Crystal structure of bis­(azido-κN)bis­[2,5-bis­(pyridin-2-yl)-1,3,4-thia­diazole-κ2 N 2,N 3]nickel(II)

Abdelhakim Laachir; Fouad Bentiss; Salaheddine Guesmi; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S2056989015000201

. 2015 Jan 14;71(Pt 2):m24–m25. doi: 10.1107/S2056989015000201

Crystal structure of bis(azido-κN)bis[2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-κ² N ²,N ³]nickel(II)

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

PMCID: PMC4384553 PMID: 25878837

Abstract

Reaction of 2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole and sodium azide with nickel(II) triflate yielded the mononuclear title complex, [Ni(N₃)₂(C₁₂H₈N₄S)₂]. The Ni^II ion is located on a centre of symmetry and is octahedrally coordinated by four N atoms of the two bidentate heterocyclic ligands in the equatorial plane. The axial positions are occupied by the N atoms of two almost linear azide ions [N—N—N = 178.8 (2)°]. The thiadiazole and pyridine rings of the heterocyclic ligand are almost coplanar, with a maximum deviation from the mean plane of 0.0802 (9) Å. The cohesion of the crystal structure is ensured by π–π interactions between parallel pyridine rings of neighbouring molecules [centroid-to-centroid distance = 3.6413 (14) Å], leading to a layered arrangement of the molecules parallel to (001).

Keywords: crystal structure; mononuclear nickel(II) complex; 1,3,4-thiadiazole; azide ligand; π–π interactions

Related literature

2,5-Bis(pyridin-2-yl)-1,3,4-thiadiazole has been used as a bidentate or tetradentate ligand forming mononuclear (Bentiss et al., 2004 ▸, 2011a ▸, 2012 ▸; Zheng et al., 2006 ▸) or dinuclear complexes (Laachir et al., 2013 ▸). Coordination of the azide ion to transition metals results in compounds with interesting magnetic properties (Machura et al., 2011 ▸; Świtlicka-Olszewska et al., 2014 ▸). The iron salt with the same heterocyclic ligand and thiocyanate as the pseudohalide was reported by Klingele et al. (2010 ▸). For the crystal structure of the related tetrafluoridoborate salt of [Ni(C₁₂H₈N₄S)₂(H₂O)₂], see: Bentiss et al. (2011b ▸). For the synthesis of the heterocyclic ligand, see: Lebrini et al. (2005 ▸).

Experimental

Crystal data

[Ni(N₃)₂(C₁₂H₈N₄S)₂]
M _r = 623.34
Monoclinic,
a = 7.7981 (3) Å
b = 8.2410 (3) Å
c = 20.1555 (7) Å
β = 93.141 (2)°
V = 1293.33 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.96 mm⁻¹
T = 296 K
0.39 × 0.31 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.640, T _max = 0.747
15710 measured reflections
3077 independent reflections
2643 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.100
S = 1.04
3077 reflections
187 parameters
H-atom parameters constrained
Δρ_max = 1.25 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015000201/wm5108sup1.cif

e-71-00m24-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000201/wm5108Isup2.hkl

e-71-00m24-Isup2.hkl^{(151KB, hkl)}

Click here for additional data file.^{(1.4MB, tif)}

x y z . DOI: 10.1107/S2056989015000201/wm5108fig1.tif

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as spheres of arbitrary radius. [Symmetry code: (i) −x + 2, −y + 1, −z + 2.]

Click here for additional data file.^{(2.1MB, tif)}

. DOI: 10.1107/S2056989015000201/wm5108fig2.tif

The crystal packing of the title compound, showing intermolecular π–π interactions between pyridyl rings (dashed green lines).

CCDC reference: 1042351

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

S1. Experimental

The 2,5-bis(2-pyridyl)-1,3,4-thiadiazole ligand (noted L) was synthesized as described previously by Lebrini et al. (2005). Ni₂L₂(N₃)₂ was obtained in bulk quantity by dropwise addition of an aqueous solution of NaN₃ (0.4 mmol, 26 mg) to an ethanol/water solution of L (0.1 mmol, 24 mg) and Ni(O₃SCF₃)₂ (0.1 mmol, 36 mg) under constant stirring at room temperature. An orange coloured solid was precipitated, filtered and washed with cold ethanol. Single crystals of Ni₂L₂(N₃)₂ were grown by slow interdiffusion of a solution of Ni(O₃SCF₃)₂ and L in acetonitrile into NaN₃ dissolved in water. Orange block-shaped single crystals appeared after one month. The crystals were washed with water and dried under vacuum (yield 50%).

CAUTION. Azide compounds are potentially explosive. Only a small amount of material should be prepared and handled with care.