Ethyl 2-(3-methyl-5-sulfanyl­idene-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetate

Karczmarzyk, Z.; Pitucha, M.; Wysocki, W.; Fruziński, A.; Olender, E.

doi:10.1107/S1600536812044716

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages o3264-o3265

doi:10.1107/S1600536812044716

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Ethyl 2-(3-methyl-5-sulfanylidene-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetate

Zbigniew Karczmarzyk,^a ^* Monika Pitucha,^b Waldemar Wysocki,^a Andrzej Fruziński ^c and Ewa Olender ^a

^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

(Received 9 October 2012; accepted 29 October 2012; online 3 November 2012)

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

C₇H₁₁N₃O₂S
M_r = 201.25
Monoclinic, P 2₁ /c
a = 6.4438 (19) Å
b = 15.2328 (15) Å
c = 9.9672 (8) Å
β = 98.416 (19)°
V = 967.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.60 × 0.30 × 0.30 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.754, T_max = 0.869
2979 measured reflections
2837 independent reflections
1571 reflections with I > 2σ(I)
R_int = 0.069
2 standard reflections every 100 reflections intensity decay: 8.9%

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.198
S = 0.93
2837 reflections
123 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: KM4B8 (Gałdecki et al., 1996 $[Gałdecki, Z., Kowalski, A., Kucharczyk, D. & Uszyński, L. (1996). KM4B8. Kuma Diffraction, Wrocław, Poland.]$ ); cell refinement: KM4B8; data reduction: DATAPROC (Gałdecki et al., 1995 $[Gałdecki, Z., Kowalski, A. & Uszyński, L. (1995). DATAPROC. Kuma Diffraction, Wrocław, Poland.]$ ); 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812044716/fj2601sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044716/fj2601Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812044716/fj2601Isup3.cml

checkCIF report

Comment top

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.

Related literature top

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 top

The title compound, (I), was prepared from acetamidrazone hydrochloride and carboethoxymethyl isothiocyanate, according to the method of Bany & Dobosz (1972).

Computing details top

Data collection: KM4B8 (Gałdecki et al., 1996); cell refinement: 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).

Figures top

	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).

Ethyl 2-(3-methyl-5-sulfanylidene-4,5-dihydro-1H-1,2,4-triazol-4-yl)acetate top

Crystal data top

C₇H₁₁N₃O₂S	F(000) = 424
M_r = 201.25	D_x = 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

Data collection top

Kuma KM-4 four-circle diffractometer	1571 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.069
Graphite monochromator	θ_max = 30.1°, θ_min = 2.5°
ω–2θ scans	h = −9→8
Absorption correction: ψ scan (North et al., 1968)	k = 0→21
T_min = 0.754, T_max = 0.869	l = 0→14
2979 measured reflections	2 standard reflections every 100 reflections
2837 independent reflections	intensity decay: 8.9%

Refinement top

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(F_o²) + (0.1344P)²] where P = (F_o² + 2F_c²)/3
2837 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₇H₁₁N₃O₂S	V = 967.8 (3) Å³
M_r = 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)°

Data collection top

Kuma KM-4 four-circle diffractometer	1571 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.069
T_min = 0.754, T_max = 0.869	2 standard reflections every 100 reflections
2979 measured reflections	intensity decay: 8.9%
2837 independent reflections

Refinement top

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	Δρ_max = 0.64 e Å⁻³
2837 reflections	Δρ_min = −0.48 e Å⁻³
123 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.754, 0.869
No. of measured, independent and observed [I > 2σ(I)] reflections	2979, 2837, 1571
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

Akhtar, T., Hameed, S., Khan, K. M. & Choudhary, M. I. (2008). Med. Chem. 4, 539–543. Web of Science CrossRef PubMed CAS Google Scholar
Al-Omar, M. A., Al-Abdullah, E. S., Shehata, I. A., Habib, E. E., Ibrahim, T. M. & El-Emam, A. A. (2010). Molecules, 15, 2526–2550. Web of Science CAS PubMed Google Scholar
Bany, T. & Dobosz, M. (1972). Ann. Univ. Mariae Curie-Sklodowska Sect AA, 26/27, 23–32. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gałdecki, Z., Kowalski, A., Kucharczyk, D. & Uszyński, L. (1996). KM4B8. Kuma Diffraction, Wrocław, Poland. Google Scholar
Gałdecki, Z., Kowalski, A. & Uszyński, L. (1995). DATAPROC. Kuma Diffraction, Wrocław, Poland. Google Scholar
Kruszynski, R., Trzesowska, A., Przybycin, M., Gil, K. & Dobosz, M. (2007). Acta Cryst. E63, o4378. Web of Science CSD CrossRef IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Pitucha, M., Polak, B., Swatko-Ossor, M., Popiołek, Ł. & Ginalska, G. (2010). Croat. Chem. Acta, 83, 299–306. CAS Google Scholar
Saadeh, H. A., Mosleh, I. M., Al-Bakri, A. G. & Mubarak, M. I. (2010). Monatsh. Chem. 141, 471–478. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siwek, A., Wujec, M., Wawrzycka-Gorczyca, I., Dobosz, M. & Paneth, P. (2008). Heteroat. Chem. 19, 337–344. Web of Science CSD CrossRef CAS Google Scholar

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Volume 68| Part 12| December 2012| Pages o3264-o3265

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