Contributions on thermal behaviour and crystal chemistry of anhydrous phosphates. XIX. Tri-chromium(II)-bis-phosphate Cr3(PO4)2 (≙ Cr6(PO4)4) – A transition metal(II)-orthophosphate with new structure type

Deep blue-violet single crystals of hitherto unknown chromous orthophosphate have been obtained reducing CrPO₄ by elemental Cr at temperatures above 1050°C in evacuated silica ampoules (NH₄I or I₂ as mineraliser). The complex structure of Cr₃(PO₄)₂ (P2₁2₁2₁, Z = 8, a = 8.4849(10) Å, b = 10.3317(10) Å, c = 14.206(2) Å) contains six crystallographically independent Cr²⁺ per unit cell. Five of them are coordinated by four oxygen atoms which form a distorted (roof shaped) square plane as first coordination sphere at interatomic distances 1.96 Å ? d(Cr? O) ? 2.15 Å. Their coordination is completed by additional oxygen atoms (2 or 3) at distances 2.32 Å ? d(Cr? O) ? 3.21 Å. The sixth Cr²⁺ shows six-fold octahedral coordination with strong radial distortion (d(Cr? O): 1.97, 2.04, 2.15, 2.28, 2.29, 2.53 Å). The four different [PO₄] groups exhibit only minor deviations from ideal tetrahedral geometry (1.51 Å ? d(P? O) ? 1.57 Å, 104.3° ? ∠(O? P? O) ? 114.4°). An unusually low magnetic moment μ_exp = 4.28(2) μ_B (θ_P = ?54.8(5) K) has been observed for Cr²⁺.     

Mercury(II) polyphosphate,Hg(PO3)2

Single crystals of mercury(II) polyphosphate, Hg(PO₃)₂, were prepared from HgO in an acidic polyphosphate melt. The structure is isotypic with α‐Cd(PO₃)₂ and comprises infinite polyphosphate chains with a period of four phosphate units. Chains of the form ¹_∞[PO₃^?] are linked by Hg²⁺ to form a three‐dimensional network. The Hg atom is located at the centre of a distorted octahedron of O atoms with distances 2.173 (5) < (Hg—O)_mean < 2.503 (6) Å. The [HgO₆] polyhedra form zigzag‐like chains of the form ¹_∞[HgO₂O_4/2] parallel to the c axis.     

Synthèse et structure d'une nouvelle variété de phosphate d'indium: InPO4-β

Synthesis and structure of a new variety of indium phosphate β-InPO₄. A new high temperature allotropie form of indium phosphate, β-InPO₄, has been obtained through quenching of an amorphous InPO₄ phase heated for one hour at 1 300 °C. The two precursor amorphous phases, prepared according to two different soft chemistry procedures, lead to the same β derivative. The β-InPO₄ structure is the same as the high-temperature varieties presented by MgSO₄ and CoSO₄, with an orthorhombic cell and the parameters a = 8.8800(1) Å, b = 6.8989(1) Å, c = 4.8082(1) Å, V= 294.56(1) ų and Z = 4. The space group is Pnma. The structure was refined using the Rietveld method (R_p = 0,04l, R_wp = 0,056 et χ² = 2,63). It is built from [InO₆] octahedra sharing edges to constitute [InO₄] chains running in one direction and linked by [PO₄] tetrahedra. The α and β structures are compared and discussed.     

Beiträge zur Kristallchemie und zum thermischen Verhalten von wasserfreien Phosphaten. XXXXII Die ersten Iridiumphosphate

The First Iridiumphosphates Two polymorphs of iridium(III)‐metaphosphate Ir(PO₃)₃ and an iridium(IV)‐silicophosphate (Ir_1?xSi_x)₃[Si₂O(PO₄)₆] (x ～ 0.5) were synthesized and their crystal structures determined from single‐crystal x‐ray data. Pale pink needles of triclinic Ir(PO₃)₃ (Ru(PO₃)₃ structure type, (No. 2), Z = 2, a = 6.9574(6) Å, b = 10.3628(9) Å, c = 5.0288(4) Å, α = 92.28(1)°, β = 92.80(1)°, γ = 98.60(1)°, 1574 independent reflections, 122 parameters, R₁ = 0.028, wR₂ = 0.061) were grown from a metaphosphoric acid melt. Pale pink prisms of C‐type Ir(PO₃)₃ (C‐Al(PO₃)₃ structure type, Cc (No. 14), Z = 12, a = 13.103(2) Å, b = 19.183(1) Å, c = 9.354(1) Å, β = 127.19(1)°, 4254 independent reflections, 354 parameter, R₁ = 0.024, wR₂ = 0.062) were obtained by chemical vapour transport (900 °C → 800 °C, addition of IrCl₃·xH₂O). Both metaphosphates are built of [Ir^IIIO₆] octahedra and infinite chains. The latter have a translation period of three phosphate tetrahedra in the triclinic modification and six in the monoclinic. 1D and double‐quantum filtered 2D ³¹P‐MAS‐NMR spectra of C‐type Ir(PO₃)₃ confirm the chain structure and reveal a chemical shift range between ?4,8 and ?30,9 ppm for the 9 crystallographically independent, however chemically similar phosphate groups. Pale orange crystals of (Ir_1?xSi_x)₃[Si₂O(PO₄)₆] (Si₃[Si₂O(PO₄)₆] structure type, (No. 148), Z = 3, a = 7.8819(8) Å, c = 24.476(4) Å, 1086 independent reflections, 56 parameters, R₁ = 0.061, wR₂ = 0.190) occurred in chemical vapour transport experiments aiming at the crystallization of C‐Ir(PO₃)₃. The crystal structure of the silicophosphate consists of isolated [Ir^IVO₆] octahedra and [Si₂O(PO₄)₆]^12? heteropolyanions.     

Synthesis and X-Ray Structure of New Copper(II) Nitrates: Cu(NO3)2 · H2O and β-modification of Cu(NO3)2

Blue crystals of a Cu(NO₃)₂ · H₂O were synthesized by interaction of CuO with boiling 100% HNO₃. Stable β-Cu(NO₃)₂ modification was obtained by the sublimation of copper(II) nitrate in evacuated ampoule over the 150→100°C temperature gradient for 24 hr. According to X-Ray single crystal analysis Cu(NO₃)₂ · H₂O is monoclinic with a = 6.377(1), b = 8.548(1), c = 9.769(1) Å, β = 100.41(1)°, Z = 4, and space group P2₁/c. β-modification Cu(NO₃)₂ is orthorhombic with a = 14.161(5), b = 7.516(3), c = 12.886(2) Å, Z = 12, and space group Pbcn. In the both structures Cu atoms are square coordinated by 4 O atoms at the distances ranging from 1.92 to 2.02 Å. In each structure there are also additional Cu? O bonds with the distance of 2.33 or 2.35 Å and some weaker ones with the distances in the range of 2.65–2.72 Å. In the Cu(NO₃)₂ · H₂O structure the [CuO₄] squares are connected by the bridging NO₃ groups into zigzag chains, which are linked into layers by the longer Cu? O bonds. In the β-Cu(NO₃)₂ structure the [CuO₄] fragments of two types are joined by the bridging NO₃ groups in a three-dimensional framework. Some correlations were found between N? O distances and coordination functions of O atoms.     

Die Kristallstruktur von Si5O[PO4]6

The crystal structure of Si₅O[PO₄]₆ has been determined and refined by least-squares, using three-dimensional X-raydata fromWeissenberg photographs: space group R 3;a=7.86₉ andc=24.13₈ Å;Z=3; 418 independent reflections;R=6.0%. The crystal structure consists of isolated [SiO₆] octahedra and [Si₂O₇] groups which are linked by [PO₄] tetrahedra forming a three-dimensional network. The average interatomic distances are: Si[6]?O=1.76₈, Si[4]?O=1.60₇ and P?O=1.52_i Å. The compound is isotypic with Ge₅O[PO₄]₆.     

Ein neues Kaliumhydrogensulfat,K(H3O)(HSO4)2 — Synthese und Struktur

A New Potassium Hydrogensulfate, K(H₃O)(HSO₄)₂ — Synthesis and Structure Single crystals of the new compound K(H₃O)(SO₄)₂ are synthesized from the system potassium sulfate/sulfuric acid. The up to day not described compound crystallizes in the monoclinic space group P2₁/c with the unit cell parameters a = 7.203(1) b = 13.585(2) and c = 8.434(1) Å, β = 105.54(1)°, V = 795.1 ų, Z = 4 and D_x = 2.107 g · cm^?3. There are two crystallographically different tetrahedral SO₃(OH) anions. The first kind S1 tetrahedra forms dimers, whereas the second kind S2 forms infinite chains bonded via hydrogen bridges. The S1 dimers are linked to the S2 chains via oxonium ions (hydrogen bonds). Potassium is coordinated by 8 oxygen atoms which belong to four different SO₃(OH) tetrahedra. These potassium oxygen polyhedra are connected by common edges forming chains running parallel z.     

Crystal structure of [ethylenediamine-<Emphasis Type="Italic">N,N</Emphasis>′-di(3-propionato)copper(II)]-<Emphasis Type="Italic">tris</Emphasis>[dichloromercury(II)] [Cu(Eddp)·(HgCl<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>n</Subscript>

Crystals of [Cu(Eddp)·(HgCl₂)₃]_n (monoclinic, a = 9.7547(7) Å, b = 18.3716(12) Å, c = 11.7811(9) Å, β = 94.828(9)°, Z = 4, space group P2₁/n) are made of infinite sheets involving dimeric complexes [Cu₂(Eddp)₂] interacting with quasi-molecules of HgCl₂ (Hg-Cl 2.29-2.36 Å). In the dimers, copper atoms are squarely surrounded by two N atoms and two O atoms of the ethylendiamine-N,N′-di(3-propionate) anion, and atom from a neighboring Eddp ion in the apical position; the second apical position is occupied by a Cl atom of one of HgCl₂ molecules. Weak Hg-Cl interactions (2.98-3.07 Å) join the molecules of HgCl₂ in almost planar centrosymmetrical Hg₆Cl₁₂ hexamers, and further (Hg-Cl 3.168(3) Å, 3.250(2) Å) in infinite chains of the hexamers. Finally, the dimeric copper complexes are linked to six Hg atoms of four adjacent hexamers by virtue of their oxygen atoms (Hg-O 2.322(8), 2.609(6) Å, 2.730(5) Å).     

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.     

Synthesis and crystal structure of KBi(C6H4O7) · 3.5H2O

A novel compound, KBi(C₆H₄O₇) · 3.5H₂O (I), has been synthesized in the Bi(NO₃)₂-K₃(HCit) system (HCit^3? is an anion of citric acid C₆H₈O₇) at a component ratio (n) of 8 in a water-glycerol mixture, and its crystal structure has been determined. The crystals are unstable in air. The crystals are triclinic: a = 7.462 Å, b = 10.064 Å, c = 17.582 Å, α = 100.27°, β = 99.31°, γ = 105.48°, V = 1221.2 ų, Z = 2, space group $P\bar 1$ . In the structure of I, asymmetric binuclear fragments [Bi₂(Cit^4?)₂(H₂O)₂]^2? are linked through inversion centers into polymeric chain anions. Ions K⁺ and crystal water molecules are arranged in channels between the chains. The Bi(1)...Bi(2) distances in the binuclear fragment are 4.62 Å, and the Bi(1)...Bi(1) and Bi(2)...Bi(2) distances between bismuth atoms in the chain are 5.83 and 5.95 Å, respectively. The chains are linked through bridging oxygen atoms of the ligands Cit to form layers. In the centrosymmetric four-membered chelate ring Bi₂O₂ formed through Bi-O(Cit) bonds, the distances Bi(1)-Bi(1) are equal to 4.55 Å, and Bi(1)-O are 2.66 and 2.84 Å. The Bi-O bond lengths in I are in the range 2.12–3.16 Å. The Cit ligands act as hexadentate chelating/bridging ligands.     

Potassium gadolinium polyphosphate,KGd(PO3)4

Potassium gadolinium polyphosphate, KGd(PO₃)₄, was synthesized using the flux method. The atomic arrangement consists of an infinite long‐chain polyphosphate organization. Two types of chains, with a period of eight PO₄ tetrahedra, run along the [101] direction. The Gd atoms have an eightfold coordination, while the K atoms have nine O‐atom neighbours.     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

New open framework in the structure of K3[Cu3FZn2(PO4)4]

K₃[Cu₃FZn₂(PO₄)₄] has been prepared by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray analysis: space group C2/c, a = 37.824(8), b = 9.813(2), c = 16.679(3) Å, β = 92.70(3)°, wR₂ = 0.057, R = 0.0255. An open framework structure is built by [CuO₅] and [CuO₄F] square pyramids, [CuO₄] flattened tetrahedra, [ZnO₄] and [PO₄] tetrahedra with potassium ions in the channels.     

Preparation,Single Crystal Structure Analysis,and Thermal Behaviour of the Acidic Mercury(I) Phosphate (Hg2)2(H2PO4)(PO4)

Yellowish single crystals of acidic mercury(I) phosphate (Hg₂)₂(H₂PO₄)(PO₄) were obtained at 200 °C under hydrothermal conditions in 32% HF from a starting complex of microcrystalline (Hg₂)₂P₂O₇. Refinement of single crystal data converged at a conventional residual R[F² > 2σ(F²)] = 3.8% (C2/c, Z = 8, a = 9.597(2) Å, b = 12.673(2) Å, c = 7.976(1) Å, β = 110.91(1)°, V = 906.2(2) ų, 1426 independent reflections > 2σ out of 4147 reflections, 66 variables). The crystal structure consists of Hg₂²⁺‐dumbbells and discrete phosphate groups H₂PO₄^– and PO₄^3–. The Hg₂²⁺ pairs are built of two crystallographically independent Hg atoms with a distance d(Hg1–Hg2) = 2.5240(6) Å. The oxygen coordination sphere around the mercury atoms is asymmetric with three O atoms for Hg1 and four O atoms for Hg2. The oxygen atoms belong to the different PO₄ tetrahedra, which in case of H₂PO₄‐groups are connected by hydrogen bonding. Upon heating over 230 °C, (Hg₂)₂(H₂PO₄)(PO₄) condenses to (Hg₂)₂P₂O₇, which in turn disproportionates at higher temperatures into Hg₂P₂O₇ and elemental mercury.     

Pentastrontium Tris[tetraoxovanadate(V)] catena‐Monoxocuprate(I), Sr5(VO4)3(CuO) – An Apatite Derivative with Inserted Linear 1Ë[CuO]1– Chains

Sr₅(VO₄)₃(CuO) was prepared via solid state reactions from mixed powders of the metal oxides or carbonates in corundum crucibles in air (1173–1740 K). The compound is transparent and stable in air. The color changes with the preparation temperature from light gray (1173 K) to gray (1740 K). The crystal structure (space group P6₃/m, No. 176; Z = 2; a = 10.126 Å, c = 7.415 Å) is a derivative of the apatite Ca₅(PO₄)₃OH, and is characterized by isolated [VO₄]^3– anions (d(V–O) = 1.710 Å) and infinite linear ^1∞[CuO]^1– chains (d(Cu–O) = 1.854 Å) inserted in the channels parallel to the hexagonal axis. The compound prepared at 1740 K contains vacancies at the copper and oxygen positions of the linear chains (about 10% and 5%, respectively).     

Hydrogensulfate mit fehlgeordneten Wasserstoffatomen – Synthese und Struktur von Li[H(HSO4)2](H2SO4)2 sowie Verfeinerung der Struktur von α-NaHSO4

Hydrogen Sulfates with Disordered Hydrogen Atoms – Synthesis and Structure of Li[H(HSO₄)₂](H₂SO₄)₂ and Refinement of the Structure of α-NaHSO₄ The structure of Li[H(HSO₄)₂](H₂SO₄)₂ has been determined for the first time whereas the structure of α-NaHSO₄ has been refined, so that direct determination of the hydrogen positions was possible. Both compounds crystallize triclinic in the space group P1 with the lattice constants a = 6.708(2), b = 6.995(1), c = 7.114(1) Å, α = 75.53(1), β = 84.09(2) and γ = 87.57(2)° (Z = 4) for α-NaHSO₄ and a = 4.915(1), b = 7.313(1), c = 8.346(2) Å, α = 82.42(3), β = 86.10(3) and γ = 80.93(3)° (Z = 1) for Li[H(HSO₄)₂](H₂SO₄)₂. In both compounds there are disordered hydrogen positions. In the structure of α-NaHSO₄ there are two crystallographically different HSO₄^? tetrahedra and two different coordinated Na atoms. The system of hydrogen bonds can be described by chains in [0–11] direction. The disordering of the H atoms reduces the differences between the S? O and S? OH distances (1.45 and 1.50 Å) while in the ordered HSO₄ unit “regular” bond lengths are observed (1.45 und 1,57 Å). In the structure of Li[H(HSO₄)₂](H₂SO₄)₂ there are two crystallographically different SO₄-tetrahedra. The first one belongs to the [H(HSO₄)₂]^? unit while the second one represents H₂SO₄ molecules. The H atom which is located nearby the symmetry centre and connects two HSO₄ units by a short O…?O distance of 2.44 Å. Li is located on a symmetry centre and is slightly distorted octahedrally coordinated by oxygen atoms of six different SO₄ tetrahedra. The system of hydrogen bonds can be regarded as consisting of double layers parallel to the xy-plane.     

Bis(tetraphenylphosphonium) tris(oxalato‐O,O′)germanate(IV)

The synthesis and structure of the title compound, (C₂₄H₂₀P)₂[Ge(C₂O₄)₃], are reported. The PPh₄⁺ cations in the structure form infinite zigzag chains in which the P?P distances alternate between 6.229 (1) and 7.118 (1) Å, and the P?P?P angle is 131.4 (1) Å. The shorter P?P distance is associated with a sixfold phenyl embrace. However, the longer P?P distance is associated with both phenyl–phenyl interactions and interactions between the cations and a twofold symmetric [Ge(C₂O₄)₃]^2? anion. In the cation–anion interactions, the P?O distance is 4.444 (2) Å, the O?P—C_distal angle is 175.0 (1)° and the shortest H?O distances are 2.74 and 3.09 Å.     

Low‐Dimensional Structural Units in Amine‐Templated Uranyl Oxoselenates(VI): Synthesis and Crystal Structures of [C3H12N2][(UO2)(SeO4)2(H2O)2](H2O), [C5H16N2]2[(UO2)(SeO4)2(H2O)](NO3)2, [C4H12N][(UO2)(SeO4)(NO3)], and [C4H14N2][(UO2)(SeO4)2(H2O)]

The crystals of four amine‐templated uranyl oxoselenates(VI), [C₃H₁₂N₂][(UO₂)(SeO₄)₂(H₂O)₂](H₂O) ( 1 ), [C₅H₁₆N₂]₂[(UO₂)(SeO₄)₂(H₂O)](NO₃)₂ ( 2 ), [C₄H₁₂N][(UO₂)(SeO₄)(NO₃)] ( 3 ), and [C₄H₁₄N₂][(UO₂)(SeO₄)₂(H₂O)] ( 4 ) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amine. The crystal structures of all four compounds have been solved by direct methods from X‐ray diffraction data. The structure of 1 (triclinic, , a = 7.5611(16), b = 7.7650(17), c = 12.925(3) Å, α = 94.605(18), β = 94.405(17), γ = 96.470(17)°, V = 748.8(3) ų, R₁ = 0.029 for 2769 unique observed reflections) is based upon 0D‐units of the composition [(UO₂)₂(SeO₄)₄(H₂O)₄]^4?. These discrete units are composed from two pentagonal [UO₇]^8? bipyramids linked via [SeO₄]^2? tetrahedra and are unknown in structural chemistry of uranium so far. The structure of 2 (monoclinic, C2/c, a = 28.916(5), b = 8.0836(10), c = 11.9856(16) Å, β = 110.909(11)°, V = 2617.1(6) ų, R₁ = 0.035 for 2578 unique observed reflections) contains [(UO₂)(SeO₄)₂(H₂O)]^2? chains of corner‐sharing pentagonal [UO₇]^8? bipyramids and [SeO₄]^2? tetrahedra. The chains run parallel to the c axis and are arranged into layers parallel to (100). In the structure of 3 (monoclinic, C2/m, a = 21.244(5), b = 7.1092(11), c = 8.6581(18) Å, β = 97.693(17)°, V = 1295.8(4) ų, R₁ = 0.027 for 1386 unique observed reflections), pentagonal [UO₇]^8? bipyramids share corners with three [SeO₄]^2? tetrahedra each and an edge with a [NO₃]^? anion to form [(UO₂)(SeO₄)(NO₃)]^? chains parallel to the b axis. In the structure of 4 (triclinic, , a = 6.853(2), b = 10.537(3), c = 10.574(3) Å, α = 99.62(3), β = 94.45(3), γ = 100.52(3)°, V = 735.6(4) ų, R₁ = 0.045 for 2713 unique observed reflections), one symmetrically independent pentagonal [UO₇]^8? bipyramid shares corners with four [SeO₄]^2? tetrahedra to form the [(UO₂)(SeO₄)₂(H₂O)]^2? chains parallel to the a axis. A comparison to related uranyl compounds is given.     

Crystal structures of copper(II) complexes with methyliminodiacetate ions and 1,10-phenanthroline or imidazole [Cu(Phen)H<Subscript>2</Subscript>O][Cu(Mida)<Subscript>2</Subscript>]·2H<Subscript>2</Subscript>O and [Cu(Mida)Im]

Methyliminodiacetic acid (H₂Mida) and imidazole react with copper(II) to form crystals of the square pyramidal complex [Cu(Mida)Im]. One N and two O atoms of the Mida ligand (Cu-N 2.010(1) Å, Cu-O 1.955(1) Å, and 1.978(1) Å) and the imidazole N atom (1.950(1) Å) lie at the base of the pyramid. The carboxyl O atom of the neighboring complex lies at the apical position (2.411(1) Å); in this way the individual complexes are linked into infinite zigzag chains. Substitution of imidazole by 1,10-phenanthroline gave [Cu₂(Mida)₂(Phen)H₂O]·2H₂O crystals with two nonequivalent centrosymmetric octahedral anions [Cu(Mida)₂]^2? of face type (Cu-N 2.023 Å and 2.028(2) Å, Cu-O_ax 2.579 Å and 2.530(2) Å, Cu-O_bas 1.952 Å and 1.936(2) Å). The anions serve as bridges in chains between the [Cu(Phen)H₂O]²⁺ cation fragments to which they are bonded by their axial carboxyl groups. The Cu atom of the cation has a [4+1] environment (with the H₂O molecule lying on the axis of the pyramid, and with two N atoms of the ligand and two O atoms of the anions lying at the base).