The first series of alkali dipyrrinato complexes

The first series of alkali dipyrrinato complexes is reported, encompassing lithium, sodium, and potassium salts of meso-unsubstituted and meso-aryl-substituted derivatives. By varying the substituents at the meso position, the intermolecular distance between the two nitrogen atoms and thus the κ2-N,N-bidentate bite angle was altered, as confirmed by comparison of crystallographic structures of dipyrrin free-bases in the solid-state. The mode of bonding varies as the ionic radius of the metal ion increases: solid-state structures reveal lithium to be accommodated in the plane of the dipyrrinato unit, whilst sodium is accommodated out of plane. The reactivity of analogous lithium, sodium, and potassium dipyrrinato complexes increases as the ionic radius of the metal ion increases, in keeping with the concept that the complexes tend towards an increasingly ionic nature as the size of the alkali metal increases.

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Solid State Structures of Cyclopentadienyllithium, -sodium, and -potassium. Determination by High-Resolution Powder Diffraction†

Organometallics ◽

10.1021/om9700122 ◽

1997 ◽

Vol 16 (17) ◽

pp. 3855-3858 ◽

Cited By ~ 94

Author(s):

Robert E. Dinnebier ◽

Ulrich Behrens ◽

Falk Olbrich

Keyword(s):

Solid State ◽

High Resolution ◽

Powder Diffraction ◽

Solid State Structures ◽

Sodium And Potassium

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Crystal structure of strontium and barium acesulafame (6-methyl-4-oxo-4H-1,2,3-oxathiazin-3-ide 2,2-dioxide)

Acta Crystallographica Section E Crystallographic Communications ◽

10.1107/s2056989018006059 ◽

2018 ◽

Vol 74 (5) ◽

pp. 698-702 ◽

Cited By ~ 1

Author(s):

Alexander Y. Nazarenko

Keyword(s):

Crystal Structure ◽

Hydrogen Bonds ◽

Coordination Number ◽

Metal Ion ◽

Ionic Radius ◽

Three Dimensional ◽

Interatomic Distances ◽

Coordination Polyhedra ◽

Dimensional Network ◽

Out Of Plane

Both strontium and barium acesulfames, namely poly[aquabis(μ3-6-methyl-2,2-dioxo-1,2λ6,3-oxathiazin-4-olato)strontium(II)], [Sr(C4H4NO4S)2(H2O)]n, and the barium(II) analogue, [Ba(C4H4NO4S)2(H2O)]n, crystallize in nearly identical isotypic forms, with barium–oxygen interatomic distances being longer due to the larger ionic radius of the barium(II) ion. The coordination number of the metal ion is 9; the coordination polyhedra can be described as distorted capped square antiprisms [Johnson solidJ10; Johnson (1966).Can. J. Math.18, 169–200]. The conformation of the acesulafame ions is a distorted envelope with an out-of-plane S atom. Metal and acesulfame ions are assembled into infinitive chains along the [100] axis. These chains are connectedviahydrogen bonds into a three-dimensional network.

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Electronic, Steric, and Ligand Influence on the Solid-State Structures of Substituted Sodium and Potassium Anilides

European Journal of Inorganic Chemistry ◽

10.1002/ejic.201100877 ◽

2011 ◽

Vol 2011 (34) ◽

pp. 5288-5298 ◽

Cited By ~ 18

Author(s):

Carsten Glock ◽

Helmar Görls ◽

Matthias Westerhausen

Keyword(s):

Solid State ◽

Solid State Structures ◽

Sodium And Potassium

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The Influence of the Axial Ligand on the Solid-State Structures of Pentacoordinate Manganese Tetraphenylporphyrin Complexes

Australian Journal of Chemistry ◽

10.1071/c98029 ◽

1998 ◽

Vol 51 (9) ◽

pp. 853 ◽

Cited By ~ 5

Author(s):

Peter Turner ◽

Maxwell J. Gunter ◽

Brian W. Skelton ◽

Allan H. White

Keyword(s):

Solid State ◽

Metal Ion ◽

Crystal Packing ◽

Intrinsic Property ◽

Axial Ligand ◽

Ligand Field ◽

Independent Molecules ◽

Solid State Structures ◽

Packing Interactions

The crystal structures of Mn(tpp)(NCO), Mn(tpp)(CH3CO2).0·5C7H8, Mn(tpp)(NCS).0·5C7H8, Mn(tpp)(Br).C7H8, Mn(tpp)(I).C7H8 and the previously reported structures Mn(tpp)(Cl).(CH3)2CO, Mn(tpp)(Cl).C7H8, Mn(tpp)(NO2).C6H6, Mn(tpp)(NO3).2C6H6, Mn(tpp)(OSO3H), Mn(tpp)(H2O).-SO3CF3 and Mn(tpp)(CN).CHCl3 are used to assess the role of the axial anion in the crystal packing of pentacoordinate manganese tetraphenylporphyrin complexes. A comparison of the packing strategies adopted by the toluene solvates suggests that the axial anion can sterically determine the lattice packing motif. Amongst the structures examined, there appears to be a hierarchy of packing strategies led by the elegant ‘slot together’ assembly pattern underpinning the Mn(tpp)(Br).C7H8 and Mn(tpp)(Cl).C7H8 lattices. The metrical parameters that have been used to assess intercomplex interactions in the solid state are shown to be crystal packing sensitive. This is clearly evident in the structure of Mn(tpp)(I).C7H8 which has two crystallographically independent molecules. The displacement of the metal ion from the porphyrin core is determined by the axial ligand field; however, this otherwise intrinsic property is also crystal packing dependent. That is, the iodo ligand field itself is modulated by crystal packing interactions. The isomorphous Mn(tpp)(CH3CO2).0·5C7H8 and Mn(tpp)(NCS).0·5C7H8 structures, which also have two crystallographically independent molecules, indicate that the axial ligand field strength can influence intercomplex interactions in the solid state, by moderating charge donation from the porphyrin to the metal.

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