Dimethyl 4,4′-(diazenedi­yl)dibenzoate at 100 K

Gajda, K.; Zarychta, B.; Domański, A.A.; Ejsmont, K.

doi:10.1107/S1600536813026846

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1607

doi:10.1107/S1600536813026846

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Dimethyl 4,4′-(diazenediyl)dibenzoate at 100 K

Katarzyna Gajda,^a Bartosz Zarychta,^a Andrzej A. Domański ^a and Krzysztof Ejsmont ^a ^*

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: eismont@uni.opole.pl

(Received 20 September 2013; accepted 30 September 2013; online 5 October 2013)

In the asymmetric part of the unit cell of the title compound, C₁₆H₁₄N₂O₄, there are two chemically equivalent but crystallographic independent half molecules. The geometric centre of each complete molecule lies on a crystallographic inversion centre. Both molecules are almost planar [mean deviations of atoms in the two molecules are 0.032 (2) and 0.044 (2) Å] and their geometries are similar. In the crystal, molecules are arranged in columns along the a axis. There are no intermolecular donor–acceptor distances shorter than 3.4 Å.

CCDC reference: 963806

Related literature

For general background to the use of azo compounds as dyes, pigments and advanced materials, see: Allmann (1997 ); Scott et al., (2002 ); Maniam et al. (2008 ); Zeitouny et al., (2009 ). For a related structure, see: Yu & Liu (2009 ); Niu et al. (2011 ). For related literature, see: Onto et al. (1998 ). For the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₁₆H₁₄N₂O₄
M_r = 298.29
Triclinic, $[P \overline 1]$
a = 3.8146 (8) Å
b = 11.2571 (18) Å
c = 16.904 (3) Å
α = 72.456 (16)°
β = 85.030 (18)°
γ = 84.468 (16)°
V = 687.6 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.35 × 0.17 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
4264 measured reflections
2405 independent reflections
1652 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.147
S = 1.05
2405 reflections
213 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 963806

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813026846/fk2074sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813026846/fk2074Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813026846/fk2074Isup3.cml

checkCIF report

Comment top

Azo compounds and its derivatives represent the dominant class of coloured compounds and are used as dyes and pigments (Allmann, 1997). Azobenzenes, due to its efficient and fully reversible photoisomerization and photoinduced anisotropy have widely been investigated as a component in photoresponsive materials (Zeitouny et al., 2009).

There are two chemically equivalent but crystallographic independent molecules in the unit cell (Figure 1), both lie on crystallographic inversion centres. The molecules are almost planar and their geometries are similar; differences do not exceed 0.2 Å for bond lengths, 2° for valence angles and 3° for torsion angles.

All bond distances and angles lie in expected ranges and are in good agreement with the geometry of other para-substituted azobenzene derivatives (Yu & Liu, 2009; Niu et al., 2011 and Allen, 2002).

The crystal packing is shown in Fig. 2. The molecules form columns along the a axis, the distance between stacked molecules is equal to 3.8146 (8) Å. There are no intermolecular C–H···O/N distances shorter than 3.4 Å.

Related literature top

For general background to the use of azo compounds as dyes, pigments and advanced materials, see: Allmann (1997); Scott et al., (2002); Maniam et al. (2008); Zeitouny et al., (2009). For a related structure, see: Yu & Liu (2009); Niu et al. (2011).. For related literature, see: Onto et al. (1998). For Cambridge Structural Database, see: Allen (2002).

Experimental top

The compound was prepared according to literature procedure, (Onto et al., 1998). Crystals of (I) suitable for X-ray crystal structure analysis was grown from benzene–n-heptane mixture (1:1).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Symmetry code: A = -x, -y, -z.
	Fig. 2. The packing diagram viewed along a-axis.

Dimethyl 4,4'-(diazenediyl)dibenzoate top

Crystal data top

C₁₆H₁₄N₂O₄	Z = 2
M_r = 298.29	F(000) = 312
Triclinic, P1	D_x = 1.441 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8146 (8) Å	Cell parameters from 4264 reflections
b = 11.2571 (18) Å	θ = 3.6–25.0°
c = 16.904 (3) Å	µ = 0.11 mm⁻¹
α = 72.456 (16)°	T = 100 K
β = 85.030 (18)°	Prism, red
γ = 84.468 (16)°	0.35 × 0.17 × 0.15 mm
V = 687.6 (2) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer	1652 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 25.0°, θ_min = 3.6°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −4→2
ω–scan	k = −13→13
4264 measured reflections	l = −20→20
2405 independent reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0791P)² + 0.205P] where P = (F_o² + 2F_c²)/3
2405 reflections	(Δ/σ)_max < 0.001
213 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₁₄N₂O₄	γ = 84.468 (16)°
M_r = 298.29	V = 687.6 (2) Å³
Triclinic, P1	Z = 2
a = 3.8146 (8) Å	Mo Kα radiation
b = 11.2571 (18) Å	µ = 0.11 mm⁻¹
c = 16.904 (3) Å	T = 100 K
α = 72.456 (16)°	0.35 × 0.17 × 0.15 mm
β = 85.030 (18)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	1652 reflections with I > 2σ(I)
4264 measured reflections	R_int = 0.025
2405 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.147	H-atom parameters constrained
S = 1.05	Δρ_max = 0.32 e Å⁻³
2405 reflections	Δρ_min = −0.25 e Å⁻³
213 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
O11	0.3301 (4)	0.15744 (14)	0.33935 (9)	0.0251 (4)
O12	0.1772 (4)	−0.04021 (15)	0.39802 (10)	0.0296 (4)
N11	0.0393 (5)	0.05005 (17)	0.00495 (12)	0.0216 (5)
C11	0.0777 (6)	0.0436 (2)	0.08962 (14)	0.0191 (5)
C12	0.2050 (6)	0.1480 (2)	0.10194 (14)	0.0196 (5)
H12	0.2585	0.2160	0.0565	0.020 (6)*
C13	0.2522 (5)	0.1511 (2)	0.18173 (14)	0.0191 (5)
H13	0.3387	0.2208	0.1898	0.025 (6)*
C14	0.1695 (5)	0.0493 (2)	0.25002 (14)	0.0194 (5)
C15	0.0372 (6)	−0.0548 (2)	0.23750 (14)	0.0204 (5)
H15	−0.0194	−0.1222	0.2830	0.020 (6)*
C16	−0.0101 (6)	−0.0585 (2)	0.15834 (14)	0.0200 (5)
H16	−0.0992	−0.1278	0.1504	0.028 (7)*
C17	0.2225 (6)	0.0484 (2)	0.33681 (14)	0.0209 (5)
C18	0.3974 (7)	0.1652 (2)	0.42107 (14)	0.0272 (6)
H18A	0.4725	0.2464	0.4158	0.037 (7)*
H18B	0.5788	0.1025	0.4448	0.031 (7)*
H18C	0.1852	0.1519	0.4565	0.038 (8)*
O21	0.6465 (4)	0.65469 (14)	0.35059 (10)	0.0248 (4)
O22	0.8894 (4)	0.45639 (15)	0.38736 (10)	0.0308 (5)
N21	0.4726 (5)	0.55083 (17)	0.00854 (12)	0.0206 (4)
C21	0.5457 (6)	0.5432 (2)	0.09183 (14)	0.0184 (5)
C22	0.4325 (6)	0.6478 (2)	0.11755 (14)	0.0193 (5)
H22	0.3167	0.7168	0.0815	0.034 (7)*
C23	0.4932 (5)	0.6485 (2)	0.19724 (13)	0.0188 (5)
H23	0.4175	0.7183	0.2145	0.027 (7)*
C24	0.6678 (6)	0.5450 (2)	0.25183 (14)	0.0194 (5)
C25	0.7813 (5)	0.4400 (2)	0.22548 (14)	0.0196 (5)
H25	0.8971	0.3710	0.2616	0.023 (6)*
C26	0.7222 (6)	0.4383 (2)	0.14616 (14)	0.0193 (5)
H26	0.7983	0.3686	0.1288	0.027 (7)*
C27	0.7478 (6)	0.5448 (2)	0.33667 (14)	0.0212 (5)
C28	0.7220 (7)	0.6663 (2)	0.43076 (14)	0.0279 (6)
H28A	0.6386	0.7481	0.4340	0.046 (8)*
H28B	0.9720	0.6542	0.4368	0.031 (7)*
H28C	0.6053	0.6044	0.4744	0.039 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0366 (10)	0.0189 (9)	0.0242 (9)	−0.0057 (7)	−0.0049 (7)	−0.0110 (7)
O12	0.0411 (11)	0.0227 (10)	0.0250 (9)	−0.0081 (8)	−0.0030 (8)	−0.0052 (7)
N11	0.0227 (10)	0.0171 (10)	0.0270 (11)	−0.0007 (8)	−0.0018 (8)	−0.0096 (8)
C11	0.0183 (11)	0.0165 (12)	0.0233 (12)	0.0047 (9)	−0.0021 (9)	−0.0089 (9)
C12	0.0205 (11)	0.0136 (12)	0.0239 (13)	−0.0017 (9)	−0.0001 (9)	−0.0047 (9)
C13	0.0184 (11)	0.0133 (11)	0.0289 (13)	−0.0003 (9)	−0.0020 (9)	−0.0114 (10)
C14	0.0163 (11)	0.0185 (12)	0.0253 (13)	0.0014 (9)	−0.0019 (9)	−0.0100 (10)
C15	0.0232 (12)	0.0140 (11)	0.0228 (12)	−0.0005 (9)	−0.0017 (10)	−0.0039 (9)
C16	0.0198 (11)	0.0150 (12)	0.0274 (13)	−0.0027 (9)	−0.0005 (10)	−0.0094 (10)
C17	0.0203 (12)	0.0174 (12)	0.0272 (13)	−0.0014 (9)	−0.0013 (9)	−0.0101 (10)
C18	0.0355 (14)	0.0250 (14)	0.0268 (14)	−0.0061 (11)	−0.0062 (11)	−0.0141 (11)
O21	0.0352 (10)	0.0200 (9)	0.0231 (9)	−0.0018 (7)	−0.0041 (7)	−0.0115 (7)
O22	0.0428 (11)	0.0240 (10)	0.0263 (10)	0.0044 (8)	−0.0080 (8)	−0.0092 (8)
N21	0.0230 (10)	0.0177 (10)	0.0229 (10)	−0.0029 (8)	−0.0008 (8)	−0.0085 (8)
C21	0.0180 (11)	0.0156 (12)	0.0226 (12)	−0.0046 (9)	0.0015 (9)	−0.0069 (9)
C22	0.0188 (11)	0.0143 (11)	0.0245 (13)	−0.0006 (9)	−0.0020 (9)	−0.0055 (9)
C23	0.0189 (11)	0.0141 (11)	0.0255 (13)	−0.0034 (9)	0.0011 (9)	−0.0091 (9)
C24	0.0189 (11)	0.0177 (12)	0.0232 (12)	−0.0057 (9)	0.0017 (9)	−0.0079 (9)
C25	0.0182 (11)	0.0145 (12)	0.0258 (13)	−0.0012 (9)	−0.0017 (9)	−0.0055 (9)
C26	0.0201 (11)	0.0132 (11)	0.0270 (13)	−0.0021 (9)	−0.0003 (9)	−0.0093 (9)
C27	0.0217 (12)	0.0173 (12)	0.0263 (13)	−0.0045 (9)	0.0017 (10)	−0.0088 (10)
C28	0.0368 (14)	0.0263 (14)	0.0264 (14)	−0.0043 (11)	−0.0040 (11)	−0.0153 (11)

Geometric parameters (Å, º) top

O11—C17	1.345 (3)	O21—C27	1.342 (3)
O11—C18	1.456 (3)	O21—C28	1.456 (3)
O12—C17	1.215 (3)	O22—C27	1.216 (3)
N11—N11ⁱ	1.255 (3)	N21—N21ⁱⁱ	1.257 (4)
N11—C11	1.431 (3)	N21—C21	1.434 (3)
C11—C12	1.391 (3)	C21—C22	1.393 (3)
C11—C16	1.409 (3)	C21—C26	1.411 (3)
C12—C13	1.387 (3)	C22—C23	1.389 (3)
C12—H12	0.9300	C22—H22	0.9300
C13—C14	1.398 (3)	C23—C24	1.401 (3)
C13—H13	0.9300	C23—H23	0.9300
C14—C15	1.398 (3)	C24—C25	1.403 (3)
C14—C17	1.495 (3)	C24—C27	1.491 (3)
C15—C16	1.379 (3)	C25—C26	1.385 (3)
C15—H15	0.9300	C25—H25	0.9300
C16—H16	0.9300	C26—H26	0.9300
C18—H18A	0.9600	C28—H28A	0.9600
C18—H18B	0.9600	C28—H28B	0.9600
C18—H18C	0.9600	C28—H28C	0.9600

C17—O11—C18	116.32 (17)	C27—O21—C28	116.58 (18)
N11ⁱ—N11—C11	114.3 (2)	N21ⁱⁱ—N21—C21	114.3 (2)
C12—C11—C16	120.0 (2)	C22—C21—C26	120.4 (2)
C12—C11—N11	115.69 (19)	C22—C21—N21	115.86 (19)
C16—C11—N11	124.25 (19)	C26—C21—N21	123.76 (19)
C13—C12—C11	120.2 (2)	C23—C22—C21	119.7 (2)
C13—C12—H12	119.9	C23—C22—H22	120.2
C11—C12—H12	119.9	C21—C22—H22	120.2
C12—C13—C14	119.88 (19)	C22—C23—C24	120.5 (2)
C12—C13—H13	120.1	C22—C23—H23	119.8
C14—C13—H13	120.1	C24—C23—H23	119.8
C15—C14—C13	119.8 (2)	C23—C24—C25	119.5 (2)
C15—C14—C17	118.83 (19)	C23—C24—C27	121.7 (2)
C13—C14—C17	121.41 (19)	C25—C24—C27	118.8 (2)
C16—C15—C14	120.7 (2)	C26—C25—C24	120.5 (2)
C16—C15—H15	119.7	C26—C25—H25	119.8
C14—C15—H15	119.7	C24—C25—H25	119.8
C15—C16—C11	119.42 (19)	C25—C26—C21	119.4 (2)
C15—C16—H16	120.3	C25—C26—H26	120.3
C11—C16—H16	120.3	C21—C26—H26	120.3
O12—C17—O11	123.6 (2)	O22—C27—O21	123.7 (2)
O12—C17—C14	124.4 (2)	O22—C27—C24	124.4 (2)
O11—C17—C14	111.96 (18)	O21—C27—C24	111.90 (19)
O11—C18—H18A	109.5	O21—C28—H28A	109.5
O11—C18—H18B	109.5	O21—C28—H28B	109.5
H18A—C18—H18B	109.5	H28A—C28—H28B	109.5
O11—C18—H18C	109.5	O21—C28—H28C	109.5
H18A—C18—H18C	109.5	H28A—C28—H28C	109.5
H18B—C18—H18C	109.5	H28B—C28—H28C	109.5

N11ⁱ—N11—C11—C12	172.7 (2)	N21ⁱⁱ—N21—C21—C22	−169.5 (2)
N11ⁱ—N11—C11—C16	−8.4 (3)	N21ⁱⁱ—N21—C21—C26	10.9 (3)
C16—C11—C12—C13	1.2 (3)	C26—C21—C22—C23	−0.2 (3)
N11—C11—C12—C13	−179.92 (18)	N21—C21—C22—C23	−179.82 (18)
C11—C12—C13—C14	−0.4 (3)	C21—C22—C23—C24	0.1 (3)
C12—C13—C14—C15	−0.4 (3)	C22—C23—C24—C25	0.0 (3)
C12—C13—C14—C17	178.97 (19)	C22—C23—C24—C27	177.82 (19)
C13—C14—C15—C16	0.5 (3)	C23—C24—C25—C26	0.1 (3)
C17—C14—C15—C16	−178.93 (19)	C27—C24—C25—C26	−177.85 (19)
C14—C15—C16—C11	0.3 (3)	C24—C25—C26—C21	−0.1 (3)
C12—C11—C16—C15	−1.1 (3)	C22—C21—C26—C25	0.2 (3)
N11—C11—C16—C15	−179.91 (19)	N21—C21—C26—C25	179.82 (19)
C18—O11—C17—O12	0.8 (3)	C28—O21—C27—O22	1.5 (3)
C18—O11—C17—C14	−178.63 (18)	C28—O21—C27—C24	−178.16 (17)
C15—C14—C17—O12	4.4 (3)	C23—C24—C27—O22	177.8 (2)
C13—C14—C17—O12	−175.0 (2)	C25—C24—C27—O22	−4.3 (3)
C15—C14—C17—O11	−176.20 (18)	C23—C24—C27—O21	−2.5 (3)
C13—C14—C17—O11	4.4 (3)	C25—C24—C27—O21	175.33 (19)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₂O₄
M_r	298.29
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	3.8146 (8), 11.2571 (18), 16.904 (3)
α, β, γ (°)	72.456 (16), 85.030 (18), 84.468 (16)
V (Å³)	687.6 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.35 × 0.17 × 0.15

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4264, 2405, 1652
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.147, 1.05
No. of reflections	2405
No. of parameters	213
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

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