ArticlePDF Available

A compound of a novel tetraaza-macrocycle with trinuclear tetracyanonickelate-bridged cations

Authors:
Neil F. Curtis at Victoria University of Wellington
Neil F. Curtis
Horst Puschmann
Horst Puschmann
Horst Puschmann
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Download full-text PDFDownload full-text PDF
Read full-text
Download citation

Abstract and Figures

The cation of the title compound, [Cu(L)]2+, is formed by Michael condensation of (4,6,6-tri­methyl-3,7-di­aza­non-3-ene-1,9-di­amine)copper(II) with methanal and nitro­propane. This cation forms a tetra­cyano­nickelate(II) compound, the unit cell of which contains two centrosymmetric tetra­cyano­nickelate(II)-bridged trinuclear cations, namely di­aqua-1,3κ2O-di-μ-cyano-1:2κ2C:N;1:3κ2C:N-di­cyano-1κ2C-bis(13-ethyl-5,7,7-tri­methyl-13-nitro-1,4,8,11-tetra­aza­cyclo­tetra­dec-4-ene)-2κ4N1,N4,N8,N11;3κ4N1,N4,N8,N11-dicopper(II)­nickel(II) di-μ-cyano-1:2κ2C:N;1:3κ2C:N-di­cyano-1κ2C-bis­(13-ethyl-5,7,7-tri­methyl-13-nitro-1,4,8,11-tetra­aza­cyclo­tetra­dec-4-ene)-2κ4N1,N4,N8,N11;3κ4N1,N4,N8,N11-dicopper(II)­nickel(II) bis­[tetra­cyano­nickelate(II)] octahydrate, [Cu2Ni(CN)4(C15H31N5O2)2(H2O)2][Cu2Ni(CN)4(C15H31N5O2)2][Ni(CN)4]2·8H2O. One cation, [(L)Cu–NC–Ni(CN)2–CN–Cu(L)]2+, has an axially coordinated bridging [Ni(CN)4]2− ion, with a Cu—N distance of 2.226 (3) Å and a Cu—N—C angle of 168.2 (3)°. The other cation, [(H2O)(L)Cu–NC–Ni(CN)2–CN–Cu(L)(OH2)]2+, has water axially coordinated trans to a weakly bound bridging [Ni(CN)4]2− ion, with a Cu—O distance of 2.396 (3) Å, a Cu—N distance of 2.677 (4) Å, an O—Cu—N angle of 168.7 (1)° and a Cu—N—C angle of 137.7 (3)°. These cations, plus independent [Ni(CN)4]2− ions and water mol­ecules, are linked into a hydrogen-bonded network. All [Ni(CN)4]2− ions are on centres of symmetry.
Figures - uploaded by Neil F. Curtis
Author content
All figure content in this area was uploaded by Neil F. Curtis
Content may be subject to copyright.
56fd875808aea6b77466ed
45.pdf
Content uploaded by Neil F. Curtis
Author content
All content in this area was uploaded by Neil F. Curtis on Mar 31, 2016
Content may be subject to copyright.
A compound of a novel tetraaza-macrocycle with trinuclear tetracyanonickelate-bridged catio
ns.pdf
Available via license: CC BY 2.0
Content may be subject to copyright.
A compound of a novel tetraaza-
macrocycle with trinuclear tetra-
cyanonickelate-bridged cations
Neil F. Curtis
a
* and Horst Puschmann
b
a
School of Chemical and Physical Sciences, Victoria University of Wellington, Box
600, Wellington, New Zealand, and
b
Durham University Chemical Crystallography
Group, Durham DH1 3LE, England
Correspondence e-mail: neil.curtis@vuw.ac.nz
Received 4 June 2004
Accepted 24 June 2004
Online 21 July 2004
The cation of the title compound, [Cu(L)]
2+
, is formed by
Michael condensation of (4,6,6-trimethyl-3,7-diazanon-3-ene-
1,9-diamine)copper(II) with methanal and nitropropane. This
cation forms a tetracyanonickelate(II) compound, the unit
cell of which contains two centrosymmetric tetracyano-
nickelate(II)-bridged trinuclear cations, namely diaqua-
1,3
2
O-di--cyano-1:2
2
C:N;1:3
2
C:N-dicyano-1
2
C-bis-
(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetra-
dec-4-ene)-2
4
N
1
,N
4
,N
8
,N
11
;3
4
N
1
,N
4
,N
8
,N
11
-dicopper(II)-
nickel(II) di--cyano-1:2
2
C:N;1:3
2
C:N-dicyano-1
2
C-bis-
(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetra-
dec-4-ene)-2
4
N
1
,N
4
,N
8
,N
11
;3
4
N
1
,N
4
,N
8
,N
11
-dicopper(II)-
nickel(II) bis[tetracyanonickelate(II)] octahydrate, [Cu
2
-
Ni(CN)
4
(C
15
H
31
N
5
O
2
)
2
(H
2
O)
2
][Cu
2
Ni(CN)
4
(C
15
H
31
N
5
O
2
)
2
]-
[Ni(CN)
4
]
2
8H
2
O. One cation, [(L)Cu±NC±Ni(CN)
2
±CN±
Cu(L)]
2+
, has an axially coordinated bridging [Ni(CN)
4
]
2ÿ
ion, with a CuÐN distance of 2.226 (3) A
Ê
and a CuÐNÐC
angle of 168.2 (3)
. The other cation, [(H
2
O)(L)Cu±NC±
Ni(CN)
2
±CN±Cu(L)(OH
2
)]
2+
, has water axially coordinated
trans to a weakly bound bridging [Ni(CN)
4
]
2ÿ
ion, with a CuÐ
O distance of 2.396 (3) A
Ê
, a CuÐN distance of 2.677 (4) A
Ê
,an
OÐCuÐN angle of 168.7 (1)
and a CuÐNÐC angle of
137.7 (3)
. These cations, plus independent [Ni(CN)
4
]
2ÿ
ions
and water molecules, are linked into a hydrogen-bonded
network. All [Ni(CN)
4
]
2ÿ
ions are on centres of symmetry.
Comment
Michael condensations of (polyamine)metal complexes with
methanal and nitroalkanes form nitroalkyl-substituted cyclic
amine complexes (Lawrance, Lye et al., 1993; Lawrance,
Maeder et al., 1993; Comba et al., 1986), such as 6-methyl-6-
nitro-1,4,8,11-tetraazacyclotetradecane)copper(II), which is
formed from (3,7-diazanonane-1,9-diamine)metal compounds,
methanal and nitroethane (Comba et al., 1988a,b). The
(tetraaza-macrocycle)copper(II) cation, [Cu(L)]
2+
, present in
the title compound, formed by an analogous reaction of (4,6,6-
trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) with me-
thanal and nitropropane, differs by the presence of the imine
function, the introduction of the 5,7,7-trimethyl substituents
and the substitution of a 6-ethyl substituent for 6-methyl.
Structures of a number of methyl/nitro-substituted aza-
macrocycle compounds obtained by reaction of (amine)metal
compounds with nitroethane and methanal have been
reported, but this is the ®rst for an ethyl/nitro-substituted
analogue derived from nitropropane.
The structures of many compounds of (amine)metal cations
with cyanometallate anions have been reported, often with
oligo- or polymeric structures with bridging cyanometallate
ions (Cernak et al., 2002).
The title compound, (I), which crystallizes from aqueous
solutions containing [Ni(CN)
4
]
2ÿ
and [Cu(L)]
2+
, has the
formal composition [Cu(L)][Ni(CN)
4
]2.5H
2
O, but has two
structurally distinct centrosymmetric tetracyanonickelate(II)-
bridged (aza-macrocycle)copper(II) trinuclear cations, two
independent tetracyanonickelate(II) anions, and one coordi-
nated and four uncoordinated water molecules (see Fig. 1 and
Table 1).
Atom Cu1A is in a square-planar coordination environment
formed by the three secondary amine atoms, viz.N1A,N8A
and N11A, and imine atom N4A of macrocycle L
a
, with atom
metal-organic compounds
m410 # 2004 International Union of Crystallography DOI: 10.1107/S0108270104015483 Acta Cryst. (2004). C60, m410±m413
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
N55 of the [Ni5(CN)
4
]
2ÿ
tetracyanonickelate(II) ion coordi-
nated axially; the result is a centrosymmetric trinuclear cation,
[(L
a
)Cu±NC±Ni(CN)
2
±CN±Cu(L
a
)]
2+
,withaCuCu
separation of 10.426 (5) A
Ê
(see Fig. 2).
Atom Cu1B is in a square-planar coordination environment
formed by the four N atoms, viz.N1B,N4B,N8B and N11B,of
macrocycle L
b
, with weaker axial interactions with water atom
O10 and atom N65 of the [Ni6(CN)
4
]
2ÿ
ion forming a weakly
bound centrosymmetric trinuclear cation, [(H
2
O)(L
b
)Cu±NC±
Ni(CN)
2
±CN±Cu(L
b
)(OH
2
)]
2+
, with a CuCu separation of
10.599 (5) A
Ê
(see Fig. 3).
For the two (aza-macrocycle)copper(II) cations, the CuÐ
N
ring
distances are similar (with the CuÐN
imine
distance ca
0.03 A
Ê
shorter than the mean CuÐN
amine
distance), the
con®guration is the same (1S,8R,11R; Spek, 2002) and the
conformations are similar. The nitro group and the C72 methyl
component of the gem-dimethyl group are axially oriented on
the same side of the N
4
macrocycle coordination plane as the
N1ÐH1 and N11ÐH11 groups, with the N8ÐH8 group and
the axial ligand (N55 for Cu1A and O10 for Cu1B) on the
other side. The N
4
plane is less tetrahedrally twisted and the
Cu atom is further displaced from this plane for the
[Cu1A(L
a
)]
2+
ion [0.017 (2) and 0.246 (2) A
Ê
] than for the
[Cu1B(L
b
)]
2+
ion [0.067 (2) and 0.088 (2) A
Ê
]; these planes
are inclined at 30.9 (2)
. The C15 methylene substituents of
both macrocycles are equatorially oriented, with the terminal
methyl group, C16A, of the [Cu(L
a
)]
2+
ion further equatorially
extended and closer to atom O18A, while the C16B group is
axially oriented on the same side as axial water ligand O10.
The coordinated isocyano atom N55 is close to the square-
pyramidal axis of the [Cu1A(L
a
)]
2+
ion, with N
ring
ÐCu1AÐ
N55 angles of between 95.1 (1) and 99.3 (1)
. The non-brid-
ging N56ÐC56ÐNi5 group is approximately aligned with the
C7AC14A axis [N56Ni5Cu1AÐC7A = ÿ1.4 (2)
].
The ion is tilted with respect to the N
4
coordination plane so
that the N8AN56 distance [6.250 (5) A
Ê
] is longer than the
N1AN56(ÿx,2ÿ y, ÿz) distance [4.998 (5) A
Ê
].
For [Cu1B(L
b
)]
2+
, the coordinated water O and isocyano N
atoms are displaced from the square-bipyramidal axis, with
N
ring
ÐCu1BÐO10 angles of 87.1 (1)±101.8 (1)
and N
ring
Ð
Cu1BÐN65 angles of 81.9 (1)±96.8 (1)
.
The dimensions of the coordinated and non-coordinated
[Ni(CN)
4
]
2ÿ
ions, all centrosymmetric, do not differ signi®-
cantly. The two tetracyanonickelate(II) anions including
atoms Ni7 and Ni8, and the water molecules including atoms
O11, O12, O13 and O14 have no direct interaction with the
copper(II) cations, though all are linked into a hydrogen-
bonding network (see Table 2).
Chain polymeric structures are present for bis(ethane-1,2-
diamine)copper(II) tetracyanonickelate(II), [±Cu(en)
2
±NC±
Ni(CN)
2
±CN±Cu(en)
2
±] (Luo et al., 2000; Lokaj et al., 1991),
metal-organic compounds
Acta Cryst. (2004). C60, m410±m413 Curtis and Puschmann
ACu
2
Ni±C
15
H
31
N
5
O
2
±CN complex m411
Figure 2
The [(L
a
)Cu±NC±Ni(CN)
2
±CN±Cu(L
a
)]
2+
cation, drawn with displace-
ment ellipsoids at the 50% probability level.
Figure 1
The structure of the title compound, drawn with displacement ellipsoids
at the 50% probability level for non-H atoms, showing the asymmetric
unit (labelled atoms and atoms of associated macrocycles), with
additional atoms generated by symmetry operations to complete the
tetracyanonickelate(II) anions and trinuclear cations.
Figure 3
The [(H
2
O)(L
a
)Cu±NC±Ni(CN)
2
±CN±Cu(L
b
)(OH
2
)]
2+
cation, drawn
with displacement ellipsoids at the 50% probability level.
and for analogous cyanometallate compounds of other
(tetraamine)copper(II) cations, including the meso-(5,5,-
7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)-
copper(II), [Cu(L
1
)]
2+
, compounds with [Fe(CN)
6
]
3ÿ
(Zou et
al., 1998) and [Cr(CN)
6
]
3ÿ
(El Fallah et al., 2001). The
[Ni(CN)
4
]
2ÿ
compounds formed by [Ni(L
1
)]
2+
(Gainsford &
Curtis, 1984) and (3,10-diethyl-1,3,5,8,10,12-hexaazacyclo-
tetradecane)nickel(II) (Kou et al., 2000) have similar struc-
tures, but with the NiÐN
cyano
distances longer than CuÐ
N
cyano
. The two faces of these (aza-macrocycle)metal(II)
cations are equivalent, favouring the symmetrical structures
observed. The two faces of the [Cu(L)]
2+
cation are inherently
different, the con®guration observed having the axial nitro
and methyl groups on the same side, which minimizes the
interaction with an axial substituent coordinated on the other
side. For the [Cu(L
a
)]
2+
ion, the isocyano N atom is coordi-
nated on this less congested side, while for the [Cu(L
b
)]
2+
ion,
water is bound on this side and the isocyano group is bound
more weakly on the other side.
Experimental
Aqua(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetra-
dec-4-ene)copper(II) bis(perchlorate), [Cu(L)(H
2
O)](ClO
4
)
2
, was
prepared by condensation of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-
diamine)copper(II) perchlorate (Blight & Curtis, 1962; Curtis, 1972;
Curtis et al., 2003), methanal and nitropropane in water, with
NaHCO
3
as base. The mauve-coloured tetracyanonickelate(II)
compound precipitated when aqueous solutions containing
[Ni(CN)
4
]
2ÿ
and [Cu(L)]
2+
were mixed. The sparingly soluble
compound was recrystallized by evaporation of an aqueous solution.
Crystal data
[Cu
2
Ni(CN)
4
(C
15
H
31
N
5
O
2
)
2
-
(H
2
O)
2
][Cu
2
Ni(CN)
4
-
(C
15
H
31
N
5
O
2
)
2
][Ni(CN)
4
]
2
8H
2
O
M
r
= 2339.23
Triclinic, P
1
a = 11.7497 (2) A
Ê
b = 14.0540 (3) A
Ê
c = 17.9014 (4) A
Ê
= 70.154 (1)
= 78.165 (1)
= 81.290 (1)
V = 2710.6 (1) A
Ê
3
Z =1
D
x
= 1.431 Mg m
ÿ3
Mo K radiation
Cell parameters from 7862
re¯ections
= 2.3±29.3
= 1.52 mm
ÿ1
T = 120 (2) K
Plate, purple
0.35 0.35 0.08 mm
Data collection
Bruker SMART 1K CCD area
detector diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
T
min
= 0.538, T
max
= 0.885
R
int
= 0.047 before correction
22 241 measured re¯ections
14 372 independent re¯ections
9857 re¯ections with I >2(I )
R
int
= 0.034
max
= 29.1
h = ÿ15 ! 15
k = ÿ19 ! 19
l = ÿ24 ! 23
Re®nement
Re®nement on F
2
R[F
2
>2(F
2
)] = 0.063
wR(F
2
) = 0.162
S = 1.05
14 372 re¯ections
666 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[
2
(F
2
o
) + (0.0668P)
2
+ 5.1175P]
where P =(F
2
o
+2F
2
c
)/3
(/)
max
= 0.006
max
= 1.41 e A
Ê
ÿ3
min
= ÿ0.73 e A
Ê
ÿ3
C- and N-bound H atoms were placed in calculated positions and
treated as riding. Water H atoms were located from difference
syntheses, and their positions were re®ned with restrained OÐH
distances [0.82 (2) A
Ê
] and HÐOÐH angles [HH = 1.35 (2) A
Ê
].
Data collection: SMART (Bruker, 1997); cell re®nement: SMART;
data reduction: SAINT (Bruker, 2001); program(s) used to solve
structure: SHELXTL (Bruker, 1997); program(s) used to re®ne
structure: SHELXTL; molecular graphics: ORTEP-3.2 (Farrugia,
1997); software used to prepare material for publication: SHELXTL.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1674). Services for accessing these data are
described at the back of the journal.
References
Blight, M. M. & Curtis, N. F. (1962). J. Chem. Soc. pp. 3016±3020.
Bruker (1997). SMART (Version 5.054) and SHELXTL (Version 5.10).
Bruker AXS Inc., Madison, Wisconsin, USA.
metal-organic compounds
m412 Curtis and Puschmann
ACu
2
Ni±C
15
H
31
N
5
O
2
±CN complex Acta Cryst. (2004). C60, m410±m413
Table 1
Selected geometric parameters (A
Ê
,
).
Cu1AÐN4A 1.999 (4)
Cu1AÐN11A 2.013 (3)
Cu1AÐN8A 2.031 (3)
Cu1AÐN1A 2.041 (3)
Cu1AÐN55 2.226 (3)
N4AÐC5A 1.304 (6)
Cu1BÐN4B 1.986 (4)
Cu1BÐN8B 2.018 (4)
Cu1BÐN1B 2.020 (3)
Cu1BÐN11B 2.026 (4)
Cu1BÐO10 2.396 (3)
Cu1BÐN65 2.677 (4)
N4BÐC5B 1.304 (6)
N4AÐCu1AÐN11A 164.6 (2)
N4AÐCu1AÐN8A 95.6 (2)
N11AÐCu1AÐN8A 85.9 (1)
N4AÐCu1AÐN1A 85.4 (2)
N11AÐCu1AÐN1A 89.7 (1)
N8AÐCu1AÐN1A 166.8 (2)
N4AÐCu1AÐN55 99.9 (2)
N11AÐCu1AÐN55 95.1 (1)
N8AÐCu1AÐN55 96.7 (2)
N1AÐCu1AÐN55 96.1 (1)
C55ÐN55ÐCu1A 168.2 (3)
N4BÐCu1BÐN8B 95.9 (2)
N4BÐCu1BÐN1B 86.0 (2)
N8BÐCu1BÐN1B 177.7 (2)
N4BÐCu1BÐN11B 170.7 (2)
N8BÐCu1BÐN11B 86.9 (2)
N1BÐCu1BÐN11B 91.0 (2)
N4BÐCu1BÐO10 101.6 (2)
N8BÐCu1BÐO10 87.0 (2)
N1BÐCu1BÐO10 93.9 (1)
N11BÐCu1BÐO10 87.3 (2)
N4BÐCu1BÐN65 88.6 (2)
N8BÐCu1BÐN65 96.8 (2)
N1BÐCu1BÐN65 81.9 (1)
N11BÐCu1BÐN65 82.2 (1)
O10ÐCu1BÐN65 168.7 (1)
C65ÐNi6ÐC66 89.1 (2)
C65ÐN65ÐCu1B 137.7 (3)
Table 2
Hydrogen-bonding geometry (A
Ê
,
).
DÐHADÐH HADADÐHA
N1AÐH1AN85
i
0.91 2.26 3.124 (5) 159
N11AÐH11AO14 0.91 2.11 2.869 (5) 140
N11AÐH11AO19A 0.91 2.41 2.978 (5) 121
N1BÐH1BO19A 0.91 2.12 2.937 (5) 149
N8BÐH8BO12 0.91 2.13 3.041 (5) 174
N8BÐH8BO10 0.91 2.58 3.052 (5) 113
N11BÐH11BO19B 0.91 2.29 2.874 (5) 122
O10ÐH10EN75
ii
0.84 (5) 1.92 (5) 2.745 (6) 168 (5)
O10ÐH10FO12 0.85 (5) 1.93 (5) 2.702 (5) 151 (5)
O11ÐH11EN66
iii
0.84 (3) 2.04 (4) 2.870 (5) 170 (6)
O11ÐH11FN56 0.83 (5) 2.28 (5) 3.106 (5) 172 (5)
O12ÐH12FN86 0.83 (4) 1.97 (4) 2.788 (5) 168 (6)
O12ÐH12EO13 0.84 (4) 1.88 (3) 2.702 (5) 171 (6)
O13ÐH13EO11
iv
0.84 (4) 1.94 (4) 2.733 (5) 158 (6)
O13ÐH13FN56
iii
0.83 (4) 2.15 (4) 2.973 (6) 170 (5)
O14ÐH14EN76
ii
0.82 (4) 2.03 (4) 2.847 (5) 174 (7)
O14ÐH14FN85
i
0.82 (5) 2.10 (5) 2.872 (6) 159 (6)
Symmetry codes: (i) x; 1 y; z; (ii) x ÿ 1; y; z; (iii) 1 ÿ x; 1 ÿ y; ÿz; (iv) x ÿ 1;
y ÿ 1; z.
Bruker (2001). SADABS (Version 2.03) and SAINT (Version 6.02A). Bruker
AXS Inc., Madison, Wisconsin, USA.
Cernak, J., Orendac, M., Potocnak, I., Chomic, J., Orendacova, A., Skorsepa, J.
& Feher, A. (2002). Coord. Chem. Rev. 224, 51±66.
Comba, P., Curtis, N. F., Lawrance, G. A., O'Leary, M. A., Skelton, B. W. &
White, A. H. (1988a). J. Chem. Soc. Dalton Trans. pp. 497±502.
Comba, P., Curtis, N. F., Lawrance, G. A., O'Leary, M. A., Skelton, B. W. &
White, A. H. (1988b). J. Chem. Soc. Dalton Trans. pp. 2145±2152.
Comba, P., Curtis, N. F., Lawrance, G. A., Sargeson, A. M., Skelton, B. W. &
White, A. H. (1986). Inorg. Chem. 25, 4260±4267.
Curtis, N. F. (1972). J. Chem. Soc. Dalton Trans. pp. 1357±1361.
Curtis, N. F., Powell, H. K. J., Puschmann, H., Rickard, C. E. F. & Waters, J. M.
(2003). Inorg. Chim. Acta, 355, 25±32.
El Fallah, M. S., Ribas, J., Solans, X. & Font-Bardia, M. (2001). J. Chem. Soc.
Dalton Trans. pp. 247±250.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Gainsford, G. J. & Curtis, N. F. (1984). Aust. J. Chem. 37, 1799±1816.
Kou, H. Z., Liao, D. Z., Jiang, Z. H., Yan, S. P., Wu, Q. J., Gao, S. & Wang, G. L.
(2000). Inorg. Chem. Commun. 3, 151±154.
Lawrance, G. A., Lye, P. G., Maeder, M. & Wilkes, E. N. (1993). Spec. Publ. R.
Soc. Chem. 131, 106±109.
Lawrance, G. A., Maeder, M. & Wilkes, E. N. (1993). Rev. Inorg. Chem. 13,
199±132.
Lokaj, J., Gyerova, K., Sopkova, A., Sivy, J., Kettmann, V. & Vrabel, V. (1991).
Acta Cryst. C47, 2447±2448.
Luo, J.-H., Wu, M.-X., Wang, Y.-M., Gao, D.-S., Li, D. & Cheng, C.-Z. (2000).
Jiegou Huaxue, 19, 187±190.
Spek, A. L. (2002). PLATON. Utrecht University, The Netherlands.
Zou, J. Z., Hu, X. D., Duan, C. Y., Xu, Z., You, X. Z. & Mak, T. C. W. (1998).
Transition Met. Chem. 23, 477±480.
metal-organic compounds
Acta Cryst. (2004). C60, m410±m413 Curtis and Puschmann
ACu
2
Ni±C
15
H
31
N
5
O
2
±CN complex m413
... Tetraazamacrocyclic ligands have received remarkable attention as they exhibit unusual characteristics related to their size, degree of unsaturation in the central framework and axial ligation properties [1][2][3][4] and play a significant role in separation techniques (for stable structure) and other spectral studies 5 . HMTAA-14 and HMTAA-16 macrocycles (HMTAA-14 = dichloro [2,4,9,13,15,20-hexamethyldibenzo-1,4,8,11-tetraazacyclotetradecatetraene]) are mimicking agents for naturally occurring systems such as porphyrins and corrin rings. ...
... The appearance of bands in the region 400-480 cm -1 corresponds to M-N vibrational modes and evidenced the coordination between metal and azomethine nitrogen. The absorption spectrum of complex (1) contain three bands at 23696, 24875 and 25512 cm -1 which are assigned to the 3 A 2g (F) → 3 T 2g (F) (ε = 5300 L mol −1 cm −1 ), 3 A 2g (F) → 3 T 1g (F) (ε = 4600 L mol −1 cm −1 ), and 3 A 2g (F)→ 3 T 1g (P) (ε = 5700 L mol −1 cm −1 ) transitions, respectively, as recorded at room temperature using methanol (0.001 M) in the range 200-800 nm . Also, the absorption spectrum of complex (2) also contain three bands at 18552, 17605 and 15552 cm -1 which are assigned to the 2 B 1g (G)→ 2 B 2g (G) (ε = 4570 L mol −1 cm −1 ), 2 B 1g (G)→ 2 E g (G) (ε = 7000 L mol −1 cm −1 ),and 2 B 1g (G)→ 2 A 1g (G) (ε = 6400 L mol −1 cm −1 ) transitions, respectively. ...
Synthesis and Electrochemical Analysis of Biologically Active Novel NiIIHMTAA and CuIIHMTAA Complexes
Article
Full-text available
  • Nov 2019
NiIIHMTAA-14 and CuIIHMTAA-14 (HMTAA-14 = dichloro[2,4,9,13,15,20-hexamethyldibenzo-1,4,8,11-tetraazacyclotetradecatetraene]) macrocyclic complexes have been synthesized by template method and characterized by multiple characterization techniques. Electrochemical studies of NiIIHMTAA-14 and CuIIHMTAA-14 macrocyclic complexes carried out on Pt disc (tip-06.1204.120.) electrode (2 mm diameter) in methanol, DMSO and acetonitrile by employing cyclic voltammetry revealing that these macrocycles undergo one-electron electrochemical processes to form stable Ni(HMTAA)0 and Cu(HMTAA)+ species. Preliminary investigation of antimicrobial activities of these novel macrocyclic complexes has also been studied.
View
... Magnetic and spectral properties accompanied by crystal structures of newly synthesized cyano-bridged bimetallic polymeric complexes have been studied recently [14][15][16][17][18][19][20][21]. Cyano-complexes, especially tetracyanonickelate complexes, have been systematically investigated [5,15,17,[22][23][24], but very little has been published to date on the structures of tetracyanopalladate complexes [19,[25][26][27]. ...
Preparation, spectra and thermal properties of two novel cyano-bridged complexes: crystal structure of one-dimensional copper(II)/palladium(II)
Article
Full-text available
  • Jan 2007
  • Z KRISTALLOGR
Two new coordination polymers, {-M(hydeten)(2)-NC-Pd(CH)(2)-CN}(n), [M = Ni and Cu, hydeten; N-(2-hydroxyethyl)-ethylenediamine)], have been synthesized and their elemental, thermal and spectroscopic (IR and UV-vis) properties have been studied. The crystal structure analysis of the Cu-Pd complex has indicated a polymeric chain -Cu(hydeten)(2)-NC-Pd(CN)(2)Cu(hydeten)(2)- in which the Pd(II) ions are four-coordinated by carbon atoms from four cyano groups in a square-planar arrangement, whereas Cu(II) ions are six-coordinated with two cis cyano N and four N atoms of bidentate hydeten ligands in a distorted octahedral arrangement.
View
Synthesis, crystal structure, electrochemical and kinetic studies on a cyano-bridged CuII–NiII–CuII hetero-trinuclear complex
Article
  • Mar 2007
  • POLYHEDRON
A cyano-bridged hetero-trinuclear complex, [Cu(HL)]2[Ni(CN)4] (2) (H2L = 3,9-dimethyl-4,8-diazaundec-3,8-diene-2,10-dione-dioxime) has been synthesized and characterized by single crystal X-ray structure determination. The square planar [Cu(HL)]+ cation (1), otherwise reluctant to bind axially, is converted to a square pyramidal geometry through axial ligation by the cyano group of [Ni(CN)4]2− ion in di-trans fashion. Electrochemical studies in MeCN give (i) E1/2(CuII/I) = −0.52 V and −0.55 V and (ii) E1/2(CuIII/II) = 1.15 and 1.23 V versus Ag/AgCl for complexes 1 and 2 respectively, whereas in aqueous solution, the corresponding E1/2(CuII/I) appear at −0.61 V and −0.58 V. The E1/2(CuIII/CuII) appears at 1.04 V for 2 only; no such process is encountered for the complex 1 at potential ⩽1.20 V. In addition to these there is a redox process, occurring in aqueous solution only, for the copper(II) bound ligand oxidation at 0.63 and 0.60 V versus Ag/AgCl for the complex 1 and 2 respectively. Both the complexes undergo acid catalyzed decomposition with a second-order dependence in H+. It is found that complex 2 decomposes at a rate ∼2 times faster than the complex 1. The kinetic studies on the periodate oxidation reveal that both HIO4 and IO4- are reacting species for the oxidation of 1, while HIO4 is the sole reacting species for the complex 2. Again, complex 2 reacts faster than 1. An inner-sphere mechanism has been invoked for both the complexes based on large Q, the association constant values.
View
Syntheses, IR spectra, thermal properties and crystal structures of novel cyano-bridged polymeric complexes of zincII and cadmiumII with tetracyanoplatinateII
Article
  • Jan 2008
  • POLYHEDRON
Two novel one-dimensional polymeric cyano-bridged platinum(II) complexes of N-(2-hydroxyethyl)-ethylenediamine (hydeten), [MII(hydeten)Pt(CN)2(μ-CN)2]n (MII = ZnII (1) and CdII (2)), were synthesized and characterized by physico-chemical methods (elemental analysis, IR spectroscopy and thermoanalytical measurements) and X-ray diffraction. Thermal behaviours of 1 and 2 were followed using TG and DTA (DSC) techniques. The 1D chain structures of 1 and 2 were verified by X-ray diffraction studies. According to the positions of the bridging cyano groups, in complex 1 the polymeric chains are built up via the 2,2-CT type, while in complex 2 the polymeric chains are built up via the 2,2-TT type.
View
View
Nickel(II) compounds of some nitro-substituted imine-triamine macrocycles; the structure of (5,7,7,13 tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene kappa(4) N-1,N-4,N-8,N-11)nickel(II) tetrachlorozincate(II)
Article
  • Apr 2006
  • POLYHEDRON
Reaction of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)nickel(II) cations with methanal and nitroethane in water or methanol plus base yields the nitro-substituted imine–triamine azamacrocyclic cation (5,7,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)nickel(II). Similar reaction with nitropropane yields the (13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)nickel(II) cation. Singlet ground state salts [Ni(L)]–(ClO4)2 and –ZnCl4 and triplet ground state compounds [Ni(L)(NCS)2], Ni(L)(NO2)]ClO4, [Ni(L)(C5H7O2)]ClO4 (pentan-2,4-dionato) and [{Ni(L)}2(C2O4)](ClO4)2 were prepared. (5,7,7,13-Tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)nickel(II) tetrachlorozincate has the nickel(II) ion in tetrahedrally twisted {±0.045(2)Å} square-planar coordination with the Ni displaced by 0.143(1)Å from the N4 mean plane, with distances Ni–N1=1.934(3), Ni–N4=1.909(3), Ni–N8=1.932(3) and Ni–N11=1.927(3)Å. The cation shows disorder in the location of the axial component of the gem-dimethyl group that was modeled with superposition of the 5,7,7,13-tetramethyl-4-ene and 5,5,7,13-tetramethyl-7-ene arrangements, with site occupation factors of 0.80(1) and 0.20(1), respectively. The nitro group is axially oriented, on the same side of the plane as the axial methyl substituent. The tetrachlorozincate ion is sited on the less crowded side of the cation plane, with one chloride ion axially located with Ni–Cl=2.921(1)Å.
View
N-rac-(5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14(1)-diene)copper(II): Structures of the perchlorate salt and a trinuclear tetracyanonickelato-bridged compound
Article
  • May 2006
  • POLYHEDRON
N-rac-(5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,14(1)-diene)copper(II) perchlorate, [C16H32CuN4](ClO4)2, is isostructural with the Ni(II) analogue. The cation has twofold symmetry (axis through Cu and the mid-points of the C2–C3 and C9–C10 bonds), with Cu–Namine=1.994(1) and Cu–Nimine=1.969(1)Å, with tetrahedral displacements of the N4 group of ±0.007(2)Å. The dimensions are compared with those of compounds of homologuous cations with 14–18 ring members. The cation forms a compound with a centrosymmetrical trinuclear tetracyanonickelate(II)-bridged cation di-μ-cyano-1:2κ2C:N;1:3κ2C:N-dicyano-1κ2C-bis(N-rac-5,7,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,1(14)-diene-κ4N1,4,8,11)copper(II)–nickel(II) tetra(cyano-κ1C)nickelate(II), [(C16H32N4)Cu–NC–Ni(CN)2–CN–Cu(C16H32N4)] [Ni(CN)4], with Cu–Namine=2.016(2), 2.002(2), Cu–Nimine=1.964(2), 1.987(2) and axial Cu–Ncyano=2.298(2)Å, Cu–NC=142.1(2)°. The CuN4 group of the azamacrocycle is appreciably bent {transN–Cu–N=160.30(7)°, 178.25(2)°}, with the Cu displaced towards the axial cyano nitrogen.
View
Copper(II) compounds of some nitro-substituted imine-triamine macrocycles: The structure of (aqua kappa(1)-O)-(13-ethyl-5,7,7-trimethyl-13 nitro-1,4,8,11-tetraazacyclotetradec-4-ene-kappa(4) -N-1,N-4,N-8,N-11)copper(II) perchlorate
Article
  • Mar 2006
  • POLYHEDRON
Reactions of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) perchlorate with methanal and nitroethane (or nitropropane) yield the nitro-substituted imine-triamine azamacrocyclic compounds (5,7,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)copper(II) {or (13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)copper(II)} perchlorate. Compounds of these cations [Cu(L)](ClO4)2, –ZnCl4, [Cu(L)(A)](ClO4)2, A=H2O, NH3 and [Cu(L)(X)]ClO4, X=NCS-,N3-,NO2-, were prepared. Aqua-(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)copper(II) perchlorate has the copper(II) ion in tetrahedrally twisted {±0.045(2)Å} square-planar coordination, with mean Cu–Namine=2.019(4)Å and Cu–Nimine=1.918(2)Å. Oxygen of water {Cu–O=2.279(2)Å} and perchlorate {Cu–O=2.905(2)Å} occupy the axial sites, with the Cu displaced by 0.143(1)Å from the N4 mean plane towards the water molecule. The cation has the 1R,8S,11S configuration, with the nitro substituent and one of the gem methyl substituents axially oriented to the side of the CuN4 plane away from the water molecule.
View
Hetero-metallic frameworks of [Pd(CN) 4] 2− and Cu(II) with triamines: A rare example of a tetracyanometallate bridged 2D coordination polymer
Article
  • Aug 2007
  • POLYHEDRON
Four cyano bridged Cu(II)–Pd(II) heterometallic complexes, [Cu(dpt)Pd(CN)4]n (1), {[Cu2(medpt)2Pd(CN)4](ClO4)2·3H2O}n (2), {[Cu2(dien)2Pd(CN)4](ClO4)2·2CH3OH}n (3) and {[Cu2(iPrdien)2Pd(CN)4](ClO4)2·2H2O}n (4) [dpt=3,3′-iminobispropylamine; medpt=3,3′-diamino-N-methyldipropylamine; dien=diethylenetriamine and iprdien=N′-isopropyldiethylenetriamine] have been synthesized and characterized by single crystal X-ray diffraction analysis, magnetic measurement and thermal study. Complexes 1, 2 and 3 are 1D coordination polymers, while 4 presents a 2D network. In 1, the cis-directed cyanide ligands of [Pd(CN)4]2− anions link two Cu(dpt) units to form a neutral coordination polymer, whereas in 2, 3 and 4, all the cyanide groups of [Pd(CN)4]2− take part in bonding with four adjacent Cu(II) ions, resulting in cationic coordination polymers counterbalanced by perchlorate anions. The structures are compared with those of analogous [Ni(CN)4]2− derivatives. The magnetic behavior shows antiferromagnetic interactions in all the complexes.
View
The structures of some (hexamethyl-1,5,9,13-tetraazacyclohexadecadiene)copper(II) compounds
Article
  • Mar 2009
  • POLYHEDRON
The structure of the crystalline azamacrocyclic product formed by reaction of bis(propane-1,3-diamine)copper(II) perchlorate with acetone has been determined as N-rac-(6,8,8,14,16,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,13-diene)copper(II)·N-meso-(6,8,8,14,14,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,16(1)-diene)copper(II) perchlorate, with the cis, 5,16(1)-diene, and trans, 5,13-diene, isomeric cations co-crystallised. The structures of three compounds crystallised from solutions of this mixture have been determined. N-rac-(6,8,8,14,14,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,16(1)-diene)copper(II) tetrachlorozincate has an irregular flattened tetrahedral coordination geometry with trans-N-Cu-N angles of 139.27(8)° and 155.94(8)°. (Hexamethyl-1,5,9,13-tetraazacyclohexadecadiene)(thiocyanato-N)copper(II) perchlorate has twofold symmetrical square-pyramidal cations. A (μ-cyano)-tetracyanonickelate(II) compound has two (hexamethyl-1,5,9,13-tetraazacyclohexadecadiene)copper(II) cations each with a single axially coordinated tetracyanonickelate(II) group. The compounds, except for the tetrachlorozincate(II) salt, show disorder in the location of the imine functions and axial methyl substituents, attributed to co-crystallisation of enantiomers for the N-rac-trans isomer and/or of rotated arrangements of the N-meso-cis isomer. For the thiocyanato and tetracyanonickelato compounds this disorder precluded unambiguous assignment of configuration.
View
Structure of bis(ethylenediamine)copper(II) tetracyanonickelate(II)
Article
Full-text available
  • Nov 1991
[Cu(C4H16N4)][Ni(CN)4], M(r) = 346.5, triclinic, P1BAR, a = 6.460 (9), b = 7.230 (10), c = 7.864 (15) angstrom, alpha = 106.81 (13), beta = 91.51 (14), gamma = 106.94 (12)-degrees, V = 333.9 (9) angstrom 3, Z = 1, D(m) = 1.71 (1), D(x) = 1.723 Mg m-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 3.55 mm-1, F(000) = 177, T = 293 K, final R = 0.056 for 1212 unique observed reflections. The structure consists of centrosymmetric [Cu(en)2]2+ (en = ethylenediamine) cations and [Ni(CN)4]2- anions linked together by two of the CN groups (the remaining two act as unidentate ligands) to form infinite chains running along the [111] direction. Bridging by the CN groups is clearly unsymmetrical [Ni-C = 1.850 (4) and Cu-N = 2.533 (4) angstrom], leading to four-coordinate Ni(II) species alternating with axially distorted octahedral Cu(II) groups along the chain [the equatorial Cu-N distances are 1.997 (3) and 2.001 (3) angstrom].
View
Synethesis and Crystal Structure of Bi(ethylenediamine)copper Tetracyanonickelate(II)
Article
  • Jan 2000
  • CHINESE J STRUC CHEM
The crystal structure of the title compound C8H16CuN8Ni has been determined by single crystal X-ray diffraction. The crystal is triclinic with space group P1, a = 6.494(3), b = 7.270(4), c = 7.936(5) Angstrom, alpha = 106.67(3), beta = 91.33(4), gamma = 106.80 (6)degrees, V = 341.3(3) Angstrom(3), Z = 1, M-r = 346.54, F (000) = 117, mu = 2.933mm(-1), D-c = 1.686 Mg/m(3). The final R factor is 0.0603 for 1214 unique observed reflections [I greater than or equal to 2 sigma(I)]. The structure consists of [Cu(en)(2)](2+) (en = ethylenediamine) cations and [Ni(CN)(4)](2-) anions linked together by two of the CN groups (the remaining two act as unidentate ligands) to form infinite chains, in the chain, the hydrogen bonds of N(4)... H-N(5) exist,with distance 3.148 Angstrom, at the same time the hydrogen bonds of N(4)... H-N(7a) and N(5)-H ... N(1a) (a: x-1, y-1, z-1) between the interchains also exist, with distances of 3.160 and 3.124 Angstrom, so it forms a three-dimensional structure of the title compound.
View
Tetracyanonickelate(II) compounds of some (tetraazamacrocycle)nickel(II) cations. The structure of catena-Di(μ-cyano)dicyano(N-meso-5,7,7,12,14,14-hexamethy1-1,4,8,11-tetraazacyclotetradeca-1, 11-diene)dinicke1(II) hydrate
Article
  • Jan 1984
Tetracyanonickelate(II) compounds of several (tetraazamacrocycle)nickel(II) cations have been prepared. The structure of the N-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca- 4,11-diene, hmtd, compound [Ni(hmtd)Ni(CN)4].H2O has been determined by X-ray diffractometry [monoclinic, a 1780.3(3), b 1063.41(7), c 1409.3(2) pm, β 120.54(1)º, 24, space group C2/c, R 0.021, Rw 0.030 for 2178 reflections] and shows a chain polymeric structure with trans singlet ground state [Ni(CN)4]2- groups linking parallel stacked triplet ground state [Ni(hmtd)]2+ groups. The triplet ground state nickel(II) ions have a tetragonally elongated coordination environment [Ni-N (mean macrocycle) 204.5(1) pm, Ni-N (N≡C) 220.7(1) pm]. Tetracyanonickelate compounds of macrocycles related to hmtd but with different substituents, macrocycle ring size, and/or numbers of imine and amine donor groups were prepared. Some are diamagnetic, with discrete cation and anion, while others are similar to the hmtd compound, and for the latter, tetragonal distortions were evaluated from the reflectance spectra. Magnetic susceptibilities and infrared spectra are reported.
View
583. Transition-metal complexes with aliphatic Schiff bases. Part III. Compounds formed by reaction of some 1,2-diamine complexes of copper(II) with some ketones
Article
  • Jan 1962
  • J Chem Soc
The reaction of the bisdiaminecopper(II) complexes of ethylenediamine, propylenediamine, and 1,1-dimethylethylenediamine with acetone are described. With ethylene- and propylene-diamine, compounds formed by reaction with two and with four mol. of acetone were obtained, while with 1,1-dimethylethylenediamine only the former could be prepared. No reaction occurred with 1,2-dimethylethylenediamine. The bisethylenediaminecopper(II) ion reacted similarly with two and with four mol. of ethyl methyl ketone. Evidence supporting a cyclic, tetradentate secondary amine-Schiff base structure for the compounds containing four ketone residues, and a tetradentate primary and secondary amine-Schiff base structure for the compounds with two ketone residues, and for their nickel(II) analogues, is presented. The visible and ultraviolet absorption spectra, and the magnetic susceptibilities of the compounds, are reported.
View
Some metal-ion complexes with ligands formed by reaction of amines with aliphatic carbonyl compounds. Part IV. Some compounds of nickel(II) and copper(II) formed by the diaminoethane?butanone reaction
Article
  • Jan 1972
  • Dalton Trans
Reaction of acetone with bis(diaminoethane)nickel(II) yields the bis-complex of the β-amino-ketone NH2CH2CH2NHC(CH3)2CH2COCH3, which acts as tridentate ligand. With bis(diaminoethane)copper(II), the complex of the linear pentadentate ligand NH2CH2CH2NHC(CH3)2CH2C(CH3):NCH2CH2NHC(CH3)2CH2COCH3 is formed. Observations on the reaction between the tris(diaminoethane) complexes and acetone, which yield isomeric macrocyclic complexes, and on the reaction between diaminoethane and acetone are reported.
View
ORTEP-3 for windows—a version of ORTEP-III with a graphical user interface (GUI)
Article
The crystallographic problem: The production, and the visibility in the published literature, of thermal ellipsoid plots for small-molecule crystallographic studies remains an important method for assessing the quality of reported results. Since the mid 1960s, the program ORTEP (Johnson, 1965) has been perhaps the most popular computer program for generating thermal ellipsoid drawings for publication. The recently released update of ORTEP-III (Johnson & Burnett, 1996) has some additional features over the earlier versions, but still relies on fixed-format input files. Many users will find this very inconvenient, and will prefer to obtain drawings directly from their crystallographic coordinate files. This new version of ORTEP-3 for Windows provides all the facilities of ORTEP-III, but with a modern Graphical User Interface (GUI). Method of solution: A Microsoft-Windows GUI has been added to ORTEP-III. All the facilities of ORTEP-III are retained, and a number of extra features have been added. The GUI is effectively an editor that writes ORTEP-III input files, but the user need not have any knowledge of the inner workings of ORTEP. The main features of this program are: (i) ORTEP-3 for Windows can directly read many of the common crystallographic ASCII file formats. Currently supported formats are SHELX (Sheldrick, 1993), GX (Mallinson & Muir, 1985), GIF (Hall, Allen & Brown, 1991), SPF (Spek, 1990), CRYSTALS (Watkin, Prout, Carruthers & Betteridge, 1996), CSD-XR and CSD-FDAT. In addition, ORTEP-3 for Windows will accept any legal ORTEP-III instruction file. (ii) Covalent radii for the first 94 elements are stored internally, and may be modified by the user. All bonds are calculated automatically, and any individual bonds may be selected for removal, or for a special representation. (iii) The graphical representations of thermal ellipsoids for any element or selected sets of atoms can be individually set. All the possible graphical representations of thermal ellipsoids in ORTEP-III are also available in ORTEP-3 for Windows. (iv) A mouse labelling routine is provided by the GUI. Any number of selected atoms may be labelled, and any available Windows font may be used for the labels. The font attributes, e.g. italic, bold, colour, point size etc. can also be selected via a standard Windows dialog box. (v) As well as HPGL and PostScript Graphics graphic metafiles, it is also possible to get high quality graphics output by printing directly to an attached printer. The screen display may be saved as BMP or PCX format metafiles, and may also be copied to the clip-board for subsequent use by other Windows programs, e.g. word processing or graphics processing programs. Colour is available for all these output modes. (vi) A simple text editor is provided, so that input files may be modified without leaving the program. (vii) Symmetry expansion of the asymmetric unit to give complete connected fragments may be carried out automatically. (viii) Unit-cell packing diagrams are produced automatically. (ix) A number of options are provided to control the view direction. The molecular view may be rotated or translated by button commands from the tool bar, and views normal to crystallographic planes may also be obtained. Software environment and program specification: The program will read several common crystallographic file formats which hold information on the anisotropic displacement parameters. The operation of the program is carried out via standard self-explanatory MS-Windows menu items and dialog boxes. Hard-copy output is either by HPGL or Encapsulated PostScript metafiles, or by directly printing the graphics screen. Hardware environment: The program is implemented for IBM PC compatible computers running MS-Windows versions 3.1x, Windows 95 or Windows NT. At least a 486-66 machine is recommended with 8 Mbytes of RAM, and at least 5 Mbytes of disk space. Documentation and availability: The executable program, together with full documentation, is available free for academic users from http://www.chem. gla.ac.uk/̃louis/ortep3. Although the program is written in Fortran77, a large number of nonstandard FTN77 calls are used to create the GUI. For this reason, the source code is not available.
View
Synthesis, structure and magnetic properties of a new one-dimensional copper(II) complex with [Cr(CN)6]3−. Comparison with the [Fe(CN)6]3− analogue
Article
  • Jan 2001
  • Dalton Trans
A new complex of formula {[Cu(L)][Cu(L)Cr(CN)6]ClO4·2H2O}n1 (L is meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been prepared from the reaction of [Cr(CN)6]3− and [Cu(L)]2+, and its structure and magnetic properties studied. The structure consists of a discrete [Cu(L)]2+ cation and an anionic fragment formed by [Cu(L)Cr(CN)6]− in which the CuII is coordinated to four N atoms of the macrocycle and two CN groups of the hexacyanometalate in trans positions to give a one-dimensional compound. The compound shows a moderate ferromagnetic coupling. In order to describe its magnetic data a new formula was developed for the magnetic susceptibility of an isotropic ferromagnetic S = 1/2 and 3/2 Heisenberg chain assuming a variation of χMTvs. the length N. The best least-squares fit gives J = 4.82 cm−1, g = 2.02 and R = 1.23 × 10−4.
View
Comparisons of thirteen- to sixteen-membered tetra-azacycloalkane copper(II) complexes derived from template syntheses involving nitroethane and formaldehyde. Crystal structures of (10-methyl-10-nitro-1,4,8,12-tetra-azacyclopentadecane)copper(II) and (3-methyl-3-nitro-1,5,9,13-tetra-azacyclohexadecane)copper(II) perchlorates
Article
  • Aug 1988
  • Dalton Trans
Reaction of the (1,11-diamino-4,8-diazaundecane)copper(II) ion with formaldehyde and nitroethane yields the co-ordinated 16-membered macrocycle 3-methyl-3-nitro-1,5,9,13-tetra-azacyclohexadecane (L4). The 13- to 15-membered analogues 12-methyl-12-nitro-1,4,7,10-tetra-azacyclotridecane (L1), 6-methyl-6-nitro-1,4,8,11-tetra-azacyclotetradecane (L2), and 10-methyl-10-nitro-1,4,8,12-tetra-azacyclopentadecane (L3) have been described, and structures reported for salts of the 13- and 14-membered complexes. Structures of compounds of the 15- and 16-membered ligands are now reported, and structural parameters for the series of copper(II) cations are compared. The [Cu(L3)]2+ and [Cu(L4)]2+ cations contain the copper in a distorted square plane of the macrocycle amine donors, with the pendant nitro group occupying one axial site (Cu–O 2.443 and 2.703 Å in the L3 and L4 compounds, respectively) and a perchlorate oxygen in the other (Cu–O ca. 2.58 Å in each case). The Cu–N distances lie in the range 2.005–2.093 Å in [Cu(L3)]2+ and 2.007–2.029 Å in [Cu(L4)]2+. The effect of ring size for the series on solution structures analysed by electronic and e.s.r. spectroscopy, on copper(II) reduction potentials, and on rate constants for acid hydrolysis are reported; the L2 cavity appears most appropriate for accommodating copper(II).
View
Synthesis of a thirteen-membered tetra-azamacrocycle employing formaldehyde and nitroalkanes directed by metal ions. Crystal structures of (12-methyl-12-nitro-1,4,7,10-tetra-azacyclotridecane)copper(II) perchlorate and �-chloro-1,1,1-trichloro-2-(12-methyl-12-nitro-1,4,7,10-tetra-azacyclotridecane)dicopper(II)
Article
  • Jan 1988
  • Dalton Trans
Reaction of formaldehyde and nitroethane or nitropropane with the copper(II) or nickel(II) complexes of 1,8-diamino-3,6-diazaoctane in methanol yields the complexed macrocycle 12-methyl-12-nitro-1,4,7,10-tetra-azacyclotridecane (L1) or the 12-ethyl analogue (L2). Both copper(II) and nickel(II) complexes were isolated as perchlorate salts. The latter exists in the singlet ground state, but tetrahydroborato and dithiocyanate nickel(II) compounds with triplet ground states were also isolated. The perchlorate salt of [Cu(L1)]2+, defined by a structure determination, consists of a linear polymer with bridging perchlorate groups occupying axial sites about a square plane of the macrocycle primary amines and the metal ion; Cu–N distances are 1.943(7) and 1.96(1)Å, with Cu–O at 2.62(1) and 2.65(2)Å. Slow crystallization of [Cu(L1)]2+ from chloride ion solution yielded a dark green complex of L1 which contained an equimolar amount of the [CuCl4]2– anion. An X-ray structure analysis defined the molecule as the binuclear neutral compound [Cu(L1)Cl(CuCl3)], with a single bridging chloride ion linking copper(II) ions in either a tetrahedron of chloride ions or a square-based pyramid of four nitrogen donors [Cu–N 2.006(4) and 2.022(3)Å] with an apical chloride ion [Cu–Cl 2.507(2)Å] which bridges to the second copper(II) ion. The Cu Cu distance is 3.928(2)Å, and there are no antiferromagnetic exchange interactions.
View
Unexpected assembly of a cyanide-bridged one-dimensional nickel(II) complex with alternating [Ni(TIM)] 2+ and [Ni(CN) 4] 2− ions (TIM=2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene)
Article
  • Apr 2000
  • INORG CHEM COMMUN
Crystals of a cyanide-bridged nickel(II) complex [Ni(TIM)][Ni(CN)4] (1) (TIM=2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) were formed by diffusion of [Ni(TIM)](ClO4)2 in MeCN and K3[Cr(CN)5(NO)] in H2O for two months. Complex 1 crystallized in the triclinic space group P-1 with a=7.610(2), b=8.096(2), c=9.392(2) Å, α=69.56(1), β=71.44(1), γ=84.66(2)°. The crystal structure confirmed the presence of cyanide-bridged nickel(II) chains. The [Ni(CN)4]2− moieties were shown to derive from the dissociation of [Cr(CN)5(NO)]3− and [Ni(TIM)]2+ owing to the stability of the [Ni(CN)4]2− ion. The coordination geometry around the six-coordinate nickel(II) ion is axially elongated octahedral with four nitrogen atoms of the macrocycle (Ni–N=2.008(2) Å) and two nitrogen atoms of the bridging cyanides (Ni–N=2.123(2) Å). The four-coordinate nickel(II) groups are square-planar with the Ni–C bond distances ranging from 1.858(2) to 1.861(3) Å.
View