Crystal structure of catena-poly[[[di-aqua-cobalt(II)]-bis-(μ-hex-3-enedi-nitrile-κ(2) N:N')] bis-(tetra-fluorido-borate)].

In the structure of the title salt, [Co(C6H6N2)2(H2O)2](BF4)2, the Co(II) atom is located on an inversion centre. The transition metal is in a slightly distorted octa-hedral coordination environment, defined by the cyano N atoms of four hex-3-enedi-nitrile ligands in equatorial positions and the O atoms of two water mol-ecules in axial positions. The bridging mode of the hex-3-enedi-nitrile ligands leads to the formation of cationic chains extending parallel to [1-10]. The BF4 (-) counter-anion is disordered over two sets of sites [occupancy ratio = 0.512 (19):0.489 (19)]. It is located in the voids between the cationic chains and is connected to the aqua ligands of the latter through O-H⋯F hydrogen bonds. One methyl-ene H atom of the hex-3-enedi-nitrile ligand forms another and weak C-H⋯O hydrogen bond with a water O atom of a neighbouring chain, thus consolidating the three-dimensional network structure.

Related literature

Aliphatic di­nitriles have gained much attention not only due to their rich coordination chemistry with transition-metal ions (Storhoff & Lewis, 1977 ▸; Heller & Sheldrick, 2004 ▸; Blount et al., 1969 ▸), but also due to their applications as functional eln class="Chemical">ectrolyte additives for lithium ion batteries (Kim et al., 2011 ▸, 2014a ▸,b ▸). While the coordination complexes of saturated aliphatic di­nitrile ligands have been extensively studied (Storhoff & Lewis, 1977 ▸; Heller & Sheldrick, 2004 ▸; Blount et al., 1969 ▸), those of unsaturated di­nitrile ligands like in the title compound have hardly been reported so far.

Experimental

Crystal data

[Co(C6H6N2)(H2O)2](BF4)2

M = 480.84

Triclinic,

a = 7.9839 (11) Å

b = 8.3434 (11) Å

c = 8.8441 (13) Å

α = 71.380 (5)°

β = 88.458 (5)°

γ = 66.184 (4)°

V = 507.21 (12) Å3

Z = 1

Mo Kα radiation

μ = 0.93 mm−1

T = 103 K

0.20 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▸) T min = 0.60, T max = 0.75

14705 measured reflections

2501 independent reflections

2233 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 3σ(F 2)] = 0.033

wR(F 2) = 0.068

S = 0.87

2202 reflections

170 parameters

20 restraints

H-atom parameters constrained

Δρmax = 0.83 e Å−3

Δρmin = −0.62 e Å−3

Data collection: APEX2 (Bruker, 2006 ▸); cell refinement: SAIn class="Chemical">NT (Bruker, 2006 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▸); molecular graphics: ATOMS (Dowty, 2000 ▸); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015009548/wm5160sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015009548/wm5160Isup2.hkl

Click here for additional data file.

4 − . DOI: 10.1107/S2056989015009548/wm5160fig1.tif

The cationic chain structure of the title compound with displacement ellipsoids drawn at the 50% probability level. The BF4 − anion is shown only with the major part of the disorder.

Click here for additional data file.

4 − . DOI: 10.1107/S2056989015009548/wm5160fig2.tif

The crystal packing of the title compound with displacement ellipsoids drawn at the 50% probability level. The BF4 − anion is shown only with the major part of the disorder. (Colour code: dark blue: Co, purple: n class="Chemical">N, blue: C, red: O, cyan: B, green: F, grey: H).

CCDC reference: 1401602

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

[Co(C6H6N2)(H2O)2](BF4)2	Z = 1
Mr = 480.84	F(000) = 241
Triclinic, P1	Dx = 1.575 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9839 (11) Å	Cell parameters from 0 reflections
b = 8.3434 (11) Å	θ = 0–0°
c = 8.8441 (13) Å	µ = 0.93 mm−1
α = 71.380 (5)°	T = 103 K
β = 88.458 (5)°	Cuboid, yellow
γ = 66.184 (4)°	0.20 × 0.20 × 0.20 mm
V = 507.21 (12) Å3

Bruker APEXII CCD diffractometer	2233 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
φ & ω scans	θmax = 28.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→10
Tmin = 0.60, Tmax = 0.75	k = −11→11
14705 measured reflections	l = −11→11
2501 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.068	Weighting scheme based on measured s.u.'s W = 1
S = 0.87	(Δ/σ)max = 0.0002
2202 reflections	Δρmax = 0.83 e Å−3
170 parameters	Δρmin = −0.62 e Å−3
20 restraints

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	Occ. (<1)
Co1	0.0000	1.0000	0.5000	0.0158
N1	0.2687 (2)	0.8866 (2)	0.6299 (2)	0.0199
N2	0.1190 (2)	0.9254 (2)	0.3036 (2)	0.0192
C1	0.4140 (2)	0.8397 (3)	0.6904 (2)	0.0179
C2	0.6004 (3)	0.7780 (3)	0.7691 (3)	0.0221
C3	0.7036 (2)	0.5683 (3)	0.8382 (2)	0.0200
C4	0.6448 (3)	0.4468 (3)	0.8245 (2)	0.0201
C5	0.7535 (3)	0.2388 (3)	0.9045 (2)	0.0244
C6	0.8244 (2)	0.1444 (2)	0.7878 (2)	0.0181
O1	0.02105 (18)	1.25018 (18)	0.41358 (16)	0.0197
B1	0.7569 (3)	0.7200 (3)	0.2131 (3)	0.0287
F1	0.77132 (18)	0.55820 (17)	0.18696 (15)	0.0295
F2	0.8571 (16)	0.6724 (15)	0.3523 (13)	0.0555	0.512 (19)
F3	0.8368 (13)	0.8076 (13)	0.0834 (11)	0.0630	0.512 (19)
F4	0.5804 (9)	0.8300 (10)	0.2014 (15)	0.0585	0.512 (19)
F21	0.9052 (8)	0.6606 (13)	0.3357 (11)	0.0255	0.489 (19)
F31	0.7671 (17)	0.8497 (11)	0.0853 (10)	0.0551	0.489 (19)
F41	0.5866 (9)	0.7929 (11)	0.2810 (16)	0.0534	0.489 (19)
H11	0.0413	1.2954	0.4771	0.034 (4)*
H12	−0.0554	1.3393	0.3416	0.043 (4)*
H21	0.5897	0.8291	0.8529	0.034 (4)*
H22	0.6694	0.8293	0.6919	0.033 (4)*
H31	0.8174	0.5253	0.8931	0.034 (4)*
H41	0.5301	0.4889	0.7639	0.035 (4)*
H51	0.6801	0.1848	0.9680	0.036 (4)*
H52	0.8570	0.2189	0.9701	0.034 (4)*

	U11	U22	U33	U12	U13	U23
Co1	0.01363 (18)	0.01074 (17)	0.0198 (2)	−0.00181 (13)	−0.00123 (13)	−0.00526 (14)
N1	0.0166 (8)	0.0169 (8)	0.0222 (8)	−0.0025 (6)	−0.0014 (6)	−0.0070 (6)
N2	0.0170 (7)	0.0163 (8)	0.0211 (8)	−0.0039 (6)	0.0006 (6)	−0.0060 (6)
C1	0.0173 (7)	0.0138 (8)	0.0201 (9)	−0.0033 (7)	0.0015 (7)	−0.0067 (7)
C2	0.0153 (7)	0.0209 (9)	0.0292 (10)	−0.0055 (7)	−0.0023 (7)	−0.0093 (8)
C3	0.0139 (7)	0.0221 (9)	0.0194 (9)	−0.0018 (7)	−0.0025 (7)	−0.0081 (7)
C4	0.0170 (7)	0.0207 (9)	0.0178 (9)	−0.0024 (7)	0.0018 (7)	−0.0076 (7)
C5	0.0266 (7)	0.0216 (10)	0.0182 (9)	−0.0031 (8)	0.0026 (8)	−0.0074 (8)
C6	0.0172 (7)	0.0135 (8)	0.0176 (9)	−0.0032 (7)	−0.0023 (7)	−0.0015 (7)
O1	0.0223 (7)	0.0126 (6)	0.0219 (7)	−0.0052 (5)	−0.0021 (5)	−0.0056 (5)
B1	0.0252 (12)	0.0159 (10)	0.0380 (14)	−0.0057 (9)	−0.0119 (10)	−0.0028 (10)
F1	0.0363 (7)	0.0211 (6)	0.0283 (7)	−0.0096 (5)	−0.0101 (5)	−0.0067 (5)
F2	0.072 (4)	0.036 (3)	0.049 (4)	−0.010 (4)	−0.032 (4)	−0.017 (2)
F3	0.046 (3)	0.047 (4)	0.071 (3)	−0.026 (3)	−0.009 (3)	0.022 (3)
F4	0.0361 (18)	0.039 (3)	0.088 (5)	0.0039 (18)	0.000 (3)	−0.031 (3)
F21	0.0208 (19)	0.021 (2)	0.032 (2)	−0.0030 (16)	−0.0089 (16)	−0.0115 (15)
F31	0.072 (4)	0.031 (3)	0.046 (2)	−0.028 (3)	−0.025 (3)	0.019 (2)
F41	0.0304 (19)	0.042 (3)	0.088 (5)	−0.0067 (18)	0.010 (3)	−0.034 (3)

Co1—N1i	2.1486 (17)	C4—H41	0.946
Co1—N2i	2.1050 (17)	C5—C6	1.460 (6)
Co1—O1i	2.0560 (15)	C5—H51	0.946
Co1—N1	2.1486 (17)	C5—H52	0.949
Co1—N2	2.1050 (17)	O1—H11	0.821
Co1—O1	2.0560 (15)	O1—H12	0.826
N1—C1	1.148 (6)	B1—F1	1.401 (3)
N2—C6ii	1.125 (5)	B1—F2	1.341 (12)
C1—C2	1.474 (8)	B1—F3	1.435 (11)
C2—C3	1.514 (9)	B1—F4	1.320 (9)
C2—H21	0.953	B1—F1	1.401 (3)
C2—H22	0.967	B1—F21	1.440 (12)
C3—C4	1.315 (4)	B1—F31	1.319 (11)
C3—H31	0.916	B1—F41	1.450 (10)
C4—C5	1.516 (3)
N1i—Co1—N2i	90.57 (6)	C4—C3—H31	118.7
N1i—Co1—O1i	87.29 (6)	C3—C4—C5	122.3 (3)
N2i—Co1—O1i	91.15 (6)	C3—C4—H41	119.7
N1i—Co1—N1	179.995	C5—C4—H41	118.0
N2i—Co1—N1	89.4 (8)	C4—C5—C6	112.18 (14)
O1i—Co1—N1	92.7 (4)	C4—C5—H51	110.9
N1i—Co1—N2	89.4 (4)	C6—C5—H51	108.7
N2i—Co1—N2	179.995	C4—C5—H52	108.2
O1i—Co1—N2	88.9 (6)	C6—C5—H52	107.0
N1—Co1—N2	90.57 (6)	H51—C5—H52	109.8
N1i—Co1—O1	92.7 (8)	C5—C6—N2ii	178.3 (2)
N2i—Co1—O1	88.9 (3)	Co1—O1—H11	119.4
O1i—Co1—O1	179.994	Co1—O1—H12	121.0
N1—Co1—O1	87.29 (6)	H11—O1—H12	105.0
N2—Co1—O1	91.15 (6)	F1—B1—F2	109.0 (6)
Co1—N1—C1	173.92 (16)	F1—B1—F3	105.3 (7)
Co1—N2—C6ii	166.34 (18)	F2—B1—F3	109.1 (7)
N1—C1—C2	179.5 (2)	F1—B1—F4	108.3 (6)
C1—C2—C3	113.2 (2)	F2—B1—F4	115.9 (6)
C1—C2—H21	108.5	F3—B1—F4	108.7 (6)
C3—C2—H21	109.3	F1—B1—F21	105.8 (6)
C1—C2—H22	108.7	F1—B1—F31	115.0 (6)
C3—C2—H22	109.9	F21—B1—F31	109.8 (7)
H21—C2—H22	107.0	F1—B1—F41	108.4 (6)
C2—C3—C4	125.87 (19)	F21—B1—F41	106.8 (6)
C2—C3—H31	115.5	F31—B1—F41	110.7 (8)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H22···O1iii	0.97	2.52	3.348 (3)	143 (1)
O1—H12···F1iv	0.83	1.89	2.72 (2)	175 (1)
O1—H11···F2iii	0.82	1.87	2.669 (13)	163 (1)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C2H22O1i	0.97	2.52	3.348(3)	143(1)
O1H12F1ii	0.83	1.89	2.72(2)	175(1)
O1H11F2i	0.82	1.87	2.669(13)	163(1)

Symmetry codes: (i) ; (ii) .