organic compounds
2-[5-(Pyridin-2-yl)-1,3,4-thiadiazol-2-yl]pyridin-1-ium perchlorate
aLaboratoire de Chimie de Coordination et d'Analytique (LCCA), Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, bLaboratoire de Catalyse et de Corrosion de Matériaux (LCCM), Faculté des Sciences, Université Chouaib Doukkali, BP 20, M-24000 El Jadida, Morocco, and cLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Batouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: salaheddine_guesmi@yahoo.fr
The cation of the title molecular salt, C12H9N4S+·ClO4−, is approximately planar, with the pyridine and pyridinium rings being inclined to the central thiadiazole ring by 6.51 (9) and 9.13 (9)°, respectively. The dihedral angle between the pyridine and pyridinium rings is 12.91 (10)°. In the crystal, the cations are linked by N—H⋯O and C—H⋯O hydrogen bonds, involving the perchlorate anion, forming chains propagating along the [100] direction. The chains are linked by weak offset π–π interactions [inter-centroid distance = 3.586 (1) Å], forming layers parallel to the ab plane.
Keywords: crystal structure; pyridine; pyridinium; thiadiazole; hydrogen bonding; offset π–π interactions.
CCDC reference: 1539885
Structure description
Transition metal complexes with the ligand 2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole (L) have attracted considerable attention owing to their magnetic properties (Klingele et al., 2010) and biological activity (Zine et al., 2016). Indeed, the ligand (L) can coordinate to different metal ions in many modes (Bentiss et al., 2002, 2011; Ahmed et al., 2015; Laachir et al., 2013, 2015a,b). However, we observed the formation of the title compound with the same ligand after the addition of perchloric acid, as a result of the proton donor-acceptor reaction between perchloric acid and 2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole (L). In this case, no metallic salt was used.
The structure of the title molecular salt is shown in Fig. 1. The cation is almost planar with the pyridine (N1/C1–C5) and pyridinium (N4/C8–C12) rings being inclined to the central thiadiazole (S1/N2/N3/C6/C7) ring by 6.51 (9) and 9.13 (9)°, respectively. The dihedral angle between the pyridine and pyridinium rings is 12.91 (10)°.
In the crystal, the cations are linked by N—H⋯O and C—H⋯O hydrogen bonds, involving the perchlorate anion, forming chains propagating along the [100] direction; Table 1 and Fig. 2. The chains are linked by weak offset π–π interactions [Cg2⋯Cg1i = 3.586 (1) Å; Cg2 and Cg1 are the centroids of the N1/C1–C5 and S1/N2/N3/C6/C7 rings, respectively; interplanar distance 3.4952 (8) Å; slippage 0.734 Å; α = 6.51 (9)°; symmetry code: (i) −x + , −y + , −z + 1], forming layers parallel to the ab plane (Fig. 2).
Synthesis and crystallization
The 2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole ligand (L) was synthesized as described previously (Lebrini et al., 2005). To a solution of L (24 mg, 0.1 mmol) in EtOH (10 ml) was added dropwise HClO4 (1 ml, 1 mol/l) with stirring at 318 K. The resulting solution was filtered after 2 h and allowed to stand in air for the solvent to evaporate slowly. After one month, colourless block-like crystals of the title compound were isolated and dried under vacuum (yield 40%, m.p. > 543 K). Elemental Analysis for C12H9N4SClO4. Calculated: C 42.30; H 2.66; N 16.44; S 9.41%, found: C 42.86; H 2.70; N 16.54; S 9.87%.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1539885
https://doi.org/10.1107/S2414314617004655/su4143sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617004655/su4143Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617004655/su4143Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) and publCIF (Westrip, 2010).C12H9N4S+·ClO4− | F(000) = 1392 |
Mr = 340.74 | Dx = 1.663 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 33.5367 (15) Å | Cell parameters from 3824 reflections |
b = 5.5506 (2) Å | θ = 2.5–29.6° |
c = 14.7248 (7) Å | µ = 0.46 mm−1 |
β = 96.873 (2)° | T = 296 K |
V = 2721.3 (2) Å3 | Block, colourless |
Z = 8 | 0.31 × 0.26 × 0.24 mm |
Bruker APEXII CCD diffractometer | 3824 independent reflections |
Radiation source: fine-focus sealed tube | 2916 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
φ and ω scans | θmax = 29.6°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −46→46 |
Tmin = 0.672, Tmax = 0.747 | k = −7→7 |
50011 measured reflections | l = −20→20 |
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)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0492P)2 + 3.1258P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3824 reflections | Δρmax = 0.64 e Å−3 |
200 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: (SHELXL2014; Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00101 (19) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.18047 (6) | 0.1642 (4) | 0.65832 (15) | 0.0455 (5) | |
H1 | 0.1681 | 0.0341 | 0.6833 | 0.055* | |
C2 | 0.15657 (6) | 0.3515 (4) | 0.62216 (14) | 0.0465 (5) | |
H2 | 0.1288 | 0.3458 | 0.6221 | 0.056* | |
C3 | 0.17455 (7) | 0.5475 (4) | 0.58611 (14) | 0.0472 (5) | |
H3 | 0.1592 | 0.6764 | 0.5615 | 0.057* | |
C4 | 0.21568 (7) | 0.5486 (4) | 0.58731 (14) | 0.0439 (4) | |
H4 | 0.2287 | 0.6793 | 0.5646 | 0.053* | |
C5 | 0.23703 (6) | 0.3505 (3) | 0.62305 (12) | 0.0360 (4) | |
C6 | 0.28059 (6) | 0.3308 (3) | 0.62037 (12) | 0.0356 (4) | |
N2 | 0.30220 (5) | 0.4922 (3) | 0.58383 (13) | 0.0462 (4) | |
C7 | 0.34788 (6) | 0.2110 (3) | 0.62361 (12) | 0.0355 (4) | |
C8 | 0.38781 (6) | 0.1017 (3) | 0.62886 (12) | 0.0352 (4) | |
C9 | 0.40005 (6) | −0.1039 (4) | 0.67636 (13) | 0.0404 (4) | |
H9 | 0.3820 | −0.1905 | 0.7069 | 0.048* | |
C10 | 0.43937 (6) | −0.1812 (4) | 0.67844 (15) | 0.0466 (5) | |
H10 | 0.4479 | −0.3192 | 0.7110 | 0.056* | |
C11 | 0.46602 (6) | −0.0542 (4) | 0.63233 (15) | 0.0506 (5) | |
H11 | 0.4926 | −0.1041 | 0.6340 | 0.061* | |
C12 | 0.45270 (6) | 0.1464 (4) | 0.58412 (15) | 0.0490 (5) | |
H12 | 0.4701 | 0.2327 | 0.5518 | 0.059* | |
N1 | 0.22023 (5) | 0.1595 (3) | 0.65940 (12) | 0.0407 (4) | |
N3 | 0.34134 (5) | 0.4227 (3) | 0.58616 (12) | 0.0451 (4) | |
N4 | 0.41472 (5) | 0.2185 (3) | 0.58340 (11) | 0.0409 (4) | |
H4A | 0.4070 | 0.3452 | 0.5526 | 0.049* | |
O1 | 0.41023 (6) | 0.6149 (4) | 0.46276 (12) | 0.0709 (5) | |
O2 | 0.44211 (5) | 0.9097 (3) | 0.38647 (13) | 0.0636 (5) | |
O3 | 0.46696 (6) | 0.5156 (4) | 0.39250 (18) | 0.0877 (7) | |
O4 | 0.40605 (5) | 0.6036 (3) | 0.30479 (11) | 0.0633 (5) | |
S1 | 0.30657 (2) | 0.07805 (9) | 0.66034 (3) | 0.03868 (13) | |
Cl1 | 0.43216 (2) | 0.66014 (8) | 0.38557 (3) | 0.03972 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0471 (11) | 0.0442 (11) | 0.0460 (11) | −0.0084 (9) | 0.0084 (9) | −0.0049 (9) |
C2 | 0.0417 (10) | 0.0575 (13) | 0.0394 (10) | −0.0001 (9) | 0.0012 (8) | −0.0126 (9) |
C3 | 0.0527 (12) | 0.0468 (12) | 0.0404 (10) | 0.0111 (10) | −0.0015 (9) | −0.0039 (9) |
C4 | 0.0538 (12) | 0.0384 (10) | 0.0396 (10) | 0.0011 (9) | 0.0063 (9) | 0.0025 (8) |
C5 | 0.0436 (10) | 0.0338 (9) | 0.0304 (8) | −0.0010 (7) | 0.0034 (7) | −0.0025 (7) |
C6 | 0.0446 (10) | 0.0312 (8) | 0.0310 (8) | −0.0020 (7) | 0.0044 (7) | 0.0000 (7) |
N2 | 0.0510 (10) | 0.0359 (8) | 0.0534 (10) | 0.0008 (7) | 0.0132 (8) | 0.0067 (8) |
C7 | 0.0413 (9) | 0.0356 (9) | 0.0300 (8) | −0.0057 (7) | 0.0063 (7) | −0.0015 (7) |
C8 | 0.0388 (9) | 0.0390 (9) | 0.0277 (8) | −0.0070 (8) | 0.0041 (7) | −0.0033 (7) |
C9 | 0.0453 (10) | 0.0409 (10) | 0.0363 (9) | −0.0046 (8) | 0.0102 (8) | 0.0025 (8) |
C10 | 0.0467 (11) | 0.0483 (11) | 0.0443 (11) | 0.0022 (9) | 0.0034 (9) | 0.0049 (9) |
C11 | 0.0377 (10) | 0.0630 (14) | 0.0506 (12) | −0.0026 (10) | 0.0036 (9) | −0.0001 (10) |
C12 | 0.0400 (10) | 0.0590 (13) | 0.0487 (11) | −0.0120 (9) | 0.0088 (9) | 0.0047 (10) |
N1 | 0.0440 (9) | 0.0354 (8) | 0.0432 (9) | −0.0012 (7) | 0.0068 (7) | 0.0003 (7) |
N3 | 0.0494 (10) | 0.0372 (8) | 0.0504 (10) | −0.0038 (7) | 0.0136 (8) | 0.0049 (7) |
N4 | 0.0420 (9) | 0.0442 (9) | 0.0368 (8) | −0.0073 (7) | 0.0059 (7) | 0.0052 (7) |
O1 | 0.0841 (13) | 0.0781 (12) | 0.0533 (10) | −0.0105 (10) | 0.0194 (9) | 0.0201 (9) |
O2 | 0.0704 (11) | 0.0440 (9) | 0.0776 (12) | −0.0167 (8) | 0.0134 (9) | 0.0017 (8) |
O3 | 0.0481 (10) | 0.0771 (13) | 0.135 (2) | 0.0194 (10) | −0.0025 (11) | −0.0011 (13) |
O4 | 0.0663 (11) | 0.0715 (11) | 0.0486 (9) | −0.0082 (9) | −0.0074 (8) | −0.0029 (8) |
S1 | 0.0399 (3) | 0.0360 (2) | 0.0406 (3) | −0.00179 (19) | 0.00645 (19) | 0.00837 (19) |
Cl1 | 0.0366 (2) | 0.0386 (2) | 0.0434 (3) | −0.00349 (18) | 0.00246 (18) | 0.00549 (18) |
C1—N1 | 1.332 (3) | C7—S1 | 1.7135 (18) |
C1—C2 | 1.380 (3) | C8—N4 | 1.352 (2) |
C1—H1 | 0.9300 | C8—C9 | 1.375 (3) |
C2—C3 | 1.380 (3) | C9—C10 | 1.384 (3) |
C2—H2 | 0.9300 | C9—H9 | 0.9300 |
C3—C4 | 1.377 (3) | C10—C11 | 1.379 (3) |
C3—H3 | 0.9300 | C10—H10 | 0.9300 |
C4—C5 | 1.382 (3) | C11—C12 | 1.366 (3) |
C4—H4 | 0.9300 | C11—H11 | 0.9300 |
C5—N1 | 1.341 (2) | C12—N4 | 1.334 (3) |
C5—C6 | 1.470 (3) | C12—H12 | 0.9300 |
C6—N2 | 1.308 (2) | N4—H4A | 0.8600 |
C6—S1 | 1.7178 (19) | O1—Cl1 | 1.4478 (17) |
N2—N3 | 1.365 (2) | O2—Cl1 | 1.4244 (17) |
C7—N3 | 1.306 (3) | O3—Cl1 | 1.4099 (19) |
C7—C8 | 1.464 (3) | O4—Cl1 | 1.4250 (17) |
N1—C1—C2 | 123.6 (2) | C8—C9—C10 | 119.62 (18) |
N1—C1—H1 | 118.2 | C8—C9—H9 | 120.2 |
C2—C1—H1 | 118.2 | C10—C9—H9 | 120.2 |
C1—C2—C3 | 118.8 (2) | C11—C10—C9 | 120.2 (2) |
C1—C2—H2 | 120.6 | C11—C10—H10 | 119.9 |
C3—C2—H2 | 120.6 | C9—C10—H10 | 119.9 |
C4—C3—C2 | 118.8 (2) | C12—C11—C10 | 118.8 (2) |
C4—C3—H3 | 120.6 | C12—C11—H11 | 120.6 |
C2—C3—H3 | 120.6 | C10—C11—H11 | 120.6 |
C3—C4—C5 | 118.3 (2) | N4—C12—C11 | 120.09 (19) |
C3—C4—H4 | 120.9 | N4—C12—H12 | 120.0 |
C5—C4—H4 | 120.9 | C11—C12—H12 | 120.0 |
N1—C5—C4 | 123.89 (19) | C1—N1—C5 | 116.58 (18) |
N1—C5—C6 | 114.72 (17) | C7—N3—N2 | 112.18 (16) |
C4—C5—C6 | 121.35 (18) | C12—N4—C8 | 123.04 (18) |
N2—C6—C5 | 124.15 (18) | C12—N4—H4A | 118.5 |
N2—C6—S1 | 114.66 (15) | C8—N4—H4A | 118.5 |
C5—C6—S1 | 121.08 (14) | C7—S1—C6 | 86.35 (9) |
C6—N2—N3 | 112.00 (17) | O3—Cl1—O2 | 111.20 (13) |
N3—C7—C8 | 120.12 (17) | O3—Cl1—O4 | 110.83 (13) |
N3—C7—S1 | 114.81 (15) | O2—Cl1—O4 | 109.99 (11) |
C8—C7—S1 | 125.04 (14) | O3—Cl1—O1 | 109.78 (14) |
N4—C8—C9 | 118.27 (18) | O2—Cl1—O1 | 107.57 (12) |
N4—C8—C7 | 115.83 (17) | O4—Cl1—O1 | 107.34 (11) |
C9—C8—C7 | 125.90 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4A···O1 | 0.86 | 2.01 | 2.820 (2) | 157 |
C11—H11···O2i | 0.93 | 2.49 | 3.228 (3) | 136 |
C12—H12···O3i | 0.93 | 2.58 | 3.268 (3) | 131 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
Funding information
Funding for this research was provided by: Chouaib Doukkali University, El Jadida, Morocco (award No. CUR CA2D–UCD).
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