−0.022 (3)	−0.020 (3)
C8	0.055 (3)	0.062 (4)	0.069 (3)	−0.003 (2)	−0.016 (3)	−0.010 (3)
C9	0.040 (2)	0.057 (3)	0.059 (2)	0.007 (2)	0.000 (2)	−0.010 (2)
C10	0.035 (2)	0.047 (3)	0.054 (2)	0.0024 (18)	−0.0015 (18)	−0.0028 (19)
C31	0.039 (2)	0.065 (3)	0.049 (2)	−0.003 (2)	0.0044 (18)	0.002 (2)
C311	0.063 (3)	0.057 (4)	0.067 (3)	−0.002 (3)	−0.003 (3)	−0.002 (3)
N32	0.050 (2)	0.061 (3)	0.059 (2)	−0.002 (2)	−0.0097 (18)	−0.0032 (19)
C33	0.049 (3)	0.078 (4)	0.066 (3)	−0.005 (3)	−0.010 (2)	−0.010 (3)
C34	0.049 (3)	0.075 (4)	0.061 (3)	−0.003 (2)	−0.002 (2)	−0.006 (3)
O35	0.071 (3)	0.068 (3)	0.067 (2)	0.001 (2)	−0.005 (2)	−0.0045 (18)

Geometric parameters (Å, º)

O1—C9	1.377 (6)	C7—H7	0.87 (6)
O1—P2	1.600 (3)	C8—C9	1.377 (7)
P2—O21	1.451 (4)	C8—H8	1.16 (7)
P2—O22	1.561 (4)	C9—C10	1.413 (6)
P2—C3	1.754 (5)	C31—N32	1.316 (6)
O22—C23	1.461 (6)	C31—C311	1.492 (8)
C23—H231	0.9600	C311—H311	0.9600
C23—H232	0.9600	C311—H312	0.9600
C23—H233	0.9600	C311—H313	0.9600
C3—C31	1.428 (6)	N32—C33	1.451 (6)
C3—C4	1.432 (7)	N32—H32	0.97 (6)
C4—O4	1.259 (6)	C33—C34	1.483 (8)
C4—C10	1.482 (6)	C33—H331	1.05 (7)
C5—C10	1.377 (7)	C33—H332	0.94 (5)
C5—C6	1.382 (8)	C34—O35	1.405 (7)
C5—H5	0.82 (6)	C34—H341	1.09 (5)
C6—C7	1.389 (8)	C34—H342	0.93 (5)
C6—H6	0.93 (6)	O35—H35	0.68 (6)
C7—C8	1.356 (9)
C9—O1—P2	120.9 (3)	O1—C9—C8	118.5 (5)
O21—P2—O22	113.7 (2)	O1—C9—C10	121.1 (4)
O21—P2—O1	107.7 (2)	C8—C9—C10	120.4 (5)
O22—P2—O1	104.9 (2)	C5—C10—C9	117.7 (4)
O21—P2—C3	119.3 (2)	C5—C10—C4	121.0 (4)
O22—P2—C3	105.3 (2)	C9—C10—C4	121.3 (4)
O1—P2—C3	104.6 (2)	N32—C31—C3	119.6 (5)
C23—O22—P2	119.6 (4)	N32—C31—C311	117.5 (5)
O22—C23—H231	109.5	C3—C31—C311	122.9 (4)
O22—C23—H232	109.5	C31—C311—H311	109.5
H231—C23—H232	109.5	C31—C311—H312	109.5
O22—C23—H233	109.5	H311—C311—H312	109.5
H231—C23—H233	109.5	C31—C311—H313	109.5
H232—C23—H233	109.5	H311—C311—H313	109.5
C31—C3—C4	122.0 (4)	H312—C311—H313	109.5
C31—C3—P2	120.4 (4)	C31—N32—C33	128.1 (5)
C4—C3—P2	117.6 (3)	C31—N32—H32	112 (3)
O4—C4—C3	122.7 (4)	C33—N32—H32	120 (3)
O4—C4—C10	116.2 (4)	N32—C33—C34	110.4 (5)
C3—C4—C10	121.0 (4)	N32—C33—H331	113 (4)
C10—C5—C6	121.5 (5)	C34—C33—H331	109 (4)
C10—C5—H5	114 (4)	N32—C33—H332	99 (3)
C6—C5—H5	124 (4)	C34—C33—H332	113 (3)
C5—C6—C7	119.6 (6)	H331—C33—H332	113 (5)
C5—C6—H6	123 (3)	O35—C34—C33	113.5 (5)
C7—C6—H6	117 (3)	O35—C34—H341	111 (2)
C8—C7—C6	120.0 (5)	C33—C34—H341	110 (2)
C8—C7—H7	122 (3)	O35—C34—H342	106 (3)
C6—C7—H7	117 (3)	C33—C34—H342	113 (3)
C7—C8—C9	120.9 (5)	H341—C34—H342	103 (4)
C7—C8—H8	129 (3)	C34—O35—H35	105 (6)
C9—C8—H8	110 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N32—H32···O4	0.97 (6)	1.76 (6)	2.601 (6)	143 (5)
N32—H32···O35	0.97 (6)	2.46 (6)	2.797 (6)	100 (4)
O35—H35···O21^i	0.68 (6)	2.25 (7)	2.790 (6)	137 (7)

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

(II) 6-methyl-2-methoxy-3-[1(2-hydroxyethylamine)ethylidene]-2,3-dihydro-2,4-dioxo- 2λ⁵-benzo[e][1,2]oxaphosphinane

Crystal data

C14H18NO5P	Dx = 1.359 Mg m^−3
Mr = 311.26	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 11.071 (1) Å	θ = 22.5–28.3°
b = 16.190 (2) Å	µ = 1.80 mm^−1
c = 8.490 (1) Å	T = 293 K
V = 1521.7 (3) Å^3	Prism, colourless
Z = 4	0.6 × 0.3 × 0.3 mm
F(000) = 656

Data collection

AFC5S Rigaku diffractometer	1450 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 72.7°, θmin = 4.8°
ω scan	h = 0→13
Absorption correction: analytical (De Meulenar & Tompa, 1965)	k = 0→20
Tmin = 0.505, Tmax = 0.650	l = 0→10
1669 measured reflections	3 standard reflections every 150 min
1669 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0636P)^2] where P = (Fo^2 + 2Fc^2)/3'
R[F^2 > 2σ(F^2)] = 0.034	(Δ/σ)max = 0.021
wR(F^2) = 0.097	Δρmax = 0.17 e Å^−3
S = 1.02	Δρmin = −0.20 e Å^−3
1669 reflections	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
230 parameters	Extinction coefficient: 0.0055 (6)
0 restraints	Absolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (4)
Hydrogen site location: difference Fourier map

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. All H-atoms from methyl groups constrained to their parent atoms as a rigid body SHELXL97 (Sheldrick, 1997). U(H311)=1.1 U_eqof its parent atom. U(H312)=1.1 U_eqof its parent atom. U(H313)=1.1 U_eqof its parent atom. U(H231)=1.1 U_eqof its parent atom. U(H232)=1.1 U_eqof its parent atom. U(H233)=1.1 U_eqof its parent atom. U(H611)=1.1 U_eqof its parent atom. U(H612)=1.1 U_eqof its parent atom. U(H613)=1.1 U_eqof its parent atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.62126 (16)	0.46337 (11)	1.0008 (3)	0.0520 (5)
P2	0.51983 (7)	0.39481 (5)	0.97479 (10)	0.0496 (2)
O21	0.40728 (19)	0.43808 (15)	0.9387 (4)	0.0696 (8)
O22	0.5176 (2)	0.34439 (13)	1.1327 (3)	0.0683 (7)
C23	0.4646 (5)	0.3834 (3)	1.2733 (5)	0.1046 (18)
H231	0.4729	0.4423	1.2656	0.115*
H233	0.5059	0.3641	1.3656	0.115*
H232	0.3806	0.3693	1.2802	0.115*
C3	0.5806 (2)	0.32639 (18)	0.8363 (4)	0.0459 (7)
C4	0.7098 (3)	0.32009 (18)	0.8266 (4)	0.0460 (7)
O4	0.76227 (18)	0.27093 (14)	0.7355 (3)	0.0573 (6)
C5	0.9122 (3)	0.35940 (19)	0.9342 (4)	0.0464 (7)
H5	0.937 (3)	0.3134 (19)	0.877 (4)	0.049 (9)*
C6	0.9894 (3)	0.41038 (18)	1.0159 (4)	0.0503 (7)
C61	1.1241 (3)	0.3948 (2)	1.0197 (5)	0.0661 (9)
H611	1.1401	0.3388	0.9891	0.073*
H612	1.1539	0.4040	1.1245	0.073*
H613	1.1638	0.4318	0.9481	0.073*
C7	0.9408 (3)	0.4789 (2)	1.0915 (5)	0.0595 (9)
H7	0.993 (3)	0.511 (2)	1.153 (5)	0.069 (11)*
C8	0.8188 (3)	0.4952 (2)	1.0885 (5)	0.0590 (8)
H8	0.777 (4)	0.546 (2)	1.151 (5)	0.086 (13)*
C9	0.7432 (3)	0.44233 (18)	1.0058 (4)	0.0482 (7)
C10	0.7872 (2)	0.37416 (16)	0.9268 (4)	0.0431 (6)
C31	0.5046 (3)	0.27695 (18)	0.7406 (4)	0.0478 (7)
C311	0.3694 (3)	0.2804 (2)	0.7469 (5)	0.0629 (9)
H311	0.3371	0.2259	0.7325	0.069*
H312	0.3402	0.3159	0.6648	0.069*
H313	0.3444	0.3016	0.8473	0.069*
N32	0.5524 (2)	0.22382 (17)	0.6404 (3)	0.0519 (7)
H32	0.647 (4)	0.219 (3)	0.645 (6)	0.112 (16)*
C33	0.4895 (3)	0.1648 (2)	0.5389 (4)	0.0564 (8)
H331	0.419 (4)	0.192 (2)	0.482 (5)	0.090 (13)*
H332	0.451 (3)	0.119 (2)	0.594 (5)	0.071 (11)*
C34	0.5788 (3)	0.1299 (2)	0.4234 (5)	0.0604 (9)
H341	0.532 (3)	0.0879 (19)	0.359 (4)	0.057 (10)*
H342	0.605 (4)	0.185 (3)	0.351 (6)	0.109 (15)*
O35	0.6800 (2)	0.09472 (16)	0.4971 (4)	0.0692 (7)
H35	0.667 (5)	0.040 (3)	0.528 (6)	0.124 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0425 (10)	0.0429 (9)	0.0707 (15)	0.0015 (8)	0.0043 (11)	−0.0085 (11)
P2	0.0417 (3)	0.0473 (4)	0.0598 (5)	0.0003 (3)	0.0053 (4)	−0.0028 (4)
O21	0.0401 (10)	0.0679 (13)	0.101 (2)	0.0111 (11)	0.0009 (12)	−0.0173 (14)
O22	0.0927 (18)	0.0556 (12)	0.0566 (14)	−0.0094 (14)	0.0192 (14)	−0.0025 (11)
C23	0.160 (5)	0.088 (3)	0.065 (3)	−0.029 (3)	0.048 (3)	−0.017 (2)
C3	0.0372 (14)	0.0451 (14)	0.0553 (19)	0.0001 (12)	0.0002 (13)	0.0016 (14)
C4	0.0414 (14)	0.0430 (14)	0.0536 (17)	−0.0007 (11)	0.0000 (13)	−0.0012 (14)
O4	0.0423 (11)	0.0611 (13)	0.0684 (14)	0.0006 (10)	0.0023 (11)	−0.0193 (12)
C5	0.0423 (15)	0.0479 (15)	0.0491 (19)	−0.0016 (12)	0.0008 (13)	0.0020 (13)
C6	0.0428 (14)	0.0606 (16)	0.0476 (17)	−0.0081 (13)	−0.0010 (13)	0.0000 (15)
C61	0.0422 (15)	0.086 (2)	0.070 (2)	−0.0077 (17)	−0.0034 (16)	−0.001 (2)
C7	0.0540 (17)	0.066 (2)	0.059 (2)	−0.0140 (16)	−0.0024 (17)	−0.0097 (18)
C8	0.0562 (18)	0.0601 (18)	0.061 (2)	−0.0083 (15)	0.0024 (16)	−0.0126 (18)
C9	0.0417 (13)	0.0468 (13)	0.0559 (18)	−0.0003 (12)	0.0025 (14)	−0.0035 (15)
C10	0.0395 (13)	0.0423 (14)	0.0474 (16)	−0.0006 (11)	0.0005 (12)	−0.0016 (12)
C31	0.0405 (14)	0.0495 (14)	0.0534 (16)	−0.0017 (12)	−0.0028 (13)	0.0037 (14)
C311	0.0426 (16)	0.068 (2)	0.078 (3)	0.0022 (15)	−0.0065 (17)	−0.0070 (19)
N32	0.0439 (13)	0.0566 (14)	0.0550 (16)	−0.0046 (11)	−0.0041 (12)	−0.0111 (13)
C33	0.0525 (17)	0.0578 (16)	0.059 (2)	−0.0111 (16)	−0.0061 (17)	−0.0067 (16)
C34	0.066 (2)	0.0612 (19)	0.054 (2)	−0.0095 (18)	−0.0049 (17)	−0.0082 (17)
O35	0.0575 (13)	0.0641 (14)	0.0861 (18)	−0.0039 (12)	−0.0028 (13)	−0.0074 (16)

Geometric parameters (Å, º)

O1—C9	1.393 (3)	C61—H613	0.9600
O1—P2	1.594 (2)	C7—C8	1.376 (5)
P2—O21	1.462 (2)	C7—H7	0.94 (4)
P2—O22	1.570 (2)	C8—C9	1.388 (4)
P2—C3	1.750 (3)	C8—H8	1.09 (4)
O22—C23	1.472 (4)	C9—C10	1.380 (4)
C23—H231	0.9600	C31—N32	1.320 (4)
C23—H233	0.9600	C31—C311	1.499 (4)
C23—H232	0.9600	C311—H311	0.9600
C3—C31	1.418 (4)	C311—H312	0.9600
C3—C4	1.436 (4)	C311—H313	0.9600
C4—O4	1.253 (3)	N32—C33	1.463 (4)
C4—C10	1.492 (4)	N32—H32	1.05 (5)
C5—C6	1.375 (4)	C33—C34	1.502 (5)
C5—C10	1.406 (4)	C33—H331	1.02 (4)
C5—H5	0.93 (3)	C33—H332	0.98 (4)
C6—C7	1.390 (5)	C34—O35	1.404 (4)
C6—C61	1.513 (4)	C34—H341	1.01 (3)
C61—H611	0.9600	C34—H342	1.12 (5)
C61—H612	0.9600	O35—H35	0.94 (5)
C9—O1—P2	121.11 (17)	C7—C8—C9	118.9 (3)
O21—P2—O22	114.48 (16)	C7—C8—H8	124 (2)
O21—P2—O1	107.20 (12)	C9—C8—H8	117 (2)
O22—P2—O1	104.79 (13)	C10—C9—C8	121.8 (3)
O21—P2—C3	119.37 (16)	C10—C9—O1	121.5 (3)
O22—P2—C3	104.52 (14)	C8—C9—O1	116.7 (3)
O1—P2—C3	105.23 (12)	C9—C10—C5	117.5 (3)
C23—O22—P2	118.4 (2)	C9—C10—C4	123.0 (2)
O22—C23—H231	109.5	C5—C10—C4	119.4 (3)
O22—C23—H233	109.5	N32—C31—C3	120.0 (3)
H231—C23—H233	109.5	N32—C31—C311	116.6 (3)
O22—C23—H232	109.5	C3—C31—C311	123.5 (3)
H231—C23—H232	109.5	C31—C311—H311	109.5
H233—C23—H232	109.5	C31—C311—H312	109.5
C31—C3—C4	121.2 (3)	H311—C311—H312	109.5
C31—C3—P2	120.9 (2)	C31—C311—H313	109.5
C4—C3—P2	117.8 (2)	H311—C311—H313	109.5
O4—C4—C3	122.9 (3)	H312—C311—H313	109.5
O4—C4—C10	117.3 (2)	C31—N32—C33	127.9 (3)
C3—C4—C10	119.8 (3)	C31—N32—H32	115 (3)
C6—C5—C10	122.1 (3)	C33—N32—H32	116 (3)
C6—C5—H5	124 (2)	N32—C33—C34	108.5 (3)
C10—C5—H5	114 (2)	N32—C33—H331	111 (2)
C5—C6—C7	118.1 (3)	C34—C33—H331	111 (2)
C5—C6—C61	121.5 (3)	N32—C33—H332	115 (2)
C7—C6—C61	120.3 (3)	C34—C33—H332	108 (2)
C6—C61—H611	109.5	H331—C33—H332	103 (3)
C6—C61—H612	109.5	O35—C34—C33	112.8 (3)
H611—C61—H612	109.5	O35—C34—H341	112 (2)
C6—C61—H613	109.5	C33—C34—H341	106 (2)
H611—C61—H613	109.5	O35—C34—H342	111 (3)
H612—C61—H613	109.5	C33—C34—H342	103 (2)
C8—C7—C6	121.6 (3)	H341—C34—H342	111 (3)
C8—C7—H7	120 (2)	C34—O35—H35	113 (3)
C6—C7—H7	118 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N32—H32···O4	1.05 (5)	1.71 (5)	2.575 (3)	136 (4)
N32—H32···O35	1.05 (5)	2.39 (5)	2.801 (4)	102 (4)
O35—H35···O21^i	0.94 (5)	1.87 (5)	2.768 (4)	162 (5)

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