Reactions of pyrrole-2,5-dicarbaldehyde with 2-aminodiphenylamine in the presence of nickel and cobalt trimethylacetates

Article abstract of DOI:10.1023/A:1020995930577

The reactions of pyrrole-2,5-dicarbaldehyde (1) with 2-aminodiphenylamine (3) taken in a ratio of 1:2 in the presence of polinuclear nickel(II) and cobalt(II) trimethylacetate complexes were studied in MeCN. The reaction with Ni₉(HOOCCMe₃)₄(μ₄-OH) ₃(μ₃-OH)₃(OOCCMe₃)₁₂ (2) afforded the mononuclear complex Ni(OOCCMe₃) ₂[(PhHN)C₆H₄NHCHC₄H ₂NCHNC₆H₄(NHPh)] (4) with a new ligand, which is the product of condensation of one molecule 1 with two molecules 3 and contains two NHPh groups. By contrast, the reaction with the polymeric complex [Co(OH)_n(OOCCMe₃)_2-n]_x (5, n = 0.05-0.1) gave rise to the tetranuclear complex Co₄(μ ₄-O)(μ-OOCCMe₃)₄L₂ (6), where L is, apparently, the product of further oxidation of Schiff's base to the benzimidazole derivative. The structures of compounds 4 and 6 were established by X-ray diffraction analysis.

Full text of DOI:10.1023/A:1020995930577

Russian Chemical Bulletin, International Edition, Vol. 51, No. 8, pp. 1575—1580, August, 2002
1575
Reactions of pyrroleꢀ2,5ꢀdicarbaldehyde with 2ꢀaminodiphenylamine
in the presence of nickel and cobalt trimethylacetates
b
b
b
A. Yu. Chernyadyev,a Yu. A. Ustynyuk,a G. G. Aleksandrov, A. A. Sidorov, V. M. Novotortsev,
ꢀ
V. N. Ikorskii,c S. E. Nefedov,b I. L. Eremenko,b and I. I. Moiseevb
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
Leninskie Gory, 119899 Moscow, Russian Federation.
Fax: +7 (095) 939 4575. Eꢀmail: yust@nmr.chem.msu.su
bN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 954 1279. Eꢀmail: ilerem@igic.ras.ru
cInternational Tomography Center, Siberian Branch of the Russian Academy of Sciences,
3А Institutskaya ul., 630090 Novosibirsk, Russian Federation
The reactions of pyrroleꢀ2,5ꢀdicarbaldehyde (1) with 2ꢀaminodiphenylamine (3) taken
in a ratio of 1 : 2 in the presence of polinuclear nickel(II) and cobalt(II) trimethylꢀ
acetate complexes were studied in MeCN. The reaction with Ni9(HOOCCMe3)4(µ ꢀ
4
OH)3(µ ꢀOH)3(OOCCMe3)12
(2)
afforded
the
mononuclear
complex
3
Ni(OOCCMe3)2[(PhHN)C6H4NHCHC4H2NCHNC6H4(NHPh)] (4) with a new ligand,
which is the product of condensation of one molecule 1 with two molecules 3 and
contains two NHPh groups. By contrast, the reaction with the polymeric complex
[Co(OH)n(OOCCMe3)2–n]x (5, n = 0.05—0.1) gave rise to the tetranuclear complex
Co4(µ ꢀO)(µꢀOOCCMe3)4L2 (6), where L is, apparently, the product of further oxidation of
4
Schiff's base to the benzimidazole derivative. The structures of compounds 4 and 6 were
established by Xꢀray diffraction analysis.
Key words: nickel, cobalt, trimethylacetate complexes, pyrroleꢀ2,5ꢀdicarbaldehyde,
2ꢀaminodiphenylamine, condensation, Xꢀray diffraction analysis, magnetic properties.
Recently,1 we have demonstrated that the reaction of
pyrroleꢀ2,5ꢀdicarbaldehyde (1) with oꢀphenylenediamine
in the presence of the nonanuclear nickel(II) cluster
Ni9(HOOCCMe3)4(µ4ꢀOH)3(µ3ꢀOH)3(OOCCMe3)12 (2)
afforded the condensation product of three diamine molꢀ
ecules and two dialdehyde molecules to form a compliꢀ
cated ligand "enveloping" the tetranuclear metal carboxyꢀ
late fragment. In the present study, we found that the
chemical properties of oꢀphenylenediamine in the reacꢀ
tions with nickel carboxylates2 differ from those of its
Nꢀphenylꢀsubstituted analog, viz., 2ꢀaminodiphenylamine
(3), although the condensation of dicarbaldehyde 1 with
oꢀphenylenediamine or diamine 3 without additional acꢀ
tivation by transition metal complexes proceeds simiꢀ
larly to yield [1+1] Schiff's bases.3,4
(4) with the ligand, which is the product of condensation
of one molecule 1 with two molecules 3 (Scheme 1).
According to the Xꢀray diffraction analysis, only three of
five N atoms capable of forming complexes are involved
in interactions with the metal atom in complex 4 (Fig. 1,
Table 1). The shortest Ni—N bond (2.009(3) Å) is that
with the central N(2) atom, whereas the bond with the
N(3) atom of the azomethine fragment (2.110(4) Å) is
somewhat longer, and the longest distance (2.187(4) Å)
is that between the Ni atom and the N(1) atom of
the diphenylamine group. The coordination enviꢀ
ronment about the NiII atom is completed to a disꢀ
torted octahedron through binding with two O atoms
of the chelate trimethylacetate group (Ni—O, 2.097
and 2.150(3) Å) and one O atom of the terminal
trimethylacetate group (Ni—O, 1.997(3) Å). The tridenꢀ
tate coordination of the ligand gives rise to two adjaꢀ
cent fiveꢀmembered Ni(1)N(1)C(17)C(18)N(2) and
Ni(1)N(2)C(23)C(24)N(3) metallocycles. Both virtually
planar fragments adopt a strongly flattened envelope
conformation with the Ni atom deviating from the
plane of the four other atoms of the metallocycles by
Results and Discussion
We found that the reactions of compounds 1
and 3 in MeCN in the presence of cluster 2
afforded
the
mononuclear
nickel
complex
Ni(OOCCMe3)2[(PhHN)C6H4NHCHC4H2NCHNC6H4(NHPh)]
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1448—1452, August, 2002.
1066ꢀ5285/02/5108ꢀ1575 $27.00 © 2002 Plenum Publishing Corporation

1576
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Chernyadyev et al.
Scheme 1
C(25)
C(24)
C(26)
C(27)
C(23)
N(2)
C(25)
C(22)
N(3)
C(20)
C(5)
O(2)
C(28)
N(4)
C(30)
C(1)
O(1)
Ni(1)
C(2)
C(31)
C(32)
C(19)
C(29)
C(17)
O(3)
C(6)
C(18)
C(4)
N(1)
C(25)
N(5)
C(16)
C(15)
C(10)
C(7)
C(33)
O(4)
C(35)
C(12)
C(40)
C(14)
C(13)
C(36)
C(8)
C(39)
C(37)
C(38)
Fig. 1. Molecular structure of complex 4.

New nickel(II) and cobalt(II) complexes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1577
Table 1. Principal bond lengths (d) and bond angles (ω) in
complex 4
the N(3) atom and the midpoint of the C(25)—C(26)
bond). The largest distortion of the symmetry associated
with coordination of the metal atom is manifested in the
difference between the first (C(11)N(1)C(17)C(22)) and
the last (C(29)C(34)N(5)C(35)) fragments in the chain.
The corresponding dihedral angles between the planes of
the phenyl groups at the C(11) and C(17) atoms and at
the C(29) and C(35) atoms are 67.4 and 46.9°, respecꢀ
tively. These Ph groups form angles of 69.3, 6.4, 12.9,
and 45.0°, respectively, with the plane of the central
pyrrole ring. The distribution of the bond lengths in the
ligand (the N(2)—C(23), C(24)—N(3), C(25)—C(26),
and C(28)—N(4) bond lengths are close to the double
bond length;5 see Table 1) is indicative of a particular
contribution of the zwitterionic form bearing a positive
charge on the N(4) and a negative charge on the C(27)
atom of the pyrrole ring. It should be noted that the
ligand is formally neutral (the positive charge of the diꢀ
valent Ni atom is compensated by the negative charges
of two trimethylacetate anions). Another perturbing facꢀ
tor responsible for a distortion of the planar structure of
the ligand is associated with the presence of three active
protons (at the N atoms) capable of hydrogen bonding.
Two protons, viz., H(1N) and H(5N), form rather strong
intramolecular N—H...O hydrogen bonds (N(1)—H(1N),
1.00(5) Å; H(1N)...O(4), 1.75(5) Å; N(5)—H(5N),
0.89(6) Å; H(5N)...O(1), 1.98(6) Å), whereas the third
hydrogen atom, viz., H(4N), is involved in a short H...O
contact to a much lesser extent (N(4)—H(4N), 0.81(4) Å;
H(4N)...O(1), 2.31(5) Å).
Bond
d/Å
Angle
ω/deg
Ni(1)—O(1)
Ni(1)—O(3)
Ni(1)—N(2)
O(1)—C(1)
O(3)—C(6)
2.097(3)
1.997(3)
2.009(3)
1.278(6)
1.270(5)
O(1)—Ni(1)—O(2)
O(1)—Ni(1)—N(1)
O(1)—Ni(1)—N(3)
O(2)—Ni(1)—N(1)
O(2)—Ni(1)—N(3)
O(3)—Ni(1)—N(2)
N(1)—Ni(1)—N(2)
N(2)—Ni(1)—N(3)
Ni(1)—O(2)—C(1)
Ni(1)—N(1)—C(11) 118.3(3)
C(11)—N(1)—C(17) 115.4(4)
Ni(1)—N(2)—C(23) 115.9(4)
Ni(1)—N(3)—C(24) 109.3(3)
C(24)—N(3)—C(27) 104.9(4)
C(34)—N(5)—C(35) 126.0(5)
O(3)—C(6)—O(4)
O(1)—Ni(1)—O(3)
O(1)—Ni(1)—N(2)
O(2)—Ni(1)—O(3)
O(2)—Ni(1)—N(2)
O(3)—Ni(1)—N(1)
O(3)—Ni(1)—N(3)
N(1)—Ni(1)—N(3)
Ni(1)—O(1)—C(1)
Ni(1)—O(3)—C(6)
61.56(13)
101.1(2)
100.5(2)
93.5(2)
94.8(2)
109.84(14)
78.8(2)
N(1)—H(1N) 1.00(5)
N(1)—C(17)
N(2)—C(23)
N(3)—C(27)
N(4)—C(28)
1.453(5)
1.289(6)
1.355(6)
1.317(6)
80.3(2)
89.0(3)
N(5)—H(5N) 0.89(6)
N(5)—C(35)
Ni(1)—O(2)
Ni(1)—N(1)
Ni(1)—N(3)
O(2)—C(1)
O(4)—C(6)
N(1)—C(11)
N(2)—C(22)
N(3)—C(24)
1.415(6)
2.150(3)
2.187(4)
2.110(4)
1.247(5)
1.247(5)
1.450(5)
1.392(6)
1.356(5)
125.0(5)
92.06(13)
158.3(2)
153.5(2)
96.7(2)
94.4(2)
87.0(2)
158.3(2)
90.7(3)
132.2(3)
N(4)—H(4N) 0.81(4)
N(4)—C(29)
N(5)—C(34)
1.429(6)
1.402(6)
Ni(1)—N(1)—C(17) 108.8(3)
Ni(1)—N(2)—C(22) 117.8(3)
C(22)—N(2)—C(23) 125.6(4)
Ni(1)—N(3)—C(27) 145.6(4)
C(28)—N(4)—C(29) 126.6(5)
The presence of a magnetic center, viz., the NiII atom
in the 20ꢀelectron configuration, is responsible for the
magnetic properties of complex 4. The magnetic suscepꢀ
tibility measurements demonstrated that the effective
magnetic moment of complex 4 varies from 0.77 to 2.89
µB in the temperature range of 2—301 К (Fig. 2).
The reaction of compound 1 with 3 in MeCN in
the presence of polymeric cobalt trimethylacetate
[Co(OH)n(OOCCMe3)2–n]x (5, n = 0.05—0.1) afforded
O(1)—C(1)—O(2)
118.6(5)
0.31 and 0.09 Å, respectively. At the same time, the
Ni atom is at a distance of only 0.15 Å from the
N(1)C(17)C(18)N(2)C(23)C(24)N(3) plane passing
through all nonꢀmetal atoms of both metallocycles. The
planar conformation of the ligand as a whole (except for
the phenyl substituents of the amino groups) is a conseꢀ
quence of conjugation between the πꢀelectron systems of
the double bonds of the pyrrole ring and two phenylene
fragments. Apparently, slight distortions can be considꢀ
ered as a result of steric nonbonded interactions between
the atoms within the ligand and redistribution of the
electron density within the organic rings through coordiꢀ
nation of some N atoms to the metal atom. The geomꢀ
etry of the ligand can be characterized by the torsion
angles in the C(11)N(1)C(17)C(22)N(2)C(23)C(24)
µ
eff/µ
B
3.0
2.5
2.0
1.5
1.0
N(3)C(27)C(28)N(4)C(29)C(34)N(5)C(35)
chain
(146.3, 2.9, 177.6, –177.0, 5.5, –177.9, 176.5, –3.8,
176.2, 174.7, 1.5, and –158.3°, respectively). Analysis of
these values shows that this ligand is nearly symmetrical
with respect to the central N(3) atom of the pyrrole ring
(i.e., it possesses a twofold pseudoaxis passing through
50
100
150
200
250
T/K
Fig. 2. Temperature dependence of the effective magnetic moꢀ
ment (µeff) for complex 4.

1578
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Chernyadyev et al.
C(39)
C(25)
C(40)
C(26)
C(24)
O(3A)
C(38)
O(4A)
C(35)
C(27)
C(37)
C(23)
O(1A)
N(5)
C(28)
C(36)
C(22)
O(2A)
Co(2A)
N(4)
N(5A)
C(20)
Co(1A)
O
N(4A)
N(3A)
O(4)
C(6)
C(8)
N(1A)
C(21)
Co(2)
N(3)
C(7)
C(39)
C(10)
O(2)
O(3)
N(2A)
C(3)
C(19)
C(9)
C(18)
C(17)
C(39)
O(1)
C(11)
C(1)
C(30)
C(12)
N(2)
C(2)
C(31)
C(32)
C(33)
C(16)
C(15)
C(29)
C(34)
C(4)
C(13)
C(14)
Fig. 3. Molecular structure of complex 6.
Table 2. Principal bond lengths (d) and bond angles (ω) in
complex 6
the tetranuclear complex Co4(µ ꢀO)(µꢀOOCCMe3)4L2
4
(6), where L is the product of condensation of two molꢀ
ecules 3 with one molecule 1 (see Scheme 1). Unlike the
analogous reactions involving nickel trimethylacetate
derivatives, condensation in the reaction under considꢀ
eration is accompanied by oxidation of Schiff's base to
the benzimidazole derivative. Xꢀray diffraction study of
brown single crystals of solvate 6•2MeCN•C6H5Me
(Fig. 3, Table 2) showed that four Co atoms in molecule
6 are linked through the bridging O atom (Co(1)—O,
1.949(3) Å; Co(2)—O, 1.928(4) Å) and are also linked
in pairs through two bridging trimethylacetate groups
(Co(1)—O(1), 2.121(6) Å; Co(1)—O(3), 2.008(6) Å;
Co(2)—O(2) 1.945(6), Å; Co(2)—O(4), 1.989(5) Å). Alꢀ
though the newly formed ligands in compound 6 are
formally built of two diamine molecules 3 and one
dicarbaldehyde molecule 1 (like in complex 4), their
geometric characteristics are substantially different. The
involvement of the Nꢀsubstituted amino groups in conꢀ
densation giving rise to two benzimidazole fragments
leads to an essential change in the coordinating ability of
the L ligand and virtually prevents the N atoms of these
groups from being involved in interactions with the metal
atoms. As a result, unlike the "enveloping" mode of coꢀ
ordination of the ligands in nickel complex 4, the bridgꢀ
Bond
d/Å
Angle
ω/deg
Co(1)—O
Co(1)—O(3)
Co(1)—N(3) 2.168(6)
Co(2)—O(2) 1.945(6)
Co(2)—N(4) 1.998(6)
1.949(3)
2.008(6)
O—Co(1)—O(3a)
O(3a)—Co(1)—N(1) 140.7(2)
O(3a)—Co(1)—O(1a) 87.6(2)
O—Co(1)—N(3)
N(1)—Co(1)—N(3)
101.9(2)
100.98(18)
80.4(3)
O(2)—C(1)
O(4)—C(6)
Co(1)—O(1)
1.279(10) O—Co(2)—O(2)
116.9(3)
100.6(3)
1.257(9)
2.121(6)
O(2)—Co(2)—O(4)
O(2)—Co(2)—N(4) 105.5(3)
Co(1)—N(1) 2.032(6)
Co(2)—O—Co(2a)
Co(2a)—O—Co(1)
O—Co(1)—N(1)
O—Co(1)—O(1a)
N(1)—Co(1)—O(1a) 87.7(2)
O(3a)—Co(1)—N(3) 90.6(2)
O(1a)—Co(1)—N(3) 158.8(2)
115.0(4)
100.09(5)
117.4(3)
Co(2)—O
1.928(4)
1.989(5)
1.259(9)
1.264(9)
Co(2)—O(4)
O(1)—C(1)
O(3)—C(6)
100.06(14)
O—Co(2)—O(4)
O—Co(2)—N(4)
104.3(2)
119.6(2)
O(4)—Co(2)—N(4) 108.1(3)
Co(2)—O—Co(1)
Co(1)—O—Co(1a)
106.35(5)
129.7(4)
Note. The atoms denoted by the index "a" are generated from
the basis atoms by the symmetry operation 1 – x, y, –z + 0.5.

New nickel(II) and cobalt(II) complexes
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1579
washed with cold toluene, and dried in vacuo. The yield was
243.5 mg (68%). IR, ν/cm–1: 3648 w, 3056 w, 2960 w, 2920 w,
2856 w, 1619 m, 1600 m, 1568 m, 1520 m, 1504 m, 1448 m,
1408 s, 1352 m, 1336 m, 1320 s, 1224 w, 1160 w, 1048 m, 1016 m,
928 w, 774 s, 696 s. Found (%): C, 67.06; H, 6.05; N, 9.84.
C40H43N5NiO4. Calculated (%): C, 67.04; H, 6.01; N, 9.78.
ing mode is observed for each new ligand in complex 6.
In the latter complex, the ligands each are coordinated
to two Co atoms, one metal atom being coordinated in a
monodentate mode through the N atom of the benzimiꢀ
dazole ring (Co(2)—N(4), 1.998(6) Å), whereas another
metal atom being coordinated in a chelating mode
through the N atoms of the pyrrole (Co(1)—N(1),
2.032(6) Å) and benzimidazole rings (Co(1)—N(3),
2.168(6) Å). As a result, only the N atoms suitable for
binding with the metal centers are involved in coordiꢀ
nation.
Apparently, the observed differences in the transforꢀ
mations of diamine 3 within the coordination spheres
about the Co and Ni atoms in the trimethylacetate comꢀ
plexes are associated with the difference in the elecꢀ
tronic characteristics of the metal centers (the CoII atom
has one less electron than the NiII atom) and, correꢀ
spondingly, with the difference in coordinating ability of
the atoms. Generally, the NiII atom in the trimethylꢀ
acetate complexes (except for the binuclear lanternꢀlike
dimers) has an octahedral ligand environment,6 unlike
the Co atom, which can have different coordination numꢀ
bers (from 4 to 6).7,8 In addition, the CoII atom in these
systems is readily oxidized to form CoIII derivatives,9,10
which can serve as intermediates in the process under
study. Probably, it is these intermediates that stimulate
oxidation of Schiff's base to the benzimidazole derivative
accompanied by reduction of the metal center to the
starting CoII state. The results of the present study demꢀ
onstrate that the chemical assembly of complicated orꢀ
ganic molecules can be controlled by choosing metal
centers at which condensation of pyrroleꢀ2,5ꢀdicarbꢀ
aldehyde with 2ꢀaminodiphenylamine proceeds under
similar conditions.
Synthesis of the Co4(µ ꢀO)(µꢀOOCCMe3)4•L2 complex (6).
4
Solid compound 1 (62 mg, 0.5 mmol) and solid compound 3
(184 mg, 1 mmol) were successively added to a solution of
polymer 5 (130 mg) in MeCN (80 mL). The resulting solution
was heated to 70 °C for 10 min. The darkꢀbrown solution was
concentrated to 15 mL, toluene (10 mL) was added, and the
reaction mixture was kept at 5 °C for 2 days. The darkꢀbrown
crystals that formed were separated from the solution by deꢀ
cantation, washed with cold MeCN, and dried in vacuo
(25 °C, 0.1 Torr). The yield was 121 mg (58%). IR, ν/cm–1
:
2960 w, 2928 w, 2872 w, 1576 s, 1480 m, 1450 m, 1416 m,
1384 m, 1328 w, 1224 m, 1152 w, 1032 w, 896 w, 792 w,
768 m, 744 m, 688 m, 632 w, 464 w. C80H76Co4N10O9•C7H8.
Found (%): C, 63.31; H, 5.07; N, 8.55. Calculated (%):
C, 63.36; H, 5.10; N, 8.50.
Xꢀray diffraction study of complexes 4 and 6. The Xꢀray difꢀ
fraction data sets for complex 4 and solvate 6•2MeCN•C6H5Me
were collected in the Center of Xꢀray Diffraction Studies
(A. N. Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences) on a Bruker AXS SMARTꢀ1000
diffractometer equipped with a CCD detector (λ(Mo), graphꢀ
ite monochromator, ω scanning technique, scan step was 0.3°,
frames were exposed for 30 s, 2θ
= 60°) according to a
max
standard procedure.13 The semiempirical absorption correcꢀ
tion was applied.14 The structure was solved by direct methods
using the SHELXS97 program package15 and refined by the
fullꢀmatrix leastꢀsquares method with anisotropic thermal paꢀ
rameters for all nonhydrogen atoms using the SHELXL97 proꢀ
gram package.16 The positions of the H atoms of the amino
groups were revealed from difference electron density maps
and refined isotropically. The positions of the remaining H atoms
were calculated geometrically and refined using the riding model.
Experimental
Table 3. Crystallographic parameters of complexes 4 and
6•2MeCN•C6H5Me
Pyrroleꢀ2,5ꢀdicarbaldehyde
(1),11
nonanuclear
nickel trimethylacetate Ni9(HOOCMe3)4(µ ꢀOH)3(µ ꢀ
4
3
OH)3(OOCCMe3)12 (2),12 and polymeric cobalt trimethylꢀ
acetate [Co(OH)n(OOCCMe3)2–n]x (5)7 (n = 0.05—0.1) were
prepared according to known procedures. All reactions were
carried out with the use of anhydrous solvents. The IR spectra
were recorded on a Specord Mꢀ80 spectrophotometer in KBr
pellets in the frequency range of 392—4000 cm–1. The static
magnetic susceptibility was measured on a SQUID MPMSꢀ59
magnetometer in the temperature range of 2—301 K.
Compound
4
6•2MeCN•C6H5Me
Compound
Space group
a/Å
b/Å
c/Å
β/deg
V/Å3
Z
C
40H43N5O4Ni
C2/c
C91H90N12O9Co4
Cc
28.789(9)
17.276(4)
19.949(5)
133.493(13)
7198(3)
8
18.554(3)
19.482(3)
25.971(4)
103.099(4)
9143(2)
4
Synthesis
of
the
Ni(OOCCMe3)2[(PhHN)C6H4NHCHC4H2NCHNC6H4(NHPh)]
complex (4). Diamine 3 (130 mg, 0.0575 mmol) and dicarbꢀ
aldehyde 1 (62 mg, 0.5 mmol) were successively dissolved in
MeCN (70 mL) and then complex 2 (184 mg, 1 mmol) was
added. The reaction solution was stirred at ∼20 °C for 30 min,
concentrated to 15 mL at 50 °C, and kept at ∼20 °C for 6 h.
The large prismatic darkꢀbrown (almost black) crystals that
formed were separated from the mother liquor by decantation,
dcalc/g cm–3
µ/mm–1
θ range/deg
Number of independent
reflections
1.322
0.587
1.56—30.25
1.258
0.773
1.54—30.01
6176
0.0798
0.2021
6632
0.0819
0.1975
R1
wR2

1580
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Chernyadyev et al.
The principal crystallographic parameters of compounds 4 and 6
are given in Table 3. The selected bond lengths and bond angles
for compounds 4 and 6 are listed in Tables 1 and 2, respecꢀ
tively.
7. M. A. Golubnichaya, A. A. Sidorov, I. G. Fomina,
M. O. Ponina, S. M. Deomidov, S. E. Nefedov, I. L.
Eremenko, and I. I. Moiseev, Izv. Akad. Nauk, Ser. Khim.,
1999, 1773 [Russ. Chem. Bull., 1999, 48, 1751 (Engl.
Transl.)].
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 99ꢀ03ꢀ
33091, 99ꢀ03ꢀ32792, 00ꢀ15ꢀ97429, and 00ꢀ03ꢀ32807) and
by the Ministry of Industry, Science, and Technology of
the Russian Federation (Grant 9.03.05).
8. M. A. Golubnichaya, A. A. Sidorov, I. G. Fomina, L. T.
Eremenko, S. E. Nefedov, I. L. Eremenko, and I. I. Moiseev,
Zh. Neorg. Khim., 1999, 44, 1479 [Russ. J. Inorg. Chem.,
1999, 44 (Engl. Transl.)].
9. А. A. Sidorov, M. O. Ponina, S. M. Deomidov, V. M.
Novotortsev, A. Demonceau, S. E. Nefedov, I. L. Eremenko,
and I. I. Moiseev, J. Chem. Soc., Chem. Commun., 2000, 1383.
10. A. A. Sidorov, M. O. Talismanova, I. G. Fomina, G. G.
Aleksandrov, V. M. Novotortsev, A. Demonceau, S. E.
Nefedov, I. L. Eremenko, and I. I. Moiseev, Izv. Akad.
Nauk, Ser. Khim., 2001, 2106 [Russ. Chem. Bull., Int. Ed.,
2001, 50, 2206].
11. R. Miller and K. Olsson, Acta Chem. Scand., 1981, B35, 303.
12. I. L. Eremenko, M. A. Golubnichaya, S. E. Nefedov, A. A.
Sidorov, I. F. Golovaneva, V. I. Burkov, O. G. Ellert, V. M.
Novotortsev, L. T. Eremenko, A. Sousa, and M. R. Bermejo,
Izv. Akad. Nauk, Ser. Khim., 1998, 725 [Russ. Chem. Bull.,
1998, 47, 704 (Engl. Transl.)].
13. SMART (Control) and SAINT (Integration) Software, Verꢀ
sion 5.0, Bruker AXS Inc., Madison, WI, 1997.
14. G. M. Sheldrick, SADABS, Program for Scaling and Correcꢀ
tion of Area Detector Data, Göttingen University, Göttingen
(Germany), 1997 (based on the method of R. H. Blessing,
Acta Crystallogr., A, 1995, 51, 33).
15. G. M. Sheldrick, SHELXS97, Program for the Solution of
Crystal Structures, Göttingen University, Göttingen (Gerꢀ
many), 1997.
16. G. M. Sheldrick, SHELXL97, Program for the Refinement of
Crystal Structures, Göttingen University, Göttingen (Gerꢀ
many), 1997.
References
1. A. Yu. Chernyadyev, Yu. A. Ustynyuk, G. G. Aleksandrov,
A. A. Sidorov, V. M. Novotortsev, V. N. Ikorskii, S. E.
Nefedov, I. L. Eremenko, and I. I. Moiseev, Izv. Akad.
Nauk, Ser. Khim., 2001, 1271 [Russ. Chem. Bull., Int. Ed.,
2001, 50, 1336 (Engl. Transl.)].
2. A. E. Malkov, G. G. Aleksandrov, V. N. Ikorskii, A. A.
Sidorov, I. G. Fomina, S. E. Nefedov, V. M. Novotortsev,
I. L. Eremenko, and I. I. Moiseev, Koord. Khim., 2001, 27,
677 [Russ. J. Coord. Chem., 2001, 27 (Engl. Transl.)].
3. I. G. Fomina, A. A. Sidorov, and A. Yu. Chernyadyev,
Abstr. XVIIth International Chernyaev Meeting on Chemistry,
Analysis and Technology of Platinum Metals, Moscow,
2001, 125.
4. A. Yu. Chernyadyev, Yu. A. Ustynyuk, O. V. Yazev, E. A.
Kataev, M. D. Reshetova, A. A. Sidorov, G. G. Aleksandrov,
V. N. Ikorskii, V. M. Novotortsev, S. E. Nefedov, I. L.
Eremenko, and I. I. Moiseev, Izv. Akad. Nauk, Ser. Khim.,
2001, 2334 [Russ. Chem. Bull., Int. Ed., 2001, 50, 2445].
5. H. A. Frank, O. Kennard, D. G. Watson, L. Brammer,
A. G. Orpen, and R. Taylor, J. Chem. Soc., Perkin Trans. 2,
1987, S1.
6. I. L. Eremenko, S. E. Nefedov, A. A. Sidorov, and I. I.
Moiseev, Izv. Akad. Nauk, Ser. Khim., 1999, 409 [Russ.
Chem. Bull., 1999, 48, 405 (Engl. Transl.)].
Received December 21, 2001