Über Reaktionen von Hexachlorodiberyllat mit Trimethylsilyl‐N‐dimethylamid. Die Kristallstrukturen von (Ph4P)3[Be2Cl5(OSiMe3)][BeCl3(Me2NSiMe3)], (Ph4P)[BeCl3(HNMe2)] und (Ph4P)(H2NMe2)[BeCl4]

On Reactions of Hexachlorodiberyllate with Trimethylsilyl‐N‐dimethylamide. Crystal Structures of (Ph₄P)₃[Be₂Cl₅(OSiMe₃)][BeCl₃(Me₂NSiMe₃)], (Ph₄P)[BeCl₃(HNMe₂)], and (Ph₄P)(H₂NMe₂)[BeCl₄] Reactions of bis‐tetraphenylphosphonium hexachlorodiberyllate, (Ph₄P)₂[Be₂Cl₆], with trimethylsilyl‐N‐dimethylamide under different conditions lead to the novel chloroberyllate derivatives (Ph₄P)₃[Be₂Cl₅(OSiMe₃)][BeCl₃(Me₂NSiMe₃)] ( 1 ), (Ph₄P)[BeCl₃(HNMe₂)] ( 2 ), and (Ph₄P)(H₂NMe₂)[BeCl₄] ( 3 ). 1 ‐ 3 were characterized by IR spectroscopy and crystal structure determinations. 1· 4CH₂Cl₂: Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1115.6(1), b = 2110.7(2), c = 2145.0(3) pm, α = 71.38(1)°, β = 85.66(1)°, γ = 85.24(1)°, R₁ = 0.0732. The [Be₂Cl₅(OSiMe₃)]^2— ion in the structure of 1 is derived from the [Be₂Cl₆]^2— ion by substitution of a μ‐Cl ligand by the oxygen atom of the (OSiMe₃)^— group. The second anion, [BeCl₃(Me₂NSiMe₃)]^—, can be described as donor acceptor complex with a short Be—N bond of 179(1) pm. 2 : Space group P1¯, Z = 2, lattice dimensions at 193 K: a = 1063.1(1), b = 1072.0(1), c = 1238.3(1) pm, α = 87.55(1)°, β = 74.86(1)°, γ = 69.73(1)°, R₁ = 0.0299. The anion of 2 forms a centrosymmetric dimer [BeCl₃(HNMe₂)]₂^2— via N—H···Cl bridges of the two donor acceptor complex units with Be—N separations of 175.2(2) pm. 3 : Space group Pbca, Z = 8, lattice dimensions at 193 K: a = 926.9(1), b = 2164.7(1), c = 2732.7(1) pm, R₁ = 0.0495. The structure of 3 contains centrosymmetric ion quadrupoles [(Me₂NH₂)(BeCl₄)]₂^2— forming by N—H···Cl bridges between (Me₂NH₂)⁺ and [BeCl₄]^2— ions.     

Trichloroberyllat‐Komplexe von Dimethylcyanamid,Morpholin und 4,4′‐Bipyridin

Trichloroberyllate Complexes of Dimethyl Cyanamide, Morpholine, and 4,4′‐Bipyridine The trichloroberyllate complexes (Ph₄P)[BeCl₃(NCNMe₂)] ( 1 ), (Ph₄P)[BeCl₃{HN(CH₂)₄O}] ( 2 ), and (Ph₄P)₂[(BeCl₃)₂(4,4′‐bipy)] ( 3 ) were prepared by reactions of (Ph₄P)₂[Be₂Cl₆] with dimethyl cyanamide, trimethylsilylmorpholinate, and 4,4′‐bipyridine, respectively, in dichloromethane solutions. 1 ‐ 3 were characterized by X‐ray crystallography and by IR‐spectroscopy. 1 ·CH₂Cl₂: Space group P1, Z = 1, lattice dimensions at 173 K: a = 714.2(1), b = 919.5(2), c = 1233.4(2) pm, α = 94.97(1)°, β = 90.86(1)°, γ = 111.90(1)°, R₁ = 0.0310. In the complex anion [BeCl₃(NCNMe₂)]^? the dimethyl cyanamide ligand is coordinated via a linear Be–N≡C‐NMe₂ arrangement, the CH₂Cl₂ molecules forming linear chains by hydrogen bridges ···HCH···Cl··· with the chlorine atoms of the {BeCl₃^?} groups. 2 : Space group , Z = 2, lattice dimensions at 173 K: a = 1050.9(1), b = 1099.7(1), c = 1308.3(2) pm, α = 87.57(1)°, β = 70.97(1)°, γ = 74.58(1)°, R₁ = 0.0397. The complex anions are dimerized by centrosymmetric puckered eight‐membered [Be–N–H···Cl]₂ rings. 3 ·2CH₂Cl₂: Space group , Z = 2, lattice dimensions at 173 K: a = 1095.4(1), b = 1559.6(2), c = 1869.8(3) pm, α = 79.12(1)°, β = 73.83(1)°, γ = 78.76(1)°, R₁ = 0.0548. The complex contains dianions [Cl₃Be(μ‐bipy)BeCl₃]^2? with Be–N distances of 177.0(6) and 178.5(6) pm. Both {BeCl₃}^? groups form C–H···Cl hydrogen bridges with the dichloromethane molecules.     

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.     

A chloro(2‐pyridinecarboxaldehyde)(2,2′:6′,2′′‐ter­pyridine)­ruthenium(II) complex

The aldehyde moiety in the title complex, chloro(2‐pyridinecarboxaldehyde‐N,O)(2,2′:6′,2′′‐terpyridine‐κ³N)ruthenium(II)–chloro­(2‐pyridine­carboxyl­ic acid‐N,O)(2,2′:6′,2′′‐ter­pyridine‐κ³N)­ruthenium(II)–perchlorate–chloro­form–water (1.8/0.2/2/1/1), [RuCl­(C₆H₅NO)­(C₁₅H₁₁N₃)]_1.8[RuCl­(C₆H₅­NO₂)(C₁₅H₁₁N₃)]_0.2­(ClO₄)₂·­CHCl₃·­H₂O, is a structural model of substrate coordination to a transfer hydrogenation catalyst. The title complex features two independent Ru^II complex cations that display very similar distorted octahedral coordination provided by the three N atoms of the 2,2′:6′,2′′‐ter­pyridine ligand, the N and O atoms of the 2‐pyridine­carbox­aldehyde (pyCHO) ligand and a chloride ligand. One of the cation sites is disordered such that the aldehyde group is replaced by a 20 (1)% contribution from a carboxyl­ic acid group (aldehyde H replaced by carboxyl O—H). Notable dimensions in the non‐disordered complex cation are Ru—N 2.034 (2) Å and Ru—O 2.079 (2) Å to the pyCHO ligand and O—C 1.239 (4) Å for the pyCHO carbonyl group.     

Reaktion von (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamin mit Me2MCl (M = Ga,In)

Reaction of (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamine with Me₂MCl (M = Ga, In) (R,R)‐(N,N′)‐Diisopropylcyclohexyl‐1,2‐diamine (H₂L) was reacted with Me₂GaCl and Me₂InCl in boiling toluene, respectively. In both cases the salt [Me₂M(H₂L)][Me₂MCl₂] [M = Ga ( 1 ), In ( 2 )] was formed. 1 and 2 were characterized by NMR and vibrational spectroscopy. In addition, an X‐ray structure determination was applied on 2 . According to the spectroscopical and structural findings 1 and 2 consist of cations [Me₂M(H₂L)]⁺ and anions [Me₂MCl₂]^?.     

New organic–inorganic frameworks incorporating iso‐ and heteropolymolybdate units and a 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium multiple hydrogen‐bond donor

Poly[bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) γ‐octamolybdate(VI) dihydrate], {(C₁₀H₁₆N₄)₂[Mo₈O₂₆]·2H₂O}_n, (I), and bis(3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium) α‐dodecamolybdo(VI)silicate tetrahydrate, (C₁₀H₁₆N₄)₂[SiMo₁₂O₄₀]·4H₂O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric γ‐type [Mo₈O₂₆]⁴⁻ anion, which produces a one‐dimensional polymeric chain by corner‐sharing, one cation and one water molecule. Three‐centre bonding with 3,3′,5,5′‐tetramethyl‐4,4′‐bi‐1H‐pyrazole‐2,2′‐diium, denoted [H₂Me₄bpz]²⁺ [N...O = 2.770 (4)–3.146 (4) Å], generates two‐dimensional layers that are further linked by hydrogen bonds involving water molecules [O...O = 2.902 (4) and 3.010 (4) Å]. In (II), each of the four independent [H₂Me₄bpz]²⁺ cations lies across a twofold axis. They link layers of [SiMo₁₂O₄₀]⁴⁻ anions into a three‐dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N...O = 2.866 (6)–2.999 (6) Å], while anion/aqua interactions occur preferentially viaμ₂‐O sites [O...O = 2.910 (6)–3.151 (6) Å].     

Silylhydrazine und dimere N,N′‐Dilithium‐N,N′‐bis(silyl)hydrazide – Synthesen,Reaktionen, Isomerisierungen

Silylhydrazines and Dimeric N,N′‐Dilithium‐N,N′‐bis(silyl)hydrazides – Syntheses, Reactions, Isomerisations Di‐tert.‐butylchlorosilane reacts with dilithiated hydrazine in a molar ratio to give the N,N′‐bis(silyl)hydrazine, [(Me₃C)₂SiHNH]₂, ( 5 ). Isomeric tris(silyl)hydrazines, N‐difluorophenylsilyl‐N′,N′‐bis(dimethylphenylsilyl)hydrazine ( 7 ) and N‐difluorophenylsilyl‐N,N′‐bis(dimethylphenylsilyl)hydrazine ( 8 ) are formed in the reaction of N‐lithium‐N′‐N′‐bis(dimethylphenylsilyl)hydrazide and F₃SiPh. Isomeric bis(silyl)hydrazines, (Me₃C)₂SiFNHNHSiMe₂Ph ( 9 ) and (Me₃C)₂‐ SiF(PhMe₂Si)N–NH₂ ( 10 ) are the result of the reaction of di‐tert.‐butylfluorosilylhydrazine and ClSiMe₂Ph in the presence of Et₃N. Quantum chemical calculations for model compounds demonstrate the dyotropic course of the rearrangement. The monolithium derivative of 5 forms a N‐lithium‐N′,N′‐bis(silyl)hydrazide ( 11 ). The dilithium salts of 5 ( 13 ) and of the bis(tert.‐butyldiphenylsilyl)hydrazine ( 12 ) crystallize as dimers with formation of a central Li₄N₄ unit. The formation of 12 from 11 occurs via a N′ → N‐silyl group migration. Results of crystal structure analyses are reported.     

A Novel Dinuclear Nickel(II) Complex with Three Bridges of Cl–, OAc– and (‐OCH2CH2O‐) Group of N,N, N′, N′‐Tetrakis(2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino) Glycol Ether

The novel dinuclear Ni²⁺ complex [Ni₂(μ‐Cl)(μ‐OAc) (EGTB)]·Cl·ClO₄·2CH₃OH, where EGTB is N, N, N′, N′‐tetrakis (2‐benzimidazolyl methyl‐1, 4‐di‐ethylene amino)glycol ether, crystallizes in the orthorhombic space group Pnma with a = 15.272(2), b = 14.768(2), c = 22.486(3) Å, V = 5071.4(12) ų, Z = 4, D_calc = 1.414 g cm^?3, and is bridged by triply bridging agents of a chloride ion, an acetate and an intra‐ligand (‐OCH₂CH₂O‐) group. The nickel coordination geometry is that of a slightly distorted octahedron with a NiN₃O₂Cl arrangement of the ligand donor atoms. The Ni–Cl distance is 2.361(2) Å, and two Ni–O distances are 1.996(5) and 2.279(6) Å. The three Ni–N distances are 2.033(7), 2.060(6), and 2.166(6) Å with the Ni–N bond trans to an ether oxygen the shortest, the Ni–N bond trans to an acetate oxygen the middle and the Ni–N bond trans to Cl the longest.     

Synthese,Struktur und Eigenschaften der Komplexe [(Me2PhP)3Cl2Re≡N‐IrCl2(C5Me5)], [(Me2PhP)3Cl2Re≡N‐IrCl(COD)], [PPh4][O3Os≡N‐IrCl2(C5Me5)] und [PPh4][O3Os≡N‐IrCl(COD)] mit Nitridobrücken Re≡N‐Ir und Os≡N‐Ir

Synthesis and Crystal Structures of the Complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)], [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)], [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)], and [PPh₄][O₃Os≡N‐IrCl(COD)] with Nitrido bridges Re≡N‐Ir and Os≡N‐Ir The heteronuclear complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)] ( 1 ), [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)] ( 2 ), [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)] ( 3 ) and [PPh₄][O₃Os≡N‐IrCl(COD)] ( 4 ) were obtained by the reaction of the nitrido complexes [ReNCl₂(PMe₂Ph)₃] and [OsO₃N]^— with the iridium compounds [IrCl₂(C₅Me₅)]₂ and [IrCl(COD)]₂ in benzonitrile. 1 forms red crystals with the composition 1 ·C₆H₅CN in the monoclinic space group P2₁/c and a = 1264.7(2); b = 1945.3(2); c = 1835.4(1) pm, β = 90.35(1)°, Z = 4. The complex fragment [IrCl₂(C₅Me₅)] in the dinuclear complex is connected by an asymmetric nitrido bridge Re≡N‐Ir to the nitrido complex [ReNCl₂(PMe₂Ph)₃]. The nitrido bridge is characterized by a Re‐N‐Ir bond angle of 179.4(2)° and distances Re‐N = 170.9(4) pm and Ir‐N = 203.3(4) pm. 2 forms brownish red, triclinic crystals with the space group P1¯ and a = 1076.6(2), b = 1373.2(2), c = 1452.4(1) pm, α = 107.513(8), β = 101.843(9), γ = 110.04(1)°, Z = 2. The nitrido bridge to the complex fragment [IrCl(COD)] has a Re‐N‐Ir bond angle of 173, 8(4)° and distances Re‐N = 170, 4(8) pm and Ir‐N = 196, 2(8) pm. 3 crystallizes as monoclinic red crystals in the space group P2₁/n and a = 1449.9(2), b = 906.74(4), c = 2628.9(5) pm, β = 103.50(1)°, Z = 4. The nitrido bridge Os≡N‐Ir is slightly bent (Os‐N‐Ir = 165.0(3)°). The distances are Os‐N = 168.3(5) pm and Ir‐N = 201.9(5) pm. 4 forms dark brown, orthorhombic crystals with the space group P2₁2₁2₁ and a = 704.35(2), b = 1228.17(6), c = 3442.0(4) pm, Z = 4. The distances in the slightly bent nitrido bridge (Os‐N‐Ir = 161.8(4)°) are Os‐N = 169.3(7) pm und Ir‐N = 197.8(7) pm.     

Synthesis and Crystal Structure of N,N＇-Dimethyldithio-arbamato-Copper（Ⅰ） Polymer {[Cu（Me2dtc）]2}n

Reactions of CuSCN with tetramethylthiuram disulfide in CH₃CN in the presence of styrene and N,N,N′,N″,N″‐pentamethyldiethylenetriamine gave rise to a new copper(I) complex ofN,N′‐dimethyldithiocabamate ([CU(S₂CNMe₂)]₂)_n. The title compound crystallized in the triclinic P‐1 space group with lattice parameters a=0.7610(4) nm, b=0.8911(4) nm, c=0.9268(5) nm, α=68.66(1)°, β=83.88(2)°, γ=79.31(2)°, V=0.5748(5) nm³, Z=2. The compound has a unique 1D chain structure composed of CuSCSCuSCS eight‐membered rings and a pair of CU? S bonds, the structure of which has been determined by singlecrystal X‐ray crystallography. The isolation of this compound may provide some helpful information for the cause of the induction periods of the reverse atom transfer radical polymerization.     

(2,2′‐Biquinoline‐κ2N,N′)dichloropalladium(II), ‐copper(II) and ‐zinc(II)

In the three title complexes, namely (2,2′‐biquinoline‐κ²N,N′)dichloro­palladium(II), [PdCl₂(C₁₈H₁₂N₂)], (I), and the corresponding copper(II), [CuCl₂(C₁₈H₁₂N₂)], (II), and zinc(II) complexes, [ZnCl₂(C₁₈H₁₂N₂)], (III), each metal atom is four‐coordinate and bonded by two N atoms of a 2,2′‐biquinoline molecule and two Cl atoms. The Pd^II atom has a distorted cis‐square‐planar coordination geometry, whereas the Cu^II and Zn^II atoms both have a distorted tetra­hedral geometry. The dihedral angles between the N—M—N and Cl—M—Cl planes are 14.53 (13), 65.42 (15) and 85.19 (9)° for (I), (II) and (III), respectively. The structure of (II) has twofold imposed symmetry.     

N‐Phenyl‐N′‐pyridylureas: stereochemical basis for anti­convulsant activity

4‐[N‐(2‐Chloro‐6‐methyl­phen­yl)ureido]pyridinium chloride, C₁₃H₁₃ClN₃O⁺·Cl⁻ (CI‐953 hydro­chloride), crystallizes with Z′ = 2 in P. In both mol­ecules, the methyl groups and Cl atoms on the benzene rings are disordered. The benzene rings of mol­ecules A and B adopt two conformations, differing by a rotation of 180° about the C—N bond to the ureido group, in an approximate 1:1 ratio. This disorder is further enhanced by the rotation of the methyl groups in both adopted positions. The pyridine and benzene rings inter­sect at angles of 102.1 (1) and 111.3 (1)° for A and B, respectively. Hydrogen bonding is mediated by Cl⁻ anions, resulting in indirect connectivity between the mol­ecules. Superposition of the mol­ecular structure, after 180° rotation about an amide bond, with that of phenytoin shows that the chemically different mol­ecules possess stereochemical features in common, which may explain their common activities.     

Chloroberyllate mit Stickstoff‐Donorliganden. Die Kristallstrukturen von (Ph4P)[BeCl3(Py)], (Ph4P)2[(BeCl3)2(TMEDA)], (Ph4P)[BeCl2{(Me3SiN)2CPh}] und (Ph4P)2[BeCl4] · 2CH2Cl2

Chloroberyllates with Nitrogen Donor Ligands. Crystal Structures of (Ph₄P)[BeCl₃(py)], (Ph₄P)₂[(BeCl₃)₂(tmeda)], (Ph₄P)[BeCl₂{(Me₃SiN)₂CPh}], and (Ph₄P)₂[BeCl₄] · 2CH₂Cl₂ The title compounds were obtained as colourless, moisture sensitive crystals by reactions of (Ph₄P)₂[Be₂Cl₆] with pyridine, tmeda (N, N′‐tetramethylethylendiamine), or with the silylated benzamidine PhC—[N(SiMe₃)₂(NSiMe₃)], whereas the tetrachloro beryllate was isolated as a by‐product from a solution in dichloromethane in the presence of the silylated phosphaneimine Me₃SiNP(tol)₃. All compounds were characterized by crystal structure determinations and by IR spectroscopy. (Ph₄P)[BeCl₃(Py)] ( 1 ): Space group Pbcm, Z = 4, lattice dimensions at 193 K: a = 756.2(1), b = 1739.2(2), c = 2016.3(2) pm, R₁ = 0.0626. The complex anion contains tetrahedrally coordinated beryllium atom with a Be—N distance of 176.5 pm. (Ph₄P)₂[(BeCl₃)₂(tmeda)]·2CH₂Cl₂ ( 2 ·2CH₂Cl₂). Space group P1¯, Z = 1, lattice dimensions at 193 K: a = 1072.7(1), b = 1132.6(1), c = 1248.9(1) pm, α = 95.34(1)°, β = 92.80(1)°, γ = 90.81(1)°, R₁ = 0.0344. Both nitrogen atoms of the tmeda molecule coordinate with BeCl₃^— units forming the centrosymmetric complex anion with Be—N distances of 181.3 pm. (PPh₄)[BeCl₂{(Me₃SiN)₂CPh}] ( 3 ). Space group C2, Z = 2, lattice dimensions at 193 K: a = 1255.4(2), b = 1401.9(2), c = 1085.2(2) pm, R₁ = 0.0288. In the complex anion the benzamidinato ligand {(Me₃SiN)₂CPh}^— acts as chelate with Be—N distances of 174.9 pm. (Ph₄P)₂[BeCl₄]·2CH₂Cl₂ ( 4 ·2CH₂Cl₂). Space group P2/c, Z = 4, lattice dimensions at 193 K: a = 2295.4(1), b = 982.5(1), c = 2197.2(2) pm, β = 99.19(1)°, R₁ = 0.0586. 4 ·2CH₂Cl₂ contains nearly ideal tetrahedral [BeCl₄]^2— ions, like the previously described 4 ·2, 5CH₂Cl₂, which crystallizes in the space group P1¯, with Be—Cl distances of 203.4 pm on average.     

(PPh4)2[Cl2Re(N3S2)(μ‐NSN)(μ‐N≡ReCl3)]2 – ein Rhenium(VII)‐Komplex mit einer Nitrido‐, einer Dinitridosulfato(II)‐ und einer Rhena‐3,5‐dithia‐2,4,6‐triazino‐Funktion

(PPh₄)₂[Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]₂ – a Rhenium(VII) Complex with a Nitrido, a Dinitridosulfato(II), and a Rhena‐3,5‐dithia‐2,4,6‐triazino Function The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals, which were suitable for a crystal structure determination. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[Cl₂Re^VII(N₃S₂)(μ‐NSN)(μ‐N≡Re^VIICl₃)]₂ ( 1 ): Space group P2₁/c, Z = 2, lattice dimensions at –80 °C: a = 1280.8(2), b = 1017.5(1), c = 2467.8(3) pm, β = 95.04(1)°, R = 0.049. The complex anion of 1 consists of a planar ReN₃S₂‐heterocycle which is connected with the second rhenium atom by a μ‐nitrido bridge as well as by a μ‐dinitridosulfato(II) ligand to form a planar Re₂(N)(NSN) six‐membered heterocycle. This [Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]^– unit dimerizes via one of the N‐atoms of the (NSN)^4– ligand to give a centrosymmetric Re₂N₂ four‐membered ring.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

Kristallstrukturen von Verbindungen A2[MnF3(SO4)] (A = Rb,NH4, Cs): Jahn‐Teller‐Ordnung in Mangan(III)‐fluoridsulfaten. I.

Jahn‐Teller Ordering in Manganese(III) Fluoride Sulphates. I. Crystal Structures of A₂[MnF₃(SO₄)] (A = Rb, NH4, Cs) The three isostructural fluorosulphatomanganates(III) A₂[MnF₃(SO₄)] (A = Rb, NH₄, Cs) crystallize in space group P2₁/c, Z = 4. Rb₂[MnF₃(SO₄)]: a = 7.271, b = 11.091, c = 8.776Å, β = 92.26°, R = 0.033; (NH₄)₂[MnF₃(SO₄)]: a = 7.299, b = 10.157, c = 8.813Å, β = 91.51°, R = 0.025; Cs₂[MnF₃(SO₄)]: a = 7.365, b = 11.611, c = 9.211, β = 92.30°, R = 0.029. In the chain anions [MnF₃(SO₄)]^2— manganese(III) is coordinated by two trans‐terminal and two trans‐bridging fluorine ligands, and by the O‐atoms of two briding sulphate ligands in trans position. The Jahn‐Teller effect induces a variety of antiferrodistortive ordering resulting in distorted [MnF₄O₂] octahedra with alternating elongation of F—Mn—F — and O—Mn—O — axes, respectively. Thus, only asymmetrical bridges are formed.     

Poly[[chlorido(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ3‐1,1,3,3‐tetracyano‐2‐ethoxypropenido‐κ3N:N′:N′′]: coordination polymer sheets linked into bilayers by hydrogen bonds

In the title compound, [Cu(C₉H₅N₄O)Cl(C₁₂H₈N₂)]_n or [Cu(tcnoet)Cl(phen)]_n, where phen is 1,10‐phenanthroline and tcnoet is 1,1,3,3‐tetracyano‐2‐ethoxypropenide, the axially elongated (4 + 2) coordination polyhedron around the Cu^II centre contains N atoms from three different tcnoet ligands. The resulting coordination polymer takes the form of sheets which are linked in pairs by a single C—H...N hydrogen bond to form bilayers. The bond lengths provide evidence for significant bond fixation in the phen ligand and extensive electronic delocalization in the tcnoet ligand, where the two –C(CN)₂ units are rotated, in conrotatory fashion, out of the plane of the central C₃O fragment.     

[1,5‐Bis(1‐methyl‐1H‐imidazol‐2‐yl­methyl‐κN3)‐1,5‐di­aza­cyclo­octane‐N,N′]chlorocobalt(II) perchlorate

The crystal structure of the title compound, [CoCl‐(C₁₆H₂₆N₆)]ClO₄, consists of discrete [CoCl­(C₁₆­H₂₆N₆)]⁺ cations and perchlorate anions. The five‐coordinate Co^II atom has four nitro­gen donors from the new mesocyclic ligand 1,5‐bis(1‐methyl‐1H‐­imidazol‐2‐ylmethyl)‐1,5‐di­aza­cyclo­octane [Co—N 2.046 (3)–2.214 (4) Å], and a chloride anion at the apical site [Co—Cl 2.3184 (13) Å]. The coordination geometry of the complex is essentially square pyramidal. The mesocyclic ligand takes a boat–chair configuration and the two imidazole pendants are not coplanar. The dihedral angle between the two imidazole planes is 15.97°. An H atom from the 1,5‐diaza­cyclo­octane group effectively blocks the axial coordination site opposite the Cl ligand.     

Heterobimetallische Komplexe von Lithium,Aluminium und Gold mit dem N‐[2‐N′,N′‐(Dimethylaminoethyl)‐N‐methyl‐aminoethyl]‐ferrocenyl‐Liganden (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}

Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with ⁿBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr₃ and AuCl · PPh₃ the heterobimetallic organo derivatives (FcN,N)AlBr₂ ( 3 ), (FcN,N)Au · PPh₃ ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.     

Kristallzucht und Strukturverfeinerung von Quecksilber(II)‐amidchlorid – HgClNH2

Crystal Growth and Refinement of the Crystal Structure of Mercury(II) Amide Chloride – HgClNH₂ Single crystals were prepared by recrystallization of HgClNH₂ from aqueous NH₃/NH₄⁺ solution at 160 °C. They were used for a single‐crystal X‐ray structure redetermination. The previously reported [W. N. Lipscomb, Acta. Crystallogr. 1951 , 4, 266.] structural topology determined on basis of X‐ray powder diffraction data is now confirmed. However, a higher symmetry is found: Space group type Pmma (instead of Pmm2), a = 6.709(1) Å, b = 4.351(1) Å, c = 5.154(1) Å, Z = 2. The crystal structure contains zig‐zag‐chains [Hg(NH₂)_2/2]⁺. Four Cl atoms complete the coordination sphere of Hg to a distorted octahedron. These share common faces and edges in layers [HgCl_4/4(NH₂)_2/2]. These layers are connected via hydrogen bonds N–H…Cl.