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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101220X/om6037sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680101220X/om6037Isup2.hkl
Contains datablock I

CCDC reference: 170927

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](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








Comment top

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°.

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing 50% displacement ellipsoids. Symmetry code: (i) 1 - x, 1 - y, 1 - z.
(I) top
Crystal data top
C38H44O2F(000) = 576
Mr = 532.7Dx = 1.187 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 8.6623 (8) Åθ = 10.1–14.3°
b = 18.1338 (13) ŵ = 0.07 mm1
c = 9.8554 (9) ÅT = 100 K
β = 105.68 (8)°Fragment, colourless
V = 1490.5 (2) Å30.70 × 0.41 × 0.30 mm
Z = 2
Data collection top
Nonius CAD-4
diffractometer
Rint = 0.014
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.2°
Graphite monochromatorh = 010
ω scansk = 1021
3130 measured reflectionsl = 1111
2618 independent reflections3 standard reflections every 120 min
2090 reflections with I > 2σ(I) intensity decay: 5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108H 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 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.22 e Å3
0 constraints
Crystal data top
C38H44O2V = 1490.5 (2) Å3
Mr = 532.7Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.6623 (8) ŵ = 0.07 mm1
b = 18.1338 (13) ÅT = 100 K
c = 9.8554 (9) Å0.70 × 0.41 × 0.30 mm
β = 105.68 (8)°
Data collection top
Nonius CAD-4
diffractometer
Rint = 0.014
3130 measured reflections3 standard reflections every 120 min
2618 independent reflections intensity decay: 5%
2090 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.21 e Å3
2618 reflectionsΔρmin = 0.22 e Å3
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
xyzUiso*/Ueq
O0.24785 (12)0.61658 (6)0.53954 (11)0.0206 (3)
C10.34016 (17)0.62189 (8)0.44455 (15)0.0160 (4)
C20.49191 (18)0.65422 (7)0.48621 (15)0.0164 (4)
C30.57635 (17)0.66457 (7)0.38569 (15)0.0159 (4)
C40.51413 (17)0.64484 (7)0.24494 (15)0.0162 (4)
C50.36333 (17)0.61112 (8)0.20863 (15)0.0164 (4)
C60.27512 (17)0.59868 (7)0.30516 (15)0.0161 (4)
C70.60159 (18)0.66004 (8)0.13151 (15)0.0187 (4)
C80.4971 (2)0.70988 (9)0.01731 (17)0.0286 (5)
C90.6320 (2)0.58680 (9)0.06472 (18)0.0274 (5)
C100.76116 (19)0.69886 (9)0.19105 (17)0.0251 (5)
C110.71823 (17)0.63838 (8)0.71049 (14)0.0162 (4)
C120.73164 (17)0.56265 (8)0.69336 (14)0.0163 (4)
C130.86748 (17)0.52339 (8)0.76416 (14)0.0162 (4)
C140.99230 (17)0.56221 (8)0.85580 (15)0.0183 (4)
C150.98116 (18)0.63753 (8)0.87292 (15)0.0197 (5)
C160.84501 (18)0.67577 (8)0.80059 (15)0.0188 (4)
C170.56603 (18)0.67929 (8)0.63652 (15)0.0185 (4)
C180.88365 (17)0.44125 (8)0.74080 (16)0.0184 (4)
C190.2696 (2)0.55006 (9)0.62082 (18)0.0304 (5)
H30.680300.685900.414300.0190*
H50.319200.596000.113700.0200*
H8A0.396400.684500.027900.0430*
H8B0.554300.721200.053400.0430*
H8C0.473700.755800.060300.0430*
H9A0.696700.554400.137800.0410*
H9B0.689400.596400.006600.0410*
H9C0.529200.562900.020300.0410*
H10A0.742500.747000.229000.0380*
H10B0.814500.705800.116100.0380*
H10C0.829300.668800.266400.0380*
H120.645300.537000.631400.0200*
H141.085700.536600.906800.0220*
H151.067500.663300.934700.0240*
H160.838600.727500.812700.0230*
H17A0.486500.672600.691200.0220*
H17B0.590400.732600.635900.0220*
H18A0.942100.434200.668200.0220*
H18B0.948700.418800.829400.0220*
H19A0.241200.507600.557500.0460*
H19B0.200500.551100.684900.0460*
H19C0.381900.546000.675700.0460*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.0217 (6)0.0235 (6)0.0178 (6)0.0025 (4)0.0075 (4)0.0011 (4)
C10.0185 (7)0.0151 (7)0.0150 (7)0.0052 (6)0.0058 (6)0.0023 (6)
C20.0197 (7)0.0138 (7)0.0137 (7)0.0053 (6)0.0009 (6)0.0016 (6)
C30.0158 (7)0.0137 (7)0.0160 (7)0.0005 (6)0.0006 (6)0.0014 (6)
C40.0195 (8)0.0135 (7)0.0148 (7)0.0029 (6)0.0031 (6)0.0018 (5)
C50.0193 (8)0.0167 (7)0.0110 (7)0.0022 (6)0.0001 (6)0.0003 (5)
C60.0155 (7)0.0134 (7)0.0171 (7)0.0031 (6)0.0006 (6)0.0010 (6)
C70.0209 (8)0.0195 (8)0.0153 (7)0.0010 (6)0.0043 (6)0.0002 (6)
C80.0304 (9)0.0360 (9)0.0197 (8)0.0037 (7)0.0074 (7)0.0087 (7)
C90.0348 (10)0.0254 (9)0.0273 (9)0.0050 (7)0.0173 (8)0.0041 (7)
C100.0249 (8)0.0303 (9)0.0206 (8)0.0065 (7)0.0071 (7)0.0013 (7)
C110.0186 (8)0.0209 (8)0.0096 (7)0.0004 (6)0.0049 (6)0.0009 (6)
C120.0155 (7)0.0214 (8)0.0102 (7)0.0021 (6)0.0004 (6)0.0013 (6)
C130.0168 (7)0.0207 (8)0.0116 (7)0.0018 (6)0.0047 (6)0.0015 (6)
C140.0141 (7)0.0253 (8)0.0140 (7)0.0003 (6)0.0010 (6)0.0014 (6)
C150.0174 (8)0.0231 (8)0.0163 (8)0.0051 (6)0.0006 (6)0.0022 (6)
C160.0229 (8)0.0177 (7)0.0157 (7)0.0027 (6)0.0052 (6)0.0010 (6)
C170.0223 (8)0.0184 (7)0.0135 (7)0.0019 (6)0.0024 (6)0.0017 (6)
C180.0169 (7)0.0209 (8)0.0165 (7)0.0018 (6)0.0029 (6)0.0013 (6)
C190.0384 (10)0.0304 (9)0.0281 (9)0.0042 (8)0.0189 (8)0.0085 (7)
Geometric parameters (Å, º) top
O—C11.3891 (18)C3—H30.95
O—C191.432 (2)C5—H50.95
C1—C21.396 (2)C8—H8A0.98
C1—C61.401 (2)C8—H8B0.98
C2—C31.394 (2)C8—H8C0.98
C2—C171.516 (2)C9—H9A0.98
C3—C41.392 (2)C9—H9B0.98
C4—C51.398 (2)C9—H9C0.98
C4—C71.535 (2)C10—H10A0.98
C5—C61.390 (2)C10—H10B0.98
C6—C18i1.511 (2)C10—H10C0.98
C7—C81.534 (2)C12—H120.95
C7—C91.536 (2)C14—H140.95
C7—C101.521 (2)C15—H150.95
C11—C121.392 (2)C16—H160.95
C11—C161.388 (2)C17—H17A0.99
C11—C171.517 (2)C17—H17B0.99
C12—C131.391 (2)C18—H18A0.99
C13—C141.397 (2)C18—H18B0.99
C13—C181.519 (2)C19—H19A0.98
C14—C151.383 (2)C19—H19B0.98
C15—C161.388 (2)C19—H19C0.98
C1—O—C19115.01 (14)H8A—C8—H8B109
O—C1—C2119.92 (15)H8A—C8—H8C109
O—C1—C6119.19 (15)H8B—C8—H8C109
C2—C1—C6120.78 (16)C7—C9—H9A109
C1—C2—C3118.74 (15)C7—C9—H9B109
C1—C2—C17121.99 (16)C7—C9—H9C109
C3—C2—C17119.27 (16)H9A—C9—H9B109
C2—C3—C4122.50 (16)H9A—C9—H9C109
C3—C4—C5116.78 (16)H9B—C9—H9C109
C3—C4—C7123.02 (15)C7—C10—H10A109
C5—C4—C7120.18 (15)C7—C10—H10B109
C4—C5—C6122.96 (15)C7—C10—H10C109
C1—C6—C5118.19 (16)H10A—C10—H10B109
C1—C6—C18i122.00 (15)H10A—C10—H10C109
C5—C6—C18i119.77 (15)H10B—C10—H10C109
C4—C7—C8109.31 (15)C11—C12—H12119
C4—C7—C9109.40 (14)C13—C12—H12119
C4—C7—C10112.22 (14)C13—C14—H14120
C8—C7—C9109.30 (15)C15—C14—H14120
C8—C7—C10107.76 (15)C14—C15—H15120
C9—C7—C10108.80 (16)C16—C15—H15120
C12—C11—C16118.80 (16)C11—C16—H16120
C12—C11—C17120.95 (15)C15—C16—H16120
C16—C11—C17120.21 (15)C2—C17—H17A109
C11—C12—C13122.08 (16)C2—C17—H17B109
C12—C13—C14117.93 (15)C11—C17—H17A109
C12—C13—C18121.73 (15)C11—C17—H17B109
C14—C13—C18120.32 (15)H17A—C17—H17B108
C13—C14—C15120.61 (16)C13—C18—H18A109
C14—C15—C16120.57 (16)C13—C18—H18B109
C11—C16—C15120.01 (16)H18A—C18—H18B108
C2—C17—C11113.98 (15)C6i—C18—H18A109
C6i—C18—C13113.66 (15)C6i—C18—H18B109
C2—C3—H3119O—C19—H19A109
C4—C3—H3119O—C19—H19B109
C4—C5—H5119O—C19—H19C109
C6—C5—H5119H19A—C19—H19B109
C7—C8—H8A109H19A—C19—H19C109
C7—C8—H8B109H19B—C19—H19C109
C7—C8—H8C109
C19—O—C1—C290.54 (18)C5—C4—C7—C10178.37 (15)
C19—O—C1—C693.37 (18)C3—C4—C7—C100.2 (2)
C1—O—C19—H19B179.79C5—C4—C7—C858.89 (19)
C1—O—C19—H19C59.79C5—C4—C7—C960.76 (19)
C1—O—C19—H19A60.21C4—C5—C6—C10.8 (2)
O—C1—C2—C3174.59 (15)C4—C5—C6—C18i177.20 (15)
O—C1—C2—C174.5 (2)C1—C6—C18i—C13i105.01 (17)
O—C1—C6—C18i8.3 (2)C5—C6—C18i—C13i72.87 (19)
C2—C1—C6—C52.2 (2)C12—C11—C16—C150.8 (2)
C2—C1—C6—C18i175.67 (15)C17—C11—C16—C15177.10 (16)
O—C1—C6—C5173.81 (15)C16—C11—C17—C2141.71 (16)
C6—C1—C2—C31.4 (2)C17—C11—C12—C13177.50 (16)
C6—C1—C2—C17179.47 (15)C12—C11—C17—C240.5 (2)
C1—C2—C3—C40.9 (2)C16—C11—C12—C130.3 (2)
C3—C2—C17—C1164.25 (19)C11—C12—C13—C140.6 (2)
C1—C2—C17—C11116.67 (17)C11—C12—C13—C18177.73 (16)
C17—C2—C3—C4178.18 (15)C12—C13—C18—C6i27.0 (2)
C2—C3—C4—C52.3 (2)C12—C13—C14—C151.1 (2)
C2—C3—C4—C7176.32 (15)C18—C13—C14—C15177.21 (16)
C3—C4—C5—C61.5 (2)C14—C13—C18—C6i154.73 (16)
C7—C4—C5—C6177.22 (15)C13—C14—C15—C160.7 (2)
C3—C4—C7—C8119.72 (17)C14—C15—C16—C110.2 (2)
C3—C4—C7—C9120.63 (17)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C17—H17A···O0.992.422.8947 (19)109
C18—H18A···Oi0.992.432.8861 (19)107
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC38H44O2
Mr532.7
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)8.6623 (8), 18.1338 (13), 9.8554 (9)
β (°) 105.68 (8)
V3)1490.5 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.70 × 0.41 × 0.30
Data collection
DiffractometerNonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3130, 2618, 2090
Rint0.014
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.108, 1.03
No. of reflections2618
No. of parameters185
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.22

Computer programs: CAD-4-PC (Enraf-Nonius, 1993), CAD-4-PC, XCAD4 (Harms, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), PLATON (Spek, 2001).

Selected geometric parameters (Å, º) top
O—C11.3891 (18)O—C191.432 (2)
C1—O—C19115.01 (14)O—C1—C6119.19 (15)
O—C1—C2119.92 (15)
 

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