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C.-W. Yeh et al. / Polyhedron 24 (2005) 539–548
2.3.5. MnCl2(o-HDMophF)2
refinements [5]. The final residuals of the final refinement
were R1 = 0.0459, wR2 = 0.1233. The crystallographic
procedures for 2, 6 and 7 were similar to those for 1.
A yellow crystal of 3 was mounted on the top of a
glass fiber with epoxy cement. The hemisphere data col-
lection method was used to scan the data points at
4.24ꢁ < 2h < 50.0ꢁ. The structure factors were obtained
after Lorentz and polarization correction. An empirical
absorption correction based on ꢀmulti-scanꢁ was applied
to the data. The positions of some of the heavier atoms,
including the Co atom, were located by direct methods.
The remaining atoms were found in a series of alternat-
ing difference Fourier maps and least-square refinements
[5]. The final residuals of the final refinement were
R1 = 0.0351, wR2 = 0.0673. The crystallographic proce-
dures for 4 and 5 were similar to those for 3. For com-
plex 4, no solution can be obtained if C2/c was used to
solve the structure. The space group Cc was then se-
lected to get the final structure.
For complexes 1, 5, 6 and 7, all the hydrogen atoms,
except the methyl hydrogen atom, H30A, H30B and
H30C in 5, were located in the difference electron density
map and refined isotropically. The hydrogen atoms of
complexes 2, 3 and 4 and H30A, H30B and H30C in 5
were placed in geometrically calculated positions using
the HADD program and refined using a riding model.
Basic information pertaining to crystal parameters and
structure refinement is summarized in Table 1.
Procedures for 5 were similar to those for 2. Yield:
0.52 g (82.3%). UV–vis (CH2Cl2): 425 nm. Anal. Calc.
for C30H32MnCl2N4O4 (MW = 638.45), C, 56.44; H,
5.05; N, 8.78. Found: C, 56.40; H, 5.07; N, 8.46%.
FT-IR (cmꢁ1) (KBr disk): 3177(s), 3033(w), 2939(m),
1648(s), 1591(s), 1513(m), 1496(s), 1463(m), 1432(w),
1378(w), 1333(m), 1299(w), 1256(w), 1239(s), 1181(w),
1157(m), 1116(s), 1048(m), 1024(s), 924(m), 851(w),
831(w), 788(w), 753(s), 721(s), 625(m), 576(w).
2.3.6. NiCl2(o-HDMophF)2
Procedures for 6 were similar to those for 2. Yield:
0.37 g (57.6%). UV–vis (CH2Cl2): 362 nm. Anal. Calc.
for C30H32NiCl2N4O4 (MW = 642.20), C, 56.11; H,
5.02; N, 8.72. Found: C, 55.78; H, 4.98; N, 8.55%.
FT-IR (cmꢁ1) (KBr disk): 3445(b), 3353(s), 3230(m),
2836(w), 1654(s), 1598(s), 1509(m), 1490(s), 1455(m),
1418(w), 1388(w), 1371(m), 1323(w), 1305(w), 1294(m),
1275(m), 1245(s), 1208(w), 1176(w), 1149(m), 1108(s),
1042(m), 1015(s), 951(m), 843(w), 787(w), 756(s),
598(m), 538(w), 507(w), 490(w), 467(w), 440(w).
2.3.7. PdCl2(o-HDMophF)2
Procedures for 7 were similar to those for 2. Yield:
0.46 g (77%). UV–vis (CH2Cl2): 502 nm. Anal. Calc.
for C30H32PdCl2N4O4 (MW = 689.93), C, 52.23; H,
4.67; N, 8.12. Found: C, 52.40; H, 4.66; N, 8.07%.
FT-IR (cmꢁ1) (KBr disk): 3448(b), 3357(s), 3233(m),
2838(w), 1655(s), 1598(s), 1514(m), 1494(s), 1458(m),
1420(w), 1389(w), 1371(m), 1328(w), 1309(w), 1297(m),
1277(m), 1246(s), 1208(w), 1185(w), 1157(m), 1115(s),
1048(m), 1023(s), 955(m), 844(w), 789(w), 757(s),
598(m), 538(w), 507(w), 490(w), 467(w), 440(w).
3. Results and discussion
3.1. Synthesis
The reactions of N,N0-di(2-methoxyphenyl)formami-
dine (o-HDMophF) with CuCl2 Æ 2H2O, CoCl2 Æ 6H2O,
CoBr2, CdCl2 Æ H2O, MnCl2, NiCl2 and PdCl2 in reflux-
ing CH2Cl2 afforded the complexes CuCl2 Æ (o-HDM-
ophF), 1, [CoX4][o-H2DMophF]2 (X = Cl, 2; Br, 3)
and MCl2(o-HDMophF)2 (M = Cd, 4; Ni, 5; Mn, 6;
Pd, 7), respectively. It is noted that although similar
reaction conditions were used to prepare 1–7, different
types of products were obtained, presumably due to
the different reactivity of the metal centers to
o-HDMophF.
2.4. X-ray crystallography
Single crystal X-ray diffraction data were collected at
22 ꢁC using either a Bruker AXS P4 (complexes 1, 2 and
6) or a Siemens CCD diffractometer (complexes 2, 4 and
5), which were equipped with graphite-monochromated
˚
Mo Ka (0.71073 A) radiation. Data reduction was car-
ried by standard methods with the use of well-estab-
lished computational procedures [4].
A light yellow crystal of 1 was mounted on the top of
a glass fiber with epoxy cement. Cell constants were de-
rived from least-squares refinement of 40 reflections
having 10.1 < 2h < 24.8. The x-scan data collection
method was used to collect the data points at
3.84ꢁ < 2h < 50.00ꢁ. The structure factors were obtained
after Lorentz and polarization correction. An empirical
absorption correction based on a series of w-scans was
applied to the data. The positions of some of the heavier
atoms, including the copper atom, were located by direct
methods. The remaining atoms were found in a series of
alternating difference Fourier maps and least-square
3.2. Structure of 1
Yellow complex 1 was solved in the space group P21/c.
Fig. 1 shows the ORTEP drawing of 1, and the correct
formulation for this complex is CuCl2 Æ (o-HDMophF).
Selected bond distances and angles are listed in Table 2.
The copper atom is bonded to two chlorine atoms to
form a linear geometry. The two Cu–Cl distances are
˚
2.1873(15) and 2.1752(15) A and the Cl–Cu–Cl angle
is 178.71(4)ꢁ. The packing diagram of complex 1 shows