Schwefeldioxid als Ligand und Synthon. IX. Reaktionen von Cobaltcarbonylen mit Schwefeldioxid – Synthese und Charakterisierung von Alkoxysulfinyl-Cobaltcarbonyl-Komplexen

Sulfur Dioxide as Ligand and Synthon. IX. Reactions of Cobalt Carbonyls with Sulfur Dioxide – Synthesis and Characterization of Alkoxysulfinyl-Cobalt Carbonyl Complexes Reactions of phosphine substituted Co₂(CO)₈, (Ph₂P–(CH₂)_n–PPh₂: n = 1, dppm; n = 2, dppe; n = 3, dppp; n = 4, dppb), alkylcobalt carbonyls and alkoxycobalt carbonyls with sulfur dioxide have been investigated. The SO₂ containing cobalt complexes are characterized by means of I.R., ¹H-NMR, and mass spectra. Further on synthesis and properties of new alkoxysulfinylphosphine-cobalttricarbonyl complexes of the type ROS(O)Co(CO)₃PR₃¹ (R = Ph₃Si, Me; R¹ = Et, i-Pr, Ph) are described.     

Triphenylphosphan-Nickel(0)-Komplexe mit Isocyanid-Liganden — [(RNC)nNi(PPh3)4–n] (n = 1–3)

Triphenylphosphane Nickel(0) Complexes with Isocyanide Ligands — [(RNC)_nNi(PPh₃)_4–n] (n = 1–3) Synthesis and properties of the isocyanide triphenylphosphane nickel(0) complexes [(RNC)Ni(PPh₃)₃], [(RNC)₂Ni(PPh₃)₂] and [(RNC)₃Ni(PPh₃)] (R = ^tBu, Cy, PhCH₂, p-TosCH₂) are described. I.r. and ³¹P n.m.r. spectra were recorded and the X-ray crystal structure of [(PhCH₂NC)₂Ni(PPh₃)₂] was determined.     

Tris(triphenylphosphan)nickel(0)-Komplexe mit Nitril-Liganden

Tris(triphenylphosphane)nickel(0) Complexes with Nitrile Ligands . Synthesis, properties and reaction behaviour of (Ph₃P)₃Ni(η¹-NCR) (R = PhCH₂, 2-MeC₆H₄, Me₃Si) complexes as well as the X-ray structure of (Ph₃P)₃Ni(η¹-NCSiMe₃) are described. With NC(CH₂)_nBr (n = 1, 2) instead of the analogous nitrile complexes (Ph₃P)₂NiBr₂ and CH₃CN or C₂H₅CN respectively are formed.     

Bis(diphenylphosphano)alkan- und 1-(Diphenylphosphano)-2-(2-pyridino)ethan-N-Arylsulfinylamin-Nickel(0)-Komplexe

Bis(diphenylphosphano)alkane- and 1-Diphenylphosphano-2-(2-pyridino)ethane-N-arylsulfinylamine Nickel(0) Complexes Synthesis and properties of the bis(diphenylphosphano)alkane-N-phenyl-sulfinylamine-nickel(0) complexes [Ni{Ph₂P(CH₂)_nPPh₂}(PhNSO)] (n = 2 dppe, n = 3 dppp, n = 4 dppb) as well as of the 1-(diphenylphosphano)-2-(2-pyridino)ethane nickel(0) complexes [Ni(dpppe)₂], [Ni(dpppe)(p-TolNSO)] and [Ni(dpppe)(PPh₃)₂] are described. These compounds have been characterized by i. r. and ³¹P n.m.r. spectroscopy. The N-arylsulfinylamine ligands are η²-(N, S)-side on coordinated.     

Schwefeldioxid als Ligand und Synthon. II. Synthese und Reaktionen der Trimethylsilyl-methansulfinsäure und ihrer Derivate

Sulfur Dioxide as Ligand and Synthon. II. Synthesis and Reaction of Trimethylsilyl Methane Sulfinic Acid and its Derivatives Synthesis and reaction of trimethylsilyl methane sulfinic acid and its derivatives, of the type Me₃SiCH₂S(O)? Y (Y = OH, OM, OR, NR₂) synthesized by insertion of SO₂ and R¹NSO, respectively, into Me₃SiCH₂MgCl are described. The compounds obtained are characterized by means of i.r., ¹H, ²⁹Si, and ¹³C n.m.r. spectroscopy.     

Bis(triphenylphosphan)Palladium-Komplexe mit Schwefeloxid-Liganden

Bis(triphenylphosphine)Palladium Complexes with Sulfur Oxide Ligands New examples in the series of sulfur oxide complexes of the type (PPh₃)₂Pd(S_nO_m) (n = 1,2; m 1–4) were found by the synthesis of (PPh₃)₂Pd(SO) and (PPh₃)₂Pd(S₂O₃. The SO complex is obtained by the reaction of Pd(PPh₃)₄ or (PPh₃)₂Pd(RCCR) (R=COOMe) and thiirane-S-oxide. The thiosulfato complex (PPh₃)₂Pd(S₂O₃) is formed from (PPh₃)₂Pd(SO) and SO₂ or, alternatively, from (PPh₃)₃Pd(SO₂) and C₂H₄SO. Both SO und SO₂ complexes can be oxidized to the corresponding sulfato compound (PPh₃)₂)Pd(SO₄). The SO complex is used as a SO-source for the formation of 3,4-dimethyldihydrothiophene-S-oxide from 2,3-dimethyl-1,3-butadiene.     

Neue neutrale und kationische Mono‐Aziridin‐Komplexe des Typs [CpMn(CO)2Az], [CpCr(NO)2Az]+ und [(Ph3P)(CO)4ReAz]+ über CO‐, Hydrid‐ und Chlorid‐Abspaltungsreaktionen

Novel Neutral and Cationic Mono‐Aziridine Complexes of the Type [CpMn(CO)₂Az], [CpCr(NO)₂Az]⁺, and [(Ph₃P)(CO)₄ReAz]⁺ via CO‐, Hydride‐, and Chloride‐Elimination Reactions The monoaziridine complexes 1 — 5 are obtained by three differently induced substitution reactions. The photolytically induced CO substitution reaction of [CpMn(CO)₃] with 2, 2‐dimethylaziridine leads to the neutral N‐coordinate aziridine complex [Cp(CO)₂Mn{$\overline{N(H)CMe₂C}$ H₂}] ( 1 ). The protonation of [(Ph₃P)(CO)₄ReH] with CF₃SO₃H and consecutive treatment with 2, 2‐dimethylaziridine or 2‐ethylaziridine gives the salt‐like aziridine complexes [(Ph₃P)(CO)₄Re{$\overline{N(H)CMe₂C}$ H₂}](CF₃SO₃) ( 2 ) or [(Ph₃P)(CO)₄Re{ H₂}](CF₃SO₃) ( 3 ) by hydride elimination reactions. The like‐wise salt‐like complexes [Cp(NO)₂Cr{$\overline{N(H)CMe₂C}$ H₂}](BF₄) ( 4 ) and [Cp(NO)₂Cr{ H₂}](CF₃SO₃) ( 5 ) are synthesized from [CpCr(NO)₂Cl] by chloride elimination with AgX (X = BF₄, CF₃SO₃) in the presence of 2, 2‐dimethylaziridine or 2‐ethylaziridine, respectively. As a result of X‐ray structure analyses, the metal atoms are trigonal pyramidally ( 1, 4, 5 ) or octahedrally ( 2, 3 , cis‐position) configurated; the intact three‐membered rings coordinate through the distorted tetrahedrally configurated N atoms. All compounds 1‐5 are stable with respect to the directed thermal alkene elimination to give the corresponding nitrene complexes; the IR, ¹H‐ and ¹³C{¹H}‐NMR, and MS spectra are reported and discussed.     

Zur Oxydation von Nickel(0)-Komplexen mit Halogenverbindungen des Kobalt(II), Kupfer(II) und Zink(II)

Oxidation of Nickel(0) Complexes by Halogen Compounds of Cobalt(II), Copper(II), and Zine(II) In aceton as a solvent Ni(PPh₃)₄ is oxidized by; cobalt(II) complexes of the type (Ph₃P)₂CoX₂ to nickel(I) compounds. In the case of X = Cl (Ph₃P)₃NiCl and (Ph₃P)₃CoCl separately crystallize, while for X = Br the lattice compound CoNi(PPh₃)₆Br₂ and for X = I CoNi(PPh₃)₅I₂ are formed. CuBr₂ and Ni(PPh₃)₄ react to (Ph₃P)₂NiBr and (Ph₃P)_nCuBr. With (Ph₃P)₂ZnCl₂ also (Ph₃P)₃NiCl is formed But in this case the oxidant is hydrogen chloride originating from hydrolysis. The magnetic moments of the new compounds were measured and their vis and fir spectra compared with those of the simple compounds (Ph₃P)_nNiX (n = 2, 3) and (Ph₃P)₃CoX. The M–X stretching frequencies are assigned. The cobalt (I) complexes (Ph₃P)₃CoCl have identical (distorted tetrahedral) structures, but most probably the nickel (I) complexes have not.     

Chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ2P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate

The aminophosphane ligand 1‐amino‐2‐(diphenylphosphanyl)ethane [Ph₂P(CH₂)₂NH₂] reacts with dichloridotris(triphenylphosphane)ruthenium(II), [RuCl₂(PPh₃)₃], to form chloridobis[2‐(diphenylphosphanyl)ethanamine‐κ²P,N](triphenylphosphane‐κP)ruthenium(II) chloride toluene monosolvate, [RuCl(C₁₈H₁₅P)(C₁₄H₁₆NP)₂]Cl·C₇H₈ or [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]Cl·C₇H₈. The asymmetric unit of the monoclinic unit cell contains two molecules of the Ru^II cation, two chloride anions and two toluene molecules. The Ru^II cation is octahedrally coordinated by two chelating Ph₂P(CH₂)₂NH₂ ligands, a triphenylphosphane (PPh₃) ligand and a chloride ligand. The three P atoms are meridionally coordinated, with the Ph₂P– groups from the ligands being trans. The two –NH₂ groups are cis, as are the chloride and PPh₃ ligands. This chiral stereochemistry of the [RuCl(PPh₃){Ph₂P(CH₂)₂NH₂}₂]⁺ cation is unique in ruthenium–aminophosphane chemistry.     

Monometallic Ni0 and Heterobimetallic Ni0/AuI Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis

The tridentate chelate nickel complexes [(CO)Ni{(PPh₂CH₂)₃CMe}] ( 2 ), [(CO)Ni{(PPh₂CH₂CH₂)₃SiMe}] ( 6 ), and [Ph₃PNi{(PPh₂CH₂CH₂)₃SiMe}] ( 7 ), as well as the bidentate complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂PPh₂}] ( 3 ) and the heterobimetallic complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂Ph₂PAuCl}] ( 4 ), have been synthesized and fully characterized in solution. All ¹H and ¹³C NMR signal assignments are based on 2D‐NMR methods. Single crystal X‐ray structures have been obtained for all complexes. Their ³¹P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2 – 4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction.     

Phosphine (oxide)‐(thio) phenolate palladium complexes: Synthesis,characterization and (co)polymerization of norbornene

A series of palladium complexes ( 2a–2g ) ( 2a : [6‐^tBu‐2‐PPh₂‐C₆H₃O]PdMe(Py); 2b : [6‐C₆F₅–2‐PPh₂‐C₆H₃O]PdMe(Py); 2c : [6‐^tBu‐2‐PPh^tBu‐C₆H₃O]PdMe(Py); 2d : [2‐PPh^tBu‐C₆H₄O] PdMe(Py); 2e : [6‐SiMe₃–2‐PPh₂‐C₆H₃O]PdMe(Py); 2f : [2‐^tBu‐6‐(Ph₂P=O)‐C₆H₃O]PdMe(Py); 2g : [6‐SiMe₃–2‐(Ph₂P=O)‐C₆H₃S]PdMe(Py)) bearing phosphine (oxide)‐(thio) phenolate ligand have been efficiently synthesized and characterized. The solid‐state structures of complexes 2d , 2f and 2g have been further confirmed by single‐crystal X‐ray diffraction, which revealed a square‐planar geometry of palladium center. In the presence of B(C₆F₅)₃, these complexes can be used as catalysts to polymerize norbornene (NB) with relatively high yields, producing vinyl‐addition polymers. Interestingly, 2a /B(C₆F₅)₃ system catalyzed the polymerization of NB in living polymerization manner at high temperature (polydispersity index 1.07, M_n up to 1.5 × 10⁴). The co‐polymerization of NB and polar monomers was also studied using catalysts 2a and 2f . All the obtained co‐polymers could dissolve in common solvent.     

Darstellung und Kristallstrukturen von Dicyanamido(triphenylphosphan)gold(I) und Nitrosodicyanmethanido(triphenylphosphan)gold(I)

Preparation and Crystal Structures of Dicyanamido(triphenylphosphane)gold(I) and Nitrosodicyanomethanido(triphenylphosphane)gold(I) The coordination compounds [(Ph₃P)Au{N(CN)₂}] ( 1 ) and [(Ph₃P)Au{ONC(CN)₂}] ( 2 ) are obtained by the reaction of [Au(PPh₃)]NO₃ with Na[N(CN)₂] or K[ONC(CN)₂] in CH₂Cl₂. The compounds are characterized by IR spectroscopy and by crystal structure determination. 1 crystallizes triclinic in the space group P 1 with a = 930.16(4), b = 1011.89(13), c = 1118.35(16) pm, α = 115.327(10), β = 90.899(8), γ = 103.394(8)°, Z = 2. 2 crystallizes monoclinic in the space group P2₁/n with a = 832.59(10), b = 1139.30(16), c = 2078.9(4) pm, β = 99.84(2)°, Z = 4. The crystal structures of both compounds are built up by pairs of antiparallel oriented molecules with linear coordinated gold atoms and weak intermolecular Au–N‐interactions.     

Metallkomplexe von Farbstoffen. VI. Phosphan-Nickel-, Palladium- und Platin-Komplexe sowie Pentamethyl-cyclopentadienyl-Rhodium- und Iridium-Komplexe von Bis(2-hydroxyaryl)azo-Farbstoffen

Metal Complexes of Dyes. Phosphine-Nickel, Palladium, Platinum Complexes and Pentamethylcyclopentadienyl Rhodium and Iridium Complexes of 2,2′-Dihydroxyazoarenes The terdentate dianions of 2,2′-dihydroxyazobenzene (L¹H), 1-(2-hydroxy-4-nitrophenylazo)-2-naphthol (L²H), 1-(2-hydroxy-5-nitrophenylazo)-2-naphthol (L³H) and 1-phenyl-3-methyl-4-(2-hydroxy-5-nitrophenylazo)-5-pyrazolone (L⁴H) form with chloro bridged complexes [(R₃P)MCl₂]₂ (M = Pd, Pt; R = Ph, nBu), [(n⁵-C₅Me₅)MCl₂]₂ (M = Rh, Ir) and with (nBu₃P)₂NiCl₂ the metal dye complexes (R₃P)ML (M = Ni, Pd, Pt) and (C₅Me₅)ML (M = Rh, Ir). The structures of (Ph₃P)PtL¹ and (nBu₃P)PdL³ have been determined by X-ray diffraction. For the complexes (n⁵-C₅Me₅)ML (M = Rh, Ir) with asymmetric metal centers two diastereoisomers are detected by nmr spectroscopy which points to the ?hydrazone”? form of the azo ligand with a pyramidalized N-atom.     

Nickel nitrosyl complexes in a sulfur-rich environment: The first poly(mercaptoimidazolyl)borate derivatives

The diamagnetic nickel mononitrosyl complexes (Tm^R)Ni(NO) (R = Bu^t, p-Tol) and (Bm^R)Ni(PPh₃)(NO) (R = Me, Bu^t) have been readily prepared from Ni(PPh₃)₂(NO)Br and the appropriate Na(Tm^R) or Na(Bm^R) reagents, respectively. These species constitute the first nickel nitrosyl complexes supported by these ligand systems. An X-ray diffraction study of (Tm^p-Tol)Ni(NO) confirmed its pseudo-tetrahedral geometry and the presence of a nearly linear nitrosyl ligand. In contrast, (Bm^Me)Ni(PPh₃)(NO) can be best described as having a trigonal pyramidal geometry, a spatial arrangement unprecedented in nickel nitrosyl chemistry, which is facilitated by the disposition of the Bm^Me ligand and the presence of a weak intramolecular Ni?H–B interaction opposite to the apical triphenylphosphine ligand.     

Interconversion of Molybdenum Imido and Amido Complexes by Proton‐Coupled Electron Transfer

Interconversion of the molybdenum amido [(^PhTpy)(PPh₂Me)₂Mo(NHtBuAr)][BArF²⁴] (^PhTpy=4′‐Ph‐2,2′,6′,2“‐terpyridine; tBuAr=4‐tert‐butyl‐C₆H₄; ArF²⁴=(C₆H₃‐3,5‐(CF₃)₂)₄) and imido [(^PhTpy)(PPh₂Me)₂Mo(NtBuAr)][BArF²⁴] complexes has been accomplished by proton‐coupled electron transfer. The 2,4,6‐tri‐tert‐butylphenoxyl radical was used as an oxidant and the non‐classical ammine complex [(^PhTpy)(PPh₂Me)₂Mo(NH₃)][BArF²⁴] as the reductant. The N?H bond dissociation free energy (BDFE) of the amido N?H bond formed and cleaved in the sequence was experimentally bracketed between 45.8 and 52.3 kcal mol^?1, in agreement with a DFT‐computed value of 48 kcal mol^?1. The N?H BDFE in combination with electrochemical data eliminate proton transfer as the first step in the N?H bond‐forming sequence and favor initial electron transfer or concerted pathways.     

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

A study regarding coordination chemistry of the bis(diphenylphosphino)amide ligand Ph₂P‐N‐PPh₂ at Group 4 metallocenes is presented herein. Coordination of N,N‐bis(diphenylphosphino)amine ( 1 ) to [(Cp₂TiCl)₂] (Cp=η⁵‐cyclopentadienyl) generated [Cp₂Ti(Cl)P(Ph₂)N(H)PPh₂] ( 2 ). The heterometallacyclic complex [Cp₂Ti(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Ti ) can be prepared by reaction of 2 with n‐butyllithium as well as from the reaction of the known titanocene–alkyne complex [Cp₂Ti(η²‐Me₃SiC₂SiMe₃)] with the amine 1 . Reactions of the lithium amide [(thf)₃Li{N(PPh₂)₂}] with [Cp₂MCl₂] (M=Zr, Hf) yielded the corresponding zirconocene and hafnocene complexes [Cp₂M(Cl){κ²‐N,P‐N(PPh₂)₂}] ( 4 Zr and 4 Hf ). Reduction of 4 Zr with magnesium gave the highly strained heterometallacycle [Cp₂Zr(κ²‐P,P‐Ph₂P‐N‐PPh₂)] ( 3 Zr ). Complexes 2 , 3 Ti , 4 Hf , and 3 Zr were characterized by X‐ray crystallography. The structures and bondings of all complexes were investigated by DFT calculations.     

Preparation and crystallographic characterization of Pd(II) complexes containing imidobis(diphenylthiophosphinato) ligand

The reactions of PdCI₂(L-L) [L-L = Ph₂PCH₂PPh₂(dppm), Ph₂PCH₂CH₂PPh₂(dppe) and Ph₂PCH₂CH₂CH₂PPh₂(dppp)] with equivalent amount of (Ph₂P(S)NHP(S)Ph₂)(dppaS₂) gave the complexes [Pd(L-L)(dppaS₂-H)]ClO₄ [L-L = dppm (1), dppe (2), dppp (3)]. The different synthetic route was used for complex 2 by using of Pd(dppe)Cl₂ and K[N(PSPh₂)₂] as starting materials (2a). All of these complexes have been characterized ³¹P{¹H} NMR, IR and elemental analyses. The complexes 2, 2a and 3 were crystallographically characterized. The coordination geometry around the Pd atoms in these complexes distorted square planar. Six membered dppaS₂-H rings are twist boat conformations in three complexes.     

Platinum group metal functionalized phosphine complexes. Part 2. Phosphinoamide rhodium(I), iridium(I), palladium(II) and platinum(II) complexes

Summary Rhodium(I), iridium(I), palladium(II) and platinum(II) complexes of the phosphinoamide ligands, Ph₂PCH₂CONHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized by using conductivity data, i.r., ¹H and ³¹P(H) n.m.r. spectral data. Reaction of the ligands with MCl(PPh₃)₃ and MCl(CO)(PPh₃)₂ (M = Rh, Ir) in CH₂Cl₂ under reflux lead to the formation of MCl(PPh₃)₂ [Ph₂PCH₂C(O)NHR] and MCl(CO)(PPh₃)[Ph₂PCH₂–C(O)HNR] respectively. The reaction of either K₂MCl₄ or cis-MCl₂(PPh₃)₂ affords complexes of the type cis-MCl₂[Ph₂PCH₂C(O)NHR]₂ (M = Pd, Pt). A similar product results even from the reaction of phosphinoamides with cis-platin. Possible structures are proposed for the complexes based on their physicochemical data     

Neue Untersuchungen zum Reaktionsverhalten von Triorganylcyclotriphosphanen. Die Kristallstrukturen von [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)6(μ2-CO)3{(PtBu)2}2] und [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)]–

New Research of Reaction Behaviour of Triorganylcyclotriphosphines. The Crystal Structures of [(PPh₃)₂Pt(P^tBu)₃], [(PPh₃)₂Pd(P^tBu)₂], [(CO)₄Cr{(PⁱPr)₃}₂], [RhCl(PPh₃)(P^tBu)₃], [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂], and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– By the reaction of triorganylcyclotriphosphines with transition metal complexes single- and polynuclear compounds are formed, in which the cyclophosphines are bonded in different ways to the metal, the ring either preserving structure or under going ring opening. Depending on the reaction conditions the following compounds can be characterized: [(PPh₃)₂Pt(P^tBu)₃] ( 1 ), [(PPh₃)₂Pd(P^tBu)₂] ( 2 ), [(CO)₄Cr{(PⁱPr)₃}₂] ( 3 ), [RhCl(PPh₃)(P^tBu)₃] ( 4 ), [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂] ( 5 ) and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– ( 6 ). The structures of 1 – 6 were obtained by X-ray single crystal structure analysis ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1279.6(3) pm, b = 1733.1(4) pm, c = 2079.1(4) pm, β = 90.20(3)°; 2 : space group P2₁/c (No. 14), Z = 4, a = 1053.3(2) pm, b = 2085.2(4) pm, c = 1855.7(4) pm, β = 98.77(3)°; 3 : space group P 1 (No. 2), Z = 2, a = 1022.6(2) pm, b = 1026.4(2) pm, c = 1706.0(3) pm, α = 82.36(3)°, β = 86.10(3)°, γ = 64.40(3)°; 4 : space group P 1 (No. 2), Z = 2, a = 980.2(2) pm, b = 1309.5(3) pm, c = 1573.4(3) pm, α = 99.09(3)°, β = 99.46(3)°, γ= 111.87(3)°; 5 : space group P2₁/c (No. 14), Z = 4, a = 1804.0(5) pm, b = 2261.2(6) pm, c = 1830.1(7) pm, β = 96.99(3)°; 6 : space group P2₁/c (No. 14), Z = 4, a = 943.2(3) pm, b = 2510.6(7) pm, c = 1325.1(6) pm, β = 98.21(3)°).