Diethyl 2-[(4-bromo-anilino)methyl-idene]malonate.

In the title compound, C(14)H(16)BrNO(4), inter-molecular C-H⋯O hydrogen bonds link the mol-ecules, forming a stable structure. An intra-molecular N-H⋯O hydrogen bond results in the formation of a six-membered ring and helps to establish the mol-ecular conformation which is almost planar, with an r.m.s deviation of 0.0842 Å.

Related literature

For the preparation, see: Lager et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C14H16BrNO4

M = 342.19

Monoclinic,

a = 9.2440 (18) Å

b = 6.5000 (13) Å

c = 13.448 (3) Å

β = 110.10 (3)°

V = 758.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 2.72 mm−1

T = 293 K

0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.496, T max = 0.773

2851 measured reflections

2790 independent reflections

1606 reflections with I > 2σ(I)

R int = 0.071

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.154

S = 1.00

2790 reflections

181 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.39 e Å−3

Absolute structure: Flack (1983 ▶), 1253 Friedel pairs

Flack parameter: −0.01 (2)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97; software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045150/bq2249sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045150/bq2249Isup2.hkl

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

C14H16BrNO4	F(000) = 348
Mr = 342.19	Dx = 1.498 Mg m−3
Monoclinic, P21	Melting point: 367 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.2440 (18) Å	Cell parameters from 25 reflections
b = 6.5000 (13) Å	θ = 9–14°
c = 13.448 (3) Å	µ = 2.72 mm−1
β = 110.10 (3)°	T = 293 K
V = 758.8 (3) Å3	Needle, colourless
Z = 2	0.30 × 0.10 × 0.10 mm

Enraf–Nonius CAD-4 diffractometer	1606 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.071
graphite	θmax = 25.4°, θmin = 1.6°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −7→7
Tmin = 0.496, Tmax = 0.773	l = −5→16
2851 measured reflections	3 standard reflections every 200 reflections
2790 independent reflections	intensity decay: 1%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066	H-atom parameters constrained
wR(F2) = 0.154	w = 1/[σ2(Fo2) + (0.078P)2 + ] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2790 reflections	Δρmax = 0.49 e Å−3
181 parameters	Δρmin = −0.39 e Å−3
1 restraint	Absolute structure: Flack (1983), 1253 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (2)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br	0.96900 (11)	0.78434 (19)	0.08931 (9)	0.1008 (4)
N	0.7057 (7)	0.0195 (9)	0.2183 (5)	0.0626 (16)
H0A	0.6242	−0.0249	0.1697	0.075*
C1	0.7111 (8)	0.2666 (15)	0.0881 (6)	0.0691 (19)
H1A	0.6318	0.1944	0.0387	0.083*
O1	0.8800 (8)	−0.2964 (10)	0.4901 (5)	0.116 (3)
O2	0.7014 (6)	−0.5254 (9)	0.4487 (4)	0.0768 (15)
C2	0.7701 (9)	0.4458 (13)	0.0594 (6)	0.068 (2)
H2A	0.7280	0.4973	−0.0091	0.082*
C3	0.8892 (9)	0.5442 (11)	0.1320 (8)	0.069 (2)
O3	0.4955 (6)	−0.2676 (8)	0.1562 (5)	0.0859 (18)
C4	0.9487 (9)	0.4794 (12)	0.2343 (7)	0.068 (2)
H4A	1.0276	0.5532	0.2832	0.082*
O4	0.4944 (6)	−0.5243 (8)	0.2634 (4)	0.0673 (13)
C5	0.8899 (8)	0.2992 (19)	0.2660 (5)	0.066 (2)
H5A	0.9301	0.2520	0.3354	0.079*
C6	0.7740 (8)	0.1980 (10)	0.1930 (6)	0.0558 (19)
C7	0.7510 (8)	−0.0856 (11)	0.3061 (6)	0.0521 (17)
H7A	0.8348	−0.0334	0.3608	0.062*
C8	0.6869 (8)	−0.2699 (11)	0.3269 (6)	0.062 (2)
C9	0.7662 (9)	−0.3565 (13)	0.4292 (6)	0.0594 (19)
C10	0.7736 (9)	−0.6258 (12)	0.5497 (6)	0.072 (2)
H10A	0.7952	−0.5273	0.6071	0.086*
H10B	0.8694	−0.6907	0.5524	0.086*
C11	0.6597 (12)	−0.7843 (17)	0.5578 (9)	0.124 (5)
H11A	0.7005	−0.8544	0.6244	0.186*
H11B	0.6411	−0.8817	0.5011	0.186*
H11C	0.5648	−0.7178	0.5530	0.186*
C12	0.5544 (9)	−0.3509 (12)	0.2415 (6)	0.0586 (18)
C13	0.3642 (9)	−0.6084 (13)	0.1829 (6)	0.079 (2)
H13A	0.3922	−0.6543	0.1233	0.094*
H13B	0.2832	−0.5063	0.1581	0.094*
C14	0.3121 (12)	−0.7836 (14)	0.2315 (8)	0.105 (4)
H14A	0.2224	−0.8442	0.1805	0.157*
H14B	0.2872	−0.7363	0.2913	0.157*
H14C	0.3927	−0.8844	0.2543	0.157*

	U11	U22	U33	U12	U13	U23
Br	0.0966 (6)	0.0669 (5)	0.1532 (9)	−0.0125 (6)	0.0612 (6)	0.0184 (7)
N	0.051 (4)	0.065 (4)	0.065 (4)	−0.003 (3)	0.011 (3)	0.000 (3)
C1	0.072 (5)	0.056 (5)	0.079 (5)	0.008 (5)	0.024 (4)	0.012 (5)
O1	0.098 (5)	0.119 (6)	0.091 (4)	−0.047 (4)	−0.019 (4)	0.038 (4)
O2	0.056 (3)	0.080 (4)	0.085 (4)	−0.008 (3)	0.013 (3)	0.031 (3)
C2	0.060 (5)	0.073 (5)	0.074 (5)	0.008 (4)	0.026 (4)	0.026 (4)
C3	0.057 (5)	0.045 (4)	0.108 (7)	−0.014 (4)	0.034 (5)	−0.009 (5)
O3	0.078 (4)	0.071 (5)	0.088 (4)	−0.021 (3)	0.002 (3)	0.013 (3)
C4	0.058 (5)	0.060 (5)	0.087 (6)	−0.003 (4)	0.026 (5)	−0.006 (5)
O4	0.067 (3)	0.059 (3)	0.077 (3)	−0.010 (3)	0.026 (3)	0.000 (3)
C5	0.064 (4)	0.072 (5)	0.058 (4)	0.022 (6)	0.014 (4)	0.023 (5)
C6	0.059 (4)	0.042 (3)	0.076 (5)	−0.016 (3)	0.036 (4)	−0.015 (4)
C7	0.047 (4)	0.055 (4)	0.055 (5)	0.007 (3)	0.019 (4)	0.002 (3)
C8	0.052 (4)	0.058 (6)	0.088 (6)	−0.002 (3)	0.040 (4)	−0.008 (4)
C9	0.052 (5)	0.074 (5)	0.040 (4)	−0.009 (4)	0.001 (4)	0.000 (4)
C10	0.061 (5)	0.075 (5)	0.072 (5)	0.003 (4)	0.013 (4)	0.028 (4)
C11	0.087 (6)	0.132 (11)	0.157 (9)	0.002 (6)	0.048 (7)	0.075 (9)
C12	0.061 (5)	0.063 (5)	0.058 (5)	0.011 (4)	0.029 (4)	0.014 (4)
C13	0.065 (5)	0.086 (6)	0.073 (5)	−0.022 (5)	0.009 (4)	−0.022 (5)
C14	0.118 (8)	0.083 (7)	0.140 (9)	−0.035 (6)	0.080 (7)	−0.024 (6)

Br—C3	1.898 (7)	C5—C6	1.349 (11)
N—C7	1.302 (8)	C5—H5A	0.9300
N—C6	1.417 (9)	C7—C8	1.407 (9)
N—H0A	0.8600	C7—H7A	0.9300
C1—C2	1.396 (11)	C8—C9	1.432 (10)
C1—C6	1.401 (10)	C8—C12	1.459 (11)
C1—H1A	0.9300	C10—C11	1.503 (11)
O1—C9	1.157 (8)	C10—H10A	0.9700
O2—C9	1.320 (9)	C10—H10B	0.9700
O2—C10	1.446 (8)	C11—H11A	0.9600
C2—C3	1.356 (11)	C11—H11B	0.9600
C2—H2A	0.9300	C11—H11C	0.9600
C3—C4	1.361 (11)	C13—C14	1.474 (11)
O3—C12	1.215 (8)	C13—H13A	0.9700
C4—C5	1.417 (14)	C13—H13B	0.9700
C4—H4A	0.9300	C14—H14A	0.9600
O4—C12	1.333 (8)	C14—H14B	0.9600
O4—C13	1.423 (8)	C14—H14C	0.9600
C7—N—C6	128.0 (6)	O1—C9—C8	126.0 (8)
C7—N—H0A	116.0	O2—C9—C8	113.6 (7)
C6—N—H0A	116.0	O2—C10—C11	105.6 (7)
C2—C1—C6	118.6 (8)	O2—C10—H10A	110.6
C2—C1—H1A	120.7	C11—C10—H10A	110.6
C6—C1—H1A	120.7	O2—C10—H10B	110.6
C9—O2—C10	117.9 (6)	C11—C10—H10B	110.6
C3—C2—C1	119.5 (8)	H10A—C10—H10B	108.8
C3—C2—H2A	120.3	C10—C11—H11A	109.5
C1—C2—H2A	120.3	C10—C11—H11B	109.5
C2—C3—C4	121.9 (7)	H11A—C11—H11B	109.5
C2—C3—Br	118.3 (7)	C10—C11—H11C	109.5
C4—C3—Br	119.8 (6)	H11A—C11—H11C	109.5
C3—C4—C5	119.8 (7)	H11B—C11—H11C	109.5
C3—C4—H4A	120.1	O3—C12—O4	120.0 (7)
C5—C4—H4A	120.1	O3—C12—C8	124.4 (7)
C12—O4—C13	117.7 (6)	O4—C12—C8	115.6 (6)
C6—C5—C4	118.3 (7)	O4—C13—C14	106.2 (7)
C6—C5—H5A	120.8	O4—C13—H13A	110.5
C4—C5—H5A	120.8	C14—C13—H13A	110.5
C5—C6—C1	121.9 (7)	O4—C13—H13B	110.5
C5—C6—N	122.1 (7)	C14—C13—H13B	110.5
C1—C6—N	116.0 (7)	H13A—C13—H13B	108.7
N—C7—C8	126.9 (7)	C13—C14—H14A	109.5
N—C7—H7A	116.5	C13—C14—H14B	109.5
C8—C7—H7A	116.5	H14A—C14—H14B	109.5
C7—C8—C9	114.5 (7)	C13—C14—H14C	109.5
C7—C8—C12	116.6 (7)	H14A—C14—H14C	109.5
C9—C8—C12	128.9 (6)	H14B—C14—H14C	109.5
O1—C9—O2	120.3 (7)
C6—C1—C2—C3	2.2 (11)	C10—O2—C9—O1	2.6 (12)
C1—C2—C3—C4	−3.4 (11)	C10—O2—C9—C8	179.5 (6)
C1—C2—C3—Br	178.8 (6)	C7—C8—C9—O1	−5.5 (11)
C2—C3—C4—C5	2.7 (12)	C12—C8—C9—O1	171.8 (9)
Br—C3—C4—C5	−179.5 (6)	C7—C8—C9—O2	177.9 (6)
C3—C4—C5—C6	−0.8 (12)	C12—C8—C9—O2	−4.9 (11)
C4—C5—C6—C1	−0.3 (11)	C9—O2—C10—C11	169.0 (7)
C4—C5—C6—N	−178.4 (7)	C13—O4—C12—O3	1.8 (9)
C2—C1—C6—C5	−0.4 (11)	C13—O4—C12—C8	179.5 (6)
C2—C1—C6—N	177.8 (6)	C7—C8—C12—O3	−1.7 (10)
C7—N—C6—C5	−8.8 (11)	C9—C8—C12—O3	−178.9 (7)
C7—N—C6—C1	173.0 (7)	C7—C8—C12—O4	−179.3 (5)
C6—N—C7—C8	−175.6 (6)	C9—C8—C12—O4	3.5 (10)
N—C7—C8—C9	176.9 (7)	C12—O4—C13—C14	−173.9 (6)
N—C7—C8—C12	−0.7 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O3	0.86	1.95	2.615 (8)	134
C1—H1A···O3i	0.93	2.49	3.190 (10)	132
C5—H5A···O1ii	0.93	2.42	3.298 (9)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O3	0.86	1.95	2.615 (8)	134
C1—H1A⋯O3i	0.93	2.49	3.190 (10)	132
C5—H5A⋯O1ii	0.93	2.42	3.298 (9)	157

Symmetry codes: (i) ; (ii) .