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In the methanol solvate crystal form of the title diacid diglycol calixarene, C54H72O10·CH4O, two calixarene mol­ecules (in the cone conformation) are dimerized via two methanol mol­ecules hydrogen bonded to the carboxyl groups. An intramolecular bond is also formed between a carboxylic proton and an ether O atom. This result is relevant to the interpretation of the acidic and complexation properties of calixarene carboxylic acids.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827019901522X/sk1335sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827019901522X/sk1335Isup2.hkl
Contains datablock I

CCDC reference: 143250

Comment top

Calixarenes are macrocyclic molecules made up of p-substituted phenolic units linked by methylene bridges ortho to the OH functions (Gutsche, 1989; Vicens & Böhmer, 1991; Böhmer, 1995). The ability of parent phenolic calixarenes, as well as of their chemically modified derivatives obtained by the substitution of the phenolic H atoms with various types of ligating groups, to bind metal ions is well established (Böhmer, 1995).

With calix[4]arenes, the substituents frequently immobilize the molecule in a single conformation: cone, partial cone, 1,2- or 1,3-alternate. Calixarene carboxylic acids, in which the carboxylic groups are attached to the phenolic O atoms, display interesting complexation properties towards alkali and alkali earth metal cations (McKervey et al., 1996), as well as towards the lanthanides and Th (Arnaud-Neu et al., 1997). The tetra(carboxymethoxy) derivative of p-tert-butylcalix[4]arene has been shown recently to display a high selectivity for AcIII cations (Chen et al., 1998). The systematic study of the acid-base and complexation properties towards alkali metal cations of a series of calixarene carboxylic acids has been reported by McKervey et al. (1996). The determination of pKa values in methanol showed that, whatever the number of carboxylic acid functions (except for one mono-acid compound), the p-tert-butylcalix[4]arene carboxylic acid derivatives in the cone conformation are less acidic than phenoxyacetic acid. This observation was interpreted in terms of stabilization of the protonated form by intramolecular hydrogen bonding. The structure of the title methanol solvate, (I), reported herein indicates that, in solution in methanol, intermolecular hydrogen bonds leading to dimerization are also to be taken into account. \scheme

The asymmetric unit of (I) comprises one calixarene and one methanol molecule. The calixarene is in a distorted cone conformation, in which the dihedral angles between the four aromatic rings and the mean plane defined by the four methylenic bridges are 49.62 (7), 84.69 (5), 48.42 (6) and 88.05 (5)°. The two rings bonded to the glycolic chains are more vertical than the other two rings. Such a pseudo-C2 geometry is rather frequent in calix[4]arenes bearing different bulky substituents and the resulting pinching of the cone has been thought to prevent solvent inclusion in the calixarene cavity (Drew et al., 1997), which is confirmed in the present case. This geometry enables one of the carboxylic O atoms (O7) to be directed towards the inside of the molecule and to form hydrogen bonds with the ether atoms O4 and O6 (see Table 1).

The methanol molecule forms two hydrogen bonds, one with the carboxylic atom O2, pertaining to the acid group directed outwards, and the other with the atom O8(-x, -y, -z) from another calixarene molecule, related to the first one by the symmetry centre. This leads to the formation of dimers, including two head-to-head calixarene molecules, with their main axis parallel to each other, interconnected by two methanol molecules. Obviously, such a dimerization would not be possible if both carboxylic groups were involved in intramolecular hydrogen bonds. On the other hand, a dimerization by direct bonding of the carboxylic groups of the two molecules would probably be hampered by the steric hindrance of the glycolic chains. The present bonding pattern must be taken into consideration when complexation equilibria in methanol, during cation transportation, are considered.

Experimental top

Compound (I) was synthesized according to the literature method of Barakat et al. (1998) and was recrystallized from methanol.

Refinement top

The carboxyl and hydroxyl (methanol) protons were found on the difference Fourier map and introduced as riding atoms with a displacement factor equal to 1.2 times that of the attached O atom. All other H atoms were introduced at calculated positions as riding atoms with a displacement factor equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the attached C atom.

Computing details top

Data collection: Kappa-CCD Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with the atom-numbering scheme. H atoms are omitted for clarity, apart from those involved in hydrogen bonds, which are drawn as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines and displacement ellipsoids are drawn at the 40% probability level [symmetry code: (i) -x, -y, -z].
(I) top
Crystal data top
C54H72O10·CH4OF(000) = 1976
Mr = 913.16Dx = 1.146 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 17.7426 (9) ÅCell parameters from 18139 reflections
b = 15.5402 (6) Åθ = 2.6–25.7°
c = 19.8147 (10) ŵ = 0.08 mm1
β = 104.279 (2)°T = 127 K
V = 5294.6 (4) Å3Platelet, colourless
Z = 40.45 × 0.28 × 0.25 mm
Data collection top
Nonius Kappa-CCD
diffractometer
6410 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 25.7°, θmin = 2.6°
Detector resolution: 18 pixels mm-1h = 2121
ϕ scansk = 018
18139 measured reflectionsl = 2424
9972 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.138 w = 1/[σ2(Fo2) + (0.0543P)2 + 1.7978P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
9972 reflectionsΔρmax = 0.27 e Å3
614 parametersΔρmin = 0.23 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0049 (4)
Crystal data top
C54H72O10·CH4OV = 5294.6 (4) Å3
Mr = 913.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.7426 (9) ŵ = 0.08 mm1
b = 15.5402 (6) ÅT = 127 K
c = 19.8147 (10) Å0.45 × 0.28 × 0.25 mm
β = 104.279 (2)°
Data collection top
Nonius Kappa-CCD
diffractometer
6410 reflections with I > 2σ(I)
18139 measured reflectionsRint = 0.050
9972 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.27 e Å3
9972 reflectionsΔρmin = 0.23 e Å3
614 parameters
Special details top

Experimental. A 180° range in ϕ was scanned during data collection, with 2° ϕ steps. The crystal-to-detector distance was fixed at 28 mm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Structure solved by direct methods. All non-hydrogen atoms refined anisotropically. Carboxyl and hydroxyl (methanol) protons found on the Fourier map and introduced as riding atoms with a displacement factor equal to 1.2 times that of the attached oxygen atom. All other hydrogen atoms introduced at calculated positions as riding atoms with a displacement factor equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the attached carbon atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.13968 (9)0.29531 (9)0.06324 (8)0.0259 (4)
O20.00504 (10)0.15557 (13)0.04012 (11)0.0519 (5)
H20.00040.10490.06460.062*
O30.12402 (10)0.15310 (11)0.02569 (9)0.0376 (4)
O40.27890 (9)0.16647 (9)0.09915 (8)0.0255 (4)
O50.26751 (11)0.00776 (11)0.14700 (10)0.0436 (5)
O60.25138 (9)0.21671 (9)0.24328 (8)0.0251 (4)
O70.14253 (10)0.14309 (11)0.14599 (9)0.0390 (4)
H70.18590.17660.14220.047*
O80.10799 (11)0.05515 (11)0.21930 (9)0.0413 (5)
O90.09765 (9)0.33020 (10)0.22086 (8)0.0277 (4)
O100.05528 (10)0.20992 (11)0.31786 (10)0.0433 (5)
C10.06426 (13)0.26069 (15)0.03285 (13)0.0301 (5)
H1A0.03200.30530.00600.036*
H1B0.04040.24320.06980.036*
C20.06648 (15)0.18467 (16)0.01386 (13)0.0332 (6)
C30.29886 (15)0.09065 (14)0.06610 (13)0.0319 (6)
H3A0.35290.07600.08610.038*
H3B0.29240.10150.01680.038*
C40.24805 (16)0.01748 (15)0.07583 (13)0.0370 (6)
H4A0.19390.03490.06200.044*
H4B0.25530.03060.04690.044*
C50.2264 (2)0.08277 (18)0.15801 (18)0.0576 (9)
H5A0.23840.09580.20690.086*
H5B0.24140.13020.13320.086*
H5C0.17150.07300.14140.086*
C60.21804 (14)0.14155 (15)0.26547 (12)0.0301 (5)
H6A0.19960.15470.30650.036*
H6B0.25720.09680.27760.036*
C70.15167 (14)0.11053 (15)0.20826 (12)0.0296 (5)
C80.03827 (14)0.34339 (16)0.25797 (14)0.0358 (6)
H8A0.00110.38230.23200.043*
H8B0.06090.36900.30310.043*
C90.00186 (15)0.25853 (18)0.26739 (14)0.0410 (7)
H9A0.04550.26780.28260.049*
H9B0.01140.22760.22350.049*
C100.02125 (17)0.13384 (18)0.33664 (16)0.0492 (8)
H10A0.05880.10370.37190.074*
H10B0.00470.09770.29640.074*
H10C0.02280.14870.35440.074*
C110.15442 (13)0.37274 (14)0.03355 (11)0.0223 (5)
C120.11685 (13)0.44731 (14)0.04680 (11)0.0244 (5)
C130.12670 (13)0.52218 (15)0.01092 (12)0.0262 (5)
H130.09880.57110.01670.031*
C140.17677 (13)0.52616 (14)0.03318 (12)0.0262 (5)
C150.21850 (13)0.45158 (14)0.03891 (12)0.0261 (5)
H150.25440.45340.06600.031*
C160.20903 (13)0.37468 (14)0.00608 (11)0.0236 (5)
C170.19029 (14)0.60923 (15)0.07041 (12)0.0284 (5)
C180.1972 (2)0.58943 (18)0.14440 (14)0.0492 (8)
H18A0.20050.64230.16850.074*
H18B0.15230.55770.16880.074*
H18C0.24320.55580.14220.074*
C190.26548 (15)0.64982 (16)0.02867 (14)0.0380 (6)
H19A0.30680.60840.02200.057*
H19B0.25900.66810.01580.057*
H19C0.27810.69860.05350.057*
C200.12502 (16)0.67481 (17)0.07499 (17)0.0477 (7)
H20A0.07660.65010.10000.072*
H20B0.13580.72530.09900.072*
H20C0.12170.69020.02890.072*
C210.26041 (13)0.29750 (14)0.00886 (12)0.0250 (5)
H21A0.28000.30080.05040.030*
H21B0.23000.24520.01150.030*
C220.32818 (13)0.29443 (14)0.05510 (11)0.0238 (5)
C230.33507 (13)0.23104 (14)0.10631 (11)0.0232 (5)
C240.39594 (13)0.23177 (14)0.16623 (11)0.0242 (5)
C250.45128 (13)0.29706 (14)0.17371 (12)0.0254 (5)
H250.49220.29780.21340.030*
C260.44767 (13)0.36092 (14)0.12421 (12)0.0250 (5)
C270.38567 (13)0.35799 (14)0.06540 (12)0.0249 (5)
H270.38230.40010.03150.030*
C280.50823 (14)0.43319 (15)0.13230 (13)0.0305 (5)
C290.56483 (17)0.43346 (19)0.20411 (15)0.0525 (8)
H29A0.60080.48020.20700.079*
H29B0.59290.38000.21130.079*
H29C0.53640.44030.23920.079*
C300.55474 (17)0.42130 (18)0.07746 (16)0.0478 (7)
H30A0.58180.36730.08490.072*
H30B0.59170.46730.08120.072*
H30C0.52000.42190.03190.072*
C310.46741 (17)0.52074 (16)0.12156 (15)0.0424 (7)
H31A0.50560.56560.12720.064*
H31B0.43720.52800.15530.064*
H31C0.43380.52350.07550.064*
C320.39989 (13)0.16848 (14)0.22558 (11)0.0257 (5)
H32A0.35900.12580.21230.031*
H32B0.44960.13900.23640.031*
C330.39010 (13)0.21808 (14)0.28834 (11)0.0236 (5)
C340.31696 (13)0.24513 (14)0.29337 (11)0.0236 (5)
C350.30700 (13)0.30302 (14)0.34429 (11)0.0242 (5)
C360.37340 (13)0.33096 (14)0.39223 (11)0.0247 (5)
H360.36790.36920.42680.030*
C370.44837 (13)0.30408 (14)0.39082 (12)0.0248 (5)
C380.45481 (13)0.24752 (14)0.33843 (11)0.0253 (5)
H380.50400.22850.33660.030*
C390.51932 (13)0.34047 (15)0.44373 (12)0.0293 (5)
C400.59507 (15)0.2969 (2)0.43802 (17)0.0536 (8)
H40A0.63770.31960.47320.080*
H40B0.60360.30790.39280.080*
H40C0.59120.23600.44450.080*
C410.52603 (16)0.43667 (16)0.42870 (14)0.0392 (6)
H41A0.47960.46570.43270.059*
H41B0.53270.44390.38240.059*
H41C0.57000.46050.46160.059*
C420.51012 (17)0.32842 (18)0.51796 (13)0.0433 (7)
H42A0.46410.35770.52280.065*
H42B0.55470.35190.55050.065*
H42C0.50580.26820.52710.065*
C430.22745 (13)0.33977 (14)0.34274 (11)0.0254 (5)
H43A0.22740.36360.38800.031*
H43B0.18870.29450.33230.031*
C440.20756 (13)0.40970 (14)0.28756 (11)0.0241 (5)
C450.14685 (13)0.40119 (14)0.22739 (11)0.0238 (5)
C460.13583 (13)0.46252 (13)0.17434 (11)0.0231 (5)
C470.18408 (13)0.53453 (14)0.18439 (12)0.0269 (5)
H470.17680.57570.14930.032*
C480.24271 (13)0.54758 (14)0.24474 (12)0.0265 (5)
C490.25313 (13)0.48331 (14)0.29502 (12)0.0274 (5)
H490.29240.49000.33550.033*
C500.29342 (15)0.62886 (15)0.25753 (14)0.0355 (6)
C510.2688 (2)0.6835 (2)0.3123 (2)0.0838 (13)
H51A0.27280.65000.35370.126*
H51B0.21590.70190.29460.126*
H51C0.30200.73290.32300.126*
C520.2884 (2)0.6791 (2)0.1906 (2)0.0871 (14)
H52A0.29860.64120.15560.131*
H52B0.32620.72460.19920.131*
H52C0.23730.70320.17470.131*
C530.37896 (16)0.60548 (19)0.28619 (16)0.0487 (7)
H53A0.38540.57650.33000.073*
H53B0.40980.65700.29260.073*
H53C0.39540.56830.25390.073*
C540.07565 (13)0.45028 (15)0.10551 (11)0.0255 (5)
H54A0.04730.39710.10650.031*
H54B0.03880.49750.09800.031*
O110.00220 (13)0.01632 (14)0.11406 (12)0.0593 (6)
H110.038 (2)0.009 (2)0.1493 (18)0.071*
C550.0693 (2)0.0368 (2)0.1036 (2)0.0707 (10)
H55A0.08140.04740.14750.106*
H55B0.05940.09050.08340.106*
H55C0.11240.00840.07280.106*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0260 (9)0.0243 (8)0.0268 (8)0.0040 (7)0.0055 (7)0.0014 (7)
O20.0339 (10)0.0530 (12)0.0657 (14)0.0123 (9)0.0063 (10)0.0214 (11)
O30.0370 (10)0.0364 (10)0.0394 (10)0.0057 (8)0.0093 (8)0.0079 (8)
O40.0276 (8)0.0230 (8)0.0266 (8)0.0019 (7)0.0081 (7)0.0031 (7)
O50.0542 (12)0.0321 (9)0.0421 (11)0.0054 (9)0.0073 (9)0.0096 (8)
O60.0244 (8)0.0265 (8)0.0229 (8)0.0049 (7)0.0028 (7)0.0012 (7)
O70.0398 (10)0.0434 (10)0.0294 (10)0.0158 (8)0.0001 (8)0.0060 (8)
O80.0451 (11)0.0431 (10)0.0340 (10)0.0213 (9)0.0065 (8)0.0013 (8)
O90.0269 (8)0.0282 (8)0.0292 (9)0.0066 (7)0.0090 (7)0.0007 (7)
O100.0364 (10)0.0413 (10)0.0503 (12)0.0089 (8)0.0070 (9)0.0153 (9)
C10.0250 (12)0.0299 (13)0.0351 (14)0.0056 (10)0.0065 (10)0.0021 (11)
C20.0309 (14)0.0352 (14)0.0320 (14)0.0071 (11)0.0052 (11)0.0008 (11)
C30.0440 (15)0.0239 (12)0.0299 (13)0.0015 (11)0.0130 (11)0.0049 (10)
C40.0470 (16)0.0254 (12)0.0364 (15)0.0037 (12)0.0063 (12)0.0045 (11)
C50.075 (2)0.0331 (15)0.072 (2)0.0061 (15)0.0303 (18)0.0100 (15)
C60.0312 (13)0.0292 (12)0.0289 (13)0.0071 (11)0.0053 (10)0.0033 (10)
C70.0310 (13)0.0280 (12)0.0301 (13)0.0041 (11)0.0081 (11)0.0000 (10)
C80.0264 (13)0.0413 (14)0.0418 (15)0.0003 (11)0.0127 (11)0.0076 (12)
C90.0279 (14)0.0503 (16)0.0435 (16)0.0066 (12)0.0061 (12)0.0124 (13)
C100.0459 (17)0.0445 (16)0.0595 (19)0.0122 (14)0.0175 (15)0.0169 (14)
C110.0226 (11)0.0232 (11)0.0197 (11)0.0007 (9)0.0027 (9)0.0027 (9)
C120.0214 (11)0.0270 (12)0.0232 (12)0.0029 (10)0.0025 (9)0.0002 (9)
C130.0247 (12)0.0256 (12)0.0271 (12)0.0023 (10)0.0038 (10)0.0002 (10)
C140.0242 (12)0.0283 (12)0.0243 (12)0.0027 (10)0.0022 (10)0.0016 (10)
C150.0244 (12)0.0325 (12)0.0218 (12)0.0004 (10)0.0063 (10)0.0017 (10)
C160.0228 (12)0.0250 (11)0.0219 (11)0.0001 (9)0.0034 (9)0.0009 (9)
C170.0288 (13)0.0282 (12)0.0276 (13)0.0021 (10)0.0056 (10)0.0055 (10)
C180.080 (2)0.0371 (15)0.0311 (14)0.0097 (15)0.0138 (15)0.0055 (12)
C190.0382 (15)0.0349 (14)0.0398 (15)0.0067 (12)0.0076 (12)0.0056 (12)
C200.0397 (15)0.0372 (15)0.067 (2)0.0027 (13)0.0155 (14)0.0235 (14)
C210.0270 (12)0.0269 (12)0.0229 (12)0.0004 (10)0.0095 (10)0.0024 (9)
C220.0235 (12)0.0256 (11)0.0243 (12)0.0050 (10)0.0095 (10)0.0020 (9)
C230.0217 (11)0.0233 (11)0.0265 (12)0.0010 (9)0.0095 (9)0.0038 (9)
C240.0281 (12)0.0221 (11)0.0248 (12)0.0040 (10)0.0108 (10)0.0009 (9)
C250.0231 (12)0.0304 (12)0.0231 (12)0.0010 (10)0.0065 (10)0.0020 (10)
C260.0245 (12)0.0254 (12)0.0262 (12)0.0002 (10)0.0080 (10)0.0038 (10)
C270.0279 (12)0.0233 (11)0.0251 (12)0.0015 (10)0.0097 (10)0.0010 (9)
C280.0296 (13)0.0274 (12)0.0352 (14)0.0039 (10)0.0094 (11)0.0004 (10)
C290.0514 (18)0.0467 (17)0.0508 (18)0.0216 (15)0.0036 (15)0.0027 (14)
C300.0418 (16)0.0451 (16)0.064 (2)0.0137 (13)0.0284 (15)0.0068 (15)
C310.0515 (17)0.0298 (13)0.0475 (17)0.0052 (13)0.0154 (14)0.0069 (12)
C320.0272 (12)0.0241 (11)0.0244 (12)0.0017 (10)0.0034 (10)0.0010 (10)
C330.0291 (12)0.0201 (11)0.0214 (12)0.0014 (10)0.0057 (10)0.0046 (9)
C340.0243 (12)0.0233 (11)0.0208 (11)0.0035 (10)0.0009 (9)0.0022 (9)
C350.0268 (12)0.0241 (11)0.0220 (12)0.0029 (10)0.0066 (10)0.0043 (9)
C360.0299 (12)0.0251 (11)0.0196 (11)0.0002 (10)0.0070 (10)0.0006 (9)
C370.0259 (12)0.0222 (11)0.0243 (12)0.0005 (9)0.0025 (10)0.0032 (9)
C380.0244 (12)0.0256 (12)0.0255 (12)0.0013 (10)0.0052 (10)0.0039 (10)
C390.0260 (12)0.0305 (12)0.0286 (13)0.0017 (10)0.0014 (10)0.0004 (10)
C400.0287 (15)0.0606 (19)0.061 (2)0.0088 (13)0.0095 (14)0.0209 (16)
C410.0420 (15)0.0356 (14)0.0386 (15)0.0128 (12)0.0074 (12)0.0012 (12)
C420.0485 (17)0.0483 (16)0.0259 (14)0.0142 (14)0.0044 (12)0.0048 (12)
C430.0269 (12)0.0294 (12)0.0204 (12)0.0017 (10)0.0067 (9)0.0003 (9)
C440.0246 (12)0.0254 (11)0.0241 (12)0.0005 (10)0.0095 (10)0.0009 (9)
C450.0235 (12)0.0236 (11)0.0261 (12)0.0010 (9)0.0096 (10)0.0014 (9)
C460.0248 (12)0.0229 (11)0.0232 (12)0.0034 (9)0.0088 (10)0.0015 (9)
C470.0323 (13)0.0236 (12)0.0258 (12)0.0031 (10)0.0095 (10)0.0025 (9)
C480.0291 (13)0.0226 (11)0.0285 (12)0.0002 (10)0.0087 (10)0.0012 (10)
C490.0255 (12)0.0289 (12)0.0264 (12)0.0006 (10)0.0035 (10)0.0037 (10)
C500.0379 (15)0.0272 (13)0.0393 (15)0.0074 (11)0.0056 (12)0.0024 (11)
C510.075 (2)0.0506 (19)0.139 (4)0.0208 (18)0.052 (2)0.054 (2)
C520.092 (3)0.064 (2)0.079 (3)0.049 (2)0.027 (2)0.0383 (19)
C530.0432 (17)0.0489 (17)0.0533 (18)0.0139 (14)0.0104 (14)0.0030 (14)
C540.0253 (12)0.0269 (12)0.0246 (12)0.0020 (10)0.0070 (10)0.0006 (10)
O110.0527 (14)0.0552 (13)0.0629 (14)0.0109 (11)0.0010 (11)0.0227 (11)
C550.064 (2)0.062 (2)0.075 (3)0.0007 (18)0.0038 (19)0.0126 (18)
Geometric parameters (Å, º) top
O1—C111.392 (3)C22—C271.398 (3)
O1—C11.430 (3)C23—C241.394 (3)
O2—C21.326 (3)C24—C251.394 (3)
O2—O112.634 (3)C24—C321.521 (3)
O3—C21.207 (3)C25—C261.386 (3)
O4—C231.397 (3)C26—C271.392 (3)
O4—C31.434 (3)C26—C281.535 (3)
O4—O72.820 (2)C28—C291.526 (4)
O5—C51.421 (3)C28—C301.529 (4)
O5—C41.422 (3)C28—C311.531 (3)
O6—C341.402 (2)C32—C331.509 (3)
O6—C61.427 (3)C33—C341.391 (3)
O7—C71.306 (3)C33—C381.397 (3)
O8—C71.214 (3)C34—C351.395 (3)
O9—C451.393 (3)C35—C361.388 (3)
O9—C81.440 (3)C35—C431.516 (3)
O10—C91.415 (3)C36—C371.401 (3)
O10—C101.418 (3)C37—C381.386 (3)
C1—C21.507 (3)C37—C391.534 (3)
C3—C41.493 (3)C39—C421.531 (3)
C6—C71.499 (3)C39—C401.534 (4)
C8—C91.500 (3)C39—C411.535 (3)
C11—C161.390 (3)C43—C441.520 (3)
C11—C121.394 (3)C44—C491.388 (3)
C12—C131.397 (3)C44—C451.402 (3)
C12—C541.520 (3)C45—C461.396 (3)
C13—C141.393 (3)C46—C471.393 (3)
C14—C151.395 (3)C46—C541.522 (3)
C14—C171.535 (3)C47—C481.393 (3)
C15—C161.390 (3)C48—C491.390 (3)
C16—C211.516 (3)C48—C501.535 (3)
C17—C191.522 (3)C50—C521.523 (4)
C17—C201.528 (3)C50—C511.524 (4)
C17—C181.532 (4)C50—C531.527 (4)
C21—C221.517 (3)O11—C551.421 (4)
C22—C231.398 (3)O11—O8i2.719 (3)
C11—O1—C1113.65 (16)C27—C26—C28120.0 (2)
C2—O2—O11108.97 (16)C26—C27—C22122.9 (2)
C23—O4—C3112.72 (17)C29—C28—C30108.5 (2)
C23—O4—O7135.05 (13)C29—C28—C31107.9 (2)
C3—O4—O7111.90 (13)C30—C28—C31109.2 (2)
C5—O5—C4111.7 (2)C29—C28—C26112.5 (2)
C34—O6—C6112.00 (16)C30—C28—C26108.9 (2)
C7—O7—O4116.37 (15)C31—C28—C26109.9 (2)
C45—O9—C8111.12 (17)C33—C32—C24108.30 (17)
C9—O10—C10112.09 (19)C34—C33—C38117.9 (2)
O1—C1—C2113.0 (2)C34—C33—C32120.83 (19)
O3—C2—O2124.0 (2)C38—C33—C32120.8 (2)
O3—C2—C1126.1 (2)C33—C34—C35122.2 (2)
O2—C2—C1109.9 (2)C33—C34—O6118.72 (19)
O4—C3—C4110.0 (2)C35—C34—O6118.9 (2)
O5—C4—C3109.4 (2)C36—C35—C34117.3 (2)
O6—C6—C7109.78 (18)C36—C35—C43121.7 (2)
O8—C7—O7120.6 (2)C34—C35—C43120.8 (2)
O8—C7—C6120.6 (2)C35—C36—C37122.9 (2)
O7—C7—C6118.8 (2)C38—C37—C36117.3 (2)
O9—C8—C9109.3 (2)C38—C37—C39122.7 (2)
O10—C9—C8108.9 (2)C36—C37—C39120.0 (2)
C16—C11—O1119.16 (19)C37—C38—C33122.3 (2)
C16—C11—C12121.4 (2)C42—C39—C40108.7 (2)
O1—C11—C12119.38 (19)C42—C39—C37110.3 (2)
C11—C12—C13118.1 (2)C40—C39—C37111.9 (2)
C11—C12—C54120.81 (19)C42—C39—C41109.7 (2)
C13—C12—C54120.6 (2)C40—C39—C41107.7 (2)
C14—C13—C12122.4 (2)C37—C39—C41108.45 (19)
C13—C14—C15116.6 (2)C35—C43—C44109.49 (18)
C13—C14—C17122.6 (2)C49—C44—C45118.3 (2)
C15—C14—C17120.7 (2)C49—C44—C43119.1 (2)
C16—C15—C14123.2 (2)C45—C44—C43122.5 (2)
C11—C16—C15117.7 (2)O9—C45—C46120.16 (19)
C11—C16—C21120.85 (19)O9—C45—C44119.08 (19)
C15—C16—C21121.3 (2)C46—C45—C44120.8 (2)
C19—C17—C20107.8 (2)C47—C46—C45118.3 (2)
C19—C17—C18109.7 (2)C47—C46—C54119.9 (2)
C20—C17—C18108.4 (2)C45—C46—C54121.74 (19)
C19—C17—C14107.90 (19)C48—C47—C46122.8 (2)
C20—C17—C14112.5 (2)C49—C48—C47116.7 (2)
C18—C17—C14110.5 (2)C49—C48—C50120.2 (2)
C16—C21—C22110.75 (18)C47—C48—C50123.0 (2)
C23—C22—C27117.5 (2)C44—C49—C48123.0 (2)
C23—C22—C21122.5 (2)C52—C50—C51111.7 (3)
C27—C22—C21119.9 (2)C52—C50—C53106.5 (3)
C24—C23—O4118.41 (19)C51—C50—C53107.5 (3)
C24—C23—C22121.5 (2)C52—C50—C48111.8 (2)
O4—C23—C22120.01 (19)C51—C50—C48108.4 (2)
C23—C24—C25118.3 (2)C53—C50—C48110.7 (2)
C23—C24—C32122.1 (2)C12—C54—C46109.03 (18)
C25—C24—C32119.4 (2)C55—O11—O2123.36 (19)
C26—C25—C24122.5 (2)C55—O11—O8i107.03 (18)
C25—C26—C27117.3 (2)O2—O11—O8i129.61 (11)
C25—C26—C28122.7 (2)
C23—O4—O7—C785.4 (2)C27—C26—C28—C29171.8 (2)
C3—O4—O7—C787.3 (2)C25—C26—C28—C30112.3 (3)
C11—O1—C1—C2105.5 (2)C27—C26—C28—C3068.0 (3)
O11—O2—C2—O33.1 (3)C25—C26—C28—C31128.1 (2)
O11—O2—C2—C1175.98 (16)C27—C26—C28—C3151.5 (3)
O1—C1—C2—O30.7 (4)C23—C24—C32—C33113.2 (2)
O1—C1—C2—O2179.8 (2)C25—C24—C32—C3361.7 (3)
C23—O4—C3—C4165.89 (19)C24—C32—C33—C3478.2 (3)
O7—O4—C3—C48.5 (2)C24—C32—C33—C3893.5 (2)
C5—O5—C4—C3174.1 (2)C38—C33—C34—C353.0 (3)
O4—C3—C4—O569.4 (3)C32—C33—C34—C35168.9 (2)
C34—O6—C6—C7176.16 (19)C38—C33—C34—O6179.56 (18)
O4—O7—C7—O8136.8 (2)C32—C33—C34—O67.6 (3)
O4—O7—C7—C642.0 (3)C6—O6—C34—C3394.2 (2)
O6—C6—C7—O8169.2 (2)C6—O6—C34—C3589.1 (2)
O6—C6—C7—O712.0 (3)C33—C34—C35—C362.3 (3)
C45—O9—C8—C9163.65 (19)O6—C34—C35—C36178.83 (19)
C10—O10—C9—C8171.9 (2)C33—C34—C35—C43172.2 (2)
O9—C8—C9—O1072.5 (3)O6—C34—C35—C434.3 (3)
C1—O1—C11—C16110.9 (2)C34—C35—C36—C370.5 (3)
C1—O1—C11—C1272.1 (2)C43—C35—C36—C37173.9 (2)
C16—C11—C12—C139.3 (3)C35—C36—C37—C380.4 (3)
O1—C11—C12—C13173.72 (19)C35—C36—C37—C39177.5 (2)
C16—C11—C12—C54162.5 (2)C36—C37—C38—C330.3 (3)
O1—C11—C12—C5414.5 (3)C39—C37—C38—C33176.7 (2)
C11—C12—C13—C144.8 (3)C34—C33—C38—C372.0 (3)
C54—C12—C13—C14166.9 (2)C32—C33—C38—C37169.9 (2)
C12—C13—C14—C151.3 (3)C38—C37—C39—C42129.5 (2)
C12—C13—C14—C17177.5 (2)C36—C37—C39—C4253.5 (3)
C13—C14—C15—C163.4 (3)C38—C37—C39—C408.4 (3)
C17—C14—C15—C16179.6 (2)C36—C37—C39—C40174.6 (2)
O1—C11—C16—C15175.68 (19)C38—C37—C39—C41110.3 (2)
C12—C11—C16—C157.3 (3)C36—C37—C39—C4166.7 (3)
O1—C11—C16—C218.7 (3)C36—C35—C43—C4497.2 (2)
C12—C11—C16—C21168.3 (2)C34—C35—C43—C4477.0 (2)
C14—C15—C16—C110.8 (3)C35—C43—C44—C4963.4 (3)
C14—C15—C16—C21174.8 (2)C35—C43—C44—C45113.6 (2)
C13—C14—C17—C1998.7 (3)C8—O9—C45—C4698.7 (2)
C15—C14—C17—C1977.3 (3)C8—O9—C45—C4481.7 (2)
C13—C14—C17—C2020.1 (3)C49—C44—C45—O9176.3 (2)
C15—C14—C17—C20163.9 (2)C43—C44—C45—O96.7 (3)
C13—C14—C17—C18141.4 (2)C49—C44—C45—C464.1 (3)
C15—C14—C17—C1842.6 (3)C43—C44—C45—C46172.9 (2)
C11—C16—C21—C2280.3 (3)O9—C45—C46—C47177.1 (2)
C15—C16—C21—C2295.1 (2)C44—C45—C46—C473.3 (3)
C16—C21—C22—C23111.3 (2)O9—C45—C46—C545.8 (3)
C16—C21—C22—C2766.9 (3)C44—C45—C46—C54173.7 (2)
C3—O4—C23—C2488.9 (2)C45—C46—C47—C480.3 (3)
O7—O4—C23—C2483.7 (2)C54—C46—C47—C48176.9 (2)
C3—O4—C23—C2293.0 (2)C46—C47—C48—C491.9 (3)
O7—O4—C23—C2294.4 (2)C46—C47—C48—C50177.0 (2)
C27—C22—C23—C241.3 (3)C45—C44—C49—C481.9 (3)
C21—C22—C23—C24177.0 (2)C43—C44—C49—C48175.2 (2)
C27—C22—C23—O4179.31 (19)C47—C48—C49—C441.0 (4)
C21—C22—C23—O41.0 (3)C50—C48—C49—C44177.8 (2)
O4—C23—C24—C25179.05 (19)C49—C48—C50—C52164.8 (3)
C22—C23—C24—C251.0 (3)C47—C48—C50—C5216.4 (4)
O4—C23—C24—C324.1 (3)C49—C48—C50—C5171.6 (3)
C22—C23—C24—C32173.9 (2)C47—C48—C50—C51107.2 (3)
C23—C24—C25—C260.3 (3)C49—C48—C50—C5346.1 (3)
C32—C24—C25—C26174.7 (2)C47—C48—C50—C53135.1 (2)
C24—C25—C26—C270.0 (3)C11—C12—C54—C4678.9 (3)
C24—C25—C26—C28179.7 (2)C13—C12—C54—C4692.7 (2)
C25—C26—C27—C220.3 (3)C47—C46—C54—C1258.9 (3)
C28—C26—C27—C22179.4 (2)C45—C46—C54—C12118.2 (2)
C23—C22—C27—C260.9 (3)C2—O2—O11—C5523.6 (3)
C21—C22—C27—C26177.4 (2)C2—O2—O11—O8i156.90 (17)
C25—C26—C28—C297.9 (3)
Symmetry code: (i) x, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O40.952.042.820 (2)138
O7—H7···O60.952.142.630 (2)111
O2—H2···O110.941.702.634 (3)176
O11—H11···O8i0.95 (3)1.77 (3)2.719 (3)176 (3)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formulaC54H72O10·CH4O
Mr913.16
Crystal system, space groupMonoclinic, P21/c
Temperature (K)127
a, b, c (Å)17.7426 (9), 15.5402 (6), 19.8147 (10)
β (°) 104.279 (2)
V3)5294.6 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.45 × 0.28 × 0.25
Data collection
DiffractometerNonius Kappa-CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
18139, 9972, 6410
Rint0.050
(sin θ/λ)max1)0.610
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.138, 1.01
No. of reflections9972
No. of parameters614
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.27, 0.23

Computer programs: Kappa-CCD Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O40.9472.0422.820 (2)138.2
O7—H7···O60.9472.1442.630 (2)110.5
O2—H2···O110.9391.6982.634 (3)175.5
O11—H11···O8i0.95 (3)1.77 (3)2.719 (3)176 (3)
Symmetry code: (i) x, y, z.
 

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