organic compounds
1,5-Dimethyl-2-phenyl-4-[phenyl(pyridin-2-ylamino)methyl]-1H-pyrazol-3(2H)-one
aDepartment of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India, bDepartment of Physics, Bishop Heber College (Autonomous), Tiruchirappalli 620 017, Tamilnadu, India, and cDepartment of Physics, National Institute of Technology, Tiruchirappalli 620 015, Tamilnadu, India
*Correspondence e-mail: xrdfrank@yahoo.co.in
In the title compound, C23H22N4O, the pyrazole ring makes dihedral angles of 45.57 (11)° with the attached phenyl ring, and 83.98 (10) and 67.85 (10) °, respectively, with the other phenyl ring and the pyridyl ring. The pyridyl ring makes a dihedral angle of 80.15 (10)° with the adjacent phenyl ring. In the crystal, N—H⋯O hydrogen bonds supplemented by weak C—H⋯O hydrogen bonds link the molecules into chains which run parallel to the a-axis direction.
Related literature
For the origin of the material studied, see: Vijayan (1971); Singh & Vijayan (1973). For related structures, see: Singh & Vijayan (1974, 1976); Tordjman et al. (1991); Yadav et al. (2003); Li & Zhang (2004); Wen (2005); Sun et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812042936/go2065sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042936/go2065Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042936/go2065Isup3.cml
5.31 mmol of 2-aminopyridine and 5.31 mmol of benzaldehyde were dissolved in ethanol solution. To this mixture 5.31 mmol of antipyrine was added and stirred well. The contents were refluxed at a temperature of 333 K for 12 h. The product obtained by Mannich base condensation was filtered, dried and then washed with distilled water. It is then dried in the air oven at 323 K. By slow evaporation technique, using ethanol, orange colour block shaped crystals of title compound suitable for X-ray
were obtained from the product.For APBA, which crystallizes in the
P212121, the Friedel equivalents were merged in the absence of significant effects prior to the final cycles and the was assigned arbitrarily. The 002 reflection was omitted because it was obscured by the beamstop. The H atom attached to N3 was refined isotropically. H atoms attached to C atoms were included in calculated positions and treated as riding atoms, with C—H=0.93 to 0.96Å, and with Uiso(H)=1.5Ueq(C) for those attached to methyl H atoms and Uiso(H)=1.2Ueq(C) for the remaining H atoms. The positions of the methyl hydrogens and that attached to N3 were checked on a final difference map.Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).C23H22N4O | F(000) = 784 |
Mr = 370.45 | Dx = 1.293 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3758 reflections |
a = 5.701 (5) Å | θ = 2.2–25.4° |
b = 12.485 (5) Å | µ = 0.08 mm−1 |
c = 26.736 (5) Å | T = 273 K |
V = 1903.0 (19) Å3 | Block, orange |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
Bruker Kappa APEXII CCD diffractometer | 2337 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω and ϕ scan | θmax = 29.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −4→7 |
Tmin = 0.976, Tmax = 0.984 | k = −17→17 |
14432 measured reflections | l = −36→34 |
2959 independent 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0435P)2 + 0.2362P] where P = (Fo2 + 2Fc2)/3 |
2959 reflections | (Δ/σ)max < 0.001 |
259 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C23H22N4O | V = 1903.0 (19) Å3 |
Mr = 370.45 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.701 (5) Å | µ = 0.08 mm−1 |
b = 12.485 (5) Å | T = 273 K |
c = 26.736 (5) Å | 0.3 × 0.2 × 0.2 mm |
Bruker Kappa APEXII CCD diffractometer | 2959 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2337 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.984 | Rint = 0.036 |
14432 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.18 e Å−3 |
2959 reflections | Δρmin = −0.19 e Å−3 |
259 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.3555 (2) | 0.08528 (11) | 0.70108 (5) | 0.0391 (3) | |
N1 | 0.2298 (3) | 0.21846 (12) | 0.75511 (6) | 0.0315 (4) | |
N2 | 0.0380 (3) | 0.28913 (12) | 0.75618 (6) | 0.0335 (4) | |
N3 | −0.2190 (3) | 0.08348 (13) | 0.63621 (6) | 0.0352 (4) | |
N4 | −0.0868 (3) | −0.01040 (13) | 0.56735 (6) | 0.0396 (4) | |
C1 | 0.1607 (4) | 0.17086 (18) | 0.84215 (8) | 0.0405 (5) | |
H1 | 0.0148 | 0.2041 | 0.8409 | 0.049* | |
C2 | 0.2324 (5) | 0.11982 (18) | 0.88527 (9) | 0.0508 (6) | |
H2 | 0.1348 | 0.1191 | 0.9131 | 0.061* | |
C3 | 0.4462 (5) | 0.0702 (2) | 0.88728 (9) | 0.0551 (7) | |
H3 | 0.492 | 0.0342 | 0.9161 | 0.066* | |
C4 | 0.5923 (5) | 0.07368 (19) | 0.84676 (9) | 0.0505 (6) | |
H4 | 0.7383 | 0.0407 | 0.8484 | 0.061* | |
C5 | 0.5254 (4) | 0.12577 (16) | 0.80329 (9) | 0.0409 (5) | |
H5 | 0.6266 | 0.1293 | 0.7761 | 0.049* | |
C6 | 0.3058 (4) | 0.17246 (15) | 0.80100 (7) | 0.0325 (4) | |
C7 | 0.2224 (3) | 0.16029 (14) | 0.71041 (7) | 0.0290 (4) | |
C8 | 0.0321 (3) | 0.20467 (14) | 0.68212 (7) | 0.0280 (4) | |
C9 | −0.0668 (4) | 0.28329 (14) | 0.71018 (7) | 0.0313 (4) | |
C10 | −0.0332 (3) | 0.16209 (15) | 0.63147 (7) | 0.0298 (4) | |
H10 | 0.1045 | 0.1232 | 0.6192 | 0.036* | |
C11 | −0.0829 (3) | 0.25022 (15) | 0.59317 (7) | 0.0282 (4) | |
C12 | −0.2876 (4) | 0.25263 (16) | 0.56545 (7) | 0.0331 (4) | |
H12 | −0.4044 | 0.2023 | 0.5715 | 0.04* | |
C13 | −0.3200 (4) | 0.32958 (17) | 0.52860 (8) | 0.0390 (5) | |
H13 | −0.458 | 0.3303 | 0.51 | 0.047* | |
C14 | −0.1491 (4) | 0.40456 (17) | 0.51947 (8) | 0.0410 (5) | |
H14 | −0.1703 | 0.4559 | 0.4947 | 0.049* | |
C15 | 0.0535 (4) | 0.40313 (17) | 0.54730 (8) | 0.0420 (5) | |
H15 | 0.1691 | 0.4541 | 0.5414 | 0.05* | |
C16 | 0.0869 (4) | 0.32708 (16) | 0.58385 (7) | 0.0355 (4) | |
H16 | 0.2247 | 0.3273 | 0.6025 | 0.043* | |
C17 | −0.2525 (4) | 0.00363 (14) | 0.60187 (7) | 0.0319 (4) | |
C18 | −0.4543 (4) | −0.06045 (16) | 0.60472 (8) | 0.0400 (5) | |
H18 | −0.5674 | −0.0482 | 0.6291 | 0.048* | |
C19 | −0.4802 (5) | −0.14120 (17) | 0.57079 (9) | 0.0497 (6) | |
H19 | −0.6112 | −0.1855 | 0.572 | 0.06* | |
C20 | −0.3093 (5) | −0.15665 (18) | 0.53444 (9) | 0.0527 (7) | |
H20 | −0.3239 | −0.2107 | 0.5107 | 0.063* | |
C21 | −0.1212 (5) | −0.09074 (17) | 0.53461 (8) | 0.0473 (6) | |
H21 | −0.007 | −0.1017 | 0.5103 | 0.057* | |
C22 | −0.2613 (4) | 0.35812 (17) | 0.69792 (9) | 0.0460 (6) | |
H22A | −0.1975 | 0.4263 | 0.6884 | 0.069* | |
H22B | −0.36 | 0.367 | 0.7267 | 0.069* | |
H22C | −0.3518 | 0.3294 | 0.6708 | 0.069* | |
C23 | 0.0838 (5) | 0.39199 (16) | 0.78084 (9) | 0.0508 (6) | |
H23A | 0.1981 | 0.4314 | 0.762 | 0.076* | |
H23B | 0.1424 | 0.3794 | 0.814 | 0.076* | |
H23C | −0.0591 | 0.4325 | 0.7827 | 0.076* | |
H3A | −0.332 (5) | 0.0995 (19) | 0.6557 (9) | 0.049 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0394 (8) | 0.0403 (8) | 0.0375 (8) | 0.0110 (7) | 0.0007 (7) | −0.0041 (6) |
N1 | 0.0361 (9) | 0.0307 (8) | 0.0278 (9) | 0.0034 (7) | −0.0035 (7) | −0.0019 (6) |
N2 | 0.0436 (9) | 0.0287 (8) | 0.0283 (9) | 0.0074 (7) | −0.0037 (7) | −0.0045 (6) |
N3 | 0.0436 (10) | 0.0328 (8) | 0.0292 (9) | −0.0055 (8) | 0.0075 (8) | −0.0056 (7) |
N4 | 0.0508 (11) | 0.0353 (9) | 0.0327 (9) | 0.0003 (9) | 0.0028 (9) | −0.0044 (7) |
C1 | 0.0454 (12) | 0.0427 (11) | 0.0335 (12) | −0.0056 (10) | −0.0035 (10) | 0.0010 (9) |
C2 | 0.0648 (16) | 0.0552 (14) | 0.0323 (12) | −0.0131 (14) | −0.0021 (12) | 0.0063 (10) |
C3 | 0.0689 (17) | 0.0550 (14) | 0.0414 (14) | −0.0137 (14) | −0.0234 (13) | 0.0140 (11) |
C4 | 0.0433 (13) | 0.0489 (14) | 0.0594 (16) | −0.0064 (11) | −0.0209 (12) | 0.0106 (11) |
C5 | 0.0359 (11) | 0.0433 (12) | 0.0434 (13) | −0.0057 (9) | −0.0056 (10) | 0.0067 (9) |
C6 | 0.0388 (11) | 0.0305 (9) | 0.0283 (10) | −0.0070 (8) | −0.0088 (9) | 0.0000 (7) |
C7 | 0.0328 (10) | 0.0284 (9) | 0.0257 (10) | −0.0024 (8) | 0.0024 (8) | −0.0005 (7) |
C8 | 0.0337 (10) | 0.0271 (9) | 0.0232 (9) | −0.0015 (8) | 0.0000 (7) | 0.0007 (7) |
C9 | 0.0390 (10) | 0.0279 (9) | 0.0269 (10) | 0.0009 (8) | −0.0015 (8) | 0.0018 (7) |
C10 | 0.0334 (9) | 0.0310 (9) | 0.0248 (9) | −0.0008 (8) | 0.0008 (8) | −0.0026 (7) |
C11 | 0.0338 (9) | 0.0309 (9) | 0.0200 (9) | 0.0000 (8) | 0.0012 (8) | −0.0035 (7) |
C12 | 0.0328 (10) | 0.0361 (9) | 0.0305 (11) | −0.0005 (9) | −0.0017 (8) | −0.0032 (8) |
C13 | 0.0420 (12) | 0.0446 (11) | 0.0304 (11) | 0.0070 (10) | −0.0078 (9) | −0.0045 (9) |
C14 | 0.0567 (14) | 0.0375 (11) | 0.0288 (11) | 0.0090 (11) | 0.0039 (10) | 0.0052 (8) |
C15 | 0.0476 (13) | 0.0390 (11) | 0.0396 (12) | −0.0055 (11) | 0.0071 (10) | 0.0057 (9) |
C16 | 0.0335 (10) | 0.0400 (11) | 0.0330 (11) | −0.0036 (9) | −0.0023 (8) | 0.0006 (8) |
C17 | 0.0415 (10) | 0.0263 (9) | 0.0278 (10) | 0.0024 (8) | −0.0037 (8) | 0.0026 (7) |
C18 | 0.0429 (12) | 0.0348 (10) | 0.0423 (13) | −0.0010 (9) | −0.0038 (10) | 0.0007 (8) |
C19 | 0.0548 (14) | 0.0384 (12) | 0.0558 (15) | −0.0077 (11) | −0.0115 (13) | −0.0040 (10) |
C20 | 0.0776 (18) | 0.0353 (11) | 0.0452 (14) | 0.0009 (13) | −0.0092 (13) | −0.0140 (10) |
C21 | 0.0679 (16) | 0.0385 (11) | 0.0354 (12) | 0.0068 (12) | 0.0022 (11) | −0.0090 (9) |
C22 | 0.0517 (13) | 0.0461 (12) | 0.0403 (13) | 0.0179 (11) | −0.0038 (11) | −0.0047 (9) |
C23 | 0.0748 (17) | 0.0324 (11) | 0.0452 (13) | 0.0050 (12) | −0.0110 (13) | −0.0129 (9) |
O1—C7 | 1.231 (2) | C10—H10 | 0.98 |
N1—C7 | 1.399 (2) | C11—C12 | 1.383 (3) |
N1—N2 | 1.405 (2) | C11—C16 | 1.386 (3) |
N1—C6 | 1.422 (2) | C12—C13 | 1.389 (3) |
N2—C9 | 1.369 (2) | C12—H12 | 0.93 |
N2—C23 | 1.467 (2) | C13—C14 | 1.373 (3) |
N3—C17 | 1.369 (2) | C13—H13 | 0.93 |
N3—C10 | 1.450 (3) | C14—C15 | 1.374 (3) |
N3—H3A | 0.85 (3) | C14—H14 | 0.93 |
N4—C17 | 1.332 (3) | C15—C16 | 1.376 (3) |
N4—C21 | 1.346 (3) | C15—H15 | 0.93 |
C1—C6 | 1.377 (3) | C16—H16 | 0.93 |
C1—C2 | 1.379 (3) | C17—C18 | 1.403 (3) |
C1—H1 | 0.93 | C18—C19 | 1.364 (3) |
C2—C3 | 1.368 (4) | C18—H18 | 0.93 |
C2—H2 | 0.93 | C19—C20 | 1.390 (4) |
C3—C4 | 1.367 (4) | C19—H19 | 0.93 |
C3—H3 | 0.93 | C20—C21 | 1.352 (4) |
C4—C5 | 1.385 (3) | C20—H20 | 0.93 |
C4—H4 | 0.93 | C21—H21 | 0.93 |
C5—C6 | 1.382 (3) | C22—H22A | 0.96 |
C5—H5 | 0.93 | C22—H22B | 0.96 |
C7—C8 | 1.434 (3) | C22—H22C | 0.96 |
C8—C9 | 1.358 (3) | C23—H23A | 0.96 |
C8—C10 | 1.502 (3) | C23—H23B | 0.96 |
C9—C22 | 1.486 (3) | C23—H23C | 0.96 |
C10—C11 | 1.530 (3) | ||
C7—N1—N2 | 108.65 (15) | C12—C11—C10 | 122.07 (17) |
C7—N1—C6 | 122.45 (15) | C16—C11—C10 | 119.27 (17) |
N2—N1—C6 | 118.22 (16) | C11—C12—C13 | 120.52 (19) |
C9—N2—N1 | 106.73 (15) | C11—C12—H12 | 119.7 |
C9—N2—C23 | 121.87 (16) | C13—C12—H12 | 119.7 |
N1—N2—C23 | 114.84 (18) | C14—C13—C12 | 120.2 (2) |
C17—N3—C10 | 122.43 (17) | C14—C13—H13 | 119.9 |
C17—N3—H3A | 118.4 (17) | C12—C13—H13 | 119.9 |
C10—N3—H3A | 116.5 (17) | C13—C14—C15 | 119.4 (2) |
C17—N4—C21 | 116.5 (2) | C13—C14—H14 | 120.3 |
C6—C1—C2 | 119.8 (2) | C15—C14—H14 | 120.3 |
C6—C1—H1 | 120.1 | C14—C15—C16 | 120.7 (2) |
C2—C1—H1 | 120.1 | C14—C15—H15 | 119.7 |
C3—C2—C1 | 120.4 (2) | C16—C15—H15 | 119.7 |
C3—C2—H2 | 119.8 | C15—C16—C11 | 120.6 (2) |
C1—C2—H2 | 119.8 | C15—C16—H16 | 119.7 |
C4—C3—C2 | 119.8 (2) | C11—C16—H16 | 119.7 |
C4—C3—H3 | 120.1 | N4—C17—N3 | 117.50 (19) |
C2—C3—H3 | 120.1 | N4—C17—C18 | 122.95 (18) |
C3—C4—C5 | 120.8 (2) | N3—C17—C18 | 119.54 (19) |
C3—C4—H4 | 119.6 | C19—C18—C17 | 118.3 (2) |
C5—C4—H4 | 119.6 | C19—C18—H18 | 120.9 |
C6—C5—C4 | 119.0 (2) | C17—C18—H18 | 120.9 |
C6—C5—H5 | 120.5 | C18—C19—C20 | 119.4 (2) |
C4—C5—H5 | 120.5 | C18—C19—H19 | 120.3 |
C1—C6—C5 | 120.20 (19) | C20—C19—H19 | 120.3 |
C1—C6—N1 | 120.80 (19) | C21—C20—C19 | 118.0 (2) |
C5—C6—N1 | 118.96 (19) | C21—C20—H20 | 121 |
O1—C7—N1 | 123.31 (17) | C19—C20—H20 | 121 |
O1—C7—C8 | 130.83 (18) | N4—C21—C20 | 124.9 (2) |
N1—C7—C8 | 105.83 (16) | N4—C21—H21 | 117.6 |
C9—C8—C7 | 107.59 (17) | C20—C21—H21 | 117.6 |
C9—C8—C10 | 130.63 (19) | C9—C22—H22A | 109.5 |
C7—C8—C10 | 121.76 (17) | C9—C22—H22B | 109.5 |
C8—C9—N2 | 110.70 (17) | H22A—C22—H22B | 109.5 |
C8—C9—C22 | 129.95 (19) | C9—C22—H22C | 109.5 |
N2—C9—C22 | 119.35 (17) | H22A—C22—H22C | 109.5 |
N3—C10—C8 | 109.99 (15) | H22B—C22—H22C | 109.5 |
N3—C10—C11 | 114.21 (16) | N2—C23—H23A | 109.5 |
C8—C10—C11 | 113.27 (15) | N2—C23—H23B | 109.5 |
N3—C10—H10 | 106.2 | H23A—C23—H23B | 109.5 |
C8—C10—H10 | 106.2 | N2—C23—H23C | 109.5 |
C11—C10—H10 | 106.2 | H23A—C23—H23C | 109.5 |
C12—C11—C16 | 118.57 (18) | H23B—C23—H23C | 109.5 |
C7—N1—N2—C9 | −7.28 (19) | N1—N2—C9—C22 | −173.48 (17) |
C6—N1—N2—C9 | −152.75 (17) | C23—N2—C9—C22 | −38.8 (3) |
C7—N1—N2—C23 | −145.59 (17) | C17—N3—C10—C8 | −154.18 (18) |
C6—N1—N2—C23 | 68.9 (2) | C17—N3—C10—C11 | 77.2 (2) |
C6—C1—C2—C3 | −0.4 (3) | C9—C8—C10—N3 | −83.2 (2) |
C1—C2—C3—C4 | 1.7 (4) | C7—C8—C10—N3 | 94.7 (2) |
C2—C3—C4—C5 | −0.8 (4) | C9—C8—C10—C11 | 46.0 (3) |
C3—C4—C5—C6 | −1.4 (3) | C7—C8—C10—C11 | −136.16 (18) |
C2—C1—C6—C5 | −1.8 (3) | N3—C10—C11—C12 | −0.6 (2) |
C2—C1—C6—N1 | 175.87 (19) | C8—C10—C11—C12 | −127.61 (19) |
C4—C5—C6—C1 | 2.7 (3) | N3—C10—C11—C16 | −177.14 (17) |
C4—C5—C6—N1 | −175.04 (19) | C8—C10—C11—C16 | 55.9 (2) |
C7—N1—C6—C1 | −121.8 (2) | C16—C11—C12—C13 | 0.9 (3) |
N2—N1—C6—C1 | 18.7 (3) | C10—C11—C12—C13 | −175.58 (18) |
C7—N1—C6—C5 | 55.9 (3) | C11—C12—C13—C14 | −0.3 (3) |
N2—N1—C6—C5 | −163.60 (16) | C12—C13—C14—C15 | −0.4 (3) |
N2—N1—C7—O1 | −173.02 (17) | C13—C14—C15—C16 | 0.4 (3) |
C6—N1—C7—O1 | −29.3 (3) | C14—C15—C16—C11 | 0.2 (3) |
N2—N1—C7—C8 | 5.19 (19) | C12—C11—C16—C15 | −0.9 (3) |
C6—N1—C7—C8 | 148.89 (17) | C10—C11—C16—C15 | 175.72 (18) |
O1—C7—C8—C9 | 176.9 (2) | C21—N4—C17—N3 | 178.70 (18) |
N1—C7—C8—C9 | −1.2 (2) | C21—N4—C17—C18 | −0.2 (3) |
O1—C7—C8—C10 | −1.4 (3) | C10—N3—C17—N4 | 10.0 (3) |
N1—C7—C8—C10 | −179.44 (16) | C10—N3—C17—C18 | −171.04 (18) |
C7—C8—C9—N2 | −3.4 (2) | N4—C17—C18—C19 | 0.6 (3) |
C10—C8—C9—N2 | 174.63 (18) | N3—C17—C18—C19 | −178.4 (2) |
C7—C8—C9—C22 | 176.7 (2) | C17—C18—C19—C20 | −0.8 (3) |
C10—C8—C9—C22 | −5.2 (4) | C18—C19—C20—C21 | 0.7 (4) |
N1—N2—C9—C8 | 6.6 (2) | C17—N4—C21—C20 | 0.1 (3) |
C23—N2—C9—C8 | 141.4 (2) | C19—C20—C21—N4 | −0.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1i | 0.85 (3) | 2.16 (3) | 2.982 (3) | 161 (2) |
C18—H18···O1i | 0.93 | 2.58 | 3.335 (3) | 138 |
C23—H23C···O1ii | 0.96 | 2.59 | 3.512 (3) | 162 |
Symmetry codes: (i) x−1, y, z; (ii) −x, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C23H22N4O |
Mr | 370.45 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 273 |
a, b, c (Å) | 5.701 (5), 12.485 (5), 26.736 (5) |
V (Å3) | 1903.0 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.976, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14432, 2959, 2337 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.694 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.095, 1.01 |
No. of reflections | 2959 |
No. of parameters | 259 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.19 |
Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O1i | 0.85 (3) | 2.16 (3) | 2.982 (3) | 161 (2) |
C18—H18···O1i | 0.93 | 2.58 | 3.335 (3) | 138 |
C23—H23C···O1ii | 0.96 | 2.59 | 3.512 (3) | 162 |
Symmetry codes: (i) x−1, y, z; (ii) −x, y+1/2, −z+3/2. |
Acknowledgements
The authors thank the SAIF at IITM Chennai, sponsored by DST India, for providing analytical facilities.
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Antipyrine (2,3-dimethyl-1-phenylpyrazol-5-one) is one of the best known pyrazole derivatives used as pain-relieving medicine. It is the first pyrazole derivative to be introduced as an analgesic and antipyretic drug. Antipyrine and its derivatives have been long known for their wide spectrum of biological activities. Their roles in biological processes have become a topic of study in recent years. Though rarely used alone, nowadays, on account of its toxicity, antipyrine forms part of some combination products used as pain-relieving medicines. Many of its derivatives like amidopyrine and metamizol are well known and widely used analgesics. Therefore a detailed knowledge of the structure and the possible modes of interaction of antipyrine are important in elucidating the molecular mechanism of the action of pain-relieving medicines. The crystal structure of antipyrine, its derivatives and some of its metallic complexes have already been reported (see related literature). Presently, the crystal structure of 2-amino pyridino benzyl antipyrine {1,2-dihydro-2,3-dimethyl-1-phenyl-4-(phenyl (pyridin-2-yl amino) methyl)pyrazol-5-one} has been elucidated. The conformational features and the hydrogen bonding analysis have been analysed in order to have a further insight in to their chemical and pharmaceutical aspects. The chemical scheme of 2-amino pyridino benzyl antipyrine is shown.
An ORTEP-3 (Farrugia, 1997) diagram of the asymmetric unit of 2-amino pyridino benzyl antipyrine (APBA) is shown in Figure 1. In APBA, the antipyrine, benzene and pyridyl amine molecules are bridged by C10 which is the asymmetric sp3 carbon in the structure. Bond lengths and angles are comparable with those of the related structures reported. Four flat fragments are present in the structure elucidated. The dihedral angles between these flat rings A (C1—C6), B (N1, N2, C7—C9), C (C11—C16) and D (C17—C21, N4) are A/B= 45.57 (11)°, A/C= 54.96 (10)°, A/D= 82.10 (11)°, B/C= 83.98 (10)°, B/D= 67.85 (10)° and C/D= 80.15 (10)°. These values show that the pyrazole (B), benzene (C) and pyridyl (D) rings are almost perpendicular to each other. The crystal packing of the compound APBA is stabilized by N3–H3A···O1 and C18—H18···O1 hydrogen bonds which link the molecules into one-dimensional chains which run parallel to the a-axis, Table 1, Figure 2. In addition there is a short contact C23–H23C···O1.