Hydrothermal Synthesis of Three Novel Multidimensional Metal

CRYSTAL GROWTH & DESIGN

Hydrothermal Synthesis of Three Novel Multidimensional Metal-Organic Frameworks with Unusual Units and Mixed Ligands Ying Yan,†,‡ Chuan-De Wu,† Xiang He,† Yan-Qiong Sun,† and Can-Zhong Lu*,†

2005 VOL. 5, NO. 2 821-827

The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese Academy of Sciences, and The Graduate School of the Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China Received August 26, 2004;

Revised Manuscript Received November 8, 2004

ABSTRACT: The hydrothermal reactions of 1,2,4-benzenetricarboxylate (H3btrc), 4,4′-bipyridine (4,4′-bpy), or 1,10phenanthroline (1,10-phen) with transition metal acetates in basified solvent gave rise to three novel coordination polymers, [Ni3(btrc)2(4,4′-bpy)2(H2O)5]n‚2nH2O (1), [Cu3(btrc)2(1,10-phen)3]n (2), and [Co(H2btrc)2(4,4′-bpy)3(H2O)2]n (3), which show respectively three-dimensional polymeric architecture, two-dimensional lamella, and one-dimensional chain architecture. Interestingly, the noncentrosymmetric compound 1 is constructed by beautiful “S” ribbons and exhibits very interesting ferromagnetic properties. Introduction Considerable effort has been devoted to the assembly of metal-organic frameworks (MOFs) from molecular building blocks due to the offered advantages for the design of such kinds of materials.1 To choose an appropriate starting building block for such a design, the synthesis has been identified as a useful tool in the construction of MOFs. Recently, the strategy of using metal ions and organic carboxylates as starting building blocks to give extended networks has been of great interest for the chemist.2-3 The organic carboxylates used include BDC,2a ADC, BTC,1a BTB,2b NDC, BPDC, HPDC, PDC, TPDC,2c and so forth. As part of our continuing investigations on carboxylate-based ligands coordinating transition metal compounds,4 we are currently interested in pursuing synthetic strategies by using mixed 1,2,4-bentricarboxylic acid and N-containing ligands to bond to transition metal atoms. Despite the rich coordination chemistry exhibited by 1,2,4bentricarboxylic and 1,2,4,5-benzenetricarboxylic acids, studies on 1,2,4-bentricarboxylic acid (H3btrc) are less often reported,5 presumably because the asymmetry of the H3btrc brings great difficulty experimentally in crystallization. However, through carefully controlling the reaction conditions, we have found that H3btrc is also a versatile organic ligand for the construction of MOFs. Furthermore, due to its asymmetry, H3btrc may act as a prechiral or noncentrosymmetric ligand to provide an effective way to the construction of some acentric materials.6 In this article, we report on the preparations, crystal structures, and preliminary property studies of three novel coordination polymers, [Ni3(btrc)2(4,4′-bpy)2(H2O)5]n‚2nH2O (1), [Cu3(btrc)2(1,10phen)3]n (2), and [Co(H2btrc)2(4,4′-bpy)3(H2O)2]n (3) (H3btrc ) 1,2,4-benzenetricarboxylate, 4,4′-bpy ) 4,4′bipyridine and 1,10-phen) 1,10-phenanthroline), wherein acentric compound 1 shows very interesting ferromagnetic properties. * To whom correspondence should be addressed. Fax: +86-59183714946. E-mail: [email protected]. † The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese Academy of Sciences. ‡ The Graduate School of the Chinese Academy of Sciences.

Figure 1. ORTEP representation of the symmetry expanded structure in 1, showing the coordination environments of NiII atoms (50% thermal ellipsoids probability and hydrogen atoms are omitted for clarity).

Results and Discussion Green crystals of 1 were obtained from the hydrothermal reaction of Ni(CH3COO)2‚2H2O, 1,2,4-benzenetricarboxylate, 4,4′-bpy, and NH3‚H2O in an aqueous solution heated at 170 °C for 5 days. Single-crystal X-ray diffraction study reveals that compound 1 is of a threedimensional noncentrosymmetrical polymeric architecture. There are three crystallographic independent nickel(II) cations in each empirical formula, which exhibit quite different coordination environments. The first one is coordinated by two nitrogen atoms from two 4,4′-bpy (Ni-N ) 2.079(6)-2.112(6) Å), two oxygen atoms from two btrc ligands (Ni-O ) 2.067(7)-2.074(7) Å) and two aqua ligands (Ni-O ) 2.046(7)-2.087(7) Å). The second one is coordinated by two nitrogen atoms from two 4,4′-bpy (Ni-N ) 2.104(6)-2.119(6) Å) and four oxygen atoms from two btrc ligands (Ni-O ) 2.015(7)-2.141(6) Å), while the last crystallographic independent nickel(II) atom is coordinated by three oxygen atoms from two btrc ligands (Ni-O ) 2.055(6)2.179(5) Å) and three aqua ligands (Ni-O ) 2.018(6)2.039(8) Å) with O(N)-Ni-O(N) angles involving the

10.1021/cg049701o CCC: $30.25 © 2005 American Chemical Society Published on Web 01/14/2005

822

Crystal Growth & Design, Vol. 5, No. 2, 2005

Yan et al. Scheme 1. The Two Different Kinds of Coordinating Modes of the btrc Ligands

Figure 2. The “S”-shaped ribbons in 1 viewed down the a axis.

Figure 3. The S-shaped chain viewed down the c axis.

neighboring atoms ranging from 62.2(2) to 104.2(2)°, of which the acute angle (62.2(2)°) is of a typical chelate carboxylate group6 (Figure 1). Remarkably, the btrc ligands in compound 1 exhibit two different coordinating modes (Scheme 1): the first one is that btrc ligand acts as a six-dentate ligand to link four nickel(II) centers (mode 1), while another as a three-dentate ligand connects two nickel(II) centers (mode 2). The cooperation of the different coordinating modes of the btrc with the different coordination environments of the NiII atoms

helps the formation of the noncentrosymmetric structural framework of 1. It is quite interesting that btrc ligands, which adopt aforementioned coordinating modes, link the nickel atoms to form a very interesting ribbon (Scheme 1 and Figure 2) in the following way: in mode 1, btrc ligands are in the middle of the ribbon, while in the mode 2 btrc ligands are on both sides of the ribbon. The ribbon possesses a certain width because btrc ligands keep three uncoordinated oxygen atoms outside the ribbon in mode 2, characteristics which are relatively rare in the reported articles. Surprisingly, the btrc ligands on both sides of the ribbon bend toward opposite directions to form a wavelike structure, which presents an “S” shape as viewed from the end of the ribbon (Figure 3). Then, the ribbons are cross-linked by 4,4′bpy into a three-dimensional network (Figure 4). The extended structure of 1 contains some small voids, which are occupied by extraframework water molecules. These water molecules inside the voids are hydrogen bonded to the btrc oxygen atoms with O‚‚‚O distances ranging from 2.774 to 2.833 Å.

Figure 4. Packing diagram of 1 viewed down the c axis, showing the noncentrosymmetrical three-dimensional connectivities via mixed ligands.

Synthesis of Metal-Organic Frameworks

Figure 5. ORTEP representation of the symmetry expanded structure in 2, showing the coordination environments of CuII atoms.

The hydrothermal reaction of copper(II) acetate, 1,2,4benzenetricarboxylate, and 1,10-ophen in basified aqueous and methanol solution heated at 110 °C for 6 days led to the formation of deep blue crystals of compound 2. Single X-ray analysis has revealed that 2 is a twodimensional neutral architecture compound. There are three crystallographic independent copper(II) centers, which exhibit two different coordination environments. The first one is coordinated by two oxygen atoms from two btrc ligands (Cu-O ) 2.075(3)-2.178(3) Å) and two nitrogen atoms from one ophen molecule (Cu-N ) 2.069(3) Å) to complete a tetrahedral coordination environment. The other two are coordinated by two nitrogen atoms from one phen (Cu-N ) 2.102(4)-2.184 (4)Å) and three oxygen atoms from two btrc ligands, respectively (Cu-O ) 1.995(3)-2.070(3) Å), showing a distorted triangle bipyramid environment. The O(N)Cu-O(N) angles involving the neighboring atoms range from 77.3 (2)° to 144.7(2)° (Figure 5). Different from the

Crystal Growth & Design, Vol. 5, No. 2, 2005 823

coordination modes of btrc ligand in 1, the btrc ligand in 2 only exhibits one coordination mode. The most interesting feature of 2 is that the btrc ligand acts as a multidentate ligand linking three copper atoms into an infinite two-dimensional lamellar framework (Figure 6), exhibiting as zigzag chains (Figure 7) viewed from the side of the lamella. The hydrothermal reaction of cobalt(II) acetate, 1,2,4benzenetricarboxylate, and 4,4′-bipy in basified aqueous solution heated at 170 °C for 5 days gave rise to a deep red solution, and the solution was evaporated at room temperature for a week to lead to the formation of deep red crystals of compound 3. Single X-ray analysis has revealed that 3 is a one-dimensional neutral architecture compound. Each cobalt(II) atom is coordinated by two nitrogen atoms from two 4,4′-bipy (Co-N ) 2.201(5)-2.255(4) Å), two oxygen atoms from two btrc ligands (Co-O ) 2.099(3) Å), and two oxygen atoms from two water molecules (Co-O ) 2.098(3) Å), completing an octahedral coordination environment (Figure 8) with the O(N)-Co-O(N) angles involving the neighboring atoms ranging from 88.0(1)° to 92.0(1)°. It is very interesting that the cobalt atoms are linked by 4,4′-bipy into a one-dimensional chain structure with only one oxygen atom of each btrc ligand coordinating to the metal center, and every two btrc ligands coordinated to a Co(II) bend in the opposite direction (Figure 9). And finally, these chains are extended in two vertical directions through hydrogen bonding ranging from 2.565(5) to 2.694(4) Å into three-dimensional frameworks (Figure 10) with some square tunnels, which were filled with the dissociative 4,4′-bipy molecules. Magnetic Properties for Compounds 1 and 2. The temperature dependence magnetic susceptibilities of 1 were measured from 300.0 to 5.1 K in a 10 kOe applied magnetic field, and all data were corrected for diamagnetism of the ligands estimated from Pascal’s constants.7 At room temperature, the χMT is 3.063 emu K mol-1, which is comparable to the spin-only value for three uncorrelated S ) 1 NiII centers (3.0 emu K mol-1) (Figure 11). Upon cooling of the sample, the χMT value increases continuously to a peak value of 3.889 emu K mol-1 at 55.1 K, and then decreases to an extreme valley of 3.711 emu K mol-1 at 44.0 K. However, upon

Figure 6. The extended layer structure in 2, viewed down the b axis.

824


Yan et al.

Figure 7. Packing diagram of 2 viewed down the a axis, showing the zigzag architectures of the layers. Figure 10. Packing diagram of 3 viewed down the b axis, showing the extended architectures with some square tunnels.

Figure 11. Plots of the experimental temperature dependences of χMT (O) and χM (2) for 1. Figure 8. ORTEP representation of the symmetry expanded structure in 3, showing the coordination environments of CoII atoms.

Figure 9. The extended chain structure in 3.

continually cooling to 9.0 K, it increases again to a maximum of 4.039 emu K mol-1, and then again it decreases to a value of 3.940 emu K mol-1 at 5.1 K. As shown in Figure 2, two of three crystallographic independent nickel ions are bridged by btrc to form two infinite chains in each ribbon, while another crystallographic independent nickel atom with its symmetry related atoms lie at the inner of the chains, which are linked together through carboxylate groups. It is very difficult to get a suitable theoretical model to fit such a complicated system. Fortunately, the given plot of 1/χM

Figure 12. Plots of the experimental temperature dependences of χMT (O) and χM (() for 2.

(χM, molar magnetic susceptibility) vs T shows a straight line down to 5.1 K, which suggests that it can be fit approximately by the Curie-Weiss law. Least-squares fitting of all experimental data gives the Curie constant values C ) 3.1526 emu K mol-1 and Θ ) 6.4386 K, indicating the presence of ferromagnetic interactions within compound 1. The Curie constant corresponds to


Figure 13. Plot of thermogravimetric analysis for 1.

the parameter g ) 2.05, which is typical for octahedral NiIIO6-type complexes with relevant spin-orbit coupling. While the distances between NiII centers linked by 4,4′-bpy and btrc ligands (11.162 and 10.269 Å between the opposite carboxylate groups) are too long for any significant magnetic interactions, it is anticipated that the relative ferromagnetic Ni-Ni exchange interaction occurs through the bridging carboxylate groups of btrc ligand in a syn-anti mode. It is very rare that a ferromagnetic coupling occurs between nickel cations bridged by a carboxylate group in the syn-anti configuration.8 It is also very interesting to note the anomalistic features from 44.0 to 55.1 K of 1, which might be due to the phase transition from antiferromagnetic to paramagnetic in solid molecular oxygen, and to the melting of this phase. The temperature dependent magnetic susceptibilities of 2 were also measured from 300.0 to 5.1 K in a 10 kOe applied magnetic field and all data were corrected for diamagnetism of the ligands estimated from Pascal’s constants. From the plots of the χMT versus T of 2, it can be seen that the value is 1.22 emu K mol-1 at room temperature, and then decreases to 1.00 emu K mol-1


upon cooling of the sample to 5 K, keeping horizontal on the whole (Figure 12). All experimental data are accurately approximated by the Curie-Weiss law for values C ) 1.22 emu K mol-1 and Θ ) -1.68 k, corresponding to the parameters g ) 2.13 and J ) -3.30 cm-1. These data verify that the relative antiferromagnetic Cu-Cu exchange interaction occurs through the bridging carboxylate groups of btrc ligand. The thermogravimetric analysis (TGA) recorded at 40-800 °C shows three-stage weight losses on the TGA curve for compound 1 (Figure 13). At the first stage, the TGA charts show the weight of 1 is almost unchanged from 40 to 153 °C. The second stage occurs between 153 and 281 °C, which is attributed to the loss of two crystal water molecules and five aqua ligands per formula. The overall observed loss (12.31%) is in agreement with the calculated value (12.26%). When the temperature is above 281°C, the product begins to lose btrc and 4,4′bpy ligands and then to decompose. Conclusion In conclusion, although there is extensive work based on using organic carboxylates in the constructions of new MOFs by conventional solution synthesis, work based on combining 1,2,4-benzenetricarboxylic acid and some other N-heteroaromatic bridging ligand is still relatively rare. The successful isolations of the three title compounds demonstrate that it is promising to apply 1,2,4-benzenetricarboxylic acid and N-heteroaromatic ligands in the designed syntheses of novel MOFs including acentric compounds under hydrothermal reacting conditions. Inspired by the success, we have optimized conditions to synthesize more novel functional solid-state materials based on mixed organic ligands of 1,2,4-benzenetricarboxylate and N-heteroaromatic ligands. Experimental Section Synthesis. [Ni3(btrc)2(4,4′-bpy)2(H2O)5]n‚2nH2O (1): A mixture of Ni(CH3COO)2‚2H2O (0.12 g, 0.50 mmol), H3btrc (0.96 g, 0.5 mmol), 4,4′-bpy (0.1 g, 0.52 mmol), and NH3‚H2O

Table 1. Crystal Data and Structure Refinements for Three Compounds compound formula formula weight crystal size (mm3) crystal color crystal system space group unit cell dimensions

volume (Å3) Z calculated density (g cm-3) F(000) absorption coefficient (mm-1) θ for data collection (°) reflections collected unique reflections (R(int)) parameters goodness-of-fit on F2 R1a, wR2 [I > 2σ(I)] R1, wR2 (all data) a

1 C38H36N4Ni3O19 1028.84 0.62 × 0.56 × 0.18 green orthogonal Pna2(1) a ) 22.556(1) Å b ) 17.239(1)Å c ) 10.023(6) Å

3897.3(4) 2 1.753 2112 1.526 1.49 to 25.15° 9266 4968 [R(int) ) 0.0401] 587 1.101 0.0526, 0.1311 0.0681, 0.1432

R1 ) ∑(|Fo| - |Fc|)/∑|Fo|, wR2 ) [∑w(Fo2 - Fc2)2/∑w(Fo2)2]0.5.

2 C54H32Cu3N6O13 1163.48 0.30 × 0.20 × 0.12 deep blue triclinic P1 h a )10.582(1) Å b ) 15.028(1) Å c ) 16.101(1) Å R ) 65.136(2)° β ) 84.715(2)° γ ) 77.397(2)° 2267.2(3) 2 1.704 1178 1.475 2.24 to 25.02° 11791 7895 [R(int) ) 0.0622] 693 1.054 0.0806, 0.1422 0.1627, 0.1773

3 C48H38CoN6O14 981.77 0.80 × 0.60 × 0.48 deep red monolinic C2/c a ) 15.106(1) Å b ) 11.593 (1) Å c ) 25.892 (2) Å β ) 99.548(1)° 4471.7(6) 4 1.458 2028 0.461 1.60 to 25.05° 6396 3893 [R(int) ) 0.0390] 330 1.059 0.0636, 0.1555 0.0801 0.1758

826


Yan et al.

Table 2. Selected Bond Lengths [Å] and Angles [°] for Three Compoundsa Ni(1)-O(17) Ni(1)-O(9)I Ni(1)-O(6) Ni(1)-N(1)II Ni(1)-O(16) Ni(1)-N(2) Ni(2)-O(10) Ni(2)-O(8) Ni(2)-N(3) Ni(2)-O(4) Ni(3)-O(13) Ni(3)-O(15) Ni(3)-O(14) Ni(3)-O(7)III Ni(3)-O(12)

Cu(1)-O(11)IV Cu(1)-O(2) Cu(1)-N(2) Cu(1)-N(3) Cu(2)-O(6)V Cu(2)-O(8) Cu(2)-N(5) Cu(2)-O(3) Cu(3)-O(4) Cu(3)-N(4) Cu(3)-N(1) Cu(3)-O(9)VI Cu(3)-O(5)V Co(1)-O(7) Co(1)-O(6) Co(1)-N(4) Co(1)-N(3)

2.046(7) 2.067(7) 2.074(7) 2.079(6) 2.087(7) 2.112(6) 2.015(7) 2.077(6) 2.104(6) 2.141(6) 2.018(6) 2.032(6) 2.039(8) 2.130(7) 2.176(5)

1.939(6) 1.975(6) 2.024(7) 2.026(7) 1.942(6) 1.998(6) 2.022(7) 2.213(7) 1.936(6) 2.032(7) 2.084(7) 2.102(7) 2.176(6) 2.092(3) 2.098(3) 2.203(5) 2.255(4)

Compound 1 O(17)-Ni(1)-O(9)I O(17)-Ni(1)-O(6) O(9)I-Ni(1)-O(6) O(17)-Ni(1)-N(1)II O(9)I-Ni(1)-N(1)II O(6)-Ni(1)-N(1)II O(17)-Ni(1)-O(16) O(9)I-Ni(1)-O(16) O(6)-Ni(1)-O(16) N(1)II-Ni(1)-O(16) O(17)-Ni(1)-N(2) O(9)I-Ni(1)-N(2) O(6)-Ni(1)-N(2) N(1)II-Ni(1)-N(2) O(16)-Ni(1)-N(2) O(10)-Ni(2)-O(5) O(10)-Ni(2)-O(8) O(5)-Ni(2)-O(8) O(10)-Ni(2)-N(3) O(5)-Ni(2)-N(3) O(8)-Ni(2)-N(3) O(10)-Ni(2)-N(4) O(5)-Ni(2)-N(4) O(8)-Ni(2)-N(4) N(3)-Ni(2)-N(4) Compound 2 O(11)IV-Cu(1)-O(2) IV O(11) -Cu(1)-N(2) O(2)-Cu(1)-N(2) O(11)IV-Cu(1)-N(3) O(2)-Cu(1)-N(3) N(2)-Cu(1)-N(3) O(6)V-Cu(2)-O(8) O(6)V-Cu(2)-N(5) O(8)-Cu(2)-N(5) O(6)V-Cu(2)-N(6) O(8)-Cu(2)-N(6) N(5)-Cu(2)-N(6) O(6)V-Cu(2)-O(3)

88.6(3) 89.7(3) 169.3(2) 87.8(3) 93.5(3) 97.0(3) 173.8(3) 97.6(3) 84.5(2) 90.8(3) 90.6(3) 85.2(3) 84.2(3) 177.9(3) 90.9(3) 176.9(2) 91.3(3) 89.2(3) 90.8(4) 92.2(4) 82.4(3) 88.9(4) 88.1(4) 97.2(3) 179.6(3)

93.5(2) 173.6(3) 92.7(3) 92.4(3) 172.5(3) 81.6(3) 87.7(2) 177.3(3) 93.9(3) 96.6(3) 152.7(3) 81.0(3) 97.3(3)

Compound 3 O(7)VII-Co(1)-O(7) 175.8(2) O(7)-Co(1)-O(6)VII 91.5(1) O(7)-Co(1)-O(6) 88.5 (1) O(6)VII-Co(1)-O(6) 179.2 (2) O(7)-Co(1)-N(4) 92.1 (1)

O(10)-Ni(2)-O(4) O(5)-Ni(2)-O(4) O(8)-Ni(2)-O(4) N(3)-Ni(2)-O(4) N(4)-Ni(2)-O(4) O(13)-Ni(3)-O(15) O(13)-Ni(3)-O(14) O(15)-Ni(3)-O(7)III O(14)-Ni(3)-O(7)III O(11)-Ni(3)-O(7)III O(13)-Ni(3)-O(12) O(15)-Ni(3)-O(12) O(14)-Ni(3)-O(12) O(11)-Ni(3)-O(12) O(7)III--Ni(3)-O(12) O(13)-Ni(3)-C(33) O(15)-Ni(3)-C(33) O(14)-Ni(3)-C(33) O(11)-Ni(3)-C(33) O(7)III--Ni(3)-C(33) O(12)-Ni(3)-C(33) O(15)-Ni(3)-O(14) O(13)-Ni(3)-O(11) O(15)-Ni(3)-O(11) O(14)-Ni(3)-O(11) O(13)-Ni(3)-O(7)III

88.6(3) 91.7(2) 164.5(2) 82.1(3) 98.2(3) 92.4(3) 85.4(3) 87.6(3) 175.0(3) 91.8(3) 104.2(2) 162.8(2) 89.3(3) 62.2(2) 86.1(3) 134.1(3) 133.4(3) 86.2(3) 31.6(3) 88.9(3) 30.6(3) 96.3(3) 163.1(3) 102.1(2) 84.4(3) 97.5(3)

O(8)-Cu(2)-O(3) N(5)-Cu(2)-O(3) N(6)-Cu(2)-O(3) O(4)-Cu(3)-N(4) O(4)-Cu(3)-N(1) N(4)-Cu(3)-N(1) O(4)-Cu(3)-O(9)VI N(4)-Cu(3)-O(9)VI N(1)-Cu(3)-O(9)VI O(4)-Cu(3)-O(5)V N(4)-Cu(3)-O(5)V N(1)-Cu(3)-O(5)V O(9)III-Cu(3)-O(5)V

95.7(2) 84.8(3) 110.4(3) 175.6(3) 95.8(3) 80.8(3) 86.0(3) 95.4(3) 149.6(3) 100.1(3) 83.8(3) 111.2(3) 98.3(3)

O(6)-Co(1)--N(4) O(7)-Co(1)-N(3) O(6)-Co(1)-N(3) N(4)-Co(1)-N(3)

90.4(1) 87.9(1) 89.61(1) 180.0 (0)

a Symmetry transformations used to generate equivalent atoms: (I) x, y, z - 1, (II) x - 1/2, -y + 1/2, z, (III) -x + 1, -y, z + 1/2, (IV) -x + 1, -y - 1, -z, (V) -x + 1, -y - 1, -z + 1, (VI) -x + 1, -y, -z, (VII) -x, y, -z + 3/2.

(0.1 mL, 1.3 mmol) in 18 mL of H2O was heated at 170 °C for 5 days in a sealed 30 mL Teflon-lined stainless steel vessel under autogenous pressure. After the reaction mixture was slowly cooled to room temperature, green crystals were produced (yield 53%, based on Ni). Anal. Calc. for 1: C, 44.36; H, 3.53; N, 5.45%. Found: C, 44.22; H, 3.56; N, 5.45%. IR (solid KBr pellet/cm-1): 1610s, 1591s, 1558s, 1535s, 1491s, 1396s, 1360s, 1348sh, 1294m, 1257m, 1223m, 1172w, 1132w, 1070m, 1012w, 937w, 927w, 872w, 864w, 848w, 814s, 766m, 752sh, 731m, 669w, 636m, 598m, 586m, 563w, 501m, 449w, 430w. [Cu3(btrc)2(1,10-phen)3]n (2): A mixture of Cu(CH3COO)2‚ H2O (0.13 g, 0.50 mmol), H3btrc (0.1 g,0.50 mmol), 1,10-phen (0.05 g, 0.50 mmol) and NH3‚H2O (0.05 mL, 0.6 mmol) in H2O (18 mL) was heated at 110 °C for 6 days under autogenous pressure in a sealed 25 mL Teflon-lined stainless steel vessel. Deep blue crystals were isolated after the reaction solution was cooled slowly to room temperature. Yield: 30% (based on Cu). Anal. Calcd. For C54H32Cu3N6O13: C, 52.27; H, 2.92; N, 10.16%. Found: C, 52.31; H, 2.85; N, 10.12%. IR: (KBr pellet): 1632s, 1612s, 1573s, 1518s, 1481m, 1425s, 1379s, 1342s, 1294sh, 1167w, 1144w, 1107w, 926w, 874m, 864m, 852s, 839sh, 823m, 750s, 773s, 725s, 667m, 646m, 579w, 523m, 430m.

[Co(H2btrc)2(4,4′-bpy)3(H2O)2]n (3): A mixture of Co(CH3COO)2‚2H2O(0.125 g, 0.50 mmol), H3btrc (0.96 g, 0.5 mmol), 4,4′-bpy(0.1 g, 0.52 mmol) and NH3‚H2O (0.1 mL, 1.3 mmol) in 18 mL of H2O was heated at 170 °C for 5 days in a sealed 30 mL Teflon-Lined stainless steel vessels under autogenous pressure. After the reaction mixture was slowly cooled to room temperature, the resulting deep red solution was evaporated at room temperature for about a week, and deep red crystals were obtained. (Yield 18%, based on Co). Anal. Calcd. For C48H38CoN6O14: C, 58.72; H, 3.90; N, 8.56%. IR: (KBr pellet): 1703s, 1601s, 1567s, 1560s, 1491m, 1412s, 1377s, 1335w, 1296s, 1248m, 1221m, 1140m, 1072m, 1012m, 928w, 901w, 858w, 829w, 812s, 781m, 762m, 700m, 646s, 575w, 555w, 515w, 484w, 430w. X-ray Crystallographic Studies. The determination of the unit cells and the data collection for the three compounds were performed on a Siemens SMART CCD, using graphitemonochromatic Mo-KR radiation (λ ) 0.071073 nm). The data sets were corrected by SADABS program.9 The structures were solved by direct methods and refined by full-matrix leastsquares. The structure solutions and refinements were carried out using the SHELXL-97 software package.10 All atoms except hydrogen atoms were refined anisotropically. Crystallographic data are summarized in Table 1, and selected bond lengths



Table 3. Selected Hydrogen Bonds Lengths (Å) for 3a D‚‚‚A

d(D‚‚‚A) Å

O(7)-H(7C)‚‚‚O(4)IV O(2)-H(2C)‚‚‚N(1)V O(3)-H(3C)‚‚‚N(2)VI

2.694(4) 2.636(5) 2.565(5)

(2)

a Symmetry transformations used to generate equivalent atoms: (I) -x, y, -z + 3/2, (II) x, y - 1, z, (III) x, y + 1, z, (IV) -x 1/2, y + 1/2, -z + 3/2, (V) -x, y + 1, -z + 3/2, (VI) -x - 1/2, y 1/2, -z + 3/2.

and angles are listed in Table 2 while selected hydrogen bond distances are in Table 3. Crystallographic data (excluding the structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication nos. CCDC-211984 (1), 226825 (2), and 226826 (3). Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambidge CB21EZ, UK (Fax: (+44) 1223-336-033; E-mail: [email protected]).

(3) (4) (5)

Acknowledgment. This work was supported by the 973 Program of the MOST (001CB108906), the National Natural Science Foundation of China (90206040, 20303021, 20333070 and 20425313), the NSF of Fujian Province (2002F015 and 2002J006) and the Chinese Academy of Sciences. Supporting Information Available: Tables of crystallographic parameters; atomic coordinates and equivalent isotropic displacement parameters; and full bond lengths and angles for compounds 1-3. This material is available free of charge via the Internet at http://pubs.acs.org.

(6)

References (1) (a) Kim, J.; Chen, B.; Reineke, T. M.; Li, H.; Eddaoudi, M.; Moler, D. B.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2001, 123, 8239. (b) Stein, A.; Keller, S. W.; Mallouk, T. E. Science 1993, 259, 1558. (c) Xu, Z.; Kiang, Y. H.; Lee, S.; Lobkovsky, E. B.; Emmott, N. J. Am. Chem. Soc. 2000, 122, 8376. (d) Chae, H. K.; Eddaoudi, M.; Kim, J.; Hauck, S. I.; Hartwing, J. F.; O’Keeffe, M.; Yaghi, O. M. J. Am. Chem. Soc. 2001, 123, 11482. (e) Stein, A.; Keller, S. W.; Mallouk, T. E. Science 1993, 259, 1558. (f) Xiong, R. G.; Wilson, S. R.; Lin, W. J. Chem. Soc., Dalton Trans. 1998, 4089. (g) Xu, Z.; Kiang, Y. H.; Lee, S.; Lobkovsky, E. B.; Emmott, N. J. Am. Chem. Soc. 2000, 122, 8376. (h) Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res. 1998, 31, 474. (i) Hennigar, T. L.; Macquarrie, D. C.; Losier, P.;

(7) (8)

(9) (10)

Rogers, R. D.; Zaworotko, M. J. Angew. Chem., Int. Ed Engl. 1997, 36, 972. (j) Hoskins, B. F.; Robson, R. J. Am. Chem. Soc. 1990, 112, 1546. (k) Yaghi, O. M.; O’Keeffe, M., Eds. J. Solid State Chem. 2000, 152, 1. (a) Rosi, N. L.; Eckert, J.; Eddaoudi, M.; Vodak, D. T.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. Science 2003, 300, 1127. (b) Chen, B.; Eddaoudi, M.; Hyde, S. T.; O’Keeffe, M.; Yaghi, O. M. Science 2001, 291, 1021. (c) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469. (d) Li, H.; Eddaoudi, M.; O’Keeffe, M.; Yaghi, O. M. Nature 1999, 402, 276. (e) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.; Eddaoudi, M.; Kim, J. Nature 2003, 423, 705. (f) Rosi, N. L.; Eddaoudi, M.; Kim, J.; O’Keeffe, M.; Yaghi, O. M. Angew. Chem., Int. Ed. 2002, 41, 284. (g) Zhao, H.; Qu, Z. R.; Ye, Q.; Wang, X. S.; Zhang, J.; Xiong, R. G.; You, X. Z. Inorg. Chem. 2004, 43, 1813. (h) Sungho, Y.; Stephen, J. L. J. Am. Chem. Soc. 2004, 126, 2666. Lu, J. Y. Coord. Chem. Rev. 2003, 246, 327. Yan, Y.; Wu, C. D.; Lu, C. Z. Z. Anorg. Allg. Chem. 2003, 629, 1991. (a) Fan, J.; Zhu, H. F.; Okamura, T. A.; Sun, W. Y.; Tanga, W. X.; Ueyamab, N. New J. Chem. 2003, 27, 1409. (b) Plater, M. J.; St Foreman, M. R.; Howie, A. R.; Skakle, J. M. S.; Slawin, A. M. Z. Inorg. Chim. Acta. 2001, 315, 132. (c) Jim, Z. S.; Duan, Z. B.; Wei, C. G.; Ni, J. Z. Jiegou Huaxue 1990, 9, 69. (d) Wei, G. C.; Duan, Z. B.; Jim, Z. S.; Ni, J. Z. Jiegou Huaxue 1992, 11, 96. (e) Wei, G. C.; Duan, Z. B.; Jim, Z. S.; Ni, J. Z. Jiegou Huaxue 1992, 11, 96. (f) Ren, Y. D.; Long, L. S.; Zheng, L. S.; Ng, S. W. Main Group Metal Chem. 2002, 25, 323. (g) Zheng, P. Q.; Long, L. S.; Huang, R. B.; Zheng, L. S. Appl. Organomet. Chem. 2003, 17, 647. (a) Evans, W. R.; Xiong, R.-G.; Wang, Z.; Wong, G. K.; Lin, W. Angew. Chem., Int. Ed. 1999, 38, 536. (b) Jouaiti, A.; Hosseini, M. W.; Kyritsakas, N. Chem. Commun. 2002, 1898. (c) Evans, O. R.; Lin, W. B. Acc. Chem. Res. 2002, 35, 511. (d) Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O’Keette, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319. Pascal, P. Ann. Chim. Phys. 1910, 19, 5. (a) Mukherjee, P. S.; Konar, S.; Zangrando, E.; Mallah, T.; Ribas, J.; Chaudhuri, N. R. Inorg. Chem. 2003, 42, 2695. (b) Du, M.; Bu, X.-H.; Guo, Y.-M.; Zhang, L.; Liao, D.-Z.; Ribas, J. Chem. Commun. 2002, 1478 and references therein. (c) Wu, C.-D.; Lu, C.-Z.; Lu, S.-F.; Zhuang, H.-H.; Huang, J.-S. Inorg. Chem. Commun. 2002, 5, 171. Sheldrick, G. M. SADABS, Siemens Analytical X-ray Instrument Division, Madison, WI, 1995. Sheldrick, G. M. SHELXL-97 software package, Universita¨t Go¨ttingen, Germany, 1997.

CG049701O

Hydrothermal Synthesis of Three Novel Multidimensional Metal

Recommend Documents