Organic-inorganic hybrid materials: Syntheses, X-ray diffraction study, and characterisations of manganese, cobalt, and copper complexes of modified bis(phosphonates)

Article abstract of DOI:10.1002/zaac.200900555

Four new cobalt, manganese, and copper bis(phosphonates), [Co ₂{Cl₂C(PO₃)₂}(H₂O) ₇·4H₂O] (1), [Co{Cl₂C(PO ₂O(C(O)C₆H₅))₂(H₂O) ₅·2H₂O(Cl₂C(PO₂O(C(O)C ₆H₅))₂} {Co(H₂O)₆}] (2), [Mn{[Cl₂C(PO₂O(C(O)C₆H₅)) ₂](H₂O)₃}] (3), and [Cu{(CH₂C ₅H₅N)C(OH)(PO₃H)₂} ₂·4H₂O] (4), were prepared by gel, liquid, and evaporation crystallisation methods. Compounds 1-4 were characterised by X-ray single-crystal diffraction, elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The effects of metal and various substituted groups in bis(phosphonate) ligands on the structure formation of bis(phosphonates) were studied. In the structure of 1, the clodronic acid ligand (Ll) is in bischelating bonding mode, and the dinuclear units of 1 are surrounded by two-dimensional water cluster patterns. The hydrogen bond network of compound 1 is extended to a threedimensional framework when the phosphonate oxygen atoms serve as hydrogen-bond acceptors. In complex 2, the CoO₆ octahedron shares a corner of one PCO₃ tetrahedron of the dibenzoyl derivative of clodronic acid ligand (L2), and forms a two-dimensional hydrogen bonding network, which consists of [Co(H₂O)₆}]₂₊ cations, lattice water molecules and L2 ligand molecules. Compound 3, in turn, consists of dimeric building blocks built up of PCO3 tetrahedra of the ligand L2, which connect the corner-sharing MnO₆ octahedra and form an overall 2D structure through hydrogen bonds of coordinated and crystal water molecules and phosphonate oxygen atoms. Complex 4 is among the first metal complexes of risedronic acid (L3). In compound 4, two L3 ligand molecules chelate tridentately the Cu^II atom at the center of symmetry, and the monomelic units of 4 are connected to a 3D structure through hydrogen bonding of coordinated and lattice water molecules to both protonated and deprotonated phosphonate oxygen atoms and protonated nitrogen, atoms in the pyridine ring.

Full text of DOI:10.1002/zaac.200900555

ARTICLE
DOI: 10.1002/zaac.200900555
Organic-Inorganic Hybrid Materials: Syntheses, X-ray Diffraction Study,
and Characterisations of Manganese, Cobalt, and Copper Complexes of
Modified Bis(phosphonates)
Susan Kunnas-Hiltunen,*[a] Elina Laurila,[a] Matti Haukka,[a] Jouko Vepsäläinen,[b] and
Markku Ahlgrén[a]
Keywords: Bisphosphonates; Organic-inorganic hybrid composites; Manganese; Copper; Cobalt
Abstract. Four new cobalt, manganese, and copper bis(phosphonates), a corner of one PCO3 tetrahedron of the dibenzoyl derivative of clo-
[Co2{Cl2C(PO3)2}(H2O)7·4H2O] (1), [Co{Cl2C(PO2O(C(O)C6H5))2-
(H2O)5}·2H2O{Cl2C(PO2O(C(O)C6H5))2}{Co(H2O)6}] (2), [Mn{[Cl2-
C(PO2O(C(O)C6H5))2](H2O)3}] (3), and [Cu{(CH2C5H5N)C(OH)-
(PO3H)2}2·4H2O] (4), were prepared by gel, liquid, and evaporation
crystallisation methods. Compounds 1–4 were characterised by X-ray
single-crystal diffraction, elemental analysis, infrared spectroscopy,
and thermogravimetric analysis. The effects of metal and various sub-
stituted groups in bis(phosphonate) ligands on the structure formation
of bis(phosphonates) were studied. In the structure of 1, the clodronic
acid ligand (L1) is in bischelating bonding mode, and the dinuclear
units of 1 are surrounded by two-dimensional water cluster patterns.
The hydrogen bond network of compound 1 is extended to a three-
dimensional framework when the phosphonate oxygen atoms serve as
dronic acid ligand (L2), and forms a two-dimensional hydrogen bond-
ing network, which consists of [Co(H2O)6}]2+ cations, lattice water
molecules and L2 ligand molecules. Compound 3, in turn, consists of
dimeric building blocks built up of PCO3 tetrahedra of the ligand L2,
which connect the corner-sharing MnO6 octahedra and form an overall
2D structure through hydrogen bonds of coordinated and crystal water
molecules and phosphonate oxygen atoms. Complex 4 is among the
first metal complexes of risedronic acid (L3). In compound 4, two L3
ligand molecules chelate tridentately the CuII atom at the center of
symmetry, and the monomeric units of 4 are connected to a 3D struc-
ture through hydrogen bonding of coordinated and lattice water mole-
cules to both protonated and deprotonated phosphonate oxygen atoms
hydrogen-bond acceptors. In complex 2, the CoO6 octahedron shares and protonated nitrogen atoms in the pyridine ring.
structure formation, these ions/molecules are able to connect
Introduction
the adjacent molecules, chains, or layers to higher dimension-
alities through coordinative bonds [3] or hydrogen bonds [2a,
4], respectively. Crystal water and coordinated water may form
water clusters through hydrogen bonding. These observations
were widely studied both theoretically and experimentally to
provide information about the bulk properties of water.
Water is a very important factor in many biological and
chemical processes, and it is also important in the designing of
new metal-organic framework structures [5]. Thus, the metal
bis(phosphonates) are capable of forming both one-dimen-
sional (1D) coordination polymers [2a, 6] as well as two-di-
mensional (2D) [7] and three-dimensional (3D) [2b–2d, 3c–
3e, 4b, 4c, 7a, 8] networks. In addition, 3D microporous and
mesoporous bis(phosphonate) frameworks may have chemi-
cally and thermally stabile voids or channels that can be filled
by inorganic cations, anions or neutral molecules [1b, 2, 9].
Hence, metal bis(phosphonates) have versatile applications, for
example, in the sorption of organic molecules and as catalysts
for inorganic and organic synthesis [1]. In addition, metal
phosphonates have magnetic properties at low temperatures if
the metal is paramagnetic [1].
Polyfunctional ligands, for example bis(phosphonates) [alter-
natively named di(phosphonates)], have interesting potential
properties for crystal engineering, since they are versatile
building blocks. Between the phosphonate groups exists a sta-
ble organic backbone (H2O3P–R–PO3H2, R = alkyl or aryl),
which is a spacer whose length and shape can be modified,
and the inorganic parts have six possible donor oxygen atoms
to form structure-strengthening chelate rings with metal cati-
ons [1]. In addition, the degree of protonation/deprotonation
and the presence of other cations, anions, or neutral molecules
in the starting mixture may have an effect on the dimensional-
ity [2]. When, for example, Na+ or lattice water participate in
* S. Kunnas-Hiltunen
Fax: +358-13-251-3390
E-Mail: Susan.Kunnas-Hiltunen@joensuu.fi
[a] Department of Chemistry
University of Joensuu
P. O. Box 111
80101 Joensuu, Finland
[b] Department of Chemistry
University of Kuopio
P. O. Box 1627
70211 Kuopio, Finland
Geminal bis(phosphonates), [H2O3P–(R1)C(R2)–PO3H2,
R1 = H, Cl, OH and R2 = Cl, CH3, amine, alkyl chain with
heterocyclic amine etc.] have a strong ability to bind metal
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.200900555 or from the
author.
710
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 636, 710–720

Mn, Co and Cu Complexes of Modified Bis(phosphonates)
cations, especially calcium in hydroxyapatite crystals. This plex of risedronic acid (L3) [Cu{(CH2C5H5N)C(OH)-
gives them an important function in the treatment of diseases (PO3H)2}2·4H2O] (4).
affecting bone tissue and in inhibiting the mineralisation of
soft tissues. The best-known drugs for the treatment of hyper-
calcaemia and osteoporosis are non-nitrogen-containing clodo- Results and Discussion
nate, e.g. disodium dichloromethylenebis(phosphonate) tetra-
Crystal Structure of [Co2{Cl2C(PO3)2}(H2O)7·4H2O] (1)
hydrate, and nitrogen-containing risedronate, e.g. monosodium
1-hydroxy-2-(3-pyridinyl)ethylidenebis(phosphonic) acid [10].
The asymmetric unit of complex 1 consists of two independ-
Clodronate and its analogues are highly hydrophilic com-
ent cobalt atoms, one L1 ligand, seven aqua ligands and four
pounds, and therefore their absorption in the human body has
lattice water molecules. The deprotonated clodronic acid li-
to be improved. The hydrophilic phosphonic acid groups can
gand L1 has a bischelating bonding mode, where two phos-
be masked so that the compound formed is more hydrophobic
phonate PCO3 tetrahedra share corners of two CoO6 octahedra.
and will release the parent clodronate after absorption by
In addition, the CoO6 octahedron shares corners through μ-
chemical and/or enzymatic hydrolysis reactions according to
H2O ligand oxygen atom O6, and thus, form a cluster-like
the prodrug principle [11]. Among the other clodronic dianhy-
structure. The other coordination sites of the atoms Co1 and
drides, P,P'-dibenzoyl-dichloromethylenebis(phosphonate) di-
Co2 are occupied by aqua ligands (see Figure 1). The variety
sodium salt is the first reported bioreversible prodrug of clo-
of the Co1–O [(Co1–O)av = 2.1095 Å] and Co2–O [(Co2–
dronate [11a]. In addition, the hydrophobic groups can be
O)av = 2.1076 Å] bond lengths shows the distortion of the
added to the carbon bridge between the phosphonate groups,
CoO6 octahedron (see Table 1), where the longest Co–O bonds
as has been done with etidronate [hydroxyethylidenebis(phos-
are between the cobalt atoms and the μ-H2O oxygen atom. The
phonate)], pamidronate [3-ammonium-1-hydroxypropylidene-
O–Co1–O angles lie in the range of 86.0–179.1 °, and the
1,1-bis(phosphonate)] and risedronate. In risedronate, the hy-
O–Co2–O angles in a range from 85.3 to 175.6 °. The interme-
droxyl group and a carbon chain, containing a nitrogen atom
tallic Co1–Co2 distance amounts 3.8380(3) Å. Compound 1
within a heterocyclic ring, enhance the binding to human bone
is isostructural with the previously published nickel and zinc
[10a]. Several metal complexes of medronate [methylene-
complexes of clodronic acid [16], and the M–O bond lengths
bis(phosphonate)] [6a, 6b, 7b, 8a], etidronate [6c–6e, 7c–7f,
and the O–M–O angles follow the same pattern. In addition, a
8b–8e], clodronate, and its derivatives [12] were prepared and
similar bischelating bonding mode is found, for example, in
characterised, but the number of metal complexes of this kind
of modified bis(phosphonates) is very limited.
the cobalt and vanadium complexes of medronate [8f, 15],
copper complexes of etidronate [8c–8d], aluminium complexes
of ethylenediphosphonate [16], magnesium complexes of clo-
dronate [3a] and calcium [12a] and cadmium [12b] complexes
of monoethyl, and cobalt complexes of P-piperidinium-P'-
methyl [12c] derivatives of clodronate.
We previously reported about the alkaline earth metal [3a,
13] and the nickel and zinc complexes of the dibenzoyl deriva-
tive of clodronic acid, as well as their hydrolysis products, the
nickel and zinc complexes of clodronic acid [14]. The results
showed that the dibenzoyl derivative of clodronic acid can ap-
pear in various bridging and chelating modes as ligand, and it
always forms 2D crystal structures with or without hydrogen
bonding, even though two of the phosphonate oxygen atoms
are masked with dibenzoyl groups. The clodronic acid ligand,
in turn, can form a 3D hydrogen bonding network through
water clusters and phosphonate oxygen atoms [14]. Our idea
was to produce single crystals of bis(phosphonate) metal com-
plexes and to study their structural properties for further re-
search in the area of solid-state chemistry. In addition, this
study provides important information in support of research
into bis(phosphonates) as pharmaceutical products. Although
the metals used in this study are toxic, the first row transition
metal complexes are good model structures; they have similar
sizes of the ionic radiuses than alkaline earth metals.
Four new manganese, cobalt, and copper bis(phosphonate)
crystal structures determined by X-ray diffraction, elemental
analysis, IR spectroscopy, and thermogravimetric analysis are re-
ported in this article. The complexes were the cobalt complex of
clodronic acid (L1) [Co2{Cl2C(PO3)2}(H2O)7·4H2O] (1),
the cobalt and manganese complexes of the dibenzoyl derivative
of clodronic acid (L2) [Co{Cl2C(PO2O(C(O)C6H5))2(H2O)5}·
2H2O{Cl2C(PO2O(C(O)C6H5))2}{Co(H2O)6}] (2), and [Mn-
In the packing scheme of complex 1, the crystal water mole-
cules surround the inorganic parts of the dinuclear motifs,
which are organised in zig-zag mode along the [100] plane
(Figure 1). After the lattice water was removed, the space that
crystal water accommodates was determined by means of the
PLATON software SOLV [17] to be 158.8 Å3 (9.1 % of the
total unit cell volume), where as the corresponding values of
the previously reported nickel and zinc complexes of clodronic
acid were 286.6 Å3 (16.8 %) and 460.0 Å3 (23.2 %), respec-
tively [14]. The shape of the solvent-accessible space in com-
plex 1 is illustrated as a space-filling model in Figure 2, made
with the PLATON software CAVITY [17]. Compound 1 has
as many coordinated and crystal water molecules as the nickel
complex of clodronic acid [Ni2{Cl2C(PO3)2}(H2O)7·4H2O]
[14]. Thus, the slightly different packing of the lattice water
has an influence on the size of the space that the water molecu-
les accommodate. In turn, the zinc complex of clodronic acid
[Zn2{Cl2C(PO3)2}(H2O)7·6H2O] has more lattice water mole-
cules, which surround the whole dimeric zinc clodronate units
[14]. In complex 1, the solvent-accessible spaces do not pene-
trate the structure continuously, as in the nickel and zinc com-
plexes, but the lattice water is blocked inside the structure.
The coordinated water molecules and the crystal water of
{[Cl2C(PO2O(C(O)C6H5))2](H2O)3}] (3), and the copper com- compound 1 form infinite hydrogen-bonded tapes along the
Z. Anorg. Allg. Chem. 2010, 710–720
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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S. Kunnas-Hiltunen et al.
ARTICLE
Table 1. Selected M–O bond lengths /Å and O–M–O angles /° for
compound 1.
1
Co1–O5
Co1–O2
Co1–O4
Co1–O1
Co1–O3
Co1–O6
2.0263(11)
2.0550(11)
2.0764(11)
2.1179(11)
2.1582(11)
2.2232(11)
Co2–O10
Co2–O7
Co2–O13
Co2–O12
Co2–O11
Co2–O6
2.0311(11)
2.0741(11)
2.0818(11)
2.1248(11)
2.1327(11)
2.2010(11)
O5–Co1–O2
O5–Co1–O4
O2–Co1–O4
O5–Co1–O1
O2–Co1–O1
O4–Co1–O1
O5–Co1–O3
O2–Co1–O3
O4–Co1–O3
O1–Co1–O3
O5–Co1–O6
O2–Co1–O6
O4–Co1–O6
O1–Co1–O6
O3–Co1–O6
179.10(5)
93.51(4)
87.39(4)
89.28(4)
89.83(4)
175.09(4)
92.96(4)
86.89(4)
97.47(4)
86.40(4)
92.75(4)
87.28(4)
89.87(4)
85.96(4)
170.40(4)
O10–Co2–O7
O10–Co2–O13
O7–Co2–O13
O10–Co2–O12
O7–Co2–O12
O13–Co2–O12
O10–Co2–O11
O7–Co2–O11
O13–Co2–O11
O12–Co2–O11
O10–Co2–O6
O7–Co2–O6
94.06(4)
174.42(5)
91.33(4)
85.30(4)
175.58(4)
89.44(4)
91.27(4)
94.70(4)
86.82(4)
89.69(4)
95.32(4)
88.10(4)
86.33(4)
87.60(4)
172.65(4)
O13–Co2–O6
O12–Co2–O6
O11–Co2–O6
Figure 1. Molecular structure of 1 with numbering scheme and ther-
mal ellipsoids (50 %, top image). Packing of the dinuclear motifs of
1 (bottom image, PCO3 tetrahedron = dark grey; CoO6 octahedron =
light grey).
crystallographic c axis, where the (H2O)10 rings are joined to-
gether by the intramolecular O16···O15 hydrogen bonds (see
the black dashed lines in Figure 2). The (H2O)10 ring includes
the intramolecular O1···O17, O12···O16, and O1···O16, and the
intermolecular O17···O15i, O15···O12ii hydrogen bonds with
an average O···O distance of 2.813 Å and O–H···O angles of
134.1–166.1 °. The O···O distance is longer than the corre-
sponding value of ice Ih (2.759 Å [5c]), and slightly shorter
than the distance of liquid water (2.854 Å [5c]), In addition,
the phosphonate oxygen atoms serve as hydrogen-bond accept-
Figure 2. Space-filling illustrations of solvent accessible voids of com-
pound 1 (top image, unoccupied space appears as white space-filling,
metal atoms as black spheres, phosphorus atoms as grey spheres, chlo-
rine atoms as grey spheres and oxygen atoms as light grey spheres).
Close view of the hydrogen bonding of the water clusters in compound
1 (bottom image, PCO3 tetrahedron = grey; oxygen atoms = dark grey;
hydrogen atoms = light grey; hydrogen bond interactions = grey and
black dashed lines.).
ors, and the overall hydrogen bond network is three-dimen- the range of 2.646(2)–3.115(2) Å and the angles of 134.1–
sional. In addition to the above mentioned hydrogen bonds, the 160.3 °. The intermolecular O16···O8iii, O12···O4iii, O6···O14iv,
intramolecular O2···O17, O14···O9, O6···O16 distances lie in O2···O10iv, O15···O8iii, O17···O9v, O3···O5v, O13···O14iv,
712
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Z. Anorg. Allg. Chem. 2010, 710–720

Mn, Co and Cu Complexes of Modified Bis(phosphonates)
O13···O7vi, O16···O9vii, O3···O15v, O11···O7vi, O11···O3iii, and can be seen in the bond lengths of Co1–O [(Co1–O)av =
O14···O8viii distances vary from 2.646(2) Å to 3.052(2) Å 2.0865 Å] and Co2–O [(Co2–O)av = 2.1028 Å] (Table 2). The
(symmetry code: i: –x, 1–y, –z; ii: x, 0.5–y, –0.5+z; iii: 1–x, – longest Co1–O bond lengths are between Co1 and the aqua
0.5+y, 0.5–z; iv: 1–x, 0.5+y, 0.5–z; v: 1–x, 1–y, –z; vi: 1–x, 1– ligand oxygen atom O10 and between Co1 and the phosphon-
y, 1–z; vii: –1+x, y, z; viii: 2–x, –0.5+y, 0.5–z); and the bond ate oxygen atom O1, respectively. The O–Co1–O angles are in
angles are in the range 145.7–172.5 °. The O16···Cl4vii and the range of 84.01(8)–175.93(9) °. The [Co(H2O)6}]2+ octahe-
O16···Cl3vii distances of 3.2726(12) and 3.2860(12) Å and the dron is distorted by the Co2–O14 and Co2–O19 bonds, which
O16···H16B···Cl4 and O16···H16B···Cl3 angles of 120.8 and are the longest bonds in the octahedron, respectively. The O–
116.9 °, respectively, indicate intermolecular interaction be- Co2–O angles range from 84.22(8)–179.28(9) °.
tween the lattice water molecule O16 and both of the chlorine
atoms.
The intramolecular hydrogen bonds are formed between the
O17···O1B, O19···O1B, O16···O21, O10···O6, O11···O5B,
O12···O19, O21···O5B, and O12···O4 atoms, with distances of
2.633(3)–2.798(3) Å and angles of 147.9–177.5 °. All mono-
meric units of 2 are packed facing in the same direction, one
on top of the other, along the crystallographic a axis as a result
of intermolecular hydrogen bonding between the aqua ligand,
lattice water molecules and phosphonate oxygen atoms
through O15···O21i, O10···O18ii, O15···O6iii and O14···O6iii
with distances of 2.690(3)–2.778(3) Å and angles of 135.3–
168.1 ° (Figure 3). The 2D layer-like hydrogen bond network
along the [001] plane is formed through intermolecular hydro-
gen bonds in the direction of the crystallographic b axis. The
Crystal Structure of [Co{Cl2C(PO2O(C(O)C6H5))2(H2O)5}·
2H2O{Cl2C(PO2O(C(O)C6H5))2}{Co(H2O)6}] (2)
The asymmetric unit of complex 2 consists of one L2 ligand
sharing a corner of one CoO6 octahedron through the PCO3
tetrahedron. The coordination sphere of the cobalt ion is com-
pleted by five aqua ligands. In addition, the asymmetric unit
consists of two lattice water molecules, one lattice L2 ligand
and one lattice [Co(H2O)6}]2+ cation (see Figure 3). All phos-
phonate oxygen atoms of the ligand L2 and the lattice ligand
L2 are unprotonated. The distortion of the CoO6 octahedron
intermolecular
O14···O5iv,
O18···O2Bi,
O13···O6Bi,
O11···O20iv, O20···O2ii, O17···O10iv, O19···O2Bi, O16···O5iv,
O21···O20iv, O18···O8Biii, O13···O4Bv, O9···O14v, O20···O1v,
O9···O8Bi, and O19···O6Bi distances vary between 2.653(3)
and 3.122(3) Å (symmetry code: i: 1+x, y, z; ii: –1+x, 1+y, z;
iii: 1+x, –1+y, z; iv: x, –1+y, z; iiv: x, 1+y, z) and the angles
are in the range 135.0–175.1 °. In addition, an intermolecular
interaction exists between the O20 and Cl1 atoms, with a
O20···Cl1v distance of 3.612(2) Å and an O20···H20O···Cl1 an-
gle of 134.9 °. As in all of the previously published metal com-
plexes of the ligand L2 [13, 14], the outer surfaces of the lay-
ers of complex 2 are hydrophobic due to the benzyl groups
and the chlorine atoms pointing towards the interlayer section.
Crystal Structure of
[Mn{[Cl2C(PO2O(C(O)C6H5))2](H2O)3}] (3)
The asymmetric unit of complex 3 includes one independent
manganese atom, one L2 ligand and three aqua ligands (Fig-
ure 4). The L2 ligand shares corners of two PCO3 tetrahedra
with a MnO6 octahedron in a bidentate fashion, and forms a
six-membered chelate ring. The structure of compound 3 con-
sists of dimeric building blocks, where the L2 ligand is also
monodentately coordinated to the adjacent manganese atom (–
x, –y, 1–z) through the PCO3 tetrahedron, forming an eight-
membered chelate ring and leaving the other phosphonate oxy-
gen atoms deprotonated. The dimeric ring is completed by
bridging of the two MnO6 octahedra by sharing overall three
corners of two PCO3 tetrahedra (see Figure 4) through the ad-
jacent L2 ligand. The other coordination sites of the manga-
nese atoms are occupied by aqua ligands, but there is no intra-
molecular hydrogen bonding in the structure. The Mn–O bond
lengths [(Mn–O)av = 2.1815 Å] and the O–Mn–O angles (in
the range of 78.3–170.4 °) show a distortion in the MnO6 octa-
hedron (see Table 2). The longest Mn–O bond lengths are Mn–
Figure 3. Molecular structure of 2 with numbering scheme and ther-
mal ellipsoids (50 %, top image). Packing of the monomeric units of
2 (bottom image, PCO3 tetrahedron = dark grey; PCO3 tetrahedron of
the lattice L2 ligand = grey; CoO6 octahedron = light grey).
Z. Anorg. Allg. Chem. 2010, 710–720
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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713

S. Kunnas-Hiltunen et al.
ARTICLE
Table 2. Selected M–O bond lengths /Åand O–M–O angles /° for compounds 2 and 3.
2
3a)
Co1–O12
Co1–O11
Co1–O9
Co1–O13
Co1–O1
Co1–O10
2.038(2)
2.061(2)
2.092(2)
2.101(2)
2.112(2)
2.115(2)
Co2–O15
Co2–O17
Co2–O16
Co2–O18
Co2–O19
Co2–O14
2.018(2)
2.036(2)
2.050(2)
2.153(2)
2.173(2)
2.187(2)
Mn1–O5
Mn1–O2A
Mn1–O11
Mn1–O10
Mn1–O9
Mn1–O1
2.1170(14)
2.1231(14)
2.1793(14)
2.2108(14)
2.224(2)
2.2347(14)
O12–Co1–O11
O12–Co1–O9
O11–Co1–O9
O12–Co1–O13
O11–Co1–O13
O9–Co1–O13
O12–Co1–O1
O11–Co1–O1
O9–Co1–O1
O13–Co1–O1
O12–Co1–O10
O11–Co1–O10
O9–Co1–O10
O13–Co1–O10
O1–Co1–O10
95.01(9)
91.82(9)
170.41(9)
91.68(8)
84.01(8)
89.08(8)
88.56(8)
91.92(8)
94.98(8)
175.93(9)
174.90(9)
85.33(8)
88.47(8)
93.42(8)
86.34(8)
O15–Co2–O17
O15–Co2–O16
O17–Co2–O16
O15–Co2–O18
O17–Co2–O18
O16–Co2–O18
O15–Co2–O19
O17–Co2–O19
O16–Co2–O19
O18–Co2–O19
O15–Co2–O14
O17–Co2–O14
O16–Co2–O14
O18–Co2–O14
O19–Co2–O14
171.18(10)
95.88(9)
92.92(9)
86.97(8)
84.22(8)
176.96(10)
90.82(8)
89.84(8)
90.15(9)
90.87(8)
89.84(8)
89.55(8)
89.50(8)
89.46(8)
179.28(9)
O5–Mn1–O2A
O5–Mn1–O11
O2A–Mn1–O11
O5–Mn1–O10
O2A–Mn1–O10
O11–Mn1–O10
O5–Mn1–O9
O2A–Mn1–O9
O11–Mn1–O9
O10–Mn1–O9
O5–Mn1–O1
93.29(6)
170.44(6)
79.98(5)
102.70(6)
161.30(6)
85.16(5)
87.90(6)
92.86(5)
99.14(6)
78.29(5)
86.30(5)
97.80(5)
87.89(5)
92.89(5)
168.13(5)
O2A–Mn1–O1
O11–Mn1–O1
O10–Mn1–O1
O9–Mn1–O1
a) In structure 3, A refers to the atom at symmetry position (–x, –y, 1–z).
O1 and Mn–O9, respectively. The dimeric units are held to-
gether by intermolecular hydrogen bonds involving all aqua
ligands as donors and phosphonate and carbonyl oxygen atoms
of the L2 ligand as acceptors, forming a 2D layer-like hydro-
gen bond network along the [001] plane (Figure 4). The inter-
molecular O10···O6i, O11···O1ii, O11···O6iii, O9···O8iv,
O10···O4ii and O9···O4v distances are in the range of 2.726(2)–
3.084(2) Å (symmetry code: i: 1+x, y, z; ii: 1–x, –y, 1–z; iii:
–x, –y, 1–z; iv: –x, 1–y, 1–z; v: x, 1+y, z) with their angles in
the range 162.8–175.3 °.
Crystal Structure of
[Cu{(CH2C5H5N)C(OH)(PO3H)2}2·4H2O] (4)
Various hydrate forms of risedronate [18a, 18b] were crystal-
lised, but among the metal complex structures, only the potas-
sium [18c], cobalt [18d], and cadmium [18e] complexes of
risedronic acid were found in literature. These metal risedron-
ates form chains, which are further connected to a 3D structure
by extensive hydrogen bonding [18c–18e]. Thus, compound 4
is among the first metal complexes of risedronate (L3). It con-
sists of centrosymmetric units constructed from Cu1II sharing
four corners of the PCO3 tetrahedron of two L3 ligands. The
octahedral coordination sphere of the Cu1 atom is completed
with the two hydroxyl oxygen atoms of both L3 ligands (see
Figure 5). The CuO6 octahedron is distorted by these Cu1–O7
bonds, due to the Jahn–Teller effect, resulting in a Cu1–O7
bond length of 2.656(2) Å. The Cu1–O1 and Cu1–O2 bond
lengths have values of 1.944(2) and 1.9621(14) Å, respectively
(Table 3). The L3 ligand chelates the Cu1 atom tridentately,
forming five- and six-membered chelate rings, with two of the
four available phosphonate oxygen atoms deprotonated. The
intramolecular hydrogen bond is formed between the lattice
Figure 4. Molecular structure of 3 with numbering scheme and ther-
mal ellipsoids (50 %, top image). Packing of the dimeric units of 3
(bottom image, PCO3 tetrahedron = dark grey; MnO6 octahedron =
light grey).
714
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 710–720

Mn, Co and Cu Complexes of Modified Bis(phosphonates)
water molecule O8 and the phosphonate oxygen atom O4, hav- (symmetry code: i: 1–x, 1–y, –z; ii: –x, –y, 1–z; iii: 1–x, –y, –
ing a O8···O4 distance of 2.767(2) Å and an O8–H8O···O4 z; iv: 1+x, y, z; v: –x, –y, –z; vi: x, –1+y, z) and the angles are
angle of 162.9 °. The intermolecular hydrogen bonds are in the range 118.8–175.3 °. In addition, intermolecular face-
formed in three dimensions, the protonated phosphonate oxy- to-face π–π stacking interactions exist between the adjacent
gen atom and the pyridyl nitrogen atoms, the hydroxyl groups pyridine rings along the crystallographic b axis.
and the lattice water molecules serve as hydrogen-bond donors
and deprotonated phosphonate oxygen atoms and lattice water
molecules serve as acceptors. The intermolecular O3···O8i,
O6···O5ii, O7···O4iii, N1···O9iv, O9···O1v, O9···O5vi, O8···O2iv,
and O9···O3vi distances are in the range 2.555(2)–3.117(2) Å
Table 3. Selected M–O bond lengths /Å and O–M–O angles /° for
compound 4.
4a)
Cu1–O1
Cu1–O2
Cu1–O7
1.944(2)
1.9621(14)
2.656(2)
O1–Cu1–O2
O1–Cu1–O1A
O2–Cu1–O2A
O1–Cu1–O7
O2–Cu1–O7
O1A–Cu1–O7
O2A–Cu1–O7
O7–Cu1–O7A
89.68(6)
180.00(8)
180.00
78.12(6)
77.61(5)
101.88(6)
102.39(5)
180.00(5)
a) In structure 4, A refers to the atom at symmetry position (–x, –y, 1–z).
Structural Comparison
To conclude thus far, the clodronate L1 tends to chelate and
bridge metals with ionic radii of 0.74(Zn2+)–1.42(Ba2+) Å [19]
to polymeric structures, which form 2D and 3D structures
through hydrogen bonding [3a, 3b, 12]. Exceptions are the
monomeric strontium [12k], nickel [14] and cobalt complexes
(compound 1) of clodronic acid and dimeric zinc clodronate
[14]. The isostructural nickel, zinc, and cobalt complexes form
an extended 3D hydrogen-bond network. There are relatively
few metal complexes from the mono ester derivatives of clo-
dronate, but they form 2D and 3D structures, where the ethyl
[12a, 12b, 12d] and phenyl ester [12a] derivatives of clodron-
ate both chelate and bridge the metal atoms. The symmetrical
diester derivatives of clodronate, in turn, both act in a chelating
manner and bridge the metal atoms with ionic radii of 0.74–
1.42 Å [19], forming monomeric [12c], dimeric [12f], tetram-
eric [12g, 12h] and polymeric [12] structures, some of which
form 1D and 2D structures through hydrogen bonding.
In compound 2, the polyfunctional ligand L2 coordinates the
metal only monodentately and does not chelate and/or bridge
the two cobalt atoms, even though the lattice L2 ligand and
the [Co(H2O)6}]2+ cation participate in forming the crystal
structure. Generally, the L2 ligand tends to chelate and/or
bridge the metal atoms, and therefore the size of the ionic radii
of the metal has an effect. In addition to the Co2+ ion (ionic
radius 0.745 Å [19]), the L2 also binds the hexacoordinate
Mg2+ ion (ionic radius 0.72 Å [19]) in a monodentate fashion
[13]. With hexacoordinate Ni2+ (ionic radius 0.69 Å [19]) and
Zn2+ ions (ionic radius 0.74 Å [19]), the L2 ligand coordinates
metals in a monodentate manner, but also bridges them to the
hexacoordinate Na+ ion (ionic radius 1.02 Å [19]), forming
polymeric chains [14]. In complex 3 with hexacoordinate Mn2+
(ionic radius 0.83 Å [19]), and with octa- and nonacoordinate
Figure 5. Molecular structure of 4 with numbering scheme and ther-
mal ellipsoids (50 %, top image). Packing of the monomeric units of
4 (bottom image, PCO3 tetrahedron = dark grey; CuO6 octahedron =
light grey).
Z. Anorg. Allg. Chem. 2010, 710–720
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
715

S. Kunnas-Hiltunen et al.
ARTICLE
Sr2+ (ionic radii 1.26 and 1.31 Å, respectively [19]), and octa- spectra of compounds 2–4. Absorptions due to the bis(phos-
coordinate Ba2+ ions (ionic radius 1.42 Å [19]), the L2 ligand phonic) acid framework of 1–4 were found at 1295–970 cm–1,
both chelates and bridges the metal atoms, and forms a dimeric which could be attributed to the stretching vibrations of the
structure with Mn2+ and also polymeric structures with Sr2+ phosphonate PO3 groups, and signals at 860–760 cm–1 were
and Ba2+ ions [13]. In consequence, the L2 ligand both che- assigned to asymmetric and symmetric ν(P–C–P) vibrations.
lates and bridges metal atoms with ionic radii > 0.80 Å, but In compounds 1–3, the asymmetric and symmetric ν(CCl2) vi-
otherwise it acts as a monodentate or bidentate ligand without brations appeared at 805–685cm–1.
forming chelate rings. All metal complexes of the L2 ligand
The difference between the IR spectra of the metal complex
form 2D structures through the hydrogen bonding of crystal of L1 (1), and the metal complexes of L2 (2, 3), is that the
water and coordinated water. In addition, the other diester de- ν(P=O) absorption is shifted approximately 150 cm–1 to higher
rivatives, where the ester group is smaller, form also 1D struc- wavenumbers in the spectra of compounds 2 and 3, due to the
tures through hydrogen bonding [12f].
benzoyl groups attached to the phosphonate groups. In addi-
Compound 4 and other geminal bisphosphonates, where the tion, the spectra of compounds 2 and 3 showed other bands
hydrophobic groups are attached to the middle carbon atom resulting from the benzoyl groups of the ligand L2. The ab-
between the two phosphonate groups, form 0–3D structures sorptions of ν(C=O) appeared at 1730 cm–1, and the absorp-
some of which are extended to 3D structures through hydrogen tions of ν(C–O) appeared at 1270 cm–1 and 1135 cm–1. The
bonding [6c–6e, 7c–7f, 8b–8e, 8g, 18c–18e]. In addition, π–π aromatic ring ν(C=C) vibrations occurred at 1605 cm–1,
stacking interactions may occur in the case of risedronate 1590 cm–1, 1495 cm–1, and 1455 cm–1 and the stretching vi-
[18c–18e].
brations of the ring C–H bonds appeared as a series of bands
In conclusion, the flexible and hydrophilic clodronic acid li- in the 3100–2800 cm–1 region. Absorptions of the monosubsti-
gand L1 is able to form a 3D hydrogen-bonded network. As tuted aromatic ring, resulting from out-of-plane C–H vibra-
mentioned before [14], the bulky organic groups attached to tions, appeared at ca. 750 cm–1 and 700 cm–1. In addition, in
the phosphonate oxygen atoms, for example the diester groups the spectrum of pyridyl compound 4, the characteristic broad
in ligand L2, lead to 2D dense packing modes without solvent- bands of the pyridine ring are in the same region than the CH2
accessible voids. The monoester derivatives, in turn, are capa- and PO3 stretching vibrations, which makes the reading of the
ble of forming a 3D hydrogen bond network. If the hydropho- spectrum difficult. The spectrum of complex 4 shows aromatic
bic groups are located in the middle carbon chain between the C–H stretching vibrations as a broad band at 3150–3010 cm–1,
phosphonate groups, as in L3, the 3D hydrogen bond network and as a weak overtone and combined bands at 2200–
may be formed. This indicates that the designing of new 3D 2000 cm–1. The signals in the latter region can also result from
porous materials from metal bisphosphonates could also be fo- protonated phosphonate groups. The C=C and C=N stretching
cused on the addition of chains with suitable coordinating vibrations give rise to a band at 1640–1360 cm–1 and a strong
groups to the middle carbon atom. In all bisphosphonate struc- broad band was observed at 1140–910 cm–1.
tures, the additional lattice ligands or guest molecules, e.g. wa-
ter and acetone etc., play a significant role in determining the
Thermogravimetric Analyses
structural properties and achieving more open structures. The
general problem is the easy removability of the guest molecu-
les without breaking the crystal structure, to open the voids for
The TGA diagram for compound 1 shows three overlapped
weight loss steps at about 50–160 °C, 160–350 °C, and 350–
other molecules entering the structure in applications. More
800 °C, which are attributable to the release of lattice water,
unusual are the additional lattice ligands, e.g. L2, in the nickel
coordinated water and chlorine atoms. The TGA diagram for
[14], zinc [14], and cobalt (2) complexes of L2, which do not
compound 2, in turn, shows three overlapped weight loss steps
participate in coordination to the metal atoms.
at about 50–200 °C, 200–250 °C, and 250–800 °C, which are
attributable to the release of aqua ligands, chlorine atoms and
three benzoyl groups. The total weight losses of 47.9 % for 1
Spectroscopic Properties
and 55.4 % for 2 are in good agreement with the theoretical
The assignments of the cobalt, manganese and copper com- values of 48.3 % and 55.1 %, respectively.
plexes 1–4 are based on earlier results, on published values for
The TGA diagram for complex 3 indicates that it is stable
similar compounds and on IR spectroscopic tables [3a, 3b, 12– up to 100 °C, probably due to the structure-strengthening che-
14]. The characteristic signals for complex 1 appeared in the late rings and the lack of crystal water. The TGA diagram
region 1636–776 cm–1, for compounds 2 and 3 the characteris- exhibit three overlapped weight loss steps at about 100–
tic signals were observed in the range 1735–685 cm–1, and for 230 °C, 230–300 °C, 300–800 °C attributable to the release of
compound 4 in the range 3150–705 cm–1. The stretching fre- aqua ligands, chlorine atoms, and finally, two benzoyl groups.
quency of the O–H bonds of the water cluster pattern in com- The total weight loss of 57.0 % for 3 is in good agreement
plex 1 was observed as a broad band at around 3420 cm–1. The with the calculated value of 59.8 %.
same frequencies of ice appear at 3220 cm–1 and of liquid wa-
The TGA diagram for complex 4 indicates that the com-
ter at 3490 cm–1 and 3280 cm–1 [5c]. In addition, broad bands pound is stable up to 150 °C. The TGA diagram shows four
of ν(H2O) around 3410–3520 cm–1 and weaker absorptions of partly overlapped weight loss steps at about 150–200 °C, 200–
δ(H–O–H) in the region 1630–1640 cm–1 were observed in the 245 °C, 245–455 °C, and 455–800 °C, which are attributable
716
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 710–720

Mn, Co and Cu Complexes of Modified Bis(phosphonates)
to the release of crystal water, coordinated water, hydroxyl and manganese complexes of L2 (2 and 3), show the typical
groups, and pyridyl groups. The total weight loss of 42.3 % 2D arrangement of the units through hydrogen bonding. Inter-
for 4 is in good agreement with the calculated value of 41.8 %. esting here is the effect of the size of the metal ion in structure
The identifiable phases of the black final multiphase pro- formation. Thus far, the L2 ligand both chelates and bridges
ducts of compounds 1–2 and 4 could not be identified defi- metal atoms with ionic radii > 0.80 Å, but otherwise it acts
nitely by means of powder X-ray diffractometry, since the co- as a monodentate or bidentate ligand without forming chelate
balt and copper complexes create strong noise due to the rings.
fluorescence. The calculable final products of compounds 1–2
In the present study we demonstrated the effects of metal
and 4 are Co(PO3)2, Co2C9OH5(PO3)4 and CuC2(PO3)4, respec- and different kind of substituted groups in bis(phosphonate)
tively. The identifiable phase of the final black crystalline and ligands on the structure formation of bis(phosphonates), on IR
multiphase product of complex 3 was identified to be manga- spectroscopic frequencies and on thermogravimetric measure-
nese phosphate Mn(P4O11), whereas the calculable final prod- ments. The water clusters of complex 1 and lattice water in
uct is MnC(PO3)2.
compounds 2 and 4 were found and refined during the struc-
tural refinement process. They were experimentally observed
and described, which might enhance our understanding of the
properties of liquid water in terms of its space-filling role in
crystal structures. In addition, this study provides important
information for research into bis(phosphonates) as pharmaceu-
tical products, since the ionic radiuses of the first row transi-
tion metals are similar to the ionic radii of the alkaline earth
metals. The investigation of the coordination properties of the
modified bis(phosphonates), drugs and possible prodrugs, to-
ward divalent metals, would be helpful in understanding the
adsorption of the drug onto human bone and the binding prop-
erties toward metal cations in the human body. The scaling of
the syntheses and studies of the complexing properties of other
bis(phosphonates) are now in progress.
Conclusions
Four new metal complexes of unique and modified bis(phos-
phonate) ligands (1–4) were synthesised and characterised.
These new metal bis(phosphonates) form 2D and 3D structures
through extensive hydrogen bond network, and thus the addi-
tional lattice ligands play a significant role in determining the
structural properties. Present and earlier studies [14] show how
monomeric and dimeric metal clodronates form a 3D hydrogen
bond network around them. In cobalt clodronate (1), the 2D
tape-like water cluster patterns formed by hydrogen bonds be-
tween the lattice water and coordinated water molecules place
themselves between the dinuclear units. 3D hydrogen bonding
interactions occur when the phosphonate oxygen atoms serve
as hydrogen-bond acceptors. The 3D hydrogen bond network
can also be seen in copper risedronate (4), where the proto-
nated pyridyl nitrogen atoms and hydroxyl group between the
phosphonate groups participate in hydrogen bonding in addi-
tion to the coordinated and crystal water and phosphonate oxy-
gen atoms. Additionally, the pyridine rings form intermolecu-
Experimental Section
General Procedures
All reagents used for the synthesis and characterisation of compounds
1–4 were of analytical reagent grade. The synthesis and characterisa-
tion of P,P'-dibenzoyl-dichloromethylenebis(phosphonate) disodium
lar π–π stacking interactions with the adjacent rings. The cobalt salt, Na2Cl2C[PO3(COC6H5)]2 (Na2L2), were reported earlier [11a].
Table 4. Crystal data for compounds 1–4.
1
2
3
4
Empirical formula CH22Cl2Co2O17P2
C30H46Cl4Co2O29P4
1254.21
100(2)
C30H32Cl4Mn2O22P4
1120.12
100(2)
C14H28CuN2O18P4
699.80
Formula weight
Temperature /K
Crystal system
Space group
a /Å
556.89
100(2)
Monoclinic
P21/c
100(2)
Triclinic
P1
Monoclinic
P21/n
Triclinic
¯
P1
8.4768(1)
13.5729(2)
15.1066(2)
90
7.0225(2)
10.5820(4)
16.9475(6)
88.204(2)
82.207(2)
72.646(2)
1190.92(7)
1
7.5320(1)
9.9230(2)
28.5510(5)
90
7.6516(3)
8.5823(5)
10.2829(5)
65.908(2)
84.953(3)
78.852(3)
604.78(5)
1
b /Å
c /Å
α /°
β /°
91.8180(9)
90
92.177(1)
90
γ /°
V /Å3
1737.21(4)
4
2132.36(6)
2
Z
ρcalc /g·cm–3
μ(Mo-Kα) /mm–1
GOF on F2
Rinat)
2.129
1.749
1.745
1.919
2.481
1.149
1.076
1.260
1.079
1.028
1.043
1.091
0.0373
0.0238
0.0548
0.0289
0.0497
0.0542
R1 (I ≥ 2σ)
0.0302
0.0321
0.0331
b)
wR2 (I ≥ 2σ)
0.0655
0.0675
0.0799
a) R1 = Σ--Fo-–-Fc--.Σ-Fo-.b) wR2 = [Σ[w(Fo –Fc ) ]. Σ[w(Fo ) ]]1.2
.
2
2 2
2 2
Z. Anorg. Allg. Chem. 2010, 710–720
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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717

S. Kunnas-Hiltunen et al.
ARTICLE
The risedronic acid was synthesised by the known method [21], but [Cu{(CH2C5H5N)C(OH)(PO3H)2}2·4H2O] (4): A solution of L3 in
the product was changed into well crystallising disodium salt form water (0.018 mmol, 0.5 mL, pH 4.4) was mixed with a solution of
Na2[(CH2C5H5N)C(OH)(PO3H)2] (Na2L3) by adjusting the pH with Cu(NO3)2·2,5H2O in water (0.018 mol, 0.5 mL, pH 4.4). Pale blue
NaOH. Compound 1 was prepared by the gel crystallisation method, block-like crystals formed within two months (pH 4.0).
compounds 2 and 3 by the liquid crystallisation method and compound
4 by evaporation from the solution. In the present study, we are inter-
ested in the structural properties of compounds 1–4, and therefore the
Table 5. Selected bond lengths .Å and angles .° for compounds 1–4.
characterisation analyses were performed by using crystals derived
from additional crystallisations.
1
2
3
4
P1–O2
P1–O1
P1–O3
P1–O4
P2–O6
P2–O5
P2–O7
1.473(2)
1.488(2)
1.641(2)
1.4720(14)
1.491(2)
Single crystals of 1–4 were selected for structural determination with
a Nonius Kappa CCD diffractometer. Elemental analyses for C and H
were carried out with CarloErba 1106 and VarioMICRO V1.7.0 CHN
Mode analysers, in which clodronate and EDTA served as standards.
The percentage values of Co, Mn, and Cu were determined by using
a Varian 220 atomic absorption spectrophotometer. The infrared spec-
1.527(2)
1.557(2)
1.500(2)
1.568(2)
1.498(2)
1.6224(14)
1.493(2)
1.482(2)
1.630(2)
1.478(2)
1.479(2)
1.632(2)
tra were recorded with a Nicolet Magna-IRTM spectrometer 750 by P2–O2
1.522(2)
P1B–O2B
1.478(2)
1.482(2)
1.649(2)
1.477(2)
1.484(2)
1.654(2)
KBr pellet technique. Thermogravimetric analyses (TGA) were per-
formed with a METTLER Toledo TGA/SDTA851e for compounds 1,
2 and 4 under a nitrogen gas flow at a heating rate of 5 °C·min–1 from
25 °C to 800 °C, and from 25 °C to 900 °C for compound 3. Powder
X-ray diffraction (XRD) data for the final products of TG analyses
were collected with a Bruker Advance D8 diffractometer by using Cu-
Kα radiation (λ = 1.5406 Å) in the 2θ range of 5–100° with a step size
of 0.05° and a counting time of 3 s per step.
P1B–O1B
P1B–O3B
P2B–O6B
P2B–O5B
P2B–O7B
P5–O9
1.5125(11)
1.5221(11)
1.5223(11)
1.5088(11)
1.5220(11)
1.5336(11)
P5–O5
P5–O10
P6–O8
P6–O4
P6–O7
Syntheses
[Co2{Cl2C(PO3)2}(H2O)7·4H2O] (1): A solution of L1 in water
(0.087 mmol, 0.9 mL, pH 3.45) was mixed with TMOS (0.1 mL). The
concentrated solution of Co(NO3)2·6H2O in water (0.006 mol, 1.0 mL,
pH 2.70) was placed above the gel (pH 3.51). After two weeks it was
replaced with acetone (1.0 mL). Pale red block-like crystals formed on
the surface of the gel (pH 2.42) within a month after the addition of
the acetone. CH22Cl2Co2O17P2 (556.89): calcd. C 2.16; H 3.98; Co
P1–C1
1.861(3)
1.848(3)
1.855(3)
1.860(3)
1.856(2)
1.850(2)
1.850(2)
1.856(2)
1.848(2)
1.840(2)
P2–C1
P1B–C1B
P2B–C1B
P5–C1
P6–C1
O2–P1–C1
O1–P1–C1
O3–P1–C1
O4–P1–C1
O6–P2–C1
O5–P2–C1
O7–P2–C1
O2–P2–C1
O2B–P1B–
C1B
109.94(14)
105.63(13)
97.16(13)
108.93(9)
107.67(9)
96.44(8)
21.16 %; found C 2.09; H 4.05; Co 20.94 %. IR (KBr): ν = 1636 (m,
˜
105.40(9)
104.22(9)
109.60(9)
105.64(9)
110.75(9)
d
P–O), 1130 (vs, νP=O), 1018 (s, νP–O), 967 (m, νP–O), 889 (m, νP–C–P),
776 (m, νP–C–P), 770 (sh, νC–Cl) cm–1.
108.06(14)
108.76(13)
99.27(13)
108.78(9)
106.46(9)
97.99(8)
[Co{Cl2C(PO2O(C(O)C6H5))2(H2O)5}·2H2O{Cl2C(PO2O(C(O)-
C6H5))2}{Co(H2O)6}] (2): Solutions of L2 in water (0.030 mmol,
1 mL, pH 3.74) and of Co(NO3)2·6H2O in water (0.030 mmol, 1 mL,
pH 4.49) were mixed with acetone (1 mL). The solution (pH 3.30)
was allowed to stand cold and pale red plate-like crystals formed after
four days (pH 3.22). C30H46Cl4Co2O29P4 (1254.21): calcd. C 28.73; H
105.52(9)
107.34(13)
108.33(13)
99.80(12)
109.44(14)
107.39(14)
96.24(13)
O1B–P1B–
C1B
3.70; Co 9.40 %; found C 28.56; H 3.71; Co 9.40 %. IR (KBr): ν =
˜
1729 and 1711 (m,νC=O), 1604 (m, νC=C), 1586 (w, νC=C), 1497 (w, O3B–P1B–
C1B
O6B–P2B–
C1B
O5B–P2B–
C1B
O7B–P2B–
C1B
O9–P5–C1 106.82(7)
O5–P5–C1 106.05(7)
O10–P5–C1 103.15(7)
O8–P6–C1 106.74(7)
O4–P6–C1 104.13(7)
O7–P6–C1 105.62(7)
νC=C), 1456 (m, νC=C), 1272 (s, νP=O, νC–O), 1183 (m, νC–O–P), 1135 (m,
νC–O), 1104 (m, νC–C), 1077 (m, νP–O), 1064 (m, νP–O), 1029 (m,
νP–O–C), 1004 (w, νP–O–C), 843 (m, νP–C–P), 774 (m, νP–C–P, νC–H, νC–Cl),
703 (s, νC–H), 685 (m, νC–Cl) cm–1.
[Mn{[Cl2C(PO2O(C(O)C6H5))2](H2O)3}] (3): Solutions of L2 in wa-
ter (0.030 mmol, 1 mL, pH 3.75) and of MnCl2·4H2O in water
(0.030 mmol, 1 mL, pH 4.94) were mixed and acetone (1 mL) was
added. The solution (pH 3.51) was allowed to stand cold and colourless
block-like crystals formed after one day (pH 3.14).
C30H32Cl4Mn2O22P4 (1120.12): calcd. C 32.21; H 2.89; Mn 9.83 %;
found: C 32.33; H 2.80; Mn 9.78 %. IR (KBr): ν = 1735 and 1720m
˜
(m, νC=O), 1605 (m, νC=C), 1590 (w, νC=C), 1496 (w, νC=C), 1457 (m,
νC=C), 1294 (s, νP=O), 1267 (s, νC–O), 1179 (w, νC–O–P), 1134 (m, νC–O),
1101 (m, νC–C), 1083 (m, νP–O), 1067 (s, νP–O), 1028 (m, νP–O–C), 1000
(vw, νP–O–C), 859 (m, νP–C–P), 805 (w, νC–Cl), 777 (m, νP–C–P), 765 (m,
νC–H), 708 (s, νC–H), 687 (m, νC–Cl) cm–1.
P1–C1–P2
P1B–C1B–
P2B
109.1(2)
108.8 (2)
109.69(10)
109.87(10)
P5–C1–P6 115.38(8)
718
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 710–720

Mn, Co and Cu Complexes of Modified Bis(phosphonates)
vey, S. J. Teat, M. P. Attfield, J. Mater. Chem. 2000, 10, 2632–
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1132–1137.
C14H28CuN2O18P4 (699.80): calcd. C 24.03; H 4.03; N 4.00 Cu
9.08 %; found C 23.89; H 3.92; N 4.00; Cu 8.91 %. IR (KBr): ν =
˜
1123 (vs, νP=O), 1061 (vs, νPO3), 978 (s, νP–O), 817 (m, νP–C–P), 762
(m, νP–C–P) cm–1.
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X-ray Crystallographic Study
Crystals of 1–4 were immersed in cryo-oil, mounted in a Nylon loop,
and measured at a temperature of 100 K. The X-ray diffraction data
were collected by means of a Nonius KappaCCD diffractometer using
Mo-Kα radiation (λ = 0.71073 Å). The Denzo-Scalepack [22] program
package was used for cell refinements and data reductions. The struc-
tures were solved by direct methods with SHELXS-97 [23] for com-
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[25] graphical user interface. A semi-empirical absorption correction
(compounds 1–3: SADABS [26], compound 4: SORTAV [27]) was
applied to all data. Structural refinements were carried out using
SHELXL-97 [23]. Despite a rather large Flack parameter [0.243(9)] in
compound 2, the introduction of a racemic twin component did not
improve the result, and the twin component was not used in the final
refinement. All water hydrogen atoms in structure 1 were located on
the difference Fourier map but were repositioned geometrically and
constrained to ride on their parent atom, with Uiso = 1.5. In complexes
2–4 all of the water hydrogen atoms (and all of the NH and OH hydro-
gen atoms in complex 4) were located on the difference Fourier map
and constrained to ride on their parent atom, with Uiso = 1.5. Other
hydrogen atoms in compounds 2–4 were positioned geometrically and
were also constrained to ride on their parent atoms, with C–H = 0.95–
0.99 Å and Uiso = 1.2·Ueq (parent atom). The crystallographic details
are summarised in Table 4 and selected bond lengths and angles are
shown in Table 5.
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Crystallographic data for the structures have been deposited with the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge
CB21EZ. Copies of the data can be obtained free of charge on quoting
the depository numbers CCDC-752487 (compound 1), CCDC-752488
(compound 2), CCDC-752489 (compound 3), and CCDC-752490
(compound
4).
(Fax:
+44-1223-336-033;
E-Mail:
de-
posit@ccdc.cam.ac.uk).
Supporting Information (see footnote on the first page of this article):
IR spectra, TGA curves and hydrogen bond tables for compounds 1–
4.
Acknowledgement
We would like to thank Tarja Virrantalo for her assistance (Dept.
Chem., Univ. Joensuu).
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Received: December 9, 2009
Published Online: February 1, 2010
720
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Z. Anorg. Allg. Chem. 2010, 710–720