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Acta Cryst. (2009). E65, m813    [ doi:10.1107/S1600536809023265 ]

catena-Poly[[diaquabis(thiocyanato-[kappa]N)cobalt(II)]-[mu]-4,4'-bipyridine-[kappa]2N:N'] 4,4'-bipyridine solvate\]

R. Yao and D. E. Wang

Abstract top

In the title complex, {[Co(NCS)2(C10H8N2)(H2O)2]·C10H8N2}n, the CoII ion is located on an inversion centre and is coordinated by two N atoms from the two 4,4'-bipyridine ligands, two O atoms from the water molecule, and two N atoms from two isothiocyanate ions in a distorted octahedral environment. In the crystal, the coordinated water molecules, isothiocyanate ions and solvent 4,4'-bipyridine molecules are linked by O-H...S and O-H...N hydrogen bonds into layers parallel to the ab plane.

Comment top

For 2-D MnII and 1-D CuII complexes constructed from 4,4'-bipy see: Yang et al. (2008) and Zhou, et al. (2008). The compound of [Co(4,4'-bipy)(NCS)2(OH2)2].(4,4'-bipy) were reported (Lu, et al. 1997) but the polymeric compound has not been synthesized, so far. Herein, we report the crystal structure of a novel polymeric compound, {[Co(4,4'-bipy)(NCS)2(OH2)2].(4,4'-bipy)}n. The CoII ion is coordinated by two N atoms from 4,4'-bipy ligand, two N atoms from isothiocyanate ions, and two O atoms from two water molecule in a distorted octahedral geometry (Fig. 1, Table 1). O(1), N(2), O(1)i and N(2)i[symmetry code: -1 + x, y, z] lie in the equatorial plane, with the O(1)—N(2)—O(1)i—N(2)i torsional angle of 0.02 (11)°, while the Co atom deviates from the equatorial plane by 0.051 Å. N(5), N(5)i atoms occupy the axial sites, which are strictly linear due to a symmetry opeartion. The bond lengths and angles of the title complex are similar to the compound {[Co(4,4'-bipy)(ambdc)(OH2)2](4,4'-bipy)(DMF)}n (He et al.,2006). In the crystal packing of (l) are linked by O—H···S and O—H···N hydrogen bonds (Table 2, Fig. 2).

Related literature top

For two-dimensional MnII and one-dimensional CuII complexes constructed from 4,4'-bipy, see: Yang et al. (2008); Zhou & He (2008). For related structures, see: Lu et al. (1997); He et al. (2006).

Experimental top

A mixture of Co(CH3COO)2(0.5 mmol), 4,4'-bipy (0.5 mmol and H2O (10.00 ml), was placed in a Parr Teflon-lined stainless steel vessel (10 ml), and then the vessel was sealed and heated at 393 K for 3 d. After the mixture was slowly cooled to room temperature, a few red crystals of [Co(4,4'-bipy)(NCS)2(OH2)2].(4,4'-bipy) were obtained.

Refinement top

H atoms of water molecule were located in a difference map and refined with O—H distance restraints of 0.82 (3)) Å, and Uiso(H) = 1.5Ueq(O). Other H atoms bonded to C atoms were introduced at calculated positions and refined using a riding model, with Uiso(H) = 1.2Ueq(C), and C—H distances of 0.93 Å.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A part of polymeric chain of CoII octahedra with 4,4-bpy bridging ligand is shown with ellipsoids at the 30% probability level. Symmetry codes used: (i) -x + 1,-y + 1,-z + 1; (ii) x - 1, y, z. (iii)-x, -y, -z.
[Figure 2] Fig. 2. The crystal packing of (I) with hydrogen bonds (dashed lines).
catena-Poly[[diaquabis(thiocyanato-κN)cobalt(II)]-µ-4,4'- bipyridine-κ2N:N'] 4,4'-bipyridine solvate] top
Crystal data top
[Co(NCS)2(C10H8N2)(H2O)2]·C10H8N2V = 612.66 (14) Å3
Mr = 523.51Z = 1
Triclinic, P1F(000) = 269
Hall symbol: -P 1Dx = 1.419 Mg m−3
a = 7.4433 (11) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.0147 (11) Åθ = 1.0–26.0°
c = 10.1114 (13) ŵ = 0.90 mm−1
α = 107.770 (2)°T = 293 K
β = 103.978 (2)°Block, red
γ = 97.038 (2)°0.20 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		2359 independent reflections
Radiation source: fine-focus sealed tube2191 reflections with I > 2σ(I)
graphiteRint = 0.012
φ and ωs scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		h = −9→4
Tmin = 0.835, Tmax = 0.835k = −11→11
3522 measured reflectionsl = −12→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0744P)2 + 0.3257P]
where P = (Fo2 + 2Fc2)/3
2359 reflections(Δ/σ)max < 0.001
157 parametersΔρmax = 0.77 e Å−3
3 restraintsΔρmin = −0.74 e Å−3
Crystal data top
[Co(NCS)2(C10H8N2)(H2O)2]·C10H8N2γ = 97.038 (2)°
Mr = 523.51V = 612.66 (14) Å3
Triclinic, P1Z = 1
a = 7.4433 (11) ÅMo Kα radiation
b = 9.0147 (11) ŵ = 0.90 mm−1
c = 10.1114 (13) ÅT = 293 K
α = 107.770 (2)°0.20 × 0.20 × 0.20 mm
β = 103.978 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2359 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1997)		2191 reflections with I > 2σ(I)
Tmin = 0.835, Tmax = 0.835Rint = 0.012
3522 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118Δρmax = 0.77 e Å−3
S = 1.04Δρmin = −0.74 e Å−3
2359 reflectionsAbsolute structure: ?
157 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Co10.50000.50000.50000.03359 (17)
S10.93240 (12)0.61882 (16)0.23801 (12)0.0837 (4)
O10.3666 (3)0.6731 (2)0.4436 (2)0.0453 (4)
H1B0.251 (3)0.659 (4)0.418 (4)0.068*
H1C0.403 (4)0.719 (4)0.394 (3)0.068*
N20.6824 (3)0.5256 (3)0.3768 (2)0.0467 (5)
N50.2992 (3)0.3143 (2)0.3142 (2)0.0365 (4)
C10.2050 (4)0.1832 (3)0.3238 (3)0.0439 (6)
H1A0.22010.17570.41540.053*
C20.0868 (4)0.0590 (3)0.2048 (3)0.0433 (6)
H2A0.0247−0.02950.21720.052*
C30.0605 (3)0.0664 (3)0.0661 (2)0.0326 (5)
C40.1567 (4)0.2036 (3)0.0576 (2)0.0390 (5)
H40.14230.2157−0.03220.047*
C50.2730 (4)0.3217 (3)0.1814 (2)0.0398 (5)
H50.33690.41150.17210.048*
C210.7868 (4)0.5654 (3)0.3206 (3)0.0439 (6)
N70.4547 (4)0.8112 (3)0.2551 (3)0.0652 (7)
C110.5596 (5)0.9552 (4)0.2955 (4)0.0664 (8)
H110.62221.00720.39390.080*
C120.5829 (5)1.0347 (4)0.2006 (3)0.0579 (7)
H120.65881.13650.23560.070*
C130.4917 (4)0.9604 (3)0.0537 (3)0.0458 (6)
C140.3805 (5)0.8079 (4)0.0096 (4)0.0590 (7)
H140.31700.7522−0.08810.071*
C150.3664 (6)0.7408 (4)0.1137 (4)0.0695 (9)
H150.29010.63970.08280.083*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0348 (3)0.0325 (3)0.0224 (2)−0.00978 (17)0.00294 (17)0.00493 (17)
S10.0513 (5)0.1408 (10)0.0912 (7)0.0135 (5)0.0309 (5)0.0798 (7)
O10.0453 (10)0.0441 (10)0.0408 (10)−0.0031 (8)0.0058 (8)0.0172 (8)
N20.0450 (12)0.0515 (12)0.0351 (11)−0.0079 (10)0.0114 (10)0.0105 (9)
N50.0366 (10)0.0335 (10)0.0271 (9)−0.0071 (8)0.0014 (8)0.0052 (8)
C10.0494 (14)0.0412 (13)0.0265 (11)−0.0144 (11)0.0032 (10)0.0067 (10)
C20.0469 (14)0.0385 (12)0.0303 (11)−0.0154 (10)0.0048 (10)0.0067 (10)
C30.0293 (10)0.0321 (11)0.0271 (10)−0.0005 (9)0.0022 (9)0.0048 (9)
C40.0471 (13)0.0326 (11)0.0266 (10)−0.0036 (10)−0.0002 (10)0.0087 (9)
C50.0451 (13)0.0311 (11)0.0318 (11)−0.0072 (10)0.0011 (10)0.0087 (9)
C210.0379 (13)0.0521 (15)0.0370 (12)−0.0010 (11)0.0043 (10)0.0180 (11)
N70.0780 (18)0.0692 (17)0.0740 (18)0.0243 (15)0.0358 (15)0.0466 (15)
C110.078 (2)0.072 (2)0.0585 (19)0.0154 (18)0.0229 (17)0.0335 (17)
C120.0635 (18)0.0549 (17)0.0609 (18)0.0066 (14)0.0204 (15)0.0285 (14)
C130.0490 (14)0.0465 (14)0.0560 (15)0.0158 (11)0.0268 (12)0.0266 (13)
C140.073 (2)0.0491 (16)0.0597 (18)0.0059 (14)0.0237 (16)0.0255 (14)
C150.085 (2)0.0537 (18)0.082 (2)0.0077 (17)0.033 (2)0.0361 (17)
Geometric parameters (Å, °) top
Co1—N2i2.089 (2)C3—C41.388 (3)
Co1—N22.089 (2)C3—C3ii1.486 (4)
Co1—O12.0964 (19)C4—C51.374 (3)
Co1—O1i2.0964 (19)C4—H40.9300
Co1—N52.1625 (18)C5—H50.9300
Co1—N5i2.1625 (18)N7—C111.318 (5)
S1—C211.630 (3)N7—C151.330 (5)
O1—H1B0.817 (18)C11—C121.390 (4)
O1—H1C0.813 (17)C11—H110.9300
N2—C211.151 (3)C12—C131.382 (4)
N5—C51.333 (3)C12—H120.9300
N5—C11.341 (3)C13—C141.394 (4)
C1—C21.378 (3)C13—C13iii1.490 (5)
C1—H1A0.9300C14—C151.382 (4)
C2—C31.393 (3)C14—H140.9300
C2—H2A0.9300C15—H150.9300
N2i—Co1—N2180.0C3—C2—H2A120.1
N2i—Co1—O190.16 (9)C4—C3—C2116.3 (2)
N2—Co1—O189.84 (9)C4—C3—C3ii121.7 (2)
N2i—Co1—O1i89.84 (9)C2—C3—C3ii122.0 (3)
N2—Co1—O1i90.16 (9)C5—C4—C3120.3 (2)
O1—Co1—O1i180.0C5—C4—H4119.9
N2i—Co1—N588.84 (8)C3—C4—H4119.9
N2—Co1—N591.16 (8)N5—C5—C4123.5 (2)
O1—Co1—N590.36 (7)N5—C5—H5118.3
O1i—Co1—N589.64 (7)C4—C5—H5118.3
N2i—Co1—N5i91.16 (8)N2—C21—S1178.8 (3)
N2—Co1—N5i88.84 (8)C11—N7—C15116.2 (3)
O1—Co1—N5i89.64 (7)N7—C11—C12124.3 (3)
O1i—Co1—N5i90.36 (7)N7—C11—H11117.8
N5—Co1—N5i180.0C12—C11—H11117.8
Co1—O1—H1B121 (2)C13—C12—C11119.1 (3)
Co1—O1—H1C121 (2)C13—C12—H12120.4
H1B—O1—H1C106 (3)C11—C12—H12120.4
C21—N2—Co1169.0 (2)C12—C13—C14117.1 (3)
C5—N5—C1116.7 (2)C12—C13—C13iii121.9 (3)
C5—N5—Co1120.28 (15)C14—C13—C13iii121.0 (3)
C1—N5—Co1122.85 (15)C15—C14—C13118.8 (3)
N5—C1—C2123.3 (2)C15—C14—H14120.6
N5—C1—H1A118.3C13—C14—H14120.6
C2—C1—H1A118.3N7—C15—C14124.4 (3)
C1—C2—C3119.9 (2)N7—C15—H15117.8
C1—C2—H2A120.1C14—C15—H15117.8
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z; (iii) −x+1, −y+2, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1C···N70.82 (3)1.92 (3)2.732 (3)171 (3)
O1—H1B···S1iv0.82 (3)2.52 (3)3.279 (2)154 (3)
Symmetry codes: (iv) x−1, y, z.
Table 1
Selected geometric parameters (Å) top
Co1—N2i2.089 (2)Co1—O1i2.0964 (19)
Co1—N22.089 (2)Co1—N52.1625 (18)
Co1—O12.0964 (19)Co1—N5i2.1625 (18)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1C···N70.82 (3)1.92 (3)2.732 (3)171 (3)
O1—H1B···S1ii0.82 (3)2.52 (3)3.279 (2)154 (3)
Symmetry codes: (ii) x−1, y, z.
references
References top

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He, H. Y., Zhou, Y. L. & Zhu, L. G. (2006). Chin. J. Inorg. Chem. 22, 142–144.

Lu, J., Paliwala, T., Lim, S. C., Yu, C., Niu, T. & Jacobson, A. J. (1997). Inorg. Chem. 36, 923–927.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yang, Y. Q., Li, C. H., Li, W., Chen, Z. M. & Wang, Y. (2008). Chin. J. Inorg. Chem. 24, 1365-1368.

Zhou, Y. L. & He, H. Y. (2008). Chin. J. Inorg. Chem. 24, 290–292.