Thomas Hamann

Polysulfonylamine: XLIII. Trimethylgermanium(IV)- und Trimethylblei(IV)-dimesylamid: Synthese und Festkörperstrukturen

Abstract The new compounds Me 3 GeN(SO 2 Me) 2 ( 3 ) and Me 3 PbN(SO 2 Me) 2 ( 4 ) were prepared from the corresponding chlorides Me 3 ECl and AgN(SO 2 Me) 2 in MeCN solution. The crystallographic data at −95°C are for 3 : triclinic, space group P 1 , a 771.7(2), b 1204.1(4), c 1388.4(5) pm, α 66.75(3), β 84.12(3), γ 74.15(2)°, V 1.1401 nm 3 , Z = 4; for 4 : monoclinic, space group P 2 1 / c , a 751.1(3), b 1065.5(4), c 1493.9(5) pm, β 100.99(3)°, V 1.1738 nm 3 , Z = 4. The crystal structure of 3 consists of two crystallographically independent, monomeric molecules with tetrahedral Ge atoms and trigonal- planar N atoms (average angle values: CGeC 112.7, CGeN 106.0, GeNS 121.1, SNS 117.3 °). The most striking features of the molecular structure are the extremely long GeN bond distances of 198.2(2) and 198.5(2) pm, which are equal to the uncorrected sum of the covalent single bond radii. In the crystal structure of 4 , Me 3 PbN(SO 2 Me) 2 units are linked by an intermolecular PbO interaction (265.3(6) pm) to form infinite parallel chains. The Pb atom has a distorted trigonal-bipyramidal arrangement (NPbO 169.3; average values: CPbC 119.2, CPbN 95.5, CPbO 84.8°), in which the N atom is trigonal-planar (SNS 119.2, mean PbNS 119.8°). The PbN distance is 248.4(6) pm, i.e. 30 pm longer than the sum of the covalent radii, suggesting a mainly ionic bond character. In both structures secondary intramolecular 1,4-interactions with Ge ⋯ O distances of 295.8 and Pb ⋯ O of 328 pm, respectively, are observed.

POLYSULFONYLAMINE: TEIL LXVIII.1 EINFLUSS DER N,N-DISULFONYLIERUNG AUF DIE C–N-BINDUNG PRIMÄRER AMINE: SYNTHESE UND FESTKÖRPERSTRUKTUREN VON VIER VERBINDUNGEN DES TYPS R′–N(SO2R)2

Abstract In order to obtain more accurate information about the bonding geometry of nitrogen in N-organyl disulfonylamines, the crystal and molecular structures of the following compounds were determined by low-temperature X-ray diffraction: N-Methyl benzene-1,2-disulfonimide (1; triclinic, space group P 1), N-methyl ditosylamine (2; monoclinic, P21/c), N-(cyclopropylmethyl) dimesylamine (3; monoclinic, P21/c), and N-phenyl dimesylamine (4; monoclinic, P21/c). In 2, 3 and 4, nitrogen displays a trigonal-planar CNS2 geometry, whereas the N atom of the cyclic imide 1 has a pyramidal coordination (mean C–N–S 118.3–119.5° for 1–4, S–N–S 112.8° for 1 and 121.0–123.3° for 2–4). All N–S bonds are short, with mean distances ranging from 166.7 to 167.9 pm. The most striking feature of the four molecular structures are the N–C bond distances (148.1 pm for 1 and 2, 149.8 pm for 3, 144.6 pm for 4), which are appreciably longer than the appropriate average N(sp2)–C(sp3) or N(sp2)–Car, values (145.4 and 137.2 pm, respe...

POLYSULFONYLAMINE: TEIL LXVI.1 AUF DER SUCRE NACH LANGEN Si(sp3)[sbnd]N(sp2)-BINDUNGEN: SYNTHESE VON N,N-DISULFONYLIERTEN SILYLAMINEN UND FESTKORPERSTRUKTUR VON (4-Cl-C6H4SO2)2N[sbnd]SiMe3

Abstract Twelve new N,N-di(organosulfonyl) silylamines (R1SO2)2N[sbnd]SiR2R3R4, where Rn = alkyl or aryl, were obtained as moisture-sensitive solids or liquids by treating the silver salts (R1SO2)2N Ag with chlorosilanes ClSiR2R4 in MeCN solution. Some of the compounds appear to establish N,O-silylotropy equilibria in solution (NMR evidence). The crystallographic data for (4-Cl-C6H4SO2)2N[sbnd]SiMe3 are (at -75°C): triclinic, space group P1, a = 659.2(3), b = 1134.5(5), c = 1334.3(6) pm, α = 96.52(3), β = 103.35(3), γ = 93.32(3)°, V = 0.9610(7) nm3, Z = 2. The Me3Si group is attached to the nitrogen atom through an unusually long Si[sbnd]N bond (184.3 pm). Concomitantly, the S[sbnd]N bonds are relatively short (166.9 and 168.1 pm). The bond angles of the trigonal-planar SiNS2 unit are distorted by an intramolecular 1.4-interaction between silicon and a sulfonyl oxygen atom (Si[sbnd]O 286.3 pm, Si[sbnd]N[sbnd]S 117.2 and 123.8, S[sbnd]N[sbnd]S 118.6°, sum of bond angles at nitrogen 359.6°).

Polysulfonylamine, XXXVI Trimethylsilyl-dimesylamin: Darstellung, NMR-spektroskopische Charakterisierung und Reaktionsfähigkeit als Silylierungsreagens / Polysulfonylamines, XXXVI Trimethylsilyl Dimesylamine: Preparation, NMR-Spectroscopic Characterization, and Reactivity as a Silylating Agent

(CH3)3SiN(SO2CH3)2 (1), m. p. 69-70 °C, is obtained by metathesis of AgN(SO2CH3)2 with (CH3)3SiCl (improvement of a known procedure) or, more conveniently, by silylation of HN(SO2CH3)2 with [(CH3)3Si]2NH. The 1H, 13C and 29Si NMR solution spectra and the 29Si NMR solid-state spectrum suggest the constitution of 1 in solution (CDC13, CD2C12, CDCl2–CDCl2) to be an equilibrium mixture of the N-silylated form (CH3)3Si–N(SO2CH3)2 (I) and the O-silylated form (CH3)3Si–O–S(O)(CH3)=NSO2CH3 (II) in a molar ratio of 2:1 at room temperature, whereas in the known crystal structure of 1 only form I is present. The solid-state NMR experiment acted as a bridge between X-ray crystallography and solution-state NMR, enabling assignments of the resonances to be made with confidence to the tautomers. At room temperature, form II undergoes a rapid intramolecular 1.5-migration of silicon between oxygen centers of the two sulfonyl groups. As shown by kinetic measurements using 1H NMR spectroscopy, 1 is a highly reactive agent for silylating ketones in the presence of triethylamine. Hydroxy and thiol functions, even when sterically hindered, are silylated by 1 in uncatalyzed reactions. It is further shown that HN(SO2CH3)2 is an efficient catalyst for silylations with [(CH3)3Si]2NH.

Polysulfonylamine, CXLIII [1], Rolle schwacher Wasserstoffbrücken (C - H···O) in den Kristallstrukturen von 2,6-Dimethylpyridinium-, 1-Hydroxypyridinium- und Imidazolium-dimesylamid / Polysulfonylamines, CXLIII [1], Role of Weak Hydrogen Bonds (C - H···O) in the Crystal Structures of 2,6-Dimethylpyridinium , 1-Hydroxypyridinium and Imidazolium Dimesylamide

In order to study hydrogen bonding networks in ionic crystals, low-temperature X-ray structures were determined for three onium salts of general formula BH+(MeSO2)2N- , where BH+ is 2,6-dimethylpyridinium (1; monoclinic, space group P21/c, Z′ = 1), 1-hydroxypyridinium (2; triclinic, P1̅, Z′ = 1), or imidazolium (3; monoclinic, Cc, Z′ = 1). The asymmetric units consist of cation-anion pairs assembled in 1 and 3 by ordinary N+ - H···N hydrogen bonds, in 2 by a very short N+ - O - H···N- bond belonging to the class (+/-)CAHB [H···O 148(3), O···N 253.5(2) pm, O - H···N 175(3)°]. The second N -H donor of the imidazolium ion is involved in a nearly symmetric N - H (···O)2 three-centre bond to two different anions. In the pyridine derivatives, the (MeSO2 )2N- ions are associated via short C(sp3) - H···O contacts to form a three-dimensional framework of corrugated and cross-linked layers (1) or an assembly of discrete corrugated layers (2). As a common feature, these anion substructures are pervaded by hexagonal channels parallel to x, each one accommodating two stacks of cations that are linked to the channel walls by the unique strong hydrogen bond and a set of short Car - H···O contacts; moreover, cations drawn from adjacent stacks in structure 2 create inversion-symmetric dimers based upon a short Car - H···O(H) - N interaction. In contrast, the structure of 3 displays planar anion layers assembled by short C(sp3 ) - H···O contacts, intercalating the cations with their ring planes perpendicular to the layer planes and binding them by means of the strong hydrogen bonds and three Car -H···O interactions. All C - H···O taken into consideration have normalized parameters d( H···O) ≤ 267 pm and θ(C - H···O) ≥ 121°.

Polysulfonylamine, CLXXIII [1]. Intermolekulare Wechselwirkungen in kristallinen Di(organosulfonyl)aminen. – Teil 2 [2]. Strukturvergleich f ¨ur Di(4-X-benzolsulfonyl)amine mit X = Fluor, Chlor, Brom oder Methyl / Polysulfonylamines, CLXXIII [1]. Intermolecular Interactions in Crystalline Di(organosulfonyl) amines. Part 2 [2]. Comparing the Stuctures of Di(4-X-benzenesulfonyl)amines, where X is Fluorine, Chlorine, Bromine, or Methyl

Low-temperature X-ray structures of the following di(4-X-benzenesulfonyl)amines, HN(SO2-C6H4-X)2, are compared in order to study the effects of the 4-substituents on the molecular packings: X = F (1, monoclinic, C2/c, Z′ = 1), X = Cl (2, monoclinic, C2/c, Z′ = 1/2, N-H bonds lying on twofold rotation axes), X = Me (3, orthorhombic, Pbca, Z′ = 1), X = Br (4A, monoclinic, P21/c, Z′ = 1), X = Br (4B, monoclinic, P21/c, Z′ = 2). As a common feature, the molecules of the halogen compounds, including two polymorphs of 4, are associated into catemers by strong hydrogen bonds of the type N-H···O in 1, 4A and 4B or N-H(···O)2 in 2. These molecular chains are assembled in the crystal structures via different packing modes, which 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 C-F···O/N contacts, but close F···F contacts are tolerated, whereas in 2 each catemer is connected to four parallel congeners by long and bifurcated C-Cl(···O)2 bonds, and both polymorphs of 4 display layers in which the molecules are connected by N-H···O bonds in one and by relatively short and approximately linear C-Br···O interactions in the other dimension. Despite the alleged steric equivalence of methyl and chloro substituents (“chloro-methyl exchange rule”), the packing architecture of the methyl compound 3 is not related to any of the preceding structures. In this case, the N-H···O bonding leads to centrosymmetric cyclodimers, which pack in such a way that each methyl group is located between two oxygen atoms and above the face of an aromatic ring in a topology consistent with C-H···O and C-H···C(π) bonding. All the structures are pervaded by weak Car-H···O hydrogen bonds; moreover, 1 displays a short C-H···F hydrogen bond and a C-F···C(π) interaction, and π-stacking of aromatic rings is observed in 1, 3 and 4B

Polysulfonylamine, CL [1]. Wasserstoffbrücken in kristallinen Oniumdimesylamiden: Ein robustes Achtring-Synthon in den Strukturen von Methyluronium- und 1,1-Dimethyluronium-dimesylamid./Polysulfonylamines, CL [1]. Hydrogen Bonding in Crystalline Onium Dimesylamides: A Robust Eight-Membered Ring Synthon in the Structures of Methyluronium and 1,1-Dimethyluronium Dimesylamide

Methyluronium dimesylamide (1) and 1,1-dimethyluronium dimesylamide (2) have been prepared by proton transfer reactions of the strong nitrogen acid HN(SO2Me)2 with the corresponding ureas and characterized by low-temperature X-ray diffraction (1: orthorhombic, space group P212121, Z′ = 1; 2: orthorhombic, Pna21, Z′ = 2). Compound 2 appears to be the first crystallographically established 1,1-dimethyluronium salt. As a common feature, the three independent formula units consist of ion pairs held together by an eight-membered ring synthon [N2 = R22(8), antidromic] constructed from a syn,syn-sequence H-O-C(sp2)-N-H ofthe cation and a V-shaped O-S(sp3)-N fragment of the anion via homonuclear two-centre hydrogen bonds. The surplus N-H donors form hydrogen bonds to O=S acceptors in adjacent formula units, leading to a three-dimensional network (1) or a pseudo-21 symmetric helical catemer ofalternatingly inequivalent formula units (2). In both structures, the activated methyl groups give rise to numerous short interionic C-H···O contacts, the more prominent of which are analyzed in terms ofweak hydrogen bonding [cut-off criteria: d(H···O) ≤ 270 pm, θ(C-H···O) ≥130°].