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Calix[4]arene and oxacalix[4]arene derivatives have eight possible conformations in the up and down directions of their four aromatic rings from the mean plane of a bridged central ring, the conformations of which determine the func­tionality of the host frameworks. Despite being a known compound for five decades, oxacalix[4]arene, C24H16O4, has not been characterized previously by crystallographic methods. It crystallizes from hexa­ne/CH2Cl2 solution to give two polymorphs, i.e. prismatic and block-shaped crystals as twisted 1,3-alternate structures with S4 and C2 symmetry, respectively. These were previously suggested as the prefered stable conformations by density functional theory (DFT) calculations.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619001517/ky3159sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229619001517/ky3159Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229619001517/ky3159IIsup3.hkl
Contains datablock II

CCDC references: 1893738; 1893737

Computing details top

For both structures, data collection: APEX3 (Bruker, 2017); cell refinement: APEX3 (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: shelXle (Hübschle et al., 2011).

Pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15(26),16,18,21,23-dodecaene (I) top
Crystal data top
C24H16O4Dx = 1.326 Mg m3
Mr = 368.37Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421cCell parameters from 165 reflections
a = 12.8946 (9) Åθ = 4.5–24.7°
c = 5.5501 (5) ŵ = 0.09 mm1
V = 922.82 (15) Å3T = 100 K
Z = 2Prismatic, colorless
F(000) = 3840.14 × 0.14 × 0.09 mm
Data collection top
Bruker D8 goniometer
diffractometer
858 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm-1Rint = 0.059
φ and ω scansθmax = 26.4°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2017)
h = 1515
Tmin = 0.91, Tmax = 0.99k = 1515
11051 measured reflectionsl = 66
940 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032 w = 1/[σ2(Fo2) + (0.0262P)2 + 0.1723P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.072(Δ/σ)max < 0.001
S = 1.19Δρmax = 0.15 e Å3
940 reflectionsΔρmin = 0.18 e Å3
64 parametersAbsolute structure: Flack x determined using 333 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
0 restraintsAbsolute structure parameter: 0.0 (8)
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.27255 (15)0.51796 (14)0.5465 (3)0.0197 (4)
C20.33818 (15)0.43542 (14)0.4950 (4)0.0189 (4)
H20.3792870.4348830.3529320.023*
C30.34176 (14)0.35388 (14)0.6576 (4)0.0195 (4)
C40.28122 (15)0.35410 (15)0.8641 (4)0.0229 (4)
H40.2851160.2982340.9753050.027*
C50.21508 (17)0.43661 (16)0.9063 (4)0.0257 (5)
H50.1723630.4362821.0457130.031*
C60.21013 (15)0.51997 (16)0.7479 (4)0.0241 (5)
H60.164970.5767440.777730.029*
O10.26544 (10)0.59978 (10)0.3825 (3)0.0230 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0168 (9)0.0191 (10)0.0233 (11)0.0034 (8)0.0028 (9)0.0002 (8)
C20.0161 (9)0.0214 (10)0.0192 (9)0.0031 (7)0.0007 (8)0.0010 (8)
C30.0167 (9)0.0178 (10)0.0240 (10)0.0027 (7)0.0020 (8)0.0022 (8)
C40.0229 (10)0.0232 (10)0.0226 (11)0.0063 (8)0.0002 (9)0.0016 (8)
C50.0231 (11)0.0299 (11)0.0242 (12)0.0059 (9)0.0046 (9)0.0048 (9)
C60.0194 (10)0.0239 (10)0.0290 (11)0.0001 (8)0.0013 (9)0.0067 (9)
O10.0172 (7)0.0210 (7)0.0308 (8)0.0006 (5)0.0023 (6)0.0028 (6)
Geometric parameters (Å, º) top
C1—C61.378 (3)C3—C41.387 (3)
C1—C21.389 (3)C4—C51.383 (3)
C1—O11.396 (2)C4—H40.95
C2—C31.386 (3)C5—C61.390 (3)
C2—H20.95C5—H50.95
C3—O1i1.385 (2)C6—H60.95
C6—C1—C2122.48 (18)C5—C4—H4120.4
C6—C1—O1118.45 (17)C3—C4—H4120.4
C2—C1—O1118.99 (17)C4—C5—C6121.07 (19)
C3—C2—C1117.86 (18)C4—C5—H5119.5
C3—C2—H2121.1C6—C5—H5119.5
C1—C2—H2121.1C1—C6—C5118.15 (18)
O1i—C3—C4116.14 (17)C1—C6—H6120.9
O1i—C3—C2122.56 (18)C5—C6—H6120.9
C4—C3—C2121.18 (18)C3ii—O1—C1117.50 (15)
C5—C4—C3119.24 (18)
C6—C1—C2—C31.6 (3)C3—C4—C5—C61.4 (3)
O1—C1—C2—C3178.32 (17)C2—C1—C6—C51.1 (3)
C1—C2—C3—O1i176.47 (16)O1—C1—C6—C5177.89 (17)
C1—C2—C3—C40.5 (3)C4—C5—C6—C10.4 (3)
O1i—C3—C4—C5175.28 (18)C6—C1—O1—C3ii119.23 (19)
C2—C3—C4—C50.9 (3)C2—C1—O1—C3ii63.9 (2)
Symmetry codes: (i) y+1, x, z+1; (ii) y, x+1, z+1.
2,8,14,20-Tetraoxapentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15(26),16,18,21,23-dodecaene (II) top
Crystal data top
C24H16O4F(000) = 768
Mr = 368.37Dx = 1.370 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 19.0935 (13) ÅCell parameters from 161 reflections
b = 5.4475 (4) Åθ = 3.9–26.2°
c = 18.9054 (12) ŵ = 0.09 mm1
β = 114.732 (2)°T = 100 K
V = 1786.0 (2) Å3Block, colorless
Z = 40.25 × 0.19 × 0.11 mm
Data collection top
Bruker D8 goniometer
diffractometer
1503 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm-1Rint = 0.049
φ and ω scansθmax = 26.4°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2017)
h = 2323
Tmin = 0.92, Tmax = 0.99k = 66
10409 measured reflectionsl = 2323
1783 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0403P)2 + 1.3406P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1783 reflectionsΔρmax = 0.19 e Å3
127 parametersΔρmin = 0.25 e Å3
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.65630 (7)0.5039 (2)0.77396 (7)0.0175 (3)
C20.60352 (7)0.3450 (2)0.72122 (7)0.0183 (3)
H20.5857750.2040980.7384740.022*
C30.57731 (7)0.3974 (2)0.64244 (7)0.0183 (3)
C40.60323 (8)0.5976 (3)0.61580 (8)0.0214 (3)
H40.584810.6291080.5615680.026*
C50.65700 (8)0.7530 (3)0.66999 (8)0.0224 (3)
H50.6757390.8911510.6525310.027*
C60.68340 (7)0.7082 (2)0.74899 (8)0.0200 (3)
H60.7196360.8156970.7857420.024*
C70.45545 (7)0.1936 (2)0.58891 (7)0.0177 (3)
C80.42206 (7)0.3547 (2)0.62244 (7)0.0183 (3)
H80.4483570.4987730.6483440.022*
C90.34904 (7)0.2995 (2)0.61709 (7)0.0178 (3)
C100.30943 (8)0.0925 (2)0.57930 (7)0.0207 (3)
H100.2596160.0575780.5765790.025*
C110.34404 (8)0.0639 (3)0.54529 (8)0.0237 (3)
H110.317210.2060550.5184140.028*
C120.41700 (8)0.0155 (2)0.55002 (7)0.0208 (3)
H120.440440.1238990.5269590.025*
O10.68795 (5)0.46424 (18)0.85344 (5)0.0207 (2)
O20.52634 (5)0.23700 (18)0.58748 (5)0.0219 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0162 (6)0.0206 (6)0.0177 (6)0.0032 (5)0.0092 (5)0.0005 (5)
C20.0188 (7)0.0184 (6)0.0213 (7)0.0002 (5)0.0120 (6)0.0007 (5)
C30.0152 (6)0.0220 (7)0.0189 (6)0.0007 (5)0.0085 (5)0.0025 (5)
C40.0200 (7)0.0270 (7)0.0194 (6)0.0026 (6)0.0104 (6)0.0043 (6)
C50.0206 (7)0.0211 (7)0.0282 (7)0.0001 (5)0.0129 (6)0.0054 (6)
C60.0170 (6)0.0188 (6)0.0253 (7)0.0000 (5)0.0100 (6)0.0012 (6)
C70.0174 (6)0.0228 (7)0.0134 (6)0.0001 (5)0.0070 (5)0.0034 (5)
C80.0208 (7)0.0186 (6)0.0148 (6)0.0018 (5)0.0067 (5)0.0004 (5)
C90.0196 (6)0.0213 (6)0.0122 (6)0.0039 (5)0.0063 (5)0.0024 (5)
C100.0181 (7)0.0242 (7)0.0190 (6)0.0023 (5)0.0071 (6)0.0011 (6)
C110.0249 (7)0.0215 (7)0.0230 (7)0.0045 (6)0.0082 (6)0.0028 (6)
C120.0247 (7)0.0203 (7)0.0182 (6)0.0021 (5)0.0098 (6)0.0011 (5)
O10.0188 (5)0.0257 (5)0.0175 (5)0.0046 (4)0.0074 (4)0.0012 (4)
O20.0201 (5)0.0295 (5)0.0191 (5)0.0050 (4)0.0111 (4)0.0064 (4)
Geometric parameters (Å, º) top
C1—O11.3820 (15)C7—C81.3844 (18)
C1—C21.3853 (18)C7—O21.3853 (15)
C1—C61.3902 (19)C7—C121.3874 (19)
C2—C31.3880 (18)C8—C91.3881 (18)
C2—H20.95C8—H80.95
C3—C41.3773 (19)C9—C101.3789 (19)
C3—O21.3943 (16)C9—O1i1.3944 (16)
C4—C51.393 (2)C10—C111.3896 (19)
C4—H40.95C10—H100.95
C5—C61.3835 (19)C11—C121.3835 (19)
C5—H50.95C11—H110.95
C6—H60.95C12—H120.95
O1—C1—C2122.70 (12)C8—C7—C12121.33 (12)
O1—C1—C6116.03 (11)O2—C7—C12115.77 (11)
C2—C1—C6121.19 (12)C7—C8—C9118.05 (12)
C1—C2—C3118.09 (12)C7—C8—H8121.0
C1—C2—H2121.0C9—C8—H8121.0
C3—C2—H2121.0C10—C9—C8122.09 (12)
C4—C3—C2122.14 (12)C10—C9—O1i118.28 (11)
C4—C3—O2117.99 (11)C8—C9—O1i119.51 (12)
C2—C3—O2119.77 (12)C9—C10—C11118.50 (12)
C3—C4—C5118.63 (12)C9—C10—H10120.8
C3—C4—H4120.7C11—C10—H10120.8
C5—C4—H4120.7C12—C11—C10120.94 (13)
C6—C5—C4120.69 (13)C12—C11—H11119.5
C6—C5—H5119.7C10—C11—H11119.5
C4—C5—H5119.7C11—C12—C7119.08 (12)
C5—C6—C1119.24 (12)C11—C12—H12120.5
C5—C6—H6120.4C7—C12—H12120.5
C1—C6—H6120.4C1—O1—C9i118.10 (10)
C8—C7—O2122.78 (12)C7—O2—C3118.39 (10)
O1—C1—C2—C3177.77 (11)C7—C8—C9—O1i176.60 (11)
C6—C1—C2—C31.06 (19)C8—C9—C10—C110.38 (19)
C1—C2—C3—C41.32 (19)O1i—C9—C10—C11175.76 (11)
C1—C2—C3—O2177.66 (11)C9—C10—C11—C120.9 (2)
C2—C3—C4—C50.6 (2)C10—C11—C12—C70.5 (2)
O2—C3—C4—C5176.96 (11)C8—C7—C12—C110.45 (19)
C3—C4—C5—C60.5 (2)O2—C7—C12—C11176.52 (11)
C4—C5—C6—C10.7 (2)C2—C1—O1—C9i17.78 (17)
O1—C1—C6—C5176.99 (11)C6—C1—O1—C9i165.35 (11)
C2—C1—C6—C50.07 (19)C8—C7—O2—C322.27 (17)
O2—C7—C8—C9176.71 (11)C12—C7—O2—C3161.72 (11)
C12—C7—C8—C90.92 (19)C4—C3—O2—C7122.97 (13)
C7—C8—C9—C100.50 (19)C2—C3—O2—C760.54 (16)
Symmetry code: (i) x+1, y, z+3/2.
Dihedral angles (°) of the four phenylene rings (A, B, C, and D) from the mean plane with Gibbs free Energy ΔG (kcal mol-1; 1 kcal mol-1 = 4.184 kJ mol-1) reported by Zuo et al. (2011) top
TypeConformationABCDΔG
c1,3-altenate, C2128.3-126.9128.3-126.90.0
d1,3-altenate, S4123.6-123.6123.6-123.60.5
hChair, C2h95.9178.7-95.9178.76.6
 

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