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
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.005 Å
- R factor = 0.038
- wR factor = 0.119
- Data-to-parameter ratio = 14.8
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ..... 0.94
Alert level B SYMMS02_ALERT_1_B The unit-cell lengths a and c should be equal for a rhombohedral cell Cell 16.1201 16.1201 11.7150 Angles 90.0000 90.0000 120.0000 SYMMS02_ALERT_1_B Cell angles alpha and gamma should be equal for a rhombohedral cell Cell 16.1201 16.1201 11.7150 Angles 90.0000 90.0000 120.0000 SYMMS02_ALERT_1_B All angles should not be 90 for a rhombohedral cell Cell 16.1201 16.1201 11.7150 Angles 90.0000 90.0000 120.0000
Alert level C PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .. 0.94 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .. ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .. 2.14 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ..... ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ... ? PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 19 O3 -CO1 -O3 -C2 -47.70 0.20 6.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 26 O3 -CO1 -O3 -NA1 93.69 0.05 6.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 27 O3 -NA1 -O3 -C2 169.30 0.30 19.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle # 34 O3 -NA1 -O3 -CO1 31.92 0.08 19.555 1.555 1.555 1.555 PLAT733_ALERT_1_C Torsion Calc 43.15(10), Rep 43.15(4) .... 2.50 su-Ratio O3 -CO1 -O3 -NA1 3.555 1.555 1.555 1.555 PLAT733_ALERT_1_C Torsion Calc -43.15(9), Rep -43.15(4) .... 2.25 su-Ratio O3 -CO1 -O3 -NA1 2.555 1.555 1.555 1.555 PLAT733_ALERT_1_C Torsion Calc 38.90(9), Rep 38.90(3) .... 3.00 su-Ratio O3 -NA1 -O3 -CO1 2.555 1.555 1.555 1.555 PLAT733_ALERT_1_C Torsion Calc 141.10(9), Rep 141.10(3) .... 3.00 su-Ratio O3 -NA1 -O3 -CO1 21.555 1.555 1.555 1.555 PLAT733_ALERT_1_C Torsion Calc -38.90(9), Rep -38.90(3) .... 3.00 su-Ratio O3 -NA1 -O3 -CO1 3.555 1.555 1.555 1.555
1 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 14 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 10 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion
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.