Quervernetzung lamellarer Schichten mit Hilfe von (O–H…O)‐Wasserstoffbrücken: Strukturen von M⊕⊖N(SO2C6H4‐4‐COOH)2 (M⊕ = K⊕, Rb⊕, Cs⊕)

Structures of Ionic Di(arenesulfonyl)amides. 4. Cross‐Linking Lamellar Layers by O–H…O Hydrogen Bonds: Structures of M^⊕⊖N(SO₂C₆H₄‐4‐COOH)₂ (M^⊕ = K^⊕, Rb^⊕, Cs^⊕) Syntheses and low‐temperature X‐ray crystal structures are reported for M^IN(SO₂C₆H₄‐4‐COOH)₂, where M = K (monoclinic, space group P2₁/c, Z = 4, Z′ = 1), M = Rb (monoclinic, P2₁, Z = 4, Z′ = 2), or M = Cs (monoclinic, P2₁/c, Z = 4, Z′ = 1). The three compounds are examples of layered inorgano‐organic solids where the inorganic component is comprised of metal cations and N(SO₂)₂ groups and the outer regions are formed by the 4‐carboxy substituted phenyl rings of the folded anions. In the two‐dimensional coordination networks, K^⊕ and Cs^⊕ adopt irregular and chemically distinct [MN₁O₇] octacoordinations, whereas the independent Rb^⊕ cations attain irregular nonacoordinations of type [RbN₂O₇] or [RbO₉] respectively. The crystal packings of the compounds are governed by self‐assembly of parallel layers through exhaustive hydrogen bonding between carboxylic acid groups, resulting in a dense array of cyclic (COOH)₂ motifs within the interlamellar regions.     

Synthese und Kristallstruktur von SMe3 ⊕[MoBr4(SMe2)2]−

Synthesis and Crystal Structure of SMe₃^⊕ [MoBr₄(SMe₂)₂]^? . The title compound is obtained from MoBr₄ and excess dimethyl sulfide, forming red crystals which are only slightly sensitive to moisture. Whereas the intermediately formed adduct of MoBr₄ and SMe₂ is unstable, the stable adduct [Mo(NO)₂Br₂(SMe₂)₂] can be prepared from Mo(NO)₂Br₂ and SMe₂. According to the structural analysis by X-ray methods, SMe₃ ^⊕[MoBr₄(SMe₂)₂]^? crystallizes orthorhombic in the space group Imma with eight formula units per unit cell, the cell dimensions being a = 1578, b = 2820, c = 856 pm (1303 observed, independent reflexions). The compound consists of S(CH₃)₃^⊕ cations with S? C bond lengths of 180 pm and C? S? C bond angles of 102° and 103° resp., and anions [MoBr₄(SMe₂)₂]^?. The molybdenum atom is coordinated octahedral by four bromine atoms in equatorial positions and the two S atomes of the SMe₂ donor molecules in axial sites with Mo? S bond lengths of 254 pm.     

N,N,N′,N′-Tetramethylethylendiamin-di(tert-butyl)aluminium-Kationen — Molekülstruktur des [(Me3C)2Al · TMEDA]⊕[(Me3C)2AlBr2]⊖

(N,N,N′,N′ -tetramethylethylendiamine) di(tert-butyl)aluminium Cations — Molecular Structure of [(Me₃C)₂Al(TMEDA)]^⊕[(Me₃C)₂AlBr₂]^? Dimeric di(tert-butyl)aluminium halides (Me₃C)₂AlX (X = Cl, Br) react with N,N,N′,N′ -tetramethylethylendiamine (TMEDA) to give three compounds: the salt-like [(Me₃C)₂Al(TMEDA)]^⊕[(Me₃C)₂AlX₂]^? 1 , characterized by crystal structure determination, and [(Me₃C)₂Al(TMEDA)]^⊕X^? 3 both with chelating amine, and the more covalent, pentane soluble (Me₃C)₂AlX(TMEDA) 2 with TMEDA bound by only one nitrogen atom. The reaction resembles the symmetrical and unsymmetrical cleavage of diborane(6). 3 (X = Cl) is also formed by treatment of 1 with boiling n-hexane in the presence of TMEDA over a period of 24 hours, while for X = Br the more covalent 2 is the main product under similar conditions. In solution 2 decomposes slowly yielding different products in dependency of the solvent: in benzene 3 and in n-pentane 1 are formed.     

S4N3⊕[ReCl4(NSCl)2]⊖ Synthese und Kristallstruktur

S₄N₃^⊕[ReCl₄(NSCl)₂]^?. Synthesis and Crystal Structure S₄N₃^⊕[ReCl₄(NSCl)₂]^? is formed as a byproduct in the reaction of Re₂(CO)₁₀ with excess trithiazyl chloride. The compound is characterized by a crystal structure analysis by X-ray methods. S₄N₃[ReCl₄(NSCl)₂] crystallizes in the noncentrosymmetric space group P2₁2₁2₁ with four formula units per unit cell and the lattice dimensions a = 980, b = 1205, c = 1362 pm (2376 observed, independent reflexions; R = 0.076). The compound consists of the well known cyclic planar S₄N₃^⊕-cations and anions [ReCl₄(NSCl)₂]^?, in which the rhenium atom is coordinated octahedral by four Cl atoms and two cis-positioned NSCl ligands. The mean Re? N and N? S bond lengths (177 pm and 158 pm) correspond to double bonds. The bond lengths and angles are much like in the structure of AsPh₄[ReCl₄(NSCl)₂]; however the chlorine atoms of the NSCl ligands are turned to each other.     

Zur Chemie der Chlorthionitrenkomplexe des Rheniums Die Kristallstruktur von [N(SCl)2]⊕ [Re2Cl9]⊖

Chemistry of Chlorothionitrene Complexes of Rhenium. Crystal Structure of [N(SCl)₂]⊕ [Re₂Cl₉]? By reaction of S₃N₂Cl₂ with ReCl₅ the chlorothionitrene complex [ReCl₃(NSCl)₂]₂ is obtained in good yield; it has a dimer structure with chloro bridges. By the same reaction in POCl₃ solution the solvate [ReCl₃(NSCl)₂OPCl₃] is obtained. Instead, when a molar ratio of ReCl₅ and S₃N₂Cl₂ of 2:1 is taken, the product is [N(SCl)₂][Re₂Cl₉]. [ReCl₄(NSCl)OPCl₃] and excess PPh₃ react to give the nitrido complex [ReNCl₂(PPh₃)₂]. The crystal structure of [N(SCl)₂][Re₂Cl₉] was determined and refined with X-ray diffraction data (1021 independent reflexions, R = 0.031). It crystalizes in the space group C2/c with four formula units per unit cell (a = 1197, b = 1288, c = 1144 pm, ß = 107.83°). The [N(SCl)₂]⊕ cations have exactly C₂ and approximately C_2v symmetry; the NS bond lengths of 162 pm and the bond angles SNS (133.6°) and NSCl (117.6°) deviate considerably from the values of known [N(SCl)₂]⊕ structures. The [Re₂Cl₉]? anion consists of two face sharing octahedra and has a Re—Re distance of 270 pm. I. r. spectra of all compounds are reported and discussed.     

Two tetranuclear zinc clusters, [Zn4(μ3‐OEt)2(μ2‐MalO)4Et2] and [Zn4(μ3‐GueO)2(μ2‐GueO)2(μ2‐MalO)2(MalO)2]·2C7H8, containing defective dicubane core geometries (MalOH is maltol and GueOH is guethol)

The zinc alkoxide molecules in di‐μ₃‐ethanolato‐diethyltetrakis(μ₂‐2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ³O³,O⁴:O³)tetrazinc(II), [Zn₄(C₂H₅)₂(C₂H₅O)₂(C₆H₅O₃)₄], (I), and bis(μ₃‐2‐ethoxyphenolato‐κ⁴O¹,O²:O¹:O¹)bis(μ₂‐2‐ethoxyphenolato‐κ³O¹,O²:O¹)bis(μ₂‐2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ³O³,O⁴:O³)bis(2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ²O³,O⁴)tetrazinc(II) toluene disolvate, [Zn₄(C₆H₅O₃)₄(C₈H₉O₂)₄]·2C₇H₈, (II), lie on crystallographic centres of inversion. The asymmetric units of (I) and (II) contain half of the tetrameric unit and additionally one molecule of toluene for (II). The Zn^II atoms are four‐ and six‐coordinated in distorted tetrahedral and octahedral geometries for (I), and six‐coordinated in a distorted octahedral environment for (II). The Zn^II atoms in both compounds are arranged in a defect dicubane Zn₄O₆ core structure composed of two EtZnO₃ tetrahedra and ZnO₆ octahedra for (I), and of four ZnO₆ octahedra for (II), sharing common corners. The maltolate ligands exist mostly in a μ₂‐bridging mode, while the guetholate ligands prefer a higher coordination mode and act as μ₃‐ and μ₂‐bridges.     

Destruktive Komplexierung des dimeren Diorganylzinn(IV)‐hydroxids [Me2Sn(A)(μ‐OH)]2 (HA = Benzol‐1,2‐disulfonsäureimid): Bildung und Strukturen der Einkernkomplexe [Me2Sn(A)2(OPPh3)2] und [Me2Sn(phen)2]2⊕ · 2 A⊖ · MeCN

Polysulfonylamines. CXVI. Destructive Complexation of the Dimeric Diorganyltin(IV) Hydroxide [Me₂Sn(A)(μ‐OH)]₂ (HA = Benzene‐1,2‐disulfonimide): Formation and Structures of the Mononuclear Complexes [Me₂Sn(A)₂(OPPh₃)₂] and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN Destructive complexation of the dimeric hydroxide [Me₂Sn(A)(μ‐OH)]₂, where A^⊖ is deprotonated benzene‐1,2‐disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10‐phenanthroline in hot MeCN produced, along with Me₂SnO and water, the novel coordination compounds [Me₂Sn(A)₂(OPPh₃)₂] ( 3 , triclinic, space group P 1) and [Me₂Sn(phen)₂]^2⊕ · 2 A^⊖ · MeCN ( 4 , monoclinic, P2₁/c). In the uncharged all‐trans octahedral complex 3 , the heteroligands are unidentally O‐bonded to the tin atom, which resides on a crystallographic centre of inversion [Sn–O(S) 227.4(2), Sn–O(P) 219.6(2) pm, cis‐angles in the range 87–93°; anionic ligand partially disordered over two equally populated sites for N, two S and non‐coordinating O atoms]. The cation occurring in the crystal of 4 has a severely distorted cis‐octahedral C₂N₄ coordination geometry around tin and represents the first authenticated example of a dicationic tin(IV) dichelate [R₂Sn(L–L′)₂]^2⊕ to adopt a cis‐structure [C–Sn–C 108.44(11)°]. The five‐membered chelate rings are nearly planar, with similar bite angles of the bidentate ligands, but unsymmetric Sn–N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N–Sn–N 71.24(7)°, Sn–N 226.81(19) and 237.5(2) pm; ring 2: 71.63(7)°, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively C_S symmetric A^⊖ ions have their five‐membered rings distorted into an envelope conformation, with N atoms displaced by 28–43 pm from the corresponding C₆S₂ mean plane.     

Dimeric Structure of [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2]

The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy)(η²‐NO₃)₂] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO₃) : terpy.; [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy) · (η²‐NO₃)₂] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N₀ = 2319.     

S5N5⊕[RuCl3(CO)3]⊖ · 0,5 CH2Cl2 Synthese,IR-Spektrum und Kristallstruktur

S₅N₅^⊕[RuCl₃(CO)₃]^⊖ · 0.5 CH₂Cl₂. Synthesis, I.R. Spectrum and Crystal Structure S₅N₅[RuCl₃(CO)₃] · 0.5 CH₂Cl₂ is prepared from Ru₃(CO)₁₂ and trithiazylchloride in boiling dichloromethane; it forms red crystals, which are characterized by it's IR spectrum and by structural determination with X-ray methods. The compound crystallizes monoclinic in the space group C2/c with 8 formula units per unit cell. The lattice dimensions are a = 2047, b = 1064, c = 1637 pm, β = 96.1° (3487 independent, observed reflexions, R = 0.075). The structure consists of planar, cyclic S₅N₅^⊕ cations in the “azulene” conformation with bond lengths SN from 155 to 159 pm, and octahedral [RuCl₃(CO)₃]^⊖ anions with fac-geometry and bond lengths Ru Cl of 242 pm and Ru C of 185 to 190 pm.     

Palladium(II) and Platinum(II) Complexes with Bisphosphanes, [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Chelating Ligands

The palladium(II) and platin(II) 1, 1‐dicyanoethylene‐2, 2‐dithiolates [(L–L)M{S₂C=C(CN)₂}] (M = Pd: L–L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L–L)MCl₂] and K₂[S₂C=C(CN)₂] or from [(PPh₃)₂M{S₂C=C(CN)₂}] and the bisphosphane. Moreover, [(dppe)Pt{S₂C=C(CN)₂}]was obtained from [(1, 5‐C₈H₁₂)Pt{S₂C=C(CN)₂}] and dppeby ligand exchange. The 1, 1‐dicyanoethylene‐2, 2‐diselenolates[(dppe)M{Se₂C=C(CN)₂}] (M = Pd, Pt) were prepared from[(dppe)MCl₂] and K₂[Se₂C=C(CN)₂]. The oxidation potentials of the square‐planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S₂C=O)] with TCNE led to a ligand fragment exchange and gave the 1, 1‐dicyanoethylene‐2, 2‐dithiolate [(dcpe)Pd{S₂C=C(CN)₂}] in good yield.     

Die ersten Röntgenstrukturen kationischer Diorganylzinn(IV)‐Dichelate [R2Sn(L–L)2]2⊕ mit zweizähnigen Phosphanoxid‐Liganden: Di(methansulfonyl)amid als nichtkoordinierendes Gegenion

Polysulfonylamines. CXI. The First X‐Ray Structures of Cationic Diorganyltin(IV) Dichelates [R₂Sn(L–L)₂]^2⊕ Involving Bidentate Phosphine Oxide Ligands: Di(methanesulfonyl)amide as a Non‐Coordinating Counter‐Ion The reaction of Me₂Sn(A)₂, where A^⊖ = (MeSO₂)₂N^⊖, with DPPOE = ethane‐1,2‐diylbis(diphenylphosphine oxide) or CDPPOET = cis‐ethene‐1,2‐diylbis(diphenylphosphine oxide) yields the ionic dichelates [Me₂Sn(dppoe)₂]^2⊕ · 2 A^⊖ ( 1 ; monoclinic, space group P2₁/c) and [Me₂Sn(cdppoet)₂]^2⊕ · 2 A^⊖ ( 2 ; monoclinic, P2₁/n). A solvated variety of 2 , [Me₂Sn(cdppoet)₂]^2⊕ · 2 A^⊖ · Et₂O · 0.15 MeCN ( 4 ; triclinic, P 1), was serendipitously obtained by thermal degradation of the new compound [Me₂Sn(A)(μ‐OH)]₂ · 2 CDPPOET in an MeCN/Et₂O medium. The crystals of 1 , 2 and 4 consist of discrete formula units (one independent unit for 1 and 2 , two independent units for 4 ); in the structure of 4 , the solvent molecules are located in lattice cavities. All the tin atoms lie on crystallographic inversion centres and display moderately distorted octahedral C₂O₄ coordinations with short Sn–O bonds in the range 218–223 pm. Within the formula units, the anions are connected to the P–CH donor groups of the chelating ligands by C–H…O/N interactions, some of which are remarkably short (e.g. in 1 : H…O 220 pm, C–H…O 170°; H…N 242 pm, C–H…N 153°).     

Kristallstrukturen der iso‐Thiocyanatoberyllate (Ph4P)2[Be(NCS)4] und (Ph4P)4[{Be2(NCS)4(μ‐NCS)2}{Be2(NCS)6(μ‐H2N2C2S2)}]

Bis(tetraphenylphosphonium) hexachloridodiberyllate, (Ph₄P)₂[Be₂Cl₆], reacts with excess trimethylsilyl‐iso‐thiocyanate to give a mixture of colourless single crystals of (Ph₄P)₂[Be(NCS)₄] ( 1 ) and (Ph₄P)₄[{Be₂(NCS)₄(μ‐NCS)₂}{Be₂(NCS)₆(μ‐H₂N₂C₂S₂)}] ( 2 ), which can be separated by selection. Both complexes were characterized by X‐ray diffraction. Compound 1 can be prepared without by‐products by treatment of (Ph₄P)₂[BeCl₄] with excess Me₃SiNCS in dichloromethane solution. 1 : Space group I4₁/a, Z = 4, lattice dimensions at 100(2) K: a = b = 1091.2(1), c = 3937.1(3) pm, R₁ = 0.0474. The [Be(NCS)₄]^2– ion of 1 forms tetragonally distorted tetrahedral anions with Be–N distances of 168.4(2) pm and weak intermolecular S ··· S contacts along [100] and [010]. 2 ·4CH₂Cl₂: Space group P , Z = 1, lattice dimensions at 100(2) K: a = 919.5(1), b = 1248.3(1), c = 2707.0(2) pm, α = 101.61(1) °, β = 95.08(1) °, γ = 94.52(1) °, R₁ = 0.103. Compound 2 contains two different anionic complexes in the ratio 1:1. In {Be₂(NCS)₄(μ‐NCS)₂}^2–, the beryllium atoms are connected by (NCS)^– bridging groups forming centrosymmetric eight‐membered Be₂(NCS)₂ rings with distances Be–N of 168(1) pm and Be–S of 235.2(9) pm. The second anion {Be₂(NCS)₆(μ‐H₂N₂C₂S₂)}^2– consists of two {Be(NCS)₃}^– units, which are linked by the nitrogen atoms of the unique dimeric cyclo‐addition product of HNCS with Be–N distances of 179(1) pm.     

S5N5⊕[GaCl4]⊖ und S5N5⊕[Ga2Cl7]⊖. Synthesen,IR-Spektren und Kristallstrukturen

S₅N₅ ^⊕[GaCl₄]^? and S₅N₅ ^⊕[Ga₂Cl₇]^?. Synthesis, IR Spectra, and Crystal Structures . S₅N₅[GaCl₄] was obtained in high yields from gallium and trithiazyl chloride; depending on the solvent, different second products are formed: S₄N₄Cl[GaCl₄] in dichloromethane and S₃N₂Cl[GaCl₄] in carbon tetrachloride. These products can be separated due to their high solubility in CH₂Cl₂, S₅N₅[GaCl₄] being only slightly soluble. S₃N₂Cl[GaCl₄] can be converted to S₅N₅[GaCl₄] with additional (NSCl)₃. By the action of GaCl₃ on S₅N₅[GaCl₄], S₅N₅[Ga₂Cl₇] is formed. The IR spectra of the title compounds are reported; they differ considerably as well in number as in frequencies of the cation bands and show that the S₅N₅^⊕ ion has different structures depending on the anion. The crystal structures of both compounds were determined by X-ray diffraction. Crystal data: S₅N₅[GaCl₄], orthorhombic, a = 943.8, b = 1369.0, c = 2068.8 pm, space group Pnma, Z = 8 (1381 observed reflexions, R = 0.075); S₅N₅[Ga₂Cl₇], monoclinic, a = 847.5, b = 1298.2, c = 1654.0 pm, β = 93.51°, space group P2₁/n, Z = 4 (1359 observed reflexions, R = 0.065). S₅N₅[GaCl₄] is isotypic with S₅N₅[AlCl₄], showing a heartshaped S₅N₅^⊕ ion, but large ellipsoids of vibration suggest the presence of some kind of disorder (statical or dynamical). In S₅N₅[Ga₂Cl₇] the S₅N₅^⊕ has an azulene-like structure. In both cases the cations are planar, all S? N bond lengths being approximately equal.     

Synthesen und Strukturen der polymeren Silber‐Komplexe [Ag2Cl2(dppbp)3]∞, [Ag2(SPh)2(dppe)3]∞ und [Ag2(SPh)2(triphos)]∞ sowie der Silber‐Chalkogenido‐Cluster [Ag7(SPh)7(dppm)3], {[Ag7(TePh)7(dppp)3]2(dppp)} und [Ag22Cl(SPh)10(PhCOO)11(dmf)3]∞

Syntheses and Structures of the Polymeric Silver Complexes [Ag₂Cl₂(dppbp)₃]_∞, [Ag₂(SPh)₂(dppe)₃]_∞ and [Ag₂(SPh)₂(triphos)]_∞ as well as the Silver Chalcogenido Clusters [Ag₇(SPh)₇(dppm)₃], {[Ag₇(TePh)₇(dppp)₃]₂(dppp)}, and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ The reaction of silver carboxylate with silylated chalcogen compounds have been found to have a possibility for the synthesis of metal‐chalcogenide‐custers. Especially phosphine ligands have been found to be useful in stabilising the cluster cores. Some of the silver carboxylate phosphine complexes, which are formed in‐situ, ([Ag₂Cl₂(dppbp)₃]_∞ ( 1 )) and some silver chalcogen complexes ([Ag₂(SPh)₂(dppe)₃]_∞ ( 2 ) und [Ag₂(SPh)₂(triphos)]_∞ ( 3 )), could be isolated and characterised by X‐ray diffraction. Using special reaction conditions, it is possible to isolate cluster species like [Ag₇(SPh)₇(dppm)₃] ( 4 ), {[Ag₇(TePh)₇(dppp)₃]₂(dppp)} ( 5 ) and [Ag₂₂Cl(SPh)₁₀(PhCOO)₁₁(dmf)₃]_∞ ( 6 ) beside the complex compounds. 1: Space group P2₁/n (No. 14), Z = 2, a = 1336, 1(2), b = 2081, 2(5), c = 2015, 4(4) pm, β = 99, 87(2)°; 2: Space group P2₁/n (No. 14), Z = 2, a = 1416, 1(3), b = 1874, 7(4), c = 1444, 8(3) pm, β = 93, 26(3)°; 3: Space group P2₁/n (No. 14), Z = 4, a = 1456, 8(3, b = 1890, 2(4), c = 1916, 1(4) pm, β = 99, 11(3)°; 4: Space group P2₁/n (No. 14), Z = 4, a = 1570, 2(3), b = 2798, 5(6), c = 2752, 7(6) pm, β = 98, 02(3)°; 5: Space group P1 (No. 2), Z = 2, a = 2115, 5(4), b = 2553, 3(5), c = 3188, 7(6) pm, α = 68, 87(3)°, β = 74, 05(3)°, γ = 69, 70(3)°; 6: Space group P1 (No. 2), Z = 2, a = 1583, 0(3), b = 1709, 6(3), c = 2990, 0(6) pm, α = 80, 41(3)°, β = 88, 86(3)°, γ = 71, 10(3)°).     

Polymorphism of [Zn(2,2′‐bipy)(H2PO4)2]2

Two polymorphs of a zero‐dimensional (molecular) zinc phosphate with the formula [Zn(2,2′‐bipy)(H₂PO₄)₂]₂ have been synthesized by a mild hydrothermal route and their crystal structures were determined by single crystal X‐ray diffraction (triclinic, space group (No. 2), Z = 2, α‐form: a = 8.664(1), b = 8.849(2), c = 10.113(2) Å, α = 97.37(2)°, β = 100.54(2)°, γ = 100.98(2)°, V = 737.5(3) ų; β‐form: a = 7.5446(15), b = 10.450(2), c = 10.750(2) Å, α = 67.32(3)°, β = 81.67(3)°, γ = 69.29(3)°, V = 731.4(3) ų). Both structures consist of distorted trigonal‐bipyramidal ZnO₃N₂ units condensed with PO₂(OH)₂ tetrahedra through common vertices giving rise to dimers [Zn(2,2′‐bipy)(H₂PO₄)₂]₂. The structures are stabilized by extensive inter‐ and intramolecular hydrogen bond interactions. Both modifications display subtle differences in their packing originating from the hydrogen bond interactions as well as π…π interactions between the organic ligands.     

Synthese und Kristallstrukturen der Seltenerd-Komplexe [LaI2(THF)5]+I3−, [SmCl3(THF)4], [ErCl2(THF)5]+ [ErCl4(THF)2]−, [ErCl3(DME)2] und [Na(18-Krone-6)(THF)2]+ [YbBr4(THF)2]−

Syntheses and Crystal Structures of the Rare-Earth Complexes [LaI₂(THF)₅]⁺I₃^?, [SmCl₃(THF)₄], [ErCl₂(THF)₅]⁺ [ErCl₄(THF)₂]^?, [ErCl₃(DME)₂], and [Na(18-Crown-6)(THF)₂]⁺[YbBr₄(THF)₂]^? [LaI₂(THF)₅]⁺I₃^? ( 1 ) is obtained as red crystals from lanthanum powder and 1,2-diiodoethane in THF on exposure to light. Space group Pbcn, Z = 4, lattice dimensions at ?83°C: a = 1264.9, b = 2218.9, c = 1199.1 pm, R = 0.031. The lanthanum atom of the cation of 1 is coordinated with iodine atoms in the axial positions in a pentagonal-bipyramidal way. [SmCl₃(THF)₄] ( 2 ) originates as colourless crystals on heating SmCl₃ with excess THF in the presence of Me₃SiNPEt₃. Space group P2₁/c, Z = 8, lattice dimensions at ?50°C: a = 3092.7, b = 826.2, c = 1758.3 pm, β = 93.85°, R = 0.054. Just like the known sample that crystallizes within the space group F2dd, 2 forms monomeric molecules in which the samarium atom is coordinated with two chlorine atoms in the axial positions in a distorted pentagonal-bipyramidal way. [ErCl₂(THF)₅]⁺[ErCl₄(THF)₂]^? ( 3 ). Pale pink single crystals of 3 were prepared according to the described method by reaction of erbium powder with trimethylchlorosilane and methanol in THF. Space group C2/c, Z = 4, lattice dimensions at ?50°C: a = 1246.3, b = 1145.7, c = 2726.0 pm, β = 91.293°, R = 0.036. The erbium atom of the cation of 3 has a pentagonal-bipyramidal coordination with the chlorine atoms in the axial positions. Within the anion the THF molecules are in trans-arrangement of the octahedrally coordinated erbium atom. [ErC1₃(DME)₂] ( 4 ) originates as pink single crystals from ₃ with excess boiling 1,2-dimethoxyethane. Space group P2₁/c, Z = 4, lattice dimensions at ?50°C: a = 1137.2, b = 886.5, c = 1561.1 pm, β = 104.746°, R = 0.032. 4 forms monomeric molecules in which the erbium atom has a pentagonal-bipyramidal surrounding with two chlorine atoms in the axial positions. [Na(18-Krone-6)(THF)₂]⁺ [YbBr₄(THF)₂]^? ( 5 ) is formed as by-product by the reaction of YbBr₃ with NaN(SiMe₃)₂ in THF in the presence-of 18-crown-6 forming colourless crystals. Space group P1 , Z = 1, lattice dimensions at ?70°C: a = 934.6, b = 988.9, c = 1208.0 pm, α = 73.82°, β = 72.98°, γ = 76.89°, R = 0.029. 5 contains isolated [YbBr₄(THF)₂]^?ions, in which the THF molecules are arranged in trans-position.     

Synthesis and X‐ray Structures of the Polycyclic Dimers {[PhB(μ‐NtBu)2AsN(tBu)H]LiI}2 and [PhB(μ‐NtBu)2AsN(tBu)Li]2

The metathesis of [PhB(μ‐NtBu)₂]AsCl and tBuN(H)Li in 1:1 molar ratio in diethyl ether produced the amido derivative [PhB(μ‐NtBu)₂AsN(tBu)H] ( 1 ) in good yield. The lithiation of 1 with one equivalent of nBuLi afforded the lithium salt [PhB(μ‐NtBu)₂AsN(tBu)Li] ( 2a ). Both 1 and 2a were characterized by multinuclear NMR spectroscopy. The crystal structure of 2a is comprised of a U‐shaped, centrosymmetric dimer in which the monomeric [PhB(μ‐NtBu)₂AsN(tBu)]^?Li⁺ units are linked by Li‐N interactions to give a six‐rung ladder. Oxidation of 2a with one‐half equivalent of I₂ in diethyl ether resulted in hydrogen abstraction from the solvent to give the dimeric lithium iodide adduct {[PhB(μ‐NtBu)₂AsN(tBu)H]LiI}₂ ( 1 ·LiI) with a central Li₂I₂ ring.     

Methanol[1‐(methoxymethanimidoyl)‐2‐(pyridin‐2‐ylmethyl)guanidine]bis(perchlorato)copper(II)

The title complex, [Cu(ClO₄)₂(C₉H₁₃N₅O)(CH₃OH)], was synthesized from a methanolysis reaction of N‐(methylpyridin‐2‐yl)cyanoguanidine (L³) and copper(II) perchlorate hexahydrate in a 1:1 molar ratio. The Cu^II ion is six‐coordinated by an N₃O₃ donor set which confers a highly distorted and asymmetric octahedral geometry. Three N‐donor atoms from the chelating 1‐(methoxymethanimidoyl)‐2‐(pyridin‐2‐ylmethyl)guanidine (L^3m) ligand and one O atom from the methanol molecule define the equatorial plane, with two perchlorate O atoms in the apical sites, one of which has a long Cu—O bond of 2.9074 (19) Å. The dihedral angle between the five‐ and six‐membered chelate rings is 8.21 (8)°. Two molecules are associated into a dimeric unit by intermolecular N—H...O(perchlorate) hydrogen bonds. Additionally, the weakly coordinated perchlorate anions also link adjacent [Cu(ClO₄)₂(L^3m)(CH₃OH)] dimers by hydrogen‐bonding interactions, resulting in a two‐dimensional layer in the (100) plane. Further C—H...O hydrogen bonds link the two‐dimensional layers along [100] to generate a three‐dimensional network.     

Synthesis and thermal decomposition reaction kinetics of complexes of [Sm2(m‐ClBA)6(phen)2] · 2H2O and [Sm2(m‐BrBA)6(phen)2] · 2H2O

Complexes of [Sm₂(m‐ClBA)₆(phen)₂] · 2H₂O and [Sm₂(m‐BrBA)₆(phen)₂] · 2H₂O (m‐ClBA = m‐chlorobenzoate, m‐BrBA = m‐bromobenzoate, and phen = 1,10‐phenanthroline) were prepared and characterized by elemental analysis and IR spectra. The thermal decomposition processes of the two complexes were studied by means of TG–DTG and IR techniques. Their thermal decomposition kinetics were investigated from the analysis of the TG and DTG curves by jointly using a new method proposed by us and a newly nonlinear isoconversional integral method. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 67–74, 2007     

Syntheses and characterizations of poly[2‐(dimethylamino)ethyl methacrylate]–poly(propylene oxide)–poly[2‐(dimethylamino)ethyl methacrylate] ABA triblock copolymers

A novel, near‐monodisperse, well‐defined ABA triblock copolymer, poly[2‐(dimethylamino)ethyl methacrylate]‐b‐poly(propylene oxide)‐b‐poly[2‐(dimethylamino)ethyl methacrylate], was synthesized via oxyanion‐initiated polymerization. The initiator was a telechelic‐type potassium alcoholate prepared from poly(propylene glycol) and KH in dry tetrahydrofuran. The copolymers produced were characterized by Fourier transform infrared, ¹H NMR, and gel permeation chromatography (GPC). GPC and ¹H NMR analyses showed that the products obtained were the desired copolymers, with narrow molecular weight distributions (ca. 1.09–1.11) very close to that of the original poly(propylene glycol). ¹H NMR, surface tension measurements, and dynamic light scattering all indicated that the triblock copolymer led to interesting aqueous solution behaviors, including temperature‐induced micellization and very high surface activity. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 624–631, 2002; DOI 10.1002/pola.10144