Investigation of the Hydrolysis Stability of Triazine Tricarboxylate in the Presence of Transition Metal(II) Ions and Synthesis and Crystal Structure of the Alkaline Earth Triazine Tricarboxylates M3[C3N3(CO2)3]2·12H2O (M = Sr,Ba)

The stability against hydrolysis of triazine tricarboxylate (TTC) in the presence of divalent transition metal and alkaline earth ions was investigated by means of X‐ray diffraction and FTIR spectroscopy. Depending on the size of the cation either formation of the respective triazine tricarboxylate salts or hydrolysis of TTC yielding oxalate was observed. The hydrolysis of TTC induced by transition metal ions could be explained in analogy to the hydrolysis of triazine tris(2‐pyrimidyl) as a result of ring tension caused by the coordination of these ions. By the reaction of potassium triazine tricarboxylate with alkaline earth salts in aqueous solution the alkaline earth triazine tricarboxylates M₃[C₃N₃(CO₂)₃]₂ · 12H₂O (M = Sr, Ba) were obtained and analyzed by single‐crystal X‐ray diffraction. The isotypic salts represent the first examples of alkaline earth triazine tricarboxylates and the first TTC salts comprising solely divalent cations.     

K3[C3N3(COO)3]·2H2O – Crystal Structure of a New Alkali Derivative of the Multidentate Ligand Triazine Tricarboxylate

Potassium‐1,3,5‐triazine‐2,4,6‐tricarboxylate dihydrate K₃[C₃N₃(COO)₃] · 2H₂O was obtained by saponification of the respective ethyl ester in aqueous solution under mild conditions and subsequent crystallization at 4 °C. The crystal structure of the molecular salt was elucidated by single‐crystal X‐ray diffraction [P , a = 696.63(14), b = 1748.5(3), c = 1756.0(3) pm, α = 119.73(3), β = 91.96(3), γ = 93.84(3)°, V = 1847.6(6) · 10⁶ pm³, Z = 6, T = 200 K]. Perpendicular to [100] the triazine tricarboxylate and potassium ions are arranged in layers alternating with layers of crystal water molecules. Two thirds of the triazine tricarboxylate units form hexagonal channels being filled with the remaining triazine tricarboxylate molecules. K₃[C₃N₃(COO)₃] · 2H₂O was additionally investigated by means of FTIR spectroscopy, TG and DTA measurements.     

The Sodium (Iso)Cyanurates Nax[H3–xC3N3O3]·yH2O (x = 1–3, y = 0, 1): A Key‐Series for Understanding the Crystal Chemistry of Metal (Iso)Cyanurates

The (iso)cyanurates Na[H₂C₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃], and Na₃[C₃N₃O₃] were synthesized phase pure from Na₂CO₃ · 10H₂O, NaOH, and cyanuric acid, respectively, in aqueous solution by carefully adjusting the crystallization conditions. The crystal structures of all compounds were determined by single‐crystal X‐ray diffraction {Na₂[HC₃N₃O₃] · H₂O: P1 , a = 3.51660(10) Å, b = 7.8300(3) Å, c = 11.3966(4) Å, α = 86.4400(10)°, β = 85.5350(10)°, γ = 85.0720(10)°, Z = 2, R₁ = 0.030, wR₂ = 0.078; Na₂[HC₃N₃O₃]: Pnma, a = 6.3409(6) Å, b = 12.2382(13) Å, c = 6.5919(7) Å, Z = 4, R₁ = 0.045, wR₂ = 0.079; Na₃[C₃N₃O₃]: R3 c, a = 11.7459(3) Å, c = 6.5286(3) Å, Z = 3, R₁ = 0.039, wR₂ = 0.066}. The structures show ribbons (Na[H₂C₃N₃O₃] · H₂O), dimers (Na₂[HC₃N₃O₃] · H₂O), chains (Na₂[HC₃N₃O₃]), or columns (Na₃[C₃N₃O₃]) of hydrogen‐bonded and parallel stacked (iso)cyanurate anions. These motifs are shown to be characteristic for certain degrees of protonation and hydration, and all (iso)cyanurate crystal structures found so far were classified accordingly. X‐ray powder patterns, thermogravimetry curves, IR and UV/Vis spectra were measured for all compounds.     

The Crystal Structures of Two No–Metal Tricyanomelaminates: Diammonium Tricyanomelaminate Dihydrate [NH4]2[C6N9H] · 2 H2O and Dimelaminium Tricyanomelaminate Melamine Dihydrate [C3N6H7]2[C6N9H] · C3N6H6 · 2 H2O

Diammonium tricyanomelaminate dihydrate [NH₄]₂[C₆N₉H] · 2 H₂O ( 1 ) and dimelaminium tricyanomelaminate melamine dihydrate [C₃N₆H₇]₂[C₆N₉H] · C₃N₆H₆ · 2 H₂O ( 2 ) were obtained by metathesis reactions from Na₃[C₆N₉] in aqueous solution and characterized by single‐crystal X‐ray diffraction and ¹⁵N solid‐state NMR spectroscopy ( 1 ). Both salts contain mono‐protonated tricyanomelaminate (TCM) anions and crystallize as dihydrates. Considering charge balance requirements, the crystal structure of 1 (C2/c, a = 3181.8(6) pm, b = 360.01(7) pm, c = 2190.4(4) pm, β = 112.39(3)°, V = 2319.9(8) 10⁶ · pm³) can best be described by assuming a random distribution of an ammonium ion – crystal water pair over two energetically similar sites. Apart from two melaminium cations, 2 (P2₁/c, a = 674.7(5) pm, b = 1123.6(5) pm, c = 3400.2(5) pm, β = 95.398(5), V = 2566(2) 10⁶ · pm³) contains one neutral melamine per formula unit acting as an additional “solvent” molecule and yielding a donor‐acceptor type of π–stacking interaction.     

[Gd(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O的晶体结构和生物活性

在水乙醇混合溶剂中，首次得到了2-羰基丙酸水杨酰腙、1，10-菲啰啉与硝酸钆形成的配合物[Gd(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]₂·phen·4H₂O，并测试了其单晶结构。该配合物属三斜晶系，空间群为P-1。每个配合物分子中有两个九配位的钆的结构单元，每个钆离子与两个三齿配体2-羰基丙酸水杨酰腙（分别以负一价和负二价形式）和三个水分子配位。每个钆单元在空间呈扭曲的单帽四方反棱柱。同时还有一个游离的1，10-菲啰啉存在于晶格中，通过氢键与配位水作用。生物活性试验表明该配合物对三种病原菌有一定的抑菌活性。     

Kristallstruktur von Natrium‐Dihydrogencyamelurat‐Tetrahydrat Na[H2(C6N7)O3] · 4 H2O

Crystal Structure of Sodium Dihydrogencyamelurate Tetrahydrate Na[H₂(C₆N₇)O₃] · 4 H₂O Sodium dihydrogencyamelurate‐tetrahydrate Na[H₂(C₆N₇)O₃]·4 H₂O was obtained by neutralisation of an aqueous solution, previously prepared by hydrolysis of the polymer melon with sodium hydroxide. The crystal structure was solved by single‐crystal X‐ray diffraction ( a = 6.6345(13), b = 8.7107(17), c = 11.632(2) Å, α = 68.96(3), β = 87.57(3), γ = 68.24(3)°, V = 579.5(2) ų, Z = 2, R1 = 0.0535, 2095 observed reflections, 230 parameters). Both hydrogen atoms of the dihydrogencyamelurate anion are directly bound to nitrogen atoms of the cyameluric nucleus, thus proving the preference of the keto‐tautomere in salts of cyameluric acid in the solid‐state. The compound forms a layer‐like structure with an extensive hydrogen bonding network.     

Three isomorphous 2,6‐dibromopyridinium tetrabromidometallates: (C5H4Br2N)2[MBr4]·2H2O (M = Cu,Cd and Hg)

The structures of three isomorphous compounds, namely bis(2,6‐dibromopyridinium) tetrabromidocuprate(II) dihydrate, (C₅H₄Br₂N)₂[CuBr₄]·2H₂O, bis(2,6‐dibromopyridinium) tetrabromidocadmate(II) dihydrate, (C₅H₄Br₂N)₂[CdBr₄]·2H₂O, and bis(2,6‐dibromopyridinium) tetrabromidomercurate(II) dihydrate, (C₅H₄Br₂N)₂[HgBr₄]·2H₂O, show a crystal supramolecularity represented by M—Br...H—O—H...Br—M intermolecular interactions along with (π)N—H...OH₂ hydrogen‐bonding interactions forming layers connected via aryl–aryl face‐to‐face stacking of cations, leading to a three‐dimensional network. The anions have significantly distorted tetrahedral geometry and crystallographic C₂ symmetry. The stability of this crystal lattice is evidenced by the crystallization of a whole series of isomorphous compounds.     

Über die Schichtstruktur von Cu2(H2O)4[C4H4N2][C6H2(COO)4]·2H2O

The Layered Structure of Cu₂(H₂O)₄[C₄H₄N₂][C₆H₂(COO)₄]·2H₂O Triclinic single crystals of Cu₂(H₂O)₄[C₄H₄N₂][C₆H₂(COO)₄]·2H₂O have been grown in an aqueous silica gel. Space group (Nr. 2), a = 723.94(7) pm, b = 813.38(14) pm, c = 931.0(2) pm, α = 74.24(2)°, β = 79.24(2)°, γ = 65.451(10)°, V = 0.47819(14) nm³, Z = 1. Cu²⁺ is coordinated in a distorted, octahedral manner by two water molecules, three oxygen atoms of the pyromellitate anions and one nitrogen atom of pyrazine (Cu—O 194.1(2)–229.3(3) pm; Cu–N 202.0(2) pm). The connection of Cu²⁺ and [C₆H₂(COO)₄)]^4? yields infinite strands, which are linked by pyrazine molecules to form a two‐dimensional coordination polymer. Thermogravimetric analysis in air showed that the dehydrated compound was stable between 175 and 248 °C. Further heating yielded CuO.     

Synthesis,Crystal Structure and Properties of Rubidium Dihydrogentricyanomelaminate Semihydrate Rb[H2C6N9] · 1/2 H2O

Rubidium dihydrogentricyanomelaminate semihydrate Rb[H₂C₆N₉] · ¹/₂ H₂O was obtained as colorless rod‐like single crystals from a solution of Rb₃[C₆N₉] · H₂O and 0.1 M HCl after water evaporation at room temperature. According to the X‐ray single‐crystal structure determination (Rb[H₂C₆N₉] · ¹/₂ H₂O: C2/c (no. 15), a = 2007.4(3) pm, b = 512.2(1) pm, c = 2168.0(4) pm, β = 111.66(2)°, Z = 8, R1 = 0.059, 2391 independent reflections, 159 parameters) Rb⁺ and cyclic planar [H₂C₆N₉]^— ions as well as hydrate water molecules occur in the crystal. Rb[H₂C₆N₉] · ¹/₂ H₂O was investigated by FTIR and Raman spectroscopy, TG measurements and temperature‐dependent X‐ray powder diffraction. According to the thermoanalytic investigations, dehydration of Rb[H₂C₆N₉] · ¹/₂ H₂O starts above 60 °C and is finished below 250 °C.     

An Organically Templated Copper Pentaborate with Infinite Metallo-chains:[Cu(C3N2H4)4][Cu(CH3COO)2(C3N2H4)2(H2O)2][B5O6(OH)4]2

A novel organically templated copper pentaborate, [Cu(C₃N₂H₄)₄][Cu(CH₃COO)₂(C₃N₂H₄)₂(H₂O)₂]‐ [B₅O₆(OH)₄]₂, was synthesized by hydrothermal reaction and characterized by elemental analysis, single‐crystal X‐ray diffraction, FT‐IR spectroscopy, Raman spectroscopy and TGA. The crystal structure of this compound consists of two copper‐centered polyhedra and two discrete [B₅O₆(OH)₄]^? pentaborate anions, which are linked together through intensive hydrogen bonding interactions, forming a 3D framework with large channels along c axis. The discrete pentaborate anions form infinite layers by hydrogen bonds. Moreover, the two crystallographically different octahedral coppers are connected by common oxygen atom to form an infinite chain.     

Imidazole Coordinated Sandwich‐type Antimony Poly‐oxotungstates Na9[{Na(H2O)2}3{M(C3H4N2)}3(SbW9O33)2]·xH2O (M=NiII,CoII, ZnII,MnII)

The imidazole covalently coordinated sandwich‐type heteropolytungstates Na₉[{Na(H₂O)₂}₃{M(C₃H₄N₂)}₃‐ (SbW₉O₃₃)₂]·xH₂O (M=Ni^II, x=32; M=Co^II, x=32; M=Zn^II, x=33; M=Mn^II, x=34) were obtained by the reaction of Na₂WO₄·2H₂O, SbCl₃·6H₂O, NiCl₂·6H₂O [MnSO₄·H₂O, Co(NO₃)₂·6H₂O, ZnSO₄·7H₂O] and imidazole at pH≈7.5. The structure of Na₉[{Na(H₂O)₂}₃{Ni(C₃H₄N₂)}₃(SbW₉O₃₃)₂]·32H₂O was determined by single crystal X‐ray diffraction. Polyanion [{Na(H₂O)₂}₃{Ni(C₃H₄N₂)}₃(SbW₉O₃₃)₂}₃]^9? has approximate C_3v symmetry, imidazole coordinated six‐nuclear cluster [{Na(H₂O)₂}₃{Ni(C₃H₄N₂)}₃]⁹⁺ is encapsulated between two (α‐SbW₉O₃₃)^9?, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals (Na‐Ni‐Na‐Ni‐Na‐Ni) in the central belt, and π‐stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60°. The compounds were also characterized by IR, UV‐Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

Synthesis and Crystal Structure of the Binuclear Complex [Pr2(C10H8N2O4)2(C10H9N2O4)2(H2O)4]·3H2O·C6H6

The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C₁₀H₁₀N₂O₄, H₂L) was prepared in H₂O‐C₂H₅OH mixed solution, and the crystal structure of [Pr₂L₂(HL)₂(H₂O)₄]·3H₂O·C₆H₆ was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr³⁺ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ₂‐bridging mode.     

NC12H8(NH)2[Gd(N3C12H8)4] und [Gd(N3C12H8)3(N3C12H9)]·PhCN: Ein Beitrag zur Reaktivität und Kristallchemie homoleptischer Selten‐Erd‐Pyridylbenzimidazolate

NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] and [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN: A Contribution to the Reactivity and Crystal Chemistry of Homoleptic Pyridylbenzimidazolates of the Rare Earth Elements Transparent colourless crystals of the compound NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] were obtained by solvent‐free reaction of gadolinium metal with molten 2‐(2‐Pyridyl)‐benzimidazole. Transparent yellow crystals of the compound [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN were obtained by further reacting NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] with benzonitrile thermally. Both compounds exhibit homoleptic pure nitrogen coordinations of gadolinium, the PhCN ligand is not coordinating. Whilst NC₁₂H₈(NH)₂[Gd(N₃C₁₂H₈)₄] is salt like and consists of (NC₁₂H₈(NH)₂)⁺ and [Gd(N₃C₁₂H₈)₄]^— ions, [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)]·PhCN has a molecular structure of uncharged [Gd(N₃C₁₂H₈)₃(N₃C₁₂H₉)] units.     

Bariumstannat‐Pulver durch hydrothermale Synthese und durch Thermolyse von Bariumzinn(IV)‐glykolaten. Synthese und Struktur von [Ba(C2H6O2)4][Sn(C2H4O2)3] und [Ba(C2H6O2)2][Sn(C2H4O2)3]·CH3OH

Barium Stannate Powders from Hydrothermal Synthesis and by Thermolysis of Barium‐Tin(IV)‐Glycolates. Synthesis and Structure of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] and [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH The hydrothermal reaction as well as the microwave assisted hydrothermal reaction of SnO₂·aq with barium hydroxide gives Ba[Sn(OH)₆] ( 1 ) as powder with bar like particles. Compound 1 of the same morphology can also be isolated from a hydrothermal reaction of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ). The reaction of SnO₂·aq with Ba(OH)₂·8H₂O in ethylene glycol yields the glycolate [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ), which forms in methanol the solvate [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH ( 4 ). Compounds 1 , 3 and 4 react at different temperatures to BaSnO₃ ( 2 ) consisting of powders with different morphologies; because of the grain size of the resulting powders compounds 3 and 4 are suitable as precursor for the fabrication of corresponding ceramics.     

Zn3(C6H14N2)3[B6P12O39(OH)12] · (C6H14N2)[HPO4]: A Chiral Borophosphate – Triethylenediammonium Hydrogenphosphate Composite

A novel borophosphate, Zn₃(C₆H₁₄N₂)₃[B₆P₁₂O₃₉(OH)₁₂] · (C₆H₁₄N₂)[HPO₄] has been synthesised under mild hydrothermal conditions at T = 165 °C. The chiral crystal structure was determined by single crystal X‐ray diffraction data (trigonal, R3 (no. 146), Z = 3, a = 2089.55(4) pm, c = 1237.03(4) pm, V = 4677.5(2) · 10⁶ pm³, R₁ = 0.066, wR₂ = 0.164 for 5100 observed reflections). The title compound can be considered as an ordered composite of the two different and neutral structures which fit into each other: An open framework of composition Zn₃(C₆H₁₄N₂)₃[B₆P₁₂O₃₉(OH)₁₂] and columns of composition (C₆H₁₄N₂)[HPO₄]. The framework structure is formed by mixed octahedral‐tetrahedral secondary building units, in a three‐dimensional arrangement reflecting a hierarchical derivative of the NbO structure type. The underlying NbO topology is illustrated with the help of Periodic Nodal Surfaces. The composite nature of the compound is resolved in the spatial segregation of two frameworks with a separating surface.     

Synthesis,Structure and Photoluminescent Properties of [C6N2H14][Nd2(C2O4)2(SO4)2(H2O)4]·H2O,a New Organically Templated Neodymium(III) Oxalate‐sulfate

An organically templated neodymium oxalate–sulfate [C₆N₂H₁₄][Nd₂(C₂O₄)₂(SO₄)₂(H₂O)₄]·H₂O ( 1 ) has been synthesized under hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction analysis. In 1 , the neodymium(III) ions are interconnected through oxalate and sulfate groups to form a neodymium oxalate–sulfate hybrid structure. A luminescence spectrum of 1 was recorded, and the luminescence decay time was also measured.     

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2‐Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O,and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L₂Pd(N₃)₂ (L = PPh₃ ( 1 ), AsPh₃ ( 2 ), and 2‐chloropyridine ( 3 )), the dimeric [(AsPh₄)₂][Pd₂(N₃)₄Cl₂] ( 4 ), the homoleptic azido palladate [(PNP)₂][Pd(N₃)₄] ( 5 ) and the homoleptic azido platinates [(AsPh₄)₂][Pt(N₃)₄] · 2 H₂O ( 6 ) and [(AsPh₄)₂][Pt(N₃)₆] ( 7 ) were determined by X‐ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1 , 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd₂(N₃)₄Cl₂]^2– anions show end‐on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C_4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N₃)₆]^2– anions in 7 are centrosymmetric (idealized S₆ symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers.     

Two new soluble iron–oxo complexes: [Fe2(μ‐O)(μ‐O2CCF3)2(O2CCF3)2(C10H8N2)2] and [Fe4(μ3‐O)2(μ‐O2CCF3)6(O2CCF3)2(C10H8N2)2]·CF3CO2H

Two new iron–oxo clusters, viz. di‐μ‐tri­fluoro­acetato‐μ‐oxo‐bis­[(2,2′‐bi­pyridine‐κ²N,N′)(tri­fluoro­acetato‐κO)­iron(III)], [Fe₂O(CF₃CO₂)₄(C₁₀H₈N₂)₂], and bis(2,2′‐bi­pyridine)­di‐μ₃‐oxo‐hexa‐μ‐tri­fluoro­acetato‐bis­(tri­fluoro­acetato)­tetrairon(III) tri­fluoro­acetic acid solvate, [Fe₄O₂(CF₃CO₂)₈(C₁₀H₈N₂)₂]·CF₃CO₂H, contain dinuclear and tetranuclear Fe^III cores, respectively. The Fe^III atoms are in distorted octahedral environments in both compounds and are linked by oxide and tri­fluoro­acetate ions. The tri­fluoro­acetate ions are either bridging (bidentate) or coordinated to the Fe^III atoms via one O atom only. The fluorinated peripheries enhance the solubility of these compounds. Formal charges for all the Fe centers were assigned by summing valences of the chemical bonds to the Fe^III atom.     

Pentazol‐Derivate und daraus entstehende Azide: [O3S—p‐C6H4—N5]— und [O3S—p‐C6H4—N3]— als Kalium‐Kronenether‐Salze

Pentazole Derivates and Azides Formed from them: Potassium‐Crown‐Ether Salts of [O₃S—p‐C₆H₄—N₅]^— and [O₃S—p‐C₆H₄—N₃]^{— —}O₃S—p‐C₆H₄—N₂⁺ was reacted with sodium azide at —50 °C in methanol, yielding a mixture of 4‐pentazolylbenzenesulfonate and 4‐azidobenzenesulfonate (amount‐of‐substance ratio 27:73 according to NMR). By addition of KOH in methanol at —50 °C a mixture of the potassium salts K[O₃S—p‐C₆H₄—N₅] and K[O₃S—p‐C₆H₄—N₃] was precipitated (ratio 60:40). A solution of this mixture along with 18‐crown‐6 in tetrahydrofurane yielded the crystalline pentazole derivate [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₅]·THF by addition of petrol ether at —70 °C. From the same solution upon evaporation and redissolution in THF/petrol ether the crystalline azide [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·THF was obtained. A solution of the latter in chloroform/toluene under air yielded [K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·1/3H₂O. According to their X‐ray crystal structure determinations [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₅]·THF and [THF‐K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·THF have the same kind of crystal packing. Differences worth mentioning exist only for the atomic positions of the pentazole ring as compared to the azido group and for one THF molecule which is coordinated to the potassium ion; different orientations of the THF molecule take account for the different space requirements of the N₅ and the N₃ group. In [K‐18‐crown‐6][O₃S—p‐C₆H₄—N₃]·1/3H₂O there exists one unit consisting of one [K‐18‐crown‐6]⁺ and one [O₃S‐C₆H₄—N₃]^— ion and another unit consisting of two [O₃S‐C₆H₄—N₃]^— ions joined via two [K‐18‐crown‐6]⁺ ions and one water molecule. The rate constants for the decomposition [O₃S‐C₆H₄—N₅]^— → [O₃S‐C₆H₄—N₃]^— + N₂ in methanol were determined at 0 °C and —20 °C.     

Two novel bis­(2,9‐dimeth­yl‐1,10‐phenanthroline)copper(I) complexes: [Cu(dmp)2]2(PF6)2·0.5(bpmh)·CH3CN and [Cu(dmp)2][N(CN)2]

Two new salts of the cation [Cu^I(dmp)₂]⁺ (dmp is 2,9‐dimeth­yl‐1,10‐phenanthroline, C₁₄H₁₂N₂), namely bis­[bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I)] bis­(hexa­fluorophos­phate) hemi[bis­(4‐pyridylmethyl­idene)hydrazine] acetonitrile solvate, [Cu(C₁₄H₁₂N₂)₂]₂(PF₆)₂·0.5C₁₂H₁₀N₄·C₂H₃N or [Cu(dmp)₂]₂(PF₆)₂·0.5(bpmh)·CH₃CN [bpmh is bis­(4‐pyridylmethyl­idene)hydrazine, C₁₂H₁₀N₄], (I), and bis­(2,9‐dimeth­yl‐1,10‐phenanthroline‐κ²N,N′)copper(I) dicyanamide, [Cu(C₁₄H₁₂N₂)₂](C₂N₃) or [Cu(dmp)₂][N(CN)₂], (II), are reported. The Cu—N bond lengths and the distortion from idealized tetra­hedral geometry of the dmp ligands are discussed and compared with related compounds. The bpmh molecule in (I) is π–π stacked with a dmp ligand at a distance of 3.4 Å, rather than coordinated to the metal atom. The molecule lies across an inversion center in the crystal. In (II), the normally coordinated dicyanamide mol­ecule is present as an uncoordinated counter‐ion.