DOI: 10.1002/anie.199704841. An Unusual Polyoxomolybdate: Giant Wheels Linked to Chains

An Unusual Polyoxomolybdate: Giant Wheels Linked to Chains

10.1002/anie.199704841

Crossref journal-article

Wiley

Angewandte Chemie International Edition in English (311)

Bibliography

MÃ¼ller, A., Krickemeyer, E., BÃ¶gge, H., Schmidtmann, M., Peters, F., Menke, C., & Meyer, J. (1997). An Unusual Polyoxomolybdate: Giant Wheels Linked to Chains. Angewandte Chemie International Edition in English, 36(5), 484â486. Portico.

Authors 7

Achim Müller (first)
Erich Krickemeyer (additional)
Hartmut Bögge (additional)
Marc Schmidtmann (additional)
Frank Peters (additional)
Carsten Menke (additional)
Jochen Meyer (additional)

References 35 Referenced 72

{'key': 'e_1_2_1_1_2', 'volume-title': 'Structural Inorganic Chemistry', 'author': 'Wells A. F.', 'year': '1984'} / Structural Inorganic Chemistry by Wells A. F. (1984)
{'key': 'e_1_2_1_1_3', 'volume-title': 'Lehrbuch der Mineralogie', 'author': 'Rösler H. J.', 'year': '1984'} / Lehrbuch der Mineralogie by Rösler H. J. (1984)
10.1002/ange.19911030107
10.1002/anie.199100341
10.1038/352115b0
10.1007/978-94-011-0920-8
10.1002/9780470166444.ch1
10.1038/383296a0
10.1002/ange.19951072104
10.1002/anie.199523281
10.1051/978-2-7598-0292-0 / De la solution à l'oxyde by Jolivet J.‐P. (1994)
10.1002/ange.19951071911
10.1002/anie.199521221
10.1007/s001140050294
10.1002/ange.19961081109
10.1002/anie.199612061
10.1002/zaac.19946200405
10.1002/ange.19941060809
10.1002/anie.199408491
10.1007/BF00811844
{'key': 'e_1_2_1_5_6', 'first-page': '291', 'volume': '42', 'author': 'Müller A.', 'year': '1994', 'journal-title': 'Bull. Pol. Acad. Sci. (Chem.)'} / Bull. Pol. Acad. Sci. (Chem.) by Müller A. (1994)
1: space groupP1;a= 2540.9(7) b= 3415.3(8) c= 4510.2(14) pm α = 91.28(2) β = 92.14(2) γ = 100.59(2)° V= 38429(18) × 106pm3(μ = 23.9 cm−1);Z= 2; solution with direct methods R= 0.124 for 39487 independent reflections (Fo> 4σ(Fo)); Siemens R3m/V diffractometer MoKαradiation graphite monochromator. Because of the long time required for data collection the deep blue crystals of1were mounted in oil when removed from the mother liquor and the measurement was conducted at – 70°C. The measurements of other individual crystals gave the same results. The data set was measured to a 2θ value of 39°. The structure was solved by using the program SHELXS‐96 and refined with the program SHELXL‐93. A. comparison of the structures of1and2showed that at the corresponding positions where electronically shielded reduced Mo centers (which means MoNO groups) occur in2[3 5] MO groups with MoVIcenters are incorporated into1. In addition the distribution of the other reduced Mo centers as well as H2O and OH ligands is practically identical in1and2. Furthermore a symmetric OMoOMo‐(H2O)↔(H2O)MoOMoO disorder is found at the linking positions in the rings in1. Our interpretation of this disorder is chemically motivated as the observed distribution of the electron density could in principle be crystallographically interpreted by the existence of HOMoOMoOH units. Our elucidation is supported by the fact that we could explain the previously mentioned disorder in related structures that show an analogous type of linking. In addition the comparable OMoH2O‐/H2OMoO disorder is found in numerous other (also mononuclear) compounds. Furthermore all molybdenum atoms with two (transpositioned) or three non‐bridging oxygen ligands (52 in total) possess a coordinated H2O ligand. The sodium atoms are disordered to the extent that it was not possible to determine all of their positions. Therefore several sodium analyses were carried out. The detection of a somewhat higher Na value than expected from the given formula for1correlated with the discovery of chloride in the elemental analysis (about 0.4% Cl corresponding to about 0.4% Na excess). The presence of about 1000 atoms in the asymmetric unit of1could indicate that we are dealing here with one of the most complicated inorganic structures. The figures were prepared with the program DIAMOND (“Diamond Informationssystem für Kristallstrukturen” by Dr. K. Brandenburg Universität Bonn Germany). Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe D‐76344 Eggenstein‐Leopoldshafen (Germany) on quoting the depository number CSD‐406337.
Due to the size of the system the complexity of the structure the quality of the measurement and the crystals and the disorder in the system it is reasonable to expect that the given formula has an error limit. The number of oxygen (409) and molybdenum (144) atoms have—in agreement with the disorder–error limits of ±5 and ±2 respectively. The related value for the anion charge is 15 ± 3 (see also ref. [6]). The results of the manganometric titration and the extinction coefficient of the IVCT band at higher energy of the type MoV→ MoVIshow in1as in2(without consideration of the electronically inert MoNO groups) that 33 ± 3 molybdenum centers are according to the present study (formally) reduced. These are distributed as in2(cf. ref. [3]) and thus only the {Mo1} and {Mo8} groups are involved in the related electron delocalization [8]. The number of delocalized electrons (in the 4d pseudo band) is 33 ± 3 also practically in agreement with the given charge of the anion of2 at the lower limit of error (20– [3a] which corresponds to the more realistic value).
The mixed‐valence compound1features a small phase range with respect to the stoichiometry a phenomenon which is certainly more common in metal chalcogenide solid‐state structures than is frequently assumed (“progress is still blocked by a slavish devotion to the cult of the molecule and a naive faith in the general applicability of Dalton's laws of chemical combination.”:
{'key': 'e_1_2_1_8_3', 'first-page': '5', 'volume-title': 'Ionic Crystals, Lattice Defects, and Nonstoichiometry', 'author': 'Greenwood N. N.', 'year': '1968'} / Ionic Crystals, Lattice Defects, and Nonstoichiometry by Greenwood N. N. (1968)
This type of compound however is found especially frequently in mixed‐valence transition metal chalcogenides which precisely because of this feature also exhibit important physical features like superconductivity (Mixed Valency Systems:
{'key': 'e_1_2_1_8_5', 'volume-title': 'Applications in Chemistry, Physics and Biology', 'author': 'Prassides K.', 'year': '1991'} / Applications in Chemistry, Physics and Biology by Prassides K. (1991)
10.1007/978-94-009-0447-7_4
{'key': 'e_1_2_1_9_2', 'first-page': '1462', 'volume-title': 'Holleman‐Wiberg: Lehrbuch der Anorganischen Chemie', 'year': '1995'} / Holleman‐Wiberg: Lehrbuch der Anorganischen Chemie (1995)
{'key': 'e_1_2_1_10_2', 'first-page': '66', 'volume-title': 'Designing the Molecular World', 'author': 'Ball P.', 'year': '1994'} / Designing the Molecular World by Ball P. (1994)
{'key': 'e_1_2_1_10_3', 'volume-title': 'Zeolite, Clay, and Heteropoly Acid in Organic Reactions', 'author': 'Izumi Y.', 'year': '1992'} / Zeolite, Clay, and Heteropoly Acid in Organic Reactions by Izumi Y. (1992)
10.1038/382313a0
{'key': 'e_1_2_1_12_2', 'volume-title': 'Biomimetic Materials Chemistry', 'author': 'Mann S.', 'year': '1996'} / Biomimetic Materials Chemistry by Mann S. (1996)
{'key': 'e_1_2_1_13_2', 'volume-title': 'Exploring Complexity', 'author': 'Nicolis G.', 'year': '1989'} / Exploring Complexity by Nicolis G. (1989)
Compound2shows interesting catalytic behavior as in its presence novel carbon cages are formed (SirH.Kroto private communication).

Dates

Type	When
Created	21 years, 7 months ago (Dec. 31, 2003, 4:33 a.m.)
Deposited	1 year, 10 months ago (Oct. 11, 2023, 2:34 p.m.)
Indexed	1 week ago (Aug. 19, 2025, 7:02 a.m.)
Issued	28 years, 5 months ago (March 14, 1997)
Published	28 years, 5 months ago (March 14, 1997)
Published Online	21 years, 8 months ago (Dec. 22, 2003)
Published Print	28 years, 5 months ago (March 14, 1997)

Funders 0

None

BibTeX

@article{M_ller_1997, title={An Unusual Polyoxomolybdate: Giant Wheels Linked to Chains}, volume={36}, ISSN={0570-0833}, url={http://dx.doi.org/10.1002/anie.199704841}, DOI={10.1002/anie.199704841}, number={5}, journal={Angewandte Chemie International Edition in English}, publisher={Wiley}, author={Müller, Achim and Krickemeyer, Erich and Bögge, Hartmut and Schmidtmann, Marc and Peters, Frank and Menke, Carsten and Meyer, Jochen}, year={1997}, month=mar, pages={484–486} }

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      "unstructured": "1: space groupP1;a= 2540.9(7) b= 3415.3(8) c= 4510.2(14) pm \u03b1 = 91.28(2) \u03b2 = 92.14(2) \u03b3 = 100.59(2)\u00b0 V= 38429(18) \u00d7 106pm3(\u03bc = 23.9 cm\u22121);Z= 2; solution with direct methods R= 0.124 for 39487 independent reflections (Fo> 4\u03c3(Fo)); Siemens R3m/V diffractometer MoK\u03b1radiation graphite monochromator. Because of the long time required for data collection the deep blue crystals of1were mounted in oil when removed from the mother liquor and the measurement was conducted at \u2013 70\u00b0C. The measurements of other individual crystals gave the same results. The data set was measured to a 2\u03b8 value of 39\u00b0. The structure was solved by using the program SHELXS\u201096 and refined with the program SHELXL\u201093. A. comparison of the structures of1and2showed that at the corresponding positions where electronically shielded reduced Mo centers (which means MoNO groups) occur in2[3 5] M\uf8feO groups with MoVIcenters are incorporated into1. In addition the distribution of the other reduced Mo centers as well as H2O and OH ligands is practically identical in1and2. Furthermore a symmetric O\uf8ffMo\uf8ffO\uf8ffMo\u2010(H2O)\u2194(H2O)Mo\uf8ffO\uf8ffMo\uf8ffO disorder is found at the linking positions in the rings in1. Our interpretation of this disorder is chemically motivated as the observed distribution of the electron density could in principle be crystallographically interpreted by the existence of HO\uf8ffMo\uf8ffO\uf8ffMo\uf8ffOH units. Our elucidation is supported by the fact that we could explain the previously mentioned disorder in related structures that show an analogous type of linking. In addition the comparable O\uf8feMo\uf8ffH2O\u2010/H2O\uf8ffMo\uf8feO disorder is found in numerous other (also mononuclear) compounds. Furthermore all molybdenum atoms with two (transpositioned) or three non\u2010bridging oxygen ligands (52 in total) possess a coordinated H2O ligand. The sodium atoms are disordered to the extent that it was not possible to determine all of their positions. Therefore several sodium analyses were carried out. The detection of a somewhat higher Na value than expected from the given formula for1correlated with the discovery of chloride in the elemental analysis (about 0.4% Cl corresponding to about 0.4% Na excess). The presence of about 1000 atoms in the asymmetric unit of1could indicate that we are dealing here with one of the most complicated inorganic structures. The figures were prepared with the program DIAMOND (\u201cDiamond Informationssystem f\u00fcr Kristallstrukturen\u201d by Dr. K. Brandenburg Universit\u00e4t Bonn Germany). Further details of the crystal structure investigation may be obtained from the Fachinformationszentrum Karlsruhe D\u201076344 Eggenstein\u2010Leopoldshafen (Germany) on quoting the depository number CSD\u2010406337."
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