From Dicarboxylic Acid to Tetranuclear Metallamacrocyclic Complex

From Dicarboxylic Acid to Tetranuclear Metallamacrocyclic Complex and 1D and 2D Polymers Yongli Wei, Hongwei Hou,* Linke Li, Yaoting Fan, and Yu Zhu Department of Chemistry, Zhengzhou University, Henan 450052, P. R. China Received November 30, 2004;

CRYSTAL GROWTH & DESIGN 2005 VOL. 5, NO. 4 1405-1413

Revised Manuscript Received March 16, 2005

ABSTRACT: A series of metal carboxylate complexes have been synthesized by treating 2,6-dicarboxamido-(2pyridyl)-pyridine (H2dcapp), pyridine-2,5-dicarboxylate acid (2,5-H2pda), and phenanthroline (phen) with metal salts under hydrothermal conditions. Carboxylate groups as building blocks are used to link adjacent metal centers forming a one-dimensional (1D) coordination polymeric chain [Mn2(2,6-pda)2(H2O)3]∞ (1) (2,6-pda ) pyridine-2,6-dicarboxylate), a two-dimensional (2D) sheet network [Pb(2,6-pda)]∞ (2), a 2D hybrid rhombic grid coordination polymer [Cd(phen)(2,5-pda)]∞ (3), a 1D hybrid zigzag chain {[Zn(phen)(2,5-pda)]‚H2O}∞ (4), and a tetranuclear metallamacrocyclic complex {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 (5). Their thermal properties were studied through TG-DT analyses. The magnetic measurement of polymer 1 reveals that typical antiferromagnetic exchange exists between Mn centers with J ) -0.215 cm-1. Introduction The chemistry of novel metal-organic hybrid coordination polymers has been the subject of intensive research in recent years1-5 due to their interesting topologies and unexpected properties for potential applications.6-9 Recent advances in this field have led to many ordered coordination networks formed through the deliberate selection of functionalized organic ligands and coordination geometries of transition metal ions.10-13 Many of them are regarded as promising materials for applications in catalysis, separation, gas storage, and molecular recognition.14-19 A successful strategy in building such networks is to employ appropriate bridging ligands that can bind metal ions in different modes and provide a possible way to achieve more robust polymeric structures.20 Many multidentate ligands containing N- or O-donors, such as N,N′-disubstituted oxamidate derivatives,21 2,2′-bipyridyl-4,4′-dicarboxylic acid,14 3,4-toluenediamine-N,N,N′,N′-tetraacetate, and 4-chloro-1,2-phenylenediamine-N,N,N′,N′tetraacetate,22 have been used in the literature. The carboxylate groups are widely used as building blocks too because they exhibit diverse coordination modes, such as monodentate terminal and monodentate bridging, bidentate chelating, and bidentate bridging.14 The different coordination modes of carboxylate groups enhance the robustness of the resulting architectures. On the other hand, the negative charge of carboxylate groups compensates the positive charge induced by the metal centers and can mitigate the counterion effect.14 Furthermore, the flexibility of carboxylate groups is always efficient to form fascinating topologies. Besides supramolecular contacts, hydrogen bonding or π-π stacking interactions further make the whole framework more stable.23-25 The above-mentioned advantages of carboxylate groups are frequently employed in the design, syntheses, and crystallization of coordination frameworks. Although * To whom correspondence should be addressed. E-mail: [email protected]. Phone: +86-371-7761744. Fax: +86-3717761744.

“self-assembly” has offered an efficient solution that may be addressed or controlled, it is still limited to a certain extent. The challenge associated with the synthesis is still the generation of high-quality crystalline materials. For a long time, the hydrothermal method has been extensively employed to generate solid-state oxides.26,27 Until recently, it is employed to prepare coordination polymers. With the hydrothermal idea in mind, we reacted pyridyl-dicarboxylate acid (H2pda) with metal ions and employed phen as an auxiliary ligand to prevent H2O from coordinating with metal ions. In this paper, we describe the synthesis of four novel polymers [Mn2(2,6-pda)2(H2O)3]∞ (1), [Pb(2,6-pda)]∞ (2), [Cd(phen)(2,5-pda)]∞ (3), and {[Zn(phen)(2,5-pda)]‚H2O}∞ (4) and a tetranuclear metallamacrocyclic complex {[Zn(2,5pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 (5) by the hydrothermal method, report the structural characterization and thermal stabilities of these compounds, and describe in detail the magnetic properties of polymer 1.

Experimental Section All chemicals were of A. R. grade and obtained commercially without further purification. The infrared spectrum was recorded on a BRUKER TENSOR 27 spectrometer using KBr pellets in 400-4000 cm-1. A PE 240C Elemental analyzer was used to perform elemental analysis. Fast atom bombardment (FAB) mass spectra were obtained on a Bruker Esquire 3000 mass spec-

10.1021/cg049596i CCC: $30.25 © 2005 American Chemical Society Published on Web 04/27/2005

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Table 1. Crystal Data and Structure Refinement for Complexes 1-5 polymer 1 identification code empirical formula formula weight temp (K) wavelength (Å) crystal system, space group unit cell dimensions

volume (Å3) calculated density (Mg/m3) absorption coefficient ( mm-1) F(000) index ranges reflections collected/unique refinement method data/restraints/ parameters final R indices [I > 2σ(I)] largest diff peak and hole

polymer 2

polymer 3

polymer 4

complex 5

P1 h C14H10Mn2N2O11 492.12 291(2) 0.71073 triclinic, P1 h

P21/n C7H3NO4Pb 372.29 291(2) 0.71073 monoclinic, P21/n

C2/C C19H11CdN3O4 457.71 291(2) 0.71073 monoclinic, C2/C

P21/c C19H13N3O5Zn 428.69 291(2) 0.71073 monoclinic, P21/c

P1 h C14H11N2O13Zn2 545.99 293(2) K 0.71073 triclinic, P1 h

a ) 8.2277(16) Å b ) 13.182(3) Å c ) 8.2269(16) Å R ) 94.89(3)° β ) 107.19(3)° γ ) 85.08(3)° 847.6(3) 1.928

a ) 9.834(2) Å b ) 5.5508(11) Å c ) 14.372(3) Å R ) 90° β ) 104.91(3)° γ ) 90° 758.1(3) 3.262

a ) 21.488(4) Å b ) 10.875(2) Å c ) 16.501(3) Å R ) 90° β ) 115.83(3)° γ ) 90° 3470.5(12) 1.752

a ) 12.710(3) Å b ) 10.176(2) Å c ) 13.658(3) Å R ) 90° β ) 107.15(3)° γ ) 90° 1687.9(6) 1.687

a ) 7.1084(14) Å b ) 11.495(2) Å c ) 11.910(4) Å R ) 107.28(3)° β ) 104.18(3)° γ ) 90.19(3)° 897.9(3) 2.019

1.558

22.231

1.290

1.495

2.751

492 0 e h e 10, -16 e k e 16, -10 e l e 10 2911/2911 [R(int) ) 0.0000] full-matrix least-squares on F2 2911/0/279


1808 -27 e h e 12, -12 e k e 13, -19 e l e 21 6272/3647 [R(int) ) 0.0284] full-matrix least-squares on F2 3647/0/245


546 -8 e h e 8, 0 e k e 13, -14 e l e 13 2629/2629 [R(int) ) 0.0000] full-matrix least-squares on F2 2629/0/281

R1 ) 0.0536, wR2 ) 0.1283 1.055 and -0.744 e Å-3

R1 ) 0.0454, wR2 ) 0.1003 2.707 and -3.214 e Å-3

R1 ) 0.0313, wR2 ) 0.0662 0.665 and -1.027 e Å-3

R1 ) 0.0411, wR2 ) 0.0839 0.361 and -0.493 e Å-3

R1 ) 0.0812, wR2 ) 0.2194 1.690 and -1.058 e. Å-3

trometer. NMR spectra were obtained using a Bruker DPX400 spectrometer. A Perkin-Elmer TGA 7 analyzer was used to carry out the thermogravimetric (TG) analysis under nitrogen at a heating rate of 10 °C/min for all measurements. The DT analysis was investigated on Perkin-Elmer DTA 7 analyzer. The field-cooled magnetic susceptibility of crystal sample was measured using a Quantum Design MPMS SQUID magnetometer. Data were collected in the range 5-300 K in an applied field of 500G. Synthesis of 2,6-Dicarboxamido-(2-pyridyl)-pyridine (H2dcapp). 2,6-Pyridyldicarboxylic acid (1.67 g, 10 mmol) was directly dissolved in 20 mL of SOCl2 in a three-necked roundbottom flask (100 mL) with constant stirring at room temperature. The resultant pale-yellow solution was refluxed for 2 h. Yellow powder could be obtained after distilling off the solvent in a vacuum at room temperature. Then we dissolved the yellow powder in 10 mL of py. A solution of 2-aminopyridine (1.90 g, 20 mmol) in 15 mL of py was added to the above py solution under stirring in an ice bath. The color of the solution changed to brown red, and a pale brown powder precipitated. After filtering of the sample, the precipitate was recrystallized from 20 mL of H2O to yield H2dcapp as paleyellow crystals. The dried production weights: 4.21 g (yielding 70%). Anal. Cald. for C17H13N5O2: C, 63.95; H, 4.08; N, 21.94. Found: C, 63.14; H, 4.51; N, 21.81. 1H NMR (400 MHz, DMSO): δ ) 7.25 (q, 2H), δ ) 7.93 (h, 2H), δ ) 8.31 (h, 3H), δ ) 8.41 (d, 2H), δ ) 8.50 (d, 2H). Positive-ion, ESI-MS: m/z: 319.9 [pdcap + H-]. Synthesis of [Mn2(2,6-pda)2(H2O)3]∞ (1). A mixture of MnSO4 (30.2 mg, 0.2 mmol), H2dcapp (32.1 mg, 0.1 mmol), and water (6 mL) in a Teflon-lined stainless steel vessel was heated at 180 °C for 24 h. Colorless prismatic crystals were isolated with a yield of 30% (15 mg) based on MnSO4. Anal. Cald. for C14H10Mn2N2O11 (%): C, 34.14; H, 2.03; N, 5.69. Found: C, 33.90; H, 2.05; N, 5.88. IR(KBr, cm-1): 3363(m), 1632(m), 1593(s), 1441(m), 1396(m), 1376(m), 722(m). Synthesis of [Pb(2,6-pda)]∞ (2). In a Teflon-lined stainless steel vessel an aqueous solution (6 mL) containing Pb(Ac)2‚ 3H2O (76 mg, 0.2 mmol) and H2dcapp (32.1 mg, 0.1 mmol) was

heated at 180 °C for 24 h, from which colorless columnar crystals were produced in a total yield of 70% (28 mg) based on Pb(Ac)2‚3H2O. Anal. Cald. for C7H3NO4Pb (%): C, 22.56; H, 0.81; N, 3.76. Found: C, 22.98; H, 1.01; N, 3.88. IR(KBr, cm-1): 3447(m), 1612(s), 1426(s), 1384(s), 1273(w), 1019(w), 914(w), 768(w), 729(m), 664(w), 423(w). Synthesis of [Cd(phen)(2,5-pda)]∞ (3). A mixture of Cd(Ac)2‚2H2O (26.8 mg, 0.1 mmol), phen (18.2 mg, 0.1 mmol), 2,5-H2pda (16.7 mg, 0.1 mmol), and water (6 mL) in a 20 mL Teflon-lined stainless steel vessel was heated at 160 °C for 36 h. After the sample was cooled to room temperature naturally, colorless block crystals were obtained in 90% yield (40 mg) based on Cd(Ac)2‚2H2O. Anal. Cald. for C19H11CdN3O4 (%): C, 49.81; H, 2.40; N, 9.18. Found: C, 49.50; H, 2.75; N, 9.45. IR(KBr, cm-1): 3424(m), 1619(s), 1387(s), 1359(s), 1515(m), 847(m), 825(m), 768(m), 727(m). Synthesis of {[Zn(phen)(2,5-pda)]‚H2O}∞ (4). An aqueous mixture (6 mL) containing Zn(Ac)2‚2H2O (21.9 mg, 0.1 mmol), phen (18.2 mg, 0.1 mmol), and 2,5-H2pda (16.7 mg, 0.1 mmol) was placed in a Teflon-lined stainless steel vessel (20 mL), and heated at 160 °C for 36 h, followed by slow cooling to room temperature. Colorless crystals of polymer 4 were separated suitable for X-ray diffraction. (Yield: 90%, 37 mg). Anal. Cald. for C19H13N3O5Zn (%): C, 53.19; H, 3.03; N, 9.80. Found: C, 53.44; H, 2.93; N, 9.36. IR(KBr, cm-1): 3473(m), 1645(s), 1610(s), 1425(m), 1354(s), 848(m), 767(m), 727(m), 528(w). Synthesis of {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 (5). A mixture of Zn(Ac)2‚2H2O (21.9 mg, 0.1 mmol), 2,5-H2pda (16.7 mg, 0.1 mmol), and water (6 mL) in a 20 mL Teflonlined stainless steel container was heated at 160 °C for 60 h. After cooling of the sample to room temperature, colorless needle crystals were collected in yield of 20% (6 mg) based on Zn(Ac)2‚3H2O. Anal. Cald. for C14H11N2O13Zn2 (%): C, 30.77; H, 2.01; N, 5.13. Found: C, 30.25; H, 2.46; N, 4.82. IR(KBr, cm-1): 3410(m), 1040(w), 827(w), 761(w), 543(w). X-ray Crystallographic Analysis. All diffraction data were collected using a Rigaku R-AXIS-IV diffractometer (MoKR radiation, graphite monochromator, λ ) 0.71073 Å). Data were corrected for Lorentz and polarization effects, and

Dicarboxylic Acid to Tetranuclear Metallamacrocyclic Complex

Crystal Growth & Design, Vol. 5, No. 4, 2005 1407

Table 2. Selected Bond Lengths (Å) and Angles (deg) for Complexes 1-5 Polymer 1a Mn(1)-O(11) Mn(1)-O(3) Mn(1)-O(5)#1 Mn(1)-O(5) Mn(1)-O(10) Mn(1)-N(1) Mn(1)-O(1) Mn(2)-O(9) O(11)-Mn(1)-O(3) O(11)-Mn(1)-O(5)#1 O(3)-Mn(1)-O(5)#1 O(3)-Mn(1)-O(5) O(5)#1-Mn(1)-O(5) O(11)-Mn(1)-O(10) O(3)-Mn(1)-O(10) O(5)#1-Mn(1)-O(10) O(5)-Mn(1)-O(10) O(11)-Mn(1)-N(1) O(9)-Mn(2)-O(1) O(9)-Mn(2)-O(7)#2 Polymer 2b Pb(1)-O(4) Pb(1)-N(1) Pb(1)-O(2)#1 Pb(1)-O(2) O(4)-Pb(1)-N(1) O(4)-Pb(1)-O(2)#1 N(1)-Pb(1)-O(2)#1 O(4)-Pb(1)-O(2) N(1)-Pb(1)-O(2) C(1)-O(2)-Pb(1)#2 C(1)-O(2)-Pb(1) Polymer 3c Cd(1)-O(2)#1 Cd(1)-O(3)#2 Cd(1)-O(3) Cd(1)-N(1) Cd(1)-N(2) Cd(1)-N(3) O(2)#1-Cd(1)-O(3)#2 O(2)#1-Cd(1)-O(3) O(3)#2-Cd(1)-O(3) O(2)#1-Cd(1)-N(1) O(3)#2-Cd(1)-N(1)

2.127(4) 2.185(4) 2.262(3) 2.268(3) 2.287(4) 2.300(4) 2.499(4) 2.127(4) 163.85(17) 89.04(17) 100.74(14) 87.76(14) 70.69(14) 91.79(17) 73.79(14) 154.13(13) 83.72(13) 104.71(18) 163.81(17) 88.85(17)

Mn(2)-O(1) Mn(2)-O(7)#2 Mn(2)-O(7) Mn(2)-O(10) Mn(2)-N(2) Mn(2)-O(3) O(5)-Mn(1)#1 O(7)-Mn(2)#2 O(9)-Mn(2)-O(7) O(1)-Mn(2)-O(7) O(9)-Mn(2)-O(10) O(1)-Mn(2)-O(10) O(7)#2-Mn(2)-O(10) O(7)-Mn(2)-O(10) O(9)-Mn(2)-N(2) O(1)-Mn(2)-N(2) Mn(2)-O(1)-Mn(1) Mn(1)-O(3)-Mn(2) Mn(1)#1-O(5)-Mn(1) Mn(2)#2-O(7)-Mn(2)

2.397(6) 2.492(8) 2.512(6) 2.641(6) 66.5(2) 80.4(2) 73.0(2) 128.9(2) 63.2(2) 96.5(5) 119.7(6)

Pb(1)-O(1) O(1)-C(1)#1 O(2)-C(1) O(2)-Pb(1)#2 O(2)#1-Pb(1)-O(2) O(4)-Pb(1)-O(1) N(1)-Pb(1)-O(1) O(2)#1-Pb(1)-O(1) O(2)-Pb(1)-O(1) C(1)#1-O(1)-Pb(1) Pb(1)#2-O(2)-Pb(1)

2.231(2) 2.2408(19) 2.343(2) 2.352(2) 2.380(2) 2.398(2) 104.34(9) 96.93(9) 69.65(8) 92.79(9) 124.98(8)

O(2)-Cd(1)#3 O(3)-Cd(1)#2 N(1)-C(5) N(2)-C(10) N(2)-C(6) N(3)-C(14) O(2)#1-Cd(1)-N(3) O(3)#2-Cd(1)-N(3) O(3)-Cd(1)-N(3) N(1)-Cd(1)-N(3) N(2)-Cd(1)-N(3)

O(3)-Cd(1)-N(1) O(2)#1-Cd(1)-N(2) O(3)#2-Cd(1)-N(2) O(3)-Cd(1)-N(2) N(1)-Cd(1)-N(2) Polymer 4d Zn(1)-O(1) Zn(1)-N(3) Zn(1)-O(4)#1 Zn(1)-N(2) Zn(1)-N(1) Zn(1)-O(3)#1 Zn(1)-C(19)#1 O(1)-Zn(1)-N(3) O(1)-Zn(1)-O(4)#1 N(3)-Zn(1)-O(4)#1 O(1)-Zn(1)-N(2) N(3)-Zn(1)-N(2) O(4)#1-Zn(1)-N(2) N(2)-Zn(1)-O(3)#1 C(5)-N(1)-Zn(1) C(10)-N(2)-C(6) 2.705(8) C(10)-N(2)-Zn(1) 1.249(12) Complex 5e 1.285(13) Zn(1)-O(8)#1 2.512(6) Zn(1)-O(10) 77.33(14) Zn(1)-O(1) 81.8(2) Zn(1)-O(11) 119.1(2) Zn(1)-O(9) 50.6(2) O(8)-Zn(1)#1 115.4(2) O(8)#1-Zn(1)-O(10 88.4(7) O(8)#1-Zn(1)-O(1) 142.6(3) O(10)-Zn(1)-O(1) O(8)#1-Zn(1)-O(11) 2.231(2) O(10)-Zn(1)-O(11) 2.2408(19) O(1)-Zn(1)-O(11) 1.357(4) O(8)#1-Zn(1)-O(9) 1.331(4) O(10)-Zn(1)-O(9) 1.348(4) O(1)-Zn(1)-O(9) 1.340(3) O(11)-Zn(1)-O(9) 88.85(9) O(8)#1-Zn(1)-N(1) 136.95(7) O(10)-Zn(1)-N(1) 68.15(7) O(1)-Zn(1)-N(1) 94.30(8) O(3)-Cd(1)-N(1) 91.38(9) O(2)#1-Cd(1)-N(2)

2.188(4) 2.265(4) 2.274(3) 2.285(4) 2.298(4) 2.500(4) 2.262(3) 2.265(4) 83.28(17) 87.72(14) 91.85(17) 73.73(14) 153.99(13) 83.50(13) 104.74(18) 90.77(15) 91.26(13) 91.29(13) 109.31(14) 109.24(14)

159.64(8) 163.39(9) 86.71(8) 98.57(8) 70.63(8)

C(13)-O(2)-Cd(1)#3 C(19)-O(3)-Cd(1)#2 C(19)-O(3)-Cd(1) Cd(1)#2-O(3)-Cd(1)

117.3(2) 127.47(17) 121.72(17) 110.35(8)

2.052(3) 2.120(3) 2.124(3) 2.151(3) 2.159(3) 2.322(3) 2.539(4) 79.03(10) 103.05(12) 97.85(11) 90.63(11) 164.80(10) 95.30(11) 103.52(11) 113.1(2) 118.1(3) 128.3(3)

N(1)-C(1) O(1)-C(13) O(2)-C(13) O(3)-C(19) O(3)-Zn(1)#2 O(4)-C(19) O(4)-Zn(1)#2 O(1)-Zn(1)-N(1) N(3)-Zn(1)-N(1) O(4)#1-Zn(1)-N(1) N(2)-Zn(1)-N(1) O(1)-Zn(1)-O(3)#1 N(3)-Zn(1)-O(3)#1 O(4)#1-Zn(1)-O(3)#1 N(1)-Zn(1)-O(3)#1 C(1)-N(1)-C(5) C(1)-N(1)-Zn(1)

1.330(4) 1.272(5) 1.229(4) 1.247(5) 2.322(3) 1.269(5) 2.124(3) 104.73(10) 94.10(11) 151.37(11) 77.65(11) 157.80(10) 89.79(11) 59.20(11) 95.07(10) 117.2(3) 129.4(2)

2.014(9) 2.058(9) 2.130(8) 2.145(11) 2.181(9) 2.014(9) 101.0(4) 87.2(3) 168.2(4) 88.4(4) 94.1(4) 94.6(4) 87.9(4) 80.4(4) 91.5(4) 172.7(4) 163.0(4) 95.7(4) 75.9(3) 159.64(8) 163.39(9)

Zn(1)-N(1) Zn(2)-O(13) Zn(2)-O(4) Zn(2)-O(12) Zn(2)-O(5) Zn(2)-N(2) O(11)-Zn(1)-N(1) O(9)-Zn(1)-N(1) O(13)-Zn(2)-O(4) O(13)-Zn(2)-O(12) O(4)-Zn(2)-O(12) O(13)-Zn(2)-O(5) O(4)-Zn(2)-O(5) O(12)-Zn(2)-O(5) O(13)-Zn(2)-N(2) O(4)-Zn(2)-N(2) O(12)-Zn(2)-N(2) O(5)-Zn(2)-N(2)

2.193(10) 2.015(9) 2.024(8) 2.069(8) 2.076(9) 2.100(10) 93.6(4) 91.7(4) 108.0(4) 105.5(4) 90.9(4) 103.7(4) 147.4(4) 87.9(3) 103.4(4) 85.8(3) 150.4(4) 79.5(3)

C(13)-O(2)-Cd(1)#3 C(19)-O(3)-Cd(1)#2

117.3(2) 127.47(17)

a Symmetry transformations used to generate equivalent atoms: #1 -x + 1/2, y - 1/2, -z + 1/2 #2 -x + 1/2, -y + 3/2, -z #3 -x + 1/2, y + 1/2, -z + 1/2. b Symmetry transformations used to generate equivalent atoms: #1 -x + 1, -y + 2, -z #2 -x + 1, -y + 1, -z. c Symmetry transformations used to generate equivalent atoms: #1 -x + 1/2, y + 1/2, -z + 1/2 #2 -x + 1/2, y - 1/2,-z + 1/2. d Symmetry transformations used to generate equivalent atoms: #1 -x - 1, y + 1/2, -z + 1/2 #2 -x - 1, y - 1/2, -z + 1/2. e Symmetry transformations used to generate equivalent atoms: #1 -x + 1, -y + 2, -z + 2.

equivalent data were averaged. The structures were solved by direct methods with SHELXS-9728 and Fourier techniques and refined by the full-matrix least-squares method on F2 with SHELXL-97.29 All non-hydrogen atoms were refined anisotropically, and hydrogen atoms were located in a different map phased on the non-hydrogen atoms and included as isotropic contributors in the final least-squares cycles. All the crystal data and structure refinement details for the five compounds are given in Table 1. Table 2 lists the data of relevant bond distances and angles.

Chart 1

Results and Discussion Syntheses. These five compounds are all prepared through the hydrothermal reactions. Depending on the extent of deprotonation, the carboxylate groups present four types of coordination modes (Chart 1). In the preparation of polymers 1 and 2, MnSO4 or Pb(Ac)2‚3H2O reacted with ligand H2dcapp at the same ratio of 2:1. Under high temperature and pressure, onedimensional (1D) [Mn2(2,6-pda)2(H2O)3]∞ (1) chains and two-dimensional (2D) [Pb(2,6-pda)]∞ (2) sheets are con-

structed by 2,6-pda from hydrolysis of H2dcapp. However, if 2,6-pda is directly used as starting building blocks, no crystal was obtained. The juxtaposed experiments were carried out at 160, 170, and 180 °C, respectively.

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Figure 1. The atom-labeling scheme and the molecular geometry of the chain in [Mn2(2,6-pda)2(H2O)3]∞ (1).

Under the same reaction conditions as the preparation of polymers 1 and 2, the reactions of Cd(Ac)2‚2H2O or Zn(Ac)2‚2H2O with H2dcapp or 2,6-pda only generated white powder products whose composition cannot be identified. When only 2,5-H2pda was used as bridging ligand, a zinc tetranuclear metallamacrocyclic complex 5 {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 could be obtained, but the corresponding Cd compounds cannot be produced. In 5, there are many coordinated H2O molecules. To prevent H2O from coordinating with metal ions, we used phen as an auxiliary ligand. When Cd(Ac)2‚2H2O or Zn(Ac)2‚2H2O were treated with phen and 2,5-H2pda, respectively, at the same ratio of 1:1:1 at 160 °C, polymers 3 and 4 were achieved. Polymer 3 has a 2D network structure, while polymer 4 displays a zigzag chain framework. The two polymers show different features, and the reason may be that the radii of the Cd(II) ion (0.84 Å) is bigger than that of the Zn(II) ion (0.60 Å). It can be seen from the above description that introduction of an auxiliary ligand has a great influence on both molecular formation and crystal packing, which can be attributed to the spatial arrangement of the bridging groups and π-π intermolecular interactions of aromatic rings. In addition, the hydrothermal method has been extensively employed for the preparation of coordination polymers, and many factors can affect the resultant products, such as reacting time, temperature, pH value, and molar ratio of reactants.16 Description of Structures 1D Polymer [Mn2(2,6-pda)2(H2O)3]∞ (1). The catenulate structure of 1 is formed by the prolongation of dinuclear Mn units with a NO6 chromophore around the metal ions. Figure 1 shows the atom-labeling scheme and the molecular geometry of the chain. Each 2,6-pda can be described as a tridentate building block linking three Mn centers. Both Mn(1) and Mn(2) are sevencoordinate. Mn(1) has a distorted pentagonal-bipyramidal geometry and is coordinated with one pyridyl nitrogen N(1), four bridging oxygen O(1), O(3), O(5), O(5A) from carboxylate groups, one bridging oxygen O(10), and one terminal oxygen O(11) from two hydrone, respectively. The equatorial plane is composed of O(5)O(5A)N(1)O(1)O(10) with deviation of 0.0407 Å. O(3) and O(11) occupy the axial positions. The similar coordination environment can be viewed around Mn(2) with N(2)O(3)O(10)O(7)O(7B) as the equatorial plane. O(1) and O(9) at two axial positions complete the coordination polyhedron. Mn(1) and Mn(2) have es-

Figure 2. The 2D architecture of [Mn2(2,6-pda)2(H2O)3]∞ (1) formed by hydrogen bonding.

sentially the same coordination geometry MnNO6 with Mn-O(N) bond distances ranging from 2.127(4) to 2.500(4) Å. In each chain Mn ions arrange in a quasi-linear array with both Mn(2)‚‚‚Mn(1)‚‚‚Mn(1A) and Mn(1B)‚‚‚ Mn(2B)‚‚‚Mn(2C) angles of 138.6° (Figure 1). Two Mn atoms in each Mn(1)‚‚‚Mn(2) pair is separated by 3.357 Å, which is much shorter than that of the reported polymers linked by carboxylate groups such as [Mn(C5H6NO3)2]∞,26 [Mn(C14H11N2O4.5)]∞,30 [Mn(C19H16N3O5)]∞,31 and [(adipate)Mn(bpe)]∞ (bpe ) 1,2bis(4-pyridyl)ethane),9a and even shorter than that in some carboxylate bridged polynuclear complexes [Mn3(µ-ClCH2COO)6(bpy)2],[Mn2(µ-ClCH2COO)2(phen)4](ClO4)2‚2CH2Cl2,31 and [Mn2(baib)(O2Cph)3(NCS)]‚DMF (baib ) 1,3-bis[(2-dimethylaminoethyl)iminomethyl]benzene).32 Mn(1) and Mn(2) in each pair are triply bridged by O(10), O(1), and O(3). All the Mn(1)‚‚‚Mn(2) pairs are extended by the µ2-O bridging functionalities. Mn(1) is further connected with Mn(1A) through O(5) and O(5A) at distance of 3.696 Å. The bridging angle Mn(1A)-O(5)-Mn(1) is 109.31(14)°. Mn(2) is connected to Mn(2B) through O(7) and O(7B) with a Mn(2)‚‚‚ Mn(2B) distance of 3.701 Å and a Mn(2)-O(7)-Mn(2B) angle of 109.24(14)°. The interpair distances of Mn‚‚‚ Mn (3.696 and 3.701Å, respectively) are much longer than the intrapair distance (3.357 Å). In this way, an infinite chain along the crystallographic b direction are achieved in a fashion of ‚‚‚[Mn(1)‚‚‚Mn(2)]‚‚‚[Mn(2)‚‚‚ Mn(1)]‚‚‚[Mn(1)‚‚‚Mn (2)]‚‚‚ (Figure 1). Figure 2 shows a 2D architecture formed by hydrogen bonds. Two pyridine rings in each unit are almost parallel with a deviation of 16.9°. The shortest distance of the two pyridine planes is 3.578 Å, which is in the limit of the common range for π‚‚‚π interactions between two aryl rings.15,33 But there is no obviously intermolecular π‚‚‚π interaction between the chains because the shortest interchain atom‚‚‚atom separation involving the pyridine rings is longer than 4.0 Å. Polymeric complexes formed by Mn(II) and 2,6-pda are rare. There are only some similar examples: polymers {[Na2(H2O)8(CH 3 OH) 0.5 ][Mn 2 Na 2 (2,6-pda) 4 (H 2 O) 8 ]‚0.25CH 3 OH‚ 2H2O}n and [MnK2(2,6-pda)2 (H2O)7]n, trinuclear complex [Mn3(2,6-pda)3(2,2′-bpy)3(H2O)2], etc.34


Figure 3. The infinite 2D sheet in polymer [Pb(2,6-pda)]∞ (2).

Figure 4. In the sheets of polymer [Pb(2,6-pda)]∞ (2), 2,6pda acts in a tetradentate mode.

2D Polymer [Pb(2,6-pda)]∞ (2). The structure of polymer 2 is built upon the stacking of 2D networks that are made by the polymerization of asymmetric [Pb(2,6pda)] units (Figure 3). Each Pb center is six-coordinate: one N atom and five O atoms from three 2,6-pda. Pb-O distances fall in the range of 2.397(6)-2.808Å, similar to the previously reported Pb-O interactions in the complex Pb2{PMIDA}‚1.5H2O (H4PMIDA ) H2O3PCH2N(CH2CO2H)2)19 (from 2.331(9) to 2.876(9) Å). Pb-N distance (2.492(8) Å) is comparatively shorter than those reported in the literature.19,22,35 The geometry of the Pb center is hemidirected, and there is a clearly identifiable gap in the Pb coordination sphere, suggesting that Pb contains a stereochemically active lone pair of electrons.19,22 It is noticeable that 2,6-pda acts as a tetradentate ligand. In Figure 4, N(1H) terminally coordinate to Pb(1H); O(4H) bridges Pb(1L) and Pb(1H) in an η1:µ2 fashion; O(2H) also joins Pb(1H) and Pb(1A) in the η2: µ2 fashion; Pb(1A) is chelated by O(2H) and O(1A). Two O(4) atoms form a double-oxo bridge between two Pb atoms showing a rhombic ring in the 2D sheet at the [1 0 0] crystalline plane. Moreover, atom‚‚‚atom contacts also exist between O(4L)‚‚‚O(4H) with a distance of


Figure 5. The 2D sheet structure of 2D polymer [Cd(phen)(2,5-pda)]∞ (3) containing a rhombic grid feature.

2.791 Å and Pb(1H)‚‚‚Pb(1L) with a distance 4.412 Å. The Pb‚‚‚Pb distance in the rhombic ring is slightly shorter than the distances of Pb(1H)‚‚‚Pb(1B) (4.881 Å) and Pb(1H)‚‚‚Pb(1I) (5.551 Å) along the crystallographic b direction but is comparable with those in the literature.35 Some Pb(II)-2,6-H2pda complexes have also been constructed; for example, {[Pb(2,6-pda)(2,6-H2pda)(H2O)2]2}n is a nine-coordinate binuclear complex with two metal fragments linked via the central fourmembered Pb2O2 ring,36 and [Pb2(2,6-pda)2(2,6-H2pda)2(H2O)6] is composed of infinitely cross-linked dimer entities.37 O(1) atoms are involved in hydrogen bonds between 2D sheets. These hydrogen bonds are relatively weak, with the distances of O(1)‚‚‚H(4) and C(4)‚‚‚O(1) of 2.469 and 3.317 Å, respectively. The angle of O(1)‚‚‚H(4)‚‚‚ C(4) is 128.8°. Such hydrogen bonds make the structure pack in a three-dimensional (3D) feature. In addition, other noncovalent interactions such as π‚‚‚π function play a role in stabilizing the structure. The shortest atom‚‚‚atom separation involving the pyridine rings is 3.756 Å. 2D Polymer [Cd(phen)(2,5-pda)]∞ (3). Single crystal X-ray analysis reveals that polymer 3 possesses a 2D rhombic grid framework (Figure 5) constructed from binuclear structural units. Two Cd centers in the unit have an inversion center (Figure 6). Each cadmium atom is located in the center of a distorted octahedral coordination environment. Cd-O distances range from 2.231(2) to 2.343(2) Å, and Cd-N distances are in the range of 2.352(2) to 2.398(2) Å, which are both similar to those in [Cd(bpdc)‚H2O]n14 (H2bpdc ) 2,2′-bipyridyl4,4′-dicarboxylic acid) and [Cd2(C2O4)2‚6H2O].38 Between the two Cd atoms, two O(3) atoms act as µ2-bridges forming a four-membered ring, with a Cd‚‚‚Cd separation of 3.763 Å. This distance is much shorter than those of the reported cadmium complexes (3.908(1) and 5.812(1) Å, respectively).8,39 In the 2D skeleton, carboxylate groups play a vital role. 2,5-pda acts as a tridentate ligand with O(3), N(3), and O(2) as donors. the O(3) atom binds to two Cd ions

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Figure 7. Each 2,5-pda group acts in a bis-bidentate mode and bridges two zinc atoms, resulting in [Zn(2,5-pda)(phen)]n (4) chains with additional phen ligands found alternately on both sides.

Figure 6. The rhombic grid feature of the 2D polymer [Cd(phen)(2,5-pda)]∞ (3).

in an η1:µ2 fashion. Concurrently, the O(2) atom connects with the third Cd in a η1 fashion, thus leading to an infinite 2D sheet. As shown in Figure 6, the sheet exhibits a rhombic grid feature. Each rhombic grid is composed of six Cd linked through 2,5-pda. The four Cd apexes, Cd(1B), Cd(1I), Cd(1E), and Cd(1H) are well coplanar with large dimensions of 7.875 × 11.083 Å2 [Cd(1I)‚‚‚Cd(1E) distance and Cd(1E)‚‚‚Cd(1H) distance]. The two Cd‚‚‚Cd diagonal distances are 13.233 and 13.950 Å. For steric reasons, two phen rings overlap to a certain degree within the rhombic grid. The shortest atom‚‚‚atom distance of 3.741 Å between two benzene rings indicates the existence of π‚‚‚π interaction. Much stronger π‚‚‚π interactions can also be found between the adjacent layers with the shortest separation of 3.481 Å. Moreover, strong O‚‚‚H-C hydrogen bonds (the O‚‚‚H distance is 2.492 Å) between layers further strengthen the stacking of the superarchitecture. And up to now, some Cd(II)-pda polymers have been reported in the literature. In polymer {[Cd(3,4-pda)(bpp)]‚0.5H2O}n (bpp ) 1,2-bis(4-pyridyl)ethane), the 3,4-pda acts as a three-connector.40 Dinuclear [Cd(2,6pda)(H2O)3]2‚2(2,5-H2pda) self-assembles into layers via hydrogen bonds.41 In the 3D framework [Cd3(3,4-pda)2(OH)2(H2O)2]n, two different types of channels exist, one being built from pyridine rings and {CdO5N} and {CdO6} building units and the other being constructed from pyridine rings and {CdO5N} building units.42 1D Polymer {[Zn(phen)(2,5-pda)]‚H2O}∞ (4). X-ray crystallography reveals that 4 shows a 1D zigzag chain structure. As shown in Figure 7, each Zn atom is coordinated in a trigonal anti-bipyramidal geometry, with two nitrogen atoms from the phen and one nitrogen and three oxygen atoms from two 2,5-pda. All these coordination atoms form the two bases of the pyramids, and the central Zn atom is the common apex. The dihedral angle of two base planes O(4A)-N(3)-O(3A) and N(2)-N(1)-O(1) is 24.3°. The average Zn-N bond distance (2.143 Å) is similar to those of the other Zn polymers with mixed ligands, such as 1D polymer [Zn(bpy)(tp)](bpy) (H2tp ) terephthalic acid) (2.132 Å),16 the dimeric zinc complex [Zn(dmit)(2,2′-bpy)]2 (dmit ) 1,3-dithiole-2-thione-4,5-dithiolate) (2.136 Å).43 The Zn-O distances fall in a wide range of 2.052(3)-2.322(3) Å,

Figure 8. Along the crystallographic c directions, the zigzag chains [Zn(2,5-pda)(phen)]n (4) are arranged in layers, with double-linked hydrogen bonds between the spaces.

which are also comparable to those in the literature.16 Each 2,5-pda acts in a tetradentate mode and bridges two Zn atoms, resulting in a [Zn(2,5-pda)(phen)]n chain. The two pyridine rings of the adjacent 2,5-pda have a dihedral angle of 86.9°. The Zn‚‚‚Zn‚‚‚Zn angle formed by three adjacent zinc atoms is 81.5°. Along the crystallographic c direction, zigzag chains are arranged in layers (Figure 8). The shortest atom‚‚‚ atom distance of the pyridine rings is calculated to be 3.725 Å, indicating an aromatic π‚‚‚π stacking interaction between adjacent chains. It is noted that π‚‚‚π stacking interactions (3.460 Å) are also apparent between adjacent layers. In combination with the C(12)H(12)‚‚‚O(3) hydrogen bond, the layers are further extended into a 3D supramolecular construction. The values of C(12)‚‚‚O(3) distance (3.078 Å) and C(12)H(12)‚‚‚O(3) angle (122.9°) indicate a strong C-H‚‚‚O hydrogen bonding. The values for C-H‚‚‚O hydrogenbond parameters are in the acceptable range reported previously (C‚‚‚O distances in the range of 3.0-4.0 Å, C-H‚‚‚O angles in the range of 110-180°).16,44 Tetranuclear Metallamacrocyclic Complex {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 (5). The struc-


Figure 9. A perspective view of tetranuclear metallamacrocycle in complex {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 (5).

ture of complex 5 can be described as a tetranuclear metallamacrocycle (Figure 9) consisting of two identical dinuclear {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]} subunits that are connected together via the bridging carboxylate groups. Each carboxylate group in 2,5-pda provides one donor in a syn or anti fashion. N(1) and O(1) chelate to Zn(1), and O(4) terminally coordinates with Zn(2). N(2) and O(5) of the other 2,5-pda chelate to Zn(2), and O(6) terminally coordinates with Zn(1A). Zn‚‚‚Zn distances are 7.448 Å for Zn(1)‚‚‚Zn(2) and Zn(1A)‚‚‚Zn(2A), and 8.474 Å for Zn(1)‚‚‚Zn(2A) and Zn(2)‚‚‚Zn(1A). These Zn‚‚‚Zn separations are significantly larger than those observed in other Zn polynuclear complexes, such as tetranuclear complex [Zn2L(µ1,1-HCO2)(µ1,3-HCO2)]2(ClO4)2 (L)2,6-bis(N-2-(2′-pyridylethyl)-formimidoyl)-4-methyl-phenol) (3.130(1)-6.053 Å),45 tetrazinc carbamato complexes (3.0-3.3 Å, av. 3.18 Å),46,47 and tri- and hexanuclear zinc(II) cages [Zn3Cl2(3,5Me2Pz)4(t-BuPO3)2] and [Zn6Cl4(3,5-Me2PzH)8(phPO3)4] (t-BuPO3 ) tert-butylphosphonic acid, 3,5-Me2Pz ) 3,5dimethylpyrazole) (3.855-4.408 Å),48 etc. Moreover, there is no guest molecule in the cavity of the macrocycle. The two Zn centers display two different coordination geometries. Zn(1) is six-coordinate by O(1), N(1), O(8A) from 2,5-pda, and O(9), O(10), O(11) from water molecules. While Zn(2) is in a square pyramidal coordina-


tion environment surrounded by N(2), O(4), O(5), O(12), and O(13). The distances of Zn(1)-O (2.014(9)-2.101(9) Å) are comparable to those of Zn(2)-O (2.015(9)2.076(9) Å). And the coordination angles around the center Zn atoms fall in the range of 75.9(3)-172.7(4)°. The macrocycles are further connected together into a three-dimension framework by hydrogen bonding and π‚‚‚π interactions. Intermolecular hydrogen bonding between coordinated H2O and carboxylate oxygen atoms extend the macrocycles into a higher super lattice, with a O(13A)‚‚‚O(1C) distance of 2.628 Å, O(13A)‚‚‚O(2C) of 2.717 Å, O(9C)‚‚‚O(5D) of 2.878 Å, O(9C)‚‚‚O(3AA) of 2.684 Å, and O(12D)‚‚‚O(3A) of 2.816 Å, respectively. Moreover, the close π‚‚‚π interactions (3.214 Å) show some importance in packing the superlattice (Figure 10). Many Zn complexes constructed from pda ligands have been reported. For example, mononuclear Zn(2,5Hpda)2(H2O) units are linked further into a 3D structure through the weak interactions of hydrogen bonds between the two O atoms.49 In a similar polymer [Zn(2,5Hpda)2(H2O)2]n‚2H2O,50 [Zn(2,5-Hpda)2(H2O)2] units are connected by hydrogen bonds to engender 1D channels. [Zn4(2,5-pda)4(H2O)8] exhibits a rectangular structure formed from four zinc(II) and four pda bridging ligands.51 Polymer [Zn(3,4-pda)]n not only possesses a 1D rectangular channel but also contains infinite double-stranded helical chains.42 And a photoluminescent three-dimensional coordination polymer [Zn2(3,4-pda)2(4,4′-bpy)‚ H2O]n containing two types of cavities was also prepared by the covalent linkage of a 2D bilayer motif with a linear connecting ligand.52 Thermal Analysis. In TG analysis of polymer 1, there is no weight loss until 180 °C. 1 releases all coordinated water molecules in the range of 180-250 °C. A continuous weight loss can be detected from 362 to 688 °C attributed to the complete decomposition of the 2,6-pda, and one strong exothermic peak is found at 447 °C. The residue remains to be MnO (Cald.: 28.74%; Found: 27.09%). Polymer 2 is very stable. There is no weight loss until 393 °C. The weight reduces to 55.87% (Cald.: 55.65%) at 530 °C, which is presumed to be the residue of Pb. A very strong exothermic peak can be found at 467.3 °C, indicating a complete decomposition of 2,6-pda. TG analyses of polymer 3 shows that there is a continuously two-step weight loss in the range of 337-854 °C, corresponding to the decomposition of

Figure 10. π‚‚‚π stacking interactions in packing the superlattice of {[Zn(2,5-pda)(H2O)2][Zn(2,5-pda)(H2O)3]}2 (5).

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Figure 11. The temperature dependence of the product of the molar magnetic susceptibility by temperature of polymer [Mn2(2,6-pda)2(H2O)3]∞ (1) investigated over the temperature range 5-300 K at 500 G, and the experimental data plotted as the thermal variation of the reciprocal susceptibility χm-1.

phen and 2,5-pda. The resulting residue is presumed to be CdO (Cald.: 28.07%; Found: 26.93%). Two exothermic peaks are investigated at 449 and 840 °C, respectively. Polymer 4 lost water below 100 °C. The TG curve of the dehydrated product shows no weight loss up to 326 °C, followed by a continuously two-step weight loss of 77.70% from 326 to 671 °C. The final weight is 19.28%, which can be refined as ZnO (Cald.: 19.19%). Correspondingly, a strong exothermic peak at 486 °C is detected by DT analysis. There is no apparent plateau region in the TGA curve of complex 5. A gradual weight loss of 68.63% is found from 68 to 489 °C. The final weight refined as ZnO is 31.37% (Cald.: 31.30%). A very strong exothermic peak at 455 °C is concomitant with the decomposition of 2,5pda. Magnetism. The magnetic property of polymer 1 has been investigated over the temperature range 5-300 K at 500 G. The temperature dependence of the molar magnetic susceptibility is illustrated in Figure 11. χmT decreases smoothly from 4.51 cm3 K mol-1 at 300 K to 3.79 cm3 K mol-1 at 50 K and then more abruptly reaches 1.24 cm3 K mol-1 at 5 K. Taking into account the structure of 1, the spin Hamiltonian considered would be H ) -JS1S2 for approximation. Moreover, Weng53 has numerically calculated the quantum behavior of a chain of antiferromagnetically interacting spins for different values of S. The magnetic behavior can be well described by a polynomial expansion for the high-spin state of Mn(II) (S ) 5/2).26,54

χmT )

(

2.9167 + 208.04(|J|/kBT)2 Nβ2 2 g kB 1 + 15.543(|J|/kBT) + 2707.2(|J|/kBT)3

)

The best least-squares fits of the experimental data were J ) -0.215 cm-1, g ) 2.00 (fixed), and reduced Chi-sqr ) 6.77 × 10-3.

The experimental data plotted as the thermal variation of the reciprocal susceptibility χm-1 is also shown in Figure 11. The variation of χm-1 is well described by the Curie-Weiss law in the experimental temperature range. The values of Cm ) 4.6138 cm3 K mol-1 and Weiss temperature θ ) -11.1105 K are typical for an overall antiferromagnetic coupling. This behavior is characteristic of two high-high (S ) 5/2) MnII ions experiencing a whole antiferromagnetic coupling with g ) 2.00. From magnetic point of view, it is important to point out some structural features. The 1D system is constructed by 2,6-pda, which links two Mn ions at very short distances (3.357, 3.696 Å). The exchange coupling is mainly conducted through two types of bridges, the monatomic µ2-O coming from carboxylate groups and deprotonated oxygen atoms. The Mn‚‚‚Mn interaction could be affected by several factors: the Mn-O distance, the Osyn-Mn-Osyn angle, the Mn-Osyn-C angle.31 Even small changes in these parameters could lead to the changes in Mn‚‚‚Mn interaction. For polymer 1, MnObridge distances ranging from 2.185(4) to 2.500(4) Å are significantly longer than those in the literature.31,55-59 But the lengths of the pathways are about 4.6 Å, which is a very short transmittance distance, helpful for the magnetic coupling. Taking the structure into consideration, only the syn-syn carboxylate bridge will be magnetically active.9a The about 136° for the Osyn-MnOsyn angle is also attributed to their antiferromagnetic coupling. Moreover, the angle at the bridging oxygen would be expected to be important for this aspect of the nature of σ and π overlap between the metal magnetic orbital and the oxygen px, py, and pz orbital that mediates the exchange.60 The bridging angles Mn-OMn range from 91.26(13) to 109.31(14)°. The large MnO-Mn angles may contribute to the antiferromagnetic coupling. Acknowledgment. We thank the National Natural Science Foundation of China (Nos. 20001006 and 20371042) and the Outstanding Young Foundation of Henan Province for support. We greatly show our appreciation for Dr. Paul T. Wood of Department of Chemistry, Cambridge University, who has given much help in the magnetism study. Supporting Information Available: X-ray crystallographic data (CIF file). This material is available free of charge via the Internet at http://pubs.acs.org.

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From Dicarboxylic Acid to Tetranuclear Metallamacrocyclic Complex

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