TY  - JOUR
AU  - Poleti, Dejan
AU  - Karanovic, Ljiljana
AU  - Balic-Zunic, Tonci
AU  - Gržetić, Ivan
PY  - 2012
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1290
AB  - The intermediate member of the (Bi,Sb)(2)S-3 solid-solution series was prepared by dry synthesis at low temperature (200 degrees C) with a long annealing period in sealed silica tube. The EDS analysis yielded an empirical formula (Bi0.96Sb1.04)S-3, which is very close to the formula (Bi0.94Sb1.06)S-3 obtained by crystal structure analysis. The crystal structure was refined to the R-factors: R-1 = 0.0288 for I  gt  2 sigma(I) and wR(2) = 0.0542 for all data. (Bi0.94Sb1.06)S-3 has orthorhombic symmetry with space group Pnma (No. 62). The asymmetric unit contains two independent mixed cation sites, both coordinated to seven S atoms in a form of mono-capped trigonal prism. They combine into infinite (M4S6)(n) rods parallel to the [010] direction with only weak interactions between rods where the lone electron pairs are directed. Our data and the revaluation of previous data resolve a controversy about the distribution of Sb and Bi over the two structural sites which exists in previously published works. It is shown that the structural constraints favour a slight preference of the larger cation for the marginal M1 site over the whole span of the solid-solution series. The unit cell parameters show a deviation form the Vegard's law connected with different rates of the parallel increase of lengths of the strong bonds and the decreasing influence of the lone electron pair with the replacement of Sb by Bi. The changes in the character of the two independent cation sites introduced by this replacement are similar to those produced during compression of Sb2S3.
PB  - E Schweizerbartsche Verlagsbuchhandlung, Stuttgart
T2  - Neues Jahrbuch Fur Mineralogie. Abhandlungen
T1  - Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series
VL  - 189
IS  - 2
SP  - 177
EP  - 187
DO  - 10.1127/0077-7757/2012/0217
ER  - 

@article{
author = "Poleti, Dejan and Karanovic, Ljiljana and Balic-Zunic, Tonci and Gržetić, Ivan",
year = "2012",
abstract = "The intermediate member of the (Bi,Sb)(2)S-3 solid-solution series was prepared by dry synthesis at low temperature (200 degrees C) with a long annealing period in sealed silica tube. The EDS analysis yielded an empirical formula (Bi0.96Sb1.04)S-3, which is very close to the formula (Bi0.94Sb1.06)S-3 obtained by crystal structure analysis. The crystal structure was refined to the R-factors: R-1 = 0.0288 for I  gt  2 sigma(I) and wR(2) = 0.0542 for all data. (Bi0.94Sb1.06)S-3 has orthorhombic symmetry with space group Pnma (No. 62). The asymmetric unit contains two independent mixed cation sites, both coordinated to seven S atoms in a form of mono-capped trigonal prism. They combine into infinite (M4S6)(n) rods parallel to the [010] direction with only weak interactions between rods where the lone electron pairs are directed. Our data and the revaluation of previous data resolve a controversy about the distribution of Sb and Bi over the two structural sites which exists in previously published works. It is shown that the structural constraints favour a slight preference of the larger cation for the marginal M1 site over the whole span of the solid-solution series. The unit cell parameters show a deviation form the Vegard's law connected with different rates of the parallel increase of lengths of the strong bonds and the decreasing influence of the lone electron pair with the replacement of Sb by Bi. The changes in the character of the two independent cation sites introduced by this replacement are similar to those produced during compression of Sb2S3.",
publisher = "E Schweizerbartsche Verlagsbuchhandlung, Stuttgart",
journal = "Neues Jahrbuch Fur Mineralogie. Abhandlungen",
title = "Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series",
volume = "189",
number = "2",
pages = "177-187",
doi = "10.1127/0077-7757/2012/0217"
}

Poleti, D., Karanovic, L., Balic-Zunic, T.,& Gržetić, I.. (2012). Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series. in Neues Jahrbuch Fur Mineralogie. Abhandlungen
E Schweizerbartsche Verlagsbuchhandlung, Stuttgart., 189(2), 177-187.
https://doi.org/10.1127/0077-7757/2012/0217

Poleti D, Karanovic L, Balic-Zunic T, Gržetić I. Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series. in Neues Jahrbuch Fur Mineralogie. Abhandlungen. 2012;189(2):177-187.
doi:10.1127/0077-7757/2012/0217 .

Poleti, Dejan, Karanovic, Ljiljana, Balic-Zunic, Tonci, Gržetić, Ivan, "Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series" in Neues Jahrbuch Fur Mineralogie. Abhandlungen, 189, no. 2 (2012):177-187,
https://doi.org/10.1127/0077-7757/2012/0217 . .

TY  - JOUR
AU  - Karanovic, Ljiljana
AU  - Poleti, Dejan
AU  - Balic-Zunic, Tonci
AU  - Makovicky, Emil
AU  - Gržetić, Ivan
PY  - 2008
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/937
AB  - Two new sulphosalts Tl(3)Ag(3)Sb(2)S(6), (1) and Tl(3)Ag(3)AS(2)S(6), (2) were prepared in reaction of synthetic binary sulfides: argentite (Ag(2)S), carlinite (Tl(2)S) and orpiment (As(2)O(3)) or stibnite (Sb(2)S(3)), and their crystal structures have been determined using single-crystal data. The compounds are isostructural and crystallize in the space group P2(1)/C (Z = 4), with a = 11.6854(17) angstrom, b = 11.8602(17) angstrom, c = 12.1294(18) angstrom, beta = 123.356(2)degrees, V = 1404.1(4) angstrom(3) for 1, and a = 11.4415(14) angstrom, b = 11.7530(15) angstrom, c = 11.9880(16) angstrom, beta = 123.516(3)degrees, V= 1344.0(3) angstrom(3) for2. Refinements involving anisotropic displacement parameters for all atoms converged to the conventional R-factors: R(1) = 0.0496 for 1 and R(1) = 0.0372 for 2. The structures consist of two kinds of slabs alternately situated along [1 0 0] direction and sharing S atoms located between them. The first slab is built up of Tl1S(8), Tl(2)S(6), Tl(3)S(5)Ag(3) coordination polyhedra and Ag(3)S(3)n(3) distorted trigonal pyramid (the average  lt  Ag(3)-S  gt  distance is 2.542 for 1 and 2.539 angstrom for 2) combined with trigonal Sb1S(3) or As1S(3) coordination pyramids ( lt  Sb1-S  gt  and  lt  As1-S  gt  are 2.438 and 2.259 angstrom, respectively). The thallium atom Tl1 is surrounded by eight S atoms forming a square anti-prism ( lt  Tl1-S  gt : 3.393 for 1 and 3.356 angstrom for 2), while the coordination polyhedron of Tl2 can be described as a significantly distorted trigonal prism or as an extremely distorted octahedron ( lt  Tl2-S  gt : 3.236 angstrom for 1 and 3.238 angstrom for 2). Thallium Tl3 is surrounded by six atoms (one Ag, four S at shorter and one S at longer distance), which form a distorted trigonal prism ( lt  Tl3-S  gt : 3.165 angstrom in 1 and 3.155 angstrom in 2). The second slab consists of trigonal Sb(2)S(3) or As(2)S(3) coordination pyramids combined with Ag1S(4) and Ag(2)S(4) coordination tetrahedra ( lt  Sb2-S  gt  and  lt  As2-S  gt  are 2.433 and 2.251 angstrom, respectively;  lt  Ag1-S  gt : 2.623 angstrom for 1 and 2.612 A for 2;  lt  Ag2-S  gt : 2.623 angstrom for 1 and 2.630 angstrom for 2). The most interesting feature of both structures is the existence of short Tl3-Ag(3) contacts of 2.959(2) angstrom in 1 and 2.922(1) angstrom in 2. These contacts are the shortest found so far and indicate very strong Tl-Ag interactions. They are discussed in terms of metallophilicity principle and relativistic effects. It is also pointed out that if only valence shell electrons are considered (Tl-Ag)(2+) group is isoelectronic with the (Hg-Hg)(2+) ion, therefore new examples of short Tl-Ag contacts could be expected. (C) 2007 Elsevier B.V. All rights reserved.
PB  - Elsevier Science Sa, Lausanne
T2  - Journal of Alloys and Compounds
T1  - Two new examples of very short thallium-transition metal contacts: Tl(3)Ag(3)Sb(2)S(6) and Tl(3)Ag(3)As(2)S(6)
VL  - 457
IS  - 1-2
SP  - 66
EP  - 74
DO  - 10.1016/j.jallcom.2007.03.014
ER  - 

@article{
author = "Karanovic, Ljiljana and Poleti, Dejan and Balic-Zunic, Tonci and Makovicky, Emil and Gržetić, Ivan",
year = "2008",
abstract = "Two new sulphosalts Tl(3)Ag(3)Sb(2)S(6), (1) and Tl(3)Ag(3)AS(2)S(6), (2) were prepared in reaction of synthetic binary sulfides: argentite (Ag(2)S), carlinite (Tl(2)S) and orpiment (As(2)O(3)) or stibnite (Sb(2)S(3)), and their crystal structures have been determined using single-crystal data. The compounds are isostructural and crystallize in the space group P2(1)/C (Z = 4), with a = 11.6854(17) angstrom, b = 11.8602(17) angstrom, c = 12.1294(18) angstrom, beta = 123.356(2)degrees, V = 1404.1(4) angstrom(3) for 1, and a = 11.4415(14) angstrom, b = 11.7530(15) angstrom, c = 11.9880(16) angstrom, beta = 123.516(3)degrees, V= 1344.0(3) angstrom(3) for2. Refinements involving anisotropic displacement parameters for all atoms converged to the conventional R-factors: R(1) = 0.0496 for 1 and R(1) = 0.0372 for 2. The structures consist of two kinds of slabs alternately situated along [1 0 0] direction and sharing S atoms located between them. The first slab is built up of Tl1S(8), Tl(2)S(6), Tl(3)S(5)Ag(3) coordination polyhedra and Ag(3)S(3)n(3) distorted trigonal pyramid (the average  lt  Ag(3)-S  gt  distance is 2.542 for 1 and 2.539 angstrom for 2) combined with trigonal Sb1S(3) or As1S(3) coordination pyramids ( lt  Sb1-S  gt  and  lt  As1-S  gt  are 2.438 and 2.259 angstrom, respectively). The thallium atom Tl1 is surrounded by eight S atoms forming a square anti-prism ( lt  Tl1-S  gt : 3.393 for 1 and 3.356 angstrom for 2), while the coordination polyhedron of Tl2 can be described as a significantly distorted trigonal prism or as an extremely distorted octahedron ( lt  Tl2-S  gt : 3.236 angstrom for 1 and 3.238 angstrom for 2). Thallium Tl3 is surrounded by six atoms (one Ag, four S at shorter and one S at longer distance), which form a distorted trigonal prism ( lt  Tl3-S  gt : 3.165 angstrom in 1 and 3.155 angstrom in 2). The second slab consists of trigonal Sb(2)S(3) or As(2)S(3) coordination pyramids combined with Ag1S(4) and Ag(2)S(4) coordination tetrahedra ( lt  Sb2-S  gt  and  lt  As2-S  gt  are 2.433 and 2.251 angstrom, respectively;  lt  Ag1-S  gt : 2.623 angstrom for 1 and 2.612 A for 2;  lt  Ag2-S  gt : 2.623 angstrom for 1 and 2.630 angstrom for 2). The most interesting feature of both structures is the existence of short Tl3-Ag(3) contacts of 2.959(2) angstrom in 1 and 2.922(1) angstrom in 2. These contacts are the shortest found so far and indicate very strong Tl-Ag interactions. They are discussed in terms of metallophilicity principle and relativistic effects. It is also pointed out that if only valence shell electrons are considered (Tl-Ag)(2+) group is isoelectronic with the (Hg-Hg)(2+) ion, therefore new examples of short Tl-Ag contacts could be expected. (C) 2007 Elsevier B.V. All rights reserved.",
publisher = "Elsevier Science Sa, Lausanne",
journal = "Journal of Alloys and Compounds",
title = "Two new examples of very short thallium-transition metal contacts: Tl(3)Ag(3)Sb(2)S(6) and Tl(3)Ag(3)As(2)S(6)",
volume = "457",
number = "1-2",
pages = "66-74",
doi = "10.1016/j.jallcom.2007.03.014"
}

Karanovic, L., Poleti, D., Balic-Zunic, T., Makovicky, E.,& Gržetić, I.. (2008). Two new examples of very short thallium-transition metal contacts: Tl(3)Ag(3)Sb(2)S(6) and Tl(3)Ag(3)As(2)S(6). in Journal of Alloys and Compounds
Elsevier Science Sa, Lausanne., 457(1-2), 66-74.
https://doi.org/10.1016/j.jallcom.2007.03.014

Karanovic L, Poleti D, Balic-Zunic T, Makovicky E, Gržetić I. Two new examples of very short thallium-transition metal contacts: Tl(3)Ag(3)Sb(2)S(6) and Tl(3)Ag(3)As(2)S(6). in Journal of Alloys and Compounds. 2008;457(1-2):66-74.
doi:10.1016/j.jallcom.2007.03.014 .

Karanovic, Ljiljana, Poleti, Dejan, Balic-Zunic, Tonci, Makovicky, Emil, Gržetić, Ivan, "Two new examples of very short thallium-transition metal contacts: Tl(3)Ag(3)Sb(2)S(6) and Tl(3)Ag(3)As(2)S(6)" in Journal of Alloys and Compounds, 457, no. 1-2 (2008):66-74,
https://doi.org/10.1016/j.jallcom.2007.03.014 . .