Structural Analysis and Controllable Fabrication of Two Pentazolate-Based 3D Topological Networks

Abstract

Two novel sodium-pentazolate frameworks (namely, MPF-3 and MPF-4) were achieved by adding simple additives. MPF-3 exhibits an aesthetic three-dimensional (3D) framework with the zeolitic MTN topology, featuring Na28N80 and Na20N60 nanocages. In MPF-4, two left-handed helical chains construct enclosed homochiral channels filled with dimethyl sulfone molecules, which constitute a zeolite-like UNJ topology. Importantly, the preparation of these two compounds provides an effective experimental means to explore the unique symmetrical structure and multiple coordination modes of pentazolium anion and demonstrates that it is possible to regulate the crystal structure through appropriate additives.

[Na4(N5)4(H2O)2]·H2O·2MeOH: a honeycomb-like sodium pentazolate framework with helical chains

“…3). A strong cyclo-N 5 − band was found at 1230 cm −1 , which is in excellent agreement with the frequencies observed in the NaN 5 frameworks [Na 8 (N 5 ) 8 (H 2 O) 3 ] n (1231 cm −1 ), 10 MPF-1 (1232 cm −1 ), 11 and MPF-4 (1233 cm −1 ), 13 and blue-shifts by more than 10 cm −1 compared to the A1 mode of Na(H 2 O) (N 5 )•2H 2 O (1219 cm −1 ) and the KN 5 framework (1217 cm −1 ). 17 This work demonstrates the structural diversity of sodium pentazolate frameworks and their self-assembly can be regulated using appropriate solvents and additives.…”

“…2a and b). The bond lengths of Na-N bonds are in the range of 2.419(5)-2.598( 5) Å (Na1-N) and 2.449(5)-2.509( 5) Å (Na2-N), which are similar to those of MPF-4 (2.405(5)-2.594(5) Å) 13 angles between 0.0(5)°and 0.9(6)°(Table S4 †).…”

“…1). 12,13 As such, based on the coordination of cyclo-N 5 − with Na + , the introduction of auxiliary ligands will bring about the formation of NaN 5 frameworks with diverse topologies.…”

Pentazolate coordination polymers self-assembled by in situ generated [Pb4(OH)4]4+ cubic cations trapping cyclo-N5−

“…[11][12][13][14] Until 2017, 15,16 breakthrough progress was made in the bulk synthesis and isolation of cyclo- and opened up a promising path for fascinating pentazole chemistry. 16 Gradually, many metal-N 5 − coordination polymers (CPs) have been reported, including [Na 8 (N 5 ) 8 (H 2 O) 3 ] n , 17 MPF-1, 18 [Ba(N 5 )(NO 3 )(H 2 O) 3 ] n , 19 [NaBa 3 (N 5 ) 6 (NO 3 )(H 2 O) 3 ] n , 19 [Cu(N 5 )(N 3 )] n , 19 [Ag(N 5 )] n , 19 [Ag(NH 3 ) 2 ] + [Ag 3 (N 5 ) 4 ] − , 20 [LiNa (N 5 ) 2 (H 2 O) 4 ]•H 2 O, 21 KN 5 , 22 Na 5 (N 5 ) 5 (H 2 O) 2 (MSN)•DMSO (MPF-2), 23 MPF-3, 24 and Na 3 (N 5 ) 3 [SO 2 (CH 3 ) 2 ] (MPF-4). 24 Cyclo-N 5 − complexes have also been characterized in high pressure chemistry from the coupling of N 2 and metal azides (MN 3 ) or N 2 and metals.…”

“…16 Gradually, many metal-N 5 − coordination polymers (CPs) have been reported, including [Na 8 (N 5 ) 8 (H 2 O) 3 ] n , 17 MPF-1, 18 [Ba(N 5 )(NO 3 )(H 2 O) 3 ] n , 19 [NaBa 3 (N 5 ) 6 (NO 3 )(H 2 O) 3 ] n , 19 [Cu(N 5 )(N 3 )] n , 19 [Ag(N 5 )] n , 19 [Ag(NH 3 ) 2 ] + [Ag 3 (N 5 ) 4 ] − , 20 [LiNa (N 5 ) 2 (H 2 O) 4 ]•H 2 O, 21 KN 5 , 22 Na 5 (N 5 ) 5 (H 2 O) 2 (MSN)•DMSO (MPF-2), 23 MPF-3, 24 and Na 3 (N 5 ) 3 [SO 2 (CH 3 ) 2 ] (MPF-4). 24 Cyclo-N 5 − complexes have also been characterized in high pressure chemistry from the coupling of N 2 and metal azides (MN 3 ) or N 2 and metals. In 2017, Oleynik et al 25 characterized the pentazolate units in CsN 5 which was synthesized in a diamond anvil cell (DAC) by compressing and laser heating CsN 3 and N 2 precursors at pressures near 60 GPa.…”