Trans-Bis(2,2-diphenylethylamine-κN)bis(5,5-diphenylhydantoinato- κN3)copper(II) and its chloroform disolvate

Article abstract of DOI:10.1107/S010827010500209X

The crystal structures of the title compounds, [Cu(C₁₅H ₁₁N₂-O₂)₂(C₁₄H ₁₅N)₂] and [Cu(C₁₅H₁₁N ₂O₂)₂(C₁₄H₁₅N) ₂]·2CHCl₃, respectively, have been determined. The red disolvate complex affords a square-planar CuN₄ coordination environment in which the Cu atom lies on a centre of symmetry. The blue solvent-free complex affords a distorted square-pyramidal CuN₄O coordination environment and adjacent molecules form centrosymmetric dimers. A comparison of the different crystal structures focuses on the role of the solvent molecules in supramolecular assemblies of the copper(II) complexes.

Full text of DOI:10.1107/S010827010500209X

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
2003) or a ®ve-coordinated square-pyramidal CuN4O coordi-
nation geometry (Akitsu et al., 1997). To date, structural
regulation by other means, such as solvent in the crystal
(Tynan et al., 2004), has not been observed for analogous
complexes. We report here a structural comparison of
trans-bis(2,2-diphenylethylamine)bis(5,5-diphenylhydantoin-
ato)copper(II) chloroform disolvate, (I), and dimeric trans-
bis(2,2-diphenylethylamine)bis(5,5-diphenylhydantoinato)-
copper(II), (II).
ISSN 0108-2701
trans-Bis(2,2-diphenylethylamine-
jN)bis(5,5-diphenylhydantoinato-
jN3)copper(II) and its chloroform
disolvate
Takashiro Akitsu* and Yasuaki Einaga
Department of Chemistry, Faculty of Science and Technology, Keio University,
3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan
Correspondence e-mail: akitsu@chem.keio.ac.jp
Received 24 September 2004
Accepted 20 January 2005
Online 11 March 2005
The crystal structures of the title compounds, [Cu(C15H11N2-
O2)2(C14H15N)2] and [Cu(C15H11N2O2)2(C14H15N)2]Á2CHCl3,
respectively, have been determined. The red disolvate
complex affords a square-planar CuN4 coordination environ-
ment in which the CuII atom lies on a centre of symmetry. The
blue solvent-free complex affords a distorted square-pyra-
midal CuN4O coordination environment and adjacent mol-
ecules form centrosymmetric dimers. A comparison of the
different crystal structures focuses on the role of the solvent
molecules in supramolecular assemblies of the copper(II)
complexes.
Complex (I), the chloroform disolvate, affords a square-
planar CuN4 coordination geometry, in which the Cu atom lies
on an inversion centre (Fig. 1). Both the neutral 2,2-
Comment
In recent years, studies of supramolecular self-assembling
metal±organic frameworks of metal complexes have been
extensively carried out with the aim of rational construction of
desired crystal structures and ®ne-tuning of their functions
(Eddaoudi et al., 2001; Evans et al., 2002; Yaghi et al., 1998). In
particular, host±guest inclusion of small molecules and
hydrogen-bonded ¯exible self-assemblies enable the realiza-
tion of appropriate crystal packing containing guest molecules
(Holman et al., 2001), which depends on the novelty of the
secondary building units. In this respect, for example, vapo-
chromic switching of optoelectronic properties may be one of
the most promising strategies for the preparation of functional
materials (Kato et al., 2002; Fernandez et al., 2003). It is well
known that copper(II) complexes exhibit a remarkable variety
in their coordination geometries and corresponding optoe-
lectronic properties. Some copper(II) complexes incorpor-
ating monodentate 5,5-diphenylhydantoinate ligands have
been studied previously. In the solid state, most of these
complexes afford a four-coordinated square-planar CuN4
coordination geometry (Akitsu, Komorita & Urushiyama,
2001) with the aid of crystal-packing forces. Appropriate steric
factors of the ligands can lead to a tetrahedrally distorted
square-planar CuN4 coordination geometry (Akitsu et al.,
Figure 1
The molecular structure of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 30% probability level. H atoms
have been omitted for clarity. Only one chloroform solvent molecule is
shown. [Symmetry code: (i) 1 x, 1 y, 1 z.]
Acta Cryst. (2005). C61, m183±m186
DOI: 10.1107/S010827010500209X
# 2005 International Union of Crystallography m183

metal-organic compounds
diphenylethylamine ligands and the anionic deprotonated 5,5-
diphenylhydantoinate ligands act as monodentate ligands with
N-atom donors, and they are coordinated on trans sites with
respect to the Cu atom. The CuÐN bond distances (Table 1)
are within the range found in related complexes, some of
which are planar and some of which exhibit some tetrahedral
distortion, viz. the CuÐN(imide) distances range from
ligands is 139.4 (1)ꢀ, and those between the ®ve-membered
C3/C2/N1/C1/N2 ring of the 5,5-diphenylhydantoinate ligand
and the connecting phenyl groups, i.e. C4±C9 and C10±C15,
are 57.7 (1) and 123.0 (1)ꢀ, respectively [symmetry code: (i)
1
x, 1 y, 1 z].
The solvent-free complex, (II), affords a slightly distorted
pyramidal CuN4 coordination geometry (Fig. 2) and adjacent
1.975 (5) to 2.05 (1) A, whereas the CuÐN(amine) distances
molecules form centrosymmetric dimers, with a Cu1ÐO3iii
Ê
x, 1 y,
Ê
Ê
range from 1.97 (1) to 2.030 (4) A (Akitsu, Komorita & Kushi,
distance of 2.397 (4) A [symmetry code: (iii) 2
2001; Akitsu et al., 2003; Akitsu & Einaga, 2004). The cis-N1Ð
Cu1ÐN3 angles are close to being right angles. The dihedral
angle between the Cu1/N1/N3/N1i/N3i mean plane of the
coordination sphere and the N1/C1/N2/C2/C3 plane of the
1
z] (Fig. 3). The CuÐN bond distances are also within the
range found in related complexes (Table 3). The dihedral
angle between the N1/Cu1/N3 and N4/Cu1/N6 planes is
16.69 (1)ꢀ. The Cu atom deviates slightly from the N1/N3/N4/
Ê
N6 plane, by 0.178 (2) A. The dihedral angle between the Cu1/
N1/N3/N4/N6 and N1/C1/N2/C2/C3 planes is 94.7 (2)ꢀ, while
that between the Cu1/N1/N3/N4/N6 and N4/C30/N5/C31/C32
planes is 35.2 (2)ꢀ. Although the planarity of the coordination
environment is broken, the sp2 character of the N-donor
atoms of the 5,5-diphenylhydantoinate ligands is still main-
tained; the C1ÐN1ÐC3 and C30ÐN4ÐC31 bond angles are
108.0 (5) and 106.2 (5)ꢀ, respectively.
To the best of our knowledge, this is the ®rst case of related
complexes which exhibit different coordination geometries in
the presence or absence of solvent molecules in the crystal. In
the crystal structure of (I), four intramolecular hydrogen
bonds are formed around the coordination sphere, i.e. N3Ð
H13Á Á ÁO2 and N3ÐH12Á Á ÁO1i (Table 2). Furthermore, adja-
cent molecules are linked by double complementary inter-
molecular N2ÐH1Á Á ÁO1ii hydrogen bonds along the
Ê
crystallographic b axis [NÁ Á ÁO = 2.900 (3) A; symmetry code:
(ii) 1 x, 1 y, z]. The chloroform solvent molecules also
play an important role in stabilizing the crystal packing of (I)
Ê
via a C30ÐH27Á Á ÁO2 hydrogen bond [CÁ Á ÁO = 3.507 (5) A].
On the other hand, the crystal-packing mode of (II) is quite
different (Fig. 4). Only two intramolecular hydrogen bonds,
namely N3ÐH12Á Á ÁO4 and N6ÐH39Á Á ÁO3, are formed on
one side of the coordination sphere (Table 4). Moreover,
Figure 2
The molecular structure of (II) as a monomer, showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 30% probability level.
H atoms have been omitted for clarity.
Figure 3
The dimeric structure of (II). Displacement ellipsoids are drawn at the
30% probability level. H atoms and phenyl groups have been omitted for
clarity. [Symmetry code: (iii) 2 x, 1 y, 1 z.]
Figure 4
A molecular packing diagram of (II), viewed down the crystallographic c
axis.
ꢁ
m184 Akitsu and Einaga
[Cu(C15H11N2O2)2(C14H15N)2]Á2CHCl3 and [Cu(C15H11N2O2)2(C14H15N)2]
Acta Cryst. (2005). C61, m183±m186

metal-organic compounds
intermolecular hydrogen bonds, i.e. N5ÐH27Á Á ÁO2iii and
N2ÐH1Á Á ÁO4iv, link adjacent molecules to form hydrogen-
bonded networks [symmetry codes: (iii) 2 x, 1 y, 1 z;
(iv) 2 x, 1 y, z].
Compound (II)
Crystal data
[Cu(C15H11N2O2)2(C14H15N)2]
Mr = 960.63
Triclinic, P1
Z = 2
Dx = 1.327 Mg m
Mo Kꢀ radiation
3
Ê
Ê
a = 14.313 (4) A
Cell parameters from 25
re¯ections
Experimental
b = 15.888 (5) A
c = 11.863 (4) A
ꢁ = 10.0±12.4ꢀ
ꢂ = 0.51 mm
T = 298 (1) K
Ê
Treatment of equimolar quantities of copper(II) acetate (0.454 g,
2.50 mmol), 5,5-diphenylhydantoin (1.26 g, 5.00 mmol) and 2,2-di-
phenylethylamine (0.99 g, 5.00 mmol) in ethanol (100 ml) at 323 K
for 2 h gave rise to crude precipitates. Red±violet plate-like crystals of
(I) were obtained from a solution in chloroform±methanol (4:1 v/v)
1
ꢀ = 90.13 (3)ꢀ
ꢅ = 95.00 (3)ꢀ
ꢆ = 63.58 (2)ꢀ
Plate, blue±violet
0.50 Â 0.40 Â 0.20 mm
3
Ê
V = 2404.7 (14) A
1
Data collection
kept at 298 K over a period of several days. IR (KBr): 1644 cm
(amide I band); m.p. 629 K (decomposition). Recrystallization of the
crude precipitates from a solution in chloroform±methanol (4:1 v/v)
at 283 K overnight yielded only a small amount of blue±violet plate-
like crystals of solvent-free complex (II). IR (KBr): 1645 cm 1 (amide
I band); m.p. 605 K (decomposition).
Rigaku AFC-7R diffractometer
!/2ꢁ scans
Absorption correction: scan
(North et al., 1968)
Tmin = 0.783, Tmax = 0.903
12 233 measured re¯ections
12 233 independent re¯ections
11 075 re¯ections with I > 0ꢃ(I)
Rint = 0.087
ꢁmax = 27.5ꢀ
h = 18 ! 18
k = 20 ! 20
l = 6 ! 15
3 standard re¯ections
every 150 re¯ections
intensity decay: 0.3%
Compound (I)
Re®nement
Crystal data
Re®nement on F2
R[F2 > 2ꢃ(F2)] = 0.069
wR(F2) = 0.161
S = 0.85
11075 re¯ections
527 parameters
H-atom parameters constrained
w = 1/[ꢃ2(Fo2) + (0.0502P)2]
3
[Cu(C15H11N2O2)2(C14H15N)2]Á-
Dx = 1.393 Mg m
Mo Kꢀ radiation
Cell parameters from 25
re¯ections
2
where P = (Fo + 2Fc2)/3
2CHCl3
Mr = 1199.34
Orthorhombic, Pbca
(Á/ꢃ)max < 0.001
3
Ê
Áꢄmax = 0.62 e A
ꢁ = 10.3±12.6ꢀ
ꢂ = 0.72 mm
T = 298 (1) K
Ê
1.31 e A
Ê
a = 19.37 (1) A
Ê
b = 29.796 (7) A
c = 9.910 (3) A
Ê
V = 5720 (4) A
Z = 4
3
Áꢄmin
=
1
Ê
3
Plate, red±violet
0.41 Â 0.16 Â 0.10 mm
Table 3
Selected geometric parameters (A, ) for (II).
ꢀ
Ê
Data collection
Cu1ÐO3i
Cu1ÐN1
Cu1ÐN3
2.397 (4)
1.990 (4)
2.030 (3)
Cu1ÐN4
Cu1ÐN6
2.026 (4)
2.032 (4)
Rigaku AFC-7R diffractometer
!/2ꢁ scans
Rint = 0.021
ꢁmax = 27.5ꢀ
Absorption correction: scan
(North et al., 1968)
Tmin = 0.872, Tmax = 0.931
8516 measured re¯ections
6565 independent re¯ections
3338 re¯ections with I > 2ꢃ(I)
h = 10 ! 25
O3iÐCu1ÐN1
O3iÐCu1ÐN3
O3iÐCu1ÐN4
O3iÐCu1ÐN6
N1ÐCu1ÐN3
109.8 (1)
92.2 (1)
86.7 (1)
91.9 (1)
86.9 (2)
N1ÐCu1ÐN4
N1ÐCu1ÐN6
N3ÐCu1ÐN4
N3ÐCu1ÐN6
N4ÐCu1ÐN6
163.5 (2)
89.1 (2)
93.7 (2)
175.0 (2)
89.2 (2)
k = 0 ! 38
l = 12 ! 5
3 standard re¯ections
every 150 re¯ections
intensity decay: 0.2%
Symmetry codes: (i) 2 x; 1 y; 1 z.
Re®nement
Re®nement on F2
R[F2 > 2ꢃ(F2)] = 0.050
wR(F2) = 0.163
S = 0.99
3338 re¯ections
302 parameters
H-atom parameters constrained
w = 1/[ꢃ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢃ)max < 0.001
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢀ
Ê
3
Ê
Áꢄmax = 0.43 e A
3
Ê
0.46 e A
Áꢄmin
=
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH1Á Á ÁO4ii
N3ÐH12Á Á ÁO4
N5ÐH27Á Á ÁO2i
N6ÐH39Á Á ÁO3
0.95
0.95
0.95
0.95
2.00
2.17
2.09
2.07
2.915 (6)
2.915 (6)
2.857 (5)
2.817 (5)
160
135
136
134
Table 1
Selected geometric parameters (A, ) for (I).
ꢀ
Ê
Cu1ÐN1
2.009 (3)
89.2 (1)
Cu1ÐN3
2.005 (3)
Symmetry codes: (i) x ‡ 2; y ‡ 1; z ‡ 1; (ii) x ‡ 2; y ‡ 1; z.
N1ÐCu1ÐN3
All H atoms were placed in calculated positions, with CÐH = NÐ
Ê
H = 0.95 A, and included in the ®nal cycles of re®nement using a
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢀ
riding model, with Uiso(H) = 1.2Ueq(parent atom). The C atoms of the
phenyl groups, viz. C4±C9, C10±C15, C18±C23 and C24±C29 for (I),
and C4±C9, C10±C15, C18±C23, C24±C29, C33±C38, C39±C44, C47±
C52 and C53±C58 for (II), were treated as rigid groups of anisotropic
atoms. The intensity of the data was relatively weak, similar to some
analogous mononuclear copper complexes with large organic ligands.
The largest hole in the difference map of (II) is near atom Cu1, at
(0.9919, 0.4909, 0.2953).
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH1Á Á ÁO1i
N3ÐH12Á Á ÁO1ii
N3ÐH13Á Á ÁO2
C30ÐH27Á Á ÁO2
0.95
0.95
0.95
0.95
2.02
2.06
2.13
2.57
2.900 (3)
2.837 (3)
2.922 (3)
3.507 (5)
153
137
140
170
Symmetry codes: (i) 1 x; 1 y; z; (ii) 1 x; 1 y; 1 z.
ꢁ
Acta Cryst. (2005). C61, m183±m186
Akitsu and Einaga
[Cu(C15H11N2O2)2(C14H15N)2]Á2CHCl3 and [Cu(C15H11N2O2)2(C14H15N)2] m185

metal-organic compounds
Akitsu, T., Komorita, S. & Tamura, H. (2003). Inorg. Chim. Acta, 348, 25±32.
Akitsu, T., Komorita, S. & Urushiyama, A. (2001). Bull. Chem. Soc. Jpn, 74,
851±860.
For both compounds, data collection: WinAFC Diffractometer
Control Software (Rigaku, 1999); cell re®nement: WinAFC Diffrac-
tometer Control Software; data reduction: TEXSAN (Molecular
Structure Corporation, 2001); program(s) used to solve structure:
SIR92 (Altomare et al., 1994); programs used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII
(Johnson, 1976); software used to prepare material for publication:
TEXSAN.
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C.,
Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. &
Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319±330.
Evans, O. R. & Lin, W. (2002). Acc. Chem. Res. 35, 511±522.
Fernandez, E. J., Lopez-de-Luzuriaga, J. M., Monge, M., Olmos, M. E., Perez,
J., Laguna, A., Mohamed, A. A. & Fackler, J. P. Jr (2003). J. Am. Chem. Soc.
125, 2022±2023.
Holman, K. T., Picocar, A. M., Swift, J. A. & Ward, M. D. (2001). Acc. Chem.
Res. 34, 107±118.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
This work was supported by a Grant-in-Aid for the 21st
Century COE programme `KEIO Life Conjugate Chemistry'
from the Ministry of Education, Culture, Sports, Science and
Technology, Japan.
Kato, M., Omura, A., Toshikawa, A., Kishi, S. & Suhimoto, Y. (2002). Angew.
Chem. Int. Ed. 41, 3183±3185.
Molecular Structure Corporation (2001). TEXSAN. Version 1.11. MSC, 9009
New Trails Drive, The Woodlands, TX 77381-5209, USA.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351±
359.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TA1482). Services for accessing these data are
described at the back of the journal.
Rigaku (1999). WinAFC Diffractmeter Control Software. Rigaku Corporation,
Tokyo, Japan.
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Tynan, E., Jensen, P., Kruger, P. E. & Lees, A. C. (2004). Chem. Commun. pp.
776±777.
Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. L. (1998). Acc. Chem.
Res. 31, 474±484.
References
Akitsu, T. & Einaga, Y. (2004). Acta Cryst. E60, m524±m526.
Akitsu, T., Komorita, S. & Kushi, Y. (2001). Inorg. Chim. Acta, 315, 18±25.
Akitsu, T., Komorita, S., Kushi, Y., Li, C., Kanehisa, N. & Kai, Y. (1997). Bull.
Chem. Soc. Jpn, 70, 821±827.
ꢁ
m186 Akitsu and Einaga
[Cu(C15H11N2O2)2(C14H15N)2]Á2CHCl3 and [Cu(C15H11N2O2)2(C14H15N)2]
Acta Cryst. (2005). C61, m183±m186