Crystal structures, thermal degradation, and biological activities of some new ammonium and hydrazinium salts of cyclohexanediaminetetraacetic acid

Article abstract of DOI:10.1080/15533174.2013.799195

Neutralization reaction in aqueous medium between cyclohexanediaminetetraacetic acid (H4CDTA) and weak bases such as hydrazine hydrate and aqueous ammonia yielded a series of new salts such as N ₂H5H₃CDTA.H₂O, (N₂H5) ₃HCDTA.H₂O, NH4H₃CDTA.2H₂O, and N₂H5NH4H₂CDTA.H₂O. The type of salt formed depends on the ratio of H4CDTA to base used and the pH of the medium. The compositions of the previous compounds were determined by hydrazine and microanalyses. The infrared spectra of the salts reveal the presence of free carboxylic acid groups. The X-ray single-crystal structures of N ₂H5H₃CDTA and NH4H₃CDTA clearly reveal that these salts exist as zwitterions in solid state. The simultaneous TG-DTA profiles show the multistep degradation with almost 100% mass loss indicating the complete decomposition. The biological screening of the aqueous solution of these salts reflects the enhanced activities of the hydrazinium salts than the free acid and the ammonium salts.

Full text of DOI:10.1080/15533174.2013.799195

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Crystal Structures, Thermal Degradation, and Biological
Activities of Some New Ammonium and Hydrazinium
Salts of Cyclohexanediaminetetraacetic Acid
C. Sonia a & B. N. Sivasankar a
a Department of Chemistry , Government Arts College, Udhagamandalam , The Nilgiris ,
Tamilnadu , India
Accepted author version posted online: 17 Dec 2013.Published online: 26 Mar 2014.
To cite this article: C. Sonia & B. N. Sivasankar (2014) Crystal Structures, Thermal Degradation, and Biological Activities of
Some New Ammonium and Hydrazinium Salts of Cyclohexanediaminetetraacetic Acid, Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry, 44:8, 1119-1127, DOI: 10.1080/15533174.2013.799195
To link to this article: http://dx.doi.org/10.1080/15533174.2013.799195
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:1119–1127, 2014
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.799195
Crystal Structures, Thermal Degradation, and Biological
Activities of Some New Ammonium and Hydrazinium Salts
of Cyclohexanediaminetetraacetic Acid
C. Sonia and B. N. Sivasankar
Department of Chemistry, Government Arts College, Udhagamandalam, The Nilgiris, Tamilnadu, India
were prepared and well characterized with H4CDTA, the corre-
sponding ammonium and hydrazinium complexes have not been
reported in the literature.[11,12] The interest in these complexes
lies in the fact that, these complexes obtained at particular pH
conditions could yield complexes with desired number of coor-
dinated water molecules. Hence, one can control the water of
hydration, which makes these complexes as a possible potential
precursor for hydroxy and hydrazine bridged poly nuclear clus-
ter which in turn can be utilized for the hydrolysis of DNA and
RNA.[13] As the initiation of the previous investigations some
new ligands, the hydrazinium and ammonium salts of H4CDTA,
which can be used for the preparation of complexes, have been
prepared and characterized by analytical, spectral, thermal, X-
ray single-crystal, and biological studies. The results of these
studies are presented in this article.
Neutralization reaction in aqueous medium between cyclo-
hexanediaminetetraacetic acid (H4CDTA) and weak bases such
as hydrazine hydrate and aqueous ammonia yielded a series
of new salts such as N2H5H3CDTA.H2O, (N2H5)3HCDTA.H2O,
NH4H3CDTA.2H2O, and N2H5NH4H2CDTA.H2O. The type of salt
formed depends on the ratio of H4CDTA to base used and the pH of
the medium. The compositions of the previous compounds were de-
termined by hydrazine and microanalyses. The infrared spectra of
the salts reveal the presence of free carboxylic acid groups. The X-
ray single-crystal structures of N2H5H3CDTA and NH4H3CDTA
clearly reveal that these salts exist as zwitterions in solid state.
The simultaneous TG-DTA profiles show the multistep degrada-
tion with almost 100% mass loss indicating the complete decom-
position. The biological screening of the aqueous solution of these
salts reflects the enhanced activities of the hydrazinium salts than
the free acid and the ammonium salts.
Keywords antibacterial and antifungal activities, H4CDTA, hy-
drazinium and ammonium salts, monoclinic, thermal
degradation, X-ray crystal structure
EXPERIMENTAL
The chemicals used were of AR grade. The solvents were
distilled before use and double distilled water was used for the
preparation and analyses. Hydrazine hydrate (99–100%) was
used as received.
INTRODUCTION
Aminopolycarboxylic acids are effective chelating agents
and forms stable complexes with transition metal ions and
lanthanide ions.[1,2] These simple and bridged binuclear and
poly nuclear complexes are known for their optical, mag-
netic, and biological applications in many areas of recent in-
terest.[3–7] Among the aminopolycarboxylic acids, iminodiacetic
acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminediacetic
acid (EDDA), and ethylenediaminetraacetic acid (EDTA) have
been widely used as a multidentate ligands during the synthe-
ses and structural investigation of simple salts, simple metal
complexes and their sodium, potassium, ammonium and hy-
drazinium derivatives.[1,2,8–10] Though few simple complexes
The hydrazine content in the salts was determined by vol-
umetric analysis under Andrew’s conditions using 0.025 M
KIO3.[14] The C, H, and N analyses were performed on a Perkin-
Elmer (model 1240) CHN analyzer. The infrared spectra of the
solid samples in the range 4000–500 cm−1 were recorded on
a Perkin-Elmer 597/1650 spectrophotometer using KBr pellets
of the samples. Simultaneous TG-DTA experiments in air were
carried out using a STA 1500 thermal analyzer using 8–10 mg
of the samples with the heating rate of 10◦C per minute and the
platinum cups as sample holders.
X-Ray Structure Determination
The X-ray intensity data was collected on a Kappa-Apex
II CCD diffractometer with graphite monochromated M-Kα
radiation (λ = 0.71073 Å). The structures were solved by direct
methods using SIR92 program and completed using Fourier
techniques. Refinement was carried out using SHELXL-97
program.[15,16] All the hydrogen atoms can be located in
different Fourier map. The C H distance in methylene (CH2)
Received 15 March 2013; accepted 17 April 2013.
Address correspondence to B. N. Sivasankar, Department of
Chemistry, Government Arts College, Udhagamandalam, The Nilgiris
643002, Tamilnadu, India. E-mail: sivabickol@yahoo.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
1119

1120
C. SONIA AND B. N. SIVASANKAR
in the experiment was the following: (a) NaCl = 6 g, (b) pep-
tone = 10 g, (c) beef extract = 3 g, (d) yeast extract = 2 g,
(e) sucrose = 1.5 g, (f) agar-agar = 3%, and (g) distilled water
= 1 L. The zones of inhibition around the discs were mea-
sured after 24 h. Ciprofloxacin was used as a standard positive
control.
and ring (CH2) were constrained to 0.97 Å. The O-H distances
in water molecules were constrained as 0.900(0.001) Å with
H O H angle restrained to be near tetrahedral. The N-H
distances of hydrazinium cations were restrained to be 0.89Å
for NH3 moiety, 0.85 Å for NH2 moiety, and 0.84 Å for
NH4+ moiety. The packing is stabilized through intermolecular
hydrogen bonding interactions.
RESULTS AND DISCUSSION
Preparation of Salts
The hydrazinium, ammonium or hydrazinium-ammonium
salts of cyclohexanediaminetetraacetic acid were obtained by
acid-base neutralization reaction between the acid and respec-
tive bases in required ratios. It was observed that excess of base
than required for the formation of the respective salts should
be added for the isolation of the salts. The replacement of the
acidic protons could be possible only with the addition of excess
amount of bases. The reaction with 1:1 acid to base ratio always
resulted in the partial dissolution of acid.
The pKa value of the protons in H4CDTA is obviously known
to be a vital factor during their replacement by bases. In the
present case, weak bases such as hydrazine and ammonia are
expected to replace only two protons with lower pKa values,
2.4 and 3.5. Further replacement of other two protons with
pKa values 6.1 and 12.4 was not successful and always yielded
viscous solutions. The chemical reactions for the formation of
salts are represented as follows:
An aqueous suspension (50 mL) of H4CDTA.H2O (18.2 g,
0.05 mol) was neutralized with an aqueous solution (20 mL)
of the respective bases such as hydrazine hydrate, aqueous am-
monia, or the mixture of two in appropriate ratio. During the
addition of base, the acid slowly dissolved and after the com-
plete addition the resulting solutions were slightly heated on
a water bath for the completion of the reaction. The solutions
thus obtained were filtered and evaporated on the water bath to
one third of their original volumes. The concentrated solutions
were then kept at room temperature for crystallization. After a
week time the colorless crystals formed were removed, washed
quickly with ice cold water and dried in air.
Biological Screening
Six pathogenic micro-organisms such as Escherichia coli,
Pseudomonas aeruginosa, Staphylococcus aureus, Bacillus
subtilis, Aspergillus niger, and Candida albicans were used
to test the biological potential of the newly synthesized hy-
drazinium and ammonium salts. These were obtained from the
stock cultures of the Microbiology Laboratory of Ramakrishna
Hospital, Coimbatore, India.
H4CDTA.H2O + 2N2H4.H2O → N2H5H3CDTA.H2O
+ N2H4.H2O + H2O
H4CDTA.H2O + 4N2H4.H2O → (N2H5)3H2CDTA.H2O
+ N2H4.H2O + 3H2O
Activity Testing
H4CDTA.H2O + 2NH3.H2O → NH4H3CDTA.2H2O
+ NH3.H2O
The anti-bacterial activities of all the salts were studied by the
usual cup-plate-agar-diffusion method. The compounds were
screened for their anti-bacterial activity against Gram-positive
and Gram-negative microorganism. The method comprises the
following steps:
2H4CDTA.H2O + 3N2H4.H2O
1. Preparation of media, sterilization, and tubing;
2. Sterilization of the cleaved glass apparatus;
3. Pouring of the seeded medium into sterilized Petri dishes and
cutting of the cups;
4. Pouring of the dilute solution of the compounds into the
tubes;
5. Incubation at a particular temperature; and
6. Determination of zone of inhibition.
The composition of test media is the factor, which often ex-
erts a great effect on the drug activity. This is particularly true
for these salts, since the inhibitors of these compounds appear
to be present in the common bacteriological culture medium.
Efficient media of known chemical composition are available
for many species such as S. aureus and E. coli. In addition to
the composition of the test media, its pH also directly or indi-
rectly influences the activity. The pHs of the media taken are
adjusted to 7.6 0.1. The composition of the test media used
FIG. 1. TG-DTA of N2H5H3CDTA.H2O.

SOME NEW AMMONIUM AND HYDRAZINIUM SALTS
1121
FIG. 2. TG-DTA of NH4H3CDTA.2H2O.
H N+ of zwitterions and O H stretching of water and free
carboxylic acid groups. The carbonyl stretching of free car-
boxylic acid groups are observed at 1700 cm−1. The νasy and
νsym stretchings of carboxylate ions are seen in the regions of
1600–1610 cm−1 and 1380–1390 cm−1, respectively. The char-
acteristic N-N stretching of N2H5+ ion is observed at 960 cm−1
for hydrazinium salt while this band is absent in the ammonium
salt.[17]
+ 3NH3.H2O → N2H5NH4H2CDTA.H2O
+ 2N2H4.H2O + 2NH3.H2O + 2H2O
The excess of hydrazine and ammonia present in the reaction
mixture are usually evolved during the evaporation for concen-
tration. The mono hydrazinium and mono ammonium salts were
prepared in the form of single crystals suitable for X-ray single-
crystal study. All the salts derived were highly crystalline and
water soluble. The compositions of the salts were assigned on
the basis of hydrazine analysis and microanalysis. The analytical
data of the salts are summarized in Table 1.
Thermal Degradation Studies
Monohydrazinium salt undergoes dehydration in the tem-
perature range 80–100◦C followed by the loss of hydrazine
Infrared Spectra
The infrared spectra of the hydrated salts show broad band molecule in the range 150–200◦C. The free acid thus formed as
in the region 3250–3400 cm−1 with several microsplittings, the intermediate then undergoes gradual and complete degrada-
which are assigned to N H stretching of N2H5+, NH4 and tion from 200 to 650◦C. The DTA shows an endotherm for
+
TABLE 1
Analytical data
Elemental analysis
C%
H%
N%
Hydrazine%
Compound
Color
Observed (Calcd.)
Observed (Calcd.)
Observed (Calcd.)
Observed (Calcd.)
N2H5H3CDTA.H2O
(N2H5)3HCDTA.H2O
NH4H3CDTA.2H2O
N2H5NH4H2CDTA.H2O
Colorless
Colorless
Colorless
Colorless
39.9 (40.18)
39.9 (40.12)
39.8 (40.18)
39.78 (40.18)
7.9 (8.19)
8.42 (8.70)
8.10 (8.37)
8.28 (8.56)
13.10 (13.39)
22.95 (23.23)
9.69 (9.97)
7.50 (7.65)
19.00 (19.8)
—
15.84 (16.10)
7.00 (7.35)

1122
C. SONIA AND B. N. SIVASANKAR
FIG. 3. ORTEP diagram of N2H5H3CDTA.H2O.
dehydration, an exotherm for dehydrazination and a broad
exotherm for pyrolysis of the acid.
The trihydrazinium salt undergoes endothermic dehydration
up to 95◦C followed by the loss of three hydrazine molecules
as a broad exotherm splitting in the region 150–200◦C. The
intermediate, the free acid decomposes similar to the case of
monohydrazinium salt in the temperature range 200–650◦C.
The ammonium salt loses two water molecules at 60–120◦C
for which the DTA shows a broad and weak endotherm. The an-
hydrous salt loses ammonia molecule in the temperature range
200–250◦C for which a sharp endotherm is observed. Subse-
quent pyrolysis of acid takes place up to 600◦C leaving no
residue in the sample holder indicating complete decomposi-
tion.
The ammonium hydrazinium salt shows two endotherms at
90◦C and 100◦C for the removal of water and ammonia and
an exotherm at 150◦C for dehydrazination. However, the TG
shows continues weight loss for these two processes. Further
FIG. 4. Packing diagram of N2H5H3CDTA.H2O.

SOME NEW AMMONIUM AND HYDRAZINIUM SALTS
1123
TABLE 2
Crystal data and structure refinement
N2H5H3CDTA.H2O
NH4H3CDTA.2H2O
CCDC No.
799930
N2H5H3CDTA.H2O
C14H28N4O9
800071
NH4H3CDTA.2H2O
C14H29N3O10
399.40
Identification code
Empirical formula
Formula weight
Temperature
396.40
293(2) K
293(2) K
Wavelength
0.71073 Å
0.71073 Å
Crystal system, space group
Unit cell dimensions
Monoclinic, P21/c
A = 8.6297(4) Å
α = 90◦
Monoclinic, P21/c
A = 8.6297(4) Å
α = 90◦
B = 9.4882(3) Å
β = 102.1660(10)◦
C = 21.7697(8) Å
γ = 90◦
B = 11.5016(5) Å
β = 90◦
C = 18.3935(9) Å
γ = 90◦
Volume
1818.18(15) Å3
4, 1.448 Mg/m3
0.121 mm−1
1860.78(11) Å 3
4, 1.426 Mg/m3
0.121 mm−1
856
Z, Calculated density
Absorption coefficient
F (000)
848
Crystal size
Theta range for data collection
Limiting indices
0.30 × 0.30 × 0.20 mm
0.22 × 0.16 × 0.16 mm
2.09−29.65◦
1.91−33.60◦
−11 ≤ h ≤ 12,
−15 ≤ k ≤ 15,
−25 ≤ l ≤ 19
21877 / 5083
−12 ≤ h ≤ 14,
−14 ≤ k ≤ 10,
−33 ≤ l ≤ 32
Reflections collected / unique
26096 / 6778
[R (int) = 0.0258]
[R (int) = 0.0240]
Completeness to theta = 25.00
Absorption correction
100.0%
100.0%
Semiempirical from equivalents
Semiempirical from
equivalents
Max. and min. transmission
Refinement method
0.9762 and 0.9646
Full-matrix least-squares on F2
5083 / 0 / 278
0.9809 and 0.9739
Full-matrix least-squares on F2
6778 / 3 / 297
Data / restraints / parameters
Goodness-of-fit on F2
1.032
1.033
Final R indices [I > 2sigma (I)]
R1 = 0.0421,
R1 = 0.0456,
wR2 = 0.1071
wR2 = 0.1288
R indices (all data)
R1 = 0.0617,
R1 = 0.0625,
wR2 = 0.1222
wR2 = 0.1422
Largest diff. Peak and hole
0.474 and−-0.210 e. Å−3
0.446 and −0.260 e.Å−3
decomposition of the acid takes place up to 600◦C with 100%
weight loss.
The simultaneous TG-DTA traces of N2H5H3CDTA.H2O
and NH4H3CDTA.2H2O are shown in Figures 1 and 2 respec-
tively.
the compound shows that it is composed of discrete N2H5+ and
H3CDTA3− ions along with a water molecule, which are in close
packing arrangement held together by hydrogen bonds. The
packing diagram reveals the presence of four such molecules
in a unit cell. The structure clearly shows that N2 consists of
two free carboxylic acid (CH2COOH) groups while N1 has two
carboxylate ions (CH2COO−). Among the two acidic protons
Structure of N2H5H3CDTA.H2O
This salt crystallizes as monoclinic crystal system with P21/c removed from two carboxylic acid groups, one attached to N1
space group. The observed crystal density from the X-ray sin- so as to give the zwitterion structure while the other attached to
gle crystal study is 1.448 mg/m3, which is very close to the hydrazine and present as hydrazinium cation. The acidic proton
experimental value of 1.441 mg/m3. The crystal structure of with pKa = 2.4 is expected to neutralize the hydrazine forming

1124
C. SONIA AND B. N. SIVASANKAR
TABLE 3
Bond lengths (Å) and bond angles (◦) for N2H5H3CDTA.H2O
Bond lengths (Å)
Bond angles (◦)
C(1)-N(1)
C(8)-O(4)
1.5194(16)
1.2586(17)
1.2341(17)
1.4602(16)
1.3122(16)
1.2092(17)
0.910(16)
0.89(3)
0.95(3)
0.97(3)
0.89(3)
1.0068
1.2414(16)
1.4988(16)
1.2633(17)
1.2061(17)
1.4536(17)
1.3132(17)
1.437(2)
0.94(2)
N(1)-C(1)-C(6)
N(1)-C(1)-H(1A)
N(2)-C(2)-C(3)
N(1)-C(7)-C(8)
N(1)-C(7)-H(7B)
O(3)-C(8)-C(7)
N(1)-C(9)-C(10)
N(1)-C(9)-H(9B)
O(2)-C(10)-O(1)
O(1)-C(10)-C(9)
N(2)-C(11)-H(11A)
O(5)-C(12)-O(6)
O(6)-C(12)-C(11)
N(2)-C(13)-H(13A)
O(7)-C(14)-O(8)
O(8)-C(14)-C(13)
C(7)-N(1)-C(1)
111.85(10)
107.3
115.36(11)
113.35(11)
108.9
114.40(12)
109.57(10)
109.8
126.05(13)
115.40(12)
109.3
N(1)-C(1)-C(2)
110.61(10)
110.38(11)
107.2
N(2)-C(2)-C(1)
N(2)-C(2)-H(2A)
N(1)-C(7)-H(7A)
O(3)-C(8)-O(4)
C(10)-O(2)
C(11)-N(2)
C(12)-O(6)
C(14)-O(7)
N(1)-H(1)
N(3)-H(5D)
N(3)-H(5E)
N(4)-H(6C)
O(1W)-H(1D)
O(8)-H(8)
108.9
126.46(13)
119.13(11)
109.8
O(4)-C(8)-C(7)
N(1)-C(9)-H(9A)
H(9A)-C(9)-H(9B)
O(2)-C(10)-C(9)
N(2)-C(11)-C(12)
N(2)-C(11)-H(11B)
O(5)-C(12)-C(11)
N(2)-C(13)-C(14)
N(2)-C(13)-H(13B)
O(7)-C(14)-C(13)
C(7)-N(1)-C(9)
108.2
118.55(12)
111.79(11)
109.3
123.54(12)
113.50(11)
108.9
125.66(13)
112.54(10)
111.16(10)
104.1(10)
112.02(10)
113.71(11)
109.0(14)
106.7(15)
116(2)
123.70(13)
112.75(11)
108.9
C(8)-O(3)
C(9)-N(1)
C(10)-O(1)
C(12)-O(5)
C(13)-N(2)
C(14)-O(8)
N(3)-N(4)
N(3)-H(5C)
N(4)-H(6D)
O(1W)-H(1C)
O(6)-H(6)
123.72(13)
110.61(12)
114.21(10)
108.4(10)
105.6(10)
113.96(10)
113.1(15)
104(2)
C(9)-N(1)-C(1)
C(9)-N(1)-H(1)
C(7)-N(1)-H(1)
C(1)-N(1)-H(1)
C(13)-N(2)-C(11)
C(11)-N(2)-C(2)
N(4)-N(3)-H(5C)
N(4)-N(3)-H(5E)
H(5C)-N(3)-H(5E)
N(3)-N(4)-H(6C)
H(1C)-O(1W)-H(1D)
C(14)-O(8)-H(8)
C(13)-N(2)-C(2)
N(4)-N(3)-H(5D)
H(5D)-N(3)-H(5C)
H(5D)-N(3)-H(5E)
N(3)-N(4)-H(6D)
H(6D)-N(4)-H(6C)
C(12)-O(6)-H(6)
0.91(3)
0.87(4)
0.9253
108(2)
102.6(18)
106(2)
103.5(14)
104(3)
109.5
109.5
TABLE 4
Hydrogen bonds for the compound N2H5H3CDTA.H2O (Å and ◦)
D H· · ·A
d (D H)
d(H· · ·A)
d(D· · ·A)
<(DHA)
O(6)-H(6). . .O(4)#1
O(8)-H(8). . .O(1)#2
O(8)-H(8). . .O(2)#2
N(1)-H(1). . .O(2)
0.93
1.01
1.01
1.69
1.56
2.59
2.6050(15)
2.5396(15)
3.1265(16)
2.6257(15)
2.8500(15)
3.053(2)
171.5
162.7
113.0
0.910(16)
0.910(16)
0.91(3)
0.97(3)
0.87(4)
0.89(3)
0.89(3)
0.94(2)
0.95(3)
2.053(16)
2.379(16)
2.34(3)
2.03(3)
2.34(4)
1.93(3)
2.04(3)
1.85(2)
2.00(3)
119.7(12)
112.2(12)
134(2)
161(2)
139(3)
176(3)
160(2)
175(2)
166(2)
N(1)-H(1). . .N(2)
N(4)-H(6D). . .O(2)#3
N(4)-H(6C). . .O(1W)
O(1W)-H(1C). . .O(2)#4
O(1W)-H(1D). . .O(1)
N(3)-H(5D). . .O(7)#3
N(3)-H(5C). . .O(3)#5
N(3)-H(5E). . .O(4)#3
2.961(2)
3.0417(19)
2.8187(18)
2.9003(18)
2.7890(17)
2.9334(17)
Symmetry transformations used to generate equivalent atoms:
#1 −x, −y + 2, −z + 1 #2 −x, −y + 1, −z + 1 #3 x + 1, y, z #4 −x + 1, −y + 1, −z + 1 #5 −x + 1, −y + 2, −z + 1.

SOME NEW AMMONIUM AND HYDRAZINIUM SALTS
1125
TABLE 5
Bond lengths (Å) and bond angles (◦) for NH4H3CDTA.2H2O
Bond lengths (Å)
Bond angles (◦)
C(1)-N(2)
C(7)-N(1)
C(8)-O(1)
1.5206(13)
1.4545
N(2)-C(1)-C(6)
N(2)-C(1)-H(1A)
N(1)-C(6)-C(5)
N(1)-C(7)-C(8)
N(1)-C(7)-H(7B)
O(2)-C(8)-C(7)
110.24(8)
107.4
114.82(8)
111.52(8)
109.3
124.12(10)
116.63(9)
112.7(9)
118.11(11)
111.04(8)
109.4
120.02(9)
113.32(9)
108.9
N(2)-C(1)-C(2) 112.42(8)
N(1)-C(6)-C(1)
N(1)-C(6)-H(6A)
N(1)-C(7)-H(7A)
O(2)-C(8)-O(1)
110.65(8)
107.4
109.3
1.3189(14)
1.5116(16)
1.2968(15)
1.2282(14)
1.4937(13
1.2471(15)
0.99(3)
0.97(3)
0.854(10)
0.76(3)
C(9)-C(10)
C(10)-O(4)
C(12)-O(5)
C(13)-N(2)
C(14)-O(7)
O(4)-H(4)
O(1W)-H(1C)
O(2W)-H(2D)
N(3)-H(3E)
N(3)-H(3F)
C(6)-N(1)
123.91(12)
111.97(10)
108.1(9)
123.69(11)
118.18(10)
109.4
126.52(10)
113.45(9)
108.9
126.69(11)
118.88(10)
112.0(14)
105(2)
117(2)
97(3)
113(3)
114.01(8)
111.45(8)
110.99(8)
108.2(9)
O(1)-C(8)-C(7)
N(1)-C(9)-C(10)
N(1)-C(9)-H(9B)
O(3)-C(10)-C(9)
N(2)-C(11)-C(12)
N(2)-C(11)-H(11B)
O(5)-C(12)-C(11)
N(2)-C(13)-C(14)
N(2)-C(13)-H(13B)
O(8)-C(14)-C(13)
C(8)-O(1)-H(1)
H(1B)-O(1W)-H(1C)
H(3D)-N(3)-H(3E)
H(3E)-N(3)-H(3C)
H(3E)-N(3)-H(3F)
C(9)-N(1)-C(7)
N(1)-C(9)-H(9B)
O(3)-C(10)-O(4)
O(4)-C(10)-C(9)
N(2)-C(11)-H(11A)
O(5)-C(12)-O(6)
O(6)-C(12)-C(11)
N(2)-C(13)-H(13A)
O(8)-C(14)-O(7)
O(7)-C(14)-C(13)
C(10)-O(4)-H(4)
H(2C) O(2W) H(2D)
H(3D)-N(3)-H(3C)
H(3D)-N(3)-H(3F)
H(3C)-N(3)-H(3F)
C(9)-N(1)-C(6)
0.84(4)
1.4760
C(8)-O(2)
C(9)-N(1)
1.2054(15)
1.4544(14)
1.2235(15)
1.5005(12)
1.2780(13)
1.2474(15)
0.85(3)
0.85(2)
0.821(9)
0.93(3)
114.43(10)
110.1(17)
90(2)
104(2)
111(2)
C(10)-O(3)
C(11)-N(2)
C(12)-O(6)
C(14)-O(8)
O(1)-H(1)
O(1W)-H(1B)
O(2W)-H(2C)
N(3)-H(3D)
N(3)-H(3C)
N(2)-H(1)
115(3)
113.80(8)
112.82(8)
114.01(8)
109.1(9)
102.6(9)
C(7)-N(1)-C(6)
C(13)-N(2)-C(11)
C(11)-N(2)-C(1)
C(11)-N(2)-H(1)
C(13)-N(2)-C(1)
C(13)-N(2)-H(1)
C(1)-N(2)-H(1)
0.90(2)
0.863(14)
TABLE 6
Hydrogen bonds for the compound NH4H3CDTA.2H2O (Å and ◦)
D H· · ·Ad
(D H)
0.99(3)
0.93(3)
0.93(3)
0.76(3)
0.85(3)
0.863(14)
0.863(14)
0.90(2)
0.84(4)
0.97(3)
0.854(10)
0.85(2)2.48(2)
0.854(10)
d(H· · ·A)
d(D· · ·A)
2.5177(12)
2.9329(17)
3.067(2)
<(DHA)
O(4)-H(4). . .O(6)#1
N(3)-H(3D). . .O(7)#2
N(3)-H(3D). . .O(2)#2
N(3)-H(3E). . .O(3)#3
O(1)-H(1). . .O(2W)
N(2)-H(1). . .N(1)
1.52(3)
2.04(3)
2.55(3)
2.23(3)
1.76(3)
2.289(13)
2.637(13)
1.93(2)
2.28(4)
1.98(3)
2.07(3)
2.9598(17)
2.58(4)
179(3)
159(2)
115(2)
170(3)
174(3)
121.3(11)
132.9(11)
163.2(18)
159(4)
159(2)
137(4)
2.980(2)
2.6037(16)
2.8351(12)
3.2864(13)
2.8082(16)
3.0752(18)
2.911(2)
2.7611(16)
116.1(16)
2.8038(17)
N(2)-H(1). . .O(2)
N(3)-H(3C). . .O(8)
N(3)-H(3F). . .O(4)#2
O(1W)-H(1C). . .O(8)
O(2W)-H(2D). . .O(7)#2
O(1W)-H(1B). . .O(6)#4
O(2W)-H(2D). . .O(3)#3
96(3)
Symmetry transformations used to generate equivalent atoms:
#1 −x + 1, −y + 1, −z #2 −x + 1, −y, −z #3 x, y − 1, z #4 −x + 2, −y, −z.

1126
C. SONIA AND B. N. SIVASANKAR
TABLE 7
Antibacterial activity of the CDTA ligands
Diameter of zone inhibition (mm)
Staphylococcus
aureus
Escherichia
coli
Pseudomonas
aeruginosa
Bacillus
subtilis
Compound
Conc. mg/disc
N2H5H3CDTA. H2O
500
250
500
250
500
250
500
250
23
20
25
22
16
13
16
14
25
20
14
26
21
18
12
18
15
27
15
11
21
15
—
—
18
13
27
18
13
25
21
13
11
21
17
27
(N2H5)3H CDTA.H2O
NH4H3CDTA .2H2O
NH4N2H5H2 CDTA
Standard
Ciprofloxacin/ disc
the hydrazinium salt. The structure is unsymmetrical due to the in the salt instead of hydrazinium ion. This salt has two water
asymmetry with respect to nitrogen atoms and carboxylic acid molecules in its crystal structure. But the CDTA moiety has
groups. The ORTEP diagram and packing diagram of the salt exactly same structure as observed in the case of hydrazinium
are shown in Figures 3 and 4, respectively. The crystal data of salt. The bond length and bond angle are summarized in Table 5
the salt is given in Table 2. The bond lengths and bond angles and hydrogen bonds are given in Table 6.
for this compound are listed in Table 3 and hydrogen bonds are
Antimicrobial Activities of the Salts
summarized in Table 4.
The newly synthesized hydrazinium and ammonium salts of
Structure of NH4H3CDTA.2H2O
CDTA were screened for their antibacterial activities against
Gram-positive and Gram-negative organisms by agar diffusion
method using ciprofloxacin as the standard. Though all the pre-
pared salts show better activity than the acid, H4CDTA, hy-
drazinium, trihydrazinium, and ammonium salts show very good
activities as evident from the zone of inhibition. The antibacte-
rial activities of the ligands are summarized in Table 7. Except
monohydrazinium and trihydrazinium salts, which show very
little activities that too only against Candida albicans, other
salts hardly show any activity against both Candida albicans
and Aspergillus niger.
The crystal data of this salt is also summarized in Table 2.
The ORTEP diagram of the ammonium salt is shown in Figure 5.
This salt also crystallizes in monoclinic system with P21/c space
group. The unit cell also consists of four molecules. The ORTEP
diagram is comparable with that of the hydrazinium salt. The
structures are almost similar except the ammonium ion present
SUPPLEMENTARY MATERIAL
Supplementary materials for X- ray crystal struc-
tures are available with the following CCDC numbers:
N2H5H3CDTA.H2O : CCDC 799930 and NH4H3CDTA.2H2O:
CCDC 800071.
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FIG. 5. ORTEP diagram of NH4H3CDTA.2H2O.

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1127
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