2,2-Dimethyl-5-[(3-nitro-anilino)methyl-ene]-1,3-dioxane-4,6-dione.

The benzene ring of the title compound, C(13)H(12)N(2)O(6), is twisted away from the planes of the amino-methyl-ene unit and the dioxane ring by 30.13 (4) and 35.89 (4)°, respectively. The dioxane ring exhibits a half-boat conformation, in which the C atom between the dioxane O atoms is 0.553 (8) Å out-of-plane. An intra-molecular N-H⋯O hydrogen bond stabilizes the conformation of the dioxane ring with the amino-methyl-ene group [the dihedral angle between the mean planes of the dioxane ring and the amino-methyl-ene group is 11.61 (4)°]. In the crystal, a three-dimensional framework is built via weak inter-molecular N-H⋯O and C-H⋯O inter-actions.

Related literature

For the synthesis of related compounds, see: Cassis et al. (1985 ▶). For the synthesis of related anti­tumor precursors, see Ruchelman et al. (2003 ▶). For the crystal structures of related 5-aryl­amino­methyl­ene-2,2-dimethyl-1,3-dioxane-4,6-dione deriv­atives, see Li et al. (2009a ▶,b ▶); Li, Shi et al. (2009 ▶).

Experimental

Crystal data

C13H12N2O6

M = 292.25

Monoclinic,

a = 11.7900 (13) Å

b = 8.7699 (9) Å

c = 14.0614 (15) Å

β = 113.8640 (10)°

V = 1329.6 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.12 mm−1

T = 153 K

0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: none

8116 measured reflections

3052 independent reflections

2572 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.101

S = 1.05

3052 reflections

197 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.18 e Å−3

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809031535/zq2002sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031535/zq2002Isup2.hkl

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

C13H12N2O6	F(000) = 608
Mr = 292.25	Dx = 1.460 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7900 (13) Å	Cell parameters from 4305 reflections
b = 8.7699 (9) Å	θ = 2.3–27.6°
c = 14.0614 (15) Å	µ = 0.12 mm−1
β = 113.864 (1)°	T = 153 K
V = 1329.6 (2) Å3	Block, colourless
Z = 4	0.20 × 0.10 × 0.10 mm

Bruker SMART CCD area-detector diffractometer	2572 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.014
graphite	θmax = 27.6°, θmin = 2.8°
φ and ω scans	h = −15→14
8116 measured reflections	k = −11→10
3052 independent reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.036	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.101	w = 1/[σ2(Fo2) + (0.045P)2 + 0.3157P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3052 reflections	Δρmax = 0.22 e Å−3
197 parameters	Δρmin = −0.18 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: 0.0195 (18)

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.

	x	y	z	Uiso*/Ueq
O1	0.45433 (8)	−0.09916 (10)	1.23372 (6)	0.0370 (2)
O3	0.47419 (8)	−0.05487 (12)	1.08661 (7)	0.0440 (2)
O2	0.25826 (8)	−0.13984 (11)	1.23681 (6)	0.0401 (2)
C4	0.40464 (11)	−0.06725 (13)	1.13054 (9)	0.0322 (2)
N1	0.26298 (10)	0.01843 (13)	0.91248 (8)	0.0359 (2)
C8	0.19585 (11)	0.06369 (14)	0.80763 (9)	0.0342 (3)
C9	0.24224 (11)	0.02544 (14)	0.73506 (9)	0.0347 (3)
H9	0.3148	−0.0312	0.7538	0.042*
C3	0.37852 (11)	−0.07324 (14)	1.29110 (9)	0.0337 (3)
O4	0.08565 (9)	−0.12773 (15)	1.09442 (8)	0.0584 (3)
C7	0.21114 (11)	−0.01291 (14)	0.97781 (9)	0.0350 (3)
H7	0.1252	−0.0055	0.9519	0.042*
O5	0.30012 (13)	−0.07262 (15)	0.57581 (10)	0.0684 (3)
C6	0.19637 (11)	−0.10611 (15)	1.13438 (9)	0.0381 (3)
C5	0.27159 (11)	−0.05534 (14)	1.08029 (9)	0.0333 (3)
C10	0.17796 (12)	0.07365 (16)	0.63388 (9)	0.0403 (3)
C13	0.08587 (14)	0.14495 (19)	0.77793 (11)	0.0510 (4)
H13	0.0545	0.1705	0.8268	0.061*
C2	0.43836 (14)	−0.16096 (17)	1.39116 (10)	0.0459 (3)
H2A	0.3876	−0.1539	1.4299	0.069*
H2B	0.5188	−0.1189	1.4315	0.069*
H2C	0.4468	−0.2660	1.3759	0.069*
N2	0.22862 (12)	0.03454 (17)	0.55739 (9)	0.0535 (3)
C1	0.36712 (15)	0.09463 (15)	1.30692 (11)	0.0481 (3)
H1A	0.3285	0.1440	1.2406	0.072*
H1B	0.4481	0.1372	1.3444	0.072*
H1C	0.3174	0.1099	1.3459	0.072*
C11	0.06978 (15)	0.1552 (2)	0.60191 (11)	0.0586 (4)
H11	0.0293	0.1874	0.5334	0.070*
O6	0.19778 (16)	0.1124 (2)	0.47934 (10)	0.0992 (6)
C12	0.02320 (15)	0.1877 (2)	0.67512 (13)	0.0672 (5)
H12	−0.0518	0.2393	0.6550	0.081*
H1	0.3441 (15)	0.0100 (18)	0.9339 (12)	0.051 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0341 (4)	0.0496 (5)	0.0266 (4)	0.0047 (4)	0.0115 (3)	0.0028 (3)
O3	0.0338 (5)	0.0665 (6)	0.0354 (5)	0.0021 (4)	0.0177 (4)	0.0058 (4)
O2	0.0413 (5)	0.0500 (5)	0.0306 (4)	−0.0094 (4)	0.0164 (4)	0.0009 (4)
C4	0.0350 (6)	0.0351 (6)	0.0270 (5)	0.0005 (4)	0.0130 (5)	0.0007 (4)
N1	0.0313 (5)	0.0478 (6)	0.0274 (5)	0.0026 (4)	0.0106 (4)	0.0029 (4)
C8	0.0332 (6)	0.0396 (6)	0.0279 (5)	−0.0008 (5)	0.0105 (5)	0.0033 (5)
C9	0.0328 (6)	0.0388 (6)	0.0302 (6)	0.0001 (5)	0.0106 (5)	0.0030 (5)
C3	0.0375 (6)	0.0384 (6)	0.0263 (5)	−0.0019 (5)	0.0140 (5)	−0.0011 (4)
O4	0.0353 (5)	0.0966 (9)	0.0440 (6)	−0.0133 (5)	0.0167 (4)	0.0000 (5)
C7	0.0312 (6)	0.0427 (6)	0.0295 (6)	−0.0006 (5)	0.0108 (5)	−0.0006 (5)
O5	0.0855 (9)	0.0756 (8)	0.0587 (7)	0.0112 (7)	0.0443 (6)	−0.0031 (6)
C6	0.0352 (6)	0.0482 (7)	0.0324 (6)	−0.0042 (5)	0.0152 (5)	−0.0021 (5)
C5	0.0315 (6)	0.0409 (6)	0.0283 (5)	−0.0007 (5)	0.0128 (5)	−0.0004 (5)
C10	0.0420 (7)	0.0496 (7)	0.0294 (6)	−0.0030 (5)	0.0146 (5)	0.0032 (5)
C13	0.0479 (8)	0.0687 (10)	0.0417 (7)	0.0176 (7)	0.0235 (6)	0.0123 (7)
C2	0.0555 (8)	0.0499 (8)	0.0300 (6)	−0.0003 (6)	0.0147 (6)	0.0052 (5)
N2	0.0583 (8)	0.0716 (9)	0.0339 (6)	−0.0037 (7)	0.0218 (5)	0.0014 (6)
C1	0.0629 (9)	0.0392 (7)	0.0427 (7)	0.0011 (6)	0.0219 (7)	−0.0044 (6)
C11	0.0521 (9)	0.0833 (12)	0.0349 (7)	0.0148 (8)	0.0118 (6)	0.0209 (7)
O6	0.1211 (13)	0.1419 (14)	0.0516 (7)	0.0380 (11)	0.0524 (8)	0.0415 (8)
C12	0.0509 (9)	0.0965 (13)	0.0529 (9)	0.0351 (9)	0.0197 (7)	0.0271 (9)

O1—C4	1.3560 (14)	C7—H7	0.9300
O1—C3	1.4441 (14)	O5—N2	1.2183 (18)
O3—C4	1.2147 (14)	C6—C5	1.4524 (16)
O2—C6	1.3580 (15)	C10—C11	1.370 (2)
O2—C3	1.4348 (15)	C10—N2	1.4665 (17)
C4—C5	1.4401 (17)	C13—C12	1.383 (2)
N1—C7	1.3219 (15)	C13—H13	0.9300
N1—C8	1.4190 (15)	C2—H2A	0.9600
N1—H1	0.882 (16)	C2—H2B	0.9600
C8—C9	1.3800 (17)	C2—H2C	0.9600
C8—C13	1.3875 (18)	N2—O6	1.2164 (17)
C9—C10	1.3802 (17)	C1—H1A	0.9600
C9—H9	0.9300	C1—H1B	0.9600
C3—C1	1.5030 (18)	C1—H1C	0.9600
C3—C2	1.5053 (17)	C11—C12	1.378 (2)
O4—C6	1.2092 (16)	C11—H11	0.9300
C7—C5	1.3754 (16)	C12—H12	0.9300
C4—O1—C3	117.92 (9)	C4—C5—C6	119.70 (10)
C6—O2—C3	117.84 (9)	C11—C10—C9	123.24 (12)
O3—C4—O1	118.31 (11)	C11—C10—N2	118.87 (12)
O3—C4—C5	124.71 (11)	C9—C10—N2	117.88 (12)
O1—C4—C5	116.96 (10)	C12—C13—C8	119.52 (13)
C7—N1—C8	124.04 (10)	C12—C13—H13	120.2
C7—N1—H1	119.2 (10)	C8—C13—H13	120.2
C8—N1—H1	116.7 (10)	C3—C2—H2A	109.5
C9—C8—C13	120.26 (11)	C3—C2—H2B	109.5
C9—C8—N1	118.62 (11)	H2A—C2—H2B	109.5
C13—C8—N1	121.12 (11)	C3—C2—H2C	109.5
C8—C9—C10	118.11 (11)	H2A—C2—H2C	109.5
C8—C9—H9	120.9	H2B—C2—H2C	109.5
C10—C9—H9	120.9	O6—N2—O5	123.59 (14)
O2—C3—O1	109.91 (9)	O6—N2—C10	117.94 (14)
O2—C3—C1	110.44 (11)	O5—N2—C10	118.46 (12)
O1—C3—C1	110.45 (10)	C3—C1—H1A	109.5
O2—C3—C2	106.13 (10)	C3—C1—H1B	109.5
O1—C3—C2	106.25 (10)	H1A—C1—H1B	109.5
C1—C3—C2	113.48 (11)	C3—C1—H1C	109.5
N1—C7—C5	126.51 (11)	H1A—C1—H1C	109.5
N1—C7—H7	116.7	H1B—C1—H1C	109.5
C5—C7—H7	116.7	C10—C11—C12	117.54 (13)
O4—C6—O2	118.33 (11)	C10—C11—H11	121.2
O4—C6—C5	125.30 (12)	C12—C11—H11	121.2
O2—C6—C5	116.25 (10)	C11—C12—C13	121.26 (14)
C7—C5—C4	122.25 (10)	C11—C12—H12	119.4
C7—C5—C6	117.66 (11)	C13—C12—H12	119.4
C3—O1—C4—O3	163.48 (11)	O3—C4—C5—C6	165.88 (12)
C3—O1—C4—C5	−18.46 (15)	O1—C4—C5—C6	−12.04 (17)
C7—N1—C8—C9	−149.73 (12)	O4—C6—C5—C7	7.2 (2)
C7—N1—C8—C13	30.4 (2)	O2—C6—C5—C7	−176.78 (11)
C13—C8—C9—C10	1.64 (19)	O4—C6—C5—C4	−165.75 (14)
N1—C8—C9—C10	−178.26 (11)	O2—C6—C5—C4	10.23 (18)
C6—O2—C3—O1	−50.49 (14)	C8—C9—C10—C11	−1.1 (2)
C6—O2—C3—C1	71.61 (13)	C8—C9—C10—N2	179.15 (11)
C6—O2—C3—C2	−164.99 (10)	C9—C8—C13—C12	−0.1 (2)
C4—O1—C3—O2	48.46 (13)	N1—C8—C13—C12	179.74 (15)
C4—O1—C3—C1	−73.64 (14)	C11—C10—N2—O6	22.6 (2)
C4—O1—C3—C2	162.88 (10)	C9—C10—N2—O6	−157.58 (15)
C8—N1—C7—C5	−179.14 (12)	C11—C10—N2—O5	−158.17 (16)
C3—O2—C6—O4	−161.51 (12)	C9—C10—N2—O5	21.6 (2)
C3—O2—C6—C5	22.23 (16)	C9—C10—C11—C12	−1.0 (3)
N1—C7—C5—C4	1.6 (2)	N2—C10—C11—C12	178.78 (16)
N1—C7—C5—C6	−171.23 (12)	C10—C11—C12—C13	2.5 (3)
O3—C4—C5—C7	−6.8 (2)	C8—C13—C12—C11	−2.0 (3)
O1—C4—C5—C7	175.30 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.882 (16)	2.150 (15)	2.7705 (14)	126.8 (13)
N1—H1···O3i	0.882 (16)	2.308 (16)	3.1101 (14)	151.2 (13)
C7—H7···O4	0.93	2.48	2.8026 (18)	101
C7—H7···O4ii	0.93	2.58	3.4527 (18)	156
C11—H11···O4iii	0.93	2.39	3.242 (2)	152
C13—H13···O4ii	0.93	2.36	3.205 (2)	151

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.882 (16)	2.150 (15)	2.7705 (14)	126.8 (13)
N1—H1⋯O3i	0.882 (16)	2.308 (16)	3.1101 (14)	151.2 (13)
C7—H7⋯O4ii	0.93	2.58	3.4527 (18)	156
C11—H11⋯O4iii	0.93	2.39	3.242 (2)	152
C13—H13⋯O4ii	0.93	2.36	3.205 (2)	151

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