Crystal structure of (2E)-1-(4-hy­droxy-1-methyl-2-oxo-1,2-di­hydro­quinolin-3-yl)-3-(4-hy­droxy-3-meth­oxy­phen­yl)prop-2-en-1-one

Mangwala Kimpende, P.; Nguyen, N.T.; Nguyen, M.T.; Vu, Q.T.; Van Meervelt, L.

doi:10.1107/S2056989015005630

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ISSN: 2056-9890

Volume 71| Part 4| April 2015| Pages 424-426

doi:10.1107/S2056989015005630

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Crystal structure of (2E)-1-(4-hydroxy-1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)-3-(4-hydroxy-3-methoxyphenyl)prop-2-en-1-one

Peter Mangwala Kimpende,^a Ngoc Thanh Nguyen,^b Minh Thao Nguyen,^c Quoc Trung Vu ^d and Luc Van Meervelt ^e ^*

^aChemistry Department, University of Kinshasa, Kinshasa XI BP 190, Democratic Republic of Congo, ^bFaculty of Chemical Technology, Hanoi University of Industry, Minh Khai Commune – Tu Liem District, Hanoi, Vietnam, ^cFaculty of Chemistry, Hanoi University of Science, 334 - Nguyen Trai – Thanh Xuan District, Hanoi, Vietnam, ^dChemistry Department, Hanoi National University of Education, 136 - Xuan Thuy – Cau Giay, Hanoi, Vietnam, and ^eChemistry Department, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven (Heverlee), Belgium
^*Correspondence e-mail: luc.vanmeervelt@chem.kuleuven.be

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 14 March 2015; accepted 18 March 2015; online 28 March 2015)

In the title compound, C₂₀H₁₇NO₅, the dihedral angle between the mean plane of the dihydroquinoline ring system (r.m.s. deviation = 0.003 Å) and the benzene ring is 1.83 (11)°. The almost planar conformation is a consequence of an intramolecular O—H⋯O hydrogen bond and the E configuration about the central C=C bond. In the crystal structure, O—H⋯O hydrogen bonds generate chains of molecules along the [10-1] direction. These chains are linked via π–π interactions [inter-centroid distances are in the range 3.6410 (16)–3.8663 (17) Å].

Keywords: crystal structure; 4-hydroxy-1,2-dihydroquinolin-2(1H)-one; α,β-unsaturated ketones; hydrogen bonding; π–π interactions.

CCDC reference: 1054894

1. Chemical context

The quinoline ring is an important component of bioactive heterocycles because of its diversity (Larsen et al., 1996 ; Chen et al., 2001 ; Roma et al., 2000 ; Dubé et al., 1998 ; Billker et al., 1998 ). Many derivatives containing 4-hydroxy-1,2-dihydroquinolin-2(1H)-one have wide applications in pharmaceuticals, such as anticancer (Hasegawa et al., 1990 ), anti-inflammatory (Ukrainets et al., 1996 ) and antiseizure (Rowley et al., 1993 ). Some α,β-unsaturated ketones are known to have antimalarial, antibacterial and antifungal properties (Katritzky & Rees, 1984 ). The anticancer ability of some α,β-unsaturated ketones containing a quinoline ring has also been reported (Rezig et al., 2000 ; Nguyen, 2007 ). A number of the α,β-unsaturated ketones containing quinoline synthesized by the Claisen–Schmidt reaction have been reported to inhibit antimalarial activity (Domínguez et al., 2001 ). Moussaoui et al. (2002 ) also described the synthesis of α,β-unsaturated ketones containing a quinoline ring and claimed cytotoxicity with human leukemia cells. Here we present the synthesis and crystal structure of an α,β-unsaturated ketone derived from 3-acetyl-4-hydroxy-N-methylquinolin-2(1H)-one and 4-hydroxy-3-methoxybenzaldehyde.

2. Structural Commentary

The molecular structure of the title compound is illustrated in Fig. 1. The whole molecule is almost planar with a maximum deviation from the best plane through all atoms of 0.147 (3) Å for atom C20. The dihydroquinoline and benzene rings make a dihedral angle of 1.83 (11)° between the best planes. The configuration of the C12=C13 bond is E, with a C9—C11—C12—C13 torsion angle of 177.0 (2)°. In addition, intramolecular O2—H2⋯O3 and C12—H12⋯O1 hydrogen bonds assure the observed planarity of the structure (Table 1). Three short intramolecular contacts are observed: H10B⋯O1 (2.18 Å), H5A⋯O4 (2.25 Å) and H13⋯O3 (2.37 Å).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.84	1.65	2.407 (3)	148
O5—H5A⋯O1ⁱ	0.84	2.05	2.730 (3)	137
C12—H12⋯O1	0.98	2.18	2.822 (3)	124
C10—H10C⋯O3ⁱⁱ	0.98	2.56	3.523 (3)	167
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z+1.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines (see Table 1

for details).

3. Supramolecular features

In the crystal, molecules are connected via O5—H5A⋯O1 hydrogen bonds, forming chains propagating along [10 $[\overline{1}]$ ] (Fig. 2 and Table 1). These chains are linked by π–π interactions involving both ring systems (Fig. 3) and C—H⋯O interactions (Table 1). The inter-centroid distances are 3.6410 (16) and 3.8663 (17) Å for π–π interactions involving Cg1⋯Cg2^iv and Cg3⋯Cg2^v, respectively, where Cg1, Cg2 and Cg3 are the centroids of the N1/C1–C2/C7–C9, C2–C7 and C14–C19 rings, respectively [symmetry codes: (iv) −x + 1, −y, −z + 2; (v) −x + 2, −y, −z + 2].

Figure 2
Infinite chains in the [10 $[\overline{1}]$ ] direction formed by O5—H5A⋯O1 hydrogen bonds (shown as red dashed lines). [Symmetry codes: (i) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iii) x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ .]

Figure 3
π–π interactions in the crystal of the title compound shown as green dashed lines. [Symmetry codes: (iv) −x + 1, −y, −z + 2; (v) −x + 2, −y, −z + 2.]

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; last update November 2014; Groom & Allen, 2014 ) for α,β-unsaturated ketones C—CH=CH—C(=O)—O gave 1281 hits of which the majority adopts an E configuration (C—C=C—C torsion angle around 180°) as in the title compound. For only 19 entries this torsion angle is centered around 0°. A search for 1,2-dihydroquinoline derivatives gave 706 hits of which none contains an α,β-unsaturated ketone at the 3-position. The angle between the best planes through the two six-membered rings in these 1,2-dihydroquinoline derivatives is in the range of 0–22.13°. In the title compound, this angle is 1.49 (12)°.

5. Synthesis and crystallization

The precursors 4-hydroxy-6-methyl-2H-pyrano[3,2-c]quinoline-2,5(6H)-dione and 3-acetyl-4-hydroxy-N-methylquinolin-2(1H)-one were prepared in high yield (87.0 and 92.5%, respectively) according to Kappe et al. (1994 ).

The title compound was synthesized by refluxing a solution of 2.17 g (0.01 mol) of 3-acetyl-4-hydroxy-N-methylquinolin-2(1H)-one, 1.52 g (0.01 mol) of 4-hydroxy-3-methoxybenzaldehyde, 22 ml of chloroform and 5 drops of piperidine (as a catalyst) in a 100 ml flask for 30 h. The precipitate was filtered off and recrystallized from ethanol to obtain the title product as yellow crystals. The yield was 2.03 g (58%); m.p. 505–506 K, R_f 0.7 (CHCl₃–C₂H₅OH = 7:1 v/v).

IR (KBr, cm⁻¹): 3357, 3115 (ν_OH); 1637 (ν_C=O); 997 (ν_{CH= trans}). ¹H NMR (δ p.p.m.; DMSO-d₆, Bruker Avance 500 MHz): 8.47 (1H, d, ²J = 16.0 Hz, H_β), 7.92 (1H, d, ²J = 16.0 Hz, H_α), 3.59 (3H, s CH₃-N), 7.33 (1H, t, ³J = 8.0 Hz, C₆-H), 7.55 (1H, d, ³J = 8.0 Hz, C₅-H), 7.81 (1H, t, ³J = 8.0 Hz, C₇-H), 8.13 (1H, d, ³J = 8.0 Hz, C₈-H), 3.85 (3H, s, OCH₃), 6.89 (2H, d, ³J = 8.0 Hz, C₁₃-H), 7.27 (1H, d, ³J = 8.0 Hz, C₁₂-H), 7.30 (1H, s, C₉-H), 9.89 (1H, s, C₄-OH). Calculation for C₂₀H₁₇NO₅: M = 351 au. Found (by ESI MS, m/z): 351 (M⁺).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were refined using a riding model with stretchable C—H and O—H distances and with U_iso = 1.2U_eq(C) (1.5 times for methyl and hydroxyl groups).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₇NO₅
M_r	351.35
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.3634 (8), 22.664 (2), 8.8079 (9)
β (°)	95.413 (3)
V (Å³)	1662.1 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.84
Crystal size (mm)	0.58 × 0.22 × 0.04

Data collection
Diffractometer	Bruker SMART 6000
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.641, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	15707, 2881, 1889
R_int	0.086
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.156, 1.02
No. of reflections	2881
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.19
Computer programs: SMART and SAINT (Bruker, 2003), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1054894

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015005630/rz5152sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015005630/rz5152Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015005630/rz5152Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(2E)-1-(4-Hydroxy-1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)-3-(4-hydroxy-3-methoxyphenyl)prop-2-en-1-one top

Crystal data top

C₂₀H₁₇NO₅	Z = 4
M_r = 351.35	F(000) = 736
Monoclinic, P2₁/n	D_x = 1.404 Mg m⁻³
a = 8.3634 (8) Å	Cu Kα radiation, λ = 1.54178 Å
b = 22.664 (2) Å	µ = 0.84 mm⁻¹
c = 8.8079 (9) Å	T = 100 K
β = 95.413 (3)°	Block, yellow
V = 1662.1 (3) Å³	0.58 × 0.22 × 0.04 mm

Data collection top

Bruker SMART 6000 diffractometer	2881 independent reflections
Radiation source: fine-focus sealed tube	1889 reflections with I > 2σ(I)
Crossed Gοbel mirrors monochromator	R_int = 0.086
w\ and φ scans	θ_max = 66.6°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
T_min = 0.641, T_max = 0.967	k = −26→26
15707 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0641P)² + 0.0033P] where P = (F_o² + 2F_c²)/3
2881 reflections	(Δ/σ)_max < 0.001
239 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7024 (3)	−0.04442 (11)	0.9256 (3)	0.0415 (6)
N1	0.7229 (2)	0.02301 (9)	1.1896 (2)	0.0420 (5)
O1	0.8821 (2)	0.08925 (8)	1.0865 (2)	0.0512 (5)
C2	0.6258 (3)	−0.06452 (11)	1.0557 (3)	0.0413 (6)
O2	0.6850 (2)	−0.07762 (9)	0.8038 (2)	0.0583 (6)
H2	0.7380	−0.0633	0.7362	0.088*
C3	0.5393 (3)	−0.11726 (12)	1.0516 (4)	0.0523 (7)
H3	0.5284	−0.1402	0.9609	0.063*
O3	0.8460 (2)	−0.00808 (8)	0.6787 (2)	0.0546 (5)
C4	0.4692 (3)	−0.13626 (13)	1.1794 (4)	0.0587 (8)
H4	0.4108	−0.1723	1.1772	0.070*
O4	1.2629 (3)	0.28691 (9)	0.7891 (2)	0.0675 (6)
C5	0.4853 (3)	−0.10230 (14)	1.3095 (4)	0.0620 (8)
H5	0.4376	−0.1152	1.3973	0.074*
O5	1.3629 (3)	0.29415 (9)	0.5092 (3)	0.0723 (7)
H5A	1.3606	0.3205	0.5759	0.109*
C6	0.5689 (3)	−0.05015 (13)	1.3150 (3)	0.0540 (7)
H6	0.5789	−0.0277	1.4064	0.065*
C7	0.6394 (3)	−0.02989 (11)	1.1873 (3)	0.0421 (6)
C8	0.8029 (3)	0.04333 (11)	1.0694 (3)	0.0394 (6)
C9	0.7893 (3)	0.00803 (10)	0.9302 (3)	0.0370 (5)
C10	0.7290 (4)	0.06001 (14)	1.3261 (3)	0.0635 (8)
H10A	0.6203	0.0733	1.3420	0.095*
H10B	0.7974	0.0944	1.3128	0.095*
H10C	0.7732	0.0372	1.4148	0.095*
C11	0.8604 (3)	0.02611 (11)	0.7932 (3)	0.0418 (6)
C12	0.9447 (3)	0.08179 (11)	0.7778 (3)	0.0447 (6)
H12	0.9507	0.1094	0.8594	0.054*
C13	1.0134 (3)	0.09468 (11)	0.6516 (3)	0.0429 (6)
H13	1.0054	0.0654	0.5741	0.051*
C14	1.0990 (3)	0.14816 (11)	0.6180 (3)	0.0420 (6)
C15	1.1320 (3)	0.19255 (11)	0.7263 (3)	0.0447 (6)
H15	1.0944	0.1890	0.8244	0.054*
C16	1.2192 (3)	0.24159 (12)	0.6913 (3)	0.0480 (7)
C17	1.2722 (3)	0.24754 (12)	0.5466 (4)	0.0536 (7)
C18	1.2366 (4)	0.20473 (12)	0.4387 (4)	0.0584 (8)
H18	1.2714	0.2090	0.3396	0.070*
C19	1.1502 (3)	0.15542 (12)	0.4737 (3)	0.0524 (7)
H19	1.1256	0.1261	0.3981	0.063*
C20	1.2328 (4)	0.28030 (14)	0.9429 (4)	0.0699 (9)
H20A	1.1166	0.2782	0.9499	0.105*
H20B	1.2773	0.3141	1.0019	0.105*
H20C	1.2834	0.2439	0.9839	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0403 (13)	0.0349 (13)	0.0493 (15)	0.0023 (10)	0.0045 (11)	−0.0069 (11)
N1	0.0485 (11)	0.0400 (12)	0.0372 (12)	0.0021 (9)	0.0034 (10)	0.0010 (8)
O1	0.0626 (11)	0.0393 (11)	0.0518 (11)	−0.0104 (9)	0.0065 (9)	−0.0053 (8)
C2	0.0355 (12)	0.0364 (14)	0.0522 (16)	0.0059 (10)	0.0046 (11)	0.0078 (11)
O2	0.0723 (13)	0.0472 (12)	0.0584 (13)	−0.0144 (10)	0.0210 (10)	−0.0155 (9)
C3	0.0465 (15)	0.0426 (16)	0.0679 (19)	−0.0003 (12)	0.0057 (14)	0.0037 (13)
O3	0.0706 (12)	0.0439 (11)	0.0515 (11)	−0.0091 (9)	0.0171 (10)	−0.0107 (8)
C4	0.0519 (16)	0.0476 (17)	0.077 (2)	−0.0073 (13)	0.0092 (15)	0.0175 (15)
O4	0.0914 (15)	0.0506 (13)	0.0635 (14)	−0.0232 (11)	0.0223 (12)	−0.0085 (10)
C5	0.0574 (18)	0.066 (2)	0.064 (2)	−0.0045 (15)	0.0134 (16)	0.0199 (15)
O5	0.0931 (16)	0.0444 (13)	0.0869 (18)	−0.0117 (11)	0.0471 (14)	0.0035 (10)
C6	0.0532 (15)	0.0613 (19)	0.0482 (16)	0.0000 (13)	0.0084 (13)	0.0105 (13)
C7	0.0345 (12)	0.0436 (15)	0.0476 (15)	0.0056 (10)	0.0016 (11)	0.0069 (11)
C8	0.0368 (12)	0.0336 (13)	0.0475 (15)	0.0028 (10)	0.0024 (11)	0.0029 (10)
C9	0.0355 (12)	0.0315 (13)	0.0443 (14)	0.0040 (10)	0.0051 (11)	0.0013 (10)
C10	0.086 (2)	0.064 (2)	0.0411 (16)	−0.0142 (17)	0.0089 (16)	−0.0072 (13)
C11	0.0407 (13)	0.0374 (14)	0.0479 (15)	0.0050 (11)	0.0068 (12)	−0.0028 (11)
C12	0.0455 (14)	0.0382 (14)	0.0519 (16)	−0.0020 (11)	0.0126 (12)	−0.0035 (11)
C13	0.0425 (13)	0.0378 (14)	0.0486 (15)	0.0030 (11)	0.0056 (12)	−0.0025 (11)
C14	0.0386 (12)	0.0382 (14)	0.0506 (16)	0.0026 (10)	0.0108 (12)	0.0028 (11)
C15	0.0451 (14)	0.0435 (15)	0.0470 (15)	−0.0019 (11)	0.0120 (12)	−0.0001 (11)
C16	0.0495 (15)	0.0400 (15)	0.0564 (17)	0.0009 (11)	0.0141 (13)	−0.0009 (12)
C17	0.0584 (17)	0.0380 (15)	0.068 (2)	0.0030 (12)	0.0270 (15)	0.0101 (13)
C18	0.077 (2)	0.0479 (17)	0.0552 (18)	0.0014 (14)	0.0308 (16)	0.0037 (13)
C19	0.0632 (17)	0.0456 (17)	0.0508 (17)	0.0012 (13)	0.0185 (14)	−0.0033 (12)
C20	0.089 (2)	0.063 (2)	0.059 (2)	−0.0198 (18)	0.0139 (18)	−0.0138 (15)

Geometric parameters (Å, º) top

C1—C2	1.439 (4)	C8—C9	1.459 (3)
C1—O2	1.307 (3)	C9—C11	1.454 (3)
C1—C9	1.392 (3)	C10—H10A	0.9800
N1—C7	1.387 (3)	C10—H10B	0.9800
N1—C8	1.384 (3)	C10—H10C	0.9800
N1—C10	1.462 (3)	C11—C12	1.458 (3)
O1—C8	1.235 (3)	C12—H12	0.9500
C2—C3	1.396 (4)	C12—C13	1.331 (4)
C2—C7	1.395 (4)	C13—H13	0.9500
O2—H2	0.8400	C13—C14	1.452 (3)
C3—H3	0.9500	C14—C15	1.396 (4)
C3—C4	1.386 (4)	C14—C19	1.389 (4)
O3—C11	1.269 (3)	C15—H15	0.9500
C4—H4	0.9500	C15—C16	1.380 (4)
C4—C5	1.377 (4)	C16—C17	1.395 (4)
O4—C16	1.367 (3)	C17—C18	1.371 (4)
O4—C20	1.409 (4)	C18—H18	0.9500
C5—H5	0.9500	C18—C19	1.381 (4)
C5—C6	1.372 (4)	C19—H19	0.9500
O5—H5A	0.8400	C20—H20A	0.9800
O5—C17	1.359 (3)	C20—H20B	0.9800
C6—H6	0.9500	C20—H20C	0.9800
C6—C7	1.396 (4)

O2—C1—C2	116.6 (2)	H10A—C10—H10B	109.5
O2—C1—C9	122.2 (2)	H10A—C10—H10C	109.5
C9—C1—C2	121.2 (2)	H10B—C10—H10C	109.5
C7—N1—C10	119.1 (2)	O3—C11—C9	118.2 (2)
C8—N1—C7	123.7 (2)	O3—C11—C12	117.7 (2)
C8—N1—C10	117.2 (2)	C9—C11—C12	124.1 (2)
C3—C2—C1	121.3 (3)	C11—C12—H12	119.4
C7—C2—C1	118.4 (2)	C13—C12—C11	121.2 (2)
C7—C2—C3	120.3 (2)	C13—C12—H12	119.4
C1—O2—H2	109.5	C12—C13—H13	116.1
C2—C3—H3	119.9	C12—C13—C14	127.8 (2)
C4—C3—C2	120.2 (3)	C14—C13—H13	116.1
C4—C3—H3	119.9	C15—C14—C13	122.1 (2)
C3—C4—H4	120.4	C19—C14—C13	119.1 (2)
C5—C4—C3	119.1 (3)	C19—C14—C15	118.8 (2)
C5—C4—H4	120.4	C14—C15—H15	119.9
C16—O4—C20	117.7 (2)	C16—C15—C14	120.2 (3)
C4—C5—H5	119.3	C16—C15—H15	119.9
C6—C5—C4	121.4 (3)	O4—C16—C15	125.4 (3)
C6—C5—H5	119.3	O4—C16—C17	114.5 (2)
C17—O5—H5A	109.5	C15—C16—C17	120.1 (3)
C5—C6—H6	119.7	O5—C17—C16	122.0 (3)
C5—C6—C7	120.5 (3)	O5—C17—C18	118.1 (3)
C7—C6—H6	119.7	C18—C17—C16	119.9 (3)
N1—C7—C2	120.0 (2)	C17—C18—H18	120.0
N1—C7—C6	121.5 (3)	C17—C18—C19	120.1 (3)
C2—C7—C6	118.5 (3)	C19—C18—H18	120.0
N1—C8—C9	117.1 (2)	C14—C19—H19	119.6
O1—C8—N1	118.6 (2)	C18—C19—C14	120.9 (3)
O1—C8—C9	124.3 (2)	C18—C19—H19	119.6
C1—C9—C8	119.5 (2)	O4—C20—H20A	109.5
C1—C9—C11	118.0 (2)	O4—C20—H20B	109.5
C11—C9—C8	122.5 (2)	O4—C20—H20C	109.5
N1—C10—H10A	109.5	H20A—C20—H20B	109.5
N1—C10—H10B	109.5	H20A—C20—H20C	109.5
N1—C10—H10C	109.5	H20B—C20—H20C	109.5

C1—C2—C3—C4	178.7 (2)	C7—C2—C3—C4	−1.4 (4)
C1—C2—C7—N1	1.1 (3)	C8—N1—C7—C2	−3.3 (4)
C1—C2—C7—C6	−178.3 (2)	C8—N1—C7—C6	176.0 (2)
C1—C9—C11—O3	−3.2 (3)	C8—C9—C11—O3	178.2 (2)
C1—C9—C11—C12	175.5 (2)	C8—C9—C11—C12	−3.1 (4)
N1—C8—C9—C1	−1.9 (3)	C9—C1—C2—C3	−179.7 (2)
N1—C8—C9—C11	176.7 (2)	C9—C1—C2—C7	0.5 (3)
O1—C8—C9—C1	177.2 (2)	C9—C11—C12—C13	177.0 (2)
O1—C8—C9—C11	−4.2 (4)	C10—N1—C7—C2	177.0 (2)
C2—C1—C9—C8	−0.1 (3)	C10—N1—C7—C6	−3.7 (4)
C2—C1—C9—C11	−178.7 (2)	C10—N1—C8—O1	4.2 (3)
C2—C3—C4—C5	0.4 (4)	C10—N1—C8—C9	−176.6 (2)
O2—C1—C2—C3	0.8 (4)	C11—C12—C13—C14	179.0 (2)
O2—C1—C2—C7	−179.0 (2)	C12—C13—C14—C15	5.8 (4)
O2—C1—C9—C8	179.5 (2)	C12—C13—C14—C19	−174.4 (3)
O2—C1—C9—C11	0.8 (4)	C13—C14—C15—C16	177.5 (2)
C3—C2—C7—N1	−178.8 (2)	C13—C14—C19—C18	−177.9 (3)
C3—C2—C7—C6	1.9 (4)	C14—C15—C16—O4	−178.0 (2)
C3—C4—C5—C6	0.1 (5)	C14—C15—C16—C17	1.2 (4)
O3—C11—C12—C13	−4.3 (4)	C15—C14—C19—C18	2.0 (4)
C4—C5—C6—C7	0.4 (4)	C15—C16—C17—O5	−177.8 (3)
O4—C16—C17—O5	1.5 (4)	C15—C16—C17—C18	0.4 (4)
O4—C16—C17—C18	179.7 (3)	C16—C17—C18—C19	−0.9 (5)
C5—C6—C7—N1	179.3 (2)	C17—C18—C19—C14	−0.4 (5)
C5—C6—C7—C2	−1.4 (4)	C19—C14—C15—C16	−2.4 (4)
O5—C17—C18—C19	177.4 (3)	C20—O4—C16—C15	7.6 (4)
C7—N1—C8—O1	−175.6 (2)	C20—O4—C16—C17	−171.6 (3)
C7—N1—C8—C9	3.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.84	1.65	2.407 (3)	148
O5—H5A···O1ⁱ	0.84	2.05	2.730 (3)	137
C12—H12···O1	0.98	2.18	2.822 (3)	124
C10—H10C···O3ⁱⁱ	0.98	2.56	3.523 (3)	167

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

Acknowledgements

We thank VLIR–UOS and the Chemistry Department of KU Leuven for support of this work.

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