Synthesis and Crystal Structure of the Tris‐bidentate Carbonatobis‐(1,10‐phenanthroline‐N,N′)nickel(II), [Ni(C12H8N2)2(CO3)]

The tris‐bidentate complex [Ni(C₁₂H₈N₂)₂(CO₃)] was synthesized by the reaction of Na₂CO₃, 1,10‐phenanthroline (phen = C₁₂H₈N₂) and NiSO₄ · 6 H₂O in the presence of succinic acid in a CH₃OH–H₂O solution. The compound crystallizes as heptahydrate. The crystal structure (monoclinic, P2₁/c (no. 14), a = 9.897(1), b = 26.384(2), c = 10.582(1) Å, β = 105.87(1)°, Z = 4, R = 0.0505, wR² = 0.1029 for 3166 observed reflections (F ≥ 2σ(F ) out of 6100 unique reflections) consists of hydrogen bonded water molecules and [Ni(phen)₂(CO₃)] complex molecules. The Ni atoms are sixfold octahedrally coordinated by the four N atoms of two bidentate chelating phen ligands and by two O atoms of the bidentate chelating carbonate group with d(Ni–N) = 2.092–2.100 Å, d(Ni–O) = 2.051, 2.079 Å. The complex molecules are stacked into 2D corrugated layers parallel to (010) via two types of intermolecular π‐π stacking interactions. One occurs between two quinoline rings of neighboring phen ligands at the distance of 3.63 Å in [010] direction and the other results from 1D π‐π stacking interactions through partially covered phen rings at alternative distances of 3.26 Å and 3.33 Å in [001] direction. The water molecules are sandwiched between 2D layers.     

The Cocrystallization of the Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and Triclinic [Ta6Br12(H2O)6]X2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl,Br, NO3) Phases with the Coexistence of [Ta6Br12]2+ and [Ta6Br12]4+ in the Latter

Cubic [Ta₆Br₁₂(H₂O)₆][CuBr₂X₂]·10H₂O and triclinic [Ta₆Br₁₂(H₂O)₆]X₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O (X = Cl, Br, NO₃) cocrystallize in aqueous solutions of [Ta₆Br₁₂]²⁺ in the presence of Cu²⁺ ions. The crystal structures of [Ta₆Br₁₂(H₂O)₆]Cl₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 1 ) and [Ta₆Br₁₂(H₂O)₆]Br₂·trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]·18H₂O ( 3 )have been solved in the triclinic space group P&1macr; (No. 2). Crystal data: 1 , a = 9.3264(2) Å, b = 9.8272(2) Å, c = 19.0158(4) Å, α = 80.931(1)?, β = 81.772(2)?, γ = 80.691(1)?; 3 , a = 9.3399(2) Å, b = 9.8796(2) Å, c = 19.0494(4) Å; α = 81.037(1)?, β = 81.808(1)?, γ = 80.736(1)?. 1 and 3 consist of two octahedral differently charged cluster entities, [Ta₆Br₁₂]²⁺ in the [Ta₆Br₁₂(H₂O)₆]²⁺ cation and [Ta₆Br₁₂]⁴⁺ in trans‐[Ta₆Br₁₂(OH)₄(H₂O)₂]. Average bond distances in the [Ta₆Br₁₂(H₂O)₆]²⁺ cations: 1 , Ta‐Ta, 2.9243 Å; Ta‐Brⁱ , 2.607 Å; Ta‐O, 2.23 Å; 3 , Ta‐Ta, 2.9162 Å; Ta‐Brⁱ , 2.603 Å; Ta‐O, 2.24 Å. Average bond distances in trans‐[Ta₆‐Br₁₂(OH)₄(H₂O)₂]: 1 , Ta‐Ta, 3.0133 Å; Ta‐Brⁱ, 2.586 Å; Ta‐O(OH), 2.14 Å; Ta‐O(H₂O), 2.258(9) Å; 3 , Ta‐Ta, 3.0113 Å; Ta‐Brⁱ, 2.580 Å; Ta‐O(OH), 2.11 Å; Ta‐O(H₂O), 2.23(1) Å. The crystal packing results in short O···O contacts along the c axes. Under the same experimental conditions, [Ta₆Cl₁₂]²⁺ oxidized to [Ta₆Cl₁₂]⁴⁺ , whereas [Nb₆X₁₂]²⁺ clusters were not affected by the Cu²⁺ ion.     

Crystal Structures of [Mn2(H2O)4(bpy)2(C8H12O4)2] · 2 H2O and [Mn(H2O)2(bpy)(C8H12O4)2/2] · H2O with bpy = 2,2′‐bipyridine

Reaction of MnSO₄ · H₂O, 2,2′‐bipyridine (bpy), suberic acid and Na₂CO₃ in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] · 2 H₂O ( 1 ) and [Mn(H₂O)₂‐ (bpy)(C₈H₁₂O₄)_2/2] · H₂O ( 2 ). In both complexes, the Mn atoms are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two trans positioned H₂O molecules and two suberato ligands (d(Mn–O) = 2.107–2.328 Å; d(Mn–N) = 2.250–2.330 Å). The bis‐monodentate suberato ligands bridge Mn atoms to form dinuclear [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] complex molecules in 1 and 1D [Mn(H₂O)₂(bpy)(C₈H₁₂O₄)_2/2] chains in 2 . Via the intermolecular hydrogen bondings and π‐π stacking interactions, the dinuclear molecules in 1 are assembled into 2D networks parallel to (100), between which the crystal H₂O molecules are sandwiched. The polymeric chains in 2 are linked together by interchain hydrogen bonding and π‐π stacking interactions into 3D networks with the crystal H₂O molecules located in tunnels along [010]. Crystal data for 1 : P2₁/c (no. 14), a = 10.092(1) Å, b = 11.916(2) Å, c = 17.296(2) Å, β = 93.41(1)° and Z = 2. Crystal data for 2 : P2₁/c (no. 14), a = 11.176(2) Å, b = 9.688(1) Å, c = 37.842(6) Å, β = 90.06(1)° and Z = 8.     

Crystal Structure,Synthesis, and Properties of tri‐Calcium di‐Citrate tetra‐Hydrate [Ca3(C6H5O7)2(H2O)2]·2H2O

From hydrothermal synthesis needle‐shaped crystals of [Ca₃(C₆H₅O₇)₂(H₂O)₂] · 2H₂O were obtained. The crystal structure was determined by single‐crystal X‐ray experiments and confirmed by powder data (P$\bar{1}$ (no. 2) a = 5.9466(4), b = 10.2247(8), c = 16.6496(13) Å, α = 72.213(7)°, β = 79.718(7)°, γ = 89.791(6)°, V = 947.06(13) Å³, Z = 2, R1 = 0.0426, wR2 = 0.1037). The structure was obtained from pseudo merohedrically polysynthetic twinned crystals using a combined data collection approach and refinement processes. The observed three‐dimensional network is dominated by eightfold coordinated Ca²⁺ cations linked by citrate anions and hydrogen bonds between two non‐coordinating crystal water molecules and two coordinating water molecules.     

Das Lanthan‐Dodekahydro‐closo‐Dodekaborat‐Hydrat [La(H2O)9]2[B12H12]3·15 H2O und sein Oxonium‐Chlorid‐Derivat [La(H2O)9](H3O)Cl2[B12H12]·H2O

The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O and its Oxonium‐Chloride Derivative [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic La₂O₃ and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B₁₂H₁₂]²⁻ anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La³⁺ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B₁₂H₁₂]²⁻ anions on La³⁺ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–O^δ–···^+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H₃O)₂[B₁₂H₁₂] with lanthanum trichloride an anion‐mixed salt with the composition [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B₁₂H₁₂]²⁻ anions and H₃O⁺ cations alternate with layers of [La(H₂O)₉]³⁺ cations (d(La–O) = 252–260 pm) and Cl⁻ anions along [001]. The [B₁₂H₁₂]²⁻ (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl⁻ anions exhibit no coordinative influence on La³⁺. Hydrogen bonds are formed between the H₃O⁺ cations and [B₁₂H₁₂]²⁻ anions, also between the water molecules of [La(H₂O)₉]³⁺ and Cl⁻ anions, which contribute to the stabilization of the crystal structure.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

One‐dimensionally linked Chain Crown Ether Complexes. Syntheses and Crystal Structures of Complexes [K(18‐Crown‐6)]2[M(SeCN)4](H2O) (M = Pd,Pt)

18‐crown‐6(18‐C‐6) complexes with K₂[M(SeCN)₄] (M = Pd, Pt): [K(18‐C‐6)]₂[Pd(SeCN)₄] (H₂O) ( 1 ) and [K(18‐C‐6)]₂[Pt(SeCN)₄](H₂O) ( 2 ) have been isolated and characterized by elemental analysis, IR spectroscopy and single crystal X‐ray analysis. The complexes crystallize in the monoclinic space group P2₁/n with cell dimensions: 1 : a = 1.1159(3) Å, b = 1.2397(3) Å, c = 1.6003(4) Å, β = 92.798(4)°, V = 2.2111(8) ų, Z = 2, F(000) = 1140, R₁ = 0.0418, wR₂ = 0.0932 and 2 : a = 1.1167(3) Å, b = 1.2394(3) Å, c = 1.5968(4) Å, β = 92.945(4)°, V = 2.2071(9) ų, Z = 2, F(000) = 1204, R₁ = 0.0341, wR₂ = 0.0745. Both complexes form one‐dimensionally linked chains of [K(18‐C‐6)]⁺ cations and [M(SeCN)₄]^2— (M = Pd, Pt) anions bridged by K‐O‐K interactions between adjacent [K(18‐C‐6)]⁺ units.     

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.     

One‐dimensional Cadmium(II) Coordination Polymers: Syntheses and Crystal Structures of [Cd(H2O)3(C5H6O4)]·2H2O,Cd(H2O)2(C6H8O4), and Cd(H2O)2(C8H12O4)

[Cd(H₂O)₃(C₅H₆O₄)]·2H₂O ( 1 ) and Cd(H₂O)₂(C₆H₈O₄) ( 2 ) were prepared from reactions of fresh CdCO₃ precipitate with aqueous solutions of glutaric acid and adipic acid, respectively, while Cd(H₂O)₂(C₈H₁₂O₄) ( 3 ) crystallized in a filtrate obtained from the hydrothermal reaction of CdCl₂·2.5H₂O, suberic acid and H₂O. Compound 1 consists of hydrogen bonded water molecules and linear {[Cd(H₂O)₃](C₅H₆O₄)_2/2} chains, which result from the pentagonal bipyramidally coordinated Cd atoms bridged by bis‐chelating glutarato ligands. In 2 and 3 , the six‐coordinate Cd atoms are bridged by bis‐chelating adipato and suberato ligands into zigzag chains according to {[Cd(H₂O)₃](C₅H₆O₄)_2/2} and {[Cd(H₂O)₂](C₈H₁₂O₄)_2/2}, respectively. The hydrogen bonds between water and the carboxylate oxygen atoms are responsible for the supramolecular assemblies of the zigzag chains into 3D networks. Crystallographic data: ( 1 ) P1¯ (no. 2), a = 8.012(1), b = 8.160(1), c = 8.939(1) Å, α = 82.29(1)°, β = 76.69(1)°, γ = 81.68(1)°, U = 559.6(1) ų, Z = 2; ( 2 ) C2/c (no. 15), a = 16.495(1), b = 5.578(1), c = 11.073(1) Å, β = 95.48(1)°, U = 1014.2(1) ų, Z = 4; ( 3 ) P2/c (no. 13), a = 9.407(2), b = 5.491(1), c = 11.317(2) Å, β = 95.93(3)°, U = 581.4(2) ų, Z = 2.     

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.     

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.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.     

New Suberato‐bridged Supramolecular Layers: Crystal Structure of [Cu2(phen)2(C8H12O4)2] · 3 H2O with phen = 1,10‐phenanthroline

The reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), suberic acid and Na₂CO₃ in a CH₃CN–H₂O solution yielded blue needle‐like crystals of [Cu₂(phen)₂(C₈H₁₂O₄)₂] · 3 H₂O. The crystal structure (monoclinic, P2₁/n, a = 10.756(2) Å, b = 9.790(2) Å, c = 18.593(4) Å, β = 91.15(3)°, Z = 2, R = 0.043, wR² = 0.1238) consists of suberato‐bridged [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers and hydrogen bonded H₂O molecules. The Cu atoms are coordinated by two N atoms from one bidentate chelating phen ligand and three carboxyl O atoms from different suberato ligands to form distorted [CuN₂O₃] square‐pyramids with one carboxyl O atom at the apical position (d(Cu–N) = 2.017(2), 2.043(3) Å, basal d(Cu–O) = 1.936(2), 1.951(2) Å and axial d(Cu–O) = 2.389(2) Å). Two [CuN₂O₃] square‐pyramids are condensed via a common O–O edge to a centrosymmetric [Cu₂N₄O₄] dimer with the Cu…Cu distance of 3.406(1) Å indicating no interaction between Cu atoms. The resultant [Cu₂N₄O₄] dimers are interlinked by the tridentate suberato ligands to form [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers parallel to (101). These are assembled via π‐π stacking interactions into 3D network with H₂O molecules in the tunnels extending in the [010] direction.     

Synthesis,Crystal Structure,and Thermal Properties of the Energetic Coordination Compound [Co(DAT)2(H2O)4](HTNR)2·2H2O (DAT = 1,5‐diaminotetrazole)

A new coordination complex, [Co(DAT)₂(H₂O)₄](HTNR)₂ · 2H₂O [DAT = 1,5‐diaminotetrazole, HTNR = 2,4,6‐trinitroresorcinol (styphnic acid)], was obtained in high yield and characterized by elemental analysis and Fourier‐transform infrared (FT‐IR) spectroscopy. The molecular structure of [Co(DAT)₂(H₂O)₄](HTNR)₂ · 2H₂O in the crystalline state is determined by X‐ray crystallography is as follows: monoclinic, C2/c, a = 19.216(3) Å, b = 5.4992(8) Å, c = 30.418(5) Å, β = 104.500(5), V = 3112.0(8) ų, Z = 4, ρ_calc. = 1.851 g · cm^–3, R₁ = 0.0271 and wR₂ = (all data) 0.0674. The central cobalt(II) cation is coordinated by two nitrogen atoms of two DAT and four oxygen atoms of four H₂O ligand molecules to form a six‐coordinate and slightly distorted octahedral structure. Extensive intermolecular hydrogen bonds link molecular units of [Co(DAT)₂(H₂O)₄(HTNR)₂ · 2H₂O together to form a 3D net structure with pore canals. The thermal decomposition mechanism for the title compound was predicted based on DSC, TG‐DTG, and FT‐IR analyses and non‐kinetic parameters of the first exothermic process were estimated by applying the Kissinger, Starink, and Ozawa–Doyle methods.     

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).     

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.     

A Hydrogen Adipato‐bridged Copper(II) Coordination Polymer: [Cu(bpy)(HL)]2L · 6H2O (bpy = 2, 2'‐Bipyridine,H2L = Adipic Acid)

Reaction of a fresh Cu(OH)_2x(CO₃)_1—x · yH₂O precipitate with adipic acid (H₂L) and 2, 2'—bipyridine (bpy) in ethanolic aqueous solution at room temperature afforded the hydrogen adipato bridged Cu^II coordination polymer [Cu(bpy)(HL)]₂L · 6H₂O consisting of double chains according to {[Cu(bpy)(HL)_2/2]₂L} and hydrogen bonded H₂O molecules. The chains result from [Cu(bpy)]²⁺ units bridged by bis—monodentate hydrogen adipato ligands and further crosslinked by bis—monodentate adipato ligands. Through the interchain π—π stacking interactions and interchain C(bpy)—H···O(adipato) hydrogen bonding interactions, the double chains are assembled into layers, between which the crystal H₂O molecules are located. The Cu atoms are square pyramidally coordinated by two N atoms of one bpy ligand and three O atoms of one adipato ligand and two hydrogen adipato ligands. The doubly bonded oxygen atom of the protonated carboxyl group occupies the apical position (Cu—N: 1.997, 2.005 Å; equatorial Cu—O: 1.925, 1.942 Å; apical Cu—O: 2.354 Å). Furthermore, the thermal behavior of the compound will be discussed. Crystal data: triclinic, P1¯ (no. 2), a = 9.618(1) Å, b = 9.933(1) Å, c = 12.782(2) Å, α = 70.88(1)°, β = 73.70(1)°, γ = 75.60(1)°, V = 1090.7(2) ų, Z = 1, R = 0.0453 and wR² = 0.1265 for 4643 observed reflections (F_o² > 2σ(F_o²)) out of 4985 unique reflections.     

Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.