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Acta Cryst. (2007). E63, m1379    [ doi:10.1107/S1600536807017461 ]

Tetrakis(pyridine-[kappa]N)bis(thiocyanato-[kappa]N)cobalt(II)

H. Zhong, X.-R. Zeng, X.-M. Yang and Q.-Y. Luo

Abstract top

In the molecule of the title complex, [Co(NCS)2(C5H5N)4], the CoII atom is bonded in a distorted octahedral arrangement to two N atoms of two SCN- and four N atoms of four pyridine ligands. A crystallographic twofold rotation axis passes through the Co atom, and the N and para-C atoms of two trans pyridine rings. In the crystal structure, weak [pi]-[pi] stacking interactions, which involve the pyridine rings of adjacent pyridine ligands with a centroid-centroid distance of 3.475 (3) Å [symmetry code: 1 - x, 2 - y, 1 - z], cause the formation of a supramolecular network structure.

Comment top

In recent years, interest in the chemistry of metal-oxygen clusters has grown because of their applications in areas including catalysis, materials, chemistry and biochemistry (Pope & Müller, 2001). The π-π stacking between aromatic rings is related to the electron-transfer process in some biological systems (Deisenhofer & Michel, 1989; Wall et al., 1999). Aromatic polycyclic compounds, such as pyridine, phenanthroline, quinoline and benzimidazole, have commonly shown π-π stacking in metal complexes (Wu et al., 2003; Pan & Xu, 2004; Liu et al., 2004; Li et al., 2005). We herein report the crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). The two N atoms of two SCN- and four N atoms of four pyridine rings are coordinated to the Co atom, in a distorted octahedral arrangement (Table 1). The planar pyridine rings A (N1/C1—C5), B (N2/C6A/C7A/C6—C8) and C (N3/C9A/C10A/C9—C11) are nearly perpendicular to each other, with dihedral angles of A/B = 110.83 (7), A/C = 87.04 (6) and B/C = 87.12 (2)°.

In the crystal structure, the weak π-π stacking interactions, involving the adjacent pyridine rings with centroid-centroid distance of 3.475 (3) %A [symmetry code: 1 - x, 2 - y, 1 - z], cause to the formation of a supramolecular network structure (Fig. 2).

Related literature top

For related literature, see: Allen et al. (1987); Deisenhofer & Michel (1989); Li et al. (2005); Liu et al. (2004); Pan & Xu (2004); Pope & Müller (2001); Wall et al. (1999); Wu et al. (2003).

Experimental top

Crystals of the title compound were synthesized using hydrothermal method in a Teflon-lined Parr bomb (23 ml), which was then sealed. Cobalt dinitrate hexahydrate (87.3 mg, 0.3 mmol), potassium thiocyanate (58.3 mg, 0.6 mmol), pyridine (2 ml), and distilled water (5 g) were placed into the bomb and sealed. The bomb was heated under autogenous pressure for 4 d at 393 K and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small brown crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

Refinement top

H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level [symmetry code (A): 2 - x, y, z].
[Figure 2] Fig. 2. A packing diagram for (I). The π-π interactions are shown as dashed lines.
Tetrakis(pyridine-κN)dithiocyanatocobalt(II) top
Crystal data top
[Co(NCS)2(C5H5N)4]F(000) = 1012
Mr = 491.49Dx = 1.384 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2235 reflections
a = 10.894 (3) Åθ = 2.3–23.8°
b = 14.735 (9) ŵ = 0.93 mm−1
c = 14.6951 (13) ÅT = 273 K
β = 90.533 (3)°Block, brown
V = 2358.8 (15) Å30.26 × 0.17 × 0.07 mm
Z = 4
Data collection top
Bruker APEXII area-detector
diffractometer		2352 independent reflections
Radiation source: fine-focus sealed tube1647 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
φ and ω scansθmax = 26.2°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→12
Tmin = 0.798, Tmax = 0.938k = −18→18
7688 measured reflectionsl = −18→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0269P)2 + 0.9897P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2352 reflectionsΔρmax = 0.26 e Å−3
144 parametersΔρmin = −0.27 e Å−3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0037 (4)
Crystal data top
[Co(NCS)2(C5H5N)4]V = 2358.8 (15) Å3
Mr = 491.49Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.894 (3) ŵ = 0.93 mm−1
b = 14.735 (9) ÅT = 273 K
c = 14.6951 (13) Å0.26 × 0.17 × 0.07 mm
β = 90.533 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer		2352 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1647 reflections with I > 2σ(I)
Tmin = 0.798, Tmax = 0.938Rint = 0.032
7688 measured reflectionsθmax = 26.2°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.099Δρmax = 0.26 e Å−3
S = 1.06Δρmin = −0.27 e Å−3
2352 reflectionsAbsolute structure: ?
144 parametersFlack parameter: ?
0 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
Co11.00000.64041 (3)0.25000.04759 (19)
S11.36252 (9)0.63317 (7)0.06612 (8)0.1097 (4)
N10.89297 (18)0.63967 (13)0.12536 (14)0.0579 (5)
N21.00000.49390 (19)0.25000.0586 (7)
N31.00000.78436 (19)0.25000.0571 (7)
N41.15772 (19)0.63712 (15)0.17626 (15)0.0653 (6)
C10.7739 (3)0.6582 (2)0.1246 (2)0.0779 (8)
H10.73930.68080.17760.094*
C20.6990 (3)0.6459 (2)0.0501 (3)0.0946 (11)
H20.61620.66090.05280.114*
C30.7470 (4)0.6116 (3)−0.0275 (3)0.1024 (11)
H30.69800.6004−0.07840.123*
C40.8670 (4)0.5946 (3)−0.0279 (2)0.1253 (15)
H40.90340.5727−0.08050.150*
C50.9369 (3)0.6090 (3)0.0479 (2)0.0967 (11)
H51.02050.59650.04490.116*
C60.9018 (2)0.44619 (19)0.2236 (2)0.0727 (8)
H60.83140.47770.20630.087*
C70.8994 (3)0.3535 (2)0.2206 (3)0.0982 (11)
H70.83010.32330.19890.118*
C81.00000.3054 (3)0.25000.1074 (17)
H81.00000.24230.25000.129*
C91.0416 (2)0.83190 (18)0.17876 (18)0.0653 (7)
H91.07110.80040.12870.078*
C101.0426 (3)0.9243 (2)0.1765 (2)0.0814 (8)
H101.07170.95480.12570.098*
C111.00000.9717 (3)0.25000.0893 (13)
H111.00001.03480.25000.107*
C121.2435 (2)0.63550 (16)0.12999 (17)0.0562 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0392 (3)0.0543 (3)0.0495 (3)0.0000.01039 (17)0.000
S10.0807 (6)0.1304 (8)0.1191 (8)0.0012 (5)0.0566 (5)0.0003 (6)
N10.0521 (12)0.0607 (13)0.0611 (12)0.0014 (10)0.0042 (9)−0.0015 (10)
N20.0494 (16)0.0570 (18)0.0694 (19)0.0000.0022 (13)0.000
N30.0534 (17)0.0600 (18)0.0581 (17)0.0000.0024 (13)0.000
N40.0516 (12)0.0781 (16)0.0663 (13)0.0019 (10)0.0149 (10)0.0005 (11)
C10.0574 (17)0.100 (2)0.0764 (19)0.0128 (15)0.0030 (13)0.0122 (16)
C20.0600 (19)0.116 (3)0.108 (3)−0.0025 (17)−0.0180 (17)0.023 (2)
C30.105 (3)0.105 (3)0.096 (3)−0.001 (2)−0.039 (2)−0.016 (2)
C40.110 (3)0.181 (4)0.085 (2)0.041 (3)−0.026 (2)−0.050 (3)
C50.074 (2)0.148 (3)0.0682 (19)0.0291 (19)−0.0084 (15)−0.0304 (19)
C60.0579 (16)0.0649 (19)0.095 (2)−0.0066 (13)−0.0034 (14)0.0021 (15)
C70.080 (2)0.067 (2)0.147 (3)−0.0114 (17)−0.018 (2)−0.001 (2)
C80.099 (4)0.056 (3)0.168 (5)0.000−0.019 (3)0.000
C90.0678 (17)0.0646 (17)0.0636 (16)−0.0040 (13)0.0039 (13)0.0068 (13)
C100.095 (2)0.069 (2)0.080 (2)−0.0076 (17)−0.0025 (16)0.0156 (16)
C110.112 (4)0.057 (3)0.098 (3)0.000−0.011 (3)0.000
C120.0509 (14)0.0587 (15)0.0591 (14)0.0044 (11)0.0078 (11)0.0006 (11)
Geometric parameters (Å, º) top
Co1—N12.162 (2)C3—C41.331 (5)
Co1—N22.159 (3)C3—H30.9300
Co1—N32.121 (3)C4—C51.360 (4)
Co1—N42.040 (2)C4—H40.9300
Co1—N4i2.040 (2)C5—H50.9300
Co1—N1i2.162 (2)C6—C71.366 (4)
S1—C121.608 (2)C6—H60.9300
N1—C51.319 (3)C7—C81.372 (4)
N1—C11.325 (3)C7—H70.9300
N2—C6i1.334 (3)C8—C7i1.372 (4)
N2—C61.334 (3)C8—H80.9300
N3—C91.342 (3)C9—C101.362 (4)
N3—C9i1.342 (3)C9—H90.9300
N4—C121.161 (3)C10—C111.371 (4)
C1—C21.371 (4)C10—H100.9300
C1—H10.9300C11—C10i1.371 (4)
C2—C31.357 (5)C11—H110.9300
C2—H20.9300
N1—Co1—N289.71 (5)C1—C2—H2120.4
N1—Co1—N390.29 (5)C4—C3—C2117.4 (3)
N1—Co1—N490.01 (8)C4—C3—H3121.3
N2—Co1—N3180.0C2—C3—H3121.3
N2—Co1—N488.64 (6)C3—C4—C5120.6 (3)
N3—Co1—N491.36 (6)C3—C4—H4119.7
N4—Co1—N4i177.28 (12)C5—C4—H4119.7
N4i—Co1—N391.36 (6)N1—C5—C4123.7 (3)
N4i—Co1—N288.64 (6)N1—C5—H5118.1
N4i—Co1—N189.98 (8)C4—C5—H5118.1
N4—Co1—N1i89.98 (8)N2—C6—C7123.4 (3)
N4i—Co1—N1i90.01 (8)N2—C6—H6118.3
N3—Co1—N1i90.29 (5)C7—C6—H6118.3
N2—Co1—N1i89.71 (5)C6—C7—C8119.5 (3)
N1—Co1—N1i179.42 (11)C6—C7—H7120.3
C5—N1—C1115.2 (2)C8—C7—H7120.3
C5—N1—Co1122.39 (19)C7—C8—C7i117.7 (4)
C1—N1—Co1121.74 (18)C7—C8—H8121.1
C6i—N2—C6116.4 (3)C7i—C8—H8121.1
C6i—N2—Co1121.79 (16)N3—C9—C10122.9 (3)
C6—N2—Co1121.79 (16)N3—C9—H9118.5
C9—N3—C9i117.1 (3)C10—C9—H9118.5
C9—N3—Co1121.46 (16)C9—C10—C11119.2 (3)
C9i—N3—Co1121.46 (16)C9—C10—H10120.4
C12—N4—Co1176.2 (2)C11—C10—H10120.4
N1—C1—C2123.7 (3)C10i—C11—C10118.7 (4)
N1—C1—H1118.1C10i—C11—H11120.7
C2—C1—H1118.1C10—C11—H11120.7
C3—C2—C1119.2 (3)N4—C12—S1179.8 (3)
C3—C2—H2120.4
Symmetry code: (i) −x+2, y, −z+1/2.
Selected geometric parameters (Å, º) top
Co1—N12.162 (2)Co1—N32.121 (3)
Co1—N22.159 (3)Co1—N42.040 (2)
N1—Co1—N289.71 (5)N2—Co1—N3180.0
N1—Co1—N390.29 (5)N2—Co1—N488.64 (6)
N1—Co1—N490.01 (8)N3—Co1—N491.36 (6)
Acknowledgements top

This work was supported by the Science and Technology Bureau of Jian, Jiangxi Province of China (grant No. 20052817).

references
References top

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