5-[(4-Acetyl­phenyl)­aminomethyl­ene]-2,2-dimethyl-1,3-dioxane-4,6-dione

Li, R.; Ding, Z.-Y.; Wei, Y.-Q.; Ding, J.

doi:10.1107/S1600536809017425

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1297

doi:10.1107/S1600536809017425

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5-[(4-Acetylphenyl)aminomethylene]-2,2-dimethyl-1,3-dioxane-4,6-dione

Rui Li,^a ^* Zhen-Yu Ding,^a Yu-Quan Wei ^a and Jian Ding ^b

^aState Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, People's Republic of China, and ^bState Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, 201203, People's Republic of China
^*Correspondence e-mail: lirui@scu.edu.cn

(Received 3 May 2009; accepted 8 May 2009; online 14 May 2009)

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—H⋯O hydrogen bonds into supramolecular chains along the b axis.

Related literature

For the biological activity of 4(1H)-quinolone structures, see: Ruchelman et al. (2003 ). 5-Arylaminomethylene-2,2-dimethyl-1,3-dioxane-4,6-diones are key intermediates in the synthesis of 4(1H)quinolone derivatives by thermolysis (Cassis et al., 1985 ).

Experimental

Crystal data

C₁₅H₁₅NO₅
M_r = 289.28
Triclinic, $[P \overline 1]$
a = 7.102 (3) Å
b = 7.356 (4) Å
c = 13.856 (4) Å
α = 82.79 (4)°
β = 83.19 (4)°
γ = 86.03 (4)°
V = 712.0 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 292 K
0.44 × 0.36 × 0.32 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2894 measured reflections
2621 independent reflections
1399 reflections with I > 2σ(I)
R_int = 0.008
3 standard reflections every 100 reflections intensity decay: 1.8%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.179
S = 1.03
2621 reflections
197 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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 code: (i) x, y-1, z.

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; 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.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809017425/xu2521sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017425/xu2521Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For the biological activity 4(1H)quinolone structures, see: Ruchelman et al. (2003). 5-Arylaminomethylene-2,2-dimethyl-1,3-dioxane-4,6-diones are key intermediates in the synthesis of 4(1H)quinolone derivatives by thermolysis (Cassis et al., 1985).

Experimental top

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.

Computing details top

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).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

5-[(4-Acetylphenyl)aminomethylene]-2,2-dimethyl-1,3-dioxane-4,6-dione top

Crystal data top

C₁₅H₁₅NO₅	Z = 2
M_r = 289.28	F(000) = 304
Triclinic, P1	D_x = 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 = 4.4–7.4°
c = 13.856 (4) Å	µ = 0.10 mm⁻¹
α = 82.79 (4)°	T = 292 K
β = 83.19 (4)°	Block, colourless
γ = 86.03 (4)°	0.44 × 0.36 × 0.32 mm
V = 712.0 (5) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 1.5°
Graphite monochromator	h = −8→8
ω/2θ scans	k = −3→8
2894 measured reflections	l = −16→16
2621 independent reflections	3 standard reflections every 100 reflections
1399 reflections with I > 2σ(I)	intensity decay: 1.8%

Refinement top

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0987P)²] where P = (F_o² + 2F_c²)/3
2621 reflections	(Δ/σ)_max < 0.001
197 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₅H₁₅NO₅	γ = 86.03 (4)°
M_r = 289.28	V = 712.0 (5) Å³
Triclinic, P1	Z = 2
a = 7.102 (3) Å	Mo Kα radiation
b = 7.356 (4) Å	µ = 0.10 mm⁻¹
c = 13.856 (4) Å	T = 292 K
α = 82.79 (4)°	0.44 × 0.36 × 0.32 mm
β = 83.19 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
2894 measured reflections	3 standard reflections every 100 reflections
2621 independent reflections	intensity decay: 1.8%
1399 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.23 e Å⁻³
2621 reflections	Δρ_min = −0.34 e Å⁻³
197 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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 code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₅
M_r	289.28
Crystal system, space group	Triclinic, P1
Temperature (K)	292
a, b, c (Å)	7.102 (3), 7.356 (4), 13.856 (4)
α, β, γ (°)	82.79 (4), 83.19 (4), 86.03 (4)
V (Å³)	712.0 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.44 × 0.36 × 0.32

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2894, 2621, 1399
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.179, 1.03
No. of reflections	2621
No. of parameters	197
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.34

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

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 code: (i) x, y−1, z.

Acknowledgements

This research is financially supported by the State Key Laboratory of Drug Research, Shanghai Institute of Materia Medica, Chinese Academy of Sciences.

References

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