organic compounds
1-Methyl-2-(4-methylphenyl)-4-morpholinopyridazine-3,6(1H,2H)-dione
aDepartment of Organic Chemistry, Poznan University of Medical Sciences, ul. Grunwaldzka 6, 60-780 Poznań, Poland, and bOptics Division, Faculty of Physics, A. Mickiewicz University, ul. Umultowska 85, 61-614 Poznań, Poland
*Correspondence e-mail: akgzella@ump.edu.pl
The structure analysis of the title compound, C16H19N3O3, has been undertaken in order to facilitate the interpretation of 1H and 13C NMR data and to determine the position of the morpholine residue in this nucleophilic substitution product. The main result is that the morpholine group, with a chair conformation, is connected at the 4-position of the pyridazine ring. The benzene and pyridazine rings make a dihedral angle of 62.17 (5)°. Molecules are linked into a two-dimensional network by non-classical C—H⋯O hydrogen bonds, in which O atoms serve as double or triple acceptors.
Related literature
For related literature, see: Allen et al. (1987); Bałoniak & Melzer (1979); Katrusiak et al. (2002).
Experimental
Crystal data
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Data collection: KM-4 Software (Kuma, 1996); cell KM-4 Software; data reduction: KM-4 Software; 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); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536808000111/cf2177sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808000111/cf2177Isup2.hkl
Compound (I) was synthesized according to a literature procedure of Bałoniak & Melzer (1979). Crystals suitable for single-crystal X-ray
were grown from ethanol by slow evaporation.All H atoms were placed in geometrically calculated positions and were refined with a riding model with C—H = 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H. The methyl groups were refined as rigid groups, allowed to rotate. The crystal polarity of (I) was established by
of the Flack (1983) parameter. The relatively large s.u. of the is due to the small contribution of atoms with measurable effects.Data collection: KM-4 Software (Kuma, 1996); cell
KM-4 Software (Kuma, 1996); data reduction: KM-4 Software (Kuma, 1996); 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); software used to prepare material for publication: WinGX (Farrugia, 1999).C16H19N3O3 | F(000) = 320 |
Mr = 301.34 | Dx = 1.345 Mg m−3 |
Monoclinic, P21 | Melting point = 475–476 K |
Hall symbol: P 2yb | Cu Kα radiation, λ = 1.54178 Å |
a = 5.6246 (6) Å | Cell parameters from 53 reflections |
b = 8.8923 (6) Å | θ = 14.8–30.5° |
c = 15.0842 (10) Å | µ = 0.78 mm−1 |
β = 99.530 (7)° | T = 293 K |
V = 744.03 (11) Å3 | Block, colourless |
Z = 2 | 0.38 × 0.35 × 0.30 mm |
Kuma Diffraction KM-4 diffractometer | 2646 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 70.1°, θmin = 3.0° |
ω–2θ scans | h = −6→6 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.716, Tmax = 0.794 | l = 0→18 |
2796 measured reflections | 2 standard reflections every 100 reflections |
2705 independent reflections | intensity decay: <2% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0538P)2 + 0.0723P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.082 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.15 e Å−3 |
2705 reflections | Δρmin = −0.13 e Å−3 |
202 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0345 (18) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983); 1249 Fiedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.07 (16) |
C16H19N3O3 | V = 744.03 (11) Å3 |
Mr = 301.34 | Z = 2 |
Monoclinic, P21 | Cu Kα radiation |
a = 5.6246 (6) Å | µ = 0.78 mm−1 |
b = 8.8923 (6) Å | T = 293 K |
c = 15.0842 (10) Å | 0.38 × 0.35 × 0.30 mm |
β = 99.530 (7)° |
Kuma Diffraction KM-4 diffractometer | 2646 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.025 |
Tmin = 0.716, Tmax = 0.794 | 2 standard reflections every 100 reflections |
2796 measured reflections | intensity decay: <2% |
2705 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.082 | Δρmax = 0.15 e Å−3 |
S = 1.07 | Δρmin = −0.13 e Å−3 |
2705 reflections | Absolute structure: Flack (1983); 1249 Fiedel pairs |
202 parameters | Absolute structure parameter: 0.07 (16) |
1 restraint |
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 | ||
N1 | 0.4950 (2) | 0.30562 (12) | 0.24834 (8) | 0.0381 (3) | |
N2 | 0.4743 (2) | 0.15882 (12) | 0.28125 (7) | 0.0339 (3) | |
C3 | 0.5939 (3) | 0.03738 (15) | 0.25416 (8) | 0.0325 (3) | |
C4 | 0.7375 (2) | 0.06485 (14) | 0.18118 (8) | 0.0300 (3) | |
C5 | 0.7609 (3) | 0.20788 (15) | 0.15387 (9) | 0.0359 (3) | |
H5 | 0.8658 | 0.2264 | 0.1135 | 0.043* | |
C6 | 0.6334 (3) | 0.33293 (15) | 0.18353 (9) | 0.0369 (3) | |
C7 | 0.3067 (3) | 0.41229 (19) | 0.25978 (12) | 0.0516 (4) | |
H7A | 0.3504 | 0.4642 | 0.3159 | 0.077* | |
H7B | 0.1577 | 0.3595 | 0.2596 | 0.077* | |
H7C | 0.2876 | 0.4837 | 0.2114 | 0.077* | |
C8 | 0.3819 (2) | 0.14755 (15) | 0.36480 (8) | 0.0326 (3) | |
C9 | 0.4878 (3) | 0.22780 (18) | 0.43950 (9) | 0.0426 (3) | |
H9 | 0.6209 | 0.2886 | 0.4367 | 0.051* | |
C10 | 0.3942 (3) | 0.2170 (2) | 0.51839 (10) | 0.0450 (4) | |
H10 | 0.4645 | 0.2717 | 0.5684 | 0.054* | |
C11 | 0.1978 (3) | 0.12600 (18) | 0.52421 (9) | 0.0408 (3) | |
C12 | 0.0964 (3) | 0.04506 (18) | 0.44820 (10) | 0.0425 (3) | |
H12 | −0.0346 | −0.0175 | 0.4510 | 0.051* | |
C13 | 0.1868 (3) | 0.05591 (17) | 0.36881 (9) | 0.0381 (3) | |
H13 | 0.1165 | 0.0018 | 0.3185 | 0.046* | |
C14 | 0.0953 (4) | 0.1141 (2) | 0.61008 (11) | 0.0581 (5) | |
H14A | 0.1592 | 0.0263 | 0.6427 | 0.087* | |
H14B | −0.0771 | 0.1064 | 0.5961 | 0.087* | |
H14C | 0.1385 | 0.2020 | 0.6461 | 0.087* | |
O15 | 0.5897 (2) | −0.08309 (11) | 0.29241 (7) | 0.0475 (3) | |
N16 | 0.8655 (2) | −0.05448 (13) | 0.15642 (7) | 0.0339 (3) | |
C17 | 0.7617 (3) | −0.20541 (15) | 0.13920 (9) | 0.0369 (3) | |
H17A | 0.6324 | −0.2196 | 0.1737 | 0.044* | |
H17B | 0.8843 | −0.2807 | 0.1582 | 0.044* | |
C18 | 0.6651 (3) | −0.22466 (16) | 0.04052 (10) | 0.0407 (3) | |
H18A | 0.6047 | −0.3264 | 0.0299 | 0.049* | |
H18B | 0.5311 | −0.1561 | 0.0234 | 0.049* | |
O19 | 0.8440 (2) | −0.19668 (12) | −0.01424 (7) | 0.0444 (3) | |
C20 | 0.9381 (3) | −0.04743 (17) | 0.00089 (9) | 0.0404 (3) | |
H20A | 0.8098 | 0.0252 | −0.0157 | 0.049* | |
H20B | 1.0604 | −0.0298 | −0.0363 | 0.049* | |
C21 | 1.0461 (3) | −0.02754 (16) | 0.09851 (9) | 0.0386 (3) | |
H21A | 1.1792 | −0.0972 | 0.1142 | 0.046* | |
H21B | 1.1088 | 0.0738 | 0.1082 | 0.046* | |
O22 | 0.6396 (2) | 0.46036 (12) | 0.15195 (8) | 0.0522 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0510 (7) | 0.0290 (6) | 0.0389 (6) | 0.0038 (5) | 0.0206 (5) | 0.0022 (5) |
N2 | 0.0453 (7) | 0.0291 (5) | 0.0311 (5) | −0.0018 (5) | 0.0176 (5) | 0.0000 (4) |
C3 | 0.0425 (7) | 0.0313 (6) | 0.0260 (5) | −0.0011 (5) | 0.0122 (5) | −0.0013 (5) |
C4 | 0.0367 (7) | 0.0308 (6) | 0.0236 (5) | −0.0012 (5) | 0.0083 (5) | −0.0018 (4) |
C5 | 0.0458 (8) | 0.0327 (7) | 0.0332 (6) | −0.0023 (6) | 0.0181 (5) | 0.0008 (5) |
C6 | 0.0489 (8) | 0.0287 (7) | 0.0362 (7) | −0.0036 (6) | 0.0157 (6) | −0.0004 (5) |
C7 | 0.0578 (10) | 0.0419 (8) | 0.0617 (9) | 0.0102 (7) | 0.0289 (8) | 0.0014 (7) |
C8 | 0.0383 (7) | 0.0353 (7) | 0.0268 (6) | −0.0004 (5) | 0.0131 (5) | −0.0021 (5) |
C9 | 0.0449 (9) | 0.0472 (8) | 0.0393 (7) | −0.0128 (6) | 0.0174 (6) | −0.0094 (6) |
C10 | 0.0507 (9) | 0.0540 (8) | 0.0324 (6) | −0.0070 (7) | 0.0131 (6) | −0.0121 (6) |
C11 | 0.0462 (8) | 0.0462 (8) | 0.0332 (7) | 0.0025 (6) | 0.0163 (6) | 0.0023 (6) |
C12 | 0.0399 (8) | 0.0488 (8) | 0.0418 (7) | −0.0085 (6) | 0.0153 (6) | 0.0005 (6) |
C13 | 0.0385 (7) | 0.0445 (8) | 0.0319 (6) | −0.0063 (6) | 0.0082 (5) | −0.0042 (5) |
C14 | 0.0687 (11) | 0.0728 (12) | 0.0394 (8) | −0.0065 (9) | 0.0278 (7) | 0.0017 (8) |
O15 | 0.0746 (7) | 0.0334 (5) | 0.0418 (5) | 0.0051 (5) | 0.0307 (5) | 0.0098 (4) |
N16 | 0.0431 (6) | 0.0301 (6) | 0.0311 (5) | −0.0007 (5) | 0.0140 (4) | −0.0022 (4) |
C17 | 0.0511 (8) | 0.0264 (6) | 0.0363 (7) | −0.0004 (6) | 0.0165 (6) | −0.0002 (5) |
C18 | 0.0489 (8) | 0.0350 (7) | 0.0415 (7) | −0.0048 (6) | 0.0173 (6) | −0.0072 (6) |
O19 | 0.0602 (7) | 0.0384 (6) | 0.0397 (5) | −0.0032 (5) | 0.0237 (5) | −0.0100 (4) |
C20 | 0.0514 (8) | 0.0364 (7) | 0.0389 (7) | −0.0003 (6) | 0.0234 (6) | −0.0009 (6) |
C21 | 0.0373 (7) | 0.0382 (7) | 0.0435 (7) | 0.0015 (6) | 0.0163 (5) | −0.0039 (6) |
O22 | 0.0788 (8) | 0.0287 (5) | 0.0565 (6) | 0.0005 (5) | 0.0326 (6) | 0.0058 (5) |
N1—C6 | 1.3686 (17) | C11—C14 | 1.5062 (18) |
N1—N2 | 1.4083 (15) | C12—C13 | 1.3796 (18) |
N1—C7 | 1.4530 (19) | C12—H12 | 0.930 |
N2—C3 | 1.3700 (18) | C13—H13 | 0.930 |
N2—C8 | 1.4440 (15) | C14—H14A | 0.960 |
C3—O15 | 1.2188 (17) | C14—H14B | 0.960 |
C3—C4 | 1.4897 (16) | C14—H14C | 0.960 |
C4—C5 | 1.3500 (18) | N16—C21 | 1.4648 (15) |
C4—N16 | 1.3685 (17) | N16—C17 | 1.4696 (17) |
C5—C6 | 1.4344 (19) | C17—C18 | 1.507 (2) |
C5—H5 | 0.930 | C17—H17A | 0.970 |
C6—O22 | 1.2319 (18) | C17—H17B | 0.970 |
C7—H7A | 0.960 | C18—O19 | 1.4256 (16) |
C7—H7B | 0.960 | C18—H18A | 0.970 |
C7—H7C | 0.960 | C18—H18B | 0.970 |
C8—C13 | 1.376 (2) | O19—C20 | 1.4330 (18) |
C8—C9 | 1.3826 (19) | C20—C21 | 1.507 (2) |
C9—C10 | 1.3819 (18) | C20—H20A | 0.970 |
C9—H9 | 0.930 | C20—H20B | 0.970 |
C10—C11 | 1.384 (2) | C21—H21A | 0.970 |
C10—H10 | 0.930 | C21—H21B | 0.970 |
C11—C12 | 1.393 (2) | ||
C6—N1—N2 | 120.42 (11) | C11—C12—H12 | 119.4 |
C6—N1—C7 | 118.75 (12) | C8—C13—C12 | 119.38 (12) |
N2—N1—C7 | 117.31 (11) | C8—C13—H13 | 120.3 |
C3—N2—N1 | 123.52 (11) | C12—C13—H13 | 120.3 |
C3—N2—C8 | 118.10 (11) | C11—C14—H14A | 109.5 |
N1—N2—C8 | 115.76 (10) | C11—C14—H14B | 109.5 |
O15—C3—N2 | 120.18 (11) | H14A—C14—H14B | 109.5 |
O15—C3—C4 | 123.32 (12) | C11—C14—H14C | 109.5 |
N2—C3—C4 | 116.39 (11) | H14A—C14—H14C | 109.5 |
C5—C4—N16 | 124.41 (12) | H14B—C14—H14C | 109.5 |
C5—C4—C3 | 118.17 (11) | C4—N16—C21 | 118.94 (11) |
N16—C4—C3 | 116.66 (11) | C4—N16—C17 | 123.00 (11) |
C4—C5—C6 | 123.79 (12) | C21—N16—C17 | 109.79 (10) |
C4—C5—H5 | 118.1 | N16—C17—C18 | 110.23 (11) |
C6—C5—H5 | 118.1 | N16—C17—H17A | 109.6 |
O22—C6—N1 | 119.68 (12) | C18—C17—H17A | 109.6 |
O22—C6—C5 | 123.02 (12) | N16—C17—H17B | 109.6 |
N1—C6—C5 | 117.28 (11) | C18—C17—H17B | 109.6 |
N1—C7—H7A | 109.5 | H17A—C17—H17B | 108.1 |
N1—C7—H7B | 109.5 | O19—C18—C17 | 112.26 (12) |
H7A—C7—H7B | 109.5 | O19—C18—H18A | 109.2 |
N1—C7—H7C | 109.5 | C17—C18—H18A | 109.2 |
H7A—C7—H7C | 109.5 | O19—C18—H18B | 109.2 |
H7B—C7—H7C | 109.5 | C17—C18—H18B | 109.2 |
C13—C8—C9 | 120.59 (12) | H18A—C18—H18B | 107.9 |
C13—C8—N2 | 118.96 (11) | C18—O19—C20 | 110.30 (10) |
C9—C8—N2 | 120.45 (12) | O19—C20—C21 | 110.04 (12) |
C10—C9—C8 | 119.45 (14) | O19—C20—H20A | 109.7 |
C10—C9—H9 | 120.3 | C21—C20—H20A | 109.7 |
C8—C9—H9 | 120.3 | O19—C20—H20B | 109.7 |
C9—C10—C11 | 121.15 (14) | C21—C20—H20B | 109.7 |
C9—C10—H10 | 119.4 | H20A—C20—H20B | 108.2 |
C11—C10—H10 | 119.4 | N16—C21—C20 | 110.87 (11) |
C10—C11—C12 | 118.17 (12) | N16—C21—H21A | 109.5 |
C10—C11—C14 | 121.26 (14) | C20—C21—H21A | 109.5 |
C12—C11—C14 | 120.57 (15) | N16—C21—H21B | 109.5 |
C13—C12—C11 | 121.25 (13) | C20—C21—H21B | 109.5 |
C13—C12—H12 | 119.4 | H21A—C21—H21B | 108.1 |
C6—N1—N2—C3 | 2.4 (2) | N1—N2—C8—C9 | −53.57 (18) |
C7—N1—N2—C3 | 160.94 (14) | C13—C8—C9—C10 | −0.8 (2) |
C6—N1—N2—C8 | 163.62 (12) | N2—C8—C9—C10 | 179.08 (14) |
C7—N1—N2—C8 | −37.79 (18) | C8—C9—C10—C11 | 0.7 (3) |
N1—N2—C3—O15 | 171.72 (13) | C9—C10—C11—C12 | 0.1 (3) |
C8—N2—C3—O15 | 10.9 (2) | C9—C10—C11—C14 | −179.93 (16) |
N1—N2—C3—C4 | −4.50 (19) | C10—C11—C12—C13 | −0.7 (2) |
C8—N2—C3—C4 | −165.37 (11) | C14—C11—C12—C13 | 179.35 (15) |
O15—C3—C4—C5 | −169.22 (15) | C9—C8—C13—C12 | 0.3 (2) |
N2—C3—C4—C5 | 6.88 (19) | N2—C8—C13—C12 | −179.65 (13) |
O15—C3—C4—N16 | 1.3 (2) | C11—C12—C13—C8 | 0.5 (2) |
N2—C3—C4—N16 | 177.35 (12) | C5—C4—N16—C21 | 1.9 (2) |
N16—C4—C5—C6 | −177.11 (13) | C3—C4—N16—C21 | −167.96 (11) |
C3—C4—C5—C6 | −7.4 (2) | C5—C4—N16—C17 | −143.29 (14) |
N2—N1—C6—O22 | 176.13 (14) | C3—C4—N16—C17 | 46.90 (17) |
C7—N1—C6—O22 | 17.8 (2) | C4—N16—C17—C18 | 93.59 (14) |
N2—N1—C6—C5 | −2.2 (2) | C21—N16—C17—C18 | −54.29 (15) |
C7—N1—C6—C5 | −160.51 (14) | N16—C17—C18—O19 | 55.96 (15) |
C4—C5—C6—O22 | −173.17 (15) | C17—C18—O19—C20 | −58.23 (16) |
C4—C5—C6—N1 | 5.1 (2) | C18—O19—C20—C21 | 58.88 (15) |
C3—N2—C8—C13 | −71.32 (17) | C4—N16—C21—C20 | −92.81 (14) |
N1—N2—C8—C13 | 126.34 (14) | C17—N16—C21—C20 | 56.56 (15) |
C3—N2—C8—C9 | 108.77 (16) | O19—C20—C21—N16 | −58.94 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17A···O15 | 0.97 | 2.21 | 2.8636 (18) | 124 |
C10—H10···O15i | 0.93 | 2.53 | 3.3508 (19) | 148 |
C14—H14C···O15i | 0.96 | 2.53 | 3.419 (2) | 155 |
C5—H5···O19ii | 0.93 | 2.49 | 3.4124 (19) | 174 |
C21—H21B···O19ii | 0.97 | 2.52 | 3.3036 (18) | 137 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+2, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C16H19N3O3 |
Mr | 301.34 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 5.6246 (6), 8.8923 (6), 15.0842 (10) |
β (°) | 99.530 (7) |
V (Å3) | 744.03 (11) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.38 × 0.35 × 0.30 |
Data collection | |
Diffractometer | Kuma Diffraction KM-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.716, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2796, 2705, 2646 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.082, 1.07 |
No. of reflections | 2705 |
No. of parameters | 202 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.13 |
Absolute structure | Flack (1983); 1249 Fiedel pairs |
Absolute structure parameter | 0.07 (16) |
Computer programs: KM-4 Software (Kuma, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C17—H17A···O15 | 0.97 | 2.21 | 2.8636 (18) | 124 |
C10—H10···O15i | 0.93 | 2.53 | 3.3508 (19) | 148 |
C14—H14C···O15i | 0.96 | 2.53 | 3.419 (2) | 155 |
C5—H5···O19ii | 0.93 | 2.49 | 3.4124 (19) | 174 |
C21—H21B···O19ii | 0.97 | 2.52 | 3.3036 (18) | 137 |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+2, y+1/2, −z. |
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bałoniak, S. & Melzer, E. (1979). Acta Pol. Pharm. 36, 147–154. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Katrusiak, A. A., Katrusiak, A., Bałoniak, S. & Zielińska, K. (2002). Pol. J. Chem. 76, 45–56. CAS Google Scholar
Kuma (1996). KM-4 User's Guide. Version 8.0.1. Kuma Diffraction, Wrocław, Poland. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Treatment of 4-bromo-1-methyl-2-(4-methylphenyl)-3,6-pyridazinedione with morpholine in anhydrous ethanol gives a mixture of ipso and cine substitution products; one of them, labelled as (I), was found as a precipitate (Bałoniak & Melzer, 1979). The crystal structure determination of (I) was carried out in order to facilitate the interpretation of 1H and 13C NMR data, to determine the position of the morpholine residue on the pyridazinedione ring, and to study the nature of the hydrogen-bond formation in the crystalline state.
The X-ray analysis revealed the molecular structure of (I) and its conformation and distortions induced in the pyridazine ring by substituents.
The geometry of the molecule of (I) is illustrated in Fig. 1. The pyridazine ring is nearly planar with an r.m.s. deviation of 0.0211 Å. The methyl, p-methylphenyl and morpholine substituents are connected at N1, N2 and C4, respectively. The mean plane of the benzene ring is oriented at an angle of 62.17 (5)° to the mean plane of the pyridazine ring. The C4—C5 bond, 1.3500 (18) Å, belonging to the latter ring, is a double bond.
The ring bonds are conjugated, and the formally single bond C5—C6 is shorter by about 14 and the bond C3—C4 is longer by about 13σ than the normal (C?)Csp2—Csp2(?O) single bond [1.465 (1) Å; Allen et al., 1987]. The elongation of the latter is a result of the presence of the morpholine residue at C4. The last two observations are consistent with that reported for 2-methyl-4-morpholino-1-phenyl-3,6-pyridazinedione (Katrusiak et al., 2002).
The C3—N1 and C6—N1 distances are similar [1.3700 (18) and 1.3686 (17) Å, respectively] and are somewhat larger than a normal C—N tertiary amide distance [1.346 (5) Å; Allen et al., 1987]. The sums of valency angles around N1 and N2 atoms are 356.5 and 357.4°. Atom C7 of the methyl group has a mutual orientation of synperiplanar and synclinal with respect to the atom C8 of the benzene ring [torsion angle C7—N1—N2—C8 = -37.79 (18)°].
The molecules in the crystal structure of (I) are linked via non-classical C—H···O hydrogen bonds (Table 1), forming a two-dimensional hydrogen-bond network parallel to the (101) plane (Figs. 2 and 3).