Kristallstruktur,Schwingungsspektren und Normalkoordinatenanalyse von (n‐Bu4N)2[{Ru(NO)ClI2}2(μ‐I2)] · 2 I2

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[{Ru(NO)ClI₂}₂(μ‐I₂)] · 2 I₂ By treatment of (n‐Bu₄N)₂[Ru(NO)I₅] with (n‐Bu₄N)Cl in dichloromethane (n‐Bu₄N)₂[{Ru(NO)ClI₂}₂(μ‐I₂)] is formed. The X‐Ray structure determination on a single crystal of (n‐Bu₄N)₂[{Ru(NO)ClI₂}₂(μ‐I₂)] · 2 I₂ (monoclinic, space group I 2/a, a = 20.446(6), b = 11.482(8), c = 27.225(3) Å, β = 107.51(4)°, Z = 4) reveals a dinuclear iodine bridged structure, in which the chlorine atoms are trans positioned to the nitrosyl groups. The low temperature IR and Raman spectra have been recorded of (n‐Bu₄N)₂[{Ru(NO)ClI₂}₂(μ‐I₂)] · 2 I₂ and are assigned by normal coordinate analysis. A good agreement between observed and calculated frequencies is achieved. The valence force constants are f_d(NO) = 14.08, f_d(RuN) = 5.58, f_d(RuCl) = 1.52, f_d(RuI_t) = 0.90 and f_d(RuI_b) = 0.76 mdyn/Å.     

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.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

Syntheses and Crystal Structures of Three Polymeric Silver(I) Terephthalate Complexes with Organic N‐Donor Ligands: [Ag(pren)]2(tp)·2H2O, [Ag(en)][Ag(μ2‐tp)]·H2O,and [Ag2(μ4‐tp)(apy)2]

Three polymeric silver(I) complexes with terephthalate anions as counterions or ligands, [Ag(pren)]₂(tp)·2H₂O ( 1 ), [Ag(en)][Ag(μ₂‐tp)]·H₂O ( 2 ), and [Ag₂(μ₄‐tp)(apy)₂] ( 3 ) (where pren = 1, 2‐propylenediamine, tp =terephthalate dianion, en = ethylenediamine, and apy = 2‐aminopyridine) were synthesized and characterized by X‐ray single crystal analysis and infrared spectroscopy. 1 crystallizes in the monoclinic space group P2₁1/c with a = 11.3221(5), b = 7.1522(3), c = 14.8128(5)Å, V = 1015.77(7)ų, β = 122.132(2), and Z = 2. 2 crystallizes in the orthorhombic space group Pnma with a = 9.6144(6), b = 11.3465(7), c = 11.4810(7)Å, V = 1252.5(1)ų, and Z = 4. 3 crystallizes in the monoclinic space group P2₁/n with a = 8.2003(5), b = 5.8869(4), c = 18.3769(11)Å, β = 92.593(1), V = 886.2(1)ų, and Z = 4. Terephthalate dianions are not coordinated to the metal atoms in 1 , but act as a μ₂‐bridging ligand in 2 and as a μ₄‐bridging ligand in 3 .     

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.     

Synthesis and Thermal Behaviour of Compounds in the System [Ph4P]Cl/BiCl3 and the Crystal Structures of [Ph4P]3[Bi2Cl9] · 2 CH2Cl2 and [Ph4P]2[Bi2Cl8] · 2 CH3COCH3

Six polynuclear chlorobismuthates are formed in the reaction between BiCl₃ and Ph₄PCl by variation of the molar ratio of the educts, the solvents and the crystallisation methods: [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂, [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃, [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃, [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN, [Ph₄P]₄[Bi₆Cl₂₂], and [Ph₄P]₄[Bi₈Cl₂₈]. We report the crystal structure of [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ which crystallises with triclinic symmetry in the S. G. P1 No. 2, with the lattice parameters a = 13.080(3) Å, b = 14.369(3) Å, c = 21.397(4) Å, α = 96.83(1)°, β = 95.96(1)°, γ = 95.94(2)°, V = 3943.9(1) ų, Z = 2. The anion is formed from two face‐sharing BiCl₆‐octahedra. [Ph₄P]₂[Bi₂Cl₈] · 2 CH₃COCH₃ crystallises with monoclinic symmetry in the S. G. P2₁/n, No. 14, with the lattice parameters a = 14.045(5) Å, b = 12.921(4) Å, c = 17.098(3) Å, β = 111.10(2)°, V = 2894.8(2) ų, Z = 2. The anion is a bi‐octahedron of two square‐pyramids, joined by a common edge. The octahedral coordination is achieved with two acetone ligands. [Ph₄P]₄[Bi₄Cl₁₆] · 3 CH₃CN crystallises in the triclinic S. G., P1, No. 2, with the lattice parameters a = 14.245(9) Å, b = 17.318(6) Å, c = 24.475(8) Å, α = 104.66(3)°, β = 95.93(3)°, γ = 106.90(4)°, V = 5486(4) ų, Z = 2. Two Bi₂Cl₈ dimers in syn‐position form the cubic anion. Lattice parameters of [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ are also given. The solvated compounds are desolvated at approximately 100 °C. [Ph₄P]₃[Bi₂Cl₉] · 2 CH₂Cl₂ and [Ph₄P]₃[Bi₂Cl₉] · CH₃COCH₃ show the same sequence of phase transitions after desolvation. All compounds melt into a liquid in which some order is observed and transform on cooling into the glassy state.     

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.     

Zwei Tetrachlorothiotantalate: [Na‐15‐Krone‐5][TaSCl4 · Dioxan] und [Na‐15‐Krone‐5]2[(TaSCl4)2Dioxan] · S8

Two Tetrachlorothiotantalates: [Na‐15‐crown‐5][TaSCl₄ · dioxane] and [Na‐15‐crown‐5]₂[(TaSCl₄)₂dioxane] · S₈ During the reaction of Na₂S₄, TaCl₅ and 15‐crown‐5 in dichloromethane the crown ether partly suffers degradation to 1,4‐dioxane. Aside from sulfur, [Na‐15‐crown‐5][TaSCl₄ · dioxane] was the first product obtained. It crystallizes in the monoclinic space group P2₁/n with a = 1066.1, b = 1781.3, c = 1258.3 pm, β = 97.14°, Z = 4. In the [TaSCl₄ · dioxane]^– ion a dioxane molecule is loosely bonded to a square‐pyramidal TaSCl₄^– unit; two chlorine atoms are in contact with an Na⁺ ion. Upon standing with the mother liquor [Na‐15‐crown‐5]₂[(TaSCl₄)₂dioxane] · S₈ was formed. It crystallizes in the monoclinic space group C2/m; a = 1768.5, b = 1084.0, c = 1517.3 pm, β = 118.46°, Z = 4. In this case a dioxane molecule is coordinated with two TaSCl₄^– units. The [(TaSCl₄)₂ · dioxane]^2– ions and S₈ molecules alternate in the stacking direction b.     

[BuN(CH2CH2)3NBu]3[Pb5I16] · 4 DMF – ein Iodoplumbat mit nahezu D5h‐symmetrischem Anion

[BuN(CH₂CH₂)₃NBu]₃[Pb₅I₁₆] · 4 DMF – an Iodoplumbate Anion with approximately D _5h Symmetry The star‐shaped anion of [BuN(CH₂CH₂)₃NBu]₃‐[Pb₅I₁₆] · 4 DMF ( 1 ) consists of a cyclic arrangement of five PbI₆ octahedra sharing one common I atom in the centre of an almost planar Pb₅ ring. Compound 1 crystallizes in space group P2₁ with a = 1657.2(1), b = 2029.2(1), c = 1773.6(1) pm, β = 113.238(8)°, Z = 2.     

Hydroxo‐bridged Tetranuclear CuII Complexes: {[Cu(bpy)(OH)]4Cl2}Cl2 · 6 H2O and {[Cu(phen)(OH)]4(H2O)2}]Cl4 · 4 H2O

The blue tetranuclear Cu^II complexes {[Cu(bpy)(OH)]₄Cl₂}Cl₂ · 6 H₂O ( 1 ) and {[Cu(phen)(OH)]₄(H₂O)₂}Cl₄ · 4 H₂O ( 2 ) were synthesized and characterized by single crystal X‐ray diffraction. ( 1 ): P 1 (no. 2), a = 9.240(1) Å, b = 10.366(2) Å, c = 12.973(2) Å, α = 85.76(1)°, β = 75.94(1)°, γ = 72.94(1)°, V = 1152.2(4) ų, Z = 1; ( 2 ): P 1 (no. 2), a = 9.770(3) Å, b = 10.118(3) Å, c = 14.258(4) Å, α = 83.72(2)°, β = 70.31(1)°, γ = 70.63(1)°, V = 1252.0(9) ų, Z = 1. The building units are centrosymmetric tetranuclear {[Cu(bpy)(OH)]₄Cl₂}²⁺ and {[Cu(phen)(OH)]₄(H₂O)₂}⁴⁺ complex cations formed by condensation of four elongated square pyramids CuN₂(OH)₂L^ap with the apical ligands L^ap = Cl, H₂O, OH. The resulting [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂] core has the shape of a zigzag band of three Cu₂(OH)₂ squares. The cations exhibit intramolecular and intermolecular π‐π stacking interactions and the latter form 2D layers with the non‐bonded Cl^– anions and H₂O molecules in between (bond lengths: Cu–N = 1.995–2.038 Å; Cu–O = 1.927–1.982 Å; Cu–Cl^ap = 2.563; Cu–O^ap(OH) = 2.334–2.369 Å; Cu–O^ap(H₂O) = 2.256 Å). The Cu…Cu distances of about 2.93 Å do not indicate direct interactions, but the strongly reduced magnetic moment of about 2.74 B.M. corresponds with only two unpaired electrons per formula unit of 1 (1.37 B.M./Cu) and obviously results from intramolecular spin couplings (χ_m(T‐θ) = 0.933 cm³ · mol^–1 · K with θ = –0.7 K).     

The Phase Diagram of the System [Ph4P]Br/BiBr3. Synthesis,Crystal Structure,Thermal Behaviour,and Vibrational Spectra of [Ph4P]3[Bi2Br9] · CH3COCH3 and two Modifications of [Ph4P]4[Bi6Br22]

The phase diagram of the system [Ph₄P]Br/BiBr₃ was investigated with the aid of DSC, TG and temperature dependent X‐ray powder diffraction measurements. By varying the reaction conditions, stoichiometry and crystallisation conditions of the reaction between BiBr₃ and [Ph₄P]Br four polynuclear bromobismuthates are formed. We report here the crystal structure of the solvation product [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃, which crystallises with monoclinic symmetry in the S. G. P2₁/n No. 14, a = 12.341(1), b = 32.005(3), c = 19.929(3) Å, β = 99.75(2)°, V = 7758(7) ų, Z = 4 and the crystal structures of two modifications of the compound [Ph₄P]₄[Bi₆Br₂₂]. The α‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.507(4) Å, b = 14.434(4) Å, c = 17.709(5) Å, α = 81.34(2)°, β = 72.42(2)°, γ = 72.53(2)°, V = 3132.7(1) ų, Z = 2. The high‐temperature β‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.893(4) Å, b = 14.267(3) Å, c = 16.580(3), α = 100.13(2)°, β = 96.56(2)°, γ = 110.01(2)°, V = 2985.5(1) ų, Z = 2. Lattice parameters of [Ph₄P]₄[Bi₈Br₂₈] are also given. The thermal behaviour of the compounds and in addition the vibrational spectra of [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃ are presented and discussed.     

The synthesis and crystal structure of a trinuclear molybdenum cluster compound [Mo3(μ-O)(μ-S)3(μ(μ-OAc)2(dtp)2·(Py)]·0.5H2O

[Mo₃,OS₃(dtp)₄(H₂O)] reacts with NaOAc·3H₂O in Py to give the title compound. The crystal data are as follows: [Mo₂OS₃)(OAc)₂(dtp)₂·Py]?0.5H,O(dtp = [S₃P(OC₂H₅)₂]^?, Py = C₅H₅N); M = 976.64; triclinic; space group P1 ; a=11.704(5), b=14.169(7), c= 11.688 (5) Å α=109.94(4) β = 91.53(4), γ = 91.93(4)°; V= 1819(1) Ų; Z=2; D_c = 1.78 g·cm^?3 λ(Mo Kα) = 0.71069 Å μ=15.15 cm^?1; F(000) = 970 T=296 K; final R=0.071 for 1652 reflections with I>3σ(I). In the molecule, the [Mo₃OS₃] core is surrounded by two bridging OAc groups and two terminal chelate dtp groups attached to the {Mo₃} triangle in a symmetric style, and the Py ligand is coordinated to the Mo atom at the apex of {Mo₃} triangle with the nitrogen. This novel configuration is obtained for the first time with Mo—N bond length being 2.27 (2) Å and three Mo—Mo bond lengths 2.584 (4), 2.587 (4) and 2.657(4) Å, respectively. As a whole, the molecule has a virtual C₂ symmetry.     

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.     

Synthese und Kristallstruktur der Monoammoniakate von Lithiumhalogeniden: LiBr·NH3 und LiI·NH3

Syntheses and Crystal Structures of the Monoammoniates of Lithium Halides: LiBr·NH₃ and LiI·NH₃ Crystals of LiBr·NH₃ and LiI·NH₃ sufficient in size and quality for X‐ray structure determinations were obtained in autoclaves by the reaction of Li with NH₄Br and LiH with NH₄I at 523 K and 423 K respectively. Lattice constants obtained from X‐ray single crystal data are: LiBr·NH₃: P2₁/n, a = 7, 077(2)Å, b = 7, 026(2)Å, c = 7, 490(2)Å β = 114, 84(3)°, Z = 4 LiI·NH₃: P2₁, a = 4, 493(1)Å, b = 6, 077(1)Å, c = 7, 512(2)Å β = 107, 15(3)°, Z = 2 The ammoniates contain different structural building units. Both of them contain layers of connected tetrahedra Li(NH₃)X_3/3 with X = Br, I. Tetrahedra‐double units with a common Br‐Br edge occur, whilst for the iodide all tetrahedra are exclusively vertex connected to puckered layers. IR‐ and Raman‐spectroscopic measurements show, that only weak H‐bridges N‐H···X are present and that the NH₃‐ligands are in fixed positions 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.     

Darstellung und Struktur der Komplexverbindungen trans‐[CoIII(py)4F2][H2F3] und [Pd(py)4]F2 · 1,5 HF · 2 H2O

Synthesis and Crystal Structures of the Complexes trans ‐[Co^III(py)₄F₂][H₂F₃] and [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O The cobalt complex trans‐[Co(III)(py)₄F₂][H₂F₃] ( 1 ) has been prepared by electrochemical oxidation of CoF₂ in a pyridine/HF mixture and the palladium complex [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O ( 2 ) has been obtained via halogen exchange between Pd(py)₂Cl₂ and AgF₂ in pyridine. 1 and 2 crystallize in the space group C2/c with a = 27.928(14), b = 9.019(3), c = 18.335(8) Å, β = 113.41(3)° for 1 and a = 28.183(9), b = 9.399(3), c = 17.397(6) Å, β = 104.66(3)° for 2 , respectively. Concerning the shape and location of the M(py)₄ fragments 1 and 2 are isostructural. The metal atoms occupy special positions in their unit cells with the result that four complex atoms have C₂ symmetry and four complex cations have C_i symmetry giving a total of Z = 8. In 1 two F^– ions complete an octahedral coordination around the Co atoms (Co–F 1.820(2) to 1.834(3) Å). In 2 the shortest Pd–F distance is 3.031(2) Å. This precludes the existence of Pd–F bonds. In 1 one can identify H₂F₃^– groups. In 2 there are larger aggregates, consisting of F^–, HF, and H₂O subunits, connected by H‐bridges. In spite of these differences, both complexes belong to the same type of structure, which may be of a common type M^x+(py)₄F_x · y HF · z H₂O.     

Crystal Structure of the Mixed‐Valent Basic Mercury Nitrate HgI2(NO3)2·HgII(OH)(NO3)·HgII(NO3)2·4HgIIO [= Hg8O4(OH)(NO3)5]

Light‐yellow single crystals of the mixed‐valent mercury‐rich basic nitrate Hg₈O₄(OH)(NO₃)₅ were obtained as a by‐product at 85 °C from a melt consisting of stoichiometric amounts of (Hg^I₂)(NO₃)₂·2H₂O and Hg^II(OH)(NO₃). The title compound, represented by the more detailed formula Hg^I₂(NO₃)₂·Hg^II(OH)(NO₃)·Hg^II(NO₃)₂·4Hg^IIO, exhibits a new structure type (monoclinic, C2/c, Z = 4, a = 6.7708(7), b = 11.6692(11), c = 24.492(2) Å, β = 96.851(2)°, 2920 structure factors, 178 parameters, R1[F² > 2σ(F²)] = 0.0316) and is made up of almost linear [O‐Hg^II‐O] and [O‐Hg^I‐Hg^I‐O] building blocks with typical Hg^II‐O distances around 2.06Å and a Hg^I‐O distance of 2.13Å. The Hg₂²⁺ dumbbell exhibits a characteristic Hg‐Hg distance of 2.5079(7) Å. The different types of mercury‐oxygen units form a complex three‐dimensional network exhibiting large cavities which are occupied by the nitrate groups. The NO₃^? anions show only weak interactions between the nitrate oxygen atoms and the mercury atoms which are at distances > 2.6Å from one another. One of the three crystallographically independent nitrate groups is disordered.     

Synthesis and Crystal Structure of Manganese(II) Bipyridine Carboxylato Complexes: [(bipy)2MnII(μ‐C2H5CO2)2MnII(bipy)2](ClO4)2 and [MnII(ClCH2CO2)(H2O)(bipy)2]ClO4 · H2O (bipy = 2,2′‐bipyridine)

Two manganese(II) bipyridine carboxylate complexes, [(bipy)₂Mn^II(μ‐C₂H₅CO₂)₂Mn^II(bipy)₂}₂](ClO₄)₂ ( 1 ), and [Mn^II(ClCH₂CO₂)(H₂O)(bipy)₂]ClO₄ · H₂O ( 2 ) were prepared. 1 crystallizes in the triclinic space group P 1 with a = 8.604(3), b = 12.062(3), c = 13.471(3) Å, α = 112.47(2), β = 93.86(2), γ = 92.87(3)°, V = 1211.1(6) ų and Z = 1. In the dimeric, cationic complex with a crystallographic center of symmetry two 2,2′‐bipyridine molecules chelate each manganese atom. These two metal fragments are then bridged by two propionato groups in a syn‐anti conformation. The Mn…Mn distance is 4.653 Å. 2 crystallizes in the monoclinic space group P2₁/c with a = 9.042(1), b = 13.891(1), c = 21.022(3) Å, β = 102.00(1)°, V = 2569.3(5) ų and Z = 4. 2  is a monomeric cationic complex in which two bipyridine ligands chelate the manganese atom in a cis fashion. A chloroacetato and an aqua ligand complete the six‐coordination. Only in 2 is the intermolecular packing controlled by weak π‐stacking besides C–H…π contacts between the bipyridine ligands.     

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.     

Synthesis and crystal structure of a cubanelike tetranuclear molybdenum cluster compound {Mo4)(μ3-S)3)(μ3-O)[S2P(OEt)2]6} · 3CH3CN

A tetranuclear molybdenum cluster compound {Mo₄(μ₃-S)₃(μ₃-O)[S₂P(OEt)₂]₅} · 3CH₃CN was obtained by the reaction of MoCl₃ · 3H₂O with P₂S₅ in ethanol and then recrystallization from acetonitrile. The compound crystallizes in the trigonal system belonging to the space group R3 with the following cell dimensions: a = b = c = 12.852 (3) Å, α = β = γ = 108.37 (2)°, V =1697.3ų Z = 1, D_c. = 1.693g.cm^?3. The structure was solved by heavy atom method and refined by full-matrix least-squares to R = 0.072 for 1781 reflections with I≥3σ(I). The results of the structure determination indicate that the cluster skeleton possesses a cubanelike cluster core formed by four Mo atoms located in a distored tetrahedron with three S atoms and one O atom as its triple bridging atoms. There are two sets of bond distances, i.e. 2.700 (1) and 2.831(1) Å in the six Mo—Mo bonds. Taking the Mo cluster core as a whole, it has a formal oxidation state of +14, leaving ten electrons to form the metal-metal bonds. Thus each Mo—Mo bond has an average bond order of 5/6.