Metal phosphonates based on {[(benzimidazol-2-ylmethyl)imino]bis- (methylene)}bis(phosphonic acid): Syntheses, structures and magnetic properties of the chain compounds [M{(C7H5N2)CH 2N(CH2PO3H)2}] (M = Mn, Fe, Co, Cu, Cd)

Article abstract of DOI:10.1002/ejic.200500788

Five compounds based on {[(benzimidazol-2-ylmethyl)imino-]bis(methylene)} bis(phosphonic acid) [(C₇H₅N₂)CH ₂N(CH₂-PO₃H₂)₂], namely [M{(C₇H₅N₂)CH₂N(CH ₂PO₃H)₂}] [M = Mn (1), Fe (2), Co (3), Cu (4), Cd (5)] have been synthesized under hydrothermal conditions. These compounds are isostructural, crystallizing in the orthorhombic space group Pbca, with a = 15.331(2), b = 10.7150(16), and c = 16.715(2) A for 1; a = 15.320(3), b = 10.477(2), and c = 16.764(3) A for 2; a = 15.207(2), b = 10.4626(16), and c = 16.794(3) A for 3; a = 15.101(3), b = 10.3517(17), and c = 16.997(3) A for 4; and a = 15.4679(19), b = 10.8923(13), and c = 16.6175(19) for 5. Each compound shows a one-dimensional chain structure where {MO ₃N₂} trigonal bipyramids are connected by {CPO ₃} tetrahedra through corner-sharing. The chains are further connected to each other through aromatic stacking of the benzimidazole rings and extensive hydrogen bonds, forming a supramolecular 3D structure. Magnetic susceptibility studies of 1-4 reveal that weak antiferromagnetic interactions occur between the metal centers. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200500788

FULL PAPER
DOI: 10.1002/ejic.200500788
Metal Phosphonates Based on {[(Benzimidazol-2-ylmethyl)imino]bis-
methylene)}bis(phosphonic Acid): Syntheses, Structures and Magnetic
Properties of the Chain Compounds [M{(C H N )CH N(CH PO H) }]
(
7
5
2
2
2
3
2
(
M = Mn, Fe, Co, Cu, Cd)
[
a]
[a]
[a]
[b]
Deng-Ke Cao, Jing Xiao, Yi-Zhi Li, Juan Modesto Clemente-Juan,
[b]
[a]
Eugenio Coronado, and Li-Min Zheng*
Keywords: Chain structures / Magnetic properties / N,O ligands / Organic–inorganic hybrid composites / Transition metals
Five compounds based on {[(benzimidazol-2-ylmethyl)imino-
bis(methylene)}bis(phosphonic acid) [(C )CH N(CH
PO ], namely [M{(C )CH N(CH H) }] [M = Mn
1), Fe (2), Co (3), Cu (4), Cd (5)] have been synthesized un-
der hydrothermal conditions. These compounds are iso-
structural, crystallizing in the orthorhombic space group
Pbca, with a = 15.331(2), b = 10.7150(16), and c = 16.715(2) Å
for 1; a = 15.320(3), b = 10.477(2), and c = 16.764(3) Å for 2;
a = 15.207(2), b = 10.4626(16), and c = 16.794(3) Å for 3; a =
compound shows a one-dimensional chain structure where
{MO } trigonal bipyramids are connected by {CPO } tetra-
]
7
H
PO
5
N
2
2
2
-
3
N
2
3
3
H
2
)
2
7
H
5
N
2
2
2
3
2
hedra through corner-sharing. The chains are further con-
nected to each other through aromatic stacking of the benz-
imidazole rings and extensive hydrogen bonds, forming a
supramolecular 3D structure. Magnetic susceptibility studies
of 1–4 reveal that weak antiferromagnetic interactions occur
between the metal centers.
(
1
1
5.101(3), b = 10.3517(17), and c = 16.997(3) Å for 4; and a =
5.4679(19), b = 10.8923(13), and c = 16.6175(19) for 5. Each
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Introduction
bibmpH ], where a benzimidazole group is incorporated
4
into the diphosphonic acid. Five isostructural compounds
based on this ligand, namely [M{(C H N )CH N-
Increasing attention has been paid in recent years to me-
tal phosphonate materials due to their potential applica-
tions in catalysis, nonlinear optics, magnetism, and biotech-
7
5
2
2
(
(
CH PO H) }] [M = Mn (1), Fe (2), Co (3), Cu (4), Cd
5)] are obtained by hydrothermal reactions; all exhibit one-
2 3 2
[
1]
nology etc. Meanwhile, the rapid development in the ra-
tional design and synthesis of coordination polymers, by
using different organic ligands, has provided a variety of
compounds with interesting architectures and possible
dimensional chain structures. The magnetic properties of 1–
were also investigated.
4
[
2]
functionalities. The integration of the inorganic phos-
phonate (CPO ) group and numerous rigid or flexible or-
Results and Discussion
3
ganic functional groups within the same composite would,
therefore, be expected to result in new inorganic–organic
hybrid materials with interesting structures and properties.
Efforts along this line have been made where the organic
Syntheses and Preliminary Characterization
The synthesis of bibmpH was previously reported from
4
2
-(2-aminomethyl)benzimidazole, phosphorus, and formal-
[
8]
[
3]
dehyde by a Mannich reaction. In this paper we describe
a new synthetic route to the same acid from the reaction
between N,N-bis(phosphonomethyl)aminoacetic acid and
moieties of the phosphonate ligand contain amino, car-
[
4]
[5]
[6]
[7]
boxylate, pyridyl, macrocyclic, and ferrocene groups
etc. In this article, we report a new route to the synthesis
1,2-diaminobenzene (Scheme 1). The final product can be
of
{[(benzimidazol-2-ylmethyl)imino]bis(methylene)}bis-
acid) [(C H N )CH N(CH PO H ) ,
easily isolated with a much higher yield (82%) than that
(phosphonic
7
5
2
2
2
3
2 2
[
8]
reported in the patent (17%).
The hydrothermal reaction of bibmpH and the appro-
[
a] State Key Laboratory of Coordination Chemistry, Coordina-
tion Chemistry Institute, Nanjing University,
Nanjing 210093, P. R. China
4
priate metal sulfate at 140 °C for one day resulted in com-
pounds 1–5, which have identical structures even though
the experimental conditions for the formation of these com-
pounds are slightly different. A series of experiments was
conducted by changing the molar ratio of the starting mate-
rials and the pH of the reaction mixture. It was found that
Fax: +86-25-8331-4502
E-mail: lmzheng@nju.edu.cn
[b] Institut de Ciència Molecular, Universitat de València,
Dr. Moliner 50, 46100 Burjassot, Spain
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
1830
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Eur. J. Inorg. Chem. 2006, 1830–1837

Metal Phosphonates with One-Dimensional Chain Structures
FULL PAPER
Scheme 1.
pure phases of compounds 1, 3, and 5 can be obtained with
The IR spectra of compounds 1–5 are almost identical.
good yields when the molar ratio of M/ligand and the pH The broad bands appearing around 3000 cm–1 can be as-
are 1:1 and 2.5–3.5 for 1, 1:1 and 3.0–4.0 for 3, and 1:1 signed to NH and OH stretching vibrations with the pres-
[
9]
and 2.0–4.0 for 5, respectively. For compounds 2 and 4, the ence of extensive hydrogen bonds. The sharp bands at
crystallization of the products is always accompanied by the around 1622, 1598, and 1522 cm–1 are characteristic of the
–1
formation of brown powdery impurities when the molar ra- phenyl ring, and the bands near 1467 and 1455 cm are
[
10]
tio of M/ligand and the pH are 1:0.75–1 and 2.9–7.0 for 2 typical for ν(C=N) of the imidazole ring.
A series of
–1
and 1:0.75–1 and 3.0–5.9 for 4, respectively. Crystals with bands between 1236 and 915 cm correspond to the the
[
11]
the best quality are formed when the pH is 7.03 for 2 and CPO groups.
3
4
.90 for 4. In preparing compound 2, Me NOH was used
4
Crystal Structures of Compounds 1–5
instead of NaOH to adjust the pH of the reaction mixture
in order to improve the crystal quality. The same product
can also be obtained with NaOH.
Compounds 1–5 are isostructural and crystallize in the
orthorhombic space group Pbca. Crystallographic and re-
Table 1. Selected bond lengths [Å] and angles [°] for 1–5.[a]
1
2
3
4
5
M1–O1
M1–O4
M1–N1
M1–N2
M1–O5A
P1–O1
P1–O2
P1–O3
2.032(3)
2.090(3)
2.486(4)
2.127(4)
2.033(3)
1.496(4)
1.517(4)
1.580(4)
1.507(4)
1.506(4)
1.552(3)
115.95(15)
79.21(13)
114.37(17)
105.68(14)
79.16(13)
115.67(15)
98.01(13)
73.63(15)
175.09(14)
104.32(16)
106.4(3)
106.2(3)
108.1(3)
119.8(5)
135.3(4)
124.9(2)
123.58(19)
135.5(2)
1.980(3)
2.029(3)
2.364(3)
2.067(3)
2.035(3)
1.501(3)
1.494(3)
1.569(3)
1.978(3)
2.004(3)
2.345(4)
2.024(4)
2.005(3)
1.504(3)
1.495(4)
1.573(3)
2.000(2)
2.142(2)
2.137(3)
1.981(3)
1.926(2)
1.509(2)
1.513(2)
1.564(2)
1.501(2)
1.513(2)
1.554(2)
113.52(9)
87.18(9)
125.68(11)
96.31(9)
84.55(9)
117.56(10)
91.09(9)
2.148(3)
2.198(3)
2.551(3)
2.213(4)
2.152(3)
1.492(3)
1.494(3)
1.604(3)
P2–O4
P2–O5
P2–O6
1.524(3)
1.494(3)
1.558(3)
1.524(3)
1.493(3)
1.563(3)
1.525(3)
1.487(3)
1.573(3)
O1–M1–O4
O1–M1–N1
O1–M1–N2
O1–M1–O5A
O4–M1–N1
O4–M1–N2
O4–M1–O5A
N1–M1–N2
O5A–M1–N1
O5A–M1–N2
M1–N1–C1
M1–N1–C2
M1–N1–C3
M1–N2–C4
M1–N2–C5
M1–O1–P1
M1–O4–P2
M1B–O5–P2
122.72(12)
82.30(11)
113.09(13)
101.24(12)
81.87(11)
115.80(13)
94.78(12)
76.41(12)
176.11(12)
103.45(13)
105.7(2)
107.9(2)
107.8(2)
118.0(3)
136.5(3)
122.96(17)
122.01(16)
138.15(19)
118.82(14)
82.49(13)
115.30(15)
100.05(13)
82.12(12)
118.10(14)
95.24(12)
77.25(14)
177.02(13)
102.92(14)
106.5(3)
107.5(3)
107.2(3)
118.5(3)
136.1(3)
122.6(2)
122.37(17)
137.95(19)
111.24(10)
78.53(10)
117.01(12)
110.01(12)
77.49(10)
114.86(12)
95.16(11)
72.34(12)
170.52(11)
106.06(13)
105.1(2)
105.7(2)
105.5(2)
119.4(3)
134.8(3)
122.86(15)
121.94(16)
128.28(19)
80.52(10)
175.25(10)
99.92(10)
107.95(17)
109.77(19)
107.02(19)
114.9(2)
139.9(2)
117.48(12)
116.85(14)
136.27(15)
[a] Symmetry codes: A: –x, y + 1/2, –z + 1/2; B: –x, y – 1/2, –z + 1/2.
Eur. J. Inorg. Chem. 2006, 1830–1837
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D.-K. Cao, J. Xiao, Y.-Z. Li, J. M. Clemente-Juan, E. Coronado, L.-M. Zheng
FULL PAPER
finement details of 1–5 are listed in the Experimental Sec- 1 contains one MnII ion and one bibmpH22– ligand. The
tion, and selected bond lengths and angles are given in Mn1 atom has a distorted trigonal bipyramidal geometry,
Table 1. Figure 1 displays the building unit of 1 with the with the basal plane defined by the atoms O1, O4, and N2
atomic labeling scheme. The asymmetric unit of compound from the same bibmpH22– ligand. The Mn1–O1, Mn1–O4,
and Mn1–N2 bond lengths are 2.032(3), 2.090(3), and
2.127(4) Å, respectively, while the O1–Mn1–O4, O1–Mn1–
N2, and O4–Mn1–N2 bond angles are 116.0(2)°, 114.4(2)°,
and 115.7(2)°, respectively. The axial positions are occupied
2–
by the atom N1 from the same bibmpH ligand and O5A
2
from the other equivalent bibmpH22– ligand. The N1–
Mn1–O5A bond angle is 175.1(1)°, and the Mn1–N1 and
Mn1–O5A bond lengths are 2.486(4) and 2.033(3) Å,
respectively.
Each bibmpH 2– behaves as a pentadentate ligand, bind-
2
ing through three phosphonate oxygen atoms (O1, O4, O5),
one imino nitrogen atom (N1), and one benzimidazole ni-
trogen atom (N2). Two phosphonate oxygen atoms (O3,
O6), each from a {CPO } terminus, are protonated [P1–O3
3
=
1.580(4), P2–O6 = 1.552(3) Å]. The remaining phos-
phonate oxygen (O2) is pendant [P1–O2 = 1.517(4) Å]. The
equivalent Mn atoms are bridged by phosphonate oxygen
atoms O4 and O5 to form a zigzag chain along the b-axis
Figure 1. Asymmetric building unit of compound 1 with atomic
labeling scheme (50% probability). All H atoms except H3A, H3B
and H6A are omitted for clarity.
Figure 2. A fragment of chain in structure 1. All H atoms except H3A, H3B and H6A are omitted for clarity.
Figure 3. The inter-chain π-π stacking and N···O hydrogen bond interactions in structure 1. All H atoms are omitted for clarity.
1832
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Eur. J. Inorg. Chem. 2006, 1830–1837

Metal Phosphonates with One-Dimensional Chain Structures
FULL PAPER
(
Figure 2). The Mn1···Mn1A distance over the O4–P2–O5 up. Figure 5 shows the packing diagram of compound 1
bridge is 5.849 Å. The benzimidazole rings are arranged viewed down the b-axis.
tilted on two sides of the chain. The structures of compounds 2–4 are analogous to 1 ex-
Between the chains, the benzimidazole rings are approxi- cept that the Mn ion in 1 is replaced by Fe in 2, Co in
II
II
II
II
II
mately parallel and are π–π stacked (the average centroid– 3, Cu in 4, and Cd in 5. The cell volume decreases in the
centroid distance between the two phenyl rings of the benz- sequence 5 Ͼ 1 Ͼ 2 Ͼ 3 Ͼ 4, in accordance with the
imidazole groups is 3.547 Å for 1; Figure 3).[ Hydrogen- decreasing sequence of the ionic radii of the corresponding
12]
[
13]
bond interactions are found between the imidazole nitrogen metal ions.
Therefore, the metal atoms in 2–5 also have
atom (N3) and the phosphonate oxygen atom (O2) approxi- distorted trigonal bipyramidal geometries. The M–N1 dis-
mately along the c-axis, and among phosphonate oxygen tance [2.364(3) Å in 2, 2.345(4) Å in 3, 2.137(3) Å in 4, and
i
atoms along the a-axis (Figures 3 and 4). The N3···O2 , 2.551(3) Å in 5] is significantly longer than the other M–
ii
iii
O3···O4 , and O6···O2 distances are 2.753(6), 2.723(5), O(N) bond lengths, although the Cu1–N1 bond length in 4
and 2.536(5) Å, respectively (symmetry codes: i: x, –y + [2.137(3) Å] is much shorter. The metal atoms are bridged
3/2, z – 1/2; ii: x + 1/2, y, –z + 1/2; iii: x – 1/2, y, –z + 1/2). by O–P–O units to form infinite chains. The M···M dis-
Therefore, a three-dimensional network structure is built tances across the O–P–O unit within the chain are 5.813 Å
for 2, 5.794 Å for 3, 5.767 Å for 4, and 5.941 Å for 5. These
chains are connected by hydrogen-bond interactions as well
as π–π stacking interactions. The average centroid–centroid
distances between the two phenyl rings of the benzimidaz-
ole groups are 3.482 Å for 2, 3.470 Å for 3, 3.490 Å for 4,
i
ii
iii
and 3.620 Å for 5. The N3···O2 , O3···O4 , and O6···O2
distances are 2.757(4), 2.690(4), and 2.583(4) Å for 2,
.739(5), 2.699(4), and 2.570(4) Å for 3, 2.715(3), 2.632(3),
2
and 2.550(3) Å for 4, and 2.805(5), 2.702(4), and 2.529(4) Å
for 5, respectively.
It could be of interest to compare the coordination capa-
bilities of the bibmp4– ligand with that of N,N-bis(phos-
5–
phonomethyl)aminoacetate (bpmaa ; Scheme 2) as both
can offer up to six phosphonate oxygen atoms for coordina-
tion with the metal ions. For the bpmaa5– ligand, the car-
boxylate group has additional two oxygen donors. Thus, se-
veral transition metal/bpmada5– compounds have been pre-
[
14]
pared that show two- and three-dimensional structures.
For the bibmp4– ligand, only one nitrogen atom of each
benzimidazole group can be used for the coordination when
the reaction pH is not high enough. Besides, the benzimid-
azole group present in this ligand also provides a topologi-
Figure 4. The inter-chain hydrogen bond interactions among the
phosphonate oxygen atoms in structure 1. All H atoms except
H3A, H3B and H6A are omitted for clarity.
Figure 5. Packing diagram of structure 1 projected along b-axis. All H atoms are omitted for clarity.
Eur. J. Inorg. Chem. 2006, 1830–1837
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D.-K. Cao, J. Xiao, Y.-Z. Li, J. M. Clemente-Juan, E. Coronado, L.-M. Zheng
FULL PAPER
cal hydrophobic environment, possible π–π stacking inter- 2.07),[17] and [Mn(OAc)(terpy)(µ1,5-dca)] [dca = N(CN) ,
–
n
2
actions between the phenyl rings, and steric hindrance as OAc = acetate, terpy = 2,2Ј:6Ј,2ЈЈ-terpyridine] (g = 2.15).[
well. Hence, it is not unexpected that different structures
18]
will be constructed when metal sources react with bibmpH4
and bpmaaH acids. This paper shows that metal/
5
2
–
bibmpH2 compounds with zigzag chain structures can be
obtained through hydrothermal reactions of metal sulfates
and the acid bibmpH4.
M M
Figure 6. The χ T and χ vs. T plots for 1.
Dominant antiferromagnetic interactions are also ob-
served in compounds 2 and 3 (Figures 7 and 8, respec-
II
II
tively). As is well known, both Fe and Co ions in octahe-
dral environments show significant single-ion anisotropies
or spin-orbital couplings. When the symmetry of the mole-
cule is lowered, the orbital contribution can be partially re-
moved. In the present case each metal atom has a distorted
trigonal-bipyramidal geometry, therefore the orbital contri-
Scheme 2.
Magnetic Properties
The temperature-dependent magnetic behaviors of com-
pounds 1–4 were investigated in the temperature range 1.8–
II
II
butions of both Fe and Co would be reduced. The
susceptibility data were initially fitted by the Fisher formula
300 K. The room-temperature effective magnetic moments
[
Equation (1)], with S = 2 for 2 and S = 3/2 for 3, which
are 6.24 µ /Mn for 1 (expected 5.92 µ for S = 5/2), 5.12 µ /
Fe for 2 (expected 4.90 µ for S = 2), 4.57 µ /Co for 3 (ex-
pected 3.87 µ for S = 3/2), and 1.82 µ /Cu for 4 (expected
B
B
B
–1
leads to the parameters g = 2.07, J = –0.33 cm , and N =
2
N = 1.7×10 cm mol for 3. The J value of compound
α
B
B
.0×10–4 cm mol for 2 and g = 2.15, J = –0.35 cm , and
3
–1
–1
B
B
–
3
3
–1
α
1
.73 µ for S = 1/2). Figure 6 shows the χM and χ T vs. T
B
M
2
is comparable to that for [NH (CH ) NH ]-
3 2 2 3
plots for compound 1. The continuous decrease of χ T
upon cooling suggests a dominant antiferromagnetic ex-
change coupling between the Mn centers. Since structure
M
II
[Fe{HO PC(CH )(OH)(PO H)} ]·2H O, in which the Fe
3 3 3 2 2
–1
II
ions are doubly bridged by O–P–O units (J = –0.46 cm )
and the same equation was employed for the data fitting.[
The Fisher formula, however, is a simplified model that as-
sumes Heisenberg exchange couplings between all spins and
does not take into account the single-ion anisotropy or
spin-orbit coupling of either Fe or Co ions. A theoretical
analysis considering both zero-field splitting (ZFS) and a
small antiferromagnetic interaction would be a more logical
19]
II
1
is one-dimensional and the Mn ions are linked purely
through O–P–O units, the susceptibility data can be ana-
lyzed by Fisher’s expression for a uniform chain based on
the Heisenberg Hamiltonian H = –J∑S ·SAi+1, with the
Ai
II
II
classical spins scaled to a real quantum spin S = 5/2 [Equa-
[
15]
tion (1)],
approach. In order to fit the χ T vs. T plots of compounds
M
2
and 3, we calculated the magnetic susceptibility of six-
membered closed rings. Due to the high-spin value we can
suppose that the magnetic behavior of these closed rings is
[
20]
very similar to that of an infinite chain. The Hamiltonian
can therefore be used in its simplified axial form with an
(
1)
where J is the coupling constant, N, g, β and k have their axial ZFS parameter (D), the antiferromagnetic exchange
usual meanings, and N accounts for both the diamagnetic interaction (J), an axial g vector, and a temperature-inde-
α
and TIP contributions. A good fit, shown as the solid line pendent paramagnetism (TIP). The analysis of the data was
–1
in Figure 6, gives the parameters g = 2.09, J = –0.075 cm , performed with the full-matrix diagonalization program
–
4
3
–1
[21]
and N = 4.0×10 cm mol . The value of g is higher than MAGPACK.
After a least-squares fitting the following
α
II
–1
–1
that expected for a high-spin Mn ion (g = 2). A higher g parameters were found: J = –0.1 cm , D = 0.51 cm , g =
value has also been reported for the compounds [Mn(N ) - 2.09, and TIP = 3.3×10 for the Fe complex 2 and J =
bte)] [bte = 1,2-bis(1,2,4-triazol-1-ylethane)] (g = 2.06),
–4
II
3
[
2
16]
–1
–1
(
[
–0.15 cm , D = 7.6 cm , g = 2.33, g = 2.08, and TIP =
z xy
2
–
–3
II
{Mn(oda)(H O)}·H O] [oda = O(CH COO) ] (g = 1.1×10 for the Co complex 3, shown as solid lines in
2 2 n 2 2
1834
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Eur. J. Inorg. Chem. 2006, 1830–1837

Metal Phosphonates with One-Dimensional Chain Structures
FULL PAPER
Figures 7 and 8, respectively. The J values obtained for
compounds 2 and 3 are comparable to that of compound 1.
M M
Figure 9. The χ T and χ vs. T plots for 4.
Conclusion
Hydrothermal reactions of metal sulfates and
benzimidazol-2-ylmethyl)imino bis(methylenephosphonic
M M
Figure 7. The χ T and χ vs. T plots for 2.
(
acid) have resulted in five isostructural compounds with the
formula [M{(C H N )CH N(CH PO H) }] [M = Mn (1),
7
5
2
2
2
3
2
Fe (2), Co (3), Cu (4), and Cd (5)]. Each compound shows
a one-dimensional chain structure where {MO N } trigonal
3
2
bipyramids are connected by {CPO } tetrahedra through
3
corner-sharing. The benzimidazole rings are involved in
both aromatic stacking and hydrogen bonds. Further work
is in progress to explore new materials with other topologies
based on the same phosphonate ligand.
Experimental Section
Materials and Methods: N,N-Bis(phosphonomethyl)aminoacetic
[
14a]
acid was synthesized according to the literature procedure.
All
other reagents were purchased as reagent-grade chemicals and used
without further purification. Elemental analyses were performed
with a Perkin–Elmer 240C elemental analyzer. The IR spectra were
obtained as KBr disks on a VECTOR 22 spectrometer. Variable-
temperature magnetic susceptibility data were obtained for micro-
M M
Figure 8. The χ T and χ vs. T plots for 3.
For compound 4 there is a maximum at around 3 K in crystalline samples using a Quantum Design MPMS-XL7 SQUID
the χM vs. T plot (Figure 7), which is consistent with the magnetometer.
antiferromagnetic nature of the magnetic interactions. Con-
Synthesis of {[(Benzimidazol-2-ylmethyl)imino]bis(methylene)}bis-
sidering that compound 4 also has a chain structure with
(
7 5 2 2 2 3 2 4
phosphonic Acid) [(C H N )CH N(CH PO H) , bibmpH ]: Bis-
II
equally spaced Cu ions (S = 1/2), the susceptibility data (phosphonomethyl)imino acetic acid (5.26 g, 20 mmol) and 1,2-di-
can be fitted by the following equation based on the Heisen- aminobenzene (2.06 g, 20 mmol) were fully mixed by grinding. The
[
15]
berg Hamiltonian H = –J∑S ·S
[Equation (2)],
mixture was transferred to an open, single-necked flask and then
heated at 190 °C until no steam was produced. After cooling, 6 
hydrochloric acid (8 mL) was added to the flask. The resulting
solution was refluxed at 120 °C for 2 h, and then concentrated to
dryness. The blue solid was taken up in water (20 mL) and KOH
2) was added until the solid had dissolved (pH about 5–6). After re-
fluxing with decoloring charcoal for 30 min, the solution was fil-
tered off. The filtrate was acidified with 6  HCl until pH Յ
Ai Ai+1
(
where x = |J|/kT. A good fit, shown as the solid line in
Figure 9, results in the parameters g = 2.18, J = –2.96 cm ,
and N = –2.9×10 cm mol . The J value is smaller than
1.0.The white precipitate was collected, washed with methanol, and
–1
dried in vacuo. Yield: 5.5 g (82%). IR (KBr): ν˜ = 3153–2346 (br)
–5
3
–1
α
–1
cm , 1625 (m), 1573 (w), 1524 (w), 1491 (w), 1460 (m), 1438 (w),
those found for compounds [{Cu (di-2-pyridylamine) (µ-
3
3
1418 (w), 1400 (m), 1383 (w), 1367 (w), 1344 (m), 1308 (m), 1285
(m), 1252 (s), 1219 (s), 1159 (s), 1134 (s), 1059 (s), 1019 (s), 992 (s),
–
1 [22]
HPO )(µ-PO )(H O)}(PF )(H O) ] (–4.98 cm )
and
4
4
2
6
2
3 n
–
1 [23]
[
{(bipy)Cu(H O)} (µ-P O )·7H O] (J = –20 cm ), where 958 (s), 926 (s), 899 (m), 887 (m), 851 (m), 828 (m), 752 (s), 727
2 2 2 7 2
II
the Cu ions are also linked by O–P–O units.
(w), 620 (w), 572 (w), 544 (w), 496 (s), 468 (m), 456 (m), 434 (w),
1835
Eur. J. Inorg. Chem. 2006, 1830–1837
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org

D.-K. Cao, J. Xiao, Y.-Z. Li, J. M. Clemente-Juan, E. Coronado, L.-M. Zheng
FULL PAPER
4
3
11 (w). C10
5.72, H 4.82, N 12.55.
H
15
N
3
O
6
P
2
: calcd. C 35.85, H 4.51, N 12.54; found C
(w), 1388 (w), 1342 (w), 1323 (w), 1311 (w), 1282 (w), 1184 (s),
1132 (s), 1093 (m), 1067 (s), 1040 (m), 1021 (w), 982 (w), 969 (w),
9
18 (s), 834 (w), 781 (w), 756 (m), 714 (w), 653 (w), 578 (s), 513
Synthesis of [Mn{(C
bibmpH (0.15 mmol, 0.0495 g) and MnSO
.0253 g) in 8 mL of H O, adjusted to pH 2.5–3.5 with 1  NaOH,
was kept in a Teflon-lined autoclave at 140 °C for 24 h. After slow
cooling to room temperature, gray-blue, block-shaped crystals were
obtained as a monophasic material (according to the powder X-
7
H
5
N
2
)CH
2
N(CH
2
PO
3
H)
2
}] (1): A mixture of
(
w), 499 (w), 472 (w), 448 (w), 423 (w), 408 (w).
4
4
·H O (0.15 mmol,
2
0
2
Synthesis of [Cu{(C )CH N(CH PO H) }] (4): A mixture of
bibmpH (0.10 mmol, 0.0330 g) and CuSO (0.13 mmol, 0.0208 g)
in 8 mL of H O, adjusted to pH 4.90 with 1  NaOH, was kept in
a Teflon-lined autoclave at 140 °C for 24 h. After slow cooling to
room temperature, green, block-shaped crystals were obtained to-
gether with a brown powder. The crystals were selected manually
and were used for single-crystal structural determination and physi-
7
H
5
N
2
2
2
3
2
4
4
2
ray diffraction pattern). Yield: 23 mg (40%). C10
3 6 2
H13MnN O P :
calcd. C 30.92, H 3.35, N 10.82; found C 30.93, H 3.21, N 10.80.
–1
IR (KBr): ν˜ = 3104 (m, br) cm , 2939 (w), 2874 (w), 1622 (w),
598 (w), 1522 (w), 1467 (m), 1455 (m), 1432 (m), 1387 (w), 1377
w), 1343 (w), 1324 (w), 1309 (w), 1282 (w), 1266 (w), 1236 (m),
1
(
cal measurements. Yield: 22 mg (55% based on bibmpH
13CuN : calcd. C 30.25, H 3.28, N 10.59; found C 30.34,
H 3.43, N 10.62. IR (KBr): ν˜ = 3121–2900 (m, br) cm , 1622 (w),
597 (w), 1529 (w), 1494 (w), 1473 (m), 1456 (m), 1434 (m), 1419
m), 1378 (w), 1341 (w), 1320 (w), 1281 (w), 1256 (m), 1238 (s),
4
).
C
10
H
3 6 2
O P
1
9
181 (s), 1133 (s), 1100 (m), 1073 (s), 1035 (m), 958 (w), 941 (w),
15 (s), 852 (w), 832 (w), 754 (m), 686 (w), 651 (w), 576 (s), 505
–1
1
(
1
9
(
w), 499 (w), 472 (w), 448 (w), 408 (w).
Synthesis of [Fe{(C )CH N(CH PO
bibmpH (0.10 mmol, 0.0330 g) and FeSO
.0556 g) in 8 mL of H O, adjusted to pH 7.03 by adding 0.2 mmol
NOH, was kept in a Teflon-lined autoclave at 140 °C for
7
H
5
N
2
2
2
3
H)
2
}] (2): A mixture of
·7H O (0.20 mmol,
193 (s), 1128 (s), 1095 (m), 1059 (m), 1035 (m), 988 (w), 961 (w),
44 (w), 918 (s), 834 (w), 784 (w), 767 (m), 757 (m), 721 (w), 653
4
4
2
0
2
(
w), 584 (s), 560 (m), 512 (w), 499 (w), 474 (w), 447 (w), 414 (w).
of Me
4
Synthesis of [Cd{(C )CH N(CH PO H) }] (5): A mixture of
7
H
5
N
2
2
2
3
2
24 h. After slow cooling to room temperature, gray-green, block-
bibmpH (0.15 mmol, 0.0495 g) and CdSO ·2.7H O (0.15 mmol,
.0380 g) in 8 mL of H O, adjusted to pH 3.0–4.0 with 1  NaOH,
4
4
2
shaped crystals were obtained together with a brown powder. The
crystals were selected manually and were used for single-crystal
structural determination and physical measurements. Yield: 16 mg
0
2
was kept in a Teflon-lined autoclave at 140 °C for 24 h. After slow
cooling to room temperature, gray-blue block-shaped crystals were
obtained as a monophasic material (according to the powder X-
ray diffraction pattern). Yield: 37 mg (55%). Anal. found (calcd.)
(41% based on bibmpH
4
). C10
3 6 2
H13FeN O P : calcd. C 30.85, H
3
2
.34, N 10.80; found C 30.35, H 3.56, N 10.46. IR (KBr): ν˜ = 3104–
886 (m, br) cm , 1623 (w), 1598 (w), 1524 (w), 1467 (m), 1456
–1
for C10
6.82, H 2.85, N 9.28. IR (KBr): ν˜ = 3102 (m) cm , 2939 (w), 2868
w), 1619 (w), 1598 (w), 1521 (w), 1490 (w), 1469 (m), 1456 (m),
432 (m), 1386 (w), 1377 (w), 1344 (w), 1325 (w), 1311 (w), 1286
w), 1266 (w), 1238 (m), 1206 (m), 1176 (s), 1129 (s), 1097 (m),
072 (s), 1038 (m), 979 (w), 967 (w), 955 (w), 942 (w), 913 (s), 853
w), 830 (w), 765 (w), 754 (m), 684 (w), 649 (w), 576 (s), 502 (w),
87 (w), 460 (w), 442 (w), 410 (w).
3 6 2
H13CdN O P : calcd. C 26.93, H 2.92, N 9.43; found C
(m), 1434 (m), 1420 (m), 1387 (w), 1377 (w), 1342 (m), 1323 (w),
–
1
2
(
1
(
1
(
4
1309 (w), 1281 (w), 1264 (w), 1236 (m), 1185 (s), 1140 (s), 1091
(
(
m), 1065 (s), 1036 (s), 1021 (s), 981 (m), 968 (m), 955 (m), 941
m), 918 (s), 898 (m), 833 (m), 778 (m), 756 (m), 704 (w), 653 (w),
5
77 (s), 560 (m), 509 (w), 496 (w), 470 (w), 447 (w), 420 (w).
Synthesis of [Co{(C )CH N(CH PO H) }] (3): A mixture of
bibmpH (0.15 mmol, 0.0495 g) and CoSO ·7H O (0.15 mmol,
.0422 g) in 8 mL of H O, adjusted to pH 3.0–4.0 with 1  NaOH,
7
H
5
N
2
2
2
3
2
4
4
2
0
2
was kept in a Teflon-lined autoclave at 140 °C for 24 h. After slow
cooling to room temperature, magenta, block-shaped crystals were
obtained as a monophasic material (according to the powder X-
X-ray Crystallographic Studies: Single crystals of dimensions
3
3
0.1×0.04×0.04 mm
for 1, 0.1×0.05×0.05 mm
for 2,
3
3
0.15×0.15×0.15 mm for 3, 0.04×0.02×0.02 mm for 4, and
3
ray diffraction pattern). Yield: 46 mg (78%). Anal. found (calcd.) 0.1×0.05×0.05 mm for 5 were used for structural determinations
for C10 Co: calcd. C 30.60, H 3.32, N 10.71; found C on a Bruker SMART APEX CCD diffractometer using graphite-
13 3 6 2
H N O P
–
1
3
1
0.66, H 3.30, N 10.53. IR (KBr): ν˜ = 3100–2887 (m, br) cm ,
625 (w), 1598 (w), 1529 (w), 1469 (m), 1457 (m), 1433 (m), 1420
α
monochromatized Mo-K radiation (λ = 0.71073 Å) at room tem-
perature. Further details can be found in Table 2. A hemisphere of
Table 2. Crystallographic data and refinement parameters for 1–5.
Compound
1
2
3
4
5
Empirical formula
Fw
C
388.11
10
H
13MnN
3
O
6
P
2
C
389.02
10
H
13FeN
3
O
6
P
2
C
392.10
10
H
13CoN
3
O
6
P
2
C
396.71
10
H
13CuN
3
O
6
P
2
C
445.57
10 3 6 2
H13CdN O P
Crystal system
Space group
a [Å]
orthorhombic
Pbca
15.331(2)
10.7150(16)
16.715(2)
2745.8(6)
8
orthorhombic
Pbca
15.320(3)
10.477(2)
16.764(3)
2690.7(9)
8
orthorhombic
Pbca
15.207(2)
10.4626(16)
16.794(3)
2672.0(7)
8
orthorhombic
Pbca
15.101(3)
10.3517(17)
16.997(3)
2656.9(7)
8
orthorhombic
Pbca
15.4679(19)
10.8923(13)
16.6175(19)
2799.7(6)
8
b [Å]
c [Å]3
V [Å ]
Z
–3
ρcalcd. [gcm ]
1.878
1.921
1.949
1.984
2.114
F(000)
1576
0.0835
1.042
1584
0.0585
1.042
1592
0.073
1.090
1608
0.0517
1.136
1760
0.056
1.141
R
int
2
Goodness of fit on F
R
1, wR
1, wR
2
[I Ͼ 2σ(I)]
(all data) –
0.0641, 0.1169
0.1107, 0.1281
0.407, –0.438
0.0484, 0.1105
0.0715, 0.1205
0.979, –1.231
0.0564, 0.0998
0.0876, 0.1110
0.550, –0.458
0.0426, 0.0901
0.0557, 0.0926
0.397, –0.433
0.0429, 0.0599
0.0707, 0.0636
0.870, –0.952
[
a]
R
2
3
(
∆ρ)max, (∆ρ)min [eÅ ]
[
a] R = ∑ ||F | – |F ||/∑||F
1
o
c
o
|; wR
2
= [∑w(F 2
o
– F
c
2)2/∑w(F 2)2]1/2.
o
1836
www.eurjic.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 1830–1837

Metal Phosphonates with One-Dimensional Chain Structures
FULL PAPER
data were collected in the θ range 2.62–26.00° for 1, 2.43–26.00°
for 2, 2.43–25.99° for 3, 2.40–25.99° for 4, and 2.45–26.00° for 5
using a narrow-frame method with scan widths of 0.30° in ω and
an exposure time of 5 s per frame. Numbers of observed and
unique [I Ͼ 2σ(I)] reflections are 13496 and 2700 (Rint = 0.0835)
for 1, 13174 and 2634 (Rint = 0.0585) for 2, 13176 and 2618 (Rint
Commun. 1998, 175; e) E. Burkholder, V. Golub, C. J.
O’Connor, J. Zubieta, Inorg. Chem. 2003, 42, 6729; f) B. A.
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1
518; g) C. Serre, N. Stock, T. Bein, G. Ferey, Inorg. Chem.
2004, 43, 3159; h) B.-P. Yang, J.-G. Mao, Y.-Q. Sun, H.-H.
Zhao, A. Clearfield, Eur. J. Inorg. Chem. 2003, 4211; i) X. Shi,
G.-S. Zhu, S.-L. Qiu, K.-L. Huang, J.-H. Yu, R.-R. Xu, Angew.
Chem. Int. Ed. 2004, 43, 6482.
=
0.073) for 3, 12675 and 2605 (Rint = 0.0517) for 4, and 14077
and 2754 (Rint = 0.056) for 5, respectively. The data were integrated
using the Siemens SAINT program,[ with the intensities cor-
rected for Lorentz factors, polarization, air absorption, and absorp-
tion due to variation in the path length through the detector face-
plate. Multi-scan absorption corrections were applied. The struc-
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T. H. Warren, W. Lin, Inorg. Chem. 2001, 40, 5954; b) X.-Y.
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2
tures were solved by direct methods and refined on F by full-ma-
trix least-squares using SHELXTL.[ All the non-hydrogen atoms
were located from the Fourier maps, and were refined anisotropi-
cally. All H atoms were refined isotropically, with the isotropic vi-
bration parameters related to the non-H atom to which they are
bonded.
25]
7
21; g) D.-K. Cao, Y.-Z. Li, L.-M. Zheng, Inorg. Chem. 2005,
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2
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Received: September 7, 2005
[
Published Online: March 13, 2006
Eur. J. Inorg. Chem. 2006, 1830–1837
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1837