A New Family of Supramolecular Complexes with 3D Cationic Hg/Z Frameworks, SnX3− Guest Anions (Z = P, As, Sb; X = Cl, Br, I): Crystal Structures and Host−Guest Interactions

Abstract

Five new inorganic supramolecular complexes, [Hg6P4Cl3](SnCl3) (I), [Hg6As4Cl3](SnCl3)Hg0.13 (II), [Hg6As4Br3](SnBr3) (III), [Hg6Sb4I3](SnI3)Hg0.16 (IV), and [Hg7P4Br3](SnBr3) (V), have been prepared and their structures determined by X‐ray single crystal experiments. They all crystallize in the cubic space group P213 (No 198) with Z = 4, and unit cell parameters a = 11.865(1) (I), 12.233(1) (II), 12.383(1) (III), 13.285(2) (IV), and 12.490(1) Å (V). The crystal structures of these compounds are composed of the 3D positively charged frameworks [Hg6Z4X3]+ (I−IV) or [Hg7P4Br3]+ (V), with SnX3− anions trapped in the larger cavities of the frameworks (X = Cl, Br, I; Z = P, As, Sb). In the structures of II and IV the smaller cavities are partly filled by mercury atoms. The structures of I−V and of previously reported [Hg7As4I3](SnI3) (VI) are discussed with respect to the matching and mutual adjusting of the host frameworks and guest anions. A comparison of the observed and calculated (ab initio, RHF level) geometry of the SnX3− anions is used to analyze the weak host−guest interactions.

Synthesis, Crystal and Band Structures, and Properties of a New Mixed Three-Dimensional Framework Metal Pnictidehalide Semiconductor, (Hg6Sb4)(CdI6)

“…The interatomic distances between the mercury atoms in the cationic moiety and the iodine atoms in the anionic moiety range from 3.110(3) to 3.142(3) Å, which are rather longer than the Hg−I covalent bond distance but shorter than the sum of van der Waals radii of Hg and I. This indicates that there are weak covalent interactions between the cationic and anionic moieties in the crystal structure of 1 , as the case found in the literature. 3a,g,h, …”

“…Analogues to the compound (Hg 6 Sb 4 )(CdI 6 )Hg 0.6 ,3g the mercury atoms are almost linearly coordinated by two antimony atoms in the present compound. The Hg−Sb bond distances range from 2.682(2) to 2.704(2) Å, which lie in the normal range of the Hg−Sb separations in mercury pnictidehalides. 3g,15a, The Cd−I bond distances range from 2.766(8) to 2.929(8) Å, which are shorter than those found in cadmium iodides and cadmium pnictidehalides , butcomparable to those found in (Hg 2 As) 2 (CdI 4 ) 3h…”

“…Unlike most of inorganic supramolecular complexes based on mercury−pnicogen or mercury−pnicogen−halogen, where the guest anions embedded in the cavities of the host framework are discrete or 1-D infinite structural units, 3a,f-h, the present compound contains a new type of “guest anions” with a 3-D I 6 octahedral anionic network mixed with 3-D cationic network. ,, In comparison with (Hg 6 Sb 4 )(CdI 6 )Hg 0.6 3g that contains discrete (CdI 6 ) octahedral anions and Hg atoms located in the different cavities of the host framework, compound 1 contains a 3-D I 6 octahedral anionic network interpenetrated with the 3-D cationic network although they have the nearly same formula except for the discrete mercury atoms.…”

Large Mid-IR Second-Order Nonlinear-Optical Effects Designed by the Supramolecular Assembly of Different Bond Types without IR Absorption

“…The Hg–P and P–P bond lengths in the cationic moiety in 1 and 2 range from 2.304(9) to 2.451(3) Å and from 2.14(3) to 2.19(1) Å, which lie in the normal range for Hg–P and P–P bond lengths in known mercury pnictidohalides, respectively . The Pb–Cl bond distance [2.745(5) Å], Hg–Cl bond distance [2.854(4) Å], and Zn–Cl bond distances [2.257(18)–2.377(13) Å] are close to those found in the literature. , …”

EuSi7P10: An Inorganic Supramolecular Nonlinear Optical Crystal Exhibiting Strong Second-Harmonic Generation Response

“…However, it is shorter than the sum of the van der Waals radii of Eu and P atoms, which is 4.13 Å. These observations suggest the presence of typical electrostatic forces, or weak supramolecular interactions, between the host and guest frameworks. − In addition, there are two P atoms (P(1) and P(9)) coordinated with two Si atoms in EuSi 7 P 10 , while other P atoms coordinate with three Si atoms (Figure S3).…”