Manganese(II) octa­uranium(IV) hepta­deca­sulfide

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](Mn-S) = 0.002 Å
• R factor = 0.026
• wR factor = 0.068
• Data-to-parameter ratio = 22.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT923_ALERT_1_A S    values in the CIF and FCF Differ by .......   -600.016

Author Response: Presumably, this arises from differences in the weighting schemes. The weighting scheme we used is clearly spelled out in this cif file. I do not know what is used in the analysis of the fcf file so I cannot comment. On the other hand, weighting schemes are on the philosophical side of modern crystallography. See the satirical discussion in Dunitz: "X-ray Analysis and the Structure of Organic Molecules", pp 213-221.

PLAT934_ALERT_3_A Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .       1502
PLAT971_ALERT_2_A Large Calcd. Non-Metal Positive Residual Density       3.52 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

Alert level B
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   U1     --  U3      ..       4.02 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   U1     --  U2      ..       4.10 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   U2     --  U1      ..       4.10 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   U2     --  U1      ..       4.10 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   U3     --  U1      ..       4.02 Ang.
PLAT774_ALERT_1_B Suspect X-Y Bond in CIF:   U3     --  U1      ..       4.02 Ang.
PLAT922_ALERT_1_B wR2 in the CIF and FCF Differ by ...............     0.0210
PLAT927_ALERT_1_B Reported and Calculated  wR2 Differ by .........     0.0109
PLAT928_ALERT_1_B Reported and Calculated    S value   Differ by .     -0.264
PLAT971_ALERT_2_B Large Calcd. Non-Metal Positive Residual Density       3.13 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_B Large Calcd. Non-Metal Positive Residual Density       2.89 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_B Large Calcd. Non-Metal Positive Residual Density       2.81 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

Alert level C
GOODF01_ALERT_2_C  The least squares goodness of fit parameter lies
            outside the range 0.80 <> 2.00
            Goodness of fit given =      2.098
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.973
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.01
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         42
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       2.33 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       2.25 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       2.08 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.96 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.87 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.87 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.81 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.77 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.73 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.73 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.65 eA-3

Author Response: This is not a simple organic; it is a heavy-atom structure (mu = 58 mm-1). The residual electron density of 3.5 eA-3 needs to be compared with the height of a S peak in this structure of about 50 eA-3. The residual density is of no consequence and probably arises from deficiences in the face- indexed absorption correction.

PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -2.25 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -2.17 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -2.05 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.73 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.67 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.65 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.64 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.62 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.61 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.61 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.60 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.57 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.55 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.52 eA-3

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT794_ALERT_5_G Note: Tentative Bond Valency for U1      (IV)          3.82
PLAT794_ALERT_5_G Note: Tentative Bond Valency for U2      (IV)          4.39
PLAT794_ALERT_5_G Note: Tentative Bond Valency for U3      (IV)          3.78
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Mn1     (II)          3.03
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   3 ALERT level A = Most likely a serious problem - resolve or explain
  12 ALERT level B = A potentially serious problem, consider carefully
  30 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

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

---

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

The structure was standardized by means of the program STRUCTURE TIDY (Gelato & Parthé, 1987). The highest peak of 3.9 (4) e/ų is 1.33 Å from atom U2 and the deepest hole of -1.9 (4) e/ų is 0.88 Å from atom U3.

Computing details

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

	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

Crystal data

MnU8S17	F(000) = 2066
Mr = 2504.20	Dx = 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) Å^3	0.15 × 0.09 × 0.08 mm
Z = 2

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	w = 1/[σ^2(Fo^2) + (0.0161Fo^2)^2]
wR(F^2) = 0.068	(Δ/σ)max = 0.001
S = 2.10	Δρmax = 3.90 e Å^−3
1609 reflections	Δρmin = −1.94 e Å^−3
73 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008a), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00082 (4)

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

	x	y	z	Uiso*/Ueq
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 (Ų)

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

U1—S3^i	2.7546 (19)	U3—U1^iv	4.0205 (4)
U1—S2	2.7621 (19)	U3—U1^vii	4.0205 (4)
U1—S1^ii	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—S1^iii	2.8469 (19)	Mn1—S2^xii	2.5168 (19)
U1—S4^iii	2.852 (2)	Mn1—S2^xiii	2.5168 (19)
U1—S7^i	2.9509 (3)	Mn1—S2^xiv	2.5168 (19)
U1—U3^iv	4.0206 (4)	S1—U2^iii	2.763 (2)
U1—U2^iii	4.0951 (5)	S1—U1^xiv	2.802 (2)
U2—S3	2.735 (3)	S1—U1^iii	2.8469 (19)
U2—S4	2.747 (3)	S2—Mn1^i	2.5168 (19)
U2—S1^iii	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—U1^iii	4.0952 (5)	S4—U1^iii	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—S2^ii	2.896 (2)	S7—U1^xi	2.9509 (3)
U3—S2^ix	2.896 (2)	S7—U1^iii	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)
S3^i—U1—S2	76.01 (7)	S2^vii—U3—S2^ix	134.99 (5)
S3^i—U1—S1^ii	79.55 (7)	S4^viii—U3—S2^ix	71.79 (6)
S2—U1—S1^ii	140.70 (6)	S5^iv—U3—S2^ix	80.27 (6)
S3^i—U1—S5	155.43 (8)	S2^ii—U3—S2^ix	68.33 (8)
S2—U1—S5	80.28 (7)	S2^iv—U3—S6	87.07 (5)
S1^ii—U1—S5	116.52 (6)	S2^vii—U3—S6	87.07 (5)
S3^i—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)
S1^ii—U1—S6	78.56 (7)	S2^ii—U3—S6	132.44 (5)
S5—U1—S6	68.37 (7)	S2^ix—U3—S6	132.44 (5)
S3^i—U1—S1^iii	130.39 (7)	S2^iv—U3—S6^iv	73.60 (4)
S2—U1—S1^iii	139.93 (6)	S2^vii—U3—S6^iv	73.60 (4)
S1^ii—U1—S1^iii	78.93 (6)	S4^viii—U3—S6^iv	148.59 (8)
S5—U1—S1^iii	73.14 (7)	S5^iv—U3—S6^iv	65.38 (8)
S6—U1—S1^iii	119.29 (6)	S2^ii—U3—S6^iv	131.75 (5)
S3^i—U1—S4^iii	83.16 (6)	S2^ix—U3—S6^iv	131.75 (5)
S2—U1—S4^iii	73.29 (7)	S6—U3—S6^iv	71.77 (8)
S1^ii—U1—S4^iii	133.46 (7)	S2^iv—U3—U1^iv	43.17 (4)
S5—U1—S4^iii	96.17 (6)	S2^vii—U3—U1^iv	107.02 (4)
S6—U1—S4^iii	147.19 (8)	S4^viii—U3—U1^iv	147.748 (6)
S1^iii—U1—S4^iii	80.27 (7)	S5^iv—U3—U1^iv	44.40 (4)
S3^i—U1—S7^i	65.25 (5)	S2^ii—U3—U1^iv	123.06 (4)
S2—U1—S7^i	127.10 (4)	S2^ix—U3—U1^iv	86.95 (4)
S1^ii—U1—S7^i	65.71 (4)	S6—U3—U1^iv	102.46 (5)
S5—U1—S7^i	137.07 (6)	S6^iv—U3—U1^iv	44.81 (3)
S6—U1—S7^i	142.74 (6)	S2^iv—U3—U1^vii	107.02 (4)
S1^iii—U1—S7^i	65.18 (4)	S2^vii—U3—U1^vii	43.17 (4)
S4^iii—U1—S7^i	67.79 (5)	S4^viii—U3—U1^vii	147.748 (6)
S3^i—U1—U3^iv	110.77 (6)	S5^iv—U3—U1^vii	44.40 (4)
S2—U1—U3^iv	41.58 (4)	S2^ii—U3—U1^vii	86.95 (4)
S1^ii—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)
S1^iii—U1—U3^iv	117.93 (4)	U1^iv—U3—U1^vii	64.432 (10)
S4^iii—U1—U3^iv	99.54 (5)	S3—Mn1—S3^x	180.0
S7^i—U1—U3^iv	166.765 (10)	S3—Mn1—S2^xi	87.41 (7)
S3^i—U1—U2^iii	98.80 (5)	S3^x—Mn1—S2^xi	92.59 (7)
S2—U1—U2^iii	114.83 (4)	S3—Mn1—S2^xii	92.59 (7)
S1^ii—U1—U2^iii	98.88 (4)	S3^x—Mn1—S2^xii	87.41 (7)
S5—U1—U2^iii	96.86 (5)	S2^xi—Mn1—S2^xii	180.00 (11)
S6—U1—U2^iii	161.01 (4)	S3—Mn1—S2^xiii	92.59 (7)
S1^iii—U1—U2^iii	42.42 (4)	S3^x—Mn1—S2^xiii	87.41 (7)
S4^iii—U1—U2^iii	42.01 (5)	S2^xi—Mn1—S2^xiii	99.50 (9)
S7^i—U1—U2^iii	44.218 (7)	S2^xii—Mn1—S2^xiii	80.50 (9)
U3^iv—U1—U2^iii	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—S1^iii	129.53 (6)	S2^xi—Mn1—S2^xiv	80.50 (9)
S4—U2—S1^iii	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)	U2^iii—S1—U2	105.75 (7)
S1^iii—U2—S1^v	72.72 (8)	U2^iii—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)	U2^iii—S1—U1^iii	104.35 (6)
S1^iii—U2—S1	74.25 (7)	U2—S1—U1^iii	93.65 (6)
S1^v—U2—S1	145.44 (5)	U1^xiv—S1—U1^iii	97.35 (6)
S3—U2—S1^vi	80.49 (5)	Mn1^i—S2—U3^iv	137.09 (8)
S4—U2—S1^vi	83.52 (5)	Mn1^i—S2—U1	96.17 (6)
S1^iii—U2—S1^vi	145.44 (5)	U3^iv—S2—U1	95.25 (6)
S1^v—U2—S1^vi	74.25 (7)	Mn1^i—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)
S1^iii—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)
S1^iii—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—U1^iii	93.99 (7)
S1^vi—U2—S7	67.46 (4)	U3^viii—S4—U1^iii	105.98 (7)
S5—U2—S7	138.10 (6)	U1^v—S4—U1^iii	91.99 (8)
S3—U2—U1^iii	101.73 (5)	U2—S5—U1	104.51 (7)
S4—U2—U1^iii	44.00 (4)	U2—S5—U1^vi	104.51 (7)
S1^iii—U2—U1^iii	89.36 (4)	U1—S5—U1^vi	99.28 (9)
S1^v—U2—U1^iii	125.64 (4)	U2—S5—U3^iv	156.22 (12)
S1—U2—U1^iii	43.93 (4)	U1—S5—U3^iv	90.65 (7)
S1^vi—U2—U1^iii	101.83 (4)	U1^vi—S5—U3^iv	90.65 (7)
S5—U2—U1^iii	149.546 (11)	U1^vi—S6—U1	98.05 (8)
S7—U2—U1^iii	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)
S1^iii—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—U1^iii	89.683 (8)
U1^iii—U2—U1^v	60.118 (10)	U2^xvi—S7—U1^iii	90.318 (8)
S2^iv—U3—S2^vii	146.88 (9)	U1^xi—S7—U1^iii	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)	U1^iii—S7—U1^v	88.075 (11)
S4^viii—U3—S5^iv	146.02 (8)	U2—S7—U1^xiv	90.317 (8)
S2^iv—U3—S2^ii	134.99 (5)	U2^xvi—S7—U1^xiv	89.682 (8)
S2^vii—U3—S2^ii	68.31 (7)	U1^xi—S7—U1^xiv	88.075 (11)
S4^viii—U3—S2^ii	71.79 (6)	U1^iii—S7—U1^xiv	91.925 (11)
S5^iv—U3—S2^ii	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.