The Diels–Alder adduct of p-benzo­quinone and anthracene: 9,10-tetra­hydro-9,10[1′,2′]­benzeno­anthracene-1′,4′(2′H,3′H)-dione

Adams, H.; Ojea-Jimenez, I.; Jones, S.

doi:10.1107/S160053680400707X

organic compounds

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ISSN: 2056-9890

Volume 60| Part 4| April 2004| Pages o690-o691

https://doi.org/10.1107/S160053680400707X

The Diels–Alder adduct of p-benzoquinone and anthracene: 9,10-tetrahydro-9,10[1′,2′]benzenoanthracene-1′,4′(2′H,3′H)-dione

Harry Adams,^a ^* Isaac Ojea-Jimenez ^a and Simon Jones ^a

^aDepartment of Chemistry, University of Sheffield, Department of Chemistry, Brookhill, Sheffield S3 7HF, England
^*Correspondence e-mail: h.adams@sheffield.ac.uk

(Received 5 March 2004; accepted 25 March 2004; online 31 March 2004)

The structure of the title compound, C₂₀H₁₄O₂, has a rigid bicyclic backbone, and the six-membered diketone ring is in a shallow boat conformation. Both carbonyl groups are orientated away from the underlying benzene rings. The structure is compared to other similar anthracene Diels–Alder adducts.

Comment

Diels–Alder adducts from the reaction of anthracene with dienophiles have been used in a variety of applications, including the synthesis of discrete molecular architectures such as molecular gears (Stevens & Richards, 1997 ). Although the crystal structures of a number of such derivatives have been disclosed, somewhat surprisingly the structure of the adduct (1) of p-benzoquinone and anthracene has not been previously reported. Tautomer (2) does appear in the Cambridge Structural Database (Version 5.25; Allen et al. 2002 ); however, its full structure has not been deposited (Hashimoto et al., 1999 ).

The 2-ene-1,4-dione ring in (1) is in a shallow boat conformation in which the bonds C15—C16 and C19—C20 are parallel, and all the atoms of both these bonds are coplanar (r.m.s. deviation 0.007 Å). The two sets of atoms O2/C18/C16/C20 and O1/C17/C19/C15 (which contain the carbonyl groups) are essentially planar (r.m.s. deviations 0.009 and 0.007 Å, respectively) and these planar groups (O2/C18/C16/C20 and O1/C17/C19/C15) have dihedral angles with the previous plane (C15/C16/C19/C20) of 12.34 (13) and 18.99 (11)°, respectively. The difference in these angles is intriguing since the molecule itself is otherwise symmetrical. Unsymmetrical 9-substituted anthracene Diels–Alder adducts (3) and (4) also show similar deviations, although this is obviously more pronounced for the carbonyl group located proximal to the 9-substituent (Bharadwaj et al., 1985 ; Watson & Nagl, 1988 ).

In the crystal structure, weak intermolecular C—H⋯O bonds (see Table 1) connect the molecules into a three-dimensional network (Fig. 2)

Figure 1
View of (1) (50% probability displacement ellipsoids). H atoms are not shown.

Figure 2
Packing diagram (Spek, 2003

) showing weak C—H⋯O interactions (dashed lines). O atoms are coloured red.

Experimental

The title compound, (1), was prepared by the thermal Diels–Alder addition reaction of anthracene with p-benzoquinone (Wasielewski et al., 1989 ). Suitable crystals for X-ray diffraction analysis were obtained by slow evaporation of a dichloromethane/petrol (60–80) solution, resulting in colourless crystals.

Crystal data

C₂₀H₁₄O₂
M_r = 286.31
Triclinic, $[P\overline 1]$
a = 6.870 (3) Å
b = 8.333 (4) Å
c = 12.707 (5) Å
α = 78.567 (7)°
β = 78.991 (7)°
γ = 79.361 (7)°
V = 691.7 (5) Å³
Z = 2
D_x = 1.375 Mg m⁻³
Mo Kα radiation
Cell parameters from 1866 reflections
θ = 5.0–54.7°
μ = 0.09 mm⁻¹
T = 150 (2) K
Block, colourless
0.46 × 0.24 × 0.16 mm

Data collection

Bruker SMART 1000 diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.961, T_max = 0.986
4302 measured reflections
2373 independent reflections
1741 reflections with I > 2σ(I)
R_int = 0.025
θ_max = 25°
h = −8 → 8
k = −9 → 9
l = −15 → 14

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.136
S = 1.03
2373 reflections
199 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0738P)² + 0.2376P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.95	2.52	3.388 (3)	151
C6—H6⋯O2ⁱⁱ	0.95	2.46	3.385 (3)	164
C10—H10⋯O2ⁱⁱⁱ	1.00	2.57	3.302 (2)	130
Symmetry codes: (i) 1-x,1-y,1-z; (ii) 2-x,-y,-z; (iii) 2-x,1-y,-z.

H atoms were positioned geometrically and refined with a riding model (including torsional freedom for methyl groups), with C—H = 0.95–0.98 Å, and with U_iso(H) values constrained to be 1.2 (1.5 for methyl groups) times U_eq of the carrier atom.

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL (Bruker, 1997).

Supporting information

Crystal structure: contains datablocks global, 1. DOI: https://doi.org/10.1107/S160053680400707X/lh6180sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S160053680400707X/lh61801sup2.hkl

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL (Bruker, 1997).

(1) top

Crystal data top

C₂₀H₁₄O₂	Z = 2
M_r = 286.31	F(000) = 300
Triclinic, P1	D_x = 1.375 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.870 (3) Å	Cell parameters from 1866 reflections
b = 8.333 (4) Å	θ = 5.1–54.7°
c = 12.707 (5) Å	µ = 0.09 mm⁻¹
α = 78.567 (7)°	T = 150 K
β = 78.991 (7)°	Plate, colourless
γ = 79.361 (7)°	0.46 × 0.24 × 0.16 mm
V = 691.7 (5) Å³

Data collection top

Bruker SMART 1000 diffractometer	1741 reflections with I > 2σ(I)
ω scans	R_int = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 1997)	θ_max = 25°, θ_min = 1.7°
T_min = 0.961, T_max = 0.986	h = −8→8
4302 measured reflections	k = −9→9
2373 independent reflections	l = −15→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.047	w = 1/[σ²(F_o²) + (0.0738P)² + 0.2376P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.136	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.24 e Å⁻³
2373 reflections	Δρ_min = −0.27 e Å⁻³
199 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
O2	1.1857 (2)	0.32714 (19)	0.04934 (12)	0.0371 (4)
O1	1.0437 (3)	0.1850 (2)	0.47566 (13)	0.0435 (5)
C1	0.3560 (3)	0.4841 (3)	0.37728 (18)	0.0303 (5)
H1	0.3297	0.4512	0.454	0.036*
C2	0.2296 (3)	0.6139 (3)	0.3246 (2)	0.0344 (6)
H2	0.1158	0.6693	0.3657	0.041*
C3	0.2696 (3)	0.6620 (3)	0.2129 (2)	0.0329 (6)
H3	0.1821	0.7497	0.1781	0.039*
C4	0.4363 (3)	0.5838 (2)	0.15056 (18)	0.0283 (5)
H4	0.4637	0.6183	0.0741	0.034*
C5	0.7541 (3)	0.0568 (2)	0.11251 (18)	0.0267 (5)
H5	0.7846	0.09	0.036	0.032*
C6	0.7347 (3)	−0.1085 (3)	0.15683 (19)	0.0315 (5)
H6	0.7483	−0.1874	0.1102	0.038*
C7	0.6957 (3)	−0.1569 (2)	0.26878 (19)	0.0310 (5)
H7	0.6827	−0.2692	0.2982	0.037*
C8	0.6754 (3)	−0.0431 (2)	0.33860 (18)	0.0269 (5)
H8	0.6519	−0.0778	0.4152	0.032*
C9	0.6743 (3)	0.2622 (2)	0.35815 (16)	0.0231 (5)
H9	0.6397	0.2253	0.4384	0.028*
C10	0.7485 (3)	0.3545 (2)	0.14796 (16)	0.0227 (5)
H10	0.7706	0.389	0.0671	0.027*
C11	0.5212 (3)	0.4039 (2)	0.31528 (17)	0.0241 (5)
C12	0.5617 (3)	0.4541 (2)	0.20263 (16)	0.0230 (5)
C13	0.7283 (3)	0.1716 (2)	0.18166 (16)	0.0217 (5)
C14	0.6898 (3)	0.1220 (2)	0.29469 (16)	0.0219 (5)
C15	0.8831 (3)	0.3280 (2)	0.32630 (16)	0.0231 (5)
H15	0.8699	0.4303	0.3586	0.028*
C16	0.9310 (3)	0.3772 (2)	0.20054 (16)	0.0230 (5)
H16	0.9459	0.4972	0.1834	0.028*
C17	1.0366 (3)	0.1979 (3)	0.37928 (17)	0.0275 (5)
C18	1.1179 (3)	0.2805 (2)	0.14419 (17)	0.0253 (5)
C19	1.1718 (3)	0.0843 (3)	0.31257 (18)	0.0306 (5)
H19	1.2319	−0.0196	0.3475	0.037*
C20	1.2121 (3)	0.1233 (3)	0.20460 (18)	0.0301 (5)
H20	1.3041	0.0481	0.165	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0384 (10)	0.0381 (9)	0.0304 (9)	−0.0078 (7)	0.0038 (7)	−0.0022 (7)
O1	0.0513 (11)	0.0500 (10)	0.0306 (10)	−0.0075 (8)	−0.0173 (8)	0.0000 (7)
C1	0.0308 (13)	0.0277 (11)	0.0351 (13)	−0.0117 (10)	−0.0005 (10)	−0.0095 (10)
C2	0.0226 (12)	0.0284 (12)	0.0553 (16)	−0.0053 (9)	−0.0009 (10)	−0.0185 (11)
C3	0.0289 (13)	0.0210 (10)	0.0518 (15)	−0.0033 (9)	−0.0124 (11)	−0.0080 (10)
C4	0.0296 (13)	0.0228 (11)	0.0356 (13)	−0.0083 (9)	−0.0104 (10)	−0.0032 (9)
C5	0.0240 (12)	0.0277 (11)	0.0303 (12)	−0.0038 (9)	−0.0059 (9)	−0.0079 (9)
C6	0.0267 (13)	0.0238 (11)	0.0486 (15)	−0.0035 (9)	−0.0096 (10)	−0.0140 (10)
C7	0.0271 (13)	0.0153 (10)	0.0511 (15)	−0.0050 (8)	−0.0111 (10)	−0.0005 (9)
C8	0.0231 (12)	0.0227 (10)	0.0341 (12)	−0.0047 (9)	−0.0083 (9)	0.0020 (9)
C9	0.0267 (12)	0.0228 (10)	0.0205 (10)	−0.0091 (9)	−0.0021 (8)	−0.0025 (8)
C10	0.0258 (12)	0.0203 (10)	0.0228 (11)	−0.0054 (8)	−0.0052 (9)	−0.0021 (8)
C11	0.0233 (12)	0.0215 (10)	0.0304 (12)	−0.0083 (9)	−0.0046 (9)	−0.0065 (8)
C12	0.0242 (12)	0.0177 (10)	0.0311 (12)	−0.0084 (8)	−0.0082 (9)	−0.0047 (8)
C13	0.0179 (11)	0.0195 (10)	0.0295 (11)	−0.0042 (8)	−0.0067 (8)	−0.0041 (8)
C14	0.0183 (11)	0.0207 (10)	0.0284 (11)	−0.0062 (8)	−0.0065 (8)	−0.0023 (8)
C15	0.0248 (12)	0.0195 (10)	0.0267 (11)	−0.0069 (8)	−0.0050 (9)	−0.0043 (8)
C16	0.0242 (12)	0.0185 (10)	0.0276 (11)	−0.0077 (8)	−0.0047 (9)	−0.0024 (8)
C17	0.0286 (12)	0.0281 (11)	0.0280 (12)	−0.0133 (9)	−0.0074 (9)	0.0013 (9)
C18	0.0249 (12)	0.0259 (11)	0.0273 (12)	−0.0111 (9)	−0.0037 (9)	−0.0036 (9)
C19	0.0242 (12)	0.0260 (11)	0.0399 (14)	−0.0046 (9)	−0.0101 (10)	0.0037 (9)
C20	0.0231 (12)	0.0268 (11)	0.0397 (14)	−0.0034 (9)	−0.0030 (10)	−0.0060 (10)

Geometric parameters (Å, º) top

O2—C18	1.220 (2)	C9—C11	1.517 (3)
O1—C17	1.218 (3)	C9—C14	1.524 (3)
C1—C11	1.393 (3)	C9—C15	1.582 (3)
C1—C2	1.401 (3)	C9—H9	1
C1—H1	0.95	C10—C12	1.521 (3)
C2—C3	1.385 (3)	C10—C13	1.524 (3)
C2—H2	0.95	C10—C16	1.585 (3)
C3—C4	1.395 (3)	C10—H10	1
C3—H3	0.95	C11—C12	1.398 (3)
C4—C12	1.392 (3)	C13—C14	1.401 (3)
C4—H4	0.95	C15—C17	1.516 (3)
C5—C13	1.389 (3)	C15—C16	1.556 (3)
C5—C6	1.401 (3)	C15—H15	1
C5—H5	0.95	C16—C18	1.518 (3)
C6—C7	1.387 (3)	C16—H16	1
C6—H6	0.95	C17—C19	1.473 (3)
C7—C8	1.394 (3)	C18—C20	1.484 (3)
C7—H7	0.95	C19—C20	1.333 (3)
C8—C14	1.392 (3)	C19—H19	0.95
C8—H8	0.95	C20—H20	0.95

C11—C1—C2	118.9 (2)	C1—C11—C12	120.52 (19)
C11—C1—H1	120.6	C1—C11—C9	126.16 (19)
C2—C1—H1	120.6	C12—C11—C9	113.30 (17)
C3—C2—C1	120.3 (2)	C4—C12—C11	120.49 (19)
C3—C2—H2	119.9	C4—C12—C10	125.93 (19)
C1—C2—H2	119.9	C11—C12—C10	113.58 (17)
C2—C3—C4	121.1 (2)	C5—C13—C14	120.47 (18)
C2—C3—H3	119.4	C5—C13—C10	126.32 (19)
C4—C3—H3	119.4	C14—C13—C10	113.12 (17)
C12—C4—C3	118.7 (2)	C8—C14—C13	120.11 (18)
C12—C4—H4	120.6	C8—C14—C9	126.38 (19)
C3—C4—H4	120.6	C13—C14—C9	113.48 (17)
C13—C5—C6	119.3 (2)	C17—C15—C16	116.20 (17)
C13—C5—H5	120.4	C17—C15—C9	107.70 (16)
C6—C5—H5	120.4	C16—C15—C9	109.37 (16)
C7—C6—C5	120.0 (2)	C17—C15—H15	107.8
C7—C6—H6	120	C16—C15—H15	107.8
C5—C6—H6	120	C9—C15—H15	107.8
C6—C7—C8	120.90 (19)	C18—C16—C15	116.24 (16)
C6—C7—H7	119.6	C18—C16—C10	106.80 (16)
C8—C7—H7	119.6	C15—C16—C10	109.35 (16)
C14—C8—C7	119.2 (2)	C18—C16—H16	108.1
C14—C8—H8	120.4	C15—C16—H16	108.1
C7—C8—H8	120.4	C10—C16—H16	108.1
C11—C9—C14	107.99 (16)	O1—C17—C19	120.9 (2)
C11—C9—C15	105.89 (16)	O1—C17—C15	120.5 (2)
C14—C9—C15	106.44 (16)	C19—C17—C15	118.58 (18)
C11—C9—H9	112	O2—C18—C20	120.10 (19)
C14—C9—H9	112	O2—C18—C16	120.82 (19)
C15—C9—H9	112	C20—C18—C16	119.02 (18)
C12—C10—C13	107.89 (16)	C20—C19—C17	121.79 (19)
C12—C10—C16	106.94 (15)	C20—C19—H19	119.1
C13—C10—C16	105.24 (16)	C17—C19—H19	119.1
C12—C10—H10	112.1	C19—C20—C18	122.1 (2)
C13—C10—H10	112.1	C19—C20—H20	118.9
C16—C10—H10	112.1	C18—C20—H20	118.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.95	2.52	3.388 (3)	151
C6—H6···O2ⁱⁱ	0.95	2.46	3.385 (3)	164
C10—H10···O2ⁱⁱⁱ	1.00	2.57	3.302 (2)	130

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

Acknowledgements

We thank the Department of Chemistry, University of Sheffield, for support (IO).

References

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