One of the nine-membered 2,3-dihydro-1,3-benzoxazole rings and the phenyl ring are almost parallel to each other, making a dihedral angle of 5.30 (18)°. These rings are almost normal to the mean plane of the other nine-membered 2,3-dihydro-1,3-benzoxazole ring. The crystal structure features C—H⋯O hydrogen bonds and π–π stacking interactions.
Keywords: crystal structure; 2,3-dihydro-1,3-benzoxazole ring; semi-empirical CNDO/2 method; HOMO; LUMO
Abstract
In the molecular structure of the title compound, C24H19Cl2N3O4, the three C atoms of the central N,N-dimethylmethanamine moiety are bonded to the N atoms of the two 5-chloro-1,3-benzoxazol-2(3H)-one groups and to the methyl C atom of the methylbenzene group. One of the nine-membered 2,3-dihydro-1,3-benzoxazole rings and the phenyl ring are almost parallel to each other, making a dihedral angle of 5.30 (18)°, but they are almost normal to the mean plane of the other nine-membered 2,3-dihydro-1,3-benzoxazole ring, subtending dihedral angles of 89.29 (16) and 85.41 (18)°, respectively. The crystal structure features C—H⋯O hydrogen bonds and π–π stacking interactions [centroid-to-centroid distances = 3.5788 (19) Å, slippage = 0.438 and 3.7773 (16) Å, and slippage = 0.716 Å].
Chemical context
2(3H)-Benzoxazolone is a privileged lead molecule for the design of potential bioactive agents, and its derivatives have been shown to posses a broad spectrum of bioactive properties such as anti-HIV (Deng et al., 2006 ▸), anticancer (Ivanova et al., 2007 ▸), analgesic (Ünlü et al., 2003 ▸), anti-inflammatory (Köksal et al., 2005 ▸), antinociceptive (Önkol et al., 2001 ▸), antimicrobial (Köksal et al., 2002 ▸), anticonvulsant (Ucar et al., 1998 ▸), antimalarial (Courtois et al., 2004 ▸) and human leukocyte MPO clorinating inhibitor activities (Soyer et al., 2005 ▸). In this context, we have investigated another benzoxazolone derivative with formula C24H19Cl2N3O4, and report here its synthesis, molecular, crystal and theoretical structures.
Structural commentary
The central part of the title molecule (Fig. 1 ▸) comprises an N,N-dimethylmethanamine unit whose three carbon atoms are bonded to the N atoms of the two 5-chloro-1,3-benzoxazol-2(3H)-one moieties and to the methyl carbon atom of the methylbenzene group. The nine-membered 2,3-dihydro-1,3-benzoxazole ring (N3/O3/C10–C16) and the phenyl ring (C19–C24) are almost parallel to each other, making a dihedral angle of 5.30 (18)°. These two entities are almost normal to the mean plane of the other 2,3-dihydro-1,3-benzoxazole ring (N1/O1/C1–C7), subtending dihedral angles of 89.29 (16) and 85.41 (18)°, respectively.
Figure 1.
View of the title molecule with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
The C7—N1—C8—N2, N2—C9—N3—C16, N2—C17—C18—C19 and C17—C18—C19—C24 torsion angles are −90.7 (3), −75.6 (3), −63.6 (3) and 106.1 (4)°, respectively. The bond lengths and angles of the title molecule (Table 1 ▸) are normal and correspond to those observed in related benzoxazolone derivatives (Aydın et al., 2004 ▸, 2012 ▸, 2017 ▸; Allen et al., 1987 ▸).
Table 1. Comparison of experimental (X-ray) and theoretical (CNDO/2) bond lenghts and angles (Å, °) for the title compound.
| Bond | X-ray | CNDO/2 |
|---|---|---|
| Cl1—C4 | 1.735 (3) | 1.7379 |
| Cl2—C14 | 1.738 (3) | 1.7382 |
| O1—C1 | 1.382 (3) | 1.3545 |
| O1—C7 | 1.384 (3) | 1.3585 |
| O2—C7 | 1.202 (3) | 1.2091 |
| O3—C10 | 1.371 (3) | 1.3573 |
| O3—C11 | 1.390 (4) | 1.3544 |
| O4—C10 | 1.200 (4) | 1.2090 |
| N1—C6 | 1.398 (3) | 1.3649 |
| N1—C7 | 1.371 (3) | 1.3593 |
| N1—C8 | 1.491 (3) | 1.4587 |
| N2—C8 | 1.430 (4) | 1.4666 |
| N2—C9 | 1.448 (4) | 1.4641 |
| N2—C17 | 1.463 (4) | 1.4672 |
| N3—C9 | 1.444 (3) | 1.4601 |
| N3—C10 | 1.370 (4) | 1.3587 |
| N3—C16 | 1.393 (3) | 1.3663 |
| C17—C18 | 1.520 (4) | 1.5425 |
| C18—C19 | 1.506 (4) | 1.5131 |
| C8—N2—C9 | 112.5 (2) | 110.47 |
| C8—N2—C17 | 114.76 (19) | 112.03 |
| C9—N2—C17 | 114.5 (2) | 110.74 |
| Cl1—C4—C3 | 118.03 (19) | 120.09 |
| Cl1—C4—C5 | 118.6 (2) | 119.73 |
| O1—C7—O2 | 123.0 (3) | 124.49 |
| O2—C7—N1 | 129.6 (3) | 127.02 |
| N1—C8—N2 | 115.9 (2) | 112.31 |
| N2—C9—N3 | 111.3 (2) | 111.17 |
| O3—C10—O4 | 123.5 (3) | 124.70 |
| O4—C10—N3 | 128.3 (3) | 126.73 |
| Cl2—C14—C13 | 118.4 (2) | 120.07 |
| Cl2—C14—C15 | 118.6 (2) | 119.71 |
| N2—C17—C18 | 111.8 (2) | 112.23 |
| C17—C18—C19 | 112.9 (2) | 114.03 |
| C18—C19—C20 | 121.2 (3) | 120.60 |
| C18—C19—C24 | 121.2 (3) | 121.28 |
Supramolecular features
The crystal structure features weak intermolecular C—H⋯O hydrogen bonds (Table 2 ▸, Fig. 2 ▸) between a methylene group and a carbonyl O atom of a neighbouring molecule. π–π stacking interactions [Cg1⋯Cg3ii = 3.5788 (19) Å, slippage = 0.438 Å and Cg2⋯Cg2iii = 3.7773 (16) Å, slippage = 0.716 Å, symmetry codes: (ii) x, −1 + y, z, (iii) 1 − x, 1 − y, 1 − z, where Cg1, Cg2 and Cg3 are the centroids of the O3/N3/C10/C11/C16 2,3-dihydro-1,3-oxazole ring, the C1–C6 benzene ring and the C19–C24 phenyl ring, respectively] additionally consolidate the crystal packing.
Table 2. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C8—H8A⋯O4i | 0.97 | 2.51 | 3.037 (4) | 114 |
Symmetry code: (i) 
.
Figure 2.
A view of the crystal packing in the title structure, showing the C—H⋯O hydrogen bonding and π–π stacking interactions. H atoms not involved in hydrogen bonds are omitted for the sake of clarity. [Symmetry codes: (a) x − 1, y, z; (b) x, y − 1, z; (c) 1 − x, 1 − y, 1 − z.]
Theoretical calculations
Semi-empirical molecular orbital (MO) calculations of the title molecule were carried out using the CNDO/2 method (Pople & Segal, 1966 ▸). It is based on the Complete Neglect of Differential Overlap integral approximation. The semi-empirical CNDO/2 parameterization is widely used to derive bond lengths, bond angles, torsion angles, atom charges, HOMO and LUMO energy levels, dipole moments, polarizability, etc. The spatial view of the title compound calculated as a closed-shell in a vacuum at 0 K is shown in Fig. 3 ▸.
Figure 3.
The molecular structure of the title compound calculated using the CNDO/2 method.
In the title molecule, the calculated charges on the Cl1, Cl2, O1, O2, O3, O4, N1, N2 and N3 atoms are −0.164, −0.226, −0.424, −0.228, −0.431, −0.117, −0.187 and −0.112 e−, respectively. The calculated dipole moment is about 2.122 Debye. The HOMO and LUMO energy levels are −10.7480 and 3.4691 eV, respectively.
The calculated bond lengths and angles of the title molecule are consistent with those obtained by X-ray structure determination within error limits (Table 1 ▸). Looking at Figs. 1 ▸ and 3 ▸, the experimental and calculated conformations appear to be quite different. This is supported by the torsion angles N1—C8—N2—C17 [experimental 70.5 (3), calculated 58.25°], N1—C8—N2—C9 [−62.8 (3), −177.78°], N2—C17—C18—C19 [−63.6 (3), −150.35°], C18—C17—N2—C8 [84.1 (3), −95.53°] and C9—N2—C17—18 [143.5 (2), −140.65°]. The small differences between the theoretical and experimental results are due to the calculations being in a vacuum and at 0 K.
Synthesis and crystallization
4-Chloro-2-aminophenol (10 mmol), urea (50 mmol) and 37%wt HCl (2.5 ml) were irradiated (300 W, 413 K) for 15 min in a microwave oven. After completion of the reaction (monitored with TLC), water (10 ml) was added to the reaction mixture and stirred at room temperature for 1 h. The resulting precipitate was filtered and washed with water. After drying the precipitate, crystallization from ethanol–water (1:1 v/v) yielded 5-chloro-2(3H)-benzoxazolone. This compound (2 mmol) was dissolved in methanol (5 ml). Phenethylamine (2 mmol) and 37%wt formalin (2.5 mmol) were added to this solution. The mixture was then stirred vigorously for 1 h. The resulting precipitate was filtered and washed with cold methanol. The crude product was recrystallized from methanol, yield 40%; m.p. 427 K.
IR υmax (FTIR/ATR): 3062, 2862, 1769, 1038 cm−1; 1H NMR (CDCl3): δ 2.79 (2H, t, J = 6.8 Hz, NCH2CH2), 3.14 (2H, t, J = 7.0 Hz, CH2CH2-phenyl) 4.90 (4H, s, 2 × CH2), 6.88–7.16 (11H, m, Ar-H) ppm; MS (ESI) m/z (%): 315 (100), 317 (37), 484 (M + H, 3), 486 (M + H + 2, 1).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 (aromatic) and 0.97 (methylene) Å and U iso = 1.2U eq(C).
Table 3. Experimental details.
| Crystal data | |
| Chemical formula | C24H19Cl2N3O4 |
| M r | 484.32 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 296 |
| a, b, c (Å) | 7.4028 (5), 7.4432 (5), 22.4616 (15) |
| α, β, γ (°) | 97.255 (5), 90.274 (5), 114.784 (5) |
| V (Å3) | 1112.36 (14) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.33 |
| Crystal size (mm) | 0.61 × 0.26 × 0.04 |
| Data collection | |
| Diffractometer | Stoe IPDS 2 |
| Absorption correction | Integration (X-RED32; Stoe & Cie, 2002 ▸) |
| T min, T max | 0.901, 0.987 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 15409, 4604, 2261 |
| R int | 0.083 |
| (sin θ/λ)max (Å−1) | 0.628 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.043, 0.089, 0.87 |
| No. of reflections | 4604 |
| No. of parameters | 298 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.13, −0.17 |
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018005984/wm5440sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005984/wm5440Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018005984/wm5440Isup3.cml
CCDC reference: 1838126
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
| C24H19Cl2N3O4 | Z = 2 |
| Mr = 484.32 | F(000) = 500 |
| Triclinic, P1 | Dx = 1.446 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.4028 (5) Å | Cell parameters from 12292 reflections |
| b = 7.4432 (5) Å | θ = 1.8–27.2° |
| c = 22.4616 (15) Å | µ = 0.33 mm−1 |
| α = 97.255 (5)° | T = 296 K |
| β = 90.274 (5)° | Plate, light yellow |
| γ = 114.784 (5)° | 0.61 × 0.26 × 0.04 mm |
| V = 1112.36 (14) Å3 |
Data collection
| Stoe IPDS 2 diffractometer | 4604 independent reflections |
| Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2261 reflections with I > 2σ(I) |
| Plane graphite monochromator | Rint = 0.083 |
| Detector resolution: 6.67 pixels mm-1 | θmax = 26.5°, θmin = 1.8° |
| ω scans | h = −9→9 |
| Absorption correction: integration (XRED-32; Stoe & Cie, 2002) | k = −9→9 |
| Tmin = 0.901, Tmax = 0.987 | l = −28→28 |
| 15409 measured reflections |
Refinement
| 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.089 | H-atom parameters constrained |
| S = 0.87 | w = 1/[σ2(Fo2) + (0.0273P)2] where P = (Fo2 + 2Fc2)/3 |
| 4604 reflections | (Δ/σ)max < 0.001 |
| 298 parameters | Δρmax = 0.13 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
Special details
| Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
| Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > 2sigma(F2) is used only for calculating -R-factor-obs 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)
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.33895 (11) | 0.91821 (11) | 0.55979 (3) | 0.0695 (3) | |
| Cl2 | −0.03618 (13) | 0.22527 (15) | 0.03733 (4) | 0.0993 (4) | |
| O1 | 0.1417 (3) | 0.1051 (3) | 0.45148 (8) | 0.0614 (7) | |
| O2 | 0.0466 (3) | −0.0234 (3) | 0.35320 (9) | 0.0774 (8) | |
| O3 | 0.7070 (3) | 0.3740 (3) | 0.16410 (8) | 0.0729 (8) | |
| O4 | 0.7524 (3) | 0.3741 (4) | 0.26394 (9) | 0.0931 (10) | |
| N1 | 0.1491 (3) | 0.3147 (3) | 0.38837 (9) | 0.0519 (7) | |
| N2 | 0.2740 (3) | 0.4370 (3) | 0.29248 (8) | 0.0487 (8) | |
| N3 | 0.4467 (3) | 0.3171 (3) | 0.21984 (9) | 0.0542 (8) | |
| C1 | 0.1949 (3) | 0.2919 (4) | 0.48420 (11) | 0.0502 (9) | |
| C2 | 0.2325 (4) | 0.3444 (4) | 0.54484 (11) | 0.0567 (10) | |
| C3 | 0.2776 (3) | 0.5405 (4) | 0.56779 (11) | 0.0548 (9) | |
| C4 | 0.2845 (3) | 0.6740 (4) | 0.52899 (11) | 0.0490 (9) | |
| C5 | 0.2442 (3) | 0.6204 (4) | 0.46734 (11) | 0.0487 (9) | |
| C6 | 0.2011 (3) | 0.4255 (4) | 0.44584 (10) | 0.0465 (9) | |
| C7 | 0.1063 (4) | 0.1186 (4) | 0.39202 (12) | 0.0598 (11) | |
| C8 | 0.1117 (4) | 0.3782 (4) | 0.33094 (10) | 0.0548 (9) | |
| C9 | 0.3282 (4) | 0.2752 (4) | 0.27152 (11) | 0.0560 (10) | |
| C10 | 0.6446 (4) | 0.3553 (4) | 0.22130 (13) | 0.0671 (11) | |
| C11 | 0.5420 (4) | 0.3407 (4) | 0.12702 (12) | 0.0570 (10) | |
| C12 | 0.5348 (4) | 0.3392 (5) | 0.06646 (13) | 0.0723 (11) | |
| C13 | 0.3512 (5) | 0.2999 (5) | 0.03966 (12) | 0.0706 (11) | |
| C14 | 0.1891 (4) | 0.2687 (4) | 0.07364 (12) | 0.0622 (11) | |
| C15 | 0.1980 (4) | 0.2725 (4) | 0.13546 (12) | 0.0575 (10) | |
| C16 | 0.3809 (4) | 0.3077 (4) | 0.16085 (10) | 0.0507 (9) | |
| C17 | 0.4427 (4) | 0.6267 (4) | 0.31468 (11) | 0.0577 (10) | |
| C18 | 0.4109 (5) | 0.8042 (4) | 0.29870 (11) | 0.0722 (11) | |
| C19 | 0.3978 (5) | 0.8067 (4) | 0.23191 (13) | 0.0697 (11) | |
| C20 | 0.5647 (6) | 0.8579 (5) | 0.19940 (15) | 0.0932 (14) | |
| C21 | 0.5538 (8) | 0.8637 (6) | 0.13801 (19) | 0.122 (2) | |
| C22 | 0.3763 (11) | 0.8152 (7) | 0.1095 (2) | 0.136 (3) | |
| C23 | 0.2082 (9) | 0.7639 (6) | 0.1404 (2) | 0.121 (2) | |
| C24 | 0.2183 (6) | 0.7582 (5) | 0.20128 (15) | 0.0887 (14) | |
| H2 | 0.22790 | 0.25200 | 0.56970 | 0.0680* | |
| H3 | 0.30310 | 0.58280 | 0.60900 | 0.0660* | |
| H5 | 0.24630 | 0.71120 | 0.44220 | 0.0580* | |
| H8A | −0.00220 | 0.26870 | 0.30880 | 0.0660* | |
| H8B | 0.07580 | 0.48940 | 0.34060 | 0.0660* | |
| H9A | 0.40320 | 0.25540 | 0.30360 | 0.0670* | |
| H9B | 0.20820 | 0.15270 | 0.26090 | 0.0670* | |
| H12 | 0.64670 | 0.36320 | 0.04440 | 0.0870* | |
| H13 | 0.33700 | 0.29450 | −0.00180 | 0.0850* | |
| H15 | 0.08810 | 0.25270 | 0.15810 | 0.0690* | |
| H17A | 0.56300 | 0.62780 | 0.29750 | 0.0690* | |
| H17B | 0.46100 | 0.63870 | 0.35800 | 0.0690* | |
| H18A | 0.28880 | 0.80080 | 0.31520 | 0.0870* | |
| H18B | 0.52020 | 0.92670 | 0.31720 | 0.0870* | |
| H20 | 0.68740 | 0.88940 | 0.21890 | 0.1120* | |
| H21 | 0.66850 | 0.90090 | 0.11680 | 0.1460* | |
| H22 | 0.36810 | 0.81670 | 0.06830 | 0.1640* | |
| H23 | 0.08630 | 0.73270 | 0.12030 | 0.1450* | |
| H24 | 0.10250 | 0.72110 | 0.22200 | 0.1070* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0777 (5) | 0.0615 (5) | 0.0641 (5) | 0.0269 (4) | 0.0050 (4) | −0.0006 (4) |
| Cl2 | 0.0934 (6) | 0.1463 (9) | 0.0720 (6) | 0.0683 (6) | −0.0183 (5) | 0.0007 (5) |
| O1 | 0.0774 (12) | 0.0546 (12) | 0.0547 (12) | 0.0289 (10) | 0.0104 (9) | 0.0128 (10) |
| O2 | 0.1047 (16) | 0.0566 (13) | 0.0598 (13) | 0.0252 (12) | 0.0167 (11) | 0.0014 (11) |
| O3 | 0.0563 (11) | 0.1035 (16) | 0.0651 (13) | 0.0394 (12) | 0.0080 (10) | 0.0133 (12) |
| O4 | 0.0797 (15) | 0.142 (2) | 0.0701 (14) | 0.0601 (15) | −0.0131 (12) | 0.0120 (14) |
| N1 | 0.0590 (13) | 0.0511 (13) | 0.0451 (12) | 0.0215 (11) | 0.0062 (10) | 0.0117 (10) |
| N2 | 0.0526 (13) | 0.0542 (14) | 0.0412 (12) | 0.0238 (12) | 0.0059 (10) | 0.0094 (10) |
| N3 | 0.0562 (14) | 0.0671 (15) | 0.0434 (13) | 0.0297 (12) | 0.0032 (10) | 0.0090 (11) |
| C1 | 0.0504 (15) | 0.0532 (17) | 0.0506 (16) | 0.0255 (14) | 0.0034 (12) | 0.0068 (13) |
| C2 | 0.0639 (17) | 0.0652 (19) | 0.0477 (16) | 0.0313 (15) | 0.0018 (13) | 0.0170 (14) |
| C3 | 0.0542 (15) | 0.0677 (19) | 0.0441 (14) | 0.0268 (15) | 0.0000 (12) | 0.0100 (14) |
| C4 | 0.0458 (15) | 0.0503 (16) | 0.0505 (16) | 0.0204 (13) | 0.0030 (12) | 0.0051 (13) |
| C5 | 0.0485 (14) | 0.0529 (16) | 0.0472 (15) | 0.0224 (13) | 0.0068 (11) | 0.0127 (12) |
| C6 | 0.0449 (14) | 0.0559 (17) | 0.0414 (15) | 0.0226 (13) | 0.0077 (11) | 0.0119 (13) |
| C7 | 0.0707 (19) | 0.061 (2) | 0.0515 (18) | 0.0301 (17) | 0.0141 (14) | 0.0125 (15) |
| C8 | 0.0573 (16) | 0.0670 (18) | 0.0434 (14) | 0.0294 (15) | 0.0018 (12) | 0.0086 (13) |
| C9 | 0.0674 (17) | 0.0600 (18) | 0.0432 (15) | 0.0283 (15) | 0.0062 (13) | 0.0117 (13) |
| C10 | 0.0627 (19) | 0.084 (2) | 0.0610 (19) | 0.0375 (17) | 0.0037 (15) | 0.0097 (17) |
| C11 | 0.0551 (17) | 0.0645 (18) | 0.0553 (17) | 0.0290 (15) | 0.0049 (13) | 0.0084 (14) |
| C12 | 0.074 (2) | 0.097 (2) | 0.0583 (19) | 0.0455 (19) | 0.0214 (15) | 0.0207 (17) |
| C13 | 0.090 (2) | 0.092 (2) | 0.0431 (16) | 0.0499 (19) | 0.0109 (16) | 0.0146 (15) |
| C14 | 0.0710 (19) | 0.072 (2) | 0.0510 (17) | 0.0381 (17) | −0.0010 (14) | 0.0069 (15) |
| C15 | 0.0579 (16) | 0.0672 (19) | 0.0540 (16) | 0.0325 (15) | 0.0094 (13) | 0.0097 (14) |
| C16 | 0.0576 (16) | 0.0556 (16) | 0.0438 (15) | 0.0283 (14) | 0.0075 (13) | 0.0087 (12) |
| C17 | 0.0647 (17) | 0.0614 (18) | 0.0443 (15) | 0.0243 (16) | 0.0019 (13) | 0.0070 (13) |
| C18 | 0.102 (2) | 0.0616 (19) | 0.0517 (17) | 0.0336 (18) | 0.0064 (16) | 0.0067 (15) |
| C19 | 0.107 (2) | 0.0455 (17) | 0.0530 (18) | 0.0285 (18) | 0.0043 (18) | 0.0077 (14) |
| C20 | 0.121 (3) | 0.075 (2) | 0.071 (2) | 0.028 (2) | 0.017 (2) | 0.0145 (19) |
| C21 | 0.188 (5) | 0.091 (3) | 0.073 (3) | 0.041 (3) | 0.045 (3) | 0.029 (2) |
| C22 | 0.254 (7) | 0.086 (3) | 0.066 (3) | 0.069 (4) | −0.008 (4) | 0.013 (2) |
| C23 | 0.184 (5) | 0.090 (3) | 0.088 (3) | 0.061 (3) | −0.041 (3) | 0.002 (3) |
| C24 | 0.123 (3) | 0.070 (2) | 0.074 (2) | 0.042 (2) | −0.011 (2) | 0.0095 (18) |
Geometric parameters (Å, º)
| Cl1—C4 | 1.735 (3) | C15—C16 | 1.373 (4) |
| Cl2—C14 | 1.738 (3) | C17—C18 | 1.520 (4) |
| O1—C1 | 1.382 (3) | C18—C19 | 1.506 (4) |
| O1—C7 | 1.384 (3) | C19—C20 | 1.375 (6) |
| O2—C7 | 1.202 (3) | C19—C24 | 1.377 (6) |
| O3—C10 | 1.371 (3) | C20—C21 | 1.388 (5) |
| O3—C11 | 1.390 (4) | C21—C22 | 1.343 (10) |
| O4—C10 | 1.200 (4) | C22—C23 | 1.361 (10) |
| N1—C6 | 1.398 (3) | C23—C24 | 1.376 (6) |
| N1—C7 | 1.371 (3) | C2—H2 | 0.9300 |
| N1—C8 | 1.491 (3) | C3—H3 | 0.9300 |
| N2—C8 | 1.430 (4) | C5—H5 | 0.9300 |
| N2—C9 | 1.448 (4) | C8—H8A | 0.9700 |
| N2—C17 | 1.463 (4) | C8—H8B | 0.9700 |
| N3—C9 | 1.444 (3) | C9—H9A | 0.9700 |
| N3—C10 | 1.370 (4) | C9—H9B | 0.9700 |
| N3—C16 | 1.393 (3) | C12—H12 | 0.9300 |
| C1—C2 | 1.362 (3) | C13—H13 | 0.9300 |
| C1—C6 | 1.383 (4) | C15—H15 | 0.9300 |
| C2—C3 | 1.381 (4) | C17—H17A | 0.9700 |
| C3—C4 | 1.388 (4) | C17—H17B | 0.9700 |
| C4—C5 | 1.387 (3) | C18—H18A | 0.9700 |
| C5—C6 | 1.369 (4) | C18—H18B | 0.9700 |
| C11—C12 | 1.360 (4) | C20—H20 | 0.9300 |
| C11—C16 | 1.368 (4) | C21—H21 | 0.9300 |
| C12—C13 | 1.382 (5) | C22—H22 | 0.9300 |
| C13—C14 | 1.377 (5) | C23—H23 | 0.9300 |
| C14—C15 | 1.386 (4) | C24—H24 | 0.9300 |
| C1—O1—C7 | 107.7 (2) | C19—C20—C21 | 121.3 (4) |
| C10—O3—C11 | 107.1 (2) | C20—C21—C22 | 119.5 (5) |
| C6—N1—C7 | 109.6 (2) | C21—C22—C23 | 120.6 (4) |
| C6—N1—C8 | 128.6 (2) | C22—C23—C24 | 120.1 (6) |
| C7—N1—C8 | 121.2 (2) | C19—C24—C23 | 120.8 (4) |
| C8—N2—C9 | 112.5 (2) | C1—C2—H2 | 121.00 |
| C8—N2—C17 | 114.76 (19) | C3—C2—H2 | 121.00 |
| C9—N2—C17 | 114.5 (2) | C2—C3—H3 | 120.00 |
| C9—N3—C10 | 123.4 (2) | C4—C3—H3 | 120.00 |
| C9—N3—C16 | 127.5 (2) | C4—C5—H5 | 122.00 |
| C10—N3—C16 | 108.9 (2) | C6—C5—H5 | 122.00 |
| O1—C1—C2 | 127.6 (2) | N1—C8—H8A | 108.00 |
| O1—C1—C6 | 109.5 (2) | N1—C8—H8B | 108.00 |
| C2—C1—C6 | 122.9 (2) | N2—C8—H8A | 108.00 |
| C1—C2—C3 | 117.2 (2) | N2—C8—H8B | 108.00 |
| C2—C3—C4 | 119.5 (2) | H8A—C8—H8B | 107.00 |
| Cl1—C4—C3 | 118.03 (19) | N2—C9—H9A | 109.00 |
| Cl1—C4—C5 | 118.6 (2) | N2—C9—H9B | 109.00 |
| C3—C4—C5 | 123.3 (2) | N3—C9—H9A | 109.00 |
| C4—C5—C6 | 115.8 (2) | N3—C9—H9B | 109.00 |
| N1—C6—C1 | 105.7 (2) | H9A—C9—H9B | 108.00 |
| N1—C6—C5 | 133.2 (2) | C11—C12—H12 | 122.00 |
| C1—C6—C5 | 121.1 (2) | C13—C12—H12 | 122.00 |
| O1—C7—O2 | 123.0 (3) | C12—C13—H13 | 120.00 |
| O1—C7—N1 | 107.5 (2) | C14—C13—H13 | 120.00 |
| O2—C7—N1 | 129.6 (3) | C14—C15—H15 | 122.00 |
| N1—C8—N2 | 115.9 (2) | C16—C15—H15 | 122.00 |
| N2—C9—N3 | 111.3 (2) | N2—C17—H17A | 109.00 |
| O3—C10—O4 | 123.5 (3) | N2—C17—H17B | 109.00 |
| O3—C10—N3 | 108.3 (2) | C18—C17—H17A | 109.00 |
| O4—C10—N3 | 128.3 (3) | C18—C17—H17B | 109.00 |
| O3—C11—C12 | 127.0 (3) | H17A—C17—H17B | 108.00 |
| O3—C11—C16 | 109.4 (2) | C17—C18—H18A | 109.00 |
| C12—C11—C16 | 123.5 (3) | C17—C18—H18B | 109.00 |
| C11—C12—C13 | 115.9 (3) | C19—C18—H18A | 109.00 |
| C12—C13—C14 | 120.7 (3) | C19—C18—H18B | 109.00 |
| Cl2—C14—C13 | 118.4 (2) | H18A—C18—H18B | 108.00 |
| Cl2—C14—C15 | 118.6 (2) | C19—C20—H20 | 119.00 |
| C13—C14—C15 | 123.0 (3) | C21—C20—H20 | 119.00 |
| C14—C15—C16 | 115.1 (3) | C20—C21—H21 | 120.00 |
| N3—C16—C11 | 106.3 (3) | C22—C21—H21 | 120.00 |
| N3—C16—C15 | 132.1 (3) | C21—C22—H22 | 120.00 |
| C11—C16—C15 | 121.6 (2) | C23—C22—H22 | 120.00 |
| N2—C17—C18 | 111.8 (2) | C22—C23—H23 | 120.00 |
| C17—C18—C19 | 112.9 (2) | C24—C23—H23 | 120.00 |
| C18—C19—C20 | 121.2 (3) | C19—C24—H24 | 120.00 |
| C18—C19—C24 | 121.2 (3) | C23—C24—H24 | 120.00 |
| C20—C19—C24 | 117.7 (3) | ||
| C7—O1—C1—C2 | 176.3 (3) | O1—C1—C2—C3 | −178.1 (3) |
| C7—O1—C1—C6 | −2.3 (3) | C2—C1—C6—N1 | −178.4 (3) |
| C1—O1—C7—N1 | 3.4 (3) | C2—C1—C6—C5 | −0.7 (4) |
| C1—O1—C7—O2 | −175.8 (3) | O1—C1—C6—C5 | 178.0 (2) |
| C11—O3—C10—N3 | −1.7 (3) | C1—C2—C3—C4 | −0.6 (4) |
| C11—O3—C10—O4 | 179.4 (3) | C2—C3—C4—Cl1 | 179.3 (2) |
| C10—O3—C11—C16 | 1.8 (3) | C2—C3—C4—C5 | 1.3 (4) |
| C10—O3—C11—C12 | −178.1 (3) | C3—C4—C5—C6 | −1.6 (4) |
| C8—N1—C7—O1 | −175.2 (2) | Cl1—C4—C5—C6 | −179.6 (2) |
| C6—N1—C7—O1 | −3.3 (3) | C4—C5—C6—N1 | 178.3 (3) |
| C6—N1—C8—N2 | 99.0 (3) | C4—C5—C6—C1 | 1.3 (4) |
| C7—N1—C8—N2 | −90.7 (3) | C12—C11—C16—C15 | −0.8 (5) |
| C7—N1—C6—C1 | 1.9 (3) | C12—C11—C16—N3 | 178.7 (3) |
| C8—N1—C6—C1 | 173.1 (3) | O3—C11—C12—C13 | 179.3 (3) |
| C7—N1—C6—C5 | −175.4 (3) | C16—C11—C12—C13 | −0.6 (5) |
| C8—N1—C6—C5 | −4.3 (5) | O3—C11—C16—N3 | −1.1 (3) |
| C6—N1—C7—O2 | 175.9 (3) | O3—C11—C16—C15 | 179.4 (2) |
| C8—N1—C7—O2 | 3.9 (5) | C11—C12—C13—C14 | 1.2 (5) |
| C17—N2—C8—N1 | −70.5 (3) | C12—C13—C14—C15 | −0.6 (5) |
| C9—N2—C17—C18 | 143.5 (2) | C12—C13—C14—Cl2 | 178.7 (3) |
| C8—N2—C9—N3 | 162.6 (2) | Cl2—C14—C15—C16 | −180.0 (2) |
| C9—N2—C8—N1 | 62.8 (3) | C13—C14—C15—C16 | −0.7 (4) |
| C8—N2—C17—C18 | −84.1 (3) | C14—C15—C16—C11 | 1.4 (4) |
| C17—N2—C9—N3 | −64.0 (3) | C14—C15—C16—N3 | −178.0 (3) |
| C9—N3—C10—O3 | 175.6 (2) | N2—C17—C18—C19 | −63.6 (3) |
| C16—N3—C10—O3 | 1.1 (3) | C17—C18—C19—C20 | −74.1 (4) |
| C10—N3—C16—C11 | 0.0 (3) | C17—C18—C19—C24 | 106.1 (4) |
| C9—N3—C16—C15 | 5.2 (5) | C18—C19—C20—C21 | −178.9 (3) |
| C9—N3—C10—O4 | −5.6 (5) | C24—C19—C20—C21 | 1.0 (5) |
| C16—N3—C10—O4 | 179.9 (3) | C18—C19—C24—C23 | 179.0 (3) |
| C10—N3—C16—C15 | 179.5 (3) | C20—C19—C24—C23 | −0.9 (5) |
| C10—N3—C9—N2 | 110.9 (3) | C19—C20—C21—C22 | −1.1 (6) |
| C16—N3—C9—N2 | −75.6 (3) | C20—C21—C22—C23 | 1.1 (7) |
| C9—N3—C16—C11 | −174.2 (2) | C21—C22—C23—C24 | −1.0 (7) |
| C6—C1—C2—C3 | 0.3 (4) | C22—C23—C24—C19 | 0.9 (6) |
| O1—C1—C6—N1 | 0.3 (3) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C8—H8A···O4i | 0.97 | 2.51 | 3.037 (4) | 114 |
| C9—H9A···O4 | 0.97 | 2.56 | 2.921 (4) | 102 |
| C17—H17A···N3 | 0.97 | 2.54 | 2.944 (3) | 105 |
Symmetry code: (i) x−1, y, 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) global, I. DOI: 10.1107/S2056989018005984/wm5440sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989018005984/wm5440Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989018005984/wm5440Isup3.cml
CCDC reference: 1838126
Additional supporting information: crystallographic information; 3D view; checkCIF report