Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017461/hk2229sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017461/hk2229Isup2.hkl |
CCDC reference: 1181016
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.
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).
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).
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).
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.
[Co(NCS)2(C5H5N)4] | F(000) = 1012 |
Mr = 491.49 | Dx = 1.384 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2235 reflections |
a = 10.894 (3) Å | θ = 2.3–23.8° |
b = 14.735 (9) Å | µ = 0.93 mm−1 |
c = 14.6951 (13) Å | T = 273 K |
β = 90.533 (3)° | Block, brown |
V = 2358.8 (15) Å3 | 0.26 × 0.17 × 0.07 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 2352 independent reflections |
Radiation source: fine-focus sealed tube | 1647 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 26.2°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→12 |
Tmin = 0.798, Tmax = 0.938 | k = −18→18 |
7688 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-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 reflections | Δρmax = 0.26 e Å−3 |
144 parameters | Δρmin = −0.27 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0037 (4) |
[Co(NCS)2(C5H5N)4] | V = 2358.8 (15) Å3 |
Mr = 491.49 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.894 (3) Å | µ = 0.93 mm−1 |
b = 14.735 (9) Å | T = 273 K |
c = 14.6951 (13) Å | 0.26 × 0.17 × 0.07 mm |
β = 90.533 (3)° |
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 = 0.938 | Rint = 0.032 |
7688 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.26 e Å−3 |
2352 reflections | Δρmin = −0.27 e Å−3 |
144 parameters |
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 | ||
Co1 | 1.0000 | 0.64041 (3) | 0.2500 | 0.04759 (19) | |
S1 | 1.36252 (9) | 0.63317 (7) | 0.06612 (8) | 0.1097 (4) | |
N1 | 0.89297 (18) | 0.63967 (13) | 0.12536 (14) | 0.0579 (5) | |
N2 | 1.0000 | 0.49390 (19) | 0.2500 | 0.0586 (7) | |
N3 | 1.0000 | 0.78436 (19) | 0.2500 | 0.0571 (7) | |
N4 | 1.15772 (19) | 0.63712 (15) | 0.17626 (15) | 0.0653 (6) | |
C1 | 0.7739 (3) | 0.6582 (2) | 0.1246 (2) | 0.0779 (8) | |
H1 | 0.7393 | 0.6808 | 0.1776 | 0.094* | |
C2 | 0.6990 (3) | 0.6459 (2) | 0.0501 (3) | 0.0946 (11) | |
H2 | 0.6162 | 0.6609 | 0.0528 | 0.114* | |
C3 | 0.7470 (4) | 0.6116 (3) | −0.0275 (3) | 0.1024 (11) | |
H3 | 0.6980 | 0.6004 | −0.0784 | 0.123* | |
C4 | 0.8670 (4) | 0.5946 (3) | −0.0279 (2) | 0.1253 (15) | |
H4 | 0.9034 | 0.5727 | −0.0805 | 0.150* | |
C5 | 0.9369 (3) | 0.6090 (3) | 0.0479 (2) | 0.0967 (11) | |
H5 | 1.0205 | 0.5965 | 0.0449 | 0.116* | |
C6 | 0.9018 (2) | 0.44619 (19) | 0.2236 (2) | 0.0727 (8) | |
H6 | 0.8314 | 0.4777 | 0.2063 | 0.087* | |
C7 | 0.8994 (3) | 0.3535 (2) | 0.2206 (3) | 0.0982 (11) | |
H7 | 0.8301 | 0.3233 | 0.1989 | 0.118* | |
C8 | 1.0000 | 0.3054 (3) | 0.2500 | 0.1074 (17) | |
H8 | 1.0000 | 0.2423 | 0.2500 | 0.129* | |
C9 | 1.0416 (2) | 0.83190 (18) | 0.17876 (18) | 0.0653 (7) | |
H9 | 1.0711 | 0.8004 | 0.1287 | 0.078* | |
C10 | 1.0426 (3) | 0.9243 (2) | 0.1765 (2) | 0.0814 (8) | |
H10 | 1.0717 | 0.9548 | 0.1257 | 0.098* | |
C11 | 1.0000 | 0.9717 (3) | 0.2500 | 0.0893 (13) | |
H11 | 1.0000 | 1.0348 | 0.2500 | 0.107* | |
C12 | 1.2435 (2) | 0.63550 (16) | 0.12999 (17) | 0.0562 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0392 (3) | 0.0543 (3) | 0.0495 (3) | 0.000 | 0.01039 (17) | 0.000 |
S1 | 0.0807 (6) | 0.1304 (8) | 0.1191 (8) | 0.0012 (5) | 0.0566 (5) | 0.0003 (6) |
N1 | 0.0521 (12) | 0.0607 (13) | 0.0611 (12) | 0.0014 (10) | 0.0042 (9) | −0.0015 (10) |
N2 | 0.0494 (16) | 0.0570 (18) | 0.0694 (19) | 0.000 | 0.0022 (13) | 0.000 |
N3 | 0.0534 (17) | 0.0600 (18) | 0.0581 (17) | 0.000 | 0.0024 (13) | 0.000 |
N4 | 0.0516 (12) | 0.0781 (16) | 0.0663 (13) | 0.0019 (10) | 0.0149 (10) | 0.0005 (11) |
C1 | 0.0574 (17) | 0.100 (2) | 0.0764 (19) | 0.0128 (15) | 0.0030 (13) | 0.0122 (16) |
C2 | 0.0600 (19) | 0.116 (3) | 0.108 (3) | −0.0025 (17) | −0.0180 (17) | 0.023 (2) |
C3 | 0.105 (3) | 0.105 (3) | 0.096 (3) | −0.001 (2) | −0.039 (2) | −0.016 (2) |
C4 | 0.110 (3) | 0.181 (4) | 0.085 (2) | 0.041 (3) | −0.026 (2) | −0.050 (3) |
C5 | 0.074 (2) | 0.148 (3) | 0.0682 (19) | 0.0291 (19) | −0.0084 (15) | −0.0304 (19) |
C6 | 0.0579 (16) | 0.0649 (19) | 0.095 (2) | −0.0066 (13) | −0.0034 (14) | 0.0021 (15) |
C7 | 0.080 (2) | 0.067 (2) | 0.147 (3) | −0.0114 (17) | −0.018 (2) | −0.001 (2) |
C8 | 0.099 (4) | 0.056 (3) | 0.168 (5) | 0.000 | −0.019 (3) | 0.000 |
C9 | 0.0678 (17) | 0.0646 (17) | 0.0636 (16) | −0.0040 (13) | 0.0039 (13) | 0.0068 (13) |
C10 | 0.095 (2) | 0.069 (2) | 0.080 (2) | −0.0076 (17) | −0.0025 (16) | 0.0156 (16) |
C11 | 0.112 (4) | 0.057 (3) | 0.098 (3) | 0.000 | −0.011 (3) | 0.000 |
C12 | 0.0509 (14) | 0.0587 (15) | 0.0591 (14) | 0.0044 (11) | 0.0078 (11) | 0.0006 (11) |
Co1—N1 | 2.162 (2) | C3—C4 | 1.331 (5) |
Co1—N2 | 2.159 (3) | C3—H3 | 0.9300 |
Co1—N3 | 2.121 (3) | C4—C5 | 1.360 (4) |
Co1—N4 | 2.040 (2) | C4—H4 | 0.9300 |
Co1—N4i | 2.040 (2) | C5—H5 | 0.9300 |
Co1—N1i | 2.162 (2) | C6—C7 | 1.366 (4) |
S1—C12 | 1.608 (2) | C6—H6 | 0.9300 |
N1—C5 | 1.319 (3) | C7—C8 | 1.372 (4) |
N1—C1 | 1.325 (3) | C7—H7 | 0.9300 |
N2—C6i | 1.334 (3) | C8—C7i | 1.372 (4) |
N2—C6 | 1.334 (3) | C8—H8 | 0.9300 |
N3—C9 | 1.342 (3) | C9—C10 | 1.362 (4) |
N3—C9i | 1.342 (3) | C9—H9 | 0.9300 |
N4—C12 | 1.161 (3) | C10—C11 | 1.371 (4) |
C1—C2 | 1.371 (4) | C10—H10 | 0.9300 |
C1—H1 | 0.9300 | C11—C10i | 1.371 (4) |
C2—C3 | 1.357 (5) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | ||
N1—Co1—N2 | 89.71 (5) | C1—C2—H2 | 120.4 |
N1—Co1—N3 | 90.29 (5) | C4—C3—C2 | 117.4 (3) |
N1—Co1—N4 | 90.01 (8) | C4—C3—H3 | 121.3 |
N2—Co1—N3 | 180.0 | C2—C3—H3 | 121.3 |
N2—Co1—N4 | 88.64 (6) | C3—C4—C5 | 120.6 (3) |
N3—Co1—N4 | 91.36 (6) | C3—C4—H4 | 119.7 |
N4—Co1—N4i | 177.28 (12) | C5—C4—H4 | 119.7 |
N4i—Co1—N3 | 91.36 (6) | N1—C5—C4 | 123.7 (3) |
N4i—Co1—N2 | 88.64 (6) | N1—C5—H5 | 118.1 |
N4i—Co1—N1 | 89.98 (8) | C4—C5—H5 | 118.1 |
N4—Co1—N1i | 89.98 (8) | N2—C6—C7 | 123.4 (3) |
N4i—Co1—N1i | 90.01 (8) | N2—C6—H6 | 118.3 |
N3—Co1—N1i | 90.29 (5) | C7—C6—H6 | 118.3 |
N2—Co1—N1i | 89.71 (5) | C6—C7—C8 | 119.5 (3) |
N1—Co1—N1i | 179.42 (11) | C6—C7—H7 | 120.3 |
C5—N1—C1 | 115.2 (2) | C8—C7—H7 | 120.3 |
C5—N1—Co1 | 122.39 (19) | C7—C8—C7i | 117.7 (4) |
C1—N1—Co1 | 121.74 (18) | C7—C8—H8 | 121.1 |
C6i—N2—C6 | 116.4 (3) | C7i—C8—H8 | 121.1 |
C6i—N2—Co1 | 121.79 (16) | N3—C9—C10 | 122.9 (3) |
C6—N2—Co1 | 121.79 (16) | N3—C9—H9 | 118.5 |
C9—N3—C9i | 117.1 (3) | C10—C9—H9 | 118.5 |
C9—N3—Co1 | 121.46 (16) | C9—C10—C11 | 119.2 (3) |
C9i—N3—Co1 | 121.46 (16) | C9—C10—H10 | 120.4 |
C12—N4—Co1 | 176.2 (2) | C11—C10—H10 | 120.4 |
N1—C1—C2 | 123.7 (3) | C10i—C11—C10 | 118.7 (4) |
N1—C1—H1 | 118.1 | C10i—C11—H11 | 120.7 |
C2—C1—H1 | 118.1 | C10—C11—H11 | 120.7 |
C3—C2—C1 | 119.2 (3) | N4—C12—S1 | 179.8 (3) |
C3—C2—H2 | 120.4 |
Symmetry code: (i) −x+2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(NCS)2(C5H5N)4] |
Mr | 491.49 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 10.894 (3), 14.735 (9), 14.6951 (13) |
β (°) | 90.533 (3) |
V (Å3) | 2358.8 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.26 × 0.17 × 0.07 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.798, 0.938 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7688, 2352, 1647 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.621 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.099, 1.06 |
No. of reflections | 2352 |
No. of parameters | 144 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.27 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996), SHELXTL.
Co1—N1 | 2.162 (2) | Co1—N3 | 2.121 (3) |
Co1—N2 | 2.159 (3) | Co1—N4 | 2.040 (2) |
N1—Co1—N2 | 89.71 (5) | N2—Co1—N3 | 180.0 |
N1—Co1—N3 | 90.29 (5) | N2—Co1—N4 | 88.64 (6) |
N1—Co1—N4 | 90.01 (8) | N3—Co1—N4 | 91.36 (6) |
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).