Polysulfonylamine. CLXXIV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 17 [2] Silber(I)‐di(methansulfonyl)amid: Ein diamantoides Netzwerk aus Ag2N2‐Vierringen und verbrückenden Mesylgruppen

Abstract

AbstractPolysulfonylamines. CLXXIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 17. Silver(I) Di(methanesulfonyl)amide: A Diamondoid Network of Four‐Membered Ag2N2 Rings and Bridging Mesyl GroupsThe crystal structure of silver(I) dimesylamide (orthorhombic, space group Fddd, Z = 16, Z′ = 1/2, single‐crystal X‐ray diffraction at −140 °C) consists of dinuclear Ag2[N(SO2Me)2]2 complexes, in which the nitrogen atoms are μ2‐bonded to the silver ions at distances of 241.83(15) pm to form planar rhombic Ag2N2 rings; the short Ag···Ag ring diagonal, 285.36(4) pm, is consistent with weak argentophilic interaction. In the packing, the ring centres lie on 222 sites, conferring crystallographic D2 symmetry on the complex and crystallographic C2 symmetry on the anions. Moreover, each complex is connected to four adjacent complexes by centrosymmetric pairs of silver‐oxygen bonds at distances 245.35(13) pm. In the resulting three‐dimensional coordination polymer, the ring centres represent the nodes of a distorted diamondoid network, whereby the high packing efficiency prevents the interpenetration of networks that is frequently observed in diamondoid solids. The primary N2O2 coordination of the cation corresponds to a distorted tetrahedron with bond angles in the range 103.62(3)–118.57(3)°; including the short Ag···Ag contact and four secondary silver‐oxygen contacts at distances of 300.18(13) pm (2×) and 333.10(13) pm (2×), the coordination number is increased to nine.