Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry
Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry
Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry
To cite this article: Imran Ali , Waseem A. Wani & Kishwar Saleem (2013) Empirical Formulae to Molecular Structures of Metal
Complexes by Molar Conductance, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:9,
1162-1170, DOI: 10.1080/15533174.2012.756898
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 43:1162–1170, 2013
Copyright C Taylor & Francis Group, LLC
1162
CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES 1163
TABLE 1 N
Molar conductance ranges for nonelectrolytes and electrolytes
in different solvents
O
Non-electrolyte Electrolyte OH
molar molar Cu
Cl
conductance conductance H2O
range range H2O
H2O
S. No. Solvent (−1cm2mol−1) (−1cm2mol−1)
1 Nitromethane <70 >75 FIG. 1. Octahedral Cu(II) complex.
2 Nitrobenzene <20 >20
3 Acetonitrile <120 >120
4 Acetone <95 >100
5 DMF <60 >65 of a metal complex can be predicted easily. By using these mo-
6 Methanol <80 >80 lar conductance data and the pre-established structure of ligand,
7 Ethanol <30 >35 one can easily predict the geometry (square planar, octahedral,
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TABLE 2
The ranges of molar conductances of metal complexes with 1:1, 1:2, 1:3, and 1:4 ratios of cationic and anionic species
Molar conductance (−1cm2mol−1) ranges
S. No. Solvents 1:1 Electrolyte 1:2 Electrolyte 1:3 Electrolyte 1:4 Electrolyte References
[16]
1 Nitromethane 75–95 150–180 220–260 290–330
[16]
2 Nitrobenzene 20–30 50–60 70–82 90–100
3 Acetonitrile 120–160 220–300 340–420 >500 [16]
TABLE 3
Molar conductance values and geometry of complexes
S. No. Complex m Solvent Nature of the organic ligand Geometry References
[30]
1 [Ni(C12 H9 SNOBr)2 ] 3.41 DMSO Mono-negative and bidentate Square-planar
[18]
2 [CuC20 H42 N6 O2 ]Cl2 152.5 Water Neutral tetradentate macrocycle Square-planar
[18]
3 [NiC20 H42 N6 O2 ]Cl2 148.7 Water Neutral tetradentate macrocycle Square-planar
[18]
4 [CoC20 H42 N6 O2 ]Cl2 192.0 Water Neutral tetradentate macrocycle Square-planar
[31]
5 [Cu(C6 H7 N3 OS)2 ]Cl2 136 DMF Neutral bidentate Schiff base Square-planar
[32]
6 [Cu(C7 H9 N3 O2 )2 ]Cl2 154 DMF Neutral bidentate Schiff base Square-planar
[32]
7 [Cu(C7 H9 N3 OS)2 ]Cl2 152 DMF Neutral bidentate Schiff base Square-planar
[32]
8 [Pt(C15 H10 N3 S)2 ]C3 H6 O·2H2 O 23.5 DMF Di-negative and bidentate Square-planar
[33]
9 [CoC22 H18 N6 O8 ](NO3 )2 120 DMSO Neutral tetradentate Schiff base Square-planar
[33]
10 [NiC22 H18 N6 O8 ](NO3 )2 113 DMSO Neutral tetradentate Schiff base Square-planar
[33]
11 [CuC22 H18 N6 O8 ](NO3 )2 117 DMSO Neutral tetradentate Schiff base Square-planar
[33]
12 [ZnC22 H18 N6 O8 ](NO3 )2 114 DMSO Neutral tetradentate Schiff base Square-planar
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[19]
13 [CoC30 H26 N2 O4 ]Cl2 185 DMSO Neutral hexadentate macrocycle Octahedral
[19]
14 [Mn(C30 H26 N2 O4 ](NO3 )2 175 DMSO Neutral hexadentate macrocycle Octahedral
[8]
15 [Mn(C15 H15 NO)2 Cl2] 18 DMF Neutral bidentate Schiff base Octahedral
[8]
16 [Ni(C15 H15 NO)2 Cl2] 18 DMF Neutral bidentate Schiff base Octahedral
[8]
17 [Co(C15 H15 NO)2 Cl2] 18 DMF Neutral bidentate Schiff base Octahedral
[34]
18 [Co(C12 H10 N3 O3 S)2 ] 23.8 DMSO Uni-negative and tridentate Octahedral
[34]
19 [Co(C13 H12 N3 O3 S)2 ] 17.25 DMSO Uni-negative and tridentate Octahedral
[34]
20 [Ni(C12 H10 N3 O3 S)2 ] 22.88 DMSO Uni-negative and tridentate Octahedral
[21]
21 [Cr(C16 H12 N4 )Cl2 ]Cl 88.5 DMF Neutral tetradentate macrocycle Octahedral
[21]
22 [Cr(C16 H12 N4 )Cl2 ]Cl 95.0 DMF Neutral tetradentate macrocycle Octahedral
[21]
23 [Cr(C22 H24 N4 )Cl2 ]Cl 81.0 DMF Neutral tetradentate macrocycle Octahedral
[21]
24 [Ni(C16 H12 N4 )Cl2 ] 8.5 DMF Neutral tetradentate macrocycle Octahedral
[21]
25 [Ni(C16 H12 N4 )Cl2 ] 8.2 DMF Neutral tetradentate macrocycle Octahedral
[21]
26 [Ni(C22 H24 N4 )] Cl2 7.4 DMF Neutral tetradentate macrocycle Octahedral
[35]
27 [Co(C28 H23 N4 OF)2 Cl2 ] 19.22 DMF Neutral bidentate Schiff base Octahedral
[35]
28 [Ni(C28 H23 N4 OF)2 Cl2 ] 22.25 DMF Neutral bidentate Schiff base Octahedral
[35]
29 [Cu(C28 H23 N4 OF)2 Cl2 ] 23.67 DMF Neutral bidentate Schiff base Octahedral
[35]
30 [Mn(C28 H23 N4 OF)2 Cl2 ] 23.4 DMF Neutral bidentate Schiff base Octahedral
[36]
31 [Co(C12 H20 N8 S2 )Cl2 ] 17 DMSO Neutral tetradentate macrocycle Octahedral
[36]
32 [Co(C12 H20 N8 S2 )(NO3 )2 ] 12 DMSO Neutral tetradentate macrocycle Octahedral
[36]
33 [Co(C12 H20 N8 S2 )(OCOCH3 )2 ] 11 DMSO Neutral tetradentate macrocycle Octahedral
[36]
34 [Ni(C12 H20 N8 S2)Cl2 ] 16 DMSO Neutral tetradentate macrocycle Octahedral
[36]
35 [Ni(C12 H20 N8 S2 )(NO3 )2 ] 15 DMSO Neutral tetradentate macrocycle Octahedral
[36]
36 [Ni(C12 H20 N8 S2 )(OCOCH3 )2 ] 12 DMSO Neutral tetradentate macrocycle Octahedral
[36]
37 [Zn(C12 H20 N8 S2 )(OCOCH3 )2 ] 12 DMSO Neutral tetradentate macrocycle Octahedral
[37]
38 [MnC22 H20 N12 O2 S2 ]Cl2 82.70 DMSO Neutral tridentate ligand Octahedral
[37]
39 [FeC22 H20 N12 O2 S2 ]Cl3 225.8 DMSO Neutral tridentate ligand Octahedral
[37]
40 [CoC22 H20 N12 O2 S2] ]Cl2 91.90 DMSO Neutral tridentate ligand Octahedral
[37]
41 [NiC22 H20 N12 O2 S2 ]Cl2 108.6 DMSO Neutral tridentate ligand Octahedral
[37]
42 [ZnC22 H20 N12 O2 S2 ]Cl2 107.6 DMSO Neutral tridentate ligand Octahedral
[20]
43 [Cu(C10 H12 N4 S4 O4 ) Cl2 ] 12 DMSO Neutral tetradentate macrocycle Tetragonal
[8]
44 [Cu(C15 H15 NO)2 Cl2] 17 DMF Neutral bidentate Schiff base Tetragonal
[34]
45 [Cu(C13 H12 N3 O3 S)2 ] 21.11 DMSO Uni-negative and tridentate Tetragonal
[36]
46 [Cu(C12 H20 N8 S2 )Cl2 ] 17 DMSO Neutral tetradentate macrocycle Tetragonal
[36]
47 [Cu(C12 H20 N8 S2 )(NO3 )2 ] 12 DMSO Neutral tetradentate macrocycle Tetragonal
[36]
48 [Cu(C12 H20 N8 S2 )(OCOCH3 )2 ] 12 DMSO Neutral tetradentate macrocycle Tetragonal
[37]
49 [CuC22 H20 N12 O2 S2 ]Cl2 79.20 DMSO Neutral tridentate ligand Tetragonal
[38]
50 [CuC22 H24 N4 O6 ] 17.9 DMSO Di-negative hexadentate ligand Tetragonal
CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES 1165
OH
HO N N
N Cu N
N N O N O
Cl2
Co
O O Cl2
N
Attempts have been made to discuss the structures of some FIG. 3. Octahedral cobalt(II) complex.
complexes by using molar conductance data, which are given in
Table 3. Let us discuss the most commonly observed geometries [CuC10 H12 N4 S4 O4 Cl2 ] as the molecular formula of this com-
(square planar, octahedral and tetragonal) in metal complexes. plex. Now, applying the knowledge of coordination chemistry,
First example is of copper complex with CuC20 H42 N6 O2 Cl2 as the complex is octahedral but in nature it exists as tetragonal
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empirical formula. In this empirical formula, the structure of the (Figure 4) due to the John Teller effect.[20] Efforts have been
main ligand has already been established as neutral tetradentate made to correlate the structures of various metal complexes
macrocyle by elemental analyses and spectroscopic data. Its with their molar conductance values and are summarized in Ta-
molar conductance in water is 152.5 (−1cm2mol−1), which in- ble 3. These data may be used to elucidate the structures of other
dicates that the complex is electrolytic in nature with 1:2 ratio newly synthesized complexes in future.
of coordinating sphere cation and anion (Table 2). This is pos-
sible only if two chloride ions exist outside the coordination Relative Size of Ligands
sphere. Therefore, the molecular formula of this complex can It is a well-known fact that electrolytic conductance is di-
be written as [CuC20 H42 N6 O2 ]Cl2 . It is known that ligand is rectly proportional to the mobility of the constituent ions (ionic
tetradentate and the only possibility is of square-planar geome- mobility) of the electrolyte. Ionic mobility measures the speed
try. This geometry has also been verified by experimental data with which ions in an electrolyte move under the influence of
(Figure 2).[18] an external electric field. A metal complex in a given solvent
Further, let us take one more example of another complex dissociates into two parts viz. a large coordination part and
(i.e., CoC30 H26 N2 O4 Cl2 ) with neutral hexadentate macrocycle the counter ions (primary valency satisfiers). Large sized ions
as ligand. The molar conductance of this complex in DMSO are expected to move slower than the small sized ions. Molar
is 185.0 −1cm2mol−1. According to Tables 1 and 2, it is conductance data gives us an insight into estimating the rela-
electrolytic in nature with 1:2 coordination sphere cation and tive size of ligands in series of structurally relevant complexes.
anion ratio. Therefore, the molecular formula is written as For example, the molar conductance of nickel(II) complexes
[CoC30 H26 N2 O4 ]Cl2 . Applying the knowledge of coordination (Figure 5) of 12-, 14-, and 16-membered macrocycles, is in the
chemistry, the complex is octahedral in nature as shown in order; 12-membered > 14-membered > 16-membered. This or-
Figure 3.[19] Similarly, the ligand of CuC10 H12 N4 S4 O4 Cl2 com- der can be explained on the basis of the fact that an increase in
plex is a neutral tetradentate macrocycle. Its molar conductance ligand size of the complexes tends to decrease their molar con-
in DMSO is 12.0 −1cm2mol−1; indicating the non-electrolytic ductance values. However, little difference exists between the
nature of the complex (Tables 1 and 2). Therefore, two chloride molar conductance of fourteen and 12 membered complexes due
anions should be inside the coordination sphere, giving rise to to their near similar sizes. In this way the molar conductance
O O
H H H H TABLE 4
Cl Molar conductance values of complexes 1, 2, and 3 in water,
Cl
N N N N methanol, acetonitrile and nitromethane
Ni Ni
Molar Conductance (−1cm2mol−1)
N N N N
Cl Complex Water Methanol Acetonitrile Nitromethane
Cl
H H H H
Twelve membered nickel complex Fourteen membered nickel complex 1 270 124 74 29
2 254 100 107 55
FIG. 5. Nickel complexes of structural isomeric 12- and 14-membered macro- 3 200 136 130 92
cycles.
data provides the structural clue for structurally related provides a clue for determining their metal-ligand stoichiome-
complexes.[21] tries. For example, a neutral organic ligand (L) with three po-
tential donor atoms (e.g., S, O, or N) while reacting with a metal
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NH
N
Co Cl PF6
N
NH
Methanol
NH NH
NH NH
N N
N Acetonitrile Co Cl Co Cl
N
Co H2 O
Co Cl PF6 Water PF6 Cl PF
PF6 N 6
N N
N NH
NH NH
NH
Solid sate
b' b"
Nitromethane
NH
N
Co Cl
PF6
N
NH
FIG. 6. (a) Structures of complex 3 in solid state, water, methanol, acetonitrile, and nitromethane. (Continued)
CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES 1167
CH3
N
MeOH
N
Co
Cl Cl
N
N
CH3
Methanol
N Acetonitrile N N
Co Co Water Co
Cl Cl Cl OH2 Cl2
N N N
N N N
CH3 CH3 CH3
Solid sate
Nitromethane
CH3
N
Cl
N
Co
Cl
N
N
CH3
FIG. 6. (b) Structures of complex 1 in solid state, water, methanol, acetonitrile, and nitromethane. (Continued)
practically formed will be decided by the molar conductance the information about the structures of complexes in solution
data. In this way, molar conductance data may be exploited to phase. Hubin and coworkers studied the solution structures of
establish metal-ligand stoichiometry. cobalt(II) and copper(II) complexes of a series of topologically
constrained and cross-bridged tetraazamacrocycles.[22,23] Hubin
Structural Variations of Complexes in Different Solvents et al. determined the molar conductances of Co(II) complexes
It is well known that the structures of metal complexes vary of topologically constrained tetraazamacrocycles in water, ace-
in different solvents. The structural variance of a complex in tonitrile, methanol and nitromethane (Table 4). The results pre-
different solvents is of prime importance in physical, chemi- sented in this table support the fact that the solution ionization
cal, and biological processes. The molar conductance data also (displacement of chloride by solvent) of these complexes is con-
provides some clue for determining the structures of metal com- sistent with the dielectric constant and coordinating ability of
plexes in different solvents. Solvent molecules themselves act as the solvent.
coordinating ligands and, therefore, coordinate to metal ions in Two of the three complexes (1 and 2; Figure 6) in water
a complex by the displacement of counterions. These displace- have molar conductance values in the range of 1:2 electrolytes
ment reactions quite significantly change the molar conductance natures, indicating the replacement of two chlorido ligands
ranges of complexes. Analysis of all such changes provides by two water molecules. Surprisingly, the conductance of the
1168 I. ALI ET AL.
CH3
N
MeOH
N
Co
Cl Cl
N
2 N
CH3
Methanol
CH3 CH3
N CH3
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N
N
Acn Cl
N N OH2
Acetonitrile Co Water N
Co Co
Cl Cl Cl Cl2
N OH2
N N
N N N
CH3 CH3 CH3
Solid sate
Nitromethane
CH 3
N
Cl
N
Co
Cl
N
N
CH 3
FIG. 6. (c) Structures of complex 2 in solid state, water, methanol, acetonitrile, and nitromethane. (Continued)
five-coordinate complex 3 is between 1:1 and 2:1 electrolytes. 3. Finally, in nitromethane, a solvent with low dielectric con-
This suggests that the single chlorido ligand is only partially stant and non-coordinating ability, the six-coordinate complexes
displaced in water. Therefore, complex 3 exists in equilibrium behave as non-electrolytes, revealing that the chlorido ligands
with the structures b and b as shown in Figure 6. How- remain in bound form. The structure of the complex in solution is
ever, in methanol, the first chlorido ligand is fully replaced six-coordinate pseudo-octahedral as in the solid state. However,
by solvent molecules and all the three complexes exceeded typ- five-coordinate complex 3 in nitromethane has a molar conduc-
ical 1:1 electrolyte behavior. Contrarily, there is no effect of tance consistent with a 1:1 electrolyte. This indicates the pres-
methanol on the second chloride. Moreover, in acetonitrile all ence of the unbound PF6 anion, without singly bound chlorido
the three complexes have conductance values slightly less than ligand dissociation. The solution structures of complexes 1 and
1:1 electrolytes. This implies that one molecule of the solvent 2 in nitromethane, acetonitrile, methanol, and water are given in
has partially displaced one chlorido ligand from the coordina- Figure 6. This type of information is very important for deter-
tion spheres of both the six-coordinate complexes. Furthermore, mining the fate of the complexes in biological and environmental
there is no chlorido displacement in the five- coordinate complex matrices.
CONDUCTANCE AND STRUCTURES OF METAL COMPLEXES 1169
CONCLUSION base and its transition metal complexes. Synth. React. Inorg. Met.-Org.
The molar conductance data is very important information Chem. 2001, 31, 1053–1061.
16. Geary, W.J. The use of conductivity measurements in organic solvents for
for the structure elucidation of metal complexes. The data of the characterisation of coordination compounds. Coord. Chem Rev. 1971,
electrolytic and non-electrolytic natures and the ratio of coordi- 7, 81–122.
nating cationic sphere and anions (in case of electrolytic metal 17. Varghese, S.; Nair, M.K. M. Spectroscopic and antimicrobial studies of
complexes) can be applied to empirical formulae of metal com- some 2-hydroxybenzilidene-3-aminophenol complexes. RJPBCS 2010, 1,
plexes for predicting their three dimensional structures. More- 347–353.
18. Arjmand, F.; Aziz, M.; Chauhan, M. Synthesis, spectroscopic studies
over, ligand sizes of structurally relevant complexes, the amount of new water-soluble Co(II) and Cu(II) macrocyclic complexes of 4,15-
of ligand forming part of a complex and the solution structures bis(2-hydroxyethyl)-2,4,6,13,15,17-hexaazatricyclodocosane: their inter-
of metal complexes can be easily established from their molar action studies with calf thymus DNA and guanosine 50 monophosphate. J.
conductance data. Briefly, this approach is highly useful for de- Incl. Phenom. Macrocycl. Chem. 2008, 61, 265–278.
termining the structures of newly synthesized metal complexes 19. Kumar, R. Singh, R.P.; Singh, R.P. Spectroscopic and electrochemical prop-
erties of organic framework of macrocylic OONNOO-donor ligand with its
without involving sophisticated paraphernalia.
metal organic framework: Host/guest stability measurements. Spectrochim.
Acta A 2008, 71, 305–311.
20. Chandra, S.; Gupta, L.K. Spectroscopic characterization of tetradentate
macrocyclic ligand: its transition metal complexes. Spectrochim. Acta A
Downloaded by [Universita degli Studi di Torino] at 17:09 18 July 2013
32. Reddy, K.H.; Reddy, P.S.; Babu, P.R. Nuclease activity of 2-substituted het- in-vitro antimicrobial studies of Co(II), Ni(II), Cu(II), Mn(II) and Fe(III)
eroaromatic thiosemicarbazones and semicarbazone copper(II) complexes. complexes. Int. J. Electrochem. Sci. 2009, 4, 717–729.
Transit. Metal Chem. 2000, 25, 154–160. 36. Singh, D.P.; Kumar, K.; Rimpi, M.N. C. Spectroscopic studies and antibac-
33. Shakira, M.; Abbasia, A.; Khan, A.U.; Khan, S.N. A series of transition terial activities of some new 16-membered octaazamacrocyclic complexes
and non-transition metal complexes from a N4 O2 hexadentate Schiff base derived from thiocarbohydrazide and pentane-2, 4-dione. Spectrochim. Acta
ligand: synthesis, spectroscopic characterization and efficient antimicrobial Part A 2011, 78, 629–634.
activities. Spectrochim. Acta Part A 2011, 78, 29–35. 37. Mohamed, G.G.; Badawya, M.A.; Omara, M.M.; Nassar, M.M.; Kamela,
34. Sangamesh, A.P.; Vinod, H.N.; Ajaykumar, D.K.; Prema, S.B.: DNA cleav- A.B. Synthesis, spectroscopic, thermal and biological activity studies on
age, antimicrobial, spectroscopic and fluorescence studies of Co(II),Ni(II) triazine metal complexes. Spectrochim. Acta Part A 2010, 77, 773–781.
and Cu(II) complexes with SNO donor coumarin Schiff bases. Spectrochim. 38. Sarkara, S.; Dey, K. A series of transition and non-transition metal com-
Acta Part A 2010, 75, 347–354. plexes from a N4 O2 hexadentate Schiff base ligand: synthesis, spectro-
35. Ajay Kumar, D.K.; Sangamesh, A.P.; Prema, S.B. Electrochemical prop- scopic characterization and efficient antimicrobial activities. Spectrochim.
erties of some transition metal complexes: synthesis, characterization and Acta Part A 2010, 77, 740–748.
Downloaded by [Universita degli Studi di Torino] at 17:09 18 July 2013