Table 1 Crystal data and structure refinement details for 3 and 4
(Ar–NO2), 129.66 (Ar–NO2), 146.06 (Ar–ONa), 149.03 (C–ONa),
164.90 (C=O) ppm.
3
4
Synthesis of 4. Method 1. To 26.5 mg (0.1 mmol) of 1 in
methanol (50 mL) were added 6.9 mg (0.1 mmol) NaNO2 and
11.2 mg (0.2 mmol) KOH, and the resulting mixture was stirred
for 10 min at r.t. Then 23.8 mg (0.1 mmol) NiCl2·6H2O was added,
the mixture was stirred for 10 min and left for slow evaporation in
air at r.t. Green X-ray quality crystals of 4 started to form in 3 d.
Method 2. To 31.0 mg (0.1 mmol) of 2 in methanol (50 mL)
were added 11.2 mg (0.2 mmol) KOH, and the resulting mixture
was stirred for 10 min at r.t. Then 23.8 mg (0.1 mmol) NiCl2·6H2O
was added, the mixture was stirred for 10 min and left for slow
evaporation in air at r.t. The product started to form in 3 d, it was
then filtered off and dried in air to give 4.
Formula unit
Formula weight
T/K
C11H8KN4O7
348.32
150(2)
Monoclinic
P21/c
5.6530(16)
13.404(4)
19.2441(18)
90
102.459(5)
90
C11H16N4NiO11
438.99
150(2)
Crystal system
Triclinic
¯
Space group
P1
˚
a/A
8.2053(2)
10.2393(3)
10.9106(2)
67.0990(10)
73.6950(10)
85.8660(10)
2
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
Z
Volume/A
Dc/g cm-3
m/mm-1
4
3
˚
1423.8(6)
1.625
0.418
8721
2598
0.1620
0.0889, 0.2053
0.963
809.74(4)
1.800
1.270
9045
2777
0.0181
0.0495, 0.1283
1.082
ꢀ
Independent reflections
Observed reflections
Rint
Compound 4. Yield: 53% (based on 1), green crystals, soluble
in ethanol, acetone, methanol and water, insoluble in chloroform.
Calcd for C11H16NiN4O11 (M = 439.0): C 30.10, H 3.67, N 13.37%;
found C 29.99, H 3.28, N 12.98%. MS (ESI): m/z: 366 [4-4H2O].
IR (KBr): 3449 (s, br) n(OH), 1629 (s) n(C=O), 1594 (s) n(C=N)
cm-1.
Final R1a, wR2b (I ≥ 2s)
GOF
ꢀ
ꢀ
ꢀ
a R1 = ||Fo| - |Fc||/ |Fo|. b wR2 = [ [w(Fo - Fc2)2]/ [w(Fo2)2]]1/2
2
Synthesis of 6. To 26.5 mg (0.1 mmol) of 1 in methanol
(50 mL) were added 11.2 mg (0.2 mmol) KOH. The resulting
mixture was stirred for 10 min and left for slow evaporation in air
at r.t. A dark red powder started to precipitate in 2 d, which was
filtered off after 7 d and dried in air to give 6.
Acknowledgements
This work has been partially supported by the Foundation for
Science and Technology (FCT), Portugal, its PPCDT (FEDER
funded) and “Science 2007” programmes. K. T. M. expresses
gratitude to the FCT for his post-doc fellowship. The authors
thank the Portuguese NMR Network (IST-UTL Centre) for
providing access to the NMR facility.
Compound 6. Yield: 61% (based on 1), dark red crystals,
soluble in ethanol, acetone, methanol and water, insoluble in
chloroform. Calcd for C11H15K2N3O8 (M = 395.0): C 33.41, H
3.82, N 10.63%; found C 33.75, H 3.53, N 9.97%. MS (ESI): m/z:
341 [6-3H2O]. IR (KBr): 3411 (s, br) n(OH), 1678 (s) n(C=O), 1650
(s) n(C–O), 1614 (s) n(C=N) cm-1. 1H NMR (300 MHz, DMSO-
d6): d = 2.41 (s, 3H, CH3) overlapped by DMSO-d6 (s, 3H, CH3),
References
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The X-ray quality single crystals of compounds 3 and 4 were
grown by slow evaporation in air at r.t. of their methanol solutions.
They were immersed in a cryo-oil, mounted in a Nylon loop
and measured at 150 K. Intensity data were collected using
a Bruker AXS-KAPPA APEX II diffractometer with graphite
monochromated Mo-Ka (l = 0.71073) radiation. Data were
collected using omega scans of 0.5◦ per frame and full sphere
of data was obtained. Cell parameters were retrieved using Bruker
SMART software and refined using Bruker SAINT13a on all the
observed reflections. Absorption corrections were applied using
SADABS.13a Structures were solved by direct methods by using
the SIR-9713b (3) or SHELXS-9713c (4) packages and refined with
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System-Version 1.80.03.13d All hydrogen atoms were inserted in
calculated positions. In 4, the O61 and O62 atoms of the nitro
group are disordered over two sites with occupancies 0.53 and
0.47. Crystal data and details of data collection for 3 and 4 are
reported in Table 1.
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This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 12472–12478 | 12477
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