organic compounds
A second monoclinic polymorph of 4-[(E)-(4-benzyloxybenzylidene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one
aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, and cDepartment of Chemistry, P.A. College of Engineering, Nadupadavu, Mangalore 574 153, India
*Correspondence e-mail: rkvk.paper11@gmail.com
In the title compound, C25H23N3O2, the central benzene ring makes dihedral angles of 77.14 (8) and 87.7 (2)° with the terminal benzene rings and an angle of 1.9 (1)° with the pyrazolone ring. The benzene ring and the N atom of the pyrazole ring bearing the phenyl substituent are disordered over two sets of sites with an occupancy ratio of 0.71 (2):0.29 (2). The N atoms of the pyrazole ring have a pyramidal environment, the sums of the valence angles around them being 354.6 (3) and 352.0 (6)/349.5 (15)°. In the crystal, molecules are packed into layers parallel to the ac plane. The other monoclinic polymorphic form was reported recently [Dutkiewicz et al. (2012). Acta Cryst. E68, o1324].
Related literature
For potential applications of et al. (2006); Shi et al.(2007); Satyanarayana et al. (2008). For related structures, see: Liu et al.(2008); Hu, (2006). For the other monoclinic polymorph, see Dutkiewicz et al., (2012).
see: PatoleExperimental
Crystal data
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); 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, 2012); software used to prepare material for publication: PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812050891/gk2544sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050891/gk2544Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050891/gk2544Isup3.cml
The title compound was synthesized by adding 4-benzyloxybenzaldehyde (0.212 g, 1 mmol) to the solution of 4-aminoantipyrine (0.203 g, 1 mmol) in methanol (30 ml) containing few drops of conc. sulfuric acid. The mixture was refluxed for 3hrs and left stirring overnight at room temperature. The resultant solid obtained was then filtered. Yellow needle-shaped single crystals suitable for X-ray
were formed after slow evaporation of dichloromethane at room temperature (431–433 K).Atom N2 and the benzene ring (C8—C13) are disordered over two positions with an occupancy ratio of 0.71 (2):0.29 (2). In the
process restraints were imposed on C—C [1.38 (1) Å] distances of the disordered molecular fragments and the displacement parameters. All H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).Schiff bases are widely used organic compounds and structurally it is a nitrogen analogue of an aldehyde or ketone in which the carbonyl group has been replaced by an imine or azomethine group. They are used as pigments and dyes, catalysts, intermediates in organic synthesis, and polymer stabilisers.
have also been shown to exhibit a broad range of biological activities including antimicrobial (Shi et al., 2007; Satyanarayana et al., 2008; antimycobacterial (Patole et al., 2006). In view of the pharmacological importance of schiff base derivatives, the title compound (I) is prepared and its is reported.All bond lengths and angles are normal and correspond to those observed in related structures(Liu et al., 2008; Hu, 2006; Dutkiewicz et al., 2012). The central benzene ring makes dihedral angles of 77.14 (8), 87.7 (2) and 87.1 (6)° with the terminal benzene rings (C24—C29),(C8—C13A)and (C8—C13B) respectively while 1.9 (1)(N2A)/ 1.7 (1)°(N2B) with the pyrazolone ring. The benzene ring (C8—C13) and atom N2 are disordered over two positions with an occupancy ratio of 0.71 (2):0.29 (2). The N atoms of the pyrazole ring have a pyramidal environment, the sums of the valence angles around them being 354.6 (3)(N1) and 352.0 (6)(N2A) / 349.5 (15)(N2B) °. The sums of the valence angles around N-atoms of the pyrazole ring in the polymorph of this compound are 353.5 for N1 and 347.3 ° for N2 (Dutkiewicz et al., 2012). Molecules are packed into layers parallel to the ac-plane (Fig.2).
For potential applications of
see: Patole et al. (2006); Shi et al.(2007); Satyanarayana et al. (2008). For related structures, see: Liu et al.(2008); Hu, (2006). For the other monoclinic polymorph, see Dutkiewicz et al., (2012).Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction ,2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).C25H23N3O2 | F(000) = 840 |
Mr = 397.46 | Dx = 1.237 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7057 reflections |
a = 13.0079 (5) Å | θ = 3.6–29.0° |
b = 9.9079 (4) Å | µ = 0.08 mm−1 |
c = 17.0469 (9) Å | T = 293 K |
β = 103.674 (4)° | Plate, white |
V = 2134.75 (16) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 4 |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 4162 independent reflections |
Radiation source: fine-focus sealed tube | 2399 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 16.1049 pixels mm-1 | θmax = 26.0°, θmin = 3.6° |
ω scans | h = −15→16 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −12→12 |
Tmin = 0.920, Tmax = 1.000 | l = −21→21 |
19519 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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.057P)2 + 0.3022P] where P = (Fo2 + 2Fc2)/3 |
4162 reflections | (Δ/σ)max = 0.001 |
292 parameters | Δρmax = 0.21 e Å−3 |
12 restraints | Δρmin = −0.15 e Å−3 |
C25H23N3O2 | V = 2134.75 (16) Å3 |
Mr = 397.46 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.0079 (5) Å | µ = 0.08 mm−1 |
b = 9.9079 (4) Å | T = 293 K |
c = 17.0469 (9) Å | 0.3 × 0.2 × 0.2 mm |
β = 103.674 (4)° |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 4162 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 2399 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 1.000 | Rint = 0.047 |
19519 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 12 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.21 e Å−3 |
4162 reflections | Δρmin = −0.15 e Å−3 |
292 parameters |
Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) 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 | Occ. (<1) | |
N1 | 0.74159 (14) | −0.03151 (19) | −0.14892 (13) | 0.0628 (5) | |
N2A | 0.8373 (6) | 0.0248 (9) | −0.1606 (6) | 0.0613 (17) | 0.707 (17) |
C9A | 0.9286 (11) | −0.0547 (11) | −0.2496 (4) | 0.0742 (16) | 0.707 (17) |
H9A | 0.8866 | 0.0057 | −0.2850 | 0.089* | 0.707 (17) |
C10A | 1.0017 (8) | −0.1332 (10) | −0.2750 (6) | 0.091 (2) | 0.707 (17) |
H10A | 1.0089 | −0.1260 | −0.3278 | 0.109* | 0.707 (17) |
C11A | 1.0640 (6) | −0.2218 (8) | −0.2229 (7) | 0.083 (3) | 0.707 (17) |
H11A | 1.1114 | −0.2774 | −0.2408 | 0.100* | 0.707 (17) |
C12A | 1.0560 (6) | −0.2277 (9) | −0.1448 (6) | 0.092 (3) | 0.707 (17) |
H12A | 1.1003 | −0.2849 | −0.1087 | 0.110* | 0.707 (17) |
C13A | 0.9831 (12) | −0.1502 (15) | −0.1191 (5) | 0.080 (2) | 0.707 (17) |
H13A | 0.9779 | −0.1548 | −0.0657 | 0.096* | 0.707 (17) |
N2B | 0.8462 (17) | 0.001 (2) | −0.1335 (11) | 0.0613 (17) | 0.293 (17) |
C9B | 0.940 (3) | −0.089 (3) | −0.2461 (10) | 0.0742 (16) | 0.293 (17) |
H9B | 0.8994 | −0.0473 | −0.2919 | 0.089* | 0.293 (17) |
C10B | 1.021 (2) | −0.173 (3) | −0.2531 (15) | 0.091 (2) | 0.293 (17) |
H10B | 1.0390 | −0.1891 | −0.3021 | 0.109* | 0.293 (17) |
C11B | 1.074 (2) | −0.233 (3) | −0.1820 (14) | 0.083 (3) | 0.293 (17) |
H11B | 1.1310 | −0.2881 | −0.1851 | 0.100* | 0.293 (17) |
C12B | 1.054 (2) | −0.220 (3) | −0.1069 (13) | 0.092 (3) | 0.293 (17) |
H12B | 1.0900 | −0.2679 | −0.0622 | 0.110* | 0.293 (17) |
C13B | 0.974 (3) | −0.129 (4) | −0.1031 (11) | 0.080 (2) | 0.293 (17) |
H13B | 0.9589 | −0.1105 | −0.0537 | 0.096* | 0.293 (17) |
O3 | 0.93832 (13) | 0.21006 (18) | −0.11143 (13) | 0.0865 (6) | |
C3 | 0.85441 (18) | 0.1476 (2) | −0.12022 (15) | 0.0626 (7) | |
C4 | 0.75575 (16) | 0.1790 (2) | −0.10095 (13) | 0.0503 (5) | |
C5 | 0.69005 (16) | 0.0687 (2) | −0.11997 (14) | 0.0530 (6) | |
C6 | 0.6960 (2) | −0.1478 (3) | −0.1940 (2) | 0.1129 (13) | |
H6A | 0.6383 | −0.1805 | −0.1731 | 0.169* | |
H6B | 0.7487 | −0.2171 | −0.1893 | 0.169* | |
H6C | 0.6705 | −0.1238 | −0.2498 | 0.169* | |
C7 | 0.57995 (17) | 0.0514 (3) | −0.11114 (17) | 0.0737 (8) | |
H7A | 0.5331 | 0.0412 | −0.1635 | 0.111* | |
H7B | 0.5596 | 0.1294 | −0.0849 | 0.111* | |
H7C | 0.5760 | −0.0274 | −0.0793 | 0.111* | |
C8 | 0.91815 (17) | −0.0660 (2) | −0.17219 (15) | 0.0558 (6) | |
N14 | 0.72512 (13) | 0.29631 (18) | −0.06847 (11) | 0.0517 (5) | |
C15 | 0.78748 (17) | 0.3983 (2) | −0.05482 (13) | 0.0542 (6) | |
H15 | 0.8538 | 0.3918 | −0.0661 | 0.065* | |
C16 | 0.75724 (16) | 0.5243 (2) | −0.02202 (13) | 0.0496 (5) | |
C17 | 0.65779 (17) | 0.5437 (2) | −0.00752 (14) | 0.0601 (6) | |
H17 | 0.6080 | 0.4748 | −0.0196 | 0.072* | |
C18 | 0.63120 (17) | 0.6619 (2) | 0.02411 (15) | 0.0619 (6) | |
H18 | 0.5636 | 0.6731 | 0.0325 | 0.074* | |
C19 | 0.70499 (17) | 0.7655 (2) | 0.04375 (13) | 0.0506 (5) | |
C20 | 0.80368 (18) | 0.7488 (2) | 0.02936 (14) | 0.0573 (6) | |
H20 | 0.8534 | 0.8178 | 0.0415 | 0.069* | |
C21 | 0.82894 (18) | 0.6293 (2) | −0.00321 (15) | 0.0588 (6) | |
H21 | 0.8960 | 0.6191 | −0.0128 | 0.071* | |
O22 | 0.67048 (11) | 0.87620 (16) | 0.07728 (10) | 0.0647 (5) | |
C23 | 0.74356 (17) | 0.9854 (2) | 0.10298 (15) | 0.0583 (6) | |
H23A | 0.7578 | 1.0319 | 0.0566 | 0.070* | |
H23B | 0.8098 | 0.9516 | 0.1359 | 0.070* | |
C24 | 0.69226 (16) | 1.0782 (2) | 0.15077 (14) | 0.0522 (6) | |
C25 | 0.64419 (18) | 1.1960 (2) | 0.11844 (15) | 0.0642 (7) | |
H25 | 0.6458 | 1.2212 | 0.0662 | 0.077* | |
C26 | 0.5933 (2) | 1.2772 (3) | 0.16364 (19) | 0.0761 (8) | |
H26 | 0.5612 | 1.3570 | 0.1417 | 0.091* | |
C27 | 0.5903 (2) | 1.2403 (3) | 0.2406 (2) | 0.0822 (9) | |
H27 | 0.5551 | 1.2941 | 0.2705 | 0.099* | |
C28 | 0.6390 (2) | 1.1244 (3) | 0.27318 (17) | 0.0788 (8) | |
H28 | 0.6375 | 1.0996 | 0.3255 | 0.095* | |
C29 | 0.68990 (19) | 1.0448 (3) | 0.22883 (15) | 0.0652 (7) | |
H29 | 0.7236 | 0.9666 | 0.2518 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0479 (11) | 0.0503 (12) | 0.0897 (15) | −0.0096 (9) | 0.0154 (9) | −0.0168 (11) |
N2A | 0.0523 (19) | 0.052 (3) | 0.085 (5) | −0.0073 (19) | 0.026 (3) | −0.016 (3) |
C9A | 0.095 (4) | 0.053 (6) | 0.074 (2) | 0.014 (4) | 0.018 (2) | −0.011 (2) |
C10A | 0.120 (5) | 0.069 (6) | 0.094 (5) | 0.005 (4) | 0.047 (4) | −0.019 (3) |
C11A | 0.071 (3) | 0.061 (3) | 0.120 (8) | 0.001 (2) | 0.027 (5) | −0.029 (5) |
C12A | 0.082 (3) | 0.072 (3) | 0.111 (8) | 0.010 (2) | 0.004 (6) | 0.021 (7) |
C13A | 0.081 (3) | 0.076 (6) | 0.085 (3) | −0.003 (2) | 0.023 (3) | 0.012 (4) |
N2B | 0.0523 (19) | 0.052 (3) | 0.085 (5) | −0.0073 (19) | 0.026 (3) | −0.016 (3) |
C9B | 0.095 (4) | 0.053 (6) | 0.074 (2) | 0.014 (4) | 0.018 (2) | −0.011 (2) |
C10B | 0.120 (5) | 0.069 (6) | 0.094 (5) | 0.005 (4) | 0.047 (4) | −0.019 (3) |
C11B | 0.071 (3) | 0.061 (3) | 0.120 (8) | 0.001 (2) | 0.027 (5) | −0.029 (5) |
C12B | 0.082 (3) | 0.072 (3) | 0.111 (8) | 0.010 (2) | 0.004 (6) | 0.021 (7) |
C13B | 0.081 (3) | 0.076 (6) | 0.085 (3) | −0.003 (2) | 0.023 (3) | 0.012 (4) |
O3 | 0.0631 (10) | 0.0667 (12) | 0.1405 (17) | −0.0236 (9) | 0.0459 (11) | −0.0353 (12) |
C3 | 0.0549 (14) | 0.0537 (15) | 0.0823 (17) | −0.0109 (12) | 0.0225 (12) | −0.0157 (13) |
C4 | 0.0473 (12) | 0.0464 (13) | 0.0565 (13) | −0.0036 (10) | 0.0109 (10) | −0.0041 (11) |
C5 | 0.0475 (12) | 0.0478 (13) | 0.0614 (14) | −0.0043 (10) | 0.0087 (10) | −0.0041 (11) |
C6 | 0.0795 (19) | 0.093 (2) | 0.169 (3) | −0.0320 (17) | 0.036 (2) | −0.077 (2) |
C7 | 0.0510 (14) | 0.0625 (17) | 0.107 (2) | −0.0074 (12) | 0.0179 (13) | −0.0091 (15) |
C8 | 0.0524 (13) | 0.0467 (13) | 0.0708 (16) | −0.0081 (11) | 0.0198 (11) | −0.0080 (12) |
N14 | 0.0528 (10) | 0.0448 (11) | 0.0569 (11) | −0.0055 (9) | 0.0118 (8) | −0.0037 (9) |
C15 | 0.0517 (12) | 0.0514 (14) | 0.0620 (15) | −0.0035 (11) | 0.0182 (10) | −0.0038 (11) |
C16 | 0.0503 (12) | 0.0436 (12) | 0.0553 (13) | −0.0017 (10) | 0.0133 (10) | −0.0004 (10) |
C17 | 0.0502 (13) | 0.0492 (14) | 0.0800 (17) | −0.0103 (11) | 0.0136 (11) | −0.0114 (12) |
C18 | 0.0448 (12) | 0.0567 (15) | 0.0838 (17) | −0.0063 (11) | 0.0144 (11) | −0.0148 (13) |
C19 | 0.0514 (12) | 0.0436 (13) | 0.0556 (13) | −0.0005 (10) | 0.0104 (10) | −0.0030 (10) |
C20 | 0.0576 (14) | 0.0453 (13) | 0.0713 (15) | −0.0138 (11) | 0.0196 (11) | −0.0047 (11) |
C21 | 0.0562 (13) | 0.0502 (14) | 0.0758 (16) | −0.0067 (11) | 0.0269 (11) | −0.0055 (12) |
O22 | 0.0539 (9) | 0.0510 (10) | 0.0889 (12) | −0.0065 (7) | 0.0160 (8) | −0.0187 (9) |
C23 | 0.0579 (13) | 0.0472 (13) | 0.0692 (15) | −0.0103 (11) | 0.0139 (11) | −0.0051 (12) |
C24 | 0.0509 (12) | 0.0420 (13) | 0.0609 (15) | −0.0090 (10) | 0.0078 (10) | −0.0097 (11) |
C25 | 0.0730 (16) | 0.0533 (15) | 0.0640 (15) | 0.0010 (13) | 0.0114 (12) | −0.0037 (13) |
C26 | 0.0736 (17) | 0.0580 (17) | 0.092 (2) | 0.0069 (13) | 0.0099 (15) | −0.0164 (16) |
C27 | 0.0699 (17) | 0.086 (2) | 0.093 (2) | −0.0173 (16) | 0.0251 (16) | −0.0460 (19) |
C28 | 0.094 (2) | 0.082 (2) | 0.0629 (17) | −0.0235 (18) | 0.0235 (15) | −0.0181 (16) |
C29 | 0.0727 (15) | 0.0585 (16) | 0.0612 (16) | −0.0133 (13) | 0.0093 (12) | −0.0018 (13) |
N1—C5 | 1.355 (3) | C6—H6A | 0.9600 |
N1—N2B | 1.36 (2) | C6—H6B | 0.9600 |
N1—N2A | 1.421 (8) | C6—H6C | 0.9600 |
N1—C6 | 1.434 (3) | C7—H7A | 0.9600 |
N2A—C3 | 1.390 (8) | C7—H7B | 0.9600 |
N2A—C8 | 1.433 (9) | C7—H7C | 0.9600 |
C9A—C8 | 1.363 (5) | N14—C15 | 1.282 (3) |
C9A—C10A | 1.375 (6) | C15—C16 | 1.459 (3) |
C9A—H9A | 0.9300 | C15—H15 | 0.9300 |
C10A—C11A | 1.369 (6) | C16—C21 | 1.384 (3) |
C10A—H10A | 0.9300 | C16—C17 | 1.387 (3) |
C11A—C12A | 1.361 (6) | C17—C18 | 1.367 (3) |
C11A—H11A | 0.9300 | C17—H17 | 0.9300 |
C12A—C13A | 1.370 (6) | C18—C19 | 1.391 (3) |
C12A—H12A | 0.9300 | C18—H18 | 0.9300 |
C13A—C8 | 1.366 (5) | C19—O22 | 1.361 (2) |
C13A—H13A | 0.9300 | C19—C20 | 1.373 (3) |
N2B—C8 | 1.43 (2) | C20—C21 | 1.380 (3) |
N2B—C3 | 1.47 (2) | C20—H20 | 0.9300 |
C9B—C10B | 1.373 (10) | C21—H21 | 0.9300 |
C9B—C8 | 1.376 (10) | O22—C23 | 1.438 (2) |
C9B—H9B | 0.9300 | C23—C24 | 1.487 (3) |
C10B—C11B | 1.377 (10) | C23—H23A | 0.9700 |
C10B—H10B | 0.9300 | C23—H23B | 0.9700 |
C11B—C12B | 1.375 (10) | C24—C25 | 1.376 (3) |
C11B—H11B | 0.9300 | C24—C29 | 1.379 (3) |
C12B—C13B | 1.377 (10) | C25—C26 | 1.385 (3) |
C12B—H12B | 0.9300 | C25—H25 | 0.9300 |
C13B—C8 | 1.381 (10) | C26—C27 | 1.371 (4) |
C13B—H13B | 0.9300 | C26—H26 | 0.9300 |
O3—C3 | 1.233 (2) | C27—C28 | 1.364 (4) |
C3—C4 | 1.432 (3) | C27—H27 | 0.9300 |
C4—C5 | 1.378 (3) | C28—C29 | 1.367 (4) |
C4—N14 | 1.386 (3) | C28—H28 | 0.9300 |
C5—C7 | 1.485 (3) | C29—H29 | 0.9300 |
C5—N1—N2B | 108.1 (10) | H7A—C7—H7C | 109.5 |
C5—N1—N2A | 106.8 (4) | H7B—C7—H7C | 109.5 |
C5—N1—C6 | 127.36 (19) | C9A—C8—C13A | 120.3 (5) |
N2B—N1—C6 | 124.3 (10) | C13A—C8—C9B | 106.0 (10) |
N2A—N1—C6 | 120.4 (4) | C9A—C8—C13B | 135.1 (12) |
C3—N2A—N1 | 108.5 (6) | C9B—C8—C13B | 121.5 (14) |
C3—N2A—C8 | 125.5 (6) | C9A—C8—N2B | 129.3 (9) |
N1—N2A—C8 | 118.0 (6) | C13A—C8—N2B | 110.4 (10) |
C8—C9A—C10A | 119.5 (7) | C9B—C8—N2B | 143.1 (14) |
C8—C9A—H9A | 120.2 | C13B—C8—N2B | 95.2 (14) |
C10A—C9A—H9A | 120.2 | C9A—C8—N2A | 109.0 (7) |
C11A—C10A—C9A | 120.4 (7) | C13A—C8—N2A | 130.6 (8) |
C11A—C10A—H10A | 119.8 | C9B—C8—N2A | 123.2 (12) |
C9A—C10A—H10A | 119.8 | C13B—C8—N2A | 115.2 (12) |
C12A—C11A—C10A | 119.4 (6) | C15—N14—C4 | 120.29 (18) |
C12A—C11A—H11A | 120.3 | N14—C15—C16 | 121.8 (2) |
C10A—C11A—H11A | 120.3 | N14—C15—H15 | 119.1 |
C11A—C12A—C13A | 120.5 (6) | C16—C15—H15 | 119.1 |
C11A—C12A—H12A | 119.7 | C21—C16—C17 | 117.4 (2) |
C13A—C12A—H12A | 119.7 | C21—C16—C15 | 120.27 (19) |
C8—C13A—C12A | 119.7 (7) | C17—C16—C15 | 122.3 (2) |
C8—C13A—H13A | 120.1 | C18—C17—C16 | 121.5 (2) |
C12A—C13A—H13A | 120.1 | C18—C17—H17 | 119.2 |
N1—N2B—C8 | 122.0 (16) | C16—C17—H17 | 119.2 |
N1—N2B—C3 | 107.4 (15) | C17—C18—C19 | 120.1 (2) |
C8—N2B—C3 | 120.1 (14) | C17—C18—H18 | 119.9 |
C10B—C9B—C8 | 120.7 (19) | C19—C18—H18 | 119.9 |
C10B—C9B—H9B | 119.6 | O22—C19—C20 | 126.0 (2) |
C8—C9B—H9B | 119.6 | O22—C19—C18 | 114.73 (19) |
C9B—C10B—C11B | 115 (2) | C20—C19—C18 | 119.3 (2) |
C9B—C10B—H10B | 122.6 | C19—C20—C21 | 119.8 (2) |
C11B—C10B—H10B | 122.6 | C19—C20—H20 | 120.1 |
C12B—C11B—C10B | 128 (2) | C21—C20—H20 | 120.1 |
C12B—C11B—H11B | 116.2 | C20—C21—C16 | 121.8 (2) |
C10B—C11B—H11B | 116.2 | C20—C21—H21 | 119.1 |
C11B—C12B—C13B | 115 (2) | C16—C21—H21 | 119.1 |
C11B—C12B—H12B | 122.6 | C19—O22—C23 | 118.30 (16) |
C13B—C12B—H12B | 122.6 | O22—C23—C24 | 106.39 (16) |
C12B—C13B—C8 | 120 (2) | O22—C23—H23A | 110.5 |
C12B—C13B—H13B | 119.8 | C24—C23—H23A | 110.5 |
C8—C13B—H13B | 119.8 | O22—C23—H23B | 110.5 |
O3—C3—N2A | 122.2 (4) | C24—C23—H23B | 110.5 |
O3—C3—C4 | 132.8 (2) | H23A—C23—H23B | 108.6 |
N2A—C3—C4 | 104.9 (4) | C25—C24—C29 | 118.6 (2) |
O3—C3—N2B | 123.0 (9) | C25—C24—C23 | 121.7 (2) |
C4—C3—N2B | 102.3 (9) | C29—C24—C23 | 119.7 (2) |
C5—C4—N14 | 122.57 (19) | C24—C25—C26 | 120.1 (2) |
C5—C4—C3 | 108.27 (19) | C24—C25—H25 | 120.0 |
N14—C4—C3 | 129.16 (19) | C26—C25—H25 | 120.0 |
N1—C5—C4 | 109.51 (18) | C27—C26—C25 | 120.2 (3) |
N1—C5—C7 | 121.67 (19) | C27—C26—H26 | 119.9 |
C4—C5—C7 | 128.8 (2) | C25—C26—H26 | 119.9 |
N1—C6—H6A | 109.5 | C28—C27—C26 | 119.9 (3) |
N1—C6—H6B | 109.5 | C28—C27—H27 | 120.0 |
H6A—C6—H6B | 109.5 | C26—C27—H27 | 120.0 |
N1—C6—H6C | 109.5 | C27—C28—C29 | 119.9 (3) |
H6A—C6—H6C | 109.5 | C27—C28—H28 | 120.0 |
H6B—C6—H6C | 109.5 | C29—C28—H28 | 120.0 |
C5—C7—H7A | 109.5 | C28—C29—C24 | 121.3 (3) |
C5—C7—H7B | 109.5 | C28—C29—H29 | 119.3 |
H7A—C7—H7B | 109.5 | C24—C29—H29 | 119.3 |
C5—C7—H7C | 109.5 | ||
C5—N1—N2A—C3 | 14.6 (7) | C10B—C9B—C8—C9A | 152 (12) |
N2B—N1—N2A—C3 | −82 (4) | C10B—C9B—C8—C13A | −6 (4) |
C6—N1—N2A—C3 | 170.3 (4) | C10B—C9B—C8—C13B | −2 (5) |
C5—N1—N2A—C8 | 165.2 (5) | C10B—C9B—C8—N2B | −176 (2) |
N2B—N1—N2A—C8 | 68 (3) | C10B—C9B—C8—N2A | 177 (2) |
C6—N1—N2A—C8 | −39.1 (9) | C12B—C13B—C8—C9A | −11 (6) |
C8—C9A—C10A—C11A | −0.3 (18) | C12B—C13B—C8—C13A | 12 (7) |
C9A—C10A—C11A—C12A | −2.6 (16) | C12B—C13B—C8—C9B | −1 (6) |
C10A—C11A—C12A—C13A | 2.8 (16) | C12B—C13B—C8—N2B | 175 (4) |
C11A—C12A—C13A—C8 | 0 (2) | C12B—C13B—C8—N2A | 179 (3) |
C5—N1—N2B—C8 | −165.2 (11) | N1—N2B—C8—C9A | 74 (2) |
N2A—N1—N2B—C8 | −76 (3) | C3—N2B—C8—C9A | −66.3 (19) |
C6—N1—N2B—C8 | 10.3 (18) | N1—N2B—C8—C13A | −106.7 (16) |
C5—N1—N2B—C3 | −20.5 (12) | C3—N2B—C8—C13A | 112.8 (14) |
N2A—N1—N2B—C3 | 69 (3) | N1—N2B—C8—C9B | 63 (4) |
C6—N1—N2B—C3 | 155.0 (7) | C3—N2B—C8—C9B | −77 (3) |
C8—C9B—C10B—C11B | 2 (5) | N1—N2B—C8—C13B | −112 (3) |
C9B—C10B—C11B—C12B | 2 (6) | C3—N2B—C8—C13B | 108 (2) |
C10B—C11B—C12B—C13B | −5 (6) | N1—N2B—C8—N2A | 79 (3) |
C11B—C12B—C13B—C8 | 4 (6) | C3—N2B—C8—N2A | −62 (3) |
N1—N2A—C3—O3 | 170.4 (4) | C3—N2A—C8—C9A | −103.3 (10) |
C8—N2A—C3—O3 | 22.6 (10) | N1—N2A—C8—C9A | 111.6 (10) |
N1—N2A—C3—C4 | −13.6 (7) | C3—N2A—C8—C13A | 73.6 (14) |
C8—N2A—C3—C4 | −161.4 (7) | N1—N2A—C8—C13A | −71.5 (13) |
N1—N2A—C3—N2B | 72 (3) | C3—N2A—C8—C9B | −110 (2) |
C8—N2A—C3—N2B | −76 (3) | N1—N2A—C8—C9B | 104 (2) |
N1—N2B—C3—O3 | −173.8 (6) | C3—N2A—C8—C13B | 69 (3) |
C8—N2B—C3—O3 | −28.3 (18) | N1—N2A—C8—C13B | −76 (3) |
N1—N2B—C3—N2A | −80 (3) | C3—N2A—C8—N2B | 80 (3) |
C8—N2B—C3—N2A | 66 (3) | N1—N2A—C8—N2B | −65 (3) |
N1—N2B—C3—C4 | 20.1 (12) | C5—C4—N14—C15 | −177.2 (2) |
C8—N2B—C3—C4 | 165.6 (12) | C3—C4—N14—C15 | 3.2 (4) |
O3—C3—C4—C5 | −176.7 (3) | C4—N14—C15—C16 | 178.91 (19) |
N2A—C3—C4—C5 | 8.0 (5) | N14—C15—C16—C21 | 175.9 (2) |
N2B—C3—C4—C5 | −12.6 (8) | N14—C15—C16—C17 | −3.4 (3) |
O3—C3—C4—N14 | 3.0 (5) | C21—C16—C17—C18 | 0.0 (4) |
N2A—C3—C4—N14 | −172.3 (5) | C15—C16—C17—C18 | 179.3 (2) |
N2B—C3—C4—N14 | 167.1 (8) | C16—C17—C18—C19 | −1.0 (4) |
N2B—N1—C5—C4 | 12.4 (8) | C17—C18—C19—O22 | −177.9 (2) |
N2A—N1—C5—C4 | −9.4 (5) | C17—C18—C19—C20 | 1.5 (4) |
C6—N1—C5—C4 | −162.9 (3) | O22—C19—C20—C21 | 178.3 (2) |
N2B—N1—C5—C7 | −166.7 (8) | C18—C19—C20—C21 | −0.9 (4) |
N2A—N1—C5—C7 | 171.5 (4) | C19—C20—C21—C16 | −0.1 (4) |
C6—N1—C5—C7 | 18.0 (4) | C17—C16—C21—C20 | 0.5 (3) |
N14—C4—C5—N1 | −178.8 (2) | C15—C16—C21—C20 | −178.7 (2) |
C3—C4—C5—N1 | 1.0 (3) | C20—C19—O22—C23 | −2.2 (3) |
N14—C4—C5—C7 | 0.3 (4) | C18—C19—O22—C23 | 177.04 (19) |
C3—C4—C5—C7 | 180.0 (2) | C19—O22—C23—C24 | −169.24 (18) |
C10A—C9A—C8—C13A | 3.0 (18) | O22—C23—C24—C25 | −101.5 (2) |
C10A—C9A—C8—C9B | −22 (8) | O22—C23—C24—C29 | 76.8 (2) |
C10A—C9A—C8—C13B | 10 (3) | C29—C24—C25—C26 | −1.0 (3) |
C10A—C9A—C8—N2B | −178.0 (14) | C23—C24—C25—C26 | 177.3 (2) |
C10A—C9A—C8—N2A | −179.7 (10) | C24—C25—C26—C27 | −0.3 (4) |
C12A—C13A—C8—C9A | −3 (2) | C25—C26—C27—C28 | 1.1 (4) |
C12A—C13A—C8—C9B | 4 (2) | C26—C27—C28—C29 | −0.5 (4) |
C12A—C13A—C8—C13B | −164 (12) | C27—C28—C29—C24 | −0.8 (4) |
C12A—C13A—C8—N2B | 178.0 (15) | C25—C24—C29—C28 | 1.6 (3) |
C12A—C13A—C8—N2A | −179.5 (9) | C23—C24—C29—C28 | −176.8 (2) |
Experimental details
Crystal data | |
Chemical formula | C25H23N3O2 |
Mr | 397.46 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.0079 (5), 9.9079 (4), 17.0469 (9) |
β (°) | 103.674 (4) |
V (Å3) | 2134.75 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Sapphire3 |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.920, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19519, 4162, 2399 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.154, 1.03 |
No. of reflections | 4162 |
No. of parameters | 292 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.15 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis PRO (Oxford Diffraction ,2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), PLATON (Spek, 2009).
Acknowledgements
RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. BN thanks the UGC for financial assistance through the BSR one-time grant for the purchase of chemicals. PSN thanks Mangalore University for research facilities and the DST–PURSE for financial assistance.
References
Dutkiewicz, G., Shetty, D. N., Narayana, B., Yathirajan, H. S. & Kubicki, M. (2012). Acta Cryst. E68, o1324. CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hu, T.-P. (2006). Acta Cryst. E62, o2270–o2271. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, S.-X., Tian, X., Zhen, X.-L., Li, Z.-C. & Han, J.-R. (2008). Acta Cryst. E64, o2245. Web of Science CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Patole, J., Shingnapurkar, D., Padhyea, S. & Ratledge, C. (2006). Bioorg. Med. Chem. Lett. 16, 1514–1517. Web of Science CrossRef PubMed CAS Google Scholar
Satyanarayana, V. S. V., Sreevani, P., Sivakumar, A. & Vijayakumar, V. (2008). Arkivoc, 17, 221–233. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, L., Ge, H., Tan, S., Li, H., Song, Y., Zhu, H. & Tan, R. (2007). Eur. J. Med. Chem. 42, 558–564. Web of Science CrossRef PubMed CAS 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.
Schiff bases are widely used organic compounds and structurally it is a nitrogen analogue of an aldehyde or ketone in which the carbonyl group has been replaced by an imine or azomethine group. They are used as pigments and dyes, catalysts, intermediates in organic synthesis, and polymer stabilisers. Schiff bases have also been shown to exhibit a broad range of biological activities including antimicrobial (Shi et al., 2007; Satyanarayana et al., 2008; antimycobacterial (Patole et al., 2006). In view of the pharmacological importance of schiff base derivatives, the title compound (I) is prepared and its crystal structure is reported.
All bond lengths and angles are normal and correspond to those observed in related structures(Liu et al., 2008; Hu, 2006; Dutkiewicz et al., 2012). The central benzene ring makes dihedral angles of 77.14 (8), 87.7 (2) and 87.1 (6)° with the terminal benzene rings (C24—C29),(C8—C13A)and (C8—C13B) respectively while 1.9 (1)(N2A)/ 1.7 (1)°(N2B) with the pyrazolone ring. The benzene ring (C8—C13) and atom N2 are disordered over two positions with an occupancy ratio of 0.71 (2):0.29 (2). The N atoms of the pyrazole ring have a pyramidal environment, the sums of the valence angles around them being 354.6 (3)(N1) and 352.0 (6)(N2A) / 349.5 (15)(N2B) °. The sums of the valence angles around N-atoms of the pyrazole ring in the polymorph of this compound are 353.5 for N1 and 347.3 ° for N2 (Dutkiewicz et al., 2012). Molecules are packed into layers parallel to the ac-plane (Fig.2).