Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614009942/sk3541sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009942/sk3541Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614009942/sk3541IIsup3.hkl |
CCDC references: 1000644; 1000645
Azobenzenes and related hydrazo and azoxy compounds have attracted significant attention owing to their electronic structure. Interest in the development of azobenzenes is connected with their potential applications in photoresponsive materials, as well as in linear and nonlinear optics or optical data-storage devices (Zeitouny et al., 2009). The interesting structural properties of the compounds are connected with their molecular dynamics (cis–trans isomerization) and their ability to transform reversibly from the thermodynamically stable trans form to the cis form by irradiation with UV or visible light (Takamiya et al., 1986; Tsuchiya, 1999; Harada & Ogawa, 2004; Zeitouny et al., 2009). The need to understand the stability of the different isomers in particular motivates analysis of azobenzene-type compounds (Allmann, 1997). From the point of view of structural chemistry, the symmetrically para-substituted azobenzenes are especially important. Different π-electron-withdrawing and/or π-electron-donating groups may change the aromaticity of the benzene rings and strongly influence the geometry and electronic structure of the system. The aim of this work is to analyse how the substituent effects of amino (diethylene), carboxylic acid and ester groups, located in para positions to the azo bridge, work in azobenzenes. The crystal and molecular structures of 4,4'-azinodibenzoic acid (Yu & Liu, 2009) and its ethyl ester (Niu et al., 2011) have been determined previously at room temperature.
We present herein the crystal and molecular structures at 100 K of two para-substituted azobenzenes, namely N,N,N',N'-tetraethyl-4,4'-(diazenediyl)dianiline, (I), and diethyl 4,4'-(diazenediyl)dibenzoate, (II) (Fig. 1), with a π-electron-withdrawing group [–NEt2] in (I) and a π-electron-donating group (–COOEt) in (II), along with a description of the effects of the substituents on the aromaticity of the benzene ring and the geometry of the azo bridge. To extend the structural studies, the molecular geometries of the studied compounds were optimized using quantum-mechanical density functional theory (DFT) calculations.
Compounds (I) and (I) were prepared according to literature procedures, viz. Kalyanaraman & George (1973) for (I) and Onto et al. (1998) for (II). Crystals of (I) and (II) suitable for X-ray crystal structure analysis were grown from solutions in a benzene–n-heptane mixture (1:1 v/v).
Based on the solid-state geometry, the molecular structures of (I) and (II) were optimized using the B3LYP hybrid functional (Becke, 1988, 1993; Lee et al., 1988) with the 6-311++G(d,p) level of theory. All species correspond to the minima at the B3LYP/6-311++G(d,p) level with no imaginary frequencies. All calculations were performed using the GAUSSIAN09 program package (Frisch et al., 2010).
Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were generated in idealized positions, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. Their parameters were not refined.
The experimental and calculated geometric parameters of the azo bridge of (I) and (II) reported in Table 2 are supplemented with those for two additional azobenzene structures, viz. dimethyl 4,4'-(diazenediyl)dibenzoate (Harada & Ogawa, 2004; Harada et al., 1997; Gajda et al., 2013) and 4,4'-azinodibenzoic acid (Yu & Liu, 2009). The geometry-based index of aromaticity, the harmonic oscillator model of aromaticity (HOMA), may serve as a convenient, reliable and easily accessible quantitative measure of π-electron delocalization (aromaticity) in chemical compounds. The HOMA index stipulates that bond lengths in aromatic systems lie between values typical for single and double bonds (Kruszewski & Krygowski, 1973; Krygowski, 1993; Krygowski & Cyrański, 1996).
The molecular structures of (I) and (II) and the atom-numbering schemes are presented in Fig. 1. The molecules of (I) and (II) are composed of two para-substituted aromatic rings and an –N═N– bridge. In the asymmetric part of the unit cell of (I), there is one crystallographically independent molecule, while in (II) the asymmetric unit contains only half a molecule with the inversion centre at the azo bridge. The aromatic rings in (II) are coplanar as the aromatic ring and ester group are coplanar, whereas in (I) they are slighty twisted. The angle between the planes calculated from the mid-positions of all six C atoms (C1–C6 and C1'–C6') is 15.27 (6)°. Taking into account the torsion angles surrounding the azo group, the C1–C6 aromatic ring is twisted by 8.59 (15)° and the C1'–C6' ring by 5.52 (16)°. This suggests a notable deformation of the benzene rings. The largest deviation from the mean plane of the aromatic rings is 0.0142 (8) Å. The deformation is also revealed in the bond lengths and angles. The bond lengths which deviate most from the average Car—Car value are those connected with the –NEt2 group [Δmax = 0.021 (1) and 0.024 (1) Å, respectively, for the C and C' rings]. The valence angles which deviate most from the ideal value of 120° are also associated with the –NEt2 group, with values of 117.11 (10) and 116.92 (10)°. Also, the C2—C1—C6 and C2'—C1'—C6' angles at the –N═N– bridge are reduced [From what value?] by 1.59 (10) and 1.96 (10)°, respectively.
The deformation around the –NEt2 group of (I) may be caused by steric hindrance of the group. Such effects are not observed for (II). This may also suggest that the π-electron-withdrawing effects of amine have a stronger influence on aromatic ring deformation than the ethyl ester group of (II). The geometry of the –N═N– bridge in both structures is almost the same. The length of the N═N bond in (I) [1.2655 (13) Å] corresponds well with the value in (II) [1.258 (2) Å]. They are slightly longer than the corresponding distances found for 4,4'-(COOH)2. In (I), the length of the one of the NN—Ph bonds is slightly longer than other [N1—C1 = 1.4230 (14) Å and N1'—C1' = 1.4196 (13) Å] and these are shorter than the corresponding bonds in the remaining structures (Table 2). The average value of the C—N—N angle is 114.17 (10)°, close to the corresponding valence angle in (II) [113.89 (15)°]. These values are in good agreement with 4,4'-(COOH)2, 4,4'-(COOMe)2 and azobenzene.
Amine atom N3 of (I) lies -0.0970 (12) Å out of the plane defined by the three neighbouring C atoms (C4, C7 and C9). On the other hand, atom N4 is exactly in the plane defined by atoms C4', C11 and C13. The sum of the valence angles around the N atom of 359.99 (9)° demonstrates clear sp2 hybridization. The geometry of the ester group of (II) is typical and corresponds well with the geometry of 4,4'-(COOMe)2 (differences in bond lengths, and in valence and dihedral angles, do not exceed 3σ). There are no significant differences between the values of the bond lengths and angles of (I) and (II) in the solid state and those found for the calculated structures. Nevertheless, some deviations are observed for the torsion angles. The main discrepancy involves the –N═N– bridge. In the calculated structures of azobenzene derivatives, the N—N—C—C torsion angle is close to 0.00°.
The substituents of azobenzene presented here differ in their electron-withdrawing properties: for the phenylazo group σp = 0.39; for N(Et)2 σp = -0.72; for COOEt, COOMe and COOH σp = 0.45; and for H σp = 0.00 (Hansch et al., 1991). Accordingly, the influence of the above-mentioned groups on the π-electron delocalization of aromatic rings has been investigated by means of HOMA. The values of HOMA are presented in Table 2. The data suggest that the –NEt2 group has the greatest influence on aromaticity. The values of the HOMA index in (I) are 0.924 and 0.908 for aromatic rings connected to atoms N3 and N4, respectively. The above-mentioned differences in the geometry of the amino groups may influence this effect.
In (I), the HOMA values are slightly different for the rings. The value for the ring connected to atom N4 (sp2-hydridized) corresponds well with the optimized structure, where both amine N atoms are strictly planar. Simultaneously, the HOMA value for the aromatic ring connected to atom N3 (partial sp3-hybridization) is decreased, indicating greater aromaticity. The lone pairs of the planar N atoms, which are shifted partially onto the N—Car bond may influence formation of a quinoid-like structure (Fig. 2) which contribute to the resonance hybrid of the molecule.
The HOMA index for (II) is 0.990, comparable with values found for 4,4'-(COOH)2 (Δ = 0.001) and azobenzene (0.985). This may suggest that these substituents do not influence the π-electron delocalization of the aromatic ring. In the case of 4,4'-(COOMe)2, the HOMA index is clearly reduced (0.960) and is close to the value obtained for calculated structures of isolated molecules [0.966 for 4,4'-(COOH)2, and 0.967 for 4,4'-(COOMe)2 and (II)]. That effect may be caused by hydrogen bonding to surrounding molecules of (II) or 4,4'-(COOH)2. Lone-electron pairs of O atoms do not take part in the electron-transmission effects as they are involved in hydrogen bonds [C5—H5···O1i for (II) (Table 4) and O1—H1A···O2ii for 4,4'-azinodibenzoic acid (Yu & Liu, 2009); symmetry codes: (i) x, -y + 7/2, z - 1/2; (ii) -x + 1, -y + 1, -z + 1], contrary to the situation in 4,4'-(COOMe)2 where no hydrogen bonding is observed (Gajda et al., 2013).
The molecular arrangement of (I) in the crystalline state is presented in Fig. 3(a). The molecules form columns with a perpendicular arrangement. Molecules belonging to neighbouring columns form a dihedral angle of 69.2 (3)°. No classical hydrogen bonds are found for (I), but there are at least three C—H···π contacts (Table 3) between columns of molecules, which stabilize the crystal structure. These contacts are formed between ethyl groups and the aromatic rings of the perpendicular molecules. The molecular arrangement of (II) in the crystalline state is presented in Fig. 3(b). The structure of (II) is stabilized by one C—H···O hydrogen bond between the ester group and the aromatic ring of a neighbouring molecule (Table 4). The dihedral angle between connected molecules [not clear] is 86.1 (3)°, and as a result molecules form chains in the [001] direction. Perpendicular molecules are arranged in stacks forming two columns. This is achieved by π–π interactions between the –N═N– bridge and the aromatic ring of a parallel molecule, resulting in a staircase-like formation. The perpendicular separation of the mean planes through the rings of adjacent molecules is 3.288 (1) Å.
For both compounds, 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).
Fig. 1. The molecular structures in the solid state of (a) (I) and
(b) (II), showing the atom-numbering schemes. Displacement ellipsoids
are drawn at the 50% probability level. The molecule of (II) is located on an
inversion centre. Fig. 2. Canonical forms of (I), with charge separation showing the resonance effect of the π-donating amino group and azobenzene. Fig. 3. Packing diagrams for (a) (I) and (b) (II), showing the C5—H5···O2i hydrogen bonds as dashed lines. [Symmetry code: (i) x, -y + 7/2, z - 1/2]. |
C20H28N4 | F(000) = 704 |
Mr = 324.46 | Dx = 1.166 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3245 reflections |
a = 14.0805 (3) Å | θ = 2.9–25.0° |
b = 7.9682 (2) Å | µ = 0.07 mm−1 |
c = 21.1890 (5) Å | T = 100 K |
β = 128.989 (2)° | Plate, red |
V = 1847.82 (9) Å3 | 0.30 × 0.20 × 0.05 mm |
Z = 4 |
Oxford Xcalibur diffractometer | 3433 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 29.0°, θmin = 2.9° |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | h = −17→19 |
ω scans | k = −10→10 |
14494 measured reflections | l = −28→21 |
4685 independent reflections |
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) = 0.126 | H-atom parameters not refined |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0734P)2 + 0.0149P] where P = (Fo2 + 2Fc2)/3 |
4685 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C20H28N4 | V = 1847.82 (9) Å3 |
Mr = 324.46 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.0805 (3) Å | µ = 0.07 mm−1 |
b = 7.9682 (2) Å | T = 100 K |
c = 21.1890 (5) Å | 0.30 × 0.20 × 0.05 mm |
β = 128.989 (2)° |
Oxford Xcalibur diffractometer | 3433 reflections with I > 2σ(I) |
14494 measured reflections | Rint = 0.019 |
4685 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.126 | H-atom parameters not refined |
S = 1.08 | Δρmax = 0.39 e Å−3 |
4685 reflections | Δρmin = −0.28 e Å−3 |
217 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.17967 (9) | 0.50576 (12) | 0.00057 (6) | 0.0237 (2) | |
N1' | 0.23450 (9) | 0.42196 (12) | −0.01860 (6) | 0.0230 (2) | |
C1 | 0.23961 (11) | 0.50331 (14) | 0.08522 (7) | 0.0218 (2) | |
C2 | 0.17922 (11) | 0.57673 (14) | 0.11037 (7) | 0.0240 (3) | |
H2 | 0.1020 | 0.6224 | 0.0718 | 0.029* | |
C3 | 0.23111 (11) | 0.58374 (15) | 0.19146 (7) | 0.0235 (3) | |
H3 | 0.1887 | 0.6348 | 0.2066 | 0.028* | |
C4 | 0.34813 (10) | 0.51408 (14) | 0.25185 (6) | 0.0197 (2) | |
C5 | 0.40912 (11) | 0.44079 (15) | 0.22546 (7) | 0.0235 (3) | |
H5 | 0.4864 | 0.3949 | 0.2636 | 0.028* | |
C6 | 0.35628 (11) | 0.43603 (15) | 0.14432 (7) | 0.0240 (3) | |
H6 | 0.3986 | 0.3876 | 0.1286 | 0.029* | |
C1' | 0.18136 (10) | 0.43145 (14) | −0.10183 (6) | 0.0205 (2) | |
C2' | 0.23709 (10) | 0.33452 (14) | −0.12477 (6) | 0.0207 (2) | |
H2' | 0.3014 | 0.2645 | −0.0865 | 0.025* | |
C3' | 0.20008 (10) | 0.33874 (14) | −0.20250 (6) | 0.0197 (2) | |
H3' | 0.2392 | 0.2714 | −0.2158 | 0.024* | |
C4' | 0.10336 (10) | 0.44435 (14) | −0.26205 (6) | 0.0181 (2) | |
C5' | 0.04457 (10) | 0.53957 (15) | −0.23872 (7) | 0.0221 (2) | |
H5' | −0.0213 | 0.6076 | −0.2770 | 0.027* | |
C6' | 0.08265 (10) | 0.53358 (15) | −0.16096 (7) | 0.0226 (2) | |
H6' | 0.0426 | 0.5978 | −0.1474 | 0.027* | |
N3 | 0.40020 (9) | 0.51423 (12) | 0.33281 (5) | 0.0222 (2) | |
N4 | 0.06828 (8) | 0.45639 (12) | −0.33873 (5) | 0.0213 (2) | |
C7 | 0.34264 (11) | 0.59969 (16) | 0.36161 (7) | 0.0253 (3) | |
H7A | 0.3702 | 0.5486 | 0.4122 | 0.030* | |
H7B | 0.2548 | 0.5846 | 0.3222 | 0.030* | |
C8 | 0.37085 (13) | 0.78535 (17) | 0.37524 (8) | 0.0368 (3) | |
H8A | 0.3305 | 0.8355 | 0.3939 | 0.055* | |
H8B | 0.3425 | 0.8372 | 0.3252 | 0.055* | |
H8C | 0.4575 | 0.8013 | 0.4153 | 0.055* | |
C9 | 0.52685 (10) | 0.46242 (15) | 0.39539 (7) | 0.0234 (3) | |
H9A | 0.5607 | 0.5252 | 0.4447 | 0.028* | |
H9B | 0.5738 | 0.4904 | 0.3777 | 0.028* | |
C10 | 0.54047 (12) | 0.27654 (17) | 0.41435 (8) | 0.0322 (3) | |
H10A | 0.6253 | 0.2502 | 0.4557 | 0.048* | |
H10B | 0.5089 | 0.2135 | 0.3662 | 0.048* | |
H10C | 0.4958 | 0.2482 | 0.4332 | 0.048* | |
C11 | 0.12613 (11) | 0.35856 (15) | −0.36443 (7) | 0.0246 (3) | |
H11A | 0.0669 | 0.3378 | −0.4223 | 0.029* | |
H11B | 0.1511 | 0.2509 | −0.3370 | 0.029* | |
C12 | 0.23654 (13) | 0.44583 (17) | −0.34632 (9) | 0.0363 (3) | |
H12A | 0.2713 | 0.3766 | −0.3642 | 0.054* | |
H12B | 0.2962 | 0.4647 | −0.2889 | 0.054* | |
H12C | 0.2120 | 0.5514 | −0.3743 | 0.054* | |
C13 | −0.02870 (10) | 0.56978 (15) | −0.39938 (7) | 0.0225 (2) | |
H13A | −0.0143 | 0.6028 | −0.4368 | 0.027* | |
H13B | −0.0262 | 0.6703 | −0.3725 | 0.027* | |
C14 | −0.15447 (11) | 0.49120 (17) | −0.44692 (7) | 0.0305 (3) | |
H14A | −0.2150 | 0.5707 | −0.4857 | 0.046* | |
H14B | −0.1698 | 0.4597 | −0.4103 | 0.046* | |
H14C | −0.1582 | 0.3934 | −0.4749 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0261 (5) | 0.0232 (5) | 0.0224 (5) | −0.0024 (4) | 0.0155 (5) | 0.0001 (4) |
N1' | 0.0270 (5) | 0.0216 (5) | 0.0233 (5) | −0.0055 (4) | 0.0172 (4) | −0.0033 (4) |
C1 | 0.0239 (6) | 0.0190 (6) | 0.0196 (6) | −0.0037 (4) | 0.0123 (5) | 0.0008 (4) |
C2 | 0.0248 (6) | 0.0216 (6) | 0.0213 (6) | 0.0016 (4) | 0.0125 (5) | 0.0033 (4) |
C3 | 0.0262 (6) | 0.0219 (6) | 0.0226 (6) | 0.0017 (4) | 0.0154 (5) | 0.0012 (4) |
C4 | 0.0228 (6) | 0.0193 (6) | 0.0171 (5) | −0.0029 (4) | 0.0126 (5) | −0.0004 (4) |
C5 | 0.0213 (6) | 0.0274 (6) | 0.0211 (6) | −0.0019 (5) | 0.0130 (5) | −0.0006 (5) |
C6 | 0.0255 (6) | 0.0262 (6) | 0.0265 (6) | −0.0032 (5) | 0.0194 (5) | −0.0025 (5) |
C1' | 0.0215 (5) | 0.0216 (6) | 0.0179 (5) | −0.0042 (4) | 0.0121 (5) | −0.0012 (4) |
C2' | 0.0188 (5) | 0.0202 (6) | 0.0193 (5) | −0.0009 (4) | 0.0101 (5) | 0.0021 (4) |
C3' | 0.0197 (5) | 0.0191 (6) | 0.0224 (6) | 0.0007 (4) | 0.0142 (5) | −0.0003 (4) |
C4' | 0.0168 (5) | 0.0195 (5) | 0.0167 (5) | −0.0020 (4) | 0.0100 (4) | −0.0019 (4) |
C5' | 0.0189 (5) | 0.0253 (6) | 0.0195 (6) | 0.0036 (4) | 0.0109 (5) | 0.0004 (4) |
C6' | 0.0231 (6) | 0.0246 (6) | 0.0226 (6) | −0.0002 (4) | 0.0156 (5) | −0.0041 (4) |
N3 | 0.0224 (5) | 0.0269 (5) | 0.0168 (5) | 0.0041 (4) | 0.0120 (4) | 0.0008 (4) |
N4 | 0.0216 (5) | 0.0255 (5) | 0.0179 (5) | 0.0058 (4) | 0.0129 (4) | 0.0018 (4) |
C7 | 0.0246 (6) | 0.0344 (7) | 0.0198 (6) | 0.0066 (5) | 0.0154 (5) | 0.0051 (5) |
C8 | 0.0501 (9) | 0.0312 (7) | 0.0325 (7) | 0.0130 (6) | 0.0276 (7) | 0.0039 (6) |
C9 | 0.0194 (6) | 0.0317 (7) | 0.0171 (5) | 0.0016 (5) | 0.0106 (5) | −0.0014 (5) |
C10 | 0.0256 (6) | 0.0345 (7) | 0.0336 (7) | 0.0091 (5) | 0.0173 (6) | 0.0065 (5) |
C11 | 0.0334 (6) | 0.0230 (6) | 0.0218 (6) | 0.0048 (5) | 0.0195 (5) | −0.0004 (5) |
C12 | 0.0469 (8) | 0.0279 (7) | 0.0570 (9) | 0.0080 (6) | 0.0437 (8) | 0.0060 (6) |
C13 | 0.0232 (6) | 0.0246 (6) | 0.0184 (5) | 0.0033 (4) | 0.0125 (5) | 0.0023 (4) |
C14 | 0.0239 (6) | 0.0362 (7) | 0.0236 (6) | 0.0003 (5) | 0.0112 (6) | −0.0042 (5) |
N1—N1' | 1.2655 (13) | N4—C13 | 1.4575 (14) |
N1—C1 | 1.4230 (14) | N4—C11 | 1.4580 (13) |
N1'—C1' | 1.4196 (13) | C7—C8 | 1.5117 (18) |
C1—C2 | 1.3855 (16) | C7—H7A | 0.9700 |
C1—C6 | 1.4020 (16) | C7—H7B | 0.9700 |
C2—C3 | 1.3818 (15) | C8—H8A | 0.9600 |
C2—H2 | 0.9300 | C8—H8B | 0.9600 |
C3—C4 | 1.4168 (16) | C8—H8C | 0.9600 |
C3—H3 | 0.9300 | C9—C10 | 1.5149 (18) |
C4—N3 | 1.3776 (13) | C9—H9A | 0.9700 |
C4—C5 | 1.4126 (15) | C9—H9B | 0.9700 |
C5—C6 | 1.3789 (15) | C10—H10A | 0.9600 |
C5—H5 | 0.9300 | C10—H10B | 0.9600 |
C6—H6 | 0.9300 | C10—H10C | 0.9600 |
C1'—C2' | 1.3888 (15) | C11—C12 | 1.5156 (18) |
C1'—C6' | 1.4044 (16) | C11—H11A | 0.9700 |
C2'—C3' | 1.3804 (15) | C11—H11B | 0.9700 |
C2'—H2' | 0.9300 | C12—H12A | 0.9600 |
C3'—C4' | 1.4116 (15) | C12—H12B | 0.9600 |
C3'—H3' | 0.9300 | C12—H12C | 0.9600 |
C4'—N4 | 1.3722 (13) | C13—C14 | 1.5160 (17) |
C4'—C5' | 1.4214 (15) | C13—H13A | 0.9700 |
C5'—C6' | 1.3759 (15) | C13—H13B | 0.9700 |
C5'—H5' | 0.9300 | C14—H14A | 0.9600 |
C6'—H6' | 0.9300 | C14—H14B | 0.9600 |
N3—C7 | 1.4544 (14) | C14—H14C | 0.9600 |
N3—C9 | 1.4606 (14) | ||
N1'—N1—C1 | 113.55 (10) | C8—C7—H7A | 109.0 |
N1—N1'—C1' | 114.80 (10) | N3—C7—H7B | 109.0 |
C2—C1—C6 | 118.41 (10) | C8—C7—H7B | 109.0 |
C2—C1—N1 | 117.27 (10) | H7A—C7—H7B | 107.8 |
C6—C1—N1 | 124.30 (10) | C7—C8—H8A | 109.5 |
C3—C2—C1 | 121.53 (11) | C7—C8—H8B | 109.5 |
C3—C2—H2 | 119.2 | H8A—C8—H8B | 109.5 |
C1—C2—H2 | 119.2 | C7—C8—H8C | 109.5 |
C2—C3—C4 | 120.78 (10) | H8A—C8—H8C | 109.5 |
C2—C3—H3 | 119.6 | H8B—C8—H8C | 109.5 |
C4—C3—H3 | 119.6 | N3—C9—C10 | 113.31 (10) |
N3—C4—C5 | 120.90 (10) | N3—C9—H9A | 108.9 |
N3—C4—C3 | 121.98 (10) | C10—C9—H9A | 108.9 |
C5—C4—C3 | 117.11 (10) | N3—C9—H9B | 108.9 |
C6—C5—C4 | 121.30 (11) | C10—C9—H9B | 108.9 |
C6—C5—H5 | 119.4 | H9A—C9—H9B | 107.7 |
C4—C5—H5 | 119.3 | C9—C10—H10A | 109.5 |
C5—C6—C1 | 120.86 (11) | C9—C10—H10B | 109.5 |
C5—C6—H6 | 119.6 | H10A—C10—H10B | 109.5 |
C1—C6—H6 | 119.6 | C9—C10—H10C | 109.5 |
C2'—C1'—C6' | 118.04 (10) | H10A—C10—H10C | 109.5 |
C2'—C1'—N1' | 115.65 (10) | H10B—C10—H10C | 109.5 |
C6'—C1'—N1' | 126.25 (10) | N4—C11—C12 | 112.66 (10) |
C3'—C2'—C1' | 122.13 (10) | N4—C11—H11A | 109.1 |
C3'—C2'—H2' | 118.9 | C12—C11—H11A | 109.1 |
C1'—C2'—H2' | 118.9 | N4—C11—H11B | 109.1 |
C2'—C3'—C4' | 120.58 (10) | C12—C11—H11B | 109.1 |
C2'—C3'—H3' | 119.7 | H11A—C11—H11B | 107.8 |
C4'—C3'—H3' | 119.7 | C11—C12—H12A | 109.5 |
N4—C4'—C3' | 121.75 (10) | C11—C12—H12B | 109.5 |
N4—C4'—C5' | 121.33 (10) | H12A—C12—H12B | 109.5 |
C3'—C4'—C5' | 116.92 (10) | C11—C12—H12C | 109.5 |
C6'—C5'—C4' | 121.65 (10) | H12A—C12—H12C | 109.5 |
C6'—C5'—H5' | 119.2 | H12B—C12—H12C | 109.5 |
C4'—C5'—H5' | 119.2 | N4—C13—C14 | 112.62 (10) |
C5'—C6'—C1' | 120.64 (10) | N4—C13—H13A | 109.1 |
C5'—C6'—H6' | 119.7 | C14—C13—H13A | 109.1 |
C1'—C6'—H6' | 119.7 | N4—C13—H13B | 109.1 |
C4—N3—C7 | 121.49 (9) | C14—C13—H13B | 109.1 |
C4—N3—C9 | 121.30 (9) | H13A—C13—H13B | 107.8 |
C7—N3—C9 | 115.84 (9) | C13—C14—H14A | 109.5 |
C4'—N4—C13 | 121.79 (9) | C13—C14—H14B | 109.5 |
C4'—N4—C11 | 122.36 (9) | H14A—C14—H14B | 109.5 |
C13—N4—C11 | 115.84 (9) | C13—C14—H14C | 109.5 |
N3—C7—C8 | 112.93 (10) | H14A—C14—H14C | 109.5 |
N3—C7—H7A | 109.0 | H14B—C14—H14C | 109.5 |
C1—N1—N1'—C1' | −175.90 (9) | C3'—C4'—C5'—C6' | 2.12 (16) |
N1'—N1—C1—C2 | −173.26 (10) | C4'—C5'—C6'—C1' | −0.34 (17) |
N1'—N1—C1—C6 | 8.59 (15) | C2'—C1'—C6'—C5' | −1.42 (16) |
C6—C1—C2—C3 | −0.35 (17) | N1'—C1'—C6'—C5' | 175.70 (11) |
N1—C1—C2—C3 | −178.61 (10) | C5—C4—N3—C7 | 175.50 (10) |
C1—C2—C3—C4 | −0.61 (18) | C3—C4—N3—C7 | −5.73 (16) |
C2—C3—C4—N3 | −177.74 (11) | C5—C4—N3—C9 | 9.43 (16) |
C2—C3—C4—C5 | 1.07 (16) | C3—C4—N3—C9 | −171.81 (11) |
N3—C4—C5—C6 | 178.22 (11) | C3'—C4'—N4—C13 | −177.80 (10) |
C3—C4—C5—C6 | −0.61 (16) | C5'—C4'—N4—C13 | 1.46 (16) |
C4—C5—C6—C1 | −0.34 (17) | C3'—C4'—N4—C11 | 1.50 (16) |
C2—C1—C6—C5 | 0.82 (17) | C5'—C4'—N4—C11 | −179.24 (10) |
N1—C1—C6—C5 | 178.95 (10) | C4—N3—C7—C8 | −83.07 (13) |
N1—N1'—C1'—C2' | −177.30 (10) | C9—N3—C7—C8 | 83.72 (12) |
N1—N1'—C1'—C6' | 5.52 (16) | C4—N3—C9—C10 | −90.23 (13) |
C6'—C1'—C2'—C3' | 1.37 (16) | C7—N3—C9—C10 | 102.95 (12) |
N1'—C1'—C2'—C3' | −176.05 (10) | C4'—N4—C11—C12 | −88.41 (13) |
C1'—C2'—C3'—C4' | 0.46 (17) | C13—N4—C11—C12 | 90.94 (12) |
C2'—C3'—C4'—N4 | 177.12 (10) | C4'—N4—C13—C14 | −86.72 (13) |
C2'—C3'—C4'—C5' | −2.17 (16) | C11—N4—C13—C14 | 93.93 (12) |
N4—C4'—C5'—C6' | −177.18 (10) |
Cg1 and Cg2 are the centroids of the C1'–C6' and C1–C6 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···C3i | 0.97 | 2.81 | 3.7155 (17) | 156 |
C13—H13B···C1′ii | 0.97 | 2.81 | 3.6049 (16) | 140 |
C12—H12A···C6i | 0.96 | 2.72 | 3.5441 (17) | 144 |
C8—H8A···Cg1iii | 0.96 | 2.75 | 3.446 (2) | 130 |
C5′—H5′···Cg1ii | 0.93 | 2.94 | 3.767 (2) | 148 |
C11—H11B···Cg2i | 0.97 | 2.84 | 3.549 (2) | 131 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z−1/2; (iii) x, −y+3/2, z+1/2. |
C18H18N2O4 | F(000) = 344 |
Mr = 326.34 | Dx = 1.419 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1345 reflections |
a = 14.7061 (11) Å | θ = 2.8–25.0° |
b = 4.5005 (4) Å | µ = 0.10 mm−1 |
c = 11.5889 (8) Å | T = 100 K |
β = 95.033 (6)° | Plate, red |
V = 764.05 (10) Å3 | 0.35 × 0.25 × 0.10 mm |
Z = 2 |
Oxford Xcalibur diffractometer | 1282 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 29.0°, θmin = 2.8° |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | h = −20→19 |
ω scans | k = −4→6 |
5744 measured reflections | l = −15→15 |
1938 independent reflections |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters not refined |
S = 0.95 | w = 1/[σ2(Fo2) + (0.071P)2] where P = (Fo2 + 2Fc2)/3 |
1938 reflections | (Δ/σ)max < 0.001 |
109 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C18H18N2O4 | V = 764.05 (10) Å3 |
Mr = 326.34 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.7061 (11) Å | µ = 0.10 mm−1 |
b = 4.5005 (4) Å | T = 100 K |
c = 11.5889 (8) Å | 0.35 × 0.25 × 0.10 mm |
β = 95.033 (6)° |
Oxford Xcalibur diffractometer | 1282 reflections with I > 2σ(I) |
5744 measured reflections | Rint = 0.031 |
1938 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters not refined |
S = 0.95 | Δρmax = 0.39 e Å−3 |
1938 reflections | Δρmin = −0.22 e Å−3 |
109 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.28116 (7) | 2.0280 (2) | 0.76163 (8) | 0.0165 (3) | |
O2 | 0.34556 (7) | 1.9518 (3) | 0.59436 (9) | 0.0212 (3) | |
N1 | 0.00148 (8) | 1.0611 (3) | 0.54895 (10) | 0.0137 (3) | |
C1 | 0.07332 (10) | 1.2740 (3) | 0.56888 (12) | 0.0130 (3) | |
C2 | 0.07752 (10) | 1.4146 (3) | 0.67623 (12) | 0.0140 (3) | |
H2 | 0.0347 | 1.3696 | 0.7280 | 0.017* | |
C3 | 0.14540 (9) | 1.6214 (3) | 0.70618 (12) | 0.0143 (3) | |
H3 | 0.1479 | 1.7152 | 0.7779 | 0.017* | |
C4 | 0.20979 (9) | 1.6885 (3) | 0.62903 (12) | 0.0133 (3) | |
C5 | 0.20441 (10) | 1.5497 (3) | 0.52072 (12) | 0.0152 (3) | |
H5 | 0.2468 | 1.5964 | 0.4686 | 0.018* | |
C6 | 0.13674 (10) | 1.3437 (3) | 0.49025 (12) | 0.0153 (3) | |
H6 | 0.1335 | 1.2525 | 0.4180 | 0.018* | |
C7 | 0.28612 (9) | 1.9012 (3) | 0.65726 (12) | 0.0143 (3) | |
C8 | 0.35446 (10) | 2.2329 (4) | 0.80038 (13) | 0.0190 (4) | |
H8A | 0.3317 | 2.3792 | 0.8521 | 0.023* | |
H8B | 0.3750 | 2.3369 | 0.7341 | 0.023* | |
C9 | 0.43345 (11) | 2.0682 (4) | 0.86218 (14) | 0.0268 (4) | |
H9A | 0.4809 | 2.2065 | 0.8869 | 0.040* | |
H9B | 0.4565 | 1.9252 | 0.8106 | 0.040* | |
H9C | 0.4133 | 1.9679 | 0.9285 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0153 (5) | 0.0223 (6) | 0.0118 (5) | −0.0038 (4) | 0.0007 (4) | −0.0032 (4) |
O2 | 0.0181 (5) | 0.0314 (7) | 0.0149 (5) | −0.0043 (5) | 0.0049 (4) | −0.0010 (5) |
N1 | 0.0158 (6) | 0.0156 (6) | 0.0095 (6) | 0.0007 (5) | −0.0003 (5) | 0.0002 (5) |
C1 | 0.0132 (7) | 0.0144 (8) | 0.0111 (7) | 0.0017 (6) | −0.0003 (5) | 0.0014 (6) |
C2 | 0.0151 (7) | 0.0186 (8) | 0.0086 (6) | 0.0013 (6) | 0.0032 (5) | 0.0025 (6) |
C3 | 0.0174 (7) | 0.0173 (8) | 0.0079 (7) | 0.0018 (6) | 0.0008 (5) | −0.0003 (6) |
C4 | 0.0138 (7) | 0.0154 (8) | 0.0107 (7) | 0.0016 (6) | 0.0004 (5) | 0.0019 (6) |
C5 | 0.0150 (7) | 0.0204 (8) | 0.0104 (7) | 0.0009 (6) | 0.0032 (5) | 0.0019 (6) |
C6 | 0.0188 (7) | 0.0195 (8) | 0.0076 (6) | 0.0011 (6) | 0.0011 (5) | −0.0007 (6) |
C7 | 0.0149 (7) | 0.0179 (8) | 0.0097 (7) | 0.0021 (6) | −0.0003 (5) | 0.0008 (6) |
C8 | 0.0181 (8) | 0.0229 (9) | 0.0157 (7) | −0.0058 (6) | −0.0001 (6) | −0.0019 (6) |
C9 | 0.0199 (8) | 0.0387 (11) | 0.0208 (8) | −0.0052 (8) | −0.0033 (6) | 0.0048 (8) |
O1—C7 | 1.3451 (17) | C4—C5 | 1.398 (2) |
O1—C8 | 1.4591 (17) | C4—C7 | 1.490 (2) |
O2—C7 | 1.2080 (17) | C5—C6 | 1.383 (2) |
N1—N1i | 1.258 (2) | C5—H5 | 0.9300 |
N1—C1 | 1.4301 (19) | C6—H6 | 0.9300 |
C1—C2 | 1.3922 (19) | C8—C9 | 1.505 (2) |
C1—C6 | 1.396 (2) | C8—H8A | 0.9700 |
C2—C3 | 1.386 (2) | C8—H8B | 0.9700 |
C2—H2 | 0.9300 | C9—H9A | 0.9600 |
C3—C4 | 1.3913 (19) | C9—H9B | 0.9600 |
C3—H3 | 0.9300 | C9—H9C | 0.9600 |
C7—O1—C8 | 116.61 (11) | C5—C6—H6 | 120.3 |
N1i—N1—C1 | 113.89 (15) | C1—C6—H6 | 120.3 |
C2—C1—C6 | 120.10 (14) | O2—C7—O1 | 124.18 (14) |
C2—C1—N1 | 115.03 (12) | O2—C7—C4 | 124.05 (13) |
C6—C1—N1 | 124.87 (13) | O1—C7—C4 | 111.77 (12) |
C3—C2—C1 | 120.21 (13) | O1—C8—C9 | 110.72 (13) |
C3—C2—H2 | 119.9 | O1—C8—H8A | 109.5 |
C1—C2—H2 | 119.9 | C9—C8—H8A | 109.5 |
C2—C3—C4 | 120.04 (13) | O1—C8—H8B | 109.5 |
C2—C3—H3 | 120.0 | C9—C8—H8B | 109.5 |
C4—C3—H3 | 120.0 | H8A—C8—H8B | 108.1 |
C3—C4—C5 | 119.46 (13) | C8—C9—H9A | 109.5 |
C3—C4—C7 | 122.73 (13) | C8—C9—H9B | 109.5 |
C5—C4—C7 | 117.81 (13) | H9A—C9—H9B | 109.5 |
C6—C5—C4 | 120.76 (13) | C8—C9—H9C | 109.5 |
C6—C5—H5 | 119.6 | H9A—C9—H9C | 109.5 |
C4—C5—H5 | 119.6 | H9B—C9—H9C | 109.5 |
C5—C6—C1 | 119.42 (13) | ||
N1i—N1—C1—C2 | 179.40 (15) | C2—C1—C6—C5 | 1.0 (2) |
N1i—N1—C1—C6 | −1.0 (2) | N1—C1—C6—C5 | −178.62 (13) |
C6—C1—C2—C3 | −0.9 (2) | C8—O1—C7—O2 | −1.6 (2) |
N1—C1—C2—C3 | 178.79 (13) | C8—O1—C7—C4 | 177.84 (11) |
C1—C2—C3—C4 | −0.2 (2) | C3—C4—C7—O2 | 176.01 (14) |
C2—C3—C4—C5 | 1.1 (2) | C5—C4—C7—O2 | −3.1 (2) |
C2—C3—C4—C7 | −178.02 (13) | C3—C4—C7—O1 | −3.48 (19) |
C3—C4—C5—C6 | −0.9 (2) | C5—C4—C7—O1 | 177.39 (12) |
C7—C4—C5—C6 | 178.21 (13) | C7—O1—C8—C9 | −87.27 (15) |
C4—C5—C6—C1 | −0.1 (2) |
Symmetry code: (i) −x, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1ii | 0.93 | 2.56 | 3.3175 (17) | 140 |
Symmetry code: (ii) x, −y+7/2, z−1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C20H28N4 | C18H18N2O4 |
Mr | 324.46 | 326.34 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 14.0805 (3), 7.9682 (2), 21.1890 (5) | 14.7061 (11), 4.5005 (4), 11.5889 (8) |
β (°) | 128.989 (2) | 95.033 (6) |
V (Å3) | 1847.82 (9) | 764.05 (10) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.10 |
Crystal size (mm) | 0.30 × 0.20 × 0.05 | 0.35 × 0.25 × 0.10 |
Data collection | ||
Diffractometer | Oxford Xcalibur diffractometer | Oxford Xcalibur diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14494, 4685, 3433 | 5744, 1938, 1282 |
Rint | 0.019 | 0.031 |
(sin θ/λ)max (Å−1) | 0.682 | 0.682 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.126, 1.08 | 0.042, 0.117, 0.95 |
No. of reflections | 4685 | 1938 |
No. of parameters | 217 | 109 |
H-atom treatment | H-atom parameters not refined | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.39, −0.28 | 0.39, −0.22 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Parameter | Azobenzene | (I) | (II) | 4,4'-(COOH)2 | 4,4'-(COOMe)2 |
N═N | |||||
X-ray | 1.259 (2) | 1.2655 (13) | 1.258 (2) | 1.239 (2) | 1.255 (3) |
1.251 (2) | 1.257 (4) | ||||
DFT | 1.252 | 1.261 | 1.253 | 1.251 | 1.253 |
C—N | |||||
X-ray | 1.431 (1) | 1.4230 (14) | 1.4301 (19) | 1.433 (2) | 1.431 (3) |
1.431 (2) | 1.4196 (13) | 1.434 (3) | |||
DFT | 1.419 | 1.406 | 1.418 | 1.418 | 1.418 |
C—N═N | |||||
X-ray | 113.5 (1) | 113.55 (10) | 113.89 (15) | 114.0 (2) | 114.3 (2) |
114.1 (1) | 114.80 (10) | 114.3 (2) | |||
DFT | 115.43 | 115.70 | 115.23 | 115.29 | 115.23 |
C—C—N═N (°) | |||||
X-ray | 21.0 (2) | 8.59 (15) | -1.0 (2) | 5.4 | -8.4 (3) |
10.1 (2) | 5.52 (16) | 10.9 (3) | |||
DFT | 0.00 | 0.42 | -0.10 | 0.00 | 0.00 |
HOMA | |||||
X-ray | 0.985 | 0.924 | 0.990 | 0.989 | 0.960 |
0.985 | 0.908 | ||||
DFT | 0.977 | 0.905 | 0.967 | 0.966 | 0.967 |
Point-group | C2h | C2 | Ci | C2h | C2h |
Cg1 and Cg2 are the centroids of the C1'–C6' and C1–C6 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···C3i | 0.97 | 2.81 | 3.7155 (17) | 156 |
C13—H13B···C1'ii | 0.97 | 2.81 | 3.6049 (16) | 140 |
C12—H12A···C6i | 0.96 | 2.72 | 3.5441 (17) | 144 |
C8—H8A···Cg1iii | 0.96 | 2.75 | 3.446 (2) | 130 |
C5'—H5'···Cg1ii | 0.93 | 2.94 | 3.767 (2) | 148 |
C11—H11B···Cg2i | 0.97 | 2.84 | 3.549 (2) | 131 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, y+1/2, −z−1/2; (iii) x, −y+3/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O1i | 0.93 | 2.56 | 3.3175 (17) | 140 |
Symmetry code: (i) x, −y+7/2, z−1/2. |