Nickel(II) uranium(IV) tris­­ulfide

Crystals of NiUS₃ were obtained from the reaction of the elements Ni, U, S, and of GeI₂ in a CsCl flux at 1173 K. Nickel(II) uranium(IV) tris­ulfide, NiUS₃, has ortho­rhom­bic (Pnma) symmetry and crystallizes in the GdFeO₃ structure type. The compound has a perovskite ABQ₃-like structure, with U occupying the inter­stitial sites of a NiS₆ framework. The U atoms are coordinated by eight S atoms in a distorted bicapped trigonal–prismatic arrangement. The Ni atoms are coordinated by six S atoms in a slightly distorted octa­hedral arrangement. The asymmetric unit comprises one U site (site symmetry .m.), one Ni site (-1), and two S sites (1 and .m.).

Related literature

Uranium chalcogenides of the composition ABQ₃ are known for Sc, V–Ni, Pd, Ru, Rh, and Ba (for a review, see: Narducci & Ibers, 1998). These compounds all have perovskite-type structures with A atoms occupying eight-coordinate inter­stitial sites within a BQ₆ framework. There are two subclasses of the ABQ₃ structure, viz. GdFeO₃ (Pnma) (Marezio et al., 1970) and FeUS₃ (Cmcm) (Noël & Padiou, 1976). Single-crystal refinements have been carried out for BaUS₃ (Brochu et al., 1970), CrUS₃ (Noël et al., 1975), FeUQ₃ (Q = S, Se) (Noël & Padiou, 1976; Jin et al., 2010), ScUS₃ (Julien et al., 1978), RhUS₃ (Daoudi & Noël, 1987), PdUSe₃ (Daoudi & Noël, 1989), and MnUSe₃ (Ijjaali et al., 2004). The unit cell of NiUS₃ was determined previously from powder diffracton experiments (Noël et al., 1971). For standardization of structural data, see: Gelato & Parthé (1987).

Experimental

Crystal data

• NiUS₃

• M_r = 392.92

• Orthorhombic, P n m a

• a = 6.8924 (3) Å

• b = 8.7570 (4) Å

• c = 6.0758 (2) Å

• V = 366.72 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 50.68 mm⁻¹

• T = 100 K

• 0.09 × 0.09 × 0.08 mm

Data collection

• Bruker APEXII CCD diffractometer

• Absorption correction: numerical (SADABS; Bruker, 2009) T_min = 0.093, T_max = 0.108

• 7334 measured reflections

• 748 independent reflections

• 728 reflections with I > 2σ(I)

• R_int = 0.047

Refinement

• R[F² > 2σ(F²)] = 0.018

• wR(F²) = 0.043

• S = 1.36

• 748 reflections

• 29 parameters

• Δρ_max = 2.80 e Å⁻³

• Δρ_min = −1.15 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2013); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: CrystalMaker (Palmer, 2009); software used to prepare material for publication: SHELXL2013.

Supporting information

S1. Comment

NiUS₃ crystallizes in the orthorhombic space group Pnma. Its unit cell was previously determined (Noël et al., 1971), revealing the compound to be isostructral with uranium compounds with analogous compositions. A number of uranium chalcogenides of the composition ABQ₃ are known (for a review, see: Narducci & Ibers, 1998) and crystallize in two subclasses, viz. GdFeO₃ (Pnma) (Marezio et al., 1970) and FeUS₃ (Cmcm) (Noël & Padiou, 1976). Most of the ABQ₃ compounds crystallize in the three-dimesional GdFeO₃ structure type. However, when B = Sc, Fe, or Mn, they crystallize in the layered FeUS₃ structure type. Refinements based on single crystal data have been carried out for BaUS₃ (Brochu et al., 1970), CrUS₃ (Noël et al., 1975), FeUQ₃ (Q = S, Se) (Noël & Padiou, 1976; Jin et al., 2010), ScUS₃ (Julien et al., 1978), RhUS₃ (Daoudi & Noël, 1987), PdUSe₃ (Daoudi & Noël, 1989), and MnUSe₃ (Ijjaali et al., 2004).

The structure is composed of one U site, one Ni site, and two S sites. The uranium atoms are coordinated by eight S atoms in a distorted bicapped trigonal-prismatic arrangement. The Ni atoms are coordinated by six S atoms in a slightly distorted octahedral arrangement. The unit cell is shown in Figure 1 and a packing diagram is shown in Figure 2. There is no evidence of S—S bonding and thus formal oxidation states may be assigned as +II,+IV, and –II for Ni, U, and S, respectively. U—S distances range from 2.6666 (13) Å to 3.0088 (8) Å. These distances compare favorably with the U—S distances in the related compound RhUS₃ (Daoudi & Noël, 1987). Ni—S distances range from 2.3386 (4) Å to 2.4739 (9) Å.

Related literature

Uranium chalcogenides of the composition ABQ₃ are known for Sc, V—Ni, Pd, Ru, Rh, and Ba (for a review, see: Narducci & Ibers, 1998). These compounds all have perovskite-type structures with A atoms occupying eight-coordinate interstitial sites within a BQ₆ framework. There are two subclasses of the ABQ₃ structure, viz. GdFeO₃ (Pnma) (Marezio et al., 1970) and FeUS₃ (Cmcm) (Noël & Padiou, 1976). Single crystal refinements have been carried out for BaUS₃ (Brochu et al., 1970), CrUS₃ (Noël et al., 1975), FeUQ₃ (Q = S, Se) (Noël & Padiou, 1976; Jin et al., 2010), ScUS₃ (Julien et al., 1978), RhUS₃ (Daoudi & Noël, 1987), PdUSe₃ (Daoudi & Noël, 1989), and MnUSe₃ (Ijjaali et al., 2004). The unit cell of NiUS₃ was previously determined from powder diffracton experiments (Noël et al., 1971). For standardization of structural data, see: Gelato & Parthé (1987).

S2. Experimental

NiUS₃ was obtained from the reaction of U (0.126 mmol), GeI₂ (0.063 mmol), Ni (0.126 mmol), and S (0.378 mmol) in a CsCl flux (0.445 mmol). The reactants were loaded into a carbon-coated fused-silica tube under an inert Ar atmosphere that was evacuated to 10 ^-4 Torr. The tube was then flame sealed. It was placed in a computer-controlled furnace and heated to 1173 K in 12 h, held there for 6 h, cooled to 1073 K in 12 h and then held there for a further 96 h. The tube was next cooled at 5 K/h to 773 K and then to 298 K in 12 h. The reaction yielded black prisms of NiUS₃ and black rectangular plates of NiU₈S₁₇ (Noël et al., 1971). The crystals were washed with water and dried with acetone to remove excess flux. They are stable to both air and moisture.

S3. Refinement

Atomic positions were standardized with the program STRUCTURE TIDY (Gelato & Parthé, 1987). The highest peak of 2.8 (3) e^-/ų is 1.81 Å from atom S2 and the deepest hole of -1.2 (3) e^-/ų is 0.96 Å from atom U1.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2013); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2013); molecular graphics: CrystalMaker (Palmer, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2013).

Figures

	Fig. 1. The unit cell of NiUS3. Displacement ellipsoids at the 95% probability level are shown.
	Fig. 2. A packing diagram of NiUS3 viewed down the a axis. Ni atoms are green, U atoms are black, and S atoms are orange.

Nickel(II) uranium(IV) trisulfide

Crystal data

NiUS3	Dx = 7.117 Mg m^−3
Mr = 392.92	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 3973 reflections
a = 6.8924 (3) Å	θ = 4.1–33.2°
b = 8.7570 (4) Å	µ = 50.68 mm^−1
c = 6.0758 (2) Å	T = 100 K
V = 366.72 (3) Å^3	Prism, black
Z = 4	0.09 × 0.09 × 0.08 mm
F(000) = 672

Data collection

Bruker APEXII CCD diffractometer	728 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
φ and ω scans	θmax = 33.2°, θmin = 4.1°
Absorption correction: numerical (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.093, Tmax = 0.108	k = −13→13
7334 measured reflections	l = −9→9
748 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0149Fo^2)^2]
R[F^2 > 2σ(F^2)] = 0.018	(Δ/σ)max < 0.001
wR(F^2) = 0.043	Δρmax = 2.80 e Å^−3
S = 1.36	Δρmin = −1.15 e Å^−3
748 reflections	Extinction correction: SHELXL2013 (Sheldrick, 2013), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
29 parameters	Extinction coefficient: 0.0039 (4)

Special details

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.

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

	x	y	z	Uiso*/Ueq
U1	0.38141 (3)	0.2500	0.05064 (3)	0.00770 (8)
Ni1	0.0000	0.0000	0.0000	0.00778 (13)
S1	0.18039 (14)	0.05448 (9)	0.33217 (13)	0.00731 (15)
S2	0.52930 (19)	0.2500	0.63121 (19)	0.0085 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.00525 (11)	0.00896 (10)	0.00890 (10)	0.000	0.00069 (5)	0.000
Ni1	0.0069 (3)	0.0081 (2)	0.0083 (2)	−0.0009 (2)	−0.0008 (2)	0.0002 (2)
S1	0.0057 (4)	0.0087 (3)	0.0075 (3)	0.0000 (3)	0.0000 (3)	0.0004 (3)
S2	0.0081 (6)	0.0079 (4)	0.0095 (5)	0.000	0.0023 (4)	0.000

Geometric parameters (Å, º)

U1—S2^i	2.6666 (13)	Ni1—S1^ix	2.4180 (8)
U1—S2^ii	2.7446 (12)	Ni1—S1	2.4180 (8)
U1—S1^iii	2.7721 (9)	Ni1—S1^i	2.4739 (9)
U1—S1^iv	2.7721 (9)	Ni1—S1^vi	2.4739 (9)
U1—S1^v	2.7888 (8)	Ni1—U1^ix	3.4349 (2)
U1—S1	2.7888 (8)	S1—Ni1^x	2.4739 (9)
U1—S1^vi	3.0088 (8)	S1—U1^i	2.7722 (9)
U1—S1^vii	3.0088 (8)	S1—U1^x	3.0088 (8)
U1—Ni1	3.4349 (2)	S2—Ni1^x	2.3386 (4)
U1—Ni1^viii	3.4349 (2)	S2—Ni1^iii	2.3386 (4)
Ni1—S2^i	2.3386 (4)	S2—U1^iv	2.6666 (13)
Ni1—S2^vi	2.3386 (4)	S2—U1^xi	2.7446 (12)
S2^i—U1—S2^ii	87.32 (2)	S2^i—Ni1—S2^vi	180.0
S2^i—U1—S1^iii	141.532 (18)	S2^i—Ni1—S1^ix	86.82 (3)
S2^ii—U1—S1^iii	87.85 (3)	S2^vi—Ni1—S1^ix	93.18 (3)
S2^i—U1—S1^iv	141.532 (18)	S2^i—Ni1—S1	93.18 (3)
S2^ii—U1—S1^iv	87.85 (3)	S2^vi—Ni1—S1	86.82 (3)
S1^iii—U1—S1^iv	76.29 (3)	S1^ix—Ni1—S1	180.00 (4)
S2^i—U1—S1^v	78.58 (3)	S2^i—Ni1—S1^i	92.11 (4)
S2^ii—U1—S1^v	138.939 (19)	S2^vi—Ni1—S1^i	87.89 (4)
S1^iii—U1—S1^v	80.362 (19)	S1^ix—Ni1—S1^i	85.654 (14)
S1^iv—U1—S1^v	126.225 (15)	S1—Ni1—S1^i	94.346 (14)
S2^i—U1—S1	78.58 (3)	S2^i—Ni1—S1^vi	87.89 (4)
S2^ii—U1—S1	138.939 (19)	S2^vi—Ni1—S1^vi	92.11 (4)
S1^iii—U1—S1	126.225 (15)	S1^ix—Ni1—S1^vi	94.346 (14)
S1^iv—U1—S1	80.362 (19)	S1—Ni1—S1^vi	85.654 (14)
S1^v—U1—S1	75.75 (3)	S1^i—Ni1—S1^vi	180.0
S2^i—U1—S1^vi	71.84 (2)	S2^i—Ni1—U1^ix	129.21 (3)
S2^ii—U1—S1^vi	69.082 (18)	S2^vi—Ni1—U1^ix	50.79 (3)
S1^iii—U1—S1^vi	139.987 (15)	S1^ix—Ni1—U1^ix	53.55 (2)
S1^iv—U1—S1^vi	70.81 (3)	S1—Ni1—U1^ix	126.45 (2)
S1^v—U1—S1^vi	138.102 (15)	S1^i—Ni1—U1^ix	58.556 (19)
S1—U1—S1^vi	69.890 (12)	S1^vi—Ni1—U1^ix	121.444 (19)
S2^i—U1—S1^vii	71.84 (2)	S2^i—Ni1—U1	50.79 (3)
S2^ii—U1—S1^vii	69.082 (18)	S2^vi—Ni1—U1	129.21 (3)
S1^iii—U1—S1^vii	70.81 (3)	S1^ix—Ni1—U1	126.45 (2)
S1^iv—U1—S1^vii	139.987 (15)	S1—Ni1—U1	53.55 (2)
S1^v—U1—S1^vii	69.890 (12)	S1^i—Ni1—U1	121.444 (19)
S1—U1—S1^vii	138.102 (15)	S1^vi—Ni1—U1	58.556 (19)
S1^vi—U1—S1^vii	124.80 (3)	U1^ix—Ni1—U1	180.0
S2^i—U1—Ni1	42.805 (10)	Ni1—S1—Ni1^x	139.81 (4)
S2^ii—U1—Ni1	101.60 (2)	Ni1—S1—U1^i	87.36 (3)
S1^iii—U1—Ni1	170.255 (18)	Ni1^x—S1—U1^i	132.47 (3)
S1^iv—U1—Ni1	101.436 (18)	Ni1—S1—U1	82.22 (2)
S1^v—U1—Ni1	93.784 (19)	Ni1^x—S1—U1	85.92 (3)
S1—U1—Ni1	44.224 (18)	U1^i—S1—U1	98.49 (2)
S1^vi—U1—Ni1	44.546 (18)	Ni1—S1—U1^x	96.93 (3)
S1^vii—U1—Ni1	114.642 (18)	Ni1^x—S1—U1^x	76.90 (2)
S2^i—U1—Ni1^viii	42.805 (10)	U1^i—S1—U1^x	109.19 (3)
S2^ii—U1—Ni1^viii	101.60 (2)	U1—S1—U1^x	152.25 (3)
S1^iii—U1—Ni1^viii	101.436 (18)	Ni1^x—S2—Ni1^iii	138.82 (6)
S1^iv—U1—Ni1^viii	170.255 (18)	Ni1^x—S2—U1^iv	86.41 (3)
S1^v—U1—Ni1^viii	44.224 (18)	Ni1^iii—S2—U1^iv	86.41 (3)
S1—U1—Ni1^viii	93.784 (19)	Ni1^x—S2—U1^xi	106.53 (3)
S1^vi—U1—Ni1^viii	114.642 (18)	Ni1^iii—S2—U1^xi	106.53 (3)
S1^vii—U1—Ni1^viii	44.546 (18)	U1^iv—S2—U1^xi	136.28 (5)
Ni1—U1—Ni1^viii	79.190 (5)

Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x, y, z−1; (iii) x+1/2, −y+1/2, −z+1/2; (iv) x+1/2, y, −z+1/2; (v) x, −y+1/2, z; (vi) −x+1/2, −y, z−1/2; (vii) −x+1/2, y+1/2, z−1/2; (viii) −x, y+1/2, −z; (ix) −x, −y, −z; (x) −x+1/2, −y, z+1/2; (xi) x, y, z+1.