The quinter­nary thio­phosphate Cs0.5Ag0.5Nb2PS10

Park, S.; Yun, H.

doi:10.1107/S1600536810021768

inorganic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages i51-i52

doi:10.1107/S1600536810021768

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The quinternary thiophosphate Cs_0.5Ag_0.5Nb₂PS₁₀

Sojeong Park ^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 25 May 2010; accepted 7 June 2010; online 16 June 2010)

The quinternary thiophosphate Cs_0.5Ag_0.5Nb₂PS₁₀, cesium silver tris(disulfido)[tetrathiophosphato(V)]diniobate(IV), has been prepared from the elements using a CsCl flux. The crystal structure is made up of _∞¹[Nb₂PS₁₀] chains expanding along [010]. These chains are built up from bicapped trigonal-prismatic [Nb₂S₁₂] units and tetrahedral [PS₄] groups and are linked through a linear S—Ag—S bridge, forming a two-dimensional layer. These layers then stack on top of each other, completing the three-dimensional structure with an undulating van der Waals gap. The disordered Cs⁺ ions reside on sites with half-occupation in the voids of this arrangement. Short [2.8843 (5) Å] and long [3.7316 (4) Å] Nb—Nb distances alternate along the chains, and anionic S₂²⁻ and S²⁻ species are observed. The charge balance of the compound can be represented by the formula [Cs⁺]_0.5[Ag⁺]_0.5[Nb⁴⁺]₂[PS₄³⁻][S₂²⁻]₃.

Related literature

For Nb₂PS₁₀-related quaternary thiophosphates, see: Do & Yun (1996 ) for KNb₂PS₁₀, Kim & Yun (2002 ) for RbNb₂PS₁₀, Kwak et al. (2007 ) for CsNb₂PS₁₀, Bang et al. (2008 ) for TlNb₂PS₁₀, and Do & Yun (2009 ) for Ag_0.88Nb₂PS₁₀. For quintenary thiophosphates, see: Kwak & Yun (2008 ) for K_0.34Cu_0.5Nb₂PS₁₀, Dong et al. (2005a ) for K_0.5Ag_0.5Nb₂PS₁₀, and Dong et al. (2005b ) for Rb_0.38Ag_0.5Nb₂PS₁₀. PLATON (Spek, 2009 ) was used for structure validation. For typical Nb—P and P—S bond length, see: Brec et al. (1983 ), and for typical Nb⁴⁺–Nb⁴⁺ bond lengths, see: Angenault et al. (2000 ). For general background, see: Lee et al. (1988 ).

Experimental

Crystal data

Cs_0.5Ag_0.5Nb₂PS₁₀
M_r = 657.78
Monoclinic, P 2₁ /c
a = 7.3594 (3) Å
b = 12.8534 (4) Å
c = 13.7788 (6) Å
β = 91.0886 (12)°
V = 1303.15 (8) Å³
Z = 4
Mo Kα radiation
μ = 5.54 mm⁻¹
T = 290 K
0.30 × 0.06 × 0.04 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.602, T_max = 1.000
12389 measured reflections
2991 independent reflections
2430 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.075
S = 1.08
2991 reflections
133 parameters
Δρ_max = 1.18 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ag—S1	2.4625 (13)
Nb1—S4ⁱ	2.4953 (13)
Nb1—S7ⁱ	2.4958 (12)
Nb1—S8ⁱ	2.5055 (13)
Nb1—S10ⁱ	2.5231 (13)
Nb1—S9	2.5658 (12)
Nb1—S2	2.5895 (12)
Nb1—S5	2.5993 (13)
Nb1—S6	2.6103 (12)
Nb2—S10	2.4910 (13)
Nb2—S7	2.4932 (13)
Nb2—S4	2.4985 (12)
Nb2—S8	2.5075 (12)
Nb2—S5	2.5643 (13)
Nb2—S9	2.5670 (12)
Nb2—S3	2.5920 (12)
Nb2—S6	2.6250 (12)
P—S1	1.9962 (18)
P—S3	2.0391 (17)
P—S2	2.0527 (17)
P—S6	2.0851 (17)

S1—Ag—S1ⁱⁱ	180
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y, -z.

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, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810021768/wm2357sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021768/wm2357Isup2.hkl

checkCIF report

Comment top

During an effort to expand representatives of group 5 transition metal thiophosphates by substituting various monovalent cations, we were able to prepare a new derivative in this system. Here we report the synthesis and characterization of the new layered quinternary thiophosphate, Cs_0.5Ag_0.5Nb₂PS₁₀.

The title compound is isostructural with the previously reported K_0.34Cu_0.5Nb₂PS₁₀ (Kwak & Yun, 2008). The _∞¹[Nb₂PS₁₀] chains found in this structure are composed of the typical biprismatic [Nb₂S₁₂] and tetrahedral [PS₄] units. The Nb atoms are surrounded by 8 S atoms in a bicapped trigonal-prismatic fashion. Two prisms are sharing a rectangular face to form the [Nb₂S₁₂] unit. These units are bound through the S—S prism edges and through one of the capping sulfur atoms to make _∞¹[Nb₂S₉] chains. One of the S atoms at the prism edge and two other capping S atoms are bound to the P atom to which an additional S atom (S1) is attached to complete the _∞¹[Nb₂PS₁₀] chains. These anionic chains propagate parallel to [010] and are linked through the linear S—Ag—S bridge to form a two-dimensional layer along (201). These layers then stack on top of each other to complete the three-dimensional structure with an undulating van der Waals gap. The disordered Cs⁺ cations reside in the voids of this arrangement.

The Nb—S and P—S distances are in agreement with those found in other related phases (Brec et al., 1983). Along the chain, The Nb(1)···Nb(2) interactions alternate in the sequence of one short (2.8843 (5) Å) and one long (3.7316 (4) Å) distance. The short distance is close to that of the typical Nb⁴⁺—Nb⁴⁺ bond (Angenault et al., 2000), and the long Nb···Nb distance shows that there is no significant intermetallic bonding interaction. Such an arrangement is consistent with the high electric resistivity of the crystal along the needle axis (b axis).

The coordination around the Ag atom (1 symmetry) can be described as a [2 + 4] interaction. Four S atoms are bound to the Ag atoms in the plane (Ag—S6, 3.139 (3) Å, Ag—S9, 3.232 (3) Å), whereas two trans S atoms are coordinated to the Ag atom at short distances of Ag—S1 = 2.4625 (13) Å. The large ADPs of Ag could be explained by the second-order Jahn-Teller coupling between the filled Ag e_g and the empty s orbitals (Lee et al., 1988), which is a common trend of d¹⁰ elements. The charge balance of the compound can be represented by the formula [Cs⁺]_0.5[Ag⁺]_0.5[Nb⁴⁺]₂[PS₄^3-][S₂^2-]₃.

Related literature top

For Nb₂PS₁₀-related quaternary thiophosphates, see: Do & Yun (1996) for KNb₂PS₁₀, Kim & Yun (2002) for RbNb₂PS₁₀, Kwak et al. (2007) for CsNb₂PS₁₀, Bang et al. (2008) for TlNb₂PS₁₀, and Do & Yun (2009) for Ag_0.88Nb₂PS₁₀. For quintenary thiophosphates, see: Kwak & Yun (2008) for K_0.34Cu_0.5Nb₂PS₁₀, Dong et al. (2005a) for K_0.5Ag_0.5Nb₂PS₁₀, and Dong et al. (2005b) for Rb_0.38Ag_0.5Nb₂PS₁₀. PLATON (Spek, 2009) was used for structure validation . For typical Nb—P and P—S bond length, see: Brec et al. (1983), and for typical Nb⁴⁺–Nb⁴⁺ bond lengths, see: Angenault et al. (2000). For general background, see: Lee et al. (1988).

Experimental top

Cs_0.5Ag_0.5Nb₂PS₁₀ was prepared by the reaction of elemental powders, using the reactive halide-flux technique. Ag powder (CERAC 99.999%), Nb powder (CERAC 99.8%), P powder (CERAC 99.5%) and S powder (Aldrich 99.999%) were mixed in a fused silica tube in a molar ratio of Ag:Nb:P:S=1:2:1:10 and then CsCl was added in a weight ratio of AgNb₂PS₁₀:CsCl=1:3. The tube was evacuated to 0.133 Pa, sealed and heated gradually (50 K/h) to 973 K, where it was kept for 72 h. The tube was cooled to room temperature at the rate of 4 K/h. The excess halide was removed with distilled water and dark red needle-shaped crystals were obtained. The crystals are stable in air and water. A qualitative X-ray fluorescence analysis of the needles indicated the presence of Cs, Ag, Nb, P, and S. The composition of the compound was determined by single-crystal X-ray diffraction.

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, 1999).

Figures top

Fig. 1. A view of the Cs_0.5Ag_0.5Nb₂PS₁₀ structure. Anisotropic displacement ellipsoids are drawn at the 90% probability level. Symmetry codes are given in Table 1.

cesium silver tris(disulfido)[tetrathiophosphato(V)]diniobate(IV) top

Crystal data top

Cs_0.5Ag_0.5Nb₂PS₁₀	F(000) = 1232
M_r = 657.78	D_x = 3.353 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8832 reflections
a = 7.3594 (3) Å	θ = 3.2–27.5°
b = 12.8534 (4) Å	µ = 5.54 mm⁻¹
c = 13.7788 (6) Å	T = 290 K
β = 91.0886 (12)°	Needle, dark brown
V = 1303.15 (8) Å³	0.30 × 0.06 × 0.04 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2430 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.602, T_max = 1.000	k = −16→14
12389 measured reflections	l = −17→17
2991 independent reflections

Refinement top

Refinement on F²	133 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0248P)² + 3.4157P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.075	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 1.18 e Å⁻³
2991 reflections	Δρ_min = −1.27 e Å⁻³

Crystal data top

Cs_0.5Ag_0.5Nb₂PS₁₀	V = 1303.15 (8) Å³
M_r = 657.78	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3594 (3) Å	µ = 5.54 mm⁻¹
b = 12.8534 (4) Å	T = 290 K
c = 13.7788 (6) Å	0.30 × 0.06 × 0.04 mm
β = 91.0886 (12)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2991 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2430 reflections with I > 2σ(I)
T_min = 0.602, T_max = 1.000	R_int = 0.049
12389 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	133 parameters
wR(F²) = 0.075	0 restraints
S = 1.08	Δρ_max = 1.18 e Å⁻³
2991 reflections	Δρ_min = −1.27 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cs	−0.0009 (4)	0.02093 (15)	0.48715 (19)	0.0512 (5)	0.5
Ag	0	0	0	0.0539 (2)
Nb1	0.42651 (5)	0.03565 (3)	0.24995 (3)	0.01333 (11)
Nb2	0.43445 (5)	0.32590 (3)	0.25353 (3)	0.01280 (11)
P	0.11427 (16)	0.18631 (9)	0.14370 (10)	0.0170 (3)
S1	−0.03805 (19)	0.18878 (10)	0.02229 (11)	0.0292 (3)
S2	0.07865 (16)	0.05281 (9)	0.22287 (10)	0.0210 (3)
S3	0.08568 (16)	0.31790 (9)	0.22464 (10)	0.0207 (3)
S4	0.33249 (16)	0.47121 (9)	0.35994 (9)	0.0187 (3)
S5	0.38477 (17)	0.18131 (9)	0.37848 (9)	0.0190 (3)
S6	0.39304 (16)	0.18214 (8)	0.11963 (9)	0.0161 (2)
S7	0.42828 (17)	0.44324 (9)	0.10942 (9)	0.0194 (3)
S8	0.58572 (16)	0.41695 (9)	0.39426 (9)	0.0184 (3)
S9	0.63765 (16)	0.17797 (9)	0.31795 (9)	0.0189 (3)
S10	0.67972 (16)	0.38737 (9)	0.14538 (9)	0.0204 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs	0.0270 (3)	0.0779 (16)	0.0489 (13)	−0.0003 (11)	0.0060 (7)	−0.0283 (10)
Ag	0.0518 (4)	0.0298 (3)	0.0800 (6)	−0.0028 (3)	0.0017 (4)	−0.0287 (4)
Nb1	0.0150 (2)	0.00814 (18)	0.0168 (2)	0.00081 (16)	−0.00185 (16)	0.00082 (16)
Nb2	0.0145 (2)	0.00802 (19)	0.0158 (2)	−0.00071 (16)	−0.00210 (16)	−0.00048 (16)
P	0.0157 (5)	0.0115 (5)	0.0235 (7)	0.0014 (5)	−0.0057 (5)	−0.0025 (5)
S1	0.0325 (7)	0.0228 (6)	0.0316 (8)	0.0023 (6)	−0.0168 (6)	−0.0038 (6)
S2	0.0181 (5)	0.0140 (5)	0.0310 (7)	−0.0014 (5)	−0.0023 (5)	0.0030 (5)
S3	0.0168 (5)	0.0146 (5)	0.0305 (7)	0.0023 (5)	−0.0034 (5)	−0.0073 (5)
S4	0.0190 (5)	0.0146 (5)	0.0225 (7)	−0.0007 (5)	0.0017 (5)	−0.0031 (5)
S5	0.0256 (6)	0.0126 (5)	0.0189 (6)	0.0001 (5)	0.0008 (5)	0.0007 (5)
S6	0.0186 (5)	0.0104 (5)	0.0193 (6)	0.0019 (5)	−0.0015 (5)	−0.0007 (5)
S7	0.0269 (6)	0.0131 (5)	0.0180 (6)	−0.0009 (5)	−0.0044 (5)	0.0004 (5)
S8	0.0233 (6)	0.0124 (5)	0.0195 (6)	−0.0013 (5)	−0.0043 (5)	0.0000 (5)
S9	0.0185 (5)	0.0128 (5)	0.0251 (7)	−0.0001 (5)	−0.0054 (5)	0.0009 (5)
S10	0.0217 (6)	0.0152 (5)	0.0244 (7)	−0.0003 (5)	0.0048 (5)	−0.0021 (5)

Geometric parameters (Å, º) top

Cs—Csⁱ	0.644 (3)	Nb2—S8	2.5075 (12)
Cs—S10ⁱⁱ	3.444 (3)	Nb2—S5	2.5643 (13)
Cs—S10ⁱⁱⁱ	3.469 (3)	Nb2—S9	2.5670 (12)
Cs—S7^iv	3.536 (3)	Nb2—S3	2.5920 (12)
Cs—S7^v	3.581 (3)	Nb2—S6	2.6250 (12)
Cs—S2	3.722 (3)	Nb2—Nb1^viii	2.8843 (5)
Cs—S1^v	3.773 (2)	P—S1	1.9962 (18)
Cs—S5	3.835 (3)	P—S3	2.0391 (17)
Cs—S3^v	3.915 (3)	P—S2	2.0527 (17)
Cs—S3^iv	3.956 (3)	P—S6	2.0851 (17)
Cs—S9^vi	4.044 (3)	S1—Cs^ix	3.773 (2)
Cs—S2ⁱ	4.157 (3)	S2—Csⁱ	4.157 (3)
Ag—S1	2.4625 (13)	S3—Cs^ix	3.915 (3)
Ag—S1^vii	2.4625 (13)	S3—Cs^x	3.956 (3)
Nb1—S4ⁱⁱⁱ	2.4953 (13)	S4—S8	2.0371 (17)
Nb1—S7ⁱⁱⁱ	2.4958 (12)	S4—Nb1^viii	2.4953 (13)
Nb1—S8ⁱⁱⁱ	2.5055 (13)	S5—S9	2.0542 (18)
Nb1—S10ⁱⁱⁱ	2.5231 (13)	S7—S10	2.0372 (17)
Nb1—S9	2.5658 (12)	S7—Nb1^viii	2.4958 (12)
Nb1—S2	2.5895 (12)	S7—Cs^x	3.536 (3)
Nb1—S5	2.5993 (13)	S7—Cs^ix	3.581 (3)
Nb1—S6	2.6103 (12)	S8—Nb1^viii	2.5055 (13)
Nb1—Nb2ⁱⁱⁱ	2.8843 (5)	S9—Cs^xi	4.044 (3)
Nb2—S10	2.4910 (13)	S10—Nb1^viii	2.5231 (13)
Nb2—S7	2.4932 (13)	S10—Cs^xii	3.444 (3)
Nb2—S4	2.4985 (12)	S10—Cs^viii	3.469 (3)

Csⁱ—Cs—S10ⁱⁱ	86.8 (5)	S9—Nb1—Nb2ⁱⁱⁱ	117.38 (3)
Csⁱ—Cs—S10ⁱⁱⁱ	82.5 (5)	S2—Nb1—Nb2ⁱⁱⁱ	115.30 (3)
S10ⁱⁱ—Cs—S10ⁱⁱⁱ	169.32 (5)	S5—Nb1—Nb2ⁱⁱⁱ	136.98 (3)
Csⁱ—Cs—S7^iv	88.8 (5)	S6—Nb1—Nb2ⁱⁱⁱ	133.76 (3)
S10ⁱⁱ—Cs—S7^iv	73.85 (7)	S10—Nb2—S7	48.25 (4)
S10ⁱⁱⁱ—Cs—S7^iv	105.80 (8)	S10—Nb2—S4	110.06 (4)
Csⁱ—Cs—S7^v	80.9 (5)	S7—Nb2—S4	90.81 (4)
S10ⁱⁱ—Cs—S7^v	105.35 (8)	S10—Nb2—S8	89.91 (4)
S10ⁱⁱⁱ—Cs—S7^v	73.00 (7)	S7—Nb2—S8	109.55 (4)
S7^iv—Cs—S7^v	169.64 (5)	S4—Nb2—S8	48.02 (4)
Csⁱ—Cs—S2	128.9 (5)	S10—Nb2—S5	138.22 (4)
S10ⁱⁱ—Cs—S2	134.71 (8)	S7—Nb2—S5	166.52 (4)
S10ⁱⁱⁱ—Cs—S2	54.41 (5)	S4—Nb2—S5	95.72 (4)
S7^iv—Cs—S2	79.52 (6)	S8—Nb2—S5	83.45 (4)
S7^v—Cs—S2	107.01 (8)	S10—Nb2—S9	91.02 (4)
Csⁱ—Cs—S1^v	139.1 (6)	S7—Nb2—S9	136.48 (4)
S10ⁱⁱ—Cs—S1^v	61.86 (5)	S4—Nb2—S9	122.02 (4)
S10ⁱⁱⁱ—Cs—S1^v	127.50 (7)	S8—Nb2—S9	80.28 (4)
S7^iv—Cs—S1^v	105.15 (7)	S5—Nb2—S9	47.20 (4)
S7^v—Cs—S1^v	82.99 (6)	S10—Nb2—S3	130.35 (5)
S2—Cs—S1^v	91.71 (4)	S7—Nb2—S3	84.19 (4)
Csⁱ—Cs—S5	131.1 (6)	S4—Nb2—S3	79.18 (4)
S10ⁱⁱ—Cs—S5	125.61 (7)	S8—Nb2—S3	124.13 (4)
S10ⁱⁱⁱ—Cs—S5	62.86 (5)	S5—Nb2—S3	85.47 (4)
S7^iv—Cs—S5	131.64 (7)	S9—Nb2—S3	126.33 (4)
S7^v—Cs—S5	57.45 (5)	S10—Nb2—S6	83.03 (4)
S2—Cs—S5	55.08 (4)	S7—Nb2—S6	82.29 (4)
S1^v—Cs—S5	64.82 (4)	S4—Nb2—S6	155.03 (4)
Csⁱ—Cs—S3^v	88.9 (5)	S8—Nb2—S6	156.36 (4)
S10ⁱⁱ—Cs—S3^v	52.55 (5)	S5—Nb2—S6	86.88 (4)
S10ⁱⁱⁱ—Cs—S3^v	126.89 (9)	S9—Nb2—S6	77.33 (4)
S7^iv—Cs—S3^v	126.40 (9)	S3—Nb2—S6	76.27 (4)
S7^v—Cs—S3^v	53.89 (5)	S10—Nb2—Nb1^viii	55.41 (3)
S2—Cs—S3^v	137.18 (6)	S7—Nb2—Nb1^viii	54.72 (3)
S1^v—Cs—S3^v	51.72 (4)	S4—Nb2—Nb1^viii	54.67 (3)
S5—Cs—S3^v	86.11 (6)	S8—Nb2—Nb1^viii	54.84 (3)
Csⁱ—Cs—S3^iv	81.7 (5)	S5—Nb2—Nb1^viii	138.05 (3)
S10ⁱⁱ—Cs—S3^iv	126.35 (9)	S9—Nb2—Nb1^viii	119.58 (3)
S10ⁱⁱⁱ—Cs—S3^iv	52.02 (5)	S3—Nb2—Nb1^viii	112.65 (3)
S7^iv—Cs—S3^iv	53.79 (5)	S6—Nb2—Nb1^viii	133.06 (3)
S7^v—Cs—S3^iv	123.87 (8)	S1—P—S3	112.52 (8)
S2—Cs—S3^iv	51.42 (5)	S1—P—S2	112.54 (8)
S1^v—Cs—S3^iv	137.41 (7)	S3—P—S2	112.78 (8)
S5—Cs—S3^iv	100.03 (7)	S1—P—S6	113.93 (9)
S3^v—Cs—S3^iv	170.63 (4)	S3—P—S6	102.73 (7)
Csⁱ—Cs—S9^vi	137.7 (6)	S2—P—S6	101.48 (7)
S10ⁱⁱ—Cs—S9^vi	75.21 (6)	P—S1—Ag	91.46 (6)
S10ⁱⁱⁱ—Cs—S9^vi	113.01 (7)	P—S1—Cs^ix	94.72 (7)
S7^iv—Cs—S9^vi	49.70 (4)	Ag—S1—Cs^ix	161.76 (7)
S7^v—Cs—S9^vi	140.51 (6)	P—S2—Nb1	90.68 (5)
S2—Cs—S9^vi	59.66 (4)	P—S2—Cs	129.50 (7)
S1^v—Cs—S9^vi	62.08 (4)	Nb1—S2—Cs	91.32 (6)
S5—Cs—S9^vi	89.44 (4)	P—S2—Csⁱ	136.28 (7)
S3^v—Cs—S9^vi	108.21 (6)	Nb1—S2—Csⁱ	89.76 (5)
S3^iv—Cs—S9^vi	79.11 (6)	P—S3—Nb2	90.27 (5)
Csⁱ—Cs—S2ⁱ	44.2 (5)	P—S3—Cs^ix	89.92 (6)
S10ⁱⁱ—Cs—S2ⁱ	50.32 (4)	Nb2—S3—Cs^ix	104.61 (6)
S10ⁱⁱⁱ—Cs—S2ⁱ	120.06 (6)	P—S3—Cs^x	99.22 (6)
S7^iv—Cs—S2ⁱ	99.18 (6)	Nb2—S3—Cs^x	103.24 (6)
S7^v—Cs—S2ⁱ	73.35 (5)	S8—S4—Nb1^viii	66.22 (5)
S2—Cs—S2ⁱ	173.07 (6)	S8—S4—Nb2	66.22 (5)
S1^v—Cs—S2ⁱ	95.19 (7)	Nb1^viii—S4—Nb2	70.56 (3)
S5—Cs—S2ⁱ	127.91 (8)	S9—S5—Nb2	66.47 (5)
S3^v—Cs—S2ⁱ	48.73 (4)	S9—S5—Nb1	65.71 (5)
S3^iv—Cs—S2ⁱ	122.41 (5)	Nb2—S5—Nb1	92.55 (4)
S9^vi—Cs—S2ⁱ	124.54 (8)	S9—S5—Cs	146.11 (7)
S1—Ag—S1^vii	180.00 (10)	Nb2—S5—Cs	140.15 (6)
S4ⁱⁱⁱ—Nb1—S7ⁱⁱⁱ	90.82 (4)	Nb1—S5—Cs	88.67 (5)
S4ⁱⁱⁱ—Nb1—S8ⁱⁱⁱ	48.08 (4)	P—S6—Nb1	89.39 (5)
S7ⁱⁱⁱ—Nb1—S8ⁱⁱⁱ	109.54 (4)	P—S6—Nb2	88.37 (5)
S4ⁱⁱⁱ—Nb1—S10ⁱⁱⁱ	109.13 (4)	Nb1—S6—Nb2	90.92 (4)
S7ⁱⁱⁱ—Nb1—S10ⁱⁱⁱ	47.89 (4)	S10—S7—Nb2	65.82 (5)
S8ⁱⁱⁱ—Nb1—S10ⁱⁱⁱ	89.23 (4)	S10—S7—Nb1^viii	66.76 (5)
S4ⁱⁱⁱ—Nb1—S9	91.47 (4)	Nb2—S7—Nb1^viii	70.64 (3)
S7ⁱⁱⁱ—Nb1—S9	78.95 (4)	S10—S7—Cs^x	171.29 (7)
S8ⁱⁱⁱ—Nb1—S9	137.40 (4)	Nb2—S7—Cs^x	118.24 (6)
S10ⁱⁱⁱ—Nb1—S9	121.46 (4)	Nb1^viii—S7—Cs^x	121.50 (5)
S4ⁱⁱⁱ—Nb1—S2	130.77 (4)	S10—S7—Cs^ix	161.56 (7)
S7ⁱⁱⁱ—Nb1—S2	124.06 (4)	Nb2—S7—Cs^ix	117.07 (6)
S8ⁱⁱⁱ—Nb1—S2	85.24 (4)	Nb1^viii—S7—Cs^ix	131.67 (5)
S10ⁱⁱⁱ—Nb1—S2	80.24 (4)	S4—S8—Nb1^viii	65.70 (5)
S9—Nb1—S2	125.60 (4)	S4—S8—Nb2	65.76 (5)
S4ⁱⁱⁱ—Nb1—S5	138.34 (4)	Nb1^viii—S8—Nb2	70.25 (3)
S7ⁱⁱⁱ—Nb1—S5	82.43 (4)	S5—S9—Nb1	67.42 (5)
S8ⁱⁱⁱ—Nb1—S5	167.42 (4)	S5—S9—Nb2	66.33 (5)
S10ⁱⁱⁱ—Nb1—S5	96.47 (4)	Nb1—S9—Nb2	93.27 (4)
S9—Nb1—S5	46.87 (4)	S5—S9—Cs^xi	111.56 (7)
S2—Nb1—S5	84.69 (4)	Nb1—S9—Cs^xi	104.00 (5)
S4ⁱⁱⁱ—Nb1—S6	83.16 (4)	Nb2—S9—Cs^xi	160.34 (6)
S7ⁱⁱⁱ—Nb1—S6	155.62 (4)	S7—S10—Nb2	65.93 (5)
S8ⁱⁱⁱ—Nb1—S6	83.80 (4)	S7—S10—Nb1^viii	65.35 (5)
S10ⁱⁱⁱ—Nb1—S6	155.76 (4)	Nb2—S10—Nb1^viii	70.23 (3)
S9—Nb1—S6	77.61 (4)	S7—S10—Cs^xii	110.68 (8)
S2—Nb1—S6	76.07 (4)	Nb2—S10—Cs^xii	176.58 (7)
S5—Nb1—S6	86.46 (4)	Nb1^viii—S10—Cs^xii	109.02 (5)
S4ⁱⁱⁱ—Nb1—Nb2ⁱⁱⁱ	54.77 (3)	S7—S10—Cs^viii	108.80 (8)
S7ⁱⁱⁱ—Nb1—Nb2ⁱⁱⁱ	54.64 (3)	Nb2—S10—Cs^viii	168.71 (5)
S8ⁱⁱⁱ—Nb1—Nb2ⁱⁱⁱ	54.91 (3)	Nb1^viii—S10—Cs^viii	98.55 (4)
S10ⁱⁱⁱ—Nb1—Nb2ⁱⁱⁱ	54.37 (3)

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

Experimental details

Crystal data
Chemical formula	Cs_0.5Ag_0.5Nb₂PS₁₀
M_r	657.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	7.3594 (3), 12.8534 (4), 13.7788 (6)
β (°)	91.0886 (12)
V (Å³)	1303.15 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.54
Crystal size (mm)	0.30 × 0.06 × 0.04

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.602, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12389, 2991, 2430
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.075, 1.08
No. of reflections	2991
No. of parameters	133
Δρ_max, Δρ_min (e Å⁻³)	1.18, −1.27

Computer programs: RAPID-AUTO (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), locally modified version of ORTEP (Johnson, 1965), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Ag—S1	2.4625 (13)	Nb2—S4	2.4985 (12)
Nb1—S4ⁱ	2.4953 (13)	Nb2—S8	2.5075 (12)
Nb1—S7ⁱ	2.4958 (12)	Nb2—S5	2.5643 (13)
Nb1—S8ⁱ	2.5055 (13)	Nb2—S9	2.5670 (12)
Nb1—S10ⁱ	2.5231 (13)	Nb2—S3	2.5920 (12)
Nb1—S9	2.5658 (12)	Nb2—S6	2.6250 (12)
Nb1—S2	2.5895 (12)	P—S1	1.9962 (18)
Nb1—S5	2.5993 (13)	P—S3	2.0391 (17)
Nb1—S6	2.6103 (12)	P—S2	2.0527 (17)
Nb2—S10	2.4910 (13)	P—S6	2.0851 (17)
Nb2—S7	2.4932 (13)

S1—Ag—S1ⁱⁱ	180.00 (10)

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

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2009–0094047). Use was made of the X-ray facilities supported by Ajou University.

References

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