Formation of carbonylrhenium cryptates with alkali metal cations: Coordination chemistry studies of [Ph2P(E)NP(E)Ph2], E = O,S, Se towards ReBr(CO)5

Reaction of ReBr(CO)₅ with Li[Ph₂P(O)NP(O)Ph₂] afforded the cryptate Li[Re₂(CO)₆{μ-Ph₂P(O)NP(O)Ph₂-κ²O,O’}₃]; whereas K[Ph₂P(O)NP(O)Ph₂] reacted with ReBr(CO)₅ to give K[Re₂(CO)₆{μ-Ph₂P(O)NP(O)Ph₂-κ²O,O′}{Ph₂P(O)NP(O)Ph₂-κ²O,O′}₂]. Other chalcogen ligands’ salts M[Ph₂P(E)NP(E)Ph₂], E = Se and S, M = K and Li gave dirhenium carbonyls with bromido and Ph₂P(E)NP(E)Ph₂, E = Se or S bridges upon reaction with ReBr(CO)₅.     

Determination of Spin-Spin Coupling Constants J(PP) on the Basis of 13C and 31p NMR Data

Abstract

The diphosphine dioxides Ph₂P (O) CH₂P (O)Ph₂.(I, Ph₂P(O)CH₂CH₂P(O)Ph₂ (II), Ph₂P(O)CH=CHP(O)Ph₂-cis (III), -trans (IV), [Ph₂P(O)] C=CH (V), [Ph₂P(O) 1₂C=PPh₃ (VI), and also non-symmetric Ph₂(P)OCH=CHP(O)PhEt-trans (VII), Et²P(O)CH=CHP(O)PhEt-trans (VIII), have been studied in CH²C1₂ and CHCl₃ solutions by means of ¹³C and ³¹P NMR.     

Potassium tetraphenylimidodiphosphinate complex of 1,4,7,10,13,16-hexaoxacyclooctadecane an inorganic (carbon-free) chelate ring

Summary Potassium tetraphenylimidodiphosphinate, [K][Ph ₂P(O)NP(O)Ph ₂], reacts with 18-crown-6 ether to give the monohydrated complex [K(18-crown-6][Ph ₂P(O)NP(O)Ph ₂]·H₂O. The compound shows an interaction potassium-oxygen, forming an inorganic (carbon free) chelate ring and it is different to the sulphur homolog which has no interaction cation-anion.

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Kaliumtetraphenylimidodiphosphinat-Komplex von 1,4,7,10,13,16-Hexaoxacyclooctadecan. Ein anorganischer (Kohlenstoff-freier) Chelat-Ring

Zusammenfassung Kaliumtetraphenylimidodiphosphinat, [K][Ph ₂P(O)NP(O)Ph ₂], reagiert mit 18-Krone-6-ether unter Ausbildung des mohydydratisierten Komplexes [K(18-Krone-6)][Ph ₂P(O)-NP(O)Ph ₂]. Die Verbindung zeigt eine Kalium-Sauerstoff-Wechselwirkung under Formierung eines anorganischen (Kohlenstoff-freien) Chelat-Ringes. Dies ist im Gegensatz zum Schwefel-Analogen, das keine Kation-Anion-Wechselwirkung zeigt.

     

Nature of the complexes formed by alkali metal halides with phosphine oxides

Reaction of alkali metal halides (MX) with methylenediphosphine oxides and various related compounds in nonaqueous solutions leads to the formation of complex compounds. The compositions, properties, and stabilities of these compounds, which have been studied in detail in acetonitrile, are determined by the nature of the cations and anions of the alkali metal halides. Formation of neutral complexes with the composition [MX · L] and cationic complexes with the composition [ML]⁺ has been established. The most characteristic representative of complexes of the first type is [NaI · L]; in the complexes studied, L=R₂P(O)CH₂P(O)R₂ (R=Bu, BuO, or Ph), Ph₂P(O)CH₂P(O) (OC₂H₅)CH₂P(O)Ph₂ and (p-OCH₃C₆H₄)₂P(O)CH₂P(O)(C₆H₄CF₃-p)₂. Compound [LiL]⁺ is characteristic of complexes of the second type; the compounds containing Ph₃P(O), Ph₂P(O)CH₂P(O)Ph₂, and Ph₂P(O)CH₂P(O)(OC₂H₅)CH₂P(O)Ph₂ as ligands have been studied. Stability constants of the complexes [NaI · L] and [LiL]⁺ have been determined by measuring the dependence of the electrical conductivity of solutions of the alkali metal halides in acetonitrile on the concentration of the ligands. The complex-forming power of phosphine oxides increases with increase in the number of P=O groups. Stabilities of the complexes [NaI · L] with ligands with identical structure decrease with increase in the electronegativity of the substituents on the phosphorus atoms.     

Zur Reaktion von Triphenylphosphan mit Thionylchlorid

Triphenylphosphine reacts with thionyl chloride to give [Ph₃PCl]Cl, Ph₃PO and Ph₃PS the formation of the anions S(O)Cl and SCl being discussed; the crystal structure of [Ph₃PCl]Cl · S(O)Cl₂ is reported.     

Application of electrochemical impedance spectroscopy for characterisation of the reduction of benzophenone in acetonitrile solutions

In this study, the reduction of benzophenone (Bzph) Ph₂C=O (Ph: phenyl group) on glassy-carbon electrode was studied in acetonitrile by means of cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Bzph undergoes two one-electron reductions. The first reduction leads to the formation of radical anion [Ph₂·–O]^? and appears to be reversible and diffusion controlled. The second reduction results in the generation of benzhydrol dianion [Ph₂C–O]^2? and seems to be irreversible. A third quasi-reversible wave observable at more anodic potentials can be ascribed to benzhydrol free radical [Ph₂CH–O] and benzydrol anion [Ph₂CH–O]^? redox couple. The EIS spectra demonstrate that the first reversible reduction of Bzph is characterised by the lowest charge transfer resistance while the resistance for the irreversible reduction is significantly greater. The electrochemical behaviour of Bzph on film consisting of multi-walled carbon nanotubes seems to be different. Thus, the findings reveal slower electrode kinetics which can be associated with electrode passivation.     

[Ph2P(O)CH2Im][F3B(μ‐OH)BF3]. Erste strukturanalytische Charakterisierung des Hexafluoro(μ‐hydroxo)diborat‐Ions [1]

[Ph₂P(O)CH₂Im][F₃B(μ‐OH)BF₃]. First Structural Characterization of the Hexafluoro(μ‐hydroxo)diborate Ion [1] The hexafluoro(μ‐hydroxo)diborate ion has been isolated as it's Ph₂P(O)CH₂Im salt [Im = 2‐(1, 3, 4, 5‐tetramethylimidazolio)] ( 2 ) through basic hydrolysis of [Ph₂P(OBF₃)CH₂Im]BF₄ ( 1 ). The crystal structure of 2 · CH₂Cl₂ reveals the presence of ion pairs linked by unsymmetrical O‐H‐O hydrogen bonds.     

Der Einfluß von Phosphoryl‐Substituenten auf die Eigenschaften P‐substituierter 2‐Methylimidazolium‐Ionen und 2‐Methylenimidazoline [1]

The Influence of Phosphoryl Substituents on the Properties of P‐Substituted 2‐Methylimidazolium Ions and 2‐Methyleneimidazolines [1] The imidazolines ImCHP(E)Ph₂ [ 6 , E = S ( a ), Se ( b )] are obtained from ImCHPPh₂ ( 4 ) and sulfur or selenium. HBF₄ reaction yields the corresponding imidazolium salts [ImCH₂P(E)Ph₂][BF₄] [ 5 , E = S ( a ), Se ( b )]. 1, 3, 4, 5‐Tetramethyl‐2‐methylenimidazoline ( 1 , ImCH₂) reacts with Ph₂P(O)Cl to give the corresponding phosphane salt [ImCH₂P(O)Ph₂]Cl ( 7 ) from which the vinyl compound ImCHP(O)Ph₂ ( 8 ) is formed through deprotonation. 8 reacts with excess HBF₄ to give the phosphine oxide BF₃ adduct [ImCH₂P(O)Ph₂ · BF₃][BF₄] ( 9 ). The crystal structures of 5a , 5b , 6b , 7 · CH₂Cl₂ and 9 · H₂O as well as preliminary data of 8 are reported and discussed on comparison with the phosphanes [ImCH₂PPh₂][BF₄] ( 3b ) and ImCHPPh₂ ( 4 ). From structural data, π‐electron delocalisation is concluded for 6b and 8 .     

Syntheses,structures and catalytic properties of new mononuclear terpyridine-manganese(II) complexes with tetraphenylimido-diphosphinate and diphenylphosphinate ligands

Treatment of manganese(II) acetate tetrahydrate [Mn(CH3COO)₂·4H₂O] with one equivalent of 2,2′:6′,2′′-terpyridine (terpy) and two equivalents of potassium tetraphenylimido-diphosphinate K[N(Ph₂PO)₂] in methanol afforded a mononuclear manganese(II) complex, [(terpy)Mn{η¹-O-N(Ph₂PO)₂}₂(H₂O)] (1), with two terminal [N(Ph₂PO)₂]– ligands. Interaction of [Mn(CH₃COO)₂·4H₂O] with one equivalent of terpy in the presence of both K[N(Ph₂PO)₂] and Ph₂PO₂K in methanol gave a mononuclear manganese(II) complex [(terpy)Mn(η¹-O-O₂PPh₂){N(Ph₂PO)₂}] (2) with a chelated [N(Ph₂PO)₂]– ligand. Treatment of manganese(II) dichloride tetrahydrate [MnCl₂·4H₂O] with three equivalents of K[N(Ph₂PO)₂] in methanol resulted in isolation of a mononuclear manganese(III) complex [Mn{η¹-O-N(Ph₂PO)₂}-{N(Ph₂PO)₂}₂] (3) with one terminal and two chelated [N(Ph₂PO)₂]– ligands. Reaction of [Mn(CH₃COO)₂·4H₂O] with one equivalent of 4′-phenyl-[2,2′:6′,2′′]-terpyridine (4-Ph-terpy) and two equivalents of Ph₂PO₂K in methanol gave [(4-Ph-terpy)Mn(η¹-O-O₂PPh₂)₂(H₂O)] (4) with a labile water molecule. Complexes 1–4 have been spectroscopically characterized and their structures have been established by single-crystal X-ray diffraction. Catalytic behavior of 1 and 4 for sulfide oxidation was also investigated.     

Structurally different divalent metallasiloxanes [Mg{O(Ph2SiO)2}2]-μ-(LiPy)-μ-{(LiPy)3(OH)(Cl)}], [Cr{O(Ph2SiO)2}-μ-(LiPy2)2], and [{O(Ph2SiO)2}Co{O(Ph2SiO)3)}-μ-(LiPy2)2] from Ph2Si(OH)2/2BuLi and the metal dichlorides

Three structurally different metallasiloxanes were formed from reactions between in situ generated suspensions of Ph₂Si(OH)₂/BuLi (1∶2) in tetrahydrofuran (THF) with, metal dichlorides MgCl₂·2THF, CrCl₂, or CoCl₂ followed by toluene/Py (Py=pyridine) work-up. The X-ray structures are reported for: [Mg{O(Ph₂SiO)₂}₂]-μ-(LiPy)-μ-{(LiPy)₃(OH)(Cl)] (1) incorporating two six-membered magnesiasiloxane rings and an MgLi₃O₃Cl cubane fragment, [{O(Ph₂SiO)₂}Co{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] (2) with both six-and eight-membered cobaltasiloxane rings and [Cr{O(Ph₂SiO)₂}₂-μ-(LiPy₂)₂] (3) with two six-membered chromiasiloxane rings. Structure assembly in these cases is apparently dictated by the metal dichloride. The compound [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(CoClPy)₂]·Py (4) is formed from [{O(Ph₂SiO)₂}Mg{O(Ph₂SiO)₃}-μ-(LiPy₂)₂] and CoCl₂ (1∶2).     

Germanium(II)‐, Zinn(II)‐ und Blei(II)‐Derivate des polycyclischen Alumosiloxans [Ph2SiO]8[Al(O)OH]4

Germanium(II)‐, Tin(II)‐ and Lead(II)‐Derivatives of the polycyclic Alumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ Five new derivatives of the polycyclic alumosiloxane [Ph₂SiO]₈[Al(O)OH]₄ have been synthesized by replacement of the protic hydrogen atoms on the hydroxy‐groups attached to the aluminium atoms by the divalent group 14 elements germanium, tin and lead. The compounds can be divided in those with one metal atom per alumosiloxane moiety, [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]M (M=Ge, Sn), and those with complete substitution of the protic hydrogen atoms by metal atoms like [Ph₂SiO]₈[AlO₂]₄M₂ (M= Sn, Pb). Always one element of the series Ge, Sn, Pb is missing in the two types of compounds. Crystal structure analyses of [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]₂M · 2 C₄H₈O₂ (M= Ge ( 1 ), Sn ( 2a )), [Ph₂SiO]₈[Al(O)OH]₂[AlO₂]₂Sn · 2 THF ( 2b ) and [Ph₂SiO]₈[AlO₂]₄M₂ (M= Sn ( 3 ), Pb ( 4 )) have been performed elucidating either polycyclic basket‐type ( 1 , 2a , 2b ) or closed polyhedral structures ( 3 , 4 ).     

Rhodium(I) phosphine complexes containing bidentate unsaturated thio ligands: II. Reactions with O2 and H2

The rhodium(I) complexes (Ph₃P)₂Rh[Me₂NC(S)NC(S)NMe₂], (Ph₃P)₂Rh[SC(S)NMe₂] and (Ph₃P)₂Rh[PhNC(S)NMe₂] react with O₂ to give 1/1 dioxygen adducts. In solution, trans-(Ph₃P)₂Rh(O₂)[Me₂NC(S)NC(S)NMe₂], cis- and trans-(Ph₃P)₂Rh(O₂)[SC(S)NMe₂] and cis- and trans-(Ph₃P)₂Rh(O₂)[PhNC(S)NMe₂] are observed. For (Ph₃P)₂Rh(O₂)[PhNC(S)NMe₂], there is a solvent effect on the initial cis—trans ratio and the rate of O=PPh₃ formation. In C₆H₆, O=PPh₃ formation from (Ph₃P)₂Rh(O₂)[PhNC(S)NMe₂] is inhibited by additional PPh₃.The reaction of (Ph₃P)₂Rh[Ph₂PC(S)NPh] with O₂ in the presence of additional PPh₃ gives O=PPh₃ and cis-(Ph₃P)₂Rh(O₂)[Ph₂P(O)C(S)NPh] as the only products. The same complex also can be prepared from (Ph₃P)₂Rh[Ph₂P(O)C(S)NPh] and O₂.Only (Ph₃P)₂Rh[PhNC(S)NMe₂] reacts with H₂ at room temperature to give (Ph₃P)₂RhH₂[PhNC(S)NMe₂], which is a catalyst for cyclohexene hydrogenation.     

Synthesis and conformational studies of palladium(II) complexes containing [PhP(O)NP(E)Ph]− (E=S or Se)

The ligands [Ph₂P(O)NP(E)Ph₂]⁻ (E=S I; E=Se II) can readily be complexed to a range of palladium(II) starting materials affording new six-membered Pd–O–P–N–P–E palladacycles. Hence ligand substitution reaction of the chloride complexes [PdCl₂(bipy)] (bipy=2,2′-bipyridine), [{Pd(μ-Cl)(L–L)}₂] (HL–L=C₉H₁₃N or C₁₂H₁₃N), [{Pd(μ-Cl)Cl(PMe₂Ph)}₂] or [PdCl₂(PR₃)₂] [PR₃=PPh₃; 2PR₃=Ph₂PCH₂CH₂PPh₂or cis-Ph₂PCH=CHPPh₂] with either I (or II) in thf or CH₃OH gave [Pd{Ph₂P(O)NP(E)Ph₂-O,E}(bipy)]PF₆, [Pd{Ph₂P(O)NP(E)Ph₂-O,E}(L–L)], [Pd{Ph₂P(O)NP(E)Ph₂-O,E}Cl(PMe₂Ph)] or [Pd{Ph₂P(O)NP(E)Ph₂-O,E} (PR₃)₂]PF₆ in good yields. All compounds described have been characterised by a combination of multinuclear NMR [31 P{1 H} and 1 H] and IR spectroscopy and microanalysis. The molecular structures of five complexes containing the selenium ligand II have been determined by single-crystal X-ray crystallography. Three different ring conformations were observed, a pseudo-butterfly, hinge and in the case of all three PR₃ complexes, pseudo-boat conformations. Within the Pd–O–P–N–P–Se rings there is evidence for π-electron delocalisation.     

ZUR KENNTNIS DES NATRIUMDIPHENYLPHOSPHINOFORMIATS Ph2PCOONa1

Abstract

Ph ₂ PCOONa 2, hergestellt dutch Reaktion von Ph₂PNa mit CO₂, wird in protischen Medien rasch unter Bildung von Ph₂PH and CO₂ hydrolysiert. Die Hydrolyse verlauft in Natronlauge sehr viel langsamer and es bilden sich zusätzlich geringe Mengen Ph₂P(O)O^? und HCOO^?, Aus 2 and stöchiometrischen Mengen RI bilden sich tertiäre Phosphine Ph₂PR (R[dbnd]Me, Et) während mit überschüssigem MeI das Phosphoniumsalz [Ph₂PMe₂]I erhalten wird. Ph₂PCOOMe, Ph₂PCOOSiMe₃ bzw. Ph₂PCSSNa wurden durch Umsetzung von 2 mit (MeO)₂SO₂, Me₃SiCl bzw. CS₂ synthetisiert. Ph₂P(O)ONa and Ph₂P(S)SNa entstanden bei der Reaktion von 2 mit O₂ oder S₈ in Benzol.

Concerning Sodiumdiphenylphosphinoformiate Ph2PCOONa¹.

Ph₂PCOONa 2, prepared from Ph₂PNa and CO₂, is readily hydrolyzed in protic media with formation of Ph ₂ PH and CO₂. Hydrolysis is much slower in NaOH and small quantities of Ph₂P(O)O^? and HCOO^? are additionally formed. Reactions of 2 with RI in stoichiometrical amounts gave tertiary phosphines Ph₂PR (R[dbnd]Me, Et) while the phosphonium compound [Ph₂PMe₂]I resulted from 2 and MeI in excess. Ph₂PCOOMe, Ph₂PCOOSiMe₃ or Ph₂PCSSNa were obtained from 2 and (MeO)₂SO₂, Me₃SiCl or CS₂. Ph₂P(O)ONa and Ph₂P(S)SNa were isolated when 2 was reacted with O₂ or S₈ in benzene.     

Synthesis and Characterization of Phosphinecarboxamide and Phosphinecarbothioamide,and Their Complexation with Palladium(II) Complex

Reactions of isocyanates/isothiocyanates with primary and secondary phosphines without solvent at room temperature afforded phosphinecarboxamide/phosphinecarbothioamide, respectively, in excellent yields. Furthermore, palladium complex Pd(COD)Cl₂ was allowed to react with Ph₂PC(O)NHPh (1a) to afford [Pd{Ph₂PC(O)NHPh-κP}₂Cl₂] (3). On the other hand, the reaction of Pd(COD)Cl₂ with 1 eq. of Ph₂PC(S)NHPh (2a) afforded [PdCl₂{Ph₂PC(S)NHPh-κP,S}] (4). In the case of a 1:2 molar ratio, [PdCl{Ph₂PC(S)NHPh-κP,S}{Ph₂PC(S)NHPh-κP}]Cl (5) was formed. The newly obtained compounds were fully characterized using multielement NMR measurements and elemental analyses. In addition, the molecular structures of Ph₂PC(O)NH(CH₂)₂Cl (1j), Ph₂PC(S)NHPh(4-Cl) (2c), and 3–5 were determined using single-crystal X-ray diffraction.     

Syntheses and Crystal Structures of Copper and Silver Complexes with the Ylide Ph3PCHP(O)PPh2 as Ligand

The reactivity of the hydrolysis product of hexaphenylcarbodiphosphorane, PPh₃CHP(O)Ph₂, towards different soft Lewis acids, such as CuI and Ag[BF₄] are reported. While CuI exclusively binds at the ylidic carbon atom, reaction of the silver cation in CH₂Cl₂ leads to proton abstraction from the solvent to give the cation [PPh₃CH₂P(O)Ph₂]⁺. Surprisingly, Ag⁺ replaces the methyl group of [PPh₃CHMeP(O)Ph₂]⁺ to produce a dimeric complex, in which Ag⁺ is coordinated to C and O forming an eight membered ring. The compounds were characterized by spectroscopic methods and X‐ray diffraction.     

The First Six-Membered “True” Heterocycle – Hydrogen-Bond-Assisted Ladder Formation in a KOCNPS Ring System

A ladder of alternating K₂S₂ and K₂O₂ rings exists in K[Ph₂P(S)NC(O)Ph]⋅MeOH, the first six-membered “true” heterocycle, in the solid state (see picture). A simple P–N bond-forming reaction between benzamide and Ph₂PCl gives the precursor Ph₂P(S)NHC(O)Ph, from which the potassium salt can be generated by reaction with KOtBu.     

Die Kristallstruktur des Oxophosphazens [Ph3PNPPh2NP(O)Ph2]

Crystal Structure of the Oxophosphazene [Ph₃PNPPh₂NP(O)Ph₂] Single crystals of [Ph₃PNPPh₂NP(O)Ph₂] were obtained as a by‐product from the synthesis of [NaNPPh₃]₆ as a result of partial hydrolysis. According to the crystal structure determination the compound forms a molecular structure with a PNPNP chain with PN distances between 155.3(6) and 159.8(5) pm and PNP bond angles of 143.2(4) and 140.7(4)°. Space group P1¯, Z = 2, lattice dimensions at 213 K: a = 922.7(1); b = 1040.1(1); c = 1908.0(1) pm; α = 90.55(1)°; β = 103.01(1)°; γ = 92.87(1)°; R = 0.0859.     

Polysulfonylamine. LXIX. Neuartige Pniktogendisulfonylamide: Synthese von Bismutdimesylamiden und Kristallstrukturen des zwölfgliedrigen Cyclodimers [Ph2BiN(SO2Me)2]2 und des ionischen Komplexes [H(OAsPh3)2]⊕(MeSO2)2N⊖

Polysulfonyl Amines. LXIX. Novel Pnictogen Disulfonylamides: Synthesis of Bismuth Dimesylamides and Crystal Structures of the Twelve-Membered Cyclodimer [Ph₂BiN(SO₂Me)₂]₂ and of the Ionic Complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? The novel bismuth(III or V) disulfonylamides Ph₂BiN(SO₂Me)₂ ( 1 ), PhBi[N(SO₂Me)₂]₂ ( 2 ), PhBi[N(SO₂Me)₂]Br ( 3 ), Bi[N(SO₂Me)₂]₂Cl ( 4 ), Bi[N(SO₂Me)₂]Cl₂ · 12-crown-4 ( 5 ) and Ph₃Bi[N(SO₂Me)₂]Cl ( 6 ) were obtained by acidolysis of Ph₃Bi with HN(SO₂Me)₂ (→ 1 ), by metathesis of AgN(SO₂Me)₂ with Ph₂BiCl (→ 1 ) or PhBiBr₂ (→ 2, 3 ), by condensation of BiCl₃ with Me₃SiN(SO₂Me)₂ (→ 4 ; in presence of 12-crown-4: → 5 ), or by oxidative addition of ClN(SO₂Me)₂ to Ph₃Bi (→ 6 ). Independently of the molar ratio employed, triphenylarsane oxide and dimesylamine form the crystalline 2/1 complex [H(OAsPh₃)₂]^⊕(MeSO₂)₂N^? ( 7 ). The crystal packing of 7 (monoclinic, space group C2/c) consists of discrete cations displaying crystallographic C_i symmetry and a strong O …? H …? O hydrogen bond (H atom located on a centre of symmetry, O …? O′ 241.2 pm, As? O …? O′ 120°, As? O 168.3 pm), and chiral anions with crystallographic C₂ symmetry (N? S 157.3 pm, S? N? S 122,9°). In the solid state, the bismuth(III) compound 1 (triclinic, space group P1 ) is a cyclodimer with crystallographic C_i symmetry, in which two Ph₂Bi^⊕ cations are connected through two (α-O, ω-O)-donating dimesylamide ligands to form a roughly twelve-membered [BiOSNSO]₂ ring (Bi? O 239.7 and 246.6, O? S 148.0 and 145.4, S? N 157.7 and 159.2 pm, Bi? O? S 126.6 and 127.5°). The bismuth atom adopts a pseudo-trigonal-bipyramidal geometry (O? Bi? O 165.4, C? Bi? C 93.0, O? Bi? C 83.8 to 86.5°). The essentially similar conformations of the discrete anion in 7 and of the bidentate bridging ligand in 1 are discussed in detail.     

Chloro­(μ‐6‐methyl­pyridine‐2‐carboxyl­ato)bis­(6‐methyl­pyridine‐2‐carboxyl­ato)triphenyl­chromium(III)­tin(IV) chloro­triphenyl­tin(IV)

The title compound, [CrSn(C₆H₅)₃(C₇H₆NO₂)₃Cl][Sn(C₆H₅)₃Cl(CH₄O)], was obtained from the reaction of Ph₃SnCl with the complex [Cr(C₇H₆NO₂)₃] in methanol. The structure contains [Ph₃SnCl(MeOH)] (A) and [Ph₃SnClCr(C₇H₆NO₂)₃] (B) mol­ecules. In mol­ecule A, the Sn atom of Ph₃SnCl is coordinated by one methanol mol­ecule. In mol­ecule B, the Sn atom of Ph₃SnCl is coordinated by one carboxyl­ate O atom of [Cr(C₇H₆NO₂)₃]. Mol­ecules A and B are connected through an O—H⋯O hydrogen bond between a carboxyl­ate O atom and the methanol OH group. Weak C—H⋯Cl inter­actions and O—H⋯O hydrogen bonds extend the components of (I) into a two‐dimensional network.