Startseite Single-crystal structure determination of Tm3B12O19(OH)7
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Single-crystal structure determination of Tm3B12O19(OH)7

  • Tobias A. Teichtmeister und Hubert Huppertz ORCID logo EMAIL logo
Veröffentlicht/Copyright: 3. April 2024

Abstract

Tm3B12O19(OH)7, monoclinic, C2 (no. 5), a = 23.9849(5) Å, b = 4.4400(1) Å, c = 7.0771(1) Å, β = 94.698(1)°, V = 751.13(3) Å3, Z = 2, R gt(F) = 0.0106, wR ref(F 2) = 0.0247, T = 298(1) K.

CCDC no.: 2331017

Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal: Colorless block
Size: 0.07 × 0.03 × 0.02 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 17.7 mm−1
Diffractometer, scan mode: Bruker D8 Quest Photon III C14, φ and ω
θ max, completeness: 42.2°, 99 %
N(hkl)measured, N(hkl)unique, R int: 41,740, 5280, 0.029
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 5263
N(param)refined: 203
Programs: SHELX [1, 2], Olex2 [3], Diamond [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

Atom x y z U iso*/U eq
Tm1 0.18015 (2) 0.13698 (2) 0.16483 (2) 0.00545 (2)
Tm2 0.000000 0.99697 (2) 0.000000 0.00439 (2)
B1 0.06367 (7) 0.4885 (5) 0.3108 (2) 0.0051 (2)
B2 0.13616 (7) 0.2662 (5) 0.5426 (2) 0.0047 (2)
B3 0.27567 (8) 0.6021 (4) 0.2851 (3) 0.0052 (3)
B4 0.31840 (8) 0.0929 (4) 0.1794 (3) 0.0048 (2)
B5 0.40700 (8) 0.0913 (4) 0.0183 (3) 0.0052 (3)
B6 0.41302 (7) 0.2667 (5) 0.3561 (2) 0.0048 (2)
O1 0.51768 (5) 0.7677 (4) 0.26816 (19) 0.00796 (18)
O2 0.09918 (6) 0.0823 (3) 0.64278 (19) 0.00582 (18)
O3 0.11635 (5) 0.3280 (3) 0.34715 (17) 0.00528 (18)
O4 0.19201 (5) 0.1515 (3) 0.53529 (17) 0.00568 (17)
O5 0.27203 (5) 0.2849 (3) 0.22268 (18) 0.00550 (17)
O6 0.28427 (6) 0.1865 (3) 0.69565 (19) 0.0068 (2)
O7 0.29678 (5) 0.7890 (3) 0.13364 (17) 0.00543 (17)
O8 0.34788 (6) 0.2006 (3) 0.01878 (19) 0.00573 (18)
O9 0.36076 (6) 0.0716 (3) 0.35141 (19) 0.00448 (18)
O10 0.40730 (5) 0.7574 (3) 0.02069 (18) 0.00579 (17)
O11 0.44120 (5) 0.2139 (3) 0.18164 (18) 0.00479 (17)
O12 0.44986 (5) 0.1632 (3) 0.52037 (17) 0.00506 (18)
O13 0.56760 (6) 0.1929 (3) 0.14960 (18) 0.00632 (19)
H6 0.2885 (18) 0.164 (10) 0.582 (3) 0.018 (10)*
H10 0.4023 (17) 0.682 (9) 0.127 (4) 0.017 (10)*
H12a 0.4820 (14) 0.159 (16) 0.486 (9) 0.003 (13)*
H1 0.4902 (18) 0.862 (14) 0.287 (8) 0.055 (18)*
  1. aOccupancy: 0.5.

1 Source of material

The formation of Tm3B12O19(OH)7 was observed during the investigation of the system Tm2O3–Cr2O3–B2O3 at elevated pressures. The starting materials Tm2O3 (0.11 mmol, ChemPur, 99.90 %), Cr(NO3)3·9H2O (0.22 mmol, Sigma Aldrich, 99 %), and H3BO3 (0.76 mmol, Roth, >99.8 %) were carefully ground in an agate mortar, and the mixture was placed in a platinum capsule, which was then centered in a 14/8 assembly of a modified Walker-type multianvil press [5], [6], [7]. Within 317 min, the sample was compressed to 12 GPa, and the temperature was subsequently raised to 850 °C within 10 min. After keeping the temperature constant for 25 min, it was slowly decreased to 500 °C in 45 min, from where the reaction was quenched to room temperature. After the decompression (951 min), the sample consisted of a greyish-green unidentifiable matrix, from which colorless single-crystals of Tm3B12O19(OH)7 could be isolated.

2 Experimental details

According to the systematic absences, possible space groups were C2/m (no. 12), Cm (no. 8), and C2 (no. 5). Out of these, space group C2 (no. 5) was derived as the correct one (Flack parameter: −0.021(4) based on 2384 quotients [2]) during the refinements of the crystal structure. A total of seven hydrogen atoms is needed for charge neutrality, and their sites could be identified by the calculation of the bond valence sums. OH-distances were fixed at 0.83(2) Å using DFIX records and the site occupation factor of the H12 was fixed at 0.5 due to the symmetry of the crystal structure.

3 Comment

The crystal structure of Tm3B12O19(OH)7 is isotypic to Tb3B12O19(OH)7 [8]. The two crystallographically different Tm-sites are nine-fold (Tm1) and eight-fold (Tm2) coordinated by oxygen. Six crystallographically different B-sites are all tetrahedrally coordinated and form [B6O13]8− building blocks of corner-sharing [BO4]5− tetrahedra. Through the connection of the building blocks, a layered crystal structure is built up, and these layers are connected along the crystallographic a-axis via hydrogen-bonding and the thulium-centered polyhedra. Notably, Tm3B12O19(OH)7 was obtained at significantly higher pressures of 12 GPa, compared to its terbium-analogue, which was synthesized at 6 GPa [8]. Investigations at increased pressures in the system Tb4O7–H3BO3 have led to the formation of a different compound with the composition Tb3B10O17(OH)5 [9]. This raises the question if thulium can also adopt this structure type, possibly at even higher pressures. However, this could not yet be determined.


Corresponding author: Hubert Huppertz, Department of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80–82 A-6020 Innsbruck, Austria, Europe, E-mail:

Acknowledgments

We thank Assoc.–Prof. Dr. Gunter Heymann for the recording of the single-crystal data. Tobias A. Teichtmeister wants to thank the Vice Rector for Research for the grant of a doctoral fellowship at the University of Innsbruck.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

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Received: 2024-02-20
Accepted: 2024-03-20
Published Online: 2024-04-03
Published in Print: 2024-06-25

© 2024 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

Artikel in diesem Heft

  1. Frontmatter
  2. New Crystal Structures
  3. The crystal structure of tris((Z)-2-hydroxy-N-((E)-pyridin-2-ylmethylene)benzohydrazonato-k2O,N)europium(III), C39H30N9O6Eu
  4. Crystal structure of (E)-3-(benzylideneamino)-2-phenylthiazolidin-4-one, C16H14N2OS
  5. The crystal structure of (E)-4-fluoro-N′-(1-(o-tolyl)ethylidene)benzohydrazide, C16H15FN2O
  6. Crystal structure of (6-chloropyridin-3-yl)methyl 2-(6-methoxynaphthalen-2-yl)propanoate, C20H18ClNO3
  7. Crystal structure of methyl 3-methoxy-4-(2-methoxy-2-oxoethoxy)benzoate, C12H14O6
  8. The crystal structure of bis[(4-methoxyphenyl)(picolinoyl)amido-κ2 N:N′]copper(II), C26H22CuN4O4
  9. The crystal structure of poly[di(μ2-aqua)-diaqua-bis(3-aminopyridine-4-carboxylate-κ2 O: O′)-tetra(μ2-3-aminopyridine-4-carboxylate-κ2 O: O′)-dineodymium(III), [Nd2(C6H5N2O2)6(H2O)4] n
  10. The crystal structure of t-butyl 7-[3-(4-fluorophenyl)-1-(propan-2-yl)-1H-indol-2-yl]-3,5-dihydroxyhept-6-enoate, C28H34FNO4
  11. Crystal structure of catena-poly[(benzylamine-κ1 N)-(sorbato-κ1 O)-(μ2-sorbato-κ2 O,O′)-copper(II), C19H23CuNO4
  12. Crystal structure of (4-(2-chlorophenyl)-1H-pyrrol-3-yl)(ferrocenyl) methanone, C21H16ClFeNO
  13. The crystal structure of N-[4-(4-bromophenyl)-1,3-thiazol-2-yl]-3-(2-methylphenyl)-2-sulfanylprop-2-enamide hydrate, C19H17BrN2O2S2
  14. The crystal structure of N′-{5-[2-(2,6-dimethylphenoxy) acetamido]-4-hydroxy-1,6-diphenylhexan-2-yl}-3-methyl-2-(2-oxo-1,3-diazinan-1-yl)butanamide hydrate
  15. Crystal structure of 2-(naphthalen-1-yl)ethyl 2-(6-methoxynaphthalen-2-yl)propanoate, C26H24O3
  16. Crystal structure of naphthalen-1-ylmethyl 2-(6-methoxynaphthalen-2-yl)propanoate, C25H22O3
  17. Crystal structure of poly[diaqua- (μ4-5-(1H-1,2,4-triazol-1-yl)benzene-1,3-dicarboxylato-κ5N:O,O’:O’’:O’’’)calcium(II), C10H9CaN3O6
  18. Crystal structure of (E)-N′-(4-((E)-3-(dimethylamino)acryloyl)-3-hydroxyphenyl)-N, N-dimethylformimidamide, C14H19N3O2
  19. Crystal structure of (E)-3-(dimethylamino)-1-(2-hydroxy-4,6-dimethoxyphenyl)prop-2-en-1-one, C13H17NO4
  20. Crystal structure of (2-chloropyridin-3-yl)methyl-2-(6-methoxynaphthalen-2-yl)propanoate, C20H18ClNO3
  21. The crystal structure of diethyl 4-(3,4-dimethylphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, C21H27NO4
  22. Crystal structure of (8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13-dimethyl-17-((4-(2-phenylpropyl)phenyl)ethynyl)-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-cyclopenta[a]phenanthren-3-one, C36H42O2
  23. Synthesis and crystal structure of 4-(4-cyclopropylnaphthalen-1-yl)-2,4-dihydro-3H-1,2,4-triazole-3-thione, C15H13N3S
  24. Crystal structure of catena-poly[aqua-(2,6-di-(2-pyridyl)-pyridine-κ3 N,N′, N″)(μ2-1,4-naphthalene dicarboxylato-κ2 O,O′)nickel(II)], C27H19NiN3O5
  25. Crystal structure of 3-(diphenylphosphoryl)-3-hydroxy-1-phenylpropan-1-one, C21H19O3P
  26. The crystal structure of R,S-{N-[(2-oxidonaphthalen-1-yl)methylidene]phenylglycinato}divinylsilicon, C23H19NO3Si
  27. The crystal structure of 1,2,4-tris(bromomethyl)benzene, C9H9Br3
  28. Crystal structure of chlorido-[4-(pyridin-2-yl)benzaldehyde-κ2 N,C]-(diethylamine-κ1 N)platinum(II), C16H18ClN2OPt
  29. Crystal structure of 3-(methoxycarbonyl)-1-(4-methoxyphenyl)-2,3,4,9- tetrahydro-1H-pyrido[3,4-b]indol-2-ium chloride hydrate, C40H48Cl2N4O9
  30. The crystal structure of 1-(2-chlorobenzyl)-3-(3-chlorophenyl)urea, C14H12Cl2N2O
  31. Hydrothermal synthesis and crystal structure of aqua-tris(4-acetamidobenzoato-κ2 O,O′)-(1,10-phenanthroline-κ2 N,N′)terbium(III) hydrate C39H36N5O11Tb
  32. The crystal structure of zwitterionic 3-aminoisonicotinic acid, C6H6N2O2
  33. The crystal structure of bis{[monoaqua-μ2-4-[(pyridine-4-carbonyl)-amino]-phthalato-κ3 N:O,O′-(2,2′-bipyridine κ2 N,N′)copper(II)]}decahydrate, C48H56N8O22Cu2
  34. Crystal structure of poly[μ10-4,4′-methylene-bis(oxy)benzoatodipotassium], C15H10K2O6
  35. The crystal structure of catena-poly[[tetraaqua[(μ2-1,4-di(4-methyl-1-imidazolyl)benzene] cobalt(II)]bis(formate)], C16H24CoN4O8
  36. The crystal structure of (E)-2-chloro-5-((2-(nitromethylene)imidazolidin-1-yl)methyl)pyridine, C10H11ClN4O2
  37. The crystal structure of (E)-1-(((2-amino-4,5-dimethylphenyl)iminio)methyl)naphthalen-2-olate, C19H18N2O
  38. Crystal structure of N-(acridin-9-yl)-2-(4-methylpiperidin-1-yl) acetamide monohydrate, C21H25N3O2
  39. The crystal structure of dichlorido-bis(3-methyl-3-imidazolium-1-ylpropionato-κ2 O,O′)-zinc(II), C14H20Cl2N4O4Zn
  40. The crystal structure of 2,8-diethyl-1,3,7,9-tetramethyl-4λ4,5λ4-spiro[dipyrrolo[1,2-c:2′,1′-f][1,3,2]diazaborinine-5,2′-naphtho[1,8-de][1,3,2]dioxaborinine], C25H29BN2O2
  41. The crystal structure of 5-tert-butyl-2-(5-tert-butyl-3-iodo-benzofuran-2-yl)-3-iodobenzofuran, C24H24I2O2
  42. Synthesis and crystal structure of methyl 2-{[4-(4-cyclopropyl-1-naphthyl)-4H-1,2,4-triazole-3-yl]thio} acetate, C18H17N3O2S
  43. The crystal structure of n-propylammonium bis(2,3-dimethylbutane-2,3-diolato)borate-boric acid (1/1), [C3H10N][C12H24BO4]·B(OH)3
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  50. The crystal structure of (2-diphenylphosphanylphenyl) 2-[7-(dimethylamino)-2-oxochromen-4-yl]acetate, C31H26NO4P
  51. Crystal structure of (E)-6-(4-ethylpiperazin-1-yl)-2-(3-fluorobenzylidene)-3,4-dihydronaphthalen-1(2H)-one, C23H25FN2O
  52. The structure of RUB-56, (C6H16N)8 [Si32O64(OH)8]·32 H2O, a hydrous layer silicate (2D-zeolite) that contains microporous levyne-type silicate layers
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  54. Crystal structure of 2-(naphthalen-1-yl)ethyl 2-acetoxybenzoate, C21H18O4
  55. Single-crystal structure determination of Tm3B12O19(OH)7
  56. Crystal structure determination of NdB3.6O7
  57. The crystal structure of NdB6O8(OH)5·H3BO3
  58. Crystal structure of 2-(5-ethylpyridin-2-yl)ethyl 2-(6-methoxynaphthalen-2-yl)propanoate, C23H25NO3
  59. Crystal structure of N-(1-(3,4-dimethoxyphenyl)-2-methylpropyl)aniline, C18H23NO2
  60. Crystal structure of Ba6Cd12Mn4SiF48
  61. Synthesis and crystal structure of 5-fluoro-1-methyl-2-oxo-3-(2-oxochroman-4-yl)indolin-3-yl acetate, C20H16FNO5
  62. The crystal structure of 6-methacryloylbenzo[d][1,3]dioxol-5-yl 4-nitrobenzenesulfonate, C17H13NO8S
  63. Crystal structure of ethyl 2-(3-benzyl-4-oxo-3,4-dihydrophthalazin-1-yl)- 2,2-difluoroacetate, C19H16F2N2O3
  64. The crystal structure of tetrakis(μ 2-(1H-benzimidazole-2-methoxo-κ2 N,O:O:O)-(n-butanol-κO)-chlorido)-tetranickel(II), C48H68Cl4N8O8Ni4
  65. Synthesis and crystal structure of trans-tetraaqua-bis((1-((7-hydroxy-3-(4-methoxy-3-sulfonatophenyl)-4-oxo-4H-chromen-8-yl)methyl)piperidin-1-ium-4-carbonyl)oxy-κO)zinc(II)hexahydrate, C46H64N2O28S2Zn
  66. The crystal structure of 1-(4-carboxybutyl)-3-methyl-1H-imidazol-3-ium hexafluoridophosphate, C9H15F6N2O2P
  67. Crystal structure of 1-(4-chlorophenyl)-4-(2-furoyl)-3-phenyl-1H-pyrazol-5-ol, C20H13ClN2O3
  68. Crystal structure of dimethyl (R)-2-(3-(1-phenylethyl)thioureido)-[1,1′-biphenyl]-4,4′-dicarboxylate, C25H24N2O4S
  69. The crystal structure of 1-(3-carboxypropyl)-1H-imidazole-3-oxide, C7H10N2O3
  70. Synthesis and crystal structure of dimethyl 4,4′-(propane-1,3-diylbis(oxy))dibenzoate, C19H20O6
  71. Crystal structure of methyl-1-(p-tolyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole-3-carboxylate, C20H20N2O2
  72. The crystal structure of 1-(1-adamantan-1-yl)ethyl-3-(3-methoxyphenyl)thiourea, C20H28N2OS
  73. The crystal structure of N,N′-carbonylbis(2,6-difluorobenzamide), C15H8F4N2O3
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