Acta Cryst.(2001). E57, m157±m158 DOI: 101107/S1600536801004391 Carlos A. L. Filgueiraset al. [V(C5H7O2)3]
m157
metal-organic papers
Acta Crystallographica Section E
Structure Reports
Online ISSN 1600-5368
a
-Form of tris(2,4-pentanedionato-
O
,
O
000)vanadium(III),
re-refinement against new intensity data
Carlos A. L. Filgueiras,aAdolfo
Horn Jr,aR. Alan Howie,b*
Janet M. S. Skakleband James L.
Wardella
aDepartamento de QuõÂmica InorgaÃnica, Instituto
de QuõÂmica, Universidad Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, andbDepartment of Chemistry,
University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
Correspondence e-mail: r.a.howie@abdn.ac.uk
Key indicators Single-crystal X-ray study T= 297 K
Mean(C±C) = 0.004 AÊ Rfactor = 0.044 wRfactor = 0.139
Data-to-parameter ratio = 25.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, V(MeCOCHCOMe)3 or [V(C5H7O2)3],
has been prepared by an unusual route. Its structure, con®rming its identity, is the same as that reported by Morosin & Montgomery [Acta Cryst. (1969), B25, 1354±1359] but enhanced in precision.
Comment
There are at least two previous reports of the preparation of the title compound, (I), which is also known as tris(acetyl-acetonato)vanadium(III). Grdenic & Korper-Colig (1964) prepared it by reaction of VO(acac)2 with Zn and
2,4-pentanedione (Hacac). It has also been obtained (Morosin & Montgomery, 1969) by the reaction of V2(SO4)3(obtained by
the electrolytic reduction of VOSO4) with Hacac in sodium
carbonate solution. Morosin & Montgomery described two crystalline forms of the material, a monoclinicform [refcode in Cambridge Structural Database (Allen & Kennard, 1993): VAACAC01], and the orthorhombic form (VAACAC) whose stucture was determined and re®ned on the basis of 3061 re¯ections with 1361 classed as observed [I> 3(I)]. The improved precision of the re-re®nement of the form (I) presented here is attributed to a more extensive and better quality set of intensity data (see Tables) in conjunction with the use of up-to-date software (SHELXL97; Sheldrick, 1997).
Fig. 1 shows the molecule and atom labelling scheme [identical to that used by Morosin & Montgomery (1969)] and Table 1 compares selected bond distances and angles between their determination and this work.
Experimental
Compound (I) was obtained from VO(acac)2(0.400 g, 1.50 mmol) and a slight excess (ca 1.75 mmol) of K[SnPh3] prepared from Ph3SnH and KH, in tetrahydrofuran solution under an argon atmo-sphere. The deep-purple solution was stirred at room temperature for 1 h, concentrated, hexane added, and the mixture left in a freezer for 3 d. After ®ltering off an amorphous brown precipitate, the solution was left for a further period after which dark-orange brown crystals of (I) were deposited and collected [m.p. 460±461 K; literature 459± 462 K (Morosin & Montgomery, 1969)].
Crystal data [V(C5H7O2)3]
Mr= 348.26 Orthorhombic,Pcab a= 15.4466 (7) AÊ
b= 16.6228 (8) AÊ
c= 13.5016 (6) AÊ
V= 3466.7 (3) AÊ3
Z= 8
Dx= 1.334 Mg mÿ3
Dm= 1.33 Mg mÿ3
Dmmeasured by ¯otation in CCl4/ EtOH (Morosin & Montgomery, 1969)
MoKradiation Cell parameters from 4494
re¯ections = 2.4±26.4
= 0.60 mmÿ1
T= 297 (2) K
Block, dark orange±brown 0.300.200.10 mm
Data collection
Bruker SMART 1000 area-detector diffractometer
'and!scans
Absorption correction: multi-scan (SADABS; Bruker, 1999)
Tmin= 0.445,Tmax= 0.928 28 129 measured re¯ections 5155 independent re¯ections
2251 re¯ections withI> 2(I)
Rint= 0.055 max= 31.0
h=ÿ22!14
k=ÿ23!24
l=ÿ17!18 Intensity decay: none
Re®nement Re®nement onF2
R[F2> 2(F2)] = 0.044
wR(F2) = 0.139
S= 0.94 5155 re¯ections 205 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0658P)2] whereP= (Fo2+ 2Fc2)/3 (/)max= 0.003
max= 0.29 e AÊÿ3 min=ÿ0.56 e AÊÿ3
Table 1
Comparison table of selected bond distances (AÊ) and angles ().
VAACAC This work
min. max. min. max.
VÐO 1.967 (8) 1.995 (8) 1.9688 (17) 1.9912 (18)
CÐO 1.235 (14) 1.268 (14) 1.257 (3) 1.268 (3)
endo-CÐC 1.376 (19) 1.408 (19) 1.363 (4) 1.390 (4)
CÐMe 1.497 (21) 1.528 (21) 1.497 (4) 1.516 (3)
Ligand bite 87.5 (6) 88.4 (6) 87.23 (8) 88.18 (7)
Re®nement was started on the basis of coordinates for non-H atoms extracted from the Cambridge Structural Database (Allen & Kennard, 1993) (VAACAC; Morosin & Montgomery, 1969) by means of the EPSRC's chemical database service at Daresbury (Fletcheret al., 1996). The non-standard space group setting and atom labels of the original determination were retained, but the cell dimensions were adjusted appropriately for the new intensity data. In the ®nal stages, H atoms were placed in calculated positions (CÐH = 0.96 and 0.93 AÊ for methyl and alkene H atoms, respectively) and re®ned in a riding-model approximation. Methyl groups were treated as rigid bodies. The incompleteness (92.95% complete) of the intensity data available for this re-re®nement is due to the presence of a few defective frames in the raw intensity data.
Data collection:SMART(Bruker, 1999); cell re®nement:SAINT
(Bruker, 1999); data reduction: SAINT; program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEP-3 (Farrugia, 1997); software used to prepare material for publication:SHELXL97.
We wish to acknowledge the use of the EPSRC's Chemical Database Service at Daresbury.
References
Allen, F. R. & Kennard, O. (1993).Chem. Des. Autom. News,8, 1, 31±37. Bruker (1999).SADABS,SMARTandSAINT. Bruker AXS Inc., Madison,
Wisconsin, USA.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.
Fletcher, D. A., McMeekin, R. F. & Parkin, D. (1996).J. Chem. Inf. Comput. Sci.36, 746±749.
Grdenic, D. & Korper-Colig, B. (1964).Inorg. Chem.3, 1328±1329. Morosin, B. & Montgomery, H. (1969).Acta Cryst.B25, 1354±1359. Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Figure 1
supporting information
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Acta Cryst. (2001). E57, m157–m158
supporting information
Acta Cryst. (2001). E57, m157–m158 [doi:10.1107/S1600536801004391]
α-Form of tris(2,4-pentanedionato-
O
,
O
′
)vanadium(III), re-refinement against
new intensity data
Carlos A. L. Filgueiras, Adolfo Horn, R. Alan Howie, Janet M. S. Skakle and James L. Wardell
S1. Comment
There are at least two previous reports of the preparation of the title compound, (I), which is also known as tris(acetyl-acetonato)vanadium(III). Grdenic & Korper-Colig (1964) prepared it by reaction of VO(acac)2 with Zn and
2,4-pentane-dione (Hacac). It has also been obtained (Morosin & Montgomery, 1969) by the reaction of V2(SO4)3 (obtained by the
electrolytic reduction of VOSO4) with Hacac in sodium carbonate solution. Morosin & Montgomery described two
crystalline forms of the material, a monoclinic β form [REFCODE in Cambridge Structural Database (Allen & Kennard, 1993): VAACAC01], and the orthorhombic α form (VAACAC) whose stucture was determined and refined on the basis of 3061 reflections with 1361 classed as observed [I>3σ(I)]. The improved precision of the rerefinement of the α form (I) presented here is attributed to a more extensive and better quality set of intensity data (see Tables) in conjunction with the use of up-to-date software (SHELXL97; Sheldrick, 1997).
Fig. 1 shows the molecule and atom labelling scheme [identical to that used by Morosin & Montgomery (1969)] and Table 1 compares selected bond distances and angles between their determination and this work.
S2. Experimental
Compound (I) was obtained from VO(acac)2 (0.400 g, 1.50 mmol) and a slight excess (ca 1.75 mmol) of K[SnPh3]
prepared from Ph3SnH and KH, in tetrahydrofuran solution under an argon atmosphere. The deep-purple solution was
stirred at room temperature for 1 h, concentrated, hexane added, and the mixture left in a freezer for 3 d. After filtering off an amorphous brown precipitate, the solution was left for a further period after which dark-orange brown crystals of (I) were deposited and collected [m. p. 460–461 K; literature 459–462 K (Morosin & Montgomery, 1969)].
S3. Refinement
Refinement was started on the basis of coordinates for non-H atoms extracted from the Cambridge Structural Database (Allen & Kennard, 1993) (VAACAC: Morosin & Montgomery, 1969) by means of the EPSRC's chemical database service at Daresbury (Fletcher et al., 1996). The non-standard space group setting and atom labels of the original determination were retained, but the cell dimensions were adjusted appropriately for the new intensity data. In the final stages, H atoms were placed in calculated positions (C—H = 0.96 and 0.93 Å for methyl and alkene H atoms,
respectively) and refined in a riding-model approximation. Methyl groups were treated as rigid bodies. The
Figure 1
The molecule of (I) showing the labelling scheme. Non-H atoms are shown as 50% probability ellipsoids. H atoms have been omitted for clarity.
Tris(2,4-pentanedionato-O,O′)-vanadium(III) (alpha form)
Crystal data
[V(C5H7O2)3] Mr = 348.26
Orthorhombic, Pcab a = 15.4466 (7) Å
b = 16.6228 (8) Å
c = 13.5016 (6) Å
V = 3466.7 (3) Å3 Z = 8
F(000) = 1456
Dx = 1.334 Mg m−3 Dm = 1.33 Mg m−3
Dm measured by flotation in CCl4/EtOH
(Morosin & Montgomery, 1969) Melting point = 460–461 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4494 reflections
θ = 2.4–26.4°
µ = 0.60 mm−1 T = 297 K
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Acta Cryst. (2001). E57, m157–m158
Data collection
Bruker SMART 1000 area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 1999)
Tmin = 0.445, Tmax = 0.928
28129 measured reflections 5155 independent reflections 2251 reflections with I > 2σ(I)
Rint = 0.055
θmax = 31.0°, θmin = 2.3°
h = −22→14
k = −23→24
l = −17→18
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.044 wR(F2) = 0.139 S = 0.94 5155 reflections 205 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0658P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.003
Δρmax = 0.29 e Å−3
Δρmin = −0.56 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. H in calculated positions and refined with a riding model.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
C1 0.0027 (2) 0.35220 (15) 0.33680 (19) 0.0682 (7) C10 −0.0267 (3) 0.40889 (19) 0.4181 (2) 0.1098 (13)
H10A −0.0192 0.3834 0.4813 0.165*
H10B −0.0867 0.4219 0.4087 0.165*
H10C 0.0072 0.4573 0.4157 0.165*
C12 −0.04869 (19) 0.33732 (18) 0.2556 (2) 0.0772 (9)
H12 −0.1024 0.3626 0.2533 0.093*
C2 −0.02683 (18) 0.28758 (18) 0.17693 (19) 0.0631 (7) C20 −0.08692 (19) 0.2776 (2) 0.0909 (2) 0.0928 (11)
H20A −0.0720 0.3155 0.0400 0.139*
H20B −0.1454 0.2869 0.1121 0.139*
H20C −0.0819 0.2239 0.0652 0.139*
C3 0.09410 (19) 0.07824 (17) 0.3143 (2) 0.0713 (8) C30 0.0465 (3) 0.0223 (2) 0.3825 (3) 0.1097 (13)
H30B 0.0842 −0.0207 0.4021 0.165*
H30C −0.0031 0.0006 0.3489 0.165*
C34 0.1382 (2) 0.04789 (18) 0.2328 (2) 0.0874 (10)
H34 0.1323 −0.0067 0.2191 0.105*
C4 0.1899 (2) 0.09232 (18) 0.1710 (2) 0.0687 (8) C40 0.2398 (2) 0.0525 (2) 0.0882 (2) 0.1090 (12)
H40A 0.2351 0.0843 0.0292 0.163*
H40B 0.2165 −0.0001 0.0762 0.163*
H40C 0.2996 0.0479 0.1067 0.163*
C5 0.30280 (18) 0.29429 (18) 0.36737 (18) 0.0641 (7) C50 0.3605 (2) 0.2859 (2) 0.4569 (2) 0.0983 (11)
H50A 0.3440 0.3249 0.5059 0.147*
H50B 0.4196 0.2948 0.4378 0.147*
H50C 0.3546 0.2328 0.4839 0.147*
C56 0.3225 (2) 0.34965 (19) 0.2937 (2) 0.0848 (9)
H56 0.3735 0.3789 0.3006 0.102*
C6 0.2732 (2) 0.36462 (16) 0.2120 (2) 0.0715 (8) C60 0.3030 (3) 0.4242 (2) 0.1347 (3) 0.1221 (15)
H60A 0.2960 0.4012 0.0699 0.183*
H60B 0.3629 0.4368 0.1454 0.183*
H60C 0.2691 0.4724 0.1395 0.183*
O1 0.07705 (12) 0.32206 (10) 0.35069 (12) 0.0639 (5) O2 0.04379 (11) 0.24907 (11) 0.17215 (12) 0.0639 (5) O3 0.09151 (13) 0.15212 (11) 0.33728 (13) 0.0676 (5) O4 0.20162 (11) 0.16752 (11) 0.17940 (12) 0.0628 (5) O5 0.23767 (12) 0.24903 (11) 0.36504 (11) 0.0629 (4) O6 0.20096 (12) 0.33224 (10) 0.19387 (12) 0.0627 (5) V1 0.14153 (3) 0.24589 (2) 0.26686 (3) 0.04841 (14)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Acta Cryst. (2001). E57, m157–m158
O2 0.0572 (10) 0.0844 (13) 0.0502 (10) 0.0034 (10) 0.0023 (7) −0.0079 (9) O3 0.0838 (13) 0.0585 (11) 0.0606 (11) −0.0119 (10) 0.0159 (9) 0.0029 (9) O4 0.0683 (12) 0.0633 (11) 0.0568 (10) 0.0062 (9) 0.0126 (8) −0.0058 (9) O5 0.0677 (11) 0.0739 (11) 0.0471 (9) −0.0018 (10) −0.0016 (8) 0.0092 (9) O6 0.0695 (12) 0.0643 (11) 0.0545 (9) −0.0074 (9) −0.0014 (9) 0.0149 (9) V1 0.0532 (2) 0.0484 (2) 0.0436 (2) −0.0010 (2) 0.00513 (16) −0.00006 (18)
Geometric parameters (Å, º)
C1—O1 1.267 (3) C40—H40A 0.9600
C1—C12 1.376 (4) C40—H40B 0.9600
C1—C10 1.516 (3) C40—H40C 0.9600
C10—H10A 0.9600 C5—O5 1.257 (3)
C10—H10B 0.9600 C5—C56 1.389 (4)
C10—H10C 0.9600 C5—C50 1.508 (4)
C12—C2 1.388 (4) C50—H50A 0.9600
C12—H12 0.9300 C50—H50B 0.9600
C2—O2 1.266 (3) C50—H50C 0.9600
C2—C20 1.497 (4) C56—C6 1.363 (4)
C20—H20A 0.9600 C56—H56 0.9300
C20—H20B 0.9600 C6—O6 1.263 (3)
C20—H20C 0.9600 C6—C60 1.511 (4)
C3—O3 1.267 (3) C60—H60A 0.9600
C3—C34 1.390 (4) C60—H60B 0.9600
C3—C30 1.501 (4) C60—H60C 0.9600
C30—H30A 0.9600 O1—V1 1.9688 (17)
C30—H30B 0.9600 O2—V1 1.9793 (17)
C30—H30C 0.9600 O3—V1 1.9825 (17)
C34—C4 1.370 (4) O4—V1 1.9881 (16)
C34—H34 0.9300 O5—V1 1.9912 (18)
C4—O4 1.268 (3) O6—V1 1.9683 (17)
C4—C40 1.510 (4)
O1—C1—C12 124.7 (2) O5—C5—C56 123.7 (3) O1—C1—C10 114.2 (3) O5—C5—C50 116.0 (3) C12—C1—C10 121.0 (3) C56—C5—C50 120.4 (3)
C1—C10—H10A 109.5 C5—C50—H50A 109.5
C1—C10—H10B 109.5 C5—C50—H50B 109.5
H10A—C10—H10B 109.5 H50A—C50—H50B 109.5
C1—C10—H10C 109.5 C5—C50—H50C 109.5
H10A—C10—H10C 109.5 H50A—C50—H50C 109.5 H10B—C10—H10C 109.5 H50B—C50—H50C 109.5 C1—C12—C2 125.2 (3) C6—C56—C5 125.3 (3)
C1—C12—H12 117.4 C6—C56—H56 117.3
C2—C12—H12 117.4 C5—C56—H56 117.3
C2—C20—H20A 109.5 C6—C60—H60A 109.5
C2—C20—H20B 109.5 C6—C60—H60B 109.5
H20A—C20—H20B 109.5 H60A—C60—H60B 109.5
C2—C20—H20C 109.5 C6—C60—H60C 109.5
H20A—C20—H20C 109.5 H60A—C60—H60C 109.5 H20B—C20—H20C 109.5 H60B—C60—H60C 109.5 O3—C3—C34 124.1 (3) C1—O1—V1 128.90 (17) O3—C3—C30 115.7 (3) C2—O2—V1 129.61 (17) C34—C3—C30 120.1 (3) C3—O3—V1 129.20 (18)
C3—C30—H30A 109.5 C4—O4—V1 129.24 (18)
C3—C30—H30B 109.5 C5—O5—V1 129.00 (17)
H30A—C30—H30B 109.5 C6—O6—V1 128.74 (17)
C3—C30—H30C 109.5 O6—V1—O1 93.14 (8)
H30A—C30—H30C 109.5 O6—V1—O2 90.73 (7) H30B—C30—H30C 109.5 O1—V1—O2 88.18 (7) C4—C34—C3 124.9 (3) O6—V1—O3 174.40 (8)
C4—C34—H34 117.5 O1—V1—O3 91.87 (8)
C3—C34—H34 117.5 O2—V1—O3 91.92 (8)
O4—C4—C34 124.0 (3) O6—V1—O4 87.87 (7) O4—C4—C40 115.2 (3) O1—V1—O4 177.41 (8) C34—C4—C40 120.7 (3) O2—V1—O4 89.42 (7)
C4—C40—H40A 109.5 O3—V1—O4 87.23 (8)
C4—C40—H40B 109.5 O6—V1—O5 88.07 (7)
H40A—C40—H40B 109.5 O1—V1—O5 88.73 (7)
C4—C40—H40C 109.5 O2—V1—O5 176.62 (7)
H40A—C40—H40C 109.5 O3—V1—O5 89.54 (8) H40B—C40—H40C 109.5 O4—V1—O5 93.69 (7)
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Acta Cryst. (2001). E57, m157–m158
