H.-W. Kuai et al. / Polyhedron 72 (2014) 8–18
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2.5. Preparation of [Mn(L)(pybim)]ꢀ3H2O (4)
(k = 0.71075 Å) using MicroMax-007HF microfocus rotating anode
X-ray generator and VariMax-Mo optics at 200 K. Their structures
were solved by direct methods with SIR92 [10] and expanded using
Fourier techniques [11]. The crystallographic data collections for
2–5, and 7–8 were carried out on a Bruker Smart Apex CCD area-
Complex 4 was obtained by the same hydrothermal procedure
as that used for synthesis of 3 except that pybim (18.2 mg,
0.1 mmol) was introduced into the reaction as auxiliary ligand.
Colorless block crystals of 4 were collected by filtration and after
washed by water and ethanol several times in 35% yield. Anal. Calc.
for C24H23N5O7Mn: C, 52.56; H, 4.23; N, 12.77. Found: C, 52.81; H,
4.52; N, 12.59%. IR (KBr pellet, cmꢁ1, Fig. S1): 3420 (w), 1620 (s),
1568 (s), 1441 (m), 1376 (s), 1325 (w), 1287 (w), 1235 (w), 1108
(w), 979 (w), 940 (w), 781 (w), 748 (s).
detector diffractometer using graphite-monochromated Mo K
a
radiation (k = 0.71073 Å) at 293 K. The diffraction data were inte-
grated by using the SAINT program [12], which was also used for
the intensity corrections for the Lorentz and polarization effects.
Semi-empirical absorption correction was applied using the SADABS
program [13]. The structures were solved by direct methods and all
non-hydrogen atoms were refined anisotropically on F2 by the full-
matrix least-squares technique using the SHELXL-97 crystallographic
software package [14]. In 1–8, all hydrogen atoms attached to the C
atoms are generated geometrically, and the ones of O6 in 2, O7 and
O8 in 7 could not be located and thus were excluded from the
refinement, while the rest hydrogen atoms of water or N atom of
pybim in 4 were found at reasonable position in the difference Fou-
rier maps and located there. The details of crystal parameters, data
collection, and refinements for the complexes are summarized in
Table 1, selected bond lengths and angles are listed in Table 2.
2.6. Preparation of [Ni(L)(bpy)]ꢀ2H2O (5)
Complex 5 was obtained by the same procedure as that used for
preparation of 2 except that Ni(NO3)2ꢀ6H2O (29.1 mg, 0.1 mmol)
was used. After cooling at a rate of 10 °C/h to the room tempera-
ture, green block crystals of 5 were collected by filtration and
washed by water and ethanol for several times with a yield of
42%. Anal. Calc. for C22H20N4O6Ni: C, 53.37; H, 4.07; N, 11.32.
Found: C, 53.56; H, 4.32; N, 11.50%. IR (KBr pellet, cmꢁ1, Fig. S1):
3432 (m), 1613 (s), 1588 (s), 1550 (s), 1441 (s), 1370 (s), 1287
(w), 1088 (m), 1024 (w), 940 (w), 838 (w), 768 (m), 723 (m), 659
(m).
3. Results and discussion
3.1. Crystal structure description of [Cu(L)(py)] (1)
2.7. Preparation of [Ni(L)(phen)]ꢀ2H2O (6)
The result of single crystal X-ray diffraction analysis revealed
that 1 crystallizes in orthorhombic Pbca space group. The asym-
metric unit of 1 consists of one Cu(II), one L2ꢁ and one coordinated
pyridine molecule. Each Cu(II) atom is four-coordinated with dis-
torted square planar coordination geometry by two carboxylate
oxygen and one imidazolyl nitrogen atoms from three different
L2ꢁ ligands, and one pyridine nitrogen atom (Fig. 1a). The bond dis-
tances vary from 1.9253 (17) to 2.027 (2) Å and the bond angles
around the Cu(II) atom are in the range of 88.21(7)–174.69(7)° (Ta-
ble 2). Two carboxylate groups in the L2ꢁ ligand link two metal ions
The title complex was obtained by the same hydrothermal pro-
cedure as that used for synthesis of 5 except that phen (18.0 mg,
0.1 mmol) was used instead of bpy. After cooling at a rate of
10 °C/h to the room temperature, aqua-blue platelet crystals of 6
were collected by filtration and washed by water and ethanol for
several times with a yield of 37%. Anal. Calc. for C24H20N4O6Ni: C,
55.53; H, 3.88; N, 10.79. Found: C, 55.31; H, 4.06; N, 10.50%. IR
(KBr pellet, cmꢁ1, Fig. S1): 3452 (m), 1620 (s), 1582 (m), 1550
(s), 1517 (m), 1428 (m), 1364 (s), 1287 (w), 1101 (m), 940 (w),
851 (m), 781 (m), 723 (s), 666 (w).
each with l1- :
g1 g0-monodentate coordination mode (Scheme 1A).
The alternate linkage of the L2ꢁ to Cu(II) forms an infinite one-
dimensional (1D) chain by ignoring the coordination of imidazolyl
group (Fig. 1b). If taking the coordination of imidazolyl group into
consideration, the 1D chains are further jointed together to form an
interesting sandwich-like two-dimensional (2D) network (Fig. 1c
and 1d). The sandwich-like 2D architecture consists of upper and
lower two layers defined by benzene ring planes of L2ꢁ ligand with
imidazolyl groups filled between the two layers. While the pyri-
dine molecules are stuck onto the external surface of 2D network.
Within the double-layer 2D network of 1, the distance of the upper
and the lower layers is 5.15 Å, the nearest distance of two parallel
pyridine molecules is 8.76 Å and interestingly, the nearest distance
of two parallel imidazolyl groups also equals 8.76 Å. For the better
insight on the nature of 2D network, suitable nodes and connectors
can be defined by using a topological approach. As mentioned
above, each L2ꢁ ligand bridges three different Cu(II) and each Cu(II)
is also coordinated by three different L2ꢁ ligands. Thus, both of
Cu(II) and L2ꢁ can be regarded as 3-connected nodes, thus 1 dis-
plays a 3-connected uninodal 2D network with Point (Schläfli)
symbol of (4.82) (Fig. 1e) [15].
2.8. Preparation of [Ni(L)(bpe)(H2O)]ꢀ2H2O (7)
Complex 7 was prepared by the same hydrothermal procedure
as that used for synthesis of 5 except that bpe (18.2 mg, 0.1 mmol)
was used instead of bpy. Green block crystals of 7 were collected
by filtration and after washed by water and ethanol several times
in 52% yield. Anal. Calc. for C24H24N4O7Ni: C, 53.46; H, 4.49; N,
10.39. Found: C, 53.71; H, 4.22; N, 10.16%. IR (KBr pellet, cmꢁ1
,
Fig. S1): 3471 (m), 1613 (s), 1543 (s), 1459 (m), 1376 (s), 1280
(w), 1094 (m), 1024 (w), 832 (m), 781 (m), 748 (m), 723 (m),
666 (w), 634 (w), 550 (m).
2.9. Preparation of [Zn(L)(bpy)]ꢀ2H2O (8)
Complex 8 was obtained by the same hydrothermal procedure
as that used for synthesis of
5
except that Zn(NO3)2ꢀ6H2O
(29.7 mg, 0.1 mmol) was used. Colorless block crystals of 8 were
isolated by filtration and washed by water and ethanol several
times in 52% yield. Anal. Calc. for C22H20N4O6Zn: C, 52.65; H,
4.02; N, 11.16. Found: C, 52.59; H, 3.93; N, 11.29%. IR (KBr pellet,
cmꢁ1, Fig. S1): 3442 (m), 1623 (s), 1580 (s), 1545 (s), 1439 (s),
1366 (s), 1283 (w), 1083 (m), 1022 (w), 938 (w), 842 (w), 766
(m), 728 (m), 651 (m).
3.2. Crystal structure description of [Cu(L)(bpy)]ꢀ1.5H2O (2),
[Mn(L)(pybim)]ꢀ3H2O (4), and [Ni(L)(phen)]ꢀ2H2O (6)
2.10. X-ray crystallography
Complexes 2, 4 and 6 crystallize in the same triclinic crystal sys-
tem P-1 space group and show similar structural feature, thus only
the structure of 2 is described here in detail while the ones of 4 and
6 are given in Figs. S2 and S3.
The X-ray diffraction data for 1 and 6 were collected on a Rigaku
Rapid II imaging plate area detector with Mo
Ka radiation
Kuai, Hai-Wei
