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.     

Darstellung und Strukturaufklärung von Ammonium‐tetraamminlithium‐amidotrithiophosphat‐Ammoniak(1/1) (NH4) [Li(NH3)4] [P(NH2)S3] · NH3

Synthesis and Crystal Structure of Ammonium Tetraamminelithium Amidotrithiophosphate‐Ammonia(1/1)(NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ Colourless crystals of (NH₄)[Li(NH₃)₄][P(NH₂)S₃]·NH₃ were prepared by the reduction of P₄S₁₀ with a solution of lithium in liquid ammonia. The X‐ray structure determination shows them to contain the pseudo‐tetrahedral amidotrithiophosphate anion [P(NH₂)S₃]²⁻ (point group C_S), which is the hitherto unknown final member of a series of previously characterized amidothiophosphates. The ammonium ion and the ammonia molecule of solvation form an diamminehydrogen(1+)‐ion N₂H₇⁺ with a short, nearly linear hydrogen bond of 2.864(3) Å.     

Preparation and Structure of Melemium Melem Perchlorate HC6N7(NH2)3ClO4·C6N7(NH2)3

A new perchlorate salt of melem (2,6,10‐triamino‐s‐heptazine, C₆N₇(NH₂)₃) was obtained from an aqueous solution of HClO₄ at lower concentration than the ones reported for the synthesis of melemium perchlorate monohydrate (HC₆N₇(NH₂)₃)ClO₄·H₂O. The new salt was identified as melemium melem perchlorate (HC₆N₇(NH₂)₃)ClO₄·C₆N₇(NH₂)₃ representing a melem adduct of water free melemium perchlorate. The crystal structure was solved by single‐crystal X‐ray methods ( , no. 2, Z = 2, a = 892.1(2), b = 992.7(2), c = 1201.5(2) pm, α = 112.30(3), β = 96.96(3), γ = 95.38(3)°, V = 965.8(4)·10⁶ pm³, 4340 data, 387 parameters, R1 = 0.039). Melemium melem perchlorate crystallizes in a layer‐like structure containing both protonated HC₆N₇(NH₂)₃ and non protonated C₆N₇(NH₂)₃ moieties in the coplanar layers as well as perchlorate ions between them, all of which being interconnected by hydrogen bonds. Vibrational spectroscopic investigations (FTIR and Raman) of the salt were conducted.     

Hydrogen Bonds in Rubidium Amide‐Ammonia(3/2), RbNH2·2/3NH3

Rubidium amide‐ammonia(3/2), RbNH₂·2/3NH₃, was synthesized from Rubidiumhydride, RbH, in liquid ammonia at ?78 °C. The compound crystallizes in the cubic space group I2₁3 with Z = 4, a = 10.0490(12) Å, and V = 1014.77(20) Å as isometric colorless crystals. The crystal structure was solved from single‐crystal X‐ray data. The structure contains a three‐dimensional network of amide anions and ammonia molecules, which are interconnected via hydrogen bonds.     

Synthesis and Crystal Structure of Cesium Hexamminesodium Decahydro‐closo‐decaborate‐Ammonia(1/1), Cs[Na(NH3)6][B10H10]·NH3

Cs[Na(NH₃)₆][B₁₀H₁₀]·NH₃ was synthesised from cesium and disodium‐decahydro‐closo‐decaborate Na₂B₁₀H₁₀ in liquid ammonia, from which it crystallized in form of temperature sensitive colorless plates (triclinic, P1¯, a = 8.4787(7) Å, b = 13.272(1) Å, c = 17.139(2) Å, α = 88.564(1)°, β = 89.773(1)°, γ = 81.630(1)°, V = 1907.5(3) ų, Z = 4). The compound is the first example of an alkali metal boranate with two different types of cations. The decahydro‐closo‐decaborate dianions [B₁₀H₁₀]^2— and the cesium cations form a equation/tex2gif-stack-1.gif[Cs₂(B₁₀H₁₀)₂]^2— layer parallel to the ac plane. These layers are separated by N—H···N‐hydrogen bonded hexamminesodium cations.     

First Characterization of an Extended Ammonium‐Ammonia Complex [{NH4(NH3)4}+(μ‐NH3)2] in the Crystal Structure of [NH4(NH3)4][Co(C2B9H11)2] · 2 NH3

The compound [NH₄(NH₃)₄][Co(C₂B₉H₁₁)₂] · 2 NH₃ ( 1 ) was prepared by the reaction of Na[Co(C₂B₉H₁₁)₂] with a proton‐charged ion‐exchange resin in liquid ammonia. The ammoniate 1 was characterized by low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of [Co(C₂B₉H₁₁)₂]^‐ complexes, which are connected via C‐H···H‐B dihydrogen bonds. Furthermore, 1 contains an infinite equation/tex2gif-stack-2.gif[{NH₄(NH₃)₄}⁺(μ‐NH₃)₂] cationic chain, which is formed by [NH₄(NH₃)₄]⁺ ions linked by two ammonia molecules. The N‐H···N hydrogen bonds range from 1.92 to 2.71Å (DHA = Donor···Acceptor angles: 136‐176°). Additional N‐H···H‐B dihydrogen bonds are observed (H···H: 2.3‐2.4Å).     

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.     

An Unexpected Diboroxane: Crystal Structure of Me2HN · (CF3)2BOB(CF3)2 · NHMe2

(CF₃)₂BNMe₂ ( 1 ) reacts at room temperature with water in a 2:1 ratio to form bis(dimethylamine)‐tetrakis(trifluoromethyl)diboroxane Me₂HN·(CF₃)₂BOB(CF₃)₂·NHMe₂ ( 2 ), whereas a 1:1 ratio at —78 °C had yielded HO(CF₃)₂B·NHMe₂ ( 3 ). The constitution of 2 has been deduced from multinuclear NMR, IR and mass spectra, and the structure has been determined by single‐crystal X‐ray diffraction. Averaging 1.396(6) Å, the B—O bond length is short, and the B—O—B bond angle, 150.4(3)°, is very wide.     

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 .     

Synthesis and Crystal Structure of [Fe(Cp)2]3(Bi2Cl9)·thf

Single crystals of [Fe(Cp)₂]₃(Bi₂Cl₉)·thf were obtained from a thf solution containing ferrocene and BiCl₃. The structure shows disorder at room temperature which disappears upon cooling, coupled with a decrease in symmetry. The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ [a = 1698.64(2), b = 2318.69(3), c = 1085.66(2) pm] with three ferrocenium ions, one nonachlorodibismutate ion and one molecule of thf in the asymmetric unit.     

Formation and Crystal Structure of the Salt (IC(PPh3)2)2I[I3]·(I2)2 with a new Polyiodide Chain

The reaction of the carbodiphosphorane Ph₃P=C=PPh₃ ( 1 ) with MeI in the presence of iodine gives the oxidation product (IC(PPh₃)₂)₂I[I₃]·(I₂)₂ ( 2 ). In the solid state dimeric units linked by indefinite ···I^?···I₂···I₃^?···I₂···I^?··· chains are found. An additional I···I contact between the cation and the I₂ molecule is formed, amounting to 359.23(5) pm. 2 crystallizes in the monoclinic space group P2/c, with the unit cell dimensions a = 2053.9(1), b = 1011.4(1), c = 1889.8(1) pm; β = 105.21(1)° and Z = 4.     

Synthesis of Ammonium‐ and 4‐Dimethylaminopyridinium Amidofluorophosphates and Crystal Structure of [DMAPH][PO2F(NH2)]

NH₄[PO₂F(NH₂)] has been prepared by the reaction of a betaine py·PO₂F with excess ammonia in acetonitrile solution, while the ammonolysis of DMAP·PO₂F with a stoichiometric amount of NH₃ yields [DMAPH][PO₂F(NH₂)]. The crystal structure of the latter was determined by single‐crystal X‐ray diffraction, which revealed that the anions [PO₂F(NH₂)]^— are linked to infinite chains by double N—H···O bridges. Additional strong N—H···O bridging bonds connect each anion with its [DMAPH]⁺ counterion. The formation of a new betaine NH₃·PO₂F in the solution of py·PO₂F in liquid ammonia was proved by ³¹P NMR spectroscopy and by identification of its hydrolysis products.     

[In2(HPO3)4]·(NH3CH2CH2NH3)的水热合成与晶体结构

用乙二胺作模板剂在水热条件下合成出一个新的三维开放骨架结构的亚磷酸铟[In2(HPO3)4]·(NH3CH2CH2NH3)(1), 并对其晶体结构进行了测定和表征.     

Palladium(II) Complexes with the Mixed‐Donor Ligand CH3S‐(CH2)3‐PPh2 Crystal Structures of [PdCl2{CH3S‐(CH2)3‐PPh2}n](n = 1, 2)

The phosphorus‐sulfur ligand 1‐(methylthio)‐3‐(diphenylphosphino)‐propane (S‐P3) has been synthesized and characterized by ¹H NMR and ¹³C NMR. Reactions of S‐P3 with [PdCl₂(PhCN)₂] afforded the complexes [PdCl₂(S‐P3)] ( I ) and [PdCl₂(S‐P3)₂] ( II ), in which S‐P3 acts as a bidentate and monodentate ligand, respectively. Compound I crystallizes in monoclinic space group P2₁/n (No. 14) with cell dimensions: a = 8.589(3), b = 15.051(3), c = 17.100(3)Å, β = 102.91(2)°, V = 2154.7(9)ų, Z = 4. Likewise, compound II crystallizes in monoclinic space group P2₁/n (No. 14) with a = 9.993(5), b = 8.613(4), c = 18.721(5)Å, β = 90.18(3)°, V = 1611.3(12)ų, Z = 2. Compound II has a trans square planar configuration with only the P‐site of the ligand bonded to the palladium atom.     

Structure and Magnetic Properties of a Novel Two‐Dimensional Complex from 1, 3, 5‐Benzenetricarboxylate and Neodymium(III) — {[Nd(1, 3, 5‐benzenetricarboxylate)(H2O)4] · H2O}n

A unique neodymium(III) complex, {[Nd(BTC)(H₂O)₄] · H₂O}_n (BTC = 1, 3, 5‐benzenetricarboxylate), was obtained from the reaction between Nd(ClO₄)₃ · xH₂O and Na₃BTC. Coordination bonds, hydrogen bonds, and π‐π stacking form a supramolecular structure with a novel, two‐dimensional framework. The temperature‐dependent magnetic susceptibilities were analyzed by the Curie‐Weiss law; the following values were found C = 1.32, θ = —18.3 K, respectively.     

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.     

Crystal Structure of Ni(NH3)Cl2 and Ni(NH3)Br2

Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ were prepared by the reaction of Ni(NH₃)₂X₂ with NiX₂ at 350 °C in a steel autoclave. The crystal structures were determined by X‐ray powder diffraction using synchrotron radiation and refined by Rietveld methods. Ni(NH₃)Cl₂ and Ni(NH₃)Br₂ are isotypic and crystallize in the space group I2/m with Z = 8 and for Ni(NH₃)Cl₂: a = 14.8976(3) Å, b = 3.56251(6) Å, c = 13.9229(3) Å, β = 106.301(1)°; Ni(NH₃)Br₂: a = 15.5764(1) Å, b = 3.74346(3) Å, c = 14.4224(1) Å, β = 105.894(1)°. The crystal structures are built up by two crystallographically distinct but chemically mostly equivalent polymeric octahedra double chains [NiX_3/3X_2/2(NH₃)] (X = Cl, Br) running along the short b‐axis. The octahedra NiX₅NH₃ share common edges therein. The crystal structures of the ammines Ni(NH₃)_mX₂ with m = 1, 2, 6 can be derived from that of the halides NiX₂ (X = Cl, Br) by successive fragmentation of its CdCl₂ like layers by NH₃.     

Synthesis and Structure of [Hg{OP(O)CF3(OH)}2(PMe3)3], a Distorted Trigonal Bipyramidal Complex Connected by Hydrogen Bridges to Polymeric Chains

The hydrolysis of [Hg{P(CF₃)₂}₂(PMe₃)₂] yields colourless crystals of [Hg{OP(O)CF₃(OH)}₂(PMe₃)₃]. The proposed multistep reaction proceeds via primary hydrolysis of the starting material giving HgO and HP(CF₃)₂. The latter is directly oxidized by HgO to (CF₃)₂P(O)OH. The bis(trifluoromethyl)phosphinic acid hydrolyses to CF₃P(O)(OH)₂ which reacts with [Hg{P(CF₃)₂}₂(PMe₃)₂] in the presence of PMe₃ to the title compound. The crystal structure was determined by X‐ray single‐crystal analysis (triclinic; P1¯; a = 860.7(1), b = 1007.6(2), c = 1625.0(3) pm; α = 96.09(2), β = 101.09(2), γ = 107.79(2)°; Z = 2) and exhibits distorted trigonal bipyramidal mercury complexes which are connected to polymeric chains. The acidic units, {OP(O)CF₃(OH)}^—, are connected via intermolecular hydrogen bridges, forming two individual centrosymmetric eight membered rings with asymmetric hydrogen bridges with O—O distances of 249.4(8) and 250.8(8) pm.     

Crystal Structure of Bis(3-hydroxy-2-pyridyl)disulfide

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