Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802011480/ob6142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802011480/ob61425sup2.hkl |
CCDC reference: 193731
Data collection: COLLECT (Nonius, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
C26H20BrNO3S | F(000) = 516 |
Mr = 506.40 | Dx = 1.553 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5502 (5) Å | Cell parameters from 8301 reflections |
b = 8.6443 (5) Å | θ = 4.5–27.5° |
c = 13.1213 (6) Å | µ = 2.02 mm−1 |
β = 91.028 (3)° | T = 120 K |
V = 1083.05 (10) Å3 | Plate, colourless |
Z = 2 | 0.25 × 0.13 × 0.03 mm |
KappaCCD diffractometer | 3754 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
CCD scans | θmax = 27.5°, θmin = 4.5° |
Absorption correction: numerical (Herrendorf et al., 1997) | h = −12→12 |
Tmin = 0.566, Tmax = 0.815 | k = −11→11 |
8301 measured reflections | l = −16→17 |
4234 independent reflections |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0225P)2 + 1.1354P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
4234 reflections | Δρmax = 0.76 e Å−3 |
289 parameters | Δρmin = −0.52 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983), 1582 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.013 (10) |
Experimental. Spectroscopic data, Compond (2): IR λ 2773, 1653, 1564, 1381, 791 cm-1; 1H-NMR (CDCl3, 400 MHz) δ 12.77 (bs, 1H), 11.72 (bs, 1H), 7.49 (d, J=8.3 Hz, 2H), 7.33 (d, J=8.3 Hz, 2H), 4.61 (q, J=7.0 Hz, 2H), 4.00 (s, 2H), 1.44 (t, J=7.0 Hz, 3H); 13C NMR (CDCl3, 400 MHz) δ 176.6, 132.3, 131.2, 130.1, 122.6, 71.2, 38.6, 13.5; Compound (3): [α]D +53° (c 0.91, CHCl3); IR λ 2951, 1739, 1618, 1487, 1435, 1201, 1012 cm-1; 1H NMR (CDCL3, 400 MHz) δ 7.41 (d, J=8.3 Hz, 2H), 7.14 (d, j=8.3 Hz, 2H), 5.07 (m, 1H), 3.86–3.74 (m, 5H), 3.54 (dd, J=11.3, 8.8 Hz, 1H), 3.46 (dd, J=11.2, 9.6 Hz, 1H); 13C NMR (CDCl3, 400 MHz) δ 172.8, 170.9, 134.4, 131.6, 130.6, 121.2, 77.7, 52.6, 39.9, 35.7; HRMS (FAB+) calcd for C12H12BrNO2S 313.9850, found 313.9854. Compound (5): [α]D -134° (c1.26, CHCl3); IR λ 3039, 2953, 1745, 1649, 1479, 1205, 1007, 777 cm-1; 1H-NMR (CDCl3, 400 MHz) δ 7.83 (d, J=7.7 Hz, 1H), 7.75 (d, J=8.2 Hz, 1H), 7.59 (d, J=8.1 Hz, 1H), 7.52 (d, J=6.6 Hz, 2H), 7.48–7.34 (m, 3H), 7.22–7.14 (m, 3H), 5.86 (s, 1H), 5.61 (dd, J=11.2, 2.1 Hz, 1H), 4.03–3.87 (m, 2H), 3.82 (s, 3H), 3.68 (dd, J=11.8, 8.6 Hz, 1H), 3.47 (dd, J=11.8, 2.2 Hz, 1H); 13C NMR (CDCl3, 400 MHz) δ 168.3, 161.1, 154.0, 146.6, 135.1, 133.8, 133.5, 132.2, 131.9, 131.6, 131.4, 128.7, 127.7, 126.1,125.6, 125.4, 122.7, 115.5, 114.8, 63.5, 53.3, 36.8, 31.7; HRMS (FAB+) calcd. for C26H20BrNO3S 506.0426, found 506.0435. |
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. Data for a crystal of the title compound was collected using a Bruker Nonius KappaCCD diffractometer. The data set showed monoclinic symmetry, the systematic absences 0k0: k=2n indicated the possible space groups P21 and P21/m of which the former, non-centrosymmetric one could be confirmed during the structure determination. Due to the shape of the crystal (thin plate) a numerical absorption correction was applied (Herrendorf, 1997). All non-hydrogen atoms could be localized using direct methods (SHELXS97) and were refined using anisotropic thermal parameters. 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 | ||
C1 | 0.2950 (5) | −0.5182 (5) | 0.5694 (3) | 0.0391 (10) | |
H1A | 0.3546 | −0.4691 | 0.6193 | 0.047* | |
H1B | 0.2219 | −0.5735 | 0.6031 | 0.047* | |
C2 | 0.3797 (5) | −0.6291 (6) | 0.5053 (3) | 0.0377 (9) | |
H2 | 0.4776 | −0.6045 | 0.5102 | 0.045* | |
C3 | 0.3919 (4) | −0.6984 (5) | 0.3219 (3) | 0.0337 (9) | |
C4 | 0.3528 (4) | −0.6548 (5) | 0.2199 (3) | 0.0320 (8) | |
H4 | 0.3864 | −0.7178 | 0.1653 | 0.038* | |
C5 | 0.2710 (4) | −0.5290 (5) | 0.1984 (3) | 0.0303 (8) | |
C6 | 0.2241 (5) | −0.4322 (5) | 0.2790 (3) | 0.0308 (9) | |
C7 | 0.2612 (4) | −0.4759 (5) | 0.3773 (3) | 0.0334 (8) | |
C8 | 0.1491 (4) | −0.2821 (5) | 0.2655 (3) | 0.0305 (9) | |
C9 | 0.0092 (4) | −0.2726 (5) | 0.2300 (3) | 0.0328 (10) | |
H9 | −0.0390 | −0.3643 | 0.2077 | 0.039* | |
C10 | −0.0597 (4) | −0.1306 (5) | 0.2274 (3) | 0.0352 (9) | |
H10 | −0.1544 | −0.1235 | 0.2019 | 0.042* | |
C11 | 0.0107 (5) | 0.0001 (5) | 0.2607 (3) | 0.0362 (9) | |
C12 | 0.1481 (5) | −0.0036 (5) | 0.2939 (3) | 0.0358 (9) | |
H12 | 0.1980 | 0.0878 | 0.3149 | 0.043* | |
C13 | 0.2160 (5) | −0.1452 (5) | 0.2969 (3) | 0.0318 (9) | |
H13 | 0.3113 | −0.1480 | 0.3213 | 0.038* | |
C14 | 0.2268 (5) | −0.4887 (5) | 0.0901 (3) | 0.0353 (9) | |
H14A | 0.1286 | −0.5093 | 0.0810 | 0.042* | |
H14B | 0.2444 | −0.3809 | 0.0783 | 0.042* | |
C15 | 0.2995 (4) | −0.5734 (5) | 0.0050 (3) | 0.0318 (8) | |
C16 | 0.3942 (4) | −0.4934 (5) | −0.0543 (3) | 0.0373 (9) | |
H16 | 0.4140 | −0.3866 | −0.0402 | 0.045* | |
C17 | 0.4650 (5) | −0.5665 (6) | −0.1351 (3) | 0.0389 (10) | |
H17 | 0.5299 | −0.5087 | −0.1751 | 0.047* | |
C18 | 0.4411 (4) | −0.7185 (6) | −0.1562 (3) | 0.0387 (10) | |
H18 | 0.4897 | −0.7669 | −0.2111 | 0.046* | |
C19 | 0.3455 (3) | −0.8050 (7) | −0.0989 (2) | 0.0328 (7) | |
C20 | 0.3199 (5) | −0.9645 (5) | −0.1194 (3) | 0.0386 (9) | |
H20 | 0.3686 | −1.0150 | −0.1735 | 0.046* | |
C21 | 0.2280 (5) | −1.0479 (5) | −0.0639 (3) | 0.0425 (10) | |
H21 | 0.2132 | −1.1553 | −0.0792 | 0.051* | |
C22 | 0.1528 (5) | −0.9754 (6) | 0.0142 (3) | 0.0430 (10) | |
H22 | 0.0881 | −1.0355 | 0.0529 | 0.052* | |
C23 | 0.1737 (4) | −0.8228 (6) | 0.0364 (3) | 0.0384 (10) | |
H23 | 0.1211 | −0.7760 | 0.0900 | 0.046* | |
C24 | 0.2718 (4) | −0.7321 (5) | −0.0183 (3) | 0.0325 (8) | |
C25 | 0.3567 (5) | −0.7897 (7) | 0.5439 (3) | 0.0433 (10) | |
C26 | 0.1871 (8) | −0.9856 (7) | 0.5625 (5) | 0.075 (2) | |
H26A | 0.0952 | −1.0133 | 0.5379 | 0.090* | |
H26B | 0.1858 | −0.9731 | 0.6352 | 0.090* | |
H26C | 0.2522 | −1.0657 | 0.5454 | 0.090* | |
Br1 | −0.08413 (5) | 0.19489 (6) | 0.25934 (3) | 0.04549 (14) | |
O1 | 0.4641 (3) | −0.8122 (5) | 0.3478 (2) | 0.0435 (6) | |
O2 | 0.4342 (4) | −0.8571 (4) | 0.6017 (3) | 0.0615 (10) | |
O3 | 0.2293 (4) | −0.8407 (4) | 0.5155 (2) | 0.0503 (9) | |
N13 | 0.3369 (4) | −0.6049 (4) | 0.3979 (2) | 0.0321 (7) | |
S1 | 0.21891 (16) | −0.37294 (16) | 0.48723 (9) | 0.0544 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.057 (3) | 0.032 (2) | 0.0281 (19) | −0.0011 (19) | 0.0023 (19) | −0.0002 (17) |
C2 | 0.042 (2) | 0.043 (2) | 0.0286 (19) | 0.0004 (19) | 0.0014 (17) | 0.0020 (18) |
C3 | 0.038 (2) | 0.032 (2) | 0.0311 (19) | −0.0042 (17) | 0.0017 (17) | −0.0022 (17) |
C4 | 0.038 (2) | 0.030 (2) | 0.0283 (18) | 0.0014 (16) | 0.0060 (16) | −0.0047 (16) |
C5 | 0.032 (2) | 0.034 (2) | 0.0252 (18) | −0.0037 (16) | 0.0058 (15) | −0.0030 (15) |
C6 | 0.037 (2) | 0.026 (2) | 0.030 (2) | −0.0038 (17) | 0.0047 (17) | −0.0006 (16) |
C7 | 0.040 (2) | 0.031 (2) | 0.0294 (19) | 0.0045 (17) | 0.0049 (16) | −0.0013 (16) |
C8 | 0.0366 (18) | 0.030 (3) | 0.0247 (15) | −0.0003 (17) | 0.0049 (13) | −0.0031 (16) |
C9 | 0.0356 (19) | 0.032 (3) | 0.0311 (18) | −0.0044 (15) | 0.0038 (15) | −0.0021 (16) |
C10 | 0.034 (2) | 0.041 (2) | 0.0305 (19) | 0.0026 (18) | 0.0011 (16) | −0.0015 (18) |
C11 | 0.048 (2) | 0.034 (2) | 0.0269 (19) | 0.0032 (18) | 0.0069 (17) | 0.0014 (17) |
C12 | 0.047 (2) | 0.0282 (19) | 0.032 (2) | −0.0044 (18) | 0.0020 (18) | −0.0006 (17) |
C13 | 0.031 (2) | 0.032 (2) | 0.032 (2) | −0.0032 (17) | 0.0027 (17) | 0.0010 (18) |
C14 | 0.044 (2) | 0.036 (2) | 0.0260 (19) | 0.0047 (18) | 0.0005 (17) | −0.0025 (17) |
C15 | 0.035 (2) | 0.034 (2) | 0.0271 (18) | 0.0035 (17) | 0.0019 (16) | −0.0027 (16) |
C16 | 0.042 (2) | 0.037 (2) | 0.033 (2) | −0.0019 (18) | 0.0005 (17) | −0.0011 (18) |
C17 | 0.041 (2) | 0.042 (2) | 0.033 (2) | −0.0067 (19) | 0.0074 (19) | 0.0029 (19) |
C18 | 0.041 (2) | 0.045 (3) | 0.0301 (19) | 0.005 (2) | 0.0032 (17) | −0.0044 (18) |
C19 | 0.0343 (17) | 0.0367 (18) | 0.0273 (16) | 0.002 (2) | −0.0028 (13) | 0.001 (2) |
C20 | 0.046 (2) | 0.038 (2) | 0.032 (2) | 0.0050 (19) | −0.0048 (18) | −0.0076 (18) |
C21 | 0.058 (3) | 0.035 (2) | 0.034 (2) | −0.006 (2) | −0.011 (2) | 0.0001 (19) |
C22 | 0.051 (3) | 0.043 (3) | 0.035 (2) | −0.011 (2) | −0.0056 (19) | 0.0053 (19) |
C23 | 0.045 (2) | 0.042 (3) | 0.0282 (16) | −0.007 (2) | 0.0017 (15) | −0.003 (2) |
C24 | 0.034 (2) | 0.035 (2) | 0.0286 (18) | 0.0017 (17) | 0.0000 (16) | −0.0004 (17) |
C25 | 0.063 (3) | 0.035 (2) | 0.0316 (18) | 0.008 (3) | 0.0101 (18) | −0.003 (2) |
C26 | 0.129 (6) | 0.040 (3) | 0.057 (3) | −0.019 (3) | 0.037 (4) | 0.000 (3) |
Br1 | 0.0605 (3) | 0.0338 (2) | 0.0426 (2) | 0.0115 (2) | 0.01229 (17) | 0.0073 (2) |
O1 | 0.0542 (15) | 0.0396 (16) | 0.0368 (13) | 0.0151 (19) | −0.0001 (12) | −0.0011 (17) |
O2 | 0.091 (3) | 0.053 (2) | 0.0403 (17) | 0.0337 (19) | 0.0048 (18) | 0.0033 (15) |
O3 | 0.074 (2) | 0.035 (2) | 0.0421 (16) | −0.0099 (15) | 0.0114 (15) | 0.0008 (13) |
N13 | 0.0398 (18) | 0.0306 (17) | 0.0257 (16) | −0.0010 (14) | 0.0013 (14) | −0.0020 (14) |
S1 | 0.0842 (9) | 0.0499 (7) | 0.0293 (5) | 0.0254 (6) | 0.0038 (6) | −0.0051 (5) |
Br1—C11 | 1.912 (4) | C10—H10 | 0.9600 |
S1—C7 | 1.748 (4) | C13—C12 | 1.386 (7) |
S1—C1 | 1.799 (5) | C13—H13 | 0.9600 |
O1—C3 | 1.245 (6) | C1—C2 | 1.518 (6) |
C19—C18 | 1.408 (6) | C1—H1A | 0.9600 |
C19—C20 | 1.425 (8) | C1—H1B | 0.9600 |
C19—C24 | 1.427 (5) | O3—C26 | 1.456 (6) |
C8—C13 | 1.403 (6) | C23—C22 | 1.365 (7) |
C8—C9 | 1.410 (5) | C23—C24 | 1.426 (6) |
C8—C6 | 1.491 (6) | C23—H23 | 0.9601 |
C6—C7 | 1.384 (6) | C18—C17 | 1.361 (6) |
C6—C5 | 1.428 (6) | C18—H18 | 0.9600 |
O2—C25 | 1.201 (6) | C12—C11 | 1.376 (6) |
C5—C4 | 1.366 (6) | C12—H12 | 0.9601 |
C5—C14 | 1.516 (5) | C14—H14A | 0.9600 |
N13—C7 | 1.353 (5) | C14—H14B | 0.9600 |
N13—C3 | 1.394 (5) | C20—C21 | 1.358 (6) |
N13—C2 | 1.476 (5) | C20—H20 | 0.9599 |
C25—O3 | 1.340 (6) | C16—C17 | 1.415 (6) |
C25—C2 | 1.495 (7) | C16—H16 | 0.9600 |
C15—C16 | 1.388 (6) | C2—H2 | 0.9599 |
C15—C24 | 1.429 (6) | C22—C21 | 1.408 (7) |
C15—C14 | 1.514 (5) | C22—H22 | 0.9601 |
C9—C10 | 1.392 (6) | C21—H21 | 0.9600 |
C9—H9 | 0.9600 | C17—H17 | 0.9600 |
C4—C3 | 1.433 (6) | C26—H26A | 0.9599 |
C4—H4 | 0.9599 | C26—H26B | 0.9600 |
C10—C11 | 1.381 (7) | C26—H26C | 0.9600 |
C7—S1—C1 | 92.4 (2) | C23—C24—C15 | 122.7 (4) |
C18—C19—C20 | 121.5 (4) | C19—C24—C15 | 119.4 (4) |
C18—C19—C24 | 119.6 (5) | C11—C12—C13 | 118.2 (4) |
C20—C19—C24 | 118.8 (4) | C11—C12—H12 | 122.5 |
C13—C8—C9 | 118.1 (4) | C13—C12—H12 | 119.3 |
C13—C8—C6 | 118.9 (3) | N13—C7—C6 | 122.5 (4) |
C9—C8—C6 | 122.7 (4) | N13—C7—S1 | 112.7 (3) |
C7—C6—C5 | 116.9 (4) | C6—C7—S1 | 124.8 (3) |
C7—C6—C8 | 117.6 (4) | C15—C14—C5 | 117.1 (3) |
C5—C6—C8 | 125.4 (4) | C15—C14—H14A | 106.2 |
C4—C5—C6 | 120.0 (4) | C5—C14—H14A | 109.2 |
C4—C5—C14 | 121.7 (3) | C15—C14—H14B | 105.5 |
C6—C5—C14 | 118.3 (4) | C5—C14—H14B | 109.1 |
C7—N13—C3 | 122.9 (3) | H14A—C14—H14B | 109.5 |
C7—N13—C2 | 116.4 (3) | C21—C20—C19 | 121.5 (4) |
C3—N13—C2 | 120.0 (3) | C21—C20—H20 | 118.8 |
O2—C25—O3 | 124.2 (5) | C19—C20—H20 | 119.7 |
O2—C25—C2 | 124.8 (5) | C15—C16—C17 | 121.5 (4) |
O3—C25—C2 | 110.4 (4) | C15—C16—H16 | 119.9 |
C16—C15—C24 | 118.5 (4) | C17—C16—H16 | 118.6 |
C16—C15—C14 | 119.0 (4) | N13—C2—C25 | 114.5 (4) |
C24—C15—C14 | 122.4 (4) | N13—C2—C1 | 107.3 (3) |
C10—C9—C8 | 120.3 (4) | C25—C2—C1 | 108.4 (3) |
C10—C9—H9 | 119.8 | N13—C2—H2 | 106.6 |
C8—C9—H9 | 119.9 | C25—C2—H2 | 109.3 |
C5—C4—C3 | 122.8 (4) | C1—C2—H2 | 110.6 |
C5—C4—H4 | 119.6 | C23—C22—C21 | 120.8 (4) |
C3—C4—H4 | 117.6 | C23—C22—H22 | 120.1 |
C11—C10—C9 | 119.1 (4) | C21—C22—H22 | 119.1 |
C11—C10—H10 | 120.5 | C20—C21—C22 | 119.8 (4) |
C9—C10—H10 | 120.4 | C20—C21—H21 | 119.7 |
C12—C13—C8 | 121.8 (4) | C22—C21—H21 | 120.5 |
C12—C13—H13 | 118.2 | C18—C17—C16 | 120.2 (4) |
C8—C13—H13 | 120.0 | C18—C17—H17 | 119.9 |
C2—C1—S1 | 108.8 (3) | C16—C17—H17 | 119.9 |
C2—C1—H1A | 110.0 | O3—C26—H26A | 109.3 |
S1—C1—H1A | 109.2 | O3—C26—H26B | 109.4 |
C2—C1—H1B | 109.9 | H26A—C26—H26B | 109.5 |
S1—C1—H1B | 109.5 | O3—C26—H26C | 109.7 |
H1A—C1—H1B | 109.5 | H26A—C26—H26C | 109.5 |
C25—O3—C26 | 114.9 (5) | H26B—C26—H26C | 109.5 |
C22—C23—C24 | 121.2 (4) | C12—C11—C10 | 122.5 (4) |
C22—C23—H23 | 119.2 | C12—C11—Br1 | 118.2 (3) |
C24—C23—H23 | 119.6 | C10—C11—Br1 | 119.3 (3) |
C17—C18—C19 | 120.8 (4) | O1—C3—N13 | 118.5 (4) |
C17—C18—H18 | 119.5 | O1—C3—C4 | 126.6 (4) |
C19—C18—H18 | 119.8 | N13—C3—C4 | 114.8 (4) |
C23—C24—C19 | 117.9 (4) |