Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105007833/av1224sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105007833/av1224Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105007833/av1224IIsup3.hkl |
CCDC references: 275535; 275536
For the preparation of (I), triethylamine (404 mg, 4 mmol) was added at 298 K under nitrogen to a stirred mixture of 4,6-dimethylpyrimidine-2-thiol (280 mg, 2 mmol) and (III) (476 mg, 2 mmol) (Hui Huang et al., 1999) in dimethylformamide (8 ml). The mixture was stirred at room temperature. The completion of the reaction was monitored using thin-layer chromatography. CH2Cl2 was added to the mixture, which was then filtered. The filtrate was washed with H2O, dried, and condensed in vacuo to give the crude product. Column chromatography gave colourless crystals of (I) (417 mg, 55%; m.p. 415.8–416.2 K). Recrystallization from petroleum–AcOEt (Ratio?) yielded crystals of (I) suitable for X-ray analysis. For the preparation of (II), to a mixture of 2-amino-4-methylthiazolyl (484 mg, 2 mmol), K2CO3 (1.11 g, 8 mmol) and tetrabutylammoniumbromide (322 mg, 1 mmol) was added CH3CN (6 ml) and (III) (476 mg, 2 mmol). The reaction solution was stirred at room temperature for 2 d. AcOEt was added and the resulting mixture was washed with water and condensed in vacuo to provide the crude product, which was purified by flash chromatography, giving (II) as a light-yellow crystals (359 mg, 51%; m.p.466.5–468 K). Recrystallization from petroleum–AcOEt (Ratio?) yielded crystals of (II).
H atoms were generated goemetrically and allowed to ride on their parent C atoms, with C—H distances of 0.96 (CH3), 0.97 (CH2), 0.98 Å (CH) or 0.93 Å (unsaturated CH), and N—H distances of 0.86°, and with Uico(H) = 1.2Ueq(C,N). Please check added text. The absolute structure was set by reference to the known chirality of the cyclohexyloxy moiety.
For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C20H30N2O3S | Dx = 1.162 Mg m−3 |
Mr = 378.52 | Melting point = 415.8–416.2 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 956 reflections |
a = 8.825 (4) Å | θ = 2.7–25.5° |
b = 14.401 (6) Å | µ = 0.17 mm−1 |
c = 17.033 (7) Å | T = 293 K |
V = 2164.5 (15) Å3 | Prism, colourless |
Z = 4 | 0.42 × 0.32 × 0.26 mm |
F(000) = 816 |
Bruker SMART CCD area-detector diffractometer | 4425 independent reflections |
Radiation source: fine-focus sealed tube | 3686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 26.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→10 |
Tmin = 0.977, Tmax = 0.996 | k = −17→17 |
12564 measured reflections | l = −21→10 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.037 | w = 1/[σ2(Fo2) + (0.0476P)2 + 0.2336P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max = 0.001 |
S = 1.06 | Δρmax = 0.15 e Å−3 |
4425 reflections | Δρmin = −0.15 e Å−3 |
242 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.033 (2) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with how many Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.00 (7) |
C20H30N2O3S | V = 2164.5 (15) Å3 |
Mr = 378.52 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.825 (4) Å | µ = 0.17 mm−1 |
b = 14.401 (6) Å | T = 293 K |
c = 17.033 (7) Å | 0.42 × 0.32 × 0.26 mm |
Bruker SMART CCD area-detector diffractometer | 4425 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3686 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.996 | Rint = 0.029 |
12564 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.097 | Δρmax = 0.15 e Å−3 |
S = 1.06 | Δρmin = −0.15 e Å−3 |
4425 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
242 parameters | Absolute structure parameter: 0.00 (7) |
0 restraints |
Experimental. 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 0.81 (3H, d, J = 6.9 Hz, H12), 0.92 (3H, d, J = 7.1 Hz, H14), 0.94 (3H, d, J = 6.6 Hz, H15), 0.97 (2H, m, H10), 1.01 (1H, m, H13), 1.29 (2H, m, H9), 1.69 (2H, m, H7), 2.13 (2H, m, H8, H11), 2.44 (6H, s, H8', H7'), 2.62 (1H, dd, J = 18.4, 2.6 Hz, H3), 3.26 (1H, dd, J = 18.4 and 9.0 Hz, H3), 3.56 (1H, dt, J = 10.7 and 4.1 Hz, H6), 4.15 (1H, dd, J = 8.8 and 1.0 Hz, H4), 5.73 (1H, s, H5), 6.79 (1H, s, H5'); 13C NMR (135DEPT, 125 MHz, CDCl3, δ, p.p.m.): 15.6 (C15), 20.9 (C14), 22.2 (C12), 3.1 (C10), 23.8 (C7',8'), 25.5 (t, C13), 31.3 (C8), 33.6 (C9), 34.3 (C3), 40.2 (C7), 44.4 (C11), 47.8 (C4), 77.6 (C6), 104.6 (C5), 116.6 (C5'), 167.6 (C4',6'), 169.1 (C2'), 175.0 (C2); IR (KBr, cm−1): ν 1778(C=O). |
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 | ||
S1 | 0.62843 (5) | 0.48529 (3) | 0.98734 (3) | 0.05309 (16) | |
N1 | 0.33120 (17) | 0.48972 (11) | 0.96069 (10) | 0.0516 (4) | |
N2 | 0.46554 (18) | 0.63351 (11) | 0.96853 (10) | 0.0533 (4) | |
O1 | 0.69087 (15) | 0.32620 (10) | 0.84871 (8) | 0.0520 (3) | |
O2 | 0.90826 (17) | 0.26210 (14) | 0.88812 (12) | 0.0808 (5) | |
O3 | 0.45180 (15) | 0.27066 (9) | 0.87819 (7) | 0.0470 (3) | |
C1 | 0.7869 (2) | 0.29372 (14) | 0.90440 (13) | 0.0527 (5) | |
C2 | 0.7177 (2) | 0.30465 (14) | 0.98371 (12) | 0.0525 (5) | |
H2A | 0.7877 | 0.3347 | 1.0195 | 0.063* | |
H2B | 0.6890 | 0.2448 | 1.0053 | 0.063* | |
C3 | 0.57801 (19) | 0.36530 (13) | 0.96988 (11) | 0.0426 (4) | |
H3 | 0.4930 | 0.3459 | 1.0031 | 0.051* | |
C4 | 0.54515 (19) | 0.34749 (13) | 0.88331 (11) | 0.0405 (4) | |
H4 | 0.4988 | 0.4019 | 0.8584 | 0.049* | |
C5 | 0.3968 (3) | 0.25032 (15) | 0.79984 (12) | 0.0563 (6) | |
H5 | 0.4758 | 0.2660 | 0.7616 | 0.068* | |
C6 | 0.3671 (4) | 0.14551 (19) | 0.79691 (13) | 0.0776 (8) | |
H6 | 0.2880 | 0.1326 | 0.8358 | 0.093* | |
C7 | 0.2994 (5) | 0.1228 (3) | 0.71627 (19) | 0.1120 (13) | |
H7A | 0.3752 | 0.1339 | 0.6761 | 0.134* | |
H7B | 0.2727 | 0.0575 | 0.7146 | 0.134* | |
C8 | 0.1606 (5) | 0.1802 (3) | 0.69856 (19) | 0.1225 (15) | |
H8A | 0.0814 | 0.1642 | 0.7357 | 0.147* | |
H8B | 0.1244 | 0.1647 | 0.6464 | 0.147* | |
C9 | 0.1900 (4) | 0.2841 (3) | 0.70275 (16) | 0.0994 (10) | |
H9 | 0.2652 | 0.2997 | 0.6625 | 0.119* | |
C10 | 0.2582 (3) | 0.3074 (2) | 0.78310 (13) | 0.0701 (7) | |
H10A | 0.2847 | 0.3727 | 0.7846 | 0.084* | |
H10B | 0.1832 | 0.2961 | 0.8236 | 0.084* | |
C11 | 0.5040 (5) | 0.08683 (19) | 0.81967 (18) | 0.0943 (10) | |
H11 | 0.5419 | 0.1112 | 0.8696 | 0.113* | |
C12 | 0.6343 (4) | 0.0926 (2) | 0.7608 (2) | 0.1152 (12) | |
H12A | 0.6049 | 0.0629 | 0.7127 | 0.173* | |
H12B | 0.7218 | 0.0620 | 0.7820 | 0.173* | |
H12C | 0.6579 | 0.1566 | 0.7507 | 0.173* | |
C13 | 0.4601 (6) | −0.0152 (2) | 0.8338 (2) | 0.1445 (18) | |
H13A | 0.3891 | −0.0187 | 0.8764 | 0.217* | |
H13B | 0.5492 | −0.0503 | 0.8466 | 0.217* | |
H13C | 0.4147 | −0.0401 | 0.7871 | 0.217* | |
C14 | 0.0495 (4) | 0.3430 (4) | 0.6878 (2) | 0.1458 (18) | |
H14A | 0.0096 | 0.3291 | 0.6367 | 0.219* | |
H14B | 0.0761 | 0.4076 | 0.6904 | 0.219* | |
H14C | −0.0256 | 0.3295 | 0.7269 | 0.219* | |
C15 | 0.4544 (2) | 0.54139 (13) | 0.97053 (11) | 0.0457 (4) | |
C16 | 0.2026 (2) | 0.53660 (16) | 0.94678 (14) | 0.0582 (5) | |
C17 | 0.2028 (2) | 0.63179 (17) | 0.94293 (15) | 0.0647 (6) | |
H17 | 0.1136 | 0.6641 | 0.9331 | 0.078* | |
C18 | 0.3372 (3) | 0.67880 (15) | 0.95390 (13) | 0.0595 (5) | |
C19 | 0.0622 (3) | 0.4795 (2) | 0.9355 (2) | 0.0914 (9) | |
H19A | 0.0545 | 0.4611 | 0.8815 | 0.137* | |
H19B | −0.0251 | 0.5156 | 0.9496 | 0.137* | |
H19C | 0.0673 | 0.4252 | 0.9681 | 0.137* | |
C20 | 0.3451 (4) | 0.78280 (18) | 0.9474 (2) | 0.0960 (9) | |
H20A | 0.4491 | 0.8023 | 0.9487 | 0.144* | |
H20B | 0.2914 | 0.8104 | 0.9906 | 0.144* | |
H20C | 0.2998 | 0.8022 | 0.8989 | 0.144* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0396 (2) | 0.0484 (3) | 0.0713 (3) | −0.0008 (2) | −0.0143 (2) | −0.0077 (2) |
N1 | 0.0377 (8) | 0.0481 (9) | 0.0691 (11) | −0.0005 (7) | −0.0016 (7) | −0.0031 (8) |
N2 | 0.0527 (10) | 0.0451 (9) | 0.0622 (11) | 0.0009 (8) | −0.0056 (8) | −0.0057 (8) |
O1 | 0.0449 (7) | 0.0633 (9) | 0.0479 (8) | −0.0031 (7) | 0.0055 (6) | 0.0076 (6) |
O2 | 0.0498 (9) | 0.0977 (14) | 0.0949 (13) | 0.0181 (9) | 0.0091 (9) | 0.0041 (10) |
O3 | 0.0532 (8) | 0.0495 (7) | 0.0385 (7) | −0.0144 (6) | 0.0019 (6) | −0.0005 (6) |
C1 | 0.0438 (11) | 0.0499 (11) | 0.0644 (14) | −0.0011 (9) | 0.0006 (10) | 0.0066 (10) |
C2 | 0.0541 (11) | 0.0511 (11) | 0.0522 (11) | 0.0065 (9) | −0.0086 (10) | 0.0074 (9) |
C3 | 0.0387 (9) | 0.0438 (9) | 0.0453 (10) | −0.0013 (7) | −0.0050 (8) | 0.0034 (8) |
C4 | 0.0374 (9) | 0.0407 (10) | 0.0433 (10) | −0.0037 (8) | −0.0019 (8) | 0.0058 (8) |
C5 | 0.0642 (14) | 0.0692 (14) | 0.0355 (11) | −0.0219 (11) | 0.0056 (9) | −0.0056 (9) |
C6 | 0.108 (2) | 0.0790 (17) | 0.0462 (12) | −0.0412 (17) | 0.0197 (14) | −0.0183 (11) |
C7 | 0.146 (3) | 0.121 (3) | 0.0694 (19) | −0.058 (3) | 0.007 (2) | −0.0386 (18) |
C8 | 0.126 (3) | 0.175 (4) | 0.0665 (19) | −0.069 (3) | −0.021 (2) | −0.025 (2) |
C9 | 0.092 (2) | 0.150 (3) | 0.0555 (16) | −0.038 (2) | −0.0197 (15) | 0.0054 (17) |
C10 | 0.0602 (14) | 0.0992 (19) | 0.0511 (13) | −0.0207 (13) | −0.0109 (10) | 0.0032 (12) |
C11 | 0.149 (3) | 0.0609 (15) | 0.0731 (18) | −0.0034 (19) | 0.0283 (19) | −0.0085 (13) |
C12 | 0.141 (3) | 0.086 (2) | 0.119 (3) | 0.009 (2) | 0.037 (3) | −0.0099 (19) |
C13 | 0.248 (5) | 0.0610 (17) | 0.124 (3) | −0.006 (3) | 0.077 (3) | −0.0092 (18) |
C14 | 0.094 (2) | 0.252 (5) | 0.091 (2) | −0.026 (3) | −0.050 (2) | 0.034 (3) |
C15 | 0.0438 (10) | 0.0480 (10) | 0.0454 (11) | 0.0018 (8) | −0.0037 (9) | −0.0044 (8) |
C16 | 0.0408 (10) | 0.0645 (14) | 0.0692 (14) | 0.0028 (10) | 0.0016 (10) | −0.0007 (11) |
C17 | 0.0476 (12) | 0.0628 (14) | 0.0837 (16) | 0.0145 (11) | −0.0034 (11) | −0.0003 (12) |
C18 | 0.0598 (13) | 0.0526 (12) | 0.0661 (13) | 0.0085 (10) | −0.0035 (11) | −0.0047 (10) |
C19 | 0.0394 (11) | 0.0879 (19) | 0.147 (3) | −0.0045 (13) | −0.0064 (14) | 0.0031 (19) |
C20 | 0.095 (2) | 0.0532 (14) | 0.140 (3) | 0.0088 (14) | −0.026 (2) | −0.0021 (15) |
S1—C15 | 1.759 (2) | C8—H8B | 0.9700 |
S1—C3 | 1.809 (2) | C9—C14 | 1.523 (5) |
N1—C15 | 1.328 (2) | C9—C10 | 1.533 (3) |
N1—C16 | 1.342 (3) | C9—H9 | 0.9800 |
N2—C18 | 1.330 (3) | C10—H10A | 0.9700 |
N2—C15 | 1.331 (2) | C10—H10B | 0.9700 |
O1—C1 | 1.355 (2) | C11—C12 | 1.528 (5) |
O1—C4 | 1.447 (2) | C11—C13 | 1.538 (4) |
O2—C1 | 1.196 (2) | C11—H11 | 0.9800 |
O3—C4 | 1.382 (2) | C12—H12A | 0.9600 |
O3—C5 | 1.450 (2) | C12—H12B | 0.9600 |
C1—C2 | 1.491 (3) | C12—H12C | 0.9600 |
C2—C3 | 1.529 (2) | C13—H13A | 0.9600 |
C2—H2A | 0.9700 | C13—H13B | 0.9600 |
C2—H2B | 0.9700 | C13—H13C | 0.9600 |
C3—C4 | 1.524 (3) | C14—H14A | 0.9600 |
C3—H3 | 0.9800 | C14—H14B | 0.9600 |
C4—H4 | 0.9800 | C14—H14C | 0.9600 |
C5—C10 | 1.501 (3) | C16—C17 | 1.372 (3) |
C5—C6 | 1.533 (3) | C16—C19 | 1.499 (3) |
C5—H5 | 0.9800 | C17—C18 | 1.378 (3) |
C6—C11 | 1.524 (5) | C17—H17 | 0.9300 |
C6—C7 | 1.533 (4) | C18—C20 | 1.503 (3) |
C6—H6 | 0.9800 | C19—H19A | 0.9600 |
C7—C8 | 1.508 (5) | C19—H19B | 0.9600 |
C7—H7A | 0.9700 | C19—H19C | 0.9600 |
C7—H7B | 0.9700 | C20—H20A | 0.9600 |
C8—C9 | 1.521 (5) | C20—H20B | 0.9600 |
C8—H8A | 0.9700 | C20—H20C | 0.9600 |
C15—S1—C3 | 101.37 (9) | C10—C9—H9 | 107.9 |
C15—N1—C16 | 115.65 (17) | C5—C10—C9 | 111.7 (2) |
C18—N2—C15 | 115.50 (17) | C5—C10—H10A | 109.3 |
C1—O1—C4 | 110.11 (14) | C9—C10—H10A | 109.3 |
C4—O3—C5 | 114.79 (14) | C5—C10—H10B | 109.3 |
O2—C1—O1 | 121.9 (2) | C9—C10—H10B | 109.3 |
O2—C1—C2 | 128.1 (2) | H10A—C10—H10B | 107.9 |
O1—C1—C2 | 109.95 (16) | C6—C11—C12 | 113.5 (3) |
C1—C2—C3 | 104.55 (16) | C6—C11—C13 | 111.7 (3) |
C1—C2—H2A | 110.8 | C12—C11—C13 | 110.1 (3) |
C3—C2—H2A | 110.8 | C6—C11—H11 | 107.0 |
C1—C2—H2B | 110.8 | C12—C11—H11 | 107.0 |
C3—C2—H2B | 110.8 | C13—C11—H11 | 107.0 |
H2A—C2—H2B | 108.9 | C11—C12—H12A | 109.5 |
C4—C3—C2 | 101.90 (15) | C11—C12—H12B | 109.5 |
C4—C3—S1 | 111.50 (13) | H12A—C12—H12B | 109.5 |
C2—C3—S1 | 108.79 (13) | C11—C12—H12C | 109.5 |
C4—C3—H3 | 111.4 | H12A—C12—H12C | 109.5 |
C2—C3—H3 | 111.4 | H12B—C12—H12C | 109.5 |
S1—C3—H3 | 111.4 | C11—C13—H13A | 109.5 |
O3—C4—O1 | 109.53 (15) | C11—C13—H13B | 109.5 |
O3—C4—C3 | 108.01 (14) | H13A—C13—H13B | 109.5 |
O1—C4—C3 | 105.10 (14) | C11—C13—H13C | 109.5 |
O3—C4—H4 | 111.3 | H13A—C13—H13C | 109.5 |
O1—C4—H4 | 111.3 | H13B—C13—H13C | 109.5 |
C3—C4—H4 | 111.3 | C9—C14—H14A | 109.5 |
O3—C5—C10 | 109.69 (17) | C9—C14—H14B | 109.5 |
O3—C5—C6 | 106.64 (17) | H14A—C14—H14B | 109.5 |
C10—C5—C6 | 113.2 (2) | C9—C14—H14C | 109.5 |
O3—C5—H5 | 109.1 | H14A—C14—H14C | 109.5 |
C10—C5—H5 | 109.1 | H14B—C14—H14C | 109.5 |
C6—C5—H5 | 109.1 | N1—C15—N2 | 128.02 (18) |
C11—C6—C5 | 113.7 (2) | N1—C15—S1 | 118.55 (14) |
C11—C6—C7 | 114.7 (3) | N2—C15—S1 | 113.42 (14) |
C5—C6—C7 | 107.8 (2) | N1—C16—C17 | 120.6 (2) |
C11—C6—H6 | 106.7 | N1—C16—C19 | 116.5 (2) |
C5—C6—H6 | 106.7 | C17—C16—C19 | 122.9 (2) |
C7—C6—H6 | 106.7 | C16—C17—C18 | 119.1 (2) |
C8—C7—C6 | 112.2 (3) | C16—C17—H17 | 120.5 |
C8—C7—H7A | 109.2 | C18—C17—H17 | 120.5 |
C6—C7—H7A | 109.2 | N2—C18—C17 | 121.1 (2) |
C8—C7—H7B | 109.2 | N2—C18—C20 | 117.6 (2) |
C6—C7—H7B | 109.2 | C16—C19—H19A | 109.5 |
H7A—C7—H7B | 107.9 | C16—C19—H19B | 109.5 |
C7—C8—C9 | 113.1 (3) | H19A—C19—H19B | 109.5 |
C7—C8—H8A | 109.0 | C16—C19—H19C | 109.5 |
C9—C8—H8A | 109.0 | H19A—C19—H19C | 109.5 |
C7—C8—H8B | 109.0 | H19B—C19—H19C | 109.5 |
C9—C8—H8B | 109.0 | C18—C20—H20A | 109.5 |
H8A—C8—H8B | 107.8 | C18—C20—H20B | 109.5 |
C8—C9—C14 | 113.7 (3) | H20A—C20—H20B | 109.5 |
C8—C9—C10 | 108.9 (3) | C18—C20—H20C | 109.5 |
C14—C9—C10 | 110.3 (3) | H20A—C20—H20C | 109.5 |
C8—C9—H9 | 107.9 | H20B—C20—H20C | 109.5 |
C14—C9—H9 | 107.9 | ||
C4—O1—C1—O2 | 171.7 (2) | C7—C8—C9—C14 | −178.0 (3) |
C4—O1—C1—C2 | −8.6 (2) | C7—C8—C9—C10 | −54.5 (4) |
O2—C1—C2—C3 | 169.3 (2) | O3—C5—C10—C9 | −176.5 (2) |
O1—C1—C2—C3 | −10.4 (2) | C6—C5—C10—C9 | −57.6 (3) |
C1—C2—C3—C4 | 23.61 (18) | C8—C9—C10—C5 | 54.4 (3) |
C1—C2—C3—S1 | −94.25 (16) | C14—C9—C10—C5 | 179.8 (3) |
C15—S1—C3—C4 | 69.56 (14) | C5—C6—C11—C12 | −67.5 (3) |
C15—S1—C3—C2 | −178.84 (13) | C7—C6—C11—C12 | 57.3 (3) |
C5—O3—C4—O1 | −72.27 (19) | C5—C6—C11—C13 | 167.3 (2) |
C5—O3—C4—C3 | 173.77 (16) | C7—C6—C11—C13 | −68.0 (3) |
C1—O1—C4—O3 | −91.68 (17) | C16—N1—C15—N2 | 0.3 (3) |
C1—O1—C4—C3 | 24.14 (19) | C16—N1—C15—S1 | −178.91 (16) |
C2—C3—C4—O3 | 88.10 (17) | C18—N2—C15—N1 | −0.9 (3) |
S1—C3—C4—O3 | −156.00 (12) | C18—N2—C15—S1 | 178.30 (16) |
C2—C3—C4—O1 | −28.76 (17) | C3—S1—C15—N1 | 8.52 (18) |
S1—C3—C4—O1 | 87.14 (15) | C3—S1—C15—N2 | −170.76 (15) |
C4—O3—C5—C10 | −84.5 (2) | C15—N1—C16—C17 | 0.3 (3) |
C4—O3—C5—C6 | 152.61 (19) | C15—N1—C16—C19 | 180.0 (2) |
O3—C5—C6—C11 | −55.1 (3) | N1—C16—C17—C18 | −0.3 (4) |
C10—C5—C6—C11 | −175.76 (19) | C19—C16—C17—C18 | −179.9 (2) |
O3—C5—C6—C7 | 176.5 (2) | C15—N2—C18—C17 | 0.9 (3) |
C10—C5—C6—C7 | 55.9 (3) | C15—N2—C18—C20 | −177.3 (2) |
C11—C6—C7—C8 | 177.6 (3) | C16—C17—C18—N2 | −0.4 (4) |
C5—C6—C7—C8 | −54.6 (3) | C16—C17—C18—C20 | 177.8 (2) |
C6—C7—C8—C9 | 56.7 (4) |
C18H28N2O3S | Dx = 1.200 Mg m−3 |
Mr = 352.48 | Melting point = 466.5–468.3 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 826 reflections |
a = 8.841 (3) Å | θ = 3.1–23.1° |
b = 11.203 (3) Å | µ = 0.18 mm−1 |
c = 19.692 (6) Å | T = 293 K |
V = 1950.3 (10) Å3 | Prism, yellow |
Z = 4 | 0.34 × 0.22 × 0.18 mm |
F(000) = 760 |
Bruker SMART CCD area-detector diffractometer | 3997 independent reflections |
Radiation source: fine-focus sealed tube | 2992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 26.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→11 |
Tmin = 0.913, Tmax = 0.970 | k = −13→14 |
11333 measured reflections | l = −24→17 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0472P)2 + 0.1182P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.013 |
3997 reflections | Δρmax = 0.16 e Å−3 |
221 parameters | Δρmin = −0.17 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (8) |
C18H28N2O3S | V = 1950.3 (10) Å3 |
Mr = 352.48 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.841 (3) Å | µ = 0.18 mm−1 |
b = 11.203 (3) Å | T = 293 K |
c = 19.692 (6) Å | 0.34 × 0.22 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 3997 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2992 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 0.970 | Rint = 0.031 |
11333 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 0.16 e Å−3 |
S = 1.06 | Δρmin = −0.17 e Å−3 |
3997 reflections | Absolute structure: Flack (1983), with how many Friedel pairs |
221 parameters | Absolute structure parameter: −0.03 (8) |
1 restraint |
Experimental. 1H NMR (500 MHz, CDCl3, δ, p.p.m.): 0.79 (3H, d, J = 6.9 Hz, H12), 0.88 (H, m, H10), 0.90 (3H, d, J = 7.1 Hz, H14), 0.96 (3H, d, J = 6.5 Hz, H15), 1.02 (2H, m, H10, H13), 1.27 (2H, m, H9), 1.67 (2H, m, H7), 2.05 (1H, m, H11), 2.19 (1H, m, H8), 2.26 (3H, s, H6'), 2.50 (1H, d, J = 18.1 Hz, H3), 3.32 (1H, dd, J = 18.1 and 7.3 Hz, H3), 3.55 (1H, dt, J = 10.7 and 6.6 Hz, H6), 4.22 (1H, d, J = 6.9 Hz, H4), 5.73 (1H, s, H5), 6.17 (1H, s, H5'); 13C NMR (125 MHz, CDCl3, δ, p.p.m): 15.6 (C15), 17.2 (C6'), 20.9 (C14), 23.1 (C10), 25.6 (C13), 31.4 (C8), 34.2 (C3, C9), 39.7 (C7), 47.6 (C11), 57.3 (C4), 77.7 (C6), 102.4 (C5), 103.7 (C5'), 138.3 (C2'), 166.6 (C5); IR (KBr, cm−1): ν 1778 (C=O). |
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 | ||
S1 | −0.14879 (8) | 0.22367 (6) | 0.22496 (4) | 0.0693 (2) | |
N1 | 0.0071 (2) | 0.32833 (17) | 0.12363 (9) | 0.0540 (5) | |
H1 | −0.0308 | 0.2749 | 0.0973 | 0.065* | |
N2 | 0.0458 (2) | 0.39337 (16) | 0.23518 (9) | 0.0497 (4) | |
O1 | 0.32722 (17) | 0.33004 (13) | 0.05899 (8) | 0.0572 (4) | |
O2 | 0.2752 (2) | 0.30145 (18) | −0.05033 (9) | 0.0882 (6) | |
O3 | 0.34001 (15) | 0.50952 (11) | 0.11756 (7) | 0.0452 (3) | |
C1 | 0.2406 (3) | 0.3434 (2) | 0.00327 (12) | 0.0560 (6) | |
C2 | 0.1045 (3) | 0.4157 (2) | 0.01931 (10) | 0.0513 (5) | |
H2A | 0.0139 | 0.3777 | 0.0019 | 0.062* | |
H2B | 0.1127 | 0.4950 | −0.0001 | 0.062* | |
C3 | 0.1008 (2) | 0.42168 (19) | 0.09624 (10) | 0.0426 (5) | |
H3 | 0.0665 | 0.5003 | 0.1118 | 0.051* | |
C4 | 0.2669 (2) | 0.40099 (18) | 0.11472 (11) | 0.0449 (5) | |
H4 | 0.2759 | 0.3582 | 0.1580 | 0.054* | |
C5 | 0.4856 (2) | 0.50793 (18) | 0.15171 (10) | 0.0411 (5) | |
H5 | 0.5394 | 0.4342 | 0.1400 | 0.049* | |
C6 | 0.5742 (2) | 0.6141 (2) | 0.12578 (11) | 0.0494 (5) | |
H6 | 0.5156 | 0.6853 | 0.1376 | 0.059* | |
C7 | 0.7230 (3) | 0.6217 (3) | 0.16558 (14) | 0.0796 (8) | |
H7A | 0.7842 | 0.5520 | 0.1555 | 0.095* | |
H7B | 0.7787 | 0.6917 | 0.1509 | 0.095* | |
C8 | 0.6973 (4) | 0.6288 (3) | 0.24116 (13) | 0.0850 (9) | |
H8A | 0.6435 | 0.7019 | 0.2517 | 0.102* | |
H8B | 0.7942 | 0.6314 | 0.2642 | 0.102* | |
C9 | 0.6075 (3) | 0.5236 (2) | 0.26728 (11) | 0.0640 (6) | |
H9 | 0.6671 | 0.4513 | 0.2591 | 0.077* | |
C10 | 0.4604 (2) | 0.5124 (2) | 0.22740 (11) | 0.0570 (6) | |
H10A | 0.4082 | 0.4405 | 0.2416 | 0.068* | |
H10B | 0.3959 | 0.5799 | 0.2380 | 0.068* | |
C11 | 0.5946 (3) | 0.6162 (2) | 0.04876 (12) | 0.0617 (6) | |
H11 | 0.4945 | 0.6016 | 0.0290 | 0.074* | |
C12 | 0.6960 (4) | 0.5201 (4) | 0.02260 (15) | 0.1237 (15) | |
H12A | 0.6963 | 0.5216 | −0.0261 | 0.186* | |
H12B | 0.6601 | 0.4439 | 0.0380 | 0.186* | |
H12C | 0.7969 | 0.5329 | 0.0391 | 0.186* | |
C13 | 0.6448 (6) | 0.7383 (4) | 0.02369 (15) | 0.1303 (16) | |
H13A | 0.7458 | 0.7541 | 0.0393 | 0.196* | |
H13B | 0.5776 | 0.7983 | 0.0410 | 0.196* | |
H13C | 0.6429 | 0.7397 | −0.0251 | 0.196* | |
C14 | 0.5763 (4) | 0.5313 (4) | 0.34349 (13) | 0.1102 (12) | |
H14A | 0.5131 | 0.5991 | 0.3526 | 0.165* | |
H14B | 0.6702 | 0.5397 | 0.3675 | 0.165* | |
H14C | 0.5260 | 0.4599 | 0.3582 | 0.165* | |
C15 | −0.0212 (2) | 0.32530 (19) | 0.19166 (11) | 0.0479 (5) | |
C16 | −0.0043 (3) | 0.3657 (2) | 0.30031 (11) | 0.0546 (6) | |
C17 | −0.1064 (3) | 0.2785 (2) | 0.30402 (13) | 0.0653 (6) | |
H17 | −0.1491 | 0.2509 | 0.3442 | 0.078* | |
C18 | 0.0602 (4) | 0.4356 (3) | 0.35836 (12) | 0.0815 (9) | |
H18A | 0.0235 | 0.5162 | 0.3565 | 0.122* | |
H18B | 0.1686 | 0.4357 | 0.3553 | 0.122* | |
H18C | 0.0298 | 0.3996 | 0.4005 | 0.122* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0646 (4) | 0.0651 (4) | 0.0783 (4) | −0.0231 (3) | 0.0202 (3) | −0.0026 (3) |
N1 | 0.0498 (11) | 0.0667 (12) | 0.0454 (10) | −0.0211 (10) | 0.0031 (9) | −0.0102 (9) |
N2 | 0.0503 (10) | 0.0568 (10) | 0.0418 (10) | −0.0091 (9) | 0.0029 (8) | 0.0002 (8) |
O1 | 0.0433 (8) | 0.0552 (9) | 0.0733 (10) | 0.0090 (7) | 0.0017 (8) | −0.0080 (8) |
O2 | 0.0916 (14) | 0.1071 (15) | 0.0658 (12) | 0.0254 (12) | 0.0211 (11) | −0.0296 (11) |
O3 | 0.0340 (7) | 0.0455 (8) | 0.0562 (8) | −0.0017 (6) | −0.0077 (7) | 0.0043 (7) |
C1 | 0.0530 (14) | 0.0582 (14) | 0.0568 (14) | 0.0021 (12) | 0.0065 (13) | −0.0054 (12) |
C2 | 0.0473 (12) | 0.0646 (14) | 0.0421 (12) | 0.0068 (11) | 0.0030 (10) | −0.0014 (10) |
C3 | 0.0367 (10) | 0.0521 (12) | 0.0389 (11) | −0.0020 (9) | 0.0019 (8) | −0.0029 (9) |
C4 | 0.0395 (11) | 0.0464 (11) | 0.0487 (12) | −0.0028 (10) | −0.0008 (10) | 0.0053 (10) |
C5 | 0.0339 (10) | 0.0433 (11) | 0.0463 (11) | 0.0039 (9) | −0.0041 (9) | 0.0000 (9) |
C6 | 0.0425 (12) | 0.0519 (12) | 0.0537 (13) | −0.0044 (10) | −0.0042 (10) | 0.0000 (10) |
C7 | 0.0581 (16) | 0.110 (2) | 0.0708 (17) | −0.0362 (16) | −0.0157 (14) | 0.0111 (16) |
C8 | 0.085 (2) | 0.097 (2) | 0.0740 (19) | −0.0230 (17) | −0.0324 (16) | −0.0075 (16) |
C9 | 0.0639 (15) | 0.0769 (16) | 0.0511 (13) | 0.0088 (14) | −0.0087 (12) | −0.0038 (12) |
C10 | 0.0495 (13) | 0.0745 (15) | 0.0470 (12) | 0.0027 (12) | 0.0018 (11) | 0.0004 (12) |
C11 | 0.0524 (14) | 0.0797 (16) | 0.0531 (14) | −0.0112 (13) | −0.0006 (11) | 0.0075 (12) |
C12 | 0.105 (3) | 0.196 (4) | 0.070 (2) | 0.060 (3) | 0.0264 (19) | 0.003 (2) |
C13 | 0.173 (4) | 0.138 (3) | 0.080 (2) | −0.076 (3) | −0.007 (2) | 0.038 (2) |
C14 | 0.127 (3) | 0.156 (3) | 0.0478 (16) | 0.008 (3) | −0.0198 (18) | −0.0037 (18) |
C15 | 0.0389 (11) | 0.0500 (12) | 0.0548 (13) | −0.0058 (10) | 0.0061 (10) | −0.0004 (10) |
C16 | 0.0561 (13) | 0.0581 (14) | 0.0496 (13) | 0.0041 (12) | 0.0088 (11) | 0.0081 (10) |
C17 | 0.0657 (16) | 0.0673 (15) | 0.0630 (15) | 0.0017 (14) | 0.0214 (12) | 0.0155 (13) |
C18 | 0.106 (2) | 0.096 (2) | 0.0426 (14) | −0.0075 (18) | 0.0019 (14) | 0.0019 (13) |
S1—C17 | 1.715 (3) | C7—H7B | 0.9700 |
S1—C15 | 1.732 (2) | C8—C9 | 1.511 (4) |
N1—C15 | 1.363 (3) | C8—H8A | 0.9700 |
N1—C3 | 1.439 (3) | C8—H8B | 0.9700 |
N1—H1 | 0.8600 | C9—C10 | 1.524 (3) |
N2—C15 | 1.291 (3) | C9—C14 | 1.528 (3) |
N2—C16 | 1.392 (3) | C9—H9 | 0.9800 |
O1—C1 | 1.347 (3) | C10—H10A | 0.9700 |
O1—C4 | 1.456 (3) | C10—H10B | 0.9700 |
O2—C1 | 1.195 (3) | C11—C12 | 1.493 (4) |
O3—C4 | 1.378 (2) | C11—C13 | 1.521 (4) |
O3—C5 | 1.452 (2) | C11—H11 | 0.9800 |
C1—C2 | 1.484 (3) | C12—H12A | 0.9600 |
C2—C3 | 1.517 (3) | C12—H12B | 0.9600 |
C2—H2A | 0.9700 | C12—H12C | 0.9600 |
C2—H2B | 0.9700 | C13—H13A | 0.9600 |
C3—C4 | 1.531 (3) | C13—H13B | 0.9600 |
C3—H3 | 0.9800 | C13—H13C | 0.9600 |
C4—H4 | 0.9800 | C14—H14A | 0.9600 |
C5—C10 | 1.508 (3) | C14—H14B | 0.9600 |
C5—C6 | 1.513 (3) | C14—H14C | 0.9600 |
C5—H5 | 0.9800 | C16—C17 | 1.332 (3) |
C6—C11 | 1.527 (3) | C16—C18 | 1.498 (3) |
C6—C7 | 1.534 (3) | C17—H17 | 0.9300 |
C6—H6 | 0.9800 | C18—H18A | 0.9600 |
C7—C8 | 1.508 (4) | C18—H18B | 0.9600 |
C7—H7A | 0.9700 | C18—H18C | 0.9600 |
C17—S1—C15 | 88.06 (11) | C8—C9—C10 | 109.7 (2) |
C15—N1—C3 | 119.47 (17) | C8—C9—C14 | 112.7 (2) |
C15—N1—H1 | 120.0 | C10—C9—C14 | 110.9 (2) |
C3—N1—H1 | 120.0 | C8—C9—H9 | 107.8 |
C15—N2—C16 | 109.52 (18) | C10—C9—H9 | 107.8 |
C1—O1—C4 | 110.18 (16) | C14—C9—H9 | 107.8 |
C4—O3—C5 | 115.06 (14) | C5—C10—C9 | 112.71 (18) |
O2—C1—O1 | 122.0 (2) | C5—C10—H10A | 109.1 |
O2—C1—C2 | 127.6 (2) | C9—C10—H10A | 109.1 |
O1—C1—C2 | 110.39 (19) | C5—C10—H10B | 109.1 |
C1—C2—C3 | 104.74 (18) | C9—C10—H10B | 109.1 |
C1—C2—H2A | 110.8 | H10A—C10—H10B | 107.8 |
C3—C2—H2A | 110.8 | C12—C11—C13 | 111.2 (3) |
C1—C2—H2B | 110.8 | C12—C11—C6 | 113.7 (2) |
C3—C2—H2B | 110.8 | C13—C11—C6 | 111.8 (2) |
H2A—C2—H2B | 108.9 | C12—C11—H11 | 106.6 |
N1—C3—C2 | 110.78 (18) | C13—C11—H11 | 106.6 |
N1—C3—C4 | 110.69 (17) | C6—C11—H11 | 106.6 |
C2—C3—C4 | 102.12 (17) | C11—C12—H12A | 109.5 |
N1—C3—H3 | 111.1 | C11—C12—H12B | 109.5 |
C2—C3—H3 | 111.1 | H12A—C12—H12B | 109.5 |
C4—C3—H3 | 111.1 | C11—C12—H12C | 109.5 |
O3—C4—O1 | 109.90 (16) | H12A—C12—H12C | 109.5 |
O3—C4—C3 | 109.03 (17) | H12B—C12—H12C | 109.5 |
O1—C4—C3 | 104.76 (16) | C11—C13—H13A | 109.5 |
O3—C4—H4 | 111.0 | C11—C13—H13B | 109.5 |
O1—C4—H4 | 111.0 | H13A—C13—H13B | 109.5 |
C3—C4—H4 | 111.0 | C11—C13—H13C | 109.5 |
O3—C5—C10 | 109.11 (16) | H13A—C13—H13C | 109.5 |
O3—C5—C6 | 107.03 (15) | H13B—C13—H13C | 109.5 |
C10—C5—C6 | 112.57 (17) | C9—C14—H14A | 109.5 |
O3—C5—H5 | 109.3 | C9—C14—H14B | 109.5 |
C10—C5—H5 | 109.3 | H14A—C14—H14B | 109.5 |
C6—C5—H5 | 109.3 | C9—C14—H14C | 109.5 |
C5—C6—C11 | 114.12 (18) | H14A—C14—H14C | 109.5 |
C5—C6—C7 | 108.40 (18) | H14B—C14—H14C | 109.5 |
C11—C6—C7 | 113.9 (2) | N2—C15—N1 | 123.60 (19) |
C5—C6—H6 | 106.6 | N2—C15—S1 | 115.84 (17) |
C11—C6—H6 | 106.6 | N1—C15—S1 | 120.53 (16) |
C7—C6—H6 | 106.6 | C17—C16—N2 | 115.4 (2) |
C8—C7—C6 | 112.2 (2) | C17—C16—C18 | 126.8 (2) |
C8—C7—H7A | 109.2 | N2—C16—C18 | 117.8 (2) |
C6—C7—H7A | 109.2 | C16—C17—S1 | 111.15 (18) |
C8—C7—H7B | 109.2 | C16—C17—H17 | 124.5 |
C6—C7—H7B | 109.2 | S1—C17—H17 | 124.5 |
H7A—C7—H7B | 107.9 | C16—C18—H18A | 109.5 |
C7—C8—C9 | 112.0 (2) | C16—C18—H18B | 109.5 |
C7—C8—H8A | 109.2 | H18A—C18—H18B | 109.5 |
C9—C8—H8A | 109.2 | C16—C18—H18C | 109.5 |
C7—C8—H8B | 109.2 | H18A—C18—H18C | 109.5 |
C9—C8—H8B | 109.2 | H18B—C18—H18C | 109.5 |
H8A—C8—H8B | 107.9 | ||
C4—O1—C1—O2 | 173.7 (2) | C11—C6—C7—C8 | 175.6 (2) |
C4—O1—C1—C2 | −5.8 (2) | C6—C7—C8—C9 | 57.5 (3) |
O2—C1—C2—C3 | 168.0 (3) | C7—C8—C9—C10 | −54.2 (3) |
O1—C1—C2—C3 | −12.4 (2) | C7—C8—C9—C14 | −178.3 (3) |
C15—N1—C3—C2 | −174.26 (19) | O3—C5—C10—C9 | −174.29 (19) |
C15—N1—C3—C4 | 73.2 (2) | C6—C5—C10—C9 | −55.7 (3) |
C1—C2—C3—N1 | −93.8 (2) | C8—C9—C10—C5 | 53.4 (3) |
C1—C2—C3—C4 | 24.1 (2) | C14—C9—C10—C5 | 178.5 (2) |
C5—O3—C4—O1 | −81.46 (19) | C5—C6—C11—C12 | −68.7 (3) |
C5—O3—C4—C3 | 164.24 (15) | C7—C6—C11—C12 | 56.5 (3) |
C1—O1—C4—O3 | −95.47 (19) | C5—C6—C11—C13 | 164.4 (3) |
C1—O1—C4—C3 | 21.5 (2) | C7—C6—C11—C13 | −70.3 (3) |
N1—C3—C4—O3 | −151.98 (16) | C16—N2—C15—N1 | −178.0 (2) |
C2—C3—C4—O3 | 90.1 (2) | C16—N2—C15—S1 | 0.1 (2) |
N1—C3—C4—O1 | 90.43 (18) | C3—N1—C15—N2 | −8.6 (3) |
C2—C3—C4—O1 | −27.5 (2) | C3—N1—C15—S1 | 173.32 (16) |
C4—O3—C5—C10 | −80.7 (2) | C17—S1—C15—N2 | −0.16 (18) |
C4—O3—C5—C6 | 157.22 (16) | C17—S1—C15—N1 | 178.03 (19) |
O3—C5—C6—C11 | −57.0 (2) | C15—N2—C16—C17 | 0.1 (3) |
C10—C5—C6—C11 | −176.81 (19) | C15—N2—C16—C18 | −179.8 (2) |
O3—C5—C6—C7 | 174.89 (19) | N2—C16—C17—S1 | −0.2 (3) |
C10—C5—C6—C7 | 55.1 (3) | C18—C16—C17—S1 | 179.7 (2) |
C5—C6—C7—C8 | −56.1 (3) | C15—S1—C17—C16 | 0.19 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.86 | 2.13 | 2.898 (2) | 149 |
C10—H10B···S1ii | 0.97 | 2.81 | 3.751 (3) | 163 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x, y+1/2, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C20H30N2O3S | C18H28N2O3S |
Mr | 378.52 | 352.48 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.825 (4), 14.401 (6), 17.033 (7) | 8.841 (3), 11.203 (3), 19.692 (6) |
V (Å3) | 2164.5 (15) | 1950.3 (10) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.17 | 0.18 |
Crystal size (mm) | 0.42 × 0.32 × 0.26 | 0.34 × 0.22 × 0.18 |
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 | 0.977, 0.996 | 0.913, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12564, 4425, 3686 | 11333, 3997, 2992 |
Rint | 0.029 | 0.031 |
(sin θ/λ)max (Å−1) | 0.627 | 0.627 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.097, 1.06 | 0.042, 0.099, 1.06 |
No. of reflections | 4425 | 3997 |
No. of parameters | 242 | 221 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.15 | 0.16, −0.17 |
Absolute structure | Flack (1983), with how many Friedel pairs | Flack (1983), with how many Friedel pairs |
Absolute structure parameter | 0.00 (7) | −0.03 (8) |
Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
S1—C15 | 1.759 (2) | N1—C16 | 1.342 (3) |
S1—C3 | 1.809 (2) | N2—C18 | 1.330 (3) |
N1—C15 | 1.328 (2) | N2—C15 | 1.331 (2) |
C4—C3—C2 | 101.90 (15) | C2—C3—S1 | 108.79 (13) |
C4—C3—S1 | 111.50 (13) | ||
C1—C2—C3—S1 | −94.25 (16) | S1—C3—C4—O1 | 87.14 (15) |
C15—S1—C3—C4 | 69.56 (14) | C3—S1—C15—N1 | 8.52 (18) |
C15—S1—C3—C2 | −178.84 (13) | C3—S1—C15—N2 | −170.76 (15) |
S1—C3—C4—O3 | −156.00 (12) |
S1—C17 | 1.715 (3) | N2—C15 | 1.291 (3) |
S1—C15 | 1.732 (2) | N2—C16 | 1.392 (3) |
N1—C15 | 1.363 (3) | C16—C17 | 1.332 (3) |
N1—C3 | 1.439 (3) | ||
N1—C3—C2 | 110.78 (18) | C2—C3—C4 | 102.12 (17) |
N1—C3—C4 | 110.69 (17) | ||
C15—N1—C3—C4 | 73.2 (2) | N1—C3—C4—O3 | −151.98 (16) |
C1—C2—C3—C4 | 24.1 (2) | C2—C3—C4—O3 | 90.1 (2) |
C5—O3—C4—C3 | 164.24 (15) | N1—C3—C4—O1 | 90.43 (18) |
C1—O1—C4—C3 | 21.5 (2) | C2—C3—C4—O1 | −27.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2i | 0.860 | 2.130 | 2.898 (2) | 149 |
C10—H10B···S1ii | 0.97 | 2.81 | 3.751 (3) | 163 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x, y+1/2, −z+1/2. |
The chemistry and biology of nucleoside analogues have been the subject of intensive study, since they possess many potent bioactivities, such as antiviral properties, for example against herpes simplex, AIDS-driven viral infections and the human immunodeficiency virus (Guillarme et al., 2003; Perbost et al., 1992; Wang et al., 2001; Remco et al., 2000). As part of our research work on nucleoside analogues, we synthesized the title compounds, (I) and (II), from 5-(R)-menthyloxy-2(5H)-furanone, (III), in order to evaluate their biological activity, and we report their structures here.
Compounds (I) and (II) are both composed of three sections, namely a cyclohexyloxy moiety, a tetrahydrofuran-2-one ring and a conjugated cyclic system, of which the first two almost have the same configuration in the two compounds, with similar bond distances and bond angles. Compounds (I) and (II) are not flat molecules (Figs. 1 and 2). The cyclohexyloxy section and the conjugated cyclic system are located on opposite sides of the tetrahydrofuran-2-one ring and the three rings are not coplanar with each other. In the cyclohexyloxy section, the six-membered ring adopts a chair conformation, with the isopropyl and methyl groups both located in the β-position, which is beneficial to the stability of the structure.
In the 4,6-dimethylpyrimidin-2-ylsulfanyl section of compound (I), all the non-H atoms of the group are coplanar, with a mean deviation of 0.013 (2) Å. The electrons of the ring are highly delocalized, with similar C—N and C—C bond distances (Table 1). The C15—S1 bond distance, which is shorter than C3—S1, arises from the conjugation of the electrons of atom S1 with the pyrimidinyl ring.
In the 4-methyl-1,3-thiazol-2-ylamino section of compound (II), all the non-H atoms of the group are coplanar, with a mean deviation of 0.009 (2) Å. The electrons on the ring are not as delocalized as those in (I). There are two obviously different C—N bond distances, C15—N2 and C16—N2. The C16—C17 bond distance is 1.332 (3) Å, characterizing a C═C double bond (Table 2). The short bond distances of C17—S1 and C15—S1 result from the conjugation of the electrons of atom S1 with atoms C15 and C17. The N1—C15 bond distance is shorter than the single bond C3—N1, but longer than that of the double bond C15—N2 [1.291 (3) Å], which can be attributed to the conjugation of the electrons of atom N1 with atoms C15 and N2.
Compound (II) contains one S atom, two N atoms and three O atoms, which are potential hydrogen-bond acceptors. One of the two N atoms (atom N1 of the NH group) is also a strong hydrogen-bond donor. However, the present results show that only two sites, one S atom (S1) and one O atom (O2), act as hydrogen-bond acceptors, and one N atom (N1) and one C atom (C10) act as hydrogen-bond donors, forming two types of intermolecular hydrogen bonds, C—H···S and N—H···O (Table 3). The C—H, H···S and C···S distances and the C—H···S angle indicate a weak hydrogen bond, while the N—H, H···O and N···O distances and the N—H···O angle indicate a strong hydrogen bond. Each molecule is connected to four adjacent ones through four intermolecular hydrogen bonds, two C—H···S hydrogen bonds and two N—H···O hydrogen bonds (Fig. 3). Through the action of these two types of hydrogen bonds, compound (II) forms a three-dimensional supramolecular architecture.
The crystal analysis shows the configuration of C3 is R in which compound?.