Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102008077/sk1542sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102008077/sk1542Isup2.hkl |
CCDC reference: 192964
The title compound was synthesized by reaction of thiacalix[4]arene (TCA) with 2-bromomethylbenzonitrile in the presence of K2CO3 as catalyst. The solid product was collected by filtration and recrystallization from dichloromethane gave the title compound as flat colorless crystals.
H atoms were placed in calculated positions and refined as riding with C—H distances of 0.93, 0.96 and 0.97 for aromatic, methyl and methylene/dichloromethane H atoms, respectively.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL (Sheldrick, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title thiacalix[4]arene showing 35% probability displacement ellipsoids. H atoms and dichloromethane solvent molecules have been omitted for clarity. |
C72H68N4O4S4·2CH2Cl2 | F(000) = 1416 |
Mr = 1351.40 | Dx = 1.278 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 80 reflections |
a = 13.768 (4) Å | θ = 2.4–24.5° |
b = 17.021 (5) Å | µ = 0.34 mm−1 |
c = 15.543 (4) Å | T = 293 K |
β = 105.424 (5)° | Plate, colorless |
V = 3511.3 (17) Å3 | 0.40 × 0.30 × 0.20 mm |
Z = 2 |
Bruker CCD area-detector diffractometer | 6105 independent reflections |
Radiation source: fine-focus sealed tube | 3885 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→16 |
Tmin = 0.877, Tmax = 0.935 | k = −20→15 |
14071 measured reflections | l = −18→13 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.9P] where P = (Fo2 + 2Fc2)/3 |
6105 reflections | (Δ/σ)max = 0.052 |
406 parameters | Δρmax = 0.53 e Å−3 |
0 restraints | Δρmin = −0.68 e Å−3 |
C72H68N4O4S4·2CH2Cl2 | V = 3511.3 (17) Å3 |
Mr = 1351.40 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.768 (4) Å | µ = 0.34 mm−1 |
b = 17.021 (5) Å | T = 293 K |
c = 15.543 (4) Å | 0.40 × 0.30 × 0.20 mm |
β = 105.424 (5)° |
Bruker CCD area-detector diffractometer | 6105 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3885 reflections with I > 2σ(I) |
Tmin = 0.877, Tmax = 0.935 | Rint = 0.039 |
14071 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.53 e Å−3 |
6105 reflections | Δρmin = −0.68 e Å−3 |
406 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.10101 (6) | 0.17507 (5) | 0.91405 (6) | 0.0419 (3) | |
S2 | −0.28260 (6) | 0.11024 (5) | 0.95247 (6) | 0.0452 (3) | |
O1 | −0.08264 (16) | 0.07209 (12) | 0.89977 (14) | 0.0392 (5) | |
O2 | 0.15811 (17) | −0.00487 (13) | 0.90518 (14) | 0.0434 (6) | |
N1 | −0.2570 (4) | 0.1175 (3) | 0.5825 (3) | 0.0871 (13) | |
N2 | 0.0477 (4) | 0.0988 (4) | 0.6007 (3) | 0.1180 (18) | |
C1 | −0.1636 (2) | 0.15912 (17) | 0.9824 (2) | 0.0377 (7) | |
C2 | −0.1590 (3) | 0.22621 (19) | 1.0359 (2) | 0.0420 (8) | |
C3 | −0.0761 (2) | 0.27638 (19) | 1.0549 (2) | 0.0414 (8) | |
C4 | 0.0034 (2) | 0.25717 (19) | 1.0190 (2) | 0.0403 (8) | |
C5 | 0.0016 (2) | 0.19038 (18) | 0.9673 (2) | 0.0361 (7) | |
C6 | −0.0828 (2) | 0.14025 (17) | 0.9486 (2) | 0.0351 (7) | |
C7 | −0.0716 (3) | 0.3515 (2) | 1.1109 (3) | 0.0525 (10) | |
C8 | −0.0696 (5) | 0.4232 (3) | 1.0510 (3) | 0.0896 (16) | |
C9 | −0.1628 (4) | 0.3577 (3) | 1.1508 (4) | 0.0984 (19) | |
C10 | 0.0237 (3) | 0.3522 (3) | 1.1884 (3) | 0.0727 (13) | |
C11 | 0.1872 (2) | 0.11592 (19) | 0.9952 (2) | 0.0363 (7) | |
C12 | 0.2436 (2) | 0.15250 (19) | 1.0734 (2) | 0.0398 (8) | |
C13 | 0.3087 (2) | 0.11139 (19) | 1.1426 (2) | 0.0411 (8) | |
C14 | 0.3127 (2) | 0.03056 (19) | 1.1320 (2) | 0.0403 (8) | |
C15 | 0.2608 (2) | −0.00792 (19) | 1.0543 (2) | 0.0383 (8) | |
C16 | 0.2008 (2) | 0.03557 (18) | 0.9818 (2) | 0.0336 (7) | |
C17 | 0.3723 (3) | 0.1555 (2) | 1.2254 (2) | 0.0507 (9) | |
C18 | 0.3042 (4) | 0.2014 (3) | 1.2691 (3) | 0.0765 (13) | |
C19 | 0.4389 (4) | 0.0984 (3) | 1.2934 (3) | 0.098 (2) | |
C20 | 0.4427 (3) | 0.2129 (3) | 1.1949 (3) | 0.0795 (14) | |
C21 | 0.1633 (3) | 0.0293 (2) | 0.8216 (2) | 0.0533 (9) | |
C22 | 0.1859 (3) | −0.0339 (2) | 0.7620 (3) | 0.0541 (10) | |
C23 | 0.2409 (3) | −0.1004 (3) | 0.7930 (3) | 0.0704 (12) | |
C24 | 0.2619 (4) | −0.1552 (3) | 0.7334 (4) | 0.0904 (16) | |
C25 | 0.2281 (5) | −0.1433 (4) | 0.6426 (4) | 0.1033 (19) | |
C26 | 0.1714 (5) | −0.0786 (4) | 0.6093 (4) | 0.0944 (18) | |
C27 | 0.1507 (3) | −0.0230 (3) | 0.6675 (3) | 0.0664 (12) | |
C28 | 0.0925 (4) | 0.0448 (4) | 0.6301 (3) | 0.0779 (14) | |
C29 | −0.1298 (3) | 0.08019 (19) | 0.8058 (2) | 0.0412 (8) | |
C30 | −0.1148 (2) | 0.0054 (2) | 0.7598 (2) | 0.0404 (8) | |
C31 | −0.0617 (3) | −0.0581 (2) | 0.8043 (3) | 0.0500 (9) | |
C32 | −0.0436 (3) | −0.1233 (2) | 0.7573 (3) | 0.0645 (11) | |
C33 | −0.0786 (4) | −0.1265 (3) | 0.6650 (3) | 0.0747 (13) | |
C34 | −0.1341 (3) | −0.0660 (3) | 0.6198 (3) | 0.0664 (12) | |
C35 | −0.1531 (3) | 0.0007 (2) | 0.6662 (2) | 0.0474 (9) | |
C36 | −0.2107 (3) | 0.0658 (3) | 0.6185 (3) | 0.0585 (10) | |
Cl1 | 0.4272 (4) | 0.2014 (2) | 0.9251 (3) | 0.2541 (19) | |
Cl2 | 0.43900 (17) | 0.03918 (17) | 0.88973 (15) | 0.1532 (8) | |
C37 | 0.4564 (5) | 0.1130 (5) | 0.9651 (7) | 0.147 (3) | |
H2A | −0.2129 | 0.2375 | 1.0593 | 0.050* | |
H4A | 0.0593 | 0.2900 | 1.0300 | 0.048* | |
H8A | −0.1292 | 0.4234 | 1.0021 | 0.134* | |
H8B | −0.0112 | 0.4204 | 1.0285 | 0.134* | |
H8C | −0.0670 | 0.4705 | 1.0853 | 0.134* | |
H9A | −0.1637 | 0.3132 | 1.1884 | 0.148* | |
H9B | −0.2239 | 0.3589 | 1.1034 | 0.148* | |
H9C | −0.1574 | 0.4050 | 1.1854 | 0.148* | |
H10A | 0.0231 | 0.3079 | 1.2265 | 0.109* | |
H10B | 0.0261 | 0.3998 | 1.2219 | 0.109* | |
H10C | 0.0818 | 0.3492 | 1.1655 | 0.109* | |
H12A | 0.2372 | 0.2065 | 1.0792 | 0.048* | |
H14A | 0.3518 | 0.0009 | 1.1788 | 0.048* | |
H18A | 0.2604 | 0.1658 | 1.2887 | 0.115* | |
H18B | 0.2645 | 0.2378 | 1.2268 | 0.115* | |
H18C | 0.3444 | 0.2298 | 1.3194 | 0.115* | |
H19A | 0.3968 | 0.0618 | 1.3138 | 0.148* | |
H19B | 0.4786 | 0.1276 | 1.3432 | 0.148* | |
H19C | 0.4826 | 0.0702 | 1.2653 | 0.148* | |
H20A | 0.4032 | 0.2495 | 1.1529 | 0.119* | |
H20B | 0.4861 | 0.1840 | 1.1671 | 0.119* | |
H20C | 0.4827 | 0.2409 | 1.2456 | 0.119* | |
H21A | 0.2157 | 0.0690 | 0.8323 | 0.064* | |
H21B | 0.0997 | 0.0543 | 0.7927 | 0.064* | |
H23A | 0.2643 | −0.1091 | 0.8541 | 0.085* | |
H24A | 0.2990 | −0.2000 | 0.7551 | 0.108* | |
H25A | 0.2439 | −0.1796 | 0.6036 | 0.124* | |
H26A | 0.1469 | −0.0719 | 0.5479 | 0.113* | |
H29A | −0.1000 | 0.1239 | 0.7818 | 0.049* | |
H29B | −0.2011 | 0.0906 | 0.7960 | 0.049* | |
H31A | −0.0380 | −0.0571 | 0.8662 | 0.060* | |
H32A | −0.0075 | −0.1655 | 0.7880 | 0.077* | |
H33A | −0.0641 | −0.1698 | 0.6341 | 0.090* | |
H34A | −0.1595 | −0.0687 | 0.5581 | 0.080* | |
H37A | 0.4167 | 0.1016 | 1.0067 | 0.176* | |
H37B | 0.5266 | 0.1131 | 0.9988 | 0.176* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0417 (5) | 0.0436 (5) | 0.0388 (5) | 0.0044 (4) | 0.0077 (4) | 0.0045 (4) |
S2 | 0.0348 (5) | 0.0340 (4) | 0.0608 (6) | 0.0011 (4) | 0.0025 (4) | −0.0065 (4) |
O1 | 0.0474 (13) | 0.0297 (11) | 0.0344 (12) | 0.0031 (10) | 0.0003 (10) | −0.0043 (9) |
O2 | 0.0446 (13) | 0.0471 (13) | 0.0355 (13) | −0.0055 (11) | 0.0051 (10) | −0.0089 (10) |
N1 | 0.108 (3) | 0.092 (3) | 0.053 (2) | 0.023 (3) | 0.008 (2) | 0.004 (2) |
N2 | 0.126 (4) | 0.142 (5) | 0.082 (3) | 0.026 (4) | 0.020 (3) | 0.028 (3) |
C1 | 0.0378 (18) | 0.0289 (16) | 0.0399 (18) | 0.0003 (13) | −0.0010 (14) | −0.0016 (13) |
C2 | 0.0436 (19) | 0.0368 (18) | 0.0422 (19) | 0.0012 (15) | 0.0056 (15) | −0.0068 (15) |
C3 | 0.0436 (19) | 0.0342 (17) | 0.0411 (19) | 0.0025 (15) | 0.0018 (15) | −0.0065 (14) |
C4 | 0.0405 (18) | 0.0331 (17) | 0.0401 (19) | −0.0045 (14) | −0.0021 (15) | −0.0012 (14) |
C5 | 0.0360 (17) | 0.0355 (17) | 0.0322 (17) | 0.0064 (13) | 0.0008 (13) | 0.0036 (13) |
C6 | 0.0398 (18) | 0.0281 (15) | 0.0320 (17) | 0.0031 (14) | 0.0000 (13) | −0.0020 (13) |
C7 | 0.060 (2) | 0.0363 (19) | 0.055 (2) | −0.0032 (17) | 0.0056 (18) | −0.0156 (16) |
C8 | 0.135 (5) | 0.043 (2) | 0.085 (4) | 0.005 (3) | 0.019 (3) | −0.011 (2) |
C9 | 0.092 (4) | 0.084 (3) | 0.128 (5) | −0.012 (3) | 0.044 (3) | −0.067 (3) |
C10 | 0.083 (3) | 0.061 (3) | 0.064 (3) | −0.004 (2) | 0.001 (2) | −0.024 (2) |
C11 | 0.0337 (16) | 0.0393 (17) | 0.0363 (18) | −0.0007 (13) | 0.0098 (13) | 0.0006 (14) |
C12 | 0.0395 (18) | 0.0356 (17) | 0.0408 (19) | −0.0047 (14) | 0.0044 (15) | −0.0058 (14) |
C13 | 0.0399 (18) | 0.0380 (18) | 0.0422 (19) | −0.0015 (15) | 0.0050 (15) | −0.0045 (15) |
C14 | 0.0356 (17) | 0.0410 (18) | 0.0397 (19) | −0.0021 (14) | 0.0016 (14) | −0.0029 (15) |
C15 | 0.0299 (16) | 0.0363 (17) | 0.046 (2) | −0.0028 (13) | 0.0060 (14) | −0.0057 (14) |
C16 | 0.0291 (16) | 0.0367 (17) | 0.0340 (17) | −0.0047 (13) | 0.0069 (13) | −0.0033 (14) |
C17 | 0.057 (2) | 0.0428 (19) | 0.042 (2) | −0.0073 (16) | −0.0045 (17) | −0.0085 (16) |
C18 | 0.079 (3) | 0.081 (3) | 0.067 (3) | −0.016 (3) | 0.015 (2) | −0.029 (2) |
C19 | 0.117 (4) | 0.069 (3) | 0.069 (3) | 0.002 (3) | −0.045 (3) | −0.013 (2) |
C20 | 0.067 (3) | 0.085 (3) | 0.079 (3) | −0.031 (3) | 0.006 (2) | −0.024 (3) |
C21 | 0.060 (2) | 0.061 (2) | 0.038 (2) | −0.0021 (19) | 0.0117 (17) | −0.0040 (17) |
C22 | 0.052 (2) | 0.062 (2) | 0.051 (2) | −0.0120 (19) | 0.0191 (18) | −0.0134 (19) |
C23 | 0.076 (3) | 0.072 (3) | 0.066 (3) | 0.005 (2) | 0.022 (2) | −0.012 (2) |
C24 | 0.102 (4) | 0.075 (3) | 0.104 (5) | 0.014 (3) | 0.045 (3) | −0.019 (3) |
C25 | 0.135 (5) | 0.100 (5) | 0.093 (5) | −0.009 (4) | 0.062 (4) | −0.042 (4) |
C26 | 0.121 (5) | 0.118 (5) | 0.057 (3) | −0.016 (4) | 0.046 (3) | −0.032 (3) |
C27 | 0.071 (3) | 0.083 (3) | 0.052 (3) | −0.013 (2) | 0.029 (2) | −0.015 (2) |
C28 | 0.085 (3) | 0.105 (4) | 0.045 (3) | 0.002 (3) | 0.019 (2) | 0.003 (3) |
C29 | 0.0472 (19) | 0.0373 (18) | 0.0347 (18) | 0.0028 (15) | 0.0031 (15) | −0.0052 (14) |
C30 | 0.0381 (18) | 0.0410 (18) | 0.042 (2) | −0.0053 (15) | 0.0097 (14) | −0.0066 (15) |
C31 | 0.053 (2) | 0.0379 (19) | 0.055 (2) | 0.0032 (16) | 0.0072 (17) | −0.0056 (16) |
C32 | 0.066 (3) | 0.046 (2) | 0.080 (3) | 0.0049 (19) | 0.017 (2) | −0.013 (2) |
C33 | 0.086 (3) | 0.056 (3) | 0.087 (4) | 0.003 (2) | 0.031 (3) | −0.031 (2) |
C34 | 0.078 (3) | 0.072 (3) | 0.053 (2) | −0.006 (2) | 0.025 (2) | −0.024 (2) |
C35 | 0.049 (2) | 0.056 (2) | 0.038 (2) | −0.0046 (17) | 0.0136 (16) | −0.0108 (17) |
C36 | 0.067 (3) | 0.067 (3) | 0.038 (2) | 0.003 (2) | 0.0072 (19) | −0.009 (2) |
Cl1 | 0.368 (5) | 0.157 (2) | 0.304 (4) | 0.026 (3) | 0.206 (4) | 0.054 (3) |
Cl2 | 0.1340 (16) | 0.199 (2) | 0.1280 (16) | 0.0160 (15) | 0.0375 (12) | 0.0098 (15) |
C37 | 0.090 (5) | 0.161 (8) | 0.211 (9) | −0.016 (5) | 0.078 (5) | −0.012 (7) |
S1—C11 | 1.794 (3) | C17—C19 | 1.545 (6) |
S1—C5 | 1.797 (3) | C18—H18A | 0.9600 |
S2—C15i | 1.775 (3) | C18—H18B | 0.9600 |
S2—C1 | 1.785 (3) | C18—H18C | 0.9600 |
O1—C6 | 1.386 (4) | C19—H19A | 0.9600 |
O1—C29 | 1.438 (4) | C19—H19B | 0.9600 |
O2—C16 | 1.365 (4) | C19—H19C | 0.9600 |
O2—C21 | 1.443 (4) | C20—H20A | 0.9600 |
N1—C36 | 1.141 (5) | C20—H20B | 0.9600 |
N2—C28 | 1.134 (7) | C20—H20C | 0.9600 |
C1—C6 | 1.388 (5) | C21—C22 | 1.504 (5) |
C1—C2 | 1.404 (4) | C21—H21A | 0.9700 |
C2—C3 | 1.393 (5) | C21—H21B | 0.9700 |
C2—H2A | 0.9300 | C22—C23 | 1.377 (6) |
C3—C4 | 1.393 (5) | C22—C27 | 1.432 (6) |
C3—C7 | 1.538 (5) | C23—C24 | 1.398 (7) |
C4—C5 | 1.389 (4) | C23—H23A | 0.9300 |
C4—H4A | 0.9300 | C24—C25 | 1.378 (8) |
C5—C6 | 1.408 (4) | C24—H24A | 0.9300 |
C7—C10 | 1.527 (5) | C25—C26 | 1.370 (9) |
C7—C9 | 1.545 (6) | C25—H25A | 0.9300 |
C7—C8 | 1.540 (6) | C26—C27 | 1.390 (7) |
C8—H8A | 0.9600 | C26—H26A | 0.9300 |
C8—H8B | 0.9600 | C27—C28 | 1.436 (8) |
C8—H8C | 0.9600 | C29—C30 | 1.501 (5) |
C9—H9A | 0.9600 | C29—H29A | 0.9700 |
C9—H9B | 0.9600 | C29—H29B | 0.9700 |
C9—H9C | 0.9600 | C30—C31 | 1.383 (5) |
C10—H10A | 0.9600 | C30—C35 | 1.412 (5) |
C10—H10B | 0.9600 | C31—C32 | 1.389 (5) |
C10—H10C | 0.9600 | C31—H31A | 0.9300 |
C11—C12 | 1.401 (4) | C32—C33 | 1.387 (6) |
C11—C16 | 1.404 (4) | C32—H32A | 0.9300 |
C12—C13 | 1.392 (5) | C33—C34 | 1.362 (7) |
C12—H12A | 0.9300 | C33—H33A | 0.9300 |
C13—C14 | 1.389 (5) | C34—C35 | 1.406 (5) |
C13—C17 | 1.545 (5) | C34—H34A | 0.9300 |
C14—C15 | 1.393 (4) | C35—C36 | 1.447 (6) |
C14—H14A | 0.9300 | Cl1—C37 | 1.637 (9) |
C15—C16 | 1.417 (4) | Cl2—C37 | 1.691 (9) |
C15—S2i | 1.775 (3) | C37—H37A | 0.9700 |
C17—C18 | 1.514 (6) | C37—H37B | 0.9700 |
C17—C20 | 1.536 (6) | ||
C11—S1—C5 | 101.54 (14) | H18A—C18—H18B | 109.5 |
C15i—S2—C1 | 108.36 (14) | C17—C18—H18C | 109.5 |
C6—O1—C29 | 114.2 (2) | H18A—C18—H18C | 109.5 |
C16—O2—C21 | 118.0 (3) | H18B—C18—H18C | 109.5 |
C6—C1—C2 | 119.8 (3) | C17—C19—H19A | 109.5 |
C6—C1—S2 | 124.5 (2) | C17—C19—H19B | 109.5 |
C2—C1—S2 | 115.3 (3) | H19A—C19—H19B | 109.5 |
C3—C2—C1 | 122.0 (3) | C17—C19—H19C | 109.5 |
C3—C2—H2A | 119.0 | H19A—C19—H19C | 109.5 |
C1—C2—H2A | 119.0 | H19B—C19—H19C | 109.5 |
C4—C3—C2 | 117.2 (3) | C17—C20—H20A | 109.5 |
C4—C3—C7 | 120.3 (3) | C17—C20—H20B | 109.5 |
C2—C3—C7 | 122.5 (3) | H20A—C20—H20B | 109.5 |
C3—C4—C5 | 121.9 (3) | C17—C20—H20C | 109.5 |
C3—C4—H4A | 119.0 | H20A—C20—H20C | 109.5 |
C5—C4—H4A | 119.0 | H20B—C20—H20C | 109.5 |
C4—C5—C6 | 120.2 (3) | O2—C21—C22 | 109.5 (3) |
C4—C5—S1 | 119.1 (3) | O2—C21—H21A | 109.8 |
C6—C5—S1 | 120.3 (2) | C22—C21—H21A | 109.8 |
O1—C6—C1 | 121.2 (3) | O2—C21—H21B | 109.8 |
O1—C6—C5 | 119.9 (3) | C22—C21—H21B | 109.8 |
C1—C6—C5 | 118.8 (3) | H21A—C21—H21B | 108.2 |
C10—C7—C9 | 107.6 (4) | C23—C22—C27 | 118.1 (4) |
C10—C7—C3 | 110.5 (3) | C23—C22—C21 | 123.9 (4) |
C9—C7—C3 | 111.7 (3) | C27—C22—C21 | 118.0 (4) |
C10—C7—C8 | 108.7 (4) | C22—C23—C24 | 120.5 (5) |
C9—C7—C8 | 109.6 (4) | C22—C23—H23A | 119.7 |
C3—C7—C8 | 108.7 (3) | C24—C23—H23A | 119.7 |
C7—C8—H8A | 109.5 | C25—C24—C23 | 120.5 (5) |
C7—C8—H8B | 109.5 | C25—C24—H24A | 119.7 |
H8A—C8—H8B | 109.5 | C23—C24—H24A | 119.7 |
C7—C8—H8C | 109.5 | C24—C25—C26 | 120.6 (5) |
H8A—C8—H8C | 109.5 | C24—C25—H25A | 119.7 |
H8B—C8—H8C | 109.5 | C26—C25—H25A | 119.7 |
C7—C9—H9A | 109.5 | C25—C26—C27 | 119.7 (5) |
C7—C9—H9B | 109.5 | C25—C26—H26A | 120.1 |
H9A—C9—H9B | 109.5 | C27—C26—H26A | 120.1 |
C7—C9—H9C | 109.5 | C26—C27—C22 | 120.5 (5) |
H9A—C9—H9C | 109.5 | C26—C27—C28 | 118.2 (5) |
H9B—C9—H9C | 109.5 | C22—C27—C28 | 121.3 (4) |
C7—C10—H10A | 109.5 | N2—C28—C27 | 179.1 (6) |
C7—C10—H10B | 109.5 | O1—C29—C30 | 108.7 (3) |
H10A—C10—H10B | 109.5 | O1—C29—H29A | 109.9 |
C7—C10—H10C | 109.5 | C30—C29—H29A | 109.9 |
H10A—C10—H10C | 109.5 | O1—C29—H29B | 109.9 |
H10B—C10—H10C | 109.5 | C30—C29—H29B | 109.9 |
C12—C11—C16 | 119.8 (3) | H29A—C29—H29B | 108.3 |
C12—C11—S1 | 118.1 (2) | C31—C30—C35 | 118.4 (3) |
C16—C11—S1 | 122.1 (2) | C31—C30—C29 | 123.0 (3) |
C13—C12—C11 | 122.8 (3) | C35—C30—C29 | 118.6 (3) |
C13—C12—H12A | 118.6 | C30—C31—C32 | 120.4 (4) |
C11—C12—H12A | 118.6 | C30—C31—H31A | 119.8 |
C14—C13—C12 | 116.4 (3) | C32—C31—H31A | 119.8 |
C14—C13—C17 | 123.3 (3) | C33—C32—C31 | 120.9 (4) |
C12—C13—C17 | 120.4 (3) | C33—C32—H32A | 119.5 |
C13—C14—C15 | 122.8 (3) | C31—C32—H32A | 119.5 |
C13—C14—H14A | 118.6 | C34—C33—C32 | 119.8 (4) |
C15—C14—H14A | 118.6 | C34—C33—H33A | 120.1 |
C14—C15—C16 | 120.1 (3) | C32—C33—H33A | 120.1 |
C14—C15—S2i | 117.2 (2) | C33—C34—C35 | 120.2 (4) |
C16—C15—S2i | 122.5 (2) | C33—C34—H34A | 119.9 |
O2—C16—C11 | 125.3 (3) | C35—C34—H34A | 119.9 |
O2—C16—C15 | 117.1 (3) | C34—C35—C30 | 120.3 (4) |
C11—C16—C15 | 117.6 (3) | C34—C35—C36 | 120.5 (3) |
C18—C17—C20 | 109.1 (4) | C30—C35—C36 | 119.3 (3) |
C18—C17—C19 | 110.1 (4) | N1—C36—C35 | 178.4 (5) |
C20—C17—C19 | 107.6 (4) | Cl1—C37—Cl2 | 116.4 (6) |
C18—C17—C13 | 110.0 (3) | Cl1—C37—H37A | 108.2 |
C20—C17—C13 | 108.4 (3) | Cl2—C37—H37A | 108.2 |
C19—C17—C13 | 111.4 (3) | Cl1—C37—H37B | 108.2 |
C17—C18—H18A | 109.5 | Cl2—C37—H37B | 108.2 |
C17—C18—H18B | 109.5 | H37A—C37—H37B | 107.3 |
C15i—S2—C1—C6 | 40.8 (3) | S1—C11—C16—O2 | 5.6 (4) |
C15i—S2—C1—C2 | −146.6 (2) | C12—C11—C16—C15 | 9.0 (4) |
C6—C1—C2—C3 | 1.6 (5) | S1—C11—C16—C15 | −172.2 (2) |
S2—C1—C2—C3 | −171.4 (3) | C14—C15—C16—O2 | 175.2 (3) |
C1—C2—C3—C4 | −0.4 (5) | S2i—C15—C16—O2 | 0.9 (4) |
C1—C2—C3—C7 | 178.0 (3) | C14—C15—C16—C11 | −6.9 (4) |
C2—C3—C4—C5 | −0.9 (5) | S2i—C15—C16—C11 | 178.9 (2) |
C7—C3—C4—C5 | −179.3 (3) | C14—C13—C17—C18 | −122.9 (4) |
C3—C4—C5—C6 | 1.0 (5) | C12—C13—C17—C18 | 57.6 (5) |
C3—C4—C5—S1 | 173.7 (2) | C14—C13—C17—C20 | 117.9 (4) |
C11—S1—C5—C4 | 93.2 (3) | C12—C13—C17—C20 | −61.6 (5) |
C11—S1—C5—C6 | −94.1 (3) | C14—C13—C17—C19 | −0.4 (5) |
C29—O1—C6—C1 | 87.0 (4) | C12—C13—C17—C19 | −179.9 (4) |
C29—O1—C6—C5 | −95.3 (3) | C16—O2—C21—C22 | 139.1 (3) |
C2—C1—C6—O1 | 176.3 (3) | O2—C21—C22—C23 | −29.9 (5) |
S2—C1—C6—O1 | −11.4 (4) | O2—C21—C22—C27 | 152.1 (3) |
C2—C1—C6—C5 | −1.5 (4) | C27—C22—C23—C24 | 0.4 (6) |
S2—C1—C6—C5 | 170.8 (2) | C21—C22—C23—C24 | −177.6 (4) |
C4—C5—C6—O1 | −177.5 (3) | C22—C23—C24—C25 | 0.2 (8) |
S1—C5—C6—O1 | 9.8 (4) | C23—C24—C25—C26 | −1.5 (9) |
C4—C5—C6—C1 | 0.2 (4) | C24—C25—C26—C27 | 2.2 (9) |
S1—C5—C6—C1 | −172.4 (2) | C25—C26—C27—C22 | −1.6 (8) |
C4—C3—C7—C10 | −55.3 (5) | C25—C26—C27—C28 | 178.9 (5) |
C2—C3—C7—C10 | 126.4 (4) | C23—C22—C27—C26 | 0.3 (6) |
C4—C3—C7—C9 | −175.1 (4) | C21—C22—C27—C26 | 178.5 (4) |
C2—C3—C7—C9 | 6.6 (5) | C23—C22—C27—C28 | 179.8 (4) |
C4—C3—C7—C8 | 63.8 (5) | C21—C22—C27—C28 | −2.1 (6) |
C2—C3—C7—C8 | −114.5 (4) | C6—O1—C29—C30 | 174.0 (3) |
C5—S1—C11—C12 | −73.6 (3) | O1—C29—C30—C31 | −1.2 (5) |
C5—S1—C11—C16 | 107.6 (3) | O1—C29—C30—C35 | −178.5 (3) |
C16—C11—C12—C13 | −4.6 (5) | C35—C30—C31—C32 | 2.4 (5) |
S1—C11—C12—C13 | 176.6 (3) | C29—C30—C31—C32 | −174.9 (4) |
C11—C12—C13—C14 | −2.2 (5) | C30—C31—C32—C33 | −0.3 (6) |
C11—C12—C13—C17 | 177.3 (3) | C31—C32—C33—C34 | −2.0 (7) |
C12—C13—C14—C15 | 4.5 (5) | C32—C33—C34—C35 | 2.1 (7) |
C17—C13—C14—C15 | −175.0 (3) | C33—C34—C35—C30 | 0.0 (6) |
C13—C14—C15—C16 | 0.0 (5) | C33—C34—C35—C36 | 179.1 (4) |
C13—C14—C15—S2i | 174.6 (3) | C31—C30—C35—C34 | −2.3 (5) |
C21—O2—C16—C11 | 47.2 (4) | C29—C30—C35—C34 | 175.2 (3) |
C21—O2—C16—C15 | −135.0 (3) | C31—C30—C35—C36 | 178.7 (4) |
C12—C11—C16—O2 | −173.2 (3) | C29—C30—C35—C36 | −3.9 (5) |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C72H68N4O4S4·2CH2Cl2 |
Mr | 1351.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.768 (4), 17.021 (5), 15.543 (4) |
β (°) | 105.424 (5) |
V (Å3) | 3511.3 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.877, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14071, 6105, 3885 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.186, 1.06 |
No. of reflections | 6105 |
No. of parameters | 406 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.68 |
Computer programs: SMART (Bruker, 1998), SMART, SHELXTL (Sheldrick, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
S1—C11 | 1.794 (3) | O2—C21 | 1.443 (4) |
S1—C5 | 1.797 (3) | N1—C36 | 1.141 (5) |
S2—C15i | 1.775 (3) | N2—C28 | 1.134 (7) |
S2—C1 | 1.785 (3) | C3—C7 | 1.538 (5) |
O1—C6 | 1.386 (4) | C13—C17 | 1.545 (5) |
O1—C29 | 1.438 (4) | C21—C22 | 1.504 (5) |
O2—C16 | 1.365 (4) | C29—C30 | 1.501 (5) |
C11—S1—C5 | 101.54 (14) | C14—C15—S2i | 117.2 (2) |
C15i—S2—C1 | 108.36 (14) | C16—C15—S2i | 122.5 (2) |
C6—O1—C29 | 114.2 (2) | O2—C16—C11 | 125.3 (3) |
C16—O2—C21 | 118.0 (3) | O2—C16—C15 | 117.1 (3) |
C6—C1—S2 | 124.5 (2) | O2—C21—C22 | 109.5 (3) |
C2—C1—S2 | 115.3 (3) | N2—C28—C27 | 179.1 (6) |
C12—C11—S1 | 118.1 (2) | O1—C29—C30 | 108.7 (3) |
C16—C11—S1 | 122.1 (2) | N1—C36—C35 | 178.4 (5) |
Symmetry code: (i) −x, −y, −z+2. |
Thiacalix[4]arenes (TCAs) have emerged very recently as new members of the well known calixarene family (Kumagai et al., 1997). It has been demonstrated that one of the remarkable results of the replacement of CH2 by S is that TCAs can quantitatively extract transition metal ions, such as Co2+, Cu2+ and Zn2+, from an aqueous phase into chloroform (Morohashi et al., 2001) and, furthermore, oxidation of the sulfur bridges to sulfoxide or sulfone moieties leads to new types of ligands with potentially interesting complexation abilities (Lhotak et al., 2000).
For the parent calix[4]arene, four limit conformers (cone, partial cone, 1,2-alternate and 1,3-alternate) are found, to the best of our knowledge, however, for most tetrasubstituted calix[4]arene derivatives, the 1,2-alternate conformation is unknown (Cambridge Structural Database; Version of April 2001; Allen & Kennard, 1993). We report herein the structure of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-cyanobenzyloxy)-2,8,14,20- tetrathiacalix[4]arene–dichloromethane (1/2), (I), which adopts an unique 1,2-alternate conformation via π–π interactions between adjacent cyanophenyl rings on the lower rim of the parent thiacalix[4]arene system.
Single-crystal analysis reveals that the molecule is centrosymmetric. Two pairs of opposite aromatic rings, C1–C6/C1A–C6A and C11–C16/C11A–C16A, are parallel to each other. The dihedral angles between adjacent aromatic rings, i.e. C1–C6 and C11–C16, and C1A–C6A and C11A–C16A, are all 102.7 (1)°. Furthermore, adjacent cyanophenyl rings on the lower rim are nearly parallel, with a dihedral angle of 7.3 (2)° and the two carbonitrile groups are oriented in roughly the same direction. The four bridging S atoms are coplanar and the average distances between two adjacent S atoms, S1···S2, and two opposite S atoms, S2···S2A, are approximately 5.581 (1) and 8.409 (1) Å, respectively. The angles C5—S1—C11 and C1—S2—C15A are 101.54 (4) and 108.36 (4)°. The two dichloromethane solvent molecules do not enter the cavity, but are located on opposite sides of the thiacalix[4]arene molecule.
In conclusion, as the precursor of a new thiacalix[4]arene derivative, the title compound adopts an unusual 1,2-alternate conformation with two pairs of distal aromatic rings and two pairs of distal cyanophenyl rings being centrosymmetric. Hydrolysis of the cyanobenzyl groups on the lower rim to the benzoxy groups and the binding ability toward metal ions of the latter derivative are currently under investigation.