2-Methyl-3-[(2-methylphenyl)carbamoyl]phenyl acetate was synthesized, characterized by IR spectroscopy, and its crystal structure was determined from single-crystal data. In the crystal, molecules are linked by N—H⋯O hydrogen bonds. The two independent molecules in the asymmetric unit adopt different conformations.
Keywords: crystal structure, amide, X-ray diffraction, Hirshfeld surface, hydrogen bonding
Abstract
The title compound, C17H17NO3, was synthesized, characterized by IR spectroscopy and its crystal structure was determined from single-crystal diffraction data. The asymmetric unit contains two molecules, which adopt different conformations. In one molecule, the acetoxy and the terminal 2-methylphenyl groups are positioned on opposite sides of the plane formed by the central benzene ring, whereas in the other molecule they lie on the same side of this plane. In the crystal, the molecules are linked through strong N—H⋯O hydrogen bonds into chains along [010]. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the solid state.
Chemical context
Amides and their derivatives are extremely important biologically active compounds. Amide groups are present in a number of natural products, polymers and pharmaceuticals (Valeur & Bradley, 2009 ▸; Xiang et al., 2012 ▸). Amide derivatives have been found to exhibit biological and pharmacological activities such as antitumor, antimicrobial, antibacterial, antifungal, anti-HSV, analgesic, anti-inflammatory and anticancer (Carbonnelle et al., 2005 ▸). Moreover, amide-based compounds represent an important group of efficient chelating ligands (Strotmeyer et al., 2003 ▸; Sliva et al., 1997 ▸; Pavlishchuk et al., 2011 ▸; Gumienna-Kontecka et al., 2007 ▸). Recently, we synthesized and studied some new substituted secondary benzamide derivatives obtained as a result of the interaction of aniline-based compounds with acyl chlorides (Çakmak et al., 2016 ▸; Kırca et al., 2018 ▸; Demir et al., 2015 ▸; Kansız, Çakmak et al., 2018 ▸). Among them, 3-acetoxy-2-methyl-N-(4-methoxyphenyl) benzamide was found to exhibit good antioxidant activity (Demir et al., 2015 ▸). As a continuation of this work, we prepared the title compound and studied its spectroscopic and structural features.
Structural commentary
The asymmetric unit of the title compound (Fig. 1 ▸) contains two molecules, A and B, which adopt different conformations that can be characterized by the mutual arrangement of the acetoxy and terminal 2-methylphenyl groups with respect to the plane of the central benzene ring: in molecule A they lie on different sides of this plane, whereas in molecule B they are positioned on the same side. The torsion angles characterizing the conformation details are summarized in Table 1 ▸. The dihedral angles subtended by the aromatic rings are 54.33 (12) and 66.68 (11)° in molecules A and B, respectively. The molecular conformations are stabilized by weak intramolecular C—H⋯O contacts (Table 2 ▸). All bond lengths and angles are typical of similar compounds, bearing in mind the effect of intermolecular hydrogen bonds on the geometry of the amido groups.
Figure 1.
The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 50% probability level.
Table 1. Selected geometric parameters (Å, °).
| O1—C1 | 1.222 (3) | O3—C9 | 1.186 (4) |
| O4—C18 | 1.224 (3) | O6—C26 | 1.188 (4) |
| N1—C1 | 1.348 (3) | N2—C18 | 1.344 (4) |
| O1—C1—N1 | 123.5 (3) | C1—N1—C11 | 123.4 (2) |
| O4—C18—N2 | 123.6 (3) | C18—N2—C28 | 124.2 (2) |
| C9—O2—C6—C7 | −100.0 (3) | C26—O5—C23—C24 | −83.7 (3) |
| N1—C1—C2—C7 | 129.1 (3) | C24—C19—C18—N2 | −113.6 (3) |
| C2—C1—N1—C11 | −172.4 (2) | C28—N2—C18—C19 | 166.2 (2) |
| C1—N1—C11—C16 | −66.4 (4) | C18—N2—C28—C33 | 66.0 (4) |
Table 2. Hydrogen-bond geometry (Å, °).
Cg1 is the centroid of the C28–C33 ring.
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C5—H5⋯O6i | 0.93 | 2.49 | 3.402 (4) | 167 |
| N2—H2⋯O1ii | 0.88 (3) | 1.96 (3) | 2.813 (3) | 164 (2) |
| N1—H1⋯O4 | 0.91 (3) | 1.91 (3) | 2.804 (3) | 166 (2) |
| C25—H25B⋯O4 | 0.96 | 2.76 | 3.117 (4) | 103 |
| C34—H34A⋯O4 | 0.96 | 2.59 | 3.100 (4) | 114 |
| C8—H8B⋯O1 | 0.96 | 2.75 | 2.986 (4) | 95 |
| C3—H3⋯Cg1 | 0.93 | 2.81 | 3.666 (3) | 153 |
Symmetry codes: (i) 
; (ii) 
.
Supramolecular features
The packing diagram of the title compounds is presented in Fig. 2 ▸. In the crystal, the molecules are linked through strong N—H⋯O hydrogen bonds (Table 2 ▸) into chains along [010]. They are further linked by C—H⋯O and C—H⋯π contacts (Table 2 ▸).
Figure 2.
Packing diagram of the title compound showing the short intermolecular contacts. Cg1 is the centroid of the C28–C33 benzene ring.
Database survey
A search in the Cambridge Structural Database (CSD version 5.39, update of August 2018; Groom et al., 2016 ▸) for 3-acetoxy-N-phenylbenzamide derivatives gave three hits: 3-acetoxy-2-methyl-N-(4-methylphenyl)benzamide (HEJBIK; Kırca et al., 2018 ▸), 3-acetoxy-2-methyl-N-phenylbenzamide and 3-acetoxy-2-methyl-N-(4-methoxyphenyl)benzamide (HEJBOQ and JUMCEB, respectively; both Demir et al., 2015 ▸). The structure of HEJBIK is especially close to that of the title compound: it also contains two molecules in an asymmetric unit and is isostructural to the title compound with the exception of one methyl group (2-Me in the title compound and 4-Me in HEJBIK). The two independent molecules in HEJBIK have different conformations in the same manner, as in the title structure. In the two structures HEJBOQ and JUMCEB, the acetoxy groups and the terminal benzene rings are positioned on opposite sides of the planes formed by the central benzene rings. In all these structures, the molecules are linked into chains by N—H⋯O hydrogen bonds.
Hirshfeld surface analysis
The molecular Hirshfeld surfaces (d norm) for molecules A and B of the title compound generated using CrystalExplorer3.1 (Wolff et al., 2012 ▸) and are presented in Fig. 3 ▸. The d norm values are mapped on the Hirshfeld surfaces using a red–blue–white colour scheme (Spackman & Jayatilaka, 2009 ▸) as follows: the dark-red spots indicate the closest contacts related to the N—H⋯O hydrogen bonds, the other short intermolecular contacts appear as light-red spots, blue regions depict positive d norm values, and in the white regions the lengths of the contacts are exactly equal to the sum of van der Waals radii (d norm = 0). Analogous dark-red spots related to the N—H⋯O interactions were observed on the Hirshfeld surfaces of similar molecules (Şen et al., 2017 ▸; Gümüş et al., 2018 ▸; Kansız & Dege, 2018 ▸). Figs. 4 ▸ and 5 ▸ show the two-dimensional fingerprint plots for molecules A and B, respectively. For both molecules, the contributions from the H⋯H/ H⋯H contacts are the largest (55.3 and 53.9% for A and B, respectively). The contributions of the other intermolecular contacts are as follows: C⋯H/H⋯C (22.5%) and O⋯H/H⋯O (20.7%) for A and C⋯H/H⋯C (23.8%) and O⋯H/H⋯O (21.7%) for B. The Hirshfeld surface mapped over the electrostatic potential n (±0.25 a.u.) is shown in Fig. 6 ▸ where blue regions correspond to positive electrostatic potential and red spots related to the oxygen atoms represent the areas of negative electrostatic potential; the distribution is analogous to that in a similar compound (Yaman et al., 2018 ▸).
Figure 3.
Hirsfeld surfaces of 3-acetoxy-2-methyl-N-(3-methylphenyl) benzamide (three-dimensional d norm surface): (a) molecule A and (b) molecule B.
Figure 4.
The fingerprint plots for molecule A: (a) all atomsinside⋯all atomsoutside (100%), (b) Hinside⋯Houtside/Houtside⋯Hinside (55.3%), (c) Cinside⋯Houtside/Houtside⋯Cinside (22.5%) and (d) Oinside⋯Houtside/Houtside⋯Oinside (20.7%).
Figure 5.
The fingerprint plots for molecule B: (a) all atomsinside⋯all atomsoutside (100%), (b) Hinside⋯Houtside/Houtside⋯Hinside (53.9%), (c) Cinside⋯Houtside/Houtside⋯Cinside (23.8%) and (d) Oinside⋯Houtside/Houtside⋯Oinside (21.7%).
Figure 6.
Electrostatic potential mapped on the Hirshfeld surface (± 0.25 a.u.).
Vibrational spectrum
The IR spectrum of the title compound (KBr, cm−1) shown in Fig. 7 ▸ exhibits the following characteristic bands: 3210 (N—H), 1761 (acetoxy C=O), 1651 (amide C=O). Because of the interaction of the aromatic group with the acetoxy carbonyl moiety, the frequency of the acetoxy C=O stretching vibration is larger compared to the normal frequency of the stretching vibrations in esters (1740 cm−1).
Figure 7.
IR spectrum of the title compound.
Synthesis and crystallization
The synthesis was performed according to the reaction scheme presented in Fig. 8 ▸ and applied earlier for the synthesis of analogous compounds (Cakmak et al., 2016 ▸; Kırca et al., 2018 ▸, Demir et al., 2015 ▸). A solution of 3-acetoxy-2-methylbenzoyl chloride (11 mmol) in THF (10 mL) was added dropwise to a solution of 2-methylaniline (10 mmol) and triethylamine (10 mmol) in THF (10 mL) at room temperature. After the reaction mixture had been stirred at room temperature for 15 h, the resulting white precipitate was filtered off and then 100 ml of water was added dropwise to the filtrate. The precipitate was filtered off and washed several times with water to remove the unreacted reagents and triethylamine hydrochloride. The crude product was recrystallized from acetonitrile (1.82 g, 58%; m.p. 435-438 K). Single crystals were obtained from an acetonitrile solution after incubation in the fridge for 20 days.
Figure 8.
Reaction scheme.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The N-bound H atoms were freely refined. C-bound hydrogen atoms were positioned geometrically and refined as riding with C—H = 0.93 Å and U iso(H) = 1.2U eq(C) for aromatic C atoms and C—H = 0.96 Å and U iso(H) = 1.5U eq(C) for methyl groups. Each methyl group was allowed to rotate about its parent C—C bond.
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | C17H17NO3 |
| M r | 283.31 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 296 |
| a, b, c (Å) | 7.7842 (5), 8.8802 (5), 22.2112 (15) |
| α, β, γ (°) | 94.791 (5), 97.620 (5), 90.043 (5) |
| V (Å3) | 1516.37 (17) |
| Z | 4 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.09 |
| Crystal size (mm) | 0.42 × 0.37 × 0.21 |
| Data collection | |
| Diffractometer | Stoe IPDS 2 |
| Absorption correction | Integration (X-RED32; Stoe & Cie, 2002 ▸) |
| T min, T max | 0.958, 0.993 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 21781, 5950, 3029 |
| R int | 0.086 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.057, 0.159, 0.90 |
| No. of reflections | 5950 |
| No. of parameters | 393 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.17, −0.14 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019000021/yk2118sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019000021/yk2118Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989019000021/yk2118Isup3.cml
CCDC reference: 1584572
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).
supplementary crystallographic information
Crystal data
| C17H17NO3 | Z = 4 |
| Mr = 283.31 | F(000) = 600 |
| Triclinic, P1 | Dx = 1.241 Mg m−3 |
| a = 7.7842 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 8.8802 (5) Å | Cell parameters from 19688 reflections |
| c = 22.2112 (15) Å | θ = 1.9–27.5° |
| α = 94.791 (5)° | µ = 0.09 mm−1 |
| β = 97.620 (5)° | T = 296 K |
| γ = 90.043 (5)° | Prism, colorless |
| V = 1516.37 (17) Å3 | 0.42 × 0.37 × 0.21 mm |
Data collection
| Stoe IPDS 2 diffractometer | 5950 independent reflections |
| Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 3029 reflections with I > 2σ(I) |
| Detector resolution: 6.67 pixels mm-1 | Rint = 0.086 |
| rotation method scans | θmax = 26.0°, θmin = 1.9° |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | h = −9→9 |
| Tmin = 0.958, Tmax = 0.993 | k = −10→10 |
| 21781 measured reflections | l = −27→27 |
Refinement
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.0763P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.90 | (Δ/σ)max < 0.001 |
| 5950 reflections | Δρmax = 0.17 e Å−3 |
| 393 parameters | Δρmin = −0.13 e Å−3 |
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 | 0.5356 (3) | 0.3278 (2) | 0.28533 (9) | 0.0605 (6) | |
| N2 | 0.6781 (3) | 1.0533 (3) | 0.32141 (11) | 0.0482 (6) | |
| O2 | 0.2232 (3) | 0.5083 (3) | 0.07897 (10) | 0.0717 (6) | |
| C1 | 0.5516 (3) | 0.4634 (3) | 0.28130 (12) | 0.0448 (7) | |
| N1 | 0.6771 (3) | 0.5500 (3) | 0.31509 (11) | 0.0486 (6) | |
| O5 | 0.7722 (3) | 1.0738 (3) | 0.07181 (9) | 0.0662 (6) | |
| C28 | 0.5682 (4) | 0.9934 (3) | 0.36083 (12) | 0.0468 (7) | |
| O4 | 0.7921 (3) | 0.8326 (2) | 0.28774 (10) | 0.0608 (6) | |
| C19 | 0.8414 (3) | 1.0503 (3) | 0.23666 (12) | 0.0438 (6) | |
| C18 | 0.7690 (3) | 0.9681 (3) | 0.28425 (13) | 0.0464 (7) | |
| C11 | 0.8180 (3) | 0.4903 (3) | 0.35334 (12) | 0.0463 (7) | |
| C16 | 0.7951 (4) | 0.4184 (3) | 0.40468 (13) | 0.0537 (7) | |
| C2 | 0.4280 (3) | 0.5450 (3) | 0.23801 (13) | 0.0452 (7) | |
| C3 | 0.3430 (4) | 0.6702 (3) | 0.26034 (15) | 0.0567 (8) | |
| H3 | 0.368858 | 0.706558 | 0.301043 | 0.068* | |
| C12 | 0.9848 (4) | 0.5130 (3) | 0.33845 (14) | 0.0572 (8) | |
| H12 | 0.999896 | 0.565609 | 0.304998 | 0.069* | |
| C7 | 0.3944 (4) | 0.4892 (3) | 0.17655 (14) | 0.0516 (7) | |
| C17 | 0.6204 (4) | 0.4057 (4) | 0.42552 (15) | 0.0705 (9) | |
| H17A | 0.558650 | 0.319989 | 0.403650 | 0.106* | |
| H17B | 0.555999 | 0.495828 | 0.417841 | 0.106* | |
| H17C | 0.634656 | 0.393102 | 0.468398 | 0.106* | |
| C20 | 0.9676 (4) | 1.1600 (3) | 0.25396 (14) | 0.0560 (8) | |
| H20 | 1.006541 | 1.184171 | 0.295057 | 0.067* | |
| C6 | 0.2705 (4) | 0.5654 (4) | 0.14029 (14) | 0.0585 (8) | |
| C24 | 0.7774 (4) | 1.0137 (3) | 0.17529 (14) | 0.0532 (7) | |
| C34 | 0.8224 (4) | 0.8962 (4) | 0.42816 (16) | 0.0729 (9) | |
| H34A | 0.864042 | 0.813155 | 0.403828 | 0.109* | |
| H34B | 0.842987 | 0.876968 | 0.470381 | 0.109* | |
| H34C | 0.882266 | 0.987300 | 0.422249 | 0.109* | |
| C23 | 0.8470 (4) | 1.0938 (3) | 0.13335 (13) | 0.0545 (8) | |
| O6 | 0.9365 (4) | 0.8729 (3) | 0.05401 (12) | 0.0885 (8) | |
| C33 | 0.6320 (4) | 0.9139 (3) | 0.40945 (14) | 0.0550 (7) | |
| C13 | 1.1258 (4) | 0.4580 (4) | 0.37307 (17) | 0.0728 (10) | |
| H13 | 1.236428 | 0.472783 | 0.362982 | 0.087* | |
| C22 | 0.9755 (4) | 1.2010 (4) | 0.14968 (15) | 0.0639 (9) | |
| H22 | 1.020909 | 1.250648 | 0.119977 | 0.077* | |
| C26 | 0.8233 (5) | 0.9545 (4) | 0.03635 (15) | 0.0646 (9) | |
| C4 | 0.2194 (4) | 0.7415 (4) | 0.22218 (18) | 0.0727 (10) | |
| H4 | 0.161175 | 0.824827 | 0.237254 | 0.087* | |
| C32 | 0.5113 (5) | 0.8545 (4) | 0.44225 (15) | 0.0713 (9) | |
| H32 | 0.550319 | 0.797517 | 0.474527 | 0.086* | |
| C29 | 0.3907 (4) | 1.0207 (3) | 0.34776 (15) | 0.0608 (8) | |
| H29 | 0.350054 | 1.078584 | 0.315939 | 0.073* | |
| C5 | 0.1834 (4) | 0.6884 (4) | 0.16207 (18) | 0.0736 (10) | |
| H5 | 0.100416 | 0.735476 | 0.136156 | 0.088* | |
| C15 | 0.9407 (4) | 0.3628 (4) | 0.43830 (15) | 0.0678 (9) | |
| H15 | 0.928027 | 0.311797 | 0.472381 | 0.081* | |
| C21 | 1.0363 (4) | 1.2343 (4) | 0.21012 (16) | 0.0680 (9) | |
| H21 | 1.123516 | 1.306624 | 0.221625 | 0.082* | |
| C9 | 0.2956 (5) | 0.5755 (5) | 0.03514 (16) | 0.0724 (10) | |
| C31 | 0.3375 (5) | 0.8771 (4) | 0.42858 (17) | 0.0758 (10) | |
| H31 | 0.260317 | 0.834551 | 0.451079 | 0.091* | |
| C14 | 1.1044 (5) | 0.3818 (4) | 0.42210 (17) | 0.0739 (10) | |
| H14 | 1.200093 | 0.342190 | 0.444874 | 0.089* | |
| C25 | 0.6354 (5) | 0.8978 (4) | 0.15608 (16) | 0.0806 (11) | |
| H25A | 0.568073 | 0.923610 | 0.119042 | 0.121* | |
| H25B | 0.562053 | 0.895667 | 0.187499 | 0.121* | |
| H25C | 0.685593 | 0.800058 | 0.149429 | 0.121* | |
| O3 | 0.4029 (4) | 0.6720 (3) | 0.04766 (13) | 0.1018 (9) | |
| C30 | 0.2768 (4) | 0.9620 (4) | 0.38199 (17) | 0.0752 (10) | |
| H30 | 0.158693 | 0.979873 | 0.373513 | 0.090* | |
| C8 | 0.4864 (5) | 0.3554 (4) | 0.15108 (15) | 0.0709 (9) | |
| H8A | 0.432986 | 0.264201 | 0.160420 | 0.106* | |
| H8B | 0.605821 | 0.358900 | 0.168815 | 0.106* | |
| H8C | 0.479238 | 0.357183 | 0.107663 | 0.106* | |
| C10 | 0.2217 (5) | 0.5106 (5) | −0.02652 (16) | 0.0945 (13) | |
| H10A | 0.118483 | 0.563994 | −0.040154 | 0.142* | |
| H10B | 0.193802 | 0.405789 | −0.025063 | 0.142* | |
| H10C | 0.304914 | 0.520111 | −0.054284 | 0.142* | |
| C27 | 0.7180 (5) | 0.9428 (5) | −0.02461 (16) | 0.0866 (11) | |
| H27A | 0.778041 | 0.882794 | −0.052970 | 0.130* | |
| H27B | 0.699550 | 1.042040 | −0.038207 | 0.130* | |
| H27C | 0.608231 | 0.896027 | −0.022119 | 0.130* | |
| H2 | 0.653 (3) | 1.146 (3) | 0.3128 (11) | 0.043 (7)* | |
| H1 | 0.696 (3) | 0.644 (3) | 0.3039 (12) | 0.050 (8)* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0662 (13) | 0.0394 (12) | 0.0731 (14) | −0.0031 (10) | −0.0063 (10) | 0.0143 (10) |
| N2 | 0.0520 (14) | 0.0373 (13) | 0.0590 (15) | 0.0039 (11) | 0.0162 (12) | 0.0120 (12) |
| O2 | 0.0670 (14) | 0.0830 (16) | 0.0625 (15) | −0.0198 (12) | −0.0088 (11) | 0.0188 (12) |
| C1 | 0.0410 (15) | 0.0385 (16) | 0.0560 (17) | −0.0008 (12) | 0.0073 (13) | 0.0098 (13) |
| N1 | 0.0473 (14) | 0.0361 (13) | 0.0616 (15) | −0.0058 (11) | −0.0006 (11) | 0.0121 (12) |
| O5 | 0.0718 (14) | 0.0768 (15) | 0.0500 (13) | 0.0150 (12) | 0.0071 (11) | 0.0076 (11) |
| C28 | 0.0541 (17) | 0.0373 (15) | 0.0503 (17) | −0.0026 (13) | 0.0124 (13) | 0.0025 (13) |
| O4 | 0.0714 (14) | 0.0373 (11) | 0.0799 (15) | 0.0040 (10) | 0.0271 (11) | 0.0141 (10) |
| C19 | 0.0424 (15) | 0.0389 (15) | 0.0523 (18) | 0.0006 (12) | 0.0119 (13) | 0.0075 (13) |
| C18 | 0.0422 (15) | 0.0405 (17) | 0.0565 (18) | −0.0036 (13) | 0.0057 (13) | 0.0064 (14) |
| C11 | 0.0478 (16) | 0.0380 (15) | 0.0510 (17) | −0.0028 (13) | 0.0001 (13) | 0.0021 (13) |
| C16 | 0.0569 (18) | 0.0495 (17) | 0.0538 (18) | −0.0046 (14) | 0.0028 (14) | 0.0064 (14) |
| C2 | 0.0387 (15) | 0.0391 (15) | 0.0582 (19) | −0.0023 (12) | 0.0039 (13) | 0.0111 (14) |
| C3 | 0.0539 (18) | 0.0506 (18) | 0.065 (2) | 0.0044 (15) | 0.0038 (15) | 0.0091 (15) |
| C12 | 0.0500 (18) | 0.0579 (19) | 0.0633 (19) | −0.0053 (15) | 0.0046 (15) | 0.0080 (15) |
| C7 | 0.0455 (16) | 0.0484 (17) | 0.0611 (19) | −0.0051 (13) | 0.0033 (14) | 0.0117 (15) |
| C17 | 0.068 (2) | 0.080 (2) | 0.067 (2) | −0.0040 (18) | 0.0158 (17) | 0.0151 (18) |
| C20 | 0.0559 (18) | 0.0562 (18) | 0.0562 (18) | −0.0131 (15) | 0.0101 (14) | 0.0026 (15) |
| C6 | 0.0532 (18) | 0.062 (2) | 0.058 (2) | −0.0064 (16) | −0.0075 (15) | 0.0158 (16) |
| C24 | 0.0503 (17) | 0.0479 (17) | 0.062 (2) | 0.0002 (14) | 0.0069 (15) | 0.0078 (15) |
| C34 | 0.065 (2) | 0.085 (2) | 0.068 (2) | 0.0039 (19) | 0.0013 (17) | 0.0160 (19) |
| C23 | 0.0582 (18) | 0.0571 (18) | 0.0504 (18) | 0.0051 (15) | 0.0124 (15) | 0.0093 (15) |
| O6 | 0.0905 (18) | 0.0892 (18) | 0.0804 (17) | 0.0270 (16) | −0.0028 (14) | −0.0017 (14) |
| C33 | 0.0586 (18) | 0.0497 (17) | 0.0571 (19) | −0.0006 (14) | 0.0090 (15) | 0.0047 (15) |
| C13 | 0.0478 (19) | 0.084 (2) | 0.085 (3) | −0.0015 (17) | 0.0010 (17) | 0.009 (2) |
| C22 | 0.069 (2) | 0.061 (2) | 0.068 (2) | −0.0093 (17) | 0.0290 (17) | 0.0134 (17) |
| C26 | 0.060 (2) | 0.075 (2) | 0.059 (2) | −0.0054 (18) | 0.0066 (17) | 0.0032 (19) |
| C4 | 0.060 (2) | 0.067 (2) | 0.090 (3) | 0.0220 (17) | 0.0032 (19) | 0.009 (2) |
| C32 | 0.085 (3) | 0.071 (2) | 0.063 (2) | −0.0019 (19) | 0.0214 (18) | 0.0162 (18) |
| C29 | 0.0547 (19) | 0.0576 (19) | 0.073 (2) | 0.0033 (15) | 0.0166 (16) | 0.0071 (16) |
| C5 | 0.056 (2) | 0.071 (2) | 0.091 (3) | 0.0117 (18) | −0.0102 (18) | 0.024 (2) |
| C15 | 0.069 (2) | 0.071 (2) | 0.062 (2) | 0.0009 (18) | −0.0044 (17) | 0.0197 (17) |
| C21 | 0.070 (2) | 0.066 (2) | 0.070 (2) | −0.0283 (17) | 0.0181 (17) | 0.0029 (18) |
| C9 | 0.059 (2) | 0.084 (3) | 0.074 (2) | −0.0010 (19) | −0.0024 (18) | 0.022 (2) |
| C31 | 0.071 (2) | 0.085 (3) | 0.079 (2) | −0.004 (2) | 0.034 (2) | 0.014 (2) |
| C14 | 0.061 (2) | 0.079 (2) | 0.079 (2) | 0.0102 (18) | −0.0053 (18) | 0.013 (2) |
| C25 | 0.074 (2) | 0.091 (3) | 0.073 (2) | −0.036 (2) | −0.0032 (18) | 0.013 (2) |
| O3 | 0.097 (2) | 0.108 (2) | 0.101 (2) | −0.0409 (18) | 0.0092 (16) | 0.0158 (17) |
| C30 | 0.054 (2) | 0.083 (2) | 0.093 (3) | 0.0012 (18) | 0.0241 (19) | 0.009 (2) |
| C8 | 0.080 (2) | 0.068 (2) | 0.063 (2) | 0.0065 (18) | 0.0068 (17) | 0.0001 (17) |
| C10 | 0.082 (3) | 0.135 (4) | 0.064 (2) | −0.010 (3) | −0.0021 (19) | 0.020 (2) |
| C27 | 0.075 (2) | 0.119 (3) | 0.063 (2) | −0.005 (2) | 0.0047 (18) | −0.008 (2) |
Geometric parameters (Å, º)
| O1—C1 | 1.222 (3) | C24—C25 | 1.504 (4) |
| O4—C18 | 1.224 (3) | C34—C33 | 1.497 (4) |
| N1—C1 | 1.348 (3) | C34—H34A | 0.9600 |
| O3—C9 | 1.186 (4) | C34—H34B | 0.9600 |
| O6—C26 | 1.188 (4) | C34—H34C | 0.9600 |
| N2—C18 | 1.344 (4) | C23—C22 | 1.372 (4) |
| N2—C28 | 1.434 (3) | C33—C32 | 1.391 (4) |
| N2—H2 | 0.88 (3) | C13—C14 | 1.357 (5) |
| O2—C9 | 1.365 (4) | C13—H13 | 0.9300 |
| O2—C6 | 1.414 (4) | C22—C21 | 1.371 (4) |
| C1—C2 | 1.499 (4) | C22—H22 | 0.9300 |
| N1—C11 | 1.427 (3) | C26—C27 | 1.483 (5) |
| N1—H1 | 0.91 (3) | C4—C5 | 1.371 (5) |
| O5—C26 | 1.359 (4) | C4—H4 | 0.9300 |
| O5—C23 | 1.409 (4) | C32—C31 | 1.365 (5) |
| C28—C33 | 1.378 (4) | C32—H32 | 0.9300 |
| C28—C29 | 1.400 (4) | C29—C30 | 1.372 (4) |
| C19—C20 | 1.378 (4) | C29—H29 | 0.9300 |
| C19—C24 | 1.399 (4) | C5—H5 | 0.9300 |
| C19—C18 | 1.502 (4) | C15—C14 | 1.383 (5) |
| C11—C16 | 1.384 (4) | C15—H15 | 0.9300 |
| C11—C12 | 1.400 (4) | C21—H21 | 0.9300 |
| C16—C15 | 1.387 (4) | C9—C10 | 1.482 (5) |
| C16—C17 | 1.501 (4) | C31—C30 | 1.365 (5) |
| C2—C3 | 1.384 (4) | C31—H31 | 0.9300 |
| C2—C7 | 1.404 (4) | C14—H14 | 0.9300 |
| C3—C4 | 1.385 (4) | C25—H25A | 0.9600 |
| C3—H3 | 0.9300 | C25—H25B | 0.9600 |
| C12—C13 | 1.369 (4) | C25—H25C | 0.9600 |
| C12—H12 | 0.9300 | C30—H30 | 0.9300 |
| C7—C6 | 1.387 (4) | C8—H8A | 0.9600 |
| C7—C8 | 1.497 (4) | C8—H8B | 0.9600 |
| C17—H17A | 0.9600 | C8—H8C | 0.9600 |
| C17—H17B | 0.9600 | C10—H10A | 0.9600 |
| C17—H17C | 0.9600 | C10—H10B | 0.9600 |
| C20—C21 | 1.383 (4) | C10—H10C | 0.9600 |
| C20—H20 | 0.9300 | C27—H27A | 0.9600 |
| C6—C5 | 1.374 (5) | C27—H27B | 0.9600 |
| C24—C23 | 1.382 (4) | C27—H27C | 0.9600 |
| O1—C1—N1 | 123.5 (3) | C32—C33—C34 | 120.9 (3) |
| O4—C18—N2 | 123.6 (3) | C14—C13—C12 | 120.1 (3) |
| C1—N1—C11 | 123.4 (2) | C14—C13—H13 | 120.0 |
| C18—N2—C28 | 124.2 (2) | C12—C13—H13 | 120.0 |
| C18—N2—H2 | 118.5 (17) | C21—C22—C23 | 119.4 (3) |
| C28—N2—H2 | 113.7 (17) | C21—C22—H22 | 120.3 |
| C9—O2—C6 | 117.7 (2) | C23—C22—H22 | 120.3 |
| O1—C1—C2 | 121.1 (2) | O6—C26—O5 | 122.6 (3) |
| N1—C1—C2 | 115.4 (2) | O6—C26—C27 | 126.8 (4) |
| C1—N1—H1 | 118.2 (17) | O5—C26—C27 | 110.6 (3) |
| C11—N1—H1 | 114.9 (17) | C5—C4—C3 | 119.6 (3) |
| C26—O5—C23 | 118.4 (2) | C5—C4—H4 | 120.2 |
| C33—C28—C29 | 121.0 (3) | C3—C4—H4 | 120.2 |
| C33—C28—N2 | 122.5 (3) | C31—C32—C33 | 122.1 (3) |
| C29—C28—N2 | 116.5 (2) | C31—C32—H32 | 118.9 |
| C20—C19—C24 | 121.4 (2) | C33—C32—H32 | 118.9 |
| C20—C19—C18 | 119.9 (3) | C30—C29—C28 | 119.8 (3) |
| C24—C19—C18 | 118.7 (2) | C30—C29—H29 | 120.1 |
| O4—C18—C19 | 121.1 (3) | C28—C29—H29 | 120.1 |
| N2—C18—C19 | 115.3 (2) | C4—C5—C6 | 119.6 (3) |
| C16—C11—C12 | 120.3 (3) | C4—C5—H5 | 120.2 |
| C16—C11—N1 | 122.5 (2) | C6—C5—H5 | 120.2 |
| C12—C11—N1 | 117.1 (2) | C14—C15—C16 | 121.3 (3) |
| C11—C16—C15 | 117.9 (3) | C14—C15—H15 | 119.4 |
| C11—C16—C17 | 121.8 (3) | C16—C15—H15 | 119.4 |
| C15—C16—C17 | 120.3 (3) | C22—C21—C20 | 119.8 (3) |
| C3—C2—C7 | 121.3 (3) | C22—C21—H21 | 120.1 |
| C3—C2—C1 | 119.0 (3) | C20—C21—H21 | 120.1 |
| C7—C2—C1 | 119.6 (2) | O3—C9—O2 | 121.8 (3) |
| C4—C3—C2 | 120.1 (3) | O3—C9—C10 | 127.5 (4) |
| C4—C3—H3 | 119.9 | O2—C9—C10 | 110.7 (3) |
| C2—C3—H3 | 119.9 | C30—C31—C32 | 120.2 (3) |
| C13—C12—C11 | 120.1 (3) | C30—C31—H31 | 119.9 |
| C13—C12—H12 | 119.9 | C32—C31—H31 | 119.9 |
| C11—C12—H12 | 119.9 | C13—C14—C15 | 120.2 (3) |
| C6—C7—C2 | 116.1 (3) | C13—C14—H14 | 119.9 |
| C6—C7—C8 | 121.5 (3) | C15—C14—H14 | 119.9 |
| C2—C7—C8 | 122.4 (3) | C24—C25—H25A | 109.5 |
| C16—C17—H17A | 109.5 | C24—C25—H25B | 109.5 |
| C16—C17—H17B | 109.5 | H25A—C25—H25B | 109.5 |
| H17A—C17—H17B | 109.5 | C24—C25—H25C | 109.5 |
| C16—C17—H17C | 109.5 | H25A—C25—H25C | 109.5 |
| H17A—C17—H17C | 109.5 | H25B—C25—H25C | 109.5 |
| H17B—C17—H17C | 109.5 | C31—C30—C29 | 119.7 (3) |
| C19—C20—C21 | 119.9 (3) | C31—C30—H30 | 120.2 |
| C19—C20—H20 | 120.0 | C29—C30—H30 | 120.2 |
| C21—C20—H20 | 120.0 | C7—C8—H8A | 109.5 |
| C5—C6—C7 | 123.1 (3) | C7—C8—H8B | 109.5 |
| C5—C6—O2 | 118.2 (3) | H8A—C8—H8B | 109.5 |
| C7—C6—O2 | 118.6 (3) | C7—C8—H8C | 109.5 |
| C23—C24—C19 | 116.4 (3) | H8A—C8—H8C | 109.5 |
| C23—C24—C25 | 121.7 (3) | H8B—C8—H8C | 109.5 |
| C19—C24—C25 | 121.8 (3) | C9—C10—H10A | 109.5 |
| C33—C34—H34A | 109.5 | C9—C10—H10B | 109.5 |
| C33—C34—H34B | 109.5 | H10A—C10—H10B | 109.5 |
| H34A—C34—H34B | 109.5 | C9—C10—H10C | 109.5 |
| C33—C34—H34C | 109.5 | H10A—C10—H10C | 109.5 |
| H34A—C34—H34C | 109.5 | H10B—C10—H10C | 109.5 |
| H34B—C34—H34C | 109.5 | C26—C27—H27A | 109.5 |
| C22—C23—C24 | 122.9 (3) | C26—C27—H27B | 109.5 |
| C22—C23—O5 | 118.5 (3) | H27A—C27—H27B | 109.5 |
| C24—C23—O5 | 118.4 (3) | C26—C27—H27C | 109.5 |
| C28—C33—C32 | 117.0 (3) | H27A—C27—H27C | 109.5 |
| C28—C33—C34 | 122.1 (3) | H27B—C27—H27C | 109.5 |
| C9—O2—C6—C7 | −100.0 (3) | C20—C19—C24—C23 | −0.3 (4) |
| N1—C1—C2—C7 | 129.1 (3) | C18—C19—C24—C23 | 179.3 (3) |
| C2—C1—N1—C11 | −172.4 (2) | C20—C19—C24—C25 | −177.9 (3) |
| C1—N1—C11—C16 | −66.4 (4) | C18—C19—C24—C25 | 1.7 (4) |
| C26—O5—C23—C24 | −83.7 (3) | C19—C24—C23—C22 | 1.8 (4) |
| C24—C19—C18—N2 | −113.6 (3) | C25—C24—C23—C22 | 179.4 (3) |
| C28—N2—C18—C19 | 166.2 (2) | C19—C24—C23—O5 | −172.5 (2) |
| C18—N2—C28—C33 | 66.0 (4) | C25—C24—C23—O5 | 5.1 (4) |
| N1—C1—C2—C3 | −53.9 (3) | C26—O5—C23—C22 | 101.7 (3) |
| O1—C1—N1—C11 | 8.5 (4) | C29—C28—C33—C32 | 3.9 (4) |
| C18—N2—C28—C29 | −114.4 (3) | N2—C28—C33—C32 | −176.5 (3) |
| C28—N2—C18—O4 | −13.4 (4) | C29—C28—C33—C34 | −173.8 (3) |
| C20—C19—C18—O4 | −114.4 (3) | N2—C28—C33—C34 | 5.8 (4) |
| C24—C19—C18—O4 | 66.0 (4) | C11—C12—C13—C14 | −0.3 (5) |
| C20—C19—C18—N2 | 66.0 (3) | C24—C23—C22—C21 | −1.6 (5) |
| C1—N1—C11—C12 | 116.4 (3) | O5—C23—C22—C21 | 172.7 (3) |
| C12—C11—C16—C15 | −3.6 (4) | C23—O5—C26—O6 | −5.3 (5) |
| N1—C11—C16—C15 | 179.2 (3) | C23—O5—C26—C27 | 174.0 (3) |
| C12—C11—C16—C17 | 173.8 (3) | C2—C3—C4—C5 | −0.8 (5) |
| N1—C11—C16—C17 | −3.3 (4) | C28—C33—C32—C31 | −2.0 (5) |
| O1—C1—C2—C3 | 125.3 (3) | C34—C33—C32—C31 | 175.7 (3) |
| O1—C1—C2—C7 | −51.7 (4) | C33—C28—C29—C30 | −3.0 (5) |
| C7—C2—C3—C4 | 1.3 (4) | N2—C28—C29—C30 | 177.4 (3) |
| C1—C2—C3—C4 | −175.6 (3) | C3—C4—C5—C6 | −0.1 (5) |
| C16—C11—C12—C13 | 3.0 (4) | C7—C6—C5—C4 | 0.6 (5) |
| N1—C11—C12—C13 | −179.7 (3) | O2—C6—C5—C4 | 176.4 (3) |
| C3—C2—C7—C6 | −0.8 (4) | C11—C16—C15—C14 | 1.6 (5) |
| C1—C2—C7—C6 | 176.1 (2) | C17—C16—C15—C14 | −175.9 (3) |
| C3—C2—C7—C8 | 179.1 (3) | C23—C22—C21—C20 | −0.1 (5) |
| C1—C2—C7—C8 | −4.0 (4) | C19—C20—C21—C22 | 1.6 (5) |
| C24—C19—C20—C21 | −1.4 (4) | C6—O2—C9—O3 | 4.8 (5) |
| C18—C19—C20—C21 | 179.0 (3) | C6—O2—C9—C10 | −175.4 (3) |
| C2—C7—C6—C5 | −0.1 (4) | C33—C32—C31—C30 | −0.9 (6) |
| C8—C7—C6—C5 | 179.9 (3) | C12—C13—C14—C15 | −1.7 (5) |
| C2—C7—C6—O2 | −175.9 (2) | C16—C15—C14—C13 | 1.0 (5) |
| C8—C7—C6—O2 | 4.1 (4) | C32—C31—C30—C29 | 2.0 (6) |
| C9—O2—C6—C5 | 84.0 (4) | C28—C29—C30—C31 | −0.1 (5) |
Hydrogen-bond geometry (Å, º)
Cg1 is the centroid of the C28–C33 ring.
| D—H···A | D—H | H···A | D···A | D—H···A |
| C5—H5···O6i | 0.93 | 2.49 | 3.402 (4) | 167 |
| N2—H2···O1ii | 0.88 (3) | 1.96 (3) | 2.813 (3) | 164 (2) |
| N1—H1···O4 | 0.91 (3) | 1.91 (3) | 2.804 (3) | 166 (2) |
| C25—H25B···O4 | 0.96 | 2.76 | 3.117 (4) | 103 |
| C34—H34A···O4 | 0.96 | 2.59 | 3.100 (4) | 114 |
| C8—H8B···O1 | 0.96 | 2.75 | 2.986 (4) | 95 |
| C3—H3···Cg1 | 0.93 | 2.81 | 3.666 (3) | 153 |
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z.
References
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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/S2056989019000021/yk2118sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019000021/yk2118Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989019000021/yk2118Isup3.cml
CCDC reference: 1584572
Additional supporting information: crystallographic information; 3D view; checkCIF report