Tetra­yttrium(III) tris­ulfide disilicate

Koscielski, L.A.; Ibers, J.A.

doi:10.1107/S1600536810054607

inorganic compounds

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Volume 67| Part 2| February 2011| Page i16

doi:10.1107/S1600536810054607

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Tetrayttrium(III) trisulfide disilicate

Lukasz A. Koscielski ^a and James A. Ibers ^a ^*

^aDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA
^*Correspondence e-mail: ibers@chem.northwestern.edu

(Received 14 December 2010; accepted 28 December 2010; online 15 January 2011)

Tetrayttrium(III) trisulfide disilicate, Y₄S₃(Si₂O₇), crystallizes in the Sm₄S₃(Si₂O₇) structure type. The structure consists of isolated (Si₂O₇)⁶⁻ units (2mm. symmetry) and two crystallographically independent Y³⁺ cations bridged by one S and one O atom. The first Y atom (site symmetry .m.) is coordinated by three O atoms and three S atoms in a trigonal–prismatic arrangement whereas the second Y atom (site symmetry ..2) is coordinated by six O atoms and three S atoms in a tricapped trigonal–prismatic arrangement.

Related literature

For lanthanide sulfide disilicates of formula Ln₄S₃(Si₂O₇), see: Zeng et al. (1999 ) for Ln = La; Hartenbach & Schleid (2002 ) for Ln = Ce; Sieke & Schleid (2000 ) for Ln = Pr; Grupe et al. (1992 ) for Ln = Nd, Er; Sieke & Schleid (1999 ) for Ln = Sm; Sieke et al. (2002 ) for Ln = Gd, Tb, Dy, Ho, Er, Tm; Range et al. (1996 ) for Ln = Yb. For lanthanide selenide disilicates of formula Ln₄Se₃(Si₂O₇), see: Deudon et al. (1993 ) for Ln = La; Grupe & Urland (1989 ) for Ln = Ce, Nd; Grupe et al. (1992) for Ln = Pr, Sm, Gd. Ionic radii were taken from Shannon (1976 ). For computational details, see: Gelato & Parthé (1987 ). For additional synthetic details, see: Larroque & Beauvy (1986 ).

Experimental

Crystal data

Y₄S₃(Si₂O₇)
M_r = 620.00
Tetragonal, I 4₁ /a m d
a = 11.6706 (16) Å
c = 13.5873 (19) Å
V = 1850.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 25.78 mm⁻¹
T = 100 K
0.10 × 0.08 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: numerical [face-indexed using SADABS (Sheldrick, 2008a )] T_min = 0.191, T_max = 0.238
10831 measured reflections
668 independent reflections
587 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.045
S = 1.25
668 reflections
47 parameters
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.77 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Y1—O2	2.279 (3)
Y1—O1ⁱ	2.428 (2)
Y1—S1ⁱⁱ	2.7714 (8)
Y1—S2	2.7874 (6)
Y2—O1ⁱⁱⁱ	2.355 (2)
Y2—O2^iv	2.3884 (15)
Y2—O1^iv	2.530 (2)
Y2—S1^iv	2.8419 (9)
Y2—S3^v	2.8652 (6)
Si1—O3	1.621 (2)
Si1—O1	1.623 (2)
Si1—O2	1.641 (3)

Y1^vi—S1—Y2^vii	90.389 (13)
Y1^viii—O1—Y2^ix	106.88 (8)
Si1^x—O3—Si1	128.1 (3)
Symmetry codes: (i) $[y-{\script{1\over 4}}, x-{\script{1\over 4}}, z+{\script{1\over 4}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iii) $[-y+{\script{1\over 4}}, x+{\script{1\over 4}}, -z+{\script{3\over 4}}]$ ; (iv) $[x, y+{\script{1\over 2}}, -z+1]$ ; (v) -x, -y+1, -z+1; (vi) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ ; (vii) $[y-{\script{1\over 4}}, -x+{\script{1\over 4}}, -z+{\script{3\over 4}}]$ ; (viii) $[y+{\script{1\over 4}}, -x+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (ix) $[x, y-{\script{1\over 2}}, -z+1]$ ; (x) $[-x, -y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: CrystalMaker (Palmer, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810054607/wm2440sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054607/wm2440Isup2.hkl

checkCIF report

Comment top

Tetrayttrium(III) trisulfide disilicate, Y₄S₃(Si₂O₇), crystallizes in the Sm₄S₃(Si₂O₇) structure type (Grupe et al., 1992). A view of the coordination environment of the atoms in Y₄S₃(Si₂O₇) is shown in Fig. 1. There are two crystallographically independent yttrium atoms. Atoms Y1 and Y2 are at sites of symmetry .m. and ..2, respectively. Atom Y1 is coordinated by three O atoms and three S atoms in a distorted trigonal-prismatic arrangement whereas atom Y2 is coordinated by six O atoms and three S atoms in the form of a distorted tri-capped trigonal prism. There are three crystallographically independent S atoms. Atoms S1, S2, and S3 are at sites of symmetry .2., 4m2, and 4m2, respectively. Atoms S1 and S2 are coordinated by four Y atoms in disphenoidal arrangements and atom S3 is coordinated by four Y atoms in a square-planar arrangement. There is one crystallographically independent Si atom at a site of symmetry .m. and three crystallographically independent O atoms at sites of symmetry 1, .m., and 2mm. . The disilicate (Si₂O₇)^6- units (symmetry 2mm.) are made up of two corner-sharing silicate tetrahedra in the form of a bow-tie. These units stack in a staggered fashion along the c-axis as seen in Fig. 2.

There exist eleven Ln₄Q₃(Si₂O₇) analogues where Ln is a lanthanide and Q is S, specifically when Ln = La–Nd, Sm, Gd–Tm (Zeng et al., 1999; Hartenbach & Schleid, 2002; Sieke & Schleid, 1999; Grupe et al., 1992; Sieke & Schleid, 1998; Sieke et al., 2002; Range et al., 1996). There exist six Ln₄Q₃(Si₂O₇) analogues of the title compound where Q = Se, specifically when Ln = La—Nd, Sm, Gd (Deudon et al., 1993; Grupe & Urland, 1989; Grupe et al., 1992). No analogues where Q = Te were found in the literature.

The title compound crystallizes with eight formula units in space group I4₁/amd. The unit-cell dimensions are a = 11.6706 (16) Å and c = 13.5873 (19) Å. For the Ln₄S₃(Si₂O₇) analogues, the unit cell varies between a = 12.098 (3) Å and c = 14.379 (5) Å for Ln = La (Zeng et al., 1999) and a = 11.543 (1) Å and c = 13.322 (1) Å for Ln = Yb (Range et al., 1996). A plot of axis length versus lanthanide crystal radius (Shannon, 1976) leads to nearly linear curves (Sieke et al., 2002) and adding Ln = Y to the plot not surprisingly keeps the near linearity. The plot is shown in Fig. 3. The unit-cell dimensions of Y₄S₃(Si₂O₇) are closest to that of Ho₄S₃(Si₂O₇), where a = 11.6595 (10) Å and c = 13.5577 (12) Å (Sieke et al., 2002). In fact, of all the lanthanide radii, the crystal radius of Ho (1.212 Å) is closest to that of Y (1.215 Å) (Shannon, 1976).

Related literature top

For lanthanide sulfide disilicates of formula Ln₄S₃(Si₂O₇), see: Zeng et al. (1999) for Ln = La; Hartenbach & Schleid (2002) for Ln = Ce; Sieke & Schleid (2000) for Ln = Pr; Grupe et al. (1992) for Ln = Nd, Er; Sieke & Schleid (1999) for Ln = Sm; Sieke et al. (2002) for Ln = Gd, Tb, Dy, Ho, Er, Tm; Range et al. (1996) for Ln = Yb. For lanthanide selenide disilicates of formula Ln₄Se₃(Si₂O₇), see: Deudon et al. (1993) for Ln = La; Grupe & Urland (1989) for Ln = Ce, Nd; Grupe et al. (1992) for Ln = Pr, Sm, Gd. Ionic radii were taken from Shannon (1976). For computational details, see: Gelato & Parthé (1987). For additional synthetic details, see: Larroque & Beauvy (1986).

Experimental top

The compound was synthesized accidentally. ThO₂ (Alfa-Aesar), Y₂S₃ (Strem, 99.9%) S (Alfa-Aesar, 99.99%), and Sb (Aldrich, 99.5%), were used as received. Sb₂S₃ was prepared from the direct reaction of the elements in a sealed fused-silica tube at 1123 K. ThOS was prepared from ThO₂ and S following a modified procedure by Larroque et al. (1986). A fused-silica tube was loaded with ThOS (35 mg, 0.125 mmol) and Y₂S₃ (35.6 mg, 0.130 mmol), evacuated to near 10 ^-4 Torr, flame sealed, and placed in a computer-controlled furnace. It was heated to 1273 K in 24 h, kept at 1273 K for 168 h, cooled to 873 K in 198 h, and then rapidly cooled to 298 K in 5 h. The resulting tan powder (50 mg) was loaded with Sb₂S₃ (20 mg, 0.6 mmol) in a fused-silica tube and heated as before. The resulting tube was etched and contained clear crystals of composition Y/S/Si/O as determined by EDX analysis. The silicon and oxygen were abstracted from the silica tube and introduced into the reaction in the second step.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: CrystalMaker (Palmer, 2009); software used to prepare material for publication: SHELXL97(Sheldrick, 2008b).

Figures top

	Fig. 1. View showing the local coordination environment of atoms Y1 and Y2 as well as the disilicate unit. The 95% probability displacement ellipsoids are depicted.
	Fig. 2. View down the b-axis (left) and down the c-axis (right). The disilicate units are staggered when viewed down the c-axis. Colour key: yttrium – blue, sulfur – brown, silicate tetrahedra – green. Unit cell is outlined.
	Fig. 3. Plot of axial length versus lanthanide crystal radius for a 9-coordinate lanthanide in the Ln₄S₃(Si₂O₇) structure family (Ln = lanthanide element). Axial length decreases as the atomic mass of the lanthanide increases owing to the lanthanide contraction. Yttrium fits on the plot closest to holmium.

Tetrayttrium(III) trisulfide disilicate top

Crystal data top

Y₄S₃(Si₂O₇)	D_x = 4.451 Mg m⁻³
M_r = 620.00	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4₁/amd	Cell parameters from 2730 reflections
Hall symbol: -I 4bd 2	θ = 2.3–27.6°
a = 11.6706 (16) Å	µ = 25.78 mm⁻¹
c = 13.5873 (19) Å	T = 100 K
V = 1850.6 (4) Å³	Polyhedron, colorless
Z = 8	0.10 × 0.08 × 0.08 mm
F(000) = 2304

Data collection top

Bruker APEXII CCD diffractometer	668 independent reflections
Radiation source: fine-focus sealed tube	587 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scans	θ_max = 29.2°, θ_min = 2.3°
Absorption correction: numerical [face-indexed using SADABS (Sheldrick, 2008a)]	h = −15→15
T_min = 0.191, T_max = 0.238	k = −15→15
10831 measured reflections	l = −18→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	w = [1/[σ²(F_o²) + (0.0199*F_o²)²]
wR(F²) = 0.045	(Δ/σ)_max = 0.001
S = 1.25	Δρ_max = 0.61 e Å⁻³
668 reflections	Δρ_min = −0.77 e Å⁻³
47 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00065 (7)

Crystal data top

Y₄S₃(Si₂O₇)	Z = 8
M_r = 620.00	Mo Kα radiation
Tetragonal, I4₁/amd	µ = 25.78 mm⁻¹
a = 11.6706 (16) Å	T = 100 K
c = 13.5873 (19) Å	0.10 × 0.08 × 0.08 mm
V = 1850.6 (4) Å³

Data collection top

Bruker APEXII CCD diffractometer	668 independent reflections
Absorption correction: numerical [face-indexed using SADABS (Sheldrick, 2008a)]	587 reflections with I > 2σ(I)
T_min = 0.191, T_max = 0.238	R_int = 0.066
10831 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	47 parameters
wR(F²) = 0.045	0 restraints
S = 1.25	Δρ_max = 0.61 e Å⁻³
668 reflections	Δρ_min = −0.77 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Y1	0.0000	0.01464 (4)	0.34012 (3)	0.00768 (13)
Y2	0.17360 (2)	0.42360 (2)	0.8750	0.00517 (13)
S1	0.35327 (9)	0.0000	0.0000	0.0096 (2)
S2	0.0000	0.2500	0.3750	0.0089 (4)
S3	0.0000	0.7500	0.1250	0.0052 (4)
Si1	0.0000	0.12512 (10)	0.09531 (9)	0.0049 (2)
O1	0.12244 (17)	0.10968 (19)	0.04018 (15)	0.0082 (5)
O2	0.0000	0.0169 (2)	0.1724 (2)	0.0062 (6)
O3	0.0000	0.2500	0.1475 (3)	0.0110 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Y1	0.0078 (2)	0.0087 (2)	0.0065 (2)	0.000	0.000	−0.00089 (16)
Y2	0.00547 (15)	0.00547 (15)	0.0046 (2)	0.00152 (15)	0.00013 (11)	−0.00013 (11)
S1	0.0059 (5)	0.0152 (6)	0.0077 (6)	0.000	0.000	0.0041 (4)
S2	0.0098 (7)	0.0098 (7)	0.0072 (11)	0.000	0.000	0.000
S3	0.0048 (6)	0.0048 (6)	0.0062 (10)	0.000	0.000	0.000
Si1	0.0055 (6)	0.0041 (5)	0.0050 (6)	0.000	0.000	0.0006 (4)
O1	0.0044 (10)	0.0116 (11)	0.0085 (12)	−0.0005 (9)	0.0019 (8)	0.0017 (9)
O2	0.0036 (14)	0.0048 (14)	0.0103 (18)	0.000	0.000	−0.0008 (12)
O3	0.020 (2)	0.007 (2)	0.006 (2)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Y1—O2	2.279 (3)	S1—Y1^xvii	2.7714 (8)
Y1—O1ⁱ	2.428 (2)	S1—Y2^xviii	2.8420 (9)
Y1—O1ⁱⁱ	2.428 (2)	S1—Y2^vii	2.8420 (9)
Y1—S1ⁱⁱⁱ	2.7714 (8)	S2—Y1^x	2.7874 (6)
Y1—S1^iv	2.7714 (8)	S2—Y1^xviii	2.7874 (6)
Y1—S2	2.7874 (6)	S2—Y1^xix	2.7874 (6)
Y1—Si1^v	3.4158 (8)	S3—Y2^xii	2.8652 (5)
Y1—Si1ⁱⁱ	3.4158 (8)	S3—Y2^xv	2.8652 (6)
Y1—Y2^vi	3.7117 (5)	S3—Y2^xx	2.8652 (6)
Y1—Y2^vii	3.7117 (5)	S3—Y2^xxi	2.8652 (5)
Y1—Y2^viii	3.9830 (6)	Si1—O3	1.621 (2)
Y1—Y2^ix	3.9830 (6)	Si1—O1	1.623 (2)
Y2—O1^x	2.355 (2)	Si1—O1^xxii	1.623 (2)
Y2—O1^xi	2.355 (2)	Si1—O2	1.641 (3)
Y2—O2^xii	2.3884 (15)	Si1—Y2^vi	3.1303 (10)
Y2—O2^xiii	2.3884 (15)	Si1—Y2^vii	3.1303 (10)
Y2—O1^xii	2.530 (2)	Si1—Y1^xxiii	3.4158 (8)
Y2—O1^xiv	2.530 (2)	Si1—Y1^xxiv	3.4158 (8)
Y2—S1^xii	2.8419 (9)	O1—Y2^xviii	2.355 (2)
Y2—S1^x	2.8419 (9)	O1—Y1^xxiii	2.428 (2)
Y2—S3^xv	2.8652 (6)	O1—Y2^vii	2.530 (2)
Y2—Si1^xiii	3.1303 (10)	O2—Y2^vi	2.3884 (15)
Y2—Si1^xii	3.1303 (10)	O2—Y2^vii	2.3884 (15)
Y2—Y1^xii	3.7117 (5)	O3—Si1^xix	1.621 (2)
S1—Y1^xvi	2.7714 (8)

O2—Y1—O1ⁱ	74.24 (7)	O1^xi—Y2—S3^xv	72.79 (6)
O2—Y1—O1ⁱⁱ	74.24 (7)	O2^xii—Y2—S3^xv	73.89 (6)
O1ⁱ—Y1—O1ⁱⁱ	84.81 (11)	O2^xiii—Y2—S3^xv	73.89 (6)
O2—Y1—S1ⁱⁱⁱ	141.68 (2)	O1^xii—Y2—S3^xv	116.11 (5)
O1ⁱ—Y1—S1ⁱⁱⁱ	126.41 (5)	O1^xiv—Y2—S3^xv	116.11 (5)
O1ⁱⁱ—Y1—S1ⁱⁱⁱ	76.13 (5)	S1^xii—Y2—S3^xv	138.038 (9)
O2—Y1—S1^iv	141.68 (2)	S1^x—Y2—S3^xv	138.038 (9)
O1ⁱ—Y1—S1^iv	76.13 (5)	Y1^xvi—S1—Y1^xvii	103.68 (4)
O1ⁱⁱ—Y1—S1^iv	126.41 (5)	Y1^xvi—S1—Y2^xviii	154.823 (15)
S1ⁱⁱⁱ—Y1—S1^iv	76.32 (4)	Y1^xvii—S1—Y2^xviii	90.389 (13)
O2—Y1—S2	99.13 (7)	Y1^xvi—S1—Y2^vii	90.389 (13)
O1ⁱ—Y1—S2	136.14 (5)	Y1^xvii—S1—Y2^vii	154.823 (15)
O1ⁱⁱ—Y1—S2	136.14 (5)	Y2^xviii—S1—Y2^vii	84.90 (3)
S1ⁱⁱⁱ—Y1—S2	85.841 (11)	Y1^x—S2—Y1^xviii	160.421 (18)
S1^iv—Y1—S2	85.841 (11)	Y1^x—S2—Y1^xix	91.657 (3)
O1^x—Y2—O1^xi	145.57 (11)	Y1^xviii—S2—Y1^xix	91.657 (3)
O1^x—Y2—O2^xii	73.66 (8)	Y1^x—S2—Y1	91.657 (3)
O1^xi—Y2—O2^xii	96.72 (8)	Y1^xviii—S2—Y1	91.657 (3)
O1^x—Y2—O2^xiii	96.72 (8)	Y1^xix—S2—Y1	160.420 (18)
O1^xi—Y2—O2^xiii	73.66 (8)	Y2^xii—S3—Y2^xv	180.0
O2^xii—Y2—O2^xiii	147.78 (12)	Y2^xii—S3—Y2^xx	90.0
O1^x—Y2—O1^xii	127.80 (7)	Y2^xv—S3—Y2^xx	90.0
O1^xi—Y2—O1^xii	69.36 (8)	Y2^xii—S3—Y2^xxi	90.0
O2^xii—Y2—O1^xii	62.05 (8)	Y2^xv—S3—Y2^xxi	90.0
O2^xiii—Y2—O1^xii	135.47 (8)	Y2^xx—S3—Y2^xxi	180.0
O1^x—Y2—O1^xiv	69.36 (8)	O3—Si1—O1	107.56 (10)
O1^xi—Y2—O1^xiv	127.80 (7)	O3—Si1—O1^xxii	107.56 (10)
O2^xii—Y2—O1^xiv	135.47 (8)	O1—Si1—O1^xxii	123.34 (16)
O2^xiii—Y2—O1^xiv	62.05 (8)	O3—Si1—O2	114.39 (18)
O1^xii—Y2—O1^xiv	127.78 (9)	O1—Si1—O2	102.07 (10)
O1^x—Y2—S1^xii	140.43 (6)	O1^xxii—Si1—O2	102.07 (10)
O1^xi—Y2—S1^xii	70.68 (5)	Si1—O1—Y2^xviii	132.95 (12)
O2^xii—Y2—S1^xii	130.09 (7)	Si1—O1—Y1^xxiii	113.44 (11)
O2^xiii—Y2—S1^xii	76.63 (6)	Y2^xviii—O1—Y1^xxiii	101.79 (7)
O1^xii—Y2—S1^xii	68.44 (5)	Si1—O1—Y2^vii	95.33 (10)
O1^xiv—Y2—S1^xii	73.32 (5)	Y2^xviii—O1—Y2^vii	103.46 (8)
O1^x—Y2—S1^x	70.68 (5)	Y1^xxiii—O1—Y2^vii	106.88 (8)
O1^xi—Y2—S1^x	140.43 (6)	Si1—O2—Y1	130.32 (16)
O2^xii—Y2—S1^x	76.63 (6)	Si1—O2—Y2^vi	100.30 (9)
O2^xiii—Y2—S1^x	130.09 (7)	Y1—O2—Y2^vi	105.32 (8)
O1^xii—Y2—S1^x	73.32 (5)	Si1—O2—Y2^vii	100.30 (9)
O1^xiv—Y2—S1^x	68.44 (5)	Y1—O2—Y2^vii	105.32 (8)
S1^xii—Y2—S1^x	83.925 (17)	Y2^vi—O2—Y2^vii	116.05 (12)
O1^x—Y2—S3^xv	72.79 (6)	Si1^xix—O3—Si1	128.1 (3)

Symmetry codes: (i) y−1/4, x−1/4, z+1/4; (ii) −y+1/4, x−1/4, z+1/4; (iii) −x+1/2, −y, z+1/2; (iv) x−1/2, y, −z+1/2; (v) y−1/4, −x−1/4, z+1/4; (vi) −y+1/4, x−1/4, z−3/4; (vii) x, y−1/2, −z+1; (viii) x−1/2, y−1/2, z−1/2; (ix) −y+3/4, x−1/4, −z+5/4; (x) −y+1/4, x+1/4, −z+3/4; (xi) x, −y+1/2, z+1; (xii) x, y+1/2, −z+1; (xiii) y+1/4, −x+1/4, z+3/4; (xiv) y+1/4, x+1/4, z+3/4; (xv) −x, −y+1, −z+1; (xvi) x+1/2, y, −z+1/2; (xvii) −x+1/2, −y, z−1/2; (xviii) y−1/4, −x+1/4, −z+3/4; (xix) −x, −y+1/2, z; (xx) y−1/4, −x+3/4, z−3/4; (xxi) −y+1/4, x+3/4, z−3/4; (xxii) −x, y, z; (xxiii) y+1/4, −x+1/4, z−1/4; (xxiv) −y−1/4, x+1/4, z−1/4.

Experimental details

Crystal data
Chemical formula	Y₄S₃(Si₂O₇)
M_r	620.00
Crystal system, space group	Tetragonal, I4₁/amd
Temperature (K)	100
a, c (Å)	11.6706 (16), 13.5873 (19)
V (Å³)	1850.6 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	25.78
Crystal size (mm)	0.10 × 0.08 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Numerical [face-indexed using SADABS (Sheldrick, 2008a)]
T_min, T_max	0.191, 0.238
No. of measured, independent and observed [I > 2σ(I)] reflections	10831, 668, 587
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.045, 1.25
No. of reflections	668
No. of parameters	47
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.77

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), CrystalMaker (Palmer, 2009), SHELXL97(Sheldrick, 2008b).

Selected geometric parameters (Å, º) top

Y1—O2	2.279 (3)	Y2—O1^iv	2.530 (2)
Y1—O1ⁱ	2.428 (2)	Y2—S1^iv	2.8419 (9)
Y1—S1ⁱⁱ	2.7714 (8)	Y2—S3^v	2.8652 (6)
Y1—S2	2.7874 (6)	Si1—O3	1.621 (2)
Y2—O1ⁱⁱⁱ	2.355 (2)	Si1—O1	1.623 (2)
Y2—O2^iv	2.3884 (15)	Si1—O2	1.641 (3)

Y1^vi—S1—Y2^vii	90.389 (13)	Si1^x—O3—Si1	128.1 (3)
Y1^viii—O1—Y2^ix	106.88 (8)

Symmetry codes: (i) y−1/4, x−1/4, z+1/4; (ii) −x+1/2, −y, z+1/2; (iii) −y+1/4, x+1/4, −z+3/4; (iv) x, y+1/2, −z+1; (v) −x, −y+1, −z+1; (vi) −x+1/2, −y, z−1/2; (vii) y−1/4, −x+1/4, −z+3/4; (viii) y+1/4, −x+1/4, z−1/4; (ix) x, y−1/2, −z+1; (x) −x, −y+1/2, z.

Acknowledgements

This research was supported by the US Department of Energy, Basic Energy Sciences, Chemical Sciences, Biosciences, and Geosciences Division and Division of Materials Sciences and Engineering Grant ER-15522.

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