4-Methyl-2H-1,3-oxazine-2,6(3H)-dione

Parrish, D.; Leuschner, F.; Rehberg, G.M.; Kastner, M.E.

doi:10.1107/S1600536809034618

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2354

doi:10.1107/S1600536809034618

Open

access

4-Methyl-2H-1,3-oxazine-2,6(3H)-dione

Damon Parrish,^a Fredrick Leuschner,^a Gretchen M. Rehberg ^a and Margaret E. Kastner ^a ^*

^aDepartment of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
^*Correspondence e-mail: kastner@bucknell.edu

(Received 13 August 2009; accepted 28 August 2009; online 5 September 2009)

In the title compound, C₅H₅NO₃, the planar (maximum deviation = 0.075 Å for the ring O atom) molecules form N—H⋯O hydrogen bonds in a zigzag chain (C—O⋯N bond angle ≃ 140°) between glide-related molecules.

Related literature

For synthetic background, see: Warren et al. (1975 ); Rehberg & Glass (1995 ). For related structures, see: Copley et al. (2005 ); Parrish, Leuschner et al. (2009 ); Parrish, Tivitmahaisoon et al. 2009 ).

Experimental

Crystal data

C₅H₅NO₃
M_r = 127.1
Monoclinic, P 2₁ /n
a = 7.254 (3) Å
b = 6.683 (2) Å
c = 11.689 (5) Å
β = 98.11 (4)°
V = 561.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.46 × 0.30 × 0.10 mm

Data collection

Bruker R3/V diffractometer
Absorption correction: none
1410 measured reflections
1294 independent reflections
910 reflections with I > 2σ(I)
R_int = 0.012
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.191
S = 0.93
1294 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O6ⁱ	0.86	2.02	2.877 (3)	173
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: XSCANS (Bruker, 1996 ); cell refinement: XSCANS (Bruker, 1996); data reduction: XSCANS (Bruker, 1996); 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: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034618/pv2197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034618/pv2197Isup2.hkl

checkCIF report

Comment top

The synthesis of derivatives of 3-oxauracil has previously been reported (Warren et al., 1975) and an improved synthesis of the unsubstituted 3-oxauracil was reported by Rehberg & Glass (1995). The structure of the unsubstituted 3-oxauracil and its monohydrate have been reported (Copley et al., 2005). Three derivatives of 3-oxauracil (4-methyl, 4-bromo, and 4,5-dichloro) have been prepared in our laboratory in route to the synthesis of 1-aza-1,3-butadienes. In this paper, we report the crystal structure of the title compound, (I).

In the title compound (Fig. 1) only one intermolecular H-bond is formed between N3 and O6 of glide-related molecules (details are given in Table 1). Although the molecules of (I) are planar, the H-bonding chains are staggered as shown in Figure 2. The hydrogen bonding networks in (I) differs significantly from the hydrogen bonding in 4,5-dichloro (Parrish, Leuschner et al., 2009) and 4-bromo (Parrish, Tivitmahaisoon et al., 2009) derivatives.

Related literature top

For synthetic background, see: Warren et al. (1975); Rehberg & Glass (1995). For related structures, see: Copley et al. (2005); Parrish, Leuschner et al. (2009); Parrish, Tivitmahaisoon et al. 2009).

Experimental top

Citraconic anhydride (3-methylfuran-2,5-dione, 2.0 ml, 22 mmol) and trimethylsilyl azide (3.0 ml, 23 mmol) were added to 10 ml dichloromethane at 273 K and stirred under nitrogen for 4 h. Upon warming to room temperature over night, a white precipitate formed. Ethanol (2.5 ml) was added, the mixture stirred 2 additional hours, and then the solvent was removed under reduced pressure to obtain the title compound; yield: 1.7 g (13 mmol, 59%). Crystals of the title compound were grown from a solution of acetone at room temperature by slow evaporation.

Computing details top

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS (Bruker, 1996); data reduction: XSCANS (Bruker, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of the title compound viewed down the a axis; intermolecular hydrogen bonds have been represented by dashed lines.

4-Methyl-2H-1,3-oxazine-2,6(3H)-dione top

Crystal data top

C₅H₅NO₃	F(000) = 264
M_r = 127.1	D_x = 1.505 Mg m⁻³ D_m = 1.46 Mg m⁻³ D_m measured by floatation in bromoform/hexane solution
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 20 reflections
a = 7.254 (3) Å	θ = 10–12.5°
b = 6.683 (2) Å	µ = 0.13 mm⁻¹
c = 11.689 (5) Å	T = 293 K
β = 98.11 (4)°	Plates, colorless
V = 561.0 (4) Å³	0.46 × 0.30 × 0.10 mm
Z = 4

Data collection top

Bruker R3/V diffractometer	R_int = 0.012
Radiation source: fine-focus sealed tube	θ_max = 27.6°, θ_min = 3.1°
Graphite monochromator	h = 0→9
θ – 2θ scans	k = 0→8
1410 measured reflections	l = −15→15
1294 independent reflections	3 standard reflections every 97 reflections
910 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.1301P)² + 0.1905P] where P = (F_o² + 2F_c²)/3
1294 reflections	(Δ/σ)_max = 0.005
83 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₅H₅NO₃	V = 561.0 (4) Å³
M_r = 127.1	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.254 (3) Å	µ = 0.13 mm⁻¹
b = 6.683 (2) Å	T = 293 K
c = 11.689 (5) Å	0.46 × 0.30 × 0.10 mm
β = 98.11 (4)°

Data collection top

Bruker R3/V diffractometer	R_int = 0.012
1410 measured reflections	3 standard reflections every 97 reflections
1294 independent reflections	intensity decay: none
910 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 0.93	Δρ_max = 0.23 e Å⁻³
1294 reflections	Δρ_min = −0.24 e Å⁻³
83 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	0.6042 (2)	0.1383 (2)	0.68042 (13)	0.0466 (5)
C2	0.4998 (3)	0.2078 (3)	0.58306 (19)	0.0422 (5)
O2	0.3337 (2)	0.2161 (3)	0.57888 (19)	0.0694 (6)
N3	0.5939 (2)	0.2571 (3)	0.49490 (14)	0.0406 (5)
H3	0.5305	0.2967	0.4312	0.049*
C4	0.7833 (3)	0.2477 (3)	0.50089 (18)	0.0392 (5)
C5	0.8847 (3)	0.1896 (3)	0.59971 (19)	0.0430 (5)
H5	1.0137	0.1846	0.6048	0.052*
C6	0.7988 (3)	0.1357 (3)	0.69668 (18)	0.0435 (5)
O6	0.8682 (3)	0.0868 (3)	0.79242 (15)	0.0695 (7)
C7	0.8619 (4)	0.3002 (5)	0.3938 (2)	0.0630 (8)
H7A	0.9955	0.2979	0.4093	0.095*
H7B	0.8210	0.4317	0.3687	0.095*
H7C	0.8201	0.2050	0.3343	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0448 (9)	0.0555 (10)	0.0417 (8)	−0.0028 (7)	0.0137 (6)	0.0020 (7)
C2	0.0329 (10)	0.0455 (12)	0.0490 (11)	0.0003 (8)	0.0086 (8)	−0.0068 (9)
O2	0.0324 (9)	0.0847 (14)	0.0936 (15)	−0.0020 (9)	0.0174 (9)	−0.0026 (11)
N3	0.0342 (9)	0.0511 (10)	0.0350 (9)	0.0041 (7)	0.0003 (7)	0.0010 (7)
C4	0.0374 (10)	0.0384 (10)	0.0445 (11)	0.0029 (8)	0.0152 (8)	−0.0025 (9)
C5	0.0294 (9)	0.0458 (12)	0.0534 (12)	0.0012 (9)	0.0049 (8)	−0.0021 (10)
C6	0.0447 (11)	0.0395 (11)	0.0435 (11)	−0.0024 (9)	−0.0038 (9)	−0.0025 (9)
O6	0.0831 (14)	0.0687 (13)	0.0494 (10)	−0.0096 (10)	−0.0167 (9)	0.0110 (9)
C7	0.0651 (16)	0.0733 (18)	0.0573 (14)	0.0053 (13)	0.0313 (12)	0.0133 (13)

Geometric parameters (Å, º) top

O1—C2	1.357 (3)	C4—C7	1.489 (3)
O1—C6	1.398 (3)	C5—C6	1.415 (3)
C2—O2	1.200 (3)	C5—H5	0.9300
C2—N3	1.354 (3)	C6—O6	1.206 (3)
N3—C4	1.368 (3)	C7—H7A	0.9600
N3—H3	0.8600	C7—H7B	0.9600
C4—C5	1.337 (3)	C7—H7C	0.9600

C2—O1—C6	123.50 (17)	C4—C5—H5	119.5
O2—C2—N3	124.6 (2)	C6—C5—H5	119.5
O2—C2—O1	119.2 (2)	O6—C6—O1	114.3 (2)
N3—C2—O1	116.10 (18)	O6—C6—C5	129.7 (2)
C2—N3—C4	124.08 (18)	O1—C6—C5	115.99 (18)
C2—N3—H3	118.0	C4—C7—H7A	109.5
C4—N3—H3	118.0	C4—C7—H7B	109.5
C5—C4—N3	118.95 (18)	H7A—C7—H7B	109.5
C5—C4—C7	124.5 (2)	C4—C7—H7C	109.5
N3—C4—C7	116.6 (2)	H7A—C7—H7C	109.5
C4—C5—C6	121.03 (19)	H7B—C7—H7C	109.5

C6—O1—C2—O2	−175.5 (2)	N3—C4—C5—C6	0.9 (3)
C6—O1—C2—N3	6.7 (3)	C7—C4—C5—C6	−177.8 (2)
O2—C2—N3—C4	179.7 (2)	C2—O1—C6—O6	173.2 (2)
O1—C2—N3—C4	−2.6 (3)	C2—O1—C6—C5	−6.9 (3)
C2—N3—C4—C5	−1.1 (3)	C4—C5—C6—O6	−177.3 (2)
C2—N3—C4—C7	177.7 (2)	C4—C5—C6—O1	2.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O6ⁱ	0.86	2.02	2.877 (3)	173

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₅H₅NO₃
M_r	127.1
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.254 (3), 6.683 (2), 11.689 (5)
β (°)	98.11 (4)
V (Å³)	561.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.46 × 0.30 × 0.10

Data collection
Diffractometer	Bruker R3/V diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	1410, 1294, 910
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.191, 0.93
No. of reflections	1294
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.24

Computer programs: XSCANS (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O6ⁱ	0.86	2.02	2.877 (3)	173.4

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Acknowledgements

The authors thank the National Science Foundation for grant No. ILI8951058.

References

Bruker (1996). XSCANS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Copley, R. C. B., Deprez, L. S., Lewis, T. C. & Price, S. L. (2005). CrystEngComm, 7, 421–428. Web of Science CSD CrossRef CAS Google Scholar
Parrish, D., Glass, B., Rehberg, G. M. & Kastner, M. E. (2009). Acta Cryst. E65, o2356. Web of Science CSD CrossRef IUCr Journals Google Scholar
Parrish, D., Tivitmahaisoon, P., Rehberg, G. M. & Kastner, M. E. (2009). Acta Cryst. E65, o2355. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rehberg, G. M. & Glass, B. M. (1995). Org. Prep. Proced. Int. 27, 651–652. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Warren, J. D., MacMillan, J. H. & Washburne, S. S. (1975). J. Org. Chem. 40, 743–746. CrossRef CAS Web of Science Google Scholar