Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031996/hb2469sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031996/hb2469Isup2.hkl |
CCDC reference: 610039
Key indicators
- Single-crystal X-ray study
- T = 297 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.058
- wR factor = 0.153
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C22 PLAT420_ALERT_2_B D-H Without Acceptor O3 - H3 ... ?
Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.131 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.13 PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 46 Perc. PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.22 Ratio PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT301_ALERT_3_C Main Residue Disorder ......................... 10.00 Perc.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 69
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title compound was synthesized according to the literature method of Gutsche & Lin (1986) and colourless plates of (I) were recrystallized from toluene.
The H atoms were placed at calculated positions (O—H = 0.82 Å, C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2eq(C) or 1.5Ueq(O, methyl C).
The disordered tetra-tert-butyl moiety [site-occupancy factors of 0.753 (9) for C44A/C88A/C99A and 0.247 (9) for C44B/C88B/C99B] was refined anisotropically, with constraints and restraints imposed on the anisotropic displacement parameters of C atoms.
For the past 20 years the calixarenes, cavity-shaped macrocycles, have attracted much attention mainly in supramolecular and analytical chemistry, because they can form typical host–guest complexes with many neutral molecules and ions, like cyclodextrins and crown ethers (Gutsche & Alam, 1988; Gutsche, 1989). Owing to their nonplanar structure, calix[4]arenes can exist in one of the four conformations, and has been designated as cone, partial cone, 1,2-alternate, and 1,3-alternate [Andreetti et al., 1991; Casnati et al., 1995; Kim et al., 1999; Kim et al., 2000). By placing substituents at OH groups larger than methyl, conformation can be locked. Very often cone and partial cone conformes were synthesized by the alkylation (Iwamoto et al., 1991) and acylation (Gutsche & Lin, 1986) reaction at lover rim of calix[4]arene. But 1,2-alternate and 1,3-alternate conformers were observed only under certain reaction conditions.
As part of our work on substituted calix[4]arenes, we report herein the crystal structure of the title compound, (I), adopting a 1,3-alternate conformation. The two phenyl groups, A and D, lie above and the other two phenyl groups, B and C, below the least-squares plane defined by the four bridging methylene group, as illustrated in Fig. 1. The complete molecule is generated by 2-fold rotation symmetry. Bond angles involving the bridging methylene groups, i.e, C5—C7—C8 [116.2 (2)°] and C3—C18—C19 [116.4 (2)°], are significantly larger than the tetrahedral angle due to repulsion among the four phenyl groups. The dihedral angles of two pairs of facing rings, namely A and D, to which the OH group is bonded, and B and C, to which the acryloiloxy group is bonded, are 35.34 (10) and 20.01 (11)° respectively, so that rings A and D are splayed out upwards, and C and B are splayed out downwards from the central axis. Dihedral angles of adjacent phenyl rings in the calix[4]arene range from 85.13 (7) to 88.82 (7)°.
In the extended structure, there are no hydrogen bonding interactions and van der Waals interactions stabilize the extended structure (Fig. 2).
For related literature, see: Andreetti et al. (1991); Casnati et al. (1995); Gutsche (1989); Gutsche & Alam (1988); Gutsche & Lin (1986); Iwamoto et al. (1991); Kim et al. (1999, 2000).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C50H60O6 | F(000) = 1632 |
Mr = 756.98 | Dx = 1.158 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 2487 reflections |
a = 15.8896 (11) Å | θ = 2.0–28.1° |
b = 26.482 (2) Å | µ = 0.07 mm−1 |
c = 10.3522 (7) Å | T = 297 K |
β = 95.047 (6)° | Plate, colorless |
V = 4339.2 (5) Å3 | 0.41 × 0.24 × 0.09 mm |
Z = 4 |
Stoe IPDS2 diffractometer | 4277 independent reflections |
Radiation source: fine-focus sealed tube | 1985 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.131 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.4° |
ω scans | h = −19→19 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −32→32 |
Tmin = 0.940, Tmax = 0.983 | l = −12→12 |
28360 measured 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)] = 0.058 | H-atom parameters constrained |
wR(F2) = 0.153 | w = 1/[σ2(Fo2) + (0.0732P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.89 | (Δ/σ)max < 0.001 |
4277 reflections | Δρmax = 0.28 e Å−3 |
291 parameters | Δρmin = −0.25 e Å−3 |
69 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (3) |
C50H60O6 | V = 4339.2 (5) Å3 |
Mr = 756.98 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.8896 (11) Å | µ = 0.07 mm−1 |
b = 26.482 (2) Å | T = 297 K |
c = 10.3522 (7) Å | 0.41 × 0.24 × 0.09 mm |
β = 95.047 (6)° |
Stoe IPDS2 diffractometer | 4277 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 1985 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.983 | Rint = 0.131 |
28360 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 69 restraints |
wR(F2) = 0.153 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.28 e Å−3 |
4277 reflections | Δρmin = −0.25 e Å−3 |
291 parameters |
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. 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 | Occ. (<1) | |
C1 | 0.39759 (18) | 0.14689 (10) | 0.4886 (3) | 0.0489 (7) | |
C2 | 0.33804 (18) | 0.17650 (10) | 0.4175 (3) | 0.0516 (7) | |
H2 | 0.2892 | 0.1612 | 0.3802 | 0.062* | |
C3 | 0.34844 (17) | 0.22828 (10) | 0.3998 (3) | 0.0502 (7) | |
C4 | 0.42153 (18) | 0.24978 (10) | 0.4597 (2) | 0.0488 (7) | |
C5 | 0.48335 (17) | 0.22247 (10) | 0.5324 (2) | 0.0484 (7) | |
C6 | 0.46870 (18) | 0.17095 (11) | 0.5453 (3) | 0.0511 (7) | |
H6 | 0.5087 | 0.1518 | 0.5945 | 0.061* | |
C7 | 0.56389 (18) | 0.24571 (11) | 0.5930 (3) | 0.0556 (7) | |
H7A | 0.5994 | 0.2189 | 0.6311 | 0.067* | |
H7B | 0.5499 | 0.2676 | 0.6630 | 0.067* | |
C8 | 0.61498 (17) | 0.27597 (10) | 0.5029 (2) | 0.0477 (7) | |
C9 | 0.63760 (17) | 0.32534 (10) | 0.5299 (3) | 0.0522 (7) | |
H9 | 0.6215 | 0.3399 | 0.6057 | 0.063* | |
C10 | 0.68349 (18) | 0.35436 (10) | 0.4487 (3) | 0.0522 (7) | |
C11 | 0.7106 (2) | 0.40896 (11) | 0.4792 (3) | 0.0611 (8) | |
C12 | 0.8071 (2) | 0.41237 (13) | 0.4860 (4) | 0.0823 (11) | |
H12A | 0.8245 | 0.4463 | 0.5076 | 0.123* | |
H12B | 0.8259 | 0.4034 | 0.4034 | 0.123* | |
H12C | 0.8313 | 0.3896 | 0.5512 | 0.123* | |
C13 | 0.6815 (3) | 0.42761 (13) | 0.6066 (4) | 0.0915 (12) | |
H13A | 0.6209 | 0.4265 | 0.6025 | 0.137* | |
H13B | 0.7004 | 0.4617 | 0.6218 | 0.137* | |
H13C | 0.7047 | 0.4064 | 0.6760 | 0.137* | |
C14 | 0.6726 (2) | 0.44401 (12) | 0.3718 (4) | 0.0833 (11) | |
H14A | 0.6121 | 0.4433 | 0.3700 | 0.125* | |
H14B | 0.6894 | 0.4328 | 0.2897 | 0.125* | |
H14C | 0.6924 | 0.4778 | 0.3884 | 0.125* | |
C15 | 0.41891 (19) | 0.33598 (11) | 0.5224 (3) | 0.0613 (8) | |
C16 | 0.4375 (2) | 0.38666 (13) | 0.4723 (5) | 0.0894 (12) | |
H16 | 0.4549 | 0.3896 | 0.3891 | 0.107* | |
C17 | 0.4307 (3) | 0.4257 (2) | 0.5384 (7) | 0.153 (2) | |
H17A | 0.4134 | 0.4234 | 0.6218 | 0.183* | |
H17B | 0.4429 | 0.4571 | 0.5043 | 0.183* | |
C18 | 0.28391 (17) | 0.25805 (11) | 0.3157 (3) | 0.0549 (7) | |
H18A | 0.2628 | 0.2849 | 0.3679 | 0.066* | |
H18B | 0.2367 | 0.2359 | 0.2900 | 0.066* | |
C19 | 0.31394 (16) | 0.28140 (10) | 0.1945 (2) | 0.0477 (7) | |
C20 | 0.35920 (17) | 0.25403 (10) | 0.1088 (3) | 0.0475 (6) | |
C21 | 0.29447 (17) | 0.33092 (10) | 0.1629 (3) | 0.0509 (7) | |
H21 | 0.2648 | 0.3496 | 0.2200 | 0.061* | |
C22 | 0.38507 (18) | 0.08963 (11) | 0.4972 (3) | 0.0563 (7) | |
O1 | 0.43527 (12) | 0.30121 (7) | 0.43395 (18) | 0.0581 (5) | |
O2 | 0.39125 (18) | 0.32601 (9) | 0.6231 (3) | 0.0931 (8) | |
O3 | 0.37741 (13) | 0.20369 (7) | 0.1318 (2) | 0.0658 (6) | |
H3 | 0.4029 | 0.1924 | 0.0726 | 0.099* | |
C88A | 0.2920 (3) | 0.07769 (17) | 0.5133 (7) | 0.088 (2) | 0.753 (9) |
H88A | 0.2857 | 0.0421 | 0.5275 | 0.133* | 0.753 (9) |
H88B | 0.2579 | 0.0875 | 0.4362 | 0.133* | 0.753 (9) |
H88C | 0.2743 | 0.0960 | 0.5862 | 0.133* | 0.753 (9) |
C99A | 0.4087 (6) | 0.0663 (2) | 0.3724 (6) | 0.101 (3) | 0.753 (9) |
H99A | 0.4678 | 0.0715 | 0.3644 | 0.152* | 0.753 (9) |
H99B | 0.3763 | 0.0818 | 0.3004 | 0.152* | 0.753 (9) |
H99C | 0.3969 | 0.0308 | 0.3729 | 0.152* | 0.753 (9) |
C44A | 0.4365 (4) | 0.06675 (19) | 0.6111 (6) | 0.099 (3) | 0.753 (9) |
H44A | 0.4234 | 0.0315 | 0.6167 | 0.148* | 0.753 (9) |
H44B | 0.4235 | 0.0834 | 0.6893 | 0.148* | 0.753 (9) |
H44C | 0.4955 | 0.0707 | 0.6003 | 0.148* | 0.753 (9) |
C44B | 0.4719 (9) | 0.0619 (5) | 0.505 (2) | 0.095 (7) | 0.247 (9) |
H44D | 0.5050 | 0.0718 | 0.5832 | 0.142* | 0.247 (9) |
H44E | 0.5014 | 0.0708 | 0.4314 | 0.142* | 0.247 (9) |
H44F | 0.4628 | 0.0261 | 0.5061 | 0.142* | 0.247 (9) |
C88B | 0.3461 (16) | 0.0783 (6) | 0.6233 (19) | 0.105 (8) | 0.247 (9) |
H88D | 0.3407 | 0.0424 | 0.6332 | 0.157* | 0.247 (9) |
H88E | 0.2913 | 0.0937 | 0.6213 | 0.157* | 0.247 (9) |
H88F | 0.3818 | 0.0916 | 0.6950 | 0.157* | 0.247 (9) |
C99B | 0.3324 (15) | 0.0678 (6) | 0.3805 (18) | 0.102 (7) | 0.247 (9) |
H99D | 0.3377 | 0.0317 | 0.3809 | 0.153* | 0.247 (9) |
H99E | 0.3522 | 0.0810 | 0.3023 | 0.153* | 0.247 (9) |
H99F | 0.2743 | 0.0769 | 0.3846 | 0.153* | 0.247 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0487 (16) | 0.0494 (17) | 0.0488 (15) | −0.0049 (13) | 0.0054 (13) | 0.0044 (13) |
C2 | 0.0460 (16) | 0.0515 (17) | 0.0573 (17) | −0.0068 (13) | 0.0054 (14) | 0.0032 (13) |
C3 | 0.0496 (16) | 0.0519 (17) | 0.0507 (16) | −0.0022 (13) | 0.0127 (14) | 0.0065 (13) |
C4 | 0.0568 (17) | 0.0441 (16) | 0.0476 (15) | −0.0075 (13) | 0.0160 (14) | 0.0049 (13) |
C5 | 0.0516 (17) | 0.0543 (18) | 0.0401 (14) | −0.0081 (13) | 0.0078 (13) | 0.0046 (13) |
C6 | 0.0524 (17) | 0.0537 (18) | 0.0468 (15) | −0.0035 (13) | 0.0011 (14) | 0.0086 (13) |
C7 | 0.0596 (18) | 0.0583 (18) | 0.0482 (16) | −0.0138 (15) | 0.0006 (14) | 0.0008 (13) |
C8 | 0.0477 (16) | 0.0484 (17) | 0.0461 (15) | −0.0067 (13) | −0.0016 (13) | 0.0013 (13) |
C9 | 0.0520 (17) | 0.0531 (18) | 0.0508 (16) | −0.0078 (13) | 0.0014 (14) | −0.0068 (13) |
C10 | 0.0538 (17) | 0.0466 (16) | 0.0563 (17) | −0.0097 (13) | 0.0051 (14) | −0.0070 (13) |
C11 | 0.070 (2) | 0.0463 (17) | 0.0679 (19) | −0.0130 (14) | 0.0108 (17) | −0.0066 (14) |
C12 | 0.076 (2) | 0.057 (2) | 0.113 (3) | −0.0241 (17) | 0.004 (2) | −0.0104 (19) |
C13 | 0.120 (3) | 0.068 (2) | 0.089 (3) | −0.032 (2) | 0.027 (2) | −0.0326 (19) |
C14 | 0.103 (3) | 0.047 (2) | 0.099 (3) | −0.0034 (18) | 0.002 (2) | −0.0021 (18) |
C15 | 0.0581 (19) | 0.0485 (19) | 0.078 (2) | −0.0042 (14) | 0.0078 (17) | 0.0011 (16) |
C16 | 0.076 (2) | 0.046 (2) | 0.144 (4) | 0.0032 (17) | −0.003 (2) | −0.018 (2) |
C17 | 0.116 (4) | 0.098 (4) | 0.248 (7) | −0.001 (3) | 0.037 (4) | −0.009 (4) |
C18 | 0.0484 (17) | 0.0525 (17) | 0.0646 (18) | 0.0048 (13) | 0.0103 (15) | 0.0075 (14) |
C19 | 0.0418 (15) | 0.0505 (17) | 0.0508 (16) | 0.0034 (12) | 0.0050 (13) | 0.0027 (13) |
C20 | 0.0485 (15) | 0.0397 (15) | 0.0537 (16) | 0.0064 (12) | 0.0014 (13) | 0.0001 (12) |
C21 | 0.0534 (17) | 0.0448 (17) | 0.0551 (16) | 0.0116 (12) | 0.0081 (14) | −0.0003 (13) |
C22 | 0.0590 (18) | 0.0488 (17) | 0.0605 (17) | −0.0030 (13) | 0.0028 (15) | 0.0060 (14) |
O1 | 0.0704 (13) | 0.0460 (12) | 0.0593 (12) | −0.0106 (9) | 0.0126 (10) | 0.0055 (9) |
O2 | 0.122 (2) | 0.0752 (16) | 0.0875 (18) | 0.0008 (14) | 0.0381 (17) | −0.0087 (13) |
O3 | 0.0848 (15) | 0.0450 (12) | 0.0699 (13) | 0.0151 (10) | 0.0190 (12) | 0.0017 (10) |
C88A | 0.081 (3) | 0.050 (3) | 0.137 (6) | −0.020 (2) | 0.025 (4) | 0.008 (3) |
C99A | 0.154 (7) | 0.065 (3) | 0.088 (4) | 0.014 (4) | 0.036 (4) | −0.009 (3) |
C44A | 0.117 (6) | 0.064 (3) | 0.107 (5) | −0.016 (3) | −0.032 (4) | 0.026 (3) |
C44B | 0.079 (8) | 0.053 (9) | 0.15 (2) | 0.003 (7) | 0.007 (8) | −0.029 (10) |
C88B | 0.15 (2) | 0.060 (10) | 0.112 (11) | 0.009 (10) | 0.069 (14) | 0.018 (9) |
C99B | 0.127 (16) | 0.049 (8) | 0.121 (11) | −0.015 (10) | −0.039 (12) | −0.016 (9) |
C1—C6 | 1.382 (4) | C16—H16 | 0.9300 |
C1—C2 | 1.389 (4) | C17—H17A | 0.9300 |
C1—C22 | 1.533 (4) | C17—H17B | 0.9300 |
C2—C3 | 1.395 (4) | C18—C19 | 1.513 (4) |
C2—H2 | 0.9300 | C18—H18A | 0.9700 |
C3—C4 | 1.389 (4) | C18—H18B | 0.9700 |
C3—C18 | 1.508 (4) | C19—C21 | 1.380 (4) |
C4—C5 | 1.388 (4) | C19—C20 | 1.394 (3) |
C4—O1 | 1.409 (3) | C20—O3 | 1.380 (3) |
C5—C6 | 1.393 (4) | C20—C8i | 1.388 (4) |
C5—C7 | 1.506 (4) | C21—C10i | 1.383 (4) |
C6—H6 | 0.9300 | C21—H21 | 0.9300 |
C7—C8 | 1.518 (4) | C22—C44A | 1.502 (5) |
C7—H7A | 0.9700 | C22—C99A | 1.509 (5) |
C7—H7B | 0.9700 | C22—C99B | 1.522 (13) |
C8—C9 | 1.378 (4) | C22—C88B | 1.523 (12) |
C8—C20i | 1.388 (4) | C22—C88A | 1.535 (5) |
C9—C10 | 1.392 (4) | C22—C44B | 1.558 (12) |
C9—H9 | 0.9300 | O3—H3 | 0.8200 |
C10—C21i | 1.383 (4) | C88A—H88A | 0.9600 |
C10—C11 | 1.534 (4) | C88A—H88B | 0.9600 |
C11—C13 | 1.518 (4) | C88A—H88C | 0.9600 |
C11—C14 | 1.531 (5) | C99A—H99A | 0.9600 |
C11—C12 | 1.531 (4) | C99A—H99B | 0.9600 |
C12—H12A | 0.9600 | C99A—H99C | 0.9600 |
C12—H12B | 0.9600 | C44A—H44A | 0.9600 |
C12—H12C | 0.9600 | C44A—H44B | 0.9600 |
C13—H13A | 0.9600 | C44A—H44C | 0.9600 |
C13—H13B | 0.9600 | C44B—H44D | 0.9600 |
C13—H13C | 0.9600 | C44B—H44E | 0.9600 |
C14—H14A | 0.9600 | C44B—H44F | 0.9600 |
C14—H14B | 0.9600 | C88B—H88D | 0.9600 |
C14—H14C | 0.9600 | C88B—H88E | 0.9600 |
C15—O2 | 1.195 (3) | C88B—H88F | 0.9600 |
C15—O1 | 1.340 (4) | C99B—H99D | 0.9600 |
C15—C16 | 1.478 (5) | C99B—H99E | 0.9600 |
C16—C17 | 1.250 (6) | C99B—H99F | 0.9600 |
C6—C1—C2 | 117.3 (3) | C3—C18—C19 | 116.4 (2) |
C6—C1—C22 | 122.5 (3) | C3—C18—H18A | 108.2 |
C2—C1—C22 | 120.2 (3) | C19—C18—H18A | 108.2 |
C1—C2—C3 | 122.8 (3) | C3—C18—H18B | 108.2 |
C1—C2—H2 | 118.6 | C19—C18—H18B | 108.2 |
C3—C2—H2 | 118.6 | H18A—C18—H18B | 107.3 |
C4—C3—C2 | 116.6 (3) | C21—C19—C20 | 117.4 (2) |
C4—C3—C18 | 122.9 (2) | C21—C19—C18 | 120.3 (2) |
C2—C3—C18 | 120.5 (3) | C20—C19—C18 | 122.2 (2) |
C5—C4—C3 | 123.6 (2) | O3—C20—C8i | 118.4 (2) |
C5—C4—O1 | 119.5 (2) | O3—C20—C19 | 120.3 (2) |
C3—C4—O1 | 116.7 (2) | C8i—C20—C19 | 121.3 (2) |
C4—C5—C6 | 116.5 (3) | C19—C21—C10i | 123.8 (2) |
C4—C5—C7 | 123.2 (3) | C19—C21—H21 | 118.1 |
C6—C5—C7 | 120.2 (3) | C10i—C21—H21 | 118.1 |
C1—C6—C5 | 123.2 (3) | C44A—C22—C99A | 110.4 (4) |
C1—C6—H6 | 118.4 | C44A—C22—C99B | 133.9 (7) |
C5—C6—H6 | 118.4 | C99A—C22—C99B | 47.6 (9) |
C5—C7—C8 | 116.2 (2) | C44A—C22—C88B | 58.7 (9) |
C5—C7—H7A | 108.2 | C99A—C22—C88B | 143.5 (7) |
C8—C7—H7A | 108.2 | C99B—C22—C88B | 111.7 (13) |
C5—C7—H7B | 108.2 | C44A—C22—C1 | 112.3 (3) |
C8—C7—H7B | 108.2 | C99A—C22—C1 | 108.2 (3) |
H7A—C7—H7B | 107.4 | C99B—C22—C1 | 113.3 (7) |
C9—C8—C20i | 118.4 (2) | C88B—C22—C1 | 108.0 (6) |
C9—C8—C7 | 121.4 (2) | C44A—C22—C88A | 107.1 (4) |
C20i—C8—C7 | 120.3 (2) | C99A—C22—C88A | 108.8 (4) |
C8—C9—C10 | 122.9 (3) | C99B—C22—C88A | 62.7 (10) |
C8—C9—H9 | 118.6 | C88B—C22—C88A | 53.0 (10) |
C10—C9—H9 | 118.6 | C1—C22—C88A | 109.9 (3) |
C21i—C10—C9 | 116.2 (2) | C44A—C22—C44B | 49.5 (8) |
C21i—C10—C11 | 120.5 (2) | C99A—C22—C44B | 64.4 (8) |
C9—C10—C11 | 123.3 (2) | C99B—C22—C44B | 106.6 (11) |
C13—C11—C14 | 107.6 (3) | C88B—C22—C44B | 106.6 (12) |
C13—C11—C12 | 108.7 (3) | C1—C22—C44B | 110.5 (6) |
C14—C11—C12 | 109.1 (3) | C88A—C22—C44B | 138.9 (7) |
C13—C11—C10 | 112.6 (2) | C15—O1—C4 | 119.5 (2) |
C14—C11—C10 | 109.7 (3) | C20—O3—H3 | 109.5 |
C12—C11—C10 | 109.1 (2) | C22—C88A—H88A | 109.5 |
C11—C12—H12A | 109.5 | C22—C88A—H88B | 109.5 |
C11—C12—H12B | 109.5 | C22—C88A—H88C | 109.5 |
H12A—C12—H12B | 109.5 | C22—C99A—H99A | 109.5 |
C11—C12—H12C | 109.5 | C22—C99A—H99B | 109.5 |
H12A—C12—H12C | 109.5 | C22—C99A—H99C | 109.5 |
H12B—C12—H12C | 109.5 | C22—C44A—H44A | 109.5 |
C11—C13—H13A | 109.5 | C22—C44A—H44B | 109.5 |
C11—C13—H13B | 109.5 | C22—C44A—H44C | 109.5 |
H13A—C13—H13B | 109.5 | C22—C44B—H44D | 109.5 |
C11—C13—H13C | 109.5 | C22—C44B—H44E | 109.5 |
H13A—C13—H13C | 109.5 | H44D—C44B—H44E | 109.5 |
H13B—C13—H13C | 109.5 | C22—C44B—H44F | 109.5 |
C11—C14—H14A | 109.5 | H44D—C44B—H44F | 109.5 |
C11—C14—H14B | 109.5 | H44E—C44B—H44F | 109.5 |
H14A—C14—H14B | 109.5 | C22—C88B—H88D | 109.5 |
C11—C14—H14C | 109.5 | C22—C88B—H88E | 109.5 |
H14A—C14—H14C | 109.5 | H88D—C88B—H88E | 109.5 |
H14B—C14—H14C | 109.5 | C22—C88B—H88F | 109.5 |
O2—C15—O1 | 123.5 (3) | H88D—C88B—H88F | 109.5 |
O2—C15—C16 | 127.3 (3) | H88E—C88B—H88F | 109.5 |
O1—C15—C16 | 109.1 (3) | C22—C99B—H99D | 109.5 |
C17—C16—C15 | 122.0 (5) | C22—C99B—H99E | 109.5 |
C17—C16—H16 | 119.0 | H99D—C99B—H99E | 109.5 |
C15—C16—H16 | 119.0 | C22—C99B—H99F | 109.5 |
C16—C17—H17A | 120.0 | H99D—C99B—H99F | 109.5 |
C16—C17—H17B | 120.0 | H99E—C99B—H99F | 109.5 |
H17A—C17—H17B | 120.0 | ||
C6—C1—C2—C3 | 1.4 (4) | C9—C10—C11—C12 | 120.5 (3) |
C22—C1—C2—C3 | −176.0 (2) | O2—C15—C16—C17 | 5.0 (6) |
C1—C2—C3—C4 | −1.4 (4) | O1—C15—C16—C17 | −177.2 (4) |
C1—C2—C3—C18 | 176.7 (2) | C4—C3—C18—C19 | 62.2 (3) |
C2—C3—C4—C5 | 1.1 (4) | C2—C3—C18—C19 | −115.7 (3) |
C18—C3—C4—C5 | −176.9 (2) | C3—C18—C19—C21 | −133.9 (3) |
C2—C3—C4—O1 | 175.4 (2) | C3—C18—C19—C20 | 48.3 (4) |
C18—C3—C4—O1 | −2.6 (3) | C21—C19—C20—O3 | −177.1 (3) |
C3—C4—C5—C6 | −0.8 (4) | C18—C19—C20—O3 | 0.8 (4) |
O1—C4—C5—C6 | −174.9 (2) | C21—C19—C20—C8i | 1.1 (4) |
C3—C4—C5—C7 | 177.7 (2) | C18—C19—C20—C8i | 179.0 (3) |
O1—C4—C5—C7 | 3.5 (4) | C20—C19—C21—C10i | 0.7 (4) |
C2—C1—C6—C5 | −1.1 (4) | C18—C19—C21—C10i | −177.2 (3) |
C22—C1—C6—C5 | 176.3 (2) | C6—C1—C22—C44A | 22.8 (5) |
C4—C5—C6—C1 | 0.8 (4) | C2—C1—C22—C44A | −159.9 (4) |
C7—C5—C6—C1 | −177.7 (2) | C6—C1—C22—C99A | −99.3 (5) |
C4—C5—C7—C8 | −52.3 (4) | C2—C1—C22—C99A | 78.0 (5) |
C6—C5—C7—C8 | 126.1 (3) | C6—C1—C22—C99B | −150.1 (12) |
C5—C7—C8—C9 | 125.0 (3) | C2—C1—C22—C99B | 27.2 (12) |
C5—C7—C8—C20i | −55.7 (4) | C6—C1—C22—C88B | 85.7 (12) |
C20i—C8—C9—C10 | 1.5 (4) | C2—C1—C22—C88B | −97.0 (12) |
C7—C8—C9—C10 | −179.2 (3) | C6—C1—C22—C88A | 142.0 (4) |
C8—C9—C10—C21i | 0.2 (4) | C2—C1—C22—C88A | −40.7 (4) |
C8—C9—C10—C11 | −178.7 (3) | C6—C1—C22—C44B | −30.6 (10) |
C21i—C10—C11—C13 | −179.1 (3) | C2—C1—C22—C44B | 146.7 (10) |
C9—C10—C11—C13 | −0.3 (4) | O2—C15—O1—C4 | −1.5 (5) |
C21i—C10—C11—C14 | 61.0 (4) | C16—C15—O1—C4 | −179.5 (3) |
C9—C10—C11—C14 | −120.1 (3) | C5—C4—O1—C15 | −83.6 (3) |
C21i—C10—C11—C12 | −58.4 (4) | C3—C4—O1—C15 | 101.9 (3) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C50H60O6 |
Mr | 756.98 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 297 |
a, b, c (Å) | 15.8896 (11), 26.482 (2), 10.3522 (7) |
β (°) | 95.047 (6) |
V (Å3) | 4339.2 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.41 × 0.24 × 0.09 |
Data collection | |
Diffractometer | Stoe IPDS2 |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.940, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28360, 4277, 1985 |
Rint | 0.131 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.153, 0.89 |
No. of reflections | 4277 |
No. of parameters | 291 |
No. of restraints | 69 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.25 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
For the past 20 years the calixarenes, cavity-shaped macrocycles, have attracted much attention mainly in supramolecular and analytical chemistry, because they can form typical host–guest complexes with many neutral molecules and ions, like cyclodextrins and crown ethers (Gutsche & Alam, 1988; Gutsche, 1989). Owing to their nonplanar structure, calix[4]arenes can exist in one of the four conformations, and has been designated as cone, partial cone, 1,2-alternate, and 1,3-alternate [Andreetti et al., 1991; Casnati et al., 1995; Kim et al., 1999; Kim et al., 2000). By placing substituents at OH groups larger than methyl, conformation can be locked. Very often cone and partial cone conformes were synthesized by the alkylation (Iwamoto et al., 1991) and acylation (Gutsche & Lin, 1986) reaction at lover rim of calix[4]arene. But 1,2-alternate and 1,3-alternate conformers were observed only under certain reaction conditions.
As part of our work on substituted calix[4]arenes, we report herein the crystal structure of the title compound, (I), adopting a 1,3-alternate conformation. The two phenyl groups, A and D, lie above and the other two phenyl groups, B and C, below the least-squares plane defined by the four bridging methylene group, as illustrated in Fig. 1. The complete molecule is generated by 2-fold rotation symmetry. Bond angles involving the bridging methylene groups, i.e, C5—C7—C8 [116.2 (2)°] and C3—C18—C19 [116.4 (2)°], are significantly larger than the tetrahedral angle due to repulsion among the four phenyl groups. The dihedral angles of two pairs of facing rings, namely A and D, to which the OH group is bonded, and B and C, to which the acryloiloxy group is bonded, are 35.34 (10) and 20.01 (11)° respectively, so that rings A and D are splayed out upwards, and C and B are splayed out downwards from the central axis. Dihedral angles of adjacent phenyl rings in the calix[4]arene range from 85.13 (7) to 88.82 (7)°.
In the extended structure, there are no hydrogen bonding interactions and van der Waals interactions stabilize the extended structure (Fig. 2).