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Acta Cryst. (2007). E63, m1549-m1550    [ doi:10.1107/S1600536807020557 ]

Bis(1,3-diphenylpropane-1,3-dionato-[kappa]2O,O')bis(morpholine-[kappa]N)cobalt(II)

B. Kaitner and E. Mestrovic

Abstract top

The title compound, [Co(C15H11O2)2(C4H4NO)2], was obtained from bis(1-phenylpropane-1,3-dionato)cobalt(II) after crystallization from morpholine. The Co atom is located on a crystallographic inversion centre with an octahedral environment formed by four O atoms of the two 1,3-diphenylpropane-1,3-dione ligands and two N atoms from two morpholine molecules. Both morpholine molecules are additionally involved in N-H...[pi] interactions with the chelate ring (N...centroid = 2.70 Å).

Comment top

High potential of metal complexes with β-diketonesas hosts in soft (and smart) supramolecular materials was recognized several years ago (Soldatov et al., 1999). These materials have a lot of attributes which qualify them for use as supramolecular ion exchange materials, flexible and smart sorbents and as functional organic zeolite analogues. Based on this results Soldatov and his group have prepared a series of modified metal β-diketonate complexes in the design of supramolecular host–guest materials (Soldatov et al., 1999, 2001, 2002, 2003). Based on molecular structural properties of metal(II)(β-diketonato)2 units different types of supramolecular assemblies can be achieved (Bučar and Meštrović, 2003, Meštrović et al., 2004, Meštrović and Kaitner 2006). Using this concepts soft supramolecular materials of specific property can be prepared. As β-diketones we used 1,3-diphenylpropane-1,3-dione (dibenzoylmethane, Hdbm) because the phenyl rings prevent formation of oligomers as in the case of cobalt(II)(acetylacetonate)2 complex (Cotton and Elder, 1965) In further research, among other neutral molecules, morpholine was introduced to the basic metal bis-chelate unit of Co(dbm). Morpholine with two different heteroatoms can be bound to the metal centre. This ligand was expected to bind to the metal ion through the N atom and with possibility for additional interaction involving oxygen atoms. After recrystallization of Co(dbm)2 from morpholine we obtained Co(dbm)2(morpholine)2. The title compound crystallizes in the monoclinic space group P21/n. The asymmetric unit comprises a half of the title complex. The complex unit is of Ci symmetry with Co atom located in the crystallographic inversion centre. The Co atom is in an octahedral environment formed by two dibenzoilmethanate moieties and two morpholine molecules. The Co—O bond distances are 2.029 (1) Å and 2.056 (1) Å. The Co—N bond distance is 2.262 (2) Å. The observed Co—N bond lengths are longer than the ones previously observed in adducts of Co(DBM)2(thiomorpholine-N)2 (2.211 Å Judaš et al., 2006). The chelate rings, formed by two benzoylacetonate anions and cobalt are almost planar. The bite distance O1···O2 is 2.910 (2) Å and it is significantly longer than in any of the polymorphs of the free ligand (2.452 Å Etter et al., 1987), 2.461 Å (Kaitner and Meštrović, 1993) and 2.459Å (Ozturk et al., 1997). The morpholine molecules are additionally involved in a N—H···π interaction between the hydrogen atoms of the morpholine molecule and the chelate rings with distance of 2.700Å (Fig. 2.) Molecules in the crystal are linked by van der Waals interactions.

Related literature top

The high potential of metal complexes with β-diketones as hosts in soft (and smart) supramolecular materials was recognized several years ago by Soldatov et al. (1999, 2001, 2002, 2003). Based on the molecular structural properties of metal(II)(β-diketonate)2 and the properties of neutral molecules, different types of supramolecular assemblies can be achieved (Bučar & Meštrović 2003; Meštrović et al. 2004; Meštrović & Kaitner, 2006). The corresponding complex has the Co atom in an octahedral environment formed by two dibenzoylmethane units and two morpholine molecules analogous to the compex with thiomorpholine (Judaš et al., 2006).

For related literature, see: Cotton & Elder (1965); Etter et al. (1987); Kaitner & Meštrović (1993); Ozturk et al. (1997); Soldatov & Ripmeester (2001a,b).

Experimental top

Bis(1-phenyl-1,3-butanedionato)cobalt(II), Co(dbm), was prepared by methods previously published (Meštrović and Kaitner, 2006). The methanol adduct was formed after dissolving of Co(dbm)2 in morpholine. Crystals suitable for single-crystal X-ray-diffraction were obtained by evaporation of solution for two weeks.

Computing details top

Data collection: STADI4 (Stoe & Cie, 1994); cell refinement: X-RED (Stoe & Cie, 1994); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of the title compound, showing the atom-numbering sheme and displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. The N—H···π interaction in Co(dbm)2(morpholine)2 shown by dashed line.
Bis(1,3-diphenylpropane-1,3-dionato-κ2O,O')bis(morpholine-κN)cobalt(II) top
Crystal data top
[Co(C15H11O2)2(C4H4NO)2]F(000) = 714
Mr = 679.65Dx = 1.335 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 11.310 (1) Åθ = 15–30°
b = 8.064 (1) ŵ = 0.56 mm−1
c = 18.642 (1) ÅT = 293 K
β = 96.09 (2)°Prism, dark red
V = 1690.6 (3) Å30.57 × 0.57 × 0.43 mm
Z = 2
Data collection top
Philips Stoe upgrade
diffractometer		3152 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.042
graphiteθmax = 30.0°, θmin = 2.0°
ω scansh = −15→15
Absorption correction: ψ scan
(North et al., 1968)		k = 0→11
Tmin = 0.784, Tmax = 0.861l = 0→26
5060 measured reflections3 standard reflections every 90 min
4924 independent reflections intensity decay: 1%
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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.1132P)2]
where P = (Fo2 + 2Fc2)/3
4924 reflections(Δ/σ)max < 0.001
220 parametersΔρmax = 0.84 e Å−3
0 restraintsΔρmin = −0.55 e Å−3
Crystal data top
[Co(C15H11O2)2(C4H4NO)2]V = 1690.6 (3) Å3
Mr = 679.65Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.310 (1) ŵ = 0.56 mm−1
b = 8.064 (1) ÅT = 293 K
c = 18.642 (1) Å0.57 × 0.57 × 0.43 mm
β = 96.09 (2)°
Data collection top
Philips Stoe upgrade
diffractometer		3152 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.042
Tmin = 0.784, Tmax = 0.861θmax = 30.0°
5060 measured reflections3 standard reflections every 90 min
4924 independent reflections intensity decay: 1%
Refinement top
R[F2 > 2σ(F2)] = 0.056H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.164Δρmax = 0.84 e Å−3
S = 0.99Δρmin = −0.55 e Å−3
4924 reflectionsAbsolute structure: ?
220 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
Co0.00000.00000.00000.04124 (14)
O10.17031 (12)0.0848 (2)0.02704 (8)0.0473 (3)
O2−0.04433 (12)0.0846 (2)0.09607 (8)0.0486 (4)
O30.1758 (2)−0.3391 (3)0.17174 (11)0.0758 (6)
N0.03864 (17)−0.2621 (2)0.03876 (11)0.0493 (4)
C10.20576 (17)0.1773 (2)0.07989 (10)0.0387 (4)
C20.13570 (19)0.2269 (3)0.13436 (12)0.0480 (5)
H20.17040.29920.16940.058*
C30.01808 (17)0.1766 (2)0.14047 (10)0.0386 (4)
C4−0.04179 (18)0.2334 (3)0.20448 (10)0.0408 (4)
C5−0.1584 (2)0.1854 (4)0.20850 (14)0.0636 (7)
H5−0.19740.12260.17140.076*
C6−0.2179 (3)0.2292 (5)0.26685 (16)0.0804 (9)
H6−0.29600.19490.26910.096*
C7−0.1611 (3)0.3239 (4)0.32154 (14)0.0705 (8)
H7−0.20080.35410.36080.085*
C8−0.0462 (3)0.3733 (4)0.31806 (13)0.0687 (7)
H8−0.00810.43730.35510.082*
C90.0141 (2)0.3295 (3)0.26016 (12)0.0582 (6)
H90.09220.36430.25840.070*
C100.33239 (17)0.2368 (2)0.08363 (10)0.0405 (4)
C110.3989 (2)0.1924 (4)0.02880 (15)0.0739 (8)
H110.36490.1265−0.00880.089*
C120.5161 (3)0.2449 (6)0.02903 (19)0.0966 (13)
H120.55970.2136−0.00840.116*
C130.5684 (2)0.3428 (4)0.08424 (17)0.0792 (9)
H130.64660.37810.08430.095*
C140.5038 (2)0.3868 (4)0.13844 (17)0.0743 (8)
H140.53810.45340.17570.089*
C150.3873 (2)0.3339 (4)0.13909 (14)0.0619 (6)
H150.34510.36390.17730.074*
C16−0.0166 (2)−0.3232 (4)0.10135 (15)0.0654 (7)
H16A−0.0240−0.44300.09890.078*
H16B−0.0957−0.27640.10120.078*
C170.0582 (3)−0.2747 (4)0.16943 (15)0.0785 (9)
H17A0.0617−0.15470.17280.094*
H17B0.0213−0.31580.21060.094*
C180.2303 (2)−0.2745 (4)0.11232 (18)0.0762 (9)
H18A0.3110−0.31640.11390.091*
H18B0.2342−0.15460.11590.091*
C190.1622 (2)−0.3223 (4)0.04198 (15)0.0641 (7)
H19A0.2003−0.27510.00250.077*
H19B0.1624−0.44200.03690.077*
H111−0.001 (2)−0.296 (5)0.0032 (17)0.073 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0365 (2)0.0505 (2)0.0363 (2)−0.00666 (16)0.00202 (13)−0.00943 (16)
O10.0397 (7)0.0591 (9)0.0430 (7)−0.0065 (7)0.0029 (6)−0.0117 (7)
O20.0425 (7)0.0612 (10)0.0423 (8)−0.0091 (7)0.0055 (6)−0.0110 (7)
O30.0928 (14)0.0659 (12)0.0636 (11)0.0021 (11)−0.0161 (10)0.0100 (9)
N0.0457 (9)0.0539 (10)0.0471 (10)−0.0028 (8)0.0003 (8)−0.0046 (8)
C10.0364 (9)0.0401 (9)0.0387 (9)−0.0024 (7)−0.0010 (7)−0.0008 (7)
C20.0440 (10)0.0568 (12)0.0433 (10)−0.0101 (9)0.0058 (8)−0.0122 (9)
C30.0401 (9)0.0401 (9)0.0352 (9)0.0001 (8)0.0024 (7)−0.0008 (7)
C40.0435 (10)0.0432 (10)0.0356 (9)0.0034 (8)0.0039 (7)0.0004 (8)
C50.0463 (12)0.094 (2)0.0511 (12)−0.0078 (13)0.0092 (10)−0.0190 (13)
C60.0522 (14)0.125 (3)0.0668 (16)−0.0032 (16)0.0209 (12)−0.0211 (17)
C70.0693 (16)0.092 (2)0.0521 (14)0.0182 (15)0.0172 (12)−0.0086 (13)
C80.0816 (18)0.0786 (18)0.0464 (12)0.0000 (14)0.0096 (12)−0.0172 (12)
C90.0580 (13)0.0718 (15)0.0451 (11)−0.0082 (12)0.0063 (10)−0.0120 (11)
C100.0371 (9)0.0441 (10)0.0396 (9)−0.0035 (8)0.0007 (7)0.0015 (8)
C110.0555 (14)0.113 (2)0.0556 (14)−0.0280 (15)0.0160 (11)−0.0254 (15)
C120.0650 (17)0.152 (4)0.077 (2)−0.039 (2)0.0307 (16)−0.032 (2)
C130.0512 (14)0.101 (2)0.086 (2)−0.0270 (15)0.0102 (13)−0.0083 (17)
C140.0489 (13)0.092 (2)0.0806 (18)−0.0205 (14)0.0030 (12)−0.0293 (16)
C150.0446 (12)0.0789 (17)0.0621 (14)−0.0103 (11)0.0055 (10)−0.0236 (13)
C160.0547 (14)0.0678 (16)0.0761 (17)0.0000 (12)0.0177 (12)0.0171 (13)
C170.110 (3)0.0733 (19)0.0538 (15)0.0222 (17)0.0170 (16)0.0115 (13)
C180.0531 (14)0.0732 (18)0.098 (2)−0.0045 (13)−0.0120 (15)0.0229 (16)
C190.0597 (14)0.0685 (16)0.0671 (16)0.0155 (12)0.0202 (12)0.0062 (13)
Geometric parameters (Å, °) top
Co—O22.0286 (14)C7—H70.9300
Co—O2i2.0286 (14)C8—C91.383 (3)
Co—O1i2.0556 (14)C8—H80.9300
Co—O12.0556 (14)C9—H90.9300
Co—Ni2.262 (2)C10—C111.379 (3)
Co—N2.262 (2)C10—C151.390 (3)
O1—C11.267 (2)C11—C121.392 (4)
O2—C31.269 (2)C11—H110.9300
O3—C181.423 (4)C12—C131.380 (4)
O3—C171.425 (4)C12—H120.9300
N—C161.466 (3)C13—C141.355 (4)
N—C191.475 (3)C13—H130.9300
N—H1110.81 (3)C14—C151.386 (3)
C1—C21.411 (3)C14—H140.9300
C1—C101.505 (3)C15—H150.9300
C2—C31.407 (3)C16—C171.501 (4)
C2—H20.9300C16—H16A0.9700
C3—C41.504 (3)C16—H16B0.9700
C4—C51.384 (3)C17—H17A0.9700
C4—C91.392 (3)C17—H17B0.9700
C5—C61.385 (3)C18—C191.499 (4)
C5—H50.9300C18—H18A0.9700
C6—C71.377 (4)C18—H18B0.9700
C6—H60.9300C19—H19A0.9700
C7—C81.367 (4)C19—H19B0.9700
O2—Co—O2i180.00 (8)C9—C8—H8119.6
O2—Co—O1i90.88 (6)C8—C9—C4120.1 (2)
O2i—Co—O1i89.12 (6)C8—C9—H9119.9
O2—Co—O189.12 (6)C4—C9—H9119.9
O2i—Co—O190.88 (6)C11—C10—C15117.5 (2)
O1i—Co—O1180.00 (8)C11—C10—C1118.30 (19)
O2—Co—Ni84.85 (7)C15—C10—C1124.18 (19)
O2i—Co—Ni95.15 (7)C10—C11—C12120.9 (3)
O1i—Co—Ni95.07 (7)C10—C11—H11119.6
O1—Co—Ni84.93 (7)C12—C11—H11119.6
O2—Co—N95.15 (7)C13—C12—C11120.6 (3)
O2i—Co—N84.85 (7)C13—C12—H12119.7
O1i—Co—N84.93 (7)C11—C12—H12119.7
O1—Co—N95.07 (7)C14—C13—C12119.0 (2)
Ni—Co—N180.00 (10)C14—C13—H13120.5
C1—O1—Co126.71 (13)C12—C13—H13120.5
C3—O2—Co126.88 (13)C13—C14—C15120.9 (3)
C18—O3—C17108.9 (2)C13—C14—H14119.5
C16—N—C19109.84 (19)C15—C14—H14119.5
C16—N—Co118.94 (16)C14—C15—C10121.1 (2)
C19—N—Co118.09 (16)C14—C15—H15119.4
C16—N—H111107 (2)C10—C15—H15119.4
C19—N—H111111 (2)N—C16—C17109.6 (2)
Co—N—H11189 (3)N—C16—H16A109.7
O1—C1—C2124.84 (18)C17—C16—H16A109.7
O1—C1—C10116.41 (17)N—C16—H16B109.7
C2—C1—C10118.75 (18)C17—C16—H16B109.7
C3—C2—C1125.80 (19)H16A—C16—H16B108.2
C3—C2—H2117.1O3—C17—C16111.8 (2)
C1—C2—H2117.1O3—C17—H17A109.3
O2—C3—C2125.52 (18)C16—C17—H17A109.3
O2—C3—C4115.42 (17)O3—C17—H17B109.3
C2—C3—C4119.06 (18)C16—C17—H17B109.3
C5—C4—C9118.4 (2)H17A—C17—H17B107.9
C5—C4—C3118.00 (19)O3—C18—C19111.2 (2)
C9—C4—C3123.61 (19)O3—C18—H18A109.4
C4—C5—C6121.1 (2)C19—C18—H18A109.4
C4—C5—H5119.4O3—C18—H18B109.4
C6—C5—H5119.4C19—C18—H18B109.4
C7—C6—C5119.7 (3)H18A—C18—H18B108.0
C7—C6—H6120.2N—C19—C18110.4 (2)
C5—C6—H6120.2N—C19—H19A109.6
C8—C7—C6119.9 (2)C18—C19—H19A109.6
C8—C7—H7120.1N—C19—H19B109.6
C6—C7—H7120.1C18—C19—H19B109.6
C7—C8—C9120.8 (2)H19A—C19—H19B108.1
C7—C8—H8119.6
Symmetry codes: (i) −x, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Co—O22.0286 (14)O2—C31.269 (2)
Co—O12.0556 (14)C1—C21.411 (3)
Co—N2.262 (2)C2—C31.407 (3)
O1—C11.267 (2)
O2—Co—O189.12 (6)C1—O1—Co126.71 (13)
O2—Co—N95.15 (7)C3—O2—Co126.88 (13)
O1—Co—N95.07 (7)
Acknowledgements top

Financial support for this research from the Ministry of Science, Education and Sport, Republic of Croatia, through grant 0119630 is gratefully acknowledged.

references
References top

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