Binuclear and polynuclear transition metal complexes with macrocyclic ligands 1. Synthesis and the structure of an antiferromagnetic binuclear nickel complex prepared by the reaction of o-phenylenediamine with pyrrole-2,5-dicarbaldehyde and nickel pivalate

Article abstract of DOI:10.1023/A:1015012302947

The reaction of pyrrole-2,5-dicarbaldehyde (1) with o-phenylenediamine (2) in anhydrous EtOH afforded a [1+1]-condensation product, viz., Schiff's base. The structure of the latter was established by NMR spectroscopy and X-ray diffraction analysis. The reaction of this product or a mixture of 1 and 2 with Ni₉(μ_n-OOCBu¹)₁₂(HOOCBu¹)₄(μ₄-OH)₃(μ₃-OH)₃ in MeCN in the presence of AcOH gave rise to an antiferromagnetic binuclear complex. According to the X-ray diffraction data, the macrocycle in the latter complex is a [2+2]-condensation product of compounds 1 and 2, μ_eff ranging from 0.569 to 2.614 μB (2-301 K), -2J = 360 cm^-1. The Ni₂(OAc)₂ fragment is located in the central cavity of the macrocycle. The structures of the condensation products are discussed based on the results of DFT quantum-chemical calculations.

Full text of DOI:10.1023/A:1015012302947

Russian Chemical Bulletin, International Edition, Vol. 50, No. 12, pp. 2445—2450, December, 2001
2445
Binuclear and polynuclear transition metal complexes
with macrocyclic ligands
1. Synthesis and the structure of an antiferromagnetic binuclear nickel complex
prepared by the reaction of o-phenylenediamine with pyrrole-2,5-dicarbaldehyde
and nickel pivalate
A. Yu. Chernyadyev,a Yu. A. Ustynyuk,a« O. V. Yazev,a E. A. Kataev,a M. D. Reshetova,a A. A. Sidorov,b
G. G. Aleksandrov,b V. N. Ikorskii,c V. M. Novotortsev,b 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 2677. E-mail: 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) 952 1279. E-mail: ilerem@igic.ras.ru
cInternational Tomography Center, Siberian Branch of the Russian Academy of Sciences, Institutskaya ul., 3À
630090 Novosibirsk, Russian Federation
The reaction of pyrrole-2,5-dicarbaldehyde (1) with o-phenylenediamine (2) in an-
hydrous EtOH afforded a [1+1]-condensation product, viz., Schiff's base. The structure of
the latter was established by NMR spectroscopy and X-ray diffraction analysis. The reaction
of this product or a mixture of 1 and 2 with Ni9(µn-OOCBut)12(HOOCBut)4(µ4-OH)3(µ3-OH)3
in MeCN in the presence of AcOH gave rise to an antiferromagnetic binuclear complex.
According to the X-ray diffraction data, the macrocycle in the latter complex is
a
[2+2]-condensation product of compounds 1 and 2, µeff ranging from 0.569 to 2.614 µB
(2—301 K), –2J = 360 cm–1. The Ni2(OAc)2 fragment is located in the central cavity of the
macrocycle. The structures of the condensation products are discussed based on the results of
DFT quantum-chemical calculations.
Key words: binuclear nickel(II) complexes, macrocyclic ligands, X-ray diffraction analy-
sis, quantum-chemical calculations, DFT.
Transition metal complexes which contain two or
ined the reaction of dialdehyde 1 with î-phenylenedi-
amine (2) in the absence of template agents and also in
the presence of the nonanuclear nickel complex
Ni9(µn-OOCBut)12(HOOCBut)4(µ4-OH)3(µ3-OH)3 (3).8
several metal ions in the immediate vicinity of each
other in the cavity of one macrocyclic ligand are of
considerable interest as models of active centers of
metal-containing proteins, molecular magnets, and po-
tential components of homogeneous catalytic systems.1—4
These complexes most commonly involve expanded por-
phyrins5 or macrocyclic Schiff's bases as the ligands.
The latter are prepared by [2+2]-condensation of α,α´-di-
carbonyl derivatives of pyrroles, pyridines, α,α´-di-
pyrroles, or phenols with aromatic or aliphatic diamines.
Homo- and heterobinuclear transition metal complexes
with macrocyclic Schiff's bases based on 4-substituted
2,6-diformylphenols have been studied in sufficient de-
tail.6 However, complexes based on pyrrole-2,5-di-
carbaldehyde (1) have received much less attention,
direct reactions of compound 1 with aromatic diamines
and its reactions in the presence of template agents
being virtually unknown.
Results and Discussion
It is well known that dialdehyde 1 exists in solutions
predominantly in the cis-cis conformation.9 In this con-
nection, the closure of the [2+2]-macrocycle would be
expected to proceed readily in the absence of template
agents. However, it appeared that the reaction of 1 with
2 in boiling ethanol (Scheme 1) afforded only rather
inert Schiff's base 4 (yellow crystals), which did not
undergo further condensation without additional activa-
tion. DFT quantum-chemical calculations,10 which were
carried out with the use of a program described previ-
ously,11 demonstrated that the minimum of the total
energy of molecule 4 corresponds to a non-planar con-
formation (the C(1)—C(6)—N(2)—C(7) torsion angle is
34.6°). The energy of another possible isomer in which
the H atom is transferred from the pyrrole N atom to
As part of our continuing studies on the synthesis
and structures of polynuclear and binuclear transition
metal complexes with macrocyclic ligands,7 we exam-
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2334—2339, December, 2001.
1066-5285/01/5012-2445 $25.00 © 2001 Plenum Publishing Corporation

2446
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Chernyadyev et al.
the O atom of the formyl group is 19 kcal mol–1 higher.
According to the results of calculations, compound 4
can form stable centrosymmetrical dimer 4...4 through
four hydrogen bonds (the energy of dimerization is
15.4 kcal mol–1).
N(3A)
C(5)
C(4)
Scheme 1
C(3)
O(1)
N(1)
6
7
H
H
H
H
C(2)
O
N(1A)
O(1A)
8
5
H
C(1)
C(6)
NH2
NH2
H
EtOH
+
H
HN
9, 10
4
3
H2N
N
N(2)
H
2
11
O
C(7)
HN
2
H
N(3)
C(8)
C(9)
1
O
C(12)
C(10)
H
1
C(11)
4
AcOH,
MeCN
t
t
Ni9(HOOCBu )4(µ4-OH)3(µ3-OH)3(µ -OOCBu )12
(3)
n
Fig. 1. Structure of the compound C12H11N3O (4).
H
dihedral angle between the planes of the pyrrole and
phenyl rings is 18.3° (the calculated value is 14.3°). The
plane passing through the atoms of the azomethine
chain C(1)C(6)N(2)C(7) forms angles of 21.5 and 4.2°
(the calculated values are 17.1° and 2.8°) with the planes
of the phenyl and pyrrole rings, respectively. The formyl
group is twisted about the C(4)—C(5) bond by 2.1° (the
calculated value is 1.2°) out of the plane of the pyrrole
ring. The molecule contains three protons (one proton
at the N(1) atom of the pyrrole ring and two protons of
the amino group at the N(3) atom) capable of hydrogen
bonding. However, only two H atoms, viz. H(N(1)) and
H(2N(3)), are involved in hydrogen bonds with the
formyl O(1) atom to form H-bonded centrosymmetrical
dimers 4...4.
Previously, it has been demonstrated that dialdehyde
1 reacts with aliphatic α,ω-diamines in the absence of
metal ions to give oligo- and polycondensation prod-
ucts.9,13 1,2-Diaminoethane and 1,3-diaminopropan-2-ol
are the exceptions; their reactions with compound 1 in
the absence of template agents gave rise to macrocyclic
Schiff's bases in rather high yields. The reaction of
3,4-diethylpyrrole-2,5-dicarbaldehyde with 1,2-diamino-
4,5-dimethoxybenzene in the presence of strong acids
(HNO3 or HCl) afforded the [2+2]-macrocycle.14
Template syntheses based on dialdehyde 1 and di-
amines are generally carried out in the presence of
deprotonating agents, an alkali, or 1,8-diamino-
N,N,N´N´-tetramethylnaphthalene ("proton sponge").13,14
Thus the reaction of copper acetate with compound 1
and 1,2-diaminoethane or 1,3-diaminopropane in metha-
nol in the presence of KOH gave rise to mononuclear
N
N
Ni
N
O
O
Me
H
H
O
Me
O
N
Ni
N
N
H
5
In a solution of compound 4 in DMSO, the H atom
of the NH group of the pyrrole ring is involved in strong
hydrogen bonding, which is unambiguously confirmed
by its chemical shift (δ 12.5) in the 1H NMR spectrum.
Two protons of the NH2 group give one substantially
broadened signal at δ 5.60, which indicates that the
rotation about the C—NH2 bond is hindered.
According to the X-ray diffraction data, compound 4
actually exists as a dimer in the crystal (Fig. 1). Dimer-
ization is realized through short hydrogen bonds be-
tween the O atoms of the aldehyde groups and the H
atoms of the amino groups of the phenylene fragment
and the NH group of the pyrrole ring (O(1)...H(NH),
2.157 Å; O(1)...H(NH2), 2.328 Å).
It should be noted that the calculated geometric
parameters of the dimer agree satisfactorily with the
corresponding values obtained in the X-ray diffraction
study. The bond lengths and bond angles have values
typical of Schiff's bases characterized previously.12 The

Binuclear transition metal complexes
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2447
neutral complexes 6 (Scheme 2), which have been char-
acterized by X-ray diffraction analysis. In these com-
plexes, the copper atom in the cavity of the macrocycle
is in a distorted planar-square environment and is bound
to two pyrrole and two azomethine N atoms. Two other
azomethine groups are not involved in coordination to
the metal atom and this portion of the macro-
cycle is nonplanar. The reactions of α,ω-diamines
H2N(CH2)nNH2 (n = 4—6) with binuclear copper
alkoxide complexes 7 afforded homobinuclear com-
plexes 8. In these complexes, the —Cu(OMe)2Cu—
fragment is located inside the macrocycle and is coordi-
nated by both pyrrole and two of four azomethine
N atoms.13
We found that the reaction of compounds 1 and 2 in
acetonitrile in the presence of AcOH and the potential
template agent, viz., the polynuclear nickel complex
Ni9(µn-OOCBut)12(HOOCBut)4(µ4-OH)3(µ3-OH)3 (3),
at room temperature afforded binuclear complex 5 (a
dark-red compound). In complex 5, two Ni atoms are
linked to each other through two bridging acetate extra
ligands. It should be noted that this complex can also be
readily prepared by the reaction of compounds 3 and 4
in MeCN in the presence of AcOH (see Scheme 1).
According to the X-ray diffraction data, both Ni
atoms in centrosymmetrical molecule 5 (Fig. 2) are
located inside the macrocycle, each atom being coordi-
nated by three N atoms (the Ni—N distances are 2.029,
2.034, and 1.937(2) Å). The coordination environment
about the Ni atoms is completed to a distorted trigonal
bipyramid with two O atoms of two acetate bridges
(Ni—O, 2.021 and 2.010(2) Å). The interatomic Ni...Ni
distance (2.5123(8) Å) is comparable with those found
in other carboxylate binuclear "lanterns" of nickel.16 The
fused macrocyclic C24H16N6 ligand in complex 5 is
virtually planar. The angle between the mean plane
passing through all non-hydrogen atoms of the ligand
(the Ni atoms are located at a distance of 0.04 Å from
this plane) and the plane of the acetate bridges is 89.5°.
The maximum deviation of the atoms of the central
macrocycle from its mean plane is ±0.09 Å. The maxi-
mum angle between the planar pyrrole and benzene
rings is 5.8°.
Scheme 2
H
H
N
H
O
O
1
MeOH KOH + Cu(AcO)2
O
O
Cu
MeO
Cu
N
Complex 5 is virtually insoluble in non-polar sol-
vents and is moderately soluble in DMF, DMSO, and
pyridine.
N
OMe
O
Each NiII atom has the spin-free electronic configu-
ration d8 and possesses two unpaired electrons. In this
connection, molecule 5 can exist in the singlet, triplet,
and quintet states. According to the results of quantum-
chemical DFT calculations, the minima on the potential
O
7
NH (CH ) NH
2
n
2
2
n = 2, 3
n = 4, 5, 6
energy surface correspond to all three states, and their
–1
total energies differ by no more than 2 kcal mol
.
The measurements of the static magnetic susceptibil-
ity for complex 5 demonstrated that its effective mag-
netic moment increased from 0.569 to 2.614 µB as the
temperature was raised from 2 to 301 K (Fig. 3). The
experimental data were interpreted using the best fit
method to fit the measured static magnetic susceptibili-
ties (χe) to the theoretical values (χt) calculated per
g-atom of the paramagnetic atoms. As a result, the
following values were obtained: S = 1, <g> = 2.01;
N
H
H
N
N
N
(CH2)n
N
N
Cu OMe
Cu
(CH2)n
N
(CH2)n
(CH2)n
N
MeO Cu
N
N
N
H
H
N
6
8
–1
–2J = 360 cm (see Fig. 3). Hence, antiferromagnetic
Mononuclear complexes with a planar macrocyclic
environment based on derivatives of compound 1 were
prepared by direct template syntheses starting from ura-
nyl nitrate, 3,4-diethylpyrrole-2,5-dicarbaldehyde, and
1,2-diamino-4,5-dimethoxybenzene or 1,2-diamino-
ethane in the presence of the "proton sponge". In these
complexes, the uranyl cation located in the cavity of the
macrocycle is bound to all six N atoms.14,15
coupling occurs between two NiII ions in the complex
under study, the first excited (triplet) level being located
–1
at a distance of 360 cm
(∼1 kal mol–1) from the
ground (singlet) level, which is comparable with the
values known for other nickel dimers with the "China-
lantern" structure (–2J = 260 cm–1).17
Thus we prepared the first binuclear antiferro-
magnetic NiII complex in which the Ni...Ni frag-

2448
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Chernyadyev et al.
C(14)
N(3)
C(12)
C(11)
C(10)
C(13)
N(1A)
O(2)
O(1A)
N(2A)
Ni(1)
C(9)
C(8)
N(2)
Ni(1A)
C(1)
O(1)
C(2)
O(2A)
N(1)
N(3A)
C(7)
C(6)
C(3)
C(5)
C(4)
Fig. 2. Structure of the complex C28H22N6Ni2O4 (5).
solutions were measured on a Specord M-400 spectrophotom-
eter in the range of 200—900 nm. The measurements of the
static magnetic susceptibility were carried out in the tempera-
ture range of 2—301 K on a MPMS-59 SQUID magnetometer
in the International Tomography Center of the Siberian Branch
of the Russian Academy of Sciences. The mass spectra were
obtained on a Finnigan MAT-50 instrument (direct inlet, EI,
70 eV). The 1H NMR spectra were recorded on a Bruker
DPX-300 spectrometer (300 MHz) with Me4Si as the internal
standard.
Quantum-chemical calculations were carried out with the
use of the PRIRODA program,19,20 which employs the
Gaussian-type basis sets for the solution of the Kohn—Sham
equations and expansion of the electron density in the auxil-
iary basis set. The PBE functional,10 which involves the
electron density gradient, was used. The geometry was opti-
mized using self-consistent application of gradient correc-
tions without restrictions imposed on the molecular sym-
metry. The orbital basis sets included the contraction sets
(5s1p)/[3s1p] for H, (11s5p2d)/[6s3p2d] for C, N, and O, and
(17s13p8d)/[12s9p4d] for Ni. The type of the stationary points
was determined based on analytical calculations of the second
derivatives of the energy.
Schiff's bases 4. A solution of dialdehyde 1 (123 mg,
1 mmol) and î-phenylenediamine (2) (108 mg, 1 mmol) in
anhydrous EtOH (50 mL) was refluxed for 1.5 h, cooled,
concentrated to 5—7 mL, and kept at 5 °C for one day. The
product crystallized as yellow-brown needles. The substance
was filtered off, washed on a filter with cold EtOH, and dried
in vacuo. Compound 4 was obtained in a yield of 158 mg
(74%), m.p. 165—167 °C. Found (%): C, 67.68; H, 5.23;
N, 19.83. C12H11N3O. Calculated (%): C, 67.61, H, 5.16,
N, 19.72.
ment is located inside the completely conjugated
macrocycle.
Experimental
Pyrrole-2,5-dicarbaldehyde (1)18 and nickel pivalate
[Ni9(HOOCBut)4(µ4-OH)3(µ3-OH)3(µn-OOCBut)12] (3)8 were
prepared according to procedures described previously. The
purified and dry solvents were used. The IR spectra were
recorded on a Specord M-80 spectrophotometer in KBr pellets
in the frequency range of 392—4000 cm–1. The diffusion
reflection electronic spectra for polycrystalline samples and
µ
eff/µB
2.5
2.0
1.5
1.0
0.5
50
100
150
200
250
T/K
Fig. 3. Magnetic properties of the binuclear complex
C28H22N6Ni2O4 (5); the dotted and solid curves correspond to
the theoretical and experimental dependences µeff(T), respec-
tively.

Binuclear transition metal complexes
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2449
1H NMR (DMSO-d6), δ: 12.50 (br.s, 1 H, H(11)); 9.60 (s,
1 H, H(1)); 8.55 (s, 1 H, H(4)); 7.17 (dd, 1 H, H(5),
J5,7 = 1.4 Hz, J5,6 = 8.0 Hz); 7.07 (d, 1 H, H(2), J2,3 = 4.0 Hz);
chromator, θ/2θ scanning technique, 2θmax .= 50°). The struc-
ture was solved by the direct method using the SHELXS-86
program package21 and refined by the least-squares method
6.94 (ddd,
1
H, H(7), J7,6
=
8.0 Hz, J7,8
=
8.0 Hz,
with anisotropic thermal parameters (isotropic thermal param-
J5,7 = 1.4 Hz); 6.80 (d, 1 H, H(3), J2,3 = 4.0 Hz); 6.68 (dd,
1 H, H(8), J8,6 = 1.4 Hz, J7,8 = 8.0 Hz); 6.51 (ddd, 1 H,
H(6), J7,6 = 8.0 Hz, J8,6 = 1.4 Hz, J5,6 = 8.0 Hz); 5.60 (br.s,
2 H, H(9), H(10)). The assignment of the signals was made
based on the NOE experiments (positive NOE was observed
on the H(3) and H(5) nuclei on irradiation of the signal at
δ 8.55) and using the 2D COSY 45 spectrum.
eters for the
package.22
H atoms) using the SHELXL-93 program
The X-ray diffraction data for 5•(Me2NCHO)2 were col-
lected on a Bruker AXS SMART 1000 diffractometer equipped
with a CCD detector (λ-Mo, graphite monochromator, 110 K,
ω scanning technique, scan step was 0.3°, frames were exposed
for 30 s, 2θmax = 60°) using a standard procedure.23 The
IR, ν/cm–1: 3456 m, 3320 m, 2920 w, 2848 w, 2800 w,
1648 s, 1616 m, 1504 m, 1416 m, 1240 m, 1168 m, 1048 m,
952 w, 784 m. MS, m/z (Irel (%)): 213 [Ì]+ (83.8),
Table 2. Selected bond lengths (d) and bond angles (ω) for
compound 4
212 [Ì
– –
H]+ (53.3), 184 [M HCO]+ (41.9), 119
[Ì – C5NOH4]+ (100). The electronic spectrum (a 0.0025 Ì
solution in MeCN), λmax/nm (ε•10–3): 238 (6.84), 256 (6.96),
323 (9.26), 405 (5.72).
Bond
d/Å
Angle
ω/deg
O(1)—C(5)
N(1)—C(1)
N(1)—C(4)
N(2)—C(6)
N(2)—C(7)
1.210(5)
1.371(5)
1.372(5)
1.268(5)
1.420(5)
C(1)—N(1)—C(4)
C(6)—N(2)—C(7)
N(1)—C(1)—C(2)
N(1)—C(1)—C(6)
C(2)—C(1)—C(6)
C(4)—C(3)—C(2)
N(1)—C(4)—C(3)
N(1)—C(4)—C(5)
O(1)—C(5)—C(4)
N(2)—C(6)—C(1)
C(8)—C(7)—C(12)
C(8)—C(7)—N(2)
C(12)—C(7)—N(2)
108.8(4)
120.2(4)
107.9(4)
122.5(4)
129.6(4)
107.8(4)
107.9(4)
122.7(4)
127.5(5)
121.6(4)
119.8(4)
125.8(4)
114.3(4)
Synthesis of binuclear complex 5. A. AcOH (0.5 mL) was
added to a solution of complex 3 (260 mg, 0.115 mmol),
dialdehyde 1 (123 mg, 1 mmol), and î-phenylenediamine 2
(108 mg, 1 mmol) in MeCN (100 mL). The reaction mixture
was kept for 24 h. The dark-red crystalline compound that
formed was filtered off, washed with cold MeCN, dried in
vacuo, and recrystallized from DMF. Solvate of 5 with DMF
was obtained in a yield of 173 mg (45%).
B. A solution of complex 3 (260 mg, 0.115 mmol) and
Schiff's base 4 (213 mg, 1 mmol) in MeCN (100 mL) was kept
for 1 h. Then AcOH (0.5 mL) was added and the mixture was
kept at ∼20 °C for 24 h. Crystals of 5 were filtered off, washed
with cold MeCN, and dried in vacuo. The product was recrys-
tallized from DMF. Solvate of 5 with DMF was obtained in a
yield of 204 mg (53%). Found (%): C, 52.96; H, 4.65;
N, 14.62. C34H36N8O6Ni2. Calculated (%): C, 52.99; H, 4.68;
N, 14.55.
N(3)—C(12) 1.363(6)
C(1)—C(6)
C(3)—C(4)
C(4)—C(5)
C(7)—C(12) 1.416(6)
C(9)—C(10) 1.377(7)
1.446(6)
1.379(6)
1.431(6)
N(3)—C(12)—C(11) 122.4(5)
N(3)—C(12)—C(7) 119.9(4)
IR (KBr), ν/cm–1: 2920 w, 1744 w, 1696 w, 1664 w,
1607 m, 1592 s, 1569 m, 1472 w, 1440 m, 1408 m, 1280 m,
1224 w, 1160 w, 1048 m, 944 w, 880 w, 752 m, 688 m, 624 w.
The diffusion reflection electronic spectrum, λmax/nm: 235,
328, 455, 503, 568, 627, 673, 869.
Table 3. Selected bond lengths (d) and bond angles (ω) for
complex 5•(Me2NCHO)2
Bond
d/Å
Angle
ω/deg
The X-ray diffraction data for compound 4 were collected
on a Siemens-P3/R3 diffractometer (λ-Mo-Kα, graphite mono-
Ni(1)—N(3)
Ni(1)—O(1)
Ni(1)—N(1)
Ni(1)—N(2)
1.937(2) N(3)—Ni(1)—O(1)
2.021(2) N(3)—Ni(1)—O(2)*
2.029(2) O(1)—Ni(1)—N(1)
2.034(2) O(1)—Ni(1)—N(2)
96.63(9)
92.64(9)
90.61(9)
91.61(9)
Table 1. Crystallographic parameters of compounds 4 and
5•(Me2NCHO)2
Ni(1)—Ni(1)* 2.5123(8) O(2)*—Ni(1)—O(1) 170.10(8)
O(1)—C(1)
O(2)—C(1)
O(2)—Ni(1)* 2.010(2) N(1)—Ni(1)—N(2)
N(3)—Ni(1)—N(1)
1.259(4) O(2)*—Ni(1)—N(1)
1.267(4) O(2)*—Ni(1)—N(2)
87.18(9)
92.84(9)
166.12(10)
82.34(10)
83.79(10)
Compound
4
5•(Me2NCHO)2
Molecular formula
Ñ12H11N3O Ñ34H36N8Ni2O6
N(3)—Ni(1)—N(2)
N(3)—Ni(1)—Ni(1)* 166.30(8)
O(1)—Ni(1)—Ni(1)* 87.36(6)
O(2)*—Ni(1)—Ni(1)* 84.41(6)
N(1)—Ni(1)—Ni(1)* 110.79(7)
N(2)—Ni(1)—Ni(1)* 83.00(7)
C(1)—O(1)—Ni(1)
C(1)—O(2)—Ni(1)* 123.6(2)
C(3)—N(1)—Ni(1) 111.25(17)
C(14)*—N(1)—Ni(1) 127.3(2)
C(10)—N(2)—Ni(1) 107.31(19)
C(13)—N(2)—Ni(1) 147.3(2)
C(8)—N(3)—Ni(1)
C(9)—N(3)—Ni(1)
Space group
a/Å
b/Å
C2/c
20.607(4)
5.5090(10)
19.962(4)
90
109.85(3)
90
2131.5(7)
4
P21/n
14.2639(10)
8.25599(6)
14.7057(11)
90
109.673(2)
90
1631.5(2)
2
c/Å
α/deg
β/deg
γ/deg
V/Å3
119.8(2)
Z
–3
ρ
calc/g cm
1.329
0.089
2.10—29.99
1.568
1.214
1.72—30.05
–1
µ/mm
θ Scan range/deg
Number of
115.95(19)
114.8(2)
independent reflections
1772
4539
R1
wR2
0.0724
0.1424
0.0495
0.1032
* The atom is related to the initial atom by the transformation
–x, –y, –z.

2450
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Chernyadyev et al.
semiempirical absorption correction was applied.24 The struc-
ture was solved by the direct method with the use of the
SHELXS-97 program package25 and refined by the full-matrix
least-squares method with anisotropic thermal parameters (the
positions of the H atoms were fixed with UH = 0.08 Å2) using
the SHELXL-97 program package.26 The atomic coordinates
were deposited with the Cambridge Structural Database.
9. D. E. Fenton and R. Moody, J. Chem. Soc., Dalton Trans.,
1987, 219.
10. J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev.
Lett., 1996, 77, 3865.
11. D. N. Laikov, Ph. D. (Phys.-Mat.) Thesis, M. V.
Lomonosov Moscow State University, Moscow, 2000 (in
Russian).
The principal crystallographic data for complexes
5•(Me2NCHO)2 are given in Table 1. The geometric param-
eters are listed in Tables 2 and 3, respectively.
4
and
12. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer,
A. G. Orpin, and R. Taylor, J. Chem Soc., Perkin Trans. 2,
1987, s1.
13. D. E. Fenton, J. Chem. Soc., Dalton Trans., 1986, 693.
14. J. L. Sessler, Inorg. Chem., 1992, 31, 529.
15. J. L. Sessler, Inorg. Chim. Acta, 1996, 23, 246.
16. I. L. Eremenko, S. E. Nefedov, A. A. Sidorov, M. A.
Golubnichaya, P. V. Danilov, V. N. Ikorskii, Yu. G.
Shvedenkov, V. M. Novotortsev, and I. I. Moiseev, Inorg.
Chem., 1999, 38, 3764.
17. Yu. V. Rakitin and V. T. Kalinnikov, Sovremennaya
magnetokhimiya [Modern Magnetochemistry], Nauka,
St. Petersburg, 1994, 272 (in Russian).
18. R. Miller and K. Olsson, Acta Chem. Scand., 1981, B35, 303.
19. L. Yu. Ustynyuk, Yu. A. Ustynyuk, D. N. Laikov, and
V. V. Lunin, Izv. Akad. Nauk, Ser. Khim., 1999, 2248
[Russ. Chem. Bull., 1999, 48, 2222 (Engl. Transl.)].
20. Yu. A. Ustynyuk, L. Yu. Ustynyuk, D. N. Laikov, and
V. V. Lunin, J. Organomet. Chem., 2000, 597, 182.
21. G. M. Sheldrick, SHELXS-86. Program for the Solution of
Crystal Structures, University of Göttingen, Germany, 1985.
22. G. M. Sheldrick, SHELXL-93. Program for the Refinement
of Crystal Structures, University of Göttingen, Ger-
many, 1993.
23. SMART (control) and SAINT (integration) Software, Ver-
sion 5.0, Bruker AXS Inc., Madison, WI, 1997.
24. G. M. Sheldrick, SADABS, Program for Scaling and Correc-
tion of Area Detector Data, University of Göttingen, 1997
(based on the method of R. H. Blessing, Acta Crystallogr.,
1995, 51A, 33).
Quantum-chemical calculations were carried out in
the Interdepartmental Supercomputer Center on a Beta
cluster. We thank V. M. Gryaznov and D. N. Laikov for
helpful discussion, V. M. Nosova for help in recording
the NMR spectra, and N. S. Kulikov for measuring the
mass spectra.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 99-03-
32792, 99-03-32806, 00-15-97429, 01-03-32553, and
01-03-32537).
References
1. J.-M. Lehn, Supramolecular Chemistry. Concepts and Per-
spectives, Weinheim, New York—Basel—Cambridge; VCH
Venlagsgesellschaft mbH, Tokyo, 1995.
2. R. H. Holm, P. Kennepohl, and E. I. Solomon, Chem.
Rev., 1996, 96, 2239.
3. L. F. Lindoy, Pure Appl. Chem., 1989, 61, 1575.
4. Molecular Electronics, Ed. G. J. Fshwell, Wiley, New
York, 1992.
5. A. Jasat and D. Dolphin, Chem. Rev., 1997, 97, 2267.
6. H. Okawa, H. Furutachi, and D. E. Fenton, Coord. Chem.
Rev., 1998, 174, 51.
7. Yu. A. Ustynyuk, N. E. Borisova, V. M. Nosova, M. D.
Reshetova, S. S. Talismanov, S. E. Nefedov, G. G.
Aleksandrov, I. L. Eremenko, and I. I. Moiseev, Izv. Akad.
Nauk, Ser. Khim., 2002, No. 3 [Russ. Chem. Bull., Int. Ed.,
2002, 51, No. 3].
25. G. M. Sheldrick, SHELXS-97. Program for the Solution of
Crystal Structures, University of Göttingen, Germany, 1997.
26. G. M. Sheldrick, SHELXS-97. Program for the Refinement
of Crystal Structures, University of Göttingen, Ger-
many, 1997.
8. V. M. Novotortsev, Yu. V. Rakitin, S. E. Nefedov, and
I. L. Eremenko, Izv. Akad. Nauk, Ser. Khim., 2000, 437
[Russ. Chem. Bull., Int. Ed., 2000, 49, 438].
Received July 11, 2001;
in revised form October 11, 2001