Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101015931/fr1336sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015931/fr1336monoclinicIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101015931/fr1336triclinicIsup3.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270101015931/fr1336sup4.pdf |
CCDC references: 179271; 179272
Details of the synthetic procedures have been published elsewhere (Gale et al., 1996). Crystals were grown by slow evaporation from a DMSO solution.
The crystals cracked when quickly immersed in a cold nitrogen gas stream at 198 K. However, the crystals generally remained intact when cooled slowly to 198 K although, at this temperature, the diffraction peaks were quite broad. The low-temperature cell had nearly monoclinic metric symmetry. Because of this and the fact that the crystals cracked upon quick cooling, we investigated the room-temperature structure as well. Crystals of the DMSO–calix[4]pyrrole complex decompose slowly at room temperature. The room-temperature data set was accomplished by mounting a crystal in a capillary containing a small amount of the mother liquor. The ends of the capillary were sealed with epoxy. A different crystal was used for the low-temperature data set. In both crystals, the DMSO molecule was found to be disordered in such a way that the S atom appears in two positions, above and below the plane through the remaining atoms of the DMSO molecule. The site-occupancy factors were initially determined by refining the S-atom site-occupancy factors to sum to 1 with a common Uiso value. In the final stages of refinement, two positions for one of the methyl C atoms could be resolved and both the S– and C-atom occupancies were refined. Interestingly, the site occupancies of the major and minor forms refined to different values for the two different crystals. The H atoms on the N atoms were observed from a difference map and refined with isotropic displacement parameters. The remaining H atoms were calculated in idealized positions. For the room-temperature structure, the regions around the methyl C atoms of the DMSO molecule where H atoms would be expected to be located showed the highest residual electron density. At this point, idealized H-atom positions with site-occupancy factors weighted to account for the disordered DMSO molecule were included in the model. The refinement of the triclinic phase proceeded normally There were no unusual correlation coefficients between parameters of atoms related by the pseudo-glide plane. High correlation coefficients were observed between parameters of atoms of the disordered DMSO molecules for both phases.
For both compounds, data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: XS in SHELXTL/PC (Sheldrick, 1998); program(s) used to refine structure: XL in SHELXTL/PC; molecular graphics: XP in SHELXTL/PC.
C28H36N4·C2H6OS | F(000) = 1096 |
Mr = 506.74 | Dx = 1.153 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.411 (2) Å | Cell parameters from 40 reflections |
b = 23.586 (6) Å | θ = 8.8–10.9° |
c = 12.482 (3) Å | µ = 0.14 mm−1 |
β = 107.71 (2)° | T = 298 K |
V = 2919.7 (12) Å3 | Trapezoidal prism, colorless |
Z = 4 | 0.34 × 0.34 × 0.24 mm |
Siemens P3 diffractometer | Rint = 0.047 |
Radiation source: normal-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = −1→12 |
ω scans | k = −1→28 |
6290 measured reflections | l = −14→14 |
5109 independent reflections | 4 standard reflections every 96 reflections |
2069 reflections with I > 2σ(I) | intensity decay: <2% |
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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0482P)2] where P = (Fo2 + 2Fc2)/3 |
5109 reflections | (Δ/σ)max = 0.016 |
359 parameters | Δρmax = 0.16 e Å−3 |
12 restraints | Δρmin = −0.17 e Å−3 |
C28H36N4·C2H6OS | V = 2919.7 (12) Å3 |
Mr = 506.74 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.411 (2) Å | µ = 0.14 mm−1 |
b = 23.586 (6) Å | T = 298 K |
c = 12.482 (3) Å | 0.34 × 0.34 × 0.24 mm |
β = 107.71 (2)° |
Siemens P3 diffractometer | Rint = 0.047 |
6290 measured reflections | 4 standard reflections every 96 reflections |
5109 independent reflections | intensity decay: <2% |
2069 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.071 | 12 restraints |
wR(F2) = 0.152 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.16 e Å−3 |
5109 reflections | Δρmin = −0.17 e Å−3 |
359 parameters |
Experimental. The data crystal was sealed in a glass capillary with a small amount of mother liquor. The ends of the capillary were sealed with epoxy. |
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 on F2 for ALL reflections except for 2 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | Occ. (<1) | |
S1 | 0.4930 (2) | 0.28633 (8) | 0.63083 (14) | 0.0507 (5) | 0.65 |
C2A | 0.3930 (11) | 0.3452 (7) | 0.6497 (12) | 0.071 (4) | 0.65 |
H2AA | 0.4155 | 0.3778 | 0.6129 | 0.106* | 0.65 |
H2AB | 0.2993 | 0.3363 | 0.6166 | 0.106* | 0.65 |
H2AC | 0.4104 | 0.3532 | 0.7282 | 0.106* | 0.65 |
S1' | 0.3615 (4) | 0.28649 (15) | 0.5995 (3) | 0.0517 (9) | 0.35 |
C2A' | 0.4632 (19) | 0.3441 (13) | 0.667 (2) | 0.071 (7) | 0.35 |
H2AD | 0.4379 | 0.3775 | 0.6216 | 0.106* | 0.35 |
H2AE | 0.4428 | 0.3494 | 0.7366 | 0.106* | 0.35 |
H2AF | 0.5581 | 0.3375 | 0.6830 | 0.106* | 0.35 |
O1A | 0.4304 (3) | 0.27117 (11) | 0.5060 (2) | 0.0636 (9) | |
C1A | 0.4305 (4) | 0.23387 (17) | 0.7049 (3) | 0.0579 (13) | |
H1AD | 0.3909 | 0.1977 | 0.6786 | 0.087* | 0.35 |
H1AE | 0.5264 | 0.2318 | 0.7194 | 0.087* | 0.35 |
H1AF | 0.4110 | 0.2437 | 0.7730 | 0.087* | 0.35 |
H1AA | 0.4764 | 0.1987 | 0.7034 | 0.087* | 0.65 |
H1AB | 0.4466 | 0.2457 | 0.7815 | 0.087* | 0.65 |
H1AC | 0.3355 | 0.2288 | 0.6699 | 0.087* | 0.65 |
N1 | 0.4188 (4) | 0.14801 (15) | 0.4498 (3) | 0.0405 (9) | |
H1N | 0.417 (4) | 0.1883 (17) | 0.476 (3) | 0.074 (14)* | |
N2 | 0.1818 (4) | 0.11346 (16) | 0.5853 (3) | 0.0490 (10) | |
H2N | 0.231 (3) | 0.0825 (14) | 0.583 (3) | 0.037 (12)* | |
N3 | 0.4256 (4) | 0.09858 (17) | 0.8519 (3) | 0.0497 (10) | |
H3N | 0.427 (4) | 0.1365 (16) | 0.871 (3) | 0.055 (14)* | |
N4 | 0.6635 (4) | 0.10802 (18) | 0.7025 (3) | 0.0507 (11) | |
H4N | 0.620 (4) | 0.0786 (17) | 0.678 (3) | 0.065 (18)* | |
C1 | 0.5309 (4) | 0.11496 (18) | 0.4599 (3) | 0.0415 (11) | |
C2 | 0.4857 (5) | 0.06287 (19) | 0.4185 (3) | 0.0550 (12) | |
H2 | 0.5414 | 0.0308 | 0.4159 | 0.066* | |
C3 | 0.3439 (5) | 0.06408 (19) | 0.3840 (3) | 0.0560 (13) | |
H3 | 0.2850 | 0.0335 | 0.3498 | 0.067* | |
C4 | 0.3034 (4) | 0.11668 (18) | 0.4038 (3) | 0.0423 (11) | |
C5 | 0.1651 (4) | 0.14086 (18) | 0.3871 (3) | 0.0466 (11) | |
C6 | 0.1447 (4) | 0.15290 (18) | 0.5001 (3) | 0.0436 (11) | |
C7 | 0.0855 (4) | 0.19645 (18) | 0.5393 (4) | 0.0525 (12) | |
H7 | 0.0477 | 0.2299 | 0.4980 | 0.063* | |
C8 | 0.0877 (4) | 0.1829 (2) | 0.6500 (4) | 0.0569 (13) | |
H8 | 0.0532 | 0.2057 | 0.6987 | 0.068* | |
C9 | 0.1466 (4) | 0.13169 (19) | 0.6781 (3) | 0.0476 (12) | |
C10 | 0.1703 (5) | 0.09393 (19) | 0.7805 (3) | 0.0569 (13) | |
C11 | 0.3089 (5) | 0.0677 (2) | 0.8091 (3) | 0.0540 (13) | |
C12 | 0.3480 (7) | 0.0141 (2) | 0.7939 (4) | 0.0829 (18) | |
H12 | 0.2866 | −0.0167 | 0.7666 | 0.099* | |
C13 | 0.4898 (7) | 0.0123 (2) | 0.8288 (4) | 0.0842 (19) | |
H13 | 0.5444 | −0.0200 | 0.8258 | 0.101* | |
C14 | 0.5381 (5) | 0.0650 (2) | 0.8650 (3) | 0.0558 (14) | |
C15 | 0.6793 (5) | 0.0885 (2) | 0.9042 (4) | 0.0627 (14) | |
C16 | 0.7033 (4) | 0.1255 (2) | 0.8130 (3) | 0.0501 (12) | |
C17 | 0.7665 (4) | 0.1757 (2) | 0.8159 (4) | 0.0598 (13) | |
H17 | 0.8060 | 0.1984 | 0.8815 | 0.072* | |
C18 | 0.7639 (4) | 0.18995 (19) | 0.7051 (4) | 0.0550 (12) | |
H18 | 0.8008 | 0.2233 | 0.6815 | 0.066* | |
C19 | 0.6992 (4) | 0.14756 (18) | 0.6354 (3) | 0.0448 (11) | |
C20 | 0.6714 (4) | 0.13673 (17) | 0.5106 (3) | 0.0449 (11) | |
C21 | 0.0566 (4) | 0.0980 (2) | 0.3243 (4) | 0.0759 (16) | |
H21A | 0.0691 | 0.0633 | 0.3663 | 0.114* | |
H21B | 0.0628 | 0.0907 | 0.2504 | 0.114* | |
H21C | −0.0306 | 0.1134 | 0.3184 | 0.114* | |
C22 | 0.1442 (5) | 0.19630 (18) | 0.3190 (3) | 0.0686 (15) | |
H22A | 0.2132 | 0.2225 | 0.3579 | 0.103* | |
H22B | 0.0574 | 0.2121 | 0.3131 | 0.103* | |
H22C | 0.1507 | 0.1894 | 0.2451 | 0.103* | |
C23 | 0.0614 (5) | 0.0473 (2) | 0.7528 (4) | 0.0907 (19) | |
H23A | 0.0703 | 0.0256 | 0.6904 | 0.136* | |
H23B | −0.0271 | 0.0637 | 0.7334 | 0.136* | |
H23C | 0.0746 | 0.0231 | 0.8170 | 0.136* | |
C24 | 0.1543 (5) | 0.1292 (2) | 0.8786 (3) | 0.0745 (16) | |
H24A | 0.2216 | 0.1584 | 0.8941 | 0.112* | |
H24B | 0.1683 | 0.1055 | 0.9436 | 0.112* | |
H24C | 0.0665 | 0.1461 | 0.8601 | 0.112* | |
C25 | 0.7807 (5) | 0.0382 (2) | 0.9287 (4) | 0.099 (2) | |
H25A | 0.7676 | 0.0165 | 0.8611 | 0.149* | |
H25B | 0.7674 | 0.0143 | 0.9866 | 0.149* | |
H25C | 0.8706 | 0.0532 | 0.9526 | 0.149* | |
C26 | 0.7013 (5) | 0.1233 (2) | 1.0124 (3) | 0.0875 (18) | |
H26A | 0.6363 | 0.1534 | 0.9949 | 0.131* | |
H26B | 0.7904 | 0.1391 | 1.0370 | 0.131* | |
H26C | 0.6873 | 0.1002 | 1.0710 | 0.131* | |
C27 | 0.7738 (4) | 0.09273 (18) | 0.4948 (3) | 0.0637 (14) | |
H27A | 0.7600 | 0.0578 | 0.5291 | 0.096* | |
H27B | 0.8643 | 0.1057 | 0.5294 | 0.096* | |
H27C | 0.7596 | 0.0867 | 0.4159 | 0.096* | |
C28 | 0.6953 (4) | 0.19200 (18) | 0.4539 (3) | 0.0636 (14) | |
H28A | 0.6327 | 0.2197 | 0.4641 | 0.095* | |
H28B | 0.6809 | 0.1862 | 0.3750 | 0.095* | |
H28C | 0.7856 | 0.2052 | 0.4885 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0548 (13) | 0.0511 (12) | 0.0472 (11) | −0.0043 (11) | 0.0171 (10) | −0.0039 (9) |
C2A | 0.107 (10) | 0.055 (6) | 0.045 (6) | 0.032 (9) | 0.016 (8) | −0.003 (5) |
S1' | 0.055 (2) | 0.054 (2) | 0.046 (2) | 0.006 (2) | 0.0151 (18) | 0.0003 (17) |
C2A' | 0.091 (15) | 0.066 (12) | 0.054 (11) | 0.012 (14) | 0.019 (13) | 0.003 (9) |
O1A | 0.089 (2) | 0.059 (2) | 0.0457 (17) | 0.0039 (19) | 0.0248 (18) | −0.0082 (15) |
C1A | 0.063 (3) | 0.060 (3) | 0.052 (3) | −0.004 (3) | 0.019 (3) | 0.011 (2) |
N1 | 0.050 (2) | 0.037 (2) | 0.0364 (19) | 0.000 (2) | 0.0156 (18) | −0.0019 (17) |
N2 | 0.065 (3) | 0.041 (2) | 0.044 (2) | 0.004 (2) | 0.021 (2) | 0.003 (2) |
N3 | 0.066 (3) | 0.040 (2) | 0.046 (2) | 0.002 (3) | 0.020 (2) | 0.002 (2) |
N4 | 0.064 (3) | 0.052 (3) | 0.037 (2) | 0.002 (2) | 0.015 (2) | 0.001 (2) |
C1 | 0.051 (3) | 0.044 (3) | 0.032 (2) | 0.002 (3) | 0.017 (2) | 0.003 (2) |
C2 | 0.071 (4) | 0.041 (3) | 0.053 (3) | 0.007 (3) | 0.020 (3) | 0.000 (2) |
C3 | 0.074 (4) | 0.038 (3) | 0.055 (3) | −0.010 (3) | 0.018 (3) | −0.008 (2) |
C4 | 0.047 (3) | 0.048 (3) | 0.029 (2) | −0.006 (3) | 0.007 (2) | 0.003 (2) |
C5 | 0.050 (3) | 0.048 (3) | 0.039 (3) | −0.010 (2) | 0.008 (2) | 0.004 (2) |
C6 | 0.042 (3) | 0.041 (3) | 0.045 (3) | −0.006 (2) | 0.011 (2) | 0.003 (2) |
C7 | 0.049 (3) | 0.046 (3) | 0.062 (3) | −0.003 (3) | 0.016 (3) | 0.010 (2) |
C8 | 0.055 (3) | 0.053 (3) | 0.066 (3) | −0.013 (3) | 0.023 (3) | −0.019 (3) |
C9 | 0.051 (3) | 0.057 (3) | 0.038 (3) | −0.020 (3) | 0.018 (2) | −0.011 (2) |
C10 | 0.065 (4) | 0.065 (3) | 0.042 (3) | −0.023 (3) | 0.017 (3) | −0.005 (2) |
C11 | 0.084 (4) | 0.043 (3) | 0.038 (3) | −0.014 (3) | 0.024 (3) | 0.003 (2) |
C12 | 0.136 (6) | 0.052 (4) | 0.064 (4) | −0.019 (4) | 0.035 (4) | −0.009 (3) |
C13 | 0.136 (6) | 0.051 (4) | 0.075 (4) | 0.025 (4) | 0.046 (4) | 0.005 (3) |
C14 | 0.084 (4) | 0.054 (3) | 0.038 (3) | 0.026 (3) | 0.032 (3) | 0.016 (2) |
C15 | 0.072 (4) | 0.075 (4) | 0.042 (3) | 0.027 (3) | 0.019 (3) | 0.010 (3) |
C16 | 0.050 (3) | 0.063 (3) | 0.035 (3) | 0.015 (3) | 0.010 (2) | 0.001 (2) |
C17 | 0.049 (3) | 0.079 (4) | 0.046 (3) | 0.010 (3) | 0.007 (2) | −0.020 (3) |
C18 | 0.047 (3) | 0.059 (3) | 0.058 (3) | 0.001 (3) | 0.014 (2) | −0.004 (3) |
C19 | 0.044 (3) | 0.049 (3) | 0.040 (3) | 0.006 (2) | 0.010 (2) | 0.007 (2) |
C20 | 0.045 (3) | 0.051 (3) | 0.041 (3) | 0.008 (2) | 0.016 (2) | 0.006 (2) |
C21 | 0.065 (3) | 0.098 (4) | 0.059 (3) | −0.027 (3) | 0.009 (3) | −0.015 (3) |
C22 | 0.064 (3) | 0.084 (4) | 0.061 (3) | 0.018 (3) | 0.023 (3) | 0.029 (3) |
C23 | 0.098 (4) | 0.106 (4) | 0.061 (3) | −0.062 (4) | 0.013 (3) | 0.013 (3) |
C24 | 0.063 (3) | 0.118 (5) | 0.050 (3) | −0.002 (3) | 0.028 (3) | −0.010 (3) |
C25 | 0.120 (5) | 0.119 (5) | 0.070 (4) | 0.071 (4) | 0.045 (4) | 0.045 (3) |
C26 | 0.082 (4) | 0.138 (5) | 0.040 (3) | 0.014 (4) | 0.015 (3) | −0.002 (3) |
C27 | 0.057 (3) | 0.083 (4) | 0.053 (3) | 0.013 (3) | 0.020 (3) | 0.000 (3) |
C28 | 0.052 (3) | 0.078 (4) | 0.058 (3) | −0.007 (3) | 0.014 (2) | 0.017 (3) |
S1—O1A | 1.537 (3) | C9—C10 | 1.515 (5) |
S1—C1A | 1.782 (4) | C10—C11 | 1.510 (6) |
S1—C2A | 1.794 (13) | C10—C24 | 1.530 (5) |
C2A—H2AA | 0.96 | C10—C23 | 1.541 (5) |
C2A—H2AB | 0.96 | C11—C12 | 1.359 (6) |
C2A—H2AC | 0.96 | C12—C13 | 1.407 (7) |
S1'—O1A | 1.587 (4) | C12—H12 | 0.96 |
S1'—C2A' | 1.77 (3) | C13—C14 | 1.365 (6) |
S1'—C1A | 1.792 (5) | C13—H13 | 0.96 |
C2A'—H2AD | 0.96 | C14—C15 | 1.507 (6) |
C2A'—H2AE | 0.96 | C15—C16 | 1.515 (6) |
C2A'—H2AF | 0.96 | C15—C26 | 1.536 (5) |
C1A—H1AD | 0.96 | C15—C25 | 1.556 (5) |
C1A—H1AE | 0.96 | C16—C17 | 1.349 (6) |
C1A—H1AF | 0.96 | C17—C18 | 1.415 (5) |
C1A—H1AA | 0.96 | C17—H17 | 0.96 |
C1A—H1AB | 0.96 | C18—C19 | 1.362 (5) |
C1A—H1AC | 0.96 | C18—H18 | 0.96 |
N1—C1 | 1.377 (5) | C19—C20 | 1.517 (5) |
N1—C4 | 1.378 (5) | C20—C28 | 1.539 (5) |
N1—H1N | 1.01 (4) | C20—C27 | 1.543 (5) |
N2—C6 | 1.377 (5) | C21—H21A | 0.96 |
N2—C9 | 1.386 (5) | C21—H21B | 0.96 |
N2—H2N | 0.90 (3) | C21—H21C | 0.96 |
N3—C11 | 1.378 (5) | C22—H22A | 0.96 |
N3—C14 | 1.382 (5) | C22—H22B | 0.96 |
N3—H3N | 0.93 (4) | C22—H22C | 0.96 |
N4—C16 | 1.377 (5) | C23—H23A | 0.96 |
N4—C19 | 1.378 (5) | C23—H23B | 0.96 |
N4—H4N | 0.83 (4) | C23—H23C | 0.96 |
C1—C2 | 1.360 (5) | C24—H24A | 0.96 |
C1—C20 | 1.497 (5) | C24—H24B | 0.96 |
C2—C3 | 1.407 (6) | C24—H24C | 0.96 |
C2—H2 | 0.96 | C25—H25A | 0.96 |
C3—C4 | 1.357 (5) | C25—H25B | 0.96 |
C3—H3 | 0.96 | C25—H25C | 0.96 |
C4—C5 | 1.503 (6) | C26—H26A | 0.96 |
C5—C6 | 1.515 (5) | C26—H26B | 0.96 |
C5—C22 | 1.538 (5) | C26—H26C | 0.96 |
C5—C21 | 1.541 (5) | C27—H27A | 0.96 |
C6—C7 | 1.363 (5) | C27—H27B | 0.96 |
C7—C8 | 1.412 (5) | C27—H27C | 0.96 |
C7—H7 | 0.96 | C28—H28A | 0.96 |
C8—C9 | 1.352 (5) | C28—H28B | 0.96 |
C8—H8 | 0.96 | C28—H28C | 0.96 |
O1A—S1—C1A | 104.8 (2) | C12—C11—C10 | 130.9 (5) |
O1A—S1—C2A | 103.2 (5) | N3—C11—C10 | 122.8 (4) |
C1A—S1—C2A | 98.7 (5) | C11—C12—C13 | 108.4 (5) |
S1—C2A—H2AA | 108.8 | C11—C12—H12 | 123.9 |
S1—C2A—H2AB | 109.2 | C13—C12—H12 | 127.7 |
H2AA—C2A—H2AB | 109.5 | C14—C13—C12 | 108.8 (5) |
S1—C2A—H2AC | 110.4 | C14—C13—H13 | 125.1 |
H2AA—C2A—H2AC | 109.5 | C12—C13—H13 | 126.1 |
H2AB—C2A—H2AC | 109.5 | C13—C14—N3 | 105.6 (5) |
S1—C2A—H2AD | 100.9 | C13—C14—C15 | 131.9 (5) |
S1—C2A—H2AE | 94.8 | N3—C14—C15 | 122.4 (4) |
O1A—S1'—C2A' | 100.8 (9) | C14—C15—C16 | 109.6 (4) |
O1A—S1'—C1A | 102.3 (2) | C14—C15—C26 | 110.6 (4) |
C2A'—S1'—C1A | 97.6 (9) | C16—C15—C26 | 109.8 (4) |
S1'—C2A'—H2AD | 109.2 | C14—C15—C25 | 108.6 (4) |
S1'—C2A'—H2AE | 105.4 | C16—C15—C25 | 109.3 (4) |
H2AA—C2A'—H2AE | 106.8 | C26—C15—C25 | 108.9 (4) |
H2AD—C2A'—H2AE | 109.5 | C17—C16—N4 | 106.6 (4) |
S1'—C2A'—H2AF | 113.7 | C17—C16—C15 | 132.5 (4) |
H2AD—C2A'—H2AF | 109.5 | N4—C16—C15 | 120.8 (4) |
H2AE—C2A'—H2AF | 109.5 | C16—C17—C18 | 108.5 (4) |
S1'—C1A—H1AD | 109.2 | C16—C17—H17 | 126.2 |
S1'—C1A—H1AE | 109.5 | C18—C17—H17 | 125.2 |
H1AD—C1A—H1AE | 109.5 | C19—C18—C17 | 108.0 (4) |
S1'—C1A—H1AF | 109.7 | C19—C18—H18 | 124.8 |
H1AD—C1A—H1AF | 109.5 | C17—C18—H18 | 127.2 |
H1AE—C1A—H1AF | 109.5 | C18—C19—N4 | 106.3 (4) |
S1—C1A—H1AA | 109.1 | C18—C19—C20 | 133.1 (4) |
S1—C1A—H1AB | 109.6 | N4—C19—C20 | 120.5 (4) |
S1'—C1A—H1AB | 116.1 | C1—C20—C19 | 110.4 (3) |
H1AA—C1A—H1AB | 109.5 | C1—C20—C28 | 111.7 (3) |
S1—C1A—H1AC | 109.8 | C19—C20—C28 | 108.8 (3) |
H1AA—C1A—H1AC | 109.5 | C1—C20—C27 | 109.8 (3) |
H1AB—C1A—H1AC | 109.5 | C19—C20—C27 | 108.8 (3) |
C1—N1—C4 | 110.0 (4) | C28—C20—C27 | 107.2 (3) |
C1—N1—H1N | 127 (2) | C5—C21—H21A | 109.0 |
C4—N1—H1N | 123 (2) | C5—C21—H21B | 110.7 |
C6—N2—C9 | 110.7 (4) | H21A—C21—H21B | 109.5 |
C6—N2—H2N | 124 (2) | C5—C21—H21C | 108.7 |
C9—N2—H2N | 125 (2) | H21A—C21—H21C | 109.5 |
C11—N3—C14 | 111.0 (4) | H21B—C21—H21C | 109.4 |
C11—N3—H3N | 123 (3) | C5—C22—H22A | 108.0 |
C14—N3—H3N | 126 (3) | C5—C22—H22B | 110.1 |
C16—N4—C19 | 110.6 (4) | H22A—C22—H22B | 109.4 |
C16—N4—H4N | 126 (3) | C5—C22—H22C | 110.3 |
C19—N4—H4N | 124 (3) | H22A—C22—H22C | 109.5 |
C2—C1—N1 | 106.9 (4) | H22B—C22—H22C | 109.4 |
C2—C1—C20 | 130.6 (4) | C10—C23—H23A | 108.5 |
N1—C1—C20 | 122.5 (4) | C10—C23—H23B | 110.8 |
C1—C2—C3 | 107.9 (4) | H23A—C23—H23B | 109.4 |
C1—C2—H2 | 125.6 | C10—C23—H23C | 109.2 |
C3—C2—H2 | 126.4 | H23A—C23—H23C | 109.5 |
C4—C3—C2 | 108.5 (4) | H23B—C23—H23C | 109.5 |
C4—C3—H3 | 125.3 | C10—C24—H24A | 107.6 |
C2—C3—H3 | 126.2 | C10—C24—H24B | 109.6 |
C3—C4—N1 | 106.7 (4) | H24A—C24—H24B | 109.5 |
C3—C4—C5 | 131.2 (4) | C10—C24—H24C | 111.2 |
N1—C4—C5 | 122.1 (4) | H24A—C24—H24C | 109.4 |
C4—C5—C6 | 110.0 (3) | H24B—C24—H24C | 109.5 |
C4—C5—C22 | 111.6 (4) | C15—C25—H25A | 109.1 |
C6—C5—C22 | 108.6 (3) | C15—C25—H25B | 110.6 |
C4—C5—C21 | 110.2 (4) | H25A—C25—H25B | 109.5 |
C6—C5—C21 | 107.9 (3) | C15—C25—H25C | 108.6 |
C22—C5—C21 | 108.5 (3) | H25A—C25—H25C | 109.5 |
C7—C6—N2 | 106.4 (4) | H25B—C25—H25C | 109.4 |
C7—C6—C5 | 133.0 (4) | C15—C26—H26A | 106.8 |
N2—C6—C5 | 120.4 (4) | C15—C26—H26B | 111.1 |
C6—C7—C8 | 107.8 (4) | H26A—C26—H26B | 109.4 |
C6—C7—H7 | 125.7 | C15—C26—H26C | 110.5 |
C8—C7—H7 | 126.5 | H26A—C26—H26C | 109.5 |
C9—C8—C7 | 109.1 (4) | H26B—C26—H26C | 109.4 |
C9—C8—H8 | 124.4 | C20—C27—H27A | 108.5 |
C7—C8—H8 | 126.5 | C20—C27—H27B | 110.4 |
C8—C9—N2 | 105.9 (4) | H27A—C27—H27B | 109.4 |
C8—C9—C10 | 133.5 (4) | C20—C27—H27C | 109.5 |
N2—C9—C10 | 120.4 (4) | H27A—C27—H27C | 109.5 |
C11—C10—C9 | 109.8 (4) | H27B—C27—H27C | 109.5 |
C11—C10—C24 | 111.3 (4) | C20—C28—H28A | 107.7 |
C9—C10—C24 | 109.0 (4) | C20—C28—H28B | 110.7 |
C11—C10—C23 | 110.2 (4) | H28A—C28—H28B | 109.5 |
C9—C10—C23 | 108.0 (4) | C20—C28—H28C | 109.9 |
C24—C10—C23 | 108.4 (4) | H28A—C28—H28C | 109.4 |
C12—C11—N3 | 106.2 (5) | H28B—C28—H28C | 109.5 |
C28H36N4·C2H6OS | Z = 4 |
Mr = 506.74 | F(000) = 1096 |
Triclinic, P1 | Dx = 1.174 Mg m−3 |
a = 10.362 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 23.468 (10) Å | Cell parameters from 27 reflections |
c = 12.373 (7) Å | θ = 8.5–11° |
α = 90.23 (4)° | µ = 0.14 mm−1 |
β = 107.64 (4)° | T = 198 K |
γ = 88.35 (3)° | Prism, colorless |
V = 2866 (2) Å3 | 0.34 × 0.34 × 0.26 mm |
Siemens P4 diffractometer | Rint = 0.042 |
Radiation source: normal-focus sealed tube | θmax = 25.0°, θmin = 2.1° |
Graphite monochromator | h = −5→12 |
/w scans | k = −27→27 |
11862 measured reflections | l = −14→14 |
10061 independent reflections | 4 standard reflections every 96 reflections |
5213 reflections with I > 2σ(I) | intensity decay: <2% |
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)] = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.155 | w = 1/[σ2(Fo2) + (0.0536P)2 + 6.1009P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = −0.028 |
10046 reflections | Δρmax = 0.40 e Å−3 |
718 parameters | Δρmin = −0.27 e Å−3 |
24 restraints | Extinction correction: SHELXTL/PC, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0015 (4) |
C28H36N4·C2H6OS | γ = 88.35 (3)° |
Mr = 506.74 | V = 2866 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 10.362 (3) Å | Mo Kα radiation |
b = 23.468 (10) Å | µ = 0.14 mm−1 |
c = 12.373 (7) Å | T = 198 K |
α = 90.23 (4)° | 0.34 × 0.34 × 0.26 mm |
β = 107.64 (4)° |
Siemens P4 diffractometer | Rint = 0.042 |
11862 measured reflections | 4 standard reflections every 96 reflections |
10061 independent reflections | intensity decay: <2% |
5213 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.081 | 24 restraints |
wR(F2) = 0.155 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.40 e Å−3 |
10046 reflections | Δρmin = −0.27 e Å−3 |
718 parameters |
Experimental. The unit cell is in a non-standard setting for comparison to the room temperature monoclinic form. |
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 on F2 for ALL reflections except for 15 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | Occ. (<1) | |
S1A | 0.4778 (2) | 0.28663 (7) | 0.62746 (13) | 0.0282 (4) | 0.76 |
C2A | 0.3737 (9) | 0.3446 (4) | 0.6482 (7) | 0.036 (2) | 0.76 |
H2AA | 0.2804 | 0.3349 | 0.6171 | 0.055* | 0.76 |
H2AB | 0.3930 | 0.3522 | 0.7278 | 0.055* | 0.76 |
H2AC | 0.3906 | 0.3779 | 0.6104 | 0.055* | 0.76 |
O1A | 0.4198 (4) | 0.27128 (15) | 0.5021 (3) | 0.0414 (10) | |
C1A | 0.4182 (6) | 0.2331 (2) | 0.7028 (4) | 0.0383 (14) | |
H1AD | 0.3798 | 0.1969 | 0.6770 | 0.057* | 0.76 |
H1AE | 0.5142 | 0.2308 | 0.7147 | 0.057* | 0.76 |
H1AF | 0.4010 | 0.2428 | 0.7727 | 0.057* | 0.76 |
H1AA | 0.4662 | 0.1977 | 0.7007 | 0.057* | 0.24 |
H1AB | 0.4341 | 0.2446 | 0.7801 | 0.057* | 0.24 |
H1AC | 0.3229 | 0.2282 | 0.6678 | 0.057* | 0.24 |
S1AA | 0.3437 (7) | 0.2857 (3) | 0.5991 (5) | 0.0411 (15) | 0.24 |
C2AA | 0.444 (3) | 0.3453 (15) | 0.663 (3) | 0.056 (10) | 0.24 |
H2AD | 0.4109 | 0.3775 | 0.6137 | 0.083* | 0.24 |
H2AE | 0.4260 | 0.3519 | 0.7338 | 0.083* | 0.24 |
H2AF | 0.5392 | 0.3399 | 0.6759 | 0.083* | 0.24 |
S1A' | 0.4820 (2) | 0.21444 (7) | 0.12888 (14) | 0.0305 (4) | 0.76 |
C2A' | 0.3887 (9) | 0.1551 (4) | 0.1504 (7) | 0.043 (2) | 0.76 |
H2AG | 0.4215 | 0.1429 | 0.2282 | 0.065* | 0.76 |
H2AH | 0.2946 | 0.1661 | 0.1320 | 0.065* | 0.76 |
H2AI | 0.3996 | 0.1243 | 0.1022 | 0.065* | 0.76 |
S1AB | 0.3490 (6) | 0.2126 (2) | 0.0986 (4) | 0.0307 (12) | 0.24 |
C2AB | 0.463 (3) | 0.1539 (12) | 0.162 (2) | 0.035 (7) | 0.24 |
H2AJ | 0.4388 | 0.1212 | 0.1143 | 0.053* | 0.24 |
H2AK | 0.5554 | 0.1626 | 0.1724 | 0.053* | 0.24 |
H2AL | 0.4505 | 0.1460 | 0.2346 | 0.053* | 0.24 |
O1A' | 0.4193 (4) | 0.22886 (15) | 0.0030 (3) | 0.0404 (10) | |
C1A' | 0.4124 (6) | 0.2669 (2) | 0.2023 (4) | 0.0382 (14) | |
H1AM | 0.4510 | 0.3031 | 0.1970 | 0.057* | 0.76 |
H1AN | 0.3159 | 0.2698 | 0.1686 | 0.057* | 0.76 |
H1AO | 0.4331 | 0.2562 | 0.2806 | 0.057* | 0.76 |
H1AJ | 0.3623 | 0.3019 | 0.1771 | 0.057* | 0.24 |
H1AK | 0.4018 | 0.2557 | 0.2736 | 0.057* | 0.24 |
H1AL | 0.5066 | 0.2723 | 0.2114 | 0.057* | 0.24 |
N1' | 0.3920 (4) | 0.3519 (2) | −0.0544 (3) | 0.0261 (10) | |
H1'N | 0.397 (5) | 0.312 (2) | −0.041 (4) | 0.047 (17)* | |
N2' | 0.1502 (5) | 0.3830 (2) | 0.0822 (3) | 0.0300 (10) | |
H2'N | 0.193 (6) | 0.412 (2) | 0.083 (4) | 0.042 (18)* | |
N3' | 0.3913 (5) | 0.4016 (2) | 0.3498 (3) | 0.0328 (11) | |
H3'N | 0.398 (5) | 0.366 (2) | 0.365 (4) | 0.033 (15)* | |
N4' | 0.6338 (5) | 0.3953 (2) | 0.1973 (3) | 0.0304 (10) | |
H4'N | 0.579 (8) | 0.426 (3) | 0.167 (6) | 0.10 (3)* | |
C1' | 0.5009 (5) | 0.3854 (2) | −0.0473 (4) | 0.0267 (11) | |
C2' | 0.4492 (6) | 0.4379 (2) | −0.0892 (4) | 0.0337 (13) | |
H2' | 0.5015 | 0.4702 | −0.0950 | 0.040* | |
C3' | 0.3075 (6) | 0.4356 (2) | −0.1230 (4) | 0.0346 (13) | |
H3' | 0.2452 | 0.4664 | −0.1563 | 0.042* | |
C4' | 0.2717 (5) | 0.3816 (2) | −0.1016 (4) | 0.0274 (12) | |
C5' | 0.1367 (5) | 0.3562 (2) | −0.1175 (4) | 0.0305 (12) | |
C6' | 0.1175 (5) | 0.3435 (2) | −0.0044 (4) | 0.0281 (12) | |
C7' | 0.0621 (5) | 0.2993 (2) | 0.0346 (4) | 0.0321 (12) | |
H7' | 0.0290 | 0.2655 | −0.0075 | 0.038* | |
C8' | 0.0596 (5) | 0.3121 (2) | 0.1460 (4) | 0.0325 (12) | |
H8' | 0.0249 | 0.2888 | 0.1938 | 0.039* | |
C9' | 0.1162 (5) | 0.3638 (2) | 0.1746 (4) | 0.0278 (12) | |
C10' | 0.1354 (5) | 0.4013 (2) | 0.2787 (4) | 0.0304 (12) | |
C11' | 0.2680 (6) | 0.4298 (2) | 0.3040 (4) | 0.0318 (12) | |
C12' | 0.2986 (6) | 0.4843 (2) | 0.2835 (4) | 0.0420 (14) | |
H12' | 0.2334 | 0.5144 | 0.2524 | 0.050* | |
C13' | 0.4409 (6) | 0.4884 (2) | 0.3172 (5) | 0.0419 (15) | |
H13' | 0.4906 | 0.5217 | 0.3125 | 0.050* | |
C14' | 0.4969 (6) | 0.4367 (2) | 0.3577 (4) | 0.0334 (13) | |
C15' | 0.6448 (6) | 0.4162 (2) | 0.3986 (4) | 0.0372 (14) | |
C16' | 0.6746 (5) | 0.3784 (2) | 0.3088 (4) | 0.0319 (13) | |
C17' | 0.7403 (5) | 0.3272 (2) | 0.3142 (4) | 0.0351 (13) | |
H17' | 0.7803 | 0.3051 | 0.3818 | 0.042* | |
C18' | 0.7399 (5) | 0.3118 (2) | 0.2014 (4) | 0.0355 (13) | |
H18' | 0.7783 | 0.2776 | 0.1793 | 0.043* | |
C19' | 0.6731 (5) | 0.3549 (2) | 0.1305 (4) | 0.0307 (12) | |
C20' | 0.6455 (5) | 0.3648 (2) | 0.0043 (4) | 0.0291 (12) | |
C21' | 0.1224 (6) | 0.3010 (2) | −0.1865 (4) | 0.0425 (15) | |
H21D | 0.1938 | 0.2745 | −0.1483 | 0.064* | |
H21E | 0.0364 | 0.2847 | −0.1934 | 0.064* | |
H21F | 0.1289 | 0.3092 | −0.2606 | 0.064* | |
C22' | 0.0228 (6) | 0.3985 (2) | −0.1811 (5) | 0.0451 (15) | |
H22D | 0.0307 | 0.4331 | −0.1384 | 0.068* | |
H22E | 0.0293 | 0.4066 | −0.2553 | 0.068* | |
H22F | −0.0632 | 0.3821 | −0.1881 | 0.068* | |
C23' | 0.0195 (6) | 0.4460 (3) | 0.2546 (5) | 0.048 (2) | |
H23D | 0.0220 | 0.4696 | 0.1921 | 0.072* | |
H23E | −0.0656 | 0.4272 | 0.2359 | 0.072* | |
H23F | 0.0295 | 0.4692 | 0.3205 | 0.072* | |
C24' | 0.1279 (6) | 0.3645 (2) | 0.3786 (4) | 0.0430 (15) | |
H24D | 0.2000 | 0.3362 | 0.3948 | 0.065* | |
H24E | 0.1375 | 0.3880 | 0.4441 | 0.065* | |
H24F | 0.0424 | 0.3461 | 0.3595 | 0.065* | |
C25' | 0.6737 (6) | 0.3820 (3) | 0.5093 (4) | 0.048 (2) | |
H25D | 0.6150 | 0.3501 | 0.4959 | 0.073* | |
H25E | 0.7664 | 0.3685 | 0.5333 | 0.073* | |
H25F | 0.6567 | 0.4056 | 0.5673 | 0.073* | |
C26' | 0.7367 (6) | 0.4677 (3) | 0.4205 (5) | 0.053 (2) | |
H26D | 0.7195 | 0.4894 | 0.3517 | 0.080* | |
H26E | 0.7198 | 0.4914 | 0.4784 | 0.080* | |
H26F | 0.8295 | 0.4543 | 0.4444 | 0.080* | |
C27' | 0.7429 (6) | 0.4093 (2) | −0.0129 (4) | 0.0423 (14) | |
H27D | 0.7254 | 0.4447 | 0.0200 | 0.063* | |
H27E | 0.8351 | 0.3968 | 0.0227 | 0.063* | |
H27F | 0.7282 | 0.4146 | −0.0926 | 0.063* | |
C28' | 0.6737 (6) | 0.3091 (2) | −0.0502 (4) | 0.0378 (13) | |
H28D | 0.6135 | 0.2810 | −0.0387 | 0.057* | |
H28E | 0.6589 | 0.3143 | −0.1300 | 0.057* | |
H28F | 0.7658 | 0.2965 | −0.0147 | 0.057* | |
N1 | 0.4153 (4) | 0.1471 (2) | 0.4481 (3) | 0.0267 (10) | |
H1N | 0.415 (5) | 0.184 (2) | 0.467 (4) | 0.035 (15)* | |
N2 | 0.1814 (5) | 0.1121 (2) | 0.5861 (3) | 0.0323 (11) | |
H2N | 0.230 (7) | 0.083 (3) | 0.587 (6) | 0.08 (3)* | |
N3 | 0.4249 (5) | 0.0995 (2) | 0.8538 (3) | 0.0334 (11) | |
H3N | 0.424 (6) | 0.138 (2) | 0.879 (5) | 0.06 (2)* | |
N4 | 0.6640 (5) | 0.1087 (2) | 0.7026 (3) | 0.0316 (10) | |
H4N | 0.617 (6) | 0.075 (2) | 0.680 (5) | 0.057 (19)* | |
C1 | 0.5314 (5) | 0.1151 (2) | 0.4581 (4) | 0.0289 (12) | |
C2 | 0.4907 (6) | 0.0617 (2) | 0.4175 (4) | 0.0356 (13) | |
H2 | 0.5494 | 0.0297 | 0.4149 | 0.043* | |
C3 | 0.3480 (6) | 0.0621 (2) | 0.3834 (4) | 0.0350 (13) | |
H3 | 0.2916 | 0.0309 | 0.3512 | 0.042* | |
C4 | 0.3026 (5) | 0.1156 (2) | 0.4024 (4) | 0.0292 (12) | |
C5 | 0.1608 (5) | 0.1390 (2) | 0.3864 (4) | 0.0313 (12) | |
C6 | 0.1406 (5) | 0.1514 (2) | 0.4996 (4) | 0.0291 (12) | |
C7 | 0.0757 (5) | 0.1952 (2) | 0.5375 (5) | 0.0355 (13) | |
H7 | 0.0352 | 0.2288 | 0.4950 | 0.043* | |
C8 | 0.0782 (6) | 0.1820 (2) | 0.6489 (4) | 0.0391 (14) | |
H8 | 0.0396 | 0.2049 | 0.6964 | 0.047* | |
C9 | 0.1434 (5) | 0.1310 (2) | 0.6778 (4) | 0.0320 (12) | |
C10 | 0.1694 (6) | 0.0932 (2) | 0.7827 (4) | 0.0417 (15) | |
C11 | 0.3112 (6) | 0.0677 (2) | 0.8116 (4) | 0.0385 (14) | |
C12 | 0.3563 (8) | 0.0138 (2) | 0.7976 (5) | 0.054 (2) | |
H12 | 0.2993 | −0.0179 | 0.7696 | 0.065* | |
C13 | 0.4986 (7) | 0.0131 (3) | 0.8319 (5) | 0.053 (2) | |
H13 | 0.5577 | −0.0190 | 0.8306 | 0.063* | |
C14 | 0.5409 (6) | 0.0668 (2) | 0.8675 (4) | 0.0366 (14) | |
C15 | 0.6806 (6) | 0.0902 (3) | 0.9061 (4) | 0.0411 (15) | |
C16 | 0.7023 (5) | 0.1269 (2) | 0.8141 (4) | 0.0327 (13) | |
C17 | 0.7601 (5) | 0.1785 (2) | 0.8154 (4) | 0.0387 (14) | |
H17 | 0.7958 | 0.2018 | 0.8811 | 0.046* | |
C18 | 0.7560 (5) | 0.1924 (2) | 0.7024 (4) | 0.0367 (13) | |
H18 | 0.7888 | 0.2262 | 0.6774 | 0.044* | |
C19 | 0.6979 (5) | 0.1486 (2) | 0.6345 (4) | 0.0289 (12) | |
C20 | 0.6718 (5) | 0.1371 (2) | 0.5080 (4) | 0.0296 (12) | |
C21 | 0.0579 (6) | 0.0952 (3) | 0.3232 (5) | 0.049 (2) | |
H21A | 0.0739 | 0.0605 | 0.3665 | 0.073* | |
H21B | −0.0321 | 0.1097 | 0.3149 | 0.073* | |
H21C | 0.0677 | 0.0879 | 0.2496 | 0.073* | |
C22 | 0.1346 (6) | 0.1944 (2) | 0.3158 (4) | 0.0427 (15) | |
H22A | 0.1994 | 0.2217 | 0.3551 | 0.064* | |
H22B | 0.1446 | 0.1873 | 0.2423 | 0.064* | |
H22C | 0.0447 | 0.2092 | 0.3075 | 0.064* | |
C23 | 0.0654 (7) | 0.0460 (3) | 0.7549 (5) | 0.062 (2) | |
H23A | 0.0766 | 0.0239 | 0.6928 | 0.093* | |
H23B | 0.0803 | 0.0219 | 0.8203 | 0.093* | |
H23C | −0.0248 | 0.0623 | 0.7347 | 0.093* | |
C24 | 0.1490 (6) | 0.1289 (3) | 0.8804 (4) | 0.050 (2) | |
H24A | 0.2132 | 0.1588 | 0.8973 | 0.074* | |
H24B | 0.0588 | 0.1453 | 0.8603 | 0.074* | |
H24C | 0.1639 | 0.1048 | 0.9459 | 0.074* | |
C25 | 0.7863 (7) | 0.0406 (3) | 0.9305 (5) | 0.060 (2) | |
H25A | 0.7750 | 0.0185 | 0.8630 | 0.090* | |
H25B | 0.8756 | 0.0557 | 0.9543 | 0.090* | |
H25C | 0.7744 | 0.0168 | 0.9895 | 0.090* | |
C26 | 0.7026 (6) | 0.1253 (3) | 1.0148 (4) | 0.054 (2) | |
H26A | 0.6363 | 0.1561 | 0.9991 | 0.080* | |
H26B | 0.6906 | 0.1016 | 1.0739 | 0.080* | |
H26C | 0.7918 | 0.1406 | 1.0387 | 0.080* | |
C27 | 0.7772 (5) | 0.0926 (2) | 0.4937 (4) | 0.0388 (14) | |
H27A | 0.7662 | 0.0574 | 0.5286 | 0.058* | |
H27B | 0.7651 | 0.0865 | 0.4145 | 0.058* | |
H27C | 0.8665 | 0.1063 | 0.5295 | 0.058* | |
C28 | 0.6900 (6) | 0.1922 (2) | 0.4510 (4) | 0.0409 (14) | |
H28A | 0.6244 | 0.2203 | 0.4590 | 0.061* | |
H28B | 0.7796 | 0.2055 | 0.4869 | 0.061* | |
H28C | 0.6782 | 0.1857 | 0.3720 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0314 (11) | 0.0305 (9) | 0.0230 (8) | −0.0040 (8) | 0.0082 (7) | −0.0021 (7) |
C2A | 0.048 (5) | 0.038 (4) | 0.023 (4) | 0.008 (4) | 0.011 (4) | −0.003 (3) |
O1A | 0.062 (3) | 0.038 (2) | 0.024 (2) | 0.002 (2) | 0.014 (2) | −0.004 (2) |
C1A | 0.045 (4) | 0.038 (3) | 0.032 (3) | −0.011 (3) | 0.012 (3) | 0.004 (2) |
S1AA | 0.050 (4) | 0.038 (3) | 0.037 (3) | 0.002 (3) | 0.016 (3) | 0.004 (3) |
C2AA | 0.059 (13) | 0.056 (12) | 0.053 (12) | −0.010 (9) | 0.018 (9) | 0.001 (8) |
S1A' | 0.0332 (11) | 0.0321 (10) | 0.0251 (9) | 0.0001 (8) | 0.0072 (8) | 0.0007 (7) |
C2A' | 0.057 (6) | 0.041 (4) | 0.030 (4) | −0.013 (5) | 0.010 (4) | 0.004 (3) |
S1AB | 0.035 (3) | 0.029 (3) | 0.028 (3) | −0.002 (2) | 0.008 (2) | −0.002 (2) |
C2AB | 0.035 (10) | 0.038 (10) | 0.027 (9) | 0.003 (9) | 0.001 (8) | 0.007 (7) |
O1A' | 0.058 (3) | 0.038 (2) | 0.028 (2) | 0.000 (2) | 0.017 (2) | 0.004 (2) |
C1A' | 0.039 (3) | 0.042 (3) | 0.030 (3) | −0.001 (3) | 0.006 (3) | −0.007 (2) |
N1' | 0.033 (3) | 0.023 (2) | 0.021 (2) | 0.000 (2) | 0.007 (2) | 0.000 (2) |
N2' | 0.036 (3) | 0.029 (3) | 0.026 (2) | −0.003 (2) | 0.011 (2) | −0.002 (2) |
N3' | 0.040 (3) | 0.029 (3) | 0.029 (2) | −0.003 (2) | 0.011 (2) | −0.001 (2) |
N4' | 0.035 (3) | 0.035 (3) | 0.023 (2) | −0.005 (2) | 0.010 (2) | −0.004 (2) |
C1' | 0.034 (3) | 0.027 (3) | 0.019 (2) | −0.006 (2) | 0.008 (2) | −0.006 (2) |
C2' | 0.047 (4) | 0.022 (3) | 0.034 (3) | −0.006 (3) | 0.016 (3) | −0.002 (2) |
C3' | 0.046 (4) | 0.023 (3) | 0.035 (3) | 0.006 (3) | 0.013 (3) | 0.004 (2) |
C4' | 0.032 (3) | 0.033 (3) | 0.015 (2) | 0.001 (2) | 0.005 (2) | −0.003 (2) |
C5' | 0.032 (3) | 0.033 (3) | 0.023 (3) | 0.004 (2) | 0.005 (2) | −0.004 (2) |
C6' | 0.022 (3) | 0.032 (3) | 0.027 (3) | 0.007 (2) | 0.002 (2) | −0.005 (2) |
C7' | 0.025 (3) | 0.030 (3) | 0.041 (3) | −0.003 (2) | 0.008 (2) | 0.000 (2) |
C8' | 0.031 (3) | 0.035 (3) | 0.033 (3) | 0.001 (2) | 0.012 (2) | 0.004 (2) |
C9' | 0.025 (3) | 0.035 (3) | 0.023 (3) | 0.006 (2) | 0.006 (2) | 0.006 (2) |
C10' | 0.029 (3) | 0.038 (3) | 0.026 (3) | 0.004 (2) | 0.011 (2) | 0.002 (2) |
C11' | 0.041 (3) | 0.036 (3) | 0.020 (3) | 0.002 (3) | 0.013 (2) | −0.005 (2) |
C12' | 0.050 (4) | 0.042 (3) | 0.035 (3) | 0.002 (3) | 0.014 (3) | 0.003 (3) |
C13' | 0.063 (4) | 0.028 (3) | 0.040 (3) | −0.015 (3) | 0.021 (3) | −0.004 (2) |
C14' | 0.041 (3) | 0.042 (3) | 0.022 (3) | −0.014 (3) | 0.015 (2) | −0.009 (2) |
C15' | 0.040 (3) | 0.049 (3) | 0.023 (3) | −0.018 (3) | 0.009 (2) | −0.008 (2) |
C16' | 0.034 (3) | 0.043 (3) | 0.018 (3) | −0.012 (3) | 0.005 (2) | −0.002 (2) |
C17' | 0.031 (3) | 0.046 (3) | 0.026 (3) | −0.007 (3) | 0.004 (2) | 0.009 (2) |
C18' | 0.033 (3) | 0.037 (3) | 0.037 (3) | −0.001 (3) | 0.010 (3) | −0.001 (2) |
C19' | 0.036 (3) | 0.030 (3) | 0.028 (3) | −0.006 (2) | 0.011 (2) | −0.003 (2) |
C20' | 0.032 (3) | 0.033 (3) | 0.024 (3) | −0.005 (2) | 0.010 (2) | −0.008 (2) |
C21' | 0.041 (4) | 0.051 (4) | 0.032 (3) | −0.011 (3) | 0.005 (3) | −0.017 (3) |
C22' | 0.036 (3) | 0.058 (4) | 0.036 (3) | 0.010 (3) | 0.005 (3) | 0.009 (3) |
C23' | 0.044 (4) | 0.061 (4) | 0.037 (3) | 0.017 (3) | 0.010 (3) | −0.003 (3) |
C24' | 0.037 (3) | 0.062 (4) | 0.030 (3) | −0.002 (3) | 0.010 (3) | 0.004 (3) |
C25' | 0.042 (4) | 0.076 (5) | 0.028 (3) | −0.011 (3) | 0.011 (3) | −0.002 (3) |
C26' | 0.057 (4) | 0.069 (4) | 0.039 (3) | −0.035 (4) | 0.020 (3) | −0.016 (3) |
C27' | 0.043 (4) | 0.055 (4) | 0.033 (3) | −0.016 (3) | 0.016 (3) | −0.006 (3) |
C28' | 0.036 (3) | 0.049 (3) | 0.027 (3) | −0.002 (3) | 0.007 (2) | −0.010 (2) |
N1 | 0.031 (3) | 0.025 (2) | 0.024 (2) | 0.000 (2) | 0.008 (2) | 0.001 (2) |
N2 | 0.042 (3) | 0.030 (3) | 0.026 (2) | −0.002 (2) | 0.011 (2) | −0.001 (2) |
N3 | 0.040 (3) | 0.032 (3) | 0.025 (2) | 0.001 (2) | 0.006 (2) | 0.000 (2) |
N4 | 0.038 (3) | 0.032 (3) | 0.023 (2) | 0.001 (2) | 0.008 (2) | 0.002 (2) |
C1 | 0.030 (3) | 0.037 (3) | 0.021 (3) | 0.003 (2) | 0.009 (2) | 0.005 (2) |
C2 | 0.041 (4) | 0.030 (3) | 0.035 (3) | 0.002 (3) | 0.011 (3) | −0.001 (2) |
C3 | 0.050 (4) | 0.024 (3) | 0.032 (3) | −0.009 (3) | 0.013 (3) | −0.006 (2) |
C4 | 0.036 (3) | 0.029 (3) | 0.022 (3) | −0.010 (2) | 0.008 (2) | 0.000 (2) |
C5 | 0.032 (3) | 0.034 (3) | 0.024 (3) | −0.009 (2) | 0.003 (2) | 0.002 (2) |
C6 | 0.029 (3) | 0.031 (3) | 0.027 (3) | −0.007 (2) | 0.007 (2) | 0.002 (2) |
C7 | 0.033 (3) | 0.030 (3) | 0.043 (3) | −0.005 (2) | 0.010 (3) | −0.004 (2) |
C8 | 0.042 (4) | 0.044 (3) | 0.035 (3) | −0.013 (3) | 0.016 (3) | −0.016 (3) |
C9 | 0.038 (3) | 0.031 (3) | 0.028 (3) | −0.013 (3) | 0.011 (2) | −0.006 (2) |
C10 | 0.052 (4) | 0.049 (4) | 0.025 (3) | −0.018 (3) | 0.011 (3) | −0.003 (2) |
C11 | 0.055 (4) | 0.043 (3) | 0.021 (3) | −0.012 (3) | 0.014 (3) | 0.001 (2) |
C12 | 0.092 (6) | 0.030 (3) | 0.042 (4) | −0.012 (3) | 0.023 (4) | −0.004 (3) |
C13 | 0.079 (5) | 0.038 (4) | 0.045 (4) | 0.015 (3) | 0.027 (4) | 0.007 (3) |
C14 | 0.054 (4) | 0.035 (3) | 0.020 (3) | 0.011 (3) | 0.011 (3) | 0.004 (2) |
C15 | 0.044 (4) | 0.060 (4) | 0.021 (3) | 0.022 (3) | 0.013 (3) | 0.007 (3) |
C16 | 0.027 (3) | 0.048 (3) | 0.019 (3) | 0.010 (3) | 0.002 (2) | −0.002 (2) |
C17 | 0.035 (3) | 0.045 (3) | 0.032 (3) | 0.005 (3) | 0.005 (3) | −0.011 (3) |
C18 | 0.032 (3) | 0.039 (3) | 0.038 (3) | −0.003 (3) | 0.008 (3) | −0.002 (2) |
C19 | 0.027 (3) | 0.034 (3) | 0.024 (3) | 0.003 (2) | 0.006 (2) | 0.000 (2) |
C20 | 0.031 (3) | 0.034 (3) | 0.024 (3) | 0.000 (2) | 0.009 (2) | 0.006 (2) |
C21 | 0.047 (4) | 0.059 (4) | 0.036 (3) | −0.013 (3) | 0.005 (3) | −0.007 (3) |
C22 | 0.039 (4) | 0.052 (4) | 0.035 (3) | 0.009 (3) | 0.008 (3) | 0.017 (3) |
C23 | 0.072 (5) | 0.077 (5) | 0.032 (3) | −0.043 (4) | 0.004 (3) | 0.010 (3) |
C24 | 0.036 (4) | 0.084 (5) | 0.029 (3) | −0.008 (3) | 0.010 (3) | −0.005 (3) |
C25 | 0.056 (4) | 0.079 (5) | 0.047 (4) | 0.029 (4) | 0.020 (3) | 0.022 (3) |
C26 | 0.054 (4) | 0.081 (5) | 0.023 (3) | 0.009 (4) | 0.009 (3) | −0.004 (3) |
C27 | 0.036 (3) | 0.051 (4) | 0.031 (3) | 0.004 (3) | 0.013 (3) | 0.001 (3) |
C28 | 0.040 (4) | 0.050 (4) | 0.032 (3) | −0.005 (3) | 0.011 (3) | 0.011 (3) |
S1A—O1A | 1.529 (4) | C22'—H22F | 0.96 |
S1A—C2A | 1.778 (8) | C23'—H23D | 0.96 |
S1A—C1A | 1.798 (5) | C23'—H23E | 0.96 |
C2A—H2AA | 0.96 | C23'—H23F | 0.96 |
C2A—H2AB | 0.96 | C24'—H24D | 0.96 |
C2A—H2AC | 0.96 | C24'—H24E | 0.96 |
O1A—S1AA | 1.652 (7) | C24'—H24F | 0.96 |
C1A—S1AA | 1.768 (8) | C25'—H25D | 0.96 |
C1A—H1AD | 0.96 | C25'—H25E | 0.96 |
C1A—H1AE | 0.96 | C25'—H25F | 0.96 |
C1A—H1AF | 0.96 | C26'—H26D | 0.96 |
C1A—H1AA | 0.96 | C26'—H26E | 0.96 |
C1A—H1AB | 0.96 | C26'—H26F | 0.96 |
C1A—H1AC | 0.96 | C27'—H27D | 0.96 |
S1AA—C2AA | 1.80 (3) | C27'—H27E | 0.96 |
C2AA—H2AD | 0.96 | C27'—H27F | 0.96 |
C2AA—H2AE | 0.96 | C28'—H28D | 0.96 |
C2AA—H2AF | 0.96 | C28'—H28E | 0.96 |
S1A'—O1A' | 1.530 (4) | C28'—H28F | 0.96 |
S1A'—C1A' | 1.788 (5) | N1—C1 | 1.374 (6) |
S1A'—C2A' | 1.784 (8) | N1—C4 | 1.371 (6) |
C2A'—H2AG | 0.96 | N1—H1N | 0.89 (5) |
C2A'—H2AH | 0.96 | N2—C6 | 1.374 (6) |
C2A'—H2AI | 0.96 | N2—C9 | 1.377 (6) |
C2A'—H2AJ | 1.10 (3) | N2—H2N | 0.83 (7) |
C2A'—H2AL | 1.06 (3) | N3—C14 | 1.373 (7) |
S1AB—O1A' | 1.617 (6) | N3—C11 | 1.375 (7) |
S1AB—C2AB | 1.80 (3) | N3—H3N | 0.96 (6) |
S1AB—C1A' | 1.796 (7) | N4—C16 | 1.385 (6) |
C2AB—H2AJ | 0.96 | N4—C19 | 1.385 (6) |
C2AB—H2AK | 0.96 | N4—H4N | 0.94 (6) |
C2AB—H2AL | 0.96 | C1—C2 | 1.376 (7) |
C1A'—H1AM | 0.96 | C1—C20 | 1.504 (7) |
C1A'—H1AN | 0.96 | C2—C3 | 1.409 (7) |
C1A'—H1AO | 0.96 | C2—H2 | 0.96 |
C1A'—H1AJ | 0.96 | C3—C4 | 1.371 (7) |
C1A'—H1AK | 0.96 | C3—H3 | 0.96 |
C1A'—H1AL | 0.96 | C4—C5 | 1.509 (7) |
N1'—C1' | 1.375 (6) | C5—C6 | 1.504 (7) |
N1'—C4' | 1.377 (6) | C5—C21 | 1.535 (7) |
N1'—H1'N | 0.94 (5) | C5—C22 | 1.540 (7) |
N2'—C9' | 1.376 (6) | C6—C7 | 1.370 (7) |
N2'—C6' | 1.382 (6) | C7—C8 | 1.407 (7) |
N2'—H2'N | 0.83 (5) | C7—H7 | 0.96 |
N3'—C14' | 1.367 (6) | C8—C9 | 1.350 (7) |
N3'—C11' | 1.380 (7) | C8—H8 | 0.96 |
N3'—H3'N | 0.87 (5) | C9—C10 | 1.526 (7) |
N4'—C16' | 1.371 (6) | C10—C11 | 1.509 (8) |
N4'—C19' | 1.387 (6) | C10—C24 | 1.531 (7) |
N4'—H4'N | 0.91 (7) | C10—C23 | 1.533 (7) |
C1'—C2' | 1.368 (7) | C11—C12 | 1.365 (8) |
C1'—C20' | 1.506 (7) | C12—C13 | 1.404 (9) |
C2'—C3' | 1.402 (7) | C12—H12 | 0.96 |
C2'—H2' | 0.96 | C13—C14 | 1.373 (8) |
C3'—C4' | 1.380 (7) | C13—H13 | 0.96 |
C3'—H3' | 0.96 | C14—C15 | 1.500 (8) |
C4'—C5' | 1.494 (7) | C15—C16 | 1.504 (7) |
C5'—C6' | 1.503 (7) | C15—C26 | 1.536 (7) |
C5'—C21' | 1.535 (7) | C15—C25 | 1.540 (7) |
C5'—C22' | 1.541 (7) | C16—C17 | 1.364 (7) |
C6'—C7' | 1.358 (7) | C17—C18 | 1.424 (7) |
C7'—C8' | 1.417 (7) | C17—H17 | 0.96 |
C7'—H7' | 0.96 | C18—C19 | 1.359 (7) |
C8'—C9' | 1.361 (7) | C18—H18 | 0.96 |
C8'—H8' | 0.96 | C19—C20 | 1.529 (7) |
C9'—C10' | 1.523 (7) | C20—C28 | 1.518 (7) |
C10'—C11' | 1.492 (7) | C20—C27 | 1.538 (7) |
C10'—C23' | 1.532 (7) | C21—H21A | 0.96 |
C10'—C24' | 1.532 (7) | C21—H21B | 0.96 |
C11'—C12' | 1.369 (7) | C21—H21C | 0.96 |
C12'—C13' | 1.412 (8) | C22—H22A | 0.96 |
C12'—H12' | 0.96 | C22—H22B | 0.96 |
C13'—C14' | 1.361 (7) | C22—H22C | 0.96 |
C13'—H13' | 0.96 | C23—H23A | 0.96 |
C14'—C15' | 1.524 (8) | C23—H23B | 0.96 |
C15'—C16' | 1.518 (7) | C23—H23C | 0.96 |
C15'—C26' | 1.532 (7) | C24—H24A | 0.96 |
C15'—C25' | 1.535 (7) | C24—H24B | 0.96 |
C16'—C17' | 1.355 (7) | C24—H24C | 0.96 |
C17'—C18' | 1.439 (7) | C25—H25A | 0.96 |
C17'—H17' | 0.96 | C25—H25B | 0.96 |
C18'—C19' | 1.367 (7) | C25—H25C | 0.96 |
C18'—H18' | 0.96 | C26—H26A | 0.96 |
C19'—C20' | 1.517 (7) | C26—H26B | 0.96 |
C20'—C28' | 1.529 (7) | C26—H26C | 0.96 |
C20'—C27' | 1.533 (7) | C27—H27A | 0.96 |
C21'—H21D | 0.96 | C27—H27B | 0.96 |
C21'—H21E | 0.96 | C27—H27C | 0.96 |
C21'—H21F | 0.96 | C28—H28A | 0.96 |
C22'—H22D | 0.96 | C28—H28B | 0.96 |
C22'—H22E | 0.96 | C28—H28C | 0.96 |
O1A—S1A—C2A | 105.0 (3) | H23D—C23'—H23F | 109.5 |
O1A—S1A—C1A | 105.2 (2) | H23E—C23'—H23F | 109.5 |
C2A—S1A—C1A | 97.9 (3) | C10'—C24'—H24D | 108.8 |
S1A—C2A—H2AA | 108.9 | C10'—C24'—H24E | 109.7 |
S1A—C2A—H2AB | 110.0 | H24D—C24'—H24E | 109.5 |
H2AA—C2A—H2AB | 109.5 | C10'—C24'—H24F | 109.9 |
S1A—C2A—H2AC | 109.5 | H24D—C24'—H24F | 109.5 |
H2AA—C2A—H2AC | 109.5 | H24E—C24'—H24F | 109.5 |
H2AB—C2A—H2AC | 109.5 | C15'—C25'—H25D | 108.7 |
S1AA—C1A—H1AD | 109.2 | C15'—C25'—H25E | 109.9 |
S1AA—C1A—H1AE | 109.5 | H25D—C25'—H25E | 109.5 |
H1AD—C1A—H1AE | 109.5 | C15'—C25'—H25F | 109.8 |
S1AA—C1A—H1AF | 109.7 | H25D—C25'—H25F | 109.5 |
H1AD—C1A—H1AF | 109.5 | H25E—C25'—H25F | 109.5 |
H1AE—C1A—H1AF | 109.5 | C15'—C26'—H26D | 109.3 |
S1A—C1A—H1AA | 109.2 | C15'—C26'—H26E | 110.3 |
S1A—C1A—H1AB | 109.5 | H26D—C26'—H26E | 109.5 |
H1AA—C1A—H1AB | 109.5 | C15'—C26'—H26F | 108.8 |
S1A—C1A—H1AC | 109.8 | H26D—C26'—H26F | 109.5 |
H1AA—C1A—H1AC | 109.5 | H26E—C26'—H26F | 109.5 |
H1AB—C1A—H1AC | 109.5 | C20'—C27'—H27D | 109.0 |
O1A—S1AA—C1A | 101.4 (4) | C20'—C27'—H27E | 110.3 |
O1A—S1AA—C2AA | 97.5 (12) | H27D—C27'—H27E | 109.5 |
C1A—S1AA—C2AA | 99.3 (12) | C20'—C27'—H27F | 109.1 |
S1AA—C2AA—H2AD | 107.2 | H27D—C27'—H27F | 109.5 |
S1AA—C2AA—H2AE | 106.3 | H27E—C27'—H27F | 109.5 |
H2AD—C2AA—H2AE | 109.5 | C20'—C28'—H28D | 108.2 |
S1AA—C2AA—H2AF | 114.8 | C20'—C28'—H28E | 110.8 |
H2AD—C2AA—H2AF | 109.5 | H28D—C28'—H28E | 109.5 |
H2AE—C2AA—H2AF | 109.5 | C20'—C28'—H28F | 109.4 |
O1A'—S1A'—C1A' | 105.1 (2) | H28D—C28'—H28F | 109.5 |
O1A'—S1A'—C2A' | 103.9 (3) | H28E—C28'—H28F | 109.5 |
C1A'—S1A'—C2A' | 98.2 (4) | C1—N1—C4 | 110.8 (4) |
S1A'—C2A'—H2AG | 109.8 | C1—N1—H1N | 124 (3) |
S1A'—C2A'—H2AH | 109.3 | C4—N1—H1N | 126 (3) |
H2AG—C2A'—H2AH | 109.5 | C6—N2—C9 | 109.6 (5) |
S1A'—C2A'—H2AI | 109.3 | C6—N2—H2N | 126 (5) |
H2AG—C2A'—H2AI | 109.5 | C9—N2—H2N | 124 (5) |
H2AH—C2A'—H2AI | 109.5 | C14—N3—C11 | 111.2 (5) |
O1A'—S1AB—C2AB | 97.4 (10) | C14—N3—H3N | 124 (4) |
O1A'—S1AB—C1A' | 101.2 (4) | C11—N3—H3N | 124 (4) |
C2AB—S1AB—C1A' | 100.1 (9) | C16—N4—C19 | 110.0 (5) |
S1AB—C2AB—H2AJ | 108.7 | C16—N4—H4N | 122 (4) |
S1AB—C2AB—H2AK | 111.8 | C19—N4—H4N | 128 (4) |
H2AJ—C2AB—H2AK | 109.5 | N1—C1—C2 | 106.5 (5) |
S1AB—C2AB—H2AL | 107.9 | N1—C1—C20 | 123.7 (4) |
H2AJ—C2AB—H2AL | 109.5 | C2—C1—C20 | 129.8 (5) |
H2AK—C2AB—H2AL | 109.5 | C1—C2—C3 | 107.9 (5) |
S1A'—C1A'—H1AM | 109.3 | C1—C2—H2 | 125.9 |
S1A'—C1A'—H1AN | 109.5 | C3—C2—H2 | 126.2 |
H1AM—C1A'—H1AN | 109.5 | C4—C3—C2 | 108.2 (5) |
S1A'—C1A'—H1AO | 109.6 | C4—C3—H3 | 125.4 |
S1AB—C1A'—H1AO | 117.1 | C2—C3—H3 | 126.4 |
H1AM—C1A'—H1AO | 109.5 | C3—C4—N1 | 106.6 (5) |
H1AN—C1A'—H1AO | 109.5 | C3—C4—C5 | 130.8 (5) |
S1AB—C1A'—H1AJ | 109.1 | N1—C4—C5 | 122.5 (4) |
H1AO—C1A'—H1AJ | 118.7 | C6—C5—C4 | 110.2 (4) |
S1A'—C1A'—H1AK | 116.9 | C6—C5—C21 | 109.3 (4) |
S1AB—C1A'—H1AK | 109.6 | C4—C5—C21 | 109.4 (4) |
H1AM—C1A'—H1AK | 118.8 | C6—C5—C22 | 108.8 (4) |
H1AJ—C1A'—H1AK | 109.5 | C4—C5—C22 | 110.8 (4) |
S1AB—C1A'—H1AL | 109.7 | C21—C5—C22 | 108.3 (4) |
H1AJ—C1A'—H1AL | 109.5 | C7—C6—N2 | 106.9 (5) |
H1AK—C1A'—H1AL | 109.5 | C7—C6—C5 | 132.5 (5) |
C1'—N1'—C4' | 111.0 (4) | N2—C6—C5 | 120.3 (4) |
C1'—N1'—H1'N | 125 (3) | C6—C7—C8 | 107.7 (5) |
C4'—N1'—H1'N | 123 (3) | C6—C7—H7 | 125.9 |
C9'—N2'—C6' | 110.6 (4) | C8—C7—H7 | 126.4 |
C9'—N2'—H2'N | 123 (4) | C9—C8—C7 | 108.3 (5) |
C6'—N2'—H2'N | 126 (4) | C9—C8—H8 | 125.6 |
C14'—N3'—C11' | 111.5 (5) | C7—C8—H8 | 126.1 |
C14'—N3'—H3'N | 126 (4) | C8—C9—N2 | 107.4 (5) |
C11'—N3'—H3'N | 122 (4) | C8—C9—C10 | 132.5 (5) |
C16'—N4'—C19' | 110.6 (4) | N2—C9—C10 | 120.0 (5) |
C16'—N4'—H4'N | 127 (5) | C11—C10—C9 | 108.9 (4) |
C19'—N4'—H4'N | 122 (5) | C11—C10—C24 | 111.7 (4) |
C2'—C1'—N1' | 106.7 (5) | C9—C10—C24 | 109.1 (5) |
C2'—C1'—C20' | 130.4 (5) | C11—C10—C23 | 110.3 (5) |
N1'—C1'—C20' | 122.9 (4) | C9—C10—C23 | 108.0 (4) |
C1'—C2'—C3' | 107.9 (5) | C24—C10—C23 | 108.8 (5) |
C1'—C2'—H2' | 125.5 | C12—C11—N3 | 106.2 (6) |
C3'—C2'—H2' | 126.6 | C12—C11—C10 | 130.9 (6) |
C4'—C3'—C2' | 108.8 (5) | N3—C11—C10 | 122.8 (5) |
C4'—C3'—H3' | 125.4 | C11—C12—C13 | 108.4 (6) |
C2'—C3'—H3' | 125.8 | C11—C12—H12 | 125.0 |
C3'—C4'—N1' | 105.5 (5) | C13—C12—H12 | 126.6 |
C3'—C4'—C5' | 131.6 (5) | C14—C13—C12 | 108.4 (6) |
N1'—C4'—C5' | 122.8 (4) | C14—C13—H13 | 124.9 |
C4'—C5'—C6' | 110.3 (4) | C12—C13—H13 | 126.7 |
C4'—C5'—C21' | 111.2 (4) | C13—C14—N3 | 105.8 (5) |
C6'—C5'—C21' | 109.0 (4) | C13—C14—C15 | 130.4 (6) |
C4'—C5'—C22' | 110.1 (4) | N3—C14—C15 | 123.6 (5) |
C6'—C5'—C22' | 107.9 (4) | C14—C15—C16 | 109.8 (4) |
C21'—C5'—C22' | 108.2 (4) | C14—C15—C26 | 111.2 (5) |
C7'—C6'—N2' | 106.3 (4) | C16—C15—C26 | 109.5 (5) |
C7'—C6'—C5' | 132.8 (5) | C14—C15—C25 | 109.5 (5) |
N2'—C6'—C5' | 120.8 (4) | C16—C15—C25 | 108.4 (4) |
C6'—C7'—C8' | 108.6 (5) | C26—C15—C25 | 108.4 (5) |
C6'—C7'—H7' | 125.2 | C17—C16—N4 | 106.6 (5) |
C8'—C7'—H7' | 126.2 | C17—C16—C15 | 132.9 (5) |
C9'—C8'—C7' | 107.9 (5) | N4—C16—C15 | 120.5 (5) |
C9'—C8'—H8' | 125.3 | C16—C17—C18 | 108.4 (5) |
C7'—C8'—H8' | 126.8 | C16—C17—H17 | 125.7 |
C8'—C9'—N2' | 106.7 (4) | C18—C17—H17 | 126.0 |
C8'—C9'—C10' | 132.6 (5) | C19—C18—C17 | 107.8 (5) |
N2'—C9'—C10' | 120.5 (4) | C19—C18—H18 | 125.2 |
C11'—C10'—C9' | 109.1 (4) | C17—C18—H18 | 127.0 |
C11'—C10'—C23' | 110.1 (5) | C18—C19—N4 | 107.2 (4) |
C9'—C10'—C23' | 109.0 (4) | C18—C19—C20 | 132.6 (5) |
C11'—C10'—C24' | 111.6 (4) | N4—C19—C20 | 120.1 (4) |
C9'—C10'—C24' | 109.2 (4) | C1—C20—C28 | 111.5 (4) |
C23'—C10'—C24' | 107.8 (4) | C1—C20—C19 | 109.6 (4) |
C12'—C11'—N3' | 105.4 (5) | C28—C20—C19 | 108.4 (4) |
C12'—C11'—C10' | 131.1 (5) | C1—C20—C27 | 109.9 (4) |
N3'—C11'—C10' | 123.3 (5) | C28—C20—C27 | 108.5 (4) |
C11'—C12'—C13' | 108.5 (5) | C19—C20—C27 | 108.9 (4) |
C11'—C12'—H12' | 125.2 | C5—C21—H21A | 108.8 |
C13'—C12'—H12' | 126.3 | C5—C21—H21B | 109.4 |
C14'—C13'—C12' | 108.3 (5) | H21A—C21—H21B | 109.5 |
C14'—C13'—H13' | 125.3 | C5—C21—H21C | 110.2 |
C12'—C13'—H13' | 126.5 | H21A—C21—H21C | 109.5 |
C13'—C14'—N3' | 106.3 (5) | H21B—C21—H21C | 109.5 |
C13'—C14'—C15' | 130.5 (5) | C5—C22—H22A | 108.3 |
N3'—C14'—C15' | 123.1 (5) | C5—C22—H22B | 110.3 |
C16'—C15'—C14' | 109.2 (4) | H22A—C22—H22B | 109.5 |
C16'—C15'—C26' | 109.9 (4) | C5—C22—H22C | 109.9 |
C14'—C15'—C26' | 109.6 (5) | H22A—C22—H22C | 109.5 |
C16'—C15'—C25' | 108.9 (5) | H22B—C22—H22C | 109.5 |
C14'—C15'—C25' | 110.5 (4) | C10—C23—H23A | 109.2 |
C26'—C15'—C25' | 108.7 (4) | C10—C23—H23B | 109.0 |
C17'—C16'—N4' | 107.1 (4) | H23A—C23—H23B | 109.5 |
C17'—C16'—C15' | 132.6 (5) | C10—C23—H23C | 110.2 |
N4'—C16'—C15' | 120.2 (5) | H23A—C23—H23C | 109.5 |
C16'—C17'—C18' | 108.3 (4) | H23B—C23—H23C | 109.5 |
C16'—C17'—H17' | 125.7 | C10—C24—H24A | 108.9 |
C18'—C17'—H17' | 126.0 | C10—C24—H24B | 110.6 |
C19'—C18'—C17' | 107.1 (5) | H24A—C24—H24B | 109.5 |
C19'—C18'—H18' | 126.0 | C10—C24—H24C | 108.8 |
C17'—C18'—H18' | 126.9 | H24A—C24—H24C | 109.5 |
C18'—C19'—N4' | 106.9 (4) | H24B—C24—H24C | 109.5 |
C18'—C19'—C20' | 132.2 (5) | C15—C25—H25A | 109.5 |
N4'—C19'—C20' | 120.9 (4) | C15—C25—H25B | 109.3 |
C1'—C20'—C19' | 109.6 (4) | H25A—C25—H25B | 109.5 |
C1'—C20'—C28' | 111.2 (4) | C15—C25—H25C | 109.6 |
C19'—C20'—C28' | 108.9 (4) | H25A—C25—H25C | 109.5 |
C1'—C20'—C27' | 110.3 (4) | H25B—C25—H25C | 109.5 |
C19'—C20'—C27' | 108.8 (4) | C15—C26—H26A | 108.0 |
C28'—C20'—C27' | 108.1 (4) | C15—C26—H26B | 109.4 |
C5'—C21'—H21D | 109.1 | H26A—C26—H26B | 109.5 |
C5'—C21'—H21E | 109.8 | C15—C26—H26C | 111.0 |
H21D—C21'—H21E | 109.5 | H26A—C26—H26C | 109.5 |
C5'—C21'—H21F | 109.5 | H26B—C26—H26C | 109.5 |
H21D—C21'—H21F | 109.5 | C20—C27—H27A | 109.5 |
H21E—C21'—H21F | 109.5 | C20—C27—H27B | 109.7 |
C5'—C22'—H22D | 108.8 | H27A—C27—H27B | 109.5 |
C5'—C22'—H22E | 110.6 | C20—C27—H27C | 109.2 |
H22D—C22'—H22E | 109.5 | H27A—C27—H27C | 109.5 |
C5'—C22'—H22F | 109.1 | H27B—C27—H27C | 109.5 |
H22D—C22'—H22F | 109.5 | C20—C28—H28A | 109.4 |
H22E—C22'—H22F | 109.5 | C20—C28—H28B | 108.9 |
C10'—C23'—H23D | 109.4 | H28A—C28—H28B | 109.5 |
C10'—C23'—H23E | 109.5 | C20—C28—H28C | 110.1 |
H23D—C23'—H23E | 109.5 | H28A—C28—H28C | 109.5 |
C10'—C23'—H23F | 109.5 | H28B—C28—H28C | 109.5 |
Experimental details
(monoclinicI) | (triclinicI) | |
Crystal data | ||
Chemical formula | C28H36N4·C2H6OS | C28H36N4·C2H6OS |
Mr | 506.74 | 506.74 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 298 | 198 |
a, b, c (Å) | 10.411 (2), 23.586 (6), 12.482 (3) | 10.362 (3), 23.468 (10), 12.373 (7) |
α, β, γ (°) | 90, 107.71 (2), 90 | 90.23 (4), 107.64 (4), 88.35 (3) |
V (Å3) | 2919.7 (12) | 2866 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.14 | 0.14 |
Crystal size (mm) | 0.34 × 0.34 × 0.24 | 0.34 × 0.34 × 0.26 |
Data collection | ||
Diffractometer | Siemens P3 diffractometer | Siemens P4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6290, 5109, 2069 | 11862, 10061, 5213 |
Rint | 0.047 | 0.042 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.071, 0.152, 0.97 | 0.081, 0.155, 1.03 |
No. of reflections | 5109 | 10046 |
No. of parameters | 359 | 718 |
No. of restraints | 12 | 24 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.17 | 0.40, −0.27 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, XS in SHELXTL/PC (Sheldrick, 1998), XL in SHELXTL/PC, XP in SHELXTL/PC.
We have shown that calix[4]pyrroles are capable of binding anions (Gale et al., 1996, 1997; Sessler et al., 1996) and neutral guest species (Allen et al., 1996) in both solution and the solid state. Anion complexes of calix[4]pyrroles have been found to adopt solely the cone conformation in the solid state, whereas neutral guest complexes adopt a range of conformations [1,3-alternate (methanol) and 1,2-alternate (dimethylformamide)]. The structure of the dimethyl sulfoxide (DMSO) complex, (I), of meso-octamethylcalix[4]pyrrole is presented herein. The crystals were found to undergo a phase change between 273 and 243 K using differential scanning calorimetry (DSC). The DSC results are not completely reversible, which may be due to solvent loss during the warming cycle of the scans.
The structure reveals that the calix[4]pyrrole exists in the 1,3-alternate conformation in both the low-temperature triclinic form and the room-temperature monoclinic form. The triclinic form is reported in a non-standard pseudo-monoclinic setting for ease of comparison with the monoclinic form. The triclinic form has two molecules per asymmetric unit. Atoms of molecule 1 are related to equivalent atoms of molecule 2 (marked by a prime) by a pseudo-glide plane given by x, 1/2 - y, -1/2 + z. There is no change in the conformation of the calix[4]pyrrole macrocycle or in the macrocycle to solvent interaction upon cooling. The DMSO O atom is hydrogen bonded to a single pyrrole group of the calix[4]pyrrole. In the monoclinic phase, the geometry of the N1—H1N···O1A hydrogen-bonding interaction is N···O = 2.982 (4) Å, H···O = 1.99 (4) Å and N—H···O = 169 (3)°. In the triclinic phase, there are two independent hydrogen-bonding interactions, i.e. N1—H1N···O1A [N···O = 2.985 (5) Å, H···O = 2.10 (5) Å and N—H···O = 177 (5)°] and N1'—H1'N···O1A' [N···O = 2.961 (5) Å, H···O = 2.03 (5) Å and N—H···O = 175 (5)°].
The calix[4]pyrrole–DMSO complex forms columns parallel to the c axis. Within a column, long-range N—H···O interactions between a pyrrole group in one complex and the DMSO O atom of an adjacent complex are observed. In the monoclinic phase, the columns are composed of molecules related by the c-glide plane operation. The N···O contact is 3.617 (5) Å between O1A and N3 related by x, 1/2 - y, -1/2 + z while the H3N···O1A contact is 2.74 (4) Å. The N—H···O angle is 158 (3)°. In the triclinic phase, the columns are composed of molecules related by a c axis translation. There are two unique long-range N—H···O contacts in the triclinic phase. The geometry of the first contact is 3.558 (6) Å between O1A and N3', 2.75 (5) Å between O1A and H3'N, with an N—H···O angle of 156 (4) Å. The geometry of the second contact is 3.554 (6) Å between O1A' and N3 (related by x, y, z - 1) and 2.63 (5) Å between H3N and O1A, with an N—H···O angle of 164 (4) Å (Fig. 2).
These long-range N—H···O contacts act to stabilize complex-to-complex interactions within a column. As a result, there is little difference in structure observed between the monoclinic and triclinic phases along a column. For example, if the atoms of the calix[4]pyrrole of molecule 1 of the triclinic phase are superimposed onto the equivalent atoms of the monoclinic phase, the c-glide symmetry relative of the monoclinic phase is nearly superimposed on top of molecule 2 of the triclinic phase. The average distance between equivalent atoms of these latter two molecules is less than 0.12 Å.
The loss of symmetry on cooling results from a change in the column-to-column packing. The change is illustrated in Fig. 3. Whereas, the atom shift within a column was found to be small, the shift between columns is substantial. To determine the change in position with reference to the monoclinic cell, a second molecule of the calix[4]pyrrole–DMSO complex for the monoclinic phase was generated by 1 - x, 1/2 + y, 3/2 - z. For the triclinic phase, molecule 2 was moved to a position that would most closely correspond to the twofold screw axis relative in the monoclinic cell. This was accomplished by inverting molecule 2 though the crystallographic inversion center at 1/2, 1/2, 1/2. Using the utility OFIT in SHELXTL/PC (Sheldrick, 1998), molecule 1 of the triclinic phase was superimposed onto the calix[4]pyrrole in the monoclinic phase. Molecule 2, related by 1 - x, 1 - y, 1 - z, lies near the twofold screw axis relative of the monoclinic phase. The average distance between equivalent atoms of these latter two molecules is 0.78 Å.