Anion Controlled Supramolecular Self‐Assembly of Tetraprotonated Tris[2‐(benzylamino)ethyl]amine

The novel supramolecular assembly of composition [{(bz₃tren)H₄}⁴⁺ · (ReO₄)^— · 3(Cl)^—] resulted from the self‐organization of a mixture of tris[2‐(benzylamino)ethyl]amine (bz₃tren), HCl and NH₄ReO₄ at a molar ratio of 1:4.7:1 in methanol. The crystal architecture is characterized by stacks of repeating sandwich‐type building blocks that contain charge‐assisted N—H···O(Re) hydrogen bonds [N···O 2.81‐2.86Å] and weaker C—H···O(Re) interactions [C···O 3.11Å]. The stacks are further linked by N—H···Cl [N···Cl 3.03Å] and weaker C—H···Cl [C···Cl 3.47‐3.74Å] interactions into two‐dimensional layers bordered by the benzyl groups of the [(bz₃tren)H₄]⁴⁺ cations. Edge‐to‐face C—H···π interactions involving the aromatic rings occur within and between the layers. The protonation constants of bz₃tren in methanol were determined by potentiometric titration. The corresponding structures of the ligand in its different protonation states were calculated at the DFT‐level.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.     

Pseudo‐Isomerie durch unterschiedliche Jahn‐Teller‐Ordnung: Die Kristallstrukturen des Hemihydrats und des Monohydrats von (pyH)[MnF(H2PO4)(HPO4)]

Pseudo‐Isomerism by Different Jahn‐Teller Ordering: Crystal Structures of the Hemihydrate and the Monohydrate of (pyH)[MnF(H₂PO₄)(HPO₄)] With pyridinium counter cations (pyH⁺) the Mn^III fluoride phosphate anion [MnF(H₂PO₄)(HPO₄)]^— can be stabilized. It forms a chain structure with Mn³⁺ ions bridged by a fluoride ion and two bidentate phosphate groups. Under sleightly differing conditions either the hemihydrate (pyH)[MnF(H₂PO₄)(HPO₄)]·0.5H₂O ( 1 ) or the monohydrate (pyH)[MnF(H₂PO₄)(HPO₄)]·H₂O ( 2 ) is formed. The hemihydrate 1 crystallizes monoclinic in space group P2₁/n, Z = 8, a = 7.295(1), b = 17.052(2), c = 18.512(3) Å, β = 100.78(1)°, R = 0.033, the monohydrate triclinic in space group P1¯, Z = 2, a = 7.374(1), b = 8.628(1), c = 10.329(1) Å, α = 83.658(8)°, β = 77.833(9)°, γ = 68.544(8)°, R = 0.025. Whereas the topology of the chain anions is identical in both structures, the Jahn‐Teller effect is expressed in different ordering patterns: in 1 antiferrodistortive ordering of [MnF₂O₄] octahedra is observed, with alternating elongation of an F—Mn—F‐axis or a O—Mn—O‐axis, respectively. This leads to asymmetrical Mn—F—Mn‐bridges. In 2 ferrodistortive ordering is found, with elongation of all octahedra along the F—Mn—F‐axis. Thus, symmetrical bridges are formed with long Mn—F distances. This unusual pseudo‐isomerism is attributed to the differing influence of inter‐chain hydrogen bonds.     

Polysulfonylamine. CLXVI [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 15 [1] Die isotypen Kristallstrukturen von Ammonium‐ und Caesium‐dimesylamid: Kristallographische Kongruenz zwischen Wasserstoffbrücken N—H···O/N und Metall‐Ligand‐Bindungen Cs—O/N

Polysulfonylamines. CLXVI. Crystal Structures of Metal Di(methanesulfonyl)amides. 15. The Isotypic Crystal Structures of Ammonium and Cesium Dimesylamide: Crystallographic Congruency of Hydrogen Bonds N—H···O/N and Metal‐Ligand Interactions Cs—O/N The ammonium salt NH₄[N(SO₂CH₃)₂] and its previously reported cesium analogue Cs[N(SO₂CH₃)₂] are isostructural (monoclinic, space group P2₁/n, Z = 4, V at —140 °C: 0.761 and 0.832 nm³ respectively). The cesium ion adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding anions, whereas in the ammonium‐based structure each of the seven Cs—O/N interactions is perfectly mimicked by an N—H···O/N hydrogen‐bond component. To this effect, three N—H donors are engaged in asymmetric three‐centre bonds, the fourth in a moderately strong and approximately linear two‐centre bond. The crystal packings consist of anion monolayers that intercalate planar zigzag rows of cations propagating around symmetry centres (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°; N···N alternatingly 397.4 and 474.1 pm, N···N···N 136.1°). Each cation row is surrounded by and bonded to four translation‐generated anion stacks, and each anion stack connects two cation rows. The net effect is that the packings display congruent three‐dimensional networks of metal‐ligand bonds or hydrogen bonds, respectively. Moreover, close C—H···O/N interanion contacts consistent with weak hydrogen bonding are observed in both structures.     

Synthesis and Characterization of Monomeric Aryloxo Palladium Complexes of the Type [Pd(N–N)(OAr)(C6F5)]. Crystal Structure of [Pd(tmeda)(C6F5)(OC6H4NO2‐p)]

Mononuclear palladium‐hydroxo complexes of the type [Pd(N–N)(C₆F₅)(OH)][(N–N) = 2,2′‐bipyridine (bipy), 4,4′‐dimethyl‐2,2′‐bipyridine (Me₂bipy), 1,10‐phenantroline (phen) or N,N,N′,N′‐tetramethylethylenediamine (tmeda) react with phenols ArOH in tetrahydrofuran giving the corresponding aryloxo complexes [Pd(N–N)(C₆F₅)(OAr)]. Elemental analyses and spectroscopic (IR, ¹H and ¹⁹F) methods have been used to characterize the new complexes. The X‐ray crystal structure of [Pd(tmeda)(C₆F₅)(OC₆H₄NO₂‐p)] has been determined. In the crystal packing the planes defined by two C₆H₄ rings show a parallel orientation. There are also intermolecular C–H···F and C‐H···O hydrogen bonds.     

Mononuclear nickel(II) and zinc(II) complexes with deprotonated forms of the tripodal hexadentate ligand 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine

In the crystal structures of both title compounds, [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]nickel(II) [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]nickel(II) chloride methanol disolvate, [Ni(C₂₆H_25.5N₃O₃)]₂Cl·2CH₄O, and [1,3‐bis(2‐hydroxybenzylidene)‐2‐methyl‐2‐(2‐oxidobenzylideneaminomethyl)propane‐1,3‐diamine]zinc(II) perchlorate [2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methyl‐1,3‐bis(2‐oxidobenzylidene)propane‐1,3‐diamine]zinc(II) methanol trisolvate, [Zn(C₂₆H₂₅N₃O₃)]ClO₄·[Zn(C₂₆H₂₆N₃O₃)]·3CH₄O, the 3d metal ion is in an approximately octahedral environment composed of three facially coordinated imine N atoms and three phenol O atoms. The two mononuclear units are linked by three phenol–phenolate O—H...O hydrogen bonds to form a dimeric structure. In the Ni compound, the asymmetric unit consists of one mononuclear unit, one‐half of a chloride anion and a methanol solvent molecule. In the O—H...O hydrogen bonds, two H atoms are located near the centre of O...O and one H atom is disordered over two positions. The Ni^II compound is thus formulated as [Ni(H_1.5L)]₂Cl·2CH₃OH [H₃L is 1,3‐bis(2‐hydroxybenzylidene)‐2‐(2‐hydroxybenzylideneaminomethyl)‐2‐methylpropane‐1,3‐diamine]. In the analogous Zn^II compound, the asymmetric unit consists of two crystallographically independent mononuclear units, one perchlorate anion and three methanol solvent molecules. The mode of hydrogen bonding connecting the two mononuclear units is slightly different, and the formula can be written as [Zn(H₂L)]ClO₄·[Zn(HL)]·3CH₃OH. In both compounds, each mononuclear unit is chiral with either a Δ or a Λ configuration because of the screw coordination arrangement of the achiral tripodal ligand around the 3d metal ion. In the dimeric structure, molecules with Δ–Δ and Λ–Λ pairs co‐exist in the crystal structure to form a racemic crystal. A notable difference is observed between the M—O(phenol) and M—O(phenolate) bond lengths, the former being longer than the latter. In addition, as the ionic radius of the metal ion decreases, the M—O and M—N bond distances decrease.     

Synthesis and Crystal Structures of Hydrogen Monofluorophosphates with N‐containing Organic Cations. The Influence of Fluorine on their Hydrogen Bond Systems

The synthesis and crystal structures of guanidinium monofluorophosphate and hydrogen monofluorophosphates with the following cations: piperazinium, di‐ and triethylammonium, guanidinium, and dimethyluronium, are described and discussed. The structures of the acid salts consist of hydrogen‐bonded HPO₃F tetrahedra, which form infinite chains or cyclic dimers. The organic cations link these units together. All of the hydrogen bond systems observed consist of short O—H···O and longer N—H···O bonds. No O—H···F or N—H···F bonds were found. The F atom avoids hydrogen acceptor positions in the structures. The thermal behavior of [NHEt₃]HPO₃F was also studied.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

[μ‐N,N′‐Bis(2‐amino­ethyl)­oxamidato(2–)]­bis­[(4,5‐di­aza­fluoren‐9‐one)­perchloratocopper(II)] 4,5‐di­aza­fluoren‐9‐one disolvate

The title compound, [Cu₂(C₆H₁₂N₄O₂)(ClO₄)₂(C₁₁H₆N₂O)₂]·2C₁₁H₆N₂O, contains a dinuclear copper(II) complex which lies about a twofold axis at the mid‐point of the C—C bond of the ox­amide ligand that bridges the two Cu^II atoms. The Cu·Cu distance is 5.215 (2) Å and the Cu atoms have distorted octahedral coordination geometry. Intramolecular N—H·O and N—H·N hydrogen bonds and intermolecular C—H·O hydrogen bonds, together with π–π stacking interactions, dominate throughout the crystal structure.     

Synthese und Kristallstruktur von Ammin(μ3‐L‐glutamato)kupfer(II)

Synthesis and Crystal Structure of Ammine(μ₃‐L‐glutamato)copper(II) [Cu(L‐Glu)H₂O]·H₂O reacts with aqueous ammonia to give the ammine complex [Cu(L‐Glu)NH₃] ( 1 ). 1 forms orthorhombic crystals, space group P 2₁2₁2 with a = 1585,1(1) pm; b = 979,46(7) pm and c = 504,70(5) pm. In the crystal structure of 1 the copper atoms are linked by μ₃‐glutamate units to give a 2D layer structure. The copper atoms exhibit a square‐pyramidal coordination with two N atoms and two O atoms in the base plane and one O atom at the apex of the pyramid. The crystal structure is stabilized by a 3D network of N–H···O hydrogen bridges.     

N‐[(R)‐1‐(2‐Hydr­oxy‐5‐methyl­phen­yl)­eth­yl]‐N‐[(R)‐1‐(2‐meth­oxy‐5‐methyl­phen­yl)‐2‐phenyl­eth­yl]aminium chloride

The title compound, C₂₅H₃₀NO₂⁺·Cl⁻, has been synthesized, and the crystal structure shows that it is mainly stabilized through inter­molecular N—H·Cl and O—H·Cl and intra­molecular N—H·O hydrogen bonds. The absolute configuration of the new stereogenic center (the C atom adjacent to the N atom on the phenol side) was determined to have an R configuration.     

Hydrogen‐bonded frameworks of bis(2‐carboxypyridinium) hexafluorosilicate and bis(2‐carboxyquinolinium) hexafluorosilicate dihydrate

In bis(2‐carboxypyridinium) hexafluorosilicate, 2C₆H₆NO₂⁺·SiF₆²⁻, (I), and bis(2‐carboxyquinolinium) hexafluorosilicate dihydrate, 2C₁₀H₈NO₂⁺·SiF₆²⁻·2H₂O, (II), the Si atoms of the anions reside on crystallographic centres of inversion. Primary inter‐ion interactions in (I) occur via strong N—H...F and O—H...F hydrogen bonds, generating corrugated layers incorporating [SiF₆]²⁻ anions as four‐connected net nodes and organic cations as simple links in between. In (II), a set of strong N—H...F, O—H...O and O—H...F hydrogen bonds, involving water molecules, gives a three‐dimensional heterocoordinated rutile‐like framework that integrates [SiF₆]²⁻ anions as six‐connected and water molecules as three‐connected nodes. The carboxyl groups of the cation are hydrogen bonded to the water molecule [O...O = 2.5533 (13) Å], while the N—H group supports direct bonding to the anion [N...F = 2.7061 (12) Å].     

Ammonium N‐(6‐amino‐3,4‐di­hydro‐3‐methyl‐5‐nitro­so‐4‐oxopyrimidin‐2‐yl)­glycinate monohydrate forms hydrogen‐bonded bilayers

In the title compound, NH₄⁺·C₇H₈N₅O₄⁻·H₂O, the independent components are linked into bilayers by an extensive series of two‐centre N—H⃛O hydrogen bonds [H⃛O = 1.85–1.96 Å, N⃛O = 2.776 (2)–2.840 (2) Å and N—H⃛O = 149–172°], and by asymmetric three‐centre N—H⃛(O)₂, O—H⃛(N,O) and O—H⃛(O)₂ hydrogen bonds.     

Ein lamellarer Schichtverband auf der Grundlage von Wasserstoffbrücken und π‐Stapelung: Kristallstruktur des Lithiumkomplexes [Li{C6H4(SO2)2N}(H2O)3] und ein Vergleich mit anderen Metall(I)‐benzol‐1, 2‐di(sulfonyl)amiden

The title complex, obtained by treating ortho‐benzenedisulfonimide (HZ) with LiOH in aqueous solution, has been characterized by low‐temperature X‐ray diffraction (triclinic, space group P&1macr;, Z' = 1). The lithium cation is bonded to one sulfonyl oxygen atom and three water molecules in a distorted tetrahedral configuration [Li‐O 189.3(3)‐201.2(3) pm, O‐Li‐O 98.5(2)‐123.2(2)?]. The zero‐dimensional [Li(Z)(H₂O)₃] complexes, which display an intramolecular O(W)‐H···O hydrogen bond, are cross‐linked via five O(W)‐H···O/N/O(W) interactions and a remarkably short C‐H···O bond (H···O 217 pm, C‐H···O 170?) to form a two‐dimensional assembly comprising an internal polar lamella of metal cations, (SO₂)₂N groups and water molecules, and hydrophobic peripheral regions consisting of protruding benzo groups. In the packing, alternate carbocycles drawn from adjacent layers set up a π‐stacking array of parallel aromatic rings (intercentroid distances 349 and 369 pm, cycle spacings 331 and 336 pm). In a short survey, the currently known crystal packings of seven M^IZ · n H₂O (n ≥ 0) complexes are examined and compared.     

Crystal Structures and Hydrogen Bonding of Two Complexes containing the [Ammine‐chlorido‐ethylenediamine‐bis(pyridine)cobalt(III)]2+ Cation

The crystal structures of two classical cobalt(III) complexes comprising the [CoCl(NH₃)(en)(py)₂]²⁺ cation were determined by single‐crystal X‐ray diffraction. Both complexes, dark red [CoCl(NH₃)(en)(py)₂]Cl₂ · H₂O ( 1 ) and purple [CoCl(NH₃)‐(en)(py)₂][HgCl₄] · 1.125H₂O ( 2 ), crystallize in the triclinic space group P1 . In both compounds, the Co atom exhibits a typical octahedral coordination and the configuration index of the complex is OC‐6‐43. In the case of the chloride ( 1 ), the asymmetric unit comprises one formula unit, whereas there are two formula units in the case of the tetrachloridomercurate ( 2 ). Complex cations, anions, and crystal water molecules are interconnected by various N–H ··· N, N–H ··· Cl, N–H ··· O, O–H ··· Cl, and O–H ··· O bridge bonds. As a result, compound 1 features a two‐dimensional layer structure and compound 2 exists as a three‐dimensional network.     

Die Kristallstrukturen der Hexachlorometallate NH4[SbCl6], NH4[WCl6], [K(18‐Krone‐6)(CH2Cl2)]2[WCl6]·6CH2Cl2 und (PPh4)2[WCl6]·4CH3CN

Crystal Structures of the Hexachlorometalates NH₄[SbCl₆], NH₄[WCl₆], [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ and (PPh₄)₂[WCl₆]·4CH₃CN The crystal structures of the title compounds were determined by single crystal X‐ray methods. NH₄[SbCl₆] and NH₄[WCl₆] crystallize isotypically in the space group C2/c with four formula units per unit cell. The NH₄⁺ ions occupy a twofold crystallographic axis, whereas the metal atoms of the [MCl₆]^— ions occupy a centre of inversion. There exist weak interionic hydrogen bridges. [K(18‐crown‐6)(CH₂Cl₂)]₂[WCl₆]·6CH₂Cl₂ crystallizes in the orthorhombic space group R3¯/m with Z = 3. The compound forms centrosymmetric ion triples, in which the potassium ions are coordinated with a WCl₃ face each. In trans‐position to it the chlorine atom of a CH₂Cl₂ molecule is coordinated so that, together with the oxygen atoms of the crown ether, coordination number 10 is achieved. (PPh₄)₂[WCl₆]·4CH₃CN crystallizes in the monoclinic space group P2₁/c with Z = 4. This compound, too, forms centrosymmetric ion triples, in which in addition the acetonitrile molecules are connected with the [WCl₆]^2— ion via weak C—H···Cl contacts.     

Mixed‐ligand Copper(II) Complexes with N‐isopropyl‐iminodiacetato(2‐) and C‐phenyl‐imidazole Ligands. Crystal Structures of H2iPIDA, [Cu(iPIDA)(H2ϕim)(H2O)]·3H2O and [Cu(iPIDA)(H5ϕim)]n

The crystal of the N‐isopropyl‐iminodiacetic acid ( 1 ) consists of a 3D H‐bonded framework where the zwitterion (H₂iPIDA^±) is intra‐stabilized by one N⁺‐H···O interaction and both carboxyl are half‐protonated and involved in linear O‐H···O inter‐molecular bridges of 2.46 Å. The mixed‐ligand complexes [Cu(iPIDA)(H2?im)(H₂O)]·3H₂O ( 2 ) and [Cu(iPIDA)(H5?im)]_n ( 3 ) have also been synthesized and studied by thermal, spectral, magnetic and X‐ray diffraction methods. Both complexes exhibit a square base pyramidal coordination, type 4+1. Compound 3 is the less steric hindered 'remote' isomer, with H5?im instead of H4?im.     

Charge‐assisted N—H·I and C—H·I hydrogen bonding in (1R,2S)‐1‐(ferrocenylmethyl)‐2‐(methoxymethyl)pyrrolidinium iodide

In the title compound, [Fe(C₅H₅)(C₁₂H₁₉NO)]I, the ferrocene moiety has an eclipsed conformation, with mean Fe—C bond lengths of 2.031 (4) and 2.020 (6) Å for the substituted and unsubstituted cyclo­penta­dienyl rings. The pyrrolidinium heterocycle adopts an envelope conformation and has its 1‐ and 2‐substituents in a relative trans disposition. Strong (+/−)‐charge‐assisted N—H·I and C—H·I hydrogen bonds are present. The crystal structure is also stabilized by weak C—H·O interactions.     

2,6‐Dimethyl‐1,4‐benzoquinone 4‐monooxime

Mol­ecules of the title compound, C₈H₉NO₂, are linked into sheets by a combination of C—H·N, O—H·N and O—H·O hydrogen bonds and C—H·π inter­actions. The hydrogen bonds are arranged as described by the graph‐set ring notations R₂²(7) and R₃³(5), and a C8 chain motif. There are two planar symmetry‐independent mol­ecules in the asymmetric unit, with a dihedral angle of 19.24 (5)° between their least‐squares mean planes.