Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029338/is6123sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029338/is6123Isup2.hkl |
CCDC reference: 287610
To a solution of cinnamaldehyde (13.2 g, 0.1 ml) in acetic anhydride was added concentrated nitric acid (3.6 ml) and acetic acid (12.0 ml) over a period of 3 h under 278 K. The reaction mixture was allowed to stand for 2 d at room temperature. 20% HCl was added and o-nitrocinnamaldehyde was obtained as a yellow solid. To a solution of o-nitrocinnamaldehyde (0.25 g, 1.4 mmol) in water (20 ml) was added a solution of o-aminophenol (0.15 g, 1.4 mmol) in ethanol (20 ml). The mixture was heated under reflux for 4 h, yielding quantities of precipitate. Yellow single crystals suitable for X-ray diffraction study were obtained by slow evaporation of a ethanol solution over a period of 3 d.
All H atoms were located in difference Fourier maps and constrained to ride on their parent atoms, with C—H = 0.93 Å and O—H = 0.82 Å, and with Uiso(H) = 1.2 Ueq(C) and 1.5Ueq(O).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C15H12N2O3 | F(000) = 1120 |
Mr = 268.27 | Dx = 1.332 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 22.654 (3) Å | Cell parameters from 2347 reflections |
b = 7.5464 (10) Å | θ = 2.6–25.7° |
c = 18.816 (2) Å | µ = 0.10 mm−1 |
β = 123.692 (2)° | T = 293 K |
V = 2676.5 (6) Å3 | Block, yellow |
Z = 8 | 0.38 × 0.22 × 0.14 mm |
Siemens SMART 1000 CCD area-detector diffractometer | 2635 independent reflections |
Radiation source: fine-focus sealed tube | 2111 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 8.33 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
ω scans | h = −15→27 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→9 |
Tmin = 0.965, Tmax = 0.987 | l = −23→22 |
7282 measured 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0584P)2 + 1.5459P] where P = (Fo2 + 2Fc2)/3 |
2635 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C15H12N2O3 | V = 2676.5 (6) Å3 |
Mr = 268.27 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 22.654 (3) Å | µ = 0.10 mm−1 |
b = 7.5464 (10) Å | T = 293 K |
c = 18.816 (2) Å | 0.38 × 0.22 × 0.14 mm |
β = 123.692 (2)° |
Siemens SMART 1000 CCD area-detector diffractometer | 2635 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2111 reflections with I > 2σ(I) |
Tmin = 0.965, Tmax = 0.987 | Rint = 0.022 |
7282 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.29 e Å−3 |
2635 reflections | Δρmin = −0.28 e Å−3 |
181 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 | −0.07054 (13) | −0.3837 (3) | −0.25409 (12) | 0.1329 (10) | |
O2 | −0.01401 (10) | −0.1927 (2) | −0.15485 (11) | 0.0980 (7) | |
O3 | 0.23510 (7) | 0.28984 (17) | 0.22499 (8) | 0.0516 (4) | |
H3A | 0.2397 | 0.3800 | 0.2520 | 0.077* | |
N1 | −0.02857 (10) | −0.3445 (2) | −0.17952 (11) | 0.0737 (6) | |
N2 | 0.23660 (8) | 0.00307 (17) | 0.14026 (9) | 0.0402 (3) | |
C1 | 0.00561 (10) | −0.4880 (2) | −0.11663 (12) | 0.0494 (5) | |
C2 | −0.03180 (11) | −0.6444 (3) | −0.13574 (14) | 0.0591 (5) | |
H2B | −0.0745 | −0.6593 | −0.1883 | 0.071* | |
C3 | −0.00529 (12) | −0.7775 (3) | −0.07628 (15) | 0.0616 (6) | |
H3B | −0.0300 | −0.8836 | −0.0882 | 0.074* | |
C4 | 0.05816 (12) | −0.7537 (3) | 0.00132 (15) | 0.0595 (5) | |
H4A | 0.0757 | −0.8429 | 0.0423 | 0.071* | |
C5 | 0.09587 (11) | −0.5978 (2) | 0.01842 (12) | 0.0506 (5) | |
H5A | 0.1390 | −0.5851 | 0.0706 | 0.061* | |
C6 | 0.07124 (9) | −0.4598 (2) | −0.04000 (11) | 0.0427 (4) | |
C7 | 0.11460 (10) | −0.3009 (2) | −0.02192 (11) | 0.0463 (4) | |
H7A | 0.1108 | −0.2436 | −0.0681 | 0.056* | |
C8 | 0.15892 (10) | −0.2323 (2) | 0.05506 (11) | 0.0459 (4) | |
H8A | 0.1637 | −0.2875 | 0.1022 | 0.055* | |
C9 | 0.19985 (10) | −0.0750 (2) | 0.06799 (11) | 0.0442 (4) | |
H9A | 0.1995 | −0.0285 | 0.0220 | 0.053* | |
C10 | 0.27698 (9) | 0.1542 (2) | 0.14842 (9) | 0.0367 (4) | |
C11 | 0.27845 (9) | 0.2986 (2) | 0.19625 (10) | 0.0386 (4) | |
C12 | 0.32100 (10) | 0.4434 (2) | 0.20983 (11) | 0.0465 (4) | |
H12A | 0.3213 | 0.5402 | 0.2407 | 0.056* | |
C13 | 0.36290 (11) | 0.4447 (3) | 0.17777 (12) | 0.0540 (5) | |
H13A | 0.3921 | 0.5413 | 0.1881 | 0.065* | |
C14 | 0.36174 (11) | 0.3038 (3) | 0.13052 (13) | 0.0534 (5) | |
H14A | 0.3899 | 0.3056 | 0.1087 | 0.064* | |
C15 | 0.31875 (10) | 0.1601 (2) | 0.11559 (11) | 0.0453 (4) | |
H15A | 0.3177 | 0.0658 | 0.0831 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1347 (18) | 0.0890 (14) | 0.0603 (11) | −0.0286 (13) | −0.0174 (12) | 0.0035 (10) |
O2 | 0.1024 (14) | 0.0484 (9) | 0.0769 (12) | 0.0056 (9) | 0.0085 (10) | 0.0037 (8) |
O3 | 0.0602 (8) | 0.0528 (7) | 0.0505 (8) | −0.0083 (6) | 0.0361 (7) | −0.0128 (6) |
N1 | 0.0656 (12) | 0.0568 (11) | 0.0512 (11) | −0.0058 (9) | 0.0027 (9) | −0.0007 (9) |
N2 | 0.0439 (8) | 0.0380 (7) | 0.0360 (7) | −0.0024 (6) | 0.0205 (7) | −0.0026 (6) |
C1 | 0.0491 (11) | 0.0436 (10) | 0.0464 (10) | −0.0024 (8) | 0.0208 (9) | −0.0079 (8) |
C2 | 0.0512 (12) | 0.0518 (11) | 0.0663 (13) | −0.0100 (9) | 0.0276 (11) | −0.0163 (10) |
C3 | 0.0668 (14) | 0.0429 (10) | 0.0879 (16) | −0.0114 (10) | 0.0508 (14) | −0.0114 (10) |
C4 | 0.0758 (15) | 0.0442 (10) | 0.0739 (14) | 0.0062 (10) | 0.0511 (13) | 0.0080 (10) |
C5 | 0.0525 (11) | 0.0470 (10) | 0.0477 (10) | 0.0026 (9) | 0.0250 (9) | −0.0004 (8) |
C6 | 0.0453 (10) | 0.0387 (9) | 0.0427 (9) | −0.0011 (7) | 0.0236 (8) | −0.0059 (7) |
C7 | 0.0518 (11) | 0.0419 (9) | 0.0395 (9) | −0.0033 (8) | 0.0218 (9) | −0.0019 (8) |
C8 | 0.0503 (11) | 0.0435 (9) | 0.0396 (9) | −0.0040 (8) | 0.0221 (9) | −0.0027 (7) |
C9 | 0.0485 (10) | 0.0448 (9) | 0.0359 (9) | −0.0027 (8) | 0.0214 (8) | −0.0004 (7) |
C10 | 0.0386 (9) | 0.0360 (8) | 0.0286 (8) | 0.0002 (7) | 0.0143 (7) | 0.0027 (6) |
C11 | 0.0405 (9) | 0.0404 (9) | 0.0305 (8) | 0.0028 (7) | 0.0171 (7) | 0.0027 (7) |
C12 | 0.0554 (11) | 0.0379 (9) | 0.0411 (10) | −0.0037 (8) | 0.0235 (9) | −0.0022 (7) |
C13 | 0.0599 (12) | 0.0476 (10) | 0.0530 (11) | −0.0150 (9) | 0.0304 (10) | −0.0010 (9) |
C14 | 0.0569 (12) | 0.0579 (11) | 0.0548 (11) | −0.0051 (9) | 0.0369 (10) | 0.0009 (9) |
C15 | 0.0510 (11) | 0.0449 (9) | 0.0423 (10) | −0.0002 (8) | 0.0273 (9) | −0.0036 (8) |
O1—N1 | 1.217 (2) | C6—C7 | 1.466 (2) |
O2—N1 | 1.211 (2) | C7—C8 | 1.327 (2) |
O3—C11 | 1.360 (2) | C7—H7A | 0.9300 |
O3—H3A | 0.8200 | C8—C9 | 1.442 (2) |
N1—C1 | 1.468 (3) | C8—H8A | 0.9300 |
N2—C9 | 1.278 (2) | C9—H9A | 0.9300 |
N2—C10 | 1.416 (2) | C10—C15 | 1.388 (2) |
C1—C2 | 1.380 (3) | C10—C11 | 1.402 (2) |
C1—C6 | 1.399 (3) | C11—C12 | 1.384 (2) |
C2—C3 | 1.369 (3) | C12—C13 | 1.379 (3) |
C2—H2B | 0.9300 | C12—H12A | 0.9300 |
C3—C4 | 1.379 (3) | C13—C14 | 1.377 (3) |
C3—H3B | 0.9300 | C13—H13A | 0.9300 |
C4—C5 | 1.383 (3) | C14—C15 | 1.379 (3) |
C4—H4A | 0.9300 | C14—H14A | 0.9300 |
C5—C6 | 1.387 (2) | C15—H15A | 0.9300 |
C5—H5A | 0.9300 | ||
C11—O3—H3A | 109.5 | C6—C7—H7A | 117.4 |
O2—N1—O1 | 123.0 (2) | C7—C8—C9 | 122.13 (17) |
O2—N1—C1 | 118.61 (17) | C7—C8—H8A | 118.9 |
O1—N1—C1 | 118.39 (19) | C9—C8—H8A | 118.9 |
C9—N2—C10 | 119.13 (14) | N2—C9—C8 | 122.51 (16) |
C2—C1—C6 | 123.14 (18) | N2—C9—H9A | 118.7 |
C2—C1—N1 | 116.61 (17) | C8—C9—H9A | 118.7 |
C6—C1—N1 | 120.18 (16) | C15—C10—C11 | 118.77 (15) |
C3—C2—C1 | 119.14 (19) | C15—C10—N2 | 122.44 (14) |
C3—C2—H2B | 120.4 | C11—C10—N2 | 118.65 (14) |
C1—C2—H2B | 120.4 | O3—C11—C12 | 123.19 (15) |
C2—C3—C4 | 119.79 (18) | O3—C11—C10 | 116.88 (14) |
C2—C3—H3B | 120.1 | C12—C11—C10 | 119.90 (15) |
C4—C3—H3B | 120.1 | C13—C12—C11 | 120.18 (16) |
C3—C4—C5 | 120.23 (19) | C13—C12—H12A | 119.9 |
C3—C4—H4A | 119.9 | C11—C12—H12A | 119.9 |
C5—C4—H4A | 119.9 | C14—C13—C12 | 120.40 (17) |
C4—C5—C6 | 121.96 (19) | C14—C13—H13A | 119.8 |
C4—C5—H5A | 119.0 | C12—C13—H13A | 119.8 |
C6—C5—H5A | 119.0 | C13—C14—C15 | 119.84 (17) |
C5—C6—C1 | 115.67 (16) | C13—C14—H14A | 120.1 |
C5—C6—C7 | 120.47 (16) | C15—C14—H14A | 120.1 |
C1—C6—C7 | 123.77 (16) | C14—C15—C10 | 120.89 (16) |
C8—C7—C6 | 125.20 (17) | C14—C15—H15A | 119.6 |
C8—C7—H7A | 117.4 | C10—C15—H15A | 119.6 |
O2—N1—C1—C2 | 151.9 (2) | C6—C7—C8—C9 | −179.85 (17) |
O1—N1—C1—C2 | −27.8 (3) | C10—N2—C9—C8 | 178.23 (15) |
O2—N1—C1—C6 | −25.1 (3) | C7—C8—C9—N2 | 172.11 (18) |
O1—N1—C1—C6 | 155.2 (2) | C9—N2—C10—C15 | −45.4 (2) |
C6—C1—C2—C3 | 2.4 (3) | C9—N2—C10—C11 | 138.87 (17) |
N1—C1—C2—C3 | −174.52 (19) | C15—C10—C11—O3 | 178.01 (14) |
C1—C2—C3—C4 | −0.2 (3) | N2—C10—C11—O3 | −6.1 (2) |
C2—C3—C4—C5 | −1.6 (3) | C15—C10—C11—C12 | 0.1 (2) |
C3—C4—C5—C6 | 1.3 (3) | N2—C10—C11—C12 | 175.92 (15) |
C4—C5—C6—C1 | 0.7 (3) | O3—C11—C12—C13 | −179.00 (16) |
C4—C5—C6—C7 | −176.22 (17) | C10—C11—C12—C13 | −1.2 (3) |
C2—C1—C6—C5 | −2.6 (3) | C11—C12—C13—C14 | 1.4 (3) |
N1—C1—C6—C5 | 174.21 (17) | C12—C13—C14—C15 | −0.4 (3) |
C2—C1—C6—C7 | 174.24 (18) | C13—C14—C15—C10 | −0.7 (3) |
N1—C1—C6—C7 | −9.0 (3) | C11—C10—C15—C14 | 0.9 (2) |
C5—C6—C7—C8 | −32.7 (3) | N2—C10—C15—C14 | −174.80 (16) |
C1—C6—C7—C8 | 150.64 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N2i | 0.82 | 2.01 | 2.761 (2) | 151 |
C7—H7A···O2 | 0.93 | 2.38 | 2.707 (3) | 100 |
C12—H12A···O3i | 0.93 | 2.55 | 3.418 (2) | 155 |
C2—H2B···Cg2ii | 0.93 | 2.69 | 3.591 (2) | 162 |
C14—H14A···Cg1iii | 0.93 | 2.80 | 3.628 (3) | 149 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y−1/2, z−1/2; (iii) −x+1/2, −y−1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H12N2O3 |
Mr | 268.27 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 22.654 (3), 7.5464 (10), 18.816 (2) |
β (°) | 123.692 (2) |
V (Å3) | 2676.5 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.38 × 0.22 × 0.14 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.965, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7282, 2635, 2111 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.127, 1.03 |
No. of reflections | 2635 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.28 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
O1—N1 | 1.217 (2) | N2—C9 | 1.278 (2) |
O2—N1 | 1.211 (2) | N2—C10 | 1.416 (2) |
O3—C11 | 1.360 (2) | C7—C8 | 1.327 (2) |
N1—C1 | 1.468 (3) | C8—C9 | 1.442 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···N2i | 0.82 | 2.01 | 2.761 (2) | 151 |
C7—H7A···O2 | 0.93 | 2.38 | 2.707 (3) | 100 |
C12—H12A···O3i | 0.93 | 2.55 | 3.418 (2) | 155 |
C2—H2B···Cg2ii | 0.93 | 2.69 | 3.591 (2) | 162 |
C14—H14A···Cg1iii | 0.93 | 2.80 | 3.628 (3) | 149 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x−1/2, −y−1/2, z−1/2; (iii) −x+1/2, −y−1/2, −z. |
For several decades, much attention has been paid to the search for new nonlinear optical (NLO) materials, because these materials have been widely applied or have great potentials in modern laser technology, optical communication and information storage (Long, 1995). The Schiff base compounds are new organic NLO materials, which have been investigated during recent years because many of them have NLO behavior and are easy to synthesize (Unver et al., 2004; Jalali-Heravi et al., 2000). We have recently prepared the novel push–pull Schiff base, (I), containing benzene rings, and C=N and C=C bonds. We report here its crystal structure (Fig. 1).
The bond lengths and angles are within normal ranges (Allen et al., 1987). The bonds between the two benzene rings show a characteristic intermediate length between single and double bonds because of the conjugated C═C and C═N double bonds (Table 1). The whole molecule is non-planar, with a dihedral angle of 83.0 (1)° between the two benzene rings. There exists an intramolecular C—H···O hydrogen bond (Table 2), forming a six-membered ring. In the crystal structure, molecules are linked into a ribbon along the b axis by weak C—H···O and O—H···N intermolecular hydrogen bonds (Fig. 2). The packing is further stabilized by C—H···π and π–π interactions involving the benzene rings [Cg1···Cg1(−x, −1 − y, −z) = 3.711 (2) Å, where Cg1 is the centroid of the C1–C6 ring].