Synthesis and crystal structure of allyl 7-(di­ethyl­amino)-2-oxo-2H-chromene-3-carboxyl­ate

Nowatschin, V.; Näther, C.; Lüning, U.

doi:10.1107/S2056989021002218

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ISSN: 2056-9890

Volume 77| Part 4| April 2021| Pages 331-334

https://doi.org/10.1107/S2056989021002218

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Synthesis and crystal structure of allyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate

Vanessa Nowatschin,^a Christian Näther ^b and Ulrich Lüning ^a ^*

^aOtto-Diels-Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Otto-Hahn-Platz 4, D-24098 Kiel, Germany, and ^bInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth Str. 2, D-24118 Kiel, Germany
^*Correspondence e-mail: luening@oc.uni-kiel.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 18 February 2021; accepted 24 February 2021; online 2 March 2021)

The title compound, C₁₇H₁₉NO₄, was synthesized by the reaction of 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid with allyl bromide and purified by flash column chromatography on silica gel. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallization from acetone. The aromatic core of the molecule is not planar with the diethylamino group and with the carboxyl group that are rotated out of the 2-oxo-2H-chromene plane by 6.7 (2)° and 11.4 (2)°. The NC₂ unit of the diethylamino group is planar with an angle sum close to 360°. Intermolecular C_ar—H⋯O_carbonyl interactions lead to the formation of chains parallel to the b axis. X-ray powder diffraction analysis proves that the title compound was obtained as a pure phase.

Keywords: crystal structure; synthesis; 2-oxo-2H-chromene; C—H⋯O hydrogen bonding.

CCDC reference: 2064943

1. Chemical context

Coumarins or 2H-1-benzopyran-2-ones are fluorophores with a wide range of biological and chemical applications (Bardajee et al., 2006a ). One of the most important aspects is the detection of enzymatic activity from bacteria like Enterococci or Streptococci (Devriese et al., 1999 ). Within the enzymatic reaction, naturally occurring aesculin is hydrolysed with a concomitant loss of fluorescence (Edberg et al., 1976 ). In addition, (coumarin-4-yl)methyl esters are often used as a photocleavable protecting group that could be useful for proton detection in biological processes (Geissler et al., 2005 ). Another emerging field of application is photoelectricity such as in organic light-emitting diodes (OLEDs) or laser dyes (Bardajee et al., 2006a; Jones et al., 1985 ; Jones & Rahman, 1992 , 1994 ; Cui et al., 2018 ). In this context, Cui et al. (2018) developed two coumarines that show solid-state fluorescence influenced by NH₃ or HCl gas.

In a current research project, we planed to insert a coumarin moiety as part of a pH-sensitive polymer to visualize material damage. For this purpose, allyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate was synthesized from 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid and allyl bromide with potassium carbonate for deprotonation and dry N,N-dimethylformamide as solvent (Fig. 1). The obtained title compound was characterized by ¹H NMR (Fig. S1 in the supporting information) and ¹³C NMR (Fig. S2) spectroscopy, mass spectrometry, IR spectroscopy and elemental analysis. Recrystallization from acetone led to crystals that were characterized by single-crystal X-ray diffraction. Based on the results of the structure determination, a powder X-ray pattern was calculated and compared with the experimental pattern, revealing that the title compound was obtained as a pure phase (Fig. S3).

Figure 1
Synthesis of allyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate by esterification of 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid with allyl bromide.

2. Structural commentary

The molecular structure of the title compound, C₁₇H₁₉NO₄, consists of a central 2-oxo-2H-chromene (2-benzopyrane) unit with a carboxylic acid allyl ester in 3-position and a diethylamino group in 7-position. All atoms of the molecule are in general positions (Fig. 2). The 2H-chromene unit is essentially planar with a maximum deviation for O2 of 0.1021 (6) Å from the least-squares plane calculated through C1–C7 and O1 and O2. The carboxyl group (C10,O3,O4) is slightly twisted from the 2-oxo-2H-chromene unit, with the dihedral angle between the plane calculated through the ring system and that of the carboxyl group being 6.7 (2)° (Fig. 3). The NC₃ unit (N1,C7,C14,C16) of the diethylamino group is nearly planar with a maximum deviation of the N atom from the mean plane of 0.0873 Å; planarity is also obvious from the sum of the C—N—C angles of 358.9°. This unit is rotated from the 2-oxo-2H-chromene plane by 11.4 (2)° (Fig. 3), which points to conjugation between the ring system and the diethylamino group. The latter feature is also reflected by the C7—N1 bond length of 1.3597 (12)°.

Figure 2
Molecular structure of the title compound with atom labelling and displacement ellipsoids drawn at the 50% probability level.

Figure 3
The orientation of the substituents in the molecular structure of the title compound.

3. Supramolecular features

In the crystal structure of the title compound, the molecules are linked by intermolecular C—H⋯O hydrogen bonding between one of the aromatic hydrogen atoms of a 2-oxo-2H-chromene unit and a carbonyl oxygen atom of a neighbouring molecule into chains extending parallel to the crystallographic b axis (Fig. 4; Table 1). The C—H⋯O angle is close to linearity, indicating that this is a relatively strong interaction. The molecules are additionally stacked into columns that are directed along the crystallographic c axis but the mean planes of the 2H-chromene rings of neighbouring molecules are not parallel (Fig. 5). They are rotated by 33.2°, which prevents π–π interactions.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2ⁱ	0.95	2.45	3.3958 (12)	171
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 4
The formation of C—H⋯O hydrogen-bonded chains in the title compound in a view along the crystallographic c axis. Hydrogen bonds are shown as dashed lines.

Figure 5
Packing of molecules in the crystal structure of the title compound in a view along the crystallographic b axis. Intermolecular C—H⋯O hydrogen bonding is shown as dashed lines.

4. Database survey

A search in the Cambridge Structural Database (CSD Version 2021; Groom et al., 2016 ) revealed eight structures of 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate derivatives. Three of them relate to the crystal structures of the carboxylic acid, which crystallizes in two different polymorphs (Bardajee et al., 2006a; Cui et al., 2018; Zhang et al., 2008 ).

Five more crystal structures relate to esterificated coumarin derivatives. One of them is 3-carboxyethyl-7-diethylaminocoumarin (Li et al., 2009 ). Another one is succinimidyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate, which was obtained as a chloroform solvate (Bardajee et al., 2006b ). The hits also include 4-cyanobiphenyl-4-yl 7-diethylamino-2-oxo-2H-chromene-3-carboxylate (Sreenivasa et al., 2013 ). Furthermore, two bischromophoric acid derivatives are reported. The first one is (2R,3R)-diethyl tartrate-2,3-bis(7-diethylaminocoumarin-3-carboxylate) and the second is (2S,3R)-N,O-bis(7-diethylaminocoumarin-3-carbonyl)-threonine methyl ester (Lo et al., 2001 ).

5. Synthesis and crystallization

All reagents and solvents were commercially available and were used without further purification: allyl bromide (abcr), 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid (Fluorochem). For the reaction, flasks were flame-dried, evacuated and flooded with a stream of nitrogen. The NMR spectra were measured with a Bruker AvanceNeo 500 (¹H NMR: 500 MHz, ¹³C NMR: 125 MHz) in dimethylsulfoxide-d₆ (deutero) as solvent. TMS was used as reference. The melting point was measured with a Melting Point Apparatus from Electrothermal. The mass spectrum was measured in the positive mode with an AccuTOF GCV 4G (Jeol, EI, 70 eV). R_f values were determined by thin-layer chromatography using ALUGRAMM^® Xtra Sil G/UV₂₅₄ plates (Machery-Nagel). Flash column chromatography was performed using cartridge SNAP Ultra 25 g (Biotage^®) on a Isolera one (Biotage^®). Infrared spectroscopy was performed on a Perkin–Elmer 1600 series FTIR spectrometer. An AG531-G Golden-Gate-Diamond-ATR unit was used. The elemental analysis was performed with a vario MICRO CUBE (Elementar). The probe was put into a zinc container and was burned in an oxygen atmosphere.

Under nitrogen atmosphere, 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid (298 mg, 1.14 mmol) and potassium carbonate (324 mg, 2.34 mmol) were suspended in dry N,N-dimethylformamide (20 ml). Allyl bromide (320 µl, 3.70 mmol) was added and the solution was stirred for 21.5 h at room temperature. After addition of water (50 ml), the mixture was extracted with dichloromethane (4 × 20 ml). The combined organic layer was washed with 1M NaOH solution (30 ml) and dried with magnesium sulfate. After filtration, the solvent was removed in vacuo. The crude product was purified by flash column chromatography on silica gel [dichloromethane:ethyl acetate = 100:0 → 80:20, R_f (dichloromethane:ethyl acetate = 8:2) = 0.67] to yield the title compound (256 mg, 850 µmol, 75%) as a yellow solid. A small amount of the title compound was recrystallized from acetone, leading to crystals suitable for single crystal X-ray diffraction.

Melting point: 361 K. ¹H NMR (500 MHz, DMSO-d₆, 298 K, TMS): δ = 8.59 (s, 1 H, H-4), 7.65 (d, ³J = 9.0 Hz, 1 H, H-5), 6.78 (dd, ³J = 9.0 Hz, ⁴J = 2.5 Hz, 1 H, H-6), 6.54 (d, ⁴J = 2.3 Hz, 1 H, H-8), 6.01 (ddt, ²J = 17.2, 10.5 Hz, ³J = 5.2 Hz, 1 H, CH=CH₂), 5.48–5.22 (m, 2 H, CH=CH₂), 4.72 (dt, ³J = 5.2 Hz, ⁴J = 1.5 Hz, 2 H, OCH₂), 3.48 (q, ³J = 7.0 Hz, 4 H, NCH₂), 1.14 (t, ³J = 7.0 Hz, 6 H, NCH₂CH₃) ppm. ¹³C NMR (125 MHz, DMSO-d₆, 298 K, TMS): δ = 163.1 (s, COOCH₂), 158.1 (s, C-8a), 157.0 (s, C-2), 152.9 (s, C-7), 149.5 (d, C-4), 132.7 (d, CH=CH₂), 131.9 (d, C-5), 117.6 (t, CH=CH₂), 109.8 (d, C-6), 107.0 (s, C-4a), 106.9 (s, C-3), 95.8 (d, C-8), 64.7 (t, OCH₂), 44.4 (t, NCH₂), 12.3 (q, NCH₂CH₃) ppm. MS (EI, 70 eV): m/z (%) = 301.13 (43) [M]^+., 244.10 (20) [M –OCH₂CH=CH₂]⁺. HR–MS (EI, 70 eV): found: m/z = 301.1313 [M]^+., calculated: m/z = 301.1314 [M]^+. (Δ = 0.32 ppm). IR (ATR) wavenumbers: 2972 (w, C—H), 1729, 1685 (s, C=O), 1585 (s, arom.), 1216, 1185, 1114 (s, C—O) cm⁻¹. Elemental analysis C₁₇H₁₉NO₄ calculated: C: 67.76, H: 6.36, N: 4.65; found: C: 67.67, H: 6.38, N: 4.54.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C—H hydrogen atoms were located in difference maps but were positioned with idealized geometry (methyl H atoms allowed to rotate but not to tip) and refined isotropically with U_iso(H) = 1.2U_eq(C) (1.5 for methyl H atoms) using a riding model.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₉NO₄
M_r	301.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	13.72487 (9), 13.05333 (9), 8.55970 (6)
β (°)	95.5220 (6)
V (Å³)	1526.40 (2)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.77
Crystal size (mm)	0.08 × 0.06 × 0.05

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 )
T_min, T_max	0.796, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	26198, 3125, 2975
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.03
No. of reflections	3125
No. of parameters	202
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.18
Computer programs: CrysAlis PRO (Rigaku OD, 2020), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ), DIAMOND (Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2064943

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002218/wm5600sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021002218/wm5600Isup2.hkl

Figure S1: 1H NMR spectrum of 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid allyl ester in dimethylsulfoxide-d6. DOI: https://doi.org/10.1107/S2056989021002218/wm5600sup3.tif

Figure S2: 13C NMR spectrum of 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylic acid allyl ester in dimethylsulfoxide-d6. DOI: https://doi.org/10.1107/S2056989021002218/wm5600sup4.tif

Figure S3: Experimental (top) and calculated XRPD pattern (botom) of the title compound measured with copper radiation. DOI: https://doi.org/10.1107/S2056989021002218/wm5600sup5.tif

Supporting information file. DOI: https://doi.org/10.1107/S2056989021002218/wm5600Isup6.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

Allyl 7-(diethylamino)-2-oxo-2H-chromene-3-carboxylate top

Crystal data top

C₁₇H₁₉NO₄	F(000) = 640
M_r = 301.33	D_x = 1.311 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 13.72487 (9) Å	Cell parameters from 18730 reflections
b = 13.05333 (9) Å	θ = 3.2–79.5°
c = 8.55970 (6) Å	µ = 0.77 mm⁻¹
β = 95.5220 (6)°	T = 100 K
V = 1526.40 (2) Å³	Block, colorless
Z = 4	0.08 × 0.06 × 0.05 mm

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	3125 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2975 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.025
Detector resolution: 10.0000 pixels mm^-1	θ_max = 74.5°, θ_min = 3.2°
ω scans	h = −17→17
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	k = −16→16
T_min = 0.796, T_max = 1.000	l = −10→9
26198 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0452P)² + 0.4857P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.090	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.27 e Å⁻³
3125 reflections	Δρ_min = −0.18 e Å⁻³
202 parameters	Extinction correction: SHELXL (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00051 (13)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.42522 (5)	0.43406 (5)	0.62496 (8)	0.02005 (16)
O2	0.30849 (5)	0.49523 (5)	0.45723 (9)	0.02685 (18)
O3	0.14546 (5)	0.22199 (6)	0.48871 (10)	0.03164 (19)
O4	0.15018 (5)	0.37908 (6)	0.38321 (9)	0.02571 (18)
N1	0.69931 (6)	0.32538 (6)	0.96569 (9)	0.02028 (19)
C1	0.33583 (7)	0.42197 (7)	0.53540 (11)	0.0200 (2)
C2	0.28755 (7)	0.32340 (7)	0.54870 (11)	0.0200 (2)
C3	0.33465 (7)	0.24639 (7)	0.63486 (11)	0.0208 (2)
H3	0.302995	0.181966	0.640621	0.025*
C4	0.42814 (7)	0.25947 (7)	0.71496 (11)	0.0196 (2)
C5	0.48286 (7)	0.18288 (7)	0.80087 (11)	0.0213 (2)
H5	0.457233	0.115320	0.802308	0.026*
C6	0.57144 (7)	0.20301 (7)	0.88188 (11)	0.0208 (2)
H6	0.606652	0.149382	0.937029	0.025*
C7	0.61162 (7)	0.30412 (7)	0.88437 (11)	0.0187 (2)
C8	0.55922 (7)	0.38049 (7)	0.79458 (11)	0.0194 (2)
H8	0.584776	0.448004	0.791190	0.023*
C9	0.47128 (7)	0.35691 (7)	0.71221 (11)	0.0184 (2)
C10	0.18826 (7)	0.30202 (8)	0.47158 (11)	0.0220 (2)
C11	0.05028 (7)	0.36342 (9)	0.31361 (13)	0.0278 (2)
H11A	0.005740	0.353447	0.396689	0.033*
H11B	0.046669	0.302041	0.245361	0.033*
C12	0.02189 (8)	0.45623 (9)	0.22007 (14)	0.0333 (3)
H12	0.056563	0.471426	0.132052	0.040*
C13	−0.04888 (9)	0.51877 (10)	0.25251 (17)	0.0408 (3)
H13A	−0.084753	0.505412	0.339854	0.049*
H13B	−0.064001	0.577191	0.188542	0.049*
C14	0.74215 (7)	0.42822 (8)	0.96559 (12)	0.0237 (2)
H14A	0.730319	0.457818	0.858963	0.028*
H14B	0.813825	0.423083	0.991818	0.028*
C15	0.69959 (9)	0.49949 (8)	1.08247 (13)	0.0303 (2)
H15A	0.630056	0.511206	1.049963	0.045*
H15B	0.734605	0.564996	1.085692	0.045*
H15C	0.706714	0.468117	1.186964	0.045*
C16	0.74742 (7)	0.25546 (8)	1.08276 (11)	0.0231 (2)
H16A	0.699758	0.202771	1.109081	0.028*
H16B	0.767645	0.294469	1.179671	0.028*
C17	0.83648 (8)	0.20262 (9)	1.02778 (14)	0.0324 (3)
H17A	0.816019	0.157826	0.938740	0.049*
H17B	0.868653	0.161646	1.113786	0.049*
H17C	0.882291	0.254245	0.995308	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0191 (3)	0.0158 (3)	0.0244 (3)	−0.0008 (2)	−0.0025 (3)	0.0018 (3)
O2	0.0244 (4)	0.0199 (4)	0.0343 (4)	−0.0021 (3)	−0.0069 (3)	0.0057 (3)
O3	0.0251 (4)	0.0236 (4)	0.0446 (5)	−0.0067 (3)	−0.0054 (3)	0.0041 (3)
O4	0.0182 (3)	0.0256 (4)	0.0319 (4)	−0.0036 (3)	−0.0048 (3)	0.0050 (3)
N1	0.0187 (4)	0.0214 (4)	0.0205 (4)	0.0016 (3)	0.0006 (3)	0.0009 (3)
C1	0.0184 (4)	0.0192 (5)	0.0222 (5)	0.0002 (4)	−0.0001 (4)	−0.0009 (4)
C2	0.0193 (5)	0.0189 (5)	0.0218 (5)	−0.0014 (4)	0.0015 (4)	−0.0017 (4)
C3	0.0227 (5)	0.0172 (4)	0.0228 (5)	−0.0026 (4)	0.0035 (4)	−0.0015 (4)
C4	0.0212 (5)	0.0176 (5)	0.0201 (4)	−0.0004 (4)	0.0027 (4)	−0.0006 (3)
C5	0.0253 (5)	0.0163 (4)	0.0225 (5)	−0.0007 (4)	0.0030 (4)	0.0004 (4)
C6	0.0240 (5)	0.0180 (5)	0.0206 (4)	0.0036 (4)	0.0029 (4)	0.0016 (3)
C7	0.0182 (4)	0.0209 (5)	0.0173 (4)	0.0018 (4)	0.0037 (3)	−0.0010 (3)
C8	0.0200 (5)	0.0168 (4)	0.0215 (5)	−0.0008 (3)	0.0021 (4)	0.0000 (3)
C9	0.0201 (4)	0.0167 (4)	0.0188 (4)	0.0020 (3)	0.0031 (3)	0.0006 (3)
C10	0.0211 (5)	0.0201 (5)	0.0245 (5)	−0.0013 (4)	0.0013 (4)	−0.0019 (4)
C11	0.0177 (5)	0.0297 (5)	0.0348 (6)	−0.0043 (4)	−0.0044 (4)	0.0022 (4)
C12	0.0241 (5)	0.0370 (6)	0.0366 (6)	−0.0075 (5)	−0.0082 (4)	0.0101 (5)
C13	0.0346 (6)	0.0311 (6)	0.0529 (8)	−0.0015 (5)	−0.0156 (6)	0.0041 (5)
C14	0.0202 (5)	0.0249 (5)	0.0253 (5)	−0.0022 (4)	−0.0011 (4)	0.0016 (4)
C15	0.0335 (6)	0.0246 (5)	0.0317 (6)	0.0004 (4)	−0.0021 (4)	−0.0030 (4)
C16	0.0223 (5)	0.0268 (5)	0.0196 (4)	0.0027 (4)	−0.0007 (4)	0.0022 (4)
C17	0.0257 (5)	0.0366 (6)	0.0348 (6)	0.0104 (5)	0.0020 (4)	0.0064 (5)

Geometric parameters (Å, º) top

O1—C1	1.3916 (11)	C8—H8	0.9500
O1—C9	1.3714 (11)	C8—C9	1.3729 (13)
O2—C1	1.2062 (12)	C11—H11A	0.9900
O3—C10	1.2142 (13)	C11—H11B	0.9900
O4—C10	1.3346 (12)	C11—C12	1.4833 (15)
O4—C11	1.4558 (11)	C12—H12	0.9500
N1—C7	1.3597 (12)	C12—C13	1.3188 (19)
N1—C14	1.4655 (13)	C13—H13A	0.9500
N1—C16	1.4648 (12)	C13—H13B	0.9500
C1—C2	1.4567 (13)	C14—H14A	0.9900
C2—C3	1.3713 (14)	C14—H14B	0.9900
C2—C10	1.4824 (13)	C14—C15	1.5233 (15)
C3—H3	0.9500	C15—H15A	0.9800
C3—C4	1.4059 (13)	C15—H15B	0.9800
C4—C5	1.4134 (13)	C15—H15C	0.9800
C4—C9	1.4041 (13)	C16—H16A	0.9900
C5—H5	0.9500	C16—H16B	0.9900
C5—C6	1.3660 (14)	C16—C17	1.5173 (14)
C6—H6	0.9500	C17—H17A	0.9800
C6—C7	1.4297 (14)	C17—H17B	0.9800
C7—C8	1.4125 (13)	C17—H17C	0.9800

C9—O1—C1	123.53 (8)	O4—C11—H11B	110.3
C10—O4—C11	115.36 (8)	O4—C11—C12	107.12 (8)
C7—N1—C14	121.47 (8)	H11A—C11—H11B	108.5
C7—N1—C16	122.79 (8)	C12—C11—H11A	110.3
C16—N1—C14	114.62 (8)	C12—C11—H11B	110.3
O1—C1—C2	116.15 (8)	C11—C12—H12	118.2
O2—C1—O1	115.24 (8)	C13—C12—C11	123.54 (12)
O2—C1—C2	128.61 (9)	C13—C12—H12	118.2
C1—C2—C10	122.49 (9)	C12—C13—H13A	120.0
C3—C2—C1	119.67 (9)	C12—C13—H13B	120.0
C3—C2—C10	117.84 (9)	H13A—C13—H13B	120.0
C2—C3—H3	118.9	N1—C14—H14A	109.1
C2—C3—C4	122.29 (9)	N1—C14—H14B	109.1
C4—C3—H3	118.9	N1—C14—C15	112.32 (8)
C3—C4—C5	125.60 (9)	H14A—C14—H14B	107.9
C9—C4—C3	117.93 (9)	C15—C14—H14A	109.1
C9—C4—C5	116.46 (9)	C15—C14—H14B	109.1
C4—C5—H5	119.0	C14—C15—H15A	109.5
C6—C5—C4	122.04 (9)	C14—C15—H15B	109.5
C6—C5—H5	119.0	C14—C15—H15C	109.5
C5—C6—H6	119.7	H15A—C15—H15B	109.5
C5—C6—C7	120.55 (9)	H15A—C15—H15C	109.5
C7—C6—H6	119.7	H15B—C15—H15C	109.5
N1—C7—C6	121.14 (9)	N1—C16—H16A	108.9
N1—C7—C8	120.91 (9)	N1—C16—H16B	108.9
C8—C7—C6	117.90 (9)	N1—C16—C17	113.25 (8)
C7—C8—H8	120.1	H16A—C16—H16B	107.7
C9—C8—C7	119.84 (9)	C17—C16—H16A	108.9
C9—C8—H8	120.1	C17—C16—H16B	108.9
O1—C9—C4	120.09 (8)	C16—C17—H17A	109.5
O1—C9—C8	116.83 (8)	C16—C17—H17B	109.5
C8—C9—C4	123.08 (9)	C16—C17—H17C	109.5
O3—C10—O4	123.31 (9)	H17A—C17—H17B	109.5
O3—C10—C2	122.88 (9)	H17A—C17—H17C	109.5
O4—C10—C2	113.80 (8)	H17B—C17—H17C	109.5
O4—C11—H11A	110.3

O1—C1—C2—C3	−5.62 (13)	C5—C6—C7—N1	179.41 (8)
O1—C1—C2—C10	174.60 (8)	C5—C6—C7—C8	−3.06 (14)
O2—C1—C2—C3	174.72 (10)	C6—C7—C8—C9	1.82 (13)
O2—C1—C2—C10	−5.06 (16)	C7—N1—C14—C15	81.70 (11)
O4—C11—C12—C13	−115.91 (12)	C7—N1—C16—C17	107.68 (11)
N1—C7—C8—C9	179.35 (8)	C7—C8—C9—O1	−178.72 (8)
C1—O1—C9—C4	−0.28 (13)	C7—C8—C9—C4	1.57 (14)
C1—O1—C9—C8	180.00 (8)	C9—O1—C1—O2	−175.17 (8)
C1—C2—C3—C4	1.44 (14)	C9—O1—C1—C2	5.12 (13)
C1—C2—C10—O3	−176.05 (10)	C9—C4—C5—C6	2.31 (14)
C1—C2—C10—O4	3.33 (13)	C10—O4—C11—C12	−179.62 (9)
C2—C3—C4—C5	−177.39 (9)	C10—C2—C3—C4	−178.77 (9)
C2—C3—C4—C9	3.51 (14)	C11—O4—C10—O3	3.12 (14)
C3—C2—C10—O3	4.17 (15)	C11—O4—C10—C2	−176.26 (8)
C3—C2—C10—O4	−176.45 (8)	C14—N1—C7—C6	178.43 (8)
C3—C4—C5—C6	−176.79 (9)	C14—N1—C7—C8	0.97 (13)
C3—C4—C9—O1	−4.15 (13)	C14—N1—C16—C17	−84.26 (11)
C3—C4—C9—C8	175.56 (9)	C16—N1—C7—C6	−14.31 (13)
C4—C5—C6—C7	0.96 (14)	C16—N1—C7—C8	168.23 (8)
C5—C4—C9—O1	176.67 (8)	C16—N1—C14—C15	−86.53 (10)
C5—C4—C9—C8	−3.62 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ⁱ	0.95	2.45	3.3958 (12)	171

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

Funding information

VN gratefully thanks the Christian-Albrechts-Universität zu Kiel for a scholarship to fund this work. We acknowledge financial support by the DFG within the funding programme `Open Access Publizieren'.

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