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The crystal structure of the dimeric title compound, C19H22O5, is dominated by a head-to-head hydrogen-bonding inter­action between centrosymmetrically related carboxyl groups in each monomer. The result is a dimeric axis of unusual length (ca 34 Å), but still shorter than what could be expected for a fully extended chain, owing to two turning points in the oligo­eth­oxy ends. This allows for an explanation of the structure of the smectic mesophase exhibited by this compound and at the same time fully validates former geometric estimations based on PM3 calculations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109001991/gd3269sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109001991/gd3269Isup2.hkl
Contains datablock I

CCDC reference: 728206

Comment top

The smectic C (SmC) mesophase is one of the oldest and best studied types of liquid crystals (LCs), from both the experimental and the theoretical point of view (Goodby, 1998). Most of these studies were conducted with the aim of understanding at the molecular level the structural features distinctive of the SmC mesophase: a lamellar arrangement of elongated molecules, tilted on average by an angle θ from the normal to the lamellae. Several techniques have been used in order to asses specific aspects of the intermolecular organization in a wide variety of SmC materials, and different theoretical approaches have been followed in order to either describe the phase transitions between the SmC, SmA and nematic (N) phases (Guillon, 1998; Huang, 1998) or suggest suitable models for the tilted lamellar organization, either in compounds with dipolar moments non-collinear with the main molecular axis or in compounds without any dipolar moment but containing molecular fragments with different lateral areas, giving rise to different packing requirements. In spite of the long time devoted to their study, interest in SmC LCs is still alive (Sanchez Ferrer & Finkelmann, 2008; Vadnais et al., 2008), owing to the applications they exhibit, for example, in electro-optic devices, such as surface stabilized ferroelectric liquid crystal displays (Shinkawa et al., 2008; Wang & Bos, 2004).

As part of a systematic (Montani et al., 2009) with calamitic (i.e. rod-shaped) mesogens of three-block molecular architecture (biphenyl, aliphatic chains, oxyethylenic chains), the LC behaviour of EtOC2H4OC2H4O biphenyloic acid, C19H22O5, (I), has been studied. This compound can be a priori considered as a calamitic mesogen consisting of dimeric units made up by hydrogen-bonding association of the carboxylic acid groups. In such a case, the central core would have five rings, and there would be two terminal oxyethylene chains, a molecular geometry suitable for smectic mesophases. As shown by polarized optical microscopy and powder X-ray diffraction (Montani et al., 2009), (I) did exhibit a SmC mesophase from 458 to 463 K, with an interlamellar distance of 30.8 Å. This value cannot be simply explained in terms of tilted extended molecules; indeed, the PM3-estimated (Stewart, 1988) molecular length for a fully extended dimer of (I) is 45 Å, significantly longer than the interlamellar distance. Even if a tilt of ca 45° could account for this difference, this value looks unacceptable, as the extreme tilt angles already found in SmC phases are 38°. A gauche conformation for the oxyethylene chains of the dimeric unit thus seems a more realistic explanation; indeed, this hypothesis finds two additional a priori supports: (i) the PM3-calculated molecular length for this conformation (35 Å) is much closer to the experimental interlamellar distance, and (ii) a search of the Cambridge Structural Database (CSD; Allen, 2002) for compounds with oxyethylene chains whose conformation is not determined by specific interactions (like cation complexation) showed anti conformations in less 25% of cases.

As a key step in validating this hypothesis, we have succeeded in crystallizing and solving the crystalline structure of (I), shown in Fig. 1. The figure also depicts the head-to-head hydrogen-bonding interaction between the centrosymmetrically related carboxyl groups (Table 1); this rather strong interaction leads to the formation of the expected extended dimeric units, with a span of ca 34 Å between the outermost methyl groups. The interatomic bond distances and angles are unexceptional, save perhaps for an apparent shortening in bond lengths while traversing the chain towards the Et end, ascribable to libration and tied to the increasing vibration of the tail (see Experimental). The main conformational aspects of the molecules are to be found in the few torsion angles differing significantly (by more than 5°) from 0 or 180°, viz. C5—C6—C7—C8 = 15.1 (3)°, O13—C14—C15—O16 = -72.1 (3)° and O16—C17—C18—O19= 72.2 (3)°. The first angle accounts for the slight rotation of the two phenyl rings, while the remaining two represent a twofold bending of the dimer's linear `spine' defined by the O13···O13i [symmetry code: (i) -x, -y + 1, -z + 2] vector, 23.688 (1) Å in length. This line, representative of the molecular direction, makes angles of 46.0 (1), 89.3 (1) and 37.8 (1)° with the a, b and c crystallographic axes, respectively; thus, the dimeric axes are almost contained by the (010) plane and nearly aligned to the crystallographic [103] direction.

The rather small rotation between phenyl rings in the monomers as well as the restraints imposed by symmetry on the related counterpart completing the dimer force the four aromatic rings plus their carboxylate ends to stay within a rather well defined plane (the mean deviation for the 30 atoms is 0.12 Å); the terminal tails in the dimers protrude outwards in an `anti' fashion and their least-squares lines subtend to the plane normal an angle of ca 120°. The dimers are organized in pairs, with their axes approximately parallel to each other but rotated around this axis by about 65 (1)°, as measured by the dihedral angle between the latter least-squares planes (see Fig. 1). There is no π stacking in the structure (no coplanarity, the minimum centre-to-centre distance is 4.80 Å). The ethyleneoxide chains of both components of each pair mutually interdigitate (the minimum O···C distance is approximately 3.4 Å), being nearly perpendicular to the mean molecular planes, as a consequence of the gauche conformations exhibited around the C14—C15 and C17—C18 bonds (all other torsion angles corresponding to trans conformations). Fig. 2 shows two packing views along the b and c axes: the way in which the dimers align, as well as the broad two-dimensional structure their association through weak C—H···O and C—H···π interactions (Table 1) gives rise to, can be clearly appreciated, with the hydrophobic methyl groups bunching at heights of x 0.50 and the hydrophilic carboxylates in the vicinity of x 0.00. Thus, the results presented here support our original hypothesis for the molecular description of the SmC phase of (I) and fully validate the geometric estimations made: in the crystalline phase the compound exhibits a gauche conformation for the oxyethylene chains, with a total molecular length of 34 Å, in excellent agreement with that predicted by PM3 calculations. Moreover, a lamellar organization is still present in the crystalline phase, also showing strong microsegregation between the aromatic parts and the oxyethylene chains, probably as a consequence of their differences both in polarity and in packing requirements. Microsegregation is widely recognized as a driving force for lamellar structures (Tschierske, 1998, 2001). The interlamellar distance measured by powder X-ray diffraction in the SmC phase of (I) is close to thatfound in the crystalline phase, which can be taken as the crystallographic a parameter [30.8 versus 25.430 (7) Å]. The difference can arise from several factors:

(i) The crystallographic structure has been solved at room temperature, and if an extrapolation of the molecular length to 460 K (corresponding to the SmC phase) is made, an additional 1.7 Å is obtained when only the dependence on temperature of the methylene volume (Guillon et al., 1986) is taken into account. For the whole molecule, this could be estimated as 2–3 Å.

(ii) In addition, the tilt angle can vary, as stated above, from its crystallographic value (ca 43°) to ca 28° (acceptable for SmC phases).

(iii) Finally, some conformational disorder at the oxyethylene chains may appear, increasing the effective molecular length. As stated above, the oxyethylene chains point towards a direction nearly orthogonal to the mean molecular plane. The effective molecular length in the direction of the C3···C10 axis is ca 32–33 Å.

This study is an additional proof of the usefulness of single-crystal analysis for providing key information in the interpretation of LC structures at the molecular level.

Related literature top

For related literature, see: Allen (2002); Goodby (1998); Guillon (1998); Guillon et al. (1986); Huang (1998); Lenz et al. (1991); Montani et al. (2009); Sanchez Ferrer & Finkelmann (2008); Shinkawa et al. (2008); Stewart (1988); Tschierske (1998, 2001); Vadnais et al. (2008); Wang & Bos (2004).

Experimental top

Reagents and solvents were purchased from Aldrich and used without further purification unless otherwise specified. The reported melting points are not corrected.

Compound (I) was obtained in four consecutive steps. First, 2-(2-ethoxyethoxy)ethyl-4-methylbenzenesulfonate was prepared from 2-(2-ethoxyethoxy)ethanol (Aldrich) following a reported procedure (Lenz et al., 1991). Secondly, the treatment of the tosylate with LiBr yielded the bromide (II), which was then attached to the biphenyl unit to afford the ester (III). Finally, the hydrolysis of (III) in a basic medium afforded the acid (I).

For the preparation of 1-(2-ethoxyethoxy)-2-bromoethane, (II), LiBr (10.4 g, 0.12 mol) and 2-(2-ethoxyethoxy)ethyl-4-methylbenzenesulfonate (Lenz et al., 1991) (34.4 g, 0.12 mol) in dry acetone (220 ml) were heated under reflux for 24 h under a nitrogen atmosphere. The mixture was allowed to cool to room temperature and the suspended solid was filtered off. The acetone was removed from the filtrate under reduced pressure. The remainig oil was dissolved in CH2Cl2 (300 ml), washed with water (2 × 150 ml) and dried (Na2SO4), and the solvent was removed under reduced pressure to afford an oil (yield 21.4 g, 91%). 1H NMR (CDCl3): δH 3.78 (t, 2H, J = 6.4 Hz), 3.74 (t, 2H, J = 6.4 Hz), 3.66 (t, 2H, J = 6.4 Hz), 3.48 (c, 2H, J = 7.06 Hz), 3.45 (t, 2H, J = 7.2 Hz), 1.18 (t, 3H, J = 7.06 Hz).

For the preparation of methyl 4'-[2-(2-ethoxyethoxy)ethoxy]-4-biphenylcarboxylate, (III), methyl 4,4'-hydroxybiphenylcarboxylate (7.5 g, 32.8 mmol) and K2CO3 (10.9 g,79 mmol) were dissolved in dimethylformamide (24 ml) and heated at 373 K for an hour. A solution of (II) (10.9 g, 79 mmol) in dimethylformamide (4 ml) was then added slowly. The reaction mixture was heated under reflux for 3 d and then poured into water (150 ml), and the solid product was isolated by filtration, dried under vacuum and then recrystallized from cyclohexane to yield the methyl ester as a yellow solid (yield 9.5 g, 84%; m.p. 368 K. 1H NMR (CDCl3): δH 8.05 (d, 2H, J = 8.40 Hz), 7.59 (d, 2H, J = 8.40 Hz), 7.53 (d, 2H, J = 8.77 Hz), 6.98 (d, 2H, J = 8.78 Hz), 4.17 (t, 2H, J = 5.01 Hz), 3.91 (s, 3H, J = 5.01 Hz), 3.87 (t, 2H, J = 5.01 Hz), 3.73 (t, 2H, J = 4.95 Hz), 3.62 (t, 2H, J = 4.95 Hz), 3.52 (c, 2H, J = 7.05 Hz), 1.20 (t, 3H, J = 7.06 Hz).

For the preparation (I), a mixture containing water (2.5 ml), methanol (47.5 ml), KOH (3.3 g, 60 mol) and the methyl ester (III) (7 g, 20.3 mmol) was heated under reflux for 24 h. The solvent was then removed under reduced pressure. The residue was treated with10 N HCl (15 ml) and ethyl ether (100 ml). The solid was filtered off and recrystallized from benzene, yielding the acid (I) as a white solid (yield 7.6 g, 70%; m.p. 458 K. 1H NMR (CDCl3): δH 8.12 (d, 2H2,4, J = 7.05), 7.62 (d, 2H1,5, J = 7.06 Hz), 7.54 (d, 2H8,12, J = 7.25 Hz), 6.99 (d, 2H9,11, J = 7.25 Hz), 4.18 (t, 2H14, J = 3.63 Hz), 3.88 (t, 2H15, J = 3.63 Hz), 3.73 (t, 2H17, J = 3.62 Hz), 3.62 (t, 2H18, J = 3.63 Hz), 3.54 (c, 2H20, J = 6.87 Hz), 1.21 (t, 3H21, J = 6.87 Hz). 13C NMR (CDCl3): δ = 170.2 (C22), 156.9 (C10), 142.0 (C6), 131.1 (C2,4), 129.5 (C3), 128.9 (C8,12), 128.5 (C7), 128.2 (C1,5), 115.5 (C9,11), 70.6 (C17), 70.3 (C18), 70.1 (C15), 69.8 (C14), 67.7 (C20), 15.4 (C21). Analysis calculated for C19H22O5 (330.4): C 69.07, H 6.71%; found: C 68.90, H 6.63%.

Small plates of colourless single crystals suitable for X-ray analysis were obtained by slow diffusion of ethyl ether into a dichloromethane solution of (I) at room temperature.

Refinement top

Atoms in the unbound –OC2H4OC2H4OEt group exhibit an increasing vibrational behaviour when traversing the tail from the phenyl-bound O atom [Ueq(O) = 0.0570 (4) Å2] towards the Et end [Ueq(C) = 0.1313 (15) Å2]. This is a feature found in many reported structures with similarly unbound end groups, as inspection of the CSD confirms (see, for instance, entries FAZFIW, LENLUL, LIXCEA, OKARUN, VIRXAV and VUMTUS [please also give original references for each refcode], all of them corresponding to reasonably well refined structures with R < 0.075 and no apparent disorder). H atoms were placed at calculated positions [C—H = 0.93 Å (aromatic), 0.96 Å (methyl) and 0.97 Å (ethyl), and O—H = 0.82 Å] and allowed to ride; in addition, methyl groups were allowed to rotate. Displacement parameters were taken as Uiso(H) = xUeq(carrier), where x = 1.5 (methyl H atoms) or x = 1.2 (all other H atoms).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The hydrogen-bonded dimeric units in (I), showing the head-to-head linking monomers. Note the relative orientation (65° apart) of the almost planar biphenyl groups in neighbouring dimers. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry codes: (i) -x, -y + 1, -z + 2; (v) x, -y + 3/2, z + 1.]
[Figure 2] Fig. 2. Projections of the structure, showing two different views of the broad two-dimensional structures formed by the interlinked dimers. Note the hydrophobic methyl groups bunching at x 0.50 and the hydrophilic carboxylates in the vicinity of x 0.00: (a) projection down b and (b) projection down c.
4'-[2-(2-Ethoxyethoxy)ethoxy]biphenyl-4-carboxylic acid top
Crystal data top
C19H22O5F(000) = 704
Mr = 330.37Dx = 1.291 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1583 reflections
a = 25.430 (7) Åθ = 2.4–22.9°
b = 7.769 (2) ŵ = 0.09 mm1
c = 8.656 (2) ÅT = 294 K
β = 96.187 (5)°Plates, colourless
V = 1700.3 (8) Å30.60 × 0.50 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3634 independent reflections
Radiation source: fine-focus sealed tube2230 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
phi and ω scansθmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
h = 3131
Tmin = 0.95, Tmax = 0.99k = 96
9420 measured reflectionsl = 1111
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)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.191H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.1098P)2]
where P = (Fo2 + 2Fc2)/3
3634 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C19H22O5V = 1700.3 (8) Å3
Mr = 330.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 25.430 (7) ŵ = 0.09 mm1
b = 7.769 (2) ÅT = 294 K
c = 8.656 (2) Å0.60 × 0.50 × 0.10 mm
β = 96.187 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3634 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
2230 reflections with I > 2σ(I)
Tmin = 0.95, Tmax = 0.99Rint = 0.026
9420 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.191H-atom parameters constrained
S = 0.99Δρmax = 0.23 e Å3
3634 reflectionsΔρmin = 0.14 e Å3
219 parameters
Special details top

Experimental. 1HNMR and 13C NMR spectra were recorded on a Bruker ARX300 spectrometer at 25 °C.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.15576 (9)0.6058 (3)0.6032 (3)0.0555 (6)
H10.18600.67420.61460.067*
C20.12236 (9)0.6057 (3)0.7180 (3)0.0568 (6)
H20.13070.67240.80650.068*
C30.07696 (8)0.5086 (3)0.7045 (2)0.0465 (5)
C40.06513 (9)0.4117 (3)0.5711 (2)0.0537 (6)
H40.03410.34730.55840.064*
C50.09869 (9)0.4100 (3)0.4580 (3)0.0532 (6)
H50.09020.34270.37000.064*
C60.14520 (8)0.5058 (2)0.4704 (2)0.0435 (5)
C70.18191 (8)0.5016 (2)0.3475 (2)0.0435 (5)
C80.16623 (9)0.4356 (3)0.2012 (3)0.0530 (6)
H80.13180.39500.17990.064*
C90.19938 (9)0.4275 (3)0.0863 (3)0.0542 (6)
H90.18730.38140.01020.065*
C100.25055 (8)0.4876 (3)0.1139 (2)0.0461 (5)
C110.26716 (9)0.5581 (3)0.2584 (2)0.0521 (6)
H110.30130.60120.27810.063*
C120.23362 (8)0.5648 (3)0.3721 (2)0.0486 (5)
H120.24560.61250.46800.058*
O130.28714 (6)0.4826 (2)0.00990 (16)0.0570 (4)
C140.27139 (10)0.4136 (3)0.1402 (3)0.0620 (6)
H14A0.24500.48750.19570.074*
H14B0.25590.30040.13070.074*
C150.31857 (10)0.4010 (3)0.2273 (3)0.0647 (7)
H15A0.34720.34560.16270.078*
H15B0.31010.33080.31930.078*
O160.33485 (6)0.56469 (19)0.27114 (18)0.0604 (5)
C170.37864 (10)0.5582 (4)0.3559 (3)0.0697 (7)
H17A0.37120.47990.44280.084*
H17B0.40890.51380.29010.084*
C180.39175 (11)0.7302 (4)0.4150 (3)0.0718 (7)
H18A0.41660.71810.49180.086*
H18B0.36000.78440.46470.086*
O190.41392 (7)0.8332 (2)0.2923 (2)0.0780 (6)
C200.43138 (15)0.9941 (5)0.3457 (4)0.1064 (11)
H20A0.40141.05820.39460.128*
H20B0.45580.97510.42260.128*
C210.45739 (17)1.0931 (5)0.2167 (6)0.1313 (15)
H21A0.43161.13010.15050.197*
H21B0.47431.19180.25610.197*
H21C0.48341.02260.15830.197*
C220.04230 (8)0.5066 (3)0.8313 (2)0.0487 (5)
O230.05595 (7)0.5912 (2)0.95267 (18)0.0711 (5)
O240.00103 (6)0.4157 (2)0.81277 (19)0.0704 (5)
H240.01800.41420.88340.084*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0581 (14)0.0547 (13)0.0545 (13)0.0142 (10)0.0106 (11)0.0051 (11)
C20.0647 (15)0.0585 (14)0.0481 (12)0.0127 (11)0.0111 (11)0.0114 (11)
C30.0461 (12)0.0448 (12)0.0484 (12)0.0039 (10)0.0049 (10)0.0036 (10)
C40.0460 (12)0.0644 (15)0.0508 (13)0.0080 (10)0.0053 (10)0.0050 (11)
C50.0521 (13)0.0594 (14)0.0482 (12)0.0077 (10)0.0053 (10)0.0095 (11)
C60.0485 (12)0.0371 (11)0.0444 (11)0.0012 (9)0.0028 (10)0.0039 (9)
C70.0469 (12)0.0390 (11)0.0441 (11)0.0010 (9)0.0025 (9)0.0024 (9)
C80.0462 (12)0.0623 (14)0.0506 (12)0.0101 (10)0.0059 (10)0.0044 (11)
C90.0570 (14)0.0608 (14)0.0449 (12)0.0111 (11)0.0069 (10)0.0082 (11)
C100.0515 (13)0.0411 (11)0.0468 (12)0.0003 (9)0.0111 (10)0.0019 (10)
C110.0480 (12)0.0554 (13)0.0526 (13)0.0097 (10)0.0039 (10)0.0002 (11)
C120.0499 (12)0.0504 (12)0.0454 (11)0.0055 (10)0.0042 (10)0.0045 (10)
O130.0575 (10)0.0665 (10)0.0489 (9)0.0096 (7)0.0145 (7)0.0072 (7)
C140.0706 (16)0.0620 (15)0.0554 (13)0.0147 (12)0.0162 (12)0.0140 (12)
C150.0732 (17)0.0622 (15)0.0622 (14)0.0063 (12)0.0225 (13)0.0125 (12)
O160.0661 (11)0.0584 (10)0.0605 (9)0.0005 (8)0.0233 (8)0.0039 (8)
C170.0705 (17)0.0801 (18)0.0630 (15)0.0056 (13)0.0278 (13)0.0026 (14)
C180.0771 (18)0.0852 (19)0.0559 (14)0.0026 (14)0.0201 (13)0.0041 (14)
O190.0857 (13)0.0820 (13)0.0679 (11)0.0156 (10)0.0151 (10)0.0085 (10)
C200.107 (3)0.100 (3)0.110 (3)0.025 (2)0.004 (2)0.028 (2)
C210.108 (3)0.105 (3)0.181 (4)0.024 (2)0.015 (3)0.007 (3)
C220.0460 (12)0.0528 (13)0.0472 (12)0.0025 (10)0.0048 (10)0.0022 (11)
O230.0705 (11)0.0887 (13)0.0564 (10)0.0138 (9)0.0170 (8)0.0174 (9)
O240.0558 (10)0.0975 (14)0.0609 (10)0.0161 (9)0.0203 (8)0.0078 (9)
Geometric parameters (Å, º) top
C1—C21.376 (3)C14—C151.487 (3)
C1—C61.390 (3)C14—H14A0.9700
C1—H10.9300C14—H14B0.9700
C2—C31.373 (3)C15—O161.402 (3)
C2—H20.9300C15—H15A0.9700
C3—C41.384 (3)C15—H15B0.9700
C3—C221.480 (3)O16—C171.399 (3)
C4—C51.367 (3)C17—C181.481 (4)
C4—H40.9300C17—H17A0.9700
C5—C61.392 (3)C17—H17B0.9700
C5—H50.9300C18—O191.399 (3)
C6—C71.490 (3)C18—H18A0.9700
C7—C81.384 (3)C18—H18B0.9700
C7—C121.398 (3)O19—C201.420 (3)
C8—C91.373 (3)C20—C211.455 (5)
C8—H80.9300C20—H20A0.9700
C9—C101.379 (3)C20—H20B0.9700
C9—H90.9300C21—H21A0.9600
C10—O131.363 (2)C21—H21B0.9600
C10—C111.389 (3)C21—H21C0.9600
C11—C121.371 (3)C22—O241.261 (3)
C11—H110.9300C22—O231.256 (2)
C12—H120.9300O24—H240.8201
O13—C141.423 (3)
C2—C1—C6121.2 (2)O13—C14—H14B109.9
C2—C1—H1119.4C15—C14—H14B109.9
C6—C1—H1119.4H14A—C14—H14B108.3
C3—C2—C1121.2 (2)O16—C15—C14110.8 (2)
C3—C2—H2119.4O16—C15—H15A109.5
C1—C2—H2119.4C14—C15—H15A109.5
C2—C3—C4118.4 (2)O16—C15—H15B109.5
C2—C3—C22120.3 (2)C14—C15—H15B109.5
C4—C3—C22121.32 (19)H15A—C15—H15B108.1
C5—C4—C3120.4 (2)C15—O16—C17112.60 (18)
C5—C4—H4119.8O16—C17—C18111.7 (2)
C3—C4—H4119.8O16—C17—H17A109.3
C4—C5—C6122.0 (2)C18—C17—H17A109.3
C4—C5—H5119.0O16—C17—H17B109.3
C6—C5—H5119.0C18—C17—H17B109.3
C5—C6—C1116.7 (2)H17A—C17—H17B107.9
C5—C6—C7121.75 (19)O19—C18—C17109.9 (2)
C1—C6—C7121.51 (19)O19—C18—H18A109.7
C8—C7—C12116.3 (2)C17—C18—H18A109.7
C8—C7—C6121.35 (19)O19—C18—H18B109.7
C12—C7—C6122.35 (19)C17—C18—H18B109.7
C9—C8—C7122.7 (2)H18A—C18—H18B108.2
C9—C8—H8118.6C18—O19—C20111.8 (2)
C7—C8—H8118.6O19—C20—C21110.3 (3)
C8—C9—C10120.1 (2)O19—C20—H20A109.6
C8—C9—H9120.0C21—C20—H20A109.6
C10—C9—H9120.0O19—C20—H20B109.6
O13—C10—C9125.11 (19)C21—C20—H20B109.6
O13—C10—C11116.28 (19)H20A—C20—H20B108.1
C9—C10—C11118.6 (2)C20—C21—H21A109.5
C12—C11—C10120.6 (2)C20—C21—H21B109.5
C12—C11—H11119.7H21A—C21—H21B109.5
C10—C11—H11119.7C20—C21—H21C109.5
C11—C12—C7121.6 (2)H21A—C21—H21C109.5
C11—C12—H12119.2H21B—C21—H21C109.5
C7—C12—H12119.2O24—C22—O23123.4 (2)
C10—O13—C14117.94 (16)O24—C22—C3117.73 (19)
O13—C14—C15108.9 (2)O23—C22—C3118.8 (2)
O13—C14—H14A109.9C22—O24—H24117.6
C15—C14—H14A109.9
C6—C1—C2—C31.0 (4)O13—C10—C11—C12178.34 (19)
C1—C2—C3—C40.7 (3)C9—C10—C11—C121.2 (3)
C1—C2—C3—C22178.3 (2)C10—C11—C12—C70.0 (3)
C2—C3—C4—C51.6 (3)C8—C7—C12—C111.3 (3)
C22—C3—C4—C5177.4 (2)C6—C7—C12—C11179.17 (19)
C3—C4—C5—C60.9 (3)C9—C10—O13—C141.4 (3)
C4—C5—C6—C10.8 (3)C11—C10—O13—C14179.1 (2)
C4—C5—C6—C7179.3 (2)C10—O13—C14—C15173.27 (19)
C2—C1—C6—C51.7 (3)O13—C14—C15—O1672.1 (3)
C2—C1—C6—C7178.3 (2)C14—C15—O16—C17178.9 (2)
C5—C6—C7—C815.1 (3)C15—O16—C17—C18174.1 (2)
C1—C6—C7—C8164.9 (2)O16—C17—C18—O1972.2 (3)
C5—C6—C7—C12165.4 (2)C17—C18—O19—C20174.8 (2)
C1—C6—C7—C1214.6 (3)C18—O19—C20—C21176.2 (3)
C12—C7—C8—C91.6 (3)C2—C3—C22—O24179.8 (2)
C6—C7—C8—C9178.9 (2)C4—C3—C22—O241.2 (3)
C7—C8—C9—C100.4 (3)C2—C3—C22—O231.9 (3)
C8—C9—C10—O13178.5 (2)C4—C3—C22—O23177.0 (2)
C8—C9—C10—C111.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O24—H24···O23i0.821.802.619 (2)176
C18—H18B···O13ii0.972.583.478 (3)154
C1—H1···Cg2iii0.932.832.83138
C14—H14B···Cg2iv0.972.742.74149
Symmetry codes: (i) x, y+1, z+2; (ii) x, y+3/2, z1/2; (iii) x, y+3/2, z+1/2; (iv) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC19H22O5
Mr330.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)294
a, b, c (Å)25.430 (7), 7.769 (2), 8.656 (2)
β (°) 96.187 (5)
V3)1700.3 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.60 × 0.50 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS in SAINT-NT; Bruker, 2002)
Tmin, Tmax0.95, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
9420, 3634, 2230
Rint0.026
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.191, 0.99
No. of reflections3634
No. of parameters219
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.14

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O24—H24···O23i0.821.802.619 (2)176
C18—H18B···O13ii0.972.583.478 (3)154
C1—H1···Cg2iii0.932.832.83138.
C14—H14B···Cg2iv0.972.742.74149
Symmetry codes: (i) x, y+1, z+2; (ii) x, y+3/2, z1/2; (iii) x, y+3/2, z+1/2; (iv) x, y+1/2, z1/2.
 

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