The Bond Indium‐Halogen in Isomorphous Complexes A2InX5 · H2O (A = K, NH4, Rb, Cs; X = Cl, Br). A 35Cl, 79,81Br, and 115In NQR study

Yamada, Koji; Weiß, Alarich

doi:10.1002/bbpc.19830871019

Cited by 21 publications

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“…dThe Rb and Cs analogs are isostructural on powder diffraction evidence (55). 'cis relative to the halogen atom.…”

Section: Isolated Octahedramentioning

confidence: 99%

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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

Knop¹,

Cameron²,

Adhikesavalu³

et al. 1987

Can. J. Chem.

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. 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...

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“…dThe Rb and Cs analogs are isostructural on powder diffraction evidence (55). 'cis relative to the halogen atom.…”

Section: Isolated Octahedramentioning

confidence: 99%

“…The existence of K21nC15.H20 is well established (18,20,21,23,55,139,156), but the K/In = 3 phase has been formulated variously as K3InCl6-H2O (18,27,28), K31nC16.8H20 (157,158), and K31nC16.2H20 (139,159). In addition, a material analyzing to K21nC15.…”

Section: K31nc16 Nhzomentioning

confidence: 99%

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

Knop¹,

Cameron²,

Adhikesavalu³

et al. 1987

Can. J. Chem.

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Nuclear quadrupole coupling in hexachlorometallates A₂[MCl₆] and A'[MCl₆], A^⊕, A'^2⊕ = several inorganic or organic cations, M = Sn, Pb, Te, Pt

Borchers

Weiß

1989

Ber Bunsenges Phys Chem

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The electric field gradient (EFG) at the chlorine site of the hexachlorometallates A2[MCl6] and A'[MCl6], M = Sn, Te, Pb, Pt, and A⊕, A'2⊕ = alkali metal ion, hexahydrated bivalent metal ion, or organic ammonium cation, is investigated and the dependence of the EFG on the size of the cation is discussed. — For the cubic alkali hexachlorometallates the observed trend in the EFG with increasing size of the cation is corroborated by quantum mechanical calculations using the Multiple‐Scattering‐Xα‐method (MS‐Xα) and the point charge model. A correlation v(35Cl) ∼ 1/r3 is found, where r is the distance between the ions in the lattice and the chlorine nucleus considered. For hexachlorometallates with organic cations, like pyridine, piperazine, 4‐picoline, ethylenediamine, 1.3‐propylenediamine, and other aliphatic or aromatic amines, this 1/r3 dependence is found for the averaged 35Cl NQR frequency, too. This is due to the distortion of the [MCl6]2⊕ octahedra, caused by hydrogen bonds N—H…Cl, and to the decrease of the lattice symmetry because of non‐sphericity of the cations. — A hydrogen bond has a large influence on the properties of one of the chlorine atoms of the hexachlorometallate complex. The M‐Cl distance is increased and therefore the EFG at the nucleus site is decreased. However, the average of the M‐Cl bond lengths or the 35Cl NQR frequencies, taken over all six chlorine atoms of a [MCl6]2⊕ complex, is not influenced by the chemical nature of the cation but only by its size or the size of the unit cell, respectively. The increase of 35Cl NQR frequency with increasing size of the cation originates from a decrease of the lattice energy.

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ChemInform Abstract: THE BOND INDIUM‐HALOGEN IN ISOMORPHOUS COMPLEXES A2INX5.H2O (A = K, NH4, RB, CS; X = CL, BR). A CHLORINE‐35, BROMINE‐79, ‐81, AND INDIUM‐115 NQR STUDY

Yamada¹,

Weiß²

1984

Chemischer Informationsdienst

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The Bond Indium‐Halogen in Isomorphous Complexes A₂InX₅ · H₂O (A = K, NH₄, Rb, Cs; X = Cl, Br). A ³⁵Cl, ^79,81Br, and ¹¹⁵In NQR study

Cited by 21 publications

References 46 publications

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

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

Nuclear quadrupole coupling in hexachlorometallates A₂[MCl₆] and A'[MCl₆], A^⊕, A'^2⊕ = several inorganic or organic cations, M = Sn, Pb, Te, Pt

ChemInform Abstract: THE BOND INDIUM‐HALOGEN IN ISOMORPHOUS COMPLEXES A2INX5.H2O (A = K, NH4, RB, CS; X = CL, BR). A CHLORINE‐35, BROMINE‐79, ‐81, AND INDIUM‐115 NQR STUDY

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The Bond Indium‐Halogen in Isomorphous Complexes A2InX5 · H2O (A = K, NH4, Rb, Cs; X = Cl, Br). A 35Cl, 79,81Br, and 115In NQR study

Cited by 21 publications

References 46 publications

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

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

Nuclear quadrupole coupling in hexachlorometallates A2[MCl6] and A'[MCl6], A⊕, A'2⊕ = several inorganic or organic cations, M = Sn, Pb, Te, Pt

ChemInform Abstract: THE BOND INDIUM‐HALOGEN IN ISOMORPHOUS COMPLEXES A2INX5.H2O (A = K, NH4, RB, CS; X = CL, BR). A CHLORINE‐35, BROMINE‐79, ‐81, AND INDIUM‐115 NQR STUDY

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The Bond Indium‐Halogen in Isomorphous Complexes A₂InX₅ · H₂O (A = K, NH₄, Rb, Cs; X = Cl, Br). A ³⁵Cl, ^79,81Br, and ¹¹⁵In NQR study

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

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

Nuclear quadrupole coupling in hexachlorometallates A₂[MCl₆] and A'[MCl₆], A^⊕, A'^2⊕ = several inorganic or organic cations, M = Sn, Pb, Te, Pt