Analytical Properties of 2,2-Bis (di-2-pyridinyl-methylene)-thiocarbohydrazone

J. R. BONILLA
ABAs~AL., A. GARCIA DE TORRES, AND J. M. CANO PAVON

Thiosemicarbazones have been widely used as analytical reagents in spectrophotometry, fluorimetry, and also as visual indicators. Their analytical applications have been reviewed (II). In general, the great ability that the atoms of sulfur have for coordinating metal cations makes the establishment of selective methods of analysis difficult; however, due to the acid dissociation of the thiosemicarbazone group, formation of chelates is pH-dependent. This fact, as well as the use of masking agents, have been used in diverse selective determinations for some metal ions, such as copper with biacetyl-bis (4-phenyl-3-thiosemicarbazone) (I) and I,2 cyclohexonodione bis thiosemicarbazone (9), manganese with biacetyl oxime (4-phenyl-3-thiosemicarbazone) (3), and divcrsc mixtures of cobalt, nickel, iron, and copper with picolinaldehyde thiosemicarbazone (4). In our department, a study has begun about the complexing properties and analytical applications of thiocarbohydrazones. These compounds show a symmetrical structure and they are obtained by the condensation of thiocarbohydrazide, H,N-NHC-NH-NH,

with an aldehyde or ketone. No analytical data have been published on these compounds, although they have been tested as antimicrobial and antitumor agents with good results (10).

I Actual address: Department sity. Malaga.

of Analytical

Chemistry,

Faculty of Sciences, The Univer-

ANALYTICAI.

PROPERTIES

OF

THIOCARBOHYDRAZONE

133

In the present article, physico-chemical properties, metal-ion interactions, and analytical possibilities of a new compound, 2-2-bis (di-2pyridinyl-methylene)-thiocarbohydrazide (DPTH)

are studied, and the results are compared with those obtained in the study of thiosemicarbazones. A detailed investigation of their chelates was made.
EXPERIMENTAL

Dissolve 0.4 g (3.8 x lo-: mol) of thiocarbohydrazide (ICN Pharmaceuticals) in 50 ml of distilled water, and add 1.7 g (9.2 x IO- mol) of di-2-pyridyl ketone in 10 ml of ethanol, and 0.S ml of glacial acetic acid. Reflux for 2 hr. Filter off the yellow product and recrystallize from ethanol (mp 172- 174C: yield 74%;). Found: C 63.2%; H 4.3%; N 25.6%: S 7.6%. Calculated for C,:,H,,N,S: C 63.01%: H 4.11%; N 25.57%: s 7.31%.
Propertics

Some physico-chemical properties of DPTH are summarized in Table 1. Solutions of DPTH (0.05%) in ethanol, dimethylformamide, and chloroform were stable for more than a week. The absorption spectra of DPTH in DMF-water solutions at various pH values show bathochromic and hipochromic shifts in neutral and alkaline media. Values of pK were calculated from the variation of absorbance with pH by the Stenstrom and Goldsmith method (12). The pK values shown in Table 1 are the arithmetic mean of the values obtained from measurements at three different wavelengths.
Chelation Studies

The reaction of 40 cations with DPTH were tested at different pH values. The most sensitive reactions were those of Co(H), Ni(II), Fe(I1). Cu(I1). Zn(II), Cd(H), and Pd(I1). A spectrophotometric study of the chelates formed was made. The solutions were prepared in 25-ml standard flasks with 2-4 ppm of metal ion, 5-10 ml of O.OS-0.1% of dimethylformamide to prevent precipitation, and dilution with distilled

134

BONILLA

ABASCAL,

GARCIA

DE TORRES, 1

AND

CAN0

PAVON

TABLE
PHYSICOCHEMI~AL

PROPERTIES

OF DPTH

Solubility in water (griliter) Solubility in ethanol (griliter) Solubility in amyl alcohol (griliter) Solubility in dimethylformamide (griliterl Solubility in chloroform (griliter) -NHFrequency (cm-) -C=NFrequency (cm-) -C=SFrequency (cm-) First pK found (Stenstrom and Goldsmith method) Second pK found (Stenstrom and Goldsmith method)

0.072 1.068 0.256 11.1 125.2 3060 w 1590 m, 1580 m 1230 s, 1210 m 3.07 9.85

water. The absorbance was measured at 350-700 nm against reagent blanks. The most important results are summarized in Table 2.
RESULTS AND DISCUSSION

DPTH shows only two ionization steps. Since the molecule is symmetrical and the distance between the four nitrogen atoms of the pyridine rings is relatively long, the values of the constants K1 to K, would be expected to lie close together, and are not distinguishable by specTABLE
CHARACTERISTICS

2
COMPOUNDS

OF DPTH

Ion Co(H) Co(lI) Ni(II1 Cu(l1) Zn(I1) Cd(H) Fe(II1 &(I) Fe(II1) Os(IV1 Hs(I) Hg(IIJ Pb(IJ1 Bi(III) Pd(IJ) WV) In(IV1 Ga(II1)

Optimum pH 3.2 10.4- 11.0 4.8-6.8 2.4-4.8 6.2-9.8 5.8-8.3 3.0-55.0 9.5 5.5 1.7 5.5 5.5 9.5 5.5 3.0 2.3 5.5 5.5 Yellow Red Yellow Yellow Yellow Yellow Green Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow

nm 410 480 410 420 415 415 670 420 410 414 412 404 430 420 414 450 420 420

liter, moles .crn-i 5.29 4.28 5.01 2.80 6.01 5.64 0.92 1.18 5.42 1.23 2.39 4.51 1.99 5.33 2.92 1.32 4.51 3.07 x x x x
x

M:R I:2 1: I I:2 I:I I:3 I:3 I:? -

x x x
x

x x x x x x x x x

lo lo* 10 10 10 IO4 104 104 10 10 IO 104 104 IO-1 IO4 104 IO 101

ANALYTICAL

PROPERTIES

OF THIOCARBOHYDRAZONE

135

trophotometry: the value found is 3.07; this value resembles the corresponding constants of pyridine rings (2,6). The second pK value found is 9.85, and can be attributed to the loss of the proton of the -SH group (5). DPTH is unstable towards strong oxidizing agents, but stable in the presence of reducing substances, and it is not hydrolyzed by acids, and can be used in acidic solutions. Stoichiometric data show that DPTH acts as a tridentate ligand with convenient steric arrangements of its donor groups in the complexes formed with Co(II), Ni, and Fe(lI), and as a bidentate ligand against Cu(II), Zn, and Cd. These data indicate that each half of the molecule behaves independently, and that the grouping thioazomethineferroine N=C-C=N-N=CS is used in the coordination as occurs in the complexes of cu-pyridyl thiosemicarbazones (7). In the case of the red cobalt-DPTH complex in alkaline media, the 1:l stoichiometric ratio seems to indicate that DPTH acts as a sexadentate ligand, with no participation of the sulfur atom. The analytical possibilities of DPTH are superior to those of di-2pyridyl ketone thiosemicarbazone (DPKT) (8) owing to the higher molar

2
I--t-----4 -

+-------4
-co ----lc

Ni

Fe(ll)

IO

12

PH

F~ti. 1. Comparison of molar absorptivity (in liters.mol of the complexes of DPTH ( ---I and DPKT (- -

cm -).

.) and optimum pH range

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BONlLLA

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GARCIA

DE

TORRES,

AND

CAN0

PAVON

absorptivities of the chelates and to the shift of the absorption peaks to longer wavelengths. Figure 1 summarizes for comparison the optimal pH zones for the formation of the complexes with DPTH and DPKT as well as the molar absorptivity. In general, the optimal pH range of DPTH complexes lies at more acidic pH values, and their molar absorptivity have the highest values. Zn and Cd form orange-yellow complexes that can be used in the spectrophotometric determination of both ions at very low concentrations.
SUMMARY
(di-?-pyridinyl-methylene)The synthesis and analytical properties of 2 .2-bis thiocarbohydrazone are described. The solubility, spectral characteristics, and pK values are reported, as well as the absorptivity and stoichiometric ratio of metal chelates formed.

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(1978).
2. 3. Brown, H. C., and McDaniel, D. H., The base strengths and ultraviolet absorption spectra of the 2- and 3-monohalopyridines. J. Amrr. Chem. SW. 77, 3752 (1955). Cano Pavon, J. M.. Jimenez Sanchez. J. C., and Pino, F., The 4-phenyl-3thiosemicarbazone of biacetylmonoxime as an analytical reagent. Spectrophotometric determination of manganese. AIILI/. Chim. Acru. 75, 335 (1975). Cano Pavon, J. M., and Perez Bendito, Determination fotometrica de Fe, Co. Ni, y Cu. en mezclas con la tiosemicarbazona del picolinaldehido. /,I,$ Qrtin~. AMJ/. 27, 20-30 (1974). Cano Pavon. J. M., and Pino, F., Comparative study of analytical properties and applications of picolinaldehyde thiosemicarbazone and selenosemicarbazone. 7a/tr/?tc1 19, 1659% 1663 (1972). Gonzalez Balairon, M.. Cano Pavon, J. M., and Pino. F., Analytical properties of bipyridylglyoxal bis (4.phenyl-3-thiosemicarbazone). Tu/art/tr 26, 71-73 (1978). Martinez Aguilar. M. T.. Cano Pavon, J. M., and Pino, F., The thioazomethine-ferroine group as a new functional group for iron( Determination of iron with 2acetylpyridine-4-phenyl-3-thiosemicarbazone. 90, 335-338 (1977). Martinez, M. P.. Valcarcel, M., and Pino, F., Di-2-pyridyl ketone thiosemicarbazone as an analytical reagent. Ancrl. Chinl. Ado 81, 157 (1976). Mutioz Leyva, J. A.. Cano Pavon, J. M., and Pino, F., Empleo de la 1.2 ciclohexanodiona ditiosemicarbazona coma reactive espectrofotometrico para la determinacion selectiva de cobre en disolucibn. An. Quim. 72, 392-395 (1976). Rhee, S., Synthesis and evaluation of antimicrobial-antitumur activities of methylthiosemicarbazones and thiocarbohidrazones. J. Pllcrrrn. SW. Korc,cr 16, 162- 175 (1972). Singh, R. B., Garg. D. S., and Singh. R. P., Analytical applications of thiosemicarbazones and semicarbazones: A review. T~/rrlltrr 25, 619 (1978). Stenstrom and Goldsmith, Determination of the dissociation constants of phenol and the hydroxyl group of tyrosine by means of absorption measurements in the ultraviolet. .I. Phys. Chem. 30, 1683 (1926).

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