Indium halides

Short description: Class of chemical compounds

There are three sets of Indium halides, the trihalides, the monohalides, and several intermediate halides. In the monohalides the oxidation state of indium is +1 and their proper names are indium(I) fluoride, indium(I) chloride, indium(I) bromide and indium(I) iodide.

The intermediate halides contain indium with oxidation states, +1, +2 and +3.

## Contents

* 1 Indium trihalides
* 1.1 Indium(III) fluoride
* 1.2 Indium(III) chloride
* 1.3 Indium(III) bromide
* 1.4 Indium(III) iodide
* 2 Intermediate halides
* 2.1 In7Cl9 and In7Br9
* 2.2 In5Br7
* 2.3 In2Cl3 and In2Br3
* 2.4 In4Br7
* 2.5 In5Cl9
* 2.6 InBr2
* 2.7 InI2
* 3 Monohalides
* 3.1 InF
* 3.2 InCl
* 3.3 InBr
* 3.4 InI
* 4 Anionic halide complexes of In(III)
* 4.1 InX−4 and InX3−6
* 4.2 InCl2−5 and InBr2−5
* 4.3 In2X−7
* 4.4 In2X3−9
* 5 Anionic halide complexes of In(I) and In(II)
* 5.1 InIX−2 and InIX2−3
* 5.2 In2Cl2−6, In2Br2−6 and In2I2−6
* 6 Neutral Indium(II) halide adducts
* 7 General sources
* 8 References

## Indium trihalides

In all of the trihalides the oxidation state of indium is +3, and their proper names are indium(III) fluoride, indium(III) chloride, indium(III) bromide, and indium(III) iodide. The trihalides are Lewis acidic. Indium trichloride is a starting point in the production of trimethylindium which is used in the semiconductor industry.

### Indium(III) fluoride

InF3 is a white solid, m.p. 1170 °C. Its structure contains 6 coordinate indium.

### Indium(III) chloride

InCl3 is a white solid, m.p. 586 °C. It is obtained by oxidation of indium with chlorine.[1] It is isostructural with AlCl3.

### Indium(III) bromide

InBr3 is a pale yellow solid, m.p. 435 °C. It is isostructural with AlCl3. It is prepared by combining the elements.[2] InBr3 finds some use in organic synthesis as a water tolerant Lewis acid.[3]

### Indium(III) iodide

Ball-and-stick model of the In2I6 molecule

InI3 is a yellow solid. It is obtained by evaporation of a solution of indium in HI.[4] Distinct yellow and a red forms are known. The red form undergoes a transition to the yellow at 57 °C. The structure of the red form has not been determined by X-ray crystallography, however spectroscopic evidence indicates that indium may be six coordinate.[5] The yellow form consists of In2I6 with 4 coordinate indium centres. It is used as an "iodide getter" in the Cativa process.

## Intermediate halides

A surprising number of intermediate chlorides and bromides are known, but only one iodide, and no difluoride. Rather than the apparent oxidation state of +2, these compounds contain indium in the +1 and +3 oxidation states. Thus the diiodide is described as InIInIIIX4. It was some time later that the existence of compounds containing the anion In
2Br2−
6 were confirmed which contains an indium-indium bond. Early work on the chlorides and bromides involved investigations of the binary phase diagrams of the trihalides and the related monohalide. Many of the compounds were initially misidentified as many of them are incongruent and decompose before melting. The majority of the previously reported chlorides and bromides have now either had their existence and structures confirmed by X Ray diffraction studies or have been consigned to history. Perhaps the most unexpected case of mistaken identity was the surprising result that a careful reinvestigation of the InCl/InCl3 binary phase diagram did not find InCl2.[6]
The reason for this abundance of compounds is that indium forms 4 and 6 coordinate anions containing indium(III) e.g. InBr−
4, InCl3−
6 as well as the anion In
2Br2−
6 that surprisingly contains an indium-indium bond.

### In7Cl9 and In7Br9

In7Cl9 is yellow solid stable up to 250 °C that is formulated InI6(InIIICl6)Cl3[7]

In7Br9 has a similar structure to In7Cl9 and can be formulated as InI6(InIIIBr6)Br3[8]

### In5Br7

In5Br7 is a pale yellow solid. It is formulated InI3(InII2Br6)Br. The InII2Br6 anion has an eclipsed ethane like structure with a metal-metal bond length of 270 pm.[9]

### In2Cl3 and In2Br3

In2Cl3 is colourless and is formulated InI3 InIIICl6[10] In contrast In2Br3 contains the In2Br6 anion as present in In5Br7, and is formulated InI2(InII2Br6) with a structure similar to Ga2Br3.[11]

### In4Br7

In4Br7 is near colourless with a pale greenish yellow tint. It is light sensitive (like TlCl and TlBr) decaying to InBr2 and In metal. It is a mixed salt containing the InBr−
4 and InBr3−
6 anions balanced by In+ cations. It is formulated InI5(InIIIBr4)2(InIIIBr6) The reasons for the distorted lattice have been ascribed to an antibonding combination between doubly filled, non-directional indium 5s orbitals and neighboring bromine 4p hybrid orbitals.[12]

### In5Cl9

In5Cl9 is formulated as InI3InIII2Cl9. The In
2Cl3−
9 anion has two 6 coordinate indium atoms with 3 bridging chlorine atoms, face sharing bioctahedra, with a similar structure to Cr
2Cl2−
9 and Tl
2Cl2−
9.[13]

### InBr2

InBr2 is a greenish white crystalline solid, which is formulated InIInIII Br4. It has the same structure as GaCl2. InBr2 is soluble in aromatic solvents and some compounds containing η6-arene In(I) complexes have been identified. (See hapticity for an explanation of the bonding in such arene-metal ion complexes). With some ligands InBr2 forms neutral complexes containing an indium-indium bond.[14]

### InI2

InI2 is a yellow solid that is formulated InIInIIII4.

## Monohalides

The solid monohalides InCl, InBr and InI are all unstable with respect to water, decomposing to the metal and indium(III) species. They fall between gallium(I) compounds, which are more reactive and thallium(I) that are stable with respect to water. InI is the most stable. Up until relatively recently the monohalides have been scientific curiosities, however with the discovery that they can be used to prepare indium cluster and chain compounds they are now attracting much more interest.[15]

### InF

InF only known as an unstable gaseous compound.

### InCl

The room temperature form of InCl is yellow, with a cubic distorted NaCl structure. The red high temperature (>390 K) form has the β-TlI structure.[15]

### InBr

InBr is a red crystalline solid, mp 285 °C. It has the same structure as β-TlI, with an orthorhombic distorted rock salt structure. It can be prepared from indium metal and InBr3.

### InI

InI is a deep red purple crystalline solid. It has the same structure as β-TlI. It can be made by direct combination of its constituent elements at high temperature. Alternatively it can be prepared from InI3 and indium metal in refluxing xylenes.[16] It is the most stable of the solid monohalides and is soluble in some organic solvents. Solutions of InI in a pyridine/m-xylene mixture are stable below 243 K.[15]

## Anionic halide complexes of In(III)

The trihalides are Lewis Acids and form addition compounds with ligands. For InF3 there are few examples known however for the other halides addition compounds with tetrahedral, trigonal bipyramidal and octahedral coordination geometries are known. With halide ions there are examples of all of these geometries along with some anions with octahedrally coordinated indium and with bridging halogen atoms, In
2X3−
9 with three bridging halogen atoms and In
2X−
7 with just one. Additionally there are examples of indium with square planar geometry in the InX52− ion. The square planar geometry of InCl2−
5 was the first found for a main group element.

### InX−
4 and InX3−

Salts of InCl−
4, InBr−
4 and InI−
4 are known. The salt LiInF4 has been prepared,[17][18] however it has an unusual layer structure with octahedrally coordinated indium center. Salts of InF63−, InCl3−
6 and InBr3−
6 [19] have all been made.

### InCl2−
5 and InBr2−

The InCl2−
5 ion has been found to be square pyramidal in the salt (NEt4)2InCl5, with the same structure as (NEt4)2 TlCl5, but is trigonal bipyramidal in tetraphenylphosphonium pentachloroindate acetonitrile solvate.[20]

The InBr2−
5 ion has similarly been found square pyramidal, albeit distorted, in the Bis(4-chloropyridinium) salt [21] and trigonal bipyramidal [22] in Bi37InBr48.

### In
2X−

The In
2X−
7 ions contain a single bridging halogen atom. Whether the bridge is bent or linear cannot be determined from the spectra. The chloride and bromide have been detected using electrospray mass spectrometry. The In
2I−
7 ion has been prepared in the salt CsIn2I7.[5]

### In
2X3−

The caesium salts of In
2Cl3−
9 and In
2Br3−
9 both contain binuclear anions with octahedrally coordinated Indium atoms.[13]

## Anionic halide complexes of In(I) and In(II)

### InI

2 and InI
X2−

InIX2− is produced when the In2X62− ion disproportionates. Salts containing the InI
X2−
3 ions have been made and their vibrational spectra interpreted as showing that they have C3v symmetry, trigonal pyramidal geometry, with structures similar to the isoelectronic SnX−
3 ions.

### In
2Cl2−
6, In
2Br2−
6 and In
2I2−

Salts of the chloride, bromide and iodide ions (Bu
4N)
2In

6 have been prepared. In non-aqueous solvents this ion disproportionates to give InI

2 and InIII

## Neutral Indium(II) halide adducts

Following the discovery of the In2Br62− a number of related neutral compounds containing the InII2X4 kernel have been formed from the reaction of indium dihalides with neutral ligands.[14] Some chemists refer to these adducts, when used as the starting point for the synthesis of cluster compounds as ‘In2X4’ e.g. the TMEDA adduct.[23]

## General sources

* WebElements Periodic Table » Indium » compounds information
* Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
* Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5

## References

1. ↑ E. Donges (1963). "Indium(III) chloride". in G. Brauer. Handbook of Preparative Inorganic Chemistry, 2nd Ed.. 1. NY, NY: Academic Press. pp. 858–859.
2. ↑ E. Donges (1963). "Indium(III) bromide". in G. Brauer. Handbook of Preparative Inorganic Chemistry, 2nd Ed.. 1. NY, NY: Academic Press. pp. 859–860.
3. ↑ Zhang, Zhan-Hui (2005). "Indium Tribromide: A Water-Tolerant Green Lewis Acid". Synlett (Georg Thieme Verlag KG) (4): 711–712. doi:10.1055/s-2005-863726. ISSN 0936-5214.
4. ↑ E. Donges (1963). "Indium(III) Iodide". in G. Brauer. Handbook of Preparative Inorganic Chemistry, 2nd Ed.. 1. NY, NY: Academic Press. pp. 861–2.
5. ↑ 5.0 5.1 Taylor, Michael J.; Kloo, Lars A. (2000). "Raman investigations of indium iodide complexes: evidence for the In2I7− ion". Journal of Raman Spectroscopy (Wiley) 31 (6): 465–468. doi:10.1002/1097-4555(200006)31:6<465::aid-jrs557>3.0.co;2-7. ISSN 0377-0486.
6. ↑ Meyer, Gerd; Blachnik, Roger (1983). "Neue Untersuchungen an gemischtvalenten Indium(I, III)- chloriden: Das Phasendiagramm In/Cl im Bereich 30-50 mol-% In und die Kristallstruktur von In5Cl9" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 503 (8): 126–132. doi:10.1002/zaac.19835030813. ISSN 0044-2313.
7. ↑ Beck, Horst Philipp; Wilhelm, Doris (1991). "In7Cl9—A New "Old" Compound in the System In-Cl". Angewandte Chemie International Edition in English (Wiley) 30 (7): 824–825. doi:10.1002/anie.199108241. ISSN 0570-0833.
8. ↑ Dronskowski, R. (1995-12-01). Dronskowski, R.. ed. "The crystal structure of In7Br9". Zeitschrift für Kristallographie - Crystalline Materials (Walter de Gruyter GmbH) 210 (12): 920–923. doi:10.1524/zkri.1995.210.12.920. ISSN 2194-4946. Bibcode: 1995ZK....210..920D.
9. ↑ Ruck, Michael; Bärnighausen, Hartmut (1999). "Zur Polymorphie von In5Br7" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 625 (4): 577–585. doi:10.1002/(sici)1521-3749(199904)625:4<577::aid-zaac577>3.0.co;2-b. ISSN 0044-2313.
10. ↑ Meyer, Gerd (1981). "Das Indiumsesquichlorid, In2Cl3: ein pseudobinäres, gemischtvalentes Indium(I)-hexachloroindat(III)" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 478 (7): 39–51. doi:10.1002/zaac.19814780705. ISSN 0044-2313.
11. ↑ Staffel, Thomas; Meyer, Gerd (1987). "The mono-, sesqui-, and dibromides of indium: InBr, In2Br3, and InBr2" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 552 (9): 113–122. doi:10.1002/zaac.19875520913. ISSN 0044-2313.
12. ↑ Dronskowski, Richard (1995-06-02). "Synthesis, Structure, and Decay of In4Br7". Angewandte Chemie International Edition in English (Wiley) 34 (10): 1126–1128. doi:10.1002/anie.199511261. ISSN 0570-0833.
13. ↑ 13.0 13.1 Meyer, Gerd (1978). "Zur Kenntnis der Chloro- und Bromo-Indate (III). A3In2Cl9 (A = Cs, Rb, In, Tl) und Cs3In2Br9−xClx (x = 0, 3, 6, 7, 8)" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 445 (1): 140–146. doi:10.1002/zaac.19784450117. ISSN 0044-2313.
14. ↑ 14.0 14.1 Sinclair, Ian; Worrall, Ian J. (1982-03-15). "Neutral complexes of the indium dihalides". Canadian Journal of Chemistry (Canadian Science Publishing) 60 (6): 695–698. doi:10.1139/v82-102. ISSN 0008-4042.
15. ↑ 15.0 15.1 15.2 Pardoe, J. A.; Downs, A. J. (2007). "Development of the chemistry of indium in formal oxidation States lower than +3". Chemical Reviews 107 (1): 2–45. doi:10.1021/cr068027+. PMID 17212469.
16. ↑ Organic Syntheses, Coll. Vol. 10, p.170 (2004); Vol. 79, p.59 (2002)
17. ↑ Gravereau, P.; Chaminade, J. P.; Gaewdang, T.; Grannec, J.; Pouchard, M.; Hagenmuller, P. (1992). "Structure of lithium tetrafluoroindate". Acta Crystallographica Section C Crystal Structure Communications 48 (5): 769–771. doi:10.1107/S0108270191011915. Bibcode: 1992AcCrC..48..769G.
18. ↑ Gravereau, P.; Chaminade, J. P.; Gaewdang, T.; Grannec, J.; Pouchard, M.; Hagenmuller, P. (1992-05-15). "Structure of lithium tetrafluoroindate". Acta Crystallographica Section C Crystal Structure Communications (International Union of Crystallography (IUCr)) 48 (5): 769–771. doi:10.1107/s0108270191011915. ISSN 0108-2701. Bibcode: 1992AcCrC..48..769G.
19. ↑ Spiro, Thomas G. (1965). "Raman Spectra of Crystalline Chlorothallates". Inorganic Chemistry (American Chemical Society (ACS)) 4 (9): 1290–1293. doi:10.1021/ic50031a013. ISSN 0020-1669.
20. ↑ Bubenheim, W.; Frenzen, G.; Müller, U. (1995-06-15). "Die Chloroindate [PPh4]2[In2Cl6] und [PPh4]2[InCl5].CH3CN". Acta Crystallographica Section C Crystal Structure Communications (International Union of Crystallography (IUCr)) 51 (6): 1120–1124. doi:10.1107/s0108270194011789. ISSN 0108-2701. Bibcode: 1995AcCrC..51.1120B.
21. ↑ Ishihara, Hideta; Dou, Shi-qi; Gesing, Thorsten M; Paulus, Helmut; Fuess, Hartmut; Weiss, Alarich (1998). "Crystal structures of [(CH3)2NH2]3InBr6 and [4-ClC5H4NH]2InBr5". Journal of Molecular Structure (Elsevier BV) 471 (1–3): 175–182. doi:10.1016/s0022-2860(98)00444-x. ISSN 0022-2860. Bibcode: 1998JMoSt.471..175I.
22. ↑ Dubenskyy, Vitaly; Ruck, Michael (2003). "Bi37InBr48: Eine polares Subhalogenid mit Bi95+-Polykationen, komplexen Bromobismutat(III)-Anionen [Bi3Br13]4— und [Bi7Br30]9— sowie Pentabromoindat(III)-Anionen [InBr5]2—" (in de). Zeitschrift für anorganische und allgemeine Chemie (Wiley) 629 (3): 375–380. doi:10.1002/zaac.200390062. ISSN 0044-2313.
23. ↑ Li, Xiao-Wang; Robinson, Gregory H.; Pennington, William T. (1996). "Disproportionation of Low Valent Indium Bromide: Synthesis and Molecular Structure of Bis (2, 6-Dimesityl-Phenyl) Indium Bromide, (2, 6-Mes2C6H3)2InBr (Mes = 2, 4, 6-Me3C6H2). When does Trigonal Planar Become T-Shaped?". Main Group Chemistry (IOS Press) 1 (3): 301–307. doi:10.1080/13583149612331338587. ISSN 1024-1221.

* v
* t
* e

Salts and covalent derivatives of the chloride ion

HCl |  |  |  | He

|
|
|
|

LiCl | BeCl2 | BCl3
B2Cl4 | CCl4 | NCl3
ClN3 | Cl2O
ClO2
Cl2O7 | ClF
ClF3
ClF5 | Ne
NaCl | MgCl2 | AlCl
AlCl3 | SiCl4 | P2Cl4
PCl3
PCl5 | S2Cl2
SCl2
SCl4 | Cl2 | Ar
KCl | CaCl
CaCl2 | ScCl3 | TiCl2
TiCl3
TiCl4 | VCl2
VCl3
VCl4
VCl5 | CrCl2
CrCl3
CrCl4 | MnCl2 | FeCl2
FeCl3 | CoCl2
CoCl3 | NiCl2 | CuCl
CuCl2 | ZnCl2 | GaCl2
GaCl3 | GeCl2
GeCl4 | AsCl3
AsCl5 | Se2Cl2
SeCl4 | BrCl | KrCl
RbCl | SrCl2 | YCl3 | ZrCl3
ZrCl4 | NbCl4
NbCl5 | MoCl2
MoCl3
MoCl4
MoCl5
MoCl6 | TcCl4 | RuCl3 | RhCl3 | PdCl2 | AgCl | CdCl2 | InCl
InCl2
InCl3 | SnCl2
SnCl4 | SbCl3
SbCl5 | Te3Cl2
TeCl4 | ICl
ICl3 | XeCl
XeCl2
CsCl | BaCl2 |  | HfCl4 | TaCl5 | WCl2
WCl3
WCl4
WCl5
WCl6 | Re3Cl9
ReCl4
ReCl5
ReCl6 | OsCl4 | IrCl2
IrCl3
IrCl4 | PtCl2
PtCl4 | AuCl
AuCl3 | Hg2Cl2,
HgCl2 | TlCl | PbCl2,
PbCl4 | BiCl3 | PoCl2,
PoCl4 | AtCl  | RnCl2
FrCl | RaCl2 |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
LaCl3 | CeCl3 | PrCl3 | NdCl2,
NdCl3 | PmCl3 | SmCl2,
SmCl3 | EuCl2,
EuCl3 | GdCl3 | TbCl3 | DyCl2,
DyCl3 | HoCl3 | ErCl3 | TmCl2
TmCl3 | YbCl2
YbCl3 | LuCl3
AcCl3 | ThCl4 | PaCl5 | UCl3
UCl4
UCl5
UCl6 | NpCl4 | PuCl3 | AmCl2
AmCl3 | CmCl3 | BkCl3 | CfCl3 | EsCl3 | Fm  | Md  | No  | LrCl3

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