Synthesis and Characterization of a Two‐Dimensional Zinc Phosphite,Zn3(tren)(HPO3)3·xH2O (x ≈ 0.5; tren = tris(2‐aminoethyl)amine)

A new zinc phosphite with the formula Zn₃(tren)(HPO₃)₃·xH₂O (x≈0.5) has been synthesized under hydrothermal conditions and characterized by FTIR, elemental analysis, powder X‐ray diffraction, single‐crystal X‐ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the triclinic system, space group (No.2), a = 10.1188(9) Å, b = 10.4194(9) Å, c = 10.5176(9) Å, α = 60.763(2)°, β = 70.6150(10)°, γ = 80.725(2)°, V = 912.77(14) ų, Z = 2. The structure consists of double crankshaft chains, which are linked by Zn‐O‐P bonds to form 8‐ and 12‐membered channels along the [100] direction. The claw‐like Zn‐centered complexes of Zn(N₄C₆H₁₈) as the supported templates, hang into the 12‐MR channels through Zn‐O‐P linkages with framework.     

Template Syntheses of Two Open‐framework Zinc Phosphites

Two new open‐framework zincophosphites, Zn(H₆C₄N₂S)(HPO₃) (TJPU‐4) and [C₆N₂H₁₄]·[Zn₃(HPO₃)₄] (TJPU‐5) have been hydrothermally synthesized by using 2‐mercapto‐1‐methylimidazole [MMI] and 1,4‐diazabicyclo[2.2.2]octane [DABCO] as templates. TJPU‐4 crystallizes in monoclinic space group P2₁/c with the cell parameters a = 8.787(4) Å, b = 9.732(4) Å, c = 10.515(4) Å, β = 105.316(6)°, V = 867.3(6) ų. The structure of TJPU‐4 is constructed by ZnO₃S tetrahedron and HPO₃ pseudo‐pyramid to generate a layer of 4, 8‐network in bc plane. The organic template locates on the both sides of the 8‐membered rings and bonds to zinc atom through Zn–S bond. TJPU‐5 crystallizes in the triclinic space group with cell parameters a = 9.294 (5) Å, b = 9.976 (5) Å, c = 9.986 (5) Å, α = 85.692 (7)°, β = 82.010 (7)° and γ = 80.184 (7)°, V = 902.1 (8) ų. A novel 4⁴8⁸ cage is found in TJPU‐5. The connections of Zn(1)O₄, Zn(3)O₄ and HPO₃ groups give rise to an infinite corner‐shared four‐ring chain. Using Zn(2)O₄ as four connected bridges, linkages of these chains produce a 3‐D framework with intersecting 8‐ring channels running along [100], [010], [001], [011] and [111] directions.     

(C5H14N2)[Zn3(HPO4)4], a New 3D Open‐framework Zincophosphate Synthesized by Hydrothermal Reversible Transformation of (C5H14N2)[Zn2(HPO4)3]·H2O

In the system ZnO/H₃PO₄/H₂O/1,4‐diazacycloheptane (C₅H₁₂N₂), a new zincophosphate (ZnPO), (C₅H₁₄N₂)[Zn₃(HPO₄)₄] ( I ), was prepared by hydrothermal transformation (180 °C) of the known ZnPO hydrate (C₅H₁₄N₂)[Zn₂(HPO₄)₃]·H₂O ( II ). The thermally‐induced transformation is reversible; upon keeping the heterogeneous mixture of I and mother liquor at 80 °C recrystallization of II was observed. Single‐crystal X‐ray crystallography revealed that I possesses a unique three‐dimensional (3D) open‐framework structure built from corner‐linked ZnO₄ and HPO₄ tetrahedra. The (3,4)‐connected framework of I differs considerably from the 3D open‐framework ZnPO structure of II . Crystal data for I : Monoclinic system, space group Cc (No. 9) , Z = 4, a = 9.1389(6), b = 23.627(2), c = 9.3073(6) Å, β = 109.463(7)°, T = 298 K.     

A Gadolinium Complex of the 5‐(1H‐Tetrazol‐5‐yl)isophthalic Acid Ligand: [Gd(C9H3N4O4)(H2O)3·2H2O]n

The reaction of Gd(ClO₄)₃·6H₂O with 5‐(1H‐tetrazol‐5‐yl)isophthalic acid affords a 3D framework gadolinium coordination polymer, [Gd(C₉H₃N₄O₄)(H₂O)₃·2H₂O]_n ( 1 ). Its crystal structure belongs to a triclinic system, space group , with a = 7.909(2) Å; b = 8.448(2) Å; c = 10.994(2) Å; α = 102.65(3)°; β = 124.32(2)°; γ = 96.28(3)°; V = 704.5(2) ų; Z = 2; R₁ = 0.0245 for 3225 reflections with I >2σ(I), wR₂ = 0.0556. Fluorescent analyses show that compound 1 exhibits purple fluorescence in the solid state at room temperature.     

Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.     

Synthesis and Comprehensive Characterization of Hydrated Alkaline Earth Metal Salts of 5‐Amino‐1H‐tetrazole

Hydrated alkaline earth metal salts of 5‐amino‐1H‐tetrazole ( B ) were synthesized by reaction of B with a suitable metal hydroxide in water. All compounds were fully characterized by analytical (elemental analysis and mass spectrometry) and spectroscopic (IR, Raman, ¹H and ¹³C NMR) methods. Additionally, the crystal structures of the magnesium [ 1· 4H₂O: triclinic, P$\bar {1}$ , a = 5.940(1) Å, b = 7.326(1) Å,c = 7.383(1) Å, α = 106.10(1)°, β = 106.51(1)°, γ = 111.85(1)°, V = 258.0(1) ų], calcium [ 2· 6H₂O: monoclinic, P2₁/m, a = 6.904(1) Å,b = 6.828(1) Å, c = 10.952(2) Å, β = 94.50(2)°, V = 514.6(1) ų], and strontium [ 3· 6H₂O: orthorhombic, Cmcm, a = 6.987(1) Å, b = 28.394(2) Å, c = 7.007(1) Å, V = 1390.3(2) ų] were determined by low temperature X‐ray diffraction. Additionally, the (gas phase) structure of the 5‐amino‐1H‐tetrazole anion ([ B ]^–) was also studied by natural bond orbital (NBO) analysis [B3LYP/6‐31+G(d,p)]. Lastly, standard tests were used to determine the sensitivity towards impact, friction, and electrostatic discharge of the compounds and the thermal stability was assessed by differential scanning calorimetry (DSC) analysis.     

6‐Amino‐3‐methyl‐5‐nitro­so­pyrimi­dine‐2,4(1H,3H)‐dione forms a three‐dimensional hydrogen‐bonded framework structure

Molecules of the title compound, C₅H₆N₄O₃, are linked into a single three‐dimensional framework by a two‐centre N—H⃛O hydrogen bond [H⃛O = 1.92 Å, N⃛O = 2.785 (2) Å and N—H⃛O = 168°], a two‐centre N—H⃛H hydrogen bond [H⃛N = 2.19 Å, N⃛N = 3.017 (2) Å and N—H⃛N = 157°] and the intermolecular component of an effectively planar three‐centre N—H⃛(O)₂ hydrogen bond [H⃛O = 2.03 and 2.31 Å, N⃛O = 2.645 (2) and 2.957 (2) Å, N—H⃛O = 126 and 130°, and O⃛H⃛O = 101°].     

Intra‐ and intermolecular Se...X (X = Se,O) interactions in selenium‐containing heterocycles: 3‐benzoylimino‐5‐(morpholin‐4‐yl)‐1,2,4‐diselenazole

In the selenium‐containing heterocyclic title compound {systematic name: N‐[5‐(morpholin‐4‐yl)‐3H‐1,2,4‐diselenazol‐3‐ylidene]benzamide}, C₁₃H₁₃N₃O₂Se₂, the five‐membered 1,2,4‐diselenazole ring and the amide group form a planar unit, but the phenyl ring plane is twisted by 22.12 (19)° relative to this plane. The five consecutive N—C bond lengths are all of similar lengths [1.316 (6)–1.358 (6) Å], indicating substantial delocalization along these bonds. The Se...O distance of 2.302 (3) Å, combined with a longer than usual amide C=O bond of 2.252 (5) Å, suggest a significant interaction between the amide O atom and its adjacent Se atom. An analysis of related structures containing an Se—Se...X unit (X = Se, S, O) shows a strong correlation between the Se—Se bond length and the strength of the Se...X interaction. When X = O, the strength of the Se...O interaction also correlates with the carbonyl C=O bond length. Weak intermolecular Se...Se, Se...O, C—H...O, C—H...π and π–π interactions each serve to link the molecules into ribbons or chains, with the C—H...O motif being a double helix, while the combination of all interactions generates the overall three‐dimensional supramolecular framework.     

π‐Stacked hydrogen‐bonded dimers in 2‐(2‐nitro­phenyl­amino­carbonyl)­benzoic acid,and hydrogen‐bonded sheets in orthorhombic and monoclinic polymorphs of 2‐(4‐nitro­phenyl­amino­carbonyl)­benzoic acid

Molecules of 2‐(2‐nitrophenylaminocarbonyl)benzoic acid, C₁₄H₁₀N₂O₅, are linked into centrosymmetric R(8) dimers by a single O—H⋯O hydrogen bond [H⋯O = 1.78 Å, O⋯O = 2.623 (2) Å and O—H⋯O = 178°] and these dimers are linked into sheets by a single aromatic π–π stacking interaction. The isomeric compound 2‐(4‐nitrophenylaminocarbonyl)benzoic acid crystallizes in two polymorphic forms. In the orthorhombic form (space group P2₁2₁2₁ with Z′ = 1, crystallized from ethanol), the mol­ecules are linked into sheets of R(22) rings by a combination of one N—H⋯O hydrogen bond [H⋯O = 1.96 Å, N⋯O = 2.833 (3) Å and N—H⋯O = 171°] and one O—H⋯O hydrogen bond [H⋯O = 1.78 Å, O⋯O = 2.614 (3) Å and O—H⋯O = 173°]. In the monoclinic form (space group P2₁/n with Z′ = 2, crystallized from acetone), the mol­ecules are linked by a combination of two N—H⋯O hydrogen bonds [H⋯O = 2.09 and 2.16 Å, N⋯O = 2.873 (4) and 2.902 (3) Å, and N—H⋯O = 147 and 141°] and two O—H⋯O hydrogen bonds [H⋯O = 1.84 and 1.83 Å, O⋯O = 2.664 (3) and 2.666 (3) Å, and O—H⋯O = 166 and 174°] into sheets of some complexity. These sheets are linked into a three‐dimensional framework by a single C—H⋯O hydrogen bond [H⋯O = 2.45 Å, C⋯O = 3.355 (4) Å and C—­H⋯O = 160°].     

A Nine‐Coordinated ZrIV Complex and a Self‐Assembling System Obtained from a Proton Transfer Compound Containing 2,6‐Pyridinedicarboxylate and 2,6‐Pyridinediammonium; Synthesis and X‐ray Crystal Structure

Starting with a zirconium salt and LH₂ , (pydaH₂)²⁺(pydc)^2?, (pyda=2, 6‐pyridinediamine; pydcH₂=2,6‐pyridinedicarboxylic acid), as a 1:1 proton transfer self‐associated compound, two different compounds were resulted. One of them is a new complex of Zr^IV with a flat pyridine containing ligand and structure of (pydaH)₂[Zr(pydc)₃] · 5H₂O (1) and the other, (pydaH)⁺(NO₃)^? (2) is an ion pair with no zirconium ion. The zirconium(IV) complex (1) is crystallized in triclinic system with space group and Z = 2, the crystallographic parameters are: a = 10.612(5) Å, b = 10.617(5) Å, c = 16.815(8) Å, α = 103.654(9)°, β = 95.821(9)°, γ = 98.891(9)° and R‐value for 16767 collected reflections is 0.0592. The ion pair (2) has crystals of monoclinic system with P2₁ space group and Z = 2. Its crystallographic parameters are: a = 3.6227(11) Å, b = 10.034(4) Å, c = 10.296(4) Å, β = 93.422(9)° and R‐value for 4031 collected reflections is 0.0521. The two compounds were characterized with elemental analysis, ESI/MS, NMR and IR spectroscopy.     

A Zipper‐like Supramolecular Double‐Chain based on 1 D π‐π Stacking Interactions: Synthesis and Crystal Structure of [Cu(phen)(C4H4O4)(H2O)]2 · C4H6O4 (phen = 1,10‐phenanthroline)

[Cu(C₁₂H₈N₂)(C₄H₄O₄)(H₂O)]₂ · C₄H₆O₄ was prepared by the reaction of succinic acid, CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen = C₁₂H₈N₂), and Na₂CO₃ in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) Å; α = 68.89(1)°, β = 88.89(1)°, γ = 73.32(1)°, Z = 1, R = 0.0308, wR² = 0.0799 for 3530 observed reflections (F ≥ 2σ(F ) out of 3946 unique reflections) consists of hydrogen bonded succinic acid molecules and succinato bridged 1 D zipperlike supramolecular [Cu(phen)(C₄H₄O₄)_2/2(H₂O)]₂ double chains based on 1 D π‐π stacking interactions between the chelating phen systems at distances of 3.71 Å and 3.79 Å. The Cu atoms are fivefold trigonal bipyramidally coordinated by two N atoms of the bidentate chelating phen ligand and three O atoms of one water molecule and two bidentate bridging succinate ligands. The water O atom and one phen N atom are at the apical positions (equatorial: d(Cu–O) = 1.945, 2.254(2) Å, d(Cu–N) = 2.034(2) Å; axial: d(Cu–O) = 1.971(2) Å, d(Cu–N) = 1.995 Å).     

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.     

Caesiumchloropalladat(II)‐hydrate – zwei neue Verbindungen mit kondensierten [Pd2Cl6]‐Baugruppen

Caesiumchloropalladate(II)‐hydrates – Two New Compounds with Condensed [Pd₂Cl₆] Groups We were able to synthesize two caesiumchloropalladate(II)‐hydrates in the CsCl/PdCl₂/H₂O system by hydrothermal methods. Both compounds show combination of monomeric and dimeric Pd–Cl groups. We characterized the crystal structures by single‐crystal X‐ray diffraction. Cs₆Pd₅Cl₁₆ · 2 H₂O ( I ) crystallizes triclinic in space group type P1 (Nr. 2) with a = 8.972(1) Å, b = 11.359(1) Å, c = 18.168(1) Å, α = 83.61(1)°, β = 76.98(1)°, γ = 76.39(1)° and Z = 2, Cs₁₂Pd₉Cl₃₀ · 2 H₂O ( II ) monoclinic, space group type C2/m (No. 12) with a = 19.952(1) Å, b = 14.428(1) Å, c = 14.411(1) Å, β = 125.29(1)°, and Z = 2.     

Synthesis and Characterization of a New Three‐dimensional Organically Templated Nickel‐Zinc Phosphate

A new organically templated nickel–zinc phosphate, [C₂N₂H₁₀]·[Ni_2.4Zn_3.6(PO₄)₄(HPO₄)]·H₂O, has been synthesized from an aqueous solution containing NiCl₂·6H₂O, Zn(OAc)₂·2H₂O, H₃PO₄ and ethylenediamine as the structure‐directing agent. The compound crystallizes in the monoclinic system, space group C2/c (No. 15), a = 19.1563(5), b = 5.0316(2), c = 21.1724(5) Å, α = 103.201(3)°, V = 1986.81(11) ų, Z = 4. It possesses a three‐dimensional framework constructed from MO₄ (M = Ni, Zn), PO₄, and HPO₄ tetrahedra through their vertices. One‐dimensional 8‐ring channels are found in the structure, with the diprotonated organic templates residing in the tunnels and interacting with the inorganic framework by extensive hydrogen bonds. The framework is characterized by infinite helical chains of corner‐sharing MO₄ (M = Ni, Zn) tetrahedra.     

1,2‐Dithioquadratato‐ und 1,2‐Dithiooxalatoindate(III)

Indium(III) chloride forms in water with potassium 1,2‐dithiooxalate (dto) and potassium 1,2‐dithiosquarate (dtsq) stable coordination compounds. Due to the higher bridging ability of the 1,2‐dithiooxalate ligand in all cases only thiooxalate bridged binuclear complexes were found. From 1,2‐dithioquadratate with an identical donor atom set mononuclear trischelates could be isolated. Five crystalline complexes, (BzlMe₃N)₄[(dto)₂In(dto)In(dto)₂] ( 1 ), (BzlPh₃P)₄[(dto)₂In(dto)In(dto)₂] ( 2 ), (BzlMe₃N)₃[In(dtsq)₃] ( 3 ), (Bu₄N)₃[In(dtsq)₃] ( 4 ) and (Ph₄P)[In(dtsq)₂(DMF)₂] ( 5 ), have been isolated and characterized by X‐ray analyses. Due to the type of the complex and the cations involved these compounds crystallize in different space groups with the following parameters: 1 , monoclinic in P2₁/c with a = 14.4035(5) Å, b = 10.8141(5) Å, c = 23.3698(9) Å, β = 124.664(2)°, and Z = 2; 2 , triclinic in P with a = 11.3872(7) Å, b = 13.6669(9) Å, c = 17.4296(10) Å, α = 88.883(5)°, β = 96.763(1)°, γ = 74.587(5)°, and Z = 1; 3 , hexagonal in R3 with a = 20.6501(16) Å, b = 20.6501(16) Å, c = 19.0706(13) Å and Z = 6; 4 , monoclinic in P2₁/c with a = 22.7650(15) Å, b = 20.4656(10) Å, c = 14.4770(9) Å, β = 101.095(5)°, and Z = 4; 5 , triclinic in P with a = 9.2227(6) Å, b = 15.3876(9) Å, c = 15.5298(9) Å, α = 110.526(1)°, β = 100.138(1)°, γ = 101.003(1)°, and Z = 2.     

2‐Amino‐5‐nitro­thia­zole monoethanol solvate: triply‐interwoven hydrogen‐bonded sheets containing centrosymmetric R(8) and R(38) rings

2‐Amino‐5‐nitro­thia­zole crystallizes from solution in ethanol as a monosolvate, C₃H₃N₃O₂S·C₂H₆O, in which the thia­zole component has a strongly polarized molecular–electronic structure. The thia­zole mol­ecules are linked into centrosymmetric dimers by paired N—H⋯N hydrogen bonds [H⋯N = 2.09 Å, N⋯N = 2.960 (6) Å and N—H⋯N = 169°], and these dimers are linked by the ethanol mol­ecules, via a two‐centred N—H⋯O hydrogen bond [H⋯O = 1.98 Å, N⋯O = 2.838 (5) Å and N—H⋯O = 164°] and a planar asymmetric three‐centred O—H⋯(O)₂ hydrogen bond [H⋯O = 2.07 and 2.53 Å, O⋯O = 2.900 (5) and 3.188 (5) Å, O—H⋯O = 169 and 136°, and O⋯H⋯O = 55°], into sheets built from alternating (8) and (38) rings. These sheets are triply interwoven.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

Synthesis and Structural Study of Copper(I) or Silver(I) Complexes of 2,11‐Dithia‐4,5,6,7,8,9‐Hexahydro[3.3]paracyclophanes

The complexes of 2,11‐dithia‐4,5,6,7,8,9‐hexahydro[3.3]paracyclophane (dthhpcp) with Cu(I), i.e. [Cu₂I₂(dthhpcp)₂]·2H₂O 1 , or with Ag(I), i.e. [Ag(dthhpcp)(NO₃)]thf 2 and [Ag(dthpcp)(CF₃COO)] 3 , were prepared for structural study by single‐crystal X‐ray diffraction analysis. For these three complexes, dthhpcp serves as a bridging group in the polymeric structure through bridging sulfur atoms via metal, while the bonding of anion with the second metal atom forms the multi‐diminished structures. Complex 1 is a novel two‐dimensional coordination polymer composed of Cu₆ motifs, in which Cu₂I₂ formed a square planar unit to link the dthhpcp molecule. The two oxygen atoms of the nitrate anion as a bridge for two Ag atoms in complex 2 provides a three‐dimensional channel framework of silver(I) with a tetrahydrofuran molecule as a guest inside the open cavities. In contrast, the analogous reaction with silver triflouroacetate gave a complex 3 , which is composed of infinite linear chains of‐Ag‐dthhpcp‐Ag‐dthhpcp‐ along the a axis. Unit cell data: complex 1 , orthorhombic system, space group P2(1)2(1)2(1), a = 19.2982(11) Å b = 16.5661(10) Å, c = 25.3006(15) Å, β = 90°, Z = 8; complex 2 , orthorhombic system, space group Pna2(1), a = 8.8595(6) Å, b = 12.6901(9) Å, c = 19.8449(14) Å, β = 90°, Z = 4; complex 3 , monoclinic system, space group P2(1)/n, a = 8.845(3) Å, b = 20.841(6) Å, c = 11.061(3) Å, β = 107.832(6)°, Z = 4.     

Copper(I) π‐Complexes with 2‐Butyne‐1,4‐diol. Synthesis and Crystal Structure of Na[CuCl2(HOCH2C≡CCH2OH)]·2H2O

Crystals of anionic Na[CuCl₂(HOCH₂C≡CCH₂OH)]·2H₂O π‐complex have been synthesized by interaction of 2‐butyne‐1,4‐diol with CuCl in a concentrated aqueous NaCl solution and characterized by X‐ray diffraction at 100 K. The crystals are triclinic: space group , a = 7.142(3), b = 7.703(3), c = 10.425(4) Å, α = 105.60(3), β = 99.49(3), γ = 110.43(3)°, V = 495.9(4) ų, Z = 2, R = 0.0203 for 3496 reflections. The structure is built of discrete [CuCl₂(HOCH₂C≡CCH₂OH)]^? anionic stacks and polymeric cations among the stacks. The Cu^I atom adopts trigonal planar coordination of two Cl^? anions and the C≡C bond of 2‐butyne‐1,4‐diol, Cu–(C≡C) distance is equal to 1.903(3) Å. Na⁺ cations environment is octahedral and consists of O and Cl atoms. The crystal packing is governed by strong hydrogen bonds of O–H···Cl and O–H···O types.     

Neue Kronenether‐stabilisierte Oxoniumhalogenochalkogenate: [H3O(Dibromo‐benzo‐18‐Krone‐6)]2[Se3Br10] und [H5O2(Bis‐dibromo‐dibenzo‐24‐Krone‐8]2[Se3Br8]

Novel Oxonium Halogenochalcogenates Stabilized by Crown Ethers: [H₃O(Dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] and [H₅O₂(Bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] Two novel complex oxonium bromoselenates(II,IV) and –(II) are reported containing [H₃O]⁺ and [H₅O₂]⁺ cations coordinated by crown ether ligands. [H₃O(dibromo‐benzo‐18‐crown‐6)]₂[Se₃Br₁₀] ( 1 ) and [H₅O₂(bis‐dibromo‐dibenzo‐24‐crown‐8]₂[Se₃Br₈] ( 2 ) were prepared as dark red crystals from dichloromethane or acetonitrile solutions of selenium tetrabromide, the corresponding unsubstituted crown ethers, and aqueous hydrogen bromide. The products were characterized by their crystal structures and by vibrational spectra. 1 is triclinic, space group (Nr. 2) with a = 8.609(2) Å, b = 13.391(3) Å, c = 13.928(3) Å, α = 64.60(2)°, β = 76.18(2)°, γ = 87.78(2)°, V = 1404.7(5) ų, Z = 1. 2 is also triclinic, space group with a = 10.499(2) Å, b = 13.033(3) Å, c = 14.756(3) Å, α = 113.77(3)°, β = 98.17(3)°, γ = 93.55(3)°. V = 1813.2(7) ų, Z = 1. In the reaction mixture complex redox reactions take place, resulting in (partial) reduction of selenium and bromination of the crown ether molecules. In 1 the centrosymmetric trinuclear [Se₃Br₁₀]^2? consists of a central Se^IVBr₆ octahedron sharing trans edges with two square planar Se^IIBr₄ groups. The novel [Se₃Br₈]^2? in 2 is composed of three planar trans‐edge sharing Se^IIBr₄ squares in a linear arrangement. The internal structure of the oxonium‐crown ether complexes is largely determined by the steric restrictions imposed by the aromatic rings in the crown ether molecules, as compared to complexes with more flexible unsubstituted crown ether ligands.