organic compounds
Ethyl 2-(3-methyl-5-sulfanylidene-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetate
aDepartment of Chemistry, Siedlce University, ul. 3 Maja 54, 08-110 Siedlce, Poland, bDepartment of Organic Chemistry, Faculty of Pharmacy with Division of Medical Analytics, Medical University, ul. Chodźki 4A, 20-093 Lublin, Poland, and cDepartment of General and Ecological Chemistry, Technical University, ul. Żeromskiego 115, 90-924 Łódź, Poland
*Correspondence e-mail: kar@uph.edu.pl
The title compound, C7H11N3O2S, exists in the 5-thioxo tautomeric form. The 1,2,4-triazoline ring is essentially planar, with a maximum deviation of 0.010 (2) Å for the substituted N atom. The ethyl acetate substituent is almost planar, with a maximum deviation of 0.061 (4) Å for the methylene C atom of the ethoxy group. The angle between the mean plane of this substituent and the mean plane of the 1,2,4-triazoline ring is 89.74 (8)°. In the crystal, molecules are linked by a combination of N—H⋯S, C—H⋯N and C—H⋯O hydrogen bonds into chains parallel to [100].
Related literature
For background information on the title compound, see: Saadeh et al. (2010); Akhtar et al. (2008); Al-Omar et al. (2010). For the biological activity of 1,2,4-triazoline-thiones, see: Pitucha et al. (2010). For their synthesis, see: Bany & Dobosz (1972). For related structures, see: Kruszynski et al. (2007); Siwek et al. (2008). For graph-set motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: KM4B8 (Gałdecki et al., 1996); cell KM4B8; data reduction: DATAPROC (Gałdecki et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 2012).
Supporting information
10.1107/S1600536812044716/fj2601sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044716/fj2601Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044716/fj2601Isup3.cml
The title compound, (I), was prepared from acetamidrazone hydrochloride and carboethoxymethyl isothiocyanate, according to the method of Bany & Dobosz (1972).
The N-bound H atom was located by difference Fourier synthesis and refined freely. The remaining H atoms were positioned geometrically and treated as riding on their C atoms with C—H distances of 0.93 Å (aromatic), 0.96 Å (CH2) and 0.97 Å (CH3). All H atoms were assigned Uiso(H) values of 1.5Ueq(N,C)]..
Data collection: KM4B8 (Gałdecki et al., 1996); cell
KM4B8 (Gałdecki et al., 1996); data reduction: DATAPROC (Gałdecki et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms. | |
Fig. 2. A view of the molecular packing in (I). |
C7H11N3O2S | F(000) = 424 |
Mr = 201.25 | Dx = 1.381 Mg m−3 |
Monoclinic, P21/c | Melting point = 446–447 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 6.4438 (19) Å | Cell parameters from 70 reflections |
b = 15.2328 (15) Å | θ = 2.7–11.9° |
c = 9.9672 (8) Å | µ = 0.31 mm−1 |
β = 98.416 (19)° | T = 293 K |
V = 967.8 (3) Å3 | Prism, colourless |
Z = 4 | 0.60 × 0.30 × 0.30 mm |
Kuma KM-4 four-circle diffractometer | 1571 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.069 |
Graphite monochromator | θmax = 30.1°, θmin = 2.5° |
ω–2θ scans | h = −9→8 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→21 |
Tmin = 0.754, Tmax = 0.869 | l = 0→14 |
2979 measured reflections | 2 standard reflections every 100 reflections |
2837 independent reflections | intensity decay: 8.9% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.062 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.198 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | w = 1/[σ2(Fo2) + (0.1344P)2] where P = (Fo2 + 2Fc2)/3 |
2837 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
C7H11N3O2S | V = 967.8 (3) Å3 |
Mr = 201.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.4438 (19) Å | µ = 0.31 mm−1 |
b = 15.2328 (15) Å | T = 293 K |
c = 9.9672 (8) Å | 0.60 × 0.30 × 0.30 mm |
β = 98.416 (19)° |
Kuma KM-4 four-circle diffractometer | 1571 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.069 |
Tmin = 0.754, Tmax = 0.869 | 2 standard reflections every 100 reflections |
2979 measured reflections | intensity decay: 8.9% |
2837 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.198 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.64 e Å−3 |
2837 reflections | Δρmin = −0.48 e Å−3 |
123 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
S6 | 0.29109 (11) | 0.08274 (5) | 0.48884 (8) | 0.0493 (3) | |
O10 | 0.2086 (3) | 0.33096 (15) | 0.4137 (2) | 0.0553 (6) | |
O11 | 0.5003 (3) | 0.34124 (13) | 0.31670 (19) | 0.0423 (5) | |
N1 | −0.1100 (3) | 0.08964 (16) | 0.3569 (2) | 0.0384 (5) | |
H1 | −0.152 (6) | 0.053 (3) | 0.402 (4) | 0.058* | |
N2 | −0.2330 (3) | 0.13342 (15) | 0.2554 (2) | 0.0400 (5) | |
N4 | 0.0940 (3) | 0.17783 (14) | 0.2764 (2) | 0.0324 (4) | |
C3 | −0.1054 (4) | 0.18780 (18) | 0.2086 (2) | 0.0348 (5) | |
C5 | 0.0896 (4) | 0.11528 (17) | 0.3742 (2) | 0.0338 (5) | |
C7 | −0.1642 (4) | 0.2523 (2) | 0.0993 (3) | 0.0449 (6) | |
H7A | −0.1073 | 0.2345 | 0.0198 | 0.067* | |
H7B | −0.1093 | 0.3089 | 0.1282 | 0.067* | |
H7C | −0.3143 | 0.2555 | 0.0788 | 0.067* | |
C8 | 0.2820 (4) | 0.22340 (18) | 0.2511 (2) | 0.0348 (5) | |
H8A | 0.2677 | 0.2399 | 0.1562 | 0.052* | |
H8B | 0.4014 | 0.1842 | 0.2700 | 0.052* | |
C9 | 0.3210 (4) | 0.30402 (17) | 0.3374 (2) | 0.0347 (5) | |
C12 | 0.5476 (5) | 0.4245 (2) | 0.3862 (4) | 0.0553 (8) | |
H12A | 0.5543 | 0.4166 | 0.4833 | 0.083* | |
H12B | 0.4386 | 0.4670 | 0.3561 | 0.083* | |
C13 | 0.7523 (7) | 0.4562 (3) | 0.3544 (5) | 0.0743 (11) | |
H13A | 0.8607 | 0.4158 | 0.3902 | 0.111* | |
H13B | 0.7818 | 0.5130 | 0.3944 | 0.111* | |
H13C | 0.7469 | 0.4604 | 0.2578 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S6 | 0.0354 (4) | 0.0521 (4) | 0.0567 (5) | −0.0037 (3) | −0.0051 (3) | 0.0156 (3) |
O10 | 0.0513 (12) | 0.0536 (13) | 0.0663 (13) | −0.0048 (10) | 0.0263 (10) | −0.0162 (10) |
O11 | 0.0342 (9) | 0.0406 (10) | 0.0530 (11) | −0.0086 (8) | 0.0094 (7) | −0.0052 (8) |
N1 | 0.0306 (10) | 0.0387 (12) | 0.0460 (12) | −0.0034 (9) | 0.0064 (8) | 0.0086 (10) |
N2 | 0.0278 (10) | 0.0463 (12) | 0.0457 (12) | −0.0014 (9) | 0.0046 (8) | 0.0046 (10) |
N4 | 0.0247 (9) | 0.0336 (10) | 0.0392 (10) | −0.0001 (8) | 0.0061 (7) | 0.0002 (8) |
C3 | 0.0280 (11) | 0.0398 (13) | 0.0367 (12) | 0.0024 (10) | 0.0052 (9) | 0.0003 (10) |
C5 | 0.0300 (11) | 0.0302 (11) | 0.0411 (13) | −0.0001 (9) | 0.0051 (9) | 0.0001 (10) |
C7 | 0.0352 (14) | 0.0523 (16) | 0.0467 (15) | 0.0049 (12) | 0.0045 (11) | 0.0091 (12) |
C8 | 0.0268 (11) | 0.0411 (13) | 0.0384 (12) | −0.0036 (10) | 0.0115 (9) | −0.0008 (10) |
C9 | 0.0329 (12) | 0.0355 (12) | 0.0360 (12) | 0.0001 (10) | 0.0062 (9) | 0.0038 (10) |
C12 | 0.0517 (17) | 0.0402 (15) | 0.072 (2) | −0.0077 (13) | 0.0029 (15) | −0.0088 (15) |
C13 | 0.063 (2) | 0.057 (2) | 0.105 (3) | −0.0248 (18) | 0.019 (2) | −0.007 (2) |
S6—C5 | 1.674 (3) | C7—H7A | 0.9600 |
O10—C9 | 1.197 (3) | C7—H7B | 0.9600 |
O11—C9 | 1.330 (3) | C7—H7C | 0.9600 |
O11—C12 | 1.455 (4) | C8—C9 | 1.499 (4) |
N1—C5 | 1.331 (3) | C8—H8A | 0.9700 |
N1—N2 | 1.364 (3) | C8—H8B | 0.9700 |
N1—H1 | 0.79 (4) | C12—C13 | 1.482 (5) |
N2—C3 | 1.301 (3) | C12—H12A | 0.9700 |
N4—C5 | 1.367 (3) | C12—H12B | 0.9700 |
N4—C3 | 1.369 (3) | C13—H13A | 0.9600 |
N4—C8 | 1.450 (3) | C13—H13B | 0.9600 |
C3—C7 | 1.475 (4) | C13—H13C | 0.9600 |
C9—O11—C12 | 115.0 (2) | N4—C8—H8A | 109.3 |
C5—N1—N2 | 113.5 (2) | C9—C8—H8A | 109.3 |
C5—N1—H1 | 123 (3) | N4—C8—H8B | 109.3 |
N2—N1—H1 | 124 (3) | C9—C8—H8B | 109.3 |
C3—N2—N1 | 104.3 (2) | H8A—C8—H8B | 108.0 |
C5—N4—C3 | 108.3 (2) | O10—C9—O11 | 124.9 (3) |
C5—N4—C8 | 124.3 (2) | O10—C9—C8 | 125.4 (2) |
C3—N4—C8 | 127.5 (2) | O11—C9—C8 | 109.7 (2) |
N2—C3—N4 | 110.5 (2) | O11—C12—C13 | 108.2 (3) |
N2—C3—C7 | 125.5 (2) | O11—C12—H12A | 110.1 |
N4—C3—C7 | 124.0 (2) | C13—C12—H12A | 110.1 |
N1—C5—N4 | 103.4 (2) | O11—C12—H12B | 110.1 |
N1—C5—S6 | 129.8 (2) | C13—C12—H12B | 110.1 |
N4—C5—S6 | 126.74 (19) | H12A—C12—H12B | 108.4 |
C3—C7—H7A | 109.5 | C12—C13—H13A | 109.5 |
C3—C7—H7B | 109.5 | C12—C13—H13B | 109.5 |
H7A—C7—H7B | 109.5 | H13A—C13—H13B | 109.5 |
C3—C7—H7C | 109.5 | C12—C13—H13C | 109.5 |
H7A—C7—H7C | 109.5 | H13A—C13—H13C | 109.5 |
H7B—C7—H7C | 109.5 | H13B—C13—H13C | 109.5 |
N4—C8—C9 | 111.52 (19) | ||
C5—N1—N2—C3 | 0.0 (3) | C8—N4—C5—N1 | −177.5 (2) |
N1—N2—C3—N4 | 1.2 (3) | C3—N4—C5—S6 | −176.9 (2) |
N1—N2—C3—C7 | −178.1 (3) | C8—N4—C5—S6 | 3.8 (4) |
C5—N4—C3—N2 | −1.9 (3) | C5—N4—C8—C9 | −88.1 (3) |
C8—N4—C3—N2 | 177.3 (2) | C3—N4—C8—C9 | 92.7 (3) |
C5—N4—C3—C7 | 177.4 (2) | C12—O11—C9—O10 | −5.1 (4) |
C8—N4—C3—C7 | −3.3 (4) | C12—O11—C9—C8 | 175.1 (2) |
N2—N1—C5—N4 | −1.1 (3) | N4—C8—C9—O10 | −3.2 (4) |
N2—N1—C5—S6 | 177.5 (2) | N4—C8—C9—O11 | 176.7 (2) |
C3—N4—C5—N1 | 1.8 (3) | C9—O11—C12—C13 | 179.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S6i | 0.79 (4) | 2.56 (4) | 3.339 (3) | 170 (4) |
C8—H8B···N2ii | 0.97 | 2.50 | 3.407 (3) | 155 |
C13—H13A···O10ii | 0.96 | 2.57 | 3.482 (5) | 159 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C7H11N3O2S |
Mr | 201.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.4438 (19), 15.2328 (15), 9.9672 (8) |
β (°) | 98.416 (19) |
V (Å3) | 967.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.60 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Kuma KM-4 four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.754, 0.869 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2979, 2837, 1571 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.705 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.198, 0.93 |
No. of reflections | 2837 |
No. of parameters | 123 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.64, −0.48 |
Computer programs: KM4B8 (Gałdecki et al., 1996), DATAPROC (Gałdecki et al., 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S6i | 0.79 (4) | 2.56 (4) | 3.339 (3) | 170 (4) |
C8—H8B···N2ii | 0.97 | 2.50 | 3.407 (3) | 155 |
C13—H13A···O10ii | 0.96 | 2.57 | 3.482 (5) | 159 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x+1, y, z. |
References
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The 1,2,4-triazoline-thiones were found to have significant antimicrobial action (Saadeh et al., 2010; Akhtar et al., 2008; Al-Omar et al., 2010). The title compound, (I), belongs to 3- and 4-substituted derivatives of 1,2,4-triazoline-thiones with potential antituberculosis activity against mycobacterium strains of Mycobacterium smegmatis, Mycobacterium phlei and Mycobacterium H37Ra (Pitucha et al., 2010).
The X-ray analysis of the title compound undertook in order to its structural characterization and to identification of the proper thiol-thione tautomeric form revealed that this compound exists as 5-thioxo tautomer in the crystalline state. The molecular geometry of (I) is very similar to that observed in related structures of 2-(3-methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetic acid (Kruszynski et al., 2007) and 4-[3-(2-methyl-furan-3-yl)-5-thioxo-1,2,4-triazol-4-yl]acetic acid (Siwek et al., 2008). The 1,2,4-triazoline ring is planar to within 0.010 (2) Å. The ethyl acetate chain is almost planar with the most deviating C12 atom from the best C8/C9/O10/O11/C12/C13 plane by 0.061 (4) Å and it adopts a gauche conformation in respect to 1,2,4-triazoline ring with the torsion angle C3—N4—C8—C9 of 92.7 (3)°. This conformation is stabilized by the C8—H8B···S6 intramolecular hydrogen bond specified as S(5) in graph set notation (Bernstein et al., 1995).
In the crystal structure, (Fig. 2), the molecules of (I) are linked by a combination of N1—H1···S6, C8—H8B···N2 and C13—H13A···O10 intermolecular hydrogen bond into chains of R22(8), R22(13) and R44(16) edge-fused rings parallel to the [100] direction.