Die Kristallstruktur des 2:1-Adduktes zwischen Antimontrichlorid und Diphenylamin, 2SbCl3 · (C6H5)2NH

The Crystal Structure of the 2:1 Addition Compound between Antimony Trichloride and Diphenylamine, 2SbCl₃ · (C₆H₅)₂NH The 2:1 molecular compound between antimony trichloride and diphenylamine, 2SbCl₃ · (C₆H₅)₂NH, crystallizes in the monoclinic space group P2₁/c with a = 7.802(2) Å, b = 9.415(3) Å, c = 26.037(8) Å, β = 91.08(2)⁰ and Z = 4. The two independent SbCl₃ molecules point with the Sb atom to a phenyl ring each of the diphenylamine molecule. Inspite of slightly different orientations the distances to the ring planes are about equal (3.08 and 3.09 Å). The conformation of the diphenylamine molecule is an intermediate between the planar and the twist form. The mean bond distance Sb? Cl is 2.37 Å. Longer Sb…Cl contacts of 3.35 to 3.50 Å and π-donor-acceptor interactions complete the distorted octahedral coordination respectively, of the and ψ-octahedral coordination, respectively, of the Sb-atoms.     

Halogenometallate von Übergangselementen mit Kationen stickstoffhaltiger heterocyclischer Basen. I. Die Kristallstrukturen von 1,4-Dimethylpiperazinium-tetrachlorocobaltat(II) und -zinkat(II), (dmpipzH2)[MIICl4] (M = Co,Zn)

Halogenometalates of Transition Elements with N-heterocyclic Base Cations. I. The Crystal Structures of 1,4-Dimethylpiperazinium Tetrachlorocobaltate(II) and -zincate(II), (dmpipzH₂)[M^IICl₄] (M = Co, Zn) The compounds (dmpipzH₂)[M^IICl₄] crystallize in the monoclinic space group P2₁/m with a = 6.133(1), b = 14.306(1), c = 6.902(1) Å, β = 90.54(2)°, Z = 2 for M = Co and with a = 6.141(1), b = 14.282(1), c = 6.907(1) Å, β = 90.60(2)°, Z = 2 for M = Zn. The structures consist of tetrahedra [MCl₄]^2? and centrosymmetric cations (dmpipzH₂)²⁺ in the chair form. Bifurcated hydrogen bridging bonds of the N? H …? Cl type connect the nitrogen atom to two chloride ions. Two short distances C …? Cl are interpreted in terms of C? H …?Cl hydrogen bridges.     

Die Kristallstruktur des 1 : 1-Adduktes zwischen Antimontrichlorid und Diphenylammoniumchlorid,SbCl3 · (C6H5)2NH2+Cl−

The Crystal Structure of the 1:1 Addition Compound between Antimony Trichloride and Diphenylammonium Chloride, SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? The 1:1 addition compound between antimony trichloride and diphenylammoniumchloride SbCl₃ · (C₆H₅)₂NH₂⁺Cl^? crystallizes in the monoclinic space group P2₁/n with a = 5.668(8), b = 20.480(12), c = 14.448(17) Å, β = 110.4(1)° and Z = 4 formula units. Chains of SbCl₃ molecules and anion cation chains are bridged by Cl ions and form square tubes. The coordination of the Sb atoms by Cl atoms by Cl atoms and Cl ions is distorted octahedral. Mean distances are Sb? Cl = 2.37 Å for Sb? Cl (3×), 3.09 Å for Sb…Cl^? (2×) and 3.42 Å for Sb…Cl (1×). The Sb…Cl^? contacts and hydrogen bonds NH…Cl^? at 3.15 Å generate tetrahedral coordination of the Cl ions.     

Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.     

Weak hydrogen and halogen bonding in 4‐[(2,2‐difluoroethoxy)methyl]pyridinium iodide and 4‐[(3‐chloro‐2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium iodide

To enable a comparison between a C—H…X hydrogen bond and a halogen bond, the structures of two fluorous‐substituted pyridinium iodide salts have been determined. 4‐[(2,2‐Difluoroethoxy)methyl]pyridinium iodide, C₈H₁₀F₂NO⁺·I⁻, (1), has a –CH₂OCH₂CF₂H substituent at the para position of the pyridinium ring and 4‐[(3‐chloro‐2,2,3,3‐tetrafluoropropoxy)methyl]pyridinium iodide, C₉H₉ClF₄NO⁺·I⁻, (2), has a –CH₂OCH₂CF₂CF₂Cl substituent at the para position of the pyridinium ring. In salt (1), the iodide anion is involved in one N—H…I and three C—H…I hydrogen bonds, which, together with C—H…F hydrogen bonds, link the cations and anions into a three‐dimensional network. For salt (2), the iodide anion is involved in one N—H…I hydrogen bond, two C—H…I hydrogen bonds and one C—Cl…I halogen bond; additional C—H…F and C—F…F interactions link the cations and anions into a three‐dimensional arrangement.     

Supramolecular architectures in the salt trimethoprimium ferrocene‐1‐carboxylate and the cocrystal 4‐amino‐5‐chloro‐2,6‐dimethylpyrimidine–ferrocene‐1‐carboxylic acid (1/1)

In the salt trimethoprimium ferrocenecarboxylate [systematic name: 2,4‐diamino‐5‐(3,4,5‐trimethoxybenzyl)pyrimidin‐1‐ium ferrocene‐1‐carboxylate], (C₁₄H₁₉N₄O₃)[Fe(C₅H₅)(C₆H₄O₂)], (I), of the antibacterial compound trimethoprim, the carboxylate group interacts with the protonated aminopyrimidine group of trimethoprim via two N—H…O hydrogen bonds, generating a robust R ₂²(8) ring motif (heterosynthon). However, in the cocrystal 4‐amino‐5‐chloro‐2,6‐dimethylpyrimidine–ferrocene‐1‐carboxylic acid (1/1), [Fe(C₅H₅)(C₆H₅O₂)]·C₆H₈ClN₃, (II), the carboxyl–aminopyrimidine interaction [R ₂²(8) motif] is absent. The carboxyl group interacts with the pyrimidine ring via a single O—H…N hydrogen bond. The pyrimidine rings, however, form base pairs via a pair of N—H…N hydrogen bonds, generating an R ₂²(8) supramolecular homosynthon. In salt (I), the unsubstituted cyclopentadienyl ring is disordered over two positions, with a refined site‐occupation ratio of 0.573 (10):0.427 (10). In this study, the two five‐membered cyclopentadienyl (Cp) rings of ferrocene are in a staggered conformation, as is evident from the C…Cg …Cg …C pseudo‐torsion angles, which are in the range 36.13–37.53° for (I) and 22.58–23.46° for (II). Regarding the Cp ring of the minor component in salt (I), the geometry of the ferrocene ring is in an eclipsed conformation, as is evident from the C…Cg …Cg …C pseudo‐torsion angles, which are in the range 79.26–80.94°. Both crystal structures are further stabilized by weak π–π interactions.     

Supramolecular structures of rhenium(I) complexes mediated by ligand planarity via the interplay of substituents

The crystal and molecular structures of two Re^I tricarbonyl complexes, namely fac‐tricarbonylchlorido[1‐(4‐fluorocinnamoyl)‐3‐(pyridin‐2‐yl‐κN)pyrazole‐κN²]rhenium(I), [ReCl(C₁₇H₁₂FN₃O)(CO)₃], (I), and fac‐tricarbonylchlorido[1‐(4‐nitrocinnamoyl)‐3‐(pyridin‐2‐yl‐κN)pyrazole‐κN²]rhenium(I) acetone monosolvate, [ReCl(C₁₇H₁₂ClN₄O₃)(CO)₃]·C₃H₆O, (II), are reported. The complexes form centrosymmetric dimers that are linked into one‐dimensional columns by C—H…Cl and N—O…H interactions in (I) and (II), respectively. C—H…Cl interactions in (II) generate two R₂¹(7) loops that merge into a single R₂¹(10) loop. These interactions involve the alkene, pyrazole and benzene rings, hence restricting the ligand rotation and giving rise to a planar conformation. Unlike (II), complex (I) exhibits a twisted conformation of the ligand and a pair of molecules forms a centrosymmetric dimer with an R₂²(10) loop via C—H…O interactions. The unique supramolecular structures of (I) and (II) are determined by their planarity and weak interactions. The planar conformation of (II) provides a base for appreciable π–π stacking interactions compared to (I). In addition, an N—O…π interaction stabilizes the supramolecular structure of (II). We report herein the first n→π* interactions of Re^I tricarbonyl complexes, which account for 0.33 kJ mol⁻¹. Intermolecular C—H…Cl and C—H…O interactions are present in both complexes, with (II) showing a greater preference for these interactions compared to (I), with cumulative contributions of 48.7 and 41.5%, respectively. The influence of inductive (fluoro) and/or resonance (nitro) effects on the π‐stacking ability was further supported by LOLIPOP (localized orbital locator‐integrated π over plane) analysis. The benzene ring of (II) demonstrated a higher π‐stacking ability compared to that of (I), which is supported by the intrinsic planar geometry. The HOMA (harmonic oscillator model of aromaticity) index of (I) revealed more aromaticity with respect to (II), suggesting that NO₂ greatly perturbed the aromaticity. The Hirshfeld fingerprint (FP) plots revealed the preference of (II) over (I) for π–π contacts, with contributions of 6.8 and 4.4%, respectively.     

Die kristallstruktur des 2;1-Adduktes zwischen Antimontrichlorid und Diphenyl, 2SbCl3 · (C6H5)2

The Crystal Structure of the 2:1 Addition Compound between Antimony Trichloride and Diphenyl, 2SbCl₃ · (C₆H₅)₂ The 2:1 adduct of antimony trichloride with diphenyl, 2SbCl₃ · (C₆H₅)₂, crystallizes in the triclinic space group P1 with a = 13.498(5) Å, b = 7.884(2) Å, c = 9.341(3) Å, α = 86.40(2)°, β = 110.05(3)⁰, γ = 91.41(2)° and Z = 2. Each SbCl₃ molecule points to a phenyl ring of the diphenyl molecule. The distances from the two independent Sb atoms to the phenyl ring planes differ (3.26 and 3.08 Å). The torsion angle between the phenyl ring planes within the diphenyl molecule is 40.5°. The mean Sb? Cl bond distance is 2.39 Å. Longer Sb…Cl contacts of 3.44 to 3.46 Å and the π-donor-acceptor interactions complete the distorted octahedral coordination, and ψ-octahedral coordination respectively, of the Sb atoms.     

Supramolecular hydrogen‐bonding patterns in salts of the antifolate drugs trimethoprim and pyrimethamine

Nine salts of the antifolate drugs trimethoprim and pyrimethamine, namely, trimethoprimium [or 2,4‐diamino‐5‐(3,4,5‐trimethoxybenzyl)pyrimidin‐1‐ium] 2,5‐dichlorothiophene‐3‐carboxylate monohydrate (TMPDCTPC, 1:1), C₁₄H₁₉N₄O₃⁺·C₅HCl₂O₂S⁻, ( I ), trimethoprimium 3‐bromothiophene‐2‐carboxylate monohydrate, (TMPBTPC, 1:1:1), C₁₄H₁₉N₄O₃⁺·C₅H₂BrO₂S⁻·H₂O, ( II ), trimethoprimium 3‐chlorothiophene‐2‐carboxylate monohydrate (TMPCTPC, 1:1:1), C₁₄H₁₉N₄O₃⁺·C₅H₂ClO₂S⁻·H₂O, ( III ), trimethoprimium 5‐methylthiophene‐2‐carboxylate monohydrate (TMPMTPC, 1:1:1), C₁₄H₁₉N₄O₃⁺·C₆H₅O₂S⁻·H₂O, ( IV ), trimethoprimium anthracene‐9‐carboxylate sesquihydrate (TMPAC, 2:2:3), C₁₄H₁₉N₄O₃⁺·C₁₅H₉O₂⁻·1.5H₂O, ( V ), pyrimethaminium [or 2,4‐diamino‐5‐(4‐chlorophenyl)‐6‐ethylpyrimidin‐1‐ium] 2,5‐dichlorothiophene‐3‐carboxylate (PMNDCTPC, 1:1), C₁₂H₁₄ClN₄⁺·C₅HCl₂O₂S⁻, ( VI ), pyrimethaminium 5‐bromothiophene‐2‐carboxylate (PMNBTPC, 1:1), C₁₂H₁₄ClN₄⁺·C₅H₂BrO₂S⁻, ( VII ), pyrimethaminium anthracene‐9‐carboxylate ethanol monosolvate monohydrate (PMNAC, 1:1:1:1), C₁₂H₁₄ClN₄⁺·C₁₅H₉O₂⁻·C₂H₅OH·H₂O, ( VIII ), and bis(pyrimethaminium) naphthalene‐1,5‐disulfonate (PMNNSA, 2:1), 2C₁₂H₁₄ClN₄⁺·C₁₀H₆O₆S₂²⁻, ( IX ), have been prepared and characterized by single‐crystal X‐ray diffraction. In all the crystal structures, the pyrimidine N1 atom is protonated. In salts ( I )–( III ) and ( VI )–( IX ), the 2‐aminopyrimidinium cation interacts with the corresponding anion via a pair of N—H…O hydrogen bonds, generating the robust R₂²(8) supramolecular heterosynthon. In salt ( IV ), instead of forming the R₂²(8) heterosynthon, the carboxylate group bridges two pyrimidinium cations via N—H…O hydrogen bonds. In salt ( V ), one of the carboxylate O atoms bridges the N1—H group and a 2‐amino H atom of the pyrimidinium cation to form a smaller R₂¹(6) ring instead of the R₂²(8) ring. In salt ( IX ), the sulfonate O atoms mimic the role of carboxylate O atoms in forming an R₂²(8) ring motif. In salts ( II )–( IX ), the pyrimidinium cation forms base pairs via a pair of N—H…N hydrogen bonds, generating a ring motif [R₂²(8) homosynthon]. Compounds ( II ) and ( III ) are isomorphous. The quadruple DDAA (D = hydrogen‐bond donor and A = hydrogen‐bond acceptor) array is observed in ( I ). In salts ( II )–( IV ) and ( VI )–( IX ), quadruple DADA arrays are present. In salts ( VI ) and ( VII ), both DADA and DDAA arrays co‐exist. The crystal structures are further stabilized by π–π stacking interactions [in ( I ), ( V ) and ( VII )–( IX )], C—H…π interactions [in ( IV )–( V ) and ( VII )–( IX )], C—Br…π interactions [in ( II )] and C—Cl…π interactions [in ( I ), ( III ) and ( VI )]. Cl…O and Cl…Cl halogen‐bond interactions are present in ( I ) and ( VI ), with distances and angles of 3.0020 (18) and 3.5159 (16) Å, and 165.56 (10) and 154.81 (11)°, respectively.     

3,5‐Bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐piperidone and 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐oxopiperidinium chloride: potential biophotonic materials

In the title compound 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐piperidone, C₂₂H₂₃NO₃, (I), the central heterocyclic ring adopts a flattened boat conformation, while in the related salt 3,5‐bis(4‐methoxy­benzyl­idene)‐1‐methyl‐4‐oxopiperidin­ium chloride, C₂₂H₂₄NO₃⁺·Cl⁻, (II), the ring exhibits a `sofa' conformation in which the N atom deviates from the planar fragment. The pendant benzene rings are twisted from the heterocyclic ring planes in both mol­ecules in the same direction, the range of dihedral angles between the ring planes being 24.5 (2)–32.7 (2)°. The dominant packing motif in (I) involves centrosymmetric dimers bound by weak intermolecular C—H⋯O hydrogen bonds. In (II), cations and anions are linked by strong N—H⋯Cl hydrogen bonds, while weak C—H⋯O and C—H⋯Cl hydrogen bonds link the cations and anions into a three‐dimensional framework.     

Supramolecular interactions in carboxylate and sulfonate salts of 2,6‐diamino‐4‐chloropyrimidinium

Two new salts, namely 2,6‐diamino‐4‐chloropyrimidinium 2‐carboxy‐3‐nitrobenzoate, C₄H₆ClN₄⁺·C₈H₄NO₆⁻, (I), and 2,6‐diamino‐4‐chloropyrimidinium p‐toluenesulfonate monohydrate, C₄H₆ClN₄⁺·C₇H₇O₃S⁻·H₂O, (II), have been synthesized and characterized by single‐crystal X‐ray diffraction. In both crystal structures, the N atom in the 1‐position of the pyrimidine ring is protonated. In salt (I), the protonated N atom and the amino group of the pyrimidinium cation interact with the carboxylate group of the anion through N—H…O hydrogen bonds to form a heterosynthon with an R ₂²(8) ring motif. In hydrated salt (II), the presence of the water molecule prevents the formation of the familiar R ₂²(8) ring motif. Instead, an expanded ring [i.e. R ₃²(8)] is formed involving the sulfonate group, the pyrimidinium cation and the water molecule. Both salts form a supramolecular homosynthon [R ₂²(8) ring motif] through N—H…N hydrogen bonds. The molecular structures are further stabilized by π–π stacking, and C=O…π, C—H…O and C—H…Cl interactions.     

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4-fluorbenzolsulfonyl)amin-Dimethylsulfoxid(2/1)

Polysulfonyl Amines. XLVI. Molecular Adducts of Di(organosulfonyl)amines with Dimethyl Sulfoxide and Triphenylphosphine Oxide. X-Ray Structure Determination of Di(4-fluorobenzenesulfonyl)amine-Dimethyl Sulfoxide(2/1) From equimolar solutions of the respective components in CH₂Cl₂/petroleum ether, the following crystalline addition compounds were obtained: (X? C₆H₄SO₂)₂NH …? OS(CH₃)₂, where X = H, 4? CH₃, 4? Cl, 4? Br, 4? I, 4? NO₂ or 3? NO₂; [(4? F? C₆H₄SO₂)₂NH]₂ · (OS(CH)₃)₂ ( 8 ); (4? I? C₆H₄SO₂)₂NH · OP(C₆H₅)₃. A (2/1) complex of (4? F? C₆H₄SO₂)₂NH with OP(C₆H₅)₃ could not be isolated. The solid-state structure of the (2/1) compound 8 is compared with the known structure of the (1/1) complex (CH₃SO₂)₂NH · OS(CH₃)₂. The crystallographic data for 8 at ?95°C are: monoclinic, space group C2/c, a = 2 369.9(13), b = 1 006.8(4), c = 2 772.6(13) pm, β = 110.71(4)°, U = 6.187 nm³, Z = 8. Two N? H …? O hydrogen bonds with N …? O 275 and 280 pm connect the disulfonylamine molecules with the dimethyl sulfoxide molecule. The O atom of the latter has a trigonal-planar environment consisting of the S atom and the two hydrogen bond H atoms.     

Synthese und Kristallstrukturen von 1,1,3,3‐Tetramethylimidazolinium‐dichlorid und 1,1,4‐Trimethylpiperazinium‐chlorid

Synthesis and Crystal Structures of 1,1,3,3‐Tetramethylimidazolinium Dichloride and 1,1,4‐Trimethylpiperazinium Chloride Single crystals of 1,1,3,3‐tetramethylimidazolinium dichloride ( 1 ) and 1,1,4‐trimethylpiperazinium chloride ( 2 ) were obtained by reaction of CH₂Cl₂ with tetramethylethylenediamine (TMEDA) and NNN′N″N″‐pentamethyldiethylenetriamine (PMDETA), respectively. Both compounds are characterized by single crystal X‐ray diffraction and by IR spectroscopy. 1: [C₇H₁₈N₂]Cl₂, space group P2₁/c, Z = 4, lattice dimensions at 193(2) K: a = 821.97(11), b = 1130.38(8), c = 1143.08(13) pm, β = 100.348(15)°, R₁ = 0.0271. The C₇N₂ heterocyclic ring has envelope conformation like other salts with this dication. 2: [C₇H₁₇N₂]Cl, space group P2₁2₁2₁, Z = 4, lattice dimensions at 100(2) K: a = 1030.37(8), b = 1036.55(6), c = 831.39(4) pm, R₁ = 0.0180. Although the heterocyclic mono‐cation is without site symmetry in the crystal, its molecular symmetry is close to C_s, forming chair conformation of the C₄N₂ six‐membered ring.     

Conformations of fused cycloalkanes in organometallic complexes : IV. The crystal and molecular structure of tricyclo-[6.4.0.02.7]dodeca-3,5-dienetricarbonyliron

The precise molecular structure of the title compound has been determined by single crystal X-ray diffractometry. It consists of a cyclohexadiene ring fused at the 5 and 6 positions to a cyclobutane ring which is in turn fused to a cyclohexane ring. The two six-membered rings are trans to each other with respect to the shared four-membered ring. The Fe(CO)₃ moiety is bound in the usual way to the conjugated diene portion of the cyclohexadiene ring. The feature of greatest interest is the mutual influence of the conformations of the two fused cycloalkane rings, whose intrinsically preferred conformations are mutually incompatible. Under the influence of the fused cyclohexadiene ring the C₄ ring would tend to be planar, while the cyclohexane ring would tend, of itself, to have a chair conformation. The actual result is a compromise, with the C₄ ring being folded by 15° along its diagonal and the C₆ ring having a conformation intermediate between planarity and a chair. Crystallographic data: space group, P2₁, Z = 2. Unit cell dimensions at 3°C are a = 6.176(1), b = 11.307(2), c = 9.781(2) Å and β = 92.89(2)°. A set of 1733 reflections having 2θ(Mo-K_α) < 63.7° and I > σ(I) was refined to convergence (R₁ = 0.055; R₂ = 0.034) with hydrogen atoms refined isotropically and all others anisotropically.     

Kristallstruktur von Dipyridiniomethan-Monohalogenohydro-closo-Decaboraten(2–), [(C5H5N)2CH2][2-XB10H9]; X  Cl,Br, I

Crystal Structures of Dipyridiniomethane Monohalogenohydro-closo-Decaborates(2–), [(C₅H₅N)₂CH₂][2-XB₁₀H₉]; X = Cl, Br, I [B₁₀H₁₀]^2? reacts with chlorine, bromine and iodine or with N-halogenosuccinimide, yielding the monohalogenodecaborates [2-XB₁₀H₉]^2? (X = Cl, Br, I), which are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from the starting compound and higher halogenated products. The X-ray structure determinations of the isotypic chloro and bromo compounds [(C₅H₅N)₂CH₂][2-XB₁₀H₉] (monoclinic, space group C2/c, Z = 8; for X ? Cl: a = 33.174(5), b = 7.2809(4), c = 16.2232(7) Å, β = 113.307(7)°; for X = Br: a = 33.525(11), b = 7.281(2), c = 16.297(4) Å, β = 113.62(2)°) and of the iodo compound [(C₅H₅N)₂CH₂][2-IB₁₀H₉] (monoclinic, space group P2₁, Z = 2, a = 7.143(3), b = 13.568(4), c = 9.479(7) Å, β = 97.57(5)°) show columns of substituted boron clusters [2-XB₁₀H₉]^2?, X = Cl, Br, I and bent dications [(C₅H₅N)₂CH₂]²⁺ along the shortest axis wich are assembled to alternating layers in the crystal lattice.     

Silber(I)‐di(arensulfonyl)amide und ein Silber(I)‐(arensulfonyl)(alkansulfonyl)amid: Von Bändern zu lamellaren Schichten mit kurzen Zwischenschichtkontakten C–H…Hal–C oder C–Br…Br–C

Structures of Ionic Di(arenesulfonyl)amides. 2. Silver(I) Di(arenesulfonyl)amides and a Silver(I) (Arenesulfonyl)(alkanesulfonyl)amide: From Ribbons to Lamellar Layers Exhibiting Short C–H…Hal–C or C–Br…Br–C Interlayer Contacts Low‐temperature X‐ray crystal structures are reported for AgN(SO₂C₆H₄‐4‐X)₂ · H₂O, where X is Cl ( 4 ) or Br ( 5 ), and for AgN(SO₂Ph)(SO₂Me) ( 6 ). Compounds 4 and 5 and the previously described F analogue ( 3 ) are isotypic, though not strictly isostructural (monoclinic, space group P2₁/c, Z = 4, but egregiously large discrepancies of x and z coordinates for corresponding atoms). Throughout this triad, glide‐plane related formula units are linked along the z axis to form infinite ribbons [(ArSO₂)₂N–Ag(μ‐H₂O)]_∞, in which Ag extends its coordination number to five by accepting one Ag–O bond from each of the (ArSO₂)₂N^⊖ ligands in the adjacent units. By means of O–H…O(S) hydrogen bonds, the ribbons are associated into lamellar layers parallel to the xz plane. Owing to the folded conformation of the anions, the layers display an inner polar region of Ag atoms, H₂O molecules and N(SO₂)₂ groups, outer apolar regions of stacked pairs of aryl rings, and interlayer regions hosting the halogen atoms. Inspection of the latter areas provides sound evidence that the distinct juxtapositions of adjacent layers arise from specific interlamellar attractions and repulsions ( 3 : two C–H…F, all F…F beyond the van der Waals limit d_W; 4 : one C–H…Cl, close packing of Cl atoms at Cl…Cl ≈ d_W; 5 : one C–H…Br, one short Br…Br contact < d_W, all other Br…Br > d_W). Structure 6 (monoclinic, P2₁/n, Z = 4) consists of a lamellar coordination polymer, in which the cation accepts one Ag–N and three Ag–O bonds drawn from four different anions. On account of crystal symmetry, the extended ligand has its Ph and Me groups distributed on both sides of the sheet, the phenyl rings forming the apolar regions of the lamella, whereas the smaller methyl groups are integrated into the corrugated inorganic region by means of weak C–H…O hydrogen bonds.     

Occurrence of the Unusual 2C5 (1C4) Chair Conformation in Two Carbohydrates and the Reverse Anomeric Effect. X-Ray Structures of 3,4,5,7-Tetra-O-Acetyl-2,6-Anhydro-D-Glycero-D-Ido-Heptonamide (1) and 3,4,5,7-Tetra-O-Acetyl-2,6-Anhydro-D-Glycero-L-Gluco-Heptonamide (2)

Abstract

The title compounds 1 and 2 (both C₁₅O₁₅NH₂₁) crystallized in the monoclinic space group P2₁ (Z = 2) with a=8.864(1), b=8.346(1), c =13.569(1)Å, β =114.12(1), V=918.1(2)A3, D(calc) = 1.358 g/cc for compound 1, and a=15–045(1), b=8.106(1), c=7.491(1)Å, β =97.23(1)°, V=906.4(3)Å3 D(calc)= 1.375 g/cc, for compound 2. The structures were solved by direct methods and refined by the full-matrix least squares technique to R indices of 0.010 and 0.046, respectively. Both compounds are in the α ? D configuration and adopt the unusual ²C₅, (¹C₄) chair conformation with the carbamoyl groups on the anomeric carbon atoms equatorially oriented. In this conformation the orientations of the substituents are 2e, 3a, 4a, 5a and 6a in 1 and 2e, 3a, 4a, 5e and 6a in 2 which leads to unfavorable 1,3-diaxial interactions. The “reverse anomeric effect” which induces the ²c₅ chair conformation in these compounds, may have its origin in the unfavorable steric interactions found in the ⁵c₂ (⁴C₁) conformation where the carbamoyl group is axially oriented. Furthermore, the ²C₅ conformation is stabilized by the N-H … O intramolecular hydrogen bond between the carbamoyl nitrogen atom and the pyranosyl ring oxygen atom. Semi-empirical energy calculations reveal that the rotational freedom of the carbamoyl group is greater for the equatorial orientation (²C₅) than for the axial orientation (⁵C₂).     

On the reaction of aminobis(diorganylamino)phosphanes with halogenophosphanes—P-hydrogeno(iminophosphoranyl)-halogenophosphanes and P-hydrogeno(iminophosphoranyl)-σ2, λ3-iminophosphanes

Reactions of triaminophosphane (R₂N)₂P–NH₂, (R = ¹Pr) 1a, with aminodihalogenophosphanes ¹Pr₂N–PX₂, 2a–c [X = CL (a), Br (b), I(c)], in the presence of a base yielded the P-hydrogeno-iminophosphoranyl-halogenophosphanes (R₂N)₂PH = N–PX–N(¹Pr)₂ 4a–c [X = Cl (a), Br (b), I(c)]. Analogous reactions between 1a and 1b (b: R = c-hexyl) and chloroiminophosphane (Cl–P = N–Mes^*, (Mes^* = 2,4,6-^tBu₃C₆H₂) 6 , gave the P-hydrogeno(iminophosphoranyl)-σ²,λ³-iminophosphanes, (R₂N)₂PH = N–P = N–Mes^* 8a and 8b. In solution 8a, 8b eliminated amine, yielding σ², λ³-iminophosphanyl-substituted 1,3,2,4-diazadiphosphetidines [(R₂N)PN(P = N–Mes^*)]₂, 10a, 10b , and 11 ( 10a and 10b : cis; 11: trans). The X-ray structure analyses of compounds 4a, 4b, 8a, and 11 are discussed. © 1996 John Wiley & Sons, Inc.     

Onium‐di(arensulfonyl)amide: Von der gestreckten zur gefalteten Konformation des (ArSO2)2N⊖‐Anions

Structures of Ionic Di(arenesulfonyl)amides. 1. Onium Di(arenesulfonyl)amides: From the Extended to the Folded Conformation of the (ArSO₂)₂N^⊖ Anion In a study preceding the investigation of lamellar metal di(arenesulfonyl)amides, the bonding and conformational characteristics of non‐coordinating (ArSO₂)₂N^⊖ ions have been established within a series of appropriate onium salts. Starting from the strong NH acids HN(Q‐4‐X)₂, where Q = SO₂C₆H₄, the following model compounds were prepared by neutralization or cocrystallization procedures and subjected to low‐temperature X‐ray analyses: Pr₄N^⊕. ^⊖N(Q‐4‐COOMe)₂ ( 2 , monoclinic, space group C2/c, Z = 4), Pr₄N^⊕ · ^⊖N(Q‐4‐COOH)₂ ( 3 , monoclinic, Cc, Z = 4, O₂SNSO₂ group disordered), Me₃NOH^⊕ · ^⊖N(Q‐4‐F)₂ ( 4 , monoclinic, P2₁/n, Z = 4), [DA18C6]^2⊕ · 2 ^⊖N(Q‐4‐H)₂ ( 6 , cation = 1,10‐diazonia‐18‐crown‐6, monoclinic, P2₁/c, Z = 2), [DA18C6]^2⊕ · 2 ^⊖N(Q‐4‐Me)₂ ( 7 , triclinic, P1, Z = 1), and [DA18C6]^2⊕ · 2 ^⊖N(Q‐4‐Cl)₂ · 2 CH₂Cl₂ ( 8 , monoclinic, P2₁/c, Z = 2). Structures 2 – 4 represent the energetically favoured, extended or open conformation of the CO₂S–N–SO₂C bridge (crystallographic twofold symmetry for 2 , pseudo‐C₂ symmetry for 3 and 4 ), whereas in 6 – 8 the anions adopt the folded or hair‐pin conformation (pseudo‐C_s symmetry), which is a prerequisite in lamellar structures. The interdependence of bond lengths and angles within ^⊖N(SO₂C)₂ and HN(SO₂C)₂ moieties is substantiated. In 6 – 8 , the [DA18C6]^2⊕ macrocycles exhibit the well‐known “biangular” C_i conformation and are connected to two symmetry related anions by N–H…O hydrogen bonds; structures 4 and 3 respectively display O–H…N bonded cation‐anion pairs or C(O)–O–H…O=S mediated anion chains. Weak hydrogen bonds C–H…O are observed in all the crystal packings. The hitherto unreported amines HN(Q‐4‐X)₂, where X is C(O)OMe or C(O)NH₂, were obtained by treating the corresponding dicarboxylic acid with OSCl₂ to form the bis(acyl chloride) and subjecting the latter to methanolysis or ammonolysis.