Half of the title compound, C38H44O2, makes up the asymmetric unit; the whole molecule possesses inversion symmetry. The calix[4]arene conformation is similar to the unsubstituted calix[4]arene. Only one intermolecular interaction is noted.
Supporting information
CCDC reference: 170927
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.002 Å
- R factor = 0.039
- wR factor = 0.108
- Data-to-parameter ratio = 14.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
The title compound was prepared by alkylation of
bis-9,12-tert-butyl-25,27-dihydrocalix[4]arene using methyl iodide and
potassium carbonate in refluxing acetonitrile. Crystals suitable for X-ray
diffraction grew from fractions obtained following chromatography (SiO2
ether/hexanes eluent).
A 1.1 mm collimator was used. All H atoms were placed in calculated positions,
refined using a riding model, and given an isotropic displacement parameter
equal to 1.2 (CH, CH2) or 1.5 (CH3) times the equivalent isotropic
displacement parameter of the atom to which they were attached. The C—H
distances used depended on the type of C atom: Cmethylene—H = 0.99,
Cmethyl—H = 0.98, and Carene—H = 0.95 Å. Methyl-H atoms were allowed
to rotate about the adjacent C—C bond.
Data collection: CAD-4-PC (Enraf-Nonius, 1993); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: PLATON (Spek, 2001).
Crystal data top
C38H44O2 | F(000) = 576 |
Mr = 532.7 | Dx = 1.187 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 8.6623 (8) Å | θ = 10.1–14.3° |
b = 18.1338 (13) Å | µ = 0.07 mm−1 |
c = 9.8554 (9) Å | T = 100 K |
β = 105.68 (8)° | Fragment, colourless |
V = 1490.5 (2) Å3 | 0.70 × 0.41 × 0.30 mm |
Z = 2 | |
Data collection top
Nonius CAD-4 diffractometer | Rint = 0.014 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→10 |
ω scans | k = −10→21 |
3130 measured reflections | l = −11→11 |
2618 independent reflections | 3 standard reflections every 120 min |
2090 reflections with I > 2σ(I) | intensity decay: 5% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.4494P] where P = (Fo2 + 2Fc2)/3 |
2618 reflections | (Δ/σ)max = 0.001 |
185 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
0 constraints | |
Crystal data top
C38H44O2 | V = 1490.5 (2) Å3 |
Mr = 532.7 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.6623 (8) Å | µ = 0.07 mm−1 |
b = 18.1338 (13) Å | T = 100 K |
c = 9.8554 (9) Å | 0.70 × 0.41 × 0.30 mm |
β = 105.68 (8)° | |
Data collection top
Nonius CAD-4 diffractometer | Rint = 0.014 |
3130 measured reflections | 3 standard reflections every 120 min |
2618 independent reflections | intensity decay: 5% |
2090 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.21 e Å−3 |
2618 reflections | Δρmin = −0.22 e Å−3 |
185 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O | 0.24785 (12) | 0.61658 (6) | 0.53954 (11) | 0.0206 (3) | |
C1 | 0.34016 (17) | 0.62189 (8) | 0.44455 (15) | 0.0160 (4) | |
C2 | 0.49191 (18) | 0.65422 (7) | 0.48621 (15) | 0.0164 (4) | |
C3 | 0.57635 (17) | 0.66457 (7) | 0.38569 (15) | 0.0159 (4) | |
C4 | 0.51413 (17) | 0.64484 (7) | 0.24494 (15) | 0.0162 (4) | |
C5 | 0.36333 (17) | 0.61112 (8) | 0.20863 (15) | 0.0164 (4) | |
C6 | 0.27512 (17) | 0.59868 (7) | 0.30516 (15) | 0.0161 (4) | |
C7 | 0.60159 (18) | 0.66004 (8) | 0.13151 (15) | 0.0187 (4) | |
C8 | 0.4971 (2) | 0.70988 (9) | 0.01731 (17) | 0.0286 (5) | |
C9 | 0.6320 (2) | 0.58680 (9) | 0.06472 (18) | 0.0274 (5) | |
C10 | 0.76116 (19) | 0.69886 (9) | 0.19105 (17) | 0.0251 (5) | |
C11 | 0.71823 (17) | 0.63838 (8) | 0.71049 (14) | 0.0162 (4) | |
C12 | 0.73164 (17) | 0.56265 (8) | 0.69336 (14) | 0.0163 (4) | |
C13 | 0.86748 (17) | 0.52339 (8) | 0.76416 (14) | 0.0162 (4) | |
C14 | 0.99230 (17) | 0.56221 (8) | 0.85580 (15) | 0.0183 (4) | |
C15 | 0.98116 (18) | 0.63753 (8) | 0.87292 (15) | 0.0197 (5) | |
C16 | 0.84501 (18) | 0.67577 (8) | 0.80059 (15) | 0.0188 (4) | |
C17 | 0.56603 (18) | 0.67929 (8) | 0.63652 (15) | 0.0185 (4) | |
C18 | 0.88365 (17) | 0.44125 (8) | 0.74080 (16) | 0.0184 (4) | |
C19 | 0.2696 (2) | 0.55006 (9) | 0.62082 (18) | 0.0304 (5) | |
H3 | 0.68030 | 0.68590 | 0.41430 | 0.0190* | |
H5 | 0.31920 | 0.59600 | 0.11370 | 0.0200* | |
H8A | 0.39640 | 0.68450 | −0.02790 | 0.0430* | |
H8B | 0.55430 | 0.72120 | −0.05340 | 0.0430* | |
H8C | 0.47370 | 0.75580 | 0.06030 | 0.0430* | |
H9A | 0.69670 | 0.55440 | 0.13780 | 0.0410* | |
H9B | 0.68940 | 0.59640 | −0.00660 | 0.0410* | |
H9C | 0.52920 | 0.56290 | 0.02030 | 0.0410* | |
H10A | 0.74250 | 0.74700 | 0.22900 | 0.0380* | |
H10B | 0.81450 | 0.70580 | 0.11610 | 0.0380* | |
H10C | 0.82930 | 0.66880 | 0.26640 | 0.0380* | |
H12 | 0.64530 | 0.53700 | 0.63140 | 0.0200* | |
H14 | 1.08570 | 0.53660 | 0.90680 | 0.0220* | |
H15 | 1.06750 | 0.66330 | 0.93470 | 0.0240* | |
H16 | 0.83860 | 0.72750 | 0.81270 | 0.0230* | |
H17A | 0.48650 | 0.67260 | 0.69120 | 0.0220* | |
H17B | 0.59040 | 0.73260 | 0.63590 | 0.0220* | |
H18A | 0.94210 | 0.43420 | 0.66820 | 0.0220* | |
H18B | 0.94870 | 0.41880 | 0.82940 | 0.0220* | |
H19A | 0.24120 | 0.50760 | 0.55750 | 0.0460* | |
H19B | 0.20050 | 0.55110 | 0.68490 | 0.0460* | |
H19C | 0.38190 | 0.54600 | 0.67570 | 0.0460* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O | 0.0217 (6) | 0.0235 (6) | 0.0178 (6) | 0.0025 (4) | 0.0075 (4) | 0.0011 (4) |
C1 | 0.0185 (7) | 0.0151 (7) | 0.0150 (7) | 0.0052 (6) | 0.0058 (6) | 0.0023 (6) |
C2 | 0.0197 (7) | 0.0138 (7) | 0.0137 (7) | 0.0053 (6) | 0.0009 (6) | 0.0016 (6) |
C3 | 0.0158 (7) | 0.0137 (7) | 0.0160 (7) | 0.0005 (6) | 0.0006 (6) | 0.0014 (6) |
C4 | 0.0195 (8) | 0.0135 (7) | 0.0148 (7) | 0.0029 (6) | 0.0031 (6) | 0.0018 (5) |
C5 | 0.0193 (8) | 0.0167 (7) | 0.0110 (7) | 0.0022 (6) | 0.0001 (6) | 0.0003 (5) |
C6 | 0.0155 (7) | 0.0134 (7) | 0.0171 (7) | 0.0031 (6) | 0.0006 (6) | 0.0010 (6) |
C7 | 0.0209 (8) | 0.0195 (8) | 0.0153 (7) | −0.0010 (6) | 0.0043 (6) | 0.0002 (6) |
C8 | 0.0304 (9) | 0.0360 (9) | 0.0197 (8) | 0.0037 (7) | 0.0074 (7) | 0.0087 (7) |
C9 | 0.0348 (10) | 0.0254 (9) | 0.0273 (9) | −0.0050 (7) | 0.0173 (8) | −0.0041 (7) |
C10 | 0.0249 (8) | 0.0303 (9) | 0.0206 (8) | −0.0065 (7) | 0.0071 (7) | −0.0013 (7) |
C11 | 0.0186 (8) | 0.0209 (8) | 0.0096 (7) | −0.0004 (6) | 0.0049 (6) | 0.0009 (6) |
C12 | 0.0155 (7) | 0.0214 (8) | 0.0102 (7) | −0.0021 (6) | 0.0004 (6) | −0.0013 (6) |
C13 | 0.0168 (7) | 0.0207 (8) | 0.0116 (7) | −0.0018 (6) | 0.0047 (6) | 0.0015 (6) |
C14 | 0.0141 (7) | 0.0253 (8) | 0.0140 (7) | 0.0003 (6) | 0.0010 (6) | 0.0014 (6) |
C15 | 0.0174 (8) | 0.0231 (8) | 0.0163 (8) | −0.0051 (6) | 0.0006 (6) | −0.0022 (6) |
C16 | 0.0229 (8) | 0.0177 (7) | 0.0157 (7) | −0.0027 (6) | 0.0052 (6) | −0.0010 (6) |
C17 | 0.0223 (8) | 0.0184 (7) | 0.0135 (7) | 0.0019 (6) | 0.0024 (6) | −0.0017 (6) |
C18 | 0.0169 (7) | 0.0209 (8) | 0.0165 (7) | 0.0018 (6) | 0.0029 (6) | 0.0013 (6) |
C19 | 0.0384 (10) | 0.0304 (9) | 0.0281 (9) | 0.0042 (8) | 0.0189 (8) | 0.0085 (7) |
Geometric parameters (Å, º) top
O—C1 | 1.3891 (18) | C3—H3 | 0.95 |
O—C19 | 1.432 (2) | C5—H5 | 0.95 |
C1—C2 | 1.396 (2) | C8—H8A | 0.98 |
C1—C6 | 1.401 (2) | C8—H8B | 0.98 |
C2—C3 | 1.394 (2) | C8—H8C | 0.98 |
C2—C17 | 1.516 (2) | C9—H9A | 0.98 |
C3—C4 | 1.392 (2) | C9—H9B | 0.98 |
C4—C5 | 1.398 (2) | C9—H9C | 0.98 |
C4—C7 | 1.535 (2) | C10—H10A | 0.98 |
C5—C6 | 1.390 (2) | C10—H10B | 0.98 |
C6—C18i | 1.511 (2) | C10—H10C | 0.98 |
C7—C8 | 1.534 (2) | C12—H12 | 0.95 |
C7—C9 | 1.536 (2) | C14—H14 | 0.95 |
C7—C10 | 1.521 (2) | C15—H15 | 0.95 |
C11—C12 | 1.392 (2) | C16—H16 | 0.95 |
C11—C16 | 1.388 (2) | C17—H17A | 0.99 |
C11—C17 | 1.517 (2) | C17—H17B | 0.99 |
C12—C13 | 1.391 (2) | C18—H18A | 0.99 |
C13—C14 | 1.397 (2) | C18—H18B | 0.99 |
C13—C18 | 1.519 (2) | C19—H19A | 0.98 |
C14—C15 | 1.383 (2) | C19—H19B | 0.98 |
C15—C16 | 1.388 (2) | C19—H19C | 0.98 |
| | | |
C1—O—C19 | 115.01 (14) | H8A—C8—H8B | 109 |
O—C1—C2 | 119.92 (15) | H8A—C8—H8C | 109 |
O—C1—C6 | 119.19 (15) | H8B—C8—H8C | 109 |
C2—C1—C6 | 120.78 (16) | C7—C9—H9A | 109 |
C1—C2—C3 | 118.74 (15) | C7—C9—H9B | 109 |
C1—C2—C17 | 121.99 (16) | C7—C9—H9C | 109 |
C3—C2—C17 | 119.27 (16) | H9A—C9—H9B | 109 |
C2—C3—C4 | 122.50 (16) | H9A—C9—H9C | 109 |
C3—C4—C5 | 116.78 (16) | H9B—C9—H9C | 109 |
C3—C4—C7 | 123.02 (15) | C7—C10—H10A | 109 |
C5—C4—C7 | 120.18 (15) | C7—C10—H10B | 109 |
C4—C5—C6 | 122.96 (15) | C7—C10—H10C | 109 |
C1—C6—C5 | 118.19 (16) | H10A—C10—H10B | 109 |
C1—C6—C18i | 122.00 (15) | H10A—C10—H10C | 109 |
C5—C6—C18i | 119.77 (15) | H10B—C10—H10C | 109 |
C4—C7—C8 | 109.31 (15) | C11—C12—H12 | 119 |
C4—C7—C9 | 109.40 (14) | C13—C12—H12 | 119 |
C4—C7—C10 | 112.22 (14) | C13—C14—H14 | 120 |
C8—C7—C9 | 109.30 (15) | C15—C14—H14 | 120 |
C8—C7—C10 | 107.76 (15) | C14—C15—H15 | 120 |
C9—C7—C10 | 108.80 (16) | C16—C15—H15 | 120 |
C12—C11—C16 | 118.80 (16) | C11—C16—H16 | 120 |
C12—C11—C17 | 120.95 (15) | C15—C16—H16 | 120 |
C16—C11—C17 | 120.21 (15) | C2—C17—H17A | 109 |
C11—C12—C13 | 122.08 (16) | C2—C17—H17B | 109 |
C12—C13—C14 | 117.93 (15) | C11—C17—H17A | 109 |
C12—C13—C18 | 121.73 (15) | C11—C17—H17B | 109 |
C14—C13—C18 | 120.32 (15) | H17A—C17—H17B | 108 |
C13—C14—C15 | 120.61 (16) | C13—C18—H18A | 109 |
C14—C15—C16 | 120.57 (16) | C13—C18—H18B | 109 |
C11—C16—C15 | 120.01 (16) | H18A—C18—H18B | 108 |
C2—C17—C11 | 113.98 (15) | C6i—C18—H18A | 109 |
C6i—C18—C13 | 113.66 (15) | C6i—C18—H18B | 109 |
C2—C3—H3 | 119 | O—C19—H19A | 109 |
C4—C3—H3 | 119 | O—C19—H19B | 109 |
C4—C5—H5 | 119 | O—C19—H19C | 109 |
C6—C5—H5 | 119 | H19A—C19—H19B | 109 |
C7—C8—H8A | 109 | H19A—C19—H19C | 109 |
C7—C8—H8B | 109 | H19B—C19—H19C | 109 |
C7—C8—H8C | 109 | | |
| | | |
C19—O—C1—C2 | −90.54 (18) | C5—C4—C7—C10 | 178.37 (15) |
C19—O—C1—C6 | 93.37 (18) | C3—C4—C7—C10 | −0.2 (2) |
C1—O—C19—H19B | 179.79 | C5—C4—C7—C8 | 58.89 (19) |
C1—O—C19—H19C | 59.79 | C5—C4—C7—C9 | −60.76 (19) |
C1—O—C19—H19A | −60.21 | C4—C5—C6—C1 | 0.8 (2) |
O—C1—C2—C3 | −174.59 (15) | C4—C5—C6—C18i | −177.20 (15) |
O—C1—C2—C17 | 4.5 (2) | C1—C6—C18i—C13i | −105.01 (17) |
O—C1—C6—C18i | −8.3 (2) | C5—C6—C18i—C13i | 72.87 (19) |
C2—C1—C6—C5 | −2.2 (2) | C12—C11—C16—C15 | −0.8 (2) |
C2—C1—C6—C18i | 175.67 (15) | C17—C11—C16—C15 | 177.10 (16) |
O—C1—C6—C5 | 173.81 (15) | C16—C11—C17—C2 | 141.71 (16) |
C6—C1—C2—C3 | 1.4 (2) | C17—C11—C12—C13 | −177.50 (16) |
C6—C1—C2—C17 | −179.47 (15) | C12—C11—C17—C2 | −40.5 (2) |
C1—C2—C3—C4 | 0.9 (2) | C16—C11—C12—C13 | 0.3 (2) |
C3—C2—C17—C11 | −64.25 (19) | C11—C12—C13—C14 | 0.6 (2) |
C1—C2—C17—C11 | 116.67 (17) | C11—C12—C13—C18 | −177.73 (16) |
C17—C2—C3—C4 | −178.18 (15) | C12—C13—C18—C6i | −27.0 (2) |
C2—C3—C4—C5 | −2.3 (2) | C12—C13—C14—C15 | −1.1 (2) |
C2—C3—C4—C7 | 176.32 (15) | C18—C13—C14—C15 | 177.21 (16) |
C3—C4—C5—C6 | 1.5 (2) | C14—C13—C18—C6i | 154.73 (16) |
C7—C4—C5—C6 | −177.22 (15) | C13—C14—C15—C16 | 0.7 (2) |
C3—C4—C7—C8 | −119.72 (17) | C14—C15—C16—C11 | 0.2 (2) |
C3—C4—C7—C9 | 120.63 (17) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17A···O | 0.99 | 2.42 | 2.8947 (19) | 109 |
C18—H18A···Oi | 0.99 | 2.43 | 2.8861 (19) | 107 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C38H44O2 |
Mr | 532.7 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 8.6623 (8), 18.1338 (13), 9.8554 (9) |
β (°) | 105.68 (8) |
V (Å3) | 1490.5 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.70 × 0.41 × 0.30 |
|
Data collection |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3130, 2618, 2090 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.108, 1.03 |
No. of reflections | 2618 |
No. of parameters | 185 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.22 |
Selected geometric parameters (Å, º) topO—C1 | 1.3891 (18) | O—C19 | 1.432 (2) |
| | | |
C1—O—C19 | 115.01 (14) | O—C1—C6 | 119.19 (15) |
O—C1—C2 | 119.92 (15) | | |
The title compound was prepared as part of our investigations into the synthesis of new calix[4]arene-based crown ether extractants (Sachleben, et al., 1999). Only half of the molecule makes up the asymmetric unit, the other half is generated by the crystallographic inversion centre [symmetry code:1 - x, 1 - y, 1 - z, denoted (i) throughout this paper]. The conformation of a calix[4]arene is generally defined in terms of the relative orientation of the arene rings with respect to the best plane defined by the four calix methylene C atoms (C17, C18, C17i, and C18i). This methylene carbon plane is referred to as the reference plane (Perrin & Oehler, 1991). The planes of the two methoxy-substituted arene rings (A1 and A1i) are nearly perpendicular to the reference plane [84.5 (1)°], while the unsubstituted arene rings (A2 and A2i) appear to be roughly parallel to it [173.9 (1)°]. This calix configuration closely resembles that of the unsubstituted parent molecule, calix[4]arene (McMurry & Phelan, 1991) and that of tetra-tert-butyl-calix[4]arene (Grynszpan et al., 1991). Strangely, the more closely related tetra-tert-butyl-diethoxy-calix[4]arene adopts a 1,3-alternate calix conformation (Ting et al., 1995).
Examination of the extended structure reveals only one intermolecular interaction worthy of mention, an edge-face arene interaction between A2 and A1. The H16···A1centroid distance is 2.64 Å and the C16—H16···A1centroid angle is 160°.