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The title compound, C6H9N3OS, was obtained by cyclization of ethyl 2-methylacetoacetate thiosemicarbazone with sodium methanolate in methanol. Single crystals suitable for X-ray analysis were obtained by slow evaporation of the mother liquor. The pyrazolone moiety is essentially planar. The S atom is cis with respect to the protonated endocyclic N2 atom, probably because the intramolecular hydrogen bonds allowed by this arrangement afford greater stability than those allowed when S is trans to N-2. Intermolecular hydrogen bonds link the molecules in interlocking pleated sheets, stacked along the c axis.
Supporting information
CCDC reference: 189914
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.046
- wR factor = 0.132
- Data-to-parameter ratio = 18.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002) and SCHAKAL (Keller, 1988).
2,5-dihydro-3,4-dimethyl-5-oxo-1
H-pyrazole-1-carbothioamide
top
Crystal data top
C6H9N3OS | F(000) = 720 |
Mr = 171.22 | Dx = 1.429 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2 n 2 a b | Cell parameters from 4044 reflections |
a = 7.9246 (13) Å | θ = 2.5–28.0° |
b = 12.543 (2) Å | µ = 0.35 mm−1 |
c = 16.015 (3) Å | T = 293 K |
V = 1591.9 (4) Å3 | Prism, colourless |
Z = 8 | 0.37 × 0.27 × 0.20 mm |
Data collection top
Bruker SMART-CCD 1000 diffractometer | 1904 independent reflections |
Radiation source: fine-focus sealed tube | 1559 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
φ and ω scans | θmax = 28.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.875, Tmax = 0.932 | k = −9→16 |
8987 measured reflections | l = −21→20 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0809P)2 + 0.2527P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1904 reflections | Δρmax = 0.37 e Å−3 |
105 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0133 (18) |
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 | |
S | 0.09270 (7) | 0.13621 (4) | 0.41542 (3) | 0.0492 (2) | |
N1 | 0.1054 (2) | −0.07459 (13) | 0.39897 (10) | 0.0530 (5) | |
H1A | 0.1321 | −0.1306 | 0.3709 | 0.064* | |
H1B | 0.0585 | −0.0809 | 0.4471 | 0.064* | |
N2 | 0.21228 (18) | 0.01946 (10) | 0.29012 (8) | 0.0369 (3) | |
N3 | 0.2586 (2) | 0.11183 (11) | 0.24929 (9) | 0.0404 (4) | |
H3 | 0.221 (3) | 0.168 (2) | 0.2680 (17) | 0.072 (8)* | |
O | 0.24333 (19) | −0.16257 (9) | 0.26406 (9) | 0.0542 (4) | |
C1 | 0.1365 (2) | 0.02105 (12) | 0.36803 (11) | 0.0368 (4) | |
C2 | 0.3316 (2) | 0.08462 (12) | 0.17618 (9) | 0.0355 (4) | |
C3 | 0.3405 (2) | −0.02382 (12) | 0.16908 (10) | 0.0361 (4) | |
C4 | 0.2656 (2) | −0.06864 (12) | 0.24109 (10) | 0.0375 (4) | |
C12 | 0.3893 (3) | 0.16841 (16) | 0.11721 (12) | 0.0498 (5) | |
H12A | 0.5076 | 0.1595 | 0.1064 | 0.075* | |
H12B | 0.3699 | 0.2374 | 0.1413 | 0.075* | |
H12C | 0.3277 | 0.1624 | 0.0658 | 0.075* | |
C13 | 0.4165 (3) | −0.08722 (16) | 0.09951 (12) | 0.0507 (5) | |
H13A | 0.3320 | −0.1014 | 0.0580 | 0.076* | |
H13B | 0.4590 | −0.1534 | 0.1211 | 0.076* | |
H13C | 0.5073 | −0.0476 | 0.0748 | 0.076* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0694 (4) | 0.0349 (3) | 0.0432 (3) | 0.0052 (2) | 0.0150 (2) | −0.00179 (17) |
N1 | 0.0788 (12) | 0.0334 (8) | 0.0468 (9) | −0.0052 (7) | 0.0195 (8) | 0.0023 (7) |
N2 | 0.0517 (8) | 0.0246 (7) | 0.0344 (7) | −0.0008 (5) | 0.0034 (6) | −0.0003 (5) |
N3 | 0.0584 (10) | 0.0245 (7) | 0.0383 (7) | 0.0006 (6) | 0.0090 (6) | 0.0014 (6) |
O | 0.0891 (11) | 0.0245 (6) | 0.0490 (8) | −0.0025 (6) | 0.0072 (7) | −0.0019 (5) |
C1 | 0.0411 (9) | 0.0338 (8) | 0.0357 (8) | −0.0009 (6) | −0.0007 (6) | 0.0012 (6) |
C2 | 0.0428 (9) | 0.0319 (8) | 0.0317 (8) | 0.0021 (7) | −0.0017 (6) | 0.0007 (6) |
C3 | 0.0449 (9) | 0.0300 (8) | 0.0334 (8) | 0.0018 (6) | −0.0037 (7) | −0.0037 (6) |
C4 | 0.0506 (10) | 0.0268 (8) | 0.0351 (8) | 0.0004 (7) | −0.0043 (7) | −0.0039 (6) |
C12 | 0.0656 (12) | 0.0395 (9) | 0.0443 (10) | −0.0002 (8) | 0.0110 (8) | 0.0075 (8) |
C13 | 0.0697 (13) | 0.0429 (10) | 0.0396 (9) | 0.0039 (9) | 0.0048 (8) | −0.0092 (8) |
Geometric parameters (Å, º) top
S—C1 | 1.6682 (17) | C2—C3 | 1.367 (2) |
N1—C1 | 1.321 (2) | C2—C12 | 1.485 (2) |
N1—H1A | 0.8600 | C3—C4 | 1.414 (2) |
N1—H1B | 0.8600 | C3—C13 | 1.495 (2) |
N2—N3 | 1.3801 (18) | C12—H12A | 0.9600 |
N2—C1 | 1.385 (2) | C12—H12B | 0.9600 |
N2—C4 | 1.420 (2) | C12—H12C | 0.9600 |
N3—C2 | 1.350 (2) | C13—H13A | 0.9600 |
N3—H3 | 0.82 (3) | C13—H13B | 0.9600 |
O—C4 | 1.2468 (19) | C13—H13C | 0.9600 |
| | | |
C1—N1—H1A | 120.0 | C4—C3—C13 | 124.43 (15) |
C1—N1—H1B | 120.0 | O—C4—C3 | 132.52 (15) |
H1A—N1—H1B | 120.0 | O—C4—N2 | 122.01 (16) |
N3—N2—C1 | 122.01 (12) | C3—C4—N2 | 105.47 (13) |
N3—N2—C4 | 108.19 (13) | C2—C12—H12A | 109.5 |
C1—N2—C4 | 129.68 (13) | C2—C12—H12B | 109.5 |
C2—N3—N2 | 108.22 (13) | H12A—C12—H12B | 109.5 |
C2—N3—H3 | 133.7 (18) | C2—C12—H12C | 109.5 |
N2—N3—H3 | 116.6 (18) | H12A—C12—H12C | 109.5 |
N1—C1—N2 | 113.93 (15) | H12B—C12—H12C | 109.5 |
N1—C1—S | 125.23 (14) | C3—C13—H13A | 109.5 |
N2—C1—S | 120.84 (11) | C3—C13—H13B | 109.5 |
N3—C2—C3 | 110.24 (14) | H13A—C13—H13B | 109.5 |
N3—C2—C12 | 120.31 (15) | C3—C13—H13C | 109.5 |
C3—C2—C12 | 129.45 (15) | H13A—C13—H13C | 109.5 |
C2—C3—C4 | 107.83 (13) | H13B—C13—H13C | 109.5 |
C2—C3—C13 | 127.73 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O | 0.86 | 1.97 | 2.661 (2) | 137 |
N3—H3···S | 0.82 (3) | 2.60 (3) | 2.9834 (16) | 110 (2) |
N1—H1B···Si | 0.86 | 2.60 | 3.4495 (17) | 169 |
N3—H3···Oii | 0.82 (3) | 2.15 (3) | 2.840 (2) | 142 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1/2, y+1/2, z. |
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