Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044340/bt2505sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044340/bt2505Isup2.hkl |
CCDC reference: 667100
The synthesis of the title compound was adapted from Watson & Lin (1966). 0.2 ml (1.2 mmol) of the β-diketonate ligand was added to a solution of 0.11 g CoCl2·6H2O (0.5 mmol) in 100 ml de-ionized water. Diluted 1:1 (v/v) NH4OH was added dropwise to the solution until no additional precipitate formed. The solution was stirred for 2 h and the precipitate was isolated by filtration. The desired product was separated from any impurities by extraction with toluene and filtration. Toluene was removed in vacuo and the product was subsequently re-crystallized from methanol.
The hydroxyl H atom was located in a difference density Fourier map. The O—H distance was restrained to 0.84 (2) Å. The other H atoms were placed in calculated positions with C—H distances of 0.980 (methyl) and 0.950 Å (CH). The methyl and hydroxyl H's were refined with an isotropic displacement parameter Uiso of 1.5 times Ueq of the adjacent carbon or oxygen atom, and the C—H hydrogen atom with Uiso = 1.2 Ueq(C). Methyl hydrogen atoms were allowed to rotate to best fit the experimental electron density.
β-Diketones such as acetylacetonate (acac), and the metal complexes of their anions, have been used as in a variety of areas including catalysis in sol-gel synthesis (Mayo et al., 2000), carbon nanotube formation (Katok et al., 2006) and also as precursors for metal organic chemical vapor deposition (MOCVD) (Bessergenev, 2004). The synthesis of metal-β-diketonates has also been studied thoroughly (Skopenko et al., 2004). We are especially interested in fluorinated metal-β-diketonates, which, due to their increased volatility, are ideally suited as precursors for vapor deposition processes (Fahlmen, 2006) and allow for the detailed study of gas phase metal and ligand association reactions by mass spectrometry (Majer & Perry, 1969; Schildcrout, 1976). Varying the substituent identity and degree of fluorination are some of the routes used to tune the properties of MOCVD precursors and are currently under investigation in the gas phase. In the course of these studies the title compound was prepared by reaction of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (tftm) with CoCl2 in a basic aqueous medium and subsequent recrystallization from methanol.
The β-diketonate ligand, as well as the methanol substituents in this crystal structure, are arranged in a trans geometry with the cobalt atom being localized on a crystallographic inversion center (Fig. 1). The CoO4 plane, formed by the oxygen atoms of the chelating ligands and the Co atom, is planar. The Co—O bond distances and angles are within the expected range, with the tftm bite angle being the smallest at 89.82 (5)° and Co—O bonds ranging between 2.0338 (14) and 2.0388 (13) Å. The tftm ligands themselves are also nearly planar with an r.m.s. deviation from the mean plane formed by the two oxygen and five carbon atoms of the two ligands of only 0.0729. With respect to the CoO4 plane however, the tftm ligands are tilted by 17.41 (7)° which compares well to values found for other similar Co compounds such as Co(acac)2(H2O)2 and Co(acac)2(MeOH)2, with angles of 16.70° and 9.71° respectively (Bullen, 1959; Werndrup & Kessler, 2001).
The hydroxyl groups of the methanol ligands are involved in O—H···O hydrogen bonds towards O1i of a tftm ligand in a neighboring molecule (symmetry operator i: x - 1, y, z). Each molecule functions as both H donor and acceptor towards each two neighboring molecules. Chains of H-bound molecules extend along the a axis due to this network of H-bonds (Fig. 2)·Also, each two of the O—H···O bonds are related to each other by an inversion center located between two neighboring molecules, resulting in an R22(8) graph set motif (Bernstein et al., 1995).
For information regarding the synthesis of various metal-β-diketonates see Skopenko et al. (2004) and Watson & Lin (1966). For similar metal–acetylacetonates refer to Bullen (1959) and Werndrup & Kessler (2001). Varying uses of metal-β-diketonates can be found in Mayo et al. (2000), Katok et al. (2006), Bessergenev (2004) and Fahlmen (2006). The paper by Bernstein et al. (1995) describes graph-set motifs. For related mass spectrometry work see Majer & Perry (1969) and Schildcrout (1976).
Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2003).
[Co(C8H10F3O2)2(CH4O)2] | Z = 1 |
Mr = 513.33 | F(000) = 265 |
Triclinic, P1 | Dx = 1.546 Mg m−3 |
a = 5.4390 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.7181 (11) Å | Cell parameters from 3517 reflections |
c = 12.0169 (15) Å | θ = 2.4–30.4° |
α = 78.835 (2)° | µ = 0.86 mm−1 |
β = 80.571 (2)° | T = 100 K |
γ = 87.946 (2)° | Plate, red |
V = 551.47 (12) Å3 | 0.49 × 0.23 × 0.08 mm |
Bruker SMART APEX CCD diffractometer | 2637 independent reflections |
Radiation source: fine-focus sealed tube | 2380 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | h = −7→7 |
Tmin = 0.572, Tmax = 0.934 | k = −11→11 |
4542 measured reflections | l = −15→15 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0734P)2 + 0.1036P] where P = (Fo2 + 2Fc2)/3 |
2637 reflections | (Δ/σ)max < 0.001 |
149 parameters | Δρmax = 0.89 e Å−3 |
1 restraint | Δρmin = −0.79 e Å−3 |
[Co(C8H10F3O2)2(CH4O)2] | γ = 87.946 (2)° |
Mr = 513.33 | V = 551.47 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.4390 (7) Å | Mo Kα radiation |
b = 8.7181 (11) Å | µ = 0.86 mm−1 |
c = 12.0169 (15) Å | T = 100 K |
α = 78.835 (2)° | 0.49 × 0.23 × 0.08 mm |
β = 80.571 (2)° |
Bruker SMART APEX CCD diffractometer | 2637 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-Plus; Bruker, 2003) | 2380 reflections with I > 2σ(I) |
Tmin = 0.572, Tmax = 0.934 | Rint = 0.021 |
4542 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 1 restraint |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.89 e Å−3 |
2637 reflections | Δρmin = −0.79 e Å−3 |
149 parameters |
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 | ||
C1 | 0.6715 (4) | 1.2223 (2) | 0.26390 (17) | 0.0224 (4) | |
C2 | 0.5746 (3) | 1.0953 (2) | 0.21029 (16) | 0.0187 (4) | |
C3 | 0.4063 (4) | 0.9910 (2) | 0.27916 (17) | 0.0209 (4) | |
H3 | 0.3564 | 1.0027 | 0.3566 | 0.025* | |
C4 | 0.3002 (3) | 0.8652 (2) | 0.24211 (17) | 0.0190 (4) | |
C5 | 0.1482 (3) | 0.7401 (2) | 0.33239 (17) | 0.0198 (4) | |
C6 | −0.0258 (4) | 0.8130 (2) | 0.42237 (18) | 0.0246 (4) | |
H6A | −0.1322 | 0.8919 | 0.3836 | 0.037* | |
H6B | 0.0738 | 0.8624 | 0.4666 | 0.037* | |
H6C | −0.1302 | 0.7313 | 0.4744 | 0.037* | |
C7 | −0.0022 (4) | 0.6457 (3) | 0.27254 (19) | 0.0277 (4) | |
H7A | 0.1114 | 0.5960 | 0.2178 | 0.042* | |
H7B | −0.1169 | 0.7155 | 0.2314 | 0.042* | |
H7C | −0.0977 | 0.5652 | 0.3300 | 0.042* | |
C8 | 0.3351 (4) | 0.6316 (2) | 0.39236 (19) | 0.0255 (4) | |
H8A | 0.2446 | 0.5499 | 0.4508 | 0.038* | |
H8B | 0.4352 | 0.6923 | 0.4290 | 0.038* | |
H8C | 0.4449 | 0.5832 | 0.3355 | 0.038* | |
C9 | 0.2186 (4) | 1.3202 (2) | 0.0062 (2) | 0.0283 (4) | |
H9A | 0.2177 | 1.3465 | 0.0820 | 0.042* | |
H9B | 0.0805 | 1.3743 | −0.0284 | 0.042* | |
H9C | 0.3768 | 1.3530 | −0.0433 | 0.042* | |
Co1 | 0.5000 | 1.0000 | 0.0000 | 0.01756 (13) | |
F1 | 0.9170 (2) | 1.20843 (16) | 0.26299 (12) | 0.0330 (3) | |
F2 | 0.6323 (3) | 1.36435 (15) | 0.20402 (13) | 0.0374 (3) | |
F3 | 0.5676 (3) | 1.22055 (17) | 0.37246 (12) | 0.0377 (4) | |
O1 | 0.6700 (2) | 1.10554 (15) | 0.10421 (12) | 0.0201 (3) | |
O2 | 0.3314 (3) | 0.84840 (16) | 0.13993 (12) | 0.0208 (3) | |
O3 | 0.1904 (3) | 1.15484 (17) | 0.01845 (13) | 0.0244 (3) | |
H3A | 0.042 (4) | 1.134 (3) | 0.049 (2) | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0234 (9) | 0.0219 (9) | 0.0237 (10) | −0.0037 (7) | −0.0007 (7) | −0.0108 (8) |
C2 | 0.0193 (9) | 0.0174 (9) | 0.0216 (9) | −0.0001 (7) | −0.0033 (7) | −0.0091 (7) |
C3 | 0.0212 (9) | 0.0228 (9) | 0.0202 (9) | −0.0023 (7) | −0.0007 (7) | −0.0094 (7) |
C4 | 0.0170 (8) | 0.0184 (9) | 0.0222 (9) | 0.0001 (7) | −0.0012 (7) | −0.0073 (7) |
C5 | 0.0188 (9) | 0.0193 (9) | 0.0222 (9) | −0.0032 (7) | 0.0003 (7) | −0.0083 (7) |
C6 | 0.0220 (9) | 0.0249 (10) | 0.0253 (10) | −0.0023 (8) | 0.0040 (8) | −0.0064 (8) |
C7 | 0.0262 (10) | 0.0320 (11) | 0.0258 (10) | −0.0128 (8) | −0.0009 (8) | −0.0082 (8) |
C8 | 0.0242 (10) | 0.0216 (10) | 0.0293 (11) | −0.0016 (8) | −0.0014 (8) | −0.0039 (8) |
C9 | 0.0318 (11) | 0.0192 (10) | 0.0339 (11) | 0.0005 (8) | −0.0016 (9) | −0.0087 (8) |
Co1 | 0.0185 (2) | 0.0168 (2) | 0.0188 (2) | −0.00344 (13) | −0.00057 (13) | −0.00835 (14) |
F1 | 0.0239 (6) | 0.0389 (7) | 0.0430 (8) | −0.0064 (5) | −0.0069 (5) | −0.0221 (6) |
F2 | 0.0544 (9) | 0.0184 (6) | 0.0456 (8) | −0.0014 (6) | −0.0175 (7) | −0.0132 (6) |
F3 | 0.0436 (8) | 0.0443 (8) | 0.0287 (7) | −0.0183 (6) | 0.0080 (6) | −0.0242 (6) |
O1 | 0.0195 (6) | 0.0202 (7) | 0.0223 (7) | −0.0038 (5) | −0.0002 (5) | −0.0101 (5) |
O2 | 0.0228 (7) | 0.0193 (7) | 0.0214 (7) | −0.0041 (5) | 0.0003 (5) | −0.0091 (5) |
O3 | 0.0197 (7) | 0.0202 (7) | 0.0340 (8) | −0.0015 (5) | −0.0003 (6) | −0.0104 (6) |
C1—F3 | 1.332 (2) | C7—H7B | 0.9800 |
C1—F1 | 1.335 (2) | C7—H7C | 0.9800 |
C1—F2 | 1.336 (2) | C8—H8A | 0.9800 |
C1—C2 | 1.532 (3) | C8—H8B | 0.9800 |
C2—O1 | 1.282 (2) | C8—H8C | 0.9800 |
C2—C3 | 1.368 (3) | C9—O3 | 1.432 (2) |
C3—C4 | 1.432 (3) | C9—H9A | 0.9800 |
C3—H3 | 0.9500 | C9—H9B | 0.9800 |
C4—O2 | 1.248 (2) | C9—H9C | 0.9800 |
C4—C5 | 1.537 (3) | Co1—O2 | 2.0338 (14) |
C5—C7 | 1.528 (3) | Co1—O2i | 2.0339 (14) |
C5—C8 | 1.535 (3) | Co1—O1i | 2.0388 (13) |
C5—C6 | 1.535 (3) | Co1—O1 | 2.0388 (13) |
C6—H6A | 0.9800 | Co1—O3 | 2.1301 (15) |
C6—H6B | 0.9800 | Co1—O3i | 2.1302 (15) |
C6—H6C | 0.9800 | O3—H3A | 0.840 (17) |
C7—H7A | 0.9800 | ||
F3—C1—F1 | 106.65 (17) | C5—C8—H8A | 109.5 |
F3—C1—F2 | 107.19 (17) | C5—C8—H8B | 109.5 |
F1—C1—F2 | 106.60 (16) | H8A—C8—H8B | 109.5 |
F3—C1—C2 | 114.14 (16) | C5—C8—H8C | 109.5 |
F1—C1—C2 | 111.10 (16) | H8A—C8—H8C | 109.5 |
F2—C1—C2 | 110.78 (16) | H8B—C8—H8C | 109.5 |
O1—C2—C3 | 130.15 (17) | O3—C9—H9A | 109.5 |
O1—C2—C1 | 112.25 (16) | O3—C9—H9B | 109.5 |
C3—C2—C1 | 117.60 (17) | H9A—C9—H9B | 109.5 |
C2—C3—C4 | 124.26 (18) | O3—C9—H9C | 109.5 |
C2—C3—H3 | 117.9 | H9A—C9—H9C | 109.5 |
C4—C3—H3 | 117.9 | H9B—C9—H9C | 109.5 |
O2—C4—C3 | 123.37 (17) | O2—Co1—O2i | 180.00 (6) |
O2—C4—C5 | 117.62 (16) | O2—Co1—O1i | 90.18 (5) |
C3—C4—C5 | 118.97 (17) | O2i—Co1—O1i | 89.82 (5) |
C7—C5—C8 | 109.26 (17) | O2—Co1—O1 | 89.82 (5) |
C7—C5—C6 | 110.21 (16) | O2i—Co1—O1 | 90.18 (5) |
C8—C5—C6 | 109.09 (17) | O1i—Co1—O1 | 180.00 (6) |
C7—C5—C4 | 109.43 (16) | O2—Co1—O3 | 89.28 (6) |
C8—C5—C4 | 107.12 (15) | O2i—Co1—O3 | 90.72 (6) |
C6—C5—C4 | 111.66 (15) | O1i—Co1—O3 | 90.09 (6) |
C5—C6—H6A | 109.5 | O1—Co1—O3 | 89.91 (6) |
C5—C6—H6B | 109.5 | O2—Co1—O3i | 90.72 (6) |
H6A—C6—H6B | 109.5 | O2i—Co1—O3i | 89.28 (6) |
C5—C6—H6C | 109.5 | O1i—Co1—O3i | 89.91 (6) |
H6A—C6—H6C | 109.5 | O1—Co1—O3i | 90.09 (6) |
H6B—C6—H6C | 109.5 | O3—Co1—O3i | 179.999 (1) |
C5—C7—H7A | 109.5 | C2—O1—Co1 | 119.97 (12) |
C5—C7—H7B | 109.5 | C4—O2—Co1 | 127.11 (13) |
H7A—C7—H7B | 109.5 | C9—O3—Co1 | 122.65 (12) |
C5—C7—H7C | 109.5 | C9—O3—H3A | 107 (2) |
H7A—C7—H7C | 109.5 | Co1—O3—H3A | 129 (2) |
H7B—C7—H7C | 109.5 | ||
F3—C1—C2—O1 | 176.81 (17) | C3—C2—O1—Co1 | 19.4 (3) |
F1—C1—C2—O1 | −62.6 (2) | C1—C2—O1—Co1 | −160.77 (12) |
F2—C1—C2—O1 | 55.7 (2) | O2—Co1—O1—C2 | −23.55 (14) |
F3—C1—C2—C3 | −3.3 (3) | O2i—Co1—O1—C2 | 156.45 (14) |
F1—C1—C2—C3 | 117.3 (2) | O3—Co1—O1—C2 | 65.73 (14) |
F2—C1—C2—C3 | −124.4 (2) | O3i—Co1—O1—C2 | −114.27 (14) |
O1—C2—C3—C4 | 0.3 (3) | C3—C4—O2—Co1 | −7.2 (3) |
C1—C2—C3—C4 | −179.48 (18) | C5—C4—O2—Co1 | 175.20 (12) |
C2—C3—C4—O2 | −7.8 (3) | O1i—Co1—O2—C4 | −160.79 (16) |
C2—C3—C4—C5 | 169.72 (18) | O1—Co1—O2—C4 | 19.21 (16) |
O2—C4—C5—C7 | −17.5 (2) | O3—Co1—O2—C4 | −70.70 (16) |
C3—C4—C5—C7 | 164.78 (18) | O3i—Co1—O2—C4 | 109.30 (16) |
O2—C4—C5—C8 | 100.8 (2) | O2—Co1—O3—C9 | 137.10 (16) |
C3—C4—C5—C8 | −76.9 (2) | O2i—Co1—O3—C9 | −42.90 (16) |
O2—C4—C5—C6 | −139.84 (19) | O1i—Co1—O3—C9 | −132.72 (16) |
C3—C4—C5—C6 | 42.5 (2) | O1—Co1—O3—C9 | 47.28 (16) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1ii | 0.84 (2) | 2.03 (2) | 2.867 (2) | 172 (3) |
Symmetry code: (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C8H10F3O2)2(CH4O)2] |
Mr | 513.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 5.4390 (7), 8.7181 (11), 12.0169 (15) |
α, β, γ (°) | 78.835 (2), 80.571 (2), 87.946 (2) |
V (Å3) | 551.47 (12) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.49 × 0.23 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-Plus; Bruker, 2003) |
Tmin, Tmax | 0.572, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4542, 2637, 2380 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.114, 1.07 |
No. of reflections | 2637 |
No. of parameters | 149 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.89, −0.79 |
Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2003), SHELXTL (Bruker, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1i | 0.840 (17) | 2.032 (18) | 2.867 (2) | 172 (3) |
Symmetry code: (i) x−1, y, z. |
β-Diketones such as acetylacetonate (acac), and the metal complexes of their anions, have been used as in a variety of areas including catalysis in sol-gel synthesis (Mayo et al., 2000), carbon nanotube formation (Katok et al., 2006) and also as precursors for metal organic chemical vapor deposition (MOCVD) (Bessergenev, 2004). The synthesis of metal-β-diketonates has also been studied thoroughly (Skopenko et al., 2004). We are especially interested in fluorinated metal-β-diketonates, which, due to their increased volatility, are ideally suited as precursors for vapor deposition processes (Fahlmen, 2006) and allow for the detailed study of gas phase metal and ligand association reactions by mass spectrometry (Majer & Perry, 1969; Schildcrout, 1976). Varying the substituent identity and degree of fluorination are some of the routes used to tune the properties of MOCVD precursors and are currently under investigation in the gas phase. In the course of these studies the title compound was prepared by reaction of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (tftm) with CoCl2 in a basic aqueous medium and subsequent recrystallization from methanol.
The β-diketonate ligand, as well as the methanol substituents in this crystal structure, are arranged in a trans geometry with the cobalt atom being localized on a crystallographic inversion center (Fig. 1). The CoO4 plane, formed by the oxygen atoms of the chelating ligands and the Co atom, is planar. The Co—O bond distances and angles are within the expected range, with the tftm bite angle being the smallest at 89.82 (5)° and Co—O bonds ranging between 2.0338 (14) and 2.0388 (13) Å. The tftm ligands themselves are also nearly planar with an r.m.s. deviation from the mean plane formed by the two oxygen and five carbon atoms of the two ligands of only 0.0729. With respect to the CoO4 plane however, the tftm ligands are tilted by 17.41 (7)° which compares well to values found for other similar Co compounds such as Co(acac)2(H2O)2 and Co(acac)2(MeOH)2, with angles of 16.70° and 9.71° respectively (Bullen, 1959; Werndrup & Kessler, 2001).
The hydroxyl groups of the methanol ligands are involved in O—H···O hydrogen bonds towards O1i of a tftm ligand in a neighboring molecule (symmetry operator i: x - 1, y, z). Each molecule functions as both H donor and acceptor towards each two neighboring molecules. Chains of H-bound molecules extend along the a axis due to this network of H-bonds (Fig. 2)·Also, each two of the O—H···O bonds are related to each other by an inversion center located between two neighboring molecules, resulting in an R22(8) graph set motif (Bernstein et al., 1995).