The copper(II) acetate complex with 2-(2-hydroxyphenyl)-4,4-diphenyl-1,2- dihydro-4H-3,1-benzoxazine

Article abstract of DOI:10.1134/S1070328407090096

The Cu(II) acetate complex with 2-(2-hydroxyphenyl)-4,4-diphenyl-1,2- dihydro-4H-3,1-benzoxazine (L) was synthesized for the first time and structurally studied by X-ray diffraction. The complex crystallizes as two crystallographically independent centros

Full text of DOI:10.1134/S1070328407090096

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2007, Vol. 33, No. 9, pp. 674–679. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © V.T. Panushkin, T.E. Apenysheva, V.I. Sokol, V.S. Sergienko, K.S. Pushkareva, S.N. Bolotin, F.A. Kolokolov, E.V. Gromachevskaya, A.A. Borodavko,
T.P. Kosulina, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 9, pp. 686–691.
The Copper(II) Acetate Complex with 2-(2-Hydroxyphenyl)-4,4-
diphenyl-1,2-dihydro-4H-3,1-benzoxazine
V. T. Panushkina, T. E. Apenyshevaa, V. I. Sokolb, V. S. Sergienkob, K. S. Pushkarevaa,
S. N. Bolotina, F. A. Kolokolova, E. V. Gromachevskayac, A. A. Borodavkoc, and T. P. Kosulinac
a Kuban’State University, ul. Stavropol’skaya 129, Krasnodar 350040 Russia
b Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow 119991 Russia
c Kuban’State Technological University, Krasnodar, Russia
Received September 25, 2006
Abstract—The Cu(II) acetate complex with 2-(2-hydroxyphenyl)-4,4-diphenyl-1,2-dihydro-4H-3,1-benzox-
azine (L) was synthesized for the first time and structurally studied by X-ray diffraction. The complex crystal-
lizes as two crystallographically independent centrosymmetric binuclear molecules [Cu2(µ-L)2Ac2] of similar
structure, where L occurs as azomethin tautomeric form. The ligand performs tridentate chelate-bridging func-
tion. Each Cu atom exhibits extended tetragonal-pyramidal coordination by two O atoms and the N atom of one
ligand L in the equatorial plane and by the O atom of the second ligand L in the axial position. The fourth equa-
torial position in the metal coordination polyhedron is occupied by the O atom of monodentate terminal acetate
group.
DOI: 10.1134/S1070328407090096
1,2-Dihydro-4H-3,1-benzoxazines are original
X-ray diffraction analysis. The rhombohedral
chemical systems, whose peculiar reactivity and struc- crystals of compound I of the dark blue color belong to
tures are specified by annelation of 1,3-oxazine cycle the triclinic crystal system. The unit cell parameters:
with benzene nucleus. Since the above compounds ‡ = 10.665(3), b = 14.322(4), Ò = 16.683(4) Å, α =
91.49(7)°, β = 98.55(6)°, γ =107.63(8)°, V = 2394(1) Å3,
have the hydroxyphenyl radical as a substituent in posi-
ρ(calcd.) = 1.317 g/cm3, µåÓ = 9.42 cm–1, F(000) =
tion 2, they are the potential tridentate ligands capable
of complex formation with the transition metals. The
formation of chelates can occur due to the elimination
980, M = 949.96, Z = 2, space group P1 .
of the acid phenol proton with the formation of the
ionic bond O–M and the donor-acceptor bonds M–O,
M–N with the N and O atoms of benzoxazine ring.
The goal of this work was to synthesize the solid
Cu(II) acetate complex with 2-(2-hydroxyphenyl-4,4-
diphenyl-1,2-dihydro-4H-3,1-benzoxazine (I) and to
study its composition and structure by X-ray diffraction.
The set of experimental data was obtained from a
single crystal at room temperature on an Enraf-Nonius
CAD-4 automated four-circle diffractometer (MoKα
radiation, graphite monochromator, ω-scan mode,
2θmax = 54°). The total of 10811 reflections was
recorded (Rint = 0.035, –13 ≤ h ≤ 13,–18 ≤ k ≤ 18,
0 ≤ l ≤ 21).
The structure was solved by the direct method
(SHELXS-97) [1] and refined by the full-matrix least-
squares method (on F2) for non-hydrogen atoms
EXPERIMENTAL
Synthesis. Cu(CH3COO)2 (0.0200 g) in 2.5 ml etha- (SHELXL-97) [2]. The H(1) and H(1') atoms at O(2)
nol was added to compound L (0.0379 g) in 2.5 ml eth- and O(2'), respectively, were localized from the Fourier
anol. The mixture was heated with a reflux condenser difference synthesis and refined in isotropic approxi-
(50–60°ë) until the dark blue precipitate of complex I mation. The positions of the remaining hydrogen atoms
was formed. After cooling, the precipitate was filtered, were calculated geometrically (C–H(Ph) 0.93, C–H(Me)
washed with cold ethanol, and dried in air. Single crys- 0.96 Å) and included in refinement with fixed posi-
tals were grown from the chloroform–alcohol mixture tional and thermal parameters UH. The latter are
(1 : 1). The yield was 87%.
0.1−0.3 Å2 as large as the Uj parameters of the corre-
sponding C atoms.
For C56H46N2O8Cu2
The final refinement parameters: R1 = 0.044, wR2 =
0.108 for 5875 reflections with Fo ≥ 4σ(Fo); R1 = 0.116,
wR2 = 0.135 for all reflections; GOOF = 1.003. The
maximum and minimum of residual electron density is
anal. calcd. (%): C, 69.69; H, 4.53; N, 2.84; Cu, 12.98.
Found, (%):
C, 69.41; H, 4.48; N, 2.34; Cu, 11.3.
674

THE COPPER(II) ACETATE COMPLEX
675
C(5)
C(4)
C(17)
C(3)
C(11)
C(6)
O(4A)
C(16)
C(18)
C(23)
C(7)
N(1)
C(12)
C(2)
O(3A)
C(15)
C(8)
C(13)
C(19)
C(1)
O(2A)
Cu(1A)
C(20)
O(1)
C(14)
C(22)
C(21)
C(26)
Cu(1)
O(1A)
O(2)
C(24)
C(25)
O(3)
O(4)
C(27)
C(28)
Fig. 1. The molecular structure of [Cu L Ac ].
2
2
2
0.425 and –0.528 Â Å3; the coefficient of extinction is
equal to 0.0000(3).
T = 50°C
Cu(Ac)2 + HL
CuLAc + HAc.
The coordinates and thermal parameters of atoms in
structure I are given in Table 1; the bond lengths and
bond angles are listed in Table 2.
The triclinic cell of compound I contains two cen-
trosymmetric crystallographically independent binu-
clear molecules of the complex [Cu2(µ-L)2Ac2] (I and
I'). Since the geometrical parameters of these mole-
cules are close, the further discussion will cover only
one of them (I) and the averaged values will be given
for the analogous bonds and angles. In the dimeric
complex I (Fig. 1), the monodeprotonated benzoxazine
ligand L occurs in azomethin tautomeric form. The H(1)
atom lies at the O(2) atom of the phenylcarbinol frag-
ment of the ligand L and participates in the formation of
a strong chelate hydrogen bond between the L molecule
RESULTS AND DISCUSSION
Dihydrobenzoxazines with no substituents in posi-
tion 4 are capable of tautomeric transformation to give
a linear azomethin form (the Schiff base) [3–5]. This
tendency is the most pronounced in compounds, where
the alternative unsaturated structure is stabilized by the
intramolecular hydrogen bond [6, 7].
As follows from IR spectrum of a solid ligand L [5] and the O(4) atom of the acetate group. All the three
recorded as KBr pellet, the absorption band at
3329 cm−1 is due to the stretching vibrations of the
N−H bond. Thus, the molecule of a solid ligand occurs
as a cyclic form Ä:
donor centers of the ligand L (two O atoms and the N
atom) are involved in the coordination with the Cu atom.
The ligand L in complex I acts as a tridentate chelate
bridge and closes two six-membered metal rings in a
molecule of the complex. The acetate group in I is the
monodentate terminal group. The coordination polyhe-
dron of the Cu atom is an extended tetragonal pyramid
(TP). The double oxygen bridge in binuclear mole-
cules of the complex is formed by the O(1) and é(1A)
atoms of the ligand phenol fragments, and in the TP of
one Cu atom, the O(1) atom lies at the vertex of a base
(Cu(1)−O(1) 1.905(3) 0.005 Å), whereas in the TP
of the inverted Cu(1A) atom, in the axial position with
considerably elongated bond (Cu(1A)–O(1) 2.405(3)
0.005 Å). The TP base contains also the O(2) and
N(1) atoms of the phenylcarbinol and azomethin frag-
ments of the L ligand and the acetate O(3) atom. The
longest bond in the TP base is Cu–OAc 1.972(3)
Ph
Ph
Ph
Ph
O
OH
X
N
H
O
N
H
OH
(A)
(B)
According to the elemental analysis data, the reac-
tion of complex formation gives, CuLAc compounds
(Ac– is the acetate ion CH3COO–) independent of the
initial ratio of the components. Thus, the reaction of 0.002 Å; the bonds Cu–N 1.955(3) 0.001 Å and
complex formation is as follows: Cu−O(2) 1.940(3) 0.009 Å are somewhat shorter.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 9 2007

676
PANUSHKIN et al.
Table 1. The atomic coordinates and thermal parameters Ueq, UH in the crystal structure of [Cu2(µ-L)2Ac2]
Atom Atom
Cu(1)
Ueq, UH, Å2
x
y
z
x
y
z
Ueq, UH, Å2
0.9824(1) 0.0820(1) –0.0587(1) 0.0371(1) Cu(1')
0.8541(2) –0.0227(2) –0.0199(2) 0.0463(6) O(1')
1.0925(3) 0.1909(2) –0.1098(2) 0.0445(7) O(2')
1.5385(1) 0.4122(1) –0.5388(1) 0.0349(1)
1.5588(2) 0.5058(2) –0.4126(1) 0.0416(6)
1.6418(3) 0.3249(2) –0.5090(2) 0.0392(6)
O(1)
O(2)
H(1)
O(3)
O(4)
N(1)
C(1)
C(2)
H(2A)
C(3)
H(3A)
C(4)
H(4A)
C(5)
H(5A)
C(6)
1.079(5)
0.174(4) –0.151(3)
0.08(2)
H(1')
1.694(6)
0.345(5)
–0.522(4)
0.12(3)
0.9704(3) –0.0061(2) –0.1545(1) 0.0461(6) O(3')
1.0570(3) 0.1010(2) –0.2413(2) 0.0544(7) O(4')
0.9900(3) 0.1731(2) 0.0325(2) 0.0427(7) N(1')
0.7647(4) –0.0120(3) 0.0239(2) 0.0497(9) C(1')
0.6530(4) –0.0923(4) 0.0273(3) 0.068(1)
0.642 –0.151 –0.001 0.06
0.5587(5) –0.0852(5) 0.0734(4) 0.087(2)
0.483 –0.139 0.074 0.10
0.5740(6) 0.0000(5) 0.1187(4) 0.095(2)
0.510 0.003 0.150 0.11
0.6828(5) 0.0798(4) 0.1178(3) 0.077(1)
0.693 0.137 0.149 0.09
1.7020(2) 0.5092(2) –0.5623(2) 0.0440(6)
1.8334(3) 0.4160(2) –0.5658(2) 0.0668(9)
1.3775(3) 0.3107(2) –0.5205(2) 0.0353(6)
1.3173(4) 0.4626(3) –0.6254(2) 0.0422(8)
1.2709(4) 0.5235(3) –0.6785(2) 0.055(1)
1.329
1.1432(5) 0.4955(4) –0.7185(3) 0.067(1)
1.116 0.537 –0.754 0.08
1.0537(5) 0.4062(4) –0.7071(3) 0.072(1)
0.966 0.388 –0.735 0..08
1.0938(4) 0.3450(3) –0.6549(3) 0.058(1)
1.033 0.286 –0.646 0.06
C(2')
H(2A')
C(3')
H(3A')
C(4')
H(4A')
C(5')
0.584
–0.686
0.06
H(5A')
C(6')
0.7810(4) 0.0754(3) 0.0696(2) 0.055(1)
0.8967(4) 0.1593(3) 0.0762(2) 0.055(1)
1.2262(3) 0.3704(3) –0.6137(2) 0.0424(8)
1.2598(4) 0.3044(3) –0.5584(2) 0.0446(9)
C(7)
C(7')
H(7A)
C(8)
0.906
0.209
0.116
0.06
H(7A')
1.190
0.251
–0.548
0.06
1.1089(4) 0.2542(3) 0.0556(2) 0.0444(9) C(8')
1.3892(3) 0.2444(2) –0.4595(2) 0.0365(8)
1.3031(4) 0.2279(3) –0.4028(2) 0.050(1)
C(9)
1.1709(5) 0.2708(3) 0.1358(2) 0.059(1)
1.134 0.229 0.174 0.07
1.2861(5) 0.3469(4) 0.1598(3) 0.073(1)
0.358 0.214 0.08
1.3420(5) 0.4072(3) 0.1033(3) 0.070(1)
H(11A) 1.419 0.459 0.119 0.07
C(12) 1.2829(4) 0.3900(3) 0.0223(2) 0.053(1)
H(12A) 1.322 0.430 –0.016 0.06
C(9')
H(9A)
C(10)
H(9A')
1.239
1.3118(4) 0.1640(3) –0.3431(2) 0.056(1)
0.152 –0.306 0.06
1.4074(4) 0.1182(3) –0.3386(2) 0.052(1)
H(11B) 1.414 0.076 –0.298 0.07
C(12') 1.4941(4) 0.1351(2) –0.3945(2) 0.0429(8)
H(12B) 1.558 0.103 –0.391 0.05
0.260
–0.405
0.05
C(10')
H(10A) 1.326
C(11)
H(10B) 1.253
C(11')
C(13)
C(14)
C(15)
C(16)
H(16A) 0.989
C(17)
1.1658(4) 0.3137(3) –0.0027(2) 0.0404(8) C(13')
1.1006(3) 0.2921(2) –0.0921(2) 0.0392(8) C(14')
0.9594(4) 0.3015(3) –0.1047(2) 0.0431(8) C(15')
1.4885(3) 0.1981(2) –0.4547(2) 0.0350(7)
1.5847(3) 0.2200(2) –0.5163(2) 0.0332(7)
1.5102(3) 0.1831(2) –0.6022(2) 0.0358(7)
1.4036(4) 0.0972(3) –0.6160(2) 0.0458(9)
0.9258(4) 0.3649(3) –0.0542(3) 0.060(1)
0.402 –0.011 0.07
0.7987(5) 0.3738(4) –0.0673(4) 0.084(2)
H(17A) 0.777 0.417 –0.033 0.10
C(18) 0.7054(5) 0.3203(4) –0.1297(4) 0.085(2)
H(18A) 0.620 0.326 –0.138 0.10
C(19) 0.7375(5) 0.2581(4) –0.1796(3) 0.084(2)
H(19A) 0.674 0.221 –0.222 0.10
C(20) 0.8653(4) 0.2485(3) –0.1678(3) 0.061(1)
H(20A) 0.887 0.206 –0.203 0.07
1.1866(4) 0.3565(3) –0.1473(2) 0.0440(9) C(21')
1.1748(4) 0.4467(3) –0.1654(3) 0.067(1) C(22')
0.467 –0.146 0.08
1.2588(5) 0.5076(4) –0.2116(3) 0.088(2)
H(23A) 1.251 0.569 –0.222 0.11
C(24) 1.3541(5) 0.4767(5) –0.2413(3) 0.084(2)
H(24A) 1.410 0.517 –0.273 0.08
C(25) 1.3670(5) 0.3881(4) –0.2246(3) 0.073(1)
H(25A) 1.432 0.367 –0.245 0.08
C(26) 1.2844(4) 0.3267(3) –0.1770(3) 0.059(1)
H(26A) 1.295 0.266 –0.165 0.07
1.0116(4) 0.0159(3) –0.2209(2) 0.0422(8) C(27')
1.0049(5) –0.0682(3) –0.2796(2) 0.065(1) C(28')
C(16')
H(16B) 1.376
C(17') 1.3378(4) 0.0633(3) –0.6935(3) 0.058(1)
H(17B) 1.267 0.005 –0.701 0.06
C(18') 1.3745(5) 0.1137(4) –0.7589(3) 0.069(1)
H(18B) 1.328 0.091 –0.811 0.08
C(19') 1.4813(5) 0.1989(4) –0.7461(3) 0.070(1)
H(19B) 1.508 0.234 –0.790 0.06
C(20') 1.5485(4) 0.2331(3) –0.6693(2) 0.052(1)
H(20B) 1.621 0.290 –0.662 0.06
0.062
–0.572
–0.05
C(21)
C(22)
H(22A) 1.109
C(23)
1.7019(3) 0.1794(2) –0.4933(2) 0.0364(8)
1.7225(4) 0.1060(3) –0.5410(2) 0.0458(9)
H(22B) 1.664
C(23') 1.8288(4) 0.0712(3) –0.5174(3) 0.060(1)
H(23B) 1.841 0.022 –0.550 0.07
C(24') 1.9153(4) 0.1076(3) –0.4466(3) 0.060(1)
H(24B) 1.987 0.083 –0.431 0.06
C(25') 1.8961(4) 0.1807(3) –0.3988(3) 0.053(1)
H(25B) 1.954 0.206 –0.350 0.05
C(26') 1.7915(4) 0.2160(3) –0.4222(2) 0.0458(9)
H(26B) 1.780 0.266 –0.390 0.05
0.080
–0.589
0.05
C(27)
C(28)
1.8117(4) 0.4973(3) –0.5700(2) 0.0456(9)
1.9209(4) 0.5843(3) –0.5868(3) 0.061(1)
H(28A) 0.969
H(28B) 1.092
H(28C) 0.949
–0.129
–0.062
–0.066
–0.257
–0.290
–0.330
0.10
0.10
0.10
H(28D) 1.890
H(28E) 1.946
H(28F) 1.996
0.641
0.572
0.596
–0.589
–0.638
–0.544
0.09
0.09
0.09
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 9 2007

THE COPPER(II) ACETATE COMPLEX
Table 2. The bond lengths (d) and bond angles (ω) in [Cu2(µ-L)2Ac2]
677
Bond
Cu(1)–O(1)
d, Å
Bond
O(3)–C(27)
d, Å
Bond
d, Å
1.900(2)
1.949(3)
1.974(2)
1.955(3)
2.400(2)
1.324(5)
0.69(5)
1.265(4)
1.244(4)
1.291(5)
1.430(5)
1.910(2)
1.931(3)
1.971(2)
1.955(3)
Cu(1')–O(1A')
O(1')–C(1')
O(2')–H(1')
O(2')–C(14')
O(3')–C(27')
O(4')–C(27')
N(1')–C(7')
N(1')–C(8')
2.410(2)
1.314(5)
0.62(7)
Cu(1)–O(2)
Cu(1)–O(3)
Cu(1)–N(1)
Cu(1)–O(1A)
O(1)–C(1)
O(4)–C(27)
N(1)–C(7)
N(1)–C(8)
1.433(4)
1.257(5)
1.256(5)
1.294(5)
1.428(4)
Cu(1')–O(1')
Cu(1')–O(2')
Cu(1')–O(3')
Cu(1')–N(1')
O(2)–H(1)
O(2)–C(14)
1.446(4)
Angle
ω, deg
Angle
ω, deg
Angle
ω, deg
O(1)Cu(1)O(2)
O(1)Cu(1)O(3)
O(1)Cu(1)N(1)
O(1)Cu(1)O(1A)
O(2)Cu(1)O(3)
O(2)Cu(1)O(1A)
O(2)Cu(1)N(1)
O(1A)Cu(1)O(3)
O(1A)Cu(1)N(1)
Cu(1)O(1)C(1)
Cu(1)O(2)C(14)
Cu(1)O(3)C(27)
Cu(1)N(1)C(7)
Cu(1)N(1)C(8)
O(1)C(1)C(2)
171.7(1)
88.5(1)
N(1)C(7)C(6)
126.3(4)
119.5(4)
120.5(3)
108.9(3)
125.1(4)
117.0(3)
117.9(3)
169.8(1)
87.8(1)
O(1A')Cu(1')N(1')
Cu(1')O(3')C(27')
Cu(1')N(1')C(7')
Cu(1')N(1')C(8')
C(7')N(1')C(8')
O(1')C(1')C(2')
O(1')C(1')C(6')
N(1')C(7')C(6')
N(1')C(8')C(9')
N(1')C(8')C(13')
O(2')C(14')C(13')
O(2')C(14')C(21')
O(2')C(14')C(15')
O(3')C(27')O(4')
O(3')C(27')C(28')
O(4')C(27')C(28')
93.3(6)
128.9(2)
122.7(3)
118.6(2)
118.5(3)
118.8(3)
123.2(3)
126.8(3)
119.2(3)
121.0(3)
104.8(3)
105.8(3)
111.2(3)
123.6(4)
118.0(3)
118.4(3)
N(1)C(8)C(9)
92.6(1)
N(1)C(8)C(13)
O(2)C(14)C(21)
O(3)C(27)O(4)
O(3)C(27)C(28)
O(4)C(27)C(28)
O(1')Cu(1')O(2')
O(1')Cu(1')O(3')
O(1')Cu(1')N(1')
O(2')Cu(1')O(3')
O(2')Cu(1')N(1')
O(3')Cu(1')N(1')
O(1A')Cu(1')O(1')
O(1A')Cu(1')O(2')
O(1A')Cu(1')O(3')
85.7(1)
89.2(1)
102.3(1)
89.3(1)
92.0(4)
90.8(4)
125.0(2)
123.0(2)
128.6(2)
122.8(3)
118.3(2)
118.7(4)
122.6(4)
118.7(3)
93.3(1)
88.7(1)
89.7(1)
176.6(1)
86.2(2)
169.8(6)
87.7(2)
O(1)C(1)C(6)
C(7)N(1)C(8)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 9 2007

678
PANUSHKIN et al.
O(3A)
O(1)
O(2A)
Cu(1)
Cu(1A)
O(2)
O(1A)
O(3)
Fig. 2. Superposition of two independent molecules L (solid line) and L' (dotted line) provided that eight atoms coincide (Cu(1),
Cu(1A), O(1), O(1A), O(2), O(2A), O(3), and O(3A)).
x
z
0
y
Fig. 3. The packing of the complex molecules in crystal I (projection onto the plane yz).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 9 2007

THE COPPER(II) ACETATE COMPLEX
679
The greatest deviations from the ideal values of 180° of the phenyl rings in the triphenylcarbinol fragment in
and 90° are observed for the TP angles L and L' slightly differ and are equal to 76.3°, 89.9° and
O(1A')Cu(2)O(2') 169.7° and O(2)Cu(1)O(1A) 103.3°. 97.9° in L and 81.7°, 86.7°, and 112.7° in L'.
The Cu···Cu distance in the dimers is equal to 3.170
0.003 Å.
The structural units of crystal I, i.e., the binuclear
molecules of the complexes, are located at two inde-
pendent inversion centers (0, 0, 0 and 0.5, 0.5, 0.5)
(Fig. 3). They show different orientation relative to the
inversion centers, which is most likely due to the opti-
mum crystal packing requirements. The shortened con-
tacts are observed between the complex molecules in
the crystal. The shortest of them are é(3)···ë(7) 3.163,
é(4)···C(10') 3.323, and é(3')···C(24) 3.372 Å.
The geometrical parameters of the chelate
é(2)−ç(1)···é(4) in the H-heterocycle of the complex
are: O(2)–H 0.69(5), é(4)···ç 1.78(5), é(2)···é(4)
2.430(4) Å, the angle O(2)H(1)O(4) is 168(3)°. The
above H-cycle, like six-membered chelate metal cycles
conjugated with the phenyl rings in complex I, has pro-
nounced nonplanar structure. The H-cycle has the
asymmetric boat conformation: the O(2) and C(27)
atoms deviate from the mean plane Cu(1)O(3)O(4)H(1)
(∆ = 0.04 Å) by 0.223 and 0.086 Å, respectively. The
chelate cycle conjugated with the triphenylcarbinol
group also has the asymmetric boat conformation: the
N(1) and C(14) atoms extend from the
Cu(1)O(2)C(8)C(13) plane (∆ = 0.03 Å) by 0.505 and
0.692 Å, respectively. The second cycle conjugated
with the phenol ring has the sofa conformation: the Cu
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
for Basic Research (project no. 06-03-32881-a).
REFERENCES
1. Sheldrick, G.M., SHELXS-97. Program for the Solution
of Crystal Structures, Göttingen (Germany): Univ. of
Göttingen, 1997.
2. Sheldrick, G.M., SHELXL-97. Program for the Refine-
ment of Crystal Structures, Göttingen (Germany): Univ.
of Göttingen, 1997.
3. Gromachevskaya, E.V., Kosulina, T.P., and Kul’ne-
vich, V.G., Khim. Geterotsikl. Soedin., 1985, no. 12,
p. 1682.
atom
deviates
by
0.501
Å
from
the
O(1)N(1)C(1)C(6)C(7) plane (∆ = 0.03 Å).
As was noted above, the geometrical parameters of
two independent ligands L and L' in the complexes I
and I' are very close, particularly, the lengths of the
analogous bonds in the ligands. The lengths of the
bonds O–C(sp3) in the triphenylcarbinol fragment
O(2)–C(14) (1.446(4) 0.007 Å), O–C(sp2) in the phe-
4. Kliege, W., Metge, J., and Retting, S.J., Can. J. Chem.,
nyl fragment O(1)-C(11) (1.311(5)
0.005 Å) and
1988, vol. 76, no. 4, p. 389.
O=C(sp2) in the acetate group O(3)–C(27) (1.261(5)
0.004 Å) and O(4)–C(27) (1.250(4) 0.006 Å) are
close to the standard values [8]. The N(1)–C(7) bond
1.292(5) 0.002 Å in the ligand L is multiple.
5. Neuvonen, K., Pohtala, R., and Pihlaja, K., Magn. Res.
Chem., 1989, vol. 27, no. 8, p. 725.
6. Saeed, A.A.H. and Ebraheem, E.K., Can. J. Spectrosc.,
1983, no. 6, p. 169.
The main difference between two independent frag-
ments CuL and Cu'L' in structure I (Fig. 2) appears in
different relative direction of the phenyl rings and ace-
tate groups. The analogous angles between the planes
7. Gromachevskaya, E.V., Kosulina, T.P., Kul’nevich, V.G.,
et al., Khim. Geterotsikl. Soedin., 1990, no. 1, p. 101.
8. Allen, F.H., Kennard, O., Watson, D., et al., J. Chem.
Soc., Perkin Trans. 2, 1987, p. S1.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 9 2007