The crystal structure of the title compound, C17H19NO4, consists of nearly planar molecules that are linked by intermolecular C—H⋯O hydrogen bonding into chains along the b-axis direction.
Keywords: crystal structure, synthesis, 2-oxo-2H-chromene, C—H⋯O hydrogen bonding
Abstract
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 Car—H⋯Ocarbonyl 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.
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.
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.
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.
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.
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 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.
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 ▸).
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-d 6 (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-d 6, 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=CH 2), 4.72 (dt, 3J = 5.2 Hz, 4J = 1.5 Hz, 2 H, OCH 2), 3.48 (q, 3J = 7.0 Hz, 4 H, NCH 2), 1.14 (t, 3J = 7.0 Hz, 6 H, NCH2CH 3) ppm. 13C NMR (125 MHz, DMSO-d 6, 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, NCH2 CH3) 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.
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[F 2 > 2σ(F 2)], wR(F 2), S | 0.033, 0.090, 1.03 |
| No. of reflections | 3125 |
| No. of parameters | 202 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.27, −0.18 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021002218/wm5600sup1.cif
Structure factors: contains datablock(s) I. DOI: 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: 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: 10.1107/S2056989021002218/wm5600sup4.tif
Figure S3: Experimental (top) and calculated XRPD pattern (botom) of the title compound measured with copper radiation. DOI: 10.1107/S2056989021002218/wm5600sup5.tif
Supporting information file. DOI: 10.1107/S2056989021002218/wm5600Isup6.cml
CCDC reference: 2064943
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Crystal data
| C17H19NO4 | F(000) = 640 |
| Mr = 301.33 | Dx = 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
| 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 | Rint = 0.025 |
| Detector resolution: 10.0000 pixels mm-1 | θmax = 74.5°, θmin = 3.2° |
| ω scans | h = −17→17 |
| Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | k = −16→16 |
| Tmin = 0.796, Tmax = 1.000 | l = −10→9 |
| 26198 measured reflections |
Refinement
| 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(Fo2) + (0.0452P)2 + 0.4857P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.090 | (Δ/σ)max < 0.001 |
| S = 1.03 | Δρmax = 0.27 e Å−3 |
| 3125 reflections | Δρmin = −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
| 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)
| x | y | z | Uiso*/Ueq | ||
| 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)
| 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)
| 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)
| 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 Statement
This work was funded by Christian-Albrechts-Universität zu Kiel grant . Deutsche Forschungsgemeinschaft grant .
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021002218/wm5600sup1.cif
Structure factors: contains datablock(s) I. DOI: 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: 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: 10.1107/S2056989021002218/wm5600sup4.tif
Figure S3: Experimental (top) and calculated XRPD pattern (botom) of the title compound measured with copper radiation. DOI: 10.1107/S2056989021002218/wm5600sup5.tif
Supporting information file. DOI: 10.1107/S2056989021002218/wm5600Isup6.cml
CCDC reference: 2064943
Additional supporting information: crystallographic information; 3D view; checkCIF report