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In the crystal structure of the title compound, C15H15N5O2S, the triazole ring forms a π56 configuration in which the N between the two C atoms is sp2 hybridized. A strong S...S(−x, −y, −z) interaction exists between adjacent mol­ecules producing a zigzag line along the c axis with an S...S distance of 3.123 (3) Å, and a three-dimensional network is formed through C—H...N and C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010091/bt6051sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010091/bt6051Isup2.hkl
Contains datablock I

CCDC reference: 170773

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.038
  • wR factor = 0.111
  • Data-to-parameter ratio = 12.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

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 CN 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.

Experimental top

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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEPII view (Johnson, 1976) of the title compound with 30% probability ellipsoids.
[Figure 2] Fig. 2. The molecular packing diagram of (I) (H atoms not mentioned in the text have been omitted for clarity).
Ethyl 1-phenyl-3-sulfanyl-5-(4H-1,2,4-triazol-4-yl)pyrazole-4-carboxylate top
Crystal data top
C15H15N5O2SDx = 1.484 Mg m3
Mr = 329.38Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 11458 reflections
a = 9.669 (5) Åθ = 2.3–25.0°
b = 17.063 (9) ŵ = 0.24 mm1
c = 17.875 (10) ÅT = 298 K
V = 2949 (3) Å3Prism, colorless
Z = 80.25 × 0.20 × 0.15 mm
F(000) = 1376
Data collection top
Bruker SMART 1000
diffractometer
1880 reflections with I > 2.0σ(I)
ω scansRint = 0.058
Absorption correction: multi-scan
[SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)]
θmax = 25.0°
Tmin = 0.943, Tmax = 0.965h = 1111
11622 measured reflectionsk = 2014
2614 independent reflectionsl = 1821
Refinement top
Refinement on F2H-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 = 1.01Δρmax = 0.19 e Å3
2614 reflectionsΔρmin = 0.27 e Å3
208 parameters
Crystal data top
C15H15N5O2SV = 2949 (3) Å3
Mr = 329.38Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.669 (5) ŵ = 0.24 mm1
b = 17.063 (9) ÅT = 298 K
c = 17.875 (10) Å0.25 × 0.20 × 0.15 mm
Data collection top
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 = 0.965Rint = 0.058
11622 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038208 parameters
wR(F2) = 0.111H-atom parameters constrained
S = 1.01Δρmax = 0.19 e Å3
2614 reflectionsΔρmin = 0.27 e Å3
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.12479 (6)0.04165 (4)0.03864 (4)0.0566 (2)
N10.41216 (17)0.13451 (10)0.14576 (10)0.0386 (4)
N20.28698 (17)0.13683 (10)0.11354 (10)0.0426 (5)
N30.59841 (17)0.04882 (10)0.16515 (10)0.0381 (4)
N40.8160 (2)0.03795 (17)0.17932 (14)0.0791 (8)
N50.7537 (2)0.00862 (14)0.24043 (13)0.0625 (6)
O10.31105 (18)0.09285 (10)0.03928 (10)0.0606 (5)
O20.51746 (16)0.08857 (8)0.08832 (9)0.0487 (4)
C10.4708 (2)0.06543 (12)0.13590 (12)0.0360 (5)
C20.3840 (2)0.02021 (12)0.09644 (12)0.0369 (5)
C30.2703 (2)0.06771 (13)0.08458 (12)0.0409 (5)
C40.0301 (3)0.12862 (14)0.04463 (15)0.0585 (7)
H4A0.05740.12190.02010.088*
H4B0.08060.17010.02080.088*
H4C0.01520.14160.09630.088*
C50.3982 (2)0.05895 (13)0.07177 (13)0.0414 (5)
C60.7211 (2)0.06113 (19)0.13576 (15)0.0663 (8)
H6A0.73620.08380.08920.080*
C70.6251 (3)0.01562 (15)0.23047 (14)0.0543 (7)
H7A0.55810.00040.26450.065*
C80.4651 (2)0.20372 (12)0.17602 (12)0.0398 (5)
C90.5439 (3)0.20235 (14)0.23805 (14)0.0507 (6)
H9A0.56130.15540.26270.061*
C100.5974 (3)0.27019 (16)0.26387 (16)0.0598 (7)
H10A0.65430.26970.30580.072*
C110.5694 (3)0.33810 (16)0.22973 (16)0.0628 (7)
H11A0.60690.38450.24800.075*
C120.4876 (3)0.33943 (15)0.16946 (16)0.0608 (7)
H12A0.46630.38700.14670.073*
C130.4356 (3)0.27205 (13)0.14139 (13)0.0487 (6)
H13A0.38030.27270.09880.058*
C140.5418 (3)0.16603 (14)0.06275 (15)0.0561 (7)
H14A0.54420.16730.00850.067*
H14B0.46900.20080.07990.067*
C150.6737 (3)0.19033 (17)0.0930 (2)0.0817 (10)
H15A0.69420.24260.07650.123*
H15B0.66970.18930.14670.123*
H15C0.74470.15530.07600.123*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0413 (4)0.0503 (4)0.0784 (5)0.0009 (3)0.0199 (3)0.0123 (3)
N10.0341 (9)0.0391 (10)0.0425 (10)0.0030 (8)0.0056 (8)0.0051 (8)
N20.0346 (10)0.0423 (11)0.0510 (11)0.0020 (8)0.0079 (8)0.0050 (9)
N30.0337 (9)0.0409 (10)0.0398 (10)0.0010 (8)0.0051 (8)0.0032 (8)
N40.0418 (12)0.129 (2)0.0668 (17)0.0135 (14)0.0089 (12)0.0151 (16)
N50.0587 (14)0.0658 (14)0.0630 (15)0.0174 (11)0.0181 (12)0.0096 (11)
O10.0560 (10)0.0487 (10)0.0773 (13)0.0024 (9)0.0223 (9)0.0157 (9)
O20.0458 (9)0.0399 (9)0.0604 (11)0.0040 (7)0.0072 (8)0.0107 (7)
C10.0337 (11)0.0378 (12)0.0364 (12)0.0004 (9)0.0006 (9)0.0014 (9)
C20.0364 (11)0.0366 (12)0.0376 (12)0.0036 (9)0.0030 (9)0.0022 (9)
C30.0365 (12)0.0429 (13)0.0433 (13)0.0036 (10)0.0018 (10)0.0013 (10)
C40.0458 (14)0.0557 (16)0.0741 (18)0.0058 (12)0.0112 (13)0.0058 (13)
C50.0428 (13)0.0412 (13)0.0404 (13)0.0031 (10)0.0030 (10)0.0010 (10)
C60.0383 (14)0.111 (2)0.0492 (16)0.0013 (14)0.0022 (12)0.0009 (15)
C70.0552 (16)0.0526 (15)0.0552 (16)0.0034 (12)0.0125 (12)0.0065 (11)
C80.0361 (11)0.0382 (12)0.0451 (13)0.0063 (9)0.0016 (10)0.0080 (10)
C90.0543 (15)0.0458 (14)0.0520 (15)0.0009 (11)0.0092 (12)0.0079 (11)
C100.0533 (15)0.0613 (18)0.0646 (17)0.0025 (12)0.0104 (13)0.0235 (14)
C110.0620 (17)0.0509 (16)0.076 (2)0.0144 (13)0.0046 (15)0.0197 (14)
C120.0778 (18)0.0406 (14)0.0640 (17)0.0066 (13)0.0076 (15)0.0033 (12)
C130.0552 (14)0.0407 (14)0.0500 (14)0.0035 (11)0.0006 (12)0.0015 (11)
C140.0633 (16)0.0407 (14)0.0644 (17)0.0067 (12)0.0007 (13)0.0092 (11)
C150.0634 (18)0.0635 (18)0.118 (3)0.0164 (15)0.0017 (18)0.0011 (18)
Geometric parameters (Å, º) top
S1—C31.689 (2)C4—H4C0.9600
S1—C41.747 (3)C6—H6A0.9300
N1—C11.320 (3)C7—H7A0.9300
N1—N21.341 (2)C8—C91.346 (3)
N1—C81.396 (3)C8—C131.350 (3)
N2—C31.298 (3)C9—C101.349 (3)
N3—C61.314 (3)C9—H9A0.9300
N3—C71.323 (3)C10—C111.337 (4)
N3—C11.370 (3)C10—H10A0.9300
N4—C61.266 (3)C11—C121.337 (4)
N4—N51.344 (3)C11—H11A0.9300
N5—C71.261 (3)C12—C131.351 (3)
O1—C51.175 (3)C12—H12A0.9300
O2—C51.294 (3)C13—H13A0.9300
O2—C141.418 (3)C14—C151.446 (4)
C1—C21.340 (3)C14—H14A0.9700
C2—C31.383 (3)C14—H14B0.9700
C2—C51.427 (3)C15—H15A0.9600
C4—H4A0.9600C15—H15B0.9600
C4—H4B0.9600C15—H15C0.9600
C3—S1—C4100.55 (12)N5—C7—H7A124.5
C1—N1—N2110.90 (16)N3—C7—H7A124.5
C1—N1—C8130.53 (18)C9—C8—C13120.8 (2)
N2—N1—C8118.17 (17)C9—C8—N1120.8 (2)
C3—N2—N1104.87 (17)C13—C8—N1118.4 (2)
C6—N3—C7104.2 (2)C8—C9—C10118.9 (2)
C6—N3—C1128.8 (2)C8—C9—H9A120.5
C7—N3—C1127.0 (2)C10—C9—H9A120.5
C6—N4—N5106.9 (2)C11—C10—C9120.6 (3)
C7—N5—N4107.0 (2)C11—C10—H10A119.7
C5—O2—C14116.01 (18)C9—C10—H10A119.7
N1—C1—C2108.39 (18)C12—C11—C10120.2 (2)
N1—C1—N3121.39 (18)C12—C11—H11A119.9
C2—C1—N3130.2 (2)C10—C11—H11A119.9
C1—C2—C3103.95 (19)C11—C12—C13120.3 (3)
C1—C2—C5130.3 (2)C11—C12—H12A119.8
C3—C2—C5125.69 (19)C13—C12—H12A119.8
N2—C3—C2111.88 (19)C8—C13—C12119.1 (2)
N2—C3—S1122.47 (17)C8—C13—H13A120.5
C2—C3—S1125.65 (17)C12—C13—H13A120.5
S1—C4—H4A109.5O2—C14—C15107.0 (2)
S1—C4—H4B109.5O2—C14—H14A110.3
H4A—C4—H4B109.5C15—C14—H14A110.3
S1—C4—H4C109.5O2—C14—H14B110.3
H4A—C4—H4C109.5C15—C14—H14B110.3
H4B—C4—H4C109.5H14A—C14—H14B108.6
O1—C5—O2124.0 (2)C14—C15—H15A109.5
O1—C5—C2123.4 (2)C14—C15—H15B109.5
O2—C5—C2112.60 (19)H15A—C15—H15B109.5
N4—C6—N3111.0 (3)C14—C15—H15C109.5
N4—C6—H6A124.5H15A—C15—H15C109.5
N3—C6—H6A124.5H15B—C15—H15C109.5
N5—C7—N3111.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O1i0.932.353.190 (4)151
C11—H11A···N5ii0.932.513.381 (3)155
Symmetry codes: (i) x+1, y, z; (ii) x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC15H15N5O2S
Mr329.38
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)298
a, b, c (Å)9.669 (5), 17.063 (9), 17.875 (10)
V3)2949 (3)
Z8
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.25 × 0.20 × 0.15
Data collection
DiffractometerBruker SMART 1000
diffractometer
Absorption correctionMulti-scan
[SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)]
Tmin, Tmax0.943, 0.965
No. of measured, independent and
observed [I > 2.0σ(I)] reflections
11622, 2614, 1880
Rint0.058
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.111, 1.01
No. of reflections2614
No. of parameters208
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.27

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1998).

Selected geometric parameters (Å, º) top
S1—C31.689 (2)N3—C11.370 (3)
S1—C41.747 (3)N4—C61.266 (3)
N1—C11.320 (3)N4—N51.344 (3)
N1—N21.341 (2)N5—C71.261 (3)
N1—C81.396 (3)O1—C51.175 (3)
N2—C31.298 (3)O2—C51.294 (3)
N3—C61.314 (3)O2—C141.418 (3)
N3—C71.323 (3)
C3—S1—C4100.55 (12)C6—N3—C1128.8 (2)
C1—N1—N2110.90 (16)C7—N3—C1127.0 (2)
C1—N1—C8130.53 (18)C6—N4—N5106.9 (2)
N2—N1—C8118.17 (17)C7—N5—N4107.0 (2)
C3—N2—N1104.87 (17)C5—O2—C14116.01 (18)
C6—N3—C7104.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···O1i.9302.3463.190 (4)150.8
C11—H11A···N5ii.9302.5143.381 (3)155.2
Symmetry codes: (i) x+1, y, z; (ii) x+3/2, y+1/2, z.
 

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