Acta Cryst. (2009). E65, o1297 [ doi:10.1107/S1600536809017425 ]
In the title compound, C15H15NO5, the six-membered dioxane ring assumes an envelope conformation with the dimethyl substituted C atom as the flap atom. An intramolecular N-H
O interaction is also present. In the crystal structure the molecules are linked via C-HO hydrogen bonds into supramolecular chains along the b axis.
A methanol solution (50 ml) of Meldrum's acid (1.44 g, 0.01 mol) and methylorthoformate (1.27 g, 0.012 mol) was heated to reflux for 2 h, then the arylamine (1.35 g, 0.01 mol) was added into the above solution. The mixture was heated under reflux for another 8 h and then filtered. Single crystals were obtained from the filtrate after 2 d.
The imino H atom was located in a difference Fourier map and refined isotropically. Other H atoms were positioned geometrically with C—H = 0.93 (aromatic) or 0.96 Å (methyl), and refined using a riding model with Uiso(H) = 1.5Ueq(C) for methyl and 1.2Ueq(C) for the others.
Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); 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).
![[Figure 1]](./xu2521fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. |
| C15H15NO5 | Z = 2 |
| Mr = 289.28 | F000 = 304 |
| Triclinic, P1 | Dx = 1.349 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 7.102 (3) Å | Cell parameters from 25 reflections |
| b = 7.356 (4) Å | θ = 4.4–7.4º |
| c = 13.856 (4) Å | µ = 0.10 mm−1 |
| α = 82.79 (4)º | T = 292 K |
| β = 83.19 (4)º | Block, colourless |
| γ = 86.03 (4)º | 0.44 × 0.36 × 0.32 mm |
| V = 712.0 (5) Å3 |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.008 |
| Radiation source: fine-focus sealed tube | θmax = 25.5º |
| Monochromator: graphite | θmin = 1.5º |
| T = 292 K | h = −8→8 |
| ω/2θ scans | k = −3→8 |
| Absorption correction: none | l = −16→16 |
| 2894 measured reflections | 3 standard reflections |
| 2621 independent reflections | every 100 reflections |
| 1399 reflections with I > 2σ(I) | intensity decay: 1.8% |
| 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)] = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.179 | w = 1/[σ2(Fo2) + (0.0987P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 2621 reflections | Δρmax = 0.23 e Å−3 |
| 197 parameters | Δρmin = −0.34 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C15H15NO5 | γ = 86.03 (4)º |
| Mr = 289.28 | V = 712.0 (5) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.102 (3) Å | Mo Kα |
| b = 7.356 (4) Å | µ = 0.10 mm−1 |
| c = 13.856 (4) Å | T = 292 K |
| α = 82.79 (4)º | 0.44 × 0.36 × 0.32 mm |
| β = 83.19 (4)º |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.008 |
| Absorption correction: none | 3 standard reflections |
| 2894 measured reflections | every 100 reflections |
| 2621 independent reflections | intensity decay: 1.8% |
| 1399 reflections with I > 2σ(I) |
| R[F2 > 2σ(F2)] = 0.064 | 197 parameters |
| wR(F2) = 0.179 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | Δρmax = 0.23 e Å−3 |
| 2621 reflections | Δρmin = −0.34 e Å−3 |
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 | 0.4606 (3) | 0.5224 (2) | 0.87501 (13) | 0.0548 (6) | |
| O2 | 0.4847 (3) | 0.3153 (3) | 0.75537 (13) | 0.0585 (6) | |
| O3 | 0.5363 (3) | 0.8104 (3) | 0.83800 (15) | 0.0713 (7) | |
| O4 | 0.5696 (3) | 0.4044 (3) | 0.60005 (14) | 0.0688 (7) | |
| O5 | 0.9300 (3) | 1.4570 (3) | 0.25900 (17) | 0.0767 (7) | |
| N1 | 0.6950 (3) | 0.7445 (3) | 0.54722 (17) | 0.0485 (6) | |
| H1N | 0.674 (4) | 0.644 (5) | 0.528 (2) | 0.066 (9)* | |
| C1 | 0.3511 (5) | 0.2250 (4) | 0.9154 (2) | 0.0677 (9) | |
| H1A | 0.3605 | 0.2286 | 0.9836 | 0.101* | |
| H1B | 0.3674 | 0.1003 | 0.9010 | 0.101* | |
| H1C | 0.2284 | 0.2754 | 0.8999 | 0.101* | |
| C2 | 0.6988 (5) | 0.2750 (5) | 0.8795 (2) | 0.0708 (9) | |
| H2A | 0.7894 | 0.3472 | 0.8371 | 0.106* | |
| H2B | 0.7236 | 0.1478 | 0.8706 | 0.106* | |
| H2C | 0.7094 | 0.2910 | 0.9463 | 0.106* | |
| C3 | 0.5022 (4) | 0.3356 (4) | 0.8554 (2) | 0.0504 (7) | |
| C4 | 0.5331 (4) | 0.6609 (4) | 0.8097 (2) | 0.0503 (7) | |
| C5 | 0.5861 (4) | 0.6195 (3) | 0.71100 (18) | 0.0440 (6) | |
| C6 | 0.5512 (4) | 0.4421 (4) | 0.6835 (2) | 0.0486 (7) | |
| C7 | 0.6522 (4) | 0.7568 (3) | 0.64119 (19) | 0.0443 (7) | |
| H7 | 0.6681 | 0.8692 | 0.6625 | 0.053* | |
| C8 | 0.7584 (4) | 0.8835 (4) | 0.47359 (19) | 0.0443 (7) | |
| C9 | 0.8222 (4) | 0.8338 (4) | 0.3821 (2) | 0.0561 (8) | |
| H9 | 0.8262 | 0.7113 | 0.3711 | 0.067* | |
| C10 | 0.8804 (4) | 0.9674 (4) | 0.3063 (2) | 0.0562 (8) | |
| H10 | 0.9233 | 0.9337 | 0.2447 | 0.067* | |
| C11 | 0.8752 (4) | 1.1500 (4) | 0.3217 (2) | 0.0475 (7) | |
| C12 | 0.8132 (4) | 1.1971 (4) | 0.4143 (2) | 0.0510 (7) | |
| H12 | 0.8113 | 1.3192 | 0.4256 | 0.061* | |
| C13 | 0.7541 (4) | 1.0661 (4) | 0.4903 (2) | 0.0491 (7) | |
| H13 | 0.7118 | 1.0998 | 0.5521 | 0.059* | |
| C14 | 0.9294 (4) | 1.2990 (4) | 0.2415 (2) | 0.0558 (8) | |
| C15 | 0.9783 (5) | 1.2522 (5) | 0.1391 (2) | 0.0731 (10) | |
| H15A | 1.0042 | 1.3622 | 0.0958 | 0.110* | |
| H15B | 0.8735 | 1.1954 | 0.1195 | 0.110* | |
| H15C | 1.0885 | 1.1690 | 0.1365 | 0.110* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0800 (14) | 0.0361 (11) | 0.0476 (11) | 0.0014 (9) | −0.0018 (10) | −0.0097 (9) |
| O2 | 0.0936 (15) | 0.0361 (11) | 0.0467 (11) | −0.0137 (10) | −0.0013 (10) | −0.0087 (9) |
| O3 | 0.125 (2) | 0.0320 (11) | 0.0598 (12) | −0.0023 (11) | −0.0121 (12) | −0.0163 (9) |
| O4 | 0.1213 (19) | 0.0381 (11) | 0.0475 (12) | −0.0173 (12) | 0.0040 (11) | −0.0130 (9) |
| O5 | 0.0993 (18) | 0.0370 (13) | 0.0893 (17) | −0.0106 (11) | 0.0019 (13) | 0.0012 (11) |
| N1 | 0.0641 (16) | 0.0299 (13) | 0.0525 (15) | −0.0091 (11) | −0.0043 (12) | −0.0071 (11) |
| C1 | 0.087 (2) | 0.056 (2) | 0.0591 (19) | −0.0135 (17) | 0.0026 (17) | −0.0095 (16) |
| C2 | 0.078 (2) | 0.053 (2) | 0.078 (2) | 0.0051 (16) | −0.0068 (18) | 0.0021 (16) |
| C3 | 0.071 (2) | 0.0296 (14) | 0.0505 (16) | 0.0001 (13) | −0.0032 (14) | −0.0068 (12) |
| C4 | 0.0647 (19) | 0.0389 (16) | 0.0488 (16) | 0.0057 (13) | −0.0135 (14) | −0.0092 (13) |
| C5 | 0.0512 (16) | 0.0371 (15) | 0.0455 (15) | 0.0007 (12) | −0.0106 (13) | −0.0086 (12) |
| C6 | 0.0670 (19) | 0.0346 (15) | 0.0435 (16) | −0.0027 (13) | −0.0018 (13) | −0.0065 (12) |
| C7 | 0.0527 (16) | 0.0300 (14) | 0.0525 (17) | −0.0017 (12) | −0.0121 (13) | −0.0086 (12) |
| C8 | 0.0449 (16) | 0.0374 (15) | 0.0520 (16) | −0.0071 (12) | −0.0067 (12) | −0.0067 (12) |
| C9 | 0.069 (2) | 0.0416 (16) | 0.0597 (18) | −0.0133 (14) | 0.0005 (15) | −0.0137 (14) |
| C10 | 0.0639 (19) | 0.0526 (19) | 0.0525 (17) | −0.0094 (15) | 0.0036 (14) | −0.0140 (14) |
| C11 | 0.0434 (16) | 0.0431 (16) | 0.0548 (17) | −0.0042 (12) | −0.0029 (13) | −0.0029 (13) |
| C12 | 0.0608 (19) | 0.0312 (14) | 0.0611 (18) | −0.0040 (12) | −0.0069 (14) | −0.0048 (13) |
| C13 | 0.0588 (18) | 0.0377 (15) | 0.0518 (16) | 0.0021 (13) | −0.0048 (13) | −0.0129 (13) |
| C14 | 0.0464 (17) | 0.0531 (19) | 0.066 (2) | 0.0003 (14) | −0.0062 (14) | −0.0001 (15) |
| C15 | 0.083 (2) | 0.063 (2) | 0.065 (2) | −0.0021 (18) | 0.0077 (18) | 0.0072 (16) |
| O1—C4 | 1.361 (3) | C5—C7 | 1.374 (4) |
| O1—C3 | 1.438 (3) | C5—C6 | 1.450 (4) |
| O2—C6 | 1.342 (3) | C7—H7 | 0.9300 |
| O2—C3 | 1.434 (3) | C8—C9 | 1.380 (4) |
| O3—C4 | 1.216 (3) | C8—C13 | 1.389 (4) |
| O4—C6 | 1.212 (3) | C9—C10 | 1.390 (4) |
| O5—C14 | 1.217 (3) | C9—H9 | 0.9300 |
| N1—C7 | 1.315 (3) | C10—C11 | 1.383 (4) |
| N1—C8 | 1.408 (3) | C10—H10 | 0.9300 |
| N1—H1N | 0.85 (3) | C11—C12 | 1.384 (4) |
| C1—C3 | 1.498 (4) | C11—C14 | 1.495 (4) |
| C1—H1A | 0.9600 | C12—C13 | 1.383 (4) |
| C1—H1B | 0.9600 | C12—H12 | 0.9300 |
| C1—H1C | 0.9600 | C13—H13 | 0.9300 |
| C2—C3 | 1.499 (4) | C14—C15 | 1.497 (4) |
| C2—H2A | 0.9600 | C15—H15A | 0.9600 |
| C2—H2B | 0.9600 | C15—H15B | 0.9600 |
| C2—H2C | 0.9600 | C15—H15C | 0.9600 |
| C4—C5 | 1.438 (3) | ||
| C4—O1—C3 | 119.3 (2) | O2—C6—C5 | 117.1 (2) |
| C6—O2—C3 | 120.1 (2) | N1—C7—C5 | 126.2 (2) |
| C7—N1—C8 | 127.6 (2) | N1—C7—H7 | 116.9 |
| C7—N1—H1N | 116 (2) | C5—C7—H7 | 116.9 |
| C8—N1—H1N | 116 (2) | C9—C8—C13 | 120.2 (3) |
| C3—C1—H1A | 109.5 | C9—C8—N1 | 117.8 (3) |
| C3—C1—H1B | 109.5 | C13—C8—N1 | 122.0 (2) |
| H1A—C1—H1B | 109.5 | C8—C9—C10 | 119.7 (3) |
| C3—C1—H1C | 109.5 | C8—C9—H9 | 120.1 |
| H1A—C1—H1C | 109.5 | C10—C9—H9 | 120.1 |
| H1B—C1—H1C | 109.5 | C11—C10—C9 | 120.7 (3) |
| C3—C2—H2A | 109.5 | C11—C10—H10 | 119.7 |
| C3—C2—H2B | 109.5 | C9—C10—H10 | 119.7 |
| H2A—C2—H2B | 109.5 | C10—C11—C12 | 118.8 (3) |
| C3—C2—H2C | 109.5 | C10—C11—C14 | 122.5 (3) |
| H2A—C2—H2C | 109.5 | C12—C11—C14 | 118.7 (3) |
| H2B—C2—H2C | 109.5 | C13—C12—C11 | 121.3 (3) |
| O2—C3—O1 | 111.4 (2) | C13—C12—H12 | 119.4 |
| O2—C3—C1 | 105.9 (2) | C11—C12—H12 | 119.4 |
| O1—C3—C1 | 106.4 (2) | C12—C13—C8 | 119.3 (3) |
| O2—C3—C2 | 110.2 (2) | C12—C13—H13 | 120.4 |
| O1—C3—C2 | 109.4 (2) | C8—C13—H13 | 120.4 |
| C1—C3—C2 | 113.4 (3) | O5—C14—C11 | 120.4 (3) |
| O3—C4—O1 | 117.5 (2) | O5—C14—C15 | 120.4 (3) |
| O3—C4—C5 | 125.9 (3) | C11—C14—C15 | 119.2 (3) |
| O1—C4—C5 | 116.5 (2) | C14—C15—H15A | 109.5 |
| C7—C5—C4 | 118.8 (2) | C14—C15—H15B | 109.5 |
| C7—C5—C6 | 120.4 (2) | H15A—C15—H15B | 109.5 |
| C4—C5—C6 | 120.5 (2) | C14—C15—H15C | 109.5 |
| O4—C6—O2 | 118.4 (2) | H15A—C15—H15C | 109.5 |
| O4—C6—C5 | 124.5 (3) | H15B—C15—H15C | 109.5 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O4 | 0.84 (4) | 2.05 (3) | 2.699 (3) | 133 (2) |
| C1—H1B···O3i | 0.96 | 2.57 | 3.480 (4) | 158 |
| C9—H9···O5i | 0.93 | 2.59 | 3.429 (4) | 150 |
| Symmetry codes: (i) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O4 | 0.84 (4) | 2.05 (3) | 2.699 (3) | 133 (2) |
| C1—H1B···O3i | 0.96 | 2.57 | 3.480 (4) | 158 |
| C9—H9···O5i | 0.93 | 2.59 | 3.429 (4) | 150 |
| Symmetry codes: (i) x, y−1, z. |
This research is financially supported by the State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences.
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The 4(1H)quinolone structure plays an extremely important role in the field of pharmaceutical chemistry. These compounds have been used as precursors for 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 is shown in Fig. 1. The six membered dioxane ring assumes an envelope conformation. The imino group links with the adjacent O atom via O—H···O hydrogen bonding. In the crystal structure the molecules are linked via C—H···O hydrogen bonding into one dimensional supra-molecualr chain along the b axis (Table 1).