Download - Stabilization of O–Mn–O clusters (Mn5) in three dimensionally extended MOF structures: synthesis, structure and properties

Stabilization of O–Mn–O clusters (Mn5) in three dimensionally extendedMOF structures: synthesis, structure and properties{

Saurav Bhattacharya,a K. V. Ramanujachary,c S. E. Lofland,d Travis Magdalenoc and Srinivasan Natarajan*ab

Received 18th October 2011, Accepted 10th April 2012

DOI: 10.1039/c2ce06386g

Four new three-dimensional Mn2+ ion-containing compounds have been prepared by employing a

hydrothermal reaction between Mn(CH3COO)2?4H2O, sulfodibenzoic acid (H2SDBA), imidazole,

alkali hydroxide and water at 220 uC for 1 day. The compounds have Mn5 (1–4) clusters connected by

SDBA, forming the three-dimensional structure. A time and temperature dependent study on the

synthesis mixture revealed the formation of a one-dimensional compound, Mn(SDBA)(H2O)2, at

lower temperatures (T ¡ 180 uC). The stabilization of the fcu related topology in the compounds is

noteworthy. Magnetic studies indicate strong anti-ferromagnetic interactions between the Mn2+ ions

within the clusters in the temperature range 75–300 K. The rare participation of a sulfonyl group in

the bonding is important and can pave way for the design of new structures.

Introduction

Metal organic framework compounds (inorganic coordination

polymers) provide new pathways for exploring the formation of

–M–O–M– clusters and networks.1 Isolated –M–O–M– clusters

were investigated with great interest for their unique physical

properties, especially their single molecule magnetism.2 Of these

molecules, those containing manganese are important and were

studied extensively during the last two decades.3 The synthesis of

isolated Mn clusters and their derivatives was achieved by

carefully controlling the experimental parameters.3

The formation of extended –M–O–M– networks within MOFs

appears to be facilitated, in general, by higher reaction

temperatures.4 Simple –M–O–M– clusters, however, can be

stabilized as part of a MOF structure at lower temperatures as

well.5 Ferey and coworkers have isolated and extensively

investigated M3 (M = Fe, Cr, Al etc) clusters stabilized as part

of a MOF structure.6 In addition to exhibiting interesting

magnetic properties, the observation of breathing-like behavior

in these compounds is noteworthy.7

From the available literature, it is clear that nitrogen-

containing ligands help the formation of –M–X–M– (X = O,

N) clusters.8 Pyridine and bipyridine-based dicarboxylic acids

have been employed to stabilize new types of metal–oxygen/

nitrogen clusters within MOFs.8 Of the many dicarboxylic acids

employed in the literature, terephthalic acid appears to be the

most dominant.9 A variant of terephthalic acid is 4,49-oxybis-

benzoic acid, OBA, (HOOC–(C6H4)–O–(C6H4)–COOH), the use

of which has resulted in many interesting compounds.10

We propose that the closely related acid, viz-sulfonyldibenzoic

acid, H2SDBA, (HOOC–(C6H4)–SO2–(C6H4)–COOH), could

also give rise to a variety of new compounds with novel

structures. To this end, we have reacted a mixture of a Mn-salt,

H2SDBA and imidazole along with a number of alkali

hydroxides (Na+, K+, Cs+ and NH4+) under hydrothermal

conditions. Our efforts were successful and we have isolated four

three-dimensional framework compounds possessing Mn5 clus-

ters as part of the framework, [Mn5(C14H8O6S)4(C14H9O6S)2]?

4.5H2O, 1, [Mn5K2(H2O)2(C14H8O6S)6], 2, [Mn5Cs2(C14H8O6S)6],

3 and [Mn5(NH4)2(C14H8O6S)6]?2H2O, 4. In this paper, the

synthesis, structure and properties of these compounds are

described and discussed.

Experimental

Synthesis

The chemicals, Mn(CH3COO)2?4H2O, 4,49-sulfonyldibenzoic

acid (H2SDBA) and CsOH were obtained from Sigma Aldrich

(Germany) and imidazole, NaOH, KOH and NH4OH were

obtained from Merck (India) and were used as received. All the

compounds were prepared via a hydrothermal method. In a

typical synthesis for [Mn5(C14H8O6S)4(C14H9O6S)2]?4.5H2O, 1,

Mn(CH3COO)2?4H2O (0.245 g, 1 mmol), H2SDBA (0.306 g,

aFramework Solids Laboratory, Solid State and Structural ChemistryUnit, Indian Institute of Science, Bangalore, 560012, IndiabDivision of Advanced Materials Science, Pohang University of Scienceand Technology (POSTECH), San 31, Hyoja-Dong, Pohang, 790-784,South Korea. E-mail: [email protected] of chemistry and Biochemistry, University, 201 Mullica HillRoad, Glassboro, New Jersey 08028, USAdDepartment of Physics and Astronomy, Rowan University, 201 MullicaHill Road, Glassboro, New Jersey 08028, USA{ Electronic supplementary information (ESI) available: Tables forselected bond distances, bond angles, hydrogen bonds, magnetic data,IR spectra, PXRD patterns, additional figures for structural description,TGA, UV, PL and magnetic plots of the compounds. CCDC referencenumbers 834723–834725, 864134. For ESI and crystallographic data inCIF or other electronic format see DOI: 10.1039/c2ce06386g

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1 mmol), imidazole (0.068 g, 1 mmol) and NaOH (0.080 g,

2 mmol) were mixed in 10 mL of water. The mixture was

homogenized for 30 min at room temperature, transferred into a

23 mL PTFE lined stainless steel autoclave, sealed and heated at

220 uC for 1 day under autogenous pressure. The final product

contained large quantities of colorless block-shaped crystals,

which were filtered under vacuum, washed with deionized water

and dried under ambient conditions. Similar synthesis proce-

dures were employed for the preparation of compounds 2–4

(Table 1).

Time and temperature variation investigations

The same reaction mixture with the composition

Mn(CH3COO)2?4H2O (1 mmol), H2SDBA (1 mmol), imidazole

(1 mmol) and NaOH/KOH/CsOH/NH4OH (2 mmol) in 10 mL

of water was reacted in a 23 mL Teflon lined stainless steel

autoclave at 75, 110, 150, 180, 200, 220 uC for varying periods of

time (typically 1–3 days). The products in each case were

separated by the usual methods of filtration, dried at ambient

conditions and subjected to PXRD analysis.

Characterizations

Initial characterizations were carried out by elemental analysis,

powder X-ray diffraction (PXRD), thermogravimetric analysis

(TGA), IR and UV-Vis spectroscopic studies. Elemental analysis

(C, H, N) was recorded in a Thermo Finnigan EA Flash 1112

Series. Powder X-ray diffraction patterns were recorded in the 2h

range of 5–50u using Cu–Ka radiation (Philips X’pert Pro). The

observed PXRD patterns were new and the patterns entirely

consistent with the simulated XRD patterns generated, based on

the structures determined using single crystal XRD (Fig. S1,

ESI{). Simulated XRD patterns of all the compounds were

generated using Mercury software (version 1.4.1). The PXRD

studies also revealed that the microcrystalline powders obtained

during the synthesis also belonged to the respective compounds.

IR spectra of all the compounds were recorded on KBr pellets

(PERKIN ELMER SPECTRUM 1000). IR spectra for all the

compounds gave sharp characteristic bands (Fig. S2, ESI{). The

presence of a peak at y3227 and 3099 cm21 in 4 suggests the

presence of symmetric and asymmetric stretching frequencies

from the ammonium ion (Table S1, ESI{).11

The thermal stability of the prepared compounds was

investigated using thermogravimetric analysis (TGA). The

studies were carried out on all the samples (1–4) in flowing air

(flow rate = 20 ml min21) in the temperature range of 30–850 uCusing a heating rate of 5 uC min21 (Fig. S3, ESI{). Details of the

TGA analysis have been tabulated (Table S2, ESI{) and the

PXRD patterns of the final products are given in Figure S4

(ESI{). The general trend appears to be consistent for all

compounds, although the individual compounds exhibit subtle

differences which depend on the amount of water molecules

present within the structure. All the compounds appear to be

stable up to 350 uC. The final product contained Mn2O3

(JCPDS: 89-4836) and MnS0.4O2.6 (JCPDS: 21-0557), along

with K3(MnO4)(MnO4) (JCPDS:79-2320) for 2 and Cs2O3

(JCPDS: 65-3154) for 3 and several other unidentifiable peaks,

as seen in the PXRD spectra (Fig. S4, ESI{).

The diffuse reflectance UV-Vis spectra was recorded at room

temperature for the Na2SDBA anion and for the as-synthesized

compounds using a UV-Vis spectrophotometer (Perkin Elmer

Lambda 35, USA). Room temperature solid state photolumines-

cence studies were carried out on the powdered samples of

Na2SDBA and compounds 1–4 using a luminescence spectro-

photometer (Perkin Elmer LS 55, USA).

To probe the magnetic behavior of the present compounds, we

carried out magnetic studies in the temperature range of 5–300 K

using a SQUID magnetometer (Quantum Design Inc., USA).

The presence of Mn5 clusters in the present compounds suggest a

possibility of interesting magnetic behavior. Single molecule

magnets based on Mn clusters have been investigated and

modeled extensively.3 The studies on extended structures

containing manganese clusters have been quite limited thus far,

as it is difficult to understand the various exchange pathways and

the interactions between the Mn clusters.

Single crystal structure determination

A suitable single crystal of each compound was carefully selected

under a polarizing microscope and glued to a glass fiber. The

data from the single crystals of the compounds were collected on

a Bruker AXS smart Apex CCD diffractometer at 120(2) K for

compound 1 and 293(2) K for compounds 2–4. The X-ray

generator was operated at 50 kV and 35 mA using Mo–Ka (l =

0.71073 A) radiation. Data was collected with a v scan width of

0.3u. A total of 606 frames were collected at three different

settings for Q (0, 90, 180u) whilst keeping the sample-to-detector

distance fixed at 6.03 cm and the detector position (2h) fixed at

225u. The data was reduced using SAINTPLUS12 and an

empirical absorption correction was applied using the SADABS

program.13 The structure was solved and refined using

Table 1 Synthesis composition and conditions employed for compounds 1–4

S no. Composition T/uC Time (h) Product Yield (%)a

1 Mn(CH3COO)2?4H2O + H2SDBA + imidazole+ 2.0 NaOH + 556?0H2O

220 24 [Mn5(C14H8O6S)4(C14H9O6S)2]?4.5H2O, 1 60

2 Mn(CH3COO)2?4H2O + H2SDBA + imidazole+ 2.0 KOH + 556?0H2O

220 24 [Mn5K2(H2O)2(C14H8O6S)6], 2 50

3 Mn(CH3COO)2?4H2O + H2SDBA + imidazole+ 2.0 CsOH + 556?0H2O

220 24 [Mn5Cs2(C14H8O6S)6], 3 75

4 Mn(CH3COO)2?4H2O + H2SDBA + imidazole+ 2.0 NH4OH + 556?0H2O

220 24 [Mn5(NH4)2(C14H8O6S)6]?2H2O, 4 60

a Yields are calculated based on the respective metals. Compositions given are molar compositions.CHN analysis for 1: Calc(%) C 46.2; H 2.6; N0.0; Found(%) : C 45.8; H 2.4; N 0.0 ; for 2: Calc(%) C 45.6; H 2.3; N 0.0; Found(%): C46; H 2.1; N 0.0; for 3: Calc(%) C 42.6; H 2.02; N 0.0;Found(%): C 43.1; H 1.9; N 0.0; for 4: Calc(%) C 46.6; H 2.70; N 1.3; Found: C 47.3; H 2.15; N 1.2.

4324 | CrystEngComm, 2012, 14, 4323–4334 This journal is � The Royal Society of Chemistry 2012

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SHELXL97,14 present in the WinGx suit of programs (Version

1.63.04a).15 All non-hydrogen positions were initially located in

the difference Fourier maps and for the final refinement, the

hydrogen atoms were placed in geometrically ideal positions and

refined in the riding mode. Restraints for the bond distances

were used during the refinement to keep the hydrogen atoms

bonded to the protonated carboxylate oxygen and the nitrogen

in the ammonium ion in compounds 1 and 4, respectively. DFIX

and DANG restraints were used to fix the hydrogens onto the

nitrogen atom in 4 in order to model the ammonium ion

properly. Final refinements included atomic positions of all the

atoms, anisotropic thermal parameters for all the non-hydrogen

atoms and isotropic thermal parameters for all the hydrogen

atoms. One of the water molecules, O(21), in compound 1 was

found to be disordered and hence only the isotropic refinement

was carried out. A full-matrix least squares refinement against

|F2| was carried out using the WinGx package of programs.15

Details of the structural parameters and final refinements for the

compounds are presented in Table 2. Crystallographic data for

compounds 1–4 (CCDC No. 864134 for 1 and 834723–834725

for 2–4) are available in the ESI.{

Results and discussion

Structure of [Mn5(C14H8O6S)4(C14H9O6S)2]?4.5H2O, 1

The asymmetric unit of 1 consists of 69 non-hydrogen atoms.

For the purpose of describing the structure, the acid is

designated as H2SDBA, the partially deprotonated acid as

HSDBA and the fully deprotonated acid as SDBA. This

nomenclature will be employed hereafter in the manuscript.

There are three Mn2+ ions, which are crystallographically

independent with Mn(1) occupying a special position (1h) with

a site multiplicity of 0.5 and thus lying on an inversion center,

along with two SDBA anions, one HSDBA anion and three

water molecules. Of the three Mn2+ ions, Mn(1) has a distorted

octahedral geometry while Mn(2) and Mn(3) have a distorted

square pyramidal geometry formed by the carboxylate oxygens

(Fig. S5, ESI{). The Mn–O bond distances are in the range

2.051(2)–2.249(2) A while the O–Mn–O bond angles are in the

range 75.83(7)–180.00u. The selected bond distances and bond

angles are listed in the ESI (Table S3 and S4).{ The close

proximity of the lattice water molecules, O(19), to the

carboxylate oxygen, O(12), gives rise to a O–H…O hydrogen

bond interaction. The O…O distance is 3.092(4) A and the

O–H…O bond angle is 164u, which suggests that the hydrogen

bond interaction is medium to strong (Table S5, ESI{).16

The structure of 1 has two types of SDBA anion connectivities:

one in which the HSDBA anion bonds with the three metal centers

via a monodentate and bidentate chelating mode and the other in

which the SDBA anions are bonded via a bidentate and tridentate

mode (Fig. 1a). The formation of the pentameric clusters can be

understood by considering the connectivity between the Mn

centers. Mn(2) and Mn(3) form a paddlewheel arrangement while

the Mn(1) octahedra connects the paddlewheel through the three

coordinate oxygen atoms, O(2) and O(3), forming the trimer. As

Mn(1) occupies a special position, the other paddlewheel is

generated automatically by the symmetry, giving rise to the

pentamer (Fig. 2a). Thus, two paddlewheel units (Mn(2) and

Mn(3)) are joined at the edges by the Mn(1) octahedra (Fig. 2a).

The Mn5 cluster units are connected through the carboxylate

bridges, giving rise to the three-dimensional structure (Fig. 2b and

2c). The lattice water molecules occupy spaces between the clusters

and form hydrogen bond interactions, giving rise to one-

dimensional units (Fig. 2b). The protonated carboxylate oxygen,

O(12), participates in the hydrogen bond interactions involving

the lattice water molecules to bridge the pentanuclear units.

Structures of [Mn5K2(H2O)2(C14H8O6S)6], 2,

[Mn5Cs2(C14H8O6S)6], 3 and [Mn5(NH4)2(C14H8O6S)6]?2H2O, 4

The structures of 2, 3 and 4 are similar where the alkali metal

ions were also found to be part of the network. There are 68

Table 2 Crystal data and structure refinement parameters for compounds 1–4

1 2 3 4

Empirical formula C84H59S6O40.5Mn5 C84H52S6O38K2Mn5 C84H48S6O36Cs2Mn5 C84H60 N2S6O38Mn5

Formula weight 2183.30 2214.48 2366.10 2172.37Crystal system Triclinic Triclinic Triclinic TriclinicSpace group P1 (no.2) P1 (no.2) P1 (no.2) P1 (no.2)a/A 12.700(5) 12.7407(3) 12.5500(6) 12.7609(6)b/A 12.714(5) 12.7787(3) 12.9301(6) 12.7682(6)c/A 15.990(5) 15.9960(4) 16.1279(7) 16.0315(7)a (u) 72.773(5) 86.701(2) 106.080(4) 87.646(4)b (u) 88.047(5) 72.142(2) 93.353(4) 72.508(4)c (u) 60.583(5) 60.438(3) 118.627(5) 60.477(5)Volume/A3 2128.8(14) 2142.27(9) 2149.86(17) 2149.71(17)Z 1 1 1 1T/K 120(2) 293(2) 293(2) 293(2)rcalcd (g cm23) 1.696 1.714 1.828 1.675m/mm21 0.968 1.056 1.787 0.957Wavelength (A) 0.71073 0.71073 0.71073 0.71073h range (deg) 1.35 to 27.63 2.40 to 26.00 2.44 to 26.00 2.42 to 26.00R index [I . 2s(I)] R1 = 0.0416 R1 = 0.0334 R1 = 0.0576 R1 = 0.0425

wR2 = 0.0948 wR2 = 0.0859 wR2 = 0.1334 wR2 = 0.0845R (all data) R1 = 0.0611 R1 = 0.0462 R1 = 0.0930 R1 = 0.0675

wR2 = 0.1036 wR2 = 0.0919 wR2 = 0.1469 wR2 = 0.0971

R1 = S|| Fo | 2 | Fc ||/S | Fo |; wR2 = {S [w (Fo2 2 Fc

2)]/S [w (Fo2) 2]}1/2. w = 1/[r2(Fo)2 + (aP)2 + bP]. P = [max (Fo, O) + 2(Fc)

22]/3, where a =0.0384 and b = 3.6886 for 1, a = 0.0419 and b = 0.6507 for 2, a = 0.0529 and b = 1.4829 for 3, and a = 0.030 and b = 0.0000 for 4.


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Fig. 1 The various connectivities of the SDBA molecule observed in compounds (a) 1, (b) 2, (c) 3, (d) 4.


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Fig. 2 (a) The Mn5 pentamer in compound 1. (b) The bridging of the Mn5 pentamers by hydrogen bonded lattice water molecules and protonated

carboxylates. (c) The overall three-dimensional structure of 1.


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non-hydrogen atoms in the asymmetric unit of 2, 67 in 3 and 68

in 4. There are three Mn2+ ions which are crystallographically

independent, with Mn(1) occupying a special position (1c for 2

and 3 and 1h for 4) with a site multiplicity of 0.5 as it lies on an

inversion center, along with three SDBA anions and one

potassium ion for 2, a cesium ion for 3 and an ammonium ion

for 4 as well as water molecules in 2 and 4 (Fig. S6–S8, ESI{). Of

the three Mn+2 ions, Mn(1) has a distorted octahedral geometry,

while Mn(2) and Mn(3) have distorted square pyramidal

geometries formed by the carboxylate oxygens. The potassium

atom in 2 has a distorted octahedral geometry formed by the

carboxylate and sulfonyl oxygen atoms and it also possesses a

coordinated water molecule, O(19) (Fig. S6, ESI{). The cesium

atom in 3 on the other hand, has a distorted seven coordinate

geometry formed from the carboxylate and sulfonyl oxygen

atoms (Fig. S7, ESI{). The ammonium ion in 4 forms N–H…O

type hydrogen bond interactions with N…O distances ranging

from 2.799(5)–3.134(6) A and N–H…O bond angles ranging

from 146–167u (Fig. S8, Table S5, ESI{ ).

Here, as a representative structure, we present the structure of

the potassium-containing compound (2) in detail. There are three

types of SDBA anion connectivity observed in 2. The first acid

has one of the carboxylate groups coordinated to two Mn2+ ions

in a chelating fashion while the other carboxylate unit is bonded

to two K+ and one Mn+2 ions, with the sulfonyl group bonded to

one K+ ion. The second acid has the carboxylate group bonded

with two Mn2+ ions in a chelating fashion, the other carboxylate

group bonded with three Mn+2 ions and the sulfonyl group

bonded to one K+ ion. The third acid has one of the carboxylates

bonded with two Mn+2 and one K+ ions and the other

carboxylate bonded with three Mn2+ ions while the sulfonyl

group remains uncoordinated (Fig. 1b). It is interesting to note

that the sulfonyl unit, which connects the two benzoic acid

groups, participates in bonding. The polydentate bonding

behavior of the carboxylate groups observed in the present

compounds 1–4 (Fig. 1b), have been observed previously.17

The connectivity between the Mn2+ ions and the carboxylate

groups lead to the formation of Mn5 pentameric clusters

(Fig. 3a). Similar to the structure of 1, the pentameric cluster

contains paddlewheel arrangements connected by the Mn(1)

octahedra. Thus, Mn(2) and Mn(3) form the paddlewheel

arrangement which are connected by the Mn(1) octahedra

through the two three-coordinated oxygen atoms (Fig. 3a).

The role of the K+ ion in the structure is important as it bridges

the pentanuclear units to form a one dimensional unit. The K+

ions are connected through the carboxylate and sulfonyl

oxygens, forming an eight membered ring which links the Mn5

pentamer units (Fig. 3b). As can be seen, the K+ ions occupy the

spaces occupied by the water molecules in the structure of 1. The

one dimensional –Mn5–K2–Mn5– chains are crosslinked by the

carboxylate units, forming the observed three-dimensional

structure (Fig. 3c).

The pentamer cluster units can be considered as nodes, similar

to the structure of 1, in the consideration of the network with

SDBA and the M+ ion dimers (M = K, Cs, NH4] as linkers. A

TOPOS analysis18a,b would then give a uninodal 12 connected

net with an fcu (cubic closed packing) topology, with the Schlafli

symbol [324.436.56]18c (Fig. 3d), while having 3, 4 and 5-mem-

bered circuits originating from the node. The superscripts in the

Schlafli symbol denote the number of such circuits originating

from a particular node.18d The distances between the Mn5

clusters (inter-cluster) range from 12.74(1)–17.12(2) A in 2,

12.55(1)–17.66(4) A in 3 and 12.77(1)–17.78(1) A in 4 (center of

the cluster to the neighbor). MOFs with an fcu topology from

cluster-ligand connectivity have been previously observed.19 For

example, in the case of the [Cu3(pdt)2(CN)] compound,19b if we

consider the Cu6S4 cluster as the node and eight pyridinethiolate

and four cyanide groups as the linkers, one could observe the

emergence of a fcu topology (Fig. 4). Mn5 clusters are not

uncommon and have been observed before. The connectivity

differences between the clusters give rise to unique topologies. In

the present structures, a fcu topology has been observed whereas

bct, hxl and bcu topologies have been observed previously.

Table 3 summarizes the different topologies observed within the

Mn5 clusters.

Four three-dimensional compounds have been prepared by the

use of different alkali metals. All the compounds have similar

Mn5 building units, connected by the acid and alkali metal ions,

forming the observed three-dimensional structure. The present

study suggests that the larger alkali metal ions are incorporated

as part of the structure, though the exact role played by the alkali

metal ions is not clear. It is likely that the subtle differences in the

basic nature of the different alkali ions might have played a role

in the outcome of the structures.

Time and temperature dependent studies on the synthesis

The role of time and temperature in the preparation of MOFs

has not been investigated in great detail in previous studies. Our

earlier studies on the role of time and temperature in

the formation of MOFs clearly points out the formation of

–M–O–M– extended networks or clusters either at higher

temperature or by prolonged heating at a relatively lower

temperature.4d The present series of compounds have been

prepared by heating the reaction mixture at 220 uC for 1 day,

which resulted in the formation of Mn5 clusters bonded through

the ligands. It occurred to us that a greater insight on the

formation of the phases could be obtained by exploring the

formation, using the same reaction mixture, at lower tempera-

tures as well as by varying the periods of time. A study of this

nature might provide valuable clues towards the formation of

other related phases. This is a labour intensive experiment and

the products in most cases were powder samples admixed with

single crystals. The single crystals were analyzed using single

crystal XRD. The powder and the single crystals were crushed

and analyzed using PXRD (Fig. S9–S12, ESI{).

From the PXRD patterns, the following observations can be

made. In all cases, a one dimensional solid, Mn(SDBA)(H2O)2,

was the only product, especially at lower temperatures (Fig. S13,

ESI{). The single crystal structure of the 1D compound was

already known21a and a careful study of the PXRD patterns

indicated that the 1D compound is generally stable up to 180 uC,

using the synthesis composition for the preparation of 1. A small

transient unidentifiable impurity phase was observed at 110 uCafter 2 days (Fig. S13a, ESI{). In spite of our best efforts, we

could not isolate suitable single crystals necessary for identifying

this unknown phase. The 3D compound (1) was the only phase

isolated at higher temperatures as well as at longer durations


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(200–220 uC) (Fig. S13a, ESI{). In the case of compound 2, the

reaction mixture yielded only the 1D21a and 3D (2) phase. We

did not observe the formation of any additional phase, though a

mixture of the 1D and 3D phases was observed at 180 uC at 1

and 2 days during the reaction (Fig. S13b, ESI{). In the case of

compound 3, we observed the formation of the 3D phase even at

75 uC after 3 days (Fig. S13c, ESI{). In addition, at 180 uC a new

unidentified product was observed. The formation of the 3D

phase (3) after prolonged heating (3 days) suggests that it could

be thermodynamically more stable. In the case of compound 4,

again, we observed only two compounds (the 1D and 3D phases)

(Fig. S13d, ESI{). A mixture of the 1D and 3D (4) phases was

observed at 150 uC after 2 and 3 days (Fig. S13d, ESI{).

During the present study, we have observed the formation of two

distinct unidentifiable phases in addition to isolating the reported

1D21a and 3D compounds (1–4). Such observations have been

made before.4a,b Although it is difficult to predict the formation of

phases under hydrothermal conditions, the repetitive formation of

two distinct phases (1D and 3D) as a function of time and

temperature suggests that, for the composition employed, they

could be the stable phases. It is likely that one could observe other

phases by varying the composition and performing further

reactions as a function of temperature and time. Such studies have

led to the formation of interesting new structures.5b

Earlier studies on the effect of time and temperature indicated

the facile formation of –M–O–M– linkages and clusters at higher

synthesis temperatures.10a The formation of –Mn–O–Mn–

clusters at 220 uC suggests that one could observe extended

–Mn–O–Mn– connectivities at even higher reaction temperatures

(T . 220 uC). Similar observations have been made previously

during the synthesis of MOFs.10a We have reacted the 1D Mn

compound, Mn(SDBA)(H2O)2, under hydrothermal conditions

at 220 uC to observe whether the 1D compound undergoes

any transformation to the 3D phase reported here. The

1D compound, however, decomposes under these reaction

Fig. 3 (a) The Mn5 pentamers in compounds 2–4. (b) The one

dimensional chains formed from the connectivity between the Mn5

clusters and the potassium dimers in 2. Similar chains are observed in

compounds 3–4. (c) The overall three dimensional structure formed from

the connectivity between the Mn5 clusters, SDBA and the potassium

dimers in 2. The green polyhedra represent the 12 connected cluster node

while the cyan spheres represent the potassium ions. (d) The connectivity

of the clusters leading to a fcu topology in compounds 2–4, compound 2

taken as a model. The purple spheres represent the Mn5 clusters while the

green spheres represent the potassium ion dimers in 2, cesium ion dimers

in 3 and ammonium ion dimers in 4.

Fig. 4 The fcu topology observed in [Cu3(pdt)2(CN)].19b The net

topology was arrived at by considering the Cu6S4 cluster as the node

and the pyridinethiolate groups and the cyano groups as the linkers. Each

red sphere indicates the 12 connected node.


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Ta

ble

3C

om

pari

son

of

the

Mn

5cl

ust

ers

rep

ort

edin

the

lite

ratu

rew

ith

the

pre

sen

tco

mp

ou

nd

s1–4

Co

mp

ou

nd

sC

lust

erU

nit

Co

nn

ecti

vit

yw

ith

inth

eM

n5

clu

ster

un

itL

ink

ers

an

dto

po

log

y(u

sin

gM

n5

clu

ster

as

no

de)

Illu

stra

tio

ns

(Mn

5cl

ust

era

nd

Fra

mew

ork

top

olo

gy

)

Co

mp

ou

nd

s1–4

[Mn

5(m

3-C

OO

) 4-

(m-C

OO

) 6]

Dis

tort

edsq

ua

rep

yra

mid

al

Mn

are

edg

eco

nn

ecte

dw

ith

oct

ah

edra

lM

nfo

rmin

ga

trim

erco

nn

ecte

dfu

rth

erb

yca

rbo

xy

late

ox

yg

ens

wit

htw

oo

ther

squ

are

py

ram

ida

lM

n.

SD

BA

an

dh

yd

rog

enb

on

ded

wa

ter

(1)

or

alk

ali

ion

dim

ers

(2–4)

con

nec

tsth

eM

n5

clu

ster

no

des

form

ing

a1

2co

nn

ecte

dn

etw

ith

fcu

top

olo

gy

.

[Mn

5(H

trz)

2-

(SO

4) 4

(OH

) 2]2

0a

[Mn

5(m

3-O

H) 2

(m-

SO

4) 4

(m2-H

trz)

2]

Oct

ah

edra

lm

an

gan

ese

con

nec

ted

thro

ugh

the

edg

esS

ulf

ate

con

nec

tsth

eM

n5

clu

ster

no

des

form

ing

a1

0co

nn

ecte

dn

etw

ith

bct

top

olo

gy

.

[Mn

5(m

3-O

H) 2

-(s

db

a) 4

(2,2

9-b

py

) 2-

(H2O

) 2]?

H2O

20b

[Mn

5(m

3-O

H) 2

(m-

CO

O) 6

]O

ctah

edra

lm

an

gan

ese

con

nec

ted

thro

ugh

the

edg

esa

nd

corn

ers.

SD

BA

con

nec

tsth

eM

n5

clu

ster

no

des

form

ing

atw

od

imen

sio

na

l6

con

nec

ted

net

wit

hh

xl

top

olo

gy

.

[Mn

5O

2(H

ND

T) 2

-(N

DT

) 2(D

MF

) 820c

[Mn

5(m

3-O

) 2(t

et) 8

]M

an

ga

nes

eo

ctah

edra

con

nec

ted

thro

ugh

thei

rco

rner

s.

ND

Tan

dH

ND

Tco

nn

ects

the

Mn

5cl

ust

ern

od

esfo

rmin

ga

n8

con

nec

ted

net

wit

hb

cuto

po

log

y

Htr

z=

1,2

,4-t

ria

zole

;b

py

=b

ipy

rid

ine;

Me 3

-TB

zIm

=1,3

,5-t

ris(

ben

zim

idazo

yl-

1-y

lmet

hyl)

-2,4

,6-t

rim

eth

ylb

enze

ne;

bp

d=

1,4

-bis

(4-p

yri

dyl)

-2,3

-d

iaza

-1,3

-bu

tad

ien

e;H

2N

DT

=2

,6-d

i(1H

-tet

razo

l-5

-y

l)n

ap

hth

ale

ne;

tet

=te

rta

zoly

lg

rou

p.


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conditions, giving rise to the H2SDBA acid (Fig. S14, ESI{).

This suggests that the 1D compound may not be the direct

precursor for the 3D compounds and the formation of the three-

dimensional compounds, reported here, might be through a

dissolution and re-crystallization pathway. Such mechanistic

pathways have been proposed previously.5d The question of

kinetic versus thermodynamic stability during the formation of

framework compounds under hydrothermal conditions is not yet

fully understood. It has been suggested that the removal of water

molecules from the system (bonded as well as free) is a

thermodynamic process4a,d,10a and there have been some reports

conforming this theory. The present understanding of the hydro-

thermal process is that the phases generally form under kinetic

control. The formation of many well known zeolites and other

related framework compounds conform to this theory.21b–d In the

present case, the 1D compound has water molecules bound to the

Mn centers. In addition, except for 3, all the other 3D compounds

contain water molecules. This suggests that the possible formation

pathway of these phases could be somewhere in between the kinetic

and the thermodynamic routes. Further investigations would be

necessary to understand and unravel this observation.

Optical studies

UV-Vis spectroscopic studies indicated that Na2SDBA exhibited

only one broad absorption peak at y298 nm, which may be due

to an intraligand charge transfer transition (Fig. S15, ESI{). For

all the compounds, five absorption bands were observed at

y254 nm, y294–298 nm, 335–365 nm, 381–420 nm and 507–

511 nm, respectively. The bands may correspond to the

transitions from the 6A1g ground state of the Mn+2 ions to the4A2g(F), 4T1g(P), 4T2g(D), 4Eg(G) or 4A1g and 4T2g exited states,

respectively.22 Similar observations for Mn(II) complexes have

been reported in the literature.22b The bands observed at y294–

298 nm could be the superposition of the charge transfer band of

the ligand as well as the 6A1g to 4T1g(P) transitions.

Fig. 5 (a) Field cooled (FC) and zero field cooled (ZFC) data for compound 1 (H = 0.1 T). (b) xmT vs. T plot and 1/xm vs. T plot (inset) for compound

1. (c) xmT vs. T plots at different fields for compound 1.


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All the compounds, as well as Na2SDBA, were excited using

an excitation wavelength of 255 nm to obtain the luminescence

spectra (Fig. S16, ESI{). A weak emission band was observed at

y330 nm for Na2SDBA and at y308 nm, y392 nm, y423 nm,

y484 nm, y530 nm for compounds 1–4. The various emission

bands could be assigned to the d–d transitions, 4T1g(P), 4T2g(D),4Eg(G), 4A1g and 4T2g to the 6A1g ground state.23 Similar

observations have been made previously in the literature.23b

Magnetic studies

For 1, the room temperature value of xmT (1000 O.e.) was found

to be 16.8 emu mol21 K, which is smaller than the expected value

of 21.2 emu mol21 K for five magnetically isolated high-spin

MnII (S = 5/2) ions with g = 2.00 (Fig. 5). This suggests that the

Mn2+ ions are strongly coupled.24 The 1/xm vs. T plot exhibits a

linear decrease as the temperature is reduced in the range of 300–

75 K, below which it shows a steep drop. A Curie–Weiss fit in the

range of 75–300 K gives values of C = 24.63 emu mol21 K and

hp = 2138.96 K (Fig. 5b inset). The xmT value also exhibits a

continuous decrease with a decrease in the temperature to a

minimum of 7.57 emu mol21 K at y48 K. On cooling below

this, the xmT values exhibit a sharp rise, reaching a maximum of

11.4 emu mol21 K at y38 K. The gradual decrease of the xmT

values with a decrease in the temperature to y48 K, along with

the negative value of hp, suggests that the interactions between

the metal centers are strongly antiferromagnetic.24,25 The rapid

increase in the value of xmT below 48 K, coupled with the steep

drop in the 1/xm vs. T plot, suggests the possibility of long range

magnetic ordering.25,26 The sharp drop in the xmT value below

y38 K may be due to the magnetic field saturation effect.25 This

behavior can also be seen in the FC–ZFC plot (Fig. 5a), where

the FC and ZFC behavior exhibits a divergence at y42 K. This

also suggests the possibility of long range magnetic correlations

between the Mn centers. The possible origin for this behavior

was investigated using a field dependent study (Fig. 5c). The

xmT–T values as a function of different applied fields exhibits

pronounced field dependent behavior. As can be noted from

Fig. 5c, at lower applied fields the increase in xmT values are

larger when compared to higher fields. This behavior is typically

observed in compounds exhibiting canted antiferromagnetism. A

similar trend has been observed previously in compounds

possessing –Mn–O–Mn– clusters and extended linkages.26–28

The M vs. H study on 1 does not exhibit any saturation up to 5 T

(Fig. S17, ESI{). The maximum magnetization value of 4.35 Nb

observed at 5 T, is considerably smaller than the expected

saturation value of 15 Nb for three unpaired Mn+2 ions. The lack

of saturation at high fields also confirms that the low

temperature magnetic ground state could be canted antiferro-

magnetic.25,26c AC magnetic studies were carried out at low

temperatures to probe the magnetic state further (Fig. 6). The

field dependent in phase (x9) and out of phase (x99) AC

susceptibilities exhibit only a single peak and no field depen-

dency was observed in the out of phase (x99) AC susceptibility.

The critical temperature (Tc) was found to be y42 K,

determined from the maximum of the x9 vs. T plot. We did not

observe any other variations either in the x9 or x99 behavior as a

function of temperature, suggesting that the present compounds

do not have any spin-glass like state. Similar behavior has also

been previously observed.27

For the compounds 2–4, the magnetic behavior and the values

of the magnetic parameters observed are similar and are given in

Table 4. The respective magnetic plots are given in the ESI (Fig.

S18–S20).{ For compounds 2–4, the Weiss constants were found

to be negative. The gradual decrease in the observed xmT values

with the decrease in temperature to y48 K, indicates that the

interactions between the metal centers could be antiferromag-

netic (Fig. S18a–S20a, ESI{). A rapid increase in the values of

xmT below y48 K, along with a steep drop in the 1/xm vs. T

behavior, suggests the possibility of long range magnetic

ordering in the compounds.25 The observed field dependence

behavior in the compounds indicates spin canted antiferromag-

netic behavior (Fig. S18c–S20c, ESI{).26–28 The saturation

magnetizations for all the compounds from the M vs. H studies

Fig. 6 (a) xm9 vs. T plot for compound 1 at a zero DC field and 10 O.e AC field at different frequencies. (b) xm99 vs. T plot for compound 1 at a zero

DC field and 10 O.e AC field at different frequencies.


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were found to be considerably smaller ((y4–4.5 Nb), Table 4)

than the expected value of 15 Nb for three unpaired Mn+2 ions,

which confirms that the low temperature magnetic ground state

of all the compounds could be canted antiferromagnetic.25 AC

magnetic susceptibility studies also do not indicate the possibility

of any spin-glass behavior in the compounds. The critical

temperature (Tc) for all the compounds was found to be y42 K

(Table 4).

Conclusions

The synthesis and structures of four manganese sulfonyldibenzo-

ates (SDBA) have been accomplished. All the compounds have

Mn–O–Mn linkages, giving rise to Mn5 clusters which are

connected to the SDBA acid, forming the three-dimensional

structure. The observation of fcu topology in all compounds is

noteworthy. Magnetic studies indicate canted antiferromagnetic

behavior. The SDBA acid, though closely related to the

terephthalic and oxy-bisbenzoic acids, has not been investigated

in detail and the present study indicates the possibilities of

forming new types of structures with interesting properties. The

participation of the sulfonyl group is interesting and we are

presently pursuing this behaviour.

Acknowledgements

The authors thank Prof. G. R. Desiraju for many insightful

discussions on the crystallographic aspects of the structures. SN

thanks the Department of Science and Technology (DST),

Government of India, for the award of a RAMANNA

Fellowship. The authors also thank the Council of Scientific

and Industrial Research, Government of India, for the award of

a research grant and a fellowship.

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Table 4 The various magnetic parameters for compounds 1–4

Compounds

CriticalTemperature(Tc) (K)

Room temperaturevalue of xmT(emu mol 21 K) hp (K)

C(emu mol21 K)

Maximummagnetizationvalues in M vs.H Plots (Nb)

Field dependencein AC susceptibilityplots

[Mn5(C14H8O6S)4-(C14H9O6S)2]?4.5H2O , 1

y42 16.83 2138.9 24.624 4.35 No

[Mn5K2(H2O)2(C14H8O6S)6], 2 y42 15.91 2204.4 26.533 4.24 No[Mn5Cs2(C14H8O6S)6], 3 y42 16.04 2315.1 32.776 4.12 No[Mn5(NH4)2(C14H8O6S)6]?2H2O, 4 y42 14.94 2210.1 25.432 4.46 No


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