Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199015231/sk1336sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199015231/sk1336Isup2.hkl |
CCDC reference: 143251
A suspension of 5-bromo-6-phenyl-3(2H)-pyridazinone (0.5 g, 1.9 mmol), ammonium chloride (0.3 g, 5.6 mmol) and ammonium hydroxide (50 ml) was heated at 458 K at pressure of 374 psi (1psi ≈ 6.895 kPa) for 3 h in a Parr reactor. The mixture was evaporated in vacuo and washed with ammonium hydroxide, and the solid obtained, (I), was recrystallized from ethanol (yield 70%; m.p. 517 K). Spectroscopic analysis: IR (KBr), cm-1: 3480–3425 (NH), 1670 (CO); 1H NMR (DMSO-δ6, p.p.m.): δ d 12.12 (s, 1H, NH, deuterium oxide exchangeable), 7.50–7.43 (m, 5H, aromatics), 5.71 (s, 1H, CH—CO), 5.96 (s, 2H, NH2); 13C NMR, p.p.m.: d 162.5 (C3), 99.1 (C4), 149.2 (C5), 140.1 (C6), 134.4 (C1'), 129.1 (C2', C6'), 128.8 (C3', C5'), 129.1 (C4'); analysis calculated: C 64.16, H 4.85, N 22.45%; found: C 64.20, H 4.78, N 22.43%.
H atoms were calculated geometrically and included in the refinement, but were restrained to ride on their parent atoms, with isotropic displacement parameters fixed to 1.3 times Ueq of their parent atoms.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 1990), PARST (Nardelli, 1983, 1995) and PARSTCIF (Nardelli, 1992).
Fig. 1. A plot of (I) showing the atomic numbering scheme. Displacement ellipsoids are drawn at 50% probability level, and H atoms are shown as spheres of arbitrary radii. |
C10H9N3O | F(000) = 784 |
Mr = 187.20 | Dx = 1.309 Mg m−3 |
Orthorhombic, Pbca | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 8.752 (2) Å | θ = 10.8–28.1° |
b = 10.525 (5) Å | µ = 0.73 mm−1 |
c = 20.619 (5) Å | T = 293 K |
V = 1899.3 (11) Å3 | Prism, light green |
Z = 8 | 0.48 × 0.20 × 0.14 mm |
Siemens P4 four-circle diffractometer | 1102 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 57.2°, θmin = 4.3° |
2θ/ω scans | h = −1→9 |
Absorption correction: ψ-scan (North et al., 1968) | k = −1→11 |
Tmin = 0.626, Tmax = 0.903 | l = −1→22 |
1733 measured reflections | 3 standard reflections every 100 reflections |
1266 independent reflections | intensity decay: <1.0% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: Full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0532P)2 + 0.757P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.002 |
1266 reflections | Δρmax = 0.14 e Å−3 |
128 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0110 (8) |
C10H9N3O | V = 1899.3 (11) Å3 |
Mr = 187.20 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 8.752 (2) Å | µ = 0.73 mm−1 |
b = 10.525 (5) Å | T = 293 K |
c = 20.619 (5) Å | 0.48 × 0.20 × 0.14 mm |
Siemens P4 four-circle diffractometer | 1102 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.024 |
Tmin = 0.626, Tmax = 0.903 | θmax = 57.2° |
1733 measured reflections | 3 standard reflections every 100 reflections |
1266 independent reflections | intensity decay: <1.0% |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.14 e Å−3 |
1266 reflections | Δρmin = −0.14 e Å−3 |
128 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. The structure was solved by direct methods and Fourier synthesis. Non-H atoms were refined anisotropically by full-matrix least-squares techniques. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.11598 (15) | 0.12824 (13) | 0.02499 (7) | 0.0510 (5) | |
N1 | 0.17603 (17) | −0.02452 (14) | −0.04753 (7) | 0.0394 (5) | |
N2 | 0.26660 (17) | −0.08609 (15) | −0.08973 (7) | 0.0385 (5) | |
N3 | 0.59357 (19) | 0.12476 (17) | −0.08433 (9) | 0.0503 (6) | |
C1 | 0.2131 (2) | 0.08360 (17) | −0.01433 (9) | 0.0361 (6) | |
C2 | 0.3567 (2) | 0.13477 (17) | −0.02767 (9) | 0.0375 (6) | |
C3 | 0.4539 (2) | 0.07773 (17) | −0.07128 (9) | 0.0348 (6) | |
C4 | 0.4014 (2) | −0.03863 (17) | −0.10159 (8) | 0.0346 (6) | |
C5 | 0.4959 (2) | −0.11395 (19) | −0.14795 (9) | 0.0387 (6) | |
C6 | 0.5656 (3) | −0.0585 (2) | −0.20123 (10) | 0.0550 (8) | |
C7 | 0.6450 (3) | −0.1341 (3) | −0.24540 (12) | 0.0736 (10) | |
C8 | 0.6569 (3) | −0.2625 (3) | −0.23604 (13) | 0.0767 (10) | |
C9 | 0.5887 (3) | −0.3180 (3) | −0.18367 (12) | 0.0635 (9) | |
C10 | 0.5084 (2) | −0.2448 (2) | −0.13948 (10) | 0.0481 (7) | |
H1 | 0.08672 | −0.05595 | −0.04081 | 0.0512* | |
H2 | 0.38729 | 0.20876 | −0.00671 | 0.0487* | |
H3A | 0.62458 | 0.19259 | −0.06515 | 0.0654* | |
H3B | 0.65179 | 0.08699 | −0.11184 | 0.0654* | |
H6 | 0.55937 | 0.02884 | −0.20754 | 0.0715* | |
H7 | 0.69038 | −0.09698 | −0.28152 | 0.0957* | |
H8 | 0.71141 | −0.31196 | −0.26538 | 0.0999* | |
H9 | 0.59621 | −0.40536 | −0.17765 | 0.0826* | |
H10 | 0.46255 | −0.28333 | −0.10386 | 0.0626* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0381 (8) | 0.0439 (9) | 0.0709 (10) | −0.0002 (6) | 0.0115 (7) | −0.0187 (7) |
N1 | 0.0320 (9) | 0.0355 (10) | 0.0506 (9) | −0.0025 (7) | 0.0050 (7) | −0.0081 (7) |
N2 | 0.0359 (9) | 0.0363 (9) | 0.0432 (9) | −0.0014 (7) | 0.0036 (7) | −0.0069 (7) |
N3 | 0.0392 (10) | 0.0461 (11) | 0.0657 (12) | −0.0100 (8) | 0.0110 (8) | −0.0147 (9) |
C1 | 0.0352 (10) | 0.0274 (10) | 0.0458 (11) | 0.0048 (8) | −0.0012 (8) | −0.0030 (8) |
C2 | 0.0359 (10) | 0.0268 (10) | 0.0498 (11) | −0.0001 (8) | −0.0026 (9) | −0.0050 (8) |
C3 | 0.0329 (10) | 0.0302 (10) | 0.0412 (10) | 0.0002 (8) | −0.0019 (8) | 0.0031 (8) |
C4 | 0.0363 (11) | 0.0315 (11) | 0.0361 (10) | −0.0006 (8) | −0.0001 (8) | −0.0008 (8) |
C5 | 0.0345 (10) | 0.0429 (12) | 0.0388 (10) | −0.0018 (9) | −0.0005 (8) | −0.0050 (9) |
C6 | 0.0555 (13) | 0.0609 (14) | 0.0485 (12) | −0.0034 (12) | 0.0095 (10) | −0.0031 (11) |
C7 | 0.0655 (16) | 0.100 (2) | 0.0552 (14) | −0.0064 (15) | 0.0222 (12) | −0.0095 (15) |
C8 | 0.0595 (16) | 0.096 (2) | 0.0746 (18) | 0.0097 (15) | 0.0132 (13) | −0.0373 (16) |
C9 | 0.0577 (14) | 0.0575 (15) | 0.0754 (16) | 0.0120 (12) | −0.0010 (13) | −0.0252 (13) |
C10 | 0.0478 (12) | 0.0457 (13) | 0.0508 (12) | −0.0003 (10) | 0.0003 (9) | −0.0097 (10) |
O1—C1 | 1.265 (2) | C5—C10 | 1.393 (3) |
N1—N2 | 1.344 (2) | C5—C6 | 1.385 (3) |
N1—C1 | 1.367 (2) | C6—C7 | 1.395 (4) |
N2—C4 | 1.304 (2) | C7—C8 | 1.369 (4) |
N3—C3 | 1.346 (3) | C8—C9 | 1.365 (4) |
N1—H1 | 0.8600 | C9—C10 | 1.385 (3) |
N3—H3A | 0.8601 | C2—H2 | 0.9300 |
N3—H3B | 0.8599 | C6—H6 | 0.9300 |
C1—C2 | 1.395 (3) | C7—H7 | 0.9301 |
C2—C3 | 1.376 (3) | C8—H8 | 0.9298 |
C3—C4 | 1.450 (3) | C9—H9 | 0.9301 |
C4—C5 | 1.492 (3) | C10—H10 | 0.9300 |
O1···N3i | 2.880 (3) | C5···H7vii | 3.0490 |
O1···C2i | 3.373 (3) | C6···H3B | 2.5122 |
O1···N1ii | 2.818 (2) | C9···H6viii | 3.0512 |
O1···H2i | 2.6629 | C9···H3Bix | 2.8900 |
O1···H3Ai | 2.0609 | H1···O1ii | 1.9577 |
O1···H1ii | 1.9577 | H1···C1ii | 2.8745 |
O1···H10iii | 2.8978 | H1···H1ii | 2.5541 |
N1···O1ii | 2.818 (2) | H1···H2iv | 2.5843 |
N2···C2iv | 3.381 (3) | H2···H3A | 2.4070 |
N3···C6 | 3.097 (3) | H2···O1vi | 2.6629 |
N3···C1v | 3.437 (3) | H2···H1iii | 2.5843 |
N3···O1vi | 2.880 (3) | H3A···H2 | 2.4070 |
N2···H7vii | 2.7396 | H3A···O1vi | 2.0609 |
N2···H10 | 2.7084 | H3A···C1vi | 2.9723 |
N3···H6 | 2.7500 | H3B···C5 | 2.6246 |
C1···N3v | 3.437 (3) | H3B···C6 | 2.5122 |
C2···N2iii | 3.381 (3) | H3B···H6 | 2.2187 |
C2···C3v | 3.451 (3) | H3B···C9x | 2.8900 |
C2···C4v | 3.551 (3) | H3B···H9x | 2.5908 |
C2···O1vi | 3.373 (3) | H6···N3 | 2.7500 |
C3···C2v | 3.451 (3) | H6···C3 | 3.0017 |
C3···C3v | 3.460 (3) | H6···H3B | 2.2187 |
C4···C2v | 3.551 (3) | H6···C9xi | 3.0512 |
C6···N3 | 3.097 (3) | H7···N2xii | 2.7396 |
C1···H1ii | 2.8745 | H7···C4xii | 3.0979 |
C1···H10iii | 2.7808 | H7···C5xii | 3.0490 |
C1···H3Ai | 2.9723 | H9···H3Bix | 2.5908 |
C3···H6 | 3.0017 | H10···N2 | 2.7084 |
C4···H7vii | 3.0979 | H10···O1iv | 2.8978 |
C5···H3B | 2.6246 | H10···C1iv | 2.7808 |
N2—N1—C1 | 125.86 (15) | C4—C5—C10 | 119.25 (17) |
N1—N2—C4 | 118.06 (15) | C5—C6—C7 | 119.8 (2) |
N2—N1—H1 | 117.07 | C6—C7—C8 | 120.6 (2) |
C1—N1—H1 | 117.08 | C7—C8—C9 | 120.0 (3) |
C3—N3—H3A | 119.99 | C8—C9—C10 | 120.3 (3) |
H3A—N3—H3B | 120.00 | C5—C10—C9 | 120.5 (2) |
C3—N3—H3B | 120.00 | C1—C2—H2 | 119.41 |
O1—C1—C2 | 126.04 (17) | C3—C2—H2 | 119.42 |
N1—C1—C2 | 115.88 (16) | C5—C6—H6 | 120.10 |
O1—C1—N1 | 118.07 (16) | C7—C6—H6 | 120.11 |
C1—C2—C3 | 121.17 (17) | C6—C7—H7 | 119.73 |
N3—C3—C2 | 122.12 (17) | C8—C7—H7 | 119.67 |
N3—C3—C4 | 120.82 (16) | C7—C8—H8 | 120.00 |
C2—C3—C4 | 117.03 (16) | C9—C8—H8 | 119.96 |
C3—C4—C5 | 123.32 (16) | C8—C9—H9 | 119.85 |
N2—C4—C5 | 114.71 (16) | C10—C9—H9 | 119.87 |
N2—C4—C3 | 121.97 (16) | C5—C10—H10 | 119.76 |
C4—C5—C6 | 121.89 (18) | C9—C10—H10 | 119.74 |
C6—C5—C10 | 118.78 (18) | ||
C1—N1—N2—C4 | −1.3 (3) | C3—C4—C5—C10 | 132.03 (19) |
N2—N1—C1—O1 | −178.29 (16) | N2—C4—C5—C6 | 129.2 (2) |
N2—N1—C1—C2 | 1.9 (3) | N2—C4—C5—C10 | −47.5 (2) |
N1—N2—C4—C3 | −0.7 (2) | C3—C4—C5—C6 | −51.3 (3) |
N1—N2—C4—C5 | 178.87 (15) | C4—C5—C6—C7 | −176.1 (2) |
O1—C1—C2—C3 | 179.65 (19) | C10—C5—C6—C7 | 0.6 (3) |
N1—C1—C2—C3 | −0.6 (3) | C4—C5—C10—C9 | 176.60 (19) |
C1—C2—C3—N3 | −179.27 (18) | C6—C5—C10—C9 | −0.2 (3) |
C1—C2—C3—C4 | −1.1 (3) | C5—C6—C7—C8 | −1.1 (4) |
N3—C3—C4—N2 | 180.00 (1) | C6—C7—C8—C9 | 1.0 (4) |
C2—C3—C4—C5 | −177.67 (17) | C7—C8—C9—C10 | −0.6 (4) |
N3—C3—C4—C5 | 0.5 (3) | C8—C9—C10—C5 | 0.1 (3) |
C2—C3—C4—N2 | 1.8 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x, −y, −z; (iii) −x+1/2, y+1/2, z; (iv) −x+1/2, y−1/2, z; (v) −x+1, −y, −z; (vi) x+1/2, −y+1/2, −z; (vii) x−1/2, y, −z−1/2; (viii) −x+1, y−1/2, −z−1/2; (ix) −x+3/2, y−1/2, z; (x) −x+3/2, y+1/2, z; (xi) −x+1, y+1/2, −z−1/2; (xii) x+1/2, y, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1ii | 0.86 | 1.96 | 2.818 (2) | 180 |
N3—H3A···O1vi | 0.86 | 2.06 | 2.880 (3) | 159 |
Symmetry codes: (ii) −x, −y, −z; (vi) x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H9N3O |
Mr | 187.20 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.752 (2), 10.525 (5), 20.619 (5) |
V (Å3) | 1899.3 (11) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.48 × 0.20 × 0.14 |
Data collection | |
Diffractometer | Siemens P4 four-circle diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.626, 0.903 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1733, 1266, 1102 |
Rint | 0.024 |
θmax (°) | 57.2 |
(sin θ/λ)max (Å−1) | 0.545 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.104, 1.10 |
No. of reflections | 1266 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.14 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997a), DIAMOND (Bergerhoff, 1996), PLATON (Spek, 1990), PARST (Nardelli, 1983, 1995) and PARSTCIF (Nardelli, 1992).
O1—C1 | 1.265 (2) | N3—C3 | 1.346 (3) |
N1—N2 | 1.344 (2) | C1—C2 | 1.395 (3) |
N1—C1 | 1.367 (2) | C2—C3 | 1.376 (3) |
N2—C4 | 1.304 (2) | C3—C4 | 1.450 (3) |
N2—N1—C1 | 125.86 (15) | N3—C3—C2 | 122.12 (17) |
N1—N2—C4 | 118.06 (15) | N3—C3—C4 | 120.82 (16) |
O1—C1—C2 | 126.04 (17) | N2—C4—C5 | 114.71 (16) |
N1—C1—C2 | 115.88 (16) | N2—C4—C3 | 121.97 (16) |
O1—C1—N1 | 118.07 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 1.96 | 2.818 (2) | 180 |
N3—H3A···O1ii | 0.86 | 2.06 | 2.880 (3) | 159 |
Symmetry codes: (i) −x, −y, −z; (ii) x+1/2, −y+1/2, −z. |
It is known that 6-aryl-3(2H)-pyridazinones and their 4,5-dihydro derivatives display several pharmacological activities, all of them related to cardiotonics, such as reduction of blood pressure, inhibition of platelet aggregation, positive inotropic activity, and others (Robertson et al., 1986). Likewise, 6-arylpyridazinones with nitro and acyl substituents at the 4- and 5- positions show good antiaggregating properties (Schudt et al., 1991). We have previously reported the synthesis of 5-aminomethyl-6-aryl-4,5-dihydropyridazinones and 6-aryl-5-aminomethyl-3(2H)-pyridazinones (Raviña et al., 1990). Some of these compounds show a good in vitro inhibitory activity on ADP-induced rat platelet aggregation. As a continuation of this previous report on the chemistry and pharmacology of this class of compounds, we carried out the crystal structure determination of 5-amino-6-phenyl-1,6-dihydropyridazin-3(2H)-one, (I). This enamine-like compound can be employed in the synthesis of hetero-condensed pyridazinones. Recently, we used this compound as an intermediate in the synthesis of pyrido[2,3-d]pyridazines (Pita et al., 1999). \scheme
There are no unusual bond distances and angles in (I), and they are in the range of calculated values using the AM1 method in related structures (Estevez et al., 1998). The bond lengths in the pyridazinone ring range from 1.304 (2) to 1.450 (3) Å. The torsion angle between the pyridazinone and the phenyl ring, found using the quantum chemical AM1 method in MOPAC (Stewart, 1990?) for the lower energy conformations, is in the range 40–140°, with a heat of formation of 38.30 Kcalmol-1. In the crystal structure this angle is -51.3 (3)°, which corresponds to the minimum in the energy calculations. The calculated favoured conformation of the enol form corresponds to torsion angles in the same range (40–140°) and a heat of formation of 34.20 Kcalmol-1, which shows that this enol is the predominant form at equilibrium. This is contrary to the fact that in the crystal the molecule is present in the amide form, which corresponds to a higher heat of formation. The dihedral angle between the respective least-squares planes of the pyridazinone ring and the phenyl ring is 49.5 (1)°. The mean Csp2—Csp2 bond length within the phenyl ring is 1.382 (1) Å.
The N3 atom of the amine and the N1 atom of the amide group in the pyridazinone ring are involved in two intermolecular hydrogen bonds with a neighbouring O1, forming an infinite two-dimensional network in the plane (001).