supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2009). E65, m355-m356    [ doi:10.1107/S1600536809006059 ]

Poly[([mu]2-2-hydroxy-2-methylpropionato-[kappa]3O1,O2:O1')([mu]2-2-hydroxy-2-methylpropionato-[kappa]2O1:[kappa]O1')dioxidouranium(VI)]

T. Yoshimura, H. Kikunaga and A. Shinohara

Abstract top

In the title compound, [UO2(C4H7O3)2]n, the dioxouranium(VI) units are linked by 2-hydroxy-2-methylpropionate ligands into a honeycomb structure. The U atom is seven-coordinate in a pentagonal-bipyramidal geometry. The uncoordinated hydroxy groups of the 2-hydroxy-2-methylpropionate ions interact with the O atom of the uranyl and with the coordinated hydroxy group of an adjacent 2-hydroxy-2-methylpropionate ion through O-H...O hydrogen bonds.

Comment top

Structural chemistry of uranyl(VI) complexes with hydroxycarboxylate or alkoxycarboxylate has been extensively studied (Back et al. (2007); Bombieri et al.(1973, 1974); Jiang et al. (2002); Thuéry (2006, 2007a,b,c, 2008); Xie et al. (2003); Yokoyama et al.(1990)). The crystals of the title compound (I) suitable for single-crystal X-ray analysis were obtained by the reaction of bis(acetato)dioxouranium dihydrate with an excess amount of 2-hydroxy-2-methylpropionic acid in water. Herein, we report on the crystal structure of I. Uranium(VI) atom is seven-coordinate in a pentagonal-bipyramidal structure. The two oxygen atoms are located at the axial positions with nearly linear O(1)—U(1)—O(2) angle (178.3 (2)°). The equatorial positions are coordinated by five oxygen atoms of 2-hydroxy-2-methylpropionate (HIB) ligands. Two kinds of HIB ligands exist in the asymmetric unit. One of the HIB ligands links two uranium atoms by the carboxyl group. The other chelates one uranium atom through the hydroxy and carboxyl groups, moreover the carboxyl group bridges the neighboring uranium atom. As a result, a two-dimensional honeycomb structure is formed. The IR spectrum of I shows stretching bands of the carboxyl group of HIB at 1614 and 1561 cm-1.

Related literature top

For related structures, see: Back et al. (2007); Bombieri et al. (1973, 1974); Jiang et al. (2002); Thuéry (2006, 2007a,b,c, 2008); Xie et al. (2003); Yokoyama et al. (1990).

Experimental top

2-Hydroxy-2-methylpropionic acid (150 mg, 1.45 mmol) was added to a solution of bis(acetato)dioxouranium dihydrate (50 mg, 0.12 mmol) in 3 ml of water. The resulting yellow solution was left for several days at room temperature to give yellow crystals, which were filtered off, washed with a small amount of water, and then dried in air.

Refinement top

H atoms bonded to C and O atoms were placed at calculated positions [C—H = 0.96 and O—H = 0.82] and refined as riding with Uiso(H) = 1.0 Ueq(C,O). The deepest hole is 0.68 Å from atom U(1).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: TEXSAN (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: TEXSAN (Rigaku/MSC, 2004).

Figures top
[Figure 1] Fig. 1. The assymmetric unit of I, with the atom-numbering scheme and displacement ellipsoids drawn at 50% probability level. Hydrogen atoms are omitted for clarity.
[Figure 2] Fig. 2. Fragment of the polymeric structure. Hydrogen atoms are omitted for clarity.
[Figure 3] Fig. 3. View of the polymeric structure. Hydrogen atoms are omitted for clarity.
Poly[(µ2-2-hydroxy-2-methylpropionato- κ3O1,O2:O1')(µ2-2-hydroxy-2- methylpropionato-κ2O1:κO1')dioxidouranium(VI)] top
Crystal data top
[U(C4H7O3)2O2]F(000) = 872.00
Mr = 476.22Dx = 2.454 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ynCell parameters from 8716 reflections
a = 9.009 (2) Åθ = 3.0–27.5°
b = 8.237 (2) ŵ = 12.62 mm−1
c = 17.552 (6) ÅT = 200 K
β = 98.246 (9)°Platelet, yellow
V = 1289.0 (6) Å30.20 × 0.11 × 0.03 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID Imaging Plate
diffractometer		2949 independent reflections
Radiation source: fine-focus sealed tube2547 reflections with I > 2σ(I)
graphiteRint = 0.050
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = 12→11
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −9→10
Tmin = 0.233, Tmax = 0.685l = −22→22
11887 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.100 w = 1/[σ2(Fo2) + (0.079P)2 + 5.354P]
where P = (Fo2 + 2Fc2)/3
S = 0.86(Δ/σ)max = 0.001
2949 reflectionsΔρmax = 0.99 e Å−3
160 parametersΔρmin = −2.15 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
[U(C4H7O3)2O2]V = 1289.0 (6) Å3
Mr = 476.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.009 (2) ŵ = 12.62 mm−1
b = 8.237 (2) ÅT = 200 K
c = 17.552 (6) Å0.20 × 0.11 × 0.03 mm
β = 98.246 (9)°
Data collection top
Rigaku R-AXIS RAPID Imaging Plate
diffractometer		2949 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2547 reflections with I > 2σ(I)
Tmin = 0.233, Tmax = 0.685Rint = 0.050
11887 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.100Δρmax = 0.99 e Å−3
S = 0.86Δρmin = −2.15 e Å−3
2949 reflectionsAbsolute structure: ?
160 parametersFlack parameter: ?
? restraintsRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
U(1)0.63772 (2)0.19668 (3)0.62425 (1)0.0180 (1)
O(1)0.7538 (6)0.3101 (5)0.5695 (3)0.028 (1)
O(2)0.5188 (6)0.0891 (6)0.6778 (3)0.032 (1)
O(3)0.4753 (5)0.4342 (5)0.6250 (3)0.026 (1)
O(4)0.6920 (5)0.3869 (6)0.7286 (3)0.029 (1)
O(5)0.6435 (5)0.6018 (6)0.7991 (3)0.0252 (10)
O(6)0.2338 (5)0.4208 (5)0.5248 (3)0.0241 (10)
O(7)0.7009 (6)−0.0415 (6)0.5630 (3)0.034 (1)
O(8)0.4514 (6)0.1975 (5)0.5169 (3)0.030 (1)
C(1)0.6115 (7)0.5015 (8)0.7435 (3)0.022 (1)
C(2)0.4611 (7)0.5295 (8)0.6929 (4)0.021 (1)
C(3)0.3351 (8)0.463 (1)0.7324 (4)0.036 (2)
C(4)0.4392 (10)0.7064 (7)0.6704 (5)0.030 (2)
C(5)0.3241 (7)0.1601 (8)0.4820 (4)0.020 (1)
C(6)0.1889 (7)0.2626 (8)0.4949 (4)0.021 (1)
C(7)0.1191 (10)0.1790 (9)0.5588 (5)0.039 (2)
C(8)0.0781 (10)0.280 (1)0.4211 (5)0.038 (2)
H(1)0.32770.52530.77790.0356*
H(2)0.24230.46980.69800.0356*
H(3)0.35550.35160.74620.0356*
H(4)0.43880.77110.71590.0297*
H(5)0.34540.71920.63740.0297*
H(6)0.51960.74090.64380.0297*
H(7)0.03210.23840.56840.0386*
H(8)0.19080.17570.60480.0386*
H(9)0.09070.07030.54320.0386*
H(10)−0.01000.33590.43220.0383*
H(11)0.05070.17460.40070.0383*
H(12)0.12370.34130.38410.0383*
H(13)0.42100.47240.58780.0255*
H(14)0.21780.48830.49020.0241*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
U(1)0.0192 (2)0.0158 (2)0.0185 (2)0.00083 (8)0.0005 (1)−0.00114 (8)
O(1)0.022 (3)0.030 (3)0.032 (3)0.007 (2)0.004 (2)0.007 (2)
O(2)0.029 (3)0.025 (2)0.044 (3)0.005 (2)0.009 (2)0.007 (2)
O(3)0.034 (3)0.022 (2)0.017 (2)0.008 (2)−0.008 (2)−0.005 (2)
O(4)0.029 (3)0.025 (2)0.030 (2)0.007 (2)−0.004 (2)−0.006 (2)
O(5)0.028 (2)0.027 (2)0.020 (2)−0.008 (2)0.001 (2)−0.010 (2)
O(6)0.030 (2)0.016 (2)0.023 (2)0.002 (2)−0.005 (2)−0.001 (2)
O(7)0.032 (3)0.027 (3)0.038 (3)0.009 (2)−0.008 (2)−0.018 (2)
O(8)0.023 (3)0.033 (3)0.033 (3)0.005 (2)−0.002 (2)−0.008 (2)
C(1)0.023 (3)0.024 (3)0.017 (3)−0.007 (3)0.000 (2)−0.001 (3)
C(2)0.027 (3)0.016 (3)0.020 (3)0.000 (3)0.000 (2)−0.008 (2)
C(3)0.032 (4)0.042 (4)0.035 (4)−0.012 (3)0.009 (3)−0.013 (3)
C(4)0.040 (4)0.015 (3)0.032 (4)0.004 (3)−0.001 (3)−0.004 (3)
C(5)0.022 (3)0.019 (3)0.020 (3)0.009 (3)0.001 (2)0.002 (3)
C(6)0.021 (3)0.018 (3)0.022 (3)0.013 (3)−0.003 (2)0.003 (3)
C(7)0.035 (4)0.036 (4)0.048 (5)−0.015 (3)0.017 (4)−0.005 (3)
C(8)0.035 (4)0.035 (4)0.040 (4)0.014 (3)−0.012 (4)−0.004 (4)
Geometric parameters (Å, °) top
U(1)—O(1)1.783 (5)C(2)—C(4)1.514 (9)
U(1)—O(2)1.762 (6)C(3)—H(1)0.960
U(1)—O(3)2.444 (5)C(3)—H(2)0.960
U(1)—O(4)2.407 (5)C(3)—H(3)0.960
U(1)—O(5)i2.355 (4)C(4)—H(4)0.960
U(1)—O(7)2.346 (5)C(4)—H(5)0.960
U(1)—O(8)2.336 (5)C(4)—H(6)0.960
O(3)—C(2)1.449 (8)C(5)—C(6)1.525 (10)
O(3)—H(13)0.820C(6)—C(7)1.53 (1)
O(4)—C(1)1.241 (8)C(6)—C(8)1.523 (10)
O(5)—C(1)1.280 (8)C(7)—H(7)0.960
O(6)—C(6)1.441 (8)C(7)—H(8)0.960
O(6)—H(14)0.820C(7)—H(9)0.960
O(7)—C(5)ii1.257 (8)C(8)—H(10)0.960
O(8)—C(5)1.259 (8)C(8)—H(11)0.960
C(1)—C(2)1.528 (8)C(8)—H(12)0.960
C(2)—C(3)1.51 (1)
O(1)—U(1)—O(2)178.3 (2)C(1)—C(2)—C(4)111.6 (6)
O(1)—U(1)—O(3)88.9 (2)C(3)—C(2)—C(4)112.9 (6)
O(1)—U(1)—O(4)89.9 (2)C(2)—C(3)—H(1)109.5
O(1)—U(1)—O(5)i88.5 (2)C(2)—C(3)—H(2)109.5
O(1)—U(1)—O(7)89.5 (2)C(2)—C(3)—H(3)109.5
O(1)—U(1)—O(8)88.5 (2)H(1)—C(3)—H(2)109.5
O(2)—U(1)—O(3)89.4 (2)H(1)—C(3)—H(3)109.5
O(2)—U(1)—O(4)89.7 (2)H(2)—C(3)—H(3)109.5
O(2)—U(1)—O(5)i93.0 (2)C(2)—C(4)—H(4)109.5
O(2)—U(1)—O(7)91.7 (2)C(2)—C(4)—H(5)109.5
O(2)—U(1)—O(8)90.6 (2)C(2)—C(4)—H(6)109.5
O(3)—U(1)—O(4)62.1 (1)H(4)—C(4)—H(5)109.5
O(3)—U(1)—O(5)i135.7 (2)H(4)—C(4)—H(6)109.5
O(3)—U(1)—O(7)148.9 (2)H(5)—C(4)—H(6)109.5
O(3)—U(1)—O(8)68.9 (2)O(7)ii—C(5)—O(8)124.4 (6)
O(4)—U(1)—O(5)i73.7 (2)O(7)ii—C(5)—C(6)116.7 (6)
O(4)—U(1)—O(7)149.0 (2)O(8)—C(5)—C(6)119.0 (6)
O(4)—U(1)—O(8)131.0 (2)O(6)—C(6)—C(5)111.4 (5)
O(5)i—U(1)—O(7)75.3 (2)O(6)—C(6)—C(7)105.3 (5)
O(5)i—U(1)—O(8)155.1 (2)O(6)—C(6)—C(8)109.8 (6)
O(7)—U(1)—O(8)80.0 (2)C(5)—C(6)—C(7)106.3 (6)
U(1)—O(3)—C(2)124.2 (3)C(5)—C(6)—C(8)111.5 (6)
U(1)—O(3)—H(13)126.3C(7)—C(6)—C(8)112.2 (6)
C(2)—O(3)—H(13)109.5C(6)—C(7)—H(7)109.5
U(1)—O(4)—C(1)126.5 (4)C(6)—C(7)—H(8)109.5
U(1)iii—O(5)—C(1)136.7 (4)C(6)—C(7)—H(9)109.5
C(6)—O(6)—H(14)109.5H(7)—C(7)—H(8)109.5
U(1)—O(7)—C(5)ii154.9 (4)H(7)—C(7)—H(9)109.5
U(1)—O(8)—C(5)153.0 (5)H(8)—C(7)—H(9)109.5
O(4)—C(1)—O(5)125.3 (6)C(6)—C(8)—H(10)109.5
O(4)—C(1)—C(2)119.3 (5)C(6)—C(8)—H(11)109.5
O(5)—C(1)—C(2)115.4 (6)C(6)—C(8)—H(12)109.5
O(3)—C(2)—C(1)102.7 (5)H(10)—C(8)—H(11)109.5
O(3)—C(2)—C(3)109.9 (5)H(10)—C(8)—H(12)109.5
O(3)—C(2)—C(4)109.3 (5)H(11)—C(8)—H(12)109.5
C(1)—C(2)—C(3)109.9 (5)
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O(3)—H(13)···O(6)0.8201.9272.597 (6)138.188
O(6)—H(14)···O(1)iv0.8201.9992.777 (6)158.201
Symmetry codes: (iv) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
U(1)—O(1)1.783 (5)U(1)—O(5)i2.355 (4)
U(1)—O(2)1.762 (6)U(1)—O(7)2.346 (5)
U(1)—O(3)2.444 (5)U(1)—O(8)2.336 (5)
U(1)—O(4)2.407 (5)
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O(3)—H(13)···O(6)0.8201.9272.597 (6)138.188
O(6)—H(14)···O(1)ii0.8201.9992.777 (6)158.201
Symmetry codes: (ii) −x+1, −y+1, −z+1.
Acknowledgements top

The present study is the result of the efficient separation and analysis of nuclear fission products for reprocessing systems entrusted to Osaka University by the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT).

references
References top

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.

Back, D. F., Manzoni de Oliveira, G. & Schulz Lang, E. (2007). Z. Anorg. Allg. Chem. 633, 729–733.

Bombieri, G., Croatto, U., Graziani, R., Forsellini, E. & Magon, L. (1974). Acta Cryst. B30, 407–411.

Bombieri, G., Graziani, R. & Forsellini, E. (1973). Inorg. Nucl. Chem. Lett. 9, 551–557.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Jiang, J., Sarsfield, M. J., Renshaw, J. C., Livens, F. R., Collison, D., Charnock, J. M., Helliwell, M. & Eccles, H. (2002). Inorg. Chem. 41, 2799–2806.

Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.

Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). TEXSAN. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Thuéry, P. (2006). Chem. Commun. pp. 853–855.

Thuéry, P. (2007a). CrystEngComm, 9, 358–360.

Thuéry, P. (2007b). Inorg. Chem. 46, 2307–2315.

Thuéry, P. (2007c). Polyhedron, 26, 101–106.

Thuéry, P. (2008). CrystEngComm, 10, 79–85.

Xie, Y.-R., Zhao, H., Wang, X.-S., Qu, Z.-R., Xiong, R.-G., Xue, X., Xue, Z. & You, X.-Z. (2003). Eur. J. Inorg. Chem. pp. 3712–3715.

Yokoyama, Y., Inaba, A., Hara, H., Yamazaki, T., Tamura, H. & Kushi, Y. (1990). Chem. Lett. pp. 671–674.