Tetra­yttrium(III) tris­ulfide disilicate

Abstract

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 Ln ₄S₃(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 Ln ₄Se₃(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,

• a = 11.6706 (16) Å

• c = 13.5873 (19) Å

• V = 1850.6 (4) ų

• 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[F ² > 2σ(F ²)] = 0.020

• wR(F ²) = 0.045

• S = 1.25

• 668 reflections

• 47 parameters

• Δρ_max = 0.61 e Å⁻³

• Δρ_min = −0.77 e Å⁻³

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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—O2iv	2.3884 (15)
Y2—O1iv	2.530 (2)
Y2—S1iv	2.8419 (9)
Y2—S3v	2.8652 (6)
Si1—O3	1.621 (2)
Si1—O1	1.623 (2)
Si1—O2	1.641 (3)

Y1vi—S1—Y2vii	90.389 (13)
Y1viii—O1—Y2ix	106.88 (8)
Si1x—O3—Si1	128.1 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Origin choice 2 of space group I4₁/amd was used. The structure was standardized by means of the program STRUCTURE TIDY (Gelato & Parthé, 1987). The highest peak (0.61 (16) e Å^-3) is 0.48 Å from atom O3 and the deepest hole (-0.77 (16) e Å^-3) is 0.45 Å from atom Y1.

Figures

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.

Crystal data

Y4S3(Si2O7)	Dx = 4.451 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0199*Fo2)2]
wR(F2) = 0.045	(Δ/σ)max = 0.001
S = 1.25	Δρmax = 0.61 e Å−3
668 reflections	Δρmin = −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)

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

Y1—O2	2.279 (3)	S1—Y1xvii	2.7714 (8)
Y1—O1i	2.428 (2)	S1—Y2xviii	2.8420 (9)
Y1—O1ii	2.428 (2)	S1—Y2vii	2.8420 (9)
Y1—S1iii	2.7714 (8)	S2—Y1x	2.7874 (6)
Y1—S1iv	2.7714 (8)	S2—Y1xviii	2.7874 (6)
Y1—S2	2.7874 (6)	S2—Y1xix	2.7874 (6)
Y1—Si1v	3.4158 (8)	S3—Y2xii	2.8652 (5)
Y1—Si1ii	3.4158 (8)	S3—Y2xv	2.8652 (6)
Y1—Y2vi	3.7117 (5)	S3—Y2xx	2.8652 (6)
Y1—Y2vii	3.7117 (5)	S3—Y2xxi	2.8652 (5)
Y1—Y2viii	3.9830 (6)	Si1—O3	1.621 (2)
Y1—Y2ix	3.9830 (6)	Si1—O1	1.623 (2)
Y2—O1x	2.355 (2)	Si1—O1xxii	1.623 (2)
Y2—O1xi	2.355 (2)	Si1—O2	1.641 (3)
Y2—O2xii	2.3884 (15)	Si1—Y2vi	3.1303 (10)
Y2—O2xiii	2.3884 (15)	Si1—Y2vii	3.1303 (10)
Y2—O1xii	2.530 (2)	Si1—Y1xxiii	3.4158 (8)
Y2—O1xiv	2.530 (2)	Si1—Y1xxiv	3.4158 (8)
Y2—S1xii	2.8419 (9)	O1—Y2xviii	2.355 (2)
Y2—S1x	2.8419 (9)	O1—Y1xxiii	2.428 (2)
Y2—S3xv	2.8652 (6)	O1—Y2vii	2.530 (2)
Y2—Si1xiii	3.1303 (10)	O2—Y2vi	2.3884 (15)
Y2—Si1xii	3.1303 (10)	O2—Y2vii	2.3884 (15)
Y2—Y1xii	3.7117 (5)	O3—Si1xix	1.621 (2)
S1—Y1xvi	2.7714 (8)
O2—Y1—O1i	74.24 (7)	O1xi—Y2—S3xv	72.79 (6)
O2—Y1—O1ii	74.24 (7)	O2xii—Y2—S3xv	73.89 (6)
O1i—Y1—O1ii	84.81 (11)	O2xiii—Y2—S3xv	73.89 (6)
O2—Y1—S1iii	141.68 (2)	O1xii—Y2—S3xv	116.11 (5)
O1i—Y1—S1iii	126.41 (5)	O1xiv—Y2—S3xv	116.11 (5)
O1ii—Y1—S1iii	76.13 (5)	S1xii—Y2—S3xv	138.038 (9)
O2—Y1—S1iv	141.68 (2)	S1x—Y2—S3xv	138.038 (9)
O1i—Y1—S1iv	76.13 (5)	Y1xvi—S1—Y1xvii	103.68 (4)
O1ii—Y1—S1iv	126.41 (5)	Y1xvi—S1—Y2xviii	154.823 (15)
S1iii—Y1—S1iv	76.32 (4)	Y1xvii—S1—Y2xviii	90.389 (13)
O2—Y1—S2	99.13 (7)	Y1xvi—S1—Y2vii	90.389 (13)
O1i—Y1—S2	136.14 (5)	Y1xvii—S1—Y2vii	154.823 (15)
O1ii—Y1—S2	136.14 (5)	Y2xviii—S1—Y2vii	84.90 (3)
S1iii—Y1—S2	85.841 (11)	Y1x—S2—Y1xviii	160.421 (18)
S1iv—Y1—S2	85.841 (11)	Y1x—S2—Y1xix	91.657 (3)
O1x—Y2—O1xi	145.57 (11)	Y1xviii—S2—Y1xix	91.657 (3)
O1x—Y2—O2xii	73.66 (8)	Y1x—S2—Y1	91.657 (3)
O1xi—Y2—O2xii	96.72 (8)	Y1xviii—S2—Y1	91.657 (3)
O1x—Y2—O2xiii	96.72 (8)	Y1xix—S2—Y1	160.420 (18)
O1xi—Y2—O2xiii	73.66 (8)	Y2xii—S3—Y2xv	180.0
O2xii—Y2—O2xiii	147.78 (12)	Y2xii—S3—Y2xx	90.0
O1x—Y2—O1xii	127.80 (7)	Y2xv—S3—Y2xx	90.0
O1xi—Y2—O1xii	69.36 (8)	Y2xii—S3—Y2xxi	90.0
O2xii—Y2—O1xii	62.05 (8)	Y2xv—S3—Y2xxi	90.0
O2xiii—Y2—O1xii	135.47 (8)	Y2xx—S3—Y2xxi	180.0
O1x—Y2—O1xiv	69.36 (8)	O3—Si1—O1	107.56 (10)
O1xi—Y2—O1xiv	127.80 (7)	O3—Si1—O1xxii	107.56 (10)
O2xii—Y2—O1xiv	135.47 (8)	O1—Si1—O1xxii	123.34 (16)
O2xiii—Y2—O1xiv	62.05 (8)	O3—Si1—O2	114.39 (18)
O1xii—Y2—O1xiv	127.78 (9)	O1—Si1—O2	102.07 (10)
O1x—Y2—S1xii	140.43 (6)	O1xxii—Si1—O2	102.07 (10)
O1xi—Y2—S1xii	70.68 (5)	Si1—O1—Y2xviii	132.95 (12)
O2xii—Y2—S1xii	130.09 (7)	Si1—O1—Y1xxiii	113.44 (11)
O2xiii—Y2—S1xii	76.63 (6)	Y2xviii—O1—Y1xxiii	101.79 (7)
O1xii—Y2—S1xii	68.44 (5)	Si1—O1—Y2vii	95.33 (10)
O1xiv—Y2—S1xii	73.32 (5)	Y2xviii—O1—Y2vii	103.46 (8)
O1x—Y2—S1x	70.68 (5)	Y1xxiii—O1—Y2vii	106.88 (8)
O1xi—Y2—S1x	140.43 (6)	Si1—O2—Y1	130.32 (16)
O2xii—Y2—S1x	76.63 (6)	Si1—O2—Y2vi	100.30 (9)
O2xiii—Y2—S1x	130.09 (7)	Y1—O2—Y2vi	105.32 (8)
O1xii—Y2—S1x	73.32 (5)	Si1—O2—Y2vii	100.30 (9)
O1xiv—Y2—S1x	68.44 (5)	Y1—O2—Y2vii	105.32 (8)
S1xii—Y2—S1x	83.925 (17)	Y2vi—O2—Y2vii	116.05 (12)
O1x—Y2—S3xv	72.79 (6)	Si1xix—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.