Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013329/na1482sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013329/na1482Isup2.hkl |
CCDC reference: 158253
p-tert-Butyltetrahomodioxacalix[4]arene was synthesized as previously reported (Dhawan & Gutsche, 1983) and recrystallized from chloroform/tetrahydrofuran (1:1).
4517 Friedel pairs have been measured. Hydroxyl and chloroform protons were found on the Fourier-difference map and introduced as riding atoms with a displacement parameter equal to 1.2 times that of the parent atom. All other hydrogen atoms were introduced at calculated positions as riding atoms with a displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. The tetrahydrofuran molecule bahaves badly on refinement and some restraints had to be applied to the displacement parameters. One of the C—C distances in this molecule is shorter than usual [1.425 (14) Å].
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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 1999) and PARST97 (Nardelli, 1995).
C46H60O6·CHCl3·C4H8O | Dx = 1.213 Mg m−3 |
Mr = 900.41 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 35687 reflections |
a = 9.2248 (5) Å | θ = 2.7–25.7° |
b = 17.6451 (15) Å | µ = 0.24 mm−1 |
c = 30.282 (3) Å | T = 100 K |
V = 4929.1 (7) Å3 | Parallelepipedic, colourless |
Z = 4 | 0.28 × 0.28 × 0.25 mm |
F(000) = 1928 |
Nonius Kappa-CCD diffractometer | 5464 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.084 |
Graphite monochromator | θmax = 25.7°, θmin = 2.7° |
Detector resolution: 18 pixels mm-1 | h = 0→10 |
ϕ scans | k = −21→21 |
35687 measured reflections | l = −36→36 |
9064 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.213 | w = 1/[σ2(Fo2) + (0.1216P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
9064 reflections | Δρmax = 0.71 e Å−3 |
562 parameters | Δρmin = −0.39 e Å−3 |
42 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 |
C46H60O6·CHCl3·C4H8O | V = 4929.1 (7) Å3 |
Mr = 900.41 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.2248 (5) Å | µ = 0.24 mm−1 |
b = 17.6451 (15) Å | T = 100 K |
c = 30.282 (3) Å | 0.28 × 0.28 × 0.25 mm |
Nonius Kappa-CCD diffractometer | 5464 reflections with I > 2σ(I) |
35687 measured reflections | Rint = 0.084 |
9064 independent reflections |
R[F2 > 2σ(F2)] = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.213 | Δρmax = 0.71 e Å−3 |
S = 0.96 | Δρmin = −0.39 e Å−3 |
9064 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
562 parameters | Absolute structure parameter: 0.00 |
42 restraints |
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 expanded by subsequent Fourier-difference synthesis. All non-hydrogen atoms have been refined anisotropically. The structure has been refined as corresponding to a racemic twin. 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.8511 (3) | 0.41297 (18) | 0.05789 (11) | 0.0224 (8) | |
H1 | 0.8944 | 0.4241 | 0.0344 | 0.027* | |
O2 | 0.9551 (3) | 0.5157 (2) | −0.00001 (11) | 0.0258 (8) | |
O3 | 0.7592 (4) | 0.4037 (2) | −0.03249 (12) | 0.0350 (9) | |
H3 | 0.7070 | 0.3578 | −0.0342 | 0.042* | |
O4 | 0.5418 (3) | 0.30084 (19) | −0.03874 (11) | 0.0233 (8) | |
H4 | 0.4826 | 0.2992 | −0.0093 | 0.028* | |
O5 | 0.3058 (3) | 0.30112 (19) | 0.01185 (11) | 0.0242 (8) | |
O6 | 0.5522 (3) | 0.38272 (19) | 0.04573 (10) | 0.0213 (7) | |
H6 | 0.6490 | 0.3939 | 0.0506 | 0.026* | |
C1 | 0.8370 (4) | 0.4743 (3) | 0.08699 (16) | 0.0195 (10) | |
C2 | 0.7533 (4) | 0.4645 (3) | 0.12435 (15) | 0.0179 (10) | |
C3 | 0.7346 (5) | 0.5263 (3) | 0.15212 (16) | 0.0217 (10) | |
H3A | 0.6772 | 0.5202 | 0.1771 | 0.026* | |
C4 | 0.7976 (5) | 0.5974 (3) | 0.14454 (16) | 0.0228 (11) | |
C5 | 0.8830 (5) | 0.6040 (3) | 0.10650 (16) | 0.0214 (10) | |
H5 | 0.9257 | 0.6505 | 0.1001 | 0.026* | |
C6 | 0.9060 (4) | 0.5433 (3) | 0.07784 (16) | 0.0197 (10) | |
C7 | 0.7738 (6) | 0.6632 (3) | 0.17627 (19) | 0.0316 (12) | |
C8 | 0.8539 (10) | 0.6492 (4) | 0.2188 (3) | 0.067 (2) | |
H8A | 0.8330 | 0.5990 | 0.2292 | 0.100* | |
H8B | 0.8236 | 0.6856 | 0.2405 | 0.100* | |
H8C | 0.9562 | 0.6542 | 0.2138 | 0.100* | |
C9 | 0.6100 (7) | 0.6699 (4) | 0.1870 (3) | 0.058 (2) | |
H9A | 0.5570 | 0.6793 | 0.1602 | 0.086* | |
H9B | 0.5948 | 0.7110 | 0.2072 | 0.086* | |
H9C | 0.5767 | 0.6235 | 0.2000 | 0.086* | |
C10 | 0.8140 (9) | 0.7389 (3) | 0.1562 (2) | 0.0534 (19) | |
H10A | 0.9170 | 0.7411 | 0.1518 | 0.080* | |
H10B | 0.7847 | 0.7790 | 0.1757 | 0.080* | |
H10C | 0.7659 | 0.7447 | 0.1283 | 0.080* | |
C11 | 1.0082 (5) | 0.5516 (3) | 0.03893 (15) | 0.0241 (11) | |
H11A | 1.0231 | 0.6050 | 0.0330 | 0.029* | |
H11B | 1.1013 | 0.5297 | 0.0466 | 0.029* | |
C12 | 0.8357 (6) | 0.5522 (3) | −0.01916 (18) | 0.0325 (12) | |
H12A | 0.8543 | 0.6062 | −0.0208 | 0.039* | |
H12B | 0.7508 | 0.5445 | −0.0008 | 0.039* | |
C13 | 0.8066 (5) | 0.5223 (3) | −0.06456 (19) | 0.0331 (13) | |
C14 | 0.7659 (5) | 0.4457 (3) | −0.06974 (18) | 0.0298 (12) | |
C15 | 0.7326 (4) | 0.4179 (3) | −0.11206 (17) | 0.0224 (10) | |
C16 | 0.7407 (5) | 0.4668 (3) | −0.14761 (17) | 0.0213 (10) | |
H16 | 0.7120 | 0.4492 | −0.1752 | 0.026* | |
C17 | 0.7899 (5) | 0.5413 (3) | −0.14414 (18) | 0.0270 (11) | |
C18 | 0.8173 (6) | 0.5681 (3) | −0.10158 (18) | 0.0341 (13) | |
H18 | 0.8437 | 0.6186 | −0.0979 | 0.041* | |
C19 | 0.7949 (5) | 0.5958 (3) | −0.18339 (17) | 0.0248 (11) | |
C20 | 0.6714 (6) | 0.6530 (4) | −0.1800 (2) | 0.0394 (14) | |
H20A | 0.6761 | 0.6875 | −0.2045 | 0.059* | |
H20B | 0.6800 | 0.6808 | −0.1529 | 0.059* | |
H20C | 0.5802 | 0.6267 | −0.1805 | 0.059* | |
C21 | 0.7839 (6) | 0.5554 (3) | −0.22760 (18) | 0.0362 (13) | |
H21A | 0.8601 | 0.5186 | −0.2299 | 0.054* | |
H21B | 0.7930 | 0.5917 | −0.2510 | 0.054* | |
H21C | 0.6917 | 0.5305 | −0.2297 | 0.054* | |
C22 | 0.9406 (6) | 0.6384 (4) | −0.1838 (2) | 0.0409 (15) | |
H22A | 1.0187 | 0.6026 | −0.1816 | 0.061* | |
H22B | 0.9444 | 0.6727 | −0.1592 | 0.061* | |
H22C | 0.9495 | 0.6664 | −0.2109 | 0.061* | |
C23 | 0.6772 (5) | 0.3363 (3) | −0.11966 (17) | 0.0219 (11) | |
H23A | 0.7044 | 0.3198 | −0.1491 | 0.026* | |
H23B | 0.7229 | 0.3025 | −0.0986 | 0.026* | |
C24 | 0.5149 (4) | 0.3311 (3) | −0.11476 (17) | 0.0193 (10) | |
C25 | 0.4507 (5) | 0.3134 (3) | −0.07492 (16) | 0.0192 (10) | |
C26 | 0.3010 (5) | 0.3069 (3) | −0.06974 (16) | 0.0217 (11) | |
C27 | 0.2140 (5) | 0.3194 (3) | −0.10703 (16) | 0.0212 (11) | |
H27 | 0.1138 | 0.3171 | −0.1039 | 0.025* | |
C28 | 0.2714 (5) | 0.3352 (3) | −0.14866 (16) | 0.0189 (10) | |
C29 | 0.4241 (5) | 0.3412 (3) | −0.15117 (16) | 0.0183 (10) | |
H29 | 0.4660 | 0.3524 | −0.1783 | 0.022* | |
C30 | 0.1784 (5) | 0.3469 (3) | −0.18981 (16) | 0.0208 (10) | |
C31 | 0.1912 (7) | 0.4284 (3) | −0.2056 (2) | 0.0431 (15) | |
H31A | 0.1353 | 0.4349 | −0.2320 | 0.065* | |
H31B | 0.2910 | 0.4399 | −0.2115 | 0.065* | |
H31C | 0.1552 | 0.4619 | −0.1831 | 0.065* | |
C32 | 0.0196 (5) | 0.3289 (4) | −0.1811 (2) | 0.0383 (14) | |
H32A | −0.0132 | 0.3570 | −0.1559 | 0.057* | |
H32B | 0.0090 | 0.2756 | −0.1756 | 0.057* | |
H32C | −0.0371 | 0.3428 | −0.2065 | 0.057* | |
C33 | 0.2310 (6) | 0.2940 (4) | −0.22643 (18) | 0.0367 (13) | |
H33A | 0.1795 | 0.3049 | −0.2532 | 0.055* | |
H33B | 0.2135 | 0.2424 | −0.2180 | 0.055* | |
H33C | 0.3329 | 0.3014 | −0.2311 | 0.055* | |
C34 | 0.2330 (5) | 0.2775 (3) | −0.02779 (16) | 0.0261 (11) | |
H34A | 0.1331 | 0.2945 | −0.0265 | 0.031* | |
H34B | 0.2320 | 0.2225 | −0.0288 | 0.031* | |
C35 | 0.2599 (5) | 0.3735 (3) | 0.02840 (16) | 0.0231 (11) | |
H35A | 0.1549 | 0.3769 | 0.0280 | 0.028* | |
H35B | 0.2987 | 0.4139 | 0.0101 | 0.028* | |
C36 | 0.3156 (4) | 0.3808 (3) | 0.07508 (16) | 0.0205 (10) | |
C37 | 0.4671 (5) | 0.3848 (3) | 0.08268 (16) | 0.0200 (10) | |
C38 | 0.5191 (4) | 0.3881 (3) | 0.12493 (16) | 0.0182 (10) | |
C39 | 0.4223 (5) | 0.3924 (3) | 0.16034 (17) | 0.0208 (10) | |
H39 | 0.4592 | 0.3965 | 0.1888 | 0.025* | |
C40 | 0.2698 (5) | 0.3907 (3) | 0.15439 (15) | 0.0195 (10) | |
C41 | 0.2207 (5) | 0.3855 (3) | 0.11068 (16) | 0.0225 (10) | |
H41 | 0.1214 | 0.3853 | 0.1053 | 0.027* | |
C42 | 0.1647 (5) | 0.4005 (3) | 0.19308 (16) | 0.0228 (11) | |
C43 | 0.1035 (5) | 0.4799 (3) | 0.1916 (2) | 0.0311 (13) | |
H43A | 0.0283 | 0.4848 | 0.2133 | 0.047* | |
H43B | 0.0643 | 0.4896 | 0.1628 | 0.047* | |
H43C | 0.1792 | 0.5157 | 0.1978 | 0.047* | |
C44 | 0.2381 (5) | 0.3865 (3) | 0.23702 (15) | 0.0253 (11) | |
H44A | 0.2814 | 0.3370 | 0.2370 | 0.038* | |
H44B | 0.1676 | 0.3895 | 0.2603 | 0.038* | |
H44C | 0.3118 | 0.4240 | 0.2417 | 0.038* | |
C45 | 0.0403 (5) | 0.3421 (3) | 0.18882 (19) | 0.0322 (12) | |
H45A | 0.0796 | 0.2917 | 0.1900 | 0.048* | |
H45B | −0.0087 | 0.3493 | 0.1612 | 0.048* | |
H45C | −0.0271 | 0.3490 | 0.2126 | 0.048* | |
C46 | 0.6821 (5) | 0.3889 (3) | 0.13465 (17) | 0.0212 (10) | |
H46A | 0.6972 | 0.3771 | 0.1656 | 0.025* | |
H46B | 0.7287 | 0.3496 | 0.1173 | 0.025* | |
C47 | 0.4073 (9) | 0.6656 (5) | 0.0445 (3) | 0.073 (2) | |
H47 | 0.3665 | 0.6632 | 0.0147 | 0.087* | |
Cl1 | 0.2803 (3) | 0.70978 (15) | 0.07854 (10) | 0.1005 (9) | |
Cl2 | 0.5685 (3) | 0.71738 (15) | 0.04176 (9) | 0.0934 (8) | |
Cl3 | 0.4431 (3) | 0.57232 (12) | 0.06175 (9) | 0.0862 (7) | |
O7 | 0.3201 (5) | 0.6469 (3) | −0.05420 (16) | 0.0573 (13) | |
C48 | 0.1989 (8) | 0.6047 (4) | −0.0688 (3) | 0.067 (2) | |
H48A | 0.1481 | 0.6328 | −0.0916 | 0.080* | |
H48B | 0.1326 | 0.5969 | −0.0443 | 0.080* | |
C49 | 0.2451 (12) | 0.5324 (7) | −0.0860 (4) | 0.109 (3) | |
H49A | 0.2164 | 0.4916 | −0.0664 | 0.131* | |
H49B | 0.2038 | 0.5234 | −0.1150 | 0.131* | |
C50 | 0.3989 (12) | 0.5381 (7) | −0.0884 (5) | 0.118 (3) | |
H50A | 0.4294 | 0.5323 | −0.1189 | 0.141* | |
H50B | 0.4422 | 0.4974 | −0.0714 | 0.141* | |
C51 | 0.4506 (10) | 0.6109 (6) | −0.0715 (4) | 0.091 (3) | |
H51A | 0.5220 | 0.6036 | −0.0484 | 0.110* | |
H51B | 0.4931 | 0.6411 | −0.0950 | 0.110* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0215 (15) | 0.0262 (18) | 0.0196 (19) | −0.0027 (13) | 0.0050 (13) | −0.0064 (15) |
O2 | 0.0301 (17) | 0.0293 (19) | 0.0182 (19) | −0.0059 (15) | −0.0014 (15) | −0.0016 (15) |
O3 | 0.0424 (19) | 0.033 (2) | 0.030 (2) | −0.0093 (16) | −0.0027 (17) | 0.0054 (17) |
O4 | 0.0239 (16) | 0.0267 (19) | 0.0192 (19) | 0.0036 (14) | −0.0009 (14) | −0.0009 (15) |
O5 | 0.0297 (17) | 0.0235 (18) | 0.0195 (19) | −0.0008 (14) | −0.0031 (14) | −0.0058 (15) |
O6 | 0.0208 (15) | 0.0293 (19) | 0.0139 (17) | −0.0055 (14) | 0.0002 (13) | −0.0005 (15) |
C1 | 0.015 (2) | 0.017 (2) | 0.026 (3) | −0.0002 (17) | −0.0071 (19) | −0.003 (2) |
C2 | 0.0132 (19) | 0.024 (3) | 0.017 (2) | −0.0007 (18) | −0.0046 (18) | 0.001 (2) |
C3 | 0.019 (2) | 0.024 (3) | 0.022 (3) | −0.0026 (19) | 0.0044 (19) | 0.001 (2) |
C4 | 0.028 (2) | 0.024 (3) | 0.017 (3) | 0.0006 (19) | −0.001 (2) | −0.004 (2) |
C5 | 0.027 (2) | 0.017 (2) | 0.020 (3) | −0.0090 (18) | −0.001 (2) | 0.001 (2) |
C6 | 0.017 (2) | 0.026 (3) | 0.017 (3) | −0.0030 (18) | 0.0003 (18) | −0.002 (2) |
C7 | 0.037 (3) | 0.025 (3) | 0.032 (3) | −0.002 (2) | 0.003 (2) | −0.002 (2) |
C8 | 0.100 (6) | 0.050 (4) | 0.050 (5) | 0.020 (4) | −0.036 (4) | −0.019 (4) |
C9 | 0.058 (4) | 0.041 (4) | 0.073 (5) | 0.001 (3) | 0.038 (4) | −0.015 (4) |
C10 | 0.091 (5) | 0.025 (3) | 0.044 (4) | −0.006 (3) | 0.022 (4) | −0.007 (3) |
C11 | 0.027 (2) | 0.033 (3) | 0.013 (3) | −0.010 (2) | 0.0002 (19) | −0.002 (2) |
C12 | 0.038 (3) | 0.033 (3) | 0.026 (3) | −0.003 (2) | −0.004 (2) | −0.006 (2) |
C13 | 0.031 (3) | 0.036 (3) | 0.032 (3) | −0.001 (2) | 0.000 (2) | −0.001 (3) |
C14 | 0.030 (3) | 0.032 (3) | 0.027 (3) | −0.003 (2) | 0.001 (2) | 0.002 (2) |
C15 | 0.017 (2) | 0.025 (3) | 0.025 (3) | −0.0045 (19) | −0.0021 (19) | 0.002 (2) |
C16 | 0.015 (2) | 0.025 (3) | 0.023 (3) | −0.0005 (19) | 0.0002 (19) | 0.000 (2) |
C17 | 0.028 (3) | 0.028 (3) | 0.025 (3) | −0.004 (2) | −0.006 (2) | 0.002 (2) |
C18 | 0.042 (3) | 0.034 (3) | 0.026 (3) | −0.007 (2) | −0.001 (2) | 0.011 (2) |
C19 | 0.028 (2) | 0.023 (3) | 0.023 (3) | 0.002 (2) | 0.001 (2) | 0.004 (2) |
C20 | 0.035 (3) | 0.052 (4) | 0.031 (3) | 0.016 (3) | −0.001 (3) | 0.008 (3) |
C21 | 0.053 (3) | 0.035 (3) | 0.020 (3) | 0.003 (3) | 0.002 (3) | 0.003 (2) |
C22 | 0.040 (3) | 0.049 (4) | 0.034 (4) | −0.011 (3) | −0.001 (3) | 0.008 (3) |
C23 | 0.022 (2) | 0.018 (2) | 0.026 (3) | −0.0032 (19) | 0.000 (2) | −0.002 (2) |
C24 | 0.021 (2) | 0.010 (2) | 0.027 (3) | −0.0019 (17) | −0.002 (2) | −0.001 (2) |
C25 | 0.023 (2) | 0.016 (2) | 0.018 (3) | 0.0026 (18) | −0.004 (2) | −0.0004 (19) |
C26 | 0.023 (2) | 0.023 (3) | 0.019 (3) | −0.0059 (19) | 0.001 (2) | 0.002 (2) |
C27 | 0.022 (2) | 0.022 (3) | 0.020 (3) | −0.0015 (18) | 0.0025 (19) | −0.004 (2) |
C28 | 0.022 (2) | 0.017 (2) | 0.018 (3) | −0.0029 (19) | −0.0029 (19) | −0.001 (2) |
C29 | 0.020 (2) | 0.019 (2) | 0.015 (3) | 0.0033 (18) | 0.0041 (18) | −0.002 (2) |
C30 | 0.018 (2) | 0.022 (3) | 0.022 (3) | 0.0009 (18) | 0.0019 (19) | 0.000 (2) |
C31 | 0.052 (3) | 0.033 (3) | 0.045 (4) | −0.004 (3) | −0.013 (3) | 0.006 (3) |
C32 | 0.029 (3) | 0.057 (4) | 0.029 (3) | −0.009 (2) | −0.006 (2) | 0.012 (3) |
C33 | 0.040 (3) | 0.047 (3) | 0.022 (3) | 0.006 (3) | −0.011 (2) | −0.008 (3) |
C34 | 0.027 (2) | 0.031 (3) | 0.020 (3) | −0.008 (2) | −0.003 (2) | −0.001 (2) |
C35 | 0.019 (2) | 0.031 (3) | 0.019 (3) | 0.004 (2) | −0.004 (2) | −0.006 (2) |
C36 | 0.017 (2) | 0.022 (3) | 0.022 (3) | 0.0018 (19) | −0.0039 (19) | −0.004 (2) |
C37 | 0.019 (2) | 0.018 (2) | 0.023 (3) | 0.0002 (19) | 0.0040 (19) | −0.003 (2) |
C38 | 0.017 (2) | 0.019 (3) | 0.018 (3) | −0.0014 (18) | −0.0019 (18) | 0.005 (2) |
C39 | 0.026 (2) | 0.016 (2) | 0.020 (3) | 0.0013 (19) | −0.006 (2) | 0.000 (2) |
C40 | 0.019 (2) | 0.019 (2) | 0.021 (3) | −0.0060 (18) | −0.0015 (18) | −0.002 (2) |
C41 | 0.020 (2) | 0.025 (3) | 0.023 (3) | −0.0010 (19) | −0.0008 (19) | 0.001 (2) |
C42 | 0.022 (2) | 0.024 (3) | 0.021 (3) | −0.0059 (19) | 0.0011 (19) | −0.006 (2) |
C43 | 0.022 (2) | 0.035 (3) | 0.036 (3) | 0.007 (2) | −0.002 (2) | −0.009 (3) |
C44 | 0.028 (2) | 0.031 (3) | 0.017 (3) | 0.003 (2) | 0.004 (2) | −0.003 (2) |
C45 | 0.028 (2) | 0.039 (3) | 0.030 (3) | −0.013 (2) | 0.006 (2) | −0.007 (3) |
C46 | 0.017 (2) | 0.022 (3) | 0.024 (3) | −0.0003 (19) | −0.0051 (19) | 0.001 (2) |
C47 | 0.082 (5) | 0.053 (5) | 0.082 (6) | 0.002 (4) | −0.030 (5) | −0.002 (4) |
Cl1 | 0.0882 (15) | 0.0866 (16) | 0.127 (2) | −0.0010 (13) | 0.0001 (14) | −0.0468 (16) |
Cl2 | 0.0961 (16) | 0.0803 (16) | 0.1037 (19) | −0.0264 (13) | −0.0120 (14) | 0.0019 (14) |
Cl3 | 0.0915 (14) | 0.0536 (12) | 0.113 (2) | −0.0001 (10) | −0.0220 (14) | 0.0112 (12) |
O7 | 0.041 (2) | 0.067 (3) | 0.064 (3) | 0.006 (2) | −0.002 (2) | −0.013 (3) |
C48 | 0.065 (3) | 0.063 (3) | 0.073 (4) | −0.007 (3) | 0.007 (3) | −0.005 (3) |
C49 | 0.108 (4) | 0.106 (4) | 0.114 (4) | 0.007 (4) | −0.004 (4) | −0.014 (4) |
C50 | 0.113 (4) | 0.115 (4) | 0.125 (5) | 0.011 (4) | 0.020 (4) | −0.009 (4) |
C51 | 0.077 (4) | 0.106 (4) | 0.091 (4) | 0.003 (4) | 0.008 (3) | 0.007 (4) |
O1—C1 | 1.402 (6) | C23—C24 | 1.507 (6) |
O2—C12 | 1.401 (6) | C24—C25 | 1.380 (7) |
O2—C11 | 1.425 (6) | C24—C29 | 1.396 (7) |
O3—C14 | 1.352 (6) | C25—C26 | 1.394 (6) |
O4—C25 | 1.398 (6) | C26—C27 | 1.403 (7) |
O5—C35 | 1.436 (6) | C26—C34 | 1.509 (7) |
O5—C34 | 1.438 (6) | C27—C28 | 1.396 (7) |
O6—C37 | 1.367 (6) | C28—C29 | 1.415 (6) |
C1—C2 | 1.381 (6) | C28—C30 | 1.527 (7) |
C1—C6 | 1.402 (7) | C30—C31 | 1.519 (8) |
C2—C3 | 1.387 (7) | C30—C33 | 1.529 (7) |
C2—C46 | 1.519 (7) | C30—C32 | 1.521 (7) |
C3—C4 | 1.401 (7) | C35—C36 | 1.510 (7) |
C4—C5 | 1.401 (7) | C36—C41 | 1.392 (7) |
C4—C7 | 1.523 (7) | C36—C37 | 1.418 (6) |
C5—C6 | 1.395 (7) | C37—C38 | 1.367 (7) |
C6—C11 | 1.516 (6) | C38—C39 | 1.397 (7) |
C7—C8 | 1.505 (9) | C38—C46 | 1.532 (6) |
C7—C10 | 1.515 (8) | C39—C40 | 1.418 (6) |
C7—C9 | 1.550 (8) | C40—C41 | 1.402 (7) |
C12—C13 | 1.497 (8) | C40—C42 | 1.531 (7) |
C13—C18 | 1.386 (8) | C42—C43 | 1.511 (7) |
C13—C14 | 1.410 (8) | C42—C44 | 1.513 (7) |
C14—C15 | 1.407 (7) | C42—C45 | 1.547 (7) |
C15—C16 | 1.382 (7) | C47—Cl1 | 1.744 (9) |
C15—C23 | 1.545 (7) | C47—Cl2 | 1.748 (9) |
C16—C17 | 1.394 (7) | C47—Cl3 | 1.758 (8) |
C17—C18 | 1.396 (8) | O7—C48 | 1.413 (9) |
C17—C19 | 1.529 (7) | O7—C51 | 1.458 (10) |
C19—C21 | 1.519 (7) | C48—C49 | 1.442 (14) |
C19—C20 | 1.526 (7) | C49—C50 | 1.425 (14) |
C19—C22 | 1.540 (7) | C50—C51 | 1.462 (16) |
C12—O2—C11 | 114.2 (4) | C24—C25—C26 | 122.8 (4) |
C35—O5—C34 | 114.3 (3) | C24—C25—O4 | 117.6 (4) |
C2—C1—C6 | 121.7 (4) | C26—C25—O4 | 119.6 (4) |
C2—C1—O1 | 118.0 (4) | C25—C26—C27 | 117.6 (4) |
C6—C1—O1 | 120.3 (4) | C25—C26—C34 | 122.3 (4) |
C1—C2—C3 | 117.9 (4) | C27—C26—C34 | 119.6 (4) |
C1—C2—C46 | 121.3 (4) | C28—C27—C26 | 122.8 (4) |
C3—C2—C46 | 120.8 (4) | C27—C28—C29 | 116.2 (4) |
C2—C3—C4 | 123.5 (4) | C27—C28—C30 | 123.5 (4) |
C3—C4—C5 | 116.3 (4) | C29—C28—C30 | 120.4 (4) |
C3—C4—C7 | 121.3 (4) | C24—C29—C28 | 123.0 (4) |
C5—C4—C7 | 122.4 (4) | C31—C30—C33 | 109.0 (5) |
C6—C5—C4 | 122.2 (4) | C31—C30—C32 | 109.1 (4) |
C5—C6—C1 | 118.3 (4) | C33—C30—C32 | 107.6 (4) |
C5—C6—C11 | 120.3 (4) | C31—C30—C28 | 109.9 (4) |
C1—C6—C11 | 121.3 (4) | C33—C30—C28 | 109.3 (4) |
C8—C7—C10 | 111.6 (5) | C32—C30—C28 | 111.8 (4) |
C8—C7—C4 | 110.1 (5) | O5—C34—C26 | 114.1 (4) |
C10—C7—C4 | 112.6 (5) | O5—C35—C36 | 107.6 (4) |
C8—C7—C9 | 108.2 (6) | C41—C36—C37 | 119.4 (4) |
C10—C7—C9 | 104.8 (5) | C41—C36—C35 | 121.1 (4) |
C4—C7—C9 | 109.3 (5) | C37—C36—C35 | 119.5 (4) |
O2—C11—C6 | 112.7 (4) | C38—C37—O6 | 124.4 (4) |
O2—C12—C13 | 111.0 (4) | C38—C37—C36 | 120.0 (4) |
C18—C13—C14 | 119.2 (5) | O6—C37—C36 | 115.6 (4) |
C18—C13—C12 | 121.6 (5) | C37—C38—C39 | 119.7 (4) |
C14—C13—C12 | 119.2 (5) | C37—C38—C46 | 121.6 (4) |
O3—C14—C15 | 123.9 (5) | C39—C38—C46 | 118.6 (4) |
O3—C14—C13 | 116.4 (5) | C38—C39—C40 | 122.3 (5) |
C15—C14—C13 | 119.6 (5) | C41—C40—C39 | 116.2 (4) |
C16—C15—C14 | 118.6 (4) | C41—C40—C42 | 121.6 (4) |
C16—C15—C23 | 118.9 (4) | C39—C40—C42 | 121.9 (4) |
C14—C15—C23 | 122.3 (4) | C40—C41—C36 | 122.1 (4) |
C15—C16—C17 | 123.2 (5) | C43—C42—C44 | 110.1 (4) |
C16—C17—C18 | 116.6 (5) | C43—C42—C40 | 108.6 (4) |
C16—C17—C19 | 122.9 (5) | C44—C42—C40 | 111.8 (4) |
C18—C17—C19 | 119.9 (5) | C43—C42—C45 | 109.8 (4) |
C13—C18—C17 | 122.4 (5) | C44—C42—C45 | 107.2 (4) |
C17—C19—C21 | 112.9 (4) | C40—C42—C45 | 109.3 (4) |
C17—C19—C20 | 109.9 (4) | C2—C46—C38 | 113.2 (4) |
C21—C19—C20 | 108.6 (4) | Cl1—C47—Cl2 | 111.5 (5) |
C17—C19—C22 | 109.9 (4) | Cl1—C47—Cl3 | 111.7 (5) |
C21—C19—C22 | 106.2 (4) | Cl2—C47—Cl3 | 110.1 (4) |
C20—C19—C22 | 109.2 (4) | C48—O7—C51 | 108.2 (6) |
C24—C23—C15 | 111.7 (4) | O7—C48—C49 | 110.1 (7) |
C25—C24—C29 | 117.5 (4) | C50—C49—C48 | 104.5 (10) |
C25—C24—C23 | 121.8 (4) | C49—C50—C51 | 111.6 (10) |
C29—C24—C23 | 120.7 (4) | O7—C51—C50 | 103.8 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.84 | 2.00 | 2.699 (8) | 140 |
O1—H1···O3 | 0.84 | 2.41 | 2.870 (8) | 116 |
O3—H3···O4 | 0.94 | 1.83 | 2.712 (8) | 154 |
O4—H4···O5 | 1.05 | 1.75 | 2.662 (8) | 143 |
O4—H4···O6 | 1.05 | 2.32 | 2.939 (8) | 117 |
O6—H6···O1 | 0.93 | 1.91 | 2.833 (8) | 177 |
C47—H47···O7 | 0.98 | 2.15 | 3.113 (10) | 168 |
Experimental details
Crystal data | |
Chemical formula | C46H60O6·CHCl3·C4H8O |
Mr | 900.41 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 9.2248 (5), 17.6451 (15), 30.282 (3) |
V (Å3) | 4929.1 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.28 × 0.28 × 0.25 |
Data collection | |
Diffractometer | Nonius Kappa-CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 35687, 9064, 5464 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.078, 0.213, 0.96 |
No. of reflections | 9064 |
No. of parameters | 562 |
No. of restraints | 42 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.71, −0.39 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | 0.00 |
Computer programs: Kappa-CCD Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1999) and PARST97 (Nardelli, 1995).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.84 | 2.00 | 2.699 (8) | 140 |
O1—H1···O3 | 0.84 | 2.41 | 2.870 (8) | 116 |
O3—H3···O4 | 0.94 | 1.83 | 2.712 (8) | 154 |
O4—H4···O5 | 1.05 | 1.75 | 2.662 (8) | 143 |
O4—H4···O6 | 1.05 | 2.32 | 2.939 (8) | 117 |
O6—H6···O1 | 0.93 | 1.91 | 2.833 (8) | 177 |
C47—H47···O7 | 0.98 | 2.15 | 3.113 (10) | 168 |
We have recently reported the first crystal structures of p-tert-butyltetrahomodioxacalix[4]arene as well as of its uranyl ion complex (Thuéry et al., 2000). Two forms presenting slightly different conformations have been found for the uncomplexed ligand, associated with some differences in the ether bridge conformations and intramolecular hydrogen-bond pattern. In each case, two solvent molecules (acetonitrile or pyridine) are included in the calixarene cavity. \sch
The main features of these structures are present in the case of the new solvate, (I), but the conformation is slightly different from the previous ones. The asymmetric unit in 1 is composed of one calixarene and two different solvent molecules. The calixarene symmetry was higher in one of the cases previously reported, in which the molecule was located around a binary axis, (II). If the plane defined by the four phenolic oxygen atoms is taken as a reference (highest deviation #from mean plane 0.324 (3) Å), the dihedral #angles made with it by the four phenyl rings are 124.5 (1), 126.4 (1), #157.5 (2) and 159.6 (1)° in 1, i.e. they span a wider range than those in the #more symmetrical and regular form 2 previously described #(132.8 (2)–141.2 (2)°). However, this from mean plane 0.459 (4) Å), the dihedral angles made with it by the four phenyl rings are 132.4 (1), 125.7 (1), 148.2 (2) and 156.2 (1)° in (I), i.e. they span a wider range than those in the more symmetrical and regular form (II) previously described [132.8 (2)–141.2 (2)°]. However, this range was even larger in the second form previously described (3) [109.4 (1)–157.3 (2)°]. The intramolecular hydrogen-bond pattern is different in the two previous forms: in 2, two phenolic units give bifurcated hydrogen bonds with the other phenolic units and the ether groups whereas in (III), one of those bifurcated bonds is replaced by a simple one (with the ether group). In (I), both hydrogen bonds are bifurcated, the phenol···phenol ones being seemingly somewhat less strong than in (II). The conformation around the ether bridges is identical to that in (II), the slight geometrical differences between those two compounds being possibly connected to the difference in the solvents included. By contrast with the parent calixarenes, in which the hydrogen-bond pattern is rather well defined and contributes to the rigidity of the molecule, the presence of the ether groups in oxacalixarenes makes this pattern more variable and the molecule more flexible.
The inclusion of two chemically different solvent molecules in a calixarene cavity is a somewhat uncommon feature, at least for small calixarenes [in both compounds (II) and (III), two identical molecules were included, acetonitrile in (II), pyridine in (III)]. It has been suggested that the ability of calixarenes to held two different species relatively close one to the other was indicative of their potential as 'enzyme mimics' (Asfari et al., 1991). The location of the choroform hydrogen atom is indicative of a possible hydrogen bond with the oxygen atom of tetrahydrofuran. Feeble interactions are thus present between the three species in this complex.