2-[5-(Pyridin-2-yl)-1,3,4-thia­diazol-2-yl]pyridin-1-ium perchlorate

Laachir, A.; Bentiss, F.; Guesmi, S.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314617004655

organic compounds

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ISSN: 2414-3146

Volume 2| Part 3| March 2017| x170465

https://doi.org/10.1107/S2414314617004655

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2-[5-(Pyridin-2-yl)-1,3,4-thiadiazol-2-yl]pyridin-1-ium perchlorate

Abdelhakim Laachir,^a Fouad Bentiss,^b Salaheddine Guesmi,^a ^* Mohamed Saadi ^c and Lahcen El Ammari ^c

^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

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 20 March 2017; accepted 23 March 2017; online 28 March 2017)

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)°.

Figure 1
The molecular structure of the title molecular salt, with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

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 + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z + 1], forming layers parallel to the ab plane (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 2
A view along the b axis of the crystal packing of the title molecular salt. The hydrogen bonds shown as dashed lines (see Table 1

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉N₄S⁺·ClO₄⁻
M_r	340.74
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	33.5367 (15), 5.5506 (2), 14.7248 (7)
β (°)	96.873 (2)
V (Å³)	2721.3 (2)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.46
Crystal size (mm)	0.31 × 0.26 × 0.24

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.672, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	50011, 3824, 2916
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.694

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.111, 1.03
No. of reflections	3824
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.36
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT2014 (Sheldrick, 2015a ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), SHELXL2014 (Sheldrick, 2015b ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1539885

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617004655/su4143sup1.cif

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

checkCIF report

Computing details top

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

2-[5-(Pyridin-2-yl)-1,3,4-thiadiazol-2-yl]pyridin-1-ium perchlorate top

Crystal data top

C₁₂H₉N₄S⁺·ClO₄⁻	F(000) = 1392
M_r = 340.74	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	3824 independent reflections
Radiation source: fine-focus sealed tube	2916 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
φ and ω scans	θ_max = 29.6°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −46→46
T_min = 0.672, T_max = 0.747	k = −7→7
50011 measured reflections	l = −20→20

Refinement top

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(F_o²) + (0.0492P)² + 3.1258P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3824 reflections	Δρ_max = 0.64 e Å⁻³
200 parameters	Δρ_min = −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)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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