Diversity of Coordination Architecture of Copper(II)−5-Sulfoisophthalic

Aug 9, 2007 - X-ray structural analyses of 1−7 reveal their structural diversity ranging from zero-dimensional (0-D) (1), one-dimensional (1-D) (2),...
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Diversity of Coordination Architecture of Copper(II)-5-Sulfoisophthalic Acid: Synthesis, Crystal Structures, and Characterization Qing-Yan Liu, Da-Qiang Yuan, and Li Xu*

CRYSTAL GROWTH & DESIGN 2007 VOL. 7, NO. 9 1832-1843

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, People’s Republic of China ReceiVed April 28, 2007; ReVised Manuscript ReceiVed June 6, 2007

ABSTRACT: Hydrothermal synthesis of a series of copper(II)-H3SIP coordination polymers (H3SIP ) 5-sulfoisophthalic acid), [Cu3(SIP)2(H2O)14] (1), {[Cu(SIP)(H2O)4](H2en)0.5}n (2), {Na[Cu2(SIP)(HSIP)(H2O)8](H2O)3}n (3), {[Cu4(OH)2(SIP)2(H2O)2](H2O)4}n (4), [Cu2(OH)(SIP)(bpy)(H2O)]n (5), [Cu4(OH)2(SIP)2(bpy)3(H2O)]n (6), and [Cu4(OH)2(SIP)2(bpy)2(H2O)2]n (7) (bpy ) 2,2′-bipyridine; en ) ethylenediamine), has been achieved by fine control over the reaction conditions including pH value, organic template, reaction temperature, starting materials, auxiliary ligand, and stoichiometry. X-ray structural analyses of 1-7 reveal their structural diversity ranging from zero-dimensional (0-D) (1), one-dimensional (1-D) (2), two-dimensional (2-D) (3, 5, and 6), to three-dimensional (3-D) (4 and 7). The relationship between the reaction conditions and the resulting structures has been rationalized. The trinuclear complex 1 represents the first example of a discrete metal-SIP coordination complex. The presence of countercations such as H2en2+ and Na+ leads to the formation of a Cu-SIP zigzag chain in 2 and 3. A larger template such as triethylenediamine (TEDA) accounts for the formation of the tetranuclear [Cu4(µ3-OH)2] secondary building unit (SBU) in 4 and hence the 3-D network structure with unprecedented (411‚614‚83)(45‚6)2 topology. Polymer 5 formed at a comparatively lower temperature has the binuclear [Cu2(µ2OH)] SBU and thus the 2-D double-sided layer structure of 4‚82 topology. The enhanced temperature results in the formation of the tetranuclear [Cu4(µ3-OH)2] SBU of 7 and hence the 3-D framework structure of rutile topology (4‚62)2(42‚610‚83). 6 contains the unusual tetranuclear [Cu4(µ3-OH)(µ2-OH)] SBU induced by one more bpy ligand that results in a 2-D layered structure of unique (3‚52)2(32‚53) topology. The temperature-dependent magnetic susceptibility data of 1-5 have been modeled using both CurieWeiss law and isotropic spin-Hamiltonian, revealing weakly ferromagnetically or antiferromagnetically magnetic interactions between the Cu2+ ions bridged by OH- or SIP ligands. Introduction The design and construction of metal-organic frameworks (MOFs) is one of the most active areas of materials research in recent years.1 The intense interest in these materials is driven by their potential applications as functional materials (catalysis, magnetism, gas separation, and nonlinear optics)2 as well as by their structural diversity and intriguing topologies.3 Hydrothermal reactions of multifunctional organic ligands and metal ions are the most powerful and widely employed tool in the preparation of MOFs, which usually produce robust extended structures desired for practical applications. A variety of metalorganic architectures with diversified topologies and interesting properties have been prepared through the judicious choice of organic ligands and metal ions.4,5 Aromatic polycarboxylates such as 1,3,5-benzenetricarboxylate (H3BTC) are one of the most successful multifunctional ligands because of their structural rigidity, chemical stability, and appropriate connectivity.6 Recently, a variation of H3BTC, namely, 5-sulfoisophthalic acid (H3SIP), has received increasing interest.7 In contrast to the carboxylate group, the sulfonate group is generally perceived as a weaker group with respect to their coordinating ability and have one more potentially coordinating oxygen atom. The weak coordination nature of -SO3- makes its coordination mode very flexible and sensitive to the chemical environment. H3SIP has been used as an efficient probe to examine the lanthanide contraction effect8a and the coordination polymer chemistry of the main group element (Pb2+).8b In the present contribution, H3SIP is used as a probe to investigate the coordination polymer chemistry of Cu(II)-5-sulfoisophthalic acid under various reac* Corresponding author. Tel.: +86-591-83705045. Fax: +86-5918370545. E-mail: [email protected].

tion conditions. Copper(II) is selected as it has multiple coordination geometry. As will be described in the text, the CuSIP system exhibits rich coordination polymer chemistry wherein reaction conditions such as pH value, temperature, template, auxiliary ligands, and the ratio of the reactants play an important role in the formation of coordination compounds. A series of zero-dimensional (0-D), one-dimensional (1-D), twodimensional (2-D), and three-dimensional (3-D) copper(II)SIP coordination polymers, [Cu3(SIP)2(H2O)14] (1), {[Cu(SIP)(H2O)4](H2en)0.5}n (2), {Na[Cu2(SIP)(HSIP)(H2O)8](H2O)3}n (3), {[Cu4(OH)2(SIP)2(H2O)2](H2O)4}n (4), [Cu2(OH)(SIP)(bpy)(H2O)]n (5), [Cu4(OH)2(SIP)2(bpy)3(H2O)]n (6), and [Cu4(OH)2(SIP)2(bpy)2(H2O)2]n (7) (bpy ) 2,2′-bipyridine; en ) ethylenediamine), have been prepared and characterized by singlecrystal X-ray diffraction, IR, temperature-dependent magnetic susceptibility, and powder X-ray diffraction. Their net topologies are discussed in detail. Experimental Section General Methods. All commercially available chemicals are of reagent grade and used as received without further purification. 5-Sulfoisophthalic acid monosodium salt (NaH2SIP) and bpy were obtained from Acros. IR (KBr pellets) spectra were recorded in the 400-4000 cm-1 range using a Perkin-Elmer Spectrum One FT-IR spectrometer. Elemental analyses were carried out on Elementar Vario EL III microanalyzer. Variable temperature susceptibility measurements were carried out in the temperature range of 5-300 K at a magnetic field of 0.5 or 1.0 T on polycrystalline samples with a Quantum Design MPMS-5 magnetometer. Powder X-ray diffraction patterns were performed on a RIGAKU DMAX2500PC diffractometer using CuKR radiation. All syntheses were carried out in 25 mL Teflon-lined autoclaves under autogenous pressure. The reaction vessels were filled to approximately 60% volume capacity. Water used in the reactions is distilled water.

10.1021/cg070407g CCC: $37.00 © 2007 American Chemical Society Published on Web 08/09/2007

Coordination of Copper(II)-5-Sulfoisophthalic Acid

Crystal Growth & Design, Vol. 7, No. 9, 2007 1833

Table 1. Crystallographic Data for Complexes 1-7

formula fw cryst size, mm temp, K cryst syst space group a, Å b, Å c, Å R, deg β, deg γ, deg V, Å3 Z Dc, g‚cm-3 µ, mm-1 measured refln independent refln observed reflna no. parameters F(000) GOF R(int) R1 [I > 2σ(I)]b wR2 [all refln] max/min, e Å-3

formula fw cryst size, mm temp, K cryst syst space group a, Å b, Å c, Å R, deg β, deg γ, deg V, Å3 Z Dc, g·cm-3 µ, mm-1 measured refln independent refln observed reflna no. parameters F(000) GOF R(int) R1 [I > 2σ(I)]b wR2 [all refln] max/min, e Å-3 a

1

2

3

4

C16H34O28S2Cu3 929.17 0.38 × 0.38 × 0.10 293(2) triclinic P1h 6.6144(13) 10.699(2) 12.180(3) 71.611(6) 74.763(7) 75.408(8) 775.7(3) 1 1.989 2.284 5932 3478 3160 265 473 1.062 0.0195 0.0238 0.0684 0.471/ -0.457

C9H16NO11SCu 409.83 0.60 × 0.40 × 0.30 293(2) monoclinic P21/n 6.9528(15) 16.301(4) 13.265(3) 90 101.835(2) 90 1471.4(6) 4 1.850 1.686 11057 3340 3246 232 840 1.008 0.0149 0.0227 0.0679 0.441/ -0.655

C16H29O25S2Cu2Na 835.58 0.28 × 0.15 × 0.15 293(2) monoclinic P21/n 12.2779(7) 17.4665(7) 13.8113(6) 90 109.442(2) 90 2793.0(2) 4 1.987 1.798 21304 6361 5821 485 1704 1.016 0.0309 0.0367 0.1043 1.627/ -1.162

C16H20O22S2Cu4 882.60 0.22 × 0.20 × 0.15 293(2) monoclinic P21/n 7.3336(7) 18.1829(19) 10.1252(9) 90 94.493(4) 90 1346.0(2) 2 2.178 3.372 10298 3082 2619 227 880 1.005 0.0418 0.0429 0.1012 0.618/ -0.631

5

6

7

C18H14N2O9SCu2 561.45 0.20 × 0.12 × 0.04 293(2) monoclinic P21/n 7.6861(13) 17.984(2) 14.580(2) 90 98.155(10) 90 1995.0(5) 4 1.869 2.294 11292 3173 2134 295 1128 1.003 0.0530 0.0760 0.2000 1.070/ -0.681

C46H34N6O17S2Cu4 1261.07 0.50 × 0.30 × 0.10 293(2) triclinic P1h 10.1864(16) 10.6594(18) 22.761(4) 88.194(4) 80.517(4) 67.384(4) 2248.8(7) 2 1.862 2.046 17496 10148 8980 688 1272 1.005 0.0185 0.0349 0.0846 0.533/ -0.588

C36H28N4O18S2Cu4 1122.90 0.55 × 0.40 × 0.05 293(2) monoclinic P21/n 10.1536(7) 18.4953(11) 10.3710(8) 90 105.270(3) 90 1878.9(2) 2 1.985 2.435 14403 4278 3819 301 1128 1.006 0.0438 0.0454 0.1136 0.577/ -0.725

Observation criterion: I > 2σ(I). b R1 ) ∑||Fo| - |Fc||/∑|Fo| and wR2 ) {∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]}1/2.

[Cu3(SIP)2(H2O)14] (1). A mixture of CuCl2 (20.1 mg, 0.15 mmol), NaH2SIP (26.8 mg, 0.1 mmol), NaOH (0.2 mL, 1 M), and water (15 mL) (pH ) 6) was heated at 160 °C for 4 days; blue prism-like crystals of 1 were obtained when the sample was cooled to room temperature at 5 °C/h. The crystals were recovered by filtering, washed with distilled water, and dried in air (yield: 16.6 mg, 33% based on Cu). Anal. Calcd for C16H34O28S2Cu3 (929.17): C, 20.67; H, 3.66%. Found: C, 20.61; H, 3.63%. IR spectrum (KBr pellet, cm-1): 3557 s, 3208 s, 2974 s, 1603 s, 1566 s, 1431 s, 1373 s, 1260 m, 1211 s, 1121 s, 1046 s, 995 m, 920 w, 842 m, 758 m, 685 w, 672 w, 618 w, 501 w. {[Cu(SIP)(H2O)4](H2en)0.5}n (2). A mixture of CuCl2 (26.9 mg, 0.2 mmol), NaH2SIP (53.6 mg, 0.2 mmol), en (0.7 mL), and water (15 mL) was heated at 160 °C for 4 days; blue rodlike crystals of 2 were obtained when the sample was cooled to room temperature at 5 °C/h. (yield: 56.5 mg, 69% based on Cu). Anal. Calcd for C9H16NO11SCu (409.83): C, 26.35; H, 3.90; N, 3.42%. Found: C, 26.37; H, 3.88; N, 3.39%. IR spectrum (KBr pellet, cm-1): 3382 s, 3244 m, 3116 s, 1672

w, 1604 s, 1546 s, 1517 s, 1439 m, 1372 s, 1203 s, 1127 w, 1047 s, 915 w, 797 w, 767 w, 730 m, 696 w, 620 s, 476 m, 421 w. {Na[Cu2(SIP)(HSIP)(H2O)8](H2O)3}n (3). A mixture of CuCl2 (26.9 mg, 0.2 mmol), NaH2SIP (53.6 mg, 0.2 mmol), NaOH (0.1 mL, 1 M), and water (15 mL) (pH ) 2) was heated at 160 °C for 4 days; blue prism-like crystals of 3 were obtained when the sample was cooled to room temperature at 5 °C/h. The crystals were recovered by filtering, washed with distilled water, and dried in air (yield: 43.4 mg, 52% based on Cu). Anal. Calcd for C16H29O25S4Cu2Na (835.58): C, 22.98; H, 3.49%. Found: C, 22.93; H, 3.42%. IR spectrum (KBr pellet, cm-1): 3546 s, 3336 s, 3232 s, 3008 s, 1603 s, 1565 s, 1431 s, 1370 s, 1259 m, 1243 s, 1194 s, 1120 s, 1047 s, 995 w, 919 w, 842 m, 758 m, 685 w, 672 w, 616 s, 501 w. {[Cu4(OH)2(SIP)2(H2O)2](H2O)4}n (4). A mixture of CuCl2 (26.9 mg, 0.2 mmol), NaH2SIP (26.8 mg, 0.1 mmol), triethylenediamine (TEDA) (35 mg, 0.16 mmol), and water (15 mL) was heated at 160 °C for 4 days; blue rodlike crystals of 4 were obtained when the sample

1834 Crystal Growth & Design, Vol. 7, No. 9, 2007

Liu et al.

Table 2. Selected Bond Lengths (Å) and Bond Angles (°) of 1-7a Complex 1 1.948(1) Cu(1)-O(8) 1.999(1) 1.938(1) Cu(1)-O(10) 2.398(2) 1.934(1) Cu(1)-O(12) 2.473(2) 1.987(1) Cu(2)-O(13) 1.948(1) 2.588(2) O(9)-Cu(1)-O(8) 91.77(6) 93.48(5) O(11)-Cu(1)-O(3) 85.02(6) 89.71(6) O(10)-Cu(1)-O(3) 85.78(5) 177.31(4) O(10)-Cu(1)-O(9) 88.07(6) 93.25(5) O(12)-Cu(1)-O(3) 91.94(5) 90.53(7) O(12)-Cu(1)-O(9) 90.66(6) 89.15(5) O(1)-Cu(2)-O(13) 89.50(5) 90.68(6) O(14)-Cu(2)-O(13) 92.07(5) 94.76(5) Complex 2 Cu(1)-O(1) 2.007(1) Cu(1)-O(8) 1.949(1) Cu(1)-O(9) 1.968(1) Cu(1)-O(10) 2.427(1) Cu(1)-O(11) 2.531(1) Cu(1)-O(3A) 1.975(1) O(8)-Cu(1)-O(1) 93.97(5) O(9)-Cu(1)-O(1) 89.53(5) O(8)-Cu(1)-O(3A) 83.35(5) O(3A)-Cu(2)-O(9) 93.46(5) O(10)-Cu(2)-O(1) 82.62(4) O(9)-Cu(2)-O(10) 83.73(4) O(10)-Cu(2)-O(3A) 93.16(4) O(8)-Cu(2)-O(10) 100.24(4) O(11)-Cu(2)-O(1) 94.98(4) O(9)-Cu(2)-O(11) 88.03(4) O(11)-Cu(2)-O(3A) 89.69(4) O(8)-Cu(2)-O(11) 88.11(4) Complex 3 Cu(1)-O(1) 1.920(2) Cu(1)-O(8) 2.042(2) Cu(1)-O(9) 2.018(2) Cu(1)-O(10) 2.273(2) Cu(1)-O(16A) 1.928(2) Cu(2)-O(3) 1.950(2) Cu(2)-O(11) 2.002(2) Cu(2)-O(12) 1.960(2) Cu(2)-O(13) 2.426(2) Cu(2)-O(14) 1.947(2) Na(1)-O(18) 2.295(2) Na(1)-O(21) 2.368(2) Na(1)-O(22) 2.414(2) Na(1)-O(21B) 2.407(3) Na(1)-O(11C) 2.465(2) O(9)-Cu(1)-O(1) 86.92(8) O(8)-Cu(1)-O(1) 90.23(8) O(16A)-Cu(2)-O(9) 89.84(8) O(8)-Cu(1)-O(16A) 94.39(8) O(9)-Cu(1)-O(10) 104.02(8) O(10)-Cu(1)-O(1) 90.82(8) O(8)-Cu(1)-O(10) 91.15(8) O(10)-Cu(1)-O(16A) 84.38(8) O(3)-Cu(2)-O(12) 90.31(8) O(3)-Cu(2)-O(11) 86.06(8) O(11)-Cu(2)-O(14) 94.89(8) O(12)-Cu(2)-O(14) 89.25(8) O(13)-Cu(2)-O(11) 99.87(8) O(13)-Cu(2)-O(3) 91.56(8) O(13)-Cu(2)-O(14) 86.22(8) O(13)-Cu(2)-O(12) 93.65(8) O(22)-Na(1)-O(11C) 74.34(8) O(21)-Na(1)-O(22) 169.44(9) O(21)-Na(1)-O(21B) 81.84(9) O(21B)-Na(1)-O(11C) 130.96(9) O(18)-Na(1)-O(22) 85.27(8) O(18)-Na(1)-O(21) 92.75(8) O(18)-Na(1)-O(21B) 84.03(8) O(18)-Na(1)-O(11C) 143.35(9) Na(1)-O(11C)-Cu(2C) 98.87(9) Na(1)-O(21)-Na(1B) 98.16(9) Complex 4 Cu(1)-O(5) 2.381(3) Cu(1)-O(8) 1.956(3) Cu(1)-O(9) 1.943(3) Cu(1)-O(1A) 1.923(3) Cu(1)-O(3B) 1.939(3) Cu(2)-O(8) 1.961(3) Cu(2)-O(2A) 1.946(3) Cu(2)-O(8D) 1.969(3) Cu(2)-O(4E) 1.914(3) Cu(2)-O(6C) 2.229(3) Cu(2)-Cu(2D) 2.940(1) O(3B)-Cu(1)-O(9) 84.91(13) O(8)-Cu(1)-O(3B) 96.01(11) O(8)-Cu(1)-O(1A) 93.46(11) O(9)-Cu(1)-O(1A) 85.82(13) O(9)-Cu(1)-O(5) 105.50(14) O(5)-Cu(1)-O(3B) 93.73(12) O(5)-Cu(1)-O(1A) 86.36(13) O(8)-Cu(1)-O(5) 79.84(11) O(8)-Cu(2)-O(8D) 83.16(11) Cu(1)-O(3) Cu(1)-O(9) Cu(1)-O(11) Cu(2)-O(1) Cu(2)-O(14) O(3)-Cu(1)-O(9) O(8)-Cu(1)-O(11) O(10)-Cu(1)-O(12) O(10)-Cu(1)-O(8) O(10)-Cu(1)-O(11) O(12)-Cu(1)-O(8) O(12)-Cu(1)-O(11) O(14)-Cu(2)-O(1)

Complex 4 (continued) O(8)-Cu(2)-O(2A) 95.77(11) O(8D)-Cu(2)-O(4E) O(4E)-Cu(2)-O(2A) 87.41(12) O(6C)-Cu(2)-O(8D) O(8)-Cu(2)-O(6C) 85.00(13) O(4E)-Cu(2)-O(6C) O(2A)-Cu(2)-O(6C) 93.13(13) Cu(1)-O(8)-Cu(2D) Cu(1)-O(8)-Cu(2) 114.65(13) Cu(2)-O(8)-Cu(2D) Complex 5 Cu(1)-O(8) 1.932(6) Cu(2)-O(2) Cu(1)-O(3A) 1.960(6) Cu(2)-N(2) Cu(1)-O(1) 1.984(6) Cu(2)-N(1) Cu(1)-O(9) 1.997(7) Cu(2)-O(5B) Cu(2)-O(8) 1.878(6) O(8)-Cu(2)-N(2) O(8)-Cu(1)-O(3A) 177.0(3) O(2)-Cu(2)-N(1) O(8)-Cu(1)-O(1) 95.4(3) N(2)-Cu(2)-N(1) O(3A)-Cu(1)-O(1) 83.4(3) O(8)-Cu(2)-O(5B) O(8)-Cu(1)-O(9) 88.9(3) O(2)-Cu(2)-O(5B) O(3A)-Cu(1)-O(9) 92.9(3) N(2)-Cu(2)-O(5B) O(1)-Cu(1)-O(9) 167.6(3) N(1)-Cu(2)-O(5B) O(8)-Cu(2)-O(2) 93.8(3) Complex 6 Cu(1)-O(15) 1.889(2) Cu(3)-O(16) Cu(1)-O(8A) 1.954(2) Cu(3)-N(3) Cu(1)-N(2) 2.017(2) Cu(3)-N(4) Cu(1)-N(1) 2.030(2) Cu(3)-O(12) Cu(1)-O(10) 2.422(2) Cu(4)-O(3) Cu(2)-O(15) 1.880(2) Cu(4)-O(17) Cu(2)-O(16) 1.945(2) Cu(4)-N(5) Cu(2)-O(2) 1.963(2) Cu(4)-N(6) Cu(2)-O(11) 1.972(2) Cu(4)-O(16) Cu(3)-O(1) 1.939(2) O(15)-Cu(2)-O(2) O(15)-Cu(1)-O(8A) 97.79(8) O(16)-Cu(2)-O(2) O(8A)-Cu(1)-N(2) 90.58(8) O(15)-Cu(2)-O(11) O(15)-Cu(1)-N(1) 93.18(8) O(16)-Cu(2)-O(11) N(2)-Cu(1)-N(1) 79.74(8) N(4)-Cu(3)-O(12) O(15)-Cu(1)-O(10) 84.03(8) O(16)-Cu(3)-O(12) O(8A)-Cu(1)-O(10) 107.14(7) O(3)-Cu(4)-O(17) N(2)-Cu(1)-O(10) 90.54(8) N(5)-Cu(4)-N(6) N(1)-Cu(1)-O(10) 90.46(8) O(17)-Cu(4)-N(5) N(3)-Cu(3)-N(4) 81.24(9) O(3)-Cu(4)-N(6) O(1)-Cu(3)-O(12) 92.66(8) O(3)-Cu(4)-O(16) N(3)-Cu(3)-O(12) 88.03(9) O(17)-Cu(4)-O(16) O(1)-Cu(3)-O(16) 88.42(7) N(5)-Cu(4)-O(16) O(16)-Cu(3)-N(3) 96.38(8) N(6)-Cu(4)-O(16) O(1)-Cu(3)-N(4) 93.96(8) Complex 7 Cu(1)-O(8) 1.931(2) Cu(2)-O(8D) Cu(1)-N(2) 1.999(3) Cu(2)-O(2B) Cu(1)-O(1A) 2.019(2) Cu(2)-O(3C) Cu(1)-N(1) 2.025(3) Cu(2)-O(9) Cu(1)-O(5) 2.396(3) Cu(2)-O(8) O(8)-Cu(1)-O(1A) 96.04(10) O(8D)-Cu(2)-O(3C) N(2)-Cu(1)-O(1A) 90.91(11) O(2B)-Cu(2)-O(3C) O(8)-Cu(1)-N(1) 91.71(11) O(8D)-Cu(2)-O(9) N(2)-Cu(1)-N(1) 80.95(12) O(2B)-Cu(2)-O(9) O(8)-Cu(1)-O(5) 95.59(9) O(3C)-Cu(2)-O(9) N(2)-Cu(1)-O(5) 88.73(10) O(8D)-Cu(2)-O(8) O(1A)-Cu(1)-O(5) 97.26(10) O(2B)-Cu(2)-O(8)

92.97(11) 90.69(12) 104.82(14) 120.28(13) 96.84(11) 1.939(6) 1.970(8) 2.010(7) 2.359(6) 95.7(3) 89.6(3) 80.6(3) 83.3(2) 94.0(3) 97.4(3) 98.2(3) 1.972(2) 1.979(2) 2.011(2) 2.214(2) 1.937(2) 1.979(2) 1.991(2) 2.009(2) 2.304(2) 91.50(8) 88.35(7) 96.13(8) 85.21(7) 113.25(8) 97.13(7) 89.09(8) 80.96(9) 97.24(8) 88.35(8) 88.48(7) 88.31(9) 105.54(8) 111.33(8) 1.949(2) 1.955(2) 1.958(2) 2.145(3) 2.365(2) 131.23(11) 121.65(11) 94.58(11) 94.89(12) 94.75(11) 81.98(10) 88.75(10)

a Symmetry transformations used to generate equivalent atoms for 2: A - x + 1/2, y -1/2, - z + 1/2. 3: A x, y + 1, z; B - x, - y + 1, - z + 1; C x - 1/2, - y + 3/2, z - 1/2. 4: A x - 1/2, - y + 1/2, z + 1/2; B - x + 3, - y, - z - 1; C x - 1, y, z; D x - 1, y, z + 1; E - x + 2, - y, - z. 5: A - x, - y + 1, - z + 1; B x - 1/2, - y + 2/3, z + 1/2. 6: A x - 1, y + 1, z. 7: A x + 1, y, z; B - x, - y, - z + 1; C x + 1/2, - y + 1/2, z - 1/2; D - x + 1, - y, - z + 1.

was cooled to room temperature at 5 °C/h. (yield: 34.3 mg, 39% based on Cu). Anal. Calcd for C16H20O22S2Cu4 (882.60): C, 21.77; H, 2.28%. Found: C, 21.73; H, 2.89%. IR spectrum (KBr pellet, cm-1): 3507 m, 3456 s, 3201, 1611 s, 1572 s, 1443 s, 1363, 1301 w, 1229 m, 1179 s, 1119 m, 1040 s, 997 w, 914 w, 872 w, 768 m, 730 m, 667 w, 618 s, 584 w, 470 m. [Cu2(OH)(SIP)(bpy)(H2O)]n (5). A mixture of Cu(OH)2 (19.5 mg, 0.2 mmol), NaH2SIP (26.8 mg, 0.1 mmol), bpy (15.6 mg, 0.1mmol), and water (15 mL) was heated at 120 °C for 4 days; blue prism-like crystals of 5 were obtained when the sample was cooled to room temperature at 5 °C/h. The crystals were recovered by filtering, washed with distilled water, and dried in air (yield: 15.2 mg, 28% based on Cu). Anal. Calcd for C18H14N2O9SCu2 (561.45): C, 38.51; H, 2.51; N, 4.99%. Found: C, 38.53.; H, 2.50; N, 4.96%. IR spectrum (KBr pellet,

cm-1): 3496 m, 3389 s, 3082 m, 1601 s, 1537 s, 1471 w, 1441 s, 1411 m, 1360 m, 1278 m, 1251 w, 1227 w, 1172 s, 1152 m, 1109 m, 1031 s, 945 w, 844 w, 814 m, 777 m, 753 w, 730 w, 618 s, 514 w, 467 w. [Cu4(OH)2(SIP)2(bpy)3(H2O)]n (6). A mixture of Cu(OH)2 (19.5 mg, 0.2 mmol), NaH2SIP (26.8 mg, 0.1 mmol), bpy (23.4 mg, 0.15 mmol), and water (15 mL) was heated at 120 °C for 4 days; blue rodlike crystals of 6 were obtained when the sample was cooled to room temperature at 5 °C/h. The crystals were recovered by filtering, washed with distilled water, and dried in air (yield: 14.5 mg, 23% based on Cu). Anal. Calcd for C46H34N6O17S2Cu4 (1261.07): C, 43.81; H, 2.72; N, 6.66%. Found: C, 43.75; H, 2.70; N, 6.61%. IR spectrum (KBr pellet, cm-1): 3518 m, 3411 m, 3063 m, 1601 s, 1560 s, 1443 m, 1357

Coordination of Copper(II)-5-Sulfoisophthalic Acid Scheme 1.

Chart 1.

Crystal Growth & Design, Vol. 7, No. 9, 2007 1835 Synthesis of Complexes 1-7

Versatile Coordination Modes of H3SIP Observed in Complexes 1-7

s, 1332 m, 1252 m, 1227 m, 1194 m, 1162 m, 1095 w, 1027 m, 915 w, 866 w, 768 m, 722 m, 627 m, 576 m, 471 w, 448 w, 421 w. [Cu4(OH)2(SIP)2(bpy)2(H2O)2]n (7). A mixture of Cu(OH)2 (19.5 mg, 0.2 mmol), NaH2SIP (26.8 mg, 0.1 mmol), bpy (15.6 mg, 0.1mmol), and water (15 mL) was heated at 180 °C for 4 days; blue sheetlike crystals of 7 were obtained when cooling to room temperature at 5 °C/h. The crystals were recovered by filtered, washed with distilled water, and dried in air (yield: 10.5 mg, 18% based on Cu). Anal. Calcd for C36H28N4O18S2Cu4 (1122.90): C, 38.51; H, 2.51; N, 4.99%. Found: C, 38.48.; H, 2.49; N, 4.97%. IR spectrum (KBr pellet, cm-1): 3560 m, 3483 s, 3122 s, 1603 s, 1562 s, 1455 s, 1397, 1340 w, 1233 m, 1189 s, 1106 m, 1040 s, 983 w, 912 w, 869 w, 771 m, 723 m, 671 w, 615 s, 587 w, 475 m. Crystallographic Analyses. Single X-ray diffraction data of compounds 1-7 were collected on a Rigaku Mercury CCD diffractometer equipped with a graphite-monochromated Mo-KR radiation (λ ) 0.71073 Å) by using the ω scan method at room temperature. The CrystalClear software was used for data reduction and empirical absorption correction.9 All structures were solved by the direct methods and successive Fourier difference syntheses, and refined by the fullmatrix least-squares method on F2 with anisotropic thermal parameters for all non-hydrogen atoms using SHELXS-97 and SHELXL-97 programs, respectively.10 The H atoms bonded to C atoms and N atoms were assigned to calculated positions and refined using a riding model [C-H ) 0.93 Å and Uiso(H) ) 1.2Uiso(C); N-H ) 0.89 Å and Uiso(H) ) 1.2Uiso(N)]. Hydrogen atoms bonded to O atoms were located from difference maps and refined with O-H distances restrained to 0.82 Å, and isotropic thermal parameters fixed at 1.5 times that of the respective oxygen atom. The hydrogen atoms of the disordered lattice water in compound 3 were not added. Details of the crystal parameters, data collection, and refinement are summarized in Table 1, and the selected bond lengths and bond angles are given in Table 2.

Results and Discussion Hydrothermal synthesis is widely employed to produce new materials with diverse structural architectures, but it is still a kind of “black box”. This method can minimize the problems associated with ligand solubility and enhance the reactivity of reactants in favor of efficient molecular building during the crystallization process. There are a variety of hydrothermal parameters such as reaction time, temperature, pH value, template, and molar ratio of reactants, and small changes in one or more of the parameters can have a profound influence on the final reaction outcome. Our synthetic strategy for the copper(II)-SIP coordination polymers is schematically depicted in Scheme 1. Complexes 1 and 3 were obtained under similar reaction reactions but at different pH values that were adjusted by the addition of NaOH. When pH > 7, uncharacterized, blue precipitates that are insoluble in most common solvents were obtained, indicating that the hydrothermal reaction outcome of CuCl2 and H3SIP is pH-dependent. The use of TEDA and en instead of sodium hydroxide to adjust the pH values (pH ) 6-7) leads to the formation of blue crystals of 4 and entemplated 2, respectively. Therefore, a template of appropriate size may also be incorporated in the reaction product. Ncontaining auxiliary ligands such as bpy have been widely used to fine-tune the polymeric structures of MOFs. Unfortunately, no single-crystal could be isolated from the hydrothermal reaction of CuCl2 (or Cu(NO3)2) with NaH2SIP in a mixture of water and bpy, presumably because the reactions run too fast to give an appropriate single crystal. The insoluble Cu(OH)2 is

1836 Crystal Growth & Design, Vol. 7, No. 9, 2007

Figure 1. ORTEP drawing of 1 with 40% probability displacement ellipsoids. H atoms are omitted for clarity.

thus used instead of CuCl2 to reduce the acid-base reaction rate in favor of the single-crystal growth. Expectedly, the hydrothermal reactions of Cu(OH)2 and NaH2SIP in a mixture of water and bpy yield well-formed single crystals of 5, 6, and 7. Interestingly, the reaction products are ratio- and temperaturedependent. At a ratio of Cu/SIP/bpy ) 2:1:1, the 2-D polymer 5 is formed over the temperature range 110-130 °C. At enhanced temperatures (180-200°C), the 3-D polymer 7 with (Cu4(µ3-OH)2) secondary building unit (SBU) is obtained presumably as a consequence of the dimerization of Cu2(µ2OH) in 5. An increase in the ratio of bpy in the mixture to 4:2:3 results in the 2-D polymer 6 as the additional bpy in 6 takes up the linking sites of Cu2+ and thus terminates the propagation of M/SIP/M linkages to the 3-D framework. Observations described above suggest that a suitable pH value and enhanced temperature favor the formation of high-dimensional reaction products. [Cu3(SIP)2(H2O)14] (1). The molecular structure of 1 is depicted in Figure 1 wherein the Cu(2) atom lies on a crystallographic inversion center. The three Cu2+ ions are connected as illustrated in Chart 1a and charge balanced by two SIP3- ligands through monodentate carboxylate groups forming a discrete trinuclear structure. Each Cu atom has distorted [CuO6] octahedral coordination geometry with the apical positions taken up by water molecules. The apical Cu-O distances (2.398(2) and 2.473(2) Å for Cu(1); 2.588 Å for Cu(2)) are considerably longer than the equatorial ones (1.934(1)-1.999(1) Å) that are close to the reported values reported in the related copper complexes.11 This axial elongation could be attributed to the strong Jahn-Teller distortion of copper(II) ions. The trinuclear [Cu3(SIP)2(H2O)14] units are self-interconnected into a 3-D supramolecular structure (Figure S1, Supporting information) through three types of hydrogen bonds between (a) the coordinated water molecules and carboxylate oxygen atoms, (b) the coordinated water molecules and sulfonate oxygen atoms, (c) the coordinated water molecules (Table S1,

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Supporting information). The whole framework structure is further stabilized by π-π interactions between the parallel aromatic rings in an off-set fashion with face-to-face distance of ca. 3.287(3) Å. {[Cu(SIP)(H2O)4](H2en)0.5}n (2). Compound 2 consists of the anionic [Cu(SIP)(H2O)4]- and half occupied H2en2+ guest molecule. The anionic host, [Cu(SIP)(H2O)4]-, has an infinite zigzag chain structure as shown in Figure 2. The 1-D chain is closely related to the discrete trinuclear structure of 1 (Figure 1). It obviously results from the linkage between the trinuclear units by additional bridging SIP via coordinating mode a (Chart 1), which replaces the equatorial water molecules trans to the coordinated caboxylate oxygen of the terminal Cu atoms in 1. The coordination geometry and bonding parameters of the Cu atom are thus similar to those of Cu(2) in 1. The guest en molecule obviously accounts for the formation of the infinite chain instead of the discrete structure of 1. Such 1-D chain has also been found in {[Cu(HSIP)(H2O)2](piperazine)1/2}n and {[Cu(HSIP)(H2O)3](hexamethylenetetramine)1/2}n, but the Cu atoms in these reported complexes are four- or five-coordinated.12 The 1-D chains are interconnected to form a supramolecular porous structure with elliptical channels (Figure 3) through hydrogen bonds of types (a) and (b) described above (Table S1, Supporting Information). The resulting elliptical channels of the dimension 5.6 × 9.3 Å are occupied by the guest H2en2+, which is H-bonded to the two sulfonate oxygen atoms (N‚‚‚O, 2.859(2) and 2.867(2) Å). It is also H-bonded to the apical coordinated water O10 (N‚‚‚O, 2.948(2) Å), which is absent in [Cu(H2O)2(HSIP)(piperazine)1/2], indicating that guest molecules have a significant influence on the coordination geometry of the host metal ions. The 3-D supramolecular open framework is further stabilized by the off-set π-π interactions between the parallel aromatic rings with a face-to-face distance of ca. 3.294(2) Å. {Na[Cu2(SIP)(HSIP)(H2O)8](H2O)3}n (3). Complex 3 consists of the anionic [Cu2(SIP)(HSIP)(H2O)6]- that is charge balanced by Na+ instead of H2en2+ in 2. The IR spectrum of 3 shows no absorption at 1690-1730 cm-1,13 indicating that the protonation of SIP needed for charge balance occurs at the sulfonate rather than the carboxylate groups. The asymmetric unit of 3 is illustrated in Figure 4. Differing from the case in 2, the Cu atoms in 3 have [CuO5] square pyramidal coordination geometry, presumably as a consequence of the missing H2en2+ that supports the six-coordinated Cu via N‚‚‚O hydrogen bonding. [Cu2(SIP)(HSIP)(H2O)6]- possesses a 1-D chain structure similar to that of 2, but in the former, the infinite chains are interconnected by ionic bonds between the centrosymmetric [Na2(µ2-OH2)2] dimeric unit and sulfonate groups into a 1-D tape as illustrated in Figure 5. The tape features a hexagonal 52-membered large ring with an approximate dimension of 22.7 × 14.6 Å,2 which contain four copper atoms, four sodium atoms,

Figure 2. View of the 1-D zigzag chain of 2. The H2en guest molecules and hydrogen atoms have been omitted for clarity.

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Figure 6. Schematic representation of the 2D framework formed from the 1D tapes consisting of a nanosized hexagonal-shaped heterometallacycle.

Figure 3. Three-dimensional supramolecular open framework of 2 viewed along the (1 0 0) direction displaying 1D elliptical channels filled by guest ethylenediamine molecules. The interchain hydrogen bonds are represented by dashed lines, and the hydrogen bonds between the guest molecules and the host chains are omitted for clarity.

Figure 7. ORTEP drawing of 4 with 40% probability displacement ellipsoids.

Figure 4. ORTEP drawing of 3 with 30% probability displacement ellipsoids. H atoms are omitted for clarity.

Figure 5. 1D tape structure with 52-membered heterometallacycles in complex 3 (Cu blue, Na green, O red, S yellow, C gray).

six SIP ligands, and two bridging water oxygen atoms. Although a number of hexagonal-shaped metallacycles are known in coordination polymers,14 such nanosized heterometallacycles are still scarce and unprecedented. The two tapes are interconnected by sharing water oxygen (O(11)) between Na(1) and Cu(2) into a double layer in a staggered arrangement along the diagonal of the ac plane as shown in Figures 6 and S2. The adjacent layers interact with other through extensive O-H‚‚‚O hydrogen bonds of types (a) and (b) resulting in a 3-D supramolecular

Figure 8. View of tetranuclear copper(II) atoms connected by SIP ligands to generate a 2D network parallel to the (101) plane.

structure (Table S1 and Figure S3, Supporting Information). The lattice water molecules in the cavities are hydrogen bonded with the host framework (Table S1, Supporting Information). {[Cu4(OH)2(SIP)2(H2O)2](H2O)4}n (4). Complex 4 displays a 3-D open framework structure as a consequence of the formation of the tetranuclear SBU, [Cu4(µ3-OH)2]6+. As shown in Figure 7, [Cu4(µ3-OH)2]6+has a centrosymmetric structure with four edges spanned by the four surrounding SIP carboxylate arms. The capping hydroxyl groups are slightly (0.61 Å) above

1838 Crystal Growth & Design, Vol. 7, No. 9, 2007

Figure 9. View of the 3D porous coordination polymer of 4 with 1D channels along the (1 0 1h) direction.

Figure 10. The coordination environment of (a) the tetranuclear copper units (eight-connecting node); (b) the SIP ligand (four-connecting node).

and below the Cu4 plane with the sum of the angles around O(8) of ca. 332°. The independent Cu(1) and Cu(2) atoms both have [CuO5] square pyramidal coordination geometry, but the sources of the oxygen atoms are somewhat different. The equatorial positions of Cu(1) are taken up by two bridging carboxylate oxygen atoms, one hydroxyl oxygen and one water molecule, and the apical one by the sulfonate oxygen. For Cu(2), two OH and two bridging carboxylate oxygen atoms occupy the basal positions with the apical one taken up by the sulfonate oxygen. The bond parameters of the Cu atoms are normal with longer apical distances (2.381(3) Å for Cu(2), 2.229(3) Å for Cu(1)) than the basal ones (1.914(3)-1.969(3) Å). In the Cu4 plane, the Cu(2)‚‚‚Cu(2D) separation of 2.940(1) Å are considerably shorter than the four edges (Cu(1)‚‚‚Cu(2), 3.29(7), Cu(1)‚‚‚Cu(2D), 3.40(4) Å). Similar planar [Cu4(µ3-OH)2]6+ SBUs but with C2 symmetry have been observed in [Cu4(OH)2-

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(SIP)2(bipy)2‚2H2O]n and [Cu4(OH)2(SIP)2(py)2‚4H2O]n (bipy ) 4,4-bipyridine, py ) pyridine),15 which are constructed from mixed ligands. Figure 8 shows how the Cu4 SBUs are interconnected by SIP into a 2-D structure. Each SIP uses all carboxylate oxygen atoms and one sulfonate oxygen to coordinate to the three neighboring Cu4 SBUs in coordination mode c (Chart 1) (the additional sulfonate oxygen is involved in 3-D linkage to be described later), resulting in a 16-membered ring A (6.9 × 5.1 Å) and ring B (3.7 × 8.8 Å). The sixth donor atom from the sulfonate group functions as a linker between the sheets to afford a 3-D open framework as depicted in Figure 9 with the interlamellar separation of ca. 10 Å. The 3-D structure features 1-D channels along the (1 0 1h) direction with a dimension of 8.6 × 7.3 Å, which accounts for 11.8% of the crystal volume estimated by the PLATON program.16 These lattice water molecules in the channels are H-bonded with the host framework with the O‚‚‚O separations ranging from 2.750(6) to 3.047(5) Å (Table S1, Supporting Information). A better insight into the nature of this intricate framework can be achieved by the application of a topological approach, i.e., reducing multidimensional structures to simple node and connection nets. As depicted in Figure 10a, each [Cu4(µ3-OH)2] SBU is coordinated by 12 oxygen atoms from eight SIP ligands. Thus, the Cu4 SBU defines an eight-connected node. Likewise, SIP serves as a four-connected node to bridge four Cu4 SBUs (Figure 10b). Therefore, the structure of 4 consists of four- and eight-connected nodes. As we know, it is usually believed that the four- and eight-connectivities would favor falling into the fluorite (CaF2) structure of (412‚612‚84)(46)2 topology (see Figure S4, Supporting Information). However, structure 4 adopts an uncommon (411‚614‚83)(45‚6)2 topology (the first symbol for Cu4 SBU and the second for SIP). To the best of our knowledge, this topology has not been reported in coordination polymer chemistry, and the finding of this unprecedented topology is useful at the basic level in the crystal engineering of coordination networks. Note that the coordination networks of high connectivity (>6) are extremely rare because of steric constrains,17 especially for the fluorite topology, which require an eightcoordinated metal (or metal cluster) center and a tetrahedral fourconnected ligand. Hitherto, only one example of a metalorganic replica of fluorite is reported.18 Interestingly, the present net topology with eight-connected SBUs and tetrahedral fourconnected ligand is different from that of fluorite (412‚612‚84)(46)2 but related to it. If we have a careful look at the two nodes of the 3-D network of 4, their similarity and differences become apparent. First, unlike fluorite in which there are six fourmembered shortest circuits around each four-connected node, the present four-connected node is surrounded by one sixmembered and three four-membered circuits (Figure 11a). Second, the number of four- and eight-membered circuits around the eight-connected node decreases with the increase of the sixmembered rings (Figure 11b). Finally, the eight four-connected nodes surrounding the central eight-connected node form two planes with a dihedral angle of 73.6° (Figure 11c), instead of 90° in fluorite. As a result of these essential differences, the topology of the material changes (412‚612‚84)(46)2 to (411‚614‚ 83)(45‚6)2 topology (Figure 11d). [Cu2(OH)(SIP)(bpy)(H2O)]n (5). Complex 5 has an undulating 2-D double-sided layered structure constructed from the [Cu2(µ2-OH)]3+ SBUs and SIP ligands. The numbering scheme of 5 is given in Figure 12. It is unusual that, differing from the cases in 1-4 as well as 6 and 7 to be described later, the coordination geometry of the two independent Cu atoms are distinct. Cu(1) has [CuO4] square coordination geometry with

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Figure 11. (a and b) A convenient view of the vertices for both kinds of nodes (the linkers highlighted with green color). (c) Schematic view of the neighboring eight four-connected nodes of the central eight-connected node to form two intersectant planes (The two planes are twisted together with a dihedral angle of 73.6° in 4). (d) Schematic view of the (411‚614‚83)(45‚6)2 topology of the 3D network of 4. (The tetranuclear copper unit is represented by blue balls and the SIP ligand is represented by red balls.)

Figure 12. ORTEP drawing of 5 with 40% probability displacement ellipsoids.

four oxygen atoms from two carboxylate oxygen atoms of two different SIP ligands, one water molecule and one hydroxyl oxygen. Cu(2) possesses [CuO5] square pyramidal geometry with the equatorial sites taken up by the hydroxyl, one carboxylate oxygen and two bpy nitrogen atoms and apical one by the sulfonate oxygen. The Cu(1)-O distances (1.929(6)1.995(7) Å) are comparable to the Cu(2)-O one (1.939(6) Å). The Cu(2)-O(8) bond (1.878(6) Å) trans to the Cu(2)N(1)(2.010(7) Å) is significantly shorter than Cu(1)-O(8) (1.932(6) Å) as a result of the trans effect. As depicted in Figure 13, the [Cu2(µ2-OH)]3+ SBUs are linked together by the tetradentate SIP in mode d (Chart 1) to generate a 2D layered structure. The layered structure features the crown-like 16membered ring B (5.1 × 5.6 Å) and the 36-membered ring C

Figure 13. View of the 4‚82 nets and three types of rings in 5 with the bpy ligands, coordinated water molecules, and hydrogen atoms omitted for clarity.

(15.3 × 9.9 Å). Thus, the 2-D structure can be regarded as having 4‚82 topology (Figure 13 and S5).19 Forming such a cyclic structure with metal ions is an important feature of the SIP ligand.8,20 Types (a) and (b) hydrogen bonds are found within the layered structure (Table S1, Supporting Information).

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Figure 16. Schematic view of 2-D network of (3‚52)2(32‚53) topology in 6 (Tetranuclear copper unit is represented by blue balls and the SIP ligand is represented by red balls.) Figure 14. ORTEP drawing of 6 with 30% probability displacement ellipsoids. H atoms are omitted for clarity.

Figure 15. View of tetranuclear copper clusters connected by SIP ligands to generate a 2D layer structure (bpy and coordination water molecules are omitted for clarity).

It is worth noting that the hydroxyl group O(8) is hydrogen bonded to the uncoordinated sulfonate oxygen O(6) (O‚‚‚O, 2.819(8) Å) from the adjacent layer to afford a 3D supramolecular framework as illustrated in Figure S6 (Supporting Information). [Cu4(OH)2(SIP)2(bpy)3(H2O)]n (6). Figure 14 shows the unprecedented Y-shaped [Cu4(µ3-OH)(µ2-OH)] SBU, wherein one µ2-OH and one µ3-OH instead of two µ3-OH in 4 and 7 link the four Cu2+ ions together. The four copper atoms are almost coplanar with a maximum deviation of 0.148 Å. However, as shown in Figure 15, one more bpy ligand leads to the formation of a 2-D instead of a 3-D structure in 7. The [Cu4(µ3-OH)(µ2-OH)] has no symmetry with all copper(II) ions crystallographically independent. Three of the Cu atoms (Cu(1), Cu(3), and Cu(4)) each chelated by an equatorial bpy ligand have a square pyramidal geometry, whereas the central copper atom (Cu(2)) bears a square coordination environment. Differing from the case in 4, only two of the three Cu‚‚‚Cu edges are spanned by the SIP carboxylate groups. Bond lengths of the

Cu atoms appear as expected for the long apical and shorter basal distances as well as the trans effect as mentioned above except for the unusually short Cu(2)-(µ2-OH) bond (1.880(2) Å) that is comparable to the Cu(1)-(µ2-OH) bond (1.889(2) Å). Two types of SIP ligands with the coordinating modes d and e (Chart 1), respectively, connect the tetranuclear [Cu4(µ3OH)(µ2-OH)] units into a 2-D layered structure (Figure 15). The three bpy ligands take up both the connecting sites and spaces and thus disfavor further linkage into a 3-D framework. As shown in Figure 15, each SIP ligand of mode d (Chart 1) acts as a three-connected node to bridge three neighboring [Cu4(µ3OH)(µ2-OH)] SBUs. Each [Cu4(µ3-OH)(µ2-OH)] SBU is linked to three SIP ligands of mode d (Chart 1) and two other tetranuclear copper SBUs via two SIP ligands of mode e (Chart 1). This gives a 2-D 3,5-connected network containing threeand five-membered rings with a novel (3‚52)2(32‚53) topology, as shown in Figure 16. [Cu4(OH)2(SIP)2(bpy)2(H2O)2]n (7). 7 contains the chairlike [Cu4(µ3-OH)2] SBU (Figure 17) instead of the Y-like [Cu4(µ3OH)(µ2-OH)] observed in 6 as a consequence of one less bpy in the present compound. The [Cu4(µ3-OH)2] can be viewed as resulting from the dimerization of [Cu2(µ2-OH)] of 5 at enhanced temperature. Unlike the case in 4 without bpy ligands, only two of the four Cu‚‚‚Cu edges are spanned by the SIP ligands. The two independent Cu atoms in the centrosymmetric [Cu4(µ3OH)2] SBU both have a square pyramidal coordination geometry. One Cu atom (Cu(1)) is chelated by an equatorial bpy ligand, but unlike the cases in 5 and 6, no obvious trans effect of the Cu-N bonds has been observed (Cu(1)-O(8), 1.931(2); Cu(1)-O(1A), 2.019(2) Å). The Cu4 SBUs are interconnected by SIP ligands of coordination mode d (Chart 1) into a 3-D framework as depicted in Figure 18 with the bpy and coordination water molecules inside the cavities. The 3-D structure may be more clearly understandable on the basis of a topological approach. As depicted in Figure 19a, each Cu4 SBU is coordinated by six SIP ligands and each SIP ligand links three Cu4 SBUs together (Figure 19b). Thus, they serve as sixconnected and three-connected nodes, respectively. The resulting structure can be viewed as derived from a rutile structure of (4‚62)2(42‚610‚83) topology wherein each Ti atom is coordinated to six O atoms and each O atom is bound to three Ti atoms (Figure S7, Supporting Information).21 However, this structure is a deformed version of the idealized rutile structure. As can be seen, in the square-like channel the adjacent sides are

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Crystal Growth & Design, Vol. 7, No. 9, 2007 1841

Figure 17. ORTEP drawing of 7 with 30% probability displacement ellipsoids. H atoms are omitted for clarity.

Figure 18. The tetranuclear copper clusters connected by SIP ligands to form a 3D open framework along the (0 1 0) direction (bpy and water molecules are omitted for clarity).

mutually inclined at an angle of ca. 67.5° rather than perpendicular as shown in the rutile prototype (TiO2). Infrared Spectrum and Powder X-ray Diffraction. The FTIR spectra of these complexes exhibit characteristic bands of the asymmetric stretching vibrations of the carboxylate groups between 1515 and 1675 cm-1, and the symmetric stretching vibrations at 1410-1475 cm-1. The absorptions in the region 1000-1230 cm-1 for all complexes are typical for sulfonate groups. The strong absorptions for all complexes around 618 cm-1 can be assigned to the S-O stretching vibrations.22 The broad bands in the range 3200-3560 cm-1 for all complexes correspond to the O-H stretching vibrations of water and/or hydroxyl group. The purities and crystallinities of the bulk samples were checked by powder X-ray diffraction (PXRD) using a RIGAKU DMAX2500PC diffractometer. The PXRD patterns of compounds 1-4 are illustrated in Figure S8, Supporting Information.

Figure 19. (a) Coordination environment of the tetranuclear copper units; (b) the three-connecting SIP ligand; (c) schematic view of the deformed rutile topology of structure 7 (Tetranuclear copper unit are represented by blue balls and the SIP ligand is represented by red balls.)

The different structures of compounds 1-4 also have been indicated by their different XRPD patterns. Their XRPD patterns in good agreement with the ones simulated from single-crystal structural data; thus, compounds 1-4 were obtained as a single phase. Magnetic Properties. The magnetic susceptibilities of complexes 1-5 were recorded at 5-300 K. The plots of χMT versus T of 1-5 are shown in Figure 20. The magnetic susceptibility data of 1-5 between 300 and 5 K obey the Curie-Weiss law, χM ) C/(T - θ), with Curie constant C and Weiss constant θ listed in Table 3. The small Weiss constants in these complexes indicate the weak magnetic interactions between the Cu(II) centers. The plots of χM (and χMT) versus T for 1-5 are given in Supporting Information (Figures S9-S13). The susceptibility

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Liu et al.

coordinating modes may act singly in 1, 2, 4, 5, and 7 or in concert with each other in 3 and 6. The magnetic interactions between Cu2+ bridged by OH- or SIP ligands have been found to be weak, either ferromagnetically or antiferromagnetically. Acknowledgment. We gratefully acknowledge the financial support of 973 program (Grant No. 2006CB932900) and National Science Foundation of China (Grant No. 20473092). Supporting Information Available: X-ray crystallographic files in CIF format, table of hydrogen bonds, hydrogen-bonded supromolecular structures, X-ray powder diffraction patterns of compounds 1-5. The fitting results of the magnetic data of complexes 1-5. This material is available free of charge via the Internet at http://pubs.acs.org.

References

Figure 20. Plots of χMT versus T for complexes 1-5. Table 3. Fitting Parameters Obtained for Complexes 1-5 compd

C (emu·K/mol)

θ (K)

J (cm-1)

1 2 3 4

1.12 0.41 0.99 1.54

0.54 -3.77 0.21 -1.55

5

0.88

1.78

0.35 -0.47 0.67 -0.63 -2.18 0.21

g

2zJ′ (cm-1)

R

2.04 2.02 2.26 1.98

-0.046 0.02 - 0.07 - 0.02

4 × 10-5 9 × 10-5 7.2 × 10-4 1.2 × 10-3

2.10

0.10

6.6 × 10-4

data of 1-5 have been modeled with the isotropic spinHamiltonian (see Supporting Information). The detailed fitting formulas and parameters are provided as supporting materials, and the calculated results are listed in Table 3. The calculated coupling constants J are qualitatively in agreement with the Weiss constant θ, although their values are slightly different. These results show that the magnetic coupling between the Cu atoms in these compounds through either SIP or a hydroxyl bridge is quite weak. The exchange coupling in the carboxylatobridged Cu2 moiety has been extensively studied, which is largely determined by the number of bridging carboxylate groups.23 The coupling constant of -2.18 cm-1 between Cu(1) and Cu(2) (Cu‚‚‚Cu, 3.29 Å) in 4 reveals a weak antiferromagnetic interaction, comparable with the value (-2.4 cm-1) observed in [meTACNCl2Cu2(µ-benzento)]+.24 The interaction between Cu(1) and Cu(2) is contributed mainly through the SIP carboxylato bridge because the coupling constant (0.63 cm-1) between Cu(2) and Cu(2D) via two hydroxyl bridges is even much smaller despite the shorter Cu‚‚‚Cu separation (2.940(1) Å). In 5 with the [Cu2(µ2-OH)(µ-SIP)] unit (Cu‚‚‚Cu, 3.082(1) Å), the interaction between the two Cu atoms are weakly ferromagnetic with the coupling constant (0.21 cm-1) within the calculated range (0-1.4 cm-1).24a Conclusion A series of seven coordination complexes of from discrete to 3-D structure were prepared from the Cu-SIP system. With a comparison to conventional solution synthesis, the hydrothermal reactions employed in this work favor the formation of the polynuclear copper SBUs of high connectivity and thus more diverse structural architectures in the Cu-SIP system. Appropriate starting materials and templates, a high pH value, and an enhanced reaction temperature favor the formation of polynuclear SBUs in the present case, which dominate the formation of the coordination polymers of high dimensionality. Diversified structural topologies of the Cu-SIP system are devoted to the varied coordination geometry of Cu and the multiple coordinating modes of SIP as illustrated in Chart 1a-e wherein modes d and e have never been reported before. These

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CG070407G