1. Chemical context
Chalcones, 1.3-disubstituted-prop-2-en-1-ones of type R1COCH=CHR2, exhibit a wide range of biological activities, particularly when they incorporate functionalized substituents; these include anticancer (Murthy et al., 2013
), antimalarial (Mishra et al., 2008
; Yadav et al., 2012
), antitripanosomal (Carvalho et al., 2012
) and antiviral (Sharma et al., 2011
) activities. With these properties in mind, we have developed a versatile and efficient route to functionalized chalcones, which are themselves the basis for further elaboration to provide a wide range of multiply substituted chalcones. Here we report the synthesis and characterization of five 3-(5-aryloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-(4-(prop-2-yn-1- yloxy)phenyl)prop-2-en-1-ones (I) and a corresponding series of five 1-(4-azidophenyl)-3-(3-methyl-1-phenyl-5-(aryloxy)-1H-pyrazol-4-yl)-prop-2-en-1-ones (II), together with the structures of a representative selection of three examples of each type, namely (Ib)
, (Ic)
and (Ie)
and (IIa)
, (IId)
and (IIe)
(Figs. 1
–6![[link]](../../../../../../logos/arrows/e_arr.gif)
![[link]](../../../../../../logos/arrows/e_arr.gif)
![[link]](../../../../../../logos/arrows/e_arr.gif)
![[link]](../../../../../../logos/arrows/e_arr.gif)
). The compounds of types (I) and (II) were prepared using a common synthetic scheme starting from the commercially available 3-methyl-1-phenyl-1H-pyrazole, which was readily converted, under Vilsmaeier–Haack conditions, to the key precursor 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (A) (Fig. 7
), which was then converted to a series of 5-aryloxy derivatives (B), by reaction with substituted phenols under basic conditions as previously described (Kiran Kumar et al., 2019
). The 5-aryloxy compounds (B) were then condensed with 1-[4-(prop-2-yn-1-yloxy)phenyl]ethan-1-one to give the products (Ia)–(Ie) (Fig. 7
) or with 1-(4-azidophenyl)ethan-1-one to give the corresponding series of products (IIa)–(IIe). Thus the synthesis of these two matched series of products (I) and (II) from common precursors, is highly efficient. The presence of the alkyne unit in the type (I) products and of the azido unit in the type (II) products means that a small library is now available for use in Huisgen-type cycloaddition reactions to form bis(chalcone)-substituted 1,2,3-triazoles. Such highly functionalized triazoles are an attractive synthetic target as 1,2,3-triazoles, which exhibit a very wide range of biological activity of potential medicinal values (Kharb et al., 2011
; Dheer et al., 2017
).
| Figure 1 The molecular structure of compound (Ib) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| Figure 2 The molecular structure of compound (Ic) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| Figure 3 The molecular structure of compound (Ie) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| Figure 4 The molecular structure of compound (IIa) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| Figure 5 The molecular structure of compound (IId) showing the atom-labelling scheme, and the disorder in the 2,4-dichlorophenyl group. The major disorder component is drawn using full lines and the minor disorder component is drawn using broken lines. Displacement ellipsoids are drawn at the 30% probability level. |
| Figure 6 The molecular structure of compound (IIe) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. |
| Figure 7 Part of the crystal structure of compound (Ib) showing the formation of a chain of centrosymmetric rings parallel to [010]. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the H atoms not involved in the motifs shown have been omitted. |
2. Structural commentary
Compounds (Ib)
and (Ic)
are geometrical isomers (Figs. 1
and 2
), although they are not isomorphous (Table 3
). Although the constitutions of compounds (Ie)
and (IIe)
differ only in the identity of the small substituent at atom C14 (Figs. 3
and 6
), these compounds crystallize in different space groups (Table 3
).
| (Ib) | (Ic) | (Ie) | Crystal data | Chemical formula | C28H21ClN2O3 | C28H21ClN2O3 | C32H24N2O3 | Mr | 468.92 | 468.92 | 484.53 | Crystal system, space group | Triclinic, P![[\overline{1}]](teximages/mw2158fi3.gif) | Triclinic, P![[\overline{1}]](teximages/mw2158fi3.gif) | Triclinic, P![[\overline{1}]](teximages/mw2158fi3.gif) | Temperature (K) | 297 | 297 | 297 | a, b, c (Å) | 9.909 (7), 10.193 (6), 12.024 (8) | 8.9959 (14), 9.7380 (15), 13.637 (2) | 8.8615 (6), 10.4973 (7), 13.6588 (10) | α, β, γ (°) | 90.94 (2), 106.27 (2), 92.75 (2) | 95.901 (4), 94.122 (4), 95.959 (4) | 79.006 (3), 89.412 (3), 80.971 (3) | V (Å3) | 1163.9 (13) | 1177.8 (3) | 1231.54 (15) | Z | 2 | 2 | 2 | Radiation type | Mo Kα | Mo Kα | Mo Kα | μ (mm−1) | 0.20 | 0.20 | 0.08 | Crystal size (mm) | 0.18 × 0.15 × 0.10 | 0.20 × 0.15 × 0.15 | 0.20 × 0.16 × 0.16 | | Data collection | Diffractometer | Bruker APEXII | Bruker APEXII | Bruker APEXII | Absorption correction | Multi-scan (SADABS; Bruker, 2016 ) | Multi-scan (SADABS; Bruker, 2016 ) | Multi-scan (SADABS; Bruker, 2016 ) | Tmin, Tmax | 0.833, 0.980 | 0.901, 0.971 | 0.898, 0.987 | No. of measured, independent and observed [I > 2σ(I)] reflections | 43789, 5884, 4402 | 49011, 4837, 3930 | 30613, 4373, 3474 | Rint | 0.061 | 0.061 | 0.055 | (sin θ/λ)max (Å−1) | 0.672 | 0.629 | 0.598 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.155, 1.10 | 0.048, 0.125, 1.15 | 0.070, 0.187, 1.07 | No. of reflections | 5884 | 4837 | 4373 | No. of parameters | 309 | 309 | 336 | No. of restraints | 0 | 0 | 0 | H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | Δρmax, Δρmin (e Å−3) | 0.43, −0.41 | 0.35, −0.45 | 0.85, −0.29 | | | (IIa) | (IId) | (IIe) | Crystal data | Chemical formula | C26H21N5O2 | C25H17Cl2N5O2 | C29H21N5O2 | Mr | 435.48 | 490.33 | 471.51 | Crystal system, space group | Triclinic, P![[\overline{1}]](teximages/mw2158fi3.gif) | Monoclinic, C2/c | Monoclinic, P21/n | Temperature (K) | 297 | 297 | 297 | a, b, c (Å) | 9.8432 (6), 11.7441 (7), 12.3005 (7) | 28.1916 (17), 8.0537 (5), 22.0446 (12) | 9.8460 (8), 22.4303 (18), 11.0490 (9) | α, β, γ (°) | 114.120 (2), 111.139 (2), 96.537 (2) | 90, 109.070 (1), 90 | 90, 104.157 (2), 90 | V (Å3) | 1152.06 (12) | 4730.5 (5) | 2366.0 (3) | Z | 2 | 8 | 4 | Radiation type | Mo Kα | Mo Kα | Mo Kα | μ (mm−1) | 0.08 | 0.31 | 0.09 | Crystal size (mm) | 0.20 × 0.20 × 0.18 | 0.18 × 0.15 × 0.15 | 0.22 × 0.21 × 0.16 | | Data collection | Diffractometer | Bruker APEXII | Bruker APEXII | Bruker APEXII | Absorption correction | Multi-scan (SADABS; Bruker, 2016 ) | Multi-scan (SADABS; Bruker, 2016 ) | Multi-scan (SADABS; Bruker, 2016 ) | Tmin, Tmax | 0.868, 0.985 | 0.881, 0.955 | 0.930, 0.986 | No. of measured, independent and observed [I > 2σ(I)] reflections | 17379, 4050, 2957 | 31508, 4174, 3181 | 43217, 4196, 2463 | Rint | 0.048 | 0.049 | 0.092 | (sin θ/λ)max (Å−1) | 0.596 | 0.595 | 0.597 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.148, 1.10 | 0.086, 0.155, 1.36 | 0.063, 0.154, 1.06 | No. of reflections | 4050 | 4174 | 4196 | No. of parameters | 301 | 382 | 327 | No. of restraints | 0 | 291 | 0 | H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | Δρmax, Δρmin (e Å−3) | 0.19, −0.22 | 0.21, −0.23 | 0.23, −0.27 | Computer programs: APEX3, SAINT and XPREP (Bruker, 2016 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and PLATON (Spek, 2020 ). | |
In each of the compounds reported here, the central core of the molecules, comprising the pyrazole ring and the adjacent prop-2-en-1-one unit is very nearly planar. However, the three substituents at atoms C1, N31 and C35 (Figs. 1
–6![[link]](../../../../../../logos/arrows/e_arr.gif)
![[link]](../../../../../../logos/arrows/e_arr.gif)
![[link]](../../../../../../logos/arrows/e_arr.gif)
![[link]](../../../../../../logos/arrows/e_arr.gif)
) are all twisted out of the plane of the molecular core, as indicated by the relevant torsional angles (Table 1
). None of the molecules, therefore, exhibits any internal symmetry, so that all are conformationally chiral: however, the space groups confirm that they have all crystallized as conformational racemates. In each case, the reference molecule was selected to be one having a positive sign for the torsional angle N32—N31—C311—C312 (Table 1
).
Parameter | (Ib) | (Ic) | (Ie) | (IIa) | (IId) | (IIe) | N32—N31—C311—C312 | 151.1 (3) | 137.0 (2) | 139.9 (3) | 135.1 (2) | 149.6 (4) | 140.9 (3) | C2—C1—C11—C12 | 168.8 (2) | −163.4 (2) | −162.8 (3) | 166.8 (2) | −172.7 (4) | −171.4 (3) | C13—C14—O14—C17 | 169.8 (2) | 3.5 (3) | −0.4 (4) | | | | C14—O14—C17—C18 | −68.7 (3) | −177.1 (2) | −174.7 (3) | | | | C13—C14—N14—N15 | | | | −2.7 (3) | −172.6 (5) | −5.0 (6) | C34—C35—O351—C351 | −76.7 (3) | −69.3 (3) | | 70.1 (3) | 78.3 (16) | | C34—C35—O451—C451 | | | | | 65.0 (12) | | C35—O351—C351—C352 | 157.6 (2) | 169.5 (2) | | −159.6 (2) | −164 (2) | | C35—O451—C451—C45 | | | | | −163.6 (18) | | C34—C35—O351—C352 | | | −70.6 (4) | | | −71.1 (5) | C35—O351—C352—C351 | | | 161.8 (2) | | | 150.9 (3) | | |
In compound (IId)
, the 2,4-dichlorophenoxy substituent was found to be disordered over two sets of atomic sites, having occupancies 0.55 (4) and 0.45 (4) (Fig. 5
). The disorder involves slight differences in the torsional angles around the bond C35-O351 (Fig. 5
), thus C34—C35—O351—Cx51 = 78.3 (16)° when x = 3, and 65.0 (12)° when x = 4: on the other hand, the torsional angles around the bonds O351—Cx51 (x = 3 or 4) are the same within experimental uncertainty, thus C35—O351—Cx51—Cx52 = −164 (2)° for x = 3 and −163.6 (18)° when x = 4.
The orientation of the OCH2CCH substituent relative to the adjacent aryl ring is different in compound (Ib)
, as compared with (Ic)
and (Ie)
(Table 1
, Figs. 1
–3![[link]](../../../../../../logos/arrows/e_arr.gif)
) and similarly the orientation of the azido substituent is different in (IId)
, as compared with (IIa)
and (IIe)
. In the case of the type (I) compounds, it is tempting to associate the observed differences with the different patterns of hydrogen bonding (Table 2
, and Section 3, below), where atom O14 acts as an acceptor only in (Ib)
while atom C19 acts as a donor in (Ic)
and (Ie)
but not in (Ib)
. However, in none of the type (II) compounds do any of the N atoms of the azido unit act as a hydrogen-bond acceptor. Hence, in these compounds, at least, the role of this substituent may be mainly that of a space filler, with the conformation adopted being that which most effectively fills any available space between the molecules.
Compound | D—H⋯A | D—A | H⋯A | D⋯A | D—H⋯A | (Ib) | C355—H355⋯O14i | 0.93 | 2.59 | 3.468 (4) | 158 | | C356—H356⋯O1ii | 0.93 | 2.51 | 3.360 (4) | 152 | (Ic) | C19—H19⋯O1iii | 0.93 | 2.25 | 3.161 (3) | 165 | | C16—H16⋯Cg2 | 0.93 | 2.98 | 3.882 (2) | 165 | | C356—H356⋯Cg1iv | 0.93 | 2.88 | 3.685 (2) | 146 | (Ie) | C19—H19⋯O1v | 0.93 | 2.32 | 3.233 (5) | 165 | | C353—H353⋯Cg1vi | 0.93 | 2.86 | 3.708 (3) | 152 | (IIa) | C357—H35B⋯O1vii | 0.96 | 2.51 | 3.396 (4) | 154 | (IId) | C356—H356⋯O1viii | 0.93 | 2.32 | 3.115 (18) | 143 | | C456—H456⋯O1viii | 0.93 | 2.47 | 3.21 (2) | 137 | (IIe) | C353—H353⋯O1ix | 0.93 | 2.47 | 3.288 (4) | 147 | | C12—H12⋯Cg3x | 0.93 | 2.93 | 3.761 (4) | 150 | | C13—H13⋯Cg4x | 0.93 | 2.73 | 3.547 (4) | 148 | Symmmetry codes: (i) 2 − x, −y, 1 − z; (ii) 2 − x, 1 − y, 1 − z; (iii) 1 + x, 1 + y, z; (iv) 1 − x, −y, 2 − z; (v) −1 + x, 1 + y, z; (vi) 1 − x, −y, 1 − z; (vii) 1 − x, 1 − y, 2 − z; (viii) 1 − x, 2 − y, 1 − z; (ix) 1 − x, 1 − y, −z; (x) −1 + x, y, z. | |
3. Supramolecular features
The supramolecular assembly in the structures reported here is dominated by C—H⋯O hydrogen bonds (Table 2
), along with C—H⋯π(arene) hydrogen bonds in compounds (Ic)
, (Ie)
and (IIe)
. However, in none of the compounds containing chlorophenoxy substituents, [(Ib), (Ic) and (IId)] are there any short C—Cl⋯π(arene) contacts (cf. Imai et al., 2008
).
There are two C—H⋯O hydrogen bonds in the structure of compound (Ib)
(Table 2
), and together these link the molecules into a chain of centrosymmetric rings running parallel to the [010] direction, with rings of R22(20) type (Etter, 1990
; Etter et al., 1990
; Bernstein et al., 1995
) centred at (1, n + 0.5, 0.5) alternating with rings of R22(30) type centred at (1, n, 0.5), where n represents an integer in each case (Fig. 7
). In addition to an intramolecular C—H⋯π(arene) hydrogen bond (Table 2
), the structure of compound (Ic)
, isomeric with (Ib)
, contains two hydrogen bonds, one each of C—H⋯O and C—H⋯π(arene) types. The C—H⋯O hydrogen bond links molecules related by translation into a C(11) running parallel to the [110] direction, and inversion-related pairs of such chains are linked by the C—H⋯π(arene) hydrogen bond to form a chain of rings running parallel to [110] (Fig. 8
). Although there are no intramolecular hydrogen bonds in the structure of compound (Ie)
, the intermolecular hydrogen bonds (Table 2
) are similar to those in compound (Ic)
, although the C—H⋯π(arene) interaction involves a different donor atom; again a chain of rings is formed, but this time it runs parallel to the [1
0] direction (Fig. 9
).
| Figure 8 Part of the crystal structure of compound (Ic) showing the formation of a chain of rings parallel to [110]. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the H atoms not involved in the motifs shown have been omitted. |
| Figure 9 Part of the crystal structure of compound (Ie) showing the formation of a chain of rings parallel to [1 0]. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the H atoms not involved in the motifs shown have been omitted. |
The only direction-specific intermolecular contact in compound (IIa)
involves a methyl group. Because such groups CH3—E generally undergo rapid rotation about the C—E bonds, even in the solid state (Riddell & Rogerson, 1996
, 1997
), particularly when, as here, the methyl group is bonded to a unit having local C2v (mm2) symmetry, when the rotational barrier is particularly low (Tannenbaum et al., 1956
; Naylor & Wilson, 1957
). Accordingly, such a contact is not regarded as structurally significant. There is a single C—H⋯O hydrogen bond in the structure of compound (IId)
, with fairly similar dimensions for each of the two disorder components. Hence it is necessary to consider only the major disorder component, where the inversion-related pairs of molecules are linked into cyclic, centrosymmetric R22(20) dimers (Fig. 10
). In the structure of compound (IIe)
, inversion-related pairs of molecules are linked by paired C—H⋯O hydrogen bonds to form cyclic, centrosymmetric R22(20) dimers, which in turn are linked into a chain of rings running parallel to the [100] direction (Fig. 11
) by the combined action of two C—H⋯π(arene) hydrogen bonds, which utilize both rings of the 2-naphthyl substituent as the acceptors.
| Figure 10 Part of the crystal structure of compound (IId) showing the formation of a centrosymmetric dimer. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the unit-cell outline, the minor disorder component and the H atoms not involved in the motifs shown have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 − x, 2 − y, 1 − z). |
| Figure 11 Part of the crystal structure of compound (IIe) showing the formation of a chain of rings parallel to [100]. Hydrogen bonds are drawn as dashed lines and, for the sake of clarity, the H atoms not involved in the motifs shown have been omitted. |
Thus, the supramolecular assembly in the isomeric pair of compounds (Ib)
and (Ic)
is different in terms of the hydrogen bonds involved (Table 2
), although chains of rings, different in each case, are found in all three of the type (I) compounds. Amongst the type (II) compounds, (IIa)
and (IId)
exhibit either no direction-specific intermolecular interactions, as in (IIa)
, or finite, zero-dimensional aggregation, as in (IId)
. In (IIe)
, a chain of rings is again found, but different from those in any of the type (I) series, although the R22(20) motif can be identified in each of (Ib)
, (IId)
and (IIe)
.
4. Database survey
The structures have recently been reported (Vinutha et al., 2014
; Glidewell et al., 2019
; Kiran Kumar et al., 2019
) of a number of carbaldehyde precursors of type (B) (Fig. 12
), including examples in which R = 2-chlorophenyl, 4-chlorophenyl and 2-naphthyl, i.e. the direct precursors for compounds (Ib)
, (Ic), (Ie)
, (IIb), (IIc) and (IIe)
. Structures have also been reported (Cuartas et al., 2017
) for both an amino analogue of (B), namely 5-[benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde and of the chalcone derived from this by condensation with 4-bromobenzaldehyde; for the 5-(N-methylpiperazino) analogue (Sunitha et al., 2016
) and for the 5-piperidino analogue (Kiran Kumar, 2019
). Finally, we note the structures of two isostructural 3-(5-aryloxy-3-methyl-1-phenyl-1H-pyrazole-1-yl)-1-thiophen-2-yl)prop-2-en-1-ones, both of which exhibit disorder in the orientation of the thiophene unit (Shaibah et al., 2020
).
| Figure 12 The synthetic pathway used for the preparation of compounds (Ia)–(Ie) and (IIa)–(IIe). |
5. Synthesis and crystallization
For the preparation of the prop-2-yn-1-yl compounds (I), a solution of potassium hydroxide (0.31g, 5.7 mmol) in ethanol (30 ml) was added to a mixture of the appropriate intermediate of type (B, Fig.7), 5.7 mmol) and 4-(prop-2-yn-1-yloxy)acetophenone (1.0 g, 5.7 mmol) in ethanol (30 ml). The mixtures were then stirred at ambient temperature for 4 h, after which time, TLC indicated that the reactions were complete. The solid products were then collected by filtration, washed with water, dried in air and recrystallized from an ethanol–dimethylformamide (initial composition 3:1, v/v). Compound (Ia). Yield 82%, m.p. 551 K. IR (cm−1) 3228 (alkyne C-H), 2312 (alkyne C-C), 1672 (C=O), 1578 (C=N). MS (m/z) 449 (M+1)+. Compound (Ib)
. Yield 67%, m.p. 438 K. IR (cm−1) 3230 (alkyne C—H), 2352 (alkyne C—C), 1661 (C=O), 1581 (C=N). MS (m/z) 469 (M+1)+. Compound (Ic)
. Yield 77%, m.p. 406–407 K. IR (cm−1) 3234 (alkyne C-H), 2356 (alkyne C—C), 1668 (C=O), 1576 (C=N). MS (m/z) 469 (M+1)+. Compound (Id). Yield 65%, m.p. 485–486 K. IR (cm−1) 3237 (alkyne C—H), 2342 (alkyne C—C), 1676 (C=O), 1559 (C=N). MS (m/z) 469 (M+1)+. Compound (Ie)
. Yield 69%, m.p. 447–449 K. IR (cm−1) 3227 (alkyne C—H), 2360 (alkyne C—C), 1654 (C=O), 1588 (C=N). MS (m/z) 485 (M+1)+. For the preparation of the azido compounds (II), a solution of potassium hydroxide (0.34g, 6.2 mmol) in ethanol (30 ml) was added to a solution of 4-azidoacetophenone (1.0 g, 6.2 mmol) in ethanol (30 ml). The appropriate intermediate (B) (6.2 mmol) was then added and the mixtures were then stirred for 30 min, after which time TLC indicated that the reactions were complete. The solid products were then collected by filtration, washed with water, dried in air and recrystallized from an ethanol–dimethylformamide (initial composition 3:1, v/v). Compound (IIa)
. Yield 96%, m.p. 385–387 K. IR (cm−1) 2359 (azide), 1650 (C=O), 1592 (C=N). MS (m/z) 436 (M+1)+. Compound (IIb). Yield 74%, m.p. 394–396 K. IR (cm−1) 2355 (azide), 1674 (C=O), 1561 (C=N). MS (m/z) 456 (M+1)+. Compound (IIc). Yield 79%, m.p. 425–427 K. IR (cm−1) 2351 (azide), 1671 (C=O), 15612 (C=N). MS (m/z) 456 (M+1)+. Compound (IId)
. Yield 70%, m.p. 505 K. IR (cm−1) 2349 (azide), 1656 (C=O), 1592 (C=N). MS (m/z) 490 (M+1)+. Compound (IIe)
. Yield 74%, m.p. 489–490 K. IR (cm−1) 2354 (azide), 1676 (C=O), 1565 (C=N). MS (m/z) 472 (M+1)+. Crystals of compounds (Ib)
, (Ic)
, (Ie)
, (IIa)
, (IId)
and (IIe)
which were suitable for single-crystal X-ray diffraction were selected directly from the prepared samples: despite repeated efforts, no crystal suitable for single-crystal X-ray diffraction have yet been obtained for compounds (Ia), (Id), (IIb) or (IIc).
6. Refinement
Crystal data, data collection and refinement details are summarized in Table 3
. For a number of the structures, [(Ie), (IIa)
, (IId)
and (IIe)], the diffraction data at values of θ > 25° were uniformly of very indifferent quality, particular in terms of the symmetry-equivalent reflections. This is probably a consequence of the indifferent crystal quality, exemplifying the general difficulty within the series (I) and (II) of growing crystals suitable for single-crystal X-ray diffraction (cf. Section 5, above). These higher-angle reflections were therefore rejected during the data-reduction process: we note also that the intensity statistics indicated that very few of these reflections were likely to be labelled as observed for compounds (Ie)
, (IIa)
, (IId)
and (IIe)
. A number of low-angle reflections for (Ib)
and (Ie)
were also discarded at this stage because of attenuation by the beam stop. Some further low-angle reflections that had been attenuated by the beam stop were omitted from the data sets before the final refinements, thus: for (Ib)
(101), (110), (002), (202) and (
02); for (Ic)
(
10) and (002); for (Ie)
(002), (111) and (012); for (IIa)
(
11); and for (IId)
(
12). In addition, the bad outlier reflections (
04) for (Id) and (130) for (IIe)
were also omitted. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions with C—H distances 0.93 Å (aromatic), 0.96 Å (CH3) or 0.97 Å (CH2), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. The final difference map for compound (Ie)
contained two significant peaks, 0.85 e Å−3 at (0.227, 0.557, 0.598), and 0.81 e Å−3 at (0.380, 0.488, 0.596), respectively 1.27 and 1.14 Å from atom C351: however, attempts to develop a plausible disorder model based upon these two peaks were not fruitful. For the minor disorder compound in compound (IId)
, the bonded distances and the [1,3] non-bonded distances were restrained to be the same as the corresponding distances in the major disorder component, subject to s.u. values of 0.01 and 0.02 Å, respectively. In addition, similarity restraints were applied to the anisotropic displacement parameters of the partial-occupancy atoms in the disorder components. Subject to these conditions, the occupancies for the two disorder components refined to values of 0.55 (4) and 0.45 (4). Examination of the final refined structures using PLATON (Spek, 2020
) showed that the structure of compound (IIa)
contained a void space, of volume 64 Å3, centred at (0.5, 0, 0), but further examination of this structure using the SQUEEZE procedure (Spek, 2015
) showed that the void contained negligible electron density, consistent with the final difference map.
Supporting information
For all structures, data collection: APEX3 (Bruker, 2016). Cell refinement: APEX3/SAINT V8.37A (Bruker, 2016) for (Ib), (Ic), (Ie), (IIa); APEX3/SAINT (Bruker, 2016) for (IId), (IIe). For all structures, data reduction: SAINT/XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2020); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and PLATON (Spek, 2020).
3-[5-(2-Chlorophenoxy)-3-methyl-1-phenyl-1
H-pyrazol-4-yl]-1-[4-(prop-2-yn-1-yloxy)phenyl]prop-2-en-1-one (Ib)
top Crystal data top C28H21ClN2O3 | Z = 2 |
Mr = 468.92 | F(000) = 488 |
Triclinic, P1 | Dx = 1.338 Mg m−3 |
a = 9.909 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.193 (6) Å | Cell parameters from 7088 reflections |
c = 12.024 (8) Å | θ = 3.0–31.0° |
α = 90.94 (2)° | µ = 0.20 mm−1 |
β = 106.27 (2)° | T = 297 K |
γ = 92.75 (2)° | Block, colourless |
V = 1163.9 (13) Å3 | 0.18 × 0.15 × 0.10 mm |
Data collection top Bruker APEXII diffractometer | 5884 independent reflections |
Radiation source: fine focussealed tube | 4402 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
φ and ω scans | θmax = 28.6°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −13→13 |
Tmin = 0.833, Tmax = 0.980 | k = −13→13 |
43789 measured reflections | l = −16→16 |
Refinement top Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.058 | w = 1/[σ2(Fo2) + (0.0448P)2 + 0.9732P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.155 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.43 e Å−3 |
5884 reflections | Δρmin = −0.41 e Å−3 |
309 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.154 (8) |
Primary atom site location: dual | |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.9482 (2) | 0.3833 (2) | 0.72250 (19) | 0.0464 (5) | |
O1 | 1.0416 (2) | 0.45886 (19) | 0.78220 (17) | 0.0709 (6) | |
C2 | 0.8469 (2) | 0.4294 (2) | 0.6173 (2) | 0.0478 (5) | |
H2 | 0.7655 | 0.3779 | 0.5825 | 0.057* | |
C3 | 0.8698 (2) | 0.5434 (2) | 0.57132 (18) | 0.0405 (4) | |
H3 | 0.9508 | 0.5925 | 0.6116 | 0.049* | |
C11 | 0.9385 (2) | 0.2433 (2) | 0.75289 (18) | 0.0417 (5) | |
C12 | 1.0483 (2) | 0.1947 (2) | 0.8398 (2) | 0.0486 (5) | |
H12 | 1.1247 | 0.2507 | 0.8778 | 0.058* | |
C13 | 1.0451 (2) | 0.0655 (2) | 0.8700 (2) | 0.0488 (5) | |
H13 | 1.1197 | 0.0347 | 0.9274 | 0.059* | |
C14 | 0.9314 (2) | −0.0192 (2) | 0.8155 (2) | 0.0446 (5) | |
C15 | 0.8204 (3) | 0.0268 (2) | 0.7302 (2) | 0.0511 (6) | |
H15 | 0.7431 | −0.0292 | 0.6939 | 0.061* | |
C16 | 0.8253 (2) | 0.1567 (2) | 0.6991 (2) | 0.0496 (5) | |
H16 | 0.7511 | 0.1868 | 0.6410 | 0.060* | |
O14 | 0.94132 (19) | −0.14583 (16) | 0.85166 (17) | 0.0576 (5) | |
C17 | 0.8187 (3) | −0.2343 (3) | 0.8139 (3) | 0.0654 (7) | |
H17A | 0.8452 | −0.3230 | 0.8345 | 0.078* | |
H17B | 0.7829 | −0.2328 | 0.7301 | 0.078* | |
C18 | 0.7077 (3) | −0.2002 (3) | 0.8653 (3) | 0.0608 (7) | |
C19 | 0.6186 (4) | −0.1767 (4) | 0.9061 (3) | 0.0824 (10) | |
H19 | 0.5469 | −0.1578 | 0.9390 | 0.099* | |
N31 | 0.62180 (18) | 0.64397 (15) | 0.30547 (16) | 0.0394 (4) | |
N32 | 0.71026 (19) | 0.75523 (16) | 0.33267 (16) | 0.0425 (4) | |
C33 | 0.8087 (2) | 0.72855 (19) | 0.42829 (19) | 0.0394 (4) | |
C34 | 0.7862 (2) | 0.60108 (18) | 0.46748 (18) | 0.0373 (4) | |
C35 | 0.6653 (2) | 0.55241 (18) | 0.38607 (18) | 0.0368 (4) | |
C311 | 0.4990 (2) | 0.6447 (2) | 0.20822 (19) | 0.0424 (5) | |
C312 | 0.4418 (4) | 0.5309 (3) | 0.1454 (3) | 0.0775 (10) | |
H312 | 0.4841 | 0.4517 | 0.1647 | 0.093* | |
C313 | 0.3214 (4) | 0.5351 (3) | 0.0534 (3) | 0.0871 (11) | |
H313 | 0.2826 | 0.4581 | 0.0117 | 0.104* | |
C314 | 0.2589 (3) | 0.6505 (3) | 0.0231 (2) | 0.0684 (8) | |
H314 | 0.1766 | 0.6523 | −0.0375 | 0.082* | |
C315 | 0.3188 (4) | 0.7634 (3) | 0.0829 (3) | 0.0777 (9) | |
H315 | 0.2781 | 0.8428 | 0.0615 | 0.093* | |
C316 | 0.4393 (3) | 0.7612 (3) | 0.1752 (2) | 0.0639 (7) | |
H316 | 0.4797 | 0.8390 | 0.2146 | 0.077* | |
C331 | 0.9235 (3) | 0.8287 (2) | 0.4843 (2) | 0.0514 (6) | |
H33A | 0.9224 | 0.9001 | 0.4330 | 0.077* | |
H33B | 1.0128 | 0.7893 | 0.5005 | 0.077* | |
H33C | 0.9093 | 0.8613 | 0.5553 | 0.077* | |
O351 | 0.58686 (15) | 0.43808 (13) | 0.38387 (13) | 0.0395 (3) | |
C351 | 0.6396 (2) | 0.32381 (17) | 0.35285 (17) | 0.0335 (4) | |
C352 | 0.5909 (2) | 0.20629 (18) | 0.38930 (17) | 0.0358 (4) | |
Cl52 | 0.47497 (6) | 0.21019 (6) | 0.47407 (5) | 0.05086 (19) | |
C353 | 0.6332 (2) | 0.08826 (19) | 0.35823 (19) | 0.0431 (5) | |
H353 | 0.6008 | 0.0102 | 0.3832 | 0.052* | |
C354 | 0.7248 (3) | 0.0858 (2) | 0.2892 (2) | 0.0478 (5) | |
H354 | 0.7528 | 0.0060 | 0.2671 | 0.057* | |
C355 | 0.7740 (2) | 0.2023 (2) | 0.2537 (2) | 0.0455 (5) | |
H355 | 0.8358 | 0.2006 | 0.2081 | 0.055* | |
C356 | 0.7321 (2) | 0.32177 (19) | 0.28541 (18) | 0.0396 (4) | |
H356 | 0.7659 | 0.3999 | 0.2616 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0496 (12) | 0.0438 (12) | 0.0403 (11) | −0.0114 (9) | 0.0060 (9) | 0.0047 (9) |
O1 | 0.0757 (13) | 0.0561 (11) | 0.0594 (11) | −0.0278 (9) | −0.0116 (9) | 0.0101 (9) |
C2 | 0.0484 (12) | 0.0413 (11) | 0.0463 (12) | −0.0082 (9) | 0.0027 (10) | 0.0037 (9) |
C3 | 0.0404 (10) | 0.0360 (10) | 0.0430 (11) | −0.0028 (8) | 0.0092 (8) | −0.0004 (8) |
C11 | 0.0438 (11) | 0.0435 (11) | 0.0346 (10) | −0.0065 (9) | 0.0072 (8) | 0.0038 (8) |
C12 | 0.0434 (11) | 0.0512 (13) | 0.0443 (11) | −0.0071 (9) | 0.0027 (9) | 0.0045 (10) |
C13 | 0.0434 (12) | 0.0514 (13) | 0.0478 (12) | 0.0026 (10) | 0.0060 (9) | 0.0089 (10) |
C14 | 0.0501 (12) | 0.0399 (11) | 0.0460 (11) | 0.0008 (9) | 0.0174 (10) | 0.0028 (9) |
C15 | 0.0495 (13) | 0.0445 (12) | 0.0525 (13) | −0.0089 (10) | 0.0050 (10) | 0.0025 (10) |
C16 | 0.0462 (12) | 0.0477 (12) | 0.0466 (12) | −0.0074 (10) | 0.0005 (10) | 0.0091 (10) |
O14 | 0.0601 (10) | 0.0410 (9) | 0.0728 (12) | 0.0041 (7) | 0.0196 (9) | 0.0106 (8) |
C17 | 0.0797 (19) | 0.0404 (13) | 0.0728 (18) | −0.0059 (12) | 0.0178 (15) | 0.0014 (12) |
C18 | 0.0536 (15) | 0.0500 (14) | 0.0678 (17) | −0.0125 (11) | 0.0010 (13) | 0.0083 (12) |
C19 | 0.0546 (17) | 0.088 (2) | 0.096 (2) | −0.0109 (16) | 0.0100 (17) | 0.0045 (19) |
N31 | 0.0418 (9) | 0.0256 (8) | 0.0468 (9) | −0.0026 (6) | 0.0067 (7) | 0.0027 (7) |
N32 | 0.0465 (10) | 0.0249 (8) | 0.0515 (10) | −0.0059 (7) | 0.0079 (8) | 0.0017 (7) |
C33 | 0.0426 (11) | 0.0283 (9) | 0.0468 (11) | −0.0032 (8) | 0.0127 (9) | −0.0023 (8) |
C34 | 0.0393 (10) | 0.0273 (9) | 0.0443 (11) | −0.0002 (7) | 0.0104 (8) | 0.0000 (8) |
C35 | 0.0401 (10) | 0.0243 (8) | 0.0460 (11) | −0.0019 (7) | 0.0127 (8) | 0.0007 (7) |
C311 | 0.0429 (11) | 0.0378 (10) | 0.0443 (11) | −0.0002 (8) | 0.0085 (9) | 0.0063 (8) |
C312 | 0.086 (2) | 0.0420 (14) | 0.0768 (19) | −0.0110 (13) | −0.0211 (16) | 0.0075 (13) |
C313 | 0.094 (2) | 0.0627 (18) | 0.074 (2) | −0.0247 (16) | −0.0216 (18) | 0.0134 (15) |
C314 | 0.0563 (15) | 0.089 (2) | 0.0507 (14) | −0.0010 (14) | 0.0002 (12) | 0.0174 (14) |
C315 | 0.087 (2) | 0.076 (2) | 0.0599 (17) | 0.0339 (17) | −0.0013 (15) | 0.0082 (15) |
C316 | 0.0765 (18) | 0.0487 (14) | 0.0565 (15) | 0.0156 (13) | 0.0005 (13) | −0.0013 (11) |
C331 | 0.0540 (13) | 0.0357 (11) | 0.0585 (14) | −0.0118 (9) | 0.0084 (11) | −0.0002 (10) |
O351 | 0.0391 (7) | 0.0245 (6) | 0.0563 (9) | −0.0031 (5) | 0.0164 (6) | 0.0009 (6) |
C351 | 0.0338 (9) | 0.0260 (8) | 0.0374 (9) | −0.0023 (7) | 0.0055 (7) | 0.0005 (7) |
C352 | 0.0353 (9) | 0.0307 (9) | 0.0382 (10) | −0.0063 (7) | 0.0063 (8) | 0.0020 (7) |
Cl52 | 0.0522 (3) | 0.0465 (3) | 0.0582 (4) | −0.0102 (2) | 0.0248 (3) | 0.0016 (2) |
C353 | 0.0521 (12) | 0.0265 (9) | 0.0479 (11) | −0.0043 (8) | 0.0106 (9) | 0.0040 (8) |
C354 | 0.0604 (14) | 0.0322 (10) | 0.0508 (12) | 0.0068 (9) | 0.0149 (11) | 0.0003 (9) |
C355 | 0.0481 (12) | 0.0432 (11) | 0.0486 (12) | 0.0061 (9) | 0.0187 (10) | 0.0035 (9) |
C356 | 0.0409 (10) | 0.0322 (10) | 0.0460 (11) | −0.0023 (8) | 0.0129 (9) | 0.0062 (8) |
Geometric parameters (Å, º) top C1—O1 | 1.228 (3) | C33—C331 | 1.492 (3) |
C1—C2 | 1.477 (3) | C34—C35 | 1.382 (3) |
C1—C11 | 1.484 (3) | C35—O351 | 1.365 (2) |
C2—C3 | 1.331 (3) | C311—C316 | 1.367 (3) |
C2—H2 | 0.9300 | C311—C312 | 1.380 (3) |
C3—C34 | 1.443 (3) | C312—C313 | 1.384 (4) |
C3—H3 | 0.9300 | C312—H312 | 0.9300 |
C11—C16 | 1.391 (3) | C313—C314 | 1.363 (5) |
C11—C12 | 1.398 (3) | C313—H313 | 0.9300 |
C12—C13 | 1.373 (3) | C314—C315 | 1.364 (5) |
C12—H12 | 0.9300 | C314—H314 | 0.9300 |
C13—C14 | 1.385 (3) | C315—C316 | 1.385 (4) |
C13—H13 | 0.9300 | C315—H315 | 0.9300 |
C14—O14 | 1.368 (3) | C316—H316 | 0.9300 |
C14—C15 | 1.384 (3) | C331—H33A | 0.9600 |
C15—C16 | 1.384 (3) | C331—H33B | 0.9600 |
C15—H15 | 0.9300 | C331—H33C | 0.9600 |
C16—H16 | 0.9300 | O351—C351 | 1.387 (2) |
O14—C17 | 1.438 (3) | C351—C356 | 1.384 (3) |
C17—C18 | 1.458 (4) | C351—C352 | 1.393 (3) |
C17—H17A | 0.9700 | C352—C353 | 1.373 (3) |
C17—H17B | 0.9700 | C352—Cl52 | 1.737 (2) |
C18—C19 | 1.157 (5) | C353—C354 | 1.391 (3) |
C19—H19 | 0.9300 | C353—H353 | 0.9300 |
N31—C35 | 1.353 (3) | C354—C355 | 1.382 (3) |
N31—N32 | 1.376 (2) | C354—H354 | 0.9300 |
N31—C311 | 1.433 (3) | C355—C356 | 1.386 (3) |
N32—C33 | 1.325 (3) | C355—H355 | 0.9300 |
C33—C34 | 1.418 (3) | C356—H356 | 0.9300 |
| | | |
O1—C1—C2 | 120.4 (2) | N31—C35—O351 | 120.93 (18) |
O1—C1—C11 | 120.4 (2) | N31—C35—C34 | 109.00 (17) |
C2—C1—C11 | 119.14 (19) | O351—C35—C34 | 129.85 (19) |
C3—C2—C1 | 121.3 (2) | C316—C311—C312 | 119.3 (2) |
C3—C2—H2 | 119.3 | C316—C311—N31 | 119.2 (2) |
C1—C2—H2 | 119.3 | C312—C311—N31 | 121.5 (2) |
C2—C3—C34 | 128.8 (2) | C311—C312—C313 | 119.8 (3) |
C2—C3—H3 | 115.6 | C311—C312—H312 | 120.1 |
C34—C3—H3 | 115.6 | C313—C312—H312 | 120.1 |
C16—C11—C12 | 117.7 (2) | C314—C313—C312 | 120.9 (3) |
C16—C11—C1 | 123.4 (2) | C314—C313—H313 | 119.6 |
C12—C11—C1 | 118.86 (19) | C312—C313—H313 | 119.6 |
C13—C12—C11 | 121.1 (2) | C313—C314—C315 | 119.1 (3) |
C13—C12—H12 | 119.5 | C313—C314—H314 | 120.5 |
C11—C12—H12 | 119.5 | C315—C314—H314 | 120.5 |
C12—C13—C14 | 120.4 (2) | C314—C315—C316 | 120.9 (3) |
C12—C13—H13 | 119.8 | C314—C315—H315 | 119.6 |
C14—C13—H13 | 119.8 | C316—C315—H315 | 119.6 |
O14—C14—C15 | 125.2 (2) | C311—C316—C315 | 120.0 (3) |
O14—C14—C13 | 115.0 (2) | C311—C316—H316 | 120.0 |
C15—C14—C13 | 119.8 (2) | C315—C316—H316 | 120.0 |
C16—C15—C14 | 119.5 (2) | C33—C331—H33A | 109.5 |
C16—C15—H15 | 120.2 | C33—C331—H33B | 109.5 |
C14—C15—H15 | 120.2 | H33A—C331—H33B | 109.5 |
C15—C16—C11 | 121.6 (2) | C33—C331—H33C | 109.5 |
C15—C16—H16 | 119.2 | H33A—C331—H33C | 109.5 |
C11—C16—H16 | 119.2 | H33B—C331—H33C | 109.5 |
C14—O14—C17 | 118.3 (2) | C35—O351—C351 | 117.09 (16) |
O14—C17—C18 | 112.3 (2) | C356—C351—O351 | 123.40 (17) |
O14—C17—H17A | 109.1 | C356—C351—C352 | 119.82 (18) |
C18—C17—H17A | 109.1 | O351—C351—C352 | 116.73 (18) |
O14—C17—H17B | 109.1 | C353—C352—C351 | 120.49 (19) |
C18—C17—H17B | 109.1 | C353—C352—Cl52 | 120.13 (15) |
H17A—C17—H17B | 107.9 | C351—C352—Cl52 | 119.38 (16) |
C19—C18—C17 | 178.1 (3) | C352—C353—C354 | 119.80 (19) |
C18—C19—H19 | 180.0 | C352—C353—H353 | 120.1 |
C35—N31—N32 | 110.06 (17) | C354—C353—H353 | 120.1 |
C35—N31—C311 | 130.75 (17) | C355—C354—C353 | 119.8 (2) |
N32—N31—C311 | 118.98 (16) | C355—C354—H354 | 120.1 |
C33—N32—N31 | 105.58 (16) | C353—C354—H354 | 120.1 |
N32—C33—C34 | 112.02 (18) | C354—C355—C356 | 120.6 (2) |
N32—C33—C331 | 120.60 (19) | C354—C355—H355 | 119.7 |
C34—C33—C331 | 127.3 (2) | C356—C355—H355 | 119.7 |
C35—C34—C33 | 103.31 (18) | C351—C356—C355 | 119.51 (18) |
C35—C34—C3 | 130.32 (19) | C351—C356—H356 | 120.2 |
C33—C34—C3 | 126.33 (19) | C355—C356—H356 | 120.2 |
| | | |
O1—C1—C2—C3 | 13.8 (4) | C311—N31—C35—C34 | −175.8 (2) |
C11—C1—C2—C3 | −164.2 (2) | C33—C34—C35—N31 | 0.5 (2) |
C1—C2—C3—C34 | 177.4 (2) | C3—C34—C35—N31 | 178.0 (2) |
O1—C1—C11—C16 | 171.0 (2) | C33—C34—C35—O351 | −174.0 (2) |
C2—C1—C11—C16 | −11.1 (4) | C3—C34—C35—O351 | 3.5 (4) |
O1—C1—C11—C12 | −9.2 (4) | C35—N31—C311—C316 | 147.1 (3) |
C2—C1—C11—C12 | 168.8 (2) | N32—N31—C311—C316 | −27.1 (3) |
C16—C11—C12—C13 | 0.7 (4) | C35—N31—C311—C312 | −34.7 (4) |
C1—C11—C12—C13 | −179.2 (2) | N32—N31—C311—C312 | 151.1 (3) |
C11—C12—C13—C14 | −0.8 (4) | C316—C311—C312—C313 | −3.1 (5) |
C12—C13—C14—O14 | 179.0 (2) | N31—C311—C312—C313 | 178.7 (3) |
C12—C13—C14—C15 | −0.1 (4) | C311—C312—C313—C314 | 0.7 (6) |
O14—C14—C15—C16 | −178.1 (2) | C312—C313—C314—C315 | 1.7 (6) |
C13—C14—C15—C16 | 0.9 (4) | C313—C314—C315—C316 | −1.6 (5) |
C14—C15—C16—C11 | −1.0 (4) | C312—C311—C316—C315 | 3.1 (5) |
C12—C11—C16—C15 | 0.1 (4) | N31—C311—C316—C315 | −178.6 (3) |
C1—C11—C16—C15 | −180.0 (2) | C314—C315—C316—C311 | −0.8 (5) |
C15—C14—O14—C17 | −11.2 (4) | N31—C35—O351—C351 | 109.4 (2) |
C13—C14—O14—C17 | 169.8 (2) | C34—C35—O351—C351 | −76.7 (3) |
C14—O14—C17—C18 | −68.7 (3) | C35—O351—C351—C356 | −24.8 (3) |
C35—N31—N32—C33 | 1.5 (2) | C35—O351—C351—C352 | 157.64 (18) |
C311—N31—N32—C33 | 176.81 (18) | C356—C351—C352—C353 | −0.4 (3) |
N31—N32—C33—C34 | −1.2 (2) | O351—C351—C352—C353 | 177.27 (18) |
N31—N32—C33—C331 | −179.43 (19) | C356—C351—C352—Cl52 | 179.92 (15) |
N32—C33—C34—C35 | 0.5 (2) | O351—C351—C352—Cl52 | −2.4 (2) |
C331—C33—C34—C35 | 178.5 (2) | C351—C352—C353—C354 | −0.4 (3) |
N32—C33—C34—C3 | −177.2 (2) | Cl52—C352—C353—C354 | 179.26 (17) |
C331—C33—C34—C3 | 0.9 (4) | C352—C353—C354—C355 | 0.9 (3) |
C2—C3—C34—C35 | −3.3 (4) | C353—C354—C355—C356 | −0.5 (4) |
C2—C3—C34—C33 | 173.7 (2) | O351—C351—C356—C355 | −176.76 (19) |
N32—N31—C35—O351 | 173.80 (17) | C352—C351—C356—C355 | 0.8 (3) |
C311—N31—C35—O351 | −0.8 (3) | C354—C355—C356—C351 | −0.3 (3) |
N32—N31—C35—C34 | −1.3 (2) | | |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C355—H355···O14i | 0.93 | 2.59 | 3.468 (4) | 158 |
C356—H356···O1ii | 0.93 | 2.51 | 3.360 (4) | 152 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1. |
3-[5-(4-Chlorophenoxy)-3-methyl-1-phenyl-1
H-pyrazol-4-yl]-1-[4-(prop-2-yn-1-yloxy)phenyl]prop-2-en-1-one (Ic)
top Crystal data top C28H21ClN2O3 | Z = 2 |
Mr = 468.92 | F(000) = 488 |
Triclinic, P1 | Dx = 1.322 Mg m−3 |
a = 8.9959 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7380 (15) Å | Cell parameters from 4839 reflections |
c = 13.637 (2) Å | θ = 2.9–26.5° |
α = 95.901 (4)° | µ = 0.20 mm−1 |
β = 94.122 (4)° | T = 297 K |
γ = 95.959 (4)° | Block, brown |
V = 1177.8 (3) Å3 | 0.20 × 0.15 × 0.15 mm |
Data collection top Bruker APEXII diffractometer | 4837 independent reflections |
Radiation source: fine focussealed tube | 3930 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
φ and ω scans | θmax = 26.5°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −11→11 |
Tmin = 0.901, Tmax = 0.971 | k = −12→12 |
49011 measured reflections | l = −17→17 |
Refinement top Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | w = 1/[σ2(Fo2) + (0.0384P)2 + 0.6832P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max = 0.001 |
S = 1.15 | Δρmax = 0.35 e Å−3 |
4837 reflections | Δρmin = −0.45 e Å−3 |
309 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.092 (6) |
Primary atom site location: dual | |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.5453 (2) | 0.2711 (2) | 0.53901 (14) | 0.0354 (4) | |
O1 | 0.49212 (18) | 0.19336 (17) | 0.46533 (11) | 0.0535 (4) | |
C2 | 0.5001 (2) | 0.2494 (2) | 0.63858 (14) | 0.0375 (4) | |
H2 | 0.5266 | 0.3202 | 0.6899 | 0.045* | |
C3 | 0.4233 (2) | 0.1329 (2) | 0.65779 (14) | 0.0360 (4) | |
H3 | 0.3999 | 0.0635 | 0.6051 | 0.043* | |
C11 | 0.65551 (19) | 0.39198 (18) | 0.52879 (13) | 0.0321 (4) | |
C12 | 0.6706 (2) | 0.4355 (2) | 0.43611 (13) | 0.0366 (4) | |
H12 | 0.6103 | 0.3890 | 0.3821 | 0.044* | |
C13 | 0.7725 (2) | 0.54596 (19) | 0.42185 (14) | 0.0373 (4) | |
H13 | 0.7803 | 0.5739 | 0.3591 | 0.045* | |
C14 | 0.8635 (2) | 0.61513 (19) | 0.50232 (14) | 0.0351 (4) | |
C15 | 0.8509 (2) | 0.5724 (2) | 0.59521 (14) | 0.0430 (5) | |
H15 | 0.9124 | 0.6180 | 0.6490 | 0.052* | |
C16 | 0.7477 (2) | 0.4627 (2) | 0.60857 (14) | 0.0408 (5) | |
H16 | 0.7394 | 0.4355 | 0.6715 | 0.049* | |
O14 | 0.96866 (16) | 0.72487 (15) | 0.49739 (10) | 0.0466 (4) | |
C17 | 0.9800 (2) | 0.7763 (2) | 0.40407 (16) | 0.0456 (5) | |
H17A | 0.8869 | 0.8110 | 0.3832 | 0.055* | |
H17B | 0.9987 | 0.7023 | 0.3548 | 0.055* | |
C18 | 1.1030 (2) | 0.8878 (2) | 0.41364 (16) | 0.0445 (5) | |
C19 | 1.2031 (3) | 0.9760 (2) | 0.41795 (18) | 0.0541 (6) | |
H19 | 1.2825 | 1.0460 | 0.4214 | 0.065* | |
N31 | 0.32759 (17) | 0.10603 (16) | 0.91019 (11) | 0.0359 (4) | |
N32 | 0.23589 (18) | −0.00607 (17) | 0.86251 (12) | 0.0387 (4) | |
C33 | 0.2648 (2) | −0.00897 (19) | 0.76832 (14) | 0.0350 (4) | |
C34 | 0.37180 (19) | 0.10233 (19) | 0.75252 (13) | 0.0324 (4) | |
C35 | 0.4074 (2) | 0.17216 (19) | 0.84574 (13) | 0.0333 (4) | |
C311 | 0.3251 (2) | 0.14030 (19) | 1.01431 (14) | 0.0376 (4) | |
C312 | 0.4578 (3) | 0.1772 (2) | 1.07284 (16) | 0.0498 (5) | |
H312 | 0.5492 | 0.1809 | 1.0449 | 0.060* | |
C313 | 0.4527 (3) | 0.2086 (3) | 1.17386 (18) | 0.0639 (7) | |
H313 | 0.5415 | 0.2351 | 1.2136 | 0.077* | |
C314 | 0.3191 (4) | 0.2013 (3) | 1.21603 (18) | 0.0660 (7) | |
H314 | 0.3172 | 0.2223 | 1.2840 | 0.079* | |
C315 | 0.1875 (3) | 0.1625 (3) | 1.15721 (19) | 0.0633 (7) | |
H315 | 0.0966 | 0.1564 | 1.1858 | 0.076* | |
C316 | 0.1892 (3) | 0.1326 (2) | 1.05553 (16) | 0.0478 (5) | |
H316 | 0.1001 | 0.1077 | 1.0158 | 0.057* | |
C331 | 0.1866 (3) | −0.1197 (2) | 0.69277 (16) | 0.0485 (5) | |
H33A | 0.1505 | −0.1984 | 0.7248 | 0.073* | |
H33B | 0.2555 | −0.1473 | 0.6458 | 0.073* | |
H33C | 0.1037 | −0.0845 | 0.6591 | 0.073* | |
O351 | 0.48920 (15) | 0.29585 (13) | 0.87828 (10) | 0.0397 (3) | |
C351 | 0.6443 (2) | 0.31066 (19) | 0.87288 (13) | 0.0335 (4) | |
C352 | 0.7128 (2) | 0.4453 (2) | 0.89176 (16) | 0.0431 (5) | |
H352 | 0.6565 | 0.5182 | 0.9075 | 0.052* | |
C353 | 0.8669 (2) | 0.4705 (2) | 0.88698 (16) | 0.0460 (5) | |
H353 | 0.9148 | 0.5607 | 0.8994 | 0.055* | |
C354 | 0.9481 (2) | 0.3613 (2) | 0.86373 (14) | 0.0415 (5) | |
Cl54 | 1.14061 (6) | 0.39375 (8) | 0.85575 (5) | 0.0630 (2) | |
C355 | 0.8803 (2) | 0.2275 (2) | 0.84574 (16) | 0.0458 (5) | |
H355 | 0.9369 | 0.1547 | 0.8305 | 0.055* | |
C356 | 0.7260 (2) | 0.2015 (2) | 0.85043 (16) | 0.0422 (5) | |
H356 | 0.6785 | 0.1112 | 0.8385 | 0.051* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0323 (9) | 0.0385 (10) | 0.0340 (9) | −0.0033 (7) | 0.0052 (7) | 0.0035 (8) |
O1 | 0.0583 (9) | 0.0560 (9) | 0.0383 (8) | −0.0266 (7) | 0.0049 (7) | 0.0008 (7) |
C2 | 0.0375 (10) | 0.0407 (10) | 0.0334 (9) | −0.0029 (8) | 0.0059 (7) | 0.0046 (8) |
C3 | 0.0340 (9) | 0.0396 (10) | 0.0338 (9) | −0.0022 (8) | 0.0067 (7) | 0.0042 (8) |
C11 | 0.0306 (9) | 0.0326 (9) | 0.0323 (9) | −0.0010 (7) | 0.0053 (7) | 0.0020 (7) |
C12 | 0.0371 (10) | 0.0393 (10) | 0.0307 (9) | −0.0050 (8) | 0.0015 (7) | 0.0014 (7) |
C13 | 0.0399 (10) | 0.0376 (10) | 0.0339 (9) | −0.0031 (8) | 0.0041 (8) | 0.0074 (8) |
C14 | 0.0329 (9) | 0.0306 (9) | 0.0401 (10) | −0.0043 (7) | 0.0071 (7) | 0.0002 (7) |
C15 | 0.0430 (11) | 0.0469 (11) | 0.0332 (10) | −0.0121 (9) | 0.0010 (8) | −0.0040 (8) |
C16 | 0.0433 (11) | 0.0464 (11) | 0.0300 (9) | −0.0092 (9) | 0.0050 (8) | 0.0045 (8) |
O14 | 0.0492 (8) | 0.0414 (8) | 0.0439 (8) | −0.0179 (6) | 0.0045 (6) | 0.0028 (6) |
C17 | 0.0423 (11) | 0.0432 (11) | 0.0492 (12) | −0.0097 (9) | 0.0002 (9) | 0.0125 (9) |
C18 | 0.0425 (11) | 0.0422 (11) | 0.0486 (12) | −0.0027 (9) | 0.0061 (9) | 0.0095 (9) |
C19 | 0.0508 (13) | 0.0523 (13) | 0.0564 (13) | −0.0144 (10) | 0.0057 (10) | 0.0119 (10) |
N31 | 0.0378 (8) | 0.0370 (8) | 0.0320 (8) | −0.0017 (7) | 0.0059 (6) | 0.0035 (6) |
N32 | 0.0384 (8) | 0.0393 (9) | 0.0370 (8) | −0.0047 (7) | 0.0066 (7) | 0.0040 (7) |
C33 | 0.0336 (9) | 0.0352 (9) | 0.0357 (9) | −0.0014 (7) | 0.0045 (7) | 0.0059 (7) |
C34 | 0.0305 (8) | 0.0340 (9) | 0.0330 (9) | 0.0010 (7) | 0.0051 (7) | 0.0062 (7) |
C35 | 0.0306 (9) | 0.0330 (9) | 0.0359 (9) | 0.0003 (7) | 0.0046 (7) | 0.0033 (7) |
C311 | 0.0488 (11) | 0.0342 (9) | 0.0317 (9) | 0.0091 (8) | 0.0076 (8) | 0.0055 (7) |
C312 | 0.0551 (13) | 0.0560 (13) | 0.0395 (11) | 0.0168 (10) | 0.0017 (9) | 0.0015 (9) |
C313 | 0.0885 (19) | 0.0621 (15) | 0.0411 (12) | 0.0254 (14) | −0.0089 (12) | −0.0017 (11) |
C314 | 0.111 (2) | 0.0559 (15) | 0.0355 (12) | 0.0270 (15) | 0.0143 (14) | 0.0046 (10) |
C315 | 0.0897 (19) | 0.0548 (14) | 0.0540 (14) | 0.0181 (13) | 0.0390 (14) | 0.0136 (11) |
C316 | 0.0553 (13) | 0.0459 (12) | 0.0455 (12) | 0.0062 (10) | 0.0177 (10) | 0.0104 (9) |
C331 | 0.0481 (12) | 0.0482 (12) | 0.0439 (11) | −0.0120 (9) | 0.0045 (9) | −0.0027 (9) |
O351 | 0.0352 (7) | 0.0334 (7) | 0.0484 (8) | −0.0014 (5) | 0.0065 (6) | −0.0024 (6) |
C351 | 0.0350 (9) | 0.0334 (9) | 0.0314 (9) | 0.0010 (7) | 0.0026 (7) | 0.0027 (7) |
C352 | 0.0432 (11) | 0.0320 (10) | 0.0518 (12) | 0.0024 (8) | 0.0019 (9) | −0.0028 (8) |
C353 | 0.0460 (11) | 0.0387 (11) | 0.0490 (12) | −0.0073 (9) | −0.0020 (9) | 0.0009 (9) |
C354 | 0.0363 (10) | 0.0530 (12) | 0.0333 (10) | 0.0000 (9) | 0.0001 (8) | 0.0024 (8) |
Cl54 | 0.0371 (3) | 0.0877 (5) | 0.0605 (4) | −0.0021 (3) | 0.0037 (2) | 0.0001 (3) |
C355 | 0.0422 (11) | 0.0451 (11) | 0.0500 (12) | 0.0100 (9) | 0.0022 (9) | 0.0000 (9) |
C356 | 0.0428 (11) | 0.0324 (10) | 0.0494 (11) | 0.0010 (8) | 0.0022 (9) | 0.0002 (8) |
Geometric parameters (Å, º) top C1—O1 | 1.229 (2) | C33—C331 | 1.493 (3) |
C1—C2 | 1.474 (3) | C34—C35 | 1.378 (3) |
C1—C11 | 1.483 (2) | C35—O351 | 1.360 (2) |
C2—C3 | 1.327 (3) | C311—C316 | 1.380 (3) |
C2—H2 | 0.9300 | C311—C312 | 1.380 (3) |
C3—C34 | 1.452 (2) | C312—C313 | 1.385 (3) |
C3—H3 | 0.9300 | C312—H312 | 0.9300 |
C11—C12 | 1.385 (3) | C313—C314 | 1.367 (4) |
C11—C16 | 1.394 (3) | C313—H313 | 0.9300 |
C12—C13 | 1.378 (3) | C314—C315 | 1.377 (4) |
C12—H12 | 0.9300 | C314—H314 | 0.9300 |
C13—C14 | 1.390 (3) | C315—C316 | 1.389 (3) |
C13—H13 | 0.9300 | C315—H315 | 0.9300 |
C14—O14 | 1.362 (2) | C316—H316 | 0.9300 |
C14—C15 | 1.382 (3) | C331—H33A | 0.9600 |
C15—C16 | 1.376 (3) | C331—H33B | 0.9600 |
C15—H15 | 0.9300 | C331—H33C | 0.9600 |
C16—H16 | 0.9300 | O351—C351 | 1.396 (2) |
O14—C17 | 1.421 (2) | C351—C356 | 1.375 (3) |
C17—C18 | 1.456 (3) | C351—C352 | 1.380 (3) |
C17—H17A | 0.9700 | C352—C353 | 1.391 (3) |
C17—H17B | 0.9700 | C352—H352 | 0.9300 |
C18—C19 | 1.172 (3) | C353—C354 | 1.374 (3) |
C19—H19 | 0.9300 | C353—H353 | 0.9300 |
N31—C35 | 1.347 (2) | C354—C355 | 1.370 (3) |
N31—N32 | 1.373 (2) | C354—Cl54 | 1.741 (2) |
N31—C311 | 1.427 (2) | C355—C356 | 1.393 (3) |
N32—C33 | 1.327 (2) | C355—H355 | 0.9300 |
C33—C34 | 1.418 (2) | C356—H356 | 0.9300 |
| | | |
O1—C1—C2 | 121.66 (17) | N31—C35—O351 | 118.65 (16) |
O1—C1—C11 | 120.01 (16) | N31—C35—C34 | 108.52 (15) |
C2—C1—C11 | 118.32 (16) | O351—C35—C34 | 132.30 (16) |
C3—C2—C1 | 122.56 (18) | C316—C311—C312 | 120.78 (19) |
C3—C2—H2 | 118.7 | C316—C311—N31 | 119.17 (19) |
C1—C2—H2 | 118.7 | C312—C311—N31 | 120.03 (18) |
C2—C3—C34 | 126.73 (18) | C311—C312—C313 | 119.0 (2) |
C2—C3—H3 | 116.6 | C311—C312—H312 | 120.5 |
C34—C3—H3 | 116.6 | C313—C312—H312 | 120.5 |
C12—C11—C16 | 118.11 (16) | C314—C313—C312 | 121.0 (3) |
C12—C11—C1 | 119.13 (16) | C314—C313—H313 | 119.5 |
C16—C11—C1 | 122.75 (16) | C312—C313—H313 | 119.5 |
C13—C12—C11 | 121.74 (17) | C313—C314—C315 | 119.5 (2) |
C13—C12—H12 | 119.1 | C313—C314—H314 | 120.2 |
C11—C12—H12 | 119.1 | C315—C314—H314 | 120.2 |
C12—C13—C14 | 119.29 (17) | C314—C315—C316 | 120.6 (2) |
C12—C13—H13 | 120.4 | C314—C315—H315 | 119.7 |
C14—C13—H13 | 120.4 | C316—C315—H315 | 119.7 |
O14—C14—C15 | 115.58 (16) | C311—C316—C315 | 119.0 (2) |
O14—C14—C13 | 124.66 (17) | C311—C316—H316 | 120.5 |
C15—C14—C13 | 119.77 (16) | C315—C316—H316 | 120.5 |
C16—C15—C14 | 120.34 (17) | C33—C331—H33A | 109.5 |
C16—C15—H15 | 119.8 | C33—C331—H33B | 109.5 |
C14—C15—H15 | 119.8 | H33A—C331—H33B | 109.5 |
C15—C16—C11 | 120.75 (17) | C33—C331—H33C | 109.5 |
C15—C16—H16 | 119.6 | H33A—C331—H33C | 109.5 |
C11—C16—H16 | 119.6 | H33B—C331—H33C | 109.5 |
C14—O14—C17 | 117.27 (15) | C35—O351—C351 | 119.84 (14) |
O14—C17—C18 | 108.51 (17) | C356—C351—C352 | 121.22 (18) |
O14—C17—H17A | 110.0 | C356—C351—O351 | 123.80 (16) |
C18—C17—H17A | 110.0 | C352—C351—O351 | 114.98 (16) |
O14—C17—H17B | 110.0 | C351—C352—C353 | 119.14 (19) |
C18—C17—H17B | 110.0 | C351—C352—H352 | 120.4 |
H17A—C17—H17B | 108.4 | C353—C352—H352 | 120.4 |
C19—C18—C17 | 177.6 (2) | C354—C353—C352 | 119.52 (19) |
C18—C19—H19 | 180.0 | C354—C353—H353 | 120.2 |
C35—N31—N32 | 110.96 (15) | C352—C353—H353 | 120.2 |
C35—N31—C311 | 129.06 (16) | C355—C354—C353 | 121.34 (19) |
N32—N31—C311 | 119.96 (15) | C355—C354—Cl54 | 119.29 (17) |
C33—N32—N31 | 104.91 (14) | C353—C354—Cl54 | 119.37 (16) |
N32—C33—C34 | 112.02 (16) | C354—C355—C356 | 119.44 (19) |
N32—C33—C331 | 120.58 (17) | C354—C355—H355 | 120.3 |
C34—C33—C331 | 127.39 (17) | C356—C355—H355 | 120.3 |
C35—C34—C33 | 103.56 (15) | C351—C356—C355 | 119.34 (18) |
C35—C34—C3 | 130.35 (17) | C351—C356—H356 | 120.3 |
C33—C34—C3 | 126.06 (17) | C355—C356—H356 | 120.3 |
| | | |
O1—C1—C2—C3 | 13.1 (3) | N32—N31—C35—C34 | −1.2 (2) |
C11—C1—C2—C3 | −168.12 (19) | C311—N31—C35—C34 | −179.14 (18) |
C1—C2—C3—C34 | −179.02 (18) | C33—C34—C35—N31 | 0.2 (2) |
O1—C1—C11—C12 | 15.4 (3) | C3—C34—C35—N31 | 178.15 (19) |
C2—C1—C11—C12 | −163.41 (18) | C33—C34—C35—O351 | −171.11 (19) |
O1—C1—C11—C16 | −163.3 (2) | C3—C34—C35—O351 | 6.8 (3) |
C2—C1—C11—C16 | 17.9 (3) | C35—N31—C311—C316 | 136.4 (2) |
C16—C11—C12—C13 | −0.4 (3) | N32—N31—C311—C316 | −41.4 (3) |
C1—C11—C12—C13 | −179.10 (18) | C35—N31—C311—C312 | −45.3 (3) |
C11—C12—C13—C14 | 0.4 (3) | N32—N31—C311—C312 | 137.0 (2) |
C12—C13—C14—O14 | 179.64 (18) | C316—C311—C312—C313 | −1.0 (3) |
C12—C13—C14—C15 | 0.1 (3) | N31—C311—C312—C313 | −179.3 (2) |
O14—C14—C15—C16 | 179.76 (19) | C311—C312—C313—C314 | 1.1 (4) |
C13—C14—C15—C16 | −0.6 (3) | C312—C313—C314—C315 | −0.2 (4) |
C14—C15—C16—C11 | 0.7 (3) | C313—C314—C315—C316 | −0.8 (4) |
C12—C11—C16—C15 | −0.2 (3) | C312—C311—C316—C315 | 0.0 (3) |
C1—C11—C16—C15 | 178.48 (19) | N31—C311—C316—C315 | 178.35 (19) |
C15—C14—O14—C17 | −176.97 (19) | C314—C315—C316—C311 | 0.9 (3) |
C13—C14—O14—C17 | 3.5 (3) | N31—C35—O351—C351 | 120.05 (18) |
C14—O14—C17—C18 | −177.14 (18) | C34—C35—O351—C351 | −69.3 (3) |
C35—N31—N32—C33 | 1.7 (2) | C35—O351—C351—C356 | −10.4 (3) |
C311—N31—N32—C33 | 179.86 (16) | C35—O351—C351—C352 | 169.43 (17) |
N31—N32—C33—C34 | −1.6 (2) | C356—C351—C352—C353 | 0.6 (3) |
N31—N32—C33—C331 | 179.10 (18) | O351—C351—C352—C353 | −179.26 (18) |
N32—C33—C34—C35 | 0.9 (2) | C351—C352—C353—C354 | −0.1 (3) |
C331—C33—C34—C35 | −179.9 (2) | C352—C353—C354—C355 | −0.4 (3) |
N32—C33—C34—C3 | −177.16 (18) | C352—C353—C354—Cl54 | 178.92 (16) |
C331—C33—C34—C3 | 2.1 (3) | C353—C354—C355—C356 | 0.4 (3) |
C2—C3—C34—C35 | −11.4 (3) | Cl54—C354—C355—C356 | −178.93 (16) |
C2—C3—C34—C33 | 166.1 (2) | C352—C351—C356—C355 | −0.6 (3) |
N32—N31—C35—O351 | 171.48 (15) | O351—C351—C356—C355 | 179.23 (18) |
C311—N31—C35—O351 | −6.4 (3) | C354—C355—C356—C351 | 0.1 (3) |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O1i | 0.93 | 2.25 | 3.161 (3) | 165 |
C16—H16···Cg2 | 0.93 | 2.98 | 3.882 (2) | 165 |
C356—H356···Cg1ii | 0.93 | 2.88 | 3.685 (2) | 146 |
Symmetry codes: (i) x+1, y+1, z; (ii) −x+1, −y, −z+2. |
3-[3-Methyl-5-(naphthalen-2-yloxy)-1-phenyl-1
H-pyrazol-4-yl]-1-[4-(prop-2-ynyloxy)phenyl]prop-2-en-1-one (Ie)
top Crystal data top C32H24N2O3 | Z = 2 |
Mr = 484.53 | F(000) = 508 |
Triclinic, P1 | Dx = 1.307 Mg m−3 |
a = 8.8615 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.4973 (7) Å | Cell parameters from 4376 reflections |
c = 13.6588 (10) Å | θ = 3.0–25.2° |
α = 79.006 (3)° | µ = 0.08 mm−1 |
β = 89.412 (3)° | T = 297 K |
γ = 80.971 (3)° | Block, brown |
V = 1231.54 (15) Å3 | 0.20 × 0.16 × 0.16 mm |
Data collection top Bruker APEXII diffractometer | 4373 independent reflections |
Radiation source: fine focussealed tube | 3474 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
φ and ω scans | θmax = 25.2°, θmin = 3.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −10→10 |
Tmin = 0.898, Tmax = 0.987 | k = −12→12 |
30613 measured reflections | l = −16→16 |
Refinement top Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.070 | w = 1/[σ2(Fo2) + (0.0694P)2 + 1.3194P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.187 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.85 e Å−3 |
4373 reflections | Δρmin = −0.29 e Å−3 |
336 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.114 (12) |
Primary atom site location: dual | |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.4597 (3) | 0.2692 (3) | 0.9522 (2) | 0.0466 (6) | |
O1 | 0.5161 (3) | 0.1921 (2) | 1.02722 (15) | 0.0682 (7) | |
C2 | 0.5008 (3) | 0.2472 (3) | 0.8514 (2) | 0.0479 (7) | |
H2 | 0.4710 | 0.3145 | 0.7970 | 0.057* | |
C3 | 0.5789 (3) | 0.1344 (3) | 0.8354 (2) | 0.0456 (6) | |
H3 | 0.6058 | 0.0694 | 0.8916 | 0.055* | |
C11 | 0.3503 (3) | 0.3873 (3) | 0.96264 (18) | 0.0421 (6) | |
C12 | 0.3407 (3) | 0.4290 (3) | 1.0532 (2) | 0.0491 (7) | |
H12 | 0.4032 | 0.3815 | 1.1063 | 0.059* | |
C13 | 0.2408 (3) | 0.5392 (3) | 1.0669 (2) | 0.0501 (7) | |
H13 | 0.2376 | 0.5664 | 1.1279 | 0.060* | |
C14 | 0.1454 (3) | 0.6086 (3) | 0.9883 (2) | 0.0463 (6) | |
C15 | 0.1510 (3) | 0.5671 (3) | 0.8978 (2) | 0.0539 (7) | |
H15 | 0.0854 | 0.6126 | 0.8457 | 0.065* | |
C16 | 0.2528 (3) | 0.4595 (3) | 0.8848 (2) | 0.0516 (7) | |
H16 | 0.2572 | 0.4340 | 0.8232 | 0.062* | |
O14 | 0.0419 (2) | 0.7179 (2) | 0.99303 (15) | 0.0600 (6) | |
C17 | 0.0309 (4) | 0.7627 (3) | 1.0852 (2) | 0.0584 (8) | |
H17A | 0.1258 | 0.7910 | 1.0999 | 0.070* | |
H17B | 0.0129 | 0.6918 | 1.1387 | 0.070* | |
C18 | −0.0948 (4) | 0.8721 (3) | 1.0781 (2) | 0.0584 (8) | |
C19 | −0.1963 (4) | 0.9573 (4) | 1.0761 (3) | 0.0695 (9) | |
H19 | −0.2776 | 1.0256 | 1.0745 | 0.083* | |
N31 | 0.6678 (2) | 0.0973 (2) | 0.58075 (16) | 0.0441 (5) | |
N32 | 0.7581 (3) | −0.0141 (2) | 0.63236 (16) | 0.0481 (6) | |
C33 | 0.7313 (3) | −0.0118 (3) | 0.72742 (19) | 0.0439 (6) | |
C34 | 0.6271 (3) | 0.1007 (3) | 0.74080 (19) | 0.0415 (6) | |
C35 | 0.5907 (3) | 0.1663 (2) | 0.64457 (19) | 0.0423 (6) | |
C311 | 0.6675 (3) | 0.1256 (3) | 0.47431 (19) | 0.0435 (6) | |
C312 | 0.5324 (3) | 0.1747 (3) | 0.4211 (2) | 0.0591 (8) | |
H312 | 0.4408 | 0.1889 | 0.4542 | 0.071* | |
C313 | 0.5349 (4) | 0.2025 (4) | 0.3179 (2) | 0.0681 (9) | |
H313 | 0.4444 | 0.2372 | 0.2819 | 0.082* | |
C314 | 0.6679 (4) | 0.1798 (3) | 0.2679 (2) | 0.0631 (9) | |
H314 | 0.6683 | 0.1990 | 0.1986 | 0.076* | |
C315 | 0.8004 (4) | 0.1285 (3) | 0.3216 (2) | 0.0640 (9) | |
H315 | 0.8910 | 0.1114 | 0.2881 | 0.077* | |
C316 | 0.8019 (3) | 0.1014 (3) | 0.4253 (2) | 0.0535 (7) | |
H316 | 0.8927 | 0.0674 | 0.4610 | 0.064* | |
C331 | 0.8082 (4) | −0.1185 (3) | 0.8078 (2) | 0.0595 (8) | |
H33A | 0.8606 | −0.1889 | 0.7786 | 0.089* | |
H33B | 0.7331 | −0.1508 | 0.8529 | 0.089* | |
H33C | 0.8805 | −0.0843 | 0.8435 | 0.089* | |
O351 | 0.5097 (2) | 0.28760 (18) | 0.60811 (15) | 0.0528 (5) | |
C351 | 0.2781 (4) | 0.4338 (3) | 0.6115 (2) | 0.0550 (7) | |
H351 | 0.3356 | 0.5017 | 0.5971 | 0.066* | |
C352 | 0.3475 (3) | 0.3071 (3) | 0.62206 (19) | 0.0507 (7) | |
C353 | 0.2669 (4) | 0.2018 (3) | 0.6420 (2) | 0.0595 (8) | |
H353 | 0.3175 | 0.1160 | 0.6483 | 0.071* | |
C354 | 0.1103 (4) | 0.2270 (3) | 0.6523 (3) | 0.0669 (9) | |
H354 | 0.0553 | 0.1573 | 0.6654 | 0.080* | |
C355 | −0.1287 (4) | 0.3815 (4) | 0.6550 (3) | 0.0695 (10) | |
H355 | −0.1864 | 0.3137 | 0.6686 | 0.083* | |
C356 | −0.1961 (4) | 0.5079 (4) | 0.6457 (3) | 0.0737 (10) | |
H356 | −0.3013 | 0.5257 | 0.6533 | 0.088* | |
C357 | −0.1145 (5) | 0.6132 (4) | 0.6250 (3) | 0.0791 (11) | |
H357 | −0.1648 | 0.6991 | 0.6188 | 0.095* | |
C358 | 0.0361 (4) | 0.5891 (4) | 0.6142 (3) | 0.0722 (10) | |
H358 | 0.0898 | 0.6596 | 0.6005 | 0.087* | |
C359 | 0.0346 (4) | 0.3537 (3) | 0.6434 (2) | 0.0589 (8) | |
C360 | 0.1159 (3) | 0.4629 (3) | 0.62260 (19) | 0.0447 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0466 (15) | 0.0465 (15) | 0.0434 (15) | 0.0048 (12) | −0.0025 (12) | −0.0100 (12) |
O1 | 0.0799 (15) | 0.0664 (14) | 0.0440 (12) | 0.0306 (12) | −0.0081 (10) | −0.0086 (10) |
C2 | 0.0506 (16) | 0.0482 (15) | 0.0404 (14) | 0.0053 (12) | −0.0009 (12) | −0.0081 (12) |
C3 | 0.0443 (14) | 0.0458 (15) | 0.0430 (14) | 0.0025 (12) | −0.0013 (11) | −0.0073 (11) |
C11 | 0.0435 (14) | 0.0418 (14) | 0.0369 (13) | 0.0038 (11) | −0.0001 (11) | −0.0057 (11) |
C12 | 0.0500 (16) | 0.0516 (16) | 0.0394 (14) | 0.0096 (13) | −0.0072 (12) | −0.0066 (12) |
C13 | 0.0572 (17) | 0.0491 (16) | 0.0403 (14) | 0.0077 (13) | −0.0031 (12) | −0.0125 (12) |
C14 | 0.0474 (15) | 0.0408 (14) | 0.0455 (15) | 0.0065 (11) | 0.0018 (12) | −0.0064 (11) |
C15 | 0.0555 (17) | 0.0577 (17) | 0.0395 (15) | 0.0138 (14) | −0.0085 (12) | −0.0047 (12) |
C16 | 0.0578 (17) | 0.0541 (17) | 0.0371 (14) | 0.0104 (13) | −0.0051 (12) | −0.0098 (12) |
O14 | 0.0669 (13) | 0.0537 (12) | 0.0499 (12) | 0.0219 (10) | −0.0050 (10) | −0.0115 (9) |
C17 | 0.0588 (18) | 0.0567 (18) | 0.0560 (18) | 0.0116 (14) | −0.0046 (14) | −0.0186 (14) |
C18 | 0.0595 (18) | 0.0551 (18) | 0.0574 (18) | 0.0067 (15) | 0.0010 (14) | −0.0154 (14) |
C19 | 0.069 (2) | 0.069 (2) | 0.065 (2) | 0.0181 (18) | 0.0005 (16) | −0.0209 (17) |
N31 | 0.0445 (12) | 0.0460 (12) | 0.0375 (12) | 0.0039 (10) | −0.0017 (9) | −0.0063 (9) |
N32 | 0.0472 (13) | 0.0491 (13) | 0.0411 (12) | 0.0104 (10) | −0.0011 (10) | −0.0058 (10) |
C33 | 0.0415 (14) | 0.0466 (15) | 0.0399 (14) | 0.0034 (11) | −0.0016 (11) | −0.0070 (11) |
C34 | 0.0405 (13) | 0.0416 (14) | 0.0402 (14) | 0.0016 (11) | −0.0006 (11) | −0.0093 (11) |
C35 | 0.0400 (13) | 0.0393 (13) | 0.0442 (14) | 0.0031 (11) | −0.0019 (11) | −0.0073 (11) |
C311 | 0.0474 (15) | 0.0425 (14) | 0.0391 (14) | −0.0045 (11) | −0.0006 (11) | −0.0063 (11) |
C312 | 0.0474 (16) | 0.080 (2) | 0.0448 (16) | −0.0008 (15) | −0.0030 (13) | −0.0073 (15) |
C313 | 0.068 (2) | 0.082 (2) | 0.0475 (18) | −0.0024 (18) | −0.0128 (15) | −0.0033 (16) |
C314 | 0.088 (2) | 0.0583 (19) | 0.0422 (16) | −0.0131 (17) | 0.0016 (16) | −0.0058 (14) |
C315 | 0.071 (2) | 0.064 (2) | 0.0561 (19) | −0.0086 (16) | 0.0194 (16) | −0.0115 (15) |
C316 | 0.0483 (16) | 0.0547 (17) | 0.0538 (17) | 0.0009 (13) | 0.0028 (13) | −0.0084 (13) |
C331 | 0.0629 (19) | 0.0568 (18) | 0.0476 (16) | 0.0169 (15) | 0.0012 (14) | −0.0034 (13) |
O351 | 0.0560 (12) | 0.0400 (10) | 0.0550 (12) | 0.0056 (9) | −0.0027 (9) | −0.0010 (8) |
C351 | 0.0598 (18) | 0.0475 (16) | 0.0546 (17) | 0.0006 (13) | −0.0104 (14) | −0.0086 (13) |
C352 | 0.0560 (17) | 0.0508 (16) | 0.0369 (14) | 0.0199 (13) | −0.0108 (12) | −0.0100 (12) |
C353 | 0.0554 (18) | 0.0525 (17) | 0.067 (2) | −0.0013 (14) | −0.0014 (15) | −0.0078 (14) |
C354 | 0.064 (2) | 0.0564 (19) | 0.078 (2) | −0.0105 (16) | −0.0048 (17) | −0.0048 (16) |
C355 | 0.0440 (17) | 0.097 (3) | 0.064 (2) | −0.0023 (17) | −0.0037 (14) | −0.0123 (18) |
C356 | 0.0541 (19) | 0.099 (3) | 0.061 (2) | 0.009 (2) | −0.0034 (16) | −0.0163 (19) |
C357 | 0.077 (3) | 0.087 (3) | 0.065 (2) | 0.025 (2) | −0.0158 (18) | −0.0249 (19) |
C358 | 0.084 (3) | 0.062 (2) | 0.065 (2) | 0.0198 (18) | −0.0179 (18) | −0.0212 (16) |
C359 | 0.0627 (19) | 0.067 (2) | 0.0421 (16) | 0.0060 (15) | −0.0094 (13) | −0.0100 (14) |
C360 | 0.0479 (15) | 0.0489 (15) | 0.0351 (13) | 0.0018 (12) | −0.0072 (11) | −0.0094 (11) |
Geometric parameters (Å, º) top C1—O1 | 1.233 (3) | C311—C312 | 1.382 (4) |
C1—C2 | 1.472 (4) | C312—C313 | 1.384 (4) |
C1—C11 | 1.478 (4) | C312—H312 | 0.9300 |
C2—C3 | 1.330 (4) | C313—C314 | 1.367 (5) |
C2—H2 | 0.9300 | C313—H313 | 0.9300 |
C3—C34 | 1.446 (4) | C314—C315 | 1.369 (5) |
C3—H3 | 0.9300 | C314—H314 | 0.9300 |
C11—C12 | 1.385 (4) | C315—C316 | 1.390 (4) |
C11—C16 | 1.399 (4) | C315—H315 | 0.9300 |
C12—C13 | 1.384 (4) | C316—H316 | 0.9300 |
C12—H12 | 0.9300 | C331—H33A | 0.9600 |
C13—C14 | 1.387 (4) | C331—H33B | 0.9600 |
C13—H13 | 0.9300 | C331—H33C | 0.9600 |
C14—O14 | 1.363 (3) | O351—C352 | 1.435 (3) |
C14—C15 | 1.384 (4) | C351—C352 | 1.356 (4) |
C15—C16 | 1.370 (4) | C351—C360 | 1.434 (4) |
C15—H15 | 0.9300 | C351—H351 | 0.9300 |
C16—H16 | 0.9300 | C352—C353 | 1.391 (4) |
O14—C17 | 1.423 (3) | C353—C354 | 1.382 (5) |
C17—C18 | 1.459 (4) | C353—H353 | 0.9300 |
C17—H17A | 0.9700 | C354—C359 | 1.376 (5) |
C17—H17B | 0.9700 | C354—H354 | 0.9300 |
C18—C19 | 1.161 (4) | C355—C356 | 1.350 (5) |
C19—H19 | 0.9300 | C355—C359 | 1.444 (4) |
N31—C35 | 1.351 (3) | C355—H355 | 0.9300 |
N31—N32 | 1.382 (3) | C356—C357 | 1.397 (6) |
N31—C311 | 1.427 (3) | C356—H356 | 0.9300 |
N32—C33 | 1.322 (3) | C357—C358 | 1.331 (5) |
C33—C34 | 1.420 (4) | C357—H357 | 0.9300 |
C33—C331 | 1.494 (4) | C358—C360 | 1.385 (4) |
C34—C35 | 1.378 (4) | C358—H358 | 0.9300 |
C35—O351 | 1.365 (3) | C359—C360 | 1.430 (4) |
C311—C316 | 1.372 (4) | | |
| | | |
O1—C1—C2 | 121.3 (2) | C311—C312—C313 | 119.2 (3) |
O1—C1—C11 | 120.0 (2) | C311—C312—H312 | 120.4 |
C2—C1—C11 | 118.8 (2) | C313—C312—H312 | 120.4 |
C3—C2—C1 | 122.2 (3) | C314—C313—C312 | 121.2 (3) |
C3—C2—H2 | 118.9 | C314—C313—H313 | 119.4 |
C1—C2—H2 | 118.9 | C312—C313—H313 | 119.4 |
C2—C3—C34 | 127.7 (3) | C313—C314—C315 | 119.0 (3) |
C2—C3—H3 | 116.2 | C313—C314—H314 | 120.5 |
C34—C3—H3 | 116.2 | C315—C314—H314 | 120.5 |
C12—C11—C16 | 117.6 (2) | C314—C315—C316 | 121.2 (3) |
C12—C11—C1 | 119.5 (2) | C314—C315—H315 | 119.4 |
C16—C11—C1 | 122.8 (2) | C316—C315—H315 | 119.4 |
C13—C12—C11 | 121.9 (2) | C311—C316—C315 | 119.1 (3) |
C13—C12—H12 | 119.0 | C311—C316—H316 | 120.4 |
C11—C12—H12 | 119.0 | C315—C316—H316 | 120.4 |
C12—C13—C14 | 119.1 (3) | C33—C331—H33A | 109.5 |
C12—C13—H13 | 120.5 | C33—C331—H33B | 109.5 |
C14—C13—H13 | 120.5 | H33A—C331—H33B | 109.5 |
O14—C14—C15 | 115.7 (2) | C33—C331—H33C | 109.5 |
O14—C14—C13 | 124.4 (2) | H33A—C331—H33C | 109.5 |
C15—C14—C13 | 119.9 (2) | H33B—C331—H33C | 109.5 |
C16—C15—C14 | 120.2 (2) | C35—O351—C352 | 118.0 (2) |
C16—C15—H15 | 119.9 | C352—C351—C360 | 119.9 (3) |
C14—C15—H15 | 119.9 | C352—C351—H351 | 120.0 |
C15—C16—C11 | 121.2 (3) | C360—C351—H351 | 120.0 |
C15—C16—H16 | 119.4 | C351—C352—C353 | 122.5 (3) |
C11—C16—H16 | 119.4 | C351—C352—O351 | 116.0 (3) |
C14—O14—C17 | 117.5 (2) | C353—C352—O351 | 121.5 (2) |
O14—C17—C18 | 109.2 (2) | C354—C353—C352 | 118.9 (3) |
O14—C17—H17A | 109.8 | C354—C353—H353 | 120.6 |
C18—C17—H17A | 109.8 | C352—C353—H353 | 120.6 |
O14—C17—H17B | 109.8 | C359—C354—C353 | 121.0 (3) |
C18—C17—H17B | 109.8 | C359—C354—H354 | 119.5 |
H17A—C17—H17B | 108.3 | C353—C354—H354 | 119.5 |
C19—C18—C17 | 177.5 (4) | C356—C355—C359 | 118.8 (4) |
C18—C19—H19 | 180.0 | C356—C355—H355 | 120.6 |
C35—N31—N32 | 110.6 (2) | C359—C355—H355 | 120.6 |
C35—N31—C311 | 129.4 (2) | C355—C356—C357 | 122.7 (3) |
N32—N31—C311 | 119.9 (2) | C355—C356—H356 | 118.6 |
C33—N32—N31 | 104.8 (2) | C357—C356—H356 | 118.6 |
N32—C33—C34 | 112.5 (2) | C358—C357—C356 | 119.3 (4) |
N32—C33—C331 | 120.9 (2) | C358—C357—H357 | 120.4 |
C34—C33—C331 | 126.6 (2) | C356—C357—H357 | 120.4 |
C35—C34—C33 | 103.3 (2) | C357—C358—C360 | 122.4 (4) |
C35—C34—C3 | 130.6 (2) | C357—C358—H358 | 118.8 |
C33—C34—C3 | 126.0 (2) | C360—C358—H358 | 118.8 |
N31—C35—O351 | 119.2 (2) | C354—C359—C360 | 120.8 (3) |
N31—C35—C34 | 108.7 (2) | C354—C359—C355 | 121.6 (3) |
O351—C35—C34 | 131.6 (2) | C360—C359—C355 | 117.6 (3) |
C316—C311—C312 | 120.3 (3) | C358—C360—C359 | 119.3 (3) |
C316—C311—N31 | 119.5 (2) | C358—C360—C351 | 123.7 (3) |
C312—C311—N31 | 120.2 (2) | C359—C360—C351 | 117.0 (3) |
| | | |
O1—C1—C2—C3 | 11.5 (5) | C3—C34—C35—O351 | 6.6 (5) |
C11—C1—C2—C3 | −169.4 (3) | C35—N31—C311—C316 | 140.2 (3) |
C1—C2—C3—C34 | −179.5 (3) | N32—N31—C311—C316 | −39.0 (4) |
O1—C1—C11—C12 | 16.3 (4) | C35—N31—C311—C312 | −40.9 (4) |
C2—C1—C11—C12 | −162.8 (3) | N32—N31—C311—C312 | 139.9 (3) |
O1—C1—C11—C16 | −162.8 (3) | C316—C311—C312—C313 | −1.7 (5) |
C2—C1—C11—C16 | 18.0 (4) | N31—C311—C312—C313 | 179.4 (3) |
C16—C11—C12—C13 | −1.1 (4) | C311—C312—C313—C314 | 1.3 (5) |
C1—C11—C12—C13 | 179.7 (3) | C312—C313—C314—C315 | 0.1 (5) |
C11—C12—C13—C14 | 1.3 (5) | C313—C314—C315—C316 | −1.1 (5) |
C12—C13—C14—O14 | 179.6 (3) | C312—C311—C316—C315 | 0.7 (4) |
C12—C13—C14—C15 | 0.1 (5) | N31—C311—C316—C315 | 179.6 (3) |
O14—C14—C15—C16 | 179.0 (3) | C314—C315—C316—C311 | 0.7 (5) |
C13—C14—C15—C16 | −1.5 (5) | N31—C35—O351—C352 | 118.5 (3) |
C14—C15—C16—C11 | 1.6 (5) | C34—C35—O351—C352 | −70.6 (4) |
C12—C11—C16—C15 | −0.3 (5) | C360—C351—C352—C353 | 1.1 (4) |
C1—C11—C16—C15 | 178.8 (3) | C360—C351—C352—O351 | 179.0 (2) |
C15—C14—O14—C17 | 179.1 (3) | C35—O351—C352—C351 | 161.8 (2) |
C13—C14—O14—C17 | −0.4 (4) | C35—O351—C352—C353 | −20.2 (4) |
C14—O14—C17—C18 | −174.7 (3) | C351—C352—C353—C354 | −0.5 (5) |
C35—N31—N32—C33 | 1.2 (3) | O351—C352—C353—C354 | −178.4 (3) |
C311—N31—N32—C33 | −179.5 (2) | C352—C353—C354—C359 | −0.2 (5) |
N31—N32—C33—C34 | −1.3 (3) | C359—C355—C356—C357 | 0.2 (5) |
N31—N32—C33—C331 | 179.5 (3) | C355—C356—C357—C358 | −0.2 (6) |
N32—C33—C34—C35 | 0.8 (3) | C356—C357—C358—C360 | 0.1 (5) |
C331—C33—C34—C35 | −180.0 (3) | C353—C354—C359—C360 | 0.5 (5) |
N32—C33—C34—C3 | −177.6 (3) | C353—C354—C359—C355 | −179.4 (3) |
C331—C33—C34—C3 | 1.6 (5) | C356—C355—C359—C354 | 179.8 (3) |
C2—C3—C34—C35 | −9.1 (5) | C356—C355—C359—C360 | 0.0 (5) |
C2—C3—C34—C33 | 168.9 (3) | C357—C358—C360—C359 | 0.1 (5) |
N32—N31—C35—O351 | 172.1 (2) | C357—C358—C360—C351 | −179.9 (3) |
C311—N31—C35—O351 | −7.1 (4) | C354—C359—C360—C358 | −180.0 (3) |
N32—N31—C35—C34 | −0.7 (3) | C355—C359—C360—C358 | −0.2 (4) |
C311—N31—C35—C34 | −180.0 (3) | C354—C359—C360—C351 | 0.0 (4) |
C33—C34—C35—N31 | −0.1 (3) | C355—C359—C360—C351 | 179.9 (3) |
C3—C34—C35—N31 | 178.3 (3) | C352—C351—C360—C358 | 179.2 (3) |
C33—C34—C35—O351 | −171.7 (3) | C352—C351—C360—C359 | −0.8 (4) |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19···O1i | 0.93 | 2.32 | 3.233 (5) | 165 |
C353—H353···Cg1ii | 0.93 | 2.86 | 3.708 (3) | 152 |
Symmetry codes: (i) x−1, y+1, z; (ii) −x+1, −y, −z+1. |
1-(4-Azidophenyl)-3-[3-methyl-5-(2-methylphenoxy)-1-phenyl-1
H-pyrazol-4-yl]prop-2-en-1-one (IIa)
top Crystal data top C26H21N5O2 | Z = 2 |
Mr = 435.48 | F(000) = 456 |
Triclinic, P1 | Dx = 1.255 Mg m−3 |
a = 9.8432 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.7441 (7) Å | Cell parameters from 4051 reflections |
c = 12.3005 (7) Å | θ = 3.2–25.1° |
α = 114.120 (2)° | µ = 0.08 mm−1 |
β = 111.139 (2)° | T = 297 K |
γ = 96.537 (2)° | Block, brown |
V = 1152.06 (12) Å3 | 0.20 × 0.20 × 0.18 mm |
Data collection top Bruker APEXII diffractometer | 4050 independent reflections |
Radiation source: fine focussealed tube | 2957 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
φ and ω scans | θmax = 25.1°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −11→11 |
Tmin = 0.868, Tmax = 0.985 | k = −13→13 |
17379 measured reflections | l = −14→14 |
Refinement top Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.4937P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.148 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.19 e Å−3 |
4050 reflections | Δρmin = −0.21 e Å−3 |
301 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.179 (14) |
Primary atom site location: dual | |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.6025 (2) | 0.4013 (2) | 0.8884 (2) | 0.0473 (5) | |
O1 | 0.66955 (18) | 0.33036 (17) | 0.9214 (2) | 0.0733 (5) | |
C2 | 0.4353 (2) | 0.3679 (2) | 0.8333 (2) | 0.0465 (5) | |
H2 | 0.3862 | 0.4229 | 0.8090 | 0.056* | |
C3 | 0.3533 (2) | 0.2591 (2) | 0.8180 (2) | 0.0459 (5) | |
H3 | 0.4098 | 0.2111 | 0.8489 | 0.055* | |
C11 | 0.6922 (2) | 0.52181 (19) | 0.90264 (19) | 0.0415 (5) | |
C12 | 0.8501 (2) | 0.5646 (2) | 0.9800 (2) | 0.0462 (5) | |
H12 | 0.8940 | 0.5193 | 1.0229 | 0.055* | |
C13 | 0.9434 (2) | 0.6725 (2) | 0.9947 (2) | 0.0471 (5) | |
H13 | 1.0487 | 0.6991 | 1.0463 | 0.057* | |
C14 | 0.8781 (2) | 0.7402 (2) | 0.9317 (2) | 0.0480 (5) | |
C15 | 0.7212 (2) | 0.7008 (2) | 0.8556 (2) | 0.0557 (6) | |
H15 | 0.6776 | 0.7473 | 0.8142 | 0.067* | |
C16 | 0.6292 (2) | 0.5923 (2) | 0.8413 (2) | 0.0519 (5) | |
H16 | 0.5239 | 0.5662 | 0.7900 | 0.062* | |
N14 | 0.9637 (2) | 0.85203 (19) | 0.9401 (2) | 0.0656 (6) | |
N15 | 1.1040 (3) | 0.8907 (2) | 1.0131 (2) | 0.0693 (6) | |
N16 | 1.2312 (3) | 0.9373 (3) | 1.0751 (3) | 0.1029 (10) | |
N31 | −0.06215 (19) | 0.16164 (16) | 0.66089 (17) | 0.0471 (4) | |
N32 | −0.0398 (2) | 0.05926 (17) | 0.68563 (18) | 0.0511 (5) | |
C33 | 0.1109 (2) | 0.0864 (2) | 0.7460 (2) | 0.0469 (5) | |
C34 | 0.1897 (2) | 0.20522 (19) | 0.7604 (2) | 0.0433 (5) | |
C35 | 0.0727 (2) | 0.24912 (19) | 0.7052 (2) | 0.0442 (5) | |
C311 | −0.2141 (2) | 0.1559 (2) | 0.5825 (2) | 0.0471 (5) | |
C312 | −0.2664 (3) | 0.2627 (2) | 0.6210 (3) | 0.0611 (6) | |
H312 | −0.2034 | 0.3406 | 0.6988 | 0.073* | |
C313 | −0.4142 (3) | 0.2524 (3) | 0.5418 (3) | 0.0711 (7) | |
H313 | −0.4506 | 0.3239 | 0.5667 | 0.085* | |
C314 | −0.5075 (3) | 0.1371 (3) | 0.4269 (3) | 0.0735 (7) | |
H314 | −0.6063 | 0.1312 | 0.3741 | 0.088* | |
C315 | −0.4550 (3) | 0.0308 (3) | 0.3900 (3) | 0.0719 (7) | |
H315 | −0.5184 | −0.0472 | 0.3124 | 0.086* | |
C316 | −0.3082 (3) | 0.0397 (2) | 0.4679 (2) | 0.0578 (6) | |
H316 | −0.2728 | −0.0324 | 0.4433 | 0.069* | |
C331 | 0.1796 (3) | −0.0017 (2) | 0.7929 (3) | 0.0645 (6) | |
H33A | 0.1019 | −0.0622 | 0.7896 | 0.097* | |
H33B | 0.2587 | 0.0498 | 0.8829 | 0.097* | |
H33C | 0.2225 | −0.0495 | 0.7365 | 0.097* | |
O351 | 0.07382 (17) | 0.36198 (13) | 0.69897 (15) | 0.0522 (4) | |
C351 | 0.1292 (2) | 0.38472 (19) | 0.6168 (2) | 0.0434 (5) | |
C352 | 0.1738 (2) | 0.5152 (2) | 0.6479 (2) | 0.0522 (5) | |
C353 | 0.2282 (3) | 0.5403 (3) | 0.5678 (3) | 0.0690 (7) | |
H353 | 0.2599 | 0.6264 | 0.5855 | 0.083* | |
C354 | 0.2367 (3) | 0.4418 (3) | 0.4633 (3) | 0.0780 (8) | |
H354 | 0.2741 | 0.4618 | 0.4116 | 0.094* | |
C355 | 0.1900 (3) | 0.3135 (3) | 0.4344 (3) | 0.0699 (7) | |
H355 | 0.1952 | 0.2469 | 0.3630 | 0.084* | |
C356 | 0.1353 (3) | 0.2839 (2) | 0.5119 (2) | 0.0547 (6) | |
H356 | 0.1032 | 0.1976 | 0.4934 | 0.066* | |
C357 | 0.1657 (4) | 0.6222 (2) | 0.7625 (3) | 0.0777 (8) | |
H35A | 0.1876 | 0.7031 | 0.7608 | 0.116* | |
H35B | 0.2393 | 0.6314 | 0.8446 | 0.116* | |
H35C | 0.0649 | 0.6010 | 0.7559 | 0.116* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0414 (11) | 0.0494 (12) | 0.0507 (12) | 0.0123 (9) | 0.0182 (9) | 0.0266 (10) |
O1 | 0.0471 (9) | 0.0702 (11) | 0.1105 (14) | 0.0170 (8) | 0.0231 (9) | 0.0615 (11) |
C2 | 0.0378 (11) | 0.0456 (11) | 0.0520 (12) | 0.0110 (9) | 0.0178 (9) | 0.0227 (9) |
C3 | 0.0441 (11) | 0.0436 (11) | 0.0474 (11) | 0.0122 (9) | 0.0214 (9) | 0.0194 (9) |
C11 | 0.0362 (10) | 0.0439 (11) | 0.0414 (10) | 0.0110 (8) | 0.0166 (8) | 0.0192 (9) |
C12 | 0.0382 (11) | 0.0490 (12) | 0.0531 (12) | 0.0147 (9) | 0.0193 (9) | 0.0270 (10) |
C13 | 0.0364 (10) | 0.0470 (11) | 0.0531 (12) | 0.0111 (9) | 0.0171 (9) | 0.0231 (10) |
C14 | 0.0467 (12) | 0.0430 (11) | 0.0500 (12) | 0.0074 (9) | 0.0213 (9) | 0.0207 (9) |
C15 | 0.0478 (12) | 0.0569 (13) | 0.0614 (13) | 0.0119 (10) | 0.0157 (10) | 0.0366 (11) |
C16 | 0.0375 (11) | 0.0573 (13) | 0.0544 (12) | 0.0091 (9) | 0.0127 (9) | 0.0298 (11) |
N14 | 0.0517 (12) | 0.0558 (12) | 0.0775 (14) | 0.0002 (9) | 0.0136 (10) | 0.0397 (11) |
N15 | 0.0585 (14) | 0.0588 (13) | 0.0799 (14) | 0.0032 (10) | 0.0187 (12) | 0.0388 (11) |
N16 | 0.0565 (15) | 0.0956 (19) | 0.130 (2) | −0.0054 (13) | 0.0099 (15) | 0.0668 (18) |
N31 | 0.0417 (9) | 0.0424 (9) | 0.0551 (10) | 0.0076 (7) | 0.0203 (8) | 0.0245 (8) |
N32 | 0.0485 (11) | 0.0443 (10) | 0.0612 (11) | 0.0080 (8) | 0.0232 (9) | 0.0291 (9) |
C33 | 0.0492 (12) | 0.0416 (11) | 0.0514 (12) | 0.0091 (9) | 0.0252 (10) | 0.0228 (9) |
C34 | 0.0422 (11) | 0.0403 (10) | 0.0463 (11) | 0.0090 (8) | 0.0219 (9) | 0.0191 (9) |
C35 | 0.0463 (11) | 0.0375 (10) | 0.0512 (11) | 0.0100 (9) | 0.0256 (9) | 0.0212 (9) |
C311 | 0.0418 (11) | 0.0519 (12) | 0.0499 (11) | 0.0116 (9) | 0.0236 (9) | 0.0246 (10) |
C312 | 0.0542 (14) | 0.0539 (14) | 0.0674 (15) | 0.0149 (11) | 0.0269 (12) | 0.0235 (12) |
C313 | 0.0613 (16) | 0.0702 (17) | 0.0894 (19) | 0.0309 (13) | 0.0369 (15) | 0.0399 (15) |
C314 | 0.0505 (14) | 0.090 (2) | 0.0758 (17) | 0.0230 (14) | 0.0233 (13) | 0.0408 (16) |
C315 | 0.0518 (14) | 0.0762 (18) | 0.0609 (15) | 0.0108 (13) | 0.0165 (12) | 0.0197 (13) |
C316 | 0.0495 (13) | 0.0558 (13) | 0.0584 (13) | 0.0142 (10) | 0.0248 (11) | 0.0193 (11) |
C331 | 0.0663 (15) | 0.0588 (14) | 0.0765 (16) | 0.0175 (12) | 0.0304 (13) | 0.0418 (13) |
O351 | 0.0583 (9) | 0.0427 (8) | 0.0694 (10) | 0.0185 (7) | 0.0374 (8) | 0.0310 (7) |
C351 | 0.0370 (10) | 0.0452 (11) | 0.0485 (11) | 0.0107 (8) | 0.0155 (9) | 0.0269 (9) |
C352 | 0.0491 (12) | 0.0476 (12) | 0.0575 (13) | 0.0125 (10) | 0.0163 (10) | 0.0307 (10) |
C353 | 0.0742 (17) | 0.0632 (16) | 0.0749 (17) | 0.0127 (13) | 0.0264 (14) | 0.0464 (14) |
C354 | 0.089 (2) | 0.091 (2) | 0.0798 (18) | 0.0248 (16) | 0.0440 (16) | 0.0589 (17) |
C355 | 0.0818 (18) | 0.0828 (18) | 0.0608 (15) | 0.0339 (15) | 0.0380 (14) | 0.0411 (14) |
C356 | 0.0580 (13) | 0.0497 (12) | 0.0547 (13) | 0.0166 (10) | 0.0219 (11) | 0.0267 (11) |
C357 | 0.104 (2) | 0.0467 (14) | 0.0809 (18) | 0.0248 (14) | 0.0384 (16) | 0.0318 (13) |
Geometric parameters (Å, º) top C1—O1 | 1.226 (3) | C311—C316 | 1.380 (3) |
C1—C2 | 1.468 (3) | C312—C313 | 1.386 (3) |
C1—C11 | 1.488 (3) | C312—H312 | 0.9300 |
C2—C3 | 1.334 (3) | C313—C314 | 1.375 (4) |
C2—H2 | 0.9300 | C313—H313 | 0.9300 |
C3—C34 | 1.440 (3) | C314—C315 | 1.373 (4) |
C3—H3 | 0.9300 | C314—H314 | 0.9300 |
C11—C16 | 1.389 (3) | C315—C316 | 1.379 (3) |
C11—C12 | 1.392 (3) | C315—H315 | 0.9300 |
C12—C13 | 1.382 (3) | C316—H316 | 0.9300 |
C12—H12 | 0.9300 | C331—H33A | 0.9600 |
C13—C14 | 1.380 (3) | C331—H33B | 0.9600 |
C13—H13 | 0.9300 | C331—H33C | 0.9600 |
C14—C15 | 1.384 (3) | O351—C351 | 1.405 (2) |
C14—N14 | 1.422 (3) | C351—C356 | 1.377 (3) |
C15—C16 | 1.383 (3) | C351—C352 | 1.391 (3) |
C15—H15 | 0.9300 | C352—C353 | 1.389 (3) |
C16—H16 | 0.9300 | C352—C357 | 1.493 (3) |
N14—N15 | 1.245 (3) | C353—C354 | 1.372 (4) |
N15—N16 | 1.124 (3) | C353—H353 | 0.9300 |
N31—C35 | 1.351 (3) | C354—C355 | 1.377 (4) |
N31—N32 | 1.378 (2) | C354—H354 | 0.9300 |
N31—C311 | 1.433 (3) | C355—C356 | 1.385 (3) |
N32—C33 | 1.326 (3) | C355—H355 | 0.9300 |
C33—C34 | 1.426 (3) | C356—H356 | 0.9300 |
C33—C331 | 1.493 (3) | C357—H35A | 0.9600 |
C34—C35 | 1.382 (3) | C357—H35B | 0.9600 |
C35—O351 | 1.358 (2) | C357—H35C | 0.9600 |
C311—C312 | 1.379 (3) | | |
| | | |
O1—C1—C2 | 120.91 (19) | C311—C312—H312 | 120.5 |
O1—C1—C11 | 119.34 (19) | C313—C312—H312 | 120.5 |
C2—C1—C11 | 119.74 (18) | C314—C313—C312 | 120.5 (2) |
C3—C2—C1 | 120.4 (2) | C314—C313—H313 | 119.8 |
C3—C2—H2 | 119.8 | C312—C313—H313 | 119.8 |
C1—C2—H2 | 119.8 | C315—C314—C313 | 120.1 (2) |
C2—C3—C34 | 129.2 (2) | C315—C314—H314 | 119.9 |
C2—C3—H3 | 115.4 | C313—C314—H314 | 119.9 |
C34—C3—H3 | 115.4 | C314—C315—C316 | 120.0 (2) |
C16—C11—C12 | 118.03 (19) | C314—C315—H315 | 120.0 |
C16—C11—C1 | 124.29 (18) | C316—C315—H315 | 120.0 |
C12—C11—C1 | 117.66 (18) | C315—C316—C311 | 119.9 (2) |
C13—C12—C11 | 121.75 (19) | C315—C316—H316 | 120.1 |
C13—C12—H12 | 119.1 | C311—C316—H316 | 120.1 |
C11—C12—H12 | 119.1 | C33—C331—H33A | 109.5 |
C14—C13—C12 | 119.10 (19) | C33—C331—H33B | 109.5 |
C14—C13—H13 | 120.5 | H33A—C331—H33B | 109.5 |
C12—C13—H13 | 120.5 | C33—C331—H33C | 109.5 |
C13—C14—C15 | 120.35 (19) | H33A—C331—H33C | 109.5 |
C13—C14—N14 | 123.5 (2) | H33B—C331—H33C | 109.5 |
C15—C14—N14 | 116.1 (2) | C35—O351—C351 | 119.16 (15) |
C16—C15—C14 | 120.0 (2) | C356—C351—C352 | 123.0 (2) |
C16—C15—H15 | 120.0 | C356—C351—O351 | 121.83 (18) |
C14—C15—H15 | 120.0 | C352—C351—O351 | 115.11 (18) |
C15—C16—C11 | 120.80 (19) | C353—C352—C351 | 116.3 (2) |
C15—C16—H16 | 119.6 | C353—C352—C357 | 122.0 (2) |
C11—C16—H16 | 119.6 | C351—C352—C357 | 121.7 (2) |
N15—N14—C14 | 116.1 (2) | C354—C353—C352 | 121.9 (2) |
N16—N15—N14 | 171.8 (3) | C354—C353—H353 | 119.1 |
C35—N31—N32 | 111.11 (17) | C352—C353—H353 | 119.1 |
C35—N31—C311 | 129.06 (18) | C353—C354—C355 | 120.3 (2) |
N32—N31—C311 | 119.38 (16) | C353—C354—H354 | 119.8 |
C33—N32—N31 | 104.82 (16) | C355—C354—H354 | 119.8 |
N32—C33—C34 | 112.21 (18) | C354—C355—C356 | 119.8 (3) |
N32—C33—C331 | 120.41 (18) | C354—C355—H355 | 120.1 |
C34—C33—C331 | 127.4 (2) | C356—C355—H355 | 120.1 |
C35—C34—C33 | 103.40 (17) | C351—C356—C355 | 118.7 (2) |
C35—C34—C3 | 131.01 (19) | C351—C356—H356 | 120.7 |
C33—C34—C3 | 125.58 (19) | C355—C356—H356 | 120.7 |
N31—C35—O351 | 119.52 (18) | C352—C357—H35A | 109.5 |
N31—C35—C34 | 108.45 (18) | C352—C357—H35B | 109.5 |
O351—C35—C34 | 131.82 (18) | H35A—C357—H35B | 109.5 |
C312—C311—C316 | 120.5 (2) | C352—C357—H35C | 109.5 |
C312—C311—N31 | 121.14 (19) | H35A—C357—H35C | 109.5 |
C316—C311—N31 | 118.35 (19) | H35B—C357—H35C | 109.5 |
C311—C312—C313 | 119.0 (2) | | |
| | | |
O1—C1—C2—C3 | −0.1 (3) | C311—N31—C35—C34 | −171.57 (19) |
C11—C1—C2—C3 | 178.86 (19) | C33—C34—C35—N31 | −0.9 (2) |
C1—C2—C3—C34 | −176.53 (19) | C3—C34—C35—N31 | 178.1 (2) |
O1—C1—C11—C16 | 164.2 (2) | C33—C34—C35—O351 | 173.7 (2) |
C2—C1—C11—C16 | −14.8 (3) | C3—C34—C35—O351 | −7.3 (4) |
O1—C1—C11—C12 | −14.2 (3) | C35—N31—C311—C312 | −53.4 (3) |
C2—C1—C11—C12 | 166.82 (18) | N32—N31—C311—C312 | 135.1 (2) |
C16—C11—C12—C13 | −1.0 (3) | C35—N31—C311—C316 | 127.5 (2) |
C1—C11—C12—C13 | 177.49 (19) | N32—N31—C311—C316 | −44.0 (3) |
C11—C12—C13—C14 | 0.4 (3) | C316—C311—C312—C313 | −0.9 (4) |
C12—C13—C14—C15 | 0.4 (3) | N31—C311—C312—C313 | −180.0 (2) |
C12—C13—C14—N14 | −179.8 (2) | C311—C312—C313—C314 | 0.2 (4) |
C13—C14—C15—C16 | −0.7 (3) | C312—C313—C314—C315 | 0.4 (4) |
N14—C14—C15—C16 | 179.5 (2) | C313—C314—C315—C316 | −0.3 (4) |
C14—C15—C16—C11 | 0.1 (4) | C314—C315—C316—C311 | −0.4 (4) |
C12—C11—C16—C15 | 0.7 (3) | C312—C311—C316—C315 | 1.0 (3) |
C1—C11—C16—C15 | −177.7 (2) | N31—C311—C316—C315 | −179.9 (2) |
C13—C14—N14—N15 | −2.7 (3) | N31—C35—O351—C351 | −115.8 (2) |
C15—C14—N14—N15 | 177.1 (2) | C34—C35—O351—C351 | 70.1 (3) |
C35—N31—N32—C33 | 0.1 (2) | C35—O351—C351—C356 | 21.6 (3) |
C311—N31—N32—C33 | 173.08 (17) | C35—O351—C351—C352 | −159.61 (18) |
N31—N32—C33—C34 | −0.7 (2) | C356—C351—C352—C353 | −1.0 (3) |
N31—N32—C33—C331 | 177.90 (19) | O351—C351—C352—C353 | −179.69 (19) |
N32—C33—C34—C35 | 1.0 (2) | C356—C351—C352—C357 | 180.0 (2) |
C331—C33—C34—C35 | −177.5 (2) | O351—C351—C352—C357 | 1.3 (3) |
N32—C33—C34—C3 | −178.03 (18) | C351—C352—C353—C354 | 0.4 (4) |
C331—C33—C34—C3 | 3.5 (3) | C357—C352—C353—C354 | 179.4 (3) |
C2—C3—C34—C35 | 0.2 (4) | C352—C353—C354—C355 | 0.3 (4) |
C2—C3—C34—C33 | 179.0 (2) | C353—C354—C355—C356 | −0.4 (4) |
N32—N31—C35—O351 | −174.87 (17) | C352—C351—C356—C355 | 0.8 (3) |
C311—N31—C35—O351 | 13.1 (3) | O351—C351—C356—C355 | 179.5 (2) |
N32—N31—C35—C34 | 0.5 (2) | C354—C355—C356—C351 | −0.1 (4) |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C357—H35B···O1i | 0.96 | 2.51 | 3.396 (4) | 154 |
Symmetry code: (i) −x+1, −y+1, −z+2. |
1-(4-Azidophenyl)-3-[5-(2,4-dichlorophenoxy)-3-methyl-1-phenyl-1
H-pyrazol-4-yl]prop-2-en-1-one (IId)
top Crystal data top C25H17Cl2N5O2 | F(000) = 2016 |
Mr = 490.33 | Dx = 1.377 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 28.1916 (17) Å | Cell parameters from 4176 reflections |
b = 8.0537 (5) Å | θ = 2.9–25.0° |
c = 22.0446 (12) Å | µ = 0.31 mm−1 |
β = 109.070 (1)° | T = 297 K |
V = 4730.5 (5) Å3 | Block, colourless |
Z = 8 | 0.18 × 0.15 × 0.15 mm |
Data collection top Bruker APEXII diffractometer | 4174 independent reflections |
Radiation source: fine focussealed tube | 3181 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
φ and ω scans | θmax = 25.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −33→33 |
Tmin = 0.881, Tmax = 0.955 | k = −9→9 |
31508 measured reflections | l = −26→21 |
Refinement top Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.086 | w = 1/[σ2(Fo2) + (0.0265P)2 + 10.5248P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.155 | (Δ/σ)max < 0.001 |
S = 1.36 | Δρmax = 0.21 e Å−3 |
4174 reflections | Δρmin = −0.23 e Å−3 |
382 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
291 restraints | Extinction coefficient: 0.0018 (3) |
Primary atom site location: dual | |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.42395 (14) | 0.7441 (5) | 0.5060 (2) | 0.0497 (10) | |
O1 | 0.42708 (11) | 0.8068 (4) | 0.55744 (16) | 0.0731 (10) | |
C2 | 0.46893 (14) | 0.7129 (5) | 0.48791 (19) | 0.0509 (10) | |
H2 | 0.4658 | 0.6524 | 0.4509 | 0.061* | |
C3 | 0.51394 (14) | 0.7686 (5) | 0.52294 (19) | 0.0505 (10) | |
H3 | 0.5154 | 0.8257 | 0.5602 | 0.061* | |
C11 | 0.37362 (14) | 0.6992 (5) | 0.45998 (19) | 0.0472 (10) | |
C12 | 0.33110 (15) | 0.7460 (6) | 0.4740 (2) | 0.0637 (12) | |
H12 | 0.3346 | 0.8036 | 0.5118 | 0.076* | |
C13 | 0.28398 (17) | 0.7089 (7) | 0.4332 (2) | 0.0741 (14) | |
H13 | 0.2558 | 0.7415 | 0.4433 | 0.089* | |
C14 | 0.27855 (15) | 0.6239 (6) | 0.3778 (2) | 0.0624 (12) | |
C15 | 0.31991 (16) | 0.5748 (6) | 0.3626 (2) | 0.0665 (13) | |
H15 | 0.3162 | 0.5164 | 0.3250 | 0.080* | |
C16 | 0.36695 (15) | 0.6129 (6) | 0.4038 (2) | 0.0616 (12) | |
H16 | 0.3950 | 0.5796 | 0.3935 | 0.074* | |
N14 | 0.22805 (15) | 0.5915 (6) | 0.3381 (2) | 0.0911 (15) | |
N15 | 0.22323 (16) | 0.4999 (7) | 0.2916 (3) | 0.0912 (15) | |
N16 | 0.2133 (2) | 0.4157 (9) | 0.2483 (3) | 0.128 (2) | |
N31 | 0.61980 (11) | 0.6957 (4) | 0.46689 (15) | 0.0498 (9) | |
N32 | 0.64431 (12) | 0.7692 (5) | 0.52519 (15) | 0.0577 (10) | |
C33 | 0.60890 (15) | 0.8028 (5) | 0.55055 (19) | 0.0539 (11) | |
C34 | 0.56086 (13) | 0.7514 (5) | 0.51031 (18) | 0.0455 (9) | |
C35 | 0.56997 (13) | 0.6852 (5) | 0.45798 (18) | 0.0449 (9) | |
C311 | 0.64806 (14) | 0.6459 (5) | 0.42690 (18) | 0.0489 (10) | |
C312 | 0.63370 (15) | 0.5118 (6) | 0.3859 (2) | 0.0576 (11) | |
H312 | 0.6047 | 0.4527 | 0.3832 | 0.069* | |
C313 | 0.66276 (18) | 0.4666 (6) | 0.3491 (2) | 0.0702 (13) | |
H313 | 0.6530 | 0.3781 | 0.3207 | 0.084* | |
C314 | 0.70616 (19) | 0.5516 (7) | 0.3541 (2) | 0.0782 (15) | |
H314 | 0.7257 | 0.5199 | 0.3293 | 0.094* | |
C315 | 0.72076 (17) | 0.6827 (7) | 0.3955 (3) | 0.0784 (15) | |
H315 | 0.7505 | 0.7383 | 0.3993 | 0.094* | |
C316 | 0.69143 (16) | 0.7326 (6) | 0.4316 (2) | 0.0672 (13) | |
H316 | 0.7008 | 0.8237 | 0.4588 | 0.081* | |
C331 | 0.62281 (17) | 0.8821 (7) | 0.6150 (2) | 0.0720 (14) | |
H33A | 0.6193 | 0.8029 | 0.6457 | 0.108* | |
H33B | 0.6011 | 0.9752 | 0.6133 | 0.108* | |
H33C | 0.6570 | 0.9194 | 0.6274 | 0.108* | |
O351 | 0.53813 (9) | 0.6158 (3) | 0.40327 (12) | 0.0483 (7) | 0.55 (4) |
C351 | 0.5093 (7) | 0.7253 (10) | 0.3559 (10) | 0.030 (5) | 0.55 (4) |
C352 | 0.4689 (8) | 0.6575 (11) | 0.3090 (11) | 0.038 (5) | 0.55 (4) |
Cl52 | 0.4590 (5) | 0.4465 (11) | 0.3077 (7) | 0.118 (4) | 0.55 (4) |
C353 | 0.4349 (9) | 0.7567 (14) | 0.2647 (12) | 0.048 (6) | 0.55 (4) |
H353 | 0.4104 | 0.7108 | 0.2295 | 0.058* | 0.55 (4) |
C354 | 0.4384 (7) | 0.9280 (13) | 0.2743 (10) | 0.039 (5) | 0.55 (4) |
Cl54 | 0.3988 (2) | 1.0506 (7) | 0.2131 (2) | 0.067 (3) | 0.55 (4) |
C355 | 0.4787 (8) | 0.9973 (14) | 0.3206 (11) | 0.043 (5) | 0.55 (4) |
H355 | 0.4832 | 1.1119 | 0.3225 | 0.051* | 0.55 (4) |
C356 | 0.5125 (8) | 0.8960 (12) | 0.3640 (12) | 0.047 (6) | 0.55 (4) |
H356 | 0.5374 | 0.9420 | 0.3987 | 0.056* | 0.55 (4) |
O451 | 0.53813 (9) | 0.6158 (3) | 0.40327 (12) | 0.0483 (7) | 0.45 (4) |
C451 | 0.5023 (8) | 0.7239 (13) | 0.3633 (11) | 0.031 (5) | 0.45 (4) |
C452 | 0.4619 (10) | 0.6533 (14) | 0.3172 (14) | 0.040 (7) | 0.45 (4) |
Cl62 | 0.4539 (3) | 0.4410 (9) | 0.3133 (5) | 0.058 (3) | 0.45 (4) |
C453 | 0.4287 (11) | 0.7504 (17) | 0.2708 (15) | 0.047 (6) | 0.45 (4) |
H453 | 0.3980 | 0.7085 | 0.2450 | 0.056* | 0.45 (4) |
C454 | 0.4429 (9) | 0.913 (2) | 0.2639 (13) | 0.050 (7) | 0.45 (4) |
Cl64 | 0.3977 (4) | 1.0402 (17) | 0.2112 (5) | 0.128 (6) | 0.45 (4) |
C455 | 0.4832 (9) | 0.9854 (19) | 0.3095 (14) | 0.045 (6) | 0.45 (4) |
H455 | 0.4889 | 1.0989 | 0.3086 | 0.054* | 0.45 (4) |
C456 | 0.5150 (8) | 0.8875 (16) | 0.3564 (13) | 0.036 (5) | 0.45 (4) |
H456 | 0.5450 | 0.9310 | 0.3835 | 0.043* | 0.45 (4) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.048 (2) | 0.045 (2) | 0.056 (3) | −0.0079 (19) | 0.016 (2) | −0.003 (2) |
O1 | 0.0606 (19) | 0.091 (3) | 0.072 (2) | −0.0197 (17) | 0.0267 (16) | −0.0303 (19) |
C2 | 0.048 (2) | 0.056 (3) | 0.047 (2) | −0.0035 (19) | 0.0118 (19) | −0.003 (2) |
C3 | 0.051 (2) | 0.053 (2) | 0.045 (2) | −0.004 (2) | 0.0127 (19) | −0.0012 (19) |
C11 | 0.048 (2) | 0.043 (2) | 0.051 (2) | 0.0000 (18) | 0.0167 (19) | 0.0025 (19) |
C12 | 0.051 (3) | 0.079 (3) | 0.061 (3) | 0.006 (2) | 0.018 (2) | −0.008 (2) |
C13 | 0.049 (3) | 0.100 (4) | 0.071 (3) | 0.011 (3) | 0.017 (2) | −0.004 (3) |
C14 | 0.045 (2) | 0.069 (3) | 0.065 (3) | −0.001 (2) | 0.006 (2) | 0.007 (2) |
C15 | 0.051 (3) | 0.079 (3) | 0.063 (3) | −0.001 (2) | 0.011 (2) | −0.016 (3) |
C16 | 0.044 (2) | 0.072 (3) | 0.070 (3) | −0.002 (2) | 0.019 (2) | −0.010 (3) |
N14 | 0.053 (3) | 0.113 (4) | 0.091 (3) | 0.001 (2) | 0.003 (2) | −0.017 (3) |
N15 | 0.061 (3) | 0.122 (4) | 0.077 (3) | −0.009 (3) | 0.004 (3) | −0.003 (3) |
N16 | 0.105 (4) | 0.175 (6) | 0.087 (4) | −0.023 (4) | 0.009 (3) | −0.030 (4) |
N31 | 0.0388 (18) | 0.061 (2) | 0.0452 (19) | −0.0027 (16) | 0.0082 (15) | 0.0027 (16) |
N32 | 0.0398 (18) | 0.081 (3) | 0.044 (2) | −0.0093 (18) | 0.0023 (15) | 0.0002 (18) |
C33 | 0.045 (2) | 0.066 (3) | 0.046 (2) | −0.008 (2) | 0.0093 (19) | 0.002 (2) |
C34 | 0.038 (2) | 0.049 (2) | 0.044 (2) | −0.0037 (18) | 0.0057 (17) | 0.0053 (19) |
C35 | 0.037 (2) | 0.047 (2) | 0.044 (2) | −0.0005 (17) | 0.0041 (17) | 0.0081 (19) |
C311 | 0.038 (2) | 0.057 (3) | 0.046 (2) | 0.0033 (19) | 0.0063 (18) | 0.012 (2) |
C312 | 0.047 (2) | 0.059 (3) | 0.065 (3) | 0.004 (2) | 0.016 (2) | 0.010 (2) |
C313 | 0.063 (3) | 0.074 (3) | 0.072 (3) | 0.015 (3) | 0.020 (3) | −0.002 (3) |
C314 | 0.065 (3) | 0.103 (4) | 0.073 (3) | 0.016 (3) | 0.032 (3) | 0.006 (3) |
C315 | 0.052 (3) | 0.105 (4) | 0.081 (4) | −0.010 (3) | 0.025 (3) | 0.006 (3) |
C316 | 0.051 (3) | 0.083 (3) | 0.064 (3) | −0.007 (2) | 0.015 (2) | −0.001 (3) |
C331 | 0.057 (3) | 0.103 (4) | 0.050 (3) | −0.017 (3) | 0.010 (2) | −0.012 (3) |
O351 | 0.0413 (14) | 0.0446 (15) | 0.0480 (16) | −0.0012 (12) | −0.0005 (12) | −0.0026 (12) |
C351 | 0.019 (5) | 0.035 (6) | 0.043 (8) | −0.004 (4) | 0.018 (5) | −0.006 (4) |
C352 | 0.035 (6) | 0.041 (6) | 0.043 (8) | 0.001 (4) | 0.017 (7) | −0.008 (5) |
Cl52 | 0.132 (7) | 0.064 (4) | 0.115 (6) | −0.019 (4) | −0.018 (4) | −0.012 (4) |
C353 | 0.035 (7) | 0.067 (9) | 0.039 (8) | −0.011 (6) | 0.008 (6) | −0.013 (6) |
C354 | 0.042 (6) | 0.046 (6) | 0.030 (7) | 0.028 (5) | 0.013 (6) | 0.010 (5) |
Cl54 | 0.058 (3) | 0.068 (4) | 0.051 (3) | 0.033 (2) | −0.014 (3) | 0.020 (2) |
C355 | 0.046 (6) | 0.045 (6) | 0.039 (7) | 0.009 (5) | 0.017 (7) | −0.007 (5) |
C356 | 0.052 (10) | 0.049 (8) | 0.035 (7) | 0.000 (6) | 0.010 (7) | −0.016 (6) |
O451 | 0.0413 (14) | 0.0446 (15) | 0.0480 (16) | −0.0012 (12) | −0.0005 (12) | −0.0026 (12) |
C451 | 0.026 (8) | 0.057 (9) | 0.018 (5) | 0.000 (5) | 0.017 (6) | 0.000 (5) |
C452 | 0.040 (9) | 0.050 (8) | 0.037 (8) | −0.011 (6) | 0.021 (7) | −0.006 (6) |
Cl62 | 0.052 (4) | 0.036 (3) | 0.073 (4) | −0.012 (2) | 0.001 (2) | −0.013 (2) |
C453 | 0.035 (8) | 0.067 (10) | 0.039 (8) | 0.002 (7) | 0.011 (8) | 0.000 (7) |
C454 | 0.042 (8) | 0.077 (11) | 0.036 (9) | 0.005 (8) | 0.020 (6) | −0.008 (7) |
Cl64 | 0.103 (8) | 0.150 (10) | 0.130 (9) | 0.036 (6) | 0.037 (7) | 0.023 (6) |
C455 | 0.057 (9) | 0.041 (8) | 0.047 (10) | 0.009 (6) | 0.032 (7) | 0.003 (7) |
C456 | 0.020 (7) | 0.047 (10) | 0.043 (10) | −0.009 (7) | 0.012 (6) | 0.002 (8) |
Geometric parameters (Å, º) top C1—O1 | 1.218 (5) | C313—H313 | 0.9300 |
C1—C2 | 1.470 (5) | C314—C315 | 1.367 (7) |
C1—C11 | 1.494 (5) | C314—H314 | 0.9300 |
C2—C3 | 1.329 (5) | C315—C316 | 1.382 (6) |
C2—H2 | 0.9300 | C315—H315 | 0.9300 |
C3—C34 | 1.445 (5) | C316—H316 | 0.9300 |
C3—H3 | 0.9300 | C331—H33A | 0.9600 |
C11—C16 | 1.378 (6) | C331—H33B | 0.9600 |
C11—C12 | 1.385 (5) | C331—H33C | 0.9600 |
C12—C13 | 1.372 (6) | O351—C351 | 1.405 (7) |
C12—H12 | 0.9300 | C351—C352 | 1.377 (7) |
C13—C14 | 1.365 (6) | C351—C356 | 1.385 (11) |
C13—H13 | 0.9300 | C352—C353 | 1.377 (8) |
C14—C15 | 1.372 (6) | C352—Cl52 | 1.721 (7) |
C14—N14 | 1.431 (6) | C353—C354 | 1.395 (13) |
C15—C16 | 1.375 (6) | C353—H353 | 0.9300 |
C15—H15 | 0.9300 | C354—C355 | 1.374 (8) |
C16—H16 | 0.9300 | C354—Cl54 | 1.748 (6) |
N14—N15 | 1.233 (7) | C355—C356 | 1.375 (8) |
N15—N16 | 1.128 (7) | C355—H355 | 0.9300 |
N31—C35 | 1.356 (5) | C356—H356 | 0.9300 |
N31—N32 | 1.378 (4) | C451—C452 | 1.378 (8) |
N31—C311 | 1.425 (5) | C451—C456 | 1.387 (12) |
N32—C33 | 1.322 (5) | C452—C453 | 1.381 (8) |
C33—C34 | 1.417 (5) | C452—Cl62 | 1.723 (7) |
C33—C331 | 1.488 (6) | C453—C454 | 1.394 (15) |
C34—C35 | 1.369 (5) | C453—H453 | 0.9300 |
C35—O351 | 1.366 (4) | C454—C455 | 1.376 (9) |
C311—C312 | 1.381 (6) | C454—Cl64 | 1.746 (8) |
C311—C316 | 1.382 (6) | C455—C456 | 1.373 (8) |
C312—C313 | 1.378 (6) | C455—H455 | 0.9300 |
C312—H312 | 0.9300 | C456—H456 | 0.9300 |
C313—C314 | 1.374 (7) | | |
| | | |
O1—C1—C2 | 121.1 (4) | C315—C314—C313 | 120.3 (5) |
O1—C1—C11 | 119.8 (4) | C315—C314—H314 | 119.8 |
C2—C1—C11 | 119.1 (4) | C313—C314—H314 | 119.8 |
C3—C2—C1 | 121.9 (4) | C314—C315—C316 | 120.1 (5) |
C3—C2—H2 | 119.0 | C314—C315—H315 | 119.9 |
C1—C2—H2 | 119.0 | C316—C315—H315 | 119.9 |
C2—C3—C34 | 128.0 (4) | C315—C316—C311 | 119.4 (5) |
C2—C3—H3 | 116.0 | C315—C316—H316 | 120.3 |
C34—C3—H3 | 116.0 | C311—C316—H316 | 120.3 |
C16—C11—C12 | 117.7 (4) | C33—C331—H33A | 109.5 |
C16—C11—C1 | 123.5 (4) | C33—C331—H33B | 109.5 |
C12—C11—C1 | 118.8 (4) | H33A—C331—H33B | 109.5 |
C13—C12—C11 | 121.2 (4) | C33—C331—H33C | 109.5 |
C13—C12—H12 | 119.4 | H33A—C331—H33C | 109.5 |
C11—C12—H12 | 119.4 | H33B—C331—H33C | 109.5 |
C14—C13—C12 | 119.8 (4) | C35—O351—C351 | 117.0 (5) |
C14—C13—H13 | 120.1 | C352—C351—C356 | 119.5 (7) |
C12—C13—H13 | 120.1 | C352—C351—O351 | 116.5 (6) |
C13—C14—C15 | 120.5 (4) | C356—C351—O351 | 122.0 (9) |
C13—C14—N14 | 115.9 (4) | C351—C352—C353 | 121.1 (6) |
C15—C14—N14 | 123.6 (5) | C351—C352—Cl52 | 119.6 (6) |
C14—C15—C16 | 119.2 (4) | C353—C352—Cl52 | 119.3 (6) |
C14—C15—H15 | 120.4 | C352—C353—C354 | 117.9 (8) |
C16—C15—H15 | 120.4 | C352—C353—H353 | 121.1 |
C15—C16—C11 | 121.6 (4) | C354—C353—H353 | 121.1 |
C15—C16—H16 | 119.2 | C355—C354—C353 | 121.0 (8) |
C11—C16—H16 | 119.2 | C355—C354—Cl54 | 120.5 (6) |
N15—N14—C14 | 115.8 (5) | C353—C354—Cl54 | 116.5 (8) |
N16—N15—N14 | 172.3 (6) | C354—C355—C356 | 119.5 (7) |
C35—N31—N32 | 110.0 (3) | C354—C355—H355 | 120.3 |
C35—N31—C311 | 130.9 (3) | C356—C355—H355 | 120.3 |
N32—N31—C311 | 119.1 (3) | C355—C356—C351 | 119.9 (8) |
C33—N32—N31 | 105.3 (3) | C355—C356—H356 | 120.0 |
N32—C33—C34 | 112.0 (4) | C351—C356—H356 | 120.0 |
N32—C33—C331 | 119.4 (4) | C452—C451—C456 | 119.5 (9) |
C34—C33—C331 | 128.5 (4) | C451—C452—C453 | 120.6 (8) |
C35—C34—C33 | 103.7 (3) | C451—C452—Cl62 | 120.6 (7) |
C35—C34—C3 | 129.5 (3) | C453—C452—Cl62 | 118.6 (7) |
C33—C34—C3 | 126.8 (4) | C452—C453—C454 | 117.7 (11) |
N31—C35—O351 | 120.3 (3) | C452—C453—H453 | 121.1 |
N31—C35—C34 | 108.9 (3) | C454—C453—H453 | 121.1 |
O351—C35—C34 | 130.8 (3) | C455—C454—C453 | 121.0 (10) |
C312—C311—C316 | 120.5 (4) | C455—C454—Cl64 | 119.3 (9) |
C312—C311—N31 | 121.4 (4) | C453—C454—Cl64 | 116.8 (11) |
C316—C311—N31 | 118.1 (4) | C456—C455—C454 | 119.2 (8) |
C313—C312—C311 | 119.2 (4) | C456—C455—H455 | 120.4 |
C313—C312—H312 | 120.4 | C454—C455—H455 | 120.4 |
C311—C312—H312 | 120.4 | C455—C456—C451 | 120.0 (9) |
C314—C313—C312 | 120.4 (5) | C455—C456—H456 | 120.0 |
C314—C313—H313 | 119.8 | C451—C456—H456 | 120.0 |
C312—C313—H313 | 119.8 | | |
| | | |
O1—C1—C2—C3 | −8.0 (6) | N32—N31—C311—C312 | 149.6 (4) |
C11—C1—C2—C3 | 171.4 (4) | C35—N31—C311—C316 | 151.0 (4) |
C1—C2—C3—C34 | −178.2 (4) | N32—N31—C311—C316 | −28.4 (5) |
O1—C1—C11—C16 | −173.2 (4) | C316—C311—C312—C313 | −0.9 (6) |
C2—C1—C11—C16 | 7.4 (6) | N31—C311—C312—C313 | −178.8 (4) |
O1—C1—C11—C12 | 6.7 (6) | C311—C312—C313—C314 | 1.5 (7) |
C2—C1—C11—C12 | −172.7 (4) | C312—C313—C314—C315 | −0.4 (8) |
C16—C11—C12—C13 | −0.5 (7) | C313—C314—C315—C316 | −1.3 (8) |
C1—C11—C12—C13 | 179.6 (4) | C314—C315—C316—C311 | 1.9 (7) |
C11—C12—C13—C14 | 0.2 (8) | C312—C311—C316—C315 | −0.8 (7) |
C12—C13—C14—C15 | 0.2 (8) | N31—C311—C316—C315 | 177.2 (4) |
C12—C13—C14—N14 | −179.7 (5) | N31—C35—O351—C351 | −102.1 (15) |
C13—C14—C15—C16 | −0.3 (8) | C34—C35—O351—C351 | 78.3 (16) |
N14—C14—C15—C16 | 179.6 (5) | C35—O351—C351—C352 | −164 (2) |
C14—C15—C16—C11 | 0.0 (7) | C35—O351—C351—C356 | 0 (4) |
C12—C11—C16—C15 | 0.4 (7) | C356—C351—C352—C353 | 8 (5) |
C1—C11—C16—C15 | −179.7 (4) | O351—C351—C352—C353 | 172 (3) |
C13—C14—N14—N15 | −172.6 (5) | C356—C351—C352—Cl52 | −169 (3) |
C15—C14—N14—N15 | 7.5 (8) | O351—C351—C352—Cl52 | −4 (4) |
C35—N31—N32—C33 | −0.3 (4) | C351—C352—C353—C354 | −9 (5) |
C311—N31—N32—C33 | 179.3 (4) | Cl52—C352—C353—C354 | 168 (3) |
N31—N32—C33—C34 | 0.6 (5) | C352—C353—C354—C355 | 10 (5) |
N31—N32—C33—C331 | 179.2 (4) | C352—C353—C354—Cl54 | 174 (3) |
N32—C33—C34—C35 | −0.6 (5) | C353—C354—C355—C356 | −9 (5) |
C331—C33—C34—C35 | −179.1 (5) | Cl54—C354—C355—C356 | −173 (3) |
N32—C33—C34—C3 | 180.0 (4) | C354—C355—C356—C351 | 8 (5) |
C331—C33—C34—C3 | 1.5 (7) | C352—C351—C356—C355 | −8 (5) |
C2—C3—C34—C35 | 5.1 (7) | O351—C351—C356—C355 | −171 (3) |
C2—C3—C34—C33 | −175.7 (4) | C456—C451—C452—C453 | −11 (6) |
N32—N31—C35—O351 | −179.8 (3) | C456—C451—C452—Cl62 | 164 (3) |
C311—N31—C35—O351 | 0.7 (6) | C451—C452—C453—C454 | 13 (6) |
N32—N31—C35—C34 | −0.1 (5) | Cl62—C452—C453—C454 | −163 (4) |
C311—N31—C35—C34 | −179.6 (4) | C452—C453—C454—C455 | −13 (6) |
C33—C34—C35—N31 | 0.4 (4) | C452—C453—C454—Cl64 | −173 (3) |
C3—C34—C35—N31 | 179.8 (4) | C453—C454—C455—C456 | 11 (6) |
C33—C34—C35—O351 | −179.9 (4) | Cl64—C454—C455—C456 | 171 (3) |
C3—C34—C35—O351 | −0.5 (7) | C454—C455—C456—C451 | −10 (6) |
C35—N31—C311—C312 | −31.0 (6) | C452—C451—C456—C455 | 10 (6) |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C356—H356···O1i | 0.93 | 2.32 | 3.115 (18) | 143 |
C456—H456···O1i | 0.93 | 2.47 | 3.21 (2) | 137 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
1-(4-Azidophenyl)-3-[3-methyl-5-(naphthalen-2-yloxy)-1-phenyl-1
H-pyrazol-4-yl]prop-2-en-1-on (IIe)
top Crystal data top C29H21N5O2 | F(000) = 984 |
Mr = 471.51 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8460 (8) Å | Cell parameters from 4197 reflections |
b = 22.4303 (18) Å | θ = 3.1–25.1° |
c = 11.0490 (9) Å | µ = 0.09 mm−1 |
β = 104.157 (2)° | T = 297 K |
V = 2366.0 (3) Å3 | Block, orange |
Z = 4 | 0.22 × 0.21 × 0.16 mm |
Data collection top Bruker APEXII diffractometer | 4196 independent reflections |
Radiation source: fine focussealed tube | 2463 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.092 |
φ and ω scans | θmax = 25.1°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −11→11 |
Tmin = 0.930, Tmax = 0.986 | k = −26→26 |
43217 measured reflections | l = −12→13 |
Refinement top Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.063 | w = 1/[σ2(Fo2) + (0.0268P)2 + 3.4386P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.154 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.23 e Å−3 |
4196 reflections | Δρmin = −0.27 e Å−3 |
327 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0143 (9) |
Primary atom site location: dual | |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.3799 (4) | 0.50783 (16) | 0.2247 (3) | 0.0478 (9) | |
O1 | 0.2646 (3) | 0.49934 (13) | 0.1526 (2) | 0.0673 (8) | |
C2 | 0.5060 (4) | 0.47779 (16) | 0.2070 (3) | 0.0489 (9) | |
H2 | 0.5904 | 0.4830 | 0.2662 | 0.059* | |
C3 | 0.5026 (4) | 0.44316 (15) | 0.1078 (3) | 0.0465 (9) | |
H3 | 0.4164 | 0.4406 | 0.0502 | 0.056* | |
C11 | 0.3908 (3) | 0.54796 (15) | 0.3332 (3) | 0.0433 (8) | |
C12 | 0.2693 (4) | 0.56999 (17) | 0.3595 (4) | 0.0543 (10) | |
H12 | 0.1831 | 0.5588 | 0.3088 | 0.065* | |
C13 | 0.2725 (4) | 0.60784 (17) | 0.4580 (4) | 0.0552 (10) | |
H13 | 0.1896 | 0.6212 | 0.4748 | 0.066* | |
C14 | 0.3990 (4) | 0.62554 (16) | 0.5309 (3) | 0.0486 (9) | |
C15 | 0.5220 (4) | 0.6051 (2) | 0.5074 (4) | 0.0656 (12) | |
H15 | 0.6078 | 0.6174 | 0.5572 | 0.079* | |
C16 | 0.5169 (4) | 0.56643 (19) | 0.4095 (4) | 0.0595 (11) | |
H16 | 0.6001 | 0.5524 | 0.3944 | 0.071* | |
N14 | 0.4149 (4) | 0.66594 (16) | 0.6335 (3) | 0.0655 (10) | |
N15 | 0.3037 (4) | 0.68821 (16) | 0.6481 (3) | 0.0621 (9) | |
N16 | 0.2126 (4) | 0.71190 (18) | 0.6714 (4) | 0.0877 (13) | |
N31 | 0.8165 (3) | 0.36482 (13) | 0.0799 (3) | 0.0495 (8) | |
N32 | 0.7208 (3) | 0.33982 (14) | −0.0191 (3) | 0.0551 (8) | |
C33 | 0.6012 (4) | 0.36732 (16) | −0.0196 (3) | 0.0487 (9) | |
C34 | 0.6151 (4) | 0.40921 (15) | 0.0783 (3) | 0.0444 (9) | |
C35 | 0.7544 (4) | 0.40565 (15) | 0.1390 (3) | 0.0446 (9) | |
C311 | 0.9557 (4) | 0.34178 (17) | 0.1152 (3) | 0.0491 (9) | |
C312 | 1.0685 (4) | 0.37933 (18) | 0.1521 (3) | 0.0530 (10) | |
H312 | 1.0555 | 0.4204 | 0.1536 | 0.064* | |
C313 | 1.2010 (4) | 0.3553 (2) | 0.1870 (4) | 0.0634 (11) | |
H313 | 1.2778 | 0.3805 | 0.2116 | 0.076* | |
C314 | 1.2215 (5) | 0.2949 (2) | 0.1861 (4) | 0.0762 (13) | |
H314 | 1.3115 | 0.2792 | 0.2102 | 0.091* | |
C315 | 1.1087 (5) | 0.2577 (2) | 0.1496 (5) | 0.0831 (15) | |
H315 | 1.1227 | 0.2167 | 0.1496 | 0.100* | |
C316 | 0.9736 (4) | 0.28021 (19) | 0.1125 (4) | 0.0704 (13) | |
H316 | 0.8971 | 0.2549 | 0.0866 | 0.084* | |
C331 | 0.4703 (4) | 0.35114 (19) | −0.1150 (4) | 0.0665 (12) | |
H33A | 0.4924 | 0.3233 | −0.1734 | 0.100* | |
H33B | 0.4298 | 0.3864 | −0.1585 | 0.100* | |
H33C | 0.4047 | 0.3333 | −0.0743 | 0.100* | |
O351 | 0.8283 (2) | 0.42967 (10) | 0.2482 (2) | 0.0485 (6) | |
C351 | 0.8655 (3) | 0.51795 (16) | 0.3666 (3) | 0.0455 (9) | |
H351 | 0.8589 | 0.4953 | 0.4355 | 0.055* | |
C352 | 0.8523 (3) | 0.49169 (15) | 0.2527 (3) | 0.0423 (8) | |
C353 | 0.8651 (4) | 0.52368 (17) | 0.1473 (3) | 0.0498 (9) | |
H353 | 0.8558 | 0.5046 | 0.0709 | 0.060* | |
C354 | 0.8917 (4) | 0.58332 (18) | 0.1585 (3) | 0.0551 (10) | |
H354 | 0.9021 | 0.6047 | 0.0893 | 0.066* | |
C355 | 0.9276 (4) | 0.67581 (18) | 0.2850 (4) | 0.0664 (12) | |
H355 | 0.9410 | 0.6977 | 0.2175 | 0.080* | |
C356 | 0.9309 (5) | 0.7037 (2) | 0.3951 (5) | 0.0732 (13) | |
H356 | 0.9446 | 0.7447 | 0.4017 | 0.088* | |
C357 | 0.9139 (4) | 0.6714 (2) | 0.4975 (4) | 0.0685 (12) | |
H357 | 0.9152 | 0.6913 | 0.5716 | 0.082* | |
C358 | 0.8951 (4) | 0.61082 (19) | 0.4919 (4) | 0.0570 (10) | |
H358 | 0.8862 | 0.5897 | 0.5620 | 0.068* | |
C359 | 0.9037 (4) | 0.61317 (16) | 0.2727 (3) | 0.0498 (9) | |
C360 | 0.8896 (3) | 0.58065 (16) | 0.3779 (3) | 0.0437 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.042 (2) | 0.052 (2) | 0.048 (2) | 0.0016 (18) | 0.0093 (17) | 0.0008 (18) |
O1 | 0.0452 (16) | 0.089 (2) | 0.0630 (17) | 0.0038 (15) | 0.0042 (14) | −0.0216 (16) |
C2 | 0.037 (2) | 0.058 (2) | 0.050 (2) | 0.0027 (17) | 0.0077 (16) | −0.0056 (19) |
C3 | 0.041 (2) | 0.051 (2) | 0.047 (2) | 0.0013 (17) | 0.0080 (16) | 0.0021 (18) |
C11 | 0.0349 (19) | 0.048 (2) | 0.046 (2) | 0.0009 (16) | 0.0098 (16) | −0.0019 (17) |
C12 | 0.036 (2) | 0.064 (3) | 0.062 (2) | −0.0024 (18) | 0.0092 (18) | −0.011 (2) |
C13 | 0.042 (2) | 0.063 (3) | 0.061 (2) | −0.0017 (19) | 0.0130 (18) | −0.014 (2) |
C14 | 0.048 (2) | 0.051 (2) | 0.045 (2) | −0.0011 (18) | 0.0082 (17) | −0.0036 (18) |
C15 | 0.037 (2) | 0.093 (3) | 0.061 (3) | 0.002 (2) | 0.0013 (19) | −0.019 (2) |
C16 | 0.039 (2) | 0.082 (3) | 0.056 (2) | 0.007 (2) | 0.0096 (18) | −0.013 (2) |
N14 | 0.054 (2) | 0.078 (2) | 0.064 (2) | 0.0027 (19) | 0.0129 (17) | −0.0171 (19) |
N15 | 0.066 (2) | 0.058 (2) | 0.061 (2) | −0.0092 (19) | 0.0140 (19) | −0.0108 (18) |
N16 | 0.076 (3) | 0.085 (3) | 0.107 (3) | 0.002 (2) | 0.032 (2) | −0.036 (2) |
N31 | 0.0454 (18) | 0.0521 (19) | 0.0493 (18) | 0.0013 (15) | 0.0080 (15) | −0.0150 (15) |
N32 | 0.0519 (19) | 0.057 (2) | 0.0527 (19) | −0.0057 (16) | 0.0061 (15) | −0.0154 (16) |
C33 | 0.048 (2) | 0.049 (2) | 0.047 (2) | −0.0067 (18) | 0.0065 (17) | −0.0048 (18) |
C34 | 0.045 (2) | 0.045 (2) | 0.042 (2) | −0.0008 (17) | 0.0099 (16) | −0.0052 (17) |
C35 | 0.046 (2) | 0.044 (2) | 0.042 (2) | −0.0012 (17) | 0.0079 (17) | −0.0064 (17) |
C311 | 0.046 (2) | 0.056 (2) | 0.047 (2) | 0.0025 (19) | 0.0137 (17) | −0.0074 (19) |
C312 | 0.050 (2) | 0.056 (2) | 0.053 (2) | 0.000 (2) | 0.0148 (18) | −0.0016 (19) |
C313 | 0.048 (2) | 0.084 (3) | 0.058 (3) | 0.001 (2) | 0.0133 (19) | −0.006 (2) |
C314 | 0.054 (3) | 0.089 (4) | 0.086 (3) | 0.017 (3) | 0.018 (2) | −0.013 (3) |
C315 | 0.072 (3) | 0.069 (3) | 0.109 (4) | 0.019 (3) | 0.024 (3) | −0.021 (3) |
C316 | 0.062 (3) | 0.059 (3) | 0.093 (3) | 0.003 (2) | 0.023 (2) | −0.023 (2) |
C331 | 0.060 (3) | 0.068 (3) | 0.066 (3) | −0.009 (2) | 0.004 (2) | −0.014 (2) |
O351 | 0.0554 (15) | 0.0442 (14) | 0.0417 (14) | −0.0010 (12) | 0.0042 (11) | −0.0085 (12) |
C351 | 0.040 (2) | 0.053 (2) | 0.040 (2) | −0.0020 (17) | 0.0057 (16) | −0.0060 (18) |
C352 | 0.0357 (19) | 0.043 (2) | 0.044 (2) | −0.0003 (16) | 0.0026 (15) | −0.0079 (18) |
C353 | 0.052 (2) | 0.056 (3) | 0.040 (2) | 0.0036 (18) | 0.0078 (17) | −0.0031 (18) |
C354 | 0.058 (2) | 0.060 (3) | 0.045 (2) | 0.005 (2) | 0.0081 (18) | 0.005 (2) |
C355 | 0.070 (3) | 0.053 (3) | 0.071 (3) | 0.002 (2) | 0.007 (2) | −0.001 (2) |
C356 | 0.074 (3) | 0.055 (3) | 0.083 (3) | 0.006 (2) | 0.005 (3) | −0.014 (3) |
C357 | 0.056 (3) | 0.072 (3) | 0.072 (3) | 0.000 (2) | 0.007 (2) | −0.029 (3) |
C358 | 0.050 (2) | 0.070 (3) | 0.049 (2) | −0.003 (2) | 0.0093 (18) | −0.018 (2) |
C359 | 0.045 (2) | 0.052 (2) | 0.047 (2) | 0.0021 (18) | 0.0028 (17) | −0.0025 (19) |
C360 | 0.0306 (18) | 0.055 (2) | 0.042 (2) | 0.0002 (16) | 0.0034 (15) | −0.0121 (18) |
Geometric parameters (Å, º) top C1—O1 | 1.232 (4) | C312—H312 | 0.9300 |
C1—C2 | 1.467 (5) | C313—C314 | 1.371 (6) |
C1—C11 | 1.482 (5) | C313—H313 | 0.9300 |
C2—C3 | 1.337 (5) | C314—C315 | 1.368 (6) |
C2—H2 | 0.9300 | C314—H314 | 0.9300 |
C3—C34 | 1.446 (5) | C315—C316 | 1.387 (6) |
C3—H3 | 0.9300 | C315—H315 | 0.9300 |
C11—C16 | 1.382 (5) | C316—H316 | 0.9300 |
C11—C12 | 1.389 (5) | C331—H33A | 0.9600 |
C12—C13 | 1.375 (5) | C331—H33B | 0.9600 |
C12—H12 | 0.9300 | C331—H33C | 0.9600 |
C13—C14 | 1.367 (5) | O351—C352 | 1.410 (4) |
C13—H13 | 0.9300 | C351—C352 | 1.367 (5) |
C14—C15 | 1.377 (5) | C351—C360 | 1.427 (5) |
C14—N14 | 1.430 (5) | C351—H351 | 0.9300 |
C15—C16 | 1.378 (5) | C352—C353 | 1.400 (5) |
C15—H15 | 0.9300 | C353—C354 | 1.363 (5) |
C16—H16 | 0.9300 | C353—H353 | 0.9300 |
N14—N15 | 1.249 (5) | C354—C359 | 1.407 (5) |
N15—N16 | 1.126 (5) | C354—H354 | 0.9300 |
N31—C35 | 1.353 (4) | C355—C356 | 1.360 (6) |
N31—N32 | 1.376 (4) | C355—C359 | 1.426 (5) |
N31—C311 | 1.427 (4) | C355—H355 | 0.9300 |
N32—C33 | 1.327 (4) | C356—C357 | 1.388 (6) |
C33—C34 | 1.414 (5) | C356—H356 | 0.9300 |
C33—C331 | 1.497 (5) | C357—C358 | 1.371 (6) |
C34—C35 | 1.374 (5) | C357—H357 | 0.9300 |
C35—O351 | 1.359 (4) | C358—C360 | 1.419 (5) |
C311—C312 | 1.374 (5) | C358—H358 | 0.9300 |
C311—C316 | 1.394 (5) | C359—C360 | 1.408 (5) |
C312—C313 | 1.377 (5) | | |
| | | |
O1—C1—C2 | 121.3 (3) | C314—C313—H313 | 119.5 |
O1—C1—C11 | 119.3 (3) | C312—C313—H313 | 119.5 |
C2—C1—C11 | 119.4 (3) | C315—C314—C313 | 119.6 (4) |
C3—C2—C1 | 121.6 (3) | C315—C314—H314 | 120.2 |
C3—C2—H2 | 119.2 | C313—C314—H314 | 120.2 |
C1—C2—H2 | 119.2 | C314—C315—C316 | 121.0 (4) |
C2—C3—C34 | 128.6 (3) | C314—C315—H315 | 119.5 |
C2—C3—H3 | 115.7 | C316—C315—H315 | 119.5 |
C34—C3—H3 | 115.7 | C315—C316—C311 | 118.2 (4) |
C16—C11—C12 | 117.2 (3) | C315—C316—H316 | 120.9 |
C16—C11—C1 | 123.5 (3) | C311—C316—H316 | 120.9 |
C12—C11—C1 | 119.3 (3) | C33—C331—H33A | 109.5 |
C13—C12—C11 | 122.1 (3) | C33—C331—H33B | 109.5 |
C13—C12—H12 | 119.0 | H33A—C331—H33B | 109.5 |
C11—C12—H12 | 119.0 | C33—C331—H33C | 109.5 |
C14—C13—C12 | 119.2 (3) | H33A—C331—H33C | 109.5 |
C14—C13—H13 | 120.4 | H33B—C331—H33C | 109.5 |
C12—C13—H13 | 120.4 | C35—O351—C352 | 118.1 (3) |
C13—C14—C15 | 120.6 (4) | C352—C351—C360 | 118.8 (3) |
C13—C14—N14 | 124.0 (3) | C352—C351—H351 | 120.6 |
C15—C14—N14 | 115.5 (3) | C360—C351—H351 | 120.6 |
C14—C15—C16 | 119.5 (3) | C351—C352—C353 | 122.5 (3) |
C14—C15—H15 | 120.2 | C351—C352—O351 | 115.8 (3) |
C16—C15—H15 | 120.2 | C353—C352—O351 | 121.7 (3) |
C15—C16—C11 | 121.5 (3) | C354—C353—C352 | 118.8 (3) |
C15—C16—H16 | 119.3 | C354—C353—H353 | 120.6 |
C11—C16—H16 | 119.3 | C352—C353—H353 | 120.6 |
N15—N14—C14 | 115.2 (3) | C353—C354—C359 | 121.4 (4) |
N16—N15—N14 | 172.4 (4) | C353—C354—H354 | 119.3 |
C35—N31—N32 | 110.9 (3) | C359—C354—H354 | 119.3 |
C35—N31—C311 | 129.0 (3) | C356—C355—C359 | 120.4 (4) |
N32—N31—C311 | 119.6 (3) | C356—C355—H355 | 119.8 |
C33—N32—N31 | 104.3 (3) | C359—C355—H355 | 119.8 |
N32—C33—C34 | 112.7 (3) | C355—C356—C357 | 120.5 (4) |
N32—C33—C331 | 120.0 (3) | C355—C356—H356 | 119.7 |
C34—C33—C331 | 127.2 (3) | C357—C356—H356 | 119.7 |
C35—C34—C33 | 103.4 (3) | C358—C357—C356 | 121.5 (4) |
C35—C34—C3 | 130.5 (3) | C358—C357—H357 | 119.3 |
C33—C34—C3 | 126.0 (3) | C356—C357—H357 | 119.3 |
N31—C35—O351 | 119.3 (3) | C357—C358—C360 | 119.2 (4) |
N31—C35—C34 | 108.6 (3) | C357—C358—H358 | 120.4 |
O351—C35—C34 | 131.6 (3) | C360—C358—H358 | 120.4 |
C312—C311—C316 | 121.1 (4) | C354—C359—C360 | 119.4 (3) |
C312—C311—N31 | 120.8 (3) | C354—C359—C355 | 122.0 (4) |
C316—C311—N31 | 118.1 (3) | C360—C359—C355 | 118.6 (4) |
C311—C312—C313 | 119.0 (4) | C359—C360—C358 | 119.7 (3) |
C311—C312—H312 | 120.5 | C359—C360—C351 | 119.1 (3) |
C313—C312—H312 | 120.5 | C358—C360—C351 | 121.2 (4) |
C314—C313—C312 | 121.1 (4) | | |
| | | |
O1—C1—C2—C3 | 4.4 (6) | C35—N31—C311—C312 | −47.2 (5) |
C11—C1—C2—C3 | −177.2 (3) | N32—N31—C311—C312 | 140.9 (3) |
C1—C2—C3—C34 | −178.0 (3) | C35—N31—C311—C316 | 132.0 (4) |
O1—C1—C11—C16 | −171.1 (4) | N32—N31—C311—C316 | −39.9 (5) |
C2—C1—C11—C16 | 10.4 (5) | C316—C311—C312—C313 | 0.0 (6) |
O1—C1—C11—C12 | 7.1 (5) | N31—C311—C312—C313 | 179.2 (3) |
C2—C1—C11—C12 | −171.4 (3) | C311—C312—C313—C314 | −0.5 (6) |
C16—C11—C12—C13 | −1.0 (6) | C312—C313—C314—C315 | 0.3 (7) |
C1—C11—C12—C13 | −179.3 (4) | C313—C314—C315—C316 | 0.4 (7) |
C11—C12—C13—C14 | 1.5 (6) | C314—C315—C316—C311 | −0.9 (7) |
C12—C13—C14—C15 | −0.9 (6) | C312—C311—C316—C315 | 0.7 (6) |
C12—C13—C14—N14 | 178.3 (4) | N31—C311—C316—C315 | −178.5 (4) |
C13—C14—C15—C16 | −0.1 (6) | N31—C35—O351—C352 | 118.1 (3) |
N14—C14—C15—C16 | −179.4 (4) | C34—C35—O351—C352 | −71.1 (5) |
C14—C15—C16—C11 | 0.6 (7) | C360—C351—C352—C353 | 1.7 (5) |
C12—C11—C16—C15 | −0.1 (6) | C360—C351—C352—O351 | −179.8 (3) |
C1—C11—C16—C15 | 178.2 (4) | C35—O351—C352—C351 | 150.9 (3) |
C13—C14—N14—N15 | −5.0 (6) | C35—O351—C352—C353 | −30.7 (4) |
C15—C14—N14—N15 | 174.2 (4) | C351—C352—C353—C354 | −0.1 (5) |
C35—N31—N32—C33 | 1.2 (4) | O351—C352—C353—C354 | −178.4 (3) |
C311—N31—N32—C33 | 174.5 (3) | C352—C353—C354—C359 | −1.2 (5) |
N31—N32—C33—C34 | −1.1 (4) | C359—C355—C356—C357 | 1.3 (6) |
N31—N32—C33—C331 | −179.2 (3) | C355—C356—C357—C358 | 0.8 (7) |
N32—C33—C34—C35 | 0.5 (4) | C356—C357—C358—C360 | −1.6 (6) |
C331—C33—C34—C35 | 178.6 (4) | C353—C354—C359—C360 | 0.7 (5) |
N32—C33—C34—C3 | −175.5 (3) | C353—C354—C359—C355 | −178.2 (4) |
C331—C33—C34—C3 | 2.5 (6) | C356—C355—C359—C354 | 176.3 (4) |
C2—C3—C34—C35 | −3.7 (7) | C356—C355—C359—C360 | −2.6 (6) |
C2—C3—C34—C33 | 171.2 (4) | C354—C359—C360—C358 | −177.1 (3) |
N32—N31—C35—O351 | 171.8 (3) | C355—C359—C360—C358 | 1.8 (5) |
C311—N31—C35—O351 | −0.6 (6) | C354—C359—C360—C351 | 0.9 (5) |
N32—N31—C35—C34 | −0.9 (4) | C355—C359—C360—C351 | 179.9 (3) |
C311—N31—C35—C34 | −173.4 (3) | C357—C358—C360—C359 | 0.2 (5) |
C33—C34—C35—N31 | 0.2 (4) | C357—C358—C360—C351 | −177.8 (3) |
C3—C34—C35—N31 | 176.0 (3) | C352—C351—C360—C359 | −2.1 (5) |
C33—C34—C35—O351 | −171.3 (4) | C352—C351—C360—C358 | 175.9 (3) |
C3—C34—C35—O351 | 4.4 (7) | | |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C353—H353···O1i | 0.93 | 2.47 | 3.288 (4) | 147 |
C12—H12···Cg3ii | 0.93 | 2.93 | 3.761 (4) | 150 |
C13—H13···Cg4ii | 0.93 | 2.73 | 3.547 (4) | 148 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z. |
Selected torsional angles (°) for compounds (Ib), (Ic), (Ie), (IIa), (IId) and (IIe) topParameter | (Ib) | (Ic) | (Ie) | (IIa) | (IId) | (IIe) |
N32—N31—C311—C312 | 151.1 (3) | 137.0 (2) | 139.9 (3) | 135.1 (2) | 149.6 (4) | 140.9 (3) |
C2—C1—C11—C12 | 168.8 (2) | -163.4 (2) | -162.8 (3) | 166.8 (2) | -172.7 (4) | -171.4 (3) |
C13—C14—O14—C17 | 169.8 (2) | 3.5 (3) | -0.4 (4) | | | |
C14—O14—C17—C18 | -68.7 (3) | -177.1 (2) | -174.7 (3) | | | |
C13—C14—N14—N15 | | | | -2.7 (3) | -172.6 (5) | -5.0 (6) |
C34—C35—O351—C351 | -76.7 (3) | -69.3 (3) | | 70.1 (3) | 78.3 (16) | |
C34—C35—O451—C451 | | | | | 65.0 (12) | |
C35—O351—C351—C352 | 157.6 (2) | 169.5 (2) | | -159.6 (2) | -164 (2) | |
C35—O451—C451—C45 | | | | | -163.6 (18) | |
C34—C35—O351—C352 | | | -70.6 (4) | | | -71.1 (5) |
C35—O351—C352—C351 | | | 161.8 (2) | | | 150.9 (3) |
Hydrogen bonds and short intra- and inter-molecular contacts (Å, °) for compounds (Ib), (Ic), (Ie), (IIa), (IId) and (IIe) topCg1, Cg2, Cg3 and Cg4 represent the centroids of the rings C311–C316), (C351–C356), (C351–C354/C359/C360) and (C355–C360), respectively |
Compound | D—H···A | D—A | H···A | D···A | D—H···A |
(Ib) | C355—H355···O14i | 0.93 | 2.59 | 3.468 (4) | 158 |
| C356—H356···O1ii | 0.93 | 2.51 | 3.360 (4) | 152 |
(Ic) | C19—H19···O1iii | 0.93 | 2.25 | 3.161 (3) | 165 |
| C16—H16···Cg2 | 0.93 | 2.98 | 3.882 (2) | 165 |
| C356—H356···Cg1iv | 0.93 | 2.88 | 3.685 (2) | 146 |
(Ie) | C19—H19···O1v | 0.93 | 2.32 | 3.233 (5) | 165 |
| C353—H353···Cg1vi | 0.93 | 2.86 | 3.708 (3) | 152 |
(IIa) | C357—H35B···O1vii | 0.96 | 2.51 | 3.396 (4) | 154 |
(IId) | C356—H356···O1viii | 0.93 | 2.32 | 3.115 (18) | 143 |
| C456—H456···O1viii | 0.93 | 2.47 | 3.21 (2) | 137 |
(IIe) | C353—H353···O1ix | 0.93 | 2.47 | 3.288 (4) | 147 |
| C12—H12···Cg3x | 0.93 | 2.93 | 3.761 (4) | 150 |
| C13—H13···Cg4x | 0.93 | 2.73 | 3.547 (4) | 148 |
Symmmetry codes: (i) 2 - x, -y, 1 - z; (ii) 2 - x, 1 - y, 1 - z; (iii) 1 + x, 1 + y, z; (iv) 1 - x, -y, 2 - z; (v) -1 + x, 1 + y, z; (vi) 1 - x, -y, 1 - z; (vii) 1 - x, 1 - y, 2 - z; (viii) 1 - x, 2 - y, 1 - z; (ix) 1 - x, 1 - y, -z; (x) -1 + x, y, z. |
Acknowledgements
HKK thanks the UGC-BSR for a stipend and the University of Mysore for research facilities.
Funding information
HSY thanks the University Grants Commission, New Delhi for the award of a BSR Faculty Fellowship for three years.
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