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The title compound, C44H54N2O8·4H2O, has twofold crystallographic symmetry and consists of a calix[4]arene moiety with four phenyl rings arranged alternately in anti-orientation fashion and two azacrown units attached on the lower rims of calix[4]arene. This seems to offer a big cavity inside the molecule which might possess a potential for forming host-guest complexes.
Supporting information
CCDC reference: 143269
Under nitrogen, into a three-neck round-bottom flask, K2CO3 (0.96 g, 6.95 mmol), pre-dried N,N-dimethylformamide (DMF) (60 ml),
25,26,27,28-tetra(5-chloro-3-oxapentyloxy)calix[4]arene (5.00 g, 5.88 mmol),
and p-toluenesulfonamide (2.11 g, 12.3 mmol) were placed and refluxed
for 24 h. DMF was completely removed in vacuo and 10% NaHCO3 aqueous
solution (100 ml) and CH2Cl2 (100 ml) were added and then the organic
layer was separated. The organic layer was washed with water (2 x 50 ml) and dried over anhydrous MgSO4 and filtered. Evaporation of the
CH2Cl2 in vacuo gave a yellowish oil which was purified by column
chromatography (Rf 0.3) using ethyl acetate: hexane (1:8) to provide
4.00 g (65%) of N-tosyl calix[4]arene bis(azacrown-5) as a white solid
(m.p. 421–424 K). To a solution of 1,4-dioxane (100 ml) and methanol (20 ml)
were carefully added N-tosyl calix[4]arene bisazacrown-5 (3.00 g, 2.86 mmol) and 6% Na(Hg) amalgam (0.853 g). The reaction mixture refluxed for 2 d
at 353 K. After cooling to room temperature the solvent was evaporated in
vacuo. CH2Cl2 (50 ml) and water (50 ml) were added and the organic
layer was separated. The CH2Cl2 layer was washed twice with 10%
Na2HPO4 aqueous solution followed by drying over anhydrous MgSO4. After
filtration of magnesium sulfate, removal of the solvent in vacuo gave
calix[4]arene bis(azacrown-5) as a white solid which can be recrystallized
with diethyl ether (30 ml) (m.p. 458–461 K, 52% yield). IR (KBr pellet,
cm-1): 2926, 1456, 1359, 1176, 1094, 928, 767, 664. 1H NMR (CDCl3,
p.p.m.): delta 7.18–6.64 (m, 12 H, Ar—H), 3.88 (s, 8 H, ArCH2Ar),
3.67–3.46 (m, 24 H, –CH2–), 2.81(s, 8 H, –OCH2CH2NCH2–): p.p.m.
157.3,134.6, 131.8, 122.7, 71.7, 71.4, 70.9, 49.6, 38.5. FAB MS m/z
(M+) calculated 738.9, found 739.1.
An H atom of the amine group and those of C3 and C14 sat on a twofold axis could
be located from a difference Fourier map and the positions of the four
hydrogen atoms of two water molecules were calculated by the program HYDROGEN
(Nardelli, 1999), and their positions were fixed with Uiso (H) =
1.2Ueq (N, C, O), while all other H atoms were placed in calculated
positions and allowed to ride upon the carbon atoms with Uiso (H) =
1.2Ueq (C).
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Johnson, 1976); software used to prepare material for publication: WinGX publication routines (Farrugia, 1998).
Crystal data top
C44H54N2O8·4H2O | Dx = 1.225 Mg m−3 |
Mr = 810.96 | Mo Kα radiation, λ = 0.71069 Å |
Orthorhombic, Pbcn | Cell parameters from 25 reflections |
a = 15.922 (2) Å | θ = 11.0–12.5° |
b = 16.7908 (16) Å | µ = 0.09 mm−1 |
c = 16.453 (4) Å | T = 288 K |
V = 4398.6 (13) Å3 | Block, colorless |
Z = 4 | 0.73 × 0.59 × 0.59 mm |
F(000) = 1744 | |
Data collection top
Enraf Nonius CAD4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→18 |
non–profiled ω/2θ scans | k = 0→19 |
4330 measured reflections | l = −19→0 |
3861 independent reflections | 3 standard reflections every 300 min |
2185 reflections with I > 2σ(I) | intensity decay: 2% |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.205 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Calculated w = 1/[σ2(Fo2) + (0.0944P)2 + 2.5719P] where P = (Fo2 + 2Fc2)/3 |
3861 reflections | (Δ/σ)max < 0.001 |
263 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
Crystal data top
C44H54N2O8·4H2O | V = 4398.6 (13) Å3 |
Mr = 810.96 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 15.922 (2) Å | µ = 0.09 mm−1 |
b = 16.7908 (16) Å | T = 288 K |
c = 16.453 (4) Å | 0.73 × 0.59 × 0.59 mm |
Data collection top
Enraf Nonius CAD4 diffractometer | Rint = 0.000 |
4330 measured reflections | 3 standard reflections every 300 min |
3861 independent reflections | intensity decay: 2% |
2185 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.205 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.55 e Å−3 |
3861 reflections | Δρmin = −0.26 e Å−3 |
263 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N | 0.83325 (17) | 0.19262 (18) | 0.21232 (18) | 0.0564 (8) | |
HN | 0.7724 | 0.1956 | 0.2139 | 0.068* | |
O1 | 0.40432 (14) | 0.29323 (13) | 0.14743 (13) | 0.0477 (6) | |
O2 | 0.57001 (14) | 0.07666 (13) | 0.13362 (14) | 0.0506 (6) | |
O3 | 0.73809 (15) | 0.09153 (15) | 0.09413 (15) | 0.0638 (7) | |
O4 | 0.23551 (15) | 0.32006 (17) | 0.18414 (16) | 0.0710 (8) | |
C1 | 0.4904 (2) | 0.29852 (18) | 0.13584 (19) | 0.0436 (8) | |
C2 | 0.5380 (2) | 0.35139 (19) | 0.1824 (2) | 0.0486 (8) | |
C3 | 0.5000 | 0.4006 (3) | 0.2500 | 0.0540 (13) | |
HC3 | 0.4531 | 0.4423 | 0.2264 | 0.065* | |
C4 | 0.6235 (2) | 0.3552 (2) | 0.1657 (2) | 0.0610 (10) | |
HC4 | 0.6569 | 0.3908 | 0.1946 | 0.073* | |
C5 | 0.6599 (2) | 0.3078 (3) | 0.1075 (3) | 0.0682 (11) | |
HC5 | 0.7170 | 0.3126 | 0.0964 | 0.082* | |
C6 | 0.6124 (2) | 0.2537 (2) | 0.0658 (2) | 0.0630 (11) | |
HC6 | 0.6380 | 0.2204 | 0.0280 | 0.076* | |
C7 | 0.5266 (2) | 0.2476 (2) | 0.0788 (2) | 0.0494 (9) | |
C8 | 0.4745 (2) | 0.1864 (2) | 0.0340 (2) | 0.0593 (10) | |
HC8A | 0.5099 | 0.1601 | −0.0058 | 0.071* | |
HC8B | 0.4302 | 0.2137 | 0.0047 | 0.071* | |
C9 | 0.4351 (2) | 0.1235 (2) | 0.0880 (2) | 0.0497 (9) | |
C10 | 0.3484 (2) | 0.1151 (2) | 0.0914 (2) | 0.0605 (10) | |
HC10 | 0.3150 | 0.1471 | 0.0586 | 0.073* | |
C11 | 0.3108 (2) | 0.0607 (2) | 0.1418 (3) | 0.0655 (11) | |
HC11 | 0.2527 | 0.0549 | 0.1419 | 0.079* | |
C12 | 0.3599 (2) | 0.0146 (2) | 0.1924 (2) | 0.0601 (10) | |
HC12 | 0.3343 | −0.0215 | 0.2274 | 0.072* | |
C13 | 0.4464 (2) | 0.02107 (19) | 0.1919 (2) | 0.0501 (9) | |
C14 | 0.5000 | −0.0279 (3) | 0.2500 | 0.0599 (14) | |
HC14 | 0.4603 | −0.0675 | 0.2801 | 0.072* | |
C15 | 0.4835 (2) | 0.07318 (18) | 0.1368 (2) | 0.0444 (8) | |
C16 | 0.6072 (2) | 0.0311 (3) | 0.0689 (3) | 0.0702 (12) | |
H16A | 0.6007 | 0.0593 | 0.0178 | 0.084* | |
H16B | 0.5790 | −0.0199 | 0.0643 | 0.084* | |
C17 | 0.6975 (2) | 0.0186 (2) | 0.0861 (3) | 0.0696 (12) | |
H17A | 0.7037 | −0.0119 | 0.1359 | 0.084* | |
H17B | 0.7228 | −0.0116 | 0.0422 | 0.084* | |
C18 | 0.8247 (2) | 0.0836 (2) | 0.1134 (2) | 0.0622 (11) | |
H18A | 0.8547 | 0.0602 | 0.0680 | 0.075* | |
H18B | 0.8316 | 0.0492 | 0.1603 | 0.075* | |
C19 | 0.8584 (2) | 0.1642 (2) | 0.1314 (2) | 0.0630 (10) | |
H19A | 0.9193 | 0.1628 | 0.1282 | 0.076* | |
H19B | 0.8384 | 0.2013 | 0.0906 | 0.076* | |
C20 | 0.8704 (2) | 0.2694 (2) | 0.2325 (3) | 0.0668 (11) | |
H20A | 0.8500 | 0.3093 | 0.1947 | 0.080* | |
H20B | 0.9309 | 0.2661 | 0.2265 | 0.080* | |
C21 | 0.1500 (2) | 0.2947 (2) | 0.1834 (3) | 0.0702 (12) | |
H21A | 0.1426 | 0.2506 | 0.1460 | 0.084* | |
H21B | 0.1136 | 0.3380 | 0.1667 | 0.084* | |
C22 | 0.2670 (2) | 0.3332 (3) | 0.1074 (2) | 0.0701 (12) | |
H22A | 0.2352 | 0.3754 | 0.0814 | 0.084* | |
H22B | 0.2605 | 0.2853 | 0.0751 | 0.084* | |
C23 | 0.3575 (2) | 0.3559 (2) | 0.1102 (2) | 0.0630 (11) | |
H23A | 0.3781 | 0.3652 | 0.0556 | 0.076* | |
H23B | 0.3642 | 0.4046 | 0.1412 | 0.076* | |
OW1 | 0.9337 (2) | 0.08721 (18) | 0.30622 (19) | 0.0895 (10) | |
H1W1 | 0.9003 | 0.1133 | 0.2746 | 0.107* | |
H2W1 | 0.9028 | 0.0496 | 0.3270 | 0.107* | |
OW2 | 0.9462 (3) | 0.0594 (2) | 0.47177 (19) | 0.1154 (13) | |
H1W2 | 0.9501 | 0.0715 | 0.4210 | 0.138* | |
H2W2 | 0.9531 | 0.0083 | 0.4738 | 0.138* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N | 0.0451 (16) | 0.0609 (19) | 0.0630 (19) | −0.0039 (14) | −0.0002 (14) | 0.0018 (16) |
O1 | 0.0504 (14) | 0.0452 (13) | 0.0475 (13) | 0.0034 (11) | −0.0032 (11) | 0.0050 (11) |
O2 | 0.0478 (14) | 0.0540 (14) | 0.0501 (14) | 0.0019 (11) | −0.0031 (11) | −0.0147 (11) |
O3 | 0.0529 (16) | 0.0665 (17) | 0.0721 (18) | 0.0063 (13) | −0.0026 (13) | −0.0025 (14) |
O4 | 0.0557 (17) | 0.087 (2) | 0.0707 (18) | 0.0031 (14) | −0.0090 (14) | 0.0063 (15) |
C1 | 0.0469 (19) | 0.0437 (18) | 0.0402 (17) | 0.0018 (16) | −0.0009 (15) | 0.0148 (16) |
C2 | 0.055 (2) | 0.0423 (19) | 0.049 (2) | −0.0025 (17) | −0.0049 (17) | 0.0150 (16) |
C3 | 0.068 (3) | 0.039 (3) | 0.055 (3) | 0.000 | −0.009 (3) | 0.000 |
C4 | 0.062 (2) | 0.059 (2) | 0.061 (2) | −0.013 (2) | −0.008 (2) | 0.018 (2) |
C5 | 0.054 (2) | 0.082 (3) | 0.069 (3) | −0.001 (2) | 0.009 (2) | 0.022 (2) |
C6 | 0.064 (3) | 0.073 (3) | 0.052 (2) | 0.010 (2) | 0.011 (2) | 0.011 (2) |
C7 | 0.060 (2) | 0.050 (2) | 0.0381 (18) | 0.0057 (17) | 0.0015 (17) | 0.0091 (16) |
C8 | 0.071 (2) | 0.066 (2) | 0.0411 (19) | 0.013 (2) | −0.0044 (18) | −0.0031 (18) |
C9 | 0.058 (2) | 0.049 (2) | 0.0428 (19) | 0.0076 (17) | −0.0097 (17) | −0.0126 (16) |
C10 | 0.057 (2) | 0.060 (2) | 0.065 (3) | 0.012 (2) | −0.018 (2) | −0.017 (2) |
C11 | 0.049 (2) | 0.069 (3) | 0.079 (3) | −0.001 (2) | −0.009 (2) | −0.016 (2) |
C12 | 0.059 (2) | 0.052 (2) | 0.069 (3) | −0.0110 (19) | −0.002 (2) | −0.009 (2) |
C13 | 0.057 (2) | 0.0392 (19) | 0.055 (2) | −0.0028 (16) | −0.0065 (18) | −0.0099 (16) |
C14 | 0.066 (3) | 0.041 (3) | 0.073 (4) | 0.000 | −0.006 (3) | 0.000 |
C15 | 0.044 (2) | 0.0414 (18) | 0.0472 (19) | 0.0009 (15) | −0.0066 (16) | −0.0174 (16) |
C16 | 0.061 (2) | 0.076 (3) | 0.074 (3) | 0.009 (2) | 0.003 (2) | −0.034 (2) |
C17 | 0.063 (3) | 0.073 (3) | 0.073 (3) | 0.013 (2) | 0.004 (2) | −0.025 (2) |
C18 | 0.054 (2) | 0.069 (3) | 0.063 (2) | 0.0112 (19) | 0.0025 (19) | −0.002 (2) |
C19 | 0.056 (2) | 0.076 (3) | 0.057 (2) | 0.002 (2) | 0.0065 (19) | 0.008 (2) |
C20 | 0.051 (2) | 0.067 (2) | 0.083 (3) | −0.009 (2) | −0.005 (2) | 0.005 (2) |
C21 | 0.053 (2) | 0.066 (3) | 0.092 (3) | 0.004 (2) | −0.014 (2) | 0.009 (2) |
C22 | 0.069 (3) | 0.084 (3) | 0.058 (2) | 0.018 (2) | −0.010 (2) | 0.009 (2) |
C23 | 0.061 (2) | 0.069 (2) | 0.059 (2) | 0.011 (2) | −0.0058 (19) | 0.021 (2) |
OW1 | 0.101 (2) | 0.088 (2) | 0.079 (2) | 0.0274 (18) | −0.0023 (17) | 0.0165 (17) |
OW2 | 0.179 (4) | 0.103 (3) | 0.065 (2) | 0.027 (3) | 0.009 (2) | −0.0020 (19) |
Geometric parameters (Å, º) top
N—C20 | 1.457 (4) | C6—C7 | 1.386 (5) |
N—C19 | 1.471 (5) | C7—C8 | 1.513 (5) |
O1—C1 | 1.386 (4) | C8—C9 | 1.516 (5) |
O1—C23 | 1.428 (4) | C9—C10 | 1.389 (5) |
O2—C15 | 1.380 (4) | C9—C15 | 1.397 (5) |
O2—C16 | 1.438 (4) | C10—C11 | 1.371 (5) |
O3—C17 | 1.392 (4) | C11—C12 | 1.379 (5) |
O3—C18 | 1.421 (4) | C12—C13 | 1.382 (5) |
O4—C22 | 1.377 (4) | C13—C15 | 1.392 (5) |
O4—C21 | 1.427 (4) | C13—C14i | 1.522 (4) |
C1—C2 | 1.397 (4) | C13—C14 | 1.522 (4) |
C1—C7 | 1.395 (4) | C14—C13i | 1.522 (4) |
C2—C4 | 1.392 (5) | C16—C17 | 1.480 (5) |
C2—C3 | 1.511 (4) | C18—C19 | 1.486 (5) |
C3—C2i | 1.511 (4) | C20—C21i | 1.482 (6) |
C4—C5 | 1.374 (5) | C21—C20i | 1.482 (6) |
C5—C6 | 1.367 (5) | C22—C23 | 1.490 (5) |
| | | |
C20—N—C19 | 112.5 (3) | C15—C9—C8 | 122.0 (3) |
C1—O1—C23 | 114.2 (2) | C11—C10—C9 | 121.8 (4) |
C15—O2—C16 | 114.6 (3) | C10—C11—C12 | 119.4 (4) |
C17—O3—C18 | 112.9 (3) | C11—C12—C13 | 121.2 (4) |
C22—O4—C21 | 112.8 (3) | C12—C13—C15 | 118.4 (3) |
O1—C1—C2 | 120.1 (3) | C12—C13—C14i | 120.9 (3) |
O1—C1—C7 | 117.5 (3) | C15—C13—C14i | 120.7 (3) |
C2—C1—C7 | 122.3 (3) | C12—C13—C14 | 120.9 (3) |
C4—C2—C1 | 116.9 (3) | C15—C13—C14 | 120.7 (3) |
C4—C2—C3 | 120.8 (3) | C13i—C14—C13 | 114.6 (4) |
C1—C2—C3 | 122.3 (3) | O2—C15—C13 | 118.3 (3) |
C2—C3—C2i | 113.7 (4) | O2—C15—C9 | 120.2 (3) |
C5—C4—C2 | 121.6 (4) | C13—C15—C9 | 121.4 (3) |
C6—C5—C4 | 120.1 (4) | O2—C16—C17 | 109.5 (3) |
C5—C6—C7 | 121.1 (4) | O3—C17—C16 | 110.1 (3) |
C6—C7—C1 | 117.8 (3) | O3—C18—C19 | 108.1 (3) |
C6—C7—C8 | 121.0 (3) | N—C19—C18 | 112.2 (3) |
C1—C7—C8 | 121.2 (3) | N—C20—C21i | 112.2 (3) |
C7—C8—C9 | 114.4 (3) | O4—C21—C20i | 106.7 (3) |
C10—C9—C15 | 117.6 (3) | O4—C22—C23 | 111.3 (3) |
C10—C9—C8 | 120.4 (3) | O1—C23—C22 | 109.3 (3) |
| | | |
C23—O1—C1—C2 | 78.6 (4) | C12—C13—C14—C14i | 0 (68) |
C23—O1—C1—C7 | −103.6 (3) | C15—C13—C14—C14i | 0 (67) |
O1—C1—C2—C4 | −178.0 (3) | C12—C13—C14—C13i | −119.5 (3) |
C7—C1—C2—C4 | 4.3 (5) | C15—C13—C14—C13i | 60.8 (2) |
O1—C1—C2—C3 | 3.9 (4) | C14i—C13—C14—C13i | 0 (100) |
C7—C1—C2—C3 | −173.7 (3) | C16—O2—C15—C13 | 99.0 (4) |
C4—C2—C3—C2i | −117.0 (3) | C16—O2—C15—C9 | −83.8 (4) |
C1—C2—C3—C2i | 61.0 (3) | C12—C13—C15—O2 | −176.8 (3) |
C1—C2—C4—C5 | −1.6 (5) | C14i—C13—C15—O2 | 2.8 (4) |
C3—C2—C4—C5 | 176.5 (3) | C14—C13—C15—O2 | 2.8 (4) |
C2—C4—C5—C6 | −1.8 (6) | C12—C13—C15—C9 | 6.0 (5) |
C4—C5—C6—C7 | 2.6 (6) | C14i—C13—C15—C9 | −174.4 (3) |
C5—C6—C7—C1 | 0.1 (5) | C14—C13—C15—C9 | −174.4 (3) |
C5—C6—C7—C8 | −178.6 (3) | C10—C9—C15—O2 | 177.4 (3) |
O1—C1—C7—C6 | 178.7 (3) | C8—C9—C15—O2 | −3.5 (5) |
C2—C1—C7—C6 | −3.6 (5) | C10—C9—C15—C13 | −5.4 (5) |
O1—C1—C7—C8 | −2.6 (4) | C8—C9—C15—C13 | 173.7 (3) |
C2—C1—C7—C8 | 175.1 (3) | C15—O2—C16—C17 | −162.5 (3) |
C6—C7—C8—C9 | 115.6 (4) | C18—O3—C17—C16 | 178.0 (3) |
C1—C7—C8—C9 | −63.0 (4) | O2—C16—C17—O3 | −58.5 (5) |
C7—C8—C9—C10 | 119.4 (4) | C17—O3—C18—C19 | −172.5 (3) |
C7—C8—C9—C15 | −59.6 (4) | C20—N—C19—C18 | 176.4 (3) |
C15—C9—C10—C11 | 1.4 (5) | O3—C18—C19—N | 76.2 (4) |
C8—C9—C10—C11 | −177.7 (3) | C19—N—C20—C21i | −175.6 (3) |
C9—C10—C11—C12 | 1.9 (6) | C22—O4—C21—C20i | 170.2 (3) |
C10—C11—C12—C13 | −1.3 (6) | C21—O4—C22—C23 | −177.3 (3) |
C11—C12—C13—C15 | −2.5 (5) | C1—O1—C23—C22 | 165.1 (3) |
C11—C12—C13—C14i | 177.8 (3) | O4—C22—C23—O1 | 59.9 (4) |
C11—C12—C13—C14 | 177.8 (3) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1W1···N | 0.86 | 1.99 | 2.842 (4) | 168 |
OW1—H2W1···OW2 | 0.87 | 2.49 | 2.771 (4) | 100 |
OW2—H1W2···OW1 | 0.86 | 1.92 | 2.771 (4) | 167 |
OW2—H2W2···OW2ii | 0.87 | 2.16 | 2.788 (7) | 129 |
Symmetry code: (ii) −x+2, −y, −z+1. |
Experimental details
Crystal data |
Chemical formula | C44H54N2O8·4H2O |
Mr | 810.96 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 288 |
a, b, c (Å) | 15.922 (2), 16.7908 (16), 16.453 (4) |
V (Å3) | 4398.6 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.73 × 0.59 × 0.59 |
|
Data collection |
Diffractometer | Enraf Nonius CAD4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4330, 3861, 2185 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.205, 0.99 |
No. of reflections | 3861 |
No. of parameters | 263 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.26 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1W1···N | 0.86 | 1.99 | 2.842 (4) | 168 |
OW1—H2W1···OW2 | 0.87 | 2.49 | 2.771 (4) | 100 |
OW2—H1W2···OW1 | 0.86 | 1.92 | 2.771 (4) | 167 |
OW2—H2W2···OW2i | 0.87 | 2.16 | 2.788 (7) | 129 |
Symmetry code: (i) −x+2, −y, −z+1. |
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Calix[4]arenes have been of particular interest as organic hosts and selective ionophores in inclusion complexation (Gutsche, 1989) and it is known that the calix[4]arenes are able to exist in the following four different conformations: cone (Guelzim et al., 1997; Harkema et al., 1998), partial cone (Kim et al., 1993), 1,2-alternate and 1,3-alternate (Ungaro & Pochini, 1991). In order to investigate the characteristics of the calix[4]arene compounds, a series of calix[4]arene derivatives has been synthesized and their structures elucidated (Kim et al., 1997; Kim, Pang et al., 1998; Kim, Yu et al., 1998; Kim, Suh et al., 1998; Kim, Kim, Lee et al., 1999; Kim, Kim, Choo et al., 1999).
In the title compound, (I), a half molecule belongs to an asymmetric unit and a molecule is completed by another half primed molecule translated by twofold symmetry along the b axis [symmetry code: (i) 1 - x, y, 1/2 - z] (Fig. 1). \sch
(I) consists of the calix[4]arene molecule adopting the 1,3-alternate conformation: two phenyl groups A and B' lie above and the other two phenyl groups A' and B below the least-squares plane defined by the four bridging methylene groups as clearly illustrated in Figure 1, two azacrown units: one of them bonded to phenyl rings A and B' and another one to phenyl rings A' and B, respectively, and four water molecules not represented in the Figure.
The aromatic Csp2– Csp2 distances in the molecule vary from 1.367 (5) to 1.397 (5) Å with an average value of 1.385 (1) Å, Csp2—Csp3 distances from 1.511 (4) to 1.522 (4) Å with a mean value of 1.516 (2) Å, Csp3—Csp3 distances from 1.480 (5) to 1.490 (5) Å with a mean value of 1.485 (3) Å, O-Csp3 distances from 1.377 (4) to 1.438 (4) Å with a mean value of 1.414 (2) Å, and a mean value of two O-Csp2 bonds is 1.383 (3) Å. All of these are very close to those in 25,27-bis(1-propyloxy)calix[4]arene- 26,28-[(5',6')(14',15')-dibenzo]crown-7 (Kim, Pang et al., 1999) and in 1,3-alternate calix[4]arenebiscrown-7 (Khrifi et al., 1997).
Bond angles involving the bridging methylenes C2—C3—C2' = 113.7 (4), C7—C8—C9 = 114.4 (3) and C13—C14—C13' = 114.6 (4)° are quite larger than the tetrahedral angle due to repulsions among the four phenyl groups.
Two adjacent phenyl rings in the calix[4]arene are perpendicular to each other with dihedral angle of A—B = 89.76 (8)° so that the calix[4]arene has a fairly perfect square cavity. However, two facing rings A and B' are slightly splayed out upwards from the central axis with a dihedral angle of 11.6 (2)° leading to C1···C15' 5.337 (4) and C5···C11' 5.870 (5) Å, and the same for the pair facing rings A' and B because of symmetry.
In the azacrown unit, O···O and N···O distances are O1···O2' 5.135 (3), O3···O4' 5.311 (4), N···O1' 4.742 (4) and N···O2 4.800 (4) Å, so that the somewhat flexible cavity lined with four oxygen atoms and a nitrogen atom might enable the molecule to introduce a guest atom. Additionally the torsion angles of O2—C16—C17—O3 and O4—C22—C23—O1 in the azacrown unit are both gauche being -58.5 (5) and 59.9 (4)°, respectively.
There are four hydrogen bonds involving the N atom in the amine group and the two water molecules in an asymmetric unit and it is especially worth mentioning that two water oxygen atoms donate and accept their hydrogen atoms with each other as shown in Table 1, where the distances between H2W1····H1W2 and H2W2····H2W2 (2 - x, -y, 1 - z) are 1.76 and 1.74 Å, respectively. This hydrogen-bond scheme makes an infinite molecular chain running in the [201] direction and the closest contact between the molecular chains is OW1···HC3 (1/2 + x, -1/2 + y, 1/2 - z) = 2.51 Å.