1,3,5-Triazapentadiene Nickel(II) Complexes
by using Ni(MeCO2)2·4H2O (249 mg, 1.00 mmol) and acetonitrile
(10 mL) as both solvent and reagent instead of NiCl2·2H2O and
acetone and 4-chlorobenzonitrile, respectively. Recrystallization of
the product from hot water gave pale-yellow crystals (of X-ray
quality) of 7. Yield: 81% (333 mg), on the basis of nickel acetate.
The compound does not have a characteristic melting point and
decomposes upon heating above 300 °C. C12H28N6NiO6 (411.1):
calcd. C 35.06, H 6.87, N 20.44; found C 34.79, H 6.88, N 20.39.
FAB-MS(+) (m-NBA): m/z = 256 [M – 2MeCOO – H]+. IR (KBr):
[1]
For recent examples, see: a) J. P. Wikstrom, A. S. Filatov, E. V.
Rybak-Akimova, Chem. Commun. 2010, 46, 424; b) J. A. Flo-
res, V. Badarinarayana, S. Singh, C. J. Lovely, H. V. R. Dias,
Dalton Trans. 2009, 7648; c) I. Hager, R. Frohlich, E. U.
Wurthwein, Eur. J. Inorg. Chem. 2009, 2415; d) A. G. Tskhovre-
bov, N. A. Bokach, M. Haukka, V. Y. Kukushkin, Inorg. Chem.
2009, 48, 8678; e) H. V. R. Dias, J. A. Flores, J. Wu, P. Kroll,
J. Am. Chem. Soc. 2009, 131, 11249; f) P. V. Gushchin, M. L.
Kuznetsov, M. Haukka, M. J. Wang, A. V. Gribanov, V. Y. Ku-
kushkin, Inorg. Chem. 2009, 48, 2583; g) C. Valdebenito, M. T.
Garland, R. Quijada, R. Rojas, J. Organomet. Chem. 2009, 694,
717; h) M. S. Zhou, Y. P. Song, T. Gong, H. B. Tong, J. P. Guo,
L. H. Weng, D. S. Liu, Inorg. Chem. 2008, 47, 6692; i) J. A.
Flores, H. V. R. Dias, Inorg. Chem. 2008, 47, 4448; j) M. S.
Zhou, P. Li, H. B. Tong, Y. P. Song, T. Gong, J. P. Guo, L. H.
Weng, D. S. Liu, Inorg. Chem. 2008, 47, 1886.
ν = 3477 [s br., ν(OH)], 3165 [s br., ν(NH)], 1666 [s, ν(C=N)], 1556
˜
[s, δ(NH)] cm–1. 1H NMR (300 MHz, D2O, Me4Si): δ = 2.06 (br. s,
CH3+CH3COO) ppm, NH protons were not observed. 13C{1H}
NMR (75.4 MHz, D2O, Me4Si): δ = 20.0 (CH3), 21.5 (CH3COO),
163.2 [C=N(–N)], 178.0 [C=O(–O)] ppm.
X-ray Crystal Structure Determination: The X-ray quality single
crystals of 1a·(Me2CO)0.33·(MeOH)0.67, 2b·2Me2CO, 4b·CHCl3,
5b·Me2CO, 6b·MeOH and 7 were mounted in inert oil within the
cold gas stream of the diffractometer. The X-ray diffraction data
were collected with a Nonius Kappa CCD diffractometer at 120
(2b, 5b, 6b, 7) or 110 K (1a, 4b). The Denzo–Scalepack[14] program
package was used for cell refinements and data reduction. Struc-
tures were solved by direct methods by using the SIR-97 (2b, 6b),
SIR-2002 (1a, 4b), SIR-2004 (7) or SHELXS-97 (5b) programs.[15]
A multiscan absorption correction based on equivalent reflections
(XPREP in SHELXTL or SADABS)[16] was applied to all data.
The structures were refined with SHELXL-97[17a] and the WinGX
graphical user interface.[17b] In 1a, the acetone and methanol sol-
vent molecules were disordered and mixed with each other. The
disordered acetone and methanol molecules were refined with oc-
cupancies of 0.33 and 0.66, respectively. Furthermore, the C–O dis-
tance in the MeOH molecule was constrained. In addition, the car-
bon atom (C98) was restrained so that its Uij components approxi-
mate isotropic behaviour. In 4b, the chloroform of crystallization
was partially lost and was refined with an occupancy of 0.5. In
addition, all the C–Cl and Cl···Cl distances were set to be similar.
Because of partial solvent loss, the crystal of 4b was only weakly
diffracting. In 1a, 4b, 5b, 6b and 7, the NH and OH hydrogen atoms
were located from the difference Fourier map but were constrained
to ride on their parent atom, with Uiso = 1.5 or 0.25. In 2b, the
NH hydrogen atoms were located from the difference Fourier map
and refined isotropically. The main crystallographic data for all
measured structures are summarized in Table 2. A search in the
Cambridge Structural Database (CSD)[2] revealed that structures
similar to those of 4b[4a] and 6b[4c] were reported by others, albeit
as an unknown solvate and measured at 298 K, respectively. Hence,
our structures 4b (with solvated chloroform molecule) and 6b (de-
termined at 120 K) are not discussed in the present work. CCDC-
757194, -757195, -757196, -757197, -757198, -757199 contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[2]
[3]
See the Cambridge Structural Database (CSD, version 5.30,
Sep 2009): F. H. Allen, Acta Crystallogr., Sect. B 2002, 58, 380.
a) M. N. Kopylovich, K. V. Luzyanin, M. Haukka, A. J. L.
Pombeiro, V. Y. Kukushkin, Dalton Trans. 2008, 5220; b) P. V.
Gushchin, K. V. Luzyanin, M. N. Kopylovich, M. Haukka,
A. J. L. Pombeiro, V. Y. Kukushkin, Inorg. Chem. 2008, 47,
3088; c) P. V. Gushchin, M. Haukka, N. A. Bokach, V. Y. Ku-
kushkin, Russ. Chem. Bull. 2008, 57, 2125; d) N. A. Bokach,
T. V. Kuznetsova, S. A. Simanova, M. Haukka, A. J. L. Pom-
beiro, V. Y. Kukushkin, Inorg. Chem. 2005, 44, 5152; e) T. Kaji-
wara, T. Ito, Eur. J. Inorg. Chem. 2004, 3084; f) A. R. Siedle,
R. J. Webb, F. E. Behr, R. A. Newmark, D. A. Weil, K. Erik-
son, R. Naujok, M. Brostrom, M. Mueller, S.-H. Chou, V. G.
Young Jr., Inorg. Chem. 2003, 42, 932.
a) I. A. Guzei, K. R. Crozier, K. J. Nelson, J. C. Pinkert, N. J.
Schoenfeldt, K. E. Shepardson, R. W. McGaff, Inorg. Chim.
Acta 2006, 359, 1169; b) S. V. Kryatov, A. Y. Nazarenko, M. B.
Smith, E. V. Rybak-Akimova, Chem. Commun. 2001, 1174; c)
J. Guo, W.-K. Wong, W.-Y. Wong, Eur. J. Inorg. Chem. 2004,
267; d) R. Norrestam, Acta Crystallogr., Sect. C 1984, 40, 955.
a) M. N. Kopylovich, J. Lasri, M. F. C. G. da Silva, A. J. L.
Pombeiro, Dalton Trans. 2009, 3074; b) P. V. Gushchin, M. R.
Tyan, N. A. Bokach, M. D. Revenco, M. Haukka, M. J. Wang,
C. H. Lai, P. T. Chou, V. Y. Kukushkin, Inorg. Chem. 2008, 47,
11487; c) G. H. Sarova, N. A. Bokach, A. A. Fedorov, M. N.
Berberan-Santos, V. Y. Kukushkin, M. Haukka, J. J. R. Fraú-
sto da Silva, A. J. L. Pombeiro, Dalton Trans. 2006, 3798; d) J.-
P. Zhang, Y.-Y. Lin, X.-C. Huang, X.-M. Chen, J. Am. Chem.
Soc. 2005, 127, 5495; e) T. Kajiwara, A. Kamiyama, T. Ito,
Chem. Commun. 2002, 1256.
a) M. N. Kopylovich, M. Haukka, A. M. Kirillov, V. Y. Ku-
kushkin, A. J. L. Pombeiro, Chem. Eur. J. 2007, 13, 786; b)
A. J. L. Pombeiro, M. N. Kopylovich, A. M. Kirillov, V. Y. Ku-
kushkin, M. Haukka. Patent PT103522, 2007.
a) N. B. McKeown, Phthalocyanine Materials: Structure, Syn-
thesis and Function, Cambridge University Press, Cambridge,
1998; b) C. C. Leznoff, A. B. P. Lever, Phthalocyanines: Proper-
ties and Applications, VCH, Weinheim, 1989 (Vol. 1), 1993 (Vol.
2), 1993 (Vol. 3), 1996 (Vol. 4); c) G. de la Torre, C. G. Claes-
sens, T. Torres, Eur. J. Org. Chem. 2000, 2821.
a) V. Y. Kukushkin, A. J. L. Pombeiro, Inorg. Chim. Acta 2005,
358,35 1; b) V. Y. Kukushkin, A. J. L. Pombeiro, Chem. Rev.
2002, 102, 1771; c) A. J. L. Pombeiro, New J. Chem. 1994, 18,
163.
a) M. N. Kopylovich, V. Y. Kukushkin, M. Haukka, K. V. Luz-
yanin, A. J. L. Pombeiro, J. Am. Chem. Soc. 2004, 126, 15040;
b) M. N. Kopylovich, V. Y. Kukushkin, M. F. C. G. da Silva,
M. Haukka, J. J. R. F. da Silva, A. J. L. Pombeiro, J. Chem.
Soc. Perkin Trans. 1 2001, 1569; c) M. N. Kopylovich, V. Y.
Kukushkin, M. Haukka, J. J. R. F. da Silva, A. J. L. Pombeiro,
Inorg. Chem. 2002, 41, 4798; d) M. N. Kopylovich, M. Haukka,
A. M. Kirillov, V. Y. Kukushkin, A. J. L. Pombeiro, Inorg.
Chem. Commun. 2008, 11, 117; e) S. Mukhopadhyay, B. G. Mu-
[4]
[5]
[6]
[7]
[8]
[9]
Acknowledgments
This work was supported by the Foundation for Science and Tech-
nology (FCT), Portugal, and its PPCDT (FEDER funded) and
“Science 2007” programs. The authors would like to thank Dr. M.
Cândida Vaz and Dr. M. Conceição Oliveira for the elemental
analyses and the ESI-MS spectra (IST-node of the RNEM/FCT),
respectively. E. A. T. and V. Y. K. are very grateful to the Russian
Fund for Basic Research for grant 09-03-12173-ofi_m.
Eur. J. Inorg. Chem. 2010, 2425–2432
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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