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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

(Received 18 September 2012; accepted 16 October 2012; online 3 November 2012)

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 ππ inter­actions [centroid–centroid distance = 3.8451 (8) Å] between the thio­phene rings.

Related literature

For a related structure, see: Skene et al. (2006[Skene, W. G., Dufresne, S., Trefz, T. & Simard, M. (2006). Acta Cryst. E62, o2382-o2384.]).

[Scheme 1]

Experimental

Crystal data
  • C11H7N3S

  • Mr = 213.26

  • Monoclinic, P 21 /c

  • a = 3.8451 (1) Å

  • b = 20.8901 (4) Å

  • c = 12.2725 (2) Å

  • β = 94.952 (1)°

  • V = 982.10 (4) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 2.64 mm−1

  • T = 296 K

  • 0.18 × 0.14 × 0.13 mm

Data collection
  • Bruker SMART 6000 diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.637, Tmax = 0.710

  • 13010 measured reflections

  • 1940 independent reflections

  • 1777 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.102

  • S = 1.08

  • 1940 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: UdMX (Marris, 2004[Marris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada.]).

Supporting information


Comment top

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 ππ interactions [3.8451 (8) Å for symmetry operation -1+x, y, z] formed between translationally related thiophene rings.

Related literature top

For a related structure, see: Skene et al. (2006).

Experimental top

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%).

Refinement top

H atoms were placed in calculated positions (C—H = 0.93 Å) and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. Molecular structure with the numbering scheme adopted and ellipsoids drawn at 30% probability level.
[Figure 2] Fig. 2. A view of the unit cell contents for (I).
2-[(E)-(Pyridin-2-ylmethylidene)amino]thiophene-3-carbonitrile top
Crystal data top
C11H7N3SF(000) = 440
Mr = 213.26Dx = 1.442 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybcCell parameters from 8225 reflections
a = 3.8451 (1) Åθ = 4.2–72.2°
b = 20.8901 (4) ŵ = 2.64 mm1
c = 12.2725 (2) ÅT = 296 K
β = 94.952 (1)°Cube, yellow
V = 982.10 (4) Å30.18 × 0.14 × 0.13 mm
Z = 4
Data collection top
Bruker SMART 6000
diffractometer
1940 independent reflections
Radiation source: Rotating Anode1777 reflections with I > 2σ(I)
Montel 200 optics monochromatorRint = 0.037
Detector resolution: 5.5 pixels mm-1θmax = 72.6°, θmin = 4.2°
ω scansh = 44
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 2522
Tmin = 0.637, Tmax = 0.710l = 1515
13010 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-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 reflectionsΔρmax = 0.20 e Å3
137 parametersΔρmin = 0.24 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0048 (8)
Crystal data top
C11H7N3SV = 982.10 (4) Å3
Mr = 213.26Z = 4
Monoclinic, P21/cCu Kα radiation
a = 3.8451 (1) ŵ = 2.64 mm1
b = 20.8901 (4) ÅT = 296 K
c = 12.2725 (2) Å0.18 × 0.14 × 0.13 mm
β = 94.952 (1)°
Data collection top
Bruker SMART 6000
diffractometer
1940 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1777 reflections with I > 2σ(I)
Tmin = 0.637, Tmax = 0.710Rint = 0.037
13010 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.102H-atom parameters constrained
S = 1.08Δρmax = 0.20 e Å3
1940 reflectionsΔρmin = 0.24 e Å3
137 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.28514 (9)0.585396 (16)0.49120 (3)0.03295 (17)
N40.3288 (3)0.55247 (5)0.27296 (10)0.0300 (3)
N60.0323 (3)0.39582 (6)0.24657 (11)0.0355 (3)
N110.6852 (4)0.70387 (7)0.16200 (12)0.0479 (4)
C10.4195 (4)0.66118 (7)0.52750 (12)0.0351 (3)
H10.41650.67770.59780.042*
C20.5305 (4)0.69438 (7)0.44255 (12)0.0330 (3)
H20.61260.73620.44790.040*
C30.5078 (4)0.65807 (6)0.34397 (12)0.0296 (3)
C40.3787 (3)0.59711 (6)0.35650 (12)0.0284 (3)
C50.1810 (4)0.49926 (7)0.29216 (12)0.0307 (3)
H50.10960.49230.36170.037*
C60.1192 (4)0.44890 (7)0.20990 (12)0.0299 (3)
C70.2076 (4)0.45613 (7)0.10312 (12)0.0331 (3)
H70.31450.49340.08160.040*
C80.1335 (4)0.40665 (7)0.02923 (14)0.0376 (4)
H80.18850.41010.04290.045*
C90.0248 (4)0.35197 (7)0.06573 (14)0.0375 (4)
H90.08100.31820.01810.045*
C100.0979 (4)0.34840 (7)0.17395 (14)0.0387 (4)
H100.19830.31100.19780.046*
C110.6052 (4)0.68224 (7)0.24209 (13)0.0343 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0387 (2)0.0311 (2)0.0296 (2)0.00353 (13)0.00597 (16)0.00229 (12)
N40.0314 (6)0.0272 (6)0.0315 (6)0.0004 (4)0.0028 (5)0.0014 (5)
N60.0401 (7)0.0303 (6)0.0359 (7)0.0054 (5)0.0016 (5)0.0021 (5)
N110.0656 (10)0.0385 (8)0.0412 (8)0.0017 (7)0.0133 (7)0.0070 (6)
C10.0394 (8)0.0340 (8)0.0323 (8)0.0001 (6)0.0043 (6)0.0036 (6)
C20.0349 (7)0.0276 (7)0.0364 (8)0.0010 (5)0.0025 (6)0.0020 (5)
C30.0306 (7)0.0262 (7)0.0319 (7)0.0005 (5)0.0026 (5)0.0021 (5)
C40.0272 (7)0.0271 (7)0.0309 (7)0.0011 (5)0.0022 (5)0.0024 (5)
C50.0334 (7)0.0291 (7)0.0295 (7)0.0016 (5)0.0024 (5)0.0027 (5)
C60.0283 (6)0.0273 (7)0.0337 (7)0.0009 (5)0.0001 (5)0.0025 (5)
C70.0353 (7)0.0286 (7)0.0357 (7)0.0010 (5)0.0048 (6)0.0015 (6)
C80.0414 (8)0.0360 (8)0.0357 (8)0.0056 (6)0.0053 (6)0.0019 (6)
C90.0370 (8)0.0303 (8)0.0444 (9)0.0033 (6)0.0013 (6)0.0068 (6)
C100.0424 (8)0.0279 (7)0.0452 (9)0.0053 (6)0.0004 (7)0.0005 (6)
C110.0402 (8)0.0256 (7)0.0374 (8)0.0011 (6)0.0048 (6)0.0009 (6)
Geometric parameters (Å, º) top
S1—C11.7122 (15)C3—C111.428 (2)
S1—C41.7392 (15)C5—C61.463 (2)
N4—C51.2795 (18)C5—H50.9300
N4—C41.3869 (18)C6—C71.390 (2)
N6—C101.342 (2)C7—C81.388 (2)
N6—C61.3478 (19)C7—H70.9300
N11—C111.147 (2)C8—C91.387 (2)
C1—C21.352 (2)C8—H80.9300
C1—H10.9300C9—C101.383 (2)
C2—C31.424 (2)C9—H90.9300
C2—H20.9300C10—H100.9300
C3—C41.3802 (19)
C1—S1—C491.99 (7)C6—C5—H5118.5
C5—N4—C4118.89 (12)N6—C6—C7123.51 (13)
C10—N6—C6116.58 (13)N6—C6—C5114.22 (13)
C2—C1—S1112.46 (11)C7—C6—C5122.26 (13)
C2—C1—H1123.8C8—C7—C6118.79 (14)
S1—C1—H1123.8C8—C7—H7120.6
C1—C2—C3112.43 (13)C6—C7—H7120.6
C1—C2—H2123.8C9—C8—C7118.26 (15)
C3—C2—H2123.8C9—C8—H8120.9
C4—C3—C2113.14 (13)C7—C8—H8120.9
C4—C3—C11123.22 (13)C10—C9—C8119.06 (14)
C2—C3—C11123.64 (13)C10—C9—H9120.5
C3—C4—N4124.48 (13)C8—C9—H9120.5
C3—C4—S1109.97 (11)N6—C10—C9123.78 (14)
N4—C4—S1125.54 (10)N6—C10—H10118.1
N4—C5—C6123.08 (13)C9—C10—H10118.1
N4—C5—H5118.5N11—C11—C3177.44 (16)
C4—S1—C1—C20.03 (12)C4—N4—C5—C6179.46 (12)
S1—C1—C2—C30.06 (17)C10—N6—C6—C70.1 (2)
C1—C2—C3—C40.15 (19)C10—N6—C6—C5179.36 (13)
C1—C2—C3—C11179.33 (13)N4—C5—C6—N6178.52 (13)
C2—C3—C4—N4179.51 (12)N4—C5—C6—C72.0 (2)
C11—C3—C4—N40.0 (2)N6—C6—C7—C80.8 (2)
C2—C3—C4—S10.17 (16)C5—C6—C7—C8178.60 (13)
C11—C3—C4—S1179.31 (11)C6—C7—C8—C90.3 (2)
C5—N4—C4—C3174.38 (13)C7—C8—C9—C100.9 (2)
C5—N4—C4—S14.86 (19)C6—N6—C10—C91.2 (2)
C1—S1—C4—C30.12 (11)C8—C9—C10—N61.7 (2)
C1—S1—C4—N4179.45 (12)

Experimental details

Crystal data
Chemical formulaC11H7N3S
Mr213.26
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)3.8451 (1), 20.8901 (4), 12.2725 (2)
β (°) 94.952 (1)
V3)982.10 (4)
Z4
Radiation typeCu Kα
µ (mm1)2.64
Crystal size (mm)0.18 × 0.14 × 0.13
Data collection
DiffractometerBruker SMART 6000
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.637, 0.710
No. of measured, independent and
observed [I > 2σ(I)] reflections
13010, 1940, 1777
Rint0.037
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.102, 1.08
No. of reflections1940
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals
First citationMarris, T. (2004). UdMX. Université de Montréal, Montréal, Québec, Canada.
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationSkene, W. G., Dufresne, S., Trefz, T. & Simard, M. (2006). Acta Cryst. E62, o2382–o2384.  Web of Science CSD CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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