bulk of the ethoxy group. We are unsure of the reason 1 and 2
adopt this structure instead of other possibilities that would also
serve to accommodate the two alkoxy groups and sp3-
hybridized carbon atoms of the macrocycle. Syntheses of a
series of similar compounds and determination of their
structures will likely help to answer this question. It is
conceivable that other structural motifs may be seen in
analogues of 1 and 2.
The outer rings of the ligands in 1 and 2 show no remarkable
features other than the aforementioned overall deviation of the
entire ligand from planarity. The bond lengths and angles
around the alkoxy-substituted carbon atoms in 1 and 2 are as
would be expected for single bonds and sp3 hybridization of
these atoms. All other carbon and nitrogen atoms in 1 and 2,
excepting those in the alkoxy groups, exhibit bond lengths and
angles indicative of conjugated double bonds and sp2 hybrid-
ization. The nickel atoms in both 1 and 2 are coordinated in a
nearly square planar fashion by four nitrogen atoms. In both
cases, two of the Ni–N bonds, on opposite sides of the Ni atom,
are longer than the other two Ni–N bonds. In the crystal
structure of 1, one methanol solvate donates a hydrogen bond to
a peripheral nitrogen atom in each molecule of the complex,
while 2 is free of solvation.
It appears that the reaction conditions employed in the
synthesis of 1 and 2 are general for primary alcohols, and they
lead to the formation of large single crystals that will be
amenable to conductivity and optical studies. We believe that
this method of synthesis will lead to the discovery of several
new phthalocyanine compounds, containing different metals
and bearing different alkoxy groups on their ligands.
Acknowledgement is made to the donors of The Petroleum
Research Fund, administered by the ACS, for partial support of
this research. We further acknowledge the Faculty Research
Committee and the College of Science and Allied Health at the
University of Wisconsin-La Crosse for additional support.
Notes and references
‡ Crystal data: for 1: M = 665.35, triclinic, space group P1, a = 7.160(2),
¯
b = 12.853(3), c = 16.936(3) Å, a = 93.33(2), b = 99.98(2), g =
105.28(4)°, V = 1471.9(6) Å3, Z = 2, m(Mo-Ka) = 0.712 mm21, T =
293(2) K. The structure, refined on F2, converged for 5620 reflections (5170
unique, Rint = 0.0892) to give R1 = 0.0558 and wR2 = 0.1295 for all
reflections for which I > 2s(I) and goodness-of-fit = 1.000.
¯
For 2: M = 661.36, triclinic, space group = P1, a = 7.950(2), b =
13.080(4), c = 15.395(5) Å, a = 109.12(3), b = 97.99(3), g = 94.14(3)°,
V = 1486.0(8) Å3, Z = 2, m(Mo-Ka) = 0.703 mm21, T = 293(2) K. The
structure, refined on F2, converged for 5587 reflections (5199 unique, Rint
= 0.1106) to give R1 = 0.0509 and wR2 = 0.1285 for all reflections for
which I > 2s(I) and goodness-of-fit = 1.018.
CCDC reference numbers 174008 and 174009.
data in CIF or other electronic format.
Fig. 2 The crystallographically determined structure, excluding hydrogen
atoms and solvated methanol, for 1. Ellipsoids are drawn at the 50%
probability level. Selected bond lengths (Å) and angles (°): Ni(1)–N(1)
1.845(4), Ni(1)–N(2) 1.867(4), Ni(1)–N(3) 1.836(4), Ni(1)–N(4) 1.862(4),
C(1)–O(2) 1.418(7), C(1)–C(2) 1.518(8), C(1)–N(8) 1.466(7), C(1)–N(1)
1.472(7), C(17)–O(1) 1.426(7), C(17)–C(18) 1.507(8), C(17)–N(3)
1.479(7), C(17)–N(6) 1.444(7), N(1)–C(8) 1.307(7), N(3)–C(24) 1.309(6);
N(1)–Ni(1)–N(2) 89.9(2), N(2)–Ni(1)–N(3) 90.8(2), N(3)–Ni(1)–N(4)
90.5(2), N(4)–Ni(1)–N(1) 90.4(2), C(2)–C(1)–N(8) 112.1(5), C(2)–C(1)–
N(1) 103.2(5), N(1)–C(1)–N(8) 112.6(5), N(1)–C(1)–O(2) 111.1(5), C(2)–
C(1)–O(2) 114.3(5), N(8)–C(1)–O(2) 103.8(4), N(3)–C(17)–C(18)
103.2(4), N(6)–C(17)–C(18) 112.9(4), N(6)–C(17)–N(3) 114.5(4), O(1)–
C(17)–C(18) 114.2(4), O(1)–C(17)–N(3) 102.6(4), O(1)–C(17)–N(6)
109.1(4).
1 (a) N. B. McKeown, Phthalocyanine Materials: Synthesis, Structure
and Function, Cambridge University Press, Cambridge, 1998 and
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B. P. Lever, VCH, Cambridge, 1989 and references therein; (d)
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(e) Phthalocyanines Properties and Applications, ed. C. C. Leznoff and
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Phthalocyanines Properties and Applications, ed. C. C. Leznoff and
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2 K. Yase, N. Yasuoka, T. Kobayashi and N. Uyeda, Acta Crystallogr.,
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Fig. 3 The crystallographically determined structure, excluding hydrogen
atoms, for 2. Ellipsoids are drawn at the 35% probability level. Selected
bond lengths (Å) and angles (°): Ni(1)–N(1) 1.831(4), Ni(1)–N(2) 1.854(4),
Ni(1)–N(3) 1.838(4), Ni(1)–N(4) 1.862(4), C(1)–O(1) 1.425(5), C(1)–C(2)
1.517(6), C(1)–N(8) 1.449(6), C(1)–N(1) 1.469(6), C(17)–O(2) 1.414(6),
C(17)–C(18) 1.519(6), C(17)–N(3) 1.478(6), C(17)–N(6) 1.452(6), N(1)–
C(8) 1.323(6), N(3)–C(24) 1.306(6), N(1)–Ni(1)–N(2) 90.5(2), N(2)–
Ni(1)–N(3) 90.8(2), N(3)–Ni(1)–N(4) 90.2(2), N(4)–Ni(1)–N(1) 90.3(2),
C(2)–C(1)–N(8) 112.3(4), C(2)–C(1)–N(1) 103.2(4), N(1)–C(1)–N(8)
113.5(4), N(1)–C(1)–O(1) 110.7(4), C(2)–C(1)–O(1) 113.7(4), N(8)–C(1)
–O(1) 103.8(3), N(3)–C(17)–C(18) 103.0(4), N(6)–C(17)–C(18) 111.8(4),
N(6)–C(17)–N(3) 113.1(4), O(2)–C(17)–C(18) 113.6(4), O(2)–C(17)–N(3)
111.8(4), O(2)–C(17)–N(6) 103.8(4).
10 K. Kasuga, M. Kawashima, K. Asano, T. Sugimori, K. Abe, T. Kikkawa
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Chem. Commun., 2001, 2644–2645
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