A Revised Structure Model for the UCl 6 Structure Type, Novel Modifications of UCl 6 and UBr 5 , and a Comment on the Modifications of Protactinium Pentabromides

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A Revised Structure Model for the UCl 6 Structure Type, Novel Modifications of UCl 6 and UBr 5 , and a Comment on the Modifications of Protactinium Pentabromides. / Deubner, H. Lars; Rudel, Stefan S.; Sachs, Malte; Pietzonka, Clemens; Karttunen, Antti J.; Ivlev, Sergei I.; Müller, Matthias; Conrad, Matthias; Müller, Ulrich; Kraus, Florian.

In: Chemistry - A European Journal, Vol. 25, No. 25, 02.05.2019, p. 6402-6411.

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Deubner, H. Lars ; Rudel, Stefan S. ; Sachs, Malte ; Pietzonka, Clemens ; Karttunen, Antti J. ; Ivlev, Sergei I. ; Müller, Matthias ; Conrad, Matthias ; Müller, Ulrich ; Kraus, Florian. / A Revised Structure Model for the UCl 6 Structure Type, Novel Modifications of UCl 6 and UBr 5 , and a Comment on the Modifications of Protactinium Pentabromides. In: Chemistry - A European Journal. 2019 ; Vol. 25, No. 25. pp. 6402-6411.

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@article{a4e7c19d9d7640479bd27e45acfa8a15,
title = "A Revised Structure Model for the UCl 6 Structure Type, Novel Modifications of UCl 6 and UBr 5 , and a Comment on the Modifications of Protactinium Pentabromides",
abstract = "The redetermination of the crystal structure of trigonal UCl 6 , which is the eponym for the UCl 6 structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U−Cl distances within the octahedral UCl 6 molecule (2.41 and 2.51 {\AA}). Within the revised structure model presented here, which is based on single crystal data as well as quantum chemical calculations, all U−Cl distances are essentially equal within standard uncertainty (2.431(5), 2.437(5), and 2.439(6) {\AA}). This room temperature modification, called rt-UCl 6 , crystallizes in the trigonal space group P (Formula presented.) m1, No. 164, hP21, with a=10.907(2), c=5.9883(12) {\AA}, V=616.9(2) {\AA} 3 , Z=3 at T=253 K. A new low-temperature (lt) modification of UCl 6 is also presented that was obtained by cooling a single crystal of rt-UCl 6. The phase change occurs between 150 and 175 K. lt-UCl 6 crystallizes isotypic to a low-temperature modification of SF 6 in the monoclinic crystal system, space group C2/m, No. 12, mS42, with a=17.847(4), b=10.8347(18), c=6.2670(17) {\AA}, β=96.68(2)°, V=1203.6(5) {\AA} 3 , Z=6 at 100 K. The Cl anions form a close-packed structure corresponding to the α-Sm type with uranium atoms in the octahedral voids. During the synthesis of UBr 5 a new modification was obtained that crystallizes in the triclinic crystal system, space group P (Formula presented.), No. 2, aP36, with a=10.4021(6), b=11.1620(6), c=12.2942(7) {\AA}, α=68.3340(10)°, β=69.6410(10)° and γ=89.5290(10)°, V=1231.84(12) {\AA} 3 , Z=3 at T=100 K. In this structure the UBr 5 units are dimerized to U 2 Br 10 molecules. The Br anions also form a close-packed structure of the α-Sm type with adjacent uranium atoms in the octahedral voids. Comparisons of the crystal structures of the compounds MX 5 (M=Pa, U; X=Cl, Br) show that the crystal structure of monoclinic α-PaBr 5 is probably not correct.",
keywords = "bromide, chloride, crystal structures, protactinium, uranium",
author = "Deubner, {H. Lars} and Rudel, {Stefan S.} and Malte Sachs and Clemens Pietzonka and Karttunen, {Antti J.} and Ivlev, {Sergei I.} and Matthias M{\"u}ller and Matthias Conrad and Ulrich M{\"u}ller and Florian Kraus",
note = "FAM on suljettu, kunnes embargoaika voidaa m{\"a}{\"a}ritell{\"a}.MSo/26.4.19",
year = "2019",
month = "5",
day = "2",
doi = "10.1002/chem.201900389",
language = "English",
volume = "25",
pages = "6402--6411",
journal = "CHEMISTRY: A EUROPEAN JOURNAL",
issn = "0947-6539",
number = "25",

}

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TY - JOUR

T1 - A Revised Structure Model for the UCl 6 Structure Type, Novel Modifications of UCl 6 and UBr 5 , and a Comment on the Modifications of Protactinium Pentabromides

AU - Deubner, H. Lars

AU - Rudel, Stefan S.

AU - Sachs, Malte

AU - Pietzonka, Clemens

AU - Karttunen, Antti J.

AU - Ivlev, Sergei I.

AU - Müller, Matthias

AU - Conrad, Matthias

AU - Müller, Ulrich

AU - Kraus, Florian

N1 - FAM on suljettu, kunnes embargoaika voidaa määritellä.MSo/26.4.19

PY - 2019/5/2

Y1 - 2019/5/2

N2 - The redetermination of the crystal structure of trigonal UCl 6 , which is the eponym for the UCl 6 structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U−Cl distances within the octahedral UCl 6 molecule (2.41 and 2.51 Å). Within the revised structure model presented here, which is based on single crystal data as well as quantum chemical calculations, all U−Cl distances are essentially equal within standard uncertainty (2.431(5), 2.437(5), and 2.439(6) Å). This room temperature modification, called rt-UCl 6 , crystallizes in the trigonal space group P (Formula presented.) m1, No. 164, hP21, with a=10.907(2), c=5.9883(12) Å, V=616.9(2) Å 3 , Z=3 at T=253 K. A new low-temperature (lt) modification of UCl 6 is also presented that was obtained by cooling a single crystal of rt-UCl 6. The phase change occurs between 150 and 175 K. lt-UCl 6 crystallizes isotypic to a low-temperature modification of SF 6 in the monoclinic crystal system, space group C2/m, No. 12, mS42, with a=17.847(4), b=10.8347(18), c=6.2670(17) Å, β=96.68(2)°, V=1203.6(5) Å 3 , Z=6 at 100 K. The Cl anions form a close-packed structure corresponding to the α-Sm type with uranium atoms in the octahedral voids. During the synthesis of UBr 5 a new modification was obtained that crystallizes in the triclinic crystal system, space group P (Formula presented.), No. 2, aP36, with a=10.4021(6), b=11.1620(6), c=12.2942(7) Å, α=68.3340(10)°, β=69.6410(10)° and γ=89.5290(10)°, V=1231.84(12) Å 3 , Z=3 at T=100 K. In this structure the UBr 5 units are dimerized to U 2 Br 10 molecules. The Br anions also form a close-packed structure of the α-Sm type with adjacent uranium atoms in the octahedral voids. Comparisons of the crystal structures of the compounds MX 5 (M=Pa, U; X=Cl, Br) show that the crystal structure of monoclinic α-PaBr 5 is probably not correct.

AB - The redetermination of the crystal structure of trigonal UCl 6 , which is the eponym for the UCl 6 structure type, showed that certain atomic coordinates had been incorrectly reported. This led to noticeably different U−Cl distances within the octahedral UCl 6 molecule (2.41 and 2.51 Å). Within the revised structure model presented here, which is based on single crystal data as well as quantum chemical calculations, all U−Cl distances are essentially equal within standard uncertainty (2.431(5), 2.437(5), and 2.439(6) Å). This room temperature modification, called rt-UCl 6 , crystallizes in the trigonal space group P (Formula presented.) m1, No. 164, hP21, with a=10.907(2), c=5.9883(12) Å, V=616.9(2) Å 3 , Z=3 at T=253 K. A new low-temperature (lt) modification of UCl 6 is also presented that was obtained by cooling a single crystal of rt-UCl 6. The phase change occurs between 150 and 175 K. lt-UCl 6 crystallizes isotypic to a low-temperature modification of SF 6 in the monoclinic crystal system, space group C2/m, No. 12, mS42, with a=17.847(4), b=10.8347(18), c=6.2670(17) Å, β=96.68(2)°, V=1203.6(5) Å 3 , Z=6 at 100 K. The Cl anions form a close-packed structure corresponding to the α-Sm type with uranium atoms in the octahedral voids. During the synthesis of UBr 5 a new modification was obtained that crystallizes in the triclinic crystal system, space group P (Formula presented.), No. 2, aP36, with a=10.4021(6), b=11.1620(6), c=12.2942(7) Å, α=68.3340(10)°, β=69.6410(10)° and γ=89.5290(10)°, V=1231.84(12) Å 3 , Z=3 at T=100 K. In this structure the UBr 5 units are dimerized to U 2 Br 10 molecules. The Br anions also form a close-packed structure of the α-Sm type with adjacent uranium atoms in the octahedral voids. Comparisons of the crystal structures of the compounds MX 5 (M=Pa, U; X=Cl, Br) show that the crystal structure of monoclinic α-PaBr 5 is probably not correct.

KW - bromide

KW - chloride

KW - crystal structures

KW - protactinium

KW - uranium

UR - http://www.scopus.com/inward/record.url?scp=85064092543&partnerID=8YFLogxK

U2 - 10.1002/chem.201900389

DO - 10.1002/chem.201900389

M3 - Article

VL - 25

SP - 6402

EP - 6411

JO - CHEMISTRY: A EUROPEAN JOURNAL

JF - CHEMISTRY: A EUROPEAN JOURNAL

SN - 0947-6539

IS - 25

ER -

ID: 33285847