Diethyl 2-[(4-bromo­anilino)methyl­idene]malonate

Feng, Z.-Q.; Yang, X.-L.; Ye, Y.-F.; Dong, T.; Wang, H.-Q.

doi:10.1107/S1600536810045150

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3119

https://doi.org/10.1107/S1600536810045150

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Diethyl 2-[(4-bromoanilino)methylidene]malonate

Zhi-Qiang Feng,^a ^* Xiao-Li Yang,^a Yuan-Feng Ye,^a Tao Dong ^a and Huai-Qing Wang ^a

^aCollege of Materials Engineering, Jinling Institute of Technology, No. 99 Hongjing Street, Nanjing 211169, People's Republic of China
^*Correspondence e-mail: fzq@jit.edu.cn

(Received 1 November 2010; accepted 4 November 2010; online 10 November 2010)

In the title compound, C₁₄H₁₆BrNO₄, intermolecular C—H⋯O hydrogen bonds link the molecules, forming a stable structure. An intramolecular N—H⋯O hydrogen bond results in the formation of a six-membered ring and helps to establish the molecular 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_r = 342.19
Monoclinic, P 2₁
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[F² > 2σ(F²)] = 0.066
wR(F²) = 0.154
S = 1.00
2790 reflections
181 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.39 e Å⁻³
Absolute structure: Flack (1983 ), 1253 Friedel pairs
Flack parameter: −0.01 (2)

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) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+1]$ .

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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810045150/bq2249Isup2.hkl

checkCIF report

Comment top

We report herein the crystal structure of the title compound, diethyl 2-((4-bromophenylamino)methylene)malonate which is an important intermediate of synthesizing pyrazoloquinolinones. In the molecule of the title compound (Fig. 1), all bond lengths and angles (Allen et al., 1987) are within normal ranges. The intramolecular N-H···O hydrogen bond (Table 1) results in the formation of a six-membered ring (N/C7/C8/C12/O3/H0A). In the crystal structure, intermolecular weak C-H···O hydrogen bonds link the molecules to form a stable structure (Fig. 2).

Related literature top

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

Experimental top

The title compound, diethyl 2-((4-bromophenylamino)methylene)malonate was prepared by the literature method (Lager et al., 2006). 4-bromoaniline (1.2 mmol) and diethyl ethoxymethylenemalonate (1.2 mmol) were mixed and heated at 403 K for 2 h. Low boiling components were evaporated at low pressure with a cold trap yielding diethyl 2-((4-bromophenylamino) methylene)malonate. The crude product was purified by recrystallization from diethyl ether yielding the title compound (73 % yield), as a white solid. Crystals suitable for X-ray analysis were obtained by slow evaporation of an methanol solution.

Structure description top

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

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1989); 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 (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines show H-bonding.
	Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed line.

Diethyl 2-[(4-bromoanilino)methylidene]malonate top

Crystal data top

C₁₄H₁₆BrNO₄	F(000) = 348
M_r = 342.19	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.078P)² + ] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2790 reflections	Δρ_max = 0.49 e Å⁻³
181 parameters	Δρ_min = −0.39 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1253 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

Crystal data top

C₁₄H₁₆BrNO₄	V = 758.8 (3) Å³
M_r = 342.19	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.2440 (18) Å	µ = 2.72 mm⁻¹
b = 6.5000 (13) Å	T = 293 K
c = 13.448 (3) Å	0.30 × 0.10 × 0.10 mm
β = 110.10 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1606 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.071
T_min = 0.496, T_max = 0.773	3 standard reflections every 200 reflections
2851 measured reflections	intensity decay: 1%
2790 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	H-atom parameters constrained
wR(F²) = 0.154	Δρ_max = 0.49 e Å⁻³
S = 1.00	Δρ_min = −0.39 e Å⁻³
2790 reflections	Absolute structure: Flack (1983), 1253 Friedel pairs
181 parameters	Absolute structure parameter: −0.01 (2)
1 restraint

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x+1, y+1/2, −z; (ii) −x+2, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆BrNO₄
M_r	342.19
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	9.2440 (18), 6.5000 (13), 13.448 (3)
β (°)	110.10 (3)
V (Å³)	758.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.72
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.496, 0.773
No. of measured, independent and observed [I > 2σ(I)] reflections	2851, 2790, 1606
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.154, 1.00
No. of reflections	2790
No. of parameters	181
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.39
Absolute structure	Flack (1983), 1253 Friedel pairs
Absolute structure parameter	−0.01 (2)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+1, y+1/2, −z; (ii) −x+2, y+1/2, −z+1.

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

References

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