Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614019147/wq3071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614019147/wq3071Isup2.hkl |
CCDC reference: 1020852
Symmetrical substituted benzenes have found widespread application as building units for the construction of attractive new metal–organic framework (MOF) structures (Kim et al., 2001; Hee et al., 2004; Kozachuk et al., 2014). In particular 4,4',4''-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]tribenzoate [benzoic acid?], which can be readily obtained by the hydrolysis of the herein reported triester, have been recently shown to produce MOF structures (MOF-180 and MOF-210; Furukawa et al., 2010) with surface areas up to 10400 m2 g-1. These materials exhibit exceptional porosities and gas (hydrogen, methane and carbon dioxide) uptake capacities. Analogous planar symmetrical benzene-based molecules have also sparked interest in the construction of new functional materials due to their adsorption on flat gold or graphite surfaces (Gutzler et al., 2009; Dienstmaier et al., 2010; Madueno et al., 2008). Clearly the structure of the title molecule is of interest in a variety of emerging research areas, and even though the organic backbones of MOFs have been structurally characterized, we report here the first crystal structure of the triethyl ester building block triethyl 4,4',4''-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]tribenzoate, (I).
Copper(I) iodide, 1,3,5-tribromobenzene and dichloridobis(triphenylphosphane)palladium were commercially available (Aldrich). 1,3,5-Triethynylbenzene (Demessence et al., 2009) and the title compound (Castellano & Rebek, 1998; Kuroda et al., 2006) were synthesized according to slight modifications of published procedures. Solid 1,3,5-tribromobenzene (9.45 g, 30.00 mmol), copper(I) iodide (50 mg, 0.26 mmol) and dichloridobis(triphenylphosphane)palladium(II) (400 mg, 0.57 mmol) were dissolved in freshly distilled triethylamine (200 ml) under a nitrogen atmosphere. Trimethysilylacetylene (10.6 g, 108 mmol) was added and the mixture was heated at 323 K for 24 h. After cooling, the resulting precipitate of triethylamine hydrobromide was removed by filtration and washed with ether. The combined filtrates were evaporated to dryness under reduced pressure and the residue was chromatographed on a column (SiO2, hexane) to yield 9.4 g (87%) of 1,3,5-tris(trimethylsilylethynyl)benzene. Aqueous NaOH (1 M, 50 ml) was then added to a solution of tris(trimethylsilylethynyl)benzene (315.6 mg, 0.862 mmol) in ethanol (80 ml), and the reaction mixture was heated with stirring at 313 K for 12 h. The solvent was evaporated and the residue was extracted with diethyl ether. The organic layer was dried over anhydrous magnesium sulfate and evaporated to dryness to yield the product. Crude 1,3,5-triethynylbenzene (123 mg, 0.82 mmol) was dissolved in dry triethylamine (40 ml) and added to a Schlenk flask containing ethyl 4-bromobenzoate (751 mg, 3.28 mmol), dichloridobis(triphenylphosphane)palladium(II) (70 mg, 0.1 mmol) and cuprous iodide (19 mg, 0.1 mmol). The reaction mixture was degassed and then stirred at 323 K for 3 d. The solution was evaporated and the residue was dissolved in ethyl acetate, washed with water and the organic layer was dried with anhydrous magnesium sulfate. The solvent was removed by evaporation and the residue was subjected to chromatography on silica gel with ethyl acetate/hexane (1:6) as the eluent to yield the product (yield 70 mg, 0.118 mmol, 14.4%). Single crystals of (I) were obtained by slow evaporation from a CDCl3 solution.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were placed at calculated positions, with C—H distances fixed at 0.93 Å for aromatic, and at 0.96 and 0.97 Å for methyl and methylene C atoms. The corresponding isotropic displacement parameters of H atoms were set equal to 1.2Ueq of the parent aromatic and methylene, and at 1.5Ueq of the methyl C atoms.
The deuterium atom from the deuterated solvent solvent molecule, CDCl3, was located in a difference Fourier map and was refined isotropically. H and D atoms were included in the SFAC and UNIT instructions separately, while both atom types employed the `H' scattering factor number.
The molecule of (I) (Fig. 1) is almost planar and has a chemical threefold axis. However, the three terminal benzene rings [B (atoms C9–C14), C (atoms C20–C25) and D (atoms C31–C36)] have slightly different orientations with respect to to the central ring A (atoms C1–C6). The planes of rings C and A exhibit the largest dihedral angle [7.3 (1)°], while the planes of rings B and D are almost coplanar with that of the central ring [dihedral angles = 3.1 (1) and 2.5 (1)°, respectively]. Bond lengths and angles (Table 2) are very similar for all three aromatic fragments in (I).
Each of the three pendent benzene rings is substituted by an ethoxycarbonyl group in the para position. The orientation of this substituent is the same in all three cases giving rise to a propeller-shaped molecule. Also in these ethyl ester groups, all non-H atoms are essentially coplanar (r.m.s. deviation of fitted atoms = 0.034, 0.017 and 0.007 Å for B, C and D, respectively). The dihedral angle between the mean plane through the ethoxycarbonyl group and the attached aromatic ring varies from 13.0 (2)° for ring B to 6.6 (2)° for ring D ring and 1.6 (2)° for ring C. Ring B exhibits the largest deviation of the ethoxycarbonyl group from coplanarity with the aromatic ring; a possible explanation for this structural difference can be found in the fact that ring B forms a C—H···O hydrogen bond to the CDCl3 solvent molecule. Considering the H···O distance as a criterion, this hydrogen bond (C40—D40···O1; symmetry code: x, y+1, z) is the most important hydrogen bond in the structure of (I) (Table 3). All carbonyl O atoms in (I) participate in weak C—H···O hydrogen bonds with neighboring molecules in the same layer, but the H···O distances in all cases are longer than 2.50 Å (Table 3).
The central benzene ring plays a significant role in the crystal packing of (I). This ring forms the most important π–π stacking interaction, with a perpendicular interplanar distance to the neighboring ring Ai at [symmetry code: (i) -x+1, -y+1, -z+1] of 3.32 (1) Å [the distance between the centroids (Cg) of the two rings is 3.549 (1) Å]. The centrosymmetric dimer formed via this intermolecular interaction is shown in Fig. 2. Within the dimer, atom C5 is almost perfectly located above the centroid of the neighboring ring (C5···CgA = 3.35 Å), while atoms C1 and C3 are positioned approximately one above the other, with a C1···C3i distance of 3.362 (3) Å. Besides the π–π interactions, ring A also participates in a relatively strong C—H···π intermolecular interaction as π-acceptor of the C27 methylene group. Atom H27B bonded to C27 is directed towards the centroid of ring A, forming a rather short H···CgA distance of 2.64 Å [perpendicular distance of H27B to ring A is 2.62 Å and the C27—H27B···CgA angle is 157°).
When the C27—H27B distance is corrected to a standard distance of ca 1.10 Å the H27B···CgA distance becomes 2.53 Å (orthogonal distance = 2.51 Å) which qualifies this interaction as a relatively strong intermolecular C—H···π interaction (Desiraju & Steiner, 2001). Molecules of (I) form parallel sheets in the crystal packing. Within a sheet, molecules are interconnected by C—H···O hydrogen bonds (see Table 3 for geometrical parameters and Fig. 3 for illustration), while the molecules in parallel neighbouring layers are interconnected by the above-described π–π and C—H···π interactions formed by ring A (Fig. 4). Ring C also participates in π–π interactions between sheets [CgC···CgCii = 3.781 (1) Å; symmetry code: (ii) -x+1, -y, -z+1, while the perpendicular interplanar distance between two C rings is 3.50 (1) Å].
In the Cambridge Structural Database (Allen, 2002), we found only five crystal structures with organic molecules having the same aromatic core as molecule (I) [see structure (II) in the Scheme]: OCUKEC (Day et al., 2001); PUBDOF (Bochkarev et al., 1998); PUBDOF01, WEVYIF and WEVYOL (Ponzini et al., 2000); ZABQUO and ZABQUO01 (Gardner et al., 1995). Unfortunately, the early crystal structures (refcodes ZABQUO and ZABQUO01) are without atomic coordinates. Nevertheless, a brief comparison of geometrical parameters and accessible information for all crystal structures confirms very similar bond distances within fragment (II), while some conformational characteristics (such as mutual orientation of terminal and central benzene rings) were found to differ significantly. Only in WEVYIF were all three terminal benzene rings approximately coplanar with the central ring (dihedral angles = 2.5–9.1°). This crystal structure is also the only case where structures form parallel layers similar to that observed in the crystal packing of (I). The central ring forms π–π interactions to a neighbouring central ring in OCUKEC and WEVYIF, while in no case does this ring participate as a π-acceptor in C—H···π interactions.
Data collection: APEX2 (Bruker–Nonius, 2005); cell refinement: SAINT (Bruker–Nonius, 2005); data reduction: SAINT (Bruker–Nonius, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2014); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and PARST (Nardelli, 1995).
C39H30O6·CDCl3 | Z = 2 |
Mr = 715.00 | F(000) = 740 |
Triclinic, P1 | Dx = 1.324 Mg m−3 |
a = 8.6557 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.0058 (7) Å | Cell parameters from 4066 reflections |
c = 16.4804 (11) Å | θ = 1.6–25.1° |
α = 111.036 (1)° | µ = 0.30 mm−1 |
β = 99.971 (1)° | T = 223 K |
γ = 97.835 (1)° | Block, colorless |
V = 1793.28 (17) Å3 | 0.40 × 0.35 × 0.25 mm |
Bruker APEXII CCD diffractometer | 6305 independent reflections |
Radiation source: fine-focus sealed tube | 4659 reflections with I > 2σ(I) |
Detector resolution: 8.3 pixels mm-1 | Rint = 0.025 |
CCD scans | θmax = 25.1°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker–Nonius, 2005) | h = −10→10 |
Tmin = 0.817, Tmax = 0.999 | k = −16→15 |
9224 measured reflections | l = 0→19 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0671P)2 + 0.4355P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
6305 reflections | Δρmax = 0.66 e Å−3 |
449 parameters | Δρmin = −0.55 e Å−3 |
C39H30O6·CDCl3 | γ = 97.835 (1)° |
Mr = 715.00 | V = 1793.28 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.6557 (4) Å | Mo Kα radiation |
b = 14.0058 (7) Å | µ = 0.30 mm−1 |
c = 16.4804 (11) Å | T = 223 K |
α = 111.036 (1)° | 0.40 × 0.35 × 0.25 mm |
β = 99.971 (1)° |
Bruker APEXII CCD diffractometer | 6305 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker–Nonius, 2005) | 4659 reflections with I > 2σ(I) |
Tmin = 0.817, Tmax = 0.999 | Rint = 0.025 |
9224 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.66 e Å−3 |
6305 reflections | Δρmin = −0.55 e Å−3 |
449 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.55597 (10) | 0.85379 (6) | 0.16761 (5) | 0.0819 (3) | |
Cl2 | 0.83258 (11) | 0.77262 (10) | 0.20884 (5) | 0.1068 (4) | |
Cl3 | 0.61616 (10) | 0.67337 (6) | 0.03549 (5) | 0.0846 (3) | |
O1 | 0.8339 (2) | −0.07156 (12) | 0.02404 (10) | 0.0569 (5) | |
O2 | 0.72253 (19) | 0.00640 (11) | −0.06110 (9) | 0.0477 (4) | |
O3 | 0.05665 (19) | 1.11764 (13) | 0.39086 (10) | 0.0507 (4) | |
O4 | 0.10205 (17) | 1.18872 (11) | 0.54032 (9) | 0.0427 (4) | |
O5 | 1.2113 (2) | 0.72269 (15) | 1.19475 (10) | 0.0639 (5) | |
O6 | 1.31069 (19) | 0.58412 (13) | 1.12539 (9) | 0.0499 (4) | |
C1 | 0.6936 (2) | 0.50539 (15) | 0.45662 (12) | 0.0334 (4) | |
C2 | 0.6049 (2) | 0.57886 (15) | 0.44871 (12) | 0.0347 (5) | |
H2 | 0.5489 | 0.5713 | 0.3925 | 0.042* | |
C3 | 0.5994 (2) | 0.66381 (15) | 0.52464 (12) | 0.0326 (4) | |
C4 | 0.6810 (2) | 0.67329 (15) | 0.60875 (13) | 0.0352 (5) | |
H4 | 0.6768 | 0.7293 | 0.6596 | 0.042* | |
C5 | 0.7686 (2) | 0.59991 (15) | 0.61750 (13) | 0.0342 (4) | |
C6 | 0.7759 (2) | 0.51645 (16) | 0.54107 (13) | 0.0368 (5) | |
H6 | 0.8360 | 0.4679 | 0.5466 | 0.044* | |
C7 | 0.6999 (2) | 0.41714 (16) | 0.37852 (13) | 0.0363 (5) | |
C8 | 0.7054 (3) | 0.34337 (16) | 0.31556 (13) | 0.0391 (5) | |
C9 | 0.7147 (2) | 0.25400 (15) | 0.23975 (13) | 0.0364 (5) | |
C10 | 0.6423 (3) | 0.24056 (17) | 0.15264 (13) | 0.0413 (5) | |
H10 | 0.5830 | 0.2880 | 0.1436 | 0.050* | |
C11 | 0.6578 (3) | 0.15769 (17) | 0.08010 (13) | 0.0408 (5) | |
H11 | 0.6101 | 0.1498 | 0.0223 | 0.049* | |
C12 | 0.7448 (3) | 0.08580 (16) | 0.09319 (13) | 0.0377 (5) | |
C13 | 0.8143 (3) | 0.09778 (16) | 0.17990 (13) | 0.0414 (5) | |
H13 | 0.8709 | 0.0491 | 0.1889 | 0.050* | |
C14 | 0.8001 (3) | 0.18121 (16) | 0.25256 (13) | 0.0413 (5) | |
H14 | 0.8476 | 0.1888 | 0.3103 | 0.050* | |
C15 | 0.7713 (3) | −0.00212 (17) | 0.01665 (13) | 0.0412 (5) | |
C16 | 0.7542 (3) | −0.07135 (18) | −0.13968 (14) | 0.0530 (6) | |
H16A | 0.6922 | −0.1404 | −0.1525 | 0.064* | |
H16B | 0.8673 | −0.0733 | −0.1296 | 0.064* | |
C17 | 0.7064 (5) | −0.0391 (2) | −0.21507 (17) | 0.0910 (11) | |
H17A | 0.5916 | −0.0489 | −0.2308 | 0.136* | |
H17B | 0.7419 | −0.0810 | −0.2657 | 0.136* | |
H17C | 0.7548 | 0.0334 | −0.1975 | 0.136* | |
C18 | 0.5107 (2) | 0.74037 (16) | 0.51521 (13) | 0.0361 (5) | |
C19 | 0.4414 (2) | 0.80532 (16) | 0.50673 (13) | 0.0375 (5) | |
C20 | 0.3584 (2) | 0.88391 (15) | 0.49637 (13) | 0.0349 (5) | |
C21 | 0.3385 (3) | 0.96449 (16) | 0.57114 (13) | 0.0399 (5) | |
H21 | 0.3798 | 0.9675 | 0.6282 | 0.048* | |
C22 | 0.2583 (3) | 1.03954 (16) | 0.56119 (13) | 0.0385 (5) | |
H22 | 0.2459 | 1.0929 | 0.6115 | 0.046* | |
C23 | 0.1957 (2) | 1.03592 (15) | 0.47637 (13) | 0.0348 (4) | |
C24 | 0.2131 (2) | 0.95524 (16) | 0.40170 (13) | 0.0384 (5) | |
H24 | 0.1696 | 0.9517 | 0.3447 | 0.046* | |
C25 | 0.2944 (2) | 0.88013 (16) | 0.41120 (13) | 0.0387 (5) | |
H25 | 0.3065 | 0.8269 | 0.3607 | 0.046* | |
C26 | 0.1104 (2) | 1.11651 (16) | 0.46243 (14) | 0.0372 (5) | |
C27 | 0.0219 (3) | 1.27170 (16) | 0.53568 (14) | 0.0412 (5) | |
H27A | −0.0901 | 1.2431 | 0.5040 | 0.049* | |
H27B | 0.0732 | 1.3093 | 0.5047 | 0.049* | |
C28 | 0.0359 (3) | 1.34363 (18) | 0.63130 (16) | 0.0557 (6) | |
H28A | −0.0232 | 1.3070 | 0.6594 | 0.084* | |
H28B | −0.0071 | 1.4036 | 0.6322 | 0.084* | |
H28C | 0.1469 | 1.3661 | 0.6631 | 0.084* | |
C29 | 0.8480 (3) | 0.60897 (16) | 0.70503 (13) | 0.0384 (5) | |
C30 | 0.9124 (3) | 0.61708 (16) | 0.77782 (13) | 0.0394 (5) | |
C31 | 0.9909 (2) | 0.62598 (16) | 0.86536 (13) | 0.0376 (5) | |
C32 | 1.0745 (3) | 0.55122 (18) | 0.87563 (13) | 0.0459 (6) | |
H32 | 1.0791 | 0.4947 | 0.8253 | 0.055* | |
C33 | 1.1503 (3) | 0.55990 (18) | 0.95916 (14) | 0.0459 (6) | |
H33 | 1.2054 | 0.5093 | 0.9651 | 0.055* | |
C34 | 1.1446 (2) | 0.64424 (17) | 1.03503 (13) | 0.0397 (5) | |
C35 | 1.0624 (3) | 0.71912 (17) | 1.02519 (14) | 0.0435 (5) | |
H35 | 1.0588 | 0.7758 | 1.0757 | 0.052* | |
C36 | 0.9858 (3) | 0.71061 (17) | 0.94152 (14) | 0.0429 (5) | |
H36 | 0.9306 | 0.7613 | 0.9358 | 0.052* | |
C37 | 1.2238 (3) | 0.65612 (19) | 1.12705 (14) | 0.0457 (5) | |
C38 | 1.3982 (3) | 0.5901 (2) | 1.21119 (14) | 0.0564 (7) | |
H38A | 1.3246 | 0.5811 | 1.2474 | 0.068* | |
H38B | 1.4724 | 0.6574 | 1.2436 | 0.068* | |
C39 | 1.4869 (4) | 0.5037 (2) | 1.19026 (16) | 0.0717 (8) | |
H39A | 1.4115 | 0.4375 | 1.1617 | 0.108* | |
H39B | 1.5530 | 0.5069 | 1.2447 | 0.108* | |
H39C | 1.5533 | 0.5110 | 1.1509 | 0.108* | |
C40 | 0.7039 (3) | 0.7919 (2) | 0.12545 (16) | 0.0563 (6) | |
D40 | 0.766 (3) | 0.836 (2) | 0.1038 (17) | 0.066 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0794 (5) | 0.0752 (5) | 0.0859 (5) | 0.0362 (4) | 0.0193 (4) | 0.0190 (4) |
Cl2 | 0.0926 (6) | 0.1798 (10) | 0.0620 (5) | 0.0683 (7) | 0.0111 (4) | 0.0528 (6) |
Cl3 | 0.0902 (6) | 0.0761 (5) | 0.0676 (5) | 0.0150 (4) | 0.0176 (4) | 0.0072 (4) |
O1 | 0.0883 (13) | 0.0444 (9) | 0.0481 (9) | 0.0364 (9) | 0.0281 (9) | 0.0165 (8) |
O2 | 0.0667 (10) | 0.0439 (9) | 0.0306 (8) | 0.0237 (8) | 0.0160 (7) | 0.0064 (7) |
O3 | 0.0604 (10) | 0.0557 (10) | 0.0433 (9) | 0.0278 (8) | 0.0079 (7) | 0.0244 (8) |
O4 | 0.0517 (9) | 0.0388 (8) | 0.0440 (8) | 0.0234 (7) | 0.0122 (7) | 0.0186 (7) |
O5 | 0.0729 (12) | 0.0831 (13) | 0.0284 (8) | 0.0366 (10) | 0.0071 (8) | 0.0090 (8) |
O6 | 0.0595 (10) | 0.0613 (10) | 0.0293 (7) | 0.0251 (8) | 0.0040 (7) | 0.0170 (7) |
C1 | 0.0394 (11) | 0.0322 (10) | 0.0291 (10) | 0.0108 (9) | 0.0110 (8) | 0.0102 (8) |
C2 | 0.0391 (11) | 0.0377 (11) | 0.0273 (10) | 0.0110 (9) | 0.0064 (8) | 0.0124 (9) |
C3 | 0.0355 (11) | 0.0304 (10) | 0.0328 (10) | 0.0103 (9) | 0.0090 (8) | 0.0120 (8) |
C4 | 0.0414 (12) | 0.0301 (10) | 0.0291 (10) | 0.0090 (9) | 0.0080 (8) | 0.0055 (8) |
C5 | 0.0379 (11) | 0.0325 (11) | 0.0299 (10) | 0.0077 (9) | 0.0051 (8) | 0.0111 (8) |
C6 | 0.0422 (12) | 0.0344 (11) | 0.0358 (11) | 0.0158 (9) | 0.0087 (9) | 0.0138 (9) |
C7 | 0.0454 (12) | 0.0347 (11) | 0.0302 (10) | 0.0133 (9) | 0.0080 (9) | 0.0131 (9) |
C8 | 0.0460 (13) | 0.0391 (12) | 0.0341 (11) | 0.0159 (10) | 0.0110 (9) | 0.0136 (10) |
C9 | 0.0422 (12) | 0.0340 (11) | 0.0325 (10) | 0.0132 (9) | 0.0128 (9) | 0.0090 (9) |
C10 | 0.0509 (13) | 0.0391 (12) | 0.0380 (11) | 0.0233 (10) | 0.0122 (9) | 0.0143 (9) |
C11 | 0.0494 (13) | 0.0436 (12) | 0.0287 (10) | 0.0173 (10) | 0.0092 (9) | 0.0108 (9) |
C12 | 0.0455 (12) | 0.0338 (11) | 0.0347 (11) | 0.0134 (9) | 0.0135 (9) | 0.0111 (9) |
C13 | 0.0521 (13) | 0.0387 (12) | 0.0382 (11) | 0.0208 (10) | 0.0136 (10) | 0.0152 (10) |
C14 | 0.0516 (13) | 0.0414 (12) | 0.0307 (10) | 0.0156 (10) | 0.0085 (9) | 0.0124 (9) |
C15 | 0.0507 (13) | 0.0364 (12) | 0.0362 (11) | 0.0135 (10) | 0.0161 (10) | 0.0099 (9) |
C16 | 0.0723 (17) | 0.0445 (13) | 0.0357 (12) | 0.0185 (12) | 0.0205 (11) | 0.0026 (10) |
C17 | 0.179 (4) | 0.0598 (18) | 0.0407 (15) | 0.047 (2) | 0.0408 (18) | 0.0131 (13) |
C18 | 0.0409 (12) | 0.0326 (11) | 0.0323 (10) | 0.0093 (9) | 0.0089 (9) | 0.0094 (9) |
C19 | 0.0390 (12) | 0.0357 (11) | 0.0358 (11) | 0.0103 (10) | 0.0087 (9) | 0.0112 (9) |
C20 | 0.0360 (11) | 0.0313 (11) | 0.0375 (11) | 0.0101 (9) | 0.0086 (9) | 0.0128 (9) |
C21 | 0.0476 (13) | 0.0413 (12) | 0.0317 (10) | 0.0173 (10) | 0.0053 (9) | 0.0143 (9) |
C22 | 0.0471 (12) | 0.0357 (11) | 0.0325 (11) | 0.0158 (10) | 0.0105 (9) | 0.0103 (9) |
C23 | 0.0339 (11) | 0.0343 (11) | 0.0390 (11) | 0.0106 (9) | 0.0083 (9) | 0.0168 (9) |
C24 | 0.0434 (12) | 0.0423 (12) | 0.0316 (10) | 0.0135 (10) | 0.0073 (9) | 0.0160 (9) |
C25 | 0.0455 (12) | 0.0362 (11) | 0.0329 (11) | 0.0138 (10) | 0.0106 (9) | 0.0095 (9) |
C26 | 0.0366 (11) | 0.0378 (12) | 0.0411 (12) | 0.0124 (9) | 0.0096 (9) | 0.0183 (10) |
C27 | 0.0407 (12) | 0.0379 (12) | 0.0519 (13) | 0.0182 (10) | 0.0114 (10) | 0.0220 (10) |
C28 | 0.0700 (17) | 0.0450 (14) | 0.0565 (14) | 0.0302 (13) | 0.0138 (12) | 0.0191 (12) |
C29 | 0.0447 (12) | 0.0358 (11) | 0.0332 (11) | 0.0134 (10) | 0.0062 (9) | 0.0115 (9) |
C30 | 0.0442 (12) | 0.0382 (12) | 0.0339 (11) | 0.0127 (10) | 0.0071 (9) | 0.0116 (9) |
C31 | 0.0387 (12) | 0.0423 (12) | 0.0294 (10) | 0.0099 (9) | 0.0055 (8) | 0.0122 (9) |
C32 | 0.0582 (14) | 0.0454 (13) | 0.0277 (10) | 0.0218 (11) | 0.0059 (9) | 0.0050 (9) |
C33 | 0.0549 (14) | 0.0478 (13) | 0.0355 (11) | 0.0246 (11) | 0.0071 (10) | 0.0140 (10) |
C34 | 0.0398 (12) | 0.0479 (13) | 0.0291 (10) | 0.0124 (10) | 0.0068 (9) | 0.0122 (9) |
C35 | 0.0505 (13) | 0.0436 (12) | 0.0309 (11) | 0.0170 (11) | 0.0098 (9) | 0.0060 (9) |
C36 | 0.0497 (13) | 0.0431 (13) | 0.0371 (11) | 0.0195 (10) | 0.0098 (9) | 0.0139 (10) |
C37 | 0.0452 (13) | 0.0571 (15) | 0.0317 (11) | 0.0136 (11) | 0.0073 (9) | 0.0140 (11) |
C38 | 0.0644 (16) | 0.0741 (17) | 0.0305 (11) | 0.0234 (14) | 0.0024 (10) | 0.0213 (11) |
C39 | 0.089 (2) | 0.095 (2) | 0.0387 (13) | 0.0494 (18) | 0.0080 (13) | 0.0269 (14) |
C40 | 0.0589 (16) | 0.0654 (17) | 0.0483 (14) | 0.0146 (13) | 0.0111 (12) | 0.0268 (13) |
Cl1—C40 | 1.747 (3) | C17—H17B | 0.9600 |
Cl2—C40 | 1.738 (3) | C17—H17C | 0.9600 |
Cl3—C40 | 1.740 (3) | C18—C19 | 1.191 (3) |
O1—C15 | 1.209 (2) | C19—C20 | 1.437 (3) |
O2—C15 | 1.331 (3) | C20—C25 | 1.396 (3) |
O2—C16 | 1.460 (2) | C20—C21 | 1.396 (3) |
O3—C26 | 1.197 (2) | C21—C22 | 1.377 (3) |
O4—C26 | 1.340 (2) | C21—H21 | 0.9300 |
O4—C27 | 1.450 (2) | C22—C23 | 1.389 (3) |
O5—C37 | 1.204 (3) | C22—H22 | 0.9300 |
O6—C37 | 1.333 (3) | C23—C24 | 1.388 (3) |
O6—C38 | 1.451 (2) | C23—C26 | 1.492 (3) |
C1—C6 | 1.393 (3) | C24—C25 | 1.381 (3) |
C1—C2 | 1.394 (3) | C24—H24 | 0.9300 |
C1—C7 | 1.445 (3) | C25—H25 | 0.9300 |
C2—C3 | 1.397 (3) | C27—C28 | 1.508 (3) |
C2—H2 | 0.9300 | C27—H27A | 0.9700 |
C3—C4 | 1.393 (3) | C27—H27B | 0.9700 |
C3—C18 | 1.438 (3) | C28—H28A | 0.9600 |
C4—C5 | 1.390 (3) | C28—H28B | 0.9600 |
C4—H4 | 0.9300 | C28—H28C | 0.9600 |
C5—C6 | 1.396 (3) | C29—C30 | 1.190 (3) |
C5—C29 | 1.439 (3) | C30—C31 | 1.438 (3) |
C6—H6 | 0.9300 | C31—C32 | 1.393 (3) |
C7—C8 | 1.186 (3) | C31—C36 | 1.396 (3) |
C8—C9 | 1.440 (3) | C32—C33 | 1.373 (3) |
C9—C14 | 1.391 (3) | C32—H32 | 0.9300 |
C9—C10 | 1.397 (3) | C33—C34 | 1.392 (3) |
C10—C11 | 1.377 (3) | C33—H33 | 0.9300 |
C10—H10 | 0.9300 | C34—C35 | 1.385 (3) |
C11—C12 | 1.391 (3) | C34—C37 | 1.492 (3) |
C11—H11 | 0.9300 | C35—C36 | 1.378 (3) |
C12—C13 | 1.391 (3) | C35—H35 | 0.9300 |
C12—C15 | 1.491 (3) | C36—H36 | 0.9300 |
C13—C14 | 1.379 (3) | C38—C39 | 1.489 (4) |
C13—H13 | 0.9300 | C38—H38A | 0.9700 |
C14—H14 | 0.9300 | C38—H38B | 0.9700 |
C16—C17 | 1.481 (4) | C39—H39A | 0.9600 |
C16—H16A | 0.9700 | C39—H39B | 0.9600 |
C16—H16B | 0.9700 | C39—H39C | 0.9600 |
C17—H17A | 0.9600 | C40—D40 | 0.97 (3) |
C15—O2—C16 | 116.53 (17) | C23—C22—H22 | 119.8 |
C26—O4—C27 | 116.92 (15) | C24—C23—C22 | 119.38 (18) |
C37—O6—C38 | 116.85 (17) | C24—C23—C26 | 118.45 (18) |
C6—C1—C2 | 119.57 (17) | C22—C23—C26 | 122.17 (18) |
C6—C1—C7 | 119.50 (17) | C25—C24—C23 | 120.62 (18) |
C2—C1—C7 | 120.93 (17) | C25—C24—H24 | 119.7 |
C1—C2—C3 | 120.48 (17) | C23—C24—H24 | 119.7 |
C1—C2—H2 | 119.8 | C24—C25—C20 | 120.17 (18) |
C3—C2—H2 | 119.8 | C24—C25—H25 | 119.9 |
C4—C3—C2 | 119.30 (17) | C20—C25—H25 | 119.9 |
C4—C3—C18 | 120.86 (17) | O3—C26—O4 | 123.73 (18) |
C2—C3—C18 | 119.84 (17) | O3—C26—C23 | 124.63 (19) |
C5—C4—C3 | 120.69 (17) | O4—C26—C23 | 111.64 (16) |
C5—C4—H4 | 119.7 | O4—C27—C28 | 106.01 (16) |
C3—C4—H4 | 119.7 | O4—C27—H27A | 110.5 |
C4—C5—C6 | 119.54 (17) | C28—C27—H27A | 110.5 |
C4—C5—C29 | 120.02 (17) | O4—C27—H27B | 110.5 |
C6—C5—C29 | 120.42 (18) | C28—C27—H27B | 110.5 |
C1—C6—C5 | 120.39 (18) | H27A—C27—H27B | 108.7 |
C1—C6—H6 | 119.8 | C27—C28—H28A | 109.5 |
C5—C6—H6 | 119.8 | C27—C28—H28B | 109.5 |
C8—C7—C1 | 178.5 (2) | H28A—C28—H28B | 109.5 |
C7—C8—C9 | 179.1 (2) | C27—C28—H28C | 109.5 |
C14—C9—C10 | 119.17 (17) | H28A—C28—H28C | 109.5 |
C14—C9—C8 | 120.06 (18) | H28B—C28—H28C | 109.5 |
C10—C9—C8 | 120.75 (18) | C30—C29—C5 | 179.2 (2) |
C11—C10—C9 | 120.60 (19) | C29—C30—C31 | 179.4 (2) |
C11—C10—H10 | 119.7 | C32—C31—C36 | 118.93 (18) |
C9—C10—H10 | 119.7 | C32—C31—C30 | 120.76 (18) |
C10—C11—C12 | 120.03 (19) | C36—C31—C30 | 120.31 (19) |
C10—C11—H11 | 120.0 | C33—C32—C31 | 120.82 (19) |
C12—C11—H11 | 120.0 | C33—C32—H32 | 119.6 |
C11—C12—C13 | 119.49 (18) | C31—C32—H32 | 119.6 |
C11—C12—C15 | 121.85 (18) | C32—C33—C34 | 120.1 (2) |
C13—C12—C15 | 118.62 (18) | C32—C33—H33 | 119.9 |
C14—C13—C12 | 120.54 (19) | C34—C33—H33 | 119.9 |
C14—C13—H13 | 119.7 | C35—C34—C33 | 119.29 (19) |
C12—C13—H13 | 119.7 | C35—C34—C37 | 118.82 (19) |
C13—C14—C9 | 120.15 (19) | C33—C34—C37 | 121.88 (19) |
C13—C14—H14 | 119.9 | C36—C35—C34 | 120.80 (19) |
C9—C14—H14 | 119.9 | C36—C35—H35 | 119.6 |
O1—C15—O2 | 123.57 (18) | C34—C35—H35 | 119.6 |
O1—C15—C12 | 124.35 (19) | C35—C36—C31 | 120.02 (19) |
O2—C15—C12 | 112.04 (18) | C35—C36—H36 | 120.0 |
O2—C16—C17 | 106.56 (19) | C31—C36—H36 | 120.0 |
O2—C16—H16A | 110.4 | O5—C37—O6 | 123.92 (19) |
C17—C16—H16A | 110.4 | O5—C37—C34 | 124.2 (2) |
O2—C16—H16B | 110.4 | O6—C37—C34 | 111.84 (18) |
C17—C16—H16B | 110.4 | O6—C38—C39 | 105.84 (18) |
H16A—C16—H16B | 108.6 | O6—C38—H38A | 110.6 |
C16—C17—H17A | 109.5 | C39—C38—H38A | 110.6 |
C16—C17—H17B | 109.5 | O6—C38—H38B | 110.6 |
H17A—C17—H17B | 109.5 | C39—C38—H38B | 110.6 |
C16—C17—H17C | 109.5 | H38A—C38—H38B | 108.7 |
H17A—C17—H17C | 109.5 | C38—C39—H39A | 109.5 |
H17B—C17—H17C | 109.5 | C38—C39—H39B | 109.5 |
C19—C18—C3 | 177.8 (2) | H39A—C39—H39B | 109.5 |
C18—C19—C20 | 179.8 (2) | C38—C39—H39C | 109.5 |
C25—C20—C21 | 118.88 (18) | H39A—C39—H39C | 109.5 |
C25—C20—C19 | 120.48 (17) | H39B—C39—H39C | 109.5 |
C21—C20—C19 | 120.64 (17) | Cl2—C40—Cl3 | 110.72 (16) |
C22—C21—C20 | 120.64 (18) | Cl2—C40—Cl1 | 110.71 (14) |
C22—C21—H21 | 119.7 | Cl3—C40—Cl1 | 110.38 (15) |
C20—C21—H21 | 119.7 | Cl2—C40—D40 | 108.4 (16) |
C21—C22—C23 | 120.30 (18) | Cl3—C40—D40 | 107.7 (16) |
C21—C22—H22 | 119.8 | Cl1—C40—D40 | 108.8 (16) |
C6—C1—C2—C3 | 0.7 (3) | C21—C22—C23—C24 | 0.8 (3) |
C7—C1—C2—C3 | 179.90 (19) | C21—C22—C23—C26 | −178.95 (19) |
C1—C2—C3—C4 | −1.3 (3) | C22—C23—C24—C25 | −1.2 (3) |
C1—C2—C3—C18 | 178.45 (19) | C26—C23—C24—C25 | 178.51 (19) |
C2—C3—C4—C5 | 0.7 (3) | C23—C24—C25—C20 | 0.8 (3) |
C18—C3—C4—C5 | −179.07 (19) | C21—C20—C25—C24 | 0.1 (3) |
C3—C4—C5—C6 | 0.6 (3) | C19—C20—C25—C24 | 179.28 (19) |
C3—C4—C5—C29 | −178.0 (2) | C27—O4—C26—O3 | 0.4 (3) |
C2—C1—C6—C5 | 0.6 (3) | C27—O4—C26—C23 | 179.88 (17) |
C7—C1—C6—C5 | −178.65 (19) | C24—C23—C26—O3 | −0.9 (3) |
C4—C5—C6—C1 | −1.2 (3) | C22—C23—C26—O3 | 178.8 (2) |
C29—C5—C6—C1 | 177.4 (2) | C24—C23—C26—O4 | 179.58 (18) |
C14—C9—C10—C11 | −1.4 (3) | C22—C23—C26—O4 | −0.7 (3) |
C8—C9—C10—C11 | 176.9 (2) | C26—O4—C27—C28 | −177.55 (19) |
C9—C10—C11—C12 | 0.7 (3) | C36—C31—C32—C33 | 0.3 (4) |
C10—C11—C12—C13 | 0.6 (3) | C30—C31—C32—C33 | 179.7 (2) |
C10—C11—C12—C15 | −177.0 (2) | C31—C32—C33—C34 | −0.2 (4) |
C11—C12—C13—C14 | −1.2 (3) | C32—C33—C34—C35 | −0.2 (4) |
C15—C12—C13—C14 | 176.5 (2) | C32—C33—C34—C37 | 179.4 (2) |
C12—C13—C14—C9 | 0.5 (3) | C33—C34—C35—C36 | 0.4 (3) |
C10—C9—C14—C13 | 0.8 (3) | C37—C34—C35—C36 | −179.2 (2) |
C8—C9—C14—C13 | −177.5 (2) | C34—C35—C36—C31 | −0.2 (4) |
C16—O2—C15—O1 | −2.5 (3) | C32—C31—C36—C35 | −0.1 (3) |
C16—O2—C15—C12 | 175.46 (19) | C30—C31—C36—C35 | −179.5 (2) |
C11—C12—C15—O1 | −173.4 (2) | C38—O6—C37—O5 | −2.0 (4) |
C13—C12—C15—O1 | 8.9 (3) | C38—O6—C37—C34 | 177.9 (2) |
C11—C12—C15—O2 | 8.6 (3) | C35—C34—C37—O5 | 5.9 (4) |
C13—C12—C15—O2 | −169.1 (2) | C33—C34—C37—O5 | −173.7 (2) |
C15—O2—C16—C17 | −173.8 (2) | C35—C34—C37—O6 | −173.9 (2) |
C25—C20—C21—C22 | −0.5 (3) | C33—C34—C37—O6 | 6.5 (3) |
C19—C20—C21—C22 | −179.7 (2) | C37—O6—C38—C39 | −178.6 (2) |
C20—C21—C22—C23 | 0.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C40—D40···O1i | 0.97 (3) | 2.24 (3) | 3.175 (3) | 162 (2) |
C36—H36···O1ii | 0.93 | 2.61 | 3.408 (3) | 144 |
C14—H14···O3iii | 0.93 | 2.58 | 3.341 (3) | 140 |
C25—H25···O5iv | 0.93 | 2.51 | 3.337 (2) | 148 |
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1; (iii) x+1, y−1, z; (iv) x−1, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C39H30O6·CDCl3 |
Mr | 715.00 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 223 |
a, b, c (Å) | 8.6557 (4), 14.0058 (7), 16.4804 (11) |
α, β, γ (°) | 111.036 (1), 99.971 (1), 97.835 (1) |
V (Å3) | 1793.28 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.40 × 0.35 × 0.25 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker–Nonius, 2005) |
Tmin, Tmax | 0.817, 0.999 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9224, 6305, 4659 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.130, 1.05 |
No. of reflections | 6305 |
No. of parameters | 449 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.55 |
Computer programs: APEX2 (Bruker–Nonius, 2005), SAINT (Bruker–Nonius, 2005), SHELXS97 (Sheldrick, 2008), SHELXL2014/6 (Sheldrick, 2014), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 2012), PLATON (Spek, 2009) and PARST (Nardelli, 1995).
O1—C15 | 1.209 (2) | O5—C37 | 1.204 (3) |
O2—C15 | 1.331 (3) | O6—C37 | 1.333 (3) |
O2—C16 | 1.460 (2) | O6—C38 | 1.451 (2) |
O3—C26 | 1.197 (2) | C7—C8 | 1.186 (3) |
O4—C26 | 1.340 (2) | C18—C19 | 1.191 (3) |
O4—C27 | 1.450 (2) | C29—C30 | 1.190 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C40—D40···O1i | 0.97 (3) | 2.24 (3) | 3.175 (3) | 162 (2) |
C36—H36···O1ii | 0.93 | 2.61 | 3.408 (3) | 144 |
C14—H14···O3iii | 0.93 | 2.58 | 3.341 (3) | 140 |
C25—H25···O5iv | 0.93 | 2.51 | 3.337 (2) | 148 |
Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z+1; (iii) x+1, y−1, z; (iv) x−1, y, z−1. |