Redetermination of di-μ-hydroxido-bis-[diaqua-chlorido-dioxido-uranium(VI)] from single-crystal synchrotron data.

The title compound, [(UO(2))(2)Cl(2)(OH)(2)(H(2)O)(4)], was obtained unintentionally as the product of an attempted reaction between uranium(VI) oxide dihydrate, UO(3)·2H(2)O, and hydrogen bis-(trifluoro-methyl-sulfon-yl)imide (HTf(2)N), in an experiment to obtain crystals of uranyl bis-(trifluoro-methyl-sulfon-yl)imide, UO(2)(Tf(2)N)(2)·xH(2)O. The structure consists of neutral dimers of uranyl (UO(2) (2+)) units, double bridged by OH(-) anions. Each uranyl unit is surrounded by one Cl and four O atoms, which form an irregular penta-gon, in a plane perpendicular to the linear uranyl groups. The coordination geometry around each U atom can be considered to be distorted penta-gonal-bipyramidal. In the crystal structure the uranyl dimers are connected to each other by hydrogen-bonding inter-actions [O⋯Cl = 3.23 (1) Å].

Related literature

For general background to the use of uranyl bis­(trifluoro­methyl­sulfon­yl)imide as a starting material for the study of the spectroscopic properties of uranyl complexes in ionic liquids, see: Nockemann et al. (2007 ▶); Binnemans (2007 ▶). For the original published structure determined from Weissenberg data, see: Åberg (1969 ▶). For related structures, see: Åberg (1970 ▶); Tsushima et al. (2007 ▶). For databases of inorganic structures, see: Bergerhoff et al. (1983 ▶); ICSD (2009 ▶).

Experimental

Crystal data

[U2Cl2O4(OH)2(H2O)4]

M = 717.04

Monoclinic,

a = 10.712 (2) Å

b = 6.1212 (12) Å

c = 17.662 (4) Å

β = 95.47 (3)°

V = 1152.8 (4) Å3

Z = 4

Synchrotron radiation

λ = 0.77000 Å

μ = 63.63 mm−1

T = 100 K

0.15 × 0.10 × 0.1 mm

Data collection

ESRF, SNBL, BM01A diffractometer

Absorption correction: multi-scan (SCALE3 in ABSPACK; Oxford Diffraction, 2006 ▶) T min = 0.008, T max = 0.056

13020 measured reflections

1846 independent reflections

1620 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.131

S = 1.11

1846 reflections

127 parameters

H atoms not located

Δρmax = 3.37 e Å−3

Δρmin = −1.67 e Å−3

Data collection: MAR345 Program Manual (Mar, 2000 ▶); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLUTON (Spek, 2009 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002394/bt5153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002394/bt5153Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[U2Cl2O4(OH)2(H2O)4]	F(000) = 1232
Mr = 717.04	Dx = 4.131 Mg m−3
Monoclinic, P21/n	Synchrotron radiation, λ = 0.77000 Å
Hall symbol: -P 2yn	Cell parameters from 4751 reflections
a = 10.712 (2) Å	θ = 2.3–26.2°
b = 6.1212 (12) Å	µ = 63.63 mm−1
c = 17.662 (4) Å	T = 100 K
β = 95.47 (3)°	Block, yellow
V = 1152.8 (4) Å3	0.15 × 0.1 × 0.1 mm
Z = 4

ESRF, SNBL, BM01A diffractometer	1846 independent reflections
Radiation source: bending magnet	1620 reflections with I > 2σ(I)
double crystal	Rint = 0.067
φ scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SCALE3 in ABSPACK; Oxford Diffraction, 2006)	h = −12→12
Tmin = 0.008, Tmax = 0.056	k = 0→7
13020 measured reflections	l = 0→20

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.045	Secondary atom site location: difference Fourier map
wR(F2) = 0.131	w = 1/[σ2(Fo2) + (0.0885P)2] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max < 0.001
1846 reflections	Δρmax = 3.37 e Å−3
127 parameters	Δρmin = −1.67 e Å−3

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
U1	0.45262 (4)	0.79563 (9)	0.83956 (3)	0.0174 (2)
U2	0.54899 (4)	1.08385 (9)	0.65373 (3)	0.0172 (2)
Cl1	0.3096 (3)	1.0768 (5)	0.91681 (19)	0.0219 (8)
Cl2	0.6957 (3)	0.8008 (6)	0.5776 (2)	0.0228 (8)
O1	0.5897 (9)	0.8918 (15)	0.8900 (5)	0.023 (2)
O2	0.3157 (9)	0.6944 (16)	0.7847 (5)	0.020 (2)
O3	0.5411 (9)	0.4358 (15)	0.8468 (5)	0.020 (2)
O4	0.3839 (10)	0.5906 (16)	0.9501 (6)	0.029 (2)
O5	0.6817 (9)	1.1917 (16)	0.7088 (5)	0.021 (2)
O6	0.4135 (9)	0.9824 (15)	0.6013 (5)	0.020 (2)
O7	0.6135 (10)	1.2896 (16)	0.5424 (6)	0.028 (2)
O8	0.4552 (9)	1.4395 (16)	0.6490 (5)	0.021 (2)
O9	0.5643 (8)	0.7649 (17)	0.7297 (5)	0.019 (2)
O10	0.4367 (9)	1.1133 (14)	0.7628 (5)	0.018 (2)

	U11	U22	U33	U12	U13	U23
U1	0.0166 (4)	0.0182 (4)	0.0173 (3)	0.00014 (19)	0.0014 (2)	0.00002 (17)
U2	0.0173 (4)	0.0174 (4)	0.0169 (3)	−0.00055 (19)	0.0016 (2)	−0.00013 (17)
Cl1	0.0245 (19)	0.0218 (18)	0.0200 (17)	0.0052 (14)	0.0052 (14)	−0.0007 (13)
Cl2	0.0264 (19)	0.0220 (18)	0.0205 (16)	0.0029 (14)	0.0048 (14)	−0.0024 (13)
O1	0.027 (6)	0.019 (5)	0.023 (5)	0.004 (4)	0.003 (4)	−0.001 (4)
O2	0.025 (5)	0.021 (6)	0.014 (4)	−0.007 (4)	0.000 (4)	−0.003 (4)
O3	0.021 (5)	0.016 (5)	0.022 (5)	0.009 (4)	−0.002 (4)	0.002 (4)
O4	0.028 (6)	0.026 (6)	0.034 (6)	0.006 (5)	0.012 (5)	0.003 (4)
O5	0.015 (5)	0.026 (6)	0.021 (5)	−0.011 (4)	0.000 (4)	0.000 (4)
O6	0.020 (5)	0.017 (5)	0.023 (5)	−0.002 (4)	−0.006 (4)	0.002 (4)
O7	0.031 (6)	0.022 (6)	0.032 (6)	−0.011 (5)	0.004 (5)	0.004 (4)
O8	0.019 (5)	0.022 (5)	0.021 (5)	0.003 (4)	−0.004 (4)	0.004 (4)
O9	0.013 (5)	0.023 (5)	0.019 (5)	−0.008 (4)	−0.007 (4)	0.003 (4)
O10	0.023 (5)	0.011 (5)	0.018 (5)	−0.004 (4)	−0.002 (4)	−0.002 (4)

U1—O1	1.746 (10)	U2—O6	1.759 (9)
U1—O2	1.789 (10)	U2—O5	1.772 (9)
U1—O10	2.367 (9)	U2—O9	2.366 (10)
U1—O9	2.382 (9)	U2—O10	2.373 (9)
U1—O3	2.397 (9)	U2—O8	2.396 (10)
U1—O4	2.490 (10)	U2—O7	2.488 (10)
U1—Cl1	2.751 (3)	U2—Cl2	2.772 (3)
U1—U2	3.9492 (10)
O1—U1—O2	177.7 (4)	O6—U2—O9	90.9 (4)
O1—U1—O10	91.5 (4)	O5—U2—O9	89.3 (4)
O2—U1—O10	87.9 (4)	O6—U2—O10	89.8 (4)
O1—U1—O9	88.8 (4)	O5—U2—O10	88.2 (4)
O2—U1—O9	88.9 (4)	O9—U2—O10	67.4 (3)
O10—U1—O9	67.2 (3)	O6—U2—O8	88.9 (4)
O1—U1—O3	88.5 (4)	O5—U2—O8	89.6 (4)
O2—U1—O3	90.6 (4)	O9—U2—O8	140.9 (3)
O10—U1—O3	142.3 (3)	O10—U2—O8	73.5 (3)
O9—U1—O3	75.2 (3)	O6—U2—O7	92.3 (4)
O1—U1—O4	93.8 (4)	O5—U2—O7	88.7 (4)
O2—U1—O4	87.8 (4)	O9—U2—O7	148.9 (3)
O10—U1—O4	148.5 (3)	O10—U2—O7	143.5 (3)
O9—U1—O4	143.9 (3)	O8—U2—O7	70.1 (3)
O3—U1—O4	68.9 (3)	O6—U2—Cl2	90.1 (3)
O1—U1—Cl1	91.0 (3)	O5—U2—Cl2	92.1 (3)
O2—U1—Cl1	91.1 (3)	O9—U2—Cl2	75.4 (2)
O10—U1—Cl1	76.0 (2)	O10—U2—Cl2	142.7 (2)
O9—U1—Cl1	143.1 (3)	O8—U2—Cl2	143.8 (2)
O3—U1—Cl1	141.7 (2)	O7—U2—Cl2	73.7 (3)
O4—U1—Cl1	72.9 (2)	O6—U2—U1	90.7 (3)
O1—U1—U2	90.0 (3)	O5—U2—U1	88.3 (3)
O2—U1—U2	88.3 (3)	O9—U2—U1	33.8 (2)
O10—U1—U2	33.6 (2)	O10—U2—U1	33.5 (2)
O9—U1—U2	33.6 (2)	O8—U2—U1	107.0 (2)
O3—U1—U2	108.7 (2)	O7—U2—U1	175.8 (2)
O4—U1—U2	175.4 (3)	Cl2—U2—U1	109.21 (8)
Cl1—U1—U2	109.56 (7)	U2—O9—U1	112.6 (4)
O6—U2—O5	177.8 (4)	U1—O10—U2	112.9 (4)