organic compounds
2-[(E)-(Pyridin-2-ylmethylidene)amino]thiophene-3-carbonitrile
aDepartment of Chemistry, Université de Montréall, CP 6128, succ. Centre-ville, Montréal, Qc, Canada
*Correspondence e-mail: w.skene@umontreal.ca
In the title compound, C11H7N3S, the thiophene and pyridine rings are coplanar, forming a dihedral angle of 3.89 (7)°. The conformation about the C=N bond [1.2795 (18) Å] is E. In the crystal, translationally related molecules along the a axis form weak π–π interactions [centroid–centroid distance = 3.8451 (8) Å] between the thiophene rings.
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: UdMX (Marris, 2004).
Supporting information
10.1107/S1600536812043188/lx2267sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812043188/lx2267Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812043188/lx2267Isup3.cdx
Supporting information file. DOI: 10.1107/S1600536812043188/lx2267Isup4.cml
In a round bottom flask, 2-pyridinecarboxaldehyde (200 mg, 1.91 mmol) and 2-amino-3-cyanothiophene (260 mg, 2.08 mmol) were dissolved in anhydrous ethanol (25 mL). A catalytic amount of trifluoroacetic acid was added to the mixture and it was stirred at 80°C under nitrogen for 20 h. The reaction was then cooled to room temperature and the resulting product filtered to get the title compound as a yellow crystals (155.9 mg, 38%).
H atoms were placed in calculated positions (C—H = 0.93 Å) and included in the
in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: UdMX (Marris, 2004).Fig. 1. Molecular structure with the numbering scheme adopted and ellipsoids drawn at 30% probability level. | |
Fig. 2. A view of the unit cell contents for (I). |
C11H7N3S | F(000) = 440 |
Mr = 213.26 | Dx = 1.442 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 8225 reflections |
a = 3.8451 (1) Å | θ = 4.2–72.2° |
b = 20.8901 (4) Å | µ = 2.64 mm−1 |
c = 12.2725 (2) Å | T = 296 K |
β = 94.952 (1)° | Cube, yellow |
V = 982.10 (4) Å3 | 0.18 × 0.14 × 0.13 mm |
Z = 4 |
Bruker SMART 6000 diffractometer | 1940 independent reflections |
Radiation source: Rotating Anode | 1777 reflections with I > 2σ(I) |
Montel 200 optics monochromator | Rint = 0.037 |
Detector resolution: 5.5 pixels mm-1 | θmax = 72.6°, θmin = 4.2° |
ω scans | h = −4→4 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −25→22 |
Tmin = 0.637, Tmax = 0.710 | l = −15→15 |
13010 measured reflections |
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-atom parameters constrained |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0705P)2 + 0.1553P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
1940 reflections | Δρmax = 0.20 e Å−3 |
137 parameters | Δρmin = −0.24 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0048 (8) |
C11H7N3S | V = 982.10 (4) Å3 |
Mr = 213.26 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 3.8451 (1) Å | µ = 2.64 mm−1 |
b = 20.8901 (4) Å | T = 296 K |
c = 12.2725 (2) Å | 0.18 × 0.14 × 0.13 mm |
β = 94.952 (1)° |
Bruker SMART 6000 diffractometer | 1940 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1777 reflections with I > 2σ(I) |
Tmin = 0.637, Tmax = 0.710 | Rint = 0.037 |
13010 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.20 e Å−3 |
1940 reflections | Δρmin = −0.24 e Å−3 |
137 parameters |
Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equiped with a Bruker SMART 4 K Charged-Coupled Device (CCD) Area Detector using the program APEX2 and a Nonius FR591 rotating anode equiped with a Montel 200 optics The crystal-to-detector distance was 5.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over four different parts of the reciprocal space (132 frames total). One complete sphere of data was collected, to better than 0.80 Å resolution. |
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 | 0.28514 (9) | 0.585396 (16) | 0.49120 (3) | 0.03295 (17) | |
N4 | 0.3288 (3) | 0.55247 (5) | 0.27296 (10) | 0.0300 (3) | |
N6 | −0.0323 (3) | 0.39582 (6) | 0.24657 (11) | 0.0355 (3) | |
N11 | 0.6852 (4) | 0.70387 (7) | 0.16200 (12) | 0.0479 (4) | |
C1 | 0.4195 (4) | 0.66118 (7) | 0.52750 (12) | 0.0351 (3) | |
H1 | 0.4165 | 0.6777 | 0.5978 | 0.042* | |
C2 | 0.5305 (4) | 0.69438 (7) | 0.44255 (12) | 0.0330 (3) | |
H2 | 0.6126 | 0.7362 | 0.4479 | 0.040* | |
C3 | 0.5078 (4) | 0.65807 (6) | 0.34397 (12) | 0.0296 (3) | |
C4 | 0.3787 (3) | 0.59711 (6) | 0.35650 (12) | 0.0284 (3) | |
C5 | 0.1810 (4) | 0.49926 (7) | 0.29216 (12) | 0.0307 (3) | |
H5 | 0.1096 | 0.4923 | 0.3617 | 0.037* | |
C6 | 0.1192 (4) | 0.44890 (7) | 0.20990 (12) | 0.0299 (3) | |
C7 | 0.2076 (4) | 0.45613 (7) | 0.10312 (12) | 0.0331 (3) | |
H7 | 0.3145 | 0.4934 | 0.0816 | 0.040* | |
C8 | 0.1335 (4) | 0.40665 (7) | 0.02923 (14) | 0.0376 (4) | |
H8 | 0.1885 | 0.4101 | −0.0429 | 0.045* | |
C9 | −0.0248 (4) | 0.35197 (7) | 0.06573 (14) | 0.0375 (4) | |
H9 | −0.0810 | 0.3182 | 0.0181 | 0.045* | |
C10 | −0.0979 (4) | 0.34840 (7) | 0.17395 (14) | 0.0387 (4) | |
H10 | −0.1983 | 0.3110 | 0.1978 | 0.046* | |
C11 | 0.6052 (4) | 0.68224 (7) | 0.24209 (13) | 0.0343 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0387 (2) | 0.0311 (2) | 0.0296 (2) | −0.00353 (13) | 0.00597 (16) | 0.00229 (12) |
N4 | 0.0314 (6) | 0.0272 (6) | 0.0315 (6) | −0.0004 (4) | 0.0028 (5) | 0.0014 (5) |
N6 | 0.0401 (7) | 0.0303 (6) | 0.0359 (7) | −0.0054 (5) | 0.0016 (5) | 0.0021 (5) |
N11 | 0.0656 (10) | 0.0385 (8) | 0.0412 (8) | −0.0017 (7) | 0.0133 (7) | 0.0070 (6) |
C1 | 0.0394 (8) | 0.0340 (8) | 0.0323 (8) | −0.0001 (6) | 0.0043 (6) | −0.0036 (6) |
C2 | 0.0349 (7) | 0.0276 (7) | 0.0364 (8) | −0.0010 (5) | 0.0025 (6) | −0.0020 (5) |
C3 | 0.0306 (7) | 0.0262 (7) | 0.0319 (7) | 0.0005 (5) | 0.0026 (5) | 0.0021 (5) |
C4 | 0.0272 (7) | 0.0271 (7) | 0.0309 (7) | 0.0011 (5) | 0.0022 (5) | 0.0024 (5) |
C5 | 0.0334 (7) | 0.0291 (7) | 0.0295 (7) | −0.0016 (5) | 0.0024 (5) | 0.0027 (5) |
C6 | 0.0283 (6) | 0.0273 (7) | 0.0337 (7) | 0.0009 (5) | −0.0001 (5) | 0.0025 (5) |
C7 | 0.0353 (7) | 0.0286 (7) | 0.0357 (7) | 0.0010 (5) | 0.0048 (6) | 0.0015 (6) |
C8 | 0.0414 (8) | 0.0360 (8) | 0.0357 (8) | 0.0056 (6) | 0.0053 (6) | −0.0019 (6) |
C9 | 0.0370 (8) | 0.0303 (8) | 0.0444 (9) | 0.0033 (6) | −0.0013 (6) | −0.0068 (6) |
C10 | 0.0424 (8) | 0.0279 (7) | 0.0452 (9) | −0.0053 (6) | −0.0004 (7) | 0.0005 (6) |
C11 | 0.0402 (8) | 0.0256 (7) | 0.0374 (8) | −0.0011 (6) | 0.0048 (6) | 0.0009 (6) |
S1—C1 | 1.7122 (15) | C3—C11 | 1.428 (2) |
S1—C4 | 1.7392 (15) | C5—C6 | 1.463 (2) |
N4—C5 | 1.2795 (18) | C5—H5 | 0.9300 |
N4—C4 | 1.3869 (18) | C6—C7 | 1.390 (2) |
N6—C10 | 1.342 (2) | C7—C8 | 1.388 (2) |
N6—C6 | 1.3478 (19) | C7—H7 | 0.9300 |
N11—C11 | 1.147 (2) | C8—C9 | 1.387 (2) |
C1—C2 | 1.352 (2) | C8—H8 | 0.9300 |
C1—H1 | 0.9300 | C9—C10 | 1.383 (2) |
C2—C3 | 1.424 (2) | C9—H9 | 0.9300 |
C2—H2 | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.3802 (19) | ||
C1—S1—C4 | 91.99 (7) | C6—C5—H5 | 118.5 |
C5—N4—C4 | 118.89 (12) | N6—C6—C7 | 123.51 (13) |
C10—N6—C6 | 116.58 (13) | N6—C6—C5 | 114.22 (13) |
C2—C1—S1 | 112.46 (11) | C7—C6—C5 | 122.26 (13) |
C2—C1—H1 | 123.8 | C8—C7—C6 | 118.79 (14) |
S1—C1—H1 | 123.8 | C8—C7—H7 | 120.6 |
C1—C2—C3 | 112.43 (13) | C6—C7—H7 | 120.6 |
C1—C2—H2 | 123.8 | C9—C8—C7 | 118.26 (15) |
C3—C2—H2 | 123.8 | C9—C8—H8 | 120.9 |
C4—C3—C2 | 113.14 (13) | C7—C8—H8 | 120.9 |
C4—C3—C11 | 123.22 (13) | C10—C9—C8 | 119.06 (14) |
C2—C3—C11 | 123.64 (13) | C10—C9—H9 | 120.5 |
C3—C4—N4 | 124.48 (13) | C8—C9—H9 | 120.5 |
C3—C4—S1 | 109.97 (11) | N6—C10—C9 | 123.78 (14) |
N4—C4—S1 | 125.54 (10) | N6—C10—H10 | 118.1 |
N4—C5—C6 | 123.08 (13) | C9—C10—H10 | 118.1 |
N4—C5—H5 | 118.5 | N11—C11—C3 | 177.44 (16) |
C4—S1—C1—C2 | 0.03 (12) | C4—N4—C5—C6 | −179.46 (12) |
S1—C1—C2—C3 | 0.06 (17) | C10—N6—C6—C7 | −0.1 (2) |
C1—C2—C3—C4 | −0.15 (19) | C10—N6—C6—C5 | 179.36 (13) |
C1—C2—C3—C11 | 179.33 (13) | N4—C5—C6—N6 | 178.52 (13) |
C2—C3—C4—N4 | 179.51 (12) | N4—C5—C6—C7 | −2.0 (2) |
C11—C3—C4—N4 | 0.0 (2) | N6—C6—C7—C8 | 0.8 (2) |
C2—C3—C4—S1 | 0.17 (16) | C5—C6—C7—C8 | −178.60 (13) |
C11—C3—C4—S1 | −179.31 (11) | C6—C7—C8—C9 | −0.3 (2) |
C5—N4—C4—C3 | −174.38 (13) | C7—C8—C9—C10 | −0.9 (2) |
C5—N4—C4—S1 | 4.86 (19) | C6—N6—C10—C9 | −1.2 (2) |
C1—S1—C4—C3 | −0.12 (11) | C8—C9—C10—N6 | 1.7 (2) |
C1—S1—C4—N4 | −179.45 (12) |
Experimental details
Crystal data | |
Chemical formula | C11H7N3S |
Mr | 213.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 3.8451 (1), 20.8901 (4), 12.2725 (2) |
β (°) | 94.952 (1) |
V (Å3) | 982.10 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.64 |
Crystal size (mm) | 0.18 × 0.14 × 0.13 |
Data collection | |
Diffractometer | Bruker SMART 6000 diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.637, 0.710 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13010, 1940, 1777 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.102, 1.08 |
No. of reflections | 1940 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.24 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), UdMX (Marris, 2004).
Acknowledgements
The authors acknowledge financial support from the Natural Sciences and Engineering Research Council Canada (NSERC), the Centre for Self-Assembled Chemical Structures, and the Canada Foundation for Innovation. AB thanks both NSERC and the Université de Montréal for graduate scholarships.
References
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Marris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Skene, W. G., Dufresne, S., Trefz, T. & Simard, M. (2006). Acta Cryst. E62, o2382–o2384. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Title compound (I) was made during our ongoing research on azomethine materials. It is one of a limited number of reported crystal structures of pyridine azomethine derivatives. The structure was confirmed by the X-ray crystallography as shown in Fig. 1. The ORTEP diagram shows that the structure adopts the thermodynamically stable E isomer.
One of the major points of interest is the azomethine bond. The bond lengths for C5—C6, C5—N4 and N4—C4 are 1.463 (2), 1.2795 (18) and 1.3869 (18) Å, respectively. The bond distances are consistent with similar compounds made of thiophene units with one azomethine bond (Skene et al., 2006). The bond lengths in a related molecule, i.e. (E)-diethyl 2-amino-5-(2-thienylmethyleneamino)thiophene-3,4-dicarboxylate, are 1.426 (3), 1.283 (3) and 1.381 (3) Å, respectively. The planes described by the thiophene and the pyridine moieties form a dihedral angle of 3.89 (7)° between each other.
A view of the crystal packing for (I) is illustrated in Fig. 2. Molecules stack along the a axis forming weak π—π interactions [3.8451 (8) Å for symmetry operation -1+x, y, z] formed between translationally related thiophene rings.