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

Shi, J.; Li, J.; Tong, R.; Lin, H.; Lu, C.

doi:10.1107/S1600536810053250

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o253

doi:10.1107/S1600536810053250

Open

access

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 and Chen Lu ^a

^aDepartment of Pharmacy, Sichuan Academy of Medical Science and Sichuan Provincial, People's Hospital, Chengdu 610072, People's Republic of China
^*Correspondence e-mail: shijianyoude@126.com

(Received 18 November 2010; accepted 18 December 2010; online 8 January 2011)

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 ).

Experimental

Crystal data

C₁₂H₁₂N₂O₄
M_r = 248.24
Monoclinic, P 2₁ /c
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 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.096
S = 1.03
2334 reflections
166 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

Experimental top

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.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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).

Figures top

Fig. 1. ORTEP-like view of the title compound.

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

Crystal data top

C₁₂H₁₂N₂O₄	F(000) = 520
M_r = 248.24	D_x = 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

Data collection top

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 monochromator	R_int = 0.018
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.4°
ω scans	h = −10→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −17→16
T_min = 0.997, T_max = 1.0	l = −11→11
4873 measured reflections

Refinement top

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(F_o²) + (0.0383P)² + 0.0655P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2334 reflections	Δρ_max = 0.14 e Å⁻³
166 parameters	Δρ_min = −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

Crystal data top

C₁₂H₁₂N₂O₄	V = 1152.4 (2) Å³
M_r = 248.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7344 (10) Å	µ = 0.11 mm⁻¹
b = 13.9712 (15) Å	T = 293 K
c = 9.4744 (11) Å	0.22 × 0.18 × 0.16 mm
β = 94.601 (11)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with an Eos CCD detector	2334 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1659 reflections with I > 2σ(I)
T_min = 0.997, T_max = 1.0	R_int = 0.018
4873 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.096	H-atom parameters constrained
S = 1.03	Δρ_max = 0.14 e Å⁻³
2334 reflections	Δρ_min = −0.14 e Å⁻³
166 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₄
M_r	248.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.7344 (10), 13.9712 (15), 9.4744 (11)
β (°)	94.601 (11)
V (Å³)	1152.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.22 × 0.18 × 0.16

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with an Eos CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.997, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	4873, 2334, 1659
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.096, 1.03
No. of reflections	2334
No. of parameters	166
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.14

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

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

References

Cassis, R., Tapia, R. & Valderrama, J. A. (1985). Synth. Commun. 15, 125–133. CrossRef CAS Web of Science Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
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. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, J.-Y., Yang, J.-C. & Yang, J.-L. (2009). Acta Cryst. E65, o2458. Web of Science CSD CrossRef IUCr Journals Google Scholar