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The quinter­nary thio­phosphate Cs0.5Ag0.5Nb2PS10, 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810021768/wm2357sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536810021768/wm2357Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 290 K
  • Mean [sigma](S-P) = 0.002 Å
  • Disorder in solvent or counterion
  • R factor = 0.034
  • wR factor = 0.075
  • Data-to-parameter ratio = 22.5

checkCIF/PLATON results

No syntax errors found



Alert level B CHEMS01_ALERT_1_B The sum formula contains elements in the wrong order. Cs precedes Ag Sequence must be alphabetical for inorganic structures. PLAT774_ALERT_1_B Suspect X-Y Bond in CIF: CS -- S9 .. 4.04 Ang. PLAT774_ALERT_1_B Suspect X-Y Bond in CIF: CS -- S2 .. 4.16 Ang. PLAT774_ALERT_1_B Suspect X-Y Bond in CIF: S2 -- CS .. 4.16 Ang. PLAT774_ALERT_1_B Suspect X-Y Bond in CIF: S9 -- CS .. 4.04 Ang.
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb1 -- S2 .. 5.82 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb1 -- S5 .. 5.03 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb1 -- S6 .. 6.32 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb1 -- S7_a .. 5.17 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb1 -- S10_a .. 5.71 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb2 -- S6 .. 5.31 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Nb2 -- S8 .. 5.67 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.16 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 3 PLAT041_ALERT_1_C Calc. and Reported SumFormula Strings Differ ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S7 .. 3.54 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S7 .. 3.58 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S2 .. 3.72 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S1 .. 3.77 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S5 .. 3.84 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S3 .. 3.91 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: CS -- S3 .. 3.96 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: S1 -- CS .. 3.77 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: S3 -- CS .. 3.91 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: S3 -- CS .. 3.96 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: S7 -- CS .. 3.54 Ang. PLAT774_ALERT_1_C Suspect X-Y Bond in CIF: S7 -- CS .. 3.58 Ang. PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 3
Alert level G PLAT302_ALERT_4_G Note: Anion/Solvent Disorder ................... 50.00 Perc.
0 ALERT level A = In general: serious problem 5 ALERT level B = Potentially serious problem 24 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 19 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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, Cs0.5Ag0.5Nb2PS10.

The title compound is isostructural with the previously reported K0.34Cu0.5Nb2PS10 (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 eg 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[PS43-][S22-]3.

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 Ag0.88Nb2PS10; for quinternary thiophosphates, see: Kwak & Yun (2008) for K0.34Cu0.5Nb2PS10, Dong et al. (2005a) for K0.5Ag0.5Nb2PS10, and Dong et al. (2005b) for Rb0.38Ag0.5Nb2PS10.

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 Ag0.88Nb2PS10. For quintenary thiophosphates, see: Kwak & Yun (2008) for K0.34Cu0.5Nb2PS10, Dong et al. (2005a) for K0.5Ag0.5Nb2PS10, and Dong et al. (2005b) for Rb0.38Ag0.5Nb2PS10. 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

Cs0.5Ag0.5Nb2PS10 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.

Refinement top

Refinement went smoothly but the anisotropic displacement parameters (ADPs) of the Cs (Wyckoff position 4e) and Ag (2a) atoms were large compared with those of the other atoms. Because non-stoichiometry in these phases is sometimes observed and the distance between Cs atoms is too short if full occupancy is assumed, the occupancies of each metal atom were checked by refining the site occupation factors (SOFs) while those of the other atoms were fixed. With the non-stoichiometric model, the SOF of the Cs site was reduced significantly from 1 to 0.49 and the residuals improved also. As no evidence was found for ordering of the Cs site at Wyckoff position 2c, a statistically disordered structure was finally modelled. The final difference Fourier map showed that the highest residual electron density (1.18 e/Å3) is 0.94 Å from the Nb2 site and the deepest hole (-1.27 e/Å3) is 0.84 Å from the Nb2 site. No additional symmetry, as tested by PLATON (Spek, 2009), has been detected in this structure.

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
[Figure 1] Fig. 1. A view of the Cs0.5Ag0.5Nb2PS10 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
Cs0.5Ag0.5Nb2PS10F(000) = 1232
Mr = 657.78Dx = 3.353 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8832 reflections
a = 7.3594 (3) Åθ = 3.2–27.5°
b = 12.8534 (4) ŵ = 5.54 mm1
c = 13.7788 (6) ÅT = 290 K
β = 91.0886 (12)°Needle, dark brown
V = 1303.15 (8) Å30.30 × 0.06 × 0.04 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2430 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 99
Tmin = 0.602, Tmax = 1.000k = 1614
12389 measured reflectionsl = 1717
2991 independent reflections
Refinement top
Refinement on F2133 parameters
Least-squares matrix: full0 restraints
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0248P)2 + 3.4157P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.075(Δ/σ)max < 0.001
S = 1.08Δρmax = 1.18 e Å3
2991 reflectionsΔρmin = 1.27 e Å3
Crystal data top
Cs0.5Ag0.5Nb2PS10V = 1303.15 (8) Å3
Mr = 657.78Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3594 (3) ŵ = 5.54 mm1
b = 12.8534 (4) ÅT = 290 K
c = 13.7788 (6) Å0.30 × 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)
Tmin = 0.602, Tmax = 1.000Rint = 0.049
12389 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034133 parameters
wR(F2) = 0.0750 restraints
S = 1.08Δρmax = 1.18 e Å3
2991 reflectionsΔρmin = 1.27 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cs0.0009 (4)0.02093 (15)0.48715 (19)0.0512 (5)0.5
Ag0000.0539 (2)
Nb10.42651 (5)0.03565 (3)0.24995 (3)0.01333 (11)
Nb20.43445 (5)0.32590 (3)0.25353 (3)0.01280 (11)
P0.11427 (16)0.18631 (9)0.14370 (10)0.0170 (3)
S10.03805 (19)0.18878 (10)0.02229 (11)0.0292 (3)
S20.07865 (16)0.05281 (9)0.22287 (10)0.0210 (3)
S30.08568 (16)0.31790 (9)0.22464 (10)0.0207 (3)
S40.33249 (16)0.47121 (9)0.35994 (9)0.0187 (3)
S50.38477 (17)0.18131 (9)0.37848 (9)0.0190 (3)
S60.39304 (16)0.18214 (8)0.11963 (9)0.0161 (2)
S70.42828 (17)0.44324 (9)0.10942 (9)0.0194 (3)
S80.58572 (16)0.41695 (9)0.39426 (9)0.0184 (3)
S90.63765 (16)0.17797 (9)0.31795 (9)0.0189 (3)
S100.67972 (16)0.38737 (9)0.14538 (9)0.0204 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cs0.0270 (3)0.0779 (16)0.0489 (13)0.0003 (11)0.0060 (7)0.0283 (10)
Ag0.0518 (4)0.0298 (3)0.0800 (6)0.0028 (3)0.0017 (4)0.0287 (4)
Nb10.0150 (2)0.00814 (18)0.0168 (2)0.00081 (16)0.00185 (16)0.00082 (16)
Nb20.0145 (2)0.00802 (19)0.0158 (2)0.00071 (16)0.00210 (16)0.00048 (16)
P0.0157 (5)0.0115 (5)0.0235 (7)0.0014 (5)0.0057 (5)0.0025 (5)
S10.0325 (7)0.0228 (6)0.0316 (8)0.0023 (6)0.0168 (6)0.0038 (6)
S20.0181 (5)0.0140 (5)0.0310 (7)0.0014 (5)0.0023 (5)0.0030 (5)
S30.0168 (5)0.0146 (5)0.0305 (7)0.0023 (5)0.0034 (5)0.0073 (5)
S40.0190 (5)0.0146 (5)0.0225 (7)0.0007 (5)0.0017 (5)0.0031 (5)
S50.0256 (6)0.0126 (5)0.0189 (6)0.0001 (5)0.0008 (5)0.0007 (5)
S60.0186 (5)0.0104 (5)0.0193 (6)0.0019 (5)0.0015 (5)0.0007 (5)
S70.0269 (6)0.0131 (5)0.0180 (6)0.0009 (5)0.0044 (5)0.0004 (5)
S80.0233 (6)0.0124 (5)0.0195 (6)0.0013 (5)0.0043 (5)0.0000 (5)
S90.0185 (5)0.0128 (5)0.0251 (7)0.0001 (5)0.0054 (5)0.0009 (5)
S100.0217 (6)0.0152 (5)0.0244 (7)0.0003 (5)0.0048 (5)0.0021 (5)
Geometric parameters (Å, º) top
Cs—Csi0.644 (3)Nb2—S82.5075 (12)
Cs—S10ii3.444 (3)Nb2—S52.5643 (13)
Cs—S10iii3.469 (3)Nb2—S92.5670 (12)
Cs—S7iv3.536 (3)Nb2—S32.5920 (12)
Cs—S7v3.581 (3)Nb2—S62.6250 (12)
Cs—S23.722 (3)Nb2—Nb1viii2.8843 (5)
Cs—S1v3.773 (2)P—S11.9962 (18)
Cs—S53.835 (3)P—S32.0391 (17)
Cs—S3v3.915 (3)P—S22.0527 (17)
Cs—S3iv3.956 (3)P—S62.0851 (17)
Cs—S9vi4.044 (3)S1—Csix3.773 (2)
Cs—S2i4.157 (3)S2—Csi4.157 (3)
Ag—S12.4625 (13)S3—Csix3.915 (3)
Ag—S1vii2.4625 (13)S3—Csx3.956 (3)
Nb1—S4iii2.4953 (13)S4—S82.0371 (17)
Nb1—S7iii2.4958 (12)S4—Nb1viii2.4953 (13)
Nb1—S8iii2.5055 (13)S5—S92.0542 (18)
Nb1—S10iii2.5231 (13)S7—S102.0372 (17)
Nb1—S92.5658 (12)S7—Nb1viii2.4958 (12)
Nb1—S22.5895 (12)S7—Csx3.536 (3)
Nb1—S52.5993 (13)S7—Csix3.581 (3)
Nb1—S62.6103 (12)S8—Nb1viii2.5055 (13)
Nb1—Nb2iii2.8843 (5)S9—Csxi4.044 (3)
Nb2—S102.4910 (13)S10—Nb1viii2.5231 (13)
Nb2—S72.4932 (13)S10—Csxii3.444 (3)
Nb2—S42.4985 (12)S10—Csviii3.469 (3)
Csi—Cs—S10ii86.8 (5)S9—Nb1—Nb2iii117.38 (3)
Csi—Cs—S10iii82.5 (5)S2—Nb1—Nb2iii115.30 (3)
S10ii—Cs—S10iii169.32 (5)S5—Nb1—Nb2iii136.98 (3)
Csi—Cs—S7iv88.8 (5)S6—Nb1—Nb2iii133.76 (3)
S10ii—Cs—S7iv73.85 (7)S10—Nb2—S748.25 (4)
S10iii—Cs—S7iv105.80 (8)S10—Nb2—S4110.06 (4)
Csi—Cs—S7v80.9 (5)S7—Nb2—S490.81 (4)
S10ii—Cs—S7v105.35 (8)S10—Nb2—S889.91 (4)
S10iii—Cs—S7v73.00 (7)S7—Nb2—S8109.55 (4)
S7iv—Cs—S7v169.64 (5)S4—Nb2—S848.02 (4)
Csi—Cs—S2128.9 (5)S10—Nb2—S5138.22 (4)
S10ii—Cs—S2134.71 (8)S7—Nb2—S5166.52 (4)
S10iii—Cs—S254.41 (5)S4—Nb2—S595.72 (4)
S7iv—Cs—S279.52 (6)S8—Nb2—S583.45 (4)
S7v—Cs—S2107.01 (8)S10—Nb2—S991.02 (4)
Csi—Cs—S1v139.1 (6)S7—Nb2—S9136.48 (4)
S10ii—Cs—S1v61.86 (5)S4—Nb2—S9122.02 (4)
S10iii—Cs—S1v127.50 (7)S8—Nb2—S980.28 (4)
S7iv—Cs—S1v105.15 (7)S5—Nb2—S947.20 (4)
S7v—Cs—S1v82.99 (6)S10—Nb2—S3130.35 (5)
S2—Cs—S1v91.71 (4)S7—Nb2—S384.19 (4)
Csi—Cs—S5131.1 (6)S4—Nb2—S379.18 (4)
S10ii—Cs—S5125.61 (7)S8—Nb2—S3124.13 (4)
S10iii—Cs—S562.86 (5)S5—Nb2—S385.47 (4)
S7iv—Cs—S5131.64 (7)S9—Nb2—S3126.33 (4)
S7v—Cs—S557.45 (5)S10—Nb2—S683.03 (4)
S2—Cs—S555.08 (4)S7—Nb2—S682.29 (4)
S1v—Cs—S564.82 (4)S4—Nb2—S6155.03 (4)
Csi—Cs—S3v88.9 (5)S8—Nb2—S6156.36 (4)
S10ii—Cs—S3v52.55 (5)S5—Nb2—S686.88 (4)
S10iii—Cs—S3v126.89 (9)S9—Nb2—S677.33 (4)
S7iv—Cs—S3v126.40 (9)S3—Nb2—S676.27 (4)
S7v—Cs—S3v53.89 (5)S10—Nb2—Nb1viii55.41 (3)
S2—Cs—S3v137.18 (6)S7—Nb2—Nb1viii54.72 (3)
S1v—Cs—S3v51.72 (4)S4—Nb2—Nb1viii54.67 (3)
S5—Cs—S3v86.11 (6)S8—Nb2—Nb1viii54.84 (3)
Csi—Cs—S3iv81.7 (5)S5—Nb2—Nb1viii138.05 (3)
S10ii—Cs—S3iv126.35 (9)S9—Nb2—Nb1viii119.58 (3)
S10iii—Cs—S3iv52.02 (5)S3—Nb2—Nb1viii112.65 (3)
S7iv—Cs—S3iv53.79 (5)S6—Nb2—Nb1viii133.06 (3)
S7v—Cs—S3iv123.87 (8)S1—P—S3112.52 (8)
S2—Cs—S3iv51.42 (5)S1—P—S2112.54 (8)
S1v—Cs—S3iv137.41 (7)S3—P—S2112.78 (8)
S5—Cs—S3iv100.03 (7)S1—P—S6113.93 (9)
S3v—Cs—S3iv170.63 (4)S3—P—S6102.73 (7)
Csi—Cs—S9vi137.7 (6)S2—P—S6101.48 (7)
S10ii—Cs—S9vi75.21 (6)P—S1—Ag91.46 (6)
S10iii—Cs—S9vi113.01 (7)P—S1—Csix94.72 (7)
S7iv—Cs—S9vi49.70 (4)Ag—S1—Csix161.76 (7)
S7v—Cs—S9vi140.51 (6)P—S2—Nb190.68 (5)
S2—Cs—S9vi59.66 (4)P—S2—Cs129.50 (7)
S1v—Cs—S9vi62.08 (4)Nb1—S2—Cs91.32 (6)
S5—Cs—S9vi89.44 (4)P—S2—Csi136.28 (7)
S3v—Cs—S9vi108.21 (6)Nb1—S2—Csi89.76 (5)
S3iv—Cs—S9vi79.11 (6)P—S3—Nb290.27 (5)
Csi—Cs—S2i44.2 (5)P—S3—Csix89.92 (6)
S10ii—Cs—S2i50.32 (4)Nb2—S3—Csix104.61 (6)
S10iii—Cs—S2i120.06 (6)P—S3—Csx99.22 (6)
S7iv—Cs—S2i99.18 (6)Nb2—S3—Csx103.24 (6)
S7v—Cs—S2i73.35 (5)S8—S4—Nb1viii66.22 (5)
S2—Cs—S2i173.07 (6)S8—S4—Nb266.22 (5)
S1v—Cs—S2i95.19 (7)Nb1viii—S4—Nb270.56 (3)
S5—Cs—S2i127.91 (8)S9—S5—Nb266.47 (5)
S3v—Cs—S2i48.73 (4)S9—S5—Nb165.71 (5)
S3iv—Cs—S2i122.41 (5)Nb2—S5—Nb192.55 (4)
S9vi—Cs—S2i124.54 (8)S9—S5—Cs146.11 (7)
S1—Ag—S1vii180.00 (10)Nb2—S5—Cs140.15 (6)
S4iii—Nb1—S7iii90.82 (4)Nb1—S5—Cs88.67 (5)
S4iii—Nb1—S8iii48.08 (4)P—S6—Nb189.39 (5)
S7iii—Nb1—S8iii109.54 (4)P—S6—Nb288.37 (5)
S4iii—Nb1—S10iii109.13 (4)Nb1—S6—Nb290.92 (4)
S7iii—Nb1—S10iii47.89 (4)S10—S7—Nb265.82 (5)
S8iii—Nb1—S10iii89.23 (4)S10—S7—Nb1viii66.76 (5)
S4iii—Nb1—S991.47 (4)Nb2—S7—Nb1viii70.64 (3)
S7iii—Nb1—S978.95 (4)S10—S7—Csx171.29 (7)
S8iii—Nb1—S9137.40 (4)Nb2—S7—Csx118.24 (6)
S10iii—Nb1—S9121.46 (4)Nb1viii—S7—Csx121.50 (5)
S4iii—Nb1—S2130.77 (4)S10—S7—Csix161.56 (7)
S7iii—Nb1—S2124.06 (4)Nb2—S7—Csix117.07 (6)
S8iii—Nb1—S285.24 (4)Nb1viii—S7—Csix131.67 (5)
S10iii—Nb1—S280.24 (4)S4—S8—Nb1viii65.70 (5)
S9—Nb1—S2125.60 (4)S4—S8—Nb265.76 (5)
S4iii—Nb1—S5138.34 (4)Nb1viii—S8—Nb270.25 (3)
S7iii—Nb1—S582.43 (4)S5—S9—Nb167.42 (5)
S8iii—Nb1—S5167.42 (4)S5—S9—Nb266.33 (5)
S10iii—Nb1—S596.47 (4)Nb1—S9—Nb293.27 (4)
S9—Nb1—S546.87 (4)S5—S9—Csxi111.56 (7)
S2—Nb1—S584.69 (4)Nb1—S9—Csxi104.00 (5)
S4iii—Nb1—S683.16 (4)Nb2—S9—Csxi160.34 (6)
S7iii—Nb1—S6155.62 (4)S7—S10—Nb265.93 (5)
S8iii—Nb1—S683.80 (4)S7—S10—Nb1viii65.35 (5)
S10iii—Nb1—S6155.76 (4)Nb2—S10—Nb1viii70.23 (3)
S9—Nb1—S677.61 (4)S7—S10—Csxii110.68 (8)
S2—Nb1—S676.07 (4)Nb2—S10—Csxii176.58 (7)
S5—Nb1—S686.46 (4)Nb1viii—S10—Csxii109.02 (5)
S4iii—Nb1—Nb2iii54.77 (3)S7—S10—Csviii108.80 (8)
S7iii—Nb1—Nb2iii54.64 (3)Nb2—S10—Csviii168.71 (5)
S8iii—Nb1—Nb2iii54.91 (3)Nb1viii—S10—Csviii98.55 (4)
S10iii—Nb1—Nb2iii54.37 (3)
Symmetry codes: (i) x, y, z+1; (ii) x1, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x, y1/2, z+1/2; (v) x, y+1/2, z+1/2; (vi) x1, y, z; (vii) x, y, z; (viii) x+1, y+1/2, z+1/2; (ix) x, y+1/2, z1/2; (x) x, y+1/2, z+1/2; (xi) x+1, y, z; (xii) x+1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaCs0.5Ag0.5Nb2PS10
Mr657.78
Crystal system, space groupMonoclinic, P21/c
Temperature (K)290
a, b, c (Å)7.3594 (3), 12.8534 (4), 13.7788 (6)
β (°) 91.0886 (12)
V3)1303.15 (8)
Z4
Radiation typeMo Kα
µ (mm1)5.54
Crystal size (mm)0.30 × 0.06 × 0.04
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.602, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
12389, 2991, 2430
Rint0.049
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.075, 1.08
No. of reflections2991
No. of parameters133
Δρmax, Δρmin (e Å3)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—S12.4625 (13)Nb2—S42.4985 (12)
Nb1—S4i2.4953 (13)Nb2—S82.5075 (12)
Nb1—S7i2.4958 (12)Nb2—S52.5643 (13)
Nb1—S8i2.5055 (13)Nb2—S92.5670 (12)
Nb1—S10i2.5231 (13)Nb2—S32.5920 (12)
Nb1—S92.5658 (12)Nb2—S62.6250 (12)
Nb1—S22.5895 (12)P—S11.9962 (18)
Nb1—S52.5993 (13)P—S32.0391 (17)
Nb1—S62.6103 (12)P—S22.0527 (17)
Nb2—S102.4910 (13)P—S62.0851 (17)
Nb2—S72.4932 (13)
S1—Ag—S1ii180.00 (10)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y, z.
 

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