Trialkylhydridoalanate RxR′3-xAlH⊖ [R = CMe3; R′ = CH(SiMe3)2]

Trialkylhydridoalanates R_xR′_3?xAlH^? [R = CMe₃; R′ = CH(SiMe₃)₂] The very strong base tert-butyl lithium reacts in the presence of chelating tetramethylethylendiamine with the aluminium organyls Al[CH(SiMe₃)₂]₂CMe₃ 1 and Al[CH(SiMe₃)₂](CMe₃)₂ 2 not under proton abstraction from the C? H acidic elementorganic substituent, but under β-elimination and addition of the thereby formed LiH to the coordinatively unsaturated aluminium atom. Two alanates — [Hal{CH(SiMe₃)₂}₂CMe₃]^? 3 and [HAl{CH(SiMe₃)₂}(CMe₃)₂]^? 4 each with Li(TMEDA)₂^⊕ as counterion — were isolated; they exhibit separate anions and cations in solid state as shown by a crystal structure determination on 3 . In absence of the chelating amine tert-butyl lithium decomposes under the catalytic effect of the aluminium compound to LiH, which does not add to aluminium and precipitates in a reactive form.     

Einfluß der Ringatome auf die Struktur von Triel‐Pentel‐Heterozyklen – Synthese und Molekülstrukturen von [Me2InAs(SiMe3)2]2 und [Me2InSb(SiMe3)2]3

Influence of the Ring Atoms on the Structure of Triel‐Pentel Heterocycles – Synthesis and X‐Ray Crystal Structures of [Me₂InAs(SiMe₃)₂]₂ and [Me₂InSb(SiMe₃)₂]₃ Triel‐pentel heterocycles [Me₂InE(SiMe₃)₂]_x have been prepared by dehalosilylation reactions from Me₂InCl and E(SiMe₃)₃ (E = As, x = 2; E = Sb, x = 3) and characterised by NMR spectroscopy and by X‐ray crystal structure analyses. In addition the X‐ray crystal structures of [Me₂GaAs(SiMe₃)₂]₂ and [Me₂InP(SiMe₃)₂]₂ are reported. The compounds complete a family of 13 identically substituted heterocycles [Me₂ME(SiMe₃)₂]_x (M = Al, Ga, In; E = N, P, As, Sb, Bi; x = 2, 3), whose structures were investigated depending on the ring atoms M and E. The tendencies that have been observed concerning the ring sizes can be explained by the interplay of the atomic radii of the central atoms and the sterical demand of the ligands. After a formal separation of the M–E bonds in σ bonds and dative bonds the characteristic differences and trends in the endocyclic and exocyclic bond angles of both centres M and E can be interpreted on the basis of a simple Lewis acid/base adduct model.     

Die Reaktion des Digalliumsubiodids R(I)Ga‐Ga(I)R [R = C(SiMe3)3] mit Lithium‐diphenylphosphanid – radikalische Öffnung der Ga‐Ga‐Bindung

The Reaction of the Digallium Subiodide R(I)Ga‐Ga(I)R [R = C(SiMe₃)₃] with Lithium Diphenylphosphanide – Radical Cleavage of the Ga‐Ga Bond The easily available organoelement digallium(II) subiodide R(I)Ga‐Ga(I)R ( 1 ) [R = C(SiMe₃)₃] reacted with two equivalents of lithium diphenylphosphanide in toluene by the replacement of both iodine atoms by two phosphanido groups. The product, [R(H)Ga‐P(C₆H₅)₂]₂ ( 2 ), contains a four‐membered Ga₂P₂ heterocycle without direct Ga‐Ga bonding interactions and the gallium atoms exclusively in an oxidation state of +III. They are attached to hydrogen atoms, which may result from a reaction of a reactive intermediate with the solvent.     

Ga2Br2R2 und Ga3I2R3 [R = C(SiMe3)3] — zwei neue elementorganische Galliumsubhalogenide mit einer bzw. zwei Ga‐Ga‐Bindungen

Ga₂Br₂R₂ and Ga₃I₂R₃ [R = C(SiMe₃)₃] — Two New Organoelement Subhalides of Gallium Containing One or Two Ga‐Ga Single Bonds The oxidation of the tetrahedral tetragallium cluster Ga₄[C(SiMe₃)₃]₄ ( 1 ) with elemental bromine in the presence of AlBr₃ yielded the corresponding gallium subhalide Ga₂Br₂R₂ [ 4 , R = C(SiMe₃)₃], which remains monomer even in the solid state and in which the Ga^II atoms are connected by a short Ga‐Ga single bond [243.2(2) pm]. The analogous diiodide Ga₂I₂R₂ ( 3 ), which was obtained on a similar route by our group only recently, did not react with lithium tert‐butanolate by substitution as originally expected. Instead, partial disproportionation occurred with the formation of the trigallium diiodide Ga₃I₂R₃ ( 6 ), in which three Ga atoms are connected by two Ga‐Ga single bonds (255.1 pm on average). Both terminal Ga atoms have a coordination number of four owing to the bridging function of both iodine atoms, while the inner one which has an oxidation number of +1 remains coordinatively unsaturated. An average oxidation state of 1.66 resulted for all atoms of the chain. The Ga^III compound {[GaI(R)(OCMe₃)(OH)]Li}₂ ( 7 ) was isolated as the second product of the disproportionation. It is a dimer in the solid state via Li‐O bridges and shows a hindered rotation of its tert‐butyl group.     

1,4‐Di(isopropyl)‐1,4‐diazabutadien als Abfangreagenz für monomere Bruchstücke des Tetragalliumclusters Ga4[C(SiMe3)3]4 – Bildung eines ungesättigten GaN2C2‐Heterocyclus und eines Oxidationsprodukts mit Ga‐O‐O‐Ga‐Gruppe

1,4‐Di(isopropyl)‐1,4‐diazabutadiene as a Reagent for the Trapping of Monomeric Fragments of the Tetragalliumcluster Ga₄[C(SiMe₃)₃]₄ – Formation of an Unsaturated GaN₂C₂ Heterocycle and an Oxidation Product Containing a Ga‐O‐O‐Ga Group The tetrahedral tetragallium cluster Ga₄[C(SiMe₃)₃]₄ ( 1 ) dissociates upon dissolution to yield the monomeric fragments Ga‐R [R = C(SiMe₃)₃]. These monomers could be trapped now by the treatment of their solutions with 1,4‐di(isopropyl)‐1,4‐diazabutadiene. The product of the cycloaddition reaction ( 2 ) possesses a five‐membered GaN₂C₂ heterocycle with a coordinatively unsaturated gallium atom and an endocyclic C=C double bond. 2 is rather sensitive towards oxidation by traces of air. The contact with oxygen yielded a digallium peroxide [(C₂N₂iPr₂)RGa‐O‐O‐GaR(C₂N₂iPr₂)] ( 3 ) which was isolated in a very low yield only and which has a gallium atom attached to each oxygen atom of the inner peroxo group. Both chelating ligands of 3 possess an unpaired electron.     

Synthese und Kristallstruktur eines μ-Methylen-μ-hydrido-dialanats [R2Al(μ-CH2)(μ-H)AlR2]− (R = CH(SiMe3)2)

Synthesis and Crystal Structure of a μ-Methylene-μ-hydrido-dialanate [R₂Al(μ-CH₂)(μ-H)AlR₂]^? (R = CH(SiMe₃)₂) tert-Butyl lithium reacts with the recently synthesized methylene bridged dialuminium compound [(Me₃Si)₂CH]₂Al? CH₂? Al[CH(SiMe₃)₂]₂ 2 in the presence of TMEDA under β-elimination; the thereby formed hydride anion is bound in a chelating manner by both unsaturated aluminium atoms forming a 3c–2e–Al? H? Al bond. The crystal structure of the product shows two independent molecules differing only slightly in bond lengths and angles, but significantly in conformation. While one of the Al₂CH heterocycles deviates little from planarity with a rough C₂ symmetry for the whole anion, the other one is folded with an angle of 21.1° and the arrangement of the substituents is best described by C_s symmetry.     

Reaktionen der Digalliumverbindung R2Ga–GaR2 [R = CH(SiMe3)2] mit Wasser und Carbonsäuren – Synthese von μ‐Hydroxo‐μ‐carboxylatodigallium‐Verbindungen unter Erhalt der Ga–Ga‐Bindungen

Treatment of the digallium compound R₂Ga–GaR₂ [ 1 , R = CH(SiMe₃)₂] with a broad variety of functionalized carboxylic acids in the presence of water yielded μ‐hydroxo‐μ‐carboxylatodigallium compounds ( 2 – 10 ) containing intact Ga–Ga bonds in high to moderate yields. The compounds form dimeric formula units in which the unsupported Ga–Ga bonds are bridged by two hydroxo and two carboxylato ligands. Each gallium atom is terminally coordinated by a bulky alkyl group. NMR spectroscopy revealed mixtures of two isomeric compounds in solution in all cases. The second component may show a different bridging mode with each Ga–Ga bond bridged by a bidentate carboxylato ligand to form Ga₂O₂C five‐membered heterocycles.     

Synthese eines funktionalen Aluminiumalkinids,Me3C‐C≡C‐AlBr2, und dessen Reaktionen mit der sperrigen Lithiumverbindung LiCH(SiMe3)2

Synthesis of a Functional Aluminium Alkynide, Me₃C‐C≡C‐AlBr₂, and its Reactions with the Bulky Lithium Compound LiCH(SiMe₃)₂ Treatment of aluminium tribromide with the lithium alkynide (Li)C≡C‐CMe₃ afforded the aluminium alkynide Me₃C‐C≡C‐AlBr₂ ( 1 ) in an almost quantitative yield. 1 crystallizes with trimeric formula units possessing Al₃C₃ heterocycles and the anionic carbon atoms of the alkynido groups in the bridging positions. A dynamic equilibrium was determined in solution which probably comprises trimeric and dimeric formula units. Reaction of 1 with one equivalent of LiCH(SiMe₃)₂ yielded the compound [Me₃C‐C≡C‐Al(Br)‐CH(SiMe₃)₂]₂ ( 2 ), which is a dimer via Al‐C‐Al bridges. Two equivalents of the lithium compound gave a mixture of four main‐products, which could be identified as 2 , Li[Me₃C‐C≡C‐Al{CH(SiMe₃)₂}₃] ( 3 ), Me₃C‐C≡C‐Al[CH(SiMe₃)₂]₂ ( 4 ), and Al[CH(SiMe₃)₂]₃. The lithium atom of 3 is coordinated by the C≡C triple bond and an inner carbon atom of one bis(trimethylsilyl)methyl group. Further interactions were observed to C‐H bonds of methyl groups.     

Neue metallorganisch substituierte Indium–Stickstoff-Verbindungen. Synthese und Kristallstrukturen von [{Cp(CO)3Mo}2InN(SiMe3)2] und [{Cp(CO)3Mo}In{N(SiMe3)2}2]

New Organometallic Indium Nitrogen Compounds. Synthesis and Crystal Structures of [{Cp(CO)₃Mo}₂InN(SiMe₃)₂] and [{Cp(CO)₃Mo}In{N(SiMe₃)₂}₂] The reaction of [{Cp(CO)₃Mo}₂InCl] with LiN · (SiMe₃)₂ leads to the formation of [{Cp(CO)₃Mo}₂InN · (SiMe₃)₂] ( 1 ). 1 is monomeric and it contains an indium atom which is coordinated in a trigonal planar manner by two {Cp(CO)₃Mo} fragments and a N(SiMe₃)₂ group. The corresponding bis-amide [{Cp(CO)₃Mo}In{N(SiMe₃)₂}₂] ( 2 ) is prepared by the reaction of [{Cp(CO)₃Mo}InCl₂] with two equivalents of LiN(SiMe₃)₂. In analogy to 1, 2 is monomeric and it contains an indium atom in a trigonal planar coordination.     

Die Kristallstruktur von cis‐ und trans‐N‐iso‐Propylamidodimethylindium, [(CH3)2In‐N(H)iC3H7]2

The Crystal Structure of cis‐ and trans‐N‐iso‐Propylamidodimethyl Indium, [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ According to the X‐ray structure determination [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ (prepared from InMe₃ (Me = CH₃) and H₂NⁱPr (ⁱPr = CH(CH₃)₂) crystallizes in the monoclinic space group P2₁/n with 3 dimeric trans as well as 3 dimeric cis isomers per unit cell. The centrosymmetric form has a planar In₂N₂ core with In—N bonds of 222.1(4) and 222.9(5) pm, respectively, the skeleton of the cis isomer with In—N bonds of 221.4(4) pm is slightly folded (13.7°). Some ¹H, ¹³C NMR, IR, and Raman data are reported.     

[2‐(2‐Pyridyl)‐1H‐benzimidazole‐κ2N2,N3]bis(p‐toluato‐κ2O,O′)manganese(II)

In the title compound, [Mn(C₈H₇O₂)₂(C₁₂H₉N₃)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2‐(2‐pyridyl)benzimidazole ligand [Mn—N = 2.1954 (13) and 2.2595 (14) Å] and two p‐toluate ligands [Mn—O = 2.1559 (13)–2.2748 (14) Å]. It displays a severely distorted octahedral geometry, with cis angles ranging from 58.87 (4) to 106.49 (5)°. Intermolecular C—H...O hydrogen bonds between the p‐toluate ligands link the molecules into infinite chains, and every two neighbouring chains are further coupled by N—H...O and C—H...O hydrogen bonds between the 2‐(2‐pyridyl)benzimidazole and p‐toluate ligands, leading to an infinite ribbon‐like double‐chain packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and possible C—H...π interactions, as well as stacking interactions involving the 2‐(2‐pyridyl)benzimidazole ligands.     

(6‐Oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylato‐κ2O5,O6)bis[2‐(2‐pyridyl)‐1H‐benzimidazole‐κ2N2,N3]manganese(II) monohydrate

In the title compound, [Mn(C₅H₂N₂O₄)(C₁₂H₉N₃)₂]·H₂O, the Mn^II centre is surrounded by three bidentate chelating ligands, namely, one 6‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (or uracil‐5‐carboxylate, Huca²⁻) ligand [Mn—O = 2.136 (2) and 2.156 (3) Å] and two 2‐(2‐pyridyl)‐1H‐benzimidazole (Hpybim) ligands [Mn—N = 2.213 (3)–2.331 (3) Å], and it displays a severely distorted octahedral geometry, with cis angles ranging from 73.05 (10) to 105.77 (10)°. Intermolecular N—H...O hydrogen bonds both between the Hpybim and the Huca²⁻ ligands and between the Huca²⁻ ligands link the molecules into infinite chains. The lattice water molecule acts as a hydrogen‐bond donor to form double O...H—O—H...O hydrogen bonds with the Huca²⁻ O atoms, crosslinking the chains to afford an infinite two‐dimensional sheet; a third hydrogen bond (N—H...O) formed by the water molecule as a hydrogen‐bond acceptor and a Hpybim N atom further links these sheets to yield a three‐dimensional supramolecular framework. Possible partial π–π stacking interactions involving the Hpybim rings are also observed in the crystal structure.     

Kristallstruktur des Zinkamids Zn[N(SiMe3)2]2

Crystal Structure of the Zinc Amide Zn[N(SiMe₃)₂]₂ X‐ray quality crystals of Zn[N(SiMe₃)₂]₂ (monoclinic, P2₁/c) are obtained by sublimation of the zinc amide Zn[N(SiMe₃)₂]₂ at —30 °C in vacuo (300 torr). According to the result of the X‐ray structural analysis, Zn[N(SiMe₃)₂]₂ contains an almost linear N‐Zn‐N unit with two short N‐Zn bonds.     

Synthese und Charakterisierung neuer cyclischer und käfigartiger Indium‐Phosphor‐ und Indium‐Arsen‐Verbindungen

Synthesis and Characterization of New Cyclic and Cage‐like Indium — Phosphorus and Indium — Arsenic Compounds The reaction of InEt₃ with H₂ESiiPr₃ initially yields the cyclic compound [Et₂InP(H)SiiPr₃]₂ ( 2 ). 2 appears as a mixture of cis and trans isomers and has been characterized by ³¹P‐NMR spectroscopy, IR spectroscopy, and mass spectrometry. 2 decomposes in solution under elimination of ethane during a few days to form [EtInPSiiPr₃]₄ ( 3 ) with a cage‐like structure. The analogous arsenic compound [EtInAsSiiPr₃]₄ ( 4 ) can be prepared by reaction of InEt₃ with H₂AsSiiPr₃. Central structural motif of 3 and 4 is an In₄E₄ heterocubane like structure (E = P, As), whereas the reaction of InEt₃ with H₂PSiMe₂Thex (Thex = CMe₂iPr) yields [EtInPSiMe₂Thex]₆ ( 5 ) with a hexagonal prismatic structure.     

Poly[tetra‐μ2‐l‐lactato‐indium(III)sodium(I)]

The asymmetric unit of the title compound, [InNa(C₃H₅O₃)₄]_n, consists of one In^III ion, one Na^I ion and four crystallographically independent l ‐lactate monoanions. The coordination of the In^III ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal–bipyramidal coordination geometry. The Na^I ion is six‐coordinated by four carboxylate O atoms and two hydroxy O atoms from four l ‐lactate ligands in a distorted octahedral geometry. Each In^III ion is coordinated by four surrounding l ‐lactate ligands to form an [In(l ‐lactate)₄]⁻ unit, which is further linked by Na^I ions through Na—O bonds to give a two‐dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.     

Pt[In–C(SiMe3)3]4 – eine zu Pt(CO)4 analoge Verbindung mit einem durch vier InR‐Liganden ideal tetraedrisch koordinierten Platinatom

Pt[In–C(SiMe₃)₃]₄ – a Pt(CO)₄ Analogous Compound with a Platinum Atom Tetrahedrally coordinated by Four InR Ligands The reaction of the tetrahedral alkylindium(I) compound In₄[C(SiMe₃)₃]₄ ( 1 ) with bis(cyclooctadiene)platinum(0) afforded the compound Pt[InC(SiMe₃)₃]₄ ( 2 ), which is an analogue of the thermally unstable carbonyl complex Pt(CO)₄ and possesses a platinum atom tetrahedrally coordinated by four InR ligands.     

Darstellung,Charakterisierung und Reaktionsverhalten von Natrium‐ und Kaliumhydridosilylamiden R2(H)Si—N(M)R′ (M = Na,K) — Kristallstruktur von [(Me3C)2(H)Si—N(K)SiMe3]2·THF

Preparation, Characterization and Reaction Behaviour of Sodium and Potassium Hydridosilylamides R₂(H)Si—N(M)R′ (M = Na, K) — Crystal Structure of [(Me₃C)₂(H)Si—N(K)SiMe₃]₂ · THF The alkali metal hydridosilylamides R₂(H)Si—N(M)R′ 1a‐Na — 1d—Na and 1a‐K — 1d‐K ( a : R = Me, R′ = CMe₃; b : R = Me, R′ = SiMe₃; c : R = Me, R′ = Si(H)Me₂; d : R = CMe₃, R′= SiMe₃) have been prepared by reaction of the corresponding hydridosilylamines 1a — 1d with alkali metal M (M = Na, K) in presence of styrene or with alkali metal hydrides MH (M = Na, K). With NaNH₂ in toluene Me₂(H)Si—NHCMe₃ ( 1a ) reacted not under metalation but under nucleophilic substitution of the H(Si) atom to give Me₂(NaNH)Si—NHCMe₃ ( 5 ). In the reaction of Me₂(H)Si—NHSiMe₃ ( 1b ) with NaNH₂ intoluene a mixture of Me₂(NaNH)Si—NHSiMe₃ and Me₂(H)Si—N(Na)SiMe₃ ( 1b‐Na ) was obtained. The hydridosilylamides have been characterized spectroscopically. The spectroscopic data of these amides and of the corresponding lithium derivatives are discussed. The ²⁹Si‐NMR‐chemical shifts and the ²⁹Si—¹H coupling constants of homologous alkali metal hydridosilylamides R₂(H)Si—N(M)R′ (M = Li, Na, K) are depending on the alkali metal. With increasing of the ionic character of the M—N bond M = K > Na > Li the ²⁹Si‐NMR‐signals are shifted upfield and the ²⁹Si—¹H coupling constants except for compounds (Me₃C)(H)Si—N(M)SiMe₃ are decreased. The reaction behaviour of the amides 1a‐Na — 1c‐Na and 1a‐K — 1c‐K was investigated toward chlorotrimethylsilane in tetrahydrofuran (THF) and in n‐pentane. In THF the amides produced just like the analogous lithium amides the corresponding N‐silylation products Me₂(H)Si—N(SiMe₃)R′ ( 2a — 2c ) in high yields. The reaction of the sodium amides with chlorotrimethylsilane in nonpolar solvent n‐pentane produced from 1a‐Na the cyclodisilazane [Me₂Si—NCMe₃]₂ ( 8a ), from 1b‐Na and 1‐Na mixtures of cyclodisilazane [Me₂Si—NR′]₂ ( 8b , 8c ) and N‐silylation product 2b , 2c . In contrast to 1b‐Na and 1c‐Na and to the analogous lithium amides the reaction of 1b‐K and 1c‐K with chlorotrimethylsilane afforded the N‐silylation products Me₂(H)Si—N(SiMe₃)R′ ( 2b , 2c ) in high yields. The amide [(Me₃C)₂(H)Si—N(K)SiMe₃]₂·THF ( 9 ) crystallizes in the space group C2/c with Z = 4. The central part of the molecule is a planar four‐membered K₂N₂ ring. One potassium atom is coordinated by two nitrogen atoms and the other one by two nitrogen atoms and one oxygen atom. Furthermore K···H(Si) and K···CH₃ contacts exist in 9 . The K—N distances in the K₂N₂ ring differ marginally.     

Dinuclear Dysprosium and Ytterbium Complexes Incorporating N,N‐Bis(pyrrolyl‐α‐methyl)‐N‐methylamine Ligand: Syntheses and Structures

Reaction of DyCl₃ with two equivalents of NaN(SiMe₃)₂ in THF yielded {Dy(μ‐Cl)[N(SiMe₃)₂]₂(THF)}₂ ( 1 ). X‐ray crystal structure analysis revealed that 1 is a centrosymmetric dimer with asymmetrically bridging chloride ligands. The metal coordination arrangement can be best described as distorted trigonal bipyramid. The bond lengths of Ln–Cl and Ln–N showed a decreasing trend with the contraction of the size of Ln³⁺. Treatment of N,N‐bis(pyrrolyl‐α‐methyl)‐N‐methylamine (H₂dpma) with 1 and known compound {Yb(μ‐Cl)[N(SiMe₃)₂]₂(THF)}₂, respectively, led to the formations of [Dy(μ‐Cl)(dpma)(THF)₂]₂ ( 2 ) and {Yb(μ‐Cl)[N(SiMe₃)₂]₂(THF)}₂ ( 3 ). Compounds 2 and 3 were fully characterized by single‐crystal X‐ray crystallography, elemental analysis, and ¹H NMR spectroscopy. Structure determination indicated that 2 and 3 exhibit as centrosymmetric dimers with asymmetrically bridging chloride ligands. One pot reactions involving LnCl₃ (Ln = Dy and Yb), LiN(SiMe₃)₂, and H₂dpma were explored and desired products 2 and 3 were not yielded, which indicated that 1 and {Yb(μ‐Cl)[N(SiMe₃)₂]₂(THF)}₂ are the demanding precursors to synthesize Dysprosium and Ytterbium complexes supported by dpma^2– ligand. Compounds 2 and 3 are the first reported lanthanide complexes chelated by dpma^2– ligand.     

A novel one‐dimensional complex: catena‐poly­[[manganese(III)‐di‐μ‐2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolato‐κ2O1,N:κO2;κO2:κ2O1] chloride]

In the title one‐dimensional complex, {[Mn^III(C₉H₁₀NO₂)₂]Cl}_n, the Schiff base ligand 2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolate (Hsae⁻) functions as both a bridging and a chelating ligand. The Mn^III ion is six‐coordinated by two N and four O atoms from four different Hsae⁻ ligands, yielding a distorted MnO₄N₂ octahedral environment. Each [Mn^III(Hsae)₂]⁺ cationic unit has the Mn atom on an inversion centre and each [Mn^III(Hsae)₂]⁺ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae⁻ rings.     

Bis(di‐2‐pyridylamine‐κ2N2,N2′)(nitrato‐κ2O,O′)nickel(II) nitrate

<!?tpct=26.8pt>In the ionic title compound, [Ni(NO₃)(C₁₀H₉N₃)₂]NO₃, the central Ni^II atom exhibits cis‐NiN₄O₂ octahedral coordination with three chelating ligands, viz. one nitrate anion and two di‐2‐pyridylamine (dpya) molecules. A second nitrate group acts as a counter‐ion. The complex cations and the nitrate anions are also linked by N—H...O hydrogen bonds. The compound was prepared in two different reproducible ways: direct synthesis from Ni(NO₃)₂ and dpya yielded systematically twinned crystals (the twinning law is discussed), while single crystals were obtained unexpectedly from the Ni(NO₃)₂/dpya/maleic acid/NaOH system.