Tetra-μ2-acetato-tetraaquadi-μ3-oxido-octaoxidotetrauranium(VI) methanol disolvate tetrahydrate

Sleem, H.; Georghiou, P.; Dawe, L.N.

doi:10.1107/S1600536811050549

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1880-m1881

https://doi.org/10.1107/S1600536811050549

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Tetra-μ₂-acetato-tetraaquadi-μ₃-oxido-octaoxidotetrauranium(VI) methanol disolvate tetrahydrate

Hisham Sleem,^a Paris Georghiou ^a and Louise N. Dawe ^b ^*

^aDepartment of Chemistry, Memorial University of Newfoundland, St. Johns, NL, A1B 3X7, Canada, and ^bDepartment of Chemistry and Centre for Chemical Analysis, Research and Training (C-CART), X-Ray Diffraction Laboratory, Memorial University of Newfoundland, St. Johns, NL, A1B 3X7, Canada
^*Correspondence e-mail: louise.dawe@mun.ca

(Received 3 November 2011; accepted 24 November 2011; online 30 November 2011)

The centrosymmetric title tetramer, [U₄(C₂H₃O₂)₄O₁₀(H₂O)₄]·2CH₄O, has a near planar core [maximum deviation from the least squares plane of 0.294 (6) Å]. It consists of two hexagonal–bipyramidally coordinated U^VI atoms connected via μ₂-O (acetate) and μ₃-O (oxide) bridges in the equatorial plane to two pentagonal–bipyramidally coordinated U^VI atoms. The equatorial plane of each U^VI atom is completed by a bound water molecule, while the axial positions are occupied by uranyl (UO₂)²⁺ O atoms. Multiple O—H⋯O hydrogen bonds are present, including a lattice methanol molecule bound to one of the pentagonal bipyramidal uranyl O atoms, as well as two different C¹₁(6) chains orginating from a donor water molecule, via a uranyl oxygen acceptor and an acetate acceptor on different, adjacent tetramers. Finally, the unit cell contains four U^VI tetramers, all connected by hydrogen bonding, forming a supramolecular R⁴₄(24) ring.

Related literature

For structurally similar tetrameric complexes with U^VI, M₄[(UO₂)₄(μ₃-O)₂L₄] (M = NH₄⁺, K⁺, Cs⁺; L = phthalate), see: Charushnikova et al. (2005 ), and with Bi, [Bi₂(μ₃-O)(OCH(CF₃)₂)₂(μ-OCH(CF₃)₂)₂(Solv)]₂ (Solv = C₇H₈, Et₂O, thf), see: Andrews et al. (2008 ). For a planar, mixed valent U^V₂U^VI₂ alkoxide, see: Zozulin et al. (1982 ). For a p-benzylcalix[7]arene complex containing a hexanuclear U^VI cluster with a planar tetrameric core, see: Thuéry et al. (1999 ), and for dinuclear uranyl-containing salen [N,N′-ethylenebis(salicylimine)] complexes, see: Amato et al. (2007 ). For bond-valence-sum calculations, see: Wills (2010 ).

Experimental

Crystal data

[U₄(C₂H₃O₂)₄O₁₀(H₂O)₄]·2CH₄O
M_r = 1484.44
Monoclinic, P 2₁ /c
a = 8.334 (3) Å
b = 10.649 (3) Å
c = 16.763 (5) Å
β = 107.632 (4)°
V = 1417.8 (8) Å³
Z = 2
Mo Kα radiation
μ = 22.87 mm⁻¹
T = 163 K
0.10 × 0.07 × 0.05 mm

Data collection

Rigaku Saturn70 CCD diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1999 ) T_min = 0.638, T_max = 0.880
15149 measured reflections
3255 independent reflections
3136 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.09
3255 reflections
188 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.71 e Å⁻³
Δρ_min = −2.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12⋯O9	0.84	2.31	3.009 (10)	141
O8—H8A⋯O7ⁱ	0.87 (6)	2.07 (6)	2.859 (8)	151 (7)
O8—H8B⋯O12ⁱⁱ	0.88 (7)	1.78 (6)	2.645 (8)	170 (9)
O11—H11A⋯O10ⁱⁱⁱ	0.87 (7)	1.88 (7)	2.736 (7)	166 (8)
O11—H11B⋯O2^iv	0.88 (7)	1.83 (7)	2.705 (7)	173 (7)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z+1; (iv) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear-SM Expert (Rigaku, 2009 ); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811050549/br2182sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050549/br2182Isup2.hkl

checkCIF report

Comment top

In connection with our on-going studies on metal-binding properties of a new series of macrocylic polyamide compounds, we were interested in determining whether such macrocycles, by analogy with analogous salen (N,N'-Ethylenebis(salicylimine)) compounds, would also form stable uranyl complexes. Using similar conditions to those which Amato et al. (2007) employed with their salens, the title compound crystallized out in the form reported herein.

Bond valence sum calculations (Wills, 2010) performed on the title compound indicate that both crystallographically independent uranium atoms are in the +6 oxidations state (U1 = 6.095, U2 = 6.074). The centrosymmetric U(VI) tetramer consists of two hexagonal bipyramids, and two pentagonal bipyramids (U1 and U2, and symmetry equivalents (-x + 1, -y, -z + 1), respectively; Figure 1), with (UO₂)²⁺ oxygen-atoms occupying the axial positions for both U1 and U2. For U1, the equatorial plane consists of trans-bidentate acetate anions, each with one bridging µ₂-O-atom (O1 and O3), and a µ₃-O^2- anion (O5) trans to a water molecule. The equatorial plane of U2 is therefore composed of the aforementioned µ₂-O and µ₃-O atoms, and their inversion-symmetry generated counter-parts, as well as water molecule (O11). Similar to the description given by Andrews et al. (2008) for [Bi₂(µ₃-O)(OCH(CF₃)₂)₂(µ-OCH(CF₃)₂)₂(Solv)]₂ (Solv = C₇H₈, Et₂O, thf) tetramers, this complex consists of a near planar, ten atom "raft", with maximum deviation from the least squares plane [U1, U2, O1–5 and symmetry equivalents (-x + 1, -y, -z + 1)] of 0.294 (6) Å for O5. Examination of longer range interactions reveals numerous hydrogen bonds, including a lattice solvent methanol molecule bound to one of the pentagonal bipyramidal uranyl oxygen atoms (O12—H12···O9; Figure 1), which further bridges to a bound water molecule of a second tetramer (O8—H8B···O12ⁱⁱⁱ, (iii) x, -y+1/2, z-1/2; Figure 2, green dashed lines.) The tetramers interact via an additional hydrogen bond, wherby the aforementioned water molecule acts as a donor to one of the hexagonal bipyramidal uranyl oxygen atoms on the first assembly (O8—H8A···O7ⁱⁱ, (ii) -x+1, y+1/2, -z+1/2; Figure 2, black dashed lines) leading to a 24-membered H-bonded ring (graph set notation R⁴₄(24)) which spans all four tetramers present in the unit cell.

Related literature top

For structurally similar tetrameric complexes with U(VI), M₄[(UO₂)₄(µ₃-O)₂L₄] (M = NH₄⁺, K⁺, Cs⁺; L = phthalate), see: Charushnikova et al. (2005), and with Bi, [Bi₂ (µ₃-O)(OCH(CF₃)₂)₂(µ-OCH(CF₃)₂)₂(Solv)]₂ (Solv = C₇H₈, Et₂O, thf), see: Andrews et al. (2008). For a planar, mixed valent U(V)₂U(VI)₂ alkoxide, see: Zozulin et al. (1982). For a p-benzylcalix[7]arene complex containing a hexanuclear U(VI) cluster with a planar tetrameric core, see: Thuéry et al. (1999), and for dinuclear uranyl-containing salen [N,N'-ethylenebis(salicylimine)] complexes, see: Amato et al. (2007). For bond-valence-sum calculations, see: Wills (2010).

Experimental top

160 mg (0.337 mmol) of uranyl acetate dihydrate (UO₂(CH₃COO)₂.2H₂O) was dissolved in 1 ml methanol, and warmed in a hot water bath (323 K) for 5 minutes. The solution was left at room temperature (293 K) for slow evaporation. Yellow prismatic crystals, suitable for analysis by X-ray diffraction, formed after one week.

Structure description top

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. 50% displacement ellipsoid representation of the title compound; hydrogen bonding indicated by dashed lines. Symmetry code: (i) -x + 1, -y, -z + 1.
	Fig. 2. 50% displacement ellipsoid representation of the packed unit cell for the title compound; hydrogen bonding indicated by dashed lines. H-bonding for O11—H11A···O10^iv and O11—H11B···O2^v not shown. Symmetry codes: (ii)-x + 1, y + 1/2, -z + 1/2, (vi) x, -y + 1/2, z + 1/2, (vii) -x + 1, -y + 1, -z + 1, (viii)x, y + 1, z, (ix) -x + 1, y + 1/2, -z + 3/2.

Tetra-µ₂-acetato-tetraaquadi-µ₃-oxido-octaoxidotetrauranium(VI) methanol disolvate tetrahydrate top

Crystal data top

[U₄(C₂H₃O₂)₄O₁₀(H₂O)₄]·2CH₄O	F(000) = 1296
M_r = 1484.44	D_x = 3.477 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 4946 reflections
a = 8.334 (3) Å	θ = 1.9–29.5°
b = 10.649 (3) Å	µ = 22.87 mm⁻¹
c = 16.763 (5) Å	T = 163 K
β = 107.632 (4)°	Prism, yellow
V = 1417.8 (8) Å³	0.10 × 0.07 × 0.05 mm
Z = 2

Data collection top

Rigaku Saturn70 CCD diffractometer	3255 independent reflections
Radiation source: fine-focus sealed tube	3136 reflections with I > 2σ(I)
Graphite - Rigaku SHINE monochromator	R_int = 0.076
Detector resolution: 14.63 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: numerical (ABSCOR; Higashi, 1999)	k = −13→13
T_min = 0.638, T_max = 0.880	l = −21→21
15149 measured reflections

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0469P)² + 6.6005P] where P = (F_o² + 2F_c²)/3
3255 reflections	(Δ/σ)_max = 0.001
188 parameters	Δρ_max = 1.71 e Å⁻³
6 restraints	Δρ_min = −2.85 e Å⁻³

Crystal data top

[U₄(C₂H₃O₂)₄O₁₀(H₂O)₄]·2CH₄O	V = 1417.8 (8) Å³
M_r = 1484.44	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.334 (3) Å	µ = 22.87 mm⁻¹
b = 10.649 (3) Å	T = 163 K
c = 16.763 (5) Å	0.10 × 0.07 × 0.05 mm
β = 107.632 (4)°

Data collection top

Rigaku Saturn70 CCD diffractometer	3255 independent reflections
Absorption correction: numerical (ABSCOR; Higashi, 1999)	3136 reflections with I > 2σ(I)
T_min = 0.638, T_max = 0.880	R_int = 0.076
15149 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	6 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 1.71 e Å⁻³
3255 reflections	Δρ_min = −2.85 e Å⁻³
188 parameters

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

	x	y	z	U_iso*/U_eq
U1	0.41912 (3)	0.20869 (2)	0.332933 (15)	0.01529 (10)
U2	0.71490 (3)	0.06455 (2)	0.542406 (14)	0.01236 (10)
O1	0.1576 (7)	0.0796 (5)	0.3408 (3)	0.0247 (11)
O2	0.1274 (7)	0.1931 (5)	0.2295 (3)	0.0272 (12)
O3	0.7084 (7)	0.2370 (6)	0.4457 (4)	0.0296 (13)
O4	0.6738 (7)	0.3262 (6)	0.3266 (4)	0.0306 (13)
O5	0.4581 (6)	0.0936 (5)	0.4484 (3)	0.0217 (11)
O6	0.3486 (7)	0.3399 (5)	0.3788 (4)	0.0277 (12)
O7	0.4880 (7)	0.0816 (5)	0.2841 (4)	0.0277 (12)
O8	0.3755 (7)	0.3336 (5)	0.2040 (3)	0.0230 (11)
H8A	0.403 (12)	0.406 (4)	0.188 (5)	0.034*
H8B	0.367 (13)	0.286 (6)	0.160 (4)	0.034*
O9	0.6588 (7)	0.1628 (5)	0.6159 (4)	0.0264 (12)
O10	0.7947 (6)	−0.0283 (5)	0.4734 (3)	0.0236 (11)
O11	0.9960 (6)	0.1499 (5)	0.5992 (3)	0.0202 (10)
H11A	1.075 (7)	0.121 (8)	0.580 (5)	0.030*
H11B	1.047 (9)	0.200 (7)	0.641 (4)	0.030*
O12	0.3208 (9)	0.2904 (6)	0.5615 (4)	0.0376 (15)
H12	0.3876	0.2346	0.5557	0.056*
C1	0.0629 (9)	0.1183 (7)	0.2696 (4)	0.0207 (14)
C2	−0.1168 (10)	0.0795 (8)	0.2383 (6)	0.0332 (19)
H2A	−0.1601	0.0663	0.2859	0.040*
H2B	−0.1261	0.0013	0.2064	0.040*
H2C	−0.1825	0.1454	0.2020	0.040*
C3	0.7675 (10)	0.2993 (7)	0.3966 (5)	0.0239 (16)
C4	0.9472 (12)	0.3420 (11)	0.4242 (7)	0.049 (3)
H4A	0.9639	0.4053	0.3850	0.059*
H4B	1.0212	0.2701	0.4252	0.059*
H4C	0.9741	0.3785	0.4803	0.059*
C5	0.4006 (16)	0.4061 (10)	0.5715 (6)	0.051 (3)
H5A	0.4034	0.4418	0.6258	0.062*
H5B	0.3388	0.4628	0.5267	0.062*
H5C	0.5159	0.3955	0.5692	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
U1	0.01397 (15)	0.01724 (15)	0.01456 (16)	0.00003 (8)	0.00417 (11)	0.00355 (8)
U2	0.00972 (14)	0.01612 (15)	0.01148 (15)	−0.00104 (8)	0.00357 (10)	0.00029 (8)
O1	0.018 (3)	0.031 (3)	0.021 (3)	−0.001 (2)	0.000 (2)	0.014 (2)
O2	0.023 (3)	0.037 (3)	0.018 (3)	−0.006 (2)	0.002 (2)	0.015 (2)
O3	0.020 (3)	0.034 (3)	0.033 (3)	−0.006 (2)	0.005 (2)	0.016 (3)
O4	0.022 (3)	0.043 (3)	0.025 (3)	−0.007 (2)	0.003 (2)	0.005 (2)
O5	0.012 (2)	0.031 (3)	0.019 (3)	−0.006 (2)	0.0002 (19)	0.010 (2)
O6	0.019 (3)	0.032 (3)	0.029 (3)	0.006 (2)	0.003 (2)	−0.001 (2)
O7	0.026 (3)	0.029 (3)	0.029 (3)	0.002 (2)	0.011 (2)	−0.001 (2)
O8	0.023 (3)	0.025 (3)	0.022 (3)	0.001 (2)	0.008 (2)	0.011 (2)
O9	0.021 (3)	0.029 (3)	0.032 (3)	0.000 (2)	0.011 (2)	−0.008 (2)
O10	0.016 (2)	0.032 (3)	0.022 (3)	−0.004 (2)	0.004 (2)	−0.009 (2)
O11	0.014 (2)	0.027 (3)	0.022 (3)	−0.006 (2)	0.009 (2)	−0.010 (2)
O12	0.042 (4)	0.040 (4)	0.033 (3)	0.004 (3)	0.014 (3)	0.004 (3)
C1	0.017 (3)	0.020 (3)	0.020 (3)	0.000 (3)	−0.001 (3)	0.006 (3)
C2	0.016 (4)	0.043 (5)	0.036 (5)	−0.006 (3)	0.001 (3)	0.014 (4)
C3	0.023 (4)	0.021 (3)	0.031 (4)	−0.005 (3)	0.012 (3)	0.003 (3)
C4	0.028 (5)	0.073 (7)	0.044 (6)	−0.014 (5)	0.006 (4)	0.021 (5)
C5	0.072 (8)	0.041 (5)	0.032 (5)	0.009 (5)	0.002 (5)	−0.005 (4)

Geometric parameters (Å, º) top

U1—O7	1.765 (6)	O4—C3	1.230 (10)
U1—O6	1.779 (6)	O5—U2ⁱ	2.252 (5)
U1—O5	2.230 (5)	O8—H8A	0.87 (2)
U1—O8	2.469 (5)	O8—H8B	0.87 (2)
U1—O4	2.494 (6)	O11—H11A	0.87 (2)
U1—O2	2.528 (6)	O11—H11B	0.87 (2)
U1—O3	2.592 (6)	O12—C5	1.385 (12)
U1—O1	2.614 (5)	O12—H12	0.8400
U2—O9	1.784 (5)	C1—C2	1.487 (10)
U2—O10	1.795 (5)	C2—H2A	0.9800
U2—O5ⁱ	2.252 (5)	C2—H2B	0.9800
U2—O5	2.261 (5)	C2—H2C	0.9800
U2—O11	2.422 (5)	C3—C4	1.498 (12)
U2—O3	2.438 (5)	C4—H4A	0.9800
U2—O1ⁱ	2.461 (5)	C4—H4B	0.9800
O1—C1	1.284 (8)	C4—H4C	0.9800
O1—U2ⁱ	2.461 (5)	C5—H5A	0.9800
O2—C1	1.262 (9)	C5—H5B	0.9800
O3—C3	1.268 (9)	C5—H5C	0.9800

O7—U1—O6	178.0 (3)	O5—U2—O1ⁱ	136.78 (17)
O7—U1—O5	89.9 (2)	O11—U2—O1ⁱ	77.77 (18)
O6—U1—O5	92.1 (2)	O3—U2—O1ⁱ	156.28 (18)
O7—U1—O8	89.4 (2)	C1—O1—U2ⁱ	159.4 (5)
O6—U1—O8	88.6 (2)	C1—O1—U1	94.1 (4)
O5—U1—O8	179.2 (2)	U2ⁱ—O1—U1	101.70 (18)
O7—U1—O4	88.0 (2)	C1—O2—U1	98.8 (4)
O6—U1—O4	91.2 (2)	C3—O3—U2	153.0 (5)
O5—U1—O4	114.24 (18)	C3—O3—U1	92.6 (5)
O8—U1—O4	66.05 (18)	U2—O3—U1	103.06 (19)
O7—U1—O2	90.7 (2)	C3—O4—U1	98.3 (5)
O6—U1—O2	88.5 (2)	U1—O5—U2ⁱ	122.8 (2)
O5—U1—O2	114.60 (17)	U1—O5—U2	122.6 (2)
O8—U1—O2	65.10 (17)	U2ⁱ—O5—U2	109.9 (2)
O4—U1—O2	131.14 (18)	U1—O8—H8A	140 (6)
O7—U1—O3	93.8 (2)	U1—O8—H8B	112 (5)
O6—U1—O3	87.1 (2)	H8A—O8—H8B	102 (4)
O5—U1—O3	64.64 (17)	U2—O11—H11A	118 (5)
O8—U1—O3	115.72 (17)	U2—O11—H11B	136 (5)
O4—U1—O3	50.00 (18)	H11A—O11—H11B	105 (4)
O2—U1—O3	175.5 (2)	C5—O12—H12	109.5
O7—U1—O1	90.8 (2)	O2—C1—O1	117.2 (6)
O6—U1—O1	90.1 (2)	O2—C1—C2	122.2 (7)
O5—U1—O1	64.63 (17)	O1—C1—C2	120.5 (7)
O8—U1—O1	115.07 (17)	C1—C2—H2A	109.5
O4—U1—O1	178.31 (18)	C1—C2—H2B	109.5
O2—U1—O1	49.97 (16)	H2A—C2—H2B	109.5
O3—U1—O1	129.03 (16)	C1—C2—H2C	109.5
O9—U2—O10	173.7 (2)	H2A—C2—H2C	109.5
O9—U2—O5ⁱ	94.8 (2)	H2B—C2—H2C	109.5
O10—U2—O5ⁱ	90.1 (2)	O4—C3—O3	118.9 (7)
O9—U2—O5	90.6 (2)	O4—C3—C4	120.7 (7)
O10—U2—O5	94.8 (2)	O3—C3—C4	120.4 (8)
O5ⁱ—U2—O5	70.1 (2)	C3—C4—H4A	109.5
O9—U2—O11	86.2 (2)	C3—C4—H4B	109.5
O10—U2—O11	87.5 (2)	H4A—C4—H4B	109.5
O5ⁱ—U2—O11	144.73 (18)	C3—C4—H4C	109.5
O5—U2—O11	145.17 (18)	H4A—C4—H4C	109.5
O9—U2—O3	93.4 (2)	H4B—C4—H4C	109.5
O10—U2—O3	85.7 (2)	O12—C5—H5A	109.5
O5ⁱ—U2—O3	136.25 (19)	O12—C5—H5B	109.5
O5—U2—O3	66.93 (18)	H5A—C5—H5B	109.5
O11—U2—O3	78.65 (18)	O12—C5—H5C	109.5
O9—U2—O1ⁱ	87.5 (2)	H5A—C5—H5C	109.5
O10—U2—O1ⁱ	90.8 (2)	H5B—C5—H5C	109.5
O5ⁱ—U2—O1ⁱ	67.08 (17)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O9	0.84	2.31	3.009 (10)	141
O12—H12···O5	0.84	2.54	3.257 (9)	143
O8—H8A···O7ⁱⁱ	0.87 (6)	2.07 (6)	2.859 (8)	151 (7)
O8—H8B···O12ⁱⁱⁱ	0.88 (7)	1.78 (6)	2.645 (8)	170 (9)
O11—H11A···O10^iv	0.87 (7)	1.88 (7)	2.736 (7)	166 (8)
O11—H11B···O2^v	0.88 (7)	1.83 (7)	2.705 (7)	173 (7)

Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+2, −y, −z+1; (v) x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[U₄(C₂H₃O₂)₄O₁₀(H₂O)₄]·2CH₄O
M_r	1484.44
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	163
a, b, c (Å)	8.334 (3), 10.649 (3), 16.763 (5)
β (°)	107.632 (4)
V (Å³)	1417.8 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	22.87
Crystal size (mm)	0.10 × 0.07 × 0.05

Data collection
Diffractometer	Rigaku Saturn70 CCD
Absorption correction	Numerical (ABSCOR; Higashi, 1999)
T_min, T_max	0.638, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	15149, 3255, 3136
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.09
No. of reflections	3255
No. of parameters	188
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.71, −2.85

Computer programs: CrystalClear-SM Expert (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O9	0.84	2.31	3.009 (10)	141
O8—H8A···O7ⁱ	0.87 (6)	2.07 (6)	2.859 (8)	151 (7)
O8—H8B···O12ⁱⁱ	0.88 (7)	1.78 (6)	2.645 (8)	170 (9)
O11—H11A···O10ⁱⁱⁱ	0.87 (7)	1.88 (7)	2.736 (7)	166 (8)
O11—H11B···O2^iv	0.88 (7)	1.83 (7)	2.705 (7)	173 (7)

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, −y, −z+1; (iv) x+1, −y+1/2, z+1/2.

Acknowledgements

The Egyptian Government is thanked for the scholarship to HS. LND would like to acknowledge Dr Amy Sarjeant, Northwestern University, for a helpful discussion about heavy atom structure refinements. Financial support from the Dean of Science and the Chemistry Department, Memorial University of Newfoundland, is acknowledged.

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