organic compounds
5-(4-tert-Butylbenzylsulfanyl)-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde
aDepartment of Chemistry, Huzhou University, Huzhou 313000, People's Republic of China
*Correspondence e-mail: chenyi_wang2006@yahoo.com.cn
The title compound, C22H24N2OS, has been synthesized as a potent fungicidal agent and its determined. In the weak intermolecular C—H⋯O interactions are observed. The dihedral angles between the planes of the pyrazole and phenyl rings, and between the benzene and pyrazole rings are 54.2 (2) and 25.0 (3)°, respectively. The methyl groups of the tert-butyl group are disordered over two positions; the site occupancies are ca 0.65 and 0.35.
Related literature
For related literature, see: Becher et al. (1986); Bekhit & Abdel-Aziem (2004); Comber et al. (1991); Dannhardt & Kiefer (2001); Gamage et al. (2002); Goekan-Kelekci et al. (2007); Hashizume et al. (2004); Park et al. (2005).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S160053680706597X/em2002sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680706597X/em2002Isup2.hkl
To a cooled solution of sodium hydride (0.023 mol) in anhydrous THF (15 ml), was added dropwise (4-tert-butylphenyl)methanethiol (0.022 mol). The reaction mixture was stirred at room temperature for 1 h, and then a solution of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde (Becher et al.,1986; 0.020 mol) in anhydrous THF (25 ml) was added dropwise. The mixture was stirred at room temperature for another 2 h, and then poured into water (50 ml) to yield a colourless precipitate (Scheme 1). The resulting precipitate was recrystallized from petroleum ether/ethyl acetate (5:1 v/v) to give colourless crystals (yield 60%).
In the t-butyl group the methyl groups were disordered over two sets positions with occupy factors 0.655 (12)/0.345 (12). The displacement parameters of atoms C20, C21, C22, C20', C21' and C22' were restrained to behave approximately isotropically. The C—C distances of the disordered t-butyl group were restrained to be 1.54 (1) Å. H atoms were placed in calculated positions, with C—H = 0.93 (aryl), 0.96 (methyl) or 0.97 (methylene) Å, using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(CH3).
The pyrazole ring is an important structural motif found in many biologically and pharmaceutically active compounds. In the past few years, pyrazoles and their derivatives have attracted much attention because they show several biological activities, such as antimicrobial, anti-inflammatory, antiviral, anticancer, insecticidal, herbicidal and plant growth regulatory (Bekhit et al., 2004; Goekan-Kelekci et al., 2007; Gamage et al., 2002; Hashizume et al., 2004). Many pyrazoles are currently being tested and clinically evaluated as potential new drugs (Dannhardt et al., 2001; Park et al., 2005). For example, the natural pyrazole C-glycoside, pyrazofurin, an antibiotic, was reported to possess a broad spectrum of antimicrobial and antiviral activities in addition to being active against several tumor cell lines (Comber et al., 1991). In the search for more biologically active pyrazole derivatives, the title compound, I, was synthesized and we report here its
(Fig.1). The title compound contains three planar groups: (a) the phenyl ring composed of atoms C6—C11, (b) the pyrazole ring composed of atoms N, N2, C2, C3 and C4, (c) the C6H4 ring composed of atoms C13—C18, The dihedral angles between the planes of (a) and (b), and between (b) and (c) are 54.2 (2) ° and 25.0 (3) ° respectively. The is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1 & Fig.2).For related literature, see: Becher et al. (1986); Bekhit & Abdel-Aziem (2004); Comber et al. (1991); Dannhardt & Kiefer (2001); Gamage et al. (2002); Goekan-Kelekci et al. (2007); Hashizume et al. (2004); Park et al. (2005).
Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).C22H24N2OS | F(000) = 1552 |
Mr = 364.49 | Dx = 1.199 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2619 reflections |
a = 11.129 (3) Å | θ = 2.4–23.4° |
b = 16.181 (4) Å | µ = 0.17 mm−1 |
c = 22.429 (6) Å | T = 294 K |
V = 4039.0 (18) Å3 | Orthorhombic, colourless |
Z = 8 | 0.24 × 0.20 × 0.16 mm |
Bruker SMART 1000 diffractometer | 3568 independent reflections |
Radiation source: fine-focus sealed tube | 1788 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
φ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −12→13 |
Tmin = 0.945, Tmax = 0.973 | k = −16→19 |
19461 measured reflections | l = −26→21 |
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)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.146 | w = 1/[σ2(Fo2) + (0.0543P)2 + 1.5678P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
3568 reflections | Δρmax = 0.19 e Å−3 |
271 parameters | Δρmin = −0.21 e Å−3 |
57 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0053 (5) |
C22H24N2OS | V = 4039.0 (18) Å3 |
Mr = 364.49 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.129 (3) Å | µ = 0.17 mm−1 |
b = 16.181 (4) Å | T = 294 K |
c = 22.429 (6) Å | 0.24 × 0.20 × 0.16 mm |
Bruker SMART 1000 diffractometer | 3568 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 1788 reflections with I > 2σ(I) |
Tmin = 0.945, Tmax = 0.973 | Rint = 0.087 |
19461 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 57 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.19 e Å−3 |
3568 reflections | Δρmin = −0.21 e Å−3 |
271 parameters |
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 | Occ. (<1) | |
S1 | 0.56005 (9) | 0.18185 (6) | 0.52594 (4) | 0.0692 (3) | |
O1 | 0.7233 (2) | −0.07664 (16) | 0.52505 (12) | 0.0888 (9) | |
N1 | 0.4568 (2) | 0.09456 (16) | 0.61696 (12) | 0.0539 (7) | |
N2 | 0.4616 (3) | 0.02084 (17) | 0.64732 (13) | 0.0622 (8) | |
C1 | 0.5704 (4) | −0.1109 (2) | 0.63859 (17) | 0.0809 (12) | |
H1A | 0.5296 | −0.1218 | 0.6755 | 0.121* | |
H1B | 0.6556 | −0.1146 | 0.6447 | 0.121* | |
H1C | 0.5461 | −0.1507 | 0.6093 | 0.121* | |
C2 | 0.5388 (3) | −0.0253 (2) | 0.61720 (16) | 0.0589 (9) | |
C3 | 0.5853 (3) | 0.0175 (2) | 0.56780 (14) | 0.0520 (8) | |
C4 | 0.5313 (3) | 0.09467 (19) | 0.56915 (13) | 0.0503 (8) | |
C5 | 0.6746 (3) | −0.0098 (2) | 0.52514 (16) | 0.0676 (10) | |
H5 | 0.6964 | 0.0273 | 0.4953 | 0.081* | |
C6 | 0.3817 (3) | 0.1594 (2) | 0.63937 (14) | 0.0535 (9) | |
C7 | 0.3931 (3) | 0.1839 (2) | 0.69794 (15) | 0.0651 (10) | |
H7 | 0.4507 | 0.1598 | 0.7224 | 0.078* | |
C8 | 0.3183 (4) | 0.2443 (3) | 0.71983 (18) | 0.0787 (12) | |
H8 | 0.3249 | 0.2607 | 0.7594 | 0.094* | |
C9 | 0.2340 (4) | 0.2806 (3) | 0.6837 (2) | 0.0861 (13) | |
H9 | 0.1839 | 0.3216 | 0.6987 | 0.103* | |
C10 | 0.2239 (4) | 0.2559 (3) | 0.6255 (2) | 0.0875 (13) | |
H10 | 0.1668 | 0.2806 | 0.6010 | 0.105* | |
C11 | 0.2967 (3) | 0.1955 (2) | 0.60299 (16) | 0.0704 (10) | |
H11 | 0.2890 | 0.1789 | 0.5635 | 0.084* | |
C12 | 0.6681 (3) | 0.2339 (2) | 0.57569 (17) | 0.0752 (11) | |
H12A | 0.7027 | 0.2808 | 0.5550 | 0.090* | |
H12B | 0.6257 | 0.2546 | 0.6104 | 0.090* | |
C13 | 0.7670 (3) | 0.17787 (19) | 0.59573 (16) | 0.0594 (9) | |
C14 | 0.7591 (3) | 0.1360 (2) | 0.64906 (15) | 0.0621 (10) | |
H14 | 0.6952 | 0.1469 | 0.6746 | 0.075* | |
C15 | 0.8436 (3) | 0.0784 (2) | 0.66528 (15) | 0.0655 (10) | |
H15 | 0.8356 | 0.0516 | 0.7018 | 0.079* | |
C16 | 0.9402 (3) | 0.0589 (2) | 0.62918 (15) | 0.0588 (9) | |
C17 | 0.9495 (3) | 0.1031 (2) | 0.57631 (17) | 0.0720 (11) | |
H17 | 1.0145 | 0.0932 | 0.5512 | 0.086* | |
C18 | 0.8651 (4) | 0.1614 (2) | 0.55988 (17) | 0.0709 (11) | |
H18 | 0.8745 | 0.1900 | 0.5242 | 0.085* | |
C19 | 1.0287 (3) | −0.0081 (2) | 0.64643 (16) | 0.0720 (11) | |
C20 | 0.9655 (8) | −0.0873 (4) | 0.6579 (6) | 0.115 (3) | 0.655 (12) |
H20A | 1.0227 | −0.1284 | 0.6699 | 0.172* | 0.655 (12) |
H20B | 0.9256 | −0.1051 | 0.6222 | 0.172* | 0.655 (12) |
H20C | 0.9073 | −0.0796 | 0.6890 | 0.172* | 0.655 (12) |
C21 | 1.1021 (7) | 0.0212 (5) | 0.7014 (3) | 0.073 (2) | 0.655 (12) |
H21A | 1.0489 | 0.0298 | 0.7345 | 0.110* | 0.655 (12) |
H21B | 1.1424 | 0.0720 | 0.6921 | 0.110* | 0.655 (12) |
H21C | 1.1605 | −0.0201 | 0.7117 | 0.110* | 0.655 (12) |
C22 | 1.1279 (8) | −0.0210 (6) | 0.5970 (3) | 0.094 (3) | 0.655 (12) |
H22A | 1.1839 | −0.0624 | 0.6100 | 0.141* | 0.655 (12) |
H22B | 1.1697 | 0.0300 | 0.5904 | 0.141* | 0.655 (12) |
H22C | 1.0905 | −0.0386 | 0.5606 | 0.141* | 0.655 (12) |
C20' | 0.9620 (13) | −0.0696 (9) | 0.6921 (7) | 0.087 (5) | 0.345 (12) |
H20D | 0.8867 | −0.0868 | 0.6753 | 0.130* | 0.345 (12) |
H20E | 0.9480 | −0.0415 | 0.7291 | 0.130* | 0.345 (12) |
H20F | 1.0116 | −0.1172 | 0.6990 | 0.130* | 0.345 (12) |
C21' | 1.1392 (14) | 0.0222 (13) | 0.6765 (9) | 0.132 (9) | 0.345 (12) |
H21D | 1.1231 | 0.0745 | 0.6952 | 0.197* | 0.345 (12) |
H21E | 1.2022 | 0.0288 | 0.6477 | 0.197* | 0.345 (12) |
H21F | 1.1638 | −0.0170 | 0.7063 | 0.197* | 0.345 (12) |
C22' | 1.0496 (18) | −0.0659 (9) | 0.5928 (5) | 0.101 (6) | 0.345 (12) |
H22D | 1.1070 | −0.1076 | 0.6035 | 0.151* | 0.345 (12) |
H22E | 1.0797 | −0.0344 | 0.5598 | 0.151* | 0.345 (12) |
H22F | 0.9751 | −0.0916 | 0.5818 | 0.151* | 0.345 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0791 (7) | 0.0673 (6) | 0.0612 (6) | 0.0141 (5) | 0.0036 (5) | 0.0218 (5) |
O1 | 0.100 (2) | 0.0657 (18) | 0.101 (2) | 0.0241 (16) | −0.0006 (17) | −0.0163 (16) |
N1 | 0.0617 (18) | 0.0461 (16) | 0.0538 (16) | 0.0022 (14) | −0.0019 (15) | 0.0038 (13) |
N2 | 0.069 (2) | 0.0478 (17) | 0.0697 (19) | −0.0030 (15) | −0.0048 (16) | 0.0110 (15) |
C1 | 0.091 (3) | 0.050 (2) | 0.102 (3) | 0.000 (2) | −0.007 (3) | 0.014 (2) |
C2 | 0.061 (2) | 0.046 (2) | 0.070 (2) | −0.0044 (19) | −0.008 (2) | 0.0021 (18) |
C3 | 0.053 (2) | 0.049 (2) | 0.054 (2) | 0.0004 (17) | −0.0086 (18) | −0.0034 (16) |
C4 | 0.056 (2) | 0.051 (2) | 0.0435 (18) | 0.0005 (16) | −0.0050 (17) | 0.0027 (15) |
C5 | 0.072 (3) | 0.063 (2) | 0.067 (2) | 0.004 (2) | −0.009 (2) | −0.008 (2) |
C6 | 0.057 (2) | 0.048 (2) | 0.055 (2) | 0.0002 (17) | 0.0020 (18) | 0.0028 (16) |
C7 | 0.074 (2) | 0.066 (2) | 0.055 (2) | −0.004 (2) | −0.0009 (19) | 0.0041 (19) |
C8 | 0.103 (3) | 0.072 (3) | 0.061 (2) | −0.005 (3) | 0.014 (3) | −0.009 (2) |
C9 | 0.097 (3) | 0.073 (3) | 0.088 (3) | 0.015 (2) | 0.022 (3) | −0.007 (2) |
C10 | 0.089 (3) | 0.090 (3) | 0.083 (3) | 0.030 (3) | 0.000 (2) | −0.009 (3) |
C11 | 0.079 (3) | 0.072 (3) | 0.061 (2) | 0.014 (2) | −0.006 (2) | −0.003 (2) |
C12 | 0.089 (3) | 0.043 (2) | 0.094 (3) | −0.002 (2) | 0.009 (2) | 0.008 (2) |
C13 | 0.065 (2) | 0.0383 (19) | 0.075 (2) | −0.0072 (18) | 0.003 (2) | 0.0000 (18) |
C14 | 0.068 (2) | 0.067 (2) | 0.051 (2) | −0.003 (2) | 0.0059 (19) | −0.0109 (19) |
C15 | 0.081 (3) | 0.066 (2) | 0.050 (2) | −0.001 (2) | −0.002 (2) | 0.0011 (18) |
C16 | 0.065 (2) | 0.056 (2) | 0.055 (2) | −0.0014 (19) | −0.003 (2) | −0.0115 (17) |
C17 | 0.065 (3) | 0.076 (3) | 0.075 (3) | 0.000 (2) | 0.018 (2) | 0.001 (2) |
C18 | 0.074 (3) | 0.066 (3) | 0.073 (3) | −0.011 (2) | 0.015 (2) | 0.014 (2) |
C19 | 0.082 (3) | 0.067 (3) | 0.068 (3) | 0.013 (2) | −0.005 (2) | −0.011 (2) |
C20 | 0.110 (6) | 0.058 (4) | 0.175 (8) | −0.011 (4) | −0.029 (6) | −0.012 (5) |
C21 | 0.053 (4) | 0.095 (5) | 0.072 (4) | 0.011 (3) | −0.006 (4) | 0.001 (4) |
C22 | 0.101 (6) | 0.100 (6) | 0.082 (4) | 0.033 (5) | −0.001 (4) | −0.015 (4) |
C20' | 0.101 (9) | 0.059 (7) | 0.100 (9) | 0.018 (6) | −0.013 (7) | −0.001 (6) |
C21' | 0.113 (11) | 0.123 (11) | 0.158 (13) | −0.008 (9) | 0.001 (9) | −0.008 (9) |
C22' | 0.120 (10) | 0.085 (8) | 0.098 (8) | 0.017 (7) | 0.014 (7) | −0.001 (7) |
S1—C4 | 1.741 (3) | C14—H14 | 0.9300 |
S1—C12 | 1.844 (4) | C15—C16 | 1.382 (5) |
O1—C5 | 1.210 (4) | C15—H15 | 0.9300 |
N1—C4 | 1.355 (4) | C16—C17 | 1.389 (5) |
N1—N2 | 1.375 (3) | C16—C19 | 1.515 (5) |
N1—C6 | 1.432 (4) | C17—C18 | 1.381 (5) |
N2—C2 | 1.324 (4) | C17—H17 | 0.9300 |
C1—C2 | 1.507 (4) | C18—H18 | 0.9300 |
C1—H1A | 0.9600 | C19—C20 | 1.485 (6) |
C1—H1B | 0.9600 | C19—C21' | 1.487 (9) |
C1—H1C | 0.9600 | C19—C22' | 1.541 (8) |
C2—C3 | 1.406 (4) | C19—C21 | 1.554 (6) |
C3—C4 | 1.386 (4) | C19—C22 | 1.578 (6) |
C3—C5 | 1.448 (4) | C19—C20' | 1.609 (8) |
C5—H5 | 0.9300 | C20—H20A | 0.9600 |
C6—C7 | 1.378 (4) | C20—H20B | 0.9600 |
C6—C11 | 1.380 (4) | C20—H20C | 0.9600 |
C7—C8 | 1.375 (5) | C21—H21A | 0.9600 |
C7—H7 | 0.9300 | C21—H21B | 0.9600 |
C8—C9 | 1.371 (5) | C21—H21C | 0.9600 |
C8—H8 | 0.9300 | C22—H22A | 0.9600 |
C9—C10 | 1.371 (5) | C22—H22B | 0.9600 |
C9—H9 | 0.9300 | C22—H22C | 0.9600 |
C10—C11 | 1.366 (5) | C20'—H20D | 0.9600 |
C10—H10 | 0.9300 | C20'—H20E | 0.9600 |
C11—H11 | 0.9300 | C20'—H20F | 0.9600 |
C12—C13 | 1.495 (5) | C21'—H21D | 0.9600 |
C12—H12A | 0.9700 | C21'—H21E | 0.9600 |
C12—H12B | 0.9700 | C21'—H21F | 0.9600 |
C13—C14 | 1.378 (4) | C22'—H22D | 0.9600 |
C13—C18 | 1.382 (5) | C22'—H22E | 0.9600 |
C14—C15 | 1.372 (5) | C22'—H22F | 0.9600 |
C4—S1—C12 | 98.81 (15) | C15—C14—H14 | 119.3 |
C4—N1—N2 | 111.6 (3) | C13—C14—H14 | 119.3 |
C4—N1—C6 | 129.3 (3) | C14—C15—C16 | 122.2 (3) |
N2—N1—C6 | 119.0 (3) | C14—C15—H15 | 118.9 |
C2—N2—N1 | 105.2 (3) | C16—C15—H15 | 118.9 |
C2—C1—H1A | 109.5 | C15—C16—C17 | 116.1 (3) |
C2—C1—H1B | 109.5 | C15—C16—C19 | 121.3 (3) |
H1A—C1—H1B | 109.5 | C17—C16—C19 | 122.6 (3) |
C2—C1—H1C | 109.5 | C18—C17—C16 | 121.9 (3) |
H1A—C1—H1C | 109.5 | C18—C17—H17 | 119.0 |
H1B—C1—H1C | 109.5 | C16—C17—H17 | 119.0 |
N2—C2—C3 | 111.3 (3) | C17—C18—C13 | 120.9 (3) |
N2—C2—C1 | 120.5 (3) | C17—C18—H18 | 119.6 |
C3—C2—C1 | 128.2 (3) | C13—C18—H18 | 119.6 |
C4—C3—C2 | 105.5 (3) | C20—C19—C16 | 110.7 (5) |
C4—C3—C5 | 125.9 (3) | C21'—C19—C16 | 114.7 (9) |
C2—C3—C5 | 128.6 (3) | C16—C19—C22' | 109.5 (6) |
N1—C4—C3 | 106.4 (3) | C20—C19—C21 | 112.0 (5) |
N1—C4—S1 | 123.6 (2) | C16—C19—C21 | 109.0 (4) |
C3—C4—S1 | 129.6 (3) | C20—C19—C22 | 109.8 (5) |
O1—C5—C3 | 125.5 (4) | C16—C19—C22 | 111.8 (4) |
O1—C5—H5 | 117.3 | C21—C19—C22 | 103.3 (4) |
C3—C5—H5 | 117.3 | C16—C19—C20' | 107.8 (6) |
C7—C6—C11 | 120.3 (3) | C19—C20—H20A | 109.5 |
C7—C6—N1 | 119.5 (3) | C19—C20—H20B | 109.5 |
C11—C6—N1 | 120.2 (3) | C19—C20—H20C | 109.5 |
C8—C7—C6 | 119.3 (4) | C19—C21—H21A | 109.5 |
C8—C7—H7 | 120.3 | C19—C21—H21B | 109.5 |
C6—C7—H7 | 120.3 | C19—C21—H21C | 109.5 |
C9—C8—C7 | 120.5 (4) | C19—C22—H22A | 109.5 |
C9—C8—H8 | 119.7 | C19—C22—H22B | 109.5 |
C7—C8—H8 | 119.7 | C19—C22—H22C | 109.5 |
C8—C9—C10 | 119.7 (4) | C19—C20'—H20D | 109.5 |
C8—C9—H9 | 120.2 | C19—C20'—H20E | 109.5 |
C10—C9—H9 | 120.2 | H20D—C20'—H20E | 109.5 |
C11—C10—C9 | 120.7 (4) | C19—C20'—H20F | 109.5 |
C11—C10—H10 | 119.6 | H20D—C20'—H20F | 109.5 |
C9—C10—H10 | 119.6 | H20E—C20'—H20F | 109.5 |
C10—C11—C6 | 119.5 (3) | C19—C21'—H21D | 109.5 |
C10—C11—H11 | 120.3 | C19—C21'—H21E | 109.5 |
C6—C11—H11 | 120.3 | H21D—C21'—H21E | 109.5 |
C13—C12—S1 | 112.7 (2) | C19—C21'—H21F | 109.5 |
C13—C12—H12A | 109.1 | H21D—C21'—H21F | 109.5 |
S1—C12—H12A | 109.1 | H21E—C21'—H21F | 109.5 |
C13—C12—H12B | 109.1 | C19—C22'—H22D | 109.5 |
S1—C12—H12B | 109.1 | C19—C22'—H22E | 109.5 |
H12A—C12—H12B | 107.8 | H22D—C22'—H22E | 109.5 |
C14—C13—C18 | 117.4 (3) | C19—C22'—H22F | 109.5 |
C14—C13—C12 | 120.8 (3) | H22D—C22'—H22F | 109.5 |
C18—C13—C12 | 121.6 (3) | H22E—C22'—H22F | 109.5 |
C15—C14—C13 | 121.4 (3) | ||
C4—N1—N2—C2 | −0.9 (3) | C9—C10—C11—C6 | −0.4 (6) |
C6—N1—N2—C2 | −178.7 (3) | C7—C6—C11—C10 | 0.1 (5) |
N1—N2—C2—C3 | 0.5 (4) | N1—C6—C11—C10 | 178.4 (3) |
N1—N2—C2—C1 | 178.1 (3) | C4—S1—C12—C13 | 50.4 (3) |
N2—C2—C3—C4 | 0.1 (4) | S1—C12—C13—C14 | −94.5 (4) |
C1—C2—C3—C4 | −177.3 (3) | S1—C12—C13—C18 | 80.7 (4) |
N2—C2—C3—C5 | 177.6 (3) | C18—C13—C14—C15 | −1.8 (5) |
C1—C2—C3—C5 | 0.2 (6) | C12—C13—C14—C15 | 173.6 (3) |
N2—N1—C4—C3 | 1.0 (3) | C13—C14—C15—C16 | −0.4 (5) |
C6—N1—C4—C3 | 178.5 (3) | C14—C15—C16—C17 | 2.2 (5) |
N2—N1—C4—S1 | −172.5 (2) | C14—C15—C16—C19 | −176.7 (3) |
C6—N1—C4—S1 | 5.0 (5) | C15—C16—C17—C18 | −1.9 (5) |
C2—C3—C4—N1 | −0.6 (3) | C19—C16—C17—C18 | 177.0 (3) |
C5—C3—C4—N1 | −178.2 (3) | C16—C17—C18—C13 | −0.3 (6) |
C2—C3—C4—S1 | 172.3 (3) | C14—C13—C18—C17 | 2.1 (5) |
C5—C3—C4—S1 | −5.3 (5) | C12—C13—C18—C17 | −173.3 (3) |
C12—S1—C4—N1 | 78.5 (3) | C15—C16—C19—C20 | 55.1 (7) |
C12—S1—C4—C3 | −93.3 (3) | C17—C16—C19—C20 | −123.7 (6) |
C4—C3—C5—O1 | 178.3 (3) | C15—C16—C19—C21' | −96.3 (11) |
C2—C3—C5—O1 | 1.2 (6) | C17—C16—C19—C21' | 84.9 (11) |
C4—N1—C6—C7 | −125.0 (4) | C15—C16—C19—C22' | 132.1 (9) |
N2—N1—C6—C7 | 52.4 (4) | C17—C16—C19—C22' | −46.8 (9) |
C4—N1—C6—C11 | 56.7 (5) | C15—C16—C19—C21 | −68.6 (5) |
N2—N1—C6—C11 | −126.0 (3) | C17—C16—C19—C21 | 112.6 (5) |
C11—C6—C7—C8 | 0.4 (5) | C15—C16—C19—C22 | 177.9 (5) |
N1—C6—C7—C8 | −177.9 (3) | C17—C16—C19—C22 | −1.0 (6) |
C6—C7—C8—C9 | −0.6 (6) | C15—C16—C19—C20' | 23.1 (8) |
C7—C8—C9—C10 | 0.4 (6) | C17—C16—C19—C20' | −155.8 (7) |
C8—C9—C10—C11 | 0.1 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12A···O2i | 0.97 | 2.54 | 3.486 (3) | 165 |
Symmetry code: (i) x+3/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C22H24N2OS |
Mr | 364.49 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 294 |
a, b, c (Å) | 11.129 (3), 16.181 (4), 22.429 (6) |
V (Å3) | 4039.0 (18) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.24 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART 1000 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2001) |
Tmin, Tmax | 0.945, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19461, 3568, 1788 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.146, 1.01 |
No. of reflections | 3568 |
No. of parameters | 271 |
No. of restraints | 57 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.21 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12A···O2i | 0.97 | 2.54 | 3.486 (3) | 165 |
Symmetry code: (i) x+3/2, −y+1/2, −z. |
Acknowledgements
This work was supported by the National Natural Science Foundation of China (NNSFC) (grant No. 30771696) and the Science and Technology Plan of Huzhou (grant No. 2007YS18).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The pyrazole ring is an important structural motif found in many biologically and pharmaceutically active compounds. In the past few years, pyrazoles and their derivatives have attracted much attention because they show several biological activities, such as antimicrobial, anti-inflammatory, antiviral, anticancer, insecticidal, herbicidal and plant growth regulatory (Bekhit et al., 2004; Goekan-Kelekci et al., 2007; Gamage et al., 2002; Hashizume et al., 2004). Many pyrazoles are currently being tested and clinically evaluated as potential new drugs (Dannhardt et al., 2001; Park et al., 2005). For example, the natural pyrazole C-glycoside, pyrazofurin, an antibiotic, was reported to possess a broad spectrum of antimicrobial and antiviral activities in addition to being active against several tumor cell lines (Comber et al., 1991). In the search for more biologically active pyrazole derivatives, the title compound, I, was synthesized and we report here its crystal structure (Fig.1). The title compound contains three planar groups: (a) the phenyl ring composed of atoms C6—C11, (b) the pyrazole ring composed of atoms N, N2, C2, C3 and C4, (c) the C6H4 ring composed of atoms C13—C18, The dihedral angles between the planes of (a) and (b), and between (b) and (c) are 54.2 (2) ° and 25.0 (3) ° respectively. The crystal structure is stabilized by weak intermolecular C—H···O hydrogen bonds (Table 1 & Fig.2).