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The crown ether portion of the title complex, C50H66O6·C3H7NO, is not pre-organized for metal binding to the four calix[4]arene O atoms. N,N-Dimethylformamide forms a hydrogen-bond bridge between two calix[4]arene-crown molecules.
Supporting information
CCDC reference: 182603
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.004 Å
- R factor = 0.058
- wR factor = 0.171
- Data-to-parameter ratio = 14.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
DIFMX_01 Alert C The maximum difference density is > 0.1*ZMAX*0.75
_refine_diff_density_max given = 0.660
Test value = 0.600
DIFMX_02 Alert C The minimum difference density is > 0.1*ZMAX*0.75
The relevant atom site should be identified.
PLAT_213 Alert C Atom C50 has ADP max/min Ratio ........... 3.10 prolate
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
The title compound was prepared as previously described (Arduini et al.,
1997) and crystallized from N,N-dimethylformamide.
A 1.1 mm collimator was used. The hydroxyl H atoms were located in a difference
map, and their coordinates refined, although their O—H bond lengths were
restrained to be equal. All other H atoms were placed in calculated positions,
and refined using a riding model. All H atoms were given an isotropic
displacement parameter equal to 1.2 (CH and CH2) or 1.5 (OH and CH3) times
the equivalent isotropic displacement parameter of the atom to which they were
attached. The C—H distances used depended on the type of C atom:
Cmethylene—H = 0.99, Cmethyl—H = 0.98, and Csp2—H = 0.95 Å. The largest peak of residual electron density in the final difference map
is 0.66 e Å-3, and is located roughly 1.3 Å from N, C51 and C52. This
peak, along with some unuusual variations in the thermal parameters in the the
DMF molecule, suggest there is some unresolved disorder in this molecule. The
next highest peak is 0.39 e Å-3, and is located near C49.
Data collection: CAD-4-PC (Nonius, 1996); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2001).
Crystal data top
C50H66O6·C3H7NO | F(000) = 1816 |
Mr = 836.1 | Dx = 1.15 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 12.6115 (13) Å | θ = 10.0–14.4° |
b = 20.000 (3) Å | µ = 0.08 mm−1 |
c = 19.995 (3) Å | T = 173 K |
β = 107.087 (9)° | Fragment, colorless |
V = 4820.7 (12) Å3 | 0.47 × 0.41 × 0.34 mm |
Z = 4 | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.0° |
Graphite monochromator | h = −14→0 |
ω scans | k = −23→13 |
10485 measured reflections | l = −22→23 |
8451 independent reflections | 3 standard reflections every 120 min |
5151 reflections with I > 2σ(I) | intensity decay: 5% |
Refinement top
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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0742P)2 + 3.2092P] where P = (Fo2 + 2Fc2)/3 |
8451 reflections | (Δ/σ)max < 0.001 |
570 parameters | Δρmax = 0.66 e Å−3 |
1 restraint | Δρmin = −0.38 e Å−3 |
0 constraints | |
Crystal data top
C50H66O6·C3H7NO | V = 4820.7 (12) Å3 |
Mr = 836.1 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.6115 (13) Å | µ = 0.08 mm−1 |
b = 20.000 (3) Å | T = 173 K |
c = 19.995 (3) Å | 0.47 × 0.41 × 0.34 mm |
β = 107.087 (9)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
10485 measured reflections | 3 standard reflections every 120 min |
8451 independent reflections | intensity decay: 5% |
5151 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.058 | 1 restraint |
wR(F2) = 0.171 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.66 e Å−3 |
8451 reflections | Δρmin = −0.38 e Å−3 |
570 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.17928 (15) | 0.58125 (9) | 0.43896 (9) | 0.0287 (6) | |
O2 | 0.12627 (18) | 0.47798 (12) | 0.57524 (12) | 0.0468 (8) | |
O3 | 0.37511 (17) | 0.52278 (10) | 0.62161 (10) | 0.0375 (7) | |
O4 | 0.38727 (15) | 0.64740 (9) | 0.55149 (9) | 0.0287 (6) | |
O5 | 0.20233 (18) | 0.75172 (10) | 0.52311 (11) | 0.0372 (7) | |
O6 | 0.03634 (17) | 0.68126 (10) | 0.43608 (10) | 0.0333 (7) | |
C1 | 0.2000 (2) | 0.57087 (13) | 0.37460 (14) | 0.0257 (8) | |
C2 | 0.3086 (2) | 0.55854 (13) | 0.37345 (14) | 0.0239 (8) | |
C3 | 0.3243 (2) | 0.54718 (13) | 0.30868 (14) | 0.0273 (9) | |
C4 | 0.2385 (2) | 0.54953 (13) | 0.24622 (14) | 0.0274 (9) | |
C5 | 0.1330 (2) | 0.56398 (14) | 0.25053 (14) | 0.0278 (8) | |
C6 | 0.1118 (2) | 0.57470 (13) | 0.31431 (14) | 0.0260 (9) | |
C7 | 0.4074 (2) | 0.56290 (14) | 0.43882 (14) | 0.0269 (9) | |
C8 | 0.4500 (2) | 0.63422 (13) | 0.44974 (14) | 0.0249 (8) | |
C9 | 0.4312 (2) | 0.67518 (14) | 0.50169 (14) | 0.0249 (8) | |
C10 | 0.4557 (2) | 0.74363 (14) | 0.50364 (14) | 0.0262 (8) | |
C11 | 0.5084 (2) | 0.76815 (14) | 0.45657 (14) | 0.0281 (9) | |
C12 | 0.5360 (2) | 0.72800 (14) | 0.40752 (15) | 0.0285 (9) | |
C13 | 0.5040 (2) | 0.66151 (14) | 0.40445 (15) | 0.0284 (9) | |
C14 | 0.4202 (2) | 0.79212 (14) | 0.55143 (14) | 0.0287 (9) | |
C15 | 0.3248 (2) | 0.83538 (14) | 0.50899 (14) | 0.0273 (9) | |
C16 | 0.2161 (2) | 0.81116 (14) | 0.49277 (14) | 0.0269 (9) | |
C17 | 0.1277 (2) | 0.84685 (14) | 0.44921 (14) | 0.0264 (9) | |
C18 | 0.1501 (2) | 0.90826 (14) | 0.42348 (14) | 0.0299 (9) | |
C19 | 0.2570 (2) | 0.93482 (14) | 0.43900 (14) | 0.0310 (9) | |
C20 | 0.3422 (2) | 0.89664 (14) | 0.48277 (14) | 0.0287 (9) | |
C21 | 0.0093 (2) | 0.82130 (14) | 0.42930 (15) | 0.0306 (9) | |
C22 | −0.0201 (2) | 0.77652 (14) | 0.36464 (14) | 0.0270 (9) | |
C23 | −0.0034 (2) | 0.70819 (14) | 0.36977 (14) | 0.0270 (9) | |
C24 | −0.0268 (2) | 0.66724 (15) | 0.31062 (14) | 0.0281 (9) | |
C25 | −0.0694 (2) | 0.69807 (15) | 0.24568 (15) | 0.0314 (9) | |
C26 | −0.0903 (2) | 0.76628 (15) | 0.23749 (15) | 0.0331 (10) | |
C27 | −0.0636 (2) | 0.80448 (15) | 0.29850 (15) | 0.0322 (9) | |
C28 | −0.0042 (2) | 0.59253 (14) | 0.31581 (15) | 0.0287 (9) | |
C29 | 0.1631 (3) | 0.51908 (15) | 0.47143 (16) | 0.0362 (10) | |
C30 | 0.1353 (3) | 0.53710 (16) | 0.53759 (16) | 0.0392 (10) | |
C31 | 0.2271 (3) | 0.44354 (17) | 0.60868 (18) | 0.0463 (11) | |
C32 | 0.3120 (3) | 0.48630 (16) | 0.65895 (16) | 0.0415 (11) | |
C33 | 0.4209 (3) | 0.58260 (16) | 0.65607 (15) | 0.0387 (10) | |
C34 | 0.4726 (2) | 0.62166 (15) | 0.61038 (15) | 0.0330 (9) | |
C35 | 0.2591 (3) | 0.53424 (15) | 0.17581 (15) | 0.0338 (10) | |
C36 | 0.2667 (6) | 0.4596 (2) | 0.1695 (2) | 0.103 (3) | |
C37 | 0.1694 (3) | 0.5615 (2) | 0.11424 (17) | 0.0620 (13) | |
C38 | 0.3675 (3) | 0.5657 (3) | 0.1729 (2) | 0.088 (2) | |
C39 | 0.5983 (3) | 0.75818 (15) | 0.35929 (16) | 0.0369 (10) | |
C40 | 0.6058 (4) | 0.7104 (2) | 0.3020 (2) | 0.0662 (17) | |
C41 | 0.5373 (3) | 0.82031 (18) | 0.3227 (2) | 0.0545 (12) | |
C42 | 0.7147 (3) | 0.7775 (2) | 0.4030 (2) | 0.0613 (16) | |
C43 | 0.2814 (3) | 1.00290 (16) | 0.41097 (16) | 0.0391 (10) | |
C44 | 0.3176 (4) | 1.05219 (18) | 0.4709 (2) | 0.0661 (16) | |
C45 | 0.3775 (3) | 0.9956 (2) | 0.3780 (2) | 0.0670 (17) | |
C46 | 0.1840 (3) | 1.02959 (19) | 0.3542 (2) | 0.0685 (14) | |
C47 | −0.1439 (3) | 0.79648 (17) | 0.16457 (16) | 0.0450 (11) | |
C48 | −0.0719 (4) | 0.7828 (3) | 0.1175 (2) | 0.107 (3) | |
C49 | −0.2556 (4) | 0.7622 (3) | 0.1315 (2) | 0.0814 (19) | |
C50 | −0.1665 (6) | 0.8703 (2) | 0.1671 (2) | 0.127 (3) | |
O7 | 0.1823 (4) | 0.60657 (18) | 0.7189 (2) | 0.119 (2) | |
N | 0.2269 (2) | 0.71322 (15) | 0.75442 (15) | 0.0502 (11) | |
C51 | 0.2019 (4) | 0.6508 (2) | 0.7640 (3) | 0.0736 (19) | |
C52 | 0.2417 (3) | 0.7603 (2) | 0.8102 (2) | 0.0726 (16) | |
C53 | 0.2354 (3) | 0.7401 (2) | 0.6886 (2) | 0.0679 (16) | |
H3 | 0.39710 | 0.53730 | 0.30680 | 0.0330* | |
H5 | 0.149 (3) | 0.7320 (17) | 0.4973 (17) | 0.0560* | |
H5A | 0.07330 | 0.56660 | 0.20860 | 0.0330* | |
H6 | 0.076 (3) | 0.6476 (15) | 0.4367 (18) | 0.0500* | |
H7A | 0.38510 | 0.54810 | 0.48000 | 0.0320* | |
H7B | 0.46720 | 0.53290 | 0.43390 | 0.0320* | |
H11 | 0.52620 | 0.81440 | 0.45800 | 0.0340* | |
H13 | 0.51940 | 0.63340 | 0.37010 | 0.0340* | |
H14A | 0.48360 | 0.82090 | 0.57580 | 0.0350* | |
H14B | 0.39660 | 0.76690 | 0.58720 | 0.0350* | |
H18 | 0.09020 | 0.93310 | 0.39410 | 0.0360* | |
H20 | 0.41570 | 0.91380 | 0.49500 | 0.0340* | |
H21A | −0.04190 | 0.86000 | 0.42050 | 0.0370* | |
H21B | −0.00190 | 0.79590 | 0.46920 | 0.0370* | |
H25 | −0.08490 | 0.67100 | 0.20490 | 0.0380* | |
H27 | −0.07570 | 0.85140 | 0.29480 | 0.0390* | |
H28A | −0.01510 | 0.57560 | 0.35980 | 0.0340* | |
H28B | −0.05870 | 0.56980 | 0.27640 | 0.0340* | |
H29A | 0.23150 | 0.49170 | 0.48250 | 0.0430* | |
H29B | 0.10180 | 0.49320 | 0.43970 | 0.0430* | |
H30A | 0.19400 | 0.56630 | 0.56710 | 0.0470* | |
H30B | 0.06430 | 0.56200 | 0.52570 | 0.0470* | |
H31A | 0.25910 | 0.42640 | 0.57240 | 0.0550* | |
H31B | 0.21000 | 0.40460 | 0.63430 | 0.0550* | |
H32A | 0.27460 | 0.51800 | 0.68260 | 0.0500* | |
H32B | 0.36220 | 0.45780 | 0.69510 | 0.0500* | |
H33A | 0.47760 | 0.57180 | 0.70080 | 0.0470* | |
H33B | 0.36190 | 0.60950 | 0.66670 | 0.0470* | |
H34A | 0.51640 | 0.65910 | 0.63730 | 0.0400* | |
H34B | 0.52330 | 0.59260 | 0.59390 | 0.0400* | |
H36A | 0.19340 | 0.43970 | 0.16310 | 0.1550* | |
H36B | 0.31900 | 0.44170 | 0.21220 | 0.1550* | |
H36C | 0.29270 | 0.44870 | 0.12920 | 0.1550* | |
H37A | 0.19050 | 0.55480 | 0.07130 | 0.0930* | |
H37B | 0.15970 | 0.60940 | 0.12110 | 0.0930* | |
H37C | 0.09950 | 0.53810 | 0.11030 | 0.0930* | |
H38A | 0.37800 | 0.55700 | 0.12700 | 0.1310* | |
H38B | 0.42930 | 0.54620 | 0.20950 | 0.1310* | |
H38C | 0.36510 | 0.61400 | 0.18020 | 0.1310* | |
H40A | 0.64680 | 0.67030 | 0.32310 | 0.0990* | |
H40B | 0.64450 | 0.73230 | 0.27210 | 0.0990* | |
H40C | 0.53090 | 0.69770 | 0.27390 | 0.0990* | |
H41A | 0.57460 | 0.83740 | 0.28960 | 0.0810* | |
H41B | 0.53770 | 0.85470 | 0.35770 | 0.0810* | |
H41C | 0.46050 | 0.80860 | 0.29750 | 0.0810* | |
H42A | 0.75470 | 0.73750 | 0.42530 | 0.0920* | |
H42B | 0.71010 | 0.80960 | 0.43910 | 0.0920* | |
H42C | 0.75440 | 0.79800 | 0.37280 | 0.0920* | |
H44A | 0.33840 | 1.09460 | 0.45360 | 0.0990* | |
H44B | 0.38150 | 1.03410 | 0.50700 | 0.0990* | |
H44C | 0.25630 | 1.05980 | 0.49080 | 0.0990* | |
H45A | 0.35640 | 0.96360 | 0.33930 | 0.1000* | |
H45B | 0.44400 | 0.97950 | 0.41350 | 0.1000* | |
H45C | 0.39300 | 1.03910 | 0.36040 | 0.1000* | |
H46A | 0.12390 | 1.04090 | 0.37410 | 0.1030* | |
H46B | 0.15820 | 0.99550 | 0.31780 | 0.1030* | |
H46C | 0.20640 | 1.06970 | 0.33380 | 0.1030* | |
H48A | −0.10620 | 0.80250 | 0.07140 | 0.1600* | |
H48B | −0.06440 | 0.73440 | 0.11270 | 0.1600* | |
H48C | 0.00160 | 0.80250 | 0.13800 | 0.1600* | |
H49A | −0.30360 | 0.76850 | 0.16160 | 0.1230* | |
H49B | −0.24370 | 0.71430 | 0.12630 | 0.1230* | |
H49C | −0.29090 | 0.78180 | 0.08540 | 0.1230* | |
H50A | −0.09620 | 0.89430 | 0.18540 | 0.1910* | |
H50B | −0.21340 | 0.87810 | 0.19770 | 0.1910* | |
H50C | −0.20470 | 0.88640 | 0.11990 | 0.1910* | |
H51 | 0.19870 | 0.63880 | 0.80930 | 0.0880* | |
H52A | 0.24020 | 0.73680 | 0.85290 | 0.1090* | |
H52B | 0.18180 | 0.79340 | 0.79780 | 0.1090* | |
H52C | 0.31320 | 0.78290 | 0.81810 | 0.1090* | |
H53A | 0.31100 | 0.75630 | 0.69490 | 0.1010* | |
H53B | 0.18300 | 0.77720 | 0.67370 | 0.1010* | |
H53C | 0.21780 | 0.70500 | 0.65290 | 0.1010* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0329 (11) | 0.0322 (11) | 0.0240 (10) | −0.0033 (9) | 0.0129 (9) | 0.0021 (8) |
O2 | 0.0372 (13) | 0.0591 (15) | 0.0465 (13) | 0.0009 (11) | 0.0158 (11) | 0.0253 (12) |
O3 | 0.0394 (12) | 0.0381 (12) | 0.0364 (12) | −0.0044 (10) | 0.0133 (10) | 0.0004 (10) |
O4 | 0.0271 (10) | 0.0340 (11) | 0.0248 (10) | 0.0000 (9) | 0.0074 (8) | 0.0060 (9) |
O5 | 0.0336 (12) | 0.0368 (13) | 0.0354 (12) | −0.0066 (10) | 0.0010 (10) | 0.0048 (10) |
O6 | 0.0350 (12) | 0.0371 (12) | 0.0271 (11) | 0.0023 (9) | 0.0080 (9) | 0.0007 (9) |
C1 | 0.0333 (16) | 0.0215 (14) | 0.0240 (14) | −0.0037 (12) | 0.0111 (13) | 0.0007 (12) |
C2 | 0.0280 (15) | 0.0193 (14) | 0.0248 (14) | −0.0023 (12) | 0.0082 (12) | 0.0031 (11) |
C3 | 0.0283 (15) | 0.0253 (15) | 0.0300 (16) | 0.0008 (12) | 0.0110 (13) | 0.0011 (12) |
C4 | 0.0339 (16) | 0.0224 (14) | 0.0276 (15) | 0.0011 (12) | 0.0115 (13) | 0.0014 (12) |
C5 | 0.0304 (15) | 0.0284 (15) | 0.0225 (14) | −0.0028 (12) | 0.0046 (12) | 0.0010 (12) |
C6 | 0.0270 (15) | 0.0232 (15) | 0.0278 (15) | −0.0033 (12) | 0.0080 (12) | 0.0009 (12) |
C7 | 0.0274 (15) | 0.0273 (15) | 0.0258 (15) | 0.0005 (12) | 0.0073 (12) | 0.0024 (12) |
C8 | 0.0204 (14) | 0.0267 (15) | 0.0256 (15) | 0.0025 (11) | 0.0037 (12) | 0.0048 (12) |
C9 | 0.0188 (14) | 0.0302 (16) | 0.0232 (14) | −0.0003 (12) | 0.0022 (11) | 0.0055 (12) |
C10 | 0.0197 (14) | 0.0303 (16) | 0.0248 (14) | 0.0014 (12) | 0.0005 (11) | 0.0028 (12) |
C11 | 0.0228 (14) | 0.0258 (15) | 0.0324 (16) | −0.0021 (12) | 0.0028 (12) | 0.0030 (13) |
C12 | 0.0246 (15) | 0.0290 (16) | 0.0315 (16) | −0.0004 (12) | 0.0078 (12) | 0.0050 (13) |
C13 | 0.0258 (15) | 0.0308 (16) | 0.0293 (15) | 0.0030 (12) | 0.0094 (12) | 0.0016 (13) |
C14 | 0.0271 (15) | 0.0327 (16) | 0.0227 (14) | −0.0022 (12) | 0.0015 (12) | −0.0016 (12) |
C15 | 0.0275 (15) | 0.0322 (16) | 0.0198 (14) | 0.0014 (13) | 0.0034 (12) | −0.0045 (12) |
C16 | 0.0311 (16) | 0.0295 (16) | 0.0200 (14) | −0.0018 (12) | 0.0075 (12) | −0.0033 (12) |
C17 | 0.0258 (15) | 0.0322 (16) | 0.0205 (14) | 0.0022 (12) | 0.0056 (12) | −0.0074 (12) |
C18 | 0.0259 (15) | 0.0357 (17) | 0.0239 (15) | 0.0048 (13) | 0.0006 (12) | −0.0040 (13) |
C19 | 0.0316 (16) | 0.0330 (16) | 0.0253 (15) | 0.0005 (13) | 0.0035 (13) | 0.0000 (13) |
C20 | 0.0264 (15) | 0.0319 (16) | 0.0253 (15) | −0.0030 (12) | 0.0039 (12) | −0.0039 (12) |
C21 | 0.0243 (15) | 0.0351 (17) | 0.0318 (16) | 0.0045 (13) | 0.0071 (12) | −0.0031 (13) |
C22 | 0.0169 (14) | 0.0365 (17) | 0.0284 (15) | −0.0003 (12) | 0.0079 (12) | −0.0040 (13) |
C23 | 0.0203 (14) | 0.0364 (17) | 0.0242 (15) | −0.0024 (12) | 0.0062 (12) | −0.0009 (13) |
C24 | 0.0194 (14) | 0.0360 (16) | 0.0291 (15) | −0.0046 (12) | 0.0076 (12) | −0.0033 (13) |
C25 | 0.0246 (15) | 0.0426 (18) | 0.0252 (15) | −0.0049 (13) | 0.0045 (12) | −0.0049 (13) |
C26 | 0.0283 (16) | 0.0382 (18) | 0.0309 (16) | −0.0028 (13) | 0.0057 (13) | 0.0015 (13) |
C27 | 0.0258 (15) | 0.0341 (17) | 0.0348 (17) | 0.0014 (13) | 0.0061 (13) | 0.0011 (14) |
C28 | 0.0238 (15) | 0.0338 (16) | 0.0270 (15) | −0.0049 (12) | 0.0052 (12) | −0.0030 (12) |
C29 | 0.0388 (18) | 0.0371 (18) | 0.0361 (17) | −0.0041 (14) | 0.0162 (14) | 0.0093 (14) |
C30 | 0.0342 (17) | 0.049 (2) | 0.0357 (17) | 0.0018 (15) | 0.0125 (14) | 0.0130 (15) |
C31 | 0.0431 (19) | 0.047 (2) | 0.050 (2) | 0.0015 (16) | 0.0155 (16) | 0.0162 (17) |
C32 | 0.049 (2) | 0.0395 (19) | 0.0370 (18) | −0.0007 (15) | 0.0142 (16) | 0.0138 (15) |
C33 | 0.0420 (19) | 0.0451 (19) | 0.0256 (16) | −0.0035 (15) | 0.0045 (14) | 0.0028 (14) |
C34 | 0.0297 (16) | 0.0368 (17) | 0.0276 (16) | −0.0023 (13) | 0.0008 (13) | 0.0035 (13) |
C35 | 0.0396 (18) | 0.0364 (17) | 0.0276 (16) | 0.0034 (14) | 0.0134 (14) | 0.0006 (13) |
C36 | 0.224 (7) | 0.052 (3) | 0.054 (3) | 0.025 (3) | 0.072 (4) | −0.005 (2) |
C37 | 0.061 (2) | 0.100 (3) | 0.0264 (18) | 0.025 (2) | 0.0152 (17) | 0.0076 (19) |
C38 | 0.055 (3) | 0.181 (5) | 0.034 (2) | −0.019 (3) | 0.0244 (19) | −0.003 (3) |
C39 | 0.0376 (17) | 0.0377 (18) | 0.0402 (18) | −0.0025 (14) | 0.0188 (15) | 0.0049 (14) |
C40 | 0.095 (3) | 0.062 (3) | 0.062 (3) | −0.009 (2) | 0.055 (2) | 0.005 (2) |
C41 | 0.056 (2) | 0.054 (2) | 0.060 (2) | 0.0030 (18) | 0.0272 (19) | 0.0257 (19) |
C42 | 0.036 (2) | 0.081 (3) | 0.071 (3) | −0.0079 (19) | 0.0219 (19) | 0.021 (2) |
C43 | 0.0383 (18) | 0.0366 (18) | 0.0359 (18) | −0.0039 (14) | 0.0007 (15) | 0.0076 (14) |
C44 | 0.087 (3) | 0.042 (2) | 0.060 (3) | −0.019 (2) | 0.007 (2) | 0.0008 (18) |
C45 | 0.067 (3) | 0.067 (3) | 0.072 (3) | −0.001 (2) | 0.028 (2) | 0.026 (2) |
C46 | 0.056 (2) | 0.051 (2) | 0.077 (3) | −0.0076 (19) | −0.014 (2) | 0.026 (2) |
C47 | 0.052 (2) | 0.047 (2) | 0.0309 (17) | 0.0031 (17) | 0.0043 (16) | 0.0053 (15) |
C48 | 0.089 (4) | 0.190 (6) | 0.045 (3) | 0.035 (4) | 0.025 (3) | 0.048 (3) |
C49 | 0.059 (3) | 0.110 (4) | 0.056 (3) | −0.001 (3) | −0.013 (2) | 0.019 (3) |
C50 | 0.238 (8) | 0.058 (3) | 0.046 (3) | 0.030 (4) | −0.019 (4) | 0.013 (2) |
O7 | 0.164 (4) | 0.069 (2) | 0.152 (4) | −0.001 (2) | 0.089 (3) | −0.027 (2) |
N | 0.0533 (18) | 0.0499 (19) | 0.0513 (18) | 0.0084 (15) | 0.0212 (15) | 0.0091 (15) |
C51 | 0.099 (4) | 0.047 (3) | 0.095 (3) | 0.018 (2) | 0.060 (3) | 0.021 (2) |
C52 | 0.049 (2) | 0.086 (3) | 0.082 (3) | 0.007 (2) | 0.018 (2) | −0.030 (3) |
C53 | 0.067 (3) | 0.094 (3) | 0.049 (2) | 0.017 (2) | 0.027 (2) | 0.033 (2) |
Geometric parameters (Å, º) top
O1—C1 | 1.402 (3) | C14—C15 | 1.522 (4) |
O1—C29 | 1.445 (4) | C15—C20 | 1.375 (4) |
O2—C30 | 1.424 (4) | C15—C16 | 1.399 (4) |
O2—C31 | 1.428 (4) | C16—C17 | 1.393 (4) |
O3—C32 | 1.440 (4) | C17—C18 | 1.392 (4) |
O3—C33 | 1.416 (4) | C17—C21 | 1.517 (4) |
O4—C9 | 1.390 (3) | C18—C19 | 1.396 (4) |
O4—C34 | 1.437 (3) | C19—C20 | 1.397 (4) |
O5—C16 | 1.369 (3) | C19—C43 | 1.538 (4) |
O6—C23 | 1.382 (3) | C21—C22 | 1.526 (4) |
O5—H5 | 0.82 (3) | C22—C23 | 1.382 (4) |
O6—H6 | 0.84 (3) | C22—C27 | 1.391 (4) |
O7—C51 | 1.235 (6) | C23—C24 | 1.397 (4) |
N—C52 | 1.429 (5) | C24—C25 | 1.395 (4) |
N—C53 | 1.454 (5) | C24—C28 | 1.519 (4) |
N—C51 | 1.315 (5) | C25—C26 | 1.390 (4) |
C1—C2 | 1.398 (4) | C26—C27 | 1.394 (4) |
C1—C6 | 1.381 (4) | C26—C47 | 1.539 (4) |
C2—C7 | 1.520 (4) | C29—C30 | 1.508 (5) |
C2—C3 | 1.385 (4) | C31—C32 | 1.502 (5) |
C3—C4 | 1.392 (4) | C33—C34 | 1.490 (4) |
C4—C35 | 1.536 (4) | C35—C38 | 1.521 (6) |
C4—C5 | 1.389 (4) | C35—C36 | 1.504 (5) |
C5—C6 | 1.394 (4) | C35—C37 | 1.508 (5) |
C6—C28 | 1.515 (4) | C39—C41 | 1.530 (5) |
C7—C8 | 1.517 (4) | C39—C40 | 1.516 (5) |
C8—C13 | 1.394 (4) | C39—C42 | 1.521 (5) |
C8—C9 | 1.397 (4) | C43—C45 | 1.547 (5) |
C9—C10 | 1.401 (4) | C43—C44 | 1.515 (5) |
C10—C14 | 1.518 (4) | C43—C46 | 1.504 (5) |
C10—C11 | 1.391 (4) | C47—C49 | 1.531 (6) |
C11—C12 | 1.389 (4) | C47—C48 | 1.512 (6) |
C12—C13 | 1.386 (4) | C47—C50 | 1.507 (5) |
C12—C39 | 1.535 (4) | | |
| | | |
C1—O1—C29 | 112.0 (2) | C18—C19—C20 | 116.5 (3) |
C30—O2—C31 | 116.7 (3) | C18—C19—C43 | 122.6 (3) |
C32—O3—C33 | 112.6 (2) | C15—C20—C19 | 123.1 (3) |
C9—O4—C34 | 111.7 (2) | C17—C21—C22 | 113.3 (2) |
C16—O5—H5 | 109 (2) | C23—C22—C27 | 118.5 (3) |
C23—O6—H6 | 112 (2) | C21—C22—C23 | 121.6 (2) |
C52—N—C53 | 115.8 (3) | C21—C22—C27 | 119.9 (3) |
C51—N—C53 | 124.6 (4) | O6—C23—C24 | 120.7 (2) |
C51—N—C52 | 119.6 (4) | O6—C23—C22 | 117.5 (2) |
O1—C1—C6 | 118.3 (2) | C22—C23—C24 | 121.8 (3) |
O1—C1—C2 | 119.3 (2) | C23—C24—C25 | 117.2 (3) |
C2—C1—C6 | 122.5 (2) | C23—C24—C28 | 122.0 (2) |
C1—C2—C3 | 117.0 (2) | C25—C24—C28 | 120.8 (3) |
C1—C2—C7 | 122.3 (2) | C24—C25—C26 | 123.5 (3) |
C3—C2—C7 | 120.5 (2) | C25—C26—C47 | 120.8 (3) |
C2—C3—C4 | 123.1 (2) | C25—C26—C27 | 116.5 (3) |
C3—C4—C35 | 121.3 (3) | C27—C26—C47 | 122.7 (3) |
C3—C4—C5 | 117.2 (2) | C22—C27—C26 | 122.5 (3) |
C5—C4—C35 | 121.4 (3) | C6—C28—C24 | 113.2 (2) |
C4—C5—C6 | 122.2 (2) | O1—C29—C30 | 106.8 (2) |
C5—C6—C28 | 120.0 (2) | O2—C30—C29 | 109.9 (3) |
C1—C6—C28 | 122.0 (2) | O2—C31—C32 | 113.6 (3) |
C1—C6—C5 | 117.9 (2) | O3—C32—C31 | 109.6 (3) |
C2—C7—C8 | 110.1 (2) | O3—C33—C34 | 109.5 (2) |
C9—C8—C13 | 118.4 (2) | O4—C34—C33 | 109.5 (2) |
C7—C8—C9 | 121.9 (2) | C36—C35—C38 | 109.1 (4) |
C7—C8—C13 | 119.6 (2) | C37—C35—C38 | 106.6 (3) |
O4—C9—C10 | 120.1 (2) | C4—C35—C36 | 107.9 (3) |
C8—C9—C10 | 120.6 (2) | C4—C35—C37 | 112.8 (3) |
O4—C9—C8 | 119.3 (2) | C4—C35—C38 | 110.4 (3) |
C11—C10—C14 | 119.2 (2) | C36—C35—C37 | 110.0 (3) |
C9—C10—C14 | 122.6 (2) | C41—C39—C42 | 109.5 (3) |
C9—C10—C11 | 118.1 (2) | C12—C39—C40 | 112.6 (3) |
C10—C11—C12 | 122.9 (3) | C12—C39—C41 | 110.0 (3) |
C11—C12—C13 | 117.1 (3) | C40—C39—C41 | 106.6 (3) |
C11—C12—C39 | 119.8 (2) | C40—C39—C42 | 109.3 (3) |
C13—C12—C39 | 123.1 (3) | C12—C39—C42 | 108.9 (3) |
C8—C13—C12 | 122.6 (3) | C19—C43—C46 | 112.5 (3) |
C10—C14—C15 | 110.1 (2) | C19—C43—C44 | 109.5 (3) |
C16—C15—C20 | 118.4 (2) | C19—C43—C45 | 109.7 (3) |
C14—C15—C20 | 122.0 (2) | C44—C43—C46 | 110.8 (3) |
C14—C15—C16 | 119.5 (2) | C45—C43—C46 | 106.3 (3) |
C15—C16—C17 | 121.1 (3) | C44—C43—C45 | 107.9 (3) |
O5—C16—C15 | 116.2 (2) | C26—C47—C50 | 112.8 (3) |
O5—C16—C17 | 122.7 (2) | C48—C47—C49 | 107.1 (3) |
C16—C17—C18 | 118.1 (2) | C26—C47—C49 | 109.0 (3) |
C18—C17—C21 | 119.4 (2) | C26—C47—C48 | 110.0 (3) |
C16—C17—C21 | 122.5 (2) | C48—C47—C50 | 110.6 (4) |
C17—C18—C19 | 122.7 (3) | C49—C47—C50 | 107.1 (4) |
C20—C19—C43 | 120.9 (3) | O7—C51—N | 125.3 (5) |
| | | |
C29—O1—C1—C2 | −85.8 (3) | C11—C12—C39—C42 | 67.5 (4) |
C29—O1—C1—C6 | 95.5 (3) | C13—C12—C39—C40 | 8.3 (4) |
C1—O1—C29—C30 | −176.9 (2) | C11—C12—C39—C41 | −52.5 (4) |
C31—O2—C30—C29 | 71.8 (4) | C11—C12—C39—C40 | −171.1 (3) |
C30—O2—C31—C32 | 56.6 (4) | C10—C14—C15—C20 | −92.7 (3) |
C33—O3—C32—C31 | 154.7 (3) | C10—C14—C15—C16 | 84.0 (3) |
C32—O3—C33—C34 | −172.9 (3) | C14—C15—C20—C19 | 174.6 (3) |
C34—O4—C9—C8 | 87.8 (3) | C14—C15—C16—O5 | 6.6 (4) |
C34—O4—C9—C10 | −92.5 (3) | C16—C15—C20—C19 | −2.0 (4) |
C9—O4—C34—C33 | −170.6 (2) | C20—C15—C16—C17 | 2.2 (4) |
C52—N—C51—O7 | 176.6 (5) | C14—C15—C16—C17 | −174.6 (2) |
C53—N—C51—O7 | 0.0 (8) | C20—C15—C16—O5 | −176.6 (2) |
O1—C1—C2—C3 | 178.6 (2) | O5—C16—C17—C21 | −2.7 (4) |
O1—C1—C2—C7 | −6.4 (4) | C15—C16—C17—C21 | 178.6 (3) |
C6—C1—C2—C3 | −2.8 (4) | O5—C16—C17—C18 | 177.2 (2) |
C6—C1—C2—C7 | 172.2 (2) | C15—C16—C17—C18 | −1.5 (4) |
O1—C1—C6—C5 | −179.7 (2) | C21—C17—C18—C19 | −179.5 (3) |
O1—C1—C6—C28 | 2.7 (4) | C16—C17—C21—C22 | −87.6 (3) |
C2—C1—C6—C5 | 1.7 (4) | C16—C17—C18—C19 | 0.7 (4) |
C2—C1—C6—C28 | −175.9 (2) | C18—C17—C21—C22 | 92.5 (3) |
C1—C2—C3—C4 | 1.9 (4) | C17—C18—C19—C43 | −179.5 (3) |
C7—C2—C3—C4 | −173.2 (2) | C17—C18—C19—C20 | −0.5 (4) |
C1—C2—C7—C8 | −86.8 (3) | C18—C19—C20—C15 | 1.2 (4) |
C3—C2—C7—C8 | 88.1 (3) | C20—C19—C43—C46 | 168.7 (3) |
C2—C3—C4—C5 | −0.1 (4) | C20—C19—C43—C45 | 50.6 (4) |
C2—C3—C4—C35 | −177.9 (3) | C43—C19—C20—C15 | −179.7 (3) |
C5—C4—C35—C37 | 21.9 (4) | C18—C19—C43—C44 | 111.4 (4) |
C3—C4—C5—C6 | −1.1 (4) | C20—C19—C43—C44 | −67.6 (4) |
C3—C4—C35—C37 | −160.4 (3) | C18—C19—C43—C45 | −130.4 (3) |
C3—C4—C35—C38 | −41.2 (4) | C18—C19—C43—C46 | −12.3 (4) |
C5—C4—C35—C36 | −99.8 (4) | C17—C21—C22—C23 | 89.3 (3) |
C3—C4—C35—C36 | 78.0 (4) | C17—C21—C22—C27 | −90.0 (3) |
C5—C4—C35—C38 | 141.1 (3) | C27—C22—C23—C24 | 1.3 (4) |
C35—C4—C5—C6 | 176.7 (3) | C27—C22—C23—O6 | −177.9 (2) |
C4—C5—C6—C28 | 178.0 (3) | C21—C22—C23—C24 | −177.9 (2) |
C4—C5—C6—C1 | 0.3 (4) | C21—C22—C27—C26 | 178.9 (2) |
C1—C6—C28—C24 | 89.4 (3) | C23—C22—C27—C26 | −0.3 (4) |
C5—C6—C28—C24 | −88.2 (3) | C21—C22—C23—O6 | 2.9 (4) |
C2—C7—C8—C9 | 105.7 (3) | O6—C23—C24—C25 | 178.3 (2) |
C2—C7—C8—C13 | −70.5 (3) | O6—C23—C24—C28 | −3.4 (4) |
C7—C8—C9—O4 | 9.9 (4) | C22—C23—C24—C28 | 177.5 (2) |
C7—C8—C9—C10 | −169.8 (2) | C22—C23—C24—C25 | −0.8 (4) |
C7—C8—C13—C12 | 174.0 (3) | C23—C24—C28—C6 | −88.6 (3) |
C13—C8—C9—O4 | −173.8 (2) | C25—C24—C28—C6 | 89.6 (3) |
C13—C8—C9—C10 | 6.5 (4) | C23—C24—C25—C26 | −0.7 (4) |
C9—C8—C13—C12 | −2.3 (4) | C28—C24—C25—C26 | −179.0 (3) |
O4—C9—C10—C14 | −9.7 (4) | C24—C25—C26—C27 | 1.7 (4) |
C8—C9—C10—C11 | −5.8 (4) | C24—C25—C26—C47 | −176.3 (3) |
C8—C9—C10—C14 | 170.0 (2) | C47—C26—C27—C22 | 176.8 (3) |
O4—C9—C10—C11 | 174.5 (2) | C25—C26—C27—C22 | −1.1 (4) |
C14—C10—C11—C12 | −175.0 (3) | C25—C26—C47—C49 | 57.5 (4) |
C9—C10—C14—C15 | −106.4 (3) | C25—C26—C47—C50 | 176.3 (4) |
C9—C10—C11—C12 | 0.9 (4) | C27—C26—C47—C48 | 122.4 (4) |
C11—C10—C14—C15 | 69.4 (3) | C27—C26—C47—C49 | −120.4 (3) |
C10—C11—C12—C39 | −177.5 (3) | C27—C26—C47—C50 | −1.6 (5) |
C10—C11—C12—C13 | 3.0 (4) | C25—C26—C47—C48 | −59.7 (4) |
C13—C12—C39—C41 | 126.9 (3) | O1—C29—C30—O2 | −175.7 (3) |
C11—C12—C13—C8 | −2.3 (4) | O2—C31—C32—O3 | −85.4 (3) |
C39—C12—C13—C8 | 178.3 (3) | O3—C33—C34—O4 | 69.8 (3) |
C13—C12—C39—C42 | −113.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O6 | 0.82 (3) | 1.88 (4) | 2.694 (3) | 175 (4) |
O6—H6···O1 | 0.84 (3) | 1.85 (3) | 2.682 (3) | 172 (4) |
C7—H7A···O4 | 0.99 | 2.44 | 2.887 (3) | 106 |
C14—H14B···O4 | 0.99 | 2.49 | 2.924 (3) | 106 |
C21—H21B···O6 | 0.99 | 2.47 | 2.820 (3) | 100 |
C28—H28A···O1 | 0.99 | 2.50 | 2.850 (3) | 100 |
C28—H28A···O2i | 0.99 | 2.42 | 3.328 (4) | 152 |
C30—H30A···O3 | 0.99 | 2.39 | 3.011 (4) | 120 |
C32—H32A···O7 | 0.99 | 2.35 | 3.324 (6) | 168 |
C53—H53C···O5 | 0.98 | 2.71 | 3.220 (4) | 113 |
C53—H53C···O7 | 0.98 | 2.48 | 2.861 (6) | 103 |
C51—H51···Cg3ii | 0.95 | 3.04 | 3.961 (6) | 165 |
C52—H52A···Cg3ii | 0.98 | 3.15 | 4.106 (4) | 165 |
C52—H52B···Cg1ii | 0.98 | 2.95 | 3.590 (4) | 124 |
C52—H52B···Cg4ii | 0.98 | 2.97 | 3.592 (4) | 122 |
C52—H52C···Cg2ii | 0.98 | 2.93 | 3.583 (4) | 125 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C50H66O6·C3H7NO |
Mr | 836.1 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 12.6115 (13), 20.000 (3), 19.995 (3) |
β (°) | 107.087 (9) |
V (Å3) | 4820.7 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.47 × 0.41 × 0.34 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10485, 8451, 5151 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.171, 1.02 |
No. of reflections | 8451 |
No. of parameters | 570 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.66, −0.38 |
Selected geometric parameters (Å, º) topO5—H5 | 0.82 (3) | N—C52 | 1.429 (5) |
O6—H6 | 0.84 (3) | N—C53 | 1.454 (5) |
O7—C51 | 1.235 (6) | N—C51 | 1.315 (5) |
| | | |
C16—O5—H5 | 109 (2) | C51—N—C53 | 124.6 (4) |
C23—O6—H6 | 112 (2) | C51—N—C52 | 119.6 (4) |
C52—N—C53 | 115.8 (3) | O7—C51—N | 125.3 (5) |
| | | |
C31—O2—C30—C29 | 71.8 (4) | C53—N—C51—O7 | 0.0 (8) |
C30—O2—C31—C32 | 56.6 (4) | O1—C29—C30—O2 | −175.7 (3) |
C33—O3—C32—C31 | 154.7 (3) | O2—C31—C32—O3 | −85.4 (3) |
C32—O3—C33—C34 | −172.9 (3) | O3—C33—C34—O4 | 69.8 (3) |
C52—N—C51—O7 | 176.6 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O6 | 0.82 (3) | 1.88 (4) | 2.694 (3) | 175 (4) |
O6—H6···O1 | 0.84 (3) | 1.85 (3) | 2.682 (3) | 172 (4) |
C30—H30A···O3 | 0.99 | 2.39 | 3.011 (4) | 120 |
C32—H32A···O7 | 0.99 | 2.35 | 3.324 (6) | 168 |
C53—H53C···O5 | 0.98 | 2.71 | 3.220 (4) | 113 |
C51—H51···Cg3i | 0.95 | 3.04 | 3.961 (6) | 165 |
C52—H52A···Cg3i | 0.98 | 3.15 | 4.106 (4) | 165 |
C52—H52B···Cg1i | 0.98 | 2.95 | 3.590 (4) | 124 |
C52—H52B···Cg4i | 0.98 | 2.97 | 3.592 (4) | 122 |
C52—H52C···Cg2i | 0.98 | 2.93 | 3.583 (4) | 125 |
Symmetry code: (i) x, −y+3/2, z+1/2. |
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We are beginning a new research effort investigating tight ion pair recognition. As a first step, we prepared the title compound (Arduini et al., 1997) in hopes of using its crown ring to partially bind a metal cation and the two remaining phenolic groups as precursors to appendages containing anion-binding groups. The structure of the title compound, (I), was determined to ascertain the degree of pre-organization for cation binding present in this molecule.
Optimal metal binding will occur when the crown ether adopts a conformation with all O—C—C—O torsion angles anti, and all C—O—C—C torsion angles gauche. Examination of Table 2 shows this is not the case for the structure reported here. The crown-ether is collapsed in upon itself, which is commonly observed in the structures of uncomplexed crown ether molecules (Bryan et al., 2001, and references therein). This collapse forms relatively short C—H···O contacts, one of which is listed in Table 3. As evident in the figures, the two crown O2 and O3 atoms are not well oriented for binding a metal cation together with the O atoms directly attached to the calix[4]arene.
The calix[4]arene adopts the cone conformation, as anticipated when two phenolic groups remain unsubstitutued (Böhmer, 1995). This conformation facilitates hydrogen bonding between the phenolic H atoms and the calix[4]arene O atoms (Table 3).
The N,N-dimethylformamide (DMF) molecule acts as a bridge between two calix–crown molecules. Within the asymmetric unit, C—H···O hydrogen bonds (Table 3) are formed both between the crown ring and the DMF O atom (O7), and between one of the DMF methyl atoms (C53) and a calix phenolic O atom (O5). The DMF molecule is enveloped by a symmetry equivalent (symmetry code: x, 3/2 - y, 1/2 + z) calix[4]arene cavity (Fig. 2). The DMF carbonyl C atom (C51) and one of its methyl groups (C52) form numerous C—H···π interactions with the interior of the calixarene rings (Table 3, where Cg1 represents the centroid for C1–6, Cg2 for C8–13, Cg3 for C15–20, and Cg4 for C22–27).