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Acta Cryst. (2008). E64, m786    [ doi:10.1107/S1600536808013007 ]

{2,6-Bis[1-(phenylimino)ethyl]pyridine-[kappa]3N,N',N''}dichloridocobalt(II)

X.-G. Li, D.-C. Zhong, R. He and H.-R. Guo

Abstract top

In the title complex, [CoCl2(C21H19N3)], the CoII atom is coordinated by one pyridine and two imine N atoms and by two chloride anions in a distorted trigonal bipyramidal geometry. The structure exhibits a pseudo-mirror plane through the metal atom, two chloride anions and the pyridine ring. In the crystal structure, the complexes are connected via intermolecular C-H...Cl hydrogen bonding.

Comment top

Recently, numerous crystal structures of metal-organic complexes with Schiff base ligands derived from 2,6-diacetylpyridine have been reported (Reardon et al., 2002; Esteruelas et al., 2003; Pradhan et al., 2003; Gibson et al., 2002; Trivedi et al., 2007) in last several years. In our ongoing investigations on this topic we report here the crystal structure of the title compound.

In the crystal stucture of the title compound the CoII atom is coordinated by three N atoms from the Schiff base ligand and two Cl atoms within a distorted trigonal-bipyramid geometry (Table 1 and Fig. 1). The pyridyl N atom and the two Cl atoms are located in the equatorial plane and the apical position are occupied by the two imino N atoms.

The molecules are connected by intermolecular nonclassical C—H···Cl hydrogen bonding between the aromatic and methyl H atoms and the Cl atoms (Table 2 and Fig 2).

Related literature top

For related literature on crystal structures of metal complexes of Schiff bases, see: Reardon et al. (2002); Esteruelad et al. (2003); Pradhan et al. (2003); Gibson et al. (2001 or 2002?); Trivedi et al. (2007); Mentes et al. (2001); Esteruelas et al. (2003).

Experimental top

The ligand Plep (2,6-bis[(1-phenylimino)ethyl]pyridine) was prepared in high yield from condensation of two equivalents of aniline with one equivalent of 2,6-diacetylpyridine in methanol according to the literature (Mentes et al., 2001). The title compound was synthesized as follows: To a solution of Plep (1 mmol) in 10 mL methanol, a solution of CoCl2.6H2O (1 mmol) in 10 mL methanol was added dropwise at 333 K. After stirring for half an hour, the mixture was allowed to cool to room temperature and filtered off. On slow evaporation of the solvent from the filtrate at room temperature, red well shaped single crystals of the title compound were obtained in one week.

Refinement top

All H atoms were placed in geometrically idealized positions (,ethyl H atoms allowed to rotate but not to tip) and constrained to ride on their parent atoms, with C—H distances of 0.93 Å (0.96 Å for methyl H atoms) Uiso(H) = 1.2Ueq(C) (1.5 for methyl H atoms).

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. Crystal structure of the title compound with 30% probability displacement ellipsoids and the atom-labeling scheme.
[Figure 2] Fig. 2. Crystal structure of the title compound with C—H···Cl hydrogen bonding shown as dashed lines.
{2,6-Bis[1-(phenylimino)ethyl]pyridine- κ3N,N',N''}dichloridocobalt(II) top
Crystal data top
[CoCl2(C21H19N3)]F000 = 908
Mr = 443.22Dx = 1.412 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1843 reflections
a = 10.4580 (3) Åθ = 2.1–25.0º
b = 15.2575 (4) ŵ = 1.09 mm−1
c = 13.1339 (3) ÅT = 273 (2) K
β = 95.8250 (10)ºBlock, red
V = 2084.86 (9) Å30.36 × 0.30 × 0.28 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2594 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.046
Monochromator: graphiteθmax = 25.0º
T = 273(2) Kθmin = 2.1º
φ and ω scansh = −10→12
Absorption correction: nonek = −15→18
11050 measured reflectionsl = −15→15
3665 independent reflections
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)] = 0.036H-atom parameters constrained
wR(F2) = 0.075  w = 1/[σ2(Fo2) + (0.0286P)2 + 0.0512P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.003
3665 reflectionsΔρmax = 0.28 e Å−3
246 parametersΔρmin = −0.26 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CoCl2(C21H19N3)]V = 2084.86 (9) Å3
Mr = 443.22Z = 4
Monoclinic, P21/nMo Kα
a = 10.4580 (3) ŵ = 1.09 mm−1
b = 15.2575 (4) ÅT = 273 (2) K
c = 13.1339 (3) Å0.36 × 0.30 × 0.28 mm
β = 95.8250 (10)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3665 independent reflections
Absorption correction: none2594 reflections with I > 2σ(I)
11050 measured reflectionsRint = 0.046
Refinement top
R[F2 > 2σ(F2)] = 0.036246 parameters
wR(F2) = 0.075H-atom parameters constrained
S = 1.01Δρmax = 0.28 e Å−3
3665 reflectionsΔρmin = −0.26 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Co10.24632 (4)0.03924 (2)0.67087 (3)0.03166 (12)
Cl10.09612 (7)0.14576 (5)0.67423 (5)0.0441 (2)
Cl20.45297 (7)0.07827 (5)0.71366 (6)0.0448 (2)
N240.2555 (2)0.04147 (15)0.50369 (15)0.0316 (5)
N220.2133 (2)−0.03183 (16)0.81359 (15)0.0343 (6)
C60.2297 (2)−0.03113 (19)0.45798 (19)0.0301 (6)
N230.20616 (19)−0.08547 (15)0.62497 (16)0.0316 (5)
C140.1919 (3)−0.1139 (2)0.8020 (2)0.0353 (7)
C30.1514 (3)−0.2543 (2)0.5634 (2)0.0436 (8)
H30.1323−0.31150.54250.052*
C50.2025 (2)−0.10652 (18)0.5251 (2)0.0308 (6)
C10.1845 (2)−0.14705 (19)0.6945 (2)0.0331 (7)
C20.1571 (3)−0.23215 (19)0.6658 (2)0.0412 (7)
H20.1426−0.27420.71460.049*
C40.1742 (3)−0.19112 (19)0.4923 (2)0.0387 (7)
H40.1705−0.20520.42310.046*
C70.2247 (3)−0.0470 (2)0.34516 (19)0.0423 (8)
H7A0.1407−0.06770.32000.063*
H7B0.2878−0.09010.33200.063*
H7C0.24240.00670.31120.063*
C160.2226 (3)0.0074 (2)0.9132 (2)0.0370 (7)
C210.1319 (3)0.0674 (2)0.9352 (2)0.0496 (9)
H210.06440.08120.88620.059*
C80.2866 (3)0.11637 (18)0.44589 (18)0.0310 (7)
C90.4113 (3)0.1313 (2)0.4257 (2)0.0484 (8)
H90.47580.09190.44870.058*
C120.2231 (3)0.2498 (2)0.3586 (2)0.0487 (8)
H120.15950.29000.33620.058*
C130.1924 (3)0.1760 (2)0.41291 (19)0.0406 (8)
H130.10810.16680.42710.049*
C150.1728 (3)−0.1794 (2)0.8837 (2)0.0557 (9)
H15A0.2453−0.21830.89190.084*
H15B0.0961−0.21260.86450.084*
H15C0.1648−0.14950.94700.084*
C100.4405 (3)0.2045 (2)0.3714 (2)0.0552 (9)
H100.52480.21400.35720.066*
C200.1406 (3)0.1075 (2)1.0304 (2)0.0615 (10)
H200.07910.14851.04480.074*
C180.3299 (4)0.0281 (2)1.0814 (2)0.0651 (11)
H180.39710.01451.13070.078*
C110.3473 (3)0.2633 (2)0.3383 (2)0.0505 (9)
H110.36810.31260.30180.061*
C170.3232 (3)−0.0119 (2)0.9863 (2)0.0546 (9)
H170.3862−0.05160.97160.065*
C190.2392 (4)0.0873 (3)1.1032 (2)0.0630 (10)
H190.24420.11381.16720.076*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0368 (2)0.0268 (2)0.0312 (2)−0.00071 (18)0.00279 (16)0.00155 (18)
Cl10.0371 (4)0.0479 (5)0.0480 (4)0.0097 (4)0.0080 (3)0.0079 (4)
Cl20.0348 (4)0.0449 (5)0.0538 (5)0.0047 (4)0.0005 (3)−0.0052 (4)
N240.0375 (14)0.0279 (14)0.0297 (12)−0.0017 (11)0.0045 (10)0.0018 (11)
N220.0395 (14)0.0349 (16)0.0289 (13)0.0041 (12)0.0053 (10)0.0033 (11)
C60.0260 (15)0.0336 (18)0.0310 (15)0.0001 (13)0.0042 (12)0.0003 (14)
N230.0330 (13)0.0288 (14)0.0331 (13)0.0000 (11)0.0040 (10)0.0038 (11)
C140.0356 (17)0.0346 (19)0.0364 (16)0.0044 (14)0.0070 (13)0.0094 (14)
C30.0452 (19)0.0274 (18)0.057 (2)−0.0019 (14)0.0012 (16)−0.0011 (16)
C50.0261 (15)0.0296 (17)0.0365 (16)−0.0010 (13)0.0017 (12)−0.0026 (13)
C10.0316 (16)0.0270 (18)0.0409 (17)0.0028 (13)0.0054 (13)0.0065 (14)
C20.0419 (19)0.0287 (19)0.0535 (19)0.0042 (14)0.0065 (15)0.0129 (15)
C40.0373 (17)0.037 (2)0.0413 (17)0.0034 (14)0.0000 (14)−0.0058 (15)
C70.052 (2)0.042 (2)0.0339 (16)−0.0104 (15)0.0106 (14)−0.0066 (14)
C160.0446 (18)0.0403 (19)0.0274 (15)−0.0006 (15)0.0099 (14)0.0070 (14)
C210.047 (2)0.059 (2)0.0435 (18)0.0041 (17)0.0103 (15)−0.0010 (17)
C80.0398 (17)0.0307 (17)0.0223 (14)−0.0041 (14)0.0025 (12)0.0012 (13)
C90.0406 (19)0.048 (2)0.057 (2)0.0016 (16)0.0094 (16)0.0159 (17)
C120.062 (2)0.042 (2)0.0404 (18)0.0053 (17)−0.0005 (16)0.0130 (16)
C130.0392 (18)0.044 (2)0.0393 (17)0.0009 (15)0.0049 (14)0.0096 (15)
C150.071 (2)0.051 (2)0.0494 (19)0.0050 (18)0.0240 (17)0.0184 (17)
C100.049 (2)0.058 (3)0.060 (2)−0.0134 (18)0.0118 (17)0.0200 (19)
C200.068 (2)0.067 (3)0.054 (2)0.003 (2)0.0279 (19)−0.008 (2)
C180.087 (3)0.069 (3)0.0357 (19)0.008 (2)−0.0104 (19)0.0108 (18)
C110.071 (2)0.045 (2)0.0363 (17)−0.0114 (19)0.0070 (17)0.0135 (16)
C170.069 (2)0.053 (2)0.0396 (19)0.0147 (18)−0.0019 (17)0.0086 (17)
C190.095 (3)0.066 (3)0.0295 (18)−0.008 (2)0.0150 (19)0.0039 (18)
Geometric parameters (Å, °) top
Co1—N232.027 (2)C16—C211.369 (4)
Co1—N242.208 (2)C16—C171.382 (4)
Co1—N222.223 (2)C21—C201.387 (4)
Co1—Cl22.2572 (8)C21—H210.9300
Co1—Cl12.2638 (8)C8—C91.376 (4)
N24—C61.276 (3)C8—C131.378 (4)
N24—C81.428 (3)C9—C101.377 (4)
N22—C141.278 (3)C9—H90.9300
N22—C161.434 (3)C12—C111.368 (4)
C6—C51.495 (4)C12—C131.388 (4)
C6—C71.497 (3)C12—H120.9300
N23—C11.345 (3)C13—H130.9300
N23—C51.347 (3)C15—H15A0.9600
C14—C11.495 (4)C15—H15B0.9600
C14—C151.495 (4)C15—H15C0.9600
C3—C41.380 (4)C10—C111.363 (4)
C3—C21.382 (4)C10—H100.9300
C3—H30.9300C20—C191.368 (4)
C5—C41.384 (4)C20—H200.9300
C1—C21.374 (4)C18—C191.361 (5)
C2—H20.9300C18—C171.386 (4)
C4—H40.9300C18—H180.9300
C7—H7A0.9600C11—H110.9300
C7—H7B0.9600C17—H170.9300
C7—H7C0.9600C19—H190.9300
N23—Co1—N2475.36 (8)H7A—C7—H7C109.5
N23—Co1—N2275.38 (8)H7B—C7—H7C109.5
N24—Co1—N22150.74 (9)C21—C16—C17119.4 (3)
N23—Co1—Cl2119.07 (6)C21—C16—N22119.2 (3)
N24—Co1—Cl296.11 (6)C17—C16—N22121.4 (3)
N22—Co1—Cl298.36 (6)C16—C21—C20120.1 (3)
N23—Co1—Cl1123.81 (6)C16—C21—H21120.0
N24—Co1—Cl196.23 (6)C20—C21—H21120.0
N22—Co1—Cl199.58 (6)C9—C8—C13119.4 (3)
Cl2—Co1—Cl1117.03 (3)C9—C8—N24120.4 (3)
C6—N24—C8119.6 (2)C13—C8—N24120.1 (2)
C6—N24—Co1115.23 (18)C10—C9—C8119.9 (3)
C8—N24—Co1125.20 (17)C10—C9—H9120.0
C14—N22—C16120.8 (2)C8—C9—H9120.0
C14—N22—Co1114.70 (18)C11—C12—C13119.7 (3)
C16—N22—Co1124.34 (18)C11—C12—H12120.1
N24—C6—C5115.7 (2)C13—C12—H12120.1
N24—C6—C7126.2 (3)C8—C13—C12120.2 (3)
C5—C6—C7118.1 (2)C8—C13—H13119.9
C1—N23—C5120.3 (2)C12—C13—H13119.9
C1—N23—Co1119.86 (18)C14—C15—H15A109.5
C5—N23—Co1119.87 (18)C14—C15—H15B109.5
N22—C14—C1115.8 (2)H15A—C15—H15B109.5
N22—C14—C15127.2 (3)C14—C15—H15C109.5
C1—C14—C15117.0 (3)H15A—C15—H15C109.5
C4—C3—C2119.6 (3)H15B—C15—H15C109.5
C4—C3—H3120.2C11—C10—C9120.7 (3)
C2—C3—H3120.2C11—C10—H10119.7
N23—C5—C4120.7 (3)C9—C10—H10119.7
N23—C5—C6113.7 (2)C19—C20—C21120.4 (3)
C4—C5—C6125.5 (3)C19—C20—H20119.8
N23—C1—C2121.2 (3)C21—C20—H20119.8
N23—C1—C14114.1 (3)C19—C18—C17120.6 (3)
C2—C1—C14124.6 (3)C19—C18—H18119.7
C1—C2—C3119.0 (3)C17—C18—H18119.7
C1—C2—H2120.5C10—C11—C12120.1 (3)
C3—C2—H2120.5C10—C11—H11120.0
C3—C4—C5119.1 (3)C12—C11—H11120.0
C3—C4—H4120.4C16—C17—C18119.8 (3)
C5—C4—H4120.4C16—C17—H17120.1
C6—C7—H7A109.5C18—C17—H17120.1
C6—C7—H7B109.5C18—C19—C20119.7 (3)
H7A—C7—H7B109.5C18—C19—H19120.2
C6—C7—H7C109.5C20—C19—H19120.2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.673.545 (3)156
C7—H7A···Cl1ii0.962.763.663 (3)158
C18—H18···Cl2iii0.932.833.714 (3)160
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Co1—N232.027 (2)Co1—Cl22.2572 (8)
Co1—N242.208 (2)Co1—Cl12.2638 (8)
Co1—N222.223 (2)
N23—Co1—N2475.36 (8)N22—Co1—Cl298.36 (6)
N23—Co1—N2275.38 (8)N23—Co1—Cl1123.81 (6)
N24—Co1—N22150.74 (9)N24—Co1—Cl196.23 (6)
N23—Co1—Cl2119.07 (6)N22—Co1—Cl199.58 (6)
N24—Co1—Cl296.11 (6)Cl2—Co1—Cl1117.03 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl2i0.932.673.545 (3)156
C7—H7A···Cl1ii0.962.763.663 (3)158
C18—H18···Cl2iii0.932.833.714 (3)160
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x, −y, −z+1; (iii) −x+1, −y, −z+2.
references
References top

Bruker (2004). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.

Esteruelas, M.-A., López, A.-M., Méndez, L., Olivá, M. & Ońate, E. (2003). Organometallics, 22, 395–406.

Gibson, V.-C., Humphries, M.-J., Tellmann, K.-P., Wass, D.-F., White, A.-J.-P. & Williams, D.-J. (2001). Chem. Commun. pp. 2252–2253. Check date – 2001 in Comment

Mentes, A., Fawcett, J. & Kemmitt, R. D. W. (2001). Acta Cryst. E57, o424–o425.

Pradhan, R., Desplanches, C., Guionneau, P. & Sutter, J.-P. (2003). Inorg. Chem. 42, 6607–6609.

Reardon, D., Aharonian, G., Gambarotta, S. & Yap, G.-P.-A. (2002). Organometallics, 21, 786–788.

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

Trivedi, M., Pandey, D.-S. & Xu, Q. (2007). Inorg. Chim. Acta, 360, 2492–, 2498.