4-(4-Oxopent-2-en-2-yl­amino)-1,2,4-triazol-1-ium-5-thiol­ate

Zhu, X.-C.; Zhang, Q.-L.; Zhang, Y.-Q.; Zhu, B.-X.

doi:10.1107/S1600536809019850

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1458

doi:10.1107/S1600536809019850

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4-(4-Oxopent-2-en-2-ylamino)-1,2,4-triazol-1-ium-5-thiolate

Xing-Cheng Zhu,^a Qi-Long Zhang,^a Yun-Qian Zhang ^a and Bi-Xue Zhu ^a ^*

^aKey Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, People's Republic of China
^*Correspondence e-mail: sci.yqzhang@gzu.edu.cn

(Received 24 May 2009; accepted 25 May 2009; online 6 June 2009)

In the title compound, C₈H₁₂N₄OS, an intramolecular N—H⋯O hydrogen bond links the imine N atom to the oxo O atom. In the crystal, molecules are linked by intermolecular N—H⋯O and N—H⋯S hydrogen bonds, forming a two-dimensional framework.

Related literature

For Schiff base metal complexes, see: Lacroix (2001 ); Sabater et al. (2001 ). For the use of 1,2,4-triazole and its derivatives as ligands to bridge metal ions, see: Yi et al. (2004 ).

Experimental

Crystal data

C₈H₁₂N₄OS
M_r = 212.28
Monoclinic, P 2₁ /n
a = 10.620 (6) Å
b = 9.520 (5) Å
c = 10.764 (5) Å
β = 99.560 (14)°
V = 1073.2 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 293 K
0.26 × 0.23 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.932, T_max = 0.952
9199 measured reflections
2071 independent reflections
1688 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.105
S = 1.06
2071 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	2.03	2.659 (2)	130
N1—H1⋯S1ⁱ	0.86	2.81	3.4127 (19)	129
N3—H3A⋯O1ⁱⁱ	0.86	1.93	2.772 (2)	166
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019850/at2792sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019850/at2792Isup2.hkl

checkCIF report

Comment top

Schiff base metal complexes have been widely investigated for their properties and applications in different fields, catalysis (Sabater et al., 2001), materials chemistry (Lacroix 2001) and simple organic molecules, such as 1,2,4-triazole and its derivatives, which usually studied as precursors of compounds with importance in medicine biology and industry, have gained more and more interest as ligands to bridge metal ions due to their potential bridging fashions (Yi et al., 2004). In this work, we report a crystal structure of 3-methyl-4-amino-5-mercapto-1,2,4- triazole, (I).

The crystal structure of the title compound is shown in Fig. 1. The molecule is a non-coplanar structure, an intramolecular N1—H1···O1 hydrogen bonds linking the amines N1 atoms to the enolic O1 atoms. As shown in Fig. 2, the molecules of the title compound are lined up by the intermolecular N1—H1···S1 and N3—H3A···O1 interactions (Table 2) forming a two-dimensional framework.

Related literature top

For Schiff base metal complexes, see: Lacroix (2001); Sabater et al. (2001). For the use of 1,2,4-triazole and its derivatives as ligands to bridge metal ions, see: Yi et al. (2004).

Experimental top

Acetylacetone (1.0 g, 10 mmol) was added to an ethanol solution containing 3-methyl-4-amino-5-mercapto-1,2,4-triazole (1.3 g, 10 mmol). The mixture was heated, stirring for 24 h. The yellow residue yielded and was removed from the solution by filtration, washing with ethanol 3 times, 1.47 g, in a yield of 69%. Single crystals suitable for X-ray diffraction were obtained from an ethanol-CH₂Cl₂ mixture (1:1, v:v) by slow evaporation at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

4-(4-Oxopent-2-en-2-ylamino)-1,2,4-triazol-1-ium-5-thiolate top

Crystal data top

C₈H₁₂N₄OS	F(000) = 448
M_r = 212.28	D_x = 1.314 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9199 reflections
a = 10.620 (6) Å	θ = 2.5–26.0°
b = 9.520 (5) Å	µ = 0.28 mm⁻¹
c = 10.764 (5) Å	T = 293 K
β = 99.560 (14)°	Prism, yellow
V = 1073.2 (10) Å³	0.26 × 0.23 × 0.18 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2071 independent reflections
Radiation source: fine-focus sealed tube	1688 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→13
T_min = 0.932, T_max = 0.952	k = −11→11
9199 measured reflections	l = −13→13

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0494P)² + 0.3337P] where P = (F_o² + 2F_c²)/3
2071 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₈H₁₂N₄OS	V = 1073.2 (10) Å³
M_r = 212.28	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.620 (6) Å	µ = 0.28 mm⁻¹
b = 9.520 (5) Å	T = 293 K
c = 10.764 (5) Å	0.26 × 0.23 × 0.18 mm
β = 99.560 (14)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	2071 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1688 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.952	R_int = 0.030
9199 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	Δρ_max = 0.24 e Å⁻³
2071 reflections	Δρ_min = −0.22 e Å⁻³
130 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.6978 (2)	0.4476 (2)	0.6177 (2)	0.0581 (6)
H1A	0.6385	0.4804	0.6695	0.087*
H1B	0.7230	0.5246	0.5697	0.087*
H1C	0.7717	0.4092	0.6702	0.087*
C2	0.63580 (17)	0.3365 (2)	0.53014 (16)	0.0413 (4)
C3	0.51805 (18)	0.2824 (2)	0.53712 (17)	0.0474 (5)
H3	0.4781	0.3133	0.6027	0.057*
C4	0.45166 (17)	0.1828 (2)	0.45229 (17)	0.0437 (4)
C5	0.31956 (19)	0.1390 (3)	0.4704 (2)	0.0598 (6)
H5A	0.2574	0.1966	0.4191	0.090*
H5B	0.3113	0.1500	0.5573	0.090*
H5C	0.3058	0.0423	0.4464	0.090*
C6	0.9660 (2)	0.1873 (2)	0.5572 (2)	0.0579 (5)
H6A	1.0551	0.1644	0.5677	0.087*
H6B	0.9162	0.1048	0.5318	0.087*
H6C	0.9457	0.2212	0.6355	0.087*
C7	0.93642 (17)	0.29676 (19)	0.45994 (16)	0.0420 (4)
C8	0.81958 (17)	0.45095 (18)	0.33090 (15)	0.0377 (4)
N1	0.70361 (13)	0.28695 (16)	0.44362 (13)	0.0430 (4)
H1	0.6761	0.2136	0.4010	0.052*
N2	0.81498 (13)	0.34888 (15)	0.42069 (13)	0.0381 (3)
N3	0.94393 (14)	0.45391 (16)	0.32250 (14)	0.0445 (4)
H3A	0.9753	0.5092	0.2723	0.053*
N4	1.01765 (14)	0.35996 (17)	0.40183 (15)	0.0483 (4)
O1	0.49708 (12)	0.13376 (15)	0.36199 (13)	0.0536 (4)
S1	0.69902 (5)	0.54628 (5)	0.25545 (4)	0.04948 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0537 (13)	0.0681 (14)	0.0536 (11)	−0.0014 (10)	0.0118 (10)	−0.0165 (10)
C2	0.0402 (10)	0.0460 (10)	0.0389 (9)	0.0044 (8)	0.0103 (8)	0.0013 (7)
C3	0.0418 (11)	0.0602 (12)	0.0439 (10)	0.0030 (9)	0.0180 (8)	−0.0033 (9)
C4	0.0370 (10)	0.0495 (11)	0.0474 (10)	0.0029 (8)	0.0151 (8)	0.0062 (8)
C5	0.0426 (12)	0.0754 (15)	0.0653 (13)	−0.0085 (10)	0.0198 (10)	0.0014 (11)
C6	0.0566 (13)	0.0560 (12)	0.0597 (12)	0.0071 (10)	0.0055 (10)	0.0110 (10)
C7	0.0369 (10)	0.0440 (10)	0.0447 (9)	0.0003 (8)	0.0055 (8)	−0.0035 (8)
C8	0.0379 (10)	0.0402 (9)	0.0360 (8)	−0.0018 (7)	0.0089 (7)	−0.0040 (7)
N1	0.0388 (9)	0.0446 (9)	0.0490 (8)	−0.0086 (7)	0.0175 (7)	−0.0082 (7)
N2	0.0316 (8)	0.0411 (8)	0.0427 (8)	−0.0030 (6)	0.0092 (6)	−0.0012 (6)
N3	0.0359 (9)	0.0500 (9)	0.0493 (9)	−0.0028 (7)	0.0116 (7)	0.0062 (7)
N4	0.0339 (8)	0.0570 (10)	0.0536 (9)	0.0008 (7)	0.0059 (7)	0.0037 (7)
O1	0.0461 (8)	0.0604 (9)	0.0591 (8)	−0.0084 (6)	0.0223 (7)	−0.0143 (7)
S1	0.0430 (3)	0.0588 (3)	0.0476 (3)	0.0104 (2)	0.0103 (2)	0.0053 (2)

Geometric parameters (Å, º) top

C1—C2	1.495 (3)	C6—C7	1.474 (3)
C1—H1A	0.9600	C6—H6A	0.9600
C1—H1B	0.9600	C6—H6B	0.9600
C1—H1C	0.9600	C6—H6C	0.9600
C2—N1	1.353 (2)	C7—N4	1.295 (2)
C2—C3	1.366 (3)	C7—N2	1.381 (2)
C3—C4	1.420 (3)	C8—N3	1.339 (2)
C3—H3	0.9300	C8—N2	1.377 (2)
C4—O1	1.245 (2)	C8—S1	1.6664 (19)
C4—C5	1.507 (3)	N1—N2	1.380 (2)
C5—H5A	0.9600	N1—H1	0.8600
C5—H5B	0.9600	N3—N4	1.386 (2)
C5—H5C	0.9600	N3—H3A	0.8600

C2—C1—H1A	109.5	C7—C6—H6B	109.5
C2—C1—H1B	109.5	H6A—C6—H6B	109.5
H1A—C1—H1B	109.5	C7—C6—H6C	109.5
C2—C1—H1C	109.5	H6A—C6—H6C	109.5
H1A—C1—H1C	109.5	H6B—C6—H6C	109.5
H1B—C1—H1C	109.5	N4—C7—N2	110.40 (16)
N1—C2—C3	120.20 (17)	N4—C7—C6	126.26 (17)
N1—C2—C1	116.86 (17)	N2—C7—C6	123.32 (16)
C3—C2—C1	122.92 (17)	N3—C8—N2	102.27 (15)
C2—C3—C4	125.30 (16)	N3—C8—S1	129.95 (14)
C2—C3—H3	117.4	N2—C8—S1	127.77 (14)
C4—C3—H3	117.4	C2—N1—N2	122.95 (15)
O1—C4—C3	122.48 (17)	C2—N1—H1	118.5
O1—C4—C5	119.12 (18)	N2—N1—H1	118.5
C3—C4—C5	118.38 (17)	C8—N2—N1	123.94 (14)
C4—C5—H5A	109.5	C8—N2—C7	109.16 (14)
C4—C5—H5B	109.5	N1—N2—C7	125.19 (15)
H5A—C5—H5B	109.5	C8—N3—N4	114.05 (15)
C4—C5—H5C	109.5	C8—N3—H3A	123.0
H5A—C5—H5C	109.5	N4—N3—H3A	123.0
H5B—C5—H5C	109.5	C7—N4—N3	104.12 (15)
C7—C6—H6A	109.5

N1—C2—C3—C4	−5.7 (3)	C2—N1—N2—C7	105.0 (2)
C1—C2—C3—C4	176.25 (19)	N4—C7—N2—C8	0.6 (2)
C2—C3—C4—O1	0.7 (3)	C6—C7—N2—C8	179.02 (17)
C2—C3—C4—C5	−177.3 (2)	N4—C7—N2—N1	166.12 (16)
C3—C2—N1—N2	171.33 (16)	C6—C7—N2—N1	−15.5 (3)
C1—C2—N1—N2	−10.5 (3)	N2—C8—N3—N4	−0.11 (19)
N3—C8—N2—N1	−166.02 (14)	S1—C8—N3—N4	179.01 (13)
S1—C8—N2—N1	14.8 (2)	N2—C7—N4—N3	−0.62 (19)
N3—C8—N2—C7	−0.27 (18)	C6—C7—N4—N3	−178.99 (18)
S1—C8—N2—C7	−179.42 (13)	C8—N3—N4—C7	0.5 (2)
C2—N1—N2—C8	−91.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.03	2.659 (2)	130
N1—H1···S1ⁱ	0.86	2.81	3.4127 (19)	129
N3—H3A···O1ⁱⁱ	0.86	1.93	2.772 (2)	166

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₈H₁₂N₄OS
M_r	212.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.620 (6), 9.520 (5), 10.764 (5)
β (°)	99.560 (14)
V (Å³)	1073.2 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.26 × 0.23 × 0.18

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.932, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	9199, 2071, 1688
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.105, 1.06
No. of reflections	2071
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.22

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.03	2.659 (2)	129.8
N1—H1···S1ⁱ	0.86	2.81	3.4127 (19)	128.9
N3—H3A···O1ⁱⁱ	0.86	1.93	2.772 (2)	165.9

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

We acknowledge the support of the Natural Science Foundation and the International Cooperation Foundation of Guizhou Province.

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