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
CCDC reference: 182025
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.
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.
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).
Crystal data top
C18H18O4·2(C4H8O2) | F(000) = 1016 |
Mr = 474.53 | Dx = 1.288 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 25.6848 (18) Å | Cell parameters from 7056 reflections |
b = 9.7131 (10) Å | θ = 3.3–25.7° |
c = 10.5531 (13) Å | µ = 0.10 mm−1 |
β = 111.630 (6)° | T = 100 K |
V = 2447.4 (4) Å3 | Parallelepiped, colourless |
Z = 4 | 0.30 × 0.20 × 0.15 mm |
Data collection top
Nonius Kappa-CCD diffractometer | 1723 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.063 |
Graphite monochromator | θmax = 25.7°, θmin = 3.3° |
Detector resolution: 18 pixels mm-1 | h = −31→31 |
ϕ scans | k = −11→11 |
7056 measured reflections | l = −12→12 |
2312 independent reflections | |
Refinement top
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-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 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C18H18O4·2(C4H8O2) | V = 2447.4 (4) Å3 |
Mr = 474.53 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.6848 (18) Å | µ = 0.10 mm−1 |
b = 9.7131 (10) Å | T = 100 K |
c = 10.5531 (13) Å | 0.30 × 0.20 × 0.15 mm |
β = 111.630 (6)° | |
Data collection top
Nonius Kappa-CCD diffractometer | 1723 reflections with I > 2σ(I) |
7056 measured reflections | Rint = 0.063 |
2312 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.20 e Å−3 |
2312 reflections | Δρmin = −0.26 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
O1 | 0.18347 (5) | 0.02013 (14) | 0.25789 (13) | 0.0256 (3) | |
H1 | 0.2129 | −0.0150 | 0.3439 | 0.031* | |
O2 | 0.19407 (5) | 0.02895 (14) | 0.52017 (13) | 0.0258 (3) | |
H2 | 0.1903 | 0.0182 | 0.6194 | 0.031* | |
C1 | 0.14009 (7) | 0.07344 (18) | 0.29069 (18) | 0.0207 (4) | |
C2 | 0.14481 (7) | 0.07759 (18) | 0.42595 (18) | 0.0211 (4) | |
C3 | 0.10113 (7) | 0.13098 (18) | 0.45892 (18) | 0.0206 (4) | |
H3 | 0.1041 | 0.1339 | 0.5494 | 0.025* | |
C4 | 0.05314 (7) | 0.17986 (18) | 0.35673 (18) | 0.0200 (4) | |
C5 | 0.04900 (7) | 0.17763 (18) | 0.22041 (17) | 0.0200 (4) | |
C6 | 0.09264 (7) | 0.12356 (18) | 0.18798 (18) | 0.0209 (4) | |
H6 | 0.0900 | 0.1210 | 0.0977 | 0.025* | |
C7 | −0.00355 (7) | 0.24621 (18) | 0.12102 (19) | 0.0214 (4) | |
C8 | −0.00171 (8) | 0.39700 (19) | 0.17547 (19) | 0.0253 (4) | |
H8A | 0.0306 | 0.4445 | 0.1699 | 0.030* | |
H8B | −0.0351 | 0.4461 | 0.1189 | 0.030* | |
C9 | −0.00750 (8) | 0.2455 (2) | −0.02641 (19) | 0.0257 (4) | |
H9A | 0.0246 | 0.2910 | −0.0327 | 0.039* | |
H9B | −0.0409 | 0.2928 | −0.0823 | 0.039* | |
H9C | −0.0087 | 0.1521 | −0.0573 | 0.039* | |
O3 | 0.28878 (5) | −0.04911 (13) | 0.41065 (14) | 0.0295 (3) | |
O4 | 0.37317 (6) | −0.07483 (14) | 0.67391 (15) | 0.0371 (4) | |
C10 | 0.32075 (9) | −0.1723 (2) | 0.4532 (2) | 0.0385 (5) | |
H10A | 0.3528 | −0.1690 | 0.4256 | 0.046* | |
H10B | 0.2980 | −0.2508 | 0.4089 | 0.046* | |
C11 | 0.34054 (10) | −0.1898 (2) | 0.6046 (2) | 0.0448 (6) | |
H11A | 0.3084 | −0.1998 | 0.6314 | 0.054* | |
H11B | 0.3629 | −0.2729 | 0.6309 | 0.054* | |
C12 | 0.34128 (8) | 0.0487 (2) | 0.6314 (2) | 0.0335 (5) | |
H12A | 0.3641 | 0.1270 | 0.6762 | 0.040* | |
H12B | 0.3091 | 0.0455 | 0.6587 | 0.040* | |
C13 | 0.32170 (8) | 0.0668 (2) | 0.4801 (2) | 0.0316 (5) | |
H13A | 0.2994 | 0.1501 | 0.4538 | 0.038* | |
H13B | 0.3539 | 0.0767 | 0.4535 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0198 (7) | 0.0351 (7) | 0.0223 (7) | 0.0050 (5) | 0.0080 (5) | 0.0007 (6) |
O2 | 0.0179 (6) | 0.0375 (8) | 0.0205 (7) | 0.0060 (6) | 0.0053 (5) | 0.0043 (6) |
C1 | 0.0192 (9) | 0.0206 (9) | 0.0249 (9) | −0.0005 (7) | 0.0112 (8) | −0.0003 (7) |
C2 | 0.0184 (9) | 0.0207 (9) | 0.0221 (9) | 0.0005 (7) | 0.0049 (7) | 0.0017 (7) |
C3 | 0.0201 (9) | 0.0216 (9) | 0.0202 (9) | −0.0012 (7) | 0.0077 (7) | 0.0000 (7) |
C4 | 0.0190 (9) | 0.0170 (8) | 0.0235 (9) | −0.0022 (7) | 0.0073 (7) | −0.0022 (7) |
C5 | 0.0189 (9) | 0.0182 (9) | 0.0210 (9) | −0.0029 (7) | 0.0053 (7) | 0.0009 (7) |
C6 | 0.0214 (9) | 0.0212 (9) | 0.0197 (9) | −0.0020 (7) | 0.0073 (8) | 0.0005 (7) |
C7 | 0.0181 (9) | 0.0218 (9) | 0.0232 (9) | −0.0011 (7) | 0.0064 (8) | 0.0025 (8) |
C8 | 0.0189 (9) | 0.0207 (9) | 0.0330 (11) | −0.0010 (7) | 0.0057 (8) | 0.0023 (8) |
C9 | 0.0208 (9) | 0.0291 (10) | 0.0263 (10) | −0.0004 (8) | 0.0076 (8) | 0.0063 (8) |
O3 | 0.0219 (7) | 0.0280 (7) | 0.0347 (8) | 0.0024 (5) | 0.0058 (6) | −0.0056 (6) |
O4 | 0.0326 (8) | 0.0330 (8) | 0.0365 (8) | −0.0052 (6) | 0.0021 (7) | 0.0036 (6) |
C10 | 0.0309 (11) | 0.0281 (11) | 0.0486 (14) | 0.0056 (9) | 0.0054 (10) | −0.0080 (10) |
C11 | 0.0419 (13) | 0.0295 (12) | 0.0506 (14) | −0.0070 (10) | 0.0023 (11) | 0.0036 (10) |
C12 | 0.0272 (11) | 0.0332 (11) | 0.0377 (12) | −0.0044 (9) | 0.0092 (9) | −0.0066 (9) |
C13 | 0.0258 (10) | 0.0256 (11) | 0.0390 (12) | −0.0018 (8) | 0.0067 (9) | −0.0023 (9) |
Geometric parameters (Å, º) top
O1—C1 | 1.383 (2) | C8—H8B | 0.9700 |
O1—H1 | 1.0025 | C9—H9A | 0.9600 |
O2—C2 | 1.373 (2) | C9—H9B | 0.9600 |
O2—H2 | 1.0911 | C9—H9C | 0.9600 |
C1—C6 | 1.387 (2) | O3—C10 | 1.426 (2) |
C1—C2 | 1.388 (2) | O3—C13 | 1.436 (2) |
C2—C3 | 1.392 (2) | O4—C11 | 1.425 (2) |
C3—C4 | 1.388 (2) | O4—C12 | 1.429 (2) |
C3—H3 | 0.9300 | C10—C11 | 1.497 (3) |
C4—C5 | 1.403 (2) | C10—H10A | 0.9700 |
C4—C7i | 1.521 (2) | C10—H10B | 0.9700 |
C5—C6 | 1.390 (2) | C11—H11A | 0.9700 |
C5—C7 | 1.524 (2) | C11—H11B | 0.9700 |
C6—H6 | 0.9300 | C12—C13 | 1.498 (3) |
C7—C4i | 1.521 (2) | C12—H12A | 0.9700 |
C7—C9 | 1.521 (3) | C12—H12B | 0.9700 |
C7—C8 | 1.568 (3) | C13—H13A | 0.9700 |
C8—C8i | 1.543 (4) | C13—H13B | 0.9700 |
C8—H8A | 0.9700 | | |
| | | |
C1—O1—H1 | 107.9 | C7—C9—H9A | 109.5 |
C2—O2—H2 | 110.1 | C7—C9—H9B | 109.5 |
O1—C1—C6 | 119.52 (15) | H9A—C9—H9B | 109.5 |
O1—C1—C2 | 119.68 (15) | C7—C9—H9C | 109.5 |
C6—C1—C2 | 120.79 (15) | H9A—C9—H9C | 109.5 |
O2—C2—C1 | 116.26 (15) | H9B—C9—H9C | 109.5 |
O2—C2—C3 | 124.05 (16) | C10—O3—C13 | 109.53 (15) |
C1—C2—C3 | 119.69 (16) | C11—O4—C12 | 109.65 (15) |
C4—C3—C2 | 120.00 (16) | O3—C10—C11 | 111.16 (18) |
C4—C3—H3 | 120.0 | O3—C10—H10A | 109.4 |
C2—C3—H3 | 120.0 | C11—C10—H10A | 109.4 |
C3—C4—C5 | 120.08 (16) | O3—C10—H10B | 109.4 |
C3—C4—C7i | 125.39 (16) | C11—C10—H10B | 109.4 |
C5—C4—C7i | 114.42 (15) | H10A—C10—H10B | 108.0 |
C6—C5—C4 | 119.67 (16) | O4—C11—C10 | 111.26 (18) |
C6—C5—C7 | 125.85 (16) | O4—C11—H11A | 109.4 |
C4—C5—C7 | 114.35 (15) | C10—C11—H11A | 109.4 |
C1—C6—C5 | 119.76 (16) | O4—C11—H11B | 109.4 |
C1—C6—H6 | 120.1 | C10—C11—H11B | 109.4 |
C5—C6—H6 | 120.1 | H11A—C11—H11B | 108.0 |
C4i—C7—C9 | 114.32 (15) | O4—C12—C13 | 111.18 (16) |
C4i—C7—C5 | 106.75 (14) | O4—C12—H12A | 109.4 |
C9—C7—C5 | 114.21 (15) | C13—C12—H12A | 109.4 |
C4i—C7—C8 | 104.66 (14) | O4—C12—H12B | 109.4 |
C9—C7—C8 | 111.16 (15) | C13—C12—H12B | 109.4 |
C5—C7—C8 | 104.88 (14) | H12A—C12—H12B | 108.0 |
C8i—C8—C7 | 110.88 (10) | O3—C13—C12 | 110.81 (16) |
C8i—C8—H8A | 109.5 | O3—C13—H13A | 109.5 |
C7—C8—H8A | 109.5 | C12—C13—H13A | 109.5 |
C8i—C8—H8B | 109.5 | O3—C13—H13B | 109.5 |
C7—C8—H8B | 109.5 | C12—C13—H13B | 109.5 |
H8A—C8—H8B | 108.1 | H13A—C13—H13B | 108.1 |
Symmetry code: (i) −x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 1.00 | 1.84 | 2.6745 (18) | 138 |
O2—H2···O1ii | 1.09 | 1.58 | 2.6644 (18) | 172 |
Symmetry code: (ii) x, −y, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C18H18O4·2(C4H8O2) |
Mr | 474.53 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 25.6848 (18), 9.7131 (10), 10.5531 (13) |
β (°) | 111.630 (6) |
V (Å3) | 2447.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Nonius Kappa-CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7056, 2312, 1723 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.609 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.113, 1.06 |
No. of reflections | 2312 |
No. of parameters | 155 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.26 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3 | 1.00 | 1.84 | 2.6745 (18) | 138.1 |
O2—H2···O1i | 1.09 | 1.58 | 2.6644 (18) | 171.8 |
Symmetry code: (i) x, −y, z+1/2. |
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.