K₉CeP₄S₁₆, a new thio­phosphate of cerium with discrete [Ce(PS₄)₄]^9- anions

The structure of nona­potassium cerium tetra­phos­phorus hexa­deca­sulfide, a zero-dimensional material isostructural with Rb₉CeP₄Se₁₆, is reported.

S1. Comment

In the quest for new Ce-containing materials with interesting chromatic properties, the K/Ce/P/S system has been explored. Hence, the title compound, K^I₉Ce^IIIP^V₄S^—II₁₆, (I), has been synthesized and structurally characterized. This yellow solid, isostructural with Rb₉CeP₄Se₁₆ (Chondroudis & Kanatzidis, 2000), contains discrete [Ce(PS₄)₄]^-9 anions built upon [CeS₈] triangular dodecahedral polyhedra sharing distinct edges with four [PS₄] tetrahedra. The resulting arrangement of this metal complex exhibits a D_{2 d} local symmetry. As cerium(III) and potassium(I) have similar ionic radii and since Ce and K5 sites are identical, a small substitution of Ce by K and, complementarily, of K by Ce is observed. All distances and angles are as expected, except for a small shrinking of the K5···S average distance due to the Ce partial substitution.

S2. Experimental

Ce₂S₃ (0.1795 g, 0.5 mmol), P (0.0591 g, 1.9 mmol), K₂S (0.0932 g, 2.4 mmol) and S (0.1682 g, 5.2 mmol) were thoroughly mixed and sealed under vacuum in a silica tube. The reaction mixture was heated to 1073 K at a rate of 4 K h^-1, maintained at this temperature for 7 d and then cooled to room temperature at a rate of 4 K h^-1. The obtained yellow plate-like crystals are air-sensitive and decompose in presence of water. A single-crystal was sealed in a quartz capillary in an argon dry box.

S3. Refinement

The structure is twinned by merohedry (twofold axis along c), twinning domain ratio refined to 0.5175 (6) and 0.4825.

Computing details

Data collection: IPDS Software (Stoe, 1996); cell refinement: IPDS Software; data reduction: JANA98 (Petricek & Dusek, 1998); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: JANA98; software used to prepare material for publication: JANA98.

Nonapotassium cerium tetraphosphorus hexadecasulfide

Crystal data

K9CeP4S16	F(000) = 2180
Mr = 1128.86	Dx = 2.389 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.242 (3) Å	Cell parameters from 2000 reflections
b = 9.788 (1) Å	θ = 2–24°
c = 17.524 (2) Å	µ = 3.91 mm^−1
β = 115.36 (1)°	T = 300 K
V = 3137.4 (8) Å^3	Block, yellow
Z = 4	0.20 × 0.18 × 0.07 mm

Data collection

IPDS Stoe diffractometer	4324 reflections with F2 > 2σ(F2)
ω scans	Rint = 0.036
Absorption correction: analytical (Becker & Coppens, 1974)	θmax = 27.9°, θmin = 2.2°
Tmin = 0.584, Tmax = 0.865	h = −26→26
22263 measured reflections	k = −12→12
5481 independent reflections	l = −22→22

Refinement

Refinement on F^2	139 parameters
R[F^2 > 2σ(F^2)] = 0.026	Weighting scheme based on measured s.u.'s w = 1/(σ^2I + 0.001024I^2)
wR(F^2) = 0.061	(Δ/σ)max = 0.005
S = 1.12	Δρmax = 1.15 e Å^−3
5481 reflections	Δρmin = −0.98 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ce	0	0.24615 (4)	0.25	0.0116 (1)	0.968 (1)
K_ce	0	0.24615	0.25	0.0116	0.032
P1	0.1293 (1)	0.00494 (6)	0.4180 (1)	0.0138 (4)
P2	0.1281 (1)	0.48587 (8)	0.2105 (1)	0.0137 (4)
S1	0.10673 (7)	0.01609 (9)	0.2920 (1)	0.0189 (4)
S2	0.10721 (6)	0.4750 (1)	0.31494 (9)	0.0187 (3)
S3	0.07693 (8)	0.1719 (1)	0.4360 (1)	0.0241 (4)
S4	0.07413 (7)	0.3214 (1)	0.13916 (9)	0.0239 (4)
S5	0.2377 (1)	0.01010 (9)	0.4924 (1)	0.0274 (5)
S6	0.2372 (1)	0.4792 (1)	0.2441 (1)	0.0256 (4)
S7	0.08625 (8)	−0.1628 (1)	0.4455 (1)	0.0282 (4)
S8	0.08588 (8)	0.6561 (1)	0.1413 (1)	0.0247 (4)
K1	0.0831 (1)	0.01408 (9)	0.6048 (1)	0.0314 (5)
K2	0.0829 (1)	0.51283 (8)	0.4782 (1)	0.0303 (5)
K3	0.24755 (4)	0.2389 (1)	0.3698 (1)	0.0321 (3)
K4	0.26455 (5)	0.2386 (1)	0.1307 (1)	0.0420 (4)
K5	0	0.7465 (1)	0.25	0.0227 (6)	0.968
Ce_k5	0	0.7465	0.25	0.0227	0.032

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ce	0.01437 (8)	0.01024 (9)	0.0116 (2)	0	0.0068 (3)	0
K_ce	0.01437	0.01024	0.0116	0	0.0068	0
P1	0.0167 (6)	0.0135 (4)	0.0109 (7)	0.0013 (2)	0.0057 (6)	0.0009 (2)
P2	0.0175 (6)	0.0117 (4)	0.0144 (7)	−0.0005 (3)	0.0093 (5)	0.0002 (3)
S1	0.0216 (6)	0.0234 (4)	0.0129 (5)	0.0042 (3)	0.0087 (4)	0.0015 (4)
S2	0.0193 (5)	0.0265 (3)	0.0126 (5)	−0.0059 (4)	0.0089 (4)	−0.0029 (5)
S3	0.0393 (6)	0.0176 (4)	0.0185 (5)	0.0096 (3)	0.0152 (4)	0.0026 (3)
S4	0.0390 (6)	0.0185 (4)	0.0202 (5)	−0.0097 (4)	0.0183 (5)	−0.0066 (4)
S5	0.0193 (6)	0.0329 (6)	0.0232 (7)	0.0001 (3)	0.0026 (5)	0.0050 (4)
S6	0.0194 (5)	0.0288 (4)	0.0343 (7)	0.0029 (4)	0.0169 (5)	0.0054 (4)
S7	0.0424 (6)	0.0163 (4)	0.0289 (6)	−0.0072 (4)	0.0182 (5)	0.0003 (4)
S8	0.0345 (5)	0.0164 (4)	0.0266 (5)	0.0054 (3)	0.0163 (5)	0.0085 (4)
K1	0.0435 (8)	0.0329 (4)	0.0206 (7)	−0.0045 (4)	0.0165 (6)	0.0005 (4)
K2	0.0414 (8)	0.0291 (4)	0.0257 (7)	−0.0005 (4)	0.0193 (6)	−0.0009 (3)
K3	0.0407 (3)	0.0230 (3)	0.0396 (5)	−0.0001 (3)	0.0238 (4)	0.0048 (4)
K4	0.0606 (4)	0.0264 (4)	0.0395 (5)	0.0025 (4)	0.0218 (6)	0.0052 (4)
K5	0.0267 (4)	0.0199 (4)	0.024 (1)	0	0.013 (1)	0
Ce_k5	0.0267	0.0199	0.024	0	0.013	0

Geometric parameters (Å, º)

Ce—S1	2.986 (1)	K2—S4^v	3.323 (3)
Ce—S1^i	2.986 (1)	K2—S5^iv	3.449 (3)
Ce—S2	2.984 (1)	K2—S7^vi	3.233 (1)
Ce—S2^i	2.984 (1)	K2—S8^i	3.449 (2)
Ce—S3	3.038 (2)	K2—S8^v	3.280 (3)
Ce—S3^i	3.038 (2)	K3—S1	3.378 (1)
Ce—S4	3.011 (2)	K3—S2	3.464 (1)
Ce—S4^i	3.011 (2)	K3—S5	3.168 (3)
P1—S1	2.057 (3)	K3—S5^iv	3.368 (3)
P1—S3	2.044 (2)	K3—S6	3.168 (2)
P1—S5	2.017 (3)	K3—S6^vii	3.326 (2)
P1—S7	2.011 (2)	K3—S8^vii	3.553 (2)
P2—S2	2.050 (3)	K4—S1^viii	3.602 (1)
P2—S4	2.044 (2)	K4—S2^vii	3.491 (2)
P2—S6	2.028 (3)	K4—S5^viii	3.410 (3)
P2—S8	2.022 (2)	K4—S5^ix	3.312 (3)
K1—S1^ii	3.121 (3)	K4—S6	3.278 (3)
K1—S3	3.292 (3)	K4—S6^vii	3.366 (3)
K1—S3^iii	3.512 (3)	K5—S1^vi	3.288 (2)
K1—S4^ii	3.358 (2)	K5—S1^x	3.288 (2)
K1—S6^iv	3.464 (2)	K5—S2	3.309 (2)
K1—S7	3.308 (3)	K5—S2^i	3.309 (2)
K1—S7^iii	3.472 (3)	K5—S7^vi	3.233 (2)
K1—S8^v	3.287 (1)	K5—S7^x	3.233 (2)
K2—S2	3.127 (3)	K5—S8	3.204 (2)
K2—S3	3.409 (1)	K5—S8^i	3.204 (2)
K2—S4^i	3.499 (2)
S1—Ce—S1^i	82.11 (3)	S2^i—Ce—S4	93.00 (4)
S1—Ce—S2	98.10 (3)	S2^i—Ce—S4^i	65.19 (4)
S1—Ce—S2^i	172.36 (5)	S3—Ce—S3^i	152.32 (3)
S1—Ce—S3	64.59 (5)	S3—Ce—S4	125.64 (4)
S1—Ce—S3^i	93.92 (4)	S3—Ce—S4^i	62.25 (4)
S1—Ce—S4	80.54 (4)	S3^i—Ce—S3	152.32 (3)
S1—Ce—S4^i	122.23 (4)	S3^i—Ce—S4	62.25 (4)
S1^i—Ce—S1	82.11 (3)	S3^i—Ce—S4^i	125.64 (4)
S1^i—Ce—S2	172.36 (5)	S4—Ce—S4^i	151.68 (3)
S1^i—Ce—S2^i	98.10 (3)	S4^i—Ce—S4	151.68 (3)
S1^i—Ce—S3	93.92 (4)	S1—P1—S3	103.39 (8)
S1^i—Ce—S3^i	64.59 (5)	S1—P1—S5	111.8 (1)
S1^i—Ce—S4	122.23 (4)	S1—P1—S7	112.38 (8)
S1^i—Ce—S4^i	80.54 (4)	S3—P1—S5	111.90 (8)
S2—Ce—S2^i	82.72 (3)	S3—P1—S7	108.0 (1)
S2—Ce—S3	79.37 (4)	S5—P1—S7	109.19 (8)
S2—Ce—S3^i	122.92 (4)	S2—P2—S4	104.1 (1)
S2—Ce—S4	65.19 (4)	S2—P2—S6	110.8 (1)
S2—Ce—S4^i	93.00 (4)	S2—P2—S8	112.5 (1)
S2^i—Ce—S2	82.72 (3)	S4—P2—S6	112.5 (1)
S2^i—Ce—S3	122.92 (4)	S4—P2—S8	107.71 (9)
S2^i—Ce—S3^i	79.37 (4)	S6—P2—S8	109.2 (1)

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