Cs0.49NbPS6

Lee, E.; Lee, Y.; Yun, H.

doi:10.1107/S1600536810052724

inorganic compounds

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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page i4

https://doi.org/10.1107/S1600536810052724

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Cs_0.49NbPS₆

Eunsil Lee,^a Yonghee Lee ^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 14 November 2010; accepted 15 December 2010; online 24 December 2010)

The quaternary thiophosphate, Cs_0.49NbPS₆, caesium hexathioniobiophosphate(V), has been synthesized by the reactive halide flux method. The title compound is isotypic with Rb_0.46TaPS₆ and is made up of a bicapped trigonal–biprismatic [Nb₂S₁₂] unit and a tetrahedral [PS₄] group. The [Nb₂S₁₂] units linked by the [PS₄] tetrahedra form infinite chains, yielding a three-dimensional network with rather large van der Waals gaps along the c axis in which the disordered Cs⁺ ions reside. The electrons released by the Cs atoms are transferred to the pairwise niobium metal site and there are substantial intermetallic Nb—Nb bonding interactions. This leads to a significant decrease of the intermetallic distance in the title compound compared to that in TaPS₆. The classical charge balance of the title compound may be represented as [Cs⁺]_0.49[Nb^4.51+][P⁵⁺][S²⁻]₄[S₂²⁻].

Related literature

For the synthesis and structural characterization of TaPS₆, see: Fiechter et al. (1980 ). For the related quaternary alkali metal thiophosphates, see: K_0.38TaPS₆ and Rb_0.46TaPS₆ (Gutzmann et al., 2004a ) and A₂Nb₂P₂S₁₂ (A = K, Rb, Cs; Gieck et al., 2004 ). Quite a few quaternary alkali metal thiophosphates having similar composition but with different structures have been reported. For compounds with layered structures, see: Gutzmann & Bensch (2003 ) for Rb₄Ta₄P₄S₂₄; Gutzmann et al. (2004b ) for Cs₄Ta₄P₄S₂₄ and Cs₂Ta₂P₂S₁₂ and Gutzmann et al. (2005) for K₄Ta₄P₄S₂₄. For Rb₂Ta₂P₂S₁₁ with a one-dimensional structure, see: Gutzmann & Bensch (2002 ).

Experimental

Crystal data

Cs_0.49NbPS₆
M_r = 380.95
Tetragonal, $[I \overline 42d ]$
a = 15.9477 (3) Å
c = 13.2461 (3) Å
V = 3368.88 (11) Å³
Z = 16
Mo Kα radiation
μ = 5.08 mm⁻¹
T = 290 K
0.30 × 0.08 × 0.06 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.751, T_max = 1.000
16125 measured reflections
1929 independent reflections
1843 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.047
S = 1.06
1929 reflections
81 parameters
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ), 851 Friedel pairs
Flack parameter: 0.452 (18)

Table 1
Selected geometric parameters (Å, °)

Nb—S1ⁱ	2.5016 (9)
Nb—S6ⁱⁱ	2.5221 (9)
Nb—S1ⁱⁱⁱ	2.5238 (8)
Nb—S6^iv	2.5457 (9)
Nb—S2	2.5457 (9)
Nb—S3	2.5730 (9)
Nb—S5^v	2.5971 (9)
Nb—S4	2.6266 (9)
Nb—Nb^vi	3.1236 (5)
P1—S2ⁱ	2.0300 (11)
P1—S2	2.0300 (11)
P1—S5^vii	2.0413 (10)
P1—S5^v	2.0413 (10)
P2—S3^viii	2.0353 (10)
P2—S3^ix	2.0353 (10)
P2—S4^ix	2.0519 (11)
P2—S4^viii	2.0519 (11)
S1—S1^x	2.0302 (17)
S6—S6^xi	2.0264 (17)

S2ⁱ—P1—S2	109.11 (7)
S2ⁱ—P1—S5^vii	102.92 (3)
S2—P1—S5^vii	113.21 (4)
S2ⁱ—P1—S5^v	113.21 (4)
S2—P1—S5^v	102.92 (3)
S5^vii—P1—S5^v	115.63 (7)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, -z+{\script{1\over 4}}]$ ; (ii) $[-y, -x+{\script{1\over 2}}, z+{\script{1\over 4}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 4}}]$ ; (iv) $[y, x-{\script{1\over 2}}, z+{\script{1\over 4}}]$ ; (v) $[y-{\script{1\over 2}}, -x+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) -x, -y, z; (vii) $[y-{\script{1\over 2}}, x, z-{\script{1\over 4}}]$ ; (viii) $[y+{\script{1\over 2}}, -x+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ix) $[y+{\script{1\over 2}}, x, z-{\script{1\over 4}}]$ ; (x) -x, -y+1, z; (xi) -x+1, -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: https://doi.org/10.1107/S1600536810052724/si2311sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052724/si2311Isup2.hkl

checkCIF report

Comment top

During an effort to find a new phase in the A_xMPS₆ family (A=alkali metals; M=Ta, Nb), a new compound was isolated. Here we report the synthesis and structure of the new quaternary thiophosphates, Cs_0.49NbPS₆.

The title compound is isostructural with the previously reported Rb_0.46TaPS₆ (Gutzmann et al., 2004a). The structure of Cs_0.49NbPS₆ is also very similar to that of ANb₂P₂S₁₂ (A=K, Rb, and Cs, Gieck et al., 2004) prepared from alkali metal sulfide fluxes. The only difference between them lies in the distribution of the alkali metals. There are two crystallographically independent sites for Cs atoms in ANb₂P₂S₁₂, while we were able to find only one in Cs_0.49NbPS₆.

The structure of Cs_0.49NbPS₆ is made up of the bicapped trigonal biprismatic [Nb₂S₁₂] unit and the tetrahedral [PS₄] group. The niobium atom is coordinated by eight sulfur atoms in a distorted bicapped trigonal prismatic arrangement. Two NbS₈ prisms share a rectangular face to form the [Nb₂S₁₂] dimeric core. Four sulfur atoms sharing rectangular prism faces are in pairs with two disulfide ions, (S—S)^2-. Each one of the capping sulfur atoms and one of the sulfur atoms at the corner of the [Nb₂S₁₂] unit are bound to a phosphorous atom (Fig. 1). Additional two sulfur atoms from the neighboring [Nb₂S₁₂] units are connected to the phosphorous atoms to complete the [PS₄] tetrahedral coordination. Each [Nb₂S₁₂] unit connects four phosphorous atoms to build up left- and right-handed helices. These helices interwind to each other forming infinite channels along the [001] direction (Fig. 2). The structural array yields rather large channels, where the Cs⁺ ions reside. The size of the cations is small compared to the diameter of the large channels and the cations can therefore rattle within the channels as indicated by the high anisotropic displacement parameters.

The Nb—S and P—S distances are in good agreement with those found in other related phases (Gutzmann et al., 2004b). The interatomic Nb—Nb distance is 3.124 (1) Å which is similar to those in K_0.38TaPS₆ (3.142 (2) Å) and Rb_0.46TaPS₆ (3.1011 (5) Å). These distances are considerably shorter compared to that in TaPS₆ (3.361 (1) Å, Fiechter et al., 1980). The electrons released by the Cs atoms are transferred to pair-wise niobium metal sites and there are substantial intermetallic Nb—Nb bonding interactions. Consequently, the classical charge balance of the title compound may be represented as [Cs⁺]_0.49[M^4.51+][P⁵⁺][S^2-]₄[S₂^2-].

Related literature top

For the synthesis and structural characterization of TaPS₆, see: Fiechter et al. (1980). For the related quaternary alkali metal thiophosphates, see: for K_0.38TaPS₆ and Rb_0.46TaPS₆, see: Gutzmann et al. (2004a) and for A₂Nb₂P₂S₁₂ (A = K, Rb, Cs), see: Gieck et al. (2004). Quite a few quaternary alkali metal thiophosphates having similar composition but with different structures have been reported. For layered compounds, see: Gutzmann & Bensch (2003) for Rb₄Ta₄P₄S₂₄; Gutzmann et al. (2004b) for Cs₄Ta₄P₄S₂₄ and Cs₂Ta₂P₂S₁₂ and Gutzmann et al. (2005) for K₄Ta₄P₄S₂₄. For the one-dimensional compound Rb₂Ta₂P₂S₁₁, see: Gutzmann & Bensch (2002).

Experimental top

Cs_0.49NbPS₆ was prepared by the reaction of elements Nb, P, and S by the reactive halide-flux technique. A combination of the pure elements, Nb powder (CERAC 99.999%), P powder (CERAC 99.5%) and S powder (Aldrich 99.999%) were mixed in a fused silica tube in molar ratio of Nb:P:S=1:1:6 in the presence of CsCl as flux. The mass ratio of the reactants and the alkali halide flux was 1:2. The tube was evacuated to 0.133 Pa, sealed, and heated gradually (60 K/h) to 973 K, where it was kept for 72 h. The tube was cooled to room temperature at the rate 4 K/h. The excess halide was removed with distilled water and shiny black needle-shaped crystals were obtained. The crystals are stable in air and water. Qualitative analysis of the crystals with an EDAX-equipped SEM indicated the presence of Cs, Nb, P, and S. The composition of the compound was determined by single-crystal X-ray diffraction.

Structure description top

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 perspective view of the bicapped trigonal biprismatic [Nb₂S₁₂] unit and its neighboring tetrahedral [PS₄] groups. The Nb—S bonds have been omitted for clarity, except for the capping S atoms. Displacement ellipsoids are drawn at the 60% probability level. [Symmetry code: (vi) -x, -y, z]
	Fig. 2. View of Cs_0.49NbPS₆ along the c axis. Atoms are as marked in Fig. 1.

caesium niobium phosphorus hexasulfide top

Crystal data top

Cs_0.49NbPS₆	D_x = 3.004 Mg m⁻³
M_r = 380.95	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I42d	Cell parameters from 14367 reflections
Hall symbol: I -4 2bw	θ = 3.3–27.5°
a = 15.9477 (3) Å	µ = 5.08 mm⁻¹
c = 13.2461 (3) Å	T = 290 K
V = 3368.88 (11) Å³	Needle, black
Z = 16	0.30 × 0.08 × 0.06 mm
F(000) = 2860

Data collection top

Rigaku R-AXIS RAPID diffractometer	1843 reflections with I > 2σ(I)
ω scans	R_int = 0.032
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	θ_max = 27.5°, θ_min = 3.2°
T_min = 0.751, T_max = 1.000	h = −20→20
16125 measured reflections	k = −20→20
1929 independent reflections	l = −16→17

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0309P)² + 0.1672P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.020	(Δ/σ)_max = 0.001
wR(F²) = 0.047	Δρ_max = 0.84 e Å⁻³
S = 1.06	Δρ_min = −0.42 e Å⁻³
1929 reflections	Absolute structure: Flack (1983), 851 Friedel pairs
81 parameters	Absolute structure parameter: 0.452 (18)

Crystal data top

Cs_0.49NbPS₆	Z = 16
M_r = 380.95	Mo Kα radiation
Tetragonal, I42d	µ = 5.08 mm⁻¹
a = 15.9477 (3) Å	T = 290 K
c = 13.2461 (3) Å	0.30 × 0.08 × 0.06 mm
V = 3368.88 (11) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	1929 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1843 reflections with I > 2σ(I)
T_min = 0.751, T_max = 1.000	R_int = 0.032
16125 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	0 restraints
wR(F²) = 0.047	Δρ_max = 0.84 e Å⁻³
S = 1.06	Δρ_min = −0.42 e Å⁻³
1929 reflections	Absolute structure: Flack (1983), 851 Friedel pairs
81 parameters	Absolute structure parameter: 0.452 (18)

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	0.31826 (2)	0.25	0.125	0.04486 (17)	0.974 (2)
Nb	0.066145 (17)	0.072220 (17)	0.24995 (2)	0.01403 (8)
P1	0.05549 (7)	0.25	0.125	0.0163 (2)
P2	0.58291 (7)	0.25	0.125	0.0161 (2)
S1	0.04769 (5)	0.54216 (5)	0.12737 (6)	0.01871 (18)
S2	0.12931 (6)	0.14853 (5)	0.09924 (7)	0.02128 (18)
S3	0.14510 (5)	0.15492 (6)	0.38699 (7)	0.0232 (2)
S4	0.22010 (5)	0.01370 (5)	0.24947 (7)	0.02042 (18)
S5	0.28529 (5)	0.48732 (5)	0.25169 (7)	0.02144 (19)
S6	0.45621 (5)	0.04603 (5)	0.12972 (6)	0.01928 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs	0.0218 (2)	0.0690 (3)	0.0438 (2)	0	0	0.0247 (2)
Nb	0.01411 (14)	0.01527 (14)	0.01272 (13)	−0.00014 (9)	−0.00042 (12)	−0.00043 (12)
P1	0.0171 (5)	0.0137 (5)	0.0181 (5)	0	0	0.0005 (5)
P2	0.0191 (5)	0.0140 (5)	0.0153 (5)	0	0	−0.0011 (5)
S1	0.0200 (4)	0.0213 (4)	0.0148 (3)	0.0027 (3)	−0.0025 (4)	−0.0031 (3)
S2	0.0219 (4)	0.0167 (4)	0.0252 (4)	0.0008 (3)	0.0066 (3)	0.0008 (3)
S3	0.0187 (4)	0.0246 (4)	0.0262 (5)	0.0045 (4)	−0.0045 (3)	−0.0115 (4)
S4	0.0200 (4)	0.0236 (4)	0.0177 (4)	0.0059 (3)	−0.0015 (4)	−0.0051 (4)
S5	0.0221 (4)	0.0227 (4)	0.0196 (4)	−0.0066 (3)	0.0028 (4)	−0.0059 (4)
S6	0.0216 (4)	0.0201 (4)	0.0161 (4)	0.0017 (4)	0.0013 (4)	−0.0020 (3)

Geometric parameters (Å, º) top

Cs—S2	3.4374 (10)	P1—S2ⁱ	2.0300 (11)
Cs—S2ⁱ	3.4373 (10)	P1—S2	2.0300 (11)
Cs—S3ⁱⁱ	3.5468 (9)	P1—S5^xi	2.0413 (10)
Cs—S3ⁱⁱⁱ	3.5468 (9)	P1—S5^ix	2.0413 (10)
Cs—S4^iv	3.5646 (9)	P2—S3^iv	2.0353 (10)
Cs—S4^v	3.5646 (9)	P2—S3^v	2.0353 (10)
Cs—S6ⁱ	3.9274 (9)	P2—S4^v	2.0519 (11)
Cs—S6	3.9274 (9)	P2—S4^iv	2.0519 (11)
Cs—S5ⁱ	4.1733 (8)	S1—S1^xii	2.0302 (17)
Cs—S5	4.1733 (8)	S1—Nbⁱ	2.5016 (9)
Cs—P1	4.1906 (12)	S1—Nb^xiii	2.5238 (8)
Cs—P2	4.2206 (13)	S3—P2^xiv	2.0353 (10)
Nb—S1ⁱ	2.5016 (9)	S3—Cs^xv	3.5468 (9)
Nb—S6^vi	2.5221 (9)	S4—P2^xiv	2.0519 (11)
Nb—S1^vii	2.5238 (8)	S4—Cs^xiv	3.5646 (9)
Nb—S6^viii	2.5457 (9)	S5—P1^xvi	2.0413 (10)
Nb—S2	2.5457 (9)	S5—Nb^xvi	2.5971 (9)
Nb—S3	2.5730 (9)	S6—S6^xvii	2.0264 (17)
Nb—S5^ix	2.5971 (9)	S6—Nb^xviii	2.5221 (9)
Nb—S4	2.6266 (9)	S6—Nb^v	2.5457 (9)
Nb—Nb^x	3.1236 (5)

S2—Cs—S2ⁱ	57.52 (3)	S1ⁱ—Nb—S2	82.33 (3)
S2—Cs—S3ⁱⁱ	104.92 (2)	S6^vi—Nb—S2	154.30 (3)
S2ⁱ—Cs—S3ⁱⁱ	91.80 (2)	S1^vii—Nb—S2	81.46 (3)
S2—Cs—S3ⁱⁱⁱ	91.80 (2)	S6^viii—Nb—S2	157.94 (3)
S2ⁱ—Cs—S3ⁱⁱⁱ	104.92 (2)	S1ⁱ—Nb—S3	155.09 (3)
S3ⁱⁱ—Cs—S3ⁱⁱⁱ	161.04 (3)	S6^vi—Nb—S3	87.62 (3)
S2—Cs—S4^iv	151.14 (2)	S1^vii—Nb—S3	157.05 (3)
S2ⁱ—Cs—S4^iv	131.09 (2)	S6^viii—Nb—S3	87.58 (3)
S3ⁱⁱ—Cs—S4^iv	102.32 (2)	S2—Nb—S3	96.58 (3)
S3ⁱⁱⁱ—Cs—S4^iv	59.903 (19)	S1ⁱ—Nb—S5^ix	125.13 (3)
S2—Cs—S4^v	131.09 (2)	S6^vi—Nb—S5^ix	79.61 (3)
S2ⁱ—Cs—S4^v	151.14 (2)	S1^vii—Nb—S5^ix	79.19 (3)
S3ⁱⁱ—Cs—S4^v	59.903 (19)	S6^viii—Nb—S5^ix	125.49 (3)
S3ⁱⁱⁱ—Cs—S4^v	102.32 (2)	S2—Nb—S5^ix	76.51 (3)
S4^iv—Cs—S4^v	58.06 (3)	S3—Nb—S5^ix	78.13 (3)
S2—Cs—S6ⁱ	151.57 (2)	S1ⁱ—Nb—S4	81.33 (3)
S2ⁱ—Cs—S6ⁱ	95.896 (19)	S6^vi—Nb—S4	126.93 (3)
S3ⁱⁱ—Cs—S6ⁱ	62.58 (2)	S1^vii—Nb—S4	127.11 (3)
S3ⁱⁱⁱ—Cs—S6ⁱ	106.020 (19)	S6^viii—Nb—S4	82.02 (3)
S4^iv—Cs—S6ⁱ	53.620 (18)	S2—Nb—S4	78.35 (3)
S4^v—Cs—S6ⁱ	67.27 (2)	S3—Nb—S4	74.12 (3)
S2—Cs—S6	95.896 (19)	S5^ix—Nb—S4	139.76 (3)
S2ⁱ—Cs—S6	151.57 (2)	S1ⁱ—Nb—Nb^x	51.888 (19)
S3ⁱⁱ—Cs—S6	106.020 (19)	S6^vi—Nb—Nb^x	52.29 (2)
S3ⁱⁱⁱ—Cs—S6	62.58 (2)	S1^vii—Nb—Nb^x	51.25 (2)
S4^iv—Cs—S6	67.27 (2)	S6^viii—Nb—Nb^x	51.61 (2)
S4^v—Cs—S6	53.620 (18)	S2—Nb—Nb^x	128.30 (2)
S6ⁱ—Cs—S6	111.87 (3)	S3—Nb—Nb^x	135.12 (2)
S2—Cs—S5ⁱ	54.738 (19)	S5^ix—Nb—Nb^x	108.56 (2)
S2ⁱ—Cs—S5ⁱ	110.88 (2)	S4—Nb—Nb^x	111.67 (2)
S3ⁱⁱ—Cs—S5ⁱ	92.93 (2)	S2ⁱ—P1—S2	109.11 (7)
S3ⁱⁱⁱ—Cs—S5ⁱ	89.45 (2)	S2ⁱ—P1—S5^xi	102.92 (3)
S4^iv—Cs—S5ⁱ	114.78 (2)	S2—P1—S5^xi	113.21 (4)
S4^v—Cs—S5ⁱ	78.539 (18)	S2ⁱ—P1—S5^ix	113.21 (4)
S6ⁱ—Cs—S5ⁱ	144.617 (19)	S2—P1—S5^ix	102.92 (3)
S6—Cs—S5ⁱ	47.615 (17)	S5^xi—P1—S5^ix	115.63 (7)
S2—Cs—S5	110.88 (2)	S2ⁱ—P1—Cs	54.56 (4)
S2ⁱ—Cs—S5	54.738 (19)	S2—P1—Cs	54.56 (4)
S3ⁱⁱ—Cs—S5	89.45 (2)	S5^xi—P1—Cs	122.18 (4)
S3ⁱⁱⁱ—Cs—S5	92.93 (2)	S5^ix—P1—Cs	122.18 (4)
S4^iv—Cs—S5	78.539 (18)	S3^iv—P2—S3^v	111.30 (8)
S4^v—Cs—S5	114.78 (2)	S3^iv—P2—S4^v	115.55 (4)
S6ⁱ—Cs—S5	47.615 (17)	S3^v—P2—S4^v	100.12 (3)
S6—Cs—S5	144.616 (19)	S3^iv—P2—S4^iv	100.12 (3)
S5ⁱ—Cs—S5	165.52 (3)	S3^v—P2—S4^iv	115.55 (4)
S2—Cs—P1	28.759 (15)	S4^v—P2—S4^iv	114.91 (8)
S2ⁱ—Cs—P1	28.759 (15)	S3^iv—P2—Cs	124.35 (4)
S3ⁱⁱ—Cs—P1	99.482 (14)	S3^v—P2—Cs	124.35 (4)
S3ⁱⁱⁱ—Cs—P1	99.482 (14)	S4^v—P2—Cs	57.46 (4)
S4^iv—Cs—P1	150.970 (14)	S4^iv—P2—Cs	57.46 (4)
S4^v—Cs—P1	150.970 (14)	S1^xii—S1—Nbⁱ	66.74 (3)
S6ⁱ—Cs—P1	124.066 (13)	S1^xii—S1—Nb^xiii	65.60 (3)
S6—Cs—P1	124.066 (13)	Nbⁱ—S1—Nb^xiii	76.86 (3)
S5ⁱ—Cs—P1	82.760 (13)	P1—S2—Nb	91.14 (3)
S5—Cs—P1	82.760 (13)	P1—S2—Cs	96.69 (4)
S2—Cs—P2	151.241 (15)	Nb—S2—Cs	119.61 (3)
S2ⁱ—Cs—P2	151.241 (15)	P2^xiv—S3—Nb	93.32 (4)
S3ⁱⁱ—Cs—P2	80.518 (14)	P2^xiv—S3—Cs^xv	100.09 (3)
S3ⁱⁱⁱ—Cs—P2	80.518 (14)	Nb—S3—Cs^xv	157.95 (4)
S4^iv—Cs—P2	29.030 (14)	P2^xiv—S4—Nb	91.38 (3)
S4^v—Cs—P2	29.030 (14)	P2^xiv—S4—Cs^xiv	93.51 (4)
S6ⁱ—Cs—P2	55.934 (13)	Nb—S4—Cs^xiv	115.76 (3)
S6—Cs—P2	55.934 (13)	P1^xvi—S5—Nb^xvi	89.43 (3)
S5ⁱ—Cs—P2	97.240 (13)	P1^xvi—S5—Cs	147.09 (5)
S5—Cs—P2	97.240 (13)	Nb^xvi—S5—Cs	108.99 (3)
P1—Cs—P2	180	S6^xvii—S6—Nb^xviii	67.04 (3)
S1ⁱ—Nb—S6^vi	104.18 (3)	S6^xvii—S6—Nb^v	65.82 (3)
S1ⁱ—Nb—S1^vii	47.65 (4)	Nb^xviii—S6—Nb^v	76.10 (3)
S6^vi—Nb—S1^vii	84.90 (3)	S6^xvii—S6—Cs	170.46 (6)
S1ⁱ—Nb—S6^viii	84.86 (3)	Nb^xviii—S6—Cs	118.42 (3)
S6^vi—Nb—S6^viii	47.14 (4)	Nb^v—S6—Cs	106.98 (3)
S1^vii—Nb—S6^viii	102.86 (3)

Symmetry codes: (i) x, −y+1/2, −z+1/4; (ii) −x+1/2, −y+1/2, z−1/2; (iii) −x+1/2, y, −z+3/4; (iv) y+1/2, −x+1/2, −z+1/2; (v) y+1/2, x, z−1/4; (vi) −y, −x+1/2, z+1/4; (vii) −x, y−1/2, −z+1/4; (viii) y, x−1/2, z+1/4; (ix) y−1/2, −x+1/2, −z+1/2; (x) −x, −y, z; (xi) y−1/2, x, z−1/4; (xii) −x, −y+1, z; (xiii) −x, y+1/2, −z+1/4; (xiv) −y+1/2, x−1/2, −z+1/2; (xv) −x+1/2, −y+1/2, z+1/2; (xvi) −y+1/2, x+1/2, −z+1/2; (xvii) −x+1, −y, z; (xviii) −y+1/2, −x, z−1/4.

Experimental details

Crystal data
Chemical formula	Cs_0.49NbPS₆
M_r	380.95
Crystal system, space group	Tetragonal, I42d
Temperature (K)	290
a, c (Å)	15.9477 (3), 13.2461 (3)
V (Å³)	3368.88 (11)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	5.08
Crystal size (mm)	0.30 × 0.08 × 0.06

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.751, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16125, 1929, 1843
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.047, 1.06
No. of reflections	1929
No. of parameters	81
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.42
Absolute structure	Flack (1983), 851 Friedel pairs
Absolute structure parameter	0.452 (18)

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

Nb—S1ⁱ	2.5016 (9)	P1—S2	2.0300 (11)
Nb—S6ⁱⁱ	2.5221 (9)	P1—S5^vii	2.0413 (10)
Nb—S1ⁱⁱⁱ	2.5238 (8)	P1—S5^v	2.0413 (10)
Nb—S6^iv	2.5457 (9)	P2—S3^viii	2.0353 (10)
Nb—S2	2.5457 (9)	P2—S3^ix	2.0353 (10)
Nb—S3	2.5730 (9)	P2—S4^ix	2.0519 (11)
Nb—S5^v	2.5971 (9)	P2—S4^viii	2.0519 (11)
Nb—S4	2.6266 (9)	S1—S1^x	2.0302 (17)
Nb—Nb^vi	3.1236 (5)	S6—S6^xi	2.0264 (17)
P1—S2ⁱ	2.0300 (11)

S2ⁱ—P1—S2	109.11 (7)	S2ⁱ—P1—S5^v	113.21 (4)
S2ⁱ—P1—S5^vii	102.92 (3)	S2—P1—S5^v	102.92 (3)
S2—P1—S5^vii	113.21 (4)	S5^vii—P1—S5^v	115.63 (7)

Symmetry codes: (i) x, −y+1/2, −z+1/4; (ii) −y, −x+1/2, z+1/4; (iii) −x, y−1/2, −z+1/4; (iv) y, x−1/2, z+1/4; (v) y−1/2, −x+1/2, −z+1/2; (vi) −x, −y, z; (vii) y−1/2, x, z−1/4; (viii) y+1/2, −x+1/2, −z+1/2; (ix) y+1/2, x, z−1/4; (x) −x, −y+1, z; (xi) −x+1, −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-2010–0029617). Use was made of the X-ray facilities supported by the Ajou University.

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