Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017318/om6156sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017318/om6156Isup2.hkl |
CCDC reference: 222795
A solution of Co(acac)3 dissolved in methanol was added to a methanol solution of NaBH4. After stirring the reaction mixture for 2 h, the solution was concentrated by removing the solvent in vacuo. Light-brown needle-shaped crystals were formed by vapor diffusion of diethyl ether.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
Na[Co(C5H7O2)3] | F(000) = 1182 |
Mr = 379.24 | Dx = 1.433 Mg m−3 |
Rhombohedral, R3c | Mo Kα radiation, λ = 0.71073 Å |
a = 16.1201 (19) Å | Cell parameters from 2493 reflections |
c = 11.715 (3) Å | θ = 2.5–25.9° |
α = 90° | µ = 1.03 mm−1 |
γ = 120° | T = 100 K |
V = 2636.3 (7) Å3 | Needle, light brown |
Z = 6 | 0.50 × 0.10 × 0.07 mm |
CCD area-detector diffractometer | 548 independent reflections |
Radiation source: fine-focus sealed tube | 404 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
ω scans | θmax = 26.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −19→19 |
Tmin = 0.624, Tmax = 0.931 | k = −19→19 |
6796 measured reflections | l = −14→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.25 | w = 1/[σ2(Fo2) + (0.05P)2 + 1P] where P = (Fo2 + 2Fc2)/3 |
548 reflections | (Δ/σ)max < 0.001 |
37 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Na[Co(C5H7O2)3] | V = 2636.3 (7) Å3 |
Mr = 379.24 | Z = 6 |
Rhombohedral, R3c | Mo Kα radiation |
a = 16.1201 (19) Å | µ = 1.03 mm−1 |
c = 11.715 (3) Å | T = 100 K |
α = 90° | 0.50 × 0.10 × 0.07 mm |
γ = 120° |
CCD area-detector diffractometer | 548 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 404 reflections with I > 2σ(I) |
Tmin = 0.624, Tmax = 0.931 | Rint = 0.039 |
6796 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.25 | Δρmax = 0.70 e Å−3 |
548 reflections | Δρmin = −0.33 e Å−3 |
37 parameters |
Experimental. The first 50 frames were remeasured at the end of data collection. These two sets of frames contained 120 common data indicating a decay of −0.21% over the course of the entire data collection. |
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. |
x | y | z | Uiso*/Ueq | ||
Na1 | 0.0000 | 0.0000 | 0.0000 | 0.0232 (7) | |
Co1 | 0.0000 | 0.0000 | 0.2500 | 0.0188 (3) | |
C1 | 0.2584 (3) | 0.0738 (3) | 0.0556 (3) | 0.0315 (8) | |
H1A | 0.2242 | 0.0451 | −0.0157 | 0.047* | |
H1B | 0.3075 | 0.0559 | 0.0680 | 0.047* | |
H1C | 0.2889 | 0.1437 | 0.0507 | 0.047* | |
C2 | 0.1884 (2) | 0.0381 (2) | 0.1539 (3) | 0.0237 (7) | |
O3 | 0.11554 (16) | 0.04730 (16) | 0.14178 (19) | 0.0234 (5) | |
C4 | 0.2092 (3) | 0.0000 | 0.2500 | 0.0256 (10) | |
H4 | 0.2712 | 0.0000 | 0.2500 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0298 (10) | 0.0298 (10) | 0.0100 (14) | 0.0149 (5) | 0.000 | 0.000 |
Co1 | 0.0245 (4) | 0.0245 (4) | 0.0073 (5) | 0.0123 (2) | 0.000 | 0.000 |
C1 | 0.0337 (19) | 0.037 (2) | 0.0246 (18) | 0.0178 (16) | 0.0078 (15) | 0.0041 (15) |
C2 | 0.0293 (17) | 0.0226 (16) | 0.0182 (15) | 0.0122 (14) | 0.0013 (13) | −0.0037 (13) |
O3 | 0.0258 (11) | 0.0328 (13) | 0.0116 (11) | 0.0146 (10) | 0.0002 (9) | −0.0009 (9) |
C4 | 0.0253 (17) | 0.026 (2) | 0.026 (2) | 0.0129 (12) | 0.0003 (10) | 0.0005 (19) |
Na1—O3 | 2.321 (2) | C1—H1B | 0.9800 |
Na1—Co1 | 2.9287 (6) | C1—H1C | 0.9800 |
Co1—O3 | 2.059 (2) | C2—O3 | 1.263 (4) |
Co1—Na1i | 2.9287 (6) | C2—C4 | 1.401 (4) |
C1—C2 | 1.510 (4) | C4—H4 | 0.9999 |
C1—H1A | 0.9800 | ||
O3—Na1—O3ii | 105.54 (9) | H1A—C1—H1B | 109.5 |
O3—Na1—O3iii | 74.46 (9) | C2—C1—H1C | 109.5 |
O3—Na1—Co1 | 44.32 (5) | H1A—C1—H1C | 109.5 |
O3iv—Na1—Co1 | 135.68 (5) | H1B—C1—H1C | 109.5 |
O3iii—Na1—Co1 | 44.32 (5) | O3—C2—C4 | 125.6 (3) |
O3v—Co1—O3i | 170.59 (12) | O3—C2—C1 | 115.5 (3) |
O3v—Co1—O3vi | 100.78 (12) | C4—C2—C1 | 118.9 (3) |
O3v—Co1—O3iii | 86.05 (9) | C2—O3—Co1 | 127.5 (2) |
O3i—Co1—O3iii | 87.96 (12) | C2—O3—Na1 | 133.0 (2) |
O3v—Co1—Na1 | 51.98 (6) | Co1—O3—Na1 | 83.70 (8) |
O3i—Co1—Na1 | 128.02 (6) | C2—C4—C2vi | 125.4 (4) |
C2—C1—H1A | 109.5 | C2—C4—H4 | 117.3 |
C2—C1—H1B | 109.5 | ||
O3—Na1—Co1—O3i | 71.95 (15) | Na1i—Co1—O3—C2 | 38.6 (3) |
O3iv—Na1—Co1—O3i | −108.05 (15) | O3v—Co1—O3—Na1 | 43.15 (4) |
O3ii—Na1—Co1—O3i | 131.95 (15) | O3i—Co1—O3—Na1 | −130.31 (9) |
O3iii—Na1—Co1—O3i | −48.05 (15) | O3vi—Co1—O3—Na1 | 144.10 (10) |
O3vii—Na1—Co1—O3i | 11.95 (15) | O3iii—Co1—O3—Na1 | −43.15 (4) |
O3v—Na1—Co1—O3i | −168.05 (15) | O3viii—Co1—O3—Na1 | 93.69 (5) |
O3—Na1—Co1—O3vi | −48.05 (15) | O3iv—Na1—O3—C2 | 169.3 (3) |
O3iv—Na1—Co1—O3vi | 131.95 (15) | O3ii—Na1—O3—C2 | −3.8 (3) |
O3vii—Na1—Co1—O3vi | −108.05 (15) | O3iii—Na1—O3—C2 | 176.2 (3) |
O3—Na1—Co1—O3viii | −168.05 (15) | O3vii—Na1—O3—C2 | −81.6 (3) |
C4—C2—O3—Co1 | −5.7 (4) | O3v—Na1—O3—C2 | 98.4 (3) |
C1—C2—O3—Co1 | 175.6 (2) | Co1—Na1—O3—C2 | 137.3 (3) |
C4—C2—O3—Na1 | −127.5 (3) | Co1iv—Na1—O3—C2 | −42.7 (3) |
C1—C2—O3—Na1 | 53.7 (4) | O3iv—Na1—O3—Co1 | 31.92 (8) |
O3v—Co1—O3—C2 | −98.2 (3) | O3iii—Na1—O3—Co1 | 38.90 (3) |
O3i—Co1—O3—C2 | 88.3 (3) | O3vii—Na1—O3—Co1 | 141.10 (3) |
O3vi—Co1—O3—C2 | 2.7 (2) | O3v—Na1—O3—Co1 | −38.90 (3) |
O3iii—Co1—O3—C2 | 175.5 (3) | O3—C2—C4—C2vi | 3.1 (2) |
O3viii—Co1—O3—C2 | −47.7 (2) | C1—C2—C4—C2vi | −178.2 (3) |
Na1—Co1—O3—C2 | −141.4 (3) |
Symmetry codes: (i) y, x, −z+1/2; (ii) y, −x+y, −z; (iii) −y, x−y, z; (iv) −x, −y, −z; (v) −x+y, −x, z; (vi) x−y, −y, −z+1/2; (vii) x−y, x, −z; (viii) −x, −x+y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | Na[Co(C5H7O2)3] |
Mr | 379.24 |
Crystal system, space group | Rhombohedral, R3c |
Temperature (K) | 100 |
a, c (Å) | 16.1201 (19), 11.715 (3) |
V (Å3) | 2636.3 (7) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 1.03 |
Crystal size (mm) | 0.50 × 0.10 × 0.07 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.624, 0.931 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6796, 548, 404 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.119, 1.25 |
No. of reflections | 548 |
No. of parameters | 37 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.70, −0.33 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1997), SHELXTL.
Metal carboxylate complexes have been the subject of interest for many years (Oldham, 1968; Doedens, 1976). Although a great deal of work has been reported on the synthesis and characterization of various cobalt(III) complexes of the acetylacetonate ligand, only a few cobalt(II) complexes have been reported (Cotton & Elder, 1965, 1966; Santarsiero, et al., 1981). As part of a general method for the preparation of stable cobalt(II) complexes, we prepared Na[Co(acac)3], (I), and its crystal structure is presented here.