Four Low-Dimensional Cobalt(II) Coordination Polymers Based on a

Article pubs.acs.org/crystal

Four Low-Dimensional Cobalt(II) Coordination Polymers Based on a New Isophthalic Acid Derivative: Syntheses, Crystal Structures, and Properties Xin-Hong Chang,† Lu-Fang Ma,*,† Guo Hui,† and Li-Ya Wang*,†,‡ †

College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, P. R. China College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, P. R. China

‡

S Supporting Information *

ABSTRACT: A isophthalic acid derivative, 5-(4′-methylphenyl)isophthalic acid (CH3C6H4-H2ip), has been prepared. Reaction of CH3C6H4-H2ip with Co(Ac)2·4H2O and four N-donor ancillary ligands gave four new coordination polymers, {[Co(CH3C6H4-ip)(bip)]·2H2O}n (1), {[Co2(CH3C6H4-ip)2(bib)]·H2O}n (2), {[Co(CH3C6H4-ip)(bpe)0.5(H2O)]·H2O}n (3), {[Co(CH3C6H4-ip) (bipy)0.5]}n (4), [bip =1, 5-bis(imidazol)pentane, bib = 1, 4-bis(imidazol)butane, bpe = 1, 2-bi(4pyridyl)ethene, bipy = 2, 2′-bipyridyl]. Complexes 1−4 were structurally characterized by elemental analysis, infrared spectra (IR), and X-ray single-crystal diffraction. These complexes all display low-dimensional features. Complex 1 exhibits an extended polythreaded network based on two-dimensional (2D) layers that are connected by CH3C6H4-ip and bip ligands. Complex 2 shows a 2D layer containing dinuclear paddle-wheel [Co2(CO2)4] secondary building units (SBUs). Complex 3 possesses a 2D layer and further stacks via hydrogen bonding interactions to generate a three-dimensional supramolecular architecture. Complex 4 shows a one-dimensional linear chain bridged by CH3C6H4-ip. These results suggest that both CH3C6H4-ip and N-donor coligands have a significant effect on the final structures. Variable-temperature magnetic susceptibility measurements reveal the existence of antiferromagnetic interactions in 2 and ferromagnetic interactions in 3, respectively.

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polymers.8 The results show that 5-R-ip in these coordination polymers have flexible conformations, diversity of binding modes, and ability to form hydrogen bonds. Dario Braga’s group prepared a series of complexes of cesium(I) based on 5R-ip (R = -OH, -CH3, -Br, -OCH3, -NO2, -C(CH3)3) and 18crown [6] ligands.9 They found that the size of the substituent can affect the shape and function of the target complexes. Du et al. demonstrated that the coordination-inert substituted groups can influence the structural diversity of the final coordination polymers.10 Zhou et al. designed a new amphiphilic ligand, 4′tert-butyl-biphenyl-3,5-dicarboxylate, and obtained three isostructural mesh-adjustable molecular sieves (MAMSs) in solvothermal reactions with M(NO3)2 (M = Zn, Co, Cu).

INTRODUCTION Design and construction of molecular assemblies through the coordination of metal ions with organic ligands has received much attention and has become an interesting research area of chemistry in recent decades due to their potential applications in adsorption,1 catalysis,2 luminescence,3 and magnetism,4 as well as their charming architectures and topologies.5 Generally, the construction of intriguing structural topologies strongly depends upon the chemical nature of the main or auxiliary ligands and the coordination geometries of central metal ions.6 Therefore, the selection of suitable organic ligands is crucial for constructing extended coordination frameworks. To our knowledge, polycarboxylate ligands are some of the most important families of organic building blocks, which can act as reliable candidates for structural assembly of various coordination species.7 In recent years, rigid 5-R-isophthalic acids (5-RH2ip) have been used in preparation of various coordination © XXXX American Chemical Society

Received: April 5, 2012 Revised: May 15, 2012

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dx.doi.org/10.1021/cg300461v | Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

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complexes were characterized by IR spectra and elemental analysis. In the IR spectra of 1−4, the absence of a characteristic absorption band of carboxyl (at ca. 1700 cm−1) indicates a complete deprotonation of the CH3C6H4-H2ip. Descriptions of Crystal Structures of 1−4. {[Co(CH3C6H4-ip)(bip)]·2H2O}n (1). Single-crystal X-ray diffraction measurement reveals that complex 1 crystallizes in the monoclinic system with P21/c space group. The asymmetric unit consists of one Co(II) ion, one CH3C6H4-ip, one bip ligand, as well as two lattice water molecules. As shown in Figure 1a, each Co(II) center is surrounded by two nitrogen atoms (N1 and N3) from two different bip ligands, and two carboxylic oxygen atoms (O1 and O3A, symmetry codes: A: x + 1/2, −y + 1/2, z + 1/2) from two CH3C6H4-ip, forming a distorted CoN2O2 tetrahedron. The bond angles around each Co(II) ion range from 94.46(13) to 126.73(12)°. The Co−N bond distances are 2.034(4) (Co−N1) and 2.038(4) (Co−N3) Å, and the Co−O bond lengths are 1.993(3) (Co−O3A) and 1.999(3) (Co−O1) Å, respectively. As shown in Figure 1b, each CH3C6H4-ip acts as a μ2-bridge linking two Co(II) ions, in which each carboxylic group adopts a μ1-η1:η0 bridging mode to connect the Co(II) ions (Scheme 3a). The adjacent Co(II) ions are bridged by CH3C6H4-ip ligands to form a 1D chain. Furthermore, these 1D chains are combined together through additional Co−N bonds by bip to construct a 2D coordination layer along the bc plane (Figure 1b). Interestingly, the CH3C6H4-ip moieties, locating up and down each 2D array, insert into the lateral voids of the adjacent networks to produce an unusual polythreaded tactic motif (Figure 1c,d). Yang’s group has prepared two Co(II) complexes, {[Co(ip)(bip)]·H2O}n (5) and {[Co(OH-ip)(bip)]}n (6), constructed from isophthalate (ip), 5-OH-isophthalate (OH-ip) and 1,5bis(imidazol)pentane (bip)13 (see Table 1). Comparison of the structures of 1, 5, and 6 indicates some differences. Compound 5 possesses a 2D layer containing 1D zigzag chains bridged by ip. Compound 6 shows a hydrogen-bonded 3D network encapsulating an undulated square layer (sql) by repeating the [Co4(OH-ip)2(bip)2] units in the ab plane. Both structures are different from that of 1. Thus, although the coordination sites of CH3C6H4-ip, ip, and OH-ip are similar, their coordination chemistries are different, presumably due to the different substituents of 5-R-ip. {[Co2(CH3C6H4-ip)2(bib)]·H2O}n (2). Single-crystal X-ray structural analysis shows that complex 2 crystallizes in the orthorhombic system with space group P21212. In each asymmetric unit, there are two independent Co(II) ions, two CH3C6H4-ip, one bib, as well as one free lattice water molecule. As shown in Figure 2a, both Co(II) centers are pentacoordinated by one nitrogen atom from one bib, and four carboxylic oxygen atoms from four CH3C6H4-ip, forming two distorted tetragonalpyramids. The bond angles around each Co1 center are in the range of 85.9(2)−162.31(17)°. The Co1−N4 bond distance is 2.042(4) Å, and the Co1−O bond lengths range from 2.029(4) to 2.043(4) Å, respectively. The bond angles around each Co2 center vary from 86.64(16) to 161.92(16)°. The Co2−N1 bond distance is 2.073(4) Å, and the Co2−O bond lengths are from 2.045(3) to 2.059(3) Å. As shown in Figure 2b, each CH3C6H4-ip acts as a μ4-bridge linking four Co(II) ions, in which each carboxylic group adopts a μ2-η1:η1 bridging mode to connect two Co(II) ions (Scheme 3b). Co1 and Co2 are bridged by four carboxylic groups to form a binuclear paddle-wheel motif. The Co···Co distance in

The three new MAMSs all exhibit a temperature-tuned molecular sieving effect.11 Our group has also reported a series of coordination polymers based on 5-R-ip. A minor change of the isophthalic acid building blocks may be applied to realize good structural control of the resulting coordination polymers.8d,12 To further probe the influence of systematic variations of the 5-substituent on the overall molecular architectures, we extended the building blocks from 5-R-ip where R = -CH3, -OH, -NO2, -OCH3, -C(CH3)3, and -Br to R = -(CH3C6H4). The use of the bulky substituent on C5 can easily generate low-dimensional complexes distinct from those of other isophthalic acid derivatives. Herein, we report the syntheses and structures of 5-(4′methylphenyl)isophthalic acid (CH3C6H4−H2ip) and its four cobalt(II) complexes, {[Co(CH3C6H4-ip)(bip)]·2H2O}n (1), {[Co2(CH3C6H4-ip)2(bib)]·H2O}n (2), {[Co(CH3C6H4-ip)(bpe)0.5(H2O)]·H2O}n (3), {[Co(CH3C6H4-ip)(bipy)0.5]}n (4) [bip = 1, 5-bis(imidazol)pentane, bib = 1, 4-bis(imidazol)butane, bpe = 1, 2-bi(4-pyridyl)ethene, bipy = 2,2′-bipyridyl]. The thermal behaviors of complexes 1−4 and magnetic properties of 2 and 3 were also discussed.

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RESULTS AND DISCUSSION Synthesis. The synthesis of CH3C6H4-H2ip is shown in Scheme 1. In order to obtain pure product and high yield, the Scheme 1. Synthesis of 5-(4′-Methylphenyl)isophthalic Acid (i = (1) KMnO4, OH−, reflux; (2) HCl, 82% yield; ii = ethanol, H2SO4, reflux, 92% yield; iii = potassium acetate, Pd (dppf)2Cl2, 1,4-dioxane, 78% yield; iv = bromobenzene, K3PO4, 1,4-dioxane, Pd(PPh3)4, reflux; v = (1) OH−, reflux; (2) HCl, 92% yield)

organic solvents used should be dried completely during the synthesis of compounds IV and V. The synthesis of V was performed under N2 atmosphere. The final product of CH3C6H4-H2ip is white if the obtained crude product of V is decolorized by refluxing in EtOH with activated carbon. Hydrothermal method has been proven to be a powerful approach for the preparation of coordination polymers. In this work, complexes 1−4 were obtained by using the hydrothermal route and the synthetic strategy is shown in Scheme 2. All B



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Scheme 2. Schematic View of the Syntheses of Complexes 1−4

Figure 1. (a) View of local coordination environment of Co(II) atom in 1. Symmetry codes: A, x + 1/2, −y + 1/2, z + 1/2; B, −x + 1/2, y + 1/2, −z + 3/2. (b) The 2D coordination network of 1. (c) A packing diagram of 1 showing the interdigitation of the 2D layers. (d) Schematic illustration of the mutual polythreading of the 2D sheets in 1.

the paddle-wheel unit is 2.8700(8) Å. The binuclear paddlewheel cobalt nodes are connected by the CH3C6H4-ip to form a 2D layer parallel to the ab plane. In addition, the binuclear paddle-wheel cobalt nodes are alternately interlinked by bib ligands along the b axis, which increase the stability of the 2D framework.

Hydrothermal reactions of cobalt(II) salt with bib and H2tbip (H2tbip = 5-tert-butyl- isophthalic acid) led to the formation of 7 in our previous work14 (see Table 1). Compound 7 is a hydrogen-bonded 3D network constructed from 2D layers which consists of alternating left- and right-handed helical chains. The result shows that the difference of the substituent on C5 has a great influence on the structure of the complexes. C



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Scheme 3. (a−c) Versatile Coordination Modes of CH3C6H4-ip Observed in 1−4

Table 1. Examples of CoII-5-R-isophthalate Coordination Polymersa no.

R group

N-donor ligand

5 6 7 8

-H -OH -C(CH3)3 -NO2

bip bip bib bpe

9 10 11 12 13

-NO2 -H -C(CH3)3 -C(CH3)3 -NO2

bpe bpe bpe bpe bipy

{[Co(ip)(bip)]·H2O}n {[Co(OH-ip)(bip)]}n {[Co2(tbip)2(bip)2]·2H2O}n {[Co4(μ3OH)2(H2nip)2(Hnip)2(bpe)2]}n {[Co(bpe)(nip)]·0.5(bpe)·H2O}n {[Co(ip)(bpe)]}n {[Co3(tbip)3(bpe)3]·0.5(bpe)·3H2O}n {[Co2(tbip)2(bpe)(H2O)]}n {[Co(nip)(bipy)(H2O)]}n

14

-NO2

bipy

{[Co(nip)(bipy)(H2O)]·0.25H2O}n

15

-OH

bipy

{[Co(OH-ip)(bipy)]·2H2O}n

16

-H

bipy

{[Co(ip)(bipy)]·4H2O}n

17

-C(CH3)3

bipy

{[Co4(tbip)4(bipy)4(H2O)4]}n

a

formula

structure

ref

bilayer with a (42·63·8) topology sql layer and linked by H-bonding to form a 3D supramolecular structure layer and linked by H-bonding to form a 3D supramolecular structure layer consisting of rhombic {Co4} clusters

13 13 14 15a

2D bilayer possessing nanoscale rectangular channels 2D layer consisting of double layer unit 3D six-connected self-penetrating 48.66.8 network 3D 2-fold interpenetrated α-Po network 1D zigzag chains and linked by H-bonding to form a 3D supramolecular structure 1D chains and linked by π−π stacking interactions and H-bonding to form a 3D supramolecular structure 1D chains and linked by H-bonding and π−π stacking interactions to form a 3D supramolecular structure 2D layers and linked by π−π stacking interactions and H-bonding to form a 3D supramolecular structure tetranuclear clusters and linked by H-bonding to form a 3D supramolecular structure

15b 15c 16 16 17a

2D 2D 2D 2D

17b 17c 17c 17d

ip = isophthalate, OH-ip = 5-OH-isophthalate, tbip = 5-tert-butyl-isophthalate, nip = 5-nitro-isophthalate.

Figure 2. (a) View of local coordination environment of Co(II) atom in 2. Symmetry codes: A, x − 1/2, −y + 3/2, −z + 2; B, −x + 3/2, y + 1/2, −z + 2; C, −x + 3/2, y − 1/2, −z + 2. (b) The 2D coordination network of 2.

{[Co(CH3C6H4-ip)(bpe)0.5(H2O)]·H2O}n (3). Compound 3 crystallizes in the triclinic system with space group P1̅. The asymmetric unit contains one Co(II) ion, one CH3C6H4-ip, one-half bpe, one coordinated water molecule, as well as one free lattice water molecule. The Co(II) center is six-coordinated by four carboxylic oxygen atoms (O1, O2, O4A, and O4B, symmetry codes: A: x, y + 1, z; B: −x, −y, −z) from three different CH3C6H4-ip, one oxygen atom (O6) from one water

molecule and one nitrogen atom (N1) from one bpe. The coordinated geometry of Co(II) ion is a distorted octahedron with one carboxylic oxygen and one bpe nitrogen atom (O1 and N1) at the axial position (see Figure 3a). The Co−N bond distance is 2.0953(16) Å, and the Co−O bond lengths are in the range of 2.0503(13) to 2.3365(15) Å. The bond angles around Co range from 58.79(5) to 171.73(5)°. D



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Figure 3. (a) View of local coordination environment of Co(II) atom in 3. Symmetry codes: A, x, y + 1, z; B, −x, −y, −z. (b) The 2D coordination network of 3. (c) Projection of 3D hydrogen bonding supramolecular architecture of 3.

CH3C6H4-ip acts as a μ3-bridge linking three Co(II) ions, in which one carboxylic group adopts a μ2-η2:η0 bridging mode to connect two Co(II) ions, the other adopts a μ1-η1:η1 chelating mode to coordinate one Co(II) ion (Scheme 3c). The adjacent Co(II) ions are bridged by CH3C6H4-ip ligands to form a 1D chain. As shown in Figure 3b, the 1D chains are further linked by bpe to form a 2D layer parallel to the bc plane. The 2D layers are linked by hydrogen bonding between coordinated water molecules and CH 3 C 6 H4 -ip O atoms O(6)−H(4W)···O(3)#7 (symmetry codes: #7: −x + 1, −y, −z) to generate a 3D supramolecular architecture, which shows channels along the c axis that are occupied by the lattice water molecules (Figure 3c). Intermolecular hydrogen bonding interactions also exist between free water molecules, coordinated-water molecules and CH3C6H4-ip O atoms (O(5)− H(1W)···O(2)#5, O(6)−H(3W)···O(5)#6, symmetry codes: #5: x, y, z + 1, #6: −x + 1, −y, −z + 1). These hydrogen bonding interactions (Table S3) bring further stability of the structure of 3. Some complexes based on 5-R-ip (R = -NO2, -C(CH3)3, and -H) with Co(II) and bpe have been prepared in the literature. These coordination polymers display various types of 2D layers (8−10)15 or 3D networks (11 and 12),16 which are different from that of 3 (see Table 1). {[Co(CH3C6H4-ip)(bipy)0.5]}n (4). Compound 4 crystallizes in the monoclinic system with space group C2/c. Single crystal Xray structure analysis reveals that the asymmetric unit of 4 contains one Co(II) ion, one CH3C6H4-ip, and one-half bipy.

As shown in Figure 4a, each Co(II) atom is located in the center of a distorted octahedral (CoO4N2) geometry, defined by two nitrogen atoms (N1 and N1C, symmetry codes: C: −x + 1, y, −z + 5/2) of one bipy [Co(1)−N(1) = Co(1)−N(1)C = 2.1260(15) Å] and four oxygen atoms from four CH3C6H4-ip [Co(1)−O(3)A = Co(1)−O(3)B = 2.0605(13) and Co(1)− O(1) = Co(1)−O(1)C = 2.0990(12) Å]. Each CH3C6H4-ip acts as a μ2-bridge linking two Co(II) ions, in which each carboxylic group adopts a μ1-η1: η0 bridging mode (Scheme 3a). The adjacent Co(II) ions are bridged by CH3C6H4-ip to form a 1D chain (Figure 4b). The bipy ligands are trans-located in the 1D chain. Hydrothermal reactions of 5-R-ip (R = -H, -NO2, -OH, -C(CH3)3) with cobalt(II) salt and bipy led to the formation of complexes 13−17 (see Table 1) in the literature.17 These complexes feature 1D → 3D (13−15), 2D → 3D (16), 0D → 3D (17) structures. According to the above descriptions, the structures of 4 are different from those of 13−17, which shows that the methylphenyl skeleton has an effect on the final structure. Thermal Analysis. Thermal behaviors of complexes 1−4 were investigated under nitrogen atmosphere by TGA (see Figure S1 in Supporting Information). For complex 1, the TGA curve shows a weight loss of 6.7% between 30 and 272 °C corresponding to the loss of the lattice water molecules (calcd 6.6 wt %). The anhydrous compound begins to decompose at 348 °C. For 2, the first weight loss corresponding to the release of a water molecule is observed before 139 °C (obsd 3.1%, E



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Figure 4. (a) View of local coordination environment of Co(II) atom in 4. Symmetry codes: A, −x + 1, −y + 1, −z + 2; B, x, −y + 1, z + 1/2; C, −x + 1, y, −z + 5/2. (b) The 1D chain of 4.

Figure 5. Temperature dependence of χMT and χM for 2 (a) and 3 (b). Open points are the experimental data, and the solid line represents the best fit obtained from the Hamiltonian given in the text.

Magnetic Properties. The magnetic susceptibilities, χM, of 2 and 3 were measured in the 2−300 K temperature range, and shown as χMT and χM versus T plots in Figure 5. As the temperature lowers to 2 K, the χMT products of 2 (Figure 5a) continuously decrease which suggests that antiferromagnetic interactions are operative in 2. The experimental χMT value of 2 at room temperature is 4.73 cm3 K mol−1, which is larger than two isolated spin-only Co2+ ions (3.75 cm3 K mol−1). This larger value is the result of contributions to the susceptibility from orbital angular momentum at high temperature. The temperature dependence of the reciprocal susceptibilities (1/

calcd 2.1%), and the departure of organic components occurs from 219 °C. The TGA curve of 3 indicates that there is a weight loss of 7.7% from 30 to 111 °C, which can be attributed to the loss of one lattice H2O molecule and one coordinated H2O molecule (calcd 8.2 wt %). The removal of the organic components occurs in the range of 390 to 550 °C. The TGA diagrams of 4 displays no weight loss before 262 °C. As the temperature further increases, 4 rapidly decomposes and the weight loss is steep until the temperature reaches 438 °C, indicating the removal of organic ligands. F



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χM) of 2 obey the Curie−Weiss law above 50 K with θ = −88.1 K, C = 5.92 cm3·K/mol, and R = 7.5 × 10−3. The moderate negative θ value indicates the presence of antiferromagnetic interactions among adjacent Co(II) ions even if a contribution from the spin−orbit coupling of Co(II) is also present.18 In 2, the Co···Co separation across the bridging two O atoms of one carboxylic group is 2.8700(9) Å, significantly shorter than 8.6543(8) and 8.6621(10) Å for the bib and the shortest two carboxylic group bridges. The magnetic susceptibility data were fitted assuming that the two O atoms of one carboxylic group bridges between Co (II) ions form a dimer with exchange constant J. The susceptibility data were thus approximately analyzed by an isotropic dimer mode of spin S = 3/2.19 The following eq 1 is induced from the Hamiltonian Ĥ = −JS1S2 χM =

Ng 2β 2 A KT B

properties have also been investigated. Further systematic works for the design and synthesis of such crystalline materials with CH3C6H4-ip, N-donor auxiliary ligands, and other metal ions are underway in our lab.

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EXPERIMENTAL SECTION

Materials and Physical Measurements. All reagents used in the syntheses were of analytical grade. 5-Bromo-3,5-dimethylbenzene (I), bis(pinacolato)diborane, Pd(dppf)2Cl2, Pd(PPh3)4 were purchased from Jinan Henghua Sci. & Tec. Co. Ltd. without further purification. Elemental analyses of C, N, and H were performed on a Vario EL III elemental analyzer. IR (KBr pellet) spectra were recorded on an Avatar 360 E. S. P. IR spectrometer. Thermogravimetric measurements were carried out in a nitrogen stream using a Netzsch STA449C apparatus with a heating rate of 10 °C min−1. Variable-temperature magnetic susceptibilities were measured using a MPMS-7 SQUID magnetometer. Diamagnetic corrections were made with Pascal’s constants for all constituent atoms.20 Synthesis of 5-(4′-Methylphenyl)isophthalic Acid. Synthesis of 5-Bromoisophthalic Acid (II). The mixture of I (1000 mmol, 18.5 g), KOH (110 mmol, 6.0 g), and 600 mL of H2O was heated to reflux. KMnO4 (440 mmol, 70.0 g) was added in portions to the refluxing solution. Refluxing was continued for 12 h. After being cooling to room temperature, the mixture was filtered and the residual manganese dioxide was washed with the solution of hydroxide sodium. The combined filtrates were acidified with concentrated hydrochloric acid. The white solid precipitate was filtered off, washed several times with water, and dried to afford II (82%). EI-MS: m/z [M − H]− 242.9 (calcd for C8H5BrO4, 243.9). Anal. (%) calcd. for C8H5BrO4: C, 39.21; H, 2.06. Found: C, 39.08; H, 2.02. Synthesis of Diethyl 5-Bromoisophthalate (III). The mixture of II (100 mmol, 24.5 g), 500 mL ethanol, and 10 mL concentrated H2SO4 was refluxed for 12 h, and then poured into 500 mL H2O. The solution was extracted with ethyl acetate (200 mL × 3), dried with anhydrous magnesium sulfate, and then concentrated on rotary evaporator to give a white powder (92%). Anal. (%) calcd. for C12H13BrO4: C, 47.86; H, 4.35. Found: C, 47.79; H, 4.32. Synthesis of 4,4,5,5-Tetramethyl-2-(diethyl 3,5-dicarboxylatephenyl)-1,3-dioxolane (IV). The mixture of III (100 mmol, 30.0 g), bis(pinacolato)diborane (11.8 mmol, 3.0 g), potassium acetate (0.29 mmol, 28.0 g), Pd (dppf)2Cl2 (7.0 mmol, 5.0 g), and dried 1,4-dioxane (500 mL) at 100 °C overnight and afterward extracted with ethyl acetate (200 mL × 3). The organic layer was decolored with activated carbon and dried by anhydrous Na2SO4. The crude product was obtained from concentration under a vacuum and purified by column chromatography (silica gel, ethylacetate/petroleum ether, 6 v %). Yield 78%. Anal. (%) calcd. for C18H25BO6: C, 62.09; H, 7.24. Found: C, 61.89; H, 7.15. Synthesis of Diethyl 5-(4′-Methylphenyl)isophthalate (V). The mixture of IV (100 mmol, 34.82 g), bromobenzene (50 mmol, 7.85 g), and K3PO4 (200 mmol, 42.4 g) were mixed in 1,4-dioxane (500 mL), and the mixture was deaerated using N2 for 10 min. Pd(PPh3)4 (4 mmol, 5.0 g) was added to the stirred reaction mixture and the mixture was heated to reflux for ca. one week under N2 atmosphere. The crude product of VI was obtained after 1,4-dioxane was removed under a vacuum. Recrystallization from methanol offered the pure diethyl 5(4′-methylphenyl)isophthalate. Anal. (%) calcd. for C19H20O4: C, 73.06; H, 6.45. Found: C, 72.88; H, 6.39. Synthesis of 5-(4′-Methylphenyl)isophthalic Acid (VI). The mixture of V (50 mmol, 25.9 g) and 10 g of NaOH in 500 mL of H2O was refluxed for 2 h, and then cooled to room temperature. The solution was neutralized with concentrated HCl. White powder was obtained with the yield of 92%. EI-MS: m/z [M − H]−, 255.2 (calcd for C15H12O4, 256.2). Anal. (%) calcd. for C15H12O4: C, 70.31; H, 4.72. Found: C, 7.15; H, 4.63. Preparation of Complexes 1−4. {[Co(CH3C6H4-ip)(bip)]·2H2O}n (1). A mixture of CH3C6H4−H2ip (0.1 mmol, 25.6 mg), bip (0.1 mmol, 20.4 mg), Co(Ac)2·4H2O (0.1 mmol, 24.9 mg), KOH (0.1 mmol, 5.6 mg), and H2O (12 mL) was placed in a Teflon-lined

(1)

A = 2 exp[−2J / KT ] + 10 exp[−6J / KT ] + 28 exp[−12J / KT ] B = 1 + 3 exp[−2J / KT ] + 5 exp[− 6J / KT ] + 7 exp[−12J / KT ]

A least-squares analysis of magnetic susceptibilities data led to J = −9.9 cm−1, g = 1.95, and R = 5.75 × 10−3. The J value indicates antiferromagnetic interactions between the nearest Co(II) ions bridged by two O atoms of one carboxylic group. The experimental χMT value of 3 at room temperature is 6.32 cm3 K mol−1, which is larger than two isolated spin-only Co2+ ions (3.75 cm3 K mol−1). As the temperature decreases to 2 K, the χMT value increases slightly (Figure 5b). The behavior indicates a dominant ferromagnetic interaction between the Co(II) ions. The temperature dependence of the reciprocal susceptibilities (1/χM) of 3 obeys the Curie−Weiss law above 50 K with θ = 4.3 K, C = 5.32 cm3·K/mol, and R = 2.6 × 10−4. The positive θ value indicates the presence of ferromagnetic interactions among adjacent Co(II) ions. As the shortest Co···Co distance across the O atom bridge is 3.3577(5) Å in 3. The observed ferromagnetic interaction, therefore, should mainly arise from the magnetic superexchange through the O atom bridges. The magnetic susceptibility data were fitted assuming that the O atoms between Co (II) ions form a dimer with exchange constant J. The susceptibility data were thus approximately analyzed by an isotropic dimer mode of spin S = 3/2.19 The least-squares analysis of magnetic susceptibility data led to J = 1.83 cm−1, g = 2.38, and R = 6.09 × 10−3. The J value indicates ferromagnetic interactions between the nearest Co(II) ions bridged by one O atom of the carboxylic group.

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CONCLUSIONS By the use of an unexplored isophthalic acid derivative ligand, 5-(4′-methylphenyl)isophthalic acid, four new low-dimensional (1D and 2D) coordination networks have been synthesized and structurally characterized. It is worth noting that the CH3C6H4ip ligand can be used as a polydentate to coordinate Co(II) ions into coordination polymers in different modes. The results indicate that the bulky steric hindrance of methylphenyl in CH3C6H4-ip plays an important role in governing the final structures. In addition, the thermal behaviors and magnetic G



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Table 2. Crystallographic Data and Details of Diffraction Experiments for Complexes 1−4 formula Mr crystal system space group a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z ρ (g cm−3) μ (mm−1) T (K) GOF R [I > 2σ(I)] R (all data)

1

2

3

4

C26H30CoN4O6 553.47 monoclinic P21/c 8.649(5) 16.573(10) 18.729(12) 90 96.097(7) 90 2670(3) 4 1.377 0.689 296(2) 1.021 R1 = 0.0710, wR2 = 0.1462 R1 = 0.1984, wR2 = 0.1856

C40H36Co2N4O9 834.59 orthorhombic P21212 19.7573(12) 19.757 10.2813(6) 90 90 90 4013.3(3) 4 1.381 0.884 296(2) 1.062 R1 = 0.0549, wR2 = 0.1487 R1 = 0.0582, wR2 = 0.1521

C21H19CoNO6 440.30 triclinic P1̅ 8.3347(9) 10.1455(11) 12.5359(13) 75.7640(10) 89.7660(10) 70.3200(10) 963.86(18) 2 1.517 0.929 296(2) 0.968 R1 = 0.0296, wR2 = 0.0722 R1 = 0.0325, wR2 = 0.0741

C40H30CoN2O8 725.59 monoclinic C2/c 10.4565(12) 19.215(2) 16.9416(18) 90 93.6110(10) 90 3397.2(6) 4 1.419 0.564 296(2) 1.040 R1 = 0.0304, wR2 = 0.0782 R1 = 0.0400, wR2 = 0.0839

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stainless steel vessel, heated to 120 °C for 4 days, and then cooled to room temperature over 24 h. Red block crystals of 1 were obtained. Yield: 43% based on Co. Anal. (%). calcd for C26H30CoN4O6: C, 56.42; H, 5.46; N, 10.12. found: C, 56.69; H, 5.28; N, 10.36. IR (cm−1): 3125 m, 1613 m, 1543 s, 1440 s, 1354 m, 1277s, 1123s, 1070 m, 994 s, 776 s, 733s, 674 m. {[Co2(CH3C6H4-ip)2(bib)]·H2O}n (2). 2 was synthesized in the similar way as that described for 1, except that bip was replaced by bib (0.1 mmol, 19.0 mg). Yield: 37% based on Co. Anal. (%): calcd for C40H36Co2N4O9: C, 57.56; H, 4.35; N, 6.71. found: C, 57.49; H, 4.39; N, 6.76. IR (cm−1): 3110 m, 1632 m, 1519 s, 1365 s, 1295 m, 1232 m, 1104 s, 945 m, 923 s, 821 m, 776 s, 724 m, 655 s. {[Co(CH3C6H4-ip)(bpe)0.5(H2O)]·H2O}n (3). 3 was synthesized in the similar way as that described for 1, except that bip was replaced by bpe (0.1 mmol, 18.1 mg). Yield: 51% based on Co. Anal. (%): calcd for C21H19CoNO6: C, 57.28; H, 4.35; N, 3.18. found: C, 57.33; H, 4.31; N, 3.15. IR (cm−1): 3183 m, 1607 m, 1547 s, 1414s, 1338 s, 1274 m, 1152 m, 1067 m, 1023 m, 960 s, 817 s, 772 s, 729 m, 666 m. {[Co(CH3C6H4-ip)(bipy)0.5]}n (4). 4 was synthesized in the similar way as that described for 1, except that bip was replaced by bipy (0.1 mmol, 15.9 mg). Yield: 45% based on Co. Anal. (%): calcd for C40H30CoN2O8: C, 66.21; H, 4.17; N, 3.86. found: C, 66.17; H, 4.22; N, 3.82. IR (cm−1): 2919 w, 1667 s, 1593 m, 1518 m, 1441 s, 1404 m, 1309 m, 1247 s, 1169 m, 1072 m, 1022 m, 911 s, 817 s, 759 s, 737 s, 706 s, 678 m. X-ray Crystallography. Single crystal X-ray diffraction analyses of 1−4 were carried out on a Bruker SMART APEX II CCD diffractometer equipped with a graphite monochromated Mo Kα radiation (λ = 0.71073 Å) by using ϕ/ω scan technique at room temperature. The structures were solved by direct methods with SHELXS-97. The hydrogen atoms were assigned with common isotropic displacement factors and included in the final refinement by use of geometrical restrains. The crystallographic data and selected bond lengths and angles for 1−4 are listed in Table 2 and Table S1− S4, shown in Supporting Information. The crystal data of complexes 1 and 2 contain some high-angle weak data which may be attributed to the small measurable crystals. Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center. CCDC reference numbers: 871676 for 1, 871677 for 2, 871678 for 3, and 871679 for 4.

ASSOCIATED CONTENT

* Supporting Information S

Crystallographic data in CIF format and TGA figures. This information is available free of charge via the Internet at http:// pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected] (L.-F.M.); [email protected] (L.Y.W.). Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (21073082, 21071074), Program for New Century Excellent Talents in University (NCET-11-0947), and Program for Science & Technology Innovation Talents in Universities of Henan Province (2011HASTIT027).

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Four Low-Dimensional Cobalt(II) Coordination Polymers Based on a

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