Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105003951/ty1004sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105003951/ty1004Isup2.hkl |
CCDC reference: 282184
2-Phenyl-5-thiol-1,3,4-thiadiazole (0.582 g, 3 mmol), α-acetobromoglucose (1.230 g, 3 mol) and KOH (0.168 g, 3 mmol) were reacted at room temperature for 12 h. The product was obtained via column-chromatograpic purification and the crystals were recrystallized by slow evaporation from petroleum ether–ethyl acetate (4:1) (m.p. 424–426 K). Spectroscopic analysis: 1H NMR (400 MHz, CDCl3, δ, p.p.m): 2.018 (s, 3 H), 2.040 (s, 3 H), 2.060 (s, 3 H), 2.088 (s, 3 H), 3.845–3.886 (m, 1 H), 4.166 (dd, J = 2.0 and 12.8 Hz, 1 H), 4.302 (dd, J = 4.8 and 12.8 Hz, 1 H), 5.137–5.205 (m, 2 H), 5.309 (t, J = 9.2 Hz, 1 H), 5.444 (d, J = 10.4 Hz, 1 H), 7.459–7.511 (m, 3 H), 7.899–7.922 (m, 2 H).
H atoms were placed in calculated positions with C—H = 0.97 Å and were included in the final cycles of refinement [Uiso(H) = 1.2Ueq(parent atom)].
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: PLATON (Spek, 2003).
Fig. 1. A view of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. |
C22H24N2O9S2 | F(000) = 1096.0 |
Mr = 524.56 | Dx = 1.440 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7511 reflections |
a = 8.010 (2) Å | θ = 3.2–27.5° |
b = 10.526 (2) Å | µ = 0.28 mm−1 |
c = 28.685 (6) Å | T = 173 K |
V = 2418.7 (9) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.25 × 0.20 mm |
Rigaku/MSC Mercury CCD area-detector diffractometer | 5151 reflections with F2 > 2σ(F2) |
Detector resolution: 28.57 pixels mm-1 | Rint = 0.037 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan TEXSAN (Molecular Structure Corporation, 1999) | h = −10→9 |
Tmin = 0.825, Tmax = 0.947 | k = −11→13 |
19569 measured reflections | l = −37→37 |
5524 independent reflections |
Refinement on F | w = 1/[σ2(Fo) + 0.00063|Fo|2] |
R[F2 > 2σ(F2)] = 0.033 | (Δ/σ)max = 0.001 |
wR(F2) = 0.046 | Δρmax = 0.25 e Å−3 |
S = 1.06 | Δρmin = −0.24 e Å−3 |
5499 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
317 parameters | Absolute structure parameter: 0.00 (5) |
H-atom parameters constrained |
C22H24N2O9S2 | V = 2418.7 (9) Å3 |
Mr = 524.56 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.010 (2) Å | µ = 0.28 mm−1 |
b = 10.526 (2) Å | T = 173 K |
c = 28.685 (6) Å | 0.35 × 0.25 × 0.20 mm |
Rigaku/MSC Mercury CCD area-detector diffractometer | 5524 independent reflections |
Absorption correction: multi-scan TEXSAN (Molecular Structure Corporation, 1999) | 5151 reflections with F2 > 2σ(F2) |
Tmin = 0.825, Tmax = 0.947 | Rint = 0.037 |
19569 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.046 | Δρmax = 0.25 e Å−3 |
S = 1.06 | Δρmin = −0.24 e Å−3 |
5499 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
317 parameters | Absolute structure parameter: 0.00 (5) |
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.27622 (5) | 0.20966 (4) | 0.68265 (2) | 0.0300 (1) | |
S2 | −0.05465 (6) | 0.13378 (4) | 0.72770 (2) | 0.0343 (1) | |
O1 | 0.1245 (1) | 0.0409 (1) | 0.62962 (4) | 0.0259 (3) | |
O2 | 0.0702 (2) | −0.2128 (1) | 0.61743 (5) | 0.0377 (3) | |
O3 | −0.0567 (2) | −0.3742 (1) | 0.58108 (8) | 0.0690 (6) | |
O4 | 0.1401 (2) | −0.0523 (1) | 0.50689 (4) | 0.0268 (3) | |
O5 | 0.2289 (2) | −0.2543 (1) | 0.50827 (6) | 0.0525 (4) | |
O6 | 0.4793 (1) | 0.0391 (1) | 0.52769 (4) | 0.0245 (3) | |
O7 | 0.4833 (2) | 0.2033 (1) | 0.47712 (5) | 0.0378 (3) | |
O8 | 0.4728 (1) | 0.2408 (1) | 0.59405 (4) | 0.0261 (3) | |
O9 | 0.6921 (2) | 0.1407 (2) | 0.62615 (8) | 0.0667 (6) | |
N1 | 0.0320 (2) | 0.3625 (1) | 0.71316 (7) | 0.0439 (5) | |
N2 | −0.1200 (2) | 0.3682 (1) | 0.73523 (7) | 0.0466 (5) | |
C1 | 0.0629 (2) | −0.0035 (1) | 0.58570 (6) | 0.0241 (4) | |
C2 | 0.2089 (2) | −0.0298 (1) | 0.55251 (5) | 0.0224 (4) | |
C3 | 0.3279 (2) | 0.0825 (1) | 0.54928 (6) | 0.0221 (3) | |
C4 | 0.3733 (2) | 0.1283 (1) | 0.59786 (5) | 0.0222 (3) | |
C5 | 0.2145 (2) | 0.1563 (1) | 0.62533 (6) | 0.0237 (4) | |
C6 | −0.0385 (2) | −0.1212 (2) | 0.59557 (6) | 0.0332 (4) | |
C7 | 0.0485 (2) | −0.3363 (2) | 0.60692 (7) | 0.0343 (4) | |
C8 | 0.1716 (3) | −0.4169 (2) | 0.63204 (7) | 0.0472 (6) | |
C9 | 0.1569 (2) | −0.1711 (2) | 0.48867 (6) | 0.0290 (4) | |
C10 | 0.0727 (2) | −0.1824 (2) | 0.44275 (7) | 0.0383 (5) | |
C11 | 0.5506 (2) | 0.1125 (1) | 0.49426 (6) | 0.0246 (4) | |
C12 | 0.7215 (2) | 0.0655 (2) | 0.48357 (7) | 0.0316 (4) | |
C13 | 0.6316 (2) | 0.2361 (2) | 0.61116 (7) | 0.0350 (5) | |
C14 | 0.7128 (3) | 0.3628 (2) | 0.60825 (8) | 0.0471 (6) | |
C15 | 0.0809 (2) | 0.2461 (1) | 0.70673 (6) | 0.0255 (4) | |
C16 | −0.1812 (2) | 0.2566 (1) | 0.74498 (6) | 0.0251 (4) | |
C17 | −0.3421 (2) | 0.2403 (2) | 0.76863 (6) | 0.0266 (4) | |
C18 | −0.4251 (2) | 0.1241 (2) | 0.76842 (7) | 0.0355 (5) | |
C19 | −0.5789 (3) | 0.1125 (2) | 0.79038 (7) | 0.0432 (5) | |
C20 | −0.6484 (3) | 0.2145 (2) | 0.81284 (7) | 0.0467 (6) | |
C21 | −0.5659 (3) | 0.3302 (2) | 0.81388 (8) | 0.0474 (6) | |
C22 | −0.4124 (3) | 0.3431 (2) | 0.79225 (7) | 0.0380 (5) | |
H1 | −0.0089 | 0.0609 | 0.5722 | 0.0289* | |
H2 | 0.2693 | −0.1045 | 0.5629 | 0.0269* | |
H3) | 0.2783 | 0.1508 | 0.5313 | 0.0266* | |
H4 | 0.4368 | 0.0628 | 0.6137 | 0.0267* | |
H5 | 0.1478 | 0.2203 | 0.6097 | 0.0284* | |
H6 | −0.0822 | −0.1556 | 0.5667 | 0.0399* | |
H7 | −0.1303 | −0.1007 | 0.6163 | 0.0399* | |
H8 | 0.1914 | −0.4940 | 0.6144 | 0.0566* | |
H9 | 0.2756 | −0.3707 | 0.6356 | 0.0566* | |
H10 | 0.1280 | −0.4386 | 0.6626 | 0.0566* | |
H11 | −0.0379 | −0.1453 | 0.4446 | 0.0460* | |
H12 | 0.1375 | −0.1378 | 0.4193 | 0.0460* | |
H13 | 0.0636 | −0.2713 | 0.4343 | 0.0460* | |
H14 | 0.7198 | −0.0264 | 0.4812 | 0.0379* | |
H15 | 0.7588 | 0.1015 | 0.4542 | 0.0379* | |
H16 | 0.7972 | 0.0909 | 0.5083 | 0.0379* | |
H17 | 0.8246 | 0.3577 | 0.6211 | 0.0565* | |
H18 | 0.7187 | 0.3894 | 0.5759 | 0.0565* | |
H19 | 0.6480 | 0.4241 | 0.6259 | 0.0565* | |
H20 | −0.3756 | 0.0514 | 0.7529 | 0.0426* | |
H21 | −0.6374 | 0.0318 | 0.7898 | 0.0518* | |
H22 | −0.7559 | 0.2057 | 0.8281 | 0.0561* | |
H23 | −0.6157 | 0.4022 | 0.8298 | 0.0569* | |
H24 | −0.3536 | 0.4236 | 0.7935 | 0.0456* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0261 (2) | 0.0371 (2) | 0.0269 (2) | 0.0004 (2) | 0.0008 (2) | −0.0063 (2) |
S2 | 0.0336 (2) | 0.0195 (2) | 0.0496 (3) | 0.0004 (2) | 0.0098 (2) | −0.0001 (2) |
O1 | 0.0282 (6) | 0.0245 (5) | 0.0250 (6) | −0.0034 (5) | 0.0033 (5) | 0.0010 (4) |
O2 | 0.0568 (8) | 0.0265 (6) | 0.0298 (6) | −0.0114 (6) | −0.0055 (6) | 0.0038 (5) |
O3 | 0.0485 (9) | 0.0416 (8) | 0.117 (2) | −0.0038 (8) | −0.027 (1) | −0.0244 (10) |
O4 | 0.0298 (6) | 0.0244 (5) | 0.0262 (6) | 0.0032 (5) | −0.0034 (5) | −0.0031 (4) |
O5 | 0.086 (1) | 0.0249 (6) | 0.0467 (9) | 0.0127 (7) | −0.0112 (8) | −0.0048 (6) |
O6 | 0.0257 (6) | 0.0205 (5) | 0.0274 (6) | 0.0032 (4) | 0.0062 (5) | 0.0022 (4) |
O7 | 0.0398 (7) | 0.0314 (6) | 0.0422 (7) | 0.0059 (6) | 0.0084 (6) | 0.0143 (6) |
O8 | 0.0254 (6) | 0.0207 (5) | 0.0323 (6) | −0.0035 (4) | 0.0004 (5) | 0.0018 (4) |
O9 | 0.0392 (9) | 0.0521 (9) | 0.109 (2) | −0.0028 (7) | −0.0309 (9) | 0.020 (1) |
N1 | 0.0446 (9) | 0.0257 (7) | 0.062 (1) | −0.0017 (7) | 0.0295 (8) | −0.0003 (7) |
N2 | 0.0466 (10) | 0.0242 (7) | 0.069 (1) | 0.0010 (7) | 0.0314 (9) | 0.0031 (8) |
C1 | 0.0233 (7) | 0.0225 (7) | 0.0264 (8) | −0.0022 (6) | 0.0004 (7) | −0.0013 (6) |
C2 | 0.0232 (7) | 0.0207 (7) | 0.0234 (7) | 0.0014 (6) | −0.0009 (6) | 0.0007 (6) |
C3 | 0.0238 (7) | 0.0169 (6) | 0.0257 (7) | 0.0043 (6) | 0.0022 (6) | 0.0012 (6) |
C4 | 0.0241 (7) | 0.0164 (6) | 0.0261 (7) | 0.0004 (6) | 0.0012 (6) | 0.0015 (6) |
C5 | 0.0240 (7) | 0.0221 (7) | 0.0249 (7) | 0.0001 (6) | −0.0002 (6) | 0.0006 (6) |
C6 | 0.0309 (8) | 0.0331 (8) | 0.0358 (9) | −0.0075 (8) | 0.0034 (7) | 0.0019 (7) |
C7 | 0.0356 (9) | 0.0294 (8) | 0.0378 (9) | −0.0112 (7) | 0.0117 (8) | −0.0036 (7) |
C8 | 0.074 (2) | 0.0338 (9) | 0.0335 (10) | −0.0056 (10) | −0.003 (1) | 0.0040 (8) |
C9 | 0.0280 (8) | 0.0265 (8) | 0.0327 (9) | −0.0041 (6) | 0.0058 (7) | −0.0063 (7) |
C10 | 0.0312 (9) | 0.050 (1) | 0.0340 (9) | −0.0054 (8) | 0.0024 (8) | −0.0130 (8) |
C11 | 0.0283 (7) | 0.0210 (7) | 0.0245 (7) | −0.0034 (6) | 0.0015 (6) | −0.0014 (6) |
C12 | 0.0280 (8) | 0.0273 (8) | 0.0396 (9) | −0.0026 (7) | 0.0078 (8) | 0.0000 (7) |
C13 | 0.0273 (8) | 0.0396 (10) | 0.0381 (10) | −0.0056 (8) | −0.0023 (8) | −0.0018 (8) |
C14 | 0.040 (1) | 0.045 (1) | 0.056 (1) | −0.0165 (10) | 0.0018 (10) | −0.0071 (10) |
C15 | 0.0294 (8) | 0.0239 (7) | 0.0233 (8) | −0.0012 (6) | 0.0030 (6) | −0.0016 (6) |
C16 | 0.0295 (8) | 0.0220 (7) | 0.0237 (7) | 0.0015 (6) | 0.0013 (6) | 0.0001 (6) |
C17 | 0.0280 (8) | 0.0291 (8) | 0.0227 (7) | −0.0003 (6) | −0.0008 (6) | 0.0041 (6) |
C18 | 0.0385 (10) | 0.0379 (9) | 0.0301 (9) | −0.0099 (8) | 0.0003 (7) | −0.0036 (7) |
C19 | 0.041 (1) | 0.053 (1) | 0.0354 (10) | −0.0194 (10) | 0.0014 (8) | 0.0008 (9) |
C20 | 0.0342 (10) | 0.073 (1) | 0.0329 (10) | −0.010 (1) | 0.0070 (8) | 0.001 (1) |
C21 | 0.043 (1) | 0.054 (1) | 0.045 (1) | 0.0030 (9) | 0.017 (1) | 0.0016 (9) |
C22 | 0.040 (1) | 0.0340 (9) | 0.041 (1) | 0.0001 (8) | 0.0133 (8) | 0.0017 (8) |
S1—C5 | 1.807 (2) | C17—C18 | 1.392 (2) |
S1—C15 | 1.753 (2) | C17—C22 | 1.396 (2) |
S2—C15 | 1.715 (2) | C18—C19 | 1.389 (3) |
S2—C16 | 1.716 (2) | C19—C20 | 1.370 (3) |
O1—C1 | 1.431 (2) | C20—C21 | 1.386 (3) |
O1—C5 | 1.418 (2) | C21—C22 | 1.384 (3) |
O2—C6 | 1.442 (2) | C1—H1 | 0.9700 |
O2—C7 | 1.346 (2) | C2—H2 | 0.9700 |
O3—C7 | 1.191 (3) | C3—H3 | 0.9700 |
O4—C2 | 1.440 (2) | C4—H4 | 0.9700 |
O4—C9 | 1.362 (2) | C5—H5 | 0.9700 |
O5—C9 | 1.190 (2) | C6—H6 | 0.9700 |
O6—C3 | 1.436 (2) | C6—H7 | 0.9700 |
O6—C11 | 1.357 (2) | C8—H8 | 0.9700 |
O7—C11 | 1.202 (2) | C8—H9 | 0.9700 |
O8—C4 | 1.433 (2) | C8—H10 | 0.9700 |
O8—C13 | 1.364 (2) | C10—H11 | 0.9700 |
O9—C13 | 1.195 (3) | C10—H12 | 0.9700 |
N1—N2 | 1.374 (2) | C10—H13 | 0.9700 |
N1—C15 | 1.299 (2) | C12—H14 | 0.9700 |
N2—C16 | 1.303 (2) | C12—H15 | 0.9700 |
C1—C2 | 1.533 (2) | C12—H16 | 0.9700 |
C1—C6 | 1.509 (2) | C14—H17 | 0.9700 |
C2—C3 | 1.521 (2) | C14—H18 | 0.9700 |
C3—C4 | 1.518 (2) | C14—H19 | 0.9700 |
C4—C5 | 1.525 (2) | C18—H20 | 0.9700 |
C7—C8 | 1.487 (3) | C19—H21 | 0.9700 |
C9—C10 | 1.484 (3) | C20—H22 | 0.9700 |
C11—C12 | 1.487 (2) | C21—H23 | 0.9700 |
C13—C14 | 1.486 (3) | C22—H24 | 0.9700 |
C16—C17 | 1.467 (2) | ||
S1···O8 | 3.0077 (14) | C13···O6 | 3.394 (2) |
S1···C13 | 3.519 (2) | C13···S1 | 3.519 (2) |
S1···C18i | 3.548 (2) | C14···O3xi | 3.418 (3) |
S1···C19i | 3.456 (2) | C14···O7vii | 3.343 (3) |
S2···O1 | 3.3061 (15) | C17···C8viii | 3.567 (3) |
S2···N2 | 2.5317 (13) | C18···C8viii | 3.530 (3) |
S2···N1ii | 3.3264 (17) | C18···S1xii | 3.548 (2) |
S2···N2ii | 3.3019 (16) | C19···S1xii | 3.456 (2) |
S1···H24ii | 3.1500 | C7···H22xiii | 3.0300 |
S2···H20 | 2.8100 | C9···H6 | 2.9500 |
O1···S2 | 3.3061 (15) | C12···H8v | 2.9200 |
O1···O2 | 2.7281 (17) | C12···H3vii | 3.0500 |
O2···O1 | 2.7281 (17) | C14···H12vii | 3.0600 |
O3···C9iii | 3.081 (3) | C17···H9viii | 3.0300 |
O3···C14iv | 3.418 (3) | C18···H9viii | 3.0000 |
O3···C10iii | 3.104 (2) | C21···H20x | 3.0500 |
O4···O6 | 2.9434 (19) | C22···H20x | 3.0600 |
O5···C7 | 3.293 (3) | H1···H5 | 2.3600 |
O5···C12iii | 3.285 (2) | H1···H16xii | 2.4200 |
O5···C10v | 3.163 (2) | H1···O7vi | 2.8600 |
O6···O4 | 2.9434 (19) | H2···O2 | 2.5100 |
O6···C13 | 3.394 (2) | H2···O5 | 2.2500 |
O6···O8 | 2.8520 (17) | H3···O7 | 2.3300 |
O7···C14vi | 3.343 (3) | H3···H5 | 2.5900 |
O7···C12vi | 3.405 (2) | H3···O7vi | 2.8300 |
O8···C11 | 3.226 (2) | H3···C12vi | 3.0500 |
O8···O6 | 2.8520 (17) | H4···O9 | 2.2300 |
O8···S1 | 3.0077 (14) | H5···H1 | 2.3600 |
O2···H2 | 2.5100 | H5···H3 | 2.5900 |
O3···H12iii | 2.4500 | H6···O3 | 2.3500 |
O3···H6 | 2.3500 | H6···O4 | 2.7000 |
O4···H6 | 2.7000 | H6···C9 | 2.9500 |
O5···H2 | 2.2500 | H6···O5iii | 2.8000 |
O5···H14iii | 2.3300 | H7···H23xiii | 2.5600 |
O5···H6v | 2.8000 | H8···C12iii | 2.9200 |
O5···H11v | 2.5400 | H8···H15iii | 2.3300 |
O7···H3vii | 2.8300 | H9···C17ii | 3.0300 |
O7···H1vii | 2.8600 | H9···C18ii | 3.0000 |
O7···H3 | 2.3300 | H10···N1xiv | 2.6600 |
O7···H16vi | 2.6600 | H11···H14xii | 2.5400 |
O7···H18vi | 2.7900 | H11···O5iii | 2.5400 |
O8···H15vi | 2.7600 | H12···O3v | 2.4500 |
O9···H4 | 2.2300 | H12···C14vi | 3.0600 |
O9···H23ii | 2.8800 | H12···H19vi | 2.6000 |
N1···S2 | 2.5400 (14) | H14···H11i | 2.5400 |
N1···S2viii | 3.3264 (17) | H14···O5v | 2.3300 |
N2···S2 | 2.5317 (13) | H15···O8vii | 2.7600 |
N2···S2viii | 3.3019 (16) | H15···H8v | 2.3300 |
N1···H10ix | 2.6600 | H16···H1i | 2.4200 |
N2···H24 | 2.5800 | H16···O7vii | 2.6600 |
N2···H21x | 2.6900 | H18···O7vii | 2.7900 |
C6···C9 | 3.483 (3) | H19···H12vii | 2.6000 |
C7···O5 | 3.293 (3) | H20···S2 | 2.8100 |
C8···C17ii | 3.567 (3) | H20···C21xiii | 3.0500 |
C8···C18ii | 3.530 (3) | H20···C22xiii | 3.0600 |
C9···C6 | 3.483 (3) | H21···N2xiii | 2.6900 |
C9···O3v | 3.081 (3) | H22···C7x | 3.0300 |
C10···O5iii | 3.163 (2) | H23···O9viii | 2.8800 |
C10···O3v | 3.104 (2) | H23···H7x | 2.5600 |
C11···O8 | 3.226 (2) | H24···N2 | 2.5800 |
C12···O7vii | 3.405 (2) | H24···S1viii | 3.1500 |
C12···O5v | 3.285 (2) | ||
C5—S1—C15 | 100.53 (8) | C6—C1—H1 | 109.00 |
C15—S2—C16 | 87.45 (8) | O4—C2—H2 | 110.00 |
C1—O1—C5 | 112.2 (1) | C1—C2—H2 | 110.00 |
C6—O2—C7 | 118.0 (2) | C3—C2—H2 | 110.00 |
C2—O4—C9 | 117.5 (1) | O6—C3—H3 | 111.00 |
C3—O6—C11 | 118.6 (1) | C2—C3—H3 | 111.00 |
C4—O8—C13 | 117.5 (1) | C4—C3—H3 | 111.00 |
N2—N1—C15 | 112.0 (1) | O8—C4—H4 | 109.00 |
N1—N2—C16 | 113.1 (1) | C3—C4—H4 | 109.00 |
O1—C1—C2 | 110.0 (1) | C5—C4—H4 | 109.00 |
O1—C1—C6 | 106.8 (1) | S1—C5—H5 | 111.00 |
C2—C1—C6 | 112.3 (1) | O1—C5—H5 | 111.00 |
O4—C2—C1 | 107.6 (1) | C4—C5—H5 | 111.00 |
O4—C2—C3 | 108.2 (1) | O2—C6—H6 | 110.00 |
C1—C2—C3 | 112.0 (1) | O2—C6—H7 | 110.00 |
O6—C3—C2 | 108.0 (1) | C1—C6—H6 | 110.00 |
O6—C3—C4 | 107.1 (1) | C1—C6—H7 | 110.00 |
C2—C3—C4 | 109.9 (1) | H6—C6—H7 | 109.00 |
O8—C4—C3 | 109.0 (1) | C7—C8—H8 | 109.00 |
O8—C4—C5 | 110.1 (1) | C7—C8—H9 | 110.00 |
C3—C4—C5 | 109.6 (1) | C7—C8—H10 | 109.00 |
S1—C5—O1 | 109.1 (1) | H8—C8—H9 | 110.00 |
S1—C5—C4 | 107.6 (1) | H8—C8—H10 | 109.00 |
O1—C5—C4 | 107.7 (1) | H9—C8—H10 | 109.00 |
O2—C6—C1 | 107.8 (1) | C9—C10—H11 | 110.00 |
O2—C7—O3 | 123.7 (2) | C9—C10—H12 | 109.00 |
O2—C7—C8 | 110.9 (2) | C9—C10—H13 | 109.00 |
O3—C7—C8 | 125.4 (2) | H11—C10—H12 | 109.00 |
O4—C9—O5 | 122.9 (2) | H11—C10—H13 | 109.00 |
O4—C9—C10 | 111.6 (2) | H12—C10—H13 | 109.00 |
O5—C9—C10 | 125.5 (2) | C11—C12—H14 | 109.00 |
O6—C11—O7 | 123.5 (2) | C11—C12—H15 | 109.00 |
O6—C11—C12 | 110.1 (1) | C11—C12—H16 | 109.00 |
O7—C11—C12 | 126.4 (2) | H14—C12—H15 | 109.00 |
O8—C13—O9 | 122.5 (2) | H14—C12—H16 | 110.00 |
O8—C13—C14 | 110.8 (2) | H15—C12—H16 | 110.00 |
O9—C13—C14 | 126.7 (2) | C13—C14—H17 | 109.00 |
S1—C15—S2 | 123.53 (9) | C13—C14—H18 | 110.00 |
S1—C15—N1 | 122.1 (1) | C13—C14—H19 | 109.00 |
S2—C15—N1 | 114.2 (1) | H17—C14—H18 | 110.00 |
S2—C16—N2 | 113.3 (1) | H17—C14—H19 | 109.00 |
S2—C16—C17 | 124.4 (1) | H18—C14—H19 | 109.00 |
N2—C16—C17 | 122.3 (1) | C17—C18—H20 | 120.00 |
C16—C17—C18 | 121.4 (2) | C19—C18—H20 | 120.00 |
C16—C17—C22 | 119.2 (1) | C18—C19—H21 | 120.00 |
C18—C17—C22 | 119.4 (2) | C20—C19—H21 | 120.00 |
C17—C18—C19 | 119.9 (2) | C19—C20—H22 | 120.00 |
C18—C19—C20 | 120.3 (2) | C21—C20—H22 | 120.00 |
C19—C20—C21 | 120.3 (2) | C20—C21—H23 | 120.00 |
C20—C21—C22 | 120.0 (2) | C22—C21—H23 | 120.00 |
C17—C22—C21 | 120.0 (2) | C17—C22—H24 | 120.00 |
O1—C1—H1 | 109.00 | C21—C22—H24 | 120.00 |
C2—C1—H1 | 109.00 | ||
S1—C5—O1—C1 | 176.6 (1) | N2—C16—C17—C18 | 163.6 (2) |
S1—C5—C4—O8 | −60.2 (1) | N2—C16—C17—C22 | −17.1 (3) |
S1—C5—C4—C3 | 179.84 (10) | C1—O1—C5—C4 | −67.0 (2) |
S1—C15—S2—C16 | 175.9 (1) | C1—C2—O4—C9 | −113.7 (1) |
S1—C15—N1—N2 | −176.0 (1) | C1—C2—C3—C4 | 49.0 (2) |
S2—C15—S1—C5 | 78.1 (1) | C1—C6—O2—C7 | −143.7 (2) |
S2—C15—N1—N2 | −0.6 (2) | C2—O4—C9—C10 | 177.0 (1) |
S2—C16—N2—N1 | 0.2 (2) | C2—C1—O1—C5 | 61.4 (2) |
S2—C16—C17—C18 | −16.7 (2) | C2—C3—O6—C11 | 136.0 (1) |
S2—C16—C17—C22 | 162.6 (1) | C2—C3—C4—C5 | −54.2 (2) |
O1—C1—C2—O4 | −170.1 (1) | C3—O6—C11—C12 | 168.3 (1) |
O1—C1—C2—C3 | −51.3 (2) | C3—C2—O4—C9 | 125.0 (1) |
O1—C1—C6—O2 | −59.6 (2) | C3—C2—C1—C6 | −170.1 (1) |
O1—C5—S1—C15 | −67.2 (1) | C3—C4—O8—C13 | −117.8 (2) |
O1—C5—C4—O8 | −177.7 (1) | C4—O8—C13—C14 | −175.2 (2) |
O1—C5—C4—C3 | 62.4 (2) | C4—C3—O6—C11 | −105.7 (1) |
O2—C6—C1—C2 | 61.0 (2) | C4—C5—S1—C15 | 176.3 (1) |
O3—C7—O2—C6 | −1.0 (3) | C5—O1—C1—C6 | −176.6 (1) |
O4—C2—C1—C6 | 71.1 (2) | C5—C4—O8—C13 | 121.9 (1) |
O4—C2—C3—O6 | −76.1 (1) | C6—O2—C7—C8 | 179.4 (2) |
O4—C2—C3—C4 | 167.4 (1) | C15—S2—C16—C17 | 179.9 (2) |
O5—C9—O4—C2 | −2.0 (2) | C15—N1—N2—C16 | 0.2 (3) |
O6—C3—C2—C1 | 165.5 (1) | C16—C17—C18—C19 | −178.7 (2) |
O6—C3—C4—O8 | 68.2 (1) | C16—C17—C22—C21 | 178.6 (2) |
O6—C3—C4—C5 | −171.2 (1) | C17—C18—C19—C20 | −0.9 (3) |
O7—C11—O6—C3 | −10.4 (2) | C17—C22—C21—C20 | 1.2 (3) |
O8—C4—C3—C2 | −174.8 (1) | C18—C17—C22—C21 | −2.1 (3) |
O9—C13—O8—C4 | 4.8 (3) | C18—C19—C20—C21 | 0.0 (3) |
N1—N2—C16—C17 | 179.9 (2) | C19—C18—C17—C22 | 2.0 (3) |
N1—C15—S1—C5 | −107.0 (2) | C19—C20—C21—C22 | −0.1 (4) |
N1—C15—S2—C16 | 0.5 (2) | C19—C20—C21—C22 | −0.1 (4) |
N2—C16—S2—C15 | −0.4 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x, y−1/2, −z+3/2; (iii) x−1/2, −y−1/2, −z+1; (iv) x−1, y−1, z; (v) x+1/2, −y−1/2, −z+1; (vi) x−1/2, −y+1/2, −z+1; (vii) x+1/2, −y+1/2, −z+1; (viii) −x, y+1/2, −z+3/2; (ix) x, y+1, z; (x) −x−1, y+1/2, −z+3/2; (xi) x+1, y+1, z; (xii) x−1, y, z; (xiii) −x−1, y−1/2, −z+3/2; (xiv) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C22H24N2O9S2 |
Mr | 524.56 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 173 |
a, b, c (Å) | 8.010 (2), 10.526 (2), 28.685 (6) |
V (Å3) | 2418.7 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.35 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Rigaku/MSC Mercury CCD area-detector diffractometer |
Absorption correction | Multi-scan TEXSAN (Molecular Structure Corporation, 1999) |
Tmin, Tmax | 0.825, 0.947 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 19569, 5524, 5151 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.046, 1.06 |
No. of reflections | 5499 |
No. of parameters | 317 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Absolute structure | Flack (1983), with how many Friedel pairs |
Absolute structure parameter | 0.00 (5) |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), TEXSAN, ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2003).
S1—C5 | 1.807 (2) | N1—C15 | 1.299 (2) |
S1—C15 | 1.753 (2) | N2—C16 | 1.303 (2) |
S2—C15 | 1.715 (2) | C1—C2 | 1.533 (2) |
S2—C16 | 1.716 (2) | C1—C6 | 1.509 (2) |
O1—C1 | 1.431 (2) | C2—C3 | 1.521 (2) |
O1—C5 | 1.418 (2) | C3—C4 | 1.518 (2) |
O2—C6 | 1.442 (2) | C4—C5 | 1.525 (2) |
O2—C7 | 1.346 (2) | C7—C8 | 1.487 (3) |
O3—C7 | 1.191 (3) | C9—C10 | 1.484 (3) |
O4—C2 | 1.440 (2) | C11—C12 | 1.487 (2) |
O4—C9 | 1.362 (2) | C13—C14 | 1.486 (3) |
O5—C9 | 1.190 (2) | C16—C17 | 1.467 (2) |
O6—C3 | 1.436 (2) | C17—C18 | 1.392 (2) |
O6—C11 | 1.357 (2) | C17—C22 | 1.396 (2) |
O7—C11 | 1.202 (2) | C18—C19 | 1.389 (3) |
O8—C4 | 1.433 (2) | C19—C20 | 1.370 (3) |
O8—C13 | 1.364 (2) | C20—C21 | 1.386 (3) |
O9—C13 | 1.195 (3) | C21—C22 | 1.384 (3) |
N1—N2 | 1.374 (2) | ||
C5—S1—C15 | 100.53 (8) | O2—C7—C8 | 110.9 (2) |
C15—S2—C16 | 87.45 (8) | O3—C7—C8 | 125.4 (2) |
C1—O1—C5 | 112.2 (1) | O4—C9—O5 | 122.9 (2) |
C6—O2—C7 | 118.0 (2) | O4—C9—C10 | 111.6 (2) |
C2—O4—C9 | 117.5 (1) | O5—C9—C10 | 125.5 (2) |
C3—O6—C11 | 118.6 (1) | O6—C11—O7 | 123.5 (2) |
C4—O8—C13 | 117.5 (1) | O6—C11—C12 | 110.1 (1) |
N2—N1—C15 | 112.0 (1) | O7—C11—C12 | 126.4 (2) |
N1—N2—C16 | 113.1 (1) | O8—C13—O9 | 122.5 (2) |
O1—C1—C2 | 110.0 (1) | O8—C13—C14 | 110.8 (2) |
O1—C1—C6 | 106.8 (1) | O9—C13—C14 | 126.7 (2) |
C2—C1—C6 | 112.3 (1) | S1—C15—S2 | 123.53 (9) |
O4—C2—C1 | 107.6 (1) | S1—C15—N1 | 122.1 (1) |
O4—C2—C3 | 108.2 (1) | S2—C15—N1 | 114.2 (1) |
C1—C2—C3 | 112.0 (1) | S2—C16—N2 | 113.3 (1) |
O6—C3—C2 | 108.0 (1) | S2—C16—C17 | 124.4 (1) |
O6—C3—C4 | 107.1 (1) | N2—C16—C17 | 122.3 (1) |
C2—C3—C4 | 109.9 (1) | C16—C17—C18 | 121.4 (2) |
O8—C4—C3 | 109.0 (1) | C16—C17—C22 | 119.2 (1) |
O8—C4—C5 | 110.1 (1) | C18—C17—C22 | 119.4 (2) |
C3—C4—C5 | 109.6 (1) | C17—C18—C19 | 119.9 (2) |
S1—C5—O1 | 109.1 (1) | C18—C19—C20 | 120.3 (2) |
S1—C5—C4 | 107.6 (1) | C19—C20—C21 | 120.3 (2) |
O1—C5—C4 | 107.7 (1) | C20—C21—C22 | 120.0 (2) |
O2—C6—C1 | 107.8 (1) | C17—C22—C21 | 120.0 (2) |
O2—C7—O3 | 123.7 (2) | ||
S1—C5—O1—C1 | 176.6 (1) | N2—C16—C17—C18 | 163.6 (2) |
S1—C5—C4—O8 | −60.2 (1) | N2—C16—C17—C22 | −17.1 (3) |
S1—C5—C4—C3 | 179.84 (10) | C1—O1—C5—C4 | −67.0 (2) |
S1—C15—S2—C16 | 175.9 (1) | C1—C2—O4—C9 | −113.7 (1) |
S1—C15—N1—N2 | −176.0 (1) | C1—C2—C3—C4 | 49.0 (2) |
S2—C15—S1—C5 | 78.1 (1) | C1—C6—O2—C7 | −143.7 (2) |
S2—C15—N1—N2 | −0.6 (2) | C2—O4—C9—C10 | 177.0 (1) |
S2—C16—N2—N1 | 0.2 (2) | C2—C1—O1—C5 | 61.4 (2) |
S2—C16—C17—C18 | −16.7 (2) | C2—C3—O6—C11 | 136.0 (1) |
S2—C16—C17—C22 | 162.6 (1) | C2—C3—C4—C5 | −54.2 (2) |
O1—C1—C2—O4 | −170.1 (1) | C3—O6—C11—C12 | 168.3 (1) |
O1—C1—C2—C3 | −51.3 (2) | C3—C2—O4—C9 | 125.0 (1) |
O1—C1—C6—O2 | −59.6 (2) | C3—C2—C1—C6 | −170.1 (1) |
O1—C5—S1—C15 | −67.2 (1) | C3—C4—O8—C13 | −117.8 (2) |
O1—C5—C4—O8 | −177.7 (1) | C4—O8—C13—C14 | −175.2 (2) |
O1—C5—C4—C3 | 62.4 (2) | C4—C3—O6—C11 | −105.7 (1) |
O2—C6—C1—C2 | 61.0 (2) | C4—C5—S1—C15 | 176.3 (1) |
O3—C7—O2—C6 | −1.0 (3) | C5—O1—C1—C6 | −176.6 (1) |
O4—C2—C1—C6 | 71.1 (2) | C5—C4—O8—C13 | 121.9 (1) |
O4—C2—C3—O6 | −76.1 (1) | C6—O2—C7—C8 | 179.4 (2) |
O4—C2—C3—C4 | 167.4 (1) | C15—S2—C16—C17 | 179.9 (2) |
O5—C9—O4—C2 | −2.0 (2) | C15—N1—N2—C16 | 0.2 (3) |
O6—C3—C2—C1 | 165.5 (1) | C16—C17—C18—C19 | −178.7 (2) |
O6—C3—C4—O8 | 68.2 (1) | C16—C17—C22—C21 | 178.6 (2) |
O6—C3—C4—C5 | −171.2 (1) | C17—C18—C19—C20 | −0.9 (3) |
O7—C11—O6—C3 | −10.4 (2) | C17—C22—C21—C20 | 1.2 (3) |
O8—C4—C3—C2 | −174.8 (1) | C18—C17—C22—C21 | −2.1 (3) |
O9—C13—O8—C4 | 4.8 (3) | C18—C19—C20—C21 | 0.0 (3) |
N1—N2—C16—C17 | 179.9 (2) | C19—C18—C17—C22 | 2.0 (3) |
N1—C15—S1—C5 | −107.0 (2) | C19—C20—C21—C22 | −0.1 (4) |
N1—C15—S2—C16 | 0.5 (2) | C19—C20—C21—C22 | −0.1 (4) |
N2—C16—S2—C15 | −0.4 (2) |
1,3,4-Thiadiazole derivatives display a broad spectrum of biological activities, such as fungicidal (Zou et al., 2002), antibacterial (Deibel et al., 2004), antidepressant (Clerici et al., 2001) and antiepileptic (Masereel et al., 2002) properties. However, the application of 1,3,4-thiadiazoles is limited because of their poor solubility, both in organic solvents and in water. In the course of identifying new chemical structures that may serve as leads in the design of novel antiviral agents, we were particularly interested in the linking of thio-1,3,4-thiadiazoles to hydrophilic moieties such as D-glucose. The present structure determination is part of an investigation into the nucleophilic substitution of a bromosugar to a thioheterocyclic compound. Here, we report the X-ray crystal structure determination of the title compound (I) (Fig. 1).
The 2,3,4,6-tetra-O-acetyglucopyranosyl ring of (I) assumes a 4C1 chair conformation, with atoms C2 and C5 displaced from the C1—C3—C4—O1 mean plane. The mean C—C and C—O(hydroxyl) bond lengths of 1.519 (2) and 1.422 (2) Å, respectively, in the sugar moiety compare well with similar averages observed in pyranose sugars (Berman et al., 1967). The two endocyclic C—O bonds, C1—O1 and C5—O1, are nearly equal [1.432 (2) and 1.422 (2) Å, respectively]. The conformation about the exocyclic C1—C6 bond is gauche–trans, with torsion angles O2—C6—C1—O1 = −59.7 (2)° and O2—C6—C1—C2 = 60.9 (2)°.
The heterocyclic phenyl-1,3,4-thiadiazole ring is planar to within experimental error and the lengths of the endocyclic bonds, C15—N1 = 1.299 (2) Å and C16—N2 = 1.306 (2) Å, clearly indicate that they are double bonds. The N1—N2 bond length of 1.375 (2) Å is slightly shorter than the single-bond value of 1.393 (4) Å in the hydrochloride of 5-(4-methoxyphenyl)-4-phenyl-1,3,4-thiadiazolium-2-phenylaminide (Cheung et al., 1992). The large deviation of the bond angle (Value?) in the ring from the value of 120° usually found in trigonal planar arrangements is common in five-membered rings (Downie et al., 1972). The phenyl ring linked to atom C16 forms a dihedral angle of 16.95 (6)° with the heterocyclic plane.
The S atom of the thioglucosidic linkage bridges the sugar and heterocyclic rings. The dihedral angles between the mean plane of the sugar ring and the thiadiazole and phenyl planes are 49.54 (4) and 33.42 (5)°, respectively. The orientation of the thiadiazole moiety relative to the glucose ring may be described by the torsion angles N1—C15—S1—C5 = −106.9 (2)°, S2—C15—S1—C5 = 78.2 (1)°, C15—S1—C5—O1 = −67.1 (1)° and C15—S1—C5—C4 = 176.3 (1)°.