8-Methyl-3-methyl­sulfanyl-8a,8b-di­hydro-5H-1-oxa-2,4-di­aza­ace­naphthyl­ene

Abou, A.; Bamba, F.; Marrot, J.; Yaya, S.; Coustard, J.-M.

doi:10.1107/S241431462100674X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 6| June 2021| x210674

https://doi.org/10.1107/S241431462100674X

Open

access

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene

Akoun Abou,^a ^* Fanté Bamba,^b Jérôme Marrot,^c Soro Yaya ^d and Jean-Marie Coustard ^e ‡

^aDepartment of Training and Research in Electrical and Electronic Engineering, Research Team: Instrumentation, Image and Spectroscopy, Félix Houphouët-Boigny National Polytechnic Institute, BP 1093 Yamoussoukro, Côte d'Ivoire, ^bLaboratoire de Constitution et Réaction de la Matière, UFR SSMT, Université Félix Houphouët-Boigny, 22 BP 582 Abidjan 22, Côte d'Ivoire, ^cLaboratoire ILV-UVSQ-UMR 8180 CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France, ^dLaboratoire des Procédés Industriels de Synthèse et d'Environnement, Institut National Polytechnique Félix Houphouët-Boigny, BP 991 Yamoussoukro, Côte d'Ivoire, and ^eLaboratoire IC2MP-UMR 7285 CNRS, 40 Avenue du Recteur Pineau, 86022 Poitiers Cedex, France
^*Correspondence e-mail: abouakoun@gmail.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 21 June 2021; accepted 28 June 2021; online 30 June 2021)

In the tricyclic title compound, C₁₁H₁₂N₂OS, the 2,3,4,5-tetrahydropyridine ring adopts a half-chair conformation. This ring makes dihedral angles of 27.72 (7) and 45.17 (7)°, respectively, with the isoxazole and the cyclohexa-1,3-diene rings while the isoxazole ring is oriented at an acute angle of 63.46 (7)° with respect to the cyclohexa-1,3-diene ring. In the crystal, molecules associate via C—H⋯N hydrogen bonds and C—H⋯π interactions, forming a three-dimensional network.

Keywords: crystal structure; diazadihydroacenaphthylene derivative; hydrogen bonding and C—H⋯π interactions.

CCDC reference: 2089097

Structure description

Diazadihydroacenaphthylene derivatives contain an isoxazoline scaffold and constitute an important class of heterocyclic compounds whose chemical properties have been investigated over the years (Jäger & Buss, 1980 ; Jäger et al., 1980 ). This scaffold is used in the synthesis of several complex natural products (Saha & Bhattacharjya, 1997 ; Copp et al.,1992 ) and is a pharmacophore of numerous medicinal chemistry compounds (Brandi et al., 2003 ; King et al., 1982 ; Bacher et al., 1997 ; You et al., 1995 ). It has also been reported that this scaffold has a multiple range of biological activities, covering the agricultural field (Liu & Howe, 1983 ), medicinal properties such as anticancer, antibiotic (Habeeb et al., 2001 ; Mallesha et al., 2001 ), antiviral and anti-HIV (Ichiba et al., 1993 ) agents.

We report herein the synthesis and crystal structure of the title compound (Fig. 1). The 2,3,4,5-tetrahydro-pyridine ring adopts a half-chair conformation with puckering parameters (Cremer & Pople, 1975 ) Q_T = 0.4779 (15) Å, θ = 129.65 (18)°, φ = 29.0 (2)° and is oriented at dihedral angles of 27.72 (7) and 45.17 (7)°, respectively, with the isoxazole and the cyclohexa-1,3-diene rings while the isoxazole ring makes an acute angle of 63.46 (7)° with respect to the cyclohexa-1,3-diene ring. These dihedral angles show that this tricycle compound is not planar, as confirmed by the total puckering amplitude Q_T of 1.4727 (15) Å.

Figure 1
The molecular structure of the title compound and the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.

In the crystal, C1—H1⋯N12(x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 2) hydrogen bonds (Table 1) link the molecules along the [010] direction (Fig. 2) and C5—H5B⋯Cg3(−x, −y + 1, −z) interactions, where Cg3 is the centroid of the cyclohexa-1,3-diene ring (Fig. 3) are observed.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the cyclohexa-1,3-diene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N12ⁱ	0.98	2.64	3.4173 (16)	136
C5—H5B⋯Cg3ⁱⁱ	0.97	2.80	3.6158 (17)	142
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ ; (ii) .

Figure 2
Part of the crystal packing of the title compound showing the formation of intermolecular C1—H1⋯N12 hydrogen bonds along the b axis. Dashed lines indicate hydrogen bond contacts. H atoms not involved in hydrogen bond interactions have been omitted for clarity.

Figure 3
A view of the crystal packing, showing the π–ring interactions (dashed lines). The yellow dots are centroids of rings. H atoms not involved in these interactions have been omitted for clarity.

Synthesis and crystallization

1-[(4-Methylbenzyl)amino]-1-methylthio-2-nitroethylene (236 mg; 1 mmol) was dissolved in 4.4 ml (50 mmol) of triflic acid at a temperature within the range −26 to −15°C under a nitrogen atmosphere. The reaction was monitored as follows: one or two drops of the reacting medium were quenched over ice (about 1 g) and extracted with CH₂Cl2₂ (0.5 ml). The organic extract was dried over Na₂CO₃ and was purified by flash chromatography on a silica column (eluent: petroleum ether/ethyl acetate: (85:15, v/v) to afford the title compound (97 mg; 0.441 mmol) as a colourless powder. The powder was dissolved in a minimum of dichloromethane by heating under agitation. To this hot mixture, petroleum ether was added until the formation of a new precipitate started, which dissolved in the resulting mixture upon heating. Upon cooling, colourless crystals suitable for single-crystal X-ray diffraction analysis were obtained, m.p. 120.1°C.

¹H NMR (CDCl₃): δ (p.p.m.) = 2.01 (s, 3 H, CH₃); 2.39 (s, 3H, SCH₃); 4.23 (d, J = 14.94 Hz, 1 H, H-8 b); 4.47 (s, 2 H, CH₂); 5.46 (d, J = 14.9 Hz, 1 H, H-8a); 5.81 (d, J = 7.1 Hz, 1 H, vinylic H); 5.84 (d, J = 7.1 Hz, 1 H, vinylic H).

¹³C NMR (CDCl₃): δ (p.p.m.) = 12.0 (SCH₃); 21.1 (CH₃); 48.0 (C-8a); 58.4 (CH₂); 82.0 (C-8 b); 117.8 (CH); 121.7 (CH); 124.8 (quaternary carbon); 130.4 (C-8); 152.6 (>C=N—O–); 155.4 (–S—C=N–).

MS (mass spectrometer, 70 eV); m/z (%): 220 [M⁺]. MS–HR(IE) m/z ([M⁺]) C₁₁H₁₂N₂OS: 220.0680.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂OS
M_r	220.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	8.0175 (2), 14.4611 (3), 18.5612 (4)
V (Å³)	2152.02 (8)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.27
Crystal size (mm)	0.30 × 0.10 × 0.06

Data collection
Diffractometer	Bruker CCD area detector
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.922, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	67637, 3155, 2560
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.129, 1.08
No. of reflections	3155
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.19
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2016 ), SIR2019 (Burla et al., 2015 ), PLATON (Spek, 2020 ), WinGX (Farrugia, 2012 ), SHELXL2018/3 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2089097

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431462100674X/xu4044sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462100674X/xu4044Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431462100674X/xu4044Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR2019 (Burla et al., 2015); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020), WinGX (Farrugia, 2012); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015) and publCIF (Westrip, 2010).

8-Methyl-3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylene top

Crystal data top

C₁₁H₁₂N₂OS	D_x = 1.360 Mg m⁻³
M_r = 220.29	Melting point: 393.1 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 8401 reflections
a = 8.0175 (2) Å	θ = 2.2–29.8°
b = 14.4611 (3) Å	µ = 0.27 mm⁻¹
c = 18.5612 (4) Å	T = 293 K
V = 2152.02 (8) Å³	Parallelepiped, colorless
Z = 8	0.30 × 0.10 × 0.06 mm
F(000) = 928

Data collection top

Bruker CCD area detector diffractometer	3155 independent reflections
Radiation source: fine-focus sealed tube	2560 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 512 pixels mm^-1	θ_max = 30.1°, θ_min = 2.8°
phi and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −20→20
T_min = 0.922, T_max = 0.984	l = −26→26
67637 measured reflections

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0606P)² + 0.5724P] where P = (F_o² + 2F_c²)/3
3155 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³
0 constraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
S1	0.87930 (6)	0.23268 (3)	0.81332 (2)	0.05945 (15)
C1	0.68279 (16)	0.11024 (8)	0.99475 (8)	0.0430 (3)
H1	0.567035	0.131511	0.991152	0.052*
C2	0.79398 (16)	0.16562 (8)	0.94630 (7)	0.0411 (3)
C3	0.78747 (16)	0.14749 (9)	0.86830 (8)	0.0441 (3)
N4	0.72257 (16)	0.07471 (9)	0.84198 (7)	0.0527 (3)
C5	0.6511 (2)	0.00367 (11)	0.89045 (9)	0.0581 (4)
H5A	0.685682	−0.056803	0.873466	0.070*
H5B	0.530492	0.006443	0.887046	0.070*
C6	0.69925 (16)	0.01268 (9)	0.96758 (8)	0.0458 (3)
C7	0.77226 (18)	−0.05134 (9)	1.00803 (9)	0.0512 (3)
H7	0.786148	−0.110657	0.989631	0.061*
C8	0.8308 (2)	−0.03094 (10)	1.08014 (9)	0.0543 (4)
H8	0.871921	−0.079538	1.107742	0.065*
C9	0.8293 (2)	0.05336 (11)	1.10934 (9)	0.0544 (3)
C10	0.7554 (2)	0.13333 (9)	1.06827 (8)	0.0492 (3)
H10	0.668392	0.162125	1.097811	0.059*
O11	0.88721 (16)	0.20355 (7)	1.05266 (6)	0.0584 (3)
N12	0.90369 (16)	0.21466 (8)	0.97783 (7)	0.0486 (3)
C13	0.8627 (3)	0.17816 (14)	0.72661 (9)	0.0685 (5)
H13A	0.748115	0.177828	0.711577	0.103*
H13B	0.902781	0.115738	0.729744	0.103*
H13C	0.928286	0.211794	0.692175	0.103*
C14	0.8944 (4)	0.07297 (16)	1.18338 (10)	0.0846 (7)
H14A	0.928090	0.016115	1.205768	0.127*
H14B	0.808424	0.101512	1.211680	0.127*
H14C	0.988454	0.113844	1.180153	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0740 (3)	0.0518 (2)	0.0525 (2)	−0.00919 (18)	0.00304 (17)	0.00618 (15)
C1	0.0366 (6)	0.0335 (5)	0.0588 (7)	0.0038 (4)	0.0087 (5)	0.0000 (5)
C2	0.0417 (6)	0.0302 (5)	0.0513 (7)	0.0016 (4)	0.0033 (5)	−0.0005 (5)
C3	0.0415 (6)	0.0407 (6)	0.0502 (7)	0.0004 (5)	−0.0010 (5)	0.0000 (5)
N4	0.0512 (6)	0.0494 (6)	0.0576 (7)	−0.0054 (5)	−0.0049 (5)	−0.0056 (5)
C5	0.0584 (8)	0.0449 (7)	0.0710 (10)	−0.0145 (7)	−0.0018 (7)	−0.0085 (7)
C6	0.0394 (6)	0.0339 (6)	0.0641 (8)	−0.0058 (5)	0.0093 (6)	−0.0037 (5)
C7	0.0477 (7)	0.0319 (5)	0.0739 (9)	−0.0012 (5)	0.0151 (7)	−0.0008 (6)
C8	0.0523 (8)	0.0436 (7)	0.0669 (9)	0.0072 (6)	0.0129 (7)	0.0123 (6)
C9	0.0590 (8)	0.0511 (8)	0.0530 (8)	0.0045 (7)	0.0112 (6)	0.0062 (6)
C10	0.0542 (7)	0.0393 (6)	0.0540 (7)	0.0051 (6)	0.0137 (6)	−0.0016 (5)
O11	0.0802 (8)	0.0458 (5)	0.0493 (6)	−0.0139 (5)	−0.0003 (5)	−0.0045 (4)
N12	0.0596 (7)	0.0358 (5)	0.0504 (6)	−0.0081 (5)	0.0009 (5)	−0.0014 (4)
C13	0.0823 (12)	0.0727 (11)	0.0507 (8)	0.0071 (9)	0.0068 (8)	−0.0005 (8)
C14	0.123 (2)	0.0730 (12)	0.0575 (10)	0.0118 (12)	−0.0060 (11)	0.0052 (9)

Geometric parameters (Å, º) top

S1—C3	1.7610 (14)	C7—H7	0.9300
S1—C13	1.7972 (18)	C8—C9	1.334 (2)
C1—C2	1.4984 (18)	C8—H8	0.9300
C1—C6	1.5039 (17)	C9—C14	1.497 (3)
C1—C10	1.521 (2)	C9—C10	1.506 (2)
C1—H1	0.9800	C10—O11	1.4942 (18)
C2—N12	1.2724 (17)	C10—H10	0.9800
C2—C3	1.4723 (19)	O11—N12	1.4045 (16)
C3—N4	1.2717 (17)	C13—H13A	0.9600
N4—C5	1.481 (2)	C13—H13B	0.9600
C5—C6	1.489 (2)	C13—H13C	0.9600
C5—H5A	0.9700	C14—H14A	0.9600
C5—H5B	0.9700	C14—H14B	0.9600
C6—C7	1.328 (2)	C14—H14C	0.9600
C7—C8	1.449 (2)

C3—S1—C13	100.43 (8)	C9—C8—C7	123.94 (14)
C2—C1—C6	104.35 (10)	C9—C8—H8	118.0
C2—C1—C10	101.16 (11)	C7—C8—H8	118.0
C6—C1—C10	118.25 (12)	C8—C9—C14	122.87 (16)
C2—C1—H1	110.8	C8—C9—C10	119.97 (15)
C6—C1—H1	110.8	C14—C9—C10	117.15 (15)
C10—C1—H1	110.8	O11—C10—C9	109.97 (13)
N12—C2—C3	125.17 (12)	O11—C10—C1	104.24 (10)
N12—C2—C1	115.67 (12)	C9—C10—C1	115.85 (12)
C3—C2—C1	118.29 (11)	O11—C10—H10	108.8
N4—C3—C2	122.66 (13)	C9—C10—H10	108.8
N4—C3—S1	121.83 (12)	C1—C10—H10	108.8
C2—C3—S1	115.49 (9)	N12—O11—C10	109.64 (10)
C3—N4—C5	119.94 (13)	C2—N12—O11	109.03 (11)
N4—C5—C6	115.04 (12)	S1—C13—H13A	109.5
N4—C5—H5A	108.5	S1—C13—H13B	109.5
C6—C5—H5A	108.5	H13A—C13—H13B	109.5
N4—C5—H5B	108.5	S1—C13—H13C	109.5
C6—C5—H5B	108.5	H13A—C13—H13C	109.5
H5A—C5—H5B	107.5	H13B—C13—H13C	109.5
C7—C6—C5	126.65 (14)	C9—C14—H14A	109.5
C7—C6—C1	120.20 (14)	C9—C14—H14B	109.5
C5—C6—C1	112.45 (13)	H14A—C14—H14B	109.5
C6—C7—C8	121.55 (13)	C9—C14—H14C	109.5
C6—C7—H7	119.2	H14A—C14—H14C	109.5
C8—C7—H7	119.2	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the cyclohexa-1,3-diene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N12ⁱ	0.98	2.64	3.4173 (16)	136
C5—H5B···Cg3ⁱⁱ	0.97	2.80	3.6158 (17)	142

Symmetry codes: (i) x−1/2, −y+1/2, −z+2; (ii) −x, −y+1, −z.

Footnotes

‡Deceased August 2013.

Acknowledgements

We thank the laboratory ILV-UVSQ-UMR 8180 CNRS, 45 Avenue des Etats Unis, 78035 Versailles Cedex, France, for the use of the spectrometer and for the spectroscopic analysis.

References

Bacher, E., Demnitz, F. W. J. & Hurni, T. (1997). Tetrahedron, 53, 14317–14326. Google Scholar
Brandi, A., Cicchi, S., Cordero, F. M. & Goti, A. (2003). Chem. Rev. 103, 1213–1270. Web of Science CrossRef CAS Google Scholar
Bruker (2016). SAINT. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2018). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). J. Appl. Cryst. 48, 306–309. Web of Science CrossRef CAS IUCr Journals Google Scholar
Copp, B. R., Ireland, C. M. & Barrows, L. R. (1992). J. Nat. Prod. 55, 822–823. Google Scholar
Cremer, D. & Pople, J. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Habeeb, A. G., Praveen Rao, P. N. & Knaus, E. E. (2001). J. Med. Chem. 44, 2921–2927. Google Scholar
Ichiba, T., Scheuer, P. J. & Kelly-Borges, M. (1993). J. Org. Chem. 58, 4149–4150. Google Scholar
Jäger, V., Buss, V. & Schwab, W. (1980). Liebigs Ann. Chem. pp. 122–139. Google Scholar
Jäger, V. & Buss, V. (1980). Liebigs Ann. Chem. pp. 101–121. Google Scholar
King, S. W., Riordan, J. M., Holt, E. M. & Stammer, C. H. (1982). J. Org. Chem. 47, 3270–3273. Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Liu, K. C. & Howe, R. K. (1983). J. Org. Chem. 48, 4590–4592. CrossRef CAS Web of Science Google Scholar
Mallesha, H., Ravi kumar, K. R., Mantelingu, K. & Rangappa, K. S. (2001). Synthesis, 10, 1459–1461. Google Scholar
Saha, A. & Bhattacharjya, A. (1997). Chem. Commun. pp. 495–496. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
You, Z., Khalil, M. A., Ko, D. & Lee, H. J. (1995). Tetrahedron Lett. 36, 3303–3306. Google Scholar