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
CCDC references: 1893738; 1893737
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[19.3.1.1
3,7.1
9,13.1
15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15(26),16,18,21,23-dodecaene (I)
top
Crystal data top
C24H16O4 | Dx = 1.326 Mg m−3 |
Mr = 368.37 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P421c | Cell parameters from 165 reflections |
a = 12.8946 (9) Å | θ = 4.5–24.7° |
c = 5.5501 (5) Å | µ = 0.09 mm−1 |
V = 922.82 (15) Å3 | T = 100 K |
Z = 2 | Prismatic, colorless |
F(000) = 384 | 0.14 × 0.14 × 0.09 mm |
Data collection top
Bruker D8 goniometer diffractometer | 858 reflections with I > 2σ(I) |
Detector resolution: 7.3910 pixels mm-1 | Rint = 0.059 |
φ and ω scans | θmax = 26.4°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2017) | h = −15→15 |
Tmin = 0.91, Tmax = 0.99 | k = −15→15 |
11051 measured reflections | l = −6→6 |
940 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 1.19 | Δρmax = 0.15 e Å−3 |
940 reflections | Δρmin = −0.18 e Å−3 |
64 parameters | Absolute structure: Flack x determined using 333 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
0 restraints | Absolute 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 | x | y | z | Uiso*/Ueq | |
C1 | 0.27255 (15) | 0.51796 (14) | 0.5465 (3) | 0.0197 (4) | |
C2 | 0.33818 (15) | 0.43542 (14) | 0.4950 (4) | 0.0189 (4) | |
H2 | 0.379287 | 0.434883 | 0.352932 | 0.023* | |
C3 | 0.34176 (14) | 0.35388 (14) | 0.6576 (4) | 0.0195 (4) | |
C4 | 0.28122 (15) | 0.35410 (15) | 0.8641 (4) | 0.0229 (4) | |
H4 | 0.285116 | 0.298234 | 0.975305 | 0.027* | |
C5 | 0.21508 (17) | 0.43661 (16) | 0.9063 (4) | 0.0257 (5) | |
H5 | 0.172363 | 0.436282 | 1.045713 | 0.031* | |
C6 | 0.21013 (15) | 0.51997 (16) | 0.7479 (4) | 0.0241 (5) | |
H6 | 0.16497 | 0.576744 | 0.77773 | 0.029* | |
O1 | 0.26544 (10) | 0.59978 (10) | 0.3825 (3) | 0.0230 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0168 (9) | 0.0191 (10) | 0.0233 (11) | −0.0034 (8) | −0.0028 (9) | 0.0002 (8) |
C2 | 0.0161 (9) | 0.0214 (10) | 0.0192 (9) | −0.0031 (7) | −0.0007 (8) | −0.0010 (8) |
C3 | 0.0167 (9) | 0.0178 (10) | 0.0240 (10) | −0.0027 (7) | −0.0020 (8) | −0.0022 (8) |
C4 | 0.0229 (10) | 0.0232 (10) | 0.0226 (11) | −0.0063 (8) | −0.0002 (9) | 0.0016 (8) |
C5 | 0.0231 (11) | 0.0299 (11) | 0.0242 (12) | −0.0059 (9) | 0.0046 (9) | −0.0048 (9) |
C6 | 0.0194 (10) | 0.0239 (10) | 0.0290 (11) | −0.0001 (8) | 0.0013 (9) | −0.0067 (9) |
O1 | 0.0172 (7) | 0.0210 (7) | 0.0308 (8) | 0.0006 (5) | −0.0023 (6) | 0.0028 (6) |
Geometric parameters (Å, º) top
C1—C6 | 1.378 (3) | C3—C4 | 1.387 (3) |
C1—C2 | 1.389 (3) | C4—C5 | 1.383 (3) |
C1—O1 | 1.396 (2) | C4—H4 | 0.95 |
C2—C3 | 1.386 (3) | C5—C6 | 1.390 (3) |
C2—H2 | 0.95 | C5—H5 | 0.95 |
C3—O1i | 1.385 (2) | C6—H6 | 0.95 |
| | | |
C6—C1—C2 | 122.48 (18) | C5—C4—H4 | 120.4 |
C6—C1—O1 | 118.45 (17) | C3—C4—H4 | 120.4 |
C2—C1—O1 | 118.99 (17) | C4—C5—C6 | 121.07 (19) |
C3—C2—C1 | 117.86 (18) | C4—C5—H5 | 119.5 |
C3—C2—H2 | 121.1 | C6—C5—H5 | 119.5 |
C1—C2—H2 | 121.1 | C1—C6—C5 | 118.15 (18) |
O1i—C3—C4 | 116.14 (17) | C1—C6—H6 | 120.9 |
O1i—C3—C2 | 122.56 (18) | C5—C6—H6 | 120.9 |
C4—C3—C2 | 121.18 (18) | C3ii—O1—C1 | 117.50 (15) |
C5—C4—C3 | 119.24 (18) | | |
| | | |
C6—C1—C2—C3 | −1.6 (3) | C3—C4—C5—C6 | −1.4 (3) |
O1—C1—C2—C3 | −178.32 (17) | C2—C1—C6—C5 | 1.1 (3) |
C1—C2—C3—O1i | 176.47 (16) | O1—C1—C6—C5 | 177.89 (17) |
C1—C2—C3—C4 | 0.5 (3) | C4—C5—C6—C1 | 0.4 (3) |
O1i—C3—C4—C5 | −175.28 (18) | C6—C1—O1—C3ii | 119.23 (19) |
C2—C3—C4—C5 | 0.9 (3) | C2—C1—O1—C3ii | −63.9 (2) |
Symmetry codes: (i) −y+1, x, −z+1; (ii) y, −x+1, −z+1. |
2,8,14,20-Tetraoxapentacyclo[19.3.1.1
3,7.1
9,13.1
15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15(26),16,18,21,23-dodecaene (II)
top
Crystal data top
C24H16O4 | F(000) = 768 |
Mr = 368.37 | Dx = 1.370 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.0935 (13) Å | Cell parameters from 161 reflections |
b = 5.4475 (4) Å | θ = 3.9–26.2° |
c = 18.9054 (12) Å | µ = 0.09 mm−1 |
β = 114.732 (2)° | T = 100 K |
V = 1786.0 (2) Å3 | Block, colorless |
Z = 4 | 0.25 × 0.19 × 0.11 mm |
Data collection top
Bruker D8 goniometer diffractometer | 1503 reflections with I > 2σ(I) |
Detector resolution: 7.3910 pixels mm-1 | Rint = 0.049 |
φ and ω scans | θmax = 26.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2017) | h = −23→23 |
Tmin = 0.92, Tmax = 0.99 | k = −6→6 |
10409 measured reflections | l = −23→23 |
1783 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-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 reflections | Δρmax = 0.19 e Å−3 |
127 parameters | Δρmin = −0.25 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
C1 | 0.65630 (7) | 0.5039 (2) | 0.77396 (7) | 0.0175 (3) | |
C2 | 0.60352 (7) | 0.3450 (2) | 0.72122 (7) | 0.0183 (3) | |
H2 | 0.585775 | 0.204098 | 0.738474 | 0.022* | |
C3 | 0.57731 (7) | 0.3974 (2) | 0.64244 (7) | 0.0183 (3) | |
C4 | 0.60323 (8) | 0.5976 (3) | 0.61580 (8) | 0.0214 (3) | |
H4 | 0.58481 | 0.629108 | 0.561568 | 0.026* | |
C5 | 0.65700 (8) | 0.7530 (3) | 0.66999 (8) | 0.0224 (3) | |
H5 | 0.675739 | 0.891151 | 0.652531 | 0.027* | |
C6 | 0.68340 (7) | 0.7082 (2) | 0.74899 (8) | 0.0200 (3) | |
H6 | 0.719636 | 0.815697 | 0.785742 | 0.024* | |
C7 | 0.45545 (7) | 0.1936 (2) | 0.58891 (7) | 0.0177 (3) | |
C8 | 0.42206 (7) | 0.3547 (2) | 0.62244 (7) | 0.0183 (3) | |
H8 | 0.448357 | 0.498773 | 0.648344 | 0.022* | |
C9 | 0.34904 (7) | 0.2995 (2) | 0.61709 (7) | 0.0178 (3) | |
C10 | 0.30943 (8) | 0.0925 (2) | 0.57930 (7) | 0.0207 (3) | |
H10 | 0.259616 | 0.057578 | 0.576579 | 0.025* | |
C11 | 0.34404 (8) | −0.0639 (3) | 0.54529 (8) | 0.0237 (3) | |
H11 | 0.31721 | −0.206055 | 0.518414 | 0.028* | |
C12 | 0.41700 (8) | −0.0155 (2) | 0.55002 (7) | 0.0208 (3) | |
H12 | 0.44044 | −0.123899 | 0.526959 | 0.025* | |
O1 | 0.68795 (5) | 0.46424 (18) | 0.85344 (5) | 0.0207 (2) | |
O2 | 0.52634 (5) | 0.23700 (18) | 0.58748 (5) | 0.0219 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0162 (6) | 0.0206 (6) | 0.0177 (6) | 0.0032 (5) | 0.0092 (5) | 0.0005 (5) |
C2 | 0.0188 (7) | 0.0184 (6) | 0.0213 (7) | −0.0002 (5) | 0.0120 (6) | 0.0007 (5) |
C3 | 0.0152 (6) | 0.0220 (7) | 0.0189 (6) | 0.0007 (5) | 0.0085 (5) | −0.0025 (5) |
C4 | 0.0200 (7) | 0.0270 (7) | 0.0194 (6) | 0.0026 (6) | 0.0104 (6) | 0.0043 (6) |
C5 | 0.0206 (7) | 0.0211 (7) | 0.0282 (7) | 0.0001 (5) | 0.0129 (6) | 0.0054 (6) |
C6 | 0.0170 (6) | 0.0188 (6) | 0.0253 (7) | 0.0000 (5) | 0.0100 (6) | −0.0012 (6) |
C7 | 0.0174 (6) | 0.0228 (7) | 0.0134 (6) | 0.0001 (5) | 0.0070 (5) | 0.0034 (5) |
C8 | 0.0208 (7) | 0.0186 (6) | 0.0148 (6) | −0.0018 (5) | 0.0067 (5) | −0.0004 (5) |
C9 | 0.0196 (6) | 0.0213 (6) | 0.0122 (6) | 0.0039 (5) | 0.0063 (5) | 0.0024 (5) |
C10 | 0.0181 (7) | 0.0242 (7) | 0.0190 (6) | −0.0023 (5) | 0.0071 (6) | 0.0011 (6) |
C11 | 0.0249 (7) | 0.0215 (7) | 0.0230 (7) | −0.0045 (6) | 0.0082 (6) | −0.0028 (6) |
C12 | 0.0247 (7) | 0.0203 (7) | 0.0182 (6) | 0.0021 (5) | 0.0098 (6) | −0.0011 (5) |
O1 | 0.0188 (5) | 0.0257 (5) | 0.0175 (5) | −0.0046 (4) | 0.0074 (4) | 0.0012 (4) |
O2 | 0.0201 (5) | 0.0295 (5) | 0.0191 (5) | −0.0050 (4) | 0.0111 (4) | −0.0064 (4) |
Geometric parameters (Å, º) top
C1—O1 | 1.3820 (15) | C7—C8 | 1.3844 (18) |
C1—C2 | 1.3853 (18) | C7—O2 | 1.3853 (15) |
C1—C6 | 1.3902 (19) | C7—C12 | 1.3874 (19) |
C2—C3 | 1.3880 (18) | C8—C9 | 1.3881 (18) |
C2—H2 | 0.95 | C8—H8 | 0.95 |
C3—C4 | 1.3773 (19) | C9—C10 | 1.3789 (19) |
C3—O2 | 1.3943 (16) | C9—O1i | 1.3944 (16) |
C4—C5 | 1.393 (2) | C10—C11 | 1.3896 (19) |
C4—H4 | 0.95 | C10—H10 | 0.95 |
C5—C6 | 1.3835 (19) | C11—C12 | 1.3835 (19) |
C5—H5 | 0.95 | C11—H11 | 0.95 |
C6—H6 | 0.95 | C12—H12 | 0.95 |
| | | |
O1—C1—C2 | 122.70 (12) | C8—C7—C12 | 121.33 (12) |
O1—C1—C6 | 116.03 (11) | O2—C7—C12 | 115.77 (11) |
C2—C1—C6 | 121.19 (12) | C7—C8—C9 | 118.05 (12) |
C1—C2—C3 | 118.09 (12) | C7—C8—H8 | 121.0 |
C1—C2—H2 | 121.0 | C9—C8—H8 | 121.0 |
C3—C2—H2 | 121.0 | C10—C9—C8 | 122.09 (12) |
C4—C3—C2 | 122.14 (12) | C10—C9—O1i | 118.28 (11) |
C4—C3—O2 | 117.99 (11) | C8—C9—O1i | 119.51 (12) |
C2—C3—O2 | 119.77 (12) | C9—C10—C11 | 118.50 (12) |
C3—C4—C5 | 118.63 (12) | C9—C10—H10 | 120.8 |
C3—C4—H4 | 120.7 | C11—C10—H10 | 120.8 |
C5—C4—H4 | 120.7 | C12—C11—C10 | 120.94 (13) |
C6—C5—C4 | 120.69 (13) | C12—C11—H11 | 119.5 |
C6—C5—H5 | 119.7 | C10—C11—H11 | 119.5 |
C4—C5—H5 | 119.7 | C11—C12—C7 | 119.08 (12) |
C5—C6—C1 | 119.24 (12) | C11—C12—H12 | 120.5 |
C5—C6—H6 | 120.4 | C7—C12—H12 | 120.5 |
C1—C6—H6 | 120.4 | C1—O1—C9i | 118.10 (10) |
C8—C7—O2 | 122.78 (12) | C7—O2—C3 | 118.39 (10) |
| | | |
O1—C1—C2—C3 | −177.77 (11) | C7—C8—C9—O1i | −176.60 (11) |
C6—C1—C2—C3 | −1.06 (19) | C8—C9—C10—C11 | −0.38 (19) |
C1—C2—C3—C4 | 1.32 (19) | O1i—C9—C10—C11 | 175.76 (11) |
C1—C2—C3—O2 | 177.66 (11) | C9—C10—C11—C12 | 0.9 (2) |
C2—C3—C4—C5 | −0.6 (2) | C10—C11—C12—C7 | −0.5 (2) |
O2—C3—C4—C5 | −176.96 (11) | C8—C7—C12—C11 | −0.45 (19) |
C3—C4—C5—C6 | −0.5 (2) | O2—C7—C12—C11 | −176.52 (11) |
C4—C5—C6—C1 | 0.7 (2) | C2—C1—O1—C9i | −17.78 (17) |
O1—C1—C6—C5 | 176.99 (11) | C6—C1—O1—C9i | 165.35 (11) |
C2—C1—C6—C5 | 0.07 (19) | C8—C7—O2—C3 | 22.27 (17) |
O2—C7—C8—C9 | 176.71 (11) | C12—C7—O2—C3 | −161.72 (11) |
C12—C7—C8—C9 | 0.92 (19) | C4—C3—O2—C7 | −122.97 (13) |
C7—C8—C9—C10 | −0.50 (19) | C2—C3—O2—C7 | 60.54 (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) topType | Conformation | A | B | C | D | ΔG |
c | 1,3-altenate, C2 | 128.3 | -126.9 | 128.3 | -126.9 | 0.0 |
d | 1,3-altenate, S4 | 123.6 | -123.6 | 123.6 | -123.6 | 0.5 |
h | Chair, C2h | 95.9 | 178.7 | -95.9 | 178.7 | 6.6 |