Acta Cryst. (2008). E64, o2150 [ doi:10.1107/S1600536808033266 ]
In the title Schiff base compound, C10H11N3O, the pyridine ring is twisted with respect to the mean plane containing the hydrazine chain, making a dihedral angle of 31.40 (9)°. The NH group interacts with the N atom of the pyridine ring through N-H
N hydrogen bonds to build up a zigzag chain developing parallel to the (
01) plane.
Pyridine-4-carboxylic acid hydrazide (1 mmol, 0.137 g) was dissolved in anhydrous methanol, H2SO4 (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, 3,4-dichlorobenzyaldehyde (1 mmol 0.070 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in dichloromethane, brown single crystals of (I) was obtained after 5 d.
H atoms were placed in calculated position and treated as riding with C—H= 0.93Å (aromatic), 0.96Å(methyl) and N-H= 0.86\%A with Uiso(H)=1.2Ueq(C,N) or Uiso(H)=1.5Ueq(methyl).
In the absence of significant anomalous scattering, the absolute structure could not be reliably determined and then the Friedel pairs were merged and any references to the Flack parameter were removed.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).; software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2392fig1thm.gif)
| Fig. 1. Molecular view of (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radii. |
![[Figure 2]](./dn2392fig2thm.gif)
| Fig. 2. Partial packing view showing the formation of the zig-zag chain through N-H···N hydrogen bonds which are shown as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity.[Symmetry code: (i) x-1/2, -y+3/2, z-1/2] |
| C10H11N3O | F(000) = 400 |
| Mr = 189.22 | Dx = 1.231 Mg m−3 |
| Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: C -2yc | Cell parameters from 2994 reflections |
| a = 9.5779 (8) Å | θ = 2.4–23.8° |
| b = 12.6191 (11) Å | µ = 0.08 mm−1 |
| c = 9.2095 (8) Å | T = 293 K |
| β = 113.511 (1)° | Block, brown |
| V = 1020.70 (15) Å3 | 0.25 × 0.23 × 0.18 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1264 independent reflections |
| Radiation source: fine-focus sealed tube | 1225 reflections with I > 2σ(I) |
| graphite | Rint = 0.012 |
| ω scans | θmax = 28.3°, θmin = 2.8° |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −12→12 |
| Tmin = 0.969, Tmax = 0.974 | k = −16→16 |
| 4639 measured reflections | l = −12→12 |
| 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.101 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0744P)2 + 0.0728P] where P = (Fo2 + 2Fc2)/3 |
| 1264 reflections | (Δ/σ)max < 0.001 |
| 128 parameters | Δρmax = 0.21 e Å−3 |
| 2 restraints | Δρmin = −0.12 e Å−3 |
| C10H11N3O | V = 1020.70 (15) Å3 |
| Mr = 189.22 | Z = 4 |
| Monoclinic, Cc | Mo Kα radiation |
| a = 9.5779 (8) Å | µ = 0.08 mm−1 |
| b = 12.6191 (11) Å | T = 293 K |
| c = 9.2095 (8) Å | 0.25 × 0.23 × 0.18 mm |
| β = 113.511 (1)° |
| Bruker SMART CCD area-detector diffractometer | 1264 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1225 reflections with I > 2σ(I) |
| Tmin = 0.969, Tmax = 0.974 | Rint = 0.012 |
| 4639 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.101 | Δρmax = 0.21 e Å−3 |
| S = 1.08 | Δρmin = −0.12 e Å−3 |
| 1264 reflections | Absolute structure: ? |
| 128 parameters | Flack parameter: ? |
| 2 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| N1 | 0.12133 (17) | 1.06196 (12) | 0.79852 (17) | 0.0441 (3) | |
| N2 | 0.21940 (16) | 0.98057 (11) | 0.87720 (16) | 0.0398 (3) | |
| H2 | 0.2126 | 0.9200 | 0.8322 | 0.048* | |
| N3 | 0.6220 (2) | 0.73212 (13) | 1.2278 (2) | 0.0512 (4) | |
| O1 | 0.33989 (17) | 1.07888 (10) | 1.10035 (17) | 0.0542 (4) | |
| C1 | −0.2651 (3) | 1.1633 (3) | 0.2819 (3) | 0.0800 (8) | |
| H1A | −0.2643 | 1.2313 | 0.3292 | 0.120* | |
| H1B | −0.3661 | 1.1344 | 0.2431 | 0.120* | |
| H1C | −0.2337 | 1.1712 | 0.1957 | 0.120* | |
| C2 | −0.1590 (3) | 1.0910 (2) | 0.4019 (3) | 0.0625 (5) | |
| H2A | −0.1514 | 1.0222 | 0.3696 | 0.075* | |
| C3 | −0.0728 (2) | 1.11582 (19) | 0.5528 (2) | 0.0546 (5) | |
| H3 | −0.0819 | 1.1824 | 0.5913 | 0.066* | |
| C4 | 0.0338 (2) | 1.04042 (16) | 0.6560 (2) | 0.0475 (4) | |
| H4 | 0.0388 | 0.9732 | 0.6170 | 0.057* | |
| C5 | 0.32562 (18) | 0.99674 (12) | 1.02479 (18) | 0.0366 (3) | |
| C6 | 0.42972 (17) | 0.90326 (12) | 1.09198 (17) | 0.0362 (3) | |
| C7 | 0.4905 (3) | 0.88762 (17) | 1.2543 (2) | 0.0529 (5) | |
| H7 | 0.4696 | 0.9347 | 1.3208 | 0.064* | |
| C8 | 0.5828 (3) | 0.80039 (19) | 1.3153 (2) | 0.0584 (5) | |
| H8 | 0.6198 | 0.7887 | 1.4239 | 0.070* | |
| C9 | 0.5679 (2) | 0.75022 (15) | 1.0721 (2) | 0.0477 (4) | |
| H9 | 0.5965 | 0.7046 | 1.0096 | 0.057* | |
| C10 | 0.47069 (19) | 0.83399 (13) | 0.99866 (19) | 0.0411 (3) | |
| H10 | 0.4341 | 0.8433 | 0.8896 | 0.049* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0439 (8) | 0.0368 (7) | 0.0431 (8) | 0.0086 (6) | 0.0081 (6) | 0.0041 (6) |
| N2 | 0.0428 (7) | 0.0303 (6) | 0.0381 (7) | 0.0045 (5) | 0.0075 (5) | −0.0011 (5) |
| N3 | 0.0596 (9) | 0.0426 (8) | 0.0425 (8) | 0.0149 (7) | 0.0108 (7) | 0.0071 (6) |
| O1 | 0.0604 (8) | 0.0401 (7) | 0.0468 (7) | 0.0119 (6) | 0.0055 (6) | −0.0113 (5) |
| C1 | 0.0650 (15) | 0.099 (2) | 0.0570 (13) | 0.0146 (14) | 0.0046 (11) | 0.0212 (14) |
| C2 | 0.0564 (11) | 0.0683 (14) | 0.0532 (12) | 0.0083 (10) | 0.0116 (9) | 0.0077 (10) |
| C3 | 0.0481 (9) | 0.0564 (11) | 0.0491 (10) | 0.0114 (8) | 0.0086 (8) | 0.0117 (8) |
| C4 | 0.0453 (9) | 0.0441 (9) | 0.0445 (9) | 0.0048 (7) | 0.0088 (7) | 0.0027 (7) |
| C5 | 0.0387 (7) | 0.0320 (7) | 0.0351 (7) | 0.0046 (5) | 0.0104 (6) | −0.0001 (5) |
| C6 | 0.0381 (7) | 0.0322 (7) | 0.0338 (7) | 0.0025 (5) | 0.0096 (6) | −0.0003 (6) |
| C7 | 0.0662 (12) | 0.0525 (11) | 0.0334 (8) | 0.0194 (9) | 0.0128 (8) | −0.0008 (7) |
| C8 | 0.0720 (12) | 0.0601 (12) | 0.0334 (8) | 0.0204 (10) | 0.0108 (8) | 0.0074 (8) |
| C9 | 0.0585 (10) | 0.0395 (8) | 0.0423 (8) | 0.0146 (7) | 0.0173 (8) | 0.0013 (6) |
| C10 | 0.0494 (8) | 0.0366 (8) | 0.0332 (7) | 0.0088 (6) | 0.0122 (6) | 0.0014 (6) |
| N1—C4 | 1.273 (2) | C3—C4 | 1.441 (3) |
| N1—N2 | 1.3853 (18) | C3—H3 | 0.9300 |
| N2—C5 | 1.349 (2) | C4—H4 | 0.9300 |
| N2—H2 | 0.8600 | C5—C6 | 1.509 (2) |
| N3—C8 | 1.332 (3) | C6—C7 | 1.385 (2) |
| N3—C9 | 1.335 (2) | C6—C10 | 1.388 (2) |
| O1—C5 | 1.225 (2) | C7—C8 | 1.383 (3) |
| C1—C2 | 1.480 (3) | C7—H7 | 0.9300 |
| C1—H1A | 0.9600 | C8—H8 | 0.9300 |
| C1—H1B | 0.9600 | C9—C10 | 1.392 (2) |
| C1—H1C | 0.9600 | C9—H9 | 0.9300 |
| C2—C3 | 1.340 (3) | C10—H10 | 0.9300 |
| C2—H2A | 0.9300 | ||
| C4—N1—N2 | 114.28 (15) | C3—C4—H4 | 118.6 |
| C5—N2—N1 | 119.75 (13) | O1—C5—N2 | 124.64 (15) |
| C5—N2—H2 | 120.1 | O1—C5—C6 | 121.51 (15) |
| N1—N2—H2 | 120.1 | N2—C5—C6 | 113.84 (13) |
| C8—N3—C9 | 117.17 (16) | C7—C6—C10 | 118.54 (14) |
| C2—C1—H1A | 109.5 | C7—C6—C5 | 118.58 (14) |
| C2—C1—H1B | 109.5 | C10—C6—C5 | 122.85 (14) |
| H1A—C1—H1B | 109.5 | C8—C7—C6 | 118.48 (16) |
| C2—C1—H1C | 109.5 | C8—C7—H7 | 120.8 |
| H1A—C1—H1C | 109.5 | C6—C7—H7 | 120.8 |
| H1B—C1—H1C | 109.5 | N3—C8—C7 | 123.92 (17) |
| C3—C2—C1 | 125.9 (2) | N3—C8—H8 | 118.0 |
| C3—C2—H2A | 117.1 | C7—C8—H8 | 118.0 |
| C1—C2—H2A | 117.1 | N3—C9—C10 | 123.32 (16) |
| C2—C3—C4 | 120.8 (2) | N3—C9—H9 | 118.3 |
| C2—C3—H3 | 119.6 | C10—C9—H9 | 118.3 |
| C4—C3—H3 | 119.6 | C6—C10—C9 | 118.48 (15) |
| N1—C4—C3 | 122.76 (18) | C6—C10—H10 | 120.8 |
| N1—C4—H4 | 118.6 | C9—C10—H10 | 120.8 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···N3i | 0.86 | 2.17 | 2.991 (2) | 160 |
| Symmetry codes: (i) x−1/2, −y+3/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···N3i | 0.86 | 2.17 | 2.991 (2) | 160 |
| Symmetry codes: (i) x−1/2, −y+3/2, z−1/2. |
The authors express their deep appreciation to the Outstanding Youth Fund for Henan Natural Scientific Research (grant No. 0512001100) and the Fund for Scientific and Technical Emphasis (grant No. 072102270006)
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Kahwa, I. A., Selbin, I., Hsieh, T. C. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185.
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844.
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Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
The chemistry of Schiff bases has attracted a great deal of interest in recent years. These compounds play an important role in the development of various proteins and enzymes(Kahwa et al., 1986; Santos et al., 2001). As part of our interest in the study of the coordination chemistry of Schiff bases, we have synthesized the title compound (I) and reported its cyrstal structure.
In the title compound. the pyridine ring is twisted with respect to the mean plane containing the hydrazine chain making a dihedral angle of 31.40 (9)° (Fig. 1). The NH interacts with the nitrogen atom of the pyridine ring through N-H···N hydrogen bond to build up a zig-zag chain developing parallel to the (-1 0 1) plane (Table 1, Fig. 2).