Related literature

Acta Crystallogr Sect E Struct Rep Online

Acta Cryst. E

Acta Crystallographica Section E: Structure Reports Online

1600-5368

International Union of Crystallography

23468779

3588814

lx2267

10.1107/S1600536812043188

ACSEBH

S1600536812043188

Organic Papers

2-[(E)-(Pyridin-2-ylmethylidene)amino]thiophene-3-carbonitrile

C₁₁H₇N₃S

Bolduc

Andréanne

aKnipping

Étienne

aSkene

W. G.

a*aDepartment of Chemistry, Université de Montréall, CP 6128, succ. Centre-ville, Montréal, Qc, Canada

Correspondence e-mail: w.skene@umontreal.ca

01122012

03112012

68Pt 12

e121200

o3262o3262189201216102012

2012

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

A full version of this article is available from Crystallography Journals Online.

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.

Related literature

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

Experimental <sec id="sec2.1.1"><title>Crystal data

C₁₁H₇N₃S

M _r = 213.26

Monoclinic,

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 ▶) T _min = 0.637, T _max = 0.710

13010 measured reflections

1940 independent reflections

1777 reflections with I > 2σ(I)

R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.035

wR(F ²) = 0.102

S = 1.08

1940 reflections

137 parameters

H-atom parameters constrained

Δρ_max = 0.20 e Å⁻³

Δρ_min = −0.24 e Å⁻³

Data collection: <italic>APEX2</italic> (Bruker, 2009<xref ref-type="bibr" rid="bb1"> ▶</xref>); cell refinement: <italic>SAINT</italic> (Bruker, 2009<xref ref-type="bibr" rid="bb1"> ▶</xref>); data reduction: <italic>SAINT</italic>; program(s) used to solve structure: <italic>SHELXS97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb5"> ▶</xref>); program(s) used to refine structure: <italic>SHELXL97</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb5"> ▶</xref>); molecular graphics: <italic>ORTEP-3 for Windows</italic> (Farrugia, 1997<xref ref-type="bibr" rid="bb2"> ▶</xref>); software used to prepare material for publication: <italic>UdMX</italic> (Marris, 2004<xref ref-type="bibr" rid="bb3"> ▶</xref>).</sec></sec><sec sec-type="supplementary-material"><title>Supplementary Material

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812043188/lx2267sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043188/lx2267Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043188/lx2267Isup3.cdx

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043188/lx2267Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LX2267).

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.

supplementary crystallographic information Comment

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.

Experimental

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%).

FiguresFig. 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).

Crystal data

C₁₁H₇N₃S	F(000) = 440
M_r = 213.26	D_x = 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

Data collection

Bruker SMART 6000 diffractometer	1940 independent reflections
Radiation source: Rotating Anode	1777 reflections with I > 2σ(I)
Montel 200 optics monochromator	R_int = 0.037
Detector resolution: 5.5 pixels mm^-1	θ_max = 72.6°, θ_min = 4.2°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −25→22
T_min = 0.637, T_max = 0.710	l = −15→15
13010 measured reflections

Refinement

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(F_o²) + (0.0705P)² + 0.1553P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1940 reflections	Δρ_max = 0.20 e Å⁻³
137 parameters	Δρ_min = −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)

Special details

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)

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å2)

	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)

Geometric parameters (Å, º)

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)

References

Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Marris, T. (2004). UdMX Université de Montréal, Montréal, Québec, Canada.

Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Skene, W. G., Dufresne, S., Trefz, T. & Simard, M. (2006). Acta Cryst. E62, o2382–o2384.