research communications
Synthesis, b]benzo[5,6][1,4]oxazino[2,3-e][1,4]oxazine
and Hirshfeld surface analysis of 1,7-dimethyl-5a,6,11a,12-tetrahydrobenzo[aDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, Samsun, 55200, Turkey, bDepartment of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayıs, University, Samsun, 55200, Turkey, and cDepartment of Computer and Electronic Engineering Technology, Sana'a Community, College, Sana'a, Yemen
*Correspondence e-mail: 'necmisamsun@gmail.com', eiad.saif@scc.edu.ye
Molecules of the title compound, C16H16N2O2, occupy special positions on the twofold rotation axes. The heterocyclic ring adopts a slightly twisted with one of the two junction carbon atoms as the flap. The mean planes through the two halves of the molecule form a dihedral angle of 72.01 (2)°. In the crystal, molecules are linked by pairs of C—H⋯O and N—H⋯C contacts into layers parallel to (100). H⋯H contacts make the largest contribution to the Hirshfeld surface (58.9%).
Keywords: crystal structure; Hirshfeld surface; DFT; oxazines.
CCDC reference: 2021045
1. Chemical context
The title oxazine derivative contains two six-membered heterocyclic rings located between two benzene rings. Oxazine-derived compounds are used in the synthesis of detergents, corrosion inhibitors and industrial dyes (Adib et al., 2006). This class of molecules has been studied extensively as they exhibit antitumor (Sriharsha et al., 2006), antibacterial and antifungal (Belz et al., 2013) activity. Oxazinooxazines are important heterocyclic precursors in the construction of heteropropellanes with applications in material sciences and medicinal chemistry (Dilmaç et al., 2017). Such heterocycles can be synthesized by several methods (Konstantinova et al., 2020), with the most direct route being the condensation of amino with either or (Hajji et al., 2003). As the amino and hydroxy groups are adjacent, 2-aminophenol readily forms heterocycles. An interesting feature of the reaction is the stereo-selective transformation of glyoxal. We report herein the and Hirshfeld surface analysis for a new oxazine derivative, 1,7-dimethyl-5a,6,11a,12-tetrahydrobenzo[b]benzo[5,6][1,4]oxazino[2,3-e][1,4]oxazine.
2. Structural commentary
The molecular structure of the title compound (I) is shown in Fig. 1. The molecules occupy special positions on the twofold rotation axes. The heterocyclic ring adopts a slightly twisted with the C8* [symmetry code: (*) −x − 1, y, −z − ] atom as the flap. Except for this atom, the symmetry-independent part of the molecule (C2–C8/O1/N1) is nearly planar, the largest separation from the mean plane being 0.1267 (10) Å for O1. The mean planes of the two halves of the molecule form a dihedral angle of 72.01 (2)°.
3. Supramolecular features
Surprisingly, no intermolecular N—H⋯O contacts are observed in the title structure. Instead, C—H⋯O and N—H⋯C contacts are formed, the latter really being of the N—H⋯π type. Pairs of C—H⋯O contacts link the molecules into zigzag chains along [001] (Table 1, Fig. 2). Pairs of N—H⋯O contacts also form zigzag chains of molecules along [001] (Table 1, Fig. 3). As a result, layers parallel to (100) are formed (Fig. 4).
4. Hirshfeld surface
The Hirshfeld surfaces were generated using Crystal Explorer 17.5 (Turner et al., 2017). The dnorm mapping was performed in the range of −0.186 to 1.019 arbitrary units. Red spots on the dnorm surface (Fig. 5) indicate regions of C—H⋯O interactions. However, the N—H⋯C contacts do not cause red spots on the Hirshfeld surface. Other red spots are due to the H⋯H interactions, as can be understood from the fingerprint plot. The characteristic flat surface patches caused by planar stacking are shown in Fig. 6a. The shape-index map (Fig. 6b) does not contain red and blue triangles related to π–π interactions. Fig. 6c,d show the di and de surfaces, respectively. Fig. 7 presents the two-dimensional fingerprint plot for the title molecule and those delineated into the specific types of interactions. The H⋯H contacts make the largest contribution to the Hirshfeld surface (58.9%). The H⋯C/C⋯H interactions are seen at the edges of two-dimensional fingerprint drawings, with a general contribution of 24.6%.
5. Database survey
A search of the Cambridge Structural Database (CSD, version 5.40, update of August 2019; Groom et al., 2016) using 1-benzyl-3,4-dihydroquinoxalin-2(1H)-one as the main skeleton revealed the presence of four structures similar to the title compound. These are 2,8-di-t-butyl-5a,6,11a,12-tetrahydro[1,4]benzoxazino[3,672-b][1,4]benzoxazine (MOYJOC; Niklas et al., 2019), 5a,6,11a,12-tetrahydro[1,4]benzoxazino[3,2-b][1,4]benzoxazine (FIGVOG; Tauer et al., 1986), 5a,6,11a,12-tetrahydro-5a,11a-dimethyl-1,4-benzoxazino[3,2-b][1,4]benzoxazine (ABEQAA; Hai-Yan et al., 2004) and N,N′-di-5a,6,11a,12-tetrahydro[1,4]benzoxazino[3,2]benzoxazine (BAJNIJ; Farfán et al., 1992). In the structures MOYJOC and FIGVOG, the dihedral angles between the two approximately planar halves of the molecule [67.11 (3) and 64.28 (2)°, respectively] are smaller than in (I). In MOYJOC, both NH groups are involved in hydrogen bonds with the heterocyclic oxygen atoms. In FIGVOG, only one NH group takes part in such hydrogen bonding, while the other makes an N—H⋯C contact similar to that observed in (I). In ABEQAA, the hydrogen atoms at the bridge C atoms (C8 and C8* in the title molecule) are replaced by methyl groups. As a result, the dihedral angle increases to 81.70 (2)°. In this structure, both NH groups form weak intermolecular N—H⋯O hydrogen bonds.
6. Synthesis and crystallization
To a solution of 2-amino-3-methylphenol (21.8 mg, 0.177 mmol) in ethanol (20 ml), was added glyoxal (40 wt % solution in H2O) (12.8 mg, 0.089 mmol) dissolved in ethanol (20 ml) and the mixture was refluxed for 12 h. The orange product obtained was washed with ether and recrystallized from ethanol at room temperature (m.p. 472-475 K, yield 67%).
7. Refinement
Crystal data, data collection and structure . All hydrogen atoms were constrained to ride on their parent atoms with C—H = 0.93, 0.96 and 0.98 Å for aromatic, methyl and methine H atoms, respectively, and with N—H = 0.86 Å. Isotropic displacement parameters of these atoms were constrained to 1.5Ueq(C) for the methyl group and to 1.2Ueq(C,N) for all other H atoms.
details are summarized in Table 2Supporting information
CCDC reference: 2021045
https://doi.org/10.1107/S2056989020010646/yk2135sup1.cif
contains datablock I. DOI:Supporting information file. DOI: https://doi.org/10.1107/S2056989020010646/yk2135Isup3.cml
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020010646/yk2135Isup4.hkl
Data collection: X-AREA (Stoe & Cie, 2002); cell
X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXT2018/3 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2020); software used to prepare material for publication: WinGX (Farrugia, 2012), SHELXL2018/3 (Sheldrick, 2015b), PLATON (Spek, 2020) and publCIF (Westrip, 2010).C16H16N2O2 | Dx = 1.381 Mg m−3 |
Mr = 268.31 | Melting point = 472–475 K |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.798 (3) Å | Cell parameters from 3858 reflections |
b = 4.7133 (4) Å | θ = 1.8–32.0° |
c = 11.5330 (14) Å | µ = 0.09 mm−1 |
β = 106.751 (9)° | T = 296 K |
V = 1290.8 (3) Å3 | Plate, orange |
Z = 4 | 0.78 × 0.42 × 0.13 mm |
F(000) = 568 |
Stoe IPDS 2 diffractometer | 2194 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus' | 1024 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.059 |
Detector resolution: 6.67 pixels mm-1 | θmax = 32.0°, θmin = 3.4° |
rotation method scans | h = −35→36 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −7→6 |
Tmin = 0.941, Tmax = 0.989 | l = −16→16 |
5580 measured reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0639P)2] where P = (Fo2 + 2Fc2)/3 |
2194 reflections | (Δ/σ)max < 0.001 |
92 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.50672 (4) | 0.7122 (2) | −0.13429 (9) | 0.0582 (3) | |
N1 | −0.57174 (5) | 0.4629 (3) | −0.34733 (13) | 0.0622 (4) | |
H1 | −0.591648 | 0.369876 | −0.409012 | 0.075* | |
C7 | −0.59760 (6) | 0.6173 (3) | −0.27650 (13) | 0.0484 (3) | |
C2 | −0.65643 (6) | 0.6435 (3) | −0.30692 (14) | 0.0531 (4) | |
C6 | −0.56462 (6) | 0.7472 (3) | −0.17100 (13) | 0.0497 (3) | |
C8 | −0.51247 (6) | 0.4590 (3) | −0.31772 (14) | 0.0545 (4) | |
H8 | −0.500090 | 0.289696 | −0.352275 | 0.065* | |
C3 | −0.67936 (7) | 0.8104 (4) | −0.23575 (17) | 0.0657 (5) | |
H3 | −0.718296 | 0.828025 | −0.255126 | 0.079* | |
C5 | −0.58834 (7) | 0.9190 (3) | −0.10285 (15) | 0.0599 (4) | |
H5 | −0.565754 | 1.011706 | −0.034970 | 0.072* | |
C1 | −0.69244 (7) | 0.4830 (4) | −0.41332 (17) | 0.0675 (5) | |
H1A | −0.682704 | 0.536853 | −0.485013 | 0.101* | |
H1B | −0.731357 | 0.526107 | −0.423392 | 0.101* | |
H1C | −0.686334 | 0.283070 | −0.399720 | 0.101* | |
C4 | −0.64605 (8) | 0.9525 (4) | −0.13620 (18) | 0.0709 (5) | |
H4 | −0.662501 | 1.070905 | −0.091513 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0456 (6) | 0.0679 (7) | 0.0562 (6) | −0.0052 (4) | 0.0068 (5) | −0.0074 (5) |
N1 | 0.0411 (7) | 0.0735 (8) | 0.0664 (8) | −0.0036 (6) | 0.0067 (6) | −0.0223 (7) |
C7 | 0.0436 (7) | 0.0457 (7) | 0.0545 (8) | −0.0027 (6) | 0.0122 (6) | 0.0014 (6) |
C2 | 0.0435 (7) | 0.0526 (8) | 0.0612 (9) | −0.0031 (6) | 0.0120 (7) | 0.0087 (7) |
C6 | 0.0449 (7) | 0.0509 (7) | 0.0534 (8) | −0.0046 (6) | 0.0146 (6) | 0.0049 (7) |
C8 | 0.0429 (7) | 0.0554 (8) | 0.0621 (9) | 0.0023 (6) | 0.0101 (7) | −0.0047 (7) |
C3 | 0.0487 (9) | 0.0707 (10) | 0.0806 (12) | 0.0037 (8) | 0.0234 (9) | 0.0044 (9) |
C5 | 0.0648 (10) | 0.0610 (9) | 0.0565 (9) | −0.0076 (7) | 0.0214 (7) | −0.0040 (7) |
C1 | 0.0450 (8) | 0.0771 (10) | 0.0726 (11) | −0.0070 (7) | 0.0044 (7) | 0.0036 (9) |
C4 | 0.0669 (11) | 0.0733 (11) | 0.0811 (12) | 0.0031 (8) | 0.0349 (10) | −0.0104 (10) |
O1—C6 | 1.3846 (17) | C8—C8i | 1.505 (3) |
O1—C8i | 1.4521 (18) | C8—H8 | 0.9800 |
N1—C7 | 1.3822 (19) | C3—C4 | 1.379 (3) |
N1—C8 | 1.4099 (19) | C3—H3 | 0.9300 |
N1—H1 | 0.8600 | C5—C4 | 1.380 (2) |
C7—C6 | 1.397 (2) | C5—H5 | 0.9300 |
C7—C2 | 1.4041 (19) | C1—H1A | 0.9600 |
C2—C3 | 1.373 (2) | C1—H1B | 0.9600 |
C2—C1 | 1.498 (2) | C1—H1C | 0.9600 |
C6—C5 | 1.373 (2) | C4—H4 | 0.9300 |
C6—O1—C8i | 113.95 (11) | O1i—C8—H8 | 109.8 |
C7—N1—C8 | 119.51 (12) | C8i—C8—H8 | 109.8 |
C7—N1—H1 | 120.2 | C2—C3—C4 | 121.60 (15) |
C8—N1—H1 | 120.2 | C2—C3—H3 | 119.2 |
N1—C7—C6 | 119.38 (12) | C4—C3—H3 | 119.2 |
N1—C7—C2 | 121.63 (14) | C6—C5—C4 | 119.27 (16) |
C6—C7—C2 | 118.98 (14) | C6—C5—H5 | 120.4 |
C3—C2—C7 | 118.72 (15) | C4—C5—H5 | 120.4 |
C3—C2—C1 | 121.82 (14) | C2—C1—H1A | 109.5 |
C7—C2—C1 | 119.43 (15) | C2—C1—H1B | 109.5 |
C5—C6—O1 | 118.20 (13) | H1A—C1—H1B | 109.5 |
C5—C6—C7 | 121.14 (13) | C2—C1—H1C | 109.5 |
O1—C6—C7 | 120.64 (12) | H1A—C1—H1C | 109.5 |
N1—C8—O1i | 109.28 (12) | H1B—C1—H1C | 109.5 |
N1—C8—C8i | 109.82 (15) | C3—C4—C5 | 120.05 (16) |
O1i—C8—C8i | 108.29 (9) | C3—C4—H4 | 120.0 |
N1—C8—H8 | 109.8 | C5—C4—H4 | 120.0 |
C8—N1—C7—C6 | −5.4 (2) | N1—C7—C6—O1 | −2.8 (2) |
C8—N1—C7—C2 | 175.60 (14) | C2—C7—C6—O1 | 176.19 (13) |
N1—C7—C2—C3 | −177.10 (14) | C7—N1—C8—O1i | −82.21 (17) |
C6—C7—C2—C3 | 3.9 (2) | C7—N1—C8—C8i | 36.44 (15) |
N1—C7—C2—C1 | 4.7 (2) | C7—C2—C3—C4 | 0.3 (2) |
C6—C7—C2—C1 | −174.29 (14) | C1—C2—C3—C4 | 178.44 (16) |
C8i—O1—C6—C5 | 159.07 (13) | O1—C6—C5—C4 | −178.67 (14) |
C8i—O1—C6—C7 | −22.75 (17) | C7—C6—C5—C4 | 3.2 (2) |
N1—C7—C6—C5 | 175.29 (14) | C2—C3—C4—C5 | −2.9 (3) |
C2—C7—C6—C5 | −5.7 (2) | C6—C5—C4—C3 | 1.1 (2) |
Symmetry code: (i) −x−1, y, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1ii | 0.93 | 2.59 | 3.513 (2) | 172 |
N1—H1···C5iii | 0.86 | 2.64 | 3.375 (2) | 144 |
Symmetry codes: (ii) −x−1, −y+2, −z; (iii) x, −y+1, z−1/2. |
Parameters | Å, ° |
O1—C6 | 1.3846 (17) |
O1—C8* | 1.4521 (18) |
N1—C8 | 1.4099 (19) |
N1—C7 | 1.3822 (19) |
C8—C8* | 1.505 (3) |
C6—C7 | 1.397 (2) |
O1*—C8—C8* | 108.29 (9) |
N1—C8—C8* | 109.82 (15) |
N1—C8—O1* | 109.28 (12) |
C6—O1—C8* | 113.95 (11) |
C7—N1—C8—C8* | 36.44 (15) |
C8*—O1—C6—C7 | -22.75 (17) |
C2—C7—C6—C5 | -5.7 (2) |
N1—C7—C6—O1 | -2.8 (2) |
Acknowledgements
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).
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