Complexes of Cu(II) and Co(II) nitrates with 3-phenyl-5,5-dimethyl-5,6- dihydro-1,2,4-triazolo[3,4-a]isoquinoline

Article abstract of DOI:10.1134/S1070328406060030

Complexes of Cu(II) and Co(II) nitrates with 3-phenyl-5,5-dimethyl-5,6- dihydro-1,2,4-triazolo[3,4-a]isoquinoline (L⁰) of the composition [CuL ₂ ⁰ (NO₃)₂] (I) and [CoL ₂ ⁰ (NO₃)₂] ? CH₃CN (II) are synthesized and their crystal structures are determined by X-ray diffraction. The L⁰ ligand is coordinated to the metal atoms through the N atom in position 2 of triazole fragment. The coordination polyhedron of the Cu(II) atom is a square with two additional axial vertices, while that of the Co(II) atom is a tetrahedron with two additional vertices. The NO ₃ ^- groups in the structures of I and II perform similar anisobidentate function. Complexes I and II are studied by IR and electronic spectroscopy. Pleiades publishing, Inc. 2006.

Full text of DOI:10.1134/S1070328406060030

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2006, Vol. 32, No. 6, pp. 402–415. © Pleiades Publishing, Inc., 2006.
Original Russian Text © V.I. Sokol, V.V. Davydov, N.Yu. Merkur’eva, V.S. Sergienko, S.A. Pervushina, Yu.V. Shklyaev, 2006, published in Koordinatsionnaya Khimiya, 2006,
Vol. 32, No. 6, pp. 419–432.
Complexes of Cu(II) and Co(II) Nitrates with 3-Phenyl-5,5-
dimethyl-5,6-dihydro-1,2,4-triazolo[3,4-a]isoquinoline
V. I. Sokola, V. V. Davydovb, N. Yu. Merkur’evab, V. S. Sergienkoa,
S. A. Pervushinab, and Yu. V. Shklyaevc
a
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31,
Moscow, 119991 Russia
Russian University of Peoples’Friendship, ul. Miklukho-Maklaya 6, Moscow 117198 Russia
b
c
Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, ul. Lenina 13, Perm 614600 Russia
Received September 12, 2005
Abstract—Complexes of Cu(II) and Co(II) nitrates with 3-phenyl-5,5-dimethyl-5,6-dihydro-1,2,4-triaz-
olo[3,4-a]isoquinoline (L0) of the composition [CuL20 (NO3)2] (I) and [CÓL02 (NO3)2] · CH3CN (II) are synthe-
sized and their crystal structures are determined by X-ray diffraction. The L0 ligand is coordinated to the metal
atoms through the N atom in position 2 of triazole fragment. The coordination polyhedron of the Cu(II) atom
is a square with two additional axial vertices, while that of the Co(II) atom is a tetrahedron with two additional
vertices. The NO–3 groups in the structures of I and II perform similar anisobidentate function. Complexes I and
II are studied by IR and electronic spectroscopy.
DOI: 10.1134/S1070328406060030
The derivatives of 3-phenyl- (L0), 3-Ó-nitrophenyl-
CH
CH
3
2
2
3
2
2
(L1), 3-Ó-tolyl- (L2), 3-(furan-2-yl)-8,9-dimethoxy-
(L3), 5,5-dimethyl-5,6-dihydro-1,2,4-triazolo[3,4-‡]iso-
quinoline, which are the subjects of our studies today,
belong to ambidentate, potentially polydentate, ligands.
R
R
CH
CH
3
3
1
1
N
R
N
R
R
R
N
N
N
N
+n
+n
M
M
‡
b
CH
6
3
2
2
R
CH
3
5
4
CH
CH
3
2
2
1
R
R
N
3
R
3
(LH)+MX–4
1
N
R
N
N
R
1
2
(Ln)
N
N
R1
L0 phenyl
R2
H
+n
+n
M /
M /
2
2
.
c
d
L1 o-nitrophenyl
H
Complexes of 1,2,4-triazole of types ‡ and b were
L2
L3
o-tolyl
H
described in [1–3], of type c in [4–7], and type d com-
plexes were reported in [8]. We synthesized and studied
coordination compounds of Cu(II), Co(II), and Fe(III)
with ligands Ln [8–13] and discovered complexes of
types ‡, b, and d among them. It was established that the
complex composition and the mode of Ln coordination
to a central atom did not depend on the nature of sub-
stituent in position 3 of compound Ln. In particular, in
furan-2-yl
O–CH3
They form complexes with metal salts owing to their
1,2,4-triazole ring. Since lone electron pair of the N
atom in position 4 is involved in heteroaromatic
π-system, but does not participate in donor–acceptor
interaction with the metal ions, one can suggest that
compounds Ln will give complexes of the following
types:
complexes [CuL12 Cl2] · 2C3H6O [9] and [CuL22 Cl2] ·
2C3H6O [10], the organic ligands Ln are coordinated to
402

COMPLEXES OF CU(II) AND CO(II) NITRATES
403
the Cu(II) atom in type ‡ mode. Complexes [CoL02 Cl2]
[11] and [CÓL32 Cl2] · CH3CN [12] show type b coordi-
nation. The (HL32 )[FeCl4] complex [8], where L3 mol-
ecule is protonated at the N atom in position 1, corre-
sponds to type d. At the same time, quantum-chemical
calculations of the Ln molecules show that the N atoms
in positions 1 and 2 are almost equivalent [13].
IR spectra of polycrystalline samples of com-
pounds I and II (KBr pellets) were recorded on a
Specord 75-IR spectrophotometer.
Electronic absorption spectra of solutions of
complexes I and II (in acetonitrile) at concentrations
10−5 mol/l and of polycrystalline samples of I and II
were recorded on a Specord UV VIS spectrophoto-
meter.
The aim of this work was to study the dependence of
the mode of Ln coordination on the nature of the metal
salt anion. We synthesized complexes of the Cu(II) and
RESULTS AND DISCUSSION
It is known [18] that the 1,2,4-triazole derivatives
can be identified by the presence of intense bands at
1520–1420 cm–1 in IR spectra. Indeed, the spectra of
compounds of L0–L3 contain in this region two intense
bands at 1496–1465 and 1462–1455 cm–1. As was
expected, the spectra of the Ln compounds in the indi-
cated region are closer to those of triazole derivatives
than to the spectra of 3,4-dihydroisoquinoline deriva-
tives, even though the latter have substituted imino
group =NR in position 1 [19]. This fact indicates that
the π-system of triazole ring is weakly affected by the
dihydroisoquinoline, phenyl, nitrophenyl, toluene, or
furyl (for L0, L1, L2, L3, respectively) substituents in
position 3 of molecules Ln. These substituents, in turn,
are responsible for low-intensity bands in a region of
1650–1520 cm–1, where unsubstituted triazole does
not absorb [13].
Co(II) nitrates with L0, [CuL20 (NO3)2] (I) and
[CÓL02 (NO3)2] · CH3CN (II) and studied their struc-
tures.
EXPERIMENTAL
Synthesis. A solution of crystal hydrate Cu(NO3)2 ·
6H2O or CÓ(NO3)2 · 6H2O (0.2 mmol) in 2 ml aceto-
nitrile was poured with stirring to a solution of L
(0.2 mmol) in 2 ml acetonitrile. The obtained crystals
of complexes I and II were washed with acetone and
dried in vacuum desiccator to a constant weight.
For C36H34CuN8O6
When analyzing the spectra of noncoordinated Ln
molecules and of their metal complexes, it turns out that
the most informative are bands due to composite
vibrations ν(C=N + C=C) at 1480–1450 cm–1.
anal. calcd. (%) (I):
M 8.61;
M 8.53;
N 15.18.
N 15.24.
Found (%):
For C38H35CoN9O6
anal. calcd. (%) (II):
Found (%):
Correlation between the structures of investigated
metal chloride complexes and their IR spectra revealed
that type a coordination of Ln to a metal is characterized
by a shift of bands ν(CN + CC) toward both high- and
low-frequency region (from 1472 and 1462 cm–1 in the
M 7.63;
M 7.70;
N 16.31.
N 16.21.
Elemental analysis for N in complexes synthesized
was performed on a EA-1108 CARLO ERBA ana-
lyzer by the known procedure [14]; the metal contents
was determined by spectrophotometry [15].
spectrum of L0 to 1482 and 1459 cm–1 in the [CÓL20 Cl2]
complex [11]). Coordination of Ln to a metal according
to type b exhibits high-frequency shift of bands in the
indicated regions (from 1473 and 1461 cm–1 in the L2
X-ray diffraction analysis. Crystallographic data,
details of data collection, and refinement parameters for
compounds I and II are given in Table 1. Experimen-
tal data for compounds I and II were obtained at room
temperature on automated four-circle Enraf-Nonius
CAD4 diffractometer (λåÓäα radiation, graphite
monochromator, ω-scan mode). The structures were
solved by the direct method (SHELXL97 [16]) and
refined by the least-squares method on F2 in full-
matrix anisotropic approximation for non-hydrogen
atoms (SHELXL97 [17]) with account for geometri-
cally calculated hydrogen atoms with fixed positional
and thermal parameters (UH = 0.08 Å2).
spectrum to 1476 and 1466 cm–1 in the [CuL22 Cl2] ·
2C3H6O spectrum [10]). Thus, if X-ray diffraction data
are unavailable, the direction of the band shift at a range
of 1480–1450 cm–1 could serve as spectroscopic crite-
rion of the type of coordination of the 1,2,3,4-tetrahy-
droisoquinoline derivatives under study. Unfortunately,
this criterion is not always reliable [12].
The low-intensity bands ν(C=N + C=C) in IR spec-
tra of Ln at 1650–1520 cm–1 also shifted toward high-
frequency region during complex formation or proto-
nation of the N atoms in positions 1 or 2.
IR spectra of the L0 compound contain in this region
low-intensity bands at 1602, 1587, 1542, and
1522 cm−1. In the spectra of complexes I and II, these
bands undergo high-frequency shift (by 2–6 cm–1). It is
The atomic coordinates and temperature factors
Ueq of atoms are presented in Table 2; bond lengths
and bond angles in structures I and II are listed in
Table 3.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

404
SOKOL et al.
Table 1. Crystallographic parameters and details of data collection for complexes I and II
Value
Parameter
I
II
M
738.25
772.68
Crystal system
Triclinic
Triclinic
Space group
P1
P1
9.867(1)
10.349(2)
18.837(3)
79.63(1)
89.22(2)
80.26(2)
1864.5(4)
2
a, Å
9.181(2)
9.836(2)
10.454(1)
69.26(2)
76.32(1)
70.92(2)
826.5(3)
1
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
Z
ρ
µ
(calcd), g/cm3
Mo, cm–1
1.483
1.376
7.20
5.19
F(000)
383
802
2θmax, deg
59.8
53.9
Range of indices
–12 < h < 12, –12 < k < 13, 0 < l < 14 –12 < h < 12, –12 < k < 13, 0 < l < 24
Total number of reflections
Number of reflections with I ≥ 2σ(I)
Number of refined reflections
R1; wR2 (I > 2σ(I))
R1; wR2 (for all reflections)
GOOF
4868
8352
2833
4595
301
498
0.046; 0.113
0.105; 0.133
1.059
0.053; 0.113
0.122; 0.138
1.000
Extinction coefficient
∆ρmax; ∆ρmin, eÅ–3
0.000(2)
0.717; –0.469
0.0017(6)
0.371; –0.458
difficult to determine in which direction the bands at crystal). Similar shift of a long-wave band was previ-
ously observed in the spectrum of the [CÓL02 Cl2] com-
1472 and 1462 shift, since they overlap with the bands
of the NO–3 ions. For the same reason, it is impossible
plex. Since no new long-wave bands were detected in
the spectra of I and II, as compared to the L0 spectrum,
one can conclude that as in [CÓL02 Cl2], in complexes I
to make reliable conclusion on the state (the type of
bonding to a metal) of the nitrate ions in the composi-
tion of the complexes.
and II, the phenyl substituent is not conjugated with tri-
azole ring.
As compared to the spectrum of a free ligand L0, the
spectra of complexes I and II show insignificant hypso-
chromic shift of the band due to π–π*-transition (from
Thus, although the spectral data confirm the
involvement of the N atoms in position 1 or 2 in coor-
262 to 260 nm in a solution and from 284 to 280 nm in dination, it is still impossible to make a choice in favor
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

COMPLEXES OF CU(II) AND CO(II) NITRATES
Table 2. Coordinates of atoms and thermal parameters U for complexes I and II
405
eq
x
y
z
Ueq, Å2*
Atom
x
y
z
Ueq, Å2*
Atom
I
II
Cu(1)
0
0
0
0.0308(2) Co(1)
–0.1861(3) 0.1519(3) 0.0570(2) 0.0559(6) O(1)
–0.2279(4) 0.3667(3) 0.0854(3) 0.102(1) O(2)
0.0826(1) 0.1152(1) 0.2217(1) 0.0342(1)
–0.0005(3) –0.0813(2) 0.2608(1) 0.0605(7)
–0.1235(2) 0.1086(2) 0.2311(2) 0.0612(7)
–0.2219(3) –0.0612(3) 0.2720(2) 0.0694(8)
0.2529(2) 0.0126(2) 0.1838(1) 0.0534(6)
0.0961(3) 0.0713(3) 0.1023(1) 0.0584(7)
0.2943(3) –0.0365(3) 0.0771(2) 0.0704(8)
0.1850(2) 0.1404(2) 0.4355(1) 0.0360(6)
0.2203(3) –0.0073(2) 0.3628(1) 0.0380(6)
0.1459(2) 0.1106(2) 0.3261(1) 0.0358(6)
–0.1184(3) –0.0141(3) 0.2552(1) 0.0470(7)
0.2157(3) 0.0152(3) 0.1186(2) 0.0485(7)
0.2420(3) 0.0130(3) 0.4278(2) 0.0343(7)
0.3114(3) –0.0839(3) 0.4874(2) 0.0380(7)
0.3416(3) –0.2184(3) 0.4842(2) 0.0454(8)
O(1)
O(2)
O(3)
N(1)
N(2)
N(3)
N(4)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
0.0055(4) 0.2392(4) 0.0284(3) 0.0870(9) O(3)
–0.0751(2) 0.2357(2) –0.4059(2) 0.0300(4) O(4)
0.1200(2) 0.1297(3) –0.2829(2) 0.0345(5) O(5)
–0.0171(2) 0.1105(2) –0.1981(2) 0.0323(5) O(6)
–0.1346(4) 0.2565(3) 0.0567(2) 0.0564(8) N(1)
0.0820(3) 0.2035(3) –0.4059(2) 0.0309(5) N(2)
0.1874(3) 0.2441(3) –0.5327(3) 0.0348(6) N(3)
0.3471(3) 0.1891(4) –0.5363(3) 0.0451(7) N(4)
0.4422(4) 0.2255(4) –0.6610(3) 0.0535(8) N(5)
0.3781(4) 0.3156(4) –0.7797(3) 0.0535(8) C(1)
0.2197(4) 0.3699(4) –0.7761(3) 0.0521(8) C(2)
0.1217(3) 0.3377(3) –0.6517(3) 0.0416(6) C(3)
–0.0513(4) 0.4066(3) –0.6400(3) 0.0468(7) H(3A)
–0.1475(3) 0.3019(3) –0.5365(3) 0.0354(6) C(4)
0.317
0.4097(4) –0.3068(4) 0.5423(2) 0.0559(9)
0.432 –0.397 0.540
0.4434(4) –0.2603(4) 0.6028(2) 0.061(1)
0.488 –0.320 0.642
0.4116(4) –0.1274(4) 0.6062(2) 0.056(1)
0.435 –0.098 0.647
–0.249
0.444
C(10) –0.1375(4) 0.1715(4) –0.5876(3) 0.0463(7) H(4A)
C(11) –0.3149(4) 0.3949(4) –0.5147(4) 0.0561(9) C(5)
C(12) –0.1325(3) 0.1723(3) –0.2722(2) 0.0289(5) H(5A)
C(13) –0.2974(3) 0.1743(3) –0.2196(2) 0.0329(5) C(6)
C(14) –0.3543(3) 0.0592(3) –0.2164(3) 0.0422(6) H(6A)
C(15) –0.5111(4) 0.0683(4) –0.1764(4) 0.0541(8) C(7)
C(16) –0.6100(4) 0.1917(5) –0.1403(3) 0.0552(9) C(8)
C(17) –0.5542(4) 0.3037(4) –0.1394(3) 0.0540(9) H(8A)
C(18) –0.3975(3) 0.2970(4) –0.1790(3) 0.0448(7) H(8B)
0.3440(3) –0.0367(3) 0.5485(2) 0.0421(8)
0.3116(3) 0.1107(3) 0.5486(2) 0.0450(8)
0.388
0.304
0.151
0.124
0.528
0.598
H(3)
H(4)
H(5)
H(6)
0.390
0.551
0.445
0.184
0.124
0.190
0.336
0.427
0.432
0.501
0.107
0.214
0.114
0.468
0.448
0.320
–0.026
–0.010
0.198
0.390
0.370
–0.455
–0.657
–0.864
–0.845
–0.734
–0.611
–0.518
–0.671
–0.610
–0.467
–0.602
–0.455
–0.244
–0.175
–0.107
–0.118
–0.179
C(9)
0.1791(3) 0.1840(3) 0.5076(2) 0.0402(7)
0.0511(3) 0.1419(4) 0.5454(2) 0.0553(9)
C(10)
H(10A) –0.030
H(10B) 0.048
H(10C) 0.055
0.190
0.162
0.048
0.519
0.593
0.548
H(8A) –0.084
H(8B) –0.082
H(10A) –0.186
H(10B) –0.189
H(10C) –0.020
H(11A) –0.316
H(11B) –0.345
H(11C) –0.382
H(14) –0.291
H(15) –0.550
H(16) –0.720
H(17) –0.615
H(18) –0.357
C(11)
0.1755(4) 0.3327(4) 0.5001(2) 0.058(1)
H(11A) 0.257
H(11B) 0.172
H(11C) 0.096
0.356
0.357
0.380
0.476
0.547
0.472
C(12)
C(13)
0.1240(3) 0.1982(3) 0.3706(2) 0.0334(6)
0.0440(3) 0.3342(3) 0.3503(2) 0.0366(7)
C(14) –0.0967(3) 0.3524(3) 0.3495(2) 0.0468(8)
H(14A) –0.142 0.280 0.362
C(15) –0.1725(4) 0.4807(4) 0.3297(2) 0.060(1)
H(15A) –0.268 0.493 0.329
C(16) –0.1078(5) 0.5870(4) 0.3108(2) 0.062(1)
H(16A) –0.159 0.672 0.298
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

406
SOKOL et al.
Table 2. (Contd.)
Atom
x
y
z
Ueq, Å2*
Atom
x
y
z
Ueq, Å2*
II
0.0330(5) 0.5697(4) 0.3104(2) 0.059(1)
H(17A) 0.077 0.643 0.297
C(18) 0.1095(4) 0.4434(3) 0.3296(2) 0.0476(8) H(11D) 0.345
H(18A) 0.205 0.432 0.329 H(11E) 0.302
0.0929(2) 0.5114(2) 0.1235(1) 0.0309(5) H(11F) 0.313
II
0.632
C(17)
H(10F) 0.021
C(11')
–0.008
0.2883(3) 0.6358(3) 0.0968(2) 0.056(1)
0.561
0.632
0.717
0.082
0.148
0.071
N(1')
N(2')
N(3')
C(1')
C(2')
C(3')
–0.0569(2) 0.3897(2) 0.1728(1) 0.0338(6) C(12')
0.0699(2) 0.3109(2) 0.1751(1) 0.0317(5) C(13')
–0.0405(3) 0.5084(3) 0.1417(1) 0.0303(6) C(14')
0.1599(3) 0.3835(3) 0.1453(1) 0.0326(6)
0.3071(3) 0.3302(3) 0.1377(2) 0.0350(7)
0.3536(3) 0.2836(3) 0.0753(2) 0.0453(8)
–0.1464(3) 0.6274(3) 0.1264(2) 0.0329(6) H(14B) 0.293
–0.2852(3) 0.6203(3) 0.1332(2) 0.0411(7) C(15') 0.4903(4) 0.2311(4) 0.0697(2) 0.058(1)
0.538 0.147 H(15B) 0.521 0.199 0.028
–0.3804(3) 0.7365(4) 0.1195(2) 0.0494(8) C(16') 0.5820(4) 0.2262(4) 0.1242(2) 0.059(1)
H(4'A) –0.474 0.733 0.125 H(16B) 0.674 0.192 0.120
C(5') –0.3385(4) 0.8582(4) 0.0984(2) 0.0563(9) C(17') 0.5366(4) 0.2730(4) 0.1861(2) 0.066(1)
H(5'A) –0.404 0.936 0.089 H(17B) 0.561
C(6') –0.2005(4) 0.8653(3) 0.0919(2) 0.0507(9) H(17C) 0.589
H(6'A) –0.173 0.947 0.078 C(18')
–0.1028(3) 0.7498(3) 0.1064(2) 0.0386(7) H(18B) 0.370
0.0490(3) 0.7535(3) 0.1050(2) 0.0423(8) N(6) –0.5850(5) 0.5840(5) 0.3147(3) 0.134(2)
C(19) –0.5116(5) 0.8121(6) 0.2860(3) 0.075(1)
0.288
0.037
H(3'A) –0.314
C(4')
0.200
0.342
0.227
0.192
0.3996(3) 0.3245(4) 0.1924(2) 0.0547(9)
0.356 0.234
C(7')
C(8')
H(8'A)
H(8'B)
C(9')
0.079
0.064
0.760
0.834
0.153
0.073
H(19A) –0.433
0.816
0.861
0.265
0.318
0.1388(3) 0.6330(3) 0.0812(2) 0.0358(7) H(19B) –0.546
0.0903
C(10')
0.1158(4) 0.6331(3) 0.0011(2) 0.0485(8) C(20) –0.5527(5) 0.6843(5) 0.3014(3) 0.072(1)
H(10D) 0.171
H(10E) 0.141
0.556
–0.012
–0.027
H(19) –0.557
0.866
0.240
0.712
2
* Fixed values of U = 0.08 Å .
H
of one of the types of L0 coordination to a metal (type a metal (through the N(3) atom in position 2 of triazole
or type b).
ring). This type of coordination was previously
detected only in the Cu complexes [9, 10]. In this case,
depending on the nature of a metal, each complex
exhibits specific coordination polyhedron (CP), while
the nitrate groups perform different structural func-
tions. In complex I, the CP of the Cu atom is almost a
regular square (2N, 2O) with additional axial interac-
tions Cu–O3(NO3). A similar coordination surrounding
of the Cu atom was found earlier in [Cu(H2O)2(NO3)2] ·
In order to obtain thorough information on the
structures of complexes I and II, we performed X-ray
diffraction study.
The structures of the L0 complexes with nitrates of
copper [CuL02 (NO3)2] (I) (Fig. 1) and cobalt
[CÓL02 (NO3)2] · CH3CN (II) (Fig. 2) have both signifi-
cant differences and similarities. Complexes I and II
show the same type of coordination of ligand L0 to a
L42 (III) [20], where L4 = 1-(3-methyl-1-phenylpyr-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

COMPLEXES OF CU(II) AND CO(II) NITRATES
Table 3. Bond lengths and bond angles in structures I and II
407
Bond
d, Å
Bond
d, Å
Bond
d, Å
Bond
d, Å
I
II
Cu(1)–O(1)
Cu(1)–O(3)
O(1)–N(4)
O(3)–N(4)
N(1)–C(9)
N(2)–N(3)
N(3)–C(12)
C(2)–C(3)
C(3)–C(4)
C(5)–C(6)
C(8)–C(9)
C(9)–C(11)
C(13)–C(14)
C(14)–C(15)
C(16)–C(17)
1.996(3) Cu(1)–N(3)
2.489(2) O(2)–N(4)
1.265(4) N(1)–C(1)
1.217(5) N(1)–C(12)
1.499(3) N(2)–C(1)
1.384(3) C(1)–C(2)
1.313(3) C(2)–C(7)
1.384(4) C(4)–C(5)
1.387(5) C(6)–C(7)
1.373(6) C(7)–C(8)
1.537(4) C(9)–C(10)
1.521(5) C(12)–C(13)
1.381(4) C(13)–C(18)
1.383(5) C(15)–C(16)
1.363(6) C(17)–C(18)
1.986(2) Co(1)–N(3)
1.225(4) O(1)–N(4)
1.372(4) O(3)–N(4)
1.367(3) O(5)–N(5)
1.300(3) N(1)–C(1)
1.457(4) N(1)–C(12)
1.393(4) N(2)–C(1)
1.377(5) C(1)–C(2)
1.393(4) C(2)–C(7)
1.504(5) C(4)–C(5)
1.524(5) C(6)–C(7)
1.479(4) C(8)–C(9)
1.392(4) C(9)–C(11)
1.372(6) C(13)–C(14)
1.386(5) C(14)–C(15)
2.061(2) Co(1)–N(3')
1.246(4) O(2)–N(4)
1.219(4) O(4)–N(5)
1.240(4) O(6)–N(5)
1.375(4) N(1)–C(9)
1.361(4) N(2)–N(3)
1.306(4) N(3)–C(12)
1.456(4) C(2)–C(3)
1.390(4) C(3)–C(4)
1.378(5) C(5)–C(6)
1.396(5) C(7)–C(8)
1.537(5) C(9)–C(10)
1.513(5) C(12)–C(13)
1.369(5) C(13)–C(18)
1.398(5) C(15)–C(16)
2.041(2)
1.262(4)
1.280(4)
1.222(4)
1.503(4)
1.383(3)
1.311(4)
1.386(5)
1.393(5)
1.371(6)
1.506(5)
1.531(5)
1.479(4)
1.389(5)
1.354(6)
Angle
ω, deg
Angle
ω, deg
C(16)–C(17)
1.370(6) C(17)–C(18)
1.383(5)
O(1)Cu(1)N(3)
O(1)Cu(1)O(3)
C(1)N(1)C(9)
C(9)N(1)C(12) 131.8(2) N(3)N(2)C(1)
Cu(1)N(3)N(2) 116.3(2) Cu(1)N(3)C(12)
N(2)N(3)C(12) 109.2(2) O(1)N(4)O(2A)
O(1)N(4)O(3)
N(1)C(1)N(2)
N(2)C(1)C(2)
C(1)C(2)C(7)
C(2)C(3)C(4)
C(4)C(5)C(6)
C(2)C(7)C(6)
91.11(9) Cu(1)O(1)N(4)
55.0(2) N(3)Cu(1)O(3)
122.4(2) C(1)N(1)C(12)
105.3(2) N(1')–C(1')
87.9(2) N(1')–C(12')
104.9(2) N(2')–N(3')
105.9(2) N(3')–C(12')
134.5(2) C(2')–C(3')
118.2(3) C(3')–C(4')
124.8(3) C(5')–C(6')
121.8(2) C(7')–C(8')
121.5(3) C(9')–C(10')
120.8(3) C(12')–C(13')
120.3(3) C(13')–C(18')
120.4(3) C(15')–C(16')
118.8(3) C(17')–C(18')
1.360(4) N(1')–C(9')
1.369(4) N(2')–C(1')
1.369(3) C(1')–C(2')
1.315(4) C(2')–C(7')
1.386(4) C(4')–C(5')
1.382(5) C(6')–C(7')
1.378(5) C(8')–C(9')
1.505(5) C(9')–C(11')
1.527(4) C(13')–C(14')
1.478(4) C(14')–C(15')
1.373(5) C(16')–C(17')
1.365(5) N(6)–C(20)
1.378(5) C(19)–C(20)
1.498(4)
1.297(4)
1.462(4)
1.394(4)
1.381(5)
1.390(5)
1.536(4)
1.514(4)
1.394(4)
1.376(5)
1.384(6)
1.121(7)
1.428(8)
117.0(3) O(2) N(4)O(3)
111.3(2) N(1)C(1)C(2)
126.8(2) C(1)C(2)C(3)
117.7(3) C(3)C(2)C(7)
119.2(3) C(3)C(4)C(5)
120.5(4) C(5)C(6)C(7)
118.7(3) C(2)C(7)C(8)
C(6)C(7)C(8)
122.4(3) C(7)C(8)C(9)
114.5(3)
Angle
ω, deg
Angle
ω, deg
N(1)C(9)C(8)
106.7(2) N(1)C(9)C(10)
107.4(2) O(1)Co(1)O(2)
111.0(3) O(1)Co(1)O(5)
111.3(3) O(2)Co(1)O(4)
125.6(2) O(4)Co(1)O(5)
57.5(1) O(2)Co(1)O(5)
90.40(9) O(2)Co(1)N(3)
138.9(1) O(1)Co(1)N(3')
57.3(1) O(5)Co(1)N(3)
88.99(9) O(1)Co(1)O(4)
98.7(1) O(5)Co(1)N(3')
94.8(1)
103.5(1)
155.59(5)
157.8(1)
90.4(1)
N(1)C(9)C(11) 111.9(2) C(8)C(9)C(10)
C(8)C(9)C(11) 108.5(3) C(10)C(9)C(11)
N(1)C(12)N(3) 108.6(2) N(1)C(12)C(13)
N(3)C(12)C(13) 125.7(2) C(12)C(13)C(14) 120.7(3) O(1)Co(1)N(3)
C(12)C(13)C(18) 119.4(3) C(14)C(13)C(18) 119.8(3) O(2)Co(1)N(3')
85.9(1)
C(13)C(14)C(15) 119.9(3) C(14)C(15)C(16) 120.0(3) O(4)Co(1)–N(3') 107.57(9) O(4)Co(1)N(3)
100.49(9)
103.38(9)
101.4(2)
C(15)C(16)C(17) 120.4(4) C(16)C(17)C(18) 120.5(3) Co(1)O(2)N(4)
99.8(2) N(3)Co(1)N(3')
121.9(2) Co(1)O(4)N(5)
C(13)C(18)C(17) 119.3(3)
C(1)N(1)C(9)
C(9)N(1)C(12)
Angle
d, Å
Angle
d, Å
132.1(2) C(1)N(1)C(12)
105.2(2)
II
Co(1)N(3)N(2)
117.8(2) N(3)N(2)C(1)
106.1(2)
Co(1)–O(2)
Co(1)–O(1)
2.050(2) Co(1)–O(4)
2.314(2) Co(1)–O(5)
2.024(2) N(2)N(3)C(12)
2.371(2) O(1)N(4)O(3)
108.8(2) Co(1)N(3)C(12) 133.3(2)
123.5(3) O(1)N(4)O(2) 114.8(3)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

408
SOKOL et al.
Table 3. (Contd.)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
II
II
O(4)N(5)O(5)
O(5)N(5)O(6)
N(1)C(1)C(2)
C(1)C(2)C(3)
C(3)C(2)C(7)
C(3)C(4)C(5)
C(5)C(6)C(7)
C(2)C(7)C(8)
C(7)C(8)C(9)
N(1)C(9)C(10)
C(8)C(9)C(10)
115.3(3) O(2)N(4)O(3)
123.8(3) O(4)N(5)O(6)
122.0(3) N(1)C(1)N(2)
121.5(3) N(2)C(1)C(2)
121.1(3) C(1)C(2)C(7)
119.9(3) C(2)C(3)C(4)
120.5(3) C(4)C(5)C(6)
118.9(3) C(2)C(7)C(6)
115.3(3) C(6)C(7)C(8)
107.1(3) N(1)C(9)C(8)
111.5(3) N(1)C(9)C(11)
121.7(3) Co(1)N(3')N(2')
120.9(3) N(2')N(3')C(12')
111.2(3) N(1')C(1')C(2')
126.7(3) C(1')C(2')C(3')
117.5(3) C(3')C(2')C(7')
119.2(3) C(3')C(4')C(5')
120.8(4) C(5')C(6')C(7')
118.6(3) C(2')C(7')C(8')
122.4(3) C(7')C(8')C(9')
106.1(3) N(1')C(9')C(10')
111.9(3) C(8')C(9')C(10')
117.1(2) N(3')N(2')C(1')
109.1(2) Co(1)N(3')C(12')
121.8(2) N(1')C(1')N(2')
121.8(3) N(2')C(1')C(2')
120.8(3) C(1')C(2')C(7')
120.6(3) C(2')C(3')C(4')
120.1(3) C(4')C(5')C(6')
118.9(3) C(2')C(7')C(6')
114.9(3) C(6')C(7')C(8')
107.9(2) N(1')C(9')C(8')
111.1(3) N(1')C(9')C(11')
106.4(2)
133.8(2)
111.1(2)
127.1(3)
117.5(3)
119.1(3)
120.2(3)
119.1(3)
122.0(3)
106.5(2)
111.6(3)
109.0(3)
108.3(2)
C(10)C(9)C(11) 111.4(3) C(8)C(9)C(11)
N(1)C(12)C(13) 127.5(3) N(1)C(12)N(3)
C(12)C(13)C(14) 119.6(3) N(3)C(12)C(13)
108.7(3) C(10')C(9')C(11') 110.8(3) C(8')C(9')C(11')
108.7(2) N(1')C(12')C(13') 128.0(3) N(1')C(12')N(3')
123.8(3) C(12')C(13')C(14') 120.4(3) N(3')C(12')C(13') 123.8(3)
C(14)C(13)C(18) 119.4(3) C(12)C(13)C(18) 120.9(3) C(14')C(13')C(18') 119.1(3) C(12')C(13')C(18') 120.5(3)
C(14)C(15)C(16) 120.5(4) C(13)C(14)C(15) 119.7(3) C(14')C(15')C(16') 120.8(4) C(13')C(14')C(15') 119.8(3)
C(16)C(17)C(18) 120.0(4) C(15)C(16)C(17) 120.3(4) C(16')C(17')C(18') 119.9(4) C(15')C(16')C(17') 119.6(4)
C(1')N(1')C(9')
122.5(2) C(13)C(18)C(17) 120.1(3) N(6)C(20)C(19)
105.1(2)
178.8(6) C(13')C(18')C(17') 120.7(3)
C(9')N(1')C(12') 132.1(2) C(1')N(1')C(12')
azole-5-onylidene-4)-3,3-dimethyl-1,2,3,4-tet-
rahydroisoquinoline.
is caused by different structural function of the nitrate
groups: in complex I, the nitrate groups are anisobiden-
tate (AB), while in complex III, these are monodentate-
terminal groups (å). The additional interaction
Cu−O(3) in III (2.627(4) Å) is substantially weaker
than in I (2.489(2) Å). In planar nitrate group of com-
plex I almost perpendicular, as in structure III, to the
coordination square (the corresponding dihedral angles
being 84° and 94°), the N(4)–O(1) bond 1.255(4) Å
with coordinated O atom is longer than two other bonds
N(4)–O(2) 1.225(4) and N(4)–O(3) 1.217(5) Å. The
Cu–O(1)(NO3) bond length 1.996(3) Å in I is commen-
surable with the values found in square complexes of
Cu chlorides with analogous ligands L1 and L2, i.e.,
CH3
CH3
N
C
C
H
O
H3C
N
N
(L4)
[CuL12 Cl2] · 2C3H6O (IV) [9] 1.978(3) Å and
[CuL22 Cl2] · 2C3H6O (V) [10] 1.972(3) Å. The presence
The comparison of the CPs in compounds I and III
is shown in Fig. 3 with superposed atoms forming the
coordination square. As follows from Fig. 3, the main
difference in CPs of I (solid line) and III (dotted line) of nitrate anions in structure I, as distinct from chloride
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

COMPLEXES OF CU(II) AND CO(II) NITRATES
409
C(10)
C(11)
C(6)
C(7)
C(8)
C(9)
C(5)
C(15)
C(14)
C(13)
N(1)
C(16)
C(17)
C(4)
C(2)
C(3)
C(1)
C(18)
C(12)
N(2)
N(3)
O(3A)
O(1)
N(4)
O(2A)
Cu(1)
O(2)
O(1A)
O(3)
Fig. 1. The structure of [CuL0 (NO ) ] (I).
3 2
2
C(11)
C(17)
C(8)
C(11')
C(19)
C(8')
C(18)
C(9)
C(16)
C(17')
C(6')
C(7')
C(7)
C(6)
C(15)
C(13)
C(9')
N(1)
C(10)
C(5')
C(20)
N(1')
C(12)
C(2')
C(18')
C(12')
C(14)
C(10')
C(4')
C(5)
C(16')
N(3')
C(2)
C(3)
C(1')
C(14')
C(1)
C(3')
N(3)
N(2')
C(15')
C(4)
N(2)
Co(1)
O(4)
O(2)
O(1)
O(5)
N(4)
N(5)
O(3)
O(6)
Fig. 2. The structure of [CÓL0 (NO ) ] · CH CN in crystal II.
3 2
3
2
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

410
SOKOL et al.
N(3)
O(1)
Cu(1)
Fig. 3. The comparison of the CPs of the Cu(II) atoms in
complexes I, [CuL0 (NO ) ] (solid line) and III,
3 2
2
Co(1)
[Cu(H O) (NO ) ] · L4 (dotted line).
2
2
3 2
2
anions in structures IV and V, underlies different orien-
tation of flattened tricyclic molecule L about coordina-
tion polyhedron: torsion angle Cl(1)Cu(1)N(3)N(2)
(73° in IV and V) differs significantly from the angle
O(1)CuN(3)N(2) in I (135°).
N(3)
N(3')
Fig. 4. The comparison of the CPs of the Co(II) atoms in
crystals II, [CÓL0 (NO ) ] · CH CN (solid line) and VI,
3 2
3
2
[CoL5 (NO ) ] (dotted line).
Unlike complexes I and III, in the Co complex II
(Fig. 2), two independent nitrate groups are asymmetric
bidentate-cyclic groups with three different N–O bond
3 2
2
lengths (aver. 1.220
0.002, 1.243
0.003,
twofold axis (L5 being 1-(2-pyridyl)-2-(2-tienyl)ethyl-
ene) was found to be very close to hexacoordinated
(4 + 2) polyhedron in II with the same structural func-
tion of the nitrate groups.
1.271 0.009 Å). Hexacoordinated polyhedron of the
Co atom (2N, 2O+2O) can be described as a distorted
tetrahedron with four stable covalent bonds (Co–N(3)
2.061(2), Co–N(3') 2.041(2), Co–O(2) 2.050(2),
Co−O(4) 2.025(2) Å) and with two additional vertices
at longer distances (Co–O(1) 2.314(3) and Co–O(5)
2.371(2)Å). The O(1) and O(5) atoms lie almost above
centers of two faces of tetrahedron, namely,
O(2)O(4)N(3) and O(2)O(4)N(3'), respectively. In this
case, in the CoN2O2 tetrahedron, the N(3)Co(1)N(3')
and O(2)Co(1)O(4) planes are mutually perpendicular
and only one angle O(2)CoO(4) (138.9(1)°) is signifi-
cantly greater than the perfect value for tetrahedron
(109.5°). The remaining tetrahedral angles in II lie in
interval 98.7(1)°–107.57(9)°. The CP of the Co atom in
II is a strongly distorted cis-octahedron (4 + 2), where
“axial” angles O(1)CoN(3') 155.59(1)°, O(5)CoN(3)
157.8(1)°, and O(2)CoO(4) 138.9(1)°, like the cyclic
angles O(1)CoO(2) 57.5(1)°, O(4)CoO(5) 57.3(1)°,
noticeably differ from the perfect values for octahedron
(180° and 90°, respectively). Note that different geom-
etry of coordination six-vertex polyhedra (4 + 2) of the
metal atoms in the two studied complexes is determined
by different mutual position of each of the two pairs of
analogous ligands: trans-position in centrosymmetric
complex I and cis-position in complex II. The average
length of the Co–N bonds 2.051 0.005(2) Å in II is
typical of Co(II) in tetrahedral surrounding (in the
Co(II) octahedra, the Co–N bonds are significantly
longer, the interval of bond lengths being 2.11–2.19 Å
[21]). The coordination polyhedron in the
C
C
S
N
(L5)
The length of the bonds Co–O(NO3) 2.060(4) and
2.272(4) Å, and Co–N 2.045(4) Å and the bond angles
at the Co atom (58.6°, 97°, and 156°) in VI are close to
the values found in II. The CP of the Co atom in com-
pound VI was described in [22] as a strongly distorted
octahedron. The superposition of the CPs of complexes
II (solid line) and VI (dotted line) with superposed
positions of the Co and N atoms is shown in Fig. 4.
Some misalignment of the CPs of II and VI can be
explained by a different mutual orientation of two
nitrate groups: the dihedral angle between the planes of
four-membered metal cycles CoNO2 in VI is somewhat
smaller than in II (85° and 90°, respectively). The
structures of the nitrate complex II and of the previ-
ously studied complexes of Co chloride with ligands L0
and L3—[CoL20 Cl2] (VII) [11] and [CoL32 Cl2] · CH3CN
(VIII) [12], noticeably differ in both the type of the
ligand coordination to the Co atom and in mutual orien-
tation of the ligands. In the nitrate complex II (Fig. 2),
the tricyclic fragments of two ligands L0 are almost
mutually perpendicular (the dihedral angle 108°),
whereas in the chloride complex VII (Fig. 5), they are
nearly coplanar (15°). In complex VIII (Fig. 6), the tri-
[CoL52 (NO3)2]complex (VI) [22] with the Co atom on a
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COMPLEXES OF CU(II) AND CO(II) NITRATES
411
C(6)
C(10)
C(9)
C(5)
C(4)
C(7)
C(11)
C(14)
C(8)
C(3)
C(2)
N(1)
C(1)
C(15)
C(12)
C(16)
C(13)
C(17)
N(2)
Cl(1)
C(18)
N(3)
Co(1)
Cl(1Ä)
Fig. 5. The structure of [CoL0 Cl ] (VII).
2
2
cyclic systems of ligands L3 lie in almost parallel planes π-electron density distribution over the Ln triazole ring
(8°). In this case, torsion angle ClCoN(2)N(3) in com- in the compounds under study depends on the type of
plex VII is equal to 149°, while in complex VIII, it is coordination of a given ligand to a metal.
equal to 18°. This difference in the structures of com-
Compounds I, II, IV, and V (with Co atom coordi-
plexes II, VII, andVIII can be characterized as rotation
nating the N(3) atom) have close lengths of analogous
isomerism.
bonds in triazole ring: the π-electron density is local-
The Co–N bonds in complexes VII (2.029(6) Å)
ized over two multiple bonds N(2)−C(1) (aver.
and VIII (2.023(4) 0.005 Å) are slightly shorter than
1.304
0.009 Å) and N(3)−C(A) (aver.
in complex II.
1.309 0.007 Å); two single bonds of a ring N(1)–
C(1) (1.371 0.005 Å) and N(1)–C(A) (aver. 1.363
0.005 Å) are noticeably longer. In compounds VII and
VIII (with the metal atom coordinated to the N(2)
atom), in triazole fragment, only one multiple bond
remains, namely, the N(3)−C(A) bond (1.310 0.000 Å).
As a result of delocalization of the π-electron density,
the N(2)–C(1) and N(1)–C(1) bonds in VII have
almost equal lengths (in compound VII, the former
bond becomes substantially longer (1.331(9) Å),
while the former bond, conversely, becomes shorter
(1.337(9) Å) than in compounds I and II), whereas in
complex VIII, the value ∆{(N(1)–C(1)) − (N(2)–
C(1))} = 0.038 Å is significantly lower than in I, II,
The geometrical parameter of ligands L0 in com-
plexes I and II are almost similar; in complex II, the
average values are considered for two independent
ligands.
In Table 4, the lengths of the N–C and N–N bonds in
triazole rings of complexes I and II are compared with
the values in the previously studied compounds of anal-
ogous ligands L0–L3. In compounds I, II, IV, V, the
N(3) atom is involved in coordination with a metal,
while in complexes VII and VIII, the N(2) atoms is
coordinated to a metal. In compounds (HL32 )[FeCl4]
(IX) [8] and L2 · 0.5H2O (X) [13], the N(2) atom partic-
ipates in hydrogen bonds. One can suggest that the IV, V (aver. 0.067 Å). Compounds IX and X with the
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412
SOKOL et al.
Cl(1)
Co(1)
Cl(2)
Fig. 6. The structure of [CoL3 Cl ] · CH CN (VIII).
2
3
2
N(2) atom involved in hydrogen bonds, an intermedi- C(8) and triazole ring in complexes I and II are equal
ate distribution of electron density is observed: the to 12° and 13°, respectively. In chloride complex
average length of the bonds N(2)–C(1) 1.319 0.001 Å, VIII, the analogous parameters of the L ligand are
N(1)–C(1) 1.366 0.001 Å, N(3)–C(Ä) 1.313
0.425, 0.824 Å, and 20°, respectively. The substituent
0.001 Å. Whatever the type of coordination and the in position 3 of triazole ring in ligands Ln is most
nature of a metal and inorganic anions, the conforma- “mobile”, since it can rotate easily about the C(12)–
tion of all considered molecules (ions) Ln (HLn) in a C(13) bond between fragments. The rotation of a
free state (in compound X), in the form of a single- cyclic substituent about the triazole fragment plane is
charged cation (in complex with Fe chloride IX), and specified, as a rule, by the requirements of the molec-
as a ligand (in compounds IV–VIII) remains almost ular packing in crystals. The angles of rotation (j) for
unchanged. The geometry of a rigid tricyclic system ligands L0–L2 in structures IV, V, VII, and X lie within
of tetrahydroisoquinoline, containing annealed 74°–85°. In structures I and II, this angle is equal to
1,2,4-triazole ring, remains nearly unaltered. In the 88° and 93°, respectively. Only in the L3 ligand (with
nitrate complexes I and II, the L0 molecules are furyl substituent in position 3), the ϕ angles differ
slightly flattened as compared to the previously stud- substantially from such angles for L0−L2: in com-
ied chloride complexes. The N(1) and C(9) atoms in plexes VIII and IX, the ϕ angle in independent
both I and II deviate by 0.322 and 0.698 Å (in I) and ligands is equal to 58° and 133°, 47° and 121°, respec-
by 0.277 and 0.710 Å (in II) from eight-atom plane of tively. In these compounds, the ϕ angles are deter-
benzene ring C(2)–C(7) and from the C(1) and C(8) mined by the presence of shortened contacts O−H(C)
atoms conjugated with this ring (and coplanar to an (2.72 and 2.46 Å) between the O atom of furane rings
accuracy of 0.036 Å in I and to 0.020 Å in II). The and one of the H atoms of the methyl group in dihy-
dihedral angles between the planes of atoms C(1)– droisoquinoline fragments.
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COMPLEXES OF CU(II) AND CO(II) NITRATES
413
Table 4. Bond lengths (Å) in triazole fragments of complexes I, II, IV, V, VII–X
Type of coordination
Complex
N(2)–C(1) N(1)–C(1) N(1)–C(A)* N(3)–C(A)* N(2)–N(3)
to a metal
[CuL0 (NO3)2] (I)
N(3)
1.300
1.300
1.313
1.304
1.331
1.316
1.372
1.367
1.376
1.370
1.337
1.354
1.367
1.361
1.358
1.367
1.386
1.375
1.314
1.315
1.302
1.304
1.310
1.310
1.384
1.378
1.378
1.381
1.381
1.387
2
[CÓL0 (NO3)2] · CH3CN (II)**
2
[CuL1 Cl2] · 2C3H6O (IV)
2
[CuL2 Cl2] · 2C3H6O (V)
2
[CoL0 Cl2] · CH3CN (VII)
N(2)
2
[CoL3 Cl2] · CH3CN (VIII)**
2
(HL3 )[FeCl4] (IX)**
L2 · 0.5H2O (X)
N(2) (H-bonds)***
1.319
1.318
1.366
1.365
1.377
1.369
1.312
1.314
1.369
1.391
2
* C(A) in structures I and II corresponds to the C(14) atom, in the remaining structures, to the C(12) atom.
** The average values are given for two independent molecules.
*** In complexes IX and X the N(2) atom is involved in hydrogen bonds.
The packing of structural units in crystals I, II is the xz plane, while in structure II, two L0 ligands are
shown in Fig. 7, 8, respectively. The flattened tricyclic parallel to the yz and xy planes, respectively. As a
fragments of ligands L0 in structure I are parallel to result, stacks of planar fragments of L0 molecules are
x
0
z
y
Fig. 7. Packing of structural units in crystal I.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 32 No. 6 2006

414
SOKOL et al.
x
z
0
y
Fig. 8. Packing of structural units in crystal II.
3. Gorter, S. and Engelfriet, D.W., Acta Crystallogr., Sect.
B: Struct. Crystallogr. Cryst. Chem., 1981, vol. 37, no. 6,
p. 1214.
formed along the y axis in structure I, and along the x
and z axes in structure II. The distance between the
planar fragments of ligands L0 in the stacks exceeds
5 Å. The shortest molecular contacts are formed in I
between the terminal O(2) atom of the NO3 group and
the C(6) atom of dihydroisoquinoline fragment:
é(2)···ç(6) 2.65, é(2)···ë(6) 3.357(3) Å, the angle
O(2)H(6)C(6) 148°; O(2)···H(10B) 2.53, O(2)···C(10)
3.421(4) Å, the angle O(2)H(10B)C(10) being 160°.
Structure II contains short intermolecular contacts
between the N atoms of solvated acetonitrile molecule
and the H atom of molecules L0 and terminal atoms
é(NO3): N(6)···H(5A) 2.72, N(6)···C(5) 3.442(4) Å,
the angle N(6)H(5A)C(5) 141°, N(6)···H(18A) 2.79,
N(6)···C(18) 3.549(3) Å, the angle N(6)H(18A)C(18)
149°; O(3)···H(8B) 2.57, O(3)···C(8) 3.451(4) Å, the
angle O(3)H(8B)C(8) 159°, O(6)···H(11'F) 2.55,
4. Jarvis, J.A., Acta Crystallogr., 1962, vol. 15, no. 5,
p. 964.
5. Roimann, C.W. and Zossi, M., Acta Crystallogr., Sect. B:
Struct. Crystallogr. Cryst. Chem., 1971, vol. 27, no. 3,
p. 682.
6. Engelfriet, D.W., Verschoor, G.C., and Brinker, W., Acta
Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem.,
1980, vol. 36, no. 5, p. 1554.
7. Sinditskii, V.P., Sokol, V.I., Fogel’zang, A.E., et al., Zh.
Neorg. Khim., 1987, vol. 32, no. 8, p. 1950.
8. Sokol, V.I., Davydov, V.V., Merkur’eva, N.Yu., et al., Zh.
Neorg. Khim., 2003, vol. 48, no. 2, p. 269 [Russ. J. Inorg.
Chem. (Engl. Transl.), vol. 48, no. 2, p. 217].
9. Sokol, V.I, Davydov, V.V., Pervushina, S.A., et al., Zh.
Neorg. Khim., 2003, vol. 48, no. 2, p. 263 [Russ. J. Inorg.
Chem. (Engl. Transl.), vol. 48, no. 2, p. 211].
O(6)···C(11')
3.355(4)
Å,
the
angle
O(6)H(11'F)C(11') 141°.
10. Sokol, V.I., Davydov, V.V., Ryabov, M.A., et al., Zh.
Neorg. Khim., 2000, vol. 45, no. 4, p. 599 [Russ. J. Inorg.
Chem. (Engl. Transl.), vol. 45, no. 4, p. 528].
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