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The title compound, [Co(C5H7O2)2(C13H14N2)]n, forms a coordination polymer in which the CoII centre is located on an inversion centre and the 1,3-di-4-pyridylpropane ligand is located on a twofold axis. The polymeric chains are parallel and are held together by weak inter­molecular C—H...O inter­actions. The complex is intended as a possible host for prochiral aldehydes and ketones, and one clathrate was isolated with p-tolyl­aldehyde.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109027589/ga3125sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270109027589/ga3125Isup2.hkl
Contains datablock I

CCDC reference: 746050

Comment top

There are only a limited number of β-diketonate complexes in the Cambridge Structural Database (CSD, Version 5.30 of November 2008; Allen, 2002) displaying the 1,3-di-4-pyridylpropane ligand. Except for (µ2-1,3-di-4-pyridylpropane)-bis(acetylacetonato)bis(1,10- phenanthroline)dicopper(II) diperchlorate hexahydrate (Madalan et al., 2005) and catena-[bis(µ2-1,3-di-4-pyridylpropane)-tetrakis(1- benzoylacetonato)dizinc trihydrate] (Han & Zhou, 2008), the published structures appear to be limited to hexafluoroacetylacetonate (hfacac) complexes of manganese, cobalt and copper. The 1,3-di-4-pyridylpropane complexes of manganese hexafluoroacetylacetonate form a number of clathrates with aromatic guest molecules. Bis[(µ2-1,3-di-4-pyridylpropane)-bis(hexafluoroacetylacetonato)]manganese(II) forms clathrates with benzene (Tabellion et al., 2001a), toluene, diphenylmethane, cis-stilbene, benzyl alcohol, nitrobenzene and benzonitrile (Tabellion et al., 2001b). Two further clathrates are formed by the coordination polymer catena-[(µ2-1,3-di-4-pyridylpropane)-bis(hexafluoroacetylacetonato)manganese(II)] with 1,3-diphenylpropane (Tabellion et al., 2001b) and 1,2-diphenylethane (Tabellion et al., 2001a). In addition, catena-[bis(µ2-1,3-di-4-pyridylpropane)-tetrakis(hexafluoroacetylacetonato)dicobalt(II)] [hereinafter (II)] forms a clathrate with dimethylformamide (CSD refcode WUTTUA; Seidel et al., 2001). These results indicate that it would be possible to use a similar system to form clathrates with prochiral aldehydes or ketones. If such a clathrate crystallized in one of the Sohncke space groups (Flack, 2003), it would be a possible candidate for use in the absolute asymmetric synthesis (Feringa & Van Delden, 1999) of alcohols. Previous work from our laboratory includes the coordination of prochiral aldehydes to tris(2,6-diphenylphenolato)aluminium (Johansson & Håkansson, 2005), π-coordination by unsaturated aldehyde to copper(I) chloride (Andersson et al., 1986) and the coordination of acetylpyridines to copper(I) halides (Lennartson, Salo & Håkansson, 2005; Lennartson et al., 2006). The principle is that slow crystallization of a stereochemically labile compound may result in an enantiomerically enriched product, a phenomenon known as total spontaneous resolution or crystallization-induced asymmetric transformation (Jacques et al., 1984).

Optical activity in stereochemically labile substances will only exist in the solid state, but can in some cases be transferred to stereochemically inert compounds by a chemical reaction. Hence, tris[2,6-diphenylphenolato(p-tolylaldehyde)]aluminium resolved by crystallization-induced asymmetric transformation reacts with solid methyllithium to give 1-(4-methylphenyl)ethanol with an enantiomeric excess (e.e.) of 17% (Johansson & Håkansson, 2005). Since no optically active reagents or catalysts were involved, such reactions may be described as absolute asymmetric synthesis. The self-assembly of a conformationally chiral clathrate from achiral building blocks in solution can proceed to completeness with a theoretical yield of 100% and a theoretical e.e. of 100%. The requirement is that all crystals grow from a single primary nucleus, to ensure that all crystals are of the same enantiomorph. We have observed such an example of high yield in combination with an e.e. close to 100%, e.g. in the optical resolution of seven-coordinate enantiomers (Lennartson, Vestergren & Håkansson, 2005). Among the clathrates described above, only one crystallizes in a Sohncke space group, viz. (II).

The title compound, (I), was found to crystallize in the centrosymmetric space group C2/c, and did not appear to show any tendencies to co-crystallize with dimethylsulfoxide under the conditions employed. The Co atom is located on an inversion centre and the 1,3-di-4-pyridylpropane ligand is located on a twofold axis. The coordination geometry around the Co atom is slightly distorted octahedral, with the two bidentate acetylacetonate ligands forming a plane and two 1,3-di-4-pyridylpropane ligands occupying the remaining two sites in a trans arrangement, resulting in the formation of infinite one-dimensional zigzag chains (Fig. 1). These features are similar to (II), but there are some differences. The deviation from planarity of the Co(acac)2 unit in (I) is much smaller than in the Co(hfacac)2 unit in (II). Both chelate rings in (I) are virtually planar [maximum deviation from the least-squares plane formed by atoms Co1/O1/O2/C2–C4 is -0.036 (1) Å]. In significant contrast, the hfacac ligands in (II) are planar excluding the Co atoms, which are out of plane by between 0.414 (1) and 0.200 (1) Å. Moreover, the planes of the two hfacac ligands (again excluding the Co atoms) are tilted at angles of 37.9 (4) and 23.1 (4)° to each other about each Co atom.

In (I), the 1,3-di-4-pyridylpropane ligand adopts a C2-symmetric conformation, since atom C12 is located on a twofold axis with a C8—C11—C12—C11i angle of 170.06 (19)° [symmetry code: (i) 1 - x, y, 1/2 - z]. The two different 1,3-di-4-pyridylpropane ligands in (II) lack similar symmetry, with corresponding torsion angles of 66.4 (9) and 175.2 (9)°. The 1,3-di-4-pyridylpropane ligand may adopt a wide variety of conformations in the solid state, and essentially achiral conformations have been reported (e.g. Jin et al., 2002). As the Co atom is (unfortunately) located on an inversion centre, each chain is centrosymmetric and achiral. In (II), on the other hand, the whole chain is conformationally chiral.

There is one set of weak intermolecular interactions in (I) (Table 2). Due to the centrosymmetry of (I), each chain interacts with four adjacent chains and the chains run parallel through the unit cell (Fig. 2). Interactions between the chains are weak and could perhaps be disrupted by the introduction of a potential guest molecule. To test this idea, approximately equivalent amounts of Co(acac)2(H2O)x and 1,3-di-4-pyridylpropane were dissolved in various prochiral aldehydes and ketones (p-tolylaldehyde, acetophenone, benzylacetone, p-ethylbenzaldehyde, benzaldehyde, butyraldehyde, salicylaldehyde, capronaldehyde, 3-methoxybenzaldehyde, 2-methoxybenzaldehyde, propiophenone, iso-propyl methyl ketone and tert-butyl methyl ketone) by gentle heating. In the cases where crystals deposited on cooling, the crystals where identified as (I), except in the case of p-tolylaldehyde where a clathrate was obtained. The quality of data was only enough to work out the basic molecular structure; the aldehyde molecules are disordered, and the crystals belong to the centrosymmetric space group C2/c and are of no use for absolute asymmetric synthesis. The polymeric chains in the clathrate appear to be similar in conformation to those in (I). It is hoped that other structures may be revealed in future, displaying well ordered keto-compounds in a chiral environment.

Experimental top

Equimolar amounts of Co(acac)2(H2O)x (where x was assumed to be 2) and 1,3-di-4-pyridylpropane were heated in dimethylsulfoxide until a clear solution was obtained. Slow cooling to ambient temperature resulted in light-red crystals of (I).

Refinement top

All H atoms were included in calculated positions and refined using a riding model, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Uiso(C).

A total of 38 reflections were not collected as the data collection was limited by the use of an image-plate system with a simple ϕ-scan. Also, 95 low-angle measured reflections were excluded since these caused saturation of the image plate.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the crystallographic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted. [Symmetry codes: (i) 1 - x, y, 1/2 - z; (ii) 2 - x, 1 - y, 1 - z; (iii) 1 + x, 1 - y, 1/2 + z.]
[Figure 2] Fig. 2. A packing diagram for (I), showing the one-dimensional coordination polymer forming zigzag-shaped chains held together by weak C—H···O interactions (dashed lines). Co atoms are shown as large shaded spheres, N atoms as darker shaded small spheres and O atoms as lighter shaded small spheres.
catena-Poly[[bis(acetylacetonato-κ2O,O')cobalt(II)]- µ-1,3-di-4-pyridylpropane-κ2N:N'] top
Crystal data top
[Co(C5H7O2)2(C13H14N2)]F(000) = 956
Mr = 455.40Dx = 1.328 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6897 reflections
a = 14.902 (4) Åθ = 2.7–25.0°
b = 8.969 (2) ŵ = 0.78 mm1
c = 18.434 (5) ÅT = 295 K
β = 112.397 (9)°Irregular, light red
V = 2277.9 (11) Å30.4 × 0.2 × 0.1 mm
Z = 4
Data collection top
Rigaku R-AXIS IIC image-plate
diffractometer
1970 independent reflections
Radiation source: rotating-anode X-ray tube, Rigaku RU-H3R1786 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 105 pixels mm-1θmax = 25.0°, θmin = 2.7°
ϕ scansh = 1717
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)
k = 910
Tmin = 0.669, Tmax = 0.926l = 2121
6897 measured reflections
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 0.98 w = 1/[σ2(Fo2) + (0.0932P)2 + 0.5514P]
where P = (Fo2 + 2Fc2)/3
1970 reflections(Δ/σ)max = 0.014
140 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Co(C5H7O2)2(C13H14N2)]V = 2277.9 (11) Å3
Mr = 455.40Z = 4
Monoclinic, C2/cMo Kα radiation
a = 14.902 (4) ŵ = 0.78 mm1
b = 8.969 (2) ÅT = 295 K
c = 18.434 (5) Å0.4 × 0.2 × 0.1 mm
β = 112.397 (9)°
Data collection top
Rigaku R-AXIS IIC image-plate
diffractometer
1970 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2000)
1786 reflections with I > 2σ(I)
Tmin = 0.669, Tmax = 0.926Rint = 0.030
6897 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.118H-atom parameters constrained
S = 0.98Δρmax = 0.22 e Å3
1970 reflectionsΔρmin = 0.25 e Å3
140 parameters
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
Co11.00000.50000.50000.0542 (2)
O11.05915 (11)0.57279 (16)0.42244 (9)0.0602 (4)
O21.03432 (11)0.70182 (16)0.55771 (9)0.0602 (4)
N10.85669 (12)0.5909 (2)0.42004 (11)0.0605 (5)
C11.1338 (2)0.7269 (3)0.35847 (15)0.0767 (7)
H1A1.16390.63860.34880.115*
H1B1.18000.80700.37310.115*
H1C1.07950.75360.31180.115*
C21.09900 (13)0.6977 (2)0.42406 (12)0.0522 (5)
C31.11304 (16)0.8071 (2)0.48057 (13)0.0602 (5)
H31.14750.89110.47660.072*
C41.08130 (13)0.8051 (2)0.54260 (12)0.0508 (5)
C51.1025 (2)0.9398 (3)0.59583 (15)0.0698 (6)
H5A1.04250.98170.59440.105*
H5B1.13681.01280.57830.105*
H5C1.14140.91030.64850.105*
C60.84230 (17)0.6495 (3)0.34991 (13)0.0697 (6)
H60.89190.64170.33120.084*
C70.75795 (17)0.7208 (3)0.30386 (14)0.0711 (6)
H70.75220.76040.25570.085*
C80.68168 (15)0.7340 (2)0.32870 (13)0.0584 (5)
C90.69650 (17)0.6708 (3)0.40065 (16)0.0724 (6)
H90.64730.67430.42000.087*
C100.78293 (17)0.6030 (3)0.44390 (16)0.0725 (6)
H100.79050.56330.49250.087*
C110.59061 (17)0.8163 (3)0.28293 (15)0.0672 (6)
H11A0.59960.86710.23970.081*
H11B0.58030.89200.31650.081*
C120.50000.7208 (3)0.25000.0590 (7)
H120.49580.65730.29120.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0550 (3)0.0477 (3)0.0693 (3)0.01422 (14)0.0342 (2)0.00772 (15)
O10.0635 (8)0.0563 (9)0.0710 (9)0.0157 (7)0.0372 (7)0.0090 (7)
O20.0680 (9)0.0517 (8)0.0716 (9)0.0137 (7)0.0386 (7)0.0081 (7)
N10.0547 (9)0.0555 (10)0.0756 (12)0.0116 (8)0.0298 (8)0.0103 (8)
C10.0893 (17)0.0809 (16)0.0711 (15)0.0204 (14)0.0432 (14)0.0010 (12)
C20.0448 (9)0.0557 (11)0.0566 (11)0.0042 (8)0.0200 (8)0.0051 (8)
C30.0647 (12)0.0493 (11)0.0712 (13)0.0181 (9)0.0309 (10)0.0009 (9)
C40.0476 (10)0.0435 (10)0.0587 (11)0.0033 (8)0.0172 (8)0.0011 (8)
C50.0837 (15)0.0518 (12)0.0747 (14)0.0125 (11)0.0312 (12)0.0084 (10)
C60.0592 (12)0.0950 (18)0.0593 (12)0.0068 (12)0.0275 (10)0.0158 (11)
C70.0657 (13)0.0961 (18)0.0539 (12)0.0107 (12)0.0255 (11)0.0086 (11)
C80.0583 (11)0.0506 (11)0.0659 (12)0.0151 (9)0.0232 (10)0.0094 (9)
C90.0601 (12)0.0778 (15)0.0900 (16)0.0024 (11)0.0409 (12)0.0144 (13)
C100.0620 (12)0.0767 (15)0.0892 (16)0.0016 (11)0.0405 (12)0.0198 (13)
C110.0699 (14)0.0571 (12)0.0758 (14)0.0076 (10)0.0289 (11)0.0011 (10)
C120.0547 (15)0.0577 (16)0.0688 (18)0.0000.0285 (14)0.000
Geometric parameters (Å, º) top
C1—C21.509 (3)C7—C81.383 (3)
C1—H1A0.9600C7—H70.9300
C1—H1B0.9600C8—C91.380 (3)
C1—H1C0.9600C8—C111.492 (3)
C2—O11.263 (2)C9—C101.372 (3)
C2—C31.388 (3)C9—H90.9300
C3—C41.394 (3)C10—N11.335 (3)
C3—H30.9300C10—H100.9300
C4—O21.255 (2)C11—C121.517 (3)
C4—C51.511 (3)C11—H11A0.9700
C5—H5A0.9600C11—H11B0.9700
C5—H5B0.9600C12—H120.9700
C5—H5C0.9600Co1—O12.0512 (15)
C6—N11.335 (3)Co1—O22.0629 (14)
C6—C71.377 (4)Co1—N12.2357 (19)
C6—H60.9300
C2—C1—H1A109.5C7—C8—C11122.7 (2)
C2—C1—H1B109.5C10—C9—C8120.8 (2)
H1A—C1—H1B109.5C10—C9—H9119.6
C2—C1—H1C109.5C8—C9—H9119.6
H1A—C1—H1C109.5N1—C10—C9123.6 (2)
H1B—C1—H1C109.5N1—C10—H10118.2
O1—C2—C3125.45 (18)C9—C10—H10118.2
O1—C2—C1115.92 (19)C8—C11—C12115.22 (19)
C3—C2—C1118.63 (19)C8—C11—H11A108.5
C2—C3—C4127.28 (18)C12—C11—H11A108.5
C2—C3—H3116.4C8—C11—H11B108.5
C4—C3—H3116.4C12—C11—H11B108.5
O2—C4—C3125.70 (19)H11A—C11—H11B107.5
O2—C4—C5116.23 (19)C11—C12—C11i111.3 (3)
C3—C4—C5118.06 (18)C11—C12—H12109.4
C4—C5—H5A109.5O1—Co1—O1ii180.0
C4—C5—H5B109.5O1—Co1—O2ii90.44 (6)
H5A—C5—H5B109.5O1—Co1—O289.56 (6)
C4—C5—H5C109.5O2ii—Co1—O2180.00 (4)
H5A—C5—H5C109.5O1—Co1—N1ii91.11 (7)
H5B—C5—H5C109.5O2—Co1—N1ii89.60 (6)
N1—C6—C7123.5 (2)O1—Co1—N188.89 (7)
N1—C6—H6118.2O2—Co1—N190.40 (6)
C7—C6—H6118.2N1ii—Co1—N1180.0
C6—C7—C8120.5 (2)C6—N1—C10116.0 (2)
C6—C7—H7119.7C6—N1—Co1122.87 (15)
C8—C7—H7119.7C10—N1—Co1120.80 (16)
C9—C8—C7115.6 (2)C2—O1—Co1126.08 (13)
C9—C8—C11121.6 (2)C4—O2—Co1125.67 (14)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11iii—H11Biii···O10.972.643.612 (3)173
Symmetry code: (iii) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Co(C5H7O2)2(C13H14N2)]
Mr455.40
Crystal system, space groupMonoclinic, C2/c
Temperature (K)295
a, b, c (Å)14.902 (4), 8.969 (2), 18.434 (5)
β (°) 112.397 (9)
V3)2277.9 (11)
Z4
Radiation typeMo Kα
µ (mm1)0.78
Crystal size (mm)0.4 × 0.2 × 0.1
Data collection
DiffractometerRigaku R-AXIS IIC image-plate
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2000)
Tmin, Tmax0.669, 0.926
No. of measured, independent and
observed [I > 2σ(I)] reflections
6897, 1970, 1786
Rint0.030
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.118, 0.98
No. of reflections1970
No. of parameters140
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.25

Computer programs: CrystalClear (Rigaku, 2000), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 2009).

Selected geometric parameters (Å, º) top
Co1—O12.0512 (15)Co1—N12.2357 (19)
Co1—O22.0629 (14)
O1—Co1—O2i90.44 (6)O2—Co1—N1i89.60 (6)
O1—Co1—O289.56 (6)O1—Co1—N188.89 (7)
O1—Co1—N1i91.11 (7)O2—Co1—N190.40 (6)
Symmetry code: (i) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11ii—H11Bii···O10.972.643.612 (3)172.8
Symmetry code: (ii) x+1/2, y1/2, z.
 

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