An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Z. Naturforsch. 2012, 67b, 1263-1272 / DOI: 10.5560/ZNB.2012-0250 Received September 26, 2012 Dedicated to Professor George M. Sheldrick on the occasion of his 70th birthday We report the first crystal structures of aniline complexes of silver, namely the three aniline-complexed silver(I) disulfonylamides 1 (aniline)(dimesylamido)silver(I), 2 bis(aniline)(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) and 3 bis(aniline)silver(I) [di(p-bromobenzenesulfonyl)amide] : aniline (1: 1). Compound 1 is molecular, with approximately linear coordination at silver; the coordination is extended to T-shaped by an Ag center dot center dot center dot O contact of 2.7136(11) angstrom to a neighbouring molecule related by a axis translation. Compound 2 is molecular, with trigonal planar coordination geometry at silver. Compound 3 is ionic, with exactly linear coordination at each of the two independent silver atoms, both of which occupy inversion centres; the third aniline is not coordinated to the silver atoms. Classical hydrogen bonds are the main feature of the packing diagrams for all three compounds. The packing of 1 and 2 can be analysed in terms of hydrogen-bonded dimers, further linked to form ribbons parallel to the a axis. In 3, the cations and anions are linked to form zigzag chains parallel to the b axis, and these are further linked to form a layer structure parallel to (001). The free aniline molecules are hydrogen bonded above and below the layer.

We report the first crystal structures of aniline complexes of silver, namely the three anilinecomplexed silver(I) disulfonylamides 1 (aniline)(dimesylamido)silver(I), 2 bis(aniline)(1,1,3,3- tetraoxo-1,3,2-benzodithiazolido)silver(I) and 3 bis(aniline)silver(I) [di(p-bromobenzenesulfonyl)- amide] : aniline (1 : 1). Compound 1 is molecular, with approximately linear coordination at silver; the coordination is extended to T-shaped by an Ag···O contact of 2.7136(11) Å to a neighbouring molecule related by a axis translation. Compound 2 is molecular, with trigonal planar coordination geometry at silver. Compound 3 is ionic, with exactly linear coordination at each of the two independent silver atoms, both of which occupy inversion centres; the third aniline is not coordinated to the silver atoms. Classical hydrogen bonds are the main feature of the packing diagrams for all three compounds. The packing of 1 and 2 can be analysed in terms of hydrogen-bonded dimers, further linked to form ribbons parallel to the a axis. In 3, the cations and anions are linked to form zigzag chains parallel to the b axis, and these are further linked to form a layer structure parallel to (001). The free aniline molecules are hydrogen bonded above and below the layer.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We report the crystal structures of five amine-complexed silver(I) disulfonylamides of composition L2AgX (L = secondary amine, X = disulfonylamide anion) [1: bis(2,2,6,6-tetramethylpiperidine)- silver(I) dimesylamide, 2: bis(2,2,6,6-tetramethylpiperidine)(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido) silver(I), 3: bis(diethylamine)(dimesylamido)silver(I), 4: bis(diethylamine)silver(I) 1,1,3,3-tetraoxo- 1,3,2-benzodithiazolide, 5: bis(dicyclohexylamine)silver(I) 1,1,3,3-tetraoxo-1,3,2-benzodithiazolide]. In the solid state 1, 4 and 5 are ionic compounds, whereas 2 and 3 appear to be molecular, but with long Ag-Ndisulfonylamide bonds (ca. 2.5 Å ), almost linear Namine-Ag-Namine bond angles (171, 158°) and S-N bond lengths more typical of purely ionic disulfonylamides. The packing of these complexes is governed by the formation of chains via motifs of Ag・ ・ ・O contacts and classical hydrogen bonds. The interaction motifs vary slightly depending on the steric demand of the amine substituents. For the molecular compounds, either new motifs appear (3) or intramolecular classical hydrogen bonds are formed, and linear arrays of molecules are generated by non-classical hydrogen bonds (2)

Abstract Cocrystallization of tetramethylurea (TMU) with one equivalent of either di(4-fluorobenzenesulfo- nyl)amine (FAH), di(4-chlorobenzenesulfonyl)amine (CAH), di(4-bromobenzenesulfonyl)amine (BAH). di(4-iodobenzenesulfonyl)amine (IAH), di(4-methylbenzenesulfonyl)aniine (MAH>, ordi(4- nitrobenzenesulfonyDamine (NAH), using dichloromethane/petroleum ether as the solvent, afforded the molecular complexes (FAH)2 · TMU (1. monoclinic. P21/c,Z' = 1. structure previously reported), CAHTMU, BAH-TMU and IAH-TMU (2-4, isomorphic series, triclinic, P1̅,Z' = 1), MAH · TMU (5, monoclinic. P21, Z' = 1). and the uranium salt TMUH+NA- (6, monoclinic. P21/c,Z' = 2). The structural results obtained by X-ray crystallography at low temperatures indicate that the varying p- substituents of the di(arenesulfonyl)amines exert a decisive influence on (i) the stoichiometry of the cocrystallization reaction (2:1 for 1 vs. 1:1 for 2-6), (ii) the degree of proton transfer between the strongly acidic (SO2)2NH moieties and the basic carbonyl function of TMU (molecular complexes assembled via N-H···O=C hydrogen bonds in 1 -5 vs. two independent ion pairs based upon charge- assisted C-O-H+ ···N- interactions in 6). and (Hi) the conformation of the disulfonylamineZ-amide units as defined by rotations about the S-N bonds (extended forms displaying anticlinal C-S ··· S'- C' torsions for the two molecules in 1 and the two anions in 6 vs. folded forms featuring synperi- planar C-S ···S'-C torsions for the molecules in 2-5). The packing modes of 1-4 underline the well-known correlation between the atomic number of halogen atoms and their propensity to form halogen bonds. Thus, the structure of 1 is devoid of short F···O contacts, whereas the isomorphic co- crystals 2-4 consist of lamellar layers in which the inner lamellae include the TMU molecules and the peripheral regions are built up from CAH, BAH or IAH molecules associated into catemers via C-Hal ··· O=S bonds. The lamellar layers of the non-isomorphic methyl congener 5. although topological^' similar to those of 2-4, are stacked according to a herringbone pattern that does not arise in the structures of 2-4. The most prominent packing feature of the uranium salt 6 are intimate dimers of two independent NA- ions, stabilized by dipolar nitro-nitro interactions and C-H ··· O=S contacts and further connected into monolayers through C-H ··· Onitro contacts. The uranium ions are inserted between these layers and bonded to the anion dimers by the strong hydrogen bonds mentioned above and numerous C-H ··· Onitro contacts. The presence of two independent formula units appears to arise from frustration between several competing interactions, e. g. dipolar nitro attractions, weak hydrogen bonding to sulfonyl and nitro acceptors and π/π stacking of aromatic rings.

Cocrystallization of tetramethylurea (TMU) with one equivalent of either di(4-fluorobenzenesulfonyl)amine (FAH), di(4-chlorobenzenesulfonyl)amine (CAH), di(4-bromobenzenesulfonyl)amine (BAH), di(4-iodobenzenesulfonyl)amine (IAH), di(4-methylbenzenesulfonyl)amine (MAH), or di(4nitrobenzenesulfonyl)amine (NAH), using dichloromethane/petroleum ether as the solvent, afforded the molecular complexes (FAH)2·TMU (1, monoclinic, P21/c, Z′ = 1, structure previously reported), CAH·TMU, BAH·TMU and IAH·TMU (2 – 4, isomorphic series, triclinic, P1̄, Z′ = 1), MAH·TMU (5, monoclinic, P21, Z′ = 1), and the uronium salt TMUH+NA− (6, monoclinic, P21/c, Z′ = 2). The structural results obtained by X-ray crystallography at low temperatures indicate that the varying psubstituents of the di(arenesulfonyl)amines exert a decisive influence on (i) the stoichiometry of the cocrystallization reaction (2 : 1 for 1 vs. 1 : 1 for 2 – 6), (ii) the degree of proton transfer between the strongly acidic (SO2)2NH moieties and the basic carbonyl function of TMU (molecular complexes assembled via N–H· · ·O=C hydrogen bonds in 1 – 5 vs. two independent ion pairs based upon chargeassisted C–O–H+ · · · N− interactions in 6), and (iii) the conformation of the disulfonylamine/-amide units as defined by rotations about the S–N bonds (extended forms displaying anticlinal C–S· · ·S′– C′ torsions for the two molecules in 1 and the two anions in 6 vs. folded forms featuring synperiplanar C–S· · ·S′–C′ torsions for the molecules in 2 – 5). The packing modes of 1 – 4 underline the well-known correlation between the atomic number of halogen atoms and their propensity to form halogen bonds. Thus, the structure of 1 is devoid of short F· · ·O contacts, whereas the isomorphic cocrystals 2 – 4 consist of lamellar layers in which the inner lamellae include the TMU molecules and the peripheral regions are built up from CAH, BAH or IAH molecules associated into catemers via C–Hal· · ·O=S bonds. The lamellar layers of the non-isomorphic methyl congener 5, although topologically similar to those of 2 – 4, are stacked according to a herringbone pattern that does not arise in the structures of 2 – 4. The most prominent packing feature of the uronium salt 6 are intimate dimers of two independent NA− ions, stabilized by dipolar nitro-nitro interactions and C–H· · ·O=S contacts and further connected into monolayers through C–H· · ·Onitro contacts. The uronium ions are inserted between these layers and bonded to the anion dimers by the strong hydrogen bonds mentioned above and numerous C–H· · ·Onitro contacts. The presence of two independent formula units appears to arise from frustration between several competing interactions, e. g. dipolar nitro attractions, weak hydrogen bonding to sulfonyl and nitro acceptors and π/π stacking of aromatic rings.

Cocrystallization of tetramethylurea (TMU) with one equivalent of either di(4-fluorobenzenesulfonyl)amine (FAH), di(4-chlorobenzenesulfonyl)amine (CAH), di(4-bromobenzenesulfonyl)amine (BAH), di(4-iodobenzenesulfonyl)amine (IAH). di(4-methylbenzenesulfonyl)amine (MAH), or di(4-nitrobenzenesulfonyl)amine (NAH), Using dichloromethane/petroleum ether as the solvent, afforded the molecular complexes (FAH)(2)center dot TMU (1, monoclinic, P2(1)/c, Z' = 1, structure previously reported), CAH.TMU, BAH.TMU and IAH.TMU (2-4, isomorphic series, triclinic, P (1) over bar Z' = 1). MAH.TMU (5, monoclinic, P2(1), Z' = 1), and the uronium salt TMUH(+)NA(-) (6, monoclinic, P2(1)/c, Z' = 2). The results obtained by X-ray crystallography at low temperatures indicate substituents of the di(arenesulfonyl)amines exert a decisive influence oil (i) the stoichiometry of the cocrystallization reaction (2: 1 for 1 vs. 1 : 1 for 2-6), (ii) the degree of proton transfer between the strongly acidic (SO2)(2)NH moieties and the basic carbonyl function of TMU (molecular complexes assembled via N-H center dot center dot center dot O=C hydrogen bonds in 1-5 vs. two independent ion pairs based upon charge-assisted C-O-H+center dot center dot center dot N- interactions in 6), and (iii) the conformation of the disulfonylamine/-amide units as defined by rotations about the S-N bonds (extended forms displaying anticlinal C-S center dot center dot center dot S'-C' torsions for the two molecules in 1 and the two anions in 6 vs. folded forms featuring synperiplanar C-S center dot center dot center dot S'-C' torsions for the molecules in 2-5). The packing modes of 1-4 underline the well-known correlation between the atomic number of halogen atoms and their propensity to form halogen bonds. Thus, the structure of I is devoid of short F center dot center dot center dot O contacts, whereas the isomorphic cocrystals 2-4 consist of lamellar layers in which the inner lamellae include the TMU molecules and the peripheral regions are built LIP from CAH. BAH or IAH molecules associated into catemers via C-Hal center dot center dot center dot O=S bonds. The lamellar layers of the non-isomorphic methyl congener 5, although topologically similar to those of 2-4. are stacked according to a herringbone pattern that does not arise ill the structures of 2-4. The most prominent packing feature of the uronium salt 6 are intimate dimers of two independent NA(-) ions, stabilized by dipolar nitro-nitro interactions and C-H center dot center dot center dot O=S contacts and further connected into monolayers through C-H center dot center dot center dot O-nito contacts. The uronium ions are inserted between these layers and bonded to the anion dimers by the strong hydrogen bonds mentioned above and numerous C-H center dot center dot center dot O-nitro contacts. The presence of two independent formula units appears to arise from frustration between several competing interactions, e.g. dipolar nitro attractions, weak hydrogen bonding to sulfonyl and nitro acceptors and pi/pi stacking of aromatic rings.

A dimorphic form of NH(4)Z center dot H2O; where Z(-) is N-deprotonated ortho-benzenedisulfonimide, has been obtained and structurally characterized (previously known form 1A: monoclinic, P2(1)/c, Z' = 1; new polymorph 1B: monoclinic, P2(1)/n, Z' = 1). Both structures are dominated by an abundance of classical hydrogen bonds N+-H/O-H center dot center dot center dot 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 center dot center dot center dot O/N hydrogen bonds, whereas the layered structure of 1A displays only one independent C-H center dot center dot center dot O bond, providing a link between adjacent layers. The compound [Ph3PNPPh3]Z (2, monoclinic. P2(1)/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 center dot center dot center dot C(pi) 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 center dot center dot center dot O/N- hydrogen bonds and C-H center dot center dot center dot C(pi) interactions.