Upon recrystallization from ethylene glycol in daylight, (E)-5-phenyl-1-(pyridin-2-yl)pent-2-en-4-yn-1-one underwent spontaneous [2 + 2] cycloaddition reaction while (E)-5-(4-methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one remained photoinert.
Keywords: vinyl ketones with acetylene fragment, cyclobutane derivatives, photoreaction, crystal structure
Abstract
Recrystallization of (E)-5-phenyl-1-(pyridin-2-yl)pent-2-en-4-yn-1-one at room temperature from ethylene glycol in daylight afforded [3,4-bis(phenylethynyl)cyclobutane-1,2-diyl)bis(pyridin-2-ylmethanone], C32H22N2O2 (3), while (E)-5-(4-methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one, C17H13NO (2), remained photoinert. This is the first experimental evidence that pentenynones can be photoreactive when fixed in nearly coplanar parallel positions. During the photoreaction, the bond lengths and angles along the pentenyne chain changed significantly, while the disposition of the pyridyl ring towards the keto group was almost unchanged. The cyclobutane ring adopts an rctt conformation.
Chemical context
Vinyl-substituted ketones are known to take part in photo-initiated reactions both in the solid state and in solution (Hopkin et al., 1991 ▸; Vatsadze et al., 2006 ▸). Both trans–cis isomerization and [2 + 2] cycloaddition reactions can be observed depending on the nature of the substituents on the alkyl chain (Vatsadze et al., 2006 ▸). Many of the compounds previously reported by us, including 1,5-diarylpentenynones (Golovanov et al., 2013 ▸; Vologzhanina et al., 2014 ▸; Voronova et al., 2016 ▸1) and cyclic ketones with vinylacetylene fragments (Voronova et al., 2018 ▸) in crystals exhibit coplanar packing with a distance between the olefin fragments of less than 4.2 Å; thus, they satisfy the Schmidt (1971 ▸) criteria for a solid-state [2 + 2] cycloaddition to occur. However, our numerous attepts to carry out [2 + 2] photocycloaddition in these compounds were unsuccessful. We aimed to synthesize pyridine-substituted representatives of this family in order to fix olefin fragments in photoreactive positions using hydrogen bonding or coordination bonding as described by Nagarathinam et al. (2008 ▸). Two novel pyridine-2-yl-containing ketones, 1 and 2 (Scheme and Fig. 1 ▸), were synthesized as described below, and recrystallized from ethanol. Single-crystal XRD data for 2 could only be obtained using synchrotron radiation, while we failed to obtain a crystal structure of 1 using single-crystal or powder X-ray diffraction. Recrystallization of 1 and 2 from ethylene glycol afforded, respectively, a dimerization reaction product, 3, and the initial solid phase.
Figure 1.
The molecular structure of 2 and 3, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
Structural commentary
The asymmetric unit of ketone 2 contains two independent molecules (Fig. 1 ▸). Their conformations are very similar to each other as shown in Fig. 2 ▸. Both molecules of 2 exhibit delocalization of charge density along the alkyl chain, as can be concluded from the bond lengths given in Table 1 ▸, the single bonds between a double and a triple bond being much shorter than the average value of 1.53–1.54 Å for a C—C bond. The corresponding values for the C=O ketone fragments in 3 are similar to those in 2, while the absence of double bonds along the alkyl chain causes shortening of the allyl bonds and elongation of single bonds. The bond lengths in the cyclobutane ring of 3 are unequal: those corresponding to a previously ‘double’ bond are characteristic of a C—C bond (ca 1.55 Å), while the single bonds between two ‘monomers’ are elongated to 1.575 (2) Å. Only the rctt isomer of a 1,2,3,4-tetrasubstituted cyclobutane was obtained of four theoretically possible (based on XRD data).
Figure 2.
Conformation of the two symmetrically independent molecules in 2 (red and blue) in superimposed representation.
Table 1. Selected geometry parameters (Å, °) for 2 and 3 .
The carbon atoms of the pentenynone fragment are numbered from 1 to 5. Φ1 is the dihedral angle between the pyridine ring and the ketone fragment and Φ2 is the dihedral angle between the pyridine and phenyl rings.
| Bond | 2 | 3 |
|---|---|---|
| C1=O | 1.226 (2), 1.228 (2) | 1.212 (2), 1.215 (2) |
| C1—Cpy | 1.498 (3)–1.498 (2) | 1.495 (2), 1.498 (2) |
| C1—C2 | 1.474 (3)–1.477 (3) | 1.509 (2), 1.513 (2) |
| C2=C3 | 1.335 (3), 1.336 (3) | – |
| Ccb—Ccb | – | 1.549 (2), 1.554 (2) |
| C3—C4 | 1.411 (3), 1.420 (3) | 1.454 (2), 1.460 (2) |
| C4≡C5 | 1.206 (3), 1.203 (3) | 1.195 (2), 1.194 (2) |
| C5—CPh | 1.426 (3), 1.430 (3) | 1.441 (2), 1.439 (2) |
| Φ1 | 11.0 (1), 11.1 (1) | 14.8 (1), 0.9 (1) |
| Φ2 | 7.4 (1), 5.1 (1) | 84.8 (1), 47.0 (1) |
The conformations of the molecules of both 2 and 3 is probably affected by intramolecular C—H⋯N contacts (Tables 2 ▸ and 3 ▸) involving the nitrogen atoms of the pyridine-2-yl rings and hydrogen atoms of ethenyl or cyclobutane moieties. The C—H⋯N angle does not exceed 102°; however, such a mutual disposition of the conjugated pyridine ring and a double bond was found not only in 2 and 3, but also in previously reported pyridine-2-yl-containing chalcones. The chalcones in the Cambridge Structural Database (CSD, Version 5.40, update of November 2019; Groom et al., 2016 ▸) [ABADUE (Fun et al., 2011b ▸), AFOPOC (Chantrapromma et al., 2013 ▸), AYUYOJ (Fun et al., 2011a ▸), BERXEC (Wang et al., 2004 ▸), CIBYIY (Brennan et al., 2018 ▸), COBJEJ (Prajapati et al., 2008 ▸), ENINOG (Lee et al., 2016 ▸), GARMAP (Fan & Wang, 2012 ▸), IJUSAI (Jasinski et al., 2011 ▸), IXOXOJ (Dudek et al., 2011 ▸), LANTAY (Qian et al., 2017 ▸), OGIZIP and VUZVET (Tan et al., 2016 ▸), PUKVEY (Rout & Mondal, 2015 ▸), QEMJOK and QEMJUQ (Albaladejo et al., 2018 ▸), SOXHAP (Lin et al., 2009 ▸), TISCEF (Jayarama et al., 2013 ▸) and YUQTEK (Li et al., 2010 ▸)] demonstrate similar conformations, but different crystal packing in the region of pyridyl ring. The majority of 1-phenyl-substituted chalcones and 1-phenyl-substituted pentenyn-1-ones also exhibit a nearly coplanar arrangement of the aryl and ketone fragments and thus no hindrance occurs between the hydrogen atoms of these fragments.
Table 2. Hydrogen-bond geometry (Å, °) for (2) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C2—H2⋯N1 | 0.95 | 2.52 | 2.832 (3) | 100 |
| C16—H16⋯N2i | 0.95 | 2.66 | 3.555 (3) | 158 |
| C20—H20⋯N2i | 0.95 | 2.71 | 3.465 (3) | 136 |
| C3—H3⋯O1ii | 0.95 | 2.43 | 3.206 (3) | 139 |
| C19—H19⋯O2iii | 0.95 | 2.57 | 3.379 (2) | 143 |
| C25—H25⋯O2iv | 0.95 | 2.65 | 3.561 (2) | 161 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
.
Table 3. Hydrogen-bond geometry (Å, °) for (3) .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C2—H2⋯N1 | 1.00 | 2.45 | 2.835 (3) | 102 |
| C3—H3⋯O1 | 1.00 | 2.49 | 2.899 (2) | 104 |
| C8—H8⋯O2 | 1.00 | 2.39 | 2.804 (2) | 104 |
| C25—H25⋯N1i | 0.95 | 2.60 | 3.445 (3) | 148 |
| C19—H19⋯N1ii | 0.95 | 2.73 | 3.665 (2) | 167 |
| C20—H20⋯O1iii | 0.95 | 2.62 | 3.263 (2) | 125 |
| C32—H32⋯O2iv | 0.95 | 2.55 | 3.487 (2) | 168 |
Symmetry codes: (i) 
; (ii) ; (iii) 
; (iv) 
.
Supramolecular features
As the independent molecules of ketone 2 have similar conformations, their crystalline environment becomes of particular interest because it can rationalize why Z ≠ 1. Previously, we found that the most abundant C—H⋯O-bonded associates in the crystals of chalcones, polyenones and pentenynones include dimers, head-to-tail chains and zigzag C—H⋯O chains with the most acidic proton of a molecule (Vologzhanina et al., 2014 ▸). The two independent molecules of ketone 2 demonstrate two of these motifs (Fig. 3 ▸). In the C—H⋯O-connected dimers, r(C⋯O) = 3.206 (3) Å, and in the head-to-tail chains r(C⋯O) and r(C⋯N) = 3.379 (2) and 3.465 (3) Å, respectively. The corresponding C—H⋯O and C—H⋯N angles are, respectively, 139, 143 and 136°. Note, that only one of two independent molecules in 2 forms head-to-tail chains via a pair of intermolecular C—H⋯O and C—N⋯N bonds. None of the previously reported pyridine-2-yl-containing chalcones nor 3 forms such associates. Instead, the nitrogen atoms interact with the hydrogen atoms of the alkyl and aryl groups. For example, in the crystal of 3, the hydrogen atoms of a pyridine-2-yl ring take part in C—H⋯N interactions [Fig. 3 ▸, r(C⋯N) = 3.445 (3)–3.665 (2) Å]. Oxygen atoms take part in C—H⋯O bonding with hydrogen atoms of the phenyl and pyridin-2-yl rings. In addition, in 2 and 3, numerous hydrophobic interactions can be found.
Figure 3.
Supramolecular aggregates in the crystals of 2 and 3. Hydrogen bonds are depicted by dashed lines.
Synthesis and crystallization
The 5-phenyl-1-(pyridin-2-yl)pent-2-en-4-yn-1-one, 1, and 5-(4-methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one, 2, were synthesized according to the previously described method (Golovanov et al., 2013 ▸). Single crystals of 3 were grown from solution of 1 in ethylene glycol. The 1H NMR spectrum indicates the presence of a mixture of reaction products and unreacted 1. Powder XRD indicated that the solid sample of the recrystallized ketone consisted of both 1 and 3, and thus solid 3 could not be characterized by other physicochemical methods. Recrystallization of 2 from ethylene glycol afforded 2 as obtained from XRD data.
For 1: yellowish needles, yield 61%, m.p. 348–351 K (from a mixture of water and ethanol). 1H NMR (300 MHz, CDCl3), δ, ppm: 8.48 s (1C, CAr, CPy), 8.09–8.16 m (2C, CAr, CPy, C2), 7.84–7.79 m (2C, CAr, CPy), 7.20–7.52 m (6C, CAr, C3). 13C NMR (75 MHz, CDCl3), δ, ppm: 188.5 (C1), 152.6, 149.0, 132.2, 131.9, 129.5, 128.6, 128.2, 128.0, 127.1, 122.1, 99.6 (C5), 88.9 (C4). Found, %: C 82.44; H 5.41. C16H11NO. Calculated, %: C 82.38; H 4.75.
For 2: yellowish needles, yield 34%, m.p. 373–374 K (from a mixture of water–ethanol. IR Spectra, ν, cm−1: 2191 (C≡C), 1649 (C=O). Found, %: C 82.44; H 5.33. C17H13NO. Calculated, %: C 82.57; H 5.30.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. Intensity data for 2 were collected at the K4.4 ‘Belok’ beamline of the Kurchatov Synchrotron Radiation Source (NRC ‘Kurchatov Institute’, Moscow, Russia) at a wavelength of 0.80248 Å using a Rayonix CCD 165 detector. Image integration was performed using iMosflm software (Battye et al., 2011 ▸). Hydrogen atoms were placed in calculated positions (0.95–1.00 Å) and refined using a riding model, with U iso(H) = 1.2U eq(C).
Table 4. Experimental details.
| (3) | (2) | |
|---|---|---|
| Crystal data | ||
| Chemical formula | C32H22N2O2 | C17H13NO |
| M r | 466.51 | 247.28 |
| Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
| Temperature (K) | 120 | 100 |
| a, b, c (Å) | 12.272 (3), 18.720 (4), 11.425 (2) | 14.859 (3), 17.747 (4), 9.995 (2) |
| β (°) | 115.850 (3) | 101.06 (3) |
| V (Å3) | 2362.0 (8) | 2586.7 (9) |
| Z | 4 | 8 |
| Radiation type | Mo Kα | Synchrotron, λ = 0.80248 Å |
| μ (mm−1) | 0.08 | 0.10 |
| Crystal size (mm) | 0.46 × 0.28 × 0.17 | 0.02 × 0.02 × 0.01 |
| Data collection | ||
| Diffractometer | Bruker SMART APEX CCD area detector | Mar CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2014 ▸) | Multi-scan (SCALA; Evans, 2006 ▸) |
| T min, T max | 0.848, 0.903 | 0.997, 0.999 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 24543, 7095, 4255 | 23024, 5645, 4453 |
| R int | 0.079 | 0.077 |
| (sin θ/λ)max (Å−1) | 0.714 | 0.640 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.056, 0.130, 0.99 | 0.060, 0.157, 1.02 |
| No. of reflections | 7095 | 5645 |
| No. of parameters | 325 | 346 |
| H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.31 | 0.23, −0.21 |
Supplementary Material
Crystal structure: contains datablock(s) global, 2, 3. DOI: 10.1107/S2056989020000055/ff2164sup1.cif
Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989020000055/ff21643sup2.hkl
Supporting information file. DOI: 10.1107/S2056989020000055/ff21643sup4.cml
Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989020000055/ff21642sup3.hkl
Supporting information file. DOI: 10.1107/S2056989020000055/ff21642sup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
This study was supported by the Russian Science Foundation (grant No 17–13-01442). The X-ray diffraction experiments of 2 and 3 were performed using, respectively, the K4.4 ‘Belok’ beamline of the Kurchatov Synchrotron Radiation Source and equipment of the Centre for Molecular Studies of INEOS RAS.
supplementary crystallographic information
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Crystal data
| C32H22N2O2 | F(000) = 976 |
| Mr = 466.51 | Dx = 1.312 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 12.272 (3) Å | Cell parameters from 4566 reflections |
| b = 18.720 (4) Å | θ = 2.2–30.0° |
| c = 11.425 (2) Å | µ = 0.08 mm−1 |
| β = 115.850 (3)° | T = 120 K |
| V = 2362.0 (8) Å3 | Prism, orange |
| Z = 4 | 0.46 × 0.28 × 0.17 mm |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Data collection
| Bruker SMART APEX CCD area detector diffractometer | 7095 independent reflections |
| Radiation source: sealed tube | 4255 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.079 |
| Detector resolution: 8 pixels mm-1 | θmax = 30.5°, θmin = 1.8° |
| ω scans | h = −15→17 |
| Absorption correction: multi-scan (SADABS; Bruker, 2014) | k = −26→26 |
| Tmin = 0.848, Tmax = 0.903 | l = −16→16 |
| 24543 measured reflections |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Refinement
| Refinement on F2 | Primary atom site location: dual |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.056 | H-atom parameters constrained |
| wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0557P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.99 | (Δ/σ)max < 0.001 |
| 7095 reflections | Δρmax = 0.33 e Å−3 |
| 325 parameters | Δρmin = −0.31 e Å−3 |
| 0 restraints |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Special details
| 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. |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.14655 (11) | 0.50117 (6) | 0.61894 (10) | 0.0224 (3) | |
| O2 | 0.44626 (12) | 0.53397 (6) | 0.81027 (11) | 0.0249 (3) | |
| N1 | 0.03170 (13) | 0.66755 (7) | 0.47517 (13) | 0.0215 (3) | |
| N2 | 0.26664 (14) | 0.68759 (7) | 0.76527 (14) | 0.0236 (3) | |
| C1 | 0.14015 (15) | 0.55793 (8) | 0.56522 (14) | 0.0167 (3) | |
| C2 | 0.23152 (15) | 0.57818 (8) | 0.51555 (15) | 0.0168 (3) | |
| H2 | 0.1954 | 0.6114 | 0.4396 | 0.020* | |
| C3 | 0.30105 (15) | 0.51652 (8) | 0.48769 (15) | 0.0173 (3) | |
| H3 | 0.3031 | 0.4743 | 0.5421 | 0.021* | |
| C4 | 0.25950 (16) | 0.49385 (8) | 0.35333 (15) | 0.0188 (3) | |
| C5 | 0.22108 (16) | 0.47470 (8) | 0.24269 (16) | 0.0202 (4) | |
| C6 | 0.38544 (15) | 0.58614 (8) | 0.75844 (15) | 0.0177 (3) | |
| C7 | 0.35663 (15) | 0.60721 (8) | 0.62014 (15) | 0.0175 (3) | |
| H7 | 0.3676 | 0.6595 | 0.6106 | 0.021* | |
| C8 | 0.42148 (16) | 0.55980 (8) | 0.55808 (15) | 0.0179 (3) | |
| H8 | 0.4875 | 0.5304 | 0.6245 | 0.021* | |
| C9 | 0.46337 (16) | 0.59998 (8) | 0.47593 (15) | 0.0198 (3) | |
| C10 | 0.50391 (16) | 0.63388 (8) | 0.41551 (15) | 0.0200 (4) | |
| C11 | 0.04630 (15) | 0.61189 (8) | 0.55421 (15) | 0.0171 (3) | |
| C12 | −0.01798 (17) | 0.60341 (8) | 0.62740 (17) | 0.0241 (4) | |
| H12 | −0.0064 | 0.5624 | 0.6805 | 0.029* | |
| C13 | −0.09935 (18) | 0.65600 (9) | 0.62137 (19) | 0.0303 (4) | |
| H13 | −0.1441 | 0.6521 | 0.6711 | 0.036* | |
| C14 | −0.11435 (18) | 0.71411 (9) | 0.54191 (18) | 0.0302 (4) | |
| H14 | −0.1687 | 0.7514 | 0.5367 | 0.036* | |
| C15 | −0.04852 (17) | 0.71700 (9) | 0.46982 (17) | 0.0270 (4) | |
| H15 | −0.0612 | 0.7565 | 0.4132 | 0.032* | |
| C16 | 0.17317 (16) | 0.45234 (8) | 0.10882 (15) | 0.0208 (4) | |
| C17 | 0.06057 (18) | 0.42003 (8) | 0.04773 (17) | 0.0282 (4) | |
| H17 | 0.0149 | 0.4108 | 0.0952 | 0.034* | |
| C18 | 0.0143 (2) | 0.40106 (9) | −0.08242 (17) | 0.0364 (5) | |
| H18 | −0.0629 | 0.3789 | −0.1238 | 0.044* | |
| C19 | 0.0804 (2) | 0.41430 (10) | −0.15217 (18) | 0.0406 (6) | |
| H19 | 0.0486 | 0.4013 | −0.2413 | 0.049* | |
| C20 | 0.1925 (2) | 0.44636 (10) | −0.09211 (18) | 0.0370 (5) | |
| H20 | 0.2375 | 0.4558 | −0.1402 | 0.044* | |
| C21 | 0.23975 (19) | 0.46490 (9) | 0.03804 (16) | 0.0274 (4) | |
| H21 | 0.3177 | 0.4862 | 0.0794 | 0.033* | |
| C22 | 0.33415 (15) | 0.63164 (8) | 0.83025 (15) | 0.0187 (3) | |
| C23 | 0.35862 (17) | 0.61505 (9) | 0.95735 (16) | 0.0244 (4) | |
| H23 | 0.4081 | 0.5753 | 1.0000 | 0.029* | |
| C24 | 0.30935 (18) | 0.65777 (10) | 1.02106 (18) | 0.0313 (4) | |
| H24 | 0.3238 | 0.6477 | 1.1081 | 0.038* | |
| C25 | 0.23927 (18) | 0.71490 (9) | 0.95603 (18) | 0.0309 (4) | |
| H25 | 0.2044 | 0.7452 | 0.9972 | 0.037* | |
| C26 | 0.22022 (18) | 0.72774 (9) | 0.82891 (18) | 0.0290 (4) | |
| H26 | 0.1713 | 0.7674 | 0.7847 | 0.035* | |
| C27 | 0.55587 (15) | 0.67731 (8) | 0.34887 (15) | 0.0187 (3) | |
| C28 | 0.56084 (16) | 0.75148 (8) | 0.36530 (16) | 0.0224 (4) | |
| H28 | 0.5309 | 0.7727 | 0.4210 | 0.027* | |
| C29 | 0.60909 (17) | 0.79383 (9) | 0.30078 (18) | 0.0279 (4) | |
| H29 | 0.6126 | 0.8442 | 0.3126 | 0.033* | |
| C30 | 0.65229 (18) | 0.76346 (9) | 0.21905 (18) | 0.0292 (4) | |
| H30 | 0.6837 | 0.7930 | 0.1733 | 0.035* | |
| C31 | 0.64973 (18) | 0.69037 (9) | 0.20388 (17) | 0.0289 (4) | |
| H31 | 0.6810 | 0.6696 | 0.1490 | 0.035* | |
| C32 | 0.60178 (17) | 0.64693 (8) | 0.26814 (16) | 0.0227 (4) | |
| H32 | 0.6002 | 0.5966 | 0.2572 | 0.027* |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0294 (8) | 0.0176 (5) | 0.0243 (6) | 0.0001 (5) | 0.0154 (6) | 0.0028 (4) |
| O2 | 0.0310 (8) | 0.0202 (6) | 0.0250 (6) | 0.0042 (5) | 0.0136 (6) | 0.0002 (5) |
| N1 | 0.0219 (9) | 0.0185 (7) | 0.0245 (7) | 0.0011 (6) | 0.0103 (7) | 0.0008 (5) |
| N2 | 0.0242 (9) | 0.0190 (7) | 0.0269 (7) | −0.0005 (6) | 0.0105 (7) | −0.0052 (6) |
| C1 | 0.0200 (10) | 0.0153 (7) | 0.0154 (7) | −0.0033 (6) | 0.0084 (7) | −0.0035 (6) |
| C2 | 0.0211 (10) | 0.0136 (7) | 0.0182 (7) | 0.0017 (6) | 0.0109 (7) | 0.0010 (6) |
| C3 | 0.0228 (10) | 0.0126 (7) | 0.0203 (8) | 0.0007 (6) | 0.0130 (7) | −0.0006 (6) |
| C4 | 0.0223 (10) | 0.0140 (7) | 0.0239 (8) | −0.0001 (6) | 0.0136 (7) | 0.0006 (6) |
| C5 | 0.0233 (10) | 0.0159 (7) | 0.0245 (8) | 0.0015 (6) | 0.0133 (8) | 0.0007 (6) |
| C6 | 0.0206 (10) | 0.0142 (7) | 0.0198 (7) | −0.0042 (6) | 0.0102 (7) | −0.0039 (6) |
| C7 | 0.0216 (10) | 0.0125 (7) | 0.0218 (8) | −0.0005 (6) | 0.0125 (7) | −0.0015 (6) |
| C8 | 0.0218 (10) | 0.0150 (7) | 0.0205 (8) | 0.0005 (6) | 0.0126 (7) | 0.0000 (6) |
| C9 | 0.0215 (10) | 0.0164 (7) | 0.0231 (8) | 0.0004 (6) | 0.0114 (7) | −0.0030 (6) |
| C10 | 0.0217 (10) | 0.0173 (7) | 0.0212 (8) | 0.0010 (6) | 0.0096 (7) | −0.0025 (6) |
| C11 | 0.0177 (10) | 0.0141 (7) | 0.0196 (8) | −0.0034 (6) | 0.0083 (7) | −0.0034 (6) |
| C12 | 0.0290 (11) | 0.0183 (8) | 0.0311 (9) | −0.0010 (7) | 0.0189 (8) | −0.0010 (7) |
| C13 | 0.0284 (12) | 0.0279 (9) | 0.0449 (11) | −0.0024 (8) | 0.0255 (10) | −0.0047 (8) |
| C14 | 0.0235 (12) | 0.0241 (9) | 0.0448 (11) | 0.0035 (7) | 0.0167 (9) | −0.0025 (8) |
| C15 | 0.0268 (12) | 0.0201 (8) | 0.0324 (10) | 0.0024 (7) | 0.0115 (8) | 0.0041 (7) |
| C16 | 0.0316 (12) | 0.0130 (7) | 0.0191 (8) | 0.0045 (6) | 0.0122 (8) | 0.0008 (6) |
| C17 | 0.0356 (13) | 0.0203 (8) | 0.0275 (9) | −0.0002 (7) | 0.0127 (9) | −0.0025 (7) |
| C18 | 0.0452 (15) | 0.0226 (9) | 0.0277 (10) | 0.0036 (8) | 0.0032 (9) | −0.0061 (7) |
| C19 | 0.0704 (18) | 0.0258 (10) | 0.0180 (9) | 0.0156 (10) | 0.0121 (10) | −0.0015 (7) |
| C20 | 0.0578 (16) | 0.0339 (10) | 0.0260 (9) | 0.0149 (10) | 0.0246 (10) | 0.0060 (8) |
| C21 | 0.0369 (13) | 0.0244 (9) | 0.0240 (9) | 0.0076 (8) | 0.0162 (9) | 0.0051 (7) |
| C22 | 0.0206 (10) | 0.0155 (7) | 0.0224 (8) | −0.0058 (6) | 0.0115 (7) | −0.0071 (6) |
| C23 | 0.0282 (12) | 0.0238 (8) | 0.0251 (9) | −0.0019 (7) | 0.0152 (8) | −0.0044 (7) |
| C24 | 0.0352 (13) | 0.0381 (10) | 0.0260 (9) | −0.0031 (8) | 0.0184 (9) | −0.0091 (8) |
| C25 | 0.0293 (12) | 0.0304 (9) | 0.0374 (10) | −0.0038 (8) | 0.0187 (9) | −0.0169 (8) |
| C26 | 0.0275 (12) | 0.0219 (8) | 0.0378 (10) | 0.0016 (7) | 0.0144 (9) | −0.0079 (7) |
| C27 | 0.0174 (10) | 0.0189 (7) | 0.0198 (8) | 0.0005 (6) | 0.0083 (7) | 0.0017 (6) |
| C28 | 0.0209 (11) | 0.0198 (8) | 0.0248 (9) | 0.0022 (7) | 0.0084 (8) | −0.0008 (6) |
| C29 | 0.0249 (11) | 0.0150 (8) | 0.0378 (10) | 0.0012 (7) | 0.0081 (9) | 0.0057 (7) |
| C30 | 0.0258 (12) | 0.0293 (9) | 0.0354 (10) | 0.0011 (7) | 0.0161 (9) | 0.0136 (8) |
| C31 | 0.0308 (12) | 0.0337 (10) | 0.0288 (9) | 0.0061 (8) | 0.0192 (9) | 0.0060 (8) |
| C32 | 0.0285 (11) | 0.0178 (8) | 0.0249 (9) | 0.0033 (7) | 0.0146 (8) | 0.0020 (6) |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Geometric parameters (Å, º)
| O1—C1 | 1.2123 (18) | C15—H15 | 0.9500 |
| O2—C6 | 1.2148 (19) | C16—C17 | 1.386 (3) |
| N1—C11 | 1.3387 (19) | C16—C21 | 1.397 (2) |
| N1—C15 | 1.333 (2) | C17—H17 | 0.9500 |
| N2—C22 | 1.341 (2) | C17—C18 | 1.387 (2) |
| N2—C26 | 1.334 (2) | C18—H18 | 0.9500 |
| C1—C2 | 1.509 (2) | C18—C19 | 1.385 (3) |
| C1—C11 | 1.495 (2) | C19—H19 | 0.9500 |
| C2—H2 | 1.0000 | C19—C20 | 1.378 (3) |
| C2—C3 | 1.549 (2) | C20—H20 | 0.9500 |
| C2—C7 | 1.575 (2) | C20—C21 | 1.384 (3) |
| C3—H3 | 1.0000 | C21—H21 | 0.9500 |
| C3—C4 | 1.454 (2) | C22—C23 | 1.384 (2) |
| C3—C8 | 1.566 (2) | C23—H23 | 0.9500 |
| C4—C5 | 1.195 (2) | C23—C24 | 1.385 (2) |
| C5—C16 | 1.441 (2) | C24—H24 | 0.9500 |
| C6—C7 | 1.513 (2) | C24—C25 | 1.370 (3) |
| C6—C22 | 1.498 (2) | C25—H25 | 0.9500 |
| C7—H7 | 1.0000 | C25—C26 | 1.388 (3) |
| C7—C8 | 1.554 (2) | C26—H26 | 0.9500 |
| C8—H8 | 1.0000 | C27—C28 | 1.399 (2) |
| C8—C9 | 1.460 (2) | C27—C32 | 1.395 (2) |
| C9—C10 | 1.194 (2) | C28—H28 | 0.9500 |
| C10—C27 | 1.439 (2) | C28—C29 | 1.380 (2) |
| C11—C12 | 1.386 (2) | C29—H29 | 0.9500 |
| C12—H12 | 0.9500 | C29—C30 | 1.381 (3) |
| C12—C13 | 1.382 (2) | C30—H30 | 0.9500 |
| C13—H13 | 0.9500 | C30—C31 | 1.378 (2) |
| C13—C14 | 1.377 (3) | C31—H31 | 0.9500 |
| C14—H14 | 0.9500 | C31—C32 | 1.387 (2) |
| C14—C15 | 1.384 (2) | C32—H32 | 0.9500 |
| C15—N1—C11 | 116.77 (14) | C17—C16—C5 | 121.14 (15) |
| C26—N2—C22 | 116.48 (15) | C17—C16—C21 | 119.21 (16) |
| O1—C1—C2 | 121.04 (14) | C21—C16—C5 | 119.63 (17) |
| O1—C1—C11 | 120.81 (14) | C16—C17—H17 | 119.9 |
| C11—C1—C2 | 118.03 (13) | C16—C17—C18 | 120.23 (18) |
| C1—C2—H2 | 111.2 | C18—C17—H17 | 119.9 |
| C1—C2—C3 | 117.15 (12) | C17—C18—H18 | 119.9 |
| C1—C2—C7 | 116.08 (12) | C19—C18—C17 | 120.2 (2) |
| C3—C2—H2 | 111.2 | C19—C18—H18 | 119.9 |
| C3—C2—C7 | 88.33 (12) | C18—C19—H19 | 120.0 |
| C7—C2—H2 | 111.2 | C20—C19—C18 | 119.94 (17) |
| C2—C3—H3 | 109.2 | C20—C19—H19 | 120.0 |
| C2—C3—C8 | 89.43 (11) | C19—C20—H20 | 119.9 |
| C4—C3—C2 | 117.61 (14) | C19—C20—C21 | 120.24 (19) |
| C4—C3—H3 | 109.2 | C21—C20—H20 | 119.9 |
| C4—C3—C8 | 120.76 (13) | C16—C21—H21 | 119.9 |
| C8—C3—H3 | 109.2 | C20—C21—C16 | 120.2 (2) |
| C5—C4—C3 | 177.49 (18) | C20—C21—H21 | 119.9 |
| C4—C5—C16 | 179.10 (19) | N2—C22—C6 | 116.52 (14) |
| O2—C6—C7 | 122.18 (14) | N2—C22—C23 | 123.73 (14) |
| O2—C6—C22 | 120.37 (14) | C23—C22—C6 | 119.75 (15) |
| C22—C6—C7 | 117.44 (13) | C22—C23—H23 | 120.7 |
| C2—C7—H7 | 112.8 | C22—C23—C24 | 118.50 (16) |
| C6—C7—C2 | 114.14 (13) | C24—C23—H23 | 120.7 |
| C6—C7—H7 | 112.8 | C23—C24—H24 | 120.7 |
| C6—C7—C8 | 113.24 (13) | C25—C24—C23 | 118.70 (16) |
| C8—C7—C2 | 88.89 (11) | C25—C24—H24 | 120.7 |
| C8—C7—H7 | 112.8 | C24—C25—H25 | 120.6 |
| C3—C8—H8 | 112.1 | C24—C25—C26 | 118.82 (16) |
| C7—C8—C3 | 88.48 (12) | C26—C25—H25 | 120.6 |
| C7—C8—H8 | 112.1 | N2—C26—C25 | 123.76 (17) |
| C9—C8—C3 | 117.03 (13) | N2—C26—H26 | 118.1 |
| C9—C8—C7 | 113.14 (12) | C25—C26—H26 | 118.1 |
| C9—C8—H8 | 112.1 | C28—C27—C10 | 119.56 (14) |
| C10—C9—C8 | 175.96 (18) | C32—C27—C10 | 121.30 (14) |
| C9—C10—C27 | 176.81 (17) | C32—C27—C28 | 119.14 (15) |
| N1—C11—C1 | 117.01 (14) | C27—C28—H28 | 119.9 |
| N1—C11—C12 | 123.50 (15) | C29—C28—C27 | 120.17 (16) |
| C12—C11—C1 | 119.46 (14) | C29—C28—H28 | 119.9 |
| C11—C12—H12 | 120.8 | C28—C29—H29 | 119.8 |
| C13—C12—C11 | 118.50 (15) | C28—C29—C30 | 120.35 (15) |
| C13—C12—H12 | 120.8 | C30—C29—H29 | 119.8 |
| C12—C13—H13 | 120.6 | C29—C30—H30 | 120.0 |
| C14—C13—C12 | 118.78 (16) | C31—C30—C29 | 119.96 (16) |
| C14—C13—H13 | 120.6 | C31—C30—H30 | 120.0 |
| C13—C14—H14 | 120.7 | C30—C31—H31 | 119.8 |
| C13—C14—C15 | 118.58 (16) | C30—C31—C32 | 120.49 (16) |
| C15—C14—H14 | 120.7 | C32—C31—H31 | 119.8 |
| N1—C15—C14 | 123.84 (16) | C27—C32—H32 | 120.1 |
| N1—C15—H15 | 118.1 | C31—C32—C27 | 119.87 (15) |
| C14—C15—H15 | 118.1 | C31—C32—H32 | 120.1 |
[3,4-Bis(phenylethynyl)cyclobutane-1,2-diyl]bis(pyridin-2-ylmethanone) (3). Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···N1 | 1.00 | 2.45 | 2.835 (3) | 102 |
| C3—H3···O1 | 1.00 | 2.49 | 2.899 (2) | 104 |
| C8—H8···O2 | 1.00 | 2.39 | 2.804 (2) | 104 |
| C25—H25···N1i | 0.95 | 2.60 | 3.445 (3) | 148 |
| C19—H19···N1ii | 0.95 | 2.73 | 3.665 (2) | 167 |
| C20—H20···O1iii | 0.95 | 2.62 | 3.263 (2) | 125 |
| C32—H32···O2iv | 0.95 | 2.55 | 3.487 (2) | 168 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x, −y+1, −z; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1.
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Crystal data
| C17H13NO | Dx = 1.270 Mg m−3 |
| Mr = 247.28 | Melting point: 373 K |
| Monoclinic, P21/c | Synchrotron radiation, λ = 0.80248 Å |
| a = 14.859 (3) Å | Cell parameters from 148 reflections |
| b = 17.747 (4) Å | θ = 3.5–25.6° |
| c = 9.995 (2) Å | µ = 0.10 mm−1 |
| β = 101.06 (3)° | T = 100 K |
| V = 2586.7 (9) Å3 | Plate, yellow |
| Z = 8 | 0.02 × 0.02 × 0.01 mm |
| F(000) = 1040 |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Data collection
| Mar CCD diffractometer | 4453 reflections with I > 2σ(I) |
| phi scans | Rint = 0.077 |
| Absorption correction: multi-scan (SCALA; Evans, 2006) | θmax = 30.9°, θmin = 3.3° |
| Tmin = 0.997, Tmax = 0.999 | h = −18→18 |
| 23024 measured reflections | k = −22→22 |
| 5645 independent reflections | l = −12→12 |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.060 | w = 1/[σ2(Fo2) + (0.057P)2 + 1.189P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.157 | (Δ/σ)max < 0.001 |
| S = 1.02 | Δρmax = 0.23 e Å−3 |
| 5645 reflections | Δρmin = −0.21 e Å−3 |
| 346 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.051 (4) |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Special details
| 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. |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.08252 (11) | 0.41331 (9) | 0.08638 (13) | 0.0493 (4) | |
| N1 | 0.19600 (11) | 0.39239 (9) | 0.42804 (15) | 0.0383 (4) | |
| C1 | 0.11482 (13) | 0.43098 (12) | 0.20438 (18) | 0.0379 (4) | |
| C2 | 0.12405 (13) | 0.51037 (11) | 0.24820 (19) | 0.0380 (4) | |
| H2 | 0.1567 | 0.5228 | 0.3367 | 0.046* | |
| C3 | 0.08643 (14) | 0.56483 (12) | 0.1634 (2) | 0.0409 (5) | |
| H3 | 0.0526 | 0.5493 | 0.0773 | 0.049* | |
| C4 | 0.09180 (14) | 0.64305 (12) | 0.1887 (2) | 0.0420 (5) | |
| C5 | 0.09537 (14) | 0.71075 (12) | 0.1993 (2) | 0.0413 (5) | |
| C6 | 0.10213 (14) | 0.79075 (12) | 0.20949 (19) | 0.0394 (4) | |
| C7 | 0.07036 (14) | 0.83675 (12) | 0.0969 (2) | 0.0418 (5) | |
| H7 | 0.0431 | 0.8147 | 0.0122 | 0.050* | |
| C8 | 0.07839 (14) | 0.91450 (12) | 0.1084 (2) | 0.0414 (5) | |
| H8 | 0.0561 | 0.9450 | 0.0311 | 0.050* | |
| C9 | 0.11833 (14) | 0.94863 (12) | 0.2305 (2) | 0.0412 (5) | |
| C10 | 0.14997 (15) | 0.90211 (13) | 0.3424 (2) | 0.0467 (5) | |
| H10 | 0.1776 | 0.9242 | 0.4269 | 0.056* | |
| C11 | 0.14194 (15) | 0.82508 (13) | 0.3329 (2) | 0.0458 (5) | |
| H11 | 0.1636 | 0.7948 | 0.4108 | 0.055* | |
| C12 | 0.12884 (16) | 1.03274 (12) | 0.2434 (2) | 0.0494 (5) | |
| H12A | 0.1932 | 1.0464 | 0.2476 | 0.074* | |
| H12B | 0.1094 | 1.0496 | 0.3268 | 0.074* | |
| H12C | 0.0908 | 1.0571 | 0.1643 | 0.074* | |
| C13 | 0.14687 (13) | 0.37043 (11) | 0.30695 (18) | 0.0353 (4) | |
| C14 | 0.12604 (14) | 0.29623 (12) | 0.2729 (2) | 0.0408 (5) | |
| H14 | 0.0903 | 0.2835 | 0.1865 | 0.049* | |
| C15 | 0.15839 (15) | 0.24046 (12) | 0.3676 (2) | 0.0449 (5) | |
| H15 | 0.1445 | 0.1889 | 0.3479 | 0.054* | |
| C16 | 0.21129 (15) | 0.26184 (12) | 0.4913 (2) | 0.0431 (5) | |
| H16 | 0.2359 | 0.2251 | 0.5575 | 0.052* | |
| C17 | 0.22753 (15) | 0.33754 (12) | 0.51642 (19) | 0.0426 (5) | |
| H17 | 0.2634 | 0.3516 | 0.6020 | 0.051* | |
| O2 | 0.45764 (10) | 0.31523 (8) | 0.50791 (12) | 0.0395 (3) | |
| N2 | 0.35093 (11) | 0.37903 (9) | 0.18087 (14) | 0.0342 (4) | |
| C18 | 0.42385 (13) | 0.31321 (11) | 0.38578 (17) | 0.0327 (4) | |
| C19 | 0.41012 (13) | 0.24154 (10) | 0.30956 (17) | 0.0331 (4) | |
| H19 | 0.3996 | 0.2414 | 0.2128 | 0.040* | |
| C20 | 0.41275 (13) | 0.17693 (10) | 0.37887 (18) | 0.0342 (4) | |
| H20 | 0.4235 | 0.1806 | 0.4755 | 0.041* | |
| C21 | 0.40113 (13) | 0.10337 (10) | 0.32236 (17) | 0.0339 (4) | |
| C22 | 0.39020 (13) | 0.03862 (11) | 0.28721 (17) | 0.0343 (4) | |
| C23 | 0.37756 (13) | −0.03916 (10) | 0.25127 (17) | 0.0328 (4) | |
| C24 | 0.41627 (13) | −0.09465 (10) | 0.34423 (17) | 0.0343 (4) | |
| H24 | 0.4510 | −0.0804 | 0.4304 | 0.041* | |
| C25 | 0.40418 (13) | −0.17024 (11) | 0.31134 (18) | 0.0362 (4) | |
| H25 | 0.4313 | −0.2073 | 0.3751 | 0.043* | |
| C26 | 0.35279 (13) | −0.19286 (11) | 0.18589 (18) | 0.0354 (4) | |
| C27 | 0.31461 (13) | −0.13723 (11) | 0.09343 (18) | 0.0369 (4) | |
| H27 | 0.2800 | −0.1516 | 0.0072 | 0.044* | |
| C28 | 0.32623 (13) | −0.06173 (11) | 0.12495 (17) | 0.0354 (4) | |
| H28 | 0.2993 | −0.0248 | 0.0607 | 0.042* | |
| C29 | 0.33893 (15) | −0.27549 (11) | 0.1537 (2) | 0.0435 (5) | |
| H29A | 0.3925 | −0.3039 | 0.2002 | 0.065* | |
| H29B | 0.3313 | −0.2831 | 0.0551 | 0.065* | |
| H29C | 0.2840 | −0.2933 | 0.1849 | 0.065* | |
| C30 | 0.39586 (12) | 0.38512 (10) | 0.31068 (16) | 0.0312 (4) | |
| C31 | 0.41532 (13) | 0.45334 (11) | 0.37716 (18) | 0.0355 (4) | |
| H31 | 0.4450 | 0.4547 | 0.4702 | 0.043* | |
| C32 | 0.39093 (14) | 0.51947 (11) | 0.30610 (19) | 0.0386 (4) | |
| H32 | 0.4052 | 0.5671 | 0.3482 | 0.046* | |
| C33 | 0.34521 (14) | 0.51431 (11) | 0.17197 (19) | 0.0380 (4) | |
| H33 | 0.3273 | 0.5585 | 0.1200 | 0.046* | |
| C34 | 0.32614 (13) | 0.44366 (11) | 0.11495 (18) | 0.0368 (4) | |
| H34 | 0.2935 | 0.4409 | 0.0235 | 0.044* |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0589 (9) | 0.0542 (9) | 0.0279 (7) | 0.0043 (7) | −0.0087 (6) | −0.0013 (6) |
| N1 | 0.0397 (9) | 0.0449 (9) | 0.0267 (8) | 0.0005 (7) | −0.0026 (6) | −0.0014 (6) |
| C1 | 0.0361 (10) | 0.0482 (11) | 0.0266 (9) | 0.0012 (8) | −0.0009 (7) | −0.0001 (7) |
| C2 | 0.0393 (10) | 0.0440 (11) | 0.0280 (9) | 0.0010 (8) | −0.0005 (7) | 0.0017 (7) |
| C3 | 0.0403 (11) | 0.0461 (11) | 0.0337 (10) | −0.0007 (9) | 0.0005 (8) | 0.0029 (8) |
| C4 | 0.0401 (11) | 0.0479 (12) | 0.0352 (10) | 0.0009 (9) | 0.0000 (8) | 0.0059 (8) |
| C5 | 0.0391 (10) | 0.0472 (12) | 0.0352 (10) | 0.0002 (9) | 0.0012 (8) | 0.0050 (8) |
| C6 | 0.0374 (10) | 0.0442 (11) | 0.0354 (10) | −0.0003 (8) | 0.0037 (8) | 0.0025 (8) |
| C7 | 0.0420 (11) | 0.0485 (12) | 0.0317 (9) | −0.0002 (9) | −0.0015 (8) | 0.0006 (8) |
| C8 | 0.0400 (11) | 0.0465 (11) | 0.0350 (10) | 0.0017 (9) | 0.0010 (8) | 0.0052 (8) |
| C9 | 0.0354 (10) | 0.0480 (12) | 0.0396 (10) | −0.0015 (9) | 0.0060 (8) | −0.0007 (8) |
| C10 | 0.0486 (12) | 0.0568 (13) | 0.0318 (10) | −0.0047 (10) | 0.0003 (8) | −0.0014 (9) |
| C11 | 0.0475 (12) | 0.0549 (13) | 0.0319 (10) | −0.0025 (10) | −0.0007 (8) | 0.0056 (9) |
| C12 | 0.0462 (12) | 0.0478 (12) | 0.0528 (13) | −0.0038 (10) | 0.0064 (10) | −0.0031 (10) |
| C13 | 0.0343 (9) | 0.0441 (10) | 0.0260 (9) | −0.0002 (8) | 0.0015 (7) | −0.0005 (7) |
| C14 | 0.0398 (11) | 0.0451 (11) | 0.0349 (10) | 0.0007 (9) | 0.0005 (8) | −0.0049 (8) |
| C15 | 0.0483 (12) | 0.0402 (11) | 0.0445 (11) | 0.0016 (9) | 0.0048 (9) | −0.0016 (8) |
| C16 | 0.0470 (12) | 0.0460 (11) | 0.0352 (10) | 0.0058 (9) | 0.0049 (8) | 0.0051 (8) |
| C17 | 0.0474 (11) | 0.0478 (11) | 0.0284 (9) | 0.0054 (9) | −0.0029 (8) | 0.0010 (8) |
| O2 | 0.0535 (8) | 0.0405 (7) | 0.0211 (6) | −0.0012 (6) | −0.0019 (5) | −0.0009 (5) |
| N2 | 0.0402 (9) | 0.0382 (8) | 0.0221 (7) | −0.0011 (7) | 0.0007 (6) | −0.0018 (6) |
| C18 | 0.0361 (9) | 0.0384 (10) | 0.0226 (8) | −0.0007 (8) | 0.0028 (7) | −0.0010 (7) |
| C19 | 0.0392 (10) | 0.0357 (10) | 0.0222 (8) | −0.0007 (8) | 0.0008 (7) | −0.0007 (7) |
| C20 | 0.0379 (10) | 0.0372 (10) | 0.0253 (8) | −0.0006 (8) | 0.0001 (7) | −0.0003 (7) |
| C21 | 0.0374 (10) | 0.0366 (10) | 0.0249 (8) | 0.0011 (8) | −0.0013 (7) | 0.0039 (7) |
| C22 | 0.0354 (9) | 0.0396 (10) | 0.0256 (8) | 0.0016 (8) | 0.0004 (7) | 0.0037 (7) |
| C23 | 0.0361 (9) | 0.0350 (9) | 0.0260 (8) | 0.0002 (8) | 0.0026 (7) | −0.0001 (7) |
| C24 | 0.0367 (10) | 0.0383 (10) | 0.0251 (8) | 0.0004 (8) | −0.0009 (7) | 0.0008 (7) |
| C25 | 0.0392 (10) | 0.0366 (10) | 0.0306 (9) | 0.0029 (8) | 0.0009 (7) | 0.0029 (7) |
| C26 | 0.0359 (10) | 0.0377 (10) | 0.0322 (9) | −0.0022 (8) | 0.0051 (7) | −0.0033 (7) |
| C27 | 0.0395 (10) | 0.0432 (11) | 0.0258 (8) | −0.0019 (8) | 0.0011 (7) | −0.0045 (7) |
| C28 | 0.0391 (10) | 0.0397 (10) | 0.0246 (8) | 0.0006 (8) | −0.0008 (7) | 0.0023 (7) |
| C29 | 0.0457 (11) | 0.0401 (11) | 0.0435 (11) | −0.0023 (9) | 0.0056 (9) | −0.0064 (8) |
| C30 | 0.0348 (9) | 0.0359 (10) | 0.0215 (8) | −0.0012 (7) | 0.0018 (7) | −0.0014 (6) |
| C31 | 0.0407 (10) | 0.0375 (10) | 0.0256 (8) | −0.0021 (8) | 0.0000 (7) | −0.0031 (7) |
| C32 | 0.0458 (11) | 0.0354 (10) | 0.0327 (9) | −0.0022 (8) | 0.0024 (8) | −0.0047 (7) |
| C33 | 0.0438 (11) | 0.0376 (10) | 0.0309 (9) | 0.0010 (8) | 0.0031 (8) | 0.0049 (7) |
| C34 | 0.0436 (11) | 0.0404 (10) | 0.0239 (8) | 0.0029 (8) | −0.0001 (7) | 0.0003 (7) |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Geometric parameters (Å, º)
| O1—C1 | 1.226 (2) | O2—C18 | 1.228 (2) |
| N1—C13 | 1.346 (2) | N2—C30 | 1.345 (2) |
| N1—C17 | 1.337 (2) | N2—C34 | 1.339 (2) |
| C1—C2 | 1.474 (3) | C18—C19 | 1.476 (2) |
| C1—C13 | 1.498 (3) | C18—C30 | 1.498 (2) |
| C2—H2 | 0.9500 | C19—H19 | 0.9500 |
| C2—C3 | 1.335 (3) | C19—C20 | 1.336 (3) |
| C3—H3 | 0.9500 | C20—H20 | 0.9500 |
| C3—C4 | 1.411 (3) | C20—C21 | 1.420 (3) |
| C4—C5 | 1.206 (3) | C21—C22 | 1.203 (3) |
| C5—C6 | 1.426 (3) | C22—C23 | 1.430 (3) |
| C6—C7 | 1.397 (3) | C23—C24 | 1.400 (2) |
| C6—C11 | 1.401 (3) | C23—C28 | 1.402 (2) |
| C7—H7 | 0.9500 | C24—H24 | 0.9500 |
| C7—C8 | 1.388 (3) | C24—C25 | 1.385 (3) |
| C8—H8 | 0.9500 | C25—H25 | 0.9500 |
| C8—C9 | 1.390 (3) | C25—C26 | 1.396 (3) |
| C9—C10 | 1.397 (3) | C26—C27 | 1.396 (3) |
| C9—C12 | 1.504 (3) | C26—C29 | 1.507 (3) |
| C10—H10 | 0.9500 | C27—H27 | 0.9500 |
| C10—C11 | 1.374 (3) | C27—C28 | 1.380 (3) |
| C11—H11 | 0.9500 | C28—H28 | 0.9500 |
| C12—H12A | 0.9800 | C29—H29A | 0.9800 |
| C12—H12B | 0.9800 | C29—H29B | 0.9800 |
| C12—H12C | 0.9800 | C29—H29C | 0.9800 |
| C13—C14 | 1.380 (3) | C30—C31 | 1.385 (2) |
| C14—H14 | 0.9500 | C31—H31 | 0.9500 |
| C14—C15 | 1.390 (3) | C31—C32 | 1.384 (3) |
| C15—H15 | 0.9500 | C32—H32 | 0.9500 |
| C15—C16 | 1.385 (3) | C32—C33 | 1.385 (3) |
| C16—H16 | 0.9500 | C33—H33 | 0.9500 |
| C16—C17 | 1.379 (3) | C33—C34 | 1.384 (3) |
| C17—H17 | 0.9500 | C34—H34 | 0.9500 |
| C17—N1—C13 | 116.36 (17) | C34—N2—C30 | 116.40 (16) |
| O1—C1—C2 | 121.82 (18) | O2—C18—C19 | 121.85 (16) |
| O1—C1—C13 | 119.30 (19) | O2—C18—C30 | 119.62 (16) |
| C2—C1—C13 | 118.88 (15) | C19—C18—C30 | 118.53 (14) |
| C1—C2—H2 | 120.0 | C18—C19—H19 | 120.5 |
| C3—C2—C1 | 119.97 (17) | C20—C19—C18 | 118.97 (16) |
| C3—C2—H2 | 120.0 | C20—C19—H19 | 120.5 |
| C2—C3—H3 | 116.7 | C19—C20—H20 | 116.8 |
| C2—C3—C4 | 126.59 (19) | C19—C20—C21 | 126.41 (17) |
| C4—C3—H3 | 116.7 | C21—C20—H20 | 116.8 |
| C5—C4—C3 | 174.8 (2) | C22—C21—C20 | 173.42 (19) |
| C4—C5—C6 | 178.1 (2) | C21—C22—C23 | 177.61 (18) |
| C7—C6—C5 | 121.09 (18) | C24—C23—C22 | 119.68 (16) |
| C7—C6—C11 | 118.38 (19) | C24—C23—C28 | 118.69 (17) |
| C11—C6—C5 | 120.53 (18) | C28—C23—C22 | 121.63 (16) |
| C6—C7—H7 | 119.9 | C23—C24—H24 | 119.8 |
| C8—C7—C6 | 120.28 (18) | C25—C24—C23 | 120.40 (16) |
| C8—C7—H7 | 119.9 | C25—C24—H24 | 119.8 |
| C7—C8—H8 | 119.3 | C24—C25—H25 | 119.5 |
| C7—C8—C9 | 121.42 (18) | C24—C25—C26 | 121.03 (17) |
| C9—C8—H8 | 119.3 | C26—C25—H25 | 119.5 |
| C8—C9—C10 | 117.8 (2) | C25—C26—C27 | 118.29 (17) |
| C8—C9—C12 | 121.87 (19) | C25—C26—C29 | 120.02 (17) |
| C10—C9—C12 | 120.29 (19) | C27—C26—C29 | 121.68 (17) |
| C9—C10—H10 | 119.3 | C26—C27—H27 | 119.4 |
| C11—C10—C9 | 121.41 (19) | C28—C27—C26 | 121.22 (17) |
| C11—C10—H10 | 119.3 | C28—C27—H27 | 119.4 |
| C6—C11—H11 | 119.7 | C23—C28—H28 | 119.8 |
| C10—C11—C6 | 120.67 (19) | C27—C28—C23 | 120.36 (17) |
| C10—C11—H11 | 119.7 | C27—C28—H28 | 119.8 |
| C9—C12—H12A | 109.5 | C26—C29—H29A | 109.5 |
| C9—C12—H12B | 109.5 | C26—C29—H29B | 109.5 |
| C9—C12—H12C | 109.5 | C26—C29—H29C | 109.5 |
| H12A—C12—H12B | 109.5 | H29A—C29—H29B | 109.5 |
| H12A—C12—H12C | 109.5 | H29A—C29—H29C | 109.5 |
| H12B—C12—H12C | 109.5 | H29B—C29—H29C | 109.5 |
| N1—C13—C1 | 117.00 (17) | N2—C30—C18 | 116.97 (15) |
| N1—C13—C14 | 123.73 (18) | N2—C30—C31 | 123.55 (16) |
| C14—C13—C1 | 119.26 (16) | C31—C30—C18 | 119.47 (15) |
| C13—C14—H14 | 120.7 | C30—C31—H31 | 120.5 |
| C13—C14—C15 | 118.67 (18) | C32—C31—C30 | 119.03 (17) |
| C15—C14—H14 | 120.7 | C32—C31—H31 | 120.5 |
| C14—C15—H15 | 120.8 | C31—C32—H32 | 120.9 |
| C16—C15—C14 | 118.4 (2) | C31—C32—C33 | 118.19 (17) |
| C16—C15—H15 | 120.8 | C33—C32—H32 | 120.9 |
| C15—C16—H16 | 120.7 | C32—C33—H33 | 120.6 |
| C17—C16—C15 | 118.59 (19) | C34—C33—C32 | 118.83 (17) |
| C17—C16—H16 | 120.7 | C34—C33—H33 | 120.6 |
| N1—C17—C16 | 124.19 (18) | N2—C34—C33 | 123.94 (16) |
| N1—C17—H17 | 117.9 | N2—C34—H34 | 118.0 |
| C16—C17—H17 | 117.9 | C33—C34—H34 | 118.0 |
(E)-5-(4-Methylphenyl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one (2) . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2···N1 | 0.95 | 2.52 | 2.832 (3) | 100 |
| C16—H16···N2i | 0.95 | 2.66 | 3.555 (3) | 158 |
| C20—H20···N2i | 0.95 | 2.71 | 3.465 (3) | 136 |
| C3—H3···O1ii | 0.95 | 2.43 | 3.206 (3) | 139 |
| C19—H19···O2iii | 0.95 | 2.57 | 3.379 (2) | 143 |
| C25—H25···O2iv | 0.95 | 2.65 | 3.561 (2) | 161 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y+1, −z; (iii) x, −y+1/2, z−1/2; (iv) −x+1, −y, −z+1.
Funding Statement
This work was funded by Russian Science Foundation grant 17-13-01442 to Anna V. Vologzhanina.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, 2, 3. DOI: 10.1107/S2056989020000055/ff2164sup1.cif
Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989020000055/ff21643sup2.hkl
Supporting information file. DOI: 10.1107/S2056989020000055/ff21643sup4.cml
Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989020000055/ff21642sup3.hkl
Supporting information file. DOI: 10.1107/S2056989020000055/ff21642sup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report