Crystal structure of rac-3-hy­droxy-2-(p-tol­yl)-2,3,3a,4,7,7a-hexa­hydro-1H-4,7-methano­isoindol-1-one

Mehmet Aslantaş; Cumali Çelik; Ömer Çelik; Arzu Karayel

doi:10.1107/S2056989015001942

. 2015 Feb 4;71(Pt 3):o143–o144. doi: 10.1107/S2056989015001942

Crystal structure of rac-3-hydroxy-2-(p-tolyl)-2,3,3a,4,7,7a-hexahydro-1H-4,7-methanoisoindol-1-one

Mehmet Aslantaş ^a,^*, Cumali Çelik ^b, Ömer Çelik ^c, Arzu Karayel ^d,^e

PMCID: PMC4350749 PMID: 25844217

Abstract

In the title compound, C₁₆H₁₇NO₂, the cyclohexene ring adopts a boat conformation, and the five-membered rings have envelope conformations with the bridging atom as the flap. Their mean planes are oriented at a dihedral angle of 86.51 (7)°. The molecular structure is stabilized by a short intramolecular C—H⋯O contact. In the crystal, molecules are linked by O—H⋯O hydrogen bonds forming chains propagating along [100]. The chains are linked by C—H⋯π interactions, forming slabs parallel to (001).

Keywords: crystal structure; methanoisoindol-1-one; methanoisoindole-1,3-dione; O—H⋯O hydrogen bonds; C—H⋯π interactions

Related literature

For medical and pharmaceutical applications of chiral tricyclic compounds, see: Abel et al. (1996 ▸); Salvati et al. (2005 ▸). For the synthesis of the starting reagent, 2-(p-tolyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione, see: Andrade & Evilazio (2004 ▸). For the reduction reaction used to synthesise the title compound, see: Hubert et al. (1975 ▸). For the crystal structure of a similar compound, see: Takebayashi et al. (2010 ▸). graphic file with name e-71-0o143-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₇NO₂
M _r = 255.31
Monoclinic,
a = 6.5067 (2) Å
b = 9.7385 (2) Å
c = 21.0780 (5) Å
β = 97.154 (1)°
V = 1325.22 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.45 × 0.25 × 0.15 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▸) T _min = 0.963, T _max = 0.988
28760 measured reflections
5019 independent reflections
3930 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.180
S = 1.09
5019 reflections
180 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015001942/su5074sup1.cif

e-71-0o143-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015001942/su5074Isup2.hkl

e-71-0o143-Isup2.hkl^{(240.9KB, hkl)}

Click here for additional data file.^{(5.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015001942/su5074Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015001942/su5074fig1.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)}

b . DOI: 10.1107/S2056989015001942/su5074fig2.tif

A partial view along the b axis of the crystal packing of the title compound. Dashed lines indicate the O—H⋯O hydrogen bonds (see Table 1 for details).

CCDC reference: 1046290

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg4 are the centroids of the N1/C8C11 and C2C7 rings, respectively.

DHA	DH	HA	D A	DHA
C4H4O2	0.93	2.33	2.860(2)	116
O1H2O2ⁱ	0.82	2.14	2.7194(15)	128
C13H13Cg1ⁱⁱ	0.93	2.94	3.6903(18)	139
C16H16A Cg4ⁱⁱⁱ	0.99(2)	2.86(2)	3.692(2)	143.4(15)

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

Acknowledgments

This research was supported by Yalova University Scientific Research Projects Coordination Department (project No. 210–07). We would also like to thank DUPTAM, Dicle University, Turkey, for the use of the X-ray diffractometer.

supplementary crystallographic information

S1. Comment

Chiral tricyclic compounds in heterocyclic chemistry are important in medicinal and pharmaceutical fields (Abel et al., 1996; Salvati et al., 2005). We report herein on the synthesis and crystal structure of the title compound, prepared by reduction of 2-(p-tolyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione, using NaBH₄.

The bond lengths and angles in the title compound, Fig. 1, are close to those reported for two similar chiral structures (Takebayashi et al., 2010). The cyclohexene ring (C9/C190/C12-C15) has a normal boat conformation [puckering parameters: θ₂ = 0.9587 (3) Å and φ₂ = 169.02 (14)°]. The main bridge angle, C12—C16—C15, which connects the two bridgeheads on the cyclohexene ring, is 93.78 (12) °. The two five-membered rings, A(C9/C10/C15/C16/C12) and B(C12-C16) have envelope conformations with the flap atom C16 deviating from their mean planes by 0.5131 (2) and 0.4027 (2) Å, respectively. The dihedral angle between their mean planes, [A/B], is 86.51 (7)°. The whole molecule is non-planar with the dihedral angle between the benzene (C2-C7) and imide (N1/C8-C11) rings being 26.12 (5)°. This is much smaller than the same dihedral angle of ca.57.22 ° in the 2-phenyl derivative (Takebayashi et al., 2010) or ca. 61.37 ° in the 2-(4-fluorophenyl) derivative (Takebayashi et al., 2010). In the molecule there is a strong C—H···O intra-molecular contact present (Table 1).

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

S2. Experimental

The starting reagent, 2-(p-tolyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione (L), is a known compound and was prepared from nadic anhydride and 4-toluidine (Andrade & Evilazio, 2004). The title compound was prepared by a reduction reaction following a modification of a literature procedure (Hubert et al., 1975). NaBH₄ (0.94 g) was added in small portions at 298 K over a period of 2 h to L (0.72 g, 2.84 mmol) dissolved in ethanol (250 ml). The excess of NaBH₄ was consumed in 15 min at 278 K by adding aqueous HCl (2 mol dm^-3) until the pH reached 3. The mixture was stirred for an additional 1 h at the same temperature then poured into water and extracted with dichloromethane. The organic layer was separated, dried over Na₂SO₄, filtered and evaporated to yield a white solid that was purified by silica gel chromatography [ethyl acetate/n-hexane (3:2 v/v)] which on slow evaporation of the solvent gave colourless crystals (yield: 65%; m.p.: 475–477 K). NMR (DMSO): δ(H) 1.38–1.42 (dd, 2H, CH₂), 2.24 (s, 3H, CH₃), 2.59–2.60 (d, H, CH), 2.61–2.62 (d, H, CH), 3.11–3.13 (m, H, CH), 3.18–3.21 (dd, H, CH), 4.81 (s, H, CH—OH), 6.03–6.05 (dd, H, ═CH), 6.16–6.18 (dd, H, ═CH), 7.09–7.11 (d, 2H, aromatic), 7.25–7.27 (d, 2H, aromatic); δ(C) 20.96 (CH₃), 45.08 (CH), 45.62 (CH), 46.56 (CH), 49.58 (CH), 51.06 (CH₂), 86.17 (CH—OH), 124.07 (Cm), 129.33 (Co), 134.37 (CH═CH), 134.93 (Cq—N), 135.87 (C—CH₃), 174.39 (C═O) p.p.m.. FT—IR (ATR): 3211 (OH), 2972, 2943, 1646 (C═O), 1613 and 1515 (aromatic, C═C), 1422, 1403, 1065 (C—N), 819 cm^-1.