Multidimensional Networks Constructed with Isomeric

Complex 1 exhibits a 2-D herringbone architecture with mononuclear building ... bonds between the H2biim and carboxylate oxygen atoms into 2-D network...
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Multidimensional Networks Constructed with Isomeric Benzenedicarboxylates and 2,2′-Biimidazole Based on Mono-, Bi-, and Trinuclear Units Bao-Hui Ye,* Bing-Bing Ding, Yan-Qin Weng, and Xiao-Ming Chen

CRYSTAL GROWTH & DESIGN 2005 VOL. 5, NO. 2 801-806

School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China Received July 28, 2004;

Revised Manuscript Received October 4, 2004

ABSTRACT: Three new complexes of [Co(H2biim)2(1,2-bdc)] (1), [Cd(H2biim)(1,3-bdc)]2 (2), and [Cd3(H2biim)2(1,4bdc)3]‚2H2O (3) (bdc ) benzenedicarboxylate, H2biim ) 2,2′-biimidazole) have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 exhibits a 2-D herringbone architecture with mononuclear building blocks assembled via a robust hydrogen-bonded synthon R22(9). The homo- and heterochiral assemblies were observed in 1 between the H2biim ligand and carboxylate group via single and double hydrogen-bonded synthons R22(9). Complex 2 is a ribbonlike polymer based on a binuclear unit, and the ribbons are alternately decorated by H2biim ligands on both sides and further packed through intercalation of the lateral H2biim ligands and hydrogen bonds between the H2biim and carboxylate oxygen atoms into 2-D networks. These layers extend into a 3-D architecture via π-π stacking interactions. Complex 3 is a 3-D coordination polymer with a R-Po net topology based on linear trinuclear {Cd3O14N4} clusters. The results indicate that isomeric benzenedicarboxylates give structural diversity in the presence of auxiliary ligand H2biim, providing a potential tool for crystal engineering. Introduction Construction of coordination polymers is experiencing great growth in crystal engineering due to their structural diversities and potential application as new materials.1 The control of dimensionality is still a major challenge in the design and synthesis of organicinorganic frameworks because the final structure is frequently modulated by various factors such as medium, temperature, metal-ligand ratio, template, and counterion.1 In the self-assembled process, the shapes of the organic ligands are very important in the control of the frameworks. Therefore, through the choice of organic ligands and metal ions, it is possible to develop a targeted architecture. Benzenedicarboxylate (bdc) anions having three isomers of 1,2-bdc, 1,3-bdc, and 1,4bdc have been widely employed in the construction of coordination polymers with or without the auxiliary ligands.2-4 On the other hand, a robust heteromeric hydrogen-bonded synthon R22(9) has been found between the carboxylate and 2,2′-biimidazole (H2biim) ligands in the solid state.5 This interaction should be particularly strong, since the N-H‚‚‚O unit is nearly linear (∼165°) and the N‚‚‚O separation (2.68 Å) is close to the lower limit of the accepted range.6 In this work, we chose bdc isomers and H2biim as mixed ligands based on the following considerations: (i) bdc is a kind of polydentate ligand that may act as a bridge to connect metal ions into multidimensional structures via various coordination modes; (ii) bdc anions have three structural isomers with different angles between the two carboxylate groups (Scheme 1), which may exhibit different geometric effects in the construction of coordination polymers; (iii) the H2biim ligand not only coordinates to metal ions in the chelate mode but also provides two noncoordinating NH groups for formation of robust * To whom correspondence should be addressed. Fax: (86)-2084112245. Tel: (86)-20-84113986. E-mail: [email protected].

Scheme 1. Presentation of the Isomers Structures of Benzenedicarboxylate Ligands and Their Possible Assembly with the 2,2′-Biimidazole Ligand via Heteromeric Hydrogen-Bonded Synthon R22(9)

heteromeric hydrogen bonds with the neighboring carboxylate group in the R22(9) synthon, extending into multidimensional networks in definite directions. In additional, to the best of our knowledge, the mixed complexes of bdc and H2biim are relatively rare.5d The structures constructed by such hydrogen-bonded donor ligands H2biim in the presence of metal ions and bdc ligands may be markedly different from those of the pure π-π interaction ligands such as 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen). In our preliminary studies of [Zn(H2biim)2(H2O)2](MeCO2)2‚(HOCH2CH2OH), the two H2biim ligands arranged trans to each other on the equatorial plane and the two acetate anions were attached to the four N-H

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Table 1. Crystal Data and Structure Refinement for 1-3 complex molecular formula formula weight crystal system space group a/Å b/Å c/Å a/° β/° γ/° V/Å3 Z Fcalc (g cm-3) µ (cm-1) reflections collected independent reflections data/restraints/parameters R indices [I > 2σ(I)] ∆Fmax/∆Fmin (eÅ-3) a

1 C20H16N8O4Co 491.34 monoclinic P21/n (No. 14) 8.4861(8) 11.5665(11) 20.602(2) 94.737(2) 2015.3(3) 4 1.619 0.900 10415 3974 3453/0/298 R1 ) 0.0335, wR2 ) 0.0912 0.36 and -0.20

2 C28H20N8O8Cd2 821.34 triclinic P1 h (No. 2) 7.9259(6) 9.0991(7) 10.0530(7) 90.4310(10) 100.3980(10) 105.8980(10) 684.58(9) 1 1.992 1.623 5933 3068 2897/0/208 R1 ) 0.0294, wR2 ) 0.0686 0.81 and - 0.44

3 C36H28N8O14Cd3 1133.86 triclinic P1 h (No. 2) 9.9002(8) 10.4185(8) 11.5481(9) 113.5080(10) 97.7890(10) 110.2960(10) 971.12(13) 1 1.939 1.708 8360 4335 3949/0/294 R1 ) 0.0228, wR2 ) 0.0567 0.64 and -0.31

R1 ) ∑||Fo| - |Fc||/∑|Fo|. b wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]1/2.

groups from the two coordinated H2biim of the building block [Zn(H2biim)2(H2O)2]2+ via strong N-H‚‚‚O hydrogen bonds.7 This implies that when the benzenedicarboxylates were employed polymeric structures should be constructed (Scheme 1). Using this strategy, we report herein the syntheses and structural characterization of three new complexes of [Co(H2biim)2(1,2-bdc)] (1), [Cd(H2biim)(1,3-bdc)]2 (2), and [Cd3(H2biim)2(1,4-bdc)3]‚ 2H2O (3). They consist of mono-, bi-, and trinuclear structural units, respectively, which are further extended into 2-D and 3-D networks via supramolecular interactions. Experimental Section Materials and Methods. The reagents and solvents employed were commercially available and used as received without further purification. The C, H, and N microanalyses were carried out with a Vario EL elemental analyzer. The FTIR spectra were recorded from KBr pellets in the range 4000400 cm-1 on a Bruker-EQUINOX 55 FT-IR spectrometer. 1H NMR spectra were recorded on a Varian 300 MHz spectrometer at 25 °C. Synthesis of H2biim. H2biim ligand was synthesized in accordance with the published procedure.8 Yield, 32%. Anal. Calcd. for C6H6N4: C, 53.73; H, 4.48; N, 41.79. Found: C, 53.41; H, 4.24; N, 41.56%. FT-IR data (cm-1): 3143 (m), 3074 (m), 3001 (s), 2896 (s), 2806 (s), 1546 (s), 1436 (m), 1405 (vs), 1333 (s), 1217 (m), 1105 (vs), 939 (s), 888 (m), 763 (m), 748 (s), 690 (m). 1H NMR data (DMSO-d6, ppm): 7.06 (C-H), 3.34 (N-H). Synthesis of [Co(H2biim)2(1,2-bdc)] (1). CoCl2‚6H2O (0.136 g, 0.5 mmol), H2biim (0.134 g, 1 mmol) and water (3 mL) were added to an aqueous solution (5 mL) containing sodium 1,2-benzenedicarboxylate (0.105 g, 0.5 mmol). The resulting mixture was adjusted to pH ≈ 6 with dilute hydrochloric acid, further stirred for 15 min in air, and then transferred and sealed in a 16-mL Teflon-lined reactor, which was heated at 170 °C for 4 days and then cooled to room temperature at a rate of 5 °C h-1. Orange product was obtained and washed with deionized water in 35% yield. Anal. Calcd. for C20H16N8O4Co 1 (Mr ) 491.34): C, 48.84; H, 3.26; N, 22.80. Found: C, 48.69; H, 3.37; N, 22.81%. FT-IR (KBr, cm-1): 3147-2614 (br, m), 1556 (s), 1485 (m), 1427 (m), 1381 (vs), 1124 (m), 994 (m), 744 (m), 693 (m). Synthesis of [Cd(H2biim)(1,3-bdc)]2 (2) and [Cd3(H2biim)2(1,4-bdc)3]‚2H2O (3). The complexes were synthesized by a similar procedure for complex 1 in 36-40% yields. Anal. Calcd. for C28H20N8O8Cd2 2 (Mr ) 821.34): C, 40.95; H, 2.45; N, 13.64. Found: C, 40.79; H, 2.14; N, 13.31%. FT-IR

(KBr, cm-1): 3347-2714 (br, m), 1560 (s), 1495 (m), 1430 (m), 1385 (vs), 1134 (m), 992 (m), 741 (m), 695 (m). Anal. Calcd. for C36H28N8O14Cd3 3 (Mr ) 1133.86): C, 38.10; H, 2.47; N, 9.88. Found: C, 38.45; H, 2.34; N, 9.72%. FT-IR (KBr, cm-1): 3407-2556 (br, m), 1566 (s), 1526 (m), 1439 (m), 1123 (m), 993 (m), 812 (m), 766 (m), 689 (m), 504 (m). X-ray Crystallography. Diffraction intensities for the complexes 1-3 were collected at 293 K on a Bruker Smart Apex CCD diffractometer with graphite-monochromated MoKR radiation (λ ) 0.71073 Å). Absorption corrections were applied using SADABS.9 The structures were solved with direct methods and refined with the full-matrix least-squares technique using the SHELXS-97 and SHELXL-97 programs, respectively.10,11 Anisotropic thermal parameters were applied to all non-hydrogen atoms. The organic hydrogen atoms were generated geometrically (C-H 0.96 Å); the aqueous hydrogen atoms were located from difference maps and refined with isotropic temperature factors. Analytical expressions of neutralatom scattering factors were employed, and anomalous dispersion corrections were incorporated. In complex 3, the lattice water molecule was disordered over two positions and refined isotropically with occupation factors of 0.8 and 0.2, respectively. Crystal data as well as details of data collection and refinement for the complexes are summarized in Table 1. Selected bond distances and bond angles are listed in Table 2. The hydrogen bonds are given in Table 3.

Results and Discussion Syntheses. The bdc anions such as 1,2-bdc, 1,3-bdc, and 1,4-bdc possess three different shapes (Scheme 1), which may play a crucial role in the construction of coordination polymers. These ligands are able to connect metal centers in various manners, for example, linking the metal centers into either infinite chains or multidimensional structures.2-5 Obviously, when the H2biim ligand was introduced as a co-ligand of bdc in the presence of metal ions, interesting inorganic-organic hybrid frameworks may be produced. Indeed, complexes 1-3 were obtained by the reaction of metal salts, H2biim, and bdc ligands under hydrothermal conditions, in which complex 1 has a 0-D motif, 2 is a helical ribbon, and 3 is a 3-D coordination polymer constructed by mono-, bi-, and trinuclear units, respectively. These may be attributed to the different shapes of the bdc ligands. The 1,3-bdc and 1,4-bdc ligands with large angles (120° and 180°) between the two carboxylate groups, in comparison with the 1,2-bdc ligand, favor the formation

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Table 2. Selected Bond Lengths (Å) and Bond Angles (°) of 1-3a 1 Co-O(1) Co-O(3) Co-N(1) O(1)-Co-O(3) O(1)-Co-N(3) O(1)-Co-N(7) O(3)-Co-N(3) O(3)-Co-N(7) N(1)-Co-N(5) N(3)-Co-N(5) N(5)-Co-N(7)

2.160(2) 2.122(2) 2.196(2) 81.90(6) 167.44(6) 97.13(6) 86.41(6) 97.71(6) 89.19(6) 104.87(7) 77.86(6)

Co-N(3) Co-N(5) Co-N(7) O(1)-Co-N(1) O(1)-Co-N(5) O(3)-Co-N(1) O(3)-Co-N(5) N(1)-Co-N(3) N(1)-Co-N(7) N(3)-Co-N(7)

Cd(1)-N(1) Cd(1)-O(1) Cd(1)-O(4b) O(1)-Cd(1)-O(2) O(1)-Cd(1)-N(3) O(1)-Cd(1)-O(3c) O(2)-Cd(1)-N(3) O(2)-Cd(1)-O(3c) O(4b)-Cd(1)-N(1) O(4b)-Cd(1)-N(3) O(4b)-Cd(1)-O(3c)

2 2.344(3) 2.305(3) 2.302(2) 53.7(1) 130.4(1) 84.9(1) 114.9(1) 105.4(1) 145.5(1) 84.3(1) 87.9(1)

Cd(1)-O(1) Cd(1)-O(5) Cd(1)-N(1) Cd(2)-O(2) Cd(2)-O(6) O(1)-Cd(1)-O(5) O(1)-Cd(1)-N(1) O(4)-Cd(1)-O(5) O(4)-Cd(1)-N(1) O(5)-Cd(1)-O(6) O(5)-Cd(1)-N(3) O(6)-Cd(1)-N(3) O(2)-Cd(2)-O(3) O(2)-Cd(2)-O(3b) O(3)-Cd(2)-O(6) O(3)-Cd(2)-O(6b) Cd(1)-O(6)-Cd(2)

2.208(2) 2.590(2) 2.376(2) 2.354(2) 2.340(2) 91.8(1) 159.9(1) 150.4(1) 92.0(1) 52.8(1) 90.3(1) 142.1(1) 87.1(1) 92.9(1) 92.8(1) 87.2(1) 103.6(1)

2.116(2) 2.118(2) 2.217(2) 98.67(6) 87.20(6) 98.11(6) 167.66(6) 78.39(6) 159.01(6) 88.94(6)

Cd(1)-N(3) 2.317(2) Cd(1)-O(2) 2.401(4) Cd(1)-O(3a) 2.314(2) O(1)-Cd(1)-N(1) 83.6(1) O(1)-Cd(1)-O(4b) 130.7(1) O(2)-Cd(1)-N(1) 130.7(1) O(2)-Cd(1)-O(4b) 82.0(1) N(1)-Cd(1)-N(3) 72.3(1) O(3c)-Cd(1)-N(1) 92.4(1) O(3c)-Cd(1)-N(3) 137.3(1)

3 Cd(1)-O(4) 2.187(2) Cd(1)-O(6) 2.315(2) Cd(1)-N(3) 2.276(2) Cd(2)-O(3) 2.194(2) O(1)-Cd(1)-O(4) 102.4(1) O(1)-Cd(1)-O(6) 100.7(1) O(1)-Cd(1)-N(3) 87.2(1) O(4)-Cd(1)-O(6) 98.6(1) O(4)-Cd(1)-N(3) 116.0(1) O(5)-Cd(1)-N(1) 82.2(1) O(6)-Cd(1)-N(1) 90.9(1) N(1)-Cd(1)-N(3) 73.7(1) O(2)-Cd(2)-O(6) 94.2(1) O(2)-Cd(2)-O(6b) 85.8(1) O(2b)-Cd(2)-O(3) 92.9(1) O(2b)-Cd(2)-O(6) 85.8(1)

a Symmetry codes for 2: b, x, y, 1 + z; c, 1 - x, 1 - y, 1 - z; for 3: b, 2 - x, 1 - y, -z.

of coordination polymers. Using the proper choice of the diversely shaped ligands and central metal ions, various dimensional networks can be developed. Crystal Structures. In complex 1, the Co(II) ion is coordinated by four nitrogen atoms from two H2biim ligands [Co-N ) 2.116(2) - 2.217(2) Å] and two oxygen atoms [Co-O(1) ) 2.160(2) and Co-O(3) ) 2.122(2) Å] to furnish a distorted octahedral geometry (Figure 1a). The bond distances of Co-N(1) ) 2.196(2) and Co-N(7) ) 2.217(2) Å are markedly longer than those of CoN(3) ) 2.116(2) and Co-N(5) ) 2.118(2) Å, because the former ones occupy the apical coordination sites (N(1)-

Co-N(7) 159.01(6)°). The two rings of each H2biim ligand are slightly twisted with dihedral angles of 8.23° and 9.79°. Although the bdc is favorable to act as a bridge and polydentate ligand,2 in our case, the 1,2-bdc displays a terminal ligand in a bidentate 1,6-chelating mode forming a neutral complex [Co(H2biim)2(1,2-bdc)]. This coordination fashion is relatively rare in dicarboxylate chemistry; only a few examples of beryllium, titanium, and copper complexes have been observed so far.12 The structure of complex 1 is different from that of [Mn(1,2-bdc)(phen)(H2O)2]‚H2O, which is a carboxylatebridged 1-D polymer.13 Each molecule in complex 1 can form four donor hydrogen bonds via two H2biim ligands and four acceptor hydrogen bonds via two carboxylate groups extending into multidimensional architecture via hydrogen bonds. The most interesting observation in complex 1 is the chiral recognition via a robust hydrogen-bonded synthon R22(9). Although the crystal is centric, there are two optical isomers, Λ-[Co(H2biim)2(1,2-bdc)] and ∆-[Co(H2biim)2(1,2-bdc)], in the solid state. They assemble via the robust heteromeric hydrogen-bond synthon R22(9) into a 2-D herringbone architecture on the bc plane, as shown in Figure 1b. The isomer of Λ-[Co(H2biim)2(1,2bdc)] or ∆-[Co(H2biim)2(1,2-bdc)] chirally recognizes each other via a hydrogen-bonded synthon R22(9) (N(2)‚‚‚O(3) ) 2.736 and N(4)‚‚‚O(4) ) 2.719 Å) into a chiral chain (-Λ-Λ-Λ- or -∆-∆-∆-) along the b-axis. Furthermore, these chiral chains connect alternately via a pair of hydrogen-bond synthons R22(9) into a 2-D herringbone architecture as shown in Scheme 2. Careful examination demonstrates that the chiral recognition between the H2biim and carboxylate groups is relative to the number of hydrogen-bonded synthons. As shown in Figure 1c, the molecules that connect each other via a single R22(9) synthon are homochiral (shown in one color), whereas those connected via double R22(9) synthons are heterochiral. Therefore, the three Λ-[Co(H2biim)2(1,2-bdc)] and three ∆-[Co(H2biim)2(1,2-bdc)] molecules are self-assembled into a cyclic hexamer with Co(II)‚‚‚Co(II) distances 7.529 Å between the homochiral molecules and 7.117 Å between the heterochiral molecules, respectively. The chiral recognition controlled by hydrogen bonds has also been found in imidazole and H2biim complexes.14,15 Although the assembly of the 1,3-bdc ligand with metal ions in the presence of auxiliary ligands such as bpy and phen has been widely observed,3 the unique example of the 1,3-bdc complex containing the H2biim ligand [Co(H2biim)2(H2O)2](1,3-bdc)‚4H2O has been synthesized;5d however, the 1,3-bdc ligand only acts as a divalent anion. In complex 2, there is one Cd(II) atom,

Table 3. Hydrogen Bonding Parameters in 1-3 D-H‚‚‚A

D-H/Å

H‚‚‚A/Å

D‚‚‚A/Å

D-H‚‚‚A/°

symmetry operation for A

162 171 152 175

-1/2 - x, -1/2 + y, -1/2 - z -1/2 - x, -1/2 + y, -1/2 - z -x, 1 - y, -z -x, 1 - y, -z

N(2)-H(2b)‚‚‚O(3) N(4)-H(4b)‚‚‚O(4) N(6)-H(6b)‚‚‚O(1) N(8)-H(8b)‚‚‚O(2)

0.86 0.86 0.86 0.86

1.91 1.89 1.96 1.89

Complex 1 2.736 2.719 2.751 2.744

N(2)-H(2b)‚‚‚O(3) N(4)-H(4a)‚‚‚O(4)

0.86 0.86

2.06 2.05

Complex 2 2.855 2.837

153 153

-x, 1 - y, 1 - z -1 + x, y, 1 + z

N(4)-H(4a)‚‚‚O(5)

0.86

1.93

Complex 3 2.772

167

3 - x, 1 - y, 1 - z

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Ye et al. Scheme 2. The [Co(H2biim)2(1,2-bdc)] Molecules Assembled into a Chiral Chains That Are Further Constructed into a 2-D Herringbone Architecture via Robust Heteromeric Hydrogen-Bonded Synthons R22(9) in 1

Figure 1. Views of the coordination environment of Co(II) (a), the 2-D herringbone network on the bc plane (b) and a cyclic hexamer via hydrogen-bond synthon R22(9) (c) in 1. The Λ-[Co(H2biim)2(1,2-bdc)] is in blue and ∆-[Co(H2biim)2(1,2-bdc)] is in red. All hydrogen atoms are omitted for clarity.

one 1,3-bdc ligand, and one H2biim ligand in each independent crystallographic unit. Every Cd(II) atom in complex 2 is primarily coordinated by two nitrogen atoms [Cd(1)-N(1) ) 2.344(3) and Cd(1)-N(3) ) 2.317(2) Å, N(1)-Cd(1)-N(3) ) 72.3(1)°] from a chelating H2biim ligand, two oxygen atoms from two µ-carboxylate ends of two 1,3-bdc ligands [Cd(1)-O(4b) ) 2.302(2) and Cd(1)-O(3a) ) 2.314(2) Å], and two oxygen

atoms from one chelating carboxylate end of one 1,3bdc ligand [Cd(1)-O(1) ) 2.305(3) and Cd(1)-O(2) ) 2.401(4) Å, O(1)-Cd(1)-O(2) ) 53.7(1)°] to furnish a highly distorted octahedral geometry as shown in Figure 2a. Two Cd(II) atoms related by a centered symmetry are bridged by a pair of the 1,3-bdc µ-carboxylate ends into a dinuclear unit [Cd(1)‚‚‚Cd(1c) ) 4.355 Å] with two H2biim ligands orientated in opposite directions. The metal-metal distance is comparable with those observed in [Cd2(1,3-bdc)2(bpy)2] (4.181 and 4.364 Å), but significantly longer than that found in [Cd(1,3-bdc)(phen)] (3.99 Å).3g These geometric differences may be attributed to the significant intramolecular π-π stacking interactions in [Cd(1,3-bdc)(phen)], in which the two phen ligands are orientated in one direction with a faceto-face distance of 3.51 Å. Compared with 1,2-bdc, the 1,3-bdc ligand possesses a wider angle between the two carboxylate groups. As a result, the V-shaped 1,3-bdc ligand acts in a chelatebidentate coordination fashion to connect the adjacent Cd(II) atoms into 1-D helical ribbons with a pitch of 10.05 Å running along the c axis (Figure 2b). The H2biim ligand is alternately decorated to both sides of the ribbon; the adjacent zigzag ribbons are packed through intercalation of the lateral H2biim ligands (face-to-face distance 3.53 Å) and hydrogen bonds between the H2biim and carboxylate oxygen atoms [N(2)‚‚‚O(3) ) 2.855 and N(4)‚‚‚O(4) )2.837 Å] in the zipper-like fashion, into 2-D networks parallel to the ac plane. Adjacent ribbons also have intermolecular π-π interactions between the phenyl rings of 1,3-bdc ligand in an offset fashion with a face-to-face distance of ca. 3.61 Å, which extend the 2-D networks into a 3-D architecture in the lattice (Figure 2c). It is notable that the structure of complex 2 is significant different from that observation in [Cd2(bpy)2(1,3-bdc)2], in which the two Cd(II) atoms are sixand seven-coordinate; the two 1,3-bdc ligands display in two coordinate modes, named a chelating bis-bidentate and chelating/bridging bis-bidentate, resulting in a 3-D coordination polymer.16 These observations indi-

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Figure 2. Views of the dimeric Cd(II) unit (a), the double chains assembled via hydrogen bonds along the c-axis (b), and the three-dimensional network (c) in 2.

cate that various auxiliary chelates have a significant effect on the architecture. The structural unit of complex 3 is given in Figure 3a. It consists of a linear trinuclear {Cd3O14N4} cluster, where each terminal Cd(1) atom is linked by three 1,4bdc ligands to the central Cd(2) atom, which is located at an inversion center. The coordination environment of Cd(1) is a distorted octahedral coordination sphere completed by two nitrogen atoms of a H2biim ligand [Cd(1)-N(1) ) 2.376(2) and Cd(1)-N(3) ) 2.276(2) Å] and four oxygen atoms [Cd(1)-O(1) ) 2.208(2), Cd(1)-O(4) ) 2.187(2), Cd(1)-O(5) ) 2.590(2) and Cd(1)-O(6) ) 2.315(2) Å] from three carboxylate groups of the three different 1,4-bdc ligands to form a distorted CdN2O4 octahedron, while the Cd(2) has a CdO6 octahedral geometry from six carboxylate groups of six 1,4-bdc ligands. Therefore, two 1,4-bdc ligands act as in a bridging bis-bidentate mode and the third one functions in the chelating/bridging bis-bidentate mode. The distance between the two metal centers [Cd(1)‚‚‚Cd(2)] is 3.658 Å. Interestingly, the trinuclear units are intercon-

Figure 3. Views of the coordination environment of the trinuclear Cd(II) unit (a), the 3-D network (b), and topology (c) in 3.

nected through six 1,4-bdc ligands to yield a 3-D supramolecular architecture in a R-Po topology (Figure 3b,c). The linear trinuclear Cd complex connected by triple carboxylate groups, to the best of our knowledge, has not been reported so far, although those bridged by mono- and double-carboxylate have been found.17-20 The similar linear trinuclear Co(II) complexes [Co3(O2CMe)6(bpy)2],21 [Co3(O2CPh)6(base)2],22 [Co3(O2C(C6H4NO2)6(base)2)],22 and [Co3(O2CMe)8],23 and Mn(II) complexes [Mn3(O2CMe)6(bpy)2],24 [Mn3(O2CMe)6(phen)2],25 and [Mn3(O2CPh)6(bpy)2]26 have also been reported. Complexes 1-3 were synthesized in similar reaction conditions with benzenedicarboxylate isomers. Three (mono-, bi-, and trinuclear) structural units are formed in complexes 1, 2, and 3, respectively, which are further assembled into 2-D and 3-D networks via supramolecular interaction. It can be predicted that the smallest

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separation of carboxylate groups in 1,2-bdc compared to those in 1,3- and 1,4-bdc isomers results in crowding of the groups, which is favorable for the terminal ligand in a bidentate 1,6-chelating mode to a Co(II) ion to form a neutral monomeric unit. It is also noted that, with the reduction of the bulk crowding of the two carboxylate groups, the dihedral angle between them becomes smaller with 94.2° in 1, 7.5° in 2, and ca. 0° in 3. Obviously, the structural diversity in complexes 1-3 may be attributed to the various shapes of the isomeric benzenedicarboxylate.

Ye et al.

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Conclusion Three new complexes have been synthesized under hydrothermal conditions exhibiting a systematic variation of architecture by the employment of isomeric benzenedicarboxylate ligands, and representing examples of structural changes from the 0-D building blocks to 3-D coordination polymeric network based on mono-, bi-, and trinuclear structural units. The isomeric benzenedicarboxylate ligands give rise to a systematic structural variation in the presence of the auxiliary ligand H2biim via hydrogen bonds and π-π stacking interactions, which implies a potential tool for crystal engineering.

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Acknowledgment. This work was supported by the NSFC (Nos. 20371052 and 20131020) and NSF of Guangdong (No. 031581). Supporting Information Available: X-ray crystallographic file in CIF format for the structure determination of 1-3. This material is available free of charge via the Internet at http://pubs.acs.org.

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