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The title compound, C16H12N4S, forms a three-dimensional layered network structure via inter­molecular hydrogen bonding and π-stacking. The azomethine molecule adopts the thermodynamically stable E regioisomer and the pyridine substituents are antiperi­planar. The mean planes of the pyridine rings and the azomethine group to which they are connected are twisted by 27.27 (5) and 33.60 (5)°. The electrochemical energy gap of 2.3 eV based on the HOMO–LUMO energy difference is in agreement with the spectroscopically derived value.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113024566/lg3122sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113024566/lg3122Isup2.hkl
Contains datablock I

cdx

Chemdraw file https://doi.org/10.1107/S0108270113024566/lg3122Isup3.cdx
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113024566/lg3122Isup4.cml
Supplementary material

CCDC reference: 969476

Introduction top

Various azomethines (–NCH–) have been prepared owing in part to their straightforward preparation by condensing complementary amines and aldehydes. The resulting heteroatomic bonds have been extensively used to coordinate various metals for obtaining optically and electrochemically active metal-coordinated compounds. It has also recently been demonstrated that metal-free azomethines similarly possess optical and electrochemical properties that are compatible for use as heteroatomic conjugated systems in plastic devices (Bolduc et al., 2013). It was shown that both the optical and electrochemical properties of the metal-free azomethines are highly contingent on the type of the aromatic rings and amines used for their preparation (Dufresne & Skene, 2008a,b).The variable properties were attributed not only to the different electron densities of the aromatics, but also to the different mean plane angles between of the aromatics and the azomethines (Dufresne & Skene, 2010a,b, 2012; Dufresne et al., 2010). For example, the mean plane angle between the aryl–azomethine bond for six-membered aromatics in aryl–azomethine–aryl–azomethine–aryl triads [compound (3) in the Scheme] is twisted by up to 65° (Bürgi & Dunitz, 1970). This is a result of steric hindrance between the azomethine and ortho-aromatic H atoms. In contrast, relatively low aryl–azomethine twist angles, ranging between 0 and 25°, were observed for triads consisting of five-membered aromatics (Bolduc et al., 2010, 2012, 2013; Guarin et al., 2007). Despite the plethora of azomethine crystallographic studies, crystal structures of azomethine triads consisting of mixed six- or five-membered rings have not been reported. The crystal structures of such triads would provide important information about the different twisting angles between the aryl-azomethine planes allowing for correlation with the optical and electrochemical properties. Additionally, a crystal structure is pivotal for determining the absolute E or Z orientation of the azomethine bond that cannot be assigned with conventional characterization techniques, such as NMR. The title compound was synthesized during the course of our on-going conjugated azomethine research for the purpose of providing the important crystallographic data.

Experimental top

Synthesis and crystallization top

All chemicals were purchased from Sigma–Aldrich. Anhydrous and deaerated solvents were obtained from an activated alumina solvent purification system.

For the synthesis of (1), DABCO (1,4-di­aza­bicyclo­[2.2.2]o­ctane; 0.47 g, 4.27 mmol) was dissolved in anhydrous toluene in a round-bottomed flask, followed by the addition of thio­phene-2,5-dicarboxaldehyde (0.10 g, 0.71 mmol). Then TiCl4 (0.1 M in toluene, 1.4 ml, 0.14 mmol) was added dropwise at 273 K. 3-Amino­pyridine (0.13 g, 1.42 mmol) was dissolved separately in anhydrous toluene. This solution was added to the TiCl4 containing reaction mixture and the resulting mixture was refluxed for 2 d. The solvent was then removed from the crude reaction mixture and the solid was redissolved in acetone. The undissolved solids were filtered. The solvent from the filtrate was then removed under reduced pressure. Purification by flash-column chromatography (80/20 hexanes/ethyl acetate) gave the title compound as a yellow powder (yield 0.21 mmol, 30%). Single crystals were obtained by slow evaporation of acetone at room temperature over a period of 3 weeks.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions (C—H = 0.95 Å) and included in the refinement in the riding-model approximation, with Uiso(H) values refined freely.

Results and discussion top

The crystal structure of the title compound N-((E)-{5-[(E)-(pyridin-3-yl­imino)­methyl]­thio­phen-2-yl}methyl­idene)pyridin-3-amine, (1), reveals that the compound adopts the thermodynamically stable E regioisomer. The molecule is not planar as the dihedral angles between mean planes of the central thio­phene and the adjacent pyridines are 27.27 (5) and 33.60 (5)°. This twisting can be attributed to the steric hindrance between the hydrogen of the imine bond and the hydrogen on the adjacent pyridine ring, as previously reported for six-membered heterocycles (Dufresne et al., 2008). This is in part responsible for the observed hypsochromic shifts in the absorbance spectra of (1) relative to its all-thio­phene analogue [compound (2) in the Scheme]. The mean plane dihedral angles of the aryl–azomethines bonds of (2) are 9.04 (4) and 25.07 (6)° (Skene et al., 2006) and they are also smaller than for the analogous six-membered homo­aryl azomethine triad, (E)-N-benzyl­idene-4-[(E)-(phenyl­imino)­methyl]­aniline [renamed to match scheme; please check that scheme shows correct structure], (3), whose mean plane torsion angle is 46 (3)° (Thyen & Zugenmaier, 1994). It is further evident from Fig. 1 that in (1) the pyridines are anti­planar.

Another point of inter­est is the bond length in the azomethines. The bond lengths for C6—N5, N5—C5 and C5—C1, as well as the bond lengths for C12—N11, N11—C11 and C11—C4 (see Table 2), are consistent with those of analogous triads consisting uniquely of thio­phenes. The analogous bond lengths for (2) are 1.439 (4), 1.278 (3) and 1.397 (3) Å (Skene et al., 2006). The azomethine bond lengths are 0.053 Å shorter than the CC bond of analogous vinyl­enes (Hoekstra et al., 1975). The different bond lengths confirm that the NCH and CHCH bonds are not isoelectronic in terms of bond distances, contrary to what is generally understood (Yang & Jenekhe, 1991).

The three-dimensional network of (1) is governed by multiple weak inter­actions. Fig. 2 shows those inter­actions with π-stacking occurring between inter­calated thio­phenes and azomethine bonds. The mean plane determined by atoms N5, C5, C1, C2, C3, C4, S1, C11 and N11 is at an acceptable π-stacking distance (Janiak, 2000) from the mean plane determined by the same atoms of the anti­periplanar molecule at (-x+1, -y+1, -z) (Fig. 2 and Table 3). π-stacking can also be observed between the central molecule and the syn molecule at (-x+1, y, -z+1/2) (Fig. 2), and between the aforementioned molecule at (-x+1, -y+1, -z) and the syn molecule at (x, -y+1, z-1/2) [-z-1/2 in Table 3] (Fig. 2). The molecules are oriented in anti or syn orientations owing to their hydrogen bonding in the crystal lattice. Table 4 and Fig. 3 describe the hydrogen-bonding pattern and the three-dimensional network of the molecules in (1).

The optical and electrochemical properties of the title compound are reported in Fig. 4. It can be seen that (1) has a maximum absorbance and emission wavelength of 365 and 495 nm, respectively. The conjugated nature of (1) is confirmed by the low optical energy gap of 2.8 eV, suggesting low twisting angles between the aryl and azomethine mean planes. However, the absorbance and fluorescence spectra of all-thio­phene analogue (2) are red shifted by 75 and 39 nm, respectively, relative to (1) (Bourgeaux et al., 2007). The degree of conjugation of (1) is further confirmed by the electrochemical properties found in the inset of Fig. 4. The oxidation at 1.06 V versus Ag/AgCl is irreversible because the resulting pyridine radical cation undergoes anodic polymerization. The reduction at -1.17 V versus Ag/AgCl is similarly irreversible. The HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) levels can be calculated from the oxidation and reduction onsets, respectively, resulting in HOMO = -5.4 eV and LUMO = -3.1 eV. The electrochemical energy gap (2.3 eV) is derived from the HOMO–LUMO energy difference and it is in agreement with the spectroscopically derived value.

Related literature top

For related literature, see: Bürgi & Dunitz (1970); Bolduc et al. (2010, 2012, 2013); Bourgeaux et al. (2007); Dufresne & Skene (2008a, 2008b, 2012); Dufresne et al. (2008, 2010); Guarin et al. (2007); Janiak (2000); Skene et al. (2006); Thyen & Zugenmaier (1994); Yang & Jenekhe (1991).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2001) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: UdMX (Maris, 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of (1), showing the atom-numbering scheme adopted. Displacement ellipsoids are drawn at 30% probability level.
[Figure 2] Fig. 2. Three-dimensional structure of (1) shown along the b axis, illustrating the π-stacking within the crystal lattice.[Symmetry codes: (i) 1 - x, y, 0.5 - z ii)1 - x, 1 - y, -z iii) x, 1 - y, -0.5 + z].
[Figure 3] Fig. 3. Three dimensional structure of 1 shown along the c axis illustrating the hydrogen-bond interactions within the crystal lattice. Only the atoms involved in hydrogen bonds are numbered and only the hydrogen involved are shown for clarity. [Symmetry codes: (i) -x+1/2, y-1/2, -z-1/2; (ii) -x+1, y+1, -z+1/2.]
[Figure 4] Fig. 4. Normalized absorbance (black dot) and emission (square) of (1) in dichloromethane. Inset: cyclic voltammogram of (1) in 0.1 M TBAPF6 in anhydrous and deaerated dichloromethane.
N-((E)-{5-[(E)-(Pyridin-3-ylimino)methyl]thiophen-2-yl}methylidene)pyridin-3-amine top
Crystal data top
C16H12N4SF(000) = 1216
Mr = 292.36Dx = 1.383 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9039 reflections
a = 33.4368 (5) Åθ = 2.8–72.1°
b = 6.0490 (1) ŵ = 0.23 mm1
c = 14.6066 (2) ÅT = 150 K
β = 108.034 (1)°Plate, yellow
V = 2809.18 (7) Å30.12 × 0.08 × 0.05 mm
Z = 8
Data collection top
Bruker SMART 6000
diffractometer
2773 independent reflections
Radiation source: Rotating Anode2581 reflections with I > 2σ(I)
Montel 200 optics monochromatorRint = 0.043
Detector resolution: 5.5 pixels mm-1θmax = 26.1°, θmin = 1.3°
ω scansh = 4040
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 77
Tmin = 0.827, Tmax = 1.000l = 1717
18280 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)] = 0.036Only H-atom displacement parameters refined
wR(F2) = 0.094 w = 1/[σ2(Fo2) + (0.0575P)2 + 1.3506P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
2773 reflectionsΔρmax = 0.23 e Å3
203 parametersΔρmin = 0.32 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: 0.0082 (6)
Crystal data top
C16H12N4SV = 2809.18 (7) Å3
Mr = 292.36Z = 8
Monoclinic, C2/cMo Kα radiation
a = 33.4368 (5) ŵ = 0.23 mm1
b = 6.0490 (1) ÅT = 150 K
c = 14.6066 (2) Å0.12 × 0.08 × 0.05 mm
β = 108.034 (1)°
Data collection top
Bruker SMART 6000
diffractometer
2773 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2581 reflections with I > 2σ(I)
Tmin = 0.827, Tmax = 1.000Rint = 0.043
18280 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.094Only H-atom displacement parameters refined
S = 1.07Δρmax = 0.23 e Å3
2773 reflectionsΔρmin = 0.32 e Å3
203 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, equipped with a Bruker SMART 4 K Charged-Coupled Device (CCD) Area Detector using the program 2 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
S10.494790 (9)0.43847 (5)0.12073 (2)0.02215 (13)
C10.46157 (4)0.6498 (2)0.06511 (9)0.0245 (3)
C20.48038 (4)0.8538 (2)0.08655 (9)0.0270 (3)
H20.46680.98910.06210.039 (4)*
C30.52212 (4)0.8394 (2)0.14898 (9)0.0272 (3)
H30.53970.96400.17160.040 (5)*
C40.53440 (4)0.6242 (2)0.17338 (9)0.0245 (3)
C50.41971 (4)0.6033 (2)0.00183 (9)0.0250 (3)
H50.40200.72220.02850.034 (4)*
C60.36502 (4)0.3683 (2)0.07637 (9)0.0253 (3)
C70.33116 (4)0.5106 (2)0.08330 (10)0.0296 (3)
H70.33610.63910.04400.038 (4)*
C80.28572 (4)0.2909 (3)0.19639 (10)0.0352 (3)
H80.25840.26480.23970.046 (5)*
C90.31693 (5)0.1366 (3)0.19210 (10)0.0337 (3)
H90.31080.00680.23060.048 (5)*
C100.35708 (4)0.1747 (2)0.13088 (9)0.0291 (3)
H100.37890.07060.12600.036 (4)*
C110.57432 (4)0.5450 (2)0.23643 (9)0.0246 (3)
H110.59560.64790.26800.035 (4)*
C120.61990 (4)0.2621 (2)0.31301 (9)0.0242 (3)
C130.61887 (4)0.0623 (2)0.36000 (10)0.0283 (3)
H130.59230.00720.34900.032 (4)*
C140.68957 (5)0.0631 (3)0.43387 (11)0.0367 (4)
H140.71410.00600.47500.051 (5)*
C150.69398 (4)0.2638 (3)0.39202 (10)0.0351 (3)
H150.72090.33080.40570.041 (4)*
C160.65884 (4)0.3655 (2)0.33020 (9)0.0294 (3)
H160.66120.50230.30030.029 (4)*
N50.40623 (3)0.40443 (19)0.01400 (8)0.0250 (3)
N70.29210 (4)0.4748 (2)0.14263 (9)0.0356 (3)
N110.58121 (3)0.33688 (18)0.24999 (7)0.0248 (2)
N130.65245 (4)0.0382 (2)0.41918 (9)0.0349 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0232 (2)0.0189 (2)0.02419 (19)0.00122 (10)0.00713 (14)0.00032 (11)
C10.0271 (6)0.0234 (6)0.0245 (6)0.0006 (5)0.0102 (5)0.0002 (5)
C20.0282 (6)0.0231 (7)0.0301 (6)0.0007 (5)0.0096 (5)0.0005 (5)
C30.0265 (6)0.0227 (6)0.0326 (7)0.0028 (5)0.0094 (5)0.0020 (5)
C40.0242 (6)0.0245 (6)0.0267 (6)0.0026 (5)0.0104 (5)0.0018 (5)
C50.0258 (6)0.0256 (6)0.0238 (6)0.0013 (5)0.0080 (5)0.0016 (5)
C60.0279 (6)0.0248 (6)0.0231 (6)0.0032 (5)0.0080 (5)0.0016 (5)
C70.0274 (7)0.0298 (7)0.0304 (7)0.0018 (5)0.0070 (5)0.0040 (6)
C80.0282 (7)0.0432 (8)0.0298 (7)0.0080 (6)0.0029 (6)0.0016 (6)
C90.0392 (8)0.0325 (7)0.0286 (7)0.0085 (6)0.0093 (6)0.0046 (6)
C100.0337 (7)0.0248 (7)0.0294 (7)0.0018 (5)0.0106 (6)0.0002 (5)
C110.0234 (6)0.0251 (7)0.0267 (6)0.0026 (5)0.0098 (5)0.0025 (5)
C120.0247 (6)0.0250 (6)0.0237 (6)0.0008 (5)0.0086 (5)0.0033 (5)
C130.0313 (7)0.0254 (7)0.0285 (7)0.0005 (5)0.0098 (6)0.0017 (5)
C140.0332 (8)0.0416 (9)0.0306 (7)0.0099 (6)0.0027 (6)0.0016 (6)
C150.0253 (7)0.0429 (8)0.0356 (7)0.0005 (6)0.0073 (6)0.0063 (6)
C160.0269 (7)0.0311 (7)0.0306 (7)0.0021 (5)0.0094 (5)0.0016 (6)
N50.0251 (6)0.0264 (6)0.0231 (5)0.0008 (4)0.0070 (4)0.0001 (4)
N70.0263 (6)0.0403 (7)0.0370 (7)0.0007 (5)0.0050 (5)0.0025 (5)
N110.0227 (5)0.0257 (6)0.0263 (5)0.0012 (4)0.0079 (4)0.0003 (4)
N130.0403 (7)0.0311 (6)0.0306 (6)0.0056 (5)0.0072 (5)0.0020 (5)
Geometric parameters (Å, º) top
S1—C11.7231 (13)C8—H80.95
S1—C41.7253 (13)C9—C101.3828 (19)
C1—C21.3768 (18)C9—H90.95
C1—C51.4459 (18)C10—H100.95
C2—C31.4138 (19)C11—N111.2839 (17)
C2—H20.95C11—H110.95
C3—C41.3785 (18)C12—C161.3953 (18)
C3—H30.95C12—C131.3959 (18)
C4—C111.4486 (18)C12—N111.4101 (16)
C5—N51.2805 (17)C13—N131.3326 (18)
C5—H50.95C13—H130.95
C6—C101.3947 (18)C14—N131.340 (2)
C6—C71.4009 (19)C14—C151.387 (2)
C6—N51.4141 (17)C14—H140.95
C7—N71.3428 (17)C15—C161.3850 (19)
C7—H70.95C15—H150.95
C8—N71.340 (2)C16—H160.95
C8—C91.387 (2)
C1—S1—C491.21 (6)C8—C9—H9120.5
C2—C1—C5127.10 (12)C9—C10—C6118.95 (13)
C2—C1—S1112.04 (10)C9—C10—H10120.5
C5—C1—S1120.83 (10)C6—C10—H10120.5
C1—C2—C3112.45 (12)N11—C11—C4120.56 (12)
C1—C2—H2123.8N11—C11—H11119.7
C3—C2—H2123.8C4—C11—H11119.7
C4—C3—C2112.36 (12)C16—C12—C13117.62 (12)
C4—C3—H3123.8C16—C12—N11126.16 (12)
C2—C3—H3123.8C13—C12—N11116.19 (11)
C3—C4—C11128.23 (12)N13—C13—C12124.72 (13)
C3—C4—S1111.95 (10)N13—C13—H13117.6
C11—C4—S1119.81 (10)C12—C13—H13117.6
N5—C5—C1120.99 (12)N13—C14—C15123.27 (14)
N5—C5—H5119.5N13—C14—H14118.4
C1—C5—H5119.5C15—C14—H14118.4
C10—C6—C7117.92 (12)C16—C15—C14119.46 (14)
C10—C6—N5118.22 (12)C16—C15—H15120.3
C7—C6—N5123.79 (12)C14—C15—H15120.3
N7—C7—C6123.38 (13)C15—C16—C12118.30 (13)
N7—C7—H7118.3C15—C16—H16120.9
C6—C7—H7118.3C12—C16—H16120.9
N7—C8—C9123.45 (13)C5—N5—C6118.69 (12)
N7—C8—H8118.3C8—N7—C7117.31 (13)
C9—C8—H8118.3C11—N11—C12119.99 (11)
C10—C9—C8118.91 (13)C13—N13—C14116.62 (13)
C10—C9—H9120.5
C4—S1—C1—C20.03 (10)S1—C4—C11—N113.27 (17)
C4—S1—C1—C5178.12 (11)C16—C12—C13—N130.8 (2)
C5—C1—C2—C3178.22 (12)N11—C12—C13—N13177.35 (12)
S1—C1—C2—C30.21 (15)N13—C14—C15—C161.4 (2)
C1—C2—C3—C40.42 (17)C14—C15—C16—C120.6 (2)
C2—C3—C4—C11178.99 (12)C13—C12—C16—C150.39 (19)
C2—C3—C4—S10.44 (15)N11—C12—C16—C15177.60 (12)
C1—S1—C4—C30.27 (10)C1—C5—N5—C6179.89 (11)
C1—S1—C4—C11178.96 (11)C10—C6—N5—C5148.52 (12)
C2—C1—C5—N5178.24 (13)C7—C6—N5—C534.63 (19)
S1—C1—C5—N50.40 (17)C9—C8—N7—C71.3 (2)
C10—C6—C7—N73.0 (2)C6—C7—N7—C80.9 (2)
N5—C6—C7—N7179.88 (13)C4—C11—N11—C12178.76 (11)
N7—C8—C9—C101.4 (2)C16—C12—N11—C1131.89 (19)
C8—C9—C10—C60.8 (2)C13—C12—N11—C11150.10 (12)
C7—C6—C10—C92.84 (19)C12—C13—N13—C140.2 (2)
N5—C6—C10—C9179.88 (12)C15—C14—N13—C130.9 (2)
C3—C4—C11—N11178.28 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···N7i0.952.663.4881 (19)146
C7—H7···N13ii0.952.623.5614 (19)173
Symmetry codes: (i) x+1/2, y1/2, z1/2; (ii) x+1, y+1, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H12N4S
Mr292.36
Crystal system, space groupMonoclinic, C2/c
Temperature (K)150
a, b, c (Å)33.4368 (5), 6.0490 (1), 14.6066 (2)
β (°) 108.034 (1)
V3)2809.18 (7)
Z8
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.12 × 0.08 × 0.05
Data collection
DiffractometerBruker SMART 6000
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.827, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
18280, 2773, 2581
Rint0.043
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.094, 1.07
No. of reflections2773
No. of parameters203
H-atom treatmentOnly H-atom displacement parameters refined
Δρmax, Δρmin (e Å3)0.23, 0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2001) and ORTEP-3 for Windows (Farrugia, 2012), UdMX (Maris, 2004).

Selected geometric parameters (Å, º) top
C1—C51.4459 (18)C6—N51.4141 (17)
C4—C111.4486 (18)C11—N111.2839 (17)
C5—N51.2805 (17)C12—N111.4101 (16)
N5—C5—C1120.99 (12)N11—C11—C4120.56 (12)
Geometry (Å, °) of π-stacking interactions top
Mean planes descriptionaπ-stacking distances (Å)π-stacking angles (°)c
M···Mi3.3–3.7c6.62 (2)
M···Mii3.433 (6)0.00 (2)
Mii···Miii3.3–3.7c6.62 (2)
Notes: (a) M is the plane formed by atoms N5, C5, C1, C2, C3, C4, S1, C11 and N11; (b) π-stacking angle is the angle between the mean planes used for π-stacking distances calculations; (c) distance range between the atoms and the planes described by the molecules, since π-stacking interactions could not be accurately calculated owing to the angle between the mean planes. Symmetry codes: (i) -x+1, y, -z+1/2; (ii) -x+1, -y+1, -z; (iii) x, -y+1, -z-1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C8—H8···N7i0.952.663.4881 (19)146
C7—H7···N13ii0.952.623.5614 (19)173
Symmetry codes: (i) x+1/2, y1/2, z1/2; (ii) x+1, y+1, z+1/2.
 

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