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I. Kalf et al. / Journal of Organometallic Chemistry 691 (2006) 2277–2285
6: 1609s, 1493w, 1454m, 1434w, 1400s, 1384s, 1359s,
1342m, 1282w, 1226w, 1201w, 1170w, 1109w, 1083w,
1054s, 1026m.
7: 1614s, 1495w, 1454m, 1397s, 1384m, 1358s, 1339m,
1292w, 1198m, 1160w, 1115w, 1084w, 1053m, 1032w.
CH3CH anion), 2.16 (3H, s, aryl-CH3), 2.56 (4H, m, broad,
2CH2N), 3.31 (1H, q, 7.1 Hz, CH3CHanion), 3.87 (2H, s,
broad, en-NH2), 4.05 (1H, m, CH3CH cation), 4.75 (2H,
s, broad, en-NH2), 4.82 (1H, m, NH2), 5.50 (1H, m,
NH2), 6.70–7.29 (8H, m, aryl H). 13C{1H} NMR
(DMSO-d6, ppm): d = 176.4, 153.9, 148.6, 145.6, 134.3,
132.5, 127.4, 127.3, 124.9, 124.0, 120.7, 58.3, 48.5, 45.6,
43.2, 24.3, 20.9, 20.3. The product may be recrystallized
from acetonitrile.
4.2.4. [Pd(p-MeC6H3CHMeNH2)(en)]C6H5CHOHCOO,
2
46 mg (0.76 mmol) ethylendiamine are added to a
solution of 210 mg (0.38 mmol) [{Pd(l-Cl)(R-MeC6H3CH-
MeNH2)}2] in 50 ml MeOH at 50 ꢁC. 198 mg (0.76 mmol)
rac-AgC6H5CHOHCOO are added; the suspension is stir-
red for 30 min and allowed to cool to room temperature,
and AgCl is removed by filtration. After evaporation of
the solvent in vacuo, the product is obtained in almost
4.3. Lattice energy minimizations
Local energy minima for the crystal structures of 1, 5, 6,
and 7 were obtained using the program PCK83 [29]. Prior to
minimization experimental distances to H atoms were nor-
malized to the following values: C–H 1.083, N–H 1.009, O–
1
quantitative yield. H NMR (DMSO-d6, ppm): d = 1.35
(3H, d, 6.4 Hz, CH3CH), 2.16 (3H, s, aryl-CH3), 2.59
(4H, m, broad, 2CH2N), 3.70 (2H, s, broad, en-NH2),
4.08 (1H, m, CH3CH), 4.48 (1H, s, CHOH), 4.69 (1H,
m, NH2), 4.76 (2H, s, broad, en-NH2), 5.36 (1H, m,
NH2), 6.71–7.39 (8H, m, aryl H). 13C{1H} NMR
(DMSO-d6, ppm): d = 173.9, 153.7, 148.1, 144.0, 134.2,
132.6, 127.1, 126.1, 125.7, 124.1, 120.8, 73.6, 58.4, 45.5,
43.3, 24.4, 20.9. The product may be recrystallized from
acetonitrile.
˚
H 0.983 A. Independent residues were treated as rigid
objects in their experimentally observed conformation
and were allowed to translate and rotate. Van-der-Waals
interactions were simulated with a Buckingham potential
using published parameters [30]. The intermolecular N–
Hꢁ ꢁ ꢁO hydrogen bonds were modelled by an additional
attractive exponential function of the type E = ꢀ8184.5 ·
exp(ꢀ2.9 · rij) (E in kJ molꢀ1, rij in A).
˚
4.4. Single crystal X-ray diffraction
4.2.5. [Pd(C6H4CHMeNH2)(en)]C6H5CHMeCOO, 3
46 mg (0.76 mmol) ethylendiamine are added to a solu-
tion of 200 mg (0.38 mmol) [{Pd(l-Cl)(R-C6H4CH-
MeNH2)}2] in 50 ml MeOH at 50 ꢁC. 196 mg (0.76 mmol)
rac-AgC6H5CHMeCOO are added; the suspension is stir-
red for 30 min and allowed to cool to room temperature,
and AgCl is removed by filtration. After evaporation of
the solvent in vacuo, the product is obtained in almost
quantitative yield as a monohydrate 3 Æ H2O. 1H NMR
(DMSO-d6, ppm): d = 1.22 (3H, d, 7.1 Hz, CH3CH cat-
ion), 1.34 (3H, d, 6.6 Hz, CH3CH anion), 2.55 (4H, m,
broad, 2CH2N), 3.23 (1H, q, 7.1 Hz, CH3CH anion), 4.05
(2H, s, broad, en-NH2), 4.15 (1H, m, CH3CH cation),
4.76 (2H, s, broad, en-NH2), 5.11 (1H, m, NH2), 5.71
(1H, m, NH2), 6.74–7.29 (9H, m, aryl H). 13C{1H} NMR
(DMSO-d6, ppm): d = 175.9, 157.2, 149.4, 146.3, 133.8,
127.4, 127.3, 124.7, 124.1, 123.3, 121.0, 58.6, 49.4, 45.8,
43.2, 24.3, 20.4. The product may be recrystallized from
methanol or methanol/water mixtures.
Intensity data were collected on a Bruker-Nonius D8
goniometer equipped with an APEX CCD area detector
at 110 K with Mo Ka radiation (graphite monochromator,
˚
k = 0.71073 A).
Empirical absorption corrections were performed with
SADABS [31]. The structures were solved by direct methods
[32] and refined on F2 [33]. Tables 2 and 3 compile crystal
data, data collection parameters and convergence results.
Packing coefficients were calculated with the help of the
program PLATON [22].
5. Supplementary material
Results of the single crystal X-ray diffraction experi-
ments on 1–7 have been deposited in CIF format at the
Cambridge Crystallographic Data Centre, CCDC, Nos.
285389 (1), 285390 (2), 285391 (3 Æ H2O), 285392 (4),
285393 (5), 285394 (6), and 285395 (7). Copies of the data
can be obtained free of charge on application to The Direc-
tor, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK,
fax: +44 1223 366 033, e-mail: deposit@ccdc.ac.uk or on
4.2.6. [Pd(p-MeC6H3CHMeNH2)(en)]C6H5CHMeCOO,
4
46 mg (0.76 mmol) ethylendiamine are added to a solu-
tion of 210 mg (0.38 mmol) [{Pd(l-Cl)(R-MeC6H3CH-
MeNH2)}2] in 50 ml MeOH at 50 ꢁC. 196 mg (0.76 mmol)
rac-AgC6H5CHMeCOO are added; the suspension is stir-
red for 30 min and allowed to cool to room temperature,
and AgCl is removed by filtration. After evaporation of
the solvent in vacuo, the product is obtained in almost
Acknowledgements
This work was supported by Deutsche Forschungsgeme-
inschaft (‘‘Racemic Crystals and Conglomerates’’). The
authors thank BASF for providing the enantiomerically
pure primary amines.
1
quantitative yield. H NMR (DMSO-d6, ppm): d = 1.25
(3H, d, 7.1 Hz, CH3CH cation), 1.34 (3H, d, 6.6 Hz,