The title compound, C
19H
16N
4O
3, was synthesized by the reaction of 5-amino-3-methyl-1-phenylpyrazole with 4-nitrobenzaldehyde and Medrum's acid in glycol under microwave irradiation. X-ray crystal structure analysis reveals that the dihydropyridine ring adopts a distorted half-chair conformation. In the crystal structure, the molecules exist as N—H
O hydrogen-bonded dimers.
Supporting information
CCDC reference: 277222
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.003 Å
- R factor = 0.062
- wR factor = 0.154
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for N4 - C17 .. 5.02 su
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
3-methyl-4-(4-nitrophenyl)–6-oxo-1-phenyl-4,5-dihydropyrazolo[3,4-
b]pyridine
top
Crystal data top
C19H16N4O3 | F(000) = 728 |
Mr = 348.36 | Dx = 1.375 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2ybc | Cell parameters from 2111 reflections |
a = 7.846 (5) Å | θ = 3.1–27.5° |
b = 16.758 (14) Å | µ = 0.10 mm−1 |
c = 12.940 (15) Å | T = 193 K |
β = 98.374 (12)° | Block, yellow |
V = 1683 (3) Å3 | 0.39 × 0.30 × 0.28 mm |
Z = 4 | |
Data collection top
Rigaku Mercury CCD area-detector diffractometer | 3850 independent reflections |
Radiation source: fine-focus sealed tube | 3234 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −21→21 |
Tmin = 0.964, Tmax = 0.974 | l = −15→16 |
18328 measured reflections | |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0624P)2 + 0.765P] where P = (Fo2 + 2Fc2)/3 |
3850 reflections | (Δ/σ)max = 0.001 |
240 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
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 | |
O1 | 0.98820 (17) | 0.54242 (9) | 0.62102 (10) | 0.0417 (4) | |
O2 | 0.0742 (3) | 0.41329 (15) | 1.02807 (18) | 0.0916 (7) | |
O3 | 0.3037 (3) | 0.35734 (11) | 1.10530 (14) | 0.0727 (6) | |
N1 | 0.8122 (2) | 0.44718 (9) | 0.54238 (11) | 0.0329 (4) | |
N2 | 0.60602 (19) | 0.34421 (9) | 0.47547 (11) | 0.0311 (3) | |
N3 | 0.44634 (19) | 0.31740 (10) | 0.49284 (12) | 0.0350 (4) | |
N4 | 0.2247 (3) | 0.39549 (12) | 1.03321 (15) | 0.0545 (5) | |
C1 | 0.6614 (2) | 0.40376 (10) | 0.54230 (13) | 0.0286 (4) | |
C2 | 0.5411 (2) | 0.41689 (11) | 0.60652 (13) | 0.0303 (4) | |
C3 | 0.5669 (2) | 0.48268 (11) | 0.68675 (14) | 0.0325 (4) | |
H3 | 0.5116 | 0.5322 | 0.6542 | 0.039* | |
C4 | 0.7619 (2) | 0.49817 (12) | 0.71309 (14) | 0.0386 (5) | |
H4A | 0.7789 | 0.5500 | 0.7498 | 0.046* | |
H4B | 0.8123 | 0.4564 | 0.7624 | 0.046* | |
C5 | 0.8614 (2) | 0.49959 (11) | 0.62127 (14) | 0.0330 (4) | |
C6 | 0.4090 (2) | 0.36127 (11) | 0.57273 (14) | 0.0333 (4) | |
C7 | 0.6904 (2) | 0.30902 (10) | 0.39569 (13) | 0.0323 (4) | |
C8 | 0.8600 (3) | 0.28510 (13) | 0.42012 (16) | 0.0439 (5) | |
H8 | 0.9171 | 0.2891 | 0.4899 | 0.053* | |
C9 | 0.9465 (3) | 0.25533 (15) | 0.34234 (19) | 0.0545 (6) | |
H9 | 1.0638 | 0.2398 | 0.3582 | 0.065* | |
C10 | 0.8617 (3) | 0.24841 (14) | 0.24228 (18) | 0.0548 (6) | |
H10 | 0.9210 | 0.2283 | 0.1888 | 0.066* | |
C11 | 0.6915 (3) | 0.27038 (13) | 0.21863 (15) | 0.0491 (6) | |
H11 | 0.6338 | 0.2645 | 0.1492 | 0.059* | |
C12 | 0.6036 (3) | 0.30103 (12) | 0.29534 (15) | 0.0399 (5) | |
H12 | 0.4861 | 0.3162 | 0.2792 | 0.048* | |
C13 | 0.2461 (3) | 0.34548 (14) | 0.61605 (19) | 0.0484 (5) | |
H13A | 0.1836 | 0.3016 | 0.5774 | 0.073* | |
H13B | 0.1743 | 0.3936 | 0.6093 | 0.073* | |
H13C | 0.2734 | 0.3309 | 0.6900 | 0.073* | |
C14 | 0.4844 (2) | 0.46347 (10) | 0.78336 (14) | 0.0320 (4) | |
C15 | 0.3325 (2) | 0.50101 (12) | 0.79778 (15) | 0.0378 (4) | |
H15 | 0.2872 | 0.5420 | 0.7509 | 0.045* | |
C16 | 0.2456 (3) | 0.47983 (13) | 0.87941 (17) | 0.0431 (5) | |
H16 | 0.1404 | 0.5050 | 0.8885 | 0.052* | |
C17 | 0.3162 (3) | 0.42104 (12) | 0.94724 (15) | 0.0408 (5) | |
C18 | 0.4689 (3) | 0.38406 (12) | 0.93707 (16) | 0.0448 (5) | |
H18 | 0.5164 | 0.3448 | 0.9859 | 0.054* | |
C19 | 0.5519 (3) | 0.40544 (12) | 0.85402 (15) | 0.0399 (5) | |
H19 | 0.6569 | 0.3799 | 0.8452 | 0.048* | |
H1 | 0.877 (3) | 0.4487 (15) | 0.4870 (19) | 0.054 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0452 (8) | 0.0457 (8) | 0.0377 (7) | −0.0143 (6) | 0.0178 (6) | −0.0103 (6) |
O2 | 0.0799 (14) | 0.1071 (18) | 0.1026 (17) | 0.0087 (12) | 0.0630 (13) | 0.0197 (13) |
O3 | 0.1160 (16) | 0.0627 (11) | 0.0485 (10) | 0.0095 (11) | 0.0426 (10) | 0.0127 (9) |
N1 | 0.0373 (8) | 0.0352 (8) | 0.0286 (7) | −0.0071 (7) | 0.0128 (6) | −0.0064 (6) |
N2 | 0.0340 (8) | 0.0337 (8) | 0.0267 (7) | −0.0028 (6) | 0.0075 (6) | −0.0041 (6) |
N3 | 0.0308 (8) | 0.0386 (9) | 0.0358 (8) | −0.0022 (6) | 0.0049 (6) | −0.0033 (7) |
N4 | 0.0751 (14) | 0.0463 (11) | 0.0503 (11) | −0.0009 (10) | 0.0371 (10) | −0.0048 (9) |
C1 | 0.0324 (9) | 0.0290 (8) | 0.0245 (8) | −0.0014 (7) | 0.0051 (7) | −0.0006 (6) |
C2 | 0.0315 (9) | 0.0317 (9) | 0.0282 (8) | 0.0009 (7) | 0.0064 (7) | 0.0000 (7) |
C3 | 0.0403 (10) | 0.0300 (9) | 0.0293 (9) | −0.0002 (7) | 0.0126 (7) | −0.0008 (7) |
C4 | 0.0443 (11) | 0.0446 (11) | 0.0302 (9) | −0.0107 (9) | 0.0161 (8) | −0.0102 (8) |
C5 | 0.0375 (9) | 0.0342 (9) | 0.0291 (9) | −0.0027 (8) | 0.0106 (7) | −0.0035 (7) |
C6 | 0.0314 (9) | 0.0351 (9) | 0.0341 (9) | 0.0017 (7) | 0.0068 (7) | −0.0024 (7) |
C7 | 0.0435 (10) | 0.0285 (9) | 0.0265 (8) | −0.0031 (7) | 0.0104 (7) | −0.0038 (7) |
C8 | 0.0424 (11) | 0.0508 (12) | 0.0389 (10) | 0.0016 (9) | 0.0076 (9) | −0.0100 (9) |
C9 | 0.0482 (12) | 0.0608 (14) | 0.0578 (14) | 0.0015 (11) | 0.0184 (11) | −0.0169 (11) |
C10 | 0.0708 (16) | 0.0532 (13) | 0.0468 (12) | −0.0082 (12) | 0.0300 (11) | −0.0159 (10) |
C11 | 0.0783 (16) | 0.0415 (11) | 0.0284 (10) | −0.0085 (11) | 0.0108 (10) | −0.0073 (8) |
C12 | 0.0532 (12) | 0.0350 (10) | 0.0309 (9) | −0.0040 (9) | 0.0042 (8) | −0.0038 (8) |
C13 | 0.0334 (10) | 0.0551 (13) | 0.0590 (13) | −0.0064 (9) | 0.0149 (9) | −0.0142 (11) |
C14 | 0.0379 (9) | 0.0302 (9) | 0.0299 (9) | −0.0028 (7) | 0.0116 (7) | −0.0045 (7) |
C15 | 0.0404 (10) | 0.0378 (10) | 0.0368 (10) | 0.0034 (8) | 0.0105 (8) | 0.0016 (8) |
C16 | 0.0399 (10) | 0.0454 (11) | 0.0476 (12) | 0.0034 (9) | 0.0188 (9) | −0.0042 (9) |
C17 | 0.0566 (12) | 0.0367 (10) | 0.0345 (10) | −0.0070 (9) | 0.0249 (9) | −0.0056 (8) |
C18 | 0.0631 (13) | 0.0359 (10) | 0.0386 (10) | 0.0081 (10) | 0.0186 (10) | 0.0052 (8) |
C19 | 0.0463 (11) | 0.0354 (10) | 0.0414 (10) | 0.0101 (8) | 0.0181 (9) | 0.0016 (8) |
Geometric parameters (Å, º) top
O1—C5 | 1.227 (2) | C8—C9 | 1.386 (3) |
O2—N4 | 1.210 (3) | C8—H8 | 0.95 |
O3—N4 | 1.222 (3) | C9—C10 | 1.372 (4) |
N1—C5 | 1.359 (2) | C9—H9 | 0.95 |
N1—C1 | 1.389 (2) | C10—C11 | 1.376 (3) |
N1—H1 | 0.94 (2) | C10—H10 | 0.95 |
N2—C1 | 1.350 (2) | C11—C12 | 1.387 (3) |
N2—N3 | 1.380 (2) | C11—H11 | 0.95 |
N2—C7 | 1.432 (2) | C12—H12 | 0.95 |
N3—C6 | 1.335 (3) | C13—H13A | 0.98 |
N4—C17 | 1.473 (3) | C13—H13B | 0.98 |
C1—C2 | 1.364 (3) | C13—H13C | 0.98 |
C2—C6 | 1.415 (3) | C14—C15 | 1.384 (3) |
C2—C3 | 1.508 (3) | C14—C19 | 1.386 (3) |
C3—C14 | 1.523 (3) | C15—C16 | 1.385 (3) |
C3—C4 | 1.540 (3) | C15—H15 | 0.95 |
C3—H3 | 1.00 | C16—C17 | 1.381 (3) |
C4—C5 | 1.514 (3) | C16—H16 | 0.95 |
C4—H4A | 0.99 | C17—C18 | 1.372 (3) |
C4—H4B | 0.99 | C18—C19 | 1.382 (3) |
C6—C13 | 1.493 (3) | C18—H18 | 0.95 |
C7—C8 | 1.382 (3) | C19—H19 | 0.95 |
C7—C12 | 1.382 (3) | | |
| | | |
C5—N1—C1 | 119.20 (15) | C7—C8—H8 | 120.2 |
C5—N1—H1 | 115.4 (15) | C9—C8—H8 | 120.2 |
C1—N1—H1 | 124.9 (14) | C10—C9—C8 | 119.7 (2) |
C1—N2—N3 | 110.59 (14) | C10—C9—H9 | 120.2 |
C1—N2—C7 | 128.79 (16) | C8—C9—H9 | 120.2 |
N3—N2—C7 | 120.62 (15) | C9—C10—C11 | 120.6 (2) |
C6—N3—N2 | 104.68 (15) | C9—C10—H10 | 119.7 |
O2—N4—O3 | 123.6 (2) | C11—C10—H10 | 119.7 |
O2—N4—C17 | 117.8 (2) | C10—C11—C12 | 120.5 (2) |
O3—N4—C17 | 118.7 (2) | C10—C11—H11 | 119.7 |
N2—C1—C2 | 108.81 (16) | C12—C11—H11 | 119.7 |
N2—C1—N1 | 125.63 (16) | C7—C12—C11 | 118.7 (2) |
C2—C1—N1 | 125.49 (16) | C7—C12—H12 | 120.7 |
C1—C2—C6 | 104.26 (16) | C11—C12—H12 | 120.7 |
C1—C2—C3 | 120.13 (16) | C6—C13—H13A | 109.5 |
C6—C2—C3 | 135.54 (16) | C6—C13—H13B | 109.5 |
C2—C3—C14 | 112.33 (16) | H13A—C13—H13B | 109.5 |
C2—C3—C4 | 107.78 (14) | C6—C13—H13C | 109.5 |
C14—C3—C4 | 112.40 (16) | H13A—C13—H13C | 109.5 |
C2—C3—H3 | 108.1 | H13B—C13—H13C | 109.5 |
C14—C3—H3 | 108.1 | C15—C14—C19 | 118.91 (17) |
C4—C3—H3 | 108.1 | C15—C14—C3 | 119.45 (17) |
C5—C4—C3 | 115.99 (16) | C19—C14—C3 | 121.51 (17) |
C5—C4—H4A | 108.3 | C14—C15—C16 | 121.06 (19) |
C3—C4—H4A | 108.3 | C14—C15—H15 | 119.5 |
C5—C4—H4B | 108.3 | C16—C15—H15 | 119.5 |
C3—C4—H4B | 108.3 | C17—C16—C15 | 118.12 (19) |
H4A—C4—H4B | 107.4 | C17—C16—H16 | 120.9 |
O1—C5—N1 | 121.19 (16) | C15—C16—H16 | 120.9 |
O1—C5—C4 | 121.47 (16) | C18—C17—C16 | 122.43 (18) |
N1—C5—C4 | 117.17 (16) | C18—C17—N4 | 118.02 (19) |
N3—C6—C2 | 111.64 (16) | C16—C17—N4 | 119.54 (19) |
N3—C6—C13 | 119.31 (17) | C17—C18—C19 | 118.30 (19) |
C2—C6—C13 | 129.01 (17) | C17—C18—H18 | 120.8 |
C8—C7—C12 | 120.87 (18) | C19—C18—H18 | 120.8 |
C8—C7—N2 | 119.04 (17) | C18—C19—C14 | 121.14 (19) |
C12—C7—N2 | 120.07 (18) | C18—C19—H19 | 119.4 |
C7—C8—C9 | 119.7 (2) | C14—C19—H19 | 119.4 |
| | | |
C1—N2—N3—C6 | −1.07 (19) | N3—N2—C7—C8 | −130.46 (19) |
C7—N2—N3—C6 | 178.58 (15) | C1—N2—C7—C12 | −129.4 (2) |
N3—N2—C1—C2 | 0.9 (2) | N3—N2—C7—C12 | 51.0 (2) |
C7—N2—C1—C2 | −178.66 (17) | C12—C7—C8—C9 | 2.3 (3) |
N3—N2—C1—N1 | −176.16 (16) | N2—C7—C8—C9 | −176.18 (19) |
C7—N2—C1—N1 | 4.2 (3) | C7—C8—C9—C10 | −1.3 (4) |
C5—N1—C1—N2 | −172.89 (17) | C8—C9—C10—C11 | −0.3 (4) |
C5—N1—C1—C2 | 10.5 (3) | C9—C10—C11—C12 | 1.0 (4) |
N2—C1—C2—C6 | −0.4 (2) | C8—C7—C12—C11 | −1.7 (3) |
N1—C1—C2—C6 | 176.69 (17) | N2—C7—C12—C11 | 176.81 (17) |
N2—C1—C2—C3 | −177.72 (15) | C10—C11—C12—C7 | 0.0 (3) |
N1—C1—C2—C3 | −0.6 (3) | C2—C3—C14—C15 | −104.8 (2) |
C1—C2—C3—C14 | −149.58 (17) | C4—C3—C14—C15 | 133.41 (19) |
C6—C2—C3—C14 | 34.2 (3) | C2—C3—C14—C19 | 71.0 (2) |
C1—C2—C3—C4 | −25.2 (2) | C4—C3—C14—C19 | −50.8 (2) |
C6—C2—C3—C4 | 158.5 (2) | C19—C14—C15—C16 | −1.9 (3) |
C2—C3—C4—C5 | 42.6 (2) | C3—C14—C15—C16 | 174.05 (18) |
C14—C3—C4—C5 | 166.95 (16) | C14—C15—C16—C17 | 1.1 (3) |
C1—N1—C5—O1 | −175.70 (17) | C15—C16—C17—C18 | 0.8 (3) |
C1—N1—C5—C4 | 9.0 (3) | C15—C16—C17—N4 | −178.32 (18) |
C3—C4—C5—O1 | 147.80 (19) | O2—N4—C17—C18 | −162.7 (2) |
C3—C4—C5—N1 | −36.9 (3) | O3—N4—C17—C18 | 16.9 (3) |
N2—N3—C6—C2 | 0.8 (2) | O2—N4—C17—C16 | 16.4 (3) |
N2—N3—C6—C13 | −177.30 (17) | O3—N4—C17—C16 | −163.9 (2) |
C1—C2—C6—N3 | −0.3 (2) | C16—C17—C18—C19 | −1.7 (3) |
C3—C2—C6—N3 | 176.41 (19) | N4—C17—C18—C19 | 177.38 (19) |
C1—C2—C6—C13 | 177.6 (2) | C17—C18—C19—C14 | 0.9 (3) |
C3—C2—C6—C13 | −5.7 (4) | C15—C14—C19—C18 | 0.9 (3) |
C1—N2—C7—C8 | 49.1 (3) | C3—C14—C19—C18 | −174.95 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O3i | 0.99 | 2.59 | 3.465 (5) | 148 |
C12—H12···O3ii | 0.95 | 2.58 | 3.285 (4) | 131 |
C16—H16···O2iii | 0.95 | 2.53 | 3.437 (3) | 160 |
N1—H1···O1iv | 0.94 (2) | 1.87 (2) | 2.814 (3) | 177 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z−1; (iii) −x, −y+1, −z+2; (iv) −x+2, −y+1, −z+1. |