Synthesis,Single Crystal Structure Determination and Rietveld Refinement of Cadmium Tetrametaphosphimate Octahydrate Cd2(PO2NH)4·8H2O

Cd₂(PO₂NH)₄ · 8H₂O crystallizes in space group P2₁/c (no. 14), Z = 2, with a = 648.5(2), b = 1070.5(2), c = 1328.7(3) pm and β = 103.11(3) °. The structure, isotypic with M₂(PO₂NH)₄ · 8H₂O (M = Mg, Mn, Co, Ni, Zn), is composed of Cd²⁺ and (PO₂NH)₄^4? ions as well as crystal water molecules. The P₄N₄ rings of the (PO₂NH)₄^4? ions exhibit a slightly distorted chair‐2 conformation, which has been described by torsion angles, displacement asymmetry parameters and puckering parameters. The tetrametaphosphimate anions are connected forming layers. These layers are linked solely by hydrogen bonds, forming a three‐dimensional network.     

Synthesis and Crystal Structure of Lithium Tetrametaphosphimate Tetrahydrate Li4(PO2NH)4 · 4 H2O

Single crystals of Li₄(PO₂NH)₄ · 4 H₂O were obtained by dissolving LiOH and H₄(PO₂NH)₄ · 2 H₂O in water and subsequent precipitation with acetone and ethanol followed by slow evaporation of the solvents. The structure of Li₄(PO₂NH)₄ · 4 H₂O was solved by single‐crystal X‐ray methods ( (No. 2), a = 489.2(2), b = 853.2(2), c = 880.5(2) pm, α = 101.71(3), β = 102.39(3), γ = 94.88(3)°, Z = 1). The structure is composed of LiO₄ tetrahedra and (PO₂NH)₄^4? ions. The P₄N₄ rings of the anions exhibit a slightly distorted chair–1 conformation, which is supported by IR data and has been described by torsion angles, displacement asymmetry parameters and puckering parameters. Via Li⁺ ions and hydrogen bonds, the tetrametaphosphimate anions are connected forming a three‐dimensional network.     

Synthesis and Crystal Structure Determination by X‐Ray Powder Diffraction of Nickel Tetrametaphosphimate Octahydrate Ni2(PO2NH)4 · 8 H2O

Ni₂(PO₂NH)₄ · 8 H₂O is isotypic with M₂(PO₂NH)₄ · 8 H₂O (M = Mg, Mn, Co, Zn) and crystallizes in the space group P2₁/c, Z = 2, with a = 641.25(1), b = 1041.42(1), c = 1278.18(2) pm and β = 104.243(1)°. The structure is composed of Ni²⁺ and (PO₂NH)₄^4? ions as well as crystal water molecules. The P₄N₄ rings of the (PO₂NH)₄^4? ions exhibit a slightly distorted chair–2 conformation, which has been described by torsion angles, displacement asymmetry parameters and puckering parameters. The tetrametaphosphimate anions are connected forming layers. These layers are linked solely by hydrogen bonds, forming a three‐dimensional network.     

Isotype Borophosphate MII(C2H10N2)[B2P3O12(OH)] (MII = Mg,Mn, Fe,Ni, Cu,Zn): Verbindungen mit Tetraeder‐Schichtverbänden

Isotypic Borophosphates M^II(C₂H₁₀N₂)[B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn): Compounds containing Tetrahedral Layers The isotypic compounds M^II(C₂H₁₀N₂) · [B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn) were prepared under hydrothermal conditions (T = 170 °C) from mixtures of the metal chloride (chloride hydrate, resp.), Ethylenediamine, H₃BO₃ and H₃PO₄. The orthorhombic crystal structures (Pbca, No. 61, Z = 8) were determined by X‐ray single crystal methods (Mg(C₂H₁₀N₂)[B₂P₃O₁₂(OH)]: a = 936.81(2) pm, b = 1221.86(3) pm, c = 2089.28(5) pm) and Rietveld‐methods (M^II = Mn: a = 931.91(4) pm, b = 1234.26(4) pm, c = 2129.75(7) pm, Fe: a = 935.1(3) pm, b = 1224.8(3) pm, c = 2088.0(6) pm, Ni: a = 939.99(3) pm, b = 1221.29(3) pm, c = 2074.05(7) pm, Cu: a = 941.38(3) pm, b = 1198.02(3) pm, c = 2110.01(6) pm, Zn: a = 935.06(2) pm, b = 1221.33(2) pm, c = 2094.39(4) pm), respectively. The anionic part of the structure contains tetrahedral layers, consisting of three‐ and nine‐membered rings. The M^II‐ions are in a distorted octahedral or tetragonal‐bipyramidal [4 + 2] (copper) coordination formed by oxygen functions of the tetrahedral layers. The resulting three‐dimensional structure contains channels running along [010]. Protonated Ethylenediamine ions are fixed within the channels by hydrogen bonds.     

Synthesis and Characterization of Three Zinc Phosphonates Based on 5‐Phosphonoisophthalic Acid, (HO2C)2C6H3PO3H2

Three new Zn‐phosphonates based on 5‐phosphonoisophthalic acid, (HO₂C)₂C₆H₃PO₃H₂ (H₄L), [Zn₂(H₂O)(O₂C)₂C₆H₃PO₃] · H₂O ( 1 ), Zn₂(H₂O)₂(O₂C)₂C₆H₃PO₃ ( 2 ), and KZn[H(O₂C)₂C₆H₃PO₃] ( 3 ) have been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction ( 1 : triclinic, , a = 742.49(3) pm, b = 846.37(4) pm, c = 992.84(4) pm, α = 80.936(2)°, β = 81.574(2)°, γ = 73.139(3)°, V = 586.28(4) · 10⁶ pm³, R1 = 0.0583, wR2 = 0.1347 (for I > 2σ(I)); 2 : monoclinic, P2₁/m, a = 464.78(9) pm, b = 1329.2(3) pm, c = 974.5(3) pm, β = 95.80(3)°, V = 599.0(2) · 10⁶ pm³, R1 = 0.0395, wR2 = 0.1086 (for I > 2σ(I)); 3 : monoclinic, P2₁/c, a = 501.9(1) pm, b = 2489.9(5) pm, c = 946.2(5) pm, β = 105.38(3)°, V = 1140.0(7) · 10⁶ pm³, R1 = 0.0365, wR2 = 0.0848 (for I > 2σ(I))). The title compounds 1 and 2 have the same chemical composition but exhibit different structures and are therefore polymorphs. Thus, in compound 1 , isolated ZnO₄‐tetrahedra, and in 2 , infinite double‐chains of corner‐sharing ZnO₆ polyhedra are observed. In, KZn[H(O₂C)₂C₆H₃PO₃] ( 3 ) K⁺‐ions have been incorporated into the structure leading to the formation of a bimetallic inorganic‐organic hybrid compound.     

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 (Z. Anorg. Allg. Chem. 2003, 629, 1012–1016)

In the article “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” (Z. Anorg. Allg. Chem. 2003 , 629, 1012–1016), some wrong parameters and bond lengths for UO₂(ClO₄)₂·7H₂O were given in table 1 and table 3 The correct parameters are: a = 1449.5(2) pm, b = 921.6(1) pm, c = 1067.5(2) pm, V = 1422.5(4)·10⁶ pm³, ρ = 2.712 g·cm^?3, μ = 119 cm^?1. The corrected bond lengths for this structure are U–O(1) 175.8(5) pm, U–O(2) 239.1(5) pm, U–O(3) 240.8(5), U–O(4) 242.0(7). A cif file with the correct data has been deposited with the ICSD.     

Three Modifications of [Pr2(ClO4)2(H2I2O10)]·8 H2O — A Theme with Variations

From solutions containing praseodymium perchlorate and periodic acid, three different modifications of [Pr₂(ClO₄)₂(H₂I₂O₁₀)] · 8 H₂O could be obtained. All of them crystallize in the monoclinic system, space group P2₁/c (α: a = 1091.47(6), b = 728.24(4), c = 1388.84(8) pm, β = 101.420(3)°; β: a = 1169.93(3), b = 728.72(2), c = 1384.50(4) pm, β = 112.303(2)°; γ: a = 1209.56(4), b = 712.53(2), c = 1361.64(5) pm, β = 115.691(1)°). The structures contain Pr³⁺ cations which are coordinated by [H₂I₂O₁₀]^4— anions yielding two‐dimensional networks. These networks are separated by ClO₄^— anions yielding a layered structure.     

Structural Patterns and Dimensionality in Magnesium Borophosphates: The Crystal Structures of Mg2(H2O)[BP3O9(OH)4] and Mg(H2O)2[B2P2O8(OH)2]·H2O

Hydrothermal investigations in the system MgO/B₂O₃/P₂O₅(/H₂O) yielded two new magnesium borophosphates, Mg₂(H₂O)[BP₃O₉(OH)₄] and Mg(H₂O)₂[B₂P₂O₈(OH)₂]·H₂O. The crystal structures were solved by means of single crystal X‐ray diffraction. While the acentric crystal structure of Mg₂(H₂O)[BP₃O₉(OH)₄] (orthorhombic, P2₁2₁2₁ (No. 19), a = 709.44(5) pm, b = 859.70(4) pm, c = 1635.1(1) pm, V = 997.3(3) × 10⁶ pm³, Z = 4) contains 1D infinite chains of magnesium coordination octahedra interconnected by a borophosphate tetramer, Mg(H₂O)₂[B₂P₂O₈(OH)₂]·H₂O (monoclinic, P2₁/c (No. 14), a = 776.04(5) pm, b = 1464.26(9) pm, c = 824.10(4) pm, β = 90.25(1)°, V = 936.44(9) × 10⁶ pm³,Z = 4) represents the first layered borophosphate with 6³ net topology. The structures are discussed and classified in terms of structural systematics.     

Hexachloroplatinates of the Lanthanides: Syntheses and Thermal Decomposition of [M(NO3)2(H2O)6]2[PtCl6]·2H2O (M = La,Pr) and [M(NO3)(H2O)7][PtCl6]·4H2O (M = Gd,Dy)

The reaction of the nitrates M(NO₃)₃·6H₂O (M = La, Pr) and (H₃O)₂PtCl₆ led to yellow single crystals of [M(NO₃)₂(H₂O)₆]₂[PtCl₆]·2H₂O (M = La, Pr) (monoclinic, P2₁/c, Z = 2, La/Pr: a = 697.4(3)/695.5(1), b = 1654.5(1)/1652.5(2), c = 1317.7(6)/1318.5(3) pm, β = 93.97°(7)/93.93°(2), R_all = 0.0169/0.0659) while the reaction of M(NO₃)₃·5H₂O (M = Gd, Dy) and (H₃O)₂PtCl₆ yielded yellow single crystals of [M(NO₃)(H₂O)₇][PtCl₆]·4H₂O (monoclinic, P2₁/n, Z = 4, Gd/Dy: a = 838.72(3)/838.40(2), b = 2131.98(6)/2139.50(7), c = 1142.63(3)/1143.10(3) pm, β = 95.670(4)/95.698(3), R_all = 0.0475/0.0337). The crystal structures consist of octahedral [PtCl₆]^2? anions and complex [M(NO₃)₂(H₂O)₆]₂⁺ and [M(NO₃)(H₂O)₇]²⁺ cations, respectively. The thermal decomposition of both types of compounds leads via various steps to elemental platinum and the oxide chlorides MOCl (M = La, Pr, Gd, Dy).     

Synthese,Struktur und Eigenschaften von drei Tetranatrium-tetrametaphosphimat-Hydraten

Synthesis, Structure, and Properties of Three Tetrasodium Tetrametaphosphimate Hydrates Single crystals of three tetrasodium tetrametaphosphimate hydrates Na₄(PO₂NH)₄ · x H₂O with x = 2 and 3, respectively, have been obtained and characterized by single crystal X-ray diffraction. Dimorphous Na₄(PO₂NH)₄ · 3 H₂O is formed at RT. It crystallizes monoclinic ( 1 ) or triclinic ( 2 ) (α-Na₄(PO₂NH)₄ · 3 H₂O ( 1 ): P2₁, a = 1002.7(2), b = 1189.7(2), c=1193.1(2)pm, β=104.93(1)°, Z=4; β-Na₄(PO₂NH)₄ · 3 H₂O ( 2 ): P 1¯, a = 843.64(9), b = 848.54(10), c = 994.7(2) pm, α = 83.07(1), β = 76.31(1), γ = 87.46(1)°, Z = 2). Compound 2 is formed in the presence of NaCl during the crystallization from aqueous solution. Tetrasodium tetrametaphosphimate dihydrate ( 3 ) is formed at 60 °C (Na₄(PO₂NH)₄ · 2 H₂O ( 3 ): C2/c, a = 2225.6(3), b = 513.0(1), c = 1566.7(2) pm, β = 134.21(1)°, Z = 4). In 1 and 2 the P₄N₄ ring of the tetrametaphosphimate ions attains a saddle and in 3 a twistboat conformation. The conformations of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The (PO₂NH)₄^4– rings of the compounds 1 , 2 , and 3 are linked by N–H · · &mid     

Syntheses and Crystal Structures of Two Cadmium Methanetetrabenzoates Featured by Open Framework and Infinite Layers

Colorless single crystals of Cd₂[μ₈‐MTB] · 3H₂O · DMF ( 1 ) were prepared in DMF/H₂O solution [ 1 : space group C2/c (no. 15) with a = 1821.30(6), b = 2175.08(6), c = 1269.87(4) pm, β = 129.684(1)°]. The connection between the methane‐p‐benzoate tetraanions (MTB^4–) and the Cd²⁺ cations leads to a three‐dimensional framework with channels extending along [1 10] and [110] with openings of 670 pm × 360 pm. The channel‐like voids accommodate water molecules and N,N‐dimethylformamide (DMF) molecules not bound to Cd²⁺. Colorless single crystals of [Cd₄(2,2′‐bipy)₄(μ₇‐MTB)₂] · 7DMF ( 2 ) were prepared in DMF in the presence of 2,2′‐bipyridine [ 2 : space group P1 (no. 2) with a = 1224.84(4), b = 1418.85(5), c = 2033.49(4) pm, α = 85.831(2)°, β = 88.351(2)°, γ = 68.261(1)°]. The coordination of MTB^4– to Cd²⁺ results in infinite layers parallel to (001). The layers, not connected by any hydrogen bonds, contain small openings of about 320 pm × 340 pm.     

Synthesis,Crystal Structures,and Vibrational Spectra of Novel Azidopalladates of the Alkali Metals Cs2[Pd(N3)4] and Rb2[Pd(N3)4]·2/3H2O

The transparent dark orange compounds Cs₂[Pd(N₃)₄] and Rb₂[Pd(N₃)₄]·²/₃H₂O are synthesized by reaction of the respective binary alkali metal azides with K₂PdCl₄ in aqueous solutions. According to single‐crystal X‐ray diffraction investigations, the novel ternary azidopalladates(II) crystallize in the monoclinic space group P2₁/c (no. 14) with a = 705.7(2) pm, b = 717.3(2) pm, c = 1125.2(5) pm, β = 104.58(2)°, mP30 for Cs₂[Pd(N₃)₄] and a = 1041.4(1) pm, b = 1292.9(2) pm, c = 1198.7(1) pm, β = 91.93(1)°, mP102 for Rb₂[Pd(N₃)₄]·²/₃H₂O, respectively. Predominant structural features of both compounds are discrete [Pd^II(N₃)₄]^2– anions with palladium in a planar coordination by nitrogen, but differing in point group symmetries., The vibrational spectra of the compounds are analyzed based on the idealized point group C_4h of the spectroscopically relevant unit, [Pd(N₃)₄]^2– taking into account the site symmetry splitting due to the symmetry reduction in the solid phase.     

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.     

New Hexachalcogeno–Hypodiphosphates of the Alkali Metals: Synthesis,Crystal Structure and Vibrational Spectra of the Hexathiodiphosphate(IV) Hydrates K4[P2S6] · 4 H2O,Rb4[P2S6] · 6 H2O,and Cs4[P2S6] · 6 H2O

The new hexathiodiphosphate(IV) hydrates K₄[P₂S₆] · 4 H₂O ( 1 ), Rb₄[P₂S₆] · 6 H₂O ( 2 ), and Cs₄[P₂S₆] · 6 H₂O ( 3 ) were synthesized by soft chemistry reactions from aqueous solutions of Na₄[P₂S₆] · 6 H₂O and the corresponding heavy alkali‐metal hydroxides. Their crystal structures were determined by single crystal X‐ray diffraction. K₄[P₂S₆] · 4 H₂O ( 1 ) crystallizes in the monoclinic space group P 2₁/n with a = 803.7(1), b = 1129.2(1), c = 896.6(1) pm, β = 94.09(1)°, Z = 2. Rb₄[P₂S₆] · 6 H₂O ( 2 ) crystallizes in the monoclinic space group P 2₁/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, β = 114.34(2)°, Z = 2. Cs₄[P₂S₆] · 6 H₂O ( 3 ) crystallizes in the triclinic space group with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, α = 95.65(2), β = 112.87(2), γ = 112.77(2)°, Z = 1. The structures are built up by discrete [P₂S₆]^4? anions in staggered conformation, the corresponding alkali‐metal cations and water molecules. O ··· S and O ··· O hydrogen bonds between the [P₂S₆]^4? anions and the water molecules consolidate the structures into a three‐dimensional network. The different water‐content compositions result by the corresponding alkali‐metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively. The FT‐Raman and FT‐IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P₂S₆]^4? group. The thermogravimetric analysis showed that K₄[P₂S₆] · 4 H₂O converted to K₄[P₂S₆] as it was heated at 100 °C.     

Syntheses and Crystal Structures of the Cyclotriphosphate Hydrates Nd(P3O9)·3H2O,Nd(P3O9)·4.5H2O,RE(P3O9)·5H2O (RE = Pr,Nd), and Na3RE(P3O9)2·6H2O (RE = Pr,Nd)

Several rare‐earth cyclotriphosphate hydrates were obtained from mixtures of sodium cyclotriphosphates and the respective rare‐earth chlorides. Nd(P₃O₉) · 3H₂O [P$\bar{6}$ , Z = 3, a = 677.90(9), c = 608.67(9) pm, R₁ = 0.016, wR₂ = 0.038, 312 data, 36 parameters] was obtained by a solid state reaction and is isotypic with respective rare‐earth phosphate hydrates, while all the others adopt new structure types. Nd(P₃O₉) · 4.5H₂O [C2/c, Z = 8, a = 1644.6(3), b = 756.11(15), c = 1856.1(4) pm, β = 97.25(3)°, R₁ = 0.032, wR₂ = 0.081, 1763 data, 194 parameters], Nd(P₃O₉) · 5H₂O [P2₁/c, Z = 4, a = 773.75(15), b = 1149.1(2), c = 1394.9(3) pm, β = 106.07(3)°, R₁ = 0.042, wR₂ = 0.082, 1338 data, 194 parameters], Pr(P₃O₉) · 5H₂O [P$\bar{1}$ , Z = 2, a = 745.64(15), b = 889.07(18), c = 934.55(19) pm, α = 79.00(3), β = 80.25(3), γ = 66.48(3), R₁ = 0.059, wR2 = 0.089, 1468 data, 193 parameters], Na₃Nd(P₃O₉)₂ · 6H₂O [P2₁/n, Z = 4, a = 1059.78(18), b = 1207.25(15), c = 1645.7(4) pm, β = 99.742(17), R₁ = 0.047, wR₂ = 0.119, 1109 data, 351 parameters] and Na₃Pr(P₃O₉)₂ · 6H₂O [P2₁/n, Z = 4, a = 1061.42(16), b = 1209.0(2), c = 1635.5(3) pm, β = 99.841(13), R₁ = 0.035, wR₂ = 0.062, 1323 data, 350 parameters] were obtained by careful crystallization at room temperature. A thorough structure discussion is given. The infrared spectrum of Nd(P₃O₉) · 4.5H₂O is also reported.     

The Crystal Structures of Two No–Metal Tricyanomelaminates: Diammonium Tricyanomelaminate Dihydrate [NH4]2[C6N9H] · 2 H2O and Dimelaminium Tricyanomelaminate Melamine Dihydrate [C3N6H7]2[C6N9H] · C3N6H6 · 2 H2O

Diammonium tricyanomelaminate dihydrate [NH₄]₂[C₆N₉H] · 2 H₂O ( 1 ) and dimelaminium tricyanomelaminate melamine dihydrate [C₃N₆H₇]₂[C₆N₉H] · C₃N₆H₆ · 2 H₂O ( 2 ) were obtained by metathesis reactions from Na₃[C₆N₉] in aqueous solution and characterized by single‐crystal X‐ray diffraction and ¹⁵N solid‐state NMR spectroscopy ( 1 ). Both salts contain mono‐protonated tricyanomelaminate (TCM) anions and crystallize as dihydrates. Considering charge balance requirements, the crystal structure of 1 (C2/c, a = 3181.8(6) pm, b = 360.01(7) pm, c = 2190.4(4) pm, β = 112.39(3)°, V = 2319.9(8) 10⁶ · pm³) can best be described by assuming a random distribution of an ammonium ion – crystal water pair over two energetically similar sites. Apart from two melaminium cations, 2 (P2₁/c, a = 674.7(5) pm, b = 1123.6(5) pm, c = 3400.2(5) pm, β = 95.398(5), V = 2566(2) 10⁶ · pm³) contains one neutral melamine per formula unit acting as an additional “solvent” molecule and yielding a donor‐acceptor type of π–stacking interaction.     

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.     

Synthese und Kristallstruktur der Übergangsmetalltrimetaphosphimate Zn3[(PO2NH)3]2 · 14 H2O und Co3[(PO2NH)3]2 · 14 H2O

Synthesis and Crystal Structure of the Transition Metal Trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O The transition metal trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O were obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with the respective metal nitrate or halide (molar ratio 1 : 4). The structure of Zn₃[(PO₂NH)₃]₂ · 14 H₂O was solved by single crystal X‐ray methods. The structure of isotypic Co₃[(PO₂NH)₃]₂ · 14 H₂O was refined from X‐ray powder diffraction data using the Rietveld method (Zn₃[(PO₂NH)₃]₂ · 14 H₂O ( 1 ): P 1, a = 743.7(2), b = 955.9(2), c = 980.1(2) pm, α = 102.70(3), β = 90.46(3), and γ = 100.12(3)°, Z = 1; Co₃[(PO₂NH)₃]₂ · 14 H₂O ( 2 ): P 1, a = 746.05(1), b = 957.06(2), c = 988.51(2) pm, α = 102.162(1), β = 90.044(1), and γ = 99.258(1)°, Z = 1). In 1 and 2 the P₃N₃ rings of the trimetaphosphimate ions attain a conformation which can be described as a combination of an ideal boat and an ideal twist conformation. The trimetaphosphimate ions act as bridging ligands. Thus chains of alternating M²⁺ and (PO₂NH)₃^3– ions are formed which are interconnected by additional M²⁺ ions forming electro‐neutral double chains. In the solid these double chains are connected by hydrogen bonds.     

[Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6 – ein Berylliumkomplex mit Cyclo‐(Be3O3)‐Kern und sein Hydrolyseprodukt [Be(H2O)4](I)2·2MeCN

Single crystals of [Be₃(μ₃‐O)₃(MeCN)₆{Be(MeCN)₃}₃](I)₆·4CH₃CN ( 1 ·4CH₃CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH₃CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R₁ = 0.0315). The hexaiodide complex cation 1 ⁶⁺consists of a cyclo‐Be₃O₃ core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH₃CN)₃}²⁺ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe₃ units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be₃O₃ unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH₃CN to moist air leads to small orange crystal plates of [Be(H₂O)₄]I₂·2CH₃CN ( 3 ·2CH₃CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R₁ = 0.0394), all hydrogen atoms of the dication [Be(H₂O)₄]²⁺ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be₃(μ₃‐O)₃(HCN)₆{Be(HCN)₃}₃]⁶⁺ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.     

Molecular and Low‐dimensional Coordination Compounds of Copper(II) and 3, 5‐Dimethylpyrazole — Synthesis,Crystal Structure,and Properties

Three 3, 5‐dimethylpyrazole (pz*) copper(II) complexes, [Cu(pz*)₄(H₂O)](ClO₄)₂ ( 1 ), [Cu(pz*)₂(NCS)₂]·H₂O ( 2 ), and [Cu(pz*)₂(OOCCH=CHCOO)(H₂O)]·1.5H₂O ( 3 ), have been synthesized and characterized with single crystal X‐ray structure analysis. 1 crystallizes in the tetragonal space group, 14/m, with a = 14.027 (3) Å, c = 16.301 (5) Å, and Z = 4. 2 crystallizes in the monoclinic space group, P2₁/c, with a = 8.008 (3) Å, b = 27.139 (9) Å, c = 8.934 (3) Å, β = 106.345 (6)°, and Z = 4. 3 crystallizes in the triclinic space group, P1¯, with a = 7.291 (9) Å, b = 10.891 (13) Å, c = 11.822 (14) Å, α = 80.90 (2)°, β = 79.73(2)°, γ = 70.60(2)°, and Z = 2. In 1 , one water molecule and four pz* ligands are coordinated to Cu^II. Two [Cu(pz*)₄(H₂O)]²⁺ units are connected to ClO₄^— via hydrogen bonds. One lattice water molecule is found in the unit cell of 2 , which forms an one‐dimensional chain via intermolecular hydrogen bonds with the N‐H atom of pz*. In 3 , the oxygen atom of the coordinated water molecule is connected with two C=O groups of two neighbouring maleic acid molecules to form a linear parallelogram structure. Another C=O group of maleic acid forms a hydrogen bond with the N‐H atom of pz* to create a two‐dimensional structure. The spectroscopic and bond properties are also discussed.