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Two compounds containing 1,3-benzodioxin groups are reported, namely (±)-6-tert-butyl-8-hydroxymethyl-2-phenyl-4H-1,3-benzodioxin, C19H22O3, (I), and 2,2,2',2',6,6'-hexamethyl-8,8'-methylenebis(4H-1,3-benzodioxin), C23H28O4, (II).The hydroxy groups of neighbouring molecules in (I) are hydrogen bonded to each other, giving rise to double-row chains. The molecule in (II) adopts a `butterfly' conformation, with the O atoms in distal positions. In both compounds, the dioxin rings are in distorted half-chair conformations.
Supporting information
CCDC references: 199427; 199428
Compound (I) was obtained from 4-tert-butyl-1,6-bis(hydroxymethyl)phenol
and benzaldehyde dimethyl acetal (Quantities?) in dimethylformamide and
p-toluensulfonic acid (Ratio?). The compound was recrystallized from
ethyl acetate-hexane (Ratio?) (m.p. 389–390 K). Spectroscopic analysis: 1H
NMR (300 MHz, CDCl3, δ, p.p.m.): 1.09 (s, 9H), 2.06 (s, 1H), 4.43 (s, 2H),
4.77 (d, J = 14.5 Hz), 4.98 (d, J = 14.5 Hz), 5.80 (s, 1H), 6.76 (d, J = 1.7 Hz), 7.04 (d, J = 1.7 Hz, 1H), 7.19–7.26 (m, 3H), 7.35–7.39, (m, 2H).
Compound (II) was an unexpected by-product obtained while performing
methylation of
5,5'-di-tert-butyl-2,2'-dihydroxy-3,3'-methanediyl-dibenzyl alcohol
with dimethyl sulfate in acetone and K2CO3 (Quantities?). Acidic
impurities in the dimethyl sulfate apparently promoted the formation of the
acetal before being neutralized by the heterogeneous base. The compound was
recrystallized from acetone (m.p. 403–404 K). Spectroscopic analysis: 1H
NMR (300 MHz, CDCl3, δ, p.p.m.): 1.48 (s, 12H), 2.20 (s, 6H), 3.78 (s, 2H),
4.80 (s, 4H), 6.60 (d, J = 1.6 Hz, 2H), 6.83 (d, J = 1.6 Hz, 2H).
The hydroxy H atoms in compound (I) were found in a difference Fourier map and
were introduced as riding atoms, with Uiso(H) = 1.2Ueq(O).
All other H atoms in both compounds were introduced at calculated positions as
riding atoms, with C—H distances of 0.93 (CH), 0.97 (CH2) and 0.96
(CH3)Å, and with Uiso(H) = 1.2Ueq(parent) for CH and
CH2, or 1.5Ueq(parent) for CH3. In the absence of suitable
anomalous scatterers, Friedel equivalents could not be used to determine the
absolute structure. Refinement of the Flack parameter (Flack, 1983) led to
inconclusive values (Flack & Bernardinelli, 2000) of 0.3 (15) for (I) and
-1.8 (14) for (II). Therefore, the 2688 and 1726 Friedel equivalents for (I)
and (II), respectively, were merged before the final refinement, resulting in
the absolute direction of the polar axis being chosen arbitrarily.
For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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 and PARST97 (Nardelli, 1995).
(I) (±)-6-
tert-butyl-8-hydroxymethyl-2-phenyl-4
H-benzo-1,3-dioxin
top
Crystal data top
C19H22O3 | F(000) = 1280 |
Mr = 298.37 | Dx = 1.208 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 24138 reflections |
a = 25.6945 (15) Å | θ = 2.7–25.7° |
b = 16.0188 (11) Å | µ = 0.08 mm−1 |
c = 7.9750 (4) Å | T = 100 K |
V = 3282.5 (3) Å3 | Parallelepipedic, colourless |
Z = 8 | 0.3 × 0.2 × 0.1 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2589 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.058 |
Graphite monochromator | θmax = 25.7°, θmin = 2.7° |
Detector resolution: 18 pixels mm-1 | h = −31→31 |
ϕ scans | k = −19→19 |
24138 measured reflections | l = −9→9 |
3349 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0267P)2 + 1.6239P] where P = (Fo2 + 2Fc2)/3 |
3349 reflections | (Δ/σ)max < 0.001 |
403 parameters | Δρmax = 0.18 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
Crystal data top
C19H22O3 | V = 3282.5 (3) Å3 |
Mr = 298.37 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 25.6945 (15) Å | µ = 0.08 mm−1 |
b = 16.0188 (11) Å | T = 100 K |
c = 7.9750 (4) Å | 0.3 × 0.2 × 0.1 mm |
Data collection top
Nonius KappaCCD area-detector diffractometer | 2589 reflections with I > 2σ(I) |
24138 measured reflections | Rint = 0.058 |
3349 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 1 restraint |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.18 e Å−3 |
3349 reflections | Δρmin = −0.21 e Å−3 |
403 parameters | |
Special details top
Experimental. A 180° range in ϕ was scanned during both data collections, with 2° ϕ steps.
The crystal-to-detector distance was fixed at 29 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 difference Fourier synthesis.
All non-H atoms were refined with anisotropic displacement parameters. The
hydroxyl H atoms were found in the difference Fourier map and introduced as
riding atoms, with an isotropic displacement parameter equal to 1.2 times that
of the parent atom. All other H 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 | |
O1A | 0.71235 (8) | 0.20850 (14) | 0.4164 (3) | 0.0306 (5) | |
O2A | 0.69524 (8) | 0.34465 (13) | 0.5049 (3) | 0.0265 (5) | |
O3A | 0.74237 (9) | 0.56711 (13) | 0.7321 (3) | 0.0313 (6) | |
H3A | 0.7592 | 0.6013 | 0.6548 | 0.038* | |
C1A | 0.78433 (12) | 0.30632 (19) | 0.4416 (4) | 0.0257 (7) | |
C2A | 0.74820 (12) | 0.36208 (18) | 0.5054 (4) | 0.0240 (7) | |
C3A | 0.76308 (12) | 0.4376 (2) | 0.5804 (4) | 0.0246 (7) | |
C4A | 0.81579 (12) | 0.4568 (2) | 0.5831 (4) | 0.0256 (8) | |
H4A | 0.8264 | 0.5059 | 0.6350 | 0.031* | |
C5A | 0.85389 (12) | 0.4050 (2) | 0.5105 (4) | 0.0263 (7) | |
C6A | 0.83700 (12) | 0.3297 (2) | 0.4431 (4) | 0.0278 (8) | |
H6A | 0.8615 | 0.2935 | 0.3973 | 0.033* | |
C7A | 0.76636 (12) | 0.2235 (2) | 0.3759 (4) | 0.0312 (8) | |
H7A1 | 0.7708 | 0.2221 | 0.2551 | 0.037* | |
H7A2 | 0.7876 | 0.1795 | 0.4238 | 0.037* | |
C8A | 0.72183 (13) | 0.4957 (2) | 0.6473 (4) | 0.0282 (8) | |
H8A1 | 0.7003 | 0.5144 | 0.5548 | 0.034* | |
H8A2 | 0.6997 | 0.4650 | 0.7242 | 0.034* | |
C9A | 0.91057 (12) | 0.4348 (2) | 0.4989 (5) | 0.0304 (8) | |
C10A | 0.94823 (13) | 0.3626 (2) | 0.4660 (5) | 0.0443 (10) | |
H10A | 0.9396 | 0.3363 | 0.3615 | 0.066* | |
H10B | 0.9456 | 0.3226 | 0.5551 | 0.066* | |
H10C | 0.9832 | 0.3837 | 0.4607 | 0.066* | |
C11A | 0.91467 (14) | 0.4978 (2) | 0.3544 (5) | 0.0416 (9) | |
H11A | 0.9497 | 0.5184 | 0.3475 | 0.062* | |
H11B | 0.8913 | 0.5435 | 0.3744 | 0.062* | |
H11C | 0.9056 | 0.4709 | 0.2509 | 0.062* | |
C12A | 0.92774 (14) | 0.4790 (3) | 0.6601 (5) | 0.0432 (10) | |
H12A | 0.9229 | 0.4423 | 0.7539 | 0.065* | |
H12B | 0.9072 | 0.5285 | 0.6759 | 0.065* | |
H12C | 0.9638 | 0.4940 | 0.6515 | 0.065* | |
C13A | 0.68296 (12) | 0.2814 (2) | 0.3857 (4) | 0.0302 (8) | |
H13A | 0.6907 | 0.3020 | 0.2727 | 0.036* | |
C14A | 0.62598 (12) | 0.2614 (2) | 0.3978 (4) | 0.0289 (8) | |
C15A | 0.59165 (12) | 0.3133 (2) | 0.4819 (4) | 0.0350 (8) | |
H15A | 0.6044 | 0.3597 | 0.5388 | 0.042* | |
C16A | 0.53831 (13) | 0.2970 (2) | 0.4827 (5) | 0.0394 (9) | |
H16A | 0.5157 | 0.3329 | 0.5385 | 0.047* | |
C17A | 0.51912 (14) | 0.2277 (3) | 0.4006 (5) | 0.0444 (10) | |
H17A | 0.4837 | 0.2162 | 0.4026 | 0.053* | |
C18A | 0.55274 (15) | 0.1756 (3) | 0.3155 (5) | 0.0448 (10) | |
H18A | 0.5398 | 0.1290 | 0.2598 | 0.054* | |
C19A | 0.60593 (14) | 0.1925 (2) | 0.3125 (4) | 0.0375 (9) | |
H19A | 0.6282 | 0.1576 | 0.2533 | 0.045* | |
O1B | 0.72685 (9) | 1.02626 (14) | 0.8314 (3) | 0.0371 (6) | |
O2B | 0.69107 (9) | 0.89325 (14) | 0.8570 (3) | 0.0314 (5) | |
O3B | 0.70063 (8) | 0.64609 (13) | 0.9952 (3) | 0.0292 (5) | |
H3B | 0.7152 | 0.6228 | 0.9020 | 0.035* | |
C1B | 0.78471 (13) | 0.9079 (2) | 0.8313 (4) | 0.0294 (8) | |
C2B | 0.74096 (12) | 0.86049 (19) | 0.8658 (4) | 0.0269 (7) | |
C3B | 0.74415 (12) | 0.77808 (19) | 0.9187 (4) | 0.0254 (7) | |
C4B | 0.79333 (12) | 0.7429 (2) | 0.9371 (4) | 0.0258 (7) | |
H4B | 0.7961 | 0.6877 | 0.9718 | 0.031* | |
C5B | 0.83876 (12) | 0.7882 (2) | 0.9051 (4) | 0.0285 (8) | |
C6B | 0.83324 (13) | 0.8705 (2) | 0.8518 (4) | 0.0303 (8) | |
H6B | 0.8630 | 0.9016 | 0.8291 | 0.036* | |
C7B | 0.77770 (13) | 0.9979 (2) | 0.7814 (5) | 0.0368 (9) | |
H7B1 | 0.8042 | 1.0319 | 0.8348 | 0.044* | |
H7B2 | 0.7815 | 1.0034 | 0.6609 | 0.044* | |
C8B | 0.69430 (12) | 0.73215 (19) | 0.9557 (4) | 0.0296 (8) | |
H8B1 | 0.6771 | 0.7594 | 1.0490 | 0.036* | |
H8B2 | 0.6716 | 0.7368 | 0.8589 | 0.036* | |
C9B | 0.89296 (12) | 0.7508 (2) | 0.9348 (4) | 0.0324 (8) | |
C10B | 0.92441 (14) | 0.7543 (3) | 0.7698 (4) | 0.0413 (9) | |
H10D | 0.9587 | 0.7324 | 0.7886 | 0.062* | |
H10E | 0.9269 | 0.8112 | 0.7325 | 0.062* | |
H10F | 0.9072 | 0.7216 | 0.6857 | 0.062* | |
C11B | 0.89039 (13) | 0.6606 (2) | 0.9924 (5) | 0.0444 (9) | |
H11D | 0.8734 | 0.6275 | 0.9083 | 0.067* | |
H11E | 0.8712 | 0.6573 | 1.0954 | 0.067* | |
H11F | 0.9250 | 0.6398 | 1.0100 | 0.067* | |
C12B | 0.92143 (15) | 0.8022 (3) | 1.0692 (5) | 0.0445 (10) | |
H12D | 0.9023 | 0.7998 | 1.1725 | 0.067* | |
H12E | 0.9241 | 0.8592 | 1.0329 | 0.067* | |
H12F | 0.9557 | 0.7797 | 1.0862 | 0.067* | |
C13B | 0.68815 (14) | 0.9716 (2) | 0.7748 (4) | 0.0336 (8) | |
H13B | 0.6920 | 0.9633 | 0.6536 | 0.040* | |
C14B | 0.63535 (14) | 1.0086 (2) | 0.8106 (4) | 0.0335 (8) | |
C15B | 0.59997 (14) | 0.9701 (2) | 0.9149 (5) | 0.0442 (10) | |
H15B | 0.6086 | 0.9200 | 0.9671 | 0.053* | |
C16B | 0.55138 (15) | 1.0060 (3) | 0.9423 (6) | 0.0528 (11) | |
H16B | 0.5272 | 0.9795 | 1.0109 | 0.063* | |
C17B | 0.53926 (17) | 1.0811 (3) | 0.8670 (6) | 0.0557 (12) | |
H17B | 0.5070 | 1.1056 | 0.8864 | 0.067* | |
C18B | 0.57460 (17) | 1.1202 (3) | 0.7632 (5) | 0.0543 (12) | |
H18B | 0.5662 | 1.1709 | 0.7129 | 0.065* | |
C19B | 0.62273 (15) | 1.0838 (2) | 0.7340 (5) | 0.0429 (10) | |
H19B | 0.6465 | 1.1097 | 0.6631 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0298 (12) | 0.0278 (13) | 0.0341 (13) | −0.0021 (10) | −0.0007 (11) | −0.0013 (10) |
O2A | 0.0221 (12) | 0.0287 (12) | 0.0287 (12) | −0.0027 (9) | −0.0013 (10) | −0.0024 (10) |
O3A | 0.0347 (14) | 0.0247 (12) | 0.0345 (13) | −0.0042 (11) | 0.0073 (11) | −0.0036 (11) |
C1A | 0.0326 (19) | 0.0219 (17) | 0.0225 (17) | 0.0001 (14) | 0.0021 (14) | 0.0017 (13) |
C2A | 0.0213 (17) | 0.0246 (17) | 0.0261 (16) | −0.0025 (13) | −0.0012 (14) | 0.0026 (14) |
C3A | 0.0238 (19) | 0.0297 (19) | 0.0204 (16) | 0.0009 (14) | −0.0025 (14) | 0.0040 (14) |
C4A | 0.0270 (19) | 0.0220 (18) | 0.0278 (18) | −0.0003 (14) | 0.0006 (15) | 0.0009 (14) |
C5A | 0.0247 (17) | 0.0283 (19) | 0.0260 (16) | 0.0029 (14) | −0.0004 (14) | 0.0034 (15) |
C6A | 0.0273 (18) | 0.0301 (19) | 0.0260 (18) | 0.0052 (15) | 0.0021 (14) | −0.0004 (14) |
C7A | 0.0306 (19) | 0.0296 (19) | 0.0335 (19) | 0.0025 (15) | 0.0028 (15) | −0.0014 (15) |
C8A | 0.0272 (19) | 0.0251 (19) | 0.0324 (18) | −0.0010 (15) | 0.0000 (14) | −0.0028 (15) |
C9A | 0.0209 (17) | 0.034 (2) | 0.0367 (18) | 0.0012 (14) | −0.0001 (15) | 0.0011 (17) |
C10A | 0.0244 (19) | 0.044 (2) | 0.065 (3) | 0.0052 (17) | −0.0007 (18) | −0.004 (2) |
C11A | 0.033 (2) | 0.049 (2) | 0.043 (2) | −0.0046 (18) | 0.0001 (17) | 0.009 (2) |
C12A | 0.032 (2) | 0.054 (3) | 0.043 (2) | −0.0101 (19) | −0.0026 (18) | −0.0021 (19) |
C13A | 0.0343 (19) | 0.0254 (19) | 0.0309 (19) | −0.0028 (15) | −0.0039 (16) | −0.0043 (15) |
C14A | 0.0277 (18) | 0.034 (2) | 0.0254 (18) | −0.0060 (15) | −0.0043 (15) | 0.0025 (15) |
C15A | 0.0289 (19) | 0.043 (2) | 0.0327 (19) | −0.0062 (16) | 0.0008 (16) | −0.0001 (17) |
C16A | 0.030 (2) | 0.053 (2) | 0.035 (2) | −0.0040 (18) | 0.0032 (17) | 0.0026 (18) |
C17A | 0.029 (2) | 0.064 (3) | 0.040 (2) | −0.014 (2) | −0.0033 (18) | 0.006 (2) |
C18A | 0.038 (2) | 0.056 (3) | 0.041 (2) | −0.017 (2) | −0.0104 (19) | 0.0006 (19) |
C19A | 0.036 (2) | 0.041 (2) | 0.036 (2) | −0.0064 (17) | −0.0001 (17) | −0.0013 (17) |
O1B | 0.0414 (15) | 0.0253 (13) | 0.0444 (15) | −0.0014 (11) | 0.0023 (12) | 0.0009 (11) |
O2B | 0.0279 (12) | 0.0245 (13) | 0.0416 (14) | 0.0060 (10) | −0.0021 (11) | 0.0010 (11) |
O3B | 0.0289 (12) | 0.0251 (12) | 0.0335 (12) | 0.0013 (10) | 0.0037 (11) | 0.0017 (10) |
C1B | 0.0317 (19) | 0.0285 (19) | 0.0279 (18) | 0.0012 (15) | 0.0021 (15) | 0.0012 (15) |
C2B | 0.0239 (17) | 0.0268 (18) | 0.0300 (18) | 0.0039 (15) | 0.0021 (15) | −0.0017 (14) |
C3B | 0.0224 (17) | 0.0264 (18) | 0.0273 (17) | −0.0007 (14) | −0.0027 (15) | −0.0011 (14) |
C4B | 0.0250 (17) | 0.0254 (17) | 0.0271 (17) | −0.0003 (14) | 0.0006 (14) | 0.0001 (14) |
C5B | 0.0245 (17) | 0.034 (2) | 0.0268 (17) | −0.0019 (15) | −0.0009 (15) | −0.0029 (15) |
C6B | 0.0275 (18) | 0.034 (2) | 0.0291 (17) | −0.0069 (15) | 0.0050 (15) | −0.0031 (15) |
C7B | 0.038 (2) | 0.031 (2) | 0.042 (2) | −0.0022 (17) | 0.0076 (17) | −0.0010 (16) |
C8B | 0.0276 (19) | 0.0241 (18) | 0.037 (2) | 0.0006 (14) | 0.0009 (15) | −0.0005 (14) |
C9B | 0.0200 (17) | 0.044 (2) | 0.0333 (19) | −0.0018 (15) | −0.0010 (15) | 0.0008 (17) |
C10B | 0.0240 (19) | 0.060 (3) | 0.040 (2) | 0.0072 (18) | 0.0044 (17) | −0.0017 (19) |
C11B | 0.0261 (19) | 0.047 (2) | 0.060 (2) | 0.0087 (17) | 0.0008 (19) | 0.009 (2) |
C12B | 0.032 (2) | 0.065 (3) | 0.037 (2) | −0.0026 (19) | −0.0041 (17) | −0.0034 (19) |
C13B | 0.040 (2) | 0.026 (2) | 0.034 (2) | 0.0047 (16) | −0.0035 (17) | 0.0020 (16) |
C14B | 0.039 (2) | 0.029 (2) | 0.033 (2) | 0.0079 (17) | −0.0034 (16) | −0.0029 (15) |
C15B | 0.042 (2) | 0.044 (2) | 0.046 (2) | 0.0134 (18) | 0.001 (2) | 0.0022 (19) |
C16B | 0.043 (2) | 0.058 (3) | 0.057 (3) | 0.013 (2) | 0.007 (2) | −0.004 (2) |
C17B | 0.050 (3) | 0.052 (3) | 0.066 (3) | 0.026 (2) | −0.004 (2) | −0.006 (2) |
C18B | 0.056 (3) | 0.051 (3) | 0.056 (3) | 0.022 (2) | −0.011 (2) | 0.003 (2) |
C19B | 0.052 (3) | 0.035 (2) | 0.042 (2) | 0.0046 (19) | −0.0083 (19) | 0.0025 (17) |
Geometric parameters (Å, º) top
O1A—C13A | 1.412 (4) | O1B—C13B | 1.400 (4) |
O1A—C7A | 1.445 (4) | O1B—C7B | 1.440 (4) |
O2A—C2A | 1.389 (3) | O2B—C2B | 1.387 (4) |
O2A—C13A | 1.424 (4) | O2B—C13B | 1.418 (4) |
O3A—C8A | 1.430 (4) | O3B—C8B | 1.424 (4) |
O3A—H3A | 0.9304 | O3B—H3B | 0.9123 |
C1A—C2A | 1.385 (4) | C1B—C2B | 1.384 (4) |
C1A—C6A | 1.404 (4) | C1B—C6B | 1.393 (5) |
C1A—C7A | 1.499 (4) | C1B—C7B | 1.506 (5) |
C2A—C3A | 1.403 (4) | C2B—C3B | 1.388 (4) |
C3A—C4A | 1.389 (4) | C3B—C4B | 1.391 (4) |
C3A—C8A | 1.508 (4) | C3B—C8B | 1.506 (4) |
C4A—C5A | 1.408 (4) | C4B—C5B | 1.397 (4) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—C6A | 1.390 (4) | C5B—C6B | 1.393 (4) |
C5A—C9A | 1.535 (4) | C5B—C9B | 1.534 (4) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—H7A1 | 0.9700 | C7B—H7B1 | 0.9700 |
C7A—H7A2 | 0.9700 | C7B—H7B2 | 0.9700 |
C8A—H8A1 | 0.9700 | C8B—H8B1 | 0.9700 |
C8A—H8A2 | 0.9700 | C8B—H8B2 | 0.9700 |
C9A—C10A | 1.530 (5) | C9B—C11B | 1.518 (5) |
C9A—C12A | 1.533 (5) | C9B—C12B | 1.537 (5) |
C9A—C11A | 1.536 (5) | C9B—C10B | 1.545 (5) |
C10A—H10A | 0.9600 | C10B—H10D | 0.9600 |
C10A—H10B | 0.9600 | C10B—H10E | 0.9600 |
C10A—H10C | 0.9600 | C10B—H10F | 0.9600 |
C11A—H11A | 0.9600 | C11B—H11D | 0.9600 |
C11A—H11B | 0.9600 | C11B—H11E | 0.9600 |
C11A—H11C | 0.9600 | C11B—H11F | 0.9600 |
C12A—H12A | 0.9600 | C12B—H12D | 0.9600 |
C12A—H12B | 0.9600 | C12B—H12E | 0.9600 |
C12A—H12C | 0.9600 | C12B—H12F | 0.9600 |
C13A—C14A | 1.502 (4) | C13B—C14B | 1.508 (5) |
C13A—H13A | 0.9800 | C13B—H13B | 0.9800 |
C14A—C15A | 1.385 (5) | C14B—C15B | 1.378 (5) |
C14A—C19A | 1.395 (5) | C14B—C19B | 1.389 (5) |
C15A—C16A | 1.395 (4) | C15B—C16B | 1.392 (5) |
C15A—H15A | 0.9300 | C15B—H15B | 0.9300 |
C16A—C17A | 1.380 (5) | C16B—C17B | 1.381 (6) |
C16A—H16A | 0.9300 | C16B—H16B | 0.9300 |
C17A—C18A | 1.379 (5) | C17B—C18B | 1.379 (6) |
C17A—H17A | 0.9300 | C17B—H17B | 0.9300 |
C18A—C19A | 1.393 (5) | C18B—C19B | 1.387 (5) |
C18A—H18A | 0.9300 | C18B—H18B | 0.9300 |
C19A—H19A | 0.9300 | C19B—H19B | 0.9300 |
| | | |
C13A—O1A—C7A | 109.7 (2) | C13B—O1B—C7B | 110.9 (2) |
C2A—O2A—C13A | 111.2 (2) | C2B—O2B—C13B | 114.0 (3) |
C8A—O3A—H3A | 109.2 | C8B—O3B—H3B | 105.2 |
C2A—C1A—C6A | 118.1 (3) | C2B—C1B—C6B | 117.9 (3) |
C2A—C1A—C7A | 119.5 (3) | C2B—C1B—C7B | 118.7 (3) |
C6A—C1A—C7A | 122.4 (3) | C6B—C1B—C7B | 123.3 (3) |
C1A—C2A—O2A | 121.7 (3) | C1B—C2B—O2B | 122.2 (3) |
C1A—C2A—C3A | 122.0 (3) | C1B—C2B—C3B | 122.3 (3) |
O2A—C2A—C3A | 116.2 (3) | O2B—C2B—C3B | 115.5 (3) |
C4A—C3A—C2A | 117.6 (3) | C2B—C3B—C4B | 118.1 (3) |
C4A—C3A—C8A | 123.0 (3) | C2B—C3B—C8B | 118.3 (3) |
C2A—C3A—C8A | 119.4 (3) | C4B—C3B—C8B | 123.6 (3) |
C3A—C4A—C5A | 122.8 (3) | C3B—C4B—C5B | 122.0 (3) |
C3A—C4A—H4A | 118.6 | C3B—C4B—H4B | 119.0 |
C5A—C4A—H4A | 118.6 | C5B—C4B—H4B | 119.0 |
C6A—C5A—C4A | 117.0 (3) | C6B—C5B—C4B | 117.5 (3) |
C6A—C5A—C9A | 122.9 (3) | C6B—C5B—C9B | 120.6 (3) |
C4A—C5A—C9A | 120.1 (3) | C4B—C5B—C9B | 121.8 (3) |
C5A—C6A—C1A | 122.4 (3) | C1B—C6B—C5B | 122.3 (3) |
C5A—C6A—H6A | 118.8 | C1B—C6B—H6B | 118.9 |
C1A—C6A—H6A | 118.8 | C5B—C6B—H6B | 118.9 |
O1A—C7A—C1A | 111.4 (3) | O1B—C7B—C1B | 109.7 (3) |
O1A—C7A—H7A1 | 109.4 | O1B—C7B—H7B1 | 109.7 |
C1A—C7A—H7A1 | 109.4 | C1B—C7B—H7B1 | 109.7 |
O1A—C7A—H7A2 | 109.4 | O1B—C7B—H7B2 | 109.7 |
C1A—C7A—H7A2 | 109.4 | C1B—C7B—H7B2 | 109.7 |
H7A1—C7A—H7A2 | 108.0 | H7B1—C7B—H7B2 | 108.2 |
O3A—C8A—C3A | 113.7 (3) | O3B—C8B—C3B | 114.8 (2) |
O3A—C8A—H8A1 | 108.8 | O3B—C8B—H8B1 | 108.6 |
C3A—C8A—H8A1 | 108.8 | C3B—C8B—H8B1 | 108.6 |
O3A—C8A—H8A2 | 108.8 | O3B—C8B—H8B2 | 108.6 |
C3A—C8A—H8A2 | 108.8 | C3B—C8B—H8B2 | 108.6 |
H8A1—C8A—H8A2 | 107.7 | H8B1—C8B—H8B2 | 107.5 |
C10A—C9A—C12A | 108.1 (3) | C11B—C9B—C5B | 112.3 (3) |
C10A—C9A—C5A | 112.0 (3) | C11B—C9B—C12B | 108.6 (3) |
C12A—C9A—C5A | 111.5 (3) | C5B—C9B—C12B | 109.3 (3) |
C10A—C9A—C11A | 108.9 (3) | C11B—C9B—C10B | 108.4 (3) |
C12A—C9A—C11A | 107.8 (3) | C5B—C9B—C10B | 109.2 (3) |
C5A—C9A—C11A | 108.3 (3) | C12B—C9B—C10B | 109.0 (3) |
C9A—C10A—H10A | 109.5 | C9B—C10B—H10D | 109.5 |
C9A—C10A—H10B | 109.5 | C9B—C10B—H10E | 109.5 |
H10A—C10A—H10B | 109.5 | H10D—C10B—H10E | 109.5 |
C9A—C10A—H10C | 109.5 | C9B—C10B—H10F | 109.5 |
H10A—C10A—H10C | 109.5 | H10D—C10B—H10F | 109.5 |
H10B—C10A—H10C | 109.5 | H10E—C10B—H10F | 109.5 |
C9A—C11A—H11A | 109.5 | C9B—C11B—H11D | 109.5 |
C9A—C11A—H11B | 109.5 | C9B—C11B—H11E | 109.5 |
H11A—C11A—H11B | 109.5 | H11D—C11B—H11E | 109.5 |
C9A—C11A—H11C | 109.5 | C9B—C11B—H11F | 109.5 |
H11A—C11A—H11C | 109.5 | H11D—C11B—H11F | 109.5 |
H11B—C11A—H11C | 109.5 | H11E—C11B—H11F | 109.5 |
C9A—C12A—H12A | 109.5 | C9B—C12B—H12D | 109.5 |
C9A—C12A—H12B | 109.5 | C9B—C12B—H12E | 109.5 |
H12A—C12A—H12B | 109.5 | H12D—C12B—H12E | 109.5 |
C9A—C12A—H12C | 109.5 | C9B—C12B—H12F | 109.5 |
H12A—C12A—H12C | 109.5 | H12D—C12B—H12F | 109.5 |
H12B—C12A—H12C | 109.5 | H12E—C12B—H12F | 109.5 |
O1A—C13A—O2A | 110.7 (2) | O1B—C13B—O2B | 111.5 (3) |
O1A—C13A—C14A | 109.5 (3) | O1B—C13B—C14B | 109.4 (3) |
O2A—C13A—C14A | 109.0 (3) | O2B—C13B—C14B | 107.9 (3) |
O1A—C13A—H13A | 109.2 | O1B—C13B—H13B | 109.3 |
O2A—C13A—H13A | 109.2 | O2B—C13B—H13B | 109.3 |
C14A—C13A—H13A | 109.2 | C14B—C13B—H13B | 109.3 |
C15A—C14A—C19A | 118.4 (3) | C15B—C14B—C19B | 120.0 (3) |
C15A—C14A—C13A | 121.6 (3) | C15B—C14B—C13B | 122.1 (3) |
C19A—C14A—C13A | 119.8 (3) | C19B—C14B—C13B | 117.9 (3) |
C14A—C15A—C16A | 121.0 (3) | C14B—C15B—C16B | 120.1 (4) |
C14A—C15A—H15A | 119.5 | C14B—C15B—H15B | 120.0 |
C16A—C15A—H15A | 119.5 | C16B—C15B—H15B | 120.0 |
C17A—C16A—C15A | 120.0 (4) | C17B—C16B—C15B | 119.6 (4) |
C17A—C16A—H16A | 120.0 | C17B—C16B—H16B | 120.2 |
C15A—C16A—H16A | 120.0 | C15B—C16B—H16B | 120.2 |
C18A—C17A—C16A | 119.7 (3) | C18B—C17B—C16B | 120.6 (4) |
C18A—C17A—H17A | 120.1 | C18B—C17B—H17B | 119.7 |
C16A—C17A—H17A | 120.1 | C16B—C17B—H17B | 119.7 |
C17A—C18A—C19A | 120.4 (4) | C17B—C18B—C19B | 119.8 (4) |
C17A—C18A—H18A | 119.8 | C17B—C18B—H18B | 120.1 |
C19A—C18A—H18A | 119.8 | C19B—C18B—H18B | 120.1 |
C18A—C19A—C14A | 120.5 (4) | C18B—C19B—C14B | 119.9 (4) |
C18A—C19A—H19A | 119.8 | C18B—C19B—H19B | 120.0 |
C14A—C19A—H19A | 119.8 | C14B—C19B—H19B | 120.0 |
| | | |
C6A—C1A—C2A—O2A | 178.4 (3) | C6B—C1B—C2B—O2B | 176.9 (4) |
C7A—C1A—C2A—O2A | −2.3 (5) | C7B—C1B—C2B—O2B | −0.5 (6) |
C6A—C1A—C2A—C3A | −4.4 (6) | C6B—C1B—C2B—C3B | −0.2 (6) |
C7A—C1A—C2A—C3A | 174.9 (4) | C7B—C1B—C2B—C3B | −177.5 (4) |
C13A—O2A—C2A—C1A | −20.0 (5) | C13B—O2B—C2B—C1B | 13.5 (5) |
C13A—O2A—C2A—C3A | 162.7 (3) | C13B—O2B—C2B—C3B | −169.2 (3) |
C1A—C2A—C3A—C4A | 2.6 (6) | C1B—C2B—C3B—C4B | 0.0 (6) |
O2A—C2A—C3A—C4A | 179.9 (3) | O2B—C2B—C3B—C4B | −177.3 (3) |
C1A—C2A—C3A—C8A | −180.0 (3) | C1B—C2B—C3B—C8B | 179.0 (4) |
O2A—C2A—C3A—C8A | −2.7 (5) | O2B—C2B—C3B—C8B | 1.8 (5) |
C2A—C3A—C4A—C5A | 1.7 (5) | C2B—C3B—C4B—C5B | 0.5 (6) |
C8A—C3A—C4A—C5A | −175.7 (3) | C8B—C3B—C4B—C5B | −178.5 (4) |
C3A—C4A—C5A—C6A | −3.8 (5) | C3B—C4B—C5B—C6B | −0.6 (5) |
C3A—C4A—C5A—C9A | 172.6 (4) | C3B—C4B—C5B—C9B | 176.5 (4) |
C4A—C5A—C6A—C1A | 1.8 (5) | C2B—C1B—C6B—C5B | 0.0 (6) |
C9A—C5A—C6A—C1A | −174.5 (4) | C7B—C1B—C6B—C5B | 177.2 (4) |
C2A—C1A—C6A—C5A | 2.2 (5) | C4B—C5B—C6B—C1B | 0.4 (6) |
C7A—C1A—C6A—C5A | −177.1 (4) | C9B—C5B—C6B—C1B | −176.8 (4) |
C13A—O1A—C7A—C1A | 44.1 (4) | C13B—O1B—C7B—C1B | −51.4 (4) |
C2A—C1A—C7A—O1A | −9.9 (5) | C2B—C1B—C7B—O1B | 19.0 (5) |
C6A—C1A—C7A—O1A | 169.4 (3) | C6B—C1B—C7B—O1B | −158.2 (4) |
C4A—C3A—C8A—O3A | −7.3 (5) | C2B—C3B—C8B—O3B | 174.8 (3) |
C2A—C3A—C8A—O3A | 175.4 (3) | C4B—C3B—C8B—O3B | −6.2 (5) |
C6A—C5A—C9A—C10A | −20.7 (5) | C6B—C5B—C9B—C11B | 179.9 (4) |
C4A—C5A—C9A—C10A | 163.1 (4) | C4B—C5B—C9B—C11B | 2.9 (5) |
C6A—C5A—C9A—C12A | −142.1 (4) | C6B—C5B—C9B—C12B | 59.3 (5) |
C4A—C5A—C9A—C12A | 41.7 (5) | C4B—C5B—C9B—C12B | −117.8 (4) |
C6A—C5A—C9A—C11A | 99.4 (4) | C6B—C5B—C9B—C10B | −59.9 (5) |
C4A—C5A—C9A—C11A | −76.8 (5) | C4B—C5B—C9B—C10B | 123.1 (4) |
C7A—O1A—C13A—O2A | −70.1 (4) | C7B—O1B—C13B—O2B | 67.8 (4) |
C7A—O1A—C13A—C14A | 169.8 (3) | C7B—O1B—C13B—C14B | −173.1 (3) |
C2A—O2A—C13A—O1A | 56.2 (4) | C2B—O2B—C13B—O1B | −46.5 (4) |
C2A—O2A—C13A—C14A | 176.6 (3) | C2B—O2B—C13B—C14B | −166.5 (3) |
O1A—C13A—C14A—C15A | 135.9 (4) | O1B—C13B—C14B—C15B | −118.2 (4) |
O2A—C13A—C14A—C15A | 14.8 (5) | O2B—C13B—C14B—C15B | 3.2 (5) |
O1A—C13A—C14A—C19A | −48.8 (5) | O1B—C13B—C14B—C19B | 62.2 (5) |
O2A—C13A—C14A—C19A | −170.0 (3) | O2B—C13B—C14B—C19B | −176.4 (4) |
C19A—C14A—C15A—C16A | 0.3 (6) | C19B—C14B—C15B—C16B | 0.6 (7) |
C13A—C14A—C15A—C16A | 175.6 (4) | C13B—C14B—C15B—C16B | −178.9 (4) |
C14A—C15A—C16A—C17A | 1.0 (6) | C14B—C15B—C16B—C17B | −1.3 (7) |
C15A—C16A—C17A—C18A | −1.3 (7) | C15B—C16B—C17B—C18B | 1.0 (8) |
C16A—C17A—C18A—C19A | 0.2 (7) | C16B—C17B—C18B—C19B | −0.1 (8) |
C17A—C18A—C19A—C14A | 1.1 (7) | C17B—C18B—C19B—C14B | −0.5 (7) |
C15A—C14A—C19A—C18A | −1.3 (6) | C15B—C14B—C19B—C18B | 0.2 (7) |
C13A—C14A—C19A—C18A | −176.7 (4) | C13B—C14B—C19B—C18B | 179.8 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3B—H3B···O3A | 0.91 | 1.77 | 2.674 (3) | 174 |
O3A—H3A···O3Bi | 0.93 | 1.79 | 2.705 (3) | 167 |
Symmetry code: (i) −x+3/2, y, z−1/2. |
(II) 2,2,2',2',6,6'-hexamethyl-8,8'-methylenebis(4
H-benzo-1,3-dioxin)
top
Crystal data top
C23H28O4 | Dx = 1.243 Mg m−3 |
Mr = 368.45 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 14507 reflections |
Hall symbol: I-4 | θ = 2.8–25.7° |
a = 20.5349 (10) Å | µ = 0.08 mm−1 |
c = 9.3356 (5) Å | T = 100 K |
V = 3936.7 (3) Å3 | Parallelepipedic, colourless |
Z = 8 | 0.30 × 0.15 × 0.15 mm |
F(000) = 1584 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1642 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 25.7°, θmin = 2.8° |
Detector resolution: 18 pixels mm-1 | h = −25→24 |
ϕ scans | k = −17→17 |
14507 measured reflections | l = −11→11 |
1992 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0333P)2 + 3.4238P] where P = (Fo2 + 2Fc2)/3 |
1992 reflections | (Δ/σ)max < 0.001 |
250 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
Crystal data top
C23H28O4 | Z = 8 |
Mr = 368.45 | Mo Kα radiation |
Tetragonal, I4 | µ = 0.08 mm−1 |
a = 20.5349 (10) Å | T = 100 K |
c = 9.3356 (5) Å | 0.30 × 0.15 × 0.15 mm |
V = 3936.7 (3) Å3 | |
Data collection top
Nonius KappaCCD area-detector diffractometer | 1642 reflections with I > 2σ(I) |
14507 measured reflections | Rint = 0.042 |
1992 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.20 e Å−3 |
1992 reflections | Δρmin = −0.19 e Å−3 |
250 parameters | |
Special details top
Experimental. A 180° range in ϕ was scanned during both data collections, with 2° ϕ steps.
The crystal-to-detector distance was fixed at 29 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 difference Fourier synthesis.
All non-H atoms were refined with anisotropic displacement parameters. H 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 | 0.87848 (9) | 0.14978 (9) | 0.9082 (2) | 0.0244 (5) | |
O2 | 0.80255 (9) | 0.10588 (9) | 1.0674 (2) | 0.0277 (5) | |
O3 | 0.91780 (9) | 0.34589 (9) | 0.5632 (2) | 0.0245 (5) | |
O4 | 0.87838 (10) | 0.38071 (10) | 0.3405 (2) | 0.0282 (5) | |
C1 | 0.84886 (13) | 0.21060 (14) | 0.9186 (3) | 0.0221 (6) | |
C2 | 0.79052 (15) | 0.21860 (15) | 0.9909 (3) | 0.0245 (7) | |
C3 | 0.75856 (14) | 0.16064 (14) | 1.0605 (4) | 0.0294 (7) | |
H3A | 0.7448 | 0.1722 | 1.1566 | 0.035* | |
H3B | 0.7202 | 0.1485 | 1.0063 | 0.035* | |
C4 | 0.83620 (15) | 0.09527 (14) | 0.9364 (3) | 0.0262 (6) | |
C5 | 0.88047 (15) | 0.03801 (15) | 0.9612 (4) | 0.0316 (7) | |
H5A | 0.9062 | 0.0455 | 1.0454 | 0.047* | |
H5B | 0.9087 | 0.0326 | 0.8800 | 0.047* | |
H5C | 0.8548 | −0.0006 | 0.9739 | 0.047* | |
C6 | 0.79056 (16) | 0.08497 (16) | 0.8102 (3) | 0.0328 (8) | |
H6A | 0.7595 | 0.0517 | 0.8336 | 0.049* | |
H6B | 0.8153 | 0.0718 | 0.7279 | 0.049* | |
H6C | 0.7681 | 0.1249 | 0.7895 | 0.049* | |
C7 | 0.88165 (13) | 0.26315 (14) | 0.8567 (3) | 0.0218 (6) | |
C8 | 0.85276 (14) | 0.32426 (14) | 0.8692 (3) | 0.0247 (7) | |
H8 | 0.8746 | 0.3601 | 0.8318 | 0.030* | |
C9 | 0.79310 (14) | 0.33410 (14) | 0.9347 (3) | 0.0258 (7) | |
C10 | 0.76234 (15) | 0.28020 (15) | 0.9963 (3) | 0.0252 (7) | |
H10 | 0.7224 | 0.2856 | 1.0417 | 0.030* | |
C11 | 0.76223 (16) | 0.40071 (14) | 0.9365 (4) | 0.0317 (7) | |
H11A | 0.7898 | 0.4304 | 0.9879 | 0.048* | |
H11B | 0.7205 | 0.3983 | 0.9827 | 0.048* | |
H11C | 0.7567 | 0.4159 | 0.8399 | 0.048* | |
C12 | 0.91809 (14) | 0.28218 (14) | 0.5157 (3) | 0.0232 (6) | |
C13 | 0.90554 (14) | 0.26667 (14) | 0.3732 (3) | 0.0243 (7) | |
C14 | 0.89157 (15) | 0.32024 (14) | 0.2684 (3) | 0.0297 (7) | |
H14A | 0.9287 | 0.3257 | 0.2053 | 0.036* | |
H14B | 0.8543 | 0.3083 | 0.2102 | 0.036* | |
C15 | 0.92227 (15) | 0.39487 (14) | 0.4526 (3) | 0.0259 (7) | |
C16 | 0.89806 (17) | 0.45657 (15) | 0.5218 (4) | 0.0342 (8) | |
H16A | 0.9026 | 0.4921 | 0.4558 | 0.051* | |
H16B | 0.9232 | 0.4654 | 0.6064 | 0.051* | |
H16C | 0.8530 | 0.4515 | 0.5472 | 0.051* | |
C17 | 0.99235 (14) | 0.39905 (15) | 0.4017 (3) | 0.0303 (7) | |
H17A | 1.0053 | 0.3579 | 0.3622 | 0.045* | |
H17B | 1.0201 | 0.4097 | 0.4811 | 0.045* | |
H17C | 0.9960 | 0.4322 | 0.3296 | 0.045* | |
C18 | 0.93054 (13) | 0.23392 (14) | 0.6187 (3) | 0.0218 (6) | |
C19 | 0.92992 (13) | 0.16928 (14) | 0.5728 (3) | 0.0249 (6) | |
H19 | 0.9379 | 0.1366 | 0.6394 | 0.030* | |
C20 | 0.91784 (14) | 0.15164 (14) | 0.4307 (3) | 0.0269 (7) | |
C21 | 0.90538 (14) | 0.20123 (15) | 0.3323 (3) | 0.0264 (7) | |
H21 | 0.8968 | 0.1905 | 0.2373 | 0.032* | |
C22 | 0.91840 (16) | 0.08130 (15) | 0.3856 (4) | 0.0334 (8) | |
H22A | 0.8895 | 0.0754 | 0.3058 | 0.050* | |
H22B | 0.9043 | 0.0545 | 0.4640 | 0.050* | |
H22C | 0.9618 | 0.0690 | 0.3581 | 0.050* | |
C23 | 0.94418 (14) | 0.25251 (14) | 0.7731 (3) | 0.0240 (6) | |
H23A | 0.9694 | 0.2183 | 0.8184 | 0.029* | |
H23B | 0.9699 | 0.2921 | 0.7751 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0242 (10) | 0.0217 (10) | 0.0272 (11) | 0.0010 (8) | 0.0019 (9) | 0.0030 (9) |
O2 | 0.0319 (12) | 0.0269 (11) | 0.0244 (11) | −0.0015 (9) | 0.0060 (10) | 0.0019 (10) |
O3 | 0.0319 (11) | 0.0206 (10) | 0.0211 (10) | −0.0025 (8) | 0.0020 (9) | 0.0026 (9) |
O4 | 0.0315 (12) | 0.0272 (12) | 0.0258 (11) | 0.0008 (9) | −0.0032 (9) | 0.0033 (9) |
C1 | 0.0213 (15) | 0.0259 (15) | 0.0192 (15) | 0.0008 (12) | 0.0004 (12) | −0.0006 (12) |
C2 | 0.0267 (16) | 0.0287 (17) | 0.0182 (15) | −0.0026 (13) | 0.0002 (13) | 0.0006 (12) |
C3 | 0.0283 (17) | 0.0305 (17) | 0.0294 (17) | −0.0027 (13) | 0.0032 (15) | 0.0006 (15) |
C4 | 0.0278 (16) | 0.0262 (16) | 0.0246 (15) | −0.0049 (13) | 0.0026 (14) | 0.0011 (14) |
C5 | 0.0360 (18) | 0.0266 (17) | 0.0322 (19) | 0.0012 (14) | 0.0042 (15) | 0.0032 (14) |
C6 | 0.0334 (18) | 0.0342 (19) | 0.0306 (18) | −0.0050 (15) | −0.0011 (14) | −0.0027 (14) |
C7 | 0.0223 (15) | 0.0279 (16) | 0.0152 (15) | −0.0023 (12) | −0.0011 (12) | −0.0007 (13) |
C8 | 0.0288 (16) | 0.0248 (16) | 0.0206 (15) | −0.0021 (12) | −0.0013 (13) | 0.0002 (13) |
C9 | 0.0296 (16) | 0.0270 (16) | 0.0206 (14) | 0.0027 (13) | −0.0027 (13) | −0.0024 (14) |
C10 | 0.0238 (16) | 0.0320 (17) | 0.0198 (15) | 0.0004 (13) | 0.0002 (13) | −0.0052 (13) |
C11 | 0.0383 (18) | 0.0274 (17) | 0.0294 (17) | 0.0042 (14) | 0.0007 (15) | −0.0034 (15) |
C12 | 0.0251 (16) | 0.0236 (16) | 0.0207 (15) | −0.0011 (13) | 0.0012 (12) | −0.0005 (12) |
C13 | 0.0248 (16) | 0.0254 (16) | 0.0226 (16) | −0.0017 (12) | 0.0005 (13) | 0.0021 (13) |
C14 | 0.0362 (18) | 0.0294 (17) | 0.0235 (16) | −0.0018 (14) | −0.0021 (14) | 0.0007 (14) |
C15 | 0.0290 (16) | 0.0254 (16) | 0.0232 (16) | −0.0012 (13) | −0.0025 (14) | 0.0049 (13) |
C16 | 0.040 (2) | 0.0257 (17) | 0.037 (2) | −0.0003 (14) | 0.0012 (15) | 0.0015 (15) |
C17 | 0.0298 (17) | 0.0289 (17) | 0.0320 (19) | −0.0036 (13) | 0.0016 (14) | 0.0074 (14) |
C18 | 0.0169 (14) | 0.0246 (15) | 0.0238 (15) | −0.0023 (12) | 0.0019 (12) | 0.0018 (13) |
C19 | 0.0212 (15) | 0.0271 (16) | 0.0263 (16) | −0.0011 (12) | 0.0020 (13) | 0.0025 (13) |
C20 | 0.0230 (15) | 0.0289 (16) | 0.0289 (16) | −0.0024 (13) | 0.0031 (14) | −0.0022 (14) |
C21 | 0.0259 (16) | 0.0323 (17) | 0.0211 (15) | −0.0020 (14) | −0.0018 (13) | −0.0029 (13) |
C22 | 0.0355 (18) | 0.0301 (18) | 0.0347 (19) | −0.0025 (14) | 0.0016 (15) | −0.0046 (15) |
C23 | 0.0240 (15) | 0.0273 (16) | 0.0207 (15) | −0.0013 (13) | −0.0019 (13) | 0.0022 (13) |
Geometric parameters (Å, º) top
O1—C1 | 1.393 (3) | C11—H11A | 0.9600 |
O1—C4 | 1.441 (3) | C11—H11B | 0.9600 |
O2—C4 | 1.422 (4) | C11—H11C | 0.9600 |
O2—C3 | 1.444 (3) | C12—C13 | 1.392 (4) |
O3—C12 | 1.381 (3) | C12—C18 | 1.404 (4) |
O3—C15 | 1.444 (3) | C13—C21 | 1.397 (4) |
O4—C15 | 1.412 (4) | C13—C14 | 1.500 (4) |
O4—C14 | 1.438 (4) | C14—H14A | 0.9700 |
C1—C2 | 1.385 (4) | C14—H14B | 0.9700 |
C1—C7 | 1.397 (4) | C15—C16 | 1.506 (4) |
C2—C10 | 1.392 (4) | C15—C17 | 1.518 (4) |
C2—C3 | 1.507 (4) | C16—H16A | 0.9600 |
C3—H3A | 0.9700 | C16—H16B | 0.9600 |
C3—H3B | 0.9700 | C16—H16C | 0.9600 |
C4—C5 | 1.504 (4) | C17—H17A | 0.9600 |
C4—C6 | 1.520 (4) | C17—H17B | 0.9600 |
C5—H5A | 0.9600 | C17—H17C | 0.9600 |
C5—H5B | 0.9600 | C18—C19 | 1.395 (4) |
C5—H5C | 0.9600 | C18—C23 | 1.516 (4) |
C6—H6A | 0.9600 | C19—C20 | 1.397 (4) |
C6—H6B | 0.9600 | C19—H19 | 0.9300 |
C6—H6C | 0.9600 | C20—C21 | 1.396 (4) |
C7—C8 | 1.393 (4) | C20—C22 | 1.505 (4) |
C7—C23 | 1.519 (4) | C21—H21 | 0.9300 |
C8—C9 | 1.384 (4) | C22—H22A | 0.9600 |
C8—H8 | 0.9300 | C22—H22B | 0.9600 |
C9—C10 | 1.398 (4) | C22—H22C | 0.9600 |
C9—C11 | 1.508 (4) | C23—H23A | 0.9700 |
C10—H10 | 0.9300 | C23—H23B | 0.9700 |
| | | |
C1—O1—C4 | 114.9 (2) | O3—C12—C18 | 116.7 (2) |
C4—O2—C3 | 112.6 (2) | C13—C12—C18 | 121.8 (3) |
C12—O3—C15 | 115.5 (2) | C12—C13—C21 | 118.8 (3) |
C15—O4—C14 | 113.9 (2) | C12—C13—C14 | 119.4 (3) |
C2—C1—O1 | 121.2 (2) | C21—C13—C14 | 121.7 (3) |
C2—C1—C7 | 121.8 (3) | O4—C14—C13 | 111.3 (2) |
O1—C1—C7 | 117.0 (2) | O4—C14—H14A | 109.4 |
C1—C2—C10 | 119.0 (3) | C13—C14—H14A | 109.4 |
C1—C2—C3 | 119.6 (3) | O4—C14—H14B | 109.4 |
C10—C2—C3 | 121.4 (3) | C13—C14—H14B | 109.4 |
O2—C3—C2 | 111.2 (2) | H14A—C14—H14B | 108.0 |
O2—C3—H3A | 109.4 | O4—C15—O3 | 110.3 (2) |
C2—C3—H3A | 109.4 | O4—C15—C16 | 106.3 (2) |
O2—C3—H3B | 109.4 | O3—C15—C16 | 105.0 (2) |
C2—C3—H3B | 109.4 | O4—C15—C17 | 112.6 (2) |
H3A—C3—H3B | 108.0 | O3—C15—C17 | 108.9 (2) |
O2—C4—O1 | 109.3 (2) | C16—C15—C17 | 113.5 (3) |
O2—C4—C5 | 106.3 (2) | C15—C16—H16A | 109.5 |
O1—C4—C5 | 105.7 (2) | C15—C16—H16B | 109.5 |
O2—C4—C6 | 112.8 (2) | H16A—C16—H16B | 109.5 |
O1—C4—C6 | 109.7 (2) | C15—C16—H16C | 109.5 |
C5—C4—C6 | 112.5 (3) | H16A—C16—H16C | 109.5 |
C4—C5—H5A | 109.5 | H16B—C16—H16C | 109.5 |
C4—C5—H5B | 109.5 | C15—C17—H17A | 109.5 |
H5A—C5—H5B | 109.5 | C15—C17—H17B | 109.5 |
C4—C5—H5C | 109.5 | H17A—C17—H17B | 109.5 |
H5A—C5—H5C | 109.5 | C15—C17—H17C | 109.5 |
H5B—C5—H5C | 109.5 | H17A—C17—H17C | 109.5 |
C4—C6—H6A | 109.5 | H17B—C17—H17C | 109.5 |
C4—C6—H6B | 109.5 | C19—C18—C12 | 117.3 (3) |
H6A—C6—H6B | 109.5 | C19—C18—C23 | 122.2 (3) |
C4—C6—H6C | 109.5 | C12—C18—C23 | 120.4 (3) |
H6A—C6—H6C | 109.5 | C20—C19—C18 | 122.7 (3) |
H6B—C6—H6C | 109.5 | C20—C19—H19 | 118.6 |
C8—C7—C1 | 117.1 (3) | C18—C19—H19 | 118.6 |
C8—C7—C23 | 122.2 (3) | C19—C20—C21 | 118.0 (3) |
C1—C7—C23 | 120.6 (3) | C19—C20—C22 | 120.9 (3) |
C9—C8—C7 | 123.1 (3) | C21—C20—C22 | 121.1 (3) |
C9—C8—H8 | 118.5 | C20—C21—C13 | 121.4 (3) |
C7—C8—H8 | 118.5 | C20—C21—H21 | 119.3 |
C8—C9—C10 | 117.8 (3) | C13—C21—H21 | 119.3 |
C8—C9—C11 | 120.6 (3) | C20—C22—H22A | 109.5 |
C10—C9—C11 | 121.6 (3) | C20—C22—H22B | 109.5 |
C2—C10—C9 | 121.1 (3) | H22A—C22—H22B | 109.5 |
C2—C10—H10 | 119.4 | C20—C22—H22C | 109.5 |
C9—C10—H10 | 119.4 | H22A—C22—H22C | 109.5 |
C9—C11—H11A | 109.5 | H22B—C22—H22C | 109.5 |
C9—C11—H11B | 109.5 | C7—C23—C18 | 111.6 (2) |
H11A—C11—H11B | 109.5 | C7—C23—H23A | 109.3 |
C9—C11—H11C | 109.5 | C18—C23—H23A | 109.3 |
H11A—C11—H11C | 109.5 | C7—C23—H23B | 109.3 |
H11B—C11—H11C | 109.5 | C18—C23—H23B | 109.3 |
O3—C12—C13 | 121.5 (3) | H23A—C23—H23B | 108.0 |
| | | |
C4—O1—C1—C2 | 18.4 (4) | O3—C12—C13—C21 | −178.9 (3) |
C4—O1—C1—C7 | −163.5 (3) | C18—C12—C13—C21 | 0.0 (5) |
O1—C1—C2—C10 | −178.9 (3) | O3—C12—C13—C14 | 0.2 (5) |
C7—C1—C2—C10 | 3.0 (5) | C18—C12—C13—C14 | 179.1 (3) |
O1—C1—C2—C3 | 0.4 (5) | C15—O4—C14—C13 | 45.0 (4) |
C7—C1—C2—C3 | −177.6 (3) | C12—C13—C14—O4 | −13.6 (4) |
C4—O2—C3—C2 | −45.7 (4) | C21—C13—C14—O4 | 165.5 (3) |
C1—C2—C3—O2 | 12.9 (5) | C14—O4—C15—O3 | −62.6 (4) |
C10—C2—C3—O2 | −167.8 (3) | C14—O4—C15—C16 | −175.8 (3) |
C3—O2—C4—O1 | 65.3 (3) | C14—O4—C15—C17 | 59.2 (3) |
C3—O2—C4—C5 | 179.0 (3) | C12—O3—C15—O4 | 46.9 (4) |
C3—O2—C4—C6 | −57.1 (4) | C12—O3—C15—C16 | 160.9 (3) |
C1—O1—C4—O2 | −50.1 (4) | C12—O3—C15—C17 | −77.2 (3) |
C1—O1—C4—C5 | −164.2 (3) | O3—C12—C18—C19 | 179.0 (3) |
C1—O1—C4—C6 | 74.2 (4) | C13—C12—C18—C19 | 0.1 (5) |
C2—C1—C7—C8 | −0.8 (5) | O3—C12—C18—C23 | −1.2 (4) |
O1—C1—C7—C8 | −178.9 (3) | C13—C12—C18—C23 | 179.9 (3) |
C2—C1—C7—C23 | −177.6 (3) | C12—C18—C19—C20 | 0.3 (5) |
O1—C1—C7—C23 | 4.3 (5) | C23—C18—C19—C20 | −179.6 (3) |
C1—C7—C8—C9 | −2.3 (5) | C18—C19—C20—C21 | −0.6 (5) |
C23—C7—C8—C9 | 174.5 (3) | C18—C19—C20—C22 | 179.3 (3) |
C7—C8—C9—C10 | 2.9 (5) | C19—C20—C21—C13 | 0.7 (5) |
C7—C8—C9—C11 | −175.9 (3) | C22—C20—C21—C13 | −179.3 (3) |
C1—C2—C10—C9 | −2.4 (5) | C12—C13—C21—C20 | −0.3 (5) |
C3—C2—C10—C9 | 178.3 (3) | C14—C13—C21—C20 | −179.4 (3) |
C8—C9—C10—C2 | −0.5 (5) | C19—C18—C23—C7 | −96.7 (4) |
C11—C9—C10—C2 | 178.4 (3) | C12—C18—C23—C7 | 83.5 (4) |
C15—O3—C12—C13 | −16.9 (4) | C8—C7—C23—C18 | −92.2 (4) |
C15—O3—C12—C18 | 164.2 (3) | C1—C7—C23—C18 | 84.4 (4) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C19H22O3 | C23H28O4 |
Mr | 298.37 | 368.45 |
Crystal system, space group | Orthorhombic, Pca21 | Tetragonal, I4 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 25.6945 (15), 16.0188 (11), 7.9750 (4) | 20.5349 (10), 20.5349 (10), 9.3356 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 3282.5 (3) | 3936.7 (3) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.3 × 0.2 × 0.1 | 0.30 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24138, 3349, 2589 | 14507, 1992, 1642 |
Rint | 0.058 | 0.042 |
(sin θ/λ)max (Å−1) | 0.610 | 0.609 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.107, 1.09 | 0.044, 0.097, 1.06 |
No. of reflections | 3349 | 1992 |
No. of parameters | 403 | 250 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.21 | 0.20, −0.19 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3B—H3B···O3A | 0.91 | 1.77 | 2.674 (3) | 174 |
O3A—H3A···O3Bi | 0.93 | 1.79 | 2.705 (3) | 167 |
Symmetry code: (i) −x+3/2, y, z−1/2. |
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In the course of the synthesis of homooxacalixarene compounds, the two cyclic acetals (I) and (II) were obtained from bishydroxymethylated phenols, as the result of a protection step in the case of compound (I), and of a spurious reaction in the case of (II). In both compounds, a heterocyclic 1,3-dioxin ring is fused to an aromatic ring, giving the 1,3-benzodioxin moiety. \sch
The asymmetric unit in (I) comprises two molecules, denoted A and B, which have almost identical geometry and conformations. The two aromatic rings are nearly parallel in molecule A and more tilted in molecule B, with dihedral angles of 6.8 (2) and 25.0 (1)°, respectively.
In both molecules, the dioxin ring is in a distorted half-chair conformation, but the deviations of atoms O1 and C13 with respect to the mean plane defined by atoms O2, C1, C2 and C7 are different in the two molecules; in molecule A, atoms O1A and C13A are 0.270 (5) and -0.492 (5) Å from the mean plane (r.m.s. deviation 0.008 Å), whereas in molecule B, the situation is reversed, with O1B 0.433 (5) Å and C13B -0.294 (6) Å from the mean plane (r.m.s. deviation 0.002 Å). Such distortions have been reported in related compounds, such as 6,8-dichloro-1,3-benzodioxin (Irving & Irving, 1989).
Atoms O3A and O3B are each close to the mean plane of the aromatic ring to which they belong, at distances of 0.088 (5) and 0.092 (6) Å from this plane, respectively. Both are involved in hydrogen bonds as both donors and acceptors, which gives rise to chains of alternating A and B molecules directed along the c axis (Table 1). These chains consist of strings of hydroxy groups, while the planes of the molecules themselves lie approximately perpendicular to the chain direction and such that they form two stacks of alternately upside-down molecules around the central string of hydrogen-bonded hydroxy groups. Each of these two stacks corresponds either to the A molecule and its symmetry equivalents, or to the B molecule and its symmetry equivalents.
Due to the small differences between the geometry of the two molecules, as indicated above, the packings in the two hydrogen-bonded rows are somewhat different, which in turn results in different intermolecular interactions. The aromatic ring defined by atoms C1A—C6A (centroid denoted Cg1) is possibly involved in two C—H···π interactions with neighbouring molecules along the c axis, on one side with atom H13Ai [H13Ai···Cg1 2.470 Å and C13Ai—H13Ai···Cg1 167°; symmetry code: (i) 3/2 - x, y, z + 1/2], and on the other side with atom H8A2ii [H8A2ii···Cg1 2.636 Å and C8Aii-H8A2ii···Cg1 143°; symmetry code: (ii) 3/2 - x, y, z - 1/2]. The aromatic ring defined by atoms C14A—C19A (centroid denoted Cg2) is possibly involved in a very loose C—H···π interaction with atom H18Biii of a molecule in the other row [H18Biii···Cg2 2.776 Å and C18Biii—H18Biii···Cg2 138°; symmetry code: (iii) x, y - 1, z].
The repeat unit in (II) comprises a single molecule possessing a pseudo-binary axis containing the central methylene C atom. A search of the Cambridge Structural Database (Version 5.23; Allen & Kennard, 1993) gives only one related molecule, obtained also as a by-product during the synthesis of bisphenols, namely 6,6',7,7'-tetrachloro-8,8'-methylenebis(4H-benzo-1,3-dioxin) (Ferguson et al., 1989). Both compounds comprise two methylene-linked aromatic rings bearing acetal rings, but they differ in the substituents on these rings. The compound previously reported possesses a crystallographic binary axis, its aromatic rings bear two Cl substituents each and the central C atoms of the acetal groups are unsubstituted. The aromatic rings in (II) bear one methyl substituent and the central C atoms of the acetals each have two methyl substituents. In both compounds, the molecule adopts a `butterfly' shape with the two phenol-derived O atoms in distal positions, which minimizes steric interactions. The two torsion angles defined by the methylene bridge in (II) are C1—C7—C23—C18 84.4 (3) and C12—C18—C23—C7 83.5 (3)°, whereas their counterpart in the previously reported compound is 88.2°. The dihedral angle between the aromatic rings in (II) is 72.17 (8)°, which is comparable with values in bisphenols (Thuéry et al., 2000).
As in compound (I), the two dioxin rings in (II) are in distorted half-chair conformations, with, in the first ring, deviations of atoms O2 and C4 with respect to the mean plane defined by atoms O1, C1, C2 and C3 (r.m.s. deviation 0.001 Å) of 0.306 (5) and -0.419 (5) Å, respectively, and in the second ring, deviations of atoms O4 and C15 with respect to the mean plane defined by atoms O3, C12, C13 and C14 (r.m.s. deviation 0.001 Å) of 0.312 (5) and -0.374 (5) Å, respectively. This conformation is close to that described in the previously reported compound as a `puckered plane' (Ferguson et al., 1989).
The packing in (II) brings the side of the molecule containing atoms C3 and C10 close to the `cup' defined by a neighbouring molecule. The shortest C—H···π contact associated with this `self-inclusion' arrangement involves the aromatic ring defined by atoms C12, C13, C18, C19, C20 and C21 (centroid denoted Cg3) and the atom H10i [H10i···Cg3 2.950 Å and C10i—H10i···Cg3 140°; symmetry code: (i) 3/2 - x, 1/2 - y, z - 1/2]. Another C—H···π contact involves the ring defined by atoms C1, C2, C7, C8, C9 and C10 (centroid denoted Cg4) and atom H14Bii of a neighbouring molecule along the c axis [H14Bii···Cg4 2.823 Å and C14ii—H14Bii···Cg4 141°; symmetry code: (ii) x, y, z + 1]. These H···Cg distances are much larger than the usual values for such bonds (Jeffrey & Saenger, 1994) and do not indicate the presence of significant C—H···π interactions.