Crystal structure of bis-(azido-κN)bis-[2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole-κ(2) N (2),N (3)]nickel(II).

Reaction of 2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole 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 octa-hedrally 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 thia-diazole 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 inter-actions between parallel pyridine rings of neighbouring mol-ecules [centroid-to-centroid distance = 3.6413 (14) Å], leading to a layered arrangement of the mol-ecules parallel to (001).

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 = 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

Δρmax = 1.25 e Å−3

Δρmin = −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 ▸).

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

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

Click here for additional data file.

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.

. 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

[Ni(N3)2(C12H8N4S)2]	F(000) = 636
Mr = 623.34	Dx = 1.601 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3077 reflections
a = 7.7981 (3) Å	θ = 2.6–27.9°
b = 8.2410 (3) Å	µ = 0.96 mm−1
c = 20.1555 (7) Å	T = 296 K
β = 93.141 (2)°	Block, orange
V = 1293.33 (8) Å3	0.39 × 0.31 × 0.18 mm
Z = 2

Bruker APEXII CCD diffractometer	3077 independent reflections
Radiation source: fine-focus sealed tube	2643 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
φ and ω scans	θmax = 27.9°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→9
Tmin = 0.640, Tmax = 0.747	k = −10→10
15710 measured reflections	l = −26→26

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0522P)2 + 0.8063P] where P = (Fo2 + 2Fc2)/3
3077 reflections	(Δ/σ)max < 0.001
187 parameters	Δρmax = 1.25 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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 > 2σ(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
C1	1.3016 (3)	0.4676 (3)	0.90640 (11)	0.0356 (5)
H1	1.3538	0.4022	0.9392	0.043*
C2	1.3853 (3)	0.4935 (3)	0.84813 (12)	0.0397 (5)
H2	1.4916	0.4460	0.8423	0.048*
C3	1.3091 (3)	0.5902 (3)	0.79925 (10)	0.0380 (5)
H3	1.3630	0.6089	0.7599	0.046*
C4	1.1511 (3)	0.6589 (3)	0.80960 (10)	0.0350 (4)
H4	1.0966	0.7246	0.7774	0.042*
C5	1.0759 (2)	0.6281 (2)	0.86873 (9)	0.0292 (4)
C6	0.9114 (3)	0.6956 (3)	0.88563 (9)	0.0304 (4)
C7	0.6422 (2)	0.8193 (2)	0.90011 (10)	0.0313 (4)
C8	0.4793 (3)	0.9088 (3)	0.89219 (11)	0.0336 (4)
C9	0.3101 (4)	1.0642 (4)	0.82288 (15)	0.0575 (7)
H9	0.2915	1.1167	0.7823	0.069*
C10	0.1844 (3)	1.0747 (3)	0.86751 (15)	0.0536 (7)
H10	0.0843	1.1332	0.8575	0.064*
C11	0.2099 (3)	0.9966 (3)	0.92746 (14)	0.0498 (6)
H11	0.1274	1.0021	0.9590	0.060*
C12	0.3601 (3)	0.9095 (3)	0.94026 (11)	0.0401 (5)
H12	0.3799	0.8534	0.9800	0.048*
N1	1.1488 (2)	0.5333 (2)	0.91692 (8)	0.0298 (4)
N2	0.8473 (2)	0.6603 (2)	0.94235 (8)	0.0313 (4)
N3	0.6911 (2)	0.7303 (2)	0.95059 (8)	0.0320 (4)
N4	0.4563 (3)	0.9844 (2)	0.83359 (11)	0.0463 (5)
N5	0.8723 (3)	0.3030 (2)	0.95247 (9)	0.0427 (4)
N6	0.8332 (2)	0.3118 (2)	0.89483 (9)	0.0385 (4)
N7	0.7973 (3)	0.3188 (3)	0.83827 (11)	0.0645 (7)
S1	0.78523 (7)	0.82456 (7)	0.83744 (3)	0.03745 (15)
Ni1	1.0000	0.5000	1.0000	0.02650 (12)

	U11	U22	U33	U12	U13	U23
C1	0.0333 (11)	0.0420 (11)	0.0319 (10)	0.0063 (9)	0.0056 (8)	0.0008 (9)
C2	0.0340 (11)	0.0477 (13)	0.0387 (12)	0.0036 (9)	0.0120 (9)	−0.0044 (9)
C3	0.0386 (11)	0.0478 (13)	0.0288 (10)	−0.0037 (10)	0.0128 (8)	−0.0036 (9)
C4	0.0374 (11)	0.0451 (12)	0.0228 (9)	0.0007 (9)	0.0050 (8)	0.0023 (8)
C5	0.0301 (9)	0.0351 (10)	0.0226 (9)	0.0005 (8)	0.0046 (7)	−0.0011 (7)
C6	0.0309 (9)	0.0385 (11)	0.0219 (9)	0.0017 (8)	0.0008 (7)	0.0026 (8)
C7	0.0290 (9)	0.0367 (10)	0.0283 (9)	0.0022 (8)	0.0027 (7)	0.0006 (8)
C8	0.0291 (10)	0.0329 (10)	0.0385 (11)	0.0033 (8)	0.0006 (8)	−0.0013 (8)
C9	0.0508 (15)	0.0563 (16)	0.0656 (17)	0.0155 (13)	0.0046 (13)	0.0247 (14)
C10	0.0362 (12)	0.0439 (14)	0.081 (2)	0.0158 (11)	0.0015 (12)	−0.0001 (13)
C11	0.0355 (12)	0.0543 (15)	0.0608 (16)	−0.0010 (10)	0.0129 (11)	−0.0183 (12)
C12	0.0398 (12)	0.0451 (13)	0.0354 (11)	−0.0025 (10)	0.0021 (9)	−0.0026 (9)
N1	0.0312 (8)	0.0357 (9)	0.0229 (8)	0.0022 (7)	0.0045 (6)	0.0003 (6)
N2	0.0298 (8)	0.0410 (9)	0.0235 (8)	0.0063 (7)	0.0045 (6)	0.0019 (7)
N3	0.0283 (8)	0.0407 (9)	0.0271 (8)	0.0072 (7)	0.0029 (6)	0.0014 (7)
N4	0.0380 (10)	0.0508 (12)	0.0507 (12)	0.0098 (9)	0.0090 (9)	0.0182 (9)
N5	0.0501 (11)	0.0467 (11)	0.0315 (9)	−0.0058 (9)	0.0040 (8)	−0.0017 (8)
N6	0.0304 (9)	0.0464 (11)	0.0387 (10)	0.0060 (8)	0.0015 (7)	−0.0129 (8)
N7	0.0631 (15)	0.0907 (19)	0.0379 (12)	0.0154 (13)	−0.0121 (10)	−0.0185 (12)
S1	0.0343 (3)	0.0496 (3)	0.0289 (3)	0.0091 (2)	0.00513 (19)	0.0117 (2)
Ni1	0.02602 (19)	0.0358 (2)	0.01789 (17)	0.00586 (14)	0.00320 (12)	0.00259 (13)

C1—N1	1.336 (3)	C9—N4	1.324 (3)
C1—C2	1.391 (3)	C9—C10	1.369 (4)
C1—H1	0.9300	C9—H9	0.9300
C2—C3	1.376 (3)	C10—C11	1.374 (4)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.382 (3)	C11—C12	1.386 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.380 (3)	C12—H12	0.9300
C4—H4	0.9300	N1—Ni1	2.1069 (17)
C5—N1	1.348 (2)	N2—N3	1.366 (2)
C5—C6	1.456 (3)	N2—Ni1	2.0885 (16)
C6—N2	1.305 (3)	N5—N6	1.187 (3)
C6—S1	1.714 (2)	N5—Ni1	2.1075 (19)
C7—N3	1.295 (2)	N6—N7	1.160 (3)
C7—C8	1.470 (3)	Ni1—N2i	2.0885 (16)
C7—S1	1.731 (2)	Ni1—N1i	2.1069 (17)
C8—N4	1.339 (3)	Ni1—N5i	2.108 (2)
C8—C12	1.379 (3)
N1—C1—C2	122.4 (2)	C10—C11—H11	120.5
N1—C1—H1	118.8	C12—C11—H11	120.5
C2—C1—H1	118.8	C8—C12—C11	117.8 (2)
C3—C2—C1	119.3 (2)	C8—C12—H12	121.1
C3—C2—H2	120.4	C11—C12—H12	121.1
C1—C2—H2	120.4	C1—N1—C5	117.71 (18)
C2—C3—C4	118.9 (2)	C1—N1—Ni1	127.46 (15)
C2—C3—H3	120.6	C5—N1—Ni1	114.79 (13)
C4—C3—H3	120.6	C6—N2—N3	113.55 (16)
C5—C4—C3	118.63 (19)	C6—N2—Ni1	113.19 (13)
C5—C4—H4	120.7	N3—N2—Ni1	133.19 (13)
C3—C4—H4	120.7	C7—N3—N2	111.69 (16)
N1—C5—C4	123.14 (19)	C9—N4—C8	116.6 (2)
N1—C5—C6	113.27 (17)	N6—N5—Ni1	119.16 (16)
C4—C5—C6	123.58 (18)	N7—N6—N5	178.8 (2)
N2—C6—C5	120.32 (18)	C6—S1—C7	86.77 (9)
N2—C6—S1	113.49 (15)	N2—Ni1—N2i	180.00 (7)
C5—C6—S1	126.18 (15)	N2—Ni1—N1	78.32 (6)
N3—C7—C8	125.80 (19)	N2i—Ni1—N1	101.68 (6)
N3—C7—S1	114.47 (15)	N2—Ni1—N1i	101.68 (6)
C8—C7—S1	119.72 (15)	N2i—Ni1—N1i	78.32 (6)
N4—C8—C12	123.7 (2)	N1—Ni1—N1i	180.000 (1)
N4—C8—C7	113.74 (19)	N2—Ni1—N5	89.63 (8)
C12—C8—C7	122.5 (2)	N2i—Ni1—N5	90.37 (8)
N4—C9—C10	124.4 (3)	N1—Ni1—N5	90.35 (7)
N4—C9—H9	117.8	N1i—Ni1—N5	89.65 (7)
C10—C9—H9	117.8	N2—Ni1—N5i	90.37 (8)
C9—C10—C11	118.3 (2)	N2i—Ni1—N5i	89.63 (8)
C9—C10—H10	120.8	N1—Ni1—N5i	89.65 (7)
C11—C10—H10	120.8	N1i—Ni1—N5i	90.35 (7)
C10—C11—C12	119.1 (2)	N5—Ni1—N5i	179.998 (1)