inorganic compounds
Rerefinement of the 3)[UCl6]
of trichloridosulfonium(IV) hexachloridouranate(V), (SClaAnorganische Chemie, Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35032 Marburg, Germany
*Correspondence e-mail: florian.kraus@chemie.uni-marburg.de
Single crystals of trichloridosulfonium(IV) hexachloridouranate(V) were obtained from the reaction of uranium(IV) chloride with an excess of disulfur dichloride and studied by single-crystal X-ray diffraction. In comparison with the structure model reported previously [Sawodny et al. (1983). Z. Anorg. Allg. Chem. 499, 81–88.], the lattice parameters and fractional atomic coordinates were determined to a much higher precision, leading overall to an improved structure model. The ionic compound contains trigonal–pyramidal (SCl3)+ cations and slightly distorted octahedral [UCl6]− anions. The structure was refined as an with a twin ratio of 4.4:1.
Keywords: crystal structure; uranium; disulfur dichloride; ion pair.
CCDC reference: 2010898
Structure description
We explored the reaction of uranium tetrachloride with disulfur dichloride out of curiosity. Moreover, we investigated whether the latter compound could be a potential solvent for uranium halides. During these studies, high-quality single crystals of (SCl3)[UCl6] were obtained.
The lattice parameters determined at 100 K from the current single-crystal X-ray ) agree with those reported previously [a = 10.668 (10), b = 10.712 (4) c = 11.333 (6) Å at T = 293 K; Sawodny et al., 1983].
(Table 3The UV atom is located on 4 a and has six chloride ligands in its slightly distorted octahedral coordination sphere (Fig. 1). The U—Cl bond lengths range between 2.4869 (16) and 2.5209 (14) Å and are in good agreement with the previously reported values [U—Cl distances = 2.485 (11)–2.531 (10) Å; Sawodny et al., 1983]. A comparison between the U—Cl bond lengths and Cl—U—Cl angles obtained from the current and the previous refinements is collated in Tables 1 and 2, respectively. Similar U—Cl distances are observed: (i) in the of the low-temperature modification of UCl6 where the coordination sphere for the U atom is also distorted octahedral but with slightly shorter U—Cl bonds of 2.4443 (15)–2.4570 (20) Å (at 100 K; Deubner et al., 2019) due to the presence of a UVI atom, and (ii) in Cs2[UCl6] with longer U—Cl bonds of 2.621 Å (at 293 K; Schleid et al., 1987) due to the presence of an UIV atom.
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The SIV atom is also located on 4 a and has three chloride atoms in its trigonal–pyramidal coordination sphere (Fig. 1). The S—Cl bond lengths are virtually the same at 100 K. In comparison, Sawodny et al. (1983) reported slightly shorter S—Cl bond lengths for (SCl3)[UCl6] at 293 K (Table 1). Nevertheless, these atomic distances are also in good agreement with those reported for the ionic compound β-[SCl3][SbCl6] [1.979 (5) to 1.992 (7) Å at 169 K; Minkwitz et al., 1992]. The Cl—S—Cl bond angles in (SCl3)[UCl6] resulting from the current and the previous refinements differ slightly (Table 2).
The packing of U and S atoms in the 3)[UCl6] is shown in Fig. 2. As can be seen, the U and S atoms are arranged according to a distorted NaCl-type of structure. The overall coordination sphere of the S atom can be regarded as [3 + 3], with the three long S—Cl interactions being 3.0721 (2), 3.160 (2) and 3.287 (2) Å. The corresponding is a distorted trigonal antiprism, with the S atom displaced from the center.
of (SClSynthesis and crystallization
(SCl3)[UCl6] was synthesized in a borosilicate Schlenk tube from uranium tetrachloride (35 mg, 0.09 mmol) in disulfur dichloride (3 ml) at 358 K over a period of four months. A selected dark-yellow crystal was chosen for single-crystal X-ray diffraction.
We assume that S2Cl2 disproportionates under the applied reaction conditions and that elemental chlorine, sulfur monochloride, as well as the sulfur chlorides S3Cl2 and S3Cl4 are produced in the chemical equilibria described in equations (1)–(3).
3 S2Cl2 → S3Cl2 + S3Cl4 [equation (1); Spong, 1933].
S3Cl4 → S2Cl2 + SCl2 [equation (2); Spong, 1933].
S3Cl4 → S3Cl2 + Cl2 [equation (3); Spong, 1933].
Chlorine is dissolved in an excess of S2Cl2 and may then act as an oxidant oxidizing uranium(IV) chloride to form UCl5 [equation (4)]. Other chlorine-sulfur species may also be responsible for the oxidation.
2 UCl4 + Cl2 → 2 UCl5 [equation (4); Cordfunke et al., 1982].
We further assume that the formed SCl2 [equation (2)] may disproportionate to S2Cl2 and SCl4 [equation (5)].
3 SCl2 → S2Cl2 + SCl4 [equation (5); Lowry et al., 1927].
Finally, the formation of the title compound may be described by the reaction of the 5 with SCl4 under abstraction of a chloride ion [equation (6)].
UClSCl4 + UCl5 → (SCl3)[UCl6] [equation (6); Sawodny et al., 1983].
Refinement
Crystal data, data collection and structure . Atomic coordinates of the previously reported (SCl3)[UCl6] structure (Sawodny et al., 1983) were used for The structure was refined as an with a twin ratio of 4.4:1. As a result of the similarity of the a and b lattice parameters, a fourfold twin was also considered; of this twin model led to insignificant twin fractions. Rint for the tetragonal was above 0.4, ruling out a higher symmetry model.
details are summarized in Table 3Structural data
CCDC reference: 2010898
https://doi.org/10.1107/S2414314620009608/wm4134sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620009608/wm4134Isup2.hkl
Data collection: X-AREA (Stoe, 2016); cell
X-AREA (Stoe, 2016); data reduction: X-AREA (Stoe, 2016); program(s) used to solve structure: coordinates from an isotypic structure; program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2019); software used to prepare material for publication: publCIF (Westrip, 2010).(SCl3)[UCl6] | Dx = 3.141 Mg m−3 |
Mr = 589.14 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 23552 reflections |
a = 10.534 (2) Å | θ = 3.6–58.9° |
b = 10.545 (2) Å | µ = 15.07 mm−1 |
c = 11.217 (2) Å | T = 100 K |
V = 1246.0 (4) Å3 | Block, dark yellow |
Z = 4 | 0.15 × 0.1 × 0.08 mm |
F(000) = 1044 |
STOE IPDS 2T diffractometer | 3364 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 3304 reflections with I > 2σ(I) |
Planar graphite monochromator | Rint = 0.046 |
Detector resolution: 6.67 pixels mm-1 | θmax = 29.2°, θmin = 2.7° |
rotation method, ω scans | h = −14→13 |
Absorption correction: numerical (X-Red32; Stoe 2016) | k = −14→14 |
Tmin = 0.036, Tmax = 0.090 | l = −15→15 |
18340 measured reflections |
Refinement on F2 | Primary atom site location: other |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0148P)2 + 3.5607P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.019 | (Δ/σ)max = 0.001 |
wR(F2) = 0.043 | Δρmax = 0.53 e Å−3 |
S = 1.08 | Δρmin = −1.01 e Å−3 |
3364 reflections | Absolute structure: Refined as an inversion twin |
101 parameters | Absolute structure parameter: 0.186 (6) |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
U1 | 0.97364 (2) | 0.42494 (2) | 0.98324 (2) | 0.01499 (6) | |
S1 | 0.42766 (14) | 0.54654 (14) | 0.91370 (13) | 0.0181 (3) | |
Cl1 | 0.82355 (14) | 0.89033 (16) | 0.63247 (14) | 0.0239 (3) | |
Cl2 | 0.59526 (14) | 0.94785 (14) | 0.86341 (13) | 0.0225 (3) | |
Cl3 | 0.93040 (17) | 0.62131 (16) | 0.86263 (15) | 0.0273 (3) | |
Cl4 | 0.85717 (15) | 0.29644 (17) | 0.83292 (15) | 0.0258 (3) | |
Cl5 | 0.72554 (14) | 0.53738 (16) | 0.59988 (14) | 0.0241 (3) | |
Cl6 | 0.97901 (16) | 0.72883 (13) | 0.39615 (13) | 0.0220 (3) | |
Cl7 | 0.92843 (16) | 0.96521 (16) | 0.91059 (14) | 0.0250 (3) | |
Cl8 | 0.60091 (14) | 0.60665 (15) | 0.87712 (15) | 0.0241 (3) | |
Cl9 | 0.32415 (15) | 0.69986 (15) | 0.88359 (15) | 0.0255 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.01381 (8) | 0.01650 (8) | 0.01466 (9) | −0.00076 (7) | −0.00008 (7) | −0.00013 (7) |
S1 | 0.0170 (6) | 0.0191 (7) | 0.0180 (6) | 0.0009 (5) | −0.0012 (5) | 0.0006 (5) |
Cl1 | 0.0180 (6) | 0.0306 (8) | 0.0232 (7) | 0.0019 (5) | 0.0051 (5) | 0.0038 (6) |
Cl2 | 0.0221 (7) | 0.0233 (8) | 0.0221 (7) | 0.0034 (5) | 0.0020 (5) | −0.0045 (5) |
Cl3 | 0.0355 (8) | 0.0223 (7) | 0.0241 (7) | 0.0010 (6) | −0.0012 (7) | 0.0060 (6) |
Cl4 | 0.0219 (7) | 0.0316 (8) | 0.0239 (7) | −0.0038 (6) | −0.0057 (6) | −0.0059 (6) |
Cl5 | 0.0170 (6) | 0.0342 (8) | 0.0211 (7) | 0.0039 (6) | −0.0024 (5) | −0.0018 (6) |
Cl6 | 0.0227 (6) | 0.0192 (6) | 0.0240 (6) | 0.0011 (6) | −0.0028 (6) | −0.0027 (5) |
Cl7 | 0.0273 (7) | 0.0295 (8) | 0.0182 (7) | −0.0015 (6) | −0.0004 (6) | 0.0028 (6) |
Cl8 | 0.0179 (6) | 0.0283 (8) | 0.0262 (7) | −0.0016 (5) | 0.0012 (5) | 0.0053 (6) |
Cl9 | 0.0240 (7) | 0.0243 (7) | 0.0280 (8) | 0.0073 (6) | −0.0025 (6) | 0.0035 (6) |
U1—Cl4 | 2.4869 (16) | U1—Cl2iii | 2.5297 (15) |
U1—Cl5i | 2.5045 (16) | S1—Cl7iv | 1.975 (2) |
U1—Cl3 | 2.5151 (16) | S1—Cl8 | 1.975 (2) |
U1—Cl6ii | 2.5209 (14) | S1—Cl9 | 1.979 (2) |
U1—Cl1ii | 2.5263 (15) | ||
Cl4—U1—Cl5i | 91.56 (6) | Cl6ii—U1—Cl1ii | 89.42 (5) |
Cl4—U1—Cl3 | 89.69 (6) | Cl4—U1—Cl2iii | 178.87 (6) |
Cl5i—U1—Cl3 | 89.92 (6) | Cl5i—U1—Cl2iii | 89.14 (5) |
Cl4—U1—Cl6ii | 90.83 (6) | Cl3—U1—Cl2iii | 91.20 (5) |
Cl5i—U1—Cl6ii | 90.89 (5) | Cl6ii—U1—Cl2iii | 88.28 (5) |
Cl3—U1—Cl6ii | 179.02 (6) | Cl1ii—U1—Cl2iii | 89.86 (5) |
Cl4—U1—Cl1ii | 89.44 (5) | Cl7iv—S1—Cl8 | 102.92 (10) |
Cl5i—U1—Cl1ii | 178.95 (6) | Cl7iv—S1—Cl9 | 102.93 (10) |
Cl3—U1—Cl1ii | 89.76 (6) | Cl8—S1—Cl9 | 102.21 (9) |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+2, y−1/2, −z+3/2; (iii) x+1/2, −y+3/2, −z+2; (iv) x−1/2, −y+3/2, −z+2. |
Bond | d (current study) | d (Sawodny et al., 1983) |
U1—Cl1ii | 2.5263 (15) | 2.510 (10) |
U1—Cl2iii | 2.5297 (15) | 2.531 (9) |
U1—Cl3 | 2.5151 (16) | 2.521 (10) |
U1—Cl4 | 2.4869 (16) | 2.485 (11) |
U1—Cl5i | 2.5045 (16) | 2.499 (10) |
U1—Cl6ii | 2.5209 (15) | 2.511 (9) |
S1—Cl7 | 1.975 (2) | 1.955 (14) |
S1—Cl8 | 1.975 (2) | 1.973 (13) |
S1—Cl9 | 1.979 (2) | 1.959 (13) |
Symmetry codes: (i) -x + 3/2, -y + 1, z + 1/2; (ii) -x + 2, y - 1/2, -z + 3/2; (iii) x + 1/2, -y + 3/2, -z + 2. |
Angle | φ (current study) | φ (Sawodny et al., 1983) |
Cl1ii—U1—Cl2iii | 89.86 (5) | 89.9 (3) |
Cl3—U1—Cl6ii | 179.02 (6) | 179.3 (4) |
Cl3—U1—Cl2iii | 91.20 (5) | 91.8 (4) |
Cl3—U1—Cl1ii | 89.76 (6) | 90.0 (4) |
Cl4—U1—Cl2iii | 178.87 (6) | 179.4 (4) |
Cl4—U1—Cl1ii | 89.44 (5) | 89.6 (4) |
Cl4—U1—Cl3 | 89.69 (6) | 88.2 (4) |
Cl4—U1—Cl5i | 91.56 (6) | 91.3 (4) |
Cl4—U1—C6ii | 90.83 (6) | 91.2 (4) |
Cl5i—U1—Cl1ii | 178.95 (6) | 179.0 (4) |
Cl5i—U1—Cl6ii | 90.89 (5) | 90.1 (4) |
Cl5i—U1—Cl2iii | 89.14 (5) | 89.2 (4) |
Cl5i—U1—Cl3 | 89.92 (6) | 89.5 (4) |
Cl6ii—U1—Cl1ii | 89.42 (5) | 90.4 (4) |
Cl6ii—U1—Cl2iii | 88.28 (5) | 88.7 (3) |
Cl7iv—S1—Cl8 | 102.92 (10) | 101.7 (7) |
Cl7i—S1—Cl9 | 102.93 (10) | 103.5 (7) |
Cl8—S1—Cl9 | 102.21 (9) | 101.8 (6) |
Symmetry codes: (i) -x + 3/2, -y + 1, z + 1/2; (ii) -x + 2, y - 1/2, -z + 3/2; (iii) x + 1/2, -y + 3/2, -z + 2; (iv) x - 1/2, -y + 3/2, -z+2. |
Funding information
FK thanks the DFG for very generous funding.
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