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

Abstract

In the title compound, C₁₃H₁₁ClN₂O₆, the dihedral angles between the benzene ring and the amino­methyl­ene unit and between the amino­methyl­ene group and the dioxane ring are 8.19 (14) and 1.39 (17)°, respectively. The dioxane ring has a half-boat conformation, in which the C atom between the dioxane O atoms is 0.662 (4)Å out of the plane through the remaining ring atoms. Intra­molecular N—H⋯O and N—H⋯Cl inter­actions occur.

Related literature

For the synthesis of related compounds, see: Cassis et al. (1985 ▶). For the biological activity of related compounds, see: Griera et al. (1997 ▶); Darque et al. (2009 ▶).

Experimental

Crystal data

• C₁₃H₁₁ClN₂O₆

• M _r = 326.69

• Monoclinic,

• a = 13.5850 (5) Å

• b = 5.04379 (14) Å

• c = 21.0272 (7) Å

• β = 104.427 (4)°

• V = 1395.35 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.31 mm⁻¹

• T = 293 K

• 0.40 × 0.40 × 0.30 mm

Data collection

• Oxford Diffraction Xcalibur Eos diffractometer

• Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) ▶ T _min = 0.984, T _max = 1.0

• 6136 measured reflections

• 2853 independent reflections

• 2141 reflections with I > 2σ(I)

• R _int = 0.021

Refinement

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.104

• S = 1.04

• 2853 reflections

• 201 parameters

• H-atom parameters constrained

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.29 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
N2—H2⋯Cl1	0.86	2.46	2.9328 (15)	115
N2—H2⋯O3	0.86	1.99	2.670 (2)	136

supplementary crystallographic information

Comment

The 4(1H)quinolone are of great importance owing to their wide biological properties (Griera et al., 1997; Darque et al.,2009). 5-{[(2-Chloro-4-nitrophenyl)amino]methylene}-2,2-dimethyl-1,3-dioxane- 4,6-dione is one of the key intermediates in our synthetic investigations of new 4(1H)quinolone derivatives. We report here its crystal structure. The title compound is approximately planar, the dihedral angles between the benzene ring and the aminomethylene unit and between the aminomethylene group and the dioxane ring are 8.19 (14)° and 1.39 (17)°, respectively. The dioxane ring has a half-boat conformation, in which the C atom between the dioxane O atoms is 0.6615 (35) Å out of the plane (Figure 1.). In the molecule, there are intramolecular N—H···O and N—H···Cl interactions (Table 1.).

Experimental

An ethanol solution (50 ml) of 2,2–dimethyl–1,3–dioxane–4,6–dione (1.44 g, 10 mmol) and triethoxymethane (1.78 g, 12 mmol) was heated to reflux for 2.5 h, then the 2-chloro-4-nitroaniline(1.72 g, 10 mmol) was added into the solution. The mixture was heated under reflux for another 8 h and then filtered. The precipitate was recrystallized from ethanol, giving the title compound. Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of ethanol.

Refinement

The H-atom of N was located in a difference Fourier map and free refined: N—H = 0.86 Å. The other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic,C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Figures

Fig. 1.

The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. The intramolecular hydrogen bonds are shown as a dashed lines.

Crystal data

C13H11ClN2O6	F(000) = 672
Mr = 326.69	Dx = 1.555 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 2432 reflections
a = 13.5850 (5) Å	θ = 3.0–29.2°
b = 5.04379 (14) Å	µ = 0.31 mm−1
c = 21.0272 (7) Å	T = 293 K
β = 104.427 (4)°	Block, colorless
V = 1395.35 (8) Å3	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur Eos diffractometer	2853 independent reflections
Radiation source: fine-focus sealed tube	2141 reflections with I > 2σ(I)
graphite	Rint = 0.021
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 3.1°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −6→6
Tmin = 0.984, Tmax = 1.0	l = −25→26
6136 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0478P)2 + 0.1291P] where P = (Fo2 + 2Fc2)/3
2853 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Special details

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.11303 (4)	0.78022 (10)	0.26632 (2)	0.05062 (18)
O1	−0.23464 (10)	0.7514 (2)	0.04172 (7)	0.0446 (4)
O2	−0.24014 (10)	0.4073 (3)	−0.03503 (6)	0.0469 (4)
O3	−0.09905 (11)	0.8273 (3)	0.12205 (7)	0.0517 (4)
O4	−0.10943 (10)	0.1444 (3)	−0.03156 (7)	0.0509 (4)
O5	0.46457 (14)	0.3369 (4)	0.35706 (9)	0.0855 (6)
O6	0.48067 (14)	0.0203 (4)	0.29216 (9)	0.0910 (6)
N1	0.43369 (14)	0.2060 (4)	0.30716 (10)	0.0592 (5)
N2	0.05320 (11)	0.4776 (3)	0.14363 (7)	0.0360 (4)
H2	0.0263	0.6155	0.1565	0.043*
C1	0.33473 (15)	0.2739 (4)	0.26352 (9)	0.0432 (5)
C2	0.27826 (15)	0.4698 (4)	0.28308 (9)	0.0431 (5)
H2A	0.3024	0.5569	0.3229	0.052*
C3	0.18530 (14)	0.5341 (3)	0.24251 (9)	0.0377 (4)
C4	0.14835 (13)	0.4042 (3)	0.18250 (8)	0.0337 (4)
C5	0.20803 (15)	0.2071 (4)	0.16447 (9)	0.0421 (5)
H5	0.1847	0.1193	0.1247	0.051*
C6	0.30095 (15)	0.1410 (4)	0.20485 (10)	0.0455 (5)
H6	0.3404	0.0086	0.1928	0.055*
C7	−0.00122 (13)	0.3622 (3)	0.08932 (8)	0.0336 (4)
H7	0.0254	0.2132	0.0736	0.040*
C8	−0.09479 (13)	0.4525 (3)	0.05552 (8)	0.0328 (4)
C9	−0.14016 (14)	0.6847 (3)	0.07640 (9)	0.0373 (4)
C10	−0.29653 (14)	0.5492 (4)	0.00333 (10)	0.0437 (5)
C11	−0.14546 (14)	0.3172 (4)	−0.00500 (9)	0.0359 (4)
C12	−0.33222 (18)	0.3613 (4)	0.04848 (13)	0.0656 (7)
H12B	−0.3779	0.2337	0.0229	0.098*
H12C	−0.3668	0.4590	0.0756	0.098*
H12A	−0.2748	0.2713	0.0758	0.098*
C13	−0.38047 (18)	0.6932 (5)	−0.04496 (12)	0.0695 (7)
H13B	−0.3514	0.8249	−0.0678	0.104*
H13C	−0.4245	0.7774	−0.0218	0.104*
H13A	−0.4188	0.5687	−0.0760	0.104*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0589 (4)	0.0482 (3)	0.0464 (3)	0.0072 (2)	0.0162 (3)	−0.0079 (2)
O1	0.0400 (8)	0.0317 (6)	0.0572 (9)	0.0054 (6)	0.0025 (7)	−0.0053 (6)
O2	0.0393 (8)	0.0582 (8)	0.0405 (8)	0.0068 (6)	0.0048 (6)	−0.0090 (7)
O3	0.0527 (9)	0.0407 (7)	0.0556 (9)	0.0058 (6)	0.0018 (7)	−0.0167 (7)
O4	0.0477 (9)	0.0585 (9)	0.0464 (8)	0.0064 (7)	0.0118 (7)	−0.0192 (7)
O5	0.0679 (12)	0.1027 (14)	0.0660 (11)	0.0073 (10)	−0.0210 (10)	−0.0129 (11)
O6	0.0689 (12)	0.1144 (15)	0.0783 (13)	0.0444 (12)	−0.0031 (10)	0.0001 (11)
N1	0.0447 (11)	0.0748 (13)	0.0522 (12)	0.0057 (10)	0.0013 (9)	0.0098 (10)
N2	0.0349 (8)	0.0370 (8)	0.0364 (9)	0.0019 (7)	0.0092 (7)	−0.0035 (7)
C1	0.0369 (11)	0.0526 (12)	0.0382 (11)	0.0015 (9)	0.0060 (9)	0.0074 (9)
C2	0.0462 (12)	0.0481 (11)	0.0327 (10)	−0.0039 (9)	0.0051 (9)	−0.0018 (9)
C3	0.0409 (11)	0.0385 (10)	0.0358 (10)	−0.0014 (8)	0.0136 (9)	0.0005 (8)
C4	0.0317 (10)	0.0373 (9)	0.0333 (10)	−0.0022 (7)	0.0107 (8)	0.0030 (8)
C5	0.0404 (11)	0.0500 (11)	0.0357 (11)	0.0028 (9)	0.0090 (9)	−0.0051 (9)
C6	0.0412 (11)	0.0497 (11)	0.0467 (12)	0.0067 (9)	0.0128 (9)	−0.0008 (10)
C7	0.0340 (10)	0.0351 (9)	0.0340 (10)	−0.0001 (8)	0.0130 (8)	−0.0005 (8)
C8	0.0342 (10)	0.0314 (9)	0.0344 (10)	−0.0008 (7)	0.0115 (8)	−0.0017 (8)
C9	0.0388 (10)	0.0308 (9)	0.0416 (11)	−0.0010 (8)	0.0086 (9)	0.0004 (8)
C10	0.0365 (10)	0.0413 (10)	0.0529 (12)	0.0015 (8)	0.0099 (9)	−0.0124 (9)
C11	0.0339 (10)	0.0400 (10)	0.0356 (10)	−0.0012 (8)	0.0120 (8)	−0.0014 (9)
C12	0.0596 (15)	0.0528 (13)	0.0971 (19)	−0.0072 (11)	0.0431 (14)	−0.0094 (13)
C13	0.0470 (14)	0.0787 (17)	0.0703 (16)	0.0174 (12)	−0.0089 (12)	−0.0148 (13)

Geometric parameters (Å, °)

Cl1—C3	1.7321 (19)	C3—C4	1.399 (2)
O1—C9	1.351 (2)	C4—C5	1.394 (2)
O1—C10	1.436 (2)	C5—H5	0.9300
O2—C10	1.434 (2)	C5—C6	1.375 (3)
O2—C11	1.362 (2)	C6—H6	0.9300
O3—C9	1.218 (2)	C7—H7	0.9300
O4—C11	1.203 (2)	C7—C8	1.371 (2)
O5—N1	1.222 (2)	C8—C9	1.442 (2)
O6—N1	1.218 (2)	C8—C11	1.457 (2)
N1—C1	1.467 (3)	C10—C12	1.505 (3)
N2—H2	0.8600	C10—C13	1.511 (3)
N2—C4	1.396 (2)	C12—H12B	0.9600
N2—C7	1.330 (2)	C12—H12C	0.9600
C1—C2	1.375 (3)	C12—H12A	0.9600
C1—C6	1.378 (3)	C13—H13B	0.9600
C2—H2A	0.9300	C13—H13C	0.9600
C2—C3	1.375 (2)	C13—H13A	0.9600
O1—C9—C8	117.28 (15)	C5—C4—N2	123.12 (16)
O1—C10—C12	109.17 (17)	C5—C4—C3	118.49 (16)
O1—C10—C13	105.94 (16)	C5—C6—C1	118.96 (19)
O2—C10—O1	110.53 (15)	C5—C6—H6	120.5
O2—C10—C12	109.99 (15)	C6—C1—N1	119.67 (19)
O2—C10—C13	106.34 (17)	C6—C5—C4	120.78 (17)
O2—C11—C8	115.76 (16)	C6—C5—H5	119.6
O3—C9—O1	117.76 (16)	C7—N2—H2	115.8
O3—C9—C8	124.94 (17)	C7—N2—C4	128.46 (15)
O4—C11—O2	118.24 (17)	C7—C8—C9	121.58 (16)
O4—C11—C8	125.91 (17)	C7—C8—C11	118.19 (16)
O5—N1—C1	118.4 (2)	C8—C7—H7	118.5
O6—N1—O5	123.2 (2)	C9—O1—C10	118.10 (13)
O6—N1—C1	118.38 (19)	C9—C8—C11	120.12 (16)
N2—C4—C3	118.39 (16)	C10—C12—H12B	109.5
N2—C7—H7	118.5	C10—C12—H12C	109.5
N2—C7—C8	123.03 (16)	C10—C12—H12A	109.5
C1—C2—H2A	120.7	C10—C13—H13B	109.5
C1—C2—C3	118.59 (17)	C10—C13—H13C	109.5
C1—C6—H6	120.5	C10—C13—H13A	109.5
C2—C1—N1	118.25 (18)	C11—O2—C10	118.74 (14)
C2—C1—C6	122.08 (18)	C12—C10—C13	114.77 (19)
C2—C3—Cl1	119.27 (14)	H12B—C12—H12C	109.5
C2—C3—C4	121.10 (17)	H12B—C12—H12A	109.5
C3—C2—H2A	120.7	H12C—C12—H12A	109.5
C4—N2—H2	115.8	H13B—C13—H13C	109.5
C4—C3—Cl1	119.63 (14)	H13B—C13—H13A	109.5
C4—C5—H5	119.6	H13C—C13—H13A	109.5

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1	0.86	2.46	2.9328 (15)	115
N2—H2···O3	0.86	1.99	2.670 (2)	136