Di - Chlorido-bis-[chlorido(4'-p-tolyl-2,2':6',2''-terpyridine-3 N,N',N'')nickel(II)]: A supra-molecular system constructed by C - H...Cl inter-actions

Article abstract of DOI:10.1107/S0108270109018812

The title complex, [Ni2Cl4(C22H17N3)2], was synthesized solvo-thermally. The mol-ecule is a centrosymmetric dimer with the unique Ni^II centre in a distorted octa-hedral N3Cl3 coordination environment. The chloride bridges are highly asymmetric.

Full text of DOI:10.1107/S0108270109018812

metal-organic compounds
the complexes exist in the form of mononuclear [M(ttp)2]n+,
except for the dinuclear manganese complex [Mn2(ꢁ1,1-
N3)2(N3)2(ttp)2] (Yu et al., 2007). Many metalloenzymes,
including nickel enzymes, employ a dinuclear active site
(Halcrow & Christou, 1994; Holm et al., 1996; Solomon et al.,
1996; Wilcox, 1996). Lack of one Ni atom in the dinuclear
active site can cause a reduction in catalytic activity or even
complete deactivation of the enzyme. Halide-bridged dinuc-
lear nickel complexes with nitrogen- and oxygen-containing
ligands are occasionally utilized in ethylene oligomerization
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
Di-l-chlorido-bis[chlorido(40-p-tolyl-
2,20:60,200-terpyridine-j3N,N0,N00)-
nickel(II)]: a supramolecular system
constructed by C—Hꢀ ꢀ ꢀCl interactions catalysis (Zhang et al., 2007; Sun et al., 2007). We present here
the first structure of
a dinuclear nickel(II) complex
constructed with ttp and chloride ligands, namely di-ꢁ-
chlorido-bis[chlorido(40-p-tolyl-2,20:60,200-terpyridine)nickel(II)],
(I).
Ying-Lin Chen, Ben-Zhen Li, Ping Yang and Jian-Zhong
Wu*
School of Chemistry and Environment, South China Normal University, Guangzhou
510006, People’s Republic of China
Correspondence e-mail: wujzh@scnu.edu.cn
Received 1 May 2009
Accepted 18 May 2009
Online 6 June 2009
The title complex, [Ni2Cl4(C22H17N3)2], was synthesized
solvothermally. The molecule is a centrosymmetric dimer
with the unique NiII centre in a distorted octahedral N3Cl3
coordination environment. The chloride bridges are highly
asymmetric. In the 40-p-tolyl-2,20:60,200-terpyridine ligand, the
p-tolyl group is perfectly coplanar with the attached pyridine
ring, and this differs from the situation found in previously
reported compounds; however, there are no ꢀ–ꢀ interactions
between the ligands. The terminal Cl atom forms four
intermolecular C—Hꢀ ꢀ ꢀCl hydrogen bonds with one methyl
and three methine groups. The methyl group also forms
intermolecular C—Hꢀ ꢀ ꢀꢀ interactions with a pyridine ring.
These nonclassical hydrogen bonds extend the molecule into a
three-dimensional network.
Complex (I) was obtained via a solvothermal reaction, but
no solvent molecule could be detected in the structure. The
complex molecule is arranged around an inversion centre and
exhibits a planar Ni2(ꢁ-Cl)2 diamond-like framework (Fig. 1).
The intramolecular Niꢀ ꢀ ꢀNi interatomic distance of
˚
3.6565 (6) A is typical of a binuclear nickel(II) complex and
virtually excludes any specific interaction between these
atoms. The coordination sphere of the NiII centre can be
interpreted as a distorted octahedron (Table 1), with ttp atoms
N1, N2 and N3 and the bridging atom Cl1 in the equatorial
plane and the other bridging atom Cl1i [symmetry code: (i)
ꢁx, ꢁy + 1, ꢁz] and the terminal atom Cl2 in axial positions.
The tridentate chelation results in the three ttp pyridine rings
being nearly coplanar, with the angles between the planes of
the two outer pyridine rings and that of the central pyridine
Comment
2,20:60,200-Terpyridine and its derivatives are well known
multidentate ligands. Among this ligand family, 40-p-tolyl-
2,20:60,200-terpyridine (ttp) plays an important role because it is
quite easy to prepare and derivatize via bromination and
oxidation, and the electron-donor nature of the terminal
methyl group is useful in certain cases. Hence, a number of
transition metal (M) complexes of ttp have been studied for a
variety of interesting properties, such as photophysics (Yosh-
ikawa et al., 2007; Abrahamsson et al., 2005), photochemistry
(Beley et al., 1991; Wilkinson et al., 2004), electrochemistry
(Al-Noaimi et al., 2004; Chamchoumis & Potvin, 1999; Bari-
gelletti et al., 2000; Collin et al., 1997; Mikel & Potvin, 2001),
magnetism (Duboc et al., 2006; Yu et al., 2007), DNA binding
(Uma et al., 2005; Jain et al., 2008; Bertrand et al., 2007; Jiang et
al., 2008) and supramolecular assembly (Zhou et al., 2007; Liu
et al., 2007; Messina et al., 2001; Yutaka et al., 2005; Hartshorn
& Zibaseresht, 2006; Bray et al., 2008; Yucesan et al., 2005). All
Figure 1
A view of the dinuclear unit of (I), showing the atom-labeling scheme.
Displacement ellipsoids are drawn at the 40% probability level and H
atoms are represented as small spheres of arbitrary radii. [Symmetry
code: (i) ꢁx, ꢁy + 1, ꢁz.]
m238 # 2009 International Union of Crystallography
doi:10.1107/S0108270109018812
Acta Cryst. (2009). C65, m238–m240

metal-organic compounds
distances fall slightly below the sum of van der Waals radii
˚
(2.95 A) and the C—Hꢀ ꢀ ꢀCl angles are fairly linear, consistent
¨
with criteria for C—Hꢀ ꢀ ꢀCl interactions (Aakeroy et al., 1999;
Freytag et al., 2000). Atoms H4, H7 and H17 from the same ttp
ligand surround atom Cl2 in a manner reminiscent of chela-
tion. The Ni—Cl coordination bond provides both charge
assistance and directionality for strengthening the C—Hꢀ ꢀ ꢀCl
interactions. The four Ni—Clꢀ ꢀ ꢀH angles are in the range 94–
105ꢂ, compatible with other C—Hꢀ ꢀ ꢀCl cases assisted by
terminal M—Cl bonds (Balamurugan et al., 2004).
Experimental
40-p-Tolyl-2,20:60,200-terpyridine (ttp) was prepared by an improved
¨
Krohnke condensation method (Wang et al., 2007; Collin et al., 1991).
A mixture of NiCl2ꢀ6H2O (0.2 mmol, 0.0476 g), ttp (0.2 mmol,
0.0646 g) and EtOH (10 ml) was placed in a 23 ml Teflon-lined
stainless steel vessel and heated under autogenous pressure at 412 K
Figure 2
for 3 d, followed by cooling to room temperature at a rate of 5 K hꢁ1
Light-green block-shaped crystals of (I) were obtained.
.
The packing in (I), showing the C—Hꢀ ꢀ ꢀCl (red dashed lines in the
electronic version of the paper) interactions. [Symmetry codes: (i) x, 32 ꢁ y,
1
2
ꢁ + z; (ii) 1 ꢁ x, 1 ꢁ y, 1 ꢁ z.]
Crystal data
3
˚
[Ni2Cl4(C22H17N3)2]
Mr = 905.99
V = 1931.2 (3) A
Z = 2
ring being 5.69 (13) and 4.22 (13)ꢂ, which is common for ttp
complexes. Compared to other ttp complexes, it is very unusal
that the substituent p-tolyl group is almost in the same plane
as the central pyridine ring; the torsion angles C7—C8—C16—
C17 and C9—C8—C16—C21 are 1.7 (5) and 2.4 (5)ꢂ, respec-
tively. The corresponding angles in previously reported
complexes involving ttp are significantly larger and only a few
are less than 10ꢂ [cf 4.58, 6.94 and 9.46ꢂ in Yucesan et al.
(2005), and 9.39ꢂ in Mikel & Potvin (2001)].
Of the two bridging Cl1 atoms around an NiII centre, that
trans to the central ttp pyridine ring is much closer to the Ni
atom than that trans to the terminal Cl2 atom (Table 1). This
reflects the difference in trans influence between pyridine and
chloride, which are ꢀ-acid and ꢀ-donor ligands in nature,
respectively. A similar difference in Ni—Cl distances is also
found in other Ni2(ꢁ-Cl)2Cl2 complexes in which the Ni atom
is hexacoordinated and which contain a pyridine ring opposite
one of two bridging Cl atoms [the two examples to date are:
Monoclinic, P21=c
a = 14.2218 (11) A
Mo Kꢃ radiation
ꢁ = 1.29 mmꢁ1
T = 298 (2) K
0.45 ꢃ 0.35 ꢃ 0.20 mm
˚
˚
b = 12.7866 (10) A
˚
c = 10.8659 (8) A
ꢂ = 102.219 (1)ꢂ
Data collection
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
Tmin = 0.594, Tmax = 0.782
10824 measured reflections
3965 independent reflections
2507 reflections with I > 2ꢄ(I)
Rint = 0.055
Refinement
R[F2 > 2ꢄ(F2)] = 0.037
wR(F2) = 0.079
S = 0.86
254 parameters
H-atom parameteꢁrs3 constrained
˚
Áꢅmax = 0.35 e A
ꢁ3
˚
3965 reflections
Áꢅmin = ꢁ0.35 e A
All H atoms were positioned geometrically and allowed to ride on
˚
their parent C atoms, with C—H distances of 0.93 or 0.96 A and
˚
2.367 versus 2.531 A (Constable et al., 2002) and 2.356 versus
Uiso(H) = 1.2 or 1.5Ueq(C) for aromatic and methyl H atoms,
respectively.
˚
2.520 A (Zhang et al., 2007)], but the difference in Ni—Cl
distances found in (I) is the largest, possibly as a result of the
good conjugation of all the ttp rings mentioned above.
However, although ttp is a good extended ꢀ-system, there is
no ꢀ–ꢀ stacking between the ttp planes in the crystal lattice in
(I). Instead, some nonclassical intermolecular hydrogen bonds
as secondary interactions play a crucial role in self-assembling
the molecules into a three-dimensional network, as discussed
below.
Table 1
Selected geometric parameters (A, ).
ꢂ
˚
Cl1—Ni1
Cl2—Ni1
N1—Ni1
2.3449 (7)
2.3980 (8)
2.077 (2)
N2—Ni1
N3—Ni1
Ni1—Cl1i
1.976 (2)
2.089 (2)
2.6231 (8)
N2—Ni1—N1
N2—Ni1—N3
N1—Ni1—N3
N2—Ni1—Cl1
N1—Ni1—Cl1
N3—Ni1—Cl1
N2—Ni1—Cl2
N1—Ni1—Cl2
78.89 (9)
78.37 (9)
157.26 (9)
170.45 (7)
100.69 (6)
101.67 (6)
90.77 (7)
91.36 (6)
N3—Ni1—Cl2
Cl1—Ni1—Cl2
N2—Ni1—Cl1i
N1—Ni1—Cl1i
N3—Ni1—Cl1i
Cl1—Ni1—Cl1i
Cl2—Ni1—Cl1i
89.31 (6)
98.78 (3)
85.07 (7)
87.10 (6)
90.60 (6)
85.38 (3)
175.77 (3)
As shown in Table 2 and the packing view (Fig. 2), the
terminal Cl2 atom acts as an acceptor of four intermolecular
C—Hꢀ ꢀ ꢀCl interactions with three aromatic CH groups from
the same neighboring molecule and one methyl group from
another adjacent molecule. One of the Hꢀ ꢀ ꢀCl distances is
˚
quite short at 2.59 A, suggesting a significant hydrogen
Symmetry code: (i) ꢁx; ꢁy þ 1; ꢁz.
bonding interaction, while the remaining three Hꢀ ꢀ ꢀCl
ꢄ
Acta Cryst. (2009). C65, m238–m240
Chen et al. [Ni2Cl4(C22H17N3)2] m239

metal-organic compounds
Bruker (2002). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin,
USA.
Table 2
Selected geometric parameters for intermolecular interactions (A, ).
ꢂ
˚
Bruker (2004). APEX2. Version 6.12. Bruker AXS Inc., Madison, Wisconsin,
USA.
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Collin, J. P., Guillerez, S., Sauvage, J. P., Barigelletti, F., DeCola, L., Flamigni,
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Collin, J. P., Kayhanian, R., Sauvage, J. P., Calogero, G., Barigelletti, F.,
DeCian, A. & Fischer, J. (1997). Chem. Commun. pp. 775–776.
Constable, E. C., Phillips, D. & Raithby, P. R. (2002). Inorg. Chem. Commun. 5,
519–522.
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
C4—H4ꢀ ꢀ ꢀCl2ii
0.93
0.93
0.93
0.96
2.59
2.91
2.93
2.82
3.512 (3)
3.837 (2)
3.851 (3)
3.693 (3)
171
170
170
151
C7—H7ꢀ ꢀ ꢀCl2ii
C17—H17ꢀ ꢀ ꢀCl2ii
C22—H22Cꢀ ꢀ ꢀCl2iii
3
2
1
2
Symmetry codes: (ii) x; ꢁy þ ; z þ ; (iii) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1.
´
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Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2;
data reduction: APEX2; program(s) used to solve structure:
SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:
SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL
(Sheldrick, 2008); software used to prepare material for publication:
SHELXTL.
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m240 Chen et al. [Ni2Cl4(C22H17N3)2]
Acta Cryst. (2009). C65, m238–m240