Download citation
Download citation
link to html
All inter­atomic distances in the title compound, C13H15N3O2S, are normal. The 1,2,4-triazole ring is planar and is inclined at 46.50 (6)° to the phenyl ring. The ethoxy­carbonyl­methyl group is also close to being planar and is inclined at 87.54 (9)° to the 1,2,4-triazole ring. The crystal was an inversion twin with a twin ratio 0.88 (3):0.12 (3).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050635/bt2537sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050635/bt2537Isup2.hkl
Contains datablock I

CCDC reference: 667396

Key indicators

  • Single-crystal X-ray study
  • T = 290 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.040
  • wR factor = 0.120
  • Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 80.74 From the CIF: _reflns_number_total 2887 Count of symmetry unique reflns 1775 Completeness (_total/calc) 162.65% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1112 Fraction of Friedel pairs measured 0.626 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The title compound (I) is a member of 1,2,4-triazoline-3-thione derivatives family, known to posses antibacterial, anitimycotical and antivirostatical activity (Veverka and Marchalin, 1987; Bohn and Karow, 1981; Potts, 1961; Santus, 1980).

All interatomic distances in (I) are normal. The 1,2,4-triazoline ring of (I) can be considered as planar in the range of experimental error. The most deviating C2 atom derives 0.0046 (12) Å from weighted least squares plane of the ring. The C3, C9, C10, S1 atoms deviate respectively -0.021 (4), 0.006 (5), 0.254 (4), -0.009 (4) from this plane. The phenyl ring is inclined at 46.50 (6)° to above mentioned heteroatomic ring. The ethoxycarbonylmethyl moiety is close to planarity (Table 1) and the most deviating atom is C12 [0.038 (3) Å from weighted O1, O2, C10, C11, C12, C13 least-squares plane]. This plane is inclined at 87.54 (9)° to weighted least squares plane of 1,2,4-triazoline ring. In the structure can not be found any unusual intermolecular contacts. The crystal was a racemic twin with the twin ratio of 0.88 (3):0.12 (3).

Related literature top

For potential applications, see: Bohn and Karow (1981), Potts (1961), Santus (1980). For structures of other 1,4,5-substitued 2,4-dihydro-3H-1,2,4-triazole-3-thiones, see: Dinçer et al., (2005), El-Gazzar et al., (1999), Saghiyan et al., (2006). For general synthesis procedures, see: Bany and Dobosz (1972), Veverka and Marchalin (1987).

Experimental top

The title compound was synthesized according to method of Bany and Dobosz (1972). Crystals were obtained by crystallization from mixture of water, methanol, ethanol and 2-butanone (1:2:3:1).

Refinement top

The hydrogen atoms were placed in calculated positions after four cycles of anisotrophic refinement and were refined as riding on adjacent atom with Uiso(H) = 1.2Ueq(C-non-methyl) and Uiso(H) = 1.5Ueq(C-methyl). The methyl groups were allowed to rotate about their local threefold axis (AFIX 137).

Structure description top

The title compound (I) is a member of 1,2,4-triazoline-3-thione derivatives family, known to posses antibacterial, anitimycotical and antivirostatical activity (Veverka and Marchalin, 1987; Bohn and Karow, 1981; Potts, 1961; Santus, 1980).

All interatomic distances in (I) are normal. The 1,2,4-triazoline ring of (I) can be considered as planar in the range of experimental error. The most deviating C2 atom derives 0.0046 (12) Å from weighted least squares plane of the ring. The C3, C9, C10, S1 atoms deviate respectively -0.021 (4), 0.006 (5), 0.254 (4), -0.009 (4) from this plane. The phenyl ring is inclined at 46.50 (6)° to above mentioned heteroatomic ring. The ethoxycarbonylmethyl moiety is close to planarity (Table 1) and the most deviating atom is C12 [0.038 (3) Å from weighted O1, O2, C10, C11, C12, C13 least-squares plane]. This plane is inclined at 87.54 (9)° to weighted least squares plane of 1,2,4-triazoline ring. In the structure can not be found any unusual intermolecular contacts. The crystal was a racemic twin with the twin ratio of 0.88 (3):0.12 (3).

For potential applications, see: Bohn and Karow (1981), Potts (1961), Santus (1980). For structures of other 1,4,5-substitued 2,4-dihydro-3H-1,2,4-triazole-3-thiones, see: Dinçer et al., (2005), El-Gazzar et al., (1999), Saghiyan et al., (2006). For general synthesis procedures, see: Bany and Dobosz (1972), Veverka and Marchalin (1987).

Computing details top

Data collection: KM-4 Software (Kuma, 1993); cell refinement: KM-4 Software (Kuma, 1993); data reduction: DATAPROC (Version 10.0.4; Gałdecki et al., 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL/PC (Sheldrick, 1990b) and ORTEP-3 for Windows (Version 1.062; Farrugia 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound (I). Displacement ellipsoids are drawn at the 50% probability level.
Ethyl (1-methyl-3-phenyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetate top
Crystal data top
C13H15N3O2SF(000) = 584
Mr = 277.34Dx = 1.320 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 99 reflections
a = 7.6493 (8) Åθ = 5–60°
b = 12.8459 (10) ŵ = 2.09 mm1
c = 14.2061 (11) ÅT = 290 K
V = 1395.9 (2) Å3Prism, colourless
Z = 40.40 × 0.20 × 0.20 mm
Data collection top
Kuma KM-4
diffractometer
2386 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Graphite monochromatorθmax = 80.7°, θmin = 4.6°
ω–2θ scansh = 89
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
k = 016
Tmin = 0.489, Tmax = 0.681l = 018
3095 measured reflections3 standard reflections every 100 reflections
2887 independent reflections intensity decay: 4.7%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040 w = 1/[σ2(Fo2) + (0.0798P)2 + 0.0731P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.21 e Å3
2887 reflectionsΔρmin = 0.26 e Å3
176 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0114 (11)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1112 Friedel pairs
Secondary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.12 (3)
Crystal data top
C13H15N3O2SV = 1395.9 (2) Å3
Mr = 277.34Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 7.6493 (8) ŵ = 2.09 mm1
b = 12.8459 (10) ÅT = 290 K
c = 14.2061 (11) Å0.40 × 0.20 × 0.20 mm
Data collection top
Kuma KM-4
diffractometer
2386 reflections with I > 2σ(I)
Absorption correction: numerical
(X-RED; Stoe & Cie, 1999)
Rint = 0.035
Tmin = 0.489, Tmax = 0.6813 standard reflections every 100 reflections
3095 measured reflections intensity decay: 4.7%
2887 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.120Δρmax = 0.21 e Å3
S = 1.05Δρmin = 0.26 e Å3
2887 reflectionsAbsolute structure: Flack (1983), 1112 Friedel pairs
176 parametersAbsolute structure parameter: 0.12 (3)
0 restraints
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. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.8202 (2)0.79745 (12)0.41689 (13)0.0570 (4)
N20.8363 (3)0.74693 (13)0.33226 (13)0.0591 (4)
C10.8901 (3)0.64742 (15)0.34141 (16)0.0578 (5)
S10.92489 (10)0.55811 (4)0.25886 (5)0.0790 (2)
N30.9083 (2)0.63576 (11)0.43724 (12)0.0526 (4)
C20.8658 (3)0.72900 (13)0.47946 (16)0.0521 (4)
C30.8649 (3)0.74947 (14)0.58079 (16)0.0539 (5)
C40.7864 (4)0.68126 (19)0.64452 (17)0.0671 (6)
H40.73730.61920.62350.081*
C50.7821 (4)0.7066 (2)0.7389 (2)0.0802 (7)
H50.73130.66090.78170.096*
C60.8528 (4)0.7995 (2)0.7705 (2)0.0807 (7)
H60.84780.81630.83410.097*
C70.9310 (4)0.86738 (19)0.70771 (19)0.0727 (6)
H70.97850.92970.72900.087*
C80.9382 (3)0.84203 (15)0.61283 (17)0.0616 (5)
H80.99210.88700.57060.074*
C90.7969 (4)0.80072 (19)0.2454 (2)0.0782 (7)
H9A0.72080.85840.25830.117*
H9C0.74050.75370.20260.117*
H9B0.90340.82580.21780.117*
C100.9964 (3)0.54664 (15)0.47858 (19)0.0618 (5)
H10A1.03970.56670.54010.074*
H10B1.09700.52990.43990.074*
C110.8880 (3)0.44955 (15)0.48975 (16)0.0579 (5)
O10.9562 (3)0.36687 (13)0.5025 (2)0.1044 (8)
O20.7171 (2)0.46454 (9)0.48593 (10)0.0537 (3)
C120.6098 (3)0.37176 (15)0.50081 (17)0.0598 (5)
H12A0.62980.34400.56340.072*
H12B0.64020.31850.45520.072*
C130.4237 (4)0.4017 (2)0.4899 (3)0.0881 (9)
H13A0.35060.34280.50320.132*
H13B0.40340.42470.42650.132*
H13C0.39660.45710.53280.132*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0613 (11)0.0365 (7)0.0731 (11)0.0006 (6)0.0050 (8)0.0019 (7)
N20.0666 (11)0.0399 (8)0.0708 (10)0.0017 (8)0.0048 (8)0.0053 (7)
C10.0555 (13)0.0393 (9)0.0785 (12)0.0046 (8)0.0038 (10)0.0006 (8)
S10.0924 (5)0.0536 (3)0.0909 (4)0.0013 (3)0.0131 (4)0.0149 (3)
N30.0492 (9)0.0319 (7)0.0767 (10)0.0004 (6)0.0013 (8)0.0021 (6)
C20.0477 (10)0.0337 (8)0.0748 (12)0.0017 (7)0.0019 (9)0.0028 (7)
C30.0491 (10)0.0380 (8)0.0746 (12)0.0004 (7)0.0013 (9)0.0028 (8)
C40.0678 (14)0.0546 (11)0.0789 (14)0.0177 (11)0.0024 (11)0.0063 (10)
C50.0914 (19)0.0750 (15)0.0743 (15)0.0184 (14)0.0008 (15)0.0112 (12)
C60.094 (2)0.0781 (16)0.0697 (14)0.0080 (15)0.0040 (13)0.0019 (12)
C70.0771 (16)0.0537 (11)0.0872 (16)0.0054 (11)0.0106 (12)0.0093 (11)
C80.0603 (13)0.0396 (9)0.0850 (14)0.0014 (8)0.0005 (11)0.0004 (9)
C90.1017 (19)0.0573 (12)0.0755 (14)0.0040 (12)0.0010 (16)0.0159 (11)
C100.0517 (12)0.0387 (9)0.0950 (16)0.0038 (8)0.0103 (10)0.0011 (10)
C110.0544 (13)0.0369 (8)0.0825 (13)0.0048 (8)0.0091 (10)0.0064 (8)
O10.0733 (12)0.0404 (8)0.200 (3)0.0123 (8)0.0145 (14)0.0236 (11)
O20.0547 (8)0.0332 (6)0.0732 (8)0.0004 (5)0.0051 (7)0.0067 (5)
C120.0671 (14)0.0365 (8)0.0759 (13)0.0059 (9)0.0022 (10)0.0089 (8)
C130.0627 (16)0.0563 (13)0.145 (3)0.0130 (11)0.0068 (17)0.0213 (15)
Geometric parameters (Å, º) top
N1—C21.298 (3)C7—H70.9300
N1—N21.372 (3)C8—H80.9300
N2—C11.349 (2)C9—H9A0.9600
N2—C91.445 (3)C9—H9C0.9600
C1—N31.377 (3)C9—H9B0.9600
C1—S11.662 (2)C10—C111.506 (3)
N3—C21.378 (2)C10—H10A0.9700
N3—C101.452 (2)C10—H10B0.9700
C2—C31.463 (3)C11—O11.197 (2)
C3—C81.391 (3)C11—O21.322 (3)
C3—C41.396 (3)O2—C121.463 (2)
C4—C51.381 (4)C12—C131.483 (4)
C4—H40.9300C12—H12A0.9700
C5—C61.385 (4)C12—H12B0.9700
C5—H50.9300C13—H13A0.9600
C6—C71.383 (4)C13—H13B0.9600
C6—H60.9300C13—H13C0.9600
C7—C81.388 (3)
C2—N1—N2104.81 (16)C3—C8—H8119.9
C1—N2—N1113.02 (18)N2—C9—H9A109.5
C1—N2—C9126.8 (2)N2—C9—H9C109.5
N1—N2—C9120.20 (18)H9A—C9—H9C109.5
N2—C1—N3103.25 (18)N2—C9—H9B109.5
N2—C1—S1129.41 (18)H9A—C9—H9B109.5
N3—C1—S1127.34 (15)H9C—C9—H9B109.5
C1—N3—C2108.18 (16)N3—C10—C11116.10 (18)
C1—N3—C10122.18 (18)N3—C10—H10A108.3
C2—N3—C10128.20 (19)C11—C10—H10A108.3
N1—C2—N3110.74 (19)N3—C10—H10B108.3
N1—C2—C3123.40 (17)C11—C10—H10B108.3
N3—C2—C3125.83 (18)H10A—C10—H10B107.4
C8—C3—C4119.9 (2)O1—C11—O2124.5 (2)
C8—C3—C2118.26 (19)O1—C11—C10120.7 (2)
C4—C3—C2121.83 (19)O2—C11—C10114.80 (16)
C5—C4—C3119.5 (2)C11—O2—C12115.50 (15)
C5—C4—H4120.2O2—C12—C13108.19 (17)
C3—C4—H4120.2O2—C12—H12A110.1
C4—C5—C6120.5 (2)C13—C12—H12A110.1
C4—C5—H5119.7O2—C12—H12B110.1
C6—C5—H5119.7C13—C12—H12B110.1
C7—C6—C5120.2 (2)H12A—C12—H12B108.4
C7—C6—H6119.9C12—C13—H13A109.5
C5—C6—H6119.9C12—C13—H13B109.5
C6—C7—C8119.7 (2)H13A—C13—H13B109.5
C6—C7—H7120.1C12—C13—H13C109.5
C8—C7—H7120.1H13A—C13—H13C109.5
C7—C8—C3120.1 (2)H13B—C13—H13C109.5
C7—C8—H8119.9
N3—C10—C11—O1162.9 (3)C10—C11—O2—C12177.40 (19)
N3—C10—C11—O218.2 (3)C11—O2—C12—C13177.5 (2)

Experimental details

Crystal data
Chemical formulaC13H15N3O2S
Mr277.34
Crystal system, space groupOrthorhombic, P212121
Temperature (K)290
a, b, c (Å)7.6493 (8), 12.8459 (10), 14.2061 (11)
V3)1395.9 (2)
Z4
Radiation typeCu Kα
µ (mm1)2.09
Crystal size (mm)0.40 × 0.20 × 0.20
Data collection
DiffractometerKuma KM-4
Absorption correctionNumerical
(X-RED; Stoe & Cie, 1999)
Tmin, Tmax0.489, 0.681
No. of measured, independent and
observed [I > 2σ(I)] reflections
3095, 2887, 2386
Rint0.035
(sin θ/λ)max1)0.640
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.120, 1.05
No. of reflections2887
No. of parameters176
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.26
Absolute structureFlack (1983), 1112 Friedel pairs
Absolute structure parameter0.12 (3)

Computer programs: KM-4 Software (Kuma, 1993), DATAPROC (Version 10.0.4; Gałdecki et al., 1998), SHELXS97 (Sheldrick, 1990a), XP in SHELXTL/PC (Sheldrick, 1990b) and ORTEP-3 for Windows (Version 1.062; Farrugia 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Selected torsion angles (º) top
N3—C10—C11—O1162.9 (3)C10—C11—O2—C12177.40 (19)
N3—C10—C11—O218.2 (3)C11—O2—C12—C13177.5 (2)
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds