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2,3,6,7-Tetra­hydroxy-9,10-di­methyl-9,10-di­hydro-9,10-ethano­anthracene crystallizes with 1,4-dioxane to give a bis-solvate, C18H18O4·2C4H8O2. The bis­(catechol) mol­ecule is located on a twofold axis and the two aromatic rings form a dihedral angle of 130.61 (4)°. Hydro­gen bonds are formed between the hydroxyl groups and either a neighbouring bis­(catechol) mol­ecule or the ether-O atom of a dioxane mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101019035/av1094sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101019035/av1094Isup2.hkl
Contains datablock I

CCDC reference: 182025

Comment top

The condensation product of hexane-2,5-dione with catechol in sulfuric acid was at first considered, erroneously, to have an indano–indane structure (Niederl & Nagel, 1940). On the basis of NMR spectral (Le Goff, 1962) and chemical (Davidson & Musgrave, 1963) data, a dihydro-ethanoanthracene structure was suggested, but this compound appears to have been practically neglected in subsequent chemical literature, notwithstanding its potential interest as a building block for the preparation of synthetic receptors. In the course of our studies on catechol derivatives, we determined the crystal structure of this compound, 2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene, subsequently denoted bis(catechol), as a bis(1,4-dioxane) solvate (I). Dihydroanthracene and also dihydroethanoanthracene are rather common building blocks, but no structure comprising the tetrahydroxydihydroethanoanthracene unit has been reported. The crystal structures of very few molecules based on the tetrahydroxydihydroanthracene skeleton, which lack the dimethylene bridge and can be viewed as comprising two catechol rings linked in 4,5-positions by two carbon atoms, are known. A search of the Cambridge Structural Database (Allen & Kennard, 1993) gave only two hits, in which the bridges are substituted differently from those in (I) and the hydroxyl groups are replaced by methoxy ones (Benetollo et al., 1990; Guy et al., 1996).

The asymmetric unit of (I) comprises half a bis(catechol) and one 1,4-dioxane molecule, the bis(catechol) molecule admitting a twofold symmetry axis. The two catechol rings make a dihedral angle of 130.61 (4)°, whereas the dihedral angles between the catechol rings and the central plane defined (with a r.m.s. deviation of 0.004 Å) by atoms C7, C8, C9 and their symmetry-related counterparts are equal to 114.64 (4)°. The geometry thus appears somewhat distorted with respect to the ideal case of three dihedral angles of 120°. It is to be noted that the molecules with different bridges mentioned above are much flatter with a dihedral angle between the aromatic rings of about 151.7° (Benetollo et al., 1990).

Two kinds of hydrogen bonds involving the hydroxyl groups are present in (I). The two H atoms are very close to the aromatic mean plane with deviations of 0.059 (3) and 0.156 (3) Å for H1 and H2, respectively. H1 is bound to the ether atom O3 of the dioxane molecule, whereas H2 is bound to the hydroxyl atom O1 of a neighbouring bis(catechol) molecule. The latter results in the formation of ribbons of alternate up and down bis(catechol) molecules, directed along the c axis. In projection on the ab plane, these ribbons present a lozenge shape. The hydrogen-bonded dioxane molecules are located on both sides of these ribbons and are located between adjacent ribbons, one above and the other below along the b axis.

Experimental top

2,3,6,7-Tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene has been synthesized as previously reported (Davidson & Musgrave, 1963) and recrystallized from 1,4-dioxane.

Refinement top

The hydroxyl protons were found on the Fourier difference map and introduced as found, in spite of O—H bond lengths slightly larger than usual. All other H atoms were introduced at calculated positions (CH 0.93, CH2 0.97, CH3 0.96 Å). All H atoms were treated as riding atoms with a displacement parameter equal to 1.2 (OH, CH, CH2) or 1.5 (CH3) times that of the parent atom.

Computing details top

Data collection: Kappa-CCD software (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999); PARST97 (Nardelli, 1995).

Figures top
[Figure 1] Fig. 1. The title molecule with the atomic numbering scheme. H atoms are drawn as small spheres of arbitrary radii and hydrogen bonds are shown as dashed lines. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) -x, y, 0.5 - z; (ii) x, -y, 0.5 + z.
[Figure 2] Fig. 2. The packing arrangement of (I). H atoms have been omitted for clarity, unless those involved in hydrogen bonds. Hydrogen bonds are shown as dashed lines.
(I) top
Crystal data top
C18H18O4·2(C4H8O2)F(000) = 1016
Mr = 474.53Dx = 1.288 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 25.6848 (18) ÅCell parameters from 7056 reflections
b = 9.7131 (10) Åθ = 3.3–25.7°
c = 10.5531 (13) ŵ = 0.10 mm1
β = 111.630 (6)°T = 100 K
V = 2447.4 (4) Å3Parallelepiped, colourless
Z = 40.30 × 0.20 × 0.15 mm
Data collection top
Nonius Kappa-CCD
diffractometer
1723 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.063
Graphite monochromatorθmax = 25.7°, θmin = 3.3°
Detector resolution: 18 pixels mm-1h = 3131
ϕ scansk = 1111
7056 measured reflectionsl = 1212
2312 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0361P)2 + 1.9711P]
where P = (Fo2 + 2Fc2)/3
2312 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C18H18O4·2(C4H8O2)V = 2447.4 (4) Å3
Mr = 474.53Z = 4
Monoclinic, C2/cMo Kα radiation
a = 25.6848 (18) ŵ = 0.10 mm1
b = 9.7131 (10) ÅT = 100 K
c = 10.5531 (13) Å0.30 × 0.20 × 0.15 mm
β = 111.630 (6)°
Data collection top
Nonius Kappa-CCD
diffractometer
1723 reflections with I > 2σ(I)
7056 measured reflectionsRint = 0.063
2312 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.113H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å3
2312 reflectionsΔρmin = 0.26 e Å3
155 parameters
Special details top

Experimental. crystal-to-detector distance 28 mm

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. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms bound to O atoms have been found on the Fourier-difference map and introduced as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other hydrogen atoms were introduced at calculated positions as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. 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 (Å2) top
xyzUiso*/Ueq
O10.18347 (5)0.02013 (14)0.25789 (13)0.0256 (3)
H10.21290.01500.34390.031*
O20.19407 (5)0.02895 (14)0.52017 (13)0.0258 (3)
H20.19030.01820.61940.031*
C10.14009 (7)0.07344 (18)0.29069 (18)0.0207 (4)
C20.14481 (7)0.07759 (18)0.42595 (18)0.0211 (4)
C30.10113 (7)0.13098 (18)0.45892 (18)0.0206 (4)
H30.10410.13390.54940.025*
C40.05314 (7)0.17986 (18)0.35673 (18)0.0200 (4)
C50.04900 (7)0.17763 (18)0.22041 (17)0.0200 (4)
C60.09264 (7)0.12356 (18)0.18798 (18)0.0209 (4)
H60.09000.12100.09770.025*
C70.00355 (7)0.24621 (18)0.12102 (19)0.0214 (4)
C80.00171 (8)0.39700 (19)0.17547 (19)0.0253 (4)
H8A0.03060.44450.16990.030*
H8B0.03510.44610.11890.030*
C90.00750 (8)0.2455 (2)0.02641 (19)0.0257 (4)
H9A0.02460.29100.03270.039*
H9B0.04090.29280.08230.039*
H9C0.00870.15210.05730.039*
O30.28878 (5)0.04911 (13)0.41065 (14)0.0295 (3)
O40.37317 (6)0.07483 (14)0.67391 (15)0.0371 (4)
C100.32075 (9)0.1723 (2)0.4532 (2)0.0385 (5)
H10A0.35280.16900.42560.046*
H10B0.29800.25080.40890.046*
C110.34054 (10)0.1898 (2)0.6046 (2)0.0448 (6)
H11A0.30840.19980.63140.054*
H11B0.36290.27290.63090.054*
C120.34128 (8)0.0487 (2)0.6314 (2)0.0335 (5)
H12A0.36410.12700.67620.040*
H12B0.30910.04550.65870.040*
C130.32170 (8)0.0668 (2)0.4801 (2)0.0316 (5)
H13A0.29940.15010.45380.038*
H13B0.35390.07670.45350.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0198 (7)0.0351 (7)0.0223 (7)0.0050 (5)0.0080 (5)0.0007 (6)
O20.0179 (6)0.0375 (8)0.0205 (7)0.0060 (6)0.0053 (5)0.0043 (6)
C10.0192 (9)0.0206 (9)0.0249 (9)0.0005 (7)0.0112 (8)0.0003 (7)
C20.0184 (9)0.0207 (9)0.0221 (9)0.0005 (7)0.0049 (7)0.0017 (7)
C30.0201 (9)0.0216 (9)0.0202 (9)0.0012 (7)0.0077 (7)0.0000 (7)
C40.0190 (9)0.0170 (8)0.0235 (9)0.0022 (7)0.0073 (7)0.0022 (7)
C50.0189 (9)0.0182 (9)0.0210 (9)0.0029 (7)0.0053 (7)0.0009 (7)
C60.0214 (9)0.0212 (9)0.0197 (9)0.0020 (7)0.0073 (8)0.0005 (7)
C70.0181 (9)0.0218 (9)0.0232 (9)0.0011 (7)0.0064 (8)0.0025 (8)
C80.0189 (9)0.0207 (9)0.0330 (11)0.0010 (7)0.0057 (8)0.0023 (8)
C90.0208 (9)0.0291 (10)0.0263 (10)0.0004 (8)0.0076 (8)0.0063 (8)
O30.0219 (7)0.0280 (7)0.0347 (8)0.0024 (5)0.0058 (6)0.0056 (6)
O40.0326 (8)0.0330 (8)0.0365 (8)0.0052 (6)0.0021 (7)0.0036 (6)
C100.0309 (11)0.0281 (11)0.0486 (14)0.0056 (9)0.0054 (10)0.0080 (10)
C110.0419 (13)0.0295 (12)0.0506 (14)0.0070 (10)0.0023 (11)0.0036 (10)
C120.0272 (11)0.0332 (11)0.0377 (12)0.0044 (9)0.0092 (9)0.0066 (9)
C130.0258 (10)0.0256 (11)0.0390 (12)0.0018 (8)0.0067 (9)0.0023 (9)
Geometric parameters (Å, º) top
O1—C11.383 (2)C8—H8B0.9700
O1—H11.0025C9—H9A0.9600
O2—C21.373 (2)C9—H9B0.9600
O2—H21.0911C9—H9C0.9600
C1—C61.387 (2)O3—C101.426 (2)
C1—C21.388 (2)O3—C131.436 (2)
C2—C31.392 (2)O4—C111.425 (2)
C3—C41.388 (2)O4—C121.429 (2)
C3—H30.9300C10—C111.497 (3)
C4—C51.403 (2)C10—H10A0.9700
C4—C7i1.521 (2)C10—H10B0.9700
C5—C61.390 (2)C11—H11A0.9700
C5—C71.524 (2)C11—H11B0.9700
C6—H60.9300C12—C131.498 (3)
C7—C4i1.521 (2)C12—H12A0.9700
C7—C91.521 (3)C12—H12B0.9700
C7—C81.568 (3)C13—H13A0.9700
C8—C8i1.543 (4)C13—H13B0.9700
C8—H8A0.9700
C1—O1—H1107.9C7—C9—H9A109.5
C2—O2—H2110.1C7—C9—H9B109.5
O1—C1—C6119.52 (15)H9A—C9—H9B109.5
O1—C1—C2119.68 (15)C7—C9—H9C109.5
C6—C1—C2120.79 (15)H9A—C9—H9C109.5
O2—C2—C1116.26 (15)H9B—C9—H9C109.5
O2—C2—C3124.05 (16)C10—O3—C13109.53 (15)
C1—C2—C3119.69 (16)C11—O4—C12109.65 (15)
C4—C3—C2120.00 (16)O3—C10—C11111.16 (18)
C4—C3—H3120.0O3—C10—H10A109.4
C2—C3—H3120.0C11—C10—H10A109.4
C3—C4—C5120.08 (16)O3—C10—H10B109.4
C3—C4—C7i125.39 (16)C11—C10—H10B109.4
C5—C4—C7i114.42 (15)H10A—C10—H10B108.0
C6—C5—C4119.67 (16)O4—C11—C10111.26 (18)
C6—C5—C7125.85 (16)O4—C11—H11A109.4
C4—C5—C7114.35 (15)C10—C11—H11A109.4
C1—C6—C5119.76 (16)O4—C11—H11B109.4
C1—C6—H6120.1C10—C11—H11B109.4
C5—C6—H6120.1H11A—C11—H11B108.0
C4i—C7—C9114.32 (15)O4—C12—C13111.18 (16)
C4i—C7—C5106.75 (14)O4—C12—H12A109.4
C9—C7—C5114.21 (15)C13—C12—H12A109.4
C4i—C7—C8104.66 (14)O4—C12—H12B109.4
C9—C7—C8111.16 (15)C13—C12—H12B109.4
C5—C7—C8104.88 (14)H12A—C12—H12B108.0
C8i—C8—C7110.88 (10)O3—C13—C12110.81 (16)
C8i—C8—H8A109.5O3—C13—H13A109.5
C7—C8—H8A109.5C12—C13—H13A109.5
C8i—C8—H8B109.5O3—C13—H13B109.5
C7—C8—H8B109.5C12—C13—H13B109.5
H8A—C8—H8B108.1H13A—C13—H13B108.1
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O31.001.842.6745 (18)138
O2—H2···O1ii1.091.582.6644 (18)172
Symmetry code: (ii) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC18H18O4·2(C4H8O2)
Mr474.53
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)25.6848 (18), 9.7131 (10), 10.5531 (13)
β (°) 111.630 (6)
V3)2447.4 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.30 × 0.20 × 0.15
Data collection
DiffractometerNonius Kappa-CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7056, 2312, 1723
Rint0.063
(sin θ/λ)max1)0.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.113, 1.06
No. of reflections2312
No. of parameters155
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.26

Computer programs: Kappa-CCD software (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999); PARST97 (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O31.001.842.6745 (18)138.1
O2—H2···O1i1.091.582.6644 (18)171.8
Symmetry code: (i) x, y, z+1/2.
 

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