Synthesis and Crystal Structure of A Novel Mixed-valent Tri-copper Complex of 4′-p-Tolyl-2,2′:6′,2′-terpyridine

Article abstract of DOI:10.1080/15533170903095052

Two copper complexes of 4′-p-tolyl-2,2′:6′,2′- terpyridine (ttpy), namely, monomer [Cu^II(ttpy)Cl₂] (1) and trinuclear complex [Cu^II(ttpy)Cl₂]. [Cu ^IICu^I(ttpy)Cl₃] (2), were prepared through solvothermal synthesis and structurally determined by single crystal X-ray diffraction. Compound 1 obtained by another way before was firstly solvothermally synthesized and structurally investigated herein. In 1 metal center Cu²⁺ ligated by a ttpy molecule and two chloride ions is in a distorted square pyramidal geometry. However, complex 2 is a novel mixed-valent tri-copper complex which contains a monomeric [Cu^II(ttpy)Cl ₂] part being very similar to 1, and a mixed-valent chloride-bridged di-nuclear [Cu^IICu^I(ttpy)Cl₃] part, presented interesting co-crystallization behavior.

Full text of DOI:10.1080/15533170903095052

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Synthesis and Crystal Structure of A Novel Mixed-
valent Tri-copper Complex of 4′-p-Tolyl-2,2′:6′,2′-
terpyridine
a
a
a
a
a
Song Wang , Bao-Ding Li , Rui-Ying Wang , Ben-Lai Wu & Hong-Yun Zhang
a
Department of Chemistry , Zhengzhou University , Zhengzhou, P. R. China
Published online: 30 Dec 2009.
To cite this article: Song Wang , Bao-Ding Li , Rui-Ying Wang , Ben-Lai Wu & Hong-Yun Zhang (2009) Synthesis and Crystal
Structure of A Novel Mixed-valent Tri-copper Complex of 4′-p-Tolyl-2,2′:6′,2′-terpyridine, Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 39:6, 355-359
To link to this article: http://dx.doi.org/10.1080/15533170903095052
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 39:355–359, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533170903095052
Synthesis and Crystal Structure of A Novel Mixed-valent
Tri-copper Complex of 4’-p-Tolyl-2,2’:6’,2’-terpyridine
Song Wang, Bao-Ding Li, Rui-Ying Wang, Ben-Lai Wu, and Hong-Yun Zhang
Department of Chemistry, Zhengzhou University, Zhengzhou, P. R. China
DNA has also been reported.[6,7] However, its accurate structure
Two copper complexes of 4 -p-tolyl-2,2 :6 ,2 -terpyridine has not been characterized by single crystal X-ray diffraction up
ꢀ
ꢀ
ꢀ
ꢀ
II
(
ttpy), namely, monomer [Cu (ttpy)Cl2] (1) and trinuclear
to now. Another complex [Cu(ttpy)2](ClO4)2, which contains
II
II
I
complex [Cu (ttpy)Cl2]. [Cu Cu (ttpy)Cl3] (2), were prepared
through solvothermal synthesis and structurally determined by
single crystal X-ray diffraction. Compound 1 obtained by an-
other way before was firstly solvothermally synthesized and struc-
six-coordinated copper in an axially-compressed distorted
octahedron ligated with two terpyridyine ligands in mer
coordination fashion, has also been reported.[ Furthermore,
9]
2
+
turally investigated herein. In 1 metal center Cu ligated by a ttpy complexes containing ttpy display intriguing co-crystallization
molecule and two chloride ions is in a distorted square pyramidal
geometry. However, complex 2 is a novel mixed-valent tri-copper
complex which contains a monomeric [Cu (ttpy)Cl2] part being
very similar to 1, and a mixed-valent chloride-bridged di-nuclear
behavior as crystallized from solution, which provides helpful
insight for further understanding how to control crystal.
Very recently, Bray et al. has reported two ttpy complexes
II
II
I
[
Cu(ttpy)(NO3)2][Cu(ttpy)(NO3)(EtOH)]NO3·MeOH and [Cu-
[
Cu Cu (ttpy)Cl3] part, presented interesting co-crystallization
ꢀ
ꢀ
behavior.
(ptpy) NO ] [Cu(ttpy)(NO ) ](NO ) (ptpy = 6 -p-tolyl-2,2 :
2
3 2
3 2
3 2
ꢀꢀ
ꢀ
2
,4 -terpyridine) present interesting co-crystallization
ꢀ
[10]
Keywords co-crystal, crystal structure, solvo-thermal synthesis, 4 - behavior.
ꢀ
ꢀ
ꢀ
p-Tolyl-2,2 :6 ,2 -terpyridine
ꢀ
In this context, our group deliberately prepared 4 -p-tolyl-
ꢀ
ꢀ
ꢀ
[11,12]
2
,2 :6 ,2 -terpyridine,
and used it to assemble with cop-
◦
per(II) under solvo-thermal ethanol systems at 135 C. The reac-
tions of ttpy with CuCl2 gave rise to a monomer [Cu (ttpy)Cl2]
II
INTRODUCTION
Terpyridine molecules with three nitrogen atoms acting as (1), and with Cu(OH) , YCl and D-camphoric acid gave rise
2
3
II
II
I
tridentate ligands to coordinate with various transition metal to a novel trinuclear complex [Cu (ttpy)Cl ][Cu Cu (ttpy)Cl ]
2
3
[
1,2]
ions have been extensively studied.
The resulting complexes (2). The referred complex 1, which was obtained by the dif-
often have unusual electronic, photophysical and/or structural ferent way in some study,[
6,7]
is structurally characterized by
properties. Therefore, the metal coordination chemistry of X-ray diffraction analysis first herein. The trinuclear complex 2
ꢀ
ꢀ
ꢀ
II
2
4
,2 :6 ,2 -terpyridine and its substituted derivatives, such as which consists of two parts: a monomeric [Cu (ttpy)Cl ] part
2
ꢀ
ꢀ
ꢀ
ꢀ
-p-tolyl-2,2 :6 ,2 -terpyridine (ttpy) have received a great being very similar to 1, and a mixed-valent chloride-bridged
deal of attention in recent decades.
[
3−5]
II
I
Especially, copper(II) di-nuclear [Cu Cu (ttpy)Cl ] part, is an intriguing example of
3
complexes with terpyridine ligands have been focused on by mixed-valent copper complex with interesting co-crystallization
[
6−8]
chemists due to their special catalysis and biologic activity.
behavior.
II
For example, the compound [Cu (ttpy)Cl2] was isolated as the
model of an enzymatic study, and the results showed that it is an
inhibitor for furin. Further investigation of its interaction with
EXPERIMENTAL
Materials and Measurements
Cu(OH)2 was prepared by adding dropwise ammonia to a so-
◦
lution of CuSO4 at 60 C until precipitation was dissolved, and
Received 11 March 2009; accepted 25 April 2009.
We gratefully acknowledge financial support from the National then a solution of NaOH (2 mol/L) was dropwise added into the
Natural Science Foundation of China (20771094), the Science and
resultant blue solution concomitantly with a lot of blue precip-
Technology Key Task of Henan Province (0524270061) and the China
itate. After filtered, the precipitate was washed with abundant
Postdoctoral Science Foundation (20070410877).
water and dried naturally (yield 87%). Other chemicals were
Address correspondence to Ben-Lai Wu, Department of Chem-
of reagent grade without further purification. Melting point (m.
p.) was measured using a Bei Jing Ke Ji Dian Guang Yi Qi
istry, Zhengzhou University, Zhengzhou, 450052, China. E-mail:
wbl@zzu.edu.cn; wzhy917@zzu.edu.cn
355

356
S. WANG ET AL.
Chang XT4A apparatus. IR spectra were recorded on a FTS-40 57.71, H 3.74, N 9.18; found: C 57.61, H 3.70, N 9.24. Selected
−
1
infrared spectrophotometer with KBr pellets in the range 4000– IR (KBr, cm ): 3060, 1604, 1554, 1475, 1426, 1407, 1022,
4
3
−1 1
00 cm . H NMR spectrum was recorded on a Bruker DPX- 791, 582, 510, 470.
00 spectrometer operating at 300 MHz, and element analyses
were performed with a Carlo-Erba 1106 elemental analyzer.
II
II
I
Preparation of [Cu (ttpy)Cl2][Cu Cu (ttpy)Cl3] (2)
ꢀ
ꢀ
ꢀ
ꢀ
Preparation of the Ligand 4 -p-tolyl-2,2 :6 ,2 -terpyridine
Cu(OH)2 (0.06 mmol), YCl3 (0.1 mmol), D-camphoric acid
0.2 mmol), ttpy (0.2 mmol), and ethanol (8 mL) were mixed in
a 23-mL teflon cup, and the mixture was stirred for 10 min. The
vessel was then sealed and heated at 135 C for 3 days. When the
autoclave was allowed to cool to room temperature, green needle
crystals 2 with a little unknown light yellow precipitate was
obtained. Elemental analysis calcd (%) for C44H34Cl5Cu3N6: C
2.08, H 3.38, N 8.28; found: C 52.13, H 3.35, N 8.30. Selected
IR (KBr, cm ): 3015, 2969, 1603, 1555, 1471, 1425, 1403,
020, 829, 790.
ꢀ
ꢀ ꢀ ꢀ
4
-p-tolyl-2,2 :6 ,2 -terpyridine ligand was prepared anal-
(
[
11,12]
ogously to the literature procedure.
16.5 g) was added to a solution of p-tolualdehyde (7.8 g) in
CH3OH (100 mL). 15% aqua KOH (10 mL) and conc. NH4OH
100 mL) were then added. The resulting solution was refluxed
for 2 days and vigorously stirred. Then the mixture was cooled
to room temperature, and extracted with CHCl3 (3 × 150 mL).
The organic layers were collected together and washed with
water (3 × 100 mL). After dried with MgSO4, the solvent was
removed by vacuo evaporation. The residue was recrystallized
from 95% ethanol to yied 8.43 g (41%) of light yellow crys-
2-Acetylpyridine
(
◦
(
5
−1
1
◦
−1
tals (m. p. 168 C). Selected IR (KBr, cm ): 3049, 1583, 1565,
1
1
3
8
466, 1386, 820, 789, 735, 504. H NMR (CDCl3) δ: 2.35 (s, X-Ray Structural Determination
H); 7.27 (d, 2H); 7.41 (m, 2H); 7.76 (d, 2H); 7.93 (m, 2H);
Crystallographic data for compounds 1 and 2 were collected
at 293(2) K on a Bruker APEX-II Area-detector diffractometer
.66 (m, 6H).
´
˚
with Mo-Ka radiation (λ = 0.71073A). Absorption corrections
II
Preparation of [Cu (ttpy)Cl2] (1)
were applied by using SADABS. The structure was solved with
CuCl2 (0.1 mmol), ttpy (0.2 mmol) and enthanol (8 mL) were direct methods and refined with full-matrix least-squares tech-
2
mixed in a 23-mL teflon cup, and the mixture was stirred for niques on F using the SHELXTL program package. All of the
◦
1
0 min. The vessel was then sealed and heated at 135 C for 3 non-hydrogen atoms were refined anisotropically. The hydro-
days. The autoclave was allowed to cool to room temperature. gen atoms were assigned with common isotropic displacement
Transparent green block crystals 1 were obtained with yield factors and included in the final refinement by using geometrical
of 83%. Elemental analysis calcd (%) for C22H17Cl2CuN3: C restrains. Crystal data are summarized in detail in Table 1.
TABLE 1
Crystallographic data and refinement parameters for the complex 1 and 2
Complex
1
2
Formula
C22H17Cl2Cu1N3
457.83
C44H34Cl5Cu3N6
1014.64
Monoclinic
P21/n
7.8133(8)
17.8917(18)
29.164(3)
90
Formula weight
Crystal system
Space group
Monoclinic
P21/n
7.8679(16)
23.659(5)
10.580(2)
90
97.03(3)
90
1954.6(7)
4
˚
a (A)
˚
b (A)
˚
c (A)
◦
α( )
◦
β( )
93.664(2)
90
4068.7(7)
4
◦
γ ( )
˚
3
Volume (A )
Z
DCalcd (g cm 3
−
)
1.556
1.656
F(000)
932
2048
Reflections collected/unique
Goodness-of-fit on F2
14151/3851 [R(int) = 0.0500] 30828/7577 [R(int) = 0.0830]
1.113
1.015
Final R indices [I >2sigma(I)]
R1 = 0.0577; wR2 = 0.1035
R1 = 0.0482; wR2 = 0.1004

A NOVEL MIXED-VALENT TRI-COPPER COMPLEX
357
RESULTS AND DISCUSSION
Synthesis
In previously studies, 1 was synthesized by mixing hot
methanolic solutions of CuCl2 and ttpy in equimolar quantities.
The authenticity of the complex was just ascertained from mass
spectral analysis.[ In this paper, 1 was obtained by solvother-
6,7]
◦
mal ethanol synthesis at 135 C, and presented as single crystals
satisfied with X-ray diffraction.
Complex 2 was accidently obtained in a comparatively mussy
system being accreted with a little light yellow precipitate. As
2+
well known, Cu prefers to coordinate with the nitrogen-donor
3+
ligands whereas Y prefers to coordinate with the oxygen-
donor ligand.[
13,14]
The possible procedure is presumed as fol-
lowing: firstly, Cu(OH)2 reacted with D-camphoric acid to pro-
3
+
2+
duce an intermediate. Then Y replaced the Cu from the
intermediate and it allowed the Cu2 to combine with ttpy to
+
create 2. The light yellow precipitate is likely to the compound
3+
+
FIG. 2. View of coordination geometry of 2, clearly presenting parts 1 and 2 in
containing Y , D-camphoric acid and ttpy. Clearly, Cu came
˚
◦
co-crystal. Selected bond lengths(A) and angles( ): Cu1–N1 2.063(4); Cu1–N2
.962(4); Cu1–N3 2.047(4); Cu1–Cl1 2.450(2); Cu1–Cl2 2.246(2); Cu2–N4
14−16]
However, there was only partial 2.032(4); Cu2–N5 1.935(4); Cu2–N6 2.034(4); Cu2–Cl3 2.213(1); Cu2–Cl4
2+
from the reduction of Cu by the excessive ttpy during the
1
[
solvothermal reaction.
2+
+
Cu which had been reduced into Cu in 2.
2.650(2); Cu3–Cl4 2.113(2); Cu3–Cl5 2.095(2); N1–Cu1–N2 78.29(15); N2–
Cu1–N3 78.27(15); Cl1–Cu1–Cl2 100.34(6); N4–Cu2–N5 79.30(16); N5–Cu2–
N6 79.36(16); Cl3–Cu2–Cl4 98.59(5); Cl4–Cu3–Cl5 178.91(9); Cu2–Cl4–Cu3
101.07(6).
Crystal Structure of Complexes 1 and 2
The coordination geometry and selected bond lengths and
angles of 1 are shown in Figure 1. The Cu2 ion is coordi-
+
−
dine rings and the phenyl are approximately planar with dihedral
angles between rings ranging from 1.9 to 5.0 .
nated by a tridentate ttpy molecule and two Cl ions to form
◦
a CuN3Cl2 sphere, which represents a twisted square pyramid.
The Cu–N bond length related to the central ring of ttpy is
slightly shorter than those to the terminal rings owing to the
constrained bite array in those tridentate ligands, and a similar
pattern is observed in complexes of 2,2 :6 ,2 -terpyridine with
a range of different metals ions. The three N atoms and one
Cl ion are located at the equatorial plane with relatively short
distances to the Cu center, while the other apical Cl (Cl1) is
found in comparatively great distance from the Cu ion. This
Complex 2 is a novel mixed-valent tri-copper compound.
Clearly, the crystal structure of 2, shown in Figure 2, includes
II
two independent parts, namely, part 1 [Cu (ttpy)Cl2] and part
II
I
ꢀ
ꢀ
ꢀ
2 [Cu Cu (ttpy)Cl ] in the asymmetry unit. Thus, the complex
3
[17]
belongs to a co-crystal. According to structure analysis, we can
II
−
get that one molecule of 2 contains two-typed [Cu (ttpy)Cl ]
2
2+
−
coordination units as the molecular formula of 1. In 2, the two
2+
2+
Cu (Cu1 and Cu2) have the same coordination mode. Each
2+
Cu cation is coordinated by a tridentate terpyridine molecule
is consistent with the geometry of [Cu(tpy)Cl2] complex (tpy =
−
ꢀ ꢀ ꢀ
[18]
and two Cl ions, and the formed CuN Cl geometry is best
3
2
2
,2 :6 ,2 -terpyridine) reported by W. Henke. The three pyri-
described as a square pyramid in a reasonable approximation,
even though the combining influence of the rigid tridentate ttpy
ligand and elongated Cu2–Cl4 bond, which is perhaps due to
the further coordination of Cl4 with cuprous Cu3, leads to slight
deviation from this geometry. Each terpyridyl molecule is ap-
proximately planar. In part 1 the phenyl ring of ttpy is twisted
from the basical plane of pyridine rings with the dihedral angle
◦
of 25.40(5) , and that in part 2 is comparatively less with the
◦
dihedral angle being 12.96(10) . Those are different from that
of 1 where the phenyl and pyridyl rings of the ttpy ligand are
II
I
almost coplanar. Notably, in the part 2 [Cu Cu (ttpy)Cl3], the
2
+
+
+
Cu (Cu2) and Cu (Cu3) are bridged through Cl4. The struc-
ture type of Cl–Cu –Cl appearing as counterion in the complex
had been reported.
Cu (Cu and Cu ) ions are bridged by a Cl ion is very rare.
Cu2–Cl4–Cu3 angle is 101.07(6) . The angle of Cl4–Cu3–Cl5
˚
FIG. 1. View of coordination geometry of 1. Selected bond lengths (A) and
[
19,20]
◦
But as far as we know, two mixed valent
angles ( ): Cu1–N1 2.052(3); Cu1–N2 1.940(3); Cu1–N3 2.035(3); Cu1–Cl1
+
2+
−
2
.522(1); Cu1–Cl2 2.228(1); N1–Cu1–N2 79.52(12); N2–Cu1–N3 78.93(12);
◦
Cl1–Cu1–Cl2 104.89(5).

358
S. WANG ET AL.
◦
is 178.91(9) with the atoms Cl4, Cu3 and Cl5 being in a line,
displaying a typical coordination geometry of cuprous ion. Ta-
ble 2 lists out the relevant Cu–Cl and Cu–N bond lengths in 1
and each part of 2, and the differential values of bond length
values in 1 minus the relevant bond length values in Part 1
II
II
I
[
Cu (ttpy)Cl2] or Part 2 [Cu Cu (ttpy)Cl3] of 2. Referred to 1,
Cu–Cl and Cu–N bond lengths take the opposite change in Part 1
II
II
I
[
Cu (ttpy)Cl2] and Part 2 [Cu Cu (ttpy)Cl3], respectively. The
˚
Cu2–Cl4 bond elongates 0.128 A in comparison with the Cu1–
Cl1 bond of 1, and bigger change degree perhaps results from
the affection of Cu3 to Cl4.
Very interestingly, some factors, such as the coordination of
−
2+
+
Cl ions to Cu ions in unequal positions, the unsymmetrical
pendant Cl–Cu –Cl group and the distortion of the phenyl ring
out the terpyridyl unit, lead to the isomerization of the part
II
II
I
1
[Cu (ttpy)Cl2] and part 2 [Cu Cu (ttpy)Cl3] in 2. Figure 3
shows all the enantiomers of two parts of 2 in theory, and thus
II
II
I
the tri-copper unit [Cu (ttpy)Cl2][Cu Cu (ttpy)Cl3] probably
has eight enantiomers, namely, A-C, A-D, A-E, A-F, B-C, B-D,
B-E and B-F. As shown in Figure 4, there lies offset face-to-face
π − π stacking between different parts of adjacent tri-copper
II
II
I
units, so the tri-copper units [Cu (ttpy)Cl2][Cu Cu (ttpy)Cl3]
FIG. 3. Illustration of the enantiomers of part 1 (a), and the enantiomers of pack up to form one dimensional chains along a axis. The
part 2 (b) in 2 in theory.
packing diagram shows that 2 contains four different chains
FIG. 4. View of face-to-face π–π stacking in 2, with relevant center–center distances of π − π stacking.

A NOVEL MIXED-VALENT TRI-COPPER COMPLEX
359
FIG. 5. The packing diagram of 2 with different packing type of enantiomers.
(
Figure 5): chain 1 and chain 2 adopt the same enantiomer type
9. Uma, V., Vaidyanathan, V.G., and Nair, B.U. Synthesis, structure, and DNA
binding studies of copper(II) complexes of terpyridine derivatives. Bull.
Chem. Soc. Jpn., 2005, 78, 845–850.
0. Bray, D.J., Clegg, J.K., Jolliffe, K.A., Lindoy, L.F., and Wei, G. Synthesis
and co-crystallisation behaviour of copper(II) complexes of two isomeric
p-tolyl-terpyridines. J. Coord. Chem., 2008, 61, 3–13.
A-F, and chain 3 and chain 4 adopt the same enantiomer type B-
E, but they have the opposite stretch along the packing direction,
respectively.
1
1
1. Ohr, K., McLaughlin, R.L., and Williams, M.E. Redox behavior of phenyl-
terpyridine-substituted artificial oligopeptides cross-linked by Co and Fe.
Inorg Chem., 2007, 46, 965–974.
CONCLUSIONS
II
II
I
The complex [Cu (ttpy)Cl2]·[Cu Cu (ttpy)Cl3] (2) was pre-
pared and characterized by X-ray diffraction and element anal- 12. Co1lin, J.P., Guillerez, S., Sauvage, J.P., Barigelletti, F., Cola, L.D.,
Flamigni, L., and Balzani, V. Photoinduced processes in dyads and tri-
ads containing a ruthenium(II)-bis(terpyridine) photosensitizer covalently
linked to electron donor and acceptor groups. Inorg. Chem., 1991, 30,
ysis. This is the first example of mixed valent copper complex
ꢀ
ꢀ
ꢀ
ꢀ
+
of 4 -p-tolyl-2,2 :6 ,2 -terpyridine, which contains chloride-
2+
bridged Cu and Cu , and two interesting co-crystallisation
parts (part 1 [Cu (ttpy)Cl2] and part 2 [Cu Cu (ttpy)Cl3]). Ad-
4
230–4238.
II
II
I
1
1
1
3. Crease, A.E., and Legzdins, P. The Lewis acidity of organolanthanides.
The interaction of cyclopenta-dienyl-lanthanides with some carbonyl and
nitrosyl complexes. J. Chem. Soc. Dalton Trans., 1973, 1501–1507.
4. Zhou, Y.F., Jiang, F.L., Yuan, D.Q., Wu, B.L., Wang, R.H., Lin, Z.Z., and
Hong, M.C. Copper complex cation templated gadolinium(iii)–isophthalate
frameworks. Angew. Chem., 2004, 43, 5665–5568.
II
ditionally, the reference complex [Cu (ttpy)Cl2] (1) was also
sovothermally prepared and characterized by X-ray diffraction
firstly.
5. Lo, S.M.F., Chui, S.S.Y., Shek, L.Y., Lin, Z., Zhang, X.X., Wen, G.H., and
Williams, I.D. Solvothermal synthesis of a stable coordination polymer with
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