Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102017481/ln1148sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017481/ln1148Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102017481/ln1148IIsup3.hkl
Contains datablock II

CCDC references: 199427; 199428

Comment top

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.

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A view of molecule A in (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii. The hydrogen bonds are shown as dashed lines. Only the hydroxy groups of symmetry-equivalent molecules involved in hydrogen bonding are represented [symmetry codes: (i) 3/2 - x, y, z - 1/2; (ii) 3/2 - x, y, z + 1/2].
[Figure 2] Fig. 2. A view of compound (II) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii.
(I) (±)-6-tert-butyl-8-hydroxymethyl-2-phenyl-4H-benzo-1,3-dioxin top
Crystal data top
C19H22O3F(000) = 1280
Mr = 298.37Dx = 1.208 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 24138 reflections
a = 25.6945 (15) Åθ = 2.7–25.7°
b = 16.0188 (11) ŵ = 0.08 mm1
c = 7.9750 (4) ÅT = 100 K
V = 3282.5 (3) Å3Parallelepipedic, colourless
Z = 80.3 × 0.2 × 0.1 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
2589 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.058
Graphite monochromatorθmax = 25.7°, θmin = 2.7°
Detector resolution: 18 pixels mm-1h = 3131
ϕ scansk = 1919
24138 measured reflectionsl = 99
3349 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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-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 parametersΔρmax = 0.18 e Å3
1 restraintΔρmin = 0.21 e Å3
Crystal data top
C19H22O3V = 3282.5 (3) Å3
Mr = 298.37Z = 8
Orthorhombic, Pca21Mo Kα radiation
a = 25.6945 (15) ŵ = 0.08 mm1
b = 16.0188 (11) ÅT = 100 K
c = 7.9750 (4) Å0.3 × 0.2 × 0.1 mm
Data collection top
Nonius KappaCCD area-detector
diffractometer
2589 reflections with I > 2σ(I)
24138 measured reflectionsRint = 0.058
3349 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0511 restraint
wR(F2) = 0.107H-atom parameters constrained
S = 1.09Δρmax = 0.18 e Å3
3349 reflectionsΔρmin = 0.21 e Å3
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
xyzUiso*/Ueq
O1A0.71235 (8)0.20850 (14)0.4164 (3)0.0306 (5)
O2A0.69524 (8)0.34465 (13)0.5049 (3)0.0265 (5)
O3A0.74237 (9)0.56711 (13)0.7321 (3)0.0313 (6)
H3A0.75920.60130.65480.038*
C1A0.78433 (12)0.30632 (19)0.4416 (4)0.0257 (7)
C2A0.74820 (12)0.36208 (18)0.5054 (4)0.0240 (7)
C3A0.76308 (12)0.4376 (2)0.5804 (4)0.0246 (7)
C4A0.81579 (12)0.4568 (2)0.5831 (4)0.0256 (8)
H4A0.82640.50590.63500.031*
C5A0.85389 (12)0.4050 (2)0.5105 (4)0.0263 (7)
C6A0.83700 (12)0.3297 (2)0.4431 (4)0.0278 (8)
H6A0.86150.29350.39730.033*
C7A0.76636 (12)0.2235 (2)0.3759 (4)0.0312 (8)
H7A10.77080.22210.25510.037*
H7A20.78760.17950.42380.037*
C8A0.72183 (13)0.4957 (2)0.6473 (4)0.0282 (8)
H8A10.70030.51440.55480.034*
H8A20.69970.46500.72420.034*
C9A0.91057 (12)0.4348 (2)0.4989 (5)0.0304 (8)
C10A0.94823 (13)0.3626 (2)0.4660 (5)0.0443 (10)
H10A0.93960.33630.36150.066*
H10B0.94560.32260.55510.066*
H10C0.98320.38370.46070.066*
C11A0.91467 (14)0.4978 (2)0.3544 (5)0.0416 (9)
H11A0.94970.51840.34750.062*
H11B0.89130.54350.37440.062*
H11C0.90560.47090.25090.062*
C12A0.92774 (14)0.4790 (3)0.6601 (5)0.0432 (10)
H12A0.92290.44230.75390.065*
H12B0.90720.52850.67590.065*
H12C0.96380.49400.65150.065*
C13A0.68296 (12)0.2814 (2)0.3857 (4)0.0302 (8)
H13A0.69070.30200.27270.036*
C14A0.62598 (12)0.2614 (2)0.3978 (4)0.0289 (8)
C15A0.59165 (12)0.3133 (2)0.4819 (4)0.0350 (8)
H15A0.60440.35970.53880.042*
C16A0.53831 (13)0.2970 (2)0.4827 (5)0.0394 (9)
H16A0.51570.33290.53850.047*
C17A0.51912 (14)0.2277 (3)0.4006 (5)0.0444 (10)
H17A0.48370.21620.40260.053*
C18A0.55274 (15)0.1756 (3)0.3155 (5)0.0448 (10)
H18A0.53980.12900.25980.054*
C19A0.60593 (14)0.1925 (2)0.3125 (4)0.0375 (9)
H19A0.62820.15760.25330.045*
O1B0.72685 (9)1.02626 (14)0.8314 (3)0.0371 (6)
O2B0.69107 (9)0.89325 (14)0.8570 (3)0.0314 (5)
O3B0.70063 (8)0.64609 (13)0.9952 (3)0.0292 (5)
H3B0.71520.62280.90200.035*
C1B0.78471 (13)0.9079 (2)0.8313 (4)0.0294 (8)
C2B0.74096 (12)0.86049 (19)0.8658 (4)0.0269 (7)
C3B0.74415 (12)0.77808 (19)0.9187 (4)0.0254 (7)
C4B0.79333 (12)0.7429 (2)0.9371 (4)0.0258 (7)
H4B0.79610.68770.97180.031*
C5B0.83876 (12)0.7882 (2)0.9051 (4)0.0285 (8)
C6B0.83324 (13)0.8705 (2)0.8518 (4)0.0303 (8)
H6B0.86300.90160.82910.036*
C7B0.77770 (13)0.9979 (2)0.7814 (5)0.0368 (9)
H7B10.80421.03190.83480.044*
H7B20.78151.00340.66090.044*
C8B0.69430 (12)0.73215 (19)0.9557 (4)0.0296 (8)
H8B10.67710.75941.04900.036*
H8B20.67160.73680.85890.036*
C9B0.89296 (12)0.7508 (2)0.9348 (4)0.0324 (8)
C10B0.92441 (14)0.7543 (3)0.7698 (4)0.0413 (9)
H10D0.95870.73240.78860.062*
H10E0.92690.81120.73250.062*
H10F0.90720.72160.68570.062*
C11B0.89039 (13)0.6606 (2)0.9924 (5)0.0444 (9)
H11D0.87340.62750.90830.067*
H11E0.87120.65731.09540.067*
H11F0.92500.63981.01000.067*
C12B0.92143 (15)0.8022 (3)1.0692 (5)0.0445 (10)
H12D0.90230.79981.17250.067*
H12E0.92410.85921.03290.067*
H12F0.95570.77971.08620.067*
C13B0.68815 (14)0.9716 (2)0.7748 (4)0.0336 (8)
H13B0.69200.96330.65360.040*
C14B0.63535 (14)1.0086 (2)0.8106 (4)0.0335 (8)
C15B0.59997 (14)0.9701 (2)0.9149 (5)0.0442 (10)
H15B0.60860.92000.96710.053*
C16B0.55138 (15)1.0060 (3)0.9423 (6)0.0528 (11)
H16B0.52720.97951.01090.063*
C17B0.53926 (17)1.0811 (3)0.8670 (6)0.0557 (12)
H17B0.50701.10560.88640.067*
C18B0.57460 (17)1.1202 (3)0.7632 (5)0.0543 (12)
H18B0.56621.17090.71290.065*
C19B0.62273 (15)1.0838 (2)0.7340 (5)0.0429 (10)
H19B0.64651.10970.66310.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0298 (12)0.0278 (13)0.0341 (13)0.0021 (10)0.0007 (11)0.0013 (10)
O2A0.0221 (12)0.0287 (12)0.0287 (12)0.0027 (9)0.0013 (10)0.0024 (10)
O3A0.0347 (14)0.0247 (12)0.0345 (13)0.0042 (11)0.0073 (11)0.0036 (11)
C1A0.0326 (19)0.0219 (17)0.0225 (17)0.0001 (14)0.0021 (14)0.0017 (13)
C2A0.0213 (17)0.0246 (17)0.0261 (16)0.0025 (13)0.0012 (14)0.0026 (14)
C3A0.0238 (19)0.0297 (19)0.0204 (16)0.0009 (14)0.0025 (14)0.0040 (14)
C4A0.0270 (19)0.0220 (18)0.0278 (18)0.0003 (14)0.0006 (15)0.0009 (14)
C5A0.0247 (17)0.0283 (19)0.0260 (16)0.0029 (14)0.0004 (14)0.0034 (15)
C6A0.0273 (18)0.0301 (19)0.0260 (18)0.0052 (15)0.0021 (14)0.0004 (14)
C7A0.0306 (19)0.0296 (19)0.0335 (19)0.0025 (15)0.0028 (15)0.0014 (15)
C8A0.0272 (19)0.0251 (19)0.0324 (18)0.0010 (15)0.0000 (14)0.0028 (15)
C9A0.0209 (17)0.034 (2)0.0367 (18)0.0012 (14)0.0001 (15)0.0011 (17)
C10A0.0244 (19)0.044 (2)0.065 (3)0.0052 (17)0.0007 (18)0.004 (2)
C11A0.033 (2)0.049 (2)0.043 (2)0.0046 (18)0.0001 (17)0.009 (2)
C12A0.032 (2)0.054 (3)0.043 (2)0.0101 (19)0.0026 (18)0.0021 (19)
C13A0.0343 (19)0.0254 (19)0.0309 (19)0.0028 (15)0.0039 (16)0.0043 (15)
C14A0.0277 (18)0.034 (2)0.0254 (18)0.0060 (15)0.0043 (15)0.0025 (15)
C15A0.0289 (19)0.043 (2)0.0327 (19)0.0062 (16)0.0008 (16)0.0001 (17)
C16A0.030 (2)0.053 (2)0.035 (2)0.0040 (18)0.0032 (17)0.0026 (18)
C17A0.029 (2)0.064 (3)0.040 (2)0.014 (2)0.0033 (18)0.006 (2)
C18A0.038 (2)0.056 (3)0.041 (2)0.017 (2)0.0104 (19)0.0006 (19)
C19A0.036 (2)0.041 (2)0.036 (2)0.0064 (17)0.0001 (17)0.0013 (17)
O1B0.0414 (15)0.0253 (13)0.0444 (15)0.0014 (11)0.0023 (12)0.0009 (11)
O2B0.0279 (12)0.0245 (13)0.0416 (14)0.0060 (10)0.0021 (11)0.0010 (11)
O3B0.0289 (12)0.0251 (12)0.0335 (12)0.0013 (10)0.0037 (11)0.0017 (10)
C1B0.0317 (19)0.0285 (19)0.0279 (18)0.0012 (15)0.0021 (15)0.0012 (15)
C2B0.0239 (17)0.0268 (18)0.0300 (18)0.0039 (15)0.0021 (15)0.0017 (14)
C3B0.0224 (17)0.0264 (18)0.0273 (17)0.0007 (14)0.0027 (15)0.0011 (14)
C4B0.0250 (17)0.0254 (17)0.0271 (17)0.0003 (14)0.0006 (14)0.0001 (14)
C5B0.0245 (17)0.034 (2)0.0268 (17)0.0019 (15)0.0009 (15)0.0029 (15)
C6B0.0275 (18)0.034 (2)0.0291 (17)0.0069 (15)0.0050 (15)0.0031 (15)
C7B0.038 (2)0.031 (2)0.042 (2)0.0022 (17)0.0076 (17)0.0010 (16)
C8B0.0276 (19)0.0241 (18)0.037 (2)0.0006 (14)0.0009 (15)0.0005 (14)
C9B0.0200 (17)0.044 (2)0.0333 (19)0.0018 (15)0.0010 (15)0.0008 (17)
C10B0.0240 (19)0.060 (3)0.040 (2)0.0072 (18)0.0044 (17)0.0017 (19)
C11B0.0261 (19)0.047 (2)0.060 (2)0.0087 (17)0.0008 (19)0.009 (2)
C12B0.032 (2)0.065 (3)0.037 (2)0.0026 (19)0.0041 (17)0.0034 (19)
C13B0.040 (2)0.026 (2)0.034 (2)0.0047 (16)0.0035 (17)0.0020 (16)
C14B0.039 (2)0.029 (2)0.033 (2)0.0079 (17)0.0034 (16)0.0029 (15)
C15B0.042 (2)0.044 (2)0.046 (2)0.0134 (18)0.001 (2)0.0022 (19)
C16B0.043 (2)0.058 (3)0.057 (3)0.013 (2)0.007 (2)0.004 (2)
C17B0.050 (3)0.052 (3)0.066 (3)0.026 (2)0.004 (2)0.006 (2)
C18B0.056 (3)0.051 (3)0.056 (3)0.022 (2)0.011 (2)0.003 (2)
C19B0.052 (3)0.035 (2)0.042 (2)0.0046 (19)0.0083 (19)0.0025 (17)
Geometric parameters (Å, º) top
O1A—C13A1.412 (4)O1B—C13B1.400 (4)
O1A—C7A1.445 (4)O1B—C7B1.440 (4)
O2A—C2A1.389 (3)O2B—C2B1.387 (4)
O2A—C13A1.424 (4)O2B—C13B1.418 (4)
O3A—C8A1.430 (4)O3B—C8B1.424 (4)
O3A—H3A0.9304O3B—H3B0.9123
C1A—C2A1.385 (4)C1B—C2B1.384 (4)
C1A—C6A1.404 (4)C1B—C6B1.393 (5)
C1A—C7A1.499 (4)C1B—C7B1.506 (5)
C2A—C3A1.403 (4)C2B—C3B1.388 (4)
C3A—C4A1.389 (4)C3B—C4B1.391 (4)
C3A—C8A1.508 (4)C3B—C8B1.506 (4)
C4A—C5A1.408 (4)C4B—C5B1.397 (4)
C4A—H4A0.9300C4B—H4B0.9300
C5A—C6A1.390 (4)C5B—C6B1.393 (4)
C5A—C9A1.535 (4)C5B—C9B1.534 (4)
C6A—H6A0.9300C6B—H6B0.9300
C7A—H7A10.9700C7B—H7B10.9700
C7A—H7A20.9700C7B—H7B20.9700
C8A—H8A10.9700C8B—H8B10.9700
C8A—H8A20.9700C8B—H8B20.9700
C9A—C10A1.530 (5)C9B—C11B1.518 (5)
C9A—C12A1.533 (5)C9B—C12B1.537 (5)
C9A—C11A1.536 (5)C9B—C10B1.545 (5)
C10A—H10A0.9600C10B—H10D0.9600
C10A—H10B0.9600C10B—H10E0.9600
C10A—H10C0.9600C10B—H10F0.9600
C11A—H11A0.9600C11B—H11D0.9600
C11A—H11B0.9600C11B—H11E0.9600
C11A—H11C0.9600C11B—H11F0.9600
C12A—H12A0.9600C12B—H12D0.9600
C12A—H12B0.9600C12B—H12E0.9600
C12A—H12C0.9600C12B—H12F0.9600
C13A—C14A1.502 (4)C13B—C14B1.508 (5)
C13A—H13A0.9800C13B—H13B0.9800
C14A—C15A1.385 (5)C14B—C15B1.378 (5)
C14A—C19A1.395 (5)C14B—C19B1.389 (5)
C15A—C16A1.395 (4)C15B—C16B1.392 (5)
C15A—H15A0.9300C15B—H15B0.9300
C16A—C17A1.380 (5)C16B—C17B1.381 (6)
C16A—H16A0.9300C16B—H16B0.9300
C17A—C18A1.379 (5)C17B—C18B1.379 (6)
C17A—H17A0.9300C17B—H17B0.9300
C18A—C19A1.393 (5)C18B—C19B1.387 (5)
C18A—H18A0.9300C18B—H18B0.9300
C19A—H19A0.9300C19B—H19B0.9300
C13A—O1A—C7A109.7 (2)C13B—O1B—C7B110.9 (2)
C2A—O2A—C13A111.2 (2)C2B—O2B—C13B114.0 (3)
C8A—O3A—H3A109.2C8B—O3B—H3B105.2
C2A—C1A—C6A118.1 (3)C2B—C1B—C6B117.9 (3)
C2A—C1A—C7A119.5 (3)C2B—C1B—C7B118.7 (3)
C6A—C1A—C7A122.4 (3)C6B—C1B—C7B123.3 (3)
C1A—C2A—O2A121.7 (3)C1B—C2B—O2B122.2 (3)
C1A—C2A—C3A122.0 (3)C1B—C2B—C3B122.3 (3)
O2A—C2A—C3A116.2 (3)O2B—C2B—C3B115.5 (3)
C4A—C3A—C2A117.6 (3)C2B—C3B—C4B118.1 (3)
C4A—C3A—C8A123.0 (3)C2B—C3B—C8B118.3 (3)
C2A—C3A—C8A119.4 (3)C4B—C3B—C8B123.6 (3)
C3A—C4A—C5A122.8 (3)C3B—C4B—C5B122.0 (3)
C3A—C4A—H4A118.6C3B—C4B—H4B119.0
C5A—C4A—H4A118.6C5B—C4B—H4B119.0
C6A—C5A—C4A117.0 (3)C6B—C5B—C4B117.5 (3)
C6A—C5A—C9A122.9 (3)C6B—C5B—C9B120.6 (3)
C4A—C5A—C9A120.1 (3)C4B—C5B—C9B121.8 (3)
C5A—C6A—C1A122.4 (3)C1B—C6B—C5B122.3 (3)
C5A—C6A—H6A118.8C1B—C6B—H6B118.9
C1A—C6A—H6A118.8C5B—C6B—H6B118.9
O1A—C7A—C1A111.4 (3)O1B—C7B—C1B109.7 (3)
O1A—C7A—H7A1109.4O1B—C7B—H7B1109.7
C1A—C7A—H7A1109.4C1B—C7B—H7B1109.7
O1A—C7A—H7A2109.4O1B—C7B—H7B2109.7
C1A—C7A—H7A2109.4C1B—C7B—H7B2109.7
H7A1—C7A—H7A2108.0H7B1—C7B—H7B2108.2
O3A—C8A—C3A113.7 (3)O3B—C8B—C3B114.8 (2)
O3A—C8A—H8A1108.8O3B—C8B—H8B1108.6
C3A—C8A—H8A1108.8C3B—C8B—H8B1108.6
O3A—C8A—H8A2108.8O3B—C8B—H8B2108.6
C3A—C8A—H8A2108.8C3B—C8B—H8B2108.6
H8A1—C8A—H8A2107.7H8B1—C8B—H8B2107.5
C10A—C9A—C12A108.1 (3)C11B—C9B—C5B112.3 (3)
C10A—C9A—C5A112.0 (3)C11B—C9B—C12B108.6 (3)
C12A—C9A—C5A111.5 (3)C5B—C9B—C12B109.3 (3)
C10A—C9A—C11A108.9 (3)C11B—C9B—C10B108.4 (3)
C12A—C9A—C11A107.8 (3)C5B—C9B—C10B109.2 (3)
C5A—C9A—C11A108.3 (3)C12B—C9B—C10B109.0 (3)
C9A—C10A—H10A109.5C9B—C10B—H10D109.5
C9A—C10A—H10B109.5C9B—C10B—H10E109.5
H10A—C10A—H10B109.5H10D—C10B—H10E109.5
C9A—C10A—H10C109.5C9B—C10B—H10F109.5
H10A—C10A—H10C109.5H10D—C10B—H10F109.5
H10B—C10A—H10C109.5H10E—C10B—H10F109.5
C9A—C11A—H11A109.5C9B—C11B—H11D109.5
C9A—C11A—H11B109.5C9B—C11B—H11E109.5
H11A—C11A—H11B109.5H11D—C11B—H11E109.5
C9A—C11A—H11C109.5C9B—C11B—H11F109.5
H11A—C11A—H11C109.5H11D—C11B—H11F109.5
H11B—C11A—H11C109.5H11E—C11B—H11F109.5
C9A—C12A—H12A109.5C9B—C12B—H12D109.5
C9A—C12A—H12B109.5C9B—C12B—H12E109.5
H12A—C12A—H12B109.5H12D—C12B—H12E109.5
C9A—C12A—H12C109.5C9B—C12B—H12F109.5
H12A—C12A—H12C109.5H12D—C12B—H12F109.5
H12B—C12A—H12C109.5H12E—C12B—H12F109.5
O1A—C13A—O2A110.7 (2)O1B—C13B—O2B111.5 (3)
O1A—C13A—C14A109.5 (3)O1B—C13B—C14B109.4 (3)
O2A—C13A—C14A109.0 (3)O2B—C13B—C14B107.9 (3)
O1A—C13A—H13A109.2O1B—C13B—H13B109.3
O2A—C13A—H13A109.2O2B—C13B—H13B109.3
C14A—C13A—H13A109.2C14B—C13B—H13B109.3
C15A—C14A—C19A118.4 (3)C15B—C14B—C19B120.0 (3)
C15A—C14A—C13A121.6 (3)C15B—C14B—C13B122.1 (3)
C19A—C14A—C13A119.8 (3)C19B—C14B—C13B117.9 (3)
C14A—C15A—C16A121.0 (3)C14B—C15B—C16B120.1 (4)
C14A—C15A—H15A119.5C14B—C15B—H15B120.0
C16A—C15A—H15A119.5C16B—C15B—H15B120.0
C17A—C16A—C15A120.0 (4)C17B—C16B—C15B119.6 (4)
C17A—C16A—H16A120.0C17B—C16B—H16B120.2
C15A—C16A—H16A120.0C15B—C16B—H16B120.2
C18A—C17A—C16A119.7 (3)C18B—C17B—C16B120.6 (4)
C18A—C17A—H17A120.1C18B—C17B—H17B119.7
C16A—C17A—H17A120.1C16B—C17B—H17B119.7
C17A—C18A—C19A120.4 (4)C17B—C18B—C19B119.8 (4)
C17A—C18A—H18A119.8C17B—C18B—H18B120.1
C19A—C18A—H18A119.8C19B—C18B—H18B120.1
C18A—C19A—C14A120.5 (4)C18B—C19B—C14B119.9 (4)
C18A—C19A—H19A119.8C18B—C19B—H19B120.0
C14A—C19A—H19A119.8C14B—C19B—H19B120.0
C6A—C1A—C2A—O2A178.4 (3)C6B—C1B—C2B—O2B176.9 (4)
C7A—C1A—C2A—O2A2.3 (5)C7B—C1B—C2B—O2B0.5 (6)
C6A—C1A—C2A—C3A4.4 (6)C6B—C1B—C2B—C3B0.2 (6)
C7A—C1A—C2A—C3A174.9 (4)C7B—C1B—C2B—C3B177.5 (4)
C13A—O2A—C2A—C1A20.0 (5)C13B—O2B—C2B—C1B13.5 (5)
C13A—O2A—C2A—C3A162.7 (3)C13B—O2B—C2B—C3B169.2 (3)
C1A—C2A—C3A—C4A2.6 (6)C1B—C2B—C3B—C4B0.0 (6)
O2A—C2A—C3A—C4A179.9 (3)O2B—C2B—C3B—C4B177.3 (3)
C1A—C2A—C3A—C8A180.0 (3)C1B—C2B—C3B—C8B179.0 (4)
O2A—C2A—C3A—C8A2.7 (5)O2B—C2B—C3B—C8B1.8 (5)
C2A—C3A—C4A—C5A1.7 (5)C2B—C3B—C4B—C5B0.5 (6)
C8A—C3A—C4A—C5A175.7 (3)C8B—C3B—C4B—C5B178.5 (4)
C3A—C4A—C5A—C6A3.8 (5)C3B—C4B—C5B—C6B0.6 (5)
C3A—C4A—C5A—C9A172.6 (4)C3B—C4B—C5B—C9B176.5 (4)
C4A—C5A—C6A—C1A1.8 (5)C2B—C1B—C6B—C5B0.0 (6)
C9A—C5A—C6A—C1A174.5 (4)C7B—C1B—C6B—C5B177.2 (4)
C2A—C1A—C6A—C5A2.2 (5)C4B—C5B—C6B—C1B0.4 (6)
C7A—C1A—C6A—C5A177.1 (4)C9B—C5B—C6B—C1B176.8 (4)
C13A—O1A—C7A—C1A44.1 (4)C13B—O1B—C7B—C1B51.4 (4)
C2A—C1A—C7A—O1A9.9 (5)C2B—C1B—C7B—O1B19.0 (5)
C6A—C1A—C7A—O1A169.4 (3)C6B—C1B—C7B—O1B158.2 (4)
C4A—C3A—C8A—O3A7.3 (5)C2B—C3B—C8B—O3B174.8 (3)
C2A—C3A—C8A—O3A175.4 (3)C4B—C3B—C8B—O3B6.2 (5)
C6A—C5A—C9A—C10A20.7 (5)C6B—C5B—C9B—C11B179.9 (4)
C4A—C5A—C9A—C10A163.1 (4)C4B—C5B—C9B—C11B2.9 (5)
C6A—C5A—C9A—C12A142.1 (4)C6B—C5B—C9B—C12B59.3 (5)
C4A—C5A—C9A—C12A41.7 (5)C4B—C5B—C9B—C12B117.8 (4)
C6A—C5A—C9A—C11A99.4 (4)C6B—C5B—C9B—C10B59.9 (5)
C4A—C5A—C9A—C11A76.8 (5)C4B—C5B—C9B—C10B123.1 (4)
C7A—O1A—C13A—O2A70.1 (4)C7B—O1B—C13B—O2B67.8 (4)
C7A—O1A—C13A—C14A169.8 (3)C7B—O1B—C13B—C14B173.1 (3)
C2A—O2A—C13A—O1A56.2 (4)C2B—O2B—C13B—O1B46.5 (4)
C2A—O2A—C13A—C14A176.6 (3)C2B—O2B—C13B—C14B166.5 (3)
O1A—C13A—C14A—C15A135.9 (4)O1B—C13B—C14B—C15B118.2 (4)
O2A—C13A—C14A—C15A14.8 (5)O2B—C13B—C14B—C15B3.2 (5)
O1A—C13A—C14A—C19A48.8 (5)O1B—C13B—C14B—C19B62.2 (5)
O2A—C13A—C14A—C19A170.0 (3)O2B—C13B—C14B—C19B176.4 (4)
C19A—C14A—C15A—C16A0.3 (6)C19B—C14B—C15B—C16B0.6 (7)
C13A—C14A—C15A—C16A175.6 (4)C13B—C14B—C15B—C16B178.9 (4)
C14A—C15A—C16A—C17A1.0 (6)C14B—C15B—C16B—C17B1.3 (7)
C15A—C16A—C17A—C18A1.3 (7)C15B—C16B—C17B—C18B1.0 (8)
C16A—C17A—C18A—C19A0.2 (7)C16B—C17B—C18B—C19B0.1 (8)
C17A—C18A—C19A—C14A1.1 (7)C17B—C18B—C19B—C14B0.5 (7)
C15A—C14A—C19A—C18A1.3 (6)C15B—C14B—C19B—C18B0.2 (7)
C13A—C14A—C19A—C18A176.7 (4)C13B—C14B—C19B—C18B179.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3B—H3B···O3A0.911.772.674 (3)174
O3A—H3A···O3Bi0.931.792.705 (3)167
Symmetry code: (i) x+3/2, y, z1/2.
(II) 2,2,2',2',6,6'-hexamethyl-8,8'-methylenebis(4H-benzo-1,3-dioxin) top
Crystal data top
C23H28O4Dx = 1.243 Mg m3
Mr = 368.45Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4Cell parameters from 14507 reflections
Hall symbol: I-4θ = 2.8–25.7°
a = 20.5349 (10) ŵ = 0.08 mm1
c = 9.3356 (5) ÅT = 100 K
V = 3936.7 (3) Å3Parallelepipedic, colourless
Z = 80.30 × 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 tubeRint = 0.042
Graphite monochromatorθmax = 25.7°, θmin = 2.8°
Detector resolution: 18 pixels mm-1h = 2524
ϕ scansk = 1717
14507 measured reflectionsl = 1111
1992 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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-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 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C23H28O4Z = 8
Mr = 368.45Mo Kα radiation
Tetragonal, I4µ = 0.08 mm1
a = 20.5349 (10) ÅT = 100 K
c = 9.3356 (5) Å0.30 × 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 reflectionsRint = 0.042
1992 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.097H-atom parameters constrained
S = 1.06Δρmax = 0.20 e Å3
1992 reflectionsΔρmin = 0.19 e Å3
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
xyzUiso*/Ueq
O10.87848 (9)0.14978 (9)0.9082 (2)0.0244 (5)
O20.80255 (9)0.10588 (9)1.0674 (2)0.0277 (5)
O30.91780 (9)0.34589 (9)0.5632 (2)0.0245 (5)
O40.87838 (10)0.38071 (10)0.3405 (2)0.0282 (5)
C10.84886 (13)0.21060 (14)0.9186 (3)0.0221 (6)
C20.79052 (15)0.21860 (15)0.9909 (3)0.0245 (7)
C30.75856 (14)0.16064 (14)1.0605 (4)0.0294 (7)
H3A0.74480.17221.15660.035*
H3B0.72020.14851.00630.035*
C40.83620 (15)0.09527 (14)0.9364 (3)0.0262 (6)
C50.88047 (15)0.03801 (15)0.9612 (4)0.0316 (7)
H5A0.90620.04551.04540.047*
H5B0.90870.03260.88000.047*
H5C0.85480.00060.97390.047*
C60.79056 (16)0.08497 (16)0.8102 (3)0.0328 (8)
H6A0.75950.05170.83360.049*
H6B0.81530.07180.72790.049*
H6C0.76810.12490.78950.049*
C70.88165 (13)0.26315 (14)0.8567 (3)0.0218 (6)
C80.85276 (14)0.32426 (14)0.8692 (3)0.0247 (7)
H80.87460.36010.83180.030*
C90.79310 (14)0.33410 (14)0.9347 (3)0.0258 (7)
C100.76234 (15)0.28020 (15)0.9963 (3)0.0252 (7)
H100.72240.28561.04170.030*
C110.76223 (16)0.40071 (14)0.9365 (4)0.0317 (7)
H11A0.78980.43040.98790.048*
H11B0.72050.39830.98270.048*
H11C0.75670.41590.83990.048*
C120.91809 (14)0.28218 (14)0.5157 (3)0.0232 (6)
C130.90554 (14)0.26667 (14)0.3732 (3)0.0243 (7)
C140.89157 (15)0.32024 (14)0.2684 (3)0.0297 (7)
H14A0.92870.32570.20530.036*
H14B0.85430.30830.21020.036*
C150.92227 (15)0.39487 (14)0.4526 (3)0.0259 (7)
C160.89806 (17)0.45657 (15)0.5218 (4)0.0342 (8)
H16A0.90260.49210.45580.051*
H16B0.92320.46540.60640.051*
H16C0.85300.45150.54720.051*
C170.99235 (14)0.39905 (15)0.4017 (3)0.0303 (7)
H17A1.00530.35790.36220.045*
H17B1.02010.40970.48110.045*
H17C0.99600.43220.32960.045*
C180.93054 (13)0.23392 (14)0.6187 (3)0.0218 (6)
C190.92992 (13)0.16928 (14)0.5728 (3)0.0249 (6)
H190.93790.13660.63940.030*
C200.91784 (14)0.15164 (14)0.4307 (3)0.0269 (7)
C210.90538 (14)0.20123 (15)0.3323 (3)0.0264 (7)
H210.89680.19050.23730.032*
C220.91840 (16)0.08130 (15)0.3856 (4)0.0334 (8)
H22A0.88950.07540.30580.050*
H22B0.90430.05450.46400.050*
H22C0.96180.06900.35810.050*
C230.94418 (14)0.25251 (14)0.7731 (3)0.0240 (6)
H23A0.96940.21830.81840.029*
H23B0.96990.29210.77510.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0242 (10)0.0217 (10)0.0272 (11)0.0010 (8)0.0019 (9)0.0030 (9)
O20.0319 (12)0.0269 (11)0.0244 (11)0.0015 (9)0.0060 (10)0.0019 (10)
O30.0319 (11)0.0206 (10)0.0211 (10)0.0025 (8)0.0020 (9)0.0026 (9)
O40.0315 (12)0.0272 (12)0.0258 (11)0.0008 (9)0.0032 (9)0.0033 (9)
C10.0213 (15)0.0259 (15)0.0192 (15)0.0008 (12)0.0004 (12)0.0006 (12)
C20.0267 (16)0.0287 (17)0.0182 (15)0.0026 (13)0.0002 (13)0.0006 (12)
C30.0283 (17)0.0305 (17)0.0294 (17)0.0027 (13)0.0032 (15)0.0006 (15)
C40.0278 (16)0.0262 (16)0.0246 (15)0.0049 (13)0.0026 (14)0.0011 (14)
C50.0360 (18)0.0266 (17)0.0322 (19)0.0012 (14)0.0042 (15)0.0032 (14)
C60.0334 (18)0.0342 (19)0.0306 (18)0.0050 (15)0.0011 (14)0.0027 (14)
C70.0223 (15)0.0279 (16)0.0152 (15)0.0023 (12)0.0011 (12)0.0007 (13)
C80.0288 (16)0.0248 (16)0.0206 (15)0.0021 (12)0.0013 (13)0.0002 (13)
C90.0296 (16)0.0270 (16)0.0206 (14)0.0027 (13)0.0027 (13)0.0024 (14)
C100.0238 (16)0.0320 (17)0.0198 (15)0.0004 (13)0.0002 (13)0.0052 (13)
C110.0383 (18)0.0274 (17)0.0294 (17)0.0042 (14)0.0007 (15)0.0034 (15)
C120.0251 (16)0.0236 (16)0.0207 (15)0.0011 (13)0.0012 (12)0.0005 (12)
C130.0248 (16)0.0254 (16)0.0226 (16)0.0017 (12)0.0005 (13)0.0021 (13)
C140.0362 (18)0.0294 (17)0.0235 (16)0.0018 (14)0.0021 (14)0.0007 (14)
C150.0290 (16)0.0254 (16)0.0232 (16)0.0012 (13)0.0025 (14)0.0049 (13)
C160.040 (2)0.0257 (17)0.037 (2)0.0003 (14)0.0012 (15)0.0015 (15)
C170.0298 (17)0.0289 (17)0.0320 (19)0.0036 (13)0.0016 (14)0.0074 (14)
C180.0169 (14)0.0246 (15)0.0238 (15)0.0023 (12)0.0019 (12)0.0018 (13)
C190.0212 (15)0.0271 (16)0.0263 (16)0.0011 (12)0.0020 (13)0.0025 (13)
C200.0230 (15)0.0289 (16)0.0289 (16)0.0024 (13)0.0031 (14)0.0022 (14)
C210.0259 (16)0.0323 (17)0.0211 (15)0.0020 (14)0.0018 (13)0.0029 (13)
C220.0355 (18)0.0301 (18)0.0347 (19)0.0025 (14)0.0016 (15)0.0046 (15)
C230.0240 (15)0.0273 (16)0.0207 (15)0.0013 (13)0.0019 (13)0.0022 (13)
Geometric parameters (Å, º) top
O1—C11.393 (3)C11—H11A0.9600
O1—C41.441 (3)C11—H11B0.9600
O2—C41.422 (4)C11—H11C0.9600
O2—C31.444 (3)C12—C131.392 (4)
O3—C121.381 (3)C12—C181.404 (4)
O3—C151.444 (3)C13—C211.397 (4)
O4—C151.412 (4)C13—C141.500 (4)
O4—C141.438 (4)C14—H14A0.9700
C1—C21.385 (4)C14—H14B0.9700
C1—C71.397 (4)C15—C161.506 (4)
C2—C101.392 (4)C15—C171.518 (4)
C2—C31.507 (4)C16—H16A0.9600
C3—H3A0.9700C16—H16B0.9600
C3—H3B0.9700C16—H16C0.9600
C4—C51.504 (4)C17—H17A0.9600
C4—C61.520 (4)C17—H17B0.9600
C5—H5A0.9600C17—H17C0.9600
C5—H5B0.9600C18—C191.395 (4)
C5—H5C0.9600C18—C231.516 (4)
C6—H6A0.9600C19—C201.397 (4)
C6—H6B0.9600C19—H190.9300
C6—H6C0.9600C20—C211.396 (4)
C7—C81.393 (4)C20—C221.505 (4)
C7—C231.519 (4)C21—H210.9300
C8—C91.384 (4)C22—H22A0.9600
C8—H80.9300C22—H22B0.9600
C9—C101.398 (4)C22—H22C0.9600
C9—C111.508 (4)C23—H23A0.9700
C10—H100.9300C23—H23B0.9700
C1—O1—C4114.9 (2)O3—C12—C18116.7 (2)
C4—O2—C3112.6 (2)C13—C12—C18121.8 (3)
C12—O3—C15115.5 (2)C12—C13—C21118.8 (3)
C15—O4—C14113.9 (2)C12—C13—C14119.4 (3)
C2—C1—O1121.2 (2)C21—C13—C14121.7 (3)
C2—C1—C7121.8 (3)O4—C14—C13111.3 (2)
O1—C1—C7117.0 (2)O4—C14—H14A109.4
C1—C2—C10119.0 (3)C13—C14—H14A109.4
C1—C2—C3119.6 (3)O4—C14—H14B109.4
C10—C2—C3121.4 (3)C13—C14—H14B109.4
O2—C3—C2111.2 (2)H14A—C14—H14B108.0
O2—C3—H3A109.4O4—C15—O3110.3 (2)
C2—C3—H3A109.4O4—C15—C16106.3 (2)
O2—C3—H3B109.4O3—C15—C16105.0 (2)
C2—C3—H3B109.4O4—C15—C17112.6 (2)
H3A—C3—H3B108.0O3—C15—C17108.9 (2)
O2—C4—O1109.3 (2)C16—C15—C17113.5 (3)
O2—C4—C5106.3 (2)C15—C16—H16A109.5
O1—C4—C5105.7 (2)C15—C16—H16B109.5
O2—C4—C6112.8 (2)H16A—C16—H16B109.5
O1—C4—C6109.7 (2)C15—C16—H16C109.5
C5—C4—C6112.5 (3)H16A—C16—H16C109.5
C4—C5—H5A109.5H16B—C16—H16C109.5
C4—C5—H5B109.5C15—C17—H17A109.5
H5A—C5—H5B109.5C15—C17—H17B109.5
C4—C5—H5C109.5H17A—C17—H17B109.5
H5A—C5—H5C109.5C15—C17—H17C109.5
H5B—C5—H5C109.5H17A—C17—H17C109.5
C4—C6—H6A109.5H17B—C17—H17C109.5
C4—C6—H6B109.5C19—C18—C12117.3 (3)
H6A—C6—H6B109.5C19—C18—C23122.2 (3)
C4—C6—H6C109.5C12—C18—C23120.4 (3)
H6A—C6—H6C109.5C20—C19—C18122.7 (3)
H6B—C6—H6C109.5C20—C19—H19118.6
C8—C7—C1117.1 (3)C18—C19—H19118.6
C8—C7—C23122.2 (3)C19—C20—C21118.0 (3)
C1—C7—C23120.6 (3)C19—C20—C22120.9 (3)
C9—C8—C7123.1 (3)C21—C20—C22121.1 (3)
C9—C8—H8118.5C20—C21—C13121.4 (3)
C7—C8—H8118.5C20—C21—H21119.3
C8—C9—C10117.8 (3)C13—C21—H21119.3
C8—C9—C11120.6 (3)C20—C22—H22A109.5
C10—C9—C11121.6 (3)C20—C22—H22B109.5
C2—C10—C9121.1 (3)H22A—C22—H22B109.5
C2—C10—H10119.4C20—C22—H22C109.5
C9—C10—H10119.4H22A—C22—H22C109.5
C9—C11—H11A109.5H22B—C22—H22C109.5
C9—C11—H11B109.5C7—C23—C18111.6 (2)
H11A—C11—H11B109.5C7—C23—H23A109.3
C9—C11—H11C109.5C18—C23—H23A109.3
H11A—C11—H11C109.5C7—C23—H23B109.3
H11B—C11—H11C109.5C18—C23—H23B109.3
O3—C12—C13121.5 (3)H23A—C23—H23B108.0
C4—O1—C1—C218.4 (4)O3—C12—C13—C21178.9 (3)
C4—O1—C1—C7163.5 (3)C18—C12—C13—C210.0 (5)
O1—C1—C2—C10178.9 (3)O3—C12—C13—C140.2 (5)
C7—C1—C2—C103.0 (5)C18—C12—C13—C14179.1 (3)
O1—C1—C2—C30.4 (5)C15—O4—C14—C1345.0 (4)
C7—C1—C2—C3177.6 (3)C12—C13—C14—O413.6 (4)
C4—O2—C3—C245.7 (4)C21—C13—C14—O4165.5 (3)
C1—C2—C3—O212.9 (5)C14—O4—C15—O362.6 (4)
C10—C2—C3—O2167.8 (3)C14—O4—C15—C16175.8 (3)
C3—O2—C4—O165.3 (3)C14—O4—C15—C1759.2 (3)
C3—O2—C4—C5179.0 (3)C12—O3—C15—O446.9 (4)
C3—O2—C4—C657.1 (4)C12—O3—C15—C16160.9 (3)
C1—O1—C4—O250.1 (4)C12—O3—C15—C1777.2 (3)
C1—O1—C4—C5164.2 (3)O3—C12—C18—C19179.0 (3)
C1—O1—C4—C674.2 (4)C13—C12—C18—C190.1 (5)
C2—C1—C7—C80.8 (5)O3—C12—C18—C231.2 (4)
O1—C1—C7—C8178.9 (3)C13—C12—C18—C23179.9 (3)
C2—C1—C7—C23177.6 (3)C12—C18—C19—C200.3 (5)
O1—C1—C7—C234.3 (5)C23—C18—C19—C20179.6 (3)
C1—C7—C8—C92.3 (5)C18—C19—C20—C210.6 (5)
C23—C7—C8—C9174.5 (3)C18—C19—C20—C22179.3 (3)
C7—C8—C9—C102.9 (5)C19—C20—C21—C130.7 (5)
C7—C8—C9—C11175.9 (3)C22—C20—C21—C13179.3 (3)
C1—C2—C10—C92.4 (5)C12—C13—C21—C200.3 (5)
C3—C2—C10—C9178.3 (3)C14—C13—C21—C20179.4 (3)
C8—C9—C10—C20.5 (5)C19—C18—C23—C796.7 (4)
C11—C9—C10—C2178.4 (3)C12—C18—C23—C783.5 (4)
C15—O3—C12—C1316.9 (4)C8—C7—C23—C1892.2 (4)
C15—O3—C12—C18164.2 (3)C1—C7—C23—C1884.4 (4)

Experimental details

(I)(II)
Crystal data
Chemical formulaC19H22O3C23H28O4
Mr298.37368.45
Crystal system, space groupOrthorhombic, Pca21Tetragonal, I4
Temperature (K)100100
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, 9090, 90, 90
V3)3282.5 (3)3936.7 (3)
Z88
Radiation typeMo KαMo Kα
µ (mm1)0.080.08
Crystal size (mm)0.3 × 0.2 × 0.10.30 × 0.15 × 0.15
Data collection
DiffractometerNonius 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
Rint0.0580.042
(sin θ/λ)max1)0.6100.609
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.107, 1.09 0.044, 0.097, 1.06
No. of reflections33491992
No. of parameters403250
No. of restraints10
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.210.20, 0.19

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL and PARST97 (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O3B—H3B···O3A0.911.772.674 (3)174
O3A—H3A···O3Bi0.931.792.705 (3)167
Symmetry code: (i) x+3/2, y, z1/2.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds