Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110040448/bi3001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110040448/bi3001Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110040448/bi3001IIsup3.hkl |
CCDC references: 810008; 810009
Compounds (I) and (II) were synthesized using a Gewald reaction (Gewald et al., 1966). meta-Cyanotoluidine [for (I)] or ortho-cyanotoluidine [for (II)] (0.04 mol) was refluxed with ethyl methyl ketone in the presence of sulfur at 313–323 K for 1 h. The products were then reacted with trimethoxybenzaldehyde in an equimolar ratio in the presence of ethanol to yield either (I) or (II), in both cases with ca 70% yield. Both compounds were recrystallized by slow evaporation from ethyl acetate to yield yellow needle-shaped crystals.
For both (I) and (II), atoms C24 and C25 of the cyclohexene ring were split into two components, with site-occupancy factors constrained to sum to unity. Atoms C24A and C25A belong to one disorder component, while C24B and C25B belong to the other; the refined site occupancies were 0.686 (7) and 0.314 (7), respectively, for (I), and 0.501 (10) and 0.499 (10), respectively, for (II). In both cases, the six C—C bond distances involving the disordered C atoms were restrained to 1.54 (1) Å. H atoms were placed in geometric positions on all disordered C atoms, with site-occupancy factors constrained to those of the parent C atoms and with Uiso(H) = 1.2Ueq(C). H atoms associated with atoms C23 and C26 were also modelled as disordered, in geometric positions consistent with the two disorder components. All other C-bound H atoms were positioned geometrically and refined as riding, with C—H = 0.93, 0.96 or 0.97 Å, and with Uiso(H) = 1.2 or 1.5Ueq(C). The amine H atoms were placed with N—H = 0.86 Å, and refined as riding with Uiso(H) = 1.2Ueq(N). All methyl groups were allowed to rotate about their local threefold axis.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2009).
C26H28N2O4S | Z = 2 |
Mr = 464.57 | F(000) = 492 |
Triclinic, P1 | Dx = 1.340 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7346 (17) Å | Cell parameters from 677 reflections |
b = 10.187 (2) Å | θ = 1.4–26.4° |
c = 14.253 (3) Å | µ = 0.18 mm−1 |
α = 70.790 (3)° | T = 290 K |
β = 76.059 (3)° | Needle, yellow |
γ = 78.143 (4)° | 0.32 × 0.12 × 0.11 mm |
V = 1151.3 (4) Å3 |
Bruker SMART CCD area-detector diffractometer | 4468 independent reflections |
Radiation source: fine-focus sealed tube | 3431 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.950, Tmax = 0.981 | k = −12→12 |
9094 measured reflections | l = −17→17 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0636P)2] where P = (Fo2 + 2Fc2)/3 |
4468 reflections | (Δ/σ)max = 0.001 |
321 parameters | Δρmax = 0.18 e Å−3 |
6 restraints | Δρmin = −0.20 e Å−3 |
C26H28N2O4S | γ = 78.143 (4)° |
Mr = 464.57 | V = 1151.3 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.7346 (17) Å | Mo Kα radiation |
b = 10.187 (2) Å | µ = 0.18 mm−1 |
c = 14.253 (3) Å | T = 290 K |
α = 70.790 (3)° | 0.32 × 0.12 × 0.11 mm |
β = 76.059 (3)° |
Bruker SMART CCD area-detector diffractometer | 4468 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3431 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.981 | Rint = 0.034 |
9094 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 6 restraints |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.18 e Å−3 |
4468 reflections | Δρmin = −0.20 e Å−3 |
321 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.09791 (5) | 0.51543 (5) | 1.12681 (3) | 0.05396 (17) | |
O1 | 0.37599 (16) | 0.04015 (13) | 1.24642 (9) | 0.0678 (4) | |
O2 | 0.40505 (16) | 0.87101 (13) | 0.59515 (9) | 0.0585 (4) | |
O3 | 0.62516 (15) | 0.68414 (14) | 0.52484 (9) | 0.0592 (4) | |
O4 | 0.70244 (15) | 0.42993 (13) | 0.64023 (8) | 0.0570 (3) | |
N1 | 0.49608 (15) | 0.14808 (13) | 1.08861 (10) | 0.0408 (3) | |
H1 | 0.4939 | 0.2266 | 1.0413 | 0.049* | |
N2 | 0.34346 (15) | 0.41569 (13) | 0.99614 (9) | 0.0381 (3) | |
C1 | 0.0561 (2) | 0.40817 (18) | 1.24863 (12) | 0.0457 (4) | |
C2 | 0.15290 (18) | 0.28338 (17) | 1.26339 (11) | 0.0395 (4) | |
C3 | 0.26671 (18) | 0.27286 (16) | 1.17358 (11) | 0.0362 (4) | |
C4 | 0.25236 (18) | 0.39208 (16) | 1.09304 (11) | 0.0381 (4) | |
C5 | 0.38372 (19) | 0.14322 (17) | 1.17302 (12) | 0.0395 (4) | |
C6 | 0.61650 (18) | 0.03984 (16) | 1.06873 (12) | 0.0372 (4) | |
C7 | 0.6310 (2) | −0.09580 (17) | 1.13464 (13) | 0.0464 (4) | |
H7 | 0.5612 | −0.1192 | 1.1963 | 0.056* | |
C8 | 0.7512 (2) | −0.19489 (18) | 1.10652 (15) | 0.0555 (5) | |
H8 | 0.7613 | −0.2858 | 1.1500 | 0.067* | |
C9 | 0.8558 (2) | −0.16263 (19) | 1.01625 (15) | 0.0541 (5) | |
H9 | 0.9351 | −0.2317 | 0.9992 | 0.065* | |
C10 | 0.84419 (19) | −0.02838 (19) | 0.95049 (13) | 0.0471 (4) | |
C11 | 0.72418 (18) | 0.07171 (18) | 0.97841 (12) | 0.0437 (4) | |
H11 | 0.7159 | 0.1629 | 0.9352 | 0.052* | |
C12 | 0.9593 (2) | 0.0052 (2) | 0.85165 (15) | 0.0662 (6) | |
H12A | 0.9137 | −0.0041 | 0.7996 | 0.099* | |
H12B | 1.0565 | −0.0584 | 0.8576 | 0.099* | |
H12C | 0.9812 | 0.0998 | 0.8345 | 0.099* | |
C13 | 0.31639 (19) | 0.53219 (17) | 0.92877 (12) | 0.0426 (4) | |
H13 | 0.2369 | 0.5994 | 0.9483 | 0.051* | |
C14 | 0.39902 (19) | 0.56843 (17) | 0.82464 (11) | 0.0390 (4) | |
C15 | 0.51463 (19) | 0.47337 (17) | 0.78672 (11) | 0.0413 (4) | |
H15 | 0.5422 | 0.3839 | 0.8285 | 0.050* | |
C16 | 0.5887 (2) | 0.51310 (18) | 0.68580 (12) | 0.0427 (4) | |
C17 | 0.5458 (2) | 0.64670 (18) | 0.62312 (11) | 0.0436 (4) | |
C18 | 0.4332 (2) | 0.74232 (17) | 0.66224 (12) | 0.0442 (4) | |
C19 | 0.3583 (2) | 0.70253 (17) | 0.76255 (12) | 0.0444 (4) | |
H19 | 0.2807 | 0.7655 | 0.7885 | 0.053* | |
C20 | 0.5353 (3) | 0.6985 (3) | 0.45040 (14) | 0.0894 (8) | |
H20A | 0.4753 | 0.6212 | 0.4715 | 0.134* | |
H20B | 0.6061 | 0.6990 | 0.3873 | 0.134* | |
H20C | 0.4637 | 0.7849 | 0.4421 | 0.134* | |
C21 | 0.3006 (3) | 0.97604 (19) | 0.63161 (15) | 0.0660 (6) | |
H21A | 0.1971 | 0.9468 | 0.6587 | 0.099* | |
H21B | 0.2929 | 1.0616 | 0.5772 | 0.099* | |
H21C | 0.3405 | 0.9914 | 0.6837 | 0.099* | |
C22 | 0.7609 (2) | 0.2980 (2) | 0.70104 (14) | 0.0646 (6) | |
H22A | 0.7962 | 0.3100 | 0.7561 | 0.097* | |
H22B | 0.8485 | 0.2546 | 0.6612 | 0.097* | |
H22C | 0.6777 | 0.2396 | 0.7273 | 0.097* | |
C23 | 0.1366 (2) | 0.17597 (19) | 1.36597 (11) | 0.0488 (4) | |
H23A | 0.2287 | 0.1679 | 1.3953 | 0.059* | 0.686 (7) |
H23B | 0.1334 | 0.0854 | 1.3584 | 0.059* | 0.686 (7) |
H23C | 0.2419 | 0.1358 | 1.3810 | 0.059* | 0.314 (7) |
H23D | 0.0855 | 0.1009 | 1.3643 | 0.059* | 0.314 (7) |
C24A | −0.0146 (5) | 0.2168 (5) | 1.4383 (4) | 0.0578 (12) | 0.686 (7) |
H24A | −0.1067 | 0.1953 | 1.4222 | 0.069* | 0.686 (7) |
H24B | −0.0067 | 0.1613 | 1.5073 | 0.069* | 0.686 (7) |
C25A | −0.0378 (5) | 0.3710 (4) | 1.4307 (2) | 0.0594 (11) | 0.686 (7) |
H25A | −0.1267 | 0.3914 | 1.4820 | 0.071* | 0.686 (7) |
H25B | 0.0570 | 0.3950 | 1.4416 | 0.071* | 0.686 (7) |
C24B | 0.0432 (10) | 0.2384 (13) | 1.4515 (7) | 0.061 (3) | 0.314 (7) |
H24C | 0.0175 | 0.1637 | 1.5134 | 0.073* | 0.314 (7) |
H24D | 0.1069 | 0.2965 | 1.4638 | 0.073* | 0.314 (7) |
C25B | −0.1091 (9) | 0.3264 (10) | 1.4190 (5) | 0.064 (3) | 0.314 (7) |
H25C | −0.1758 | 0.3575 | 1.4749 | 0.077* | 0.314 (7) |
H25D | −0.1675 | 0.2696 | 1.4012 | 0.077* | 0.314 (7) |
C26 | −0.0702 (2) | 0.4565 (2) | 1.32661 (13) | 0.0585 (5) | |
H26A | −0.1741 | 0.4452 | 1.3197 | 0.070* | 0.686 (7) |
H26B | −0.0689 | 0.5551 | 1.3170 | 0.070* | 0.686 (7) |
H26C | −0.1653 | 0.5014 | 1.2988 | 0.070* | 0.314 (7) |
H26D | −0.0328 | 0.5240 | 1.3475 | 0.070* | 0.314 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0572 (3) | 0.0502 (3) | 0.0350 (3) | 0.0146 (2) | 0.0018 (2) | −0.0076 (2) |
O1 | 0.0810 (9) | 0.0466 (7) | 0.0433 (8) | 0.0103 (7) | 0.0091 (7) | 0.0033 (6) |
O2 | 0.0766 (9) | 0.0434 (7) | 0.0397 (7) | −0.0044 (6) | −0.0079 (6) | 0.0042 (6) |
O3 | 0.0692 (8) | 0.0663 (9) | 0.0292 (6) | −0.0155 (7) | 0.0008 (6) | −0.0005 (6) |
O4 | 0.0676 (8) | 0.0544 (8) | 0.0330 (6) | 0.0012 (6) | 0.0090 (6) | −0.0106 (6) |
N1 | 0.0429 (8) | 0.0347 (7) | 0.0345 (7) | 0.0010 (6) | −0.0017 (6) | −0.0043 (6) |
N2 | 0.0424 (7) | 0.0386 (7) | 0.0273 (7) | −0.0017 (6) | −0.0007 (6) | −0.0085 (6) |
C1 | 0.0448 (9) | 0.0527 (10) | 0.0312 (9) | −0.0014 (8) | 0.0026 (7) | −0.0117 (8) |
C2 | 0.0391 (9) | 0.0466 (10) | 0.0297 (8) | −0.0067 (7) | −0.0007 (7) | −0.0109 (7) |
C3 | 0.0381 (8) | 0.0387 (9) | 0.0293 (8) | −0.0048 (7) | −0.0036 (7) | −0.0089 (7) |
C4 | 0.0408 (9) | 0.0389 (9) | 0.0288 (8) | −0.0006 (7) | −0.0013 (7) | −0.0091 (7) |
C5 | 0.0434 (9) | 0.0387 (9) | 0.0308 (8) | −0.0028 (7) | −0.0050 (7) | −0.0059 (7) |
C6 | 0.0359 (8) | 0.0384 (9) | 0.0389 (9) | −0.0013 (7) | −0.0099 (7) | −0.0135 (7) |
C7 | 0.0454 (9) | 0.0394 (9) | 0.0493 (10) | −0.0027 (7) | −0.0071 (8) | −0.0094 (8) |
C8 | 0.0570 (11) | 0.0374 (10) | 0.0657 (13) | 0.0053 (8) | −0.0159 (10) | −0.0109 (9) |
C9 | 0.0491 (10) | 0.0494 (11) | 0.0635 (13) | 0.0128 (8) | −0.0152 (9) | −0.0246 (10) |
C10 | 0.0385 (9) | 0.0573 (11) | 0.0462 (10) | 0.0049 (8) | −0.0108 (8) | −0.0212 (9) |
C11 | 0.0410 (9) | 0.0446 (10) | 0.0411 (9) | 0.0026 (7) | −0.0089 (8) | −0.0111 (8) |
C12 | 0.0501 (11) | 0.0834 (15) | 0.0554 (12) | 0.0143 (10) | −0.0041 (9) | −0.0259 (11) |
C13 | 0.0463 (9) | 0.0392 (9) | 0.0340 (9) | 0.0030 (7) | −0.0018 (7) | −0.0093 (7) |
C14 | 0.0436 (9) | 0.0390 (9) | 0.0304 (8) | −0.0067 (7) | −0.0038 (7) | −0.0065 (7) |
C15 | 0.0501 (10) | 0.0371 (9) | 0.0298 (8) | −0.0061 (7) | −0.0034 (7) | −0.0035 (7) |
C16 | 0.0456 (9) | 0.0450 (10) | 0.0342 (9) | −0.0093 (8) | 0.0005 (7) | −0.0111 (8) |
C17 | 0.0508 (10) | 0.0487 (10) | 0.0262 (8) | −0.0153 (8) | −0.0007 (7) | −0.0037 (7) |
C18 | 0.0524 (10) | 0.0400 (9) | 0.0344 (9) | −0.0104 (8) | −0.0100 (8) | 0.0003 (7) |
C19 | 0.0505 (10) | 0.0386 (9) | 0.0375 (9) | −0.0020 (8) | −0.0067 (8) | −0.0061 (8) |
C20 | 0.132 (2) | 0.109 (2) | 0.0365 (11) | −0.0496 (17) | −0.0137 (13) | −0.0139 (12) |
C21 | 0.0903 (15) | 0.0417 (11) | 0.0564 (12) | −0.0005 (10) | −0.0216 (11) | −0.0011 (9) |
C22 | 0.0756 (14) | 0.0552 (12) | 0.0459 (11) | 0.0066 (10) | 0.0072 (10) | −0.0149 (10) |
C23 | 0.0518 (10) | 0.0553 (11) | 0.0300 (9) | −0.0089 (8) | 0.0017 (8) | −0.0062 (8) |
C24A | 0.056 (3) | 0.073 (2) | 0.0343 (19) | −0.015 (2) | 0.0065 (19) | −0.0096 (16) |
C25A | 0.054 (2) | 0.084 (3) | 0.0356 (16) | −0.0101 (18) | 0.0113 (15) | −0.0249 (16) |
C24B | 0.049 (5) | 0.089 (7) | 0.035 (4) | −0.006 (5) | −0.002 (4) | −0.012 (4) |
C25B | 0.043 (4) | 0.102 (7) | 0.037 (4) | −0.003 (4) | 0.000 (3) | −0.016 (4) |
C26 | 0.0521 (11) | 0.0696 (13) | 0.0432 (10) | 0.0034 (9) | 0.0076 (9) | −0.0214 (10) |
S1—C1 | 1.7182 (17) | C15—C16 | 1.388 (2) |
S1—C4 | 1.7376 (16) | C15—H15 | 0.9300 |
O1—C5 | 1.2141 (18) | C16—C17 | 1.394 (2) |
O2—C18 | 1.3600 (19) | C17—C18 | 1.388 (2) |
O2—C21 | 1.408 (2) | C18—C19 | 1.383 (2) |
O3—C17 | 1.3700 (18) | C19—H19 | 0.9300 |
O3—C20 | 1.420 (2) | C20—H20A | 0.9600 |
O4—C16 | 1.354 (2) | C20—H20B | 0.9600 |
O4—C22 | 1.408 (2) | C20—H20C | 0.9600 |
N1—C5 | 1.351 (2) | C21—H21A | 0.9600 |
N1—C6 | 1.4099 (19) | C21—H21B | 0.9600 |
N1—H1 | 0.8600 | C21—H21C | 0.9600 |
N2—C13 | 1.2770 (19) | C22—H22A | 0.9600 |
N2—C4 | 1.3889 (18) | C22—H22B | 0.9600 |
C1—C2 | 1.358 (2) | C22—H22C | 0.9600 |
C1—C26 | 1.497 (2) | C23—C24B | 1.541 (8) |
C2—C3 | 1.439 (2) | C23—C24A | 1.543 (4) |
C2—C23 | 1.505 (2) | C23—H23A | 0.9699 |
C3—C4 | 1.378 (2) | C23—H23B | 0.9700 |
C3—C5 | 1.496 (2) | C23—H23C | 0.9700 |
C6—C11 | 1.384 (2) | C23—H23D | 0.9700 |
C6—C7 | 1.393 (2) | C24A—C25A | 1.513 (5) |
C7—C8 | 1.382 (2) | C24A—H24A | 0.9700 |
C7—H7 | 0.9300 | C24A—H24B | 0.9700 |
C8—C9 | 1.370 (2) | C25A—C26 | 1.513 (4) |
C8—H8 | 0.9300 | C25A—H25A | 0.9700 |
C9—C10 | 1.380 (2) | C25A—H25B | 0.9700 |
C9—H9 | 0.9300 | C24B—C25B | 1.523 (8) |
C10—C11 | 1.387 (2) | C24B—H24C | 0.9700 |
C10—C12 | 1.501 (3) | C24B—H24D | 0.9700 |
C11—H11 | 0.9300 | C25B—C26 | 1.558 (7) |
C12—H12A | 0.9600 | C25B—H25C | 0.9700 |
C12—H12B | 0.9600 | C25B—H25D | 0.9700 |
C12—H12C | 0.9600 | C26—H26A | 0.9700 |
C13—C14 | 1.447 (2) | C26—H26B | 0.9700 |
C13—H13 | 0.9300 | C26—H26C | 0.9700 |
C14—C15 | 1.389 (2) | C26—H26D | 0.9700 |
C14—C19 | 1.390 (2) | ||
C1—S1—C4 | 91.96 (8) | O3—C20—H20A | 109.5 |
C18—O2—C21 | 117.93 (14) | O3—C20—H20B | 109.5 |
C17—O3—C20 | 115.75 (15) | H20A—C20—H20B | 109.5 |
C16—O4—C22 | 117.93 (13) | O3—C20—H20C | 109.5 |
C5—N1—C6 | 127.79 (14) | H20A—C20—H20C | 109.5 |
C5—N1—H1 | 116.1 | H20B—C20—H20C | 109.5 |
C6—N1—H1 | 116.1 | O2—C21—H21A | 109.5 |
C13—N2—C4 | 119.94 (13) | O2—C21—H21B | 109.5 |
C2—C1—C26 | 126.59 (16) | H21A—C21—H21B | 109.5 |
C2—C1—S1 | 112.29 (12) | O2—C21—H21C | 109.5 |
C26—C1—S1 | 121.08 (13) | H21A—C21—H21C | 109.5 |
C1—C2—C3 | 112.47 (14) | H21B—C21—H21C | 109.5 |
C1—C2—C23 | 120.23 (15) | O4—C22—H22A | 109.5 |
C3—C2—C23 | 127.29 (15) | O4—C22—H22B | 109.5 |
C4—C3—C2 | 112.49 (14) | H22A—C22—H22B | 109.5 |
C4—C3—C5 | 126.32 (14) | O4—C22—H22C | 109.5 |
C2—C3—C5 | 121.19 (14) | H22A—C22—H22C | 109.5 |
C3—C4—N2 | 126.91 (14) | H22B—C22—H22C | 109.5 |
C3—C4—S1 | 110.80 (11) | C2—C23—C24B | 113.0 (5) |
N2—C4—S1 | 122.28 (11) | C2—C23—C24A | 111.6 (2) |
O1—C5—N1 | 122.85 (15) | C2—C23—H23A | 109.5 |
O1—C5—C3 | 120.19 (14) | C24A—C23—H23A | 108.7 |
N1—C5—C3 | 116.96 (14) | C2—C23—H23B | 109.1 |
C11—C6—C7 | 119.14 (15) | C24A—C23—H23B | 109.9 |
C11—C6—N1 | 117.46 (14) | H23A—C23—H23B | 108.0 |
C7—C6—N1 | 123.40 (15) | C2—C23—H23C | 109.1 |
C8—C7—C6 | 118.65 (16) | C24B—C23—H23C | 107.6 |
C8—C7—H7 | 120.7 | C2—C23—H23D | 108.9 |
C6—C7—H7 | 120.7 | C24B—C23—H23D | 110.3 |
C9—C8—C7 | 121.70 (17) | H23A—C23—H23D | 127.9 |
C9—C8—H8 | 119.2 | H23C—C23—H23D | 107.9 |
C7—C8—H8 | 119.2 | C25A—C24A—C23 | 111.8 (3) |
C8—C9—C10 | 120.43 (16) | C25A—C24A—H24A | 109.3 |
C8—C9—H9 | 119.8 | C23—C24A—H24A | 109.3 |
C10—C9—H9 | 119.8 | C25A—C24A—H24B | 109.3 |
C9—C10—C11 | 118.16 (17) | C23—C24A—H24B | 109.3 |
C9—C10—C12 | 119.82 (17) | H24A—C24A—H24B | 107.9 |
C11—C10—C12 | 122.01 (17) | C26—C25A—C24A | 108.9 (4) |
C6—C11—C10 | 121.91 (16) | C26—C25A—H25A | 109.9 |
C6—C11—H11 | 119.0 | C24A—C25A—H25A | 109.9 |
C10—C11—H11 | 119.0 | C26—C25A—H25B | 109.9 |
C10—C12—H12A | 109.5 | C24A—C25A—H25B | 109.9 |
C10—C12—H12B | 109.5 | H25A—C25A—H25B | 108.3 |
H12A—C12—H12B | 109.5 | C25B—C24B—C23 | 108.1 (7) |
C10—C12—H12C | 109.5 | C25B—C24B—H24C | 110.1 |
H12A—C12—H12C | 109.5 | C23—C24B—H24C | 110.1 |
H12B—C12—H12C | 109.5 | C25B—C24B—H24D | 110.1 |
N2—C13—C14 | 125.47 (15) | C23—C24B—H24D | 110.1 |
N2—C13—H13 | 117.3 | H24C—C24B—H24D | 108.4 |
C14—C13—H13 | 117.3 | C24B—C25B—C26 | 110.7 (8) |
C15—C14—C19 | 120.48 (14) | C24B—C25B—H25C | 109.5 |
C15—C14—C13 | 121.80 (14) | C26—C25B—H25C | 109.5 |
C19—C14—C13 | 117.73 (15) | C24B—C25B—H25D | 109.5 |
C16—C15—C14 | 119.38 (15) | C26—C25B—H25D | 109.5 |
C16—C15—H15 | 120.3 | H25C—C25B—H25D | 108.1 |
C14—C15—H15 | 120.3 | C1—C26—C25A | 108.99 (18) |
O4—C16—C15 | 124.81 (15) | C1—C26—C25B | 108.5 (3) |
O4—C16—C17 | 115.05 (14) | C1—C26—H26A | 109.9 |
C15—C16—C17 | 120.13 (16) | C25A—C26—H26A | 110.2 |
O3—C17—C18 | 121.14 (15) | C1—C26—H26B | 109.6 |
O3—C17—C16 | 118.59 (15) | C25A—C26—H26B | 109.7 |
C18—C17—C16 | 120.10 (14) | H26A—C26—H26B | 108.4 |
O2—C18—C19 | 125.17 (16) | C1—C26—H26C | 110.1 |
O2—C18—C17 | 115.04 (15) | C25B—C26—H26C | 109.8 |
C19—C18—C17 | 119.79 (15) | C1—C26—H26D | 109.9 |
C18—C19—C14 | 120.06 (16) | C25B—C26—H26D | 110.1 |
C18—C19—H19 | 120.0 | H26C—C26—H26D | 108.4 |
C14—C19—H19 | 120.0 | ||
C4—S1—C1—C2 | −0.82 (14) | C19—C14—C15—C16 | −0.5 (2) |
C4—S1—C1—C26 | 176.92 (15) | C13—C14—C15—C16 | 179.13 (15) |
C26—C1—C2—C3 | −177.15 (16) | C22—O4—C16—C15 | −6.1 (3) |
S1—C1—C2—C3 | 0.44 (19) | C22—O4—C16—C17 | 174.72 (16) |
C26—C1—C2—C23 | 1.4 (3) | C14—C15—C16—O4 | −179.86 (15) |
S1—C1—C2—C23 | 178.94 (12) | C14—C15—C16—C17 | −0.7 (2) |
C1—C2—C3—C4 | 0.3 (2) | C20—O3—C17—C18 | −74.3 (2) |
C23—C2—C3—C4 | −178.04 (15) | C20—O3—C17—C16 | 110.4 (2) |
C1—C2—C3—C5 | −179.36 (14) | O4—C16—C17—O3 | −3.0 (2) |
C23—C2—C3—C5 | 2.3 (2) | C15—C16—C17—O3 | 177.76 (14) |
C2—C3—C4—N2 | −179.98 (14) | O4—C16—C17—C18 | −178.36 (14) |
C5—C3—C4—N2 | −0.3 (3) | C15—C16—C17—C18 | 2.4 (3) |
C2—C3—C4—S1 | −0.92 (18) | C21—O2—C18—C19 | 5.1 (3) |
C5—C3—C4—S1 | 178.75 (12) | C21—O2—C18—C17 | −175.55 (15) |
C13—N2—C4—C3 | −179.96 (16) | O3—C17—C18—O2 | 2.4 (2) |
C13—N2—C4—S1 | 1.1 (2) | C16—C17—C18—O2 | 177.65 (15) |
C1—S1—C4—C3 | 0.99 (13) | O3—C17—C18—C19 | −178.19 (15) |
C1—S1—C4—N2 | −179.90 (14) | C16—C17—C18—C19 | −2.9 (3) |
C6—N1—C5—O1 | 2.0 (3) | O2—C18—C19—C14 | −178.86 (15) |
C6—N1—C5—C3 | −178.52 (13) | C17—C18—C19—C14 | 1.8 (3) |
C4—C3—C5—O1 | −173.70 (16) | C15—C14—C19—C18 | −0.1 (2) |
C2—C3—C5—O1 | 5.9 (2) | C13—C14—C19—C18 | −179.70 (15) |
C4—C3—C5—N1 | 6.8 (2) | C1—C2—C23—C24B | −17.4 (5) |
C2—C3—C5—N1 | −173.54 (14) | C3—C2—C23—C24B | 160.9 (4) |
C5—N1—C6—C11 | −176.58 (14) | C1—C2—C23—C24A | 10.0 (3) |
C5—N1—C6—C7 | 3.8 (2) | C3—C2—C23—C24A | −171.7 (2) |
C11—C6—C7—C8 | −1.2 (2) | C2—C23—C24A—C25A | −43.2 (5) |
N1—C6—C7—C8 | 178.38 (14) | C23—C24A—C25A—C26 | 65.8 (6) |
C6—C7—C8—C9 | 0.3 (3) | C2—C23—C24B—C25B | 48.5 (11) |
C7—C8—C9—C10 | 0.4 (3) | C23—C24B—C25B—C26 | −66.0 (13) |
C8—C9—C10—C11 | −0.1 (3) | C2—C1—C26—C25A | 19.8 (3) |
C8—C9—C10—C12 | −179.75 (17) | S1—C1—C26—C25A | −157.6 (2) |
C7—C6—C11—C10 | 1.5 (2) | C2—C1—C26—C25B | −16.8 (5) |
N1—C6—C11—C10 | −178.13 (14) | S1—C1—C26—C25B | 165.8 (4) |
C9—C10—C11—C6 | −0.8 (2) | C24A—C25A—C26—C1 | −51.2 (4) |
C12—C10—C11—C6 | 178.82 (15) | C24A—C25A—C26—C25B | 44.1 (5) |
C4—N2—C13—C14 | −178.07 (15) | C24B—C25B—C26—C1 | 48.8 (9) |
N2—C13—C14—C15 | 2.9 (3) | C24B—C25B—C26—C25A | −48.1 (7) |
N2—C13—C14—C19 | −177.44 (16) |
C26H28N2O4S | F(000) = 1968 |
Mr = 464.56 | Dx = 1.305 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 953 reflections |
a = 13.437 (5) Å | θ = 1.6–25.4° |
b = 12.993 (5) Å | µ = 0.17 mm−1 |
c = 27.088 (10) Å | T = 290 K |
V = 4729 (3) Å3 | Plate, yellow |
Z = 8 | 0.20 × 0.10 × 0.02 mm |
Bruker SMART CCD area-detector diffractometer | 4639 independent reflections |
Radiation source: fine-focus sealed tube | 3186 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.105 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→16 |
Tmin = 0.991, Tmax = 0.997 | k = −16→16 |
34929 measured reflections | l = −33→33 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0779P)2] where P = (Fo2 + 2Fc2)/3 |
4639 reflections | (Δ/σ)max = 0.001 |
321 parameters | Δρmax = 0.25 e Å−3 |
6 restraints | Δρmin = −0.21 e Å−3 |
C26H28N2O4S | V = 4729 (3) Å3 |
Mr = 464.56 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.437 (5) Å | µ = 0.17 mm−1 |
b = 12.993 (5) Å | T = 290 K |
c = 27.088 (10) Å | 0.20 × 0.10 × 0.02 mm |
Bruker SMART CCD area-detector diffractometer | 4639 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3186 reflections with I > 2σ(I) |
Tmin = 0.991, Tmax = 0.997 | Rint = 0.105 |
34929 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 6 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.25 e Å−3 |
4639 reflections | Δρmin = −0.21 e Å−3 |
321 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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.14272 (4) | −0.00513 (3) | 1.074313 (16) | 0.05282 (16) | |
O1 | 0.12602 (12) | 0.33596 (10) | 0.99466 (5) | 0.0741 (4) | |
O2 | 0.16017 (11) | −0.39749 (9) | 0.87262 (5) | 0.0648 (4) | |
O3 | 0.17610 (11) | −0.28899 (10) | 0.78908 (5) | 0.0665 (4) | |
O4 | 0.14553 (12) | −0.08710 (10) | 0.78690 (5) | 0.0736 (4) | |
N1 | 0.05707 (11) | 0.21285 (10) | 0.94742 (5) | 0.0494 (4) | |
H1 | 0.0361 | 0.1503 | 0.9468 | 0.059* | |
N2 | 0.11737 (10) | 0.01441 (10) | 0.97348 (5) | 0.0425 (3) | |
C1 | 0.14862 (13) | 0.10822 (14) | 1.10742 (6) | 0.0506 (4) | |
C2 | 0.13757 (12) | 0.19242 (13) | 1.07856 (6) | 0.0443 (4) | |
C3 | 0.12155 (12) | 0.16633 (12) | 1.02753 (6) | 0.0406 (4) | |
C4 | 0.12432 (11) | 0.06153 (12) | 1.01937 (6) | 0.0411 (4) | |
C5 | 0.10361 (12) | 0.24629 (12) | 0.98878 (6) | 0.0446 (4) | |
C6 | 0.04076 (13) | 0.27504 (12) | 0.90481 (6) | 0.0452 (4) | |
C7 | −0.03079 (14) | 0.35203 (13) | 0.90469 (7) | 0.0523 (4) | |
C8 | −0.04259 (18) | 0.40738 (15) | 0.86111 (8) | 0.0711 (6) | |
H8 | −0.0895 | 0.4600 | 0.8600 | 0.085* | |
C9 | 0.0127 (2) | 0.38679 (19) | 0.81985 (8) | 0.0838 (7) | |
H9 | 0.0027 | 0.4247 | 0.7911 | 0.101* | |
C10 | 0.0828 (2) | 0.3103 (2) | 0.82086 (8) | 0.0823 (7) | |
H10 | 0.1209 | 0.2963 | 0.7930 | 0.099* | |
C11 | 0.09637 (15) | 0.25484 (16) | 0.86316 (7) | 0.0626 (5) | |
H11 | 0.1438 | 0.2027 | 0.8639 | 0.075* | |
C12 | −0.09230 (18) | 0.37620 (18) | 0.94946 (9) | 0.0823 (7) | |
H12A | −0.1287 | 0.3160 | 0.9593 | 0.123* | |
H12B | −0.1381 | 0.4306 | 0.9418 | 0.123* | |
H12C | −0.0495 | 0.3974 | 0.9759 | 0.123* | |
C13 | 0.12594 (12) | −0.08263 (12) | 0.96839 (6) | 0.0453 (4) | |
H13 | 0.1310 | −0.1226 | 0.9967 | 0.054* | |
C14 | 0.12833 (12) | −0.13450 (12) | 0.92091 (6) | 0.0440 (4) | |
C15 | 0.12869 (13) | −0.08025 (13) | 0.87659 (6) | 0.0489 (4) | |
H15 | 0.1208 | −0.0091 | 0.8766 | 0.059* | |
C16 | 0.14085 (14) | −0.13244 (14) | 0.83260 (6) | 0.0513 (4) | |
C17 | 0.15145 (13) | −0.23933 (13) | 0.83244 (6) | 0.0498 (4) | |
C18 | 0.14773 (13) | −0.29353 (13) | 0.87641 (7) | 0.0491 (4) | |
C19 | 0.13699 (13) | −0.24112 (13) | 0.92072 (6) | 0.0480 (4) | |
H19 | 0.1356 | −0.2773 | 0.9503 | 0.058* | |
C20 | 0.09857 (19) | −0.3362 (2) | 0.76310 (9) | 0.0974 (8) | |
H20A | 0.0664 | −0.3858 | 0.7840 | 0.146* | |
H20B | 0.1249 | −0.3701 | 0.7345 | 0.146* | |
H20C | 0.0512 | −0.2850 | 0.7531 | 0.146* | |
C21 | 0.15016 (15) | −0.45680 (14) | 0.91664 (7) | 0.0586 (5) | |
H21A | 0.2007 | −0.4369 | 0.9398 | 0.088* | |
H21B | 0.1573 | −0.5285 | 0.9089 | 0.088* | |
H21C | 0.0857 | −0.4449 | 0.9308 | 0.088* | |
C22 | 0.1492 (2) | 0.01910 (18) | 0.78447 (8) | 0.0942 (9) | |
H22A | 0.0897 | 0.0474 | 0.7987 | 0.141* | |
H22B | 0.1543 | 0.0402 | 0.7506 | 0.141* | |
H22C | 0.2060 | 0.0435 | 0.8024 | 0.141* | |
C23 | 0.14303 (15) | 0.29924 (14) | 1.10008 (7) | 0.0579 (5) | |
H23A | 0.0764 | 0.3265 | 1.1043 | 0.069* | 0.501 (10) |
H23B | 0.1789 | 0.3440 | 1.0776 | 0.069* | 0.501 (10) |
H23C | 0.0872 | 0.3393 | 1.0880 | 0.069* | 0.499 (10) |
H23D | 0.2038 | 0.3324 | 1.0891 | 0.069* | 0.499 (10) |
C24A | 0.1968 (7) | 0.2971 (5) | 1.1504 (2) | 0.074 (2) | 0.501 (10) |
H24A | 0.2671 | 0.2841 | 1.1452 | 0.089* | 0.501 (10) |
H24B | 0.1902 | 0.3637 | 1.1662 | 0.089* | 0.501 (10) |
C25A | 0.1542 (8) | 0.2146 (5) | 1.1839 (3) | 0.086 (2) | 0.501 (10) |
H25A | 0.1873 | 0.2177 | 1.2157 | 0.103* | 0.501 (10) |
H25B | 0.0839 | 0.2278 | 1.1892 | 0.103* | 0.501 (10) |
C24B | 0.1398 (7) | 0.2975 (6) | 1.15622 (19) | 0.0722 (19) | 0.499 (10) |
H24C | 0.1610 | 0.3638 | 1.1689 | 0.087* | 0.499 (10) |
H24D | 0.0720 | 0.2856 | 1.1671 | 0.087* | 0.499 (10) |
C25B | 0.2067 (6) | 0.2140 (4) | 1.1768 (3) | 0.071 (2) | 0.499 (10) |
H25C | 0.2092 | 0.2194 | 1.2125 | 0.085* | 0.499 (10) |
H25D | 0.2736 | 0.2228 | 1.1641 | 0.085* | 0.499 (10) |
C26 | 0.16727 (18) | 0.10818 (17) | 1.16209 (7) | 0.0701 (6) | |
H26A | 0.2347 | 0.0850 | 1.1684 | 0.084* | 0.501 (10) |
H26B | 0.1218 | 0.0603 | 1.1778 | 0.084* | 0.501 (10) |
H26C | 0.2163 | 0.0559 | 1.1700 | 0.084* | 0.499 (10) |
H26D | 0.1061 | 0.0924 | 1.1795 | 0.084* | 0.499 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0641 (3) | 0.0496 (3) | 0.0448 (3) | 0.0031 (2) | −0.0041 (2) | 0.00924 (19) |
O1 | 0.1141 (13) | 0.0475 (8) | 0.0606 (9) | −0.0191 (7) | −0.0286 (8) | 0.0074 (6) |
O2 | 0.0942 (11) | 0.0411 (7) | 0.0590 (9) | 0.0063 (6) | 0.0090 (7) | −0.0034 (6) |
O3 | 0.0791 (10) | 0.0693 (9) | 0.0510 (8) | −0.0074 (7) | 0.0082 (7) | −0.0138 (7) |
O4 | 0.1202 (13) | 0.0595 (8) | 0.0411 (8) | −0.0155 (8) | −0.0132 (7) | 0.0031 (6) |
N1 | 0.0650 (10) | 0.0374 (7) | 0.0458 (8) | −0.0037 (6) | −0.0135 (7) | 0.0053 (6) |
N2 | 0.0442 (8) | 0.0405 (7) | 0.0429 (8) | −0.0015 (6) | −0.0013 (6) | 0.0000 (6) |
C1 | 0.0477 (10) | 0.0635 (11) | 0.0404 (10) | 0.0026 (8) | −0.0012 (8) | 0.0028 (8) |
C2 | 0.0399 (9) | 0.0525 (10) | 0.0406 (9) | 0.0009 (7) | −0.0017 (7) | −0.0022 (7) |
C3 | 0.0393 (9) | 0.0433 (9) | 0.0393 (9) | −0.0007 (7) | −0.0003 (7) | 0.0008 (7) |
C4 | 0.0387 (9) | 0.0462 (9) | 0.0384 (9) | 0.0003 (7) | −0.0019 (7) | 0.0019 (7) |
C5 | 0.0488 (10) | 0.0405 (9) | 0.0444 (10) | −0.0035 (8) | −0.0036 (7) | 0.0014 (7) |
C6 | 0.0519 (10) | 0.0425 (9) | 0.0411 (9) | −0.0056 (7) | −0.0101 (8) | 0.0025 (7) |
C7 | 0.0520 (11) | 0.0493 (10) | 0.0556 (11) | 0.0007 (8) | −0.0105 (9) | 0.0071 (8) |
C8 | 0.0787 (15) | 0.0615 (12) | 0.0730 (14) | 0.0068 (11) | −0.0267 (12) | 0.0134 (10) |
C9 | 0.114 (2) | 0.0845 (16) | 0.0529 (13) | −0.0178 (15) | −0.0250 (13) | 0.0245 (11) |
C10 | 0.0979 (19) | 0.1030 (18) | 0.0459 (12) | −0.0064 (15) | 0.0030 (12) | 0.0048 (11) |
C11 | 0.0684 (13) | 0.0700 (12) | 0.0492 (11) | 0.0058 (10) | −0.0043 (9) | −0.0021 (9) |
C12 | 0.0724 (15) | 0.0916 (16) | 0.0828 (16) | 0.0263 (13) | 0.0059 (13) | 0.0062 (13) |
C13 | 0.0499 (10) | 0.0428 (9) | 0.0430 (10) | −0.0038 (7) | 0.0027 (7) | 0.0053 (7) |
C14 | 0.0446 (10) | 0.0416 (9) | 0.0458 (9) | −0.0044 (7) | 0.0013 (7) | 0.0003 (7) |
C15 | 0.0584 (11) | 0.0384 (9) | 0.0501 (10) | −0.0043 (8) | −0.0064 (8) | 0.0013 (7) |
C16 | 0.0614 (12) | 0.0511 (10) | 0.0414 (10) | −0.0097 (8) | −0.0085 (8) | 0.0033 (8) |
C17 | 0.0548 (11) | 0.0492 (10) | 0.0454 (10) | −0.0047 (8) | 0.0017 (8) | −0.0069 (8) |
C18 | 0.0529 (11) | 0.0408 (9) | 0.0536 (11) | −0.0014 (7) | 0.0043 (8) | −0.0015 (8) |
C19 | 0.0561 (11) | 0.0424 (9) | 0.0455 (10) | −0.0022 (8) | 0.0066 (8) | 0.0032 (7) |
C20 | 0.0954 (19) | 0.120 (2) | 0.0770 (16) | −0.0041 (15) | −0.0131 (14) | −0.0419 (15) |
C21 | 0.0637 (12) | 0.0428 (10) | 0.0692 (13) | 0.0036 (8) | −0.0026 (9) | 0.0030 (9) |
C22 | 0.157 (3) | 0.0728 (15) | 0.0530 (13) | −0.0317 (15) | −0.0195 (14) | 0.0193 (11) |
C23 | 0.0668 (13) | 0.0595 (12) | 0.0474 (11) | 0.0010 (9) | −0.0067 (9) | −0.0103 (8) |
C24A | 0.089 (5) | 0.082 (4) | 0.050 (3) | −0.009 (4) | −0.013 (3) | −0.014 (2) |
C25A | 0.100 (6) | 0.110 (5) | 0.047 (3) | 0.010 (4) | −0.004 (4) | −0.010 (3) |
C24B | 0.075 (4) | 0.087 (4) | 0.054 (3) | 0.004 (4) | 0.001 (3) | −0.026 (3) |
C25B | 0.086 (5) | 0.088 (4) | 0.039 (3) | 0.000 (3) | −0.014 (3) | −0.009 (3) |
C26 | 0.0812 (15) | 0.0904 (16) | 0.0388 (11) | 0.0041 (12) | −0.0020 (9) | 0.0068 (10) |
S1—C1 | 1.7259 (19) | C15—C16 | 1.381 (2) |
S1—C4 | 1.7397 (17) | C15—H15 | 0.930 |
O1—C5 | 1.214 (2) | C16—C17 | 1.396 (3) |
O2—C18 | 1.365 (2) | C17—C18 | 1.385 (2) |
O2—C21 | 1.426 (2) | C18—C19 | 1.387 (2) |
O3—C17 | 1.381 (2) | C19—H19 | 0.930 |
O3—C20 | 1.399 (3) | C20—H20A | 0.960 |
O4—C16 | 1.373 (2) | C20—H20B | 0.960 |
O4—C22 | 1.382 (3) | C20—H20C | 0.960 |
N1—C5 | 1.355 (2) | C21—H21A | 0.960 |
N1—C6 | 1.426 (2) | C21—H21B | 0.960 |
N1—H1 | 0.860 | C21—H21C | 0.960 |
N2—C13 | 1.274 (2) | C22—H22A | 0.960 |
N2—C4 | 1.389 (2) | C22—H22B | 0.960 |
C1—C2 | 1.353 (2) | C22—H22C | 0.960 |
C1—C26 | 1.502 (2) | C23—C24B | 1.522 (5) |
C2—C3 | 1.440 (2) | C23—C24A | 1.543 (6) |
C2—C23 | 1.507 (2) | C23—H23A | 0.970 |
C3—C4 | 1.380 (2) | C23—H23B | 0.970 |
C3—C5 | 1.496 (2) | C23—H23C | 0.970 |
C6—C11 | 1.378 (2) | C23—H23D | 0.970 |
C6—C7 | 1.387 (2) | C24A—C25A | 1.517 (8) |
C7—C8 | 1.391 (2) | C24A—H24A | 0.970 |
C7—C12 | 1.501 (3) | C24A—H24B | 0.970 |
C8—C9 | 1.369 (3) | C25A—C26 | 1.514 (6) |
C8—H8 | 0.930 | C25A—H25A | 0.970 |
C9—C10 | 1.369 (3) | C25A—H25B | 0.970 |
C9—H9 | 0.930 | C24B—C25B | 1.514 (7) |
C10—C11 | 1.366 (3) | C24B—H24C | 0.970 |
C10—H10 | 0.930 | C24B—H24D | 0.970 |
C11—H11 | 0.930 | C25B—C26 | 1.526 (6) |
C12—H12A | 0.960 | C25B—H25C | 0.970 |
C12—H12B | 0.960 | C25B—H25D | 0.970 |
C12—H12C | 0.960 | C26—H26A | 0.970 |
C13—C14 | 1.452 (2) | C26—H26B | 0.970 |
C13—H13 | 0.9300 | C26—H26C | 0.970 |
C14—C19 | 1.390 (2) | C26—H26D | 0.970 |
C14—C15 | 1.392 (2) | ||
C1—S1—C4 | 91.51 (8) | C14—C19—H19 | 120.0 |
C18—O2—C21 | 117.40 (14) | O3—C20—H20A | 109.5 |
C17—O3—C20 | 117.02 (16) | O3—C20—H20B | 109.5 |
C16—O4—C22 | 118.23 (16) | H20A—C20—H20B | 109.5 |
C5—N1—C6 | 123.96 (13) | O3—C20—H20C | 109.5 |
C5—N1—H1 | 118.0 | H20A—C20—H20C | 109.5 |
C6—N1—H1 | 118.0 | H20B—C20—H20C | 109.5 |
C13—N2—C4 | 121.83 (14) | O2—C21—H21A | 109.5 |
C2—C1—C26 | 126.04 (17) | O2—C21—H21B | 109.5 |
C2—C1—S1 | 112.63 (13) | H21A—C21—H21B | 109.5 |
C26—C1—S1 | 121.31 (14) | O2—C21—H21C | 109.5 |
C1—C2—C3 | 112.39 (15) | H21A—C21—H21C | 109.5 |
C1—C2—C23 | 121.06 (16) | H21B—C21—H21C | 109.5 |
C3—C2—C23 | 126.55 (15) | O4—C22—H22A | 109.5 |
C4—C3—C2 | 112.47 (14) | O4—C22—H22B | 109.5 |
C4—C3—C5 | 125.25 (15) | H22A—C22—H22B | 109.5 |
C2—C3—C5 | 122.29 (14) | O4—C22—H22C | 109.5 |
C3—C4—N2 | 125.21 (14) | H22A—C22—H22C | 109.5 |
C3—C4—S1 | 110.98 (12) | H22B—C22—H22C | 109.5 |
N2—C4—S1 | 123.77 (12) | C2—C23—C24B | 111.8 (3) |
O1—C5—N1 | 122.07 (15) | C2—C23—C24A | 110.4 (3) |
O1—C5—C3 | 122.30 (15) | C2—C23—H23A | 109.7 |
N1—C5—C3 | 115.58 (14) | C24A—C23—H23A | 109.6 |
C11—C6—C7 | 120.72 (16) | C2—C23—H23B | 109.5 |
C11—C6—N1 | 118.12 (16) | C24A—C23—H23B | 109.4 |
C7—C6—N1 | 121.13 (16) | H23A—C23—H23B | 108.3 |
C6—C7—C8 | 116.98 (18) | C2—C23—H23C | 109.0 |
C6—C7—C12 | 122.04 (16) | C24B—C23—H23C | 108.9 |
C8—C7—C12 | 120.97 (18) | C2—C23—H23D | 109.3 |
C9—C8—C7 | 122.0 (2) | C24B—C23—H23D | 109.8 |
C9—C8—H8 | 119.0 | H23C—C23—H23D | 108.0 |
C7—C8—H8 | 119.0 | C25A—C24A—C23 | 111.4 (6) |
C8—C9—C10 | 119.9 (2) | C25A—C24A—H24A | 109.3 |
C8—C9—H9 | 120.0 | C23—C24A—H24A | 109.3 |
C10—C9—H9 | 120.0 | C25A—C24A—H24B | 109.3 |
C11—C10—C9 | 119.4 (2) | C23—C24A—H24B | 109.3 |
C11—C10—H10 | 120.3 | H24A—C24A—H24B | 108.0 |
C9—C10—H10 | 120.3 | C26—C25A—C24A | 111.6 (6) |
C10—C11—C6 | 120.9 (2) | C26—C25A—H25A | 109.3 |
C10—C11—H11 | 119.5 | C24A—C25A—H25A | 109.3 |
C6—C11—H11 | 119.5 | C26—C25A—H25B | 109.3 |
C7—C12—H12A | 109.5 | C24A—C25A—H25B | 109.3 |
C7—C12—H12B | 109.5 | H25A—C25A—H25B | 108.0 |
H12A—C12—H12B | 109.5 | C25B—C24B—C23 | 111.2 (5) |
C7—C12—H12C | 109.5 | C25B—C24B—H24C | 109.4 |
H12A—C12—H12C | 109.5 | C23—C24B—H24C | 109.4 |
H12B—C12—H12C | 109.5 | C25B—C24B—H24D | 109.4 |
N2—C13—C14 | 123.87 (15) | C23—C24B—H24D | 109.4 |
N2—C13—H13 | 118.1 | H24C—C24B—H24D | 108.0 |
C14—C13—H13 | 118.1 | C24B—C25B—C26 | 110.1 (6) |
C19—C14—C15 | 120.08 (15) | C24B—C25B—H25C | 109.6 |
C19—C14—C13 | 117.87 (15) | C26—C25B—H25C | 109.6 |
C15—C14—C13 | 121.92 (15) | C24B—C25B—H25D | 109.6 |
C16—C15—C14 | 119.73 (16) | C26—C25B—H25D | 109.6 |
C16—C15—H15 | 120.1 | H25C—C25B—H25D | 108.2 |
C14—C15—H15 | 120.1 | C1—C26—C25A | 111.4 (4) |
O4—C16—C15 | 124.96 (17) | C1—C26—C25B | 108.3 (3) |
O4—C16—C17 | 114.80 (16) | C1—C26—H26A | 109.2 |
C15—C16—C17 | 120.22 (16) | C25A—C26—H26A | 108.9 |
O3—C17—C18 | 120.19 (16) | C1—C26—H26B | 109.2 |
O3—C17—C16 | 119.48 (16) | C25A—C26—H26B | 109.9 |
C18—C17—C16 | 119.97 (16) | H26A—C26—H26B | 108.2 |
O2—C18—C17 | 115.73 (16) | C1—C26—H26C | 109.4 |
O2—C18—C19 | 124.30 (16) | C25B—C26—H26C | 109.7 |
C17—C18—C19 | 119.89 (16) | C1—C26—H26D | 109.8 |
C18—C19—C14 | 120.06 (15) | C25B—C26—H26D | 110.9 |
C18—C19—H19 | 120.0 | H26C—C26—H26D | 108.7 |
C4—S1—C1—C2 | −0.16 (14) | N2—C13—C14—C15 | 4.8 (3) |
C4—S1—C1—C26 | −178.47 (16) | C19—C14—C15—C16 | −2.0 (3) |
C26—C1—C2—C3 | 179.42 (17) | C13—C14—C15—C16 | 173.65 (16) |
S1—C1—C2—C3 | 1.21 (19) | C22—O4—C16—C15 | 7.4 (3) |
C26—C1—C2—C23 | −0.2 (3) | C22—O4—C16—C17 | −171.42 (19) |
S1—C1—C2—C23 | −178.41 (14) | C14—C15—C16—O4 | −177.88 (17) |
C1—C2—C3—C4 | −2.0 (2) | C14—C15—C16—C17 | 0.8 (3) |
C23—C2—C3—C4 | 177.63 (16) | C20—O3—C17—C18 | 86.6 (2) |
C1—C2—C3—C5 | 177.74 (14) | C20—O3—C17—C16 | −100.2 (2) |
C23—C2—C3—C5 | −2.7 (3) | O4—C16—C17—O3 | 7.0 (2) |
C2—C3—C4—N2 | −175.86 (14) | C15—C16—C17—O3 | −171.82 (16) |
C5—C3—C4—N2 | 4.5 (3) | O4—C16—C17—C18 | −179.83 (16) |
C2—C3—C4—S1 | 1.80 (17) | C15—C16—C17—C18 | 1.3 (3) |
C5—C3—C4—S1 | −177.89 (12) | C21—O2—C18—C17 | −175.88 (16) |
C13—N2—C4—C3 | 176.09 (16) | C21—O2—C18—C19 | 7.4 (3) |
C13—N2—C4—S1 | −1.3 (2) | O3—C17—C18—O2 | −6.1 (2) |
C1—S1—C4—C3 | −0.96 (13) | C16—C17—C18—O2 | −179.15 (16) |
C1—S1—C4—N2 | 176.74 (14) | O3—C17—C18—C19 | 170.83 (16) |
C6—N1—C5—O1 | 7.9 (3) | C16—C17—C18—C19 | −2.3 (3) |
C6—N1—C5—C3 | −174.59 (15) | O2—C18—C19—C14 | 177.65 (17) |
C4—C3—C5—O1 | −161.09 (18) | C17—C18—C19—C14 | 1.1 (3) |
C2—C3—C5—O1 | 19.3 (3) | C15—C14—C19—C18 | 1.1 (3) |
C4—C3—C5—N1 | 21.4 (2) | C13—C14—C19—C18 | −174.76 (16) |
C2—C3—C5—N1 | −158.22 (15) | C1—C2—C23—C24B | −12.0 (4) |
C5—N1—C6—C11 | 107.9 (2) | C3—C2—C23—C24B | 168.5 (4) |
C5—N1—C6—C7 | −73.8 (2) | C1—C2—C23—C24A | 19.8 (4) |
C11—C6—C7—C8 | −0.5 (3) | C3—C2—C23—C24A | −159.8 (4) |
N1—C6—C7—C8 | −178.81 (16) | C2—C23—C24A—C25A | −49.7 (9) |
C11—C6—C7—C12 | −179.77 (18) | C23—C24A—C25A—C26 | 61.9 (12) |
N1—C6—C7—C12 | 1.9 (3) | C2—C23—C24B—C25B | 44.0 (9) |
C6—C7—C8—C9 | 0.7 (3) | C23—C24B—C25B—C26 | −65.7 (11) |
C12—C7—C8—C9 | 179.9 (2) | C2—C1—C26—C25A | 10.3 (5) |
C7—C8—C9—C10 | −0.6 (3) | S1—C1—C26—C25A | −171.7 (4) |
C8—C9—C10—C11 | 0.4 (4) | C2—C1—C26—C25B | −19.2 (4) |
C9—C10—C11—C6 | −0.2 (3) | S1—C1—C26—C25B | 158.9 (3) |
C7—C6—C11—C10 | 0.3 (3) | C24A—C25A—C26—C1 | −40.1 (10) |
N1—C6—C11—C10 | 178.67 (19) | C24A—C25A—C26—C25B | 48.7 (8) |
C4—N2—C13—C14 | −174.16 (14) | C24B—C25B—C26—C1 | 50.3 (8) |
N2—C13—C14—C19 | −179.37 (16) | C24B—C25B—C26—C25A | −51.1 (8) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C26H28N2O4S | C26H28N2O4S |
Mr | 464.57 | 464.56 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pbca |
Temperature (K) | 290 | 290 |
a, b, c (Å) | 8.7346 (17), 10.187 (2), 14.253 (3) | 13.437 (5), 12.993 (5), 27.088 (10) |
α, β, γ (°) | 70.790 (3), 76.059 (3), 78.143 (4) | 90, 90, 90 |
V (Å3) | 1151.3 (4) | 4729 (3) |
Z | 2 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.18 | 0.17 |
Crystal size (mm) | 0.32 × 0.12 × 0.11 | 0.20 × 0.10 × 0.02 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.950, 0.981 | 0.991, 0.997 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9094, 4468, 3431 | 34929, 4639, 3186 |
Rint | 0.034 | 0.105 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.115, 1.02 | 0.045, 0.123, 0.94 |
No. of reflections | 4468 | 4639 |
No. of parameters | 321 | 321 |
No. of restraints | 6 | 6 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.20 | 0.25, −0.21 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2 | 0.86 | 2.10 | 2.8169 (18) | 140.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···N2 | 0.86 | 2.20 | 2.793 (2) | 126.1 |
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Thiophene derivatives have recently been incorporated into new pharmaceutical and chemical compounds tested as anti-inflammatory agents (Pillai et al., 2004, 2005). The double functionality of carboxamide/thiophene derivatives drives the study of the structural properties of both 2-thiophenecarboxamides and 2-thiophenecarbamates, in an attempt to elucidate the structure–activity relationships involved in their pharmacological activity (Ribeiro da Silva et al., 2007). Various ligands based on the benzo[b]thiophene molecular framework, in an appropriately substituted form, have demonstrated moderate to strong binding affinity for the oestrogen receptor (Jones et al., 1984; Pinney & Katzenellenbogen, 1991; Pinney et al., 1991; Palkowitz et al., 1997). In view of the clinical applications of these classes of compounds, single-crystal structure determinations have been performed on a series of biologically active thiophene-3-carboxamide derivatives (Vasu et al., 2003, 2004a,b, 2005, 2008). In the majority of these structures, the invariant molecular skeleton comprises the N-phenyl-2-{[(1E)-phenylmethylene]amino}-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide unit. This molecular skeleton is divided into three parts, namely the cyclohexene fused thiophene part, the N-phenyl ring and the benzylideneamine unit. Most of the reported structure determinations involve various substituents on the N-phenyl and benzylideneamine parts. The title compounds contain a methyl group in the meta [for (I)] or ortho [for (II)] position of the N-phenyl ring, and three methoxy groups on the benzylideneamine unit.
Compounds (I) and (II) crystallize in space groups P1 and Pbca, respectively, in both cases with one molecule in the asymmetric unit. For both structures, atoms C24 and C25 of the cyclohexene ring were modelled as disordered, with refined site occupancies of 0.686 (7):0.314 (7) for the two disorder components in (I), and 0.501 (10):0.499 (10) for the two components in (II). All of the disorder components for the cyclohexene ring correspond to a half-chair conformation. The thiophene ring C1–C4/S1 is planar in both structures, with the maximum deviation from the least-squares plane being −0.007 (2) and 0.009 (2) Å for atom C4 in (I) and (II), respectively.
The bond angles C9—C10—C11 in (I) and C6—C7—C8 in (II) are 118.16 (17) and 116.98 (18)°, respectively, which deviate from the ideal value of 120° on account of the electron-releasing inductive effect of the methyl group. Similar variations in bond angles have been observed in 2-[(E)-(4-chlorophenyl)methyleneamino]-N-(X-methylphenyl)-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide, where X = 2 or 3 (Vasu et al., 2004a), and in 2-{[(E)-(4-methoxyphenyl)methylene]amino}-N-(3-methylphenyl)-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide and N-(4-methylphenyl)-2-{[(E)-(4-methylphenyl)methylene]amino}-4,5,6,7-tetrahydro-1-benzothiophene-3-carboxamide (Vasu et al., 2004b). Similarly, the bond angles C4—N2—C13 (around the imine N atom) and C5—N1—C6 (around the amide N atom) are 119.94 (13) and 127.79 (14)°, respectively, in (I), and 121.83 (14) and 123.96 (13)°, respectively, in (II). This implies delocalization of the lone pair of electrons on N over the thiophene and N-phenyl rings in both compounds. This is further corroborated by the fact that the bond lengths corresponding to the imine and carboxamide groups are significantly different: in (I), the C5—N1, C4—N2 and C13—N2 bond lengths are 1.351 (2), 1.3889 (18) and 1.2770 (19) Å, respectively, while in (II) the corresponding values are 1.355 (2), 1.389 (2) and 1.274 (2) Å. Similar bond lengths have been reported for analogous systems (Vasu et al., 2003, 2004a,b; Kumar et al., 2005). The dihedral angles formed by the meta-toluidine ring in (I) and ortho-toluidine ring in (II) with the plane of the thiophene ring are 11.39 (6) and 48.74 (6)° for (I) and (II), respectively. It is noteworthy that the distortion from planarity is considerably larger for (II) than for (I).
In the 2,3,4-tris-methoxyphenyl group, all bond lengths and angles are comparable with standard literature values [Standard reference?]. The C16—O4, C17—O3 and C21—O2 bond lengths suggest some double-bond character due to resonance delocalization of the O-atom lone pairs with the benzene ring. In both structures, two of the methyl groups lie essentially in the plane of the benzene ring, with the C22—O4—C16—C17 and C21—O2—C18—C17 torsion angles being 174.72 (16) and −175.55 (15)°, respectively, for (I), and 171.42 (19) and −175.88 (16)°, respectively, for (II). The third methyl group lies out of the plane of the benzene ring in both structures, with the C20—O3—C17—C18 torsion angle being −74.3 (2) and 86.6 (2)° in (I) and (II), respectively.
An intramolecular N—H···N hydrogen bond is present in both structures (Table 1; Figs. 1 and 2), in spite of the presence of the carbonyl group. The absence of any intermolecular N—H···O═C hydrogen bond is based on the fact that there is restricted rotation about the C13═N2 double bond. The observed E configuration places the bulky thiophene and trimethoxyphenyl groups on opposite sides of double bond, thereby placing the lone pair on atom N2 in a suitable orientation for formation of the intramolecular hydrogen bond. The hydrogen bond in (II) is significantly distorted compared with that in (I), on account of the twist of the N-phenyl ring from the plane of the remainder of the molecule. There are no primary intermolecular interactions that obviously dictate the crystal packing in (I) and (II). The structures of both compounds are essentially layered, with the molecular planes lying approximately parallel within the planes of the layers (Figs. 3 and 4). Compound (I) has a significantly higher density than (II) [1.340 cf 1.305 Mg m−3], indicating that the molecular packing in the meta isomer is overall more efficient than in the ortho isomer.