Buy article online - an online subscription or single-article purchase is required to access this article.
In the title compounds 5-(3-fluoro-4-phenoxyphenyl)-1,3-biphenyl-4,5-dihydro-1
H-pyrazole, C
27H
21FN
2O, (I), 3-(4-chlorophenyl)-5-(3-fluoro-4-phenoxyphenyl)-1-phenyl-4,5-dihydro-1
H-pyrazole, C
27H
20ClFN
2O, (II), 5-(3-fluoro-4-phenoxyphenyl)-3-(4-methylphenyl)-1-phenyl-4,5-dihydro-1
H-pyrazole, C
28H
23FN
2O, (III), and 5-(3-fluoro-4-phenoxyphenyl)-3-(4-methoxyphenyl)-1-phenyl-4,5-dihydro-1
H-pyrazole, C
28H
23FN
2O
2, (IV), the five-membered pyrazole ring exists in an envelope conformation. The crystal structure of (I) has three independent C—H
π intermolecular interactions. In (II), an intermolecular C—Cl
π contact is present, forming molecular chains. Replacement of this chloro group in (II) by a methyl group yields an isomorphic crystal structure, (III).
Supporting information
CCDC references: 265742; 265743; 265744; 265745
A mixture of chalcone (with different substitutions; 0.01 mol), acetic acid (20 ml) and phenylhydrazine (0.01 mol) was refluxed for 12 h. The resulting
mixture was cooled to 283 K and filtered. The progress of the reaction and the
purity of the products were monitored by thin-layer chromatography. The crude
products thus obtained were recrystallized from propan-2-ol (Mogilaiah &
Sudhakar, 2003; Dandia et al., 1993; Bhatt et al., 2001; Mohan,
2006). All four compounds were characterized using mass, NMR and IR spectra,
m. p. measurements, and elemental analyses. A small quantity of each sample
was dissolved in a suitable solvent or solvent combination, such as
dichloromethane, dichloromethane–hexane (Ratio?), acetonitrile, ethyl
acetate or ethyl acetate–hexane (Ratio?). The crystals used for data
collection were obtained from ethyl acetate–hexane (Ratio?).
Friedel-equivalent relections were averaged before refinement in (I). The H
atoms of the methyl groups in (III) and (IV) were fixed in geometrical
positions and allowed to ride on their parent C atoms, with C—H = 0.96 Å
and Uiso(H) = 1.5Ueq(C). The remaining H atoms in all four
structures were located in a difference Fourier map and refined isotropically.
The C—H bond lengths are in the range of 0.85 (4)–1.03 (3) Å.
For all compounds, data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).
(I) (5
S)-5-(3-fluoro-4-phenoxyphenyl)-1,3-biphenyl-4,5-dihydro-1
H-pyrazole
top
Crystal data top
C27H21FN2O | F(000) = 428 |
Mr = 408.46 | Dx = 1.281 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 625 reflections |
a = 5.9774 (14) Å | θ = 1.4–26.4° |
b = 10.484 (3) Å | µ = 0.08 mm−1 |
c = 16.896 (4) Å | T = 290 K |
β = 90.762 (4)° | Needle, colourless |
V = 1058.7 (5) Å3 | 0.34 × 0.23 × 0.09 mm |
Z = 2 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2272 independent reflections |
Radiation source: fine-focus sealed tube | 1984 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
Tmin = 0.941, Tmax = 0.992 | k = −12→13 |
8402 measured reflections | l = −20→21 |
Refinement top
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 1.26 | w = 1/[σ2(Fo2) + (0.0468P)2 + 0.0049P] where P = (Fo2 + 2Fc2)/3 |
2272 reflections | (Δ/σ)max < 0.001 |
364 parameters | Δρmax = 0.12 e Å−3 |
1 restraint | Δρmin = −0.12 e Å−3 |
Crystal data top
C27H21FN2O | V = 1058.7 (5) Å3 |
Mr = 408.46 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.9774 (14) Å | µ = 0.08 mm−1 |
b = 10.484 (3) Å | T = 290 K |
c = 16.896 (4) Å | 0.34 × 0.23 × 0.09 mm |
β = 90.762 (4)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2272 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1984 reflections with I > 2σ(I) |
Tmin = 0.941, Tmax = 0.992 | Rint = 0.018 |
8402 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 1.26 | Δρmax = 0.12 e Å−3 |
2272 reflections | Δρmin = −0.12 e Å−3 |
364 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.3696 (3) | 0.49694 (16) | 0.86252 (7) | 0.0938 (5) | |
O1 | 0.1136 (2) | 0.29288 (16) | 0.82474 (8) | 0.0716 (4) | |
N1 | 0.5919 (3) | 0.03263 (15) | 0.63601 (9) | 0.0584 (4) | |
N2 | 0.4082 (3) | 0.00675 (17) | 0.58801 (9) | 0.0589 (4) | |
C1 | 0.3883 (3) | 0.09556 (19) | 0.53612 (10) | 0.0524 (5) | |
C2 | 0.5663 (4) | 0.1959 (2) | 0.54431 (12) | 0.0569 (5) | |
C3 | 0.6664 (4) | 0.16526 (19) | 0.62545 (11) | 0.0534 (5) | |
C4 | 0.5846 (3) | 0.25293 (18) | 0.69013 (10) | 0.0461 (4) | |
C5 | 0.7061 (4) | 0.3613 (2) | 0.70950 (11) | 0.0539 (5) | |
C6 | 0.6334 (4) | 0.4441 (2) | 0.76682 (12) | 0.0630 (6) | |
C7 | 0.4407 (4) | 0.4180 (2) | 0.80499 (10) | 0.0597 (5) | |
C8 | 0.3147 (3) | 0.3118 (2) | 0.78722 (11) | 0.0527 (5) | |
C9 | 0.3861 (3) | 0.2305 (2) | 0.72911 (11) | 0.0526 (5) | |
C10 | 0.1108 (3) | 0.21570 (19) | 0.89140 (10) | 0.0516 (4) | |
C11 | −0.0833 (4) | 0.2215 (2) | 0.93383 (13) | 0.0640 (6) | |
C12 | −0.1063 (5) | 0.1468 (3) | 1.00022 (14) | 0.0768 (7) | |
C13 | 0.0624 (5) | 0.0666 (3) | 1.02321 (14) | 0.0791 (7) | |
C14 | 0.2548 (4) | 0.0613 (3) | 0.97995 (14) | 0.0743 (7) | |
C15 | 0.2810 (4) | 0.1363 (2) | 0.91360 (12) | 0.0622 (6) | |
C16 | 0.6137 (3) | −0.03519 (18) | 0.70726 (12) | 0.0564 (5) | |
C17 | 0.7959 (4) | −0.0128 (2) | 0.75727 (15) | 0.0712 (6) | |
C18 | 0.8204 (5) | −0.0802 (3) | 0.82630 (15) | 0.0836 (8) | |
C19 | 0.6672 (6) | −0.1699 (3) | 0.84788 (16) | 0.0889 (8) | |
C20 | 0.4860 (5) | −0.1925 (3) | 0.79898 (15) | 0.0840 (7) | |
C21 | 0.4585 (4) | −0.1255 (2) | 0.72916 (14) | 0.0686 (6) | |
C22 | 0.2111 (3) | 0.0925 (2) | 0.47531 (10) | 0.0549 (5) | |
C23 | 0.0446 (4) | 0.0010 (2) | 0.47625 (13) | 0.0613 (5) | |
C24 | −0.1211 (4) | 0.0010 (3) | 0.41856 (14) | 0.0706 (6) | |
C25 | −0.1211 (4) | 0.0903 (3) | 0.35895 (13) | 0.0738 (7) | |
C26 | 0.0432 (5) | 0.1799 (3) | 0.35723 (14) | 0.0744 (7) | |
C27 | 0.2087 (4) | 0.1819 (2) | 0.41487 (12) | 0.0663 (6) | |
H2A | 0.506 (3) | 0.279 (2) | 0.5408 (10) | 0.056 (5)* | |
H2B | 0.683 (4) | 0.185 (2) | 0.5028 (12) | 0.065 (6)* | |
H3 | 0.831 (3) | 0.1692 (17) | 0.6273 (9) | 0.043 (5)* | |
H5 | 0.851 (4) | 0.371 (2) | 0.6832 (11) | 0.061 (6)* | |
H6 | 0.712 (4) | 0.516 (3) | 0.7803 (13) | 0.079 (7)* | |
H9 | 0.298 (4) | 0.157 (2) | 0.7168 (11) | 0.066 (6)* | |
H11 | −0.203 (4) | 0.276 (3) | 0.9139 (13) | 0.085 (8)* | |
H12 | −0.247 (5) | 0.157 (3) | 1.0292 (16) | 0.106 (9)* | |
H13 | 0.044 (4) | 0.017 (3) | 1.0669 (16) | 0.094 (8)* | |
H14 | 0.372 (4) | 0.009 (3) | 0.9943 (13) | 0.079 (7)* | |
H15 | 0.407 (4) | 0.132 (2) | 0.8850 (12) | 0.063 (6)* | |
H17 | 0.897 (4) | 0.053 (3) | 0.7421 (14) | 0.082 (7)* | |
H18 | 0.943 (4) | −0.067 (2) | 0.8614 (14) | 0.084 (7)* | |
H19 | 0.685 (4) | −0.217 (3) | 0.8980 (15) | 0.096 (8)* | |
H20 | 0.368 (5) | −0.261 (3) | 0.8097 (15) | 0.097 (8)* | |
H21 | 0.337 (4) | −0.138 (2) | 0.6944 (13) | 0.075 (7)* | |
H23 | 0.039 (4) | −0.058 (2) | 0.5180 (13) | 0.065 (6)* | |
H24 | −0.233 (4) | −0.059 (3) | 0.4195 (13) | 0.077 (7)* | |
H25 | −0.236 (4) | 0.087 (2) | 0.3177 (14) | 0.082 (7)* | |
H26 | 0.054 (4) | 0.239 (3) | 0.3143 (15) | 0.094 (8)* | |
H27 | 0.326 (4) | 0.241 (3) | 0.4139 (13) | 0.079 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.1201 (12) | 0.0920 (11) | 0.0700 (8) | 0.0086 (9) | 0.0256 (8) | −0.0247 (8) |
O1 | 0.0538 (8) | 0.0888 (11) | 0.0727 (9) | 0.0183 (8) | 0.0202 (6) | 0.0298 (8) |
N1 | 0.0667 (11) | 0.0445 (9) | 0.0639 (10) | −0.0023 (8) | −0.0079 (8) | −0.0020 (8) |
N2 | 0.0697 (11) | 0.0489 (9) | 0.0579 (9) | −0.0015 (8) | −0.0064 (8) | −0.0023 (8) |
C22 | 0.0643 (12) | 0.0525 (11) | 0.0481 (10) | 0.0084 (10) | 0.0062 (8) | −0.0050 (9) |
C1 | 0.0628 (12) | 0.0455 (10) | 0.0492 (10) | 0.0027 (9) | 0.0077 (8) | −0.0045 (9) |
C2 | 0.0681 (13) | 0.0504 (13) | 0.0526 (10) | 0.0017 (11) | 0.0178 (9) | −0.0031 (9) |
C3 | 0.0480 (11) | 0.0508 (12) | 0.0614 (11) | −0.0028 (9) | 0.0074 (8) | −0.0039 (9) |
C4 | 0.0467 (10) | 0.0441 (10) | 0.0474 (9) | −0.0024 (8) | 0.0024 (7) | 0.0028 (8) |
C5 | 0.0565 (12) | 0.0554 (12) | 0.0499 (10) | −0.0103 (10) | 0.0083 (9) | 0.0014 (9) |
C7 | 0.0775 (14) | 0.0586 (13) | 0.0433 (10) | 0.0079 (12) | 0.0085 (10) | −0.0012 (9) |
C6 | 0.0780 (15) | 0.0553 (13) | 0.0559 (12) | −0.0133 (12) | 0.0041 (10) | −0.0079 (10) |
C8 | 0.0507 (10) | 0.0573 (12) | 0.0501 (10) | 0.0083 (9) | 0.0076 (8) | 0.0146 (9) |
C9 | 0.0475 (10) | 0.0474 (12) | 0.0628 (11) | −0.0030 (9) | 0.0040 (8) | 0.0043 (9) |
C10 | 0.0533 (11) | 0.0513 (11) | 0.0504 (9) | −0.0034 (9) | 0.0051 (8) | 0.0015 (9) |
C11 | 0.0586 (13) | 0.0626 (14) | 0.0713 (13) | −0.0025 (11) | 0.0188 (10) | 0.0033 (11) |
C12 | 0.0781 (16) | 0.0791 (17) | 0.0737 (14) | −0.0120 (14) | 0.0250 (13) | 0.0047 (13) |
C13 | 0.0920 (19) | 0.0856 (19) | 0.0600 (13) | −0.0188 (15) | 0.0092 (12) | 0.0157 (13) |
C14 | 0.0740 (16) | 0.0769 (17) | 0.0717 (14) | −0.0025 (13) | −0.0088 (12) | 0.0190 (12) |
C15 | 0.0537 (12) | 0.0746 (15) | 0.0585 (11) | 0.0007 (11) | 0.0057 (10) | 0.0083 (11) |
C16 | 0.0650 (12) | 0.0408 (10) | 0.0630 (11) | 0.0055 (9) | −0.0061 (9) | −0.0069 (9) |
C17 | 0.0768 (15) | 0.0552 (14) | 0.0812 (14) | −0.0020 (12) | −0.0165 (12) | −0.0023 (12) |
C18 | 0.1001 (19) | 0.0690 (16) | 0.0808 (16) | 0.0085 (15) | −0.0339 (15) | −0.0041 (13) |
C19 | 0.125 (2) | 0.0653 (16) | 0.0752 (15) | 0.0119 (16) | −0.0228 (15) | 0.0106 (13) |
C20 | 0.105 (2) | 0.0618 (15) | 0.0850 (17) | −0.0058 (15) | −0.0098 (15) | 0.0170 (13) |
C21 | 0.0775 (15) | 0.0548 (13) | 0.0731 (14) | −0.0025 (12) | −0.0141 (12) | 0.0022 (11) |
C23 | 0.0691 (14) | 0.0589 (13) | 0.0562 (12) | 0.0031 (12) | 0.0070 (10) | −0.0040 (11) |
C24 | 0.0612 (14) | 0.0738 (16) | 0.0768 (14) | 0.0002 (13) | 0.0050 (11) | −0.0188 (13) |
C25 | 0.0767 (16) | 0.0834 (17) | 0.0611 (13) | 0.0240 (14) | −0.0096 (11) | −0.0132 (13) |
C26 | 0.0900 (18) | 0.0719 (16) | 0.0613 (13) | 0.0134 (14) | −0.0030 (12) | 0.0037 (12) |
C27 | 0.0742 (15) | 0.0647 (15) | 0.0599 (12) | 0.0031 (12) | 0.0026 (11) | 0.0018 (11) |
Geometric parameters (Å, º) top
F1—C7 | 1.350 (2) | C6—H6 | 0.91 (3) |
O1—C8 | 1.381 (2) | C8—C7 | 1.374 (3) |
O1—C10 | 1.387 (2) | C5—H5 | 0.98 (2) |
N1—N2 | 1.383 (2) | C15—C14 | 1.380 (3) |
N1—C16 | 1.403 (2) | C15—H15 | 0.90 (2) |
N1—C3 | 1.472 (3) | C2—H2A | 0.94 (2) |
N2—C1 | 1.284 (2) | C2—H2B | 1.00 (2) |
C10—C15 | 1.363 (3) | C24—C25 | 1.375 (4) |
C10—C11 | 1.374 (3) | C24—H24 | 0.92 (2) |
C22—C23 | 1.383 (3) | C21—C20 | 1.381 (3) |
C22—C27 | 1.386 (3) | C21—H21 | 0.94 (2) |
C22—C1 | 1.466 (3) | C27—C26 | 1.379 (3) |
C1—C2 | 1.501 (3) | C27—H27 | 0.94 (3) |
C16—C21 | 1.379 (3) | C17—C18 | 1.370 (4) |
C16—C17 | 1.389 (3) | C17—H17 | 0.95 (3) |
C3—C4 | 1.514 (3) | C25—C26 | 1.359 (4) |
C3—C2 | 1.523 (3) | C25—H25 | 0.97 (2) |
C3—H3 | 0.981 (18) | C13—C12 | 1.365 (4) |
C9—C8 | 1.373 (3) | C13—C14 | 1.371 (4) |
C9—C4 | 1.385 (3) | C13—H13 | 0.91 (3) |
C9—H9 | 0.95 (2) | C12—H12 | 0.99 (3) |
C4—C5 | 1.385 (3) | C26—H26 | 0.96 (3) |
C23—C24 | 1.380 (3) | C14—H14 | 0.92 (2) |
C23—H23 | 0.94 (2) | C20—C19 | 1.374 (4) |
C11—C12 | 1.376 (3) | C20—H20 | 1.03 (3) |
C11—H11 | 0.97 (2) | C18—C19 | 1.365 (4) |
C6—C7 | 1.355 (3) | C18—H18 | 0.95 (2) |
C6—C5 | 1.376 (3) | C19—H19 | 0.98 (3) |
| | | |
C8—O1—C10 | 118.46 (13) | C6—C7—C8 | 121.77 (18) |
N2—N1—C16 | 117.91 (16) | C10—C15—C14 | 118.6 (2) |
N2—N1—C3 | 110.68 (15) | C10—C15—H15 | 120.8 (14) |
C16—N1—C3 | 123.93 (15) | C14—C15—H15 | 120.5 (14) |
C1—N2—N1 | 108.89 (16) | C1—C2—C3 | 101.83 (16) |
C15—C10—C11 | 121.05 (19) | C1—C2—H2A | 111.9 (12) |
C15—C10—O1 | 124.25 (16) | C3—C2—H2A | 113.4 (11) |
C11—C10—O1 | 114.67 (17) | C1—C2—H2B | 111.1 (12) |
C23—C22—C27 | 118.50 (19) | C3—C2—H2B | 109.9 (11) |
C23—C22—C1 | 121.37 (18) | H2A—C2—H2B | 108.6 (18) |
C27—C22—C1 | 120.1 (2) | C25—C24—C23 | 120.7 (2) |
N2—C1—C22 | 121.49 (18) | C25—C24—H24 | 119.1 (14) |
N2—C1—C2 | 112.71 (16) | C23—C24—H24 | 120.2 (14) |
C22—C1—C2 | 125.78 (18) | C16—C21—C20 | 120.4 (2) |
C21—C16—C17 | 118.5 (2) | C16—C21—H21 | 116.6 (14) |
C21—C16—N1 | 121.51 (18) | C20—C21—H21 | 123.1 (14) |
C17—C16—N1 | 120.0 (2) | C26—C27—C22 | 120.7 (2) |
N1—C3—C4 | 112.65 (15) | C26—C27—H27 | 121.9 (14) |
N1—C3—C2 | 101.09 (16) | C22—C27—H27 | 117.4 (14) |
C4—C3—C2 | 113.30 (17) | C18—C17—C16 | 120.3 (3) |
N1—C3—H3 | 109.8 (10) | C18—C17—H17 | 122.7 (15) |
C4—C3—H3 | 106.5 (10) | C16—C17—H17 | 117.0 (14) |
C2—C3—H3 | 113.6 (10) | C26—C25—C24 | 119.5 (2) |
C8—C9—C4 | 120.73 (19) | C26—C25—H25 | 121.0 (15) |
C8—C9—H9 | 118.7 (12) | C24—C25—H25 | 119.4 (15) |
C4—C9—H9 | 120.6 (12) | C12—C13—C14 | 119.7 (2) |
C9—C4—C5 | 118.47 (17) | C12—C13—H13 | 119.0 (17) |
C9—C4—C3 | 121.79 (17) | C14—C13—H13 | 121.4 (17) |
C5—C4—C3 | 119.70 (16) | C13—C12—C11 | 120.1 (2) |
C24—C23—C22 | 120.1 (2) | C13—C12—H12 | 124.1 (16) |
C24—C23—H23 | 119.8 (13) | C11—C12—H12 | 115.8 (16) |
C22—C23—H23 | 120.0 (13) | C25—C26—C27 | 120.5 (2) |
C10—C11—C12 | 119.6 (2) | C25—C26—H26 | 121.2 (15) |
C10—C11—H11 | 118.1 (14) | C27—C26—H26 | 118.2 (15) |
C12—C11—H11 | 122.3 (14) | C13—C14—C15 | 120.9 (2) |
C7—C6—C5 | 119.1 (2) | C13—C14—H14 | 121.6 (14) |
C7—C6—H6 | 119.1 (15) | C15—C14—H14 | 117.4 (14) |
C5—C6—H6 | 121.8 (15) | C19—C20—C21 | 120.7 (3) |
C9—C8—C7 | 118.97 (17) | C19—C20—H20 | 123.5 (14) |
C9—C8—O1 | 121.33 (19) | C21—C20—H20 | 115.8 (14) |
C7—C8—O1 | 119.60 (18) | C19—C18—C17 | 121.2 (3) |
C6—C5—C4 | 120.96 (19) | C19—C18—H18 | 116.8 (15) |
C6—C5—H5 | 122.7 (12) | C17—C18—H18 | 122.0 (15) |
C4—C5—H5 | 116.1 (12) | C18—C19—C20 | 119.0 (3) |
F1—C7—C6 | 119.7 (2) | C18—C19—H19 | 120.6 (15) |
F1—C7—C8 | 118.50 (19) | C20—C19—H19 | 120.4 (15) |
| | | |
C16—N1—N2—C1 | 165.44 (16) | C9—C4—C5—C6 | 0.8 (3) |
C3—N1—N2—C1 | 14.4 (2) | C3—C4—C5—C6 | 178.56 (18) |
C8—O1—C10—C15 | −14.0 (3) | C5—C6—C7—F1 | 178.60 (19) |
C8—O1—C10—C11 | 167.89 (18) | C5—C6—C7—C8 | −0.9 (3) |
N1—N2—C1—C22 | 178.38 (16) | C9—C8—C7—F1 | −179.64 (16) |
N1—N2—C1—C2 | 0.0 (2) | O1—C8—C7—F1 | 4.0 (3) |
C23—C22—C1—N2 | 6.7 (3) | C9—C8—C7—C6 | −0.1 (3) |
C27—C22—C1—N2 | −172.81 (19) | O1—C8—C7—C6 | −176.52 (18) |
C23—C22—C1—C2 | −175.13 (19) | C11—C10—C15—C14 | 0.0 (3) |
C27—C22—C1—C2 | 5.3 (3) | O1—C10—C15—C14 | −178.0 (2) |
N2—N1—C16—C21 | 0.3 (3) | N2—C1—C2—C3 | −13.3 (2) |
C3—N1—C16—C21 | 147.2 (2) | C22—C1—C2—C3 | 168.44 (17) |
N2—N1—C16—C17 | 179.76 (18) | N1—C3—C2—C1 | 19.52 (19) |
C3—N1—C16—C17 | −33.3 (3) | C4—C3—C2—C1 | −101.27 (18) |
N2—N1—C3—C4 | 99.68 (18) | C22—C23—C24—C25 | 1.0 (3) |
C16—N1—C3—C4 | −49.3 (2) | C17—C16—C21—C20 | −0.6 (3) |
N2—N1—C3—C2 | −21.56 (19) | N1—C16—C21—C20 | 178.9 (2) |
C16—N1—C3—C2 | −170.54 (18) | C23—C22—C27—C26 | 0.3 (3) |
C8—C9—C4—C5 | −1.8 (2) | C1—C22—C27—C26 | 179.9 (2) |
C8—C9—C4—C3 | −179.57 (17) | C21—C16—C17—C18 | 0.6 (3) |
N1—C3—C4—C9 | −29.4 (2) | N1—C16—C17—C18 | −178.9 (2) |
C2—C3—C4—C9 | 84.6 (2) | C23—C24—C25—C26 | −0.4 (3) |
N1—C3—C4—C5 | 152.93 (16) | C14—C13—C12—C11 | 0.2 (4) |
C2—C3—C4—C5 | −93.1 (2) | C10—C11—C12—C13 | −0.6 (3) |
C27—C22—C23—C24 | −0.9 (3) | C24—C25—C26—C27 | −0.2 (3) |
C1—C22—C23—C24 | 179.52 (18) | C22—C27—C26—C25 | 0.2 (3) |
C15—C10—C11—C12 | 0.5 (3) | C12—C13—C14—C15 | 0.3 (4) |
O1—C10—C11—C12 | 178.6 (2) | C10—C15—C14—C13 | −0.4 (4) |
C4—C9—C8—C7 | 1.5 (3) | C16—C21—C20—C19 | 0.4 (4) |
C4—C9—C8—O1 | 177.84 (16) | C16—C17—C18—C19 | −0.4 (4) |
C10—O1—C8—C9 | 88.3 (2) | C17—C18—C19—C20 | 0.2 (4) |
C10—O1—C8—C7 | −95.4 (2) | C21—C20—C19—C18 | −0.2 (4) |
C7—C6—C5—C4 | 0.6 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18···Cg3i | 0.95 (3) | 2.84 (2) | 3.566 (3) | 134 (2) |
C26—H26···Cg4ii | 0.96 (3) | 2.93 (3) | 3.755 (3) | 145 (2) |
C2—H2B···Cg5i | 1.00 (2) | 2.80 (2) | 3.764 (3) | 162 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1. |
(II) (5
S)-3-(4-chlorophenyl)-5-(3-fluoro-4-phenoxyphenyl)-1-phenyl-
4,5-dihydro-1
H-pyrazole
top
Crystal data top
C27H20ClFN2O | F(000) = 920 |
Mr = 442.90 | Dx = 1.344 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 725 reflections |
a = 17.728 (3) Å | θ = 1.6–26.4° |
b = 11.0132 (17) Å | µ = 0.21 mm−1 |
c = 11.2709 (17) Å | T = 290 K |
β = 95.729 (3)° | Needle, pale yellow |
V = 2189.6 (6) Å3 | 0.29 × 0.17 × 0.07 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4469 independent reflections |
Radiation source: fine-focus sealed tube | 2393 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.067 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→22 |
Tmin = 0.937, Tmax = 0.986 | k = −13→13 |
17206 measured reflections | l = −14→14 |
Refinement top
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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0477P)2 + 0.0424P] where P = (Fo2 + 2Fc2)/3 |
4469 reflections | (Δ/σ)max < 0.001 |
369 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C27H20ClFN2O | V = 2189.6 (6) Å3 |
Mr = 442.90 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.728 (3) Å | µ = 0.21 mm−1 |
b = 11.0132 (17) Å | T = 290 K |
c = 11.2709 (17) Å | 0.29 × 0.17 × 0.07 mm |
β = 95.729 (3)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4469 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2393 reflections with I > 2σ(I) |
Tmin = 0.937, Tmax = 0.986 | Rint = 0.067 |
17206 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.135 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.23 e Å−3 |
4469 reflections | Δρmin = −0.16 e Å−3 |
369 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | −0.14938 (5) | 0.07794 (9) | 0.93387 (8) | 0.0825 (3) | |
F1 | 0.36663 (10) | 0.52203 (15) | 0.48064 (17) | 0.0752 (6) | |
O1 | 0.36171 (13) | 0.35176 (19) | 0.64496 (19) | 0.0722 (7) | |
N1 | 0.16461 (13) | 0.0477 (2) | 0.4709 (2) | 0.0506 (6) | |
N2 | 0.12363 (13) | 0.0251 (2) | 0.5646 (2) | 0.0487 (6) | |
C1 | 0.07004 (16) | 0.1043 (3) | 0.5655 (3) | 0.0467 (7) | |
C2 | 0.06958 (19) | 0.1933 (3) | 0.4649 (3) | 0.0552 (9) | |
C3 | 0.14286 (16) | 0.1617 (3) | 0.4093 (3) | 0.0486 (8) | |
C4 | 0.20398 (15) | 0.2574 (2) | 0.4272 (2) | 0.0408 (7) | |
C5 | 0.20967 (18) | 0.3478 (3) | 0.3430 (3) | 0.0520 (8) | |
C6 | 0.26321 (19) | 0.4372 (3) | 0.3607 (3) | 0.0565 (9) | |
C7 | 0.31297 (17) | 0.4349 (3) | 0.4613 (3) | 0.0504 (8) | |
C8 | 0.30998 (17) | 0.3452 (3) | 0.5456 (3) | 0.0476 (7) | |
C9 | 0.25438 (17) | 0.2584 (3) | 0.5288 (3) | 0.0484 (8) | |
C10 | 0.39964 (16) | 0.2493 (3) | 0.6902 (3) | 0.0535 (8) | |
C11 | 0.43454 (19) | 0.2617 (4) | 0.8037 (3) | 0.0626 (9) | |
C12 | 0.4766 (2) | 0.1661 (5) | 0.8544 (4) | 0.0805 (12) | |
C13 | 0.4831 (2) | 0.0600 (5) | 0.7938 (4) | 0.0842 (12) | |
C14 | 0.4478 (2) | 0.0488 (4) | 0.6812 (4) | 0.0814 (12) | |
C15 | 0.40646 (19) | 0.1434 (4) | 0.6279 (3) | 0.0654 (10) | |
C16 | 0.22564 (16) | −0.0264 (3) | 0.4501 (3) | 0.0498 (8) | |
C17 | 0.26613 (19) | −0.0053 (3) | 0.3537 (3) | 0.0578 (9) | |
C18 | 0.3252 (2) | −0.0813 (3) | 0.3313 (4) | 0.0728 (11) | |
C19 | 0.3447 (3) | −0.1772 (4) | 0.4047 (4) | 0.0927 (14) | |
C20 | 0.3051 (2) | −0.1972 (4) | 0.5013 (4) | 0.0897 (13) | |
C21 | 0.2461 (2) | −0.1232 (3) | 0.5242 (3) | 0.0670 (10) | |
C22 | 0.01699 (16) | 0.1006 (3) | 0.6562 (3) | 0.0458 (7) | |
C23 | 0.02627 (19) | 0.0184 (3) | 0.7499 (3) | 0.0542 (8) | |
C24 | −0.02392 (19) | 0.0119 (3) | 0.8335 (3) | 0.0581 (9) | |
C25 | −0.08522 (17) | 0.0885 (3) | 0.8269 (3) | 0.0542 (8) | |
C26 | −0.09649 (18) | 0.1718 (3) | 0.7360 (3) | 0.0584 (9) | |
C27 | −0.04526 (17) | 0.1775 (3) | 0.6517 (3) | 0.0530 (8) | |
H2A | 0.0242 (17) | 0.184 (3) | 0.409 (3) | 0.070 (10)* | |
H2B | 0.0711 (16) | 0.276 (3) | 0.489 (3) | 0.071 (10)* | |
H3 | 0.1331 (14) | 0.146 (2) | 0.325 (2) | 0.053 (8)* | |
H5 | 0.1738 (16) | 0.347 (3) | 0.273 (2) | 0.067 (10)* | |
H6 | 0.2688 (14) | 0.502 (2) | 0.307 (2) | 0.050 (8)* | |
H9 | 0.2522 (13) | 0.199 (2) | 0.583 (2) | 0.040 (8)* | |
H11 | 0.4279 (15) | 0.337 (3) | 0.845 (2) | 0.056 (9)* | |
H12 | 0.4976 (19) | 0.181 (3) | 0.929 (3) | 0.079 (12)* | |
H13 | 0.511 (2) | −0.008 (3) | 0.834 (3) | 0.104 (13)* | |
H14 | 0.4506 (18) | −0.027 (3) | 0.638 (3) | 0.092 (13)* | |
H15 | 0.3822 (16) | 0.135 (3) | 0.552 (3) | 0.067 (10)* | |
H17 | 0.2523 (16) | 0.060 (3) | 0.305 (3) | 0.064 (10)* | |
H18 | 0.3501 (15) | −0.063 (2) | 0.263 (3) | 0.064 (9)* | |
H19 | 0.386 (2) | −0.224 (3) | 0.388 (3) | 0.096 (12)* | |
H20 | 0.318 (2) | −0.263 (3) | 0.553 (3) | 0.104 (14)* | |
H21 | 0.2214 (14) | −0.139 (2) | 0.589 (2) | 0.058 (8)* | |
H23 | 0.0671 (14) | −0.035 (2) | 0.756 (2) | 0.047 (8)* | |
H24 | −0.0187 (15) | −0.043 (2) | 0.891 (2) | 0.049 (9)* | |
H26 | −0.1396 (14) | 0.224 (2) | 0.729 (2) | 0.052 (7)* | |
H27 | −0.0558 (14) | 0.229 (2) | 0.588 (2) | 0.050 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0743 (6) | 0.0961 (7) | 0.0812 (6) | −0.0117 (5) | 0.0275 (5) | −0.0099 (5) |
F1 | 0.0707 (12) | 0.0494 (11) | 0.1054 (15) | −0.0104 (10) | 0.0084 (11) | −0.0012 (10) |
O1 | 0.0851 (17) | 0.0513 (14) | 0.0727 (15) | −0.0006 (13) | −0.0296 (13) | −0.0075 (12) |
N1 | 0.0555 (16) | 0.0412 (16) | 0.0565 (16) | 0.0025 (13) | 0.0116 (13) | 0.0015 (13) |
N2 | 0.0478 (15) | 0.0441 (15) | 0.0534 (16) | −0.0036 (13) | 0.0013 (12) | −0.0033 (12) |
C1 | 0.0409 (17) | 0.0460 (19) | 0.0516 (19) | −0.0058 (15) | −0.0032 (15) | −0.0071 (15) |
C2 | 0.049 (2) | 0.056 (2) | 0.060 (2) | 0.0012 (17) | −0.0005 (17) | 0.0045 (19) |
C3 | 0.0524 (19) | 0.047 (2) | 0.0449 (19) | 0.0024 (15) | −0.0027 (15) | 0.0008 (16) |
C4 | 0.0421 (17) | 0.0396 (17) | 0.0402 (17) | 0.0038 (14) | 0.0025 (14) | 0.0001 (14) |
C5 | 0.050 (2) | 0.057 (2) | 0.048 (2) | 0.0061 (18) | 0.0002 (16) | 0.0059 (18) |
C6 | 0.059 (2) | 0.048 (2) | 0.062 (2) | 0.0055 (18) | 0.0080 (19) | 0.0142 (19) |
C7 | 0.0450 (18) | 0.0346 (18) | 0.072 (2) | −0.0010 (15) | 0.0089 (17) | −0.0045 (17) |
C8 | 0.0535 (19) | 0.0388 (18) | 0.0487 (19) | 0.0048 (16) | −0.0047 (15) | −0.0037 (16) |
C9 | 0.061 (2) | 0.0385 (19) | 0.0451 (19) | 0.0014 (16) | −0.0002 (16) | 0.0074 (16) |
C10 | 0.0455 (19) | 0.057 (2) | 0.056 (2) | −0.0027 (16) | −0.0061 (16) | 0.0032 (18) |
C11 | 0.057 (2) | 0.070 (3) | 0.059 (2) | −0.010 (2) | −0.0050 (18) | −0.001 (2) |
C12 | 0.064 (3) | 0.105 (4) | 0.068 (3) | −0.003 (3) | −0.014 (2) | 0.015 (3) |
C13 | 0.063 (3) | 0.092 (4) | 0.094 (3) | 0.020 (2) | −0.008 (2) | 0.020 (3) |
C14 | 0.067 (3) | 0.084 (3) | 0.091 (3) | 0.026 (2) | −0.002 (2) | −0.003 (3) |
C15 | 0.058 (2) | 0.074 (3) | 0.061 (2) | 0.014 (2) | −0.0071 (19) | −0.004 (2) |
C16 | 0.0538 (19) | 0.0353 (18) | 0.060 (2) | −0.0042 (16) | 0.0048 (16) | −0.0057 (16) |
C17 | 0.061 (2) | 0.046 (2) | 0.067 (2) | −0.0018 (18) | 0.0084 (19) | −0.0018 (19) |
C18 | 0.075 (3) | 0.061 (2) | 0.087 (3) | 0.006 (2) | 0.032 (2) | 0.000 (2) |
C19 | 0.092 (3) | 0.063 (3) | 0.130 (4) | 0.025 (2) | 0.044 (3) | 0.008 (3) |
C20 | 0.099 (3) | 0.065 (3) | 0.109 (3) | 0.031 (2) | 0.032 (3) | 0.023 (3) |
C21 | 0.074 (3) | 0.052 (2) | 0.078 (3) | 0.0084 (19) | 0.025 (2) | 0.007 (2) |
C22 | 0.0456 (18) | 0.0397 (18) | 0.0503 (18) | −0.0082 (15) | −0.0047 (15) | −0.0060 (15) |
C23 | 0.053 (2) | 0.048 (2) | 0.061 (2) | 0.0024 (18) | 0.0033 (18) | −0.0002 (17) |
C24 | 0.067 (2) | 0.050 (2) | 0.056 (2) | −0.0057 (19) | 0.0039 (19) | 0.0055 (19) |
C25 | 0.054 (2) | 0.051 (2) | 0.058 (2) | −0.0135 (17) | 0.0043 (16) | −0.0121 (18) |
C26 | 0.0407 (19) | 0.053 (2) | 0.080 (3) | 0.0021 (17) | 0.0031 (18) | −0.0076 (19) |
C27 | 0.047 (2) | 0.049 (2) | 0.061 (2) | −0.0023 (17) | −0.0034 (17) | 0.0025 (18) |
Geometric parameters (Å, º) top
Cl1—C25 | 1.742 (3) | C26—H26 | 0.95 (2) |
F1—C7 | 1.354 (3) | C2—H2A | 0.98 (3) |
O1—C8 | 1.377 (3) | C2—H2B | 0.95 (3) |
O1—C10 | 1.384 (4) | C6—C5 | 1.369 (4) |
N1—N2 | 1.363 (3) | C6—H6 | 0.94 (3) |
N1—C16 | 1.394 (3) | C23—C24 | 1.360 (4) |
N1—C3 | 1.467 (3) | C23—H23 | 0.93 (2) |
N2—C1 | 1.291 (3) | C5—H5 | 0.96 (3) |
C16—C21 | 1.380 (4) | C17—C18 | 1.384 (4) |
C16—C17 | 1.381 (4) | C17—H17 | 0.92 (3) |
C4—C9 | 1.380 (4) | C24—H24 | 0.89 (3) |
C4—C5 | 1.386 (4) | C27—H27 | 0.92 (3) |
C4—C3 | 1.511 (4) | C15—C14 | 1.377 (5) |
C3—C2 | 1.537 (4) | C15—H15 | 0.92 (3) |
C3—H3 | 0.97 (3) | C21—C20 | 1.370 (5) |
C22—C23 | 1.388 (4) | C21—H21 | 0.90 (2) |
C22—C27 | 1.388 (4) | C18—C19 | 1.364 (5) |
C22—C1 | 1.457 (4) | C18—H18 | 0.95 (3) |
C9—C8 | 1.373 (4) | C11—C12 | 1.381 (5) |
C9—H9 | 0.90 (2) | C11—H11 | 0.96 (3) |
C1—C2 | 1.498 (4) | C12—C13 | 1.364 (6) |
C10—C11 | 1.372 (4) | C12—H12 | 0.90 (3) |
C10—C15 | 1.372 (4) | C14—C13 | 1.363 (5) |
C7—C6 | 1.365 (4) | C14—H14 | 0.97 (3) |
C7—C8 | 1.375 (4) | C13—H13 | 0.98 (4) |
C25—C24 | 1.372 (4) | C19—C20 | 1.370 (5) |
C25—C26 | 1.375 (4) | C19—H19 | 0.93 (3) |
C26—C27 | 1.380 (4) | C20—H20 | 0.95 (4) |
| | | |
Cl1···Cg2i | 3.560 (2) | | |
| | | |
C8—O1—C10 | 121.1 (2) | C5—C6—H6 | 124.3 (16) |
N2—N1—C16 | 120.4 (2) | C24—C23—C22 | 121.6 (3) |
N2—N1—C3 | 112.8 (2) | C24—C23—H23 | 118.4 (16) |
C16—N1—C3 | 126.4 (2) | C22—C23—H23 | 120.0 (16) |
C1—N2—N1 | 109.4 (2) | C9—C8—C7 | 118.8 (3) |
C21—C16—C17 | 118.7 (3) | C9—C8—O1 | 124.0 (3) |
C21—C16—N1 | 120.8 (3) | C7—C8—O1 | 117.2 (3) |
C17—C16—N1 | 120.5 (3) | C6—C5—C4 | 120.9 (3) |
C9—C4—C5 | 118.5 (3) | C6—C5—H5 | 121.3 (17) |
C9—C4—C3 | 120.8 (3) | C4—C5—H5 | 117.7 (17) |
C5—C4—C3 | 120.7 (3) | C16—C17—C18 | 120.3 (4) |
N1—C3—C4 | 112.5 (2) | C16—C17—H17 | 118.2 (18) |
N1—C3—C2 | 101.2 (2) | C18—C17—H17 | 121.6 (18) |
C4—C3—C2 | 114.3 (3) | C23—C24—C25 | 120.0 (3) |
N1—C3—H3 | 108.8 (16) | C23—C24—H24 | 121.1 (17) |
C4—C3—H3 | 108.4 (15) | C25—C24—H24 | 118.9 (17) |
C2—C3—H3 | 111.5 (15) | C26—C27—C22 | 121.5 (3) |
C23—C22—C27 | 117.3 (3) | C26—C27—H27 | 118.0 (16) |
C23—C22—C1 | 121.1 (3) | C22—C27—H27 | 120.3 (16) |
C27—C22—C1 | 121.6 (3) | C10—C15—C14 | 119.3 (4) |
C8—C9—C4 | 121.1 (3) | C10—C15—H15 | 120.0 (19) |
C8—C9—H9 | 119.6 (16) | C14—C15—H15 | 121 (2) |
C4—C9—H9 | 119.2 (16) | C20—C21—C16 | 120.4 (4) |
N2—C1—C22 | 120.9 (3) | C20—C21—H21 | 118.5 (17) |
N2—C1—C2 | 112.6 (3) | C16—C21—H21 | 121.1 (17) |
C22—C1—C2 | 126.5 (3) | C19—C18—C17 | 120.5 (4) |
C11—C10—C15 | 120.5 (3) | C19—C18—H18 | 123.1 (17) |
C11—C10—O1 | 114.8 (3) | C17—C18—H18 | 116.3 (17) |
C15—C10—O1 | 124.7 (3) | C10—C11—C12 | 119.0 (4) |
F1—C7—C6 | 120.4 (3) | C10—C11—H11 | 118.2 (17) |
F1—C7—C8 | 118.2 (3) | C12—C11—H11 | 122.8 (17) |
C6—C7—C8 | 121.4 (3) | C13—C12—C11 | 121.0 (4) |
C24—C25—C26 | 120.4 (3) | C13—C12—H12 | 125 (2) |
C24—C25—Cl1 | 119.4 (3) | C11—C12—H12 | 113 (2) |
C26—C25—Cl1 | 120.3 (3) | C13—C14—C15 | 120.8 (5) |
C25—C26—C27 | 119.1 (3) | C13—C14—H14 | 120 (2) |
C25—C26—H26 | 121.1 (14) | C15—C14—H14 | 119 (2) |
C27—C26—H26 | 119.7 (15) | C14—C13—C12 | 119.3 (4) |
C1—C2—C3 | 102.7 (3) | C14—C13—H13 | 121 (2) |
C1—C2—H2A | 111.5 (17) | C12—C13—H13 | 119 (2) |
C3—C2—H2A | 112.7 (16) | C18—C19—C20 | 119.2 (4) |
C1—C2—H2B | 114.6 (18) | C18—C19—H19 | 118 (2) |
C3—C2—H2B | 109.3 (17) | C20—C19—H19 | 123 (2) |
H2A—C2—H2B | 106 (2) | C21—C20—C19 | 121.0 (4) |
C7—C6—C5 | 119.3 (3) | C21—C20—H20 | 119 (2) |
C7—C6—H6 | 116.4 (16) | C19—C20—H20 | 120 (2) |
| | | |
C16—N1—N2—C1 | −179.5 (2) | C4—C9—C8—C7 | 2.6 (4) |
C3—N1—N2—C1 | 7.4 (3) | C4—C9—C8—O1 | 179.7 (3) |
N2—N1—C16—C21 | −0.5 (4) | F1—C7—C8—C9 | 178.0 (2) |
C3—N1—C16—C21 | 171.6 (3) | C6—C7—C8—C9 | −1.6 (4) |
N2—N1—C16—C17 | 178.5 (3) | F1—C7—C8—O1 | 0.7 (4) |
C3—N1—C16—C17 | −9.4 (4) | C6—C7—C8—O1 | −178.9 (3) |
N2—N1—C3—C4 | 111.1 (3) | C10—O1—C8—C9 | 46.3 (4) |
C16—N1—C3—C4 | −61.5 (4) | C10—O1—C8—C7 | −136.5 (3) |
N2—N1—C3—C2 | −11.3 (3) | C7—C6—C5—C4 | 1.9 (4) |
C16—N1—C3—C2 | 176.1 (3) | C9—C4—C5—C6 | −1.0 (4) |
C9—C4—C3—N1 | −28.2 (4) | C3—C4—C5—C6 | 177.6 (3) |
C5—C4—C3—N1 | 153.2 (3) | C21—C16—C17—C18 | 1.0 (5) |
C9—C4—C3—C2 | 86.5 (3) | N1—C16—C17—C18 | −178.1 (3) |
C5—C4—C3—C2 | −92.1 (3) | C22—C23—C24—C25 | −0.5 (5) |
C5—C4—C9—C8 | −1.3 (4) | C26—C25—C24—C23 | 0.2 (5) |
C3—C4—C9—C8 | −179.9 (3) | Cl1—C25—C24—C23 | 179.4 (2) |
N1—N2—C1—C22 | 179.5 (2) | C25—C26—C27—C22 | 0.5 (4) |
N1—N2—C1—C2 | 0.5 (3) | C23—C22—C27—C26 | −0.8 (4) |
C23—C22—C1—N2 | 5.4 (4) | C1—C22—C27—C26 | 178.3 (3) |
C27—C22—C1—N2 | −173.6 (3) | C11—C10—C15—C14 | 0.9 (5) |
C23—C22—C1—C2 | −175.7 (3) | O1—C10—C15—C14 | 177.8 (3) |
C27—C22—C1—C2 | 5.2 (4) | C17—C16—C21—C20 | −0.6 (5) |
C8—O1—C10—C11 | −164.6 (3) | N1—C16—C21—C20 | 178.5 (3) |
C8—O1—C10—C15 | 18.4 (4) | C16—C17—C18—C19 | −0.6 (5) |
C24—C25—C26—C27 | −0.2 (5) | C15—C10—C11—C12 | 0.1 (5) |
Cl1—C25—C26—C27 | −179.4 (2) | O1—C10—C11—C12 | −177.1 (3) |
N2—C1—C2—C3 | −7.4 (4) | C10—C11—C12—C13 | −0.8 (6) |
C22—C1—C2—C3 | 173.7 (3) | C10—C15—C14—C13 | −1.2 (6) |
N1—C3—C2—C1 | 10.4 (3) | C15—C14—C13—C12 | 0.5 (6) |
C4—C3—C2—C1 | −110.8 (3) | C11—C12—C13—C14 | 0.6 (6) |
F1—C7—C6—C5 | 179.7 (3) | C17—C18—C19—C20 | −0.3 (6) |
C8—C7—C6—C5 | −0.6 (4) | C16—C21—C20—C19 | −0.3 (6) |
C27—C22—C23—C24 | 0.8 (4) | C18—C19—C20—C21 | 0.7 (7) |
C1—C22—C23—C24 | −178.3 (3) | | |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
(III) (5
R)-5-(3-fluoro-4-phenoxyphenyl)-3-(4-methylphenyl)-1-phenyl-
4,5-dihydro-1
H-pyrazole
top
Crystal data top
C28H23FN2O | F(000) = 888 |
Mr = 422.48 | Dx = 1.279 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 650 reflections |
a = 17.742 (6) Å | θ = 1.7–25.4° |
b = 11.099 (4) Å | µ = 0.08 mm−1 |
c = 11.187 (4) Å | T = 290 K |
β = 95.293 (6)° | Needle, colourless |
V = 2193.5 (13) Å3 | 0.40 × 0.40 × 0.12 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4427 independent reflections |
Radiation source: fine-focus sealed tube | 2845 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 26.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −22→22 |
Tmin = 0.921, Tmax = 0.990 | k = −12→13 |
16874 measured reflections | l = −13→13 |
Refinement top
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.2251P] where P = (Fo2 + 2Fc2)/3 |
4427 reflections | (Δ/σ)max = 0.026 |
370 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
Crystal data top
C28H23FN2O | V = 2193.5 (13) Å3 |
Mr = 422.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 17.742 (6) Å | µ = 0.08 mm−1 |
b = 11.099 (4) Å | T = 290 K |
c = 11.187 (4) Å | 0.40 × 0.40 × 0.12 mm |
β = 95.293 (6)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4427 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2845 reflections with I > 2σ(I) |
Tmin = 0.921, Tmax = 0.990 | Rint = 0.031 |
16874 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.15 e Å−3 |
4427 reflections | Δρmin = −0.14 e Å−3 |
370 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.36457 (6) | 0.52122 (10) | 0.48041 (11) | 0.0789 (4) | |
N1 | 0.16717 (8) | 0.04657 (13) | 0.47688 (13) | 0.0561 (4) | |
N2 | 0.12514 (8) | 0.02362 (13) | 0.57057 (13) | 0.0522 (4) | |
O1 | 0.36300 (8) | 0.35104 (12) | 0.64487 (12) | 0.0743 (4) | |
C1 | 0.07122 (9) | 0.10149 (15) | 0.57005 (15) | 0.0485 (4) | |
C2 | 0.07102 (11) | 0.1889 (2) | 0.46820 (19) | 0.0595 (5) | |
C3 | 0.14470 (10) | 0.15831 (16) | 0.41309 (17) | 0.0532 (5) | |
C4 | 0.20465 (9) | 0.25532 (15) | 0.43068 (14) | 0.0465 (4) | |
C5 | 0.20859 (11) | 0.34545 (18) | 0.34638 (17) | 0.0559 (5) | |
C6 | 0.26171 (11) | 0.43565 (19) | 0.36304 (19) | 0.0612 (5) | |
C7 | 0.31209 (10) | 0.43342 (16) | 0.46265 (18) | 0.0548 (5) | |
C8 | 0.31083 (10) | 0.34383 (16) | 0.54660 (15) | 0.0521 (4) | |
C9 | 0.25569 (10) | 0.25630 (17) | 0.53151 (16) | 0.0504 (4) | |
C10 | 0.40066 (10) | 0.24909 (18) | 0.69112 (17) | 0.0562 (5) | |
C11 | 0.43529 (11) | 0.2623 (2) | 0.80495 (18) | 0.0655 (5) | |
C12 | 0.47669 (12) | 0.1678 (3) | 0.8572 (2) | 0.0800 (7) | |
C13 | 0.48311 (13) | 0.0620 (3) | 0.7966 (3) | 0.0845 (7) | |
C14 | 0.44831 (13) | 0.0499 (2) | 0.6836 (3) | 0.0828 (7) | |
C15 | 0.40713 (11) | 0.1437 (2) | 0.6287 (2) | 0.0682 (6) | |
C16 | 0.22829 (10) | −0.02612 (16) | 0.45608 (17) | 0.0536 (5) | |
C17 | 0.26903 (11) | −0.00421 (19) | 0.3588 (2) | 0.0612 (5) | |
C18 | 0.32853 (13) | −0.0784 (2) | 0.3367 (2) | 0.0768 (6) | |
C19 | 0.34846 (16) | −0.1737 (2) | 0.4101 (3) | 0.0946 (8) | |
C20 | 0.30878 (15) | −0.1941 (2) | 0.5075 (3) | 0.0941 (8) | |
C21 | 0.24916 (13) | −0.12180 (18) | 0.5313 (2) | 0.0703 (6) | |
C22 | 0.01698 (9) | 0.09830 (15) | 0.65971 (15) | 0.0495 (4) | |
C23 | 0.02339 (11) | 0.01524 (19) | 0.75263 (18) | 0.0598 (5) | |
C24 | −0.02915 (12) | 0.0104 (2) | 0.83540 (19) | 0.0652 (5) | |
C25 | −0.09007 (11) | 0.08810 (18) | 0.83000 (17) | 0.0604 (5) | |
C26 | −0.09657 (11) | 0.17169 (19) | 0.7384 (2) | 0.0658 (6) | |
C27 | −0.04383 (11) | 0.17657 (18) | 0.6547 (2) | 0.0611 (5) | |
C28 | −0.14806 (12) | 0.0796 (2) | 0.9199 (2) | 0.0850 (7) | |
H2A | 0.0283 (11) | 0.1762 (16) | 0.4122 (17) | 0.069 (6)* | |
H2B | 0.0712 (10) | 0.2710 (19) | 0.4959 (16) | 0.071 (6)* | |
H3 | 0.1352 (8) | 0.1420 (14) | 0.3288 (15) | 0.050 (5)* | |
H5 | 0.1739 (10) | 0.3470 (16) | 0.2778 (16) | 0.063 (5)* | |
H6 | 0.2658 (10) | 0.4977 (17) | 0.3069 (17) | 0.070 (6)* | |
H9 | 0.2545 (9) | 0.1947 (15) | 0.5877 (14) | 0.049 (5)* | |
H11 | 0.4289 (10) | 0.3385 (17) | 0.8470 (16) | 0.070 (6)* | |
H12 | 0.4996 (12) | 0.1772 (19) | 0.936 (2) | 0.094 (7)* | |
H13 | 0.5117 (15) | 0.000 (2) | 0.834 (2) | 0.112 (9)* | |
H14 | 0.4518 (12) | −0.023 (2) | 0.639 (2) | 0.097 (8)* | |
H15 | 0.3844 (10) | 0.1351 (17) | 0.5476 (17) | 0.072 (6)* | |
H17 | 0.2576 (10) | 0.0616 (16) | 0.3080 (16) | 0.061 (6)* | |
H18 | 0.3528 (11) | −0.0596 (17) | 0.2694 (18) | 0.075 (6)* | |
H19 | 0.3918 (14) | −0.221 (2) | 0.394 (2) | 0.108 (8)* | |
H20 | 0.3226 (13) | −0.256 (2) | 0.562 (2) | 0.101 (8)* | |
H21 | 0.2236 (10) | −0.1371 (17) | 0.6002 (17) | 0.074 (6)* | |
H23 | 0.0642 (10) | −0.0404 (17) | 0.7614 (16) | 0.067 (6)* | |
H24 | −0.0234 (12) | −0.0509 (19) | 0.903 (2) | 0.096 (7)* | |
H26 | −0.1418 (10) | 0.2305 (17) | 0.7325 (15) | 0.067 (5)* | |
H27 | −0.0503 (9) | 0.2336 (16) | 0.5906 (15) | 0.056 (5)* | |
H28A | −0.1979 | 0.0795 | 0.8785 | 0.127* | |
H28B | −0.1428 | 0.1475 | 0.9733 | 0.127* | |
H28C | −0.1404 | 0.0066 | 0.9653 | 0.127* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0740 (8) | 0.0545 (7) | 0.1088 (10) | −0.0111 (6) | 0.0116 (7) | −0.0003 (6) |
N1 | 0.0577 (9) | 0.0494 (9) | 0.0627 (10) | 0.0037 (7) | 0.0131 (8) | 0.0014 (7) |
N2 | 0.0530 (9) | 0.0479 (9) | 0.0556 (9) | −0.0041 (7) | 0.0045 (7) | −0.0052 (7) |
O1 | 0.0839 (9) | 0.0552 (8) | 0.0774 (9) | 0.0001 (8) | −0.0269 (8) | −0.0069 (7) |
C1 | 0.0439 (10) | 0.0478 (11) | 0.0520 (10) | −0.0033 (9) | −0.0041 (8) | −0.0071 (8) |
C2 | 0.0496 (12) | 0.0611 (14) | 0.0668 (13) | 0.0014 (10) | −0.0011 (10) | 0.0021 (11) |
C3 | 0.0536 (11) | 0.0565 (12) | 0.0487 (11) | 0.0038 (9) | 0.0003 (9) | −0.0003 (9) |
C4 | 0.0463 (10) | 0.0486 (10) | 0.0445 (9) | 0.0068 (8) | 0.0039 (8) | −0.0001 (8) |
C5 | 0.0546 (11) | 0.0634 (13) | 0.0490 (11) | 0.0095 (10) | 0.0008 (9) | 0.0072 (10) |
C6 | 0.0632 (13) | 0.0562 (13) | 0.0654 (13) | 0.0092 (11) | 0.0134 (11) | 0.0178 (11) |
C7 | 0.0496 (10) | 0.0428 (11) | 0.0730 (13) | 0.0008 (9) | 0.0116 (10) | −0.0021 (10) |
C8 | 0.0542 (10) | 0.0469 (11) | 0.0539 (11) | 0.0063 (9) | −0.0022 (9) | −0.0036 (9) |
C9 | 0.0607 (11) | 0.0446 (11) | 0.0456 (10) | 0.0040 (9) | 0.0031 (9) | 0.0055 (9) |
C10 | 0.0479 (10) | 0.0597 (13) | 0.0597 (11) | −0.0044 (9) | −0.0024 (9) | 0.0035 (10) |
C11 | 0.0589 (12) | 0.0750 (15) | 0.0605 (12) | −0.0118 (11) | −0.0052 (10) | −0.0002 (12) |
C12 | 0.0618 (14) | 0.110 (2) | 0.0653 (15) | −0.0062 (14) | −0.0107 (11) | 0.0145 (15) |
C13 | 0.0600 (14) | 0.097 (2) | 0.0943 (19) | 0.0162 (14) | −0.0049 (13) | 0.0194 (17) |
C14 | 0.0665 (14) | 0.0834 (18) | 0.0969 (19) | 0.0238 (13) | −0.0004 (13) | −0.0037 (15) |
C15 | 0.0605 (13) | 0.0784 (16) | 0.0636 (13) | 0.0131 (11) | −0.0055 (10) | −0.0058 (12) |
C16 | 0.0521 (11) | 0.0427 (10) | 0.0662 (12) | −0.0027 (9) | 0.0063 (9) | −0.0098 (9) |
C17 | 0.0621 (13) | 0.0527 (13) | 0.0697 (13) | 0.0007 (10) | 0.0114 (10) | −0.0039 (10) |
C18 | 0.0756 (15) | 0.0670 (15) | 0.0920 (17) | 0.0028 (12) | 0.0299 (13) | −0.0039 (13) |
C19 | 0.0862 (17) | 0.0717 (17) | 0.132 (2) | 0.0227 (14) | 0.0410 (17) | 0.0062 (16) |
C20 | 0.0980 (19) | 0.0669 (16) | 0.122 (2) | 0.0277 (14) | 0.0325 (17) | 0.0224 (16) |
C21 | 0.0750 (14) | 0.0524 (13) | 0.0861 (16) | 0.0076 (11) | 0.0213 (12) | 0.0074 (11) |
C22 | 0.0443 (10) | 0.0482 (11) | 0.0547 (11) | −0.0051 (8) | −0.0015 (8) | −0.0073 (9) |
C23 | 0.0566 (12) | 0.0575 (13) | 0.0650 (13) | 0.0038 (10) | 0.0032 (10) | −0.0010 (10) |
C24 | 0.0674 (13) | 0.0626 (13) | 0.0664 (13) | −0.0044 (11) | 0.0101 (11) | −0.0016 (11) |
C25 | 0.0560 (11) | 0.0575 (12) | 0.0687 (13) | −0.0120 (10) | 0.0108 (10) | −0.0106 (10) |
C26 | 0.0488 (11) | 0.0604 (14) | 0.0892 (15) | 0.0008 (10) | 0.0112 (11) | −0.0061 (12) |
C27 | 0.0515 (11) | 0.0581 (13) | 0.0732 (14) | −0.0016 (10) | 0.0038 (10) | 0.0033 (11) |
C28 | 0.0739 (14) | 0.0914 (17) | 0.0929 (16) | −0.0115 (13) | 0.0258 (12) | −0.0105 (13) |
Geometric parameters (Å, º) top
F1—C7 | 1.350 (2) | C25—C26 | 1.380 (3) |
N2—C1 | 1.289 (2) | C25—C28 | 1.507 (3) |
N2—N1 | 1.365 (2) | C10—C11 | 1.370 (3) |
C16—C17 | 1.383 (3) | C10—C15 | 1.372 (3) |
C16—C21 | 1.384 (3) | C17—C18 | 1.379 (3) |
C16—N1 | 1.388 (2) | C17—H17 | 0.937 (17) |
N1—C3 | 1.468 (2) | C24—H24 | 1.01 (2) |
C1—C22 | 1.453 (2) | C2—H2A | 0.948 (19) |
C1—C2 | 1.496 (3) | C2—H2B | 0.96 (2) |
C8—C7 | 1.369 (2) | C21—C20 | 1.373 (3) |
C8—O1 | 1.373 (2) | C21—H21 | 0.946 (19) |
C8—C9 | 1.378 (2) | C15—C14 | 1.383 (3) |
C22—C27 | 1.382 (2) | C15—H15 | 0.963 (18) |
C22—C23 | 1.386 (3) | C11—C12 | 1.379 (3) |
C7—C6 | 1.363 (3) | C11—H11 | 0.979 (19) |
C27—C26 | 1.384 (3) | C26—H26 | 1.032 (18) |
C27—H27 | 0.956 (17) | C28—H28A | 0.9600 |
C9—C4 | 1.380 (2) | C28—H28B | 0.9600 |
C9—H9 | 0.930 (16) | C28—H28C | 0.9600 |
C5—C6 | 1.376 (3) | C14—C13 | 1.361 (3) |
C5—C4 | 1.381 (2) | C14—H14 | 0.96 (2) |
C5—H5 | 0.938 (18) | C13—C12 | 1.366 (4) |
C4—C3 | 1.514 (2) | C13—H13 | 0.93 (3) |
O1—C10 | 1.389 (2) | C18—C19 | 1.366 (3) |
C3—C2 | 1.534 (3) | C18—H18 | 0.92 (2) |
C3—H3 | 0.960 (16) | C12—H12 | 0.95 (2) |
C23—C24 | 1.374 (3) | C20—C19 | 1.369 (3) |
C23—H23 | 0.950 (18) | C20—H20 | 0.94 (2) |
C6—H6 | 0.940 (19) | C19—H19 | 0.96 (2) |
C25—C24 | 1.379 (3) | | |
| | | |
C1—N2—N1 | 109.22 (14) | C15—C10—O1 | 124.37 (17) |
C17—C16—C21 | 118.94 (19) | C18—C17—C16 | 120.0 (2) |
C17—C16—N1 | 120.19 (18) | C18—C17—H17 | 119.0 (11) |
C21—C16—N1 | 120.87 (17) | C16—C17—H17 | 121.0 (11) |
N2—N1—C16 | 120.71 (15) | C23—C24—C25 | 121.6 (2) |
N2—N1—C3 | 112.82 (14) | C23—C24—H24 | 120.0 (13) |
C16—N1—C3 | 126.22 (15) | C25—C24—H24 | 118.4 (13) |
N2—C1—C22 | 121.27 (16) | C1—C2—C3 | 102.72 (15) |
N2—C1—C2 | 112.83 (16) | C1—C2—H2A | 110.6 (11) |
C22—C1—C2 | 125.89 (16) | C3—C2—H2A | 111.1 (11) |
C7—C8—O1 | 117.04 (17) | C1—C2—H2B | 111.7 (11) |
C7—C8—C9 | 118.96 (17) | C3—C2—H2B | 111.2 (11) |
O1—C8—C9 | 123.90 (16) | H2A—C2—H2B | 109.4 (16) |
C27—C22—C23 | 117.27 (18) | C20—C21—C16 | 119.9 (2) |
C27—C22—C1 | 121.38 (17) | C20—C21—H21 | 119.3 (12) |
C23—C22—C1 | 121.34 (16) | C16—C21—H21 | 120.8 (12) |
F1—C7—C6 | 119.92 (17) | C10—C15—C14 | 118.8 (2) |
F1—C7—C8 | 118.55 (17) | C10—C15—H15 | 121.1 (12) |
C6—C7—C8 | 121.53 (18) | C14—C15—H15 | 120.1 (12) |
C22—C27—C26 | 121.4 (2) | C10—C11—C12 | 119.2 (2) |
C22—C27—H27 | 119.1 (10) | C10—C11—H11 | 118.5 (11) |
C26—C27—H27 | 119.4 (10) | C12—C11—H11 | 122.2 (11) |
C8—C9—C4 | 120.71 (17) | C25—C26—C27 | 120.9 (2) |
C8—C9—H9 | 119.7 (10) | C25—C26—H26 | 119.0 (10) |
C4—C9—H9 | 119.5 (10) | C27—C26—H26 | 120.1 (10) |
C6—C5—C4 | 120.78 (19) | C25—C28—H28A | 109.5 |
C6—C5—H5 | 119.1 (11) | C25—C28—H28B | 109.5 |
C4—C5—H5 | 120.1 (11) | H28A—C28—H28B | 109.5 |
C9—C4—C5 | 118.80 (17) | C25—C28—H28C | 109.5 |
C9—C4—C3 | 120.81 (16) | H28A—C28—H28C | 109.5 |
C5—C4—C3 | 120.38 (16) | H28B—C28—H28C | 109.5 |
C8—O1—C10 | 121.09 (14) | C13—C14—C15 | 120.9 (3) |
N1—C3—C4 | 112.45 (14) | C13—C14—H14 | 121.6 (14) |
N1—C3—C2 | 101.25 (15) | C15—C14—H14 | 117.4 (14) |
C4—C3—C2 | 113.88 (16) | C14—C13—C12 | 119.6 (3) |
N1—C3—H3 | 109.5 (10) | C14—C13—H13 | 121.5 (16) |
C4—C3—H3 | 108.7 (9) | C12—C13—H13 | 118.9 (16) |
C2—C3—H3 | 110.9 (9) | C19—C18—C17 | 121.0 (2) |
C24—C23—C22 | 121.2 (2) | C19—C18—H18 | 123.3 (12) |
C24—C23—H23 | 117.6 (11) | C17—C18—H18 | 115.7 (13) |
C22—C23—H23 | 121.2 (11) | C13—C12—C11 | 120.6 (2) |
C7—C6—C5 | 119.14 (19) | C13—C12—H12 | 120.7 (13) |
C7—C6—H6 | 118.3 (12) | C11—C12—H12 | 118.7 (14) |
C5—C6—H6 | 122.6 (12) | C19—C20—C21 | 121.3 (3) |
C24—C25—C26 | 117.67 (19) | C19—C20—H20 | 121.1 (14) |
C24—C25—C28 | 120.82 (19) | C21—C20—H20 | 117.5 (14) |
C26—C25—C28 | 121.50 (19) | C18—C19—C20 | 118.9 (2) |
C11—C10—C15 | 120.8 (2) | C18—C19—H19 | 118.7 (14) |
C11—C10—O1 | 114.72 (18) | C20—C19—H19 | 122.3 (14) |
| | | |
C1—N2—N1—C16 | −178.90 (15) | C27—C22—C23—C24 | 0.7 (3) |
C1—N2—N1—C3 | 6.47 (19) | C1—C22—C23—C24 | −178.25 (17) |
C17—C16—N1—N2 | 178.02 (16) | F1—C7—C6—C5 | −179.99 (16) |
C21—C16—N1—N2 | −1.5 (3) | C8—C7—C6—C5 | −0.3 (3) |
C17—C16—N1—C3 | −8.1 (3) | C4—C5—C6—C7 | 1.8 (3) |
C21—C16—N1—C3 | 172.35 (18) | C8—O1—C10—C11 | −163.65 (17) |
N1—N2—C1—C22 | 179.59 (14) | C8—O1—C10—C15 | 19.4 (3) |
N1—N2—C1—C2 | 0.9 (2) | C21—C16—C17—C18 | 1.1 (3) |
N2—C1—C22—C27 | −175.60 (16) | N1—C16—C17—C18 | −178.40 (18) |
C2—C1—C22—C27 | 2.9 (3) | C22—C23—C24—C25 | −0.3 (3) |
N2—C1—C22—C23 | 3.3 (2) | C26—C25—C24—C23 | −0.2 (3) |
C2—C1—C22—C23 | −178.28 (18) | C28—C25—C24—C23 | 178.63 (19) |
O1—C8—C7—F1 | 1.0 (2) | N2—C1—C2—C3 | −7.3 (2) |
C9—C8—C7—F1 | 177.61 (15) | C22—C1—C2—C3 | 174.14 (16) |
O1—C8—C7—C6 | −178.74 (16) | N1—C3—C2—C1 | 9.83 (19) |
C9—C8—C7—C6 | −2.1 (3) | C4—C3—C2—C1 | −111.09 (18) |
C23—C22—C27—C26 | −0.5 (3) | C17—C16—C21—C20 | −1.0 (3) |
C1—C22—C27—C26 | 178.41 (17) | N1—C16—C21—C20 | 178.5 (2) |
C7—C8—C9—C4 | 3.1 (3) | C11—C10—C15—C14 | 1.1 (3) |
O1—C8—C9—C4 | 179.42 (16) | O1—C10—C15—C14 | 177.88 (18) |
C8—C9—C4—C5 | −1.6 (3) | C15—C10—C11—C12 | −0.4 (3) |
C8—C9—C4—C3 | 179.17 (16) | O1—C10—C11—C12 | −177.49 (17) |
C6—C5—C4—C9 | −0.9 (3) | C24—C25—C26—C27 | 0.3 (3) |
C6—C5—C4—C3 | 178.40 (16) | C28—C25—C26—C27 | −178.46 (18) |
C7—C8—O1—C10 | −138.84 (17) | C22—C27—C26—C25 | 0.0 (3) |
C9—C8—O1—C10 | 44.7 (2) | C10—C15—C14—C13 | −1.2 (3) |
N2—N1—C3—C4 | 111.48 (16) | C15—C14—C13—C12 | 0.7 (4) |
C16—N1—C3—C4 | −62.8 (2) | C16—C17—C18—C19 | −0.3 (3) |
N2—N1—C3—C2 | −10.44 (19) | C14—C13—C12—C11 | 0.0 (4) |
C16—N1—C3—C2 | 175.28 (17) | C10—C11—C12—C13 | −0.2 (3) |
C9—C4—C3—N1 | −25.8 (2) | C16—C21—C20—C19 | 0.0 (4) |
C5—C4—C3—N1 | 154.98 (16) | C17—C18—C19—C20 | −0.7 (4) |
C9—C4—C3—C2 | 88.7 (2) | C21—C20—C19—C18 | 0.8 (4) |
C5—C4—C3—C2 | −90.6 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28C···Cg2i | 0.96 | 3.00 | 3.663 (3) | 128 |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
(IV) (5
S)-5-(3-fluoro-4-phenoxyphenyl)-3-(4-methoxyphenyl)-1-phenyl-
4,5-dihydro-1
H-pyrazole
top
Crystal data top
C28H23FN2O2 | F(000) = 920 |
Mr = 438.48 | Dx = 1.312 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 560 reflections |
a = 20.274 (4) Å | θ = 1.6–25.4° |
b = 5.7588 (12) Å | µ = 0.09 mm−1 |
c = 21.241 (4) Å | T = 290 K |
β = 116.438 (4)° | Needle, colourless |
V = 2220.6 (8) Å3 | 0.40 × 0.35 × 0.09 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4445 independent reflections |
Radiation source: fine-focus sealed tube | 2297 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
ϕ and ω scans | θmax = 26.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −25→24 |
Tmin = 0.943, Tmax = 0.992 | k = −7→7 |
16344 measured reflections | l = −26→26 |
Refinement top
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)] = 0.076 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0344P)2] where P = (Fo2 + 2Fc2)/3 |
4445 reflections | (Δ/σ)max < 0.001 |
379 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
Crystal data top
C28H23FN2O2 | V = 2220.6 (8) Å3 |
Mr = 438.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 20.274 (4) Å | µ = 0.09 mm−1 |
b = 5.7588 (12) Å | T = 290 K |
c = 21.241 (4) Å | 0.40 × 0.35 × 0.09 mm |
β = 116.438 (4)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4445 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2297 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 0.992 | Rint = 0.084 |
16344 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.18 | Δρmax = 0.15 e Å−3 |
4445 reflections | Δρmin = −0.14 e Å−3 |
379 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
F1 | 0.44345 (11) | 0.4707 (4) | 0.15403 (11) | 0.0920 (8) | |
O1 | 0.49444 (13) | 0.0567 (4) | 0.12657 (13) | 0.0800 (8) | |
O2 | 1.00036 (13) | 0.0144 (4) | 0.08204 (12) | 0.0692 (7) | |
N1 | 0.77153 (14) | 0.0767 (4) | 0.28946 (14) | 0.0506 (7) | |
N2 | 0.82019 (14) | 0.0002 (5) | 0.26409 (14) | 0.0515 (7) | |
C1 | 0.82552 (17) | 0.1524 (6) | 0.22232 (18) | 0.0491 (9) | |
C2 | 0.7789 (2) | 0.3617 (7) | 0.2148 (3) | 0.0631 (11) | |
C3 | 0.74785 (19) | 0.3177 (6) | 0.2673 (2) | 0.0527 (10) | |
C4 | 0.66598 (17) | 0.3562 (5) | 0.23776 (16) | 0.0464 (9) | |
C5 | 0.6389 (2) | 0.5567 (6) | 0.25252 (19) | 0.0574 (10) | |
C6 | 0.5639 (2) | 0.5979 (8) | 0.2232 (2) | 0.0653 (11) | |
C7 | 0.5169 (2) | 0.4351 (7) | 0.1806 (2) | 0.0603 (10) | |
C8 | 0.5418 (2) | 0.2327 (6) | 0.16490 (17) | 0.0547 (10) | |
C9 | 0.6165 (2) | 0.1948 (6) | 0.19355 (17) | 0.0510 (9) | |
C10 | 0.44082 (19) | 0.1015 (6) | 0.0590 (2) | 0.0608 (10) | |
C11 | 0.4453 (3) | 0.2707 (9) | 0.0169 (3) | 0.0990 (18) | |
C12 | 0.3896 (3) | 0.2967 (10) | −0.0498 (3) | 0.1010 (17) | |
C13 | 0.3310 (3) | 0.1541 (9) | −0.0743 (2) | 0.0799 (13) | |
C14 | 0.3276 (3) | −0.0146 (9) | −0.0322 (3) | 0.0909 (16) | |
C15 | 0.3828 (2) | −0.0449 (7) | 0.0346 (2) | 0.0780 (13) | |
C16 | 0.78237 (18) | −0.0112 (5) | 0.35506 (18) | 0.0467 (9) | |
C17 | 0.7372 (2) | 0.0600 (7) | 0.3844 (2) | 0.0675 (11) | |
C18 | 0.7443 (2) | −0.0366 (8) | 0.4468 (2) | 0.0787 (13) | |
C19 | 0.7970 (2) | −0.1995 (8) | 0.4807 (2) | 0.0716 (12) | |
C20 | 0.8420 (2) | −0.2680 (7) | 0.4522 (2) | 0.0678 (12) | |
C21 | 0.8352 (2) | −0.1758 (6) | 0.3903 (2) | 0.0562 (10) | |
C22 | 0.87143 (17) | 0.1128 (6) | 0.18632 (17) | 0.0485 (9) | |
C23 | 0.9171 (2) | −0.0806 (6) | 0.20101 (19) | 0.0579 (10) | |
C24 | 0.9607 (2) | −0.1188 (7) | 0.16775 (19) | 0.0574 (10) | |
C25 | 0.95985 (18) | 0.0375 (6) | 0.11848 (18) | 0.0531 (9) | |
C26 | 0.9152 (2) | 0.2306 (7) | 0.1032 (2) | 0.0613 (11) | |
C27 | 0.8720 (2) | 0.2672 (7) | 0.1370 (2) | 0.0589 (10) | |
C28 | 1.03949 (19) | −0.1965 (7) | 0.0894 (2) | 0.0834 (13) | |
H2A | 0.8059 (16) | 0.504 (5) | 0.2237 (16) | 0.065 (11)* | |
H2B | 0.7425 (18) | 0.372 (5) | 0.1680 (18) | 0.075 (13)* | |
H3 | 0.7718 (13) | 0.411 (4) | 0.3086 (13) | 0.044 (8)* | |
H5 | 0.6718 (17) | 0.671 (6) | 0.2822 (17) | 0.080 (12)* | |
H6 | 0.5448 (16) | 0.737 (5) | 0.2322 (15) | 0.063 (11)* | |
H9 | 0.6338 (14) | 0.053 (5) | 0.1869 (13) | 0.044 (9)* | |
H11 | 0.480 (2) | 0.371 (7) | 0.033 (2) | 0.100 (16)* | |
H12 | 0.391 (2) | 0.419 (8) | −0.078 (2) | 0.132 (19)* | |
H13 | 0.2925 (19) | 0.176 (6) | −0.1223 (19) | 0.094 (13)* | |
H14 | 0.291 (2) | −0.108 (7) | −0.045 (2) | 0.097 (16)* | |
H15 | 0.3828 (18) | −0.162 (6) | 0.0672 (19) | 0.095 (14)* | |
H17 | 0.6991 (18) | 0.181 (6) | 0.3599 (17) | 0.092 (13)* | |
H18 | 0.7098 (19) | 0.021 (6) | 0.4633 (18) | 0.088 (13)* | |
H19 | 0.8003 (15) | −0.271 (5) | 0.5224 (16) | 0.063 (11)* | |
H20 | 0.8761 (18) | −0.385 (6) | 0.4743 (17) | 0.082 (13)* | |
H21 | 0.8677 (15) | −0.212 (5) | 0.3718 (14) | 0.048 (10)* | |
H23 | 0.9164 (14) | −0.189 (5) | 0.2350 (14) | 0.049 (9)* | |
H24 | 0.9922 (16) | −0.263 (6) | 0.1797 (16) | 0.073 (11)* | |
H26 | 0.9140 (16) | 0.334 (6) | 0.0679 (16) | 0.074 (12)* | |
H27 | 0.8416 (14) | 0.400 (5) | 0.1249 (13) | 0.052 (8)* | |
H28A | 1.0770 | −0.2112 | 0.1369 | 0.125* | |
H28B | 1.0619 | −0.1958 | 0.0580 | 0.125* | |
H28C | 1.0060 | −0.3251 | 0.0783 | 0.125* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F1 | 0.0511 (14) | 0.1177 (19) | 0.1039 (17) | 0.0223 (12) | 0.0316 (13) | 0.0378 (14) |
O1 | 0.0571 (16) | 0.0650 (17) | 0.0776 (19) | −0.0179 (14) | −0.0064 (15) | 0.0244 (14) |
O2 | 0.0629 (17) | 0.0748 (18) | 0.0728 (18) | 0.0035 (14) | 0.0330 (15) | 0.0106 (14) |
N1 | 0.0470 (18) | 0.0454 (17) | 0.0516 (19) | 0.0095 (14) | 0.0149 (15) | 0.0049 (14) |
N2 | 0.0495 (18) | 0.0498 (18) | 0.0465 (18) | 0.0045 (14) | 0.0135 (15) | −0.0006 (15) |
C1 | 0.044 (2) | 0.045 (2) | 0.046 (2) | −0.0033 (17) | 0.0082 (18) | 0.0033 (18) |
C2 | 0.058 (3) | 0.052 (3) | 0.074 (3) | −0.002 (2) | 0.025 (3) | 0.009 (2) |
C4 | 0.045 (2) | 0.043 (2) | 0.044 (2) | 0.0025 (17) | 0.0130 (17) | 0.0052 (17) |
C3 | 0.047 (2) | 0.045 (2) | 0.052 (3) | 0.0002 (18) | 0.0088 (19) | −0.0062 (19) |
C16 | 0.040 (2) | 0.045 (2) | 0.042 (2) | −0.0008 (17) | 0.0059 (17) | −0.0020 (18) |
C5 | 0.059 (3) | 0.046 (2) | 0.059 (3) | 0.005 (2) | 0.019 (2) | −0.003 (2) |
C6 | 0.066 (3) | 0.062 (3) | 0.068 (3) | 0.023 (3) | 0.030 (2) | 0.011 (2) |
C7 | 0.039 (2) | 0.078 (3) | 0.062 (3) | 0.012 (2) | 0.021 (2) | 0.026 (2) |
C8 | 0.045 (2) | 0.052 (2) | 0.052 (2) | −0.002 (2) | 0.0083 (19) | 0.0172 (19) |
C9 | 0.051 (3) | 0.038 (2) | 0.055 (2) | 0.003 (2) | 0.0152 (19) | 0.0032 (18) |
C10 | 0.041 (2) | 0.062 (2) | 0.062 (3) | −0.003 (2) | 0.007 (2) | 0.010 (2) |
C11 | 0.073 (3) | 0.120 (4) | 0.074 (4) | −0.044 (3) | 0.006 (3) | 0.030 (3) |
C12 | 0.091 (4) | 0.119 (4) | 0.062 (3) | −0.028 (3) | 0.007 (3) | 0.025 (3) |
C13 | 0.079 (4) | 0.083 (3) | 0.049 (3) | −0.002 (3) | 0.004 (3) | −0.006 (3) |
C14 | 0.065 (3) | 0.085 (4) | 0.086 (4) | −0.017 (3) | 0.001 (3) | −0.004 (3) |
C15 | 0.063 (3) | 0.072 (3) | 0.073 (3) | −0.016 (2) | 0.006 (3) | 0.013 (3) |
C17 | 0.060 (3) | 0.082 (3) | 0.053 (3) | 0.026 (2) | 0.019 (2) | 0.006 (2) |
C18 | 0.069 (3) | 0.104 (4) | 0.066 (3) | 0.022 (3) | 0.033 (3) | 0.001 (3) |
C19 | 0.074 (3) | 0.084 (3) | 0.055 (3) | 0.009 (3) | 0.026 (3) | 0.009 (3) |
C20 | 0.065 (3) | 0.074 (3) | 0.054 (3) | 0.017 (2) | 0.017 (2) | 0.008 (2) |
C21 | 0.047 (2) | 0.064 (3) | 0.053 (3) | 0.010 (2) | 0.017 (2) | 0.003 (2) |
C22 | 0.042 (2) | 0.045 (2) | 0.045 (2) | −0.0070 (18) | 0.0070 (18) | −0.0004 (18) |
C23 | 0.062 (3) | 0.055 (3) | 0.047 (2) | 0.004 (2) | 0.016 (2) | 0.014 (2) |
C24 | 0.054 (3) | 0.060 (3) | 0.057 (3) | 0.008 (2) | 0.024 (2) | 0.006 (2) |
C25 | 0.043 (2) | 0.060 (3) | 0.049 (2) | −0.009 (2) | 0.0152 (19) | 0.001 (2) |
C26 | 0.061 (3) | 0.056 (3) | 0.062 (3) | −0.002 (2) | 0.023 (2) | 0.012 (2) |
C27 | 0.055 (3) | 0.046 (2) | 0.067 (3) | 0.005 (2) | 0.020 (2) | 0.005 (2) |
C28 | 0.068 (3) | 0.102 (3) | 0.092 (3) | 0.023 (3) | 0.045 (2) | 0.020 (3) |
Geometric parameters (Å, º) top
F1—C7 | 1.352 (3) | C9—H9 | 0.92 (3) |
O1—C8 | 1.384 (4) | C10—C15 | 1.349 (5) |
O1—C10 | 1.386 (4) | C10—C11 | 1.352 (5) |
O2—C25 | 1.363 (4) | C20—C19 | 1.360 (5) |
O2—C28 | 1.421 (4) | C20—H20 | 0.93 (3) |
N1—N2 | 1.390 (3) | C25—C24 | 1.375 (5) |
N1—C16 | 1.405 (4) | C25—C26 | 1.378 (5) |
N1—C3 | 1.476 (4) | C23—C24 | 1.373 (5) |
N2—C1 | 1.286 (4) | C23—H23 | 0.96 (3) |
C22—C27 | 1.378 (4) | C2—H2A | 0.96 (3) |
C22—C23 | 1.392 (4) | C2—H2B | 0.94 (3) |
C22—C1 | 1.462 (4) | C24—H24 | 1.01 (3) |
C1—C2 | 1.496 (5) | C26—H26 | 0.95 (3) |
C16—C21 | 1.376 (4) | C13—C14 | 1.343 (6) |
C16—C17 | 1.380 (5) | C13—C12 | 1.344 (6) |
C4—C5 | 1.374 (4) | C13—H13 | 0.98 (3) |
C4—C9 | 1.384 (4) | C17—C18 | 1.385 (5) |
C4—C3 | 1.507 (4) | C17—H17 | 1.00 (3) |
C8—C7 | 1.370 (5) | C19—C18 | 1.362 (5) |
C8—C9 | 1.374 (4) | C19—H19 | 0.95 (3) |
C3—C2 | 1.526 (5) | C12—C11 | 1.372 (5) |
C3—H3 | 0.96 (2) | C12—H12 | 0.94 (4) |
C21—C20 | 1.367 (5) | C28—H28A | 0.9600 |
C21—H21 | 0.93 (3) | C28—H28B | 0.9600 |
C27—C26 | 1.373 (5) | C28—H28C | 0.9600 |
C27—H27 | 0.94 (2) | C18—H18 | 0.97 (3) |
C6—C7 | 1.356 (5) | C14—C15 | 1.372 (5) |
C6—C5 | 1.382 (5) | C14—H14 | 0.86 (4) |
C6—H6 | 0.94 (3) | C15—H15 | 0.97 (3) |
C5—H5 | 0.95 (3) | C11—H11 | 0.85 (4) |
| | | |
C8—O1—C10 | 119.5 (3) | C6—C7—C8 | 121.6 (4) |
C25—O2—C28 | 118.0 (3) | O2—C25—C24 | 124.2 (4) |
N2—N1—C16 | 116.5 (3) | O2—C25—C26 | 116.4 (4) |
N2—N1—C3 | 111.1 (3) | C24—C25—C26 | 119.5 (4) |
C16—N1—C3 | 122.7 (3) | C24—C23—C22 | 122.0 (4) |
C1—N2—N1 | 110.1 (3) | C24—C23—H23 | 120.9 (16) |
C27—C22—C23 | 117.1 (4) | C22—C23—H23 | 117.2 (16) |
C27—C22—C1 | 121.4 (3) | C1—C2—C3 | 103.6 (3) |
C23—C22—C1 | 121.5 (3) | C1—C2—H2A | 113.0 (18) |
N2—C1—C22 | 121.6 (3) | C3—C2—H2A | 112.6 (19) |
N2—C1—C2 | 112.3 (3) | C1—C2—H2B | 109 (2) |
C22—C1—C2 | 126.1 (3) | C3—C2—H2B | 114 (2) |
C21—C16—C17 | 118.2 (4) | H2A—C2—H2B | 105 (3) |
C21—C16—N1 | 121.8 (3) | C23—C24—C25 | 119.6 (4) |
C17—C16—N1 | 119.9 (3) | C23—C24—H24 | 119.0 (18) |
C5—C4—C9 | 118.4 (3) | C25—C24—H24 | 121.4 (18) |
C5—C4—C3 | 120.5 (3) | C27—C26—C25 | 120.4 (4) |
C9—C4—C3 | 121.0 (3) | C27—C26—H26 | 121.2 (19) |
C7—C8—C9 | 118.8 (3) | C25—C26—H26 | 118.4 (19) |
C7—C8—O1 | 122.1 (3) | C14—C13—C12 | 118.8 (5) |
C9—C8—O1 | 118.9 (3) | C14—C13—H13 | 122 (2) |
N1—C3—C4 | 114.4 (3) | C12—C13—H13 | 119 (2) |
N1—C3—C2 | 102.0 (3) | C16—C17—C18 | 120.4 (4) |
C4—C3—C2 | 114.1 (3) | C16—C17—H17 | 119 (2) |
N1—C3—H3 | 106.1 (15) | C18—C17—H17 | 120 (2) |
C4—C3—H3 | 108.3 (15) | C20—C19—C18 | 119.3 (5) |
C2—C3—H3 | 111.7 (15) | C20—C19—H19 | 120.3 (18) |
C20—C21—C16 | 120.7 (4) | C18—C19—H19 | 120.3 (18) |
C20—C21—H21 | 122.1 (18) | C13—C12—C11 | 120.9 (5) |
C16—C21—H21 | 117.0 (18) | C13—C12—H12 | 119 (3) |
C26—C27—C22 | 121.5 (4) | C11—C12—H12 | 120 (3) |
C26—C27—H27 | 118.2 (16) | O2—C28—H28A | 109.5 |
C22—C27—H27 | 120.3 (16) | O2—C28—H28B | 109.5 |
C7—C6—C5 | 119.2 (4) | H28A—C28—H28B | 109.5 |
C7—C6—H6 | 119.3 (18) | O2—C28—H28C | 109.5 |
C5—C6—H6 | 121.5 (19) | H28A—C28—H28C | 109.5 |
C4—C5—C6 | 120.9 (4) | H28B—C28—H28C | 109.5 |
C4—C5—H5 | 120.0 (19) | C19—C18—C17 | 120.4 (4) |
C6—C5—H5 | 119.1 (19) | C19—C18—H18 | 125 (2) |
C8—C9—C4 | 121.1 (4) | C17—C18—H18 | 115 (2) |
C8—C9—H9 | 119.5 (17) | C13—C14—C15 | 121.4 (5) |
C4—C9—H9 | 119.1 (17) | C13—C14—H14 | 122 (3) |
C15—C10—C11 | 120.1 (4) | C15—C14—H14 | 116 (3) |
C15—C10—O1 | 115.4 (4) | C10—C15—C14 | 119.2 (5) |
C11—C10—O1 | 124.5 (3) | C10—C15—H15 | 116 (2) |
C19—C20—C21 | 121.0 (4) | C14—C15—H15 | 125 (2) |
C19—C20—H20 | 119 (2) | C10—C11—C12 | 119.6 (5) |
C21—C20—H20 | 120 (2) | C10—C11—H11 | 120 (3) |
F1—C7—C6 | 119.4 (4) | C12—C11—H11 | 120 (3) |
F1—C7—C8 | 119.0 (4) | | |
| | | |
C16—N1—N2—C1 | −153.6 (3) | C16—C21—C20—C19 | −0.1 (6) |
C3—N1—N2—C1 | −6.4 (3) | C5—C6—C7—F1 | 177.4 (3) |
N1—N2—C1—C22 | −178.0 (2) | C5—C6—C7—C8 | −1.1 (6) |
N1—N2—C1—C2 | 0.5 (4) | C9—C8—C7—F1 | −178.3 (3) |
C27—C22—C1—N2 | 174.3 (3) | O1—C8—C7—F1 | −4.4 (5) |
C23—C22—C1—N2 | −6.6 (5) | C9—C8—C7—C6 | 0.3 (5) |
C27—C22—C1—C2 | −4.0 (5) | O1—C8—C7—C6 | 174.2 (3) |
C23—C22—C1—C2 | 175.1 (4) | C28—O2—C25—C24 | 7.4 (5) |
N2—N1—C16—C21 | −4.1 (4) | C28—O2—C25—C26 | −171.9 (3) |
C3—N1—C16—C21 | −147.2 (3) | C27—C22—C23—C24 | −0.5 (5) |
N2—N1—C16—C17 | 178.8 (3) | C1—C22—C23—C24 | −179.7 (3) |
C3—N1—C16—C17 | 35.7 (4) | N2—C1—C2—C3 | 5.2 (4) |
C10—O1—C8—C7 | 59.7 (5) | C22—C1—C2—C3 | −176.3 (3) |
C10—O1—C8—C9 | −126.4 (3) | N1—C3—C2—C1 | −8.1 (4) |
N2—N1—C3—C4 | 132.8 (3) | C4—C3—C2—C1 | −132.0 (3) |
C16—N1—C3—C4 | −82.4 (4) | C22—C23—C24—C25 | 0.2 (5) |
N2—N1—C3—C2 | 9.1 (4) | O2—C25—C24—C23 | −179.3 (3) |
C16—N1—C3—C2 | 153.9 (3) | C26—C25—C24—C23 | 0.0 (5) |
C5—C4—C3—N1 | 141.5 (3) | C22—C27—C26—C25 | −0.6 (5) |
C9—C4—C3—N1 | −40.5 (4) | O2—C25—C26—C27 | 179.5 (3) |
C5—C4—C3—C2 | −101.5 (4) | C24—C25—C26—C27 | 0.2 (5) |
C9—C4—C3—C2 | 76.4 (4) | C21—C16—C17—C18 | −1.4 (5) |
C17—C16—C21—C20 | 0.8 (5) | N1—C16—C17—C18 | 175.9 (3) |
N1—C16—C21—C20 | −176.4 (3) | C21—C20—C19—C18 | 0.1 (6) |
C23—C22—C27—C26 | 0.7 (5) | C14—C13—C12—C11 | 0.3 (8) |
C1—C22—C27—C26 | 179.9 (3) | C20—C19—C18—C17 | −0.6 (6) |
C9—C4—C5—C6 | −0.8 (5) | C16—C17—C18—C19 | 1.3 (6) |
C3—C4—C5—C6 | 177.2 (3) | C12—C13—C14—C15 | −0.7 (8) |
C7—C6—C5—C4 | 1.4 (6) | C11—C10—C15—C14 | −2.2 (7) |
C7—C8—C9—C4 | 0.3 (5) | O1—C10—C15—C14 | −179.2 (4) |
O1—C8—C9—C4 | −173.8 (3) | C13—C14—C15—C10 | 1.6 (7) |
C5—C4—C9—C8 | 0.0 (5) | C15—C10—C11—C12 | 1.9 (7) |
C3—C4—C9—C8 | −178.0 (3) | O1—C10—C11—C12 | 178.6 (4) |
C8—O1—C10—C15 | −158.2 (4) | C13—C12—C11—C10 | −1.0 (8) |
C8—O1—C10—C11 | 24.9 (6) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28A···Cg1i | 0.96 | 2.77 | 3.681 (4) | 160 |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C27H21FN2O | C27H20ClFN2O | C28H23FN2O | C28H23FN2O2 |
Mr | 408.46 | 442.90 | 422.48 | 438.48 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 290 | 290 | 290 | 290 |
a, b, c (Å) | 5.9774 (14), 10.484 (3), 16.896 (4) | 17.728 (3), 11.0132 (17), 11.2709 (17) | 17.742 (6), 11.099 (4), 11.187 (4) | 20.274 (4), 5.7588 (12), 21.241 (4) |
β (°) | 90.762 (4) | 95.729 (3) | 95.293 (6) | 116.438 (4) |
V (Å3) | 1058.7 (5) | 2189.6 (6) | 2193.5 (13) | 2220.6 (8) |
Z | 2 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.21 | 0.08 | 0.09 |
Crystal size (mm) | 0.34 × 0.23 × 0.09 | 0.29 × 0.17 × 0.07 | 0.40 × 0.40 × 0.12 | 0.40 × 0.35 × 0.09 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.941, 0.992 | 0.937, 0.986 | 0.921, 0.990 | 0.943, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8402, 2272, 1984 | 17206, 4469, 2393 | 16874, 4427, 2845 | 16344, 4445, 2297 |
Rint | 0.018 | 0.067 | 0.031 | 0.084 |
(sin θ/λ)max (Å−1) | 0.625 | 0.625 | 0.625 | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.087, 1.26 | 0.071, 0.135, 1.06 | 0.050, 0.116, 1.06 | 0.076, 0.135, 1.18 |
No. of reflections | 2272 | 4469 | 4427 | 4445 |
No. of parameters | 364 | 369 | 370 | 379 |
No. of restraints | 1 | 0 | 0 | 0 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.12, −0.12 | 0.23, −0.16 | 0.15, −0.14 | 0.15, −0.14 |
Selected geometric parameters (Å, º) for (I) topN1—N2 | 1.383 (2) | N1—C3 | 1.472 (3) |
N1—C16 | 1.403 (2) | N2—C1 | 1.284 (2) |
| | | |
C27—C22—C1—C2 | 5.3 (3) | C2—C3—C4—C5 | −93.1 (2) |
C3—N1—C16—C17 | −33.3 (3) | N2—C1—C2—C3 | −13.3 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C18—H18···Cg3i | 0.95 (3) | 2.84 (2) | 3.566 (3) | 134 (2) |
C26—H26···Cg4ii | 0.96 (3) | 2.93 (3) | 3.755 (3) | 145 (2) |
C2—H2B···Cg5i | 1.00 (2) | 2.80 (2) | 3.764 (3) | 162 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1. |
Selected geometric parameters (Å, º) for (II) topCl1—C25 | 1.742 (3) | N1—C3 | 1.467 (3) |
N1—N2 | 1.363 (3) | N2—C1 | 1.291 (3) |
N1—C16 | 1.394 (3) | | |
| | | |
Cl1···Cg2i | 3.560 (2) | | |
| | | |
C3—N1—C16—C17 | −9.4 (4) | C27—C22—C1—C2 | 5.2 (4) |
C5—C4—C3—C2 | −92.1 (3) | N2—C1—C2—C3 | −7.4 (4) |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
Selected geometric parameters (Å, º) for (III) topN2—C1 | 1.289 (2) | C16—N1 | 1.388 (2) |
N2—N1 | 1.365 (2) | N1—C3 | 1.468 (2) |
| | | |
C17—C16—N1—C3 | −8.1 (3) | C5—C4—C3—C2 | −90.6 (2) |
C2—C1—C22—C27 | 2.9 (3) | N2—C1—C2—C3 | −7.3 (2) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28C···Cg2i | 0.96 | 3.00 | 3.663 (3) | 128 |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
Selected geometric parameters (Å, º) for (IV) topN1—N2 | 1.390 (3) | N1—C3 | 1.476 (4) |
N1—C16 | 1.405 (4) | N2—C1 | 1.286 (4) |
| | | |
C27—C22—C1—C2 | −4.0 (5) | C5—C4—C3—C2 | −101.5 (4) |
C3—N1—C16—C17 | 35.7 (4) | N2—C1—C2—C3 | 5.2 (4) |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
C28—H28A···Cg1i | 0.96 | 2.77 | 3.681 (4) | 160 |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
Displacement of atom C3 from the least-squares plane formed by the atoms
C1/C2/N1/N2 (Å) for compounds (I)–(IV) topCompound | D |
(I) | -0.342 (2) |
(II) | -0.182 (3) |
(III) | 0.169 (2) |
(IV) | -0.146 (4) |
Dihedral angles between the least-squares planes (°) for compounds (I)–(IV) topCompound | 1/2 | 1/3 | 1/4 | 2/3 | 2/4 | 3/4 |
(I) | 80.3 (1) | 17.3 (1) | 10.5 (1) | 77.8 (2) | 77.8 (2) | 7.4 (4) |
(II) | 75.6 (1) | 4.3 (1) | 7.5 (1) | 78.4 (2) | 71.8 (1) | 7.4 (3) |
(III) | 74.2 (1) | 4.6 (1) | 5.0 (1) | 77.6 (2) | 71.9 (2) | 5.9 (3) |
(IV) | 77.0 (1) | 24.3 (1) | 7.3 (1) | 82.9 (3) | 82.0 (2) | 17.2 (4) |
Langer et al. (2007) | 74.28 (12) | 8.79 (10) | 5.75 (12) | 82.7 (9) | 68.9 (9) | 13.8 (9) |
Notes:
1 is the least-squares plane through atoms C1/C2/C3/N1/N2,
2 is the least-squares plane through atoms C4/C5/C6/C7/C8/C9,
3 is the least-squares plane through atoms C16/C17/C18/C19/C20/C21 and
4 is the least-squares plane through atoms C22/C23/C24/C25/C26/C27. |
Cremer & Pople (1975) puckering parameters for the five-membered
pyrazole ring
(Å, °) for compounds (I)–(IV) topCompound | Q2 | ϕ |
(I) | 0.211 (2) | 143.2 (5) |
(II) | 0.111 (2) | 321.7 (3) |
(III) | 0.105 (2) | 138.8 (9) |
(IV) | 0.088 (4) | 326 (3) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Pyrazolines are an important class of compounds found to possess extensive physiological properties including antibacterial (Nauduri & Reddy, 1998; Azarifar & Shaabanzadeh, 2002), anti-inflammatory (Kuroda et al., 1992; Udupi, Kushnoor & Bhat, 1998; Udupi, Rao & Bhat, 1998), antifungal (Korgaokar et al., 1996), analgesic (Udupi, Kushnoor & Bhat, 1998; Udupi, Rao & Bhat, 1998),antitumour (Chen et al., 1997), antidepressant (Bilgin et al., 1993) and antiprotozoal (Cetin et al., 2003). They also possess fungicidal or herbicidal properties (Takao et al., 1994; Ohvchi & Okada, 1998; Malhotra et al., 1997), and are used as scintillation solutes and antioxidants in lubrication oils (Beher et al., 1967). Previous studies have demonstrated the monoamine oxidase (MAO) inhibitory activities of 1,3,5-triphenyl-2-pyrazolines (Soni et al., 1987; Chimenti et al., 2004). Several recent structural determinations of this class of compounds have also been carried out (Köysal et al., 2005; Langer et al., 2007).
In view of the diverse applications of this class of compounds, we report here the crystal structures of four substituted pyrazoles, namely (5S)-5-(3-fluoro-4-phenoxyphenyl)-1,3-biphenyl-4,5-dihydro-1H-pyrazole, (I), (5S)-3-(4-chlorophenyl)-5-(3-fluoro-4-phenoxyphenyl)-1-phenyl-4,5-dihydro-1H-pyrazole, (II), (5R)-5-(3-fluoro-4-phenoxyphenyl)-3-(4-methylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazole, (III), and (5S)-5-(3-fluoro-4-phenoxyphenyl)-3-(4-methoxyphenyl)-1-phenyl-4,5-dihydro-1H-pyrazole, (IV). The effect of varying molecular substituents on the molecular geometry, the conformational changes and the associated packing features have also been analysed. All four structures have pyrazoline (ring A), 3-fluoro-4-phenoxyphenyl (attached to C5, rings B and C), phenyl (attached to N1, ring D) and substituted phenyl (attached to C3, ring E) moieties in the molecule. The different groups present on ring E are the chloro, methyl and methoxy substituents in compounds (II)–(IV), respectively. All four compounds crystallize with one molecule in the asymmetric unit. In contrast with the unsubstituted pyrazoline, (I), which crystallizes in a noncentrosymmetric space group, the other three compounds crystallize in centrosymmetric space groups. The absolute configuration in (I) was not defined and so is shown to match the configurations shown in the other three structures.
Figs. 1–4 depict the molecular structures of the four pyrazolines with their different substitutions, with the corresponding atom-numbering schemes. In all four compounds, the central ring A exists in an envelope conformation with the chiral atom C3 (crystallographic numbering) forming the flap; deviations from the least-squares planes for (I)–(IV) are given in Table 8. The remaining atoms N1, N2, C1 and C2 of ring A are coplanar, with the out-of-plane distances being -0.0004 (2) and -0.003 (3) Å for atom N2 in (I) and (IV), respectively. The corresponding distances are 0.002 (2) and 0.005 (2) Å for atom C2 in (III) and (IV), respectively. The bond lengths and torsion angles of the five-membered ring (Tables 1, 3, 4 and 6) in all compounds are in agreement with the expected values reported in the literature (Allen et al., 1987; Allen, 2002). The N—N bond lengths of the pyrazoline ring in (I) [1.383 (2) Å] and (IV) [1.390 (3) Å] are similar. In case of (II) [1.363 (3) Å] and (III)[1.365 (2) Å], these are shorter, indicating greater double-bond character due to resonance delocalization between the lone pair of electrons on atom N1 and the C═N double bond of ring A and extending to ring E.
In all four compounds, the 3-fluoro-4-phenoxyphenyl moiety occupies a pseudo-axial position and hence is approximately perpendicular to the mean plane of the pyrazoline ring, the dihedral angle being 80.25 (6)° in (I) (Table 9). This value is comparable with that observed in 3-(4-bromophenyl)-5-(4-dimethylaminophenyl)-1-phenyl-2-pyrazoline (Langer et al., 2007),in which the 4-dimethylaminophenyl moiety makes an angle of 74.3 (1)° with the central pyrazoline ring. Similar geometric characteristics are observed in N-substituted 3,5-diphenyl-2-pyrazoline-1-thiocarboxamides (Köysal et al., 2005), where the methoxyphenyl and methylphenyl moieties make dihedral angles of 89.29 (8) and 80.39 (10)°, respectively. A similar orientation at the C5 atom is also observed in spiro compounds (Bruno et al., 2004), where the isoxazoline ring is connected to the substituted pyrazoline ring with the dihedral angle lying in the range 87.7 (1)–89.0 (1)°. In the isomorphic compounds (II) and (III), the dihedral angles between ring A and rings D and E are similar to those observed in 3-(4-bromophenyl)-5-(4-dimethylaminophenyl)-1-phenyl-2-pyrazoline (Langer et al., 2007), where rings D and E are taken as the phenyl and 4-bromo groups, respectively (Table 9). A ring-puckering analysis (Cremer & Pople, 1975) of the five-membered pyrazoline ring gives the parameters listed in Table 10.
In the absence of strong hydrogen-bond donors in the molecule, the crystal packing is controlled by the involvement of weak C—H···π intermolecular interactions (Nishio et al., 1995; Takahashi et al., 2000; Umezawa et al., 1999). The molecules in (I) are held by three different weak yet directional C—H···π interactions, involving atoms H18 and H2B with rings C and E and forming chains along the crystallographic a axis, coupled with the formation of chains along b axis involving atom H26 and ring D (see Fig. 5 and Table 2).
In the crystal structure of (II), the packing is controlled by a non-covalent C—Cl···π interaction involving the lone pair of electrons on the Cl atom with the antibonding orbitals of the phenyl ring B [C25—Cl1···Cg2 = 137.2 (1)°; Cg2 is the centroid of ring B] (Fig. 6 and Table 3). These interactions are well documented in the literature and have been extensively studied in small molecules and in proteins (Prasanna & Guru Row, 2000; Saraogi et al., 2003) using the Cambridge Structural Database (Version?; Allen, 2002). In (II), these interactions form molecular chains along the crystallographic screw b axis. Replacement of the Cl atom by a methyl group in the isomorphic structure, (III), sees the C—Cl···π interaction being replaced by a C—H···π intermolecular interaction, involving atom H28C of the methyl group and phenyl ring B (Table 5).
In compound (IV), the presence of a methoxy group results in a change in the molecular conformation around the C16—N1 bond, with the torsion angle increasing from -8.1 (3)° in the case of (III) to 35.7 (4)° in (IV). The structure is stabilized by a C—H···π intermolecular interaction, involving atom H28A and the five-membered pyrazoline ring A, forming molecular chains along the screw b axis (Fig. 7 and Table 7).