Mn(II)-Binaphthalenyl Dicarboxylate Complexes: Helical Rectangular

Sep 15, 2009 - Mn(II)-Binaphthalenyl Dicarboxylate Complexes: Helical Rectangular Tubes, (4,4) Grid Chiral Layer and Three-Dimensional Cubic Diamond ...
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DOI: 10.1021/cg9008366

Mn(II)-Binaphthalenyl Dicarboxylate Complexes: Helical Rectangular Tubes, (4,4) Grid Chiral Layer and Three-Dimensional Cubic Diamond Frameworks

2010, Vol. 10 184–190

Qiang Gao, Fei-Long Jiang, Ming-Yan Wu, You-Gui Huang, Wei Wei, and Mao-Chun Hong* Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China Received July 19, 2009; Revised Manuscript Received August 31, 2009

ABSTRACT: Reactions of 2,20 -dihydroxyl-[1,10 ]-binaphthalene-3,30 -dicarboxylate acid (H2bna) with manganese chloride by a solvent or solvothermal method in the presence of pyridine (py) or 4-picoline (pic) give birth to three 1D to 3D frameworks: [Mn(bna)(DMF)2(H2O)2]n 3 nDMF (1), {(Hpic)2[Mn3(bna)4(C2H5OH)2(H2O)2] 3 5H2O}n (2), and {(Hpy)2[Mn3(bna)4(py)2(H2O)2] 3 4H2O}n (3) (DMF=N,N0 -dimethylformamide). Crystal structure analyses reveal that 1 is a mesomer with equivalent R- and L-helical rectangular tubes constructed from homochiral ligands, which is further assembled into a 3D supramolecular network through hydrogen bonds and C-H 3 3 3 π interactions. Complex 2 consists of a (4,4) grid chiral layer structure, while 3 features a 3D cubic diamond network with Schlafli symbol 66 topology, though they both comprise of [Mn3(μ2-COO)6(COO)2] pinwheel molecular building blocks which act as 4-connected nodes and bna2- as linkers. Magnetic studies indicate that antiferromagnetic couplings exist in both 2 and 3.

Introduction The rational and controlled design of metal-organic frameworks (MOFs) is one of the most challenging areas of research in the field of coordination chemistry, due to their aesthetically intriguing topology architectures and highly promising chemical and physic applications in many perspectives, such as gas adsorption and separation, catalytic activities, luminescence, magnetism, and so on.1 Crystal engineering strategies are widely exploited in directing the construction of MOFs.2 In this process, the choice of organic ligands and metal ions is crucial. Polycarboxylate ligands and various inorganic molecular building blocks (MBBs) are widely exploited for the search of novel MOFs.3 Nevertheless, the careful control of reaction conditions also plays an important role in producing frameworks with diverse topologies and various desirable properties.4 In this perspective, different synthesis methods, that is, the solvent method, or hydrothermal or solvothermal method, the addition of counterions and templates all have a considerable influence on the final products. The tetratopic 2,20 -dihydroxy-1,10 -binaphthyl-3,30 -dicarboxylate acid (H2bna) is a multifunctional ligand containing both carboxylic and phenolic groups, and can potentially afford various coordination modes and diverse MOF architectures. Meanwhile, the naphthyl rings can be severely twisted at different degrees across the C-C single bond due to a steric effect, which may endow H2bna with chirality. Up to now, there are only four reports on this ligand, and their results indicate that this ligand is a good candidate in constructing MOFs with diverse architectures.5 On the other hand, carboxylate-bridged trinuclear metal ions pinwheel MBBs have been well documented and studied as the building units of MOFs.6 Among them, many efforts are devoted to the [Mn3(μ2-COO)6] pinwheel MBBs, which, however, are mostly *To whom correspondence should be addressed. Tel: þ86-591-83792460. Fax: þ86-591-83794946. E-mail: [email protected]. pubs.acs.org/crystal

Published on Web 09/15/2009

focused on isolated structures and 1D structures. To the best of our knowledge, 2D or 3D frameworks based on a [Mn3(μ2COO)6] pinwheel MBB have never been reported so far.7 Moreover, via appropriate variation of the terminal coordination molecules, it may be possible to fine-tune the pathway of the magnetic interaction and the final interaction behavior. Herein we utilized H2bna and manganese chloride to construct three complexes: [Mn(bna)(DMF)2(H2O)2]n 3 nDMF (1), {(Hpic)2[Mn3(bna)4(C2H5OH)2(H2O)2] 3 5H2O}n (2), and {(Hpy)2[Mn3(bna)4(py)2(H2O)2] 3 4H2O}n (3) by a solvent or solvothermal method in the presence of pyridine (py) or 4-picoline (pic). 1 exhibits unique R(L) helical rectangular tubes constructed from homochiral ligands, which is further assembled into a 3D supramolecular network through hydrogen bonds and C-H 3 3 3 π interactions. Complex 2 consists of a (4,4) grid chiral layer structure, while 3 features a 3D cubic diamond network with Schlafli symbol 66 topology, though they both comprise of [Mn3(μ2-COO)6(COO)2] pinwheel molecular building blocks which act as 4-connected nodes and bna2- as linkers. Magnetic studies indicate that antiferromagnetic couplings exist in both 2 and 3. Experimental Section Materials and Instruments. All chemicals were obtained from commercial sources and used without further purification. The ligand H2bna was synthesized according to the literature.8 Elemental analyses were performed on a German Elementary Vario EL III instrument. The FT-IR spectra were recorded on a Nicolet Magna 750 FT-IR spectrometer using KBr pellets in the range of 4000400 cm-1. Thermogravimetric analyses were carried out on a NETZSCH STA 449C unit at a heating rate of 10 °C /min under nitrogen atmosphere. The power X-ray diffraction (XRD) patterns of the as-synthesized samples were recorded by a RIGAKUDMAX2500 X-ray diffractometer using Cu KR radiation (λ = 0.154 nm) at a scanning rate of 5°/min for 2θ ranging from 5° to 85°. Magnetic data were obtained with a Quantum Design MPMS XL SQUID magnetometer. r 2009 American Chemical Society

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drops of pyridine was then added to the solution. The solution was stirred for 30 min at room temperature, and then left undisturbed for two days. Light yellow prism crystals were obtained, filtered, and dried at ambient temperature to give about 110 mg of complex 1 (yield 80% based on H2bna). Elemental analysis for C31H37MnN3O11 (Mr = 682.58): calcd: C 54.55%, H 5.46%, N 6.16%; found: C 54.47%, H 5.39%, N 6.11%. Selected IR data (KBr pellet, cm-1): 3387 (br, m), 2931 (w), 1655 (s), 1563 (s), 1503 (m), 1460 (s), 1435 (m), 1391 (m), 1339 (m), 1306 (m), 1245 (m), 1110 (s), 939 (m), 810 (w), 750 (s), 680 (m) cm-1. Synthesis of {(Hpic)2[Mn3(bna)4(C2H5OH)2(H2O)2] 3 5H2O}n (2). A mixture of MnCl2 (0.15 mmmol, 30.0 mg), H2bna (0.2 mmol, 78.0 mg), pic (0.01 mL), H2O (4 mL), and ethanol (4 mL) was placed in 30 mL

Synthesis of {[Mn(bna)(DMF)2(H2O)2] 3 DMF}n (1). MnCl2 (0.2 mmmol, 40.0 mg) and H2bna (0.2 mmol, 78.0 mg) was dissolved in N,N0 -dimethylformamide (DMF) (4 mL) and H2O (2 mL), and five Table 1. Crystallographic Data for 1-3 identification code empirical formula formula weight crystal system space group a [A˚] b [A˚] c [A˚] β [°] V [A˚3] Z Dc [g/cm-3] μ [mm-1] goodness-of-fit on F2 final R indices [I > 2σ(I)]a R indices (all data) a

1

2

3

C31H37MnN3O11 682.58 monoclinic P21/n 12.765 (3) 11.320 (2) 23.281 (5) 91.217 (3) 3363.4 (13) 4 1.348 0.454 1.043 R1 = 0.0769, wR2 = 0.2193 R1 = 0.0848, wR2 = 0.2302

C104H88Mn3N2O33 2058.58 monoclinic P2/n 15.598 (4) 11.889 (3) 27.430 (7) 98.167 (4) 5035 (2) 2 1.358 0.454 1.082 R1 = 0.0773, wR2 = 0.2134 R1 = 0.1000, wR2 = 0.2342

C108H82Mn3N4O30 2080.60 monoclinic C2/c 16.240 (4) 26.255 (7) 23.181 (6) 98.086 (5) 9785 (4) 4 1.412 0.466 1.052 R1= 0.0815, wR2 = 0.2049 R1 = 0.1263, wR2 = 0.2398

185

Scheme 1. The Observed Coordination Modes of bna2- Ligands in Complexes 1-3

R1 = Σ||Fo| - |Fc||/Σ|Fo|. wR2 = [Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2. Table 2. Selected Bond Lengths (A˚) and Bond Angles (°) for 1-3a 1

Mn1;O1 Mn1;O9 O1;Mn1;O9 O1;Mn1;O4i O9;Mn1;O4i O1;Mn1;O7 O9;Mn1;O7

2.158 (2) 2.160 (2) 88.67 (10) 88.55 (10) 94.39 (9) 91.48 (12) 93.34 (12)

i

Mn1;O4 Mn1;O7 O4i;Mn1;O7 O1;Mn1;O8 O9;Mn1;O8 O4i;Mn1;O8 O7;Mn1;O8

2.168 (2) 2.172 (3) 172.26 (11) 176.91 (13) 88.75 (13) 89.96 (12) 90.37 (14)

Mn1;O8 Mn1;O10 O1;Mn1;O10 O9;Mn1;O10 O4i;Mn1;O10 O7;Mn1;O10 O8;Mn1;O10

2.174 (3) 2.277 (2) 91.61 (8) 178.03 (9) 87.57 (8) 84.70 (11) 91.03 (12)

2.225 (3) 2.237 (4) 2.142 (3) 2.142 (3) 83.15 (14) 90.66 (18) 82.58 (14) 91.7 (2) 166.11 (15) 163.35 (16) 110.55 (11) 81.56 (10) 81.56 (10) 110.55 (11)

Mn2;O6 Mn2;O6iii Mn2;O1iv Mn2;O1v O6;Mn2;O6iii O7;Mn2;O1iv O7iii;Mn2;O1iv O6;Mn2;O1iv O6iii;Mn2;O1iv O7;Mn2;O1v O7iii;Mn2;O1v O6;Mn2;O1v O6iii;Mn2;O1v O1iv;Mn2;O1v

2.183 (3) 2.183 (3) 2.215 (2) 2.215 (2) 90.21 (16) 80.18 (10) 88.36 (11) 91.45 (11) 161.05 (10) 88.36 (11) 80.18 (10) 161.05 (10) 91.45 (11) 93.07 (14)

Mn1;O1iv Mn1;O1v 2.089 (3) 2.138 (3) 93.77 (14) 166.77 (14) 91.11 (12) 84.83 (13) 94.43 (15) 97.61 (13) 96.49 (12) 98.95 (13) 172.60 (13) 89.61 (14)

Mn2;O2 Mn2;O7 Mn2;N1 Mn2;O13 O2;Mn2;O7 O6vi;Mn2;N1 O12iv;Mn2;N1 O2;Mn2;N1 O7;Mn2;N1 O6vi;Mn2;O13 O12iv;Mn2;O13 O2;Mn2;O13 O7;Mn2;O13 N1;Mn2;O13

2.147 (3) 2.153 (3) 2.295 (4) 2.328 (4) 83.91 (12) 88.34 (14) 165.06 (15) 93.94 (14) 84.26 (14) 89.94 (14) 81.34 (15) 173.46 (12) 89.57 (13) 85.00 (15)

2 i

ii

Mn1;O2 Mn1;O5ii Mn1;O10 Mn1;O13 O2i;Mn1;O5ii O2i;Mn1;O10 O5ii;Mn1;O10 O2i;Mn1;O13 O5ii;Mn1;O13 O10;Mn1;O13 O2i;Mn1;O8ii O5ii;Mn1;O8ii O10;Mn1;O8ii O13;Mn1;O8ii

2.097 (3) 2.175 (3) 2.191 (2) 2.216 (3) 99.18 (12) 165.73 (12) 80.89 (10) 96.28 (12) 164.53 (11) 84.27 (11) 110.20 (11) 90.94 (11) 84.05 (11) 83.20 (13)

Mn1;O8 Mn1;O14 Mn2;O7 Mn2;O7iii O2i;Mn1;O14 O5ii;Mn1;O14 O10;Mn1;O14 O13;Mn1;O14 O8ii;Mn1;O14 O7;Mn2;O7iii O7;Mn2;O6 O7iii;Mn2;O6 O7;Mn2;O6iii O7iii;Mn2;O6iii

Mn1;O11i Mn1;O11 Mn1;O5ii Mn1;O5iii O11i;Mn1;O11 O11i;Mn1;O5ii O11;Mn1;O5ii O11i;Mn1;O5iii O11;Mn1;O5iii O5ii;Mn1;O5iii O11i;Mn1;O1iv O11;Mn1;O1iv O5ii;Mn1;O1iv O5iii;Mn1;O1iv

2.148 (3) 2.148 (3) 2.179 (3) 2.179 (3) 80.2 (2) 105.38 (15) 79.31 (14) 79.31 (14) 105.38 (15) 174.0 (2) 166.77 (14) 93.77 (14) 84.83 (13) 91.11 (12)

Mn1;O1iv Mn1;O1v Mn2;O6vi Mn2;O12iv O11i;Mn1;O1v O11;Mn1;O1v O5ii;Mn1;O1v O5iii;Mn1;O1v O1iv;Mn1;O1v O6vi;Mn2;O12iv O6vi;Mn2;O2 O12iv;Mn2;O2 O6vi;Mn2;O7 O12iv;Mn2;O7

3

Symmetry codes: 1: (i) 3/2 - x, -1/2 þ y, 1/2 - z. 2: (i) -x, 2 - y, 1 - z; (ii) -x, 1 - y, 1 - z; (iii) 1/2 - x, y, 3/2 - z; (iv) x, -1 þ y, z; (v) 1/2 - x, -1 þ y, 3/2 - z. 3: (i) 1 - x, y, 3/2 - z; (ii) 1/2 þ x, -1/2 þ y, z; (iii) 1/2 - x, -1/2 þ y, 3/2 - z; (iv) 1/2 - x, 1/2 - y, 1 - z; (v) 1/2 þ x, 1/2 - y, 1/2 þ z; (vi) x, 1 - y, -1/2 þ z. a

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Figure 1. The coordination environment around Mn(II) in 1 with the thermal ellipsoid at the 30% probability level. Symmetry codes: A: 3/2 - x, -1/2 þ y, 1/2 - z. Teflon-lined stainless steel autoclave. The autoclave was sealed, heated to 140 °C under autogenous pressure for 96 h, and then cooled to room temperature at 6 °C 3 h-1. A light yellow crystalline product was filtered, washed with distilled water, and dried at ambient temperature to give about 72 mg of complex 2 (yield 70% based on H2bna). Elemental analysis for C104H88Mn3N2O33 (Mr = 2058.58): calcd: C 60.68%, H 4.31%, N 1.36%; found: C 60.56%, H 4.28%, N 1.42%. Selected IR data (KBr pellet, cm-1): 3492 (s), 1640 (s), 1545 (m), 1505 (m), 1456 (s), 1395 (s), 1372 (m), 1339 (m), 1302 (m), 1242 (w), 1077 (w), 941 (w), 879 (w), 811 (m), 752 (m) cm-1. Synthesis of {(Hpy)2[Mn3(bna)4(py)2(H2O)2] 3 4H2O}n (3). A mixture of MnCl2 (0.2 mmmol, 40.0 mg), H2bna (0.1 mmol, 39.0 mg), py (0.5 mL), H2O (4 mL), and methanol (4 mL) was placed in 30 mL Teflon-lined stainless steel autoclave. The autoclave was sealed, heated to 120 °C under autogenous pressure for 72 h, and then cooled to room temperature at 6 °C 3 h-1. Light yellow crystalline product was filtered, washed with distilled water, and dried at ambient temperature to give about 39 mg of complex 3 (yield 75% based on H2bna). Elemental analysis for C108H82Mn3N4O30 (Mr = 2080.60): calcd: C 62.34%, H 3.97%, N 2.69%; found: C 62.28%, H 3.91%, N 2.74%. Selected IR data (KBr pellet, cm-1): 3430 (br, s), 3068 (m), 1637 (s), 1559 (s), 1503 (w), 1488 (w), 1457 (s), 1395 (s), 1370 (s), 1338 (s), 1301 (m), 1241 (m), 1152 (w), 1077 (w), 1006 (w), 938 (m), 812 (m), 751 (s), 698 (w) cm-1. X-ray Crystallography. Single crystals of compounds 1-3 were mounted on either a Rigaku Mercury CCD diffractometer (for 2) or a RIGAKU SATURN70 (for 1 and 3), both equipped with a graphite-monochromated MoKR radiation (λ=0.71073 A˚). Intensity data were collected by the narrow frame method at 293 K. All three structures were solved by the direct methods and refined by full-matrix least-squares fitting on F2 by SHELX-97.9 All nonhydrogen atoms except C31 in 1, free water molecules O17, O18 atoms in 2 and O14, O15, O16, O17 atoms in 3 were refined with anisotropic thermal parameters. Hydrogen atoms excluding those for water molecules in complexes 2 and 3 were located at geometrically calculated positions and refined with isotropical thermal parameters. Crystallographic data and structural refinements for compounds 1-3 are summarized in Table 1. Selected bond lengths and bond angles are listed in Table 2. More details on the crystallographic studies as well as atomic displacement parameters are given in Supporting Information as CIF files.

Results and Discussion Description of the Crystal Structures. The coordination modes of the bna ligand are listed in Scheme 1. The following structure discussion is based on CIF files for 1-3. The

Figure 2. (a) Representation of the helical rectangular tubes along the b-axis in 1. (b) Side view of the helical chains. (c) Ball-and-stick representation of hydrogen bonding linked 2D chiral supramolecular layer. (d) Packing of the layers into a 3D supramolecular network.

formulas of complexes 1-3 are further confirmed by elemental analysis (EA) and thermogravimetric (TG) studies. [Mn(bna)(DMF)2(H2O)2]n 3 nDMF (1). Complex 1 is a mesomer with equivalent R- and L- helical rectangular tubes. As illustrated in Figure 1, Mn(II) ion is coordinated by two oxygen atoms of two monodentate carboxylic groups from two individual bna2- ligands, two oxygen atoms from two DMF molecules, and two water molecules in the apical positions. As shown in Scheme 1, bna2- ligands in this paper have three kinds of coordination modes: κ1-κ1-μ2 (A), (κ1-κ1)κ1-μ3 (B), and (κ1-κ1)-(κ1-κ1)-μ4 (C), in which all of their phenol groups are not deprotonated, but form hydrogen bonds with oxygen atoms of o-carboxylic groups. In complex 1, each bna2- adopts coordination mode A to bridge two metal centers along the b-axis, forming a uniform chain. Notably, the ligands in the chain are of the same chirality, thus endowing the chain with same chirality as the ligands. The helix resembles a rectangular tube due to the conformation of the ligand (Figure 2a,b). Two coordination water molecules (O9 and O10) of the helix each forms one group of hydrogen bonds with another two coordination water molecules of the adjacent helix, which are of the same chirality. The O 3 3 3 O distance is 2.864(3) A˚ and the angle is 171.8°. Interestingly and rationally, the Mn-H2O 3 3 3 H2O-Mn chains formed through these groups of hydrogen bonding are also helices with the same chirality as the two Mn-bna helices. In this way, the helices are assembled into a 2D supramolecular chiral layer (Figure 2c). The layers of the opposite chirality are alternatively packed into a 3D supramolecular network through C-H 3 3 3 π interactions. The C-H 3 3 3 phenyl centroid distance is 2.685 A˚ and the C-H 3 3 3 phenyl centroid angle is 159.28°. The guest DMF molecules all reside in the rectangular tubes, which also form hydrogen bonds with the coordination

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Figure 3. The coordination environment around Mn(II) in 2 with the thermal ellipsoid at the 30% probability level. Symmetry codes: A: -x, 2 - y, 1 - z; B: -x, 1 - y, 1 - z; C: 1/2 - x, y, 3/2 - z; D: x, -1 þ y, z; E: 1/2 - x, -1 þ y, 3/2 - z.

Figure 4. (a) Ball-and-stick representation of [Mn3(μ2-COO)6(COO)2] pinwheel MBB in 2. (b) Schematic representation of the connectivity between the MBBs. (c) Schematic representation of the chiral 2D layer. (d) Topological view of the layer structure. The node is highlighted in yellow.

water molecules (Figure 2d). The O 3 3 3 O distance is 2.623 A˚ and the O-H 3 3 3 O angle is 172.8° (Figure S1, Supporting Information). {(Hpic)2[Mn3(bna)4(C2H5OH)2(H2O)2] 3 5H2O}n (2). Single crystal X-ray diffraction study indicates that complex 2 crystallizes in a monoclinic P2/n space group. There are two crystallographically independent Mn(II) ions in the asymmetrical unit, which are both coordinated by six oxygen atoms. For Mn1, four oxygen atoms are from four carboxylic groups of four individual bna2- ligands, the other two are afforded by one water molecule and one ethanol molecule, while for Mn2, all the six coordination oxygen atoms come from six carboxylic groups of six different bna2-

ligands (Figure 3). The bna2- ligands in complex 2 adopt two kinds of coordination modes: B and C, which are donated as bna(1) and bna(2). Six bidentate carboxylic groups from six diverse bna2- ligands bridge two Mn1 ions and one Mn2 ion together, and two monodentate carboxylic groups from another two bna2- ligands coordinate to two external Mn1 ions, giving rise to a [Mn3(μ2-COO)6(COO)2] pinwheel MBB. There are two types of six carboxylic groups-bridged Mn3 building blocks: in one type of them, all the carboxylic groups are coordinated in the syn-syn mode, giving a triple bridge between the central and external manganese ions, while in the other type, the central and external manganese ions are connected by two syn-syn carboxylic groups and one μ2-O,O,O0 carboxylic group.10 The MBBs in 2 and 3 all adopt the first type. Four solvent molecules act as monodentate terminal ligands to fulfill the coordination spheres (Figure 4a). The Mn1-Mn2 distance is 4.035 A˚ and the Mn1-Mn2-Mn1 angle is 147.31°. The MMB is connected to another four MMBs by four bna(1) and four bna(2) ligands. Each pair of bna(1) ligands uses two bidentate carboxylic groups and two monodentate carboxylic groups to connect two MBBs together. In a similar way, each pair of bna(2) ligands connects two MBBs with four bidentate carboxylic groups. It is worth noting that all these four bna(1) ligands are of the same chirality, which is the same case for the bna(2) ligands. Moreover, the chirality of bna(1) and bna(2) is opposite (Figure 4b). The MBBs are then stretched into a 2D chiral layer by the ligands in this way. From topological view, the MBBs can be considered as planar 4-connected nodes and the bna2- ligands as linkers, leading to a (4,4) grid plane (Figure 4c,d). The layers with opposite chirality then pack alternatively into a 3D network. The 4-picoline (pic) molecules are protonated to balance the charge of the framework, and interact with two naphthyl rings from a single layer through two groups of π-π interactions, and with one oxygen atom from one carboxylic group through hydrogen bonding. The distances between the planes are 3.290 and 3.289 A˚, respectively. The N 3 3 3 O

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Figure 5. The coordination environment around Mn(II) in 3 with the thermal ellipsoid at the 30% probability level. Symmetry codes: A: 1 - x, y, 3/2 - z; B: 1/2 þ x, -1/2 þ y, z; C: 1/2 - x, -1/2 þ y, 3/2 - z; D: 1/2 - x, 1/2 - y, 1 - z; E: 1/2 þ x, 1/2 - y, 1/2 þ z, F: x, 1 - y, -1/2 þ z.

Figure 6. (a) Ball-and-stick representation of [Mn3(μ2-COO)6(COO)2] pinwheel MBB in 3. (b) Schematic representation of the connectivity between the MBBs. (c) Highlight of an adamantanetype unit. (d) Topological view of the 3D framework. The node is highlighted in yellow.

distance is 2.967 A˚ and the N-H 3 3 3 O angle is 152.26° (Figure S2, Supporting Information). The guest water molecules reside between the layers. {(Hpy)2[Mn3(bna)4(py)2(H2O)2] 3 4H2O}n (3). Complex 3 features a 3D cubic diamond network. There are also two crystallographically unequivalent Mn(II) ions and two bna2- ligands in the asymmetrical unit, and the ligands also connect the metal centers into [Mn3(μ2-COO)6(COO)2] pinwheel MBBs as in complex 2. The difference lies in that the terminal ligands are two pyridine molecules in complex 3, instead of ethanol molecules in 2 (Figure 5). The MBB is connected to another four MBBs in a similar way as that of 2. However, there are still some remarkable differences between them. First, each pair of bna2- ligands which connect two MBBs together is enantiomer in 3. Second, its Mn1-Mn2 distance is 4.187 A˚ and thet Mn2-Mn1-Mn2 angle is 152.77°. Third, the MBBs should be considered as distorted tetrahedral 4-connected nodes rather than planar

Figure 7. TG plots of 1-3.

in 2, bringing forth a 3D cubic diamond network with Schlafli symbol 66 topology in 3. The potential porosity is 1227.1 A˚3, which accounts for 12.5% of the total cell volume as calculated by PLATON.11 There are two types of void space in 3. The protonated pyridine (py) molecules are located in the former type of void space and interact with the naphthyl rings through one group of π-π interactions (the distance between the planes is 3.473 A˚). The phenolic groups protrude into the latter type and the guest water molecules are located in it (Figure S3, Supporting Information). Effect of Protonated Cationic Pyridine Templates. The use of positive-charged organic templates, such as tetraalkylammonium cations or protonated cationic amines, also called structure-directing agents, to direct the self-assembly of molecular precursors into extended frameworks is widely found in inorganic framework materials. However, the research of their influence on MOFs based on well-defined

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Figure 8. χMT vs T curve for complexes 2 (a) and 3 (b). The solid line represents the best fit curve. Inset: the χM vs T plot.

[Mn3(μ2-COO)6(COO)2] pinwheel MBBs is unprecedented.12 In complexes 1-3, the utilization of distinct positive-charged organic templates, namely, py and pic, has shown prominent influence on the frameworks and properties of the complexes. Py is used as a deprotonation reagent in the synthesis of 1, and not included in the structure, while in 2 and 3, the organic bases pic and py are the components of the structures. Further study reveals that 1 cannot be produced without the addition of py. In 2, pic molecules do not coordinate to the metal centers, while in 3, py molecules are engaged in coordination. We figured out that this may result from the much more steric hindrance of pic due to its p-methyl group. However, with two py molecules on each side, the MBBs in 3 are much larger than those in 2. This justifies the different conformations of the nodes, since the space conformation of tetrahedral 4-connected nodes can better accommodate the larger nodes than the planar ones, which rationalizes the different dimensionalities of 2 and 3. Furthermore, the different terminal ligands lead to different Mn-Mn distances and Mn-Mn-Mn angles, which further affect the magnetic properties of these two complexes as discussed in the following text. TG Research. The thermal stabilities were investigated and the results are shown in Figure 7. Complex 1 loses the free DMF molecules around 200 °C (calculated: 10.89%, found: 11.00%), and the following thermal behavior may be the loss of coordination water molecules and DMF molecules and the subsequent decomposition of the framework. For 2, the loss of free water molecules occurs from 30 to 350 °C (calculated: 4.37%, found: 4.40%), and then the framework undergoes rapid decomposition. The loss of free molecules in 3 takes place from 30 to 135 °C (calculated: 3.47%, found: 3.61%), followed by the further loss of the coordination water molecules as well as the pyridine molecules and the collapse of the host skeleton. Magnetic Properties. The temperature-dependent magnetic properties of complexes 2 and 3 were measured on crystalline samples in the temperature range of 2-300 K at an applied magnetic field of 2000 Oe. They are plotted as χMT and χM versus T (χM is the magnetic susceptibility per Mn(II) ion) in Figure 8. For complex 2, χMT is equal to 3.82 emu mol-1 K at 300 K, which is a little smaller than the value for one isolated Mn(II) ion (4.375 emu mol-1 K). Upon cooling, the value of χMT first decreases smoothly to

3.79 emu mol-1 K from 300 K to 90 K, while from 90 to 2 K, there is a dramatic decline of the χMT value, reaching 0.84 emu mol-1 K. The value of χMT for complex 3 is equal to 3.42 emu mol-1 K at 300 K. As the temperature is lowered from 300 to 145 K, there is a slight increase of the value of χMT to 3.52 emu mol-1 K, whereas below 145 K, the χMT value decreases sharply and reaches 1.30 emu mol-1 K at 2 K. The plots indicate that there are antiferromagnetic behaviors in both complexes. The major difference in the plots of these two complexes is that there is a slight increase of the χMT value in 3. This may be attributed to the weak ferromagnetic interactions between the trinuclear units. The interaction between two external Mn(II) ions as well as the trinuclear units can be ignored considering the long distances between them. The magnetic analysis was then  carried out by using the spin Hamiltonian H=-2J (S^1 3 S^2 þ ^ ^ ^ S 2 3 S3), where S i is the spin of the Mn ion number i. The eigenvalues are given by EðS13 , SÞ ¼ - J½SðSþ1Þ - S13 ðS13 þ1Þ where S is the total spin of the molecule and S13 is the spin quantum number associated with the spin S^13 = S^1 þ S^3 of the external Mn ions. The resulting magnetic susceptibility is given by equation below.13 h i P EðS13 , SÞ 2 2 SðS þ1Þð2S þ1Þ exp S13 , S kT Ng β h i χM T ¼ P EðS13 , SÞ 3k ð2S þ1Þ exp S13 , S kT The best fit for complex 2 was obtained for J=-0.75 cm-1, and g = 1.93. The agreement factor R = Σ([ χMT ]obs [χMT ]calc)2/([χMT ]obs)2 is 6.8  10-3. For complex 3, the best fit was obtained for J=-0.67 cm-1 and g=1.83. The agreement factor R=Σ([χMT ]obs - [χMT ]calc)2/([χMT ]obs)2 is 5.7  10-3. The values of J fall in the range of the reported manganese(II) literature with only carboxylic groups as the bridging ligands.14 Conclusion Three manganese(II)-binaphthalenyl dicarboxylate complexes were synthesized by a solvent or solvothermal method. Complex 1 exhibits a 1D chiral nanotubular structure, while 2 and 3 are based on the similar [Mn3(μ2-COO)6(COO)2] pinwheel MBBs. From a topology perspective, the trinuclear

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units in both 2 and 3 act as 4-connected nodes. Complex 2 is a (4,4) layer structure, while 3 features a 3D cubic diamond network with Schlafli symbol 66 topology, and its potential porosity per unit cell is 1227.1 A˚3. The choices of organic bases show remarkable influence on the assembly and the dimensionality of the complexes. Moreover, the terminal solvent ligands have some impact on the magnetic properties of the [Mn3(μ2-COO)6(COO)2] pinwheel MBB based complexes. Acknowledgment. This work was supported by grants from the National Natural Science Foundation of China and the Natural Science Foundation of Fujian Province. Supporting Information Available: Crystallographic data in CIF format; some additional figures. This material is available free of charge via the Internet at http://pubs.acs.org.

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