Acta Cryst. (2009). E65, o963 [ doi:10.1107/S160053680901157X ]
A new tetradentate unsymmetrical Schiff base, C15H10N4O, has been synthesized from 4,5-dicyano-o-phenylenediamine and o-vanillin in refluxing ethanol. The dihedral angle between the two benzene rings is 39.0 (1)°. There are intramolecular O-H
N and weak intermolecular N-HO and N-HN interactions.
(I) was prepared according to the method reported in the literature (Kannappan et al., 2005). 4,5-dicyano-o-phenylenediamine (2.16 g, 0.02 mol) was added to a stirred ethanol solution of O-vanillin (3.04 g, 0.02 mol (10 ml). The reaction mixture was stirred about 3 h and then the mixture was allowed to stand at room temperature for about two days. Yellow cystals suitable for X-ray diffraction analysis were then collected with a yield of 60%.
The H atoms of the amino group were located from difference density maps and were refined with distance restraints of d(N–H) = 0.93 (2) Å. H atoms bound to C and O atoms were visible in difference maps and were placed using the HFIX commands in SHELXL97. All H atoms were allowed for as riding atoms (C–H 0.97 Å, O–H 0.86 Å) with the constraint Uiso(H) = 1.5Ueq(methyl carrier), 1.5Ueq(O) and 1.2Ueq(carrier) for all other H atoms.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./fl2237fig1thm.gif)
| Fig. 1. A view of the structure of (I), showing the atmoic numbering scheme and 30% probability displacement ellipsoids. |
| C15H10N4O | F(000) = 544 |
| Mr = 262.27 | Dx = 1.387 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1728 reflections |
| a = 14.0158 (15) Å | θ = 2.2–26.3° |
| b = 12.3650 (13) Å | µ = 0.09 mm−1 |
| c = 7.3557 (8) Å | T = 273 K |
| β = 99.904 (2)° | Block, yellow |
| V = 1255.8 (2) Å3 | 0.12 × 0.10 × 0.08 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 2838 independent reflections |
| Radiation source: fine-focus sealed tube | 1770 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| φ and ω scans | θmax = 27.5°, θmin = 1.5° |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −18→15 |
| Tmin = 0.989, Tmax = 0.993 | k = −16→11 |
| 7234 measured reflections | l = −9→9 |
| 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.170 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.105P)2] where P = (Fo2 + 2Fc2)/3 |
| 2838 reflections | (Δ/σ)max = 0.001 |
| 187 parameters | Δρmax = 0.14 e Å−3 |
| 2 restraints | Δρmin = −0.16 e Å−3 |
| C15H10N4O | V = 1255.8 (2) Å3 |
| Mr = 262.27 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 14.0158 (15) Å | µ = 0.09 mm−1 |
| b = 12.3650 (13) Å | T = 273 K |
| c = 7.3557 (8) Å | 0.12 × 0.10 × 0.08 mm |
| β = 99.904 (2)° |
| Bruker APEXII CCD area-detector diffractometer | 2838 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1770 reflections with I > 2σ(I) |
| Tmin = 0.989, Tmax = 0.993 | Rint = 0.027 |
| 7234 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.046 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.170 | Δρmax = 0.14 e Å−3 |
| S = 1.00 | Δρmin = −0.16 e Å−3 |
| 2838 reflections | Absolute structure: ? |
| 187 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
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 | ||
| C1 | 0.91817 (12) | 0.53191 (15) | 0.1796 (2) | 0.0451 (5) | |
| H1 | 0.9143 | 0.4649 | 0.1213 | 0.054* | |
| C2 | 0.75504 (12) | 0.55664 (15) | 0.0486 (2) | 0.0447 (5) | |
| C3 | 0.72462 (12) | 0.45035 (16) | 0.0422 (3) | 0.0467 (5) | |
| H3 | 0.7640 | 0.3982 | 0.1084 | 0.056* | |
| C4 | 1.01931 (14) | 0.66149 (16) | 0.3888 (3) | 0.0495 (5) | |
| C5 | 0.60770 (13) | 0.60523 (16) | −0.1573 (3) | 0.0513 (5) | |
| H5 | 0.5687 | 0.6568 | −0.2258 | 0.062* | |
| C6 | 0.48595 (14) | 0.46643 (17) | −0.2707 (3) | 0.0517 (5) | |
| C7 | 1.00930 (12) | 0.56357 (15) | 0.2900 (2) | 0.0433 (5) | |
| C8 | 0.57855 (12) | 0.49920 (16) | −0.1632 (3) | 0.0478 (5) | |
| C9 | 0.63646 (13) | 0.41989 (15) | −0.0612 (3) | 0.0487 (5) | |
| C10 | 0.69528 (13) | 0.63652 (15) | −0.0496 (3) | 0.0491 (5) | |
| C11 | 0.60376 (14) | 0.30994 (18) | −0.0585 (3) | 0.0585 (6) | |
| C12 | 1.09021 (14) | 0.49709 (18) | 0.2966 (3) | 0.0551 (5) | |
| H12 | 1.0840 | 0.4315 | 0.2338 | 0.066* | |
| C13 | 1.10904 (16) | 0.69001 (19) | 0.4891 (3) | 0.0629 (6) | |
| H13 | 1.1160 | 0.7542 | 0.5559 | 0.075* | |
| C14 | 1.18721 (16) | 0.6233 (2) | 0.4895 (3) | 0.0685 (7) | |
| H14 | 1.2472 | 0.6437 | 0.5554 | 0.082* | |
| C15 | 1.17898 (14) | 0.5268 (2) | 0.3944 (3) | 0.0671 (7) | |
| H15 | 1.2327 | 0.4824 | 0.3962 | 0.080* | |
| N1 | 0.57748 (15) | 0.22349 (18) | −0.0536 (3) | 0.0888 (7) | |
| N2 | 0.41430 (13) | 0.43718 (16) | −0.3475 (3) | 0.0680 (6) | |
| N3 | 0.72491 (14) | 0.74135 (15) | −0.0435 (3) | 0.0700 (6) | |
| N4 | 0.84233 (10) | 0.59191 (12) | 0.1583 (2) | 0.0462 (4) | |
| O1 | 0.94357 (11) | 0.72904 (11) | 0.3901 (2) | 0.0692 (5) | |
| H1A | 0.8950 | 0.7034 | 0.3268 | 0.104* | |
| H1B | 0.6802 (13) | 0.7949 (13) | −0.087 (3) | 0.080* | |
| H1C | 0.7813 (10) | 0.7570 (18) | 0.039 (3) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0428 (10) | 0.0454 (10) | 0.0451 (10) | −0.0030 (8) | 0.0018 (8) | 0.0023 (8) |
| C2 | 0.0359 (9) | 0.0493 (11) | 0.0464 (10) | −0.0008 (8) | 0.0002 (8) | −0.0008 (8) |
| C3 | 0.0373 (10) | 0.0505 (11) | 0.0491 (11) | 0.0030 (8) | −0.0015 (8) | 0.0021 (8) |
| C4 | 0.0475 (11) | 0.0520 (11) | 0.0461 (11) | −0.0053 (9) | 0.0000 (8) | 0.0062 (9) |
| C5 | 0.0389 (10) | 0.0566 (12) | 0.0540 (12) | 0.0045 (9) | −0.0047 (8) | 0.0050 (9) |
| C6 | 0.0411 (11) | 0.0574 (12) | 0.0544 (12) | 0.0012 (9) | 0.0019 (9) | −0.0047 (9) |
| C7 | 0.0367 (10) | 0.0496 (11) | 0.0412 (10) | −0.0016 (8) | −0.0003 (7) | 0.0078 (8) |
| C8 | 0.0355 (10) | 0.0589 (12) | 0.0464 (11) | 0.0001 (8) | −0.0006 (8) | −0.0024 (8) |
| C9 | 0.0391 (10) | 0.0527 (12) | 0.0522 (11) | −0.0018 (8) | 0.0019 (8) | −0.0026 (8) |
| C10 | 0.0408 (10) | 0.0495 (11) | 0.0539 (11) | 0.0007 (8) | −0.0004 (8) | 0.0031 (9) |
| C11 | 0.0426 (11) | 0.0556 (13) | 0.0708 (15) | −0.0043 (10) | −0.0088 (10) | −0.0018 (10) |
| C12 | 0.0479 (11) | 0.0643 (13) | 0.0514 (12) | 0.0038 (9) | 0.0036 (9) | 0.0068 (9) |
| C13 | 0.0586 (13) | 0.0691 (14) | 0.0556 (13) | −0.0205 (11) | −0.0052 (10) | 0.0022 (10) |
| C14 | 0.0441 (12) | 0.0998 (19) | 0.0557 (13) | −0.0192 (12) | −0.0083 (10) | 0.0163 (13) |
| C15 | 0.0405 (11) | 0.0969 (19) | 0.0615 (14) | 0.0076 (11) | 0.0022 (10) | 0.0150 (12) |
| N1 | 0.0665 (13) | 0.0643 (14) | 0.124 (2) | −0.0132 (11) | −0.0155 (12) | 0.0018 (12) |
| N2 | 0.0467 (10) | 0.0788 (14) | 0.0724 (13) | −0.0042 (9) | −0.0071 (9) | −0.0107 (10) |
| N3 | 0.0556 (11) | 0.0517 (11) | 0.0917 (15) | −0.0012 (9) | −0.0185 (10) | 0.0126 (10) |
| N4 | 0.0375 (8) | 0.0481 (9) | 0.0490 (9) | 0.0002 (7) | −0.0036 (7) | 0.0033 (7) |
| O1 | 0.0627 (10) | 0.0562 (9) | 0.0816 (11) | 0.0064 (7) | −0.0076 (8) | −0.0126 (8) |
| C1—N4 | 1.283 (2) | C7—C12 | 1.395 (3) |
| C1—C7 | 1.445 (2) | C8—C9 | 1.405 (3) |
| C1—H1 | 0.9300 | C9—C11 | 1.436 (3) |
| C2—C3 | 1.380 (3) | C10—N3 | 1.360 (3) |
| C2—C10 | 1.411 (3) | C11—N1 | 1.133 (3) |
| C2—N4 | 1.414 (2) | C12—C15 | 1.376 (3) |
| C3—C9 | 1.387 (2) | C12—H12 | 0.9300 |
| C3—H3 | 0.9300 | C13—C14 | 1.371 (3) |
| C4—O1 | 1.352 (2) | C13—H13 | 0.9300 |
| C4—C13 | 1.390 (3) | C14—C15 | 1.378 (3) |
| C4—C7 | 1.407 (3) | C14—H14 | 0.9300 |
| C5—C8 | 1.372 (3) | C15—H15 | 0.9300 |
| C5—C10 | 1.396 (3) | N3—H1B | 0.930 (18) |
| C5—H5 | 0.9300 | N3—H1C | 0.930 (19) |
| C6—N2 | 1.124 (2) | O1—H1A | 0.8200 |
| C6—C8 | 1.456 (2) | ||
| N4—C1—C7 | 123.06 (17) | C3—C9—C11 | 120.39 (17) |
| N4—C1—H1 | 118.5 | C8—C9—C11 | 120.79 (16) |
| C7—C1—H1 | 118.5 | N3—C10—C5 | 121.11 (18) |
| C3—C2—C10 | 119.77 (16) | N3—C10—C2 | 119.97 (17) |
| C3—C2—N4 | 123.04 (16) | C5—C10—C2 | 118.88 (17) |
| C10—C2—N4 | 117.10 (16) | N1—C11—C9 | 178.9 (3) |
| C2—C3—C9 | 121.21 (17) | C15—C12—C7 | 121.2 (2) |
| C2—C3—H3 | 119.4 | C15—C12—H12 | 119.4 |
| C9—C3—H3 | 119.4 | C7—C12—H12 | 119.4 |
| O1—C4—C13 | 118.65 (19) | C14—C13—C4 | 119.9 (2) |
| O1—C4—C7 | 121.79 (16) | C14—C13—H13 | 120.1 |
| C13—C4—C7 | 119.57 (19) | C4—C13—H13 | 120.1 |
| C8—C5—C10 | 120.72 (18) | C13—C14—C15 | 121.5 (2) |
| C8—C5—H5 | 119.6 | C13—C14—H14 | 119.2 |
| C10—C5—H5 | 119.6 | C15—C14—H14 | 119.2 |
| N2—C6—C8 | 176.6 (2) | C12—C15—C14 | 119.1 (2) |
| C12—C7—C4 | 118.76 (17) | C12—C15—H15 | 120.5 |
| C12—C7—C1 | 119.65 (18) | C14—C15—H15 | 120.5 |
| C4—C7—C1 | 121.57 (17) | C10—N3—H1B | 118.9 (14) |
| C5—C8—C9 | 120.58 (16) | C10—N3—H1C | 116.1 (14) |
| C5—C8—C6 | 121.05 (17) | H1B—N3—H1C | 122 (2) |
| C9—C8—C6 | 118.34 (17) | C1—N4—C2 | 120.57 (16) |
| C3—C9—C8 | 118.78 (17) | C4—O1—H1A | 109.5 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H1B···N2i | 0.93 (2) | 2.21 (2) | 3.126 (3) | 171 (2) |
| N3—H1C···O1ii | 0.93 (2) | 2.69 (2) | 3.206 (3) | 116 (2) |
| O1—H1A···N4 | 0.82 | 1.91 | 2.639 (2) | 147 |
| Symmetry codes: (i) −x+1, y+1/2, −z−1/2; (ii) x, −y+3/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H1B···N2i | 0.93 (2) | 2.21 (2) | 3.126 (3) | 171 (2) |
| N3—H1C···O1ii | 0.93 (2) | 2.69 (2) | 3.206 (3) | 116 (2) |
| O1—H1A···N4 | 0.82 | 1.91 | 2.639 (2) | 147 |
| Symmetry codes: (i) −x+1, y+1/2, −z−1/2; (ii) x, −y+3/2, z−1/2. |
Boskovic, C., Bircher, R., Tregenna-Piggott, P. L. W., Gudel, H. U., Paulsen, C., Wernsdorfer, W., Barra, A. L., Khatsko, E., Neels, A. & Stoeckli-Evans, H. (2003). J. Am. Chem. Soc. 125, 14046–14058.
Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Kannappan, R., Tanase, S., Mutikainen, I., Turpeinen, U. & Reedijk, J. (2005). Inorg. Chim. Acta, 358, 383–388.
Koizumi, S., Nihei, M., Nakano, M. & Oshio, H. (2005). Inorg. Chem. 44, 1208–1210.
Oshiob, H., Nihei, M., Koizumi, S., Shiga, T., Nojiri, H., Nakano, M., Shirakawa, N. & Akatsu, M. (2005). J. Am. Chem. Soc. 127, 4568–4569.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Zhang, Y., Khoo, L. E. & Ng, S. W. (2003). Acta Cryst. E59, o1496–o1497.
During the past decades, Schiff bases have been intensively investigated not only because of their strong coordination capability but also due to their diverse biological activities, such as antibacterial, antitumor, etc. (Koizumi et al., 2005; Boskovic et al., 2003; Oshiob et al., 2005). The halide groups in schiff base ligands could effectively optimize the properties of the coordination complexes.
X-ray diffraction analysis indicates that (I) is an unsymmetrical Schiff base ligand (fig. 1). The imide bond length 1.283 (2)(2) Å for C(1)–N(4) is slightly longer than that of 4-Bromo-2-(2-pyridylmethyliminomethyl)phenol (1.269 (4) Å) (Zhang et al., 2003). It is noteworthy that there exists relatively weak intermolecular interactions involving the NH moieties and one intramolecular interaction with OH as the donor (Table 1), which are similar to those of its derivative 4-Bromo-2-(2-pyridylmethyliminomethyl)phenol (Zhang et al., 2003).