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

Abstract

The crystal of the title compound, C₁₃H₁₂N₂O₆, contains a bifurcated intra­molecular hydrogen bond between the N—H group and one of the O atoms from both the nitro group and the dioxane-4,6-dione moiety. In addition, mol­ecules are linked by a series of inter­molecular C—H⋯O secondary inter­actions. The dihedral angles between the benzene ring and the nitro group and the conjugated part of the dioxane-4,6-dione moiety are 19.1 (2) and 17.89 (7)°, respectively.

Related literature

The title compound is an important intermediate drug discovery. For the synthesis and structures of related antitumor precursors, see: Cassis et al. (1985 ▶). For related literature, see Dolomanov et al. (2009 ▶).

Experimental

Crystal data

• C₁₃H₁₂N₂O₆

• M _r = 292.25

• Monoclinic,

• a = 6.3860 (2) Å

• b = 17.3800 (5) Å

• c = 11.9338 (3) Å

• β = 90.622 (3)°

• V = 1324.44 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 150 K

• 0.42 × 0.35 × 0.25 mm

Data collection

• Oxford Diffraction Xcalibur Eos diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.993, T _max = 1.0

• 9157 measured reflections

• 2693 independent reflections

• 2212 reflections with I > 2σ(I)

• R _int = 0.027

Refinement

• R[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 0.097

• S = 1.03

• 2693 reflections

• 192 parameters

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5	0.88	1.97	2.6403 (16)	132
N1—H1⋯O3	0.88	2.10	2.7439 (16)	130
C7—H7⋯O4i	0.95	2.40	3.0852 (18)	129
C10—H10⋯O6ii	0.95	2.48	3.4219 (19)	170
C11—H11⋯O1iii	0.95	2.53	3.4508 (18)	162
C13—H13⋯O4i	0.95	2.53	3.4445 (18)	161

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

2,2-Dimethyl-5-[(2-nitrophenylamino)-methylene]-[1,3]dioxane-4,6-dione, C₁₃H₁₂N₂O₆, is a key intermediate which can be used to synthesize the 4(1H)quinolone derivatives by thermolysis, which can then be used as precursors for anti-malarial agents or anti-cancer agents. The structure contains an bifurcated intramolecular hydrogen bond between the N-H and one of the O's from both the nitro group and the dioxane-4,6-dione moiety. In addition the molecules are linked by a series of intermolecular C-H···O secondary interactions. The dihedral angles between the phenyl group and both the nitro and conjugated part of the dioxane-4,6-dione moiety are 19.1 (2)° and 17.89 (7)°, respectively.

Experimental

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 heated to reflux for 0.5 h, then 2-nitroaniline(1.38 g, 0.01 mol) in ethanol (20 mL) was added into the above solution. The mixture was heated under reflux for another 2 h and poured into cold water then filtered to obtain a powder. Single crystals were obtained from the powder in CH₂Cl₂ and methanol after 3 days.

Refinement

H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C) [U_iso(H) = 1.5U_eq(C) for the CH₃ groups).

Figures

Fig. 1.

The molecular structure of the title compound showing the bifurcated intramolecular hydrogen bond.

Fig. 2.

Fi. 2. The packing diagram for the title compound viewed down the a axis, showing the intermolecular C—H···O interactions.

Crystal data

C13H12N2O6	F(000) = 608
Mr = 292.25	Dx = 1.466 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 3956 reflections
a = 6.3860 (2) Å	θ = 2.9–29.1°
b = 17.3800 (5) Å	µ = 0.12 mm−1
c = 11.9338 (3) Å	T = 150 K
β = 90.622 (3)°	Block, colourless
V = 1324.44 (7) Å3	0.42 × 0.35 × 0.25 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur Eos diffractometer	2693 independent reflections
Radiation source: fine-focus sealed tube	2212 reflections with I > 2σ(I)
graphite	Rint = 0.027
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 2.9°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = 0→21
Tmin = 0.993, Tmax = 1.0	l = 0→14
9157 measured reflections

Refinement

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0439P)2 + 0.3082P] where P = (Fo2 + 2Fc2)/3
2693 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.38713 (16)	0.72407 (6)	0.58099 (8)	0.0262 (3)
O2	0.14846 (17)	0.64025 (6)	0.66934 (8)	0.0260 (3)
O3	0.57240 (17)	0.68777 (6)	0.43461 (9)	0.0287 (3)
O4	0.10877 (16)	0.51978 (6)	0.61477 (8)	0.0255 (3)
O5	0.7590 (2)	0.62314 (7)	0.21713 (11)	0.0434 (3)
O6	0.9663 (2)	0.55108 (8)	0.12201 (10)	0.0452 (3)
N1	0.45628 (19)	0.55433 (7)	0.32793 (9)	0.0215 (3)
H1	0.5390	0.5948	0.3241	0.026*
N2	0.7992 (2)	0.56246 (8)	0.16919 (10)	0.0302 (3)
C1	0.1846 (2)	0.71834 (8)	0.63308 (12)	0.0254 (3)
C2	0.4337 (2)	0.67221 (8)	0.49964 (11)	0.0218 (3)
C3	0.3173 (2)	0.60086 (8)	0.50100 (11)	0.0204 (3)
C4	0.1833 (2)	0.58240 (8)	0.59513 (11)	0.0211 (3)
C5	0.1985 (3)	0.76619 (10)	0.73797 (13)	0.0358 (4)
H5A	0.3132	0.7472	0.7856	0.054*
H5B	0.0664	0.7626	0.7787	0.054*
H5C	0.2249	0.8200	0.7180	0.054*
C6	0.0136 (3)	0.74320 (10)	0.55292 (13)	0.0329 (4)
H6A	0.0098	0.7084	0.4884	0.049*
H6B	0.0413	0.7958	0.5273	0.049*
H6C	−0.1215	0.7417	0.5910	0.049*
C7	0.3356 (2)	0.54685 (8)	0.41734 (12)	0.0204 (3)
H7	0.2563	0.5009	0.4240	0.025*
C8	0.4737 (2)	0.50006 (8)	0.24088 (12)	0.0216 (3)
C9	0.6411 (2)	0.50180 (8)	0.16525 (12)	0.0238 (3)
C10	0.6632 (3)	0.44616 (9)	0.08294 (12)	0.0295 (4)
H10	0.7784	0.4482	0.0333	0.035*
C11	0.5182 (3)	0.38812 (9)	0.07327 (13)	0.0323 (4)
H11	0.5328	0.3498	0.0171	0.039*
C12	0.3506 (3)	0.38574 (9)	0.14598 (14)	0.0334 (4)
H12	0.2503	0.3456	0.1394	0.040*
C13	0.3277 (2)	0.44111 (9)	0.22799 (13)	0.0283 (4)
H13	0.2105	0.4390	0.2763	0.034*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0282 (6)	0.0224 (5)	0.0279 (6)	−0.0010 (4)	−0.0001 (5)	−0.0038 (4)
O2	0.0299 (6)	0.0280 (6)	0.0201 (5)	0.0010 (5)	0.0039 (4)	−0.0033 (4)
O3	0.0266 (6)	0.0276 (6)	0.0322 (6)	−0.0059 (5)	0.0055 (5)	0.0002 (5)
O4	0.0235 (6)	0.0290 (6)	0.0239 (5)	−0.0056 (4)	0.0029 (4)	0.0009 (4)
O5	0.0497 (8)	0.0287 (6)	0.0524 (8)	−0.0103 (6)	0.0263 (6)	−0.0056 (6)
O6	0.0343 (7)	0.0534 (8)	0.0484 (8)	−0.0045 (6)	0.0235 (6)	−0.0030 (6)
N1	0.0198 (7)	0.0203 (6)	0.0245 (6)	−0.0010 (5)	0.0048 (5)	−0.0014 (5)
N2	0.0316 (8)	0.0324 (7)	0.0269 (7)	−0.0017 (6)	0.0115 (6)	0.0042 (6)
C1	0.0283 (8)	0.0248 (8)	0.0230 (7)	0.0031 (7)	0.0007 (6)	−0.0027 (6)
C2	0.0213 (8)	0.0227 (7)	0.0213 (7)	0.0017 (6)	−0.0027 (6)	0.0006 (6)
C3	0.0178 (7)	0.0214 (7)	0.0219 (7)	0.0012 (6)	0.0014 (6)	0.0000 (6)
C4	0.0172 (7)	0.0268 (8)	0.0193 (7)	0.0002 (6)	−0.0024 (6)	−0.0004 (6)
C5	0.0463 (11)	0.0336 (9)	0.0275 (8)	0.0052 (8)	−0.0038 (8)	−0.0085 (7)
C6	0.0332 (10)	0.0365 (9)	0.0289 (8)	0.0100 (7)	−0.0046 (7)	−0.0062 (7)
C7	0.0159 (7)	0.0209 (7)	0.0245 (7)	0.0001 (6)	0.0000 (6)	0.0024 (6)
C8	0.0226 (8)	0.0208 (7)	0.0214 (7)	0.0045 (6)	0.0015 (6)	0.0007 (6)
C9	0.0250 (8)	0.0245 (7)	0.0219 (7)	0.0029 (6)	0.0044 (6)	0.0039 (6)
C10	0.0344 (9)	0.0317 (9)	0.0227 (8)	0.0095 (7)	0.0068 (7)	0.0028 (6)
C11	0.0435 (10)	0.0284 (8)	0.0251 (8)	0.0078 (7)	0.0017 (7)	−0.0064 (6)
C12	0.0368 (10)	0.0286 (8)	0.0347 (9)	−0.0043 (7)	0.0009 (7)	−0.0065 (7)
C13	0.0247 (9)	0.0310 (8)	0.0294 (8)	−0.0021 (7)	0.0055 (7)	−0.0044 (6)

Geometric parameters (Å, °)

O1—C2	1.3600 (17)	C5—H5A	0.9800
O1—C1	1.4446 (17)	C5—H5B	0.9800
O2—C4	1.3598 (17)	C5—H5C	0.9800
O2—C1	1.4438 (17)	C6—H6A	0.9800
O3—C2	1.2144 (17)	C6—H6B	0.9800
O4—C4	1.2118 (17)	C6—H6C	0.9800
O5—N2	1.2283 (17)	C7—H7	0.9500
O6—N2	1.2276 (17)	C8—C13	1.393 (2)
N1—C7	1.3292 (18)	C8—C9	1.4066 (19)
N1—C8	1.4084 (18)	C9—C10	1.387 (2)
N1—H1	0.8808	C10—C11	1.373 (2)
N2—C9	1.460 (2)	C10—H10	0.9500
C1—C5	1.505 (2)	C11—C12	1.386 (2)
C1—C6	1.507 (2)	C11—H11	0.9500
C2—C3	1.446 (2)	C12—C13	1.382 (2)
C3—C7	1.376 (2)	C12—H12	0.9500
C3—C4	1.4551 (19)	C13—H13	0.9500
C2—O1—C1	117.73 (11)	H5B—C5—H5C	109.5
C4—O2—C1	118.16 (10)	C1—C6—H6A	109.5
C7—N1—C8	125.29 (12)	C1—C6—H6B	109.5
C7—N1—H1	118.2	H6A—C6—H6B	109.5
C8—N1—H1	116.4	C1—C6—H6C	109.5
O6—N2—O5	122.62 (14)	H6A—C6—H6C	109.5
O6—N2—C9	118.24 (13)	H6B—C6—H6C	109.5
O5—N2—C9	119.12 (12)	N1—C7—C3	124.77 (14)
O2—C1—O1	109.90 (11)	N1—C7—H7	117.6
O2—C1—C5	106.16 (12)	C3—C7—H7	117.6
O1—C1—C5	105.96 (13)	C13—C8—C9	117.22 (13)
O2—C1—C6	110.05 (13)	C13—C8—N1	121.06 (13)
O1—C1—C6	110.67 (12)	C9—C8—N1	121.70 (13)
C5—C1—C6	113.91 (13)	C10—C9—C8	121.56 (14)
O3—C2—O1	118.37 (13)	C10—C9—N2	116.77 (13)
O3—C2—C3	125.22 (13)	C8—C9—N2	121.67 (13)
O1—C2—C3	116.35 (12)	C11—C10—C9	119.87 (15)
C7—C3—C2	121.94 (13)	C11—C10—H10	120.1
C7—C3—C4	117.71 (13)	C9—C10—H10	120.1
C2—C3—C4	120.28 (12)	C10—C11—C12	119.61 (14)
O4—C4—O2	118.07 (12)	C10—C11—H11	120.2
O4—C4—C3	125.65 (13)	C12—C11—H11	120.2
O2—C4—C3	116.21 (12)	C13—C12—C11	120.75 (15)
C1—C5—H5A	109.5	C13—C12—H12	119.6
C1—C5—H5B	109.5	C11—C12—H12	119.6
H5A—C5—H5B	109.5	C12—C13—C8	120.97 (14)
C1—C5—H5C	109.5	C12—C13—H13	119.5
H5A—C5—H5C	109.5	C8—C13—H13	119.5
C4—O2—C1—O1	−49.01 (16)	C2—C3—C7—N1	−0.9 (2)
C4—O2—C1—C5	−163.17 (13)	C4—C3—C7—N1	−177.98 (13)
C4—O2—C1—C6	73.12 (16)	C7—N1—C8—C13	15.3 (2)
C2—O1—C1—O2	50.40 (15)	C7—N1—C8—C9	−163.14 (14)
C2—O1—C1—C5	164.70 (12)	C13—C8—C9—C10	−1.6 (2)
C2—O1—C1—C6	−71.36 (15)	N1—C8—C9—C10	176.90 (14)
C1—O1—C2—O3	160.00 (13)	C13—C8—C9—N2	178.09 (14)
C1—O1—C2—C3	−22.41 (18)	N1—C8—C9—N2	−3.4 (2)
O3—C2—C3—C7	−8.8 (2)	O6—N2—C9—C10	−18.5 (2)
O1—C2—C3—C7	173.82 (13)	O5—N2—C9—C10	159.99 (15)
O3—C2—C3—C4	168.19 (14)	O6—N2—C9—C8	161.84 (14)
O1—C2—C3—C4	−9.2 (2)	O5—N2—C9—C8	−19.7 (2)
C1—O2—C4—O4	−163.13 (13)	C8—C9—C10—C11	0.7 (2)
C1—O2—C4—C3	19.81 (18)	N2—C9—C10—C11	−178.97 (14)
C7—C3—C4—O4	10.9 (2)	C9—C10—C11—C12	0.1 (2)
C2—C3—C4—O4	−166.25 (14)	C10—C11—C12—C13	0.0 (2)
C7—C3—C4—O2	−172.34 (13)	C11—C12—C13—C8	−1.0 (3)
C2—C3—C4—O2	10.6 (2)	C9—C8—C13—C12	1.7 (2)
C8—N1—C7—C3	−178.89 (14)	N1—C8—C13—C12	−176.80 (14)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.88	1.97	2.6403 (16)	132.
N1—H1···O3	0.88	2.10	2.7439 (16)	130.
C7—H7···O4i	0.95	2.40	3.0852 (18)	129.
C10—H10···O6ii	0.95	2.48	3.4219 (19)	170.
C11—H11···O1iii	0.95	2.53	3.4508 (18)	162.
C13—H13···O4i	0.95	2.53	3.4445 (18)	161.

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2.