ARTICLE pubs.acs.org/crystal
pH Dependent Structural Diversity of Metal Complexes with 5-(4H-1,2,4-Triazol-4-yl)benzene-1,3-dicarboxylic Acid Min Chen,† Shui-Sheng Chen,† Taka-aki Okamura,‡ Zhi Su,† Man-Sheng Chen,† Yue Zhao,† Wei-Yin Sun,*,† and Norikazu Ueyama‡ †
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, China ‡ Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
bS Supporting Information ABSTRACT: A ligand 5-(4H-1,2,4-triazol-4-yl)benzene-1,3dicarboxylic acid (H2L) with N- and O-donors was successfully applied to construct a series of coordination complexes [Cu3(μ 3 -OH)2 (HL)4 ]n (1), [Co(HL)2 (H 2 O)4 ] 3 3H 2 O (2), [Ni(HL)2(H2O)4] 3 3H2O (3), [Mn(HL)2]n (4), {[Cu2(L)2(μOH2)2] 3 3H2O}n (5), {[Co2(L)2(μ-OH2)2] 3 3H2O}n (6), {[Ni2(L)2(μ-OH2)2] 3 3H2O}n (7), and {[Mn(L)(μ-OH2)] 3 2H2O}n (8) under hydrothermal conditions. By adjusting the reaction pH, H2L ligand is partially deprotonated to give HL form in 14 and completely deprotonated to afford L2 form in 58. The structural analyses revealed that complex 1 is a threedimensional (3D) (3,3,5,6)-connected framework with Point (Schl€afli) symbol of (4.6.8)2(42.65.83)2(42.66.86.10)(42.6)2, while 2 and 3 are discrete mononuclear complexes which are extended by hydrogen bonds to form 3D frameworks. The (3,6)-connected 3D framework of 4 is defined as a metalorganic replica of anatase (ant) net with Point (Schl€afli) symbol of (42.6)2(44.62.88.10). Complexes 57 are isostructural and display (4,5)-connected 3D frameworks with Point (Schl€afli) symbol of (42.52.62)(42.53.62.73), and 8 is a binodal (4,6)-connected 3D net with the Point (Schl€afli) symbol of (3.54.6)(32.56.66.9). The results revealed that the reaction pH and the metal center play important role in determining the structures of the complexes. Magnetic studies indicate that the mixed μ3-hydroxo and triazolyl bridges in 1 and the double synsyn carboxylate bridges in 4 mediate antiferromagnetic interactions. The alternating triazolyl and water bridges show alternating ferro- and antiferromagnetic interactions in 5 but antiferromagnetic interactions in 6 and 7. The mixed triazolyl and water bridges show antiferromagnetic interactions in 8.
’ INTRODUCTION In recent years, the rational design and synthesis of coordination frameworks have attracted intense attention from chemists because of their fascinating structures and interesting properties.1,2 Most of the reported coordination frameworks are constructed by linking transition metal atoms through multidentate bridging ligands.3 In this context, coordination frameworks with aromatic multicarboxylate ligands such as 1,3-/1,4benzene dicarboxylate, 1,3,5-benzenetricarboxylate, and so on as functional linkers have been widely studied due to their rigid characters, diverse coordination modes as well as high thermal stability.4 Apart from this, the organic linkers with an amalgamation of heterocyclic and carboxylate groups were well used in construction of coordination frameworks in recent years and have been becoming an active research field.57 In addition, the coordination of aromatic polycarboxylate ligands is markedly sensitive to the synthetic conditions, leading to the difficulty in the structural predictions of the resulted complexes. Factors such as the reaction temperature, solvent system, counterions, pH value, and metal-to-ligand ratio have been found to exert influence on the formation of coordination frameworks.812 In r 2011 American Chemical Society
Scheme 1. Schematic Drawing for the Ligand H2L
this regard, we chose a ligand combined with 1,2,4-triazole and aromatic carboxylate groups in this work, namely 5-(4H-1,2,4triazol-4-yl)benzene-1,3-dicarboxylic acid (H2L) (Scheme 1). On the basis of the different forms of the ligand controlled by reaction pH and varied coordination modes, a family of Received: January 17, 2011 Revised: March 19, 2011 Published: March 29, 2011 1901
dx.doi.org/10.1021/cg200068v | Cryst. Growth Des. 2011, 11, 1901–1912
Crystal Growth & Design coordination complexes, [Cu3(μ3-OH)2(HL)4]n (1), [Co(HL)2(H2O)4] 3 3H2O (2), [Ni(HL)2(H2O)4] 3 3H2O (3), [Mn(HL)2]n (4), {[Cu2(L)2(μ-OH2)2] 3 3H2O}n (5), {[Co2(L)2(μ-OH2)2] 3 3H2O}n (6), {[Ni2(L)2(μ-OH2)2] 3 3H2O}n (7), and {[Mn(L)(μ-OH2)] 3 2H2O}n (8), were obtained. All the complexes are characterized by X-ray crystallographic, IR, elemental, thermal stability and powder X-ray diffraction analyses. The magnetic properties of 1 and 48 were investigated.
’ EXPERIMENTAL SECTION All commercially available chemicals and solvents are of reagent grade and were used as received without further purification. The ligand H2L was synthesized according to the reported procedure.13 Elemental analyses for C, H, and N were performed on a Perkin-Elmer 240C elemental analyzer at the analysis center of Nanjing University. Thermogravimetric analyses (TGA) were performed on a simultaneous SDT 2960 thermal analyzer under nitrogen with a heating rate of 10 °C min1. FT-IR spectra were recorded in the range of 4004000 cm1 on a Bruker Vector22 FT-IR spectrophotometer using KBr pellets. Power X-ray diffraction (PXRD) patterns were measured on a Shimadzu XRD6000 X-ray diffractometer with Cu KR (λ = 1.5418 Å) radiation at room temperature. The magnetic measurements in the temperature range of 1.8300 K were carried out on a Quantum Design MPMS7 SQUID magnetometer in a field of 2000 Oe. Diamagnetic corrections were made with Pascal’s constants for all samples. Preparation of [Cu3(μ3-OH)2(HL)4]n (1). A mixture of CuCl2 3 2H2O (8.5 mg, 0.05 mmol), H2L (11.7 mg, 0.05 mmol), and H2O (8 mL) was adjusted to pH = 4 with 0.5 mol L1 NaOH solution. The mixture was then sealed into Teflon-lined stainless steel container and heated at 160 °C for 3 days. After cooling to room temperature, darkblue block crystals were obtained in 43% yield. Anal. Calcd for C40H26N12O18Cu3: C 41.66; H, 2.27; N, 14.57%. Found: C, 41.72; H, 2.34; N, 14.48%. IR (KBr pellet, cm1): 3423 (w, br), 1702(s), 1561 (s), 1536 (s), 1405 (m), 1372 (m), 1263 (m), 1073 (m), 1060 (m), 852 (m), 764 (m), 708 (m), 672 (w), 508 (w). Preparation of [Co(HL)2(H2O)4] 3 3H2O (2). Complex 2 was obtained by the same procedure used for preparation of 1 except that the metal salt was replaced by CoCl2 3 6H2O (12.0 mg, 0.05 mmol). Paleorange block crystals of 2 were obtained in 72% yield. Anal. Calcd for C20H26N6O15Co: C 36.99, H 4.04, N 12.94%. Found: C 37.13, H 4.08, N 12.86%. IR (KBr pellet, cm1): 3353 (m, br), 1708 (s), 1572(s), 1426 (m), 1378 (m), 1266 (m), 1216 (m), 1168 (m), 1098(m), 883(w), 766 (m), 728 (m), 610 (w), 541 (w), 472 (w). Preparation of [Ni(HL)2(H2O)4] 3 3H2O (3). Complex 3 was also obtained by the same method used for preparation of 1 except that CuCl2 3 2H2O was replaced by NiCl2 3 6H2O (12.0 mg, 0.05 mmol). Pale-blue block crystals of 3 were obtained in 87% yield. Anal. Calcd for C20H26N6O15Ni: C 37.00, H 4.04, N 12.95%. Found: C 36.96, H 4.11, N 12.89%. IR (KBr pellet, cm1): 3355 (m, br), 1709 (s), 1570 (s), 1425 (m), 1377 (m), 1267 (m), 1215 (m), 1169 (m), 1099(m), 884(w), 767 (m), 730 (m), 609 (w), 540 (w), 470 (w). Preparation of [Mn(HL)2]n (4). Complex 4 was prepared by the same procedure used for preparation of 1 except that the metal salt was replaced by MnCl2 3 4H2O (10.0 mg, 0.05 mmol). Colorless prism crystals of 4 were obtained in 67% yield. Anal. Calcd for C20H12N6O8Mn: C 46.26, H 2.33, N 16.18%. Found: C 46.34, H 2.28, N 16.24%. IR (KBr pellet, cm1): 3406 (m, br), 1711 (s), 1578 (s), 1425 (m), 1370 (m), 1277 (m), 1234 (m), 1094 (m), 1054 (m), 879 (m), 768 (m), 719 (m), 648(m), 546(w), 454(w). Preparation of {[Cu2(L)2(μ-OH2)2] 3 3H2O}n (5). Complex 5 was obtained by the same procedure used for preparation of 1 except that the pH value of reaction mixture was adjusted to 7 instead of 4. Blue block crystals of 5 were obtained in 73% yield. Anal. Calcd for
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C20H20N6O13Cu2: C 35.35; H, 2.97; N, 12.37%. Found: C, 35.42; H, 2.93; N, 12.32%. IR (KBr pellet, cm1): 3345 (m, br), 1574 (s), 1361 (s), 1104 (m), 1065 (w), 1023(w), 874(w), 811 (m), 777 (m), 745 (m), 606 (m), 567 (w), 484 (w). Preparation of {[Co2(L)2(μ-OH2)2] 3 3H2O}n (6). Complex 6 was obtained by the same procedure used for preparation of 2 except that the pH value was adjusted to 7 instead of 4. Orange prism crystals of 6 were obtained in 64% yield. Anal. Calcd for C20H20N6O13Co2: C 35.84, H 3.01, N 12.54%. Found: C 35.92, H 2.96, N 12.61%. IR (KBr pellet, cm1): 3423 (m, br), 1558 (s), 1367 (s), 1105 (m), 1064 (w), 1019(w), 879 (w), 774 (m), 715 (m), 668 (m), 565 (w), 479 (w). Preparation of {[Ni2(L)2(μ-OH2)2] 3 3H2O}n (7). Complex 7 was obtained by the same procedure used for preparation of 3 except that the pH value was adjusted to 7 instead of 4. Green prism crystals of 7 were obtained in 76% yield. Anal. Calcd for C20H20N6O13Ni2: C 35.86, H 3.01, N 12.55%. Found: C 35.93, H 2.94, N 12.60%. IR (KBr pellet, cm1): 3420 (m, br), 1561 (s), 1368 (s), 1107 (m), 1060 (w), 1022(w), 880 (w), 776 (m), 719 (m), 670 (m), 566 (w), 481 (w). Preparation of {[Mn(L)(μ-OH2)] 3 2H2O}n (8). Complex 8 was obtained by the same procedure used for preparation of 4 except that the pH value was adjusted to 7 instead of 4. Colorless block crystals of 8 were obtained in 52% yield. Anal. Calcd for C10H11N3O7Mn: C 35.31, H 3.26, N 12.35%. Found: C 35.38, H 3.19, N 12.42%. IR (KBr pellet, cm1): 3330 (m, br), 1558 (s), 1367 (s), 1105 (m), 1062 (w), 1010 (w), 878(w), 780 (m), 715 (m), 641 (m), 530 (w), 460 (w). X-ray Crystallography. The X-ray diffraction measurements for 13 and 8 were made on a Rigaku Rapid II imaging plate area detector with Mo KR radiation (0.71075 Å) using MicroMax-007HF microfocus rotating anode X-ray generator and VariMax-Mo optics at 200 K. The structures of 1 and 8 were solved by direct methods with SHELXS-97 and expanded using Fourier techniques with DIRFID-99.14,15 The structures of 2 and 3 were solved by direct methods with SIR9216 and expanded using Fourier techniques by DIRFID-99.15 The non-hydrogen atoms were refined anisotropically by the full matrix least-squares method on F2. The hydrogen atoms of H6, H12, H13 in 1, H6, H7, H8, H9 in 2, water molecules in 3, and H4, H5, H6 in 8 were located from the difference Fourier map directly while all the other hydrogen atoms were generated geometrically and refined isotropically using the riding model. All calculations for 13 and 8 were performed using the CrystalStructure crystallographic software package.17 The crystallographic data collections for 47 were carried out on a Bruker Smart Apex CCD with graphite-monochromated Mo KR radiation (λ = 0.71073 Å) at 293(2) K using the ω-scan technique. The data were integrated by using the SAINT program,18 which was also used for the intensity corrections for the Lorentz and polarization effects. Semiempirical absorption correction was applied using the SADABS program.19 The structures were solved by direct methods, and all non-hydrogen atoms were refined anisotropically on F2 by the full-matrix least-squares technique using the SHELXTL crystallographic software package.20 The hydrogen atoms of carboxylate group in 4 and free water molecules in 57 were located from the Fourier map, and all the other hydrogen atoms were generated geometrically and refined isotropically using the riding model. The details of the crystal parameters, data collection, and refinements for the complexes are summarized in Table 1, and selected bond lengths and angles are listed in Table 2.
’ RESULTS AND DISCUSSION Crystal Structure of [Cu3(μ3-OH)2(HL)4]n (1). The result of single crystal X-ray diffraction analysis revealed that the asymmetric unit of 1 consists of two Cu(II) atoms, one of which sitting on the inversion center, one μ3-hydroxo bridge, and two HL ligands. The partial deprotonation of H2L to give HL in 1 is also confirmed by the IR spectral data of 1 since a strong band 1902
dx.doi.org/10.1021/cg200068v |Cryst. Growth Des. 2011, 11, 1901–1912
Crystal Growth & Design
ARTICLE
Table 1. Crystal Data and Structure Refinements for Complexes 18 1
3
4 C20H12N6O8Mn
empirical formula
C40H26N12O18Cu3
C20H26N6O15Co
C20H26N6O15Ni
formula weight
1153.35
649.40
649.18
519.30
crystal system
triclinic
monoclinic
monoclinic
monoclinic
space group
P1
C2/c
C2/c
C2/c
a (Å)
6.709(2)
26.458(8)
26.495(4)
17.949(3)
b (Å)
11.932(5)
6.5936(15)
6.6189(11)
12.708(3)
c (Å)
12.869(4)
16.939(5)
16.996(3)
9.6065(16)
R (deg) β (deg)
107.062(13) 95.121(12)
90.00 118.205(12)
90.00 118.296(8)
90.00 112.333(4)
γ (deg)
100.054(14)
90.00
90.00
90.00
T (K)
200
200
200
293(2)
V (Å3)
958.8(6)
2604.2(12)
2624.4(7)
2026.7(6)
Z
1
4
4
4
Fcalcd (g 3 cm3)
1.997
1.656
1.643
1.702
μ (mm1)
1.756
0.747
0.826
0.717
F (000) data collected
581 9127
1340 11941
1344 9098
1052 4957
independent data
4362
2981
2309
1784
goodness-of-fit
1.113
1.120
1.056
1.032
R1a (I > 2σ (I))
0.0297
0.0368
0.0625
0.0333
wR2b (I > 2σ (I))
0.0747
0.0988
0.1325
0.0823
5
a
2
6
7
8
empirical formula
C20H20N6O13Cu2
C20H20N6O13Co2
C20H20N6O13Ni2
C10H11N3O7Mn
formula weight crystal system
679.52 monoclinic
670.28 monoclinic
669.84 monoclinic
340.16 orthorhombic
space group
C2/c
C2/c
C2/c
Pbcn
a (Å)
20.064(5)
20.555(3)
20.625(4)
10.531(3)
b (Å)
7.7666(19)
7.4526(10)
7.3923(15)
14.549(6)
c (Å)
17.110(4)
17.229(3)
17.250(3)
7.681(3)
R (deg)
90.00
90.00
90.00
90.00
β (deg)
122.820(4)
123.504(5)
123.574(3)
90.00
γ (deg) T (K)
90.00 293(2)
90.00 293(2)
90.00 293(2)
90.00 200
V (Å3)
2240.6(10)
2200.8(6)
2191.3(8)
1176.9(8)
Z
4
4
4
4
Fcalcd (g 3 cm3)
2.014
2.023
2.030
1.920
μ (mm1)
1.989
1.600
1.811
1.165
F (000)
1376
1360
1368
692
data collected
5396
5165
5390
10043
independent data goodness-of-fit
1973 1.009
1914 1.067
2018 1.016
1348 1.136
R1a (I > 2σ (I))
0.0373
0.0354
0.0339
0.0258
wR2b (I > 2σ (I))
0.0795
0.0996
0.1060
0.0700
R1 = ∑||Fo| |Fc||/Σ|Fo|. b wR2 = |∑w(|Fo|2 |Fc|2)|/∑|w(Fo)2|1/2, where w = 1/[σ2(Fo2) þ (aP)2 þ bP]. P = (Fo2 þ 2Fc2)/3.
at 1702 cm1 from COOH was observed (see Experimental Section). As depicted in Figure 1a, each Cu1 is five-coordinated by two N atoms from two different HL ligands and three O from another HL and two μ3-hydroxo groups to form distorted squarepyramidal coordination geometry with a τ valve of 0.30.21 Each Cu2 exhibits a slightly elongated octahedral coordination sphere with two N atoms from two distinct HLand four O ones from two HL and two μ3-hydroxo groups. The HL ligands in 1 have two different coordination modes I and II,
respectively, as shown in Scheme 2. Each HL with mode I connects three Cu(II) atoms through two N atoms of the triazolyl group and one O atom of μ1-η1:η0 monodentate carboxylate group, while the one with mode II links two Cu(II) atoms through one N atom of the triazolyl group and one O atom from a μ1-η1:η0 carboxylate group. If the linkage of HL ligand with mode II is neglected, the Cu1 and Cu2 are linked together by HL ligands with mode I to generate a two-dimensional (2D) network (Figure 1b). The Cu 3 3 3 Cu distances bridged by 1903
dx.doi.org/10.1021/cg200068v |Cryst. Growth Des. 2011, 11, 1901–1912
Crystal Growth & Design
ARTICLE
Table 2. Selected Bond Lengths (Å) and Angles (deg) for Complexes 18 a
Table 2. Continued 8 Mn(1)O(1)#1 Mn(1)N(12) O(1)#1Mn(1)N(12) O(1)#1Mn(1)O(3) N(12)Mn(1)O(3)
1 Cu(1)O(9) Cu(1)N(113) Cu(1)O(9)#2 Cu(2)N(112) O(9)Cu(1)N(12) O(9)Cu(1)N(113) O(5)#1Cu(1)N(12) O(9)Cu(2)N(112) N(112)Cu(2)O(1)#3
1.9140(14) 2.0338(16) 2.4477(15) 2.0262(16) 173.74(6) 84.50(6) 88.07(6) 83.83(6) 84.60(6)
Cu(1)N(12) Cu(1)O(5)#1 Cu(2)O(9) Cu(2)O(1)#3 O(9)Cu(1)O(5)#1 N(12)Cu(1)N(113) O(5)#1Cu(1)N(113) O(9)Cu(2)O(1)#3 O(9)Cu(2)O(1)#4
1.9782(16) 1.9730(14) 2.0058(14) 2.3578(14) 97.82(6) 91.02(6) 155.64(6) 95.50(5) 84.50(5)
2 Co(1)O(5) Co(1)N(12) O(5)Co(1)N(12) O(6)Co(1)N(12)
2.0839(12) 2.1126(15) 91.21(5) 85.85(5)
Ni(1)N(12) Ni(1)O(6) N(12)Ni(1)O(5) N(12)Ni(1)O(6)
2.067(3) 2.078(3) 93.07(10) 87.52(11)
Mn(1)O(1)#1 Mn(1)N(3)#2 O(1)#1Mn(1)O(1)#3 O(1)#3Mn(1)O(2) O(1)#1Mn(1)N(3)#2 O(2)Mn(1)N(3)#2 N(3)#2Mn(1)N(3)#5
2.1259(14) 2.2875(17) 94.45(8) 90.10(6) 174.49(6) 89.16(6) 83.59(9)
Cu(1)O(2) Cu(1)N(3)#2 Cu(1)N(2)#3 O(2)Cu(1)O(4)#1 O(2)Cu(1)N(3)#2 N(3)#2Cu(1)O(5) O(4)#1Cu(1)N(2)#3 O(5)Cu(1)N(2)#3
1.924(2) 1.980(3) 2.411(3) 170.69(10) 97.88(11) 172.55(11) 87.53(11) 86.64(10)
Co(1)O(2) Co(1)N(3)#2 Co(1)O(5) O(2)Co(1)O(4)#1 O(4)#1Co(1)N(3)#2 O(4)#1Co(1)N(2)#3 O(2)Co(1)O(5) N(3)#2Co(1)O(5) O(2)Co(1)O(5)#4 N(3)#2Co(1)O(5)#4 O(5)Co(1)O(5)#4
1.992(2) 2.125(2) 2.205(2) 173.26(9) 89.38(9) 88.90(9) 87.52(9) 94.41(9) 85.24(8) 170.02(9) 75.99(9)
Co(1)O(6)
2.0910(12)
O(5)Co(1)O(6)
89.38(5)
3 Ni(1)O(5)
2.071(3)
O(5)Ni(1)O(6)
89.76(11)
4 Mn(1)O(2)
2.1620(14)
O(1)#1Mn(1)O(2) O(2)#4Mn(1)O(2) O(1)#3Mn(1)N(3)#2 O(2)#4Mn(1)N(3)#2
91.71(6) 177.34(8) 90.99(6) 88.86(6)
5 Cu(1)O(4)#1 Cu(1)O(5)
1.950(2) 2.015(2)
O(2)Cu(1)O(5) O(4)#1Cu(1)N(3)#2 O(4)#1Cu(1)O(5) O(2)Cu(1)N(2)#3 N(3)#2Cu(1)N(2)#3
85.38(10) 91.42(11) 85.42(10) 90.50(11) 99.99(11)
Co(1)O(4)#1 Co(1)N(2)#3 Co(1)O(5)#4 O(2)Co(1)N(3)#2 O(2)Co(1)N(2)#3 N(3)#2Co(1)N(2)#3 O(4)#1Co(1)O(5) N(2)#3Co(1)O(5) O(4)#1Co(1)O(5)#4 N(2)#3Co(1)O(5)#4
2.026(2) 2.133(2) 2.230(2) 97.24(9) 91.18(9) 99.78(10) 90.75(8) 165.80(9) 88.02(8) 89.81(9)
Ni(1)O(1) Ni(1)N(2)#3 Ni(1)O(5)#4 O(3)#1Ni(1)N(3)#2 O(3)#1Ni(1)N(2)#3 N(3)#2Ni(1)N(2)#3 O(1)Ni(1)O(5) N(2)#3Ni(1)O(5) O(1)Ni(1)O(5)#4 N(2)#3Ni(1)O(5)#4
2.036(2) 2.110(3) 2.221(2) 98.16(9) 90.65(9) 100.22(10) 91.04(8) 164.86(9) 87.45(8) 89.45(9)
6
7 Ni(1)O(3)#1 Ni(1)N(3)#2 Ni(1)O(5) O(3)#1Ni(1)O(1) O(1)Ni(1)N(3)#2 O(1)Ni(1)N(2)#3 O(3)#1Ni(1)O(5) N(3)#2Ni(1)O(5) O(3)#1Ni(1)O(5)#4 N(3)#2Ni(1)O(5)#4 O(5)Ni(1)O(5)#4
1.990(2) 2.100(3) 2.183(2) 172.27(9) 89.56(9) 88.30(9) 87.97(9) 94.90(9) 84.89(9) 169.78(9) 75.40(9)
2.1206(12) 2.2583(13) 91.78(4) 93.31(3) 87.64(5)
Mn(1)O(1)#2 Mn(1)O(3) O(1)#2Mn(1)N(12) O(1)#2Mn(1)O(3) N(12)#3Mn(1)O(3)
2.1207(12) 2.2621(10) 88.22(4) 86.69(3) 92.36(5)
a Symmetry transformations used to generate equivalent atoms: #1 x, y þ 1, z; #2 x þ 2, y þ 1, z þ 1; #3 x þ 1, y, z þ 1; #4 x þ 2, y þ 1, z for 1. #1 x þ 1, y þ 1, z þ 1; #2 x þ 3/2, y þ 3/2, z þ 2; #3 x, y þ 1, z þ 1/2; #4 x þ 1, y, z þ 3/2; #5 x 1/2, y þ 3/2, z 1/2 for 4. #1 x þ 1/2, y þ 1/2, z; #2 x þ1/2, y þ 1/2, z þ 1/2; #3 x þ 3/2, y þ 1/2, z þ 1/2 for 5. #1 x 1/2, y þ 1/2, z; #2 x 1/2, y þ 5/2, z 1/2; #3 x þ 3/2, y þ 1/2, z þ 3/2; #4 x þ 1, y þ 2, z þ 1 for 6. #1 x þ 1/2, y 1/2, z; #2 x, y þ 1, z 1/2; #3 x þ 2, y, z þ 3/2; #4 x þ 2, y, z þ 1 for 7. #1 x þ 1/2, y þ 3/2, z 1/2; #2 x þ 1/2, y þ 1/2, z þ 3/2; #3 x þ 1, y þ 2, z þ 1 for 8.
μ3-hydroxo group are 3.12, 3.30, and 4.06 Å. The 2D layers are further pillared by HL ligands with mode II to produce a 3D framework (Figure 1c). To further understand the structure of 1, topological analysis by reducing multidimensional structure to simple node-andlinker net was performed. On the basis of the simplification principle,22 HL ligand with mode I and μ3-hydroxo group are both connect two Cu1 and one Cu2, thus can be regarded as 3-connectors, while the one with mode II acts as a 2-connector. The 5-coordinated Cu1 and 6-coordinated Cu2 atoms are considered as 5- and 6-connected nodes, respectively. Hence, the overall structure of 1 is a (3,3,5,6)-connected 4-nodal 3D net with stoichiometry (3-c)2(3-c)2(5-c)2(6-c), as shown in Figure 1d. Topology analysis by TOPOS program23 suggests the Point (Schl€afli) symbol of the net is (4.6.8)2(42.65.83)2(42.66.86.10)(42.6)2. Crystal Structure of [Co(HL)2(H2O)4] 3 3H2O (2) and [Ni(HL)2(H2O)4] 3 3H2O (3). The same space group and similar cell parameters as listed in Table 1 indicate that complexes 2 and 3 are isomorphous and isostructural, so 2 is used for detailed structural description. The results of structure analysis show that 2 consists of neutral centrosymmetric [Co(HL)2(H2O)4] mononuclear unit and free water molecules. Each Co(II) is surrounded by two N atoms of triazolyl groups provided by two HL ligands and four coordinated water O atoms to give a slightly compressed octahedral geometry (Figure 2a). Similar to that in 1, the H2L ligand is partially deprotonated to give the HL form in 2. However, each HL ligand utilizes only one N atom of the triazolyl group to coordinate with one Co(II) atom (Scheme 2, mode III). The mononuclear units of 2 are further linked together by hydrogen bonds to give 3D framework. The hydrogen bonding data are summarized in Supporting Information Table S1. The presence of O3H6 3 3 3 O1#1 (#1: x, y þ 1, z þ 1/2) hydrogen bond leads to the formation of onedimensional (1D) chain (Supporting Information Figure S1), which is connected by O8H9 3 3 3 O2 hydrogen bonds to form a 2D network (Figure 2b). Furthermore, a 3D supramolecular framework is generated by the combination of O7H7 3 3 3 N13#2 (#2: x þ 1, y, z þ 1/2) and O7H8 3 3 3 O8#3 (#3: x þ 1/2, y þ 1/2, z) hydrogen bonds (Figure 2c). A local view of the hydrogen bonds around the free water molecules is exhibited in Supporting Information Figure S2. The O 3 3 3 O distances between the coordinated water molecules and carboxylate or free water molecules range from 2.728 to 2.825 Å (Supporting Information Table S1) and indicate the existence of OH 3 3 3 O hydrogen 1904
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Figure 1. (a) Coordination environment of Cu(II) atoms in 1 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. (b) 2D layer structure of 1: blue, Cu1; dark-blue, Cu2. (c) 3D framework of 1: green, the HL ligands of mode II. (d) Schematic representation of the (3,3,5,6)-connected 4-nodal 3D network of 1 with (4.6.8)2(42.65.83)2(42.66.86.10)(42.6)2 topology: blue, Cu1; dark-blue, Cu2; orange, HL ligands of mode I; red, μ3-hydroxo groups.
Scheme 2. Coordination Modes of HL/L2 Appeared in Complexes 18
bonds although the H atoms of coordinated water molecules could not be located in 2. Crystal Structure of [Mn(HL)2]n (4). When MnCl2 3 4H2O was used to react with H2L under pH 4, complex 4 with different structure was obtained. In 4, each Mn(II) atom is coordinated by four O and two N atoms from six different HL ligands to form a slightly distorted octahedral coordination geometry, as illustrated in Figure 3a. Different from the coordination modes of HL in
13, each HL ligand in 4 connects three metal atoms using its two O atoms from a μ2-η1:η1 carboxylate group and one N atom of the triazolyl group (Scheme 2, mode IV). If one of the MnO linkage from μ2-η1:η1 carboxylate group of HL ligand is ignored, a (4,4) grid 2D network with Mn 3 3 3 Mn distance of 12.15 Å is obtained (Figure 3b). The 2D networks are further linked by the just neglected MnO linkage to generate a 3D framework (Figure 3c). The topological analysis was carried out to get insight of the structure of 4. As mentioned above, each HL ligand is neighbored by three Mn(II) atoms which can be viewed as a 3-connector. Meanwhile, each Mn(II) atom can be regarded as a 6-connected node because it links six HL ligands. Thus, the resulting structure of 4 is a (3,6)-connected binodal 3D net with stoichiometry of (3-c)2(6-c), as shown in Figure 3d. The Point (Schl€afli) symbol for the net is (42.6)2(44.62.88.10) calculated by TOPOS program,23 which has been referred by O’Keeffe and Wells to the ant (anatase) notation.24 Crystal Structure of {[Cu2(L)2(μ-OH2)2] 3 3H2O}n (5), {[Co2(L)2(μ-OH2)2] 3 3H2O}n (6), and {[Ni2(L)2(μ-OH2)2] 3 3H2O}n (7). When the pH value of reaction system was changed from 4 to 7, complexes 58 with complete deprotonated L2 ligand were obtained. Single crystal X-ray diffraction analysis revealed that 57 have the same framework structure (Table 1), thus only the structure of 5 is discussed here in detail. The asymmetric unit of 5 contains one Cu(II) atom, one L2 ligand, one coordinated and one and half free water molecules. As depicted in Figure 4a, each Cu(II) atom adopts six-coordinated octahedral geometry formed by two N atoms of triazolyl group from two distinct L2 ligands, 1905
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Figure 2. (a) Coordination environment of Co(II) atom in 2 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms and free water molecules are omitted for clarity. (b) 2D layer structure of 2 with the lattice water molecules fixed by hydrogen bonds. (c) 3D framework of 2: different colors for different 2D layers.
four O atoms from two different L2 ligands and two coordinated water molecules. It is notable that the Cu1O5D distance of 2.60 Å is longer than the ones in the previously reported Cu(II) complexes25 and indicates the weak coordination interaction between Cu1 and O5D. However, the corresponding bond distances in 6 and 7 are 2.230(2) and 2.221(2) Å, similar to other related CoO and NiO distances.26,27 Each L2 ligand in turn connects four Cu(II) atoms using its two N atoms of the triazolyl group and two O atoms from two μ1-η1:η0 monodentate carboxylate groups (Scheme 2, mode V). The alternate bridging coordinated water molecules and triazolyl groups from L2 ligands in 5 connect Cu(II) atoms to form a 1D chain (Supporting Information Figure S3). There are two different kinds of rings in the 1D chain: one is formed by two coordinated water molecules and two Cu(II) atoms with a Cu 3 3 3 Cu distance of 3.69 Å and the other one consists of four coordinated N atoms from two triazolyl groups and two Cu(II) atoms with a Cu 3 3 3 Cu separation of 4.13 Å. Then the 1D chains are linked together by one of the two μ1-η1:η0 carboxylate groups from L2 ligands to form a 2D network (Figure 4b), which is further joined together by another μ1-η1:η0 carboxylate group to generate the final 3D framework of 5 as illustrated in Figure 4c. From topological view, each 2-connected bridging coordinated water molecule can be regarded as a linear linker. Each L2 ligand connects four Cu(II) atoms and can be treated as a 4-connector. Each Cu(II) atom can
be regarded as 5-connected node because it links four L2 ligands and one Cu(II) atom though the water bridges. Therefore, the overall structure of 5 is a (4,5)-connected binodal 3D net with stoichiometry (4-c)(5-c), as shown in Figure 4d. The Point (Schl€afli) symbol for the (4,5)-connected net is (42.52.62)(42.53.62.73) calculated by TOPOS program.23 Crystal Structure of {[Mn(L)(μ-OH2)] 3 2H2O}n (8). The asymmetric unit of 8 contains one Mn(II) atom sitting on an inversion center, half L2 ligand, half coordinated and one free water molecules. As shown in Figure 5a, each Mn(II) atom displays a slightly distorted octahedral coordination geometry formed by two N atoms from two L2 ligands and four O atoms from two L2 ligands and two coordinated water molecules. The L2 ligand in 8 shows the same coordination fashion as that in 57 (Scheme 2, mode V). However, the structure of 8 is different from that of 57. If the connections through the carboxylate groups are ignored, the triazolyl groups and coordinated water molecules connect Mn(II) atoms to form a 1D chain (Figure 5b). Only one kind of ring formed by one bridging coordinated water molecule, two N atoms from one triazolyl group and two Mn(II) atoms is found in the 1D chain with a Mn 3 3 3 Mn distance of 3.85 Å. Furthermore, the 1D chains are linked together by the linkages of carboxylate groups to result in the final 3D framework of 8 (Figure 5c). The topological analysis was also carried out for 8. The coordinated water molecule is 1906
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Figure 3. (a) Coordination environment of Mn(II) atom in 4 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted for clarity. (b) 2D layer structure of 4. (c) 3D framework of 4: different colors for different 2D layers. (d) Schematic representation of the 3D ant net of 4 with (42.6)2(44.62.88.10) topology: pink, Mn(II); orange, L2 ligands.
2-connector which can be regarded as linear linker in the topological analysis, and each L2 ligand is a 4-connector because one L2 links four Mn(II) atoms. Each Mn(II) atom is attached to two Mn(II) atoms though the water bridges and four L2 ligands, and thus can be regarded as 6-connected node. On the basis of the simplification, complex 8 possesses a binodal (4,6)-connected binodal 3D net with stoichiometry (4-c)(6-c) as shown in Figure 5d. Topology analysis by TOPOS program23 suggests the (4,6)-connected net with the Point (Schl€afli) symbol (3.54.6)(32.56.66.9). Synthesis of the Complexes and Comparison of the Structures. Complexes 18 were readily prepared by reactions of H2L ligand with corresponding metal chloride under different pH value and characterized by elemental analysis, IR and X-ray diffraction as described above. The phase purity of bulk products of the complexes was further confirmed by PXRD, and each PXRD pattern of the as-synthesized sample is well consistent with the simulated one (Supporting Information Figure S4). The results of structural analysis indicate that the complexes have diverse structures from discrete mononuclear to polymeric 3D frameworks with different topologies. The different structure of 14 as well as 58 is caused by different metal center in each complex because 14 (58) were prepared under the same reaction temperature and pH but different metal chloride. While the difference between 14 and 58 is ascribed to the different reaction pH leading to the partial (in 14) and complete deprotonation (in 58) of the H2L ligand (vide supra). The results not only imply that the metal center and reaction pH are important in determining the structure of the complexes but also
show that the triazolyl- and carboxylate-containing ligand is versatile in construction of metalorganic frameworks due to the variable coordination mode of the triazolyl and carboxylate groups (Scheme 2, modes IV). Thermal Stability of the Complexes. The thermal stability of 18 was examined by thermogravimetric analysis (TGA) in the N2 atmosphere from 25750 °C, and the results are shown in Supporting Information Figure S5. No obvious weight losses were found for 1 and 4 before the decomposition of the frameworks occurred at about 320 and 400 °C, respectively, which are in good agreement with the results of their crystal structure. For 2 and 3, weight losses of 18.83% and 19.43% were observed in the temperature range of ca. 50200 °C, which correspond to the liberation of the free and coordinated water molecules (calcd 19.42% for 2 and 19.43% for 3), respectively, and further weight losses were observed at about 300 °C, owing to the collapse of the frameworks of 2 and 3. Complex 5 shows a weight loss of 12.80% in the temperature range of 120180 °C corresponding to the release of free and coordinated water molecules (calcd 13.26%) and the decomposition of the residue occurred at 300 °C. The TGA curves for 6 and 7 display initial weight losses of 13.35% and 13.09% from 200 °C, respectively, suggesting the loss of the free and coordinated water molecules (calcd 13.44% for 6 and 13.45% for 7), and the frameworks of 6 and 7 are stable up to about 350 °C. For 8, a total weight loss of 15.69% in the temperature range of 120200 °C consists of the corresponding calculated values of 15.89% due to the loss of free and coordinated water molecules, and the residue is stable up to about 300 °C. 1907
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Figure 4. (a) Coordination environment of Cu(II) atom in 5 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms and free water molecules are omitted for clarity. (b) 2D layer structure of 5. (c) 3D framework of 5: different colors for different 2D layers. (d) Schematic representation of the (4,5)-connected binodal 3-D framework of 5 with (42.52.62)(42.53.62.73) topology: blue, Cu(II); orange, L2 ligands.
Magnetic Properties of the Complexes. The metal atoms of Cu(II), Co(II), Ni(II) and Mn(II) in 1 and 48 are bridged by OH/H2O and/or HL/L2 ligands which may mediate magnetic interactions. Thus the magnetic properties of complexes 1 and 48 were investigated over the temperature range of 1.8300 K with a 2000 Oe applied magnetic field. The magnetic behaviors of 1 and 48 in the form of χM and χMT vs T are depicted in Figure 6af. For 1, the χMT value is 1.60 emu K mol1 at 300 K, which is higher than the value expected for three uncoupled Cu(II) atoms (1.13 emu K mol1, g = 2.0). As the temperature is lowered, the χMT value decreases continuously to a minimum at 7 K and finally increases slightly. Meanwhile, the χM value increases monotonically (Figure 6a). The data above 110 K follow the CurieWeiss law with C = 3.30 emu K mol1 and θ = 377.77 K, indicating antiferromagnetic interactions between the neighboring Cu(II) centers (Supporting Information Figure S6). As described in the crystal structure, the magnetostucture for 1 can be considered as 1D chain in which there are three different magnetic interactions between the Cu(II) atoms: double hydroxo bridges, hydroxo-triazolyl mixed-bridges, and single hydroxo bridge as illustrated in Supporting Information Figure S7. It is difficult to estimate the parameters because of the lack of an appropriate model for such a system, but qualitative analysis is given on the nature of the interactions based on the known magnetostructural information for related systems. Reported studies show that the nature and strength of the CuOCu
exchange are mainly affected by the CuOCu bond angle (θ): the CuOCu pathway with θ larger than 98° mostly transfers antiferromagnetic interactions (J < 0), while ferromagnetism appears for smaller values of θ.28 In 1, θ = 90.6°, ferromagnetic behavior is expected for the double hydroxo-bridged interactions, as demonstrated in the reported complexes, for example, [Cu4(μ5-btc)2(μ3-OH)2(μ4-btre)] 3 2H2O (H3btc = benzene-1,3,5tricarboxylic acid and btre = 1,2-bis(1,2,4-triazol-4-yl)ethane),29 in which the CuOCu bridging angles is 96.5°, has the ferromagnetic coupling between the two Cu(II) atoms. The linkage between Cu and Cu via single hydroxo bridges always induces antiferromagnetic coupling, for example, in complex [Cu2(terpy)2(μ-OH)(H2O)(ClO4)3] (terpy = 2,20 ;60 ,200 -terpyridine), the single hydroxo group bridging two Cu(II) atoms shows strong antiferromagnetic exchange interaction.30 The superexchange through hydroxo and triazolyl bridges also leads to antiferromagnetic coupling such as in [Cu4(μ5-btc)2(μ3-OH)2(μ4-btre)] 3 2H2O.29 As shown in Figure 6b, the χMT value of 4 at 300 K is about 4.17 emu K mol1, slightly lower than the value expected for single magnetically isolated Mn(II) atom (4.38 emu K mol1, g = 2.0). As the sample is cooled from room temperature, the χMT value decreases continuously, while the χM value increases to a maximum at about 9 K and then decreases upon further cooling. The data above 24 K follow the CurieWeiss law with C = 4.35 emu K mol1 and θ = 11.62 K (Supporting Information Figure S8), indicating antiferromagnetic coupling interactions between the neighboring Mn(II) centers. According to the structure of 4, 1908
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Figure 5. (a) Coordination environment of Mn(II) in 8 with the ellipsoids drawn at the 30% probability level. The hydrogen atoms and free water molecules are omitted for clarity. (b) 2D layer structure of 8. (c) 3D framework of 8: different colors for different 2D layers. (d) Schematic representation of the (4,6)-connected binodal 3-D network of 8 with (3.54.6)(32.56.66.9) topology: pink, Mn(II); orange, L2 ligands.
the system can magnetically be treated as an infinite uniform chain in which the magnetic coupling is mediated through the double synsyn carboxylate bridges. Consequently, the interaction (J) through the double bridge can be evaluated by the conventional equation derived by Fisher for a uniform chain of classical spins based on the Hamiltonian H = J∑SiSiþ1:31 χM T ¼ ½Ng 2 β2 SðS þ 1Þ=3k=½ð1 þ uÞ=ð1 uÞ where u is the Langevin function defined as u = coth[JS(S þ 1)/ kT] kT/[JS(S þ 1)] with S = 5/2. The best fit led to g = 2.00, J = 1.41 cm1, and R = 4.5 104 for 4. The results confirm the antiferromagnetic interactions through the double synsyn carboxylate bridges, as revealed by experimental and theoretical studies.32 For 5, the room temperature value of χMT is 0.89 emu K mol1, which is higher than the expected value for two uncoupled Cu(II) atoms (0.75 emu K mol1, g = 2.0) (Figure 6c). Upon cooling, the χMT is almost constant until near 30 K from where it gradually increases. The value of χM is 0.0030 emu mol1 at room temperature, and it increases smoothly to a maximum of 0.53 emu mol1 at 2 K. The data follow the CurieWeiss law with C = 0.89 emu K mol1 and θ = þ0.27 K, indicating the presence of weak ferromagnetic interactions (Supporting Information Figure S9). According to the structure, the alternate bridging water and triazolyl groups offer two different pathways. The symmetrical double water bridges with CuOCu bond angle of 104.3° always induces antiferromagnetic coupling.33 For the double triazolyl bridges, the correlation between the experimental exchange constants and the CuNNCu torsion
angles indicates that the complexes are generally ferromagnetic for large torsion angles. For example, in [Cu(hyetrz)3](CF3SO3)2 3 H2O [hyetrz = 4-(20 -hydroxyethyl)-1,2, 4-triazole] with the CuNNCu torsion angle of 20° shows a ferromagnetic coupling.34 In 5, the CuNNCu torsion angle is up to 41.5° and indicates the ferromagnetic interactions through the double triazolyl groups. Thus, the system can magnetically be treated as an alternating AFF chain of classical spins based on the Hamiltonian H = ∑(JAFS2iS2iþ1þJFS2iS2i1):35 χM T ¼ ðNg 2 β2 =2kÞFðR, xÞ FðR, xÞ ¼ ðA1 x4 þ A2 x3 þ A3 x2 þ A4 xÞ=ðx4 þ A5 x3 þ A6 x2 þ A7 x þ A8 Þ R ¼ JF =jJAF j;
x ¼ kT=jJAF j;
An ¼
i¼3
∑ RniRi
i¼0
where Ri denotes the ith power of R, i.e., Ri = (JF/|JAF|)i. The best fit led to g = 2.18, JF = 0.62 cm1, JAF = 0.27 cm1, and R = 3.2 106 for 5. For 6, the χMT value at 300 K is 5.94 emu K mol1, higher than the spin-only value for two isolated Co(II) atoms (3.75 emu K mol1, g = 2.0). Upon cooling, the χMT value decreases smoothly to reach a value of 0.13 emu K mol1 at 1.8 K, while the χM increases continuously until it reaches a maximum value of 0.14 emu mol1 at 12.0 K and further decreases to 0.07 emu mol1 1909
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Figure 6. Temperature dependences of magnetic susceptibility χM and χMT for 1 (a), 4 (b), 58 (cf).
at 1.8 K (Figure 6d). The data above 20 K follow the CurieWeiss law with C = 6.61 emu K mol1 and θ = 29.38 K (Supporting Information Figure S10). Such behavior reveals the presence of antiferromagnetic interaction between the Co(II) atoms. The magnetic structure of 6 is best described as alternating chain with Co(II) atoms linked by alternate water and triazolyl bridges. The relevant parameters could not be evaluated because of the absence of suitable model for such a system with alternating bridges, but some tentative comments can be made on the nature of the magnetic interactions. For the double water bridges, the antiferromagnetic interaction is found in the reported complexes such as [Co2(O2CFcCO2)2(2,20 -bpy)2(μ-OH2)2] 3 CH3OH 3 2H2O [Fc = (η5-C5H4)Fe(η5-C5H4)],36 [Co(dpa)(C4O4)(μ-OH2)] (dpa = 2,20 -dipyridylamine),37 and [Co2(μ-OH2)2(H2O)8][H2(TCTTF)]2 3 2H2O [H4(TC-TTF) = tetra(carboxyl)-tetrathiafulvalene].38 For the double triazolyl bridges, it should mediate
antiferromagnetic coupling, as demonstrated in 6 and previous reported complexes such as [Co2(altrz)4(H2O)(NCS)4] 3 2(H2O)39 and [Co2(atrz)3(H2O)4(tp)2] 3 11H2O (atrz = 4-aminotriazole and tp = terephthalate).40 For 7, the room temperature χMT value of 1.94 emu K mol1 is lower than the expected one for two magnetically isolated Ni(II) atoms (2.00 emu K mol1, g = 2.0). As the temperature is lowered, the χMT value decreases smoothly to a value of 0.13 emu K mol1 at 1.8 K, while χM increases smoothly to reach 0.40 emu mol1 at about 1.8 K (Figure 6e). The data above 14 K follow the CurieWeiss law with C = 2.02 emu K mol1 and θ = 9.50 K (Supporting Information Figure S11). The above features indicate that antiferromagnetic interactions are operative in 7. Considering that the chain in 7 actually contains two structurally different sets of double water and triazolyl bridges alternating in the ABAB sequence, it is best described as a 1D Heisenberg system with the 1910
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Hamiltonian H = J1∑(S2iS2iþ1þRS2iS2i1):41 χM T ¼ ð2Ng 2 β2 =3J1 ÞFðR, xÞ FðR, xÞ ¼ ðA1 x2 þ A2 x þ A3 Þ=ðx3 þ A4 x2 þ A5 x þ A6 Þ J2 ¼ RJ1 ;
x ¼ kT=jJ1 j;
An ¼
’ ACKNOWLEDGMENT This work was financially supported by the National Natural Science Foundation of China (grant no. 20731004 and 21021062) and the National Basic Research Program of China (grant no. 2007CB925103 and 2010CB923303). We thank Prof. You Song and Dr. Tian-Wei Wang for discussion and magnetic measurements.
i¼2
Rni Ri ∑ i¼0
where Ri denotes the ith power of R, i.e., Ri = (J2/J1)i. By applying the expression for the AF/AF case with the R > 0.5, a good quality fit with optimized coupling parameters g = 2.31, J1 = 3.14 cm1, and J2 = 4.27 cm1 and R = 5.0 104 are obtained. The J1 and J2 values confirm the antiferromagnetic interactions through the alternating double bridges, as have been observed in the reported complexes.37,39,42 For 8, the room temperature value of χMT is 4.00 emu K mol1 at 300 K, which is lower than the expected value for an uncoupled Mn(II) atoms (4.38 emu K mol1, g = 2.0). As the temperature is lowered, the χMT value decreases continuously, while the χM value first increases to a maximum at 14 K, then decreases until 6 K, and finally increases slightly again (Figure 6f). The data above 40 K follow the CurieWeiss law with C = 4.38 emu K mol1 and θ = 26.40 K (Supporting Information Figure S12). The magnetic behavior suggests antiferromagnetic coupling between adjacent Mn(II) atoms through water and triazolyl mixed-bridges, except the slight increase of χM below 6 K, which could be attributed to the paramagnetic impurity, a common occurrence in magnetic studies and known as a Curie tail.36 The magnetic structure of 8 can be treated as a system of uniform chain and was fitted using the similar equations used for 4 except including a paramagnetic impurity (F). The best fit led to parameters g = 1.99, J = 2.62 cm1, F = 0.01, and R = 6.0 105 for 8.
’ CONCLUSIONS Eight new coordination complexes with diverse structures were successfully constructed from 5-(4H-1,2,4-triazol-4-yl)benzene-1,3-dicarboxylic acid (H2L) ligand and divalent metal salts by hydrothermal method under different reaction pH values. The results of present work further illustrate that the multifunctional ligands incorporating with both heterocyclic and aromatic carboxylate groups are effective building blocks in construction of coordination frameworks because the multicarboxylate groups can have versatile coordination modes and the triazolyl group exhibits strong coordination ability in monodentate or bidentate mode with metal centers. ’ ASSOCIATED CONTENT
bS Supporting Information. X-ray crystallographic file in CIF format, hydrogen bonding data, crystal structures, PXRD, TGA, and magnetic properties. This material is available free of charge via the Internet at http://pubs.acs.org. ’ AUTHOR INFORMATION Corresponding Author
*Phone: 86 25 8359 3485. Fax: 86 25 8331 4502. E-mail: sunwy@ nju.edu.cn.
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