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organic compounds
4-{1-[4-(4-Bromophenyl)-1,3-thiazol-2-yl]-5-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-3-yl}-5-methyl-1-(4-methylphenyl)-1H-1,2,3-triazole
aApplied Organic Chemistry Department, National Research Centre, Dokki, 12622 Giza, Egypt, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: Edward.Tiekink@gmail.com
In the title compound, C28H22BrFN6S, the central pyrazole ring has an with the methine C atom being the flap atom. The dihedral angles between the least-squares plane through this ring and the adjacent thiazole [18.81 (15)°] and triazole [1.83 (16)°] rings indicate a twist in the molecule. A further twist is evident by the dihedral angle of 64.48 (16)° between the triazole ring and the attached benzene ring. In the crystal, C—H⋯N, C—H⋯F, C—H⋯π and π–π interactions [occurring between the thiazole and triazole rings, centroid–centroid distance = 3.571 (2) Å] link molecules into a three-dimensional architecture. The sample studied was a non-merohedral twin; the minor twin component refined to 47.16 (7)%.
Related literature
For the biological activity of related compounds, see: Abdel-Wahab et al. (2009, 2012a
). For a related pyrazolyl-1,2,3-triazole structure, see: Abdel-Wahab et al. (2012b
). For the deconvolution of twinned data, see: Spek (2009
).
Experimental
Crystal data
|
|
Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: ORTEP-3 (Farrugia, 1997
) and DIAMOND (Brandenburg, 2006
); software used to prepare material for publication: publCIF (Westrip, 2010
).
Supporting information
10.1107/S1600536812024257/su2440sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812024257/su2440Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812024257/su2440Isup3.cml
The title compound was prepared according to the reported method (Abdel-Wahab et al., 2012a). Crystals were obtained from its DMF solution by slow evaporation at room temperature.
C-bound H-atoms were placed in calculated positions [N—H = 0.88 Å and C—H = 0.95 to 1.00 Å, Uiso(H) = 1.2Ueq(N,C) or = 1.5Ueq(C-methyl)] and were included in the
in the riding model approximation. The sample studied is a non-merohedral twin and a full sphere of reflections was measured. As it was not possible to separate the diffraction spots in two domains, the twin domains were separated using the TwinRotMat routine of PLATON (Spek, 2009). The minor twin component refined to 47.16 (7)%. Two reflections, i.e. (-11 -8 2) and (0 -2 4), were omitted owing to poor agreement. The maximum and minimum residual electron density peaks of 1.44 and 0.53 e Å-3, respectively, were located 0.51 Å and 0.81 Å from the H13C and F9 atoms, respectively.Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C28H22BrFN6S | F(000) = 1168 |
Mr = 573.49 | Dx = 1.497 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3622 reflections |
a = 11.3476 (7) Å | θ = 2.6–27.5° |
b = 14.0549 (8) Å | µ = 1.74 mm−1 |
c = 15.954 (7) Å | T = 100 K |
V = 2544.5 (12) Å3 | Prism, light-brown |
Z = 4 | 0.40 × 0.20 × 0.10 mm |
Agilent SuperNova Dual diffractometer with an Atlas detector | 5293 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 4819 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.029 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.6° |
ω scan | h = −14→10 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −17→12 |
Tmin = 0.695, Tmax = 1.000 | l = −20→11 |
7265 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0325P)2 + 0.2812P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
5293 reflections | Δρmax = 0.36 e Å−3 |
336 parameters | Δρmin = −0.50 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2028 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.001 (7) |
C28H22BrFN6S | V = 2544.5 (12) Å3 |
Mr = 573.49 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.3476 (7) Å | µ = 1.74 mm−1 |
b = 14.0549 (8) Å | T = 100 K |
c = 15.954 (7) Å | 0.40 × 0.20 × 0.10 mm |
Agilent SuperNova Dual diffractometer with an Atlas detector | 5293 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | 4819 reflections with I > 2σ(I) |
Tmin = 0.695, Tmax = 1.000 | Rint = 0.029 |
7265 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.077 | Δρmax = 0.36 e Å−3 |
S = 1.02 | Δρmin = −0.50 e Å−3 |
5293 reflections | Absolute structure: Flack (1983), 2028 Friedel pairs |
336 parameters | Absolute structure parameter: 0.001 (7) |
0 restraints |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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 | ||
Br1 | 0.23440 (3) | 0.94410 (2) | −0.361341 (19) | 0.02124 (8) | |
S1 | 0.66530 (6) | 0.86176 (5) | 0.08004 (5) | 0.01822 (17) | |
F1 | 0.94395 (17) | 1.26252 (12) | −0.25372 (13) | 0.0294 (5) | |
N1 | 1.2170 (2) | 0.77775 (16) | 0.21438 (15) | 0.0152 (5) | |
N2 | 1.2929 (2) | 0.78394 (16) | 0.14807 (16) | 0.0174 (5) | |
N3 | 1.2310 (2) | 0.81441 (16) | 0.08489 (15) | 0.0154 (5) | |
N4 | 0.9210 (2) | 0.87452 (17) | 0.06940 (16) | 0.0171 (5) | |
N5 | 0.8648 (2) | 0.91513 (18) | 0.00017 (16) | 0.0170 (5) | |
N6 | 0.6859 (2) | 0.91897 (16) | −0.07364 (16) | 0.0155 (5) | |
C1 | 1.2602 (3) | 0.7492 (2) | 0.29537 (18) | 0.0167 (6) | |
C2 | 1.2594 (3) | 0.8146 (2) | 0.36070 (19) | 0.0208 (6) | |
H2 | 1.2265 | 0.8761 | 0.3532 | 0.025* | |
C3 | 1.3073 (3) | 0.7883 (2) | 0.4366 (2) | 0.0255 (7) | |
H3 | 1.3062 | 0.8322 | 0.4818 | 0.031* | |
C4 | 1.3573 (3) | 0.6990 (2) | 0.4485 (2) | 0.0247 (7) | |
C5 | 1.3549 (3) | 0.6346 (2) | 0.3825 (2) | 0.0247 (8) | |
H5 | 1.3869 | 0.5728 | 0.3902 | 0.030* | |
C6 | 1.3067 (3) | 0.6589 (2) | 0.3059 (2) | 0.0204 (7) | |
H6 | 1.3055 | 0.6144 | 0.2611 | 0.024* | |
C7 | 1.4158 (3) | 0.6738 (3) | 0.5301 (2) | 0.0366 (9) | |
H7A | 1.3946 | 0.6086 | 0.5458 | 0.055* | |
H7B | 1.3895 | 0.7179 | 0.5739 | 0.055* | |
H7C | 1.5016 | 0.6785 | 0.5238 | 0.055* | |
C8 | 1.0046 (3) | 0.8013 (2) | 0.2515 (2) | 0.0178 (6) | |
H8A | 1.0048 | 0.7410 | 0.2823 | 0.027* | |
H8B | 0.9310 | 0.8072 | 0.2199 | 0.027* | |
H8C | 1.0112 | 0.8543 | 0.2912 | 0.027* | |
C9 | 1.1057 (3) | 0.8035 (2) | 0.1929 (2) | 0.0151 (6) | |
C10 | 1.1170 (3) | 0.8273 (2) | 0.10935 (19) | 0.0142 (6) | |
C11 | 1.0306 (3) | 0.8628 (2) | 0.05071 (18) | 0.0138 (6) | |
C12 | 1.0619 (3) | 0.8935 (2) | −0.03664 (19) | 0.0170 (6) | |
H12A | 1.1013 | 0.8416 | −0.0678 | 0.020* | |
H12B | 1.1138 | 0.9501 | −0.0361 | 0.020* | |
C13 | 0.9411 (2) | 0.9169 (2) | −0.07472 (19) | 0.0148 (6) | |
H13 | 0.9171 | 0.8647 | −0.1138 | 0.018* | |
C14 | 0.9378 (2) | 1.0115 (2) | −0.12096 (18) | 0.0159 (6) | |
C15 | 0.8894 (3) | 1.0932 (2) | −0.0868 (2) | 0.0196 (7) | |
H15 | 0.8547 | 1.0910 | −0.0326 | 0.024* | |
C16 | 0.8913 (3) | 1.1791 (2) | −0.1314 (2) | 0.0241 (7) | |
H16 | 0.8576 | 1.2353 | −0.1085 | 0.029* | |
C17 | 0.9427 (3) | 1.1797 (2) | −0.2088 (2) | 0.0208 (7) | |
C18 | 0.9940 (3) | 1.1004 (2) | −0.2437 (2) | 0.0188 (7) | |
H18 | 1.0310 | 1.1036 | −0.2971 | 0.023* | |
C19 | 0.9906 (3) | 1.0161 (2) | −0.1994 (2) | 0.0177 (6) | |
H19 | 1.0247 | 0.9604 | −0.2229 | 0.021* | |
C20 | 0.7446 (3) | 0.90135 (18) | −0.00607 (17) | 0.0152 (6) | |
C21 | 0.5397 (3) | 0.8702 (2) | 0.0193 (2) | 0.0190 (7) | |
H21 | 0.4623 | 0.8560 | 0.0382 | 0.023* | |
C22 | 0.5671 (3) | 0.8999 (2) | −0.0593 (2) | 0.0171 (7) | |
C23 | 0.4858 (2) | 0.91170 (19) | −0.1308 (2) | 0.0155 (6) | |
C24 | 0.5272 (2) | 0.9486 (2) | −0.20621 (19) | 0.0180 (6) | |
H24 | 0.6073 | 0.9676 | −0.2105 | 0.022* | |
C25 | 0.4538 (3) | 0.9581 (2) | −0.27493 (19) | 0.0197 (7) | |
H25 | 0.4831 | 0.9831 | −0.3262 | 0.024* | |
C26 | 0.3367 (3) | 0.9305 (2) | −0.26774 (19) | 0.0168 (6) | |
C27 | 0.2930 (3) | 0.8929 (2) | −0.1943 (2) | 0.0204 (7) | |
H27 | 0.2129 | 0.8736 | −0.1906 | 0.025* | |
C28 | 0.3677 (3) | 0.8836 (2) | −0.1253 (2) | 0.0197 (7) | |
H28 | 0.3383 | 0.8581 | −0.0743 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.02349 (14) | 0.02282 (14) | 0.01741 (15) | −0.00056 (13) | −0.00417 (13) | 0.00095 (13) |
S1 | 0.0157 (3) | 0.0244 (4) | 0.0145 (4) | −0.0021 (3) | 0.0021 (3) | 0.0024 (3) |
F1 | 0.0288 (10) | 0.0224 (9) | 0.0372 (12) | −0.0012 (9) | −0.0056 (10) | 0.0159 (9) |
N1 | 0.0152 (12) | 0.0186 (11) | 0.0117 (13) | −0.0003 (10) | −0.0012 (10) | −0.0026 (10) |
N2 | 0.0187 (12) | 0.0181 (11) | 0.0153 (14) | 0.0005 (10) | 0.0004 (11) | −0.0009 (11) |
N3 | 0.0176 (12) | 0.0168 (11) | 0.0119 (12) | 0.0000 (11) | −0.0006 (11) | 0.0005 (10) |
N4 | 0.0181 (12) | 0.0197 (12) | 0.0137 (14) | 0.0004 (11) | −0.0021 (11) | 0.0045 (11) |
N5 | 0.0126 (11) | 0.0257 (13) | 0.0128 (13) | −0.0008 (10) | 0.0031 (10) | 0.0055 (11) |
N6 | 0.0126 (11) | 0.0174 (12) | 0.0166 (13) | 0.0018 (10) | 0.0022 (10) | 0.0014 (10) |
C1 | 0.0150 (13) | 0.0222 (13) | 0.0130 (14) | −0.0009 (13) | −0.0013 (13) | 0.0050 (11) |
C2 | 0.0214 (14) | 0.0231 (13) | 0.0178 (15) | 0.0020 (12) | −0.0002 (16) | −0.0005 (13) |
C3 | 0.0273 (17) | 0.0338 (18) | 0.0153 (17) | −0.0043 (15) | −0.0011 (14) | −0.0030 (14) |
C4 | 0.0226 (16) | 0.0355 (18) | 0.0161 (17) | −0.0044 (15) | −0.0018 (13) | 0.0095 (15) |
C5 | 0.0236 (15) | 0.0221 (15) | 0.028 (2) | 0.0002 (14) | −0.0025 (14) | 0.0073 (14) |
C6 | 0.0188 (14) | 0.0219 (15) | 0.0204 (17) | −0.0012 (13) | −0.0020 (13) | −0.0002 (13) |
C7 | 0.033 (2) | 0.057 (2) | 0.020 (2) | −0.0065 (19) | −0.0102 (17) | 0.0115 (18) |
C8 | 0.0159 (13) | 0.0236 (15) | 0.0139 (15) | 0.0004 (12) | 0.0026 (12) | 0.0021 (13) |
C9 | 0.0143 (14) | 0.0143 (14) | 0.0166 (16) | −0.0011 (12) | 0.0012 (12) | −0.0013 (12) |
C10 | 0.0175 (13) | 0.0129 (13) | 0.0123 (15) | −0.0016 (12) | 0.0007 (12) | 0.0018 (11) |
C11 | 0.0160 (13) | 0.0145 (13) | 0.0109 (15) | −0.0034 (12) | 0.0020 (12) | −0.0032 (12) |
C12 | 0.0147 (14) | 0.0203 (15) | 0.0161 (16) | 0.0012 (12) | 0.0024 (13) | 0.0046 (13) |
C13 | 0.0146 (13) | 0.0171 (14) | 0.0128 (15) | −0.0004 (12) | 0.0007 (12) | 0.0010 (12) |
C14 | 0.0116 (13) | 0.0197 (14) | 0.0165 (17) | −0.0018 (12) | −0.0034 (12) | 0.0045 (12) |
C15 | 0.0190 (14) | 0.0231 (15) | 0.0167 (17) | 0.0005 (13) | 0.0012 (13) | 0.0015 (13) |
C16 | 0.0200 (14) | 0.0212 (15) | 0.031 (2) | 0.0050 (12) | −0.0010 (16) | −0.0028 (16) |
C17 | 0.0183 (15) | 0.0195 (15) | 0.0244 (18) | −0.0034 (13) | −0.0075 (14) | 0.0130 (14) |
C18 | 0.0135 (14) | 0.0278 (16) | 0.0152 (16) | −0.0032 (13) | −0.0026 (13) | 0.0070 (14) |
C19 | 0.0140 (14) | 0.0199 (14) | 0.0191 (17) | 0.0012 (12) | −0.0035 (13) | −0.0010 (13) |
C20 | 0.0152 (14) | 0.0159 (12) | 0.0146 (14) | 0.0030 (12) | 0.0020 (12) | 0.0017 (11) |
C21 | 0.0154 (14) | 0.0218 (15) | 0.0198 (17) | −0.0011 (13) | 0.0004 (13) | 0.0017 (14) |
C22 | 0.0163 (14) | 0.0161 (14) | 0.0190 (17) | 0.0017 (12) | −0.0014 (13) | −0.0002 (13) |
C23 | 0.0152 (13) | 0.0138 (12) | 0.0175 (16) | 0.0025 (11) | 0.0003 (13) | 0.0018 (13) |
C24 | 0.0150 (13) | 0.0164 (14) | 0.0226 (16) | −0.0011 (13) | 0.0009 (12) | 0.0011 (14) |
C25 | 0.0217 (14) | 0.0193 (15) | 0.0180 (16) | 0.0031 (13) | 0.0014 (13) | 0.0037 (13) |
C26 | 0.0184 (14) | 0.0163 (14) | 0.0158 (15) | 0.0043 (13) | −0.0044 (12) | −0.0001 (12) |
C27 | 0.0145 (15) | 0.0253 (16) | 0.0215 (17) | −0.0012 (12) | 0.0009 (13) | −0.0001 (13) |
C28 | 0.0185 (14) | 0.0243 (15) | 0.0161 (18) | 0.0005 (12) | 0.0029 (13) | 0.0016 (13) |
Br1—C26 | 1.901 (3) | C8—H8C | 0.9800 |
S1—C21 | 1.728 (3) | C9—C10 | 1.381 (4) |
S1—C20 | 1.734 (3) | C10—C11 | 1.445 (4) |
F1—C17 | 1.367 (3) | C11—C12 | 1.501 (4) |
N1—C9 | 1.358 (4) | C12—C13 | 1.535 (4) |
N1—N2 | 1.367 (3) | C12—H12A | 0.9900 |
N1—C1 | 1.439 (4) | C12—H12B | 0.9900 |
N2—N3 | 1.300 (3) | C13—C14 | 1.521 (4) |
N3—C10 | 1.363 (4) | C13—H13 | 1.0000 |
N4—C11 | 1.290 (4) | C14—C19 | 1.389 (4) |
N4—N5 | 1.397 (3) | C14—C15 | 1.385 (4) |
N5—C20 | 1.381 (4) | C15—C16 | 1.402 (4) |
N5—C13 | 1.475 (4) | C15—H15 | 0.9500 |
N6—C20 | 1.291 (4) | C16—C17 | 1.365 (5) |
N6—C22 | 1.394 (4) | C16—H16 | 0.9500 |
C1—C6 | 1.384 (4) | C17—C18 | 1.376 (4) |
C1—C2 | 1.390 (4) | C18—C19 | 1.380 (4) |
C2—C3 | 1.377 (4) | C18—H18 | 0.9500 |
C2—H2 | 0.9500 | C19—H19 | 0.9500 |
C3—C4 | 1.390 (5) | C21—C22 | 1.357 (4) |
C3—H3 | 0.9500 | C21—H21 | 0.9500 |
C4—C5 | 1.388 (5) | C22—C23 | 1.476 (4) |
C4—C7 | 1.504 (4) | C23—C24 | 1.392 (4) |
C5—C6 | 1.383 (4) | C23—C28 | 1.400 (4) |
C5—H5 | 0.9500 | C24—C25 | 1.383 (4) |
C6—H6 | 0.9500 | C24—H24 | 0.9500 |
C7—H7A | 0.9800 | C25—C26 | 1.390 (4) |
C7—H7B | 0.9800 | C25—H25 | 0.9500 |
C7—H7C | 0.9800 | C26—C27 | 1.378 (4) |
C8—C9 | 1.480 (4) | C27—C28 | 1.396 (4) |
C8—H8A | 0.9800 | C27—H27 | 0.9500 |
C8—H8B | 0.9800 | C28—H28 | 0.9500 |
C21—S1—C20 | 87.81 (15) | C13—C12—H12B | 111.3 |
C9—N1—N2 | 112.0 (2) | H12A—C12—H12B | 109.2 |
C9—N1—C1 | 128.1 (3) | N5—C13—C14 | 113.2 (2) |
N2—N1—C1 | 119.9 (2) | N5—C13—C12 | 101.5 (2) |
N3—N2—N1 | 106.3 (2) | C14—C13—C12 | 113.6 (2) |
N2—N3—C10 | 109.5 (2) | N5—C13—H13 | 109.4 |
C11—N4—N5 | 108.0 (2) | C14—C13—H13 | 109.4 |
C20—N5—N4 | 116.8 (2) | C12—C13—H13 | 109.4 |
C20—N5—C13 | 121.5 (3) | C19—C14—C15 | 119.2 (3) |
N4—N5—C13 | 112.3 (2) | C19—C14—C13 | 117.9 (3) |
C20—N6—C22 | 109.0 (2) | C15—C14—C13 | 122.9 (3) |
C6—C1—C2 | 121.2 (3) | C14—C15—C16 | 120.5 (3) |
C6—C1—N1 | 119.6 (3) | C14—C15—H15 | 119.7 |
C2—C1—N1 | 119.1 (3) | C16—C15—H15 | 119.7 |
C3—C2—C1 | 118.6 (3) | C17—C16—C15 | 118.1 (3) |
C3—C2—H2 | 120.7 | C17—C16—H16 | 120.9 |
C1—C2—H2 | 120.7 | C15—C16—H16 | 120.9 |
C2—C3—C4 | 121.6 (3) | C16—C17—F1 | 119.0 (3) |
C2—C3—H3 | 119.2 | C16—C17—C18 | 122.8 (3) |
C4—C3—H3 | 119.2 | F1—C17—C18 | 118.2 (3) |
C3—C4—C5 | 118.5 (3) | C17—C18—C19 | 118.4 (3) |
C3—C4—C7 | 120.8 (3) | C17—C18—H18 | 120.8 |
C5—C4—C7 | 120.8 (3) | C19—C18—H18 | 120.8 |
C6—C5—C4 | 121.2 (3) | C14—C19—C18 | 120.9 (3) |
C6—C5—H5 | 119.4 | C14—C19—H19 | 119.6 |
C4—C5—H5 | 119.4 | C18—C19—H19 | 119.6 |
C5—C6—C1 | 119.0 (3) | N6—C20—N5 | 122.9 (3) |
C5—C6—H6 | 120.5 | N6—C20—S1 | 117.1 (2) |
C1—C6—H6 | 120.5 | N5—C20—S1 | 120.0 (2) |
C4—C7—H7A | 109.5 | C22—C21—S1 | 110.5 (2) |
C4—C7—H7B | 109.5 | C22—C21—H21 | 124.7 |
H7A—C7—H7B | 109.5 | S1—C21—H21 | 124.7 |
C4—C7—H7C | 109.5 | C21—C22—N6 | 115.6 (3) |
H7A—C7—H7C | 109.5 | C21—C22—C23 | 127.2 (3) |
H7B—C7—H7C | 109.5 | N6—C22—C23 | 117.1 (3) |
C9—C8—H8A | 109.5 | C24—C23—C28 | 118.9 (3) |
C9—C8—H8B | 109.5 | C24—C23—C22 | 119.9 (3) |
H8A—C8—H8B | 109.5 | C28—C23—C22 | 121.2 (3) |
C9—C8—H8C | 109.5 | C25—C24—C23 | 121.2 (3) |
H8A—C8—H8C | 109.5 | C25—C24—H24 | 119.4 |
H8B—C8—H8C | 109.5 | C23—C24—H24 | 119.4 |
N1—C9—C10 | 102.8 (3) | C24—C25—C26 | 118.9 (3) |
N1—C9—C8 | 123.8 (3) | C24—C25—H25 | 120.6 |
C10—C9—C8 | 133.4 (3) | C26—C25—H25 | 120.6 |
N3—C10—C9 | 109.4 (3) | C27—C26—C25 | 121.4 (3) |
N3—C10—C11 | 120.3 (3) | C27—C26—Br1 | 119.2 (2) |
C9—C10—C11 | 130.2 (3) | C25—C26—Br1 | 119.4 (2) |
N4—C11—C10 | 123.3 (3) | C26—C27—C28 | 119.2 (3) |
N4—C11—C12 | 114.0 (3) | C26—C27—H27 | 120.4 |
C10—C11—C12 | 122.7 (3) | C28—C27—H27 | 120.4 |
C11—C12—C13 | 102.6 (2) | C27—C28—C23 | 120.4 (3) |
C11—C12—H12A | 111.3 | C27—C28—H28 | 119.8 |
C13—C12—H12A | 111.3 | C23—C28—H28 | 119.8 |
C11—C12—H12B | 111.3 | ||
C9—N1—N2—N3 | 0.7 (3) | C11—C12—C13—C14 | 132.8 (3) |
C1—N1—N2—N3 | −177.6 (2) | N5—C13—C14—C19 | −169.6 (3) |
N1—N2—N3—C10 | −0.4 (3) | C12—C13—C14—C19 | 75.3 (3) |
C11—N4—N5—C20 | 156.5 (3) | N5—C13—C14—C15 | 13.2 (4) |
C11—N4—N5—C13 | 9.4 (3) | C12—C13—C14—C15 | −101.9 (3) |
C9—N1—C1—C6 | 118.3 (3) | C19—C14—C15—C16 | 1.3 (4) |
N2—N1—C1—C6 | −63.7 (4) | C13—C14—C15—C16 | 178.5 (3) |
C9—N1—C1—C2 | −64.7 (4) | C14—C15—C16—C17 | −0.5 (5) |
N2—N1—C1—C2 | 113.3 (3) | C15—C16—C17—F1 | 179.1 (3) |
C6—C1—C2—C3 | 0.7 (5) | C15—C16—C17—C18 | −1.0 (5) |
N1—C1—C2—C3 | −176.2 (3) | C16—C17—C18—C19 | 1.7 (5) |
C1—C2—C3—C4 | 0.9 (5) | F1—C17—C18—C19 | −178.5 (3) |
C2—C3—C4—C5 | −2.0 (5) | C15—C14—C19—C18 | −0.7 (4) |
C2—C3—C4—C7 | 176.2 (3) | C13—C14—C19—C18 | −178.0 (3) |
C3—C4—C5—C6 | 1.6 (5) | C17—C18—C19—C14 | −0.8 (4) |
C7—C4—C5—C6 | −176.6 (3) | C22—N6—C20—N5 | −178.7 (3) |
C4—C5—C6—C1 | 0.0 (5) | C22—N6—C20—S1 | −0.4 (3) |
C2—C1—C6—C5 | −1.2 (5) | N4—N5—C20—N6 | −166.6 (3) |
N1—C1—C6—C5 | 175.8 (3) | C13—N5—C20—N6 | −22.6 (4) |
N2—N1—C9—C10 | −0.7 (3) | N4—N5—C20—S1 | 15.2 (4) |
C1—N1—C9—C10 | 177.5 (3) | C13—N5—C20—S1 | 159.2 (2) |
N2—N1—C9—C8 | 178.3 (3) | C21—S1—C20—N6 | −0.3 (2) |
C1—N1—C9—C8 | −3.5 (5) | C21—S1—C20—N5 | 178.0 (2) |
N2—N3—C10—C9 | −0.1 (3) | C20—S1—C21—C22 | 1.0 (2) |
N2—N3—C10—C11 | 178.7 (2) | S1—C21—C22—N6 | −1.5 (3) |
N1—C9—C10—N3 | 0.5 (3) | S1—C21—C22—C23 | 176.9 (2) |
C8—C9—C10—N3 | −178.4 (3) | C20—N6—C22—C21 | 1.2 (4) |
N1—C9—C10—C11 | −178.2 (3) | C20—N6—C22—C23 | −177.4 (2) |
C8—C9—C10—C11 | 2.9 (6) | C21—C22—C23—C24 | 176.1 (3) |
N5—N4—C11—C10 | 176.4 (3) | N6—C22—C23—C24 | −5.6 (4) |
N5—N4—C11—C12 | −1.1 (3) | C21—C22—C23—C28 | −6.0 (5) |
N3—C10—C11—N4 | 178.4 (3) | N6—C22—C23—C28 | 172.4 (3) |
C9—C10—C11—N4 | −3.1 (5) | C28—C23—C24—C25 | 0.3 (4) |
N3—C10—C11—C12 | −4.3 (4) | C22—C23—C24—C25 | 178.3 (3) |
C9—C10—C11—C12 | 174.2 (3) | C23—C24—C25—C26 | 0.3 (5) |
N4—C11—C12—C13 | −6.8 (3) | C24—C25—C26—C27 | −0.8 (5) |
C10—C11—C12—C13 | 175.6 (2) | C24—C25—C26—Br1 | 179.5 (2) |
C20—N5—C13—C14 | 79.6 (3) | C25—C26—C27—C28 | 0.8 (4) |
N4—N5—C13—C14 | −135.1 (2) | Br1—C26—C27—C28 | −179.5 (2) |
C20—N5—C13—C12 | −158.3 (3) | C26—C27—C28—C23 | −0.3 (4) |
N4—N5—C13—C12 | −12.9 (3) | C24—C23—C28—C27 | −0.3 (4) |
C11—C12—C13—N5 | 11.0 (3) | C22—C23—C28—C27 | −178.2 (3) |
Cg1 is the centroid of the C23–C28 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···N2i | 1.00 | 2.58 | 3.488 (4) | 151 |
C27—H27···F1ii | 0.95 | 2.53 | 3.358 (4) | 146 |
C8—H8A···Cg1iii | 0.98 | 2.84 | 3.401 (3) | 117 |
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) −x+1, y−1/2, −z−1/2; (iii) −x, y+3/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C28H22BrFN6S |
Mr | 573.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 11.3476 (7), 14.0549 (8), 15.954 (7) |
V (Å3) | 2544.5 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.40 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with an Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2011) |
Tmin, Tmax | 0.695, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7265, 5293, 4819 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.077, 1.02 |
No. of reflections | 5293 |
No. of parameters | 336 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.50 |
Absolute structure | Flack (1983), 2028 Friedel pairs |
Absolute structure parameter | 0.001 (7) |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
Cg1 is the centroid of the C23–C28 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···N2i | 1.00 | 2.58 | 3.488 (4) | 151 |
C27—H27···F1ii | 0.95 | 2.53 | 3.358 (4) | 146 |
C8—H8A···Cg1iii | 0.98 | 2.84 | 3.401 (3) | 117 |
Symmetry codes: (i) x−1/2, −y+3/2, −z; (ii) −x+1, y−1/2, −z−1/2; (iii) −x, y+3/2, −z+1/2. |
Footnotes
‡Additional correspondence author: bakrfatehy@yahoo.com
Acknowledgements
We thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).
References
Abdel-Wahab, B. F., Abdel-Aziz, H. A. & Ahmed, E. M. (2009). Eur. J. Med. Chem. 44, 2632–2635. Web of Science PubMed CAS Google Scholar
Abdel-Wahab, B. F., Abdel-Latif, E., Mohamed, H. A. & Awad, G. E. A. (2012a). Eur. J. Med. Chem. 52, 263–268. Web of Science CAS PubMed Google Scholar
Abdel-Wahab, B. F., Abdel-Latif, E., Ng, S. W. & Tiekink, E. R. T. (2012b). Acta Cryst. E68, o1954–o1955. CSD CrossRef IUCr Journals Google Scholar
Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
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The crystal structure determination of the title compound, 4-(4-bromophenyl)-2-(5-(4-fluorophenyl)-3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-4,5-dihydro-1H-pyrazol-1-yl)thiazole (I), was investigated in relation to the established biological activities exhibited by 3-(benzofuran-2-yl)-4,5-dihydro-5-phenyl-1-(4-phenylthiazol-2-yl)-1H-pyrazole and 1,2,3-triazol-4-yl-pyrazolylthiazoles (Abdel-Wahab et al. 2012a; Abdel-Wahab et al. 2009) and related structural studies (Abdel-Wahab et al., 2012b).
The molecule of (I), Fig. 1, comprises a sequence of three linked five-membered rings with a benzene ring linked to each of these. The central pyrazole ring (r.m.s. deviation = 0.087 Å) adopts an envelope conformation with the methine-C13 atom being the flap atom. The molecule is twisted as seen in the dihedral angles between the least-squares plane through the pyrazole ring and the thiazole (r.m.s. deviation = 0.008 Å) and triazole (r.m.s. deviation = 0.004 Å) rings are 18.81 (15) and 1.83 (16)°, respectively. While the attached benzene ring to the thiazole ring is almost co-planar [dihedral angle = 7.00 (13)°], the benzene ring linked to the triazole ring is twisted out of its plane [dihedral angle = 64.48 (16)°].
In the crystal, C—H···N and C—H···π (Table 1), as well as π—π interactions occurring between the thiazole and triazole [inter-centroid distance = 3.571 (2) Å, angle of inclination = 5.08 (15)° for symmetry operation: -1/2 + x, 3/2 - y, -z] link molecules into layers in the ac plane. These layers are linked by C—H···F interactions (Fig. 2 and Table 1).