Syntheses of new sulfur-nitrogen palladacycles - Crystal structures of [(AMTTO)PdBr2]2·3.5THF, [(AMTTO)PdI2]2·3MeOH, [(AMTTO)Pd(PPh3)Br]Br·MeOH, and [(AMTTO)Pd(PPh3)I]·2MeOH (AMTTO = 4- amino-6-methyl-l,2,4-triazine-3-thione-5-one)

Article abstract of DOI:10.1002/1099-0682(200008)2000:8<1877::aid-ejic1877>3.0.co;2-k

Reactions of [(AMTTO)PdCl₂]·MeOH (1) with sodium bromide and sodium iodide led to the palladacycles [(AMTTO)PdBr₂]₂·3.5THF (2) and [(AMTTO)PdI₂]₂·3MeOH (3) in excellent yields. Treatment of 2 and 3 with triphenyl-phosphane gave the complexes [(AMTTO)Pd(PPh₃)Br]-Br·MeOH (4) and [(AMTTO)Pd(PPh₃)I]·2MeOH (5), respectively. All the complexes have been characterized by IR spectroscopy, elemental analysis, as well as by X-ray diffraction studies. In addition, 4 and 5 have been characterized by ³¹p NMR spectroscopy. Crystal data for 2 at -80 °C: triclinic, space group P1, a = 1150.8(1), b = 1234.1(1), c = 1398.1(1) pm, α = 84.01(1)°, β = 86.84(1)°, γ = 66.40(1)°, Z = 2, R₁ = 0.0366; for 3 at -50 °C: orthorhombic, space group Pbcn, a = 1476.2(1), b = 1333.1(1), c = 1440.1(1) pm, Z = 4, R₁ = 0.0302; for 4 at -80 °C: monoclinic, space group P2₁/c, a = 993.0(1), b = 993.6(1), c = 2735.5(2) pm, β = 97.64(1)°, Z = 4, R₁ = 0.0464; for 5 at -70 °C: monoclinic, space group P2₁/c, a = 865.7(2), b = 3760.5(3), c = 861.1(1) pm, β = 97.56(1)°, Z = 4, R₁ = 0.0613.

Full text of DOI:10.1002/1099-0682(200008)2000:8<1877::aid-ejic1877>3.0.co;2-k

FULL PAPER
Syntheses of New Sulfur؊Nitrogen Palladacycles ؊ Crystal Structures of
[(AMTTO)PdBr2]2·3.5THF, [(AMTTO)PdI2]2·3MeOH,
[(AMTTO)Pd(PPh3)Br]Br·MeOH, and [(AMTTO)Pd(PPh3)I]·2MeOH
(AMTTO ؍ 4-Amino-6-methyl-1,2,4-triazine-3-thione-5-one)
Mitra Ghassemzadeh,*[a] Mohammad Bolourtchian,[a] Soheila Chitsaz,[b]
Bernhard Neumüller,[b] and Majid M. Heravi[c]
Keywords: Palladium / Triazines / Metallacycles / N ligands / S ligands
¯
Reactions of [(AMTTO)PdCl2]·MeOH (1) with sodium brom-
ide and sodium iodide led to the palladacycles
[(AMTTO)PdBr2]2·3.5THF (2) and [(AMTTO)PdI2]2·3MeOH
(3) in excellent yields. Treatment of 2 and 3 with triphenyl-
space group P1, a = 1150.8(1), b = 1234.1(1), c = 1398.1(1)
pm, α = 84.01(1)°, β = 86.84(1)°, γ = 66.40(1)°, Z = 2, R1
=
0.0366; for 3 at −50 °C: orthorhombic, space group Pbcn, a =
1476.2(1), b = 1333.1(1), c = 1440.1(1) pm, Z = 4, R1 = 0.0302;
phosphane gave the complexes [(AMTTO)Pd(PPh3)Br]- for 4 at −80 °C: monoclinic, space group P21/c, a = 993.0(1),
Br·MeOH (4) and [(AMTTO)Pd(PPh3)I]·2MeOH (5), respect-
ively. All the complexes have been characterized by IR spec-
troscopy, elemental analysis, as well as by X-ray diffraction
studies. In addition, 4 and 5 have been characterized by 31P
NMR spectroscopy. Crystal data for 2 at −80 °C: triclinic,
b = 993.6(1), c = 2735.5(2) pm, β = 97.64(1)°, Z = 4, R1 =
0.0464; for 5 at −70 °C: monoclinic, space group P21/c, a =
865.7(2), b = 3760.5(3), c = 861.1(1) pm, β = 97.56(1)°, Z = 4,
R1 = 0.0613.
Introduction
1,2,4-Triazines are well-known compounds and a variety
of synthetic methods for the preparation of substituted de-
rivatives are available. Compounds containing the 1,2,4-tri-
azine moiety are found in natural materials and some of
these exhibit biological activity. A large number of synthetic
1,2,4-triazines also show biological activity and have been
used for various purposes. For example, 1,2,4-triazine-3,5-
diones (I) represent aza analogues of pyrimidine nucleic
acid bases. A number of neutral antibiotics are derivatives
of pyrimido[5,4-e]-1,2,4-triazine (II). 4-Amino-6-tert-butyl-
3-methylthio-1,2,4-triazine-5-one (III) and 4-amino-3-
methyl-6-phenyl-1,2,4-triazine-5-one (IV) are used as herbi-
cides (Scheme 1).[1a] Metal complexes of ligands such as
S,N-heterocycles, amino acids, and proteins often exhibit
enhanced biological activities compared to the uncom-
plexed ligand.[1b][1c]
Scheme 1. Four important classes of N-containing heterocycles
[2]
In our investigations, we have shown that AMTTO Ϫ a
representative of 4-amino-6-alkyl-1,2,4-triazine-5-one Ϫ
acts as a chelating ligand in a 1ϩ1 fashion towards AgNO3
in methanol {one strong AgϪS bond and a weak AgϪN
contact leading to a distortion of a ideal linear [AMTTO-
Ag-AMTTO]ϩ ion} and as a bidentate chelating ligand to-
wards PdCl2 in methanol/acetonitrile to give the air-stable
complexes [(AMTTO)2Ag]NO3
and [(AMTTO)-
PdCl2]·MeOH (1),[3] respectively. To the best of our know-
ledge, the latter constitutes the first palladacycle of
AMTTO.
We have already studied the reactions of 1 with triphenyl-
phosphane and sodium thiocyanate, which led to the air-
stable complexes [(AMTTO)Pd(PPh3)Cl]Cl·MeOH and
[(AMTTO)Pd(SCN)2]·MeOH, respectively.[4]
[a]
Chemistry and Chemical Engineering Research Center of Iran,
P.O. Box 18335-186, Tehran, Iran
[b]
Fachbereich Chemie der Universität,
Hans-Meerwein-Straße, D-35032 Marburg, Germany
In this paper, we wish to report the halide exchange reac-
tions of 1 using sodium bromide and sodium iodide, as well
[c]
Department of Chemistry, School of Sciences,
Azzahra University, Vanak, Tehran, Iran
Eur. J. Inorg. Chem. 2000, 1877Ϫ1882
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ1948/00/0808Ϫ1877 $ 17.50ϩ.50/0
1877

M. Ghassemzadeh, M. Bolourtchian, S. Chitsaz, B. Neumüller, M. M. Heravi
FULL PAPER
as the reactions of the bromine and iodine palladacycles 268 cmϪ1 for 2, at 445, 373, and 173 cmϪ1 for 3, at 450,
with triphenylphosphane.
382, and 259 cmϪ1 for 4, and at 449, 374, and 198 cmϪ1 for
5, which can be assigned to ν(PdN), ν(PdS), and ν(PdX)
absorptions.[5] CϭO and CϭN vibrations give rise to two
bands at 1703 and 1604 cmϪ1 for 2, at 1718 and 1612 cmϪ1
for 3, at 1719 and 1595 cmϪ1 for 4, and at 1725 and
1625 cmϪ1 for 5. PϪC vibrations of the PPh3 moiety are
seen in the range 749Ϫ711 cmϪ1 for 4 and in the range
745Ϫ691 cmϪ1 for 5. The NϪH valence vibrations give rise
to broad bands at 3254 (2), 3230 (3), 3205 (4), and
3250 cmϪ1 (5). Broad OϪH absorptions, attributable to hy-
drogen bonding, give rise to the bands at 3620, 3554, and
3472 cmϪ1 (3) and at 3446 cmϪ1 (5). The corresponding
band for 4 could not localized accurately because of the
measured line width.
Results and Discussion
Syntheses and Characterization of 2, 3, 4, and 5
Treatment of 1 with sodium bromide in THF at 20 °C
gave 2; similar treatment with sodium iodide in methanol/
acetonitrile gave 3 [Equation (1) and (2)].
Crystal Structures of 2؊5
The structural data of the palladacycles show that 2 (Fig-
ure 1), 3 (Figure 2), and 5 (Figure 4) are neutral molecules
incorporating [(AMTTO)Pd] complex fragments. 4 is a salt
consisting of [(AMTTO)Pd(PPh3)Br]ϩ and BrϪ ions, while
5 incorporates the anionic ligand [AMTTO]Ϫ. The coor-
dination geometry about the palladium center in each of
these complexes is essentially square planar. In all the com-
plexes, the bidentate AMTTO ligand is coordinated to pal-
ladium(II) forming a five-membered chelate ring. The coor-
dination sphere of 2 is completed by two bromide anions,
while that of 3 is completed by two iodide ions. The coor-
dination sites in 4 and 5 are occupied by one halide ion
(BrϪ in 4; IϪ in 5, Figure 3 and 4) and a triphenylphos-
phane ligand. The PdϪS bond lengths of 225.2(2)/225.9(2)
and 227.4(2) pm found in 2 and 3, respectively, do not differ
significantly from the PdϪS distances of 227.5(2) and
226.6(2) pm in 4 and 5. On comparing the data with the
lowest literature values for thioether-palladium complexes,
i.e. 228Ϫ229 pm, these distances are seen to be rather
short.[6,7] The PdϪN atom distances are within the range
observed for related compounds.[7] The PdϪN bond lengths
[211.0(5) pm in 4; 209.2(7) pm in 5] are longer than those
in 2 and 3 [204.2(6) and 207.9(5) pm, respectively]. This
lengthening reflects the trans influence of the phosphane
ligand. The PdϪX bonds trans to the sulfur atom
[Pd1ϪBr1 and Pd2ϪBr4, 244.7(1) and 244.1(9) pm in 2;
Pd1ϪI2 259.73(6) pm in 3] are somewhat longer than the
PdϪX distances cis to S1 [Pd1ϪBr2 240.75(6) pm and
Pd2ϪBr3 242.5(1) pm in 2; Pd1ϪI1 257.50(6) pm in 3], re-
flecting the greater trans influence of the sulfur atom as
compared to the nitrogen atom. The presence of an
[AMTTO]Ϫ ligand in 5 leads only to marginal differences
Further treatment of 2 and 3 with PPh3 in methanol at
20 °C led to 4 and 5, respectively, according to Equation (3)
and (4).
In contrast to Equation (3), reaction according to Equa-
tion (4) gives the complex 5 incorporating the anionic li-
gand [AMTTO]Ϫ (V). This results from an abstraction of
HI owing to the relatively high acidity of this particular
NH group. The coordination of the sulfur atom leads to
additional acidification of the amine function (see
Scheme 2).
Scheme 2. Mesomeric forms of the anionic AMTTO ligand
Compounds 2؊5 were found to be air-stable crystalline in the bonding parameters due to the delocalization of the
solids. The 13C NMR spectrum of the ligand AMTTO has charge in V (Scheme 2).
[2]
been published for the Ag complex [Ag(AMTTO)2]NO3
The halide atoms in 4 and 5 are oriented cis to the nitro-
and the data are almost unchanged in the spectra of 2؊5. gen ligands of the heterocycle, indicating the strong influ-
The 31P NMR spectra of 4 and 5 feature only one sharp ence of the π-acids CϭS and PPh3. The PdϪBr and PdϪI
singlet at δ ϭ 30.3 and δ ϭ 26.2, respectively, in accordance bond lengths (PdϪBr, mean 243 pm; PdϪI, mean 259.5
with the geometries of these compounds. In the IR spectra pm) are shorter than the sum of the single bond radii for
of 2؊5, three absorptions are seen at 452, 369, and palladium and the halides (Pd: 131 pm, Br: 114 pm, I: 133
1878
Eur. J. Inorg. Chem. 2000, 1877Ϫ1882

Syntheses of New SulfurϪNitrogen Palladacycles
FULL PAPER
Figure 3. Molecular structure of 4 (most of the H atoms are
omitted for the sake of clarity)
Figure 1. Molecular structure of 2 with showing disorder of the
THF molecules (the C atoms are shown as spheres; most of the H
atoms are omitted for the sake of clarity; 50% probability level)
Figure 4. Molecular structure of 5 (most of the H atoms are
omitted for the sake of clarity)
There are several medium to strong hydrogen bonds in
the complexes. The two independent palladacycle units in
2 are held together by H···Br contacts [N2···Br4: 346.5(7);
N6···Br1: 334.2(6) pm]. This leads to an angle of 7° between
the ‘‘best’’ planes of the two complexes. THF molecules are
hydrogen-bonded to H2 [N2···O3: 286.9(9) pm], H3
[N4···O4: 270.2(7) pm], H4 [N6···O6: 277.1(8) pm], and H6
[N8···O5: 265.3(9) pm]. The THF molecule O3ǞC12 is dis-
ordered about a center of symmetry (see Figure 1).
Figure 2. Molecular structure of 3 with showing disorder of the
central methanol molecule (most of the H atoms are omitted for
the sake of clarity)
In 3, two palladacycles are connected through a meth-
anol molecule, which lies on a twofold axis. This means a
pm),[8] but fall within the range observed for similar com- disorder of the OH moiety O3ϪH5 over two positions
pounds.[9]
[N2···O3: 287.9(8)°]. An additional methanol molecule is
The PdϪP atom distances (average 225 pm) are shorter hydrogen-bonded to each NH2 group [N2···O2: 282.6(7)°
than the sum of the single bond radii for palladium and pm]. Each [(AMTTO)PdI2]2·3MeOH building block is part
phosphorus, i.e. 241 pm,[10] are remarkably shorter than the of a chain built up by N2ϪH1···O2 hydrogen bonds
PdIIϪPPh3 bond reference value (230.2 pm) encountered in [N2···O2: 282.6(7)°; Figure 5] that extends along [010]. The
248 entries,[11] and fall at the short end of a wide range palladacycles in 3 are slightly bent. The dihedral angle be-
(221Ϫ246 pm). The XϪPdϪP angles, which measure tween the plane Pd1/I1/I2/N2/S2 and the ligand AMTTO
92.04(4)° in 4 and 92.64(7)° in 5, are similar to values re- amounts to 7°. In 4, isotypical to the corresponding com-
ported in the literature.[12]
plex [(AMTTO)PdCl(PPh3)]Cl·MeOH,[4] N3 (NH function)
Eur. J. Inorg. Chem. 2000, 1877Ϫ1882
1879

M. Ghassemzadeh, M. Bolourtchian, S. Chitsaz, B. Neumüller, M. M. Heravi
FULL PAPER
Figure 5. Stereoscopic view of the unit cell of 3; the chains extending along [010] as a result of hydrogen bonding are also shown
is connected through the methanol molecule [N3···O2: Experimental Section
265.4(7) pm] to Br2 [counterion; O2···Br2: 322.3(5) pm] and
General Remarks: AMTTO[13] and 1[3] were prepared according to
literature procedures. IR spectra were recorded on
then to two nitrogen atoms [N2a, N2b; NH2 function;
N2···Br2a: 338.1(5); N2···Br2b: 320.8(5) pm; Figure 3]. The
Ϫ
a
PerkinϪElmer spectrometer 883 (KBr pellets, Nujol mulls,
4000Ϫ250 cmϪ1) or on a Bruker IFS 88 instrument (CsBr discs,
4000Ϫ400 cmϪ1; polyethylene discs, 500Ϫ100 cmϪ1; Nujol mulls).
packing of
4
has already been demonstrated for
[(AMTTO)PdCl(PPh3)]Cl·MeOH.[4] In 5, medium to strong
hydrogen bonds link the methanol molecules to N3 and to
NH2 groups of the adjacent AMTTO ligands, respectively
(Figure 4). The contacts O3···O2 [266.7(9) pm], O2···N3
[286.9(9) pm], O3···N2a [278.7(9) pm], and N4···N2b
[294.8(9) pm] give rise to a 2D-network of complex and
solvate molecules that extends parallel to (010) (Figure 6).
Ϫ
31P NMR spectra were recorded on a Bruker AC-200 spectro-
meter using 85% aqueous H3PO4 as an external standard. Ϫ Ele-
mental analyses were performed by the following methods: C, H,
N analyses: combustion method; halogen analyses: combustion and
titration with AgNO3; sulfur analyses: combustion and titration
with Ba(ClO4)2; phosphorus: decomposition with HClO4 and pho-
tometric analysis of the molybdophosphate; palladium analyses:
decomposition with HClO4 and analysis by atomic absorption
spectroscopy. Ϫ The following chemicals were purchased from
Merck and used without further purification: sodium bromide, so-
dium iodide, triphenylphosphane, methanol, and acetonitrile.
Synthesis of [(AMTTO)PdBr2]2·3.5THF (2): A solution of 1 (0.36 g,
0.98 mmol) in THF (20 mL) was treated with NaBr (0.20 g,
1.9 mmol) and the resulting mixture was stirred for 3 h at 20 °C.
The white precipitate formed was filtered off and the filtrate was
concentrated to a small volume (ca. 5 mL) until an orange solid
separated. The crude product was filtered off and the clear solution
was kept at 4 °C to give a second crop of orange crystals of 2. Ϫ
Yield: 0.96 g (95%). Ϫ C22H40Br4N8O5.5Pd2S2 (1011.19): calcd. C
13.16, H 2.21, N 12.27, Br 35.01, Pd 23.31, S 7.02; found C 13.01,
H 2.14, N 12.17, Br 34.90, Pd 23.35, S 6.97. Ϫ IR (Nujol): ν˜ ϭ
3254 [w, br, ν(NH)], 1703 [s, ν(CϭO)], 1604 [m, ν(NϭC)], 1588 (m),
1520 (m), 1321 (m), 1304 (s), 1233 (m), 1166 (m), 1036 (m), 974
(w), 930 (w), 875 (w), 802 (w), 749 (s), 675 (m), 646 (w), 606 (m),
528 (w), 506 (m), 452 [m, ν(PdN)], 409 (w), 369 [w, ν(PdS)], 310
(m), 268 [w, ν(PdBr2)], 246 (w), 198 (w), 165 (w).
Synthesis of [(AMTTO)PdI2]2·3MeOH (3): To a stirred solution of
1 (0.36 g, 0.98 mmol) in methanol/acetonitrile (1:1 v/v, 30 mL) at
20 °C was added NaI (0.29 g, 1.9 mmol). The reaction mixture was
stirred for a further 5 h. The white solid formed was filtered off
and the filtrate was concentrated to a volume of 10 mL and filtered
once more. The filtrate was stored at 4 °C overnight to give orange
crystals of 3, which were collected by filtration and washed with
cold methanol. Ϫ Yield: 1.05 g (93%). Ϫ C11H24I4N8O5Pd2S2
(1133.0): calcd. C 11.66, H 2.14, N 9.89, I 44.81, Pd 18.79, S 5.66;
found C 11.55, H 2.10, N 9.56, I 44.92, Pd 18.56, S 5.34. Ϫ IR
(Nujol): ν˜ ϭ 3620 [vw, br, ν(OH)], 3554 [w, br, ν(OH)], 3472 [w, br,
ν(OH)], 3230 [w, br, ν(NH)], 1719 [s, ν(CϭO)], 1595 [m, ν(CϭC)],
1538 (w), 1516 (w), 1492 (w), 1335 (m), 1301 (s), 1218 (w), 1150
(w), 1112 (w), 1048 (w), 973 (w), 926 (w), 602 (w), 512 (m), 445 [m,
ν(PdN)], 409 (w), 373 [w, ν(PdS)], 325 (vw), 305 (w), 280 (vw), 253
(w), 228 (w), 201 (vw), 173 [w, ν(PdI2)], 128 (vw) 112 (vw).
Figure 6. View of the unit cell of 5; 5 forms layers built-up by
hydrogen bonds parallel to (010)
1880
Eur. J. Inorg. Chem. 2000, 1877Ϫ1882

Syntheses of New SulfurϪNitrogen Palladacycles
FULL PAPER
Reactions with PPh3. ؊ General Procedure: A solution of 2 (or 3)
[w, br, ν(NH)], 1719 [vs, ν(CϭO)], 1612 [m, ν(CϭC)], 1573 (m),
(1.00 mmol) in methanol (30 mL) was treated with PPh3 (0.26 g,
1537 (m), 1435 (s), 1348 (m), 1301 (m), 1185 (w), 1146 (w), 1097
0.99 mmol) and the resulting mixture was stirred for 3 h at 20 °C. (s), 1045 (w), 1024 (w), 1000 (m), 966 (m), 936 (w), 750 (s), 712
The solution was then concentrated to a small volume (ca. 10 mL)
(m), 692 (s), 655 (w), 619 (w), 601 (w), 536 (s), 507 (s), 450 [m,
until a yellow solid separated. The crude product was filtered off ν(NH)], 412 (w), 382 [m, ν(PdS)], 310 (vw), 259 [w, ν(PdBr)], 195
and the clear filtrate was kept at 4 °C to give yellow crystals of 4
(or 5).
(m), 132 (vw). Ϫ 31P NMR (CD3OD): δ ϭ 30.3 (s).
Synthesis of [(AMTTO)Pd(PPh3)I]·2MeOH (5): Yield: 0.65 g
(91%). Ϫ C24H28IN4O3PPdS (716.87): calcd. C 40.21, H 3.94, N
7.82, I 17.78, P 4.32, Pd 14.85, S 4.47; found C 39.89, H 3.87, N
7.71, I 17.65, P 4.26, Pd 13.99, S 4.36. Ϫ IR (Nujol): ν˜ ϭ 3446 [vw,
br, ν(OH)], 3250 [vw, br, ν(NH)], 1728 [vs, ν(CϭO)], 1625 (m, Cϭ
Synthesis of [(AMTTO)Pd(PPh3)Br]Br·MeOH (4): Yield: 0.64 g
(90%). Ϫ C23H25Br2N4O2PPdS (718.73): calcd. C 38.44, H 3.51, N
7.80, Br 22.23, P 4.31, Pd 14.81, S 4.46; found C 38.26, H 3.46, N
7.72, Br 21.98, P 4.15, Pd 14.68, S 4.31. Ϫ IR (Nujol): ν˜ ϭ 3205
Table 1. Crystallographic data for 2Ϫ5
Compound
2
3
4
5
Empirical formula
Formula mass
Crystal size (mm)
Crystal system
Space group
a [pm]
C22H40Br4N8O5.5Pd2S2
1101.19
C11H24I4N8O5Pd2S2
1133.0
C23H25Br2N4O2PPdS
718.73
C24H28IN4O3PPdS
716.87
0.25 ϫ 0.17 ϫ 0.05
0.51 ϫ 0.2 ϫ 0.09
orthorhombic
Pbcn (no.60)
1476.2(1)
1333.1(1)
1440.1(1)
Ϫ
0.38 ϫ 0.13 ϫ 0.09
monoclinic
P21/n (no.14)
993.0(1)
993.6(1)
2735.5(2)
Ϫ
0.39 ϫ 0.1 ϫ 0.1
monoclinic
P21/c (no.14)
865.7(2)
3760.5(3)
861.1(1)
Ϫ
triclinic
[20]
¯
P1 (no.2)
1150.8(1)
1234.1(1)
1398.1(1)
84.01(1)
86.84(1)
66.40(1)
1809.4(3)
2
b [pm]
c [pm]
α [°]
β [°]
Ϫ
Ϫ
97.64(1)
Ϫ
97.56(1)
Ϫ
γ [°]
Volume [pm3·106]
Z
2834.0(3)
2675.0(4)
4
2778.9(8)
4
4
Dcalcd. [g·cmϪ3
]
2.021
2.655
1.785
1.713
Absorption correction
numerical
55.7
empirical
58.1
numerical
38.5
empirical
19.4
µMo-Kα [cmϪ1
]
Temperature [K]
2θ range
193
223
193
183
4.0Ϫ52.06
Ϫ14Ǟ14
Ϫ15Ǟ15
Ϫ17Ǟ17
14079
2.0Ϫ50.0
Ϫ1Ǟ17
Ϫ2Ǟ15
Ϫ1Ǟ17
3896
4.22Ϫ51.9
Ϫ12Ǟ12
Ϫ12Ǟ12
Ϫ33Ǟ33
20729
5.76Ϫ50.0
Ϫ10Ǟ10
Ϫ44Ǟ0
0Ǟ10
Index range
h
l
k
Reflections collected
5346
Unique reflections (Rint
)
6530 (0.069)
3262
2498 (0.0244)
1996
5214 (0.0628)
3502
4898 (0.0698)
3129
Reflections with Fo Ͼ 4 σ(Fo)
Parameters
443
170
407
331
R1
0.0366
0.0302
0.0464
0.0611
wR2 (all data)
0.0579[a]
0.0735[b]
0.106[c]
0.1352[d]
largest diff. peak and hole
[(e·pmϪ3)·10Ϫ6
]
Ϫ0.72/0.59
Ϫ0.58/0.71
Ϫ0.82/0.8
Ϫ1.33/0.73
[a]
[b]
2
2
[c]
[d]
w ϭ 1/[σ2(Fo)2]. Ϫ
w ϭ 1/[σ2(Fo) ϩ (0.0375·P)2]; P ϭ [max(Fo ,0) ϩ 2Fc ]/3. Ϫ
w ϭ 1/[σ2(Fo) ϩ (0.0555·P)2]. Ϫ
w ϭ 1/
[σ2(Fo) ϩ (0.0375·P)2 ϩ 3.91·P].
Table 2. Selected bond lengths [pm] and bond angles [°] in 2؊5
2
3
4
5
Pd1ϪBr1
Pd1ϪBr2
Pd1ϪS1
Pd1ϪN2
S1ϪC1
N1ϪN2
C1ϪN1
O1ϪC2
N4ϪC1
N3ϪN4
244.7(1) Pd2ϪBr3
240.75(9) Pd2ϪBr4
225.2(2) Pd2ϪS2
204.2(6) Pd2ϪN6
169.4(7) S2ϪC5
144.7(8) N5ϪN6
136.8(7) N5ϪC5
124.7(8) O2ϪC6
131.3(8) N8ϪC5
136.5(8) N7ϪN8
242.5(1) Pd1ϪI1
244.10(9) Pd1ϪI2
225.9(2) Pd1ϪS1
205.3(8) Pd1ϪN2
168.5(8) S1ϪC1
144.3(8) N1ϪN2
137.3(8) N1ϪC1
121.2(8) O1ϪC2
133.2(9) N1ϪC2
257.50(6) Pd1ϪBr1
259.73(6) Pd1ϪP1
227.4(2) Pd1ϪS1
207.9(5) Pd1ϪN2
169.2(6) S1ϪC1
144.3(6) N1ϪN2
135.3(7) N1ϪC1
121.2(7) O1ϪC2
138.7(7) N1ϪC2
136.2(7) N3ϪN4
242.75(8) Pd1ϪI1
225.0(1) Pd1ϪP1
227.5(2) Pd1ϪS1
211.0(5) Pd1ϪN2
171.1(5) S1ϪC1
141.3(7) N1ϪN2
135.0(7) N1ϪC1
119.8(8) O1ϪC2
140.7(7) N1ϪC1
137.4(6) N3ϪN4
261.58(9)
225.0(3)
226.6(2)
209.5(7)
173.1(9)
143(1)
137(1)
122(1)
140(1)
137(1)
N3ϪN4
138(1)
Br1ϪPd1ϪBr2 93.46(4) Br3ϪPd2ϪBr4 92.80(4) I1ϪPd1ϪI2
Br1ϪPd1ϪS1 176.43(6) Br3ϪPd2ϪS2 91.21(6) I1ϪPd1ϪS1
Br2ϪPd1ϪS1 89.82(6) Br4ϪPd2ϪS2 174.48(6) I2ϪPd1ϪS1
91.78(2) Br1ϪPd1ϪS1 172.90(4) I1ϪPd1ϪS1
91.04(4) Br1ϪPd1ϪP1 92.09(4) I1ϪPd1ϪP1
171.38(7)
92.64(7)
177.19(5) S1ϪPd1ϪP1
93.97(5) S1ϪPd1ϪP1 92.73(9)
Br1ϪPd1ϪN2 89.5(2)
Br2ϪPd1ϪN2 176.6(2) Br4ϪPd2ϪN6 89.2(2)
S1ϪPd1ϪN2 87.3(2) S2ϪPd2ϪN6 86.9(2)
Br3ϪPd2ϪN6 177.9(2) I1ϪPd1ϪN2 176.8(1) Br1ϪPd1ϪN3 88.8(1)
I1ϪPd1ϪN2 89.6(2)
S1ϪPd1ϪN2 85.3(2)
I2ϪPd1ϪN2 91.2(1)
S1ϪPd1ϪN2 86.0(1)
S1ϪPd1ϪN2 84.8(1)
P1ϪPd1ϪN2 174.5(1) P1ϪPd1ϪN2 176.7(2)
Pd1ϪN2ϪN1 114.3(4) Pd2ϪN6ϪN5 114.3(5) Pd1ϪN2ϪN1 114.1(3) Pd1ϪS1ϪC1 97.3(2)
Pd1ϪS1ϪC1 99.7(3)
Pd1ϪS1ϪC1
97.6(3)
Pd2ϪS2ϪC5
97.9(3)
Pd1ϪS1ϪC1 97.9(2)
Pd1ϪN2ϪN1 114.0(3) Pd1ϪN2ϪN1 114.8(5)
Eur. J. Inorg. Chem. 2000, 1877Ϫ1882
1881

M. Ghassemzadeh, M. Bolourtchian, S. Chitsaz, B. Neumüller, M. M. Heravi
FULL PAPER
ensbourg, Inorg. Chem. 1995, 34, 6279Ϫ6286. Ϫ [7b] J. Real, M.
C), 1552 (m), 1500 (m), 1437 (m), 1322 (m), 1301 (m), 1228 (m),
1160 (vw), 1097 (m), 1008 (m), 968 (m), 928 (w), 847 (w), 746 (m),
691 (m), 639 (w), 602 (w), 534 (m), 506 (m), 449 [m, ν(PdN)], 409
(w), 374 [w, ν(PdS)], 308 (w), 285 (w), 227 (w), 198 [w, ν(PdI)], 139
(vw), 124 (vw). Ϫ 31P NMR (CD3OD): δ ϭ 26.2 (s).
Pages, A. Polo, J. F. Piniella, A. Alvarez-Larena, Chem. Com-
mun. 1999, 277Ϫ278. Ϫ [7c]M. Gupta, R. E. Cramer, K. Ho,
C. Pettersen, S. Mishina, J. Belli, C. M. Jensen, Inorg. Chem.
1995, 34, 60Ϫ65.
[8]
J. E. Huheey, Anorganische Chemie, de Gruyter, Berlin, 1988.
[9] [9a]
R. Martin, H. J. Keller, B. Müller, Z. Naturforsch. 1985,
[9b]
40B, 57Ϫ60. Ϫ
T. N. Margulis, L. J. Zompa, Inorg. Chim.
Crystal Structure Analyses of 2, 3, 4, and 5 (Table 1 and 2): The
selected crystals of 2؊5 were covered with a perfluorinated oil and
mounted on the tip of a glass capillary under a flow of cold gaseous
nitrogen. The orientation matrix and preliminary unit cell dimen-
sions were determined from 2000 (2, Stoe IPDS), 2000 (3, Stoe
IPDS), 15 (4, Siemens P4), and 15 (5, Enraf-Nonius CAD4)
reflections (graphite-monochromated Mo-Kα radiation in all cases;
λ ϭ 71.073 pm). The final cell parameters were determined from
5000 reflections for 2 and 5, and from 25 high-angle reflections for
3 and 4. The intensities were corrected for Lorentz and polarization
effects. In addition, absorption corrections were applied for 2 (nu-
merical), 3 (empirical, 10 psi-scans), 4 (numerical), and 5 (empir-
ical, 10 psi-scans). The structures were solved by the Patterson
[9c]
Acta 1992, 201, 61Ϫ67. Ϫ
T. J. Giordano, W. M. Butler, P.
G. Rasmussen, Inorg. Chem. 1978, 17, 1917Ϫ1922. Ϫ [9d] H. A.
Ankersmit, P. T. Witte, M. Kooijman, M. T. Lakin, A. L. Spek,
K. Goubitz, K. Vrieze, G. van Koten, Inorg. Chem. 1996, 35,
6053Ϫ6063. Ϫ [9e]P. F. Kelly, A. M. Z. Slawin, A. Soriano-
[9f]
Rama, J. Chem. Soc., Dalton Trans. 1996, 53Ϫ59. Ϫ
A. D.
Ryabov, L. G. KuzЈmina, V. A. Polyakov, G. M. Kazankov, E.
S. Ryabova, M. Pfeffer, R. van Eldik, J. Chem. Soc., Dalton
[9g]
Trans. 1995, 999Ϫ1006. Ϫ
A. Mayr, L.-F. Mao, Inorg.
[9h]
Chem. 1998, 37, 5776Ϫ5780. Ϫ
A. S. Hirschon, W. K.
Musker, M. M. Olmstead, J. L. Dallas, Inorg. Chem. 1981, 20,
1702Ϫ1706. Ϫ [9i] Z. Guo, U. Caselatto, G. Faraglia, R. Grazi-
ani, S. Sitran, J. Chem. Soc., Dalton Trans. 1993, 2509Ϫ2513.
[9j]
Ϫ
M. Kubota, S. Ohba, Y. Saito, Acta Crystallogr. 1991,
C47, 1727Ϫ1729.
[10]
[11]
L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell
University Press, New York, 1960.
Established by a search of the Cambridge Structural Database:
see F. H. Allen, O. Kennard, R. Taylor, Acc. Chem. Res. 1983,
16, 146Ϫ153.
method for 2 and by direct methods for 3؊5 (SHELXTL-Plus[14]
)
and refined against F2 by full-matrix least-squares using the pro-
gram SHELXL-97.[15] The hydrogen atoms (CϪH) in 2 and 5 were
calculated in ideal positions (refinement with a common displace-
ment parameter). The hydrogen atoms of the NH groups were fixed
at 85 pm (2) or freely refined (5). The positions of the H atoms in
3 were freely refined, except for the N2ϪH2, N3ϪH3, and O2ϪH4
distances, which were fixed at 85 pm. The hydrogen atoms in 4 were
freely refined. Programs used were SHELXTL-Plus, SHELXL-97,
SHELXTL,[16] ORTEP,[17] and PLATON.[18] Splitting models were
applied to the following atoms: C181, C182 (and adjacent H atoms,
occupancy factors: 0.7, 0.3; 2); O3, C9, C10, C11, C12 (occupancy
factor: 0.5; 2), H5, H61, H62, H63 (occupancy factor: 0.5; 3).[19]
[12] [12a]
J. Vincente, I. Saura-Llames, M. G. Palin, P. G. Jones, M.
[12b]
C. R. de Arellano, Organometallics 1997, 16, 826Ϫ833. Ϫ
J. Vicente, I. Saura-Llamas, P. G. Jones, J. Chem. Soc., Dalton
Trans. 1993, 3619Ϫ3624. Ϫ [12c] J. Albert, J. Granell, A. Luque,
M. Font-Bardia, X. Solans, J. Organomet. Chem. 1997, 545,
[12d]
131Ϫ137. Ϫ
J. Albert, J. Granell, R. Moragas, M. Font-
Bardia, X. Solans, J. Organomet. Chem. 1996, 522, 59Ϫ67. Ϫ
[12e]
J. Albert, J. Granell, A. Luque, J. Minguez, R. Moragas,
M. Font-Bardia, X. Solans, J. Organomet. Chem. 1996, 522,
[12f]
87Ϫ95. Ϫ
J. Albert, J. Granell, J. Sales, M. Font-Bardia,
X. Solans, Organometallics 1995, 14, 1393Ϫ1404. Ϫ [12g] T. De-
baerdemaeker, A. Kutoglo, G. Schmid, L. Weber, Acta Crys-
[12h]
tallogr. 1973, B29, 1283Ϫ1288. Ϫ
E. van der Voort, P. van
der Sluis, A. L. Spek, Acta Crystallogr. 1987, C43, 461Ϫ463.
Ϫ
[12i] R. F. Wu, I. J. B. Lin, G. H. Lee, M. C. Cheng, Y. Wang,
Acknowledgments
Organometallics 1990, 9, 126Ϫ130.
[13]
[14]
A. Dornow, H. Menzel, P. Marx, Chem. Ber. 1964, 97,
Support of this work by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie is gratefully acknowledged.
2173Ϫ2178.
G. M. Sheldrick, SHELXTL-Plus, Release 4.2 for Siemens R3
Crystallographic Systems, Siemens Analytical X-ray Instru-
ments Inc., Madison (WI), 1990.
G. M. Sheldrick, SHELXL-97, Universität Göttingen, 1997.
G. M. Sheldrick, SHELXTL, Release 5.05/VMS for Siemens
R3 Crystallographic Research Systems, Siemens Analytical X-
ray Instruments Inc., Madison (WI), 1996.
C. K. Johnson, ORTEP, ORNL-3794, Oak Ridge National
Laboratory, Tennessee, 1965.
A. L. Spek, PLATON-98, Universiteit Utrecht, 1998.
Further details can be obtained free of charge on application to
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, U.K. [Fax: (internat.) ϩ44 (0)1223
336033; E-mail: deposit@ccdc.cam.ac.uk] quoting the deposit-
ory nos. CCDC-141168 (2), -141169 (3), -141170 (4), and
-141171 (5).
International Tables for Crystallography, 2nd ed., vol. A,
Kluwer Academic Publishers, Dordrecht, 1989.
Received March 2, 2000
[1] [1a]
H. Neunhoeffer, in Comprehensive Heterocyclic Chemistry,
[15]
[16]
vol. 3 (Eds.: A. R. Katritzky, C. W. Rees), Pergamon Press,
[1b]
Oxford, 1984, p. 385Ϫ456. Ϫ
M. Akbar Ali, S. E. Liv-
[1c]
ingstone, Coord. Chem. Rev. 1974, 13, 101Ϫ132. Ϫ
K.
Severin, R. Bergs, W. Beck, Angew. Chem. Int. Ed. 1998, 37,
[17]
1722Ϫ1743.
[2]
[3]
[4]
[5]
[6]
F. Adhami, M. Ghassemzadeh, M. M. Heravi, A. Taeb, B. Ne-
umüller, Z. Anorg. Allg. Chem. 1999, 625, 1411Ϫ1412.
M. Ghassemzadeh, K. Aghapoor, M. M. Heravi, B. Neumüller,
[18]
[19]
Z. Anorg. Allg. Chem. 1998, 624, 1969Ϫ1972.
B. Neumüller, M. M. Heravi, M. Ghassemzadeh, Z. Anorg.
Allg. Chem. 1999, 625, 1908Ϫ1911.
J. Weidlein, U. Müller, K. Dehnicke, Schwingungsfrequenzen II,
Thieme Verlag, Stuttgart, 1986.
[20]
A. G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G.
Watson, R. Taylor, J. Chem. Soc., Dalton Trans. 1989, S1ϪS83.
[7] [7a]
T. Tuntulani, G. Musie, J. H. Reibenspies, M. Y. Dar-
[I00082]
1882
Eur. J. Inorg. Chem. 2000, 1877Ϫ1882