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

Lan, X.-Q.; Zhang, X.-F.; Yang, Y.-H.; Luo, Y.-F.

doi:10.1107/S160053681100095X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o392

doi:10.1107/S160053681100095X

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

Xian-Qiu Lan,^a Xiao-Feng Zhang,^a Ying-Hong Yang ^a and You-Fu Luo ^a,^b ^*

^aDepartment of Pharmaceutical and Bioengineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China, and ^bState Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: luo_youfu@foxmail.com

(Received 23 December 2010; accepted 7 January 2011; online 15 January 2011)

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, P 2₁ /c
a = 13.5850 (5) Å
b = 5.04379 (14) Å
c = 21.0272 (7) Å
β = 104.427 (4)°
V = 1395.35 (8) Å³
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) $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ 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[F² > 2σ(F²)] = 0.041
wR(F²) = 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

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

Data collection: CrysAlis PRO (Oxford Diffraction, 2010) $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ; cell refinement: CrysAlis PRO $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ; data reduction: CrysAlis PRO $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England.]$ ; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100095X/bq2269sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100095X/bq2269Isup2.hkl

checkCIF report

Comment top

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.).

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 (Dolomanov et al., 2009).

Figures top

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.

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

Crystal data top

C₁₃H₁₁ClN₂O₆	F(000) = 672
M_r = 326.69	D_x = 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 top

Oxford Diffraction Xcalibur Eos diffractometer	2853 independent reflections
Radiation source: fine-focus sealed tube	2141 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.1°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −6→6
T_min = 0.984, T_max = 1.0	l = −25→26
6136 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0478P)² + 0.1291P] where P = (F_o² + 2F_c²)/3
2853 reflections	(Δ/σ)_max < 0.001
201 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₃H₁₁ClN₂O₆	V = 1395.35 (8) Å³
M_r = 326.69	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.5850 (5) Å	µ = 0.31 mm⁻¹
b = 5.04379 (14) Å	T = 293 K
c = 21.0272 (7) Å	0.40 × 0.40 × 0.30 mm
β = 104.427 (4)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	2853 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2141 reflections with I > 2σ(I)
T_min = 0.984, T_max = 1.0	R_int = 0.021
6136 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.04	Δρ_max = 0.17 e Å⁻³
2853 reflections	Δρ_min = −0.29 e Å⁻³
201 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₁ClN₂O₆
M_r	326.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.5850 (5), 5.04379 (14), 21.0272 (7)
β (°)	104.427 (4)
V (Å³)	1395.35 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.40 × 0.40 × 0.30

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.984, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	6136, 2853, 2141
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.104, 1.04
No. of reflections	2853
No. of parameters	201
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.29

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

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

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

Cassis, R., Tapia, R. & Valderrama, J. A. (1985). Synth. Commun. 15, 125–133. CrossRef CAS Web of Science Google Scholar
Darque, A., Dumetre, A., Hutter, S., Casano, G., Robin, M., Pannecouque, C. & Azas, N. (2009). Bioorg. Med. Chem. Lett. 19, 5962–5964. Web of Science CrossRef PubMed CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Griera, R., Armengol, M., Reyes, A., Alvarez, M., Palomer, A., Cabre, F., Pascual, J., Garcia, M. L. & Mauleon, D. (1997). Eur. J. Med. Chem. 32, 547–570. CrossRef CAS Web of Science Google Scholar
Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar