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

The bidentate 1,3,4-thia-diazole ligand substituted by two 2-pyridyl rings (denoted L) has been found to produce the new monomeric title complex, [Co(C(12)H(8)N(4)S)(2)(H(2)O)(2)](BF(4))(2). The thia-diazole and pyridyl rings surrounding the Co atom are almost coplanar [dihedral angle = 4.35 (7)°]. The mean plane defined by these heterocyclic moieties makes a dihedral angle of 18.72 (6)° with the non-coordinated pyridyl ring. The Co(2+) cation, located at a crystallographic center of symmetry, is bonded to two ligands and two water mol-ecules in a trans configuration in an octa-hedral environment. 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 along the [010] and [101] directions of O-H⋯F hydrogen bonds.

Related literature

For background to compounds with the same ligand, see: Bentiss et al. (2002 ▶, 2004 ▶); Zheng et al. (2006 ▶). For an improved synthesis of the ligand, see: Lebrini et al. (2005 ▶).

Experimental

Crystal data

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

M = 749.15

Monoclinic,

a = 10.8319 (2) Å

b = 11.0623 (2) Å

c = 13.2120 (3) Å

β = 101.114 (1)°

V = 1553.45 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.77 mm−1

T = 100 K

0.39 × 0.30 × 0.19 mm

Data collection

Bruker X8 APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.757, T max = 0.863

32328 measured reflections

3055 independent reflections

2877 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.064

S = 1.04

3055 reflections

214 parameters

H-atom parameters constrained

Δρmax = 0.54 e Å−3

Δρmin = −0.36 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: 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/S1600536811020125/im2290sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811020125/im2290Isup2.hkl

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

[Co(C12H8N4S)2(H2O)2](BF4)2	F(000) = 754
Mr = 749.15	Dx = 1.602 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3055 reflections
a = 10.8319 (2) Å	θ = 2.5–26.0°
b = 11.0623 (2) Å	µ = 0.77 mm−1
c = 13.2120 (3) Å	T = 100 K
β = 101.114 (1)°	Prism, pink
V = 1553.45 (5) Å3	0.39 × 0.30 × 0.19 mm
Z = 2

Bruker X8 APEXII diffractometer	3055 independent reflections
Radiation source: fine-focus sealed tube	2877 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
Tmin = 0.757, Tmax = 0.863	k = −13→13
32328 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.028P)2 + 1.2095P] where P = (Fo2 + 2Fc2)/3
3055 reflections	(Δ/σ)max = 0.001
214 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.36 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 > σ(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	0.57309 (16)	0.64485 (16)	0.25732 (14)	0.0216 (3)
F1	0.67597 (12)	0.59356 (14)	0.32121 (9)	0.0571 (4)
F2	0.58207 (9)	0.62506 (10)	0.15136 (7)	0.0332 (2)
F3	0.46504 (11)	0.59451 (11)	0.27939 (11)	0.0506 (3)
F4	0.57202 (12)	0.76967 (9)	0.27725 (9)	0.0446 (3)
C1	0.40758 (13)	0.75359 (13)	−0.02371 (11)	0.0182 (3)
C2	0.47872 (13)	1.25525 (13)	0.07062 (11)	0.0183 (3)
C3	0.43647 (14)	1.36225 (14)	0.10807 (12)	0.0217 (3)
H3	0.4818	1.4354	0.1061	0.026*
C4	0.32601 (15)	1.36036 (14)	0.14872 (12)	0.0247 (3)
H4	0.2948	1.4323	0.1740	0.030*
C5	0.26323 (15)	1.25161 (14)	0.15134 (12)	0.0245 (3)
H5	0.1882	1.2476	0.1784	0.029*
C6	0.31236 (14)	1.14767 (14)	0.11331 (12)	0.0224 (3)
H6	0.2695	1.0732	0.1161	0.027*
C7	0.22011 (13)	0.74718 (13)	0.04650 (11)	0.0196 (3)
C8	0.10139 (14)	0.71559 (14)	0.07978 (11)	0.0206 (3)
C9	0.01592 (15)	0.80486 (16)	0.09485 (13)	0.0278 (3)
H9	0.0326	0.8880	0.0854	0.033*
C10	−0.09485 (16)	0.76752 (18)	0.12427 (14)	0.0327 (4)
H10	−0.1560	0.8253	0.1349	0.039*
C11	−0.11496 (16)	0.64530 (17)	0.13791 (13)	0.0317 (4)
H11	−0.1899	0.6180	0.1578	0.038*
C12	−0.02334 (16)	0.56355 (16)	0.12188 (13)	0.0295 (4)
H12	−0.0372	0.4800	0.1322	0.035*
Co1	0.5000	1.0000	0.0000	0.01779 (9)
N1	0.41821 (12)	1.14819 (11)	0.07273 (10)	0.0196 (3)
N2	0.37922 (11)	0.85730 (11)	0.01641 (10)	0.0195 (3)
N3	0.27082 (12)	0.85445 (11)	0.05733 (10)	0.0210 (3)
N4	0.08401 (12)	0.59657 (12)	0.09253 (10)	0.0243 (3)
O1	0.61489 (10)	0.95481 (10)	0.14452 (9)	0.0267 (2)
H1W	0.6833	0.9925	0.1697	0.032*
H2W	0.6079	0.9000	0.1892	0.032*
S1	0.30230 (3)	0.64074 (3)	−0.01342 (3)	0.01990 (10)

	U11	U22	U33	U12	U13	U23
B1	0.0179 (8)	0.0198 (8)	0.0261 (9)	0.0022 (6)	0.0013 (7)	0.0020 (7)
F1	0.0467 (7)	0.0832 (10)	0.0362 (6)	0.0401 (7)	−0.0049 (5)	0.0013 (6)
F2	0.0322 (5)	0.0381 (6)	0.0277 (5)	−0.0042 (4)	0.0018 (4)	−0.0023 (4)
F3	0.0409 (6)	0.0405 (7)	0.0801 (9)	−0.0129 (5)	0.0361 (6)	−0.0168 (6)
F4	0.0673 (8)	0.0217 (5)	0.0455 (6)	−0.0078 (5)	0.0126 (6)	−0.0022 (5)
C1	0.0168 (7)	0.0148 (7)	0.0213 (7)	−0.0023 (5)	−0.0009 (5)	0.0027 (5)
C2	0.0170 (7)	0.0176 (7)	0.0185 (7)	−0.0009 (5)	−0.0012 (5)	0.0018 (5)
C3	0.0230 (8)	0.0164 (7)	0.0250 (8)	−0.0022 (6)	0.0024 (6)	0.0006 (6)
C4	0.0273 (8)	0.0204 (8)	0.0270 (8)	0.0026 (6)	0.0070 (6)	−0.0017 (6)
C5	0.0224 (7)	0.0252 (8)	0.0268 (8)	−0.0006 (6)	0.0074 (6)	0.0007 (6)
C6	0.0213 (7)	0.0198 (7)	0.0266 (8)	−0.0046 (6)	0.0061 (6)	0.0006 (6)
C7	0.0178 (7)	0.0185 (7)	0.0212 (7)	−0.0003 (6)	0.0006 (6)	0.0010 (6)
C8	0.0177 (7)	0.0232 (8)	0.0201 (7)	−0.0033 (6)	0.0018 (5)	−0.0013 (6)
C9	0.0220 (8)	0.0259 (8)	0.0348 (9)	0.0002 (6)	0.0032 (7)	−0.0001 (7)
C10	0.0219 (8)	0.0428 (10)	0.0341 (9)	0.0051 (7)	0.0074 (7)	−0.0038 (8)
C11	0.0226 (8)	0.0463 (11)	0.0284 (9)	−0.0080 (7)	0.0103 (7)	−0.0017 (8)
C12	0.0305 (9)	0.0300 (9)	0.0302 (8)	−0.0106 (7)	0.0114 (7)	−0.0016 (7)
Co1	0.01571 (14)	0.01254 (14)	0.02481 (16)	−0.00254 (10)	0.00315 (11)	−0.00077 (10)
N1	0.0184 (6)	0.0159 (6)	0.0235 (6)	−0.0018 (5)	0.0017 (5)	0.0012 (5)
N2	0.0166 (6)	0.0164 (6)	0.0253 (6)	−0.0018 (5)	0.0033 (5)	−0.0002 (5)
N3	0.0173 (6)	0.0194 (6)	0.0264 (7)	−0.0028 (5)	0.0043 (5)	0.0004 (5)
N4	0.0239 (7)	0.0229 (7)	0.0275 (7)	−0.0059 (5)	0.0083 (5)	−0.0016 (5)
O1	0.0244 (6)	0.0220 (6)	0.0306 (6)	−0.0050 (4)	−0.0027 (5)	0.0039 (5)
S1	0.01719 (18)	0.01395 (17)	0.0284 (2)	−0.00295 (13)	0.00399 (14)	0.00011 (14)

B1—F3	1.377 (2)	C7—S1	1.7543 (15)
B1—F1	1.383 (2)	C8—N4	1.345 (2)
B1—F4	1.406 (2)	C8—C9	1.394 (2)
B1—F2	1.439 (2)	C9—C10	1.393 (2)
C1—N2	1.3245 (19)	C9—H9	0.9500
C1—C2i	1.485 (2)	C10—C11	1.387 (3)
C1—S1	1.7138 (14)	C10—H10	0.9500
C2—N1	1.3565 (19)	C11—C12	1.389 (3)
C2—C3	1.394 (2)	C11—H11	0.9500
C2—C1i	1.485 (2)	C12—N4	1.345 (2)
C3—C4	1.403 (2)	C12—H12	0.9500
C3—H3	0.9500	Co1—N2	2.0880 (12)
C4—C5	1.386 (2)	Co1—N2i	2.0880 (12)
C4—H4	0.9500	Co1—O1i	2.1280 (11)
C5—C6	1.400 (2)	Co1—O1	2.1280 (11)
C5—H5	0.9500	Co1—N1i	2.1734 (13)
C6—N1	1.356 (2)	Co1—N1	2.1734 (13)
C6—H6	0.9500	N2—N3	1.3845 (17)
C7—N3	1.3039 (19)	O1—H1W	0.8597
C7—C8	1.479 (2)	O1—H2W	0.8597
F3—B1—F1	108.81 (15)	C9—C10—H10	120.3
F3—B1—F4	108.63 (14)	C10—C11—C12	118.70 (15)
F1—B1—F4	108.86 (14)	C10—C11—H11	120.6
F3—B1—F2	111.36 (14)	C12—C11—H11	120.6
F1—B1—F2	109.49 (13)	N4—C12—C11	123.37 (16)
F4—B1—F2	109.65 (13)	N4—C12—H12	118.3
N2—C1—C2i	119.94 (13)	C11—C12—H12	118.3
N2—C1—S1	112.95 (11)	N2—Co1—N2i	180.0
C2i—C1—S1	127.10 (11)	N2—Co1—O1i	90.06 (5)
N1—C2—C3	122.76 (13)	N2i—Co1—O1i	89.94 (5)
N1—C2—C1i	113.20 (13)	N2—Co1—O1	89.94 (5)
C3—C2—C1i	124.03 (13)	N2i—Co1—O1	90.06 (5)
C2—C3—C4	119.07 (14)	O1i—Co1—O1	180.0
C2—C3—H3	120.5	N2—Co1—N1i	78.03 (5)
C4—C3—H3	120.5	N2i—Co1—N1i	101.97 (5)
C5—C4—C3	118.77 (14)	O1i—Co1—N1i	89.90 (5)
C5—C4—H4	120.6	O1—Co1—N1i	90.10 (5)
C3—C4—H4	120.6	N2—Co1—N1	101.97 (5)
C4—C5—C6	118.80 (14)	N2i—Co1—N1	78.03 (5)
C4—C5—H5	120.6	O1i—Co1—N1	90.10 (5)
C6—C5—H5	120.6	O1—Co1—N1	89.90 (5)
N1—C6—C5	123.17 (14)	N1i—Co1—N1	180.0
N1—C6—H6	118.4	C6—N1—C2	117.42 (13)
C5—C6—H6	118.4	C6—N1—Co1	128.27 (10)
N3—C7—C8	123.68 (14)	C2—N1—Co1	114.19 (10)
N3—C7—S1	114.88 (11)	C1—N2—N3	114.59 (12)
C8—C7—S1	121.44 (11)	C1—N2—Co1	114.52 (10)
N4—C8—C9	124.24 (14)	N3—N2—Co1	130.79 (9)
N4—C8—C7	114.78 (13)	C7—N3—N2	110.42 (12)
C9—C8—C7	120.97 (14)	C8—N4—C12	116.84 (14)
C10—C9—C8	117.47 (16)	Co1—O1—H1W	123.1
C10—C9—H9	121.3	Co1—O1—H2W	131.9
C8—C9—H9	121.3	H1W—O1—H2W	105.0
C11—C10—C9	119.38 (16)	C1—S1—C7	87.15 (7)
C11—C10—H10	120.3
N1—C2—C3—C4	−0.8 (2)	O1—Co1—N1—C2	91.44 (10)
C1i—C2—C3—C4	178.56 (14)	N1i—Co1—N1—C2	7.1 (4)
C2—C3—C4—C5	0.7 (2)	C2i—C1—N2—N3	179.69 (12)
C3—C4—C5—C6	0.0 (2)	S1—C1—N2—N3	−0.59 (16)
C4—C5—C6—N1	−0.7 (2)	C2i—C1—N2—Co1	2.91 (17)
N3—C7—C8—N4	−160.18 (14)	S1—C1—N2—Co1	−177.38 (6)
S1—C7—C8—N4	20.91 (18)	N2i—Co1—N2—C1	−137 (5)
N3—C7—C8—C9	20.5 (2)	O1i—Co1—N2—C1	89.03 (11)
S1—C7—C8—C9	−158.44 (12)	O1—Co1—N2—C1	−90.97 (11)
N4—C8—C9—C10	−0.5 (2)	N1i—Co1—N2—C1	−0.85 (10)
C7—C8—C9—C10	178.78 (14)	N1—Co1—N2—C1	179.15 (10)
C8—C9—C10—C11	0.5 (2)	N2i—Co1—N2—N3	47 (5)
C9—C10—C11—C12	0.1 (3)	O1i—Co1—N2—N3	−87.11 (12)
C10—C11—C12—N4	−0.8 (3)	O1—Co1—N2—N3	92.89 (12)
C5—C6—N1—C2	0.7 (2)	N1i—Co1—N2—N3	−176.99 (13)
C5—C6—N1—Co1	−174.93 (11)	N1—Co1—N2—N3	3.01 (13)
C3—C2—N1—C6	0.0 (2)	C8—C7—N3—N2	−178.29 (13)
C1i—C2—N1—C6	−179.34 (12)	S1—C7—N3—N2	0.69 (16)
C3—C2—N1—Co1	176.30 (11)	C1—N2—N3—C7	−0.07 (18)
C1i—C2—N1—Co1	−3.08 (15)	Co1—N2—N3—C7	176.07 (10)
N2—Co1—N1—C6	−2.87 (14)	C9—C8—N4—C12	−0.1 (2)
N2i—Co1—N1—C6	177.13 (14)	C7—C8—N4—C12	−179.41 (14)
O1i—Co1—N1—C6	87.21 (13)	C11—C12—N4—C8	0.7 (2)
O1—Co1—N1—C6	−92.79 (13)	N2—C1—S1—C7	0.78 (11)
N1i—Co1—N1—C6	−177.1 (5)	C2i—C1—S1—C7	−179.52 (13)
N2—Co1—N1—C2	−178.64 (10)	N3—C7—S1—C1	−0.86 (12)
N2i—Co1—N1—C2	1.36 (10)	C8—C7—S1—C1	178.15 (13)
O1i—Co1—N1—C2	−88.56 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···F1ii	0.86	1.88	2.7014 (16)	161
O1—H2W···F4	0.86	1.94	2.7927 (16)	172

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	2.7014 (16)	161
O1—H2W⋯F4	0.86	1.94	2.7927 (16)	172

Symmetry code: (i) .