1,2,3,5-Tetra­hydro­naphtho­[2,1-c]oxepine

Lough, A.J.; Pounder, A.; Wicks, C.; Tam, W.

doi:10.1107/S2414314620002886

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 3| March 2020| x200288

https://doi.org/10.1107/S2414314620002886

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1,2,3,5-Tetrahydronaphtho[2,1-c]oxepine

Alan J. Lough,^a ^* Austin Pounder,^b Christopher Wicks ^b and William Tam ^b

^aDepartment of Chemistry, University of Toronto, Toronto, Ontario, M5S 3H6, Canada, and ^bDepartment of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada
^*Correspondence e-mail: alan.lough@utoronto.ca

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 February 2020; accepted 1 March 2020; online 5 March 2020)

In the title compound, C₁₄H₁₄O, the seven-membered ring is in a pseudo-chair conformation. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds forming layers parallel to (010). In addition, there are weak π–π stacking interactions between inversion-related naphthalene ring systems, with a ring centroid–ring centroid distance of 3.518 (5) Å.

Keywords: crystal structure; ring-opening reaction; regioisomer; weak hydrogen bonds.

CCDC reference: 1987387

Structure description

In past years, our research group has investigated the ring-opening reactions of cyclopropanated oxabenzonorbornadienes (CPOBD) (Carlson et al., 2014 , 2016 , 2018 ; Tait et al., 2016 ; Tigchelaar et al., 2014 ). Recently, we have examined the intramolecular ring-opening of reaction of CPOBD with tethered alcohol nucleophiles (Wicks et al., 2019 ). Based on previous work done in our research group, we anticipated two possible modes of ring-opening through nucleophilic attack at either the proximal or distal cyclopropyl carbon atom. Reaction of the C₁-alcohol tethered CPOBD I (see Fig. 3) in the presence of p-TsOH·H₂O in toluene afforded the Type 2 II and Type 3 III ring-opened products in 12% and 59% yields, respectively. The title structure of the Type 2 (II) regioisomer was verified by single-crystal X-ray analysis.

Figure 3
The reaction scheme.

The molecular structure of the title compound is shown in Fig. 1. The seven-membered ring (C1–C6/O1) is in a pseudo-chair conformation. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds (Table 1), forming layers parallel to (010) (Fig. 2). In addtion, there are weak π–π stacking interaction between inversion related naphthalene ring systems (C1/C2/C7–C14) with a ring centroid–ring centroid distance of 3.518 (5) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯O1ⁱ	0.970 (16)	2.558 (16)	3.4803 (14)	159.0 (11)
C12—H12A⋯O1ⁱⁱ	0.976 (15)	2.560 (15)	3.4661 (14)	154.5 (11)
Symmetry codes: (i) x-1, y, z-1; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

Figure 2
Part of the crystal structure with weak hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonds are shown.

Synthesis and crystallization

To a 6 dram vial open to air were added the alcohol-tethered cyclopropanated oxabenzonorbornadiene I (0.3547 g, 1.64 mmol), and p-TsOH·H₂O (57.7 mg, 20 mol%) dissolved in 7 ml of toluene (see Fig. 3). The reaction was left to stir at 333 K for 1.5 h, after which the reaction mixture was cooled and quenched with 10 ml of water. The aqueous layers were combined and back extracted with EtOAc (3 × 5 ml). The organic layers were combined, washed with brine, dried over MgSO₄, and concentrated in vacuo. The resulting crude oil was purified by flash chromatography (EtOAc:hexanes, 10: 90) to obtain ring-opened products II (38.5 mg, 0.194 mmol, 12%) and III (189.8 mg, 0.957 mmol) as a white solid and clear oil, respectively. The title compound II was subsequently crystallized from DCM solution by slow evaporation of the solvent to afford colourless blocks.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₄O
M_r	198.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	9.4559 (3), 12.8405 (4), 8.9638 (3)
β (°)	111.445 (1)
V (Å³)	1013.02 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.26 × 0.25

Data collection
Diffractometer	Bruker Kappa APEX DUO CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.723, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	21543, 2347, 2055
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 1.07
No. of reflections	2347
No. of parameters	192
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.20
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1987387

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620002886/hb4340sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620002886/hb4340Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620002886/hb4340Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: APEX3 (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

1,2,3,5-Tetrahydronaphtho[2,1-c]oxepine top

Crystal data top

C₁₄H₁₄O	F(000) = 424
M_r = 198.25	D_x = 1.300 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.4559 (3) Å	Cell parameters from 9948 reflections
b = 12.8405 (4) Å	θ = 2.3–27.5°
c = 8.9638 (3) Å	µ = 0.08 mm⁻¹
β = 111.445 (1)°	T = 150 K
V = 1013.02 (6) Å³	Block, colourless
Z = 4	0.37 × 0.26 × 0.25 mm

Data collection top

Bruker Kappa APEX DUO CCD diffractometer	2055 reflections with I > 2σ(I)
Radiation source: selaed tube with Bruker Triumph monochromator	R_int = 0.021
φ and ω scans	θ_max = 27.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −12→12
T_min = 0.723, T_max = 0.746	k = −16→16
21543 measured reflections	l = −11→11
2347 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	All H-atom parameters refined
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.052P)² + 0.3073P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2347 reflections	Δρ_max = 0.30 e Å⁻³
192 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

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
O1	1.00150 (8)	0.34280 (6)	0.72056 (9)	0.02263 (19)
C1	0.77678 (11)	0.44489 (7)	0.56216 (11)	0.0171 (2)
C2	0.65678 (11)	0.37620 (7)	0.53419 (11)	0.0163 (2)
C3	0.66501 (11)	0.29413 (8)	0.65822 (12)	0.0209 (2)
H3A	0.5679 (16)	0.2539 (11)	0.6272 (16)	0.029 (3)*
H3B	0.6758 (16)	0.3299 (11)	0.7608 (17)	0.031 (3)*
C4	0.79563 (12)	0.21581 (8)	0.68926 (13)	0.0235 (2)
H4A	0.7759 (16)	0.1550 (11)	0.7461 (16)	0.029 (3)*
H4B	0.7980 (16)	0.1911 (12)	0.5840 (18)	0.035 (4)*
C5	0.95069 (12)	0.25805 (9)	0.79119 (14)	0.0254 (2)
H5A	0.9486 (16)	0.2824 (11)	0.8993 (18)	0.033 (4)*
H5B	1.0304 (15)	0.2034 (10)	0.8079 (16)	0.025 (3)*
C6	0.91744 (11)	0.43684 (8)	0.71202 (13)	0.0214 (2)
H6A	0.9889 (14)	0.4953 (11)	0.7133 (14)	0.023 (3)*
H6B	0.8913 (15)	0.4415 (10)	0.8106 (17)	0.028 (3)*
C7	0.77109 (12)	0.52380 (7)	0.45040 (12)	0.0194 (2)
H7A	0.8559 (16)	0.5724 (11)	0.4711 (16)	0.029 (3)*
C8	0.64771 (12)	0.53392 (7)	0.31122 (12)	0.0198 (2)
H8A	0.6454 (15)	0.5891 (11)	0.2355 (16)	0.027 (3)*
C9	0.52464 (11)	0.46395 (7)	0.27548 (11)	0.0172 (2)
C10	0.39883 (12)	0.47042 (8)	0.12770 (12)	0.0218 (2)
H10A	0.4011 (15)	0.5267 (11)	0.0541 (16)	0.026 (3)*
C11	0.28267 (12)	0.40005 (9)	0.08940 (13)	0.0248 (2)
H11A	0.1987 (17)	0.4037 (11)	−0.0128 (19)	0.036 (4)*
C12	0.28495 (12)	0.32073 (9)	0.19878 (13)	0.0236 (2)
H12A	0.2036 (16)	0.2691 (11)	0.1702 (16)	0.031 (3)*
C13	0.40269 (11)	0.31364 (8)	0.34385 (12)	0.0201 (2)
H13A	0.4012 (15)	0.2577 (11)	0.4170 (16)	0.027 (3)*
C14	0.52804 (10)	0.38377 (7)	0.38733 (11)	0.0157 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0183 (4)	0.0229 (4)	0.0269 (4)	0.0028 (3)	0.0085 (3)	0.0040 (3)
C1	0.0174 (4)	0.0164 (4)	0.0174 (5)	0.0016 (3)	0.0064 (4)	−0.0017 (3)
C2	0.0178 (4)	0.0157 (4)	0.0168 (4)	0.0018 (3)	0.0080 (4)	0.0008 (3)
C3	0.0190 (5)	0.0241 (5)	0.0207 (5)	0.0002 (4)	0.0086 (4)	0.0058 (4)
C4	0.0254 (5)	0.0193 (5)	0.0274 (5)	0.0016 (4)	0.0115 (4)	0.0069 (4)
C5	0.0217 (5)	0.0276 (6)	0.0268 (5)	0.0052 (4)	0.0088 (4)	0.0092 (4)
C6	0.0197 (5)	0.0203 (5)	0.0215 (5)	0.0003 (4)	0.0043 (4)	−0.0025 (4)
C7	0.0215 (5)	0.0142 (4)	0.0239 (5)	−0.0025 (4)	0.0099 (4)	−0.0024 (4)
C8	0.0260 (5)	0.0143 (4)	0.0207 (5)	0.0010 (4)	0.0105 (4)	0.0016 (4)
C9	0.0190 (5)	0.0160 (4)	0.0175 (5)	0.0034 (4)	0.0077 (4)	−0.0004 (3)
C10	0.0231 (5)	0.0234 (5)	0.0185 (5)	0.0061 (4)	0.0070 (4)	0.0015 (4)
C11	0.0192 (5)	0.0324 (6)	0.0197 (5)	0.0048 (4)	0.0035 (4)	−0.0043 (4)
C12	0.0177 (5)	0.0265 (5)	0.0265 (5)	−0.0023 (4)	0.0080 (4)	−0.0074 (4)
C13	0.0194 (5)	0.0195 (5)	0.0231 (5)	−0.0011 (4)	0.0099 (4)	−0.0025 (4)
C14	0.0167 (4)	0.0151 (4)	0.0170 (4)	0.0017 (3)	0.0081 (4)	−0.0016 (3)

Geometric parameters (Å, º) top

O1—C5	1.4277 (13)	C6—H6B	1.003 (14)
O1—C6	1.4323 (12)	C7—C8	1.3675 (14)
C1—C2	1.3858 (13)	C7—H7A	0.979 (14)
C1—C7	1.4120 (14)	C8—C9	1.4112 (14)
C1—C6	1.5092 (13)	C8—H8A	0.975 (14)
C2—C14	1.4327 (13)	C9—C10	1.4229 (13)
C2—C3	1.5131 (13)	C9—C14	1.4292 (13)
C3—C4	1.5372 (14)	C10—C11	1.3657 (16)
C3—H3A	1.000 (14)	C10—H10A	0.984 (14)
C3—H3B	0.999 (14)	C11—C12	1.4084 (16)
C4—C5	1.5163 (15)	C11—H11A	0.969 (15)
C4—H4A	0.987 (14)	C12—C13	1.3712 (15)
C4—H4B	1.004 (15)	C12—H12A	0.976 (14)
C5—H5A	1.025 (15)	C13—C14	1.4248 (13)
C5—H5B	1.000 (13)	C13—H13A	0.977 (14)
C6—H6A	1.007 (13)

C5—O1—C6	113.34 (8)	O1—C6—H6B	108.3 (8)
C2—C1—C7	120.80 (9)	C1—C6—H6B	111.0 (8)
C2—C1—C6	120.95 (9)	H6A—C6—H6B	109.0 (10)
C7—C1—C6	118.24 (9)	C8—C7—C1	120.93 (9)
C1—C2—C14	119.18 (9)	C8—C7—H7A	118.6 (8)
C1—C2—C3	119.45 (9)	C1—C7—H7A	120.5 (8)
C14—C2—C3	121.38 (8)	C7—C8—C9	120.28 (9)
C2—C3—C4	114.25 (8)	C7—C8—H8A	119.9 (8)
C2—C3—H3A	111.1 (8)	C9—C8—H8A	119.8 (8)
C4—C3—H3A	107.9 (8)	C8—C9—C10	120.90 (9)
C2—C3—H3B	108.5 (8)	C8—C9—C14	119.61 (9)
C4—C3—H3B	109.2 (8)	C10—C9—C14	119.47 (9)
H3A—C3—H3B	105.5 (11)	C11—C10—C9	121.14 (10)
C5—C4—C3	114.27 (9)	C11—C10—H10A	122.0 (8)
C5—C4—H4A	107.2 (8)	C9—C10—H10A	116.8 (8)
C3—C4—H4A	108.7 (8)	C10—C11—C12	119.82 (10)
C5—C4—H4B	109.3 (8)	C10—C11—H11A	120.8 (9)
C3—C4—H4B	109.2 (8)	C12—C11—H11A	119.4 (9)
H4A—C4—H4B	108.0 (12)	C13—C12—C11	120.57 (10)
O1—C5—C4	114.42 (9)	C13—C12—H12A	119.5 (8)
O1—C5—H5A	108.2 (8)	C11—C12—H12A	119.9 (8)
C4—C5—H5A	109.3 (8)	C12—C13—C14	121.55 (10)
O1—C5—H5B	104.1 (8)	C12—C13—H13A	118.7 (8)
C4—C5—H5B	110.4 (8)	C14—C13—H13A	119.7 (8)
H5A—C5—H5B	110.3 (11)	C13—C14—C9	117.41 (9)
O1—C6—C1	113.36 (8)	C13—C14—C2	123.42 (9)
O1—C6—H6A	105.7 (7)	C9—C14—C2	119.15 (8)
C1—C6—H6A	109.2 (7)

C7—C1—C2—C14	2.09 (14)	C7—C8—C9—C14	1.43 (14)
C6—C1—C2—C14	−177.41 (8)	C8—C9—C10—C11	177.03 (9)
C7—C1—C2—C3	−178.58 (9)	C14—C9—C10—C11	−1.35 (15)
C6—C1—C2—C3	1.92 (14)	C9—C10—C11—C12	1.34 (15)
C1—C2—C3—C4	−62.32 (12)	C10—C11—C12—C13	0.19 (16)
C14—C2—C3—C4	117.00 (10)	C11—C12—C13—C14	−1.72 (15)
C2—C3—C4—C5	76.33 (12)	C12—C13—C14—C9	1.66 (14)
C6—O1—C5—C4	69.71 (12)	C12—C13—C14—C2	−176.93 (9)
C3—C4—C5—O1	−63.49 (12)	C8—C9—C14—C13	−178.54 (9)
C5—O1—C6—C1	−87.27 (10)	C10—C9—C14—C13	−0.14 (13)
C2—C1—C6—O1	65.29 (12)	C8—C9—C14—C2	0.11 (13)
C7—C1—C6—O1	−114.22 (10)	C10—C9—C14—C2	178.51 (8)
C2—C1—C7—C8	−0.56 (15)	C1—C2—C14—C13	176.72 (9)
C6—C1—C7—C8	178.95 (9)	C3—C2—C14—C13	−2.60 (14)
C1—C7—C8—C9	−1.23 (15)	C1—C2—C14—C9	−1.84 (13)
C7—C8—C9—C10	−176.95 (9)	C3—C2—C14—C9	178.83 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···O1ⁱ	0.970 (16)	2.558 (16)	3.4803 (14)	159.0 (11)
C12—H12A···O1ⁱⁱ	0.976 (15)	2.560 (15)	3.4661 (14)	154.5 (11)

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

Acknowledgements

The University of Toronto thanks NSERC for funding.

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