Polysulfonylamine. CLX [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 10 [2] Die dreidimensionalen Koordinationspolymere M[(CH3SO2)2N] mit M = Kalium,Rubidium, Caesium (isotype Strukturen für M = K,Rb)

Polysulfonylamines. CLX. Crystal Structures of Metal Di(methanesulfonyl)amides. 10. The Three‐Dimensional Coordination Polymers M[(CH₃SO₂)₂N], where M is Potassium, Rubidium, Cesium (Isotypic Structures for M = K, Rb) Low‐temperature X‐ray crystal structures are reported for KA (monoclinic, space group P2₁/c, Z′ = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2₁/n, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO₂)₂NH. In KA and RbA, the anion is distorted into a rare C₁ conformation, whereas the standard C₂ conformation is retained in the cesium complex. The structures consist of three‐dimensional coordination networks, in which each cation adopts an irregular (O₆N)‐heptacoordination by forming close contacts to one (O, N)‐chelating, one (O, O)‐chelating and three κ¹O‐bonding ligands; however, the coordination number for Cs⁺ is effectively increased to 8 by a very short Cs···Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand‐metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M—O bond cross‐linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs···Cs alternatingly 422.5 and 487.5 pm, Cs···Cs···Cs 135.7°), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C—H···A interanion contacts consistent with weak hydrogen bonding.     

Polysulfonylamine. CLXIII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 12 [1] Das orthorhombische Doppelsalz Na2Cs2[(CH3SO2)2N]4·3H2O: Ein dreidimensionales Koordinationspolymer aus (Caesium‐Anion‐Wasser)‐Schichten und intercalierten Natriumionen

Polysulfonylamines. CLXIII. Crystal Structures of Metal Di(methanesulfonyl)amides. 12. The Orthorhombic Double Salt Na₂Cs₂[(CH₃SO₂)₂N]₄·3H₂O: A Three‐Dimensional Coordination Polymer Built up from Cesium‐Anion‐Water Layers and Intercalated Sodium Ions The packing arrangement of the three‐dimensional coordination polymer Na₂Cs₂[(MeSO₂)₂N]₄·3H₂O (orthorhombic, space group Pna2₁, Z′ = 1) is in some respects similar to that of the previously reported sodium‐potassium double salt Na₂K₂[(MeSO₂)₂N]₄·4H₂O (tetragonal, P4₃2₁2, Z′ = 1/2). In the present structure, four multidentately coordinating independent anions, three independent aquo ligands and two types of cesium cation form monolayer substructures that are associated in pairs to form double layers via a Cs(1)—H₂O—Cs(2) motif, thus conferring upon each Cs⁺ an irregular O₈N₂ environment drawn from two N, O‐chelating anions, two O, O‐chelating anions and two water molecules. Half of the sodium ions occupy pseudo‐inversion centres situated between the double layers and have an octahedral O₆ coordination built up from four anions and two water molecules, whereas the remaining Na⁺ are intercalated within the double layers in a square‐pyramidal and pseudo‐C₂ symmetric O₅ environment provided by four anions and the water molecule of the Cs—H₂O—Cs motif. The net effect is that each of the four independent anions forms bonds to two Cs⁺ and two Na⁺, two independent water molecules are involved in Cs—H₂O—Na motifs, and the third water molecule acts as a μ₃‐bridging ligand for two Cs⁺ and one Na⁺. The crystal cohesion is reinforced by a three‐dimensional network of conventional O—H···O=S and weak C—H···O=S/N hydrogen bonds.     

Polysulfonylamine. CLIV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 7 [2] Ein dreidimensionales Koordinationspolymer aus Schichten und Pfeilern: Kristallstruktur von Ba[(CH3SO2)2N]2·2H2O

Polysulfonylamines. CLIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 7. A Three‐Dimensional Coordination Polymer Built up from Layers and Pillars: Crystal Structure of Ba[(CH₃SO₂)₂N]₂·2H₂O The barium compound BaA₂·2H₂O, derived from HA = di(methanesulfonyl)amine, has been characterized by single crystal X‐ray diffraction at —95 °C (monoclinic, space group P2₁/n, Z = 4). Despite numerous metal‐ligand bonds, the independent anions A^— and A′^— retain the pseudo‐C₂ symmetric conformation that commonly occurs in organic onium salts BH⁺A^—. The large cation attains ninefold coordination via interactions with one (O, N)‐chelating A^—, three κ¹O‐bonding A^—, two κ¹O‐bonding A′^— and two monodentate water molecules; if a distinctly longer barium‐water distance is included, the coordination number may alternatively be viewed as 9 + 1 and one water molecule regarded as an asymmetrically μ₂‐bridging ligand. In contrast to the previously reported layer structures of SrA₂ and PbA₂, the present crystal displays a three‐dimensional coordination assembly consisting of layers formed by the cations, the water molecules and the pentadentate A^— ligands, and of interlayer pillars provided by the bidentate A′^— ligands; however, the Ba²⁺/A^— substructure turns out to be topologically and crystallographically congruent with the corresponding M²⁺/A^— substructures in SrA₂ and PbA₂. The crystal cohesion of the barium complex is reinforced by four O(W)—H···O=S hydrogen bonds and several non‐classical C—H···O=S hydrogen bonds.     

Polysulfonylamine. CLXV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 14 [1] Cs3Ag[(MeSO2)2N]4 und CsAg[(MeSO2)2N]2: Ein dreidimensionales und ein schichtförmiges Koordinationspolymer mit Bis(dimesylamido‐N)argentat‐Baugruppen

Polysulfonylamines. CLXV. Crystal Structures of Metal Di(methanesulfonyl)amides. 14. Cs₃Ag[(MeSO₂)₂N]₄ and CsAg[(MeSO₂)₂N]₂: A Three‐Dimensional and a Layered Coordination Polymer Containing Bis(dimesylamido‐N)argentate Building Blocks Serendipitous formation pathways and low‐temperature X‐ray structures are reported for the coordination compounds Cs₃A₂[AgA₂] ( 1 ) and Cs[AgA₂] ( 2 ), where A^— represents the pentadentate dimesylamide ligand (MeSO₂)₂N^—. Both phases (monoclinic, space group C2/c, Z′ = 1/2) contain inversion‐symmetric bis(dimesylamido‐N)argentate units displaying exactly linear N—Ag—N cores and short, predominantly covalent Ag—N bonds [ 1 : 213.5(2), 2 : 213.35(12) pm]; in each case, the coordination number of the silver ion is extended to 2 + 6 by four internal and two external Ag···O secondary interactions. The three‐dimensional coordination polymer 1 is built up from alternating layer substructures [{Cs(1)}{A}_4/2]^— with Cs(1) lying on twofold rotation axes and [{Cs(2)}₂{AgA₂}_4/4]⁺ with Cs(2) occupying general positions. Within the substructural layers, both types of cesium cation have approximately planar O₄ environments, whereas the final coordination spheres including interlayer bonds are extended to O₆ for Cs(1) and to O₈N for Cs(2). Compound 2 , in contrast, forms a genuine layer structure. The layers are constructed from Cs⁺ chains located on twofold rotation axes, alternating with [AgA₂]^— stacks reinforced by Ag···O secondary interactions and weak C—H···O hydrogen bonds; Cs⁺ is embedded in an O₈ environment. Both structures are pervaded by a three‐dimensional C—H···O network.     

Lamellare Schichten auf der Grundlage von Wasserstoffbrücken und π‐Stapelung: Kristallstrukturen der Metall(II)‐Komplexe [Cd{C6H4(SO2)2N}2(H2O)4] und [Cu{C6H4(SO2)2N}2(H2O)4]·2 H2O

The title complexes, obtained by treating hot aqueous solutions of ortho‐benzenedisulfonimide with solid CdCO₃ or CuO, have been characterized by low‐temperature X‐ray diffraction (both triclinic, space group P&1macr;, Z = 1, metal ions on inversion centres). The cations have trans‐octahedral coordinations provided by two Cd‐N bonded or two Cu‐O bonded anions and four water molecules [Cd‐N 234.7(2) pm; Cu‐O(anion) 240.4(1) pm, elongated by Jahn‐Teller distortion]; the copper complex contains two further, non‐coordinating, water molecules per formula unit. In both structures, the uncharged zero‐dimensional building blocks are associated via strong hydrogen bonds O(W)‐H···A and one short C‐H···O bond to form two‐dimensional assemblies comprising an internal polar lamella of metal cations, (SO₂)₂N groups and water molecules, and hydrophobic peripheral regions consisting of vertically protruding benzo rings. Carbocycles drawn alternatingly from adjacent layers form π‐stacking arrays, in which the parallel aromatic rings display intercentroid distances in the range 365‐385 pm and vertical ring spacings in the range 345‐385 pm.     

Polysulfonylamine. CLII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 6 [2] Drei Schichtstrukturen: Die isotypen binären Verbindungen M[(MeSO2)2N]2 (M = Sr,Pb) und das Ethanol‐Solvat Pb[(MeSO2)2N]2 · EtOH

Polysulfonylamines. CLII. Crystal Structures of Metal Di(methanesulfonyl) amides. 6. Three Layer Structures: The Isotypic Binary Compounds M[(MeSO₂)₂N]₂ (M = Sr, Pb) and the Ethanol Solvate Pb[(MeSO₂)₂N]₂ · EtOH Low‐temperature X‐ray crystal structures are reported for the layer compounds SrA₂ (monoclinic, space group P2₁/n, Z′ = 1), PbA₂ (isotypic and isostructural with SrA₂), and PbA₂·EtOH (triclinic, P1¯, Z′ = 1), where A^— denotes the anion obtained by deprotonation of the strong NH acid (MeSO₂)₂NH. The ternary compound appears to be the first crystallographically established ethanol solvate of a lead(II) complex. In the two‐dimensional coordination networks, the cations adopt either a distorted cubic or, in the solvate, an irregular (O₆N₂)‐octacoordination, the metal centres of the isotypic structures forming close contacts to two (O, N)‐chelating and four κ¹O‐bonding anions, whereas in the solvate one of the latter ligands is displaced by an EtOH molecule. In the isotypic structures, the Pb—O distances are systematically longer than the Sr—O distances and the Pb—N bonds shorter than the Sr—N bonds, which correlates with the softer character of Pb²⁺ as compared to Sr²⁺. The 6s lone pair on Pb²⁺ is stereochemically inactive in both lead compounds. Analogies and discrepancies between the layer architectures are discussed in detail, including an evaluation of short C—H···O contacts in terms of weak hydrogen bonding. Two complexes of composition PbA₂·2 L, where L is pyridine or 1, 10‐phenanthroline, have been synthesized and characterized by analytical methods.     

Polysulfonylamine. CLXIV Kristallstrukturen von Metall‐di(methansulfonyl)amiden. Dithallium‐tris(dimesylamido‐N)argentat: Ein zweidimensionales Koordinationspolymer

Polysulfonylamines. CLXIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 13. Dithallium Tris(dimesylamido‐N)argentate: A Two‐Dimensional Coordination Polymer The complex salt Tl₂[Ag{N(SO₂Me)₂}₃] (monoclinic, space group P2₁/n, Z′ = 1) was obtained by serendipity. Its layer structure displays two unprecedented characteristics, viz. one (MeSO₂)₂N^— ion that strongly deviates from the C₂‐symmetric standard conformation of this species and approximates to mirror symmetry, and a tris(dimesylamido)argentate anion featuring a trigonal‐planar AgN₃ core with Ag—N bond lengths of 225.6(6), 226.0(6), 236.3(6) pm and N—Ag—N angles in accordance with VSEPR concepts [149.8(2) vs. 102.8(2) and 107.3(2)°]. The independent thallium ions are coordinated by the complex anions to form monolayer substructures, in which Tl(1) attains an O₆ and Tl(2) an O₅ environment; the monolayers are associated into bilayers via one independent set of Tl(2)—O bonds that concomitantly raise the coordination number for Tl(2) to six. Both TlO₆ polyhedra may be viewed as extremely distorted octahedra reflecting the stereochemical activity of the 6s lone pair of electrons. The two‐dimensional Ag—N/Tl—O bonding system is reinforced by a three‐dimensional network of weak C—H···O hydrogen bonds.     

Strukturen ionischer Di(arensulfonyl)amide. 8. Natrium‐bis[di(4‐fluorbenzolsulfonyl)amido‐N]argentat: Ein Heterobimetallkomplex mit lamellarer Schichtstruktur und kurzen Zwischenschichtkontakten C–H···F–C

Structures of Ionic Di(arenesulfonyl)amides. 8. Sodium Bis[di(4‐fluorobenzenesulfonyl)amido‐N]argentate: A Heterobimetallic Complex Exhibiting a Lamellar Layer Structure and Short C–H···F–C Interlayer Contacts Na[Ag{N(SO₂–C₆H₄–4‐F)₂}₂] (monoclinic, C2/c, Z′ = 1/2) is the first heterobimetallic representative in a well‐documented class of layered inorgano‐organic solids where the inorganic component is comprised of metal cations and coordinating N(SO₂)₂ groups and the outer regions are formed by the aromatic rings of the di(arenesulfonyl)amide entities, which adopt a folded conformation approximating to mirror symmetry. The inversion‐symmetric bis(amido)argentate unit of the novel compound displays an exactly linear N–Ag–N core and short Ag–N bonds of 217.55(17) pm (at ?140 °C); the coordination number of the silver ion is extended to 2 + 6 by four internal and two external Ag···O secondary interactions. The polar lamella is constructed from rows of Na⁺ ions located on twofold axes, alternating with bis(amido)argentate strands reinforced by Ag···O interactions and weak C–H···O hydrogen bonds; Na⁺ is embedded in an O₆ environment. Adjacent layers are cross‐linked via short C–H···F–C contacts suggestive of weak hydrogen bonding enhanced by cooperativity.     

New coordination modes in potassium edta salts: K2[H2edta]·2H2O,K3[Hedta]·2H2O and K4[edta]·3.92H2O

Three potassium edta (edta is ethylenediaminetetraacetic acid, H₄Y) salts which have different degrees of ionization of the edta anion, namely dipotassium 2‐({2‐[bis(carboxylatomethyl)azaniumyl]ethyl}(carboxylatomethyl)azaniumyl)acetate dihydrate, 2K⁺·C₁₀H₁₄N₂O₈²⁻·2H₂O, (I), tripotassium 2,2′‐({2‐[bis(carboxylatomethyl)amino]ethyl}ammonio)diacetate dihydrate, 3K⁺·C₁₀H₁₃N₂O₈³⁻·2H₂O, (II), and tetrapotassium 2,2′,2′′,2′′′‐(ethane‐1,2‐diyldinitrilo)tetraacetate 3.92‐hydrate, 4K⁺·C₁₀H₁₂N₂O₈⁴⁻·3.92H₂O, (III), were obtained in crystalline form from water solutions after mixing edta with potassium hydroxide in different molar ratios. In (II), a new mode of coordination of the edta anion to the metal is observed. The HY³⁻ anion contains one deprotonated N atom coordinated to K⁺ and the second N atom is involved in intramolecular bifurcated N—H...O and N—H...N hydrogen bonds. The overall conformation of the HY³⁻ anions is very similar to that of the Y⁴⁻ anions in (III), although a slightly different spatial arrangement of the –CH₂COO⁻ groups in relation to (III) is observed, whereas the H₂Y²⁻ anions in (I) adopt a distinctly different geometry. The preferred synclinal conformation of the –NCH₂CH₂N– moiety was found for all edta anions. In all three crystals, the anions and water molecules are arranged in three‐dimensional networks linked via O—H...O and C—H...O [and N—H...O in (I) and (II)] hydrogen bonds. K...O interactions also contribute to the three‐dimensional polymeric architecture of the salts.     

Correlation between the reactivity and spectroscopic properties of N‐substituted secondary thioamides. New intramolecular N···H+···N binding approach and proton complexes based on thioamide ligation

On the basis of a comparison of chemical shifts and wavenumbers of several secondary thioamides and amides having monocationic substituents attached to thiocarbamoyl or carbamoyl groups by a polymethylene chain, new intramolecular unconventional N···H⁺···N hydrogen bonding effects were discovered. It is argued that the CH₂—N rotation is hindered and two ⁺H···NHCH₃ non‐equivalent protons occur in a proton spectrum of hydrochloride 1a (at 10.68 and 2.77 ppm, respectively) instead of two ⁺NH₂CH₃ protons. Presumably, the above steric factors inhibit the acidic hydrolysis of 1a (stabilized by strong intramolecular N···H⁺···N hydrogen bonds) to an amide and prevent intramolecular cyclization of 2a (stabilized by strong intramolecular neutral–neutral N···HN hydrogen bonds) to a cyclic amidine. Postulation of additional dihydrogen bond formation is helpful in understanding the spectroscopic differences of 4 and 5 . The above new bonding is also compared with intramolecular N···H—N⁺ hydrogen bonds in primary amine salts 7 and 8 . In contrast to 3 , a cooperative hydrogen bonded system is observed in 9 and 10 . The weak hydrogen bonds in 7 – 10 facilitate the hydrolysis and cyclization reactions of secondary thioamides. The spectroscopic data for secondary (thio)amides are especially useful for characterizing the electronic situation at the (thio)carbamoyl nitrogen atoms and they are perfectly correlated with the reactivity. Examples of chelation of protons by thioamides ( 11 and 12 ), which contain strongly electron‐donating pyrimidine groups, are presented to show the contribution of dihydrogen bonding in the protonation reaction similar to 1 and 4 . Copyright © 2003 John Wiley & Sons, Ltd.     

Anion Controlled Supramolecular Self‐Assembly of Tetraprotonated Tris[2‐(benzylamino)ethyl]amine

The novel supramolecular assembly of composition [{(bz₃tren)H₄}⁴⁺ · (ReO₄)^— · 3(Cl)^—] resulted from the self‐organization of a mixture of tris[2‐(benzylamino)ethyl]amine (bz₃tren), HCl and NH₄ReO₄ at a molar ratio of 1:4.7:1 in methanol. The crystal architecture is characterized by stacks of repeating sandwich‐type building blocks that contain charge‐assisted N—H···O(Re) hydrogen bonds [N···O 2.81‐2.86Å] and weaker C—H···O(Re) interactions [C···O 3.11Å]. The stacks are further linked by N—H···Cl [N···Cl 3.03Å] and weaker C—H···Cl [C···Cl 3.47‐3.74Å] interactions into two‐dimensional layers bordered by the benzyl groups of the [(bz₃tren)H₄]⁴⁺ cations. Edge‐to‐face C—H···π interactions involving the aromatic rings occur within and between the layers. The protonation constants of bz₃tren in methanol were determined by potentiometric titration. The corresponding structures of the ligand in its different protonation states were calculated at the DFT‐level.     

Synthesis and Crystal Structure of Cesium Hexamminesodium Decahydro‐closo‐decaborate‐Ammonia(1/1), Cs[Na(NH3)6][B10H10]·NH3

Cs[Na(NH₃)₆][B₁₀H₁₀]·NH₃ was synthesised from cesium and disodium‐decahydro‐closo‐decaborate Na₂B₁₀H₁₀ in liquid ammonia, from which it crystallized in form of temperature sensitive colorless plates (triclinic, P1¯, a = 8.4787(7) Å, b = 13.272(1) Å, c = 17.139(2) Å, α = 88.564(1)°, β = 89.773(1)°, γ = 81.630(1)°, V = 1907.5(3) ų, Z = 4). The compound is the first example of an alkali metal boranate with two different types of cations. The decahydro‐closo‐decaborate dianions [B₁₀H₁₀]^2— and the cesium cations form a equation/tex2gif-stack-1.gif[Cs₂(B₁₀H₁₀)₂]^2— layer parallel to the ac plane. These layers are separated by N—H···N‐hydrogen bonded hexamminesodium cations.     

Polysulfonylamine. CLVIII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 9 [2] Erhöhung der Kristallsymmetrie durch Kokristallisation: Monoklines Na[(CH3SO2)2N]·H2O und tetragonales NaK[(CH3SO2)2N]2·2H2O

Polysulfonylamines. CLVIII. Crystal Structures of Metal Di(methanesulfonyl)amides. 9. Enhancing Crystal Symmetry by Co‐crystallization: Monoclinic Na[(CH₃SO₂)₂N]·H₂O and Tetragonal NaK[(CH₃SO₂)₂N]₂·2H₂O The three‐dimensional coordination polymers NaA·H₂O ( 1 ) and NaKA₂·2H₂O ( 2 ), derived from the strong NH acid (MeSO₂)₂NH = HA, have been characterized by single crystal X‐ray diffraction at —95 °C ( 1 : monoclinic, space group C2/c, Z′ = 2; 2 : tetragonal, P4₃2₁2, Z′ = 1). The results suggest that structures with Z′ > 1 are good candidates for co‐crystallization experiments. Both packings display layer substructures built up from the multidentately coordinating anions, the aquo ligands and two kinds of chemically and/or crystallographically distinct cations, whereas cations of a third type are intercalated between the layers. All anions have the extended standard conformation of this species; 1 contains two pseudo‐C₂ symmetric A^—, 2 one pseudo‐C₂ and two crystallographically C₂ symmetric A^—. Details for structure 1 : a) The layer‐forming Na(1) and Na(3) cations are distributed over three distinctly separated planes, Na(1) occupies general positions and has a non‐octahedral O₅N environment, Na(3) resides on inversion centres that generate an octahedral O₆ coordination; b) one independent A^— is oriented vertically, the other parallel to the layer plane; c) the intercalated Na(2) ions occupy twofold rotation axes within a single plane and possess a non‐octahedral O₆ environment. Details for structure 2 : a) The layer‐forming K(1) and K(2) cations occupy twofold rotation axes within a unique plane and have chemically identically O₆N₂ coordination polyhedra approximating to hexagonal bipyramids; b) all A^— are oriented vertically to the layer plane; c) the intercalated sodium ions reside on pseudo‐inversion centres, have an octahedral O₆ environment and are distributed over two closely adjacent planes. Owing to the enhanced packing efficiency of the bimetal complex, the vertical layer repeat‐distance is reduced from 1140 pm for 1 to 720 pm for 2 . Each structure exhibits an infinite cation‐water chain that propagates in the direction of the layer stacking and contains the three independent cations.     

复合物HNO···H2O2内N-H···O蓝移氢键的理论研究

A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complexHNO…H_2O_2 was conducted by employment of both standard and counterpoise-corrected methods to calculate thegeometric structures and vibrational frequencies at the MP2/6-31G(d),MP2/6-31 G(d,p),MP2/6-311 q G(d,p),B3LYP/6-31G(d),B3LYP/6-31 G(d,p) and B3LYP/6-311 G(d,p) levels.In the H-bond N-H…O,the calcu-lated blue shift of N-H stretching frequency is in the vicinity of 120 cm~(-1) and this is indeed the largest theoreticalestimate of a blue shift in the X-H…Y H-bond ever reported in the literature.From the natural bond orbital analy-sis,the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation.For the blue-shifted H-bond N-H…O,the hyperconjugation was inhibited due to the existence of significant elec-tron density redistribution effect,and the large blue shift of the N-H stretching frequency was prominently due tothe rehybridization of sp~n N-H hybrid orbital.     

Ein lamellarer Schichtverband auf der Grundlage von Wasserstoffbrücken und π‐Stapelung: Kristallstruktur des Lithiumkomplexes [Li{C6H4(SO2)2N}(H2O)3] und ein Vergleich mit anderen Metall(I)‐benzol‐1, 2‐di(sulfonyl)amiden

The title complex, obtained by treating ortho‐benzenedisulfonimide (HZ) with LiOH in aqueous solution, has been characterized by low‐temperature X‐ray diffraction (triclinic, space group P&1macr;, Z' = 1). The lithium cation is bonded to one sulfonyl oxygen atom and three water molecules in a distorted tetrahedral configuration [Li‐O 189.3(3)‐201.2(3) pm, O‐Li‐O 98.5(2)‐123.2(2)?]. The zero‐dimensional [Li(Z)(H₂O)₃] complexes, which display an intramolecular O(W)‐H···O hydrogen bond, are cross‐linked via five O(W)‐H···O/N/O(W) interactions and a remarkably short C‐H···O bond (H···O 217 pm, C‐H···O 170?) to form a two‐dimensional assembly comprising an internal polar lamella of metal cations, (SO₂)₂N groups and water molecules, and hydrophobic peripheral regions consisting of protruding benzo groups. In the packing, alternate carbocycles drawn from adjacent layers set up a π‐stacking array of parallel aromatic rings (intercentroid distances 349 and 369 pm, cycle spacings 331 and 336 pm). In a short survey, the currently known crystal packings of seven M^IZ · n H₂O (n ≥ 0) complexes are examined and compared.     

Charge‐assisted N—H·I and C—H·I hydrogen bonding in (1R,2S)‐1‐(ferrocenylmethyl)‐2‐(methoxymethyl)pyrrolidinium iodide

In the title compound, [Fe(C₅H₅)(C₁₂H₁₉NO)]I, the ferrocene moiety has an eclipsed conformation, with mean Fe—C bond lengths of 2.031 (4) and 2.020 (6) Å for the substituted and unsubstituted cyclo­penta­dienyl rings. The pyrrolidinium heterocycle adopts an envelope conformation and has its 1‐ and 2‐substituents in a relative trans disposition. Strong (+/−)‐charge‐assisted N—H·I and C—H·I hydrogen bonds are present. The crystal structure is also stabilized by weak C—H·O interactions.     

7‐Vinyl‐8‐aza‐7‐de­aza‐2′‐deoxy­adenosine monohydrate

In the title compound, 4‐amino‐1‐(2‐deoxy‐β‐d ‐eythro‐pento­furan­osyl)‐3‐vinyl‐1H‐pyrazolo­[3,4‐d]­pyrimidine monohydrate, C₁₂H₁₅N₅O₃·H₂O, the conformation of the gly­cosyl bond is anti. The furan­ose moiety is in an S conformation with an unsymmetrical twist, and the conformation at the exocyclic C—C(OH) bond is +sc (gauche, gauche). The vinyl side chain is bent out of the heterocyclic ring plane by 147.5 (5)°. The three‐dimensional packing is stabilized by O—H·O, O—H·N and N—H·O hydrogen bonds.     

Metallsalze des Benzol‐1, 2‐di(sulfonyl)amins. 9 [1, 2] Der Bariumkomplex [Ba{C6H4(SO2)2N}2(H2O)22: Ein säulenförmiges Koordinationspolymer mit lamellarer Kristallpackung

Metal Salts of Benzene‐1, 2‐di(sulfonyl)amine. 9. The Barium Complex [[Ba{C₆H₄(SO₂)₂N}₂(H₂O)2₂]: A Columnar Coordination Polymer with Lamellar Crystal Packing The title complex, obtained by treating ortho‐benzenedi‐sulfonimide with Ba(OH)₂ in aqueous solution, has been characterized by low‐temperature X‐ray diffraction (monoclinic, space group C2/c, Z = 4, Ba²⁺ on a crystallographic twofold axis). The cation attains a tenfold coordination by accepting bonds from two water molecules, four κ¹O‐bonding anions and two (O, N)‐chelating anions. The cation‐anion interactions create columnar strands parallel to the z axis, from which protrude twin stacks of benzo rings in the directions ±x, and water molecules and non‐coordinating sulfonyl oxygen atoms in the directions ±y. Adjacent strands related by translation parallel to y are associated via O(W)—H···O=S hydrogen bonds to form lamellar sandwich layers. The contiguous benzo rings of adjacent layers are markedly interlocked.     

Polysulfonylamine. CLXXVIII Onium‐Salze des Benzol‐1,2‐di(sulfonyl)amins (HZ): Eine zweite Kristallform des Ammonium‐Salzes NH4Z·H2O und Kristallstruktur des Bis(triphenylphosphoranyliden)ammonium‐Salzes [Ph3PNPPh3]Z

Polysulfonylamines. CLXXVIII. Onium Salts of Benzene‐1,2‐di(sulfonyl)amine (HZ): A Second Crystal Form of the Ammonium Salt NH₄Z·H₂O and Crystal Structure of the Bis(triphenylphosphoranylidene)ammonium Salt [Ph₃PNPPh₃]Z A dimorphic form of NH₄Z·H₂O, where Z^? is N‐deprotonated ortho‐benzenedisulfonimide, has been obtained and structurally characterized (previously known form 1A : monoclinic, P2₁/c, Z′ = 1; new polymorph 1B : monoclinic, P2₁/n, Z′ = 1). Both structures are dominated by an abundance of classical hydrogen bonds N⁺–H/O–H···O=S/OH₂, whereby the anionic N^? function does not act as an acceptor. The major difference between the dimorphs arises from the topology of the hydrogen bond network, which is two‐dimensional in 1A , leading to a packing of discrete lamellar layers, but three‐dimensional in 1B . Moreover, the latter network is reinforced by a set of weak C–H··O/N hydrogen bonds, whereas the layered structure of 1A displays only one independent C–H···O bond, providing a link between adjacent layers. The compound [Ph₃PNPPh₃]Z ( 2 , monoclinic, P2₁/c, Z′ = 1) is the first structurally authenticated example of an ionic Z^? derivative in which the cation contains neither metal bonding sites nor strong hydrogen bond donors. This structure exhibits columns of anions, surrounded by four parallel columns of cations, giving a square array. The large cations are associated into a three‐dimensional framework via weak C–H···C(π) interactions and an offset face‐to‐face phenyl interaction, while the anions occupy tunnels in this framework and are extensively bonded to the surrounding cations by C–H···O/N^? hydrogen bonds and C–H···C(π) interactions.     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.