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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1296.
Published online 2009 May 14. doi:  10.1107/S1600536809017437
PMCID: PMC2969579

2-{4-[(2,2-Dimethyl-4,6-dioxo-1,3-dioxan-5-yl­idene)methyl­amino]phen­yl}acetonitrile

Abstract

The title compound, C15H14N2O4, is approximately planar, with a dihedral angle of 6.48 (4)° between the amino­methyl­ene unit and the planar five-atom part of the dioxane ring, and a dihedral angle of 2.40 (4)° between amino­methyl­ene unit and the phenyl­ene ring. The dioxane ring is envelope shaped, with the dimethyl-substituted C atom that represents the flap 0.535 (8) Å out of the plane. The mol­ecule has an intra­molecular N—H(...)O hydrogen bond.

Related literature

For the synthesis of related compounds, see: Cassis et al. (1985 [triangle]). For the synthesis of related anti­tumor precursors, see: Ruchelman et al. (2003 [triangle]). For the crystal structure of a related compound, see: da Silva et al. (2006 [triangle]). For Meldrum’s acid, see: Meldrum (1908 [triangle]).

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Object name is e-65-o1296-scheme1.jpg

Experimental

Crystal data

  • C15H14N2O4
  • M r = 286.28
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1296-efi1.jpg
  • a = 5.204 (3) Å
  • b = 11.239 (3) Å
  • c = 12.209 (4) Å
  • α = 85.51 (3)°
  • β = 82.30 (3)°
  • γ = 84.54 (2)°
  • V = 702.9 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 292 K
  • 0.52 × 0.48 × 0.23 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 3217 measured reflections
  • 2609 independent reflections
  • 1610 reflections with I > 2σ(I)
  • R int = 0.003
  • 3 standard reflections every 150 reflections intensity decay: 1.3%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.150
  • S = 1.09
  • 2609 reflections
  • 196 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: DIFRAC (Gabe & White, 1993 [triangle]); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809017437/ng2579sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017437/ng2579Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

In the structure of the title molecule (Fig. 1), it is approximately planar with the dihedral angles of 6.48 (4)° and 2.40 (4)° between the connecting aminomethylene unit and the planar part of the dioxane ring, and between the dimethoxybenzyl ring and the aminomethylene group, respectively. Besides, the dioxane ring of the title compound exhibits a half-boat conformation, in which the C atom between the dioxane oxygen atoms is -0.535 (8) Å out-of-plane.

The intramolecular N—H···O hydrogen bond (Table 1) is stabilizing the planar conformation in the molecule. Intermolecular weak C—H···O hydrogen bonding contacts (Table 1) result in the formation of sheets running parallel to the a-c plane in the crystal structure (Fig. 2).

Experimental

A 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 arylamine (1.32 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.

Refinement

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 Uĩso(H) = 1.5Ueq(C) for methyl and 1.2Ueq(C) for the others.

Figures

Fig. 1.
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
A packing diagram of the title compound showing the layer-like aggregation of the title molecules in the unit cell.

Crystal data

C15H14N2O4Z = 2
Mr = 286.28F(000) = 300
Triclinic, P1Dx = 1.353 Mg m3
a = 5.204 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.239 (3) ÅCell parameters from 26 reflections
c = 12.209 (4) Åθ = 5.5–9.7°
α = 85.51 (3)°µ = 0.10 mm1
β = 82.30 (3)°T = 292 K
γ = 84.54 (2)°Block, colourless
V = 702.9 (5) Å30.52 × 0.48 × 0.23 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.003
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 1.7°
graphiteh = −6→6
ω/2–θ scansk = −2→13
3217 measured reflectionsl = −14→14
2609 independent reflections3 standard reflections every 150 reflections
1610 reflections with I > 2σ(I) intensity decay: 1.3%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: mixed
wR(F2) = 0.150H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0853P)2] where P = (Fo2 + 2Fc2)/3
2609 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.20 e Å3

Special details

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)

xyzUiso*/Ueq
O10.5677 (3)0.03464 (12)0.29695 (11)0.0620 (4)
O20.8342 (3)0.19500 (12)0.26775 (11)0.0573 (4)
O30.2465 (3)0.02806 (12)0.43304 (11)0.0639 (4)
O40.7647 (3)0.35124 (12)0.36881 (12)0.0634 (4)
N10.1001 (3)0.22676 (14)0.54592 (13)0.0498 (4)
H1N0.074 (5)0.145 (2)0.5335 (18)0.091 (8)*
N2−0.9365 (5)0.3352 (2)0.9847 (2)0.1123 (9)
C10.9231 (5)0.0301 (2)0.1573 (2)0.0831 (8)
H1A1.01960.07540.09840.125*
H1B0.8480−0.03290.12710.125*
H1C1.0377−0.00400.20900.125*
C20.5317 (5)0.1765 (2)0.13934 (18)0.0744 (7)
H2A0.39120.22030.18230.112*
H2B0.46290.11980.09860.112*
H2C0.62680.23110.08860.112*
C30.7107 (4)0.11099 (19)0.21537 (16)0.0573 (6)
C40.4120 (4)0.08606 (17)0.38115 (16)0.0519 (5)
C50.4624 (4)0.20480 (16)0.40360 (15)0.0471 (5)
C60.6901 (4)0.25836 (17)0.34787 (15)0.0477 (5)
C70.3046 (4)0.26618 (16)0.48329 (15)0.0493 (5)
H70.34590.34280.49410.059*
C8−0.0785 (4)0.29056 (16)0.62235 (15)0.0472 (5)
C9−0.2817 (4)0.23184 (17)0.67757 (17)0.0568 (6)
H9−0.29710.15280.66380.068*
C10−0.4632 (4)0.28879 (18)0.75328 (16)0.0573 (6)
H10−0.59970.24760.79010.069*
C11−0.4454 (4)0.40591 (18)0.77514 (16)0.0507 (5)
C12−0.2402 (4)0.46434 (17)0.71855 (16)0.0535 (5)
H12−0.22530.54350.73210.064*
C13−0.0575 (4)0.40860 (17)0.64268 (16)0.0541 (5)
H130.07860.44970.60550.065*
C14−0.6446 (4)0.47201 (19)0.85500 (16)0.0608 (6)
H14A−0.55480.51840.89940.073*
H14B−0.75410.52780.81300.073*
C15−0.8082 (5)0.3952 (2)0.92822 (19)0.0722 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0652 (9)0.0508 (8)0.0660 (9)−0.0175 (7)0.0196 (7)−0.0113 (7)
O20.0452 (8)0.0627 (8)0.0639 (9)−0.0173 (7)0.0036 (7)−0.0054 (7)
O30.0655 (9)0.0509 (8)0.0712 (9)−0.0237 (7)0.0208 (7)−0.0066 (7)
O40.0655 (10)0.0527 (8)0.0744 (9)−0.0237 (7)−0.0061 (8)−0.0008 (7)
N10.0521 (10)0.0400 (9)0.0560 (9)−0.0069 (8)0.0003 (8)−0.0045 (7)
N20.112 (2)0.0951 (17)0.1082 (18)−0.0057 (15)0.0499 (16)0.0130 (14)
C10.0696 (17)0.0865 (18)0.0876 (17)−0.0170 (15)0.0277 (14)−0.0232 (15)
C20.0662 (15)0.0952 (18)0.0641 (14)−0.0285 (14)−0.0041 (12)−0.0003 (13)
C30.0520 (12)0.0619 (12)0.0571 (12)−0.0221 (11)0.0108 (10)−0.0073 (10)
C40.0511 (12)0.0481 (11)0.0539 (11)−0.0108 (10)0.0060 (10)−0.0019 (9)
C50.0457 (11)0.0442 (10)0.0507 (11)−0.0097 (9)−0.0017 (9)0.0007 (9)
C60.0449 (11)0.0456 (10)0.0523 (11)−0.0087 (9)−0.0041 (9)0.0016 (9)
C70.0522 (12)0.0413 (10)0.0537 (11)−0.0080 (9)−0.0031 (10)0.0001 (9)
C80.0477 (11)0.0442 (10)0.0489 (11)−0.0069 (9)−0.0019 (9)−0.0016 (8)
C90.0632 (14)0.0410 (11)0.0657 (13)−0.0151 (10)0.0017 (11)−0.0055 (10)
C100.0567 (13)0.0499 (11)0.0631 (13)−0.0166 (10)0.0086 (10)−0.0036 (10)
C110.0506 (12)0.0497 (11)0.0501 (11)−0.0044 (9)−0.0022 (9)0.0003 (9)
C120.0563 (13)0.0397 (10)0.0630 (12)−0.0061 (9)0.0018 (10)−0.0068 (9)
C130.0505 (12)0.0472 (11)0.0628 (12)−0.0106 (10)0.0037 (10)−0.0029 (9)
C140.0619 (14)0.0592 (12)0.0572 (12)−0.0039 (11)0.0071 (11)−0.0049 (10)
C150.0707 (16)0.0721 (15)0.0639 (14)0.0053 (13)0.0158 (12)0.0019 (12)

Geometric parameters (Å, °)

O1—C41.352 (2)C4—C51.438 (2)
O1—C31.439 (2)C5—C71.371 (3)
O2—C61.356 (2)C5—C61.444 (3)
O2—C31.426 (2)C7—H70.9300
O3—C41.210 (2)C8—C91.371 (3)
O4—C61.205 (2)C8—C131.386 (3)
N1—C71.316 (2)C9—C101.379 (3)
N1—C81.412 (2)C9—H90.9300
N1—H1n0.96 (2)C10—C111.378 (3)
N2—C151.125 (3)C10—H100.9300
C1—C31.500 (3)C11—C121.383 (3)
C1—H1A0.9600C11—C141.508 (3)
C1—H1B0.9600C12—C131.377 (3)
C1—H1C0.9600C12—H120.9300
C2—C31.505 (3)C13—H130.9300
C2—H2A0.9600C14—C151.444 (3)
C2—H2B0.9600C14—H14A0.9700
C2—H2C0.9600C14—H14B0.9700
C4—O1—C3118.27 (15)O4—C6—C5125.76 (19)
C6—O2—C3118.41 (15)O2—C6—C5115.95 (15)
C7—N1—C8127.60 (16)N1—C7—C5126.03 (17)
C7—N1—H1N112.8 (15)N1—C7—H7117.0
C8—N1—H1N119.5 (15)C5—C7—H7117.0
C3—C1—H1A109.5C9—C8—C13119.39 (18)
C3—C1—H1B109.5C9—C8—N1117.65 (16)
H1A—C1—H1B109.5C13—C8—N1122.96 (17)
C3—C1—H1C109.5C8—C9—C10120.69 (17)
H1A—C1—H1C109.5C8—C9—H9119.7
H1B—C1—H1C109.5C10—C9—H9119.7
C3—C2—H2A109.5C11—C10—C9120.89 (19)
C3—C2—H2B109.5C11—C10—H10119.6
H2A—C2—H2B109.5C9—C10—H10119.6
C3—C2—H2C109.5C10—C11—C12117.88 (19)
H2A—C2—H2C109.5C10—C11—C14122.30 (19)
H2B—C2—H2C109.5C12—C11—C14119.80 (17)
O2—C3—O1110.49 (15)C13—C12—C11121.86 (17)
O2—C3—C1106.90 (17)C13—C12—H12119.1
O1—C3—C1105.58 (18)C11—C12—H12119.1
O2—C3—C2109.82 (18)C12—C13—C8119.30 (18)
O1—C3—C2110.28 (17)C12—C13—H13120.4
C1—C3—C2113.65 (19)C8—C13—H13120.4
O3—C4—O1117.85 (16)C15—C14—C11114.09 (18)
O3—C4—C5125.29 (18)C15—C14—H14A108.7
O1—C4—C5116.83 (16)C11—C14—H14A108.7
C7—C5—C4120.65 (17)C15—C14—H14B108.7
C7—C5—C6118.69 (16)C11—C14—H14B108.7
C4—C5—C6120.53 (17)H14A—C14—H14B107.6
O4—C6—O2118.25 (17)N2—C15—C14179.5 (3)
C6—O2—C3—O1−49.2 (2)C8—N1—C7—C5−174.51 (18)
C6—O2—C3—C1−163.65 (17)C4—C5—C7—N10.3 (3)
C6—O2—C3—C272.6 (2)C6—C5—C7—N1−175.62 (18)
C4—O1—C3—O246.8 (2)C7—N1—C8—C9178.79 (18)
C4—O1—C3—C1162.08 (18)C7—N1—C8—C13−0.7 (3)
C4—O1—C3—C2−74.8 (2)C13—C8—C9—C10−0.4 (3)
C3—O1—C4—O3162.19 (19)N1—C8—C9—C10−179.96 (18)
C3—O1—C4—C5−19.5 (3)C8—C9—C10—C110.1 (3)
O3—C4—C5—C7−5.6 (3)C9—C10—C11—C120.2 (3)
O1—C4—C5—C7176.25 (17)C9—C10—C11—C14178.25 (19)
O3—C4—C5—C6170.2 (2)C10—C11—C12—C13−0.1 (3)
O1—C4—C5—C6−7.9 (3)C14—C11—C12—C13−178.27 (19)
C3—O2—C6—O4−158.33 (18)C11—C12—C13—C8−0.2 (3)
C3—O2—C6—C523.8 (2)C9—C8—C13—C120.4 (3)
C7—C5—C6—O44.2 (3)N1—C8—C13—C12179.96 (18)
C4—C5—C6—O4−171.73 (19)C10—C11—C14—C1516.7 (3)
C7—C5—C6—O2−178.17 (16)C12—C11—C14—C15−165.3 (2)
C4—C5—C6—O25.9 (3)C11—C14—C15—N2−69 (31)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1n···O30.97 (2)1.94 (2)2.710 (3)135 (2)
C7—H7···O40.932.492.816 (3)100
C9—H9···O3i0.932.413.292 (3)159
C13—H13···O4ii0.932.513.208 (3)132
C14—H14B···O4iii0.972.513.343 (3)143

Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2579).

References

  • Cassis, R., Tapia, R. & Valderrama, J. A. (1985). Synth. Commun.15, 125–133.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Gabe, E. J. & White, P. S. (1993). DIFRAC American Crystallographic Association Meeting, Pittsburgh, Abstract PA 104.
  • Meldrum, A. N. (1908). J. Chem. Soc. Trans.93, 598–601.
  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Silva, L. E. da, Joussef, A. C., Silva, L. L., Foro, S. & Schmidt, B. (2006). Acta Cryst. E62, o3866–o3867.
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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