Ethyl 5-amino-3-methyl­sulfan­yl-1H-pyrazole-4-carboxyl­ate

Li, Y.; Shao, T.-F.; Wang, J.-W.

doi:10.1107/S1600536808035095

organic compounds

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Volume 64| Part 12| December 2008| Page o2280

doi:10.1107/S1600536808035095

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Ethyl 5-amino-3-methylsulfanyl-1H-pyrazole-4-carboxylate

Yan Li,^a Teng-Fei Shao ^a and Jian-Wu Wang ^a ^*

^aSchool of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: yugp2005@yahoo.com.cn

(Received 27 October 2008; accepted 28 October 2008; online 8 November 2008)

In the title compound, C₇H₁₁N₃O₂S, bond lengths and angles are within normal ranges. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds, linking the molecules into infinite one-dimensional chains along the a axis.

Related literature

For the biological activity, see: Hanefeld et al. (1996 ). For a similar structure, see: Ren et al. (2004 ).

Experimental

Crystal data

C₇H₁₁N₃O₂S
M_r = 201.25
Triclinic, $[P \overline 1]$
a = 7.0012 (7) Å
b = 7.5870 (8) Å
c = 10.1055 (10) Å
α = 81.038 (2)°
β = 72.173 (2)°
γ = 65.643 (1)°
V = 465.26 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 273 (2) K
0.10 × 0.10 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.969, T_max = 0.984
2317 measured reflections
1624 independent reflections
1488 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.127
S = 1.08
1624 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯O2ⁱ	0.86	2.16	2.914 (3)	146
N2—H2C⋯O2ⁱ	0.86	2.34	3.019 (3)	137
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035095/hg2437sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035095/hg2437Isup2.hkl

checkCIF report

Comment top

The title compound, is an important intermediate in synthesis of heterocyclic compounds (Hanfeld et al., 1996) in particular, in producing imidazo[1,2-b]pyrazole derivatives. Here, we report the crystal structure of (I).

In compound (I), all bond lengths and angles are normal and in a good agreement with those reported previously (Ren et al., 2004). The pyrazole ring C4/C5/C5/N2/N3 and bonded atoms N1, S1, C3, O1, C2 and C1 are coplanar, the largest deviation from the mean plane being 0.053 (2)Å for atom C3. The crystal packing is stabilized by intermolecular N—H···O hydrogen bonds, linking the molecules into infinite one-dimensional chain along the a axis.

Related literature top

For the biological activity, see: Hanfeld et al. (1996). For a similar structure, see: Ren et al. (2004).

Experimental top

A round-bottomed flask fitted with a dropping funnel was charged with 11.2 g (0.2 mol) potassium hydroxide in 200 ml MeCN. The solution was cooled in an ice bath. Through the dropping funnel 22.7 g (0.2 mol) ethyl cyanoacetate was added gradually. After stirring at 273K for 0.5 h, 15.2 g(0.2 mol) carbon bisulfide was added while vigorous stirring. Keep stirring for 1 h, 50.4 g(0.4 mol) dimethyl sulfate was added through the drop funnel, then left overnight. The reaction mixture was filtered and filtrate evaporated on a rotary evaporator to remove the solvent. The mixture was dissolved in 50 ml ethanol, then through a drop funnel 12.5 g (0.2 mol) of hydrazine hydrate was added. The solution was evaporated in vacuo to afford crude product, which was purified by column chromatography to give the desired product 34.7 g, yield 86.3%. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a methanol solution at room temperature for one week.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

Ethyl 5-amino-3-methylsulfanyl-1H-pyrazole-4-carboxylate top

Crystal data top

C₇H₁₁N₃O₂S	Z = 2
M_r = 201.25	F(000) = 212
Triclinic, P1	D_x = 1.437 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0012 (7) Å	Cell parameters from 1750 reflections
b = 7.5870 (8) Å	θ = 3.0–27.5°
c = 10.1055 (10) Å	µ = 0.32 mm⁻¹
α = 81.038 (2)°	T = 273 K
β = 72.173 (2)°	Block, yellow
γ = 65.643 (1)°	0.10 × 0.10 × 0.05 mm
V = 465.26 (8) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1624 independent reflections
Radiation source: fine-focus sealed tube	1488 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.969, T_max = 0.984	k = −8→9
2317 measured reflections	l = −5→11

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0669P)² + 0.2967P] where P = (F_o² + 2F_c²)/3
1624 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₇H₁₁N₃O₂S	γ = 65.643 (1)°
M_r = 201.25	V = 465.26 (8) Å³
Triclinic, P1	Z = 2
a = 7.0012 (7) Å	Mo Kα radiation
b = 7.5870 (8) Å	µ = 0.32 mm⁻¹
c = 10.1055 (10) Å	T = 273 K
α = 81.038 (2)°	0.10 × 0.10 × 0.05 mm
β = 72.173 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1624 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1488 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.984	R_int = 0.013
2317 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.08	Δρ_max = 0.45 e Å⁻³
1624 reflections	Δρ_min = −0.24 e Å⁻³
118 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
S1	0.46271 (10)	0.72168 (10)	0.13781 (7)	0.0506 (3)
O1	0.3262 (3)	0.7811 (3)	0.61242 (17)	0.0461 (4)
O2	0.1914 (3)	0.7558 (3)	0.44317 (18)	0.0486 (5)
N2	0.8938 (3)	0.7010 (3)	0.3056 (2)	0.0435 (5)
H2C	1.0232	0.6889	0.3013	0.052*
C3	0.3414 (4)	0.7574 (3)	0.4801 (2)	0.0383 (5)
N1	0.7639 (3)	0.7355 (3)	0.5482 (2)	0.0510 (6)
H1D	0.8881	0.7260	0.5535	0.061*
H1E	0.6578	0.7515	0.6223	0.061*
C5	0.7355 (3)	0.7256 (3)	0.4242 (2)	0.0368 (5)
C2	0.1246 (4)	0.8045 (4)	0.7109 (3)	0.0418 (6)
H2A	0.0903	0.6923	0.7138	0.050*
H2B	0.0088	0.9182	0.6866	0.050*
C6	0.6221 (4)	0.7165 (3)	0.2425 (3)	0.0387 (5)
N3	0.8282 (3)	0.6970 (3)	0.1904 (2)	0.0450 (5)
C4	0.5518 (3)	0.7352 (3)	0.3906 (2)	0.0360 (5)
C1	0.1484 (5)	0.8274 (4)	0.8514 (3)	0.0542 (7)
H1A	0.0146	0.8433	0.9215	0.081*
H1B	0.1818	0.9392	0.8472	0.081*
H1C	0.2638	0.7143	0.8740	0.081*
C7	0.6528 (5)	0.7014 (5)	−0.0316 (3)	0.0626 (8)
H7A	0.5843	0.7025	−0.1009	0.094*
H7B	0.7777	0.5824	−0.0347	0.094*
H7C	0.6977	0.8085	−0.0493	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0384 (4)	0.0712 (5)	0.0510 (4)	−0.0245 (3)	−0.0179 (3)	−0.0052 (3)
O1	0.0381 (9)	0.0649 (11)	0.0429 (9)	−0.0248 (8)	−0.0141 (7)	−0.0026 (8)
O2	0.0306 (9)	0.0707 (12)	0.0543 (11)	−0.0249 (8)	−0.0170 (8)	−0.0035 (9)
N2	0.0280 (9)	0.0626 (13)	0.0486 (12)	−0.0232 (9)	−0.0139 (8)	−0.0029 (9)
C3	0.0304 (11)	0.0412 (12)	0.0469 (13)	−0.0150 (9)	−0.0144 (10)	0.0001 (10)
N1	0.0336 (11)	0.0840 (16)	0.0477 (12)	−0.0301 (11)	−0.0154 (9)	−0.0060 (11)
C5	0.0286 (11)	0.0430 (12)	0.0450 (12)	−0.0174 (9)	−0.0143 (9)	−0.0002 (10)
C2	0.0311 (11)	0.0468 (13)	0.0547 (14)	−0.0174 (10)	−0.0189 (10)	−0.0003 (11)
C6	0.0324 (11)	0.0389 (12)	0.0460 (13)	−0.0151 (9)	−0.0100 (10)	−0.0022 (9)
N3	0.0335 (10)	0.0597 (13)	0.0463 (12)	−0.0218 (9)	−0.0105 (9)	−0.0043 (9)
C4	0.0254 (10)	0.0398 (11)	0.0475 (13)	−0.0141 (9)	−0.0141 (9)	−0.0016 (9)
C1	0.0513 (15)	0.0736 (18)	0.0446 (14)	−0.0320 (14)	−0.0093 (12)	−0.0064 (13)
C7	0.0547 (17)	0.095 (2)	0.0483 (16)	−0.0347 (16)	−0.0180 (13)	−0.0050 (15)

Geometric parameters (Å, º) top

S1—C6	1.744 (2)	C5—C4	1.399 (3)
S1—C7	1.801 (3)	C2—C1	1.522 (3)
O1—C3	1.343 (3)	C2—H2A	0.9700
O1—C2	1.415 (3)	C2—H2B	0.9700
O2—C3	1.222 (3)	C6—N3	1.328 (3)
N2—C5	1.336 (3)	C6—C4	1.435 (3)
N2—N3	1.385 (3)	C1—H1A	0.9600
N2—H2C	0.8600	C1—H1B	0.9600
C3—C4	1.429 (3)	C1—H1C	0.9600
N1—C5	1.346 (3)	C7—H7A	0.9600
N1—H1D	0.8600	C7—H7B	0.9600
N1—H1E	0.8600	C7—H7C	0.9600

C6—S1—C7	100.66 (12)	N3—C6—C4	111.9 (2)
C3—O1—C2	116.79 (18)	N3—C6—S1	122.18 (19)
C5—N2—N3	113.11 (18)	C4—C6—S1	125.90 (17)
C5—N2—H2C	123.4	C6—N3—N2	104.02 (19)
N3—N2—H2C	123.4	C5—C4—C3	129.2 (2)
O2—C3—O1	123.1 (2)	C5—C4—C6	103.93 (19)
O2—C3—C4	125.2 (2)	C3—C4—C6	126.9 (2)
O1—C3—C4	111.67 (19)	C2—C1—H1A	109.5
C5—N1—H1D	120.0	C2—C1—H1B	109.5
C5—N1—H1E	120.0	H1A—C1—H1B	109.5
H1D—N1—H1E	120.0	C2—C1—H1C	109.5
N2—C5—N1	122.8 (2)	H1A—C1—H1C	109.5
N2—C5—C4	107.0 (2)	H1B—C1—H1C	109.5
N1—C5—C4	130.2 (2)	S1—C7—H7A	109.5
O1—C2—C1	106.85 (18)	S1—C7—H7B	109.5
O1—C2—H2A	110.4	H7A—C7—H7B	109.5
C1—C2—H2A	110.4	S1—C7—H7C	109.5
O1—C2—H2B	110.4	H7A—C7—H7C	109.5
C1—C2—H2B	110.4	H7B—C7—H7C	109.5
H2A—C2—H2B	108.6

C2—O1—C3—O2	0.2 (3)	N1—C5—C4—C3	−0.4 (4)
C2—O1—C3—C4	−179.98 (19)	N2—C5—C4—C6	−0.8 (2)
N3—N2—C5—N1	−179.3 (2)	N1—C5—C4—C6	179.9 (2)
N3—N2—C5—C4	1.3 (3)	O2—C3—C4—C5	−176.5 (2)
C3—O1—C2—C1	179.7 (2)	O1—C3—C4—C5	3.6 (3)
C7—S1—C6—N3	−1.3 (2)	O2—C3—C4—C6	3.1 (4)
C7—S1—C6—C4	177.5 (2)	O1—C3—C4—C6	−176.7 (2)
C4—C6—N3—N2	0.6 (3)	N3—C6—C4—C5	0.1 (3)
S1—C6—N3—N2	179.63 (16)	S1—C6—C4—C5	−178.88 (17)
C5—N2—N3—C6	−1.2 (3)	N3—C6—C4—C3	−179.6 (2)
N2—C5—C4—C3	178.9 (2)	S1—C6—C4—C3	1.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O2ⁱ	0.86	2.16	2.914 (3)	146
N2—H2C···O2ⁱ	0.86	2.34	3.019 (3)	137

Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₇H₁₁N₃O₂S
M_r	201.25
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	7.0012 (7), 7.5870 (8), 10.1055 (10)
α, β, γ (°)	81.038 (2), 72.173 (2), 65.643 (1)
V (Å³)	465.26 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.10 × 0.10 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.969, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	2317, 1624, 1488
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.08
No. of reflections	1624
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.24

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O2ⁱ	0.86	2.16	2.914 (3)	146.0
N2—H2C···O2ⁱ	0.86	2.34	3.019 (3)	136.7

Symmetry code: (i) x+1, y, z.

References

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin. Google Scholar
Hanefeld, U., Rees, C. W. & White, A. J. P. (1996). J. Chem. Soc., Perkin Trans. 1, pp. 1545–1552. Google Scholar
Ren, X. L., Wu, C., Hu, F. Z., Zou, X. M. & Yang, H. Z. (2004). Chin. J. Chem. 22, 194–198. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2280

doi:10.1107/S1600536808035095

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