lal Pratihar et al.
3244, 3187 cm-1, νNdN 1386, cm-1, νRh-Cl 339, 328 cm-1. 1H NMR
(CDCl3): 4.30(s, NH2, 2H), 5.60(s, NH2, 2H), 7.270-7.324 (m,
2H), 7.349-7.439(m, 5H), 7.466-7.521(m, 3H), 7.628(s, 1H),
8.223(d, 2H). Electronic spectral data in dichloromethane solu-
tion: (λ, nm,(ꢀ, M-1, cm-1)): 525 (4800), 370 (21900), 270
(30000), 245 (27650), 230 (47630).
(L2)(HL2)RhCl2 (2b) and (L2)(p-MeC6H4NH2)RhCl2 (3b).The
complexes 2b and 3b were prepared following the same procedure
as in the cases of 2a and 3a using 2-(p-tolylazo)aniline, 1b (160
mg, 0.76 mmol), in place of 1a. The solvent used for thin layer
chromatographic separation was toluene-acetonitrile (95:5 V/V)
mixed solvent. Yield: 46% (for complex 2b) and 12% (for complex
3b). Complex 2b calcd: C, 52.42%; H, 4.23%; N, 14.12%.
Table 3. Crystal Data for Complexes 2a and 3a
param
formula
2a
3a
C24H21N6RhCl2
567.28
(C18H17N4Rh Cl2)2,O
942.33
M
space group
a/Å
b/Å
monoclinic, C2/c
27.216(3)
10.299(8)
20.577(1)
90.000(0)
122.024(4)
90.000(0)
0.71073
4890.2(8)
8
triclinic, P1h
12.251(1)
12.438(1)
13.836(1)
91.210(2)
98.510(2)
101.850(3)
0.71073
2038(3)
2
c/Å
R/deg
â/deg
γ/deg
λ/Å
V/Å3
Z
T/K
273
1.541
0.941
0.036
0.088
0.97
273
1.536
1.111
0.039
0.102
1.02
D/mg/m-3
µ/mm-1
R(all data)
wR2c [I > 2σ(I)]
R1a/GOFb
Found: C, 52.32%; H, 4.12%; N, 14.02%. IR (KBr disk): νNH2
)
.
3300, 3225, 3150 cm-1, νNdN 1380, 1384 cm-1, νRh-Cl 329 cm-1
1H NMR (CDCl3): 4.586(s, NH2, 2H), 6.630(s, NH2, 2H), 2.394
(s, p-CH3, 3H), 2.543 (s, p-CH3, 3H), 7.132(d, 1H), 7.230-7.281
(m, 4H), 7.325-7.423(m, 3H), 7.523(t, 1H), 7.542 (s, 1H), 7.898-
7.927(m, 2H), 7.969(d, 1H), 8.107(d, 1H), 8.176 (d, 1H). Electronic
spectral data in dichloromethane solution: (λ, nm (ꢀ, M-1, cm-1)):
520 (9000), 360 (64200), 260(48043), 230 (67700).
a Observation criterion: I > 2σ(I). R1 ) ∑||Fo| - |Fo||/∑|Fo|. b GOF
) [∑[w(Fo2 - Fc )2]/(n - p)]1/2
.
c wR2 ) [∑[w(Fo2 - Fc )2]/∑[w(Fo )2]1/2
2 2
2
2
2
2
where w ) 1/ σ2(Fo ) + (aP)2 + bP, P ) (Fo + 2 Fc )/3.
Complex 3b calcd: C, 48.88%; H, 4.27%; N, 11.40%. Found:
C, 48.42%; H, 4.18%; N, 11.20%. IR (KBr disk): νNH2 ) 3313,
tropic refinements were performed on all the atoms. Hydrogen
atoms were included at calculated positions. The data collection
parameters and relevant crystal data are collected in Table 3.
3240,3175 cm-1, νNdN 1395 cm-1, νRh-Cl 321 cm-1 1H NMR
.
(CDCl3): 4.319(s, NH2, 2H), 5.506(s, NH2, 2H), 2.395 (s, p-CH3,
3H), 2.509 (s, p-CH3, 3H), 7.114(d, 1H), 7.203 (d, 2H), 7.287(d,
1H), 7.347(t, 1H), 7.404-7.430 (m, 4H), 8.101(d, 1H), 8.186(d,
1H). Electronic spectral data in dichloromethane solution: (λ, nm
(ꢀ, M-1, cm-1)): 525 (4800), 370 (21900), 270 (29800), 230
(47630).
Reaction of 2a with RhCl3. RhCl3‚3H2O (9 mg, 0.035 mmol)
was added to a methanolic (10 mL) solution of 2a (20 mg, 0.035
mmol), and refluxed for 0.5 h. The solid mass obtained upon
evaporation of methanol was introduced on a thin-layer chromato-
graphic plate prepared by silica gel. 3a was separated almost
exclusively using toluene-acetonitrile (95:5 V/V) mixed solvent.
The pure 3a was isolated from the TLC plate. Yield: 90%. The
product obtained was characterized by matching the UV-vis
spectrum.
Acknowledgment. We are thankful to the DST (New
Delhi) for funding and fellowship to J.P. under the DST-
SERC project. The necessary laboratory and infrastructural
facility are provided by the Department of Chemistry,
University of Kalyani. The support of DST under FIST
program to the Department of Chemistry, University of
Kalyani is acknowledged. We acknowledge Prof. Jui-Hsien
Huang, National Changhua University of Education, Chan-
ghua, Taiwan for X-ray studies. We are thankful to Prof.
Biswanath Chakraborty, Department of Chemistry, Univer-
sity of Kalyani, for donating some costly metal salts.
Supporting Information Available: Figures S1-S8 (pdf) and
crystallographic details for complexes 2a and 3a in CIF format.
This material is available free of charge via the Internet at
X-ray Crystallography. Data were collected on a Brucker
SMART CCD diffractometer using a Mo KR monochromator (λ
) 0.71043). Structure solutions were performed using the Shelx
97 PC version program. The full matrix least-squares and aniso-
IC050551W
6114 Inorganic Chemistry, Vol. 44, No. 17, 2005