10-Methyl-9,11-annulated dibenzobarrelene

Devassia, T.; Mathew, E.M.; Sithambaresan, M.; Unnikrishnan, P.A.; Kurup, M.R.P.

doi:10.1107/S2414314618011021

organic compounds

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Volume 3| Part 8| August 2018| x181102

https://doi.org/10.1107/S2414314618011021

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10-Methyl-9,11-annulated dibenzobarrelene

Tomson Devassia,^a Eason M. Mathew,^a M. Sithambaresan,^b ^* P. A. Unnikrishnan ^a and M. R. Prathapachandra Kurup ^c

^aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi-22, Kerala, India, ^bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka, and ^cDepartment of Chemistry, School of Physical Sciences, Central University of Kerala, Riverside Transit Campus, Nileshwar 671 314, India
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 25 July 2018; accepted 2 August 2018; online 10 August 2018)

In the title compound (systematic name: 8-methyl-16-oxapentacyclo[6.6.5.0^1,18.0^2,7.0^9,14]nonadeca-2,4,6,9(14),10,12,18-heptaen-15-one), C₁₉H₁₄O₂, the benzene rings form a dihedral angle of 64.84 (7)°. In the crystal, π–π stacking interactions, with a centroid–centroid distance of 3.7695 (8) Å, and weak C—H⋯π interactions link molecules along the b-axis direction.

Keywords: crystal structure; dibenzobarrelene; 9,11-annulated dibenzobarrelene.

CCDC reference: 1859772

Structure description

Dibenzobarrelene systems have attracted interest over the years because of their biological (Khalil et al., 2010 ) and photochemical properties (Zimmerman & Grunewald, 1966 ). Suitably substituted dibenzobarrelenes exhibit interesting physical properties (Ishii et al., 2016 ). Mathew et al. (2013 , 2014 ) reported two dibenzobarrelene derivatives and discussed their structural features. A recent report highlighted the applications of dibenzobarrelenes in OLEDs and photoluminescent materials (Ishii et al., 2018 ).

In the present study, an intramolecular Diels–Alder reaction was employed for the synthesis of 9,11-annulated dibenzobarrelenes and their diffraction-quality single crystals could be obtained by crystallization from suitable solvents. The derivatives can be easily modified structurally by using different substituents on the bridgehead positions. In the case of the title compound, the bridgehead position 10 is substituted with a methyl group and we obtained good-quality single crystals by recrystallization from acetonitrile. The molecular structure of the title compound is shown in Fig. 1. The two benzene rings form a dihedral of 64.84 (7)°. These rings form angles of 58.86 (8) and 56.96 (6)°, respectively, with the annulated ring at the vinyllic bridge head position.

Figure 1
The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.

In the crystal, π–π stacking interactions are present between inversion-related rings (C1–C4/C18/C19) with a centroid–centroid distance of 3.7695 (8) Å. Pairs of weak C—H⋯π interactions are also present between these inversion-related molecules (Table 1, Fig. 2). A further C—H⋯π interaction links the inversion-related molecules along the b-axis direction (Figs. 2 and 3).

Table 1
C—H⋯π interactions (Å, °)

Cg1 and Cg2 are the centroids of the C6–C9/C16/C17 and C1–C4/C18/C19 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg1ⁱ	0.93	2.80	3.582 (2)	142
C11—H11B⋯Cg2ⁱⁱ	0.97	2.74	3.675 (2)	163
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 2
The π–π (blue) and C—H⋯π (brown) interactions present in the title compound.

Figure 3
The packing viewed along the b axis.

Synthesis and crystallization

The title compound was synthesized by a reported procedure (Ciganek, 1980 ). 10-Methyl-9-anthracenecarboxylic acid (1.1 g, 5 mmol) was dissolved in acetone and stirred at room temperature for 1 h with trimethylamine (0.70 ml, 5 mmol) and cyanuric chloride (0.92 g, 5 mmol). The acid chloride obtained was treated with propargyl alcohol (0.30 ml, 5 mmol) for about 4 h to obtain propargyl-9-anthroate, which underwent an intramolecular Diels–Alder reaction to give the target 9,11-anulated barrelene derivative. The product was purified by silica column chromatography, eluting with a 1:1 DCM–hexane mixture. Recrystallization was carried out in an acetonitrile solvent by slow evaporation.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₁₄O₂
M_r	274.30
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	296
a, b, c (Å)	19.7403 (10), 9.3294 (3), 15.0595 (7)
V (Å³)	2773.4 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.967, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	21513, 3394, 2487
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.132, 1.04
No. of reflections	3394
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXT (Sheldrick, 2015a ), ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2010 ), SHELXL2018 (Sheldrick, 2015b ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1859772

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314618011021/lh4037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618011021/lh4037Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618011021/lh4037Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b) and publCIF (Westrip, 2010).

8-Methyl-16-oxapentacyclo[6.6.5.0^1,18.0^2,7.0^9,14]nonadeca-2,4,6,9(14),10,12,18-heptaen-15-one top

Crystal data top

C₁₉H₁₄O₂	D_x = 1.314 Mg m⁻³
M_r = 274.30	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 8066 reflections
a = 19.7403 (10) Å	θ = 4.8–56.3°
b = 9.3294 (3) Å	µ = 0.08 mm⁻¹
c = 15.0595 (7) Å	T = 296 K
V = 2773.4 (2) Å³	Block, colorless
Z = 8	0.40 × 0.30 × 0.20 mm
F(000) = 1152

Data collection top

Bruker Kappa APEXII CCD diffractometer	2487 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
ω and φ scan	θ_max = 28.3°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −26→19
T_min = 0.967, T_max = 0.983	k = −9→12
21513 measured reflections	l = −19→18
3394 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.046	w = 1/[σ²(F_o²) + (0.068P)² + 0.5261P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.132	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.22 e Å⁻³
3394 reflections	Δρ_min = −0.25 e Å⁻³
192 parameters	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0118 (12)

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.

Refinement. Carbon bound H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å and with U_iso(H) = 1.2 U_eq(C) (1.5 times U_eq(C) for methyl groups).

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

	x	y	z	U_iso*/U_eq
O1	0.29033 (7)	0.80423 (15)	−0.15003 (8)	0.0740 (4)
O2	0.40199 (8)	0.83530 (16)	−0.15059 (9)	0.0827 (5)
C1	0.44196 (8)	0.28888 (15)	−0.00666 (12)	0.0503 (4)
H1	0.461537	0.199210	0.001693	0.060*
C2	0.45800 (7)	0.36683 (16)	−0.08067 (11)	0.0483 (4)
H2	0.487959	0.329543	−0.122356	0.058*
C3	0.42961 (7)	0.50186 (15)	−0.09380 (9)	0.0410 (3)
H3	0.440680	0.555812	−0.143655	0.049*
C4	0.38498 (6)	0.55377 (13)	−0.03171 (8)	0.0331 (3)
C5	0.34901 (7)	0.69910 (14)	−0.03169 (9)	0.0368 (3)
C6	0.37181 (6)	0.77210 (13)	0.05361 (9)	0.0348 (3)
C7	0.40604 (7)	0.90020 (15)	0.06192 (11)	0.0461 (4)
H7	0.417357	0.953570	0.011919	0.055*
C8	0.42329 (8)	0.94811 (17)	0.14604 (13)	0.0574 (5)
H8	0.446029	1.034771	0.152578	0.069*
C9	0.40712 (8)	0.86881 (18)	0.21974 (12)	0.0569 (5)
H9	0.419167	0.901980	0.275796	0.068*
C10	0.27445 (7)	0.66803 (16)	−0.02136 (10)	0.0432 (3)
C11	0.23853 (9)	0.7332 (2)	−0.09881 (11)	0.0650 (5)
H11A	0.216396	0.659710	−0.133955	0.078*
H11B	0.204683	0.801348	−0.078902	0.078*
C12	0.35311 (10)	0.78600 (18)	−0.11548 (11)	0.0561 (4)
C13	0.25779 (7)	0.59227 (16)	0.04863 (10)	0.0449 (4)
H13	0.213399	0.566592	0.061862	0.054*
C14	0.31846 (6)	0.55000 (14)	0.10663 (9)	0.0371 (3)
C15	0.29780 (9)	0.46275 (18)	0.18740 (11)	0.0576 (4)
H15A	0.267777	0.518400	0.223819	0.086*
H15B	0.337410	0.437734	0.220981	0.086*
H15C	0.275158	0.376981	0.168433	0.086*
C16	0.35485 (6)	0.69107 (14)	0.12803 (9)	0.0345 (3)
C17	0.37298 (7)	0.73966 (17)	0.21144 (10)	0.0456 (4)
H17	0.362351	0.686079	0.261617	0.055*
C18	0.36800 (6)	0.47459 (13)	0.04359 (9)	0.0336 (3)
C19	0.39709 (7)	0.34135 (15)	0.05595 (11)	0.0445 (4)
H19	0.386568	0.287351	0.105994	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0880 (9)	0.0844 (9)	0.0496 (7)	0.0323 (8)	−0.0154 (6)	0.0128 (6)
O2	0.0991 (11)	0.0788 (9)	0.0700 (9)	0.0036 (8)	0.0134 (8)	0.0381 (7)
C1	0.0412 (7)	0.0315 (7)	0.0783 (11)	0.0040 (5)	−0.0036 (7)	−0.0066 (7)
C2	0.0359 (7)	0.0475 (8)	0.0614 (10)	0.0043 (6)	−0.0002 (6)	−0.0193 (7)
C3	0.0391 (7)	0.0451 (8)	0.0388 (7)	−0.0007 (6)	0.0002 (5)	−0.0058 (6)
C4	0.0316 (6)	0.0313 (6)	0.0364 (7)	0.0003 (5)	−0.0044 (5)	−0.0038 (5)
C5	0.0402 (7)	0.0349 (7)	0.0354 (7)	0.0055 (5)	−0.0019 (5)	0.0024 (5)
C6	0.0326 (6)	0.0292 (6)	0.0427 (7)	0.0065 (5)	−0.0021 (5)	−0.0009 (5)
C7	0.0433 (7)	0.0285 (7)	0.0663 (10)	0.0049 (5)	−0.0029 (7)	0.0012 (6)
C8	0.0497 (9)	0.0350 (8)	0.0876 (13)	0.0030 (6)	−0.0151 (8)	−0.0172 (8)
C9	0.0541 (9)	0.0559 (10)	0.0607 (11)	0.0107 (7)	−0.0162 (8)	−0.0271 (8)
C10	0.0376 (7)	0.0464 (8)	0.0457 (8)	0.0108 (6)	−0.0099 (6)	−0.0113 (7)
C11	0.0595 (10)	0.0828 (13)	0.0526 (10)	0.0290 (9)	−0.0197 (8)	−0.0119 (9)
C12	0.0744 (11)	0.0493 (9)	0.0447 (9)	0.0154 (8)	−0.0008 (8)	0.0096 (7)
C13	0.0294 (6)	0.0511 (8)	0.0541 (9)	−0.0009 (6)	−0.0009 (6)	−0.0109 (7)
C14	0.0345 (6)	0.0381 (7)	0.0386 (7)	−0.0030 (5)	0.0024 (5)	0.0016 (5)
C15	0.0599 (9)	0.0592 (10)	0.0536 (10)	−0.0109 (8)	0.0153 (8)	0.0074 (8)
C16	0.0294 (6)	0.0366 (7)	0.0376 (7)	0.0051 (5)	−0.0006 (5)	−0.0051 (5)
C17	0.0433 (7)	0.0536 (8)	0.0399 (8)	0.0096 (6)	−0.0013 (6)	−0.0090 (6)
C18	0.0305 (6)	0.0298 (6)	0.0404 (7)	−0.0036 (5)	−0.0032 (5)	−0.0018 (5)
C19	0.0420 (7)	0.0320 (7)	0.0594 (9)	−0.0034 (6)	−0.0030 (6)	0.0061 (6)

Geometric parameters (Å, º) top

O1—C12	1.355 (2)	C8—H8	0.9300
O1—C11	1.442 (3)	C9—C17	1.386 (2)
O2—C12	1.193 (2)	C9—H9	0.9300
C1—C2	1.368 (2)	C10—C13	1.311 (2)
C1—C19	1.383 (2)	C10—C11	1.494 (2)
C1—H1	0.9300	C11—H11A	0.9700
C2—C3	1.393 (2)	C11—H11B	0.9700
C2—H2	0.9300	C13—C14	1.5339 (19)
C3—C4	1.3730 (18)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.5194 (19)
C4—C18	1.3943 (18)	C14—C16	1.5336 (18)
C4—C5	1.5305 (17)	C14—C18	1.5338 (18)
C5—C12	1.502 (2)	C15—H15A	0.9600
C5—C10	1.5081 (19)	C15—H15B	0.9600
C5—C6	1.5220 (18)	C15—H15C	0.9600
C6—C7	1.3786 (19)	C16—C17	1.3825 (19)
C6—C16	1.3927 (19)	C17—H17	0.9300
C7—C8	1.386 (2)	C18—C19	1.3819 (18)
C7—H7	0.9300	C19—H19	0.9300
C8—C9	1.372 (3)

C12—O1—C11	112.66 (13)	O1—C11—H11A	110.6
C2—C1—C19	121.02 (13)	C10—C11—H11A	110.6
C2—C1—H1	119.5	O1—C11—H11B	110.6
C19—C1—H1	119.5	C10—C11—H11B	110.6
C1—C2—C3	120.22 (13)	H11A—C11—H11B	108.8
C1—C2—H2	119.9	O2—C12—O1	121.43 (16)
C3—C2—H2	119.9	O2—C12—C5	128.62 (17)
C4—C3—C2	118.72 (14)	O1—C12—C5	109.95 (15)
C4—C3—H3	120.6	C10—C13—C14	113.61 (12)
C2—C3—H3	120.6	C10—C13—H13	123.2
C3—C4—C18	121.41 (12)	C14—C13—H13	123.2
C3—C4—C5	127.61 (12)	C15—C14—C16	114.66 (12)
C18—C4—C5	110.96 (10)	C15—C14—C18	114.89 (12)
C12—C5—C10	104.06 (12)	C16—C14—C18	103.01 (9)
C12—C5—C6	116.85 (12)	C15—C14—C13	112.58 (12)
C10—C5—C6	106.71 (11)	C16—C14—C13	105.35 (11)
C12—C5—C4	116.94 (11)	C18—C14—C13	105.27 (10)
C10—C5—C4	106.41 (11)	C14—C15—H15A	109.5
C6—C5—C4	105.03 (10)	C14—C15—H15B	109.5
C7—C6—C16	121.02 (13)	H15A—C15—H15B	109.5
C7—C6—C5	127.55 (13)	C14—C15—H15C	109.5
C16—C6—C5	111.42 (11)	H15A—C15—H15C	109.5
C6—C7—C8	118.88 (15)	H15B—C15—H15C	109.5
C6—C7—H7	120.6	C17—C16—C6	119.40 (13)
C8—C7—H7	120.6	C17—C16—C14	126.41 (12)
C9—C8—C7	120.57 (14)	C6—C16—C14	114.16 (11)
C9—C8—H8	119.7	C16—C17—C9	119.53 (15)
C7—C8—H8	119.7	C16—C17—H17	120.2
C8—C9—C17	120.60 (15)	C9—C17—H17	120.2
C8—C9—H9	119.7	C19—C18—C4	119.09 (12)
C17—C9—H9	119.7	C19—C18—C14	126.46 (12)
C13—C10—C11	136.70 (15)	C4—C18—C14	114.43 (10)
C13—C10—C5	115.56 (12)	C18—C19—C1	119.52 (14)
C11—C10—C5	107.72 (13)	C18—C19—H19	120.2
O1—C11—C10	105.55 (13)	C1—C19—H19	120.2

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C6–C9/C16/C17 and C1–C4/C18/C19 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg1ⁱ	0.93	2.80	3.582 (2)	142
C11—H11B···Cg2ⁱⁱ	0.97	2.74	3.675 (2)	163

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

Acknowledgements

We acknowledge the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi-22, India, for single-crystal X-ray diffraction measurements.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

10-Methyl-9,11-annulated dibenzobarrelene

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds