Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300494X/bt6246sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680300494X/bt62462sup2.hkl |
CCDC reference: 209922
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.002 Å
- R factor = 0.034
- wR factor = 0.085
- Data-to-parameter ratio = 19.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.49 From the CIF: _reflns_number_total 6225 Count of symmetry unique reflns 3518 Completeness (_total/calc) 176.95% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2707 Fraction of Friedel pairs measured 0.769 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
Compound (2) was conveniently prepared in a one-step procedure starting from the dibromocalixarene, (1) (see Scheme), and crystallized from dichloromethane/methanol.
Methyl H atoms were located in difference syntheses, idealized (C—H = 0.99 Å and H—C—H = 109.5°) and refined on the basis of rigid groups allowed to rotate but not to tip. Other H atoms were included using a riding model, with fixed C—H bond lengths of 0.95 Å (sp2 C atoms) or 0.98 Å (methylenes). Uiso(H) values were fixed at 1.2Ueq of the parent atom. The absolute configuration was established solely for the measured crystal, because the bulk sample is racemic.
Data collection: XSCANS (Fait, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP5 (Siemens, 1994); software used to prepare material for publication: SHELXL97.
C64H66O6P2 | Dx = 1.217 Mg m−3 |
Mr = 993.11 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21212 | Cell parameters from 65 reflections |
a = 12.1097 (15) Å | θ = 5–25° |
b = 24.311 (3) Å | µ = 0.13 mm−1 |
c = 9.2090 (15) Å | T = 173 K |
V = 2711.1 (6) Å3 | Block, colourless |
Z = 2 | 0.7 × 0.6 × 0.5 mm |
F(000) = 1056 |
Siemens R3 diffractometer | Rint = 0.022 |
Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 3.0° |
Graphite monochromator | h = −15→8 |
ω scans | k = −31→31 |
9442 measured reflections | l = −11→0 |
6225 independent reflections | 3 standard reflections every 247 reflections |
5469 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0541P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
6225 reflections | Δρmax = 0.26 e Å−3 |
327 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2713 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.01 (7) |
C64H66O6P2 | V = 2711.1 (6) Å3 |
Mr = 993.11 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 12.1097 (15) Å | µ = 0.13 mm−1 |
b = 24.311 (3) Å | T = 173 K |
c = 9.2090 (15) Å | 0.7 × 0.6 × 0.5 mm |
Siemens R3 diffractometer | Rint = 0.022 |
9442 measured reflections | 3 standard reflections every 247 reflections |
6225 independent reflections | intensity decay: none |
5469 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.26 e Å−3 |
S = 1.00 | Δρmin = −0.21 e Å−3 |
6225 reflections | Absolute structure: Flack (1983), 2713 Friedel pairs |
327 parameters | Absolute structure parameter: −0.01 (7) |
0 restraints |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 11.7321 (0.0027) x − 5.0650 (0.0144) y + 1.2352 (0.0063) z = 5.6805 (0.0082) * 0.0246 (0.0010) C31 * −0.0138 (0.0011) C32 * −0.0076 (0.0012) C33 * 0.0181 (0.0012) C34 * −0.0075 (0.0011) C35 * −0.0138 (0.0011) C36 Rms deviation of fitted atoms = 0.0154 7.8140 (0.0035) x − 3.2968 (0.0107) y + 6.9235 (0.0023) z = 2.2586 (0.0060) Angle to previous plane (with approximate e.s.d.) = 41.04 (0.05) * 0.0000 (0.0000) C17 * 0.0000 (0.0000) C37 * 0.0000 (0.0000) C17_$1 * 0.0000 (0.0000) C37_$1 Rms deviation of fitted atoms = 0.0000 1.4393 (0.0072) x + 14.3213 (0.0121) y + 7.3606 (0.0036) z = 4.3664 (0.0056) Angle to previous plane (with approximate e.s.d.) = 53.29 (0.04) * −0.0313 (0.0010) C11 * 0.0172 (0.0010) C12 * 0.0102 (0.0011) C13 * −0.0233 (0.0011) C14 * 0.0096 (0.0011) C15 * 0.0177 (0.0010) C16 Rms deviation of fitted atoms = 0.0197 |
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 | ||
P | 0.39807 (3) | 0.241170 (15) | 0.04263 (4) | 0.02217 (9) | |
O1 | 0.46602 (9) | 0.43428 (4) | −0.34478 (12) | 0.0247 (2) | |
O2 | 0.73665 (8) | 0.47728 (4) | −0.38228 (11) | 0.0223 (2) | |
O3 | 0.27820 (9) | 0.23354 (5) | 0.07135 (13) | 0.0316 (3) | |
C11 | 0.45334 (12) | 0.38908 (6) | −0.25670 (16) | 0.0206 (3) | |
C12 | 0.34718 (13) | 0.37690 (6) | −0.20567 (17) | 0.0215 (3) | |
C13 | 0.33389 (12) | 0.33143 (6) | −0.11555 (17) | 0.0219 (3) | |
H13 | 0.2622 | 0.3223 | −0.0812 | 0.026* | |
C14 | 0.42380 (12) | 0.29903 (6) | −0.07464 (16) | 0.0218 (3) | |
C15 | 0.52986 (13) | 0.31416 (6) | −0.12035 (17) | 0.0216 (3) | |
H15 | 0.5917 | 0.2932 | −0.0893 | 0.026* | |
C16 | 0.54621 (12) | 0.35927 (6) | −0.21022 (16) | 0.0205 (3) | |
C17 | 0.66284 (12) | 0.37859 (6) | −0.24160 (17) | 0.0204 (3) | |
H17A | 0.7162 | 0.3500 | −0.2108 | 0.025* | |
H17B | 0.6719 | 0.3845 | −0.3473 | 0.025* | |
C18 | 0.49722 (14) | 0.42224 (7) | −0.49194 (17) | 0.0299 (4) | |
H18A | 0.5473 | 0.3901 | −0.4923 | 0.036* | |
H18B | 0.5385 | 0.4540 | −0.5319 | 0.036* | |
C19 | 0.39991 (16) | 0.41026 (8) | −0.58889 (19) | 0.0378 (4) | |
H19A | 0.3497 | 0.4424 | −0.5909 | 0.045* | |
H19B | 0.3583 | 0.3783 | −0.5507 | 0.045* | |
C20 | 0.44104 (19) | 0.39780 (9) | −0.7423 (2) | 0.0493 (5) | |
H20A | 0.4683 | 0.4317 | −0.7873 | 0.059* | |
H20B | 0.3802 | 0.3829 | −0.8005 | 0.059* | |
H20C | 0.5010 | 0.3708 | −0.7376 | 0.059* | |
C31 | 0.71789 (12) | 0.47961 (6) | −0.23317 (16) | 0.0194 (3) | |
C32 | 0.68638 (12) | 0.43172 (6) | −0.16129 (17) | 0.0209 (3) | |
C33 | 0.67197 (14) | 0.43371 (7) | −0.01123 (18) | 0.0276 (3) | |
H33 | 0.6515 | 0.4014 | 0.0399 | 0.033* | |
C34 | 0.68731 (15) | 0.48250 (7) | 0.06394 (18) | 0.0321 (4) | |
H34 | 0.6798 | 0.4832 | 0.1666 | 0.038* | |
C35 | 0.71347 (13) | 0.53000 (6) | −0.01056 (18) | 0.0274 (3) | |
H35 | 0.7213 | 0.5635 | 0.0415 | 0.033* | |
C36 | 0.72860 (12) | 0.52981 (6) | −0.16015 (17) | 0.0213 (3) | |
C37 | 0.74712 (12) | 0.58406 (6) | −0.23887 (18) | 0.0238 (3) | |
H37A | 0.8178 | 0.6006 | −0.2071 | 0.029* | |
H37B | 0.7513 | 0.5775 | −0.3448 | 0.029* | |
C38 | 0.85048 (14) | 0.46708 (8) | −0.41490 (19) | 0.0351 (4) | |
H38A | 0.8772 | 0.4354 | −0.3574 | 0.042* | |
H38B | 0.8953 | 0.4996 | −0.3885 | 0.042* | |
C39 | 0.86309 (17) | 0.45522 (8) | −0.5732 (2) | 0.0426 (5) | |
H39A | 0.9428 | 0.4539 | −0.5969 | 0.051* | |
H39B | 0.8301 | 0.4859 | −0.6291 | 0.051* | |
C40 | 0.80993 (18) | 0.40174 (9) | −0.6214 (2) | 0.0465 (5) | |
H40A | 0.8407 | 0.3712 | −0.5651 | 0.056* | |
H40B | 0.8248 | 0.3958 | −0.7249 | 0.056* | |
H40C | 0.7300 | 0.4037 | −0.6056 | 0.056* | |
C51 | 0.46214 (13) | 0.18042 (6) | −0.03542 (18) | 0.0247 (3) | |
C52 | 0.43896 (16) | 0.13109 (7) | 0.0353 (2) | 0.0394 (4) | |
H52 | 0.3928 | 0.1313 | 0.1187 | 0.047* | |
C53 | 0.48199 (18) | 0.08209 (7) | −0.0140 (2) | 0.0472 (5) | |
H53 | 0.4646 | 0.0487 | 0.0344 | 0.057* | |
C54 | 0.55027 (16) | 0.08154 (8) | −0.1337 (2) | 0.0426 (5) | |
H54 | 0.5807 | 0.0478 | −0.1673 | 0.051* | |
C55 | 0.57424 (18) | 0.12983 (9) | −0.2043 (2) | 0.0494 (5) | |
H55 | 0.6216 | 0.1295 | −0.2865 | 0.059* | |
C56 | 0.52972 (18) | 0.17911 (7) | −0.1563 (2) | 0.0415 (5) | |
H56 | 0.5458 | 0.2122 | −0.2069 | 0.050* | |
C61 | 0.47378 (14) | 0.25090 (6) | 0.21071 (16) | 0.0254 (3) | |
C62 | 0.41416 (15) | 0.25503 (8) | 0.34008 (18) | 0.0365 (4) | |
H62 | 0.3358 | 0.2529 | 0.3383 | 0.044* | |
C63 | 0.46896 (18) | 0.26218 (9) | 0.4715 (2) | 0.0468 (5) | |
H63 | 0.4279 | 0.2649 | 0.5591 | 0.056* | |
C64 | 0.58217 (18) | 0.26534 (8) | 0.4750 (2) | 0.0447 (5) | |
H64 | 0.6193 | 0.2702 | 0.5650 | 0.054* | |
C65 | 0.64226 (16) | 0.26148 (9) | 0.3476 (2) | 0.0401 (4) | |
H65 | 0.7205 | 0.2639 | 0.3503 | 0.048* | |
C66 | 0.58826 (14) | 0.25409 (7) | 0.21505 (17) | 0.0307 (3) | |
H66 | 0.6298 | 0.2512 | 0.1279 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P | 0.01952 (18) | 0.01737 (16) | 0.0296 (2) | −0.00170 (15) | 0.00139 (16) | 0.00544 (15) |
O1 | 0.0279 (6) | 0.0189 (5) | 0.0274 (6) | 0.0014 (4) | 0.0024 (5) | 0.0059 (4) |
O2 | 0.0212 (5) | 0.0230 (5) | 0.0225 (5) | −0.0003 (4) | 0.0044 (4) | 0.0006 (4) |
O3 | 0.0215 (6) | 0.0277 (6) | 0.0458 (7) | −0.0035 (4) | 0.0036 (5) | 0.0125 (5) |
C11 | 0.0223 (8) | 0.0159 (6) | 0.0236 (7) | −0.0017 (6) | 0.0005 (6) | 0.0000 (6) |
C12 | 0.0201 (7) | 0.0162 (7) | 0.0282 (8) | −0.0001 (6) | −0.0038 (6) | −0.0026 (6) |
C13 | 0.0169 (7) | 0.0205 (7) | 0.0284 (8) | −0.0027 (6) | 0.0000 (6) | −0.0006 (6) |
C14 | 0.0227 (8) | 0.0160 (6) | 0.0266 (8) | −0.0028 (5) | 0.0002 (6) | 0.0038 (6) |
C15 | 0.0204 (7) | 0.0189 (6) | 0.0254 (7) | 0.0007 (6) | −0.0020 (6) | 0.0016 (6) |
C16 | 0.0194 (8) | 0.0186 (7) | 0.0234 (7) | −0.0007 (6) | 0.0005 (6) | −0.0018 (6) |
C17 | 0.0179 (7) | 0.0182 (7) | 0.0252 (7) | 0.0009 (5) | 0.0030 (6) | 0.0021 (6) |
C18 | 0.0322 (9) | 0.0311 (8) | 0.0262 (8) | 0.0023 (7) | 0.0043 (7) | 0.0065 (7) |
C19 | 0.0382 (10) | 0.0401 (9) | 0.0350 (9) | 0.0094 (8) | −0.0055 (8) | 0.0007 (8) |
C20 | 0.0655 (15) | 0.0503 (12) | 0.0322 (10) | 0.0163 (10) | −0.0100 (10) | −0.0001 (9) |
C31 | 0.0134 (7) | 0.0220 (7) | 0.0227 (7) | 0.0025 (6) | 0.0016 (6) | −0.0007 (6) |
C32 | 0.0157 (7) | 0.0226 (7) | 0.0244 (7) | 0.0019 (6) | 0.0000 (6) | −0.0003 (6) |
C33 | 0.0309 (9) | 0.0262 (7) | 0.0259 (8) | −0.0003 (7) | 0.0009 (7) | 0.0042 (6) |
C34 | 0.0373 (10) | 0.0378 (9) | 0.0211 (8) | 0.0028 (8) | −0.0020 (7) | −0.0020 (7) |
C35 | 0.0266 (8) | 0.0266 (8) | 0.0291 (8) | 0.0015 (6) | −0.0043 (7) | −0.0074 (7) |
C36 | 0.0144 (7) | 0.0216 (7) | 0.0279 (8) | 0.0003 (6) | −0.0003 (6) | −0.0003 (6) |
C37 | 0.0187 (7) | 0.0189 (7) | 0.0338 (8) | −0.0010 (6) | 0.0042 (6) | −0.0012 (6) |
C38 | 0.0238 (8) | 0.0441 (10) | 0.0373 (10) | −0.0039 (8) | 0.0098 (7) | −0.0096 (8) |
C39 | 0.0397 (11) | 0.0487 (11) | 0.0392 (11) | −0.0060 (9) | 0.0171 (8) | −0.0048 (9) |
C40 | 0.0462 (12) | 0.0517 (12) | 0.0417 (11) | −0.0070 (9) | 0.0158 (9) | −0.0142 (10) |
C51 | 0.0226 (8) | 0.0203 (7) | 0.0313 (8) | −0.0004 (6) | −0.0052 (7) | 0.0000 (6) |
C52 | 0.0432 (10) | 0.0253 (8) | 0.0497 (11) | 0.0030 (7) | 0.0074 (9) | 0.0066 (8) |
C53 | 0.0571 (13) | 0.0236 (8) | 0.0608 (13) | 0.0074 (8) | −0.0020 (11) | 0.0049 (9) |
C54 | 0.0395 (11) | 0.0306 (9) | 0.0577 (12) | 0.0096 (8) | −0.0172 (10) | −0.0155 (9) |
C55 | 0.0504 (13) | 0.0477 (11) | 0.0502 (12) | −0.0007 (10) | 0.0115 (10) | −0.0180 (10) |
C56 | 0.0519 (12) | 0.0299 (9) | 0.0426 (11) | −0.0067 (8) | 0.0110 (10) | −0.0029 (8) |
C61 | 0.0289 (8) | 0.0196 (7) | 0.0277 (7) | 0.0006 (6) | 0.0028 (6) | 0.0039 (6) |
C62 | 0.0331 (10) | 0.0428 (10) | 0.0336 (9) | −0.0035 (8) | 0.0069 (7) | 0.0047 (8) |
C63 | 0.0541 (13) | 0.0575 (12) | 0.0287 (9) | −0.0009 (10) | 0.0120 (9) | −0.0006 (9) |
C64 | 0.0567 (13) | 0.0482 (11) | 0.0293 (9) | 0.0027 (10) | −0.0057 (9) | −0.0021 (8) |
C65 | 0.0357 (10) | 0.0474 (10) | 0.0374 (9) | 0.0026 (9) | −0.0052 (8) | −0.0028 (9) |
C66 | 0.0291 (9) | 0.0348 (8) | 0.0283 (8) | 0.0040 (7) | −0.0003 (7) | −0.0004 (7) |
P—O3 | 1.4871 (11) | C35—C36 | 1.390 (2) |
P—C14 | 1.8006 (15) | C35—H35 | 0.9500 |
P—C61 | 1.8144 (16) | C36—C37 | 1.522 (2) |
P—C51 | 1.8164 (16) | C37—H37A | 0.9900 |
O1—C11 | 1.3744 (17) | C37—H37B | 0.9900 |
O1—C18 | 1.4369 (19) | C38—C39 | 1.494 (2) |
O2—C31 | 1.3930 (18) | C38—H38A | 0.9900 |
O2—C38 | 1.4323 (19) | C38—H38B | 0.9900 |
C11—C12 | 1.400 (2) | C39—C40 | 1.518 (3) |
C11—C16 | 1.405 (2) | C39—H39A | 0.9900 |
C12—C13 | 1.392 (2) | C39—H39B | 0.9900 |
C12—C37i | 1.516 (2) | C40—H40A | 0.9800 |
C13—C14 | 1.396 (2) | C40—H40B | 0.9800 |
C13—H13 | 0.9500 | C40—H40C | 0.9800 |
C14—C15 | 1.401 (2) | C51—C56 | 1.382 (3) |
C15—C16 | 1.388 (2) | C51—C52 | 1.393 (2) |
C15—H15 | 0.9500 | C52—C53 | 1.377 (3) |
C16—C17 | 1.516 (2) | C52—H52 | 0.9500 |
C17—C32 | 1.515 (2) | C53—C54 | 1.378 (3) |
C17—H17A | 0.9900 | C53—H53 | 0.9500 |
C17—H17B | 0.9900 | C54—C55 | 1.373 (3) |
C18—C19 | 1.507 (2) | C54—H54 | 0.9500 |
C18—H18A | 0.9900 | C55—C56 | 1.386 (3) |
C18—H18B | 0.9900 | C55—H55 | 0.9500 |
C19—C20 | 1.529 (3) | C56—H56 | 0.9500 |
C19—H19A | 0.9900 | C61—C66 | 1.389 (2) |
C19—H19B | 0.9900 | C61—C62 | 1.397 (2) |
C20—H20A | 0.9800 | C62—C63 | 1.391 (3) |
C20—H20B | 0.9800 | C62—H62 | 0.9500 |
C20—H20C | 0.9800 | C63—C64 | 1.373 (3) |
C31—C32 | 1.393 (2) | C63—H63 | 0.9500 |
C31—C36 | 1.399 (2) | C64—C65 | 1.384 (3) |
C32—C33 | 1.394 (2) | C64—H64 | 0.9500 |
C33—C34 | 1.386 (2) | C65—C66 | 1.396 (2) |
C33—H33 | 0.9500 | C65—H65 | 0.9500 |
C34—C35 | 1.380 (2) | C66—H66 | 0.9500 |
C34—H34 | 0.9500 | ||
O3—P—C14 | 111.90 (7) | C36—C35—H35 | 119.3 |
O3—P—C61 | 110.96 (7) | C35—C36—C31 | 117.84 (14) |
C14—P—C61 | 108.81 (7) | C35—C36—C37 | 119.25 (14) |
O3—P—C51 | 112.70 (7) | C31—C36—C37 | 122.73 (13) |
C14—P—C51 | 108.90 (7) | C12i—C37—C36 | 109.61 (12) |
C61—P—C51 | 103.16 (7) | C12i—C37—H37A | 109.7 |
C11—O1—C18 | 115.04 (11) | C36—C37—H37A | 109.7 |
C31—O2—C38 | 111.76 (12) | C12i—C37—H37B | 109.7 |
O1—C11—C12 | 118.01 (13) | C36—C37—H37B | 109.7 |
O1—C11—C16 | 120.18 (13) | H37A—C37—H37B | 108.2 |
C12—C11—C16 | 121.58 (13) | O2—C38—C39 | 109.66 (15) |
C13—C12—C11 | 118.31 (13) | O2—C38—H38A | 109.7 |
C13—C12—C37i | 122.04 (14) | C39—C38—H38A | 109.7 |
C11—C12—C37i | 119.43 (13) | O2—C38—H38B | 109.7 |
C12—C13—C14 | 121.27 (14) | C39—C38—H38B | 109.7 |
C12—C13—H13 | 119.4 | H38A—C38—H38B | 108.2 |
C14—C13—H13 | 119.4 | C38—C39—C40 | 114.07 (17) |
C13—C14—C15 | 119.07 (13) | C38—C39—H39A | 108.7 |
C13—C14—P | 117.90 (11) | C40—C39—H39A | 108.7 |
C15—C14—P | 122.96 (11) | C38—C39—H39B | 108.7 |
C16—C15—C14 | 121.16 (14) | C40—C39—H39B | 108.7 |
C16—C15—H15 | 119.4 | H39A—C39—H39B | 107.6 |
C14—C15—H15 | 119.4 | C39—C40—H40A | 109.5 |
C15—C16—C11 | 118.36 (14) | C39—C40—H40B | 109.5 |
C15—C16—C17 | 119.42 (13) | H40A—C40—H40B | 109.5 |
C11—C16—C17 | 121.87 (13) | C39—C40—H40C | 109.5 |
C32—C17—C16 | 110.25 (12) | H40A—C40—H40C | 109.5 |
C32—C17—H17A | 109.6 | H40B—C40—H40C | 109.5 |
C16—C17—H17A | 109.6 | C56—C51—C52 | 118.42 (15) |
C32—C17—H17B | 109.6 | C56—C51—P | 126.18 (12) |
C16—C17—H17B | 109.6 | C52—C51—P | 115.40 (13) |
H17A—C17—H17B | 108.1 | C53—C52—C51 | 120.94 (18) |
O1—C18—C19 | 113.11 (14) | C53—C52—H52 | 119.5 |
O1—C18—H18A | 109.0 | C51—C52—H52 | 119.5 |
C19—C18—H18A | 109.0 | C54—C53—C52 | 119.95 (17) |
O1—C18—H18B | 109.0 | C54—C53—H53 | 120.0 |
C19—C18—H18B | 109.0 | C52—C53—H53 | 120.0 |
H18A—C18—H18B | 107.8 | C55—C54—C53 | 119.82 (17) |
C18—C19—C20 | 109.34 (17) | C55—C54—H54 | 120.1 |
C18—C19—H19A | 109.8 | C53—C54—H54 | 120.1 |
C20—C19—H19A | 109.8 | C54—C55—C56 | 120.40 (19) |
C18—C19—H19B | 109.8 | C54—C55—H55 | 119.8 |
C20—C19—H19B | 109.8 | C56—C55—H55 | 119.8 |
H19A—C19—H19B | 108.3 | C51—C56—C55 | 120.46 (18) |
C19—C20—H20A | 109.5 | C51—C56—H56 | 119.8 |
C19—C20—H20B | 109.5 | C55—C56—H56 | 119.8 |
H20A—C20—H20B | 109.5 | C66—C61—C62 | 119.16 (15) |
C19—C20—H20C | 109.5 | C66—C61—P | 122.42 (12) |
H20A—C20—H20C | 109.5 | C62—C61—P | 118.41 (13) |
H20B—C20—H20C | 109.5 | C63—C62—C61 | 120.30 (17) |
C32—C31—O2 | 118.64 (13) | C63—C62—H62 | 119.9 |
C32—C31—C36 | 121.74 (13) | C61—C62—H62 | 119.9 |
O2—C31—C36 | 119.60 (13) | C64—C63—C62 | 120.25 (17) |
C31—C32—C33 | 118.46 (14) | C64—C63—H63 | 119.9 |
C31—C32—C17 | 122.15 (13) | C62—C63—H63 | 119.9 |
C33—C32—C17 | 119.34 (14) | C63—C64—C65 | 120.05 (18) |
C34—C33—C32 | 120.55 (15) | C63—C64—H64 | 120.0 |
C34—C33—H33 | 119.7 | C65—C64—H64 | 120.0 |
C32—C33—H33 | 119.7 | C64—C65—C66 | 120.24 (17) |
C35—C34—C33 | 119.91 (15) | C64—C65—H65 | 119.9 |
C35—C34—H34 | 120.0 | C66—C65—H65 | 119.9 |
C33—C34—H34 | 120.0 | C61—C66—C65 | 119.99 (15) |
C34—C35—C36 | 121.34 (14) | C61—C66—H66 | 120.0 |
C34—C35—H35 | 119.3 | C65—C66—H66 | 120.0 |
C18—O1—C11—C12 | −113.28 (15) | C33—C34—C35—C36 | −2.2 (3) |
C18—O1—C11—C16 | 72.08 (18) | C34—C35—C36—C31 | −0.8 (2) |
O1—C11—C12—C13 | −179.53 (13) | C34—C35—C36—C37 | 174.54 (15) |
C16—C11—C12—C13 | −5.0 (2) | C32—C31—C36—C35 | 4.0 (2) |
O1—C11—C12—C37i | −4.8 (2) | O2—C31—C36—C35 | −177.51 (14) |
C16—C11—C12—C37i | 169.77 (14) | C32—C31—C36—C37 | −171.23 (14) |
C11—C12—C13—C14 | 1.0 (2) | O2—C31—C36—C37 | 7.3 (2) |
C37i—C12—C13—C14 | −173.61 (14) | C35—C36—C37—C12i | −55.51 (19) |
C12—C13—C14—C15 | 2.8 (2) | C31—C36—C37—C12i | 119.62 (16) |
C12—C13—C14—P | 179.86 (11) | C31—O2—C38—C39 | 170.17 (14) |
O3—P—C14—C13 | 4.41 (15) | O2—C38—C39—C40 | −67.0 (2) |
C61—P—C14—C13 | −118.57 (12) | O3—P—C51—C56 | 131.21 (16) |
C51—P—C14—C13 | 129.66 (12) | C14—P—C51—C56 | 6.42 (18) |
O3—P—C14—C15 | −178.66 (12) | C61—P—C51—C56 | −109.05 (16) |
C61—P—C14—C15 | 58.37 (15) | O3—P—C51—C52 | −48.46 (15) |
C51—P—C14—C15 | −53.40 (15) | C14—P—C51—C52 | −173.25 (13) |
C13—C14—C15—C16 | −2.7 (2) | C61—P—C51—C52 | 71.28 (14) |
P—C14—C15—C16 | −179.65 (12) | C56—C51—C52—C53 | −0.2 (3) |
C14—C15—C16—C11 | −1.1 (2) | P—C51—C52—C53 | 179.53 (16) |
C14—C15—C16—C17 | 172.26 (14) | C51—C52—C53—C54 | 0.9 (3) |
O1—C11—C16—C15 | 179.46 (13) | C52—C53—C54—C55 | −0.7 (3) |
C12—C11—C16—C15 | 5.0 (2) | C53—C54—C55—C56 | −0.3 (3) |
O1—C11—C16—C17 | 6.3 (2) | C52—C51—C56—C55 | −0.8 (3) |
C12—C11—C16—C17 | −168.14 (14) | P—C51—C56—C55 | 179.50 (16) |
C15—C16—C17—C32 | −107.02 (15) | C54—C55—C56—C51 | 1.1 (3) |
C11—C16—C17—C32 | 66.07 (18) | O3—P—C61—C66 | 174.20 (13) |
C11—O1—C18—C19 | 85.98 (16) | C14—P—C61—C66 | −62.26 (15) |
O1—C18—C19—C20 | −179.80 (14) | C51—P—C61—C66 | 53.28 (14) |
C38—O2—C31—C32 | −92.89 (16) | O3—P—C61—C62 | −5.49 (15) |
C38—O2—C31—C36 | 88.53 (17) | C14—P—C61—C62 | 118.05 (13) |
O2—C31—C32—C33 | 177.48 (14) | C51—P—C61—C62 | −126.41 (13) |
C36—C31—C32—C33 | −4.0 (2) | C66—C61—C62—C63 | −0.1 (3) |
O2—C31—C32—C17 | −5.1 (2) | P—C61—C62—C63 | 179.63 (15) |
C36—C31—C32—C17 | 173.42 (13) | C61—C62—C63—C64 | 0.1 (3) |
C16—C17—C32—C31 | −121.97 (15) | C62—C63—C64—C65 | 0.1 (3) |
C16—C17—C32—C33 | 55.40 (19) | C63—C64—C65—C66 | −0.3 (3) |
C31—C32—C33—C34 | 0.9 (2) | C62—C61—C66—C65 | −0.2 (3) |
C17—C32—C33—C34 | −176.61 (14) | P—C61—C66—C65 | −179.85 (14) |
C32—C33—C34—C35 | 2.2 (3) | C64—C65—C66—C61 | 0.4 (3) |
Symmetry code: (i) −x+1, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O3ii | 0.95 | 2.36 | 3.2546 (19) | 158 |
C17—H17A···O3ii | 0.99 | 2.52 | 3.4410 (18) | 155 |
C66—H66···O3ii | 0.95 | 2.59 | 3.512 (2) | 163 |
Symmetry code: (ii) x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C64H66O6P2 |
Mr | 993.11 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 173 |
a, b, c (Å) | 12.1097 (15), 24.311 (3), 9.2090 (15) |
V (Å3) | 2711.1 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.7 × 0.6 × 0.5 |
Data collection | |
Diffractometer | Siemens R3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9442, 6225, 5469 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.085, 1.00 |
No. of reflections | 6225 |
No. of parameters | 327 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.21 |
Absolute structure | Flack (1983), 2713 Friedel pairs |
Absolute structure parameter | −0.01 (7) |
Computer programs: XSCANS (Fait, 1991), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP5 (Siemens, 1994), SHELXL97.
P—O3 | 1.4871 (11) | P—C61 | 1.8144 (16) |
P—C14 | 1.8006 (15) | P—C51 | 1.8164 (16) |
O3—P—C14 | 111.90 (7) | O3—P—C51 | 112.70 (7) |
O3—P—C61 | 110.96 (7) | C14—P—C51 | 108.90 (7) |
C14—P—C61 | 108.81 (7) | C61—P—C51 | 103.16 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C15—H15···O3i | 0.95 | 2.36 | 3.2546 (19) | 158 |
C17—H17A···O3i | 0.99 | 2.52 | 3.4410 (18) | 155 |
C66—H66···O3i | 0.95 | 2.59 | 3.512 (2) | 163 |
Symmetry code: (i) x+1/2, −y+1/2, −z. |
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Phosphine oxides constitute an important class of molecules that have been extensively studied in coordination chemistry for three main reasons: (i) they may specifically bind certain metal ions, in particular, lanthanides and actinides; (ii) they constitute valuable precursors for the preparation of tertiary phosphines, suitable in turn for the preparation of transition metal complexes; (iii) when used as additional ligands in transition metal catalyzed reactions, e.g. carbonylations, they may drastically modify the outcome of the reaction (Clark et al., 2002).
As part of our ongoing investigations of the preparations of phosphorus-functionalized calixarenes (Bagatin et al., 1999), we recently reported the synthesis of the upper rim diphosphorylated calix[4]arene, (2) (Wieser-Jeunesse et al., 1998). The extraction properties of (2) towards rare-earth metal ions are similar to those of triphenylphosphine oxide (Burgard et al., 2000). Here we present the structure of (2).
The molecule of (2) is shown in Fig. 1; it displays crystallographic twofold symmetry. Bond lengths and angles (e.g. those at phosphorus, Table 1) may be considered normal. The cone conformation of the calixarene core is retained from the precursor (1). The reference plane of the calixarene, defined as the mean plane of the bridging C atoms (here C17, C37 and their equivalents) is exact by symmetry; the rings C11–C16 and C31–C36 subtend angles of 36.94 (3) and 82.29 (4)°, respectively, to this plane. The distances between centroids are 4.95 Å for C31–C36 and its symmetry-equivalent ring, and 7.68 Å for C11–C16 and its equivalent.
The phosphoryl O atom is directed away from the ring system in such a way that the angle between the P═O vector and the normal to the reference plane is 79.8°. This enables O3 to accept three C—H···O hydrogen bonds from a neighbouring molecule (Table 2 and Fig. 2) related by the 21 axis parallel to a.