Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010091/bt6051sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010091/bt6051Isup2.hkl |
CCDC reference: 170773
To a solution of 1.00 g (3 mmol) ethyl N-(1-phenyl-3-methylsulfanyl-4-ethoxycarbonyl-pyrazol-5-yl)formimidate in 15 ml anhydrous acetonitrile, 0.39 g (3 mmol) 2-hydroxybenzal hydrazine was added, then 2 drops of Et2O solution of BF3. After stirring for 2 h, the mixture was filtered. The solution was evaporated and purified by silica-gel column chromatography to give the title compound (yield: 23%). m.p.: 465–467 K. Analysis calculated for the title compound: C 54.69, H 4.59, N 21.27%; found: C 54.42, H 4.63, N 21.16%. FT–IR data (KBr pellet, cm-1): 3115, 2997, 2930, 1695, 1594, 1576, 1496. 1H NMR (CDCl3, δ, p.p.m.): 1.16–1.24 (t, 3H), 2.60 (s, 3H), 4.10–4.36 (q, 2H), 7.18–7.50 (m, 5H), 8.30 (s, 2H). Crystals of (I) were obtained as blocks by recrystallization from a petroleum ether/ethyl acetate mixture.
The H atoms bonded to C atoms were placed in their geometrically calculated positions and included in the final refinement in the riding model approximation with displacement parameters derived from the atoms to which they were bonded. Data collection: SMART (BRUKER, 1998); cell refinement: SMART1000; data reduction: SAINT (BRUKER, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998).
C15H15N5O2S | Dx = 1.484 Mg m−3 |
Mr = 329.38 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 11458 reflections |
a = 9.669 (5) Å | θ = 2.3–25.0° |
b = 17.063 (9) Å | µ = 0.24 mm−1 |
c = 17.875 (10) Å | T = 298 K |
V = 2949 (3) Å3 | Prism, colorless |
Z = 8 | 0.25 × 0.20 × 0.15 mm |
F(000) = 1376 |
Bruker SMART 1000 diffractometer | 1880 reflections with I > 2.0σ(I) |
ω scans | Rint = 0.058 |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | θmax = 25.0° |
Tmin = 0.943, Tmax = 0.965 | h = −11→11 |
11622 measured reflections | k = −20→14 |
2614 independent reflections | l = −18→21 |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0551P)2 + 0.857P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.111 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.19 e Å−3 |
2614 reflections | Δρmin = −0.27 e Å−3 |
208 parameters |
C15H15N5O2S | V = 2949 (3) Å3 |
Mr = 329.38 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.669 (5) Å | µ = 0.24 mm−1 |
b = 17.063 (9) Å | T = 298 K |
c = 17.875 (10) Å | 0.25 × 0.20 × 0.15 mm |
Bruker SMART 1000 diffractometer | 2614 independent reflections |
Absorption correction: multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] | 1880 reflections with I > 2.0σ(I) |
Tmin = 0.943, Tmax = 0.965 | Rint = 0.058 |
11622 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 208 parameters |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.19 e Å−3 |
2614 reflections | Δρmin = −0.27 e Å−3 |
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. Full-MATRIX |
x | y | z | Uiso*/Ueq | ||
S1 | 0.12479 (6) | 0.04165 (4) | 0.03864 (4) | 0.0566 (2) | |
N1 | 0.41216 (17) | 0.13451 (10) | 0.14576 (10) | 0.0386 (4) | |
N2 | 0.28698 (17) | 0.13683 (10) | 0.11354 (10) | 0.0426 (5) | |
N3 | 0.59841 (17) | 0.04882 (10) | 0.16515 (10) | 0.0381 (4) | |
N4 | 0.8160 (2) | 0.03795 (17) | 0.17932 (14) | 0.0791 (8) | |
N5 | 0.7537 (2) | 0.00862 (14) | 0.24043 (13) | 0.0625 (6) | |
O1 | 0.31105 (18) | −0.09285 (10) | 0.03928 (10) | 0.0606 (5) | |
O2 | 0.51746 (16) | −0.08857 (8) | 0.08832 (9) | 0.0487 (4) | |
C1 | 0.4708 (2) | 0.06543 (12) | 0.13590 (12) | 0.0360 (5) | |
C2 | 0.3840 (2) | 0.02021 (12) | 0.09644 (12) | 0.0369 (5) | |
C3 | 0.2703 (2) | 0.06771 (13) | 0.08458 (12) | 0.0409 (5) | |
C4 | 0.0301 (3) | 0.12862 (14) | 0.04463 (15) | 0.0585 (7) | |
H4A | −0.0574 | 0.1219 | 0.0201 | 0.088* | |
H4B | 0.0806 | 0.1701 | 0.0208 | 0.088* | |
H4C | 0.0152 | 0.1416 | 0.0963 | 0.088* | |
C5 | 0.3982 (2) | −0.05895 (13) | 0.07177 (13) | 0.0414 (5) | |
C6 | 0.7211 (2) | 0.06113 (19) | 0.13576 (15) | 0.0663 (8) | |
H6A | 0.7362 | 0.0838 | 0.0892 | 0.080* | |
C7 | 0.6251 (3) | 0.01562 (15) | 0.23047 (14) | 0.0543 (7) | |
H7A | 0.5581 | −0.0004 | 0.2645 | 0.065* | |
C8 | 0.4651 (2) | 0.20372 (12) | 0.17602 (12) | 0.0398 (5) | |
C9 | 0.5439 (3) | 0.20235 (14) | 0.23805 (14) | 0.0507 (6) | |
H9A | 0.5613 | 0.1554 | 0.2627 | 0.061* | |
C10 | 0.5974 (3) | 0.27019 (16) | 0.26387 (16) | 0.0598 (7) | |
H10A | 0.6543 | 0.2697 | 0.3058 | 0.072* | |
C11 | 0.5694 (3) | 0.33810 (16) | 0.22973 (16) | 0.0628 (7) | |
H11A | 0.6069 | 0.3845 | 0.2480 | 0.075* | |
C12 | 0.4876 (3) | 0.33943 (15) | 0.16946 (16) | 0.0608 (7) | |
H12A | 0.4663 | 0.3870 | 0.1467 | 0.073* | |
C13 | 0.4356 (3) | 0.27205 (13) | 0.14139 (13) | 0.0487 (6) | |
H13A | 0.3803 | 0.2727 | 0.0988 | 0.058* | |
C14 | 0.5418 (3) | −0.16603 (14) | 0.06275 (15) | 0.0561 (7) | |
H14A | 0.5442 | −0.1673 | 0.0085 | 0.067* | |
H14B | 0.4690 | −0.2008 | 0.0799 | 0.067* | |
C15 | 0.6737 (3) | −0.19033 (17) | 0.0930 (2) | 0.0817 (10) | |
H15A | 0.6942 | −0.2426 | 0.0765 | 0.123* | |
H15B | 0.6697 | −0.1893 | 0.1467 | 0.123* | |
H15C | 0.7447 | −0.1553 | 0.0760 | 0.123* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0413 (4) | 0.0503 (4) | 0.0784 (5) | −0.0009 (3) | −0.0199 (3) | −0.0123 (3) |
N1 | 0.0341 (9) | 0.0391 (10) | 0.0425 (10) | −0.0030 (8) | −0.0056 (8) | −0.0051 (8) |
N2 | 0.0346 (10) | 0.0423 (11) | 0.0510 (11) | −0.0020 (8) | −0.0079 (8) | −0.0050 (9) |
N3 | 0.0337 (9) | 0.0409 (10) | 0.0398 (10) | 0.0010 (8) | −0.0051 (8) | −0.0032 (8) |
N4 | 0.0418 (12) | 0.129 (2) | 0.0668 (17) | 0.0135 (14) | −0.0089 (12) | −0.0151 (16) |
N5 | 0.0587 (14) | 0.0658 (14) | 0.0630 (15) | 0.0174 (11) | −0.0181 (12) | −0.0096 (11) |
O1 | 0.0560 (10) | 0.0487 (10) | 0.0773 (13) | −0.0024 (9) | −0.0223 (9) | −0.0157 (9) |
O2 | 0.0458 (9) | 0.0399 (9) | 0.0604 (11) | 0.0040 (7) | −0.0072 (8) | −0.0107 (7) |
C1 | 0.0337 (11) | 0.0378 (12) | 0.0364 (12) | −0.0004 (9) | −0.0006 (9) | 0.0014 (9) |
C2 | 0.0364 (11) | 0.0366 (12) | 0.0376 (12) | −0.0036 (9) | −0.0030 (9) | −0.0022 (9) |
C3 | 0.0365 (12) | 0.0429 (13) | 0.0433 (13) | −0.0036 (10) | −0.0018 (10) | −0.0013 (10) |
C4 | 0.0458 (14) | 0.0557 (16) | 0.0741 (18) | 0.0058 (12) | −0.0112 (13) | −0.0058 (13) |
C5 | 0.0428 (13) | 0.0412 (13) | 0.0404 (13) | −0.0031 (10) | −0.0030 (10) | −0.0010 (10) |
C6 | 0.0383 (14) | 0.111 (2) | 0.0492 (16) | 0.0013 (14) | 0.0022 (12) | 0.0009 (15) |
C7 | 0.0552 (16) | 0.0526 (15) | 0.0552 (16) | 0.0034 (12) | −0.0125 (12) | 0.0065 (11) |
C8 | 0.0361 (11) | 0.0382 (12) | 0.0451 (13) | −0.0063 (9) | 0.0016 (10) | −0.0080 (10) |
C9 | 0.0543 (15) | 0.0458 (14) | 0.0520 (15) | 0.0009 (11) | −0.0092 (12) | −0.0079 (11) |
C10 | 0.0533 (15) | 0.0613 (18) | 0.0646 (17) | −0.0025 (12) | −0.0104 (13) | −0.0235 (14) |
C11 | 0.0620 (17) | 0.0509 (16) | 0.076 (2) | −0.0144 (13) | 0.0046 (15) | −0.0197 (14) |
C12 | 0.0778 (18) | 0.0406 (14) | 0.0640 (17) | −0.0066 (13) | 0.0076 (15) | −0.0033 (12) |
C13 | 0.0552 (14) | 0.0407 (14) | 0.0500 (14) | −0.0035 (11) | −0.0006 (12) | −0.0015 (11) |
C14 | 0.0633 (16) | 0.0407 (14) | 0.0644 (17) | 0.0067 (12) | 0.0007 (13) | −0.0092 (11) |
C15 | 0.0634 (18) | 0.0635 (18) | 0.118 (3) | 0.0164 (15) | −0.0017 (18) | −0.0011 (18) |
S1—C3 | 1.689 (2) | C4—H4C | 0.9600 |
S1—C4 | 1.747 (3) | C6—H6A | 0.9300 |
N1—C1 | 1.320 (3) | C7—H7A | 0.9300 |
N1—N2 | 1.341 (2) | C8—C9 | 1.346 (3) |
N1—C8 | 1.396 (3) | C8—C13 | 1.350 (3) |
N2—C3 | 1.298 (3) | C9—C10 | 1.349 (3) |
N3—C6 | 1.314 (3) | C9—H9A | 0.9300 |
N3—C7 | 1.323 (3) | C10—C11 | 1.337 (4) |
N3—C1 | 1.370 (3) | C10—H10A | 0.9300 |
N4—C6 | 1.266 (3) | C11—C12 | 1.337 (4) |
N4—N5 | 1.344 (3) | C11—H11A | 0.9300 |
N5—C7 | 1.261 (3) | C12—C13 | 1.351 (3) |
O1—C5 | 1.175 (3) | C12—H12A | 0.9300 |
O2—C5 | 1.294 (3) | C13—H13A | 0.9300 |
O2—C14 | 1.418 (3) | C14—C15 | 1.446 (4) |
C1—C2 | 1.340 (3) | C14—H14A | 0.9700 |
C2—C3 | 1.383 (3) | C14—H14B | 0.9700 |
C2—C5 | 1.427 (3) | C15—H15A | 0.9600 |
C4—H4A | 0.9600 | C15—H15B | 0.9600 |
C4—H4B | 0.9600 | C15—H15C | 0.9600 |
C3—S1—C4 | 100.55 (12) | N5—C7—H7A | 124.5 |
C1—N1—N2 | 110.90 (16) | N3—C7—H7A | 124.5 |
C1—N1—C8 | 130.53 (18) | C9—C8—C13 | 120.8 (2) |
N2—N1—C8 | 118.17 (17) | C9—C8—N1 | 120.8 (2) |
C3—N2—N1 | 104.87 (17) | C13—C8—N1 | 118.4 (2) |
C6—N3—C7 | 104.2 (2) | C8—C9—C10 | 118.9 (2) |
C6—N3—C1 | 128.8 (2) | C8—C9—H9A | 120.5 |
C7—N3—C1 | 127.0 (2) | C10—C9—H9A | 120.5 |
C6—N4—N5 | 106.9 (2) | C11—C10—C9 | 120.6 (3) |
C7—N5—N4 | 107.0 (2) | C11—C10—H10A | 119.7 |
C5—O2—C14 | 116.01 (18) | C9—C10—H10A | 119.7 |
N1—C1—C2 | 108.39 (18) | C12—C11—C10 | 120.2 (2) |
N1—C1—N3 | 121.39 (18) | C12—C11—H11A | 119.9 |
C2—C1—N3 | 130.2 (2) | C10—C11—H11A | 119.9 |
C1—C2—C3 | 103.95 (19) | C11—C12—C13 | 120.3 (3) |
C1—C2—C5 | 130.3 (2) | C11—C12—H12A | 119.8 |
C3—C2—C5 | 125.69 (19) | C13—C12—H12A | 119.8 |
N2—C3—C2 | 111.88 (19) | C8—C13—C12 | 119.1 (2) |
N2—C3—S1 | 122.47 (17) | C8—C13—H13A | 120.5 |
C2—C3—S1 | 125.65 (17) | C12—C13—H13A | 120.5 |
S1—C4—H4A | 109.5 | O2—C14—C15 | 107.0 (2) |
S1—C4—H4B | 109.5 | O2—C14—H14A | 110.3 |
H4A—C4—H4B | 109.5 | C15—C14—H14A | 110.3 |
S1—C4—H4C | 109.5 | O2—C14—H14B | 110.3 |
H4A—C4—H4C | 109.5 | C15—C14—H14B | 110.3 |
H4B—C4—H4C | 109.5 | H14A—C14—H14B | 108.6 |
O1—C5—O2 | 124.0 (2) | C14—C15—H15A | 109.5 |
O1—C5—C2 | 123.4 (2) | C14—C15—H15B | 109.5 |
O2—C5—C2 | 112.60 (19) | H15A—C15—H15B | 109.5 |
N4—C6—N3 | 111.0 (3) | C14—C15—H15C | 109.5 |
N4—C6—H6A | 124.5 | H15A—C15—H15C | 109.5 |
N3—C6—H6A | 124.5 | H15B—C15—H15C | 109.5 |
N5—C7—N3 | 111.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O1i | 0.93 | 2.35 | 3.190 (4) | 151 |
C11—H11A···N5ii | 0.93 | 2.51 | 3.381 (3) | 155 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+3/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C15H15N5O2S |
Mr | 329.38 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 9.669 (5), 17.063 (9), 17.875 (10) |
V (Å3) | 2949 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.25 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Multi-scan [SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)] |
Tmin, Tmax | 0.943, 0.965 |
No. of measured, independent and observed [I > 2.0σ(I)] reflections | 11622, 2614, 1880 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.111, 1.01 |
No. of reflections | 2614 |
No. of parameters | 208 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.27 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1998).
S1—C3 | 1.689 (2) | N3—C1 | 1.370 (3) |
S1—C4 | 1.747 (3) | N4—C6 | 1.266 (3) |
N1—C1 | 1.320 (3) | N4—N5 | 1.344 (3) |
N1—N2 | 1.341 (2) | N5—C7 | 1.261 (3) |
N1—C8 | 1.396 (3) | O1—C5 | 1.175 (3) |
N2—C3 | 1.298 (3) | O2—C5 | 1.294 (3) |
N3—C6 | 1.314 (3) | O2—C14 | 1.418 (3) |
N3—C7 | 1.323 (3) | ||
C3—S1—C4 | 100.55 (12) | C6—N3—C1 | 128.8 (2) |
C1—N1—N2 | 110.90 (16) | C7—N3—C1 | 127.0 (2) |
C1—N1—C8 | 130.53 (18) | C6—N4—N5 | 106.9 (2) |
N2—N1—C8 | 118.17 (17) | C7—N5—N4 | 107.0 (2) |
C3—N2—N1 | 104.87 (17) | C5—O2—C14 | 116.01 (18) |
C6—N3—C7 | 104.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6A···O1i | .930 | 2.346 | 3.190 (4) | 150.8 |
C11—H11A···N5ii | .930 | 2.514 | 3.381 (3) | 155.2 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+3/2, y+1/2, z. |
In studies on new pharmaceuticals and agrochemicals, heterocycles are worthy of very important consideration. Pyrazoles and their derivatives were reported to show a broad spectrum of biological activities (Liu et al., 1998; Morimoto et al., 1997). In our earlier study on this type of compounds, we have found that substituted arylpyrazoles exhibit good biological activity (Chen et al., 2000); also, pesticidal properties were reported, analgesic and anti-inflammatory activities have been observed (Reddy et al., 1999), and xanthine oxidase inhibition and central depressant activity have also been studied (Ishibuchi et al., 1998; Darias et al., 1998). Since knowledge of the stereochemistry is useful in the rational design of pharmaceuticals and agrochemicals, we herein report the synthesis and X-ray crystal structure of the title compound, (I).
In the title compound, the N1—C1, N3—C6 and N3—C7 bond lengths are remarkably shorter than a single C—N (1.47 Å; Sasada, 1984) and close to the value of C═N double-bond distance (1.28 Å; Wang et al., 1998), which is indicative of significant double-bond character. The triazole ring forms a π56 configuration in which the N3 atom is sp2 hybridized. The C3—S1 bond length (1.689 Å) is slight shorter than that of C4—S1 (1.747 Å), which may due to the conjugation of S1 with pyrazole ring. The C5—O2 bond length (1.294 Å) is longer than that of C5—O1 (1.175 Å) and remarkably shorter than C14—O2 (1.418 Å), which demonstrate the conjugation of O2 with C5—O1. The pyrazole ring makes dihedral angles of 140.2 (3) and 86.5 (3)° with the phenyl and triazole plane, respectively, and the dihedral angle between them is 109.2 (4)°.
An important feature to note is that a strong S···S(-x, -y, -z) interaction exists between the adjacent molecule to make a zigzag linear structure along c axis with the S···S distance of 3.123 (3) Å. In addition, weak intermolecular interactions are found to exist between C6—H6A···O1(1 - x, -y, -z) and C11—H11···N5(-1.5 - x, 0.5 + y, z), and forms a three-dimensional network as shown in Fig. 2.