2,2-Dimethyl-5-(1-naphthyl­amino­methyl­ene)-1,3-dioxane-4,6-dione

Li, Z.; Li, R.; Ding, Z.-Y.

doi:10.1107/S1600536809033984

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2289

doi:10.1107/S1600536809033984

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2,2-Dimethyl-5-(1-naphthylaminomethylene)-1,3-dioxane-4,6-dione

Zhi Li,^a Rui Li ^a ^* and Zhen-Yu Ding ^a

^aState Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: lirui@scu.edu.cn

(Received 29 July 2009; accepted 25 August 2009; online 29 August 2009)

The benzyl ring of the title compound, C₁₇H₁₅NO₄, is twisted away from the plane defined by five atoms of the dioxane ring by 34.83 (4)°. The dioxane ring exhibits a half-boat conformation, with the C atom between the dioxane O atoms 0.571 (8) Å out of the plane through the remainder of the ring. An intramolecular N—H⋯O hydrogen bond may contribute to the stabilization of the planar conformation of the molecule. In the crystal, inversion dimers linked by pairs of C—H⋯O bonds occur.

Related literature

For the synthesis of related compounds, see: Cassis et al. (1985 ). For the pharmacological activity of 4(1H)-quinolone structures, see: Ruchelman et al. (2003 ).

Experimental

Crystal data

C₁₇H₁₅NO₄
M_r = 297.30
Triclinic, $[P \overline 1]$
a = 7.4696 (11) Å
b = 8.0805 (12) Å
c = 12.1240 (18) Å
α = 98.601 (2)°
β = 96.428 (2)°
γ = 92.198 (2)°
V = 717.87 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
4513 measured reflections
3194 independent reflections
2571 reflections with I > 2σ(I)
R_int = 0.014

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.110
S = 1.03
3194 reflections
206 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.920 (18)	1.982 (18)	2.7130 (16)	135.2 (15)
C1—H1C⋯O4ⁱ	0.98	2.60	3.3709 (19)	136
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2000 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033984/ez2178sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033984/ez2178Isup2.hkl

checkCIF report

Comment top

4(1H)-Quinolone structures have long attracted pharmacological interest as anticancer agents, anti-malarial agents and reversible (H+/K+) ATPase inhibitors (Ruchelman et al., 2003). Thermolysis of 5-arylaminomethylene-2,2-dimethyl-1,3-dioxane-4,6-diones is an effective method to synthesize 4(1H)quinolone derivatives (Cassis et al., 1985).

The benzyl ring is twisted away from the plane defined by the dioxane ring by 34.83 (4)°. In turn, the dioxane ring of the title compound exhibits an envelope conformation, in which the flap atom, the C atom between the dioxane oxygen atoms, is -0.571 (8) Å out of the plane. An intramolecular N—H···O hydrogen bond (Table 1) could lead to the dioxane ring and the aminomethylene group taking up their planar conformation.

Related literature top

For the synthesis of related compounds, see: Cassis et al. (1985) and of related antitumor precursors, see Ruchelman et al. (2003).

Experimental top

An ethanol solution (50 ml) of 2,2-dimethyl-1,3-dioxane-4,6-dione (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 naphthalen-1-amine (1.43 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 days.

Computing details top

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 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. The hydrogen bond is shown by a dashed line.

2,2-Dimethyl-5-(1-naphthylaminomethylene)-1,3-dioxane-4,6-dione top

Crystal data top

C₁₇H₁₅NO₄	Z = 2
M_r = 297.30	F(000) = 312
Triclinic, P1	D_x = 1.375 Mg m⁻³
a = 7.4696 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0805 (12) Å	Cell parameters from 2197 reflections
c = 12.1240 (18) Å	θ = 2.6–27.5°
α = 98.601 (2)°	µ = 0.10 mm⁻¹
β = 96.428 (2)°	T = 153 K
γ = 92.198 (2)°	Block, colourless
V = 717.87 (18) Å³	0.25 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2571 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.014
Graphite monochromator	θ_max = 27.6°, θ_min = 2.6°
ϕ and ω scans	h = −9→6
4513 measured reflections	k = −10→10
3194 independent reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0462P)² + 0.1278P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3194 reflections	Δρ_max = 0.18 e Å⁻³
206 parameters	Δρ_min = −0.16 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: 0.204 (9)

Crystal data top

C₁₇H₁₅NO₄	γ = 92.198 (2)°
M_r = 297.30	V = 717.87 (18) Å³
Triclinic, P1	Z = 2
a = 7.4696 (11) Å	Mo Kα radiation
b = 8.0805 (12) Å	µ = 0.10 mm⁻¹
c = 12.1240 (18) Å	T = 153 K
α = 98.601 (2)°	0.25 × 0.20 × 0.20 mm
β = 96.428 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2571 reflections with I > 2σ(I)
4513 measured reflections	R_int = 0.014
3194 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.18 e Å⁻³
3194 reflections	Δρ_min = −0.16 e Å⁻³
206 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	0.75507 (13)	0.44446 (12)	0.48110 (8)	0.0482 (3)
O2	0.61634 (12)	0.29559 (12)	0.60505 (7)	0.0468 (3)
O3	0.66547 (15)	0.40648 (13)	0.29855 (8)	0.0567 (3)
O4	0.36615 (13)	0.13711 (12)	0.54766 (8)	0.0501 (3)
N1	0.41749 (15)	0.15238 (15)	0.21325 (9)	0.0431 (3)
H1	0.496 (3)	0.236 (2)	0.2012 (15)	0.074 (5)*
C1	0.9036 (2)	0.21096 (19)	0.54644 (13)	0.0529 (4)
H1A	0.9247	0.1511	0.6109	0.079*
H1B	1.0193	0.2541	0.5281	0.079*
H1C	0.8432	0.1340	0.4816	0.079*
C2	0.8669 (2)	0.4816 (2)	0.67397 (13)	0.0583 (4)
H2A	0.7830	0.5704	0.6887	0.087*
H2B	0.9809	0.5306	0.6571	0.087*
H2C	0.8895	0.4262	0.7404	0.087*
C3	0.78588 (18)	0.35520 (17)	0.57518 (11)	0.0433 (3)
C4	0.64805 (18)	0.36396 (16)	0.38885 (11)	0.0420 (3)
C5	0.51881 (17)	0.23873 (16)	0.40821 (10)	0.0384 (3)
C6	0.49111 (17)	0.21600 (16)	0.52166 (10)	0.0393 (3)
C7	0.41364 (17)	0.14044 (16)	0.32061 (10)	0.0401 (3)
H7	0.3322	0.0579	0.3385	0.048*
C8	0.32676 (17)	0.04147 (17)	0.12053 (10)	0.0412 (3)
C9	0.2809 (2)	−0.12053 (18)	0.12899 (12)	0.0502 (3)
H9	0.3068	−0.1605	0.1986	0.060*
C10	0.1953 (2)	−0.2285 (2)	0.03460 (14)	0.0598 (4)
H10	0.1584	−0.3399	0.0416	0.072*
C11	0.1648 (2)	−0.1750 (2)	−0.06667 (13)	0.0593 (4)
H11	0.1097	−0.2505	−0.1301	0.071*
C12	0.21389 (18)	−0.0086 (2)	−0.07868 (11)	0.0495 (4)
C13	0.1908 (2)	0.0502 (3)	−0.18422 (12)	0.0624 (5)
H13	0.1415	−0.0247	−0.2495	0.075*
C14	0.2376 (2)	0.2106 (3)	−0.19338 (13)	0.0663 (5)
H14	0.2247	0.2460	−0.2650	0.080*
C15	0.3050 (2)	0.3242 (2)	−0.09805 (13)	0.0608 (4)
H15	0.3325	0.4378	−0.1047	0.073*
C16	0.3315 (2)	0.2734 (2)	0.00486 (12)	0.0513 (4)
H16	0.3775	0.3521	0.0690	0.062*
C17	0.29151 (17)	0.10513 (18)	0.01706 (10)	0.0428 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0558 (6)	0.0465 (5)	0.0405 (5)	−0.0043 (4)	−0.0028 (4)	0.0094 (4)
O2	0.0450 (5)	0.0633 (6)	0.0309 (5)	−0.0001 (4)	0.0023 (4)	0.0057 (4)
O3	0.0686 (7)	0.0633 (6)	0.0400 (6)	−0.0081 (5)	0.0034 (5)	0.0195 (5)
O4	0.0499 (6)	0.0620 (6)	0.0394 (5)	−0.0027 (5)	0.0111 (4)	0.0081 (4)
N1	0.0441 (6)	0.0532 (7)	0.0315 (6)	0.0003 (5)	0.0015 (4)	0.0076 (5)
C1	0.0452 (8)	0.0568 (8)	0.0550 (9)	0.0065 (6)	−0.0014 (6)	0.0080 (7)
C2	0.0610 (9)	0.0622 (9)	0.0457 (8)	−0.0021 (7)	−0.0061 (7)	−0.0001 (7)
C3	0.0440 (7)	0.0503 (7)	0.0346 (7)	0.0002 (6)	0.0001 (5)	0.0074 (5)
C4	0.0478 (7)	0.0433 (7)	0.0349 (7)	0.0044 (5)	0.0014 (5)	0.0081 (5)
C5	0.0398 (7)	0.0448 (7)	0.0311 (6)	0.0056 (5)	0.0023 (5)	0.0079 (5)
C6	0.0398 (7)	0.0447 (7)	0.0335 (6)	0.0069 (5)	0.0037 (5)	0.0055 (5)
C7	0.0391 (7)	0.0483 (7)	0.0341 (6)	0.0060 (5)	0.0047 (5)	0.0087 (5)
C8	0.0357 (6)	0.0547 (8)	0.0322 (6)	0.0057 (5)	0.0033 (5)	0.0030 (5)
C9	0.0539 (8)	0.0557 (8)	0.0414 (7)	0.0080 (6)	0.0071 (6)	0.0062 (6)
C10	0.0617 (10)	0.0548 (9)	0.0594 (10)	0.0020 (7)	0.0080 (7)	−0.0026 (7)
C11	0.0517 (9)	0.0699 (10)	0.0475 (9)	0.0058 (7)	−0.0028 (7)	−0.0136 (7)
C12	0.0386 (7)	0.0714 (9)	0.0354 (7)	0.0127 (6)	0.0010 (5)	−0.0017 (6)
C13	0.0523 (9)	0.0978 (13)	0.0327 (7)	0.0195 (8)	−0.0036 (6)	−0.0017 (8)
C14	0.0590 (10)	0.1060 (14)	0.0386 (8)	0.0215 (9)	0.0055 (7)	0.0229 (9)
C15	0.0567 (9)	0.0829 (11)	0.0477 (9)	0.0095 (8)	0.0052 (7)	0.0246 (8)
C16	0.0489 (8)	0.0663 (9)	0.0391 (7)	0.0034 (7)	0.0023 (6)	0.0119 (6)
C17	0.0343 (6)	0.0622 (8)	0.0315 (6)	0.0089 (6)	0.0040 (5)	0.0044 (6)

Geometric parameters (Å, º) top

O1—C4	1.3622 (15)	C7—H7	0.9500
O1—C3	1.4403 (15)	C8—C9	1.362 (2)
O2—C6	1.3632 (15)	C8—C17	1.4271 (18)
O2—C3	1.4405 (16)	C9—C10	1.405 (2)
O3—C4	1.2142 (15)	C9—H9	0.9500
O4—C6	1.2072 (15)	C10—C11	1.360 (2)
N1—C7	1.3229 (16)	C10—H10	0.9500
N1—C8	1.4170 (16)	C11—C12	1.413 (2)
N1—H1	0.920 (18)	C11—H11	0.9500
C1—C3	1.510 (2)	C12—C17	1.4204 (19)
C1—H1A	0.9800	C12—C13	1.425 (2)
C1—H1B	0.9800	C13—C14	1.353 (3)
C1—H1C	0.9800	C13—H13	0.9500
C2—C3	1.5063 (19)	C14—C15	1.396 (2)
C2—H2A	0.9800	C14—H14	0.9500
C2—H2B	0.9800	C15—C16	1.367 (2)
C2—H2C	0.9800	C15—H15	0.9500
C4—C5	1.4345 (18)	C16—C17	1.414 (2)
C5—C7	1.3743 (17)	C16—H16	0.9500
C5—C6	1.4508 (17)

C4—O1—C3	116.84 (10)	N1—C7—H7	117.6
C6—O2—C3	118.48 (10)	C5—C7—H7	117.6
C7—N1—C8	126.21 (12)	C9—C8—N1	121.29 (12)
C7—N1—H1	113.8 (11)	C9—C8—C17	121.54 (12)
C8—N1—H1	119.7 (11)	N1—C8—C17	117.13 (12)
C3—C1—H1A	109.5	C8—C9—C10	119.85 (14)
C3—C1—H1B	109.5	C8—C9—H9	120.1
H1A—C1—H1B	109.5	C10—C9—H9	120.1
C3—C1—H1C	109.5	C11—C10—C9	120.64 (15)
H1A—C1—H1C	109.5	C11—C10—H10	119.7
H1B—C1—H1C	109.5	C9—C10—H10	119.7
C3—C2—H2A	109.5	C10—C11—C12	120.82 (14)
C3—C2—H2B	109.5	C10—C11—H11	119.6
H2A—C2—H2B	109.5	C12—C11—H11	119.6
C3—C2—H2C	109.5	C11—C12—C17	119.39 (13)
H2A—C2—H2C	109.5	C11—C12—C13	122.49 (14)
H2B—C2—H2C	109.5	C17—C12—C13	118.11 (15)
O1—C3—O2	110.06 (10)	C14—C13—C12	121.36 (15)
O1—C3—C2	106.69 (11)	C14—C13—H13	119.3
O2—C3—C2	105.71 (11)	C12—C13—H13	119.3
O1—C3—C1	109.85 (11)	C13—C14—C15	120.28 (15)
O2—C3—C1	110.62 (11)	C13—C14—H14	119.9
C2—C3—C1	113.75 (12)	C15—C14—H14	119.9
O3—C4—O1	118.14 (12)	C16—C15—C14	120.52 (16)
O3—C4—C5	125.52 (12)	C16—C15—H15	119.7
O1—C4—C5	116.31 (11)	C14—C15—H15	119.7
C7—C5—C4	121.36 (11)	C15—C16—C17	120.84 (15)
C7—C5—C6	117.92 (11)	C15—C16—H16	119.6
C4—C5—C6	120.69 (11)	C17—C16—H16	119.6
O4—C6—O2	118.28 (11)	C16—C17—C12	118.73 (13)
O4—C6—C5	125.74 (12)	C16—C17—C8	123.65 (12)
O2—C6—C5	115.95 (11)	C12—C17—C8	117.61 (13)
N1—C7—C5	124.76 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.920 (18)	1.982 (18)	2.7130 (16)	135.2 (15)
C1—H1C···O4ⁱ	0.98	2.60	3.3709 (19)	136

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅NO₄
M_r	297.30
Crystal system, space group	Triclinic, P1
Temperature (K)	153
a, b, c (Å)	7.4696 (11), 8.0805 (12), 12.1240 (18)
α, β, γ (°)	98.601 (2), 96.428 (2), 92.198 (2)
V (Å³)	717.87 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4513, 3194, 2571
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.110, 1.03
No. of reflections	3194
No. of parameters	206
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.16

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.920 (18)	1.982 (18)	2.7130 (16)	135.2 (15)
C1—H1C···O4ⁱ	0.98	2.60	3.3709 (19)	136

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

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

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