Two Succinato‐bridged Zinc(II) Phenanthroline Complexes: [Zn(phen)L2/2](H2L) and [(phen)2Zn(μ‐L)Zn(phen)2]L � 11H2O with H2L = Succinic Acid

Two mixed ligand Zn^II complexes [Zn(phen)L_2/2](H₂L) ( 1 ) and [(phen)₂Zn(μ‐L)Zn(phen)₂]L � 11H₂O ( 2 ) with H₂L = suc‐cinic acid were prepared and crystallographically characterized. Complex 1 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.618(1) Å, b = 9.585(1) Å, c = 15.165(1) Å, β = 96.780(6)°, V = 1965.6(3)ų, Z = 4 and complex 2 in the triclinic space group P 1¯ (no. 2) with a = 12.989(2)Å, b = 14.464(2)Å, c = 18.025(3)Å, α = 90.01(1)°, β = 109.69(1)°, γ = 112.32(1)°, V = 2917.4(8) ų, Z = 2. 1 consists of succinic acid molecules and 1D zigzag [Zn(phen)(C₄H₄O₄)_2/2] polymeric chains, in which the tetrahedrally coordinated Zn atoms are bridged by bis ‐ monodentate succinato ligands. Succinic acid molecules play an important role in supramolecular assemblies of the polymeric chains into 2D layers as well as in the stacking of 2D layers. 2 is composed of [(phen)₂Zn(μ‐L)Zn(phen)₂]²⁺ complex cations, succinate anions and hydrogen bonded water molecules. Within the divalent cations, Zn atoms are octahedrally coordinated by four N atoms of two phen ligands and two O atoms of one bis‐chelating succinato ligand. Through the intermolecular π—π stacking interactions, the complex cations form positively charged 2D layers, between which the noncoordinating succinate anions and water molecules are sandwiched.     

Syntheses,Crystal Structures,and Thermal Behavior of Co(phen)(HL)2 and [Co2(phen)2(H2O)4L2]·H2O with H2L = Pimelic Acid

Two Co^II complexes, Co(phen)(HL)₂ ( 1 ) and [Co₂(phen)₂(H₂O)₄L₂]·H₂O ( 2 ) (H₂L = HOOC‐(CH₂)₅‐COOH), were synthesized and structurally characterized on the basis of single crystal X‐ray diffraction data. In complex 1 the Co atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different hydrogenpimelato ligands. Through π—π stacking interactions between carboxyl group and phen ligand, the complex molecules are assembled into 1D columnar chains, which are connected by intermolecular hydrogen bonds. Complex 2 consists of the centrosymmetric dinuclear [Co₂(phen)₂(H₂O)₄L₂] molecules and hydrogen bonded H₂O molecules. The Co atoms are each octahedrally surrounded by two N atoms of one phen ligand and four O atoms from two bis‐monodentate pimelato ligands and two H₂O molecules at the trans positions. The results about thermal analyses, which were performed in flowing N₂ atmosphere, on both complexes were discussed. Crystal data: ( 1 ) C2/c (no. 15), a = 13.491(1)Å, b = 9.828(1)Å, c = 19.392(2)Å, β = 100.648(1)°, U = 2526.9(4)ų, Z = 4; ( 2 ) P1 (no. 2), a = 11.558(1)Å, b = 11.947(3)Å, c = 15.211(1)Å, α = 86.17(1)°, β = 75.55(1)°, γ = 69.95(1)°, U = 1910.3(3)ų, Z = 2.     

Cobalt(II) Complexes with Dicyanamide — from Binuclear Entities to Chains

One binuclear complex [Co(bpm*)₂(dca)]₂(ClO₄)₂ ( 1 ) and two 1D chain Co^II complexes, {[Co(bpm)₂(dca)](ClO₄)}_n ( 2 ) and [Co(dmf)₂(dca)₂]_n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R₁ = 0.0672, wR₂ = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each Co^II ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R₁ = 0.0609, wR₂ = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of Co^II ions bridged by one dca ligand. Each Co^II ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C₂, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R₁ = 0.0260, wR₂ = 0.0760. 3 has a one‐dimensional linear chain of Co^II ions bridged by two dca ligands, in which each Co^II ion is coordinated with two dmf molecules.     

Hydrothermal Preparation,Crystal Structure and Properties of {[ZnTCPP(EtOH)][Zn(en)]2}n(EtOH)2n with a Novel Two‐Dimensional (2‐D) Motif

A novel zinc porphyrin, {[ZnTCPP(EtOH)][Zn(en)]₂}_n(EtOH)_2n ( 1 ) (TCPP=meso‐tetra(4‐carboxyphenyl)‐porphyrin; EtOH=ethanol; en=ethylenediamine) was obtained via a hydrothermal reaction and characterized by single‐crystal X‐ray diffraction. Complex 1 crystallizes in the space group C2/c of the monoclinic system with eight formula units in a cell: a=32.465(4) Å, b=10.527(3) Å, c=31.845(3) Å, β=95.524(6) °, V=10832(4) ų, C₅₈H₅₇N₈O₁₁Zn₃, M_r=1238.23, D_c=1.518 g/cm³, S=1.005, µ(Mo Kα) =1.388 mm^?1, F(000) =5112, R=0.0650 and wR=0.1574. Complex 1 features a novel 2‐D layered motif. The spectral data of UV‐vis, FT‐IR and fluorescence are reported.     

Das Lanthaniodidethanid o‐La5I9(C2) – Die orthorhombische Hochtemperaturmodifikation

The Lanthanumiodideethanide o‐La₅I₉(C₂) – The Orthorhombic High Temperature Modification o‐La₅I₉(C₂) is synthesized by reaction of LaI₃, La metal and graphite powder in sealed Ta containers at 850 °C < T < 900 °C. It crystallizes in the orthorhombic space group Pbca with a = 8.0247(16) Å, b = 16.887(3) Å, c = 35.886(7) Å. o‐Ce₅I₉(C₂) is isotypic with the lattice parameters a = 7.9284(4) Å, b = 16.714(1) Å, c = 35.530(3) Å. o‐La₅I₉(C₂) transforms at 800 °C to the triclinic low temperature modification t‐La₅I₉(C₂). The transformation is reversible. The La atoms form trigonal bipyramids centered by C₂ groups. These units are connected by iodine atoms above the faces (f), edges (e) and corners according to La₅(C₂)I(f)ⁱI(e)^i?i_2/2I(e)^i?a_7/2I(e)^a?i_7/2. The C‐C distance in the C₂ unit is 1.45(2) Å. The crystals with greenish luster are moisture sensitive.     

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.     

Three Crystal Structures,One Chemical Formula – Barium Dihydrogen‐hypodiphosphate(IV)‐dihydrate,BaH2P2O6·2H2O

Three polymorphs of barium dihydrogen‐hypodiphosphate(IV)‐dihydrate, BaH₂P₂O₆ · 2H₂O ( A , B and C ), were obtained and structurally characterized by single‐crystal X‐ray diffraction. A crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 7.459(1) Å, b = 8.066(1) Å, c = 12.460(2) Å, β = 91.27(1) ° and Z = 4. B crystallizes in the monoclinic space group C2/c (no. 15) with a = 11.049(8) Å, b = 6.486(3) Å, c = 10.956(6) Å, β = 106.89(5) ° and Z = 4. C crystallizes in the orthorhombic space group C222₁ (no. 20) with a = 9.193(3) Å, b = 6.199(2) Å, c = 12.888(4) Å and Z = 4. Discrete [H₂P₂O₆]^2– units, barium cations and water molecules, held together by intermolecular hydrogen bonds of the type O–H ··· O, build up the structures of the three polymorphs. The phase purity of A and C was verified by powder diffraction measurements.     

[{Er(NC5H4COOH)(H2O)2}2(H5O2)(HgCl5)(HgCl4)2(H2O)2]n – Synthesis,Crystal Structure and Properties

The first heterometallic 4f‐5d inorganic‐organic metal‐isonicotinic acid hybrid [{Er(NC₅H₄COOH)(H₂O)₂}₂(H₅O₂)(HgCl₅)(HgCl₄)₂(H₂O)₂]_n ( 1 ) has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of the monoclinic system with four formula units per unit cell: a = 24.194(3), b = 20.792(3), c = 15.289(4) Å, β = 128.39(2)°, V = 6028(2) ų, C₃₆H₄₇Cl₁₃Er₂Hg₃N₆O₂₀, M_r = 2280.94, D_c = 2.513 g/cm³, S = 0.929, μ(MoKα) = 11.017 mm^?1, F(000) = 4248, R = 0.0425 and wR = 0.0739. The crystal structure analysis reveals that the title complex is characteristic of a one‐dimensional chain‐like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.45 eV. The magnetic properties show that complex 1 exhibits antiferromagnetic interactions.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

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.     

Bis[N,N′‐bis(2‐nitrocinnamaldehyde)phenylenediimine]copper(I) Perchlorate

The complex [Cu(nitroca₂ph)₂]ClO₄, where nitroca₂ph is N,N′‐bis(2‐nitrocinnamaldehyde)phenylenediimine, crystallizes in the triclinic space group with a = 13.167(1), b = 13.209(1), c = 14.465(1) Å, α = 83.209(9)°, β = 68.438(2)°, γ = 70.803(2)°, V = 2209.4(3) ų, Z = 2, D_calc = 1.527 mg/m³. The coordination polyhedron about the Cu(I) atom is best described as a distorted tetrahedron. 2‐nitroca₂en acts as a bidentate ligand coordinating via two N atoms to the copper. The four Cu–N distances are 2.04 (2), 2.038(2), 2.046(2), and 2.062(2) Å.     

Effects of Bis(aromatic) Pendants on Recognition of Nucleobase Thymine by Zn2+ -1,4,7,10-tetraazacyclododecane (Zn2+ -cyclen)

We have previously shown that the nucleobase thymine binding to Zn²⁺ -cyclen (cyclen=1,4,7,10-tetraazacyclododecane) complex became stronger by appending acridine, naphthalene, or quinoline rings to the cyclen. Amongst these, the pendant bis((1-naphthyl)methyl) or bis((4-quinolyl)methyl) groups yielded the most effective thymine-recognizing Zn²⁺ -cyclen complexes [J. Am. Chem. Soc., 121 (1999) 5426]. The present study was undertaken to find causes of the bis(aromatic) ring effect by X-ray crystal structure analysis and NMR studies. The crystal structure of the Zn²⁺ -bis((1-naphthyl)methyl)-cyclen complex with a deprotonated 1-methylthymine (1-MeT) failed to show the anticipated evidence for the double ~ - ~ stacking interactions between the two naphthalenes and the Zn 2+ -bound 1-MeT m (1-MeT m =N(3')-deprotonated 1-MeT). Crystal data: formula C₃₆ H₄₇ N₇ O₇ Zn, M r =755.19, monoclinic, space group P2₁/ c (No. 14), a =15.438(2) Å, b =14.093(3) Å, c =16.726(2) Å, g =90.53(1) V =3638.7(8) Å 3 Z =4, R =0.035, R _w =0.049. However, the ¹H NMR studies of Zn²⁼ -bis((4-quinolyl)methyl)-cyclen with 1-MeT in varying H₂O/CH₃ CN solution showed increasing upfield shifts of Me(5') and H(6') of the Zn²⁺ -bound 1-MeT in more aqueous media, indicating that the double intercalation with the two quinolines became more significant in more protic environments. We conclude that the double ~ - ~ stacking effect accounts for the enhanced recognition of thymine base by the appended bis((1-naphthyl)methyl) or bis((4-quinolinyl)methyl) groups.     

Synthesis,Crystal Structure and Properties of [Mn(hdpa)2(N(CN)2)2] and [Co(hdpa)2(N(CN)2)2] (hdpa = 2, 2'‐Dipyridylamine)

Two new transition metal(II) complexes [M(hdpa)₂(N(CN)₂)₂] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) ų for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)ų for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)^— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated.     

Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

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.     

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.     

Grid‐like Cobalt(II) Layered Complex with an Unprecedented Double 1,2‐Bis(1,2,4‐triazole‐1‐yl)methane Bridges

A novel two‐dimensional cobalt complex, [Co(btrm)₂(dca)]ClO₄ ( 1 , btrm = 1,2‐bis(1,2,4‐triazole‐1‐yl)methane, dca = dicyanamide), was synthesized and characterized. X‐ray diffraction analyses reveal that the title complex crystallizes in the monoclinic space group C2/m with a = 29.507(13)Å, b = 17.804(8) Å, c = 14.709(7) Å, β = 119.916(7)°, Z = 12, and R₁ = 0.0784, wR₂ = 0.2041. The cobalt atom involves a six‐coordinated CoN₆ environment, with a distorted octahedral coordination. Two btrm ligands connect the Co^II atoms with the exodentate nitrogen atoms on the 4‐position of triazole rings to form a sixteen‐membered rhombic grid. The unprecedented double btrm bridges and μ_1,5‐dca bridge connect the cobalt atoms to form a two‐dimensional grid‐like layered structure. The spectroscopic and magnetic properties have also been investigated.     

Seltenerdhalogenide Ln4X5Z. Teil 1: C und/oder C2 in Ln4X5Z

Rare Earth Halides Ln₄X₅Z. Part 1: C and/or C₂ in Ln₄X₅Z The compounds Ln₄X₅C_n (Ln = La, Ce, Pr; X = Br, I and 1.0 < n < 2.0) are prepared by the reaction of LnX₃, Ln metal and graphite in sealed Ta‐ampoules at temperatures 850 °C < T < 1050 °C. They crystallize in the monoclinic space group C2/m. La₄I₅C_1.5: a = 19.849(4) Å, b = 4.1410(8) Å, c = 8.956(2) Å, β = 103.86(3)°, La₄I₅C_2.0: a = 19.907(4) Å, b = 4.1482(8) Å, c = 8.963(2) Å, β = 104.36(3)°, Ce₄Br₅C_1.0: a = 18.306(5) Å, b = 3.9735(6) Å, c = 8.378(2) Å, β=104.91(2)°, Ce₄Br₅C_1.5: a = 18.996(2) Å, b = 3.9310(3) Å, c = 8.282(7) Å, β = 106.74(1)°, Pr₄Br₅C_1.3: a = 18.467(2) Å, b = 3.911(1) Å, c = 8.258(7) Å, β = 105.25(1)° and Pr₄Br₅C_1.5: a = 19.044(2) Å, b = 3.9368(1) Å, c = 8.254(7) Å, β = 106.48(1)°. In the crystal structure the lanthanide metals are connected to Ln₆‐octahedra centered by carbon atoms or C₂‐groups. The Ln₆‐octahedra are condensed via opposite edges to chains and surrounded by X atoms which interconnect the chains. A part n of isolated C‐atoms is substituted by 1‐n C₂‐groups. The C‐C distances range between 1.26 and 1.40Å. In the ionic formulation (Ln³⁺)₄(X^?)₅(C^4?)_n(C₂^m?)_1?n·e^? with 0 < n < 1 and m = 2, 4, 6 (C₂^2?, C₂^4? C₂^6?), there are 1 < e^? < 5 electrons centered in metal‐metal bonds.     

Syntheses and Structures of two 1‐D Complexes, [Co(dmf)2(NCNCN)2] and [Cu(bipy)(NCNCN)]ClO4 with Bridging Dicyanamide Ligands

Two novel dicyanamide complexes [Co(dmf)₂(NCNCN)₂] ( 1 ) and [Cu(bipy)(NCNCN)]ClO₄ ( 2 ) have been synthesized and structurally characterized. 1 crystallizes in the monoclinic space group C2 with a = 13.568(6)Å, b = 7.403(3)Å, c = 8.118(3)Å and Z = 2, whereas 2 crystallizes in the monoclinic system, Cc group, a = 14.270(7)Å, b = 9.143(5)Å, c = 12.371(1) Å, β = 118.612(7)°, and Z = 4. According to X‐ray crystallographic studies, in complex 1 each Co^II ion is six‐coordinated with four nitrogen atoms from four μ_{1, 5}‐dca (dca = dicyanamide) ligands and two oxygen atoms from two dmf ligands to form distorted octahedra. 1 forms a 1‐D network bridged via μ_{1, 5}‐dca. 2 consists of a uniform Cu(NCNCN)Cu chain, each Cu^II ion is octahedrally coordinated with four nitrogen atoms from two μ_{1, 5}‐dca ligands and one bipy ligand and two oxygen atoms from two ClO₄^— ions. The octahedral Cu^II ion shows a significant Jahn‐Teller distortion, with two axial oxygen atoms considerably farther from the copper than the four equatorial nitrogens.     

Synthesis,Structural Characterization and Thermal Stability of [Mn(3‐bpd)2(NCS)2(H2O)2]·2H2O (1) and {[Mn(bpe)(NCS)2(H2O)2]·(3‐bpd)·(bpe)·H2O}n (2) from One‐Pot Crystallization

Two supramolecular architectures, [Mn(3‐bpd)₂(NCS)₂(H₂O)₂]·2H₂O ( 1 ) and {[Mn(bpe)(NCS)₂(H₂O)₂]·(3‐bpd)·(bpe)·H₂O}_n ( 2 ) [bpe = 1,2‐bis(4‐pyridyl)ethylene and 3‐bpd = 1,4‐bis(3‐pyridyl)‐2,3‐diaza‐1,3‐butadiene] have been synthesized and characterized by spectroscopic, elemental and single crystal X‐ray diffraction analyses. Compound 1 crystallizes in the monoclinic system, space group P2₁/c, with chemical formula C₂₆H₂₈Mn N₁₀O₄S₂, a = 9.1360(6), b = 9.7490(6), c = 17.776(1) Å, β = 93.212(1)°, and Z = 2 while compound 2 crystallizes in the orthorhombic system, space group P2₁2₁2₁, with chemical formula C₃₈H₃₆Mn₁N₁₀O₃S₂, a = 14.1902(6), b = 15.4569(7), c = 18.2838(8) Å, α = β = γ = 90°, and Z = 4. Structural determination reveals that the coordination geometry at Mn(II) in compound 1 or 2 is a distorted octahedral which consists of two nitrogen donors of two NCS^?ligands, two oxygen donors of two water molecules, and two nitrogen donors of two 3‐bpd ligands for 1 and two dpe ligands for 2 , respectively. The two 3‐bpd ligands in 1 adopt a monodentate binding mode and the dpe in 2 adopts a bismonodentate bridging mode to connect the Mn(II) ions forming a 1D chain‐like coordination polymer. Both the π‐π stacking interactions between the coordinated and the free pyridyl‐based ligands and intermolecular hydrogen bonds among the coordinated and the crystallized water molecules and the free pyridyl‐based ligands play an important role in construction of these 3D supramolecular architectures.