Acta Cryst. (2009). E65, o2171 [ doi:10.1107/S1600536809031535 ]
The benzene ring of the title compound, C13H12N2O6, is twisted away from the planes of the aminomethylene unit and the dioxane ring by 30.13 (4) and 35.89 (4)°, respectively. The dioxane ring exhibits a half-boat conformation, in which the C atom between the dioxane O atoms is 0.553 (8) Å out-of-plane. An intramolecular N-H
O hydrogen bond stabilizes the conformation of the dioxane ring with the aminomethylene group [the dihedral angle between the mean planes of the dioxane ring and the aminomethylene group is 11.61 (4)°]. In the crystal, a three-dimensional framework is built via weak intermolecular N-HO and C-HO interactions.
An ethanol solution (50 ml) of 2,2-dimethyl-1,3-dioxane-4,6-dione (1.44 g, 0.01 mol) and methylorthoformate (1.27 g, 0.012 mol) was heated to reflux for 1 h, then the 3-nitrobenzenamine (1.38 g, 0.01 mol) was added into the solution. The mixture was heated under reflux for another 8 h and then filtered. Single crystals were obtained from the filtrate after 3 days.
The imino H atom was located in a difference Fourier map and refined isotropically. The other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic, C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./zq2002fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. The intramolecular hydrogen bond is shown as a dashed line. |
![[Figure 2]](./zq2002fig2thm.gif)
| Fig. 2. Crystal packing of the title compound, showing the intermolecular hydrogen bonds as dashed lines. [Symmetry codes: (i) -x + 1, -y, -z + 2; (ii) -x, -y, -z + 2]. |
| C13H12N2O6 | F(000) = 608 |
| Mr = 292.25 | Dx = 1.460 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 11.7900 (13) Å | Cell parameters from 4305 reflections |
| b = 8.7699 (9) Å | θ = 2.3–27.6° |
| c = 14.0614 (15) Å | µ = 0.12 mm−1 |
| β = 113.864 (1)° | T = 153 K |
| V = 1329.6 (2) Å3 | Block, colourless |
| Z = 4 | 0.20 × 0.10 × 0.10 mm |
| Bruker SMART CCD area-detector diffractometer | 2572 reflections with I > 2σ(I) |
| Radiation source: sealed tube | Rint = 0.014 |
| graphite | θmax = 27.6°, θmin = 2.8° |
| φ and ω scans | h = −15→14 |
| 8116 measured reflections | k = −11→10 |
| 3052 independent reflections | l = −18→18 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.3157P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 3052 reflections | Δρmax = 0.22 e Å−3 |
| 197 parameters | Δρmin = −0.18 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0195 (18) |
| C13H12N2O6 | V = 1329.6 (2) Å3 |
| Mr = 292.25 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.7900 (13) Å | µ = 0.12 mm−1 |
| b = 8.7699 (9) Å | T = 153 K |
| c = 14.0614 (15) Å | 0.20 × 0.10 × 0.10 mm |
| β = 113.864 (1)° |
| Bruker SMART CCD area-detector diffractometer | 2572 reflections with I > 2σ(I) |
| 8116 measured reflections | Rint = 0.014 |
| 3052 independent reflections | θmax = 27.6° |
| R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | Δρmax = 0.22 e Å−3 |
| S = 1.05 | Δρmin = −0.18 e Å−3 |
| 3052 reflections | Absolute structure: ? |
| 197 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.45433 (8) | −0.09916 (10) | 1.23372 (6) | 0.0370 (2) | |
| O3 | 0.47419 (8) | −0.05487 (12) | 1.08661 (7) | 0.0440 (2) | |
| O2 | 0.25826 (8) | −0.13984 (11) | 1.23681 (6) | 0.0401 (2) | |
| C4 | 0.40464 (11) | −0.06725 (13) | 1.13054 (9) | 0.0322 (2) | |
| N1 | 0.26298 (10) | 0.01843 (13) | 0.91248 (8) | 0.0359 (2) | |
| C8 | 0.19585 (11) | 0.06369 (14) | 0.80763 (9) | 0.0342 (3) | |
| C9 | 0.24224 (11) | 0.02544 (14) | 0.73506 (9) | 0.0347 (3) | |
| H9 | 0.3148 | −0.0312 | 0.7538 | 0.042* | |
| C3 | 0.37852 (11) | −0.07324 (14) | 1.29110 (9) | 0.0337 (3) | |
| O4 | 0.08565 (9) | −0.12773 (15) | 1.09442 (8) | 0.0584 (3) | |
| C7 | 0.21114 (11) | −0.01291 (14) | 0.97781 (9) | 0.0350 (3) | |
| H7 | 0.1252 | −0.0055 | 0.9519 | 0.042* | |
| O5 | 0.30012 (13) | −0.07262 (15) | 0.57581 (10) | 0.0684 (3) | |
| C6 | 0.19637 (11) | −0.10611 (15) | 1.13438 (9) | 0.0381 (3) | |
| C5 | 0.27159 (11) | −0.05534 (14) | 1.08029 (9) | 0.0333 (3) | |
| C10 | 0.17796 (12) | 0.07365 (16) | 0.63388 (9) | 0.0403 (3) | |
| C13 | 0.08587 (14) | 0.14495 (19) | 0.77793 (11) | 0.0510 (4) | |
| H13 | 0.0545 | 0.1705 | 0.8268 | 0.061* | |
| C2 | 0.43836 (14) | −0.16096 (17) | 1.39116 (10) | 0.0459 (3) | |
| H2A | 0.3876 | −0.1539 | 1.4299 | 0.069* | |
| H2B | 0.5188 | −0.1189 | 1.4315 | 0.069* | |
| H2C | 0.4468 | −0.2660 | 1.3759 | 0.069* | |
| N2 | 0.22862 (12) | 0.03454 (17) | 0.55739 (9) | 0.0535 (3) | |
| C1 | 0.36712 (15) | 0.09463 (15) | 1.30692 (11) | 0.0481 (3) | |
| H1A | 0.3285 | 0.1440 | 1.2406 | 0.072* | |
| H1B | 0.4481 | 0.1372 | 1.3444 | 0.072* | |
| H1C | 0.3174 | 0.1099 | 1.3459 | 0.072* | |
| C11 | 0.06978 (15) | 0.1552 (2) | 0.60191 (11) | 0.0586 (4) | |
| H11 | 0.0293 | 0.1874 | 0.5334 | 0.070* | |
| O6 | 0.19778 (16) | 0.1124 (2) | 0.47934 (10) | 0.0992 (6) | |
| C12 | 0.02320 (15) | 0.1877 (2) | 0.67512 (13) | 0.0672 (5) | |
| H12 | −0.0518 | 0.2393 | 0.6550 | 0.081* | |
| H1 | 0.3441 (15) | 0.0100 (18) | 0.9339 (12) | 0.051 (4)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0341 (4) | 0.0496 (5) | 0.0266 (4) | 0.0047 (4) | 0.0115 (3) | 0.0028 (3) |
| O3 | 0.0338 (5) | 0.0665 (6) | 0.0354 (5) | 0.0021 (4) | 0.0177 (4) | 0.0058 (4) |
| O2 | 0.0413 (5) | 0.0500 (5) | 0.0306 (4) | −0.0094 (4) | 0.0164 (4) | 0.0009 (4) |
| C4 | 0.0350 (6) | 0.0351 (6) | 0.0270 (5) | 0.0005 (4) | 0.0130 (5) | 0.0007 (4) |
| N1 | 0.0313 (5) | 0.0478 (6) | 0.0274 (5) | 0.0026 (4) | 0.0106 (4) | 0.0029 (4) |
| C8 | 0.0332 (6) | 0.0396 (6) | 0.0279 (5) | −0.0008 (5) | 0.0105 (5) | 0.0033 (5) |
| C9 | 0.0328 (6) | 0.0388 (6) | 0.0302 (6) | 0.0001 (5) | 0.0106 (5) | 0.0030 (5) |
| C3 | 0.0375 (6) | 0.0384 (6) | 0.0263 (5) | −0.0019 (5) | 0.0140 (5) | −0.0011 (4) |
| O4 | 0.0353 (5) | 0.0966 (9) | 0.0440 (6) | −0.0133 (5) | 0.0167 (4) | 0.0000 (5) |
| C7 | 0.0312 (6) | 0.0427 (6) | 0.0295 (6) | −0.0006 (5) | 0.0108 (5) | −0.0006 (5) |
| O5 | 0.0855 (9) | 0.0756 (8) | 0.0587 (7) | 0.0112 (7) | 0.0443 (6) | −0.0031 (6) |
| C6 | 0.0352 (6) | 0.0482 (7) | 0.0324 (6) | −0.0042 (5) | 0.0152 (5) | −0.0021 (5) |
| C5 | 0.0315 (6) | 0.0409 (6) | 0.0283 (5) | −0.0007 (5) | 0.0128 (5) | −0.0004 (5) |
| C10 | 0.0420 (7) | 0.0496 (7) | 0.0294 (6) | −0.0030 (5) | 0.0146 (5) | 0.0032 (5) |
| C13 | 0.0479 (8) | 0.0687 (10) | 0.0417 (7) | 0.0176 (7) | 0.0235 (6) | 0.0123 (7) |
| C2 | 0.0555 (8) | 0.0499 (8) | 0.0300 (6) | −0.0003 (6) | 0.0147 (6) | 0.0052 (5) |
| N2 | 0.0583 (8) | 0.0716 (9) | 0.0339 (6) | −0.0037 (7) | 0.0218 (5) | 0.0014 (6) |
| C1 | 0.0629 (9) | 0.0392 (7) | 0.0427 (7) | 0.0011 (6) | 0.0219 (7) | −0.0044 (6) |
| C11 | 0.0521 (9) | 0.0833 (12) | 0.0349 (7) | 0.0148 (8) | 0.0118 (6) | 0.0209 (7) |
| O6 | 0.1211 (13) | 0.1419 (14) | 0.0516 (7) | 0.0380 (11) | 0.0524 (8) | 0.0415 (8) |
| C12 | 0.0509 (9) | 0.0965 (13) | 0.0529 (9) | 0.0351 (9) | 0.0197 (7) | 0.0271 (9) |
| O1—C4 | 1.3560 (14) | C7—H7 | 0.9300 |
| O1—C3 | 1.4441 (14) | O5—N2 | 1.2183 (18) |
| O3—C4 | 1.2147 (14) | C6—C5 | 1.4524 (16) |
| O2—C6 | 1.3580 (15) | C10—C11 | 1.370 (2) |
| O2—C3 | 1.4348 (15) | C10—N2 | 1.4665 (17) |
| C4—C5 | 1.4401 (17) | C13—C12 | 1.383 (2) |
| N1—C7 | 1.3219 (15) | C13—H13 | 0.9300 |
| N1—C8 | 1.4190 (15) | C2—H2A | 0.9600 |
| N1—H1 | 0.882 (16) | C2—H2B | 0.9600 |
| C8—C9 | 1.3800 (17) | C2—H2C | 0.9600 |
| C8—C13 | 1.3875 (18) | N2—O6 | 1.2164 (17) |
| C9—C10 | 1.3802 (17) | C1—H1A | 0.9600 |
| C9—H9 | 0.9300 | C1—H1B | 0.9600 |
| C3—C1 | 1.5030 (18) | C1—H1C | 0.9600 |
| C3—C2 | 1.5053 (17) | C11—C12 | 1.378 (2) |
| O4—C6 | 1.2092 (16) | C11—H11 | 0.9300 |
| C7—C5 | 1.3754 (16) | C12—H12 | 0.9300 |
| C4—O1—C3 | 117.92 (9) | C4—C5—C6 | 119.70 (10) |
| C6—O2—C3 | 117.84 (9) | C11—C10—C9 | 123.24 (12) |
| O3—C4—O1 | 118.31 (11) | C11—C10—N2 | 118.87 (12) |
| O3—C4—C5 | 124.71 (11) | C9—C10—N2 | 117.88 (12) |
| O1—C4—C5 | 116.96 (10) | C12—C13—C8 | 119.52 (13) |
| C7—N1—C8 | 124.04 (10) | C12—C13—H13 | 120.2 |
| C7—N1—H1 | 119.2 (10) | C8—C13—H13 | 120.2 |
| C8—N1—H1 | 116.7 (10) | C3—C2—H2A | 109.5 |
| C9—C8—C13 | 120.26 (11) | C3—C2—H2B | 109.5 |
| C9—C8—N1 | 118.62 (11) | H2A—C2—H2B | 109.5 |
| C13—C8—N1 | 121.12 (11) | C3—C2—H2C | 109.5 |
| C8—C9—C10 | 118.11 (11) | H2A—C2—H2C | 109.5 |
| C8—C9—H9 | 120.9 | H2B—C2—H2C | 109.5 |
| C10—C9—H9 | 120.9 | O6—N2—O5 | 123.59 (14) |
| O2—C3—O1 | 109.91 (9) | O6—N2—C10 | 117.94 (14) |
| O2—C3—C1 | 110.44 (11) | O5—N2—C10 | 118.46 (12) |
| O1—C3—C1 | 110.45 (10) | C3—C1—H1A | 109.5 |
| O2—C3—C2 | 106.13 (10) | C3—C1—H1B | 109.5 |
| O1—C3—C2 | 106.25 (10) | H1A—C1—H1B | 109.5 |
| C1—C3—C2 | 113.48 (11) | C3—C1—H1C | 109.5 |
| N1—C7—C5 | 126.51 (11) | H1A—C1—H1C | 109.5 |
| N1—C7—H7 | 116.7 | H1B—C1—H1C | 109.5 |
| C5—C7—H7 | 116.7 | C10—C11—C12 | 117.54 (13) |
| O4—C6—O2 | 118.33 (11) | C10—C11—H11 | 121.2 |
| O4—C6—C5 | 125.30 (12) | C12—C11—H11 | 121.2 |
| O2—C6—C5 | 116.25 (10) | C11—C12—C13 | 121.26 (14) |
| C7—C5—C4 | 122.25 (10) | C11—C12—H12 | 119.4 |
| C7—C5—C6 | 117.66 (11) | C13—C12—H12 | 119.4 |
| C3—O1—C4—O3 | 163.48 (11) | O3—C4—C5—C6 | 165.88 (12) |
| C3—O1—C4—C5 | −18.46 (15) | O1—C4—C5—C6 | −12.04 (17) |
| C7—N1—C8—C9 | −149.73 (12) | O4—C6—C5—C7 | 7.2 (2) |
| C7—N1—C8—C13 | 30.4 (2) | O2—C6—C5—C7 | −176.78 (11) |
| C13—C8—C9—C10 | 1.64 (19) | O4—C6—C5—C4 | −165.75 (14) |
| N1—C8—C9—C10 | −178.26 (11) | O2—C6—C5—C4 | 10.23 (18) |
| C6—O2—C3—O1 | −50.49 (14) | C8—C9—C10—C11 | −1.1 (2) |
| C6—O2—C3—C1 | 71.61 (13) | C8—C9—C10—N2 | 179.15 (11) |
| C6—O2—C3—C2 | −164.99 (10) | C9—C8—C13—C12 | −0.1 (2) |
| C4—O1—C3—O2 | 48.46 (13) | N1—C8—C13—C12 | 179.74 (15) |
| C4—O1—C3—C1 | −73.64 (14) | C11—C10—N2—O6 | 22.6 (2) |
| C4—O1—C3—C2 | 162.88 (10) | C9—C10—N2—O6 | −157.58 (15) |
| C8—N1—C7—C5 | −179.14 (12) | C11—C10—N2—O5 | −158.17 (16) |
| C3—O2—C6—O4 | −161.51 (12) | C9—C10—N2—O5 | 21.6 (2) |
| C3—O2—C6—C5 | 22.23 (16) | C9—C10—C11—C12 | −1.0 (3) |
| N1—C7—C5—C4 | 1.6 (2) | N2—C10—C11—C12 | 178.78 (16) |
| N1—C7—C5—C6 | −171.23 (12) | C10—C11—C12—C13 | 2.5 (3) |
| O3—C4—C5—C7 | −6.8 (2) | C8—C13—C12—C11 | −2.0 (3) |
| O1—C4—C5—C7 | 175.30 (11) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O3 | 0.882 (16) | 2.150 (15) | 2.7705 (14) | 126.8 (13) |
| N1—H1···O3i | 0.882 (16) | 2.308 (16) | 3.1101 (14) | 151.2 (13) |
| C7—H7···O4 | 0.93 | 2.48 | 2.8026 (18) | 101 |
| C7—H7···O4ii | 0.93 | 2.58 | 3.4527 (18) | 156 |
| C11—H11···O4iii | 0.93 | 2.39 | 3.242 (2) | 152 |
| C13—H13···O4ii | 0.93 | 2.36 | 3.205 (2) | 151 |
| Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2; (iii) −x, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O3 | 0.882 (16) | 2.150 (15) | 2.7705 (14) | 126.8 (13) |
| N1—H1···O3i | 0.882 (16) | 2.308 (16) | 3.1101 (14) | 151.2 (13) |
| C7—H7···O4 | 0.93 | 2.48 | 2.8026 (18) | 101 |
| C7—H7···O4ii | 0.93 | 2.58 | 3.4527 (18) | 156 |
| C11—H11···O4iii | 0.93 | 2.39 | 3.242 (2) | 152 |
| C13—H13···O4ii | 0.93 | 2.36 | 3.205 (2) | 151 |
| Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x, −y, −z+2; (iii) −x, y+1/2, −z+3/2. |
This research was supported financially by the State Key Laboratory of Drug Research (Shanghai Institute of Materia Medica, Chinese Academy of Sciences).
Bruker (2000). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Cassis, R., Tapia, R. & Valderrama, J. A. (1985). Synth. Commun. 15, 125-133.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Li, R., Ding, Z.-Y., Wei, Y.-Q. & Ding, J. (2009a). Acta Cryst. E65, o1296.
Li, R., Ding, Z.-Y., Wei, Y.-Q. & Ding, J. (2009b). Acta Cryst. E65, o1297.
Li, R., Shi, J.-Y., Ding, Z.-Y., Wei, Y.-Q. & Ding, J. (2009). Acta Cryst. E65, o1298–o1299.
Ruchelman, A. L., Singh, S. K., Ray, A., Wu, X. H., Yang, J. M., Li, T. K., Liu, A., Liu, L. F. & LaVoie, E. J. (2003). Bioorg. Med. Chem. 11, 2061–2073.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
The 4(1H)quinolone structure have long attracted pharmacological interest as anticancer agents, anti-malarial agents and reversible (H+/K+) ATPase inhibitors (Ruchelman et al., 2003). 5-Arylaminomethylene-2,2-dimethyl-1,3-dioxane-4,6-diones are the key intermediates which can be used to synthesize the 4(1H)quinolone derivatives by thermolysis (Cassis et al., 1985).
The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the mean planes formed by the benzyl and aminomethylene units is 30.13 (4)°, while the angle between the mean planes of the dioxane ring and the aminomethylene group is only 11.61 (4)° due to the intramolecular N1—H1···O3 hydrogen bond (Table 1). Apart from that, the dioxane ring exhibits a half-boat conformation, in which the C atom between the dioxane oxygen atoms is 0.553 (8) Å out-of-plane.
The three-dimensional framework is built by the weak intermolecular N1—H1···O3i, C7—H7···O4ii, C13—H13···O4ii and C11—H11···O4iii interactions (Fig. 2).