Crystal structure of (Bi0.94Sb1.06)S-3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series
Апстракт
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 pu...blished 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.
Кључне речи:
bismuthinite / stibnite / crystal structure / solid-solution / Sb-Bi substitution / lone electron pairИзвор:
Neues Jahrbuch Fur Mineralogie. Abhandlungen, 2012, 189, 2, 177-187Издавач:
- E Schweizerbartsche Verlagsbuchhandlung, Stuttgart
Финансирање / пројекти:
- 0-3D наноструктуре за примену у електроници и обновљивим изворима енергије: синтеза, карактеризација и процесирање (RS-MESTD-Integrated and Interdisciplinary Research (IIR or III)-45007)
- National Research Council of Denmark
DOI: 10.1127/0077-7757/2012/0217
ISSN: 0077-7757
WoS: 000303482700005
Scopus: 2-s2.0-84864408447
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - 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 . .