organic compounds
(7E)-5-Benzyl-7-(2-chlorobenzylidene)-3-(2-chlorophenyl)-2-phenyl-3,3a,4,5,6,7-hexahydro-2H-pyrazolo[4,3-c]pyridine
aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, India, bSchool of Chemistry, University of Hyderabad, Hyderabad 500 046, India, and cBioinformatics Infrastructure Facility, Department of Biotechnology, School of Life Science, University of Hyderabad, Hyderabad 500 046, India
*Correspondence e-mail: ravindranath_rathore@yahoo.com
In the title 2H-pyrazolo[4,3-c]pyridine derivative, C32H27Cl2N3, the dihydropyrazole ring adopts an and the piperidine fused ring a twisted-chair conformation. Two short intramolecular C—H⋯Cl contacts are observed. The crystal packing is characterized by dimeric C—Cl⋯π interactions involving the 5-benzyl ring, with Cl⋯centroid and closest atomic Cl⋯π distances of 3.778 (2) and 3.366 (4) Å, respectively.
Related literature
For the anti-inflammatory activity of 2H-pyrazolo[4,3-c]pyridine derivatives, see Krapcho & Turk (1975). For π-halogen-dimer interactions and their role in host–guest chemistry, see: Noman et al. (2004); Nagaraj et al. (2005).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 and PLATON.
Supporting information
10.1107/S1600536810023317/ng2791sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810023317/ng2791Isup2.hkl
1-benzyl-3, 5-dibenzylidenepiperidin-4-one (0.003 mol) and phenyl hydrazine (0.003 mol) were dissolved in 2-propanol. The reaction mixture was refluxed for 1–2 h on a water bath and tested with TLC at regular intervals for completeness of reaction. Following that, the resulting mixture was cooled and poured into crushed ice. The solid so obtained was separated, washed with water and subjected to
using ethyl acetate and n-hexane. Final yield 89%, m.p. 153–155° C. Suitable single crystals for data collection were grown from ethanol and tetrahydrofuran mixture in 1:1 ratio.H atoms were placed in their stereochemically expected positions and refined with the riding options. The distances with hydrogen atoms are: C(aromatic/sp2)—H = 0.93 Å, C(methylene)—H = 0.97 Å, C(methine)—H = 0.98 Å, and Uiso = 1.2 Ueq(parent atom).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell
CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C32H27Cl2N3 | F(000) = 1096 |
Mr = 524.47 | Dx = 1.307 Mg m−3 |
Monoclinic, P21/c | Melting point: 427(2) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 13.7117 (7) Å | Cell parameters from 2998 reflections |
b = 15.4451 (6) Å | θ = 2.6–29.1° |
c = 13.6896 (9) Å | µ = 0.27 mm−1 |
β = 113.135 (7)° | T = 294 K |
V = 2666.0 (2) Å3 | Plate, colorless |
Z = 4 | 0.36 × 0.26 × 0.22 mm |
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 5436 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 2483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
Detector resolution: 16.3291 pixels mm-1 | θmax = 26.4°, θmin = 2.6° |
ω scan | h = −14→17 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −19→17 |
Tmin = 0.909, Tmax = 0.943 | l = −15→17 |
11774 measured reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.83 | w = 1/[σ2(Fo2) + (0.0389P)2] where P = (Fo2 + 2Fc2)/3 |
5436 reflections | (Δ/σ)max < 0.001 |
334 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C32H27Cl2N3 | V = 2666.0 (2) Å3 |
Mr = 524.47 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.7117 (7) Å | µ = 0.27 mm−1 |
b = 15.4451 (6) Å | T = 294 K |
c = 13.6896 (9) Å | 0.36 × 0.26 × 0.22 mm |
β = 113.135 (7)° |
Oxford Diffraction Xcalibur Eos Gemini diffractometer | 5436 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2483 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.943 | Rint = 0.049 |
11774 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 0.83 | Δρmax = 0.17 e Å−3 |
5436 reflections | Δρmin = −0.23 e Å−3 |
334 parameters |
Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.33.55 (release 05–01-2010 CrysAlis171. NET) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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 | ||
C3 | 0.68994 (17) | 0.48100 (13) | 0.39914 (17) | 0.0384 (6) | |
H3 | 0.7343 | 0.4316 | 0.3979 | 0.046* | |
C3A | 0.60177 (16) | 0.44975 (13) | 0.43353 (18) | 0.0372 (6) | |
H3A | 0.5847 | 0.4958 | 0.4735 | 0.045* | |
C4 | 0.62227 (17) | 0.36610 (14) | 0.49646 (19) | 0.0466 (7) | |
H4A | 0.6489 | 0.3225 | 0.4623 | 0.056* | |
H4B | 0.6753 | 0.3756 | 0.5675 | 0.056* | |
C6 | 0.44171 (18) | 0.31461 (13) | 0.39584 (19) | 0.0483 (7) | |
H6A | 0.3770 | 0.2970 | 0.4031 | 0.058* | |
H6B | 0.4665 | 0.2659 | 0.3671 | 0.058* | |
C7 | 0.41706 (18) | 0.38915 (13) | 0.31845 (19) | 0.0399 (6) | |
C7A | 0.51168 (17) | 0.43857 (14) | 0.32849 (19) | 0.0396 (6) | |
C8 | 0.67598 (17) | 0.52120 (13) | 0.21565 (19) | 0.0372 (6) | |
C9 | 0.78552 (18) | 0.51570 (14) | 0.24683 (19) | 0.0440 (6) | |
H9 | 0.8286 | 0.5028 | 0.3170 | 0.053* | |
C10 | 0.8300 (2) | 0.52943 (15) | 0.1736 (2) | 0.0538 (7) | |
H10 | 0.9033 | 0.5261 | 0.1954 | 0.065* | |
C11 | 0.7685 (2) | 0.54792 (15) | 0.0691 (2) | 0.0565 (7) | |
H11 | 0.7992 | 0.5561 | 0.0202 | 0.068* | |
C12 | 0.6598 (2) | 0.55403 (15) | 0.0385 (2) | 0.0563 (7) | |
H12 | 0.6173 | 0.5671 | −0.0317 | 0.068* | |
C13 | 0.61374 (19) | 0.54113 (14) | 0.1102 (2) | 0.0491 (7) | |
H13 | 0.5406 | 0.5458 | 0.0882 | 0.059* | |
C14 | 0.75983 (17) | 0.55254 (13) | 0.46627 (18) | 0.0371 (6) | |
C15 | 0.86179 (18) | 0.53885 (15) | 0.54037 (19) | 0.0496 (7) | |
C16 | 0.9251 (2) | 0.60585 (19) | 0.5984 (2) | 0.0626 (8) | |
H16 | 0.9935 | 0.5946 | 0.6474 | 0.075* | |
C17 | 0.8869 (2) | 0.68811 (19) | 0.5834 (2) | 0.0629 (8) | |
H17 | 0.9297 | 0.7336 | 0.6211 | 0.075* | |
C18 | 0.7853 (2) | 0.70400 (16) | 0.5126 (2) | 0.0603 (8) | |
H18 | 0.7584 | 0.7601 | 0.5038 | 0.072* | |
C19 | 0.72281 (19) | 0.63714 (15) | 0.4546 (2) | 0.0494 (7) | |
H19 | 0.6542 | 0.6489 | 0.4064 | 0.059* | |
C20 | 0.5425 (2) | 0.25732 (14) | 0.5690 (2) | 0.0565 (7) | |
H20A | 0.5710 | 0.2125 | 0.5381 | 0.068* | |
H20B | 0.4757 | 0.2366 | 0.5688 | 0.068* | |
C21 | 0.6183 (2) | 0.27240 (15) | 0.6818 (2) | 0.0503 (7) | |
C22 | 0.7124 (2) | 0.22752 (18) | 0.7258 (3) | 0.0785 (10) | |
H22 | 0.7295 | 0.1863 | 0.6855 | 0.094* | |
C23 | 0.7823 (3) | 0.2434 (2) | 0.8303 (4) | 0.0997 (14) | |
H23 | 0.8460 | 0.2132 | 0.8594 | 0.120* | |
C24 | 0.7569 (3) | 0.3035 (2) | 0.8899 (3) | 0.0999 (14) | |
H24 | 0.8035 | 0.3141 | 0.9596 | 0.120* | |
C25 | 0.6636 (3) | 0.34798 (18) | 0.8477 (2) | 0.0777 (9) | |
H25 | 0.6462 | 0.3886 | 0.8884 | 0.093* | |
C26 | 0.5955 (2) | 0.33212 (16) | 0.7442 (2) | 0.0601 (8) | |
H26 | 0.5322 | 0.3628 | 0.7156 | 0.072* | |
C27 | 0.32178 (17) | 0.41049 (14) | 0.2455 (2) | 0.0456 (6) | |
H27 | 0.3200 | 0.4618 | 0.2092 | 0.055* | |
C28 | 0.21940 (17) | 0.36564 (15) | 0.21350 (18) | 0.0413 (6) | |
C29 | 0.12329 (18) | 0.41044 (14) | 0.1697 (2) | 0.0454 (6) | |
C30 | 0.02629 (18) | 0.36958 (16) | 0.1313 (2) | 0.0552 (7) | |
H30 | −0.0359 | 0.4017 | 0.1019 | 0.066* | |
C31 | 0.0221 (2) | 0.28080 (17) | 0.1368 (2) | 0.0593 (8) | |
H31 | −0.0429 | 0.2524 | 0.1113 | 0.071* | |
C32 | 0.1142 (2) | 0.23457 (15) | 0.1800 (2) | 0.0570 (8) | |
H32 | 0.1115 | 0.1746 | 0.1845 | 0.068* | |
C33 | 0.21102 (19) | 0.27578 (15) | 0.21688 (19) | 0.0507 (7) | |
H33 | 0.2726 | 0.2428 | 0.2448 | 0.061* | |
N1 | 0.52729 (14) | 0.47054 (11) | 0.24903 (16) | 0.0431 (5) | |
N2 | 0.62818 (14) | 0.51001 (11) | 0.28892 (15) | 0.0403 (5) | |
N5 | 0.52271 (14) | 0.33591 (11) | 0.50228 (15) | 0.0428 (5) | |
Cl1 | 0.91528 (6) | 0.43491 (4) | 0.56217 (7) | 0.0870 (3) | |
Cl2 | 0.12374 (5) | 0.52302 (4) | 0.16351 (7) | 0.0764 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C3 | 0.0318 (12) | 0.0456 (13) | 0.0375 (14) | 0.0018 (11) | 0.0133 (12) | 0.0007 (12) |
C3A | 0.0334 (13) | 0.0410 (14) | 0.0401 (14) | −0.0001 (10) | 0.0174 (12) | −0.0006 (12) |
C4 | 0.0388 (14) | 0.0504 (15) | 0.0494 (16) | −0.0005 (11) | 0.0161 (14) | 0.0036 (13) |
C6 | 0.0433 (15) | 0.0498 (15) | 0.0512 (17) | −0.0036 (12) | 0.0179 (14) | −0.0057 (13) |
C7 | 0.0361 (14) | 0.0483 (14) | 0.0384 (15) | −0.0021 (11) | 0.0179 (13) | −0.0016 (12) |
C7A | 0.0332 (14) | 0.0460 (14) | 0.0429 (16) | 0.0006 (11) | 0.0187 (13) | 0.0023 (12) |
C8 | 0.0335 (14) | 0.0410 (13) | 0.0380 (14) | −0.0044 (11) | 0.0152 (13) | −0.0030 (12) |
C9 | 0.0394 (15) | 0.0571 (15) | 0.0380 (15) | 0.0010 (12) | 0.0180 (13) | −0.0014 (12) |
C10 | 0.0424 (15) | 0.0719 (17) | 0.0555 (18) | −0.0033 (13) | 0.0281 (16) | −0.0068 (15) |
C11 | 0.0635 (19) | 0.0644 (17) | 0.0556 (19) | −0.0102 (14) | 0.0384 (17) | −0.0052 (15) |
C12 | 0.0599 (19) | 0.0697 (17) | 0.0403 (16) | −0.0072 (14) | 0.0208 (16) | 0.0048 (14) |
C13 | 0.0379 (14) | 0.0639 (17) | 0.0440 (16) | −0.0046 (12) | 0.0143 (14) | 0.0015 (14) |
C14 | 0.0351 (13) | 0.0438 (14) | 0.0352 (14) | −0.0031 (11) | 0.0167 (12) | −0.0005 (12) |
C15 | 0.0405 (14) | 0.0607 (16) | 0.0414 (15) | −0.0023 (13) | 0.0095 (14) | −0.0021 (13) |
C16 | 0.0460 (16) | 0.084 (2) | 0.0463 (18) | −0.0079 (16) | 0.0063 (15) | −0.0097 (16) |
C17 | 0.063 (2) | 0.074 (2) | 0.0553 (19) | −0.0245 (16) | 0.0269 (17) | −0.0207 (16) |
C18 | 0.070 (2) | 0.0479 (15) | 0.072 (2) | −0.0065 (14) | 0.0376 (19) | −0.0086 (15) |
C19 | 0.0418 (15) | 0.0516 (16) | 0.0548 (17) | 0.0009 (13) | 0.0187 (14) | −0.0034 (14) |
C20 | 0.0609 (17) | 0.0449 (15) | 0.0643 (19) | −0.0002 (13) | 0.0252 (17) | 0.0074 (14) |
C21 | 0.0457 (16) | 0.0430 (15) | 0.0597 (19) | 0.0010 (13) | 0.0179 (16) | 0.0206 (15) |
C22 | 0.063 (2) | 0.0688 (19) | 0.102 (3) | 0.0148 (16) | 0.031 (2) | 0.037 (2) |
C23 | 0.051 (2) | 0.090 (3) | 0.130 (4) | 0.010 (2) | 0.007 (3) | 0.064 (3) |
C24 | 0.073 (3) | 0.095 (3) | 0.090 (3) | −0.032 (2) | −0.013 (2) | 0.049 (2) |
C25 | 0.083 (2) | 0.077 (2) | 0.057 (2) | −0.0231 (18) | 0.010 (2) | 0.0085 (18) |
C26 | 0.0543 (18) | 0.0576 (17) | 0.0574 (19) | −0.0043 (14) | 0.0100 (17) | 0.0125 (16) |
C27 | 0.0397 (15) | 0.0499 (14) | 0.0486 (17) | −0.0030 (12) | 0.0189 (14) | 0.0001 (13) |
C28 | 0.0369 (14) | 0.0516 (15) | 0.0361 (15) | −0.0030 (12) | 0.0152 (13) | −0.0033 (12) |
C29 | 0.0399 (15) | 0.0487 (14) | 0.0493 (16) | −0.0047 (12) | 0.0193 (14) | 0.0013 (13) |
C30 | 0.0377 (15) | 0.0598 (17) | 0.0600 (19) | 0.0001 (12) | 0.0104 (15) | 0.0037 (15) |
C31 | 0.0448 (16) | 0.0624 (18) | 0.0586 (19) | −0.0144 (14) | 0.0072 (16) | −0.0048 (15) |
C32 | 0.0527 (17) | 0.0477 (15) | 0.0564 (18) | −0.0077 (13) | 0.0060 (16) | −0.0058 (14) |
C33 | 0.0448 (16) | 0.0528 (16) | 0.0465 (16) | −0.0005 (12) | 0.0093 (14) | −0.0077 (13) |
N1 | 0.0299 (11) | 0.0542 (12) | 0.0451 (13) | −0.0051 (9) | 0.0145 (11) | −0.0001 (11) |
N2 | 0.0287 (11) | 0.0570 (12) | 0.0350 (12) | −0.0049 (9) | 0.0124 (10) | 0.0001 (10) |
N5 | 0.0400 (12) | 0.0443 (11) | 0.0434 (12) | −0.0051 (9) | 0.0156 (11) | 0.0044 (10) |
Cl1 | 0.0653 (5) | 0.0766 (5) | 0.0839 (6) | 0.0217 (4) | −0.0087 (5) | 0.0038 (4) |
Cl2 | 0.0549 (4) | 0.0535 (4) | 0.1194 (7) | 0.0007 (3) | 0.0327 (5) | 0.0127 (4) |
C3—N2 | 1.480 (3) | C17—C18 | 1.372 (3) |
C3—C14 | 1.514 (3) | C17—H17 | 0.9300 |
C3—C3A | 1.537 (3) | C18—C19 | 1.377 (3) |
C3—H3 | 0.9800 | C18—H18 | 0.9300 |
C3A—C7A | 1.493 (3) | C19—H19 | 0.9300 |
C3A—C4 | 1.517 (3) | C20—N5 | 1.478 (3) |
C3A—H3A | 0.9800 | C20—C21 | 1.503 (3) |
C4—N5 | 1.474 (3) | C20—H20A | 0.9700 |
C4—H4A | 0.9700 | C20—H20B | 0.9700 |
C4—H4B | 0.9700 | C21—C26 | 1.373 (3) |
C6—N5 | 1.481 (3) | C21—C22 | 1.377 (3) |
C6—C7 | 1.510 (3) | C22—C23 | 1.397 (4) |
C6—H6A | 0.9700 | C22—H22 | 0.9300 |
C6—H6B | 0.9700 | C23—C24 | 1.368 (5) |
C7—C27 | 1.337 (3) | C23—H23 | 0.9300 |
C7—C7A | 1.464 (3) | C24—C25 | 1.364 (4) |
C7A—N1 | 1.287 (3) | C24—H24 | 0.9300 |
C8—C13 | 1.392 (3) | C25—C26 | 1.379 (3) |
C8—C9 | 1.393 (3) | C25—H25 | 0.9300 |
C8—N2 | 1.408 (3) | C26—H26 | 0.9300 |
C9—C10 | 1.379 (3) | C27—C28 | 1.470 (3) |
C9—H9 | 0.9300 | C27—H27 | 0.9300 |
C10—C11 | 1.375 (3) | C28—C33 | 1.395 (3) |
C10—H10 | 0.9300 | C28—C29 | 1.398 (3) |
C11—C12 | 1.383 (3) | C29—C30 | 1.376 (3) |
C11—H11 | 0.9300 | C29—Cl2 | 1.741 (2) |
C12—C13 | 1.375 (3) | C30—C31 | 1.376 (3) |
C12—H12 | 0.9300 | C30—H30 | 0.9300 |
C13—H13 | 0.9300 | C31—C32 | 1.367 (3) |
C14—C15 | 1.383 (3) | C31—H31 | 0.9300 |
C14—C19 | 1.388 (3) | C32—C33 | 1.376 (3) |
C15—C16 | 1.383 (3) | C32—H32 | 0.9300 |
C15—Cl1 | 1.741 (2) | C33—H33 | 0.9300 |
C16—C17 | 1.359 (3) | N1—N2 | 1.411 (2) |
C16—H16 | 0.9300 | ||
N2—C3—C14 | 111.73 (17) | C18—C17—H17 | 120.1 |
N2—C3—C3A | 101.74 (17) | C17—C18—C19 | 120.2 (2) |
C14—C3—C3A | 115.45 (19) | C17—C18—H18 | 119.9 |
N2—C3—H3 | 109.2 | C19—C18—H18 | 119.9 |
C14—C3—H3 | 109.2 | C18—C19—C14 | 121.5 (2) |
C3A—C3—H3 | 109.2 | C18—C19—H19 | 119.2 |
C7A—C3A—C4 | 110.32 (17) | C14—C19—H19 | 119.2 |
C7A—C3A—C3 | 101.19 (18) | N5—C20—C21 | 113.11 (18) |
C4—C3A—C3 | 116.68 (18) | N5—C20—H20A | 109.0 |
C7A—C3A—H3A | 109.4 | C21—C20—H20A | 109.0 |
C4—C3A—H3A | 109.4 | N5—C20—H20B | 109.0 |
C3—C3A—H3A | 109.4 | C21—C20—H20B | 109.0 |
N5—C4—C3A | 109.35 (17) | H20A—C20—H20B | 107.8 |
N5—C4—H4A | 109.8 | C26—C21—C22 | 118.0 (3) |
C3A—C4—H4A | 109.8 | C26—C21—C20 | 120.6 (2) |
N5—C4—H4B | 109.8 | C22—C21—C20 | 121.5 (3) |
C3A—C4—H4B | 109.8 | C21—C22—C23 | 120.5 (3) |
H4A—C4—H4B | 108.3 | C21—C22—H22 | 119.8 |
N5—C6—C7 | 113.30 (17) | C23—C22—H22 | 119.8 |
N5—C6—H6A | 108.9 | C24—C23—C22 | 119.8 (3) |
C7—C6—H6A | 108.9 | C24—C23—H23 | 120.1 |
N5—C6—H6B | 108.9 | C22—C23—H23 | 120.1 |
C7—C6—H6B | 108.9 | C25—C24—C23 | 120.3 (3) |
H6A—C6—H6B | 107.7 | C25—C24—H24 | 119.8 |
C27—C7—C7A | 120.7 (2) | C23—C24—H24 | 119.8 |
C27—C7—C6 | 126.6 (2) | C24—C25—C26 | 119.3 (3) |
C7A—C7—C6 | 112.69 (19) | C24—C25—H25 | 120.4 |
N1—C7A—C7 | 123.8 (2) | C26—C25—H25 | 120.4 |
N1—C7A—C3A | 114.9 (2) | C21—C26—C25 | 122.1 (3) |
C7—C7A—C3A | 121.2 (2) | C21—C26—H26 | 119.0 |
C13—C8—C9 | 118.6 (2) | C25—C26—H26 | 119.0 |
C13—C8—N2 | 119.9 (2) | C7—C27—C28 | 130.2 (2) |
C9—C8—N2 | 121.5 (2) | C7—C27—H27 | 114.9 |
C10—C9—C8 | 120.0 (2) | C28—C27—H27 | 114.9 |
C10—C9—H9 | 120.0 | C33—C28—C29 | 115.5 (2) |
C8—C9—H9 | 120.0 | C33—C28—C27 | 122.7 (2) |
C11—C10—C9 | 121.4 (2) | C29—C28—C27 | 121.6 (2) |
C11—C10—H10 | 119.3 | C30—C29—C28 | 122.9 (2) |
C9—C10—H10 | 119.3 | C30—C29—Cl2 | 117.43 (18) |
C10—C11—C12 | 118.5 (3) | C28—C29—Cl2 | 119.63 (17) |
C10—C11—H11 | 120.7 | C31—C30—C29 | 119.4 (2) |
C12—C11—H11 | 120.7 | C31—C30—H30 | 120.3 |
C13—C12—C11 | 121.1 (3) | C29—C30—H30 | 120.3 |
C13—C12—H12 | 119.5 | C32—C31—C30 | 119.6 (2) |
C11—C12—H12 | 119.5 | C32—C31—H31 | 120.2 |
C12—C13—C8 | 120.4 (2) | C30—C31—H31 | 120.2 |
C12—C13—H13 | 119.8 | C31—C32—C33 | 120.7 (2) |
C8—C13—H13 | 119.8 | C31—C32—H32 | 119.6 |
C15—C14—C19 | 116.5 (2) | C33—C32—H32 | 119.6 |
C15—C14—C3 | 123.4 (2) | C32—C33—C28 | 121.9 (2) |
C19—C14—C3 | 120.10 (19) | C32—C33—H33 | 119.1 |
C16—C15—C14 | 122.2 (2) | C28—C33—H33 | 119.1 |
C16—C15—Cl1 | 117.7 (2) | C7A—N1—N2 | 107.59 (19) |
C14—C15—Cl1 | 120.18 (18) | C8—N2—N1 | 115.95 (18) |
C17—C16—C15 | 119.7 (2) | C8—N2—C3 | 121.56 (17) |
C17—C16—H16 | 120.2 | N1—N2—C3 | 110.18 (17) |
C15—C16—H16 | 120.2 | C4—N5—C20 | 110.11 (18) |
C16—C17—C18 | 119.9 (2) | C4—N5—C6 | 111.69 (18) |
C16—C17—H17 | 120.1 | C20—N5—C6 | 108.06 (17) |
N2—C3—C3A—C7A | 18.3 (2) | C26—C21—C22—C23 | −0.6 (4) |
C14—C3—C3A—C7A | 139.43 (18) | C20—C21—C22—C23 | 179.1 (2) |
N2—C3—C3A—C4 | 137.96 (19) | C21—C22—C23—C24 | 0.5 (5) |
C14—C3—C3A—C4 | −100.9 (2) | C22—C23—C24—C25 | 0.0 (5) |
C7A—C3A—C4—N5 | −52.9 (2) | C23—C24—C25—C26 | −0.4 (5) |
C3—C3A—C4—N5 | −167.63 (18) | C22—C21—C26—C25 | 0.2 (4) |
N5—C6—C7—C27 | −141.8 (2) | C20—C21—C26—C25 | −179.5 (2) |
N5—C6—C7—C7A | 39.4 (3) | C24—C25—C26—C21 | 0.3 (4) |
C27—C7—C7A—N1 | −36.8 (3) | C7A—C7—C27—C28 | 172.6 (2) |
C6—C7—C7A—N1 | 142.1 (2) | C6—C7—C27—C28 | −6.1 (4) |
C27—C7—C7A—C3A | 147.8 (2) | C7—C27—C28—C33 | −31.2 (4) |
C6—C7—C7A—C3A | −33.3 (3) | C7—C27—C28—C29 | 153.8 (3) |
C4—C3A—C7A—N1 | −135.4 (2) | C33—C28—C29—C30 | −0.6 (4) |
C3—C3A—C7A—N1 | −11.3 (2) | C27—C28—C29—C30 | 174.7 (2) |
C4—C3A—C7A—C7 | 40.4 (3) | C33—C28—C29—Cl2 | 178.85 (18) |
C3—C3A—C7A—C7 | 164.53 (19) | C27—C28—C29—Cl2 | −5.9 (3) |
C13—C8—C9—C10 | −0.4 (3) | C28—C29—C30—C31 | 0.9 (4) |
N2—C8—C9—C10 | −178.2 (2) | Cl2—C29—C30—C31 | −178.6 (2) |
C8—C9—C10—C11 | −0.6 (4) | C29—C30—C31—C32 | −0.2 (4) |
C9—C10—C11—C12 | 1.1 (4) | C30—C31—C32—C33 | −0.8 (4) |
C10—C11—C12—C13 | −0.6 (4) | C31—C32—C33—C28 | 1.1 (4) |
C11—C12—C13—C8 | −0.3 (4) | C29—C28—C33—C32 | −0.4 (4) |
C9—C8—C13—C12 | 0.8 (3) | C27—C28—C33—C32 | −175.6 (2) |
N2—C8—C13—C12 | 178.6 (2) | C7—C7A—N1—N2 | −177.40 (19) |
N2—C3—C14—C15 | −140.5 (2) | C3A—C7A—N1—N2 | −1.7 (3) |
C3A—C3—C14—C15 | 103.9 (3) | C13—C8—N2—N1 | 35.8 (3) |
N2—C3—C14—C19 | 39.0 (3) | C9—C8—N2—N1 | −146.42 (19) |
C3A—C3—C14—C19 | −76.6 (3) | C13—C8—N2—C3 | 174.33 (19) |
C19—C14—C15—C16 | −1.5 (4) | C9—C8—N2—C3 | −7.9 (3) |
C3—C14—C15—C16 | 178.0 (2) | C7A—N1—N2—C8 | 158.2 (2) |
C19—C14—C15—Cl1 | 179.33 (19) | C7A—N1—N2—C3 | 15.1 (2) |
C3—C14—C15—Cl1 | −1.2 (3) | C14—C3—N2—C8 | 74.5 (2) |
C14—C15—C16—C17 | 0.3 (4) | C3A—C3—N2—C8 | −161.78 (18) |
Cl1—C15—C16—C17 | 179.5 (2) | C14—C3—N2—N1 | −144.89 (18) |
C15—C16—C17—C18 | 1.3 (4) | C3A—C3—N2—N1 | −21.2 (2) |
C16—C17—C18—C19 | −1.8 (4) | C3A—C4—N5—C20 | −176.51 (18) |
C17—C18—C19—C14 | 0.6 (4) | C3A—C4—N5—C6 | 63.4 (2) |
C15—C14—C19—C18 | 1.1 (4) | C21—C20—N5—C4 | 61.7 (3) |
C3—C14—C19—C18 | −178.5 (2) | C21—C20—N5—C6 | −176.1 (2) |
N5—C20—C21—C26 | 59.8 (3) | C7—C6—N5—C4 | −56.7 (2) |
N5—C20—C21—C22 | −119.9 (2) | C7—C6—N5—C20 | −178.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl1 | 0.98 | 2.61 | 3.101 (2) | 111 |
C27—H27···Cl2 | 0.93 | 2.68 | 3.043 (3) | 104 |
Experimental details
Crystal data | |
Chemical formula | C32H27Cl2N3 |
Mr | 524.47 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 13.7117 (7), 15.4451 (6), 13.6896 (9) |
β (°) | 113.135 (7) |
V (Å3) | 2666.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.36 × 0.26 × 0.22 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Eos Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.909, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11774, 5436, 2483 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.098, 0.83 |
No. of reflections | 5436 |
No. of parameters | 334 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.23 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···Cl1 | 0.98 | 2.61 | 3.101 (2) | 111 |
C27—H27···Cl2 | 0.93 | 2.68 | 3.043 (3) | 104 |
Acknowledgements
The Bioinformatics Infrastructure Facility and the Single Crystal X-ray Diffractometer Facility at the University of Hyderabad are gratefully acknowledged are gratefully acknowledged for computation and data collection. RSR thanks the CSIR, New Delhi, for support under the scientist's pool scheme and NSK thanks the CSIR, New Delhi, for a Senior Research Fellowship.
References
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Krapcho, J. & Turk, C. F. (1975). US Patent No. 3 923 816. Google Scholar
Nagaraj, B., Narasimhamurthy, T., Yathirajan, H. S., Nagaraja, P., Narasegowda, R. S. & Rathore, R. S. (2005). Acta Cryst. C61, o177–o180. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Noman, A., Rehman, M. M., Bishop, R., Craig, D. C. & Scudder, M. L. (2004). J. Org. Biomol. Chem. 2, 175–182. Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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.
Derivatives of 2H-pyrazolo[4,3-c]pyridine have been tested for anti-inflammatory activity (Krapcho & Turk, 1975). A search in Cambridge Structural Database (version 5.31) for such compounds retrieved zero hits. With a purpose to study hitherto unexplored structures of these compounds, we here report the synthesis and structural investigations on, 5-benzyl-(7E)-7-(2-chlorobenzylidene)-3-(2-chlorophenyl)-2-phenyl- 3,3a,4,5,6,7-hexahydro-2H-pyrazolo[4,3-c]pyridine, (I).
The structure of (I) with adopted atomic numbering scheme is shown in Fig 1. (I) is a racemic mixture. In the reported model, the stereogenic centers C3 and C3A possess R-configurations. The five-membered dihydropyrazole ring (N1/N2/C3/C3A/C7A) adopt an envelope conformation with atom C3 at the flap of the envelope (Ring puckering parameters are: q2 = 0.204 (2) Å, ϕ2 = 248.3 (6)°). The adjacent 6-membered piperidine ring (C3A/C4/N5/C6/C7/C7A) assumes a chair conformation which is substantially twisted from ideal geometry. The puckering parameters are as follows: q2 = 0.189 (2) Å, q3 = -0.468 (2) Å, θ = 158.0 (2)°, ϕ = 209.5 (8)°, and total puckering amplitude, Q = 0.505 (2) Å.
Two short intra-molecular contacts C3—H3···Cl1 and C27—H27···Cl2 were observed (Table 1). Intermolecular C—Halogen···π contact stabilizes the dimeric units in (I) (Fig 2). A dimer is formed by C29—Cl2···Cg5i [symmetry code (i): 1 - x, 1 - y, 1 - z]. The Cl2..Cg5 distance and C29—Cl2···Cg5 angle are 3.778 (2)Å and 141.2 (1)° respectively, whereas the minimum atomic distance in Cl2···π is 3.366 (4) Å. Cg5 is the centroid of (C21–C26) ring. The C—Halogen···π dimeric interactions [also referred as PHD; π-halogen-dimer interactions (Noman et al. 2004)] have been shown recently, to play an important role in host–guest chemistry (Nagaraj et al., 2005; references therein).