Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014076/ob6061sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014076/ob6061Isup2.hkl |
CCDC reference: 172195
Model compound (2) was synthesized using successive Williamson's method (Kuboniwa et al., 1985). Ion-transport experiment using (2) through a ClCH2CH2Cl liquid membrane was carried out in a U-tube apparatus as described previously (Yamaguchi et al., 1988), however, transported ions were analyzed by atomic absorption spectrometry instead of flame analysis. The analysis showed that 22% of Na+ and 73% of K+ were transported by (2) with errors of about 5% in 5 d. A solution of RbOH in MeOH (0.54 ml, 3.74 mM) was added to the solution of (2) (11.3 mg) in 20 ml MeOH and the mixture was stirred overnight. After removal of the solvent, the solid was dried in vacuo. Compound (2) and its Rb salt were characterized by EA, IR, 1H and 13C NMR. A chloroform solution of the Rb salt of (2) was slowly evaporated to give single crystals of (I). Crystals of the K salt of (2) were also obtained from chloroform solution, however, the quality of the reflection data was not good.
H atoms attached to C atoms were included in idealized positions and refined using a riding model (C—H = 0.93 Å). H atoms attached to O atoms were found in the difference Fourier maps and their positional parameters were refined with restraints on the O—H distances. The O—H distances were 0.803 (18)–1.00 (4) Å.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Molecular Structure Corporation and Rigaku, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. An ORTEP-3 drawing (Farrugia, 1997) of (I) with 50% probability displacement ellipsoids. |
[Rb(C32H33O10)]·H2O | F(000) = 704 |
Mr = 681.07 | Dx = 1.50 Mg m−3 |
Triclinic, P1 | Melting point: not measured K |
a = 10.0948 (10) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 11.2408 (10) Å | Cell parameters from 1053 reflections |
c = 14.055 (3) Å | θ = 2.3–13.7° |
α = 85.524 (11)° | µ = 1.70 mm−1 |
β = 71.679 (11)° | T = 123 K |
γ = 89.852 (14)° | Platelet, colorless |
V = 1509.0 (4) Å3 | 0.30 × 0.10 × 0.05 mm |
Z = 2 |
Rigaku RAXIS-RAPID Imaging Plate diffractometer | 6684 independent reflections |
Radiation source: rotor | 4520 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
Detector resolution: 10.0 pixels mm-1 | θmax = 27.3°, θmin = 1.5° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −14→14 |
Tmin = 0.616, Tmax = 0.919 | l = −18→18 |
12683 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
6684 reflections | (Δ/σ)max < 0.001 |
413 parameters | Δρmax = 0.53 e Å−3 |
4 restraints | Δρmin = −0.52 e Å−3 |
[Rb(C32H33O10)]·H2O | γ = 89.852 (14)° |
Mr = 681.07 | V = 1509.0 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0948 (10) Å | Mo Kα radiation |
b = 11.2408 (10) Å | µ = 1.70 mm−1 |
c = 14.055 (3) Å | T = 123 K |
α = 85.524 (11)° | 0.30 × 0.10 × 0.05 mm |
β = 71.679 (11)° |
Rigaku RAXIS-RAPID Imaging Plate diffractometer | 6684 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 4520 reflections with I > 2σ(I) |
Tmin = 0.616, Tmax = 0.919 | Rint = 0.054 |
12683 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 4 restraints |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.53 e Å−3 |
6684 reflections | Δρmin = −0.52 e Å−3 |
413 parameters |
Experimental. Compound 2. Anal. Calcd. for C32H32O9 0.5H2O. C 67.47, H 5.84. Found. C 67.53, H 5.69. 1H NMR (500 MHz, CDCl3) δ 3.85(2H, t, J=4.1 Hz), 4.04(2H, t, J=4.1 Hz), 4.33–4.37(8H,m), 5.39(2H, s), 6.85–6.96(12H, m), 7.31(1H, t, J=7.7 Hz), 7.44(1H, t, J=7.7 Hz), 7.59(1H, d, J=7.7 Hz), 7.82(1H, d, J=7.7 Hz). 13C NMR (125 MHz, CDCl3) δ 61.09, 67.98, 68.05(2 C), 68.30, 70.19, 71.77, 114.60, 114.88, 115.12, 115.54, 115.64, 115.93, 121.83(2 C), 121.87, 122.02, 122.25(2 C), 127.56, 128.45, 128.79, 130.95, 132.31, 139.00, 148.57, 148.74, 148.88, 149.01, 149.10(2 C), 169.60. IR (KBr) ν C=O 1684 cm-1. Rb salt of 2. Anal. Calcd. for C32H31O9Rb 0.25H2O. C, 59.17 H, 4.89 O, 22.78 Rb, 13.16. Found (E. Pascher, Remagen, Germany) C 59.05, H 5.03, O 22.4, Cl < 0.1, Rb, 13.2. IR (KBr) ν C=O 1637 cm-1. 1H NMR (500 MHz, CDCl3) δ 3.85(2H, m), 3.96 (2H, m), 4.07(2H, m), 4.15(2H, m), 4.26(2H, m), 4.34(2H, m), 5.30(2H, s), 6.63(1H, d, J=8.1 Hz), 6.76–7.02 (11H, m), 7.09–7.18 (3H, m), 7.62(1H, d, J=7.3 Hz). 13C NMR (125 MHz, CDCl3) δ 59.78, 66.72, 67.31, 67.42, 68.07, 70.07, 70.65, 112.80, 113.07, 113.67, 114.25, 114.59, 114.78, 120.86, 120.91, 122.17, 122.21, 122.32, 122.75, 127.13, 128.38, 128.89, 130.05, 132.88, 142.59, 147.04, 147.37, 147.57, 147.98, 148.23, 148.92, 174.72. |
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 | ||
C4 | 0.7051 (4) | 0.4217 (3) | 0.3119 (3) | 0.0181 (8) | |
C5 | 0.8510 (3) | 0.4029 (3) | 0.3179 (2) | 0.0161 (7) | |
C6 | 0.9029 (4) | 0.2873 (4) | 0.3098 (3) | 0.0220 (8) | |
H6 | 0.8519 | 0.2274 | 0.2940 | 0.026* | |
C7 | 1.0295 (4) | 0.2609 (4) | 0.3251 (3) | 0.0270 (9) | |
H7 | 1.0634 | 0.1840 | 0.3186 | 0.032* | |
C8 | 1.1049 (4) | 0.3490 (4) | 0.3499 (3) | 0.0316 (10) | |
H8 | 1.1875 | 0.3308 | 0.3635 | 0.038* | |
C9 | 1.0568 (4) | 0.4646 (4) | 0.3545 (3) | 0.0239 (9) | |
H9 | 1.1093 | 0.5238 | 0.3697 | 0.029* | |
C10 | 0.9324 (4) | 0.4948 (3) | 0.3372 (3) | 0.0176 (8) | |
C11 | 0.8946 (4) | 0.6252 (3) | 0.3314 (3) | 0.0181 (8) | |
H11A | 0.8071 | 0.6372 | 0.3833 | 0.022* | |
H11B | 0.9662 | 0.6738 | 0.3432 | 0.022* | |
C13 | 1.0020 (3) | 0.6608 (3) | 0.1519 (3) | 0.0149 (7) | |
C14 | 1.1362 (3) | 0.6664 (3) | 0.1586 (3) | 0.0173 (8) | |
H14 | 1.1490 | 0.6706 | 0.2209 | 0.021* | |
C15 | 1.2521 (3) | 0.6656 (3) | 0.0721 (3) | 0.0193 (8) | |
H15 | 1.3418 | 0.6675 | 0.0772 | 0.023* | |
C16 | 1.2332 (4) | 0.6622 (3) | −0.0211 (3) | 0.0206 (8) | |
H16 | 1.3102 | 0.6632 | −0.0788 | 0.025* | |
C17 | 1.0989 (3) | 0.6571 (3) | −0.0285 (3) | 0.0174 (8) | |
H17 | 1.0868 | 0.6554 | −0.0913 | 0.021* | |
C18 | 0.9827 (3) | 0.6547 (3) | 0.0575 (3) | 0.0150 (7) | |
C20 | 0.8282 (3) | 0.6411 (3) | −0.0405 (3) | 0.0169 (8) | |
H20A | 0.8775 | 0.5741 | −0.0738 | 0.020* | |
H20B | 0.8652 | 0.7138 | −0.0822 | 0.020* | |
C21 | 0.6742 (4) | 0.6276 (3) | −0.0251 (3) | 0.0183 (8) | |
H21A | 0.6603 | 0.6151 | −0.0889 | 0.022* | |
H21B | 0.6371 | 0.5579 | 0.0208 | 0.022* | |
C23 | 0.6229 (3) | 0.8331 (3) | −0.0510 (3) | 0.0168 (8) | |
C24 | 0.5756 (4) | 0.8421 (4) | −0.1333 (3) | 0.0222 (8) | |
H24 | 0.5329 | 0.7763 | −0.1486 | 0.027* | |
C25 | 0.5913 (4) | 0.9488 (4) | −0.1937 (3) | 0.0281 (9) | |
H25 | 0.5583 | 0.9551 | −0.2486 | 0.034* | |
C26 | 0.6566 (4) | 1.0448 (4) | −0.1706 (3) | 0.0313 (10) | |
H26 | 0.6679 | 1.1162 | −0.2107 | 0.038* | |
C27 | 0.7058 (4) | 1.0368 (4) | −0.0887 (3) | 0.0264 (9) | |
H27 | 0.7495 | 1.1026 | −0.0743 | 0.032* | |
C28 | 0.6899 (4) | 0.9308 (3) | −0.0283 (3) | 0.0193 (8) | |
C30 | 0.7926 (4) | 1.0163 (3) | 0.0827 (3) | 0.0208 (8) | |
H30A | 0.7226 | 1.0770 | 0.1000 | 0.025* | |
H30B | 0.8713 | 1.0494 | 0.0274 | 0.025* | |
C31 | 0.8388 (4) | 0.9786 (3) | 0.1713 (3) | 0.0220 (8) | |
H31A | 0.9035 | 0.9137 | 0.1557 | 0.026* | |
H31B | 0.8852 | 1.0448 | 0.1891 | 0.026* | |
C33 | 0.7335 (4) | 0.9188 (3) | 0.3464 (3) | 0.0194 (8) | |
C34 | 0.8582 (4) | 0.9322 (3) | 0.3667 (3) | 0.0241 (9) | |
H34 | 0.9394 | 0.9559 | 0.3152 | 0.029* | |
C35 | 0.8607 (4) | 0.9099 (4) | 0.4645 (3) | 0.0285 (9) | |
H35 | 0.9443 | 0.9176 | 0.4784 | 0.034* | |
C36 | 0.7414 (4) | 0.8767 (4) | 0.5407 (3) | 0.0278 (9) | |
H36 | 0.7438 | 0.8652 | 0.6064 | 0.033* | |
C37 | 0.6160 (4) | 0.8600 (4) | 0.5209 (3) | 0.0237 (8) | |
H37 | 0.5357 | 0.8356 | 0.5730 | 0.028* | |
C38 | 0.6112 (4) | 0.8799 (3) | 0.4235 (3) | 0.0187 (8) | |
C40 | 0.3705 (4) | 0.8165 (3) | 0.4715 (3) | 0.0200 (8) | |
H40A | 0.3376 | 0.8730 | 0.5221 | 0.024* | |
H40B | 0.3903 | 0.7424 | 0.5040 | 0.024* | |
C41 | 0.2611 (4) | 0.7952 (4) | 0.4225 (3) | 0.0218 (8) | |
H41A | 0.1749 | 0.7691 | 0.4740 | 0.026* | |
H41B | 0.2438 | 0.8699 | 0.3894 | 0.026* | |
O2 | 0.6344 (2) | 0.5027 (2) | 0.36233 (18) | 0.0200 (6) | |
O3 | 0.6603 (3) | 0.3542 (3) | 0.2613 (2) | 0.0271 (6) | |
O12 | 0.8813 (2) | 0.6621 (2) | 0.23368 (17) | 0.0152 (5) | |
O19 | 0.8465 (2) | 0.6454 (2) | 0.05654 (17) | 0.0157 (5) | |
O22 | 0.5985 (2) | 0.7317 (2) | 0.01520 (17) | 0.0165 (5) | |
O29 | 0.7355 (3) | 0.9132 (2) | 0.05368 (18) | 0.0209 (6) | |
O32 | 0.7169 (2) | 0.9406 (2) | 0.25301 (18) | 0.0207 (6) | |
O39 | 0.4953 (2) | 0.8634 (2) | 0.39466 (17) | 0.0183 (5) | |
O42 | 0.3000 (3) | 0.7082 (3) | 0.35054 (19) | 0.0216 (6) | |
O44 | 0.3517 (3) | 0.4964 (3) | 0.4390 (2) | 0.0233 (6) | |
O43 | 0.4577 (3) | 0.4757 (3) | 0.2049 (2) | 0.0256 (6) | |
Rb1 | 0.59851 (3) | 0.70710 (3) | 0.22048 (3) | 0.01660 (10) | |
H42 | 0.309 (4) | 0.648 (2) | 0.383 (3) | 0.018 (11)* | |
H43A | 0.518 (4) | 0.420 (4) | 0.231 (3) | 0.025* | |
H43B | 0.384 (3) | 0.470 (4) | 0.251 (2) | 0.025* | |
H44A | 0.436 (2) | 0.493 (3) | 0.415 (3) | 0.019* | |
H44B | 0.336 (4) | 0.490 (4) | 0.4988 (15) | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C4 | 0.0182 (17) | 0.022 (2) | 0.0129 (17) | 0.0008 (15) | −0.0038 (14) | 0.0022 (15) |
C5 | 0.0190 (17) | 0.019 (2) | 0.0083 (15) | −0.0007 (14) | −0.0021 (14) | 0.0040 (14) |
C6 | 0.0219 (19) | 0.025 (2) | 0.0180 (18) | −0.0029 (15) | −0.0056 (16) | 0.0014 (16) |
C7 | 0.024 (2) | 0.019 (2) | 0.036 (2) | 0.0033 (16) | −0.0078 (18) | 0.0060 (18) |
C8 | 0.0167 (19) | 0.034 (3) | 0.043 (3) | 0.0007 (17) | −0.0123 (18) | 0.014 (2) |
C9 | 0.0195 (18) | 0.024 (2) | 0.029 (2) | −0.0042 (15) | −0.0114 (17) | 0.0070 (17) |
C10 | 0.0175 (17) | 0.021 (2) | 0.0138 (17) | −0.0011 (14) | −0.0060 (14) | 0.0042 (15) |
C11 | 0.0168 (17) | 0.024 (2) | 0.0146 (17) | −0.0027 (14) | −0.0066 (14) | −0.0012 (15) |
C13 | 0.0152 (17) | 0.0082 (17) | 0.0182 (17) | −0.0026 (13) | −0.0012 (14) | 0.0004 (14) |
C14 | 0.0197 (18) | 0.0108 (18) | 0.0224 (18) | −0.0030 (13) | −0.0086 (15) | 0.0011 (15) |
C15 | 0.0113 (16) | 0.0152 (19) | 0.032 (2) | −0.0011 (13) | −0.0073 (15) | −0.0011 (16) |
C16 | 0.0168 (17) | 0.0138 (19) | 0.026 (2) | −0.0024 (14) | 0.0001 (15) | −0.0015 (16) |
C17 | 0.0187 (17) | 0.0143 (19) | 0.0167 (17) | −0.0002 (14) | −0.0020 (15) | −0.0009 (15) |
C18 | 0.0145 (16) | 0.0107 (18) | 0.0194 (18) | −0.0002 (13) | −0.0046 (15) | −0.0006 (14) |
C20 | 0.0203 (17) | 0.016 (2) | 0.0139 (17) | 0.0023 (14) | −0.0048 (15) | −0.0024 (14) |
C21 | 0.0215 (18) | 0.0144 (19) | 0.0203 (18) | 0.0005 (14) | −0.0084 (15) | −0.0021 (15) |
C23 | 0.0159 (17) | 0.017 (2) | 0.0155 (17) | 0.0047 (14) | −0.0032 (14) | 0.0010 (15) |
C24 | 0.0180 (18) | 0.030 (2) | 0.0187 (18) | 0.0051 (15) | −0.0057 (15) | −0.0036 (17) |
C25 | 0.034 (2) | 0.034 (3) | 0.0150 (18) | 0.0106 (18) | −0.0075 (17) | 0.0043 (17) |
C26 | 0.043 (2) | 0.027 (2) | 0.020 (2) | 0.0109 (19) | −0.0054 (18) | 0.0059 (17) |
C27 | 0.038 (2) | 0.015 (2) | 0.022 (2) | 0.0010 (17) | −0.0041 (18) | 0.0014 (16) |
C28 | 0.0214 (18) | 0.017 (2) | 0.0164 (18) | 0.0033 (14) | −0.0026 (15) | 0.0006 (15) |
C30 | 0.0233 (18) | 0.014 (2) | 0.0223 (19) | −0.0065 (15) | −0.0031 (16) | −0.0001 (15) |
C31 | 0.0175 (18) | 0.019 (2) | 0.026 (2) | −0.0048 (15) | −0.0016 (16) | −0.0046 (16) |
C33 | 0.0258 (19) | 0.0140 (19) | 0.0224 (19) | 0.0016 (15) | −0.0119 (16) | −0.0069 (15) |
C34 | 0.024 (2) | 0.018 (2) | 0.034 (2) | −0.0001 (15) | −0.0130 (18) | −0.0073 (17) |
C35 | 0.034 (2) | 0.021 (2) | 0.042 (2) | 0.0084 (17) | −0.027 (2) | −0.0128 (19) |
C36 | 0.040 (2) | 0.023 (2) | 0.029 (2) | 0.0100 (18) | −0.022 (2) | −0.0063 (18) |
C37 | 0.034 (2) | 0.020 (2) | 0.0207 (19) | 0.0070 (16) | −0.0129 (17) | −0.0039 (16) |
C38 | 0.0236 (19) | 0.0128 (19) | 0.0215 (19) | 0.0032 (14) | −0.0093 (16) | −0.0035 (15) |
C40 | 0.0232 (19) | 0.020 (2) | 0.0144 (17) | −0.0012 (15) | −0.0016 (15) | −0.0014 (15) |
C41 | 0.0193 (18) | 0.025 (2) | 0.0187 (18) | 0.0017 (15) | −0.0026 (15) | −0.0021 (16) |
O2 | 0.0156 (12) | 0.0259 (15) | 0.0179 (13) | 0.0009 (10) | −0.0044 (10) | −0.0014 (11) |
O3 | 0.0264 (14) | 0.0303 (17) | 0.0303 (15) | 0.0028 (12) | −0.0148 (12) | −0.0120 (13) |
O12 | 0.0144 (11) | 0.0176 (14) | 0.0122 (12) | 0.0004 (9) | −0.0027 (10) | 0.0012 (10) |
O19 | 0.0117 (11) | 0.0199 (14) | 0.0157 (12) | −0.0008 (9) | −0.0049 (10) | −0.0009 (10) |
O22 | 0.0170 (12) | 0.0146 (13) | 0.0174 (12) | 0.0012 (10) | −0.0051 (10) | 0.0011 (10) |
O29 | 0.0308 (14) | 0.0134 (14) | 0.0206 (13) | −0.0031 (11) | −0.0117 (11) | 0.0011 (11) |
O32 | 0.0200 (13) | 0.0245 (15) | 0.0169 (13) | −0.0053 (11) | −0.0053 (11) | 0.0016 (11) |
O39 | 0.0190 (12) | 0.0231 (15) | 0.0133 (12) | −0.0014 (10) | −0.0064 (10) | 0.0010 (11) |
O42 | 0.0254 (14) | 0.0226 (16) | 0.0172 (13) | −0.0020 (12) | −0.0080 (11) | 0.0012 (12) |
O44 | 0.0169 (13) | 0.0328 (17) | 0.0185 (13) | −0.0003 (12) | −0.0035 (12) | −0.0007 (13) |
O43 | 0.0221 (14) | 0.0348 (18) | 0.0211 (14) | −0.0015 (13) | −0.0079 (12) | −0.0052 (13) |
Rb1 | 0.01534 (16) | 0.01794 (19) | 0.01532 (17) | −0.00006 (12) | −0.00305 (13) | −0.00152 (13) |
C4—O3 | 1.253 (4) | C27—H27 | 0.9300 |
C4—O2 | 1.273 (4) | C28—O29 | 1.370 (4) |
C4—C5 | 1.515 (5) | C30—O29 | 1.438 (4) |
C5—C6 | 1.399 (5) | C30—C31 | 1.492 (5) |
C5—C10 | 1.415 (5) | C30—H30A | 0.9700 |
C6—C7 | 1.389 (5) | C30—H30B | 0.9700 |
C6—H6 | 0.9300 | C31—O32 | 1.433 (4) |
C7—C8 | 1.381 (6) | C31—H31A | 0.9700 |
C7—H7 | 0.9300 | C31—H31B | 0.9700 |
C8—C9 | 1.385 (6) | C33—O32 | 1.378 (4) |
C8—H8 | 0.9300 | C33—C34 | 1.386 (5) |
C9—C10 | 1.388 (5) | C33—C38 | 1.406 (5) |
C9—H9 | 0.9300 | C34—C35 | 1.386 (6) |
C10—C11 | 1.516 (5) | C34—H34 | 0.9300 |
C11—O12 | 1.450 (4) | C35—C36 | 1.366 (6) |
C11—H11A | 0.9700 | C35—H35 | 0.9300 |
C11—H11B | 0.9700 | C36—C37 | 1.395 (5) |
C13—O12 | 1.389 (4) | C36—H36 | 0.9300 |
C13—C14 | 1.389 (5) | C37—C38 | 1.385 (5) |
C13—C18 | 1.407 (5) | C37—H37 | 0.9300 |
C14—C15 | 1.398 (5) | C38—O39 | 1.371 (4) |
C14—H14 | 0.9300 | C40—O39 | 1.445 (4) |
C15—C16 | 1.386 (5) | C40—C41 | 1.502 (5) |
C15—H15 | 0.9300 | C40—H40A | 0.9700 |
C16—C17 | 1.393 (5) | C40—H40B | 0.9700 |
C16—H16 | 0.9300 | C41—O42 | 1.427 (4) |
C17—C18 | 1.393 (5) | C41—H41A | 0.9700 |
C17—H17 | 0.9300 | C41—H41B | 0.9700 |
C18—O19 | 1.383 (4) | O2—Rb1 | 3.020 (3) |
C20—O19 | 1.437 (4) | O12—Rb1 | 2.958 (2) |
C20—C21 | 1.507 (5) | O19—Rb1 | 2.945 (2) |
C20—H20A | 0.9700 | O22—Rb1 | 2.877 (3) |
C20—H20B | 0.9700 | O29—Rb1 | 3.147 (3) |
C21—O22 | 1.449 (4) | O32—Rb1 | 3.012 (3) |
C21—H21A | 0.9700 | O39—Rb1 | 3.037 (2) |
C21—H21B | 0.9700 | O42—Rb1 | 2.994 (3) |
C23—C24 | 1.380 (5) | O43—Rb1 | 3.023 (3) |
C23—O22 | 1.385 (4) | O42—O43 | 3.510 (4) |
C23—C28 | 1.399 (5) | O42—H42 | 0.807 (19) |
C24—C25 | 1.394 (6) | O42—O44 | 2.724 (4) |
C24—H24 | 0.9300 | O43—O44 | 3.151 (4) |
C25—C26 | 1.377 (6) | O44—H44A | 0.816 (18) |
C25—H25 | 0.9300 | O44—H44B | 0.803 (18) |
C26—C27 | 1.386 (6) | O43—H43A | 1.00 (4) |
C26—H26 | 0.9300 | O43—H43B | 0.819 (18) |
C27—C28 | 1.387 (5) | ||
O3—C4—O2 | 124.6 (3) | C31—C30—H30B | 110.1 |
O3—C4—C5 | 118.4 (3) | H30A—C30—H30B | 108.4 |
O2—C4—C5 | 117.0 (3) | O32—C31—C30 | 107.6 (3) |
C6—C5—C10 | 119.1 (3) | O32—C31—H31A | 110.2 |
C6—C5—C4 | 117.7 (3) | C30—C31—H31A | 110.2 |
C10—C5—C4 | 123.1 (3) | O32—C31—H31B | 110.2 |
C7—C6—C5 | 120.9 (4) | C30—C31—H31B | 110.2 |
C7—C6—H6 | 119.6 | H31A—C31—H31B | 108.5 |
C5—C6—H6 | 119.6 | O32—C33—C34 | 124.9 (3) |
C8—C7—C6 | 120.0 (4) | O32—C33—C38 | 114.5 (3) |
C8—C7—H7 | 120.0 | C34—C33—C38 | 120.6 (4) |
C6—C7—H7 | 120.0 | C33—C34—C35 | 119.4 (4) |
C7—C8—C9 | 119.5 (4) | C33—C34—H34 | 120.3 |
C7—C8—H8 | 120.2 | C35—C34—H34 | 120.3 |
C9—C8—H8 | 120.2 | C36—C35—C34 | 120.6 (4) |
C8—C9—C10 | 122.0 (4) | C36—C35—H35 | 119.7 |
C8—C9—H9 | 119.0 | C34—C35—H35 | 119.7 |
C10—C9—H9 | 119.0 | C35—C36—C37 | 120.6 (4) |
C9—C10—C5 | 118.4 (3) | C35—C36—H36 | 119.7 |
C9—C10—C11 | 119.1 (3) | C37—C36—H36 | 119.7 |
C5—C10—C11 | 122.4 (3) | C38—C37—C36 | 119.9 (4) |
O12—C11—C10 | 110.7 (3) | C38—C37—H37 | 120.1 |
O12—C11—H11A | 109.5 | C36—C37—H37 | 120.1 |
C10—C11—H11A | 109.5 | O39—C38—C37 | 125.0 (3) |
O12—C11—H11B | 109.5 | O39—C38—C33 | 116.0 (3) |
C10—C11—H11B | 109.5 | C37—C38—C33 | 118.9 (3) |
H11A—C11—H11B | 108.1 | O39—C40—C41 | 108.3 (3) |
O12—C13—C14 | 124.1 (3) | O39—C40—H40A | 110.0 |
O12—C13—C18 | 116.1 (3) | C41—C40—H40A | 110.0 |
C14—C13—C18 | 119.8 (3) | O39—C40—H40B | 110.0 |
C13—C14—C15 | 120.4 (3) | C41—C40—H40B | 110.0 |
C13—C14—H14 | 119.8 | H40A—C40—H40B | 108.4 |
C15—C14—H14 | 119.8 | O42—C41—C40 | 113.0 (3) |
C16—C15—C14 | 119.9 (3) | O42—C41—H41A | 109.0 |
C16—C15—H15 | 120.1 | C40—C41—H41A | 109.0 |
C14—C15—H15 | 120.1 | O42—C41—H41B | 109.0 |
C15—C16—C17 | 120.1 (3) | C40—C41—H41B | 109.0 |
C15—C16—H16 | 120.0 | H41A—C41—H41B | 107.8 |
C17—C16—H16 | 120.0 | C13—O12—C11 | 116.5 (3) |
C18—C17—C16 | 120.5 (3) | C18—O19—C20 | 116.2 (2) |
C18—C17—H17 | 119.7 | C23—O22—C21 | 115.1 (3) |
C16—C17—H17 | 119.7 | C28—O29—C30 | 116.3 (3) |
O19—C18—C17 | 123.8 (3) | C33—O32—C31 | 116.9 (3) |
O19—C18—C13 | 116.8 (3) | C38—O39—C40 | 117.1 (3) |
C17—C18—C13 | 119.3 (3) | C41—O42—H42 | 104 (3) |
O19—C20—C21 | 108.0 (3) | H44A—O44—H44B | 105 (4) |
O19—C20—H20A | 110.1 | H43A—O43—H43B | 102 (4) |
C21—C20—H20A | 110.1 | O22—Rb1—O19 | 59.55 (7) |
O19—C20—H20B | 110.1 | O22—Rb1—O12 | 111.69 (6) |
C21—C20—H20B | 110.1 | O19—Rb1—O12 | 53.18 (6) |
H20A—C20—H20B | 108.4 | O22—Rb1—O42 | 106.89 (7) |
O22—C21—C20 | 111.9 (3) | O19—Rb1—O42 | 159.16 (7) |
O22—C21—Rb1 | 53.94 (16) | O12—Rb1—O42 | 140.90 (7) |
C20—C21—Rb1 | 90.3 (2) | O22—Rb1—O32 | 105.10 (7) |
O22—C21—H21A | 109.2 | O19—Rb1—O32 | 95.62 (7) |
C20—C21—H21A | 109.2 | O12—Rb1—O32 | 72.46 (7) |
Rb1—C21—H21A | 158.9 | O42—Rb1—O32 | 103.64 (7) |
O22—C21—H21B | 109.2 | O22—Rb1—O2 | 135.12 (7) |
C20—C21—H21B | 109.2 | O19—Rb1—O2 | 93.21 (7) |
Rb1—C21—H21B | 71.3 | O12—Rb1—O2 | 61.61 (6) |
H21A—C21—H21B | 107.9 | O42—Rb1—O2 | 86.59 (7) |
C24—C23—O22 | 122.0 (3) | O32—Rb1—O2 | 113.06 (7) |
C24—C23—C28 | 120.2 (3) | O22—Rb1—O43 | 78.18 (7) |
O22—C23—C28 | 117.7 (3) | O19—Rb1—O43 | 89.54 (7) |
C23—C24—C25 | 120.7 (4) | O12—Rb1—O43 | 110.32 (7) |
C23—C24—H24 | 119.7 | O42—Rb1—O43 | 71.37 (7) |
C25—C24—H24 | 119.7 | O32—Rb1—O43 | 174.79 (7) |
C26—C25—C24 | 118.8 (4) | O2—Rb1—O43 | 65.74 (7) |
C26—C25—H25 | 120.6 | O22—Rb1—O39 | 133.16 (7) |
C24—C25—H25 | 120.6 | O19—Rb1—O39 | 143.85 (6) |
C25—C26—C27 | 121.2 (4) | O12—Rb1—O39 | 98.52 (6) |
C25—C26—H26 | 119.4 | O42—Rb1—O39 | 56.96 (7) |
C27—C26—H26 | 119.4 | O32—Rb1—O39 | 50.51 (6) |
C26—C27—C28 | 120.1 (4) | O2—Rb1—O39 | 90.40 (7) |
C26—C27—H27 | 120.0 | O43—Rb1—O39 | 124.30 (7) |
C28—C27—H27 | 120.0 | O22—Rb1—O29 | 51.97 (7) |
O29—C28—C27 | 124.7 (4) | O19—Rb1—O29 | 63.52 (7) |
O29—C28—C23 | 116.2 (3) | O12—Rb1—O29 | 87.19 (7) |
C27—C28—C23 | 119.0 (4) | O42—Rb1—O29 | 122.75 (7) |
O29—C30—C31 | 108.2 (3) | O32—Rb1—O29 | 53.81 (7) |
O29—C30—H30A | 110.1 | O2—Rb1—O29 | 148.71 (6) |
C31—C30—H30A | 110.1 | O43—Rb1—O29 | 129.94 (7) |
O29—C30—H30B | 110.1 | O39—Rb1—O29 | 96.95 (7) |
C10—C11—O12—C13 | −65.0 (4) | C24—C23—O22—C21 | 69.8 (4) |
C21—C20—O19—C18 | 178.4 (3) | C27—C28—O29—C30 | 5.6 (5) |
C20—C21—O22—C23 | 70.4 (4) | C34—C33—O32—C31 | 0.7 (5) |
C31—C30—O29—C28 | −178.8 (3) | C37—C38—O39—C40 | −2.9 (5) |
C30—C31—O32—C33 | −170.6 (3) | O19—C20—C21—O22 | 65.6 (4) |
C41—C40—O39—C38 | −175.0 (3) | O29—C30—C31—O32 | −64.8 (4) |
C14—C13—O12—C11 | −22.4 (5) | O39—C40—C41—O42 | 62.6 (4) |
C17—C18—O19—C20 | −1.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O42—H42···O44 | 0.81 (2) | 1.93 (2) | 2.724 (4) | 169 (4) |
Experimental details
Crystal data | |
Chemical formula | [Rb(C32H33O10)]·H2O |
Mr | 681.07 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 10.0948 (10), 11.2408 (10), 14.055 (3) |
α, β, γ (°) | 85.524 (11), 71.679 (11), 89.852 (14) |
V (Å3) | 1509.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.30 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Rigaku RAXIS-RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.616, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12683, 6684, 4520 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.644 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.115, 0.94 |
No. of reflections | 6684 |
No. of parameters | 413 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.53, −0.52 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Molecular Structure Corporation and Rigaku, 2001), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
O2—Rb1 | 3.020 (3) | O32—Rb1 | 3.012 (3) |
O12—Rb1 | 2.958 (2) | O39—Rb1 | 3.037 (2) |
O19—Rb1 | 2.945 (2) | O42—Rb1 | 2.994 (3) |
O22—Rb1 | 2.877 (3) | O43—Rb1 | 3.023 (3) |
O29—Rb1 | 3.147 (3) | ||
C10—C11—O12—C13 | −65.0 (4) | C24—C23—O22—C21 | 69.8 (4) |
C21—C20—O19—C18 | 178.4 (3) | C27—C28—O29—C30 | 5.6 (5) |
C20—C21—O22—C23 | 70.4 (4) | C34—C33—O32—C31 | 0.7 (5) |
C31—C30—O29—C28 | −178.8 (3) | C37—C38—O39—C40 | −2.9 (5) |
C30—C31—O32—C33 | −170.6 (3) | O19—C20—C21—O22 | 65.6 (4) |
C41—C40—O39—C38 | −175.0 (3) | O29—C30—C31—O32 | −64.8 (4) |
C14—C13—O12—C11 | −22.4 (5) | O39—C40—C41—O42 | 62.6 (4) |
C17—C18—O19—C20 | −1.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O42—H42···O44 | 0.807 (19) | 1.93 (2) | 2.724 (4) | 169 (4) |
Naturally occurring acid ionophores are known to mediate active ion transport through lipophilic membranes by formation of hydrophobic complexes with ions (Taylor et al., 1982, and references therein) and their structures were studied to provide information on their function (Duesler & Paul, 1983, and references therein). We have synthesized a series of relatively simple ω-hydroxycarboxylic acids as model compounds for the naturally occurring ionophores to investigate the relationship between the primary molecular structures and ion-transport properties (Kuboniwa et al., 1982, 1985; Yamazaki et al., 1978, 1979; Yamaguchi et al., 1988, 1989).
The model compounds, (1)–(3), transport K+ over Na+ through the ClCH2CH2Cl membrane using the pH gradient of outer aqueous phases. The competitive ion-transport experiments show that the amount of transported ions, as well as K+ selectivity over Na+, increases in the order of (1) → (2) → (3) (Kuboniwa et al., 1985; Yamaguchi et al., 1988). The model compound, (1), having five ethereal O atoms, forms a 2:2 dimer with K+. The polyether chain of (1) encloses K+ and adopts an S-like conformation. One hydroxy group, six ethereal O atoms including one from the polyether chain of the dimer, and two water molecules coordinate to K+ and the cation is a ninefold coordination. Two O atoms of the carboxylate group do not coordinate to the cation. Solvent water molecules are located between the K salt molecules (Kasuga et al., 1995). Compound (3), having eight ethereal O atoms, forms 1:1 salts with K+, Rb+ and Cs+. The conformation of three alkali metal salts of (3) are very similar to each other. The backbone of three salts of (3) forms a pseudocyclic ring by head-to-tail hydrogen bonding between the terminal carboxylate and hydroxy groups. The main chain of (3) is bent at O12 and O39 and wraps the cation like the seam of a tennis ball to give a complex with a lipophilic exterior. One hydroxy group, eight ethereal O atoms of the main chain and one O atom of the carboxylate group participate in the coordination and K+ is tenfold coordinated. The chloroform molecules, used as the recrystallization solvent, fill the space between the salt molecules in the crystals (Kuboniwa et al., 1988; Kasuga et al., 1991). Slow evaporation of a chloroform solution of the Rb salt of (2), which has six ethereal O atoms and shows ion-transport properties intermediate between those of (1) and (3), afforded single crystals. This paper reports the structure of the Rb salt of (2), i.e. (I).
The molecular structure of (I) (Fig. 1) reveals that the salt forms a 1:1 monomeric structure. The Rb—O distances [2.877 (3)–3.147 (3) Å] indicate that one O atom of the carboxylate group, six ethereal O atoms, the terminal hydroxy group and a water molecule coordinate to Rb+. As a result, Rb+ is ninefold coordinated. Water coordination to the cation is observed in the structure of the K salt of (1), but not in the structure of the K salt of (3). In (I), another water molecule (O44) lies near the coordinating water molecule (O43), with an O43···O44 distance of 3.151 (4) Å. The O42···O44 distance of 2.724 (4) Å shows that intermolecular hydrogen bonding is formed between the terminal hydroxy group and the solvent water molecule. The head-to-tail hydrogen bonding seen in the structure of the K salt of (3) is not observed in (I). Generally, Csp3—Csp3—O—Csp2(quaternary) torsion angles are near 180°, Csp2—Csp2(quaternary)—O—Csp3 are 0° and O—Csp3—Csp3—O are gauche. In (I), this rule also holds except four torsion angles, C10—C11—O12—C13 [-65.0 (4)°], C14—C13—O12—C11 [-22.4 (5)°], C20—C21—O22—C23 [70.4 (4)°] and C24—C23—O22—C21 [69.8 (4)°]. Consequently, the backbone bend of (2) in (I) occurs in a shorter period (O12 and O22) compared with that in the alkali metal salts of (3) (O12 and O39).
In conclusion, the three-dimensional structure of the Rb salt of (2) is intermediate between that of the K salt of (1) and that of the alkali metal salts of (3).