Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807058606/wm2163sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807058606/wm2163Isup2.hkl |
Single crystals of the title compound were grown by fusion of the elemental constituents (Alfa Aesar; purity > 99.9%wt) in the stoichiometric ratio of La:Si:S = 2:1:5 in an evacuated silica ampoule. The ampoule was heated in a tube furnace with a heating rate of 30 K/h to 1420 K and was kept at this temperature for 4 h. It was then cooled down slowly (10 K/h) to 770 K and annealed at this temperature for further 240 h and finally quenched in cold water. The obtained yellow crystals were selected from the brown-coloured compact product. The crystals had a prismatic habit and maximal lengths of 0.2 mm.
The highest peak is located 2.19 Å away from Si and the deepest hole 0.02 Å away from La2.
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: publCIF (Westrip, 2007).
Fig. 1. The structure of La2SiS5 viewed along the a axis. Displacement ellipsoids are shown at the 50% probability level. |
La2SiS5 | F(000) = 832 |
Mr = 466.21 | Dx = 4.153 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1465 reflections |
a = 7.6208 (12) Å | θ = 3.1–28.3° |
b = 12.6407 (15) Å | µ = 12.75 mm−1 |
c = 7.8998 (12) Å | T = 293 K |
β = 101.559 (13)° | Prism, yellow |
V = 745.57 (19) Å3 | 0.13 × 0.09 × 0.06 mm |
Z = 4 |
KUMA KM-4 with CCD area-detector diffractometer | 1818 independent reflections |
Radiation source: fine-focus sealed tube | 1465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm-1 | θmax = 28.3°, θmin = 3.1° |
ω–scan | h = −10→9 |
Absorption correction: numerical (CrysAlis-RED; Oxford Diffraction, 2006) | k = −15→16 |
Tmin = 0.208, Tmax = 0.567 | l = −9→10 |
9434 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.023 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.040 | w = 1/[σ2(Fo2) + (0.0134P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max = 0.001 |
1818 reflections | Δρmax = 0.97 e Å−3 |
73 parameters | Δρmin = −1.22 e Å−3 |
La2SiS5 | V = 745.57 (19) Å3 |
Mr = 466.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.6208 (12) Å | µ = 12.75 mm−1 |
b = 12.6407 (15) Å | T = 293 K |
c = 7.8998 (12) Å | 0.13 × 0.09 × 0.06 mm |
β = 101.559 (13)° |
KUMA KM-4 with CCD area-detector diffractometer | 1818 independent reflections |
Absorption correction: numerical (CrysAlis-RED; Oxford Diffraction, 2006) | 1465 reflections with I > 2σ(I) |
Tmin = 0.208, Tmax = 0.567 | Rint = 0.052 |
9434 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 73 parameters |
wR(F2) = 0.040 | 0 restraints |
S = 0.97 | Δρmax = 0.97 e Å−3 |
1818 reflections | Δρmin = −1.22 e Å−3 |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
La1 | 0.74054 (4) | 0.09529 (2) | 0.04559 (3) | 0.00735 (8) | |
La2 | 0.66488 (4) | 0.66522 (2) | 0.13363 (4) | 0.00926 (8) | |
Si | 0.83032 (18) | 0.38347 (10) | 0.09619 (16) | 0.0080 (3) | |
S1 | 1.02312 (17) | 0.27396 (9) | 0.05064 (15) | 0.0111 (3) | |
S2 | 0.92134 (17) | 0.50034 (9) | 0.28160 (15) | 0.0092 (3) | |
S3 | 0.36080 (16) | 0.12101 (9) | 0.00203 (15) | 0.0085 (3) | |
S4 | 0.67558 (17) | 0.47033 (9) | −0.11162 (15) | 0.0103 (3) | |
S5 | 0.62829 (17) | 0.29811 (9) | 0.19537 (15) | 0.0100 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
La1 | 0.00743 (15) | 0.00657 (14) | 0.00813 (14) | 0.00046 (11) | 0.00170 (11) | 0.00066 (11) |
La2 | 0.00955 (16) | 0.00836 (15) | 0.00978 (14) | 0.00071 (12) | 0.00175 (12) | 0.00164 (11) |
Si | 0.0087 (7) | 0.0075 (7) | 0.0078 (6) | −0.0011 (5) | 0.0019 (5) | −0.0009 (5) |
S1 | 0.0101 (7) | 0.0090 (6) | 0.0154 (6) | −0.0001 (5) | 0.0056 (5) | −0.0010 (5) |
S2 | 0.0098 (7) | 0.0081 (6) | 0.0094 (6) | −0.0015 (5) | 0.0011 (5) | −0.0023 (5) |
S3 | 0.0071 (6) | 0.0074 (6) | 0.0110 (6) | 0.0005 (5) | 0.0021 (5) | −0.0007 (5) |
S4 | 0.0119 (7) | 0.0107 (6) | 0.0078 (6) | 0.0013 (5) | 0.0012 (5) | −0.0003 (5) |
S5 | 0.0111 (7) | 0.0084 (6) | 0.0109 (6) | −0.0025 (5) | 0.0029 (5) | −0.0009 (5) |
La1—S1 | 3.1154 (13) | Si—S1 | 2.1015 (18) |
La1—S2i | 2.9213 (13) | Si—S2 | 2.0980 (17) |
La1—S2ii | 2.9767 (13) | Si—S4 | 2.1249 (18) |
La1—S3iii | 2.8456 (12) | Si—S5 | 2.1522 (19) |
La1—S3 | 2.8635 (13) | S1—La2v | 3.1226 (13) |
La1—S4iv | 2.9670 (13) | S1—La2i | 3.3745 (13) |
La1—S5 | 3.0184 (13) | S2—La1viii | 2.9213 (13) |
La1—S5ii | 3.0420 (13) | S2—La1iv | 2.9767 (13) |
La2—S1v | 3.1226 (14) | S3—La1iii | 2.8456 (12) |
La2—S2 | 2.9350 (13) | S3—La2vi | 2.8991 (12) |
La2—S3vi | 2.8991 (12) | S3—La2ix | 2.9767 (13) |
La2—S3vii | 2.9767 (13) | S4—La1ii | 2.9670 (13) |
La2—S4vi | 3.0850 (13) | S4—La2vi | 3.0850 (13) |
La2—S4 | 3.1453 (12) | S5—La1iv | 3.0420 (13) |
La2—S5vi | 3.1040 (13) | S5—La2vi | 3.1040 (13) |
La2—S5vii | 3.2936 (13) | S5—La2ix | 3.2936 (13) |
La2—S1viii | 3.3745 (13) | ||
S3iii—La1—S3 | 81.50 (4) | S4vi—La2—S5vii | 71.00 (3) |
S3iii—La1—S2i | 81.81 (3) | S5vi—La2—S5vii | 80.42 (3) |
S3—La1—S2i | 151.44 (4) | S1v—La2—S5vii | 135.08 (3) |
S3iii—La1—S4iv | 76.21 (3) | S4—La2—S5vii | 139.07 (3) |
S3—La1—S4iv | 77.99 (4) | S3vi—La2—S1viii | 83.05 (3) |
S2i—La1—S4iv | 75.61 (4) | S2—La2—S1viii | 71.37 (3) |
S3iii—La1—S2ii | 70.65 (3) | S3vii—La2—S1viii | 62.28 (3) |
S3—La1—S2ii | 124.09 (4) | S4vi—La2—S1viii | 136.72 (3) |
S2i—La1—S2ii | 70.84 (4) | S5vi—La2—S1viii | 147.19 (3) |
S4iv—La1—S2ii | 135.33 (3) | S1v—La2—S1viii | 75.80 (3) |
S3iii—La1—S5 | 141.01 (4) | S4—La2—S1viii | 132.30 (3) |
S3—La1—S5 | 65.90 (3) | S5vii—La2—S1viii | 85.67 (3) |
S2i—La1—S5 | 117.29 (3) | S2—Si—S1 | 116.02 (8) |
S4iv—La1—S5 | 76.55 (3) | S2—Si—S4 | 103.31 (7) |
S2ii—La1—S5 | 145.78 (3) | S1—Si—S4 | 120.45 (8) |
S3iii—La1—S5ii | 106.62 (3) | S2—Si—S5 | 105.04 (7) |
S3—La1—S5ii | 75.35 (4) | S1—Si—S5 | 107.93 (7) |
S2i—La1—S5ii | 131.91 (4) | S4—Si—S5 | 102.33 (8) |
S4iv—La1—S5ii | 152.37 (4) | Si—S1—La1 | 88.54 (6) |
S2ii—La1—S5ii | 68.16 (3) | Si—S1—La2v | 122.78 (6) |
S5—La1—S5ii | 85.99 (2) | La1—S1—La2v | 139.60 (4) |
S3iii—La1—S1 | 150.10 (3) | Si—S1—La2i | 123.71 (6) |
S3—La1—S1 | 126.77 (3) | La1—S1—La2i | 95.57 (3) |
S2i—La1—S1 | 75.47 (3) | La2v—S1—La2i | 87.44 (3) |
S4iv—La1—S1 | 115.61 (3) | Si—S2—La1viii | 138.84 (7) |
S2ii—La1—S1 | 83.54 (3) | Si—S2—La2 | 96.97 (6) |
S5—La1—S1 | 68.20 (3) | La1viii—S2—La2 | 110.42 (4) |
S5ii—La1—S1 | 76.01 (3) | Si—S2—La1iv | 93.92 (6) |
S3vi—La2—S2 | 143.07 (4) | La1viii—S2—La1iv | 109.16 (4) |
S3vi—La2—S3vii | 121.32 (3) | La2—S2—La1iv | 101.69 (4) |
S2—La2—S3vii | 69.46 (3) | La1iii—S3—La1 | 98.50 (4) |
S3vi—La2—S4vi | 120.21 (3) | La1iii—S3—La2vi | 148.24 (5) |
S2—La2—S4vi | 96.52 (3) | La1—S3—La2vi | 98.16 (4) |
S3vii—La2—S4vi | 74.50 (3) | La1iii—S3—La2ix | 103.86 (4) |
S3vi—La2—S5vi | 64.36 (3) | La1—S3—La2ix | 99.54 (4) |
S2—La2—S5vi | 138.56 (3) | La2vi—S3—La2ix | 99.78 (3) |
S3vii—La2—S5vi | 131.45 (4) | Si—S4—La1ii | 113.10 (6) |
S4vi—La2—S5vi | 65.14 (3) | Si—S4—La2vi | 94.98 (6) |
S3vi—La2—S1v | 66.39 (3) | La1ii—S4—La2vi | 94.91 (3) |
S2—La2—S1v | 81.49 (3) | Si—S4—La2 | 90.44 (5) |
S3vii—La2—S1v | 134.48 (3) | La1ii—S4—La2 | 144.17 (4) |
S4vi—La2—S1v | 145.17 (3) | La2vi—S4—La2 | 110.15 (4) |
S5vi—La2—S1v | 93.47 (4) | Si—S5—La1 | 90.20 (6) |
S3vi—La2—S4 | 120.70 (3) | Si—S5—La1iv | 91.02 (5) |
S2—La2—S4 | 65.91 (3) | La1—S5—La1iv | 133.05 (4) |
S3vii—La2—S4 | 117.61 (3) | Si—S5—La2vi | 93.88 (5) |
S4vi—La2—S4 | 69.85 (4) | La1—S5—La2vi | 90.66 (3) |
S5vi—La2—S4 | 72.80 (3) | La1iv—S5—La2vi | 136.01 (4) |
S1v—La2—S4 | 77.85 (3) | Si—S5—La2ix | 176.92 (6) |
S3vi—La2—S5vii | 71.04 (3) | La1—S5—La2ix | 89.79 (3) |
S2—La2—S5vii | 130.63 (3) | La1iv—S5—La2ix | 86.74 (3) |
S3vii—La2—S5vii | 61.17 (3) | La2vi—S5—La2ix | 89.20 (3) |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y, −z; (iv) x, −y+1/2, z+1/2; (v) −x+2, −y+1, −z; (vi) −x+1, −y+1, −z; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+2, y+1/2, −z+1/2; (ix) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | La2SiS5 |
Mr | 466.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.6208 (12), 12.6407 (15), 7.8998 (12) |
β (°) | 101.559 (13) |
V (Å3) | 745.57 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 12.75 |
Crystal size (mm) | 0.13 × 0.09 × 0.06 |
Data collection | |
Diffractometer | KUMA KM-4 with CCD area-detector diffractometer |
Absorption correction | Numerical (CrysAlis-RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.208, 0.567 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9434, 1818, 1465 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.040, 0.97 |
No. of reflections | 1818 |
No. of parameters | 73 |
Δρmax, Δρmin (e Å−3) | 0.97, −1.22 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005), publCIF (Westrip, 2007).
La1—S1 | 3.1154 (13) | La2—S3vii | 2.9767 (13) |
La1—S2i | 2.9213 (13) | La2—S4vi | 3.0850 (13) |
La1—S2ii | 2.9767 (13) | La2—S4 | 3.1453 (12) |
La1—S3iii | 2.8456 (12) | La2—S5vi | 3.1040 (13) |
La1—S3 | 2.8635 (13) | La2—S5vii | 3.2936 (13) |
La1—S4iv | 2.9670 (13) | La2—S1viii | 3.3745 (13) |
La1—S5 | 3.0184 (13) | Si—S1 | 2.1015 (18) |
La1—S5ii | 3.0420 (13) | Si—S2 | 2.0980 (17) |
La2—S1v | 3.1226 (14) | Si—S4 | 2.1249 (18) |
La2—S2 | 2.9350 (13) | Si—S5 | 2.1522 (19) |
La2—S3vi | 2.8991 (12) |
Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y, −z; (iv) x, −y+1/2, z+1/2; (v) −x+2, −y+1, −z; (vi) −x+1, −y+1, −z; (vii) −x+1, y+1/2, −z+1/2; (viii) −x+2, y+1/2, −z+1/2. |
The formation of the ternary compound La2SiS5 has been reported previously (Michelet et al., 1970), but only lattice parameters were determined and isotypism with the La2GeS5 structure was established during the original study. The crystal structure of La2SiS5 has now been investigated by means of single-crystal X-ray diffraction data and is presented in this communication.
The unit cell and coordination polyhedra of the La and Si atoms are shown in Fig. 1. Six S atoms surround both independent La atoms leading to a distorted trigonal-prismatic arrangement. For La1, two additional S atoms and for La2 three additional S augment these basic polyhedra to bi- and tri-capped trigonal prisms, respectively. The Si atom has a slightly distorted tetrahedral environment of S atoms. The capped trigonal prisms are linked to the [SiS4] tetrahedra by corners and edges, whereas the capped trigonal prisms are connected to each other also by sharing faces.