X-ray Structure Analysis Online 2011, VOL. 27
2011 © The Japan Society for Analytical Chemistry
51
X-ray Structure Analysis Online
Crystal Structure of Isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridine-2ylmethyl)propane-1,3-diaminecopper(II) Perchlorate
Takashi YOKOYAMA,*† Masakazu YOSHISE,* Shintaroh HASE,* Ayumi KAWATE,* Haruo AKASHI,**
and Michio ZENKI*
*Department of Chemistry, Faculty of Science, Okayama University of Science,
1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan
**Research Institute of Natural Sciences, Okayama University of Science,
1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan
The complex of an isothiocyanato-N,N¢-dimethyl-N,N¢-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II) perchlorate
([Cu(NCS)(LMe2)]ClO4) was prepared.
Its crystal structure was determined by X-ray diffractometry.
[Cu(NCS)(LMe2)]ClO4 crystallized in a triclinic system, and was characterized thus: P1, a = 9.257(3), b = 9.883(4), c =
11.806(5)Å, a = 89.638(12), b = 81.053(10), g = 88.841(12)˚, Z = 2, V = 1066.7(7)Å3. The crystal structure was solved
by direct methods and refined by full-matrix least squares on F2 to final values of R1 = 0.058.
(Received May 26, 2011; Accepted August 8, 2011; Published on web September 13, 2011)
The synthesis, electrochemistry, and reactivities of a complex
cation,
trans-dioxo-N,N¢-dimethyl-N,N¢-bis(pyridine-2ylmethyl)propane-1,3-diamineruthenium(VI)
(trans[Ru(LMe2)O2]2+), have been reported.1
It can oxidize
tetrahydrofuran and aromatic hydrocarbons under mild
conditions. Its pyridine functional group increases both the
redox potential and the reactivity of the ruthenium oxo oxidant.
It is considered that its reactivity would also depend on the
geometry of the pyridine functional group on the structure of the
complex cation. The redox behaviors of [Cu(LMe2)]2+ have also
been reported.2,3 The crystal structures of chromium(III)4 and
manganese(II)5 with LMe2 and [Cu(ClO4)2(LMe2)]6 have been
reported. A couple of perchlorate ions in the [Cu(ClO4)2(LMe2)]
coordinate to the [Cu(LMe2)]2+. Each N-methyl group of
[Cu(ClO4)2(LMe2)] is placed at a trans configuration. The
crystal structure of copper(II) with its analogous N,N¢-dimethylN,N¢-bis(pyridine-2-ylmethyl)ethane-1,2-diamine (L¢Me2) and
perchlorate ions has been also reported.6 Only one perchlorate
ion in [Cu(ClO4)(L¢Me2)]ClO4 coordinates to the Cu2+ ion. Each
N-methyl group of the [Cu(ClO4)(L¢Me2)]ClO4 is placed at a cis
Fig. 1
Chemical diagram of the title compound.
† To whom correspondence should be addressed.
E-mail: [email protected]
configuration. The crystal structures of manganese(II) and
copper(II) with its L¢Me2 included in these binuclear complexes
have been reported.5,7 The pyridine functional group on the
complex cation with an ethylene group between two N-pyridine2-ylmethylamines would have a more rigid geometry than that
with the propylene group.8 The Cu–N4 square-planar geometry
of [Cu(ClO4)2(LMe2)] is distorted more than that of N,
N¢-bis(pyridine-2-ylmethyl)propane-1,3-diaminecopper(II)
Table 1
Crystal and experimental data
Chemical formula: C18H24N5CuClO4S
Formula weight = 505.48
T = 93 K
Crystal system: triclinic
Space group: P1
a = 9.257(3)Å
a = 89.638(12)˚
b = 9.883(4)Å
b = 81.053(10)˚
c = 11.806(5)Å
g = 88.841(12)˚
V = 1066.7(7)Å3
Z=2
Dx = 1.574 g/cm3
Radiation: Mo Ka (l = 0.71070 Å)
m(Mo Ka) = 1.2823 mm–1
F(0 0 0) = 522
Crystal size = 0.20 ¥ 0.20 ¥ 0.20 mm3
No. of relections collected = 7095
No. of independent relections = 3736
q range for data collections = 3.0 to 25.7˚
Data/Restraints/Parameters = 3736/0/272
Goodness-of-fit on F2 = 1.132
R indeces [I > (2s(I)]: R1 = 0.0576
R indeces (all data): R1 = 0.058, wR2 = 0.1788
(D/s)max = 0.000
(Dr)min = –0.96 eÅ3
(Dr)max = 1.25 eÅ3
Measurement: Rigaku RAXIS IV
Program systems: CrystalStructure3.8, SHELXL97
Structure determination: SIR92
CCDC deposition number: 818658
52
X-ray Structure Analysis Online 2011, VOL. 27
Table 2
Fig. 2 ORTEP structure of [Cu(NCS)(LMe2)]ClO4, showing 50%
probability ellipsoids. Hydrogen atoms are omitted for clarity.
perchlorate [Cu(LH2)](ClO4)2 with two NH protons in place of
two N-methyl groups. Since the coordination of the perchlorate
ion to copper(II) is generally weak, it is considered that its
distortion would be small, compared to that of [Cu(LMe2)]2+
coordinated a relatively strong coordinating ion, such as
isothiocyanate ion.
Furthermore, the isothiocyanate ion
coordinates to [Co(LH2)]3+ 9 and [Zn(LH2)]2+ 9 as a cis-sixcoordinated species. On the other hand, it coordinates to
[Cu(LH2)]2+ 10 as a five-coordinated species. It is, therefore,
interesting to investigate the crystal structure of a complex of
[Cu(LMe2)]2+ with the isothiocyanate ion.
The ligand LH2 was prepared, according to a published
preparation method.1,4 The LH2 of a liquid was purified through
an amino silica gel (100 – 200 mesh, Fuji Silysia Chem., Aichi,
Japan) column by an eluent-mixed ethyl acetate (Wako, Osaka,
Japan) with hexane (Wako) at a volume ratio of 1:1. The ligand
LMe2 was prepared by refluxing a mixture of LH2 with
formaldehyde (Wako) and formic acid (Wako), according to a
published method.1,4 The ligand LMe2 of a liquid was purified
by the same method as in the purification of LH2. Green-blue
single crystals of a complex of [Cu(LMe2)]2+ with an
isothiocyanate ion, [Cu(NCS)(LMe2)]ClO4, were grown from a
mixed methanolic solution of Cu(ClO4)2·6H2O (Aldrich,
Milwaukee, WI) and NaNCS (Wako) with LMe2 at a mole ratio
of 1:1:1.
The chemical structure of [Cu(NCS)(LMe2)]ClO4 is shown in
Fig. 1. Figure 2 shows a labeling diagram of [Cu(NCS)(LMe2)]
ClO4. The crystal data are summarized in Table 1. [Cu(NCS)
(LMe2)]ClO4 crystallized in a triclinic system, and was
characterized thus: P1, a = 9.257(3), b = 9.883(4), c = 11.806(5)
Å, a = 89.638(12), b = 81.053(10), g = 88.841(12)˚, Z = 2, V =
1066.7(7)Å3. The crystal structure was solved by direct
methods and refined by full-matrix least squares on F2 to final
values of R1 = 0.058. The selected bond distances and angles
for non-hydrogen atoms are summarized in Table 2. The atomic
coordinates and the other bond distances and angles for nonhydrogen atoms are summarized in Tables S1 – S3 (Supporting
Information).
The N-methyl groups for [Cu(NCS)(LMe2)]ClO4 were placed
at a cis configuration to each other, although those for
[Cu(ClO4)2(LMe2)] were at a trans configuration. When the
isothiocyanate ion strongly coordinated to [Cu(LMe2)]2+ of the
trans-configuration for N-methyl groups, it would largely distort
[Cu(NCS)(LMe2)]+. The large distortion of the [Cu(NCS)
Selected bond distances (Å) and angles (˚)
Cu1-N1
Cu1-N3
Cu1-N5
2.113(3)
2.065(3)
2.061(4)
Cu1-N2
Cu1-N4
2.049(3)
2.017(3)
N1-Cu1-N2
N1-Cu1-N4
N2-Cu1-N3
N2-Cu1-N5
N3-Cu1-N5
96.29(13)
82.03(13)
83.71(13)
93.26(15)
111.37(15)
N1-Cu1-N3
N1-Cu1-N5
N2-Cu1-N4
N3-Cu1-N4
N4-Cu1-N5
132.78(13)
115.75(14)
177.45(15)
96.01(13)
89.21(15)
(LMe2)]+ could decrease when the [Cu(NCS)(LMe2)]+ was
transformed from the trans- to the cis-configuration for
N-methyl groups. Resultantly, the [Cu(NCS)(LMe2)]2+ of the
cis-configuration for N-methyl groups would be more stable
than that of the trans-configuration.
Furthermore, the
[Cu(NCS)(LMe2)]+ was a trigonal bipyramidal geometry,
compared to the square bipyramidal geometry of
[Cu(ClO4)2(LMe2)]. The bond distances of Cu1–N1, Cu1–N2,
Cu1–N3, Cu1–N4, and Cu1–N5 were 2.113, 2.049, 2.065, 2.017,
and 2.061 Å, respectively, in Table 2. The bond angles of N2–
Cu1–N4, N1–Cu1–N3, N1–Cu1–N5, and N3–Cu1–N5 were
177.45, 132.78, 115.75, and 111.37˚, respectively, in Table 2.
Therefore, the [Cu(NCS)(LMe2)]+ was slightly distorted from
the trigonal bipyramidal geometry.
Supporting Information
Atomic coordinates (Table S1) and bond distances (Table S2)
and angles (Table S3) for non-hydrogen atoms. These materials
are available free of charge on the Web at http://www.jsac.or.jp/
analscix/.
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