In the title compound, C
16H
18N
2O
3S, the pyrazole and ester fragments are almost coplanar and the dihedral angle between the pyrazole and benzene rings is 46.08 (13)°. There are three intramolecular interactions in the structure, forming three six-membered rings. The crystal packing is stabilized by C—H
O and C—H
π interactions.
Supporting information
CCDC reference: 242336
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.043
- wR factor = 0.109
- Data-to-parameter ratio = 13.7
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT480_ALERT_4_B Long H...A H-Bond Reported H8A .. CGP .. 2.84 Ang.
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT481_ALERT_4_C Long D...A H-Bond Reported C8 .. CGP .. 3.73 Ang.
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Ethyl
3-methyl-1-(3-methylbenzoyl)-5-(methylsulfanyl)-1
H-pyrazole-4-carboxylate
top
Crystal data top
C16H18N2O3S | Z = 2 |
Mr = 318.38 | F(000) = 336 |
Triclinic, P1 | Dx = 1.327 Mg m−3 |
Hall symbol: -P 1 | Melting point: 388–389 K K |
a = 7.677 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.228 (3) Å | Cell parameters from 4133 reflections |
c = 12.271 (4) Å | θ = 2.8–25.0° |
α = 81.745 (5)° | µ = 0.22 mm−1 |
β = 73.352 (5)° | T = 293 K |
γ = 73.583 (5)° | Needle, colourless |
V = 797.1 (5) Å3 | 0.30 × 0.24 × 0.16 mm |
Data collection top
Simens SMART 1000 CCD area-detector diffractometer | 2789 independent reflections |
Radiation source: fine-focus sealed tube | 2224 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
ω scans | h = −9→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −8→10 |
Tmin = 0.938, Tmax = 0.966 | l = −14→12 |
4133 measured reflections | |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.049P)2 + 0.2362P] where P = (Fo2 + 2Fc2)/3 |
2789 reflections | (Δ/σ)max = 0.002 |
203 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
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 | 0.22441 (9) | 0.21759 (6) | 0.42329 (5) | 0.04722 (19) | |
O1 | 0.2516 (2) | 0.51069 (16) | 0.31410 (12) | 0.0531 (4) | |
O2 | 0.2780 (3) | 0.70988 (17) | 0.38665 (14) | 0.0631 (5) | |
O3 | 0.2104 (3) | 0.48758 (19) | 0.84848 (14) | 0.0754 (6) | |
N1 | 0.2424 (2) | 0.39648 (18) | 0.68027 (14) | 0.0391 (4) | |
N2 | 0.2274 (2) | 0.27860 (18) | 0.62814 (14) | 0.0404 (4) | |
C1 | 0.2393 (3) | 0.3771 (3) | 0.79767 (18) | 0.0482 (5) | |
C2 | 0.2685 (3) | 0.2214 (2) | 0.85222 (17) | 0.0439 (5) | |
C3 | 0.3944 (3) | 0.0966 (3) | 0.79842 (19) | 0.0542 (6) | |
H3 | 0.4612 | 0.1068 | 0.7227 | 0.065* | |
C4 | 0.4199 (4) | −0.0427 (3) | 0.8580 (2) | 0.0663 (7) | |
H4 | 0.5053 | −0.1266 | 0.8226 | 0.080* | |
C5 | 0.3193 (4) | −0.0584 (3) | 0.9701 (2) | 0.0678 (7) | |
H5 | 0.3364 | −0.1536 | 1.0088 | 0.081* | |
C6 | 0.1939 (4) | 0.0643 (3) | 1.02589 (19) | 0.0550 (6) | |
C7 | 0.1713 (3) | 0.2034 (3) | 0.96572 (18) | 0.0488 (5) | |
H7 | 0.0886 | 0.2877 | 1.0021 | 0.059* | |
C8 | 0.0860 (5) | 0.0472 (3) | 1.1494 (2) | 0.0801 (9) | |
H8A | −0.0056 | −0.0079 | 1.1550 | 0.120* | |
H8B | 0.0237 | 0.1455 | 1.1775 | 0.120* | |
H8C | 0.1717 | −0.0070 | 1.1938 | 0.120* | |
C9 | 0.2558 (3) | 0.5219 (2) | 0.60699 (17) | 0.0373 (5) | |
C10 | 0.2497 (3) | 0.4844 (2) | 0.50384 (16) | 0.0361 (4) | |
C11 | 0.2330 (3) | 0.3318 (2) | 0.52228 (16) | 0.0354 (4) | |
C12 | 0.2142 (4) | 0.0463 (2) | 0.5116 (2) | 0.0622 (7) | |
H12A | 0.3217 | 0.0137 | 0.5425 | 0.093* | |
H12B | 0.2137 | −0.0309 | 0.4669 | 0.093* | |
H12C | 0.1015 | 0.0642 | 0.5728 | 0.093* | |
C13 | 0.2759 (3) | 0.6652 (2) | 0.6379 (2) | 0.0509 (6) | |
H13A | 0.3299 | 0.7202 | 0.5701 | 0.076* | |
H13B | 0.3562 | 0.6424 | 0.6886 | 0.076* | |
H13C | 0.1544 | 0.7255 | 0.6748 | 0.076* | |
C14 | 0.2616 (3) | 0.5824 (2) | 0.39850 (17) | 0.0411 (5) | |
C15 | 0.2594 (4) | 0.5934 (3) | 0.20422 (19) | 0.0570 (6) | |
H15A | 0.3661 | 0.6376 | 0.1816 | 0.068* | |
H15B | 0.1456 | 0.6741 | 0.2073 | 0.068* | |
C16 | 0.2784 (5) | 0.4832 (3) | 0.1217 (2) | 0.0840 (9) | |
H16A | 0.3988 | 0.4114 | 0.1122 | 0.126* | |
H16B | 0.2679 | 0.5361 | 0.0497 | 0.126* | |
H16C | 0.1808 | 0.4310 | 0.1501 | 0.126* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0667 (4) | 0.0381 (3) | 0.0425 (3) | −0.0158 (3) | −0.0183 (3) | −0.0071 (2) |
O1 | 0.0863 (12) | 0.0412 (8) | 0.0373 (8) | −0.0221 (8) | −0.0231 (8) | 0.0067 (6) |
O2 | 0.1004 (14) | 0.0413 (9) | 0.0545 (10) | −0.0309 (9) | −0.0234 (9) | 0.0082 (7) |
O3 | 0.1353 (18) | 0.0554 (10) | 0.0468 (10) | −0.0331 (11) | −0.0300 (11) | −0.0078 (8) |
N1 | 0.0525 (11) | 0.0340 (9) | 0.0348 (9) | −0.0134 (8) | −0.0152 (8) | −0.0025 (7) |
N2 | 0.0535 (11) | 0.0332 (9) | 0.0383 (9) | −0.0139 (8) | −0.0148 (8) | −0.0027 (7) |
C1 | 0.0620 (15) | 0.0486 (13) | 0.0383 (12) | −0.0163 (11) | −0.0164 (10) | −0.0051 (10) |
C2 | 0.0490 (13) | 0.0494 (12) | 0.0354 (11) | −0.0123 (10) | −0.0153 (10) | −0.0016 (9) |
C3 | 0.0530 (15) | 0.0642 (15) | 0.0364 (12) | −0.0061 (11) | −0.0089 (11) | 0.0019 (11) |
C4 | 0.0735 (18) | 0.0572 (15) | 0.0470 (14) | 0.0088 (13) | −0.0091 (13) | −0.0014 (11) |
C5 | 0.088 (2) | 0.0542 (15) | 0.0472 (14) | −0.0054 (13) | −0.0143 (14) | 0.0070 (12) |
C6 | 0.0659 (16) | 0.0590 (15) | 0.0369 (12) | −0.0148 (12) | −0.0119 (11) | 0.0014 (11) |
C7 | 0.0551 (14) | 0.0533 (13) | 0.0383 (11) | −0.0109 (11) | −0.0135 (10) | −0.0071 (10) |
C8 | 0.104 (2) | 0.0789 (19) | 0.0437 (15) | −0.0228 (17) | −0.0033 (15) | 0.0051 (13) |
C9 | 0.0402 (12) | 0.0307 (10) | 0.0402 (11) | −0.0066 (8) | −0.0106 (9) | −0.0037 (8) |
C10 | 0.0394 (11) | 0.0309 (10) | 0.0367 (11) | −0.0070 (8) | −0.0095 (9) | −0.0026 (8) |
C11 | 0.0402 (11) | 0.0314 (10) | 0.0353 (11) | −0.0088 (8) | −0.0106 (9) | −0.0033 (8) |
C12 | 0.0902 (19) | 0.0386 (12) | 0.0683 (16) | −0.0254 (12) | −0.0282 (14) | −0.0030 (11) |
C13 | 0.0666 (16) | 0.0361 (11) | 0.0538 (14) | −0.0132 (10) | −0.0187 (12) | −0.0088 (10) |
C14 | 0.0466 (12) | 0.0346 (11) | 0.0411 (11) | −0.0108 (9) | −0.0109 (10) | 0.0007 (9) |
C15 | 0.0742 (17) | 0.0584 (14) | 0.0403 (13) | −0.0210 (12) | −0.0220 (12) | 0.0138 (11) |
C16 | 0.125 (3) | 0.082 (2) | 0.0448 (15) | −0.0200 (18) | −0.0290 (16) | −0.0018 (14) |
Geometric parameters (Å, º) top
S1—C11 | 1.7448 (19) | C7—H7 | 0.93 |
S1—C12 | 1.792 (2) | C8—H8A | 0.96 |
O1—C14 | 1.337 (2) | C8—H8B | 0.96 |
O1—C15 | 1.445 (3) | C8—H8C | 0.96 |
O2—C14 | 1.202 (2) | C9—C10 | 1.376 (3) |
O3—C1 | 1.205 (3) | C9—C13 | 1.486 (3) |
N1—C9 | 1.369 (2) | C10—C11 | 1.429 (3) |
N1—N2 | 1.385 (2) | C10—C14 | 1.463 (3) |
N1—C1 | 1.420 (3) | C12—H12A | 0.96 |
N2—C11 | 1.314 (3) | C12—H12B | 0.96 |
C1—C2 | 1.481 (3) | C12—H12C | 0.96 |
C2—C3 | 1.386 (3) | C13—H13A | 0.96 |
C2—C7 | 1.390 (3) | C13—H13B | 0.96 |
C3—C4 | 1.376 (3) | C13—H13C | 0.96 |
C3—H3 | 0.93 | C15—C16 | 1.485 (3) |
C4—C5 | 1.381 (3) | C15—H15A | 0.97 |
C4—H4 | 0.93 | C15—H15B | 0.97 |
C5—C6 | 1.381 (4) | C16—H16A | 0.96 |
C5—H5 | 0.93 | C16—H16B | 0.96 |
C6—C7 | 1.378 (3) | C16—H16C | 0.96 |
C6—C8 | 1.514 (3) | | |
| | | |
C11—S1—C12 | 99.70 (10) | C10—C9—C13 | 129.37 (19) |
C14—O1—C15 | 117.30 (16) | C9—C10—C11 | 105.51 (17) |
C9—N1—N2 | 112.32 (15) | C9—C10—C14 | 125.97 (17) |
C9—N1—C1 | 128.35 (16) | C11—C10—C14 | 128.51 (17) |
N2—N1—C1 | 119.33 (16) | N2—C11—C10 | 111.77 (17) |
C11—N2—N1 | 104.49 (15) | N2—C11—S1 | 120.27 (14) |
O3—C1—N1 | 118.8 (2) | C10—C11—S1 | 127.95 (15) |
O3—C1—C2 | 123.2 (2) | S1—C12—H12A | 109.5 |
N1—C1—C2 | 118.01 (18) | S1—C12—H12B | 109.5 |
C3—C2—C7 | 119.2 (2) | H12A—C12—H12B | 109.5 |
C3—C2—C1 | 123.5 (2) | S1—C12—H12C | 109.5 |
C7—C2—C1 | 117.1 (2) | H12A—C12—H12C | 109.5 |
C4—C3—C2 | 119.5 (2) | H12B—C12—H12C | 109.5 |
C4—C3—H3 | 120.3 | C9—C13—H13A | 109.5 |
C2—C3—H3 | 120.3 | C9—C13—H13B | 109.5 |
C3—C4—C5 | 120.3 (2) | H13A—C13—H13B | 109.5 |
C3—C4—H4 | 119.8 | C9—C13—H13C | 109.5 |
C5—C4—H4 | 119.8 | H13A—C13—H13C | 109.5 |
C4—C5—C6 | 121.3 (2) | H13B—C13—H13C | 109.5 |
C4—C5—H5 | 119.3 | O2—C14—O1 | 123.26 (19) |
C6—C5—H5 | 119.3 | O2—C14—C10 | 126.17 (19) |
C7—C6—C5 | 117.8 (2) | O1—C14—C10 | 110.56 (16) |
C7—C6—C8 | 121.0 (2) | O1—C15—C16 | 106.90 (19) |
C5—C6—C8 | 121.2 (2) | O1—C15—H15A | 110.3 |
C6—C7—C2 | 121.9 (2) | C16—C15—H15A | 110.3 |
C6—C7—H7 | 119.1 | O1—C15—H15B | 110.3 |
C2—C7—H7 | 119.1 | C16—C15—H15B | 110.3 |
C6—C8—H8A | 109.5 | H15A—C15—H15B | 108.6 |
C6—C8—H8B | 109.5 | C15—C16—H16A | 109.5 |
H8A—C8—H8B | 109.5 | C15—C16—H16B | 109.5 |
C6—C8—H8C | 109.5 | H16A—C16—H16B | 109.5 |
H8A—C8—H8C | 109.5 | C15—C16—H16C | 109.5 |
H8B—C8—H8C | 109.5 | H16A—C16—H16C | 109.5 |
N1—C9—C10 | 105.91 (16) | H16B—C16—H16C | 109.5 |
N1—C9—C13 | 124.71 (18) | | |
| | | |
C9—N1—N2—C11 | 0.4 (2) | N2—N1—C9—C13 | −179.20 (19) |
C1—N1—N2—C11 | 179.46 (18) | C1—N1—C9—C13 | 1.9 (3) |
C9—N1—C1—O3 | 15.2 (4) | N1—C9—C10—C11 | −0.3 (2) |
N2—N1—C1—O3 | −163.7 (2) | C13—C9—C10—C11 | 178.8 (2) |
C9—N1—C1—C2 | −165.9 (2) | N1—C9—C10—C14 | −179.29 (19) |
N2—N1—C1—C2 | 15.2 (3) | C13—C9—C10—C14 | −0.2 (4) |
O3—C1—C2—C3 | −142.9 (3) | N1—N2—C11—C10 | −0.6 (2) |
N1—C1—C2—C3 | 38.2 (3) | N1—N2—C11—S1 | 178.35 (13) |
O3—C1—C2—C7 | 33.1 (3) | C9—C10—C11—N2 | 0.5 (2) |
N1—C1—C2—C7 | −145.7 (2) | C14—C10—C11—N2 | 179.54 (19) |
C7—C2—C3—C4 | 0.4 (4) | C9—C10—C11—S1 | −178.28 (15) |
C1—C2—C3—C4 | 176.4 (2) | C14—C10—C11—S1 | 0.7 (3) |
C2—C3—C4—C5 | 0.7 (4) | C12—S1—C11—N2 | −1.2 (2) |
C3—C4—C5—C6 | −1.2 (5) | C12—S1—C11—C10 | 177.55 (19) |
C4—C5—C6—C7 | 0.4 (4) | C15—O1—C14—O2 | −0.6 (3) |
C4—C5—C6—C8 | −179.0 (3) | C15—O1—C14—C10 | 179.36 (19) |
C5—C6—C7—C2 | 0.8 (4) | C9—C10—C14—O2 | −0.2 (4) |
C8—C6—C7—C2 | −179.8 (2) | C11—C10—C14—O2 | −179.0 (2) |
C3—C2—C7—C6 | −1.2 (3) | C9—C10—C14—O1 | 179.84 (19) |
C1—C2—C7—C6 | −177.4 (2) | C11—C10—C14—O1 | 1.0 (3) |
N2—N1—C9—C10 | −0.1 (2) | C14—O1—C15—C16 | 170.6 (2) |
C1—N1—C9—C10 | −179.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N2 | 0.93 | 2.48 | 2.853 (3) | 104 |
C12—H12B···O2i | 0.96 | 2.58 | 3.508 (3) | 162 |
C13—H13A···O2 | 0.96 | 2.42 | 3.047 (3) | 123 |
C13—H13B···O3 | 0.96 | 2.45 | 2.850 (3) | 105 |
C8—H8A···CgPii | 0.96 | 2.84 | 3.735 (4) | 155 |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y, −z+2. |