Synthesis and Characterization of the Synthetic Minerals Villyaellenite and Sarkinite,Mn5(AsO4)2(HAsO4)2 · 4H2O and Mn2(AsO4)(OH)

Using hydrothermal methods, two manganese arsenates have been synthesized and characterized by single crystal X‐ray diffraction. The products Mn₅(AsO₄)₂(HAsO₄)₂ ?4H₂O ( 1 ) and Mn₂AsO₄(OH) ( 2 ), the Mn end‐members of the minerals villyaellenite and sarkinite, respectively, have been obtained (crystal data 1 : monoclinic, C2/c, a = 18.109(4), b = 9.332(2), c = 9.809(2) Å, β = 96.172(4)?, Z = 4; 2 : monoclinic, P2₁/c, a = 10.219(2), b = 13.613(2), c = 12.780(2) Å, β = 108.834(2)?, Z = 16). In both compounds a three‐dimensional framework of edge‐sharing MnO polyhedra is observed. Based on the availability of the all Mn2containing form of villyaellenite ( 1 ), the ordering scheme of the impurity cations of the natural samples could be confirmed. Magnetic susceptibility measurements of 1 indicate the presence of high‐spin Mn²⁺ ions. The comparison of the data on sarkinite ( 2 ) with the data obtained from the natural sample indicates that the mineral has either a very high Mn content, or an absence of impurity cation ordering.     

IR- und Raman-Spektren der isotypen Iodathydrate M(IO3)2 · 4 H2O (M = Mg,Ni, Co); Kristallstruktur von Co(IO3)2 · 4 H2O

Infrared and Raman Spectroscopy of the Isostructural Iodate Hydrates M(IO₃)₂ · 4 H₂O (M = Mg, Ni, Co)-Crystal Structure of Cobalt Iodate Tetrahydrate The iodate tetrahydrates Mg(IO₃)₂ · 4 H₂O, β-Ni(IO₃)₂ · 4 H₂O, Co(IO₃)₂ · 4 H₂O and their deuterated specimens were studied by X-ray, infrared and Raman spectroscopic methods. The title compounds are isostructural crystallising in the monoclinic space group P2₁/c (Z = 2). The crystal structure of Co(IO₃)₂ · 4 H₂O (a = 836.8(5), b = 656.2(3), c = 850.2(5) pm and β = 100.12(5)°) has been refined by single-crystal X-ray methods (R_obs = 3.08%, 693 unique reflections I₀ > 2σ(I)). Isolated Co(IO₃)₂(H₂O)₄ octahedra form layers parallel (100). Within these layers, the two crystallographically different hydrate water molecules form nearly linear hydrogen bonds to adjacent IO₃^– ions (ν_OD of matrix isolated HDO of Co(IO₃)₂ · 4 H₂O (isotopically diluted samples) 2443 (H3), 2430 (H2), and 2379 cm^–1 (H1 and H4), –180 °C). Intramolecular O–H and intermolecular H…O distances were derived from the novel ν_OD vs. r_OH and the traditional ν_OD vs. r_H…O correlation curves, respectively. The internal modes of the iodate ions of the title compounds are discussed with respect to their coupling with the librations of the hydrate H₂O molecules, the distortion of the IO₃^– ions, and the influence of the lattice potential.     

Zinkiodate – Schwingungsspektren (IR,Raman) und Kristallstruktur von Zn(IO3)2 · 2 H2O

Zinc Iodates – Infrared and Raman Spectra, Crystal Structure of Zn(IO₃)₂ · 2 H₂O The zinc iodates Zn(IO₃)₂ · 2 H₂O and Zn(IO₃)₂ as well as α‐Co(IO₃)₂ · 2 H₂O were studied by X‐ray, IR‐ and Raman spectroscopic methods. The crystal structure of the dihydrate, which is isostructural with the respective cobalt compound, was determined by X‐ray single‐crystal studies (space group P1, Z = 2, a = 490,60(4), b = 667,31(5), c = 1088,85(9) pm, α = 98,855(6), β = 91,119(7), and γ = 92,841(6)°, R1 = 2,55%, 2639 unique reflections I > 2σ(I)). Transconfigurated Zn(IO₃)₄(H₂O)₂ octahedra are threedimensionally connected via common IO₃^– ions parallel to [001] and hydrogen bonds parallel to [100] and [010], respectively. Anhydrous Zn(IO₃)₂ crystallizes in space group P2₁ (Z = 2) with a = 548,9(2), b = 512,4(1), c = 941,8(2) pm, and β = 90,5(3)°. The structure of Zn(IO₃)₂ is a monoclinically distorted variant of the structures of β‐Ni(IO₃)₂ (space group P6₃) and Co(IO₃)₂ (P3). The O–H … O–IO₂ hydrogen bonds of the crystallographically different H₂O molecules of the dihydrates (ν_OD (OD stretching modes of isotopically dilute samples) 2430, 2415, 2333 and 2300 cm^–1, Zn(IO₃)₂ · 2 H₂O, 90 K) are examples to the matter of fact that O … O distances are only a bad measure for the strength of hydrogen bonds. The infrared and Raman spectra as well as a group theoretical treatment are presented and discussed with respect to mutual exclusion principle (possible space groups), the strength of the hydrogen bonds and the distortion of the IO₃^– ions at the C₁ lattice sites.     

Competitive Coordination of the Uranyl Ion by Perchlorate and Water ‐ The Crystal Structures of UO2(ClO4)2·3H2O and UO2(ClO4)2·5H2O and a Redetermination of UO2(ClO4)2·7H2O

By slow evaporation of solutions containing UO₂(ClO₄)₂ and an excess of HClO₄, single crystals of [UO₂(ClO₄)₂(H₂O)₃] ( 1 ) and [UO₂(H₂O)₅](ClO₄)₂ ( 2 ) were obtained and their structures were determined. From similar solutions prepared from stoichiometric amounts of UO₃ and perchloric acid, crystals of [UO₂(H₂O)₅](ClO₄)₂·2H₂O ( 3 ) were obtained. The trihydrate (monoclinic, P2₁/c, a = 545.44(1) pm, b = 1811.09(5) pm, c = 1032.46(2) pm, β = 90.016(1)°) consists of uranyl ions, which are coordinated by two monodentate perchlorate ions and three water molecules. The pentahydrate (monoclinic, P2₁/n, a = 529.35(2) pm, b = 1645.43(6) pm, c = 1480.18(6) pm, β = 99.847(1)°) contains uranyl ions coordinated by five water molecules. The same structural unit can be found in the heptahydrate, whose structure was re‐determined (orthorhombic, Pbcn, a = 920.9(3) pm, b = 1067.9(3) pm, c = 1445.7(3) pm). In this structure, two molecules of water of crystallization are present.     

[(C2H5)3NH]2Sn3Se7 · 0,25 H2O und [(C3H7)2NH2]4Sn4Se10 · 4 H2O

Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C₂H₅)₃NH]₂Sn₃Se₇ · 0,25 H₂O and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O The new selenidostannate hydrates [(C₂H₅)₃NH]₂Sn₃Se₇ · 0.25 H₂O ( I ) and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P2₁/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se₃Se₇]^2– units and nets from trigonal SnSe₅ bipyramids. II crystallizes at ambient temperature in the tetragonal space group I4₁/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn₄Se₁₀]^4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.     

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 .     

Das Chloridnitrat PrCl2(NO3) · 5 H2O mit kationischen und anionischen Komplexen gemäß [PrCl2(H2O)6][PrCl2(NO3)2(H2O)4]

The Chloride Nitrate PrCl₂(NO₃) · 5 H₂O with Cationic and Anionic Complexes according to [PrCl₂(H₂O)₆][PrCl₂(NO₃)₂(H₂O)₄] Green single crystals of PrCl₂(NO₃) · 5 H₂O have been obtained from an aqueous solution of PrCl₃ and Pr(NO₃)₃. The crystal structure [monoclinic, P2/c, Z = 4, a = 1228.8(3), b = 648.4(1), c = 1266.0(4) pm, β = 91.91(3)°] contains cationic and anionic Pr³⁺ complexes according to [PrCl₂(H₂O)₆][PrCl₂(NO₃)₂(H₂O)₄]. Both nitrate groups of the anionic complex act as bidentate chelating ligands. Hydrogen bonds are observed with water molecules as donors and chlorine as well as oxygen atoms as acceptors.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

Synthesis and Crystal Structure of a Novel Dinuclear Copper(II) Complex, [Cu2(phen)2(H2O)2(OH)2](HCO3)2 · 6 H2O with phen = 1,10‐phenanthroline

Dark blue plate‐like crystals of [Cu₂(phen)₂ · (H₂O)₂(OH)₂](HCO₃)₂ · 6 H₂O were obtained from a CH₃OH–H₂O solution containing CuCl₂, 1,10‐phenanthroline (phen), sebacic acid and Na₂CO₃. The crystal structure (triclinic, P 1 (no. 2), a = 8.118(1), b = 9.624(1), c = 10.536(1) Å, α = 81.35(1)°, β = 88.51(1)°, γ = 75.77(1)°, Z = 1, R = 0.0332, wR² = 0.0981 for 4163 observed reflections (F ≥ 2σ(F ) out of 4595 unique reflections) consists of divalent [Cu₂(phen)₂(H₂O)₂(OH)₂]²⁺ complex cations, anionic (HCO₃)₂^2– dimers and H₂O molecules. The divalent complex cations (d(Cu…Cu) = 2.905(1) Å) are centered at inversion centers. The Cu atoms are fivefold square‐pyramidally coordinated by two nitrogen and three oxygen atoms from one bidentate chelating phen ligand, two bridging hydroxide groups and one axial water molecule (d(Cu–N)phen = 2.021(2), 2.024(2) Å; d(Cu–O)_OH = 1.941(1), 1.949(1) Å; d(Cu–O)_H2O = 2.254(2) Å). The divalent complex cations are stacked to form 2 D layers parallel (001) with 1 D π‐π stacking interactions along [100] via the terminal phen rings. The dimeric (HCO₃)₂^2– anions and the hydrogen bonded H₂O molecules are sandwiched between the 2 D layers.     

Ab‐initio‐Berechnung des Tetracarbonatoscandat‐Ions in Na5[Sc(CO3)4] · 2 H2O. Einkristallstrukturbestimmung,Schwingungsspektren und thermischer Abbau

Ab Initio Calculation of the Tetracarbonatoscandate‐Ion in Na₅[Sc(CO₃)₄] · 2 H₂O. Single Crystal Structure Determination, Vibrational Spectra, and Thermal Decomposition Normal modes of the tetracarbonatoscandate‐ion, [Sc(CO₃)₄]^5–, were determined by ab initio calculations and were compared with experimental data of Infrared‐ and Raman‐spectra of the compound Na₅[Sc(CO₃)₄] · 2 H₂O. A necessary redetermination of the structure with single crystal x‐ray diffraction data (tetragonal, P42₁c (Nr. 114), Z = 2, a = 746,37(4) pm, c = 1157,0(2) pm, V_EZ = 644,5(1) 10⁶ pm³) allows the discussion of existing hydrogen bonds. Determination of the thermal behaviour indicates a two‐stage decomposition reaction, but no corresponding intermediate could be isolated.     

Orthotelluric Acid as Substitute for Crystal‐Water: Syntheses and Crystal Structure of the Co‐crystallate [Te(OH)6 · 2 Adenine · 4 H2O] and the Disodium Ditellurate(VI) Aggregate {[Te2O2(OH)6(ONa)2]2[NaOH · 12.5 H2O]}

Supramolecular aspects on Te(OH)₆ as substitute for crystal‐water in adenine hydrate complexes and the first disodium ditellurate(VI) are reported. The co‐crystallate [Te(OH)₆ · 2 adenine · 4 H₂O] ( 1 ) has been prepared in 41% yield from the 1 : 1 mixing of Te(OH)₆ with the nitrogenous base adenine. The adduct of infinite stacks of adenine molecules, Te(OH)₆ and water not only proves that Te(OH)₆ mimicks the role of water in the related hydrate adenine · 3 H₂O but also shows that the inclusion of Te(OH)₆ raises the number of HO–H and N–HO contacts and therefore increases the distance between the adenine rings to 3.31 Å in 1 in comparison to that in adenine trihydrate (3.22 Å). Additionally, the disodium ditellurate(VI) aggregate {[Te₂(O)₂(OH)₆(ONa)₂]₂ [NaOH · 12.5 H₂O]} ( 2 ) resulted from the reaction of 1 with 2 molar equivalents of aqueous NaOH. Dinuclear 2 represents the first X‐ray diffraction characterized example of a sodium tellurate(VI) constructed from [Te₂O₄(OH)₆]^2– dianions.     

Kristallstruktur,Infrarot‐ und Ramanspektren von Kupfertrihydrogenperiodatmonohydrat,CuH3IO6 · H2O

Crystal Structure, Infrared and Raman Spectra of Copper Trihydrogenperiodate Monohydrate, CuH₃IO₆ · H₂O The hitherto unknown compound CuH₃IO₆ · H₂O was studied by X‐ray, IR‐ and Raman spectroscopic methods. The crystal structure was determined by X‐ray single‐crystal studies (space group P2₁2₁2₁, Z = 4, a = 532.60(10), b = 624.00(10), c = 1570.8(3) pm, R1 = 1.85%, 1559 unique reflections (I > 2σ(I))). Isolated, meridionally configurated H₃IO₆^2– ions are coordinated to the copper ions forming double‐ropes in [100]. These ropes are connected in [010] and [001] by hydrogen bonds. The copper ions possess a square pyramidal co‐ordination with the hydrate H₂O on top. The infrared and Raman spectra as well as group theoretical treatment are presented and discussed with respect to the strength of the hydrogen bonds and the co‐ordination of the CuO₅₍₊₁₎ polyhedra and the H₃IO₆^2– ions at the C₁ lattice sites. The hydrogen bonds of the H₂O molecules and H₃IO₆^2– ions (HO–H…O–IO₅H₃ and H₂IO₅O–H…O–IO₅H₃) greatly differ in strength, as shown from both the respective O…O distances: 282.6 and 298.6 pm (H₂O), and 258.8, 259.7, and 270.9 pm (H₃IO₆^2–) and the OD stretching modes of isotopically dilute samples: 2498 and 2564 cm^–1 (90 K) (HDO), and 1786, 2024, and 2188 cm^–1 (H₂DIO₆^2–). The IO stretching modes of the H₃IO₆^2– ions (696–788 cm^–1 and 555–658 cm^–1, 295 K) display the different strength of the respective I–O and I–O(H) bonds (r_I–O: 181.1–188.3 pm and 189.2–194.5 pm).     

Bildung und Kristallstruktur von FcCH(t‐Bu)NHCH(Me)CH2OMe · LiI · Et2O

Formation and Crystal Structure of FcCH( t ‐Bu)NHCH(Me)CH₂OMe · LiI · Et₂O The title compound FcCH(t‐Bu)NHCH(Me)CH₂OMe · LiI · Et₂O ( 1 · LiI · Et₂O) was obtained by reaction of FcCH(t‐Bu)N(Li)CH(Me)CH₂OMe with MeI in a molar ratio 1 : 1 in diethylether. The Li atom is substituted by an H atom yielding the secondary amine. The formation of the expected N‐methyl substituted species could not be observed. 1 creates monomeric molecules with four coordinate Li atoms as a result of Li–N and Li–O interactions of the corresponding atoms of the ferrocenyl ligand and a solvent molecule. 1 · LiI · Et₂O: Space group P2₁2₁2₁, Z = 4, lattice dimensions at –60 °C: a = 10.492(2), b = 13.225(2), c = 18.846(3) Å, β = 90°, R₁ = 0.0478, wR₂ = 0.0801.     

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.     

Structure Determination of a Twinned Rb(H2NC10H6SO3) · H2O Crystal and Comparison to Related Alkali Metal Aminonaphthalenesulfonates

Rb(H₂NC₁₀H₆SO₃) · H₂O crystallizes in space group P2₁ with two formula units in the asymmetric unit, the crystal being twinned by a 180° rotation about [1 0 0]. The structure was determined from X‐ray diffraction data, and refined, based on two twin components, to yield a final R value of 0.0557 for 2754 reflections. The structure consists of alternating layers of aminonaphthalenesulfonate and rubidium ions. There are two distinct rubidium environments, the metal ions linked by the sulfonate groups and bridging water molecules into an infinite sheet. The sulfonate groups are bidentate, monodentate and bridging, all oxygen atoms being bound to at least one metal. The amino groups do not participate in coordination to the metal. Aromatic moieties from neighboring hydrophilic metallo‐layers interleave to form the hydrophobic layers. There is some similarity to the analogous sodium and potassium structures, however the rubidium compound is distinguished by an infinite cationic layer, rather than columns observed for the other two structures.     

Tetraammonium Diglycinyl‐octamolybdate(VI) Dihydrate, (NH4)4[(NH3CH2CO)2(Mo8O28)] · 2 H2O

The reaction of ammonium heptamolybdate with hydrazine sulfate in an aqueous solution of glycine at room temperature yielded colorless crystals of (NH₄)₄[(NH₃CH₂CO)₂(Mo₈O₂₈)] · 2 H₂O. The crystal is monoclinic, space group C2/c (no. 15), a = 17.234 Å, b = 10.6892 Å, c = 18.598 Å, β = 108.280°, V = 3253.2 ų, Z = 4. The crystal structure contains ammonium cations and isolated octamolybdate(4–) anions, [(NH₃CH₂CO)₂(Mo₈O₂₈)]^4–, with two zwitterionic glycine molecules as ligands.     

Carbonat‐Hydrate der schweren Alkalimetalle: Darstellung und Struktur von Rb2CO3 · 1,5 H2O und Cs2CO3 · 3 H2O

Carbonate Hydrates of the Heavy Alkali Metals: Preparation and Structure of Rb₂CO₃ · 1.5 H₂O und Cs₂CO₃ · 3 H₂O Rb₂CO₃ · 1.5 H₂O and Cs₂CO₃ · 3 H₂O were prepared from aqueous solution and by means of the reaction of dialkylcarbonates with RbOH and CsOH resp. in hydrous alcoholes. Based on four‐circle diffractometer data, the crystal structures were determined (Rb₂CO₃ · 1.5 H₂O: C2/c (no. 15), Z = 8, a = 1237.7(2) pm, b = 1385.94(7) pm, c = 747.7(4) pm, β = 120.133(8)°, V_EZ = 1109.3(6) · 10⁶ pm³; Cs₂CO₃ · 3 H₂O: P2/c (no. 13), Z = 2, a = 654.5(2) pm, b = 679.06(6) pm, c = 886.4(2) pm, β = 90.708(14)°, V_EZ = 393.9(2) · 10⁶ pm³). Rb₂CO₃ · 1.5 H₂O is isostructural with K₂CO₃ · 1.5 H₂O. In case of Cs₂CO₃ · 3 H₂O no comparable structure is known. Both structures show [(CO₃^2–)(H₂O)]‐chains, being connected via additional H₂O forming columns (Rb₂CO₃ · 1.5 H₂O) and layers (Cs₂CO₃ · 3 H₂O), respectively.     

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).     

Synthese,Kristallstruktur und Eigenschaften der käfigartigen,sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Syntheses, Crystal Structure, and Properties of the Cage‐like, Hexaacidic P₁₂S₁₂N₈(NH)₆ · 14 H₂O and its Salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O, (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O, and K₆[P₁₂S₁₂N₁₄] · 8 H₂O The cage‐like acid P₁₂S₁₂N₈(NH)₆ · 14 H₂O was obtained by the reaction of KSCN with P₄S₁₀ via the formation of K₆[P₁₂S₁₂N₁₄] · 8 H₂O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O and (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O were synthesized. According to X‐ray single‐crystal structure analyses the compounds are built up by isosteric P–N cages [P₁₂S₁₂N^[3]₈N^[2]₆]^6–. Each of them is made up of twelve P₃N₃ rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P₁₂S₁₂N₈(NH)₆ · 14 H₂O: P1, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, α = 80.186(4), β = 60.391(4), γ = 60.605(4)°, Z = 1; Li₆[P₁₂S₁₂N₁₄] · 26 H₂O: Fm3, a = 1797.4(1) pm, Z = 4; (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O: P6₃, a = 1153.2(1), c = 2035.6(2) pm, Z = 2; K₆[P₁₂S₁₂N₁₄] · 8 H₂O: R3c, a = 1142.37(5), c = 6009.6(3) pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high‐mobility and are located between the cages.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.