organic compounds
5-[(4-Chlorophenyl)diazenyl]-2-[5-(4-fluorophenyl)-3-(furan-2-yl)-4,5-dihydro-1H-pyrazol-1-yl]-4-methylthiazole
aDepartment of Optometry, College of Applied Medical Sciences, King Saud University, PO Box 10219, Riyadh 11433, Saudi Arabia, bDepartment of Chemistry, College of Science and Humanities, Shaqra University, Duwadimi, Saudi Arabia, cApplied Organic Chemistry Department, National Research Centre, Dokki, Giza, Egypt, dDepartment of Chemistry, College of Science, Al-Nahrain University, Baghdad 64021, Iraq, eNational Center for Petrochemicals Technology, King Abdulaziz City for Science and Technology, PO Box 6086, Riyadh 11442, Saudi Arabia, and fSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
*Correspondence e-mail: gelhiti@ksu.edu.sa
The title compound, C23H17ClFN5OS, comprises fluorophenyl (A), furanyl (B), pyrazolyl (C), methylthiazoyl (D) and chlorophenyl (E) rings. The B–C–D–E linked ring system is close to planar with the dihedral angles B/C, C/D and D/E being 7.6 (1), 3.4 (1) and 8.4 (1)°, respectively. The fluorophenyl group is almost perpendicular to the pyrazoyl ring, as indicated by an A/C twist angle of 79.4 (1)°. In the crystal, inversion dimers linked by pairs of C—H⋯S contacts are observed.
Keywords: crystal structure; furan; pyrazole.
CCDC reference: 1895864
Structure description
Thiazoles are of importance in medicinal chemistry as they have various biological activities (Kashyap et al., 2012) and occur in natural products (Chhabria et al., 2016). Pyrazoles have a broad spectrum of biological activities (Faria et al., 2017). As part of our studies in these areas, we now describe the structure of the title compound.
The A), furanyl (B), pyrazolyl (C), methylthiazoyl (D) and chlorophenyl (E) rings (Fig. 1). The B–C–D–E linked ring system is close to planar with the B/C, C/D and D/E angles between neighbouring rings being 7.6 (1), 3.4 (1) and 8.4 (1)°, respectively. The fluorophenyl group (A) is almost perpendicular to the B–E system as indicated by an A/C twist angle of 79.4 (1)°. In the crystal, inversion dimers linked by pairs of C—H⋯S bonds (Table 1) generate R22(18) loops, which are stacked in the [100] direction (Fig. 2).
consists of one molecule of the title compound and comprises fluorophenyl (Synthesis and crystallization
The title compound was synthesized by the condensation of 5-(4-fluorophenyl)-3-(furan-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothioamide with N′-(4-chlorophenyl)-2-oxopropanehydrazonoyl chloride in ethanol containing catalytic amount of triethylamine as previously reported (Abdel-Wahab et al., 2013). The product was recrystallized from dimethylformamide solution to give colourless crystals (74%), m.p. 227–228°C.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1895864
https://doi.org/10.1107/S2414314619002116/hb4284sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619002116/hb4284Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314619002116/hb4284Isup3.cml
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell
CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows and WinGX (Farrugia, 2012); software used to prepare material for publication: CHEMDRAW Ultra (Cambridge Soft, 2001).C23H17ClFN5OS | F(000) = 960 |
Mr = 465.92 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2879 (3) Å | Cell parameters from 6690 reflections |
b = 26.3742 (10) Å | θ = 4.2–28.8° |
c = 15.7872 (7) Å | µ = 0.31 mm−1 |
β = 98.293 (4)° | T = 298 K |
V = 2178.72 (18) Å3 | Needle, colourless |
Z = 4 | 0.49 × 0.16 × 0.14 mm |
Rigaku Oxford Diffraction SuperNova, Dual, Cu at zero, Atlas diffractometer | 4143 reflections with I > 2σ(I) |
ω scans | Rint = 0.028 |
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015) | θmax = 29.7°, θmin = 3.5° |
Tmin = 0.993, Tmax = 0.997 | h = −6→6 |
21057 measured reflections | k = −33→36 |
5523 independent reflections | l = −18→21 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.7096P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
5523 reflections | Δρmax = 0.16 e Å−3 |
290 parameters | Δρmin = −0.31 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. All hydrogen atoms were placed in calculated positions and refined using a riding model. Bond distances for aromatic, methine and methylene C—H hydrogen atoms were set to 0.93 Å, 0.98 Å and 0.93 Å, respectively and their Uiso values set to 1.2 times Ueq(C). Bond distances for methyl C—H hydrogen atoms were set to 0.96 Å and their Uiso set to 1.5 times Ueq(C) with the group free to rotate about the C—C bond. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0781 (5) | 0.26438 (8) | 0.25920 (13) | 0.0626 (6) | |
C2 | −0.0593 (4) | 0.22058 (9) | 0.25800 (12) | 0.0632 (6) | |
H2 | −0.188107 | 0.216992 | 0.291921 | 0.076* | |
C3 | −0.0025 (4) | 0.18144 (8) | 0.20494 (11) | 0.0508 (4) | |
H3 | −0.094947 | 0.151351 | 0.202736 | 0.061* | |
C4 | 0.1904 (3) | 0.18705 (6) | 0.15553 (10) | 0.0385 (3) | |
C5 | 0.3267 (4) | 0.23211 (6) | 0.15976 (11) | 0.0465 (4) | |
H5 | 0.458123 | 0.235950 | 0.126987 | 0.056* | |
C6 | 0.2705 (5) | 0.27143 (7) | 0.21185 (13) | 0.0594 (5) | |
H6 | 0.361295 | 0.301722 | 0.214416 | 0.071* | |
C7 | 0.2489 (3) | 0.14657 (6) | 0.09325 (11) | 0.0414 (4) | |
H7 | 0.427871 | 0.148875 | 0.084020 | 0.050* | |
C8 | 0.0710 (4) | 0.14838 (6) | 0.00674 (11) | 0.0458 (4) | |
H8A | −0.030811 | 0.179117 | 0.001392 | 0.055* | |
H8B | 0.167553 | 0.146253 | −0.040917 | 0.055* | |
C9 | −0.0937 (3) | 0.10222 (6) | 0.01124 (10) | 0.0406 (4) | |
C10 | −0.3123 (4) | 0.09025 (6) | −0.05042 (11) | 0.0431 (4) | |
C11 | −0.4169 (4) | 0.11166 (7) | −0.12524 (11) | 0.0510 (4) | |
H11 | −0.358838 | 0.140346 | −0.150784 | 0.061* | |
C12 | −0.6331 (4) | 0.08164 (8) | −0.15704 (12) | 0.0559 (5) | |
H12 | −0.743848 | 0.086687 | −0.207690 | 0.067* | |
C13 | −0.6459 (4) | 0.04478 (8) | −0.09992 (13) | 0.0568 (5) | |
H13 | −0.770705 | 0.019689 | −0.104760 | 0.068* | |
C14 | 0.3140 (3) | 0.07128 (6) | 0.19213 (11) | 0.0413 (4) | |
C15 | 0.5955 (4) | 0.05794 (7) | 0.30614 (11) | 0.0453 (4) | |
C16 | 0.4562 (4) | 0.01408 (6) | 0.30647 (11) | 0.0451 (4) | |
C17 | 0.8202 (4) | 0.07168 (8) | 0.37081 (13) | 0.0588 (5) | |
H17A | 0.963604 | 0.079446 | 0.342109 | 0.088* | |
H17B | 0.862443 | 0.043675 | 0.409091 | 0.088* | |
H17C | 0.778770 | 0.100733 | 0.402770 | 0.088* | |
C18 | 0.3905 (4) | −0.10285 (7) | 0.40559 (11) | 0.0457 (4) | |
C19 | 0.6009 (4) | −0.10844 (8) | 0.46822 (13) | 0.0598 (5) | |
H19 | 0.722638 | −0.082798 | 0.477058 | 0.072* | |
C20 | 0.6311 (4) | −0.15181 (8) | 0.51757 (13) | 0.0628 (6) | |
H20 | 0.772774 | −0.155580 | 0.559425 | 0.075* | |
C21 | 0.4493 (4) | −0.18944 (7) | 0.50416 (11) | 0.0475 (4) | |
C22 | 0.2386 (4) | −0.18456 (7) | 0.44334 (12) | 0.0565 (5) | |
H22 | 0.116268 | −0.210100 | 0.435302 | 0.068* | |
C23 | 0.2105 (4) | −0.14106 (7) | 0.39398 (13) | 0.0563 (5) | |
H23 | 0.068133 | −0.137504 | 0.352340 | 0.068* | |
N1 | 0.1930 (3) | 0.09521 (5) | 0.12251 (9) | 0.0466 (4) | |
N2 | −0.0195 (3) | 0.07306 (5) | 0.07564 (9) | 0.0444 (3) | |
N3 | 0.5145 (3) | 0.09084 (5) | 0.24081 (9) | 0.0452 (3) | |
N4 | 0.5021 (3) | −0.02481 (6) | 0.36380 (9) | 0.0480 (4) | |
N5 | 0.3409 (3) | −0.06088 (6) | 0.34945 (10) | 0.0503 (4) | |
F1 | 0.0203 (4) | 0.30294 (6) | 0.31041 (9) | 0.1010 (6) | |
S2 | 0.20523 (9) | 0.01261 (2) | 0.22069 (3) | 0.04565 (13) | |
Cl1 | 0.49098 (13) | −0.24529 (2) | 0.56357 (3) | 0.07087 (18) | |
O1 | −0.4519 (3) | 0.04886 (5) | −0.03373 (8) | 0.0550 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0723 (15) | 0.0617 (12) | 0.0474 (10) | 0.0251 (11) | −0.0127 (10) | −0.0170 (9) |
C2 | 0.0544 (13) | 0.0884 (16) | 0.0475 (10) | 0.0187 (11) | 0.0095 (9) | −0.0047 (10) |
C3 | 0.0451 (11) | 0.0570 (11) | 0.0504 (10) | −0.0036 (8) | 0.0076 (8) | −0.0034 (8) |
C4 | 0.0371 (9) | 0.0372 (8) | 0.0398 (8) | −0.0012 (6) | 0.0012 (6) | 0.0004 (6) |
C5 | 0.0482 (11) | 0.0399 (9) | 0.0491 (9) | −0.0048 (7) | −0.0007 (8) | 0.0001 (7) |
C6 | 0.0702 (15) | 0.0404 (10) | 0.0604 (12) | 0.0013 (9) | −0.0152 (10) | −0.0079 (8) |
C7 | 0.0424 (10) | 0.0352 (8) | 0.0473 (9) | −0.0052 (7) | 0.0087 (7) | −0.0015 (7) |
C8 | 0.0553 (11) | 0.0403 (9) | 0.0417 (9) | −0.0062 (8) | 0.0071 (8) | −0.0021 (7) |
C9 | 0.0450 (10) | 0.0357 (8) | 0.0416 (8) | −0.0002 (7) | 0.0078 (7) | −0.0031 (6) |
C10 | 0.0469 (10) | 0.0380 (8) | 0.0445 (9) | −0.0023 (7) | 0.0073 (7) | −0.0038 (7) |
C11 | 0.0572 (12) | 0.0473 (10) | 0.0472 (9) | 0.0034 (8) | 0.0035 (8) | 0.0022 (8) |
C12 | 0.0574 (13) | 0.0578 (11) | 0.0486 (10) | 0.0084 (9) | −0.0050 (9) | −0.0065 (8) |
C13 | 0.0500 (12) | 0.0548 (11) | 0.0613 (11) | −0.0068 (9) | −0.0066 (9) | −0.0083 (9) |
C14 | 0.0432 (10) | 0.0344 (8) | 0.0460 (9) | 0.0005 (7) | 0.0048 (7) | −0.0042 (7) |
C15 | 0.0430 (10) | 0.0462 (9) | 0.0460 (9) | 0.0013 (7) | 0.0038 (7) | −0.0081 (7) |
C16 | 0.0466 (10) | 0.0436 (9) | 0.0434 (9) | 0.0026 (7) | 0.0007 (7) | −0.0034 (7) |
C17 | 0.0512 (12) | 0.0675 (13) | 0.0543 (11) | −0.0070 (10) | −0.0043 (9) | −0.0089 (9) |
C18 | 0.0461 (11) | 0.0468 (9) | 0.0428 (9) | 0.0037 (8) | 0.0013 (7) | 0.0001 (7) |
C19 | 0.0511 (12) | 0.0591 (12) | 0.0647 (12) | −0.0075 (9) | −0.0071 (9) | 0.0090 (9) |
C20 | 0.0536 (13) | 0.0695 (13) | 0.0588 (11) | −0.0006 (10) | −0.0136 (9) | 0.0128 (10) |
C21 | 0.0543 (12) | 0.0478 (9) | 0.0399 (8) | 0.0058 (8) | 0.0054 (8) | 0.0036 (7) |
C22 | 0.0565 (13) | 0.0495 (10) | 0.0592 (11) | −0.0059 (9) | −0.0066 (9) | 0.0042 (8) |
C23 | 0.0532 (12) | 0.0534 (11) | 0.0559 (11) | −0.0018 (9) | −0.0138 (9) | 0.0042 (8) |
N1 | 0.0522 (9) | 0.0332 (7) | 0.0506 (8) | −0.0070 (6) | −0.0060 (7) | 0.0001 (6) |
N2 | 0.0472 (9) | 0.0367 (7) | 0.0469 (8) | −0.0040 (6) | −0.0011 (6) | −0.0018 (6) |
N3 | 0.0457 (9) | 0.0403 (7) | 0.0485 (8) | −0.0033 (6) | 0.0024 (6) | −0.0046 (6) |
N4 | 0.0510 (10) | 0.0463 (8) | 0.0456 (8) | 0.0020 (7) | 0.0030 (7) | −0.0001 (6) |
N5 | 0.0530 (10) | 0.0462 (8) | 0.0493 (8) | 0.0020 (7) | −0.0006 (7) | 0.0027 (6) |
F1 | 0.1302 (14) | 0.0924 (10) | 0.0740 (9) | 0.0464 (10) | −0.0072 (9) | −0.0408 (8) |
S2 | 0.0486 (3) | 0.0353 (2) | 0.0500 (2) | −0.00246 (17) | −0.00321 (19) | −0.00071 (16) |
Cl1 | 0.0867 (4) | 0.0649 (3) | 0.0580 (3) | 0.0043 (3) | 0.0002 (3) | 0.0203 (2) |
O1 | 0.0565 (9) | 0.0499 (7) | 0.0546 (7) | −0.0141 (6) | −0.0052 (6) | 0.0049 (6) |
C1—C6 | 1.359 (3) | C13—H13 | 0.9300 |
C1—F1 | 1.361 (2) | C14—N3 | 1.321 (2) |
C1—C2 | 1.363 (3) | C14—N1 | 1.346 (2) |
C2—C3 | 1.389 (3) | C14—S2 | 1.7330 (17) |
C2—H2 | 0.9300 | C15—N3 | 1.369 (2) |
C3—C4 | 1.379 (2) | C15—C16 | 1.372 (3) |
C3—H3 | 0.9300 | C15—C17 | 1.495 (3) |
C4—C5 | 1.386 (2) | C16—N4 | 1.366 (2) |
C4—C7 | 1.513 (2) | C16—S2 | 1.7546 (18) |
C5—C6 | 1.382 (3) | C17—H17A | 0.9600 |
C5—H5 | 0.9300 | C17—H17B | 0.9600 |
C6—H6 | 0.9300 | C17—H17C | 0.9600 |
C7—N1 | 1.475 (2) | C18—C23 | 1.380 (3) |
C7—C8 | 1.543 (2) | C18—C19 | 1.386 (3) |
C7—H7 | 0.9800 | C18—N5 | 1.419 (2) |
C8—C9 | 1.504 (2) | C19—C20 | 1.380 (3) |
C8—H8A | 0.9700 | C19—H19 | 0.9300 |
C8—H8B | 0.9700 | C20—C21 | 1.377 (3) |
C9—N2 | 1.290 (2) | C20—H20 | 0.9300 |
C9—C10 | 1.435 (2) | C21—C22 | 1.368 (3) |
C10—C11 | 1.353 (2) | C21—Cl1 | 1.7432 (18) |
C10—O1 | 1.365 (2) | C22—C23 | 1.383 (3) |
C11—C12 | 1.422 (3) | C22—H22 | 0.9300 |
C11—H11 | 0.9300 | C23—H23 | 0.9300 |
C12—C13 | 1.334 (3) | N1—N2 | 1.3823 (19) |
C12—H12 | 0.9300 | N4—N5 | 1.276 (2) |
C13—O1 | 1.359 (2) | ||
C6—C1—F1 | 118.3 (2) | O1—C13—H13 | 124.6 |
C6—C1—C2 | 123.24 (18) | N3—C14—N1 | 122.60 (15) |
F1—C1—C2 | 118.4 (2) | N3—C14—S2 | 117.77 (13) |
C1—C2—C3 | 118.5 (2) | N1—C14—S2 | 119.63 (13) |
C1—C2—H2 | 120.8 | N3—C15—C16 | 115.32 (16) |
C3—C2—H2 | 120.8 | N3—C15—C17 | 119.51 (16) |
C4—C3—C2 | 120.21 (19) | C16—C15—C17 | 125.17 (17) |
C4—C3—H3 | 119.9 | N4—C16—C15 | 126.26 (17) |
C2—C3—H3 | 119.9 | N4—C16—S2 | 122.47 (14) |
C3—C4—C5 | 119.12 (16) | C15—C16—S2 | 111.26 (13) |
C3—C4—C7 | 121.94 (15) | C15—C17—H17A | 109.5 |
C5—C4—C7 | 118.85 (15) | C15—C17—H17B | 109.5 |
C6—C5—C4 | 121.13 (19) | H17A—C17—H17B | 109.5 |
C6—C5—H5 | 119.4 | C15—C17—H17C | 109.5 |
C4—C5—H5 | 119.4 | H17A—C17—H17C | 109.5 |
C1—C6—C5 | 117.82 (19) | H17B—C17—H17C | 109.5 |
C1—C6—H6 | 121.1 | C23—C18—C19 | 118.99 (17) |
C5—C6—H6 | 121.1 | C23—C18—N5 | 115.16 (16) |
N1—C7—C4 | 112.05 (14) | C19—C18—N5 | 125.85 (17) |
N1—C7—C8 | 100.45 (13) | C20—C19—C18 | 120.42 (19) |
C4—C7—C8 | 113.43 (14) | C20—C19—H19 | 119.8 |
N1—C7—H7 | 110.2 | C18—C19—H19 | 119.8 |
C4—C7—H7 | 110.2 | C21—C20—C19 | 119.30 (18) |
C8—C7—H7 | 110.2 | C21—C20—H20 | 120.4 |
C9—C8—C7 | 102.49 (13) | C19—C20—H20 | 120.4 |
C9—C8—H8A | 111.3 | C22—C21—C20 | 121.34 (17) |
C7—C8—H8A | 111.3 | C22—C21—Cl1 | 118.96 (15) |
C9—C8—H8B | 111.3 | C20—C21—Cl1 | 119.67 (15) |
C7—C8—H8B | 111.3 | C21—C22—C23 | 118.96 (18) |
H8A—C8—H8B | 109.2 | C21—C22—H22 | 120.5 |
N2—C9—C10 | 121.82 (15) | C23—C22—H22 | 120.5 |
N2—C9—C8 | 114.04 (15) | C18—C23—C22 | 120.99 (18) |
C10—C9—C8 | 124.13 (15) | C18—C23—H23 | 119.5 |
C11—C10—O1 | 109.75 (16) | C22—C23—H23 | 119.5 |
C11—C10—C9 | 133.48 (17) | C14—N1—N2 | 119.53 (14) |
O1—C10—C9 | 116.77 (15) | C14—N1—C7 | 126.37 (14) |
C10—C11—C12 | 106.40 (17) | N2—N1—C7 | 113.86 (13) |
C10—C11—H11 | 126.8 | C9—N2—N1 | 107.54 (14) |
C12—C11—H11 | 126.8 | C14—N3—C15 | 109.17 (14) |
C13—C12—C11 | 106.48 (17) | N5—N4—C16 | 113.09 (15) |
C13—C12—H12 | 126.8 | N4—N5—C18 | 114.36 (15) |
C11—C12—H12 | 126.8 | C14—S2—C16 | 86.48 (8) |
C12—C13—O1 | 110.85 (17) | C13—O1—C10 | 106.51 (14) |
C12—C13—H13 | 124.6 |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···S2i | 0.93 | 2.85 | 3.612 (2) | 140 |
Symmetry code: (i) −x−1, −y, −z. |
Footnotes
‡Additional correspondence author: e-mail kariukib@cardiff.ac.uk.
Acknowledgements
The authors thank King Saud and Cardiff Universities for continuous support.
Funding information
Funding for this research was provided by: King Abdulaziz City for Science and Technology (KACST), Saudi Arabia (award No. 020-0180).
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