(3Z,3′Z)-3,3′-(Ethane-1,2-diyl­idene)­bis[isobenzofuran-1(3H)-one]

Abstract

The title compound, C₁₈H₁₀O₄, has been isolated as an impurity in commercially available 6,11-dihydr­oxy-5,12-naphth­acenedione. The title compound exhibits yellow fluorescence in the solid state. The mol­ecule has crystallographic inversion symmetry and is planar, with an r.m.s. deviation of 0.031 (1) Å. The crystal structure is stabilized by C—H⋯O hydrogen bonds and π–π stacking inter­actions between 3-methyl­eneisobenzofuran-1(3H)-one units [inter­planar distance 3.43 (1) Å].

Related literature

For the crystallographic analysis and functionalization of 6,11-dihydr­oxy-5,12-naphthacenedione, see: Tomura et al. (2008 ▶); Ono et al. (2009 ▶). For the synthesis of the title compound, see: Ji et al. (2006 ▶).

Experimental

Crystal data

• C₁₈H₁₀O₄

• M _r = 290.26

• Triclinic,

• a = 6.9030 (13) Å

• b = 7.0374 (16) Å

• c = 7.7792 (13) Å

• α = 112.190 (5)°

• β = 95.696 (2)°

• γ = 107.239 (8)°

• V = 324.53 (11) ų

• Z = 1

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 173 K

• 1.00 × 0.50 × 0.40 mm

Data collection

• Rigaku/MSC Mercury CCD diffractometer

• Absorption correction: none

• 2656 measured reflections

• 1661 independent reflections

• 1323 reflections with I > 2σ(I)

• R _int = 0.044

Refinement

• R[F ² > 2σ(F ²)] = 0.066

• wR(F ²) = 0.176

• S = 0.97

• 1661 reflections

• 100 parameters

• H-atom parameters constrained

• Δρ_max = 0.35 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2i	0.95	2.70	3.459 (2)	137
C5—H5⋯O1ii	0.95	2.66	3.406 (2)	136
C6—H6⋯O2iii	0.95	2.71	3.4700 (19)	138
C9—H9⋯O2iii	0.95	2.55	3.3209 (18)	139

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

supplementary crystallographic information

Comment

Through the study of the crystallographic analysis and functionalities of 6,11-dihydroxy-5,12-naphthacenedione (Tomura et al., 2008; Ono et al., 2009), we found the existence of a yellow fluorescent compound as a by-product in the commercially available chemical reagent. After the separation of the by-product, the structure was determined to be the title compound, (I). Although the synthesis of (I) was already reported (Ji et al., 2006), the characterization has not been performed. In this paper, we report the separation, spectral data, and molecular and crystal structures of (I).

The molecular structure of (I) is shown in Fig. 1. The molecule is centrosymmetric and planar with an r.m.s. deviation of 0.031 (1) Å. The distances of the C9—C9 (-x + 1, -y, -z + 1) and C8—C9 bonds are 1.433 (3) and 1.345 (2) Å, respectively, indicating a butadiene skeleton. The bond length of C1—O2 [1.201 (2) Å] is reasonable for carbonyl group. Further, the O1—C1 and O1—C8 bonds result in O—C single bonds with a bond distance of 1.394 (2) Å. These bond distances support the molecular structure of (I).

In the crystal structure, the molecules are linked to each other through intermolecular C—H···O interactions (Table 1). The molecular arrangements shown in Figs. 2 and 3 run stepwise along the b and c axes, respectively. Fig. 4 also exhibits a stepwise arrangement along the (021) direction with C—H···O contacts. Furthermore, the 3-methyleneisobenzofuran-1(3H)-one rings overlap each other to form a π-stacking structure with an interplanar distance of 3.43 Å, as shown in Fig. 5.

Experimental

The commercially available 6,11-dihydroxy-5,12-naphthacenedione (100 mg, Aldrich) was recrystallized from ethyl acetate (280 ml) to afford pure red crystals of 6,11-dihydroxy-5,12-naphthacenedione (70 mg). The filtrate containing the title compound, (I) was concentrated, and the residue (25 mg) was dissolved in toluene (100 ml). The solution was washed with 1 M NaOH solutions (100 ml) ten times over until the NaOH solution was colorless. The organic solution was dried over Na₂SO₄ and concentrated to provide a yellow solid of (I) (ca 9% yield). Yellow prisms of the title compound, suitable for X-ray analysis were grown from a dichloromethane solution.

Refinement

All H atoms were placed in geometrically calculated positions, with C—H = 0.95 (aromatic) Å and U_iso(H) = 1.2U_eq(C) (aromatic), and refined using a riding model.

Figures

Fig. 1.

The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms and H atoms are shown as small spheres of arbitrary radii.

Fig. 2.

Aggregation along the b axis with C—H···O contacts.

Fig. 3.

Aggregation along the c axis with C—H···O contacts.

Fig. 4.

Aggregation along the (021) direction with C—H···O contacts.

Fig. 5.

π-Stacking structure with an interplanar distance of 3.43 Å.

Crystal data

C18H10O4	Z = 1
Mr = 290.26	F(000) = 150
Triclinic, P1	Dx = 1.485 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9030 (13) Å	Cell parameters from 1131 reflections
b = 7.0374 (16) Å	θ = 4.8–30.8°
c = 7.7792 (13) Å	µ = 0.11 mm−1
α = 112.190 (5)°	T = 173 K
β = 95.696 (2)°	Prism, yellow
γ = 107.239 (8)°	1.00 × 0.50 × 0.40 mm
V = 324.53 (11) Å3

Data collection

Rigaku/MSC Mercury CCD diffractometer	1323 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.044
Graphite Monochromator	θmax = 30.8°, θmin = 3.7°
Detector resolution: 14.62 pixels mm-1	h = −9→9
φ and ω scans	k = −9→5
2656 measured reflections	l = −7→10
1661 independent reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176	H-atom parameters constrained
S = 0.97	w = 1/[σ2(Fo2) + (0.1211P)2] where P = (Fo2 + 2Fc2)/3
1661 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

Special details

Experimental. IR (KBr, cm-1): 1784, 1645, 1472, 1343, 1281, 1073, 974, 766, 689; 1H NMR (CDCl3, δ p.p.m.): 6.86 (s, 2H), 7.60 (t, J = 7.6 Hz, 2H), 7.77 (t, J = 7.6 Hz, 2H), 7.81 (d, J = 7.6 Hz, 2H), 7.96 (d, J = 7.6 Hz, 2H); MS (EI): m/z 290 (M+), 104; UV-vis (CH2Cl2, nm): 406, 383.

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7382 (2)	0.6230 (2)	0.8120 (2)	0.0242 (4)
C2	0.7695 (2)	0.5873 (2)	0.9849 (2)	0.0216 (4)
C3	0.8463 (2)	0.7402 (2)	1.1749 (2)	0.0285 (4)
H3	0.8898	0.8939	1.2100	0.034*
C4	0.8568 (2)	0.6597 (3)	1.3105 (2)	0.0320 (4)
H4	0.9049	0.7593	1.4421	0.038*
C5	0.7974 (2)	0.4324 (3)	1.2568 (2)	0.0310 (4)
H5	0.8079	0.3814	1.3531	0.037*
C6	0.7236 (2)	0.2804 (2)	1.0665 (2)	0.0267 (4)
H6	0.6859	0.1271	1.0308	0.032*
C7	0.7070 (2)	0.3616 (2)	0.9299 (2)	0.0204 (3)
C8	0.6284 (2)	0.2534 (2)	0.7233 (2)	0.0207 (3)
C9	0.5404 (2)	0.0392 (2)	0.6005 (2)	0.0223 (4)
H9	0.5313	−0.0668	0.6501	0.027*
O1	0.65059 (16)	0.41594 (15)	0.65779 (15)	0.0248 (3)
O2	0.77382 (19)	0.78743 (17)	0.78771 (18)	0.0364 (4)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0231 (7)	0.0198 (7)	0.0242 (8)	0.0061 (6)	0.0010 (6)	0.0061 (6)
C2	0.0187 (6)	0.0193 (7)	0.0207 (7)	0.0044 (5)	0.0025 (5)	0.0046 (5)
C3	0.0263 (8)	0.0231 (7)	0.0245 (8)	0.0056 (6)	0.0027 (6)	0.0016 (6)
C4	0.0296 (8)	0.0343 (9)	0.0180 (8)	0.0048 (7)	0.0024 (6)	0.0027 (6)
C5	0.0287 (8)	0.0389 (9)	0.0197 (8)	0.0053 (7)	0.0045 (6)	0.0125 (7)
C6	0.0252 (7)	0.0270 (7)	0.0234 (8)	0.0050 (6)	0.0038 (6)	0.0101 (6)
C7	0.0176 (7)	0.0207 (7)	0.0188 (7)	0.0050 (5)	0.0031 (5)	0.0059 (5)
C8	0.0209 (7)	0.0205 (7)	0.0185 (7)	0.0070 (5)	0.0017 (5)	0.0072 (5)
C9	0.0221 (7)	0.0197 (7)	0.0208 (8)	0.0058 (5)	0.0009 (5)	0.0066 (6)
O1	0.0294 (6)	0.0188 (5)	0.0205 (6)	0.0055 (4)	−0.0005 (4)	0.0063 (4)
O2	0.0436 (7)	0.0221 (6)	0.0382 (7)	0.0073 (5)	−0.0006 (5)	0.0136 (5)

Geometric parameters (Å, °)

C1—O2	1.2007 (18)	C5—C6	1.388 (2)
C1—O1	1.3935 (17)	C5—H5	0.9500
C1—C2	1.465 (2)	C6—C7	1.393 (2)
C2—C3	1.389 (2)	C6—H6	0.9500
C2—C7	1.3914 (18)	C7—C8	1.4543 (19)
C3—C4	1.378 (2)	C8—C9	1.3447 (19)
C3—H3	0.9500	C8—O1	1.3944 (17)
C4—C5	1.405 (2)	C9—C9i	1.433 (3)
C4—H4	0.9500	C9—H9	0.9500
O2—C1—O1	120.77 (15)	C4—C5—H5	119.2
O2—C1—C2	132.22 (15)	C5—C6—C7	117.42 (14)
O1—C1—C2	107.01 (12)	C5—C6—H6	121.3
C3—C2—C7	122.43 (14)	C7—C6—H6	121.3
C3—C2—C1	129.48 (14)	C2—C7—C6	120.35 (14)
C7—C2—C1	108.08 (13)	C2—C7—C8	107.24 (13)
C4—C3—C2	117.22 (14)	C6—C7—C8	132.40 (13)
C4—C3—H3	121.4	C9—C8—O1	120.45 (13)
C2—C3—H3	121.4	C9—C8—C7	131.48 (13)
C3—C4—C5	120.95 (14)	O1—C8—C7	108.04 (11)
C3—C4—H4	119.5	C8—C9—C9i	124.02 (16)
C5—C4—H4	119.5	C8—C9—H9	118.0
C6—C5—C4	121.59 (15)	C9i—C9—H9	118.0
C6—C5—H5	119.2	C1—O1—C8	109.58 (12)
O2—C1—C2—C3	2.1 (3)	C5—C6—C7—C2	2.1 (2)
O1—C1—C2—C3	−177.95 (14)	C5—C6—C7—C8	−176.59 (13)
O2—C1—C2—C7	−177.93 (16)	C2—C7—C8—C9	−176.24 (14)
O1—C1—C2—C7	2.00 (15)	C6—C7—C8—C9	2.6 (3)
C7—C2—C3—C4	−0.7 (2)	C2—C7—C8—O1	1.63 (15)
C1—C2—C3—C4	179.22 (13)	C6—C7—C8—O1	−179.57 (13)
C2—C3—C4—C5	1.7 (2)	O1—C8—C9—C9i	−1.6 (3)
C3—C4—C5—C6	−0.8 (2)	C7—C8—C9—C9i	176.07 (16)
C4—C5—C6—C7	−1.1 (2)	O2—C1—O1—C8	178.96 (12)
C3—C2—C7—C6	−1.2 (2)	C2—C1—O1—C8	−0.98 (16)
C1—C2—C7—C6	178.83 (12)	C9—C8—O1—C1	177.79 (11)
C3—C2—C7—C8	177.76 (13)	C7—C8—O1—C1	−0.36 (16)
C1—C2—C7—C8	−2.20 (15)

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ii	0.95	2.70	3.459 (2)	137
C5—H5···O1iii	0.95	2.66	3.406 (2)	136
C6—H6···O2iv	0.95	2.71	3.4700 (19)	138
C9—H9···O2iv	0.95	2.55	3.3209 (18)	139

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