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

1998 ◽  
Vol 51 (9) ◽  
pp. 853 ◽  
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.

scholarly journals Visualising crystal packing interactions in solid-state NMR: Concepts and applications

2017 ◽  
Vol 147 (14) ◽  
pp. 144203 ◽  
Author(s):  
Miri Zilka ◽  
Simone Sturniolo ◽  
Steven P. Brown ◽  
Jonathan R. Yates
Keyword(s):  
Solid State ◽  
Solid State Nmr ◽  
Crystal Packing ◽  
Packing Interactions

The first series of alkali dipyrrinato complexes

2010 ◽  
Vol 88 (8) ◽  
pp. 725-735 ◽  
Author(s):  
Adeeb Al-Sheikh Ali ◽  
Judy Cipot-Wechsler ◽  
Sarah M. Crawford ◽  
Omar Selim ◽  
Rhonda L. Stoddard ◽  
...  
Keyword(s):  
Solid State ◽  
Metal Ion ◽  
Ionic Radius ◽  
Bite Angle ◽  
Out Of Plane ◽  
Ionic Nature ◽  
Meso Position ◽  
Crystallographic Structures ◽  
Solid State Structures ◽  
Sodium And Potassium

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.

scholarly journals Switching the Conformation of 3,2′:6′,3″-tpy Domains in 4′-(4-n-Alkyloxyphenyl)-3,2′:6′,3″-Terpyridines

Molecules ◽  
2020 ◽  
Vol 25 (14) ◽  
pp. 3162 ◽  
Author(s):  
Dalila Rocco ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Crystal Structures ◽  
Dominant Role ◽  
Van Der Waals Interactions ◽  
Single Crystal Structures ◽  
Solid State Structures ◽  
Packing Interactions ◽  
Adjacent Sheet

The preparation and characterization of 4′-(4-n-octyloxyphenyl)-3,2′:6′,3″-terpyridine (8) and 4′-(4-n-nonyloxyphenyl)-3,2′:6′,3″-terpyridine (9) are reported. The single crystal structures of 4′-(4-n-hexyloxyphenyl)-3,2′:6′,3″-terpyridine (6), 4′-(4-n-heptyloxyphenyl)-3,2′:6′,3″-terpyridine (7), and compounds 8 and 9 have been determined. The conformation of the 3,2′:6′,3″-tpy unit is trans,trans in 6 and 7, but switches to cis,trans in 8 and 9. This is associated with significant changes in the packing interactions with a more dominant role for van der Waals interactions between adjacent n-alkyloxy chains and C–Hmethylene... π interactions in 8 and 9. The solid-state structures of 6 and 7 with the n-hexyloxy and n-heptyloxy chains feature interwoven sheets of supramolecular assemblies of molecules, with pairs of n-alkyloxy chains threaded through cavities in an adjacent sheet.

Z′ = 4 structure without obvious pseudosymmetry: implications for the formation of solid-state compounds

2001 ◽  
Vol 58 (1) ◽  
pp. 140-147 ◽  
Author(s):  
Hans-Joachim Lehmler ◽  
Larry W. Robertson ◽  
Sean Parkin ◽  
Carolyn Pratt Brock
Keyword(s):  
Solid State ◽  
Crystal Packing ◽  
Structure Type ◽  
Hydroxyl Groups ◽  
Approximate Symmetry ◽  
Compound Formation ◽  
Hydrogen Bond Formation ◽  
Molecular Arrangement ◽  
Independent Molecules ◽  
Packing Arrangement

Crystals of 4-chloro-2′-biphenylol grown at 263 K and studied at both 293 and 142 K are loosely packed and contain OH...O bonded tetramers composed of four crystallographically independent molecules (Z′ = 4). Approximate symmetry relationships between independent molecules are apparent in many, perhaps even most, structures with Z′ > 1, but are not obvious in this structure. The inefficient crystal packing, the surprisingly large value of Z′ and the absence of pseudosymmetry reflect the difficulty of finding a dense molecular arrangement that also allows for hydrogen-bond formation. Impediments to good packing are the steric congestion around the ortho hydroxyl groups and the difficulty in filling space with significantly twisted biphenyl fragments. The packing arrangement adopted is strongly reminiscent of the structure type found for eight simple 4,4′-biphenyl derivatives, but one of the four independent 4-chloro-2′-biphenylol molecules has an orientation that is significantly different from the orientations of the other three and that does not fit the 4,4′-XPhPhY pattern. It is suggested that molecules that crystallize with Z′ > 1 are good candidates for solid-state compound formation.

scholarly journals The Influence of Halogenated Hypercarbon on Crystal Packing in the Series of 1-Ph-2-X-1,2-dicarba-closo-dodecaboranes (X = F, Cl, Br, I)

Molecules ◽  
2020 ◽  
Vol 25 (5) ◽  
pp. 1200
Author(s):  
Miroslav Havránek ◽  
Maksim A. Samsonov ◽  
Josef Holub ◽  
Zdeňka Růžičková ◽  
Ladislav Drož ◽  
...  
Keyword(s):  
Solid State ◽  
Electrostatic Potential ◽  
Crystal Packing ◽  
Heat Of Formation ◽  
Solid State Structures

Although 1-Ph-2-X-closo-1,2-C2B10H10 (X = F, Cl, Br, I) derivatives had been computed to have positive values of the heat of formation, it was possible to prepare them. The corresponding solid-state structures were computationally analyzed. Electrostatic potential computations indicated the presence of highly positive σ-holes in the case of heavy halogens. Surprisingly, the halogen•••π interaction formed by the Br atom was found to be more favorable than that of I.

A theoretical insight into non-covalent supramolecular interactions in the solid state structures of two octahedral iron(iii) complexes

CrystEngComm ◽  
2020 ◽  
Vol 22 (35) ◽  
pp. 5731-5742 ◽  
Author(s):  
Tanmoy Basak ◽  
Antonio Frontera ◽  
Shouvik Chattopadhyay
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Crystal Packing ◽  
Supramolecular Interactions ◽  
Interaction Energies ◽  
Π Interactions ◽  
Solid State Structures ◽  
Theoretical Insight ◽  
Insight Into

The nature and characteristics of the C–H⋯π interactions that play an important role in crystal packing of two iron(iii) complexes have been discussed. The DFT calculations have been conducted to determine the interaction energies in these complexes.

scholarly journals (Z)-5-(4-Bromophenyl)-3-{[(3,5-dichlorophenyl)amino]methylidene}furan-2(3H)-one

IUCrData ◽  
2020 ◽  
Vol 5 (7) ◽  
Author(s):  
Oksana A. Mayorova ◽  
Vyacheslav S. Grinev ◽  
Alevtina Yu. Yegorova
Keyword(s):  
Solid State ◽  
Title Compound ◽  
Crystal Packing ◽  
Large Cell ◽  
Monoclinic Space Group ◽  
Stacking Interactions ◽  
Asymmetric Unit ◽  
Compound C ◽  
Benzene Rings ◽  
Independent Molecules

The title compound, C17H10BrCl2NO2, crystallizes in the monoclinic space group C2/c with a large cell volume of 6207 (3) Å3. The asymmetric unit of the title compound investigated at 120 K contains two crystallographically independent molecules (Z′ = 2). Each molecule demonstrates slight non-planarity in the solid state and a Z-configuration for the exocyclic C=C bond. The crystal packing reveals the presence of π-π stacking interactions between the substituted benzene rings [centroid–centroid distances of 3.836 (5) Å, shift distances in the range 1.272–1.843 Å].

Solid-State Structures of Double-Long-Chain Imidazolium Ionic Liquids: Influence of Anion Shape on Cation Geometry and Crystal Packing

2011 ◽  
Vol 11 (5) ◽  
pp. 1974-1988 ◽  
Author(s):  
Xinjiao Wang ◽  
Carola S. Vogel ◽  
Frank W. Heinemann ◽  
Peter Wasserscheid ◽  
Karsten Meyer
Keyword(s):  
Ionic Liquids ◽  
Solid State ◽  
Crystal Packing ◽  
Imidazolium Ionic Liquids ◽  
Solid State Structures ◽  
Long Chain
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