Acta Cryst. (2008). E64, o719 [ doi:10.1107/S1600536808004960 ]
The title compound, C11H9N3OS, was prepared to investigate the coordination chemistry of thiophene-containing ligands as precursors to interesting metallopolymers. The molecule is nearly planar. The angle between the thiophene and pyridine rings is 8.63 (4)° and features the expected trans configuration about the imine bond. The structure is stabilized by a weak intermolecular N-H
O hydrogen bond. The distance between centroids of adjacent thiophene rings [3.67 (8) Å] suggests the presence of ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions.
Pyridine-2-carbonohydrazide (Klingele & Brooker, 2004) (2.28 g, 16.6 mmol)was dissolved in 50 ml of absolute ethanol and cooled in an ice-water bath. A solution of 3-formylthiophene (2.91 g, 17.0 mmol) in 25 ml of absolute ethanol was added slowly dropwise to the cold hydrazide solution. Following the addition the ice-water bath was removed and the reaction was let stir at room temperature for 4 hr. While warming to room temperature, the appearance of a white microcrystalline precipitate was observed. The reaction flask was cooled in ice and the product was isolated by vacuum filtration, washed with cold ethanol and dried (yield 2.5 g, 65%). The compound was recrystallized by slow evaporation of a methanol solution to give large transparent blocks. MS (EI) = m/z 231 (M+, 20%), 79 (py+, 100%). FT—IR (KBr pellet) = 3295 (w, νN-H), 3072 (w), 1677 (s, νC=O), 1607 (m), 1533 (s), 1344 (m), 799 (m), 741 (m), 603 cm-1 (m). 1H NMR (CDCl3) = δ 10.91 (s, 1H, N—H), 8.60 (d, 1H, Ar—H), 8.42 (s, 1H, H—C=N), 8.33 (d, 1H, Ar—H), 7.92 (dd, 1H, Ar—H), 7.70 (d, 1H, Ar—H), 7.66 (d, 1H, Ar—H), 7.5 (dd, 1H, Ar—H), 7.38 (dd, 1H, Ar—H).
All non-hydrogen atoms were refined using anisotropic thermal parameters and hydrogen atoms were determined using the difference map and refined using isotropic thermal parameters.
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./fl2185fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms. |
![[Figure 2]](./fl2185fig2thm.gif)
| Fig. 2. The packing of the title compound viewed along the c axis. The intermolecular hydrogen bond (N2—H2···O1) and other close contacts (H4···N1 and H5···O1) are indicated as dotted lines. |
| C11H9N3OS | F000 = 480 |
| Mr = 231.27 | Dx = 1.464 Mg m−3 |
| Monoclinic, P2(1)/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 9922 reflections |
| a = 11.6817 (3) Å | θ = 2.9–39.5º |
| b = 9.1454 (3) Å | µ = 0.29 mm−1 |
| c = 10.0890 (3) Å | T = 173 (2) K |
| β = 103.2300 (10)º | Block, colourless |
| V = 1049.24 (5) Å3 | 0.40 × 0.30 × 0.20 mm |
| Z = 4 |
| Bruker APEXII CCD area-detector diffractometer | 6449 independent reflections |
| Radiation source: fine-focus sealed tube | 5355 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.024 |
| T = 173(2) K | θmax = 40.5º |
| φ and ω scans | θmin = 1.8º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −21→20 |
| Tmin = 0.908, Tmax = 0.959 | k = −16→16 |
| 32428 measured reflections | l = −18→14 |
| 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)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0599P)2 + 0.1403P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 6449 reflections | Δρmax = 0.48 e Å−3 |
| 181 parameters | Δρmin = −0.44 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C11H9N3OS | V = 1049.24 (5) Å3 |
| Mr = 231.27 | Z = 4 |
| Monoclinic, P2(1)/c | Mo Kα |
| a = 11.6817 (3) Å | µ = 0.29 mm−1 |
| b = 9.1454 (3) Å | T = 173 (2) K |
| c = 10.0890 (3) Å | 0.40 × 0.30 × 0.20 mm |
| β = 103.2300 (10)º |
| Bruker APEXII CCD area-detector diffractometer | 6449 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5355 reflections with I > 2σ(I) |
| Tmin = 0.908, Tmax = 0.959 | Rint = 0.024 |
| 32428 measured reflections |
| R[F2 > 2σ(F2)] = 0.035 | Δρmax = 0.48 e Å−3 |
| wR(F2) = 0.109 | Δρmin = −0.44 e Å−3 |
| S = 1.05 | Absolute structure: ? |
| 6449 reflections | Flack parameter: ? |
| 181 parameters | Rogers parameter: ? |
| H atoms treated by a mixture of independent and constrained refinement |
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 | ||
| S1 | 0.463771 (16) | 0.23464 (2) | 0.454041 (19) | 0.02568 (5) | |
| O1 | 0.85993 (5) | 0.78873 (6) | 0.23484 (5) | 0.02601 (10) | |
| C1 | 0.58685 (6) | 0.33166 (8) | 0.52713 (7) | 0.02334 (11) | |
| H1 | 0.6218 (12) | 0.3226 (15) | 0.6255 (14) | 0.038 (3)* | |
| N1 | 0.76136 (5) | 0.59050 (6) | 0.38381 (5) | 0.01975 (9) | |
| N2 | 0.86362 (5) | 0.66685 (7) | 0.43407 (6) | 0.02150 (10) | |
| H2 | 0.8983 (11) | 0.6677 (15) | 0.5159 (14) | 0.041 (3)* | |
| C2 | 0.62431 (5) | 0.41837 (7) | 0.43437 (6) | 0.01909 (9) | |
| C3 | 0.54986 (6) | 0.40473 (8) | 0.30101 (6) | 0.02346 (11) | |
| H3 | 0.5598 (11) | 0.4576 (15) | 0.2219 (14) | 0.038 (3)* | |
| N3 | 1.06794 (5) | 0.77731 (7) | 0.55311 (6) | 0.02522 (11) | |
| C4 | 0.45955 (6) | 0.30881 (8) | 0.29705 (7) | 0.02585 (12) | |
| H4 | 0.4001 (12) | 0.2786 (15) | 0.2207 (14) | 0.039 (3)* | |
| C5 | 0.72865 (5) | 0.50925 (7) | 0.47217 (6) | 0.02064 (10) | |
| H5 | 0.7741 (11) | 0.5050 (14) | 0.5620 (12) | 0.032 (3)* | |
| C6 | 0.90780 (5) | 0.75931 (7) | 0.35325 (6) | 0.01910 (10) | |
| C7 | 1.02436 (5) | 0.82307 (7) | 0.42481 (6) | 0.01914 (10) | |
| C8 | 1.08096 (6) | 0.92324 (8) | 0.35862 (7) | 0.02498 (12) | |
| H8 | 1.0462 (10) | 0.9482 (14) | 0.2685 (12) | 0.030 (3)* | |
| C9 | 1.18816 (7) | 0.98075 (9) | 0.42927 (9) | 0.02855 (13) | |
| H9 | 1.2275 (12) | 1.0512 (16) | 0.3916 (13) | 0.040 (3)* | |
| C10 | 1.23335 (6) | 0.93561 (9) | 0.56184 (9) | 0.02901 (13) | |
| H10 | 1.3068 (12) | 0.9703 (17) | 0.6115 (13) | 0.042 (4)* | |
| C11 | 1.17048 (6) | 0.83398 (10) | 0.61907 (8) | 0.02998 (14) | |
| H11 | 1.2008 (13) | 0.7924 (18) | 0.7155 (16) | 0.050 (4)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.02498 (8) | 0.02603 (8) | 0.02706 (9) | −0.00757 (5) | 0.00809 (6) | −0.00236 (5) |
| O1 | 0.0262 (2) | 0.0318 (2) | 0.01804 (19) | −0.00370 (18) | 0.00077 (16) | 0.00251 (17) |
| C1 | 0.0225 (2) | 0.0263 (3) | 0.0206 (2) | −0.0040 (2) | 0.00363 (19) | 0.0013 (2) |
| N1 | 0.01699 (19) | 0.0214 (2) | 0.0198 (2) | −0.00233 (16) | 0.00210 (15) | −0.00098 (16) |
| N2 | 0.0187 (2) | 0.0259 (2) | 0.0182 (2) | −0.00545 (17) | 0.00069 (16) | 0.00143 (17) |
| C2 | 0.0182 (2) | 0.0192 (2) | 0.0193 (2) | −0.00147 (17) | 0.00317 (17) | −0.00077 (17) |
| C3 | 0.0258 (3) | 0.0244 (3) | 0.0189 (2) | −0.0053 (2) | 0.00249 (19) | −0.00152 (19) |
| N3 | 0.0194 (2) | 0.0311 (3) | 0.0230 (2) | −0.00334 (19) | 0.00019 (17) | 0.0037 (2) |
| C4 | 0.0265 (3) | 0.0271 (3) | 0.0223 (3) | −0.0072 (2) | 0.0022 (2) | −0.0045 (2) |
| C5 | 0.0191 (2) | 0.0224 (2) | 0.0193 (2) | −0.00278 (18) | 0.00200 (17) | −0.00012 (18) |
| C6 | 0.0181 (2) | 0.0202 (2) | 0.0184 (2) | −0.00070 (17) | 0.00300 (17) | −0.00088 (17) |
| C7 | 0.0173 (2) | 0.0199 (2) | 0.0199 (2) | −0.00059 (17) | 0.00357 (17) | −0.00080 (17) |
| C8 | 0.0246 (3) | 0.0252 (3) | 0.0248 (3) | −0.0050 (2) | 0.0050 (2) | 0.0016 (2) |
| C9 | 0.0240 (3) | 0.0273 (3) | 0.0346 (3) | −0.0067 (2) | 0.0072 (2) | 0.0005 (2) |
| C10 | 0.0191 (2) | 0.0302 (3) | 0.0355 (3) | −0.0043 (2) | 0.0017 (2) | −0.0033 (3) |
| C11 | 0.0210 (3) | 0.0380 (4) | 0.0271 (3) | −0.0042 (2) | −0.0023 (2) | 0.0025 (3) |
| S1—C1 | 1.7067 (7) | N3—C11 | 1.3347 (9) |
| S1—C4 | 1.7133 (8) | N3—C7 | 1.3446 (9) |
| O1—C6 | 1.2274 (8) | C4—H4 | 0.953 (14) |
| C1—C2 | 1.3724 (9) | C5—H5 | 0.941 (12) |
| C1—H1 | 0.987 (13) | C6—C7 | 1.5052 (8) |
| N1—C5 | 1.2841 (8) | C7—C8 | 1.3873 (9) |
| N1—N2 | 1.3764 (7) | C8—C9 | 1.3944 (10) |
| N2—C6 | 1.3559 (8) | C8—H8 | 0.935 (12) |
| N2—H2 | 0.832 (14) | C9—C10 | 1.3838 (12) |
| C2—C3 | 1.4306 (9) | C9—H9 | 0.922 (14) |
| C2—C5 | 1.4523 (8) | C10—C11 | 1.3895 (11) |
| C3—C4 | 1.3655 (10) | C10—H10 | 0.944 (14) |
| C3—H3 | 0.963 (14) | C11—H11 | 1.029 (15) |
| H4···N1i | 2.591 (14) | H5···O1ii | 2.609 (12) |
| C1—S1—C4 | 92.11 (3) | C2—C5—H5 | 119.0 (8) |
| C2—C1—S1 | 111.98 (5) | O1—C6—N2 | 124.80 (6) |
| C2—C1—H1 | 127.7 (8) | O1—C6—C7 | 122.86 (6) |
| S1—C1—H1 | 120.3 (8) | N2—C6—C7 | 112.34 (5) |
| C5—N1—N2 | 114.13 (5) | N3—C7—C8 | 123.49 (6) |
| C6—N2—N1 | 120.83 (5) | N3—C7—C6 | 116.28 (5) |
| C6—N2—H2 | 115.1 (9) | C8—C7—C6 | 120.23 (6) |
| N1—N2—H2 | 123.7 (9) | C7—C8—C9 | 118.31 (7) |
| C1—C2—C3 | 111.77 (6) | C7—C8—H8 | 118.7 (7) |
| C1—C2—C5 | 122.07 (6) | C9—C8—H8 | 123.0 (7) |
| C3—C2—C5 | 126.15 (6) | C10—C9—C8 | 118.74 (7) |
| C4—C3—C2 | 112.51 (6) | C10—C9—H9 | 119.4 (8) |
| C4—C3—H3 | 122.5 (8) | C8—C9—H9 | 121.8 (8) |
| C2—C3—H3 | 124.9 (8) | C9—C10—C11 | 118.70 (7) |
| C11—N3—C7 | 117.26 (6) | C9—C10—H10 | 120.8 (8) |
| C3—C4—S1 | 111.64 (5) | C11—C10—H10 | 120.5 (8) |
| C3—C4—H4 | 128.8 (8) | N3—C11—C10 | 123.50 (7) |
| S1—C4—H4 | 119.6 (8) | N3—C11—H11 | 113.8 (9) |
| N1—C5—C2 | 120.94 (6) | C10—C11—H11 | 122.7 (8) |
| N1—C5—H5 | 120.0 (8) | ||
| C4—S1—C1—C2 | −0.15 (6) | C11—N3—C7—C8 | 0.86 (11) |
| C5—N1—N2—C6 | −178.74 (6) | C11—N3—C7—C6 | −179.13 (7) |
| S1—C1—C2—C3 | 0.21 (8) | O1—C6—C7—N3 | −177.94 (7) |
| S1—C1—C2—C5 | −178.92 (5) | N2—C6—C7—N3 | 1.78 (8) |
| C1—C2—C3—C4 | −0.17 (9) | O1—C6—C7—C8 | 2.06 (10) |
| C5—C2—C3—C4 | 178.92 (7) | N2—C6—C7—C8 | −178.21 (6) |
| C2—C3—C4—S1 | 0.05 (8) | N3—C7—C8—C9 | −0.69 (11) |
| C1—S1—C4—C3 | 0.05 (6) | C6—C7—C8—C9 | 179.30 (6) |
| N2—N1—C5—C2 | −178.20 (6) | C7—C8—C9—C10 | 0.02 (11) |
| C1—C2—C5—N1 | −179.36 (6) | C8—C9—C10—C11 | 0.42 (12) |
| C3—C2—C5—N1 | 1.64 (11) | C7—N3—C11—C10 | −0.38 (13) |
| N1—N2—C6—O1 | 3.95 (11) | C9—C10—C11—N3 | −0.25 (13) |
| N1—N2—C6—C7 | −175.76 (5) |
| 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 |
| N2—H2···O1ii | 0.83 (1) | 2.38 (1) | 3.0717 (8) | 140 (1) |
| Symmetry codes: (ii) x, −y+3/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.83 (1) | 2.38 (1) | 3.0717 (8) | 140 (1) |
| Symmetry codes: (i) x, −y+3/2, z+1/2. |
The authors thank the Natural Sciences and Engineering Research Council for financial support. Martin Lemaire thanks Brock University and Research Corporation for a Cottrell College grant (No. CC6686) in support of this research. The X-ray crystallographic analyses were performed at the McMaster Analytical X-ray (MAX) Diffraction Facility.
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We are interested in the coordination chemistry of thiophene containing ligands as precursors to interesting metallopolymers. The title compound (I, Fig. 1) features a pyridine-2-carbonohydrazide moiety grafted onto the 3 position of the thiophene ring and offers a number of possible coordination modes to metal ions, which we are currently exploring.
Bond lengths and angles are in the normal range reported for other molecules containing the pyridine-2-carbonohydrazide moiety (Xie et al., 2006; Zhang et al., 2006). Bond parameters within the thiophene and pyridine rings are also within normal ranges. The C5 - N1 bond is 1.284 (8) Å, typical for a double bond and features the expected trans configuration. The C6 - N2 bond of 1.356 (8) Å is in the range between the expected values for purely single or double bonds as a result of the π-conjugation. The molecule is nearly planar; the angle between the thiophene and pyridine ring is 8.63° (4). The structure is stabilized by an intermolecular hydrogen-bond (H2···O1 = 2.38 (1) Å) between the amide hydrogen and carbonyl oxygen atoms. Other weak intermolecular interactions are suggested by close contacts between H4···N1 (2.591 (14) Å) and H5···O1 (2.609 (12) Å), Fig. 2. The structure is further stabilized by π-π interactions between adjacent thiophene rings (ring centroids are 3.6720(0.0818 Å apart).