Crystal structure of catena-poly[[[di­aqua­cobalt(II)]-bis­(μ-hex-3-enedi­nitrile-κ2N:N′)] bis­(tetra­fluorido­borate)]

Son, J.-S.; Lim, S.-C.; Lee, H.; Hong, S.-T.

doi:10.1107/S2056989015009548

metal-organic compounds

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Volume 71| Part 6| June 2015| Pages m135-m136

doi:10.1107/S2056989015009548

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Crystal structure of catena-poly[[[diaquacobalt(II)]-bis(μ-hex-3-enedinitrile-κ²N:N′)] bis(tetrafluoridoborate)]

Jung-Su Son,^a ‡ Sung-Chul Lim,^a ‡ Hochun Lee ^a ^* and Seung-Tae Hong ^a ^*

^aDaegu Gyeongbuk Institue of Science & Technology (DGIST), Daegu 711-873, Republic of Korea
^*Correspondence e-mail: dukelee@dgist.ac.kr, st.hong@dgist.ac.kr

Edited by M. Weil, Vienna University of Technology, Austria (Received 8 May 2015; accepted 19 May 2015; online 23 May 2015)

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 octahedral coordination environment, defined by the cyano N atoms of four hex-3-enedinitrile ligands in equatorial positions and the O atoms of two water molecules in axial positions. The bridging mode of the hex-3-enedinitrile 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 methylene H atom of the hex-3-enedinitrile 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.

Keywords: crystal structure; cobalt; hex-3-enedinitrile; hydrogen bonding.

CCDC reference: 1401602

1. 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 electrolyte 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.

2. Experimental

2.1. Crystal data

[Co(C₆H₆N₂)(H₂O)₂](BF₄)₂
M_r = 480.84
Triclinic, $[P \overline 1]$
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

2.2. 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

2.3. Refinement

R[F² > 3σ(F²)] = 0.033
wR(F²) = 0.068
S = 0.87
2202 reflections
170 parameters
20 restraints
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H22⋯O1ⁱ	0.97	2.52	3.348 (3)	143 (1)
O1—H12⋯F1ⁱⁱ	0.83	1.89	2.72 (2)	175 (1)
O1—H11⋯F2ⁱ	0.82	1.87	2.669 (13)	163 (1)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x-1, y+1, z.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (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.

Supporting information

CCDC reference: 1401602

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

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

checkCIF report

Experimental top

A solvent was prepared first by mixing ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in an 1:2 volume ratio (3.3 ml and 6.6 ml, respectively). 0.934 g of lithium tetrafluoridoborate (LiBF₄) were added to the solvent, and it was stirred for about 5 hours to dissolve the salt completely to form an 1M solution. 0.60 g (5 wt.%) of cobalt(II) tetrafluoridoborate hexahydrate and 0.24 g (2 wt.%) hex-3-enedinitrile were added and dissolved in the solution. The solution was kept for 48 hours in an argon-atmosphere glove-box at room temperature, resulting in the growth of red crystals. The crystals were washed with pure EMC solvent three times in the argon-atmosphere glove-box.

Refinement top

H atoms attached to C atoms of the title compound were placed in geometrically idealized positions and treated as rigid bodies with C—H distances constrained to 0.92–0.97 Å. Water H atoms were located from a difference map and refined with a distance of 0.82 Å. The BF₄^- counter anion was refined with a positional disorder model where F2, F3 and F4 atoms are split into two positions while B1 and F1 atoms are not. Such a disorder model resulted in a slightly better refinement, reducing the R1 factor values from 0.041 to 0.033.

Related literature top

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 electrolyte 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.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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 (Betteridge et al., 2003).

Figures top

	Fig. 1. 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.
	Fig. 2. 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, blue: C, red: O, cyan: B, green: F, grey: H).

catena-poly[[[diaquacobalt(II)]-bis(µ-hex-3-enedinitrile-κ²N:N')] bis(tetrafluoridoborate)] top

Crystal data top

[Co(C₆H₆N₂)(H₂O)₂](BF₄)₂	Z = 1
M_r = 480.84	F(000) = 241
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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	Δρ_max = 0.83 e Å⁻³
170 parameters	Δρ_min = −0.62 e Å⁻³
20 restraints

Crystal data top

[Co(C₆H₆N₂)(H₂O)₂](BF₄)₂	γ = 66.184 (4)°
M_r = 480.84	V = 507.21 (12) Å³
Triclinic, P1	Z = 1
a = 7.9839 (11) Å	Mo Kα radiation
b = 8.3434 (11) Å	µ = 0.93 mm⁻¹
c = 8.8441 (13) Å	T = 103 K
α = 71.380 (5)°	0.20 × 0.20 × 0.20 mm
β = 88.458 (5)°

Data collection top

Bruker APEXII CCD diffractometer	2501 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	2233 reflections with I > 2σ(I)
T_min = 0.60, T_max = 0.75	R_int = 0.038
14705 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	20 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 0.87	Δρ_max = 0.83 e Å⁻³
2202 reflections	Δρ_min = −0.62 e Å⁻³
170 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···F1^iv	0.83	1.89	2.72 (2)	175 (1)
O1—H11···F2ⁱⁱⁱ	0.82	1.87	2.669 (13)	163 (1)

Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) x−1, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H22···O1ⁱ	0.970	2.520	3.348 (3)	143.1 (3)
O1—H12···F1ⁱⁱ	0.830	1.890	2.72 (2)	174.58 (8)
O1—H11···F2ⁱ	0.820	1.873	2.669 (13)	163.0 (4)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y+1, z.

Footnotes

‡contributed equally.

Acknowledgements

This work was supported by the DGIST R&D Program of Ministry of Science, ICT and Future Planning of Korea (grant No. 15-HRLA-01).

References

Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Blount, J. F., Freeman, H. C., Hemmerich, P. & Sigwart, C. (1969). Acta Cryst. B25, 1518–1524. CSD CrossRef IUCr Journals Google Scholar
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dowty, E. (2000). ATOMS for Windows. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Heller, M. & Sheldrick, W. S. (2004). Z. Anorg. Allg. Chem. 630, 1869–1874. CSD CrossRef CAS Google Scholar
Kim, Y. S., Kim, T. H., Lee, H. & Song, H. K. (2011). Energ. Environ. Sci. 4, 4038–4045. CrossRef CAS Google Scholar
Kim, Y. S., Lee, S. H., Son, M. Y., Jung, Y. M., Song, H. K. & Lee, H. (2014a). ACS Appl. Mat. Interfaces, 6, 2039–2043. CrossRef CAS Google Scholar
Kim, Y. S., Lee, H. & Song, H. K. (2014b). ACS Appl. Mater. Interfaces, 6, 8913–8920. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Storhoff, B. N. & Lewis, H. C. Jr (1977). Coord. Chem. Rev. 23, 1–29. CAS Google Scholar

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Volume 71| Part 6| June 2015| Pages m135-m136

doi:10.1107/S2056989015009548

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