TY - JOUR
T1 - Crystal structure refinement of MnTe2, MnSe2, and MnS2
T2 - Cation-anion and anion-anion bonding distances in pyrite-type structures
AU - Tokuda, Makoto
AU - Yoshiasa, Akira
AU - Mashimo, Tsutomu
AU - Arima, Hiroshi
AU - Hongu, Hidetomo
AU - Tobase, Tsubasa
AU - Nakatsuka, Akihiko
AU - Sugiyama, Kazumasa
PY - 2019/6/1
Y1 - 2019/6/1
N2 - The stability of hauerite (MnS2) as compared to that of pyrite (FeS2) can be explained by the long Mn-S distance and departure from the typical pyrite-type structures. The structural differences of MnX2 compounds (X=S, Se, and Te) are the result of spin configurations that are different than those of other MX2 compounds; however, the arrangement of d-electrons and the size of the ions in MnX2 compounds do not clearly explain why Mn2+ in MnX2 does not exist as a low spin state. To investigate the structural differences of MnX2 compounds, we synthesized single-crystal MnTe2 and MnSe2 and performed single-crsytal X-ray diffraction experiments. The single-crystal X-ray diffraction experiments were conducted on MnTe2 [a=6.9513(1) Å, u-parameter=0.38554(2), space group Pa3̄ , Z=4], MnSe2 [a=6.4275(2) Å, u-parameter=0.39358(2)], MnS2 [hauerite; a=6.1013(1) Å, u-parameter=0.40105(4), obtained from Osorezan, Aomori, Japan], and FeS2 [pyrite; a=5.4190(1) Å, u-parameter 0.38484(5), obtained from Kawarakoba, Nagasaki, Japan]. The X-ray intensity datasets of these compounds do not show any evidence of symmetry reduction. In MnS2, the S-S distance is 2.0915(8) Å, which is significantly shorter than that of FeS2 (2.1618(9) Å), and the mean square displacement of S (U11=0.00915(9) Å2) is smaller than that of Mn (U11=0.01137(9) Å2). The thermal vibration characteristics of MnX2 compounds are significantly different than those of FeS2. Based on structural refinement data, we discuss the low spin state of MnX2 compounds and the structural stability of pyrite-type structures.
AB - The stability of hauerite (MnS2) as compared to that of pyrite (FeS2) can be explained by the long Mn-S distance and departure from the typical pyrite-type structures. The structural differences of MnX2 compounds (X=S, Se, and Te) are the result of spin configurations that are different than those of other MX2 compounds; however, the arrangement of d-electrons and the size of the ions in MnX2 compounds do not clearly explain why Mn2+ in MnX2 does not exist as a low spin state. To investigate the structural differences of MnX2 compounds, we synthesized single-crystal MnTe2 and MnSe2 and performed single-crsytal X-ray diffraction experiments. The single-crystal X-ray diffraction experiments were conducted on MnTe2 [a=6.9513(1) Å, u-parameter=0.38554(2), space group Pa3̄ , Z=4], MnSe2 [a=6.4275(2) Å, u-parameter=0.39358(2)], MnS2 [hauerite; a=6.1013(1) Å, u-parameter=0.40105(4), obtained from Osorezan, Aomori, Japan], and FeS2 [pyrite; a=5.4190(1) Å, u-parameter 0.38484(5), obtained from Kawarakoba, Nagasaki, Japan]. The X-ray intensity datasets of these compounds do not show any evidence of symmetry reduction. In MnS2, the S-S distance is 2.0915(8) Å, which is significantly shorter than that of FeS2 (2.1618(9) Å), and the mean square displacement of S (U11=0.00915(9) Å2) is smaller than that of Mn (U11=0.01137(9) Å2). The thermal vibration characteristics of MnX2 compounds are significantly different than those of FeS2. Based on structural refinement data, we discuss the low spin state of MnX2 compounds and the structural stability of pyrite-type structures.
KW - Debye temperature
KW - MnSe
KW - MnTe
KW - hauerite
KW - pyrite-type
UR - http://www.scopus.com/inward/record.url?scp=85061119141&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85061119141&partnerID=8YFLogxK
U2 - 10.1515/zkri-2018-2134
DO - 10.1515/zkri-2018-2134
M3 - Article
AN - SCOPUS:85061119141
VL - 234
SP - 371
EP - 377
JO - Zeitschrift fur Kristallographie - Crystalline Materials
JF - Zeitschrift fur Kristallographie - Crystalline Materials
SN - 2194-4946
IS - 6
ER -