Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012457/fr1219sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012457/fr1219Isup2.hkl |
CCDC reference: 140964
5'-Allyl-2'-hydroxy-3'-methoxy-4-nitroazobenzene (1 g, 3.19 mmol) was dissolved in NaoH (1M, 100 ml) by heating. After cooling the solution, benzoyl chloride was added, and the mixture was refluxed for 1 h. After cooling, a precipitate was obtained when Na2O3 (1 g, 9.43 mmol) was added. The precipitate was washed with pure water, filtered and dried. Diffraction-quality crystals were obtained by recrystallization from ethyl acetate (m.p. 428–434 K). 1H NMR (CDCl3): δ 8.5–7.0 (m, Aromatic), 6.2–5.8 (m, –CH=), 5.4–5.1 (m, =CH2), 3.9 (s,-CH3), 3.6–3.4 (s,-CH2); 13C-NMR (CDCl3):δ 170 (C=O), 145–120 (Aromatic), 140–130 (–CH=), 116–112 (=CH2), 54.3 (–OCH3), 40–10 (–CH2); IR (cm−1): 3080–2800 (CH2, CH), 1635 (Allyl, C=C), 1450–1400 (N=N), 1600–1450 (C6H5), 1385 (OCH3), 1740 (C=O); UV[λ(nm), ε (mol−1cm−1)]: 271.1 (6268.1), 241.4 (9664.8), 206.2 (1229.05); analysis calculated for C23H19N3O5 (%): C 68.18, H 4.55, N 10.07; Found (%): C 68.19, H 4.62, N 10.02.
All H atoms were located geometrically 0.93 Å from the parent C atoms except for the C20 and methyl-H atoms which were located 0.97 and 0.96 Å, respectively. A riding model was used for all H atoms with an isotropic displacement parameter 1.5 (for methyl-H atoms) or 1.2 (for the other H atoms) times the value of the equivalent isotropic displacemnt parameter of the carrier atom.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXTL and PARST (Nardelli, 1995).
| Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and atom-numbering scheme. Fig. 2. Packing along [100] for (I). Dashed lines indicate C—H···O interactions. |
C23H19N3O5 | F(000) = 872 |
Mr = 417.41 | Dx = 1.286 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7564 (1) Å | Cell parameters from 4481 reflections |
b = 22.3441 (5) Å | θ = 1.5–33° |
c = 12.5552 (2) Å | µ = 0.09 mm−1 |
β = 97.766 (1)° | T = 293 K |
V = 2155.98 (7) Å3 | Slab, light yellow |
Z = 4 | 0.32 × 0.24 × 0.08 mm |
Siemens SMART CCD area detector diffractometer | 1920 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.073 |
Graphite monochromator | θmax = 28.3°, θmin = 1.8° |
ω scans | h = −10→8 |
15921 measured reflections | k = −14→29 |
5166 independent reflections | l = −16→16 |
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)] = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.197 | w = 1/[σ2(Fo2) + (0.0819P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
5166 reflections | Δρmax = 0.24 e Å−3 |
281 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0025 (11) |
C23H19N3O5 | V = 2155.98 (7) Å3 |
Mr = 417.41 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.7564 (1) Å | µ = 0.09 mm−1 |
b = 22.3441 (5) Å | T = 293 K |
c = 12.5552 (2) Å | 0.32 × 0.24 × 0.08 mm |
β = 97.766 (1)° |
Siemens SMART CCD area detector diffractometer | 1920 reflections with I > 2σ(I) |
15921 measured reflections | Rint = 0.073 |
5166 independent reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.197 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.24 e Å−3 |
5166 reflections | Δρmin = −0.20 e Å−3 |
281 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. The data collection was covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 3 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating thirty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible. The structure was solved by direct methods and refined by full-matrix least-square techniques. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.9882 (4) | 0.15459 (13) | −0.0585 (3) | 0.1368 (11) | |
O2 | 0.9476 (4) | 0.07217 (15) | 0.0203 (3) | 0.1467 (12) | |
O3 | −0.2560 (2) | 0.17466 (9) | 0.37821 (16) | 0.0800 (6) | |
O4 | 0.0105 (2) | 0.12748 (8) | 0.29568 (15) | 0.0672 (5) | |
O5 | 0.1935 (3) | 0.14157 (9) | 0.44743 (17) | 0.0857 (7) | |
N1 | 0.9096 (4) | 0.12358 (16) | −0.0020 (3) | 0.0999 (9) | |
N2 | 0.3269 (3) | 0.22698 (11) | 0.14856 (19) | 0.0737 (7) | |
N3 | 0.2361 (3) | 0.19428 (10) | 0.19837 (19) | 0.0684 (6) | |
C1 | 0.7564 (4) | 0.14978 (14) | 0.0392 (2) | 0.0706 (8) | |
C2 | 0.7162 (4) | 0.20842 (14) | 0.0180 (2) | 0.0725 (8) | |
H2B | 0.7841 | 0.2317 | −0.0215 | 0.087* | |
C3 | 0.5737 (4) | 0.23221 (13) | 0.0562 (2) | 0.0693 (8) | |
H3B | 0.5448 | 0.2722 | 0.0435 | 0.083* | |
C4 | 0.4734 (3) | 0.19698 (13) | 0.1131 (2) | 0.0642 (7) | |
C5 | 0.5164 (4) | 0.13759 (13) | 0.1341 (2) | 0.0768 (8) | |
H5A | 0.4480 | 0.1140 | 0.1729 | 0.092* | |
C6 | 0.6596 (4) | 0.11378 (13) | 0.0976 (2) | 0.0812 (9) | |
H6A | 0.6911 | 0.0741 | 0.1118 | 0.097* | |
C7 | 0.0905 (3) | 0.22464 (12) | 0.2342 (2) | 0.0622 (7) | |
C8 | 0.0532 (4) | 0.28463 (13) | 0.2188 (2) | 0.0717 (8) | |
H8A | 0.1265 | 0.3085 | 0.1840 | 0.086* | |
C9 | −0.0911 (4) | 0.30969 (13) | 0.2542 (2) | 0.0739 (8) | |
C10 | −0.1966 (4) | 0.27341 (14) | 0.3085 (2) | 0.0726 (8) | |
H10A | −0.2930 | 0.2900 | 0.3341 | 0.087* | |
C11 | −0.1614 (4) | 0.21360 (13) | 0.3252 (2) | 0.0655 (7) | |
C12 | −0.0169 (3) | 0.18897 (12) | 0.2867 (2) | 0.0606 (7) | |
C13 | 0.1219 (4) | 0.10782 (12) | 0.3815 (2) | 0.0637 (7) | |
C14 | 0.1395 (3) | 0.04205 (12) | 0.3816 (3) | 0.0662 (8) | |
C15 | 0.2212 (4) | 0.01497 (14) | 0.4741 (3) | 0.0872 (10) | |
H15A | 0.2692 | 0.0384 | 0.5319 | 0.105* | |
C16 | 0.2320 (5) | −0.04649 (16) | 0.4812 (4) | 0.1039 (11) | |
H16A | 0.2859 | −0.0645 | 0.5437 | 0.125* | |
C17 | 0.1632 (5) | −0.08085 (16) | 0.3958 (4) | 0.1032 (12) | |
H17A | 0.1689 | −0.1223 | 0.4010 | 0.124* | |
C18 | 0.0860 (5) | −0.05493 (16) | 0.3028 (4) | 0.1005 (11) | |
H18A | 0.0428 | −0.0788 | 0.2445 | 0.121* | |
C19 | 0.0719 (4) | 0.00697 (14) | 0.2953 (3) | 0.0815 (9) | |
H19A | 0.0173 | 0.0247 | 0.2326 | 0.098* | |
C20 | −0.1345 (5) | 0.37473 (15) | 0.2338 (3) | 0.1015 (11) | |
H20A | −0.0795 | 0.3880 | 0.1730 | 0.122* | |
H20B | −0.2593 | 0.3784 | 0.2138 | 0.122* | |
C21 | −0.0827 (7) | 0.41336 (19) | 0.3218 (4) | 0.1466 (19) | |
H21A | −0.1225 | 0.4008 | 0.3848 | 0.176* | |
C22 | 0.0042 (7) | 0.4603 (2) | 0.3338 (5) | 0.185 (3) | |
H22A | 0.0504 | 0.4769 | 0.2758 | 0.222* | |
H22B | 0.0229 | 0.4788 | 0.4007 | 0.222* | |
C23 | −0.4073 (4) | 0.19738 (15) | 0.4184 (3) | 0.0865 (10) | |
H23A | −0.4616 | 0.1658 | 0.4536 | 0.130* | |
H23B | −0.4877 | 0.2125 | 0.3597 | 0.130* | |
H23C | −0.3741 | 0.2290 | 0.4687 | 0.130* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.137 (2) | 0.125 (2) | 0.169 (3) | −0.0211 (18) | 0.095 (2) | −0.0158 (19) |
O2 | 0.150 (2) | 0.117 (2) | 0.192 (3) | 0.0325 (19) | 0.089 (2) | 0.010 (2) |
O3 | 0.0746 (13) | 0.0879 (14) | 0.0814 (16) | 0.0020 (11) | 0.0246 (11) | 0.0038 (12) |
O4 | 0.0695 (11) | 0.0648 (12) | 0.0672 (13) | −0.0041 (9) | 0.0094 (10) | −0.0044 (10) |
O5 | 0.1033 (15) | 0.0669 (12) | 0.0811 (16) | 0.0004 (11) | −0.0089 (12) | −0.0086 (11) |
N1 | 0.101 (2) | 0.101 (2) | 0.104 (3) | −0.009 (2) | 0.0395 (18) | −0.020 (2) |
N2 | 0.0755 (15) | 0.0805 (16) | 0.0652 (17) | −0.0032 (14) | 0.0099 (13) | 0.0115 (13) |
N3 | 0.0721 (15) | 0.0741 (15) | 0.0598 (15) | −0.0029 (13) | 0.0117 (12) | 0.0020 (13) |
C1 | 0.0734 (19) | 0.078 (2) | 0.062 (2) | −0.0125 (16) | 0.0155 (15) | −0.0109 (16) |
C2 | 0.0724 (19) | 0.087 (2) | 0.059 (2) | −0.0156 (17) | 0.0119 (15) | 0.0052 (16) |
C3 | 0.0750 (19) | 0.0707 (18) | 0.062 (2) | −0.0079 (16) | 0.0086 (15) | 0.0091 (15) |
C4 | 0.0660 (18) | 0.0705 (18) | 0.0554 (19) | −0.0017 (15) | 0.0059 (14) | 0.0005 (14) |
C5 | 0.081 (2) | 0.074 (2) | 0.079 (2) | −0.0130 (16) | 0.0259 (16) | 0.0024 (17) |
C6 | 0.088 (2) | 0.0702 (19) | 0.090 (2) | −0.0021 (17) | 0.0284 (18) | −0.0021 (17) |
C7 | 0.0631 (16) | 0.0681 (18) | 0.0546 (18) | −0.0005 (14) | 0.0054 (14) | 0.0006 (14) |
C8 | 0.076 (2) | 0.0718 (19) | 0.066 (2) | 0.0003 (16) | 0.0053 (15) | 0.0111 (15) |
C9 | 0.087 (2) | 0.0713 (19) | 0.060 (2) | 0.0105 (17) | −0.0021 (16) | 0.0076 (16) |
C10 | 0.0692 (18) | 0.085 (2) | 0.062 (2) | 0.0134 (16) | 0.0029 (15) | −0.0009 (16) |
C11 | 0.0678 (18) | 0.0755 (19) | 0.0525 (18) | 0.0017 (16) | 0.0057 (14) | −0.0012 (15) |
C12 | 0.0667 (17) | 0.0597 (17) | 0.0546 (18) | 0.0031 (14) | 0.0049 (13) | −0.0012 (14) |
C13 | 0.0677 (18) | 0.0630 (17) | 0.063 (2) | −0.0024 (14) | 0.0185 (15) | −0.0024 (15) |
C14 | 0.0644 (17) | 0.0631 (17) | 0.075 (2) | −0.0008 (14) | 0.0223 (15) | −0.0093 (16) |
C15 | 0.103 (2) | 0.070 (2) | 0.090 (3) | 0.0054 (18) | 0.0164 (19) | −0.0001 (18) |
C16 | 0.122 (3) | 0.072 (2) | 0.121 (3) | 0.018 (2) | 0.028 (2) | 0.008 (2) |
C17 | 0.109 (3) | 0.062 (2) | 0.148 (4) | 0.004 (2) | 0.053 (3) | −0.008 (2) |
C18 | 0.100 (3) | 0.078 (2) | 0.129 (4) | −0.010 (2) | 0.036 (2) | −0.030 (2) |
C19 | 0.081 (2) | 0.073 (2) | 0.094 (3) | −0.0017 (16) | 0.0245 (17) | −0.0154 (18) |
C20 | 0.118 (3) | 0.091 (2) | 0.094 (3) | 0.032 (2) | 0.009 (2) | 0.009 (2) |
C21 | 0.200 (5) | 0.080 (3) | 0.149 (4) | 0.040 (3) | −0.017 (4) | 0.009 (3) |
C22 | 0.229 (6) | 0.094 (3) | 0.224 (6) | 0.035 (3) | −0.001 (5) | −0.011 (4) |
C23 | 0.0660 (18) | 0.119 (3) | 0.078 (2) | 0.0084 (18) | 0.0208 (16) | 0.0013 (19) |
O1—N1 | 1.213 (3) | C9—C20 | 1.506 (4) |
O2—N1 | 1.209 (4) | C10—C11 | 1.374 (4) |
O3—C11 | 1.368 (3) | C10—H10A | 0.9300 |
O3—C23 | 1.432 (3) | C11—C12 | 1.392 (4) |
O4—C13 | 1.359 (3) | C13—C14 | 1.476 (4) |
O4—C12 | 1.393 (3) | C14—C19 | 1.382 (4) |
O5—C13 | 1.200 (3) | C14—C15 | 1.385 (4) |
N1—C1 | 1.479 (4) | C15—C16 | 1.378 (4) |
N2—N3 | 1.241 (3) | C15—H15A | 0.9300 |
N2—C4 | 1.440 (3) | C16—C17 | 1.367 (5) |
N3—C7 | 1.441 (3) | C16—H16A | 0.9300 |
C1—C2 | 1.365 (4) | C17—C18 | 1.367 (5) |
C1—C6 | 1.377 (4) | C17—H17A | 0.9300 |
C2—C3 | 1.371 (4) | C18—C19 | 1.390 (4) |
C2—H2B | 0.9300 | C18—H18A | 0.9300 |
C3—C4 | 1.373 (4) | C19—H19A | 0.9300 |
C3—H3B | 0.9300 | C20—C21 | 1.417 (5) |
C4—C5 | 1.385 (4) | C20—H20A | 0.9700 |
C5—C6 | 1.366 (4) | C20—H20B | 0.9700 |
C5—H5A | 0.9300 | C21—C22 | 1.245 (5) |
C6—H6A | 0.9300 | C21—H21A | 0.9300 |
C7—C8 | 1.379 (4) | C22—H22A | 0.9300 |
C7—C12 | 1.383 (3) | C22—H22B | 0.9300 |
C8—C9 | 1.378 (4) | C23—H23A | 0.9600 |
C8—H8A | 0.9300 | C23—H23B | 0.9600 |
C9—C10 | 1.394 (4) | C23—H23C | 0.9600 |
C11—O3—C23 | 117.7 (2) | C7—C12—O4 | 120.8 (2) |
C13—O4—C12 | 117.2 (2) | C11—C12—O4 | 118.9 (2) |
O2—N1—O1 | 123.5 (3) | O5—C13—O4 | 122.0 (3) |
O2—N1—C1 | 118.5 (3) | O5—C13—C14 | 126.2 (3) |
O1—N1—C1 | 118.0 (3) | O4—C13—C14 | 111.8 (3) |
N3—N2—C4 | 114.0 (2) | C19—C14—C15 | 119.5 (3) |
N2—N3—C7 | 113.7 (2) | C19—C14—C13 | 122.6 (3) |
C2—C1—C6 | 122.5 (3) | C15—C14—C13 | 117.9 (3) |
C2—C1—N1 | 119.0 (3) | C16—C15—C14 | 120.4 (3) |
C6—C1—N1 | 118.4 (3) | C16—C15—H15A | 119.8 |
C1—C2—C3 | 118.6 (3) | C14—C15—H15A | 119.8 |
C1—C2—H2B | 120.7 | C17—C16—C15 | 119.7 (4) |
C3—C2—H2B | 120.7 | C17—C16—H16A | 120.1 |
C2—C3—C4 | 120.0 (3) | C15—C16—H16A | 120.1 |
C2—C3—H3B | 120.0 | C16—C17—C18 | 120.8 (3) |
C4—C3—H3B | 120.0 | C16—C17—H17A | 119.6 |
C3—C4—C5 | 120.7 (3) | C18—C17—H17A | 119.6 |
C3—C4—N2 | 114.8 (3) | C17—C18—C19 | 120.1 (4) |
C5—C4—N2 | 124.5 (3) | C17—C18—H18A | 120.0 |
C6—C5—C4 | 119.7 (3) | C19—C18—H18A | 120.0 |
C6—C5—H5A | 120.2 | C14—C19—C18 | 119.5 (3) |
C4—C5—H5A | 120.2 | C14—C19—H19A | 120.2 |
C5—C6—C1 | 118.5 (3) | C18—C19—H19A | 120.2 |
C5—C6—H6A | 120.7 | C21—C20—C9 | 114.9 (3) |
C1—C6—H6A | 120.7 | C21—C20—H20A | 108.5 |
C8—C7—C12 | 119.9 (3) | C9—C20—H20A | 108.5 |
C8—C7—N3 | 124.9 (3) | C21—C20—H20B | 108.5 |
C12—C7—N3 | 115.2 (2) | C9—C20—H20B | 108.5 |
C9—C8—C7 | 120.9 (3) | H20A—C20—H20B | 107.5 |
C9—C8—H8A | 119.5 | C22—C21—C20 | 134.4 (6) |
C7—C8—H8A | 119.5 | C22—C21—H21A | 112.8 |
C8—C9—C10 | 118.5 (3) | C20—C21—H21A | 112.8 |
C8—C9—C20 | 120.7 (3) | C21—C22—H22A | 120.0 |
C10—C9—C20 | 120.8 (3) | C21—C22—H22B | 120.0 |
C11—C10—C9 | 121.5 (3) | H22A—C22—H22B | 120.0 |
C11—C10—H10A | 119.3 | O3—C23—H23A | 109.5 |
C9—C10—H10A | 119.3 | O3—C23—H23B | 109.5 |
O3—C11—C10 | 125.7 (3) | H23A—C23—H23B | 109.5 |
O3—C11—C12 | 115.3 (2) | O3—C23—H23C | 109.5 |
C10—C11—C12 | 119.0 (3) | H23A—C23—H23C | 109.5 |
C7—C12—C11 | 120.2 (2) | H23B—C23—H23C | 109.5 |
C4—N2—N3—C7 | 179.6 (2) | C9—C10—C11—C12 | 0.0 (4) |
O2—N1—C1—C2 | 177.5 (3) | C8—C7—C12—C11 | −0.8 (4) |
O1—N1—C1—C2 | −4.1 (4) | N3—C7—C12—C11 | 179.8 (2) |
O2—N1—C1—C6 | −2.5 (5) | C8—C7—C12—O4 | 174.9 (2) |
O1—N1—C1—C6 | 175.8 (3) | N3—C7—C12—O4 | −4.5 (3) |
C6—C1—C2—C3 | −0.2 (4) | O3—C11—C12—C7 | −178.4 (2) |
N1—C1—C2—C3 | 179.7 (2) | C10—C11—C12—C7 | 1.1 (4) |
C1—C2—C3—C4 | −0.9 (4) | O3—C11—C12—O4 | 5.8 (3) |
C2—C3—C4—C5 | 1.0 (4) | C10—C11—C12—O4 | −174.7 (2) |
C2—C3—C4—N2 | −179.8 (2) | C13—O4—C12—C7 | 87.8 (3) |
N3—N2—C4—C3 | 178.9 (2) | C13—O4—C12—C11 | −96.5 (3) |
N3—N2—C4—C5 | −1.9 (4) | C12—O4—C13—O5 | 0.4 (4) |
C3—C4—C5—C6 | −0.1 (4) | C12—O4—C13—C14 | 180.0 (2) |
N2—C4—C5—C6 | −179.3 (2) | O5—C13—C14—C19 | −170.8 (3) |
C4—C5—C6—C1 | −0.9 (4) | O4—C13—C14—C19 | 9.7 (4) |
C2—C1—C6—C5 | 1.0 (4) | O5—C13—C14—C15 | 11.8 (4) |
N1—C1—C6—C5 | −178.9 (3) | O4—C13—C14—C15 | −167.7 (2) |
N2—N3—C7—C8 | −1.6 (4) | C19—C14—C15—C16 | −1.4 (4) |
N2—N3—C7—C12 | 177.8 (2) | C13—C14—C15—C16 | 176.1 (3) |
C12—C7—C8—C9 | −0.6 (4) | C14—C15—C16—C17 | 0.7 (5) |
N3—C7—C8—C9 | 178.8 (2) | C15—C16—C17—C18 | 1.0 (5) |
C7—C8—C9—C10 | 1.6 (4) | C16—C17—C18—C19 | −2.0 (5) |
C7—C8—C9—C20 | −177.9 (3) | C15—C14—C19—C18 | 0.4 (4) |
C8—C9—C10—C11 | −1.3 (4) | C13—C14—C19—C18 | −176.9 (3) |
C20—C9—C10—C11 | 178.2 (3) | C17—C18—C19—C14 | 1.3 (5) |
C23—O3—C11—C10 | 1.3 (4) | C8—C9—C20—C21 | −99.4 (4) |
C23—O3—C11—C12 | −179.2 (2) | C10—C9—C20—C21 | 81.2 (4) |
C9—C10—C11—O3 | 179.4 (2) | C9—C20—C21—C22 | 127.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···O1 | 0.93 | 2.43 | 2.712 (3) | 98 |
C6—H6A···O2 | 0.93 | 2.43 | 2.715 (3) | 98 |
C15—H15A···O5 | 0.93 | 2.57 | 2.854 (1) | 98 |
C19—H19A···O4 | 0.93 | 2.43 | 2.735 (1) | 99 |
C16—H16A···O3i | 0.93 | 2.67 | 3.356 (2) | 131 |
C23—H23A···O5ii | 0.96 | 2.72 | 3.400 (4) | 129 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C23H19N3O5 |
Mr | 417.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.7564 (1), 22.3441 (5), 12.5552 (2) |
β (°) | 97.766 (1) |
V (Å3) | 2155.98 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.32 × 0.24 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15921, 5166, 1920 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.197, 0.96 |
No. of reflections | 5166 |
No. of parameters | 281 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.20 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1996), SHELXTL and PARST (Nardelli, 1995).
O1—N1 | 1.213 (3) | N2—N3 | 1.241 (3) |
O2—N1 | 1.209 (4) | N2—C4 | 1.440 (3) |
N1—C1 | 1.479 (4) | N3—C7 | 1.441 (3) |
C11—O3—C23 | 117.7 (2) | N2—N3—C7 | 113.7 (2) |
O2—N1—O1 | 123.5 (3) | O5—C13—O4 | 122.0 (3) |
N3—N2—C4 | 114.0 (2) | ||
N3—N2—C4—C3 | 178.9 (2) | C23—O3—C11—C10 | 1.3 (4) |
N3—N2—C4—C5 | −1.9 (4) | C12—O4—C13—O5 | 0.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···O1 | 0.93 | 2.43 | 2.712 (3) | 97.7 |
C6—H6A···O2 | 0.93 | 2.43 | 2.715 (3) | 97.9 |
C15—H15A···O5 | 0.93 | 2.57 | 2.854 (1) | 98.0 |
C19—H19A···O4 | 0.93 | 2.43 | 2.735 (1) | 98.8 |
C16—H16A···O3i | 0.93 | 2.67 | 3.356 (2) | 131.1 |
C23—H23A···O5ii | 0.96 | 2.72 | 3.400 (4) | 128.6 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y, z. |
The crystal and molecular structures of the title compound, (I), were investigated in order to determine the conformation, crystal packing and also to confirm the stereochemistry. In the molecule, bond lengths and angles are very similar to the structures of azo compounds studied previously (Işık et al., 1997; Işık, Aygün, Kocaokutgen, Tahir et al., 1998; Işık, Aygün, Kocaokutgen & Tahir, 1998).
The numbering scheme and a displacement ellipsoid plot of (I) are shown in Fig. 1. In the azo frame, the average C—N bond length is 1.441 (3) Å, that indicates the single-bond character. The C—NO2 bond length is 1.479 (4) Å, which is similar to the observed values in the literature (Zhu et al., 1996; Zhang et al., 1998). The N2=N3 bond length of 1.241 (3) Å is typical for a double bond. The angles C4—N2—N3 and N2—N3—C7 are 114.0 (2) and 113.7 (2)°, respectively. The torsion angles about the C—N bond [N3—N2—C4—C3 = 178.9 (2) and N3—N2—C4—C5 = −1.9 (4)°] are comparable with trans azo compounds. The three phenyl rings are planar within experimental error and the largest deviation of −0.010 (2) Å is at the C18 atom of the C14—C19 ring. While the twist angle of the nitro group relative to the phenyl ring is 3.7 (1)°, C1—C6 and C7—C12 rings in the azobenzene frame are twisted by 1.83 (2) and 1.68 (2)° out of the azo group plane, respectively. These results show that the azo group moiety is almost planar. The C7—C12 ring and the other groups those are adjacent to the C7—C12 ring, except the methoxy group, are not coplanar. Also, dihedral angles between the C14—C19 ring and the C1—C6, and C7—C12 rings are 97.7 (1) and 96.2 (1)°, respectively.
The compound has four intramolecular C—H···O contacts. Two of these are C2—H2B···O1 and C6—H6A···O2 which maintain the coplanarity of the phenyl ring and the nitro group. The other two intramolecular hydrogen bonds, C15—H15A···O5 and C19—H19A···O4, are located between the unsubstituted phenyl ring and the benzoyloxy group. Also, the crystal packing involves two C—H···O intermolecular hydrogen bonds. Details of these interactions are shown in Table 2.
Displacement parameters of C20, C21 and C22 atoms of the allyl group are larger than other atoms. This behaviour may be due to considerable freedom of movement of the group in the crystal. Also, this accounts for the apparent shortening of the C21—C22 bond length [1.245 (5) Å].