Crystal structure of (diphenyl)(morpholino)phosphiniminocyclotrithiazene
01 Jun 1996-Journal of Chemical Crystallography (Kluwer Academic Publishers-Plenum Publishers)-Vol. 26, Iss: 6, pp 403-406
TL;DR: The title compound (C6H5)2(OC4H8N)P=N−S3N3 crystallizes in the space group\(P\bar 1\) with unit cell parametersa=9.3900(2),b= 9.4747(1),c=11.3850(3) A, α=95.73(4), β=96.85(6), γ=104.26(2)o, and Z=2.683(4) A as mentioned in this paper.
Abstract: The title compound (C6H5)2(OC4H8N)P=N−S3N3 crystallizes in the space group\(P\bar 1\) with unit cell parametersa=9.3900(2),b=9.4747(1),c=11.3850(3) A, α=95.73(4), β=96.85(6), γ=104.26(2)o, and Z=2. The tricoordinated sulfur of the cyclotrithiazene ring deviates from the mean plane of other skeletal atoms by 0.683(4) A. The angle at this atom is the smallest in the ring and is enclosed by the longest S−N bonds observed in the ring.
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TL;DR: In this paper, the coordination behavior of several symmetrically and unsymmetrically substituted phosphiniminocyclotrithiazenes have been studied and shown to have different reduction potentials.
Abstract: Electrochemical (polarographic, cyclic voltammetric, and coulometric) and coordination behaviour of several symmetrically and unsymmetrically substituted phosphiniminocyclotrithiazenes have been studied. Polarograms of R3PN-S3N3 (R = C6H5, p-ClC6H4, p-H3CC6H4, and (OC4H8N)), Ph2(OC4H8N)PN-S3N3, and Ph(OC4H8N)2PN-S3N3 give two cathodic waves. Cyclic voltammograms of Ph3PN-S3N3 (1) and (OC4H8N)3PN-S3N3 (2) reveal nearly the same oxidation peak potential but different reduction potentials. Controlled potential electrolysis of 1 and 2 at +0.6 V indicates exocyclic cleavage and ring degradation. Cathodic reduction behaviour of Ph3PN-S3N3 suggests the possibility for the formation of 1,5-(Ph3PN)2S4N4 under electrochemical conditions. Reaction of nickel chloride hexahydrate with heterocycle 1 in 1:2 molar ratio in acetonitrile affords the complex, [Ni(S2N2H)2] (A) (90% yield) and [Ph3PNH2]Cl salt as products. Analogous reactions with other ligands of this type (two symmetrical (sym.) and three unsymmetrical (uns...
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TL;DR: The title compound (OC4H8N)3P=N-S3N3 crystallizes in a monoclinic crystal system with unit cell parameters a = 89996(3), b = 172895(7), and c = 123648(9) A, β = 9063(5)°, Z = 4, and space group P21/n.
Abstract: The title compound (OC4H8N)3P=N–S3N3 crystallizes in a monoclinic crystal system with unit cell parameters a = 89996(3), b = 172895(7), and c = 123648(9) A, β = 9063(5)°, Z = 4, and space group P21/n Strikingly the exocylic S1–N4 bond length is 1545(3) AR and is accompanied by the largest angle at P–N4–S1 as 1312(2)° The tricoordinated sulfur atom of the cyclotrithiazene ring deviates from the mean plane of other five atoms by 0654(1) A
5 citations
TL;DR: In this paper, the tricoordinated sulfur atom (S1) in the cyclotrithiazene was shown to be highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or −1.0) for the cyclic and acyclic substituents in the (R)(C6H5)2]P{-S3N3 series.
Abstract: The title compound (NC4H8NCH3)(C6H5)[N(C6H11)2]P{—N–S3N3 crystallizes in the triclinic crystal system with unit cell dimensions: a = 9.7572(2), b = 10.6845(1), c = 16.9381(3) A, α = 71.75(1)∘, β = 80.65(2)∘, γ = 65.93(1)∘, and Z = 2. The tricoordinated sulfur atom (S1) in the cyclotrithiazene deviates from the mean plane of the other five atoms by 0.716(6) A, which is the highest among the known phosphiniminocyclotrithiazene structures. In the exocyclic P{—N4–S1 moiety, the two bond distances are short: 1.585(6) and 1.527(6) A; but the bond angle is large 135.3(4)∘. The S1 displacement is highly correlated with the endocyclic angle at the nitrogen atom (diagonally opposite to S1), but the nature of correlation is bimodal (R = 1.0 + or −1.0) for the cyclic and acyclic substituents (R) in the (R)(C6H5)[N(C6H11)2]P{—N–S3N3 series. On the other hand, the S1–N4 bond distances are negatively correlated (R = −0.94) with the P{—N4–S1 bond angle in the above series.
4 citations
TL;DR: The title compound (C6H5)(C4H8NO)[N(C 6H11)2]P=N-S3N3 crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4), b = 10.6075(1) A, c = 14.2276(2), α = 78.14(3)°, β = 79.31°, λ = 65.42°, V = 1319.44°, Z = 2, and space group
Abstract: The title compound (C6H5)(C4H8NO)[N(C6H11)2]P=N-S3N3 crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4) A, b = 10.6075(1) A, c = 14.2276(2) A, α = 78.14(3)°, β = 79.31(1)°, λ = 65.42(2)°, V = 1319.44(6) A3, Z = 2, and space group \(P\bar 1\). The cyclotrithiazene ring adopts a “distorted chair” conformation with a deviation of 0.682(7) A for the tricoordinated sulfur atom. Remarkably, a short exocyclic S-N bond length 1.489(4) A along with a large P-N-S angle 136.2(3)° are observed with the iminophosphorus moiety.
3 citations
TL;DR: Iodination reactions of various phosphiniminocyclotrithiazenes [R3PNS3N3; R = (i) phenyl-, (ii) morpholino-, and (iii) p-chlorophenyl-] have been studied under different experimental conditions.
Abstract: Iodination reactions of various phosphiniminocyclotrithiazenes [R3PNS3N3; R = (i) phenyl-, (ii) morpholino-, and (iii) p-chlorophenyl-] have been studied under different experimental conditions. Iodination of Ph3PNS3N3 yields interesting products such as [(Ph3PN)2S3N3]I3, ((Ph3PN)3S)2I4, (Ph3PNH2)I3, ((Ph3PSI2)2I2, and [(Ph3PN)3SO]2I6 depending on the experimental conditions. All the products have been isolated and characterized by the spectroscopic and analytical techniques.
2 citations
References
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83 citations
TL;DR: The deformation electron density in sulfamic acid (H3NSO3) has been determined by a combined X-ray and neutron diffraction study at 78 K as discussed by the authors.
Abstract: The deformation electron density in sulfamic acid (H3NSO3) has been determined by a combined X-ray and neutron diffraction study at 78 K. X-N maps show strong bond populations in all bonds. The nature of the S--N and S O bonds is found to be similar to bonds between first-row atoms. The O atoms show single, fairly broad lone-pair peaks and are shifted towards the lone pairs in comparison with the neutron parameters. This shift disappears when only X-ray reflections with sin 0//1, > 0.85 A -1 are considered. A population analysis shows a net charge of +0.7 to +1.0 e on the S atom, -0 .3 to -0 .5 e on the O atoms and + 0.12 e on the H atoms, while the N atom is close to neutral.
65 citations
TL;DR: In this paper, a ring system containing Ferrocenyl Substituents is synthesized starting from FcPCl2 (1, FcPH2 (2), FcAsCl2(3) and Fe(C5H4A6H2)2 (4), which contains an eight-membered As2S2N4 ring.
Abstract: Ausgehend von FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) und Fe(C5H4AsCl2)2 (4) werden drei-, vier-, funf- und achtgliedrige Heterocyclen mit Ferrocenyl-Substitutenten synthetisiert (Fc = Ferrocenyl). Durch Umsetzung von 1 mit 2 in Gegenwart von DBU entsteht (FcP)n, das mit (Ph3P)2Pt(C2H4) zu (7) reagiert. Der analoge As2Pt-Ring 9 ist uber (FcAs)3 (8) in guter Ausbeute zuganglich. Die Reduktion von 1 mit LiAlH4 liefert (FcP)4 (10). Ein funfgliedriger Arsen-Schwefel-Heterocyclus, Fc2As2S3 (12), entsteht durch Umsetzung von FcAs=P(2,4,6-tBu3C6H2) (11) mit Schwefel. FcAsCl2 (3) reagiert mit Me3SiNSNSiMe3 zu FcAs(NSN)2AsFc (13), das einen achtgliedrigen As2S2N4-Ring enthalt. Dessen Komplexierung mit (Norbornadien)M(CO)4 fuhrt zu den Tetracarbonyl-Komplexen [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). Ein Arsenuberbrucktes Ferrocenophan 16 kann bei der Reaktion von Fe(C5H4Li)2 × TMEDA mit AsCl3 isoliert werden. Auch die Umsetzung von 4 mit Me3SiNSNSiMe3 liefert ein kondensiertes Ferrocenophan-Derivat der Zusammensetzung (C5H4)2FeAs2N6S4 (17). Die Molekulstrukturen von 13 und 17 wurden rontgenographisch bestimmt.
Inorganic Ring System Containing Ferrocenyl Substituents
Three-, four-, five-, and eight-membered heterocycles are synthesized starting from FcPCl2 (1), FcPH2 (2), FcAsCl2 (3) and Fe(C5H4AsCl2)2 (4) (Fc = Ferrocenyl). Treatment of 1 with 2 in the presence of DBU yields (FcP)n, which reacts with (Ph3P)2Pt(C2H4) to give (7). The corresponding As2Pt ring system 9 is available in high yield via (FcAs)3 (8). The reduction of 1 with LiAlH4 yields (FcP)4 (10). A five-membered arsenic sulfur heterocycle, Fc2As2S3 (12), is formed in the reaction of FcAs=P(2,4,6-tBu3C6H2) (11) with sulfur. FcAsCl2 (3) reacts with Me3SiNSNSiMe3 to give FcAs(NSN)2AsFc (13), which contains an eight-membered As2S2N4 ring. Its complexation with (norbornadiene)M(CO)4 leads to the tetracarbonyl complexes [FcAs(NSN)2AsFc]M(CO)4 (14, 15; M = Cr, Mo). An arsenic-bridged ferrocenophane 16 can be isolated from the reaction of Fe(C5H4Li)2 x TMEDA with AsCl3. The reaction of 4 with Me3SiNSNSiMe3 also produces a condensed ferrocenophane derivative, (C5H4)2FeAs2N6S4 (17). The molecular structures of 13 and 17 have been determined by X-ray diffraction.
56 citations