Stan A. Duraj

Cleveland State University, Cleveland, Ohio

Aloysius F. Hepp

Glenn Research Center, Cleveland, Ohio

Robert Woloszynek and John D. Protasiewicz

Case Western Reserve University, Cleveland, Ohio 

Michael Dequeant

Hendrix College, Conway, Arkansas 

Tong Ren

Purdue University, West Lafayette, Indiana 

Synthesis of Two New Group 13 Benzoato-Chloro 

Complexes: A Structural Study of Gallium and 

Indium Chelating Carboxylates

NASA/TM—2010-216826 INOR–432

December 2010
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Stan A. Duraj

Cleveland State University, Cleveland, Ohio

Aloysius F. Hepp

Glenn Research Center, Cleveland, Ohio

Robert Woloszynek and John D. Protasiewicz

Case Western Reserve University, Cleveland, Ohio 

Michael Dequeant

Hendrix College, Conway, Arkansas 

Tong Ren

Purdue University, West Lafayette, Indiana 

Synthesis of Two New Group 13 Benzoato-Chloro 

Complexes: A Structural Study of Gallium and 

Indium Chelating Carboxylates

NASA/TM—2010-216826 INOR–432

December 2010

National Aeronautics and

Space Administration

Glenn Research Center

Cleveland, Ohio 44135

Prepared for the

Spring 2010 National Meeting and Exposition

sponsored by the American Chemical Society

San Francisco, California, March 21–25, 2010
Acknowledgments

S.A. Duraj thanks Cleveland State University for support during a sabbatical at Case Western Reserve University. A.F. Hepp 

acknowledges support from the NASA Glenn Research Center’s Internal Research and Development Fund. S.A. Duraj, 

R.A. Woloszynek, and J.D. Protasiewicz acknowledge support from the Department of Chemistry, Case Western Reserve University. 

M. Dequeant and T. Ren acknowledge support from the Department of Chemistry at University of Miami Coral Gables, Florida, 

where the structural data were collected and solved.

Available from

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Available electronically at http://gltrs.grc.nasa.gov

Trade names and trademarks are used in this report for identifi cation 

only. Their usage does not constitute an offi cial endorsement, 

either expressed or implied, by the National Aeronautics and 

Space Administration.

Level of Review: This material has been technically reviewed by technical management. 
Synthesis of Two New Group 13 Benzoato-Chloro Complexes: 

A Structural Study of Gallium and Indium Chelating Carboxylates

Stan A. Duraj

Cleveland State University

Cleveland, Ohio 44115 

Aloysius F. Hepp 

National Aeronautics and Space Administration

Glenn Research Center

Cleveland, Ohio 44135 

Robert Woloszynek and John D. Protasiewicz

Case Western Reserve University

Cleveland, Ohio 44106 

Michael Dequeant

Hendrix College 

Conway, Arkansas 72032 

Tong Ren 

Purdue University 

West Lafayette, Indiana 47907 

Abstract

Two new heteroleptic chelated-benzoato gallium (III) and indium (III) complexes have been prepared 

and structurally characterized. The molecular structures of [GaCl2(4-Mepy)2(O2CPh)]•4-Mepy (1) and 

[InCl(4-Mepy)2(O2CPh)2]•4-Mepy (2) have been determined by single-crystal x-ray diffraction. The 

gallium compound (1) is a distorted octahedron with cis-chloride ligands co-planar with the chelating 

benzoate and the 4-methylpyridines trans to each other. This is the first example of a Ga(III) structure 

with a chelating benzoate. The indium compound (2) is a distorted pentagonal bipyramid with two 

chelating benzoates, one 4-methylpyridine in the plane and a chloride trans to the other 4-methylpyridine. 

The indium bis-benzoate is an unusual example of a seven-coordinate structure with classical ligands.

Both complexes, which due to the chelates, could also be described as pseudo-trigonal bipyramidal, 

include a three-bladed motif with three roughly parallel aromatic rings that along with a solvent of 

crystallization and electron-withdrawing chloride ligand(s) stabilize the solid-state structures. 

1.0 Introduction

In recent years, there has been an intense and ongoing interest in the study of gallium and indium 

complexes for use as potential precursors for electronic materials via chemical spray pyrolysis or 

chemical solution deposition (Refs. 1 to 4). Ideally, such precursors should be readily prepared from 

inexpensive starting materials, be easily handled or preferably air-stable, and decompose cleanly for 

chemically-driven processing to be economically viable (Refs. 5 and 6). In our on-going research, we are 

preparing derivatives of gallium and indium chlorides with chalcogenide ligands, determining their 

single-crystal structures and studying further reactions to produce new precursors for solid-state materials 

(Refs. 6 to 9). For example, oxidative addition of lower-valent Ga and In chlorides (or metal) via addition 

of carboxylate (RCO2

–

) or dithiocarbamate (S2C-NR2

–

) ligands by reaction with the respective 

NASA/TM—2010-216826 1
chalcogenide-bonded dimers affords compounds that are amenable to characterization, particularly 

complexes that are stabilized by pyridine-like ligands (Refs. 1 to 10). Use of 4-methylpyridine or γpicoline solvent (ligands) has yielded complexes that most readily provide single crystals suitable for 

x-ray diffraction studies. Previously, reaction of sodium benzoate with Ga2Cl4 in 4-methylpyridine 

resulted in isolation and structural characterization of the first oxo-centered main group trinuclear 

carboxylate, [Ga3(μ3-O)(μ-O2CC6H5)6(4-MeC5H5N)3](GaCl4] (Ref. 9). Similarly, oxidation of indium 

powder with benzoyl peroxide produced the first example of a mononuclear eight-coordinate indium (III) 

benzoate, In(η2

-O2CC6H5)3(4-MeC5H5N)2 (Ref. 10). In this report, we detail two further examples of 

structurally characterized examples of mixed-ligand chelated-benzoato complexes prepared by this 

straightforward synthetic approach with classical ligands. We discuss the structures and compare them to 

other molecular and metal-organic framework structures of indium and gallium. 

2.0 Experimental

2.1 Materials and Methods

All manipulations were performed either in an MBRAUN Labmaster 130 drybox or utilizing standard 

Schlenk techniques under an atmosphere of nitrogen. All solvents were distilled from sodium 

benzophenone ketyl just prior to use. Celite was purchased from ACROS and heated under vacuum for 

24 hr prior to use. All glassware used was flame-dried and stored in an oven prior to use. Solutions were 

transferred via stainless steel cannulae and/or syringes. Gallium (II) chloride (99.999 percent) and indium 

(I) chloride (99.995 percent) (both from Alfa Aesar) were purchased in argon-filled ampoules and 

transferred in an inert atmosphere glove box. Benzoyl peroxide ((C6H5CO2)2 - Aldrich) was deaerated 

under vacuum at room temperature prior to use.

2.2 Preparation of [GaCl2(4-Mepy)2(O2CPh)]•4-Mepy (1) 

Gallium (II) chloride (0.302 g, 0.996 mmol) and a 2:1 excess of benzoyl peroxide (0.480 g, 

1.98 mmol) were added to a Schlenk flask charged with a stirbar in a drybox. The flask was sealed with a 

septum, removed from the drybox, and taken to a fume hood where the flask was placed under nitrogen. 

4-methylpyridine (10 mL) was slowly added via cannula with rapid stirring. The solution immediately 

turned a deep crimson red color and the solution was allowed to stir at room temperature for 48 hr. During 

the course of the reaction, the solution gradually changed from crimson red to orange in color. The 

reaction mixture was then filtered through a pad of Celite. An equal amount of hexanes was layered on 

the filtrate via cannula. Colorless single crystals, suitable for x-ray diffraction studies were observed at 

the solvent interface after standing for 72 hr at room temperature.

2.3 Preparation of [InCl(4-Mepy)2(O2CPh)2]•4-Mepy (2)

Indium (I) chloride (0.150 g, 0.998 mmol) and benzoyl peroxide (0.240 g, 0.998 mmol) were added to 

a Schlenk flask charged with a stirbar in a drybox. The flask was sealed with a septum, removed from the 

drybox and taken to a fume hood where the reaction flask was placed under nitrogen. 4-methylpyridine 

(10 mL) was slowly added via cannula with rapid stirring, and a cloudy solution was evident. The 

solution was allowed to stir for 7 days at room temperature. The reaction mixture was filtered through a 

pad of Celite to yield a colorless solution. An equal amount of hexanes was layered on the filtrate via 

cannula. Colorless single crystals, suitable for x-ray diffraction studies were isolated from the resulting 

filtrate after standing for 3 weeks at room temperature. 

NASA/TM—2010-216826 2
2.4 X-Ray Crystallographic Study of 1 and 2 

X-ray intensity data from previously described single crystals were measured at 300 K on a Bruker 

SMART1000 (Bruker AXS, Inc.) CCD-based x-ray diffractometer system using Mo Kα (λ = 0.71073 Å). 

Crystals used for data collection were cemented to a quartz fiber with epoxy glue. Data were measured 

using ω scans of 0.3° per frame for 10 seconds for both 1 and 2 so that a hemisphere (1271 frames) was 

collected with a final resolution of 0.75 Å. No decay was indicated by the recollection of the first 50 

frames at the end of data collection. The frames were integrated with the Bruker SAINT (Bruker AXS, 

Inc.) software package (Ref. 11) using a narrow-frame integration algorithm, which also corrects for the 

Lorentz and polarization effects. Absorption corrections were applied using SADABS (Refs. 12 and 13) 

supplied by George Sheldrick (Ref. 14). Structures were solved and refined using the Bruker SHELXTL 

(Bruker AXS, Inc.) (version 5.1) software package (Refs. 14 and 15) in space groups of P-1bar (1) and 

P21/n (2). All non-hydrogen atoms were derived from the direct method solution. With all non-hydrogen 

atoms being anisotropic and hydrogen atoms being isotropic, the structure was refined to convergence by 

least squares method on F2

, SHELXL-97, incorporated in SHELXTL.PC V 5.03 (Ref. 14). 

Crystallographic data are given in Table 1, selected bond lengths and angles are given in Table 2. 

TABLE 1.—SUMMARY OF X-RAY DIFFRACTION DATA

Compound 1 2 

Empirical Formula C25H26Cl2GaN3O2 C32H31ClInN3O4

Molecular Weight 541.11 671.87

Crystal System Triclinic Monoclinic

Space Group P-1(bar) (No. 2) P21/n (No. 14)

a, Å 10.5987 (13) 13.1565 (13)

b, Å 11.3705 (15) 8.2116 (8)

c, Å 12.6660 (17) 28.796 (3)

α, deg. 104.525 (2) 90

β, deg. 101.976 (3) 94.460 (2)

γ, deg. 111.981 (2) 90

V, Å3 1290.7 (3) 3101.6 (5)

Z 2 4 

Dcalc, g cm–3 1.392 1.439

μ, mm–1 1.30 0.89

F 556 1368

Crystal size, mm 0.38 by 0.23 by 0.09 0.31 by 0.14 by 0.08

θ range for collection, deg. 2.2 to 22.3 2.5 to 22.2

No. collected 6882 15267

No. ind. (Rint) 4505 (0.029) 5462 (0.054)

Tmax, Tmin 1.000, 0.537 1.000, 0.580

R [F2 > 2σ(F2)] 0.044 0.053

wR(F2) 0.084a 0.119b

Largest diff. peak and hole, e Å–3 0.48, –0.41 1.17, –0.47

Goodness of fit (GOF) on F2 1.000 0.999

CCDC deposit no. 753437 753438

a

w = 1/[σ2(Fo

2

) + (0.0202P)

2

], where P = (Fo

2 + 2Fc2

)/3 b

w = 1/[σ2(Fo

2

) + (0.0584P)

2

], where P = (Fo

2 + 2Fc2

)/3.

NASA/TM—2010-216826 3
TABLE 2.—SELECT BOND DISTANCE (Å) AND ANGLES (°) FOR COMPOUNDS 1 AND 2

Ga(1)-O(1) 2.099(2) In(1)-O(1) 2.274(3)

Ga(1)-O(2) 2.102(3) In(1)-O(2) 2.292(4)

 In(1)-O(3) 2.212(3)

 In(1)-O(4) 2.417(4)

Ga(1)-N(1) 2.099(3) In(1)-N(1) 2.312(4)

Ga(1)-N(2) 2.111(3) In(1)-N(2) 2.286(4)

Ga(1)-Cl(1) 2.2455(11) In(1)-Cl(2) 2.4132(15)

Ga(1)-Cl(2) 2.2365(11) O(1)-C(13) 1.261(6)

O(1)-C(1) 1.288(4) O(2)-C(13) 1.259(6)

O(2)-C(1) 1.271(4) O(3)-C(20) 1.248(6)

O(4)-C(20) 1.249(6)

O(1)-Ga(1)-N(1) 85.47(10) O(3)-In(1)-O(1) 162.40(15)

O(1)-Ga(1)-O(2) 62.83(10) O(3)-In(1)-N(2) 82.98(14)

N(1)-Ga(1)-O(2) 87.21(11) O(1)-In(1)-N(2) 83.94(14)

O(1)-Ga(1)-N(2) 86.64(11) O(3)-In(1)-O(2) 134.10(14)

N(1)-Ga(1)-N(2) 171.04(12) O(1)-In(1)-O(2) 56.99(12)

O(2)-Ga(1)-N(2) 85.43(11) N(2)-In(1)-O(2) 140.78(14)

O(1)-Ga(1)-Cl(2) 159.73(8) O(3)-In(1)-N(1) 86.83(14)

N(1)-Ga(1)-Cl(2) 93.01(9) O(1)-In(1)-N(1) 81.50(14)

O(2)-Ga(1)-Cl(2) 96.92(8) N(2)-In(1)-N(1) 90.28(15)

N(2)-Ga(1)-Cl(2) 92.92(10) O(2)-In(1)-N(1) 81.33(14)

O(1)-Ga(1)-Cl(1) 95.30(8) O(3)-In(1)-Cl(2) 97.07(11)

N(1)-Ga(1)-Cl(1) 92.62(10) O(1)-In(1)-Cl(2) 95.43(11)

O(2)-Ga(1)-Cl(1) 158.09(8) N(2)-In(1)-Cl(2) 93.44(11)

N(2)-Ga(1)-Cl(1) 92.32(10) O(2)-In(1)-Cl(2) 93.60(10)

Cl(2)-Ga(1)-Cl(1) 104.96(4) N(1)-In(1)-Cl(2) 174.91(10)

O(2)-C(1)-O(1) 117.6(4) O(3)-In(1)-O(4) 55.57(13)

O(1)-In(1)-O(4) 135.57(13)

N(2)-In(1)-O(4) 138.45(14)

O(2)-In(1)-O(4) 79.23(13)

N(1)-In(1)-O(4) 85.11(14)

Cl(2)-In(1)-O(4) 94.37(10)

O(2)-C(13)-O(1) 119.6(5)

O(4)-C(20)-O(3) 120.2(5)

3.0 Results and Discus0sion

3.1 Synthesis of Compounds 1 and 2 

The synthesis of both compound 1 and 2 can be simply described as oxidative addition, see (1) and 

(2) respectively, below, with the cleavage of the peroxide bond and subsequent electron transfer 

producing benzoate ligands and oxidizing the In and Ga centers to produce trivalent metal complexes.

Ga2Cl4 + H5C6C(O)O-OC(O)C6H5  2 GaCl2(4-Mepy)2(O2CC6H5) (1)

InCl + H5C6C(O)O-OC(O)C6H5  InCl(4-Mepy)2(O2CC6H5)2 (2)

The starting material for reaction (1) is actually more accurately described as a Ga(I)Ga(III) species: 

Ga+

[GaCl4]

–

. The reaction most likely proceeds through an intermediate ethane-like formally Ga(II) 

complex, Ga2Cl4(γ-pic)2 (3). An unsuccessful attempt to produce a gallium basic carboxylate (Ref. 9), 

resulted in the isolation and structural characterization of the Ga(II) dimer (Ref. 7). In the same study, an 

NASA/TM—2010-216826 4
attempt to produce a mixed-metal Ga-Ni species resulted in the isolation of the solvated mixed-oxidation 

state salt, [GaCl2(γ-pic)4]

+

[GaCl4]

–

 (4) (Ref. 7). The isolation and structural characterization of 1 brings to 

five the number of related structures from the reaction of benzoate-containing reagents and Ga2Cl4 in γpicoline, reinforcing the utility of Ga2Cl4 as an extremely versatile entry into Ga coordination chemistry.

The oxidizing potential of benzoyl peroxide is amply demonstrated in reaction (2). We had previously 

exploited this chemistry when we prepared the first example of an eight-coordinate indium benzoate, 

In(O2CC6H5)3(4-Mepy)2, by oxidation of indium metal powder with a 3:2 excess of benzoyl peroxide in γpicoline (Ref. 10). The use of the indium (I) chloride starting material provides a site for further chemistry 

to be utilized for preparation of mixed-metal complexes or clusters (Refs. 5 and 6).

3.2 Structural Features of Compound 1

A key structural feature of 1 is the chelating benzoate ligand; compound 1 (shown in Fig. 1) is the

first example of such a structurally characterized gallium benzoate. A recent review of mononuclear sixcoordinated Ga compounds did not include a single example of a homoleptic, tris-bidentate or chelating 

carboxylate structure (Ref. 16). A structural and theoretical study by Barron et al. demonstrated that 

chelated-group 13 carboxylate structures (particularly Al) are not energetically favorable, relative to 

bridged on mono-dentate coordination (Ref. 17). A very thorough discussion of coordination of metal 

carboxylates can be found in a classic monograph (Ref. 18).

The angle formed by the chelating benzoate in 1, O1-Ga-O2, is 62.83(10)°, and is significantly larger 

than the average angle for compound 2 of 56.28(13)° but is comparable to an average angle of 62.6(1)° 

for three structurally characterized chelating carboxylates previously reported (Refs. 19 to 21); a more 

thorough consideration of indium carboxylate-chelate bonding angles is given below. The previously 

reported chelating carboxylates include a four-coordinate doubly-chelating dicarboxylate organometallic 

complex (Ref. 19) and two compounds stabilized by chelating hetrocyclic ligands, one with 

(pyrazolyl)borate (Ref. 20) and the other with benzoxazole (Ref. 21). 

Previously, we prepared a trimeric basic carboxylate (compound 5) with syn-syn bridging benzoates 

(Ref. 18) obtained through a similar reaction involving sodium benzoate instead of benzoyl peroxide 

(Ref. 9); see reaction (3). The source of the central oxygen atom is likely water from the sodium benzoate.

2 Ga2Cl4 + 6 NaCO2C6H5  [Ga3(μ3-O)(μ-O2CC6H5)6(4-Mepy)3][GaCl4] (3)

NASA/TM—2010-216826 5
The Ga-O bond distances of the bridging benzoates in 5 ranged from 1.959 (5) to 2.006 (9) Å, with an 

average distance of 1.985(6) Å (Ref. 9). This is shorter than the average Ga-O bond distance for the 

chelating benzoate found in 1 of 2.101(3) Å. These intermolecular distances are comparable to those found 

in the three chelating carboxylates (Refs. 19 to 21) that range from 2.042(2) to 2.127(3) Å, with the fourcoordinate organometallic compound having the shortest average bond length (2.049(2) Å) (Ref. 19). Of the 

four structurally characterized chelating gallium carboxylates, only the (pyrazolyl) borate compound had 

asymmetrical coordination of the carboxylate moiety (∆Ga-O = 0.079(3) Å) (Ref. 20). 

This can be contrasted to the surprisingly complex structure of methylgallium diacetate, H3CGa(O2CCH3)2 (Ref. 22). This structure includes dative, bridging, and monodentate acetate coordination 

resulting in Ga-O bond distances ranging from 1.873(3) to 2.219(3) Å. As noted previously (Ref. 17), 

several reports of related organometallic indium compounds, dimethyl (Ref. 23) and diethyl (Ref. 24) 

acetate include simultaneously bridging and chelating acetate coordination. A much more straightforward 

Ga acetate monodentate interaction is found in a neutral acetato tetraphenylporphyrin complex 

(Ga(OAc)(tpp) with Ga-O bond length of 1.874(4) Å (Ref. 25), very similar to the mondentate Ga-O bond 

length of 1.873(3) Å (Ref. 22). 

A further example of a lengthened M-O bond for a chelating versus bridging carboxylate group is 

demonstrated by a series of silver complexes (AgO2CR) 2 where a dimer (R = C(Me)=C(Me)H) with 

bridging carboxylates is stabilized as a monomer by the addition of triphenylphosphine ligands: 

[AgO2CR(PPh3)2] (R = CH2CN, CH2CH2=C(H)CH2, and C(Me)=C(Me)H) with a subsequent average 

increase of 0.235(3) Å for a chelated versus bridging Ag-O bond length (Ref. 26). 

The carboxylate moiety in 1 is fairly symmetrical with an average C-O bond length of 1.280(4) Å. This 

is comparable to an average C-O bond length of 1.274(5) Å for the bridging acetates of 

methylgalliumdiacetate (Ref. 22), 1.25(2) Å for the bridging benzoates of compound 5 (Ref. 9), 1.255(2) Å 

for the chelating acetate of the benzoxazole (Ref. 21), and 1.254(6) Å for compound 2 of this study. A 

recent study of solvent-free synthesis of a bismuth carboxylate reported a C-O bond range of 1.249(2) Å to 

1.301(2) Å for dimeric substituted benzoates with multiple coordination modes (Ref. 27). 

The 2.105(3) Å average Ga-N bond length for the ligated picolines is comparable to 2.105(5) Å for 4

(Ref. 7) and 2.085(9) Å for 5 (Ref. 9). This is slightly longer than Ga-N bond length of 2.058(4) Å for the 

(pyrazolyl)borate (Ref. 20) and 2.034(2) Å for the benzoxazole (Ref. 21) compounds. It is longer than the 

Ga-N (picoline) bond length of 2.005 (6) Å of the Ga(II) complex, 3 (Ref. 7). Finally, the Ga-Cl average 

bond length of 2.2410(11) Å is comparable to Ga-Cl bond lengths determined for compounds 3 (2.195(2) 

Å) and 4 (cation – 2.320(2) Å; anion – 2.157(3) Å)) (Ref. 7), 5 (anion – 2.126(12) Å) (Ref. 9), and 

2.2827(16) Å averaged for [GaCl2(γ-pic)2(S2CNR2)] (R = Me (Ref. 8), Et (Ref. 7)).

The N1-Ga-N2 angle is 171.04(12)°; as expected the picoline rings tilt towards the chelated benzoate.

The three aromatic rings are roughly parallel; giving the complex a semi-paddlewheel appearance, more 

typically associated with bridging carboxylate structures (Refs. 9 and 28). The narrow angle of the benzoate 

results in a larger Cl2-Ga-Cl1 angle of 104.96(4)°. The O2-C1-O1 angle of 117.6(4)° is slightly smaller than 

the 120° expected for an sp2 hybridized RCO2

– moiety; this is likely due to the steric hindrance of the 

chelated benzoate bonding to a Ga(III) center. For the less-constrained six bridging benzoates in complex 5, 

the CO2

– angle ranged from 123° to 128° (Ref. 9). In CH3Ga(OAc)2, the average bridging CO2– bonding 

angle was 120.3(3)°; the monodentate acetate had a 122.0(5)° CO2

– bonding angle (Ref. 19); and the 

monodentate acetate of (Ga(OAc)(tpp) had a 122.9(5)° CO2

– bonding angle (Ref. 22). The other chelating 

carboxylates (Refs. 19 and 21) had more narrow O-C-O angles of approximately 118°, expected for the 

wider O-Ga-O chelate.

3.3 Structural Features of Compound 2

As has been noted previously, bidentate chelating In (III) carboxylate bonding has not frequently been 

observed (Refs. 17 and 18). Compound 2 (shown in Fig. 2) had In-O bond distances ranging from 

2.212(3) Å to 2.417(4) Å with one symmetrical benzoate, like complex 1, with an average In-O distance of 

2.283(4) Å, the other unsymmetrical with a 0.205 Å ∆In-O bond length. A review of In-O bond lengths in 

NASA/TM—2010-216826 6
chelating In carboxylates exhibits a range from 2.142(5) to 2.875(8) Å from (nearly) symmetrical to 

asymmetrical (Refs. 4, 10, 29 to 36). In our previously reported eight-coordinate In benzoate complex, one 

benzoate was symmetrical with an In-O bond distance of 2.286(5) Å, and the other two were asymmetrical 

with distances of 2.225(6) Å and 2.413(5) Å (Ref. 10). Asymmetrical bonding of chelating carboxylate 

groups to an In(III) center has been observed for other eight-coordinate carboxylates: In(O2CMe)3L (L = 

phen, ∆In-O = 0.157(7) Å and 0.198(7) Å ; L = bipy, ∆In-O = 0.172(6) Å) (Ref. 37). A related but simpler, 

cis-dichloro chelating-benzoato octahedral complex with two trans pyridine ligands had similar, nearly 

symmetrical In-O bond lengths of 2.246(4) Å and 2.280(4) Å (Ref. 32). Another octahedral benzoate 

compound with a tetradentate N2S2 bis(aminoethanethiol) chelate had a significantly more asymmetric 

benzoate coordination with In-O bond lengths of 2.247(3) Å and 2.390(3) Å (Ref. 30). Another sevencoordinate carboxylate with a terpyridine and two azide ligands had a slightly less asymmetric carboxylate 

with In-O bond lengths of 2.274(2) Å and 2.354(2) Å (Ref. 4). A similar degree of asymmetry is observed 

for a series of trinuclear and tetranuclear metal cluster butyrates containing In, and Co or Ni atoms (Ref. 31).

An unsymmetrical acetate is found in a (TPP)In(O2CCH3) (TPP = tetraphenylporphinato) complex with 

In-O bond lengths of 2.215(4) Å and 2.322(4) Å (Ref. 33). A pair of related tetra-arylporphyrinato indium 

acetates (TRP)In(O2CCH3) (R = py, 4-pyridyl; mp, 4-methoxyphenyl) resulted in nearly symmetrical (R = 

py, In-O range from 2.24(1) to 2.34(1) Å) and unsymmetrical (R = mp, In-O = 2.185(6) Å and 2.412(6) Å) 

acetates (Ref. 34). An asymmetrically-bound acetate is also found in an (OEP)In(O2CCH3) (OEP = 

octaethylporphyrinato) complex with In-O bond lengths of 2.60(2) Å and 2.14(1) Å (Ref. 35). Two related 

ylide-containing halide compounds had In-O coordination that varied from slightly (< 0.1 Å) to moderately 

asymmetric (> 0.25 Å) (Ref. 29). Finally, the most asymmetric bidentate chelate is found in a dimeric μ-oxo 

bridged neutral seven-coordinate complex [L2In2(CH3CO2)4(μ-O)]•2NaClO4 (L = 1,4,7-triazacyclononane) 

with each In(III) bound to a monodentate and chelating acetate group; significantly different average In-O 

bond lengths in the chelating groups of 2.142(5) Å and 2.863(7) Å (Ref. 36) are present.

The In-Cl bond length in 2 is 2.4132(15) Å and similar to the related octahedral chloro-benzoato compound, 

2.391(2) Å (Ref. 32). It is also comparable to the cis-In-Cl bond length in mer-InCl3(4-Etpy)3 of 2.41 Å but 

shorter than the trans-In-Cl bond length of 2.46 Å (Ref. 38). The cis- (2.471(1) Å) and trans (2.476(2) Å) 

In-Cl bond lengths in mer-InCl3(py)3•py (Ref. 39) are practically equal within experimental error. The ylide 

compound with chloride ligands has an In-Cl bond length that ranges from 2.26(1) to 2.49(1) Å (Ref. 29). 

NASA/TM—2010-216826 7
The In-N bond lengths are unremarkable but slightly unsymmetrical; there is a slight lengthening of the 

In-N bond trans to the Cl (2.312(4) Å versus 2.286(4) Å in the plane). The two In-N bond lengths for the 

trans pyridines in the related octahedral compound are (2.250(5) and 2.300(6) Å (Ref. 32). This is typically 

not observed in the family of mer-InX3(Rpy)3 (R = H, X = I, Br; R = Et; X = Cl; R = Me, X = I) complexes 

where the average In-N bond length is 2.31 Å (Refs. 38 to 41). There is some asymmetry in merInCl3(py)3•py where there is a some lengthening of the In-N bond trans to a Cl (2.377(21) Å) versus

2.302(7) Å (for trans pyridines). The In-N bond lengths were similar for the two seven-coordinate 

compounds with terpyridine (2.292(2) – 2.341(2) Å) and azide (2.203(3) Å) ligands (Ref. 4) and the 

triazacyclononane chelate (2.271(5) to 2.324(5) Å) (Ref. 36). The tetradentate bis(aminoethanethiol) 

octahedral compound (2.298(3) and 2.367(3) Å) was also similar (Ref. 30). The In-N bond lengths for the 

porphyrin compounds were shorter and ranged from 2.16 to 2.18 Å (Refs. 33 to 35).

The Cl(2)-In(1)-N(1) bond angle is 174.91(10)°, the apical Cl atom is inclined away from the other five 

coordinated atoms in the InO4N plane at angles from 93.44(11)° (N(2)-In(1)-Cl(2)) to 97.07(11)° (O(3)-

In(1)-Cl(2)). The two In-N bonds are nearly perpendicular forming a (N(2)-In(1)-N(1) angle of 90.28(15)°.

The four In-O bonds are bent towards the apical N(1) forming O-In(1)-N(1) angles that vary from an 

average of 81.42(14)° for In-O(1) and In-O(2) to 86.83(14)° for In-O(3). Steric factors can be invoked to 

explain this structural feature. As with the gallium complex above, the two chelating benzoates and the 

apical picoline are roughly parallel and form a semi-paddlewheel structure.

The benzoate chelates contain smaller angles of 56.99(12)° and 55.57(13)° for (O(1)-In(1)-O(2)) and 

(O(3)-In(1)-O(4)), respectively in the indium complex (2) than the gallium complexes (1) and (Refs. 19 

to 21). The individual nearest-neighbor atoms in the InO4N plane form five angles that add up to 

approximately 359°; the non-chelated atoms form average angles of 82°. The larger size of the In(III) center 

results in less steric strain for the chelates and a nearly symmetrical RCO2

– average bond angle of 119.9(5)°. 

The closely-related eight-coordinate tris-benzoato bis-picoline indium (III) complex had quite similar O-InO angles of 56.5(3) ° and 55.9(2)° (Ref. 10). The eight-coordinate complex also had a nearly symmetrical 

RCO2

– average bond angle of 119.5(8)°. The octahedral benzoato complex, isostructural with compound 1, 

had a similar RCO2

– angle (118.9(6)°), with a wider O-In-O angle of 57.5(1)° (Ref. 32), similar to the larger 

of the two angles of compound 2, but significantly less than the O-Ga-O angle of 62.83(10)° of 1. With a 

few exceptions, the O-In-O benzoate angle ranged from a low of 55.57(13) to 56.99(12) for many of the six, 

seven, or eight-coordinate carboxylates. The six-coordinate porphyrin acetate compounds had slightly 

smaller average O-In-O (54.6(3)°) and RCO2

– (118.5(4)°) angles (Refs. 33 and 34). The dimeric μ-oxo 

bridged neutral seven-coordinate complex [L2In2(CH3CO2)4(μ-O)]•2NaClO4 (L = 1,4,7-triazacyclononane) 

with asymmetric chelating acetate groups had a significantly constrained O-In-O bond angle of 48.9(2)°.

The smaller O-In-O angle with the porphyrin-containing structures is expected as the macrocycles impose 

steric strain. The ylide compounds (Ref. 29) and the multi-nuclear cluster compounds (Ref. 31) had larger 

bond angles ranging from around 57° to 59°.

As noted above and compiled in Table 3, there are nearly 15 chelated In(III) carboxylate or related 

molecular structures that are five (Ref. 29) six (Refs. 29 to 36), seven (2 and (Refs. 4, 31, and 36)), and eight 

(Refs. 10 and 37) coordinate. Many of these chelating carboxylate structures consist of a macrocyclic or 

large heterocyclic chelating ligand (Refs. 4, 30, 33 to 36) or multi-nuclear cluster structure (Ref. 31). It is 

reasonable to assert that the aromatic benzoato chelate and pyridine-like ligands (Refs. 10 and 32), electronwithdrawing halide ligands (2, (Refs. 29 and 32)) and solvent of crystallization (2, (Ref. 10) stabilize the 

structures in a similar fashion without undue steric hindrance. Two other macrocycle-stabilized structures of 

seven-coordinate In(III) to note are two related pentagonal bipyramid complexes, [InCl3(L’)(MeOH)] and 

[InCl(η2

-C2O4)(L’)(OH2)] (L’ = 2,6-bis(acetyloxime)-pyridine) (Refs. 42 and 43). A final observation to 

make is that compounds 1 and 2 adopt a roughly pentagonal bipyramidal structure. Compound 1, and the 

isostructural In complex (Ref. 32), can be described as semi-paddlewheel with three roughly parallel 

aromatic rings. The semi-paddlewheel motif of compound 2 has a more propeller-like appearance with a 

bowl-shaped triple aromatic-ring coordination plane.

NASA/TM—2010-216826 8
TABLE 3.—SELECTED BOND DISTANCES (Å) AND ANGLES (°) FOR MOLECULAR COMPLEXES WITH 

CHELATING CARBOXYLATES OF Ga, In AND OTHER METALS WITH SIMILAR IONIC RADII

Compound CN dM-O 

(Å)

O-M-O 

(°)

O-C-O 

(°)

Reference

[Ag(O2CR)(P(C6H5)3)2] 

R = CH2CN, (CH2)2CH=CH2, or C(Me)=C(H)Me 4 2.401(3) – 2.495(2) 52.61(7) – 53.86(6) 122.6(2) – 126.4(3) Ref. 26

[(Ga((Me3Si)2CH)2)2(ndc)]•2MeC5H9 

H2ndc = 1,6-naphthalenedicarboxylic acid 4 2.042(2), 2.056(2) 64.53(8) 118.0(3) Ref. 19

[InCl3(η2-O2CC{P(C6H5)3}2] 5 2.181(6), 2.304(6) 58.7(2) 118.6(8) Ref. 29

[InI2(η2-O2CC{P(C6H5)3}2

+

][I-] 6 2.168(5) – 2.437(5) 57.0(2), 58.6(2) 117.9(7), 120.1(7) Ref. 29

[H2B(pz)2]2Ga(O2CCH3)

pz = {N2(CH)3} 6 2.048(3), 2.127(3) 62.3(1) Ref. 20

[Ga(hbo)2(O2CCH3)] 

Hhbo = 2-(2’-hydroxyphenyl)-2-benzoxazole 6 2.117(2) 61.1(1) 118.2(4) Ref. 21

[GaCl2(O2CPh)(4-Mepy)2]•4-Mepy 6 2.099(2), 2.102(3) 62.83(10) 117.6(4) This work

[In (BAT-TM)(O2CC6H5)] 

BAT-TM = N2S2 tetradentate ligand 6 2.247(3), 2.390(3) 56.3(1) 120.7(4) Ref. 30

[In2M2(OH)2(O2CtBu)8L2]

a

(M,L = Co, MeCN; M,L = Ni, MeCN/HO2CtBu) 6 2.2091(13) –2.275(8) 56.9(3) –59.1(3) 117.1(10) –120.6(10) Ref. 31

[InCl2(O2CPh)(py)2] 6 2.246(4), 2.280(4) 57.5(1) 118.9(6) Ref. 32

[In(TPP)(O2CCH3)]

TPP = tetraphenylporphyrin 6 2.215(4), 2.322(4) 54.4(2) 118.5(4) Ref. 33

[In(TRP)(O2CCH3)] 

R = 4-pyridyl or 4-methoxyphenyl 6 2.185(6) – 2.412(6) 54.4(4), 55.0(2) 115(2) –121.1(7) Ref. 34

[InCl(O2CPh)2(4-Mepy)2]•(4-Mepy) 7 2.212(3) – 2.417(4) 55.57(13),

56.99(12) 119.6(5), 120.2(5) This work

[L2In2(O2CCH3)4(μ-O)]•2NaClO4 

L = 1,4,7-triazacyclononane 7 2.142(5) – 2.875(8) 48.9(2) Ref. 36

[In2Ni(OH)(O2CtBu)7(HO2CtBu)x]

a

 

(x = 1,2) 7 2.208(6) – 2.249(6) 58.4(2),

58.5(2)

118.6(8),

119.0(8) Ref. 31

[(terpy)In(N3)2(O2C(CH2)2CH2OH)]

terpy = terpyridine 7 2.274(2), 2.354(2) 56.31(7) 120.2(2) Ref. 4

[SbCl(C6H5)2(O2C(2-Me)C6H4)2] 7 2.213(3) – 2.296(3) 57.46(11), 57.58(11) 118.8(6), 120.5(7) Ref. 44

[Cd(O2C(3,4-OH)C6H3)2(H2O)3] 7 2.304(4) – 2.513(4) 54.0(1), 54.3(1) 117.3(4), 117.6(4), Ref. 45

[MoBr(O2CCF3)(CO)2(P(C6H5)3)2] 7 2.304(9), 2.320(9) 56.5(3) 126.0(1) Ref. 46

[Bi(O2C(2-EtO)C6H4)3]2 8 2.207(1), 2.532(1) 55.06(4) 120.2(2) Ref. 27

[In(O2CPh)3(4-Mepy)2]•4H2O 8 2.225(6) – 2.413(5) 55.9(2), 56.5(3) 119(1), 120.0(7) Ref. 10

[In(O2CCH3)3L]

L = 2,2’-bipy or 1,10-phen 8 2.221(3) – 2.422(6) 54.4(2) – 56.5(3) Ref. 37

a

Data for In coordination environment only.

3.4 Comparison of Compounds 1 and 2 with Similar Molecular Complexes of Other 

Metals

It is interesting to include a survey of other related chelating-carboxylate complexes of other metals 

similar in size to In(III) ions. Table 3 includes compounds 1 and 2, other related indium and gallium 

structures, and other related structures of mostly main group complexes with higher coordination numbers 

and similar ionic radii (0.8 ~ 0.92 Å) to In(III) complexes. A key feature of nearly every compound in 

Table 3 is complexation with aromatic rings for electronic and steric stability. These chelating compounds 

rely on a variety of motifs for supporting the chelating structure: macrocyclic and/or multi-dentate ligands 

(Refs. 4, 10, 19 to 21, 26, 30, 33 to 37), carboxylates with unsaturated bonds or pendant groups for 

structural or electronic stabilization (Refs. 4, 26, 27, 29, 44, and 45), or electronic-withdrawing ligands 

such as halides and CF3CO2

–

 (1, 2, (Refs. 29, 32, 37, 38, and 46)). Interestingly, several structures 

contained multiple modes of coordination to identical carboxylate groups (Refs. 27 and 31). 

The structure most similar to compound 1 is the analogous six-coordinate In benzoate complex (Ref. 32). 

However, due to the larger size of the In(III) ion, this structure does not contain as much strain around the 

chelating benzoate. The seven-coordinate Sb(V) organometallic compound is most similar in structure to 2

(Ref. 44). The other structurally-characterized seven-coordinate In(III) carboxylate environments are sterically 

constrained by tri-dentate chelating ligands (Refs. 4 and 36) or a multi-nuclear cluster environment (Ref. 31). 

Apparently, electron-withdrawing chloride ligand(s) and the inherent stability of the semi-paddlewheel 

NASA/TM—2010-216826 9
structure of the aromatic rings enables the use of simpler ligands via a straightforward synthesis used to 

produce compounds 1 and 2 and the related octahedral indium complex (Ref. 27). 

3.5 Comparison of Molecular Indium Benzoates with Indium Coordination Polymers

While a slight departure from the major thrust of this paper, it is useful to include a brief survey of 

recently reported chelating-carboxylate indium coordination polymers (Refs. 47 to 61), part of a recent 

wave of a literature describing intriguing new hybrid organic-inorganic materials with many potential 

applications. Table 4 includes numerous examples of indium carboxylate polymer framework materials 

and seven- and eight-coordinate indium benzoates from this study (compound 2) and Reference 10, 

respectively. Table 4 includes five basic types of In polymers constructs: seven-coordinate In polymers 

from di- (Refs. 47 to 49), tri- (Refs. 50 to 53) and tetracarboxylates (Ref. 54 and 55) and eight-coordinate 

In polymers from di- (Refs. 56 to 59) and tricarboxylates (Refs. 60 and 61), several of which are chiral 

(Refs. 51, 58, and 59). 

TABLE 4.—SELECTED BOND DISTANCES (Å) AND ANGLES (°) FOR 

INDIUM COORDINATION POLYMERS AND MOLECULAR BENZOATES

Compound CN dM-O 

(Å)

O-M-O 

(°)

O-C-O 

(°)

Reference

[InCl(O2CPh)2(4-Mepy)2]•(4-Mepy) 7 2.212(3) – 2.417(4) 55.57 (13), 56.99(12) 119.6(5), 120.2(5) This work

[In(OH)(ndc)2(H2O)]n 

H2ndc = 2,6- or 2,7-naphthalenedicarboxylic acid 7 2.247(2) – 2.3458(18) 56.39(12), 58.00(8) 119.1(2), 119.5(3) Ref. 47

[In2OH)2(pdc)2(H2O)]n 

H2pdc = 3,5-pyridinedicarboxylic acid 7 2.255(2), 2.311(2) 57.53(5) 121.36(18) Ref. 48

[In(OH)(tca)(H2O)]n

H2tca = thiophene-2,5-dicarboxylic acid 7 2.209(2) – 2.391(2) 56.86(7), 57.53(7) 119.8(2),120.2(2) Ref. 49

{[Hbipy+][In(Hbtc)2(bipy)–]•0.5H2O}n 

H3btc = benzenetricarboxylic acid

bipy = 4,4’-bipyridine

7 2.208(4) – 2.360(5) 54.4(4), 55.0(2) 120.1(6),

120.3(6) Ref. 50

{[Hpy+]2[In2(btc)2(μ-OH)2

2–

]}n 

H3btc = benzenetricarboxylic acid

py = pyridine

7 2.140(11) – 2.569(10) 54.8(3) – 57.1(4) 119.5(13) –124.1(14) Ref. 51

{[In2(btc)2(bipy)2]•4H2O}n 

H3btc = benzenetricarboxylic acid

bipy = 2,2’-bipyridine

7 2.170(4) – 2.434(4) 56.06(13), 56.38(12) 119.4(5),120.4(5) Ref. 52

{[In2(btc)2(H2O)2]•2H2O}n 

H3btc = benzenetricarboxylic acid 7 2.575(2), 2.580(2) 56.75(11), 58.10(11) 119.4(4),119.8(4) Ref. 53

[In2(btec)(bipy)2Cl2]n 

H4btec = benzenetetracarboxylic acid

bipy = 2,2’-bipyridine

7 2.176(8) – 2.551(9) 54.7(2) –57.5(2) 118.8(7) –122.3(11) Refs. 54 

and 55

[In(O2CPh)3(4-Mepy)2]•4H2O 8 2.225(6) – 2.413(5) 55.9(2), 56.5(3) 119(1), 120.0(7) Ref. 10

{[H+][In(bdc)2

–

]}n 

H2bdc = benzenedicarboxylic acid 8 2.267(7), 2.283(7) 57.7(3) 120.8(9) Ref. 56

{[M(H2O)6

3+][In3(μ2-pdc)63–

]•15H2O}n 

H2pdc = 2,3-pyrazinedicarboxylic acid

M = In, Cr0.7In0.3, or Fe0.3In0.7

8 2.236(4) – 2.446(6) 54.9(2) – 55.4(3) 120.3(5) – 123.4(8) Ref. 57

{[(Htmdp)+][In(pdc)2

–

]•(EtOH)(H2O)2}n 

tmdp = 4,4’-trimethylenedipiperidine

H2pdc = 2,5-pyridinedicarboxylic acid

8 2.205(5), 2.588(5) 54.29(17) 122.5(7) Ref. 58

{[NR4

+

][In(DL-cam)2

–

]•(H2O)2}n 

R = CH3; D- and L-camphorate

NR4

+ = choline; D-camphorate

8 2.188(7) – 2.407(8) 55.4(3) – 57.3(3) 119.0(10) –120.7(9) Ref. 59

a

{[NR4

+

][In(DL-cam)2

–

]•(H2O)2}n 

R = n-propyl; D- or DL-camphorate

NR4

+ = imidizolium; D-camphorate*

8 2.163(3) – 2.481(3) 54.7(4) – 58.2(4) 117(2) –124.8(16) Ref. 60

[In(btc)1.5(bipy)]n

H3btc = 1,4-benzenetricarboxylic acid

bipy = 2,2’-bipyridine

8 2.204(3) – 2.551(4) 53.50(11) – 57.22(10) 120.1(4), 120.5(4) Ref. 61

{[H2tmdp2+]3[In6(btc)8

6–

]•40H2O}n 

tmdp = 4,4’-trimethylene dipiperidine

H3btc = benzenetricarboxylic acid

8 2.155(5) –2.409(5) 56.36(18) 120.3(6) Ref. 62

a

Table entry also includes three more related structures (total of six) from same publication.

NASA/TM—2010-216826 10
The most notable observation to make when viewing the relevant bond distances and angles of the 

polymer materials as compared to the respective molecular species is the striking similarity of the In 

coordination environments; this is expected due to a lack of steric strain around In atoms from the flexible 

polymer coordination environment, it is this flexibility that gives rise to a variety of intriguing 2–D and 

3–D structural features. The In-O bond distances and O-In-O and O-C-O carboxylate angles of the 

polymer materials are quite similar to the molecular benzoates.

4.0 Conclusion

In summary, we have prepared two new simple chelating benzoate complexes of gallium and indium 

by straightforward oxidation of the Ga(II) and In(I) chlorides by benzoyl peroxide in 4-methylpyridine at 

room temperature. The six-coordinate gallium complex, which also includes two chloride and two gpicoline ligands, is the first example of a structurally-characterized chelating gallium benzoate. It is 

isostructural with a previously characterized analagous In(III) benzoate complex. The seven-coordinate 

In(III) bis-benzoate also includes one chloride and two g-picoline ligands and is the first example of its 

type with a simple ligand set; it is a structural analogue to a seven-coordinate Sb(V) organometallic 

compound. The most striking feature of these surprisingly simple compounds is a semi-paddlewheel 

geometry of roughly parallel aromatic rings of the benzoate and picoline ligands, which seems to lend an 

enhanced stability to the solid-state structures. This stability is further demonstrated by the similarity of 

the metal coordination environment for a number of seven or eight-coordinate indium carboxylate 

coordination polymer materials.

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NASA/TM—2010-216826 12
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(2007) pp. 1712–1715. 

NASA/TM—2010-216826 13

Appendix A.—Alternate Diagram of and Extensive Structural 

Information for Compound (1) - [GaCl2(4-Mepy)2(O2CPh)]•4-Mepy

NASA/TM—2010-216826 15
	


	
 





 





 







 
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Appendix B.—Alternate Diagram of and Extensive Structural 

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NASA/TM—2010-216826 30
REPORT DOCUMENTATION PAGE Form Approved 

OMB No. 0704-0188 

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1. REPORT DATE (DD-MM-YYYY)

01-12-2010 

2. REPORT TYPE

Technical Memorandum 

3. DATES COVERED (From - To)

4. TITLE AND SUBTITLE

Synthesis of Two New Group 13 Benzoato-Chloro Complexes: A Structural Study of Gallium 

and Indium Chelating Carboxylates 

5a. CONTRACT NUMBER

5b. GRANT NUMBER

5c. PROGRAM ELEMENT NUMBER

6. AUTHOR(S)

Duraj, Stan, A.; Hepp, Aloysius, F.; Woloszynek, Robert; Protasiewicz, John, D.; Dequeant, 

Michael; Ren, Tong 

5d. PROJECT NUMBER

5e. TASK NUMBER

5f. WORK UNIT NUMBER

WBS 387498.01.03.02.05 

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration 

John H. Glenn Research Center at Lewis Field 

Cleveland, Ohio 44135-3191 

8. PERFORMING ORGANIZATION

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E-17455 

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)

National Aeronautics and Space Administration 

Washington, DC 20546-0001 

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NASA 

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NASA/TM-2010-216826 

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Unclassified-Unlimited 

Subject Categories: 25 and 44 

Available electronically at http://gltrs.grc.nasa.gov 

This publication is available from the NASA Center for AeroSpace Information, 443-757-5802

13. SUPPLEMENTARY NOTES

14. ABSTRACT

Two new heteroleptic chelated-benzoato gallium (III) and indium (III) complexes have been prepared and structurally characterized. The 

molecular structures of [GaCl2(4-Mepy)2(O2CPh)]4-Mepy (1) and [InCl(4-Mepy)2(O2CPh)2]4-Mepy (2) have been determined by singlecrystal x-ray diffraction. The gallium compound (1) is a distorted octahedron with cis-chloride ligands co-planar with the chelating benzoate 

and the 4-methylpyridines trans to each other. This is the first example of a Ga(III) structure with a chelating benzoate. The indium 

compound (2) is a distorted pentagonal bipyramid with two chelating benzoates, one 4-methylpyridine in the plane and a chloride trans to 

the other 4-methylpyridine. The indium bis-benzoate is an unusual example of a seven-coordinate structure with classical ligands. Both 

complexes, which due to the chelates, could also be described as pseudo-trigonal bipyramidal, include a three-bladed motif with three 

roughly parallel aromatic rings that along with a solvent of crystallization and electron-withdrawing chloride ligand(s) stabilize the solidstate structures. 

15. SUBJECT TERMS

Indium compounds; Gallium compounds; Chlorides; Vapor deposition; Solar cells; Crystal structure 

16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF

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36 

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