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Acta Cryst. (2007). E63, m2427-m2428    [ doi:10.1107/S160053680704161X ]

Bis(1-benzofuro[3,2-c]pyridine-[kappa]N)dichloridocobalt(II)

V. Vrábel, L. Svorc, N. Juristová, J. Miklovic and J. Kozísek

Abstract top

In the title complex, [CoCl2(C11H7NO)2], the CoII atom lies on a twofold rotation axis four-coordinated by two Cl atoms and two N-donor atoms from two 1-benzofuro[3,2-c]pyridine ligands, giving a slightly distorted tetrahedral coordination environment. The N/Co/N and Cl/Co/Cl planes are nearly perpendicular, with a dihedral angle of 87.1 (1)°. The dihedral angle between the two benzofuropyridine ligands is 45.8 (1)°. In the crystal structure, molecules are linked into a two-dimensional network parallel to the ab plane by C-H...Cl hydrogen bonds.

Comment top

Cobalt complexes are of great interest in coordination chemistry in relation to catalysis and enzymatic reactions, magnetism and molecular architectures (Billson et al., 2000; Fritsky et al., 2003; Kotera et al., 2003). Most of these compounds represent discrete mononuclear complexes (Masaki et al., 2002; Khalaji et al., 2006; Zhao et al., 2006) but in some of them the Co atoms are connected into dinuclear units or polymers (Lumme et al., 1996; Yang et al., 2006; Jensen et al., 2000; Lee & Wang, 2007). The furo[3,2-c]pyridine and its derivatives represent quinoline isosters, in which the benzene ring is replaced by the furan and pyridine ring can be readily coordinated to metal centers through N-donor atom (Miklovič et al., 2004; Baran et al., 2005). We report here the synthesis and crystal structure of the title compound, a mononuclear CoII compound with a benzofuropyridine (BFP) ligand.

The CoII atom lying on a twofold rotation axis is in a tetrahedral geometry and is coordinated by two BFP ligands and two chloride anions (Fig. 1). The Co—N [2.033 (4) Å] and Co—Cl [2.2259 (15) Å] bond lengths in the title compound are in good agreement with the correspoding mean distances in the related complexes (Amirnasr et al., 2002; Zhao et al., 2006; Khalaji et al., 2006). The bond angles subtended at the Co1 atom range from 103.65 (12) to 118.59 (10)°, indicating a slightly distorted tetrahedral coordination. The dihedral angle between the nearly planar BFP ligands is 45.8 (1)°.

In the crystal structure of the title compound, C—H···Cl interactions (Table 2) involving atoms H2A and Cl1 connect the molecules into a two-dimensional network parallel to the ab plane. The formation of a four-coordinate complex, rather than a possible six-coordinate one, is attributed to the large volume of the monodentate BFP ligand.

Related literature top

For ligand synthesis, see: Bobošík et al. (1995); Bencková & Krutošíková (1995, 1999). For general background, see: Baran et al. (2005); Billson et al. (2000); Fritsky et al. (2003); Jensen et al. (2000); Kotera et al. (2003); Lee & Wang (2007); Lumme et al. (1996); Masaki et al. (2002); Miklovič et al. (2004); Yang et al. (2006). For related structures, see: Amirnasr et al. (2002); Khalaji et al. (2006); Zhao et al. (2006).

Experimental top

The organic ligand, [1]benzofuro[3,2-c]pyridine, was prepared according to literature procedures of Bobošík et al. (1995) and Bencková & Krutošíková (1995, 1999). To a CoCl2·6H2O (1 mmol) solution in ethanol (4 ml) was added the solution of [1]benzofuro[3,2-c]pyridine (3 mmol) in ethanol (4 ml) at room temperature. Small blue crystals were formed after 3 d. These were filtered off, washed with ethanol and recrystallized from tetrahydrofuran.

Refinement top

All H atoms were placed in geometrically calculated positions and allowed to ride on their parent atoms, with C—H distances of 0.93 Å and Uiso set at 1.2Ueq of the parent atom.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by the symmetry operation (−x, y, 1/2 − z).
Bis(1-benzofuro[3,2-c]pyridine-κN)dichloridocobalt(II) top
Crystal data top
[CoCl2(C11H7NO)2]F000 = 948
Mr = 468.21Dx = 1.629 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 8019 reflections
a = 7.7063 (2) Åθ = 3.1–28.1º
b = 12.1886 (3) ŵ = 1.20 mm−1
c = 20.4444 (5) ÅT = 298 (2) K
β = 96.217 (3)ºPlate, blue
V = 1909.03 (8) Å30.38 × 0.28 × 0.03 mm
Z = 4
Data collection top
Oxford Diffraction Gemini R CCD
diffractometer		1942 independent reflections
Radiation source: fine-focus sealed tube1667 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 298(2) Kθmax = 26.4º
Rotation method data acquisition using ω and φ scansθmin = 4.1º
Absorption correction: analytical
(Clark & Reid, 1995)		h = −9→9
Tmin = 0.698, Tmax = 0.967k = −15→15
15916 measured reflectionsl = −25→25
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)] = 0.053H-atom parameters constrained
wR(F2) = 0.196  w = 1/[σ2(Fo2) + (0.041P)2 + 12.9573P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
1942 reflectionsΔρmax = 0.97 e Å−3
132 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CoCl2(C11H7NO)2]V = 1909.03 (8) Å3
Mr = 468.21Z = 4
Monoclinic, C2/cMo Kα
a = 7.7063 (2) ŵ = 1.20 mm−1
b = 12.1886 (3) ÅT = 298 (2) K
c = 20.4444 (5) Å0.38 × 0.28 × 0.03 mm
β = 96.217 (3)º
Data collection top
Oxford Diffraction Gemini R CCD
diffractometer		1942 independent reflections
Absorption correction: analytical
(Clark & Reid, 1995)		1667 reflections with I > 2σ(I)
Tmin = 0.698, Tmax = 0.967Rint = 0.030
15916 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.196  w = 1/[σ2(Fo2) + (0.041P)2 + 12.9573P]
where P = (Fo2 + 2Fc2)/3
S = 1.07Δρmax = 0.97 e Å−3
1942 reflectionsΔρmin = −0.49 e Å−3
132 parameters
Special details top

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C20.0900 (7)0.1711 (5)0.3404 (3)0.0465 (12)
H2A0.12350.13780.30280.056*
C30.1133 (8)0.1134 (5)0.3987 (3)0.0505 (13)
H3A0.15870.04260.40100.061*
C5−0.0026 (9)0.2030 (6)0.6201 (3)0.0629 (18)
H5A0.03220.14090.64450.076*
C6−0.0707 (9)0.2930 (7)0.6481 (3)0.067 (2)
H6A−0.08070.29240.69300.080*
C7−0.1249 (9)0.3847 (6)0.6118 (3)0.0609 (17)
H7A−0.17170.44390.63260.073*
C8−0.1110 (7)0.3902 (5)0.5448 (3)0.0484 (13)
H8A−0.14720.45210.52050.058*
C9−0.0246 (7)0.3226 (4)0.3884 (2)0.0390 (11)
H9A−0.07180.39280.38470.047*
C100.0656 (7)0.1663 (4)0.4527 (3)0.0418 (11)
C110.0114 (7)0.2096 (5)0.5533 (3)0.0471 (13)
C12−0.0411 (7)0.3001 (4)0.5151 (2)0.0418 (12)
C13−0.0044 (6)0.2728 (4)0.4488 (2)0.0359 (10)
N10.0219 (6)0.2728 (3)0.33452 (19)0.0388 (9)
O40.0769 (6)0.1264 (3)0.51576 (19)0.0527 (10)
Cl10.2471 (2)0.45525 (13)0.24621 (7)0.0552 (4)
Co10.00000.36200 (8)0.25000.0387 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.051 (3)0.043 (3)0.047 (3)0.006 (2)0.014 (2)−0.003 (2)
C30.057 (3)0.037 (3)0.057 (3)0.011 (2)0.003 (3)0.002 (2)
C50.070 (4)0.081 (5)0.037 (3)−0.022 (4)−0.003 (3)0.018 (3)
C60.071 (4)0.100 (6)0.029 (3)−0.031 (4)0.005 (3)−0.004 (3)
C70.066 (4)0.074 (4)0.046 (3)−0.021 (3)0.016 (3)−0.016 (3)
C80.050 (3)0.055 (3)0.041 (3)−0.011 (3)0.010 (2)−0.008 (2)
C90.044 (3)0.037 (2)0.037 (2)0.000 (2)0.008 (2)0.001 (2)
C100.041 (3)0.041 (3)0.042 (3)0.000 (2)−0.001 (2)0.008 (2)
C110.052 (3)0.053 (3)0.036 (3)−0.013 (2)0.000 (2)0.007 (2)
C120.045 (3)0.050 (3)0.031 (2)−0.010 (2)0.004 (2)0.003 (2)
C130.039 (2)0.035 (2)0.034 (2)−0.005 (2)0.0050 (19)0.0010 (19)
N10.045 (2)0.039 (2)0.034 (2)0.0006 (18)0.0096 (17)0.0008 (17)
O40.063 (3)0.048 (2)0.044 (2)0.0023 (19)−0.0042 (18)0.0157 (17)
Cl10.0641 (9)0.0577 (9)0.0452 (7)−0.0172 (7)0.0122 (6)0.0013 (6)
Co10.0484 (6)0.0396 (6)0.0298 (5)0.0000.0116 (4)0.000
Geometric parameters (Å, °) top
C2—N11.346 (7)C8—H8A0.93
C2—C31.379 (8)C9—N11.340 (6)
C2—H2A0.93C9—C131.369 (7)
C3—C101.362 (8)C9—H9A0.93
C3—H3A0.93C10—O41.373 (6)
C5—C61.368 (11)C10—C131.405 (7)
C5—C111.384 (8)C11—C121.385 (7)
C5—H5A0.93C11—O41.397 (7)
C6—C71.382 (11)C12—C131.454 (7)
C6—H6A0.93N1—Co12.033 (4)
C7—C81.386 (8)Cl1—Co12.2259 (15)
C7—H7A0.93Co1—N1i2.033 (4)
C8—C121.391 (8)Co1—Cl1i2.2259 (15)
N1—C2—C3124.0 (5)C3—C10—C13121.8 (5)
N1—C2—H2A118.0O4—C10—C13111.4 (5)
C3—C2—H2A118.0C5—C11—C12123.5 (6)
C10—C3—C2115.9 (5)C5—C11—O4124.8 (6)
C10—C3—H3A122.0C12—C11—O4111.7 (4)
C2—C3—H3A122.0C11—C12—C8119.1 (5)
C6—C5—C11116.2 (6)C11—C12—C13105.6 (5)
C6—C5—H5A121.9C8—C12—C13135.3 (5)
C11—C5—H5A121.9C9—C13—C10117.7 (5)
C5—C6—C7122.0 (6)C9—C13—C12136.5 (5)
C5—C6—H6A119.0C10—C13—C12105.7 (4)
C7—C6—H6A119.0C9—N1—C2118.7 (4)
C6—C7—C8121.3 (6)C9—N1—Co1116.8 (3)
C6—C7—H7A119.4C2—N1—Co1124.3 (3)
C8—C7—H7A119.4C10—O4—C11105.6 (4)
C7—C8—C12117.9 (6)N1i—Co1—N1115.3 (2)
C7—C8—H8A121.0N1i—Co1—Cl1103.65 (12)
C12—C8—H8A121.0N1—Co1—Cl1108.07 (13)
N1—C9—C13121.8 (5)N1i—Co1—Cl1i108.07 (13)
N1—C9—H9A119.1N1—Co1—Cl1i103.65 (12)
C13—C9—H9A119.1Cl1—Co1—Cl1i118.59 (10)
C3—C10—O4126.8 (5)
N1—C2—C3—C10−1.3 (9)O4—C10—C13—C12−0.7 (6)
C11—C5—C6—C71.0 (10)C11—C12—C13—C9179.2 (6)
C5—C6—C7—C8−0.7 (10)C8—C12—C13—C9−1.0 (11)
C6—C7—C8—C120.3 (9)C11—C12—C13—C100.8 (6)
C2—C3—C10—O4−179.7 (5)C8—C12—C13—C10−179.4 (6)
C2—C3—C10—C130.6 (8)C13—C9—N1—C20.0 (8)
C6—C5—C11—C12−0.8 (9)C13—C9—N1—Co1−175.6 (4)
C6—C5—C11—O4−179.8 (6)C3—C2—N1—C91.0 (8)
C5—C11—C12—C80.4 (8)C3—C2—N1—Co1176.3 (4)
O4—C11—C12—C8179.5 (5)C3—C10—O4—C11−179.5 (6)
C5—C11—C12—C13−179.8 (5)C13—C10—O4—C110.3 (6)
O4—C11—C12—C13−0.7 (6)C5—C11—O4—C10179.3 (5)
C7—C8—C12—C11−0.1 (8)C12—C11—O4—C100.3 (6)
C7—C8—C12—C13−179.8 (6)C9—N1—Co1—N1i−157.1 (4)
N1—C9—C13—C10−0.6 (7)C2—N1—Co1—N1i27.5 (4)
N1—C9—C13—C12−178.9 (5)C9—N1—Co1—Cl187.5 (4)
C3—C10—C13—C90.3 (8)C2—N1—Co1—Cl1−87.9 (4)
O4—C10—C13—C9−179.4 (4)C9—N1—Co1—Cl1i−39.2 (4)
C3—C10—C13—C12179.1 (5)C2—N1—Co1—Cl1i145.4 (4)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Cl1ii0.932.683.481 (6)145
Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å, °) top
N1—Co12.033 (4)Cl1—Co12.2259 (15)
N1i—Co1—N1115.3 (2)N1—Co1—Cl1i103.65 (12)
N1—Co1—Cl1108.07 (13)Cl1—Co1—Cl1i118.59 (10)
Symmetry codes: (i) −x, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···Cl1ii0.932.683.481 (6)145
Symmetry codes: (ii) −x+1/2, y−1/2, −z+1/2.
Acknowledgements top

The authors thank the Grant Agency of the Ministry of Education of the Slovak Republic (grant Nos. 1/3584/06 and 1/2449/05), and Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.

references
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