5-(4-Bromo-anilinomethyl-ene)-2,2-dimethyl-1,3-dioxane-4,6-dione.

In the title compound, C(13)H(12)BrNO(4), the dihedral angles between the amino-methyl-ene group and the dioxane ring and between the benzyl ring and the amino-methyl-ene 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 intra-molecular N-H⋯O hydrogen bond may stabilize the planar conformation of the mol-ecule. An inter-molecular C-H⋯O inter-action 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. (2009 ▶).

Experimental

Crystal data

C13H12BrNO4

M = 326.14

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.160

S = 0.99

2279 reflections

179 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.97 e Å−3

Δρmin = −0.96 e Å−3

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 ▶).

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

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

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

C13H12BrNO4	F(000) = 656
Mr = 326.14	Dx = 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

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

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(Fo2) + (0.0585P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
2279 reflections	Δρmax = 0.97 e Å−3
179 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) .