4-[(2-Chloro-4-nitro­phen­yl)diazen­yl]-N,N-diethyl­aniline

Gong, L.; Lu, L.

doi:10.1107/S160053681100537X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o662

doi:10.1107/S160053681100537X

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4-[(2-Chloro-4-nitrophenyl)diazenyl]-N,N-diethylaniline

Liangyu Gong ^a and Lihua Lu ^a ^*

^aCollege of Chemical & Pharmaceutical Sciences, Qingdao Agriculture University, Qingdao 266109, People's Republic of China
^*Correspondence e-mail: lhedlut2002@yahoo.com.cn

(Received 4 February 2011; accepted 14 February 2011; online 19 February 2011)

In the title compound, C₁₆H₁₇ClN₄O₂, the aromatic ring is twisted slightly with respect to the plane of the diazene group [N—N—C—C torsion angle = −3.9 (4)°]. The NO₂ group is twisted by 16.2 (4)° relative to the aromatic ring. The two ethyl chains are positioned such that one ethyl chain lies above and the other below the ring.

Related literature

For background to disperse dyes, see: Freeman & Posey (1992 ); Freeman et al. (1997 ). For related structures, see: He et al. (2009 ); Maginn et al. (1993 ).

Experimental

Crystal data

C₁₆H₁₇ClN₄O₂
M_r = 332.79
Monoclinic, C 2/c
a = 25.745 (2) Å
b = 7.5774 (6) Å
c = 18.8628 (15) Å
β = 121.795 (5)°
V = 3127.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 110 K
0.40 × 0.06 × 0.04 mm

Data collection

Bruker–Nonius X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.903, T_max = 0.990
21470 measured reflections
3105 independent reflections
1987 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.132
S = 1.03
3105 reflections
276 parameters
All H-atom parameters refined
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100537X/ng5115sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100537X/ng5115Isup2.hkl

checkCIF report

Comment top

It is important to investigate the structural properties of disperse dyes in solid state because the absorption and dyeing performance such as dye uptake by the fibers are dependent not only on the conformation of the solid dye but also on the interactions between fiber surface and dye in molecular level. Here, we report the crystal structure of 4-(N,N-diethylamino)-2'-chloro-4'-nitroazobenzene.

In the title compound, C₁₆H₁₇ClN₄O₂, the aromatic rings in the azobenzene skeleton is essentially planar with respect to the plane of the azo group, although the N1—N2—C7—C8 torsion angle is -3.9 (4) °. The NO₂ group is twisted relative to the aryl group to which it is bonded by 16.2 (4)° (O1—N3—C4—C3). In the N,N-diethylamino group, two ethyl chains tend to be sepatated as far apart as possible with one ethyl being above the aminobenzene plane and another one below both it.

Related literature top

For background to disperse dyes, see: Freeman & Posey (1992); Freeman et al. (1997). For related structures, see: He et al. (2009); Maginn et al. (1993).

Experimental top

The crystal was obtained by dissolving 0.5 g title compound in 50 ml acetone at room temperature and the resulting solution was covered with Parafilm plastic containing pin holes for slow evaporation of the solvent.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP drawing of 4-(N,N-diethylamino)-2'-chloro-4'-nitroazobenzene showing 50% probability ellipsoids.

4-[(2-Chloro-4-nitrophenyl)diazenyl]-N,N-diethylaniline top

Crystal data top

C₁₆H₁₇ClN₄O₂	F(000) = 1392
M_r = 332.79	D_x = 1.413 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
a = 25.745 (2) Å	Cell parameters from 4405 reflections
b = 7.5774 (6) Å	θ = 2.5–25.5°
c = 18.8628 (15) Å	µ = 0.26 mm⁻¹
β = 121.795 (5)°	T = 110 K
V = 3127.6 (4) Å³	Prism, red
Z = 8	0.40 × 0.06 × 0.04 mm

Data collection top

Bruker–Nonius X8 APEXII diffractometer	3105 independent reflections
Radiation source: fine-focus sealed tube	1987 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
ϕ and ω scans	θ_max = 26.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −31→31
T_min = 0.903, T_max = 0.990	k = −9→8
21470 measured reflections	l = −23→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	All H-atom parameters refined
S = 1.03	w = 1/[σ²(F_o²) + (0.0616P)² + 3.7461P] where P = (F_o² + 2F_c²)/3
3105 reflections	(Δ/σ)_max < 0.001
276 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₆H₁₇ClN₄O₂	V = 3127.6 (4) Å³
M_r = 332.79	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.745 (2) Å	µ = 0.26 mm⁻¹
b = 7.5774 (6) Å	T = 110 K
c = 18.8628 (15) Å	0.40 × 0.06 × 0.04 mm
β = 121.795 (5)°

Data collection top

Bruker–Nonius X8 APEXII diffractometer	3105 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1987 reflections with I > 2σ(I)
T_min = 0.903, T_max = 0.990	R_int = 0.062
21470 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.132	All H-atom parameters refined
S = 1.03	Δρ_max = 0.30 e Å⁻³
3105 reflections	Δρ_min = −0.37 e Å⁻³
276 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.05101 (3)	0.47275 (10)	0.39144 (4)	0.0324 (2)
O1	−0.16973 (10)	0.5393 (3)	0.13154 (12)	0.0404 (5)
O2	−0.23165 (9)	0.4835 (3)	0.17351 (13)	0.0406 (6)
N1	0.01886 (10)	0.2751 (3)	0.49659 (12)	0.0221 (5)
N2	0.00367 (10)	0.1881 (3)	0.54089 (13)	0.0235 (5)
N3	−0.18043 (11)	0.4861 (3)	0.18396 (14)	0.0312 (6)
C1	−0.03294 (12)	0.3220 (3)	0.41830 (15)	0.0230 (6)
C2	−0.02263 (12)	0.4170 (3)	0.36330 (16)	0.0232 (6)
C3	−0.07057 (13)	0.4702 (4)	0.28604 (16)	0.0254 (6)
H3	−0.0649 (13)	0.545 (4)	0.2500 (19)	0.034 (8)*
C4	−0.12889 (12)	0.4255 (3)	0.26414 (15)	0.0258 (6)
C5	−0.14133 (13)	0.3303 (4)	0.31635 (16)	0.0268 (6)
H5	−0.1831 (14)	0.302 (4)	0.3003 (18)	0.034 (8)*
C6	−0.09304 (12)	0.2792 (4)	0.39309 (17)	0.0248 (6)
H6	−0.0984 (13)	0.214 (4)	0.4299 (18)	0.035 (8)*
C7	0.05212 (12)	0.1399 (3)	0.61996 (15)	0.0213 (6)
C8	0.11401 (12)	0.1691 (3)	0.65168 (16)	0.0205 (6)
H8	0.1255 (12)	0.223 (4)	0.6154 (16)	0.029 (7)*
C9	0.15720 (13)	0.1204 (3)	0.73204 (16)	0.0220 (6)
H9	0.1982 (14)	0.138 (4)	0.7512 (17)	0.035 (8)*
C10	0.14028 (11)	0.0425 (3)	0.78528 (15)	0.0204 (6)
C11	0.07782 (12)	0.0103 (4)	0.75163 (16)	0.0236 (6)
H11	0.0638 (12)	−0.040 (3)	0.7845 (17)	0.026 (7)*
C12	0.03514 (13)	0.0575 (4)	0.67093 (17)	0.0241 (6)
H12	−0.0068 (13)	0.034 (3)	0.6497 (17)	0.025 (7)*
N4	0.18316 (9)	−0.0024 (3)	0.86547 (13)	0.0233 (5)
C13	0.24663 (12)	0.0550 (4)	0.90619 (17)	0.0251 (6)
H13A	0.2599 (11)	0.074 (3)	0.9655 (17)	0.019 (7)*
H13B	0.2482 (12)	0.170 (4)	0.8836 (16)	0.023 (7)*
C14	0.28708 (14)	−0.0772 (4)	0.8975 (2)	0.0293 (7)
H14A	0.2819 (14)	−0.196 (5)	0.917 (2)	0.053 (10)*
H14B	0.3270 (15)	−0.039 (4)	0.9279 (18)	0.031 (8)*
H14C	0.2750 (13)	−0.088 (4)	0.8404 (19)	0.030 (8)*
C15	0.16615 (14)	−0.0922 (4)	0.91908 (17)	0.0271 (6)
H15A	0.2026 (13)	−0.159 (4)	0.9614 (18)	0.034 (8)*
H15B	0.1330 (11)	−0.175 (3)	0.8853 (15)	0.015 (6)*
C16	0.14643 (15)	0.0348 (5)	0.96314 (19)	0.0341 (7)
H16A	0.1835 (15)	0.110 (4)	1.005 (2)	0.047 (9)*
H16B	0.1328 (14)	−0.027 (4)	0.994 (2)	0.044 (9)*
H16C	0.1166 (13)	0.112 (4)	0.9259 (18)	0.029 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0281 (4)	0.0469 (4)	0.0259 (4)	0.0027 (3)	0.0167 (3)	0.0077 (3)
O1	0.0482 (14)	0.0484 (13)	0.0190 (11)	0.0144 (10)	0.0140 (10)	0.0060 (9)
O2	0.0262 (12)	0.0426 (13)	0.0366 (12)	0.0003 (9)	0.0053 (10)	0.0060 (10)
N1	0.0257 (12)	0.0269 (12)	0.0140 (11)	0.0030 (9)	0.0106 (10)	0.0017 (9)
N2	0.0266 (13)	0.0275 (13)	0.0165 (11)	0.0023 (9)	0.0113 (10)	−0.0005 (9)
N3	0.0362 (15)	0.0270 (13)	0.0199 (13)	0.0060 (10)	0.0074 (11)	−0.0003 (10)
C1	0.0290 (15)	0.0255 (14)	0.0153 (13)	0.0025 (11)	0.0122 (12)	−0.0029 (11)
C2	0.0236 (14)	0.0273 (15)	0.0194 (14)	0.0027 (11)	0.0117 (12)	−0.0007 (11)
C3	0.0348 (16)	0.0240 (14)	0.0195 (14)	0.0058 (12)	0.0158 (13)	0.0015 (11)
C4	0.0274 (15)	0.0278 (15)	0.0151 (13)	0.0070 (11)	0.0064 (12)	−0.0015 (11)
C5	0.0280 (16)	0.0278 (15)	0.0221 (15)	0.0012 (12)	0.0115 (13)	−0.0028 (12)
C6	0.0297 (16)	0.0265 (15)	0.0206 (14)	0.0008 (12)	0.0147 (13)	−0.0013 (12)
C7	0.0258 (15)	0.0226 (14)	0.0174 (13)	0.0031 (11)	0.0127 (12)	0.0003 (10)
C8	0.0272 (15)	0.0214 (13)	0.0184 (14)	0.0005 (10)	0.0158 (12)	0.0009 (10)
C9	0.0209 (14)	0.0262 (14)	0.0206 (14)	−0.0018 (11)	0.0121 (12)	−0.0015 (11)
C10	0.0249 (14)	0.0221 (13)	0.0168 (13)	0.0042 (11)	0.0127 (11)	0.0004 (10)
C11	0.0262 (15)	0.0323 (15)	0.0191 (14)	0.0010 (11)	0.0165 (12)	0.0020 (11)
C12	0.0225 (15)	0.0307 (15)	0.0233 (15)	−0.0004 (12)	0.0149 (13)	0.0003 (12)
N4	0.0223 (12)	0.0320 (13)	0.0171 (11)	0.0015 (9)	0.0114 (10)	0.0049 (9)
C13	0.0256 (15)	0.0308 (16)	0.0179 (14)	0.0004 (12)	0.0107 (12)	0.0020 (12)
C14	0.0247 (17)	0.0366 (18)	0.0286 (17)	0.0031 (13)	0.0156 (14)	0.0059 (13)
C15	0.0279 (16)	0.0371 (17)	0.0191 (14)	0.0053 (13)	0.0143 (13)	0.0090 (12)
C16	0.0328 (18)	0.0495 (19)	0.0223 (16)	0.0079 (16)	0.0161 (15)	0.0034 (15)

Geometric parameters (Å, º) top

Cl1—C2	1.731 (3)	C9—H9	0.93 (3)
O1—N3	1.226 (3)	C10—N4	1.365 (3)
O2—N3	1.226 (3)	C10—C11	1.405 (4)
N1—N2	1.276 (3)	C11—C12	1.375 (4)
N1—C1	1.418 (3)	C11—H11	0.95 (3)
N2—C7	1.398 (3)	C12—H12	0.95 (3)
N3—C4	1.464 (3)	N4—C13	1.458 (3)
C1—C6	1.397 (4)	N4—C15	1.465 (3)
C1—C2	1.398 (4)	C13—C14	1.514 (4)
C2—C3	1.384 (4)	C13—H13A	0.99 (3)
C3—C4	1.373 (4)	C13—H13B	0.98 (3)
C3—H3	0.95 (3)	C14—H14A	1.01 (3)
C4—C5	1.388 (4)	C14—H14B	0.92 (3)
C5—C6	1.376 (4)	C14—H14C	0.96 (3)
C5—H5	0.98 (3)	C15—C16	1.523 (4)
C6—H6	0.92 (3)	C15—H15A	0.99 (3)
C7—C8	1.393 (4)	C15—H15B	0.98 (3)
C7—C12	1.396 (4)	C16—H16A	1.03 (3)
C8—C9	1.376 (4)	C16—H16B	0.95 (3)
C8—H8	0.97 (3)	C16—H16C	0.93 (3)
C9—C10	1.417 (4)

N2—N1—C1	111.5 (2)	C11—C10—C9	117.3 (2)
N1—N2—C7	115.1 (2)	C12—C11—C10	120.8 (2)
O1—N3—O2	123.7 (2)	C12—C11—H11	118.2 (17)
O1—N3—C4	118.0 (2)	C10—C11—H11	120.9 (17)
O2—N3—C4	118.3 (2)	C11—C12—C7	121.4 (3)
C6—C1—C2	118.4 (2)	C11—C12—H12	119.1 (16)
C6—C1—N1	124.2 (2)	C7—C12—H12	119.5 (16)
C2—C1—N1	117.4 (2)	C10—N4—C13	122.5 (2)
C3—C2—C1	121.3 (3)	C10—N4—C15	121.3 (2)
C3—C2—Cl1	118.5 (2)	C13—N4—C15	115.8 (2)
C1—C2—Cl1	120.2 (2)	N4—C13—C14	112.9 (2)
C4—C3—C2	118.2 (3)	N4—C13—H13A	105.2 (15)
C4—C3—H3	119.1 (18)	C14—C13—H13A	111.6 (14)
C2—C3—H3	122.5 (18)	N4—C13—H13B	109.2 (15)
C3—C4—C5	122.6 (2)	C14—C13—H13B	110.5 (15)
C3—C4—N3	119.0 (2)	H13A—C13—H13B	107 (2)
C5—C4—N3	118.3 (2)	C13—C14—H14A	108.4 (18)
C6—C5—C4	118.3 (3)	C13—C14—H14B	109.2 (18)
C6—C5—H5	120.2 (17)	H14A—C14—H14B	112 (3)
C4—C5—H5	121.5 (17)	C13—C14—H14C	110.1 (17)
C5—C6—C1	121.2 (3)	H14A—C14—H14C	109 (2)
C5—C6—H6	122.2 (18)	H14B—C14—H14C	109 (2)
C1—C6—H6	116.6 (18)	N4—C15—C16	113.0 (3)
C8—C7—C12	118.5 (2)	N4—C15—H15A	107.0 (16)
C8—C7—N2	126.3 (2)	C16—C15—H15A	109.2 (16)
C12—C7—N2	115.1 (2)	N4—C15—H15B	108.9 (14)
C9—C8—C7	120.5 (2)	C16—C15—H15B	109.6 (14)
C9—C8—H8	121.5 (16)	H15A—C15—H15B	109 (2)
C7—C8—H8	118.0 (16)	C15—C16—H16A	108.9 (18)
C8—C9—C10	121.4 (2)	C15—C16—H16B	111.3 (19)
C8—C9—H9	118.9 (18)	H16A—C16—H16B	107 (3)
C10—C9—H9	119.7 (18)	C15—C16—H16C	111.5 (17)
N4—C10—C11	121.5 (2)	H16A—C16—H16C	107 (3)
N4—C10—C9	121.2 (2)	H16B—C16—H16C	110 (3)

C1—N1—N2—C7	−178.7 (2)	N1—N2—C7—C8	−3.9 (4)
N2—N1—C1—C6	0.3 (4)	N1—N2—C7—C12	175.0 (2)
N2—N1—C1—C2	−179.6 (2)	C12—C7—C8—C9	−1.2 (4)
C6—C1—C2—C3	0.9 (4)	N2—C7—C8—C9	177.7 (2)
N1—C1—C2—C3	−179.1 (2)	C7—C8—C9—C10	−1.1 (4)
C6—C1—C2—Cl1	−179.81 (19)	C8—C9—C10—N4	−178.7 (2)
N1—C1—C2—Cl1	0.1 (3)	C8—C9—C10—C11	2.6 (4)
C1—C2—C3—C4	−0.7 (4)	N4—C10—C11—C12	179.5 (2)
Cl1—C2—C3—C4	180.0 (2)	C9—C10—C11—C12	−1.8 (4)
C2—C3—C4—C5	0.2 (4)	C10—C11—C12—C7	−0.5 (4)
C2—C3—C4—N3	177.8 (2)	C8—C7—C12—C11	2.0 (4)
O1—N3—C4—C3	16.2 (4)	N2—C7—C12—C11	−177.0 (2)
O2—N3—C4—C3	−162.6 (2)	C11—C10—N4—C13	−169.7 (2)
O1—N3—C4—C5	−166.1 (2)	C9—C10—N4—C13	11.6 (4)
O2—N3—C4—C5	15.0 (4)	C11—C10—N4—C15	2.3 (4)
C3—C4—C5—C6	0.0 (4)	C9—C10—N4—C15	−176.4 (2)
N3—C4—C5—C6	−177.5 (2)	C10—N4—C13—C14	−92.7 (3)
C4—C5—C6—C1	0.2 (4)	C15—N4—C13—C14	94.9 (3)
C2—C1—C6—C5	−0.7 (4)	C10—N4—C15—C16	−85.4 (3)
N1—C1—C6—C5	179.4 (2)	C13—N4—C15—C16	87.1 (3)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₇ClN₄O₂
M_r	332.79
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	110
a, b, c (Å)	25.745 (2), 7.5774 (6), 18.8628 (15)
β (°)	121.795 (5)
V (Å³)	3127.6 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.40 × 0.06 × 0.04

Data collection
Diffractometer	Bruker–Nonius X8 APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.903, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	21470, 3105, 1987
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.132, 1.03
No. of reflections	3105
No. of parameters	276
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.37

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

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