NMR analysis of a series of 1,2-bis­(1-R-5-oxo-2,3-di­hydro-1H-pyrrol-4-yl­idene)ethanes and X-ray crystal structure analysis of the R = mesityl compound

Four tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­[1-R-5-oxo-4,5-di­hydro-1H-pyrrole-2,3-di­carboxyl­ate] compounds, denoted class (1), are a series of conjugated buta-1,3-dienes substituted with a heterocyclic group. The compounds can be used as dyes and pigments due to their long-range conjugated systems. Four structures were studied using ¹H NMR, ¹³C NMR and mass spectroscopy, viz. with R = 2,4,6-tri­methyl­phenyl, (1a), R = cyclo­hexyl, (1b), R = tert-butyl, (1c), and R = isopropyl, (1d). A detailed discussion is presented regarding the characteristics of the three-dimensional structures based on NMR analysis and the X-ray crystal structure of (1a), namely tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­[5-oxo-1-(2,4,6-tri­methyl­phen­yl)-4,5-di­hydro-1H-pyr­role-2,3-di­carboxyl­ate], C₃₆H₃₆N₂O₁₀. The conjugation plane and stability were also studied via quantum chemical calculations.

S1. Introduction

Conjugated dienes are a useful and fundamental structural motif found in a wide range of organic materials and biologically active molecules (Erb & Zhu, 2013; Biermann et al., 2011). Molecules containing diene groups are typically versatile rea­cta­nts in numerous reactions, such as Diels–Alder and cyclo­addition reactions (Dzhemilev et al., 2009; Welker, 2008; Yang et al., 2013; Bouillon et al., 2012). Similar heterocyclic substituted conjugated dienes have been prepared and can be used as dyes and pigments because of their long-range conjugation (Adam et al., 2004). However, the relatively complex synthetic routes and unknown structural details for these compounds have limited their application. To provide a new synthetic route to heterocyclic substituted conjugated dienes and to elucidate their structural properties, a new series of heterocyclic substituted 1,2-bis­(1-R-5-oxo-2,3-di­hydro-1H-pyrrol-4-yl­idene)ethanes, denoted class (1), was synthesized, and the compound with R = mesityl, namely tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­(5-oxo-1-mesityl-4,5-di­hydro-1H-pyrrole-2,3-di­carboxyl­ate), (1a), was taken as a representative example and subjected to full structural studies.

The four examples of class (1) reported here, i.e. compound (1a) and the analogues with mesityl replaced by cyclo­hexyl, (1b), tert-butyl, (1c), and iso­propyl, (1d), are conjugated buta-1,3-dienes containing two 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene groups. The compounds were prepared by reaction of the appropriate amine, glyoxal and di­methyl acetyl­enedi­carboxyl­ate (see Scheme 1). NMR analysis was used to characterize the structural changes of the four compounds of class (1) caused by conjugation. In terms of the three-dimensional structure, the X-ray crystal structure of one of the compounds, (1a), was solved to determine its stereoisomer and explain the conjugation of buta-1,3-dienes and 4,5-di­hydro-1H-pyrrol-4-yl, which has a planar backbone. The frontier molecular orbitals (FMOs) were used to investigate the conjugation plane of the four compounds, and the stability was determined from geometry optimizations using quantum chemical calculations.

S2. Experimental

S2.1. Physical measurements

The chemicals used in this work were purchased from commercial sources and used without further purification. The melting points were determined using an X-5 apparatus (open capillaries, uncorrected values). All of the NMR spectra were recorded on a Bruker AV400 spectrometer at 400 MHz for the ¹H NMR and 100 MHz for the ¹³C NMR at ambient temperature (298 K). Mass spectra were recorded on a Bruker Esquire 6000 mass spectrometer.

S2.2. General synthesis of 1,2-bis­(1-R-5-oxo-2,3-di­hydro-1H-pyrrol-4-yl­idene)ethanes, (1)

A mixture of the appropriate amine (57 mmol), glyoxal (86 mmol), di­methyl acetyl­enedi­carboxyl­ate (57 mmol) and γ-cyclo­dextrin (3 mmol) was stirred in water at room temperature. After approximately 2 h, followed by thin-layer chromatography, the aqueous mixture was extracted with ethyl acetate (3 × 50 ml), and the combined organic layers were dried with Na₂SO₄. After evaporation of the solvent, the residue was purified by flash chromatography using acetone–petroleum ether (1:8 v/v). Vials containing the pure product were combined and concentrated in vacuo. The red solids were collected and dried to obtain the pure product.

S2.2.1. Data for tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­(5-oxo-1-mesityl-4,5-di­hydro-1H-pyrrole-2,3-di­carboxyl­ate), (1a)

Compound (1a) was obtained in 40.2% yield (m.p. 560–562 K). ¹H NMR (400 MHz, CDCl₃): δ 2.17 (s, 12H, –CH₃), 2.31 (s, 6H, –CH₃), 3.70 (s, 6H, –OCH₃), 3.85 (s, 6H, –OCH₃), 6.94 (s, 4H, Ar–H), 9.36 (s, 2H, –CH). ¹³C NMR (100 MHz, CDCl₃): δ 17.7, 20.1, 52.0, 53.1, 105.9, 128.7, 129.2, 130.5, 135.9, 137.1, 139.7, 147.1, 161.3, 162.2, 164.8. HRMS (ESI+) m/z: calculated 656.2370 for C₃₆H₃₆N₂O₁₀ [M+H]⁺; found 657.2400.

S2.2.2. Data for tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­(1-cyclo­hexyl-5-oxo-4,5-di­hydro-1H-pyrrole-2,3-di­carboxyl­ate), (1b)

Compound (1b) was obtained in 35.8% yield (m.p. 511–512 K). ¹H NMR (400 MHz, CDCl₃): δ 1.15–1.96 (m, 20H, -CH₂), 3.77–3.83 (m, 2H, –CH), 3.86 (s, 6H, –OCH₃), 4.00 (s, 6H, –OCH₂), 9.25 (s, 2H, –CH). ¹³C NMR (100 MHz, CDCl₃): δ 25.0, 26.1, 30.6, 52.0, 53.4, 55.3, 104.8, 131.0, 135.2, 146.8, 162.2, 162.8, 165.6. HRMS (ESI+) m/z: calculated 584.2370 for C₃₀H₃₆N₂O₁₀ [M+H]⁺; found 585.2402.

S2.2.3. Data for tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­(1-tert-butyl-5-oxo-4,5-di­hydro-1H-pyrrole-2,3-di­carboxyl­ate), (1c)

Compound (1c) was obtained in 36.0% yield (m.p. 508–509 K). ¹H NMR (400 MHz, CDCl₃): δ 1.58 (s, 18H, –CH₃), 3.86 (s, 6H, –OCH₃), 3.96 (s, 6H, –OCH₃), 9.20 (s, 2H, –CH). ¹³C NMR (100 MHz, CDCl₃): δ 28.5, 51.9, 53.3, 59.7, 105.3, 130.6, 134.7, 147.5, 162.5, 164.2, 166.8. HRMS (ESI+) m/z: calculated 532.2057 for C₂₆H₃₂N₂O₁₀ [M+H]⁺; found 533.2072.

S2.2.4. Data for tetra­methyl 4,4'-(ethane-1,2-diyl­idene)bis­(1-iso­propyl-5-oxo-4,5-di­hydro-1H-pyrrole-2,3-di­carboxyl­ate), (1d)

Compound (1d) was obtained in 42.1% yield (m.p. 436–439 K). ¹H NMR (400 MHz, CDCl₃): δ 1.41 (d, J = 7.2 Hz, 12H, –CH₃), 3.85 (s, 6H, –OCH₃), 3.98 (s, 6H, –OCH₃), 4.22 (m, J = 6.8 Hz, 2H, –CH), 9.23 (s, 2H, –CH). ¹³C NMR (100 MHz, CDCl₃): δ 20.5, 47.2, 51.9, 53.4, 104.8, 135.1, 146.5, 162.2, 162.7, 165.5. HRMS (ESI+) m/z calculated 504.1744 for C₂₄H₂₈N₂O₁₀ [M+H]⁺; found 505.1740.

S2.3. X-ray crystallography

Crystal data, data collection and structure refinement details are summarized in Table 1. All of the H atoms were fixed in positions of ideal geometry and refined isotropically based on the corresponding C atoms [U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms].

S2.4. Computational details

The optimized molecular structure and FMOs of (1a)–(1d) have been calculated using the DFT/B3LYP method with the 6-31G(d) basis set. All of the quantum-chemical calculations were carried out using the GAUSSIAN03 program (Frisch et al., 2004) and the Gauss View molecular visualization program. The initial coordinates of (1a), which were obtained from the X-ray diffraction experiment, were fully optimized using density functional theory (Kohn & Sham, 1965) with the hybrid Becke–Lee–Yang–Parr exchange-correlation functional (B3LYP) (Dobson et al., 1998) and the 6-31G(d) basis set for all of the atoms.

S3. Results and discussion

The four 1,2-bis­(1-R-5-oxo-2,3-di­hydro-1H-pyrrol-4-yl­idene)ethanes (1a)–(1d) were prepared by reaction of the appropriate amines, glyoxal and di­methyl acetyl­enedi­carboxyl­ate in water and accelerated by γ-cyclo­dextrin, which acted as a phase transfer catalyst (Bricout et al., 2009). These compounds were obtained as a red solid with a yield of approximately 40%. The structures were confirmed by ¹H NMR, ¹³C NMR, MS and X-ray diffraction. Compound (1a) will be used as a representative example for discussing the details of the structures of (1a)–(1d).

S3.1. NMR spectroscopy analysis

In the ¹H NMR spectrum of (1a), there are six signals. The methyl groups are observed at 2.17 and 2.31 p.p.m., the meth­oxy groups at 3.70 and 3.85 p.p.m., the tri­methyl­phenyl groups at 6.94 p.p.m., and the H atom of the vinylic group at 9.36 p.p.m. The o-methyl group is located in the magnetic shielding area of the carbonyl group and is in a position of relatively higher magnetic field compared to the p-methyl group. The chemical shift difference of the two meth­oxy groups is primarily due to the configuration and the substituent effect on the chemical environment. In the NOE (nuclear Overhauser effect) spectrum, the meth­oxy peak (at 3.70 p.p.m.) has a positive NOESY (nuclear Overhauser effect spectroscopy) cross peak to the H atom of the methyl groups (at 2.17 p.p.m.). This indicates that there are shorter distances between the H atoms of the meth­oxy group and the o-methyl groups. The H atom on the vinylic group at 9.36 p.p.m., which was shifted downfield, may be due to the geometry configuration of the buta-1,3-diene group and its chemical environment.

In the ¹³C NMR spectra of (1a), 15 signals are observed. The signals for the carbonyl C atoms are observed at 162.5, 164.2 and 166.8 p.p.m., and the signals for the phenyl and vinylic C atoms in the range 105.6–147.0 p.p.m. The vinylic C-atom signal appears at 105.6 p.p.m. and this signal is largely shielded compared to the other unsaturated C atoms. In the HSQC (heteronuclear single quantum coherence) spectrum, the signals appear at 52.0 and 53.1 p.p.m., corresponding to the meth­oxy groups correlated to the proton signals at 3.85 and 3.70 p.p.m., which confirms that these carbon signals belong to the two meth­oxy groups. In addition, the methyl-group signal at 21.1 p.p.m. is inter­acting with the proton signals at 2.31 p.p.m., and the carbon signal at 17.7 p.p.m. is inter­acting with the 2.17 p.p.m. proton signals, meaning that the C atoms at 17.7 and 21.1 p.p.m. are the two methyl groups on benzene. In the HMBC (heteronuclear multiple-bond correlation) spectrum, the signals at 162.5 and 164.2 p.p.m. belong to the carbonyl group of two ester groups through the C—H long-range correlation between the proton and carbonyl, and the signals at 9.36 p.p.m. coupling with three signals at 105.9 p.p.m. belong to the vinylic C atom of the 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene group. In addition, the signals at 135.9 p.p.m. belong to the vinylic C atom of the buta-1,3-diene group, and the signals at 166.8 p.p.m. belong to the carbonyl group.

To determine the structures of (1b) (R = cyclo­hexyl), (1c) (R = tert-butyl) and (1d) (R = iso­propyl), the ¹H and ¹³C NMR spectra are shown in Tables 2 and 3. The ¹H NMR spectra of compounds (1b), (1c) and (1d) indicate that there are three types of H atom in common with (1a) due to the ethyl ester moiety and the proton located on the olefin C atom. The chemical shifts and splitting mode are very similar, which confirms that the remaining H atoms are the same except for the substituted groups on the N atom of the 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene moiety. The ¹³C NMR spectrum of compounds (1b), (1c) and (1d) exhibited nine common resonance lines corresponding to OCH₃, C═O and C═C (Table 3). A comparison of the ¹H and ¹³C NMR spectra indicate that the main carbon skeleton of compounds (1b), (1c) and (1d) is the same as that of (1a).

S3.2. Crystal structure analysis

To confirm the Z/E isomers of the buta-1,3-diene group, single crystals were grown for X-ray analysis by slow evaporation from di­chloro­methane and cyclo­hexane, and single-crystal diffraction analysis was performed to unambiguously establish the molecular structure (Fig. 2). The molecule of compound (1a) is the 1Z,3Z geometric isomer with the middle bond of the buta-1,3-diene entity lying on a crystallographic centre of inversion and a planar backbone. The 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene moiety is essentially coplanar with the buta-1,3-diene group (Fig. 3a). This is a consequence of the extended electron delocalization from each five-membered ring through the buta-1,3-diene group, as indicated by the bond lengths given in Table 4. The planes of the mesityl rings are nearly perpendicular to that of the buta-1,3-diene group which reduces the steric hindrance between the mesityl methyl groups and the substituents on the five-membered ring (Fig. 3b). The two ester groups on the 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene group also exhibit two different orientations with respect to the pyrrolyl­idene ring so as to lower the energy of the molecule; that at atom C11 is almost coplanar with the ring and therefore can conjugate with the ring, while that at atom C10 is nearly perpendicular to the pyrrolyl­idene ring so as to relieve steric repulsion between the mesityl methyl groups (C7 and C9) and the adjacent ester group O atoms (Fig. 4). The H atom in the buta-1,3-diene group is polarized by the adjacent ester O atom, O4, due to the short H···O distance of 2.36 Å, which shifts the vinylic proton downfield in the ¹H NMR spectrum (9.36 p.p.m.). The structure of (1a) has weak dipole–dipole inter­actions between the H atoms in the mesityl C7 and C9 methyl groups with atoms O2 and O1, respectively, of the ester group at C10 (H···O = 2.87 and 2.83 Å, respectively). The results were confirmed by the NOESY NMR spectrum, and the meth­oxy signal (3.70 p.p.m.) is correlated with the H atom of the methyl signal.

In the crystal, molecules of (1a) are stacked along the crystallographic a axis via weak C—H···π inter­actions involving the C9 mesityl methyl group and the buta-1,3-diene group of a neighbouring molecule (Fig. 5a). The projection of the layers on the crystallographic bc plane indicates that this arrangement is further stabilized by a weak C—H···O contact between carbonyl atom O5 and atom H3 of the mesityl ring of an adjacent centrosymmetrically-related molecule (H···O = 2.63 Å; Fig. 5b and Table 5), which then by extension through the symmetry relationships leads to ribbons of molecules running parallel to the [101] direction. A further inter­molecular C—H···O inter­action involves the para-methyl group of mesityl unit C8 and carbonyl atom O3 of the ester group at C11 of an adjacent molecule. This inter­action links the molecules into sheets which lie parallel to (102). This sheet is reinforced by another weak inter­molecular C—H···O inter­action involving the ester methyl group at C17 and ester carbonyl atom O1 (Table 5).

S3.3. Computational analysis

To further study the conjugation planes and the stability of the four compounds of class (1), the initial coordinates of (1a), which were obtained via X-ray diffraction experiments, were fully optimized using density functional theory (DFT) with the hybrid Becke–Lee–Yang–Parr exchange-correlation functional (B3LYP) and the 6-31G(d) basis set for all of the atoms. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) were calculated using the DFT/B3LYP method.

The optimized bond distances and angles were in very good agreement with the X-ray diffraction results (Fig. 6). The molecule exists a nearly planar conformation, which can be explained when the shapes of the HOMO and LUMO are considered (Fig. 7). The moieties of (1a) form a conjugated system because the electron density of both the HOMO and LUMO are localized on the buta-1,3-diene, 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene and ester groups. The FMOs of (1b), (1c) and (1d) are very similar to those of (1a) and have a conjugated plane.

The stability of (1) can be determined by the hardness value (η) calculated from the HOMO–LUMO energy gap, which indicates whether the molecular is relatively stable or unstable. The hardness value (η) of a molecule can be determined by the formula:

η = (-ε_HOMO + ε_LUMO)/2

where ε_HOMO and ε_LUMO are the energies of the HOMO and LUMO molecular orbitals. The value of η for (1a), (1b), (1c) and (1d) are 1.252, 1.208, 1.213 and 1.210 eV, respectively. Therefore, compounds (1) are stable, and (1a) is more stable than the other three compounds.

S4. Conclusions

The structures of four buta-1,4-dienes, or 1,2-bis­(1-R-5-oxo-2,3-di­hydro-1H-pyrrol-4-yl­idene)ethanes, were characterized by ¹H NMR, ¹³C NMR and MS. The NMR explained the connecting modes and spin-coupling effects between the atoms caused by the stereoisomer. The single-crystal X-ray diffraction results indicated that (1a) exists in a conjugated plane with a 1E,3E geometry. In addition, (1a) forms a compact and ordered structure due to the planarity of its backbone and the steric hindrance of its substituent groups. The quantum chemical calculations revealed that class (1) is stabilized by the π-conjugation system between the buta-1,3-diene, 5-oxo-4,5-di­hydro-1H-pyrrol-4-yl­idene and ester groups.

Related literature

For related literature, see: Adam et al. (2004); Biermann et al. (2011); Bouillon et al. (2012); Bricout et al. (2009); Dobson et al. (1998); Dzhemilev et al. (2009); Erb & Zhu (2013); Frisch et al. (2004); Kohn & Sham (1965); Welker (2008); Yang et al. (2013).

Computing details

Data collection: CrystalClear (Rigaku, 2013); cell refinement: CrystalClear (Rigaku, 2013); data reduction: CrystalClear (Rigaku, 2013); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. NOESY (nuclear Overhauser effect spectroscopy) spectrum of (1a).
	Fig. 2. Single-crystal X-ray structure of (1a). Displacement ellipsoids are drawn at the ??% probability level.
	Fig. 3. Torsion angles between the 5-oxo-4,5-dihydro-1H-pyrrol-4-ylidene group and (a) the buta-1,3-diene or (b) the mesityl group.
	Fig. 4. Torsion angles between the methoxycarbonyl group and the 5-oxo-4,5-dihydro-1H-pyrrol-4-ylidene group, showing (a) the N1—C10—C14—O2 torsion angle and (b) the C11—C10—C14—O2 torsion angle.
	Fig. 5. Packing of the (1a) molecules in the unit cell, showing (a) C—H···π interactions along the a axis and (b) a projection on the bc plane of the molecule of (1a).
	Fig. 6. (a) The optimized bond distances (Å) and (b) optimized bond angles (°) in (1a).
	Fig. 7. (a) The HOMO (highest occupied molecular orbital) and (b) the LUMO (lowest unoccupied molecular orbital) of (1a).

Tetramethyl 4,4'-(ethane-1,2-diylidene)bis[5-oxo-1-(2,4,6-trimethylphenyl)-4,5-dihydro-1H-pyrrole-2,3-dicarboxylate]

Crystal data

C36H36N2O10	F(000) = 692
Mr = 656.67	Dx = 1.265 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.4573 (17) Å	Cell parameters from 3848 reflections
b = 19.181 (4) Å	θ = 2.1–27.9°
c = 10.936 (2) Å	µ = 0.09 mm^−1
β = 103.74 (3)°	T = 293 K
V = 1723.3 (6) Å^3	Prism, colourless
Z = 2	0.18 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn 70 CCD diffractometer	2339 reflections with I > 2σ(I)
Detector resolution: 7.31 pixels mm^-1	Rint = 0.048
ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2013)	h = −10→10
Tmin = 0.783, Tmax = 1.000	k = −23→23
15252 measured reflections	l = −13→12
3376 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.068	w = 1/[σ^2(Fo^2) + (0.117P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.198	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.30 e Å^−3
3376 reflections	Δρmin = −0.24 e Å^−3
223 parameters	Extinction correction: SHELXL2013 (Sheldrick, 2013), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.035 (7)

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.

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

	x	y	z	Uiso*/Ueq
N1	0.3756 (2)	0.40142 (8)	0.21264 (16)	0.0496 (5)
O1	0.4903 (2)	0.25116 (9)	0.15631 (17)	0.0724 (6)
O2	0.3284 (2)	0.24035 (9)	0.29003 (17)	0.0734 (6)
O3	0.0977 (2)	0.23459 (8)	0.02489 (17)	0.0784 (6)
O4	−0.0493 (2)	0.31772 (9)	−0.09074 (19)	0.0950 (8)
O5	0.3207 (2)	0.51858 (7)	0.17683 (15)	0.0628 (5)
C1	0.5194 (3)	0.40672 (10)	0.31378 (19)	0.0456 (5)
C2	0.5018 (3)	0.40498 (10)	0.4364 (2)	0.0477 (5)
C3	0.6427 (3)	0.40839 (11)	0.5322 (2)	0.0544 (6)
H3	0.6339	0.4072	0.6153	0.065*
C4	0.7959 (3)	0.41354 (11)	0.5081 (2)	0.0565 (6)
C5	0.8064 (3)	0.41580 (12)	0.3842 (2)	0.0606 (6)
H5	0.9086	0.4193	0.3670	0.073*
C6	0.6702 (3)	0.41303 (11)	0.2841 (2)	0.0547 (6)
C7	0.3383 (3)	0.40062 (13)	0.4662 (2)	0.0648 (7)
H7A	0.2636	0.4309	0.4108	0.097*
H7B	0.3474	0.4147	0.5518	0.097*
H7C	0.2992	0.3535	0.4551	0.097*
C8	0.9464 (3)	0.41689 (15)	0.6131 (2)	0.0788 (9)
H8A	1.0203	0.4505	0.5929	0.118*
H8B	0.9976	0.3719	0.6241	0.118*
H8C	0.9175	0.4304	0.6895	0.118*
C9	0.6859 (4)	0.41629 (18)	0.1501 (2)	0.0884 (9)
H9A	0.7949	0.4296	0.1487	0.133*
H9B	0.6107	0.4500	0.1044	0.133*
H9C	0.6622	0.3713	0.1115	0.133*
C10	0.3009 (3)	0.33985 (10)	0.16504 (19)	0.0470 (5)
C11	0.1610 (3)	0.35221 (10)	0.07672 (19)	0.0487 (6)
C12	0.1374 (2)	0.42707 (10)	0.06727 (18)	0.0455 (5)
C13	0.2820 (3)	0.45818 (10)	0.1554 (2)	0.0484 (5)
C14	0.3846 (3)	0.27156 (11)	0.2021 (2)	0.0527 (6)
C15	0.3969 (5)	0.17247 (15)	0.3300 (3)	0.1035 (12)
H15A	0.4579	0.1561	0.2721	0.155*
H15B	0.3106	0.1402	0.3318	0.155*
H15C	0.4675	0.1761	0.4126	0.155*
C16	0.0680 (3)	0.29476 (11)	0.0051 (2)	0.0589 (7)
C17	−0.1398 (5)	0.26387 (17)	−0.1710 (4)	0.141 (2)
H17A	−0.0652	0.2317	−0.1943	0.211*
H17B	−0.2063	0.2848	−0.2454	0.211*
H17C	−0.2079	0.2395	−0.1264	0.211*
C18	0.0083 (3)	0.46328 (10)	−0.00094 (18)	0.0464 (5)
H18	−0.0752	0.4380	−0.0527	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0496 (11)	0.0438 (10)	0.0507 (10)	0.0025 (7)	0.0024 (8)	0.0017 (7)
O1	0.0647 (12)	0.0653 (11)	0.0886 (13)	0.0195 (8)	0.0208 (10)	0.0102 (9)
O2	0.0997 (15)	0.0564 (10)	0.0692 (11)	0.0217 (9)	0.0303 (10)	0.0193 (8)
O3	0.0788 (13)	0.0397 (9)	0.1023 (14)	0.0034 (8)	−0.0071 (11)	0.0018 (8)
O4	0.0837 (14)	0.0496 (10)	0.1172 (16)	−0.0068 (9)	−0.0448 (12)	0.0044 (9)
O5	0.0700 (11)	0.0409 (9)	0.0683 (11)	−0.0014 (7)	−0.0020 (8)	−0.0018 (7)
C1	0.0455 (12)	0.0409 (11)	0.0472 (12)	0.0005 (8)	0.0044 (10)	0.0023 (8)
C2	0.0497 (13)	0.0396 (11)	0.0525 (12)	0.0016 (8)	0.0096 (10)	0.0019 (9)
C3	0.0608 (15)	0.0500 (12)	0.0495 (13)	0.0009 (10)	0.0075 (11)	0.0012 (9)
C4	0.0547 (14)	0.0460 (12)	0.0620 (15)	0.0010 (9)	0.0004 (12)	−0.0063 (10)
C5	0.0465 (14)	0.0595 (14)	0.0750 (17)	−0.0051 (10)	0.0130 (12)	−0.0064 (12)
C6	0.0529 (14)	0.0558 (13)	0.0563 (14)	−0.0031 (10)	0.0147 (11)	−0.0003 (10)
C7	0.0589 (15)	0.0704 (16)	0.0686 (16)	0.0011 (11)	0.0218 (13)	0.0012 (12)
C8	0.0657 (18)	0.0754 (18)	0.0804 (19)	−0.0022 (13)	−0.0121 (15)	−0.0081 (14)
C9	0.078 (2)	0.127 (3)	0.0671 (18)	−0.0113 (17)	0.0305 (15)	0.0010 (15)
C10	0.0490 (13)	0.0421 (11)	0.0488 (12)	0.0021 (9)	0.0094 (10)	0.0034 (9)
C11	0.0461 (12)	0.0401 (11)	0.0565 (13)	0.0036 (8)	0.0054 (10)	0.0026 (9)
C12	0.0449 (12)	0.0403 (11)	0.0498 (12)	0.0028 (8)	0.0082 (9)	0.0036 (9)
C13	0.0520 (13)	0.0416 (11)	0.0503 (12)	0.0048 (9)	0.0094 (10)	0.0035 (9)
C14	0.0522 (14)	0.0478 (12)	0.0529 (13)	0.0048 (10)	0.0018 (11)	0.0013 (10)
C15	0.159 (3)	0.0629 (18)	0.096 (2)	0.0368 (19)	0.045 (2)	0.0384 (16)
C16	0.0503 (13)	0.0420 (12)	0.0769 (16)	0.0015 (10)	0.0003 (12)	0.0037 (11)
C17	0.133 (3)	0.071 (2)	0.160 (4)	−0.0229 (19)	−0.080 (3)	−0.008 (2)
C18	0.0451 (12)	0.0443 (11)	0.0481 (11)	0.0028 (8)	0.0079 (9)	0.0048 (9)

Geometric parameters (Å, º)

N1—C10	1.382 (3)	C7—H7B	0.9600
N1—C13	1.403 (2)	C7—H7C	0.9600
N1—C1	1.440 (3)	C8—H8A	0.9600
O1—C14	1.190 (3)	C8—H8B	0.9600
O2—C14	1.314 (3)	C8—H8C	0.9600
O2—C15	1.449 (3)	C9—H9A	0.9600
O3—C16	1.190 (3)	C9—H9B	0.9600
O4—C16	1.335 (3)	C9—H9C	0.9600
O4—C17	1.451 (3)	C10—C11	1.359 (3)
O5—C13	1.212 (2)	C10—C14	1.498 (3)
C1—C2	1.384 (3)	C11—C12	1.450 (3)
C1—C6	1.394 (3)	C11—C16	1.468 (3)
C2—C3	1.389 (3)	C12—C18	1.358 (3)
C2—C7	1.496 (3)	C12—C13	1.490 (3)
C3—C4	1.386 (3)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.379 (3)	C15—H15C	0.9600
C4—C8	1.500 (3)	C17—H17A	0.9600
C5—C6	1.389 (3)	C17—H17B	0.9600
C5—H5	0.9300	C17—H17C	0.9600
C6—C9	1.505 (3)	C18—C18^i	1.416 (4)
C7—H7A	0.9600	C18—H18	0.9300
C10—N1—C13	109.63 (17)	H9A—C9—H9B	109.5
C10—N1—C1	125.24 (16)	C6—C9—H9C	109.5
C13—N1—C1	124.90 (17)	H9A—C9—H9C	109.5
C14—O2—C15	116.3 (2)	H9B—C9—H9C	109.5
C16—O4—C17	115.3 (2)	C11—C10—N1	111.20 (17)
C2—C1—C6	122.8 (2)	C11—C10—C14	128.35 (18)
C2—C1—N1	118.5 (2)	N1—C10—C14	120.07 (18)
C6—C1—N1	118.67 (19)	C10—C11—C12	107.79 (17)
C1—C2—C3	117.4 (2)	C10—C11—C16	120.95 (19)
C1—C2—C7	122.0 (2)	C12—C11—C16	131.16 (18)
C3—C2—C7	120.6 (2)	C18—C12—C11	128.67 (19)
C4—C3—C2	122.2 (2)	C18—C12—C13	125.43 (18)
C4—C3—H3	118.9	C11—C12—C13	105.81 (16)
C2—C3—H3	118.9	O5—C13—N1	123.9 (2)
C5—C4—C3	118.1 (2)	O5—C13—C12	130.59 (19)
C5—C4—C8	120.7 (2)	N1—C13—C12	105.51 (16)
C3—C4—C8	121.3 (2)	O1—C14—O2	126.6 (2)
C4—C5—C6	122.6 (2)	O1—C14—C10	121.8 (2)
C4—C5—H5	118.7	O2—C14—C10	111.5 (2)
C6—C5—H5	118.7	O2—C15—H15A	109.5
C5—C6—C1	117.0 (2)	O2—C15—H15B	109.5
C5—C6—C9	121.2 (2)	H15A—C15—H15B	109.5
C1—C6—C9	121.9 (2)	O2—C15—H15C	109.5
C2—C7—H7A	109.5	H15A—C15—H15C	109.5
C2—C7—H7B	109.5	H15B—C15—H15C	109.5
H7A—C7—H7B	109.5	O3—C16—O4	123.2 (2)
C2—C7—H7C	109.5	O3—C16—C11	124.6 (2)
H7A—C7—H7C	109.5	O4—C16—C11	112.05 (18)
H7B—C7—H7C	109.5	O4—C17—H17A	109.5
C4—C8—H8A	109.5	O4—C17—H17B	109.5
C4—C8—H8B	109.5	H17A—C17—H17B	109.5
H8A—C8—H8B	109.5	O4—C17—H17C	109.5
C4—C8—H8C	109.5	H17A—C17—H17C	109.5
H8A—C8—H8C	109.5	H17B—C17—H17C	109.5
H8B—C8—H8C	109.5	C12—C18—C18^i	124.8 (2)
C6—C9—H9A	109.5	C12—C18—H18	117.6
C6—C9—H9B	109.5	C18^i—C18—H18	117.6
C10—N1—C1—C2	−84.0 (3)	C14—C10—C11—C16	1.8 (4)
C13—N1—C1—C2	89.9 (2)	C10—C11—C12—C18	−174.2 (2)
C10—N1—C1—C6	95.7 (3)	C16—C11—C12—C18	9.6 (4)
C13—N1—C1—C6	−90.4 (3)	C10—C11—C12—C13	2.4 (2)
C6—C1—C2—C3	−1.3 (3)	C16—C11—C12—C13	−173.7 (2)
N1—C1—C2—C3	178.40 (18)	C10—N1—C13—O5	−178.0 (2)
C6—C1—C2—C7	177.9 (2)	C1—N1—C13—O5	7.3 (4)
N1—C1—C2—C7	−2.5 (3)	C10—N1—C13—C12	0.9 (2)
C1—C2—C3—C4	0.2 (3)	C1—N1—C13—C12	−173.78 (19)
C7—C2—C3—C4	−179.0 (2)	C18—C12—C13—O5	−6.4 (4)
C2—C3—C4—C5	0.5 (3)	C11—C12—C13—O5	176.8 (2)
C2—C3—C4—C8	−179.8 (2)	C18—C12—C13—N1	174.8 (2)
C3—C4—C5—C6	−0.1 (3)	C11—C12—C13—N1	−2.0 (2)
C8—C4—C5—C6	−179.8 (2)	C15—O2—C14—O1	−3.6 (4)
C4—C5—C6—C1	−0.9 (3)	C15—O2—C14—C10	177.9 (2)
C4—C5—C6—C9	179.4 (2)	C11—C10—C14—O1	93.9 (3)
C2—C1—C6—C5	1.6 (3)	N1—C10—C14—O1	−78.5 (3)
N1—C1—C6—C5	−178.03 (19)	C11—C10—C14—O2	−87.5 (3)
C2—C1—C6—C9	−178.7 (2)	N1—C10—C14—O2	100.2 (2)
N1—C1—C6—C9	1.6 (3)	C17—O4—C16—O3	−0.1 (4)
C13—N1—C10—C11	0.6 (3)	C17—O4—C16—C11	176.1 (3)
C1—N1—C10—C11	175.31 (19)	C10—C11—C16—O3	6.6 (4)
C13—N1—C10—C14	174.22 (19)	C12—C11—C16—O3	−177.6 (2)
C1—N1—C10—C14	−11.1 (3)	C10—C11—C16—O4	−169.5 (2)
N1—C10—C11—C12	−2.0 (3)	C12—C11—C16—O4	6.2 (4)
C14—C10—C11—C12	−174.9 (2)	C11—C12—C18—C18^i	176.3 (3)
N1—C10—C11—C16	174.7 (2)	C13—C12—C18—C18^i	0.2 (4)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5^ii	0.93	2.63	3.423 (3)	143
C8—H8B···O3^iii	0.96	2.55	3.405 (3)	148
C17—H17B···O1^iv	0.96	2.63	3.260 (5)	124

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