3
1
0 mmol) and an aqueous solution (50 cm ) of hydroxylamine
hydrochloride (1.04 g, 15 mmol) were mixed and together
3
with an aqueous solution (10 cm ) of NaOH (0.60 g, 15 mmol)
were refluxed for 5 hours and then evaporated to dryness. The
residue was stirred with an aqueous NaHCO solution (5%,
3
3
1
00 cm ), and the aqueous extract separated from any insoluble
material was neutralized with dilute hydrochloric acid to give a
colorless precipitate. This was filtered off, thoroughly washed
with water and dried in vacuo. The yield was 1.31 g (72%). Anal.
Found: C, 52.15; H, 3.96; N, 7.67. Calcd for C H NO : C, 53.04;
8
7
4
Ϫ1
H, 3.90; N, 7.73%. IR [ν/cm ] as KBr disk: 3217, 1660, 1611,
450, 1317, 1249, 1228, 1189, 957, 761, 681.
1
[
Cu (HL) ]ؒ0.5H O (1). A solution of H L (18 mg, 0.1 mmol)
2 2 2 3
3
in dimethylformamide (DMF) (3 cm ) was layered with a solu-
tion of copper() perchlorate hexahydrate (37 mg, 0.1 mmol)
3
in water (2 cm ) and allowed to stand at ambient temperature.
After several days the resulting green microcrystals were separ-
ated, washed with diethyl ether and dried in vacuo. The yield
was 21 mg (85%). Anal. Found: C, 38.69; H, 2.20; N, 5.82; Cu,
2
5.46. Calcd for C Cu H N O : C, 38.87; H, 2.24; N, 5.67;
16 2 11 2 8.5
Ϫ1
Cu, 25.71%. IR [ν/cm ] as KBr disk: 3367, 1600, 1573, 1432,
Ϫ1
1
360, 1267, 1230, 981, 883, 766, 696, 626. UV-vis [λ/nm (ε/M
Ϫ1
cm )]: 657 [powder]; 628 (315) [in 0.1 M NaOH solution].
Fig. 1 An ORTEP view of Na[Cu (HL)(L)(H O)] (2Ј) with the atom
2
2
numbering scheme.
Na[Cu (HL)(L)]ؒ3H O (2). H L (181 mg, 1.0 mmol) was dis-
solved in an aqueous solution (100 cm ) of NaOH (120 mg,
.0 mmol). To this was added an aqueous solution of copper()
acetate monohydrate (200 mg, 1 mmol), and the mixture was
heated at reflux for one hour. The resulting green crystals were
2
2
3
3
glass fiber and a single crystal of [Ni (HL) (H O) ]ؒ8H O (3Ј)
2
2
2
4
2
3
sealed in a glass tube were used for X-ray crystallographic
measurements using a Rigaku AFC7R diffractometer with
graphite monochromated Mo-Kα radiation (λ = 0.71069 Å)
and a 12 kW rotating anode generator. Cell constants and the
orientation matrix for the data collection were obtained from
separated and recrystallized from an aqueous NaOH solution
3
(
3
0.4%, 100 cm ). The yield was 160 mg (57%). Anal. Found: C,
4.11; H, 2.62; N, 4.97; Cu, 22.62. Calcd for C Cu H N -
16
2
15
2
Ϫ1
2
5 reflections and the ω–2θ scan mode was used for the inten-
NaO : C, 34.23; H, 2.69; H, 4.99; Cu, 22.64%. IR [ν/cm ]
11
sity collections at 23 ± 1 ЊC. A single crystal of [Mn{Cu (HL)-
2
as KBr disk: 3488, 3076, 2998, 2923, 2853, 1607, 1586, 1430,
(
L)} (H O) ]ؒ4H Oؒ2DMF (4Ј) was mounted on a glass fiber
2 2 4 2
Ϫ1
Ϫ1
1
[
348, 1269, 992, 754. UV-vis [λ/nm (ε/M cm )]: 566 and 664
and used for crystallographic measurements using a Rigaku
RAXIS-RAPID imaging plate area detector. Intensity data
were collected by taking oscillation photographs. Pertinent
crystallographic parameters for 2Ј, 3Ј and 4Ј are summarized in
Table 1)
The structures were solved by direct methods and expanded
using Fourier techniques. The non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were included in the structure
analysis but not refined. Computations were carried out on
an IRIS O2 computer using the TEXSAN crystallographic
powder]; 627 (320) [in 0.1 M NaOH solution].
[
Ni (HL) ]ؒ2.5H O (3). H L (181 mg, 1.0 mmol) was dis-
2 2 2 3
3
solved in an aqueous solution (100 cm ) of NaOH (80 mg,
.0 mmol). To this was added an aqueous solution (50 cm )
3
2
of nickel() acetate tetrahydrate (248 mg, 1.0 mmol), and the
mixture was allowed to stand for several days to afford
[
Ni (HL) (H O) ]ؒ8H O (3Ј) as green crystals. Because they
2 2 2 4 2
were highly efflorescent, elemental analyses were performed on
the sample dried in air (3). The yield was 217 mg (83%). Anal.
Found: C, 37.16; H, 2.78; N, 5.38; Ni, 22.14. Calcd for
C H N Ni O10.5: C, 36.91; H, 2.90; N, 5.38; Ni, 22.55%. IR
14
software package.
CCDC reference numbers 162982–162984.
See http://www.rsc.org/suppdata/dt/b1/b103384k/ for crystal-
lographic data in CIF or other electronic format.
16
15
Ϫ1
2
2
[
1
ν/cm ] as KBr disk: 3447, 3369, 1595, 1568, 1449, 1341, 1267,
Ϫ1
Ϫ1
228, 968, 882, 762, 679, 621. UV-vis [λ/nm (ε/M cm )]: 617
and 1120 [powder]; 620 (43) and 1137 (10) [in 0.1 M NaOH aq.
solution].
Results and discussion
[
Mn{Cu (HL)(L)} (H O) ]ؒH Oؒ2DMF (4). To a solution of
Crystal structures
2
2
2
4
2
2
6
(52 mg, 0.1 mmol) in a DMF–H O mixture (1 : 1 in volume,
15
2
Na[Cu (HL)(L)(H O)] (2Ј). An ORTEP view of 2Ј is shown
3
2
2
0 cm ) was added a solution of manganese() perchlorate
in Fig. 1 together with the atom numbering scheme. Relevant
bond distances and angles are given in Table 2.
The results clearly demonstrate the cis arrangement of the
two ligands (HL and L ) providing nonequivalent {CuN O }
and {CuO } chromophores, sharing the two phenolic oxygen
atoms. The Cu2 ؒ ؒ ؒ Cu1 interatomic separation is 2.961(1)
Å. The N O2 cavity has a hydrogen-bonded N1–O1 ؒ ؒ ؒ
H ؒ ؒ ؒ O5–N2 linkage formed by the dioximate group. The Cu1
in the N O site has a square-pyramidal geometry with a water
molecule at the apical site. The basal Cu-to-donor bond dis-
tances range from 1.943(3) to 1.958(2) Å. The axial Cu–O9
bond distance (2.378(2) Å) is elongated due to the Jahn–Teller
effect of a d electronic configuration. The O1 ؒ ؒ ؒ O5 separation
2.444(3) Å) is very short relative to the O ؒ ؒ ؒ O sep-
3
hexahydrate (18 mg, 0.05 mmol) in DMF (10 cm ), and the
mixture was allowed to stand at ambient temperature forming
green needles after a few days. The crystals were obtained as
2Ϫ
3Ϫ
2
2
[Mn{Cu (HL)(L)} (H O) ]ؒ4H Oؒ2DMF (4Ј) based on X-ray
2 2 2 4 2
4
crystallography as discussed later. In open air the compound
loses three molecules of water to give [Mn{Cu (HL)(L)} -
2
2
2
(
H O) ]ؒH Oؒ2DMF (4). The yield was 12 mg (19%). Anal.
2 4 2
Found: C, 36.35; H, 3.35; N, 6.73; Cu, 19.96; Mn, 4.42. Calcd
for C Cu H MnN O : C, 36.23; H, 3.36; N, 6.67; Cu, 20.17;
Mn, 4.36%. IR [ν/cm ] as KBr disk: 3369, 1655, 1603, 1548,
2
2
38
4
42
6
23
Ϫ1
1
433, 1234, 994, 765. UV-vis [λ/nm]: 650 [powder].
9
X-Ray crystallography
(
A single crystal of Na[Cu (HL)(L)(H O)] (2Ј) mounted on a
aration (2.53–2.70 Å) of bis(dimethylglyoximato)copper()
2
2
3
120
J. Chem. Soc., Dalton Trans., 2001, 3119–3124