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.     

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°).     

Rubidium-di(methansulfonyl)amid, 18-Krone-6 und Wasser als Bausteine eines dreidimensionalen Wasserstoffbrücken-Netzwerks: Darstellung und Kristallstruktur von [Rb(18-Krone-6)(H2O)2{(MeSO2)2N}] · H2O

Polysulfonylamines. CXV. Rubidium Di(methanesulfonyl)amide, 18-Crown-6, and Water as Building Blocks of a Three-Dimensional Hydrogen-Bond Network: Preparation and Crystal Structure of [Rb(18-crown-6)(H₂O)₂{(MeSO₂)₂N}] · H₂O The title complex (orthorhombic, space group P2₁2₁2₁, Z = 4, X-ray analysis at –130 °C) was obtained by co-crystallizing equimolar amounts of RbN(SO₂Me)₂ and 18-crown-6 from water/methanol (1/1). The crown ether displays effective D_3d symmetry; the Rb^⊕ ion is displaced by 99.5(1) pm from the mean plane of the macrocyclic oxygen atoms [Rb–O 290.2(3)–309.7(3) pm] and thus adopts a typical “sunrise coordination”. Two Rb–O contacts from water molecules [295.1(4) and 323.0(4) pm] and a Rb–O contact from the anion [292.0(4) pm], all situated on the opposite side from the crown ether, complete the coordination of the cation. Hydrogen bonding plays a major role in the crystal packing. The complex units, excluding the non-coordinating water molecules, are associated into strands by (H₂O)_∞ catenation and water…anion hydrogen bonds. The non-coordinating water molecules, located between the parallel strands, cross-link each of them with four adjacent equivalents via water…anion bonds to generate a three-dimensional network.     

From Isolated Polyanions to 1‐D Structure: Synthesis and Crystal Structure of Hybrid Fluorides {[(C2H4NH3)3NH]4+}2 · (H3O)+ · [Al7F30]9– and {[(C2H4NH3)3NH]4+}2 · [Al7F29]8– · (H2O)2

Two new hybrid fluorides, {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · (H₃O)⁺ · [Al₇F₃₀]^9– ( I ) and {[(C₂H₄NH₃)₃NH]⁴⁺}₂ · [Al₇F₂₉]^8– · (H₂O)₂ ( II ), are synthesized by solvothermal method. The structure determinations are performed by single crystal technique. The symmetry of both crystals is triclinic, sp. gr. P 1, I : a = 9.1111(6) Å, b = 10.2652(8) Å, c = 11.3302(8) Å, α = 110.746(7)°, β = 102.02(1)°, γ = 103.035(4)°, V = 915.9(3) ų, Z = 1, R = 0.0489, R_w = 0.0654 for 2659 reflections, II : a = 8.438(2) Å, b = 10.125(2) Å, c = 10.853(4) Å, α = 106.56(2)°, β = 96.48(4)°, γ = 94.02(2)°, V = 877.9(9) ų, Z = 1, R = 0.0327, R_w = 0.0411 for 3185 reflections. In I , seven corner‐sharing AlF₆ octahedra form a [Al₇F₃₀]^9– anion with pseudo 3 symmetry; such units are found in the pyrochlore structure. The aluminum atoms lie at the corners of two tetrahedra, linked by a common vertex. In II , similar heptamers are linked in order to build infinite (Al₇F₂₉)_n^8– chains oriented along a axis. In both compounds, organic moieties are tetra protonated and establish a system of hydrogen bonds N–H…F with four Al₇F₃₀^9– heptamers in I and with three inorganic chains in II .     

N–H(N)…S Bonding in Tetrahedral [Zn(NCS)2L]0 Complexes (L = MexH2–xN(CH2)2NH2–yMey,x, y = 0 – 2)

The crystal structures of uncharged tetrahedral dithiocyanato zinc complexes with N-methylated ethylenediamines have been determined with a view to a study of intermolecular hydrogen-bonding interactions in these compounds. It is found that the H(N) hydrogen atoms are exhaustively engaged in N–H(N) … S bonds. The majority of these bonds are branched (bifurcated or trifurcated), and the hydrogen-bond systems they form all contain one of the two characteristic primitive core motifs: either a discrete centrosymmetric […S…H…]₂ dimer or an infinite […S…H…]_∞ helix about a 2₁ or pseudo-2₁ axis. The hydrogen bonding is analyzed in detail, with particular attention to the existence of correlations between the N–H(N)–S angles and the H(N) … S distances as well as between the corresponding N–H(N)–S/H(N)…S pairs in the bifurcated N–H(N)…2 S bonds.     

Zinkiodate – Schwingungsspektren (IR,Raman) und Kristallstruktur von Zn(IO3)2 · 2 H2O

Zinc Iodates – Infrared and Raman Spectra, Crystal Structure of Zn(IO₃)₂ · 2 H₂O The zinc iodates Zn(IO₃)₂ · 2 H₂O and Zn(IO₃)₂ as well as α‐Co(IO₃)₂ · 2 H₂O were studied by X‐ray, IR‐ and Raman spectroscopic methods. The crystal structure of the dihydrate, which is isostructural with the respective cobalt compound, was determined by X‐ray single‐crystal studies (space group P1, Z = 2, a = 490,60(4), b = 667,31(5), c = 1088,85(9) pm, α = 98,855(6), β = 91,119(7), and γ = 92,841(6)°, R1 = 2,55%, 2639 unique reflections I > 2σ(I)). Transconfigurated Zn(IO₃)₄(H₂O)₂ octahedra are threedimensionally connected via common IO₃^– ions parallel to [001] and hydrogen bonds parallel to [100] and [010], respectively. Anhydrous Zn(IO₃)₂ crystallizes in space group P2₁ (Z = 2) with a = 548,9(2), b = 512,4(1), c = 941,8(2) pm, and β = 90,5(3)°. The structure of Zn(IO₃)₂ is a monoclinically distorted variant of the structures of β‐Ni(IO₃)₂ (space group P6₃) and Co(IO₃)₂ (P3). The O–H … O–IO₂ hydrogen bonds of the crystallographically different H₂O molecules of the dihydrates (ν_OD (OD stretching modes of isotopically dilute samples) 2430, 2415, 2333 and 2300 cm^–1, Zn(IO₃)₂ · 2 H₂O, 90 K) are examples to the matter of fact that O … O distances are only a bad measure for the strength of hydrogen bonds. The infrared and Raman spectra as well as a group theoretical treatment are presented and discussed with respect to mutual exclusion principle (possible space groups), the strength of the hydrogen bonds and the distortion of the IO₃^– ions at the C₁ lattice sites.     

Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

IR- und Raman-Spektren der isotypen Iodathydrate M(IO3)2 · 4 H2O (M = Mg,Ni, Co); Kristallstruktur von Co(IO3)2 · 4 H2O

Infrared and Raman Spectroscopy of the Isostructural Iodate Hydrates M(IO₃)₂ · 4 H₂O (M = Mg, Ni, Co)-Crystal Structure of Cobalt Iodate Tetrahydrate The iodate tetrahydrates Mg(IO₃)₂ · 4 H₂O, β-Ni(IO₃)₂ · 4 H₂O, Co(IO₃)₂ · 4 H₂O and their deuterated specimens were studied by X-ray, infrared and Raman spectroscopic methods. The title compounds are isostructural crystallising in the monoclinic space group P2₁/c (Z = 2). The crystal structure of Co(IO₃)₂ · 4 H₂O (a = 836.8(5), b = 656.2(3), c = 850.2(5) pm and β = 100.12(5)°) has been refined by single-crystal X-ray methods (R_obs = 3.08%, 693 unique reflections I₀ > 2σ(I)). Isolated Co(IO₃)₂(H₂O)₄ octahedra form layers parallel (100). Within these layers, the two crystallographically different hydrate water molecules form nearly linear hydrogen bonds to adjacent IO₃^– ions (ν_OD of matrix isolated HDO of Co(IO₃)₂ · 4 H₂O (isotopically diluted samples) 2443 (H3), 2430 (H2), and 2379 cm^–1 (H1 and H4), –180 °C). Intramolecular O–H and intermolecular H…O distances were derived from the novel ν_OD vs. r_OH and the traditional ν_OD vs. r_H…O correlation curves, respectively. The internal modes of the iodate ions of the title compounds are discussed with respect to their coupling with the librations of the hydrate H₂O molecules, the distortion of the IO₃^– ions, and the influence of the lattice potential.     

Neue Koordinationsverbindungen aus Triorganylzinn(IV)-dimesylamiden und Neutralliganden: Einkern- und Mehrkernkomplexe mit molekularer oder ionischer Kristallstruktur

Polysulfonylamines. CII. New Coordination Compounds Derived from Triorganyltin(IV) Dimesylamides and Uncharged Ligands: Mononuclear and Polynuclear Complexes with Molecular or Ionic Crystal Structures The purpose of this report is to draw attention to the remarkable versatility of the dimesylamides R₃SnA [A^– = (MeSO₂)₂N^–; R = Me ( 1 a ) or Ph ( 1 b )] as precursors for pentacoordinate triorganyltin(IV) complexes belonging to four distinct structural types. Representative complexes were prepared by treating 1 a or 1 b in the appropriate molar ratios with unidentate thiourea or urea-type ligands or with the bidentate ligand [Ph₂P(O)CH₂]₂ (DPPOE). The following compounds were characterized by X-ray analysis: [Me₃Sn(A)(thiourea)] ( 2 a ; monoclinic, space group P2₁/n), [Ph₃Sn(A)(tetramethylthiourea)] ( 2 b ; monoclinic, P2₁, two independent formula units), [Me₃Sn(1-methylurea)₂]⁺ · A^– ( 3 a ; monoclinic, P2₁/c), [Ph₃Sn(1,1-dimethylurea)₂]⁺ · A^– ( 3 c ; triclinic, P1), [{Ph₃Sn(A)}₂(μ-dppoe)] ( 4 ; triclinic, P1), [Ph₃Sn(μ-dppoe)]_nⁿ⁺ · n A^– · n MeCN ( 5 ; monoclinic, P2₁/c). The lattices of 2 a , 2 b and 4 contain discrete uncharged formula units which are mononuclear for 2 a and 2 b or dinuclear for 4 , whereas 3 a , 3 c and 5 have ionic structures featuring mononuclear cations for 3 a and 3 c or an infinite linear-polymeric cation for 5 . In all the structures, the tin atoms adopt trigonal-bipyramidal geometries, the apical positions being occupied in 2 a and 2 b by the S atom of the thiourea and one O atom of A^–, in 3 a and 3 c by the O atoms of two urea-type ligands, in 4 by an O atom of the bridging DPPOE molecule and one O atom of A^–, and in 5 by two phosphoryl O atoms from different bridging DPPOE ligands. In the structures of 2 a , 3 a and 3 c , the (thio)urea NH functions are connected to A^– via intermolecular or interionic N–H … O and N–H … N hydrogen bonds. Crystals of [{Me₃Sn(bipyH⁺ … A^–)}₂(μ-bipy)]²⁺ · 2 A^– ( 6 ; monoclinic, C2/c) formed adventitiously in a reaction mixture containing 1 a and 4,4′-bipyridine. The rod-like supramolecular cation of 6 (length ca. 4 nm) is built up from two Me₃Sn⁺ units bridged through bipy and unidentally coordinated by a monoprotonated bipy (= bipyH⁺), resulting in a trigonal-bipyramidal geometry around tin (N atoms apical); each of the terminal bipyH⁺ ligands forms an ⁺N–H … N^– hydrogen bond with one A^–.     

Kristallstruktur,Infrarot‐ und Ramanspektren von Kupfertrihydrogenperiodatmonohydrat,CuH3IO6 · H2O

Crystal Structure, Infrared and Raman Spectra of Copper Trihydrogenperiodate Monohydrate, CuH₃IO₆ · H₂O The hitherto unknown compound CuH₃IO₆ · H₂O was studied by X‐ray, IR‐ and Raman spectroscopic methods. The crystal structure was determined by X‐ray single‐crystal studies (space group P2₁2₁2₁, Z = 4, a = 532.60(10), b = 624.00(10), c = 1570.8(3) pm, R1 = 1.85%, 1559 unique reflections (I > 2σ(I))). Isolated, meridionally configurated H₃IO₆^2– ions are coordinated to the copper ions forming double‐ropes in [100]. These ropes are connected in [010] and [001] by hydrogen bonds. The copper ions possess a square pyramidal co‐ordination with the hydrate H₂O on top. The infrared and Raman spectra as well as group theoretical treatment are presented and discussed with respect to the strength of the hydrogen bonds and the co‐ordination of the CuO₅₍₊₁₎ polyhedra and the H₃IO₆^2– ions at the C₁ lattice sites. The hydrogen bonds of the H₂O molecules and H₃IO₆^2– ions (HO–H…O–IO₅H₃ and H₂IO₅O–H…O–IO₅H₃) greatly differ in strength, as shown from both the respective O…O distances: 282.6 and 298.6 pm (H₂O), and 258.8, 259.7, and 270.9 pm (H₃IO₆^2–) and the OD stretching modes of isotopically dilute samples: 2498 and 2564 cm^–1 (90 K) (HDO), and 1786, 2024, and 2188 cm^–1 (H₂DIO₆^2–). The IO stretching modes of the H₃IO₆^2– ions (696–788 cm^–1 and 555–658 cm^–1, 295 K) display the different strength of the respective I–O and I–O(H) bonds (r_I–O: 181.1–188.3 pm and 189.2–194.5 pm).     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

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.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

Synthesis,Spectroscopic, and X‐Ray Diffraction Studies of cis‐Dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl3 H‐pyrazol‐3‐onato) Tin(IV)

Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O₂ gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C₂₆H₂₆N₄O₄)SnCl₂]. The compound has a six‐coordinated Sn^IV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and D_x = 1.575 g cm^–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, ¹H NMR and ¹¹⁹Sn Mössbauer spectral data of the compound are reported and discussed.     

Polysulfonylamine. LXXXVIII. Drei bindungsisomere Komplexmoleküle im gleichen Kristall: Bildung und Struktur des dimeren Diorganylzinn(IV)-hydroxids [Me2{(MeSO2)2N}(phen)Sn(μ-OH)]2

Polysulfonylamines. LXXXVIII. Occurrence of Three Linkage-Isomeric Complex Molecules in One Crystal: Formation and Structure of the Dimeric Dioganyltin(IV) Hydroxide [Me₂{(MeSO₂)₂N}(phen)Sn(μ-OH)]₂ Crystal of the title compound (triclinic, space group P1 ) were obtained from Me₂Sn[N(SO₂Me)₂]₂ and 1,10-phenanthroline by adventitious hydrolysis. The structure consists of four independent [Me₂{(MeSO₂)₂N}(phen)Sn(OH)] moieties A , A ′, B , B ′ that are associated via four-membered [SnO(H)]₂ rings to form two centrosymmetric homodimers AA , BB and one asymmetric heterodimer A ′ B ′. The four crystallographically independent tin atoms attain moderately distorted pentagonalbipyramidal coordinations, the apical positions being occupied by the methyl groups and the equatorial sites by the oxygen atoms of the μ-OH groups, the nitrogen atoms of the bidentate phen ligand and one oxygen atom of the (MeSO₂)₂N? anion. Each anion is further connected to the respective complex core through an Sn? O? H…? A hydrogen bond, where the acceptor A is nitrogen in AA and the A ′ fragment of A ′ B ′, or oxygen in BB and the B ′ fragment of A ′ B ′. The distinct hydrogen bond motifs in the three linkageisomeric complex units originate from two essentially different conformations of the dimesylamide anions.     

Synthesis and Crystal Structure of Copper(II) Trifluoroacetates,Cu2(CF3COO)4 · 2 CH3CN and Cu(CF3COO)2(H2O)4

Cu₂(CF₃COO)₄ · 2 CH₃CN ( I ) and Cu(CF₃COO)₂(H₂O)₄ ( II ) have been prepared by concentrating of acetonitrile and aqueous solutions respectively. According to X-ray data, the complex I consists of binuclear molecules with Cu–O 1.969 Å, Cu–N 2.114 Å. The Cu…Cu distance was found to be 2.766 Å, one of the longest for dimeric structures, apparently, due to the high acidity of trifluoroacetic acid. The coordination environment of Cu atom in II can be described as 4 + 2: 2 Cu–O (H₂O) 1.937 Å, 2 Cu–O (CF₃COO) 1.985 Å, 2 Cu–O (H₂O) 2.447 Å. The mononuclear structure is stabilized by formation of two intra- and six intermolecular hydrogen bonds.     

Synthese,Kristallstruktur und Eigenschaften von Tetranatrium‐bis(trimetaphosphimato)cuprat(II)‐Decahydrat,Na4{Cu[(PO2NH)3]2} · 10 H2O

Synthesis, Crystal Structure, and Properties of Tetrasodium Bis(trimetaphosphimato)cuprate(II) Decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O Tetrasodium bis(trimetaphosphimato)cuprate(II) decahydrate, Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O, was obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with Cu(NO₃)₂ · 3 H₂O (molar ratio 2 : 1). The structure of Na₄{Cu[(PO₂NH)₃]₂} · 10 H₂O ( 1 ) was solved by single‐crystal X‐ray methods (P 1, a = 912.51(6), b = 932.14(6), c = 966.10(6) pm, α = 94.840(5), β = 108.652(6), γ = 118.588(6)°, Z = 1). The P₃N₃ rings of the trimetaphosphimate ions exhibit a slightly distorted sofa conformation. The conformation of the anions have been analysed using torsion angles, displacement asymmetry parameters, and puckering parameters. The trimetaphosphimate ions act as bidentate ligands of Cu²⁺. With additionally coordinated water molecules, anionic complexes {Cu[(PO₂NH)₃]₂ · 2 H₂O}^4– are formed. In the crystal these complexes are interconnected by N–H…O und O–H…O hydrogen bonds and they coordinate the Na⁺. Thus, a three‐dimensional network is formed.     

Zweidimensionale Polymere mit hydrophober Umhüllung: Kristallstrukturen der isostrukturellen Metallkomplexe [M{C6H4(SO2)2N}(H2O)] (M = K,Rb) und des strukturverwandten Ammoniumsalzes [(NH4){C6H4(SO2)2N}(H2O)]

Metal Salts of Benzene‐1,2‐di(sulfonyl)amine. 4. Hydrophobically Wrapped Two‐Dimensional Polymers: Crystal Structures of the Isostructural Metal Complexes [M{C₆H₄(SO₂)₂N}(H₂O)] (M = K, Rb) and of the Structurally Related Ammonium Salt [(NH₄){C₆H₄(SO₂)₂N}(H₂O)] The previously unreported compounds KZ · H₂O ( 1 ), RbZ · H₂O ( 2 ) and NH₄Z · H₂O ( 3 ), where Z^– is Ndeprotonated ortho‐benzenedisulfonimide, are examples of layered inorgano‐organic solids, in which the inorganic component is comprised of metal or ammonium cations, N(SO₂)₂ groups and water molecules and the outer regions are formed by the planar benzo rings of the anions. The metal complexes 1 and 2 were found to be strictly isostructural, whereas 3 is structurally related to them by a non‐crystallographic mirror plane ( 1 – 3 : monoclinic, space group P2₁/c, Z = 4; single crystal X‐ray diffraction at low temperatures). In each structure, the five‐membered 1,3,2‐dithiazolide heterocycle possesses an envelope conformation, the N atom lying about 40 pm outside the mean plane of the S–C–C–S moiety. The metal complexes feature two‐dimensional coordination networks interwoven with O–H…O hydrogen bonds originating from the water molecules. The metal centres adopt an irregular nonacoordination formed by five sulfonyl O atoms, two N atoms and two μ₂‐bridging water molecules; each M⁺ is connected to four different anions. When NH₄⁺ is substituted for M⁺, the metal–ligand bonds are replaced by N⁺–H…O hydrogen bonds, but the general topology of the lamella is not affected. In the three structures, the lipophilic benzo groups protrude obliquely from the surfaces of the polar lamellae and display marked interlocking between adjacent layers.     

A Novel Adipate Bridged Supramolecular Layer: Crystal Structure of the Cobalt(II) Complex [(μ‐C6H8O4)4/2Co(μ‐H2O)2Co(H2O)4] · 4 H2O

The pale‐rose compound [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] · 4 H₂O was prepared from adipic acid and CoCO₃ in aqueous solution. The crystal structure (monoclinic, P2₁/n (no. 14), a = 8.061(1), b = 15.160(2), c = 9.708(2) Å, β = 90.939(7)°, Z = 2, R = 0.0405, wR² = 0.0971) consists of adipate bridged supramolecular [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] layers and hydrogen bonded H₂O molecules. The cobalt atoms Co1 and Co2 are distorted octahedrally coordinated by the O atoms of two bridging trans‐H₂O molecules and four bidentate adipate anions (Co1) and by the O atoms of two bridging trans‐H₂O molecules and four monodentate H₂O molecules (Co2), respectively. Equatorial bonds: d(Co1–O) = 2.048 Å (2 × ), 2.060 Å (2 × ); d(Co2–O) = 2.057 Å (2 × ), 2.072 Å (2 × ). Axial bonds: d(Co1–O) = 2.235 Å (2 × ); d(Co2–O) = 2.156 Å (2 × ).     

Synthesis and Crystal Structure of [Cu2(H2O)2(phen)2(OH)2][Cu2(phen)2(OH)2(CO3)2] · 10 H2O with phen = 1,10‐phenanthroline

The blue copper complex [Cu₂(H₂O)₂(phen)₂(OH)₂][Cu₂(phen)₂(OH)₂(CO₃)₂] · 10 H₂O, which was prepared by reaction of 1,10‐phenanthroline monohydrate, CuCl₂ · 2 H₂O and Na₂CO₃ in the presence of succinic acid in CH3OH/H₂O at pH = 13.0, crystallized in the triclinic space group P1 (no. 2) with cell dimensions: a = 9.515(1) Å, b = 12.039(1) Å, c = 12.412(2) Å, α = 70.16(1)°, β = 85.45(1)°, γ = 81.85(1)°, V = 1323.2(2) ų, Z = 1. The crystal structure consists of dinuclear [Cu₂(H₂O)₂(phen)₂(OH)₂]²⁺ complex cations, dinuclear [Cu₂(phen)₂(OH)₂(CO₃)₂]^2– complex anions and hydrogen bonded H₂O molecules. In both the centrosymmetric dinuclear cation and anion, the Cu atoms are coordinated by two N atoms of one phen ligand, three O atoms of two μ‐OH groups and respectively one H₂O molecule or one CO₃^2– anion to complete distorted [CuN₂O₃] square‐pyramids with the H₂O molecule or the CO₃^2– anion at the apical position (equatorial d(Cu–O) = 1.939–1.961 Å, d(Cu–N) = 2.026–2.051 Å and axial d(Cu–O) = 2.194, 2.252 Å). Two adjacent [CuN₂O₃] square pyramids are condensed via two μ‐OH groups. Through the interionic hydrogen bonds, the dinuclear cations and anions are linked into 1D chains with parallel phen ligands on both sides. Interdigitation of phen ligands of neighboring 1D chains generated 2D layers, between which the hydrogen bonded water molecules are sandwiched.