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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Jan 8;67(Pt 2):o253. doi: 10.1107/S1600536810053250

2,2-Dimethyl-5-[(pyridin-2-yl­amino)­methyl­idene]-1,3-dioxane-4,6-dione

Jian-you Shi a,*, Jin-qi Li a, Rong-sheng Tong a, He Lin a, Chen Lu a
PMCID: PMC3051715  PMID: 21522947

Abstract

In the title compound, C12H12N2O4, the dihedral angle between the pyridine and enamine planes is 3.5 (3)°, while the angle between the dioxanedione (seven atoms) and enamine planes is 4.6 (3)°. The dioxane ring approximates an envelope conformation.

Related literature

The title compound is an inter­mediate in the synthesis of 4(1H)-quinolone-based drugs. For the synthesis and structures of related anti­tumor precursors, see: Cassis et al. (1985 ▶); Ruchelman et al. (2003 ▶); Shi et al. (2009 ▶).graphic file with name e-67-0o253-scheme1.jpg

Experimental

Crystal data

  • C12H12N2O4

  • M r = 248.24

  • Monoclinic, Inline graphic

  • a = 8.7344 (10) Å

  • b = 13.9712 (15) Å

  • c = 9.4744 (11) Å

  • β = 94.601 (11)°

  • V = 1152.4 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.11 mm−1

  • T = 293 K

  • 0.22 × 0.18 × 0.16 mm

Data collection

  • Oxford Diffraction Xcalibur diffractometer with an Eos CCD detector

  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.997, T max = 1.0

  • 4873 measured reflections

  • 2334 independent reflections

  • 1659 reflections with I > 2σ(I)

  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040

  • wR(F 2) = 0.096

  • S = 1.03

  • 2334 reflections

  • 166 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.14 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053250/bh2327sup1.cif

e-67-0o253-sup1.cif (16.2KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053250/bh2327Isup2.hkl

e-67-0o253-Isup2.hkl (114.7KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Mr Zhihua Mao of the Analysis and Testing Center (Sichuan University) for the data collection.

supplementary crystallographic information

Comment

The title compound is a key intermediates, which can be used to synthesize 4(1H)-quinolone derivatives by thermolysis. These compounds can be used as precursors for anti-malarial and anticancer agents (Cassis et al., 1985; Ruchelman et al., 2003; Shi et al., 2009).

Experimental

A mixture 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 refluxed for 2.5 h. Then pyridin-2-amine (0.94 g, 0.01 mol) was added and the mixture was refluxed for 4 h, then poured into cold water and filtered, to afford the title compound as a powder. Single crystals were obtained by slow evaporation of a CH2Cl2-methanol solution over 3 days.

Refinement

All H atoms were placed in calculated positions, with C—H bond lengths fixed to 0.93 (aromatic CH), 0.96 (methyl CH3) or 0.86 Å (NH group). Isotropic displacement parameters for H atoms were calculated as 1.5 (methyl) or 1.2 (other H atoms) times that of the equivalent displacement parameter of the carrier C atom.

Figures

Fig. 1.

Fig. 1.

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ORTEP-like view of the title compound.

Crystal data

C12H12N2O4 F(000) = 520
Mr = 248.24 Dx = 1.431 Mg m−3
Monoclinic, P21/c Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc Cell parameters from 1780 reflections
a = 8.7344 (10) Å θ = 3.1–29.2°
b = 13.9712 (15) Å µ = 0.11 mm−1
c = 9.4744 (11) Å T = 293 K
β = 94.601 (11)° Block, colourless
V = 1152.4 (2) Å3 0.22 × 0.18 × 0.16 mm
Z = 4
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Data collection

Oxford Diffraction Xcalibur diffractometer with an Eos CCD detector 2334 independent reflections
Radiation source: fine-focus sealed tube 1659 reflections with I > 2σ(I)
graphite Rint = 0.018
Detector resolution: 16.0874 pixels mm-1 θmax = 26.4°, θmin = 3.4°
ω scans h = −10→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) k = −17→16
Tmin = 0.997, Tmax = 1.0 l = −11→11
4873 measured reflections
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Refinement

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)] = 0.040 H-atom parameters constrained
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0383P)2 + 0.0655P] where P = (Fo2 + 2Fc2)/3
S = 1.03 (Δ/σ)max < 0.001
2334 reflections Δρmax = 0.14 e Å−3
166 parameters Δρmin = −0.14 e Å−3
1 restraint Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints Extinction coefficient: 0.0060 (9)
Primary atom site location: structure-invariant direct methods
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
O3 0.21039 (13) 0.15916 (7) 0.50800 (11) 0.0497 (3)
O4 0.37760 (12) 0.11610 (7) 0.33485 (12) 0.0504 (3)
C6 0.22965 (17) −0.10004 (11) 0.49185 (16) 0.0421 (4)
H6 0.1613 −0.1134 0.5596 0.050*
O1 0.10857 (14) 0.05240 (7) 0.64457 (11) 0.0556 (3)
O2 0.44968 (12) −0.03377 (8) 0.30745 (12) 0.0559 (3)
N2 0.29233 (14) −0.17386 (8) 0.43038 (13) 0.0455 (3)
H2 0.3571 −0.1614 0.3692 0.055*
C7 0.25719 (16) −0.00541 (10) 0.46383 (15) 0.0388 (3)
N1 0.17056 (15) −0.28950 (8) 0.55799 (13) 0.0474 (4)
C1 0.1423 (2) −0.38227 (11) 0.58158 (18) 0.0532 (4)
H1 0.0776 −0.3976 0.6515 0.064*
C9 0.18429 (18) 0.06634 (10) 0.54492 (16) 0.0428 (4)
C8 0.36562 (17) 0.02142 (11) 0.36380 (16) 0.0434 (4)
C5 0.26224 (16) −0.27096 (10) 0.45637 (16) 0.0400 (4)
C3 0.2993 (2) −0.43431 (11) 0.40519 (18) 0.0547 (5)
H3 0.3432 −0.4829 0.3548 0.066*
C4 0.32929 (19) −0.34013 (11) 0.37743 (17) 0.0487 (4)
H4 0.3930 −0.3233 0.3074 0.058*
C12 0.11654 (19) 0.16341 (11) 0.26210 (16) 0.0493 (4)
H12B 0.1452 0.1783 0.1689 0.074*
H12C 0.0343 0.2048 0.2851 0.074*
H12A 0.0833 0.0980 0.2649 0.074*
C11 0.3145 (2) 0.27839 (11) 0.36841 (19) 0.0606 (5)
H11A 0.3519 0.2923 0.2781 0.091*
H11C 0.3969 0.2843 0.4412 0.091*
H11B 0.2342 0.3226 0.3864 0.091*
C2 0.2036 (2) −0.45560 (11) 0.50844 (18) 0.0582 (5)
H2A 0.1806 −0.5189 0.5286 0.070*
C10 0.25227 (18) 0.17780 (10) 0.36764 (16) 0.0439 (4)
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
O3 0.0704 (8) 0.0405 (6) 0.0386 (6) −0.0001 (5) 0.0061 (5) −0.0014 (5)
O4 0.0432 (7) 0.0437 (6) 0.0656 (8) −0.0011 (5) 0.0137 (5) 0.0085 (5)
C6 0.0384 (9) 0.0485 (9) 0.0395 (9) 0.0012 (7) 0.0042 (7) −0.0004 (7)
O1 0.0669 (8) 0.0573 (7) 0.0448 (7) 0.0015 (6) 0.0178 (6) 0.0005 (5)
O2 0.0470 (7) 0.0543 (7) 0.0692 (8) 0.0047 (6) 0.0208 (6) 0.0026 (6)
N2 0.0452 (8) 0.0426 (8) 0.0502 (8) 0.0012 (6) 0.0140 (6) 0.0015 (6)
C7 0.0374 (8) 0.0399 (8) 0.0390 (8) −0.0006 (7) 0.0034 (6) 0.0022 (7)
N1 0.0516 (9) 0.0447 (8) 0.0471 (8) 0.0022 (6) 0.0102 (6) 0.0016 (6)
C1 0.0620 (11) 0.0477 (10) 0.0511 (10) −0.0035 (9) 0.0121 (8) 0.0056 (8)
C9 0.0460 (9) 0.0445 (9) 0.0373 (9) −0.0010 (7) −0.0001 (7) 0.0006 (7)
C8 0.0372 (9) 0.0438 (9) 0.0491 (9) −0.0005 (7) 0.0020 (7) 0.0017 (7)
C5 0.0376 (8) 0.0403 (9) 0.0418 (9) −0.0009 (7) 0.0022 (6) 0.0015 (7)
C3 0.0624 (12) 0.0465 (10) 0.0557 (11) 0.0058 (8) 0.0072 (9) −0.0100 (8)
C4 0.0478 (10) 0.0521 (10) 0.0477 (10) 0.0015 (8) 0.0123 (8) −0.0025 (7)
C12 0.0534 (10) 0.0523 (9) 0.0422 (10) 0.0029 (8) 0.0047 (7) 0.0012 (7)
C11 0.0704 (13) 0.0451 (10) 0.0651 (12) −0.0087 (9) −0.0009 (9) 0.0058 (8)
C2 0.0728 (13) 0.0414 (9) 0.0606 (12) −0.0031 (9) 0.0069 (9) 0.0017 (8)
C10 0.0495 (10) 0.0411 (9) 0.0419 (9) −0.0002 (7) 0.0078 (7) 0.0016 (7)
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Geometric parameters (Å, °)

O3—C9 1.3671 (16) C1—C2 1.370 (2)
O3—C10 1.4311 (18) C5—C4 1.381 (2)
O4—C8 1.3567 (17) C3—H3 0.9300
O4—C10 1.4465 (18) C3—C4 1.371 (2)
C6—H6 0.9300 C3—C2 1.370 (2)
C6—N2 1.3242 (18) C4—H4 0.9300
C6—C7 1.374 (2) C12—H12B 0.9600
O1—C9 1.2112 (17) C12—H12C 0.9600
O2—C8 1.2172 (17) C12—H12A 0.9600
N2—H2 0.8600 C12—C10 1.502 (2)
N2—C5 1.4072 (18) C11—H11A 0.9600
C7—C9 1.442 (2) C11—H11C 0.9600
C7—C8 1.442 (2) C11—H11B 0.9600
N1—C1 1.3415 (19) C11—C10 1.507 (2)
N1—C5 1.3263 (18) C2—H2A 0.9300
C1—H1 0.9300
O3—C9—C7 115.68 (13) C5—N2—H2 117.1
O3—C10—O4 110.21 (11) C5—N1—C1 116.06 (13)
O3—C10—C12 110.33 (13) C5—C4—H4 120.9
O3—C10—C11 106.51 (12) C3—C4—C5 118.16 (15)
O4—C8—C7 116.85 (13) C3—C4—H4 120.9
O4—C10—C12 110.35 (12) C3—C2—C1 118.99 (15)
O4—C10—C11 106.15 (13) C3—C2—H2A 120.5
C6—N2—H2 117.1 C4—C5—N2 119.12 (13)
C6—N2—C5 125.74 (13) C4—C3—H3 120.6
C6—C7—C9 118.33 (13) C12—C10—C11 113.15 (13)
C6—C7—C8 120.77 (14) H12B—C12—H12C 109.5
O1—C9—O3 117.68 (13) H12B—C12—H12A 109.5
O1—C9—C7 126.57 (14) H12C—C12—H12A 109.5
O2—C8—O4 118.03 (13) H11A—C11—H11C 109.5
O2—C8—C7 125.08 (14) H11A—C11—H11B 109.5
N2—C6—H6 117.3 H11C—C11—H11B 109.5
N2—C6—C7 125.42 (14) C2—C1—H1 118.2
C7—C6—H6 117.3 C2—C3—H3 120.6
N1—C1—H1 118.2 C2—C3—C4 118.84 (15)
N1—C1—C2 123.64 (15) C10—C12—H12B 109.5
N1—C5—N2 116.58 (13) C10—C12—H12C 109.5
N1—C5—C4 124.30 (14) C10—C12—H12A 109.5
C1—C2—H2A 120.5 C10—C11—H11A 109.5
C9—O3—C10 118.08 (11) C10—C11—H11C 109.5
C9—C7—C8 120.72 (13) C10—C11—H11B 109.5
C8—O4—C10 117.75 (11)
C6—N2—C5—N1 −4.6 (2) C9—O3—C10—C11 −165.07 (13)
C6—N2—C5—C4 175.96 (15) C9—C7—C8—O4 −9.6 (2)
C6—C7—C9—O3 −177.16 (12) C9—C7—C8—O2 168.03 (15)
C6—C7—C9—O1 6.0 (2) C8—O4—C10—O3 47.99 (17)
C6—C7—C8—O4 175.36 (13) C8—O4—C10—C12 −74.10 (16)
C6—C7—C8—O2 −7.0 (2) C8—O4—C10—C11 162.95 (12)
N2—C6—C7—C9 −177.35 (14) C8—C7—C9—O3 7.7 (2)
N2—C6—C7—C8 −2.2 (2) C8—C7—C9—O1 −169.19 (15)
N2—C5—C4—C3 179.53 (14) C5—N1—C1—C2 0.7 (2)
C7—C6—N2—C5 −178.57 (14) C4—C3—C2—C1 −0.7 (3)
N1—C1—C2—C3 0.0 (3) C2—C3—C4—C5 0.6 (2)
N1—C5—C4—C3 0.2 (2) C10—O3—C9—O1 −159.37 (14)
C1—N1—C5—N2 179.83 (13) C10—O3—C9—C7 23.48 (19)
C1—N1—C5—C4 −0.8 (2) C10—O4—C8—O2 162.84 (14)
C9—O3—C10—O4 −50.35 (17) C10—O4—C8—C7 −19.38 (19)
C9—O3—C10—C12 71.76 (16)
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2327).

References

  1. Cassis, R., Tapia, R. & Valderrama, J. A. (1985). Synth. Commun 15, 125–133.
  2. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.
  3. Oxford Diffraction (2009). CrysAlis PRO Oxford Diffraction Ltd, Yarnton, England.
  4. 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. [DOI] [PubMed]
  5. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  6. Shi, J.-Y., Yang, J.-C. & Yang, J.-L. (2009). Acta Cryst. E65, o2458. [DOI] [PMC free article] [PubMed]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053250/bh2327sup1.cif

e-67-0o253-sup1.cif (16.2KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053250/bh2327Isup2.hkl

e-67-0o253-Isup2.hkl (114.7KB, hkl)

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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