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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2280.
Published online 2008 November 8. doi:  10.1107/S1600536808035095
PMCID: PMC2959851

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

Abstract

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 [triangle]). For a similar structure, see: Ren et al. (2004 [triangle]).

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Object name is e-64-o2280-scheme1.jpg

Experimental

Crystal data

  • C7H11N3O2S
  • M r = 201.25
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2280-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.127
  • S = 1.08
  • 1624 reflections
  • 118 parameters
  • H-atom parameters constrained
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.24 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å, N–H = 0.86 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2 (1.5 times for methyl) times Ueq(C,N).

Figures

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

Crystal data

C7H11N3O2SZ = 2
Mr = 201.25F000 = 212
Triclinic, P1Dx = 1.437 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.0012 (7) ÅCell parameters from 1750 reflections
b = 7.5870 (8) Åθ = 3.0–27.5º
c = 10.1055 (10) ŵ = 0.32 mm1
α = 81.038 (2)ºT = 273 (2) K
β = 72.173 (2)ºBlock, yellow
γ = 65.6430 (10)º0.10 × 0.10 × 0.05 mm
V = 465.26 (8) Å3

Data collection

Bruker SMART CCD area-detector diffractometer1624 independent reflections
Radiation source: fine-focus sealed tube1488 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.013
T = 273(2) Kθmax = 25.0º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.969, Tmax = 0.984k = −8→9
2317 measured reflectionsl = −5→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.0669P)2 + 0.2967P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1624 reflectionsΔρmax = 0.45 e Å3
118 parametersΔρmin = −0.24 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
S10.46271 (10)0.72168 (10)0.13781 (7)0.0506 (3)
O10.3262 (3)0.7811 (3)0.61242 (17)0.0461 (4)
O20.1914 (3)0.7558 (3)0.44317 (18)0.0486 (5)
N20.8938 (3)0.7010 (3)0.3056 (2)0.0435 (5)
H2C1.02320.68890.30130.052*
C30.3414 (4)0.7574 (3)0.4801 (2)0.0383 (5)
N10.7639 (3)0.7355 (3)0.5482 (2)0.0510 (6)
H1D0.88810.72600.55350.061*
H1E0.65780.75150.62230.061*
C50.7355 (3)0.7256 (3)0.4242 (2)0.0368 (5)
C20.1246 (4)0.8045 (4)0.7109 (3)0.0418 (6)
H2A0.09030.69230.71380.050*
H2B0.00880.91820.68660.050*
C60.6221 (4)0.7165 (3)0.2425 (3)0.0387 (5)
N30.8282 (3)0.6970 (3)0.1904 (2)0.0450 (5)
C40.5518 (3)0.7352 (3)0.3906 (2)0.0360 (5)
C10.1484 (5)0.8274 (4)0.8514 (3)0.0542 (7)
H1A0.01460.84330.92150.081*
H1B0.18180.93920.84720.081*
H1C0.26380.71430.87400.081*
C70.6528 (5)0.7014 (5)−0.0316 (3)0.0626 (8)
H7A0.58430.7025−0.10090.094*
H7B0.77770.5824−0.03470.094*
H7C0.69770.8085−0.04930.094*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0384 (4)0.0712 (5)0.0510 (4)−0.0245 (3)−0.0179 (3)−0.0052 (3)
O10.0381 (9)0.0649 (11)0.0429 (9)−0.0248 (8)−0.0141 (7)−0.0026 (8)
O20.0306 (9)0.0707 (12)0.0543 (11)−0.0249 (8)−0.0170 (8)−0.0035 (9)
N20.0280 (9)0.0626 (13)0.0486 (12)−0.0232 (9)−0.0139 (8)−0.0029 (9)
C30.0304 (11)0.0412 (12)0.0469 (13)−0.0150 (9)−0.0144 (10)0.0001 (10)
N10.0336 (11)0.0840 (16)0.0477 (12)−0.0301 (11)−0.0154 (9)−0.0060 (11)
C50.0286 (11)0.0430 (12)0.0450 (12)−0.0174 (9)−0.0143 (9)−0.0002 (10)
C20.0311 (11)0.0468 (13)0.0547 (14)−0.0174 (10)−0.0189 (10)−0.0003 (11)
C60.0324 (11)0.0389 (12)0.0460 (13)−0.0151 (9)−0.0100 (10)−0.0022 (9)
N30.0335 (10)0.0597 (13)0.0463 (12)−0.0218 (9)−0.0105 (9)−0.0043 (9)
C40.0254 (10)0.0398 (11)0.0475 (13)−0.0141 (9)−0.0141 (9)−0.0016 (9)
C10.0513 (15)0.0736 (18)0.0446 (14)−0.0320 (14)−0.0093 (12)−0.0064 (13)
C70.0547 (17)0.095 (2)0.0483 (16)−0.0347 (16)−0.0180 (13)−0.0050 (15)

Geometric parameters (Å, °)

S1—C61.744 (2)C5—C41.399 (3)
S1—C71.801 (3)C2—C11.522 (3)
O1—C31.343 (3)C2—H2A0.9700
O1—C21.415 (3)C2—H2B0.9700
O2—C31.222 (3)C6—N31.328 (3)
N2—C51.336 (3)C6—C41.435 (3)
N2—N31.385 (3)C1—H1A0.9600
N2—H2C0.8600C1—H1B0.9600
C3—C41.429 (3)C1—H1C0.9600
N1—C51.346 (3)C7—H7A0.9600
N1—H1D0.8600C7—H7B0.9600
N1—H1E0.8600C7—H7C0.9600
C6—S1—C7100.66 (12)N3—C6—C4111.9 (2)
C3—O1—C2116.79 (18)N3—C6—S1122.18 (19)
C5—N2—N3113.11 (18)C4—C6—S1125.90 (17)
C5—N2—H2C123.4C6—N3—N2104.02 (19)
N3—N2—H2C123.4C5—C4—C3129.2 (2)
O2—C3—O1123.1 (2)C5—C4—C6103.93 (19)
O2—C3—C4125.2 (2)C3—C4—C6126.9 (2)
O1—C3—C4111.67 (19)C2—C1—H1A109.5
C5—N1—H1D120.0C2—C1—H1B109.5
C5—N1—H1E120.0H1A—C1—H1B109.5
H1D—N1—H1E120.0C2—C1—H1C109.5
N2—C5—N1122.8 (2)H1A—C1—H1C109.5
N2—C5—C4107.0 (2)H1B—C1—H1C109.5
N1—C5—C4130.2 (2)S1—C7—H7A109.5
O1—C2—C1106.85 (18)S1—C7—H7B109.5
O1—C2—H2A110.4H7A—C7—H7B109.5
C1—C2—H2A110.4S1—C7—H7C109.5
O1—C2—H2B110.4H7A—C7—H7C109.5
C1—C2—H2B110.4H7B—C7—H7C109.5
H2A—C2—H2B108.6
C2—O1—C3—O20.2 (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—C6179.9 (2)
N3—N2—C5—C41.3 (3)O2—C3—C4—C5−176.5 (2)
C3—O1—C2—C1179.7 (2)O1—C3—C4—C53.6 (3)
C7—S1—C6—N3−1.3 (2)O2—C3—C4—C63.1 (4)
C7—S1—C6—C4177.5 (2)O1—C3—C4—C6−176.7 (2)
C4—C6—N3—N20.6 (3)N3—C6—C4—C50.1 (3)
S1—C6—N3—N2179.63 (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—C3178.9 (2)S1—C6—C4—C31.4 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1D···O2i0.862.162.914 (3)146
N2—H2C···O2i0.862.343.019 (3)137

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2437).

References

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

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