Manganese(II) octa­uranium(IV) hepta­deca­sulfide

Oh, G.N.; Ibers, J.A.

doi:10.1107/S1600536811030546

inorganic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page i46

doi:10.1107/S1600536811030546

Open

access

Manganese(II) octauranium(IV) heptadecasulfide

George N. Oh ^a and James A. Ibers ^a ^*

^aDepartment of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, IL 60208-3113, USA
^*Correspondence e-mail: ibers@chem.northwestern.edu

(Received 10 July 2011; accepted 28 July 2011; online 6 August 2011)

Single crystals of manganese(II) octauranium(IV) heptadecasulfide, MnU₈S₁₇, were grown from the reaction of the elements in a RbCl flux. MnU₈S₁₇ crystallizes in the space group C2/m in the CrU₈S₁₇ structure type. The asymmetric unit is composed of the following atoms with site symmetries shown: U1 (1), U2 (m), U3 (m), Mn1 (2/m), S1 (1), S2 (1); S3 (m), S4 (m), S5 (m), S6 (m) and S7 (2/m). The three U^IV atoms are each coordinated by eight S atoms in a bicapped trigonal–prismatic arrangement. The Mn^II atom is coordinated by six S atoms in a distorted octahedral arrangement.

Related literature

MnU₈S₁₇ was previously determined to be isostructural with CrU₈S₁₇ (Noël et al., 1975) from powder diffraction data (Noël, 1973 ). Single-crystal refinements have been carried out for the Cr, Fe (Kohlmann et al., 1997 ), and Sc (Vovan & Rodier, 1979 ) analogues. Magnetic data for these compounds are available (Noël & Troc, 1979 ). The Mn—S distances are consistent with those expected for low-spin Mn^II (Shannon, 1976 ). For synthetic details, see: Bugaris & Ibers (2008 ); Haneveld & Jellinek (1969 ). For computational details, see: Gelato & Parthé (1987 ).

Experimental

Crystal data

MnU₈S₁₇
M_r = 2504.20
Monoclinic, C 2/m
a = 13.3549 (6) Å
b = 8.3893 (4) Å
c = 10.4927 (5) Å
β = 101.658 (2)°
V = 1151.33 (9) Å³
Z = 2
Mo Kα radiation
μ = 58.10 mm⁻¹
T = 100 K
0.15 × 0.09 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: numerical face indexed (SADABS; Sheldrick, 2008a ) T_min = 0.043, T_max = 0.085
8422 measured reflections
1609 independent reflections
1578 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.068
S = 2.10
1609 reflections
73 parameters
Δρ_max = 3.90 e Å⁻³
Δρ_min = −1.94 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: CrystalMaker (Palmer, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030546/wm2512sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030546/wm2512Isup2.hkl

checkCIF report

Comment top

Single crystals of MnU₈S₁₇ were obtained in an attempt to synthesize a quaternary arsenic-containing compound (see Experimental).

MnU₈S₁₇ crystallizes in the CrU₈S₁₇ structure type (Noël et al., 1975). Structure determinations based on single crystal data for isostructural ScU₈S₁₇ (Vovan & Rodier, 1979) and FeU₈S₁₇ (Kohlmann et al., 1997) have also been reported, and MnU₈S₁₇ was also determined to be isostructural from powder diffraction experiments (Noël, 1973).

The structure comprises three independent U atoms, each coordinated by eight S atoms in a bicapped trigonal prismatic arrangement, and one independent Mn atom that is coordinated by six S atoms in a distorted octahedral arrangement (Figs. 1,2). There are no S—S bonds in the structure, so formal oxidation states of +IV, +II, and -II may be assigned to U, Mn, and S, respectively. U—S distances have the following ranges: U1—S: 2.7546 (19) Å to 2.9509 (3) Å; U2—S: 2.735 (3) Å to 2.8559 (4) Å; U3—S: 2.680 (2) Å to 3.031 (3) Å. These distances are similar to those found in the structures of the Cr and Fe analogues. Mn—S distances range from 2.398 (3) Å to 2.5168 (19) Å; these are shorter than a typical high-spin six-coordinate Mn^II—S distance of 2.66 Å, but are consistent with the typical low-spin six-coordinate Mn^II—S distance of 2.51 Å (Shannon, 1976). Low-spin Mn^II is consistent with the ⁶S_5/2 configuration assigned from magnetic studies (Noël & Troc, 1979).

Related literature top

MnU₈S₁₇ was previously determined to be isostructural with CrU₈S₁₇ (Noël et al., 1975) from powder diffraction data (Noël, 1973). Single-crystal refinements have been carried out for the Cr, Fe (Kohlmann et al., 1997), and Sc (Vovan & Rodier, 1979) analogues. Magnetic data for these compounds are available (Noël & Troc, 1979). The Mn—S distances are consistent with those expected for low-spin Mn^II (Shannon, 1976). For synthetic details, see: Bugaris & Ibers (2008); Haneveld & Jellinek (1969). For computational details, see: Gelato & Parthé (1987).

Experimental top

Black blocks of MnU₈S₁₇ were obtained by combining U (0.126 mmol), Mn (Johnson Matthey 99.3%, 0.126 mmol), and S (Mallinckrodt 99.6% sublimed, 0.504 mmol) in a RbCl flux (Alfa 99.8%, 1.26 mmol) with As as a mineralizer (Strem 2N, 0.126 mmol). U filings (Oak Ridge National Laboratory) were powdered by hydridization and subsequent decomposition under heat and vacuum (Bugaris & Ibers, 2008), in a modification of a previous literature method (Haneveld & Jellinek, 1969). The mixture was loaded into a carbon-coated fused-silica tube in an Ar filled glove box and then sealed under 10 ^-4 Torr vacuum. The vessel was heated in a computer-controlled furnace to 1073 K in 96 h, held for 96 h, cooled to 673 K in 96 h, then cooled to 298 K in 48 h. The flux was washed off with water and surface impurities were mechanically removed from a single crystal.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: CrystalMaker (Palmer, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008b).

Figures top

	Fig. 1. A packing diagram for MnU₈S₁₇, viewed nearly along the b axis. U atoms are black, S atoms are yellow, and the MnSe₆ octahedra are green.
	Fig. 2. The asymmetric unit of MnU₈S₁₇. Displacement ellipsoids at the 95% probability level are shown.

Manganese(II) octauranium(IV) heptadecasulfide top

Crystal data top

MnU₈S₁₇	F(000) = 2066
M_r = 2504.20	D_x = 7.223 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 8717 reflections
a = 13.3549 (6) Å	θ = 2.9–30.5°
b = 8.3893 (4) Å	µ = 58.10 mm⁻¹
c = 10.4927 (5) Å	T = 100 K
β = 101.658 (2)°	Rectangular block, black
V = 1151.33 (9) Å³	0.15 × 0.09 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1609 independent reflections
Radiation source: fine-focus sealed tube	1578 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 29.1°, θ_min = 2.0°
Absorption correction: numerical face indexed (SADABS; Sheldrick, 2008a)	h = −18→17
T_min = 0.043, T_max = 0.085	k = −10→11
8422 measured reflections	l = −14→14

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)] = 0.026	w = 1/[σ²(F_o²) + (0.0161F_o²)²]
wR(F²) = 0.068	(Δ/σ)_max = 0.001
S = 2.10	Δρ_max = 3.90 e Å⁻³
1609 reflections	Δρ_min = −1.94 e Å⁻³
73 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00082 (4)

Crystal data top

MnU₈S₁₇	V = 1151.33 (9) Å³
M_r = 2504.20	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 13.3549 (6) Å	µ = 58.10 mm⁻¹
b = 8.3893 (4) Å	T = 100 K
c = 10.4927 (5) Å	0.15 × 0.09 × 0.08 mm
β = 101.658 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1609 independent reflections
Absorption correction: numerical face indexed (SADABS; Sheldrick, 2008a)	1578 reflections with I > 2σ(I)
T_min = 0.043, T_max = 0.085	R_int = 0.034
8422 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	73 parameters
wR(F²) = 0.068	0 restraints
S = 2.10	Δρ_max = 3.90 e Å⁻³
1609 reflections	Δρ_min = −1.94 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
U1	0.44179 (2)	0.25549 (3)	0.29633 (3)	0.00531 (11)
U2	0.20440 (3)	0.0000	0.45685 (4)	0.00510 (12)
U3	0.68285 (3)	0.0000	0.02025 (4)	0.00541 (12)
Mn1	0.0000	0.0000	0.0000	0.0058 (5)
S1	0.12730 (15)	0.3047 (2)	0.46870 (18)	0.0065 (4)
S2	0.36424 (15)	0.3062 (2)	0.03492 (18)	0.0064 (4)
S3	0.0598 (2)	0.0000	0.2314 (3)	0.0066 (5)
S4	0.2086 (2)	0.0000	0.7197 (3)	0.0061 (5)
S5	0.3030 (2)	0.0000	0.2463 (3)	0.0058 (5)
S6	0.5211 (2)	0.0000	0.1694 (3)	0.0061 (5)
S7	0.0000	0.0000	0.5000	0.0056 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
U1	0.0056 (2)	0.00542 (18)	0.00528 (17)	−0.00005 (10)	0.00195 (13)	0.00004 (10)
U2	0.0053 (2)	0.0054 (2)	0.0051 (2)	0.000	0.00217 (15)	0.000
U3	0.0063 (2)	0.0052 (2)	0.00499 (19)	0.000	0.00170 (16)	0.000
Mn1	0.0047 (12)	0.0068 (11)	0.0064 (10)	0.000	0.0024 (9)	0.000
S1	0.0062 (10)	0.0067 (9)	0.0069 (8)	−0.0004 (8)	0.0017 (7)	0.0000 (7)
S2	0.0064 (10)	0.0058 (9)	0.0075 (8)	−0.0008 (7)	0.0023 (7)	0.0000 (7)
S3	0.0079 (14)	0.0067 (13)	0.0057 (11)	0.000	0.0024 (10)	0.000
S4	0.0059 (14)	0.0056 (12)	0.0071 (12)	0.000	0.0018 (10)	0.000
S5	0.0059 (14)	0.0062 (12)	0.0058 (11)	0.000	0.0027 (10)	0.000
S6	0.0067 (14)	0.0059 (12)	0.0055 (12)	0.000	0.0006 (10)	0.000
S7	0.0034 (19)	0.0050 (16)	0.0091 (17)	0.000	0.0025 (14)	0.000

Geometric parameters (Å, º) top

U1—S3ⁱ	2.7546 (19)	U3—U1^iv	4.0205 (4)
U1—S2	2.7621 (19)	U3—U1^vii	4.0205 (4)
U1—S1ⁱⁱ	2.802 (2)	Mn1—S3	2.398 (3)
U1—S5	2.8129 (19)	Mn1—S3^x	2.398 (3)
U1—S6	2.8390 (18)	Mn1—S2^xi	2.5168 (19)
U1—S1ⁱⁱⁱ	2.8469 (19)	Mn1—S2^xii	2.5168 (19)
U1—S4ⁱⁱⁱ	2.852 (2)	Mn1—S2^xiii	2.5168 (19)
U1—S7ⁱ	2.9509 (3)	Mn1—S2^xiv	2.5168 (19)
U1—U3^iv	4.0206 (4)	S1—U2ⁱⁱⁱ	2.763 (2)
U1—U2ⁱⁱⁱ	4.0951 (5)	S1—U1^xiv	2.802 (2)
U2—S3	2.735 (3)	S1—U1ⁱⁱⁱ	2.8469 (19)
U2—S4	2.747 (3)	S2—Mn1ⁱ	2.5168 (19)
U2—S1ⁱⁱⁱ	2.763 (2)	S2—U3^iv	2.680 (2)
U2—S1^v	2.763 (2)	S2—U3^xv	2.896 (2)
U2—S1	2.768 (2)	S3—U1^xi	2.7546 (19)
U2—S1^vi	2.768 (2)	S3—U1^xiv	2.7546 (19)
U2—S5	2.791 (3)	S4—U3^viii	2.819 (3)
U2—S7	2.8559 (4)	S4—U1^v	2.852 (2)
U2—U1ⁱⁱⁱ	4.0952 (5)	S4—U1ⁱⁱⁱ	2.852 (2)
U2—U1^v	4.0952 (5)	S5—U1^vi	2.8130 (19)
U3—S2^iv	2.680 (2)	S5—U3^iv	2.841 (3)
U3—S2^vii	2.680 (2)	S6—U1^vi	2.8390 (18)
U3—S4^viii	2.819 (3)	S6—U3^iv	3.031 (3)
U3—S5^iv	2.841 (3)	S7—U2^xvi	2.8559 (4)
U3—S2ⁱⁱ	2.896 (2)	S7—U1^xi	2.9509 (3)
U3—S2^ix	2.896 (2)	S7—U1ⁱⁱⁱ	2.9509 (3)
U3—S6	2.912 (3)	S7—U1^v	2.9509 (3)
U3—S6^iv	3.031 (3)	S7—U1^xiv	2.9509 (3)

S3ⁱ—U1—S2	76.01 (7)	S2^vii—U3—S2^ix	134.99 (5)
S3ⁱ—U1—S1ⁱⁱ	79.55 (7)	S4^viii—U3—S2^ix	71.79 (6)
S2—U1—S1ⁱⁱ	140.70 (6)	S5^iv—U3—S2^ix	80.27 (6)
S3ⁱ—U1—S5	155.43 (8)	S2ⁱⁱ—U3—S2^ix	68.33 (8)
S2—U1—S5	80.28 (7)	S2^iv—U3—S6	87.07 (5)
S1ⁱⁱ—U1—S5	116.52 (6)	S2^vii—U3—S6	87.07 (5)
S3ⁱ—U1—S6	99.20 (7)	S4^viii—U3—S6	76.83 (8)
S2—U1—S6	75.58 (7)	S5^iv—U3—S6	137.15 (8)
S1ⁱⁱ—U1—S6	78.56 (7)	S2ⁱⁱ—U3—S6	132.44 (5)
S5—U1—S6	68.37 (7)	S2^ix—U3—S6	132.44 (5)
S3ⁱ—U1—S1ⁱⁱⁱ	130.39 (7)	S2^iv—U3—S6^iv	73.60 (4)
S2—U1—S1ⁱⁱⁱ	139.93 (6)	S2^vii—U3—S6^iv	73.60 (4)
S1ⁱⁱ—U1—S1ⁱⁱⁱ	78.93 (6)	S4^viii—U3—S6^iv	148.59 (8)
S5—U1—S1ⁱⁱⁱ	73.14 (7)	S5^iv—U3—S6^iv	65.38 (8)
S6—U1—S1ⁱⁱⁱ	119.29 (6)	S2ⁱⁱ—U3—S6^iv	131.75 (5)
S3ⁱ—U1—S4ⁱⁱⁱ	83.16 (6)	S2^ix—U3—S6^iv	131.75 (5)
S2—U1—S4ⁱⁱⁱ	73.29 (7)	S6—U3—S6^iv	71.77 (8)
S1ⁱⁱ—U1—S4ⁱⁱⁱ	133.46 (7)	S2^iv—U3—U1^iv	43.17 (4)
S5—U1—S4ⁱⁱⁱ	96.17 (6)	S2^vii—U3—U1^iv	107.02 (4)
S6—U1—S4ⁱⁱⁱ	147.19 (8)	S4^viii—U3—U1^iv	147.748 (6)
S1ⁱⁱⁱ—U1—S4ⁱⁱⁱ	80.27 (7)	S5^iv—U3—U1^iv	44.40 (4)
S3ⁱ—U1—S7ⁱ	65.25 (5)	S2ⁱⁱ—U3—U1^iv	123.06 (4)
S2—U1—S7ⁱ	127.10 (4)	S2^ix—U3—U1^iv	86.95 (4)
S1ⁱⁱ—U1—S7ⁱ	65.71 (4)	S6—U3—U1^iv	102.46 (5)
S5—U1—S7ⁱ	137.07 (6)	S6^iv—U3—U1^iv	44.81 (3)
S6—U1—S7ⁱ	142.74 (6)	S2^iv—U3—U1^vii	107.02 (4)
S1ⁱⁱⁱ—U1—S7ⁱ	65.18 (4)	S2^vii—U3—U1^vii	43.17 (4)
S4ⁱⁱⁱ—U1—S7ⁱ	67.79 (5)	S4^viii—U3—U1^vii	147.748 (6)
S3ⁱ—U1—U3^iv	110.77 (6)	S5^iv—U3—U1^vii	44.40 (4)
S2—U1—U3^iv	41.58 (4)	S2ⁱⁱ—U3—U1^vii	86.95 (4)
S1ⁱⁱ—U1—U3^iv	126.98 (4)	S2^ix—U3—U1^vii	123.06 (4)
S5—U1—U3^iv	44.95 (6)	S6—U3—U1^vii	102.46 (5)
S6—U1—U3^iv	48.80 (6)	S6^iv—U3—U1^vii	44.81 (3)
S1ⁱⁱⁱ—U1—U3^iv	117.93 (4)	U1^iv—U3—U1^vii	64.432 (10)
S4ⁱⁱⁱ—U1—U3^iv	99.54 (5)	S3—Mn1—S3^x	180.0
S7ⁱ—U1—U3^iv	166.765 (10)	S3—Mn1—S2^xi	87.41 (7)
S3ⁱ—U1—U2ⁱⁱⁱ	98.80 (5)	S3^x—Mn1—S2^xi	92.59 (7)
S2—U1—U2ⁱⁱⁱ	114.83 (4)	S3—Mn1—S2^xii	92.59 (7)
S1ⁱⁱ—U1—U2ⁱⁱⁱ	98.88 (4)	S3^x—Mn1—S2^xii	87.41 (7)
S5—U1—U2ⁱⁱⁱ	96.86 (5)	S2^xi—Mn1—S2^xii	180.00 (11)
S6—U1—U2ⁱⁱⁱ	161.01 (4)	S3—Mn1—S2^xiii	92.59 (7)
S1ⁱⁱⁱ—U1—U2ⁱⁱⁱ	42.42 (4)	S3^x—Mn1—S2^xiii	87.41 (7)
S4ⁱⁱⁱ—U1—U2ⁱⁱⁱ	42.01 (5)	S2^xi—Mn1—S2^xiii	99.50 (9)
S7ⁱ—U1—U2ⁱⁱⁱ	44.218 (7)	S2^xii—Mn1—S2^xiii	80.50 (9)
U3^iv—U1—U2ⁱⁱⁱ	128.230 (12)	S3—Mn1—S2^xiv	87.41 (7)
S3—U2—S4	137.38 (8)	S3^x—Mn1—S2^xiv	92.59 (7)
S3—U2—S1ⁱⁱⁱ	129.53 (6)	S2^xi—Mn1—S2^xiv	80.50 (9)
S4—U2—S1ⁱⁱⁱ	82.29 (6)	S2^xii—Mn1—S2^xiv	99.50 (9)
S3—U2—S1^v	129.53 (6)	S2^xiii—Mn1—S2^xiv	180.00 (9)
S4—U2—S1^v	82.29 (6)	U2ⁱⁱⁱ—S1—U2	105.75 (7)
S1ⁱⁱⁱ—U2—S1^v	72.72 (8)	U2ⁱⁱⁱ—S1—U1^xiv	148.40 (8)
S3—U2—S1	80.49 (5)	U2—S1—U1^xiv	95.33 (6)
S4—U2—S1	83.52 (5)	U2ⁱⁱⁱ—S1—U1ⁱⁱⁱ	104.35 (6)
S1ⁱⁱⁱ—U2—S1	74.25 (7)	U2—S1—U1ⁱⁱⁱ	93.65 (6)
S1^v—U2—S1	145.44 (5)	U1^xiv—S1—U1ⁱⁱⁱ	97.35 (6)
S3—U2—S1^vi	80.49 (5)	Mn1ⁱ—S2—U3^iv	137.09 (8)
S4—U2—S1^vi	83.52 (5)	Mn1ⁱ—S2—U1	96.17 (6)
S1ⁱⁱⁱ—U2—S1^vi	145.44 (5)	U3^iv—S2—U1	95.25 (6)
S1^v—U2—S1^vi	74.25 (7)	Mn1ⁱ—S2—U3^xv	104.41 (7)
S1—U2—S1^vi	134.89 (9)	U3^iv—S2—U3^xv	111.68 (7)
S3—U2—S5	71.28 (8)	U1—S2—U3^xv	106.32 (6)
S4—U2—S5	151.35 (9)	Mn1—S3—U2	155.27 (12)
S1ⁱⁱⁱ—U2—S5	74.75 (6)	Mn1—S3—U1^xi	99.23 (8)
S1^v—U2—S5	74.75 (6)	U2—S3—U1^xi	97.20 (7)
S1—U2—S5	105.95 (4)	Mn1—S3—U1^xiv	99.23 (8)
S1^vi—U2—S5	105.95 (4)	U2—S3—U1^xiv	97.20 (7)
S3—U2—S7	66.83 (6)	U1^xi—S3—U1^xiv	96.26 (9)
S4—U2—S7	70.55 (6)	U2—S4—U3^viii	150.90 (11)
S1ⁱⁱⁱ—U2—S7	134.75 (4)	U2—S4—U1^v	93.99 (7)
S1^v—U2—S7	134.75 (4)	U3^viii—S4—U1^v	105.98 (7)
S1—U2—S7	67.46 (4)	U2—S4—U1ⁱⁱⁱ	93.99 (7)
S1^vi—U2—S7	67.46 (4)	U3^viii—S4—U1ⁱⁱⁱ	105.98 (7)
S5—U2—S7	138.10 (6)	U1^v—S4—U1ⁱⁱⁱ	91.99 (8)
S3—U2—U1ⁱⁱⁱ	101.73 (5)	U2—S5—U1	104.51 (7)
S4—U2—U1ⁱⁱⁱ	44.00 (4)	U2—S5—U1^vi	104.51 (7)
S1ⁱⁱⁱ—U2—U1ⁱⁱⁱ	89.36 (4)	U1—S5—U1^vi	99.28 (9)
S1^v—U2—U1ⁱⁱⁱ	125.64 (4)	U2—S5—U3^iv	156.22 (12)
S1—U2—U1ⁱⁱⁱ	43.93 (4)	U1—S5—U3^iv	90.65 (7)
S1^vi—U2—U1ⁱⁱⁱ	101.83 (4)	U1^vi—S5—U3^iv	90.65 (7)
S5—U2—U1ⁱⁱⁱ	149.546 (11)	U1^vi—S6—U1	98.05 (8)
S7—U2—U1ⁱⁱⁱ	46.101 (7)	U1^vi—S6—U3	129.76 (5)
S3—U2—U1^v	101.73 (5)	U1—S6—U3	129.76 (5)
S4—U2—U1^v	44.00 (4)	U1^vi—S6—U3^iv	86.39 (7)
S1ⁱⁱⁱ—U2—U1^v	125.64 (4)	U1—S6—U3^iv	86.39 (7)
S1^v—U2—U1^v	89.36 (4)	U3—S6—U3^iv	108.23 (8)
S1—U2—U1^v	101.83 (4)	U2—S7—U2^xvi	180.0
S1^vi—U2—U1^v	43.93 (4)	U2—S7—U1^xi	90.317 (8)
S5—U2—U1^v	149.546 (10)	U2^xvi—S7—U1^xi	89.682 (8)
S7—U2—U1^v	46.101 (7)	U2—S7—U1ⁱⁱⁱ	89.683 (8)
U1ⁱⁱⁱ—U2—U1^v	60.118 (10)	U2^xvi—S7—U1ⁱⁱⁱ	90.318 (8)
S2^iv—U3—S2^vii	146.88 (9)	U1^xi—S7—U1ⁱⁱⁱ	180.0
S2^iv—U3—S4^viii	105.15 (4)	U2—S7—U1^v	89.683 (8)
S2^vii—U3—S4^viii	105.15 (4)	U2^xvi—S7—U1^v	90.318 (8)
S2^iv—U3—S5^iv	81.18 (4)	U1^xi—S7—U1^v	91.925 (11)
S2^vii—U3—S5^iv	81.18 (4)	U1ⁱⁱⁱ—S7—U1^v	88.075 (11)
S4^viii—U3—S5^iv	146.02 (8)	U2—S7—U1^xiv	90.317 (8)
S2^iv—U3—S2ⁱⁱ	134.99 (5)	U2^xvi—S7—U1^xiv	89.682 (8)
S2^vii—U3—S2ⁱⁱ	68.31 (7)	U1^xi—S7—U1^xiv	88.075 (11)
S4^viii—U3—S2ⁱⁱ	71.79 (6)	U1ⁱⁱⁱ—S7—U1^xiv	91.925 (11)
S5^iv—U3—S2ⁱⁱ	80.27 (6)	U1^v—S7—U1^xiv	180.0
S2^iv—U3—S2^ix	68.31 (7)

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

Experimental details

Crystal data
Chemical formula	MnU₈S₁₇
M_r	2504.20
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	100
a, b, c (Å)	13.3549 (6), 8.3893 (4), 10.4927 (5)
β (°)	101.658 (2)
V (Å³)	1151.33 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	58.10
Crystal size (mm)	0.15 × 0.09 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Numerical face indexed (SADABS; Sheldrick, 2008a)
T_min, T_max	0.043, 0.085
No. of measured, independent and observed [I > 2σ(I)] reflections	8422, 1609, 1578
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.068, 2.10
No. of reflections	1609
No. of parameters	73
Δρ_max, Δρ_min (e Å⁻³)	3.90, −1.94

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), CrystalMaker (Palmer, 2009).

Acknowledgements

The research was kindly supported by the US Department of Energy, Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division and Divison of Materials Science and Engineering Grant ER-15522. Use was made of the IMSERC X-ray Facility at Northwestern University, supported by the International Institute of Nanotechnology (IIN).

References

Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bugaris, D. E. & Ibers, J. A. (2008). Acta Cryst. E64, i55–i56. Web of Science CrossRef IUCr Journals Google Scholar
Gelato, L. M. & Parthé, E. (1987). J. Appl. Cryst. 20, 139–143. CrossRef Web of Science IUCr Journals Google Scholar
Haneveld, A. J. K. & Jellinek, F. (1969). J. Less Common Met. 18, 123–129. CrossRef CAS Web of Science Google Scholar
Kohlmann, H., Stöwe, K. & Beck, H. P. (1997). Z. Anorg. Allg. Chem. 623, 897–900. CrossRef CAS Google Scholar
Noël, H. (1973). C. R. Seances Acad. Sci. Ser. C, 277, 463–464. Google Scholar
Noël, H., Potel, M. & Padiou, J. (1975). Acta Cryst. B31, 2634–2637. CrossRef IUCr Journals Web of Science Google Scholar
Noël, H. & Troc, R. (1979). J. Solid State Chem. 27, 123–135. Google Scholar
Palmer, D. (2009). CrystalMaker. CrystalMaker Software Ltd, Oxfordshire, England. Google Scholar
Shannon, R. D. (1976). Acta Cryst. A32, 751–767. CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008b). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vovan, T. & Rodier, N. (1979). C. R. Seances Acad. Sci. Ser. C, 289, 17–20. CAS Google Scholar