Acta Cryst. (2009). E65, o1249 [ doi:10.1107/S1600536809016742 ]
The title compound, C9H12N4O4S, was proven to be the product of the reaction of methyl 5-amino-1H-pyrazole-3-carboxylate with ethyl isothiocyanatocarbonate. All non-H atoms of the molecule are planar, the mean deviation from the least squares plane being 0.048 Å. The intramolecular N-H
O bond involving the NH-group, which links the thiourea and pyrazole fragments, closes a six-membered pseudo-heterocyclic ring, and two more hydrogen bonds (N-HO with the participation of the pyrazole NH group and N-HS involving the second thiourea NH group) link the molecules into infinite chains running along [1
0].
A suspension of methyl 5-amino-1H-pyrazole-3-carboxylate (2.0 g, 14.2 mmol) in 10 ml of ethyl acetate and 40 ml of benzene was cooled to 0°C and stirred. To this solution, ethyl isothiocyanatocarbonate (2.04 g, 15.6 mmol) in 10 ml benzene was added dropwise. The resulting reaction mixture was allowed to warm up to room temperature, and stirring was continued for 5 h. The reaction mixture was filtered, and washed with plenty of ether to afford the desired product (3.32 g, 12.2 mmol, 86.0% yield). 1H NMR (400 MHz, DMSO-d6) δ p.p.m.: 13.99 (br. s., 1 H), 12.12 (br. s., 1 H), 11.48 (br. s., 1 H), 7.51 (s, 1 H), 4.22 (q, J=7.07 Hz, 2 H), 3.85 (s, 3 H), 1.26 (t, J=7.07 Hz, 3 H).
All H atoms were placed in geometrically calculated positions (N—H 0.87 Å, C—H 0.94 Å, 0.97 Å, 0.98 Å, for aromatic, methyl and methylene H atoms respectively) and included in the refinement in riding motion approximation. The Uiso(H) were set to 1.2Ueq of the carrying atom for aromatic, methylene, methyne and amine groups, and 1.5Ueq for methyl H atoms.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./dn2451fig1thm.gif)
| Fig. 1. Molecular structure of the title compound showing 50% probability displacement ellipsoids and atom numbering scheme; H atoms are drawn as circles with arbitrary small radius. |
![[Figure 2]](./dn2451fig2thm.gif)
| Fig. 2. Packing diagram for the title compound viewed approximately along the a axis; H-bonds are shown as dashed lines. |
| C9H12N4O4S | Z = 2 |
| Mr = 272.29 | F000 = 284 |
| Triclinic, P1 | Dx = 1.465 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 8.0855 (8) Å | Cell parameters from 3767 reflections |
| b = 9.0035 (8) Å | θ = 2.5–27.8º |
| c = 9.5959 (9) Å | µ = 0.28 mm−1 |
| α = 64.510 (1)º | T = 208 K |
| β = 82.294 (1)º | Block, colorless |
| γ = 78.716 (1)º | 0.20 × 0.15 × 0.10 mm |
| V = 617.39 (10) Å3 |
| Siemens P4 diffractometer with APEX CCD | 2653 independent reflections |
| Radiation source: fine-focus sealed tube | 2255 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.044 |
| T = 208 K | θmax = 28.2º |
| φ and ω scans | θmin = 2.4º |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −5→10 |
| Tmin = 0.947, Tmax = 0.973 | k = −11→11 |
| 5852 measured reflections | l = −11→12 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.040 | w = 1/[σ2(Fo2) + (0.0521P)2 + 0.1805P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.113 | (Δ/σ)max = 0.001 |
| S = 1.04 | Δρmax = 0.39 e Å−3 |
| 2653 reflections | Δρmin = −0.28 e Å−3 |
| 166 parameters | Extinction correction: SHELXL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.064 (8) |
| Secondary atom site location: difference Fourier map |
| C9H12N4O4S | γ = 78.716 (1)º |
| Mr = 272.29 | V = 617.39 (10) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.0855 (8) Å | Mo Kα |
| b = 9.0035 (8) Å | µ = 0.28 mm−1 |
| c = 9.5959 (9) Å | T = 208 K |
| α = 64.510 (1)º | 0.20 × 0.15 × 0.10 mm |
| β = 82.294 (1)º |
| Siemens P4 diffractometer with APEX CCD | 2653 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2255 reflections with I > 2σ(I) |
| Tmin = 0.947, Tmax = 0.973 | Rint = 0.044 |
| 5852 measured reflections |
| R[F2 > 2σ(F2)] = 0.040 | 166 parameters |
| wR(F2) = 0.113 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.39 e Å−3 |
| 2653 reflections | Δρmin = −0.28 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.7861 (3) | 0.9454 (2) | −0.0198 (2) | 0.0539 (6) | |
| H1A | 0.6653 | 0.9725 | −0.0320 | 0.081* | |
| H1B | 0.8446 | 1.0106 | −0.1156 | 0.081* | |
| H1C | 0.8125 | 0.9706 | 0.0626 | 0.081* | |
| C2 | 0.8414 (3) | 0.7653 (2) | 0.0194 (2) | 0.0451 (5) | |
| H2A | 0.8135 | 0.7375 | −0.0619 | 0.054* | |
| H2B | 0.9638 | 0.7366 | 0.0301 | 0.054* | |
| C3 | 0.7832 (2) | 0.5090 (2) | 0.22047 (19) | 0.0319 (4) | |
| C4 | 0.6784 (2) | 0.27556 (19) | 0.44802 (18) | 0.0285 (4) | |
| C5 | 0.7965 (2) | −0.00499 (19) | 0.46055 (19) | 0.0300 (4) | |
| C6 | 0.7316 (2) | −0.1229 (2) | 0.5968 (2) | 0.0310 (4) | |
| H6 | 0.6562 | −0.1048 | 0.6734 | 0.037* | |
| C7 | 0.8050 (2) | −0.2725 (2) | 0.59165 (19) | 0.0312 (4) | |
| C8 | 0.7909 (2) | −0.4462 (2) | 0.6958 (2) | 0.0328 (4) | |
| C9 | 0.6497 (3) | −0.6292 (2) | 0.9141 (2) | 0.0435 (5) | |
| H9A | 0.6341 | −0.6894 | 0.8550 | 0.065* | |
| H9B | 0.5509 | −0.6267 | 0.9831 | 0.065* | |
| H9C | 0.7486 | −0.6844 | 0.9741 | 0.065* | |
| N1 | 0.69023 (19) | 0.44206 (16) | 0.35749 (16) | 0.0322 (3) | |
| H1 | 0.6316 | 0.5127 | 0.3917 | 0.039* | |
| N2 | 0.77543 (19) | 0.16936 (16) | 0.39615 (16) | 0.0327 (3) | |
| H2 | 0.8340 | 0.2152 | 0.3099 | 0.039* | |
| N3 | 0.9003 (2) | −0.07384 (17) | 0.37579 (17) | 0.0360 (4) | |
| N4 | 0.9033 (2) | −0.23814 (17) | 0.46052 (17) | 0.0344 (3) | |
| H4 | 0.9626 | −0.3141 | 0.4333 | 0.041* | |
| O1 | 0.75193 (17) | 0.67399 (14) | 0.16595 (14) | 0.0374 (3) | |
| O2 | 0.87813 (18) | 0.43041 (15) | 0.15826 (15) | 0.0425 (3) | |
| O3 | 0.87755 (18) | −0.56425 (14) | 0.67884 (15) | 0.0407 (3) | |
| O4 | 0.67259 (17) | −0.46002 (15) | 0.80911 (15) | 0.0397 (3) | |
| S1 | 0.54880 (6) | 0.22717 (5) | 0.60563 (5) | 0.03395 (17) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0681 (15) | 0.0334 (10) | 0.0449 (11) | −0.0077 (10) | 0.0106 (10) | −0.0060 (8) |
| C2 | 0.0512 (12) | 0.0338 (9) | 0.0352 (9) | −0.0029 (8) | 0.0133 (8) | −0.0061 (8) |
| C3 | 0.0347 (9) | 0.0267 (8) | 0.0311 (8) | 0.0000 (7) | 0.0010 (7) | −0.0119 (6) |
| C4 | 0.0312 (9) | 0.0247 (7) | 0.0300 (8) | 0.0008 (6) | −0.0025 (7) | −0.0137 (6) |
| C5 | 0.0340 (9) | 0.0240 (8) | 0.0333 (8) | 0.0005 (6) | −0.0013 (7) | −0.0154 (7) |
| C6 | 0.0343 (9) | 0.0257 (8) | 0.0346 (8) | 0.0005 (6) | 0.0007 (7) | −0.0171 (7) |
| C7 | 0.0346 (9) | 0.0259 (8) | 0.0359 (9) | −0.0010 (7) | −0.0003 (7) | −0.0174 (7) |
| C8 | 0.0356 (9) | 0.0295 (8) | 0.0373 (9) | −0.0036 (7) | 0.0003 (7) | −0.0189 (7) |
| C9 | 0.0499 (12) | 0.0310 (9) | 0.0460 (11) | −0.0095 (8) | 0.0089 (9) | −0.0147 (8) |
| N1 | 0.0393 (8) | 0.0234 (7) | 0.0306 (7) | −0.0001 (6) | 0.0074 (6) | −0.0127 (6) |
| N2 | 0.0405 (8) | 0.0234 (7) | 0.0313 (7) | −0.0012 (6) | 0.0061 (6) | −0.0124 (6) |
| N3 | 0.0436 (9) | 0.0251 (7) | 0.0383 (8) | −0.0008 (6) | 0.0038 (7) | −0.0160 (6) |
| N4 | 0.0403 (9) | 0.0256 (7) | 0.0396 (8) | −0.0003 (6) | 0.0042 (7) | −0.0195 (6) |
| O1 | 0.0432 (7) | 0.0254 (6) | 0.0341 (6) | −0.0013 (5) | 0.0113 (5) | −0.0091 (5) |
| O2 | 0.0514 (8) | 0.0321 (7) | 0.0377 (7) | 0.0001 (6) | 0.0138 (6) | −0.0160 (6) |
| O3 | 0.0490 (8) | 0.0263 (6) | 0.0472 (7) | −0.0015 (6) | 0.0073 (6) | −0.0204 (6) |
| O4 | 0.0455 (8) | 0.0274 (6) | 0.0448 (7) | −0.0050 (5) | 0.0098 (6) | −0.0174 (5) |
| S1 | 0.0400 (3) | 0.0257 (2) | 0.0328 (2) | −0.00173 (17) | 0.00760 (18) | −0.01324 (18) |
| C1—C2 | 1.486 (3) | C5—N2 | 1.401 (2) |
| C1—H1A | 0.9700 | C6—C7 | 1.380 (2) |
| C1—H1B | 0.9700 | C6—H6 | 0.9400 |
| C1—H1C | 0.9700 | C7—N4 | 1.343 (2) |
| C2—O1 | 1.463 (2) | C7—C8 | 1.466 (2) |
| C2—H2A | 0.9800 | C8—O3 | 1.214 (2) |
| C2—H2B | 0.9800 | C8—O4 | 1.329 (2) |
| C3—O2 | 1.214 (2) | C9—O4 | 1.452 (2) |
| C3—O1 | 1.3278 (19) | C9—H9A | 0.9700 |
| C3—N1 | 1.374 (2) | C9—H9B | 0.9700 |
| C4—N2 | 1.338 (2) | C9—H9C | 0.9700 |
| C4—N1 | 1.387 (2) | N1—H1 | 0.8700 |
| C4—S1 | 1.6617 (16) | N2—H2 | 0.8700 |
| C5—N3 | 1.340 (2) | N3—N4 | 1.344 (2) |
| C5—C6 | 1.397 (2) | N4—H4 | 0.8700 |
| C2—C1—H1A | 109.5 | N4—C7—C6 | 107.60 (14) |
| C2—C1—H1B | 109.5 | N4—C7—C8 | 119.72 (14) |
| H1A—C1—H1B | 109.5 | C6—C7—C8 | 132.67 (16) |
| C2—C1—H1C | 109.5 | O3—C8—O4 | 123.84 (16) |
| H1A—C1—H1C | 109.5 | O3—C8—C7 | 123.32 (16) |
| H1B—C1—H1C | 109.5 | O4—C8—C7 | 112.84 (14) |
| O1—C2—C1 | 106.83 (15) | O4—C9—H9A | 109.5 |
| O1—C2—H2A | 110.4 | O4—C9—H9B | 109.5 |
| C1—C2—H2A | 110.4 | H9A—C9—H9B | 109.5 |
| O1—C2—H2B | 110.4 | O4—C9—H9C | 109.5 |
| C1—C2—H2B | 110.4 | H9A—C9—H9C | 109.5 |
| H2A—C2—H2B | 108.6 | H9B—C9—H9C | 109.5 |
| O2—C3—O1 | 125.25 (16) | C3—N1—C4 | 127.95 (13) |
| O2—C3—N1 | 125.62 (15) | C3—N1—H1 | 116.0 |
| O1—C3—N1 | 109.13 (13) | C4—N1—H1 | 116.0 |
| N2—C4—N1 | 114.69 (14) | C4—N2—C5 | 129.41 (14) |
| N2—C4—S1 | 126.73 (12) | C4—N2—H2 | 115.3 |
| N1—C4—S1 | 118.59 (11) | C5—N2—H2 | 115.3 |
| N3—C5—C6 | 112.89 (14) | C5—N3—N4 | 103.49 (14) |
| N3—C5—N2 | 114.22 (15) | C7—N4—N3 | 112.76 (13) |
| C6—C5—N2 | 132.89 (15) | C7—N4—H4 | 123.6 |
| C7—C6—C5 | 103.26 (14) | N3—N4—H4 | 123.6 |
| C7—C6—H6 | 128.4 | C3—O1—C2 | 116.14 (14) |
| C5—C6—H6 | 128.4 | C8—O4—C9 | 115.46 (13) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···S1i | 0.87 | 2.51 | 3.347 (1) | 161 |
| N2—H2···O2 | 0.87 | 1.92 | 2.657 (2) | 141 |
| N4—H4···O3ii | 0.87 | 2.03 | 2.876 (2) | 164 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y−1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···S1i | 0.87 | 2.51 | 3.347 (1) | 161 |
| N2—H2···O2 | 0.87 | 1.92 | 2.657 (2) | 141 |
| N4—H4···O3ii | 0.87 | 2.03 | 2.876 (2) | 164 |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y−1, −z+1. |
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Wen, L.-R., Li, M., Zhou, J.-X. & Liu, P. (2006). Acta Cryst. E62, o940–o941.
The reaction of methyl 5-amino-1H-pyrazole-3-carboxylate with ethyl isothiocyanatocarbonate produces the pyrazole-thiourea deivative; its structure was established by the present X-ray study (Fig.1).
All non-H atoms of the molecule are planar (mean deviation from its least squares plane is 0.048 Å), in contrast to previously studied pyrazole-thiourea derivative (Wen et al., 2006), where the pyrazole fragment has a nitrile substituent in position 4 and pyrazole/thiourea fragments form dihedral angle of 46.2°. Another similar compound, where pyrazole has no substituents in position 4 (Pask et al., 2006), is also essentially planar, just like the title compound.
There are three NH-groups in the molecule which are responsible for the formation of three independent H-bonds in the crystal (Table 2). The intramolecular N2—H2···O2 bond closes the 6-membered pseudo-cycle, whereas two intermolecular H-bonds each produce typical centrosymmmetric pairing motive, and their combination thus gives rise to infinite chains running along the [1,-2,0]. direction in the crystal (Fig. 2).