α-Tris(2,4-pentanedionato-κ²O,O′)cobalt(III) at 240, 210, 180, 150 and 110 K

The crystal structure of the title compound, [Co(C₅H₇O₂)₃], has been investigated by a multi-temperature measurement. In contrast to the isomorphous Al compound, the title compound exists in the studied temperature range as its monoclinic α polymorph (space group P2₁/c) and does not undergo a phase transition. Rigid-body TLS analyses have been performed and the anisotropic thermal expansion tensor α_ij has been determined. The cell axes show a linear expansion behavior with respect to the temperature, but the slope is significantly different. A possible explanation are the different strengths of different inter­molecular C—H...O contacts, which run in different crystallographic directions.

S1. Comment

Metal complexes, especially transition metal complexes, play an important role in catalytic processes. Trivalent metal acetylacetonate (pentane-2,4-dionate, acac) complexes are particularly accessible species for studying structure, bonding and ligand coordination in organometallic systems. Polymorphism is well known for these complexes [see e.g. Geremia & Demitri (2005) for Mn(acac)₃]. In the course of our ongoing studies on these complexes (von Chrzanowski et al., 2006, 2007), we have now determined the crystal structure of Co(acac)₃, (I). According to an old nomenclature of Astbury & Morgan (1926), the α polymorph crystallizes in the monoclinic crystal system with space group P2₁/c. In our temperature-dependent study of α-Al(acac)₃, which is isomorphous to α-Co(acac)₃, we observed a phase transition to a new δ polymorph. This phase transition occurs between 150 and 110 K.

To our knowledge, all previous crystallographic investigations of Co(acac)₃ were carried out at room temperature. Only the α polymorph of Co(acac)₃ has been reported, crystallizing in the monoclinic crystal system with space group P2₁/c (Hon & Pfluger, 1973; Krüger & Reynhardt, 1974). We report here a multi-temperature measurement with the temperatures 240, (Ia), 210, (Ib), 180, (Ic), 150, (Id), and 110 K, (Ie), which are the same as in our previous publication on α-Al(acac)₃ (von Chrzanowski et al., 2007).

Co(acac)₃ crystallizes as an α polymorph with one independent molecule in the asymmetric unit. No phase transition was observed in the chosen temperature range. The temperature-dependent measurement shows, as expected, a decrease of the anisotropic displacement parameters with decreasing temperature and therefore a decrease of the thermal motion (Fig. 1). The molecule has an approximate noncrystallographic D₃ symmetry, with r.m.s. deviations between 0.114 [for (IIe)] and 0.122 Å [for (Ia)] from ideal symmetry (Pilati & Forni, 1998).

It is known that it is difficult to reach the precision of four-circle diffractometer cell parameters from area-detector data (Herbstein, 2000). Two difficulties are noteworthy: (A) The detector is moveable and the detector–crystal distance is highly correlated with the unit-cell volume. (B) The precise peak position in rotation direction (time axis) is unknown. In order to overcome some of these difficulties we carried out temperature-dependent cell parameter determinations with a fixed detector position and the Phi/Phi-Chi routine (Duisenberg et al., 2000), which is designed to provide accurate peak positions for the reflections. A different crystal was used than for the above-described intensity measurements for the crystal structure determinations. The chosen temperature range was from 290 to 110 K, with steps of 20 K and a cooling rate of 120 K h^-1. The cell axes and the cell volume decrease linearly, the a axis being the most sensitive to change of temperature. The slope ratio b:c:a is approximately 1:1.8:2.7 (Fig. 2). The cell parameters of the known crystal structure determinations of Co(acac)₃ at room temperature are summarized in Table 1. It can be clearly seen that the consistancy of these data is much worse than the internal consistency given in Fig. 2, which is based on one single-crystal and one diffractometer.

The thermal expansion can also be represented by a symmetrical second-rank tensor, α_ij. Calculations for the tensor components, eigenvalues and eigenvectors were performed by the program ALPHA (Jessen & Küppers, 1991). 20 reflections were included in the calculation with θ values calculated from the cell parameters. In a monoclinic unit cell, two off-diagonal terms of the tensor are zero and one axis is parallel to the crystallographic b axis. The behavior of the thermal expansion is anisotropic, as can be seen in the values for the tensor components of thermal expansion α_ij (Table 2). The largest expansion of Co(acac)₃ occurs along the crystallographic a axis. This expansion is represented by the eigenvalue of α₃, which is almost parallel to the crystallographic a axis (Table 3). Note that the β angle and its change cannot be determined reliably; for example, a relatively large change in β from 98.5 to 98.6° results in an extremely small change in θ of 0.006° for the (002) reflection.

The anisotropic thermal expansion tensor might give valuable insight into the strengths of intermolecular interactions (Salud et al., 1998; Kitaigorodsky 1973), while in other cases such a direct relation has been questioned (Boldyreva et al., 1997). It has been noted that acetylacetonate complexes are linked together in the crystal by pure van der Waals interactions (Alekseev et al., 2006), but in the case of α-Co(acac)₃, we detect three different C—H···O hydrogen bonds of different lengths (Table 4). Methyl H atoms act as hydrogen-bond donors and metal-coordinated O atoms as acceptors, with C—H···O angles between 170 and 180° for I(a)–I(e). The weakest interaction is C11—H11B···O1ⁱⁱⁱ [from 2.78 for (Ia) to 2.65 Å for (Ie); symmetry code: (iii) -x, -y + 1, -z + 1], and the vector C11···O1ⁱⁱⁱ forms an angle of 33° to the crystallographic a axis. The other two interactions are shorter [C6—H6B···O6ⁱⁱ and C1—H1A···O4ⁱ [2.53 for (Ia) to 2.47 for (Ie), and 2.54 for (Ia) to 2.52 Å for (Ie); symmetry codes: (i) x, y + 1, z; (ii) x, -y + 1/2, z - 1/2] and form angles of 84 and 72°, respectively, with the crystallographic a axis (Fig. 3). The lengths of these hydrogen bonds are linearly dependent on the temperature (Fig. 4). Interesting enough, the longest distance, C11···O1ⁱⁱⁱ, has the largest slope. This hydrogen bond has the smallest angle to the crystallographic a axis, which has also the largest temperature dependence of the cell parameters (see above). The other two hydrogen bonds are approximately in the bc plane and have a smaller temperature dependence.

The eigenvalues of the translation T and libration L tensors obtained from rigid-body analyses (PLATON; Spek, 2003) show that the decrease of the thermal motion is linear in the whole temperature range (Fig. 5). The agreement factors of the rigid-body analyses are rather high {R = 0.104–0.129; R = [Σ(U_obs - U_calc)²/ΣU_obs²]^1/2}. This situation is similar to that for α-Al(acac)₃, where the agreement factors (R = 0.155–0.167) are even higher. The corresponding internal motion is visualized by difference plots (Hummel et al., 1990) between the observed displacement parameters and the rigid-body models (Fig. 6). The nonrigid behavior is mainly expressed by only one acac ligand (C11–C15). This behavior is also observed in the aluminium compound.

Considering the displacement parameters at a particular temperature, the internal motions are also reflected in a relatively large variation of the bond lengths. F_o example, the Co—O distances range between 1.8746 (18) and 1.8892 (17) Å at 240 K (Ia). The corresponding Al—O distances in α-Al(acac)₃ for 240 K are 1.8712 (13)–1.8862 (12) Å and show a similar variation (von Chrzanowski et al., 2007). Because octahedral, low-spin Co^III with electron configuration d⁶ does not express Jahn–Teller distortions (Wiberg, 1985), this variation can only be explained by internal thermal motion. The thermal motion also contributes to a shortening of the Co—O distances (Table 5) of the crystal structure determinations compared with the value of 1.899 Å obtained for Co(acac)₃ from high-level density functional theory (6–31 G^* for C, H, O and triple-zeta for Co) calculations (Diaz-Acosta et al., 2003).

Related literature

For related literature, see: Alekseev et al. (2006); Astbury & Morgan (1926); Boldyreva et al. (1997); Chrzanowski et al. (2006, 2007); Diaz-Acosta, Baker, Hinton & Pulay (2003); Duisenberg et al. (2000); Geremia & Demitri (2005); Herbstein (2000); Hon & Pfluger (1973); Hummel et al. (1990); Jessen & Küppers (1991); Kitaigorodsky (1973); Kottke & Stalke (1993); Krüger & Reynhardt (1974); Pilati & Forni (1998); Salud et al. (1998); Spek (2003); Wiberg (1985).

S2. Experimental

Dark-green crystals were obtained by slow evaporation of a solution of the commercially available material (Aldrich) in ethyl acetate at room temperature.

S3. Refinement

The crystal stucture determinations of I(a)–I(e) were all carried out on the same crystal, which was mounted on a glass capillary with perfluoro polyether oil (Kottke & Stalke, 1993). The X-ray intensities of (Ia)–(Id) were obtained with an exposure time of 40 s per frame and a rotation angle of 1°. 258 ϕ and 125 ω scans were measured. The X-ray intensities of (Ie) were obtained with two different exposure times and rotation angles of 1°. 258 ϕ and 323 ω scans were measured with an exposure time of 60 s per frame and 173 ϕ scans with an exposure time of 12 s per frame.

All H atoms were introduced in geometrically idealized positions, refined with a riding model and subsequently confirmed in a difference Fourier map. Their U_iso(H) values were set at 1.2U_eq(C) for H atoms of the central CH groups and 1.5U_eq(C) for methyl H atoms.

Because the above-mentioned oil mounting technique is not suitable for ambient temperatures, a second, different crystal was selected and mounted with Super Glue for the cell parameter determinations. The detector position was kept fixed and the Phi/Phi-Chi routine (Duisenberg et al., 2000) was used.

Computing details

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: PEAKREF (Schreurs, 2005); data reduction: EVALCCD (Duisenberg et al., 2003) and SADABS (Sheldrick, 2002). Program(s) used to solve structure: coordinates taken from α-Al(acac)₃ (von Chrzanowski et al., 2007) for (Ia); coordinates taken from Ia for (Ib); coordinates taken from Ib for (Ic); coordinates taken from Ic for (Id); coordinates taken from Id for (Ie). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: manual editing of SHELXL97 (Sheldrick, 1997) output.

Figures

	Fig. 1. Displacement ellipsoid plots and atomic numbering schemes of (Ia) at 240 K, (Ib) at 210 K, (Ic) at 180 K, (Id) at 150 K and (Ie) at 110 K. Ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. All plots are drawn in the same orientation and have the same labeling scheme.
	Fig. 2. (a) Unit-cell lengths a (middle line), b (lower line) and c (top line), (b) cell angle β and (c) cell volume as a function of temperature. (a = 13.486 + 1.32 × 10 ^-3 T, b = 7.313 + 0.50 × 10 ^-3 T, c = 15.932 + 0.88 × 10 ^-3 T and V = 1552.6 + 0.357 T.)
	Fig. 3. Hydrogen-bond interactions in (Ie). The C—H···O contacts are shown with dashed lines. (a) The C1—H11B···O1^iii contact, viewed along the crystallographic c axis. (b) The C6—H6B···O6^ii contact, viewed along the crystallographic b axis. (c) The C1—H1A···O4^i contact, viewed along the crystallographic a axis. [Symmetry codes: (i) x, y + 1, z; (ii) x, -y, + 1/2 z - 1/2; (iii) -x, -y + 1, -z + 1.]
	Fig. 4. D···A distances for the hydrogen contacts C1—H1A···O4^i (middle line), C6—H6B···O6^ii (lower line) and C11—H11B···O1^iii (top line) as a function of temperature [C1···O4^i = 3.482 + 0.13 × 10 ^-3 T, C6···O6^ii = 3.399 + 0.38 × 10 ^-3 T and C11···O1^iii = 3.530 + 0.89 × 10 ^-3 T; symmetry codes: (i) x, y + 1, z; (ii) x, -y + 1/2, z - 1/2; (iii) -x, -y + 1, -z + 1.]
	Fig. 5. Eigenvalues of translation Ti (top) and libration Li (bottom) tensors from rigid-body analyses (PLATON; Spek, 2003) as a function of temperature. (T1 = 1.68 × 10^-3 + 0.15 × 10 ^-3 T, T2 = 0.95 × 10^-3 + 0.13 × 10 ^-3 T, T3 = 0.76 × 10^-3 + 0.11 × 10 ^-3 T, L1 = -0.67 + 0.06 T, L2 = -0.86 + 0.02 T, L3 = -0.22 + 0.02 T.]
	Fig. 6. Peanut plots of (Ia) at 240 K, (Ib) at 210 K, (Ic) at 180 K, (Id) at 150 K and (Ie) at 110 K, showing the difference between the measured displacement parameters and the parameters obtained by rigid-body analyses using the program THMA11 (Schomaker & Trueblood, 1998). A scale factor of 3.08 was used for the r.m.s. surfaces. Blue lines indicate positive differences and purple lines negative ones.

(Ia) α-Tris(pentane-2,4-dionato-κ²O,O')cobalt(III)

Crystal data

[Co(C5H7O2)3]	F(000) = 744
Mr = 356.25	Dx = 1.443 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4640 reflections
a = 13.8094 (7) Å	θ = 2.8–26.7°
b = 7.4331 (4) Å	µ = 1.07 mm^−1
c = 16.1484 (9) Å	T = 240 K
β = 98.430 (3)°	Hexagonal plate, dark green
V = 1639.66 (15) Å^3	0.23 × 0.15 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3762 independent reflections
Radiation source: rotating anode	2578 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
258 ϕ and 231 ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −17→17
Tmin = 0.47, Tmax = 0.95	k = −9→9
18651 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0368P)^2 + 0.6573P] where P = (Fo^2 + 2Fc^2)/3
3762 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.24194 (2)	0.26923 (4)	0.46867 (2)	0.03240 (12)
O1	0.25285 (13)	0.5029 (2)	0.51514 (10)	0.0373 (4)
O2	0.36630 (12)	0.1878 (2)	0.51874 (11)	0.0370 (4)
O3	0.30162 (13)	0.3565 (2)	0.37905 (10)	0.0387 (4)
O4	0.21755 (12)	0.0347 (2)	0.42653 (11)	0.0382 (4)
O5	0.12231 (14)	0.3415 (2)	0.40755 (11)	0.0432 (5)
O6	0.19163 (13)	0.1917 (2)	0.56466 (10)	0.0392 (4)
C1	0.3214 (2)	0.7522 (3)	0.59027 (18)	0.0511 (7)
H1A	0.2913	0.8284	0.5449	0.077*
H1B	0.3861	0.7978	0.6115	0.077*
H1C	0.2813	0.7522	0.6348	0.077*
C2	0.3299 (2)	0.5628 (3)	0.55848 (15)	0.0355 (6)
C3	0.4168 (2)	0.4681 (4)	0.57869 (17)	0.0435 (7)
H3	0.4705	0.5301	0.6081	0.052*
C4	0.43070 (18)	0.2896 (4)	0.55889 (16)	0.0367 (6)
C5	0.5273 (2)	0.2011 (4)	0.58784 (19)	0.0544 (8)
H5A	0.5224	0.1288	0.6370	0.082*
H5B	0.5772	0.2926	0.6016	0.082*
H5C	0.5448	0.1248	0.5436	0.082*
C6	0.3566 (2)	0.3605 (4)	0.24872 (17)	0.0528 (8)
H6A	0.3693	0.4846	0.2655	0.079*
H6B	0.3140	0.3573	0.1954	0.079*
H6C	0.4180	0.3012	0.2433	0.079*
C7	0.30816 (17)	0.2655 (4)	0.31353 (15)	0.0364 (6)
C8	0.27609 (19)	0.0892 (4)	0.29927 (16)	0.0418 (7)
H8	0.2828	0.0381	0.2472	0.050*
C9	0.23519 (17)	−0.0170 (3)	0.35514 (16)	0.0349 (6)
C10	0.2077 (2)	−0.2088 (3)	0.33435 (18)	0.0451 (7)
H10A	0.2384	−0.2867	0.3788	0.068*
H10B	0.2299	−0.2418	0.2821	0.068*
H10C	0.1372	−0.2218	0.3287	0.068*
C11	−0.0460 (2)	0.3751 (5)	0.3695 (2)	0.0751 (11)
H11A	−0.0292	0.4832	0.3411	0.113*
H11B	−0.1014	0.3996	0.3984	0.113*
H11C	−0.0631	0.2801	0.3288	0.113*
C12	0.0404 (2)	0.3167 (4)	0.43198 (19)	0.0498 (7)
C13	0.0261 (2)	0.2402 (5)	0.5075 (2)	0.0622 (9)
H13	−0.0387	0.2244	0.5174	0.075*
C14	0.1005 (2)	0.1853 (4)	0.56930 (18)	0.0478 (7)
C15	0.0776 (3)	0.1152 (5)	0.6519 (2)	0.0719 (10)
H15A	0.1246	0.0227	0.6726	0.108*
H15B	0.0122	0.0646	0.6443	0.108*
H15C	0.0814	0.2130	0.6920	0.108*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0375 (2)	0.0331 (2)	0.02644 (18)	0.00398 (16)	0.00405 (13)	−0.00139 (15)
O1	0.0448 (10)	0.0334 (9)	0.0332 (10)	0.0071 (8)	0.0041 (8)	−0.0044 (8)
O2	0.0375 (10)	0.0365 (10)	0.0369 (10)	0.0069 (8)	0.0053 (8)	−0.0027 (8)
O3	0.0526 (11)	0.0361 (10)	0.0288 (10)	−0.0003 (8)	0.0104 (8)	−0.0024 (8)
O4	0.0482 (11)	0.0340 (9)	0.0323 (10)	−0.0019 (8)	0.0052 (8)	−0.0030 (8)
O5	0.0432 (11)	0.0494 (11)	0.0345 (10)	0.0068 (9)	−0.0031 (8)	−0.0006 (9)
O6	0.0433 (11)	0.0439 (11)	0.0309 (9)	0.0037 (9)	0.0071 (8)	0.0007 (8)
C1	0.073 (2)	0.0366 (16)	0.0442 (16)	−0.0044 (15)	0.0106 (15)	−0.0054 (13)
C2	0.0524 (16)	0.0315 (14)	0.0244 (13)	−0.0037 (13)	0.0115 (12)	0.0006 (11)
C3	0.0415 (15)	0.0432 (16)	0.0443 (16)	−0.0059 (13)	0.0011 (13)	−0.0044 (13)
C4	0.0333 (14)	0.0474 (16)	0.0308 (13)	0.0015 (12)	0.0091 (11)	0.0039 (12)
C5	0.0386 (16)	0.070 (2)	0.0539 (19)	0.0071 (15)	0.0052 (14)	−0.0006 (16)
C6	0.067 (2)	0.0587 (19)	0.0344 (16)	−0.0053 (16)	0.0149 (14)	−0.0007 (14)
C7	0.0350 (13)	0.0449 (16)	0.0283 (13)	0.0081 (12)	0.0014 (11)	0.0016 (12)
C8	0.0539 (17)	0.0425 (16)	0.0293 (14)	0.0046 (13)	0.0067 (13)	−0.0073 (12)
C9	0.0325 (13)	0.0350 (14)	0.0336 (15)	0.0081 (11)	−0.0068 (11)	−0.0029 (11)
C10	0.0498 (16)	0.0386 (15)	0.0435 (16)	0.0007 (13)	−0.0046 (13)	−0.0087 (13)
C11	0.054 (2)	0.099 (3)	0.065 (2)	0.0210 (19)	−0.0156 (17)	−0.015 (2)
C12	0.0410 (16)	0.061 (2)	0.0433 (17)	0.0059 (14)	−0.0071 (14)	−0.0136 (14)
C13	0.0326 (15)	0.102 (3)	0.0519 (19)	−0.0028 (17)	0.0057 (14)	−0.0047 (19)
C14	0.0472 (18)	0.0565 (19)	0.0415 (16)	−0.0078 (14)	0.0127 (14)	−0.0062 (14)
C15	0.069 (2)	0.097 (3)	0.054 (2)	−0.015 (2)	0.0237 (18)	0.008 (2)

Geometric parameters (Å, º)

Co1—O5	1.8746 (18)	C6—C7	1.499 (3)
Co1—O6	1.8798 (17)	C6—H6A	0.9700
Co1—O3	1.8826 (17)	C6—H6B	0.9700
Co1—O4	1.8841 (17)	C6—H6C	0.9700
Co1—O2	1.8872 (17)	C7—C8	1.391 (4)
Co1—O1	1.8892 (17)	C8—C9	1.381 (4)
O1—C2	1.265 (3)	C8—H8	0.9400
O2—C4	1.271 (3)	C9—C10	1.500 (3)
O3—C7	1.270 (3)	C10—H10A	0.9700
O4—C9	1.272 (3)	C10—H10B	0.9700
O5—C12	1.265 (3)	C10—H10C	0.9700
O6—C14	1.272 (3)	C11—C12	1.509 (4)
C1—C2	1.509 (3)	C11—H11A	0.9700
C1—H1A	0.9700	C11—H11B	0.9700
C1—H1B	0.9700	C11—H11C	0.9700
C1—H1C	0.9700	C12—C13	1.385 (4)
C2—C3	1.389 (4)	C13—C14	1.385 (4)
C3—C4	1.384 (4)	C13—H13	0.9400
C3—H3	0.9400	C14—C15	1.509 (4)
C4—C5	1.499 (4)	C15—H15A	0.9700
C5—H5A	0.9700	C15—H15B	0.9700
C5—H5B	0.9700	C15—H15C	0.9700
C5—H5C	0.9700
O5—Co1—O6	96.79 (8)	C7—C6—H6A	109.5
O5—Co1—O3	87.01 (8)	C7—C6—H6B	109.5
O6—Co1—O3	174.86 (8)	H6A—C6—H6B	109.5
O5—Co1—O4	88.74 (8)	C7—C6—H6C	109.5
O6—Co1—O4	86.89 (7)	H6A—C6—H6C	109.5
O3—Co1—O4	96.68 (7)	H6B—C6—H6C	109.5
O5—Co1—O2	173.61 (8)	O3—C7—C8	125.4 (2)
O6—Co1—O2	88.37 (8)	O3—C7—C6	115.1 (2)
O3—Co1—O2	88.08 (8)	C8—C7—C6	119.5 (2)
O4—Co1—O2	87.79 (7)	C9—C8—C7	125.5 (2)
O5—Co1—O1	87.62 (8)	C9—C8—H8	117.2
O6—Co1—O1	88.40 (7)	C7—C8—H8	117.2
O3—Co1—O1	88.30 (7)	O4—C9—C8	124.8 (2)
O4—Co1—O1	173.67 (7)	O4—C9—C10	114.4 (2)
O2—Co1—O1	96.31 (7)	C8—C9—C10	120.8 (2)
C2—O1—Co1	123.70 (16)	C9—C10—H10A	109.5
C4—O2—Co1	123.54 (16)	C9—C10—H10B	109.5
C7—O3—Co1	123.34 (16)	H10A—C10—H10B	109.5
C9—O4—Co1	123.98 (16)	C9—C10—H10C	109.5
C12—O5—Co1	123.61 (19)	H10A—C10—H10C	109.5
C14—O6—Co1	123.25 (18)	H10B—C10—H10C	109.5
C2—C1—H1A	109.5	C12—C11—H11A	109.5
C2—C1—H1B	109.5	C12—C11—H11B	109.5
H1A—C1—H1B	109.5	H11A—C11—H11B	109.5
C2—C1—H1C	109.5	C12—C11—H11C	109.5
H1A—C1—H1C	109.5	H11A—C11—H11C	109.5
H1B—C1—H1C	109.5	H11B—C11—H11C	109.5
O1—C2—C3	125.4 (2)	O5—C12—C13	125.7 (3)
O1—C2—C1	114.6 (2)	O5—C12—C11	113.9 (3)
C3—C2—C1	120.0 (3)	C13—C12—C11	120.4 (3)
C4—C3—C2	125.1 (3)	C12—C13—C14	124.7 (3)
C4—C3—H3	117.4	C12—C13—H13	117.6
C2—C3—H3	117.4	C14—C13—H13	117.6
O2—C4—C3	125.3 (2)	O6—C14—C13	125.6 (3)
O2—C4—C5	115.0 (2)	O6—C14—C15	113.7 (3)
C3—C4—C5	119.7 (3)	C13—C14—C15	120.7 (3)
C4—C5—H5A	109.5	C14—C15—H15A	109.5
C4—C5—H5B	109.5	C14—C15—H15B	109.5
H5A—C5—H5B	109.5	H15A—C15—H15B	109.5
C4—C5—H5C	109.5	C14—C15—H15C	109.5
H5A—C5—H5C	109.5	H15A—C15—H15C	109.5
H5B—C5—H5C	109.5	H15B—C15—H15C	109.5
O5—Co1—O1—C2	−169.71 (19)	Co1—O1—C2—C3	−0.2 (3)
O6—Co1—O1—C2	93.42 (19)	Co1—O1—C2—C1	−179.13 (16)
O3—Co1—O1—C2	−82.63 (19)	O1—C2—C3—C4	−4.3 (4)
O2—Co1—O1—C2	5.24 (19)	C1—C2—C3—C4	174.6 (3)
O6—Co1—O2—C4	−96.43 (19)	Co1—O2—C4—C3	6.5 (3)
O3—Co1—O2—C4	79.85 (19)	Co1—O2—C4—C5	−175.39 (17)
O4—Co1—O2—C4	176.61 (19)	C2—C3—C4—O2	0.8 (4)
O1—Co1—O2—C4	−8.22 (19)	C2—C3—C4—C5	−177.3 (3)
O5—Co1—O3—C7	−83.63 (19)	Co1—O3—C7—C8	−2.3 (3)
O4—Co1—O3—C7	4.7 (2)	Co1—O3—C7—C6	178.88 (17)
O2—Co1—O3—C7	92.28 (19)	O3—C7—C8—C9	−2.4 (4)
O1—Co1—O3—C7	−171.34 (19)	C6—C7—C8—C9	176.4 (3)
O5—Co1—O4—C9	82.57 (19)	Co1—O4—C9—C8	1.3 (3)
O6—Co1—O4—C9	179.44 (19)	Co1—O4—C9—C10	−178.76 (16)
O3—Co1—O4—C9	−4.27 (19)	C7—C8—C9—O4	3.0 (4)
O2—Co1—O4—C9	−92.07 (19)	C7—C8—C9—C10	−177.0 (2)
O6—Co1—O5—C12	−5.7 (2)	Co1—O5—C12—C13	2.5 (4)
O3—Co1—O5—C12	177.7 (2)	Co1—O5—C12—C11	−176.06 (19)
O4—Co1—O5—C12	81.0 (2)	O5—C12—C13—C14	2.6 (5)
O1—Co1—O5—C12	−93.8 (2)	C11—C12—C13—C14	−178.8 (3)
O5—Co1—O6—C14	5.9 (2)	Co1—O6—C14—C13	−2.9 (4)
O4—Co1—O6—C14	−82.5 (2)	Co1—O6—C14—C15	178.9 (2)
O2—Co1—O6—C14	−170.3 (2)	C12—C13—C14—O6	−2.4 (5)
O1—Co1—O6—C14	93.3 (2)	C12—C13—C14—C15	175.7 (3)

(Ib) α-Tris(pentane-2,4-dionato-κ²O,O')cobalt(III)

Crystal data

[Co(C5H7O2)3]	F(000) = 744
Mr = 356.25	Dx = 1.452 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5079 reflections
a = 13.7708 (8) Å	θ = 2.8–27.4°
b = 7.4195 (3) Å	µ = 1.08 mm^−1
c = 16.1242 (7) Å	T = 210 K
β = 98.455 (2)°	Hexagonal plate, dark green
V = 1629.54 (14) Å^3	0.23 × 0.15 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3741 independent reflections
Radiation source: rotating anode	2680 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
258 ϕ and 231 ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −17→17
Tmin = 0.52, Tmax = 0.95	k = −9→9
18555 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.087	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0353P)^2 + 0.6301P] where P = (Fo^2 + 2Fc^2)/3
3741 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.24197 (2)	0.26957 (4)	0.468616 (19)	0.02782 (11)
O1	0.25288 (12)	0.5035 (2)	0.51525 (10)	0.0324 (4)
O2	0.36674 (12)	0.1877 (2)	0.51862 (10)	0.0318 (4)
O3	0.30175 (12)	0.3569 (2)	0.37877 (10)	0.0340 (4)
O4	0.21735 (12)	0.0346 (2)	0.42637 (10)	0.0332 (4)
O5	0.12202 (13)	0.3424 (2)	0.40742 (10)	0.0374 (4)
O6	0.19161 (12)	0.1914 (2)	0.56482 (10)	0.0338 (4)
C1	0.3222 (2)	0.7534 (3)	0.59070 (17)	0.0444 (7)
H1A	0.2923	0.8301	0.5453	0.067*
H1B	0.3872	0.7986	0.6122	0.067*
H1C	0.2819	0.7536	0.6352	0.067*
C2	0.33036 (19)	0.5641 (3)	0.55876 (14)	0.0310 (5)
C3	0.41765 (18)	0.4686 (3)	0.57876 (16)	0.0370 (6)
H3	0.4716	0.5305	0.6082	0.044*
C4	0.43134 (17)	0.2898 (3)	0.55878 (15)	0.0312 (5)
C5	0.52864 (18)	0.2009 (4)	0.58784 (18)	0.0459 (7)
H5A	0.5242	0.1300	0.6377	0.069*
H5B	0.5788	0.2926	0.6007	0.069*
H5C	0.5457	0.1230	0.5439	0.069*
C6	0.3570 (2)	0.3606 (4)	0.24813 (16)	0.0452 (7)
H6A	0.3654	0.4869	0.2629	0.068*
H6B	0.3164	0.3497	0.1939	0.068*
H6C	0.4207	0.3066	0.2456	0.068*
C7	0.30835 (17)	0.2652 (3)	0.31320 (14)	0.0311 (5)
C8	0.27599 (18)	0.0889 (3)	0.29848 (15)	0.0364 (6)
H8	0.2824	0.0379	0.2462	0.044*
C9	0.23499 (17)	−0.0174 (3)	0.35489 (15)	0.0314 (5)
C10	0.2074 (2)	−0.2099 (3)	0.33412 (17)	0.0400 (6)
H10A	0.2395	−0.2882	0.3780	0.060*
H10B	0.2281	−0.2421	0.2811	0.060*
H10C	0.1368	−0.2235	0.3299	0.060*
C11	−0.0471 (2)	0.3764 (5)	0.3697 (2)	0.0651 (9)
H11A	−0.0303	0.4851	0.3416	0.098*
H11B	−0.1025	0.4004	0.3989	0.098*
H11C	−0.0643	0.2819	0.3286	0.098*
C12	0.0398 (2)	0.3169 (4)	0.43210 (17)	0.0439 (7)
C13	0.0252 (2)	0.2405 (5)	0.50768 (19)	0.0555 (8)
H13	−0.0397	0.2245	0.5177	0.067*
C14	0.1004 (2)	0.1860 (4)	0.56963 (17)	0.0417 (7)
C15	0.0774 (2)	0.1138 (5)	0.65211 (19)	0.0625 (9)
H15A	0.1238	0.0194	0.6720	0.094*
H15B	0.0113	0.0649	0.6443	0.094*
H15C	0.0822	0.2105	0.6930	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03260 (18)	0.02829 (18)	0.02240 (16)	0.00374 (15)	0.00354 (12)	−0.00118 (14)
O1	0.0396 (10)	0.0285 (9)	0.0290 (9)	0.0060 (8)	0.0044 (8)	−0.0038 (7)
O2	0.0313 (9)	0.0328 (9)	0.0311 (9)	0.0060 (7)	0.0035 (7)	−0.0019 (7)
O3	0.0455 (10)	0.0315 (9)	0.0264 (9)	−0.0003 (8)	0.0100 (8)	−0.0014 (7)
O4	0.0420 (10)	0.0297 (9)	0.0276 (9)	−0.0006 (8)	0.0039 (8)	−0.0018 (7)
O5	0.0368 (10)	0.0431 (10)	0.0302 (9)	0.0064 (8)	−0.0020 (8)	−0.0014 (8)
O6	0.0356 (10)	0.0399 (10)	0.0262 (9)	0.0043 (8)	0.0055 (7)	0.0017 (7)
C1	0.0629 (18)	0.0337 (15)	0.0372 (14)	−0.0025 (13)	0.0090 (13)	−0.0047 (12)
C2	0.0444 (15)	0.0296 (13)	0.0209 (12)	−0.0039 (11)	0.0104 (11)	0.0011 (10)
C3	0.0337 (13)	0.0387 (15)	0.0379 (15)	−0.0042 (12)	0.0031 (11)	−0.0024 (12)
C4	0.0300 (13)	0.0402 (14)	0.0246 (12)	0.0017 (11)	0.0081 (10)	0.0041 (11)
C5	0.0323 (14)	0.0568 (18)	0.0481 (17)	0.0080 (13)	0.0044 (12)	0.0008 (14)
C6	0.0562 (18)	0.0511 (17)	0.0300 (14)	−0.0032 (14)	0.0115 (13)	−0.0005 (13)
C7	0.0307 (12)	0.0376 (14)	0.0240 (12)	0.0057 (11)	0.0012 (10)	0.0007 (11)
C8	0.0481 (16)	0.0376 (15)	0.0233 (13)	0.0026 (12)	0.0045 (12)	−0.0066 (11)
C9	0.0290 (12)	0.0319 (13)	0.0300 (13)	0.0069 (11)	−0.0065 (10)	−0.0032 (11)
C10	0.0437 (15)	0.0336 (14)	0.0400 (15)	0.0031 (12)	−0.0029 (12)	−0.0082 (12)
C11	0.0472 (18)	0.086 (2)	0.055 (2)	0.0161 (17)	−0.0157 (16)	−0.0109 (18)
C12	0.0383 (15)	0.0527 (17)	0.0373 (15)	0.0057 (13)	−0.0061 (12)	−0.0116 (13)
C13	0.0293 (14)	0.091 (2)	0.0464 (17)	−0.0021 (16)	0.0062 (13)	−0.0031 (17)
C14	0.0423 (16)	0.0483 (17)	0.0360 (15)	−0.0070 (13)	0.0107 (13)	−0.0046 (12)
C15	0.057 (2)	0.085 (2)	0.0496 (19)	−0.0123 (18)	0.0219 (16)	0.0091 (18)

Geometric parameters (Å, º)

Co1—O5	1.8748 (17)	C6—C7	1.503 (3)
Co1—O6	1.8815 (16)	C6—H6A	0.9700
Co1—O3	1.8834 (16)	C6—H6B	0.9700
Co1—O4	1.8846 (16)	C6—H6C	0.9700
Co1—O2	1.8878 (16)	C7—C8	1.391 (3)
Co1—O1	1.8884 (16)	C8—C9	1.385 (3)
O1—C2	1.270 (3)	C8—H8	0.9400
O2—C4	1.271 (3)	C9—C10	1.503 (3)
O3—C7	1.272 (3)	C10—H10A	0.9700
O4—C9	1.272 (3)	C10—H10B	0.9700
O5—C12	1.268 (3)	C10—H10C	0.9700
O6—C14	1.270 (3)	C11—C12	1.512 (4)
C1—C2	1.507 (3)	C11—H11A	0.9700
C1—H1A	0.9700	C11—H11B	0.9700
C1—H1B	0.9700	C11—H11C	0.9700
C1—H1C	0.9700	C12—C13	1.385 (4)
C2—C3	1.391 (3)	C13—C14	1.389 (4)
C3—C4	1.385 (3)	C13—H13	0.9400
C3—H3	0.9400	C14—C15	1.510 (4)
C4—C5	1.505 (3)	C15—H15A	0.9700
C5—H5A	0.9700	C15—H15B	0.9700
C5—H5B	0.9700	C15—H15C	0.9700
C5—H5C	0.9700
O5—Co1—O6	96.88 (7)	C7—C6—H6A	109.5
O5—Co1—O3	86.96 (8)	C7—C6—H6B	109.5
O6—Co1—O3	174.90 (7)	H6A—C6—H6B	109.5
O5—Co1—O4	88.78 (7)	C7—C6—H6C	109.5
O6—Co1—O4	86.80 (7)	H6A—C6—H6C	109.5
O3—Co1—O4	96.66 (7)	H6B—C6—H6C	109.5
O5—Co1—O2	173.54 (7)	O3—C7—C8	125.8 (2)
O6—Co1—O2	88.36 (7)	O3—C7—C6	115.0 (2)
O3—Co1—O2	88.04 (7)	C8—C7—C6	119.2 (2)
O4—Co1—O2	87.75 (7)	C9—C8—C7	125.1 (2)
O5—Co1—O1	87.54 (7)	C9—C8—H8	117.5
O6—Co1—O1	88.42 (7)	C7—C8—H8	117.5
O3—Co1—O1	88.39 (7)	O4—C9—C8	124.9 (2)
O4—Co1—O1	173.58 (7)	O4—C9—C10	114.5 (2)
O2—Co1—O1	96.40 (7)	C8—C9—C10	120.6 (2)
C2—O1—Co1	123.81 (15)	C9—C10—H10A	109.5
C4—O2—Co1	123.43 (15)	C9—C10—H10B	109.5
C7—O3—Co1	123.25 (15)	H10A—C10—H10B	109.5
C9—O4—Co1	124.05 (15)	C9—C10—H10C	109.5
C12—O5—Co1	123.35 (17)	H10A—C10—H10C	109.5
C14—O6—Co1	123.20 (17)	H10B—C10—H10C	109.5
C2—C1—H1A	109.5	C12—C11—H11A	109.5
C2—C1—H1B	109.5	C12—C11—H11B	109.5
H1A—C1—H1B	109.5	H11A—C11—H11B	109.5
C2—C1—H1C	109.5	C12—C11—H11C	109.5
H1A—C1—H1C	109.5	H11A—C11—H11C	109.5
H1B—C1—H1C	109.5	H11B—C11—H11C	109.5
O1—C2—C3	125.1 (2)	O5—C12—C13	126.1 (3)
O1—C2—C1	114.9 (2)	O5—C12—C11	113.8 (3)
C3—C2—C1	120.0 (2)	C13—C12—C11	120.1 (3)
C4—C3—C2	125.2 (2)	C12—C13—C14	124.2 (3)
C4—C3—H3	117.4	C12—C13—H13	117.9
C2—C3—H3	117.4	C14—C13—H13	117.9
O2—C4—C3	125.5 (2)	O6—C14—C13	125.9 (2)
O2—C4—C5	115.0 (2)	O6—C14—C15	113.7 (2)
C3—C4—C5	119.5 (2)	C13—C14—C15	120.4 (3)
C4—C5—H5A	109.5	C14—C15—H15A	109.5
C4—C5—H5B	109.5	C14—C15—H15B	109.5
H5A—C5—H5B	109.5	H15A—C15—H15B	109.5
C4—C5—H5C	109.5	C14—C15—H15C	109.5
H5A—C5—H5C	109.5	H15A—C15—H15C	109.5
H5B—C5—H5C	109.5	H15B—C15—H15C	109.5
O5—Co1—O1—C2	−169.55 (18)	Co1—O1—C2—C3	−0.3 (3)
O6—Co1—O1—C2	93.49 (18)	Co1—O1—C2—C1	−179.20 (15)
O3—Co1—O1—C2	−82.53 (18)	O1—C2—C3—C4	−4.3 (4)
O2—Co1—O1—C2	5.32 (18)	C1—C2—C3—C4	174.6 (2)
O6—Co1—O2—C4	−96.51 (17)	Co1—O2—C4—C3	6.5 (3)
O3—Co1—O2—C4	79.88 (17)	Co1—O2—C4—C5	−175.39 (16)
O4—Co1—O2—C4	176.63 (17)	C2—C3—C4—O2	0.8 (4)
O1—Co1—O2—C4	−8.28 (18)	C2—C3—C4—C5	−177.2 (2)
O5—Co1—O3—C7	−83.87 (18)	Co1—O3—C7—C8	−1.9 (3)
O4—Co1—O3—C7	4.54 (19)	Co1—O3—C7—C6	178.92 (16)
O2—Co1—O3—C7	92.04 (18)	O3—C7—C8—C9	−2.9 (4)
O1—Co1—O3—C7	−171.49 (18)	C6—C7—C8—C9	176.3 (2)
O5—Co1—O4—C9	82.60 (18)	Co1—O4—C9—C8	1.1 (3)
O6—Co1—O4—C9	179.56 (18)	Co1—O4—C9—C10	−178.83 (15)
O3—Co1—O4—C9	−4.19 (18)	C7—C8—C9—O4	3.3 (4)
O2—Co1—O4—C9	−91.96 (18)	C7—C8—C9—C10	−176.8 (2)
O6—Co1—O5—C12	−5.9 (2)	Co1—O5—C12—C13	2.9 (4)
O3—Co1—O5—C12	177.5 (2)	Co1—O5—C12—C11	−176.28 (18)
O4—Co1—O5—C12	80.7 (2)	O5—C12—C13—C14	2.5 (5)
O1—Co1—O5—C12	−94.0 (2)	C11—C12—C13—C14	−178.3 (3)
O5—Co1—O6—C14	5.5 (2)	Co1—O6—C14—C13	−2.1 (4)
O4—Co1—O6—C14	−82.9 (2)	Co1—O6—C14—C15	178.39 (19)
O2—Co1—O6—C14	−170.7 (2)	C12—C13—C14—O6	−3.0 (5)
O1—Co1—O6—C14	92.8 (2)	C12—C13—C14—C15	176.5 (3)

(Ic) α-Tris(pentane-2,4-dionato-κ²O,O')cobalt(III)

Crystal data

[Co(C5H7O2)3]	F(000) = 744
Mr = 356.25	Dx = 1.461 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5763 reflections
a = 13.7338 (6) Å	θ = 2.8–27.5°
b = 7.4070 (3) Å	µ = 1.08 mm^−1
c = 16.0959 (7) Å	T = 180 K
β = 98.467 (1)°	Hexagonal plate, dark green
V = 1619.53 (12) Å^3	0.23 × 0.15 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3713 independent reflections
Radiation source: rotating anode	2765 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
258 ϕ and 231 ω scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −17→17
Tmin = 0.51, Tmax = 0.95	k = −9→9
18433 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0299P)^2 + 0.9397P] where P = (Fo^2 + 2Fc^2)/3
3713 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.24188 (2)	0.26991 (4)	0.468544 (18)	0.02385 (10)
O1	0.25304 (11)	0.5044 (2)	0.51528 (9)	0.0280 (4)
O2	0.36719 (11)	0.1878 (2)	0.51843 (9)	0.0272 (3)
O3	0.30186 (11)	0.3574 (2)	0.37845 (9)	0.0292 (4)
O4	0.21708 (11)	0.0344 (2)	0.42624 (9)	0.0291 (4)
O5	0.12137 (12)	0.3430 (2)	0.40746 (9)	0.0320 (4)
O6	0.19158 (11)	0.1914 (2)	0.56495 (9)	0.0291 (4)
C1	0.32292 (19)	0.7544 (3)	0.59080 (15)	0.0374 (6)
H1A	0.2918	0.8316	0.5450	0.056*
H1B	0.3888	0.8006	0.6117	0.056*
H1C	0.2829	0.7545	0.6365	0.056*
C2	0.33088 (17)	0.5650 (3)	0.55891 (13)	0.0264 (5)
C3	0.41855 (17)	0.4695 (3)	0.57882 (15)	0.0315 (5)
H3	0.4734	0.5320	0.6084	0.038*
C4	0.43201 (16)	0.2896 (3)	0.55872 (13)	0.0268 (5)
C5	0.52963 (17)	0.2008 (4)	0.58740 (16)	0.0390 (6)
H5A	0.5253	0.1282	0.6376	0.058*
H5B	0.5804	0.2936	0.6006	0.058*
H5C	0.5468	0.1226	0.5426	0.058*
C6	0.35762 (19)	0.3608 (4)	0.24765 (15)	0.0390 (6)
H6A	0.3679	0.4880	0.2633	0.058*
H6B	0.3158	0.3527	0.1929	0.058*
H6C	0.4213	0.3037	0.2443	0.058*
C7	0.30840 (15)	0.2657 (3)	0.31271 (13)	0.0266 (5)
C8	0.27601 (17)	0.0889 (3)	0.29815 (14)	0.0308 (5)
H8	0.2828	0.0371	0.2453	0.037*
C9	0.23460 (15)	−0.0178 (3)	0.35453 (14)	0.0264 (5)
C10	0.20658 (18)	−0.2104 (3)	0.33381 (15)	0.0337 (5)
H10A	0.2363	−0.2891	0.3796	0.051*
H10B	0.2304	−0.2452	0.2816	0.051*
H10C	0.1348	−0.2225	0.3267	0.051*
C11	−0.0482 (2)	0.3771 (4)	0.37002 (18)	0.0562 (8)
H11A	−0.0315	0.4880	0.3421	0.084*
H11B	−0.1045	0.3998	0.3995	0.084*
H11C	−0.0652	0.2820	0.3280	0.084*
C12	0.03889 (18)	0.3176 (3)	0.43228 (16)	0.0370 (6)
C13	0.02462 (18)	0.2400 (4)	0.50804 (16)	0.0469 (7)
H13	−0.0412	0.2238	0.5183	0.056*
C14	0.09994 (18)	0.1846 (3)	0.56992 (15)	0.0354 (6)
C15	0.0772 (2)	0.1123 (4)	0.65230 (17)	0.0532 (8)
H15A	0.1254	0.0190	0.6730	0.080*
H15B	0.0110	0.0600	0.6443	0.080*
H15C	0.0806	0.2107	0.6933	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02776 (16)	0.02445 (16)	0.01921 (15)	0.00333 (13)	0.00304 (11)	−0.00107 (13)
O1	0.0331 (8)	0.0262 (8)	0.0245 (8)	0.0058 (7)	0.0032 (7)	−0.0026 (6)
O2	0.0278 (8)	0.0266 (8)	0.0271 (8)	0.0050 (7)	0.0033 (7)	−0.0018 (7)
O3	0.0385 (9)	0.0268 (8)	0.0231 (8)	−0.0006 (7)	0.0074 (7)	−0.0016 (7)
O4	0.0375 (9)	0.0260 (8)	0.0238 (8)	−0.0008 (7)	0.0043 (7)	−0.0020 (7)
O5	0.0326 (9)	0.0364 (9)	0.0251 (8)	0.0050 (7)	−0.0016 (7)	−0.0011 (7)
O6	0.0307 (9)	0.0337 (9)	0.0233 (8)	0.0033 (7)	0.0055 (7)	0.0011 (7)
C1	0.0520 (15)	0.0283 (13)	0.0326 (13)	−0.0010 (12)	0.0085 (11)	−0.0033 (11)
C2	0.0382 (13)	0.0251 (11)	0.0178 (11)	−0.0024 (10)	0.0102 (10)	0.0008 (9)
C3	0.0292 (12)	0.0330 (13)	0.0315 (13)	−0.0043 (10)	0.0022 (10)	−0.0027 (10)
C4	0.0266 (11)	0.0344 (12)	0.0205 (11)	0.0011 (10)	0.0067 (9)	0.0045 (10)
C5	0.0297 (13)	0.0489 (16)	0.0379 (14)	0.0057 (12)	0.0037 (11)	0.0000 (12)
C6	0.0472 (15)	0.0445 (15)	0.0264 (13)	−0.0037 (12)	0.0098 (11)	0.0003 (11)
C7	0.0257 (11)	0.0335 (12)	0.0199 (10)	0.0064 (10)	0.0009 (9)	0.0013 (10)
C8	0.0389 (13)	0.0312 (13)	0.0218 (12)	0.0016 (10)	0.0030 (10)	−0.0066 (9)
C9	0.0238 (11)	0.0279 (12)	0.0245 (12)	0.0067 (9)	−0.0063 (9)	−0.0026 (9)
C10	0.0375 (13)	0.0277 (12)	0.0333 (13)	0.0011 (11)	−0.0040 (10)	−0.0045 (10)
C11	0.0419 (16)	0.075 (2)	0.0457 (17)	0.0162 (15)	−0.0118 (13)	−0.0102 (16)
C12	0.0313 (13)	0.0450 (15)	0.0316 (13)	0.0037 (11)	−0.0056 (11)	−0.0116 (11)
C13	0.0266 (13)	0.076 (2)	0.0384 (14)	−0.0021 (14)	0.0050 (11)	−0.0032 (15)
C14	0.0364 (14)	0.0410 (15)	0.0296 (13)	−0.0059 (11)	0.0074 (11)	−0.0059 (11)
C15	0.0489 (17)	0.072 (2)	0.0413 (16)	−0.0109 (15)	0.0165 (14)	0.0065 (15)

Geometric parameters (Å, º)

Co1—O5	1.8762 (16)	C6—C7	1.502 (3)
Co1—O6	1.8813 (15)	C6—H6A	0.9800
Co1—O3	1.8851 (15)	C6—H6B	0.9800
Co1—O4	1.8853 (15)	C6—H6C	0.9800
Co1—O2	1.8893 (15)	C7—C8	1.392 (3)
Co1—O1	1.8902 (15)	C8—C9	1.387 (3)
O1—C2	1.271 (3)	C8—H8	0.9500
O2—C4	1.270 (3)	C9—C10	1.502 (3)
O3—C7	1.272 (2)	C10—H10A	0.9800
O4—C9	1.273 (2)	C10—H10B	0.9800
O5—C12	1.270 (3)	C10—H10C	0.9800
O6—C14	1.274 (3)	C11—C12	1.509 (3)
C1—C2	1.504 (3)	C11—H11A	0.9800
C1—H1A	0.9800	C11—H11B	0.9800
C1—H1B	0.9800	C11—H11C	0.9800
C1—H1C	0.9800	C12—C13	1.388 (4)
C2—C3	1.393 (3)	C13—C14	1.388 (4)
C3—C4	1.389 (3)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.505 (3)
C4—C5	1.504 (3)	C15—H15A	0.9800
C5—H5A	0.9800	C15—H15B	0.9800
C5—H5B	0.9800	C15—H15C	0.9800
C5—H5C	0.9800
O5—Co1—O6	96.82 (7)	C7—C6—H6A	109.5
O5—Co1—O3	87.09 (7)	C7—C6—H6B	109.5
O6—Co1—O3	174.87 (7)	H6A—C6—H6B	109.5
O5—Co1—O4	88.82 (7)	C7—C6—H6C	109.5
O6—Co1—O4	86.73 (7)	H6A—C6—H6C	109.5
O3—Co1—O4	96.69 (6)	H6B—C6—H6C	109.5
O5—Co1—O2	173.57 (7)	O3—C7—C8	125.6 (2)
O6—Co1—O2	88.40 (7)	O3—C7—C6	115.1 (2)
O3—Co1—O2	87.93 (7)	C8—C7—C6	119.3 (2)
O4—Co1—O2	87.73 (7)	C9—C8—C7	125.3 (2)
O5—Co1—O1	87.52 (7)	C9—C8—H8	117.4
O6—Co1—O1	88.51 (7)	C7—C8—H8	117.4
O3—Co1—O1	88.35 (6)	O4—C9—C8	124.8 (2)
O4—Co1—O1	173.61 (7)	O4—C9—C10	114.4 (2)
O2—Co1—O1	96.40 (7)	C8—C9—C10	120.8 (2)
C2—O1—Co1	123.80 (14)	C9—C10—H10A	109.5
C4—O2—Co1	123.50 (14)	C9—C10—H10B	109.5
C7—O3—Co1	123.30 (14)	H10A—C10—H10B	109.5
C9—O4—Co1	124.05 (14)	C9—C10—H10C	109.5
C12—O5—Co1	123.46 (16)	H10A—C10—H10C	109.5
C14—O6—Co1	123.39 (15)	H10B—C10—H10C	109.5
C2—C1—H1A	109.5	C12—C11—H11A	109.5
C2—C1—H1B	109.5	C12—C11—H11B	109.5
H1A—C1—H1B	109.5	H11A—C11—H11B	109.5
C2—C1—H1C	109.5	C12—C11—H11C	109.5
H1A—C1—H1C	109.5	H11A—C11—H11C	109.5
H1B—C1—H1C	109.5	H11B—C11—H11C	109.5
O1—C2—C3	125.2 (2)	O5—C12—C13	125.9 (2)
O1—C2—C1	114.9 (2)	O5—C12—C11	113.9 (2)
C3—C2—C1	120.0 (2)	C13—C12—C11	120.2 (2)
C4—C3—C2	125.0 (2)	C12—C13—C14	124.5 (2)
C4—C3—H3	117.5	C12—C13—H13	117.8
C2—C3—H3	117.5	C14—C13—H13	117.8
O2—C4—C3	125.5 (2)	O6—C14—C13	125.6 (2)
O2—C4—C5	115.0 (2)	O6—C14—C15	113.8 (2)
C3—C4—C5	119.4 (2)	C13—C14—C15	120.6 (2)
C4—C5—H5A	109.5	C14—C15—H15A	109.5
C4—C5—H5B	109.5	C14—C15—H15B	109.5
H5A—C5—H5B	109.5	H15A—C15—H15B	109.5
C4—C5—H5C	109.5	C14—C15—H15C	109.5
H5A—C5—H5C	109.5	H15A—C15—H15C	109.5
H5B—C5—H5C	109.5	H15B—C15—H15C	109.5
O5—Co1—O1—C2	−169.72 (16)	Co1—O1—C2—C3	−0.1 (3)
O6—Co1—O1—C2	93.39 (16)	Co1—O1—C2—C1	−179.23 (14)
O3—Co1—O1—C2	−82.56 (16)	O1—C2—C3—C4	−4.6 (4)
O2—Co1—O1—C2	5.17 (17)	C1—C2—C3—C4	174.6 (2)
O6—Co1—O2—C4	−96.40 (16)	Co1—O2—C4—C3	6.2 (3)
O3—Co1—O2—C4	80.02 (16)	Co1—O2—C4—C5	−175.26 (14)
O4—Co1—O2—C4	176.80 (16)	C2—C3—C4—O2	1.1 (4)
O1—Co1—O2—C4	−8.09 (17)	C2—C3—C4—C5	−177.4 (2)
O5—Co1—O3—C7	−83.88 (17)	Co1—O3—C7—C8	−2.1 (3)
O4—Co1—O3—C7	4.59 (17)	Co1—O3—C7—C6	179.18 (15)
O2—Co1—O3—C7	92.06 (17)	O3—C7—C8—C9	−2.5 (4)
O1—Co1—O3—C7	−171.48 (17)	C6—C7—C8—C9	176.2 (2)
O5—Co1—O4—C9	82.65 (17)	Co1—O4—C9—C8	1.4 (3)
O6—Co1—O4—C9	179.55 (17)	Co1—O4—C9—C10	−178.69 (14)
O3—Co1—O4—C9	−4.28 (17)	C7—C8—C9—O4	2.9 (4)
O2—Co1—O4—C9	−91.93 (17)	C7—C8—C9—C10	−177.0 (2)
O6—Co1—O5—C12	−5.86 (19)	Co1—O5—C12—C13	2.6 (4)
O3—Co1—O5—C12	177.47 (19)	Co1—O5—C12—C11	−176.22 (17)
O4—Co1—O5—C12	80.71 (18)	O5—C12—C13—C14	2.6 (5)
O1—Co1—O5—C12	−94.06 (19)	C11—C12—C13—C14	−178.6 (3)
O5—Co1—O6—C14	6.03 (19)	Co1—O6—C14—C13	−3.0 (4)
O4—Co1—O6—C14	−82.39 (18)	Co1—O6—C14—C15	178.31 (17)
O2—Co1—O6—C14	−170.21 (18)	C12—C13—C14—O6	−2.4 (5)
O1—Co1—O6—C14	93.35 (18)	C12—C13—C14—C15	176.2 (3)

(Id) α-Tris(pentane-2,4-dionato-κ²O,O')cobalt(III)

Crystal data

[Co(C5H7O2)3]	F(000) = 744
Mr = 356.25	Dx = 1.471 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6515 reflections
a = 13.6927 (6) Å	θ = 1.5–27.5°
b = 7.3920 (3) Å	µ = 1.09 mm^−1
c = 16.0641 (6) Å	T = 150 K
β = 98.499 (2)°	Hexagonal plate, dark green
V = 1608.11 (11) Å^3	0.23 × 0.15 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3698 independent reflections
Radiation source: rotating anode	2812 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
258 ϕ and 231 ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −17→17
Tmin = 0.47, Tmax = 0.95	k = −9→9
18370 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0331P)^2 + 0.8216P] where P = (Fo^2 + 2Fc^2)/3
3698 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.24183 (2)	0.27053 (4)	0.468420 (17)	0.02031 (9)
O1	0.25312 (10)	0.50561 (19)	0.51531 (9)	0.0238 (3)
O2	0.36763 (10)	0.18808 (19)	0.51824 (9)	0.0236 (3)
O3	0.30189 (11)	0.35818 (19)	0.37823 (9)	0.0250 (3)
O4	0.21668 (10)	0.03447 (19)	0.42615 (9)	0.0246 (3)
O5	0.12086 (11)	0.3444 (2)	0.40745 (9)	0.0277 (3)
O6	0.19170 (11)	0.1917 (2)	0.56505 (9)	0.0251 (3)
C1	0.32341 (18)	0.7560 (3)	0.59119 (15)	0.0317 (5)
H1A	0.2945	0.8346	0.5449	0.047*
H1B	0.3893	0.8005	0.6142	0.047*
H1C	0.2813	0.7565	0.6355	0.047*
C2	0.33132 (16)	0.5659 (3)	0.55892 (13)	0.0223 (4)
C3	0.41933 (16)	0.4704 (3)	0.57908 (14)	0.0273 (5)
H3	0.4741	0.5330	0.6091	0.033*
C4	0.43300 (15)	0.2901 (3)	0.55851 (13)	0.0233 (5)
C5	0.53088 (16)	0.2009 (3)	0.58720 (15)	0.0326 (5)
H5A	0.5265	0.1280	0.6375	0.049*
H5B	0.5818	0.2939	0.6006	0.049*
H5C	0.5481	0.1228	0.5423	0.049*
C6	0.35804 (18)	0.3607 (3)	0.24726 (14)	0.0322 (5)
H6A	0.3686	0.4881	0.2629	0.048*
H6B	0.3161	0.3528	0.1924	0.048*
H6C	0.4218	0.3030	0.2440	0.048*
C7	0.30842 (15)	0.2662 (3)	0.31230 (13)	0.0230 (4)
C8	0.27564 (16)	0.0887 (3)	0.29740 (13)	0.0256 (5)
H8	0.2821	0.0368	0.2444	0.031*
C9	0.23437 (15)	−0.0174 (3)	0.35418 (13)	0.0223 (4)
C10	0.20612 (17)	−0.2112 (3)	0.33361 (14)	0.0288 (5)
H10A	0.2345	−0.2894	0.3802	0.043*
H10B	0.2314	−0.2474	0.2821	0.043*
H10C	0.1340	−0.2226	0.3251	0.043*
C11	−0.04953 (19)	0.3780 (4)	0.37037 (17)	0.0474 (7)
H11A	−0.0323	0.4870	0.3410	0.071*
H11B	−0.1051	0.4045	0.4005	0.071*
H11C	−0.0682	0.2813	0.3294	0.071*
C12	0.03809 (17)	0.3185 (3)	0.43229 (15)	0.0312 (5)
C13	0.02394 (17)	0.2396 (4)	0.50809 (16)	0.0398 (6)
H13	−0.0420	0.2226	0.5183	0.048*
C14	0.09980 (17)	0.1839 (3)	0.57006 (14)	0.0299 (5)
C15	0.0771 (2)	0.1108 (4)	0.65245 (16)	0.0446 (7)
H15A	0.1240	0.0143	0.6721	0.067*
H15B	0.0098	0.0622	0.6447	0.067*
H15C	0.0827	0.2083	0.6942	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02347 (15)	0.02090 (15)	0.01648 (14)	0.00277 (12)	0.00273 (11)	−0.00085 (12)
O1	0.0280 (8)	0.0214 (7)	0.0219 (8)	0.0043 (6)	0.0032 (7)	−0.0028 (6)
O2	0.0234 (8)	0.0229 (8)	0.0242 (8)	0.0035 (6)	0.0026 (6)	−0.0010 (6)
O3	0.0332 (8)	0.0231 (8)	0.0196 (8)	−0.0001 (7)	0.0071 (6)	−0.0009 (6)
O4	0.0315 (8)	0.0229 (8)	0.0195 (8)	−0.0008 (7)	0.0041 (6)	−0.0016 (6)
O5	0.0281 (8)	0.0312 (9)	0.0223 (8)	0.0036 (7)	−0.0012 (6)	−0.0007 (7)
O6	0.0261 (8)	0.0290 (8)	0.0206 (8)	0.0033 (7)	0.0046 (6)	0.0012 (6)
C1	0.0449 (14)	0.0228 (12)	0.0277 (12)	−0.0024 (10)	0.0069 (10)	−0.0038 (10)
C2	0.0327 (12)	0.0206 (11)	0.0145 (10)	−0.0018 (9)	0.0071 (9)	0.0001 (8)
C3	0.0237 (11)	0.0297 (12)	0.0279 (12)	−0.0033 (10)	0.0017 (9)	−0.0022 (10)
C4	0.0224 (10)	0.0299 (11)	0.0186 (10)	0.0007 (9)	0.0067 (8)	0.0031 (9)
C5	0.0235 (11)	0.0412 (14)	0.0331 (13)	0.0044 (10)	0.0041 (10)	0.0002 (11)
C6	0.0395 (13)	0.0347 (13)	0.0233 (12)	−0.0051 (11)	0.0071 (10)	−0.0005 (10)
C7	0.0220 (10)	0.0279 (11)	0.0185 (10)	0.0059 (9)	0.0006 (8)	0.0022 (9)
C8	0.0326 (12)	0.0267 (12)	0.0172 (11)	0.0027 (9)	0.0026 (9)	−0.0045 (9)
C9	0.0198 (10)	0.0236 (11)	0.0209 (11)	0.0053 (9)	−0.0053 (8)	−0.0021 (9)
C10	0.0328 (12)	0.0241 (11)	0.0277 (12)	0.0010 (10)	−0.0015 (10)	−0.0042 (9)
C11	0.0356 (14)	0.0624 (19)	0.0398 (16)	0.0128 (13)	−0.0094 (12)	−0.0094 (14)
C12	0.0268 (12)	0.0373 (14)	0.0274 (12)	0.0042 (10)	−0.0030 (10)	−0.0095 (10)
C13	0.0230 (12)	0.0620 (18)	0.0347 (13)	−0.0020 (12)	0.0054 (10)	−0.0039 (13)
C14	0.0301 (12)	0.0345 (13)	0.0262 (12)	−0.0054 (10)	0.0076 (10)	−0.0053 (10)
C15	0.0411 (15)	0.0596 (18)	0.0355 (15)	−0.0093 (13)	0.0133 (12)	0.0057 (13)

Geometric parameters (Å, º)

Co1—O5	1.8766 (15)	C6—C7	1.500 (3)
Co1—O6	1.8801 (14)	C6—H6A	0.9800
Co1—O3	1.8835 (14)	C6—H6B	0.9800
Co1—O4	1.8856 (14)	C6—H6C	0.9800
Co1—O2	1.8899 (14)	C7—C8	1.396 (3)
Co1—O1	1.8912 (14)	C8—C9	1.385 (3)
O1—C2	1.271 (2)	C8—H8	0.9500
O2—C4	1.272 (3)	C9—C10	1.507 (3)
O3—C7	1.273 (2)	C10—H10A	0.9800
O4—C9	1.275 (2)	C10—H10B	0.9800
O5—C12	1.270 (3)	C10—H10C	0.9800
O6—C14	1.274 (3)	C11—C12	1.506 (3)
C1—C2	1.507 (3)	C11—H11A	0.9800
C1—H1A	0.9800	C11—H11B	0.9800
C1—H1B	0.9800	C11—H11C	0.9800
C1—H1C	0.9800	C12—C13	1.389 (3)
C2—C3	1.393 (3)	C13—C14	1.391 (3)
C3—C4	1.392 (3)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.504 (3)
C4—C5	1.503 (3)	C15—H15A	0.9800
C5—H5A	0.9800	C15—H15B	0.9800
C5—H5B	0.9800	C15—H15C	0.9800
C5—H5C	0.9800
O5—Co1—O6	96.85 (6)	C7—C6—H6A	109.5
O5—Co1—O3	87.16 (7)	C7—C6—H6B	109.5
O6—Co1—O3	174.78 (7)	H6A—C6—H6B	109.5
O5—Co1—O4	88.93 (7)	C7—C6—H6C	109.5
O6—Co1—O4	86.63 (6)	H6A—C6—H6C	109.5
O3—Co1—O4	96.81 (6)	H6B—C6—H6C	109.5
O5—Co1—O2	173.63 (6)	O3—C7—C8	125.76 (19)
O6—Co1—O2	88.37 (6)	O3—C7—C6	115.20 (19)
O3—Co1—O2	87.84 (6)	C8—C7—C6	119.03 (19)
O4—Co1—O2	87.74 (6)	C9—C8—C7	124.84 (19)
O5—Co1—O1	87.38 (6)	C9—C8—H8	117.6
O6—Co1—O1	88.52 (6)	C7—C8—H8	117.6
O3—Co1—O1	88.34 (6)	O4—C9—C8	125.29 (19)
O4—Co1—O1	173.51 (6)	O4—C9—C10	114.05 (19)
O2—Co1—O1	96.42 (6)	C8—C9—C10	120.66 (19)
C2—O1—Co1	123.68 (13)	C9—C10—H10A	109.5
C4—O2—Co1	123.59 (14)	C9—C10—H10B	109.5
C7—O3—Co1	123.28 (14)	H10A—C10—H10B	109.5
C9—O4—Co1	123.77 (14)	C9—C10—H10C	109.5
C12—O5—Co1	123.49 (15)	H10A—C10—H10C	109.5
C14—O6—Co1	123.42 (15)	H10B—C10—H10C	109.5
C2—C1—H1A	109.5	C12—C11—H11A	109.5
C2—C1—H1B	109.5	C12—C11—H11B	109.5
H1A—C1—H1B	109.5	H11A—C11—H11B	109.5
C2—C1—H1C	109.5	C12—C11—H11C	109.5
H1A—C1—H1C	109.5	H11A—C11—H11C	109.5
H1B—C1—H1C	109.5	H11B—C11—H11C	109.5
O1—C2—C3	125.46 (19)	O5—C12—C13	125.8 (2)
O1—C2—C1	114.78 (19)	O5—C12—C11	114.1 (2)
C3—C2—C1	119.8 (2)	C13—C12—C11	120.0 (2)
C4—C3—C2	124.9 (2)	C12—C13—C14	124.4 (2)
C4—C3—H3	117.6	C12—C13—H13	117.8
C2—C3—H3	117.6	C14—C13—H13	117.8
O2—C4—C3	125.4 (2)	O6—C14—C13	125.6 (2)
O2—C4—C5	115.12 (19)	O6—C14—C15	114.0 (2)
C3—C4—C5	119.5 (2)	C13—C14—C15	120.4 (2)
C4—C5—H5A	109.5	C14—C15—H15A	109.5
C4—C5—H5B	109.5	C14—C15—H15B	109.5
H5A—C5—H5B	109.5	H15A—C15—H15B	109.5
C4—C5—H5C	109.5	C14—C15—H15C	109.5
H5A—C5—H5C	109.5	H15A—C15—H15C	109.5
H5B—C5—H5C	109.5	H15B—C15—H15C	109.5
O5—Co1—O1—C2	−169.72 (16)	Co1—O1—C2—C3	−0.3 (3)
O6—Co1—O1—C2	93.35 (16)	Co1—O1—C2—C1	−179.10 (13)
O3—Co1—O1—C2	−82.49 (16)	O1—C2—C3—C4	−4.0 (4)
O2—Co1—O1—C2	5.15 (16)	C1—C2—C3—C4	174.8 (2)
O6—Co1—O2—C4	−96.53 (16)	Co1—O2—C4—C3	6.6 (3)
O3—Co1—O2—C4	79.87 (16)	Co1—O2—C4—C5	−175.32 (14)
O4—Co1—O2—C4	176.78 (16)	C2—C3—C4—O2	0.4 (4)
O1—Co1—O2—C4	−8.21 (16)	C2—C3—C4—C5	−177.5 (2)
O5—Co1—O3—C7	−84.05 (16)	Co1—O3—C7—C8	−1.9 (3)
O4—Co1—O3—C7	4.53 (16)	Co1—O3—C7—C6	179.43 (14)
O2—Co1—O3—C7	91.99 (16)	O3—C7—C8—C9	−2.8 (3)
O1—Co1—O3—C7	−171.52 (16)	C6—C7—C8—C9	175.8 (2)
O5—Co1—O4—C9	82.81 (16)	Co1—O4—C9—C8	1.2 (3)
O6—Co1—O4—C9	179.74 (16)	Co1—O4—C9—C10	−178.82 (13)
O3—Co1—O4—C9	−4.20 (16)	C7—C8—C9—O4	3.2 (3)
O2—Co1—O4—C9	−91.76 (16)	C7—C8—C9—C10	−176.8 (2)
O6—Co1—O5—C12	−6.13 (18)	Co1—O5—C12—C13	2.6 (3)
O3—Co1—O5—C12	177.21 (18)	Co1—O5—C12—C11	−176.09 (16)
O4—Co1—O5—C12	80.34 (17)	O5—C12—C13—C14	2.9 (4)
O1—Co1—O5—C12	−94.32 (18)	C11—C12—C13—C14	−178.5 (2)
O5—Co1—O6—C14	6.55 (18)	Co1—O6—C14—C13	−3.4 (3)
O4—Co1—O6—C14	−81.96 (17)	Co1—O6—C14—C15	178.05 (16)
O2—Co1—O6—C14	−169.79 (17)	C12—C13—C14—O6	−2.4 (4)
O1—Co1—O6—C14	93.74 (17)	C12—C13—C14—C15	176.0 (2)

(Ie) α-Tris(pentane-2,4-dionato-κ²O,O')cobalt(III)

Crystal data

[Co(C5H7O2)3]	F(000) = 744
Mr = 356.25	Dx = 1.483 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 10583 reflections
a = 13.6376 (5) Å	θ = 1.5–27.5°
b = 7.3758 (3) Å	µ = 1.10 mm^−1
c = 16.0446 (9) Å	T = 110 K
β = 98.594 (2)°	Hexagonal plate, dark green
V = 1595.78 (12) Å^3	0.23 × 0.15 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3656 independent reflections
Radiation source: rotating anode	3018 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
431 ϕ and 323 ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −17→17
Tmin = 0.57, Tmax = 0.95	k = −9→9
27696 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0257P)^2 + 0.9857P] where P = (Fo^2 + 2Fc^2)/3
3656 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.241815 (17)	0.27167 (3)	0.468196 (14)	0.01426 (7)
O1	0.25340 (9)	0.50735 (16)	0.51508 (7)	0.0173 (3)
O2	0.36822 (9)	0.18839 (16)	0.51789 (7)	0.0170 (3)
O3	0.30183 (9)	0.35948 (16)	0.37758 (7)	0.0179 (3)
O4	0.21613 (9)	0.03514 (16)	0.42586 (7)	0.0175 (3)
O5	0.12013 (9)	0.34613 (17)	0.40741 (8)	0.0200 (3)
O6	0.19172 (9)	0.19233 (16)	0.56511 (7)	0.0180 (3)
C1	0.32419 (14)	0.7581 (2)	0.59136 (12)	0.0230 (4)
H1A	0.2940	0.8364	0.5452	0.034*
H1B	0.3905	0.8035	0.6136	0.034*
H1C	0.2828	0.7582	0.6363	0.034*
C2	0.33220 (13)	0.5676 (2)	0.55906 (10)	0.0162 (3)
C3	0.42066 (13)	0.4720 (2)	0.57912 (11)	0.0196 (4)
H3	0.4758	0.5345	0.6092	0.024*
C4	0.43412 (12)	0.2907 (2)	0.55826 (11)	0.0170 (3)
C5	0.53249 (13)	0.2013 (3)	0.58689 (12)	0.0244 (4)
H5A	0.5280	0.1266	0.6367	0.037*
H5B	0.5835	0.2945	0.6011	0.037*
H5C	0.5502	0.1246	0.5415	0.037*
C6	0.35897 (14)	0.3609 (3)	0.24652 (11)	0.0227 (4)
H6A	0.3689	0.4890	0.2618	0.034*
H6B	0.3175	0.3515	0.1913	0.034*
H6C	0.4234	0.3038	0.2441	0.034*
C7	0.30856 (12)	0.2664 (2)	0.31169 (10)	0.0164 (3)
C8	0.27562 (13)	0.0890 (2)	0.29670 (11)	0.0190 (4)
H8	0.2821	0.0369	0.2437	0.023*
C9	0.23383 (12)	−0.0175 (2)	0.35377 (11)	0.0163 (3)
C10	0.20524 (13)	−0.2117 (2)	0.33317 (11)	0.0202 (4)
H10A	0.2317	−0.2896	0.3807	0.030*
H10B	0.2327	−0.2496	0.2829	0.030*
H10C	0.1328	−0.2221	0.3225	0.030*
C11	−0.05123 (15)	0.3801 (3)	0.37053 (13)	0.0347 (5)
H11A	−0.0337	0.4886	0.3407	0.052*
H11B	−0.1066	0.4081	0.4009	0.052*
H11C	−0.0707	0.2829	0.3298	0.052*
C12	0.03699 (14)	0.3199 (3)	0.43237 (12)	0.0236 (4)
C13	0.02286 (14)	0.2398 (3)	0.50824 (13)	0.0288 (4)
H13	−0.0433	0.2221	0.5184	0.035*
C14	0.09955 (14)	0.1838 (2)	0.57015 (12)	0.0216 (4)
C15	0.07695 (16)	0.1089 (3)	0.65256 (13)	0.0331 (5)
H15A	0.1249	0.0136	0.6724	0.050*
H15B	0.0098	0.0581	0.6445	0.050*
H15C	0.0815	0.2064	0.6945	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01652 (12)	0.01502 (12)	0.01115 (11)	0.00205 (9)	0.00182 (8)	−0.00067 (9)
O1	0.0196 (6)	0.0166 (6)	0.0151 (6)	0.0032 (5)	0.0011 (5)	−0.0022 (5)
O2	0.0174 (6)	0.0172 (6)	0.0165 (6)	0.0029 (5)	0.0020 (5)	−0.0017 (5)
O3	0.0234 (6)	0.0169 (6)	0.0139 (6)	0.0004 (5)	0.0047 (5)	−0.0007 (5)
O4	0.0215 (6)	0.0164 (6)	0.0148 (6)	−0.0005 (5)	0.0029 (5)	−0.0010 (5)
O5	0.0204 (6)	0.0227 (6)	0.0156 (6)	0.0031 (5)	−0.0012 (5)	−0.0012 (5)
O6	0.0189 (6)	0.0212 (6)	0.0141 (6)	0.0020 (5)	0.0027 (5)	0.0009 (5)
C1	0.0329 (10)	0.0173 (9)	0.0192 (9)	−0.0014 (8)	0.0055 (8)	−0.0028 (7)
C2	0.0239 (9)	0.0160 (8)	0.0099 (8)	−0.0010 (7)	0.0067 (7)	0.0015 (6)
C3	0.0177 (8)	0.0217 (9)	0.0188 (9)	−0.0027 (7)	0.0006 (7)	−0.0018 (7)
C4	0.0168 (8)	0.0228 (9)	0.0125 (8)	0.0013 (7)	0.0056 (6)	0.0033 (7)
C5	0.0184 (9)	0.0299 (10)	0.0248 (10)	0.0050 (8)	0.0027 (7)	0.0003 (8)
C6	0.0275 (10)	0.0265 (10)	0.0147 (9)	−0.0027 (8)	0.0051 (7)	0.0002 (7)
C7	0.0149 (8)	0.0213 (9)	0.0123 (8)	0.0038 (7)	−0.0003 (6)	0.0006 (7)
C8	0.0239 (9)	0.0205 (9)	0.0123 (9)	0.0019 (7)	0.0019 (7)	−0.0034 (7)
C9	0.0139 (8)	0.0181 (8)	0.0151 (9)	0.0041 (6)	−0.0035 (6)	−0.0016 (7)
C10	0.0230 (9)	0.0175 (8)	0.0188 (9)	0.0002 (7)	−0.0015 (7)	−0.0024 (7)
C11	0.0255 (10)	0.0458 (13)	0.0293 (12)	0.0089 (9)	−0.0079 (9)	−0.0071 (10)
C12	0.0201 (9)	0.0275 (10)	0.0214 (10)	0.0035 (7)	−0.0029 (7)	−0.0069 (8)
C13	0.0157 (9)	0.0453 (13)	0.0256 (10)	−0.0009 (9)	0.0037 (7)	−0.0004 (9)
C14	0.0225 (9)	0.0235 (10)	0.0197 (9)	−0.0032 (7)	0.0057 (7)	−0.0031 (7)
C15	0.0309 (11)	0.0440 (13)	0.0261 (11)	−0.0064 (9)	0.0096 (9)	0.0048 (9)

Geometric parameters (Å, º)

Co1—O5	1.8770 (12)	C6—C7	1.505 (2)
Co1—O6	1.8827 (12)	C6—H6A	0.9800
Co1—O4	1.8859 (12)	C6—H6B	0.9800
Co1—O3	1.8865 (12)	C6—H6C	0.9800
Co1—O2	1.8906 (12)	C7—C8	1.393 (2)
Co1—O1	1.8913 (12)	C8—C9	1.392 (2)
O1—C2	1.274 (2)	C8—H8	0.9500
O2—C4	1.274 (2)	C9—C10	1.508 (2)
O3—C7	1.275 (2)	C10—H10A	0.9800
O4—C9	1.277 (2)	C10—H10B	0.9800
O5—C12	1.272 (2)	C10—H10C	0.9800
O6—C14	1.273 (2)	C11—C12	1.507 (3)
C1—C2	1.507 (2)	C11—H11A	0.9800
C1—H1A	0.9800	C11—H11B	0.9800
C1—H1B	0.9800	C11—H11C	0.9800
C1—H1C	0.9800	C12—C13	1.392 (3)
C2—C3	1.393 (2)	C13—C14	1.393 (3)
C3—C4	1.397 (2)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.507 (3)
C4—C5	1.504 (2)	C15—H15A	0.9800
C5—H5A	0.9800	C15—H15B	0.9800
C5—H5B	0.9800	C15—H15C	0.9800
C5—H5C	0.9800
O5—Co1—O6	96.79 (5)	C7—C6—H6A	109.5
O5—Co1—O4	88.93 (5)	C7—C6—H6B	109.5
O6—Co1—O4	86.52 (5)	H6A—C6—H6B	109.5
O5—Co1—O3	87.18 (5)	C7—C6—H6C	109.5
O6—Co1—O3	174.88 (5)	H6A—C6—H6C	109.5
O4—Co1—O3	96.81 (5)	H6B—C6—H6C	109.5
O5—Co1—O2	173.67 (5)	O3—C7—C8	125.98 (16)
O6—Co1—O2	88.35 (5)	O3—C7—C6	115.06 (15)
O4—Co1—O2	87.70 (5)	C8—C7—C6	118.95 (15)
O3—Co1—O2	87.90 (5)	C9—C8—C7	124.76 (16)
O5—Co1—O1	87.28 (5)	C9—C8—H8	117.6
O6—Co1—O1	88.64 (5)	C7—C8—H8	117.6
O4—Co1—O1	173.46 (5)	O4—C9—C8	125.15 (16)
O3—Co1—O1	88.33 (5)	O4—C9—C10	114.19 (15)
O2—Co1—O1	96.55 (5)	C8—C9—C10	120.66 (16)
C2—O1—Co1	123.67 (11)	C9—C10—H10A	109.5
C4—O2—Co1	123.46 (11)	C9—C10—H10B	109.5
C7—O3—Co1	123.19 (11)	H10A—C10—H10B	109.5
C9—O4—Co1	123.89 (11)	C9—C10—H10C	109.5
C12—O5—Co1	123.52 (12)	H10A—C10—H10C	109.5
C14—O6—Co1	123.46 (12)	H10B—C10—H10C	109.5
C2—C1—H1A	109.5	C12—C11—H11A	109.5
C2—C1—H1B	109.5	C12—C11—H11B	109.5
H1A—C1—H1B	109.5	H11A—C11—H11B	109.5
C2—C1—H1C	109.5	C12—C11—H11C	109.5
H1A—C1—H1C	109.5	H11A—C11—H11C	109.5
H1B—C1—H1C	109.5	H11B—C11—H11C	109.5
O1—C2—C3	125.50 (16)	O5—C12—C13	125.87 (17)
O1—C2—C1	114.66 (15)	O5—C12—C11	114.15 (18)
C3—C2—C1	119.83 (16)	C13—C12—C11	119.97 (18)
C2—C3—C4	124.72 (16)	C12—C13—C14	124.20 (17)
C2—C3—H3	117.6	C12—C13—H13	117.9
C4—C3—H3	117.6	C14—C13—H13	117.9
O2—C4—C3	125.52 (16)	O6—C14—C13	125.68 (17)
O2—C4—C5	115.14 (15)	O6—C14—C15	114.02 (16)
C3—C4—C5	119.31 (16)	C13—C14—C15	120.28 (17)
C4—C5—H5A	109.5	C14—C15—H15A	109.5
C4—C5—H5B	109.5	C14—C15—H15B	109.5
H5A—C5—H5B	109.5	H15A—C15—H15B	109.5
C4—C5—H5C	109.5	C14—C15—H15C	109.5
H5A—C5—H5C	109.5	H15A—C15—H15C	109.5
H5B—C5—H5C	109.5	H15B—C15—H15C	109.5
O5—Co1—O1—C2	−170.08 (13)	Co1—O1—C2—C3	0.2 (2)
O6—Co1—O1—C2	93.05 (13)	Co1—O1—C2—C1	−178.96 (11)
O3—Co1—O1—C2	−82.82 (13)	O1—C2—C3—C4	−4.3 (3)
O2—Co1—O1—C2	4.87 (13)	C1—C2—C3—C4	174.81 (16)
O6—Co1—O2—C4	−96.58 (13)	Co1—O2—C4—C3	6.7 (2)
O4—Co1—O2—C4	176.84 (13)	Co1—O2—C4—C5	−175.31 (11)
O3—Co1—O2—C4	79.94 (13)	C2—C3—C4—O2	0.4 (3)
O1—Co1—O2—C4	−8.14 (13)	C2—C3—C4—C5	−177.50 (17)
O5—Co1—O3—C7	−84.60 (13)	Co1—O3—C7—C8	−1.3 (2)
O4—Co1—O3—C7	3.99 (13)	Co1—O3—C7—C6	179.94 (11)
O2—Co1—O3—C7	91.42 (13)	O3—C7—C8—C9	−3.1 (3)
O1—Co1—O3—C7	−171.96 (13)	C6—C7—C8—C9	175.65 (16)
O5—Co1—O4—C9	83.14 (13)	Co1—O4—C9—C8	1.1 (2)
O6—Co1—O4—C9	−179.99 (13)	Co1—O4—C9—C10	−178.91 (10)
O3—Co1—O4—C9	−3.90 (13)	C7—C8—C9—O4	3.2 (3)
O2—Co1—O4—C9	−91.50 (13)	C7—C8—C9—C10	−176.84 (16)
O6—Co1—O5—C12	−6.25 (14)	Co1—O5—C12—C13	2.4 (3)
O4—Co1—O5—C12	80.11 (14)	Co1—O5—C12—C11	−176.12 (12)
O3—Co1—O5—C12	176.99 (14)	O5—C12—C13—C14	3.2 (3)
O1—Co1—O5—C12	−94.55 (14)	C11—C12—C13—C14	−178.37 (19)
O5—Co1—O6—C14	6.88 (14)	Co1—O6—C14—C13	−3.7 (3)
O4—Co1—O6—C14	−81.62 (14)	Co1—O6—C14—C15	177.58 (13)
O2—Co1—O6—C14	−169.42 (14)	C12—C13—C14—O6	−2.4 (3)
O1—Co1—O6—C14	93.98 (14)	C12—C13—C14—C15	176.19 (19)