The quinter­nary thio­phosphate Cs_0.5Ag_0.5Nb₂PS₁₀

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.

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

---

S1. Comment

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.

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 quinternary 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.

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).

S2. Experimental

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.

S3. Refinement

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/ų) is 0.94 Šfrom the Nb2 site and the deepest hole (-1.27 e/ų) is 0.84 Šfrom the Nb2 site. No additional symmetry, as tested by PLATON (Spek, 2009), has been detected in this structure.

Computing details

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

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)

Crystal data

Cs0.5Ag0.5Nb2PS10	F(000) = 1232
Mr = 657.78	Dx = 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) Å^3	0.30 × 0.06 × 0.04 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	133 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0248P)^2 + 3.4157P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.075	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 1.18 e Å^−3
2991 reflections	Δρmin = −1.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

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

Cs—Cs^i	0.644 (3)	Nb2—S8	2.5075 (12)
Cs—S10^ii	3.444 (3)	Nb2—S5	2.5643 (13)
Cs—S10^iii	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—S2^i	4.157 (3)	S2—Cs^i	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—S4^iii	2.4953 (13)	S4—S8	2.0371 (17)
Nb1—S7^iii	2.4958 (12)	S4—Nb1^viii	2.4953 (13)
Nb1—S8^iii	2.5055 (13)	S5—S9	2.0542 (18)
Nb1—S10^iii	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—Nb2^iii	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)
Cs^i—Cs—S10^ii	86.8 (5)	S9—Nb1—Nb2^iii	117.38 (3)
Cs^i—Cs—S10^iii	82.5 (5)	S2—Nb1—Nb2^iii	115.30 (3)
S10^ii—Cs—S10^iii	169.32 (5)	S5—Nb1—Nb2^iii	136.98 (3)
Cs^i—Cs—S7^iv	88.8 (5)	S6—Nb1—Nb2^iii	133.76 (3)
S10^ii—Cs—S7^iv	73.85 (7)	S10—Nb2—S7	48.25 (4)
S10^iii—Cs—S7^iv	105.80 (8)	S10—Nb2—S4	110.06 (4)
Cs^i—Cs—S7^v	80.9 (5)	S7—Nb2—S4	90.81 (4)
S10^ii—Cs—S7^v	105.35 (8)	S10—Nb2—S8	89.91 (4)
S10^iii—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)
Cs^i—Cs—S2	128.9 (5)	S10—Nb2—S5	138.22 (4)
S10^ii—Cs—S2	134.71 (8)	S7—Nb2—S5	166.52 (4)
S10^iii—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)
Cs^i—Cs—S1^v	139.1 (6)	S7—Nb2—S9	136.48 (4)
S10^ii—Cs—S1^v	61.86 (5)	S4—Nb2—S9	122.02 (4)
S10^iii—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)
Cs^i—Cs—S5	131.1 (6)	S4—Nb2—S3	79.18 (4)
S10^ii—Cs—S5	125.61 (7)	S8—Nb2—S3	124.13 (4)
S10^iii—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)
Cs^i—Cs—S3^v	88.9 (5)	S8—Nb2—S6	156.36 (4)
S10^ii—Cs—S3^v	52.55 (5)	S5—Nb2—S6	86.88 (4)
S10^iii—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)
Cs^i—Cs—S3^iv	81.7 (5)	S5—Nb2—Nb1^viii	138.05 (3)
S10^ii—Cs—S3^iv	126.35 (9)	S9—Nb2—Nb1^viii	119.58 (3)
S10^iii—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)
Cs^i—Cs—S9^vi	137.7 (6)	S2—P—S6	101.48 (7)
S10^ii—Cs—S9^vi	75.21 (6)	P—S1—Ag	91.46 (6)
S10^iii—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—Cs^i	136.28 (7)
S3^v—Cs—S9^vi	108.21 (6)	Nb1—S2—Cs^i	89.76 (5)
S3^iv—Cs—S9^vi	79.11 (6)	P—S3—Nb2	90.27 (5)
Cs^i—Cs—S2^i	44.2 (5)	P—S3—Cs^ix	89.92 (6)
S10^ii—Cs—S2^i	50.32 (4)	Nb2—S3—Cs^ix	104.61 (6)
S10^iii—Cs—S2^i	120.06 (6)	P—S3—Cs^x	99.22 (6)
S7^iv—Cs—S2^i	99.18 (6)	Nb2—S3—Cs^x	103.24 (6)
S7^v—Cs—S2^i	73.35 (5)	S8—S4—Nb1^viii	66.22 (5)
S2—Cs—S2^i	173.07 (6)	S8—S4—Nb2	66.22 (5)
S1^v—Cs—S2^i	95.19 (7)	Nb1^viii—S4—Nb2	70.56 (3)
S5—Cs—S2^i	127.91 (8)	S9—S5—Nb2	66.47 (5)
S3^v—Cs—S2^i	48.73 (4)	S9—S5—Nb1	65.71 (5)
S3^iv—Cs—S2^i	122.41 (5)	Nb2—S5—Nb1	92.55 (4)
S9^vi—Cs—S2^i	124.54 (8)	S9—S5—Cs	146.11 (7)
S1—Ag—S1^vii	180.00 (10)	Nb2—S5—Cs	140.15 (6)
S4^iii—Nb1—S7^iii	90.82 (4)	Nb1—S5—Cs	88.67 (5)
S4^iii—Nb1—S8^iii	48.08 (4)	P—S6—Nb1	89.39 (5)
S7^iii—Nb1—S8^iii	109.54 (4)	P—S6—Nb2	88.37 (5)
S4^iii—Nb1—S10^iii	109.13 (4)	Nb1—S6—Nb2	90.92 (4)
S7^iii—Nb1—S10^iii	47.89 (4)	S10—S7—Nb2	65.82 (5)
S8^iii—Nb1—S10^iii	89.23 (4)	S10—S7—Nb1^viii	66.76 (5)
S4^iii—Nb1—S9	91.47 (4)	Nb2—S7—Nb1^viii	70.64 (3)
S7^iii—Nb1—S9	78.95 (4)	S10—S7—Cs^x	171.29 (7)
S8^iii—Nb1—S9	137.40 (4)	Nb2—S7—Cs^x	118.24 (6)
S10^iii—Nb1—S9	121.46 (4)	Nb1^viii—S7—Cs^x	121.50 (5)
S4^iii—Nb1—S2	130.77 (4)	S10—S7—Cs^ix	161.56 (7)
S7^iii—Nb1—S2	124.06 (4)	Nb2—S7—Cs^ix	117.07 (6)
S8^iii—Nb1—S2	85.24 (4)	Nb1^viii—S7—Cs^ix	131.67 (5)
S10^iii—Nb1—S2	80.24 (4)	S4—S8—Nb1^viii	65.70 (5)
S9—Nb1—S2	125.60 (4)	S4—S8—Nb2	65.76 (5)
S4^iii—Nb1—S5	138.34 (4)	Nb1^viii—S8—Nb2	70.25 (3)
S7^iii—Nb1—S5	82.43 (4)	S5—S9—Nb1	67.42 (5)
S8^iii—Nb1—S5	167.42 (4)	S5—S9—Nb2	66.33 (5)
S10^iii—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)
S4^iii—Nb1—S6	83.16 (4)	Nb2—S9—Cs^xi	160.34 (6)
S7^iii—Nb1—S6	155.62 (4)	S7—S10—Nb2	65.93 (5)
S8^iii—Nb1—S6	83.80 (4)	S7—S10—Nb1^viii	65.35 (5)
S10^iii—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)
S4^iii—Nb1—Nb2^iii	54.77 (3)	S7—S10—Cs^viii	108.80 (8)
S7^iii—Nb1—Nb2^iii	54.64 (3)	Nb2—S10—Cs^viii	168.71 (5)
S8^iii—Nb1—Nb2^iii	54.91 (3)	Nb1^viii—S10—Cs^viii	98.55 (4)
S10^iii—Nb1—Nb2^iii	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.