[LiNa(N5)2(H2O)4]·H2O: a novel heterometallic cyclo- $$\rm{N}_5^-$$ N 5 − framework with helical chains

Abstract

Over the past decades, there has been an intensive quest for theoretical studies and experimental detection of polynitrogen species (e.g., N 4 Fig. 2). The synthetic details are provided in the Supplementary information (Experimental Section, Fig. S1). Crystal of 1 suitable for single crystal X-ray diffraction (XRD) was obtained by recrystallization in ethyl alcohol (Fig. S2). The crystal structures were resolved and refined by direct methods and full-matrix least-squares methods on F2 using SHELXTL program package, respectively (Table S1-S3).Compound 1 crystallizes in monoclinic C2/c space group with a density of 1.547 g cm −3 at 173 K. There are one independent Li(I) ion, one Na(I) ion, two cyclo-N 5 − anions, and four and two halves water molecules contained in the asymmetric unit of 1 (Fig. 2a). Each lithium ion is connected with two different cyclo-N 5 − anions and two water molecules to form a two-connected tetrahedral configuration, while each sodium ion is coordinated to two adjacent cyclo-N 5 − anions and four water molecules to construct an octahedral structure. The bond length of Li-N and Na-N are in the range of 2.0440(3)-2.0680(3) Å and 2.5406(14)-2.6185(14) Å, respectively (Table S2). The adjacent lithium and sodium ions are connected to each other by cyclo-N 5 − anions to form an inorganic chain {LiNa(H 2 O) 2 (N 5 ) 2 } n , while the lithium and sodium ions are alternating in the hybrid chain strictly (Fig. 2b). The adjacent and parallel hybrid chains are further connected by the bridged water molecules, forming the layered

Synthesis, characterization, and theoretical analysis of three new nonlinear optical materials K7MRE2B15O30 (M= Ca and Ba, RE= La and Bi)

“…The crystal structures data of the title compounds were collected by single-crystal XRD on a Bruker SMART APEX II 4K CCD diffractometer using monochromatic Mo Kα radiation with λ = 0.71073 Å at 296(2) K and integrated with the SAINT program [53]. All calculations were performed with programs from the SHELXTL and Olex2 crystallographic program package [54][55][56]. These structures were checked for possible higher symmetry using the ADDSYM algorithm from the program PLA-TON [57].…”

Stabilization of the [cyclo‐N5]− anion by Lewis acid‐base interactions

“…Stable full‐nitrogen energetic materials, such as N 2 , N 3 − N 4 , N 5 + , [cyclo‐N 5 ] − , N 8 , polymeric nitrogen, etc., attract much interest because of their extreme high‐energy contents and environment‐friendly products. [ 1–5 ] With the successful synthesis of complex (N 5 ) 6 (H 3 O) 3 (NH 4 ) 4 Cl, confirmation of the structure of cyclopentazolate anion ([cyclo‐N 5 ] − ) is important because of its very broad application in the energetic area. In 2002, Vij et al first pointed out the structure of [cyclo‐N 5 ] − in the gas phase.…”

Syntheses of Energetic cyclo‐Pentazolate Salts

“…After the bulk synthesis of the cyclo-N 5 À ,alarge amount of metal-N 5 À compounds emerged including [LiNa(N 5 ) 2 (H 2 O) 4 ]· H 2 4 ] À , [Na 5 (CH 6 N 3 )(N 5 ) 9 ] 3À ,a nd [(NaN 5 ) 2 (C 2 H 4 N 4 )]. [1,[3][4][5][6][7][8][9][10][11] However,t he current synthesized metal containing pentazolate salts are limited in energy,t hey cannot be used directly as energetic materials.…”

“…After the bulk synthesis of the cyclo ‐N 5 − , a large amount of metal‐N 5 − compounds emerged including [LiNa(N 5 ) 2 (H 2 O) 4 ]⋅H 2 O, [Na(H 2 O)(N 5 )]⋅2 H 2 O, [Na 8 (N 5 ) 8 (H 2 O) 3 ] n , MPF‐1, [M(H 2 O) 4 (N 5 ) 2 ]⋅4 H 2 O (M=Mn, Fe, Co, and Zn), [Mg (H 2 O) 6 (N 5 ) 2 ]⋅4 H 2 O, [Ba(N 5 )(NO 3 )(H 2 O) 3 ] n , [NaBa 3 (N 5 ) 6 (NO 3 )(H 2 O) 3 ] n , [Cu(N 5 )(N 3 )] n , [Ag(N 5 )] n , [Ag(NH 3 ) 2 ] + [Ag 3 (N 5 ) 4 ] − , [Na 5 (CH 6 N 3 )(N 5 ) 9 ] 3− , and [(NaN 5 ) 2 (C 2 H 4 N 4 )] . However, the current synthesized metal containing pentazolate salts are limited in energy, they cannot be used directly as energetic materials.…”