Crystal structure of 1′-(prop-2-yn-1-yl)-1,4-di­hydro­spiro­[benzo[d][1,3]oxazine-2,3′-indolin]-2′-one

Y AaminaNaaz; J Kamalraja; G Vimala; P T Perumal; A SubbiahPandi

doi:10.1107/S2056989015011949

. 2015 Jun 27;71(Pt 7):o510–o511. doi: 10.1107/S2056989015011949

Crystal structure of 1′-(prop-2-yn-1-yl)-1,4-dihydrospiro[benzo[d][1,3]oxazine-2,3′-indolin]-2′-one

Y AaminaNaaz ^a, J Kamalraja ^b, G Vimala ^a, P T Perumal ^b, A SubbiahPandi ^a,^*

PMCID: PMC4518956 PMID: 26279936

Abstract

In the title compound, C₁₈H₁₄N₂O₂, the six-membered oxazine ring adopts a half-chair conformation and its mean plane makes a dihedral angle of 83.23 (7)° with the pyrrolidine ring of the indoline ring system. In the crystal, molecules are linked via N—H⋯O hydrogen bonds, forming chains along [100]. The chains are linked by C—H⋯π interactions, forming slabs parallel to (001).

Keywords: crystal structure, spiro compounds, spirooxazines, oxazine, indoline, N—H⋯O hydrogen bonding

Related literature

For the biological activity of spiro compounds, see: James et al. (1991 ▸); Kobayashi et al. (1991 ▸). For the use of 1,3-dipolar cycloaddition reactions in the construction of spiro compounds, see: Caramella & Grunanger (1984 ▸). For applications of spirooxazine derivatives, see: Chibisov & Görner (1999 ▸). For the synthetic method, see: Kamalraja et al. (2014 ▸). graphic file with name e-71-0o510-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₄N₂O₂
M _r = 290.31
Triclinic,
a = 5.5571 (3) Å
b = 8.5404 (4) Å
c = 15.4542 (9) Å
α = 85.884 (3)°
β = 86.814 (3)°
γ = 74.125 (3)°
V = 703.17 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.981, T _max = 0.984
16184 measured reflections
3231 independent reflections
2350 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 1.06
3231 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015011949/su5155sup1.cif

e-71-0o510-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011949/su5155Isup2.hkl

e-71-0o510-Isup2.hkl^{(158.5KB, hkl)}

Click here for additional data file.^{(2.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011949/su5155Isup3.cml

Click here for additional data file.^{(2.4MB, tif)}

. DOI: 10.1107/S2056989015011949/su5155fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(1.3MB, tif)}

c . DOI: 10.1107/S2056989015011949/su5155fig2.tif

The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1408024

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg3 and Cg4 are the centroids of rings C1C6 and C9C14, respectively.

DHA	DH	HA	D A	DHA
N1H1O2ⁱ	0.86	2.13	2.9641(16)	164
C4H4Cg4ⁱⁱ	0.93	2.90	3.6572(19)	140
C8H8A Cg4ⁱⁱⁱ	0.97	2.86	3.6636(17)	141
C16H16B Cg3^iv	0.97	2.79	3.5341(18)	134

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

S1. Synthesis and crystallization

A mixture of N-propargylisatin (1.0 mmol), and 2-aminobenzylalcohol (1.0 mmol) was refluxed in ethanol, in the presence of InCl₃ (10 mol%), for 2 h. After the reaction was complete as indicated by TLC, the reaction mixture was cooled to room temperature. The solid that formed was filtered, dried and recrystallized in ethanol or dichloromethane to obtain in good yield (89%) of the pure title product as block-like colourless crystals.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The N- and C-bound H atoms were positioned geometrically (N—H = 0.86 Å, C–H = 0.93–0.97 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(N,C).

S3. Structural commentary

Spiro compounds represent an important class of naturally occurring substances, which in many cases exhibit useful biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-dipolar cycloaddition reactions are widely used for construction of spiro-compounds (Caramella & Grunanger, 1984). It has also been reported that spiro-oxazine derivatives have real or potential applications in many fields such as protection, decoration, display, memory, switches, photography, photometry and photomechanics (Chibisov & Görner, 1999). Efforts have been made to design this industrially and biologically active hetrocyclic compounds by making or breaking carbon-carbon (C—C) and carbon-hetero atom (C—X) (Kamalraja et al., 2014). This InCl₃-mediated compound have been synthesized as a part of the effort carried to develop eco-friendly potential compound by new synthetic method.

The molecular structure of the title compound is illustrated in Fig 1. The oxazine ring (O1/N1/C7/C8/C9/C14) adopts a half chair confirmation, and its mean plane makes a dihedral angle of 83.23 (7) ° with the pyrrolidine ring (O1/N1/C8/C9/C14) of the indolinone ring system. The indole ring system is essentially planar, with atoms C16 and O2 deviating from its mean plane by -0.0130 and 0.0273 Å, respectively. The dihedral angle between the benzene ring (C1—C6) of the indoline ring system and the benzene ring (C9—C14) of the mean plane of the 2,4-dihydro-1H-benzo[d][1,3] oxazine ring system is 76.94 (8) °.

In the crystal, molecules are linked via N—H···O hydrogen bonds (Table 1) forming chains along [100], as shown in Fig 2. The chains are linked by C—H···π interactions forming slabs parallel to (001); see Table 1.