Crystal chemistry of complex indium(III) and other M(III) halides, with a discussion of M—Cl bond lengths in complex M(III) chlorides and of the structures of and hydrogen bonding in (NH₄)₂[InCl₅(H₂O)], K₃InCl₆•nH₂O, (MeNH₃)₄[InCl₆]Cl, and (Me₂NH₂)₄[InCl₆]Cl

Abstract

. 1527 (1987). 65,The crystal chemistry of complex In(II1) halides is discussed and compared with that of other Group 111 elements and Fe(III), with critical comments and analysis of the available information. The cation/anion packing types occurring among A+ [M3+X4] halides are classified according to volume per formula unit and the relative ionic sizes of M, X, and A, and the structural trends in this class of compounds are identified. The effect of systematic factors responsible for variation in M(II1)-C1 bond lengths is examined in detail. It is shown that the mean M(II1)-C1 bond lengths in [MC1,,L,,,Ie (M = Al, Ga, Fe, In, T1; L = C1 or a neutral ligand) complexes can be approximated, to within about 0.02 A, by a linear function of the coordination number CN = n + m and the charge E over the range 3 5 CN 5 6 and -3 5 E 5 2. This analytical expression provides a norm for comparing M(II1)-Cl bond lengths and demonstrates that the CN is always a more important factor than E in determining thevariation in the mean bond length and that it becomes dominant when M is small. The crystal structure of (Me2NH2) The water in K31nC16. nH20 appears to be in part zeolitic; the hydrate examined contained more water than the monohydrate reported previously. Hydrogen bonding in these and related structures is described and discussed in detail; descriptions of the hydrogen-bonding schemes in (NH4) 65, 1527 (1987).On discute de la chimie des cristaux des complexes des halogknures de l'In(II1) et on la compare a celle des complexes du Fe(II1) et des autres tlCments du groupe 111; on fait des commentaires critiques ainsi qu'une analyse des informations disponibles. In this contribution to the structural chemistry of In-halogen compounds we offer ( A ) a catalogue raisonne' of the crystal chemistry of halogeno complexes of In(II1) and related compounds; (B) a detailed analysis of the systematic factors responsible for variation in M-Cl bond lengths in Group I11 and Fe(II1) complex chlorides, and a resulting scheme which permits these bond lengths to be rationalized and predicted; (C) crystal-structure determinations or re-determinations of the four title compounds; and (D) a discussion of hydrogen bonding in these and other In(II1) halides. Our discussion of the crystal 'To whom correspondence may be addressed.older of NSERC (1983of NSERC ( -1986 and Killam (1984Killam ( -1986 chemistry attempts not merely to unify results published to date, but also to offer critical comment and identify gaps in our present knowledge. It therefore includes complex In(II1) fluorides, which are usually treated as belonging to the solidstate rather than to the coordination chemistry of indium, even though their structures often contain recognizable InF,,E units (some of which may exist in fluoride melts). A few pseudohalogeno complexes are also mentioned. On the other hand, halogeno complexes containing In-C bonds have been deliberately excluded; the presence of the covalent In-C bond introduces factors, additional to the coordination number (C...

Some errors from the crystallographic literature, some amplifications and a questionable result

“…There is a hydrogen-bonded arrangement of two independent (CH 3 NH 3 ) + cations, two independent octahedral (MX 6 ) À anions centered at Wyckoff positions a (0,0,0; 1 2 , 0, 1 2 ) and d (0, 0, 1 2 ; 1 2 , 0, 0), and two independent Cl À anions at Wyckoff positions e ( 3 4 , y, 3 4 ; 1 4 , Ày, 1 4 ) and f ( 3 4 , y, 1 4 ; 1 4 , Ày, 3 4 ) on twofold axes. This arrangement was ®rst described in detail by Knop et al (1987) for (CH 3 NH 3 ) 4 InCl 7 , the structure of which had been determined earlier by Schlimper & Ziegler (1972).…”

“…The ®rst four compounds all crystallize in space group P2/n with Z = 4. FOXTIV10 was reported as monoclinic, Z = 2, space group P2, but can be transformed to the pseudo cell given in the Knop et al (1987); (2) James et al (1996); (3) Halepoto et al (1995). These authors do not mention the earlier work in references (1), (4) or (5); (4) Khan & Tuck (1981);(5) Czjzek et al (1992).…”

Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte

“…Thec orresponding X-ray diffraction (XRD) patterns were not matched to any particular chemicals including LiCl, InCl 3 ,InCl 3 •x H 2 O, and Li 3 InCl 6 .The obtained product was probably ah ydrated form of lithium indium chloride as Li 3 InCl 6 •x H 2 Os imilar to other indium halide hydrates,s uch as Cs 2 InBr 5 •H 2 O, [14] (NH 4 ) 2 InCl 5 •H 2 O [15] and K 3 InCl 6 •n H 2 O. [15] Coordinating water was confirmed by Fourier transform infrared spectroscopy (Figure S2). The number of coordinated water (x in Li 3 InCl 6 •x H 2 O) was estimated to be 2b yt hermogravimetric analysis (TGA, Figure S3).…”

Bayesian optimization based on a unified figure of merit for accelerated materials screening: A case study of halide perovskites

“…We calculated the lowest decomposition energies (∆H d ) of perovskites that have been reported, as shown in Table S2. According to the results, we concluded that double perovskites could been synthesized when ∆H d is greater than 0 meV per atom, [32,37,40,[52][53][54][55][56][57][58][59] and there is no synthesis in the experiment when ∆H d is lower than −29 meV per atom. It is worth noting that ∆H d is between −29-0 meV per atom, that is, Cs 2 AgSbCl 6 [44,60], Rb 2 NaInCl 6 [53], Cs 2 AgSbBr 6 [44], Cs 2 NaInBr 6 [53], Cs 2 KBiCl 6 [61], Cs 2 NaSbBr 6 [54], Cs 2 NaBiI 6 [43] and Cs 2 AgBiI 6 [62] are experimentally synthesized by synthesizing nanocrystals or controlling the experimental temperature.…”