organic compounds
2-[3-(4-Chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-8H-indeno[1,2-d]thiazole
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, dPharmaceutical Chemistry Department, College of Pharmacy, Umm Al-Qura University, Makkah, Saudi Arabia, and eSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
*Correspondence e-mail: gelhiti@ksu.edu.sa
The title molecule, C25H17ClFN3S, contains indenothiazolyl (A), pyrazolyl (B), fluorophenyl (C) and chlorophenyl (D) groups. The dihedral angles between the ring planes A/B, B/C and B/D are 14.2 (1), 83.0 (1) and 6.5 (2)°, respectively. In the crystal, pairs of molecules related by inversion symmetry are linked by pairwise weak C—H⋯N interactions, forming dimers. These dimers interact through π–π contacts between the thiazolyl units [centroid-to-centroid distance = 3.826 (1) Å], forming chains along [010].
Keywords: crystal structure; pyrazole; thiazole; indole.
CCDC reference: 1896426
Structure description
Indeno[1,2-d]thiazoles act as histone deacetylase inhibitors (Zhou et al., 2013; Chordia et al., 2005). Thiazoles and pyrazoles have various biological activities (Chhabria et al., 2016; Faria et al., 2017). As part of our studies in these areas we now report the synthesis and structure of the title compound.
The A) and pyrazolyl (B), fluorophenyl (C) and chlorophenyl (D) rings (Fig. 1). The twist angles between the planes through neighbouring ring pairs A/B, B/C and B/D are 14.2 (1)°, 83.0 (1)° and 6.5 (2)°, respectively. In the crystal, pairs of molecules related by inversion symmetry are linked by C—H⋯N interactions, forming dimers in the (Table 1, Fig. 2). Neighbouring dimers interact through π–π contacts involving the thiazolyl fragments with centroid-to-centroid distances of 3.826 (1) Å, forming chains along [010].
consists of one molecule of the title compound. The molecule contains an indenothiazolyl ring system (Synthesis and crystallization
The title compound was synthesized from the condensation reaction between 3-(4-chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide (0.67 g, 2.0 mmol) and 2-bromo-2,3-dihydro-1H-inden-1-one (1.10 g, 2.0 mmol) in anhydrous ethanol (20 ml) under reflux for 2 h. The solid obtained was recrystallized from dimethylformamide solution to give colourless crystals (72%), m.p. 510–511 K.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1896426
https://doi.org/10.1107/S2414314619002189/lh4044sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619002189/lh4044Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314619002189/lh4044Isup3.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).C25H17ClFN3S | F(000) = 920 |
Mr = 445.92 | Dx = 1.406 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6975 (6) Å | Cell parameters from 5333 reflections |
b = 11.0671 (5) Å | θ = 4.0–27.3° |
c = 16.5395 (10) Å | µ = 0.31 mm−1 |
β = 100.303 (6)° | T = 296 K |
V = 2106.6 (2) Å3 | Plate, colourless |
Z = 4 | 0.44 × 0.32 × 0.06 mm |
Rigaku Oxford Diffraction SuperNova, Dual, Cu at zero, Atlas diffractometer | 3547 reflections with I > 2σ(I) |
ω scans | Rint = 0.043 |
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015) | θmax = 30.0°, θmin = 3.4° |
Tmin = 0.989, Tmax = 0.998 | h = −15→15 |
21492 measured reflections | k = −15→13 |
5397 independent reflections | l = −22→22 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0434P)2 + 0.7878P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
5397 reflections | Δρmax = 0.25 e Å−3 |
280 parameters | Δρmin = −0.22 e Å−3 |
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 methine and aromatic C—H H atoms were set to 0.98 Å and 0.93 Å respectively. Bond distances for methylene C—H H atoms were set to 0.97 Å and all Uiso(H) set to 1.2 times Ueq(C). |
x | y | z | Uiso*/Ueq | ||
C1 | 0.36830 (18) | −0.00576 (17) | −0.10974 (13) | 0.0483 (5) | |
C2 | 0.44396 (17) | 0.08820 (17) | −0.10383 (13) | 0.0462 (5) | |
C3 | 0.52516 (17) | 0.06919 (17) | −0.15981 (12) | 0.0464 (5) | |
C4 | 0.49318 (18) | −0.03929 (17) | −0.20216 (13) | 0.0475 (5) | |
C5 | 0.3909 (2) | −0.09670 (18) | −0.17192 (14) | 0.0538 (5) | |
H5A | 0.324551 | −0.105536 | −0.215951 | 0.065* | |
H5B | 0.411204 | −0.174911 | −0.146943 | 0.065* | |
C6 | 0.61892 (19) | 0.13560 (19) | −0.17651 (14) | 0.0544 (5) | |
H6 | 0.641714 | 0.206470 | −0.147914 | 0.065* | |
C7 | 0.6778 (2) | 0.0942 (2) | −0.23659 (15) | 0.0624 (6) | |
H7 | 0.740834 | 0.137899 | −0.248192 | 0.075* | |
C8 | 0.6448 (2) | −0.0103 (2) | −0.27944 (15) | 0.0624 (6) | |
H8 | 0.684815 | −0.035674 | −0.320197 | 0.075* | |
C9 | 0.5523 (2) | −0.0782 (2) | −0.26226 (14) | 0.0575 (6) | |
H9 | 0.530384 | −0.149161 | −0.291019 | 0.069* | |
C10 | 0.34436 (18) | 0.15028 (16) | −0.01316 (13) | 0.0471 (5) | |
C11 | 0.35404 (19) | 0.33553 (17) | 0.07738 (13) | 0.0514 (5) | |
H11 | 0.439164 | 0.333925 | 0.086955 | 0.062* | |
C12 | 0.3099 (2) | 0.33867 (18) | 0.15953 (13) | 0.0540 (5) | |
H12A | 0.371666 | 0.320498 | 0.205330 | 0.065* | |
H12B | 0.276437 | 0.416657 | 0.168531 | 0.065* | |
C13 | 0.21881 (18) | 0.24094 (17) | 0.14765 (13) | 0.0497 (5) | |
C14 | 0.30859 (17) | 0.44092 (17) | 0.02312 (12) | 0.0448 (4) | |
C15 | 0.37269 (18) | 0.54709 (18) | 0.02780 (13) | 0.0483 (5) | |
H15 | 0.446141 | 0.549470 | 0.060477 | 0.058* | |
C16 | 0.32965 (19) | 0.64896 (18) | −0.01498 (14) | 0.0530 (5) | |
H16 | 0.373157 | 0.719698 | −0.011724 | 0.064* | |
C17 | 0.2220 (2) | 0.6434 (2) | −0.06206 (14) | 0.0569 (6) | |
C18 | 0.1550 (2) | 0.5415 (2) | −0.06839 (15) | 0.0623 (6) | |
H18 | 0.081432 | 0.540603 | −0.100926 | 0.075* | |
C19 | 0.19912 (19) | 0.4400 (2) | −0.02540 (14) | 0.0553 (5) | |
H19 | 0.154650 | 0.369904 | −0.029061 | 0.066* | |
C20 | 0.13608 (18) | 0.21879 (18) | 0.20216 (13) | 0.0495 (5) | |
C21 | 0.1378 (2) | 0.2885 (2) | 0.27216 (14) | 0.0600 (6) | |
H21 | 0.193419 | 0.348873 | 0.284704 | 0.072* | |
C22 | 0.0585 (2) | 0.2697 (2) | 0.32356 (15) | 0.0647 (6) | |
H22 | 0.059898 | 0.317708 | 0.369871 | 0.078* | |
C24 | −0.0221 (2) | 0.1798 (2) | 0.30554 (15) | 0.0591 (6) | |
C25 | −0.0244 (2) | 0.1081 (2) | 0.23778 (17) | 0.0673 (6) | |
H25 | −0.078825 | 0.046278 | 0.226694 | 0.081* | |
C26 | 0.0535 (2) | 0.1274 (2) | 0.18630 (15) | 0.0632 (6) | |
H26 | 0.051152 | 0.078706 | 0.140185 | 0.076* | |
N1 | 0.43084 (15) | 0.17969 (14) | −0.04911 (11) | 0.0488 (4) | |
N2 | 0.30655 (17) | 0.21900 (15) | 0.04455 (12) | 0.0582 (5) | |
N3 | 0.22147 (16) | 0.17424 (15) | 0.08447 (12) | 0.0529 (4) | |
F1 | 0.17949 (14) | 0.74318 (13) | −0.10484 (10) | 0.0883 (5) | |
Cl1 | −0.12023 (6) | 0.15339 (7) | 0.37082 (5) | 0.0860 (2) | |
S1 | 0.27382 (5) | 0.01232 (4) | −0.04205 (3) | 0.05072 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0528 (12) | 0.0401 (10) | 0.0530 (12) | 0.0004 (9) | 0.0120 (10) | −0.0012 (9) |
C2 | 0.0492 (11) | 0.0405 (10) | 0.0490 (11) | 0.0013 (8) | 0.0090 (9) | 0.0003 (9) |
C3 | 0.0492 (11) | 0.0431 (10) | 0.0466 (11) | 0.0056 (9) | 0.0080 (9) | 0.0056 (9) |
C4 | 0.0545 (12) | 0.0413 (10) | 0.0464 (11) | 0.0058 (9) | 0.0084 (9) | 0.0033 (9) |
C5 | 0.0631 (13) | 0.0428 (11) | 0.0560 (13) | 0.0009 (10) | 0.0123 (11) | −0.0032 (9) |
C6 | 0.0576 (13) | 0.0480 (11) | 0.0594 (14) | −0.0001 (10) | 0.0154 (11) | 0.0005 (10) |
C7 | 0.0642 (14) | 0.0611 (14) | 0.0668 (15) | 0.0035 (11) | 0.0247 (12) | 0.0086 (12) |
C8 | 0.0743 (16) | 0.0621 (14) | 0.0560 (14) | 0.0138 (12) | 0.0260 (12) | 0.0073 (11) |
C9 | 0.0729 (15) | 0.0490 (12) | 0.0520 (13) | 0.0080 (11) | 0.0153 (12) | −0.0003 (10) |
C10 | 0.0531 (12) | 0.0372 (9) | 0.0520 (12) | −0.0001 (8) | 0.0122 (10) | −0.0003 (9) |
C11 | 0.0544 (12) | 0.0423 (10) | 0.0591 (13) | −0.0048 (9) | 0.0149 (10) | −0.0069 (9) |
C12 | 0.0653 (14) | 0.0468 (11) | 0.0499 (12) | −0.0032 (10) | 0.0106 (11) | −0.0019 (9) |
C13 | 0.0553 (12) | 0.0419 (10) | 0.0520 (12) | 0.0014 (9) | 0.0103 (10) | −0.0012 (9) |
C14 | 0.0474 (11) | 0.0453 (10) | 0.0441 (11) | −0.0066 (8) | 0.0148 (9) | −0.0082 (8) |
C15 | 0.0460 (11) | 0.0515 (11) | 0.0489 (12) | −0.0086 (9) | 0.0128 (9) | −0.0069 (9) |
C16 | 0.0599 (13) | 0.0466 (11) | 0.0557 (13) | −0.0113 (10) | 0.0191 (11) | −0.0031 (10) |
C17 | 0.0667 (14) | 0.0527 (12) | 0.0525 (13) | 0.0027 (11) | 0.0141 (11) | 0.0022 (10) |
C18 | 0.0561 (13) | 0.0701 (15) | 0.0568 (14) | −0.0075 (11) | −0.0007 (11) | −0.0016 (12) |
C19 | 0.0555 (12) | 0.0529 (12) | 0.0574 (13) | −0.0152 (10) | 0.0097 (11) | −0.0070 (10) |
C20 | 0.0552 (12) | 0.0435 (10) | 0.0503 (12) | 0.0047 (9) | 0.0108 (10) | 0.0026 (9) |
C21 | 0.0714 (15) | 0.0521 (12) | 0.0591 (14) | −0.0044 (11) | 0.0186 (12) | −0.0020 (11) |
C22 | 0.0825 (17) | 0.0596 (14) | 0.0559 (14) | 0.0024 (12) | 0.0231 (13) | −0.0005 (11) |
C24 | 0.0531 (13) | 0.0668 (14) | 0.0605 (14) | 0.0118 (11) | 0.0187 (11) | 0.0170 (12) |
C25 | 0.0587 (14) | 0.0705 (15) | 0.0743 (17) | −0.0080 (12) | 0.0163 (13) | 0.0031 (13) |
C26 | 0.0623 (14) | 0.0668 (14) | 0.0622 (15) | −0.0082 (11) | 0.0164 (12) | −0.0100 (12) |
N1 | 0.0522 (10) | 0.0406 (8) | 0.0554 (10) | −0.0033 (7) | 0.0143 (8) | −0.0059 (7) |
N2 | 0.0699 (12) | 0.0414 (9) | 0.0705 (12) | −0.0104 (8) | 0.0324 (10) | −0.0115 (8) |
N3 | 0.0598 (11) | 0.0432 (9) | 0.0601 (11) | −0.0049 (8) | 0.0224 (9) | −0.0049 (8) |
F1 | 0.0987 (11) | 0.0689 (9) | 0.0919 (12) | 0.0080 (8) | 0.0023 (9) | 0.0216 (8) |
Cl1 | 0.0753 (4) | 0.1069 (6) | 0.0848 (5) | 0.0073 (4) | 0.0388 (4) | 0.0210 (4) |
S1 | 0.0565 (3) | 0.0401 (3) | 0.0580 (3) | −0.0045 (2) | 0.0169 (3) | −0.0028 (2) |
C1—C2 | 1.358 (3) | C12—H12B | 0.9700 |
C1—C5 | 1.496 (3) | C13—N3 | 1.284 (3) |
C1—S1 | 1.720 (2) | C13—C20 | 1.457 (3) |
C2—N1 | 1.385 (3) | C14—C19 | 1.384 (3) |
C2—C3 | 1.455 (3) | C14—C15 | 1.389 (3) |
C3—C6 | 1.388 (3) | C15—C16 | 1.378 (3) |
C3—C4 | 1.406 (3) | C15—H15 | 0.9300 |
C4—C9 | 1.377 (3) | C16—C17 | 1.359 (3) |
C4—C5 | 1.516 (3) | C16—H16 | 0.9300 |
C5—H5A | 0.9700 | C17—F1 | 1.357 (3) |
C5—H5B | 0.9700 | C17—C18 | 1.366 (3) |
C6—C7 | 1.384 (3) | C18—C19 | 1.379 (3) |
C6—H6 | 0.9300 | C18—H18 | 0.9300 |
C7—C8 | 1.375 (3) | C19—H19 | 0.9300 |
C7—H7 | 0.9300 | C20—C21 | 1.388 (3) |
C8—C9 | 1.389 (3) | C20—C26 | 1.391 (3) |
C8—H8 | 0.9300 | C21—C22 | 1.382 (3) |
C9—H9 | 0.9300 | C21—H21 | 0.9300 |
C10—N1 | 1.303 (3) | C22—C24 | 1.367 (3) |
C10—N2 | 1.355 (3) | C22—H22 | 0.9300 |
C10—S1 | 1.7605 (19) | C24—C25 | 1.369 (3) |
C11—N2 | 1.469 (2) | C24—Cl1 | 1.735 (2) |
C11—C14 | 1.509 (3) | C25—C26 | 1.371 (3) |
C11—C12 | 1.538 (3) | C25—H25 | 0.9300 |
C11—H11 | 0.9800 | C26—H26 | 0.9300 |
C12—C13 | 1.506 (3) | N2—N3 | 1.381 (2) |
C12—H12A | 0.9700 | ||
C2—C1—C5 | 111.81 (19) | N3—C13—C20 | 121.49 (19) |
C2—C1—S1 | 110.52 (15) | N3—C13—C12 | 113.55 (19) |
C5—C1—S1 | 137.66 (16) | C20—C13—C12 | 124.95 (18) |
C1—C2—N1 | 117.39 (19) | C19—C14—C15 | 118.22 (19) |
C1—C2—C3 | 109.55 (18) | C19—C14—C11 | 122.01 (18) |
N1—C2—C3 | 133.06 (18) | C15—C14—C11 | 119.43 (18) |
C6—C3—C4 | 120.1 (2) | C16—C15—C14 | 121.32 (19) |
C6—C3—C2 | 132.74 (19) | C16—C15—H15 | 119.3 |
C4—C3—C2 | 107.13 (17) | C14—C15—H15 | 119.3 |
C9—C4—C3 | 120.2 (2) | C17—C16—C15 | 118.24 (19) |
C9—C4—C5 | 129.37 (19) | C17—C16—H16 | 120.9 |
C3—C4—C5 | 110.41 (18) | C15—C16—H16 | 120.9 |
C1—C5—C4 | 101.07 (17) | F1—C17—C16 | 118.5 (2) |
C1—C5—H5A | 111.6 | F1—C17—C18 | 118.7 (2) |
C4—C5—H5A | 111.6 | C16—C17—C18 | 122.8 (2) |
C1—C5—H5B | 111.6 | C17—C18—C19 | 118.4 (2) |
C4—C5—H5B | 111.6 | C17—C18—H18 | 120.8 |
H5A—C5—H5B | 109.4 | C19—C18—H18 | 120.8 |
C7—C6—C3 | 118.7 (2) | C18—C19—C14 | 121.0 (2) |
C7—C6—H6 | 120.7 | C18—C19—H19 | 119.5 |
C3—C6—H6 | 120.7 | C14—C19—H19 | 119.5 |
C8—C7—C6 | 121.2 (2) | C21—C20—C26 | 117.9 (2) |
C8—C7—H7 | 119.4 | C21—C20—C13 | 120.70 (19) |
C6—C7—H7 | 119.4 | C26—C20—C13 | 121.4 (2) |
C7—C8—C9 | 120.5 (2) | C22—C21—C20 | 121.2 (2) |
C7—C8—H8 | 119.8 | C22—C21—H21 | 119.4 |
C9—C8—H8 | 119.8 | C20—C21—H21 | 119.4 |
C4—C9—C8 | 119.3 (2) | C24—C22—C21 | 119.2 (2) |
C4—C9—H9 | 120.4 | C24—C22—H22 | 120.4 |
C8—C9—H9 | 120.4 | C21—C22—H22 | 120.4 |
N1—C10—N2 | 123.99 (18) | C22—C24—C25 | 120.8 (2) |
N1—C10—S1 | 117.21 (15) | C22—C24—Cl1 | 119.6 (2) |
N2—C10—S1 | 118.80 (16) | C25—C24—Cl1 | 119.6 (2) |
N2—C11—C14 | 112.88 (18) | C24—C25—C26 | 120.0 (2) |
N2—C11—C12 | 100.47 (16) | C24—C25—H25 | 120.0 |
C14—C11—C12 | 111.69 (17) | C26—C25—H25 | 120.0 |
N2—C11—H11 | 110.5 | C25—C26—C20 | 120.8 (2) |
C14—C11—H11 | 110.5 | C25—C26—H26 | 119.6 |
C12—C11—H11 | 110.5 | C20—C26—H26 | 119.6 |
C13—C12—C11 | 102.13 (16) | C10—N1—C2 | 107.54 (16) |
C13—C12—H12A | 111.3 | C10—N2—N3 | 119.31 (16) |
C11—C12—H12A | 111.3 | C10—N2—C11 | 127.12 (18) |
C13—C12—H12B | 111.3 | N3—N2—C11 | 113.29 (17) |
C11—C12—H12B | 111.3 | C13—N3—N2 | 107.89 (17) |
H12A—C12—H12B | 109.2 | C1—S1—C10 | 87.31 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16···N1i | 0.93 | 2.59 | 3.392 (3) | 145 |
Symmetry code: (i) −x+1, −y+1, −z. |
Footnotes
‡Additional correspondence author, e-mail: kariukib@cardiff.ac.uk.
Acknowledgements
The authors thank Umm Al-Qura and Cardiff Universities for their continuing support.
Funding information
Funding for this research was provided by: Deanship of Scientific Research at Umm Al-Qura University (award No. 17-MED-1-03-0007).
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