Sur les carbonates basiques de fer (III): II. Préparation,radiocristallographie et spectres IR. du (NH4)2Fe2(OH)4(CO3)2 · H2O

The obtention of the crystalline basic carbonate of iron (III) and ammonium, (NH₄)₂Fe₂(OH)₄(CO₃)₂ · H₂O, is described and its formula is established by chemical analysis and infrared spectroscopy. The powder X-ray diagram could be indexed tetragonally leading to a body centred elementary cell with a = 12,04 ± 0,02 Å and c = 6,62 ± 0,01 Å. The infrared spectra show that in the CO groups either one oxygen atom is linked to one iron atom or, rather, two oxygen atoms are linked to two iron atoms. The symmetry of the NH groups is lower than C_3v. The OH-groups are linked by hydrogen bonds of 2,75 Å. Two sorts of OH-groups can be distinguished, with a radius of approximately 1,34 Å and 1, 48 Å, respectively. The iron atoms are octahedrally coordinated by oxygen atoms, but either the octahedra are deformed or the iron atoms are in part coordinated tetrahedrally.     

A New Sulfato‐bridged Manganese(II) Phenanthroline Complex: [Mn(phen)(H2O)2(SO4)]

The sulfato bridged Mn^II phen complex [Mn(phen)(H₂O)₂SO₄] ( 4 ) consists of [Mn(H₂O)₂(phen)(SO₄)_2/2] chains, which are generated from Mn atoms in distorted octahedral sites interlinked by bidentate sulfato bridges. Interdigitation of phen ligands leads to the formation of [Mn(H₂O)₂(phen)(SO₄)_2/2] double‐chains stabilized by significant π—π stacking interactions. The double‐chains are held together via interchain hydrogen bonds formed between water and sulfato O atoms. Crystal data: orthorhombic, P2₁2₁2₁ (no. 19), a = 6.674(1), b = 10.359(1), c = 19.913(3)Å, V = 1376.7(3)ų, Z = 4, R = 0.0439 and wR² = 0.0935 for 1830 out of 2286 reflections with F_o² > 2σ(F_o²).     

Darstellung und Struktur eines Ammoniumdiamidodioxophosphats(V), NH4PO2(NH2)2

Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH₄PO₂(NH₂)₂ The ammonolysis of P₃N₅ under ammonothermal conditions (T = 400°C, p(NH₃) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH₄PO₂(NH₂)₂. The structure was solved by single crystal X-ray methods. NH₄PO₂(NH₂)₂: P2₁/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R₁/wR₂ = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH₄PO₂(NH₂)₂ the anions [PO₂(NH₂)₂]^? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally.     

Kristallstrukturen und Wasserstoffbrückenbindungen bei β-Be(OH)2 und ϵ-Zn(OH)2

Crystal Structures and Hydrogen Bonding for β-Be(OH)₂ and ϵ-Zn(OH)₂ Crystals of β-Be(OH)₂ sufficient for x-ray structure determination were grown from a saturated hot solution of freshly prepared Be(OH)₂ in NaOH by slowly cooling down and in the case of ϵ-Zn(OH)₂ by electrochemical oxidation of zinc in a NaOH/NH₃ solution. The structures of the isotypic compounds were determined including the H-positions: β-Be(OH)₂: P2₁2₁2₁, Z = 4, a = 4.530(2) Å, b = 4.621(2) Å, c = 7.048(2) Å N(F > 3σ F) = 432, N(parameters) = 36, R/R_w = 0.044/0.052 ϵ-Zn(OH)₂: P2₁2₁2₁, Z = 4, a = 4.905(3) Å, b = 5.143(4) Å, c = 8.473(2) Å N(F > 3σ F) = 1107, N(parameters) = 36, R/R_w = 0.025/0.027For neutron diffraction experiments microcrystalline β-Be(OD)₂ was prepared. With time-of-flight data the D positions were determined giving d(O–D) = 0.954(4) Å. The structures are closely related to that of β-cristobalite: As in SiO₂ a quarter of tetrahedral interstices in a distorted cubic close packed arrangement of O is regularily occupied by the metal atoms. The filled O tetrahedra are twisted against one another in such a way, that O–H…O–H hydrogen bonds are favoured which are surprisingly stronger in the zinc than in the beryllium compound.     

Darstellung und Kristallstruktur von trans-(Ph4As)2[OsCl2(NCS)(SCN)], Schwingungsspektren und Normalkoordinatenanalyse

Preparation and Crystal Structure of trans-(Ph₄As)₂[OsCl₂(NCS) (SCN) ], Vibrational Spectra and Normal Coordinate Analysis By treatment of trans-[OsCl₂I₄]^2? with (SCN)₂ in dichloromethane a mixture of different linkage isomers is formed, from which trans-[OsCl₂(NCS)(SCN)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determination on a single crystal of trans-(Ph₄As)₂[OsCl₂(NCS)(SCN)] (triclinic, space group P 1 , a = 12.505(5), b = 12.056(5), c = 19.833(5) Å, α = 108.047(5)°, β = 91.964(5)°, γ = 117.048(5)°, Z = 2) reveals that two cis-positioned Thiocyanate(N) groups are coordinated with Os? N? C angles of 172.1° and 173.0° and two cis-positioned Thiocyanate(S) groups are coordinated with Os? S? C angles of 106.9° and 108.7°. Using the molecular parameters of the X-Ray determination the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the linkage isomer are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.63 and f_d(OsS) = 1.30 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

The crystal structure of tris (ethylenediamine), cobalt(III) hexacyanoferrate(III)dihydrate,Co(C2H8N2)3[Fe(CN)6] · 2H2O

The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2_l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)₃ Q(CN)₆ · H₂O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous.     

Cadmium in tetragonal pyramidaler Koordination im Barium-Cadmium-Oxovanadat: Ba2Cd3(VO4)2(V2O7)

Cadmium in Square Pyramids of Oxygen in the Barium Cadmium Oxovanadate: Ba₂Cd₃(VO₄)₂(V₂O₇) Single crystals of Ba₂Cd₃(VO₄)₂(V₂O₇) have been prepared by crystallization of a melt of BaCO₃, CdO and V₂O₅. It shows orthorhombic symmetry, space group D? P2₁2₁2₁, a = 7.206(2), b = 9.978(1), c = 19.617(3) Å, Z = 4. The crystal structure is characterized by (VO₄)^3? and (V₂O₇)^4? groups, CdO₆ octahedra, BaO₁₂ and BaO₉ polyhedra and with respect to Cd containing oxides unusual square pyramids of O^2? around Cd²⁺. The observed [CdO₄] zickzack chains are connected by VO₄ tetrahedra, V₂O₇ double tetrahedra and CdO₅ pyramids, forming a tunnel structure along [100]. The tunnels are filled by barium.     

Zur Kristallstruktur von CaZn2(OH)6 · 2 H2O

Crystal Structure of CaZn₂(OH)₆ · 2 H₂O The electrochemical oxidation of zinc in a zinc/iron-pair leads in an aqueous NH₃ solution of calciumhydroxide at room temperature to colourless crystals of CaZn₂(OH)₆ · 2 H₂O. The X-ray structure determination was now successful including all hydrogen positions. P2₁/c, Z = 2, a = 6.372(1) Å, b = 10.940(2) Å, c = 5.749(2) Å, β = 101.94(2)° N(F ≥ 3σF) = 809, N(Var.) = 69, R/R_W = 0.011/0.012 The compound CaZn₂(OH)₆ · 2H₂O contains Zn²⁺ in tetrahedral coordination by OH^? and Ca²⁺ in octahedral coordination by four OH^? and two H₂O. The tetrahedra around Zn²⁺ form corner sharing chains, three-dimensionally linked by isolated polyhedra around Ca²⁺. Weak hydrogen bridge bonds result between H₂O as donor and OH^?.     

Crystal Structures of {[Cd(phen)](C6H8O4)3/3} and {[Cd(phen)](C7H10O4)3/3} · 2H2O with C6H10O4 = Adipic Acid and C7H12O4 = Pimelic Acid

Two coordination polymers {[Cd(phen)](C₆H₈O₄)_3/3} ( 1 ) and {[Cd(phen)](C₇H₁₀O₄)_3/3} · 2H₂O ( 2 ) were structurally characterized by single crystal X‐ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)Å, b = 15.485(2)Å, c = 14.044(2)Å, β = 112.701(8)°, U = 3243.9(7)ų, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono‐capped trigonal prisms with d(Cd‐O) = 2.271‐2.583Å and d(Cd‐N) = 2.309, 2.390Å. The [Cd(phen)] moieties are bridged by adipato ligands to generate {[Cd(phen)](C₆H₈O₄)_3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)Å, b = 10.230(3)Å, c = 11.243(1)Å, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)ų, Z = 2) consists of {[Cd(phen)](C₇H₁₀O₄)_3/3} chains and hydrogen bonded H₂O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd‐O) = 2.213—2.721Å and d(Cd‐N) = 2.329, 2.372Å. Through interchain π—π stacking interactions, the {[Cd(phen)](C₇H₁₀O₄)_3/3} chains resulting from [Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H₂O molecules are sandwiched.     

Zur Kristallstruktur von SrZn(OH)4 · H2O

Crystal Structure of SrZn(OH)₄ · H₂O Colorless crystals of SrZn(OH)₄ · H₂O are obtained by electrochemical oxidation of Zn in a zinc/iron pair in an aqueous ammonia solution saturated with strontium hydroxide. The X-ray crystal structure determination was now successful including all hydrogen positions: P1 , Z = 2, a = 6.244(1) Å, b = 6.3000(8) Å, c = 7.701(1) Å, α = 90.59(1)°, β = 112.56(2)°, γ = 108.66(2)°, N(F ≥ 3σF) = 1967, N(Var.) = 84, R/R_w = 0.020/0.024. In SrZn(OH)₄ · H₂O Zn²⁺ is tetrahedrally coordinated by four OH^? -ions while Sr²⁺ has 6 OH^? and one H₂O as neighbours. The polyhedra around Sr²⁺ are connected to chains which are linked three-dimensionally by isolated tetrahedra [Zn(OH)₄]. Hydrogen bonds between H₂O as donor and OH^? are characterized by raman spectroscopy.     

Rb2Co3(H2O)2[B4P6O24(OH)2]: Ein Borophosphat mit ‐Tetraeder‐Anionenteilstruktur und Oktaeder‐Trimeren (CoO12(H2O)2)

Rb₂Co₃(H₂O)₂[B₄P₆O₂₄(OH)₂]: A Borophosphate with ‐Tetrahedral Anionic Partial Structure and Trimers of Octahedra (Co O₁₂(H₂O)₂) Rb₂Co₃(H₂O)₂[B₄P₆O₂₄(OH)₂] is formed under mild hydrothermal conditions (T = 165 °C) from mixtures of RbOH_(aq), CoCl₂, H₃BO₃, and H₃PO₄ (molar ratio 1 : 1 : 1 : 2). The crystal structure (orthorhombic system) was solved by X‐ray single crystal methods (space group Pbca, No. 61; R‐values (all data): R1 = 0.0699, wR2 = 0.0878): a = 950.1(1) pm, b = 1227.2(2) pm, c = 2007.4(2) pm; Z = 4. The anionic partial structure consists of tetrahedral [B₄P₆O₂₄(OH)₂^8–] layers, which contain three‐ and nine‐membered rings. Co^II is octahedrally coordinated by oxygen and oxygen and H₂O ligands, respectively (coordination octahedra CoO₆ and CoO₄(H₂O)₂). Three adjacent coordination octahedra are condensed via common edges to form trimeric units (CoO₁₂(H₂O)₂). The oxidation state +2 of cobalt was confirmed by magnetic measurements. The octahedral trimers are quasi‐isolated. No long‐range magnetic ordering occurs down to 2 K. Rb⁺ is disordered over three crystallographically independent sites within channels of the structure running parallel [010]; the coordination sphere of Rb⁺ is formed by nine oxygen species of the tetrahedral layers, one OH group and one H₂O molecule.     

Kristallstruktur und schwingungsspektrometrische Daten von cis-Na2[Pd(SO3)2en] · 4 H2O

Crystal Structure and Data from Vibrational Spectra of cis-Na₂[Pd(SO₃)₂en] · 4 H₂O The compound cis-Na₂[Pd(SO₃)₂en] · 4 H₂O (en = 1,2-diaminoethane) crystallizes in the orthorhombic space group Pnma with a = 623.7(2), = 1070.9(10), c = 1989.5(30) pm and Z = 4. In the [Pd(SO₃)₂en]^2? anions the trans-influence of the sulfite ligands manifests itself in long Pd? N bonds with short Pd? S distances. A set of Na⁺ ions is present in face-sharing octahedra Na(OH₂)₆⁺, forming rods [Na(OH₂)_6/2]⁺ parallel to [100]. A second set of Na⁺ ions is surrounded by two H₂O molecules and four O atoms from SO₃ ligands of two anions to form likewise octahedra with face-sharing, yielding rods [Na(OH₂)_2/2{(OSO₂)₂Pd en}_2/2]^? parallel to [100]. Comparatively low v(Pd? N)-frequencies reveal the trans-influence of the sulfite ligands also in the vibrational spectra.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

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.     

Mehrkernige Kobaltkomplexe. III. Über meso-[(en)2Co(OH)2Co(en)2] (NO3)4

Polynuclear Cobalt Complexes. III. On meso-[(en)₂Co(OH)₂Co(en)₂] (NO₃)₄ The structure of the title compound has been determined by X-ray analysis and refined to R = 0,060. The crystals are monoclinic, space group very probably C2/m, with cell dimensions a = 16,113(3), b = 10,946(2), c = 7,193(2) Å, β = 113,22(2)° and Z = 2. The configuration of the cation is ΔΛ IR. and UV./VIS. spectroscopic data are given.     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Die Kristallstruktur von H3Co(CN)6

The crystal structure of the hexagonal H₃Co(CN)₆ (a = 6.43 Å, c = 5.70 Å, Z = 1) has been determined by X-ray powder methods. The space group is D (at least pseudo), the cobalt atoms being in (0, 0, 0). Structure factor calculations lead to a final R-value of 13.2%, based on F²-sums of coinciding reflections. The carbon and nitrogen atoms are located at the vertices of a slightly distorted octahedron around the cobalt atom; the angle Co? C? N is 177°. The interatomic distances are: Co? C = 1.89 Å, Co? N = 2,98 Å, C? N = 1.09 Å. The pseudo-octahedral units of Co(CN)₆ are linked together by N? H? N bridges. Infrared spectra show that the most probable linkage is the one with a N? H? N-bond length of 2.7 Å.     

Die Kristallstrukturen von Tl2AgI3 und NaAgI2 · 3 H2O

Crystal Structure Investigations of Tl₂AgI₃ und NaAgI₂ · 3 H₂O Tl₂AgI₃ was synthesized by the reaction of TlI with AgI in aqueous HI (25%) in a pressure vessel. The compound crystallizes in the rhombohedral space group R3 ; a = 1044,3(2); c = 1993,5(3)pm; Z = 9. The crystal structure contains trinuclear anions [Ag₃I₈]^5? and [ITl₆]⁵⁺ octahedra. The anions are composed of two AgI₄-tetrahedra which are connected to an AgI₆ octahedron via common faces. Single crystals of NaAgI₂ · 3 H₂O were formed by reaction of NaI with AgI in aqueous solution. The compound crystallizes in the orthorhombic space group Pbca with lattice parameters a = 711,2(2); b = 939,8(3); c = 2462,2(4) pm; Z = 8. The crystal structure is built up by polymeric layers [AgI_3/3I_½^1/2?] of corner sharing AgI₄ tetrahedra (GaOCl type) and [Na(H₂O)_4/2(H₂O)I_½^1/2+] octahedra chains.     

Ba5AlIr2O11: Eine neue Verbindung mit Iridium(IV,V)

Ba₅AlIr₂O₁₁: A New Compound with Iridium(IV, V) The hitherto unknown compound Ba₅AlIr₂O₁₁ was prepared and investigated by X-ray technique (space group D–Pnma, a = 18.8360; b = 5.7887; c = 11.1030 Å; Z = 4). Iridium has an octahedral coordination in each case two octahedra are connected by a plane. These double octahedra form with corner connected AlO₄ tetrahedra [Ir₂AlO₁₁]^10? units. Ba₅AlIr₂O₁₁ is not related to the perovskite type compounds.