‘Rhythmite’, Ca29(SiO4)8Cl26, an Anthropogenic Phase from the Chelyabinsk Coal Basin (Ural, Russia) with a Complex Modular Structure Related to α-Ca3SiO4Cl2 (‘Albovite’): Crystal Structure, Raman Spectra, and Thermal Expansion

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‘Rhythmite’, Ca29(SiO4)8Cl26, an Anthropogenic Phase from the Chelyabinsk Coal Basin (Ural, Russia) with a Complex Modular Structure Related to α-Ca3SiO4Cl2 (‘Albovite’): Crystal Structure, Raman Spectra, and Thermal Expansion. / Avdontceva, Margarita S.; Zolotarev, Andrey A.; Brazhnikova, Anastasia S.; Bocharov, Vladimir N.; Vlasenko, Natalia S.; Rassomakhin, Mikhail A.; Krivovichev, Sergey V.

In: Minerals, Vol. 14, No. 10, 1048, 18.10.2024.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{817a8c1fae0d43428adc36ada8a4e7d9,

title = "{\textquoteleft}Rhythmite{\textquoteright}, Ca29(SiO4)8Cl26, an Anthropogenic Phase from the Chelyabinsk Coal Basin (Ural, Russia) with a Complex Modular Structure Related to α-Ca3SiO4Cl2 ({\textquoteleft}Albovite{\textquoteright}): Crystal Structure, Raman Spectra, and Thermal Expansion",

abstract = "{\textquoteleft}Rhythmite{\textquoteright}, Ca29(SiO4)8Cl26, an anthropogenic calcium chloride silicate from the Chelyabinsk coal basin (South Ural, Russia), was investigated using chemical microprobe analysis, in situ single-crystal X-ray diffraction analysis (27–727 °C), and Raman spectroscopy. {\textquoteleft}Rhythmite{\textquoteright} is orthorhombic, Pnma: a = 17.0749(6), b = 15.1029(5), c = 13.2907(4) {\AA}, and V = 3427.42(18) {\AA}3 (R1 = 0.045). The crystal structure of {\textquoteleft}rhythmite{\textquoteright} consists of a porous framework formed by Ca-O bonds and SiO4 tetrahedra with additional Ca2+ cations and Cl− anions in the structure interstices. The framework is built up from multinuclear [Ca15(SiO4)4]14+ fundamental building blocks (FBBs) cut from the crystal structure of α-Ca3SiO4Cl2 ({\textquoteleft}albovite{\textquoteright}). The FBBs are linked by sharing common Ca atoms to form a network with an overall pcu topology. The empirical chemical formula was calculated as Ca29.02(Si7.89Al0.05P0.05)Ʃ7.99O32Cl26 (on the basis of Cl + O = 58). {\textquoteleft}Rhythmite{\textquoteright} is stable up to 627 °C and expands slightly anisotropically (αmax/αmin = 1.40) in the ab and bc planes and almost isotropically in the ac plane (α33/α11 = 1.02) with the following thermal expansion coefficients (×106 °C−1): α11 = 14.6(1), α22 = 20.5(4), α33 = 15.0(3), and αV = 50.1(6) (room temperature). During expansion, the silicate tetrahedra remain relatively rigid with average bond length changes of less than 0.5%. A structural complexity analysis indicates that {\textquoteleft}rhythmite{\textquoteright} is complex, with IG,total = 920.313 (bits/u.c.), which significantly exceeds the average value of structural complexity for silicates and is caused by the modular framework construction and the presence of a large number of independent positions in the crystal structure.",

keywords = "Raman spectroscopy, crystal structure solution, mineral-like phase, thermal behaviour, thermal stability, {\textquoteleft}rhythmite{\textquoteright}",

author = "Avdontceva, {Margarita S.} and Zolotarev, {Andrey A.} and Brazhnikova, {Anastasia S.} and Bocharov, {Vladimir N.} and Vlasenko, {Natalia S.} and Rassomakhin, {Mikhail A.} and Krivovichev, {Sergey V.}",

year = "2024",

month = oct,

day = "18",

doi = "10.3390/min14101048",

language = "English",

volume = "14",

journal = "Minerals",

issn = "2075-163X",

publisher = "MDPI AG",

number = "10",

}

RIS

TY - JOUR

T1 - ‘Rhythmite’, Ca29(SiO4)8Cl26, an Anthropogenic Phase from the Chelyabinsk Coal Basin (Ural, Russia) with a Complex Modular Structure Related to α-Ca3SiO4Cl2 (‘Albovite’): Crystal Structure, Raman Spectra, and Thermal Expansion

AU - Avdontceva, Margarita S.

AU - Zolotarev, Andrey A.

AU - Brazhnikova, Anastasia S.

AU - Bocharov, Vladimir N.

AU - Vlasenko, Natalia S.

AU - Rassomakhin, Mikhail A.

AU - Krivovichev, Sergey V.

PY - 2024/10/18

Y1 - 2024/10/18

N2 - ‘Rhythmite’, Ca29(SiO4)8Cl26, an anthropogenic calcium chloride silicate from the Chelyabinsk coal basin (South Ural, Russia), was investigated using chemical microprobe analysis, in situ single-crystal X-ray diffraction analysis (27–727 °C), and Raman spectroscopy. ‘Rhythmite’ is orthorhombic, Pnma: a = 17.0749(6), b = 15.1029(5), c = 13.2907(4) Å, and V = 3427.42(18) Å3 (R1 = 0.045). The crystal structure of ‘rhythmite’ consists of a porous framework formed by Ca-O bonds and SiO4 tetrahedra with additional Ca2+ cations and Cl− anions in the structure interstices. The framework is built up from multinuclear [Ca15(SiO4)4]14+ fundamental building blocks (FBBs) cut from the crystal structure of α-Ca3SiO4Cl2 (‘albovite’). The FBBs are linked by sharing common Ca atoms to form a network with an overall pcu topology. The empirical chemical formula was calculated as Ca29.02(Si7.89Al0.05P0.05)Ʃ7.99O32Cl26 (on the basis of Cl + O = 58). ‘Rhythmite’ is stable up to 627 °C and expands slightly anisotropically (αmax/αmin = 1.40) in the ab and bc planes and almost isotropically in the ac plane (α33/α11 = 1.02) with the following thermal expansion coefficients (×106 °C−1): α11 = 14.6(1), α22 = 20.5(4), α33 = 15.0(3), and αV = 50.1(6) (room temperature). During expansion, the silicate tetrahedra remain relatively rigid with average bond length changes of less than 0.5%. A structural complexity analysis indicates that ‘rhythmite’ is complex, with IG,total = 920.313 (bits/u.c.), which significantly exceeds the average value of structural complexity for silicates and is caused by the modular framework construction and the presence of a large number of independent positions in the crystal structure.

AB - ‘Rhythmite’, Ca29(SiO4)8Cl26, an anthropogenic calcium chloride silicate from the Chelyabinsk coal basin (South Ural, Russia), was investigated using chemical microprobe analysis, in situ single-crystal X-ray diffraction analysis (27–727 °C), and Raman spectroscopy. ‘Rhythmite’ is orthorhombic, Pnma: a = 17.0749(6), b = 15.1029(5), c = 13.2907(4) Å, and V = 3427.42(18) Å3 (R1 = 0.045). The crystal structure of ‘rhythmite’ consists of a porous framework formed by Ca-O bonds and SiO4 tetrahedra with additional Ca2+ cations and Cl− anions in the structure interstices. The framework is built up from multinuclear [Ca15(SiO4)4]14+ fundamental building blocks (FBBs) cut from the crystal structure of α-Ca3SiO4Cl2 (‘albovite’). The FBBs are linked by sharing common Ca atoms to form a network with an overall pcu topology. The empirical chemical formula was calculated as Ca29.02(Si7.89Al0.05P0.05)Ʃ7.99O32Cl26 (on the basis of Cl + O = 58). ‘Rhythmite’ is stable up to 627 °C and expands slightly anisotropically (αmax/αmin = 1.40) in the ab and bc planes and almost isotropically in the ac plane (α33/α11 = 1.02) with the following thermal expansion coefficients (×106 °C−1): α11 = 14.6(1), α22 = 20.5(4), α33 = 15.0(3), and αV = 50.1(6) (room temperature). During expansion, the silicate tetrahedra remain relatively rigid with average bond length changes of less than 0.5%. A structural complexity analysis indicates that ‘rhythmite’ is complex, with IG,total = 920.313 (bits/u.c.), which significantly exceeds the average value of structural complexity for silicates and is caused by the modular framework construction and the presence of a large number of independent positions in the crystal structure.

KW - Raman spectroscopy

KW - crystal structure solution

KW - mineral-like phase

KW - thermal behaviour

KW - thermal stability

KW - ‘rhythmite’

UR - https://www.mendeley.com/catalogue/dff02b31-1076-3083-b56c-ec1bec05a8be/

U2 - 10.3390/min14101048

DO - 10.3390/min14101048

M3 - Article

VL - 14

JO - Minerals

JF - Minerals

SN - 2075-163X

IS - 10

M1 - 1048

ER -

ID: 126384984