Phenylmalonate-containing copper(II) complexes: Synthesis, crystal structure and magnetic properties

Article abstract of DOI:10.1002/ejic.200400260

Three new copper(II) complexes of formula [Cu(2,2′-bpy)(Phmal)(H ₂O)]·2H₂O (1), [{Cu(2,2′-bpym)(Phmal)}] _n (2) and [{Cu(phen)(Phmal)}]_n·3nH₂O (3) (Phmal = phenylmalonate; 2,2′-bpy = 2,2′-bipyridine; 2,2′-bpym = 2,2′-bipyrimidine; phen = 1,10-phenanthroline) have been prepared and their structures determined by X-ray diffraction techniques. Complex 1 is mononuclear whereas 2 and 3 are uniform chain compounds. The copper atoms in 1-3 are distorted square-pyramidal: two nitrogen atoms from the bidentate nitrogen heterocycle and two carboxylate oxygen atoms from the phenylmalonate ligand build the equatorial plane; the axial position is filled either by a water molecule (1) or a carboxylate oxygen atom from another phenylmalonate group (2 and 3). The values of the intrachain copper-copper separation through the phenylmalonate-carboxylate bridge in the anti-syn conformation are 4.6853(7) (2) and 5.014(3) A (3). The phenyl ring of the Phmal ligand in 1 produces an unusual intramolecular π-π stacking interaction with the Cu^II-(aromatic 2,2′-bpy) chelate ring. Intrachain edge-to-face phenyl-pyridyl and offset phen-phen-type interactions occur in 2 and 3, respectively. Magnetic susceptibility measurements of 2 and 3 in the temperature range 1.9-290 K show the occurrence of weak intrachain ferromagnetic interactions between the copper(II) ions through the phenylmalonate-carboxylate bridge [J = +0.10(1) (2) and +0.31(1) cm^-1 (3)]. These values are compared with those reported for malonate-containing copper(II) complexes with the same exchange pathway through the anti-syn carboxylate bridge. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400260

FULL PAPER
Phenylmalonate-Containing Copper(II) Complexes: Synthesis, Crystal
Structure and Magnetic Properties
[a]
[b]
[a]
[c]
´
´
´
Jorge Pasan, Joaquın Sanchiz, Catalina Ruiz-Perez,* Francesc Lloret, and
Miguel Julve[c]
Keywords: Copper / Magnetic properties / N ligands / O ligands
˚
) complexes of formula [Cu(2,2Ј- anti-syn conformation are 4.6853(7) (2) and 5.014(3) A (3).
Three new copper(II
bpy)(Phmal)(H2O)]·2H2O (1), [{Cu(2,2Ј-bpym)(Phmal)}]n (2) The phenyl ring of the Phmal ligand in 1 produces an unu-
and [{Cu(phen)(Phmal)}]n·3nH2O (3) (Phmal = phenylmalon- sual intramolecular π−π stacking interaction with the
ate; 2,2Ј-bpy = 2,2Ј-bipyridine; 2,2Ј-bpym = 2,2Ј-bipyrimid- CuII−(aromatic 2,2Ј-bpy) chelate ring. Intrachain edge-to-
ine; phen = 1,10-phenanthroline) have been prepared and face phenyl−pyridyl and offset phen−phen-type interactions
their structures determined by X-ray diffraction techniques. occur in 2 and 3, respectively. Magnetic susceptibility measu-
Complex 1 is mononuclear whereas 2 and 3 are uniform rements of 2 and 3 in the temperature range 1.9−290 K show
chain compounds. The copper atoms in 1−3 are distorted the occurrence of weak intrachain ferromagnetic interactions
square-pyramidal: two nitrogen atoms from the bidentate ni- between the copper(II) ions through the phenylmalonate-car-
trogen heterocycle and two carboxylate oxygen atoms from boxylate bridge [J = +0.10(1) (2) and +0.31(1) cm−1 (3)]. These
the phenylmalonate ligand build the equatorial plane; the values are compared with those reported for malonate-con-
axial position is filled either by a water molecule (1) or a car- taining copper(II) complexes with the same exchange path-
boxylate oxygen atom from another phenylmalonate group way through the anti-syn carboxylate bridge.
(2 and 3). The values of the intrachain copper−copper separa- ( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
tion through the phenylmalonate-carboxylate bridge in the Germany, 2004)
Introduction
prepare a large number of compounds with different struc-
tures and properties whose dimensionality goes from zero
in the mononuclear species [Cu(mal)(2,2Ј-bpym)][14] (2,2Ј-
bpym ϭ 2,2Ј-bipyrimidine) to three in the compound [Cu-
(mal)(pyz)]n (pyz ϭ pyrazine).[15] The variety of the coordi-
nation modes of the malonate ligand in these compounds
has been reviewed very recently.[9] From a magnetic point
of view, the parameters governing the nature and magni-
tude of the magnetic interactions between copper() ions
are the conformation of the bridge (anti-anti, anti-syn, syn-
syn), the environment of the metal atom,[16,17] and the rela-
tive orientation of the malonate-carboxylate bridge with re-
spect to the metal environment (equatorial-equatorial,
equatorial-apical and apical-apical with relatively strong,
weak and negligible interactions, respectively), in addition
to the CuϪO(carboxylate) distances.[10]
The design of synthetic pathways to obtain systems with
desired properties continues to be a challenge for inorganic
chemists. In this context, a great interest has been devoted
to the development of rational synthetic routes to novel po-
lynuclear compounds of tuneable dimensionality which
may have applications as molecule-based magnetic
materials.[1Ϫ3] Many recent reports have focused on the syn-
thesis and magneto-structural characterization of polymeric
transition metal compounds using malonate (dianion of
propanedioic acid, H2mal) as both blocking and bridging
ligand.[4Ϫ10] In the framework of our research with malon-
ate-containing metal complexes[8Ϫ13] we have been able to
[a]
Laboratorio de Rayos
X
y
Materiales Moleculares,
´
Departamento de Fısica Fundamental II, Universidad de La
Laguna,
More recently, we have started a systematic study on cop-
per() complexation by substituted malonate ligands such
as phenylmalonate (dianion of phenylmalonic acid,
H2Phmal). One of the aims of this study is to analyze the
influence that factors such as the withdrawing effect, the
rigidity and the possibility of specific attractive interactions
between phenyl rings can exert on the structure and mag-
netic coupling of phenylmalonate-containing copper()
complexes.[17] In a previous work, we have observed that
´
´
Av. Astrofısico Francisco Sanchez s/n, 38206 La Laguna
(Tenerife), Spain
E-mail: caruiz@ull.es
[b]
[c]
Laboratorio de Rayos
X
y
Materiales Moleculares,
´
´
Departamento de Quımica Inorganica, Universidad de La
Laguna,
´
´
Av. Astrofısico Francisco Sanchez s/n, 38204 La Laguna
(Tenerife), Spain
´
`
Departament de Quımica Inorganica/Instituto de Ciencia
´
`
Molecular, Facultat de Quımica, Universitat de Valencia,
Av. Dr. Moliner 50, 46100 Burjassot (Valencia), Spain
Eur. J. Inorg. Chem. 2004, 4081Ϫ4090
DOI: 10.1002/ejic.200400260
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FULL PAPER
the complex [{Cu(H2O)3}{Cu(Phmal)2}]n has a layered factor responsible for this structural feature.[19] A search in
structure induced by the phenyl groups and intralayer ferro- the Cambridge Structural Database has shown the existence
magnetic couplings through phenylmalonate-carboxylate of several compounds which present the same conformation
and -oxo bridges. Here we show how the structure and mag- (listed in Table 2). The value of the dihedral angle between
netic properties of this layered system are modified by the the mean planes in complex 1 is larger (25.5°) than in the
presence of coligands such as 2,2Ј-bipyridine (2,2Ј-bpy), other compounds (1.2Ϫ14.5°) due to geometrical con-
2,2Ј-bipyrimidine (2,2Ј-bpym) and 1,10-phenanthroline straints that preclude the parallel arrangement of the phenyl
(phen). These are all aromatic nitrogen heterocycles that, in group above the chelate ring. All the structures found in the
addition to their good coordinating ability (metalϪligand search contain a ligand with the nitrogen atoms inside the
bonds), can interact with the phenyl ring of the Phmal aromatic rings (i.e. always 2,2Ј-bpy or phen but never N,NЈ-
group (supramolecular interactions), making this system ethylenediamine). According to Janiak,[18] phenyl rings do
very appropriate to illustrate the effects of both types of in- not like to stack above each other but to adopt an offset
teractions.
(parallel displaced) arrangement, thus leading to CϪH···π-
We report herein the synthesis, crystallographic analysis type interactions. Therefore, we suggest that this is respon-
and magnetic study of the copper() complexes of formula sible for the situation of the phenyl group above the chelate
[Cu(2,2Ј-bpy)(Phmal)(H2O)]·2H2O (1), [{Cu(2,2Ј-bpym)- ring (i.e. displaced from the stacked position over the pyri-
(Phmal)}]n (2) and [{Cu(phen)(Phmal)}]n·3nH2O (3). Com- dyl groups). We can compare this structure with that of the
plex 1 is a magnetically isolated mononuclear species reported mononuclear complex [Cu(2,2Ј-bpy)(mal)-
whereas 2 and 3 are uniform chains with intrachain ferro- (H2O)]·H2O,[30] where the monomeric units are distributed
magnetic interactions.
in bilayers in the bc plane through hydrogen bonds involv-
ing the malonate-carboxylate groups and the coordinated
and uncoordinated water molecules. The hydrophobic inter-
actions in 1 form layers of different hydrophilic character
with the aromatic rings in one and the phenylmalonate oxy-
gen atoms and water molecules in the other one. A remark-
able difference between both compounds is the position of
the methylene group: it is directed toward the coordinated
water molecule in the malonate compound whereas the me-
talloaromaticity in the case of 1 causes the methylene CϪH
bond to point towards the opposite side of the coordinated
water molecule.
Results and Discussion
Synthesis of the Complexes
Complexes 1Ϫ3 were prepared by reaction of stoichio-
metric amounts copper() phenylmalonate with the appro-
priate heterocyclic N-donor in a methanol water mixture.
X-ray quality crystals of the mononuclear complex 1 and
the chain compounds 2 and 3 were grown from concen-
trated solutions by slow solvent evaporation.
Each copper atom in 1 exhibits a somewhat distorted
square-pyramidal environment, with a τ value[31] of 0.14.
The copper atom is bound to two 2,2Ј-bpy nitrogen atoms
Description of the Crystal Structures
˚
[2.001(2) and 1.998(2) A for Cu(1)ϪN(1) and Cu(1)ϪN(2),
[Cu(2,2Ј-bpy)(Phmal)(H2O)]·2H2O (1)
respectively] and to two carboxylate oxygen atoms from the
˚
The structure of 1 consists of neutral [Cu(Phmal)(2,2Ј- Phmal ligand [1.954(2) and 1.933(2) A for Cu(1)ϪO(2) and
bpy)(H2O)] mononuclear entities (Figure 1a) and crystalli- Cu(1)ϪO(4)] in the basal plane, and to a water molecule in
zation water molecules. The molecular units are linked by the apical position [2.143(2) A for Cu(1)ϪO(1w)]. The 2,2Ј-
˚
hydrogen bonding involving the uncoordinated phenylma- bpy and Phmal groups in 1 adopt a bidentate coordination
lonate oxygen atoms and the crystallization water mol- mode, the values of the angles subtended at the copper
ecules, with O···O distances ranging from 2.667(3) to atom by them being 80.53(8)° and 90.09(7)°, respectively.
˚
2.972(4) A (see Table 1). A surprising two-dimensional (6,3) The 2,2Ј-bpy ligand is practically planar [the value of the
net results (Figure 2) which contributes to the stabilization dihedral angle between the mean pyridyl planes is 1.1(1)°]
of the whole structure. Adjacent layers are linked by weak and its bond lengths and angles are in agreement with those
offset πϪπ-stacking interactions between pyridyl rings. The reported for free 2,2Ј-bpy.[32] The Phmal group exhibits the
shortest offset angle between pyridyl rings is 28.5° while boat conformation as in [{Cu(H2O)3}{Cu(Phmal)2}]n.[17]
˚
the shortest centroidϪcentroid contact is 3.966(4) A, values However, the Phmal group in this last compound simul-
which are slightly larger than the average values in πϪπ taneously exhibits bidentate (through two oxygen atoms of
interactions with pyridine-like groups previously re- the two carboxylate groups) and bis(monodentate) (through
ported.[18]
two trans carboxylate oxygen atoms from two Phmal li-
The molecular structure of 1 is remarkably similar to gands) coordination modes, leading to a layered structure.
that of the recently
reported[19,20] complexes The [Cu(Phmal)2]2Ϫ units in this compound tend also to
[Cu(Bzmal)(phen)(H2O)]·3H2O and [Cu(Bzmal)(2,2Ј- align their aromatic rings in the same direction, preventing
bpy)(H2O)]·2H2O (Bzmal 2-benzylmalonate) com- the occupation of one of the axial positions of the cop-
ϭ
pounds. The phenyl rings of Bzmal and Phmal are located per() coordination sphere, while the other apical site is
over the NϪCϪCϪNϪCu chelate ring in the three com- filled by another [Cu(Phmal)2]2Ϫ unit. This also occurs in
plexes and metalloaromaticity was pointed out to be the 1 where the aromatic ring practically fills one of the axial
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Phenylmalonate-Containing Copper(II) Complexes
FULL PAPER
Figure 1. Asymmetric unit of [Cu(2,2Ј-bpy)(Phmal)(H2O)]·2H2O (1) (a) and molecular fragments of [{Cu(2,2Ј-bpym)(Phmal)}]n (2) (b)
and [{Cu(phen)(Phmal)}]n·3nH2O (3) (c) with the numbering scheme
Eur. J. Inorg. Chem. 2004, 4081Ϫ4090
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FULL PAPER
Table 1. Hydrogen bonds in complex 1
DϪH···A[a]
D···A
ЄDϪH···A[b]
Symmetry operator[c]
O(1w)ϪH(1wa)···O(2w)
O(1w)ϪH(1wb)···O(3)
O(2w)ϪH(2wa)···O(1)
O(2w)ϪH(2wb)···O(3w)
O(3w)ϪH(3wa)···O(3)
O(3w)ϪH(3wb)···O(1)
2.667(3)
2.735(3)
2.881(4)
2.763(4)
2.972(4)
2.815(3)
170(4)
172(4)
172(6)
171(4)
167(5)
158(5)
x, y Ϫ 1, z ϩ 1
x ϩ 1/2, Ϫy, Ϫz ϩ 5/2
x, y ϩ 1/2, Ϫz ϩ 3/2
x ϩ 1, y, z
x Ϫ 1/2, Ϫy ϩ 1/2, z Ϫ 1
x Ϫ 1/2, Ϫy ϩ 1, Ϫz ϩ 3/2
[a]
[b]
[c]
˚
Values of the distances and angles in A and °, respectively.
D ϭ donor and A ϭ acceptor. Symmetry operation concerning the
acceptor atom.
positions of the copper coordination sphere and the other
one is occupied by a water molecule. The shortest intermo-
˚
lecular copperϪcopper separation in 1 is 7.6494(5) A
[Cu(1)ϪCu(1a); (a) ϭ Ϫx ϩ 2, Ϫy, Ϫz ϩ 2].
[{Cu(2,2Ј-bpym)(Phmal)}]n (2)
The structure of 2 consists of chains of [Cu(2,2Ј-
bpym)(Phmal)] units that are linked through one phenylmal-
onate-carboxylate group in an anti-syn conformation (Fig-
ure 1b). These chains run parallel to the a axis and interact
between themselves by means of πϪπ- and CϪH···π-type
interactions (Figure 3). There are two hydrophobic cavities
where 2,2Ј-bpym molecules and the phenyl rings from the
Phmal groups are constrained. The 2,2Ј-bpym groups are
involved in πϪπ interactions, with the shortest
˚
centroidϪcentroid contact being 3.798(6) A and the short-
est parallel displacement angle between pyrimidyl rings be-
ing 25.7°, values which are similar to the average ones ob-
served in πϪπ interactions with pyridine-like groups.[18]
Weak CϪH···π interactions are also present between the
phenyl rings and 2,2Ј-bpym groups inside the chains and
between phenyl groups of different chains, with the shortest
Figure 2. (6,3) pattern formed by hydrogen bonding involving the
coordinated and crystallization water molecules and the malonate
oxygen atoms; such a regular net contributes to the stabilization of
the structure; the 2,2Ј-bpy ligands have been omitted for clarity
˚
H···centroid distance being 2.86(4) A, and CϪH···centroid
Table 2. Stacking parameters of some compounds found in the Cambridge Structural Database with the same conformation as complex 1
Compound
Stacking parameters[a]
Ref.
˚
˚
˚
d(c1Ϫc2) [A]/α [°]
d[Ќc1ϪP(2)] [A]/β [°]
d[Ќc2ϪP(1)] [A]/γ [°]
[b]
[21]
[22]
[Cu(L1)(L2)]SbF6·CH2Cl2
[Cu(L3)(L4)(L5)]
[Cu(L3)(L4)](NO3)2·3H2O
3.58/1.2
3.49/13.1
3.45/14.3
3.43/18.5
3.37/8.0
3.49/13.2
3.38/8.2
3.49/7.2
3.50/10.2
3.44/6.46
3.39/10.1
3.53/14.5
3.49/2.1
3.51/8.2
3.48/5.2
3.32/11.4
3.41/12.1
3.29/4.3
[23]
[24]
[25]
[19]
[20]
[26]
[27]
[27]
[28]
[29]
catena-[Cu(L4)(L6)]ClO4·H2O
[Cu(L7)(L8)H2O]BF4·3H2O
[Cu(L9)(L8)H2O]Cl·H2O
[Cu(L10)(L4)H2O]·3H2O
[Cu(L10)(L8)H2O]·2H2O
[Cu(L11)(L8)H2O]NO3·MeOH·H2O
[Cu(L9)(L4)H2O]ClO4·1.5H2O
[Cu(L12)(L4)Cl]·3H2O
3.38/14.2
3.32/15.8
3.39/15.5
3.37/10.7
3.41/15.7
3.31/16.6, 3.32/12.0
3.41/5.6
3.39/19.7
3.36 /13.9
3.45/16.4
3.35/11.3
3.24/11.8, 3.30/10.3
3.44/9.2
3.38/8.8, 3.38/5.4
3.45/6.7
[Cu(L12)(L8)H2O]ClO4
[Cu(L9)(L13)H2O]ClO4·H2O
1
3.37/7.4
3.42/3.7
3.683/25.5
3.35/13.2
3.29/17.1
3.152/31.5
3.28/5.8
3.27/16.1
3.562/14.7
this work
[a]
P(1) ϭ plane 1; P(2) ϭ plane 2; c1 ϭ centroid of P(1); c2 ϭ centroid of P(2); α ϭ angle between mean planes; β ϭ angle between the
[b]
normal of P(1) and P(2); γ ϭ angle between the normal of P(2) and P(1). L1 ϭ (S,S)-2,6-bis(4-phenyl-2-oxazolin-2-yl)pyridine; L2 ϭ
benzyloxyacetaldehyde; L3 ϭ -4,5-dihydroxyphenylalanine; L4 ϭ 1,10-phenanthroline; L5 ϭ n-propanol; L6 ϭ -tryptophanate; L7 ϭ
,-2,5-dihydroxytyrosine; L8 ϭ 2,2Ј-bipyridine; L9 ϭ -tyrosinate; L10 ϭ 2-benzylmalonate; L11 ϭ -3-iodotyrosinate; L12 ϭ -phenyl-
alanine; L13 ϭ 1,4,8,9-tetraazatriphenylene.
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Phenylmalonate-Containing Copper(II) Complexes
FULL PAPER
groups being almost collinear. The building units of the bpym)(mal)(H2O)]·6H2O[14] shows once more the structural
chain are rotated 90° through the normal axis of the planar influence of the hydrophobic phenyl ring of the Phmal li-
2,2Ј-bpym group in a twist fashion (i.e. odd units in the gand. The complexation reaction between the preformed
same position and even units rotated by 90°; Figure 3).
[Cu(2,2Ј-bpym)]2ϩ species and the dicarboxylate mal and
Phmal ligands affords neutral hydrated mononuclear (mal)
and anhydrous chain (Phmal, 2) compounds. The structure
of the former exhibits extensive hydrogen bonds involving
coordinated and uncoordinated water molecules, whereas
carboxylate-bridging and supramolecular CϪH···π-type in-
teractions counterbalance the lack of hydrogen bonds in
the latter.
The shortest intrachain copperϪcopper separation in 2 is
˚
4.6853(7) A [Cu(1)···Cu(1c); (c) ϭ 1/2 ϩ x, 1/2 Ϫ y, z], a
value which is much shorter than the shortest interchain
˚
metalϪmetal distance [7.3634(8) A for Cu(1)···Cu(1d);
(d) ϭ Ϫx, 1 Ϫ y, 1 Ϫ z].
[{Cu(phen)(Phmal)}]n·3nH2O (3)
The structure of complex 3 consists of chains of [Cu-
(phen)(Phmal)] units linked through anti-syn carboxylate
bridges and crystallization water molecules (Figure 1c). The
chains run parallel to the a axis and they are linked by pairs
along the [011] direction through hydrogen bonds involving
the water molecules and noncoordinated carboxylate oxy-
gen atoms [the values of the O···O distance range from
˚
2.338(13) to 3.084(5) A; Figure 4]. Intrachain offset πϪπ
interactions between phen ligands occur, the shortest
centroidϪcentroid distance being 3.907(4) A and parallel
Figure 3. Fragment of the uniform chain of compound 2 showing
the rotation of the units by 90° and the intrachain CϪH···π interac-
tion (dashed line)
˚
displacement angle being 28.6°, in agreement with pre-
viously reported values.[18]
Each copper() atom has a slightly distorted square-pyr-
amidal surrounding, the τ value[31] being 0.08. Two nitrogen
Each copper() atom presents a slightly distorted square-
atoms of the 2,2Ј-bpym ligand [N(1) and N(2)] and two pyramidal environment, with a τ value[31] of 0.10. Two car-
carboxylate oxygen atoms from the Phmal ligand [O(2) and boxylate oxygen atoms from the Phmal ligand [O(2) and
O(4)] build the basal plane, whereas the symmetry-related O(4)] and the two nitrogen atoms of phen [N(1) and N(2)]
carboxylate oxygen atom [O(3b); (b) ϭ Ϫ1/2 ϩ x, 1/2 Ϫ y, form the equatorial plane, whereas a symmetry-related car-
z] occupies the apical position. The equatorial bond lengths boxylate oxygen atom [O(3e); (e) ϭ x ϩ 1, y, z] occupies
˚
vary in the range 1.900(3)Ϫ2.003(3) A and the apical bond the apical position. The equatorial bond lengths vary in the
˚
˚
length is 2.262(3) A. The 2,2Ј-bpym ligand is quasi planar range 1.913(2)Ϫ2.026(3) A and the apical bond amounts to
˚
[the dihedral angle between the pyrimidyl rings being 2.314(3) A. The angle subtended by the planar bidentate
3.5(1)°] and it acts as a bidentate ligand through two [N(1) phen ligand at the copper atom is 81.86(11)°. The bond
and N(2)] of its four nitrogen atoms. This coordination lengths and angles of the phen ligand in 3 agree well with
mode has previously been observed in several mono- those reported for the free molecule.[36] The conformation
and polynuclear 2,2Ј-bpym-containing copper() com- and coordination mode of the Phmal ligand in 3 are ident-
plexes.[14,33,34] The outer N(3) and N(4) 2,2Ј-bpym nitrogen ical to those in 2. However, πϪπ stacking between phen
atoms remain free, the N(3)···N(4) bite distance being some- ligands occurs in 3 instead of the CϪH(phenyl)···π(N-heter-
˚
what longer [2.811(6) A] than the N(1)···N(2) one [2.584(5) ocycle)-type interaction which occurs in 2. Moreover, the
˚
A] due to the bidentate coordination of the 2,2Ј-bpym to [Cu(phen)(Phmal)] chain units in 3 are not rotated by 90°,
the copper atom through N(1) and N(2). The inter-ring in contrast to what it is observed in 2; this modification of
˚
carbonϪcarbon bond length of 2,2Ј-bpym in 2 [1.480(6) A the crystal packing in 3 is due most likely to the crystalliza-
for C(13)ϪC(14)] is close to that found in the free ligand in tion water molecules which are present in the structure of
[35]
˚
the solid state [1.497(1) and 1.502(4) A].
As in 1, the the latter compound. A comparison between the structure
and that of the mononuclear complex
Phmal ligand adopts a boat conformation; the phenyl ring of
3
in 2 is placed perpendicular to the boat skeleton of the ma- [Cu(phen)(mal)(H2O)]·1.5H2O[37] reveals that weak πϪπ
lonate in order to establish the weak intrachain stacking interactions between phen ligands are present in
CϪH(phenyl)···π (pyrimidyl) interactions mentioned above. both compounds. However, the mononuclear units are gro-
Finally, a comparison between the structure of 2 and that uped by pairs in the malonato-containing complex, whereas
of the related mononuclear complex [Cu(2,2Ј- a uniform chain is formed in 3.
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J. Pasan, J. Sanchiz, C. Ruiz-Perez, F. Lloret, M. Julve
FULL PAPER
Figure 4. View of the uniform chain of compound 3 showing the phenylmalonate-carboxylate bridge in axial-equatorial anti-syn confor-
mation
The shortest intrachain copperϪcopper separation is
5.014(3) A [Cu(1)ϪCu(1f); (f) ϭ Ϫ1 ϩ x, y, z], a value
χ
M ϭ (Nβ2g2/4kT)(A/B)2/3
(1)
˚
where
which is much shorter than the shortest interchain
˚
metalϪmetal distance [7.5872(16) A for Cu(1)ϪCu(1g);
A ϭ 1.0 ϩ 5.7979916y ϩ 16.902653y2 ϩ 29.376885y3
29.832959y4 ϩ 14.036918y5
ϩ
ϩ
(g) ϭ Ϫ1/2 ϩ x, 1/2 Ϫ y, Ϫ1/2 ϩ z].
(2)
(3)
B ϭ 1.0 ϩ 2.7979916y ϩ 7.0086780y2 ϩ 8.6538644y3
4.5743114y4
Magnetic Properties
The χMT product of compound 1 obeys the Curie law in
the 5Ϫ300 K temperature range. Its value is 0.365 and y ϭ J/2kT, the spin Hamiltonian, H, being defined as
cm3molϪ1K, as expected for a magnetically isolated spin Σi ϪJ Si Siϩ1; J is the intrachain magnetic-coupling para-
doublet of a copper() ion. This is in agreement with its meter and N, g, and β have their usual meanings.
mononuclear nature.
The best fit obtained using a nonlinear regression analy-
The magnetic properties of compounds 2 and 3 in the sis leads to J ϭ ϩ0.10(1) cmϪ1, g ϭ 2.091(1) and R ϭ 2.6
form of χMT vs. T plots [χM being the molar susceptibility ϫ 10Ϫ5 for compound 2 and J ϭ ϩ0.31(1) cmϪ1, g ϭ
per copper() ion] are shown in Figure 5; χMT at room tem- 2.092(1) and R ϭ 2.1 ϫ 10Ϫ6 for compound 3 (R is the
perature is 0.41 cm3molϪ1K for both compounds, a value agreement factor defined as Σi[(χMT)obsd.(i)
Ϫ
which is as expected for a magnetically isolated spin doub- (χMT)calcd.(i)]2/Σ[(χMT)obsd.(i)]2. The calculated curves
let. Upon cooling, χMT remains almost constant for com- match very well the experimental data in the whole tem-
pound 2 down to 10 K and then smoothly increases at perature range, as seen in Figure 5. The fact that the mag-
lower temperatures to reach a value of 0.44 cm3molϪ1K at netization data of 3 at 2.0 K (see inset of Figure 5) are
1.9 K; χMT remains constant upon cooling down to 25 K clearly above the Brillouin function for a magnetically iso-
for compound 3 and then it increases at lower temperatures lated spin doublet (this is also observed for the correspond-
reaching a value of 0.50 cm3molϪ1K at 2.0 K. These fea- ing plot in 2) confirms the ferromagnetic nature of the in-
tures are indicative of an overall weak ferromagnetic coup- trachain magnetic coupling.
ling between the copper() ions in both compounds. Given
The weak ferromagnetic interactions in 2 and 3 can be
that the structures of 2 and 3 consist of uniform chains, understood in a simple manner by analysing the exchange
where the copper() ions are bridged by the phenylmalon- pathway which is involved and the relative arrangement of
ate-carboxylate group, we analyzed their magnetic proper- the magnetic orbitals. The unpaired electron of the cop-
ties through the numerical expression proposed by Baker per() ion in 2 and 3 (square-pyramidal environment) lies
and Rushbrooke[38] for a ferromagnetic uniform copper() in the equatorial plane [N(1)N(2)O(2)O(4)] and it is defined
2
2
chain [Equation (1)]:
by a dx Ϫy -type magnetic orbital [the x and y axes corre-
4086
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4081Ϫ4090

Phenylmalonate-Containing Copper(II) Complexes
FULL PAPER
for 2 [J ϭ ϩ0.10(1) cmϪ1] could be due to the greater value
of the angle between the apical-oxygen-to-copper vector
and the normal to the equatorial mean plane of the copper
atom (7° in 2 and only 3.6° in 3). In general, this shift influ-
ences the effectiveness of the bridge in the transmission of
the magnetic coupling because it modifies the overlap be-
tween the magnetic orbitals.
Another interesting point looking at the results listed in
Table 3 concerns compounds 3 and [{Cu(mal)(Im)}]n. Al-
though the structural parameters of 3 are similar to those
of [{Cu(mal)(Im)}]n, the value of the ferromagnetic coup-
ling for 3 is somewhat smaller. Most likely, the carboxylate
group of the phenylmalonate is less effective in the trans-
mission of the magnetic coupling than the carboxylate
group of the malonate ligand. The magnetic coupling is es-
sentially an electronic effect and the phenylene ring of the
phenylmalonate exerts an electron-withdrawing effect that
delocalizes some electron density of the copper() towards
the aromatic ring, decreasing the electronic delocalization
towards the carboxylate bridge. The decrease of the electron
delocalization towards the bridge would decrease the size
of the magnetic coupling. This could be one of the factors
to account for the weaker magnetic interaction between the
copper() ions in 3 (and also in 2) through the phenylma-
lonate-carboxylate bridge with respect to the malonate-car-
boxylate one.
Figure 5. Experimental temperature dependence of the χMT prod-
uct of 2 (circles) and 3 (triangles) at T Ͻ 50 K; (—) curves calcu-
lated from Equation (1); the inset shows the magnetization versus
H plot for 3 at 2.0 K, experimental data (circles), (—) Brillouin
function for a magnetically isolated spin doublet with g ϭ 2.09
sponding roughly to the equatorial bonds to the copper
atom]. The O(4)C(3)O(3) carboxylate bridge provides the
intrachain exchange pathway in 2 and 3: it links one equa-
torial position from Cu(1) [O(4)] with the axial one [O(3)]
at Cu(1c) (2) and Cu(1f) (3) (see Scheme 1) adopting the
anti-syn bridging mode. This exchange pathway produces a
very poor overlap between the magnetic orbitals due to the
weak spin density in the apical site.[39] Thus, the antiferro-
magnetic contribution, which is proportional to the square
of the overlap between the magnetic orbitals, is minimized
and the resulting magnetic coupling is most likely ferromag-
netic, as observed.[40]
Conclusions
Three new compounds have been prepared in which the
phenylmalonate ligand acts either as blocking (1) or as
bridging ligand (2 and 3). Weak interactions (hydrogen
bonding and πϪπ stacking) govern the structure of the
compounds leading to molecular (1) and one-dimensional
(2 and 3) structures. A comparison with the related malon-
ato-containing complexes reveals that the influence of the
phenyl group in the Phmal compounds is decisive: [Cu(2,2Ј-
bpy)(mal)(H2O)]·H2O presents different conformation and
crystal packing of the mononuclear units from those in
compound 1; compounds 2 and 3 are uniform chains
whereas the malonato-containing copper() complexes of
2,2Ј-bpym and phen are mononuclear compounds. The nat-
ure of the magnetic coupling between copper() ions
through the phenylmalonate-carboxylate bridge (ferromag-
netic) is the same as that through the malonate-carboxylate,
but its magnitude is somewhat smaller, probably due to the
electron-withdrawing effect which is exerted by the phenyl
ring. In the near future, magneto-structural studies on phe-
nylmalonate-containing copper() complexes will be pur-
sued to check this observation and to gain further insights
into the structural possibilities they provide.
Scheme 1
Previous examples of carboxylate-(anti-syn-)bridged cop-
per() complexes with an axial-equatorial exchange path-
way exhibit ferromagnetic couplings with values of J rang-
ing from ϩ0.05 to ϩ1.9 cmϪ1 (see Table 3).[8,10,16,41Ϫ43] The
intensity of the magnetic coupling is affected by the
CuϪO(axial) distance and the distortion of the metal en-
vironment — the longer the distance and the greater the
distortion, the weaker the coupling is. The values of J for 2
and 3 fall in this range, but they are smaller than those with
similar structural parameters [distortion and CuϪO(axial)
Experimental Section
General: Phenylmalonic acid (H2Phmal), copper() acetate hydrate
distance]. The low value observed for the coupling constant ([Cu(CH3COO)2·H2O]), 2,2Ј-bipyridine (2,2Ј-bpy), 2,2Ј-bipyrim-
Eur. J. Inorg. Chem. 2004, 4081Ϫ4090
www.eurjic.org  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 4087

´
´
J. Pasan, J. Sanchiz, C. Ruiz-Perez, F. Lloret, M. Julve
FULL PAPER
Table 3. Selected magneto-structural data for some (malonate-/phenylmalonate-)carboxylate-bridged copper() complexes
Compound[a]
Carboxylate pathway
CuϪ(O)ap
τ[31] Cu1/Cu2
J [cmϪ1 [b]
]
Ref.
[8]
[Cu(H2O)4][Cu(mal)2(H2O)2]
[Cu(H2O)4]2[Cu(mal)2(H2O)]2ϩ
[{Cu(H2O)3}{Cu(mal)2(H2O)}]n
[Cu(Im)2(mal)]n
equatorial-apical
equatorial-apical
equatorial-apical
equatorial-apical
equatorial-apical
equatorial-apical
equatorial-apical
equatorial-apical
2.383
2.381
2.185
2.394
2.270
2.611
2.262
2.314
oct[c]/0.05
oct[c]/0.12
0.24/0.28
0.02/0.02
0.18/0.18
oct[c]/oct[c]
0.08/0.08
0.10/0.10
ϩ1.8
ϩ1.2
ϩ1.9
ϩ1.6
[8]
[8]
[16]
[16]
[41]
[Cu(2-MeIm)2(mal)]n
{(H2bpe)[Cu(mal)2}]n·4nH2O
2
ϩ0.4
ϩ0.049
ϩ0.10
ϩ0.31
this work
this work
3
[a]
[b]
Abbreviations: Im ϭ imidazole; 2-MeIm ϭ 2-methylimidazole; bpe ϭ 1,2-bis(4-pyridyl)ethylene.
Values of the coupling constant
[c]
(J). Octahedral.
idine (2,2Ј-bpym), 1,10-phenanthroline (phen) and methanol were
purchased from Aldrich and used as received. Elemental analyses
(C, H and N) were performed with an EA 1108 CHNS-O micro-
stirring. The resulting pale-blue solution was concentrated to dry-
ness in a rotary evaporator. The green solid obtained was washed
thoroughly with acetone to remove the acetic acid and then the
analytical analyzer. IR spectra (450Ϫ4000 cmϪ1) were recorded green product was dissolved in water (15 mL).
with a Bruker IF S55 spectrophotometer with the sample prepared
[Cu(2,2Ј-bpy)(Phmal)(H2O)]·2H2O (1): 2,2Ј-Bipyridine (0.156 g,
as KBr pellets. Magnetic susceptibility measurements on polycrys-
talline samples of compounds 1Ϫ3 were carried out in the tempera-
ture range 1.9Ϫ290 K with a Quantum Design SQUID magnet-
ometer. Diamagnetic corrections of the constituent atoms were esti-
mated from Pascal’s constants[44] as Ϫ228 ϫ 10Ϫ6, Ϫ189 ϫ 10Ϫ6
and Ϫ251 ϫ 10Ϫ6 cm3·molϪ1 for compounds 1, 2 and 3, respec-
tively. Experimental susceptibilities were also corrected for the tem-
perature-independent paramagnetism (60 ϫ 10Ϫ6 cm3·molϪ1 per
CuII) and the magnetization of the sample holder.
1 mmol) was dissolved in methanol/water (50:50, 10 mL) and then
an aqueous solution (15 mL) of copper() phenylmalonate was ad-
ded whilst stirring. The solution was allowed to concentrate in a
fumehood at room temperature. Prismatic blue single crystals of 1
had grown after a few days. Yield: 0.34 g (75% based on copper).
C19H20CuN2O7 (451.55): calcd. C 50.49, H 4.43, N 6.20; found C
50.41, H 4.40, N 6.05. IR (KBr): ν(CϪH, ϭCϪH): 3090, 3062,
2950, 2923; ν(CϭC, COO): 1637, 1605, 1590, 1577, 1445, 1409
cmϪ1
.
Synthesis: The general procedure to prepare compounds 1Ϫ3 starts
with the preparation of an aqueous solution (15 mL) of copper()
phenylmalonate (1 mmol) which was prepared by adding phe-
nylmalonic acid (0.180 g, 1 mmol) to a warm methanolic solution
[{Cu(2,2Ј-bpym)(Phmal)}]n (2): Compound 2 was prepared similarly
to 1 but using a solution of 2,2Ј-bpyrimidine (0.158 g, 1 mmol) in-
stead of 2,2Ј-bipyridine. Prismatic greenish-blue single crystals of 2
(20 mL) of copper() acetate (1 mmol, 0.200 g) under continuous were grown after a few days. Yield: 0.24 g (60% based on copper).
Table 4. Crystallographic data for complexes 1Ϫ3
1
2
3
Empirical formula
Formula mass
Crystal system
Space group
C19H20CuN2O7
451.91
orthorhombic
Pcab
14.6113(5)
16.1928(4)
16.5067(5)
90
3905.5(2)
8
11.63
293(2)
1.537
0.71073
Ϫ18 Յ h Յ 20
Ϫ22 Յ k Յ 22
Ϫ23 Յ l Յ 13
5537 (0.060)
3552
C17H12CuN4O4
399.85
orthorhombic
Pcab
8.9331(3)
11.7577(3)
29.8171(4)
90
3131.77(14)
8
14.28
293(2)
1.696
0.71073
Ϫ12 Յ h Յ 9
Ϫ16 Յ k Յ 16
Ϫ41 Յ l Յ 41
4545 (0.132)
2985
C21H20CuN2O7
475.88
monoclinic
P21/n
5.014(3)
26.403(3)
14.685(3)
94.75
1937.3(12)
4
11.76
293(2)
1.611
0.71073
Ϫ7 Յ h Յ 5
Ϫ32 Յ k Յ 37
Ϫ13 Յ l Յ 20
5284 (0.051)
2872
˚
a [A]
˚
b [A])
˚
c [A]
β [°]
3
˚
V [A ]
Z
µ(Mo-Kα) [cmϪ1
T [K]
]
ρcalcd. [gcmϪ3
λ [A]
]
˚
Index ranges
Independent reflections (Rint
Observed reflections [I Ͼ 2σ(I)]
Parameters
)
343
283
336
Goodness-of-fit
R [I Ͼ 2σ(I)]
Rw [I Ͼ 2σ(I)]
1.043
0.0429
0.0837
1.138
0.0742
0.1462
1.012
0.0591
0.1098
R (all data)
Rw (all data)
0.0866
0.1004
0.1217
0.1615
0.1376
0.1302
4088
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 4081Ϫ4090

Phenylmalonate-Containing Copper(II) Complexes
C17H12CuN4O4 (399.55): calcd. C 51.05, H 3.00, N 14.02; found C nipulations were carried out with PARST97[47] and CRYS-
FULL PAPER
51.20, H 3.14, N 14.10. IR (KBr): ν(CϪH, ϭCϪH): 3057, 3027,
TALMAKER[48] programs. CCDC-235074 (1), -235075 (2) and
-235076 (3) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk].
2925; ν(CϭC, COO): 1646, 1606, 1578, 1557, 1420, 1403 cmϪ1
.
[{Cu(phen)(Phmal)}]n·3nH2O (3): Compound 3 was prepared simi-
larly to 1 but using a solution of 1,10-phenanthroline (0.180 g,
1 mmol) instead of 2,2Ј-bipyridine. Prismatic blue single crystals of
3 separated from the mother liquor on standing at room tempera-
ture after
a week. Yield: 0.38 g (80% based on copper).
C21H20CuN2O7 (475.55): calcd. C 52.99, H 4.21, N 5.89; found C
52.79, H 4.32, N 5.80. IR (KBr): ν(CϪH, ϭCϪH): 3060, 3030,
2923, 2850; ν(CϭC, COO): 1628, 1615, 1595, 1576, 1425, 1405 Acknowledgments
cmϪ1
.
This work was supported by the Ministerio Espan˜ol de Ciencia y
´
´
Tecnologıa (project BQU2001-3794) and the Gobierno Autonomo
X-ray Crystallographic Study: Single crystals of 1Ϫ3 were used for
data collection with a Nonius KappaCCD diffractometer. The data
collection was carried out at 293 K using graphite-monochromated
de Canarias (project PI2002/175). J. P. acknowledges the Ministerio
Espan˜ol de Educacion, Cultura y Deporte for a predoctoral fellow-
ship (ref. AP2001-3322).
´
˚
Mo-Kα radiation (λ ϭ 0.71073 A). A summary of the crystallo-
graphic data and structure refinement is given in Table 4 and selec-
ted interatomic distances and angles are listed in Table 5. The struc-
tures were solved by direct methods and refined with a full-matrix
least-squares technique on F2 using the SHELXL-97[45] program
included in the WINGX[46] software package. All non-hydrogen
atoms were refined anisotropically. All hydrogen atoms of struc-
tures 1Ϫ3 were located from difference maps and refined with iso-
tropic temperature factors, except those of the water molecules of
complex 3. The final geometrical calculations and graphical ma-
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1.933(2) Cu(1)ϪO(1w)
2.001(2)
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1.922(3) Cu(1)ϪN(2)
1.900(3) Cu(1)ϪO(3b)
2.003(3)
1.996(3)
2.262(3)
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O(2)ϪCu(1)ϪO(3b) 106.32(12) N(1)ϪCu(1)ϪO(3b) 85.78(12)
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´
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1.934(2) Cu(1)ϪO(3e)
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91.90(10) N(2)ϪCu(1)ϪO(3e)
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