Article pubs.acs.org/crystal
Tuning Cobalt Coordination Architectures by Bis(1,2,4-triazol-1ylmethyl)benzene Position Isomers and 5-Nitroisophthalate Xia Zhu, Peng-Peng Sun, Jian-Gang Ding, Bao-Long Li,* and Hai-Yan Li Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China S Supporting Information *
ABSTRACT: In our effect to tune the Co(II) coordination polymer architectures, three position isomers 1,2-, 1,3-, 1,4-bis(1,2,4-triazol-1ylmethyl)benzene and rigid 5-nitroisophthalate were used to assembly Co(II) coordination polymers [Co(obtz)(NO2-1,3-bdc)]n (1), [Co(mbtz)(NO2-1,3-bdc)(CH3OH)]n (2), and [Co(bbtz)(NO2-1,3-bdc)(H2O)]n (3). 1 is comprised of undulated twodimensional (2D) (4,4) networks. Two identical undulated layers are parallel interpenetrated to each other to give a (2D → 2D) polycatenated 2D network. The adjacent polycatenated 2D layers parallel polythreaded to form a unique 3D network. 1 is an unusual 2D → 3D polythreaded framework based on the polycatenated 2D layers. 2 shows the double-layer structure through the hydrogen bonds and π···π stacking interactions based on the undulated 2D (4,4) network. A 3D supramolecular network is constructed through the π···π stacking interactions interdouble layers. 3 exhibits a 3-fold interpenetrating 4-connected 65·8-CdSO4 3D network. The powder X-ray diffraction, thermal stabilities, and UV−vis spectroscopy of 1, 2, and 3 were investigated.
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INTRODUCTION The rational design and synthesis of novel coordination polymers is of great interest in modern inorganic chemistry steming not only from their potential applications as functional materials in fields such as gas storage, chemical separation, catalysis, ion exchange, and so on but also from their intriguing variety of topologies.1−6 In order to get such intriguing topologies and functional materials, the crucial step is to employ appropriate organic building blocks as well as metal ions. The networks of coordination polymers containing flexible bidentate ligands are less predictable due to the possible occurrence of supramolecular isomerism involving the adoption of different conformations.7 Previously we synthesized some new coordination polymers using flexible bis(triazole) building blocks such as 1,3-bis(1,2,4-triazol-1-yl)propane (btp), 1,4-bis(1,2,4-triazol-1-yl)butane (btb), and 1,4-bis(1,2,4-triazol1-ylmethyl)benzene (bbtz).8−10 For example, {[Zn(btp)(1,4bdc)][Zn(btp)(1,4-bdc)0.5Cl]·H2O}n (1,4-bdc = 1,4-benzenedicarboxylate) represents a new type of entanglement that only a half of the loops of two-dimensional (2D) networks are polythreading by one-dimensional (1D) chains containing alternating rings and rods.8 [2D-Mn(btb)2(NCS)2][1D-Mn(btb)2(NCS)2] and [Cd3(bbtz)6(H2O)6](BF4)6·1.75H2O show 2D (4,4) networks and 1D ribbons of rings polycatenated in a three-dimensional (3D) array.9a,10a Meanwhile, because of the diversity of the coordination modes and high structural stability, carboxylate ligands are frequently used for construction MOFs.11 5-Nitroisophthalate (NO2-1,3-bdc) with the bending © 2012 American Chemical Society
angle of ca. 120° between two carboxylate groups can construct novel topologies.12 The combination of flexible bis(triazole) ligands and polycarboxylate ligand may induce novel topologies. Besides the usual interpenetrating networks, polycatenation, and polyknotting species, another more interesting subgroup of entanglement system described as polythreading still remains less explored that is reminiscent of molecular rotaxanes or pseudorotaxanes.13−21 Polythreaded structures are characterized by the presence of closed loops, as well as of elements that can thread through the loops, and can be considered as extended periodic analogues of molecular rotaxanes and pseudorotaxanes.15−21 However, only a few examples of (2D → 3D) polythreaded network assembly from 2D motifs have been reported.19 With this background information, we sought to investigate the role of three isomeric ligands 1,2-, 1,3-, 1,4-bis(1,2,4-triazol1-ylmethyl)benzene (obtz, mbtz, bbtz) (Scheme 1) and rigid 5nitroisophthalate (NO2-1,3-bdc) in the construction of cobalt(II) coordination polymers. In the present work, three Co(II) coordination polymers [Co(obtz)(NO2-1,3-bdc)]n (1), [Co(mbtz)(NO2-1,3-bdc)(CH3OH)]n (2), and [Co(bbtz)(NO21,3-bdc)(H2O)]n (3) were synthesized. 1 is an unusual 2D → 3D polythreaded framework based on the polycatenated 2D Received: April 5, 2012 Revised: June 23, 2012 Published: June 28, 2012 3992
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Synthesis of [Co(mbtz)(NO2-1,3-bdc)(CH3OH)]n (2). The synthetic procedure of 2 was similar to the synthesis of 1, except that mbtz (0.20 mmol) was used instead of obtz. The red block crystals 2 (yield: 64%) were obtained after three weeks at room temperature. Anal. Calcd. for C21H19CoN7O7 (2): C, 46.68; H, 3.54; N, 18.15%. Found: C, 46.64; H, 3.48; N, 18.13. IR data (cm−1): 3411s, 1621s, 1559s, 1528s, 1451m, 1351s, 1289m, 1250w, 1204w, 1135m, 1088w, 1050w, 1019w, 996w, 888w, 795w, 725s, 679m, 656w, 602w. Synthesis of [Co(bbtz)(NO2-1,3-bdc)(H2O)]n (3). The synthetic procedure of 3 was similar to the synthesis of 1, except that bbtz (0.20 mmol) was used instead of obtz. The pink block crystals of 3 (yield: 72%) were obtained after one month at room temperature. Anal. Calcd. for C20H17CoN7O7 (3): C, 45.64; H, 3.26; N, 18.63%. Found: C, 45.58; H, 3.23; N, 18.58. IR data (cm−1): 3420s, 1628s, 1563s, 1534s, 1452w, 1368m, 1342m, 1281m, 1206w, 1136s, 1099w, 1074w, 1024w, 987s, 928w, 884m, 790w, 735s, 674m, 651w, 513w. X-ray Crystallography. Suitable single crystals of 1, 2, and 3 were carefully selected under an optical microscope and glued to thin glass fibers. The diffraction data were collected on the Rigaku Mercury or Saturn CCD diffractometers with graphite monochromated Mo Kα radiation. Intensities were collected by the ω scan technique. The structures were solved by direct methods and refined with full-matrix least-squares technique (SHELXTL-97).23 The positions of hydrogen atoms of obtz, mbtz, bbtz, and NO2-1,3-bdc were determined with theoretical calculation. The hydrogen atoms of the water molecules were obtained from the successive Fourier syntheses. The parameters of the crystal data collection and refinement of 1, 2, and 3 are given in Table 1. Selected bond lengths and bond angles are given in the Supporting Information (Table S1 in the Supporting Information).
Scheme 1. Ligands obtz, mbtz, and bbtz in 1, 2, and 3
Table 1. Crystallographic Data for 1, 2, and 3 1 formula fw crystal system space group temp (K) a (Å) b (Å) c (Å) α (°) β (°) γ (°) V (Å3) Z ρcalc (g/cm3) μ (mm−1) F(000) reflections collected unique reflections parameters goodness of fit R1 [I > 2σ(I)] wR2 (all data)
layers. The structure of 2 is an undulated 2D (4,4) network. The hydrogen bond and π···π stacking interactions stabilize the 3D supramolecular network in 2. The structure of 3 is a 3-fold interpenetrating 4-connected 65·8-CdSO4 3D network.
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EXPERIMENTAL SECTION
Materials and General Methods. All reagents were of analytical grade and used without further purification. Three bis(1,2,4-triazol-1ylmethyl)benzene position isomers obtz, mbtz, and bbtz were synthesized according to the literature method.22 Elemental analyses for C, H, and N were performed on a Perkin-Elmer 240C analyzer. IR spectra were obtained for KBr pellets on a Nicolet 170SX FT-IR spectrophotometer in the 4000−400 cm−1 region. Powder X-ray diffraction (PXRD) were performed on a D/MAX-3C diffractometer with the CuKa radiation (λ = 1.5406 Å) at room temperature. Thermogravimetric analysis (TGA) was carried out using a Thermal Analyst 2100 TA Instrument and SDT 2960 Simultaneous TGA-DTA Instrument in flowing dinitrogen at a heating rate of 10 °C/min. Diffuse reflectance UV−vis spectra for the solid samples were recorded on an Lambda 900 spectrometer in the range of 200−1200 nm. Synthesis of [Co(obtz)(NO2-1,3-bdc)]n (1). A solution of NO2− H2-1,3-bdc (0.2 mmol) in 10 mL of H2O was adjusted to approximately pH 6.5 with dilute NaOH solution. Then obtz (0.2 mmol) in 10 mL of CH3OH was added. This mixture was added to one side of the “H-shape” tube, and Co(NO3)2·6H2O (0.2 mmol) in 20 mL of water was added to the other side of the “H-shape” tube. The blue block crystals of 1 (yield: 53%) were obtained after one month at room temperature. Anal. Calcd. for C20H15CoN7O6 (1): C, 47.26; H, 2.97; N, 19.29%. Found: C, 47.23; H, 2.95; N, 19.25. IR data (cm−1): 1624s, 1570s, 1544s, 1474m, 1387m, 1346m, 1288m, 1192w, 1138m, 1088w, 1018m, 981m, 902w, 798m, 732s, 674m, 541w.
2
3
C20H15CoN7O6 508.32 monoclinic P21/c 293(2) 10.323(3) 20.812(5) 10.166(3) 90 108.736(6) 90 2068.4(9) 4 1.632 0.886 1036 19383
C21H19CoN7O7 540.36 monoclinic P21/c 293(2) 10.1925(13) 28.769(4) 7.7372(10) 90 102.751(3) 90 2212.8(5) 4 1.622 0.837 1108 18413
C20H17CoN7O7 526.34 monoclinic Cc 293(2) 16.413(4) 16.914(4) 7.4606(16) 90 95.163(8) 90 2062.8(8) 4 1.695 0.895 1076 9866
3769 [R(int) = 0.0470] 307 1.078 0.0534 0.1252
4034 [R(int) = 0.0264] 329 1.075 0.0429 0.1063
3341 [R(int) = 0.0397] 324 1.030 0.0387 0.0867
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RESULTS AND DISCUSSION Structure of [Co(obtz)(NO2-1,3-bdc)]n (1). X-ray diffraction analysis shows that 1 is comprised of undulated 2D (4,4) networks. The asymmetric unit of 1 has one Co(II) atom, one obtz, and one NO2-1,3-bdc. Each Co(II) is mainly four coordinated in a distorted tetrahedral geometry by two triazole nitrogen atoms from two obtz ligands (Co(1)−N(3) 2.030(3) 3993
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Å, Co(1)−N(6B) 2.026(3) Å) and two carboxylate oxygen atoms from two NO2-1,3-bdc (Co(1)−O(1) 1.967(2) Å, Co(1)−O(3A) 2.000(3) Å) (Figure S1 in the Supporting Information). There is weak coordination bond between the Co(1) and the other carboxylate oxygen atom (Co(1)−O(4A) 2.590(3) Å). Each NO2-1,3-bdc ligand acts as a binode (Scheme 2) and bridges two Co(II) atoms with the Co···Co Scheme 2. Coordination Mode of NO2-1,3-bdc Ligand in 1, 2, and 3
distance of 10.166(30) Å. Each obtz ligand shows the transconformation. The dihedral angles between two triazole ring planes, between the N(1)−N(3)/C(9)/C(10), N(4)−N(6)/ C(11)/C(12) triazole ring plane and benzene ring planes, are 41.1, 72.2, and 88.1°, respectively. Each obtz acts as bidentate bridging ligand and joins two Co(II) atoms with the Co···Co distance of 12.587(2) Å. Each Co(II) is coordinated two obtz and two NO2-1,3-bdc ligands and extend to form a neutral undulated 2D (4,4) network (Figure 1a). The 2D layers of 1 are strongly undulated. Two identical undulated layers are parallel interpenetrated to each other to give a (2D → 2D) polycatenated 2D network (Figure 1b). This parallel interpenetration do not increase the dimension. Batten and co-workers have already classified and described the n-fold interpenetrated 2D structures with no increase in dimensionality.13a Among the known 2D interpenetrating polymers, the most examples are the mode of 2D → 2D interpenetration by adjacent networks or 2D → 3D polycatenation by infinite networks.13,14 Recently, several unusual polycatenated networks involving 2D motifs have been described. [Cu3(btp)4(SIP)2(H2O)4][Cu(btp)(SIP)(H2O)][Cu0.5(btp)(H2O)]35H2O}n (NaH2SIP = 5-sulfoisophthalic acid monosodium salt) affords the novel (2D + 2D + 1D → 3D) supramolecular architecture.14f [Zn3(BIDPE)3(OHbdc)3·4H2O]n (BIDPE = 4,4′-bis(imidazol-1-yl)diphenylether) exhibits six identical 2D sheets polycatenated in parallel to form a rare 2D → 2D framework.14h Zhang and co-workers synthesized a homochiral Cu(II) compound with 4,4′-oxybisbenzoic acid and 1,3-di(4-pyridyl)propane in which the chiral bilayers polycatenate each other to give an interesting 3D supramolecular framework.14i [Cd(HEtIDC)(bix)0.5(H2O)]n has the first 2D → 3D parallel polycatenation pattern based on 4·82-fes networks (H3EtIDC = 1H-imidazole-4,5-dicarboxlylic acid, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), whereas [Cd2(HEtIDC)2(dpe)(H2O)]n displays a new (3,4)-connected self-catenated framework (dpe = 1,2-di(4-pyridyl)-ethylene).14l The most striking structural feature of 1 is that adjacent polycatenated 2D layers parallel polythreaded to form an unique 3D network. The adjacent polycatenated 2D layers are parallel stacked in an offset fashion such that the convex bow of one layers extends into the concave bay of the neighboring layers (Figure S2 in the Supporting Information). On the other
Figure 1. (a) An undulated 2D (4,4) network in 1. (b) A polycatenated 2D network of 1 (top) and schematic depiction of a polycatenated 2D network of 1 (bottom). The sticks represent the obtz and NO 2 -1,3-bdc ligands. (c) The polythread of two polycatenated 2D networks in 1. Four colors (red, blue, pink, and bright green) represent four 2D (4,4) networks. The long sticks exhibit obtz bridgings. The green dashed lines show the π−π interactions between the benzene rings in the polythreaded network.
hand, the nitro groups of NO2-1,3-bdc with the extended lengths (from one Co(II) center to two oxygen atoms of NO21,3-bdc) of 6.94 and 8.13 Å give premise to the formation of a polythreaded network. In fact, each NO2-1,3-bdc of one layer is inserted into the large grids of two adjacent layers up and down. Therefore, each grid is penetrated by a pair of NO2-1,3-bdc entities from the opposite directions. As a consequence, adjacent 2D layers are entangled into an unique 3D polythreaded architecture (2D → 3D) (Figure 1c). The adjacent benzene rings of NO2-1,3-bdc inter 2D polythreaded networks overlap parallel to each other to form a suitable space (3.673 Å) for π···π stacking interactions. The 3D supra3994
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molecular architecture is sustained by the π···π stacking interactions. Polythreaded structures with finite components are unusual.13,15,21 The few species known include polythreaded 0D rings with side arms that give 1D or 2D arrays,15 1D chains of alternating rings and rods (1D → 1D),16 molecular ladders with dangling arms, resulting in (1D → 2D) or (1D → 3D) polythreaded arrays,17 1D chains and 2D sheets (1D + 2D → 2D) or (1D + 2D → 3D),8,18 2D sheets (2D → 2D)19 or (2D → 3D)20 and (3D + 1D).21 So far, only several 2D → 3D polythreaded frameworks were reported. Most of the 3D polythreaded frameworks are constructed from simple 2D (4,4) or (6,3) layers with side arms.20 [Ni2(Tipa)2(bdc)2(H2O)2]3.25H2O (Tipa = tri(4-imidazolylphenyl)amine, bdc = 1,4benzenedicarboxylate) shows a 2D → 3D polythreaded framework with both polyrotaxane and polypeseudo-rotaxane character.20k One example of 2D square grids Cu2(OHbdc)2(4,4′-bipy)2(H2O)2]n (A) and irregular layers [Cu3(OHbdc)2 (2-PyC)2(4,4′-bipy)2(H2O)4]n (B) (2-PyC = pyridine-2carboxylate) shows the simultaneous polycatenation and polythreading in a unique 3D framework [(A)(B)]·6.5nH2O.20l But in 1, two 2D networks first polycatenate each other to form a 2D layer. Then the 2D layers construct a (2D → 3D) 3D polythreaded network. Structure of [Co(mbtz)(NO2-1,3-bdc)(CH3OH)]n (2). The structure of 2 is an undulated 2D (4,4) network (Figure 2a). The asymmetry unit consists of one Co(II) atom, one mbtz, one NO2-1,3-bdc, and one coordination methanol molecule. Each Co(II) atom displays a distorted octahedral coordination geometry, coordinated by four oxygen atoms from two NO2-
1,3-bdc and one coordination methanol and two nitrogen atoms from two mbtz (Figure S3 in the Supporting Information). Each NO2-1,3-bdc ligand acts as the monodentate and bidentate chelating modes (Scheme 2). Each node (Co(II)) of the 2D network is surrounded by four nodes (Co(II) atoms) which are bridged by mbtz and NO2-1,3-bdc ligands. Each mbtz exhibits trans-conformation (Scheme 1). The dihedral angles between two triazole ring planes, between the N(1)−N(3)/C(9)/C(10), N(4)−N(6)/C(11)/C(12) triazole ring plane and benzene ring planes are 39.7, 69.4, and 73.4°, respectively. Four Co(II) atoms, two mbtz, and two NO2-1,3-bdc ligands forms a [Co4(mbtz)2(NO2-1,3-bdc)2] unit with the Co···Co distances 11.355(2) and 10.193(2) Å for mbtz and NO2-1,3bdc bridgings, and extend to from an undulated 2D (4,4) network (Figure S4 in the Supporting Information). Two adjacent 2D layers construct the double-layer structure through the hydrogen bond interactions between the coordination methanol molecules and carboxylate oxygen atoms of NO2-1,3bdc intrasheets (O7···O4 (−x + 1, −y, −z + 1) 2.739(3) Å) (Figure 2b, Table S2 in the Supporting Information). The adjacent benzene ring of NO2-1,3-bdc ligands from two 2D (4,4) networks in the double-layer show the suitable space (3.570 Å) for π···π stacking interactions. These hydrogen bonds and π···π stacking interactions sustain the double-layer in 2. The adjacent benzene rings of mbtz ligands in the double-layers overlap parallel to each other with a suitable space (3.902 Å) to form the π···π stacking interactions and stabilize the 3D supramolecular network in 2 (Figure 2b). Structure of [Co(bbtz)(NO2-1,3-bdc)(H2O)]n (3). The structure of 3 is a 4-connected 65·8-CdSO4 3D network. The asymmetry unit consists of one Co(II) atom, one bbtz, one NO2-1,3-bdc, and one coordination water molecule. Each Co(II) atom displays a distorted octahedral coordination geometry, coordinated by four oxygen atoms from two NO21,3-bdc and one coordination water and two nitrogen atoms from two bbtz (Figure S5 in the Supporting Information). Each NO2-1,3-bdc ligand acts as the monodentate and bidentate chelating modes (Scheme 2). Each bbtz exhibits transconformation (Scheme 1). The dihedral angles between two triazole ring planes, between the N(1)−N(3)/C(9)/C(10), N(4)−N(6)/C(11)/C(12) triazole ring plane and benzene ring planes are 7.0, 109.5, and 116.2°, respectively. Each Co(II) atom is coordinated by two bbtz and two NO2-1,3-bdc ligands and is 4-connected. Each Co(II) atom connects four adjacent Co(II) atoms through two bbtz and two NO2-1,3-bdc ligands and extend to build a 3D 4-connected 65·8-CdSO4 coordination network (Figure 3a,b). The MOFs exhibiting 65·8-CdSO4 coordination network are relatively few.24 Because the single 3D CdSO4 network has large spacious voids, it allows two other identical CdSO4 networks to interpenetrate giving rise to a 3fold interpenetrating 3D CdSO4 network (Figure 3c). There are hydrogen bond interactions between the coordination water molecules and the carboxylate oxygen and 2-position triazole nitrogen atoms (Table S2 in the Supporting Information). PXRD, IR, Thermal Analysis, and Diffuse Reflectance UV−vis Spectroscopy. The measured and simulated PXRDs confirm the purity of the products 1, 2, and 3 (Figures S7−S9 of Supporting Materials). The network of 2 is destroyed after solvent loss and cannot regenerate to the original 2 after reabsorbing solvent. The network of 3 is stable after solvent loss when 3 is heated at 200 °C for 10 min.
Figure 2. (a) An undulated 2D (4,4) network in 2. (b) The 3D supramolecular architecture in 2. The green and red dashed lines show the π−π stacking interaction between the benzene rings. The blue dashed lines exhibit the O−H···O hydrogen bond interactions between the methanol and carboxylate oxygen atoms. 3995
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methanol molecules were lost from 50 to 170 °C (calculated: 5.92%, found: 6.09%) and the product was stable to approximately 276 °C. Then the weight loss occurred continuously and did not stop upon 690 °C which is assigned to NO2-1,3-bdc (residue one oxygen atom) and mbtz (calculated: 80.21%, found: 80.06%). For compound 3, the coordination water molecules were lost from 50 to 180 °C (calculated: 3.42%, found: 3.54%) and the network was stable upon to 380 °C. Then two main weight losses happened. One is from 390 to 440 °C which is main attributed to the NO2-1,3bdc (calculated for C8H3NO5 due to residue one oxygen atom: 36.37%; found: 36.22%). The second is from 440 to 660 °C which is assigned to bbtz (calculated: 45.65%; found: 44.69%). The residue is stable to 1000 °C which is CoO (calculated: 14.75% for 1, 13.88% for 2 and 14.25% for 3; found: 14.90% for 1, 13.76% for 2 and 14.16% for 3). The diffuse reflectance UV−vis spectra of 1, 2, 3 and free ligands obtz, mbtz, and bbtz are shown in Figure S11 (Supporting Information). The sharp emission maxim at 421, 425, and 424 nm in 1, 2, and 3 are contributed to the mixed ligands obtz, mbtz, bbtz, and NO2-1,3-bdc. The emission maximum at 701 nm for 1 is attibuted to the electronic spectrum of the d−d electronic transitions. The broad absorption bands in the 600−800 nm region for 2, and 550− 1000 nm for 3 are assigned to the electronic spectra of the d−d electronic transitions.
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CONCLUSION In summary, three Co(II) coordination polymers were synthesized by the combination of three position isomers obtz, mbtz, bbtz, and rigid NO2-1,3-bdc. 1 is an unusual 2D → 3D polythreaded framework based on the polycatenated 2D layers. 2 shows a 3D supramolecular network. The structure of 3 is a 3-fold interpenetrating 4-connected 65·8-CdSO4 3D network. The structural versatility of 1, 2, and 3 show that the structures can be tuned by the position isomers. The successful synthesis of these compounds not only provides an intriguing example of a polythreaded system but also provides new perspectives to devise novel extended entanglements.
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Figure 3. (a) The 3D network in 3. (b) Schematic representation of the 3D CdSO4 topology in 3. The bright green and the pink sticks represent the bbtz and NO2-1,3-bdc ligands, respectively. (c) Schematic representation of the 3-fold interpenetrating 3D CdSO4 topology in 3.
ASSOCIATED CONTENT
* Supporting Information S
Crystallographic data in CIF format (CCDC 873499, 873500, and 873501), the selected bond lengths and bond angles, the hydrogen bond, the additional plots of the structures, and figures of the power X-ray diffraction, thermal stability and UVvis spectroscopy. This material is available free of charge via the Internet at http://pubs.acs.org.
The IR spectrum determination shows that the triazole ring vibrations in 1, 2, and 3 are at 1544 and 1288, 1528 and 1289, 1534, and 1281 cm−1, respectively.9,10 The absorptions of 1, 2, and 3 at 1624 and 1570, 1621 and 1559, 1628, and 1563 are asigned to carboxylate and nitro groups of NO2-1,3-bdc.12 To characterize the compounds more fully in terms of thermal stability, the thermal behaviors of 1, 2, and 3 were examined by TGA. The experiments were performed on samples consisting of numerous single crystals with a heating rate of 10 °C/min (Figure S10 in the Supporting Information). Compound 1 was stable to 370 °C. Then two main weight losses happened. One is from 380 to 410 °C which is main attributed to the NO2-1,3-bdc (calculated for C8H3NO5 due to residue one oxygen atom: 37.99%; found: 38.52%). The second is from 410 to 665 °C which is assigned to obtz (calculated: 47.27%; found: 46.59%). For compound 2, the coordination
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by the Natural Science Foundation of China (No. 21171126), the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the Funds of Key Laboratory of Organic Synthesis of Jiangsu Province. 3996
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dx.doi.org/10.1021/cg300465r | Cryst. Growth Des. 2012, 12, 3992−3997
