organic compounds
5-(3,4-Dimethoxybenzylidene)-1,3-dimethyl-1,3-diazinane-2,4,6-trione
aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
*Correspondence e-mail: muller.theunis@gmail.com
In the title compound, C15H16N2O5, the dihedral angle between 1,3-diazinane and benzene rings is only 4.27 (1)°. The essentially planar molecular structure is characterized by a short intramolecular C—H⋯O separation and by an exceptionally large bond angle of 138.25 (14)° at the bridging methine C atom. The methoxy groups deviate somewhat from the plane of the benzene ring, with C—C—O—C torsion angles of −15.6 (1) and 9.17 (6)°. In the crystal, molecules form centrosymmetric dimers via donor–acceptor π–π interactions, with a centroid–centroid distance of 3.401 (1) Å.
Related literature
For the biological activity of 1,3-diazinane derivatives, see: Negwar (2001); Tanaka et al. (1986, 1988). For the use of pyridine-type ligands in catalysis models, see: Roodt et al. (2011); van der Westhuizen et al. (2010). For related structures, see: Panchatcharam et al. (2009); Rezende et al. (2005). For the synthesis, see: Prajapati et al. (2006). For standard bond lengths, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenberg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536811052986/ld2039sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811052986/ld2039Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811052986/ld2039Isup3.cml
Mixture of N,N-dimethylbarbituric acid (0.50 g, 3.2 mmol) and 4,5-dimethoxy benzaldehyde (0.53 g, 3.2 mmol) in ethanol (10 ml) was stirred at room temperature until completion of the reaction (monitored by TLC). The solids that precipitated during the course of the reaction were filtered and washed with diethyl ether (5 ml). The precipitate was subsequently dissolved in hot acetonitrile. Upon cooling to room temperature with a slow evaporation of the acetonitrile the crystals (mp 229–230 °C) suitable for single-crystal X-ray diffraction were obtained.
1H NMR (600 MHz): 3.42 (s, 3H, N—Me), 3.43 (s, 3H, N—Me), 3.99 (s, 3H, OMe), 3.40 (s, 3H, OMe), 6.97 (d, 1H), 7.81 (dd, 1H), 8.41 (d, 1H), 8.51(s, 1H).
13C {1H} NMR (150Mz): 28.5, 29.1, 56.1, 56.2, 110.4, 114.2, 116.6, 125.9, 132.6, 148.4, 151.4, 154.4, 159.2, 161.1, 163.3.
The aromatic H atoms were positioned geometrically and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(parent) of the parent atom with a C—H distance of 0.93. The methyl H atoms were placed in geometrically idealized positions and constrained to ride on its parent atoms with Uiso(H) = 1.5Ueq(C) and at a distance of 0.96 Å; their torsion angles were optimized from electron density
Data collection: APEX2 (Bruker, 2008); cell
SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenberg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).C15H16N2O5 | Z = 2 |
Mr = 304.3 | F(000) = 320 |
Triclinic, P1 | Dx = 1.508 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3086 (2) Å | Cell parameters from 3146 reflections |
b = 8.4033 (3) Å | θ = 2.6–28.2° |
c = 11.8705 (5) Å | µ = 0.11 mm−1 |
α = 82.5685 (18)° | T = 100 K |
β = 77.6686 (17)° | Plate, yellow |
γ = 71.1469 (15)° | 0.15 × 0.12 × 0.06 mm |
V = 672.58 (4) Å3 |
Bruker APEXII CCD diffractometer | 2478 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 28°, θmin = 3.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −9→9 |
Tmin = 0.984, Tmax = 0.994 | k = −11→11 |
12172 measured reflections | l = −15→15 |
3233 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0512P)2 + 0.239P] where P = (Fo2 + 2Fc2)/3 |
3233 reflections | (Δ/σ)max = 0.003 |
203 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C15H16N2O5 | γ = 71.1469 (15)° |
Mr = 304.3 | V = 672.58 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.3086 (2) Å | Mo Kα radiation |
b = 8.4033 (3) Å | µ = 0.11 mm−1 |
c = 11.8705 (5) Å | T = 100 K |
α = 82.5685 (18)° | 0.15 × 0.12 × 0.06 mm |
β = 77.6686 (17)° |
Bruker APEXII CCD diffractometer | 3233 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2478 reflections with I > 2σ(I) |
Tmin = 0.984, Tmax = 0.994 | Rint = 0.032 |
12172 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
3233 reflections | Δρmin = −0.30 e Å−3 |
203 parameters |
Experimental. The intensity data was collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 15 s/frame. A total of 1821 frames were collected with a frame width of 0.5° covering up to θ = 28.18° with 99.7% completeness accomplished. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | ||
C1 | 0.4027 (2) | 0.72599 (19) | 0.80997 (12) | 0.0160 (3) | |
C2 | 0.5148 (2) | 0.43533 (18) | 0.75097 (12) | 0.0150 (3) | |
C3 | 0.61438 (19) | 0.49161 (18) | 0.63713 (12) | 0.0135 (3) | |
C4 | 0.59797 (19) | 0.67081 (18) | 0.61360 (12) | 0.0144 (3) | |
C5 | 0.70824 (19) | 0.36478 (18) | 0.56448 (12) | 0.0139 (3) | |
H5 | 0.6895 | 0.2635 | 0.5979 | 0.017* | |
C6 | 0.82904 (19) | 0.34247 (18) | 0.44990 (12) | 0.0138 (3) | |
C7 | 0.89371 (19) | 0.46673 (18) | 0.37541 (12) | 0.0142 (3) | |
H7 | 0.8572 | 0.576 | 0.3985 | 0.017* | |
C8 | 1.01025 (19) | 0.42763 (18) | 0.26903 (12) | 0.0138 (3) | |
C9 | 1.06655 (19) | 0.26239 (18) | 0.23180 (12) | 0.0142 (3) | |
C10 | 1.0028 (2) | 0.13956 (18) | 0.30414 (12) | 0.0160 (3) | |
H10 | 1.0382 | 0.0306 | 0.2807 | 0.019* | |
C11 | 0.8865 (2) | 0.17974 (18) | 0.41127 (12) | 0.0155 (3) | |
H11 | 0.8452 | 0.0963 | 0.459 | 0.019* | |
C12 | 0.4873 (2) | 0.95348 (18) | 0.68221 (13) | 0.0186 (3) | |
H12A | 0.3864 | 1.0081 | 0.6375 | 0.028* | |
H12B | 0.6109 | 0.9644 | 0.6403 | 0.028* | |
H12C | 0.4551 | 1.0052 | 0.7544 | 0.028* | |
C13 | 0.3059 (2) | 0.5045 (2) | 0.93915 (13) | 0.0215 (3) | |
H13A | 0.2832 | 0.5852 | 0.9949 | 0.032* | |
H13B | 0.3826 | 0.396 | 0.9664 | 0.032* | |
H13C | 0.1822 | 0.498 | 0.9283 | 0.032* | |
C14 | 0.9864 (2) | 0.71432 (18) | 0.21141 (14) | 0.0203 (3) | |
H14A | 0.8468 | 0.7402 | 0.2177 | 0.03* | |
H14B | 1.0356 | 0.7815 | 0.1479 | 0.03* | |
H14C | 1.0144 | 0.7384 | 0.2817 | 0.03* | |
C15 | 1.2176 (2) | 0.08217 (19) | 0.07552 (14) | 0.0215 (3) | |
H15A | 1.29 | −0.0087 | 0.122 | 0.032* | |
H15B | 1.2928 | 0.0848 | −0.0012 | 0.032* | |
H15C | 1.0949 | 0.0657 | 0.0724 | 0.032* | |
N1 | 0.41279 (17) | 0.55732 (16) | 0.82856 (10) | 0.0161 (3) | |
N2 | 0.50181 (17) | 0.77434 (15) | 0.70439 (10) | 0.0151 (3) | |
O5 | 1.18050 (15) | 0.23929 (13) | 0.12565 (9) | 0.0181 (2) | |
O1 | 0.31031 (16) | 0.82697 (14) | 0.88192 (9) | 0.0229 (3) | |
O2 | 0.51855 (15) | 0.28912 (13) | 0.77753 (9) | 0.0216 (3) | |
O3 | 0.66023 (15) | 0.73491 (13) | 0.52101 (9) | 0.0210 (3) | |
O4 | 1.07951 (14) | 0.53932 (13) | 0.19183 (9) | 0.0174 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0140 (6) | 0.0205 (8) | 0.0140 (7) | −0.0057 (6) | −0.0022 (5) | −0.0026 (6) |
C2 | 0.0151 (6) | 0.0175 (7) | 0.0130 (7) | −0.0061 (6) | −0.0020 (5) | −0.0008 (6) |
C3 | 0.0134 (6) | 0.0152 (7) | 0.0116 (7) | −0.0049 (5) | −0.0022 (5) | 0.0006 (5) |
C4 | 0.0129 (6) | 0.0161 (7) | 0.0135 (7) | −0.0035 (5) | −0.0013 (5) | −0.0022 (6) |
C5 | 0.0138 (6) | 0.0149 (7) | 0.0135 (7) | −0.0058 (5) | −0.0027 (5) | 0.0013 (6) |
C6 | 0.0128 (6) | 0.0156 (7) | 0.0128 (7) | −0.0041 (5) | −0.0024 (5) | −0.0010 (5) |
C7 | 0.0148 (6) | 0.0137 (7) | 0.0141 (7) | −0.0048 (5) | −0.0006 (5) | −0.0028 (5) |
C8 | 0.0136 (6) | 0.0147 (7) | 0.0134 (7) | −0.0061 (5) | −0.0014 (5) | 0.0009 (5) |
C9 | 0.0134 (6) | 0.0164 (7) | 0.0124 (7) | −0.0042 (5) | −0.0015 (5) | −0.0023 (6) |
C10 | 0.0172 (7) | 0.0137 (7) | 0.0167 (7) | −0.0040 (5) | −0.0024 (5) | −0.0032 (6) |
C11 | 0.0161 (6) | 0.0151 (7) | 0.0160 (7) | −0.0070 (6) | −0.0023 (5) | 0.0012 (6) |
C12 | 0.0216 (7) | 0.0140 (7) | 0.0201 (8) | −0.0058 (6) | −0.0013 (6) | −0.0034 (6) |
C13 | 0.0228 (8) | 0.0279 (9) | 0.0138 (8) | −0.0110 (7) | 0.0020 (6) | −0.0015 (6) |
C14 | 0.0237 (7) | 0.0153 (8) | 0.0203 (8) | −0.0067 (6) | 0.0005 (6) | −0.0010 (6) |
C15 | 0.0267 (8) | 0.0176 (8) | 0.0184 (8) | −0.0053 (6) | 0.0009 (6) | −0.0067 (6) |
N1 | 0.0171 (6) | 0.0192 (7) | 0.0118 (6) | −0.0075 (5) | 0.0008 (5) | −0.0008 (5) |
N2 | 0.0164 (6) | 0.0144 (6) | 0.0143 (6) | −0.0055 (5) | −0.0007 (5) | −0.0013 (5) |
O5 | 0.0226 (5) | 0.0156 (5) | 0.0142 (5) | −0.0063 (4) | 0.0041 (4) | −0.0049 (4) |
O1 | 0.0253 (6) | 0.0234 (6) | 0.0184 (6) | −0.0077 (5) | 0.0040 (4) | −0.0085 (5) |
O2 | 0.0284 (6) | 0.0173 (6) | 0.0177 (6) | −0.0099 (5) | 0.0016 (4) | 0.0015 (4) |
O3 | 0.0271 (6) | 0.0154 (5) | 0.0160 (6) | −0.0056 (4) | 0.0031 (4) | 0.0008 (4) |
O4 | 0.0214 (5) | 0.0133 (5) | 0.0154 (5) | −0.0067 (4) | 0.0033 (4) | −0.0008 (4) |
C1—O1 | 1.2150 (18) | C10—C11 | 1.385 (2) |
C1—N1 | 1.386 (2) | C10—H10 | 0.93 |
C1—N2 | 1.3897 (19) | C11—H11 | 0.93 |
C2—O2 | 1.2212 (19) | C12—N2 | 1.467 (2) |
C2—N1 | 1.3826 (19) | C12—H12A | 0.96 |
C2—C3 | 1.489 (2) | C12—H12B | 0.96 |
C3—C5 | 1.365 (2) | C12—H12C | 0.96 |
C3—C4 | 1.466 (2) | C13—N1 | 1.4716 (19) |
C4—O3 | 1.2235 (17) | C13—H13A | 0.96 |
C4—N2 | 1.3914 (19) | C13—H13B | 0.96 |
C5—C6 | 1.453 (2) | C13—H13C | 0.96 |
C5—H5 | 0.93 | C14—O4 | 1.4331 (19) |
C6—C11 | 1.402 (2) | C14—H14A | 0.96 |
C6—C7 | 1.413 (2) | C14—H14B | 0.96 |
C7—C8 | 1.377 (2) | C14—H14C | 0.96 |
C7—H7 | 0.93 | C15—O5 | 1.4400 (19) |
C8—O4 | 1.3650 (18) | C15—H15A | 0.96 |
C8—C9 | 1.416 (2) | C15—H15B | 0.96 |
C9—O5 | 1.3525 (17) | C15—H15C | 0.96 |
C9—C10 | 1.389 (2) | ||
O1—C1—N1 | 121.71 (14) | N2—C12—H12A | 109.5 |
O1—C1—N2 | 121.60 (14) | N2—C12—H12B | 109.5 |
N1—C1—N2 | 116.69 (12) | H12A—C12—H12B | 109.5 |
O2—C2—N1 | 119.59 (13) | N2—C12—H12C | 109.5 |
O2—C2—C3 | 123.24 (13) | H12A—C12—H12C | 109.5 |
N1—C2—C3 | 117.16 (13) | H12B—C12—H12C | 109.5 |
C5—C3—C4 | 127.56 (13) | N1—C13—H13A | 109.5 |
C5—C3—C2 | 113.69 (13) | N1—C13—H13B | 109.5 |
C4—C3—C2 | 118.73 (12) | H13A—C13—H13B | 109.5 |
O3—C4—N2 | 118.37 (14) | N1—C13—H13C | 109.5 |
O3—C4—C3 | 125.11 (13) | H13A—C13—H13C | 109.5 |
N2—C4—C3 | 116.51 (13) | H13B—C13—H13C | 109.5 |
C3—C5—C6 | 138.25 (14) | O4—C14—H14A | 109.5 |
C3—C5—H5 | 110.9 | O4—C14—H14B | 109.5 |
C6—C5—H5 | 110.9 | H14A—C14—H14B | 109.5 |
C11—C6—C7 | 117.75 (13) | O4—C14—H14C | 109.5 |
C11—C6—C5 | 115.55 (13) | H14A—C14—H14C | 109.5 |
C7—C6—C5 | 126.71 (13) | H14B—C14—H14C | 109.5 |
C8—C7—C6 | 120.66 (13) | O5—C15—H15A | 109.5 |
C8—C7—H7 | 119.7 | O5—C15—H15B | 109.5 |
C6—C7—H7 | 119.7 | H15A—C15—H15B | 109.5 |
O4—C8—C7 | 124.60 (13) | O5—C15—H15C | 109.5 |
O4—C8—C9 | 114.77 (12) | H15A—C15—H15C | 109.5 |
C7—C8—C9 | 120.64 (13) | H15B—C15—H15C | 109.5 |
O5—C9—C10 | 125.58 (13) | C2—N1—C1 | 124.99 (13) |
O5—C9—C8 | 115.28 (12) | C2—N1—C13 | 117.62 (13) |
C10—C9—C8 | 119.14 (13) | C1—N1—C13 | 117.39 (12) |
C11—C10—C9 | 119.85 (14) | C1—N2—C4 | 125.56 (13) |
C11—C10—H10 | 120.1 | C1—N2—C12 | 117.23 (12) |
C9—C10—H10 | 120.1 | C4—N2—C12 | 116.91 (12) |
C10—C11—C6 | 121.96 (13) | C9—O5—C15 | 117.89 (11) |
C10—C11—H11 | 119 | C8—O4—C14 | 116.37 (11) |
C6—C11—H11 | 119 |
Experimental details
Crystal data | |
Chemical formula | C15H16N2O5 |
Mr | 304.3 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.3086 (2), 8.4033 (3), 11.8705 (5) |
α, β, γ (°) | 82.5685 (18), 77.6686 (17), 71.1469 (15) |
V (Å3) | 672.58 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.15 × 0.12 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.984, 0.994 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12172, 3233, 2478 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.113, 1.05 |
No. of reflections | 3233 |
No. of parameters | 203 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.30 |
Computer programs: APEX2 (Bruker, 2008), SAINT-Plus (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenberg & Putz, 2005), WinGX (Farrugia, 1999).
Acknowledgements
The University of the Free State and Sasol Ltd are gratefully acknowledged, for financial support, and Johannes van Tonder for the NMR data and help with the synthesis of the title compound. Special thanks are due to Professor Andreas Roodt.
References
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Barbituric acid is the parent compound of barbiturate drugs, although by itself it is not pharmacologically active (Negwar et al., 2001). Benzyledenebarbituric acids are important building block in the synthesis of pyrazolo-[3,4]-1,3-diazinane derivatives which shows broad-spectrum biological activities (Tanaka et al., 1986 and 1988). We also synthesized some of the benzyledene barbituric acids which were successfully used to prepare pyrano[2,3-d]- and furopyrano[2,3-d] 1,3-diazinane derivatives (Prajapati et al., 2006). The title compound having molecular formula C15H16N2O5 can be prepared by the condensation of barbituric acid and 4,5-dimethoxybenzaldehyde. The bond C5—C6 of 1.453 (2) Å is longer than C3—C5 bond of 1.365 (2) Å that indicates C3—C5 as a formally double bond. This is in accordance with the literature (Panchatcharam et al. 2009 and Rezende et al. 2005).