Synthesis and Reactivity in Inorganic, Metal-Organic, and

Nano-Metal Chemistry

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Synthesis and Reactivity of 1-[(2-

methoxy)benzene]- 3-[benzothiazole]Triazene With
Copper(II) or Cobalt(II) Chloride

Qi-ying Lv , Wei Li & Shu-zhong Zhan

To cite this article: Qi-ying Lv , Wei Li & Shu-zhong Zhan (2012) Synthesis and Reactivity of 1-
[(2-methoxy)benzene]- 3-[benzothiazole]Triazene With Copper(II) or Cobalt(II) Chloride, Synthesis
and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:5, 764-769, DOI:
10.1080/15533174.2011.615786

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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:764–769, 2012
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C Taylor & Francis Group, LLC

ISSN: 1553-3174 print / 1553-3182 online

DOI: 10.1080/15533174.2011.615786

Synthesis and Reactivity of 1-[(2-methoxy)benzene]-

3-[benzothiazole]Triazene With Copper(II) or Cobalt(II)
Chloride
Qi-ying Lv, Wei Li, and Shu-zhong Zhan
College of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou,
P. R. China

as these compounds can serve as a monodentate (a),[1,2] a biden-

A new triazene, 1-[(2-methoxy)benzene]-3-[benzothiazole] tate chelating (b),[3–5] or a bridging ligand (c) (Scheme 1).[1,2,6–8]
triazene (HL), has been synthesized and charaterized. In the With this mind, we extended our interests to the synthesis and
presence of Et3 N, the reaction of HL and CuCl2 ·2H2 O or their reactivity with transition metals of new triazenide ligands
CoCl2 ·6H2 O gives the triazenide complexes [Cu4 L
4 (µ-OMe)4 ] 1
(L
1-[benzothiazole]triazene ion) and [Co2 L4 ] 2, respectively. The (such as Scheme 1).
X-ray crystal structures of both complexes have been obtained. As part of this research, a new triazenide ligand, namely
Magnetic studies indicate significant antiferromagnetic coupling 1-[(2-methoxy)benzene]-3-[benzothiazole]triazene (HL), has
between the copper(II) centers or cobalt(II) centers for complexes been synthesized from the reaction of o-anisidine, sodium ni-
1 and 2, with coupling constants (J) of –587 cm−1 for 1 and –147 trite, and 2-aminobenzothiazole. In the presence of Et3 N, the re-
cm−1 for 2. Complex 2 shows one reversible one-electron redox
wave at –0.835 V, and one irreversible oxidation at –0.193 V, which action of H2 L and CuCl2 ·2H2 O or CuCl2 ·2H2 O or CoCl2 ·6H2 O
are in accord with the redox potentials of [CoIII-CoII]/[CoII-CoII] affords the complex [Cu4 L 4 (µ-OMe)4 ] 1 or [Co2 L4 ] 2, respec-
and [CoIII-CoIII]/[CoII-CoII] couples, respectively. tively. In this paper, we present the synthesis and characteri-
zation of H2 L, its complexes 1 and 2, as well as the possible
Keywords electrochemical property, C-N bond cleavage, crystal procedure of the formation of 1-[benzothiazole]triazene (L )
structures, magnetic properties, reactivity of triazene from HL thereof.

EXPERIMENTAL
INTRODUCTION
A fundamental aim of coordination chemistry is the assem- Physical Measurements
1
bly of compounds that exhibit novel properties. An approach H NMR spectrum was measured on a Bruker AM 500 spec-
toward this important goal is the preparation of unique ligands trometer in CDCl3 (Switzerland). Magnetic susceptibility data
that impart novel chemistry when incorporated into the metal for crystal samples were collected in the temperature range of
coordination sphere. By designing the appropriate ligands, we 2–300 K with a Quantum Design SQUID Magnetometer MPMS
can chelate metal centers in special frame and control the elec- XL-7 (USA). Effective
magnetic moments were calculated by
tron withdrawal from the metal ion core, thereby modifying the equation µeff = g[ ZS(S+1)]1/2, where χ M is the molar
the intramolecular exchange interactions. The use of different magnetic susceptibility. The electrolytic cell used was a con-
bridging and polydentate ligands has afforded an impressive ar- ventional three-compartment cell, in which a Pt working elec-
ray of nuclear coordination complexes with new architectures. trode, a Pt auxiliary electrode, and a saturated calomel electrode
Among them, the triazenide ligands have attracted our attention, (SCE) was employed. The CV measurement was performed
at room temperature using 0.10 mol·L−1 tetrabutylammonium
hexafluorophosphate (TBAP) as the supporting electrolyte.
Synthesis of 1-[(2-methoxy)benzene]-3-[benzothiazole]
Received 17 May 2011; accepted 16 August 2011.
This work was supported by the Research Foundation for Re- Triazene (HL)
turned Chinese Scholars Overseas of Chinese Education Ministry (No. O-anisidine (1.23 g, 10 mmol) in water (5 mL) was mixed
B7050170), the National Science Foundation of China (No. 20971045), with 1 mol·L−1 HCl 30 mL (30 mmol) at 0◦ C. An aqueous
and the Student Research Program (SRP) of South China University of solution (15%) of sodium nitrite (15 mmol) was added dropwise
Technology.
Address correspondence to Shu-zhong Zhan, College of Chem- with stirring. Once the amine was dissolved, a 15% solution of
istry & Chemical Engineering, South China University of Technology, 2-aminobenzothiazole in ethanol (1.50 g, 10 mmol) was added
Guangzhou 510640, P. R. China. E-mail: [email protected] at 0◦ C and stirred for 8 h. The reaction mixture was neutralized

764
 TRANSITION METAL COMPLEXES 765

TABLE 1
Crystallographic data for complexes 1 and 2
Parameter 1 2
Empirical formula C32 H28 Cu4 N16 O4 S4 C56 H44 Co2 N16 O4 S4
SCH. 1. Generic triazenido binding modes and new triazenes. Formula weight 1083.18 1251.17
λ(Å) 0.71073 0.71073
Temperature (K) 295 150
Crystal system triclinic monoclinic
with a 15% aqueous of CH3 CO2 Na to give a yellow precipitate. Space group P-1 C2/c
The reaction mixture was filtered, and the solid was purified by Unit cell dimension (Å,◦ )
crystallization at –4◦ C from 9:1 ethyl acetate/hexanes to obtain a 8.976(6) 31.977(3)
yellow crystals. The crystals were collected and dried in vacuo b 11.950(8) 22.7264(19)
(1.89 g, 67%). Anal. Calcd. for C14 H12 N4 OS: C, 59.16; H, 4.23; c 12.065(8) 20.8859(17)
N, 19.72. Found: C, 58.67; H, 4.19; N, 19.90. 1H NMR (CDCl3 , α 91.318(8) 90.00
ppm): δ 13.04 (s, 1H, N-H), 8.09 (d, J = 2.7 Hz, 1H, Ar), 8.03 β 100.804(8) 120.032(2)
(d, J = 2.5 Hz, 1H, Ar), 7.96 (d, J = 2.8 Hz, 1H, Ar), 7.82 (d, J γ 102.832(8) 90.00
= 2.5 Hz, 1H, Ar), 7.64 (t, J = 5.2 Hz, 1H, Ar), 7.47 (t, J = 5 Z 1 8
Hz, 1H, Ar), 7.39 (t, J = 5 Hz, 1 Hz, Ar), 7.21 (t, J = 5 Hz, 1 Dc(Mgm−3) 1.455 1.265
Hz, Py), 3.99 (s, 3H, -OCH3 ). F(000) 544 5136
θ range for data 2.37–25.50◦ 3.07–26.00◦
collection
Synthesis of Complex [Cu4 (␮-OMe)4 L
4 ] 1 Reflections 8066/4515 28798/12507
To a solution of HL (0.29 g, 1.0 mmol) and triethylamine collected/unique
(0.10 g, 1.0 mmol) in ethanol (25 ml), CuCl2 ·2H2 O (0.17 g, Data/restraints/ 4515/0/271 12507/0/744
1.0 mmol) was added and stirred for 30 min. Slow evaporation parameters
afforded deep green crystals, which were collected and dried in Goodness-of-fit on 1.045 0.971
vacuo (0.15 g, 54.1%). Anal. Calcd. for C16 H14 Cu2 N8 O2 S2 : C, F2
35.45; H, 2.59; N, 20.68. Found: C, 35.89; H, 2.85; N, 20.12. Final R indices R1 = 0.0403 R1 = 0.0868
[I > 2σ (I)]
wR2 = 0.1166 wR2 = 0.2280
Synthesis of Complex [Co2 L4 ] 2 R ı́ndices (all data) R1 = 0.0565 R1 = 0.1479
The procedure was performed in the same way as that for the wR2 = 0.1237 wR2 = 0.2770
synthesis of complex 1 except that CuCl2 ·2H2 O was replaced
by CoCl2 ·6H2 O, complex 2 was obtained in 54.1% yield (0.15
g). Calcd for C56 H44 Co2 N16 O4 S4 : C, 53.71; H, 3.52; N, 17.90. RESULTS AND DISCUSSION
Found: C, 52.87; H, 3.46; N, 18.41.
Synthesis
The reaction of o-anisidine, sodium nitrite, and 2-
X-Ray Crystallography aminobenzothiazole provided a triazene (HL). Complexes 1
Data were collected with a Bruker SMART CCD area de- and 2 were obtained by the reaction of HL and CuCl2 ·2H2 O
tector using graphite monochromated Mo-K radiation (0.71073 or CoCl2 ·6H2 O, respectively. Interestingly, the reaction of
Å). All empirical absorption corrections were applied by using HL and CuCl2 ·2H2 O in the presence of Et3 N provided
the SADABS program.[9] The structures were solved using di- complex 1 [Cu4 L 4 (µ-OMe)4 ] with a new L− ligand (1-
rect methods and the corresponding non-hydrogen atoms were [benzothiazole]triazene ion) (Scheme 2). The procedure of the
refined anisotropically. All the hydrogen atoms of the ligands formation of L− can be illustrated by Scheme 3, the treat-
were placed in calculated positions with fixed isotropic thermal ment of HL with Et3 N gives a triethylammonium triazenide salt
parameters and included in the structure factor calculations in ([Et3 NH]L) A.[11] Furthermore, the rearrangement of A provides
the final stage of full-matrix least-squares refinement. All cal- an intermediate B. Finally, C-N bond cleavage of HL affords a
culations were performed using the SHELXTL computer pro- new L− ligand, accompanied loss of phenyl methyl ether.
gram.[10] Table 1 lists details of the crystal parameters, data
collection, and refinement for complexes 1 and 2. The selected Structures of Complexes 1 and 2
bond distances and angles for complexes 1 and 2 are listed in As shown in Figure 1, the metallic core comprises four cop-
Tables 2 and 3. per centers, all in distorted planar geometries, arranged in a
766 Q.-Y. LV ET AL.

TABLE 2
Selected bond distances (Å) and angles (◦ ) for complex 1
Cu(1)-N(5) 1.969 (3) Cu (1)-N(2) 2.025 (3)
Cu(2)-N(6) 2.009 (3) Cu(2)-N(1) 1.979 (3)
Cu(2)-O(1)# 1.927 (3) Cu(2)-O(2)# 1.907 (3)
Cu(2)-Cu(1) 3.0163 (17) Cu (2)-Cu(1)# 2.9697 (15)
O(1)-Cu(1)-O(2) 77.09 (12) Cu(1)-O(1)-Cu(2)# 100.89 (12)
Cu(1)-(O(2)-Cu(2)# 102.33 (13)
Cu(1)-Cu(2)-Cu(2)#-Cu(1)#1 0 O(1)-Cu(1)-Cu(2)#-O(2) 5.91
Symmetry transformations used to generate equivalent atoms: –x, –y + 1, –z + 1.

square-planar array with the torsion angle Cu(1)-Cu(2)-Cu(2)#- 3.0163(17) Å is longer than that found in Cu2 (Ac)3 (triazenide)
Cu(1)#1 of 0◦ . The structure of 1 consists of two symmetry- (2.5316(6) Å).[15]
related di-µ2 -methoxo-bridged copper(II) dimeric units (Cu(1)- As shown in Figure 2, the structure of complex 2 shows the
Cu(2)# and Cu(1)-Cu(2)#). The Cu-O bond lengths are within L− ligand doesn’t bind in a bis(bidentate) manner bridging the
the range of 1.906(3) to 1.927(3) Å, and Cu-O-Cu angles fall in two cobalt centers, but coordinate to the cobalt center by two
100.87(12) to 102.33(13)◦ . terminal N atoms of each L− ligand. The average N-N-N angle
Similar to the “roof-shaped” Cu2 (µ2 -OMe)2 geometry of 108.4(5)◦ and the average N-N bond length of 1.3219 Å agree
found in [Cu4 Ldur(µ2 -OMe)4 ]4+ (Ldur = 1,4,7-triazacyclonon) with those reported for the Co(dpt)3 complex.[17]
complex,[12] the Cu2 O2 bridging units in complex 1 also Two cobalt atoms are bridged by four L− ligands to form two
adopt bent, or “roof-shaped” conformations. This distor- 12-membered Co2 N8 C2 rings, which lie vertically. Each cobalt
tion is evident from the torsion angle O(1)-Cu(1)-Cu(2)#- sphere may be described as a distorted octahedral geometry
O(2) of 5.97◦ . In the case of 1, the Cu···Cu separa- with axial and equatorial ligands, the axial atoms being N(1)
tion (2.9697 Å) is similar to that found in [Cu4 Ldur(µ2 - and N(9) for Co(1) and N(5) and N(13) for Co(2). The Co-Nax
OMe)4 ]4+ (2.962(1) Å). “Roof-shaped” Cu2 O2 cores have distances are homogeneous with an average value of 2.133 Å,
been observed in [Cu2 (C6 H11 NH2 )4 (µ2 -OH)2 ](ClO4 )2 [13] and but the Co-Neq distances are in the 2.148–2.226 Å range for
[Cu2 (CH3 NH2 )4 (µ2 -OH)2 ](SO4 )·H2 O,[14] and Cu···Cu dis- both cobalt spheres.
tances of 2.934(8) and 2.782(5) Å, respectively.
The two Cu2 O2 units are capped by four L− ligands. The Magnetic Properties of Complexes 1 and 2
bond distances of between Cu and N fall in the range 1.969(3) The magnetic behavior of 1 is shown in Figure 3 in the form
to 2.025(3) Å, which are similar to those found in copper(II) tri- of χ M versus T or χ M T versus T. Copper(II), which has the
azenide complexes 1.973 to 2.088 Å.[15,16] The Cu···Cu distance, d9 configuration, is expected to exhibit paramagnetic behavior.

TABLE 3
Selected bond distances (Å) and angles (◦ ) for complex 2
Co(1)-N(9) 2.124 (5) Co(1)-N(1) 2.136 (5)
Co(1)-N(6) 2.148 (5) Co(1)-N(16) 2.179 (5)
Co(1)-N(8) 2.187 (6) Co(1)-N(14) 2.208 (6)
Co(2)-N(5) 2.120 (6) Co(2)-N(13) 2.146 (5)
Co(2)-N(2) 2.148 (5) Co(2)-N(12) 2.172 (5)
Co(2)-N(10) 2.184 (5) Co(2)-N(4) 2.226 (5)
N(2)-N(3) 1.325 (6) N(3)-N(4) 1.304 (7)
N(6)-N(7) 1.371 (7) N(7)-N(8) 1.289 (6)
N(10)-N(11) 1.330 (7) N(11)-N(12) 1.295 (7)
N(14)-N(15) 1.340 (7) N(15)-N(16) 1.321 (7)
N(1)-Co(1)-N(9) 166.85 (19) N(14)-Co(1)-N(16) 58.7 (2)
N(6)-Co(1)-N(8) 59.60 (18) N(5)-Co(2)-N(13) 166.96 (19)
N(10)-Co(2)-N(12) 58.66 (18) N(2)-Co(2)-N(4) 58.48 (18)
N(4)-N(3)-N(2) 108.9 (5) N(8)-N(7)-N(6) 108.2 (5)
N(12)-N(11)-N(10) 108.7 (5) N(16)-N(15)-N(14) 107.8 (5)
 TRANSITION METAL COMPLEXES 767

FIG. 1. X-ray structure of complex 1 (color figure available online).

SCH. 2. Schematic representation of the synthesis of HL, 1 and 2.

sis of the Heisenberg model H = –2JS1 ·S2 . The molar magnetic
susceptibility for Cu(II)-Cu(II) units is expressed as Eq. 1.[18]
However, complex 1 is diamagnetic at 300 K, because of strong   −1
coupled interactions between copper(II) ions. Nβ 2 g 2 1 2J Nβ 2 g 2
χM = 1 + exp − (1−ρ)+ ρ+N α
Two different exchange pathways can occur in complex 1: 3kT 3 kT 4kT
Cu-N-C-N-Cu and Cu-O-Cu. To explain the magnetic behavior [1]
of complex 1, its structure can consequently be reduced to a cen- Least-squares fitting of the experimental data led to J = –587
tral Cu4 N4 O4 core. The Cu-N-C-N-Cu pathway in complex 1, is cm−1, g = 2.1, Nα = 1.1 × 10−3 cm3mol−1, and ρ = 0.001.
assumed to have only a second-order effect on the magnetic ex- As a consequence, there are very strong antiferromagnetic ex-
change between the copper centers. The tetranuclear copper(II) change interactions between copper(II) ions. The major factor
complex 1 can be formally divided into two dinuclear Cu2 O2 controlling the exchange interactions in hydroxy-, alkoxy-, and
subunits. The interdimer coupling via nitrogen atoms is assumed phenoxy-bridged copper(II) is the Cu-O-Cu bridge angle.[19,20]
to be weaker than the intradimer exchange interactions via the The average Cu-O-Cu bridge angle of 102◦ for 1 would re-
oxygen atoms (µ-OMe). Hence the data can be fitted on the ba- sult in an approximate J value of –350 cm−1 according to the

SCH. 3. The possible mechanism of the formation of L .

768 Q.-Y. LV ET AL.

FIG. 4. Plot of the χ M T versus T and χ M versus T (inset) for complex 2 at

2000 Oe. Solid line corresponds to the best fit.
FIG. 2. X-ray structure of complex 2 (color figure available online).
two isolated CoII ions (S = 3/2) and decreases linearly with
decreasing temperature between 300–2 K, and reaches to 0.227
empirical equation reported in the literature and it deviates ap-
cm3Kmol−1 at 2.0 K.
preciably from the experimentally determined value of –585
The magnetism of 2 can be well reproduced by a modified
cm−1 for complex 1. A possible reason for the strong exchange
Bleaney-Bowers Eq. 2.[24]
coupling in complex 1 is that the methoxide ion, with shorter Cu-
  −1
O (average 1.923 Å) distance and a larger Cu(1)-O(5)-Cu(2)# 2Nβ 2 g 2 J Nβ 2 g 2
angle (102.89◦ ) than those with the phenoxide ion, provides a χM = 3 + exp − (1−ρ)+ ρ+2N α
kT kT 2kT
better pathway for antiferromagnetic exchange coupling.[21–23] [2]
The magnetic behavior of complex 2 is shown in Figure 4 Least-squares fitting of the experimental data led to J =
in the form of χ M T versus T or χ M T versus T. With decreas- –147 cm−1, Nα = 7.1 × 10−3 cm3mol−1, and ρ = 0.007. As
ing temperature, the χ M T value decreases rapidly in an unusual a consequence, there are strong antiferromagnetic exchange in-
linear fashion. This behavior can be ascribed to an antiferro- teractions between Co(II) ions.
magnetic interaction modified by the contribution of anisotropic
exchange. The value of χ M T at 300 K, 5.16 cm3Kmol−1 (6.42 Electrochemical Property of Complex 2
µB ), is larger than the value of 3.75 cm3Kmol−1 (5.48 µB ) of The electrochemical property of complex 2 was measured by
cyclic voltammetry in CH3 CN. As shown in Figure 5, complex

FIG. 3. Plot of the χ M T versus T and χ M versus T (inset) for complex 1 at FIG. 5. CV of complex 2 in CH3 CN/0.1 mol·L−1 [Bu4 N]PF6 at 100 mV s−1
3000 Oe. Solid line corresponds to the best fit. scan rate.
 TRANSITION METAL COMPLEXES 769

2 shows one reversible one-electron redox wave at –0.835 V, 8. Lei, W.-J.; Tan, X.-W.; Han, L.-J.; Zhan, S.-Z.; Li, B.-T. Design, synthesis
and one irreversible oxidation at –0.193 V, which are in accord and properties of a trinuclear copper(I) cluster with a triazenide ligand.
Inorg. Chem. Commun. 2010, 13, 1325–1328.
with the redox potentials of [CoIII-CoII]/[CoII-CoII] and [CoIII-
9. Sheldrick, G.M. SADABS, Program for Empirical Absorption Correction of
CoIII]/[CoII-CoII] couples, respectively. Area Detector Data; University of Göttingen: Göttingen, Germany, 1996.
1-[(2-methoxy)benzene]-3-[benzothiazole]triazene (HL) 10. Sheldrick, G.M. SHELXS 97, Program for Crystal Structure Refinement;
was synthesized by the reaction of o-anisidine and 2- University of Göttingen: Göttingen, Germany, 1997.
aminobenzothiazole, using half an equivalent of sodium nitrite. 11. Virag, A.; Meden, A.; Kocevar, M.; Polanc, S. Synthesis and characteriza-
tion of new triazenide salts. J. Org. Chem. 2006, 71, 4014–4017.
This technique is facile and gives HL in high yield (67%). HL
12. Graham, B.; Hearn, M.T.W.; Junk, P.C.; Kepert, C.M.; Mabbs, F.E.;
can chelate and bridge copper or nickel centers to give two Moubaraki, B.; Murray, K.S.; Spiccia, L. Syntheses, crystal structures,
complexes 1 and 2, which reveal significant antiferromagnetic magnetic properties, and EPR spectra of tetranuclear copper(II) complexes
character. Currently we are exploring this area further, including featuring pairs of “roof-shaped” Cu2 ×2 dimers with hydroxide, methoxide,
the design and synthesis of new triazenes, as well as their and azide bridges. Inorg. Chem. 2001, 40, 1536–1543.
13. Charlot, M.F.; Jeannin, S.; Jeannin, Y.; Kahn, O.; Lucrece-Aubal,
reactivity with metals.
J.; Martin-Frere, J.S. Crystal structure and magnetic properties of
tetrakis(cyclohexylamine)di-.mu.-hydroxo-dicopper(II) perchlorate. The
first example of a roof-shaped hydroxo-bridged copper(II) dimer. Inorg.
SUPPLEMENTARY MATERIALS Chem. 1979, 18, 1675–1681.
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crystallographic data for complexes 1, and 2, respectively. roof-shaped hydroxo-bridged copper(II) dimmers. Inorg. Chem. 1980, 19,
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www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cam- sis and structure of a dinuclear copper complex of a bis(bidentate)triazenide
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