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Synthesis and crystal structure of Cu2[bbimb]: A metal-organic framework with zeolite ABW topology
Microporous and Mesoporous Materials 119 (2009) 344–348
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Synthesis and crystal structure of Cu2[bbimb]: A metal-organic framework with zeolite ABW topology Lirong Zhang, Xuejian Qu, Minghui Bi, Shuang Wang, Shuzhe Gong, Qisheng Huo, Yunling Liu * State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, PR China
a r t i c l e
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Article history: Received 7 August 2008 Received in revised form 29 October 2008 Accepted 31 October 2008 Available online 11 November 2008 Keywords: Solvothermal synthesis Crystal structure Metal-organic framework Imidazolate derivate
a b s t r a c t A new copper(I) imidazolate metal-organic framework, Cu2[bbimb] (1), has been synthesized by solvothermal reaction of Cu(NO3)2 3H2O and 1,3-bis(2-benzimidazol)benzene (H2bbimb) in an ammonium/ methanol mixture. Single-crystal X-ray diffraction analysis reveals that the structure of compound 1 contains three crystallographically independent Cu(I) ions and one bbimb2 ligand. Each copper center in 1 is linearly coordinated by two nitrogen atoms from two different bbimb ligands and each bbimb coordinates four copper ions to form a neutral three-dimensional metal-organic framework with zeolite ABW topology. Crystal data for 1: Monoclinic, C2/c, a = 22.1660(9) Å, b = 14.9825(7) Å, c = 11.4773(4) Å, b = 107.972(2)o, V = 3625.7(3) Å3, Z = 8. Ó 2008 Elsevier Inc. All rights reserved.
1. Introduction Among the vast family of porous materials [1], metal-organic frameworks constitute an important class. Synthesis of metal-organic frameworks (MOFs) has increased enormously due to their fascinating structures, properties and their various potential applications in catalysis, separation, gas storage and molecular recognition [2–7]. Especially, constructing MOFs with expanded zeolite and zeolite-like topologies still remains a great challenge. Recently, scientists have successfully acquired some ZMOFs (ZMOF = zeolitelike MOF) with zeolite SOD, MTN, ABW, GIS, ANA and RHO topologies by utilizing effective synthetic strategies [8–25]. Most of the ZMOFs explored to date are based on metal-imidazolates, and it is accepted that imidazolates and its derivatives are very unique and important ligands for the fabrication of MOFs with zeolitic topologies. Besides zeolitic topologies of metal-imidazolates, metal-imidazolates with zero-dimensional (0D) rings, 1D zigzag and helical chains, and 2D layer structures have been reported so far [26–32]. Based on our earlier research [21,32,33] and the study of known metal-imidazolates, we have extended our research to the metal-imidazolate derivatives system, and we have found that 1,3-bis(2-benzimidazol)benzene (H2bbimb), as a new ligand, can be used as a building block for constructing MOFs. This ligand, as well as the related molecule 1,3-bis(1-methylbenzimidazol-2-yl)benzene (mbzimpH), presents multiple * Corresponding author. Tel.: +86 431 85168614; fax: +86 431 85168624. E-mail address: [email protected] (Y. Liu). 1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2008.10.037
nitrogen-donor sites with the possibility of reversible protonation and deprotonation, properties that have been capitalized upon in supramolecular chemistry for the preparation of mononuclear [34], dinuclear [35,36] and trinuclear cyclometalated coordination compounds [37] with interesting helical, chiral cavity structural features and photophysical properties. To the best of our knowledge, there is no 3D structure reported yet based on H2bbimb. The H2bbimb ligand features multidentate character; that is, it possesses two imine N atoms and two amine NH groups. After the H2bbimb ligand is partially or fully deprotonated at different pH conditions, the amine N atoms can act as coordination donors. Herein, we report the synthesis and crystal structure of a new metal-organic framework, Cu2[bbimb] (1), based on copper(I) ions and the [bbimb]2 ligands. 2. Experimental 2.1. Physical measurements X-ray powder diffraction (XRPD) data were collected on a Rigaku/max-2550 diffractometer with CuKa radiation (k = 1.5418 Å). The elemental analyses were performed on a Perkin–Elmer 2400 LSII C.H.N. analyzer. The inductively coupled plasma (ICP) analyses were carried out on a Perkin–Elmer Optima 3300DV ICP instrument. The infrared (IR) spectra were recorded within the 400– 4000 cm1 region on a Nicolet Impact 410 FTIR spectrometer using KBr pellets. The thermal gravimetric analyses (TGA) were performed on NETZSCH STA449C thermogravimetric analyzer in N2 flow with a heating rate of 10 oC min1.
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L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 344–348 Table 1 Crystal data and structure refinement for 1.
Fig. 1. Simulated and experimental X-ray powder diffraction patterns of compound 1.
Empirical formula Formula weight Temperature (K) Wavelength (Å) Crystal system Space group a (Å) b (Å) c (Å) a (o) b (o) c (o) V (Å3) Z Dcalc (Mg m3) Absorption coefficient (mm1) Reflections collected Reflections unique Goodness-of-fit on F2 Final R indices [I>2r(I)] Largest difference peak and hole (e Å3)
C20 H12 Cu2 N4 435.42 293(2) 0.71073 Monoclinic C2/c 22.1660(9) 14.9825(7) 11.4773(4) 90 107.972(2) 90 3625.7(3) 8 1.595 2.356 13130 4519 (Rint = 0.0727) 0.868 R1 = 0.0415 wR2 = 0.0781 0.451, 0.485
of one bbimb ligand (calcd. 70.81 wt%). XRD analyses indicated that the compounds became amorphous after the decomposition. 2.3. Structural determination Suitable single-crystal of 1 (0.29 0.21 0.18 mm3) was selected for single-crystal X-ray diffraction analyses. The intensity data was collected on a Siemens Smart CCD diffractometer using graphite-monochromated Mo-Ka radiation (k = 0.71073 Å). The number of collected reflections and independent reflections were 13130 and 4519 for 1. Data processing was accomplished with the SAINT processing program. The structure was solved by direct
Table 2 Atomic coordinates (104) and equivalent isotropic displacement parameters (Å2 03) for 1.
Fig. 2. Thermal gravimetric analysis curve for 1.
2.2. Synthesis The ligand 1,3-bis(2-benzimidazol)benzene (H2bbimb) was prepared according to a literature procedure [38]. Cu(NO3)2 3H2O (0.24 g, 1 mmol) and H2bbimb (0.155 g, 0.5 mmol) were suspended in a mixture of ammonium (5 mL) and methanol (5 mL), which was heated at 180 oC for 2 days in a 15 mL teflon-lined stainless-steel autoclave under autogeneous pressure. The resulting yellow block-like crystals of Cu2[bbimb] 1, were isolated by filtration, washed with distilled water, and dried in air (70% yield based on Cu(NO3)2 3H2O). Compound 1 was insoluble in water and all common organic solvents, such as ethanol, acetone, acetonitrile, benN,N0 zene, tetrahydrofuran, N,N0 -dimethylformamide, diethylformamide, and dimethyl sulfoxide. The agreement between the experimental and simulated XRD patterns indicated the phase purity of the product (Fig. 1). Elemental analysis for C20H12Cu2N4: found (wt%): C, 55.02; H, 2.71; N, 12.91. Calcd. (wt%): C, 55.17; H, 2.78; N, 12.87. The TG curve of 1 exhibited a total weight loss of 69.6 wt% from around 100–1000 oC (as shown in Fig. 2), corresponding to the loss
Atom
x
y
z
Ua (eq)
Cu(1) Cu(2) Cu(3) N(1) N(2) N(3) N(4) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20)
2500 0 1056(1) 1848(1) 874(1) 1059(1) 1118(1) 1097(2) 933(1) 480(2) 206(2) 369(2) 815(2) 994(2) 1224(2) 1253(2) 1396(2) 1571(2) 1598(2) 1459(2) 1286(2) 1910(2) 2437(2) 2337(2) 1731(2) 1209(2) 1303(2)
2500 1136(1) 5170(1) 1742(2) 1149(2) 5508(2) 5303(2) 3351(2) 2455(2) 2202(2) 2841(3) 3728(3) 3997(2) 4941(2) 1777(2) 6306(2) 7131(3) 7808(3) 7683(3) 6872(3) 6177(2) 1007(2) 646(3) 79(3) 445(3) 86(3) 643(2)
5000 2500 7545(1) 4104(2) 3230(3) 5987(2) 4075(2) 4552(3) 4556(3) 5111(3) 5666(3) 5653(3) 5090(3) 5052(3) 3962(3) 5597(3) 6170(3) 5525(4) 4338(4) 3770(3) 4411(3) 3395(3) 3156(4) 2385(4) 1856(4) 2083(4) 2869(3)
27(1) 32(1) 29(1) 24(1) 27(1) 26(1) 26(1) 23(1) 23(1) 30(1) 35(1) 30(1) 22(1) 23(1) 23(1) 29(1) 43(1) 54(1) 54(1) 40(1) 27(1) 27(1) 41(1) 55(1) 60(1) 48(1) 28(1)
a
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 344–348
Table 3 Selected bond lengths (Å) and bond angles (o) for 1. Cu(1)–N(1) Cu(1)–N(1)#1 Cu(2)–N(2) Cu(2)–N(2)#2 Cu(3)–N(4)#3 Cu(3)–N(3) N(1)–C(8) N(1)–C(15) N(2)–C(8) N(2)–C(20) N(3)–C(7) N(3)–C(9) N(4)–C(7) N(4)–C(14) N(4)–Cu(3)#4 C(15)–C(20) C(16)–C(17) C(17)–C(18) N(1)–Cu(1)–N(1)#1 N(2)–Cu(2)–N(2)#2 N(4)#3–Cu(3)–N(3) C(8)–N(1)–C(15) C(8)–N(1)–Cu(1) C(15)–N(1)–Cu(1) C(8)–N(2)–C(20) C(8)–N(2)–Cu(2) C(20)–N(2)–Cu(2) C(7)–N(3)–C(9) C(7)–N(3)–Cu(3) C(9)–N(3)–Cu(3) C(7)–N(4)–C(14) C(7)–N(4)–Cu(3)#4 C(14)–N(4)–Cu(3)#4 C(2)–C(1)–C(6) C(1)–C(2)–C(3) C(1)–C(2)–C(8) C(3)–C(2)–C(8) C(4)–C(3)–C(2) C(5)–C(4)–C(3) C(4)–C(5)–C(6) C(5)–C(6)–C(1) C(5)–C(6)–C(7) C(1)–C(6)–C(7) C(19)–C(20)–C(15)
1.876(3) 1.876(3) 1.859(3) 1.859(3) 1.859(3) 1.861(3) 1.343(4) 1.400(4) 1.338(4) 1.376(4) 1.340(4) 1.389(4) 1.348(4) 1.384(4) 1.859(3) 1.403(4) 1.374(5) 1.403(6) 180.00(19) 178.75(18) 172.10(12) 104.1(3) 129.2(2) 126.7(2) 104.9(3) 127.7(2) 125.4(2) 104.8(3) 124.4(2) 129.5(2) 104.8(3) 131.1(2) 124.0(2) 120.9(3) 119.3(3) 120.6(3) 120.1(3) 120.0(3) 120.3(3) 120.6(3) 118.9(3) 121.7(3) 119.4(3) 121.1(3)
C(1)–C(2) C(1)–C(6) C(2)–C(3) C(2)–C(8) C(3)–C(4) C(4)–C(5) C(5)–C(6) C(6)–C(7) C(9)–C(10) C(9)–C(14) C(10)–C(11) C(11)–C(12) C(12)–C(13) C(13)–C(14) C(15)–C(16) C(18)–C(19) C(19)–C(20)
1.391(5) 1.396(4) 1.396(5) 1.478(4) 1.390(5) 1.379(5) 1.395(4) 1.474(5) 1.390(5) 1.399(4) 1.381(6) 1.394(6) 1.369(5) 1.395(5) 1.390(5) 1.372(6) 1.391(5)
N(3)–C(7)–N(4) N(3)–C(7)–C(6) N(4)–C(7)–C(6) N(2)–C(8)–N(1) N(2)–C(8)–C(2) N(1)–C(8)–C(2) N(3)–C(9)–C(10) N(3)–C(9)–C(14) C(10)–C(9)–C(14) C(11)–C(10)–C(9) C(10)–C(11)–C(12) C(13)–C(12)–C(11) C(12)–C(13)–C(14) N(4)–C(14)–C(13) N(4)–C(14)–C(9) C(13)–C(14)–C(9) C(16)–C(15)–N(1) C(16)–C(15)–C(20) N(1)–C(15)–C(20) C(17)–C(16)–C(15) C(16)–C(17)–C(18) C(19)–C(18)–C(17) C(18)–C(19)–C(20) N(2)–C(20)–C(19) N(2)–C(20)–C(15)
114.3(3) 123.2(3) 122.5(3) 115.0(3) 121.5(3) 123.5(3) 131.4(3) 108.0(3) 120.7(3) 117.4(3) 121.9(4) 120.9(4) 118.0(3) 130.8(3) 108.1(3) 121.1(3) 131.3(3) 121.0(3) 107.6(3) 117.1(3) 122.0(4) 121.0(4) 117.7(4) 130.4(3) 108.4(3)
Symmetry transformations used to generate equivalent atoms: #1 x+1/2, y+1/2, z+1 #2 x,y, z+1/2 #3 x, y+1, z+1/2 #4 x, y+1, z1/2.
methods and refined by full-matrix least-squares on F2 using SHELXTL Version 5.1 [39]. All the copper atoms were first located. Then carbon, nitrogen atoms, and hydrogen atoms of the organic framework subsequently were found in difference Fourier maps. The hydrogen atoms of the ligand molecule were placed geometrically. All non-hydrogen atoms were refined anisotropically. Crystal data and refinement parameters for the structure determination are presented in Table 1. The final atomic coordinates and the selected bond distances and angles are given in Tables 2 and 3, respectively.
perature should be an important factor in controlling the reduction of Cu(II) ions into Cu(I). In compound 1, each bbimb2 ligand binds to four Cu(I) ions, and in turn each Cu(I) is linearly coordinated by two nitrogen atoms from two independent bbimb2 ligands. The average Cu–N bond length is 1.865(3) Å, which is slightly shorter than that observed in [Cu2(L3)2](ClO4)2, 1.890 (7) Å (L3 stand for 1,3-bis(1-methylbenzimidazol-2-yl)benzene ligand) [35]. The N– Cu–N bond angles for Cu(1) and Cu(2) atoms are almost linear, 180.00(19) and 178.75(18)o, respectively. The N–Cu–N bond angles for Cu(3) is 172.10(12)o, deviated slightly from the ideal 180o. Two benzimidazole rings are not coplanar with respect to the central benzene ring, showing dihedral angles of 38.2 and 44.7o, respectively. Compound 1 exhibits a novel three-dimensional metal-organic framework based on the assembly of Cu(I) and the bbimb2 ligand (Fig. 3). Each bbimb2 ligand binds to four Cu(I) atoms, and can be viewed as a 4-connected tetrahedral node due to the deviation of benzimidazole rings from the central benzene ring (Fig. 3b); all these bbimb2 ligands link together through the linearly coordinated monovalent Cu ions to form a neutral 3D framework (Fig. 3c and d). From the perspective of network topology, the linearly coordinated Cu atoms serve to replace the O2 bridges in traditional zeolites, and the bbimb2 ligands act as tetrahedral nodes. Thus, compound 1 represents a 3D 4-connected net with zeolite ABW topology (the analyzed vertex symbol and coordination sequence of compound 1 from the program package TOPOS 4.0 are the same as those of ABW in the zeolite database) (Fig. 3e and f) [40,41]. As known, the framework symmetry of zeolite ABW is higher then compound 1 (orthorhombic, Imma for zeolite ABW; monoclinic, C2/c for compound 1). When the bbimb2 ligands are regarded as 4-connected vertices, both the vertex symbol and coordination sequence are same as those for the zeolite ABW structure. The framework of compound 1 also contain eight-membered rings as the structure of a zeolite ABW, but the channels are occupied with phenyl groups and copper metal ions. The channels of the structure are viewed along the [1 0 0] direction, as shown in Fig. 3d. 4. Conclusion In this paper, we have successfully synthesized a new metal-organic framework, Cu2[bbimb], using 1,3-bis(2-benzimidazol)benzene as a new organic bridging ligand. This study reveals that new nitrogen-donor H2bbimb ligand can be used as a tetrahedral building block to construct zeolite-like MOFs. Here we present the first structure based on such ligand, the assembly of the ligand with Cu(I) has led to the construction of a zeolite-like structure having ABW topology. Work is in progress to expand our work with this ligand to other metals. Also similar expanded ligands will synthesized to allow the access of accessible large cavities suitable for inclusion chemistry. Acknowledgments
3. Results and discussion 3.1. Crystal structure of Cu2[bbimb] 1 Single-crystal X-ray diffraction analysis indicates that compound 1 crystallizes in the monoclinic space group C2/c with the formula of Cu2[bbimb]. The asymmetric unit of 1 contains 27 non-hydrogen atoms, of which 24 atoms belong to one bbimb2 ligand (20 oC and 4 N atoms) and 3 atoms are crystallographically distinct Cu(I) ions. We started the reaction with Cu(II) ions, and only Cu(I) was found in the final compound 1. It should be mentioned that there were several reports of a hydrothermal approach for the generation of Cu(I) imidazolate polymers [26–29]. The tem-
The authors acknowledge the financial support of the Natural Science Foundation of China (Nos. 20671041, 20701015) and the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University. Appendix A. Supplementary data Crystallographic data for the structure reported in this paper, in the form of a CIF file, have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 692102 for 1. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2
L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 344–348
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Fig. 3. Single-crystal structure of 1: (a) the bbimb2 ligand, (b) each bbimb2 ligand coordinated to four Cu atoms that can be viewed as four-connected tetrahedral building units, (c) ball-and-stick view of 1 along the [0 0 1] direction, (d) ball-and-stick view of 1 along the [1 0 0] direction, (e) framework of 1 showing the Cu bridges and tetrahedral ligands, (f) topology of the framework of 1 viewed along c direction. Color code: Cu: orange; C: gray; N: blue; the bbimb2 ligand as 4-connected nodes are denoted by green spheres. Hydrogen atoms are omitted for clarity. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
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Microporous and Mesoporous Materials journal homepage: www.elsevier.com/locate/micromeso
Synthesis and crystal structure of Cu2[bbimb]: A metal-organic framework with zeolite ABW topology Lirong Zhang, Xuejian Qu, Minghui Bi, Shuang Wang, Shuzhe Gong, Qisheng Huo, Yunling Liu * State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, PR China
a r t i c l e
i n f o
Article history: Received 7 August 2008 Received in revised form 29 October 2008 Accepted 31 October 2008 Available online 11 November 2008 Keywords: Solvothermal synthesis Crystal structure Metal-organic framework Imidazolate derivate
a b s t r a c t A new copper(I) imidazolate metal-organic framework, Cu2[bbimb] (1), has been synthesized by solvothermal reaction of Cu(NO3)2 3H2O and 1,3-bis(2-benzimidazol)benzene (H2bbimb) in an ammonium/ methanol mixture. Single-crystal X-ray diffraction analysis reveals that the structure of compound 1 contains three crystallographically independent Cu(I) ions and one bbimb2 ligand. Each copper center in 1 is linearly coordinated by two nitrogen atoms from two different bbimb ligands and each bbimb coordinates four copper ions to form a neutral three-dimensional metal-organic framework with zeolite ABW topology. Crystal data for 1: Monoclinic, C2/c, a = 22.1660(9) Å, b = 14.9825(7) Å, c = 11.4773(4) Å, b = 107.972(2)o, V = 3625.7(3) Å3, Z = 8. Ó 2008 Elsevier Inc. All rights reserved.
1. Introduction Among the vast family of porous materials [1], metal-organic frameworks constitute an important class. Synthesis of metal-organic frameworks (MOFs) has increased enormously due to their fascinating structures, properties and their various potential applications in catalysis, separation, gas storage and molecular recognition [2–7]. Especially, constructing MOFs with expanded zeolite and zeolite-like topologies still remains a great challenge. Recently, scientists have successfully acquired some ZMOFs (ZMOF = zeolitelike MOF) with zeolite SOD, MTN, ABW, GIS, ANA and RHO topologies by utilizing effective synthetic strategies [8–25]. Most of the ZMOFs explored to date are based on metal-imidazolates, and it is accepted that imidazolates and its derivatives are very unique and important ligands for the fabrication of MOFs with zeolitic topologies. Besides zeolitic topologies of metal-imidazolates, metal-imidazolates with zero-dimensional (0D) rings, 1D zigzag and helical chains, and 2D layer structures have been reported so far [26–32]. Based on our earlier research [21,32,33] and the study of known metal-imidazolates, we have extended our research to the metal-imidazolate derivatives system, and we have found that 1,3-bis(2-benzimidazol)benzene (H2bbimb), as a new ligand, can be used as a building block for constructing MOFs. This ligand, as well as the related molecule 1,3-bis(1-methylbenzimidazol-2-yl)benzene (mbzimpH), presents multiple * Corresponding author. Tel.: +86 431 85168614; fax: +86 431 85168624. E-mail address: [email protected] (Y. Liu). 1387-1811/$ - see front matter Ó 2008 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2008.10.037
nitrogen-donor sites with the possibility of reversible protonation and deprotonation, properties that have been capitalized upon in supramolecular chemistry for the preparation of mononuclear [34], dinuclear [35,36] and trinuclear cyclometalated coordination compounds [37] with interesting helical, chiral cavity structural features and photophysical properties. To the best of our knowledge, there is no 3D structure reported yet based on H2bbimb. The H2bbimb ligand features multidentate character; that is, it possesses two imine N atoms and two amine NH groups. After the H2bbimb ligand is partially or fully deprotonated at different pH conditions, the amine N atoms can act as coordination donors. Herein, we report the synthesis and crystal structure of a new metal-organic framework, Cu2[bbimb] (1), based on copper(I) ions and the [bbimb]2 ligands. 2. Experimental 2.1. Physical measurements X-ray powder diffraction (XRPD) data were collected on a Rigaku/max-2550 diffractometer with CuKa radiation (k = 1.5418 Å). The elemental analyses were performed on a Perkin–Elmer 2400 LSII C.H.N. analyzer. The inductively coupled plasma (ICP) analyses were carried out on a Perkin–Elmer Optima 3300DV ICP instrument. The infrared (IR) spectra were recorded within the 400– 4000 cm1 region on a Nicolet Impact 410 FTIR spectrometer using KBr pellets. The thermal gravimetric analyses (TGA) were performed on NETZSCH STA449C thermogravimetric analyzer in N2 flow with a heating rate of 10 oC min1.
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L. Zhang et al. / Microporous and Mesoporous Materials 119 (2009) 344–348 Table 1 Crystal data and structure refinement for 1.
Fig. 1. Simulated and experimental X-ray powder diffraction patterns of compound 1.
Empirical formula Formula weight Temperature (K) Wavelength (Å) Crystal system Space group a (Å) b (Å) c (Å) a (o) b (o) c (o) V (Å3) Z Dcalc (Mg m3) Absorption coefficient (mm1) Reflections collected Reflections unique Goodness-of-fit on F2 Final R indices [I>2r(I)] Largest difference peak and hole (e Å3)
C20 H12 Cu2 N4 435.42 293(2) 0.71073 Monoclinic C2/c 22.1660(9) 14.9825(7) 11.4773(4) 90 107.972(2) 90 3625.7(3) 8 1.595 2.356 13130 4519 (Rint = 0.0727) 0.868 R1 = 0.0415 wR2 = 0.0781 0.451, 0.485
of one bbimb ligand (calcd. 70.81 wt%). XRD analyses indicated that the compounds became amorphous after the decomposition. 2.3. Structural determination Suitable single-crystal of 1 (0.29 0.21 0.18 mm3) was selected for single-crystal X-ray diffraction analyses. The intensity data was collected on a Siemens Smart CCD diffractometer using graphite-monochromated Mo-Ka radiation (k = 0.71073 Å). The number of collected reflections and independent reflections were 13130 and 4519 for 1. Data processing was accomplished with the SAINT processing program. The structure was solved by direct
Table 2 Atomic coordinates (104) and equivalent isotropic displacement parameters (Å2 03) for 1.
Fig. 2. Thermal gravimetric analysis curve for 1.
2.2. Synthesis The ligand 1,3-bis(2-benzimidazol)benzene (H2bbimb) was prepared according to a literature procedure [38]. Cu(NO3)2 3H2O (0.24 g, 1 mmol) and H2bbimb (0.155 g, 0.5 mmol) were suspended in a mixture of ammonium (5 mL) and methanol (5 mL), which was heated at 180 oC for 2 days in a 15 mL teflon-lined stainless-steel autoclave under autogeneous pressure. The resulting yellow block-like crystals of Cu2[bbimb] 1, were isolated by filtration, washed with distilled water, and dried in air (70% yield based on Cu(NO3)2 3H2O). Compound 1 was insoluble in water and all common organic solvents, such as ethanol, acetone, acetonitrile, benN,N0 zene, tetrahydrofuran, N,N0 -dimethylformamide, diethylformamide, and dimethyl sulfoxide. The agreement between the experimental and simulated XRD patterns indicated the phase purity of the product (Fig. 1). Elemental analysis for C20H12Cu2N4: found (wt%): C, 55.02; H, 2.71; N, 12.91. Calcd. (wt%): C, 55.17; H, 2.78; N, 12.87. The TG curve of 1 exhibited a total weight loss of 69.6 wt% from around 100–1000 oC (as shown in Fig. 2), corresponding to the loss
Atom
x
y
z
Ua (eq)
Cu(1) Cu(2) Cu(3) N(1) N(2) N(3) N(4) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20)
2500 0 1056(1) 1848(1) 874(1) 1059(1) 1118(1) 1097(2) 933(1) 480(2) 206(2) 369(2) 815(2) 994(2) 1224(2) 1253(2) 1396(2) 1571(2) 1598(2) 1459(2) 1286(2) 1910(2) 2437(2) 2337(2) 1731(2) 1209(2) 1303(2)
2500 1136(1) 5170(1) 1742(2) 1149(2) 5508(2) 5303(2) 3351(2) 2455(2) 2202(2) 2841(3) 3728(3) 3997(2) 4941(2) 1777(2) 6306(2) 7131(3) 7808(3) 7683(3) 6872(3) 6177(2) 1007(2) 646(3) 79(3) 445(3) 86(3) 643(2)
5000 2500 7545(1) 4104(2) 3230(3) 5987(2) 4075(2) 4552(3) 4556(3) 5111(3) 5666(3) 5653(3) 5090(3) 5052(3) 3962(3) 5597(3) 6170(3) 5525(4) 4338(4) 3770(3) 4411(3) 3395(3) 3156(4) 2385(4) 1856(4) 2083(4) 2869(3)
27(1) 32(1) 29(1) 24(1) 27(1) 26(1) 26(1) 23(1) 23(1) 30(1) 35(1) 30(1) 22(1) 23(1) 23(1) 29(1) 43(1) 54(1) 54(1) 40(1) 27(1) 27(1) 41(1) 55(1) 60(1) 48(1) 28(1)
a
U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.
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Table 3 Selected bond lengths (Å) and bond angles (o) for 1. Cu(1)–N(1) Cu(1)–N(1)#1 Cu(2)–N(2) Cu(2)–N(2)#2 Cu(3)–N(4)#3 Cu(3)–N(3) N(1)–C(8) N(1)–C(15) N(2)–C(8) N(2)–C(20) N(3)–C(7) N(3)–C(9) N(4)–C(7) N(4)–C(14) N(4)–Cu(3)#4 C(15)–C(20) C(16)–C(17) C(17)–C(18) N(1)–Cu(1)–N(1)#1 N(2)–Cu(2)–N(2)#2 N(4)#3–Cu(3)–N(3) C(8)–N(1)–C(15) C(8)–N(1)–Cu(1) C(15)–N(1)–Cu(1) C(8)–N(2)–C(20) C(8)–N(2)–Cu(2) C(20)–N(2)–Cu(2) C(7)–N(3)–C(9) C(7)–N(3)–Cu(3) C(9)–N(3)–Cu(3) C(7)–N(4)–C(14) C(7)–N(4)–Cu(3)#4 C(14)–N(4)–Cu(3)#4 C(2)–C(1)–C(6) C(1)–C(2)–C(3) C(1)–C(2)–C(8) C(3)–C(2)–C(8) C(4)–C(3)–C(2) C(5)–C(4)–C(3) C(4)–C(5)–C(6) C(5)–C(6)–C(1) C(5)–C(6)–C(7) C(1)–C(6)–C(7) C(19)–C(20)–C(15)
1.876(3) 1.876(3) 1.859(3) 1.859(3) 1.859(3) 1.861(3) 1.343(4) 1.400(4) 1.338(4) 1.376(4) 1.340(4) 1.389(4) 1.348(4) 1.384(4) 1.859(3) 1.403(4) 1.374(5) 1.403(6) 180.00(19) 178.75(18) 172.10(12) 104.1(3) 129.2(2) 126.7(2) 104.9(3) 127.7(2) 125.4(2) 104.8(3) 124.4(2) 129.5(2) 104.8(3) 131.1(2) 124.0(2) 120.9(3) 119.3(3) 120.6(3) 120.1(3) 120.0(3) 120.3(3) 120.6(3) 118.9(3) 121.7(3) 119.4(3) 121.1(3)
C(1)–C(2) C(1)–C(6) C(2)–C(3) C(2)–C(8) C(3)–C(4) C(4)–C(5) C(5)–C(6) C(6)–C(7) C(9)–C(10) C(9)–C(14) C(10)–C(11) C(11)–C(12) C(12)–C(13) C(13)–C(14) C(15)–C(16) C(18)–C(19) C(19)–C(20)
1.391(5) 1.396(4) 1.396(5) 1.478(4) 1.390(5) 1.379(5) 1.395(4) 1.474(5) 1.390(5) 1.399(4) 1.381(6) 1.394(6) 1.369(5) 1.395(5) 1.390(5) 1.372(6) 1.391(5)
N(3)–C(7)–N(4) N(3)–C(7)–C(6) N(4)–C(7)–C(6) N(2)–C(8)–N(1) N(2)–C(8)–C(2) N(1)–C(8)–C(2) N(3)–C(9)–C(10) N(3)–C(9)–C(14) C(10)–C(9)–C(14) C(11)–C(10)–C(9) C(10)–C(11)–C(12) C(13)–C(12)–C(11) C(12)–C(13)–C(14) N(4)–C(14)–C(13) N(4)–C(14)–C(9) C(13)–C(14)–C(9) C(16)–C(15)–N(1) C(16)–C(15)–C(20) N(1)–C(15)–C(20) C(17)–C(16)–C(15) C(16)–C(17)–C(18) C(19)–C(18)–C(17) C(18)–C(19)–C(20) N(2)–C(20)–C(19) N(2)–C(20)–C(15)
114.3(3) 123.2(3) 122.5(3) 115.0(3) 121.5(3) 123.5(3) 131.4(3) 108.0(3) 120.7(3) 117.4(3) 121.9(4) 120.9(4) 118.0(3) 130.8(3) 108.1(3) 121.1(3) 131.3(3) 121.0(3) 107.6(3) 117.1(3) 122.0(4) 121.0(4) 117.7(4) 130.4(3) 108.4(3)
Symmetry transformations used to generate equivalent atoms: #1 x+1/2, y+1/2, z+1 #2 x,y, z+1/2 #3 x, y+1, z+1/2 #4 x, y+1, z1/2.
methods and refined by full-matrix least-squares on F2 using SHELXTL Version 5.1 [39]. All the copper atoms were first located. Then carbon, nitrogen atoms, and hydrogen atoms of the organic framework subsequently were found in difference Fourier maps. The hydrogen atoms of the ligand molecule were placed geometrically. All non-hydrogen atoms were refined anisotropically. Crystal data and refinement parameters for the structure determination are presented in Table 1. The final atomic coordinates and the selected bond distances and angles are given in Tables 2 and 3, respectively.
perature should be an important factor in controlling the reduction of Cu(II) ions into Cu(I). In compound 1, each bbimb2 ligand binds to four Cu(I) ions, and in turn each Cu(I) is linearly coordinated by two nitrogen atoms from two independent bbimb2 ligands. The average Cu–N bond length is 1.865(3) Å, which is slightly shorter than that observed in [Cu2(L3)2](ClO4)2, 1.890 (7) Å (L3 stand for 1,3-bis(1-methylbenzimidazol-2-yl)benzene ligand) [35]. The N– Cu–N bond angles for Cu(1) and Cu(2) atoms are almost linear, 180.00(19) and 178.75(18)o, respectively. The N–Cu–N bond angles for Cu(3) is 172.10(12)o, deviated slightly from the ideal 180o. Two benzimidazole rings are not coplanar with respect to the central benzene ring, showing dihedral angles of 38.2 and 44.7o, respectively. Compound 1 exhibits a novel three-dimensional metal-organic framework based on the assembly of Cu(I) and the bbimb2 ligand (Fig. 3). Each bbimb2 ligand binds to four Cu(I) atoms, and can be viewed as a 4-connected tetrahedral node due to the deviation of benzimidazole rings from the central benzene ring (Fig. 3b); all these bbimb2 ligands link together through the linearly coordinated monovalent Cu ions to form a neutral 3D framework (Fig. 3c and d). From the perspective of network topology, the linearly coordinated Cu atoms serve to replace the O2 bridges in traditional zeolites, and the bbimb2 ligands act as tetrahedral nodes. Thus, compound 1 represents a 3D 4-connected net with zeolite ABW topology (the analyzed vertex symbol and coordination sequence of compound 1 from the program package TOPOS 4.0 are the same as those of ABW in the zeolite database) (Fig. 3e and f) [40,41]. As known, the framework symmetry of zeolite ABW is higher then compound 1 (orthorhombic, Imma for zeolite ABW; monoclinic, C2/c for compound 1). When the bbimb2 ligands are regarded as 4-connected vertices, both the vertex symbol and coordination sequence are same as those for the zeolite ABW structure. The framework of compound 1 also contain eight-membered rings as the structure of a zeolite ABW, but the channels are occupied with phenyl groups and copper metal ions. The channels of the structure are viewed along the [1 0 0] direction, as shown in Fig. 3d. 4. Conclusion In this paper, we have successfully synthesized a new metal-organic framework, Cu2[bbimb], using 1,3-bis(2-benzimidazol)benzene as a new organic bridging ligand. This study reveals that new nitrogen-donor H2bbimb ligand can be used as a tetrahedral building block to construct zeolite-like MOFs. Here we present the first structure based on such ligand, the assembly of the ligand with Cu(I) has led to the construction of a zeolite-like structure having ABW topology. Work is in progress to expand our work with this ligand to other metals. Also similar expanded ligands will synthesized to allow the access of accessible large cavities suitable for inclusion chemistry. Acknowledgments
3. Results and discussion 3.1. Crystal structure of Cu2[bbimb] 1 Single-crystal X-ray diffraction analysis indicates that compound 1 crystallizes in the monoclinic space group C2/c with the formula of Cu2[bbimb]. The asymmetric unit of 1 contains 27 non-hydrogen atoms, of which 24 atoms belong to one bbimb2 ligand (20 oC and 4 N atoms) and 3 atoms are crystallographically distinct Cu(I) ions. We started the reaction with Cu(II) ions, and only Cu(I) was found in the final compound 1. It should be mentioned that there were several reports of a hydrothermal approach for the generation of Cu(I) imidazolate polymers [26–29]. The tem-
The authors acknowledge the financial support of the Natural Science Foundation of China (Nos. 20671041, 20701015) and the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University. Appendix A. Supplementary data Crystallographic data for the structure reported in this paper, in the form of a CIF file, have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 692102 for 1. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2
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Fig. 3. Single-crystal structure of 1: (a) the bbimb2 ligand, (b) each bbimb2 ligand coordinated to four Cu atoms that can be viewed as four-connected tetrahedral building units, (c) ball-and-stick view of 1 along the [0 0 1] direction, (d) ball-and-stick view of 1 along the [1 0 0] direction, (e) framework of 1 showing the Cu bridges and tetrahedral ligands, (f) topology of the framework of 1 viewed along c direction. Color code: Cu: orange; C: gray; N: blue; the bbimb2 ligand as 4-connected nodes are denoted by green spheres. Hydrogen atoms are omitted for clarity. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
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