organic compounds
R)-[1-(4-bromophenyl)ethyl]iminomethyl}-4-(phenyldiazenyl)phenol, a chiral photochromic Schiff base
of 2-{(aDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
*Correspondence e-mail: akitsu@rs.kagu.tus.ac.jp
The title chiral photochromic Schiff base compound, C21H18BrN3O, was synthesized from (R)-(+)-1-(4-bromophenyl)ethylamine and the salicylaldehyde of an azobenzene derivative. The molecule corresponds to the phenol–imine tautomer, the C=N and N—C bond distances being 1.285 (3) and 1.470 (3) Å, respectively. The diazenyl group adopts a trans form, with an N=N distance of 1.256 (3) Å. The hydroxy group is involved in intramolecular O—H⋯N hydrogen bonding. In the crystal, C—H⋯π interactions consolidate the crystal packing of one-dimensional chains, which exhibits short intermolecular Br⋯C contacts of 3.400 (3) Å.
Keywords: crystal structure; Schiff base; azobenzene; photochromic.
CCDC reference: 1432412
1. Related literature
For applications of (chiral) photochromic Schiff base compounds, see: Akitsu & Einaga (2006b); Akitsu et al. (2004); Aritake et al. (2010); Miura et al. (2009). For the crystal structures of related compounds, see: Akitsu & Einaga (2005a,b, 2006a); Akitsu (2007); Akitsu & Itoh (2010); Aslantas et al. (2007); Hadjoudis & Mavridis (2004); Khandar & Rezvani (1999).
2. Experimental
2.1. Crystal data
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Data collection: APEX2 (Bruker, 1998); cell SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 1432412
https://doi.org/10.1107/S2056989015019866/cv5499sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019866/cv5499Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015019866/cv5499Isup3.cml
Treatment of aniline (0.951 g, 10.0 mmol) in 15 ml of 6M HCl and NaNO2 (0.690 g, 10 mmol) in 15 ml of H2O for 30 min at 278 K gave rise to the yellow precursor. Treatment of the precursor and salicylaldehyde (1.22 g 10 mmol) in 30 ml of 10% NaOH aqueous solution for 1 h at 278 K, and the resulting brown precipitates were filtrated and washed with water and ethanol, and dried in a desiccator for several days. Treatment of the brown precipitates (0.226 g, 1.00 mmol) and (R)-(+)-1-(4-Bromophenyl)ethylamine (0.200 g, 1.00 mmol) for 2 h at 298 K under a nitrogen atmosphere gave rise to orange compound after evaporation(yield 0.0598 g, 29.3%). This crude orange compound was filtered and recrystallized slow evaporation from aceton to give orange prismatic single crystals. Anal. Calc. for C21H18BrN3O: C, 61.78; H, 4.44; N, 10.29. Found: C, 61.66; H, 4.67; N, 10.17%. IR (KBr,(cm-1)): 1585 (N=N), 1632(C=N). 1H NMR (300 MHz, DMSO) δ(p.p.m.): 1.60 (d,3H), 2.50 (m,2H), 4.80 (dd,1H), 7.03 (d,2H), 7.41 (tt,2H), 7.56 (m,5H), 7.84 (tt,2H), 7.95 (dd,1H), 8.12 (d,1H), 8.88(s,1H).
In recent years, there is a growing interest in the organic/inorganic metal complexes and photochromic compounds. For example, cis-trans
of azobenzene could switch conformation of chiral ligands (Akitsu & Einaga, 2005a, 2005b), chiral conformation change in a solution induced by a photochromic solute (Akitsu & Einaga, 2006a; Akitsu, 2007) and optical anisotropy in polymeric films (Akitsu & Itoh, 2010). Also free Schiff base ligands may act as photochromic, thermochromics, and fluorescence materials (Akitsu et al., 2004; Hadjoudis & Mavridis, 2004; Akitsu & Einaga, 2006b). Recently, we have synthesized the title compound (I). Herewith we present its crystal structure.The molecule of (I) (Fig. I) adopts an E configuration with respect to the imine C═N double bond with C13—C12—N3—C14 torsion angle of 178.6 (2) °. Thus, the π-conjugated system around the imine group is essentially planar. All bond lengths and angles in (I) correspond well to those observed in similar Schiff base ligands (Akitsu & Einaga, 2006b; Miura et al., 2009; Aritake et al., 2010) and azobenzene derivatives (Aslantas et al., 2007; Khandar & Rezvani, 1999). The C11—O1 bond distance of 1.350 (3) Å suggests that it is the phenol-imine tautomer. The contraction of the C12═N3 bond [1.285 (3) Å] is also in agreement with the phenol-imine tautomer. As for the azobenzene moiety, the azo N═N double bond adopts an E configuration with the N═N distance of 1.256 (3) Å. Hydroxyl group is involved in intramolecular O—H···N hydrogen bond (Table 1).
In the crystal, C—H···π interactions (Table 1) consolidate the crystal packing, which exhibits short intermolecular Br1···C20(1/2+x, 1/2-y, 2-z) contact of 3.400 (3) Å.
For applications of chiral photochromic Schiff base compounds, see: Akitsu & Einaga (2005a,b; 2006a,b); Akitsu (2007); Akitsu & Itoh (2010). For the crystal structures of related compounds, see: Akitsu et al. (2004); Aslantas et al. (2007); Aritake et al. (2010); Hadjoudis & Mavridis (2004); Khandar & Rezvani (1999); Miura et al. (2009).
Data collection: APEX2 (Bruker, 1998); cell
SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Molecular structure of (I) showing the atomic numbering and 50% probability displacement ellipsoids. |
C21H18BrN3O | Dx = 1.496 Mg m−3 |
Mr = 408.29 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21212 | Cell parameters from 10349 reflections |
a = 7.271 (3) Å | θ = 2.8–27.7° |
b = 41.901 (15) Å | µ = 2.28 mm−1 |
c = 5.952 (2) Å | T = 113 K |
V = 1813.3 (11) Å3 | Needle, orange |
Z = 4 | 0.37 × 0.23 × 0.08 mm |
F(000) = 832 |
Bruker APEXII CCD diffractometer | 4176 independent reflections |
Radiation source: fine-focus sealed tube | 3723 reflections with I > 2σ(I) |
Detector resolution: 8.333 pixels mm-1 | Rint = 0.027 |
φ and ω scans | θmax = 27.7°, θmin = 2.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −8→9 |
Tmin = 0.486, Tmax = 0.833 | k = −54→33 |
10349 measured reflections | l = −7→7 |
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)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.047 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.002 |
4176 reflections | Δρmax = 0.57 e Å−3 |
237 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 1360 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.005 (4) |
C21H18BrN3O | V = 1813.3 (11) Å3 |
Mr = 408.29 | Z = 4 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 7.271 (3) Å | µ = 2.28 mm−1 |
b = 41.901 (15) Å | T = 113 K |
c = 5.952 (2) Å | 0.37 × 0.23 × 0.08 mm |
Bruker APEXII CCD diffractometer | 4176 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3723 reflections with I > 2σ(I) |
Tmin = 0.486, Tmax = 0.833 | Rint = 0.027 |
10349 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.047 | Δρmax = 0.57 e Å−3 |
S = 1.01 | Δρmin = −0.40 e Å−3 |
4176 reflections | Absolute structure: Flack x determined using 1360 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
237 parameters | Absolute structure parameter: 0.005 (4) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.09221 (4) | 0.26333 (2) | 0.94955 (5) | 0.02934 (9) | |
C1 | 0.2882 (4) | 0.55533 (6) | 0.2777 (4) | 0.0162 (6) | |
H1 | 0.347 | 0.54 | 0.185 | 0.019* | |
C2 | 0.2286 (3) | 0.54700 (5) | 0.4928 (4) | 0.0132 (6) | |
C3 | 0.2610 (4) | 0.58613 (6) | 0.2004 (5) | 0.0191 (6) | |
H3 | 0.3033 | 0.5919 | 0.0551 | 0.023* | |
C4 | 0.1732 (4) | 0.60841 (6) | 0.3323 (5) | 0.0193 (7) | |
H4 | 0.1531 | 0.6294 | 0.2766 | 0.023* | |
C5 | 0.1136 (4) | 0.60022 (5) | 0.5478 (5) | 0.0189 (6) | |
H5 | 0.0549 | 0.6157 | 0.6397 | 0.023* | |
C6 | 0.1400 (3) | 0.56948 (5) | 0.6277 (4) | 0.0153 (6) | |
H6 | 0.098 | 0.5638 | 0.7733 | 0.018* | |
C7 | 0.3225 (3) | 0.45296 (5) | 0.6999 (4) | 0.0130 (6) | |
H7 | 0.3679 | 0.4579 | 0.5543 | 0.016* | |
C8 | 0.2539 (4) | 0.47727 (5) | 0.8343 (4) | 0.0133 (6) | |
C9 | 0.1948 (3) | 0.47027 (5) | 1.0517 (5) | 0.0147 (5) | |
H9 | 0.1538 | 0.487 | 1.1473 | 0.018* | |
C10 | 0.1954 (4) | 0.43923 (6) | 1.1290 (4) | 0.0147 (6) | |
H10 | 0.1524 | 0.4347 | 1.2762 | 0.018* | |
C11 | 0.2586 (3) | 0.41462 (5) | 0.9931 (4) | 0.0152 (6) | |
C12 | 0.3926 (4) | 0.39625 (5) | 0.6274 (4) | 0.0142 (5) | |
H12 | 0.4383 | 0.4015 | 0.4826 | 0.017* | |
C13 | 0.3259 (4) | 0.42154 (5) | 0.7748 (4) | 0.0120 (6) | |
C14 | 0.4556 (3) | 0.34250 (5) | 0.5321 (5) | 0.0170 (6) | |
H14 | 0.5028 | 0.3533 | 0.394 | 0.02* | |
C15 | 0.2920 (4) | 0.32168 (6) | 0.4678 (5) | 0.0273 (7) | |
H15A | 0.2462 | 0.3106 | 0.6014 | 0.041* | |
H15B | 0.3305 | 0.306 | 0.3551 | 0.041* | |
H15C | 0.1941 | 0.3351 | 0.4054 | 0.041* | |
C16 | 0.6884 (4) | 0.29788 (5) | 0.5224 (5) | 0.0206 (6) | |
H16 | 0.6402 | 0.2924 | 0.3791 | 0.025* | |
C17 | 0.6118 (4) | 0.32344 (5) | 0.6378 (4) | 0.0148 (6) | |
C18 | 0.6859 (4) | 0.33094 (6) | 0.8466 (4) | 0.0212 (7) | |
H18 | 0.637 | 0.3484 | 0.9289 | 0.025* | |
C19 | 0.8302 (4) | 0.31341 (5) | 0.9371 (5) | 0.0220 (6) | |
H19 | 0.8799 | 0.3189 | 1.0796 | 0.026* | |
C20 | 0.9003 (4) | 0.28803 (5) | 0.8183 (4) | 0.0186 (6) | |
C21 | 0.8323 (4) | 0.28005 (6) | 0.6082 (5) | 0.0214 (7) | |
H21 | 0.8831 | 0.2628 | 0.5253 | 0.026* | |
N1 | 0.2355 (3) | 0.50990 (4) | 0.7656 (4) | 0.0149 (5) | |
N2 | 0.2565 (3) | 0.51440 (4) | 0.5585 (4) | 0.0150 (5) | |
N3 | 0.3906 (3) | 0.36692 (4) | 0.6905 (3) | 0.0169 (5) | |
O1 | 0.2552 (3) | 0.38445 (4) | 1.0728 (3) | 0.0200 (4) | |
H1A | 0.2988 | 0.372 | 0.9758 | 0.03* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.03065 (17) | 0.02551 (13) | 0.03187 (16) | 0.01116 (13) | −0.00603 (16) | −0.00168 (14) |
C1 | 0.0158 (16) | 0.0182 (13) | 0.0147 (15) | −0.0033 (11) | −0.0014 (12) | −0.0026 (11) |
C2 | 0.0111 (13) | 0.0139 (11) | 0.0148 (17) | −0.0035 (9) | −0.0047 (11) | 0.0012 (10) |
C3 | 0.0191 (16) | 0.0228 (14) | 0.0154 (15) | −0.0084 (12) | −0.0061 (13) | 0.0028 (11) |
C4 | 0.0186 (16) | 0.0148 (13) | 0.0246 (17) | −0.0040 (11) | −0.0077 (14) | 0.0051 (12) |
C5 | 0.0162 (15) | 0.0147 (11) | 0.0258 (14) | 0.0011 (10) | −0.0031 (16) | −0.0051 (12) |
C6 | 0.0130 (16) | 0.0177 (12) | 0.0151 (14) | −0.0012 (10) | −0.0021 (11) | −0.0001 (11) |
C7 | 0.0099 (14) | 0.0172 (12) | 0.0118 (14) | −0.0022 (10) | −0.0003 (11) | 0.0005 (11) |
C8 | 0.0117 (15) | 0.0122 (12) | 0.0161 (15) | 0.0003 (10) | −0.0025 (12) | 0.0009 (11) |
C9 | 0.0127 (14) | 0.0186 (12) | 0.0128 (13) | 0.0002 (10) | −0.0016 (14) | −0.0050 (12) |
C10 | 0.0140 (15) | 0.0229 (13) | 0.0071 (13) | −0.0014 (11) | −0.0001 (11) | 0.0019 (11) |
C11 | 0.0119 (14) | 0.0159 (12) | 0.0176 (18) | 0.0004 (10) | −0.0017 (11) | 0.0051 (10) |
C12 | 0.0106 (14) | 0.0176 (12) | 0.0145 (13) | 0.0000 (11) | −0.0009 (12) | 0.0013 (10) |
C13 | 0.0091 (14) | 0.0147 (12) | 0.0123 (14) | 0.0014 (10) | −0.0006 (12) | 0.0004 (10) |
C14 | 0.0213 (16) | 0.0132 (11) | 0.0166 (14) | 0.0005 (10) | 0.0031 (13) | −0.0004 (11) |
C15 | 0.0249 (17) | 0.0213 (13) | 0.0357 (18) | −0.0018 (11) | −0.0050 (16) | −0.0010 (14) |
C16 | 0.0267 (16) | 0.0190 (13) | 0.0162 (16) | −0.0006 (11) | −0.0005 (14) | −0.0027 (11) |
C17 | 0.0183 (15) | 0.0101 (11) | 0.0159 (13) | −0.0032 (11) | 0.0042 (13) | 0.0015 (10) |
C18 | 0.0292 (18) | 0.0126 (12) | 0.0219 (16) | 0.0034 (11) | −0.0003 (14) | −0.0041 (11) |
C19 | 0.0277 (16) | 0.0200 (12) | 0.0182 (14) | 0.0008 (11) | −0.0032 (15) | −0.0047 (13) |
C20 | 0.0186 (15) | 0.0148 (12) | 0.0224 (15) | 0.0015 (12) | 0.0000 (15) | 0.0052 (11) |
C21 | 0.0271 (17) | 0.0166 (13) | 0.0206 (17) | 0.0048 (11) | 0.0045 (13) | −0.0051 (11) |
N1 | 0.0144 (13) | 0.0154 (11) | 0.0149 (13) | −0.0001 (9) | 0.0004 (10) | 0.0007 (9) |
N2 | 0.0160 (12) | 0.0145 (10) | 0.0146 (12) | −0.0005 (8) | 0.0010 (12) | 0.0021 (10) |
N3 | 0.0157 (13) | 0.0151 (10) | 0.0198 (12) | 0.0015 (9) | 0.0020 (12) | 0.0012 (9) |
O1 | 0.0279 (12) | 0.0150 (8) | 0.0172 (10) | 0.0034 (7) | 0.0064 (10) | 0.0036 (8) |
Br1—C20 | 1.905 (3) | C11—C13 | 1.419 (4) |
C1—C3 | 1.384 (3) | C12—N3 | 1.285 (3) |
C1—C2 | 1.396 (3) | C12—C13 | 1.459 (3) |
C1—H1 | 0.95 | C12—H12 | 0.95 |
C2—C6 | 1.395 (3) | C14—N3 | 1.470 (3) |
C2—N2 | 1.435 (3) | C14—C15 | 1.524 (3) |
C3—C4 | 1.376 (4) | C14—C17 | 1.524 (4) |
C3—H3 | 0.95 | C14—H14 | 1.0 |
C4—C5 | 1.397 (4) | C15—H15A | 0.98 |
C4—H4 | 0.95 | C15—H15B | 0.98 |
C5—C6 | 1.386 (3) | C15—H15C | 0.98 |
C5—H5 | 0.95 | C16—C21 | 1.383 (4) |
C6—H6 | 0.95 | C16—C17 | 1.389 (3) |
C7—C8 | 1.388 (3) | C16—H16 | 0.95 |
C7—C13 | 1.390 (3) | C17—C18 | 1.390 (4) |
C7—H7 | 0.95 | C18—C19 | 1.389 (4) |
C8—C9 | 1.395 (3) | C18—H18 | 0.95 |
C8—N1 | 1.433 (3) | C19—C20 | 1.375 (3) |
C9—C10 | 1.380 (3) | C19—H19 | 0.95 |
C9—H9 | 0.95 | C20—C21 | 1.386 (4) |
C10—C11 | 1.389 (3) | C21—H21 | 0.95 |
C10—H10 | 0.95 | N1—N2 | 1.256 (3) |
C11—O1 | 1.350 (3) | O1—H1A | 0.84 |
C3—C1—C2 | 119.6 (2) | C7—C13—C12 | 120.1 (2) |
C3—C1—H1 | 120.2 | C11—C13—C12 | 121.1 (2) |
C2—C1—H1 | 120.2 | N3—C14—C15 | 108.0 (2) |
C6—C2—C1 | 120.1 (2) | N3—C14—C17 | 109.8 (2) |
C6—C2—N2 | 123.5 (2) | C15—C14—C17 | 112.67 (19) |
C1—C2—N2 | 116.4 (2) | N3—C14—H14 | 108.8 |
C4—C3—C1 | 120.6 (3) | C15—C14—H14 | 108.8 |
C4—C3—H3 | 119.7 | C17—C14—H14 | 108.8 |
C1—C3—H3 | 119.7 | C14—C15—H15A | 109.5 |
C3—C4—C5 | 120.1 (2) | C14—C15—H15B | 109.5 |
C3—C4—H4 | 120.0 | H15A—C15—H15B | 109.5 |
C5—C4—H4 | 120.0 | C14—C15—H15C | 109.5 |
C6—C5—C4 | 120.0 (3) | H15A—C15—H15C | 109.5 |
C6—C5—H5 | 120.0 | H15B—C15—H15C | 109.5 |
C4—C5—H5 | 120.0 | C21—C16—C17 | 122.5 (3) |
C5—C6—C2 | 119.6 (2) | C21—C16—H16 | 118.7 |
C5—C6—H6 | 120.2 | C17—C16—H16 | 118.7 |
C2—C6—H6 | 120.2 | C16—C17—C18 | 117.4 (2) |
C8—C7—C13 | 121.1 (2) | C16—C17—C14 | 119.9 (2) |
C8—C7—H7 | 119.4 | C18—C17—C14 | 122.6 (2) |
C13—C7—H7 | 119.4 | C19—C18—C17 | 121.3 (2) |
C7—C8—C9 | 119.4 (2) | C19—C18—H18 | 119.3 |
C7—C8—N1 | 124.7 (2) | C17—C18—H18 | 119.3 |
C9—C8—N1 | 115.9 (2) | C20—C19—C18 | 119.3 (3) |
C10—C9—C8 | 120.4 (2) | C20—C19—H19 | 120.3 |
C10—C9—H9 | 119.8 | C18—C19—H19 | 120.3 |
C8—C9—H9 | 119.8 | C19—C20—C21 | 121.2 (3) |
C9—C10—C11 | 120.5 (2) | C19—C20—Br1 | 118.8 (2) |
C9—C10—H10 | 119.8 | C21—C20—Br1 | 120.02 (19) |
C11—C10—H10 | 119.8 | C16—C21—C20 | 118.2 (2) |
O1—C11—C10 | 119.0 (2) | C16—C21—H21 | 120.9 |
O1—C11—C13 | 121.3 (2) | C20—C21—H21 | 120.9 |
C10—C11—C13 | 119.7 (2) | N2—N1—C8 | 114.3 (2) |
N3—C12—C13 | 121.0 (2) | N1—N2—C2 | 113.1 (2) |
N3—C12—H12 | 119.5 | C12—N3—C14 | 118.3 (2) |
C13—C12—H12 | 119.5 | C11—O1—H1A | 109.5 |
C7—C13—C11 | 118.8 (2) | ||
C3—C1—C2—C6 | 0.8 (4) | C21—C16—C17—C18 | 0.3 (4) |
C3—C1—C2—N2 | 178.1 (2) | C21—C16—C17—C14 | 178.9 (2) |
C2—C1—C3—C4 | −1.0 (4) | N3—C14—C17—C16 | 176.7 (2) |
C1—C3—C4—C5 | 1.2 (4) | C15—C14—C17—C16 | 56.2 (3) |
C3—C4—C5—C6 | −1.1 (4) | N3—C14—C17—C18 | −4.8 (3) |
C4—C5—C6—C2 | 0.9 (4) | C15—C14—C17—C18 | −125.3 (3) |
C1—C2—C6—C5 | −0.8 (4) | C16—C17—C18—C19 | −0.5 (4) |
N2—C2—C6—C5 | −177.9 (2) | C14—C17—C18—C19 | −179.0 (2) |
C13—C7—C8—C9 | 2.8 (4) | C17—C18—C19—C20 | −0.4 (4) |
C13—C7—C8—N1 | −176.2 (2) | C18—C19—C20—C21 | 1.3 (4) |
C7—C8—C9—C10 | −3.3 (4) | C18—C19—C20—Br1 | −177.8 (2) |
N1—C8—C9—C10 | 175.8 (2) | C17—C16—C21—C20 | 0.6 (4) |
C8—C9—C10—C11 | 1.4 (4) | C19—C20—C21—C16 | −1.5 (4) |
C9—C10—C11—O1 | −179.2 (2) | Br1—C20—C21—C16 | 177.69 (19) |
C9—C10—C11—C13 | 1.1 (4) | C7—C8—N1—N2 | 11.8 (4) |
C8—C7—C13—C11 | −0.3 (4) | C9—C8—N1—N2 | −167.2 (2) |
C8—C7—C13—C12 | 177.8 (2) | C8—N1—N2—C2 | 177.17 (19) |
O1—C11—C13—C7 | 178.7 (2) | C6—C2—N2—N1 | −16.5 (3) |
C10—C11—C13—C7 | −1.6 (4) | C1—C2—N2—N1 | 166.3 (2) |
O1—C11—C13—C12 | 0.5 (4) | C13—C12—N3—C14 | 178.6 (2) |
C10—C11—C13—C12 | −179.8 (2) | C15—C14—N3—C12 | −113.7 (3) |
N3—C12—C13—C7 | −177.4 (2) | C17—C14—N3—C12 | 123.1 (3) |
N3—C12—C13—C11 | 0.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N3 | 0.84 | 1.84 | 2.585 (3) | 148 |
C12—H12···Cg1i | 0.95 | 2.80 | 3.399 (3) | 122 |
C10—H10···Cg1ii | 0.95 | 2.74 | 3.415 (3) | 128 |
C6—H6···Cg2iii | 0.95 | 2.75 | 3.423 (3) | 128 |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x, −y+1, z+1; (iii) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N3 | 0.84 | 1.84 | 2.585 (3) | 148 |
C12—H12···Cg1i | 0.95 | 2.80 | 3.399 (3) | 122 |
C10—H10···Cg1ii | 0.95 | 2.74 | 3.415 (3) | 128 |
C6—H6···Cg2iii | 0.95 | 2.75 | 3.423 (3) | 128 |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x, −y+1, z+1; (iii) x, y, z+1. |
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In recent years, there is a growing interest in the organic/inorganic metal complexes and photochromic compounds. For example, cis-trans photoisomerization of azobenzene could switch conformation of chiral ligands (Akitsu & Einaga, 2005a, 2005b), chiral conformation change in a solution induced by a photochromic solute (Akitsu & Einaga, 2006a; Akitsu, 2007) and optical anisotropy in polymeric films (Akitsu & Itoh, 2010). Also free Schiff base ligands may act as photochromic, thermochromics, and fluorescence materials (Akitsu et al., 2004; Hadjoudis & Mavridis, 2004; Akitsu & Einaga, 2006b). Recently, we have synthesized the title compound (I). Herewith we present its crystal structure.
The molecule of (I) (Fig. I) adopts an E configuration with respect to the imine C═N double bond with C13—C12—N3—C14 torsion angle of 178.6 (2) °. Thus, the π-conjugated system around the imine group is essentially planar. All bond lengths and angles in (I) correspond well to those observed in similar Schiff base ligands (Akitsu & Einaga, 2006b; Miura et al., 2009; Aritake et al., 2010) and azobenzene derivatives (Aslantas et al., 2007; Khandar & Rezvani, 1999). The C11—O1 bond distance of 1.350 (3) Å suggests that it is the phenol-imine tautomer. The contraction of the C12═N3 bond [1.285 (3) Å] is also in agreement with the phenol-imine tautomer. As for the azobenzene moiety, the azo N═N double bond adopts an E configuration with the N═N distance of 1.256 (3) Å. Hydroxyl group is involved in intramolecular O—H···N hydrogen bond (Table 1).
In the crystal, C—H···π interactions (Table 1) consolidate the crystal packing, which exhibits short intermolecular Br1···C20(1/2+x, 1/2-y, 2-z) contact of 3.400 (3) Å.