Synthesis and structure of an unprecedented high-symmetry [Fe4S4Cl4] cubane-type unit in supramolecular [K4(FeCl4)(C12H24O6)4][Fe4S4Cl4]

Willems, J.; Köckerling, Martin

doi:10.1039/b103871k

Cited by 13 publications

(8 citation statements)

References 14 publications

(15 reference statements)

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“…In previous studies, anions have widely been introduced into the crown ether supramolecular cages as "guests". [25][26][27] In this case, however, the two water molecules act as the "guests" and are encapsulated in the cagelike crown ether "hosts", which has never been reported.…”

Section: Resultsmentioning

confidence: 76%

“…The unusual feature here is that three umbrella-like [Na(DB18C6)(H 2 O) 2 ] + units are linked together by two dissociated water molecules via OW(1)−H···OW(3) hydrogen bonds (2.733 Å) and form a semiopen cagelike supramolecular cation (Figure ). In previous studies, anions have widely been introduced into the crown ether supramolecular cages as “guests”. − In this case, however, the two water molecules act as the “guests” and are encapsulated in the cagelike crown ether “hosts”, which has never been reported.…”

Section: Resultsmentioning

confidence: 99%

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New High-Dimensional Networks Based on Polyoxometalate and Crown Ether Building Blocks

Hao

Wang

et al. 2003

Inorg. Chem.

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Three novel supramolecular assemblies constructed from polyoxometalate and crown ether building blocks, [(DB18C6)Na(H(2)O)(1.5)](2)Mo(6)O(19).CH(3)CN, 1, and [(Na(DB18C6)(H(2)O)(2))(3)(H(2)O)(2)]XMo(12)O(40).6DMF.CH(3)CN (X = P, 2, and As, 3; DB18C6 = dibenzo-18-crown-6; DMF = N,N-dimethylfomamide), have been synthesized and characterized by elemental analyses, IR, UV-vis, EPR, TG, and single crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal space group P4/mbm with a = 16.9701(6) A, c = 14.2676(4) A, and Z = 2. Compound 2 crystallizes in the hexagonal space group P6(3)/m with a = 15.7435(17) A, c = 30.042(7) A, gamma = 120 degrees, and Z = 2. Compound 3 crystallizes in the hexagonal space group P6(3)/m with a = 15.6882(5) A, c = 29.9778(18) A, gamma = 120 degrees, and Z = 2. Compound 1 exhibits an unusual three-dimensional network with one-dimensional sandglasslike channels based on the extensive weak forces between the oxygen atoms on the [Mo(6)O(19)](2)(-) polyoxoanions and the CH(2) groups of crown ether molecules. Compounds 2 and 3 are isostructural, and both contain a novel semiopen cagelike trimeric cation [(Na(DB18C6)(H(2)O)(2))(3)(H(2)O)(2)](3+). In their packing arrangement, an interesting 2-D "honeycomblike" "host" network is formed, in which the [XMo(12)O(40)](3)(-) (X = As and P) polyoxoanion "guests" resided.

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Section: Resultsmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

New High-Dimensional Networks Based on Polyoxometalate and Crown Ether Building Blocks

Hao

Wang

et al. 2003

Inorg. Chem.

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“…The tetragonal distortions from T d symmetry are much more pronounced and less variable in the more oxidized [4Fe−4S] 2+ cores. These generally appear as tetragonal compressions, although exceptions include a core elongation in (Me 3 NCH 2 CONH 2 ) 2 [Fe 4 S 4 (S t Bu) 4 ] and the crystallographically imposed T d symmetry of (K(18C6)) 4 [FeCl 4 ][Fe 4 S 4 Cl 4 ], where the cluster is surrounded by a regular array of K + …”

Section: Resultsmentioning

confidence: 99%

A Continuous Symmetry Measure of [4Fe−4S]⁺ Core Distortions and Analysis of Supramolecular Synthons in Crystal Structures of (Et₄N)₃[Fe₄S₄Cl₄]·Et₄NCl at 100 and 295 K

Hagen

Uddin

2008

Inorg. Chem.

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Distortions of the [4Fe-4S](+) cores of synthetic models from T(d) symmetry are analyzed in terms of the continuous symmetry measures (CSM, S(T(d))), and these are related to lattice effects in terms of the supramolecular synthon terminology common to crystal engineering of small molecule structures. The small tetragonal compression to D(2d) from idealized T(d) symmetry observed at low temperature is attributed to environmental factors. New members of the isomorphous series of compositional variations of double salts of the air-sensitive reduced cluster (Et(4)N)(3)[Fe(4)S(4)Cl(4)].Et(4)NCl (1) are prepared in modest yield by treatment of FeCl(2) with NaHS, or (Et(4)N)(2)[FeCl(4)] with Et(4)NSH and a base. The crystals are isomorphous with the corresponding HS(-) ligated cluster. Crystal data: tetragonal, P42(1)c, Z = 2, a = b = 12.2550 (4), c = 16.278 (1) A at 100 K, and a = b = 12.385 (1), c = 16.344 (2) A at 295 K. The crystallographically imposed S(4) symmetry obtained with sterically unincumbering ligands affords a better view of the intrinsic geometry of the core structure. The cocrystallization of the halide ion affords the opportunity to compare three types of weak C-H...X hydrogen bonds, or hydrogen bridges, between tetraalkylammonium cations and anions within the same crystal lattice. The C...Cl(-) distances (3.590 and 3.634 at 100 K increase to 3.616 and 3.655 A, respectively, at 295 K) are virtually temperature independent, indicative of hard hydrogen bridges, whereas the C...Cl-Fe distances are 3.702-3.718 A at 100 K but are 3.753-3.764 A at room temperature, suggesting a softer hydrogen bridge. A similar trend applies to the two sets of C...mu(3)-S distances (3.766-3.788 A and 3.594-3.604 A at 100 K and 3.821-3.848 A and 3.614-3.676 A at room temperature). The longer hydrogen bridges are more linear (170 degrees ) than the shorter ones (134 degrees ). The core distortions are correlated with spatial distribution of cations around the clusters.

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“…The full set of analogue structures can be obtained from Table . No analogue cluster has perfect T d symmetry; with Fe 4 S 4 clusters that limiting symmetry has been found only in one salt of [Fe 4 S 4 Cl 4 ] 2- …”

Section: 6 Principal Structural Featuresmentioning

confidence: 99%

“…No analogue cluster has perfect T d symmetry; with Fe 4 S 4 clusters that limiting symmetry has been found only in one salt of [Fe 4 S 4 Cl 4 ] 2-. 276 Among the structural deviations from cubic core symmetry, a compressed tetragonal distortion with four "short" bonds and eight "long" Fe-S bonds, approximately parallel and perpendicular, respectively, to an idealized 4-axis is frequently encountered. Under this D 2d distortion mode, core distances and angles divide as FesS and S‚‚‚S (4 + 8), FesFe (2 + 4), and FesFesFe, SsFesS, FesSsFe (4 + 8).…”

Section: Principal Structural Featuresmentioning

confidence: 99%

Synthetic Analogues of the Active Sites of Iron−Sulfur Proteins

2003

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Contents 1. Introduction 527 2. Rubredoxin Site Analogues 530 2.1. Preparation 530 2.2. Structures 530 2.3. Properties 531 3. Analogues of Binuclear (Fe 2 S 2 ) Sites 532 3.1. Preparation 532 3.2. Structures 533 3.3. Properties 533 3.4. Heteroligated Clusters 534 4. Analogues of Trinuclear (Fe 3 S 4 ) Sites 535 4.1. Linear Clusters 535 4.2. Cuboidal Clusters 536 4.3. Reactivity 537 5. Analogues of Tetranuclear (Fe 4 S 4 ) Sites 538 5.1. Electron-Transfer Series 538 5.2. [Fe 4 S 4 ] 3+ Clusters 540 5.3. [Fe 4 S 4 ] 2+ Clusters 542 5.4. [Fe 4 S 4 ] + Clusters 543 5.5. [Fe 4 S 4 ] 0 Clusters 543 5.6. Principal Structural Features 544 5.7. Specialized Clusters 545 5.7.1. Peptide Clusters 545 5.7.2. Site-Differentiated Clusters 546 5.7.3. Bridged Assemblies 549 6. Mo ¨ssbauer Parameters and Oxidation States 551 7. Structural Conversions 552 8. Perspective 554 9. Acknowledgement 555 10. Abbreviations 555 11. References 555Richard H. Holm was born in Boston, MA, spent his younger years on Nantucket Island and Cape Cod, and graduated from the University of Massachusetts (B.S.) and Massachusetts Institute of Technology (Ph.D.) He has served on the faculties of the University of Wisconsin, Massachusetts Institute of Technology, and Stanford University. Since 1980, he has been at Harvard University, where he has been Chair of the Department of Chemistry and, from 1983, Higgins Professor of Chemistry. His research interests are centered in inorganic and bioinorganic chemistry, with particular reference to the synthesis and properties of molecules whose structures and reactions are pertinent to biological processes. Venkateswara Rao Pallem was born in Hyderabad, India. He received his M.Sc. degree in chemistry in 1995 from Osmania University, Hyderabad, and his Ph.D. in chemistry in 2001 at the Indian Institute of Technology, Bombay, India, under the guidance of Professor Chebrolu P. Rao. He is currently working as a postdoctoral fellow with Professor Richard H. Holm. His research interests include the design and study of synthetic analogues of biologically related molecules.

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Synthesis and structure of an unprecedented high-symmetry [Fe4S4Cl4] cubane-type unit in supramolecular [K4(FeCl4)(C12H24O6)4][Fe4S4Cl4]

Cited by 13 publications

References 14 publications

New High-Dimensional Networks Based on Polyoxometalate and Crown Ether Building Blocks

New High-Dimensional Networks Based on Polyoxometalate and Crown Ether Building Blocks

A Continuous Symmetry Measure of [4Fe−4S]⁺ Core Distortions and Analysis of Supramolecular Synthons in Crystal Structures of (Et₄N)₃[Fe₄S₄Cl₄]·Et₄NCl at 100 and 295 K

Synthetic Analogues of the Active Sites of Iron−Sulfur Proteins

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Synthesis and structure of an unprecedented high-symmetry [Fe4S4Cl4] cubane-type unit in supramolecular [K4(FeCl4)(C12H24O6)4][Fe4S4Cl4]

Cited by 13 publications

References 14 publications

New High-Dimensional Networks Based on Polyoxometalate and Crown Ether Building Blocks

New High-Dimensional Networks Based on Polyoxometalate and Crown Ether Building Blocks

A Continuous Symmetry Measure of [4Fe−4S]+ Core Distortions and Analysis of Supramolecular Synthons in Crystal Structures of (Et4N)3[Fe4S4Cl4]·Et4NCl at 100 and 295 K

Synthetic Analogues of the Active Sites of Iron−Sulfur Proteins

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A Continuous Symmetry Measure of [4Fe−4S]⁺ Core Distortions and Analysis of Supramolecular Synthons in Crystal Structures of (Et₄N)₃[Fe₄S₄Cl₄]·Et₄NCl at 100 and 295 K