The mixed-metal tris­(di­sulfide) thio­phosphate, KNb1.77Ta0.23PS10

Lee, Y.; Yoon, W.; Yun, H.

doi:10.1107/S1600536814000592

inorganic compounds

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Page i8

doi:10.1107/S1600536814000592

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The mixed-metal tris(disulfide) thiophosphate, KNb_1.77Ta_0.23PS₁₀

Yoonjeong Lee,^a Woojin Yoon ^a and Hoseop Yun ^a ^*

^aDivision of Energy Systems Research and Department of Chemistry, Ajou University, Suwon 443-749, Republic of Korea
^*Correspondence e-mail: hsyun@ajou.ac.kr

(Received 6 January 2014; accepted 9 January 2014; online 15 January 2014)

The title compound catena-poly[potassium [tri-μ-disulfido-μ-tetrathiophosphato-di[niobate(IV)/tantalate(IV)(0.885/0.115)]]], has been obtained through the reaction of the elements with KCl. The title compound is isostructural with KNb₂PS₁₀, with the Nb sites occupied by statistically disordered Nb (88.5%) and Ta (11.5%) atoms. The structure is composed of anionic _∞¹[M₂PS₁₀]⁻ chains along [100] (M = Nb/Ta) and K⁺ ions. This chain is built up from distorted bicapped trigonal prisms [MS₈] and [PS₄] tetrahedra. There are no interchain bonding interactions, except for electrostatic and van der Waals forces. The S₂²⁻ and S²⁻ anionic species and the M⁴⁺–M⁴⁺ pair [M—M = 2.8939 (3) Å] are observed. The classical charge balance is represented by [K⁺][M⁴⁺]₂[PS₄³⁻][S₂²⁻]₃.

CCDC reference: 980749

Related literature

For the related mixed-metallic phase KNb_1.75V_0.25PS₁₀, see: Yu & Yun (2011 ). For related quaternary compounds, see: Goh et al. (2002 ); Do & Yun (1996 , 2009 ); Kim & Yun (2002 ); Kwak et al. (2007 ); Bang et al. (2008 ) and for quintenary compounds, see: Kwak & Yun (2008 ); Dong et al. (2005a ,b ). For Cs_0.5Ag_0.5Nb₂PS₁₀, see: Park & Yun (2010 ). For a typical Nb⁴⁺—Nb⁴⁺ bond length, see: Angenault et al. (2000 ).

Experimental

Crystal data

KNb_1.77Ta_0.23PS₁₀
M_r = 596.52
Orthorhombic, P c a 2₁
a = 13.0049 (3) Å
b = 7.5262 (2) Å
c = 13.3616 (3) Å
V = 1307.81 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.45 mm⁻¹
T = 290 K
0.32 × 0.06 × 0.04 mm

Data collection

Rigaku R-AXIS RAPID S diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.724, T_max = 1.000
12074 measured reflections
2974 independent reflections
2842 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.019
wR(F²) = 0.040
S = 1.08
2974 reflections
130 parameters
1 restraint
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.64 e Å⁻³
Absolute structure: Flack (1983 )
Absolute structure parameter: 0.102 (14)

Table 1
Selected bond lengths (Å)

Nb1/Ta1—S8ⁱ	2.4753 (10)
Nb1/Ta1—S7ⁱⁱ	2.4895 (9)
Nb1/Ta1—S2ⁱⁱⁱ	2.5133 (10)
Nb1/Ta1—S9ⁱ	2.5255 (9)
Nb1/Ta1—S6ⁱ	2.5545 (9)
Nb1/Ta1—S10ⁱⁱ	2.5653 (8)
Nb1/Ta1—S1	2.5831 (9)
Nb1/Ta1—S4	2.6438 (8)
Nb2/Ta2—S9^iv	2.4742 (9)
Nb2/Ta2—S2ⁱ	2.4805 (9)
Nb2/Ta2—S8^iv	2.5185 (10)
Nb2/Ta2—S7	2.5513 (9)
Nb2/Ta2—S6ⁱ	2.5568 (9)
Nb2/Ta2—S10ⁱⁱ	2.5597 (8)
Nb2/Ta2—S5	2.5802 (8)
Nb2/Ta2—S4	2.6369 (8)
P—S3	1.9725 (14)
P—S5	2.0470 (14)
P—S1	2.0568 (13)
P—S4	2.0888 (14)
S2—S8ⁱⁱ	2.0302 (16)
S6—S10^v	2.0568 (13)
S7—S9^iv	2.0452 (15)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y, z]$ ; (iii) $[-x, -y, z-{\script{1\over 2}}]$ ; (iv) $[-x+1, -y, z-{\script{1\over 2}}]$ ; (v) $[-x+1, -y, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2006 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: locally modified version of ORTEP (Johnson, 1965 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 980749

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814000592/ru2056sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000592/ru2056Isup2.hkl

checkCIF report

Comment top

A number of monovalent metal Nb thiophosphates have been investigated. Among them are NaNb₂PS₁₀ (Goh et al., 2002), KNb₂PS₁₀ (Do & Yun, 1996), RbNb₂PS₁₀ (Kim & Yun, 2002), CsNb₂PS₁₀ (Kwak et al., 2007), TlNb₂PS₁₀ (Bang et al., 2008), Ag_0.88Nb₂PS₁₀ (Do & Yun, 2009), K_0.34Cu_0.5Nb₂PS₁₀ (Kwak & Yun, 2008), K_0.5Ag_0.Nb₂PS₁₀ (Dong et al., 2005a), Rb_0.38Ag_0.5Nb₂PS₁₀ (Dong et al., 2005b), Cs_0.5Ag_0.5Nb₂PS₁₀ (Park & Yun, 2010), and KNb_1.75V_0.25PS₁₀ (Yu & Yun, 2011). As a result of efforts to find new phases in this family, we have found a mixed-metallic phase,. In this paper we report the synthesis and structure of another mixed-metallic quintenary thiophosphate, KNb_1.77Ta_0.23PS₁₀.

The structure of KNb_1.77Ta_0.23PS₁₀ is isostructural with KNb₂PS₁₀ and mixed-metallic KNb_1.75V_0.25PS₁₀. Detailed description of the structure is given previously (Do & Yun, 1996; Yu & Yun, 2011). The title compound is made up of the usual bicapped trigonal biprismatic [M₂S₁₂] unit (M=Nb/Ta) and the tetrahedral [PS₄] group. The M sites are occupied by the statistically disordered Nb(88.5%) and Ta(11.5%) atoms. The bicapped biprismatic [M₂S₁₂] units and its neighboring tetrahedral [PS₄] groups are given in Figure 1. These [M₂S₁₂] units are linked together to form the one-dimensional chains, ∞¹[M₂PS₁₀^-] by sharing the S₂^2- prism edge.

The M atoms associate in pairs with M—M interactions alternating in the sequence of one short (2.8939 (3) Å) and one long (3.7670 (3) Å) distances. The short distance is typical of Nb⁴⁺—Nb⁴⁺ bonding interactions (Angenault et al., 2000). There are no interchain bonding interactions except the van der Waals forces and the K⁺ ions in this van der Waals gap stabilize the structure through the electrostatic interactions (Figure 2).

The structural studies of the three different crystals from the same reaction tube implied that the stoichiometry of each metal can vary, KNb_{2 -} _xTa_xPS₁₀, 0.18≤x≤0.26 and they seem to form a random substitutional solid solution. However Ta analogue of this phase, ATa₂PS₁₀ has never been synthsized and thus the maximum x should be small. Finally, the classical charge balance of this phase can be represented by [K⁺][M⁴⁺]₂[PS₄^3-][S₂^2-]₃.

Related literature top

For the related mixed-metallic phase KNb_1.75V_0.25PS₁₀, see: Yu & Yun (2011). For related quaternary compounds, see: Goh et al. (2002); Do & Yun (1996, 2009); Kim & Yun (2002); Kwak et al. (2007); Bang et al. (2008) and for quintenary compounds, see: Kwak & Yun (2008); Dong et al. (2005a,b). For Cs_0.5Ag_0.5Nb₂PS₁₀, see: Park & Yun (2010). For a typical Nb⁴⁺—Nb⁴⁺ bond length, see: Angenault et al. (2000).

Experimental top

The title compound, KNb_1.77Ta_0.23PS₁₀ was prepared by the reaction of the elemental with the use of the reactive alkali metal halides-flux technique. A combination of the pure elements, Nb powder (CERAC 99.8%), Ta powder (CERAC 99.9%), P powder(Aldrich 99.9%), and S powder (Aldrich 99.999%) were mixed in a fused silica tube in a molar ratio of Nb: Ta: P: S = 1:1:1:10 with KCl (CERAC 99.9%). The mass ratio of the reactants and the alkali metal halides flux was 1:1. The tube was evacuated to 0.133 Pa, sealed and heated gradually (70 K/h) to 1073 K, where it was kept for 72 h. The tube was cooled to 473 K at 6 K/h and then was quenched to room temperature. The excess halides were removed with distilled water and black needle-shaped single crystals were obtained. The crystals are stable in air and water. Qualitative analysis of these crystals using XRF showed the presence of K, Nb, Ta, P, and S.

Structure description top

For the related mixed-metallic phase KNb_1.75V_0.25PS₁₀, see: Yu & Yun (2011). For related quaternary compounds, see: Goh et al. (2002); Do & Yun (1996, 2009); Kim & Yun (2002); Kwak et al. (2007); Bang et al. (2008) and for quintenary compounds, see: Kwak & Yun (2008); Dong et al. (2005a,b). For Cs_0.5Ag_0.5Nb₂PS₁₀, see: Park & Yun (2010). For a typical Nb⁴⁺—Nb⁴⁺ bond length, see: Angenault et al. (2000).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: locally modified version of ORTEP (Johnson, 1965); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. A view of the bicapped trigonal biprismatic [M₂S₁₂] unit (M=Nb/Ta) and its neighboring tetrahedral [PS₄] groups. Yellow circles are S atoms, blue circles are Nb atoms, pink and dark green circles are P and K atoms, respectively. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (v) 0.5 - x, y, -0.5 + z; (vi) -0.5 + x, -y, z; (viii) 1 - x, -y, -0.5 + z]

Fig. 2. View of the KNb_1.77Ta_0.23PS₁₀ down the b axis showing the one-dimensional nature of the compound. Atoms are as marked in Fig. 1.

catena-Poly[potassium [tri-µ-disulfido-µ-tetrathiophosphato-di[niobate(IV)/tantalate(IV)(0.885/0.115)]]] top

Crystal data top

KNb_1.77Ta_0.23PS₁₀	F(000) = 1133
M_r = 596.52	D_x = 3.03 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 10926 reflections
a = 13.0049 (3) Å	θ = 3.1–27.4°
b = 7.5262 (2) Å	µ = 5.45 mm⁻¹
c = 13.3616 (3) Å	T = 290 K
V = 1307.81 (6) Å³	Needle, black
Z = 4	0.32 × 0.06 × 0.04 mm

Data collection top

Rigaku R-AXIS RAPID S diffractometer	2974 independent reflections
Radiation source: sealed X-ray tube	2842 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.4°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −16→16
T_min = 0.724, T_max = 1.000	k = −9→9
12074 measured reflections	l = −17→17

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0132P)² + 0.4965P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.019	(Δ/σ)_max = 0.001
wR(F²) = 0.040	Δρ_max = 0.40 e Å⁻³
S = 1.08	Δρ_min = −0.64 e Å⁻³
2974 reflections	Absolute structure: Flack (1983)
130 parameters	Absolute structure parameter: 0.102 (14)

Crystal data top

KNb_1.77Ta_0.23PS₁₀	V = 1307.81 (6) Å³
M_r = 596.52	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 13.0049 (3) Å	µ = 5.45 mm⁻¹
b = 7.5262 (2) Å	T = 290 K
c = 13.3616 (3) Å	0.32 × 0.06 × 0.04 mm

Data collection top

Rigaku R-AXIS RAPID S diffractometer	2974 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2842 reflections with I > 2σ(I)
T_min = 0.724, T_max = 1.000	R_int = 0.031
12074 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.019	1 restraint
wR(F²) = 0.040	Δρ_max = 0.40 e Å⁻³
S = 1.08	Δρ_min = −0.64 e Å⁻³
2974 reflections	Absolute structure: Flack (1983)
130 parameters	Absolute structure parameter: 0.102 (14)

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
K	0.38318 (10)	0.50405 (16)	0.30118 (10)	0.0643 (3)
Nb1	0.024329 (14)	0.05323 (3)	0.03456 (2)	0.01373 (8)	0.8870 (16)
Ta1	0.024329 (14)	0.05323 (3)	0.03456 (2)	0.01373 (8)	0.1130 (16)
Nb2	0.313802 (14)	0.07133 (3)	0.03507 (2)	0.01349 (8)	0.8848 (16)
Ta2	0.313802 (14)	0.07133 (3)	0.03507 (2)	0.01349 (8)	0.1152 (16)
P	0.16059 (6)	0.40111 (13)	0.11222 (8)	0.02029 (19)
S1	0.03152 (5)	0.39563 (11)	0.02331 (9)	0.0241 (2)
S2	0.05537 (7)	0.15129 (15)	0.40771 (7)	0.0231 (2)
S3	0.15181 (9)	0.58446 (14)	0.21735 (9)	0.0393 (3)
S4	0.16755 (6)	0.14082 (12)	0.16603 (6)	0.01689 (19)
S5	0.29233 (6)	0.41195 (10)	0.02861 (11)	0.0285 (2)
S6	0.33066 (6)	0.05475 (12)	0.40561 (7)	0.0189 (2)
S7	0.44837 (7)	0.13315 (14)	0.16957 (6)	0.0207 (2)
S8	0.60107 (7)	0.10612 (14)	0.39842 (7)	0.0235 (2)
S9	0.60965 (7)	0.11936 (13)	0.66622 (6)	0.0201 (2)
S10	0.67408 (5)	0.16023 (11)	0.00053 (6)	0.01866 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K	0.0846 (8)	0.0454 (7)	0.0629 (8)	0.0038 (6)	−0.0317 (7)	0.0034 (6)
Nb1	0.00877 (11)	0.01781 (13)	0.01460 (12)	−0.00086 (7)	0.00002 (16)	0.00118 (14)
Ta1	0.00877 (11)	0.01781 (13)	0.01460 (12)	−0.00086 (7)	0.00002 (16)	0.00118 (14)
Nb2	0.00838 (11)	0.01692 (13)	0.01516 (12)	0.00106 (7)	0.00005 (15)	−0.00009 (14)
Ta2	0.00838 (11)	0.01692 (13)	0.01516 (12)	0.00106 (7)	0.00005 (15)	−0.00009 (14)
P	0.0158 (4)	0.0172 (4)	0.0279 (5)	0.0018 (3)	−0.0010 (4)	−0.0027 (4)
S1	0.0156 (3)	0.0208 (4)	0.0359 (6)	0.0022 (3)	−0.0026 (5)	0.0045 (5)
S2	0.0139 (4)	0.0342 (6)	0.0213 (5)	−0.0031 (4)	−0.0019 (4)	0.0071 (4)
S3	0.0450 (6)	0.0281 (5)	0.0449 (7)	0.0070 (5)	−0.0044 (5)	−0.0179 (5)
S4	0.0138 (4)	0.0200 (5)	0.0169 (4)	0.0004 (3)	0.0002 (3)	−0.0011 (4)
S5	0.0160 (3)	0.0192 (4)	0.0503 (6)	−0.0005 (3)	0.0068 (6)	0.0056 (6)
S6	0.0125 (4)	0.0275 (5)	0.0166 (4)	0.0000 (3)	0.0002 (3)	0.0027 (4)
S7	0.0168 (4)	0.0267 (5)	0.0185 (5)	0.0007 (4)	−0.0008 (4)	−0.0050 (4)
S8	0.0150 (4)	0.0354 (6)	0.0202 (5)	0.0047 (4)	0.0029 (4)	0.0084 (5)
S9	0.0166 (4)	0.0253 (5)	0.0183 (5)	0.0017 (4)	−0.0009 (4)	−0.0033 (4)
S10	0.0152 (4)	0.0169 (4)	0.0239 (4)	−0.0001 (3)	−0.0012 (3)	0.0018 (3)

Geometric parameters (Å, º) top

K—S3	3.2671 (16)	S2—S8^vi	2.0302 (16)
K—S1ⁱ	3.2720 (16)	S2—Ta2ⁱ	2.4805 (9)
K—S9ⁱⁱ	3.3606 (15)	S2—Nb2ⁱ	2.4805 (9)
K—S7	3.4064 (16)	S2—Nb1^x	2.5133 (10)
K—S2ⁱⁱⁱ	3.7107 (16)	S2—Ta1^x	2.5133 (10)
K—S6	3.7213 (15)	S2—K^xi	3.7107 (16)
K—S3ⁱⁱⁱ	3.7288 (19)	S3—K^xi	3.7288 (19)
K—S10^iv	3.7461 (16)	S6—S10^xii	2.0568 (13)
Nb1—S8^v	2.4753 (10)	S6—Ta1ⁱ	2.5545 (9)
Nb1—S7^vi	2.4895 (9)	S6—Nb1ⁱ	2.5545 (9)
Nb1—S2^vii	2.5133 (10)	S6—Ta2ⁱ	2.5568 (9)
Nb1—S9^v	2.5255 (9)	S6—Nb2ⁱ	2.5568 (9)
Nb1—S6^v	2.5545 (9)	S7—S9^viii	2.0452 (15)
Nb1—S10^vi	2.5653 (8)	S7—Ta1^ix	2.4895 (9)
Nb1—S1	2.5831 (9)	S7—Nb1^ix	2.4895 (9)
Nb1—S4	2.6438 (8)	S8—S2^ix	2.0302 (17)
Nb1—Nb2^vi	2.8939 (3)	S8—Nb1ⁱ	2.4753 (10)
Nb1—Ta2^vi	2.8939 (3)	S8—Ta1ⁱ	2.4753 (10)
Nb2—S9^viii	2.4742 (9)	S8—Nb2^xii	2.5185 (10)
Nb2—S2^v	2.4805 (9)	S8—Ta2^xii	2.5185 (10)
Nb2—S8^viii	2.5185 (10)	S9—S7^xii	2.0452 (15)
Nb2—S7	2.5513 (9)	S9—Ta2^xii	2.4742 (9)
Nb2—S6^v	2.5568 (9)	S9—Nb2^xii	2.4742 (9)
Nb2—S10^vi	2.5597 (8)	S9—Nb1ⁱ	2.5255 (9)
Nb2—S5	2.5802 (8)	S9—Ta1ⁱ	2.5255 (9)
Nb2—S4	2.6369 (8)	S9—K^iv	3.3606 (15)
Nb2—Ta1^ix	2.8939 (3)	S10—S6^viii	2.0568 (13)
Nb2—Nb1^ix	2.8939 (3)	S10—Ta2^ix	2.5597 (8)
P—S3	1.9725 (14)	S10—Nb2^ix	2.5597 (8)
P—S5	2.0470 (14)	S10—Nb1^ix	2.5653 (8)
P—S1	2.0568 (13)	S10—Ta1^ix	2.5653 (8)
P—S4	2.0888 (14)	S10—Kⁱⁱ	3.7461 (16)
S1—K^v	3.2720 (16)

S3—K—S1ⁱ	132.02 (6)	S5—Nb2—Ta1^ix	115.097 (18)
S3—K—S9ⁱⁱ	71.66 (3)	S4—Nb2—Ta1^ix	138.44 (2)
S1ⁱ—K—S9ⁱⁱ	133.45 (4)	S9^viii—Nb2—Nb1^ix	55.46 (2)
S3—K—S7	101.77 (4)	S2^v—Nb2—Nb1^ix	55.12 (2)
S1ⁱ—K—S7	100.34 (4)	S8^viii—Nb2—Nb1^ix	53.89 (2)
S9ⁱⁱ—K—S7	114.03 (5)	S7—Nb2—Nb1^ix	53.97 (2)
S3—K—S2ⁱⁱⁱ	123.90 (4)	S6^v—Nb2—Nb1^ix	132.67 (2)
S1ⁱ—K—S2ⁱⁱⁱ	67.78 (3)	S10^vi—Nb2—Nb1^ix	116.78 (2)
S9ⁱⁱ—K—S2ⁱⁱⁱ	66.39 (3)	S5—Nb2—Nb1^ix	115.097 (18)
S7—K—S2ⁱⁱⁱ	128.37 (5)	S4—Nb2—Nb1^ix	138.44 (2)
S3—K—S6	97.35 (4)	Ta1^ix—Nb2—Nb1^ix	0.000 (14)
S1ⁱ—K—S6	59.70 (3)	S3—P—S5	114.15 (6)
S9ⁱⁱ—K—S6	166.57 (4)	S3—P—S1	112.22 (6)
S7—K—S6	59.64 (3)	S5—P—S1	111.63 (7)
S2ⁱⁱⁱ—K—S6	127.02 (4)	S3—P—S4	114.42 (7)
S3—K—S3ⁱⁱⁱ	142.46 (6)	S5—P—S4	100.89 (5)
S1ⁱ—K—S3ⁱⁱⁱ	84.85 (3)	S1—P—S4	102.44 (5)
S9ⁱⁱ—K—S3ⁱⁱⁱ	87.91 (4)	P—S1—Nb1	90.91 (4)
S7—K—S3ⁱⁱⁱ	57.68 (3)	P—S1—K^v	104.02 (5)
S2ⁱⁱⁱ—K—S3ⁱⁱⁱ	71.02 (3)	Nb1—S1—K^v	108.29 (4)
S6—K—S3ⁱⁱⁱ	97.02 (4)	S8^vi—S2—Ta2ⁱ	67.02 (4)
S3—K—S10^iv	86.32 (4)	S8^vi—S2—Nb2ⁱ	67.02 (4)
S1ⁱ—K—S10^iv	65.83 (3)	Ta2ⁱ—S2—Nb2ⁱ	0.000 (15)
S9ⁱⁱ—K—S10^iv	79.53 (3)	S8^vi—S2—Nb1^x	65.01 (4)
S7—K—S10^iv	165.76 (4)	Ta2ⁱ—S2—Nb1^x	70.83 (3)
S2ⁱⁱⁱ—K—S10^iv	51.37 (3)	Nb2ⁱ—S2—Nb1^x	70.83 (3)
S6—K—S10^iv	108.05 (4)	S8^vi—S2—Ta1^x	65.01 (4)
S3ⁱⁱⁱ—K—S10^iv	121.36 (4)	Ta2ⁱ—S2—Ta1^x	70.83 (3)
S8^v—Nb1—S7^vi	111.20 (3)	Nb2ⁱ—S2—Ta1^x	70.83 (3)
S8^v—Nb1—S2^vii	48.02 (4)	Nb1^x—S2—Ta1^x	0.000 (11)
S7^vi—Nb1—S2^vii	88.85 (3)	S8^vi—S2—K^xi	145.11 (5)
S8^v—Nb1—S9^v	91.47 (3)	Ta2ⁱ—S2—K^xi	147.85 (4)
S7^vi—Nb1—S9^v	48.13 (3)	Nb2ⁱ—S2—K^xi	147.85 (4)
S2^vii—Nb1—S9^v	107.82 (3)	Nb1^x—S2—K^xi	115.97 (4)
S8^v—Nb1—S6^v	89.43 (3)	Ta1^x—S2—K^xi	115.97 (4)
S7^vi—Nb1—S6^v	141.65 (3)	P—S3—K	93.51 (5)
S2^vii—Nb1—S6^v	81.51 (3)	P—S3—K^xi	98.23 (5)
S9^v—Nb1—S6^v	168.03 (3)	K—S3—K^xi	136.62 (6)
S8^v—Nb1—S10^vi	118.08 (3)	P—S4—Nb2	89.36 (4)
S7^vi—Nb1—S10^vi	94.41 (3)	P—S4—Nb1	88.54 (4)
S2^vii—Nb1—S10^vi	79.05 (3)	Nb2—S4—Nb1	91.02 (3)
S9^v—Nb1—S10^vi	140.41 (3)	P—S5—Nb2	91.88 (4)
S6^v—Nb1—S10^vi	47.37 (3)	S10^xii—S6—Ta1ⁱ	66.59 (3)
S8^v—Nb1—S1	79.67 (3)	S10^xii—S6—Nb1ⁱ	66.59 (3)
S7^vi—Nb1—S1	128.22 (3)	Ta1ⁱ—S6—Nb1ⁱ	0.000 (13)
S2^vii—Nb1—S1	125.92 (3)	S10^xii—S6—Ta2ⁱ	66.37 (3)
S9^v—Nb1—S1	82.47 (3)	Ta1ⁱ—S6—Ta2ⁱ	94.95 (3)
S6^v—Nb1—S1	85.96 (3)	Nb1ⁱ—S6—Ta2ⁱ	94.95 (3)
S10^vi—Nb1—S1	125.95 (3)	S10^xii—S6—Nb2ⁱ	66.37 (3)
S8^v—Nb1—S4	155.83 (3)	Ta1ⁱ—S6—Nb2ⁱ	94.95 (3)
S7^vi—Nb1—S4	86.48 (3)	Nb1ⁱ—S6—Nb2ⁱ	94.95 (3)
S2^vii—Nb1—S4	153.05 (3)	Ta2ⁱ—S6—Nb2ⁱ	0.000 (6)
S9^v—Nb1—S4	88.51 (3)	S10^xii—S6—K	162.09 (5)
S6^v—Nb1—S4	85.81 (3)	Ta1ⁱ—S6—K	96.98 (3)
S10^vi—Nb1—S4	74.88 (3)	Nb1ⁱ—S6—K	96.98 (3)
S1—Nb1—S4	76.37 (3)	Ta2ⁱ—S6—K	110.13 (4)
S8^v—Nb1—Nb2^vi	55.28 (2)	Nb2ⁱ—S6—K	110.13 (4)
S7^vi—Nb1—Nb2^vi	55.97 (2)	S9^viii—S7—Ta1^ix	66.86 (4)
S2^vii—Nb1—Nb2^vi	54.06 (2)	S9^viii—S7—Nb1^ix	66.86 (4)
S9^v—Nb1—Nb2^vi	53.81 (2)	Ta1^ix—S7—Nb1^ix	0.000 (14)
S6^v—Nb1—Nb2^vi	134.55 (2)	S9^viii—S7—Nb2	64.03 (3)
S10^vi—Nb1—Nb2^vi	121.05 (2)	Ta1^ix—S7—Nb2	70.06 (2)
S1—Nb1—Nb2^vi	110.949 (17)	Nb1^ix—S7—Nb2	70.06 (2)
S4—Nb1—Nb2^vi	138.22 (2)	S9^viii—S7—K	132.92 (5)
S8^v—Nb1—Ta2^vi	55.28 (2)	Ta1^ix—S7—K	159.16 (5)
S7^vi—Nb1—Ta2^vi	55.97 (2)	Nb1^ix—S7—K	159.16 (5)
S2^vii—Nb1—Ta2^vi	54.06 (2)	Nb2—S7—K	110.02 (4)
S9^v—Nb1—Ta2^vi	53.81 (2)	S2^ix—S8—Nb1ⁱ	66.97 (4)
S6^v—Nb1—Ta2^vi	134.55 (2)	S2^ix—S8—Ta1ⁱ	66.97 (4)
S10^vi—Nb1—Ta2^vi	121.05 (2)	Nb1ⁱ—S8—Ta1ⁱ	0.000 (12)
S1—Nb1—Ta2^vi	110.949 (17)	S2^ix—S8—Nb2^xii	65.06 (4)
S4—Nb1—Ta2^vi	138.22 (2)	Nb1ⁱ—S8—Nb2^xii	70.83 (3)
Nb2^vi—Nb1—Ta2^vi	0.000 (16)	Ta1ⁱ—S8—Nb2^xii	70.83 (3)
S9^viii—Nb2—S2^v	110.53 (3)	S2^ix—S8—Ta2^xii	65.06 (4)
S9^viii—Nb2—S8^viii	91.66 (3)	Nb1ⁱ—S8—Ta2^xii	70.83 (3)
S2^v—Nb2—S8^viii	47.92 (4)	Ta1ⁱ—S8—Ta2^xii	70.83 (3)
S9^viii—Nb2—S7	48.00 (3)	Nb2^xii—S8—Ta2^xii	0.000 (13)
S2^v—Nb2—S7	88.20 (2)	S7^xii—S9—Ta2^xii	67.97 (4)
S8^viii—Nb2—S7	107.81 (3)	S7^xii—S9—Nb2^xii	67.97 (4)
S9^viii—Nb2—S6^v	138.29 (3)	Ta2^xii—S9—Nb2^xii	0.000 (13)
S2^v—Nb2—S6^v	92.96 (3)	S7^xii—S9—Nb1ⁱ	65.01 (3)
S8^viii—Nb2—S6^v	78.85 (3)	Ta2^xii—S9—Nb1ⁱ	70.73 (2)
S7—Nb2—S6^v	171.69 (3)	Nb2^xii—S9—Nb1ⁱ	70.73 (2)
S9^viii—Nb2—S10^vi	91.05 (3)	S7^xii—S9—Ta1ⁱ	65.01 (3)
S2^v—Nb2—S10^vi	121.90 (3)	Ta2^xii—S9—Ta1ⁱ	70.73 (2)
S8^viii—Nb2—S10^vi	79.64 (3)	Nb2^xii—S9—Ta1ⁱ	70.73 (2)
S7—Nb2—S10^vi	137.57 (3)	Nb1ⁱ—S9—Ta1ⁱ	0.000 (11)
S6^v—Nb2—S10^vi	47.41 (3)	S7^xii—S9—K^iv	141.46 (5)
S9^viii—Nb2—S5	130.06 (4)	Ta2^xii—S9—K^iv	149.10 (4)
S2^v—Nb2—S5	79.06 (4)	Nb2^xii—S9—K^iv	149.10 (4)
S8^viii—Nb2—S5	123.38 (4)	Nb1ⁱ—S9—K^iv	124.00 (4)
S7—Nb2—S5	85.22 (4)	Ta1ⁱ—S9—K^iv	124.00 (4)
S6^v—Nb2—S5	86.92 (3)	S6^viii—S10—Ta2^ix	66.22 (3)
S10^vi—Nb2—S5	126.41 (3)	S6^viii—S10—Nb2^ix	66.22 (3)
S9^viii—Nb2—S4	86.29 (3)	Ta2^ix—S10—Nb2^ix	0.000 (17)
S2^v—Nb2—S4	154.41 (3)	S6^viii—S10—Nb1^ix	66.04 (3)
S8^viii—Nb2—S4	154.60 (3)	Ta2^ix—S10—Nb1^ix	94.62 (3)
S7—Nb2—S4	89.49 (3)	Nb2^ix—S10—Nb1^ix	94.62 (3)
S6^v—Nb2—S4	85.91 (3)	S6^viii—S10—Ta1^ix	66.04 (3)
S10^vi—Nb2—S4	75.09 (3)	Ta2^ix—S10—Ta1^ix	94.62 (3)
S5—Nb2—S4	75.35 (3)	Nb2^ix—S10—Ta1^ix	94.62 (3)
S9^viii—Nb2—Ta1^ix	55.46 (2)	Nb1^ix—S10—Ta1^ix	0.000 (16)
S2^v—Nb2—Ta1^ix	55.12 (2)	S6^viii—S10—Kⁱⁱ	94.94 (4)
S8^viii—Nb2—Ta1^ix	53.89 (2)	Ta2^ix—S10—Kⁱⁱ	136.76 (3)
S7—Nb2—Ta1^ix	53.97 (2)	Nb2^ix—S10—Kⁱⁱ	136.76 (3)
S6^v—Nb2—Ta1^ix	132.67 (2)	Nb1^ix—S10—Kⁱⁱ	113.42 (3)
S10^vi—Nb2—Ta1^ix	116.78 (2)	Ta1^ix—S10—Kⁱⁱ	113.42 (3)

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

Selected bond lengths (Å) top

Nb1—S8ⁱ	2.4753 (10)	Nb2—S6ⁱ	2.5568 (9)
Nb1—S7ⁱⁱ	2.4895 (9)	Nb2—S10ⁱⁱ	2.5597 (8)
Nb1—S2ⁱⁱⁱ	2.5133 (10)	Nb2—S5	2.5802 (8)
Nb1—S9ⁱ	2.5255 (9)	Nb2—S4	2.6369 (8)
Nb1—S6ⁱ	2.5545 (9)	Nb2—Ta1^v	2.8939 (3)
Nb1—S10ⁱⁱ	2.5653 (8)	Nb2—Nb1^v	2.8939 (3)
Nb1—S1	2.5831 (9)	P—S3	1.9725 (14)
Nb1—S4	2.6438 (8)	P—S5	2.0470 (14)
Nb1—Nb2ⁱⁱ	2.8939 (3)	P—S1	2.0568 (13)
Nb1—Ta2ⁱⁱ	2.8939 (3)	P—S4	2.0888 (14)
Nb2—S9^iv	2.4742 (9)	S2—S8ⁱⁱ	2.0302 (16)
Nb2—S2ⁱ	2.4805 (9)	S6—S10^vi	2.0568 (13)
Nb2—S8^iv	2.5185 (10)	S7—S9^iv	2.0452 (15)
Nb2—S7	2.5513 (9)

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (grant No. 2011–0011309).

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