Cu(II) complexes with pyrazole-derived ligands. Crystal structure of {[diaquanitrato(3-phenyl-5-(2-pyridyl)pyrazole)]copper(II)} nitrate

Article abstract of DOI:10.1016/S0277-5387(01)00858-0

Reaction of the ligands 3-phenyl-5-(2-pyridyl)pyrazole (HL⁰) and 3-phenyl-5-(6-methyl-(2-pyridyl))pyrazole (HL¹) with Cu(NO₃)₂·3H₂O and CuX₂·xH₂O (X= Cl, Br) gives complexes with stoichiometry Cu(HL⁰)₂X₂·xH₂O, Cu(HL¹)₂X₂??EtOH, Cu(HL)X₂, Cu(HL)₂(NO₃)₂·xH₂O (HL = HL⁰, HL¹) and Cu(HL⁰)(NO₃)₂·2H₂O. The new complexes were characterised by elemental analyses, conductivity measurements and infrared and electronic spectroscopy. The crystal and molecular structure of [Cu(HL⁰)(NO₃)(H₂O)₂](NO ₃) consists of discrete cations and NO₃^- anions linked by hydrogen bonds. The cation complex [Cu(HL⁰)(NO₃)(H₂O)₂]⁺ contains a copper(II) with a distorted tetragonal pyramid geometry (τ = 0.094), with a H₂O ligand occupying the apical site. The penta-coordinated metal atom is bonded to one pyridinic nitrogen, one pyrazolic nitrogen, one nitrate and two water molecules. The ligand HL⁰ is not completely planar.

Full text of DOI:10.1016/S0277-5387(01)00858-0

Polyhedron 20 (2001) 2531–2536
www.elsevier.com/locate/poly
Cu(II) complexes with pyrazole-derived ligands. Crystal structure
of {[diaquanitrato(3-phenyl-5-(2-pyridyl)pyrazole)]copper(II)}
nitrate
a
Josefina Pons a,*, Arafa Chadghan a, Jaume Casabo´ , Angel Alvarez-Larena b,
Joan Francesc Piniella b, Josep Ros a
a Departament de Qu´ımica, Unitat de Qu´ımica Inorga`nica, Uni6ersitat Auto`noma de Barcelona, E-08193 Bellaterra-Cerdanyola, Barcelona, Spain
b Departament de Geologia, Unitat de Cristallografia, Uni6ersitat Auto`noma de Barcelona, E-08193 Bellaterra-Cerdanyola, Barcelona, Spain
Received 21 February 2001; accepted 17 May 2001
Abstract
Reaction of the ligands 3-phenyl-5-(2-pyridyl)pyrazole (HL0) and 3-phenyl-5-(6-methyl-(2-pyridyl))pyrazole (HL1) with
Cu(NO3)2·3H2O and CuX2·xH2O (X=Cl, Br) gives complexes with stoichiometry Cu(HL0)2X2·xH2O, Cu(HL1)2X2·EtOH,
Cu(HL)X2, Cu(HL)2(NO3)2·xH2O (HL=HL0, HL1) and Cu(HL0)(NO3)2·2H2O. The new complexes were characterised by
elemental analyses, conductivity measurements and infrared and electronic spectroscopy. The crystal and molecular structure of
[Cu(HL0)(NO3)(H2O)2](NO3) consists of discrete cations and NO3− anions linked by hydrogen bonds. The cation complex
[Cu(HL0)(NO3)(H2O)2]+ contains a copper(II) with a distorted tetragonal pyramid geometry (~=0.094), with a H2O ligand
occupying the apical site. The penta-coordinated metal atom is bonded to one pyridinic nitrogen, one pyrazolic nitrogen, one
nitrate and two water molecules. The ligand HL0 is not completely planar. © 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Copper complexes; Pyrazole complexes; Crystal structures
bered heterocycle like pyrazole are thus directly linked
in a single ligand system [8], because the electronic
communication between these two heterocycles can be
avoided.
1. Introduction
Research on the coordination chemistry of pyrazole-
derived ligands has progressed very rapidly over the last
two decades. Mukherjee published an extensive review
in 2000 [1], which complements those presented by La
Monica and Ardizzoia in 1997 [2], and by Trofimenko
in 1986 and 1993 [3,4].
Bidentate and tridentate nitrogen heterocyclic com-
pounds containing six-membered rings such as 2,2%-
bipyridine, 1,10-phenantroline and 2,2%:6%,2¦-terpyridine
have been extensively used in transition metal chemistry
[5–7]. The incorporation of pyrazole groups in the
design of new ligands allows both the electronic and
steric control of the properties of metal complexes. A
six-membered heterocycle like pyridine and a five-mem-
The bidentate ligands 3-(2-pyridyl)pyrazole [9–11],
3-methyl-5-(2-pyridyl)pyrazole [12] and 3-tert-butyl-5-
(2-pyridyl)pyrazole [12] have been described elsewhere,
revealing a remarkable coordination chemistry [12–21].
Our group has reported the preparation of the lig-
ands 3,5-bis(2-pyridyl)pyrazole (HL%), 3-(6-methyl-2-
pyridyl)-5-(2-pyridyl)pyrazole (HL¦) and 3,5-bis-2-
(6-methylpyridyl)pyrazole (HL§) and studied their reac-
tivity with the divalent metal ions Ni(II), Co(II), Zn(II)
and Cu(II) [22–25]. In 1995, Munakata et al. [26]
described three HL% complexes, two of Ag(I) and one of
Cu(II).
We have recently reported the synthesis of the lig-
ands 3-phenyl-5-(2-pyridyl) pyrazole (HL0) and 3-
phenyl-5-(6-methyl-(2-pyridyl))pyrazole (HL1) (Fig. 1)
and that of several Co(II), Pd(II) and Ni(II) complexes
[27–29].
* Corresponding author. Tel.: +34-93-581-2895; fax: +34-93-581-
3101.
E-mail address: josefina.pons@uab.es (J. Pons).
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00858-0

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J. Pons et al. / Polyhedron 20 (2001) 2531–2536
0.10 g; HL1, 0.11 g) in ethanol (10 ml). The resulting
solution was stirred at r.t. for 20 h; crystalline solids
were obtained which were filtered off and dried in
vacuum, washed with ethanol–acetonitrile (50%) and
vacuum dried. The same products (stoichiometry and
yield) were obtained when a 1:1 Cu/HL ratio was used.
1: IR (KBr, cm−1): w(NꢀH) 3205; w(CꢀH)ar 3011;
w(CꢁC), w(CꢁN) 1614, 1574; l(CꢀH)OOP 788, 762;
w(CuꢀN) 410; w(CuꢀCl) 320, 296; w(CuꢀN) 258. UV–
Vis: u(m) (nm) (DMF 1.31×10−3 M): 811(166). UV–
Vis: u (nm) (KBr): 820, 490.
Fig. 1. Pyrazole-derived ligands HL0 and HL1.
Here, we study the synthesis and structural determi-
nation of the Cu(II) complexes of the ligands HL0 and
HL1. The crystal structure of [Cu(HL0)(NO3)(H2O)2]-
(NO3) is described and compared with that of closely
related structures.
2: IR (KBr, cm−1): w(NꢀH) 3198; w(CꢀH)ar 3053;
w(CꢁC), w(CꢁN) 1612, 1572; l(CꢀH)OOP 788, w(CuꢀN)
408; w(CuꢀBr) 292, 268; w(CuꢀN) 258. UV–Vis: u(m)
(nm) (DMF 1.16×10−3 M): 806(165). UV–Vis: u (nm)
(KBr): 818, 453.
3: IR (KBr, cm−1): w(NꢀH) 3109; w(CꢀH)ar 3061;
w(CꢁC), w(CꢁN) 1616, 1578; l(CꢀH)OOP 793, 764;
w(CuꢀN) 531; w(CuꢀCl) 281, 266; w(CuꢀN) 226. UV–
Vis: u(m) (nm) (DMF 1.19×10−3 M): 874(201). UV–
Vis: u (nm) (KBr): 820, 460.
2. Experimental
2.1. General methods
Preparations were performed under nitrogen using
usual Schlenk techniques. All reagents were commercial
grade materials and were used without further purifica-
tion. All solvents (ethanol, acetonitrile and ether) were
previously deoxygenated in a vacuum line.
4: IR (KBr, cm−1): w(NꢀH) 3108; w(CꢀH)ar 3059;
w(CꢁC), w(CꢁN) 1614, 1576; l(CꢀH)OOP 794, 768;
w(CuꢀN) 530; w(CuꢀBr) 278, 266; w(CuꢀN) 228. UV–
Vis: u(m) (nm) (DMF 1.08×10−3 M): 874(300). UV–
Vis: u (nm) (KBr): 820, 500.
Analysis (C, H, N) were performed in our analytical
laboratory on a Perkin–Elmer 240-B instrument. Con-
ductivity measurements were performed at room tem-
perature (r.t.) in 10−3 M in DMF and 10−3 M in
DMSO solutions employing a Radiometer CDM-3
conductimeter.
Infrared spectra were recorded from KBr disks or
Nujol films on a Perkin–Elmer 2000 spectrometer in
the region 4000–100 cm−1. UV–Vis electronic spectra
between 750 and 350 nm, in DMF solution, were run
on a Kontron-Uvikon 860 and in solid state (KBr
pellets, diffuse reflectance) on a Kontron-Tegimenta
CH-6343 Rotkreuz AG. NIR electronic spectra be-
tween 1750 and 750 nm, in DMF solution, were run on
a NIRSystem.
2.3.2. Complexes Cu(HL)X2 where HL=HL0, X=Cl
(5), HL=HL0, X=Br (6) HL=HL1, X=Cl (7), and
HL=HL1, X=Br (8)
To a Schlenk flask containing deoxygenated warm
ethanol (20 ml) was added, in this order HL (0.45
mmol: HL0, 0.10 g; HL1 0.11 g) and CuX2·xH2O (0.90
mmol). The resulting solution was stirred at r.t. for 24
h. Crystalline solids were obtained, which were filtered
off, washed with ethanol and ether and vacuum dried.
5: IR (KBr, cm−1): w(NꢀH) 3129; w(CꢀH)ar 3058;
w(CꢁC), w(CꢁN) 1615, 1571; l(CꢀH)OOP 776, 762;
w(CuꢀN) 414; w(CuꢀCl) 320, 273; w(CuꢀN) 248. UV–
Vis: u(m) (nm) (DMF 1.70×10−3 M): 822(113). UV–
Vis: u (nm) (KBr): 734, 490.
6: IR (KBr, cm−1): w(NꢀH) 3225; w(CꢀH)ar 3091;
w(CꢁC), w(CꢁN) 1615, 1563; l(CꢀH)OOP 778, 763;
w(CuꢀN) 410; w(CuꢀBr) 306, 269; w(CuꢀN) 262. UV–
Vis: u(m) (nm) (DMF 1.35×10−3 M): 848(178). UV–
Vis: u (nm) (KBr): 720, 516.
2.2. Synthesis of ligands
The compounds 3-phenyl-5-(2-pyridyl)pyrazole (HL0)
and 3-phenyl-5-(6-methyl-(2-pyridyl))pyrazole (HL1)
were synthesised as previously reported [27] (Fig. 1).
7: IR (KBr, cm−1): w(NꢀH) 3126; w(CꢀH)ar 3067;
w(CꢁC), w(CꢁN) 1615, 1564; l(CꢀH)OOP 799, 771;
w(CuꢀN) 530; w(CuꢀCl) 276, 254; w(CuꢀN) 232. UV–
Vis: u(m) (nm) (DMF 1.08×10−3 M): 970(156). UV–
Vis: u (nm) (KBr): 780, 550.
2.3. Synthesis of the metal complexes
2.3.1. Complexes Cu(HL0)2X2·xH2O where X=Cl,
x=2 (1), X=Br, x=1 (2) and Cu(HL1)2X2·EtOH
where X=Cl (3) and X=Br (4)
The appropriate metal salt (0.22 mmol: CuCl2·2H2O,
0.037 g; CuBr2, 0.049 g) dissolved in ethanol (10 ml)
was added to a solution of the ligand (0.45 mmol: HL0,
8: IR (KBr, cm−1): w(NꢀH) 3233; w(CꢀH)ar 3060;
w(CꢁC), w(CꢁN) 1614, 1562; l(CꢀH)OOP 795, 762;
w(CuꢀN) 530; w(CuꢀBr) 278, 266; w(CuꢀN) 232. UV–
Vis: u(m) (nm) (DMF 1.09×10−3 M): 900(158). UV–
Vis: u (nm) (KBr): 797, 535.

J. Pons et al. / Polyhedron 20 (2001) 2531–2536
2533
Table 1
Physical and analytical data for the complexes
Compound
Colour
Yield (%)
Analysis a
C (%)
Conductivity d (V−1 cm2 mol−1
)
N (%)
H (%)
Cu(HL0)2Cl2·2H2O (1)
Cu(HL0)2Br2·H2O (2)
Cu(HL1)2Cl2·EtOH (3)
Cu(HL1)2Br2·EtOH (4)
Cu(HL0)Cl2 (5)
green
green
green
green
green
brown
brown
brown
green
green
green
41
76
92
95
80
80
95
94
85
40
58
(54.9)
54.3
(49.2)
48.9
(59.0)
58.7
(51.9)
51.6
(47.3)
47.2
(37.8)
37.8
(48.7)
48.7
(39.3)
39.6
(13.7)
13.7
(12.3)
12.1
(12.9)
12.7
(11.4)
11.2
(11.8)
11.8
(9.4)
9.4
(11.4)
11.2
(9.2)
8.9
(4.3)
4.1
(3.5)
3.6
(4.9)
4.7
(4.4)
4.3
(3.1)
3.1
(2.5)
2.4
(3.5)
3.6
(2.9)
2.9
27 b
45 c
53 b
62 c
54 b
50 c
69 b
68 c
24 b
52 c
47 b
49 c
38 b
56 c
86 b
55 c
94 b
58 c
125 b
57 c
95 b
68 c
Cu(HL0)Br2 (6)
Cu(HL1)Cl2 (7)
Cu(HL1)Br2 (8)
Cu(HL0)2(NO3)2 (9)
Cu(HL1)2(NO3)2·H2O (10)
Cu(HL0)(NO3)2·2H2O (11)
(53.3)
53.1
(53.3)
53.1
(37.8)
37.3
(17.8)
17.4
(16.6)
16.2
(15.7)
15.6
(3.5)
3.6
(4.2)
4.3
(3.4)
3.2
a Calculated analytical values are given in parentheses.
b 10−3 M in DMF.
c 10−3 M in DMSO.
d The reported values for 1:1 and 1:2 electrolytes in DMF are 65–90 and 130–170 V−1 cm2 mol−1 conductivity, respectively, and in DMSO, the
values for 1:1 electrolytes are 50–70 V−1 cm2 mol−1 [32–34].
2.3.3. Complexes Cu(HL)2(NO3)2·xH2O where
HL=HL0, x=0 (9), HL=HL1, x=1 (10)
The resulting solution was stirred at r.t. for 5 h and
concentrated on a vacuum line to one-fifth of the initial
volume. After standing at r.t. for 2 h, a crystalline solid
was obtained, which was filtered off and dried in vac-
uum, washed with ethanol and vacuum dried.
11: IR (KBr, cm−1): w(NꢀH) 3212; w(CꢀH)ar 3096;
w(CꢁC), w(CꢁN) 1616, 1573; l(CꢀH)OOP 787, 763;
w(CuꢀN) 417; w(CuꢀO) 278, w(CuꢀN) 250. IR (Nujol,
cm−1): w1+w3(NO3) 1767, 1750, 1734, 1717. UV–Vis:
u(m) (nm) (DMF 1.22×10−3 M): 646(91). UV–Vis: u
(nm) (KBr): 720, 488.
The appropriate ligand (0.45 mmol: HL0, 010 g; HL1,
0.11 g) was added to a solution of Cu(NO3)2·3H2O
(0.22 mmol, 0.053 g) in ethanol (10 ml). Upon addition
no appreciable change in colour was observed, but after
1 h crystalline solids were obtained, which were filtered
off and dried in vacuum.
9: IR (KBr, cm−1): w(NꢀH) 3121; w(CꢀH)ar 3065;
w(CꢁC), w(CꢁN) 1610, 1575; l(CꢀH)OOP 786, 763;
w(CuꢀN) 412; w(CuꢀO) 272, w(CuꢀN) 244. IR (Nujol,
cm−1): w1+w3(NO3) 1770, 1749, 1735, 1715. UV–Vis:
u(m) (nm) (DMF 1.10×10−3 M): 616(96). UV–Vis: u
(nm) (KBr): 767, 480.
Table 1 shows other analytical and physical data for
all complexes.
10: IR (KBr, cm−1): w(NꢀH) 3105; w(CꢀH)ar 3064;
w(CꢁC), w(CꢁN) 1616, 1575; l(CꢀH)OOP 798, 767;
w(CuꢀN) 439; w(CuꢀO) 278, w(CuꢀN) 248. IR (Nujol,
cm−1): w1+w3(NO3) 1767, 1763, 1750, 1746. UV–Vis:
u(m) (nm) (DMF 1.18×10−3 M): 844(82). UV–Vis: u
(nm) (KBr): 820, 500.
2.4. X-ray crystal structure analysis
Suitable crystals for X-ray diffraction experiments of
compound [Cu(HL0)(NO3)(H2O)2](NO3) (11) were ob-
tained by crystallisation from an acetonitrile solution.
One of them was mounted on an Enraf–Nonius CAD
4
diffractometer. Intensities were collected using the ꢀ–
2q scan mode to a 2qmax=50°. Graphite monochro-
mated Mo Ka radiation was used. The structure was
solved by direct methods (SHELXS-86) [30] and refined
by full-matrix least-squares methods on F2 for all
2.3.4. Complex Cu(HL0)(NO3)2·2H2O (11)
To a Schlenk flask containing deoxygenated warm
ethanol (20 ml) was added, in this order, HL0 (0.45
mmol, 0.10 g) and Cu(NO3)2·3H2O (0.45 mmol, 0.11 g).

2534
J. Pons et al. / Polyhedron 20 (2001) 2531–2536
reflections (SHELXL-97) [31]. The non-coordinated ni-
trate group is disordered. Two oxygen sets have been
included with sof 0.6/0.4. The final R(F) and RW(F2)
values as well as the number of parameters refined and
other details concerning the refinement of the crystal
structure are presented in Table 2. The weight was
w
−1=|2(Fo2)+(0.0561P)2+0.1067P
where
P=
(Fo2+2Fc2)/3.
3. Results and discussion
3.1. Synthesis and spectroscopic properties of the
complexes
Fig. 2. An ORTEP view of the structure of the cation of 11. The
displacement ellipsoids enclose 50% probability.
The complexes Cu(HL)2X2 and Cu(HL)X2 (X=Cl,
Br) were obtained by reacting the appropriate metal
salt with the corresponding pyrazole ligand in a M/L
ratio of 1:2 or 1:1, respectively. Analogously, the com-
plexes Cu(HL)2(NO3)2 and Cu(HL0)(NO3)2 were ob-
tained when the M/L ratio was 1:2 and 1:1
stoichiometry, respectively. We failed to isolate the
complex Cu(HL1)(NO3)2.
The conductivity measurements of the complexes are
shown in Table 1. For nitrate complexes, the electrolyte
nature depends on the solvent. Conductivity in DMF
ranged from 94 to 125 V−1 cm2 mol−1, i.e. between the
values of electrolytes 1:1 and 1:2, whereas conductivity
in DMSO ranged from 57 to 68 V−1 cm2 mol−1, which
is consistent with the value of electrolyte 1:1. For the
complexes of formula Cu(HL)2X2 and Cu(HL)X2, the
conductivity in DMF and DMSO is high enough to
assess the non-coordinated nature of the halide anion.
The IR spectra of the complexes containing the ni-
trate anion, measured in the 1800–1600 cm−1 region,
allowed us to determine the coordination mode of the
NO3− anion. Lever and Montovani [35] studied the IR
absorptions of the NO3− group in this region for
various coordinations. The complexes Cu(HL0)2(NO3)2
(9), Cu(HL1)2(NO3)2·H2O (10) and Cu(HL0)(NO3)2·
2H2O (11) show a complicated spectrum in this region,
which is consistent with the presence of both ionic and
coordinated NO3− groups, confirmed in the case of
complex 11 by X-ray diffraction.
The IR spectra of halide complexes in the region
400–100 cm−1 were also measured. The complexes
Cu(HL)Cl2 and Cu(HL)2Cl2 display two well-defined
w(CuꢀCl) bands at 320–254 and 320–266 cm−1, respec-
tively. The bromide derivatives Cu(HL)Br2 and
Cu(HL)2Br2 show two bands w(CuꢀBr) at 306–266 and
292–266 cm−1, respectively. The w(CuꢀN) absorptions
appear in the range 531–226 cm−1, in agreement with
available data [36–39].
Table 2
Crystal data and structure refinement of 11
Compound
[Cu(HL0)(NO3)(H2O)2](NO3)
C14H15CuN5O8
444.85
293(2)
Empirical formula
Formula weight
Temperature (K)
,
Wavelength (A)
0.71069
triclinic
Crystal system
Space group
(
P1 (no. 2)
Unit cell dimensions
,
a (A)
8.349(3)
10.3623(10)
10.6886(7)
66.516(8)
88.116(14)
88.979(14)
847.7(3)
2
,
b (A)
Electronic spectra for the synthesised complexes were
measured in DMF, and in KBr pellets (diffuse
reflectance).
The spectra of Cu(II) compounds in DMF solution
show one band in the NIR or visible regions, 970–616
nm (m=82–300 mol−1 cm−1 l). Electronic spectra us-
ing diffuse reflectance methods show an additional
band at 550–453 nm. These results did not allow us to
infer the geometry of the metal centre [40–43].
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
Z
Dcalc (Mg m−3
)
1.743
1.347
Absorption coefficient (mm−1
)
Crystal size (mm)
0.50×0.20×0.10
Unique data/restraints/parameters 2974/20/292
R indices [I\2|(I)]
R indices (all data)
Goodness-of-fit on F2
R(F)=0.029, Rw(F2)=0.079
R(F)=0.033, Rw(F2)=0.080
1.077
3.2. Crystal structure of [Cu(HL0)(NO3)(H2O)2](NO3)
Largest difference peak and hole
0.37 and −0.40
The molecular structure of the complex (Fig. 2)
consists of discrete [Cu(HL0)(NO3)(H2O)2]+ cations
−3
,
(e A
)

J. Pons et al. / Polyhedron 20 (2001) 2531–2536
2535
Table 3
Table 4
,
,
Selected bond lengths (A) and bond angles (°) of 11
Hydrogen-bond parameters (A, °) of 11
Bond lengths
DꢀH
A···H
D···A
DꢀH···A
CuꢀO5(H2O)
CuꢀO4(H2O)
CuꢀO1(NO3)
CuꢀN2(pz)
2.1543(19)
1.9772(17)
2.0290(15)
1.9722(18)
2.0191(18)
N3ꢀH3···O1i a
O4ꢀH42···O3ii b
0.86
0.77(2)
2.15
2.959(3)
3.048(3)
2.729(7)
2.827(5)
2.962(8)
156
2.29(2)
1.97(2)
2.05(3)
2.24(3)
168(2)
171(2)
161(3)
150(3)
CuꢀN1(py)
O4ꢀH41···O71iii b 0.77(2)
O5ꢀH52···O81iii b 0.81(3)
O5ꢀH51···O61iv b 0.80(4)
Bond angles
O4ꢀCuꢀO5
O4ꢀCuꢀO1
O5ꢀCuꢀO1
O4ꢀCuꢀN1
O5ꢀCuꢀN1
92.09(8)
88.63(7)
91.88(8)
95.07(8)
105.67(8)
O1ꢀCuꢀN1
O4ꢀCuꢀN2
O5ꢀCuꢀN2
O1ꢀCuꢀN2
N2ꢀCuꢀN1
161.88(7)
167.55(8)
100.29(8)
92.22(7)
80.43(7)
(i) −x, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x, y, z+1;
(iv) −x, −y+1, −z+1.
a NꢀH distances have been fixed.
b The non-coordinated nitrate is disordered. Only the main compo-
nent of disorder is presented here.
a terminal nitrate 33 [47]. The other oxygen of this
NO3−, O2, is close to copper by 2.6121(17) A. If this
,
distance is long enough to be considered a CuꢀO
interaction, the coordination polyhedron around Cu is
a highly distorted octahedral.
The bond distance of CuꢀNpy is clearly longer than
that of CuꢀNpz. Both bond distances are consistent
,
with previously described values (1.996–2.092 A)
,
[24,26,45,46]
respectively.
and
(1.929–2.056
A)
[24,26,46],
The bite angle of N1ꢀCuꢀN2, 80.4(8)°, is similar to
that of tetranuclear copper(II) compounds with the
related ligand HL%: 79.8(2)° [24], 80.3(2)° [26] and to
that of other complexes with the ligands HL0 and HL1:
75.3–80.2° [27–29].
The ligand HL0 is not completely planar. The pyridyl
and phenyl groups are slightly twisted with respect to
the pyrazole. The angles between rings are: pyꢀpz
5.79(7)°, pyꢀph 2.51(6)° and pzꢀph 5.65(9)° in this
complex. These values are lower than the other pub-
lished data [27–29].
Fig. 3. A parallel view of the infinite 2D-lattice parallel to (001) plane
formed by the different units of [Cu(HL0)(NO3)(H2O)2](NO3) bonded
by hydrogen bonds.
Cations are linked by hydrogen bonding, yielding
infinite chains parallel to the crystallographic vector a.
Each cation is bonded to two neighbours, each one
of them is related with it by an inversion centre.
Two N3ꢀH···O1 (coordinated nitrate) hydrogen
bonds are established with one neighbour and two O
(water) O4ꢀH···O3 (coordinated nitrate) hydrogen
bonds are established with the other.
The chains and the non-coordinated nitrate are also
bonded by (water) OꢀH···O (nitrate) hydrogen bonds,
yielding an infinite 2D-lattice parallel to the (001) plane
(Fig. 3, Table 4).
and NO3− anions. The cation complex is mononuclear.
Table 3 lists selected bond distances and angles.
In the cation, the metal atom is coordinated to one
HL0 ligand, via one pyrazole nitrogen and one pyridine
nitrogen, to one NO3− anion and to two H2O
molecules. HL0 behaves as a bidentate ligand and uses
only two of their three donor nitrogen atoms, forming
a five-membered metallocycle.
The coordination around Cu is a distorted square
pyramid. The trigonality index is ~=0.094 [44].
A H2O ligand occupies the apical site [CuꢀO5=
,
2.1543(19) A] whereas the CuꢀO4 distance is 1.9772(17)
,
A (in basal position). These values are similar to those
4. Supplementary material
reported for other examples of CuꢀH2O bond distances
[45,46].
,
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 157492 for compound 11.
The CuꢀO1(NO3) bond distance is 2.0290(15) A,
comparable to the CuꢀO(NO3) distance in other cop-
per(II) complexes in which the metal is coordinated by

2536
J. Pons et al. / Polyhedron 20 (2001) 2531–2536
F.E. Mabbs, E.J.L. McInnes, P.C. Reidi, G.M. Smith, J. Chem.
Soc., Dalton Trans. (1999) 338.
[21] L.S. Harimanow, K.H. Sugiyarto, D.C. Craig, M.L. Scudder,
H.A. Goodwin, Aust. J. Chem. 52 (1999) 109.
[22] J. Casabo´, J. Pons, K. Siddiqi, F. Teixidor, E. Molins, C.
Miravitlles, J. Chem. Soc., Dalton Trans. (1989) 1401.
[23] J. Pons, X. Lo´pez, E. Benet, J. Casabo´, F. Teixidor, F.J.
Sa´nchez, Polyhedron 9 (1990) 2839.
Copies of this information can be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
[24] J. Pons, X. Lo´pez, J. Casabo´, F. Teixidor, A. Caubet, J. Rius, C.
Miravitlles, Inorg. Chim. Acta 195 (1992) 61.
Acknowledgements
[25] J. Pons, F.J. Sa´nchez, A. Labarta, J. Casabo´, F. Teixidor, A.
Caubet, Inorg. Chim. Acta 208 (1993) 167.
[26] M. Munakata, L.P. Wu, M. Yamamoto, T. Kurodasowa, M.
Maekawa, S. Kawata, S. Kitagawa, J. Chem. Soc., Dalton
Trans. (1995) 4099.
We thank CICYT (MAT91-0952) and DGICYT
(PB96-1146) for financial support. A.C. is grateful for a
grant from Ministerio de Asuntos Exteriores: Agencia
Espan˜ola de Cooperacio´n Internacional (Instituto de
cooperacio´n con el mundo a´rabe).
[27] A. Chadghan, J. Pons, A. Caubet, J. Casabo´, J. Ros, A. Alvarez-
Larena, J.F. Piniella, Polyhedron 19 (2000) 855.
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Piniella, X. Solans, M. Font-Bardia, J. Ros, Polyhedron 20
(2001) 1029.
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