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Acta Cryst. (2008). E64, o789    [ doi:10.1107/S1600536808003085 ]

(E)-2-{N-Ethyl-4-[(4-nitrophenyl)diazenyl]anilino}ethyl acrylate

M. Yousefi, H. Hosseini, V. Amani, M. Arab Chamjangali and H. R. Khavasi

Abstract top

In the molecule of the title compound, C19H20N4O4, the rings are almost coplanar, forming a dihedral angle of 0.76 (3)°. In the crystal structure, intermolecular C-H...O hydrogen bonds link the molecules.

Comment top

It is well known for many years that dyes have been most widely used in fields such as dyeing textile fibers, biomedical studies, advanced applications in organic synthesis and high technology areas like lasers, liquid crystalline displays, electrooptical devices and ink-jet printers (Peters & Freeman, 1991; Gregory 1991; Gur et al., 2007). Azo colorants are the most versatile class of dyes (Venkataraman 1970). They can also be used as indicators in chemical laboratories and as stains in the biological field (Srinivasa et al., 2003). We report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are within normal ranges (Lacroix et al., 2000; Gunnlaugsson et al., 2001). Rings A (C1—C6) and B (C7—C12) are, of course, planar and the dihedral angle between them is 0.76 (3)°, so they are also almost coplanar. The atoms N1, N2, N3, N4, O1 and O2 are at the distances of -0.124 (2) Å, 0.070 (3) Å, -0.016 (2) Å, 0.162 (3) Å, -0.066 (3) Å and -0.255 (2) Å, respectively, to the best plane of the coplanar rings.

In the crystal structure, intermolecular C—H···O hydrogen bonds link the molecules, in which they may be effective in the stabilization of the structure.

Related literature top

For related literature, see: Peters & Freeman (1991); Gregory (1991); Gur et al. (2007); Venkataraman (1970); Srinivasa et al. (2003); For bond-length data, see: Lacroix et al. (2000); Gunnlaugsson et al. (2001).

Experimental top

For the preparation of the title compound, (I), to a magnetically stirred solution of 4-nitro-4'-[N-ethyl-N-(2-hydroxyethyl)-amino]azobenzene (2.48 mmol) in THF (20 ml), was added dropwise acryloyl chloride (2.48 mmol) in dry nitrogen atmosphere. After 2 h, the mixture was filtered and the desired product was precipitated out by adding water. The solid filtered and washed several times with water, and then dried. The orange precipitated product was recrystallized from ethyl alcohol. After 72 h, orange plate crystals of (I) were isolated (yield; 52.0%, m.p. 397–398 K).

Refinement top

H atoms were positioned geometrically with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, respectively, (the two H atoms of atom C19 with C—H = 0.93 Å) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-STEP32 (Stoe & Cie, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.
(E)-2-{N-Ethyl-4-[(4-nitrophenyl)diazenyl]anilino}ethyl acrylate top
Crystal data top
C19H20N4O4F000 = 776
Mr = 368.39Dx = 1.361 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 5000 reflections
a = 8.1518 (9) Åθ = 2.0–27.9º
b = 10.6651 (11) ŵ = 0.10 mm−1
c = 20.6782 (19) ÅT = 120 (2) K
V = 1797.8 (3) Å3Plate, orange
Z = 40.5 × 0.2 × 0.06 mm
Data collection top
Stoe IPDSII
diffractometer		2456 independent reflections
Radiation source: fine-focus sealed tube2346 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
Detector resolution: 0.15 mm pixels mm-1θmax = 27.9º
T = 120(2) Kθmin = 2.0º
rotation method scansh = −10→10
Absorption correction: numerical
[shape of crystal determined optically (X-SHAPE and X-RED; Stoe & Cie, 2005)]		k = −14→14
Tmin = 0.980, Tmax = 0.990l = −27→26
15596 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.079  w = 1/[σ2(Fo2) + (0.041P)2 + 0.3046P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.005
2456 reflectionsΔρmax = 0.21 e Å−3
244 parametersΔρmin = −0.21 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C19H20N4O4V = 1797.8 (3) Å3
Mr = 368.39Z = 4
Orthorhombic, P212121Mo Kα
a = 8.1518 (9) ŵ = 0.10 mm−1
b = 10.6651 (11) ÅT = 120 (2) K
c = 20.6782 (19) Å0.5 × 0.2 × 0.06 mm
Data collection top
Stoe IPDSII
diffractometer		2456 independent reflections
Absorption correction: numerical
[shape of crystal determined optically (X-SHAPE and X-RED; Stoe & Cie, 2005)]		2346 reflections with I > 2σ(I)
Tmin = 0.980, Tmax = 0.990Rint = 0.047
15596 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031Δρmax = 0.21 e Å−3
wR(F2) = 0.079Δρmin = −0.21 e Å−3
S = 1.12Absolute structure: ?
2456 reflectionsFlack parameter: ?
244 parametersRogers parameter: ?
H-atom parameters constrained
Special details top

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
xyzUiso*/Ueq
O11.10305 (16)0.14200 (13)0.09457 (7)0.0364 (3)
O21.03152 (16)−0.04894 (11)0.07258 (7)0.0313 (3)
O3−0.36429 (14)0.34551 (10)0.47252 (5)0.0216 (2)
O4−0.21122 (16)0.32212 (12)0.56227 (6)0.0294 (3)
N11.00462 (17)0.05502 (13)0.09634 (7)0.0222 (3)
N20.40683 (16)0.13800 (12)0.22729 (6)0.0205 (3)
N30.30983 (16)0.04473 (12)0.22891 (6)0.0192 (3)
N4−0.29651 (17)0.09198 (12)0.35372 (6)0.0190 (3)
C10.84626 (18)0.07543 (14)0.12848 (7)0.0189 (3)
C20.8210 (2)0.18816 (14)0.16069 (8)0.0207 (3)
H20.90100.25030.16070.025*
C30.6730 (2)0.20566 (14)0.19291 (8)0.0207 (3)
H30.65330.28030.21480.025*
C40.55405 (18)0.11203 (14)0.19253 (7)0.0188 (3)
C50.5827 (2)−0.00013 (15)0.15898 (8)0.0236 (3)
H50.5026−0.06220.15850.028*
C60.7296 (2)−0.01923 (14)0.12656 (8)0.0224 (3)
H60.7493−0.09340.10420.027*
C70.16339 (18)0.06323 (14)0.26308 (7)0.0182 (3)
C80.12233 (19)0.17040 (14)0.29917 (7)0.0184 (3)
H80.19620.23670.30200.022*
C9−0.02636 (19)0.17795 (13)0.33038 (7)0.0185 (3)
H9−0.05050.24920.35450.022*
C10−0.14435 (18)0.07970 (14)0.32673 (7)0.0170 (3)
C11−0.0979 (2)−0.03058 (13)0.29288 (7)0.0190 (3)
H11−0.1685−0.09900.29170.023*
C120.05171 (19)−0.03651 (14)0.26169 (7)0.0190 (3)
H120.0791−0.10890.23910.023*
C13−0.4126 (2)−0.01280 (14)0.35654 (8)0.0218 (3)
H13A−0.4112−0.05650.31540.026*
H13B−0.52230.02020.36290.026*
C14−0.3749 (2)−0.10628 (16)0.41043 (9)0.0302 (4)
H14A−0.3785−0.06420.45140.036*
H14B−0.2676−0.14110.40390.036*
H14C−0.4549−0.17230.40980.036*
C15−0.35038 (19)0.21176 (14)0.38075 (8)0.0197 (3)
H15A−0.46820.21950.37560.024*
H15B−0.29900.27970.35710.024*
C16−0.3070 (2)0.22308 (14)0.45203 (7)0.0212 (3)
H16A−0.36050.15750.47680.025*
H16B−0.18940.21610.45810.025*
C17−0.3027 (2)0.38472 (15)0.52915 (8)0.0218 (3)
C18−0.3577 (2)0.51211 (16)0.54784 (8)0.0263 (3)
H18−0.33650.53850.58990.032*
C19−0.4339 (3)0.58999 (18)0.50938 (10)0.0398 (5)
H19A−0.45700.56670.46700.048*
H19B−0.46490.66870.52440.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0293 (6)0.0269 (6)0.0529 (8)−0.0081 (5)0.0145 (6)−0.0026 (6)
O20.0316 (6)0.0222 (5)0.0401 (7)0.0030 (5)0.0113 (6)−0.0058 (5)
O30.0232 (5)0.0183 (5)0.0235 (5)0.0039 (4)−0.0010 (4)−0.0038 (4)
O40.0289 (6)0.0331 (6)0.0261 (6)0.0055 (6)−0.0039 (5)−0.0022 (5)
N10.0223 (6)0.0194 (6)0.0250 (7)0.0007 (5)0.0034 (5)0.0016 (5)
N20.0205 (6)0.0176 (6)0.0233 (6)−0.0009 (5)0.0001 (5)−0.0010 (5)
N30.0196 (6)0.0169 (6)0.0211 (6)−0.0001 (5)0.0006 (5)0.0007 (5)
N40.0204 (6)0.0143 (5)0.0224 (6)0.0011 (5)0.0014 (5)−0.0009 (5)
C10.0198 (7)0.0177 (7)0.0193 (7)0.0007 (6)0.0014 (6)0.0012 (6)
C20.0211 (7)0.0161 (6)0.0248 (7)−0.0023 (6)−0.0005 (6)0.0008 (6)
C30.0235 (8)0.0145 (6)0.0240 (7)−0.0001 (6)−0.0003 (6)−0.0021 (6)
C40.0187 (7)0.0179 (7)0.0198 (6)0.0003 (6)−0.0006 (6)0.0005 (6)
C50.0242 (7)0.0185 (7)0.0281 (8)−0.0051 (6)0.0029 (6)−0.0048 (6)
C60.0256 (8)0.0165 (7)0.0252 (7)−0.0015 (6)0.0029 (6)−0.0038 (6)
C70.0189 (7)0.0161 (7)0.0195 (7)0.0015 (6)−0.0007 (6)0.0008 (5)
C80.0208 (7)0.0138 (6)0.0206 (6)−0.0004 (6)−0.0007 (6)0.0005 (6)
C90.0233 (7)0.0124 (6)0.0196 (6)0.0010 (6)−0.0005 (6)−0.0006 (5)
C100.0199 (7)0.0146 (6)0.0166 (6)0.0018 (5)−0.0014 (5)0.0018 (5)
C110.0217 (7)0.0144 (6)0.0208 (7)−0.0014 (6)−0.0008 (6)−0.0008 (6)
C120.0232 (7)0.0129 (6)0.0210 (7)0.0025 (6)−0.0001 (6)−0.0019 (6)
C130.0197 (7)0.0199 (7)0.0258 (7)−0.0021 (6)0.0009 (6)−0.0009 (6)
C140.0395 (9)0.0207 (7)0.0303 (8)−0.0048 (7)0.0005 (8)0.0047 (7)
C150.0205 (7)0.0154 (6)0.0233 (7)0.0049 (6)0.0012 (6)0.0009 (6)
C160.0247 (7)0.0167 (6)0.0221 (7)0.0042 (6)0.0005 (6)−0.0005 (6)
C170.0208 (7)0.0231 (7)0.0214 (7)−0.0010 (6)0.0037 (6)−0.0002 (6)
C180.0306 (8)0.0232 (7)0.0251 (7)−0.0011 (7)0.0025 (7)−0.0063 (6)
C190.0603 (13)0.0257 (8)0.0333 (9)0.0090 (9)−0.0009 (9)−0.0063 (8)
Geometric parameters (Å, °) top
C1—C61.388 (2)C13—N41.466 (2)
C1—C21.390 (2)C13—C141.527 (2)
C1—N11.4681 (19)C13—H13A0.9700
C2—C31.391 (2)C13—H13B0.9700
C2—H20.9300C14—H14A0.9600
C3—C41.392 (2)C14—H14B0.9600
C3—H30.9300C14—H14C0.9600
C4—C51.402 (2)C15—N41.4618 (18)
C4—N21.4261 (19)C15—C161.520 (2)
C5—C61.387 (2)C15—H15A0.9700
C5—H50.9300C15—H15B0.9700
C6—H60.9300C16—O31.4500 (17)
C7—C121.400 (2)C16—H16A0.9700
C7—N31.4012 (19)C16—H16B0.9700
C7—C81.406 (2)C17—O41.213 (2)
C8—C91.376 (2)C17—O31.3412 (19)
C8—H80.9300C17—C181.482 (2)
C9—C101.424 (2)C18—C191.307 (3)
C9—H90.9300C18—H180.9300
C10—N41.367 (2)C19—H19A0.9300
C10—C111.420 (2)C19—H19B0.9300
C11—C121.381 (2)N1—O11.2271 (18)
C11—H110.9300N1—O21.2323 (18)
C12—H120.9300N2—N31.2712 (18)
C6—C1—C2122.79 (14)N4—C13—H13B108.9
C6—C1—N1118.80 (13)C14—C13—H13B108.9
C2—C1—N1118.39 (13)H13A—C13—H13B107.7
C1—C2—C3118.30 (14)C13—C14—H14A109.5
C1—C2—H2120.8C13—C14—H14B109.5
C3—C2—H2120.8H14A—C14—H14B109.5
C2—C3—C4120.35 (14)C13—C14—H14C109.5
C2—C3—H3119.8H14A—C14—H14C109.5
C4—C3—H3119.8H14B—C14—H14C109.5
C3—C4—C5119.92 (14)N4—C15—C16111.73 (13)
C3—C4—N2116.35 (13)N4—C15—H15A109.3
C5—C4—N2123.73 (14)C16—C15—H15A109.3
C6—C5—C4120.54 (15)N4—C15—H15B109.3
C6—C5—H5119.7C16—C15—H15B109.3
C4—C5—H5119.7H15A—C15—H15B107.9
C5—C6—C1118.09 (14)O3—C16—C15106.25 (12)
C5—C6—H6121.0O3—C16—H16A110.5
C1—C6—H6121.0C15—C16—H16A110.5
C12—C7—N3115.89 (13)O3—C16—H16B110.5
C12—C7—C8118.28 (13)C15—C16—H16B110.5
N3—C7—C8125.81 (14)H16A—C16—H16B108.7
C9—C8—C7120.43 (14)O4—C17—O3123.49 (15)
C9—C8—H8119.8O4—C17—C18122.93 (15)
C7—C8—H8119.8O3—C17—C18113.59 (14)
C8—C9—C10121.81 (13)C19—C18—C17124.60 (16)
C8—C9—H9119.1C19—C18—H18117.7
C10—C9—H9119.1C17—C18—H18117.7
N4—C10—C11121.51 (13)C18—C19—H19A120.0
N4—C10—C9121.39 (13)C18—C19—H19B120.0
C11—C10—C9117.09 (13)H19A—C19—H19B120.0
C12—C11—C10120.23 (14)O1—N1—O2123.50 (13)
C12—C11—H11119.9O1—N1—C1118.44 (13)
C10—C11—H11119.9O2—N1—C1118.05 (13)
C11—C12—C7121.99 (14)N3—N2—C4112.63 (12)
C11—C12—H12119.0N2—N3—C7115.66 (12)
C7—C12—H12119.0C10—N4—C15120.84 (13)
N4—C13—C14113.39 (14)C10—N4—C13121.96 (12)
N4—C13—H13A108.9C15—N4—C13117.20 (13)
C14—C13—H13A108.9C17—O3—C16114.54 (12)
C6—C1—C2—C30.8 (2)O3—C17—C18—C19−11.8 (3)
N1—C1—C2—C3−177.92 (13)C6—C1—N1—O1175.31 (15)
C1—C2—C3—C40.0 (2)C2—C1—N1—O1−6.0 (2)
C2—C3—C4—C5−0.6 (2)C6—C1—N1—O2−4.8 (2)
C2—C3—C4—N2179.52 (14)C2—C1—N1—O2173.98 (15)
C3—C4—C5—C60.6 (2)C3—C4—N2—N3−174.90 (13)
N2—C4—C5—C6−179.55 (15)C5—C4—N2—N35.3 (2)
C4—C5—C6—C10.1 (2)C4—N2—N3—C7179.20 (12)
C2—C1—C6—C5−0.8 (2)C12—C7—N3—N2176.24 (13)
N1—C1—C6—C5177.89 (14)C8—C7—N3—N2−5.4 (2)
C12—C7—C8—C9−2.1 (2)C11—C10—N4—C15−171.70 (14)
N3—C7—C8—C9179.54 (14)C9—C10—N4—C157.2 (2)
C7—C8—C9—C10−0.9 (2)C11—C10—N4—C137.9 (2)
C8—C9—C10—N4−174.91 (14)C9—C10—N4—C13−173.24 (14)
C8—C9—C10—C114.0 (2)C16—C15—N4—C10−90.19 (16)
N4—C10—C11—C12174.82 (13)C16—C15—N4—C1390.21 (17)
C9—C10—C11—C12−4.1 (2)C14—C13—N4—C1078.35 (18)
C10—C11—C12—C71.2 (2)C14—C13—N4—C15−102.06 (16)
N3—C7—C12—C11−179.50 (14)O4—C17—O3—C16−2.6 (2)
C8—C7—C12—C112.0 (2)C18—C17—O3—C16177.69 (13)
N4—C15—C16—O3179.17 (12)C15—C16—O3—C17−164.62 (13)
O4—C17—C18—C19168.5 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15A···O4i0.972.403.189 (2)138
Symmetry codes: (i) x−1/2, −y+1/2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C15—H15A···O4i0.972.403.189 (2)138
Symmetry codes: (i) x−1/2, −y+1/2, −z+1.
Acknowledgements top

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, and Imam Hossein University for financial support.

references
References top

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