In the title molecule, the five- and six-membered rings are oriented at a dihedral angle of 75.88 (8)°. In the crystal, N—H⋯N hydrogen bonds form chains of molecules extending along the c-axis direction that are connected by inversion-related pairs of O—H⋯N into ribbons. The ribbons are linked by C—H⋯π(ring) interactions, forming layers parallel to the ab plane.
Supporting information
CCDC reference: 2327436
Ethyl
2-cyano-3-(3-hydroxy-5-methyl-1
H-pyrazol-4-yl)-3-phenylpropanoate
top
Crystal data top
C16H17N3O3 | Z = 2 |
Mr = 299.32 | F(000) = 316 |
Triclinic, P1 | Dx = 1.300 Mg m−3 |
a = 9.1397 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 9.4879 (2) Å | Cell parameters from 8141 reflections |
c = 10.0063 (2) Å | θ = 4.7–72.2° |
α = 79.554 (1)° | µ = 0.75 mm−1 |
β = 63.787 (1)° | T = 150 K |
γ = 83.054 (1)° | Prism, clear colourless |
V = 764.75 (3) Å3 | 0.16 × 0.09 × 0.03 mm |
Data collection top
Bruker D8 VENTURE PHOTON 3 CPAD diffractometer | 2998 independent reflections |
Radiation source: INCOATEC IµS micro–focus source | 2207 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.112 |
Detector resolution: 7.3910 pixels mm-1 | θmax = 72.4°, θmin = 4.7° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | k = −11→11 |
Tmin = 0.88, Tmax = 0.98 | l = −12→12 |
36885 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: mixed |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0565P)2 + 0.3004P] where P = (Fo2 + 2Fc2)/3 |
2998 reflections | (Δ/σ)max < 0.001 |
207 parameters | Δρmax = 0.19 e Å−3 |
2 restraints | Δρmin = −0.23 e Å−3 |
Special details top
Experimental. The diffraction data were obtained from sets of frames,
each of width 0.5° in ω or φ, collected with scan parameters
determined by the "strategy" routine in APEX4. The scan
time was sec/frame. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 > 2sigma(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. H-atoms attached to carbon
were placed in calculated positions (C—H = 0.95 - 1.00 Å) and were
included as riding contributions with isotropic displacement parameters
1.2 - 1.5 times those of the attached atoms. Those attached to nitrogen
and to oxygen were placed in locations derived from a difference map and
refined with DFIX 0.91 0.01 and DFIX 0.85 0.01 instructions, respectively. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.31072 (17) | 0.88849 (16) | 0.53196 (17) | 0.0374 (4) | |
O2 | 0.34195 (18) | 0.66225 (16) | 0.47923 (18) | 0.0396 (4) | |
O3 | 0.5608 (2) | 0.97967 (16) | 0.16765 (17) | 0.0380 (4) | |
H3 | 0.510 (3) | 1.038 (2) | 0.124 (3) | 0.057* | |
N1 | 0.6348 (2) | 0.70329 (19) | −0.03454 (19) | 0.0340 (4) | |
H1 | 0.641 (3) | 0.670 (3) | −0.1172 (19) | 0.051* | |
N2 | 0.5886 (2) | 0.84391 (19) | −0.01623 (19) | 0.0327 (4) | |
N3 | 0.6355 (2) | 0.7145 (2) | 0.6688 (2) | 0.0441 (5) | |
C1 | 0.0507 (3) | 0.8091 (3) | 0.7386 (3) | 0.0574 (7) | |
H1A | −0.067805 | 0.824670 | 0.774657 | 0.086* | |
H1B | 0.085342 | 0.844719 | 0.805661 | 0.086* | |
H1C | 0.079772 | 0.706292 | 0.737677 | 0.086* | |
C2 | 0.1346 (3) | 0.8881 (3) | 0.5822 (3) | 0.0453 (6) | |
H2A | 0.112275 | 0.842376 | 0.512074 | 0.054* | |
H2B | 0.089410 | 0.988276 | 0.579737 | 0.054* | |
C3 | 0.3974 (2) | 0.7698 (2) | 0.4823 (2) | 0.0306 (4) | |
C4 | 0.5793 (2) | 0.7876 (2) | 0.4307 (2) | 0.0278 (4) | |
H4 | 0.604261 | 0.890474 | 0.389034 | 0.033* | |
C5 | 0.6124 (2) | 0.7486 (2) | 0.5641 (2) | 0.0333 (5) | |
C6 | 0.5994 (2) | 0.8562 (2) | 0.1099 (2) | 0.0301 (4) | |
C7 | 0.6532 (2) | 0.7267 (2) | 0.1720 (2) | 0.0278 (4) | |
C8 | 0.6750 (2) | 0.6317 (2) | 0.0746 (2) | 0.0316 (4) | |
C9 | 0.7316 (3) | 0.4776 (2) | 0.0780 (3) | 0.0443 (6) | |
H9A | 0.680821 | 0.428399 | 0.032257 | 0.066* | |
H9B | 0.700504 | 0.432922 | 0.182580 | 0.066* | |
H9C | 0.850573 | 0.470104 | 0.021522 | 0.066* | |
C10 | 0.6881 (2) | 0.6924 (2) | 0.3084 (2) | 0.0277 (4) | |
H10 | 0.660923 | 0.590388 | 0.352463 | 0.033* | |
C11 | 0.8671 (2) | 0.7065 (2) | 0.2704 (2) | 0.0276 (4) | |
C12 | 0.9482 (2) | 0.5996 (2) | 0.3305 (2) | 0.0335 (5) | |
H12 | 0.892943 | 0.516295 | 0.391447 | 0.040* | |
C13 | 1.1095 (3) | 0.6133 (3) | 0.3023 (2) | 0.0391 (5) | |
H13 | 1.163765 | 0.539442 | 0.343921 | 0.047* | |
C14 | 1.1906 (3) | 0.7340 (3) | 0.2139 (3) | 0.0410 (5) | |
H14 | 1.300235 | 0.744139 | 0.195775 | 0.049* | |
C15 | 1.1118 (3) | 0.8403 (3) | 0.1519 (3) | 0.0399 (5) | |
H15 | 1.168056 | 0.922894 | 0.090037 | 0.048* | |
C16 | 0.9514 (3) | 0.8269 (2) | 0.1793 (2) | 0.0356 (5) | |
H16 | 0.898446 | 0.900196 | 0.135782 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0302 (8) | 0.0378 (8) | 0.0425 (9) | 0.0015 (6) | −0.0144 (6) | −0.0070 (7) |
O2 | 0.0342 (8) | 0.0396 (9) | 0.0476 (9) | −0.0058 (6) | −0.0179 (7) | −0.0090 (7) |
O3 | 0.0555 (10) | 0.0341 (8) | 0.0356 (8) | 0.0037 (7) | −0.0318 (7) | −0.0034 (6) |
N1 | 0.0400 (10) | 0.0407 (10) | 0.0253 (8) | −0.0016 (7) | −0.0176 (7) | −0.0055 (7) |
N2 | 0.0360 (9) | 0.0390 (10) | 0.0265 (8) | −0.0032 (7) | −0.0173 (7) | −0.0013 (7) |
N3 | 0.0489 (12) | 0.0569 (13) | 0.0323 (10) | 0.0084 (9) | −0.0241 (9) | −0.0097 (9) |
C1 | 0.0411 (14) | 0.0526 (16) | 0.0616 (17) | −0.0039 (11) | −0.0058 (12) | −0.0099 (13) |
C2 | 0.0330 (12) | 0.0523 (14) | 0.0522 (14) | 0.0081 (10) | −0.0198 (10) | −0.0138 (11) |
C3 | 0.0314 (10) | 0.0362 (11) | 0.0256 (10) | −0.0001 (8) | −0.0145 (8) | −0.0027 (8) |
C4 | 0.0304 (10) | 0.0312 (10) | 0.0241 (9) | −0.0026 (8) | −0.0148 (8) | −0.0003 (8) |
C5 | 0.0320 (11) | 0.0404 (12) | 0.0294 (10) | 0.0002 (8) | −0.0150 (9) | −0.0061 (9) |
C6 | 0.0312 (10) | 0.0385 (11) | 0.0245 (9) | −0.0039 (8) | −0.0154 (8) | −0.0035 (8) |
C7 | 0.0264 (9) | 0.0358 (11) | 0.0218 (9) | −0.0037 (7) | −0.0117 (7) | −0.0004 (8) |
C8 | 0.0333 (10) | 0.0367 (11) | 0.0257 (9) | −0.0043 (8) | −0.0143 (8) | −0.0011 (8) |
C9 | 0.0606 (15) | 0.0409 (13) | 0.0370 (12) | 0.0051 (11) | −0.0265 (11) | −0.0095 (10) |
C10 | 0.0319 (10) | 0.0275 (10) | 0.0264 (9) | −0.0037 (7) | −0.0161 (8) | 0.0004 (8) |
C11 | 0.0291 (10) | 0.0324 (10) | 0.0232 (9) | −0.0018 (8) | −0.0127 (8) | −0.0041 (8) |
C12 | 0.0349 (11) | 0.0376 (12) | 0.0291 (10) | −0.0014 (9) | −0.0160 (9) | −0.0017 (9) |
C13 | 0.0340 (11) | 0.0511 (14) | 0.0359 (11) | 0.0050 (9) | −0.0204 (9) | −0.0054 (10) |
C14 | 0.0293 (11) | 0.0595 (15) | 0.0378 (12) | −0.0053 (10) | −0.0152 (9) | −0.0119 (10) |
C15 | 0.0380 (12) | 0.0437 (13) | 0.0374 (12) | −0.0119 (10) | −0.0146 (9) | −0.0021 (10) |
C16 | 0.0359 (11) | 0.0360 (12) | 0.0346 (11) | −0.0048 (9) | −0.0167 (9) | 0.0019 (9) |
Geometric parameters (Å, º) top
O1—C3 | 1.335 (2) | C6—C7 | 1.409 (3) |
O1—C2 | 1.460 (3) | C7—C8 | 1.380 (3) |
O2—C3 | 1.204 (2) | C7—C10 | 1.506 (3) |
O3—C6 | 1.340 (2) | C8—C9 | 1.490 (3) |
O3—H3 | 0.857 (10) | C9—H9A | 0.9800 |
N1—C8 | 1.348 (3) | C9—H9B | 0.9800 |
N1—N2 | 1.370 (2) | C9—H9C | 0.9800 |
N1—H1 | 0.914 (10) | C10—C11 | 1.524 (3) |
N2—C6 | 1.335 (2) | C10—H10 | 1.0000 |
N3—C5 | 1.141 (3) | C11—C12 | 1.389 (3) |
C1—C2 | 1.501 (4) | C11—C16 | 1.394 (3) |
C1—H1A | 0.9800 | C12—C13 | 1.391 (3) |
C1—H1B | 0.9800 | C12—H12 | 0.9500 |
C1—H1C | 0.9800 | C13—C14 | 1.379 (3) |
C2—H2A | 0.9900 | C13—H13 | 0.9500 |
C2—H2B | 0.9900 | C14—C15 | 1.383 (3) |
C3—C4 | 1.529 (3) | C14—H14 | 0.9500 |
C4—C5 | 1.470 (3) | C15—C16 | 1.385 (3) |
C4—C10 | 1.552 (3) | C15—H15 | 0.9500 |
C4—H4 | 1.0000 | C16—H16 | 0.9500 |
| | | |
C3—O1—C2 | 116.68 (17) | N1—C8—C7 | 107.38 (18) |
C6—O3—H3 | 109.6 (19) | N1—C8—C9 | 122.35 (18) |
C8—N1—N2 | 112.28 (16) | C7—C8—C9 | 130.27 (18) |
C8—N1—H1 | 127.6 (17) | C8—C9—H9A | 109.5 |
N2—N1—H1 | 120.0 (17) | C8—C9—H9B | 109.5 |
C6—N2—N1 | 103.85 (16) | H9A—C9—H9B | 109.5 |
C2—C1—H1A | 109.5 | C8—C9—H9C | 109.5 |
C2—C1—H1B | 109.5 | H9A—C9—H9C | 109.5 |
H1A—C1—H1B | 109.5 | H9B—C9—H9C | 109.5 |
C2—C1—H1C | 109.5 | C7—C10—C11 | 112.75 (16) |
H1A—C1—H1C | 109.5 | C7—C10—C4 | 111.51 (16) |
H1B—C1—H1C | 109.5 | C11—C10—C4 | 109.52 (15) |
O1—C2—C1 | 111.9 (2) | C7—C10—H10 | 107.6 |
O1—C2—H2A | 109.2 | C11—C10—H10 | 107.6 |
C1—C2—H2A | 109.2 | C4—C10—H10 | 107.6 |
O1—C2—H2B | 109.2 | C12—C11—C16 | 118.64 (18) |
C1—C2—H2B | 109.2 | C12—C11—C10 | 119.87 (17) |
H2A—C2—H2B | 107.9 | C16—C11—C10 | 121.46 (18) |
O2—C3—O1 | 125.49 (19) | C11—C12—C13 | 120.77 (19) |
O2—C3—C4 | 123.93 (19) | C11—C12—H12 | 119.6 |
O1—C3—C4 | 110.57 (17) | C13—C12—H12 | 119.6 |
C5—C4—C3 | 107.30 (16) | C14—C13—C12 | 120.0 (2) |
C5—C4—C10 | 110.20 (16) | C14—C13—H13 | 120.0 |
C3—C4—C10 | 112.11 (15) | C12—C13—H13 | 120.0 |
C5—C4—H4 | 109.1 | C13—C14—C15 | 119.8 (2) |
C3—C4—H4 | 109.1 | C13—C14—H14 | 120.1 |
C10—C4—H4 | 109.1 | C15—C14—H14 | 120.1 |
N3—C5—C4 | 177.9 (2) | C14—C15—C16 | 120.4 (2) |
N2—C6—O3 | 122.06 (18) | C14—C15—H15 | 119.8 |
N2—C6—C7 | 112.33 (18) | C16—C15—H15 | 119.8 |
O3—C6—C7 | 125.61 (17) | C15—C16—C11 | 120.4 (2) |
C8—C7—C6 | 104.16 (17) | C15—C16—H16 | 119.8 |
C8—C7—C10 | 125.22 (18) | C11—C16—H16 | 119.8 |
C6—C7—C10 | 130.58 (18) | | |
| | | |
C8—N1—N2—C6 | −0.9 (2) | C8—C7—C10—C11 | 83.8 (2) |
C3—O1—C2—C1 | 79.9 (2) | C6—C7—C10—C11 | −93.6 (2) |
C2—O1—C3—O2 | −1.9 (3) | C8—C7—C10—C4 | −152.51 (19) |
C2—O1—C3—C4 | 178.73 (17) | C6—C7—C10—C4 | 30.1 (3) |
O2—C3—C4—C5 | −93.5 (2) | C5—C4—C10—C7 | 178.19 (16) |
O1—C3—C4—C5 | 85.9 (2) | C3—C4—C10—C7 | 58.8 (2) |
O2—C3—C4—C10 | 27.6 (3) | C5—C4—C10—C11 | −56.3 (2) |
O1—C3—C4—C10 | −152.99 (16) | C3—C4—C10—C11 | −175.76 (15) |
N1—N2—C6—O3 | −178.86 (18) | C7—C10—C11—C12 | −133.87 (19) |
N1—N2—C6—C7 | 0.7 (2) | C4—C10—C11—C12 | 101.4 (2) |
N2—C6—C7—C8 | −0.2 (2) | C7—C10—C11—C16 | 47.9 (3) |
O3—C6—C7—C8 | 179.32 (19) | C4—C10—C11—C16 | −76.9 (2) |
N2—C6—C7—C10 | 177.66 (19) | C16—C11—C12—C13 | 1.0 (3) |
O3—C6—C7—C10 | −2.8 (3) | C10—C11—C12—C13 | −177.28 (18) |
N2—N1—C8—C7 | 0.9 (2) | C11—C12—C13—C14 | 0.0 (3) |
N2—N1—C8—C9 | −179.08 (19) | C12—C13—C14—C15 | −0.9 (3) |
C6—C7—C8—N1 | −0.4 (2) | C13—C14—C15—C16 | 0.7 (3) |
C10—C7—C8—N1 | −178.39 (17) | C14—C15—C16—C11 | 0.3 (3) |
C6—C7—C8—C9 | 179.5 (2) | C12—C11—C16—C15 | −1.2 (3) |
C10—C7—C8—C9 | 1.5 (3) | C10—C11—C16—C15 | 177.08 (19) |
Hydrogen-bond geometry (Å, º) topCg1 is the centroid of the five-membered ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···N2i | 0.86 (1) | 1.85 (1) | 2.706 (2) | 175 (3) |
N1—H1···N3ii | 0.91 (1) | 2.13 (2) | 2.948 (2) | 149 (2) |
C14—H14···Cg1iii | 0.95 | 2.71 | 3.627 (3) | 162 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) x, y, z−1; (iii) x+1, y, z. |
Comparison of selected X-ray and DFT geometric data
(Å, °) topBonds/angles | X-ray | B3LYP/6-311G(d,p) |
O1—C3 | 1.335 (2) | 1.345 |
O1—C2 | 1.460 (3) | 1.521 |
O2—C3 | 1.204 (2) | 1.235 |
O3—C6 | 1.340 (2) | 1.337 |
N1—C8 | 1.348 (3) | 1.331 |
N1—N2 | 1.368 (2) | 1.377 |
N1—H1 | 0.914 (10) | 0.87 |
N2—C6 | 1.335 (2) | 1.322 |
N3—C5 | 1.141 (3) | 1.128 |
C3—O1—C2 | 116.67 (17) | 115.6 |
C8—N1—N2 | 112.35 (16) | 113.1 |
C6—N2—N1 | 103.86 (16) | 104.6 |
O2—C3—O1 | 125.51 (19) | 124.5 |
N2—C6—O3 | 122.03 (18) | 123.1 |
Calculated energies topMolecular energy (a.u.) (eV) | Compound (I) |
ELUMO (eV) | -0.82 |
EHOMO (eV) | -6.59 |
Gap ΔE (eV) | 5.77 |
Ionization potential I | 6.59 |
Electron affinity A | 0.82 |
Chemical hardness η | 2.88 |
Chemical softness σ | 0.17 |
Electronegativity χ | 3.70 |
Chemical potential µ | -3.71 |
Electrophilicity index ω | 2.38 |
Total energy TE (eV) | -27476.33 |