supplementary materials
Ethyl 5-amino-3-methylsulfanyl-1H-pyrazole-4-carboxylate
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.
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.
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).
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).
Ethyl 5-amino-3-methylsulfanyl-1
H-pyrazole-4-carboxylate
top
Crystal data top
| C7H11N3O2S | Z = 2 |
| Mr = 201.25 | F(000) = 212 |
| Triclinic, P1 | Dx = 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 | Rint = 0.013 |
| φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.969, Tmax = 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(Fo2) + (0.0669P)2 + 0.2967P]
where P = (Fo2 + 2Fc2)/3 |
| 1624 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.45 e Å−3 |
| 0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
| C7H11N3O2S | γ = 65.643 (1)° |
| Mr = 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) |
| Tmin = 0.969, Tmax = 0.984 | Rint = 0.013 |
| 2317 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
| wR(F2) = 0.127 | Δρmax = 0.45 e Å−3 |
| S = 1.08 | Δρmin = −0.24 e Å−3 |
| 1624 reflections | Absolute structure: ? |
| 118 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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, °) 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 codes: (i) x+1, y, z. |
Table 1
Hydrogen-bond geometry (Å, °) 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 codes: (i) x+1, y, z. |
I do not need acknowledegements.
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin
Hanfeld, U., Rees, C. W. & White, A. J. P. (1996). J. Chem. Soc., Perkin Trans. 1, pp. 1545–1552. Check spelling – was Hanefeld in text
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.
![[Figure 1]](./hg2437fig1thm.gif)
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.