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Reactions of 1,10‐phenanthroline (phen) and 2‐(3,4‐dichlorophenyl)acetic acid (dcaH) with Mn(CO3) (M = LiI, NaI and MgII; n = 1 and 2) in MeOH yield the mononuclear lithium complex aqua[2‐(3,4‐dichlorophenyl)acetato‐κO](1,10‐phenanthroline‐κ2N,N′)lithium(I), [Li(C8H5Cl2O2)(C12H8N2)(H2O)] or [Li(dca)(phen)(H2O)] (1), the dinuclear sodium complex di‐μ‐aqua‐bis{[2‐(3,4‐dichlorophenyl)acetato‐κO](1,10‐phenanthroline‐κ2N,N′)sodium(I)}, [Na2(C8H5Cl2O2)2(C12H8N2)2(H2O)2] or [Na2(dca)2(phen)2(H2O)2] (2), and the one‐dimensional chain magnesium complex catena‐poly[[[diaqua(1,10‐phenanthroline‐κ2N,N′)magnesium]‐μ‐2‐(3,4‐dichlorophenyl)acetato‐κ2O:O′] 2‐(3,4‐dichlorophenyl)acetate monohydrate], {[Mg(C8H5Cl2O2)(C12H8N2)(H2O)2](C8H5Cl2O2)·H2O}n or {[Mg(dca)(phen)(H2O)2](dca)·H2O}n (3). In these complexes, phen binds via an N,N′‐chelate pocket, while the deprotonated dca− ligands coordinate either in a monodentate (in 1 and 2) or bidentate (in 3) fashion. The remaining coordination sites around the metal ions are occupied by water molecules in all three complexes. Complex 1 crystallizes in the triclinic space group P with one molecule in the asymmetric unit. The Li+ ion adopts a four‐coordinated distorted seesaw geometry comprising an [N2O2] donor set. Complex 2 crystallizes in the triclinic space group P with half a molecule in the asymmetric unit, in which the Na+ ion adopts a five‐coordinated distorted spherical square‐pyramidal geometry, with an [N2O3] donor set. Complex 3 crystallizes in the orthorhombic space group P212121, with one Mg2+ ion, one phen ligand, two dca− ligands and three water molecules in the asymmetric unit. Both dcaH ligands are deprotonated, however, one dca− anion is not coordinated, whereas the second dca− anion coordinates in a bidentate fashion bridging two Mg2+ ions, resulting in a one‐dimensional chain structure for 3. The Mg2+ ion adopts a distorted octahedral geometry, with an [N2O4] donor set. Complexes 1–3 were evaluated against urease and α‐glucosidase enzymes for their inhibition potential and were found to be inactive. Reactions of 1,10‐phenanthroline (phen) and 2‐(3,4‐dichlorophenyl)acetic acid (dcaH) with Mn(CO3) (M = LiI, NaI and MgII; n = 1 and 2) in MeOH yield the mononuclear lithium complex, the dinuclear sodium complex and the one‐dimensional chain magnesium complex. In these complexes, phen binds via an N,N′‐chelate pocket, while the deprotonated dca− ligands coordinate either in a monodentate or bidentate fashion. [ABSTRACT FROM AUTHOR]

Formation of radical–radical cocrystals is an important step towards the design of organic ferrimagnets. We describe a simple approach to generate radical–radical cocrystals through the identification and implementation of well‐defined supramolecular synthons which favor cocrystallization over phase separation. In the current paper we implement the structure‐directing interactions of the E−E bond (E=S, Se) of dithiadiazolyl (DTDA) and diselenadiazolyl (DSDA) radicals to form close contacts to electronegative groups. This is exemplified through the preparation and structural characterization of three sets of radical cocrystals; the 2:2 cocrystal [PhCNSSN]2[MBDTA]2 (4) [MBDTA=methyl benzodithiazolyl] and the 2:1 cocrystals [C6F5CNEEN]2[TEMPO] (E=S, 5; E=Se, 6). In 4 the two types of radical are linked via bifurcated inter‐dimer δ+S⋅⋅⋅Nδ− interactions whereas 5 and 6 exhibit a set of five‐centre δ+E⋅⋅⋅Oδ− contacts (E=S, Se). SOMO wrestling: Cocrystallization of radicals requires different open‐shell molecules to interact with each other rather than themselves. This process can be driven by careful selection of favorable electrostatic interactions between molecules. [ABSTRACT FROM AUTHOR]

We show that the αi and βj parameters developed by Hunter to describe the hydrogen‐bond donor and acceptor properties of particular functional groups can be successfully applied to understand favourable intermolecular interactions between molecules containing heavier p‐block elements, notwithstanding the increasing dispersion terms associated with these elements. Although dispersion is an important contribution to the dimerisation enthalpy of dithiadiazolyls, we show that many aspects of the crystal packing of dimers can successfully be interpreted through such an electrostatic analysis. This approach is exemplified through analysis of the crystal structures of a series of fluoro‐ and trifluoromethyl‐substituted 1,2,3,5‐dithiadiazolyl radicals. Comparison of fluoro‐ and trifluoromethyl‐substituted aryl dithiadiazolyls reveals that the trifluoromethyl group has a pronounced electron‐withdrawing effect, enhancing the electrostatic contribution, but also adding steric bulk. The possible intermolecular interactions between these molecules are close in energy, resulting in structural diversity and at least one case of polymorphism. Despite neglecting the significant favourable dimerisation enthalpy in the analysis of the electrostatic potential, this approach provides a very clear rationalisation of many aspects of the observed crystal structures.|||||| [ABSTRACT FROM AUTHOR]

The crystal structure of a novel dithiadiazolyl co-crystal, the second such co-crystal to be reported, has been determined, and is described in the context of the structures of the co-crystal formers. It is also shown that both known dithiadiazolyl co-crystals ([PhCN2S2][C6F5CN2S2] and [PhCN2S2][NC5F4CN2S2]) can be made via co-sublimation or by mixing co-crystal formers in solution, but not mechanochemically. DSC and theoretical calculations reveal that the thermodynamics of co-crystal formation in these systems is very finely balanced. [ABSTRACT FROM AUTHOR]

Double deprotonation of N,N′-bis(2,6-diisopropylphenyl)-o-phenylenediamine (H2L) with n-BuLi in THF yields the dilithium complex Li2L(thf)3. The reaction of Li2L(thf)3 with FeBr2(thf)2 and subsequent replacement of the solvent with toluene yield LFe(η6-toluene), which can also be synthesized from Fe(HMDS)2(thf) and H2L in toluene. The NMR data, bond lengths obtained from an X-ray diffraction study, and DFT calculations indicate that the diamide ligand L2− undergoes oxidization to a radical ligand L1−. Reaction of LFe(η6-toluene) with 1 atm CO yields the tricarbonyl complex LFe(CO)3. MoCl4(thf)2 reacts with two equivalents of Li2L(thf)3 to yield (LiL)2MoCl2(thf)4 in which the phenylene backbone of the ligand has been dearomatized. One-electron oxidation of Li2L(thf)3 by EuCl3(dme)2 yields the open-shell species LiL(OEt2), which was characterized by X-ray crystallography and EPR spectroscopy. [ABSTRACT FROM AUTHOR]

Reaction of ArSNᆖC(py)2 [Ar = 2,4-dinitrophenyl, (O2N)2C6H3] with CuCl2·2H2O in DMF yielded the tetranuclear complex [Me2NH2][Cu4Cl6{py2CO2}{py2C(OH)O}] (1) through metal-catalysed hydrolysis of both DMF and the thiazyl chain. Notably direct reaction of dipyridylketone (py2CO) with CuCl2·2H2O in DMF yielded the mononuclear pseudo-octahedral complex [CuCl2(py2C(OH)2)(DMF)]·DMF (2) in which the 1,1-gem diol, py2C(OH)2 acts as a tripodal ligand. Heating of 2 in DMF/MeOH promoted aggregation and formation of the polymer [Cu2Cl3{py2(OMe)O}]∞ (3). The structures of 1–3 were determined by X-ray diffraction. [ABSTRACT FROM AUTHOR]

Oxidation of equimolar amounts of [p-BrC[sub 6] H[sub 4] CNSSN]Cl and [p-O[sub 2] NC[sub 6] H[sub 4] CNSSN]Cl with elemental O[sub 2] in the presence of Ph[sub 3] Sb in MeCN yields a mixture of the symmetric dithiatetrazocines, O[sub 2] NC[sub 6] H[sub 4] CN[sub 4] S[sub 2] CC[sub 6] H[sub 4] NO[sub 2] (1) and BrC[sub 6] H[sub 4] CN[sub 4] S[sub 2] CC[sub 6] H[sub 4] Br (2) as well as the unsymmetrically substituted derivative BrC[sub 6] H[sub 4] CN[sub 4] S[sub 2] CC[sub 6] H[sub 4] NO[sub 2] (3). The structures of compounds 1–3 are determined by X-ray diffraction: 1 crystallizes in the monoclinic space group P2[sub 1] /c (a = 8.6397(4), b = 5.8359(4), c = 14.9767(11) Å, β = 92.088(4)°) with half a molecule in the asymmetric unit; 2 crystallizes in the triclinic space group P1 (a = 6.5330(5), b = 8.2084(6), c = 14.7264(9) Å, α = 84.483(4)°, β = 77.112(4)°, γ = 87.879(3)°); 3 was found to crystallize in two forms: recrystallization from CH[sub 2] Cl[sub 2] at room temperature yielded a solvent-free, triclinic phase, space group P1 (a = 6.5060(9), b = 7.0739(9), c = 9.1164(8) Å, α = 81.860(3)°, β = 83.406(5)°, γ = 66.589(5)°), whereas cooling a solution to –5°C yielded a solvated form, 3·CH[sub 2] Cl[sub 2] , which crystallizes in the monoclinic space group P2[sub 1] /m (a = 6.179(1), b = 10.960(2), c = 13.884(3) Å, β = 92.69(3)°). The NO[sub 2] ···Br intermolecular interactions observed in the unsolvated structure of 3 are disrupted in the solvate structure; the CH[sub 2] Cl[sub 2] molecule in the latter is aligned such that its molecular dipole interacts with both nitro and bromo groups, retaining a molecular chain motif. The structures are discussed in relation to their semi-empirically calculated molecular electrostatic potentials and calculations of intermolecular interactions using van der Waals forces combined with an electrostatic point charge model.Key words: dithiatetrazocine, crystal structure, crystal engineering, molecular electrostatic potential.L'oxydation de quantités équimolaires de [p-BrC[sub 6] H[sub 4] CNSSN]Cl et de [p-O[sub 2] NC[sub 6] H[sub 4] CNSSN]Cl avec de l'oxygène élémentaire, en présence de Ph[sub 3] Sb, dans du MeCN, conduit à un mélange de dithiatétrazocines symétriques, O[sub 2] NC[sub 6] H[sub 4] CN[sub 4] S[sub 2] CC[sub 6] H[sub 4] NO[sub 2] (1) et BrC[sub 6] H[sub 4] CN[sub 4] S[sub 2] CC[sub 6] H[sub 4] Br (2), aux côtés du dérivé substitué de façon non symétrique, BrC[sub 6] H[sub 4] CN[sub 4] S[sub 2] CC[sub 6] H[sub 4] NO[sub 2] (3). On a déterminé les structures des composés 1–3 par diffraction des rayons X: le composé 1 cristallise dans le groupe d'espace monoclinique P2[sub 1] /c (a = 8,6397(4), b = 5,8359(4) et c = 14,9767(11) Å, β = 92,088(4)°), avec une demi-molécule dans la maille asymétrique; 2 cristallise dans le groupe d'espace triclinique P1 (a = 6,5330(5), b = 8,2084(6) et c = 14,7264(9) Å, α = 84,483(4)°, β = 77,112(4)° et γ = 87,879(3)°); on a trouvé que 3 cristallise sous deux formes, la recristallisation dans le CH[sub 2] Cl[sub 2] , à température ambiante, conduit à des cristaux ne contenant pas de solvant, de phase triclinique et de groupe d'espace P1 (a = 6,5060(9), b = 7,0739(9) et c = 9,1164(8) Å, α = 81,860(3)°, β = 83,406(5)° et γ = 66,589(5)°) alors que le refroidissement de la solution à –5°C livre une forme solvatée, 3·CH[sub 2] Cl[sub 2] qui cristallise dans le groupe d'espace monoclinique P2[sub 1] /m (a = 6,179(1), b = 10,960(2) et c = 13,884(3) Å, β = 92,69(3)°). Les interactions intermoléculaires NO[sub 2] ···Br observées dans la structure non solvatée de 3 sont interrompues dans la structure solvatée; la molécule de CH[sub 2] Cl[sub 2] de cette dernière est alignée d'une façon telle que son dipôle moléculaire interagit à la fois avec le groupe nitro et le bromo tout en maintenant un motif de chaîne moléculaire. On discute des structures en fonction de leurs potentiels électrostatiques moléculaires calculés de façon semi-empirique et de calculs d'interactions intermoléculaires à l'aide de forces de van der Waals combinées à un modèle de charge ponctuelle électrostatique.Mots clés : dithiatétrazocine, structure cristalline, génie cristallin, potentiel électrostatique moléculaire.[Traduit par la Rédaction] [ABSTRACT FROM AUTHOR]

Abstract Reaction of the phenanthridine ligand (phend) with ZnBr 2 in DMSO/MeOH or MeOH yielded the complexes ZnBr 2 (phend)(DMSO) (1) and ZnBr 2 (phend) 2 (2) respectively. These complexes were characterized by single crystal X-ray diffraction, IR spectroscopy and elemental analyses. Sonochemical preparation of complexes 1 and 2 in methanolic solution generated porous texture (pt) crystals 1 pt and 2 pt. Comparison of the X-ray powder diffraction data confirmed identical crystal structures for 1 and 1 pt as well as 2 and 2 pt. The porous texture (the mixture of nano-porous and micro-pores) morphologies of the sonochemical products were confirmed by scanning electron microscopy. Reaction conditions, such as solvent and the concentration of the initial reagents, played important roles in the size and growth process of the crystalline products. Graphical abstract Image 1 Highlights • Changing solvent has a significant impact on the crystal packing of a series of Zn(II) coordination complexes. • The C H⋯Br hydrogen bonds interactions have a great role in the formation of the multi-dimensional crystal structure. • The C H.⋯Br hydrogen bonds and C H ... π interactions administer the crystal structure. [ABSTRACT FROM AUTHOR]