inorganic compounds
TiGeS3
aDivision of Energy Systems Research and Department of Chemistry, Ajou University, Suwon 443-749, Republic of Korea
*Correspondence e-mail: hsyun@ajou.ac.kr
The new ternary titanium(II) thiogermanate(IV), TiGeS3, was synthesized using the reactive halide method. The title compound shows features of a ribbon-type structure formed from double chains composed of edge-sharing octahedral TiS6 and pyramidal GeS3 units, with all atoms in the asymmmetric unit positioned on mirror planes. While the TiS6 octahedron is regular, the coordination around the Ge atom is rather irregular, which can be described as [3 + 3]. Three S atoms build up a triangle that is bound to the Ge atom, the coordination of which is augmented by three additional S atoms at considerably longer distances. The charge balance can formally be described as [Ti4+][Ge2+][S2−]3.
Related literature
For related structures, see: Brasseur & Pauling (1938) for NH4CdCl3; Kniep et al. (1982) for SnIISnIVS3. For isostructural compounds, see: Lelieveld & Ijdo (1978) for PbZrS3; Gressier et al. (1987) for Sn1.2Ti0.8S3. For usual bond lengths and angles for the TiS6 octahedron, see: Jandali et al. (1980) for TiP2S6. A similar coordination of Ge to that observed in the title compound can be found in divalent germanium sulfide, GeS, see: Bissert & Hesse (1978).
Experimental
Crystal data
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Refinement
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Data collection: RAPID-AUTO (Rigaku, 2006); cell RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536812037087/ru2041sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037087/ru2041Isup2.hkl
The title compound, TiGeS3 was prepared by the reaction of elements with the use of the reactive halide-flux technique. A combination of the pure elements, Ti powder(Aldrich 99.7%), Ge powder(CERAC 99.9%) and S powder(Aldrich 99.999%) were mixed in a fused silica tube in molar ratio of Ti:Ge:S=4:2:7 and then KCl(CERAC 99.9%) was added. The mass ratio of the reactants and the halide was 1:2. The tube was evacuated to 0.133 Pa, sealed, and heated gradually (20 K/h) to 923 K, where it was kept for 72 h. The tube was cooled to room temperature at the rate 3 K/h. The excess halide was removed with distilled water and black needle-shaped crystals were obtained. The crystals are stable in air and water. A qualitative
of the needles indicated the presence of Ti, Ge, and S. The composition of the compound was determined by single-crystal X-ray diffraction.The Ti site in Sn1.2Ti0.8S3 has been reported to be occupied by disordered Ti4+ and Sn4+ ions (Gressier et al., 1987) and the nonstoichiometry of the Ti site in the title compound was checked by refining the occupancy and anisotropic displacement parameters while those of the other atoms were fixed. With the nonstoichiometric model, both parameters were not changed significantly and the residuals (wR2, R1 indices) remained the same. The highest peak(1.69 e/Å-3) and the deepest hole (-1.44 e/ Å-3) are 0.77 Å and 0.86 Å from the atom Ge, respectively.
During an effort to find a new phase in the A—Ti—Ge—S system (A=alkali metals), a new compound was isolated. Here we report the synthesis and structure of the new ternary thiogermanate, TiGeS3.
The title compound shows the features of the ribbon-type structure (Fig. 1). Its structure is closely related to that of NH4CdCl3 (Brasseur & Pauling, 1938) and it is isostructural with the previously reported SnIISnIVS3 (Kniep et al., 1982), PbZrS3 (Lelieveld & Ijdo, 1978), and Sn1.2Ti0.8S3 (Gressier et al., 1987). The Ti atom is coordinated by six sulfur atoms in an octahedral arrangement (Fig. 2). The TiS6 octahedra share an edge to form the one-dimensional chains along the b axis. These chains are fused together sharing two S atoms to form the double chain. These double octahedral chains are capped by the Ge atom to complete the one-dimensional chain.
While the TiS6 octahedra are regular and the Ti—S distances are in good agreement with those found in other titanium
(Jandali et al., 1980), the coordination around the Ge atom is rather irregular. It can be described as [3 + 3]. Three S atoms built up a triangle that is bound to the Ge atom (Ge—S, 2.397 (1)–2.475 (1) Å; S—Ge—S, 91.13 (3)–92.65 (4) °), the coordination of which is augmented by three additional S atoms at considerably longer distances of 3.056 (1)–3.436 (1) Å. The similar Ge coordination observed in the title compound can be found in divalent germanium sulfide, GeS (Bissert & Hesse, 1978) and the charge balance can be described by [Ti4+][Ge2+][S2-]3.For related structures, see: Brasseur & Pauling (1938) for NH4CdCl3; Kniep et al. (1982) for SnIISnIVS3. For isostructural compounds, see: Lelieveld & Ijdo (1978) for PbZrS3; Gressier et al. (1987) for Sn1.2Ti0.8S3. For usual bond lengths and angles for the TiS6 octahedron, see: Jandali et al. (1980) for TiP2S6 A similar Ge coordination to that observed in the title compound can be found in divalent germanium sulfide, GeS, see: Bissert & Hesse (1978).
Data collection: RAPID-AUTO (Rigaku, 2006); cell
RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).Fig. 1. A perspective view of TiGeS3 down the b axis showing the ribbon-type structure of the chain. | |
Fig. 2. A view showing the local coordination environments of Ti and Ge atoms with the atom labelling scheme. Displacement ellipsoids are drawn at the 80% probability level. [Symmetry codes: (i) x, 1+y, z; (ii) -x, 1/2+y, -z; (iii) -1/2+x, 1/2-y, 1/2-z.] |
TiGeS3 | F(000) = 408 |
Mr = 216.68 | Dx = 3.507 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 3487 reflections |
a = 8.9263 (8) Å | θ = 3.1–27.4° |
b = 3.4673 (3) Å | µ = 10.56 mm−1 |
c = 13.2596 (15) Å | T = 290 K |
V = 410.39 (7) Å3 | Needle, black |
Z = 4 | 0.60 × 0.08 × 0.06 mm |
Rigaku R-AXIS RAPID diffractometer | 525 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω scans | θmax = 27.4°, θmin = 3.1° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −11→11 |
Tmin = 0.674, Tmax = 1.000 | k = −4→4 |
3802 measured reflections | l = −17→17 |
550 independent reflections |
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)] = 0.032 | w = 1/[σ2(Fo2) + (0.0422P)2 + 0.885P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.076 | (Δ/σ)max < 0.001 |
S = 1.16 | Δρmax = 1.69 e Å−3 |
550 reflections | Δρmin = −1.44 e Å−3 |
32 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008) |
0 restraints | Extinction coefficient: 0.049 (3) |
TiGeS3 | V = 410.39 (7) Å3 |
Mr = 216.68 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 8.9263 (8) Å | µ = 10.56 mm−1 |
b = 3.4673 (3) Å | T = 290 K |
c = 13.2596 (15) Å | 0.60 × 0.08 × 0.06 mm |
Rigaku R-AXIS RAPID diffractometer | 550 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 525 reflections with I > 2σ(I) |
Tmin = 0.674, Tmax = 1.000 | Rint = 0.031 |
3802 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 32 parameters |
wR(F2) = 0.076 | 0 restraints |
S = 1.16 | Δρmax = 1.69 e Å−3 |
550 reflections | Δρmin = −1.44 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 | ||
Ti | 0.34548 (8) | −0.25 | 0.04861 (5) | 0.0133 (3) | |
Ge | 0.06572 (5) | 0.25 | 0.16292 (4) | 0.0227 (2) | |
S1 | 0.51690 (10) | 0.25 | 0.10897 (7) | 0.0102 (3) | |
S2 | 0.23401 (12) | −0.25 | 0.21536 (7) | 0.0146 (3) | |
S3 | 0.17500 (11) | 0.25 | −0.00866 (8) | 0.0125 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ti | 0.0111 (4) | 0.0142 (4) | 0.0145 (4) | 0 | 0.0012 (3) | 0 |
Ge | 0.0145 (3) | 0.0144 (3) | 0.0393 (4) | 0 | 0.00642 (19) | 0 |
S1 | 0.0083 (5) | 0.0108 (5) | 0.0116 (5) | 0 | −0.0002 (3) | 0 |
S2 | 0.0167 (5) | 0.0124 (5) | 0.0148 (5) | 0 | 0.0045 (4) | 0 |
S3 | 0.0089 (5) | 0.0111 (5) | 0.0174 (5) | 0 | −0.0021 (3) | 0 |
Ti—S1i | 2.4238 (12) | Ge—S3 | 2.4754 (11) |
Ti—S2 | 2.4246 (12) | Ge—S1iv | 3.0558 (11) |
Ti—S3ii | 2.4286 (8) | Ge—S3v | 3.4360 (10) |
Ti—S3 | 2.4286 (8) | Ge—S3vi | 3.4360 (10) |
Ti—S1 | 2.4469 (8) | S1—Tii | 2.4238 (12) |
Ti—S1ii | 2.4469 (8) | S1—Tiiii | 2.4469 (8) |
Ge—S2iii | 2.3970 (8) | S2—Geii | 2.3970 (8) |
Ge—S2 | 2.3970 (8) | S3—Tiiii | 2.4286 (8) |
S1i—Ti—S2 | 173.78 (5) | S1—Ti—S1ii | 90.22 (4) |
S1i—Ti—S3ii | 92.75 (4) | S2iii—Ge—S2 | 92.65 (4) |
S2—Ti—S3ii | 91.60 (4) | S2iii—Ge—S3 | 91.13 (3) |
S1i—Ti—S3 | 92.75 (4) | S2—Ge—S3 | 91.13 (3) |
S2—Ti—S3 | 91.60 (4) | Tii—S1—Ti | 92.00 (3) |
S3ii—Ti—S3 | 91.10 (4) | Tii—S1—Tiiii | 92.00 (3) |
S1i—Ti—S1 | 88.00 (3) | Ti—S1—Tiiii | 90.22 (4) |
S2—Ti—S1 | 87.61 (3) | Geii—S2—Ge | 92.65 (4) |
S3ii—Ti—S1 | 179.11 (4) | Geii—S2—Ti | 89.58 (3) |
S3—Ti—S1 | 89.33 (2) | Ge—S2—Ti | 89.58 (3) |
S1i—Ti—S1ii | 88.00 (3) | Tiiii—S3—Ti | 91.10 (4) |
S2—Ti—S1ii | 87.61 (3) | Tiiii—S3—Ge | 87.68 (3) |
S3ii—Ti—S1ii | 89.33 (2) | Ti—S3—Ge | 87.68 (3) |
S3—Ti—S1ii | 179.11 (4) |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x−1/2, y, −z+1/2; (v) −x, −y, −z; (vi) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | TiGeS3 |
Mr | 216.68 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 290 |
a, b, c (Å) | 8.9263 (8), 3.4673 (3), 13.2596 (15) |
V (Å3) | 410.39 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.56 |
Crystal size (mm) | 0.60 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.674, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3802, 550, 525 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.076, 1.16 |
No. of reflections | 550 |
No. of parameters | 32 |
Δρmax, Δρmin (e Å−3) | 1.69, −1.44 |
Computer programs: RAPID-AUTO (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999).
Ti—S1i | 2.4238 (12) | Ge—S2iii | 2.3970 (8) |
Ti—S2 | 2.4246 (12) | Ge—S2 | 2.3970 (8) |
Ti—S3ii | 2.4286 (8) | Ge—S3 | 2.4754 (11) |
Ti—S3 | 2.4286 (8) | Ge—S1iv | 3.0558 (11) |
Ti—S1 | 2.4469 (8) | Ge—S3v | 3.4360 (10) |
Ti—S1ii | 2.4469 (8) | Ge—S3vi | 3.4360 (10) |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x−1/2, y, −z+1/2; (v) −x, −y, −z; (vi) −x, −y+1, −z. |
Acknowledgements
This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2009–0094046). The authors are grateful to Ajou University for financial support (S2011G000100088-COR– 0101-S000100).
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During an effort to find a new phase in the A—Ti—Ge—S system (A=alkali metals), a new compound was isolated. Here we report the synthesis and structure of the new ternary thiogermanate, TiGeS3.
The title compound shows the features of the ribbon-type structure (Fig. 1). Its structure is closely related to that of NH4CdCl3 (Brasseur & Pauling, 1938) and it is isostructural with the previously reported SnIISnIVS3 (Kniep et al., 1982), PbZrS3 (Lelieveld & Ijdo, 1978), and Sn1.2Ti0.8S3 (Gressier et al., 1987). The Ti atom is coordinated by six sulfur atoms in an octahedral arrangement (Fig. 2). The TiS6 octahedra share an edge to form the one-dimensional chains along the b axis. These chains are fused together sharing two S atoms to form the double chain. These double octahedral chains are capped by the Ge atom to complete the one-dimensional chain.
While the TiS6 octahedra are regular and the Ti—S distances are in good agreement with those found in other titanium sulfides (Jandali et al., 1980), the coordination around the Ge atom is rather irregular. It can be described as [3 + 3]. Three S atoms built up a triangle that is bound to the Ge atom (Ge—S, 2.397 (1)–2.475 (1) Å; S—Ge—S, 91.13 (3)–92.65 (4) °), the coordination of which is augmented by three additional S atoms at considerably longer distances of 3.056 (1)–3.436 (1) Å. The similar Ge coordination observed in the title compound can be found in divalent germanium sulfide, GeS (Bissert & Hesse, 1978) and the charge balance can be described by [Ti4+][Ge2+][S2-]3.