1

CHAPTER 1

INTRODUCTION

1.1 HYDRAZINE

Hydrazine is the simplest diamine in its class of compounds and may be

thought of as derived from ammonia by replacement of a hydrogen atom by the –
NH2 group. The hydrated hydrazine, N2H4.H2O was first prepared by Curtius in
1887. The anhydrous hydrazine as a water free base was prepared by De Bruyn for
the first time. Preparation of hydrazine by the oxidation of NH3 with hypochlorite –
a process that became the chief commercial method of manufacture was first
demonstrated by Raschig.

For many years hydrazine was considered as a special chemical available

only in aqueous solution and in the formation of few salts. It remained as a
laboratory curiosity for over 50 years. During the Second World War, Germany
discovered the interesting property of hydrazine as a rocket fuel. Now it is one of the
most powerful liquid fuels among current rocket propellants. However, the chemical
uses of hydrazine now far surpass its use as a fuel. The bibliographic works on
hydrazine (Bottomley 1970, Schmidt 1984) are indispensable bibles for hydrazine
chemists. The field of hydrazine chemistry and its applications are over widening.

1.1.1 Applications

Anhydrous hydrazine (m.p. 2 °C, b.p.114 °C), a fuming colourless liquid,

is surprisingly stable in view of its endothermic nature(∆Hf = 50.43KJ /mol) and its
simple methyl and dimethyl derivatives have endothermic heats of formation and
 2

high heats of combustion. They have nitrogen in -2 valence state. Nitrogen's natural
tendency, however, is towards zero valency (N ≡ N), which gives off nearly six
times as much as energy as the N-N bond. Thus tremendous amount of energy is
released not only during decomposition of N2H4 to N2 but also at the time of the
mixing with the oxidizer. Hence they are used as fuels in rocket and spacecraft
powered engines. As a strong reducing agent, hydrazine is used for corrosion control
in boilers and hot water heating systems, for metal plating, and for reducing noble
metal catalysts and unsaturated bonds in organic compounds. It is also an oxidizing
agent under suitable conditions with two active nucleophilic nitrogens and four
replaceable hydrogens. It is the starting material for many derivatives; among which,
foaming agents for plastics, antioxidants, polymers, polymer cross linking and chain
extending agents, as well as biologically active pesticides, herbicides, plant growth
regulators and pharmaceuticals are important. As it is a good complexing ligand,
numerous complexes have been studied (Bottomley 1970 and Schmidt 1984). Many
heterocyclics are based on hydrazine, with rings containing from 1 to 5 nitrogen
atoms as well as other hetero atoms. The many advantageous properties of hydrazine
are exploited in the field of photographic chemicals and dyes. New uses for
hydrazine derivatives are discovered daily.

1.1.2 Basicity and Salt Forming Ability

As an Arrhenius base, hydrazine is a weaker base than ammonia because

the more electronegative group NH2 has the - I effect on the lone pair of electron of
the neighbouring nitrogen, making it less basic for protonation.

NH3 + H2O → NH4+ + OH - Kb =1.8 X 10-5 (1.1)

N2H4 + H2O → N2H5 + + OH - Kb = 8.5 X 10-7 (1.2)
 3

N2H5+ + H2O → N2H62+ + OH - Kb = 8.9 X 10-16 (1.3)

In principle, it can form two series of salts with monobasic acids, one
having the hydrazinium (+1) cation, N2H5+ and the other, hydrazinium(+2) cation,
N2H62+. The basic ionization constants of hydrazine in water suggest that N2H62+
exists only in the solid state or in conc. acid solutions. The salts containing this
cation are extensively hydrolyzed in water to give highly acidic solutions containing
the N2H5+ ion.

N2H62+ + H2O → N2H5+ + H3O+ (1.4)

The divalent cation seems to violate Pauling’s adjacent charge rule,

H3N+- NH3+, but is likely that this is in equilibrium with other tautomeric forms, e.g.
H3N+- NH2H+.The N2H5+ salts have been prepared with carboxylic acids and
numerous examples of them have been reported (Schmidt 1984), whereas the salts of
N2H62+ are limited (Starosta and Leciejewicz 2007, Starosta and Leciejewicz 2008).

1.2 TYPES OF HYDRAZINE SALTS

The hydrazinium salts are inorganic derivatives, well-crystallized and

colorless compounds, comparable to the corresponding ammonium salts. The
reducing property and the lack of thermal stability of hydrazinium salts differentiate
them from ammonium salts.

Hydrazine forms not only mono- and di acid salts of the types, N2H4·HA,
N2H4·2HA where HA represents a simple mono-basic acid, but also compounds of
the types 2N2H4·H2B and N2H4·H2B where H2B represents a dibasic acid. The best
known of these are N2H4·HA or 2N2H4·H2B [N2H5A or (N2H5)2B] and N2H4·2HA or
 4

N2H4·H2B [N2H6A2 or N2H6B] and not N2H4·2H2B. The N2H5+ and N2H62+ salts are
generally referred to as hydrazinium(+1) and hydrazinium(+2) salts respectively.

Even though N2H62+ salts are generally formed with strong acids, double
salts of this cation with ammonium ion are also formed. For example,
(NH4)2N2H6(ClO4)4 and (NH4)2N2H6(SO4)2 (Frech et al 1993) salts have been
prepared and characterized. Recently redetermination of hydrazinium (+2)
dichloride (N2H62+.2Cl-) has been reported (Kruszynski and Trzesowska 2007). In
many cases the preparation of hydrazinium salts is very easy, but in other cases,
such as in the preparation of hydrazinium nitrates or perchlorates, special
precautions are necessary to prevent unexpected explosions.

It is interesting to note that a few hydrazine salts form hydrates: e.g.

N2H5ClO4.0.5H2O, N2H6X2.2H2O, X = ClO4-, Br- and I-. It has been shown by IR,
thermal and conductivity measurements that water in these compounds is partially
present as oxonium ion H3O+ and involved in hydrogen bonding with N2H4 (Patil et
al 1983), (N2H5)2SO3.H2O (Patil et al 1980).

1.2.1 Methods of Preparation of Simple Hydrazinium Salts

1.2.1.1 Acid -Base Neutralization Method

In this method, the base is directly neutralized by the addition of the

corresponding acids in the aqueous medium. The pH of the solution is an important
factor to get the type of salt desired. The reactions are represented as given below:

N2H4.H2O + HA → N2H5A + H2O (1.5)

N2H4. H2O + 2HA → N2H6A2 + H2O (1.6)
N2H4. H2O + H2B → N2H6B + H2O (1.7)
 5

where HA is a monobasic acid, e.g., HCl, CH3COOH, HNO3 etc. and H2B is a
dibasic acid, e.g. H2SO4, H2C2O4 etc.Acids like H2SO4 (Hudson et al 1967) and HF
(Patil et al 1979) react with N2H4.H2O to form exclusively N2H62+ salts because of
their strong acidic nature and the low solubility of the resulting salts.
1.2.1.2 Double Decomposition Method

Hydrazinium sulphate (N2H5)2SO4, reacts with the corresponding barium

salts (Jones 1975) in the aqueous medium to form the salts. For example,

(N2H5)2SO4 + Ba(NO3)2 → BaSO4 + 2 N2H5NO3 (1.8)

1.2.1.3 Decomposition Method of Ammonium Salts

The reaction of stoichiometric quantities of N2H4.H2O and the simple

ammonium salts (Soundararajan 1979) produces the hydrazinium salts with the
liberation of NH3.

NH4X + N2H4.H2O → N2H5X + NH3+ H2O (1.9)

where x = halides, NO3-, N3-, CH3COO -, H2PO4 -, HF2-, HSO4- etc.

(NH4)2Y + 2N2H4.H2O → (N2H5)2Y + 2NH3 + 2H2O (1.10)

where Y = SO42-, C2O42-, HPO42-, S2O32- etc.

This method is a heterogeneous reaction. The salts N2H5HF2 (Patil et al

1979) and N2H5HSO4 (Vittal 1981) which could not be prepared by other methods,
can be prepared by this method.

The hydrazinium (+2) salts containing one molecule of a simple binary

acid are stable in solution. The diacid salts, however, exist in the solid state and
undergo immediate hydrolysis when dissolved in water (Nesamani 1982). The
monoacid salts N2H4.HA [N2H5 A] are usually more soluble in water than the diacid
 6

salts N2H4·2HA (N2H6 A2). Again N2H5+ salts are mostly hygroscopic and even some
of them are in liquid state (Patil et al 1980), while N2H62+ salts are not so, with an
exception of N2H6(ClO4)2.2H2O which is highly hygroscopic.

1.2.2 Salts of Hydrazine with Different Acids

1.2.2.1 With Inorganic acids

Hydrazine hydrate reacts with halogen acids to give salts of the type
N2H5X and N2H6X2 under different reaction conditions (Patil et al 1979, Patil et al
1978), where X = Cl-, Br-, I- or F-. When pure hydrazine reacts with nitric acid it
forms hydrazinium (+) nitrate and its crystal structure is reported (Grigoriev et al
2005). Hydrazine and nitrous acid undergo mutual destructive reaction. In neutral
solution it is possible to obtain hydrazinium(+1) nitrite as colorless to yellowish
hygroscopic solid.

Hydrazinium (+1) hydrogensulphate, has been prepared (Patil and Vittal

1982) for the first time by the reaction of solid ammonium hydrogen sulphate with
hydrazine hydrate.

2N2H6SO4 + BaCO3 → BaSO4 + (N2H5)2SO4 + H2O + CO2 (1.11)

Hydrazinium (+2) dithionate, N2H6S2O6 can be prepared from

hydrazinium (+2) sulphate and barium dithionate. Hydrazinium (+2) sulphamate is
prepared in a similar fashion from N2H6SO4 and Ba(SO3NH2)2.

When SO2 gas is passed through a 1:1 aqueous solution of hydrazine,

N2H5HSO3 is formed in less concentrated solution, whereas (N2H5)2S2O5 is formed
in more concentrated solution, no hydrazinium sulphate formation is observed.
Earlier studies have reported the formation of dihydrazinium hydrazodisulphite,
(HNSOON2H5)2 by the same reaction. Bubbling SO2 into an alcoholic solution of
 7

hydrazine hydrate, precipitates (N2H5)2SO3, which can also be prepared (Patil et al

1980) by the heterogeneous reaction between solid ammonium sulphite and
hydrazine hydrate. The reaction of hydrazine with a mixture of SO2 and CO2 results
in dual substitution on both nitrogen atoms to give a mixed sulphinate carbazate
N2H5OOSNHNHCOON2H5. On passing SO3 into an excess anhydrous hydrazine, it
gives the hydrazinium salt of hydrazinosulphuric acid, N2H3SO3N2H5. The
hydrazinium thiocyanate has been prepared from solid ammonium thiocyanate and
hydrazine hydrate (Patil et al 1980).

The latter salt also forms 1:1 adduct with phosphoric acid: N2H5H2PO4
.H3PO4. The salts N2H5H2PO4 and (N2H5)2HPO4 have been prepared by the reaction
between the corresponding ammonium phosphate and hydrazine hydrate and
characterized (Patil et al 1978) by chemical analysis and IR spectra(νN-N = 980 cm -1).

NH4 H2PO4 (S) + N2H4.H2O → N2H5H2PO4 (S) + H2O + NH3 (1.12)

(NH4)2HPO4 (S) + 2N2H4.H2O → (N2H5)2HPO4 (S) + 2H2O + 2NH3 (1.13)

The crystal structures of N2H5H2PO4 and N2H6(H2PO4)2 have also been

studied (Liminga 1965 and Liminga 1966).

Trihydrazinium (+1) dihydrogentriphosphate, (N2H5)3H2P3O10

and tetra hydrazinium (+1) tetrametaphosphate, (N2H5)4P4O12 were prepared
as anhydrous salts, whereas tetrahydrazinium(+1) pyrophosphate, (N2H5)4P2O7.H2O
and octa meta phosphate, (N2H5)8P8O24 .H2O were obtained as hydrates.
 8

1.2.2.2 With carboxylic acids

The hydrazinium salts of a number of aliphatic mono and di carboxylic

acids, and aromatic mono, di, tri and tetra carboxylic acids have been reported.

Hydrazinium (+1) formate (hydrazinium monoformate), though reported

(Schmidt 1984) to have been prepared from formic acid and hydrazine hydrate, has
not been well characterized. The preparation of hydrazinium(+1) acetate has
been reported by the decomposition of ammonium acetate by hydrazine hydrate
(Patil et al 1980). The dihydrazinium(+1) oxalate, (N2H5)2C2O4, has been repeatedly
studied, because it is a well crystallized solid and also forms double salts with other
cations. The metathetical reaction of ammonium oxalate monohydrate with excess of
N2H4.H2O gives (COON2H5)2.N2H4, which begins to lose solvated hydrazine at 90
°C and then melts at 153 °C (Patil et al 1979 and Patil et al 1978). The
hydrazinium(+1) oxalate can be obtained by treating hydrazinium(+2) oxalate in
aqueous solution with N2H4.H2O until the solution becomes permanently alkaline.
The N2H5HC2O4 has been prepared by mixing hot aqueous solutions, whereas
(N2H5)2C2O4 has been prepared in cold condition. Efforts to crystallize the latter
from hot solution always resulted in the former only.

Numerous salts of hydrazine with several organic acids are available in

the literature. Some of the common salts are N2H5.C7H4NO3S (Banerjee et al 2006),
hydrazinium propionate, butyrate(Schmidt 1984). Moreover, hydrazinium salts of a
series of dicarboxylic acids like hydrazinium hydrogenmalonate, hydrogenglutarate,
hydrogenadipate and dihydrazinium succinate (Sivasankar 1994), higher
homologous dicarboxylic acids viz. pimelic, suberic, azelaic, alpha keto glutaric and
iminodiacetic, malic, aspartic and glutamic acids (Yasodhai and Govindarajan
1999), oxydiacetic acid (Yasodhai and Govindarajan 2000), heteroaromatic acids
 9

like pyridine dicarboxylic acids (Saravanan and Govindarajan 2003) and pyrazine
carboxylic acids (Premkumar et al 2003) have been prepared by the acid-base
neutralisation method and characterized. Hydrazine also forms salts with aromatic
carboxylic acids like benzoic, salicylic, phthalic acids (Kuppusamy 1995), trimesic,
trimellitic, hemimellitic and pyromellitic acids (Vairam and Govindarajan 2004),
naphthoic, hydroxy naphthoic and naphthoxy acetic acids (Arunadevi 2009).

Simple hydrazinium salts have numerous applications (Schmidt 1984),

such as a source of anhydrous hydrazine, additives in propellants, drugs, to treat
cancer and Hodgkin’s disease, explosives(Schimidt 1984) and as ligands to prepare
metal hydrazine/hydrazinium complexes(Govindarjan et al 1986, Govindarajan et al
1986a and Yasodhai et al 1999) . A few of them are also used as flame retardants
(Patil et al 1980 and Patil et al 1981) and proton conductors (Chandra and Singh
1983).

1.3 THERMAL PROPERTIES OF HYDRAZINE AND ITS SIMPLE

SALTS

Heating of hydrazine salts, in most cases causes decomposition. A very

few of them are stable at their melting points. The diacid salts on heating decompose
to yield the monoacid salts as intermediates.

N2H4.2HA → N2H4.HA + HA (1.14)

The hydrazinium salts of the type N2H5X [X = Cl-, Br-, I-, 0.5SO42-,
H2PO4-] decompose exothermally in air to the corresponding ammonium salts with
the evolution of ammonia and nitrogen (Patil et al 1979 and Jasim 1988). Some of
the hydrazinium salts like N2H5N3 (Patil et al 1979), N2H5HF2 (Patil et al 1979) and
N2H5F (Soundararajan 1979) do not decompose exothermally, but volatilize under
the conditions employed. The simultaneous TG, DTA and EGA thermolysis of
hydrazinium sulphate has also been studied (Jasim 1988). The hydrazine salts such
 10

as hydrazinium perchlorate and nitrate are used as high energy oxidisers in

propellants. Hence, thermal decomposition of these compounds has been
investigated in detail (Pai Verneker et al 1976, Breisacher et al 1972 and Patil et al
1980). Thermal studies on hydrazinium sulphite hydrate (Patil et al 1980) shows that
it melts before decomposition. In the same report, an interesting and quantitative
conversion of hydrazinium thiocyanate to thiosemicarbazide has been discussed.

The thermal decomposition of hydrazinium carboxylates is more

interesting. The hydrazinium formate hemihydrate (Sivasankar and Govindarajan
1995) melts before undergoing endothermic decomposition to gaseous products. The
hydrazinium acetate also follows the same pattern of thermal decomposition as
already reported (Patil et al 1980). The thermal decomposition of hydrazinium
hydrogen oxalate and dihydrazinium oxalate has been investigated in detail (Udupa
1982, Gajapathy et al 1983). An interesting behaviour in their thermal properties is
that dihydrazinium salt is converted to monohydrazinium salt after melting and
losing one N2H4 molecule.

The thermal decomposition of hydrazinium dicarboxylates of malonic,

succinic, glutaric, adipic acid (Yasodhai and Govindarajan 1999) and phthalic acids
has been studied by TG-DTA method. All of them, except terephthalate and
isophthalates, decompose to gaseous products endothermally (Sivasankar 1994).
Terephthalate and isophthalate salts (Kuppusamy et al 1995) undergo exothermic
and endothermic decompositions. Hemimellitate, trimellitate, trimesate and
pyromellitate salts undergo strong exothermic decomposition with the formation of
carbon residue as the final product (Vairam and Govindarajan 2004).
 11

1.4 METAL HYDRAZINE COMPLEXES

The hydrazine does not frequently act as a reducing agent in reactions

with transition metals but acts as a ligand to form complexes. This broad area of
hydrazine complexes has been reviewed earlier (Bottomley 1970, Dilworth 1976).

1.4.1 Hydrazine as a Ligand

Hydrazine, like other polybasic ligands, offers the possibility of several

different types of coordination behavior towards metal ions. It can, of course,
function as a monodentate ligand but may also serve as either a bridging or chelating
bidentate ligand. Although numerous examples of both monodentate and bridging
hydrazine have been demonstrated crystallographically, no verified examples
(with the possible exception of (i-pro)4MN2H4, M = Ti or Zr) of chelatively bound
hydrazine have been reported.

Monoprotonated hydrazine, hydrazinium cation (N2H5+) still retains a

basic site and is capable of coordination. It is potentially a monodentate ligand and
complexes containing it are known. The donor abilities of hydrazine from
complexometric titration (Bisacchi and Goldwhite 1970) are shown in the order:

N2H4 > CH3NHNH2 > C2H5NHNH2 > (CH3)2NNH2 (1.15)

A number of complexes with substituted hydrazines have been reviewed

by Heaton et al 1996.
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1.4.2 Synthesis of Metal Hydrazine Complexes

1.4.2.1 Reactions of Hydrazine and its Salts with Metal

The high dielectric constant of anhydrous hydrazine suggests that it would

be a moderate solvent for many ionic compounds. It is not altogether unexpected to
find that hydrazine salts when dissolved in hydrazine or hydrazine hydrate behave as
acids. Thus, metals like Mg, Fe, Co, Ni, Zn, or Cd dissolved in a solution containing
hydrazine hydrate and hydrazinium or ammonium salts liberate hydrogen (Patil et al
1982).

M + 2N2H5X → M(N2H4)2X2+ H2 (1.16)

where X = 0.5 SO42-, 0.5 C2O42-, N3-, ClO4- etc.

Some mixed metal oxalate derivatives such as MFe2(C2O4)3(N2H4)x (M =

Mg, Mn, Co, Ni, or Zn: x = 5 and 6 ) and MgFe2(N2O2)3(N2H4)5 (Gajapathy 1982)
have been synthesized using the above procedure. The complex (N2H5)2Mg(SO4)2
has been prepared by the reaction of magnesium powder and ammonium sulphate in
the presence of hydrazine hydrate (Patil
et al 1981).

1.4.2.2 Reactions of Hydrazine with Metal Salts

The insoluble complexes M(N2H4)2X2, (M = Mn, Co, Ni, Zn or Cd and X

= Cl-, Br-, I-, 0.5SO42-, NCS-, HCOO-, CH3COO-, 0.5C2O42-, H2NCH2COO-,
HOCH2COO- etc.) (Srivastava et al 1980, House and Vandenbrook 1989, House and
Vandenbrook 1990, Anagnostopoulos et al 1979, Ravindranathan and Patil 1983 and
 13

Mahesh and Patil 1986) are the usual products of reaction between hydrazine
hydrate and first row transition metal salts.

The tris-hydrazine complexes M(N2H4)3X2(X= 0.5 SO42-, 0.5SO3-,

0.5S2O3-, NO3- etc.) (Anagnostopoulos and Nicholls 1976 and Athavale and
Padmamabha Iyer 1967) have been prepared by the reaction between the transition
metal salts and hydrazine hydrate. The tris-hydrazine metal glycinates and glycolates
M(XCH2COO)2(N2H4)3,(X = NH2- or OH- and M = Mn, Co, Ni, Zn or Cd) have
been prepared (Sivasankar and Govindarajan 1994) by mixing the metal nitrate
hydrates and a mixture of the acid and excess hydrazine hydrate. The copper (II)
complex, however, is particularly difficult to isolate from aqueous solution because
of its ease of reduction. Synthesis of bis(hydrazine) complexes,
[Fe(RNHNH2)2{PPh(OEt)2}4](Albertin et al 2001) was achieved by reacting
bis(nitrile)complex [Fe(CH3CN)2{PPh(OEt)2}4](BPh4)2 with an excess of hydrazine.
Also, with the triethyl phosphate complex [Fe(CH3CN)2{P(OEt)3}4](BPh4)2 as a
precursor, the reaction with NH2NH2 gave the new nitrile-hydrazine
[Fe(NH2NH2)(CH3CN)2{P(OEt)3}3](BPh 4)2 derivative.

1.4.2.3 Reactions of Hydrazinium Salts with Metal Salts

The hydrazinum salts such as N2H6BeF4, N2H6F2, N2H5F, N2H4.2HF,

N2H5Cl, N2H4.HCl, N2H4.2HCl, N2H5Br, N2H6SO4, (N2H5)2SO4, (N2H5)2C2O4,
(N2H5)2H2EDTA, N2H3COON2H5, N2H5NCS etc., react directly with transition
metal salts to form normally hydrazinium(+1) metal complexes (Tedenac et al 1971,
Satpathy and Sahoo 1970, Bukovec and Golic 1976, Kumar et al 1991, Cheng et al
1977, Reiff et al 1977, Witteveen and Reedijk 1973, Witteveen and Reedijk 1974,
Nieuwpoort and Reedijk 1973, Govindarajan et al 1986, Gajapathy et al 1983,
Saravanan et al 1994) or hydrazine adducts of the corresponding metal salts
 14

(Sivasankar and Govindarajan 1994, Patil et al 1983 and Sivasankar and

Govindarajan 1995).
The hydrazinium (+2) metal complexes have also been isolated and
studied (Glavic et al 1975, Slivnik et al 1968, Frlec et al 1980). The hydrazinium
(+1) lanthanide metal sulphate complexes have been prepared by the reaction
between the lanthanide salts and N2H6SO4 and studied systematically (Bukovec and
Miliev 1987 and Govindarajan et al 1986).

1.4.2.4 Reactions of Hydrazine Hydrate and the Acid Mixture with Metal
Salts

Instead of hydrazinium salts, the mixture of hydrazine hydrate and the

acid of the corresponding anion can be added to the metal salt solution which
precipitates the complexes containing bidentate bridging hydrazine, N2H5+ or
N2H62+. This method is suitable when the particular hydrazinium salts cannot be
prepared in the solid form. A report describes the preparation of MX(N2H4)2 (M =
Co, Ni, Zn or Cd ; X = malonate or succinate) complexes by adding a mixture of
hydrazine hydrate and the acids to the metal nitrate hydrates (Sivasankar and
Govindarajan 1994).

The complexes of propionate, M(CH3CH2COO)2(N2H4)2 (M = Mn, Co,

Ni, Zn or Cd) and M1/3Co2/3(CH3CH2COO)2(N2H4)2 (M = Mg, Mn, Ni, Zn or Cd)
have been prepared by this method. The N2H62+ containing complexes like
N2H6SbF5 (Ballard et al 1976), N2H6CrF5.H2O (Bukovec 1974) have been prepared
by adding the mixture of 40 % HF and N2H4.H2O to CrF3 in the aqueous medium.
 15

1.4.2.5 Reactions of Hydrazinium Salt with Metal Salts in the Presence

of Excess Acid

This method is suitable to prepare the complexes in acidic pH, so that

N2H5+ or N2H62+ cation containing complexes can be obtained. For example,
N2H5CuCl3, (N2H5)2CuCl4.2H2O and (N2H5)2Cu3Cl6 complexes (Brown et al 1979)
have been prepared by adding 3M HCl and N2H6Cl2 mixture to the aqueous solution
of CuCl2.2H2O under different conditions. Under this condition of acidic pH the
reduction of Cu(II) is also prevented. The complexes of the type
(N2H5)Ln(SO4)2.H2O (Ln = La, Ce, Pr, Nd, Sm) have been prepared (Govindarajan
et al 1986) by this technique. The N2H6FeF5 has been synthesized from metallic Fe,
HF and aqueous N2H6F2 (Hanzel et al 1977 and Hanzel et al 1974). A number of
N2H62+ containing metal complexes with fluoride anion have been prepared by this
method in which metal fluorides react with a mixture of HF and N2H6F2 in the
aqueous medium (Slivnik 1976, Frlec et al 1981 and Chakravorti and Pandit 1974).
The hydrazinium formato and acetato complexes, (N2H5)2M(XCOO)4, (X = H or
CH3; M= Co, Ni or Zn) have been prepared (Sivasankar 1994 and Sivasankar and
Govindarajan 1995) by the reaction of metal nitrate hydrates with the corresponding
hydrazinium salts and acid mixture.

1.4.2.6 Reactions of Hydrazine Carboxylate Complexes with Acids

Whenever it is not possible to prepare hydrazinium metal complexes with

particular anion, the same can be prepared conveniently by decomposing
hydrazinium metal hydrazine carboxylates with dilute acids of the corresponding
anion. For example, (N2H5)2M(NCS)4.2H2O (M = Co or Ni) complexes have been
prepared (Kumar et al 1991) by adding freshly prepared solid
 16

N2H5M(N2H3COO)3.H2O to dilute thiocyanic acid in small portions while

maintaining the reaction temperature around 0°C. The (N2H5)2MnF4,
(N2H5)2MCl4.2H2O (M = Co or Ni) (Kumar et al 1991) and (N2H5)UO2(CH3COO)3
complexes have been prepared by the same procedure.

In spite of a number of methods described for the preparation of the

complexes, it is not possible to detail all the possibilities as it is still a growing field.
For example, some complexes have been prepared in non-aqueous medium and
(N2H5)2UF6 has been prepared by the reaction between UF6 and N2H5F in anhydrous
hydrazine (Glavic and Slivnik 1970). The lanthanide hydrazine complexes with
anions like halides, carbonate, nitrate, sulphate, perchlorate, acetate, oxalate
(Schmidt 1984) and squarate(Vairam and Govindarajan 2006) have been prepared
by the addition of hydrazine hydrate to the metal salts in an aqueous or alcoholic
medium.

1.5 THERMAL REACTIVITY

Thermal reactivity of the complexes varies from explosion → deflagration

→ decomposition depending upon the anion. Transition metal perchlorate, nitrate
and azide hydrazines are primarily explosives, non-transition metal (Li+, Mg2+, Al3+)
perchlorate, nitrate and azide hydrazines and transition metal oxalate, sulphite and
hydrazine carboxylate hydrazine complexes deflagrate and the rest simply
decompose with the loss of hydrazine. The deflagrating nature of metal hydrazines
has been used in the preparation of ferrites (Gajapathy and Patil 1983) and cobaltites
(Ravindranathan et al 1987). It is rather surprising that thermolysis of
Mg(N3)2(N2H4)2 gave a blue coloured residue which showed a strong IR absorption
at 2100 cm -1 characteristic of molecular nitrogen. The composition of the residue has
been fixed as Mg(NH2)2N2 by chemical analysis and TG studies (Patil et al 1982).
The tris-hydrazine complexes are considerably less stable both thermally and in air
than the corresponding bis- hydrazine complexes. The complexes
 17

M(XCH2COO)2(N2H4)3, (X = NH2- or OH- and M = Mn, Co, Ni, Zn or Cd)

decompose violently above 200 °C in an exothermic single step to form metal
powders (Sivasankar and Govindarajan 1994). Thus, thermal properties of the
complexes differ depending on the composition, the metal ion, and type of the anion,
the coordination mode of hydrazine and the atmosphere used in the experiments.

1.5.1 Thermal Decomposition of Metal Hydrazine Complexes

Thermal decomposition of metal hydrazine complexes with a variety of

anions such as halides, NCS- (Vittal 1981), NO3- and N3- (Patil et al 1982) have been
studied. Depending upon the anion, the decomposition path changes dramatically
(violently) giving mostly metal oxides as the final residue, whereas hydrazine
complexes, M(N2H4)nX2 (Patil et al 1981, Glavic et al 1977, Glavic et al 1979 and
Glavic et al 1980 ), to MX2, MOX2, MO, M2O3 or M. Thermal reactivity of
MFe2(C2O4)3(N2H4)x, (Patil et al 1983), (M = Mg, Co, Ni or Zn and x = 5 or 6 ) and
MFe2(N2H4)5(C2O4)3 (Gajapathy 1982) has been reported and these complexes
decompose at low temperature to give ferrites as the final product. Preparation and
thermal reactivity of MgC2O4(N2H4)2 (Patil et al 1982) have also been reported.

Thermal decomposition of metal carboxylate hydrazines are more

interesting due to their easier combustibility. For example, metal hydrazine formate
(Ravidranathan and Patil 1983), acetate (Mahesh and Patil 1986), propionate,
chloroacetate, glycinate and glycolate (Sivasankar 1994), oxalate (Patil et al 1982),
malonate and succinate (Sivasankar and Govindarajan 1994), benzoate, salicylate
(Kuppusamy 1995), trimellitate(Vairam et al 2010) and pyromellitate(Vairam et al
2010a) complexes have been studied by simultaneous DTA-TG-DTG
thermoanalytical method. These complexes have been reported to decompose at
lower temperatures than their non-carboxylate counterparts. Moreover, the oxalate
complexes exhibit autocatalytic decomposition. This behaviour has been attributed
to the simultaneous exothermic decomposition of hydrazine and metal salt (Patil et
 18

al 1982). This phenomenon has been made use of in the preparation of fine particle
ferrites (Gajapathy and Patil 1983) and cobaltites (Patil et al 1983) by the low
temperature decomposition of M1/3Fe2/3(C2O4)(N2H4)2 (M = Mg, Mn, Co, Ni or Zn)
and M1/3Co2/3(C2O4)(N2H4)2 (M = Mg or Ni), respectively. Large surface area CeO2
has been prepared by the thermal decomposition of cerium oxalate hydrazine
complex. The thermal behaviour of metal maleate and fumarate hydrazine
complexes have also been reported (Govindarajan et al 1995). The decomposition of
nickel hydrazine glycinate complexes (Sivasankar 1994) have been reported to be
violently exothermic and lead to explosion if the samples are heated in bulk. They
give metal powder as the final product, even in air, unusually. Metal (Co, Ni and Zn)
hydrazine phthalate complexes produce metal powder and benzoate, isophthalate
and terephthalate complexes, the oxides as residue (Kuppusamy 1995).
Metal hydrazine carboxylates decompose in air at a low temperature (75-
200°C) to yield fine particle oxide materials. Thermal studies on
M(N2H3COO)2.nH2O, (M = Ca, Mg, Mn, Fe, Co, Ni, Zn or Cu; n = 0, 0.5, 1, 2, 3)
are carried out extensively in air or inert atmosphere (Ravidranathan and Patil 1985,
Macek and Rahten 1989, Macek and Rahten 1993, Braibanti et al 1967, Manoharan
and Patil 1989). The thermal property of Nd(N2H3COO)3.3H2O in an inert
atmosphere, (Macek and Rahten 1989, Macek and Rahten 1993) the synthesis of
La(N2H3COO)3.2H2O and, thermal reactivity of Ln(N2H3COO)3.3H2O,(Ln = Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb or Y) and UO2(N2H3COO)2N2H4.H2O
(Mahesh et al 1986) have been reported already. The decomposition is autocatalytic
and accompanied by swelling due to the evolution of large amounts of gases like
NH3, H2O, H2 and CO2. The preparation of γ-Fe2O3 and Co doped γ-Fe2O3 the
commonly used recording material has been achieved by the thermal decomposition
of iron hydrazine carboxylates in a single step. Similarly ultra fine ferrites and fine
particle cobaltites have been obtained at very low temperatures by the thermal
decomposition/combustion, of solid solution precursors (Ravindranathan and Patil
1987, Arunadevi et al 2009).
 19

The thermal decomposition of metal sulphite hydrazine hydrates

(Budkuley 1987) has been reported. The decomposition of mixed metal sulphite
hydrazine occurs at low temperature due to high exothermicity of hydrazine
decomposition in the complex. Iron is also known to catalyze the decomposition of
hydrazine (Patil 1986). Hence these compounds undergo auto combustion once
ignited. The thermal decomposition behavior of metal hydrazine sulphate was
reported for the first time (Sivasankar and Govindarajan 1994). The thermal
decomposition of the metal hydrazine phenyl acetate complexes have been reported
(Jiji and Aravindakshan 1993).

1.5.2 Thermal Decomposition of N2H5+ and N2H62+ Metal Complexes

The simultaneous TG-DTA studies of (N2H5)2M(SO4)2 ( M= Mn or Co)

have been reported (Banerjee et al 1981). The complexes decompose exothermally
at 275°C to MSO4 via an intermediate compound, M(N2H4)0.5HSO4(SO4)0.5. The
thermal decomposition of (N2H5)2Mg(SO4)2, (N2H5)2M(SO4)2 and
(N2H5)2M(SO4)2(N2H4)3 has been studied thoroughly (Patil et al 1981). The thermal
properties of hydrazinium aluminium sulphate have been studied (Govindarajan and
Patil 1982). Govindarajan et al, 1986 reported the thermal reactivity by TG -DTA
methods of hydrazinium lanthanide sulphate hydrates, (N2H5)Ln(SO4)2.H2O.
Thermal and structural studies on hydrazinium metal chlorides dihydrates were
reported (Kumar et al 1991) and these complexes were found to yield metal oxide as
the final residue via metal chloride. But the iron complex form FeO and the copper
complex, Cu2O instead of the usual products Fe2O3 and CuO respectively.

Slivink et al, 1968 and others have studied the thermal decomposition of
N2H5+ and N2H62+ fluorometallates of transition metals (Frlec et al 1980, Frlec et al
1981, Slivnik et al 1966, Siftar and Bukovec 1970 and Bukovec et al 1971). The
intermediate products of thermal decomposition are either hydrazinium(+1)
fluorometallates, which further decompose to ammonium fluorometallates or
 20

adducts of metal fluorides and hydrazine. It is observed that the formation of

ammonium fluorometallates is highly exothermic. In all the cases, the final products
of decomposition are metal fluorides, except in the case of copper complex, which
forms the metal as the end product.

Thermal behaviour of hydrazinium (+2) hexafluorogermenate has been

studied (Gantar et al 1985). The thermal decomposition of some methyl hydrazine
and methyl hydrazinium complexes of copper (II), copper (I) and mixed valence
species has been studied by Dowling and Class, 1988.

The simultaneous DTA-TG-DTG studies of hydrazinium metal formate

hydrates of the formula, (N2H5)2M(HCOO)4.H2O, (M = Co, Ni or Zn) have been
prepared (Sivasankar and Govindarajan 1995). The Co and Zn complexes form
metal oxides and Ni complex forms metal as the final product of decomposition.
Thermal behaviour of (N2H5)2M(CH3COO)4 (M = Co, Ni or Zn) has been reported
(Sivasankar 1994). These complexes decompose at a lower temperature than the
corresponding metal carboxylate hydrazine complexes. They have also studied the
thermal behaviour of hydrazinium metal glycinates, malonate and mixed metal
malonate dihydrates (M = Co, Ni or Zn). Glycinate complexes gave metal and the
malonate complexes gave metal oxides as the final products of decomposition.

The thermal behaviour of (N2H5)2M(C2O4)2.nH2O (M = Co, Ni or Cu and

n = 3, 2 and 1 respectively) have been studied (Gajapathy et al 1983). Copper
compound after melting undergoes exothermic decomposition whereas Co and Ni
complexes decompose endothermally.

Thermal studies of hydrazinium (+1) metal hydrazinecarboxylate

hydrates, (N2H5)M(N2H3COO)3.H2O have been reported by a number of authors, at
different periods, at different atmospheres viz., air, nitrogen or argon. Premkumar,
2002 who carried out the analysis in air and nitrogen atmosphere have reported the
 21

formation of the metal oxides as the final products of decomposition. However, the
authors (Macek and Rahten 1989 and Macek and Rahten 1993) who experimented
the thermal decomposition in argon atmosphere for Fe, Co and Ni complexes have
reported the metal powders as the end products, which are very reactive and
sensitive to oxidation by the impurities in the argon. All of them decompose
exothermally.

1.6 INFRARED SPECTRA OF HYDRAZINE, ITS SALTS AND

COMPLEXES

One of the best features of an infrared spectrum is that the absorption or

the lack of absorption in specific frequency regions can be correlated with specific
stretching and bending motions and in some cases, with the relationship of these
groups to the remainder of the molecule. IR spectra of hydrazine and its derivatives
are studied in the finger print region between 1300 cm-1 and 650 cm-1. They have
been reported for several hydrazine derivatives (Savoie and Guay 1975, Glavic and
Hadzi 1972) and metal complexes (Nieuwpoort and Reedijik 1973, Brown et al
1979, Braibanti et al 1968). Normal coordinate analysis for N2H2, N2H4, N2H5+,
N2H62+ has been carried out (Mielke and Ratajczak 1973).

Of special interest in the vibrational assignment of hydrazine is N-N

stretching frequency, since the presence of this frequency, has been used as a
criterion for determining the mode of bonding of hydrazine to metal ions as well as
to distinguish it from N2H5+ and N2H62+ ions.

Braibanti et al, 1968 have given a thumb rule on the basis of earlier
studies. In the complexes examined by them and others, νN-N could be found at the
following frequency ranges:
 22

N2H4 (in solid state) 875 cm -1

N2H4 (unidendate) 930-940 cm -1
N2H4 ( bridging ) 948 - 985 cm-1

NH2NHY (Y = COO, CSS) 986-1012 cm-1

N2H5+ cation (non-coordinated) 960 - 970 cm-1
N2H5+ cation (coordinated) 990 - 1015 cm -1
N2H62+ cation 1020-1045 cm -1

Hydrazine as a unidentate ligand (Schmidt 1984), also shows N-N

stretching at higher wave numbers, for example, 956 cm -1 in Мe3В.N2H4,
952 cm -1 in [Hg(N2H4)2]Cl2 or 950 cm -1 in SiF4(N2H4)2.

Although the N-N stretchings for free N2H5+ and bridging N2H4 overlap,
fixing the molecular formulae can identify them by analytical and other techniques.

The assignment of the band at 875 cm -1 in the spectrum of hydrazine to

νN-N was questioned by Durig et al (Durig et al 1966), who assigned this band to -
NH2 rocking vibration and the band at 1126 cm-1 to νN-N. The infrared spectra of
M(N2H4)2Cl2 (M = Mn, Fe, Co, Ni or Zn) complexes were recorded (Satyanarayana
and Nicholis 1978 ) and the absorption in the region 1150 -1170 cm -1 were assigned
to νN-N of bridged hydrazine. Despite these reservations, the frequency of νN-N is a
useful indication of the type of coordinated hydrazine.
 23

1.7 STRUCTURAL STUDIES OF HYDRAZINE COMPOUNDS

1.7.1 Structure and Bonding in Hydrazine

Infrared, Raman, microwave, NMR, photoelectron spectra and

X-ray diffraction have been used to elucidate the structure and bonding of hydrazine
(Shvo 1975 and Durig et al 1975). The high values of the melting point, boiling
point and Trouton's constant of hydrazine indicate that it is extensively associated
through an intermolecular H - bonding in the condensed phase, but monomeric in
the gas phase. Electron diffraction data give N-N-H angle as 112° and N-N bond
length as 1.45- 1.47 A° suggesting sp 3 hybridisation for the nitrogen atoms. Thus the
two nitrogen atoms are joined by a σ-bond, rotation around which can give rise to
one of the conformational isomers illustrated in Figure 1.1.

Figure 1.1 The possible isomers of hydrazine (a) Staggered trans C2h
(b) Eclipsed cis C2v (c) Semi-eclipsed half cis C2 (d) Gauche C

The high value of dipole moment (Verstakov et al 1978) for hydrazine

(1.83 -1.84 D) eliminates the trans (C2h) formation and the gauche form is
 24

considered to be the equilibrium conformation as both the eclipsed and the semi-
eclipsed conformations would involve coplanar repulsions.

Electronic, infrared, Raman and microwave spectra show that the

molecule has C2 symmetry in the vapour and liquid states (Durig et al 1975).
However, X-ray and neutron diffraction investigations in the solid state show that
the molecule to have either the gauche (C2) or cis (C2V) conformation.

1.7.2 Simple Hydrazine Compounds

Two types of simple hydrazine compounds have been reported:

(i) Simple molecular compounds of hydrazine of the formula,

N2H4.nROH, where R = H, CH3 or C2H5, and n = 1 for H, 2 or 4 for
CH3 and 2 for C2H5.

(ii) Salts of hydrazine with HCl, HF, HBr, H2SO4, HCIO4, H3PO4,
H2C2O4.2H2O, CH3COOH, 2, 3 pyrazinedicarboxylic acid, 3, 5-
pyrazoledicarboxylic acid etc.

Extensive work has been done by Liminga and his coworkers (Liminga
and Olovsson 1964, Liminga and Alex Mehlsen 1969 and Liminga 1967). The
crystal structure of N2H5+C4H5O6- consists of infinite chain of tartrate anions linked
by head to tail by O – H…O hydrogen bonds. Two such chains are cross-connected
by O – H....O hydrogen bonds to form dimeric chains. The hydrazinium cation sits at
the center of four tartrate dimers and bridges them by two center and three center N -
H....O hydrogen bonds. As a whole, the structure is stabilized by numerous hydrogen
bonds.
 25

1.7.3 Complexes Containing Hydrazine as a Unidentate Ligand

The crystal structure of the Zn(N2H3COO)2(N2H4)2 and

Co(N2H3COO)2(N2H4)2 are found to consist of chelates of the type as shown in
Figure 1.2.

NH2

NH2 H
O

C NH2 N
O
M

O C
N NH2
NH2 O
H

NH2

Figure 1.2 Structure of M(N2H 3COO)2(N2H4)2, where M= Co or Zn

The hydrazine molecule, which acts as a unidentate ligand and the

hydrazinecarboxylate anion, which acts as a bidentate ligand, are both coordinated in
the trans position. The coordination around the metal is octahedral. Manganese and
nickel form complexes isomorphous with zinc and cobalt analogues
(Ravindranathan and Patil 1985).

1.7.4 Complexes Containing Hydrazine as a Bidentate Bridging Ligand

Many stable complexes of metal salts with one, two or three hydrazine
molecules are known, but their structures have so far received very little attention.
 26

The only available crystal structures are on the complexes M(N2H4)2X2 (Ferrari et al
1963 and Ferrari et al 1965) (M= Mn, Co, Ni, Zn or Cd and X= Cl- (Ferrari et al
1963), NCS- (Ferrari et al 1965) and CH3COO- (Ferrari et al 1965). The above
complexes have infinite chain structures (Figure 1.3) with cis bridging hydrazine
molecules and respective anions in the trans positions.

X X
NH2
NH2 NH2 NH2

M M

NH2 NH2 NH2 NH2

X X

Figure 1.3 Structure of [M(N2H4)2X2]n where M= Mn, Co, Ni, Zn and Cd; X=
Cl-, NCS– and CH3COO–

It has been pointed out that chains of complexes are not held together by
hydrogen bonds, thus favouring twinning which is observed in the crystals.

Infrared (Sivasankar and Govindarajan 1994 and Braibanti et al 1968) and

preliminary X-ray investigation of the complexes [M(N2H4)3]X2 (X= NO3-,
H2NCH2COO-, HOCH2COO- and M = Mn, Fe, Co, Ni, Zn or Cd) appear to suggest
a structure with three bridging hydrazine molecules linking metal ions which have
an octahedral coordination. Recently, crystal structure of
[Ni6(N2H4)6(SO4)4(OH)2(H2O)8](SO4)(H2O)10 has been determined. The structure of
the complex is shown in Figure 1.4
 27

Figure 1.4 Structure of [Ni6(N2H4)6(SO4)4(OH)2(H 2O)8](SO 4)(H2O)10

The complex cation in the compound has a remarkable structure with

unusual diversity of bridging groups including hydrazine molecules, sulphate ions
and hydroxo group (Gustafsson et al 2010).

1.7.5 Complexes with Bidentate Chelating (η2) Hydrazine

The present crystallographically characterized complexes containing

η2N2H4 are, [W(NAr)(N(NTs)2)Cl(η2 - N2H4)] (Cai and Schrock 1991) where Ar =
2,6-C6H3Pr2, N(NTs)2 = 2,6 –N(C5H3) (CH2Ts)2, [Cp*WMe3(η2-N2H4)]+(Schrock et
al 1993), [Co(tripod)(η2-N2H4)]2+ (tripod = MeC(CH2PPh 2)3 and [Cp2*Sm(THF)(η2
-N2H4)]+ (Heaton et al 1996). As an example the structure of [Co(tripod)( η2-
N2H4)]2+ is given in Fig 1.5.

2+

CH3

P
C

P NH2

Co

P NH2

Figure 1.5 Structure of [Co(tripod)(η2 -N2H4)]2+

 28

1.7.6 Compounds Containing N2H 5+ as a Ligand

The crystal structure of iron complex, (N2H5)2FeCl4.2H2O has been

studied (Kumar et al 1991). The complex consists of chloride ions and complex
cation [Fe(N2H5)2(H2O)2Cl2]2+. The metal coordinated site in the molecule is a
distorted octahedron made up of two nitrogen atoms (one from each N2H5+ ion), two
oxygen atoms(from water molecule) and two chlorine atoms. The complex is found
to be isomorphous with the corresponding Co, Ni and Cu analogues.

The crystal structure of (N2H5)Nd(SO4)2.H2O has also been reported

(Govindarajan et al 1986). Recently, crystal structure of {(N2H5)[Li3(C6H2-
N2O4)2(H2O)2].H2O}n has been reported(Starosta and Leciejewicz 2012). The
structure is composed of molecular dimmers, each built up of two symmetry –related
LiI ions with distorted trigonal - bipyramidal coordinations bridged by two
deprotonated ligand molecules. The layers are held together by hydrogen bonds in
which the hydrazinium cations coordinated and crystal water molecules act as
donors and carboxylate O atoms acts as acceptors.

The crystal structure of the complex (N2H5)2Co(NCS)4.2H2O has been

studied (Kumar et al 1991). The crystal structure consists of discrete
(N2H5)2Co(NCS)4 and H2O molecules. The cobalt ion is six coordinated by two
hydrazinium and four thiocyanate ions. All the four thiocyanate groups are terminal
N bonded. The structure of [Co(N2H5)2(NCS)4] is illustrated in Figure 1.6. The
nickel complex is iso-structural with the cobalt complex.
 29

+
NH3
S
S

C NH2
C

N N
Co
N N

C NH2 C

S NH3 S
+

Figure 1.6 Structure of [Co(N2H 5)2(NCS)4]

The structure of the complex, (N2H5)2PtCl4.2H2O has been determined by

a single crystal X-ray crystallography (Kumar et al 1991). This consists of
[Pt(N2H5)2Cl2]2+ cations and water molecules. The platinum ion has a square planar
coordination, bonded by two chlorine atoms and two nitrogen atoms from the N2H5+
ions through trans positions.

Sivasankar and Govindarajan (Sivasankar and Govindarajan 1995 and

Sivasankar 1994) have proposed an octahedral structure for [(N2H5)2MX4] (M = Co,
Ni or Zn and X = HCOO-, CH3COO- and H2NCH2COO- and
(N2H5)2M(OOCCH2COO)2.2H2O, (M = Co, Ni, Zn or Cd) on the basis of IR and
electronic spectra, magnetic and thermal studies.

Recently crystal structures of [Cr(N2H5)2(SO4)2](Parkins et al 2001),

[Cd(N2H5)2(SO4)2](Srinivasan et al 2006) and [Mn(N2H5)2(SO4)2](Srinivasan et al
2007) have been determined.
 30

1.7.7 Compounds Containing Non-coordinated N2H 5+ Ion

Though N2H5+ ion is a potential coordinating group, in some compounds

it behaves like the ammonium ion, i.e. it is outside the coordination sphere. The
compounds with halides and hydrazinecarboxylate anions fall under this category.

In the halide group the crystal structures of (N2H5)3CrF6 (Kojic-Prodic et

al 1972), N2H5InF4.H2O (Bukovec and Golic 1976), N2H5LiBeF4 (Anderson et al
1973) and N2H5BeF3 (Anderson et al 1973a) have been determined. In these
compounds N2H5+ ion is not coordinated to the metal ion. In N2H5LiSO4 also, N2H5+
is not coordinated (Anderson and Brown 1974)

In the case of hydrazinium metal hydrazinecarboxylate

hydrates, the crystal structure of N2H5[Ni(N2H3COO)3].H2O(Braibanti et al 1967)
has been investigated. It has N2H5+ cation, complex anion and water molecules. In
the complex anion, the nickel(II) is octahedrally coordinated by three bidentate
hydrazine carboxylate anions. The crystals of the nickel compound,
(N2H5)[Ni(N2H3COO)3].H2O are piezoelectric. The corresponding cobalt and zinc
compounds are isomorphous with the nickel compound (Jesih et al 2004). A novel
coordination mode for hydrazine carboxylate in a polymeric, ten-coordinate barium
complex has been established crystallographically (Edwards et al 1993).
The crystal structure of N2H5[Cu(C2O4)2].H2O (Gajapathy et al 1983) has
revealed that the molecule contains discrete N2H5+ ions, [Cu(C2O4)2]2- ions and
water molecules. It is shown in Figure 1.7. The same authors have reported the non-
coordination of N2H5+ in (N2H5)2Co(C2O4)2.3H2O.
 31

2-

O O

C O O C

Cu

C O O C

O O

Figure 1.7 Structure of [Cu(C2O4)2] 2- anion

Recently the crystal structure of (N2H5)2[Ln(pyzCOO)5].2H2O where Ln =

La, Ce & (pyzCOO) = 2-pyrazine carboxylic acid and
(N2H5)3[Ln(pyzCOO)4(H2O)].2NO3 where Ln = Pr, Nd, Sm and Dy have been
synthesized(Premkumar et al 2009). The crystal structure consists of N2H5+ cations,
La(pyzCOO)2- anions and water molecules. In these crystals, there are independent
N2H5+ ions present in asymmetric unit and are not coordinated to the metal ion.

The crystal structure of (N2H5)[Nd(C2O4)2(H2O)].4H2O and

(N2H5)[Gd(C2O4)2(H2O)].4.5H2O have been synthesized(Arab et al 2005). The Nd
atom is surrounded by nine oxygen atoms in which eight from four bidentate oxalate
ions and one from aqua ligand. The coordination polyhedron around Nd(III) metal
ion can be described as tri-capped trigonal prism.

1.7.8 Compounds Containing N2H 62+ Cation

In this class of compounds N2H62+ ion exists as a cation to compensate the

negative charges of the anionic complexes. Most of the compounds are known with
fluoride anion and the crystal structures of (N2H6)[TiF6] (Kojic-Prodic et al 1971),
N2H6SiF6 (Frlec et al 1980), N2H6[GeF6].H2O (Frlec et al 1981), N2H6[ZrF6] (Kojic-
Prodic et al 1971), (N2H6)2[TiF6]F2 (Golic et al 1980), N2H6[SnF3]2(Kaucic et al
 32

1988), (N2H6)3[Zr2F13].F (Rahten et al 1990), N2H6[GaF5(H2O)](Meden et al 1996),

(N2H6)[Ca(C7H2O6)2(H2O)2](Yasodha et al 2007)have been investigated.

1.7.9 Compounds Containing N2H 5+ and N2H 62+ Cations

In this class of compounds two types of cations coexist in the atomic

arrangement (hydrazinium(+1) ion, NH2-NH3+ and hydrazinium(+2) ion, NH3+-
NH3+). The crystal structure of (N2H5)2(N2H6)2P6O18 (Pouchot and Durif 1991) has
been reported.

1.8 SCOPE AND OBJECTIVE

The literature survey detailed so far illustrate the interaction of hydrazine

hydrate with inorganic, aliphatic and aromatic carboxylic acids and metal ions
leading to the formation of compounds with a variety of structures. With the view to
understand the structure of metal complexes with carboxylic acids and functional
group containing sulphur this work was undertaken. Moreover there is no report on
sulphur containing carboxylic acids in the hydrazine system. In this work a
systematic study has been carried out to find the results of interaction of hydrazine
hydrate with the acids like thioglycolic, thiomalic, thiobenzoic and 5-sulphosalicylic
acids in the presence of divalent metal ions like, Co2+, Ni2+, Zn2+, Cd2+, Cu2+, Hg2+
and Pb2+ and inner transition metal ions like, La3+, Pr3+, Nd3+, Sm 3+ and Gd3+ are
reported. An attempt has also been made to use these complexes as precursors to
prepare nano metal oxides. Single crystals are prepared using 5-sulphosalicylic acid
with hydrazine and the structure has been found for the first time.

For clarity the structure of acids and the different coordination modes of
hydrazine are shown in Figure 1.8(a-d) and 1.9(a-c) respectively.
 33

SH-CHCOOH
SHCH2COOH COSH
CH 2 COOH

(a) Thioglycolic acid (b) Thiomalic acid (c) Thiobenzoic acid

HO

O
HO
S
OH
O O

(d) 5-Sulphosalicylic acid

Figure 1.8(a-d) Structure of the acids

(a)Monodentate hydrazine (b)Bidentate hydrazine (c)Monodentate hydrazinium

cation

Figure 1.9(a-c) Structure of hydrazine

 34

The main objectives of the present work are:

 To prepare hydrazinium salts of thioglycolic, thiomalic, thiobenzoic and

sulphosalicylic acids and characterize them by analytical, IR spectroscopic,
thermal analysis and single crystal XRD analysis

 To prepare metal hydrazine complexes of thioglycolic, thiomalic,

thiobenzoic and 5 – sulphosalicylic acids by the reaction of hydrazine hydrate
with metal nitrate hydrates, and characterize them by different physico-chemical
techniques

 To correlate structure and thermal reactivity relationship among the

complexes

 Hydrazine complexes are found to yield metal oxides at low temperatures

in the nano scale, hence it was aimed to use the complexes to prepare nano metal
oxides using them as precursors

 To find the conductivity of the complexes in their solid state

 To study the isomorphism among the complexes using powder X-ray

diffraction technique

 To evaluate the kinetic parameters of dehydration and dehydrazination

/decarboxylation of all the complexes and hydrazinium salts

Based on the above objectives, this research work was performed and
the results obtained are discussed in the following chapters.