Synthesis and characterisation of polymeric manganese and zinc 5-hydroxyisophthalates

Article abstract of DOI:10.1016/S0277-5387(01)00804-X

The crystallisation of 5-hydroxyisophthalic acid with divalent Mn or with Mn or Zn and either 2,2-bipyridine (2,2-bipy) or pyridine-2-(1H-pyrazol-3-yl) gave solids of composition [Mn(C₈H₄O₅) (H₂O)₃]·2

Full text of DOI:10.1016/S0277-5387(01)00804-X

Polyhedron 20 (2001) 2293–2303
www.elsevier.com/locate/poly
Synthesis and characterisation of polymeric manganese and zinc
5-hydroxyisophthalates
M. John Plater a,*, Mark R.St.J. Foreman a, R. Alan Howie a, Janet M.S. Skakle a,
Susan A. McWilliam a, Eugenio Coronado b,1, Carlos J. Go´mez-Garc´ıa b
a Room G103, Meston Building, Department of Chemistry, Uni6ersity of Aberdeen, Meston Walk, Aberdeen, AB24 3UE, UK
b Instituto de Ciencia Molecular, Uni6ersidad de Valencia, Dr. Moliner 50, 46100 Burjassot, Spain
Received 5 February 2001; accepted 3 April 2001
Abstract
The crystallisation of 5-hydroxyisophthalic acid with divalent Mn or with Mn or Zn and either 2,2-bipyridine (2,2-bipy) or
pyridine-2-(1H-pyrazol-3-yl) gave solids of composition [Mn(C8H4O5)(H2O)3]·2H2O (1), [Mn(C8H4O5)(2,2%-bipy)]·H2O (2),
[Mn2(C8H4O5)2(C8H7N3)2]·H2O (3) and [Zn(C8H4O5)(2,2%-bipy)] (4). Each compound has 1D co-ordinative chains that are
connected by hydrogen bonds. Compounds 2–4 contain M2C2O4 rings with pseudo-chair geometries. The Mn atoms in 2 are
coupled antiferromagnetically. © 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Manganese; Hydrothermal; Co-ordination polymer
1. Introduction
2. Experimental
Encouraged by our successful synthesis of co-ordina-
tion polymers using metal acetates, benzene-1,3,5-tri-
carboxylic acid (H3BTC) and 2,2%-bipyridine (2,2-bipy)
[1], we chose to investigate the effect of replacing
H3BTC with 5-hydroxyisophthalic acid. This was se-
lected because like H3BTC it has two carboxylic acids
arranged meta, but at a position meta to both carboxyl
groups is a phenol hydroxyl group. The phenol hy-
droxyl was intended as a mimic for the third carboxyl
group which remains protonated in our recently re-
ported layered polymers [1]. Manganese(II) metal-ions
were of interest because high spin manganese(II) ions
possess five unpaired electrons which can couple ferro-
magnetically [1].
All organic chemicals were purchased from Lancaster
while metal salts were purchased from Aldrich or BDH.
Hydrothermal, infra-red and TGA experiments were
performed using previously described equipments [1].
2.1. [Mn(C8H4O5)(H2O)3]·2H2O (1)
5-Hydroxyisophthalic acid (2.81 g, 15.6 mmol), man-
ganese(II) acetate tetrahydrate (3.8 g, 15.5 mmol) and
water (100 ml) were heated under reflux for 5 min
before being allowed to cool. After cooling to room
temperature (r.t.) the mixture was filtered. The volume
was reduced in vacuo until a white solid formed to
which water (10 ml) was added. After allowing the
mixture to stand overnight a solid was collected by
filtration, washed with water and air-dried to give 1 as
a white microcrystaline solid (4.2 g, 83%). Anal. Found:
C, 29.2; H, 4.2; N, B0.3. Calc. for [Mn(C8H4O5)-
(H2O)3]·2H2O: C, 29.6; H, 4.3; N, 0.0%. IR (KBr,
cm−1): 3546br, 3460br, 3411br, 3250br, 1663w, 1654w,
1636m, 1619m, 1559s, 1543s, 1507m, 1500m, 1458m,
1397s, 1368sh, 1308m, 1280m, 1233w, 1134w, 1107w,
1002w, 983m, 941w, 914w, 891w, 817m, 780s, 739s.
* Corresponding author. Tel.: +44-1224-272927; fax: +44-1224-
272921.
E-mail addresses: m.j.plater@abdn.ac.uk (M. John Plater), euge-
nio.coronado@uv.es (E. Coronado).
1 Tel./fax: +34-96-3864859.
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00804-X

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M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
TGA: an endothermic mass loss of 26.7% occurs be-
tween r.t. and 110°C (for total dehydration a mass loss
of 27.7% is required).
bipyridyl (89 mg, 0.57 mmol) and water (10 ml) were
placed in a 23 ml Parr bomb. After sealing this bomb
was heated at 100°C h−1 to 220°C. After 2 h the bomb
was cooled at 5°C h−1 to 180°C. After a further 6 h the
bomb was cooled at 2°C h−1 to r.t. The colourless crys-
tals (170 mg, 75%) were collected by filtration, washed
with water and dried in air. Anal. Found: C, 53.3; H, 2.8;
N, 6.7. Calc. for [Zn(C8H4O5)(C10H8N2)]: C, 53.8; H,
3.0; N, 7.0%. IR (KBr, cm−1): 3440brs, 3240br, 1626s,
1609s, 1574vs, 1547sh, 1493m, 1475m, 1442s, 1425s,
1384s, 1318w, 1288w, 1276w, 1250w, 1224w, 1211w,
1174w, 1159w, 1126w, 1103w, 1078w, 1057w, 1020m,
1004w, 976m, 933w, 913w, 889m, 787m, 768m, 734m,
718m, 651w, 628w, 467m, 417m. TGA: above 190°C a
mass loss due to general decomposition occurred.
2.2. [Mn(C8H4O5)(2,2%-bipy)]·H2O (2)
5-Hydroxyisophthalic acid (101 mg, 0.56 mmol), man-
ganese(II) acetate tetrahydrate (137 mg, 0.56 mmol),
2,2%-bipyridyl (87 mg, 0.56 mmol) and water (10 ml)
were placed in a 23 ml Parr bomb. After sealing the
bomb was heated at 100°C h−1 to 220°C. After 2 h the
bomb was cooled at 5°C h−1 to 180°C. After a further 6
h the bomb was cooled at 5°C h−1 to r.t. The yellow
crystalline product (147 mg, 65%) was collected by filtra-
tion, washed with water and air-dried. When the experi-
ment was repeated with slower cooling from 180°C
(2°C h−1) darker particles were produced in addition to
2. Anal. Found: C, 52.6; H, 3.2; N, 6.7. Calc. for
[Mn(C8H4O5)(C10H8N2)(H2O)]: C, 52.8; H, 3.5; N, 6.8%.
IR (KBr, cm−1): 3402brs, 1664m, 1655m, 1619m, 1604s,
1595w, 1577s, 1541vs, 1488m, 1473m, 1439s, 1415w,
1385vs, 1313m, 1298w, 1273m, 1247w, 1215m, 1152w,
1119w, 1103m, 1093sh, 1062w, 1044w, 1018m, 1009w,
1000w, 977m, 946w, 936w, 906w, 890w, 846w, 801m,
786m, 765m, 736sh, 725m, 685w, 650m, 627w, 564w,
490w, 470w, 455w. TGA: between 80 and 190°C a mass
loss of 4.5% occurred (for the conversion of the mono-
hydrate to an anhydrous solid a mass loss of 4.4% is re-
quired). Above 330°C decomposition occurred.
2.5. X-ray crystallographic studies
2.5.1. Structure determinations
Data for 1 and 4 were collected on a Bruker SMART
1000 CCD diffractometer at 295 K, with data collection
using SMART [2] and data reduction using SAINT [2]. Ab-
sorption correction was applied using SADABS [2]. Data
for 2 and 3 were collected on an Enraf–Nonius Kappa-
CCD diffractometer at 150 K with data collection and
reduction using DENZO [3] and COLLECT [4]. Absorption
correction was applied using SORTAV [5]. All structures
were solved by direct methods using SHELXS-97 [6] and
refined by least-squares methods using SHELXL-97 [6]. In
all cases, refinement proceeded smoothly to the values
given and all non-water H-atoms were placed geometri-
cally. For structures 1–3, H atoms on water molecules
were identified from the difference Fourier map.
2.3. [Mn2(C8H4O8)2(C8H7N3)2]·H2O (3)
5-Hydroxyisophthalic acid (102 mg, 0.57 mmol),
manganese(II) acetate tetrahydrate (138 mg, 0.56
mmol), pyridine-2-(1H-pyrazol-3-yl) (149 mg, 1.026
mmol) and water (20 ml) were placed in a 45 ml
bomb. The resulting mixture was heated at 100°C h−1
to 240°C. After 2 h the bomb was cooled to 180°C
at 5°C h−1 and after 6 h the bomb was cooled at
2°C h−1 to r.t. before being opened. The colourless solid
(161 mg, 74%) was harvested but was not phase pure. IR
(KBr, cm−1): 1615m, 1577m, 1561m, 1541s, 1516w,
1489w, 1433m, 1411sh, 1386s, 1361m, 1300m, 1272m,
1218w, 1105w, 1089w, 1059w, 1018w, 1002w, 978w,
2.6. Magnetic measurements
Variable-temperature susceptibility measurements
were carried out in the temperature range of 2–300 K at
a magnetic field of 0.1 T for a polycrystalline sample
with
a SQUID magnetometer (Quantum Design
MPMS-XL-5). The susceptibility data were corrected
from the diamagnetic contributions as deduced by using
Pascal’s constant tables and were fitted with the van
Vleck equation for a S=5/2 dimer with a monomeric
paramagnetic impurity (c):
NAg2i2 2e2x+10e6x+28e12x+60e20x+110e30x
kBT 1+3e2x+5e6x+7e12x+9e20x+11e30x
35g2
32
m=(1−c)
+c
968w, 930w, 890w, 814w, 801m, 784m, 766m, 725m,
640w, 617w.
where x=J/kBT.
With the molecular field approach the expression for
the susceptibility becomes:
2.4. [Zn(C8H4O5)(2,2%-bipy)] (4)

m
% =
m
2zJ%
NAg2i2
m
5-Hydroxyisophthalic acid (103 mg, 0.57 mmol),
zinc(II) acetate dihydrate (124 mg, 0.565 mmol), 2,2%-
1−

M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
2295
Fig. 1. Top: drawing of the manganese co-ordination environment in 1. Middle: drawing of a 1D co-ordinative chain. Bottom: drawing showing
hydrogen bonds between adjacent layers.

2296
M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
Table 3
The theoretical curve of the magnetisation has been
calculated by using the computation program MAG-
PACK [7].
,
Selected bond lengths (A) and angles (°) for 2
Mn1ꢀO3c1
Mn1ꢀO4c2
Mn1ꢀN1
Mn1ꢀN2
Mn1ꢀO2
2.1175(15)
2.1524(15)
2.2362(18)
2.2507(18)
2.2512(14)
2.2868(14)
2.1175(15)
2.1524(15)
O3c3ꢀMn1ꢀO4c2 94.67(6)
N1ꢀMn1ꢀN2
O1ꢀMn1ꢀO2
72.31(7)
58.00(5)
3. Results and discussion
Mn1ꢀO1
3.1. [Mn(C8H4O5)(H2O)3]·2H2O (1)
Mn1c1ꢀO3
Mn1c3ꢀO4
5-Hydroxyisophthalic acid was chosen as a co-ordi-
nation polymer precursor because it has tridentate
functionality like benzene-1,3,5-tricarboxylic acid, ex-
cept that one of the carboxylic acid groups has been
replaced with a hydroxyl group. No crystal structures
of 5-hydroxyisophthalates were found in the Cambridge
Structural Database [8] although an infinite array has
been reported which contains 5-hydroxyisophthalic acid
as a building block [9]. After alkylation of the phenol
group the diacid has been used as a building block in
polymers [10]. An initial attempt at the hydrothermal
Symmetry transformations used to generate equivalent atoms: c1
−x+1, −y, −z, c2 x+1/2, −y, z+1/2, c3 x−1/2, −y, z−1/2.
Table 4
,
Hydrogen bonds (A and °) for 2
DꢀH···A
d(DꢀH)
d(H···A)
d(D···A)
Ú(DHA)
O5ꢀH5···O1W
O1WꢀH2W···O2
O1WꢀH1W···O4
0.840
0.827
0.821
1.830
2.120
2.025
2.649
2.863
2.795
164.45
149.37
156.05
synthesis
of
manganese(II)-5-hydroxyisophthalate
Symmetry transformations used to generate equivalent atoms: c1
−x+1, −y, −z; c2 x+1/2, −y, z+1/2; c3 x−1/2, −y, z−1/2;
c4 −x −1/2, y, −z−1/2; and c5 −x, −y, −z.
yielded a colourless solution. Slow evaporation gave
crystals of the hydrated polymeric carboxylate 1 (Fig.
1). The manganese has a distorted pentagonal bipyra-
midal co-ordination geometry. In equatorial sites are
four-carboxylate oxygens from chelating carboxylate
ligands and one-water oxygen O6. In the axial sites are
two-water oxygens O7 and O8. Two non-co-ordinated
waters are present which hydrogen bond to carboxylate
groups, the phenol group and other waters. The solid
contains 1D co-ordinative chains of manganese atoms
bridged by the carboxylate ligands. These chains are
interlinked by means of a network of hydrogen bonds.
The hydrogen bond network links each chain to other
Table 1
,
Selected bond lengths (A) and angles (°) for 1
Mn(1)ꢀO(7)
Mn(1)ꢀO(8)
Mn(1)ꢀO(6)
2.120(2)
2.166(2)
2.178(2)
O(7)ꢀMn(1)ꢀO(8)
O(7)ꢀMn(1)ꢀO(6)
O(8)ꢀMn(1)ꢀO(6)
177.95(10)
89.33(11)
90.28(10)
82.96(8)
55.66(6)
83.21(6)
Mn(1)ꢀO(4)c1 2.2550(19) O(6)ꢀMn(1)ꢀO(2)
Mn(1)ꢀO(2)
Mn(1)ꢀO(1)
2.2767(18) O(2)ꢀMn(1)ꢀO(1)
2.4059(19) O(4)c1ꢀMn(1)ꢀO(1)
Mn(1)ꢀO(5)c1 2.4477(18) O(4)c1ꢀMn(1)ꢀO(5)c1 55.38(6)
O(6)ꢀMn(1)ꢀO(5)c1
83.12(8)
Symmetry transformations used to generate equivalent atoms: c1
−x+1/2, y+1/2, −z; c2 −x+1/2, y−1/2, −z.
,
parallel chains which are approximately 3.8 A above
and below and to chains which are alongside (Tables
1–9).
Table 2
,
Hydrogen bonds (A and °) for 1
One-water HW6B hydrogen bonds to a carboxylate
oxygen O2 forming a Mn2O4H2 ring which interlinks
the chains. While the phenol hydrogen H3A hydrogen
bonds to a water oxygen O10, one of the water hydro-
gens HW1B then hydrogen bonds to O5 forming a
bridge between the chains. Carboxylate oxygen O4
hydrogen bonds to HW7A while HW7B binds to a
water oxygen O9. Also binding to O9 is another water
hydrogen HW8B while the other hydrogen in this water
HW8A binds to O1 forming a hydrogen bond bridge
between O1 and O4 within a chain. A water molecule
oxygen O9 hydrogen bonds to the axial waters O7 and
O8 which are co-ordinating to the manganese. Hydro-
gens within axial waters hydrogen bond to carboxylate
oxygens forming two further bridges between the
stacked chains. These hydrogen bonds exist between
carboxylate oxygens O1 and O4 and water hydrogens
DꢀH···A
d(DꢀH) d(H···A) d(D···A) Ú(DHA)
O(3)ꢀH(3A)···O(10)c3
O(6)ꢀHW6A···O(3)c4
O(6)ꢀHW6B···O(2)c3
O(7)ꢀHW7A···O(4)c5
O(7)ꢀHW7B···O(9)c3
O(8)ꢀHW8A···O(1)c6
O(8)ꢀHW8B···O(9)c7
O(9)ꢀHW9A···O(2)
0.82
1.80
2.610(3) 170.7
2.749(3) 170(4)
2.827(4) 162(3)
2.818(3) 167(4)
2.712(4) 175(3)
2.756(3) 152.9
3.115(4) 168.3
2.868(3) 133.6
3.038(4) 123.1
2.853(4) 165(5)
2.864(4) 169(6)
0.93(4) 1.83(4)
0.70(3) 2.15(3)
0.78(4) 2.05(4)
0.89(4) 1.83(4)
0.96
0.85
0.96
0.96
1.87
2.28
2.12
2.41
O(9)ꢀHW9B···O(3)c8
O(10)ꢀHW1A···O(5)c9 0.78(5) 2.09(5)
O(10)ꢀHW1B···O(5)c1 0.71(5) 2.16(5)
Symmetry transformations used to generate equivalent atoms: c1
−x+1/2, y+1/2, −z; c2 −x+1/2, y−1/2, −z; c3 −x+1,
−y+1, −z+1; c4 −x+1/2, y+1/2, −z+1; c5 x+1/2, −y+1/2,
z; c6 −x, −y+1, −z; c7 −x, −y+1, −z+1; c8 x−1/2,
−y+1/2, z; and c9 −x+1, −y+1, −z.

M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
2297
HW8A and HW7A, respectively. The water hydrogens
attached to O10 hydrogen bond to carboxylate oxygens
O5 in different layers. The water hydrogens attached to
O6 are hydrogen bonded to the phenol oxygen and a
carboxylate oxygen O2 forming a link between the
layers.
Table 5
,
Selected bond lengths (A) and angles (°) for 3
3.2. [Mn(C8H4O5)(2,2%-bipy)]·H2O (2)
Mn1ꢀO2c1
Mn1ꢀO1
2.128(3)
2.134(3)
2.234(3)
2.239(3)
2.247(4)
2.328(3)
O2c1ꢀMn1ꢀO1
O2c1ꢀMn1ꢀO3c2
O1ꢀMn1ꢀO3c2
O2c1ꢀMn1ꢀN2
O1ꢀMn1ꢀN2
O3c2ꢀMn1ꢀN2
O2c1ꢀMn1ꢀN1
O1ꢀMn1ꢀN1
93.8(1)
89.5(1)
96.4(1)
124.1(1)
96.2(1)
143.0(1)
83.5(1)
164.2(1)
99.2(1)
72.9(1)
The hydrothermal reaction of 5-hydroxyisophthalic
acid with manganese acetate and 2,2%-bipyridyl gave 2
as a bright yellow crystalline solid. In the structure of 2
manganese cations and carboxylate ligands form 1D
chains which are linked by a hydrogen bonding net-
work consisting of the phenol proton, the water
molecule and carboxylate oxygens into sheets (Fig. 2).
Between the mats of carboxylates are layers of parallel
bipy ligands. The closest approach between two bipy
Mn1ꢀO3c2
Mn1ꢀN2
Mn1ꢀN1
Mn1ꢀO4c2
O3c2ꢀMn1ꢀN1
N2ꢀMn1ꢀN1
O2c1ꢀMn1ꢀO4c2 145.2(1)
O1ꢀMn1ꢀO4c2
O3c2ꢀMn1ꢀO4c2
N2ꢀMn1ꢀO4c2
N1ꢀMn1ꢀO4c2
100.1(1)
57.5(1)
86.1(1)
90.7(1)
,
ligands is 3.379 A (C9ꢀC9 distance). The manganese
atoms are in pairs in a Mn2C2O4 ring and the inter-
,
manganese distance is 4.058 A. The next-nearest neigh-
,
bouring manganese atom is 6.223 A away. The
Symmetry transformations used to generate equivalent atoms: c1
−x+3/2, y, −z+1/2; c2 x−1/2, −y, z−1/2; and c3 x+1/2, −y,
z+1/2.
substitution of the carboxylic acid group in H3BTC for
a hydroxyl group has resulted in a considerable change
in the crystal structure. The different hydrogen bonding
properties of the two groups are likely to have a greater
influence on the structure.
Table 6
,
Hydrogen bonds (A and °) for 3
The manganese atoms are in a grossly distorted
octahedral environment. One carboxylate group
O1ꢀC8ꢀO2 and a 2,2%-bipy are chelating the manganese
while two other carboxylates are bridging between
manganese atoms forming an eight-membered boat
shaped ring. The torsion angle Mn1ꢀO4c2ꢀO3c
2ꢀMn1c4 is −40.4°. The nitrogen atoms of the bipy
are cis to O1 while only one nitrogen is cis to O2. The
O1ꢀMn1ꢀO2 and N1ꢀMn1ꢀN2 angles are much smaller
than the 90° expected for a perfect octahedral complex.
While the O4c2ꢀMn1ꢀO3c3 angle is significantly
different from 90° it is closer to the ideal octahedral
angle. Three hydrogen bonds help hold the layers of
manganese carboxylates together. The phenol proton
H5 hydrogen bonds to the water molecule O1W which
then hydrogen bonds to oxygens O4 and O2 in car-
boxylate groups in different molecules. The aromatic
DꢀH···A
d(DꢀH) d(H···A) d(D···A) Ú(DHA)
N(3)ꢀH(3A)···O(4)c4 0.88
2.05
1.81
2.06(5)
2.02(8)
2.875(5)
2.640(4)
2.781(4)
2.859(4)
155.0
169.9
154(5)
149(6)
O(5)ꢀH(5)···O(6)c5
O(6)ꢀH(6WA)···O(1)
O(6)ꢀH(6WB)···O(3)
0.84
0.78(5)
0.93(8)
c2
Symmetry transformations used to generate equivalent atoms: c1
−x+3/2, y, −z+1/2; c2 x−1/2, −y, z−1/2; c3 x+1/2, −y,
z+1/2; c4 −x+1, −y, −z+1; and c5 −x+1/2, y, −z+1/2.
Table 7
,
Selected bond lengths (A) and angles (°) for 4
Zn1ꢀO2c1
Zn1ꢀO5c2
Zn1ꢀO1
Zn1ꢀN2
Zn1ꢀN1
1.985(1)
1.985(1)
2.054(1)
2.156(1)
2.163(2)
O2c1ꢀZn1ꢀO5c2 118.3(1)
O2c1ꢀZn1ꢀO1
O5c2ꢀZn1ꢀO1
O2c1ꢀZn1ꢀN2
O5c2ꢀZn1ꢀN2
O1ꢀZn1ꢀN2
103.96(6)
88.5(1)
98.2(1)
143.4(1)
85.2(1)
101.3(1)
93.7(1)
,
rings of the bipy ligands are approximately 3.6 A from
O2c1ꢀZn1ꢀN1
each other and appear to be p stacked.
O5c2ꢀZn1ꢀN1
A large number of Mn2C2O4 rings containing six
co-ordinate manganese linked together by bridging car-
boxylate ligands are present in the crystallographic
literature. Many rings contain additional bridging lig-
ands such as oxide [11–13], water [14,15] or more
complex ligands [11]. However, some examples do exist
of Mn2C2O4 rings which are not supported by addi-
tional bridging ligands. These include mixed
Mn(II)ꢀMn(III) carboxylates [16] and Mn(II) carboxy-
lates [17–22].
Symmetry transformations used to generate equivalent atoms: c1
−x, −y, −z; c2 −x+1, −y, −z.
Table 8
,
Hydrogen bonds (A and °) for 4
DꢀH···A
O3ꢀH3a···O4
d(DꢀH)
0.820
d(H···A)
1.910
d(D···A)
2.724
Ú(DHA)
171.44
Symmetry transformations used to generate equivalent atoms: c1
−x, −y, −z; c2 −x+1, −y, −z; and c3 −x+2, −y−1, −z.

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M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
Table 9
Summary of key crystallographic data for compounds 1–4
Compound
1
2
3
4
Empirical formula
Formula weight
Temperature (K)
Crystal system
C8H14MnO10
325.13
302(2)
P2(1)/a
monoclinic
C
409.25
150(2)
P2/n
18H14MnN2O6
C16H13MnN3O6
398.23
150(2)
P2/n
monoclinic
C18H12ZnN2O5
401.67
301(2)
(
P1
Space group
monoclinic
triclinic
Unit cell dimensions
,
a (A)
7.5211(7)
18.4930(18)
9.5673(9)
8.5040(2)
11.0319(4)
18.4365(5)
8.2886(3)
10.9165(4)
17.9845(6)
8.5027(4)
10.1489(5)
10.7619(5)
85.3720(10)
67.254(1)
69.267(1)
799.3(1)
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
V (A )
108.00(1)
102.81(2)
100.38(2)
3
,
1265.6(2)
4
1.706
1686.6(1)
4
1.612
1600.6(1)
4
1.653
Z
2
Dcalc (Mg m−3
)
1.669
1.570
Absorption coefficient (mm−1
Absorption correction
Crystal size (mm)
)
1.089
0.823
0.866
semi-empirical
0.3×0.1×0.05
8062/0.0564
81.9%
3984/0/207
0.881
0.0452/0.0911
0.0937/0.1090
0.374 and −0.547
empirical
0.25×0.25×0.10
8181/0.0437
98.4%
3416/0/252
1.040
0.0387/0.0833
0.0591/0.0903
0.323 and −0.387
empirical
0.1×0.1×0.1
12 932/0.0565
79.6%
4141/0/244
1.044
0.0636/0.1392
0.1070/0.1550
0.945 and −0.928
semi-empirical
0.37×0.20×0.20
7726/0.0164
90.2%
4612/0/236
1.098
0.0319/0.0860
0.0391/0.0886
0.461 and −0.424
Reflections collected/Rint
Completeness to max 2q
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices R1/ꢀR2 [F2\2|(F2)]
R indices (all data)
−3
,
Largest difference peak and hole (e A
)
Fig. 2. Left: drawing of the Mn co-ordination environment in 2. Right: drawing showing the hydrogen bonding between sheets.

M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
2299
3.3. [Mn2(C8H4O8)2(C8H7N3)2]·H2O (3)
3.4. [Zn(C8H4O5)(2,2%-bipy)] (4)
The Mn(II) has a distorted octahedral co-ordination
environment which contains four oxygen and two nitro-
gen atoms (Fig. 3). Two oxygens from a chelating
carboxylate and one oxygen from a bridging carboxy-
late are cis to the pyridine nitrogen. The site trans to
the pyridine nitrogen is occupied by an oxygen from a
bridging carboxylate. Like the solids formed from zinc
and manganese acetates, hydroxyisophalic acid and
2,2%-bipy, eight-membered M2C2O4 rings are present.
The structure consists of layers of metal atoms and
carboxylate ligands which are separated by layers of the
nitrogen heterocycles. The structure is similar to that of
2 which is not surprising in view of the similarity of
2,2%-bipyridyl and pyridine-2-(1H-pyrazol-3-yl).
By heating zinc acetate, 5-hydroxyisophthalic acid
and 2,2-bipy under hydrothermal conditions 4 was ob-
tained as a colourless solid (Fig. 4). The zinc has a
distorted square-pyramidal geometry. The 2,2-bipy ni-
trogens and two carboxylate oxygens are equatorial
while a third carboxylate oxygen is in the axial site. In
common with structure 2 the metal atoms are in eight-
membered M2C2O4 rings. The relative arrangement of
the eight-membered rings to the carboxylate layers is
different to that observed for 2. An interlayer hydrogen
bond between the phenolic hydrogen H3A and a car-
boxylate oxygen O4 exists. A number of zinc carboxy-
lates containing five co-ordinate zinc atoms in Zn2C2O4
rings are known [23–29]. However, only two [23,29] of
Fig. 3. Top: drawing of the Mn co-ordination environment in 3. Bottom: drawing showing the sheets.

2300
M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
Fig. 4. Top: drawing showing the Zn co-ordination environment in 4. Bottom: drawing showing the different orientation of the sheets.
these Zn2C2O4 rings lacked bridging ligands which
provide additional links between the zincs.
continuous decrease upon cooling, reaching a value of
1.78 emu K mol−1 at 2 K. Such a behaviour is charac-
teristic of antiferromagnetic coupling between two spin
sextuplets of the manganese(II) ions. This behaviour is
better observed in the  versus temperature plot (Fig.
4. Magnetic properties
m
6) where a maximum in the susceptibility can be ob-
served at very low temperatures (2.8 K). Accordingly,
the susceptibility data were analysed with the van Vleck
equation for a dimer of high spin octahedral mangane-
se(II) ions (S=5/2) with the isotropic Heisenberg
hamiltonian Hex= −2JSASB, where J is the magnetic
coupling parameter (see Section 2). A fitting of the data
to this model leads to g=1.99, J= −0.37 cm−1 and a
monomeric Mn(II) paramagnetic impurity of 1.5%. The
The magnetic properties of compound [Mn(C8H4O5)-
(2,2%-bipy)(H2O)] (2) are depicted in Fig. 5 with a plot
of the product of mT (proportional to the square of
the magnetic moment) versus temperature. At room
temperature the mT value is 8.52 emu K mol−1 per
manganese dimer, which is very close to the value
expected for two magnetically isolated manganese(II)
centres with a spin sextuplet (S=5/2). mT reveals a

M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
2301
agreement is excellent in the whole temperature range
(solid lines in Figs. 5 and 6). This result indicates that
although the structure of compound 2 consists of
chains of manganese dimers, the exchange interaction is
restricted to the Mn(II)ꢀMn(II) pairs which are mag-
netically coupled through two ꢀOCOꢀ bridges. In this
case the spin coupling through the 5-hydroxyisophtha-
late anion is negligible. This antiferromagnetic coupling
between the manganese(II) ions connected only through
two ꢀOCOꢀ bridges has already been observed in other
similar Mn(II) dimers and chains, where J values rang-
ing from −0.33 to −1.76 cm−1 have been determined
[30–35].The good magnetic isolation produced by the
5-hydroxyisophthalate anion resembles that observed in
the related benzene-1,3,5-tricarboxylate [1], isophthalate
[35] and terephthalate anions [32,36] In fact, the intro-
duction of a molecular mean field [35] in the fitting
procedure, accounting for interdimer interactions (via
the 5-hydroxyisophthalate anion) or interchain interac-
tions (via the hydrogen bonding network), does not
improve the agreement with the experiment and the
values of the parameters remain unaffected. For exam-
ple, this model leads to g=1.99, J= −0.37 cm−1
,
zJ%= −0.005 cm−1 and a paramagnetic impurity of
1.3%. The obtained molecular field parameter, zJ%, is
very small (−0.005 cm−1) compared to those reported
for the isophthalate (−0.03 cm−1) [30] and terephtha-
late bridges (−0.04 and −0.065 cm−1) [32,36].
The isothermal magnetisation data at 2 K (Fig. 7)
also indicate that there is no significant interdimer
interactions even at very low temperatures. Thus, the
magnetisation data can be very well reproduced with
Fig. 5. Plot of the product of the susceptibility times the temperature per Mn dimer vs. temperature for compound 2. The solid line is the best-fit
to a model of antiferromagnetic coupled Mn(II) dimer (see text). Inset: the low temperature region.
Fig. 6. Plot of the susceptibility per Mn dimer vs. temperature for compound 2. The solid line is the best-fit to a model of antiferromagnetic
coupled Mn(II) dimer (see text). Inset: the low temperature region showing the maximum in the susceptibility data.

2302
M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
Fig. 7. Plot of the isothermal magnetisation at 2 K for compound 2. Solid line represents the theoretical behavior for a Mn(II) dimer with the
same parameters as those obtained from the susceptibility data.
[4] R. Hooft, COLLECT, Nonius BVm Delft, The Netherlands, 1998.
[5] (a) R.H. Blessing, Acta Crystallogr., Sect. A 51 (1995) 33;
(b) R.H. Blessing, J. Appl. Crystallogr. 30 (1997) 421.
[6] G.M. Sheldrick, SHELXS-97 and SHELXL-97, University of Go¨t-
the same parameters as those deduced from the suscep-
tibility versus temperature data without introducing
any molecular field term (solid line in Fig. 7). Magnetic
data for compound 3 was not obtained because this
solid was not prepared phase pure. However, because it
has a similar structure to 2 it is likely that similar
magnetic properties would be observed.
tingen, Germany, 1997.
[7] (a) J.J. Borras-Almenar, J.M. Clemente-Juan, E. Coronado, B.
Tsukerblat, Inorg. Chem. 38 (1999) 6081;
(b) J.J. Borras-Almenar, J.M. Clemente-Juan, E. Coronado, B.
Tsukerblat, J. Comput. Chem. (2001), in press.
[8] 3D Search and Research using the Cambridge Structural Data-
base: F.H. Allen, O. Kennard, Chem. Design Automation News
8 (1993) 1.
5. Supplementary material
[9] P.S. Wheatley, A.J. Lough, G. Ferguson, C. Glidewell, Acta
Crystallogr., Sect. C 55 (1999) 1486.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 156783–156786 for com-
pounds 1–3, respectively. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
ac.uk or www: http://www.ccdc.cam.ac.uk).
[10] S. Valiyaveettil, V. Enkelmann, K. Mullen, Chem. Commun.
(1994) 2097.
[11] A.R.E. Baikie, M.B. Hursthouse, L. New, P. Thornton, R.G.
White, Chem. Commun. (1980) 684.
[12] L.W. Hessel, C. Romers, Recl. Trav. Chim. Pays-Bas (Rec. J. R.
Neth. Chem. Soc.) 88 (1969) 545.
[13] S. Menage, J.-J. Girerd, A. Gleizes, Chem. Commun. (1988) 431.
[14] Bao-Hui Ye, T. Mak, I.D. Williams, Xiao-yuan Li, Chem.
Commun. (1997) 1813.
[15] Shi-Bao Yu, S.J. Lippard, I. Shweky, A. Bino, Inorg. Chem. 31
(1992) 3502.
[16] M. Hirotsu, M. Kojima, W. Mori, Y. Yoshikawa, Bull. Chem.
Soc. Jpn. 71 (1998) 2873.
[17] A. Caneschi, D. Gatteschi, M.C. Melandri, P. Rey, R. Sessoli,
Inorg. Chem. 29 (1990) 4228.
[18] B. Albela, M. Corbella, J. Ribas, I. Castro, J. Sletten, H.
Stoeckli-Evans, Inorg. Chem. 37 (1998) 788.
[19] P.-R. Wei, Qi Li, W.-P. Leung, T.C.W. Mak, Polyhedron 16
(1997) 897.
Acknowledgements
We are grateful to the Leverhulme Trust for financial
support and to the National EPSRC X-ray crystallo-
graphic characterisation service.
[20] C.S. Hong, Y. Do, Inorg. Chem. 36 (1997) 5684.
[21] M. Andruh, H.W. Roesky, M. Noltemeyer, H.-G. Schmidt,
Polyhedron 12 (1993) 2901.
References
[22] C.-M. Che, W.-T. Tang, K.-Y. Wong, W.-T. Wong, T.-F. Lai, J.
Chem. Res. 30 (1991) 401.
[23] W. Clegg, I.R. Little, B.P. Straughan, J. Chem. Soc., Dalton
Trans. (1986) 1283.
[1] M.R.St.J. Foreman, M.J. Plater, A.M.Z. Slawin, J. Chem. Soc.,
Dalton Trans. (1999) 4209.
[2] Bruker, SMART, SAINT and SADABS. Bruker AXS Inc., Madison,
WI, 1999.
[24] X.-M. Chen, Y.-X. Tong, T.C.W. Mak, Inorg. Chem. 33 (1994)
4586.
[25] W. Clegg, P.A. Hunt, B.P. Straughan, Acta Crystallogr., Sect. C
51 (1995) 613.
[3] Z. Otwinowski, W. Minor, Methods in Enzymology, in: C.W.
Carter, R.M. Sweet (Eds.), Macromolecular Crystallography, Pt.
A, vol. 276, Academic Press, New York, 1997, pp. 307–326.

M. John Plater et al. / Polyhedron 20 (2001) 2293–2303
2303
[26] B. Singh, J.R. Long, F.F. de Biani, D. Gatteschi, P. Stavropou-
los, J. Am. Chem. Soc. 119 (1997) 7030.
[32] J. Cano, G. De Munno, J. Sanz, R. Ruiz, F. Lloret, J. Faus, M.
Julve, J. Chem. Soc., Dalton Trans. (1994) 3465.
[33] H. Oshio, E. Ino, I. Mogi, T. Ito, Inorg. Chem. 32 (1993) 5697.
[34] B. Albela, M. Corbella, J. Ribas, I. Castro, J. Sletten, H.
Stoeckli-Evans, Inorg. Chem. 37 (1998) 788.
[27] M. Mikuriya, S. Tashima, Polyhedron 17 (1998) 207.
[28] J. Skorsepa, K. Gyoryova, M. Melnik, K. Smolander, M.
Ahlgren, Acta Crystallogr., Sect. C 51 (1995) 1069.
[29] T. Tanase, J.W. Yun, S.J. Lippard, Inorg. Chem. 34 (1995)
4220.
[35] X.S. Tan, D.F. Xiang, W.X. Tang, K.B. Yu, Polyhedron 16
(1997) 1411.
[30] W. Lin, M.E. Chapman, Z. Wang, G.T. Yee, Inorg. Chem. 39
(2000) 4169.
[31] G.R. Wagner, S.A. Friedberg, Phys. Lett. 9 (1964) 11.
[36] J. Cano, G. De Munno, J.L. Sanz, R. Ruiz, J. Faus, F. Lloret,
M. Julve, A. Caneschi, J. Chem. Soc., Dalton Trans. (1997)
1915.
.