Synthese, Kristallstruktur und Eigenschaften von Tetraaminophosphoniumchlorid [P(NH2)4]Cl / Synthesis, Crystal Structure, and Properties of Tetraaminophosphonium Chloride [P(NH2)4]Cl

1996 ◽  
Vol 51 (1) ◽  
pp. 127-132 ◽  
Author(s):  
Stefan Horstmann ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Room Temperature ◽  
Phosphorus Pentachloride ◽  
Mean Value ◽  
Acetonitrile Solution ◽  
Anomeric Effect ◽  
Electron Pairs ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Ray Methods

Abstract [P(NH2)4]Cl has been prepared by ammonolysis of phosphorus pentachloride in liquid ammonia. The product was purified by reacting the byproduct, ammonium chloride, with diethylamine and removing the diethylamine hydrochloride. Suitable single crystals were obtained from an acetonitrile solution in a temperature gradient between 60 °C and room temperature. The crystal structure of [P(NH2)4]Cl has been determined by single crystal X-ray methods (Pbcn, a = 470.8(2), b = 1622.3(3), c = 756.3(2) pm, Z = 4). In the solid, [P(NH2)4]+ and Cl- ions are found, resembling a TlI-analogous structure. The N-H···Cl distances indicate N-H···Cl hydrogen bonding interactions. The distortion of the P-N sceleton of the cation and the very short P-NH2 distances (mean value: 161.2 pm) have been confirmed by ab initio calculations, which show a generalized anomeric effect of the electron pairs at nitrogen and pπdπ bonding.

Synthese, Kristallstruktur und Eigenschaften von Tetraaminophosphoniumiodid [P(NH2)4]I / Synthesis, Crystal Structure, and Properties of Tetraaminophosphonium Iodide [P(NH2)4]I

1994 ◽  
Vol 49 (10) ◽  
pp. 1381-1386 ◽  
Author(s):  
Stefan Horstmann ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Room Temperature ◽  
Bond Distance ◽  
Acetonitrile Solution ◽  
Structure And Properties ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Anions And Cations ◽  
Ray Methods

Abstract The title compound has been prepared starting from phosphorothionic triamide SP(NH2)3 by methylation of the sulfur atom and subsequent ammonolysis reaction in dry acetonitrile and dichloromethane, respectively, both at room temperature. Suitable single crystals are obtained from an acetonitrile solution in a temperature gradient between 70 °C and room temperature. The crystal structure of [P(NH2)4]I has been determined by single crystal X-ray methods (P4/nbm; a = 842.6(2), c = 486.7(2) pm, Z = 2). In the solid [P(NH2)4]+ - and I−-ions are found with significant N - H···I-hydrogen bonding interactions between anions and cations (H -I: 276.4 pm). The P - N - bond length in the cation (160.7(2) pm) represents the shortest P - NH2 bond distance reported to date indicating a significant electrostatic strengthening. The condensation behaviour of [P(NH2)4]I in solution and in the solid has been investigated.

Synthese, Kristallstruktur und Eigenschaften von 1,1,3,3,3-Pentaaminol- 1-thio-1 λ5,3λ5-diphosphaz-2-en (NH2)2P(S)N=P(NH2)3 / Synthesis, Crystal Structure, and Properties of 1,1,3,3,3-Pentaam 1-thio-1 λ5,3λ5-diphosphaz-2-en (NH2)2P(S)N=P(NH2)3

1997 ◽  
Vol 52 (4) ◽  
pp. 490-495 ◽  
Author(s):  
Stefan Horstmann ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Hydrogen Atom ◽  
Room Temperature ◽  
Acetonitrile Solution ◽  
Structure And Properties ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Ray Methods

Abstract (NH2)2P(S)N=P(NH2)3 has been prepared by a two step synthesis. Suitable single crystals were obtained from an acetonitrile solution in a temperature gradient between 60 °C and room temperature. The crystal structure of (NH2)2P(S)N=P(NH2)3 has been determined by single crystal X-ray methods (P21/c, a = 998.27(9) b = 762.78(8), c = 1007.70(15) pm, β = 107.340(7)°, Z = 4). In the crystal structure each hydrogen atom is subject to a hydrogen bond. Four N-H -N hydrogen bonding interactions per molecule build up a framework connecting two molecules in eight-membered rings. Each sulfur atom shows six distances N-H···S in the range of weak hydrogen bonding interactions.

Synthese, Kristallstruktur und Eigenschaften von 1,1,3,3,3-Pentaamino-1-oxo- 1λ5 ,3λ5-diphosphaz-2-en, (NH2)2(O)P-N=P(NH2)3 / Synthesis, Crystal Structure, and Properties of 1,1,3,3,3-Pentaamino-1-oxo-1λ5, 3λ5-diphosphaz-2-ene, (NH2)2(O)P-N=P(NH2)3

1996 ◽  
Vol 51 (8) ◽  
pp. 1079-1083 ◽  
Author(s):  
N. Stock ◽  
W. Schnick
Keyword(s):  
Crystal Structure ◽  
Thermal Properties ◽  
Room Temperature ◽  
Three Dimensional ◽  
Intermolecular Hydrogen Bonding ◽  
Structure And Properties ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Dimensional Network ◽  
Ray Methods

Coarse crystalline (NH2)2(O)P-N=P(NH2)3 is obtained from a NH3 saturated CH2Cl2 suspension of (NH2)2(O)P-N=P(NH2)3 NH4Cl at room temperature. (NH2)2(O)P-N=P(NH2)3·NH4Cl is synthesized by slow addition of Cl2(O)P-N=PCl3 to a solution of NH3 in CH2Cl2 at -78 °C. Excess NH4Cl is removed by treatment with HNEt2 followed by extraction with CH2Cl2. The crystal structure of (NH2)2(O)P-N=P(NH2)3 has been determined by single crystal X-ray methods (P21/c; a = 1462.8(3), b = 944.8(2), c = 1026.9(2) pm, β = 110.69(3)°; Z = 8). In the unit cell there are two crystallographically unique molecules. They form a three dimensional network by intermolecular hydrogen bonding interactions (N-H···N ≥ 313 pm. N-H···O ≥ 293 pm). The investigation of the thermal properties shows decomposition with evolution of NH3 above 80 °C.

Synthese, Kristallstruktur und Eigenschaften von 1,1,1,3,3, 3 - Hexaamino - 1λ5,3λ5-diphosphazeniumehlorid [(NH2)3PNP(NH2)3]Cl / Synthesis, Crystal Structure, and Properties of 1,1,1,3,3,3-Hexaamino- 1λ5 ,3λ5-diphosphazenium Chloride [(NH2)3 PNP(NH2)3 ]Cl

1996 ◽  
Vol 51 (12) ◽  
pp. 1732-1738 ◽  
Author(s):  
Stefan Horstmann ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Phase Transition ◽  
Temperature Gradient ◽  
Single Crystal ◽  
Single Crystals ◽  
Room Temperature ◽  
Acetonitrile Solution ◽  
Structure And Properties ◽  
X Ray ◽  
Ray Methods

[(NH2)3PNP(NH2)3]Cl has been prepared by a three step synthesis. The last step is the ammonolysis of [Cl3PNPCl3]Cl. Single crystals of 1,1,1,3,3,3-hexaamino-1λ5, 3λ5-diphosphazenium chloride were obtained from an acetonitrile solution in a temperature gradient between 60 °C and room temperature. Between room temperature and -100 °C [(NH2)3PNP(NH2)3]Cl is subject to a phase transition. Therefore, the crystal structure was determined by single crystal X-ray methods at room temperature (P1̄, a = 584.7(1) pm, b = 732.1(1) pm, c = 1092.0(2) pm. q = 71.05(3)°, β = 76.36(3)°, γ = 89.83(3)°, Z = 2, R = 4.75 %, wR = 2.47 %). The cation [(NH2)3PNP(NH2)3]+ is built up by two corner sharing PN4 tetrahedra. Remarkably short P-N bonding distances have been observed and both PN4 tetrahedra exhibit a significant distortion resulting in two large and four small N-P-N bond angles.

Synthese, Struktur und thermisches Verhalten von Thiophosphorsäuretriamid SP(NH2)3 [1] / Synthesis, Structure, and Thermal Behaviour of Phosphorothionic Triamide SP(ΝΗ2)3 [1]

1989 ◽  
Vol 44 (8) ◽  
pp. 942-945 ◽  
Author(s):  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Thermal Properties ◽  
Single Crystal ◽  
Melting Temperature ◽  
Intermolecular Hydrogen Bonding ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Ray Methods ◽  
Single Bonds

Phosphorothionic triamide SP(NH2)3 is obtained by slow addition of SPCl3 dissolved in dry CH2Cl2 to a satured solution of NH3 in CH2Cl2 at —50°C. Ammonium chloride is removed from the resulting precipitate by treatment with HNEt2 followed by extraction with CH2Cl2. Coarse crystalline SP(NH2)3 is obtained after recrystallization from dry methanol. The crystal structure of SP(NH2)3 has been determined by single crystal X-ray methods (Pbca; a = 922.3(1), b = 953.8(1), c = 1058.4(2) pm, Z = 8). In the crystals the molecules show non-crystallographic point symmetry C8. The P—S bond (195.4(1) pm) is slightly longer than in SPCl3. From P—N bond lengths of about 166 pm a significant electrostatic strengthening of the P—N single bonds is assumed. Weak intermolecular hydrogen bonding interactions (N —H · · · N ≥ 329.5 pm; N — H · · · S ≥ 348.3 pm) are observed.Investigation of thermal properties shows a melting temperature of 115°C for SP(NH2)3. According to combined DTA/TG and MS investigations above this temperature the compound decomposes by evolution of H2S and NH3 to yield amorphous phosphorus(V)nitride.

Synthese und Kristallstruktur von [(Cl3Si)2N]2TiCl2 -ein perchloriertes N-Silyl-titanamid /Synthesis and Crystal Structure of [(Cl3Si)2N]2TiCl2 -a Fully Chlorinated N-Silyl Titanium Amide

1997 ◽  
Vol 52 (7) ◽  
pp. 819-822 ◽  
Author(s):  
Bernd Schwarze ◽  
Wolfgang Milius ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Room Temperature ◽  
Titanium Atom ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Ray Methods ◽  
Cl Atoms

Abstract The chlorinated titanium amides [(Cl3Si)2N]2TiCl2 (1) and (Cl3Si)2NTiCl3 have been syn­thesized selectively from hexachlorodisilazane lithium and TiCl4. The crystal structure of 1 was determined by single crystal X-ray methods at room temperature (P212121, a = 1232.4(2), b = 1265.5(2), c -1469.1(2) pm, Z = 4). The central titanium atom of 1 is bound to two nitrogen atoms and two Cl atoms and is weakly coordinated further by two Cl atoms of the trichlorosilyl groups.

Neue Tetraaminophosphonium-Salze durch Anionenaustausch in flüssigem Ammoniak

1999 ◽  
Vol 54 (8) ◽  
pp. 1019-1026 ◽  
Author(s):  
Kai Landskron ◽  
Stefan Horstmann ◽  
Wolfgang Schnick
Keyword(s):  
Complex System ◽  
Temperature Gradient ◽  
Hydrogen Bonds ◽  
Single Crystals ◽  
Room Temperature ◽  
Liquid Ammonia ◽  
Acetonitrile Solution ◽  
X Ray ◽  
Cscl Type ◽  
Ray Methods

[P(NH2)4]Br and [P(NH2)4][NO3] have been prepared by anion exchange in liquid ammonia. Single crystals of [P(NH2)4]Br were obtained from an acetonitrile solution in a temperature gradient between 60 °C and room temperature while attempts to grow single crystals of [P(NH2)4][NO3] yielded [P(NH2)4][NO3](OP(NH2)3). Both crystal structures were determined by single crystal X-ray methods at room temperature ([P(NH2)4]Br: P4/nbm, a = 809.2(1), c = 468.1(1) pm, Z = 2, R1 = 0.042, wR2 = 0.077; [P(NH2)4][NO3](OP(NH2)3): Pna21, Z = 4, a = 1023.4(1), b = 1704.7(1), c = 618.0(1) pm, R1 =0.025, wR2 = 0.067. In the solid [P(NH2)4]Br forms a tetragonally distorted variant of the CsCl type of structure. [P(NH2)4][NO3](OP(NH2)3) consists of [P(NH2)4]+cations, [NO3]- anions, and OP(NH2)3 molecules which are interconnected by a complex system of hydrogen bonds.

Synthese und Kristallstruktur von [H2NMe2]+[(Me2NH)2 TiCl4]-/Synthesis and Crystal Structure of [H2NMe2]+[(Me2NH)2TiCl4]-

1998 ◽  
Vol 53 (2) ◽  
pp. 239-241 ◽  
Author(s):  
Regina Bettenhausen ◽  
Wolfgang Milius ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Title Compound ◽  
Room Temperature ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Ionic Salt ◽  
Ray Methods ◽  
Cl Atoms

Abstract The title compound has been synthesized as a green solid by the reaction of MeCl2 SiNHSiMe3 and Ti(NMe2)4 in CH2Cl2. The crystal structure was determined by single crystal X-ray methods at room temperature (C2/c, a = 1825,7(4), b = 909,9(2), c = 1116,1(2) pm, β = 125,09(3)°, Z = 4,R1= 0,047, wR2 = 0,147) to be an ionic salt [H2NMe2]+[(Me2NH)2TiCl4]- . The central titanium(III) atom of the anion is bound to four Cl atoms and weakly coordinated by two Me2NH ligands.

Synthese und Kristallstruktur neuer 1,1,1,3,3,3-Hexaamino-1λ5,3λ5- diphosphazenium-Salze/ Synthesis and Crystal Structure of Novel 1,1,1,3,3,3-Hexaamino-1λ5,3λ5- diphosphazenium Salts

1999 ◽  
Vol 54 (11) ◽  
pp. 1363-1370 ◽  
Author(s):  
Kai Landskron ◽  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Aqueous Solution ◽  
Temperature Gradient ◽  
Single Crystals ◽  
Room Temperature ◽  
Gauche Conformation ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Acetonitrile Solutions ◽  
Ray Methods

1,1,1,3,3,3-Hexaamino-1λ5,3λ5-diphosphazenium bromide [(NH2)3PNP(NH2)3]Br, nitrate [(NH2)3PNP(NH2)3][NO3], and toluene-4-sulfonate [(NH2)3PNP(NH2)3][CH3C6H4SO3] have been prepared by anion exchange in aqueous solution. Single crystals were obtained from acetonitrile solutions in a temperature gradient between 60 °C and room temperature. The crystal structures were determined by single crystal X-ray methods at room temperature. ([(NH2)3PNP(NH2)3]Br: P1̄̄ , Z = 2, a = 596.2( 1 ),b = 744.5( 1), c = 1114.4( 1) pm, α = 108.78( 1), β = 104.18(1), γ = 90.64(1)°, R 1 = 0.048, wR2 = 0.104; [(NH2)3PNP(NH2)3][NO3]: P1̄̄, Z = 2, a = 550.9( 1), b = 796.3( 1), c = 1115.7( 1) pm, α = 94.45( 1), β= 99.55( 1), γ = 101,53( 1)°, R1 = 0.033, wR2 = 0.095; [(NH2)3PNP(NH2)3][CH3C6H4SO3]: P21/c, Z = 4, a = 804.1(1), b = 596.1(1), c = 3218.7(3) pm, β = 94.59(1)°, R1 = 0.052, wR2 = 0.136). In the solid the three salts consist of discrete [(NH2)3PNP(NH2)3]+ cations and their corresponding anions. The PN4 tetrahedra in [(NH2)3PNP(NH2)3]Br are staggered, while in [(NH2)3PNP(NH2)3][NO3] the eclipsed conformation is preferred. The PN4 tetrahedra of [(NH2)3PNP(NH2)3][CH3C6H4SO3] show gauche conformation.

Group 15 Metal Complexes With Carboxylic Acids. Preparation and Crystal Structure of Polymeric Ammonium Aquabis[(+)-tartrato(2-)]bismuthate(III) Hydrate

1992 ◽  
Vol 45 (6) ◽  
pp. 1027 ◽  
Author(s):  
DS Sagatys ◽  
EJ Oreilly ◽  
S Patel ◽  
RC Bott ◽  
DE Lynch ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Metal Complexes ◽  
Tartaric Acid ◽  
Carboxylic Acids ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
A Cell ◽  
Ray Methods

The crystal structure of the bismuth(III) complex with (+)-tartaric acid, ammonium aquabis [(+)-tartrato (2-)] bismuthate (III) hydrate, has been determined by X-ray methods and refined to a residual R 0.020 for 1288 observed reflections. Crystals are orthorhombic, space group P 212121 with Z 4 in a cell of dimensions a 7.4712(4), b 10.856(1), c 17.609(3) � . Each nine-coordinate MO9 bismuth centre comprises three bidentate α-hydroxy carboxy residues from two tartrato (2-) ligands (with one bridging), an asymmetric bidentate carboxylato (O,O') group, and a water. The Bi-O range is 2.372(7)-2.738(6) � [mean 2.509(6) >� ]. The resultant structure is a linear polymer which is stabilized by extensive hydrogen-bonding interactions.

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