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access2,3-Bis(thiophen-3-yl)quinoxaline
aDepartment of Chemistry, Central Connecticut State University, New Britain, CT 06053, USA
*Correspondence e-mail: crundwellg@mail.ccsu.edu
In the title compound, C16H10N2S2, the thienyl rings are inclined to one another by 62.71 (10)°, and are inclined by 63.94 (8) and 21.35 (8)° to the quinoline mean plane [maximum deviation = 0.031 (2) Å]. In the crystal, the molecules pack in a herringbone pattern, with π–π stacking interactions [centroid–centroid distances = 3.7381 (15) and 3.7268 (15) Å].
Related literature
For the synthesis of the title compound, and the of the 2,3-di(thiophen-2-yl)quinoxaline analogue, see: Crundwell et al. (2003![[Crundwell, G., Sayers, D., Herron, S. R. & Kantardjieff, K. A. (2003). Acta Cryst. E59, o314-o315.]](../../../../../../logos/arrows/e_arr.gif "Crundwell, G., Sayers, D., Herron, S. R. & Kantardjieff, K. A. (2003). Acta Cryst. E59, o314-o315.")
). For the structure of a similar compound, see: Cantalupo et al. (2010).
![[Scheme 1]](su2562scheme1.gif)
Experimental
Crystal data
|
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536813004248/su2562sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536813004248/su2562Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813004248/su2562Isup3.cml
The title compound was prepared and purified according to literature methods (Crundwell et al., 2003). Equal mole amounts of o-phenylenediamine (1.62 g, 15.0 mmol) and 3,3'-thenil (3.33 g, 15.0 mmol) were dissolved in 95% ethanol and heated in an Erlenmeyer flask in a hot water bath. Recrystallization of the crude product from boiling ethanol sufficiently purified the quinoxaline product as a pale white solid (3.71 g, 12.6 mmol; 84% yield; M.p. 403 K). Spectroscopic data for the title compound are available in the archived CIF.
Hydrogen atoms were included in calculated positions and included in the in the riding motion approximation: C-H = 0.93 Å with Uiso = 1.2Ueq(C).
Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./su2562fig1thm.gif) | Fig. 1. A view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. |
| C16H10N2S2 | F(000) = 608 |
| Mr = 294.38 | Dx = 1.420 Mg m−3 |
| Monoclinic, P21/c | Melting point: 406 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 15.966 (2) Å | Cell parameters from 3293 reflections |
| b = 5.5741 (15) Å | θ = 4.1–33.0° |
| c = 15.629 (4) Å | µ = 0.38 mm−1 |
| β = 98.25 (2)° | T = 293 K |
| V = 1376.5 (6) Å3 | Block, white |
| Z = 4 | 0.45 × 0.44 × 0.39 mm |
| Oxford Diffraction Xcalibur Sapphire3 diffractometer | 4745 independent reflections |
| Radiation source: fine-focus sealed tube | 2660 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.087 |
| Detector resolution: 16.1790 pixels mm-1 | θmax = 32.5°, θmin = 4.2° |
| ω scans | h = −23→23 |
| Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −8→8 |
| Tmin = 0.731, Tmax = 1.000 | l = −23→23 |
| 30279 measured reflections |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.183 | H-atom parameters constrained |
| S = 0.92 | w = 1/[σ2(Fo2) + (0.1124P)2] where P = (Fo2 + 2Fc2)/3 |
| 4745 reflections | (Δ/σ)max = 0.001 |
| 181 parameters | Δρmax = 0.44 e Å−3 |
| 0 restraints | Δρmin = −0.50 e Å−3 |
| C16H10N2S2 | V = 1376.5 (6) Å3 |
| Mr = 294.38 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 15.966 (2) Å | µ = 0.38 mm−1 |
| b = 5.5741 (15) Å | T = 293 K |
| c = 15.629 (4) Å | 0.45 × 0.44 × 0.39 mm |
| β = 98.25 (2)° |
| Oxford Diffraction Xcalibur Sapphire3 diffractometer | 4745 independent reflections |
| Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 2660 reflections with I > 2σ(I) |
| Tmin = 0.731, Tmax = 1.000 | Rint = 0.087 |
| 30279 measured reflections |
| R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
| wR(F2) = 0.183 | H-atom parameters constrained |
| S = 0.92 | Δρmax = 0.44 e Å−3 |
| 4745 reflections | Δρmin = −0.50 e Å−3 |
| 181 parameters |
Experimental. Spectroscopic data for the title compound: 1H NMR (300 MHz, (CD3)2CO) d 8.088 (m, 1H), 7.840 (m, 1H), 7.678 (dd, 1H),7.539 (dd, 1H), 7.331 (dd, 1H); 13C NMR (300 MHz,CDCl3) d 148.81, 140.86, 140.51, 129.88, 128.90, 128.60, 127.02, 125.50. |
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 | ||
| N1 | 0.29116 (9) | 0.2491 (3) | −0.02718 (9) | 0.0397 (3) | |
| C1 | 0.29649 (11) | 0.4316 (3) | 0.02698 (11) | 0.0360 (4) | |
| C2 | 0.22246 (11) | 0.5650 (3) | 0.04216 (11) | 0.0373 (4) | |
| N2 | 0.14724 (10) | 0.5169 (3) | −0.00197 (10) | 0.0423 (4) | |
| C3 | 0.14154 (11) | 0.3343 (4) | −0.06015 (11) | 0.0406 (4) | |
| C4 | 0.06234 (12) | 0.2759 (4) | −0.10817 (13) | 0.0531 (5) | |
| H4 | 0.0146 | 0.3653 | −0.1010 | 0.064* | |
| C5 | 0.05559 (14) | 0.0887 (4) | −0.16501 (14) | 0.0586 (6) | |
| H5 | 0.0034 | 0.0525 | −0.1970 | 0.070* | |
| C6 | 0.12757 (15) | −0.0510 (4) | −0.17559 (14) | 0.0543 (5) | |
| H6 | 0.1222 | −0.1786 | −0.2143 | 0.065* | |
| C7 | 0.20477 (13) | 0.0005 (4) | −0.12934 (13) | 0.0466 (5) | |
| H7 | 0.2516 | −0.0929 | −0.1361 | 0.056* | |
| C8 | 0.21308 (11) | 0.1952 (3) | −0.07156 (11) | 0.0391 (4) | |
| C9 | 0.43076 (12) | 0.3380 (4) | 0.12458 (12) | 0.0478 (5) | |
| H9 | 0.4125 | 0.1877 | 0.1400 | 0.057* | |
| C10 | 0.38308 (11) | 0.4901 (3) | 0.07058 (11) | 0.0367 (4) | |
| C11 | 0.42746 (12) | 0.7043 (4) | 0.05750 (12) | 0.0469 (5) | |
| H11 | 0.4048 | 0.8291 | 0.0220 | 0.056* | |
| C12 | 0.50766 (12) | 0.7072 (4) | 0.10303 (14) | 0.0535 (5) | |
| H12 | 0.5458 | 0.8328 | 0.1019 | 0.064* | |
| S1 | 0.52814 (3) | 0.45345 (12) | 0.16120 (4) | 0.0617 (2) | |
| C13 | 0.28349 (12) | 0.7946 (4) | 0.17905 (12) | 0.0453 (4) | |
| H13 | 0.3306 | 0.6973 | 0.1940 | 0.054* | |
| C14 | 0.22447 (11) | 0.7587 (3) | 0.10719 (11) | 0.0387 (4) | |
| C15 | 0.15839 (13) | 0.9348 (4) | 0.10173 (13) | 0.0459 (5) | |
| H15 | 0.1122 | 0.9381 | 0.0581 | 0.055* | |
| C16 | 0.17121 (12) | 1.1020 (4) | 0.16974 (13) | 0.0439 (4) | |
| H16 | 0.1355 | 1.2304 | 0.1765 | 0.053* | |
| S2 | 0.26067 (4) | 1.03661 (12) | 0.23738 (4) | 0.0598 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0331 (7) | 0.0495 (9) | 0.0355 (7) | −0.0031 (6) | 0.0019 (6) | −0.0029 (7) |
| C1 | 0.0306 (8) | 0.0450 (10) | 0.0321 (8) | −0.0010 (7) | 0.0028 (6) | 0.0029 (7) |
| C2 | 0.0324 (8) | 0.0463 (11) | 0.0324 (8) | −0.0016 (7) | 0.0020 (6) | 0.0040 (7) |
| N2 | 0.0338 (8) | 0.0528 (10) | 0.0387 (8) | −0.0007 (6) | 0.0000 (6) | 0.0033 (7) |
| C3 | 0.0352 (9) | 0.0495 (11) | 0.0353 (8) | −0.0035 (8) | −0.0007 (7) | 0.0041 (8) |
| C4 | 0.0373 (10) | 0.0663 (14) | 0.0523 (11) | −0.0016 (9) | −0.0054 (8) | −0.0031 (10) |
| C5 | 0.0437 (11) | 0.0759 (16) | 0.0515 (12) | −0.0120 (10) | −0.0088 (9) | −0.0036 (11) |
| C6 | 0.0559 (12) | 0.0628 (14) | 0.0414 (10) | −0.0125 (10) | −0.0028 (9) | −0.0093 (10) |
| C7 | 0.0445 (10) | 0.0530 (12) | 0.0418 (10) | −0.0057 (8) | 0.0043 (8) | −0.0053 (8) |
| C8 | 0.0346 (8) | 0.0497 (11) | 0.0322 (8) | −0.0066 (7) | 0.0019 (6) | 0.0027 (8) |
| C9 | 0.0388 (10) | 0.0525 (12) | 0.0490 (11) | −0.0023 (8) | −0.0045 (8) | 0.0020 (9) |
| C10 | 0.0306 (8) | 0.0470 (10) | 0.0322 (8) | −0.0010 (7) | 0.0030 (6) | −0.0044 (7) |
| C11 | 0.0424 (10) | 0.0518 (12) | 0.0461 (10) | −0.0055 (8) | 0.0049 (8) | 0.0037 (9) |
| C12 | 0.0373 (10) | 0.0597 (13) | 0.0635 (13) | −0.0132 (9) | 0.0076 (9) | −0.0124 (11) |
| S1 | 0.0398 (3) | 0.0779 (5) | 0.0612 (4) | 0.0005 (2) | −0.0134 (2) | −0.0057 (3) |
| C13 | 0.0437 (10) | 0.0523 (11) | 0.0398 (9) | 0.0014 (9) | 0.0052 (7) | −0.0036 (9) |
| C14 | 0.0358 (8) | 0.0446 (10) | 0.0368 (8) | −0.0011 (7) | 0.0092 (7) | 0.0008 (7) |
| C15 | 0.0408 (10) | 0.0519 (12) | 0.0462 (10) | 0.0024 (8) | 0.0104 (8) | 0.0049 (9) |
| C16 | 0.0397 (9) | 0.0428 (10) | 0.0518 (11) | 0.0044 (8) | 0.0154 (8) | 0.0022 (8) |
| S2 | 0.0572 (4) | 0.0705 (4) | 0.0532 (3) | −0.0039 (3) | 0.0130 (3) | −0.0152 (3) |
| N1—C1 | 1.318 (2) | C9—C10 | 1.351 (3) |
| N1—C8 | 1.370 (2) | C9—S1 | 1.7040 (19) |
| C1—C2 | 1.445 (2) | C9—H9 | 0.9300 |
| C1—C10 | 1.487 (2) | C10—C11 | 1.418 (3) |
| C2—N2 | 1.324 (2) | C11—C12 | 1.373 (3) |
| C2—C14 | 1.480 (2) | C11—H11 | 0.9300 |
| N2—C3 | 1.359 (2) | C12—S1 | 1.688 (2) |
| C3—C8 | 1.413 (3) | C12—H12 | 0.9300 |
| C3—C4 | 1.413 (2) | C13—C14 | 1.373 (2) |
| C4—C5 | 1.365 (3) | C13—S2 | 1.697 (2) |
| C4—H4 | 0.9300 | C13—H13 | 0.9300 |
| C5—C6 | 1.417 (3) | C14—C15 | 1.435 (3) |
| C5—H5 | 0.9300 | C15—C16 | 1.406 (3) |
| C6—C7 | 1.367 (3) | C15—H15 | 0.9300 |
| C6—H6 | 0.9300 | C16—S2 | 1.690 (2) |
| C7—C8 | 1.406 (3) | C16—H16 | 0.9300 |
| C7—H7 | 0.9300 | ||
| C1—N1—C8 | 117.70 (15) | C10—C9—S1 | 112.20 (16) |
| N1—C1—C2 | 121.58 (16) | C10—C9—H9 | 123.9 |
| N1—C1—C10 | 115.70 (15) | S1—C9—H9 | 123.9 |
| C2—C1—C10 | 122.72 (16) | C9—C10—C11 | 111.71 (17) |
| N2—C2—C1 | 120.83 (17) | C9—C10—C1 | 123.50 (17) |
| N2—C2—C14 | 115.76 (16) | C11—C10—C1 | 124.71 (16) |
| C1—C2—C14 | 123.41 (15) | C12—C11—C10 | 112.53 (18) |
| C2—N2—C3 | 117.98 (16) | C12—C11—H11 | 123.7 |
| N2—C3—C8 | 121.18 (16) | C10—C11—H11 | 123.7 |
| N2—C3—C4 | 119.79 (17) | C11—C12—S1 | 111.33 (16) |
| C8—C3—C4 | 118.99 (18) | C11—C12—H12 | 124.3 |
| C5—C4—C3 | 120.2 (2) | S1—C12—H12 | 124.3 |
| C5—C4—H4 | 119.9 | C12—S1—C9 | 92.21 (10) |
| C3—C4—H4 | 119.9 | C14—C13—S2 | 112.35 (15) |
| C4—C5—C6 | 120.42 (19) | C14—C13—H13 | 123.8 |
| C4—C5—H5 | 119.8 | S2—C13—H13 | 123.8 |
| C6—C5—H5 | 119.8 | C13—C14—C15 | 111.18 (18) |
| C7—C6—C5 | 120.5 (2) | C13—C14—C2 | 127.79 (17) |
| C7—C6—H6 | 119.7 | C15—C14—C2 | 121.00 (17) |
| C5—C6—H6 | 119.7 | C16—C15—C14 | 112.50 (18) |
| C6—C7—C8 | 119.8 (2) | C16—C15—H15 | 123.8 |
| C6—C7—H7 | 120.1 | C14—C15—H15 | 123.8 |
| C8—C7—H7 | 120.1 | C15—C16—S2 | 110.37 (15) |
| N1—C8—C7 | 119.34 (17) | C15—C16—H16 | 124.8 |
| N1—C8—C3 | 120.58 (17) | S2—C16—H16 | 124.8 |
| C7—C8—C3 | 120.08 (16) | C16—S2—C13 | 93.60 (10) |
Experimental details
| Crystal data | |
| Chemical formula | C16H10N2S2 |
| Mr | 294.38 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 15.966 (2), 5.5741 (15), 15.629 (4) |
| β (°) | 98.25 (2) |
| V (Å3) | 1376.5 (6) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.38 |
| Crystal size (mm) | 0.45 × 0.44 × 0.39 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur Sapphire3 diffractometer |
| Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
| Tmin, Tmax | 0.731, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 30279, 4745, 2660 |
| Rint | 0.087 |
| (sin θ/λ)max (Å−1) | 0.757 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.183, 0.92 |
| No. of reflections | 4745 |
| No. of parameters | 181 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.44, −0.50 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).
Acknowledgements
This research was funded by a CCSU–AAUP research grant.
References
Cantalupo, S. A., Crundwell, G. & Glagovich, N. (2010). Acta Cryst. E66, o2184. Web of Science CSD CrossRef IUCr Journals Google Scholar
Crundwell, G., Sayers, D., Herron, S. R. & Kantardjieff, K. A. (2003). Acta Cryst. E59, o314–o315. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD, CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
In the title compound, Fig. 1, the quinoxaline moiety is flat, with a dihedral angle involving rings N1/N2/C1-C3/C8 and C3-C8 of 1.71 (9) °, and the two thienyl rings, S1/C9-C12 and S2/C13-C16, are inclined to the quinoxaline mean plane by 63.94 (8) and 21.35 (8) °, respectively. All bond lengths and angles fall within the typical ranges found in similar compounds (Cantalupo et al., 2010; Crundwell et al., 2003).
In the crystal, molecules pack in a herringbone pattern with π···π intermolecular contacts of 3.7381 (15) and 3.7268 (15) Å, for Cg1···Cg1i and Cg2···Cg3ii, respectively [where Cg1 is ring S1/C9-C12; Cg2 is ring S2/C13-C16; Cg3 is ring N1/N2/C1-C3/C8; symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y+1, z].