Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050635/bt2537sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050635/bt2537Isup2.hkl |
CCDC reference: 667396
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (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
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).
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).
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).
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).
Fig. 1. Molecular structure of the title compound (I). Displacement ellipsoids are drawn at the 50% probability level. |
C13H15N3O2S | F(000) = 584 |
Mr = 277.34 | Dx = 1.320 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 99 reflections |
a = 7.6493 (8) Å | θ = 5–60° |
b = 12.8459 (10) Å | µ = 2.09 mm−1 |
c = 14.2061 (11) Å | T = 290 K |
V = 1395.9 (2) Å3 | Prism, colourless |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
Kuma KM-4 diffractometer | 2386 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 80.7°, θmin = 4.6° |
ω–2θ scans | h = −8→9 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1999) | k = 0→16 |
Tmin = 0.489, Tmax = 0.681 | l = 0→18 |
3095 measured reflections | 3 standard reflections every 100 reflections |
2887 independent reflections | intensity decay: 4.7% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-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 = 1.05 | Δρmax = 0.21 e Å−3 |
2887 reflections | Δρmin = −0.26 e Å−3 |
176 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0114 (11) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 1112 Friedel pairs |
Secondary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.12 (3) |
C13H15N3O2S | V = 1395.9 (2) Å3 |
Mr = 277.34 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 7.6493 (8) Å | µ = 2.09 mm−1 |
b = 12.8459 (10) Å | T = 290 K |
c = 14.2061 (11) Å | 0.40 × 0.20 × 0.20 mm |
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 = 0.681 | 3 standard reflections every 100 reflections |
3095 measured reflections | intensity decay: 4.7% |
2887 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.120 | Δρmax = 0.21 e Å−3 |
S = 1.05 | Δρmin = −0.26 e Å−3 |
2887 reflections | Absolute structure: Flack (1983), 1112 Friedel pairs |
176 parameters | Absolute structure parameter: 0.12 (3) |
0 restraints |
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 | ||
N1 | 0.8202 (2) | 0.79745 (12) | 0.41689 (13) | 0.0570 (4) | |
N2 | 0.8363 (3) | 0.74693 (13) | 0.33226 (13) | 0.0591 (4) | |
C1 | 0.8901 (3) | 0.64742 (15) | 0.34141 (16) | 0.0578 (5) | |
S1 | 0.92489 (10) | 0.55811 (4) | 0.25886 (5) | 0.0790 (2) | |
N3 | 0.9083 (2) | 0.63576 (11) | 0.43724 (12) | 0.0526 (4) | |
C2 | 0.8658 (3) | 0.72900 (13) | 0.47946 (16) | 0.0521 (4) | |
C3 | 0.8649 (3) | 0.74947 (14) | 0.58079 (16) | 0.0539 (5) | |
C4 | 0.7864 (4) | 0.68126 (19) | 0.64452 (17) | 0.0671 (6) | |
H4 | 0.7373 | 0.6192 | 0.6235 | 0.081* | |
C5 | 0.7821 (4) | 0.7066 (2) | 0.7389 (2) | 0.0802 (7) | |
H5 | 0.7313 | 0.6609 | 0.7817 | 0.096* | |
C6 | 0.8528 (4) | 0.7995 (2) | 0.7705 (2) | 0.0807 (7) | |
H6 | 0.8478 | 0.8163 | 0.8341 | 0.097* | |
C7 | 0.9310 (4) | 0.86738 (19) | 0.70771 (19) | 0.0727 (6) | |
H7 | 0.9785 | 0.9297 | 0.7290 | 0.087* | |
C8 | 0.9382 (3) | 0.84203 (15) | 0.61283 (17) | 0.0616 (5) | |
H8 | 0.9921 | 0.8870 | 0.5706 | 0.074* | |
C9 | 0.7969 (4) | 0.80072 (19) | 0.2454 (2) | 0.0782 (7) | |
H9A | 0.7208 | 0.8584 | 0.2583 | 0.117* | |
H9C | 0.7405 | 0.7537 | 0.2026 | 0.117* | |
H9B | 0.9034 | 0.8258 | 0.2178 | 0.117* | |
C10 | 0.9964 (3) | 0.54664 (15) | 0.47858 (19) | 0.0618 (5) | |
H10A | 1.0397 | 0.5667 | 0.5401 | 0.074* | |
H10B | 1.0970 | 0.5299 | 0.4399 | 0.074* | |
C11 | 0.8880 (3) | 0.44955 (15) | 0.48975 (16) | 0.0579 (5) | |
O1 | 0.9562 (3) | 0.36687 (13) | 0.5025 (2) | 0.1044 (8) | |
O2 | 0.7171 (2) | 0.46454 (9) | 0.48593 (10) | 0.0537 (3) | |
C12 | 0.6098 (3) | 0.37176 (15) | 0.50081 (17) | 0.0598 (5) | |
H12A | 0.6298 | 0.3440 | 0.5634 | 0.072* | |
H12B | 0.6402 | 0.3185 | 0.4552 | 0.072* | |
C13 | 0.4237 (4) | 0.4017 (2) | 0.4899 (3) | 0.0881 (9) | |
H13A | 0.3506 | 0.3428 | 0.5032 | 0.132* | |
H13B | 0.4034 | 0.4247 | 0.4265 | 0.132* | |
H13C | 0.3966 | 0.4571 | 0.5328 | 0.132* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0613 (11) | 0.0365 (7) | 0.0731 (11) | 0.0006 (6) | 0.0050 (8) | 0.0019 (7) |
N2 | 0.0666 (11) | 0.0399 (8) | 0.0708 (10) | −0.0017 (8) | 0.0048 (8) | 0.0053 (7) |
C1 | 0.0555 (13) | 0.0393 (9) | 0.0785 (12) | −0.0046 (8) | 0.0038 (10) | 0.0006 (8) |
S1 | 0.0924 (5) | 0.0536 (3) | 0.0909 (4) | −0.0013 (3) | 0.0131 (4) | −0.0149 (3) |
N3 | 0.0492 (9) | 0.0319 (7) | 0.0767 (10) | −0.0004 (6) | 0.0013 (8) | 0.0021 (6) |
C2 | 0.0477 (10) | 0.0337 (8) | 0.0748 (12) | −0.0017 (7) | 0.0019 (9) | 0.0028 (7) |
C3 | 0.0491 (10) | 0.0380 (8) | 0.0746 (12) | −0.0004 (7) | −0.0013 (9) | 0.0028 (8) |
C4 | 0.0678 (14) | 0.0546 (11) | 0.0789 (14) | −0.0177 (11) | −0.0024 (11) | 0.0063 (10) |
C5 | 0.0914 (19) | 0.0750 (15) | 0.0743 (15) | −0.0184 (14) | 0.0008 (15) | 0.0112 (12) |
C6 | 0.094 (2) | 0.0781 (16) | 0.0697 (14) | −0.0080 (15) | −0.0040 (13) | −0.0019 (12) |
C7 | 0.0771 (16) | 0.0537 (11) | 0.0872 (16) | −0.0054 (11) | −0.0106 (12) | −0.0093 (11) |
C8 | 0.0603 (13) | 0.0396 (9) | 0.0850 (14) | −0.0014 (8) | −0.0005 (11) | 0.0004 (9) |
C9 | 0.1017 (19) | 0.0573 (12) | 0.0755 (14) | −0.0040 (12) | 0.0010 (16) | 0.0159 (11) |
C10 | 0.0517 (12) | 0.0387 (9) | 0.0950 (16) | 0.0038 (8) | −0.0103 (10) | 0.0011 (10) |
C11 | 0.0544 (13) | 0.0369 (8) | 0.0825 (13) | 0.0048 (8) | −0.0091 (10) | 0.0064 (8) |
O1 | 0.0733 (12) | 0.0404 (8) | 0.200 (3) | 0.0123 (8) | −0.0145 (14) | 0.0236 (11) |
O2 | 0.0547 (8) | 0.0332 (6) | 0.0732 (8) | −0.0004 (5) | −0.0051 (7) | 0.0067 (5) |
C12 | 0.0671 (14) | 0.0365 (8) | 0.0759 (13) | −0.0059 (9) | 0.0022 (10) | 0.0089 (8) |
C13 | 0.0627 (16) | 0.0563 (13) | 0.145 (3) | −0.0130 (11) | −0.0068 (17) | 0.0213 (15) |
N1—C2 | 1.298 (3) | C7—H7 | 0.9300 |
N1—N2 | 1.372 (3) | C8—H8 | 0.9300 |
N2—C1 | 1.349 (2) | C9—H9A | 0.9600 |
N2—C9 | 1.445 (3) | C9—H9C | 0.9600 |
C1—N3 | 1.377 (3) | C9—H9B | 0.9600 |
C1—S1 | 1.662 (2) | C10—C11 | 1.506 (3) |
N3—C2 | 1.378 (2) | C10—H10A | 0.9700 |
N3—C10 | 1.452 (2) | C10—H10B | 0.9700 |
C2—C3 | 1.463 (3) | C11—O1 | 1.197 (2) |
C3—C8 | 1.391 (3) | C11—O2 | 1.322 (3) |
C3—C4 | 1.396 (3) | O2—C12 | 1.463 (2) |
C4—C5 | 1.381 (4) | C12—C13 | 1.483 (4) |
C4—H4 | 0.9300 | C12—H12A | 0.9700 |
C5—C6 | 1.385 (4) | C12—H12B | 0.9700 |
C5—H5 | 0.9300 | C13—H13A | 0.9600 |
C6—C7 | 1.383 (4) | C13—H13B | 0.9600 |
C6—H6 | 0.9300 | C13—H13C | 0.9600 |
C7—C8 | 1.388 (3) | ||
C2—N1—N2 | 104.81 (16) | C3—C8—H8 | 119.9 |
C1—N2—N1 | 113.02 (18) | N2—C9—H9A | 109.5 |
C1—N2—C9 | 126.8 (2) | N2—C9—H9C | 109.5 |
N1—N2—C9 | 120.20 (18) | H9A—C9—H9C | 109.5 |
N2—C1—N3 | 103.25 (18) | N2—C9—H9B | 109.5 |
N2—C1—S1 | 129.41 (18) | H9A—C9—H9B | 109.5 |
N3—C1—S1 | 127.34 (15) | H9C—C9—H9B | 109.5 |
C1—N3—C2 | 108.18 (16) | N3—C10—C11 | 116.10 (18) |
C1—N3—C10 | 122.18 (18) | N3—C10—H10A | 108.3 |
C2—N3—C10 | 128.20 (19) | C11—C10—H10A | 108.3 |
N1—C2—N3 | 110.74 (19) | N3—C10—H10B | 108.3 |
N1—C2—C3 | 123.40 (17) | C11—C10—H10B | 108.3 |
N3—C2—C3 | 125.83 (18) | H10A—C10—H10B | 107.4 |
C8—C3—C4 | 119.9 (2) | O1—C11—O2 | 124.5 (2) |
C8—C3—C2 | 118.26 (19) | O1—C11—C10 | 120.7 (2) |
C4—C3—C2 | 121.83 (19) | O2—C11—C10 | 114.80 (16) |
C5—C4—C3 | 119.5 (2) | C11—O2—C12 | 115.50 (15) |
C5—C4—H4 | 120.2 | O2—C12—C13 | 108.19 (17) |
C3—C4—H4 | 120.2 | O2—C12—H12A | 110.1 |
C4—C5—C6 | 120.5 (2) | C13—C12—H12A | 110.1 |
C4—C5—H5 | 119.7 | O2—C12—H12B | 110.1 |
C6—C5—H5 | 119.7 | C13—C12—H12B | 110.1 |
C7—C6—C5 | 120.2 (2) | H12A—C12—H12B | 108.4 |
C7—C6—H6 | 119.9 | C12—C13—H13A | 109.5 |
C5—C6—H6 | 119.9 | C12—C13—H13B | 109.5 |
C6—C7—C8 | 119.7 (2) | H13A—C13—H13B | 109.5 |
C6—C7—H7 | 120.1 | C12—C13—H13C | 109.5 |
C8—C7—H7 | 120.1 | H13A—C13—H13C | 109.5 |
C7—C8—C3 | 120.1 (2) | H13B—C13—H13C | 109.5 |
C7—C8—H8 | 119.9 | ||
N3—C10—C11—O1 | 162.9 (3) | C10—C11—O2—C12 | −177.40 (19) |
N3—C10—C11—O2 | −18.2 (3) | C11—O2—C12—C13 | −177.5 (2) |
Experimental details
Crystal data | |
Chemical formula | C13H15N3O2S |
Mr | 277.34 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 290 |
a, b, c (Å) | 7.6493 (8), 12.8459 (10), 14.2061 (11) |
V (Å3) | 1395.9 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.09 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Kuma KM-4 |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1999) |
Tmin, Tmax | 0.489, 0.681 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3095, 2887, 2386 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.640 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.120, 1.05 |
No. of reflections | 2887 |
No. of parameters | 176 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.26 |
Absolute structure | Flack (1983), 1112 Friedel pairs |
Absolute structure parameter | 0.12 (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).
N3—C10—C11—O1 | 162.9 (3) | C10—C11—O2—C12 | −177.40 (19) |
N3—C10—C11—O2 | −18.2 (3) | C11—O2—C12—C13 | −177.5 (2) |
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).