supplementary materials
N'-[(E)-3-Pyridylmethylidene]benzohydrazide
The title compound, C13H11N3O, was prepared by the reaction of benzohydrazide and nicotinaldehyde. The dihedral angle between the planes of the two aromatic rings is 47.78 (9)°. The crystal structure is stabilized by intermolecular N-H
N hydrogen-bonding interactions.
A mixture of benzohydrazide (10 mmol) and nicotinaldehyde (10 mmol) was
refluxed in ethanol (40 ml) for 2 h at 353K. After the solution had cooled
down to room temperature yellow sediment appeared. The product was
crystallized from a solution of methanol to yield yellow block-shaped crystals
of the title compound (yield 78%). Anal. Calcd (%) for C13H11N3O (Mr =
225.25): C,69.32; H, 4.92; N, 18.65. Found (%): C, 69.21; H, 4.97; N, 18.76.
In the absence of significant anomalous scattering effects, Friedel pairs were
averaged. The C—H and N—H H atoms were positioned with idealized geometry
(N—H = 0.86 Å and C—H = 0.93 Å) and were refined using a riding model
approximation with Uiso(H) = 1.2 Ueq(C, N).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).
N'-[(
E)-3-Pyridylmethylidene]benzohydrazide
top
Crystal data top
| C13H11N3O | F(000) = 472 |
| Mr = 225.25 | Dx = 1.365 Mg m−3 |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2ac 2ab | Cell parameters from 764 reflections |
| a = 7.6193 (13) Å | θ = 2.4–25.1° |
| b = 10.6291 (17) Å | µ = 0.09 mm−1 |
| c = 13.530 (2) Å | T = 298 K |
| V = 1095.7 (3) Å3 | Block, yellow |
| Z = 4 | 0.21 × 0.18 × 0.08 mm |
Data collection top
Siemens SMART CCD
diffractometer | 1136 independent reflections |
| Radiation source: fine-focus sealed tube | 612 reflections with I > 2σ(I) |
| graphite | Rint = 0.073 |
| φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −9→8 |
| Tmin = 0.981, Tmax = 0.993 | k = −12→11 |
| 5473 measured reflections | l = −12→16 |
Refinement top
| 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) = 0.104 | H-atom parameters constrained |
| S = 1.18 | w = 1/[σ2(Fo2) + (0.0242P)2 + 0.2399P]
where P = (Fo2 + 2Fc2)/3 |
| 1136 reflections | (Δ/σ)max < 0.001 |
| 154 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
| C13H11N3O | V = 1095.7 (3) Å3 |
| Mr = 225.25 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 7.6193 (13) Å | µ = 0.09 mm−1 |
| b = 10.6291 (17) Å | T = 298 K |
| c = 13.530 (2) Å | 0.21 × 0.18 × 0.08 mm |
Data collection top
Siemens SMART CCD
diffractometer | 1136 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 612 reflections with I > 2σ(I) |
| Tmin = 0.981, Tmax = 0.993 | Rint = 0.073 |
| 5473 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
| wR(F2) = 0.104 | Δρmax = 0.20 e Å−3 |
| S = 1.18 | Δρmin = −0.20 e Å−3 |
| 1136 reflections | Absolute structure: ? |
| 154 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| N1 | 0.1276 (5) | 0.7488 (3) | 0.4106 (3) | 0.0430 (12) | |
| H1 | 0.1551 | 0.8129 | 0.3750 | 0.052* | |
| N2 | 0.1085 (5) | 0.7596 (4) | 0.5111 (3) | 0.0410 (11) | |
| N3 | 0.1881 (5) | 1.0185 (4) | 0.7966 (3) | 0.0450 (12) | |
| O1 | 0.0701 (5) | 0.5389 (3) | 0.4181 (2) | 0.0544 (10) | |
| C1 | 0.1015 (7) | 0.6334 (4) | 0.3688 (4) | 0.0386 (13) | |
| C2 | 0.1109 (6) | 0.6291 (4) | 0.2602 (3) | 0.0327 (12) | |
| C3 | 0.0535 (7) | 0.7257 (4) | 0.2001 (4) | 0.0438 (14) | |
| H3 | 0.0107 | 0.7992 | 0.2285 | 0.053* | |
| C4 | 0.0588 (7) | 0.7150 (5) | 0.0986 (4) | 0.0523 (15) | |
| H4 | 0.0175 | 0.7805 | 0.0594 | 0.063* | |
| C5 | 0.1247 (7) | 0.6078 (5) | 0.0548 (4) | 0.0559 (17) | |
| H5 | 0.1301 | 0.6013 | −0.0137 | 0.067* | |
| C6 | 0.1826 (7) | 0.5105 (4) | 0.1136 (4) | 0.0515 (15) | |
| H6 | 0.2268 | 0.4376 | 0.0848 | 0.062* | |
| C7 | 0.1748 (6) | 0.5212 (4) | 0.2156 (4) | 0.0448 (14) | |
| H7 | 0.2132 | 0.4547 | 0.2547 | 0.054* | |
| C8 | 0.1525 (6) | 0.8640 (5) | 0.5499 (3) | 0.0446 (14) | |
| H8 | 0.1941 | 0.9288 | 0.5101 | 0.054* | |
| C9 | 0.1968 (6) | 0.9926 (4) | 0.6998 (3) | 0.0432 (14) | |
| H9 | 0.2460 | 1.0533 | 0.6588 | 0.052* | |
| C10 | 0.1383 (6) | 0.8825 (4) | 0.6558 (4) | 0.0365 (13) | |
| C11 | 0.0676 (6) | 0.7933 (4) | 0.7186 (4) | 0.0416 (14) | |
| H11 | 0.0272 | 0.7173 | 0.6933 | 0.050* | |
| C12 | 0.0567 (7) | 0.8168 (5) | 0.8183 (4) | 0.0492 (15) | |
| H12 | 0.0094 | 0.7572 | 0.8610 | 0.059* | |
| C13 | 0.1173 (6) | 0.9306 (5) | 0.8537 (4) | 0.0497 (15) | |
| H13 | 0.1080 | 0.9465 | 0.9211 | 0.060* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| N1 | 0.066 (3) | 0.036 (2) | 0.026 (2) | −0.006 (2) | 0.001 (2) | −0.0031 (19) |
| N2 | 0.051 (3) | 0.039 (2) | 0.033 (3) | −0.002 (2) | 0.003 (2) | 0.0001 (19) |
| N3 | 0.048 (3) | 0.046 (2) | 0.041 (3) | −0.003 (2) | 0.001 (2) | −0.008 (2) |
| O1 | 0.080 (3) | 0.0399 (19) | 0.044 (2) | −0.009 (2) | −0.004 (2) | 0.0059 (18) |
| C1 | 0.043 (3) | 0.036 (3) | 0.037 (3) | −0.005 (3) | −0.006 (3) | −0.003 (3) |
| C2 | 0.030 (3) | 0.033 (3) | 0.035 (3) | −0.004 (3) | 0.002 (3) | −0.004 (2) |
| C3 | 0.057 (4) | 0.033 (3) | 0.042 (4) | 0.004 (3) | 0.005 (3) | −0.005 (3) |
| C4 | 0.063 (4) | 0.054 (3) | 0.040 (4) | −0.002 (3) | −0.007 (3) | 0.003 (3) |
| C5 | 0.077 (4) | 0.056 (4) | 0.035 (3) | −0.002 (3) | 0.002 (3) | −0.006 (3) |
| C6 | 0.063 (4) | 0.037 (3) | 0.055 (4) | 0.004 (3) | 0.005 (3) | −0.011 (3) |
| C7 | 0.050 (4) | 0.036 (3) | 0.049 (4) | −0.004 (3) | 0.000 (3) | −0.001 (3) |
| C8 | 0.057 (4) | 0.039 (3) | 0.038 (3) | −0.003 (3) | 0.001 (3) | 0.003 (3) |
| C9 | 0.056 (4) | 0.038 (3) | 0.036 (3) | −0.002 (3) | 0.002 (3) | 0.000 (3) |
| C10 | 0.044 (3) | 0.035 (3) | 0.030 (3) | −0.002 (3) | 0.000 (3) | 0.002 (2) |
| C11 | 0.045 (4) | 0.038 (3) | 0.042 (4) | −0.002 (3) | 0.000 (3) | −0.002 (3) |
| C12 | 0.060 (4) | 0.048 (3) | 0.039 (3) | −0.010 (3) | 0.004 (3) | 0.006 (3) |
| C13 | 0.052 (4) | 0.061 (3) | 0.037 (3) | −0.002 (3) | 0.004 (3) | −0.006 (3) |
Geometric parameters (Å, °) top
| N1—C1 | 1.365 (5) | C5—H5 | 0.9300 |
| N1—N2 | 1.372 (5) | C6—C7 | 1.386 (6) |
| N1—H1 | 0.8600 | C6—H6 | 0.9300 |
| N2—C8 | 1.273 (6) | C7—H7 | 0.9300 |
| N3—C13 | 1.327 (6) | C8—C10 | 1.451 (6) |
| N3—C9 | 1.340 (5) | C8—H8 | 0.9300 |
| O1—C1 | 1.229 (5) | C9—C10 | 1.386 (6) |
| C1—C2 | 1.473 (6) | C9—H9 | 0.9300 |
| C2—C3 | 1.380 (6) | C10—C11 | 1.381 (6) |
| C2—C7 | 1.385 (6) | C11—C12 | 1.375 (6) |
| C3—C4 | 1.378 (6) | C11—H11 | 0.9300 |
| C3—H3 | 0.9300 | C12—C13 | 1.381 (6) |
| C4—C5 | 1.379 (6) | C12—H12 | 0.9300 |
| C4—H4 | 0.9300 | C13—H13 | 0.9300 |
| C5—C6 | 1.377 (6) | | |
| | | |
| C1—N1—N2 | 118.1 (4) | C7—C6—H6 | 120.0 |
| C1—N1—H1 | 121.0 | C2—C7—C6 | 121.1 (5) |
| N2—N1—H1 | 121.0 | C2—C7—H7 | 119.5 |
| C8—N2—N1 | 117.0 (4) | C6—C7—H7 | 119.5 |
| C13—N3—C9 | 116.4 (4) | N2—C8—C10 | 120.4 (5) |
| O1—C1—N1 | 122.5 (5) | N2—C8—H8 | 119.8 |
| O1—C1—C2 | 121.7 (5) | C10—C8—H8 | 119.8 |
| N1—C1—C2 | 115.7 (4) | N3—C9—C10 | 125.2 (4) |
| C3—C2—C7 | 118.1 (4) | N3—C9—H9 | 117.4 |
| C3—C2—C1 | 123.4 (5) | C10—C9—H9 | 117.4 |
| C7—C2—C1 | 118.5 (5) | C11—C10—C9 | 116.2 (4) |
| C4—C3—C2 | 121.1 (5) | C11—C10—C8 | 122.9 (5) |
| C4—C3—H3 | 119.5 | C9—C10—C8 | 120.9 (5) |
| C2—C3—H3 | 119.5 | C12—C11—C10 | 120.1 (5) |
| C3—C4—C5 | 120.5 (5) | C12—C11—H11 | 119.9 |
| C3—C4—H4 | 119.8 | C10—C11—H11 | 119.9 |
| C5—C4—H4 | 119.8 | C11—C12—C13 | 118.6 (5) |
| C6—C5—C4 | 119.2 (5) | C11—C12—H12 | 120.7 |
| C6—C5—H5 | 120.4 | C13—C12—H12 | 120.7 |
| C4—C5—H5 | 120.4 | N3—C13—C12 | 123.4 (5) |
| C5—C6—C7 | 120.0 (5) | N3—C13—H13 | 118.3 |
| C5—C6—H6 | 120.0 | C12—C13—H13 | 118.3 |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···N3i | 0.86 | 2.40 | 3.236 (5) | 164 |
| Symmetry codes: (i) −x+1/2, −y+2, z−1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···N3i | 0.86 | 2.40 | 3.236 (5) | 164 |
| Symmetry codes: (i) −x+1/2, −y+2, z−1/2. |
We acknowledge the National Natural Science Foundation of China (20771053), the
Natural Science Foundation of Shandong Province (Y2008B48) and the Students
Technology Cultural Innovation Fund of Liaocheng University (SRT08044HX2) for
financial support.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Yin, H., Cui, J. & Qiao, Y. (2008). Polyhedron, 27, 2157–2166.
![[Figure 1]](./gk2228fig1thm.gif)
![[Figure 2]](./gk2228fig2thm.gif)
Acylhydrazones, as an example of Schiff bases, and their metal complexes have been widely studied due to their versatile applications in the fields of analytical and medicinal chemistry and biotechnology. These ligands, owing to their facile keto-enol tautomerization and the availability of several potential donor sites, can coordinate with metals (Yin et al., 2008). We report here the synthesis and structure of the title compound. The molecular structure of the title compound is shown in Fig. 1. The hydrazone molecule crystallizes as an E isomer. In the crystal structure, there exist intermolecular N—H···N hydrogen bonds (Table 1). As seen in Fig. 2, the molecules are linked into one-dimensional extended chain structure.