Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107008566/sq3058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107008566/sq3058Isup2.hkl |
CCDC reference: 652516
For related literature, see: Ajtai & Burghardt (1995); Balzani et al. (2000); Cody (1987); Feringa (2001); Kelly et al. (1994); Stoddart & Tseng (2002); Tremayne et al. (1997); Wang et al. (2001); Willner et al. (1997); Yamaguchi et al. (1997).
Fluorescein (Amount?) was dissolved in methanol (Volume?) along with a catalytic amount of concentrated sulfuric acid. The orange–red solution was refluxed for 12 h and was then poured into ice–water (100 ml). The resulting precipitate was filtered off to yield the product as an orange solid. This isolated product (Amount?) was added to dimethylformamide (Volume?) followed by potassium carbonate (Amount?) and 11-bromo-undecan-1-ol (Amount?), and the mixture was then heated at 333 K for 2 d. The resulting red precipitate was filtered off and washed with aqueous sodium hydroxide. The product was then solubilized in anhydrous tetrahydrofuran along with sodium hydride. The mixture was subsequently refluxed for 8 h and the title compound, (I), was isolated in 41% yield after column chromatography. Compound (I) was crystallized by slow diffusion of hexanes into a saturated solution of the compound in diisopropyl ether.
H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 2003); cell refinement: SMART; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1997) and SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (Marris, 2004).
C31H32O5 | Z = 2 |
Mr = 484.57 | F(000) = 516 |
Triclinic, P1 | Dx = 1.261 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 7.9010 (9) Å | Cell parameters from 2494 reflections |
b = 12.7844 (13) Å | θ = 42.0–65.3° |
c = 12.9683 (14) Å | µ = 0.68 mm−1 |
α = 91.895 (2)° | T = 100 K |
β = 102.655 (3)° | Block, yellow |
γ = 92.167 (3)° | 0.18 × 0.16 × 0.11 mm |
V = 1276.0 (2) Å3 |
Bruker Microstar diffractometer | 3831 independent reflections |
Radiation source: Micro source | 3392 reflections with I > 2σ(I) |
Helios optics monochromator | Rint = 0.024 |
Detector resolution: 5.5 pixels mm-1 | θmax = 65.7°, θmin = 3.5° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.804, Tmax = 0.931 | l = −15→15 |
4699 measured reflections |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0904P)2 + 0.243P] where P = (Fo2 + 2Fc2)/3 |
3831 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C31H32O5 | γ = 92.167 (3)° |
Mr = 484.57 | V = 1276.0 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9010 (9) Å | Cu Kα radiation |
b = 12.7844 (13) Å | µ = 0.68 mm−1 |
c = 12.9683 (14) Å | T = 100 K |
α = 91.895 (2)° | 0.18 × 0.16 × 0.11 mm |
β = 102.655 (3)° |
Bruker Microstar diffractometer | 3831 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3392 reflections with I > 2σ(I) |
Tmin = 0.804, Tmax = 0.931 | Rint = 0.024 |
4699 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.24 e Å−3 |
3831 reflections | Δρmin = −0.24 e Å−3 |
325 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 | ||
O1 | 0.26332 (14) | 0.96074 (7) | 0.53997 (7) | 0.0163 (3) | |
O2 | 0.70831 (16) | 1.17496 (8) | 0.75752 (9) | 0.0252 (3) | |
O3 | 0.41286 (16) | 0.73500 (9) | 0.95279 (8) | 0.0286 (3) | |
O4 | 0.31487 (14) | 0.74150 (7) | 0.77611 (7) | 0.0162 (3) | |
O5 | −0.15862 (14) | 0.75431 (7) | 0.30093 (8) | 0.0186 (3) | |
C1 | 0.0429 (2) | 0.86821 (11) | 0.61197 (11) | 0.0153 (3) | |
C2 | −0.1044 (2) | 0.79814 (11) | 0.58950 (11) | 0.0170 (3) | |
H2 | −0.1561 | 0.7777 | 0.6457 | 0.020* | |
C3 | −0.1758 (2) | 0.75835 (11) | 0.48769 (12) | 0.0180 (3) | |
H3 | −0.2756 | 0.7119 | 0.4745 | 0.022* | |
C4 | −0.0986 (2) | 0.78758 (10) | 0.40396 (11) | 0.0156 (3) | |
C5 | 0.0494 (2) | 0.85553 (10) | 0.42302 (11) | 0.0154 (3) | |
H5 | 0.1027 | 0.8743 | 0.3669 | 0.018* | |
C6 | 0.1165 (2) | 0.89482 (10) | 0.52570 (11) | 0.0141 (3) | |
C7 | 0.3409 (2) | 1.00386 (11) | 0.63895 (11) | 0.0151 (3) | |
C8 | 0.4853 (2) | 1.06742 (11) | 0.64617 (11) | 0.0169 (3) | |
H8 | 0.5284 | 1.0800 | 0.5846 | 0.020* | |
C9 | 0.5745 (2) | 1.11650 (11) | 0.74759 (12) | 0.0189 (4) | |
C10 | 0.4985 (2) | 1.09401 (11) | 0.83952 (12) | 0.0193 (4) | |
H10 | 0.5513 | 1.1257 | 0.9067 | 0.023* | |
C11 | 0.3559 (2) | 1.02951 (11) | 0.83032 (11) | 0.0175 (3) | |
H11 | 0.3123 | 1.0165 | 0.8916 | 0.021* | |
C12 | 0.2669 (2) | 0.97935 (10) | 0.72952 (11) | 0.0149 (3) | |
C13 | 0.1241 (2) | 0.91083 (10) | 0.71682 (11) | 0.0146 (3) | |
C14 | 0.0520 (2) | 0.88019 (10) | 0.81032 (11) | 0.0149 (3) | |
C15 | −0.1002 (2) | 0.92336 (11) | 0.82502 (12) | 0.0210 (4) | |
H15 | −0.1604 | 0.9683 | 0.7739 | 0.025* | |
C16 | −0.1662 (2) | 0.90136 (12) | 0.91458 (12) | 0.0227 (4) | |
H16 | −0.2719 | 0.9299 | 0.9230 | 0.027* | |
C17 | −0.0761 (2) | 0.83749 (11) | 0.99121 (12) | 0.0218 (4) | |
H17 | −0.1191 | 0.8238 | 1.0526 | 0.026* | |
C18 | 0.0764 (2) | 0.79394 (11) | 0.97775 (11) | 0.0175 (3) | |
H18 | 0.1375 | 0.7508 | 1.0303 | 0.021* | |
C19 | 0.1413 (2) | 0.81314 (10) | 0.88705 (11) | 0.0146 (3) | |
C20 | 0.3036 (2) | 0.76046 (10) | 0.87735 (11) | 0.0160 (3) | |
C21 | 0.4714 (2) | 0.69102 (11) | 0.76174 (12) | 0.0191 (4) | |
H21A | 0.4706 | 0.6181 | 0.7853 | 0.023* | |
H21B | 0.5760 | 0.7296 | 0.8041 | 0.023* | |
C22 | 0.4739 (2) | 0.69153 (11) | 0.64483 (12) | 0.0190 (4) | |
H22A | 0.5851 | 0.6639 | 0.6353 | 0.023* | |
H22B | 0.4707 | 0.7650 | 0.6228 | 0.023* | |
C23 | 0.3242 (2) | 0.62741 (11) | 0.57123 (11) | 0.0184 (4) | |
H23A | 0.2134 | 0.6606 | 0.5722 | 0.022* | |
H23B | 0.3171 | 0.5560 | 0.5978 | 0.022* | |
C24 | 0.3488 (2) | 0.61966 (11) | 0.45671 (11) | 0.0191 (4) | |
H24A | 0.3521 | 0.6911 | 0.4299 | 0.023* | |
H24B | 0.4623 | 0.5893 | 0.4567 | 0.023* | |
C25 | 0.2054 (2) | 0.55266 (11) | 0.38085 (12) | 0.0204 (4) | |
H25A | 0.0920 | 0.5840 | 0.3785 | 0.024* | |
H25B | 0.1997 | 0.4814 | 0.4080 | 0.024* | |
C26 | 0.2384 (2) | 0.54468 (12) | 0.26808 (12) | 0.0226 (4) | |
H26A | 0.3576 | 0.5212 | 0.2722 | 0.027* | |
H26B | 0.2323 | 0.6153 | 0.2388 | 0.027* | |
C27 | 0.1090 (2) | 0.46876 (12) | 0.19075 (13) | 0.0272 (4) | |
H27A | 0.1363 | 0.4715 | 0.1199 | 0.033* | |
H27B | 0.1269 | 0.3965 | 0.2148 | 0.033* | |
C28 | −0.0827 (2) | 0.49196 (12) | 0.18052 (12) | 0.0242 (4) | |
H28A | −0.1111 | 0.4867 | 0.2509 | 0.029* | |
H28B | −0.1547 | 0.4374 | 0.1328 | 0.029* | |
C29 | −0.1330 (2) | 0.60021 (12) | 0.13807 (12) | 0.0227 (4) | |
H29A | −0.0392 | 0.6525 | 0.1704 | 0.027* | |
H29B | −0.1417 | 0.5978 | 0.0607 | 0.027* | |
C30 | −0.3052 (2) | 0.63661 (12) | 0.16031 (12) | 0.0232 (4) | |
H30A | −0.3438 | 0.6963 | 0.1156 | 0.028* | |
H30B | −0.3947 | 0.5789 | 0.1401 | 0.028* | |
C31 | −0.2917 (2) | 0.66999 (11) | 0.27598 (12) | 0.0195 (4) | |
H31A | −0.4043 | 0.6947 | 0.2864 | 0.023* | |
H31B | −0.2588 | 0.6105 | 0.3220 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0172 (6) | 0.0187 (5) | 0.0133 (5) | −0.0031 (4) | 0.0047 (4) | −0.0009 (4) |
O2 | 0.0219 (7) | 0.0272 (6) | 0.0261 (6) | −0.0068 (5) | 0.0064 (5) | −0.0033 (5) |
O3 | 0.0269 (8) | 0.0407 (7) | 0.0157 (6) | 0.0136 (5) | −0.0026 (5) | −0.0012 (5) |
O4 | 0.0162 (6) | 0.0196 (5) | 0.0137 (5) | 0.0061 (4) | 0.0042 (4) | 0.0006 (4) |
O5 | 0.0207 (7) | 0.0193 (5) | 0.0146 (5) | −0.0044 (4) | 0.0024 (4) | −0.0002 (4) |
C1 | 0.0181 (9) | 0.0135 (7) | 0.0154 (7) | 0.0049 (6) | 0.0048 (6) | 0.0029 (5) |
C2 | 0.0170 (9) | 0.0190 (7) | 0.0173 (7) | 0.0022 (6) | 0.0076 (6) | 0.0050 (6) |
C3 | 0.0155 (9) | 0.0182 (7) | 0.0202 (8) | −0.0006 (6) | 0.0040 (6) | 0.0029 (6) |
C4 | 0.0181 (9) | 0.0135 (7) | 0.0147 (7) | 0.0045 (6) | 0.0018 (6) | 0.0013 (5) |
C5 | 0.0185 (9) | 0.0151 (7) | 0.0138 (7) | 0.0022 (6) | 0.0055 (6) | 0.0030 (5) |
C6 | 0.0134 (8) | 0.0123 (7) | 0.0177 (7) | 0.0023 (5) | 0.0051 (6) | 0.0025 (5) |
C7 | 0.0175 (9) | 0.0144 (7) | 0.0135 (7) | 0.0056 (6) | 0.0031 (6) | 0.0008 (5) |
C8 | 0.0180 (9) | 0.0184 (7) | 0.0154 (7) | 0.0010 (6) | 0.0061 (6) | 0.0013 (6) |
C9 | 0.0197 (9) | 0.0147 (7) | 0.0219 (8) | 0.0025 (6) | 0.0035 (7) | 0.0002 (6) |
C10 | 0.0224 (10) | 0.0184 (7) | 0.0159 (7) | 0.0031 (6) | 0.0020 (7) | −0.0023 (6) |
C11 | 0.0229 (10) | 0.0165 (7) | 0.0143 (7) | 0.0041 (6) | 0.0061 (6) | 0.0012 (5) |
C12 | 0.0180 (9) | 0.0131 (7) | 0.0149 (7) | 0.0052 (6) | 0.0054 (6) | 0.0030 (5) |
C13 | 0.0163 (9) | 0.0123 (7) | 0.0167 (7) | 0.0067 (5) | 0.0057 (6) | 0.0035 (5) |
C14 | 0.0171 (9) | 0.0140 (7) | 0.0134 (7) | −0.0004 (5) | 0.0035 (6) | −0.0007 (5) |
C15 | 0.0224 (10) | 0.0226 (8) | 0.0194 (8) | 0.0072 (6) | 0.0063 (7) | 0.0042 (6) |
C16 | 0.0208 (10) | 0.0259 (8) | 0.0247 (8) | 0.0056 (6) | 0.0114 (7) | −0.0005 (6) |
C17 | 0.0281 (10) | 0.0223 (8) | 0.0185 (8) | −0.0007 (6) | 0.0131 (7) | 0.0014 (6) |
C18 | 0.0223 (9) | 0.0154 (7) | 0.0149 (7) | −0.0011 (6) | 0.0048 (6) | 0.0007 (5) |
C19 | 0.0168 (8) | 0.0127 (7) | 0.0132 (7) | −0.0025 (5) | 0.0022 (6) | −0.0024 (5) |
C20 | 0.0192 (9) | 0.0150 (7) | 0.0130 (7) | 0.0000 (6) | 0.0025 (6) | −0.0004 (5) |
C21 | 0.0149 (9) | 0.0221 (8) | 0.0211 (8) | 0.0058 (6) | 0.0050 (6) | −0.0002 (6) |
C22 | 0.0167 (9) | 0.0206 (7) | 0.0222 (8) | 0.0028 (6) | 0.0093 (6) | 0.0006 (6) |
C23 | 0.0184 (9) | 0.0184 (7) | 0.0204 (8) | 0.0024 (6) | 0.0080 (6) | 0.0010 (6) |
C24 | 0.0204 (9) | 0.0182 (7) | 0.0201 (8) | 0.0026 (6) | 0.0069 (6) | 0.0001 (6) |
C25 | 0.0204 (9) | 0.0198 (7) | 0.0219 (8) | 0.0022 (6) | 0.0065 (7) | −0.0002 (6) |
C26 | 0.0245 (10) | 0.0221 (8) | 0.0224 (8) | 0.0025 (6) | 0.0078 (7) | −0.0015 (6) |
C27 | 0.0354 (11) | 0.0224 (8) | 0.0238 (8) | 0.0018 (7) | 0.0076 (7) | −0.0046 (6) |
C28 | 0.0292 (10) | 0.0193 (8) | 0.0232 (8) | −0.0031 (6) | 0.0057 (7) | −0.0040 (6) |
C29 | 0.0319 (11) | 0.0210 (8) | 0.0149 (7) | −0.0030 (6) | 0.0056 (7) | −0.0014 (6) |
C30 | 0.0254 (10) | 0.0203 (8) | 0.0197 (8) | −0.0031 (6) | −0.0031 (7) | 0.0010 (6) |
C31 | 0.0168 (9) | 0.0180 (7) | 0.0226 (8) | −0.0023 (6) | 0.0023 (6) | 0.0007 (6) |
O1—C7 | 1.3821 (17) | C17—H17 | 0.95 |
O1—C6 | 1.3826 (18) | C18—C19 | 1.407 (2) |
O2—C9 | 1.252 (2) | C18—H18 | 0.95 |
O3—C20 | 1.2167 (18) | C19—C20 | 1.498 (2) |
O4—C20 | 1.3498 (17) | C21—C22 | 1.521 (2) |
O4—C21 | 1.4612 (19) | C21—H21A | 0.99 |
O5—C4 | 1.3640 (17) | C21—H21B | 0.99 |
O5—C31 | 1.4542 (17) | C22—C23 | 1.537 (2) |
C1—C2 | 1.413 (2) | C22—H22A | 0.99 |
C1—C6 | 1.414 (2) | C22—H22B | 0.99 |
C1—C13 | 1.449 (2) | C23—C24 | 1.540 (2) |
C2—C3 | 1.388 (2) | C23—H23A | 0.99 |
C2—H2 | 0.95 | C23—H23B | 0.99 |
C3—C4 | 1.411 (2) | C24—C25 | 1.539 (2) |
C3—H3 | 0.95 | C24—H24A | 0.99 |
C4—C5 | 1.402 (2) | C24—H24B | 0.99 |
C5—C6 | 1.390 (2) | C25—C26 | 1.542 (2) |
C5—H5 | 0.95 | C25—H25A | 0.99 |
C7—C8 | 1.360 (2) | C25—H25B | 0.99 |
C7—C12 | 1.460 (2) | C26—C27 | 1.551 (2) |
C8—C9 | 1.458 (2) | C26—H26A | 0.99 |
C8—H8 | 0.95 | C26—H26B | 0.99 |
C9—C10 | 1.479 (2) | C27—C28 | 1.533 (3) |
C10—C11 | 1.352 (2) | C27—H27A | 0.99 |
C10—H10 | 0.95 | C27—H27B | 0.99 |
C11—C12 | 1.457 (2) | C28—C29 | 1.540 (2) |
C11—H11 | 0.95 | C28—H28A | 0.99 |
C12—C13 | 1.379 (2) | C28—H28B | 0.99 |
C13—C14 | 1.505 (2) | C29—C30 | 1.537 (3) |
C14—C15 | 1.390 (2) | C29—H29A | 0.99 |
C14—C19 | 1.4203 (19) | C29—H29B | 0.99 |
C15—C16 | 1.406 (2) | C30—C31 | 1.526 (2) |
C15—H15 | 0.95 | C30—H30A | 0.99 |
C16—C17 | 1.396 (2) | C30—H30B | 0.99 |
C16—H16 | 0.95 | C31—H31A | 0.99 |
C17—C18 | 1.389 (2) | C31—H31B | 0.99 |
C7—O1—C6 | 120.83 (12) | C22—C21—H21A | 110.1 |
C20—O4—C21 | 115.67 (11) | O4—C21—H21B | 110.1 |
C4—O5—C31 | 118.92 (12) | C22—C21—H21B | 110.1 |
C2—C1—C6 | 116.72 (13) | H21A—C21—H21B | 108.4 |
C2—C1—C13 | 124.23 (14) | C21—C22—C23 | 115.05 (13) |
C6—C1—C13 | 119.02 (14) | C21—C22—H22A | 108.5 |
C3—C2—C1 | 121.97 (14) | C23—C22—H22A | 108.5 |
C3—C2—H2 | 119 | C21—C22—H22B | 108.5 |
C1—C2—H2 | 119 | C23—C22—H22B | 108.5 |
C2—C3—C4 | 119.33 (14) | H22A—C22—H22B | 107.5 |
C2—C3—H3 | 120.3 | C22—C23—C24 | 111.90 (13) |
C4—C3—H3 | 120.3 | C22—C23—H23A | 109.2 |
O5—C4—C5 | 115.05 (13) | C24—C23—H23A | 109.2 |
O5—C4—C3 | 124.38 (14) | C22—C23—H23B | 109.2 |
C5—C4—C3 | 120.57 (13) | C24—C23—H23B | 109.2 |
C6—C5—C4 | 118.63 (14) | H23A—C23—H23B | 107.9 |
C6—C5—H5 | 120.7 | C25—C24—C23 | 113.78 (13) |
C4—C5—H5 | 120.7 | C25—C24—H24A | 108.8 |
O1—C6—C5 | 116.11 (13) | C23—C24—H24A | 108.8 |
O1—C6—C1 | 121.11 (13) | C25—C24—H24B | 108.8 |
C5—C6—C1 | 122.76 (14) | C23—C24—H24B | 108.8 |
C8—C7—O1 | 117.07 (13) | H24A—C24—H24B | 107.7 |
C8—C7—C12 | 123.39 (13) | C24—C25—C26 | 111.85 (13) |
O1—C7—C12 | 119.54 (13) | C24—C25—H25A | 109.2 |
C7—C8—C9 | 120.56 (14) | C26—C25—H25A | 109.2 |
C7—C8—H8 | 119.7 | C24—C25—H25B | 109.2 |
C9—C8—H8 | 119.7 | C26—C25—H25B | 109.2 |
O2—C9—C8 | 122.43 (15) | H25A—C25—H25B | 107.9 |
O2—C9—C10 | 121.05 (14) | C25—C26—C27 | 114.30 (14) |
C8—C9—C10 | 116.52 (14) | C25—C26—H26A | 108.7 |
C11—C10—C9 | 121.68 (13) | C27—C26—H26A | 108.7 |
C11—C10—H10 | 119.2 | C25—C26—H26B | 108.7 |
C9—C10—H10 | 119.2 | C27—C26—H26B | 108.7 |
C10—C11—C12 | 122.15 (14) | H26A—C26—H26B | 107.6 |
C10—C11—H11 | 118.9 | C28—C27—C26 | 114.70 (13) |
C12—C11—H11 | 118.9 | C28—C27—H27A | 108.6 |
C13—C12—C11 | 124.21 (14) | C26—C27—H27A | 108.6 |
C13—C12—C7 | 120.10 (13) | C28—C27—H27B | 108.6 |
C11—C12—C7 | 115.67 (14) | C26—C27—H27B | 108.6 |
C12—C13—C1 | 119.33 (14) | H27A—C27—H27B | 107.6 |
C12—C13—C14 | 120.80 (13) | C27—C28—C29 | 114.69 (14) |
C1—C13—C14 | 119.87 (13) | C27—C28—H28A | 108.6 |
C15—C14—C19 | 119.30 (14) | C29—C28—H28A | 108.6 |
C15—C14—C13 | 119.12 (12) | C27—C28—H28B | 108.6 |
C19—C14—C13 | 121.48 (14) | C29—C28—H28B | 108.6 |
C14—C15—C16 | 120.77 (14) | H28A—C28—H28B | 107.6 |
C14—C15—H15 | 119.6 | C30—C29—C28 | 113.93 (13) |
C16—C15—H15 | 119.6 | C30—C29—H29A | 108.8 |
C17—C16—C15 | 119.88 (15) | C28—C29—H29A | 108.8 |
C17—C16—H16 | 120.1 | C30—C29—H29B | 108.8 |
C15—C16—H16 | 120.1 | C28—C29—H29B | 108.8 |
C18—C17—C16 | 120.01 (14) | H29A—C29—H29B | 107.7 |
C18—C17—H17 | 120 | C31—C30—C29 | 113.08 (12) |
C16—C17—H17 | 120 | C31—C30—H30A | 109 |
C17—C18—C19 | 120.63 (13) | C29—C30—H30A | 109 |
C17—C18—H18 | 119.7 | C31—C30—H30B | 109 |
C19—C18—H18 | 119.7 | C29—C30—H30B | 109 |
C18—C19—C14 | 119.38 (14) | H30A—C30—H30B | 107.8 |
C18—C19—C20 | 117.11 (12) | O5—C31—C30 | 106.36 (13) |
C14—C19—C20 | 123.52 (13) | O5—C31—H31A | 110.5 |
O3—C20—O4 | 123.11 (15) | C30—C31—H31A | 110.5 |
O3—C20—C19 | 123.65 (13) | O5—C31—H31B | 110.5 |
O4—C20—C19 | 113.22 (12) | C30—C31—H31B | 110.5 |
O4—C21—C22 | 107.88 (11) | H31A—C31—H31B | 108.6 |
O4—C21—H21A | 110.1 | ||
C6—C1—C2—C3 | −1.0 (2) | C6—C1—C13—C12 | 2.5 (2) |
C13—C1—C2—C3 | −179.05 (13) | C2—C1—C13—C14 | 0.4 (2) |
C1—C2—C3—C4 | 0.6 (2) | C6—C1—C13—C14 | −177.63 (12) |
C31—O5—C4—C5 | 169.31 (12) | C12—C13—C14—C15 | 104.52 (17) |
C31—O5—C4—C3 | −11.0 (2) | C1—C13—C14—C15 | −75.38 (17) |
C2—C3—C4—O5 | −179.26 (13) | C12—C13—C14—C19 | −71.70 (18) |
C2—C3—C4—C5 | 0.4 (2) | C1—C13—C14—C19 | 108.39 (16) |
O5—C4—C5—C6 | 178.63 (11) | C19—C14—C15—C16 | 0.0 (2) |
C3—C4—C5—C6 | −1.1 (2) | C13—C14—C15—C16 | −176.33 (13) |
C7—O1—C6—C5 | −179.79 (11) | C14—C15—C16—C17 | 1.6 (2) |
C7—O1—C6—C1 | −1.0 (2) | C15—C16—C17—C18 | −1.4 (2) |
C4—C5—C6—O1 | 179.48 (11) | C16—C17—C18—C19 | −0.3 (2) |
C4—C5—C6—C1 | 0.7 (2) | C17—C18—C19—C14 | 1.8 (2) |
C2—C1—C6—O1 | −178.40 (12) | C17—C18—C19—C20 | −178.19 (12) |
C13—C1—C6—O1 | −0.2 (2) | C15—C14—C19—C18 | −1.7 (2) |
C2—C1—C6—C5 | 0.3 (2) | C13—C14—C19—C18 | 174.56 (12) |
C13—C1—C6—C5 | 178.46 (13) | C15—C14—C19—C20 | 178.36 (13) |
C6—O1—C7—C8 | 179.69 (12) | C13—C14—C19—C20 | −5.4 (2) |
C6—O1—C7—C12 | 0.07 (19) | C21—O4—C20—O3 | −2.1 (2) |
O1—C7—C8—C9 | 179.69 (11) | C21—O4—C20—C19 | 179.47 (11) |
C12—C7—C8—C9 | −0.7 (2) | C18—C19—C20—O3 | −27.0 (2) |
C7—C8—C9—O2 | 179.56 (14) | C14—C19—C20—O3 | 152.99 (15) |
C7—C8—C9—C10 | −0.6 (2) | C18—C19—C20—O4 | 151.42 (12) |
O2—C9—C10—C11 | −178.78 (14) | C14—C19—C20—O4 | −28.60 (18) |
C8—C9—C10—C11 | 1.4 (2) | C20—O4—C21—C22 | −171.42 (11) |
C9—C10—C11—C12 | −0.8 (2) | O4—C21—C22—C23 | −63.84 (15) |
C10—C11—C12—C13 | 178.13 (14) | C21—C22—C23—C24 | −172.41 (12) |
C10—C11—C12—C7 | −0.5 (2) | C22—C23—C24—C25 | 177.85 (12) |
C8—C7—C12—C13 | −177.40 (13) | C23—C24—C25—C26 | −178.38 (12) |
O1—C7—C12—C13 | 2.2 (2) | C24—C25—C26—C27 | 173.90 (12) |
C8—C7—C12—C11 | 1.3 (2) | C25—C26—C27—C28 | 55.42 (18) |
O1—C7—C12—C11 | −179.15 (11) | C26—C27—C28—C29 | 61.34 (18) |
C11—C12—C13—C1 | 178.06 (12) | C27—C28—C29—C30 | −161.88 (12) |
C7—C12—C13—C1 | −3.4 (2) | C28—C29—C30—C31 | 73.30 (16) |
C11—C12—C13—C14 | −1.8 (2) | C4—O5—C31—C30 | −169.17 (12) |
C7—C12—C13—C14 | 176.69 (12) | C29—C30—C31—O5 | 58.49 (15) |
C2—C1—C13—C12 | −179.52 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.95 | 2.51 | 3.355 (2) | 149 (2) |
C8—H8···O1i | 0.95 | 2.60 | 3.4639 (19) | 151 (3) |
C10—H10···O3ii | 0.95 | 2.47 | 3.3454 (19) | 154 (2) |
C23—H23A···Cg1 | 0.99 | 2.93 | 3.82 (2) | 150 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C31H32O5 |
Mr | 484.57 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.9010 (9), 12.7844 (13), 12.9683 (14) |
α, β, γ (°) | 91.895 (2), 102.655 (3), 92.167 (3) |
V (Å3) | 1276.0 (2) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.18 × 0.16 × 0.11 |
Data collection | |
Diffractometer | Bruker Microstar diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.804, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4699, 3831, 3392 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.591 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.129, 1.07 |
No. of reflections | 3831 |
No. of parameters | 325 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.24 |
Computer programs: SMART (Bruker, 2003), SMART, SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Farrugia, 1997) and SHELXTL (Bruker, 1997), UdMX (Marris, 2004).
O2—C9 | 1.252 (2) | C5—C6 | 1.390 (2) |
O5—C4 | 1.3640 (17) | C7—C8 | 1.360 (2) |
O5—C31 | 1.4542 (17) | C10—C11 | 1.352 (2) |
C1—C13 | 1.449 (2) | C12—C13 | 1.379 (2) |
C2—C3 | 1.388 (2) | ||
C12—C13—C14 | 120.80 (13) | C1—C13—C14 | 119.87 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.95 | 2.51 | 3.355 (2) | 149 (2) |
C8—H8···O1i | 0.95 | 2.60 | 3.4639 (19) | 151 (3) |
C10—H10···O3ii | 0.95 | 2.47 | 3.3454 (19) | 154 (2) |
C23—H23A···Cg1 | 0.99 | 2.93 | 3.82 (2) | 150 (2) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+2, −z+2. |
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The investigation of macrocycles has been pursued recently along many avenues of science, due to their potential applications as nanomolecular machines (Stoddart & Tseng, 2002, Balzani et al., 2000). Many interesting properties can be obtained by incorporating steric elements into the macrocycle that increase activation barriers such as that to rotation (Feringa, 2001, Kelly et al., 1994). These properties are responsible for novel devices such as field-effect transducers, molecular sensors, switches etc. Because of these activation barriers, macrocycles can be used as actuators and are useful for temperature probes or monitors. Macrocyclic formation is, however, challenging and numerous difficulties are encountered during the synthesis of such nanoactuators. Consequently, macrocycles have attracted much attention in order to find more efficient protocols for their synthesis and for the preparation of new materials with desired functional properties. We have incorporated fluorescein as a core unit in the title compound, (I), because this fluorescent scaffold ensures that unique photophysical properties can be obtained. The benefits of our approach are the ease and versatility of the macrocyclic synthesis, which can ultimately be used for the synthesis of macrocycles with various ring sizes. The synthesis of our macrocycle was achieved in three relatively easy steps starting from fluorescein.
The structure of (I) consists of two planar aryl units linked by an undecanyl alkyl tether. The aryl units are twisted with respect to one another because of the steric hindrance between atom H15 and atoms H2 and H11 (all bonded to the C atoms of the same numbers; Fig. 1) that would result from the coplanarization of the two aryl rings. The angle between the two mean planes of the aryl units is 72.98 (3)°. The 17.02° twist from perpendicularity allows the macrocycle to accommodate the long tether chain, as shown in Fig. 1. This is in contrast with linear fluorescein derivatives whose xanthene–benzyl mean plane angles are rotated by between 85 and 90° (Cody, 1987; Tremayne et al., 1997; Willner et al., 1997; Ajtai & Burghardt, 1995; Wang et al., 2001). The intramolecular C—H···π interaction C23—H23A···Cg1, where Cg1 is the centroid of the C1–C6 ring, also contributes to the observed conformation.
The xanthene moiety consists of three different six-membered rings, namely the central pyrane ring, and the terminal quinone and benzene rings. These individual cycles are generally difficult to identify unequivocally by common techniques such as 1H NMR. Despite these challenges, the bond distances of the different elements that comprise the three unique cycles were expected to be substantially dissimilar, allowing them to be observed in the isolated crystal structure. It is, therefore, not surprising that the isolated xanthene is unsymmetric, with longer bond distances on the side containing the alkyl chain. For example, C2—C3 and C5—C6 are 0.036 (4) and 0.030 (4) Å longer than their respective counterparts C10—C11 and C7—C8, and C1—C13 is also 0.070 (4) Å longer than its corresponding C12—C13 bond. Even though the O1—C7 and O1—C6 bond distances are identical, the C1—C13 and C12—C13 bond distances are considerably different, further contributing to the unsymmetric nature of the compound.
The C12—C13 bond is understood to have greater double-bond-like character owing to its shorter length relative to C1—C13. This configuration confers an aromatic character on the xanthene. The O2—C9 bond is also 0.112 (4) Å shorter than O5—C4, which is 0.079 (5) Å shorter than the reported value for a similar fluorescein (Yamaguchi et al., 1997). The O2—C9 and O5—C4 bond distances correspond to a ketone and an aryl ether group, respectively, which cannot be readily identified by other standard characterization techniques. The presence of these two different groups further contributes to the unsymmetric nature of the fluorescein. The combined bond distances confirm that the xanthene consists of three different six-membered cycles. These different aromatic cycles collectively contribute to the high fluorescence exhibited by this compound. Moreover, of the many known conformations of fluorescein, the isolated structure confirms that the highly conjugated quinoid conformation is formed.
Owing to the possible rotation around the C13—C14 bond, the long alkyl chain can potentially lay on either side of the xanthene face, leading to two possible isomers. The asymmetric molecule has a C12—C3—C14—C19 torsion angle of -71.7 (2)°. Since the compound crystallizes in the P-1 space group there is an exact inversion related molecule with the corresponding torsion angle of +71.7 (2)°. No disorder was found in the structure even with the long C11 tether. Even though the alkyl chain forms a rectangular cage-like structure with the xanthene moiety, no solvent was found within the structure. The cavity size was calculated to be 7.88 (1) Å wide by 3.762 (6) Å in height. The height was calculated according to the absolute distance between the planes of the xanthene and the alkyl chain, while the width was calculated from the distance between the two average mean planes described by C14—C19—C20 and C27—C28—C29.
The xanthene moieties of different isomers adopt an anti-parallel arrangement in the crystal lattice. Conversely, the benzyl units of the two isomers are parallel. The arrangement of the xanthene and the benzyl moieties affords a close packed network that is present in the crystal lattice involving the two inversion-related molecules of (I) (Fig. 2), which extends along the z-direction. Even though π-stacking is common for such highly conjugated compounds, no such interactions were found for (I). Despite the xanthene-xanthene and benzene-benzene plane distances being ideal for π-interactions at 3.341 (4) Å and 3.73 (1) Å, respectively, the aryl units do not overlap. In fact, the centroid-centroid distances of xanthene and benzene are much greater resulting in no apparent intermolecular interactions. However, a van der Waals interaction occurs between the alkyl chains of two molecules separated by 3.89 (1) Å. The observed van der Waals interactions take place between two different isomers.
A total of six intermolecular C—H···O hydrogen bonds are present and these are responsible for the supramolecular network represented in Fig. 4. Two such interactions occur between C5—H5···O2 of two separate molecules. There are two additional donor—acceptor bonds involving C8—H8···O1. These two donor—acceptor pairs are separated by 3.355 (2) and 3.4639 (19) Å, respectively, and form a dimer-like structure. Two additional hydrogen bonds occur between two complementary C10—H10···O3 units of two molecules, which are separated by 3.3454 (19) Å. More specifically, a non-traditional donor–acceptor–donor–acceptor hydrogen-bonding motif was found between the two isolated isomers involving the xanthene unit, leading to a dimer-like arrangement. This is illustrated in Fig. 4, which also shows the interactions between the two isomers involving O2···H5i—C5i, O1···H8i—C8i, O2i···H5—C5 and O1i···H8—C8 (Table 2). Hydrogen bonds between atoms O3 and H10ii and the other isomer involving O3i and H10iv were also observed. All the intermolecular distances are less than 3.5 Å and the D—H···A angles are ca 150°, so they can therefore be categorized as ideal hydrogen bonds.