trans-Diaqua-bis-[2,5-bis-(pyridin-2-yl)-1,3,4-thia-diazole]nickel(II) bis-(tetra-fluoridoborate).

The bidentate 1,3,4-thia-diazole ligand, namely, 2,5-bis-(2-pyrid-yl)-1,3,4-thia-diazole (denoted L), untested as a polydentate ligand, has been found to form the monomeric title complex, [Ni(C(12)H(8)N(4)S)(2)(H(2)O)(2)](BF(4))(2). The complex shows an octa-hedral environment of the nickel cation in which the Ni(2+) ion is located on a center of symmetry, linked to two ligands and two water molecules. In this 1:2 complex (one metal for two organic ligands) each thia-diazole ligand uses one pyridyl and one thia-diazole N atom for chelate binding. In the second pyridyl substituent, the N atom is oriented towards the same direction as the S atom of the 1,3,4-thiadiazole ring. The mean plane of the thia-diazole and pyridyl rings linked to the nickel cation forms a dihedral angle with the other pyridine ring of 18.63 (8)°. The tetra-fluorido-borate ions can be regarded as free anions in the crystal lattice. Nevertheless, they are involved in an infinite two-dimensional network parallel to ([Formula: see text]01) through O-H⋯F hydrogen bonds.

Related literature

For NiII and CuII complexes containing a five n class="Chemical">azide ring, see: Keij et al. (1984 ▶). For background to similar structures, see: Bentiss et al. (2002 ▶, 2004 ▶, 2011 ▶); Zheng et al. (2006 ▶). For an improved synthesis of the ligand, see: Lebrini et al. (2005 ▶).

Experimental

Crystal data

[Ni(C12H8N4S)2(H2O)2](BF4)2

M = 748.93

Monoclinic,

a = 10.8164 (15) Å

b = 11.0126 (13) Å

c = 13.2333 (16) Å

β = 101.455 (6)°

V = 1544.9 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.85 mm−1

T = 100 K

0.26 × 0.21 × 0.13 mm

Data collection

Bruker X8 APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.809, T max = 0.898

28021 measured reflections

3120 independent reflections

2729 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.073

S = 1.05

3120 reflections

214 parameters

H-atom parameters constrained

Δρmax = 0.60 e Å−3

Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811026420/dn2703sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026420/dn2703Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C12H8N4S)2(H2O)2](BF4)2	F(000) = 756
Mr = 748.93	Dx = 1.610 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3120 reflections
a = 10.8164 (15) Å	θ = 2.7–26.3°
b = 11.0126 (13) Å	µ = 0.85 mm−1
c = 13.2333 (16) Å	T = 100 K
β = 101.455 (6)°	Prism, colourless
V = 1544.9 (3) Å3	0.26 × 0.21 × 0.13 mm
Z = 2

Bruker X8 APEXII CCD area-detector diffractometer	3120 independent reflections
Radiation source: fine-focus sealed tube	2729 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 26.3°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
Tmin = 0.809, Tmax = 0.898	k = −13→13
28021 measured reflections	l = −16→16

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0302P)2 + 1.3259P] where P = (Fo2 + 2Fc2)/3
3120 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.60 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
B1	0.5722 (2)	0.6450 (2)	0.25602 (17)	0.0236 (4)
F1	0.67390 (15)	0.59474 (18)	0.32316 (11)	0.0707 (6)
F2	0.58436 (11)	0.62341 (12)	0.15219 (9)	0.0362 (3)
F3	0.46260 (14)	0.59379 (14)	0.27433 (14)	0.0583 (4)
F4	0.56853 (15)	0.77036 (12)	0.27479 (11)	0.0494 (4)
C1	0.40875 (16)	0.75569 (16)	−0.02295 (14)	0.0202 (4)
C2	0.47768 (16)	1.25248 (17)	0.06948 (13)	0.0200 (4)
C3	0.43547 (18)	1.35965 (17)	0.10676 (14)	0.0236 (4)
H3	0.4806	1.4333	0.1048	0.028*
C4	0.32542 (18)	1.35711 (18)	0.14729 (15)	0.0258 (4)
H4	0.2940	1.4292	0.1726	0.031*
C5	0.26311 (18)	1.24770 (18)	0.14982 (15)	0.0265 (4)
H5	0.1883	1.2433	0.1770	0.032*
C6	0.31231 (18)	1.14360 (18)	0.11167 (15)	0.0248 (4)
H6	0.2696	1.0686	0.1144	0.030*
C7	0.22180 (17)	0.74859 (17)	0.04687 (14)	0.0210 (4)
C8	0.10347 (17)	0.71642 (18)	0.08024 (14)	0.0222 (4)
C9	0.01756 (18)	0.80507 (19)	0.09554 (16)	0.0296 (4)
H9	0.0335	0.8887	0.0859	0.036*
C10	−0.09264 (19)	0.7670 (2)	0.12544 (17)	0.0342 (5)
H10	−0.1541	0.8246	0.1364	0.041*
C11	−0.11154 (19)	0.6445 (2)	0.13902 (16)	0.0329 (5)
H11	−0.1862	0.6166	0.1591	0.040*
C12	−0.0195 (2)	0.5627 (2)	0.12282 (16)	0.0310 (5)
H12	−0.0326	0.4787	0.1334	0.037*
Ni1	0.5000	1.0000	0.0000	0.01936 (10)
N1	0.41765 (14)	1.14452 (14)	0.07112 (12)	0.0218 (3)
N2	0.38061 (14)	0.85992 (14)	0.01661 (12)	0.0210 (3)
N3	0.27253 (14)	0.85652 (14)	0.05732 (12)	0.0226 (3)
N4	0.08724 (15)	0.59655 (15)	0.09286 (13)	0.0260 (4)
O1	0.61598 (13)	0.95553 (13)	0.14395 (11)	0.0307 (3)
H1W	0.6844	0.9932	0.1692	0.037*
H2W	0.6090	0.9007	0.1886	0.037*
S1	0.30384 (4)	0.64191 (4)	−0.01275 (4)	0.02147 (12)

	U11	U22	U33	U12	U13	U23
B1	0.0194 (10)	0.0233 (11)	0.0268 (11)	0.0023 (8)	0.0017 (8)	0.0008 (9)
F1	0.0620 (10)	0.1029 (14)	0.0388 (8)	0.0561 (10)	−0.0106 (7)	−0.0066 (9)
F2	0.0351 (7)	0.0440 (8)	0.0285 (6)	−0.0059 (6)	0.0039 (5)	−0.0035 (6)
F3	0.0514 (9)	0.0459 (9)	0.0907 (12)	−0.0177 (7)	0.0457 (9)	−0.0236 (8)
F4	0.0759 (10)	0.0240 (7)	0.0503 (8)	−0.0093 (7)	0.0178 (7)	−0.0030 (6)
C1	0.0189 (9)	0.0170 (9)	0.0231 (9)	−0.0021 (7)	0.0004 (7)	0.0028 (7)
C2	0.0188 (9)	0.0196 (9)	0.0203 (8)	−0.0010 (7)	0.0005 (7)	0.0021 (7)
C3	0.0248 (10)	0.0184 (9)	0.0270 (10)	−0.0014 (7)	0.0034 (8)	0.0006 (8)
C4	0.0283 (10)	0.0214 (10)	0.0283 (10)	0.0025 (8)	0.0073 (8)	−0.0018 (8)
C5	0.0248 (10)	0.0258 (10)	0.0302 (10)	−0.0003 (8)	0.0090 (8)	0.0004 (8)
C6	0.0243 (9)	0.0213 (10)	0.0297 (10)	−0.0038 (8)	0.0078 (8)	0.0001 (8)
C7	0.0197 (9)	0.0197 (9)	0.0226 (9)	0.0002 (7)	0.0015 (7)	0.0009 (7)
C8	0.0194 (9)	0.0246 (10)	0.0218 (9)	−0.0032 (8)	0.0020 (7)	−0.0011 (8)
C9	0.0247 (10)	0.0270 (11)	0.0362 (11)	0.0009 (8)	0.0040 (8)	−0.0007 (9)
C10	0.0246 (10)	0.0425 (13)	0.0365 (11)	0.0058 (9)	0.0086 (9)	−0.0034 (10)
C11	0.0244 (10)	0.0476 (14)	0.0295 (10)	−0.0075 (9)	0.0116 (8)	−0.0016 (10)
C12	0.0337 (11)	0.0290 (11)	0.0331 (11)	−0.0092 (9)	0.0131 (9)	0.0009 (9)
Ni1	0.01766 (17)	0.01400 (17)	0.02659 (18)	−0.00261 (13)	0.00479 (13)	−0.00057 (13)
N1	0.0205 (8)	0.0182 (8)	0.0264 (8)	−0.0019 (6)	0.0039 (6)	0.0009 (6)
N2	0.0186 (7)	0.0179 (8)	0.0267 (8)	−0.0013 (6)	0.0048 (6)	0.0000 (6)
N3	0.0193 (8)	0.0208 (8)	0.0282 (8)	−0.0032 (6)	0.0056 (6)	0.0012 (7)
N4	0.0267 (8)	0.0233 (9)	0.0299 (8)	−0.0047 (7)	0.0099 (7)	−0.0014 (7)
O1	0.0270 (7)	0.0276 (8)	0.0337 (8)	−0.0075 (6)	−0.0030 (6)	0.0064 (6)
S1	0.0188 (2)	0.0158 (2)	0.0299 (2)	−0.00252 (17)	0.00479 (18)	0.00033 (18)

B1—F3	1.377 (3)	C7—S1	1.7517 (19)
B1—F1	1.385 (3)	C8—N4	1.346 (3)
B1—F4	1.404 (3)	C8—C9	1.390 (3)
B1—F2	1.426 (2)	C9—C10	1.393 (3)
C1—N2	1.322 (2)	C9—H9	0.9500
C1—C2i	1.482 (2)	C10—C11	1.382 (3)
C1—S1	1.7137 (18)	C10—H10	0.9500
C2—N1	1.357 (2)	C11—C12	1.391 (3)
C2—C3	1.391 (3)	C11—H11	0.9500
C2—C1i	1.482 (2)	C12—N4	1.345 (2)
C3—C4	1.400 (3)	C12—H12	0.9500
C3—H3	0.9500	Ni1—N2	2.0515 (15)
C4—C5	1.384 (3)	Ni1—N2i	2.0515 (15)
C4—H4	0.9500	Ni1—O1i	2.1197 (14)
C5—C6	1.400 (3)	Ni1—O1	2.1197 (14)
C5—H5	0.9500	Ni1—N1i	2.1320 (16)
C6—N1	1.352 (2)	Ni1—N1	2.1320 (16)
C6—H6	0.9500	N2—N3	1.381 (2)
C7—N3	1.305 (2)	O1—H1W	0.8564
C7—C8	1.478 (2)	O1—H2W	0.8588
F3—B1—F1	108.98 (19)	C9—C10—H10	120.4
F3—B1—F4	108.44 (17)	C10—C11—C12	118.91 (18)
F1—B1—F4	109.02 (18)	C10—C11—H11	120.5
F3—B1—F2	110.41 (17)	C12—C11—H11	120.5
F1—B1—F2	109.73 (17)	N4—C12—C11	123.3 (2)
F4—B1—F2	110.22 (17)	N4—C12—H12	118.4
N2—C1—C2i	119.49 (16)	C11—C12—H12	118.4
N2—C1—S1	113.30 (13)	N2—Ni1—N2i	180.00 (9)
C2i—C1—S1	127.21 (14)	N2—Ni1—O1i	89.84 (6)
N1—C2—C3	123.10 (16)	N2i—Ni1—O1i	90.16 (6)
N1—C2—C1i	113.09 (16)	N2—Ni1—O1	90.16 (6)
C3—C2—C1i	123.81 (16)	N2i—Ni1—O1	89.84 (6)
C2—C3—C4	118.89 (17)	O1i—Ni1—O1	180.00 (8)
C2—C3—H3	120.6	N2—Ni1—N1i	79.22 (6)
C4—C3—H3	120.6	N2i—Ni1—N1i	100.78 (6)
C5—C4—C3	118.81 (18)	O1i—Ni1—N1i	90.02 (6)
C5—C4—H4	120.6	O1—Ni1—N1i	89.98 (6)
C3—C4—H4	120.6	N2—Ni1—N1	100.78 (6)
C4—C5—C6	118.84 (17)	N2i—Ni1—N1	79.22 (6)
C4—C5—H5	120.6	O1i—Ni1—N1	89.98 (6)
C6—C5—H5	120.6	O1—Ni1—N1	90.02 (6)
N1—C6—C5	123.20 (17)	N1i—Ni1—N1	180.0
N1—C6—H6	118.4	C6—N1—C2	117.16 (16)
C5—C6—H6	118.4	C6—N1—Ni1	128.93 (13)
N3—C7—C8	123.90 (17)	C2—N1—Ni1	113.82 (12)
N3—C7—S1	114.75 (13)	C1—N2—N3	114.22 (15)
C8—C7—S1	121.34 (14)	C1—N2—Ni1	114.28 (12)
N4—C8—C9	124.27 (17)	N3—N2—Ni1	131.42 (12)
N4—C8—C7	114.47 (16)	C7—N3—N2	110.73 (15)
C9—C8—C7	121.26 (17)	C12—N4—C8	116.68 (17)
C8—C9—C10	117.7 (2)	Ni1—O1—H1W	123.4
C8—C9—H9	121.2	Ni1—O1—H2W	131.6
C10—C9—H9	121.2	H1W—O1—H2W	105.0
C11—C10—C9	119.2 (2)	C1—S1—C7	87.00 (9)
C11—C10—H10	120.4
N1—C2—C3—C4	−0.5 (3)	C3—C2—N1—Ni1	176.49 (14)
C1i—C2—C3—C4	178.72 (17)	C1i—C2—N1—Ni1	−2.83 (19)
C2—C3—C4—C5	0.7 (3)	C2i—C1—N2—N3	179.76 (15)
C3—C4—C5—C6	−0.1 (3)	S1—C1—N2—N3	−0.4 (2)
C4—C5—C6—N1	−0.7 (3)	C2i—C1—N2—Ni1	2.7 (2)
N3—C7—C8—N4	−160.31 (18)	S1—C1—N2—Ni1	−177.46 (8)
S1—C7—C8—N4	20.7 (2)	C8—C7—N3—N2	−178.38 (16)
N3—C7—C8—C9	20.3 (3)	S1—C7—N3—N2	0.6 (2)
S1—C7—C8—C9	−158.62 (15)	C1—N2—N3—C7	−0.1 (2)
N4—C8—C9—C10	−0.3 (3)	Ni1—N2—N3—C7	176.26 (13)
C7—C8—C9—C10	179.01 (18)	C11—C12—N4—C8	1.1 (3)
C8—C9—C10—C11	0.3 (3)	C9—C8—N4—C12	−0.4 (3)
C9—C10—C11—C12	0.3 (3)	C7—C8—N4—C12	−179.74 (17)
C10—C11—C12—N4	−1.0 (3)	N2—C1—S1—C7	0.63 (14)
C5—C6—N1—C2	0.9 (3)	C2i—C1—S1—C7	−179.58 (17)
C5—C6—N1—Ni1	−175.27 (14)	N3—C7—S1—C1	−0.72 (15)
C3—C2—N1—C6	−0.2 (3)	C8—C7—S1—C1	178.31 (16)
C1i—C2—N1—C6	−179.56 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···F1ii	0.86	1.88	2.704 (2)	160.
O1—H2W···F4	0.86	1.94	2.7880 (19)	171.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯F1i	0.86	1.88	2.704 (2)	160
O1—H2W⋯F4	0.86	1.94	2.7880 (19)	171

Symmetry code: (i) .