5-(4-Bromo­anilinomethyl­ene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Shi, J.-Y.; Yang, J.-C.; Yang, J.-L.

doi:10.1107/S1600536809035776

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2458

doi:10.1107/S1600536809035776

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5-(4-Bromoanilinomethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione

Jian-You Shi,^a Jin-Cheng Yang ^a ^* and Jin-Liang Yang ^b

^aDepartment of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, 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: jlyang01@163.com

(Received 10 August 2009; accepted 4 September 2009; online 12 September 2009)

In the title compound, C₁₃H₁₂BrNO₄, the dihedral angles between the aminomethylene group and the dioxane ring and between the benzyl ring and the aminomethylene unit are 7.96 (4) and 12.15 (4)°, respectively. The dioxane ring shows a half-boat conformation, in which the C atom between the dioxane ring O atoms is 0.460 (8) Å out of the plane through the remaining ring atoms. An intramolecular N—H⋯O hydrogen bond may stabilize the planar conformation of the molecule. An intermolecular C—H⋯O interaction is also present.

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 ,c ).

Experimental

Crystal data

C₁₃H₁₂BrNO₄
M_r = 326.14
Monoclinic, P 2₁ /c
a = 13.837 (3) Å
b = 13.019 (3) Å
c = 7.4900 (15) Å
β = 105.24 (3)°
V = 1301.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.17 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.04 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.570, T_max = 0.884
9108 measured reflections
2279 independent reflections
1063 reflections with I > 2σ(I)
R_int = 0.113

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.160
S = 0.99
2279 reflections
179 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.96 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O4	0.98 (7)	2.06 (8)	2.770 (7)	128 (6)
C9—H9⋯O3ⁱ	0.93	2.49	3.345 (8)	152
Symmetry code: (i) -x+2, -y, -z+2.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035776/rk2160sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035776/rk2160Isup2.hkl

checkCIF report

Comment top

The 4(1H)quinolone structure plays an extremely important role in the field of pharmaceutical chemistry. The 5–arylaminomethylene–2,2–dimethyl–1,3–dioxane–4,6–diones are the key intermediates which can be used to synthesize the 4(1H)quinolone derivatives by thermolysis (Cassis et al., 1985), that can be used as precursors foranti–malarial agents, anticancer agents, and reversible (H+/K+) ATPase inhibitors (Ruchelman et al., 2003). The conformation of the title compound is similar with those reported early by Li et al., (2009a,b,c), which is almost planar with the dihedral angles of 7.96 (4)° and 12.15 (4)° between the aminomethylene group and the dioxane ring, and between the benzyl ring and the aminomethylene unit, respectively. Besides, the dioxane ring of the title compound exhibits a half–boat conformation, in which the C atom between the dioxane oxygen atoms is -0.460 (8) Å out–of–plane. The intramolecular N—H···O hydrogen bond (Table 1) is stabilizing the planar conformation in the molecule.

Related literature top

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,c).

Experimental top

A solution 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 2.5 h, then the arylamine (1.32 g, 0.01 mol) was added into the above solution. The mixture was heated under reflux for another 4 h and then filtered. Single crystals were obtained from the filtrate after 2 days.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. Crystal packing of the title compound, showing the intermolecular hydrogen bonds as dashed lines. H atoms not involved in these interactions have been omitted. Symmetry code: (i) -x+2, -y, -z+2.

5-(4-Bromoanilinomethylene)-2,2-dimethyl-1,3-dioxane-4,6-dione top

Crystal data top

C₁₃H₁₂BrNO₄	F(000) = 656
M_r = 326.14	D_x = 1.664 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4079 reflections
a = 13.837 (3) Å	θ = 2.2–27.7°
b = 13.019 (3) Å	µ = 3.17 mm⁻¹
c = 7.4900 (15) Å	T = 113 K
β = 105.24 (3)°	Plate, colourless
V = 1301.8 (5) Å³	0.20 × 0.18 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2279 independent reflections
Radiation source: rotating anode	1063 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.113
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω and ϕ scans	h = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −15→15
T_min = 0.570, T_max = 0.884	l = −7→8
9108 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.066	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.160	w = 1/[σ²(F_o²) + (0.0585P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
2279 reflections	Δρ_max = 0.97 e Å⁻³
179 parameters	Δρ_min = −0.96 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: 0.017 (3)

Crystal data top

C₁₃H₁₂BrNO₄	V = 1301.8 (5) Å³
M_r = 326.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.837 (3) Å	µ = 3.17 mm⁻¹
b = 13.019 (3) Å	T = 113 K
c = 7.4900 (15) Å	0.20 × 0.18 × 0.04 mm
β = 105.24 (3)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2279 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1063 reflections with I > 2σ(I)
T_min = 0.570, T_max = 0.884	R_int = 0.113
9108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.97 e Å⁻³
2279 reflections	Δρ_min = −0.96 e Å⁻³
179 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
Br1	0.55042 (5)	0.35263 (5)	1.07667 (10)	0.0385 (4)
O1	1.2599 (3)	0.2261 (3)	0.9075 (6)	0.0281 (11)
O2	1.2115 (3)	0.0519 (3)	0.8410 (5)	0.0263 (11)
O3	1.0562 (3)	0.0009 (3)	0.8058 (6)	0.0335 (12)
O4	1.1515 (3)	0.3439 (3)	0.9505 (6)	0.0310 (12)
N1	0.9664 (4)	0.2768 (4)	0.9800 (7)	0.0235 (13)
H1N	1.008 (7)	0.337 (5)	0.978 (11)	0.08 (3)*
C1	1.0970 (5)	0.1708 (4)	0.9159 (8)	0.0232 (16)
C2	1.1680 (5)	0.2526 (5)	0.9294 (8)	0.0269 (16)
C3	1.2909 (5)	0.1209 (5)	0.9352 (9)	0.0270 (16)
C4	1.1175 (5)	0.0689 (5)	0.8546 (8)	0.0260 (16)
C5	1.3741 (5)	0.1084 (5)	0.8402 (9)	0.0324 (17)
H5A	1.3500	0.1275	0.7124	0.049*
H5B	1.3955	0.0380	0.8485	0.049*
H5C	1.4294	0.1516	0.8994	0.049*
C6	1.3222 (5)	0.0959 (5)	1.1391 (8)	0.0351 (18)
H6A	1.3725	0.1438	1.2018	0.053*
H6B	1.3490	0.0275	1.1562	0.053*
H6C	1.2652	0.1004	1.1890	0.053*
C7	1.0035 (5)	0.1867 (5)	0.9435 (8)	0.0250 (16)
H7	0.9624	0.1294	0.9362	0.030*
C8	0.8705 (5)	0.2914 (5)	1.0096 (7)	0.0212 (15)
C9	0.8101 (5)	0.2096 (5)	1.0358 (8)	0.0294 (17)
H9	0.8340	0.1426	1.0388	0.035*
C10	0.7156 (5)	0.2274 (5)	1.0571 (8)	0.0284 (16)
H10	0.6755	0.1730	1.0746	0.034*
C11	0.6813 (5)	0.3276 (5)	1.0521 (8)	0.0241 (16)
C12	0.7412 (5)	0.4097 (4)	1.0325 (8)	0.0259 (16)
H12	0.7180	0.4766	1.0339	0.031*
C13	0.8362 (5)	0.3912 (5)	1.0109 (8)	0.0252 (16)
H13	0.8768	0.4459	0.9973	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0334 (6)	0.0385 (6)	0.0460 (6)	0.0036 (3)	0.0148 (4)	−0.0078 (3)
O1	0.038 (3)	0.020 (2)	0.031 (3)	0.000 (2)	0.019 (2)	0.000 (2)
O2	0.030 (3)	0.022 (2)	0.032 (3)	0.001 (2)	0.016 (2)	−0.004 (2)
O3	0.042 (3)	0.022 (3)	0.044 (3)	−0.005 (2)	0.024 (3)	−0.001 (2)
O4	0.040 (3)	0.018 (3)	0.038 (3)	0.000 (2)	0.016 (2)	−0.006 (2)
N1	0.028 (4)	0.019 (3)	0.025 (3)	0.001 (3)	0.010 (3)	−0.003 (2)
C1	0.035 (5)	0.019 (4)	0.019 (3)	−0.003 (3)	0.013 (3)	0.004 (3)
C2	0.037 (5)	0.027 (4)	0.019 (3)	0.006 (3)	0.012 (3)	0.005 (3)
C3	0.029 (5)	0.020 (4)	0.034 (4)	0.008 (3)	0.012 (3)	−0.003 (3)
C4	0.030 (4)	0.023 (4)	0.027 (4)	0.003 (3)	0.010 (3)	0.006 (3)
C5	0.034 (5)	0.023 (4)	0.043 (4)	0.002 (3)	0.014 (4)	−0.006 (3)
C6	0.047 (5)	0.030 (4)	0.024 (4)	0.015 (3)	0.002 (3)	−0.004 (3)
C7	0.034 (5)	0.024 (4)	0.019 (3)	0.002 (3)	0.010 (3)	0.005 (3)
C8	0.030 (4)	0.020 (4)	0.014 (3)	−0.004 (3)	0.008 (3)	−0.002 (3)
C9	0.047 (5)	0.018 (4)	0.028 (4)	0.009 (3)	0.019 (3)	0.000 (3)
C10	0.037 (5)	0.030 (4)	0.022 (3)	−0.006 (3)	0.014 (3)	−0.005 (3)
C11	0.028 (4)	0.022 (4)	0.022 (4)	0.001 (3)	0.007 (3)	−0.003 (3)
C12	0.042 (5)	0.013 (3)	0.023 (4)	0.008 (3)	0.010 (3)	0.005 (3)
C13	0.041 (5)	0.016 (3)	0.022 (4)	−0.001 (3)	0.014 (3)	0.000 (3)

Geometric parameters (Å, º) top

Br1—C11	1.895 (6)	C5—H5B	0.9600
O1—C2	1.369 (7)	C5—H5C	0.9600
O1—C3	1.433 (7)	C6—H6A	0.9600
O2—C4	1.350 (7)	C6—H6B	0.9600
O2—C3	1.449 (7)	C6—H6C	0.9600
O3—C4	1.214 (7)	C7—H7	0.9300
O4—C2	1.229 (6)	C8—C13	1.385 (8)
N1—C7	1.338 (7)	C8—C9	1.399 (8)
N1—C8	1.415 (8)	C9—C10	1.378 (8)
N1—H1N	0.98 (7)	C9—H9	0.9300
C1—C7	1.378 (8)	C10—C11	1.386 (8)
C1—C2	1.434 (8)	C10—H10	0.9300
C1—C4	1.455 (8)	C11—C12	1.383 (8)
C3—C6	1.509 (8)	C12—C13	1.386 (8)
C3—C5	1.513 (8)	C12—H12	0.9300
C5—H5A	0.9600	C13—H13	0.9300

C2—O1—C3	118.4 (5)	C3—C6—H6B	109.5
C4—O2—C3	118.9 (5)	H6A—C6—H6B	109.5
C7—N1—C8	125.2 (6)	C3—C6—H6C	109.5
C7—N1—H1N	117 (5)	H6A—C6—H6C	109.5
C8—N1—H1N	118 (5)	H6B—C6—H6C	109.5
C7—C1—C2	122.1 (6)	N1—C7—C1	126.0 (6)
C7—C1—C4	116.9 (6)	N1—C7—H7	117.0
C2—C1—C4	120.8 (6)	C1—C7—H7	117.0
O4—C2—O1	118.0 (6)	C13—C8—C9	119.7 (6)
O4—C2—C1	125.5 (6)	C13—C8—N1	117.7 (5)
O1—C2—C1	116.4 (5)	C9—C8—N1	122.6 (6)
O1—C3—O2	111.2 (5)	C10—C9—C8	120.5 (6)
O1—C3—C6	110.4 (5)	C10—C9—H9	119.7
O2—C3—C6	109.8 (5)	C8—C9—H9	119.7
O1—C3—C5	105.7 (5)	C9—C10—C11	119.0 (6)
O2—C3—C5	106.1 (5)	C9—C10—H10	120.5
C6—C3—C5	113.6 (6)	C11—C10—H10	120.5
O3—C4—O2	117.9 (6)	C12—C11—C10	121.3 (6)
O3—C4—C1	125.5 (6)	C12—C11—Br1	119.5 (5)
O2—C4—C1	116.4 (6)	C10—C11—Br1	119.2 (5)
C3—C5—H5A	109.5	C11—C12—C13	119.5 (6)
C3—C5—H5B	109.5	C11—C12—H12	120.3
H5A—C5—H5B	109.5	C13—C12—H12	120.3
C3—C5—H5C	109.5	C8—C13—C12	120.0 (6)
H5A—C5—H5C	109.5	C8—C13—H13	120.0
H5B—C5—H5C	109.5	C12—C13—H13	120.0
C3—C6—H6A	109.5

C3—O1—C2—O4	162.6 (5)	C2—C1—C4—O2	10.3 (8)
C3—O1—C2—C1	−20.6 (8)	C8—N1—C7—C1	−179.4 (6)
C7—C1—C2—O4	−6.4 (10)	C2—C1—C7—N1	2.0 (10)
C4—C1—C2—O4	167.6 (6)	C4—C1—C7—N1	−172.3 (6)
C7—C1—C2—O1	177.0 (5)	C7—N1—C8—C13	−168.0 (5)
C4—C1—C2—O1	−8.9 (8)	C7—N1—C8—C9	11.5 (9)
C2—O1—C3—O2	46.4 (7)	C13—C8—C9—C10	2.0 (9)
C2—O1—C3—C6	−75.7 (7)	N1—C8—C9—C10	−177.5 (5)
C2—O1—C3—C5	161.1 (5)	C8—C9—C10—C11	0.1 (9)
C4—O2—C3—O1	−44.9 (7)	C9—C10—C11—C12	−2.3 (9)
C4—O2—C3—C6	77.5 (6)	C9—C10—C11—Br1	178.8 (5)
C4—O2—C3—C5	−159.4 (5)	C10—C11—C12—C13	2.3 (9)
C3—O2—C4—O3	−166.3 (5)	Br1—C11—C12—C13	−178.7 (4)
C3—O2—C4—C1	17.6 (7)	C9—C8—C13—C12	−1.9 (8)
C7—C1—C4—O3	8.9 (9)	N1—C8—C13—C12	177.6 (5)
C2—C1—C4—O3	−165.4 (6)	C11—C12—C13—C8	−0.2 (8)
C7—C1—C4—O2	−175.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.98 (7)	2.06 (8)	2.770 (7)	128 (6)
C9—H9···O3ⁱ	0.93	2.49	3.345 (8)	152

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂BrNO₄
M_r	326.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	13.837 (3), 13.019 (3), 7.4900 (15)
β (°)	105.24 (3)
V (Å³)	1301.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.17
Crystal size (mm)	0.20 × 0.18 × 0.04

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.570, 0.884
No. of measured, independent and observed [I > 2σ(I)] reflections	9108, 2279, 1063
R_int	0.113
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.160, 0.99
No. of reflections	2279
No. of parameters	179
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.97, −0.96

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4	0.98 (7)	2.06 (8)	2.770 (7)	128 (6)
C9—H9···O3ⁱ	0.93	2.49	3.345 (8)	152

Symmetry code: (i) −x+2, −y, −z+2.

References

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Ruchelman, A. L., Singh, S. K., Ray, A., Wu, X. H., Yang, J. M., Li, T. K., Liu, A., Liu, L. F. & LaVoie, E. J. (2003). Bioorg. Med. Chem. 11, 2061–2073. Web of Science CrossRef PubMed CAS Google Scholar
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COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2458

doi:10.1107/S1600536809035776

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access