Rerefinement of the crystal structure of tri­chlorido­sulfonium­(IV) hexa­chlorido­uranate(V), (SCl₃)[UCl₆]

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 inversion twin with a twin ratio of 4.4:1.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](Cl-S) = 0.002 Å
• R factor = 0.019
• wR factor = 0.043
• Data-to-parameter ratio = 33.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact  Cl1      ..S1       .       3.16 Ang.
                                            1-x,1/2+y,3/2-z  =      3_656 Check

Author Response: Feature of the compound, the SCl3 monocation.

PLAT431_ALERT_2_B Short Inter HL..A Contact  Cl6      ..S1       .       3.07 Ang.
                                           3/2-x,1-y,-1/2+z  =      2_664 Check

Author Response: Feature of the compound, the SCl3 monocation.

Alert level C
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2      ..S1       .       3.29 Ang.
                                            1-x,1/2+y,3/2-z  =      3_656 Check

Author Response: Feature of the compound, the SCl3 monocation.

PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          2 Report

Author Response: missing cusp of data

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          3 Info
PLAT033_ALERT_4_G Flack x Value Deviates > 3.0 * sigma from Zero .      0.186 Note
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by a Factor ...       0.50 Check
PLAT434_ALERT_2_G Short Inter HL..HL Contact Cl4      ..Cl9              3.25 Ang.
                                           1-x,-1/2+y,3/2-z  =      3_646 Check
PLAT794_ALERT_5_G Tentative Bond Valency for U1        (V)       .       5.19 Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   2 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: X-AREA (Stoe, 2016); cell refinement: 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).

Trichloridosulfonium(IV) hexachloridouranate(V)

Crystal data

(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) Å^3	Block, dark yellow
Z = 4	0.15 × 0.1 × 0.08 mm
F(000) = 1044

Data collection

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

Refinement on F^2	Primary atom site location: other
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0148P)^2 + 3.5607P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.019	(Δ/σ)max = 0.001
wR(F^2) = 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

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

U1—Cl4	2.4869 (16)	U1—Cl2^iii	2.5297 (15)
U1—Cl5^i	2.5045 (16)	S1—Cl7^iv	1.975 (2)
U1—Cl3	2.5151 (16)	S1—Cl8	1.975 (2)
U1—Cl6^ii	2.5209 (14)	S1—Cl9	1.979 (2)
U1—Cl1^ii	2.5263 (15)
Cl4—U1—Cl5^i	91.56 (6)	Cl6^ii—U1—Cl1^ii	89.42 (5)
Cl4—U1—Cl3	89.69 (6)	Cl4—U1—Cl2^iii	178.87 (6)
Cl5^i—U1—Cl3	89.92 (6)	Cl5^i—U1—Cl2^iii	89.14 (5)
Cl4—U1—Cl6^ii	90.83 (6)	Cl3—U1—Cl2^iii	91.20 (5)
Cl5^i—U1—Cl6^ii	90.89 (5)	Cl6^ii—U1—Cl2^iii	88.28 (5)
Cl3—U1—Cl6^ii	179.02 (6)	Cl1^ii—U1—Cl2^iii	89.86 (5)
Cl4—U1—Cl1^ii	89.44 (5)	Cl7^iv—S1—Cl8	102.92 (10)
Cl5^i—U1—Cl1^ii	178.95 (6)	Cl7^iv—S1—Cl9	102.93 (10)
Cl3—U1—Cl1^ii	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.