Two Metal-Carboxylate Frameworks Featuring Uncommon 2D + 3D

Publication Date (Web): March 27, 2009. Copyright © 2009 American Chemical Society .... and Yuan-Gen Yao. Crystal Growth & Design 2016 16 (7), 4012-4...
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Two Metal-Carboxylate Frameworks Featuring Uncommon 2D + 3D and 3-Fold-Interpenetration: (3,5)-Connected Isomeric hms and gra Nets Lei Hou, Jie-Peng Zhang,* and Xiao-Ming Chen*

CRYSTAL GROWTH & DESIGN 2009 VOL. 9, NO. 5 2415–2419

MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen UniVersity, Guangzhou 510275, China ReceiVed December 2, 2008; ReVised Manuscript ReceiVed February 22, 2009

ABSTRACT: Two new interpenetrated metal-carboxylate frameworks (MCFs) [(CH3)2NH2][Zn2(BDC)(BTB)][Zn3(BTB)2(H2O)2] · 4DMA · 2C2H5OH · 7H2O (MCF-25, 1, H2BDC ) 1,4-benzenedicarboxylic acid, H3BTB ) benzene-1,3,5-tribenzoic acid), and [(CH3)2NH2][Zn2(BDC)(BTB)] · 3DMF · 2H2O (MCF-26, 2), synthesized by solvothermal reaction and room-temperature evaporation, respectively, are constructed by Zn2(O2CR)5 (in 1 and 2) and Zn3(O2CR)6 (in 1) units incorporating mixed BDC2- and BTB3ligands. 1 is composed of two different frameworks with 2D 63 bilayers and a rare (3,5)-connected 3D hms net giving an interesting 2D + 3D framework, whereas 2 features a novel 3-fold interpenetrated (3,5)-connected gra net with chiral, hexagonal helical channels. Structural analysis shows that the two 3D nets of hms in 1 and gra in 2 are strict isomers with the same components but different steric arrangements, which are derived from different orientations of the two axial carboxylate bridges in two isomeric Zn2(O2CR)5 SBUs. Introduction Increasing interest has been ignited by interpenetrated coordination polymers because of their unique advantages in enhancing stability, specific surface area, gas sorption, selective separation, molecular dynamics, and abundant structural aesthetics.1 A large number of interpenetrations have been found from 2-fold to even beyond 10-fold,2 because of the fact that Nature abhors a vacuum and interpenetration reduces voids. Among them, the interpenetrations between the same networks are very common because the same molecular fragments favor the same periodicity. In contrast, as noted recently,1g,2a,3 the interpenetrations of chemically or crystallographically distinct nets are not common, whereas those with different dimensions interpenetrated, such as zero-dimensional (0D) + 1D, 1D + 2D, 1D + 3D, and 2D + 3D, are still rare, despite their intrinsic topological appeal for chemists.4 Small-sized, low-nuclear secondary building units (SBUs) and lengthy bridging ligands usually facilitate interpenetrated frameworks. In contrast, high-nuclear clusters are more likely to form high-connected and noninterpenetrated nets.5 Benzene-1,3,5tribenzoic acid (H3BTB, Scheme 1) is a tritopic ligand for linking low-nuclear Cu2(O2CR)4 and Zn3(OH)(O2CR)6 SBUs or higher-nuclear Zn4O(O2CR)6 motifs to give either interpenetrated or noninterpenetrated porous networks.6 Meanwhile, incorporating linear 1,4-benzenedicarboxylic acid (H2BDC) linker as coligands into BTB-Zn4O species was found to generate a different topology, [Zn4O(BDC)(BTB)4/3] (UMCM-1).7 Therefore, it can be anticipated that new types of interpenetrated networks can be formed by interlinking low-nuclear clusters with mixed BDC2- and BTB3- ligands. This consideration led to our successful construction of two new interpenetrated metalcarboxylate frameworks (MCFs) by mixed BDC2- and BTB3ligands, [(CH3)2NH2][Zn2(BDC)(BTB)][Zn3(BTB)2(H2O)2] · 4DMA · 2C2H5OH · 7H2O (MCF-25, 1) and [(CH3)2NH2][Zn2(BDC)(BTB)] · 3DMF · 2H2O (MCF-26, 2) containing Zn2* To whom correspondence should be addressed. E-mail: zhangjp7@ mail.sysu.edu.cn (J.-P.Z.); [email protected] (X.-M.C.). Fax: (86)-2084112245; Tel: (86)-20-84113986.

Scheme 1. Structures of the H2BDC and H3BTB Ligands

(O2CR)5 (in 1 and 2) and Zn3(O2CR)6 (in 1) SBUs. In contrast to a totally (3,6)-connected net in UMCM-1, 1 exhibits 2D 63 bilayers interpenetrated into a rarely observed (3,5)-connected 3D hms net, whereas 2 features a novel 3-fold interpenetrated (3,5)-connected 3D gra net. Interestingly, the hms net in 1 and the gra net in 2 are structural isomers with the same components, resulting from two isomeric Zn2(O2CR)5 SBUs. Experimental Section Materials and General Methods. All solvents and starting materials for the synthesis were purchased commercially and were used as received. H3BTB was synthesized according to a documented procedure by 1,3,5-tri(4-methylphenyl)benzene.6b Infrared spectra were obtained from KBr pellets on a Bruker TENSOR 27 Fourier transform infrared spectrometer in the 400-4000 cm-1 region. Elemental analyses (C, H, N) were performed on a Perkin-Elmer 240 elemental analyzer. Thermogravimetric analyses (TGA) were performed at a rate of 10 °C/ min under air using a NETZSCH TG 209 system. Powder X-ray diffraction (PXRD) data were recorded on a Bruker D8 ADVANCE X-ray powder diffractometer (CuKR, 1.5418 Å). Synthesis of [(CH3)2NH2][Zn2(BDC)(BTB)][Zn3(BTB)2(H2O)2] · 4DMA · 2C2H5OH · 7H2O (MCF-25, 1). A mixture of H2BDC (0.025 g, 0.15 mmol), H3BTB (0.033 g, 0.075 mmol), and Zn(NO3)2 · 6H2O (0.067 g, 0.225 mmol) in N,N′-dimethylacetamide (DMA) (6 mL), ethanol (2 mL), and H2O (1 mL) was placed in a Teflon-lined stainless steel vessel and heated at 90 °C for 50 h, and then cooled to room temperature at a rate of 0.1 °C/min. A small quantity of pale-yellow crystals were mechanically separated (ca. 1.8 mg). Anal. Calcd for C111H123Zn5N5O37: C, 54.50; H, 5.07; N, 2.86. Found: C, 54.58; H, 5.02; N, 2.91%. IR (KBr, cm-1): 3410m, 2933w, 1614vs, 1540s, 1503m, 1405vs, 1260v, 1185v, 1018m, 860w, 788m.

10.1021/cg801308u CCC: $40.75  2009 American Chemical Society Published on Web 03/27/2009

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Table 1. Crystallographic Data and Structural Refinements for 1 and 2a

formula weight T (K) cryst syst space group a (Å) b (Å) c (Å) β (deg) V (Å3) Z Dc (g cm-3) µ (mm-1) reflns collected/unique Rint R1b (>2σ/all data) wR2b (>2σ/all data) GOF Flack param

C89H49Zn5O24

C35H19Zn2O10

1829.13 295(2) monoclinic C2 16.783(6) 28.062(11) 13.894(5) 96.420(7) 6503(4) 2 0.934 0.958 16756/8898 0.0762 0.0593/0.1116 0.1120/0.1262 0.931 0.24(2)

730.24 295(2) hexagonal P6522 16.5748(7) 16.5748(7) 28.129(2) 90 6692.4(6) 6 1.087 1.117 23135/4398 0.0862 0.0601/0.1065 0.1576/0.2067 0.942 0.11(5)

a PLATON/SQUEEZE was employed. b R1 ) Σ|Fo| - |Fc|/Σ|Fo|; wR2 ) [Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2. Without employing PLATON/ SQUEEZE: for 1, R1 ) 0.1127 and wR2 ) 0.2742 (I > 2σ[I]), S ) 1.187; for 2, R1 ) 0.1011 and wR2 ) 0.2391 (I > 2σ[I]), and S ) 1.166.

Synthesis of [(CH3)2NH2][Zn2(BDC)(BTB)] · 3DMF · 2H2O (MCF26, 2). A mixture of H2BDC (0.013 g, 0.075 mmol), H3BTB (0.033 g, 0.075 mmol), acetamide (0.013 g, 0.225 mmol), and Zn(ClO4)2 · 6H2O (0.084 g, 0.225 mmol) in N,N′-dimethylformamide (DMF) (6 mL) was stirred at room temperature for 4 h. After filtrating, the filtrate was stood for about 6 months with the pale-yellow crystals of 2 gradually

Hou et al. appeared, which can be collected by filtrating and washing with ethanol. The yield was ca. 6.5 mg. Anal. Calcd for C46H52Zn2N4O15: C, 53.55; H, 5.08; N, 5.43. Found: C, 53.61; H, 5.04; N, 5.49%. IR (KBr, cm-1): 3422m, 2933w, 1658s, 1614s, 1531w, 1406vs, 1253w, 1107v, 1014w, 866w, 788m. Crystallography. The diffraction data were collected at 295(2) K with a Bruker AXS Smart Apex diffractometer using ω rotation scans with a scan width of 0.3° and Mo KR radiation (λ ) 0.71073 Å). The structures were solved by direct methods and refined by full-matrix least-squares refinements based on F2.8 All non-hydrogen atoms were refined anisotropically with the hydrogen atoms added to their geometrically ideal positions and refined isotropically. In 1, the Zn2 atom, carboxylate O2 atom of BTB3- ligands, and aqua ligands are 2-fold disordered, which were refined in two positions, respectively. The crystals of 1 and 2 scattered weakly and only low-angle data could be detected because of the presence of heavily disordered solvent molecules in the cavities. Thus the SQUEEZE routine of PLATON9 was applied to remove the contributions to the scattering from the solvent molecules. The final formulas were determined by combining single-crystal structures, elemental microanalyses, and TGA data. Selected crystallographic data and structural determination parameters are given in Table 1.

Results and Discussion Crystal Structure of 1. Solvothermal reaction of H2BDC, H3BTB and Zn(NO3)2 with a molar ratio 2:1:3 in DMA/ C2H5OH/H2O at 90 °C for 50 h gave the pale-yellow crystals of 1. X-ray crystallography reveals that 1 crystallizes in the chiral space group C2. 1 shows an interesting 2D + 3D interpenetrated framework built from 63 bilayers and (3,5)-

Figure 1. (a) Perspective views of the [Zn3(O2CR)6(H2O)2] and [Zn2(O2CR)5] SBUs in the 2D bilayers and 3D net in 1, respectively. (b) One 2D layer (purple) interpenetrated the space between two sheets of 3D net in 1 (SBU1, Zn orange polyhedron; SBU2, Zn blue polyhedron). (c) The 2D + 3D nets in 1 viewed along the c-axis showing 1D elliptic channels. (d) Schematic representation of 63 bilayers + (63)(698) hms nets in 1 with the 5-connected SBU2 highlighted (orange balls), and Zn2 atoms acting as 2-connected sticks (blue).

Metal-Carboxylate Frameworks with 2D + 3D and 3-Fold Interpenetration

Figure 2. (a) Perspective view of [Zn2(O2CR)5] SBU3 in 2. (b) The 3D framework in 2 viewed along the c-axis with staggered alignments between neighboring sheets within one net (SBU3, Zn blue polyhedron). (c) Schematic representation of 3-fold interpenetrated (63)(698) gra nets in 2.

Figure 3. 3-fold interpenetrated structure in 2 with a hexagonal helical channel along the c-axis highlighted.

connected 3D nets based on tri- and dinuclear zinc clusters, respectively. The asymmetric unit of 1 contains two discrete fragments (see Figure S1 in the Supporting Information) with three independent zinc atoms. As shown in Figure 1a, Zn1 atom is trigonal-bipyramidally coordinated to one chelating, two bridging carboxylate groups, and one terminal aqua ligand, and two pairs of symmetry-related carboxylate bridges are further converged to the central Zn2 atom to give a trinuclear

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Figure 4. Evolution from hms net in 1 to gra net in 2, achieved through opposite 90° rotations of the two axial carboxylate groups in SBU2 into isomeric SBU3 and corresponding to a 180° rotation of one layer in hms net (Zn, blue; C, white; O, red).

Zn3(O2CR)6(H2O)2 cluster, namely SBU1. Each SBU1 connects six BTB3- ligands, and each BTB3- ligand links three SBU1 to form a (3,6)-connected bilayer parallel to the ab plane (images b and c in Figure 1 and S3 in the Supporting Information). The bilayer has a hexagonal ring with a diameter of ca. 12.2 Å (excluding van der Waals radii), which can be viewed as a 63 net, being distinct from those documented 6-connected bilayers with similar SBU1 but featuring 36 net.10 The adjacent bilayers are eclipsed along the c-axis with interbilayer separations of 7.17 Å (the closest Zn · · · Zn separation). A second independent fragment exists in 1, in which two tetrahedral zinc atoms are ligated by three carboxylate bridges from three BTB3- ligands and two axial carboxylate groups from two BDC2- linkers, to form a dinuclear Zn2(O2CR)5 cluster, SBU2 (Figure 1a). Each SBU2 is connected by three BTB3ligands to form a 63 layer parallel to the ab plane. The SBU2 also stands for a new type of 5-connected metal-carboxylate SBU in 3D frameworks. The layers are arranged in an eclipsed fashion (separation 10.63 Å) and are extended by BDC2- linkers into a 3D open network, featuring a hexagonal channel with a diameter of ca. 11.7 Å along the c-axis (Figure 1c and S4 in the Supporting Information). This 3D framework can be simplified as a (3,5)-connected hms net [Schla¨fli symbol (63)(698)],11 upon considering SBU2 as 5-connected trigonalbipyramidal nodes and BTB3- as 3-connected nodes (Figure 1d). In contrast to the extensive investigations on (3,4)- and (3,6)-connected nets, there have been only a few on (3,5)connected net, especially the (63)(698) topology; it has been observed only in several coordination polymers,1f,2a,12 where monometal ions acting as 5-connected nodes are linked by trigonal 1,3,5-benzenetricarboxylate or C(CN)3- ligands, as well as axial N- or O-containing pillars. To the best of our knowledge, the (3,5)-connected net based on dinuclear metalcarboxylate clusters is very rare,13 owing to that such clusters are more possible to serve as 4- or 6-connected nodes. A striking feature of 1 is that each 2D bilayer is parallelly penetrated into the space between two sheets of the 3D network to yield a 2D

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Figure 5. Hypothetic interpenetration between 2D bilayers in 1 and 3D gra net in 2 (left, viewed along the c-axis), which will be prevented by the heavily steric repulsions arising from the center BTB3- phenyl rings in 3D net and terminal aqua ligands of SBU1 (right, C · · · O contacts of ca. 1.96 Å).

+ 3D interpenetrated framework (Figure 1b). The alignment exhibits an offset along the c-axis and leads to the reduction of the original hexagonal windows of 3D net into elliptic 10.4 × 6.0 Å2 channels (Figure 1c). Though the interpenetration exists in 1, a solvent accessible volume of 50.5% estimated by PLATON9 remains available, which is occupied by [(CH3)2NH2]+ counterions and solvent molecules. The mutual interpenetration between 2D and 3D frameworks is unusual, and only a few such examples, such as 6-connected 3D R-Po nets interwoven with 2D 63 hydrogen-bonded sheets4a and 4-connected 3D CdSO4-like nets inserted with 2D 44 layers, have been documented to date.4b-d The structure with mutually interpenetrated (3,5)-connected 3D net and 2D layers was not reported for coordination polymers, hydrogen-bonded nets, or inorganic compounds.1g,14 In addition, substituting H2BDC with other ditopic carboxylate bridges, such as cyclohexane-1,4dicarboxylic acid, HOOC-(CH2)n-COOH (n ) 2-4), and p-phenylenediacrylic acid, to produce the same 2D + 3D net in 1 failed, which also reflects that such a 2D + 3D net is indeed scarce. Crystal Structure of 2. The rarely heterogeneous interpenetration in 1 reminds us that a common network with the same nets interpenetrated may exist and may be obtained through tuning the reaction condition. By replacing Zn(NO3)2 in DMA/ethanol/water with Zn(ClO4)2 in DMF/acetamide at room temperature, the pale-yellow prism crystals of 2 were yielded. 2 has a chiral hexagonal space group P6522 and exhibits a homogeneously 3-fold interpenetrated (3,5)connected framework built by mixed BDC2-/BTB3- ligands and 5-connected dinuclear zinc carboxylate clusters (SBU3). Interestingly, SBU3 with the component of Zn2(O2CR)5 is an structural isomer of SBU2 (Figure 2a), in which two zinc atoms are coordinated by three carboxylate bridges from three BTB3- ligands and two axial carboxylate groups from two BDC2- linkers. A significant difference is that the two axial carboxylate groups in SBU3 show opposite orientations, whereas those in SBU2 point to the same directions. Such a delicate difference is very uncommon for the documented SBUs. Similar to SBU2 in 1, each SBU3 in 2 binds three BTB3- ligands to generate 63 sheets with the hexagonal rings of 12.6 Å, which are further axially connected by BDC2-

pillars to give a 3D framework with interlayer spans of 10.75 Å (Zn · · · Zn). In 2, adjacent 63 layers are arranged in a staggered fashion, thus the hexagonal window is divided by a BTB3- ligand from neighboring sheet into three parts along the c-axis (Figure 2b), which is different with that of 3D net in 1. The framework of 2 exhibits a (3,5)-connected gra net, having the same Schla¨fli symbol (63)(698) with that of hms net (Figure 2c). Such two nets are isomers with the only difference derived from different alignments between the adjacent sheets.15 The gra net is also few, and only observed in several compounds.14b,15,16 As expected, in virtue of long BDC2- pillars and hexagonal rings within one framework, the overall structure of 2 discloses a Class IIa 3-fold interpenetration (Figure 2c) related by a 61 screw axis, which is rare as only four cases with Z > 2 have been reported.1f Meanwhile, the adjacent layers from independent nets are packed with ABC cubic close-packed modes, which is very unusual in 3D coordination polymers.17 Moreover, such stacks lead to a unique chiral hexagonal channel running along the c-axis with a diameter of ca. 8.3 Å (Figure 3), which exhibits a solvent accessible volume of 43.1% occupied by [(CH3)2NH2]+ counterions and solvent molecules.9 Structural Difference and Evolution between 1 and 2. Upon further structural analysis, we noticed that the two axial carboxylate groups and 2-fold-axis-threaded C43 carboxylate plane in SBU2 in 1 are almost coplanar with a torsion angle (C47-O10-Zn3–O9) of 6.8°, as shown in Figures 1a and 4. However, two such groups of SBU3 in 2 are heavily deviated from the C16 carboxylate plane with a torsion angle (C17O4-Zn1-O1) of 94.2° (Figures 2a and 4). In fact, opposite rotations of the two axial carboxylate groups in SBU2 along the Zn · · · Zn axis by 90° give the equivalent of SBU3, which will result in a 180° rotation of one of the adjacent 63 layers in the 3D net of 1 into the staggered fashion in 2. Consequently, a gra net in 2 can be evolved from an hms net in 1 (Figure 4), or vice versa. Such result also implies that the different orientations of the two axial carboxylate groups in SBU2 and SBU3 are critical to the different packing fashions of the two 3D isomeric nets in 1 and 2. To the best of our knowledge, such a pair of strictly isomeric networks with the same Schla¨fli symbol and components has not been reported.

Metal-Carboxylate Frameworks with 2D + 3D and 3-Fold Interpenetration

In fact, the 2D bilayers in 1 cannot penetrate into the 3D gra net in 2. It can be noted that the axial size of 10.77 Å (Ow · · · Ow) of SBU1 is basically equivalent to the interlayer distance (Zn · · · Zn ) 10.75 Å) of the gra net in 2. Therefore, if such penetration occurred, steric hindrances would appear between SBU1 and the BTB3- phenyl rings in gra net because of a staggered interlayer arrangement of the gra net. As a typical result shown in Figure 5, the SBU1 in 2D sheets would pile up with the central BTB3- phenyl rings of the 3D net, resulting in the very short C · · · Ow distance of ca. 1.96 Å between these phenyl rings and terminal aqua ligands of SBU1, which suggests very heavily steric repulsions. However, the 63 layers of the hms net have an interlayer eclipsed arrangement and exhibit open hexagonal channels, thus the wavy 2D bilayers can be placed between the 63 layers of the hms net with an offset. The distinct nets in 1 and 2 are derived from the different synthesis conditions of 1 and 2. Besides the solvent effect, it is reasonable that the high pressure and temperature in the solvothermal reaction of 1 may drive the generation of trinuclear SBU1 to form the bilayer, which concurrently induces the formation of hms net in 1, rather than a gra net. TGA and PXRD. The bulk samples of 1 and 2 for PXRD characterization can be obtained by several runs of synthesis. The PXRD patterns of 1 and 2 measured at 298 K are in good agreement with their corresponding simulated patterns, indicating phase purities of these samples (see Figures S6 and S7 in the Supporting Information). Thermogravimetric analyses of 1 and 2 under air environment show gradual solvent weight losses of 22.9% and 23.8% in the range 30-230 °C and 30-320 °C for 1 (4 DMA, 2 C2H5OH, and 7 H2O per formula unit, calcd 23.2%) and 2 (3 DMF and 2 H2O per formula unit, calcd 24.7%), respectively (see Figures S8 and S9 in the Supporting Information). Above 230 °C, 1 starts to release the aqua ligands and neutral (CH3)2NH molecules with a weight loss of 3.2% (calcd 3.3%) before 280 °C. The removal of (CH3)2NH molecules leads to the framework becoming protonated and thus unstable.18 Consequently, another abrupt weight loss is followed by the departure of BDC2- and BTB3- ligands up to 520 °C (found 59.5%; calcd 60.1%). Similar to 1, beyond 320 °C, the escape of the (CH3)2NH molecules in 2 induces the destruction of the structure with a total weight loss of 61.4% (calcd 62.5%) ending at 565 °C, leaving a white residue of ZnO (found 15.0%; calcd 15.8%). The TGA results basically agree with the formulas of 1 and 2. Conclusions In summary, we have successfully synthesized two unprecedented interpenetrated MCFs by mixed BDC2- and BTB3ligands incorporating low-nuclear metal-carboxylate SBUs. Several features are endowed to 1 and 2. Among them, 1 possesses a rare example of interpenetration among 2D bilayers and a 3D hms net, whereas 2 exhibits novel 3-fold interpenetrated gra nets with chiral, hexagonal helical channels. Interestingly, the two 3D nets of hms in 1 and gra in 2 are strict isomers and can be theoretically translated between each other by rotations of the two axial carboxylate groups in two isomeric Zn2(O2CR)5 SBUs. The SBU2 and SBU3 also represent the first pair of 5-connected pure metal-carboxylate clusters in 3D coordination polymers. These findings are representative of uncommon topological aesthetics and helpful for the development of crystal engineering. Acknowledgment. This work was supported by the “973 Program” (2007CB815302) and NSFC (20821001 & 20525102).

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Supporting Information Available: PXRD, TGA, additional crystallographic figures (PDF); CIF files. This material is available free of charge via the Internet at http://pubs.acs.org.

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