organic compounds
(4S,5R)-3-(4-Chlorophenyl)-5-(4-methoxyphenyl)-4-methyl-1-phenyl-4,5-dihydro-1H-pyrazole
aLaboratoire de Chimie Moléculaire, Faculté des Sciences Semlalia, BP 2390, Université Cadi Ayyad, 40001, Marrakech, Morocco, bLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco, and cLaboratoire de Chimie des Substances Naturelles, URAC16, Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, 40000 Marrakech, Morocco
*Correspondence e-mail: berraho@uca.ma
The title compound, C23H21ClN2O, was obtained via the condensation of trans anethole [systematic name: (E)-1-Methoxy-4-(1-propenyl)benzene] with diarylnitrilimine. In the molecule, the pyrazole ring adopts a twisted conformation. Dihedral angles between the pyrazole group and the three aromatic subunits (chlorophenyl, methoxyphenyl and phenyl) are 9.44 (14), 83.14 (1) and 20.86 (15)°, respectively. In the crystal, no classic hydrogen bonds are found; however C—H⋯π interactions link the molecules into chains parallel to the c axis.
Keywords: crystal structure; pyrazole; C—H⋯π interactions.
CCDC reference: 1487208
Structure description
Trans-anethole is the active ingredient of the anise essential oil and the source of the anise scent. It has anticarcinogenic (Chainy et al., 2000), antigenotoxic (Abraham et al., 2001), gastroprotective and anti-oxidative (Freire et al., 2005), antithrombotic (Tognolini et al., 2007), antimicrobial and antiviral (Astani et al., 2011) properties. The double bond in the aromatic α position confers some reactivity. In this work, we focused our efforts on the preparation of new heterocyclic systems by the 1,3-dipolar cycloaddition reaction from trans-anethole and diarylnitrilimine. The condensation of trans-anethole with diarylnitrilimine generated in situ by the action of triethylamine on N-phenylarylohydrazonoyl chloride (Huisgen et al., 1962) is carried out in dichloromethane at room temperature. The obtained residue was purified by on silica gel and the adduct was isolated in a satisfactory yield.
The structure of this new product (Fig. 1) was determined using its single-crystal X-ray diffraction data. The pyrazole ring has a twist conformation as indicated by the total puckering amplitude QT =0.158 (2) Å and φ =86.1 (8)°. The dihedral angles between the five-membered ring and the chlorophenyl, methoxyphenyl and phenyl rings are 9.44 (14), 83.14 (1) and 20.86 (15)°, respectively. The features C—H⋯π interactions (Table 1), which link the molecules into chains parallel to the c axis as shown in Fig. 2.
Synthesis and crystallization
Triethylamine (9 mmol) dissolved in dichloromethane (5 mL) was added dropwise to a solution of trans-anethole (6.74 mmol) and the precursor diarylnitrilimine (6.74 mmol) contained in a three-necked flask in dichloromethane (15 mL). After stirring for one day at room temperature, the mixture was washed several times with water (20 mL). The organic layers were separated, dried by anhydrous sodium sulfate, filtered and evaporated. The residue was purified in a silica-gel column (eluent: hexane/ethyl acetate 2/98), giving the title compound in 54% yield.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1487208
10.1107/S2414314616010221/bt4016sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616010221/bt4016Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616010221/bt4016Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).C23H21ClN2O | F(000) = 792 |
Mr = 376.87 | Dx = 1.279 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.564 (16) Å | Cell parameters from 3988 reflections |
b = 9.127 (8) Å | θ = 2.5–26.4° |
c = 11.001 (10) Å | µ = 0.21 mm−1 |
β = 94.88 (4)° | T = 298 K |
V = 1957 (3) Å3 | Prism, colourless |
Z = 4 | 0.30 × 0.26 × 0.17 mm |
Bruker X8 APEX diffractometer | 3988 independent reflections |
Radiation source: fine-focus sealed tube | 1917 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
φ and ω scans | θmax = 26.4°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −24→24 |
Tmin = 0.658, Tmax = 0.747 | k = −11→11 |
16805 measured reflections | l = −7→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0513P)2] where P = (Fo2 + 2Fc2)/3 |
3988 reflections | (Δ/σ)max < 0.001 |
246 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against all reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on all data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.04749 (4) | 0.25816 (8) | 0.48890 (8) | 0.0981 (3) | |
O1 | 0.51903 (9) | 0.34290 (18) | 0.41122 (18) | 0.0765 (5) | |
N2 | 0.25023 (10) | 0.4231 (2) | 0.05057 (19) | 0.0617 (6) | |
N1 | 0.19177 (9) | 0.43689 (19) | 0.10970 (18) | 0.0553 (5) | |
C4 | 0.35035 (11) | 0.3054 (2) | 0.1608 (2) | 0.0485 (6) | |
C1 | 0.18069 (12) | 0.3154 (2) | 0.1641 (2) | 0.0522 (6) | |
C10 | 0.26488 (12) | 0.5215 (2) | −0.0399 (2) | 0.0521 (6) | |
C3 | 0.28620 (12) | 0.2843 (2) | 0.0788 (2) | 0.0554 (6) | |
H3 | 0.2971 | 0.2364 | 0.0030 | 0.066* | |
C8 | 0.41134 (12) | 0.4210 (2) | 0.3330 (2) | 0.0553 (6) | |
H8 | 0.4138 | 0.4934 | 0.3927 | 0.066* | |
C9 | 0.35455 (12) | 0.4104 (2) | 0.2521 (2) | 0.0539 (6) | |
H9 | 0.3181 | 0.4747 | 0.2584 | 0.065* | |
C2 | 0.23065 (11) | 0.1962 (2) | 0.1382 (2) | 0.0551 (6) | |
H2 | 0.2502 | 0.1530 | 0.2150 | 0.066* | |
C7 | 0.46469 (12) | 0.3248 (2) | 0.3262 (2) | 0.0537 (6) | |
C18 | 0.06354 (13) | 0.1616 (3) | 0.3852 (3) | 0.0634 (7) | |
H18 | 0.0594 | 0.0769 | 0.4310 | 0.076* | |
C5 | 0.40490 (13) | 0.2124 (2) | 0.1551 (2) | 0.0607 (7) | |
H5 | 0.4035 | 0.1421 | 0.0937 | 0.073* | |
C19 | 0.01805 (13) | 0.2738 (3) | 0.3930 (3) | 0.0648 (7) | |
C16 | 0.12361 (12) | 0.3001 (2) | 0.2407 (2) | 0.0523 (6) | |
C17 | 0.11574 (12) | 0.1745 (2) | 0.3091 (2) | 0.0590 (7) | |
H17 | 0.1463 | 0.0973 | 0.3036 | 0.071* | |
C11 | 0.32179 (13) | 0.5030 (3) | −0.1049 (2) | 0.0584 (6) | |
H11 | 0.3523 | 0.4269 | −0.0847 | 0.070* | |
C15 | 0.22128 (13) | 0.6379 (2) | −0.0700 (2) | 0.0657 (7) | |
H15 | 0.1835 | 0.6542 | −0.0259 | 0.079* | |
C21 | 0.07674 (13) | 0.4117 (3) | 0.2509 (2) | 0.0646 (7) | |
H21 | 0.0806 | 0.4970 | 0.2057 | 0.077* | |
C6 | 0.46144 (13) | 0.2201 (3) | 0.2374 (3) | 0.0641 (7) | |
H6 | 0.4974 | 0.1542 | 0.2327 | 0.077* | |
C12 | 0.33373 (14) | 0.5966 (3) | −0.1997 (2) | 0.0684 (7) | |
H12 | 0.3722 | 0.5832 | −0.2425 | 0.082* | |
C23 | 0.19815 (13) | 0.0763 (3) | 0.0553 (2) | 0.0766 (8) | |
H23A | 0.1622 | 0.0292 | 0.0950 | 0.115* | |
H23B | 0.2324 | 0.0053 | 0.0390 | 0.115* | |
H23C | 0.1794 | 0.1190 | −0.0200 | 0.115* | |
C20 | 0.02443 (13) | 0.3997 (3) | 0.3264 (3) | 0.0689 (7) | |
H20 | −0.0064 | 0.4763 | 0.3324 | 0.083* | |
C14 | 0.23385 (15) | 0.7297 (3) | −0.1652 (3) | 0.0763 (8) | |
H14 | 0.2041 | 0.8071 | −0.1850 | 0.092* | |
C22 | 0.56136 (14) | 0.2214 (3) | 0.4389 (3) | 0.0920 (10) | |
H22A | 0.5343 | 0.1422 | 0.4666 | 0.138* | |
H22B | 0.5963 | 0.2472 | 0.5018 | 0.138* | |
H22C | 0.5824 | 0.1915 | 0.3672 | 0.138* | |
C13 | 0.28932 (17) | 0.7088 (3) | −0.2310 (3) | 0.0769 (8) | |
H13 | 0.2967 | 0.7701 | −0.2961 | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0884 (6) | 0.0939 (5) | 0.1166 (8) | −0.0106 (4) | 0.0361 (5) | 0.0046 (5) |
O1 | 0.0652 (12) | 0.0747 (12) | 0.0852 (15) | 0.0043 (9) | −0.0190 (11) | 0.0003 (10) |
N2 | 0.0594 (13) | 0.0641 (12) | 0.0614 (15) | 0.0122 (10) | 0.0035 (11) | 0.0200 (11) |
N1 | 0.0532 (12) | 0.0553 (12) | 0.0565 (14) | 0.0051 (9) | −0.0015 (10) | 0.0106 (10) |
C4 | 0.0522 (15) | 0.0453 (12) | 0.0479 (15) | 0.0079 (11) | 0.0034 (12) | 0.0062 (12) |
C1 | 0.0551 (15) | 0.0484 (13) | 0.0500 (16) | 0.0001 (11) | −0.0128 (13) | 0.0054 (12) |
C10 | 0.0590 (15) | 0.0464 (13) | 0.0488 (15) | −0.0071 (12) | −0.0073 (12) | 0.0029 (12) |
C3 | 0.0636 (16) | 0.0502 (13) | 0.0512 (16) | 0.0115 (12) | −0.0019 (13) | 0.0037 (12) |
C8 | 0.0650 (16) | 0.0458 (13) | 0.0551 (17) | 0.0041 (12) | 0.0051 (14) | −0.0022 (12) |
C9 | 0.0563 (15) | 0.0461 (13) | 0.0590 (17) | 0.0119 (11) | 0.0043 (13) | 0.0005 (13) |
C2 | 0.0613 (16) | 0.0498 (13) | 0.0515 (16) | 0.0065 (12) | −0.0105 (12) | 0.0071 (12) |
C7 | 0.0523 (16) | 0.0533 (14) | 0.0548 (17) | −0.0016 (12) | 0.0012 (14) | 0.0062 (13) |
C18 | 0.0651 (17) | 0.0564 (15) | 0.0662 (19) | −0.0136 (13) | −0.0082 (15) | 0.0092 (13) |
C5 | 0.0636 (17) | 0.0606 (15) | 0.0587 (18) | 0.0132 (13) | 0.0096 (14) | −0.0101 (13) |
C19 | 0.0578 (16) | 0.0647 (16) | 0.071 (2) | −0.0088 (13) | 0.0018 (14) | −0.0002 (15) |
C16 | 0.0539 (15) | 0.0495 (13) | 0.0508 (16) | −0.0022 (11) | −0.0105 (13) | 0.0046 (12) |
C17 | 0.0560 (16) | 0.0527 (14) | 0.0665 (18) | −0.0021 (12) | −0.0061 (14) | 0.0061 (13) |
C11 | 0.0680 (17) | 0.0523 (14) | 0.0532 (16) | −0.0053 (12) | −0.0051 (13) | −0.0035 (13) |
C15 | 0.0741 (18) | 0.0476 (14) | 0.074 (2) | −0.0006 (13) | −0.0006 (15) | 0.0078 (14) |
C21 | 0.0689 (17) | 0.0551 (14) | 0.0685 (19) | 0.0026 (13) | −0.0013 (15) | 0.0117 (14) |
C6 | 0.0515 (16) | 0.0656 (16) | 0.075 (2) | 0.0175 (12) | 0.0034 (15) | −0.0051 (15) |
C12 | 0.086 (2) | 0.0581 (15) | 0.0615 (19) | −0.0192 (15) | 0.0115 (15) | −0.0076 (15) |
C23 | 0.0889 (19) | 0.0564 (15) | 0.081 (2) | 0.0011 (14) | −0.0101 (16) | −0.0044 (14) |
C20 | 0.0661 (18) | 0.0619 (16) | 0.078 (2) | 0.0083 (13) | 0.0034 (16) | 0.0054 (15) |
C14 | 0.094 (2) | 0.0478 (15) | 0.085 (2) | 0.0013 (14) | −0.0043 (18) | 0.0201 (16) |
C22 | 0.071 (2) | 0.098 (2) | 0.103 (3) | 0.0150 (17) | −0.0181 (18) | 0.0142 (19) |
C13 | 0.109 (2) | 0.0524 (16) | 0.069 (2) | −0.0153 (16) | 0.0058 (18) | 0.0062 (15) |
Cl1—C19 | 1.734 (3) | C5—C6 | 1.370 (3) |
O1—C7 | 1.365 (3) | C5—H5 | 0.9300 |
O1—C22 | 1.402 (3) | C19—C20 | 1.373 (3) |
N2—N1 | 1.369 (2) | C16—C21 | 1.382 (3) |
N2—C10 | 1.389 (3) | C16—C17 | 1.387 (3) |
N2—C3 | 1.469 (3) | C17—H17 | 0.9300 |
N1—C1 | 1.287 (3) | C11—C12 | 1.383 (3) |
C4—C5 | 1.369 (3) | C11—H11 | 0.9300 |
C4—C9 | 1.386 (3) | C15—C14 | 1.380 (3) |
C4—C3 | 1.495 (3) | C15—H15 | 0.9300 |
C1—C16 | 1.462 (3) | C21—C20 | 1.377 (3) |
C1—C2 | 1.506 (3) | C21—H21 | 0.9300 |
C10—C11 | 1.384 (3) | C6—H6 | 0.9300 |
C10—C15 | 1.385 (3) | C12—C13 | 1.368 (3) |
C3—C2 | 1.541 (3) | C12—H12 | 0.9300 |
C3—H3 | 0.9800 | C23—H23A | 0.9600 |
C8—C9 | 1.366 (3) | C23—H23B | 0.9600 |
C8—C7 | 1.371 (3) | C23—H23C | 0.9600 |
C8—H8 | 0.9300 | C20—H20 | 0.9300 |
C9—H9 | 0.9300 | C14—C13 | 1.368 (4) |
C2—C23 | 1.527 (3) | C14—H14 | 0.9300 |
C2—H2 | 0.9800 | C22—H22A | 0.9600 |
C7—C6 | 1.365 (3) | C22—H22B | 0.9600 |
C18—C19 | 1.365 (3) | C22—H22C | 0.9600 |
C18—C17 | 1.380 (3) | C13—H13 | 0.9300 |
C18—H18 | 0.9300 | ||
C7—O1—C22 | 117.7 (2) | C20—C19—Cl1 | 119.9 (2) |
N1—N2—C10 | 120.85 (19) | C21—C16—C17 | 117.4 (2) |
N1—N2—C3 | 112.56 (18) | C21—C16—C1 | 121.4 (2) |
C10—N2—C3 | 125.8 (2) | C17—C16—C1 | 121.2 (2) |
C1—N1—N2 | 108.79 (18) | C18—C17—C16 | 121.5 (2) |
C5—C4—C9 | 117.6 (2) | C18—C17—H17 | 119.3 |
C5—C4—C3 | 120.7 (2) | C16—C17—H17 | 119.3 |
C9—C4—C3 | 121.5 (2) | C12—C11—C10 | 120.6 (2) |
N1—C1—C16 | 121.2 (2) | C12—C11—H11 | 119.7 |
N1—C1—C2 | 113.4 (2) | C10—C11—H11 | 119.7 |
C16—C1—C2 | 125.4 (2) | C14—C15—C10 | 120.1 (3) |
C11—C10—C15 | 118.5 (2) | C14—C15—H15 | 120.0 |
C11—C10—N2 | 121.0 (2) | C10—C15—H15 | 120.0 |
C15—C10—N2 | 120.5 (2) | C20—C21—C16 | 121.5 (2) |
N2—C3—C4 | 112.25 (19) | C20—C21—H21 | 119.3 |
N2—C3—C2 | 101.37 (18) | C16—C21—H21 | 119.3 |
C4—C3—C2 | 113.40 (19) | C7—C6—C5 | 119.7 (2) |
N2—C3—H3 | 109.8 | C7—C6—H6 | 120.2 |
C4—C3—H3 | 109.8 | C5—C6—H6 | 120.2 |
C2—C3—H3 | 109.8 | C13—C12—C11 | 120.5 (3) |
C9—C8—C7 | 120.0 (2) | C13—C12—H12 | 119.7 |
C9—C8—H8 | 120.0 | C11—C12—H12 | 119.7 |
C7—C8—H8 | 120.0 | C2—C23—H23A | 109.5 |
C8—C9—C4 | 121.0 (2) | C2—C23—H23B | 109.5 |
C8—C9—H9 | 119.5 | H23A—C23—H23B | 109.5 |
C4—C9—H9 | 119.5 | C2—C23—H23C | 109.5 |
C1—C2—C23 | 112.7 (2) | H23A—C23—H23C | 109.5 |
C1—C2—C3 | 101.28 (17) | H23B—C23—H23C | 109.5 |
C23—C2—C3 | 113.2 (2) | C19—C20—C21 | 119.7 (2) |
C1—C2—H2 | 109.8 | C19—C20—H20 | 120.2 |
C23—C2—H2 | 109.8 | C21—C20—H20 | 120.2 |
C3—C2—H2 | 109.8 | C13—C14—C15 | 121.2 (3) |
C6—C7—O1 | 124.2 (2) | C13—C14—H14 | 119.4 |
C6—C7—C8 | 119.9 (2) | C15—C14—H14 | 119.4 |
O1—C7—C8 | 115.9 (2) | O1—C22—H22A | 109.5 |
C19—C18—C17 | 119.6 (2) | O1—C22—H22B | 109.5 |
C19—C18—H18 | 120.2 | H22A—C22—H22B | 109.5 |
C17—C18—H18 | 120.2 | O1—C22—H22C | 109.5 |
C4—C5—C6 | 121.8 (2) | H22A—C22—H22C | 109.5 |
C4—C5—H5 | 119.1 | H22B—C22—H22C | 109.5 |
C6—C5—H5 | 119.1 | C12—C13—C14 | 119.1 (3) |
C18—C19—C20 | 120.3 (2) | C12—C13—H13 | 120.4 |
C18—C19—Cl1 | 119.7 (2) | C14—C13—H13 | 120.4 |
Cg3 and Cg4 are the centroids of the C10–C15 and C16–C21 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg3i | 0.98 | 2.98 | 3.847 (3) | 148 |
C23—H23C···Cg4ii | 0.96 | 2.80 | 3.679 (3) | 153 |
Symmetry codes: (i) x, −y−1/2, z−1/2; (ii) x, −y−1/2, z−3/2. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
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