Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048593/wm2149sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048593/wm2149Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (e-S) = 0.001 Å
- Disorder in main residue
- R factor = 0.013
- wR factor = 0.022
- Data-to-parameter ratio = 24.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT301_ALERT_3_C Main Residue Disorder ......................... 1.00 Perc.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 29.57 From the CIF: _reflns_number_total 945 Count of symmetry unique reflns 538 Completeness (_total/calc) 175.65% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 407 Fraction of Friedel pairs measured 0.757 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For investigations of the phase relations in the quasi-ternary Ce2S3–MgS–GeS2 system and a previous structure refinement of the title compound from powder data, see Huch et al. (2006). For studies of Ln3Ag1-δSnS7 (Ln = La, Ce; δ = 0.18–0.19) and Ln3Ag1-δSiS7 (Ln = La–Nd, Sm; δ = 0.10–0.23) compounds, see Daszkiewicz et al. (2007a, b), respectively.
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 Ce:Ge:Mg:S = 3:1:0.5:7 in evacuated silica ampoules. In order to avoid reaction of magnesium with SiO2, the ampoule was covered with graphite. The ampoule was heated in a tube furnace with a heating rate of 30 K/h to 1420 K and were kept at this temperature for 3 h. It was then cooled down slowly (10 K/h) to 870 K and annealed at this temperature for further 240 h and finally quenched in cold water. The obtained red crystals had a prismatic habit with a maximal length of 0.3 mm.
The site occupancy factor for Mg atom was constrained (s.o.f.=0.5) during refinement in order to satisfy the charge balance requirement. Results of single-crystal reinvestigation of Ce3Mg0.5GeS7 agree well with those reported on the basis of the powder diffraction study (lattice parameters: a = 10.262 (2), c = 7.7849 (7) Å; Huch et al., 2006), but with improved precision on atomic coordinates and interatomic distances.
The formation of the quaternary compound Ce3Mg0.5GeS7 has been investigated very recently during phase formation studies in the quasi-ternary Ce2S3—MgS-GeS2 system at 870 K, and its crystal structure was originally refined from X-ray powder diffraction data (Huch et al., 2006). To obtain more accurate results we have now re-investigated the structure from single-crystal data.
The unit cell and coordination polyhedra of the Ce, Mg and Ge atoms in the structure of the title compound are shown in Fig. 1. The Ce atoms are surrounded by 8 S atoms which form distorted bi-capped trigonal prisms. The magnesium position is half-occupied and is in the centre of a trigonal antiprism which has 3 symmetry. This position correlates well with the disordered Ag2 position in the structures of Ln3Ag1-δSnS7 (Ln = La, Ce; δ = 0.18–0.19) (Daszkiewicz et al., 2007a) and Ln3Ag1-δSiS7 (Ln = La—Nd, Sm; δ = 0.10–0.23) (Daszkiewicz et al., 2007b). The Ge atom is situated on a position with 3 symmetry, and is surrounded tetrahedrally by four S atoms with one short and three longer Ge—S bonds.
For investigations of the phase relations in the quasi-ternary Ce2S3–MgS–GeS2 system and a previous structure refinement of the title compound from powder data, see Huch et al. (2006). For studies of Ln3Ag1-δSnS7 (Ln = La, Ce; δ = 0.18–0.19) and Ln3Ag1-δSiS7 (Ln = La–Nd, Sm; δ = 0.10–0.23) compounds, see Daszkiewicz et al. (2007a, b), respectively.
Data collection: CrysAlis (Oxford Diffraction, 2006); cell refinement: CrysAlis (Oxford Diffraction, 2006); data reduction: CrysAlis (Oxford Diffraction, 2006); 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).
Ce3Mg0.50GeS7 | Dx = 4.605 Mg m−3 |
Mr = 729.53 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63 | Cell parameters from 919 reflections |
Hall symbol: P 6c | θ = 4.2–29.6° |
a = 10.2626 (15) Å | µ = 16.91 mm−1 |
c = 5.7679 (12) Å | T = 293 K |
V = 526.09 (15) Å3 | Prism, red |
Z = 2 | 0.13 × 0.11 × 0.08 mm |
F(000) = 648 |
Kuma KM-4 diffractometer with CCD area detector | 945 independent reflections |
Radiation source: fine-focus sealed tube | 919 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 1024x1024 with blocks 2x2, 33.133pixel/mm pixels mm-1 | θmax = 29.6°, θmin = 4.2° |
ω scans | h = −14→13 |
Absorption correction: numerical (CrysAlis; Oxford Diffraction, 2006) | k = −13→14 |
Tmin = 0.175, Tmax = 0.367 | l = −7→8 |
7638 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0105P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.013 | (Δ/σ)max = 0.001 |
wR(F2) = 0.022 | Δρmax = 0.53 e Å−3 |
S = 1.01 | Δρmin = −0.56 e Å−3 |
945 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
38 parameters | Extinction coefficient: 0.0111 (3) |
1 restraint | Absolute structure: Flack (1983), 409 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.017 (12) |
Ce3Mg0.50GeS7 | Z = 2 |
Mr = 729.53 | Mo Kα radiation |
Hexagonal, P63 | µ = 16.91 mm−1 |
a = 10.2626 (15) Å | T = 293 K |
c = 5.7679 (12) Å | 0.13 × 0.11 × 0.08 mm |
V = 526.09 (15) Å3 |
Kuma KM-4 diffractometer with CCD area detector | 945 independent reflections |
Absorption correction: numerical (CrysAlis; Oxford Diffraction, 2006) | 919 reflections with I > 2σ(I) |
Tmin = 0.175, Tmax = 0.367 | Rint = 0.032 |
7638 measured reflections |
R[F2 > 2σ(F2)] = 0.013 | 1 restraint |
wR(F2) = 0.022 | Δρmax = 0.53 e Å−3 |
S = 1.01 | Δρmin = −0.56 e Å−3 |
945 reflections | Absolute structure: Flack (1983), 409 Friedel pairs |
38 parameters | Absolute structure parameter: −0.017 (12) |
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 | Occ. (<1) | |
Ce | 0.357264 (14) | 0.231380 (14) | 0.23296 (6) | 0.00788 (5) | |
Ge1 | 0.6667 | 0.3333 | 0.81575 (8) | 0.00757 (11) | |
Mg1 | 0.0000 | 0.0000 | 0.4694 (10) | 0.0089 (6) | 0.50 |
S1 | 0.6667 | 0.3333 | 0.4400 (2) | 0.0098 (3) | |
S2 | 0.08688 (7) | 0.24688 (7) | 0.21849 (17) | 0.01013 (12) | |
S3 | 0.52030 (8) | 0.10633 (8) | 0.96601 (13) | 0.00851 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce | 0.00658 (7) | 0.00734 (7) | 0.00894 (7) | 0.00289 (5) | 0.00076 (9) | −0.00015 (10) |
Ge1 | 0.00819 (15) | 0.00819 (15) | 0.0063 (2) | 0.00409 (8) | 0.000 | 0.000 |
Mg1 | 0.0063 (7) | 0.0063 (7) | 0.0141 (16) | 0.0031 (4) | 0.000 | 0.000 |
S1 | 0.0115 (4) | 0.0115 (4) | 0.0064 (6) | 0.00574 (18) | 0.000 | 0.000 |
S2 | 0.0080 (3) | 0.0102 (3) | 0.0123 (3) | 0.0046 (2) | −0.0012 (4) | 0.0000 (4) |
S3 | 0.0067 (3) | 0.0077 (3) | 0.0099 (3) | 0.0026 (3) | −0.0008 (3) | 0.0004 (3) |
Ce—S2i | 2.8567 (7) | Ge1—S3ix | 2.2216 (8) |
Ce—S2 | 2.8589 (7) | Mg1—S2x | 2.655 (3) |
Ce—S3ii | 2.8972 (8) | Mg1—S2 | 2.655 (3) |
Ce—S2iii | 2.9720 (12) | Mg1—S2i | 2.655 (3) |
Ce—S3iv | 2.9941 (8) | Mg1—S2iii | 2.650 (3) |
Ce—S3v | 3.0351 (8) | Mg1—S2xi | 2.650 (3) |
Ce—S1 | 3.0465 (7) | Mg1—S2xii | 2.650 (3) |
Ce—S2vi | 3.1298 (12) | Mg1—Mg1xi | 2.8839 (6) |
Ce—Mg1 | 3.498 (2) | Mg1—Mg1vii | 2.8840 (6) |
Ce—Mg1vii | 3.562 (3) | Mg1—Cei | 3.498 (2) |
Ge1—S1 | 2.1671 (14) | Mg1—Cex | 3.498 (2) |
Ge1—S3viii | 2.2216 (8) | Mg1—Cexii | 3.562 (3) |
Ge1—S3 | 2.2216 (8) | ||
S2i—Ce—S2 | 84.84 (3) | S2xi—Mg1—Cei | 55.79 (3) |
S2i—Ce—S3ii | 142.14 (3) | S2xii—Mg1—Cei | 126.72 (3) |
S2—Ce—S3ii | 108.53 (2) | S2x—Mg1—Ce | 124.03 (19) |
S2i—Ce—S2iii | 77.34 (2) | S2—Mg1—Ce | 53.26 (5) |
S2—Ce—S2iii | 77.31 (2) | S2i—Mg1—Ce | 53.21 (5) |
S3ii—Ce—S2iii | 139.37 (2) | S2iii—Mg1—Ce | 55.79 (3) |
S2i—Ce—S3iv | 73.94 (2) | S2xi—Mg1—Ce | 126.72 (3) |
S2—Ce—S3iv | 140.79 (3) | S2xii—Mg1—Ce | 126.77 (3) |
S3ii—Ce—S3iv | 73.92 (3) | Cei—Mg1—Ce | 105.79 (10) |
S2iii—Ce—S3iv | 127.211 (19) | S2x—Mg1—Cex | 53.26 (5) |
S2i—Ce—S3v | 144.09 (2) | S2—Mg1—Cex | 53.21 (5) |
S2—Ce—S3v | 71.09 (2) | S2i—Mg1—Cex | 124.03 (19) |
S3ii—Ce—S3v | 72.593 (16) | S2iii—Mg1—Cex | 126.72 (3) |
S2iii—Ce—S3v | 71.74 (2) | S2xi—Mg1—Cex | 126.77 (3) |
S3iv—Ce—S3v | 140.464 (19) | S2xii—Mg1—Cex | 55.79 (3) |
S2i—Ce—S1 | 115.164 (15) | Cei—Mg1—Cex | 105.79 (10) |
S2—Ce—S1 | 150.03 (2) | Ce—Mg1—Cex | 105.79 (10) |
S3ii—Ce—S1 | 70.08 (2) | S2x—Mg1—Cexii | 127.74 (2) |
S2iii—Ce—S1 | 85.33 (3) | S2—Mg1—Cexii | 58.29 (3) |
S3iv—Ce—S1 | 68.84 (2) | S2i—Mg1—Cexii | 127.69 (2) |
S3v—Ce—S1 | 80.388 (17) | S2iii—Mg1—Cexii | 52.29 (5) |
S2i—Ce—S2vi | 74.81 (2) | S2xi—Mg1—Cexii | 121.89 (19) |
S2—Ce—S2vi | 74.78 (2) | S2xii—Mg1—Cexii | 52.33 (5) |
S3ii—Ce—S2vi | 75.01 (2) | Cei—Mg1—Cexii | 177.67 (17) |
S2iii—Ce—S2vi | 141.90 (2) | Ce—Mg1—Cexii | 75.523 (7) |
S3iv—Ce—S2vi | 68.07 (2) | Cex—Mg1—Cexii | 75.523 (7) |
S3v—Ce—S2vi | 121.248 (19) | Ge1—S1—Ceviii | 113.08 (2) |
S1—Ce—S2vi | 130.18 (3) | Ge1—S1—Ceix | 113.08 (2) |
Mg1—Ce—Mg1vii | 48.212 (11) | Ceviii—S1—Ceix | 105.63 (3) |
S1—Ge1—S3viii | 112.96 (2) | Ge1—S1—Ce | 113.08 (2) |
S1—Ge1—S3 | 112.96 (2) | Ceviii—S1—Ce | 105.63 (3) |
S3viii—Ge1—S3 | 105.77 (3) | Ceix—S1—Ce | 105.63 (3) |
S1—Ge1—S3ix | 112.96 (2) | Mg1—S2—Mg1vii | 65.87 (2) |
S3viii—Ge1—S3ix | 105.77 (3) | Mg1—S2—Cex | 78.69 (2) |
S3—Ge1—S3ix | 105.77 (3) | Mg1vii—S2—Cex | 80.52 (2) |
S2x—Mg1—S2 | 93.12 (15) | Mg1—S2—Ce | 78.65 (2) |
S2x—Mg1—S2i | 93.12 (15) | Mg1vii—S2—Ce | 80.48 (2) |
S2—Mg1—S2i | 93.12 (15) | Cex—S2—Ce | 154.89 (3) |
S2x—Mg1—S2iii | 179.8 (2) | Mg1—S2—Cev | 142.58 (11) |
S2—Mg1—S2iii | 86.754 (14) | Mg1vii—S2—Cev | 76.72 (11) |
S2i—Mg1—S2iii | 86.754 (14) | Cex—S2—Cev | 95.74 (2) |
S2x—Mg1—S2xi | 86.754 (14) | Ce—S2—Cev | 95.69 (2) |
S2—Mg1—S2xi | 179.8 (2) | Mg1—S2—Cexii | 75.51 (11) |
S2i—Mg1—S2xi | 86.754 (14) | Mg1vii—S2—Cexii | 141.38 (11) |
S2iii—Mg1—S2xi | 93.37 (15) | Cex—S2—Cexii | 92.36 (2) |
S2x—Mg1—S2xii | 86.754 (14) | Ce—S2—Cexii | 92.32 (2) |
S2—Mg1—S2xii | 86.754 (14) | Cev—S2—Cexii | 141.90 (2) |
S2i—Mg1—S2xii | 179.8 (2) | Ge1—S3—Cexiii | 91.41 (3) |
S2iii—Mg1—S2xii | 93.37 (15) | Ge1—S3—Cexiv | 88.90 (2) |
S2xi—Mg1—S2xii | 93.37 (15) | Cexiii—S3—Cexiv | 110.96 (3) |
S2x—Mg1—Cei | 53.21 (5) | Ge1—S3—Ceiii | 122.24 (3) |
S2—Mg1—Cei | 124.03 (19) | Cexiii—S3—Ceiii | 140.35 (3) |
S2i—Mg1—Cei | 53.26 (5) | Cexiv—S3—Ceiii | 91.63 (2) |
S2iii—Mg1—Cei | 126.77 (3) |
Symmetry codes: (i) −x+y, −x, z; (ii) −x+y+1, −x+1, z−1; (iii) y, −x+y, z+1/2; (iv) x, y, z−1; (v) x−y, x, z−1/2; (vi) y, −x+y, z−1/2; (vii) −x, −y, z−1/2; (viii) −y+1, x−y, z; (ix) −x+y+1, −x+1, z; (x) −y, x−y, z; (xi) −x, −y, z+1/2; (xii) x−y, x, z+1/2; (xiii) −y+1, x−y, z+1; (xiv) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | Ce3Mg0.50GeS7 |
Mr | 729.53 |
Crystal system, space group | Hexagonal, P63 |
Temperature (K) | 293 |
a, c (Å) | 10.2626 (15), 5.7679 (12) |
V (Å3) | 526.09 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 16.91 |
Crystal size (mm) | 0.13 × 0.11 × 0.08 |
Data collection | |
Diffractometer | Kuma KM-4 diffractometer with CCD area detector |
Absorption correction | Numerical (CrysAlis; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.175, 0.367 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7638, 945, 919 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.694 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.013, 0.022, 1.01 |
No. of reflections | 945 |
No. of parameters | 38 |
No. of restraints | 1 |
Δρmax, Δρmin (e Å−3) | 0.53, −0.56 |
Absolute structure | Flack (1983), 409 Friedel pairs |
Absolute structure parameter | −0.017 (12) |
Computer programs: CrysAlis (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005), publCIF (Westrip, 2007).
Ce—S2i | 2.8567 (7) | Ce—S1 | 3.0465 (7) |
Ce—S2 | 2.8589 (7) | Ce—S2vi | 3.1298 (12) |
Ce—S3ii | 2.8972 (8) | Ge1—S1 | 2.1671 (14) |
Ce—S2iii | 2.9720 (12) | Ge1—S3 | 2.2216 (8) |
Ce—S3iv | 2.9941 (8) | Mg1—S2 | 2.655 (3) |
Ce—S3v | 3.0351 (8) | Mg1—S2iii | 2.650 (3) |
Symmetry codes: (i) −x+y, −x, z; (ii) −x+y+1, −x+1, z−1; (iii) y, −x+y, z+1/2; (iv) x, y, z−1; (v) x−y, x, z−1/2; (vi) y, −x+y, z−1/2. |
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The formation of the quaternary compound Ce3Mg0.5GeS7 has been investigated very recently during phase formation studies in the quasi-ternary Ce2S3—MgS-GeS2 system at 870 K, and its crystal structure was originally refined from X-ray powder diffraction data (Huch et al., 2006). To obtain more accurate results we have now re-investigated the structure from single-crystal data.
The unit cell and coordination polyhedra of the Ce, Mg and Ge atoms in the structure of the title compound are shown in Fig. 1. The Ce atoms are surrounded by 8 S atoms which form distorted bi-capped trigonal prisms. The magnesium position is half-occupied and is in the centre of a trigonal antiprism which has 3 symmetry. This position correlates well with the disordered Ag2 position in the structures of Ln3Ag1-δSnS7 (Ln = La, Ce; δ = 0.18–0.19) (Daszkiewicz et al., 2007a) and Ln3Ag1-δSiS7 (Ln = La—Nd, Sm; δ = 0.10–0.23) (Daszkiewicz et al., 2007b). The Ge atom is situated on a position with 3 symmetry, and is surrounded tetrahedrally by four S atoms with one short and three longer Ge—S bonds.