Coordination Polymers Constructed by p-Sulfonated Calixarenes and

ARTICLE pubs.acs.org/crystal

Two Unusual 3D Copper(II) Coordination Polymers Constructed by p-Sulfonated Calixarenes and Bis(triazolyl) Ligands Chun Chen, Jian-Fang Ma,* Bo Liu, Jin Yang,* and Ying-Ying Liu Key Lab of Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China

bS Supporting Information ABSTRACT: Two novel Cu(II) compounds [Cu2(btb)3.5(C4AS)(H2O)] 3 2.5(H2O) (1) and [Cu2.5(btp)2(C4AS)(htz)(H2O)3] 3 4.75(H2O) (2) have been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction analyses (btb = 1,4-bis(1,2,4-triazol-1-yl)butane, btp = 1,5bis(1,3,4-triazol-1-yl)pentane, htz = 1,3,4-triazolate, and C4AS = p-sulfonato-calix[4]arene). In 1, the btb ligands connect Cu(II) atoms to form a 3D porous framework. The 1D chains constructed by C4AS and Cu(II) atoms are further bonded to the 3D porous framework through the Cu
O bonds. Topologically, structure 1 belongs to a 3D (3,6)-connected net with the Schl€afli symbol of (42 3 6)(46 3 68 3 8). In 2, the C4AS links the Cu(II) atoms to form 1D chains, which are further connected by the btp and htz to generate a 3D (3,4,6)-connected framework with the Schl€afli symbol of (62 3 8)(52 3 62 3 7 3 8)(54 3 62 3 7 3 87 3 9). The two compounds have been further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses, and UV
vis absorption spectra.

’ INTRODUCTION The current interest in water-soluble calix[4]arenes stems not only from their potential applications in porous materials and in biomedical and heterogeneous catalysis but also from their interesting variety of structures.1
3 The self-assembly of p-sulfonatocalix[4]arene (C4AS) with metal ions and organic molecules can afford various wonderful structures, such as molecular capsules, nanospheroids, tubular arrangements, and coordination polymers.4 So far, a number of 0D, 1D, and 2D complexes based on C4AS have been reported.5
7 In the reported complexes, the 0D, 1D, and 2D structures are further extended into 2D or 3D supramolecular architectures via weak intermolecular forces such as π
π or hydrogen-bonding interactions. However, the selfassembly of C4AS and metals into 3D coordination polymers is a significant challenge. As far as we know, only several 3D Ln(III) coordination frameworks based on C4AS ligands have been reported by Atwood and Liao et al. so far.6 It is well established that the introduction of the N-donor chelating ligand (1,10-phen or 2,20 -bipyridine) into the metal/ C4AS system can modify the structures of the complexes. Nevertheless, they are mainly focused on 0D, 1D, or 2D structures. On one hand, the bulk aromatic chelating ligands employed in the reaction system increased the steric hindrance at the metal centers, which affects the coordination behaviors of other bridging ligands to the metals. On the other hand, the chelating ligand occupied two additional coordination sites of the metals, which leads to low-dimensional structures. It is anticipated that if a secondary N-donor bridging ligand can be used in r 2011 American Chemical Society

the reaction system, the dimensions of the complex structures will be greatly improved. Among the N-donor bridging ligand, bis(triazolyl) is a good candidate for this system.8 It can adopt diverse conformations to meet the different coordination requirements of the metal ions, resulting in the formation of highdimensional frameworks. Taking inspiration from the aforementioned points, we successfully synthesized two coordination polymers in the reaction system of C4AS/bis(triazolyl)/copper(II), [Cu2(btb)3.5(C4AS)(H2O)] 3 2.5(H2O) (1) and [Cu2.5(btp)2(C4AS)(htz)(H2O)3] 3 4.75(H2O) (2) (btb = 1,4-bis(1,2,4-triazol-1-yl)butane, btp = 1,5-bis(1,3,4-triazol-1-yl)pentane, and htz = 1,3,4-triazolate). It is the first time that the 3D coordination polymers assembled by transitional metals/C4AS/N-donor ligands have been reported.

’ EXPERIMENTAL SECTION Materials and Methods. All reagents and solvents for syntheses were purchased from commercial sources and used as received. Na4[psulfonato-calix[4]arene] (Na4C4AS),9a btb, and btp were synthesized by the procedures described previously.9b,c Synthesis of [Cu2(btb)3.5(C4AS)(H2O)] 3 2.5(H2O) (1). Cu(Ac)2 3 H2O, C4AS, and btb (2:1:3) were dissolved in 10 mL of water, and HCl was added until the pH value of the system was adjust to about 2.0. The resulting solution was stirred for about 30 min at room Received: June 8, 2011 Revised: August 30, 2011 Published: September 16, 2011 4491

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temperature, sealed in a 20 mL Teflon-lined stainless steel aotoclave, and heated at 130
C for 3 days at autogenous pressure. After the mixture was cooled to room temperature at 10
C 3 h
1, blue crystals of compound 1 were obtained (yield: 58%). Anal. Calcd for C56H69N21O19.5S4Cu2 (Mr = 1603.63): C, 41.94; H, 4.34; N, 18.34, Cu, 7.93. Found: C, 41.45; H, 3.93; N, 18.20; Cu, 8.01. IR (cm
1): 3422(m), 3263(m), 3126(s), 2953(w), 2210(w), 1770(w), 1534(s), 1375(w), 1289(m), 1179(s), 1134(s), 1041(s), 831(m), 628(s), 555(s).

Synthesis of [Cu2.5(btp)2(C4AS)(htz)(H2O)3] 3 4.75(H2O) (2).

The preparation of compound 2 was similar to that of 1 except that btp and htz were used instead of btb. Blue crystals of 2 were obtained (yield: 5%). Anal. Calcd for C96H123N30O48S8Cu5 (Mr = 3039.42): C, 37.94; H, 4.08; N, 13.80; Cu, 10.45. Found: C, 38.51; H, 3.91; N, 13.89; Cu, 10.57. IR (cm
1): 3419(w), 3119(m), 2947(s), 2953(w), 2210(w),

Table 1. Crystal Data and Structure Refinements for Compounds 1 and 2 1

2

formula

C56H61N21O19.50S4Cu2

C96H86N30O46S8Cu5

fw crystal system

1595.58 monoclinic

3031.42 monoclinic

space group

P21/n

P21/c

a (Å)

20.6238(6)

13.6903(12)

b (Å)

16.4559(3)

13.2671(12)

c (Å)

21.8274(6)

37.029(3)

α (deg)

90

90

β (deg)

112.992(3)

99.371(2)

γ (deg) V (Å3)

90 6819.4(3)

90 6635.8(10)

Z

4

2

Dcalcd (g cm
3)

1.554

1.517

F(000)

3320

3124

Rint

0.0433

0.0647

GOF on F2

0.823

1.174

R1 [I > 2σ(I)]

0.0371

0.0721

wR2 [I > 2σ(I)]

0.0781

0.1694

1791(w), 1640(s), 1535(s), 1449(m), 1361(s), 1175(m), 1039(s), 891(s), 628(s), 554(s). Physical Measurements. The C, H, and N elemental analysis was conducted on a Perkin
Elmer 240C elemental analyzer. The content of Cu was determined with a Plasma-SPEC(I) ICP atomic emission spectrometer. The FT-IR spectra were recorded from KBr pellets in the range 4000
400 cm
1 on a Mattson Alpha-Centauri spectrometer. Diffuse reflectivity was measured from 200 to 800 nm using barium sulfate as a standard with 100% reflectance. Thermogravimetric analysis (TGA) was performed on a Perkin-Elmer TG-7 analyzer heated from 40 to 800
C under nitrogen gas. Powder X-ray diffraction (XRD) patterns of the samples were collected on a Rigaku Dmax 2000 X-ray diffractometer with graphite monochromatized Cu Kα radiation (λ = 0.154 nm) and with 2θ ranging from 5 to 50
. The experimental powder XRD patterns are in good agreement with the corresponding simulated ones except for the relative intensity variation because of preferred orientations of the crystals. Therefore, the phase purity of the as-synthesized products is substantiated (Figure S1 of the Supporting Information). Crystal Structure Determination. Single-crystal X-ray diffraction data for 1 was recorded on an Oxford Diffraction Gemini R Ultra diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 293 K. Single-crystal X-ray diffraction data for 2 was collected on a Bruker Apex CCD diffractometer with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at 193 K. Absorption corrections were applied using a multiscan technique. All the structures were solved by Direct Method of SHELXS-9710 and refined by fullmatrix least-squares techniques using the SHELXL-9711 program. Nonhydrogen atoms of the complexes were refined with anisotropic temperature parameters. The H atoms bound to carbon were refined using a riding model with d(C
H) = 0.93 Å, Uiso = 1.2 Ueq(C) for aromatic atoms and 0.97 Å, Uiso = 1.5 Ueq(C) for CH2 atoms. Some water H atoms were located in a difference Fourier map and refined as riding atoms with d(O
H) = 0.85
0.89 Å and Uiso = 1.5 Ueq(O). Some water H atoms of compounds 1 and 2 were not included in the model. Disordered atoms (O4, O40 , O5, O50 , O10, O100 , O11, O110 , C47, C470 , C48, C480 , C49, C490 for 1 and O1, O10 , O3, O30 , O7, O70 , O9, O90 , C34, C340 , C35, C350 , C36, C360 , C37, C370 , C41, C410 , C42, C420 , N4, N40 , N5, N50 for 2) were split over two sites, with a total occupancy of 1. Thermogravimetric analysis indicates the presence of 7.75 water molecules in the structure of 2. The detailed crystallographic data and structure refinement parameters for 1

Table 2. Selected Bond Distances (Å) and Angles (deg) for 1a

a

Cu(1)
N(15)

2.001(3)

Cu(1)
N(20)

2.001(3)

Cu(1)
N(17)#1

2.005(3)

Cu(1)
N(1)

2.021(3)

Cu(1)
O(7)#2

2.338(2)

Cu(1)
O(12)#1

2.348(2)

Cu(2)
O(2W)

1.968(2)

Cu(2)
N(6)

1.977(3)

Cu(2)
N(11)#3

1.985(3)

Cu(2)
N(7)

1.994(2)

Cu(2)
O(1W)

2.432(2)

N(15)
Cu(1)
N(20)

88.23(11)

N(15)
Cu(1)
N(17)#1 N(15)
Cu(1)
N(1)

91.82(11) 173.95(11)

N(20)
Cu(1)
N(17)#1 N(20)
Cu(1)
N(1)

176.82(11) 87.98(11)

N(17)#1
Cu(1)
N(1)

92.22(11)

N(15)
Cu(1)
O(7)#2

85.91(9)

N(20)
Cu(1)
O(7)#2

88.73(9)

N(17)#1
Cu(1)
O(7)#2

94.45(10)

N(1)
Cu(1)
O(7)#2

89.29(10)

N(15)
Cu(1)
O(12)#1

93.69(10)

N(20)
Cu(1)
O(12)#1

85.97(10)

N(17)#1
Cu(1)
O(12)#1

90.85(10)

N(1)
Cu(1)
O(12)#1

90.75(10)

O(7)#2
Cu(1)
O(12)#1

174.69(9)

O(2W)
Cu(2)
N(6)

178.18(11)

O(2W)
Cu(2)
N(11)#3

89.55(10)

N(6)
Cu(2)
N(11)#3 N(6)
Cu(2)
N(7)

91.86(11) 91.67(10)

O(2W)
Cu(2)
N(7) N(11)#3
Cu(2)
N(7)

86.80(10) 173.11(11)

O(2W)
Cu(2)
O(1W)

88.58(11)

N(6)
Cu(2)
O(1W)

92.47(11)

N(11)#3
Cu(2)
O(1W)

93.92(10)

N(7)
Cu(2)
O(1W)

91.84(9)

Symmetry transformations used to generate equivalent atoms: (#1)
x + 1/2, y
1/2,
z + 3/2; (#2)
x + 1,
y + 1,
z + 2; (#3) x + 1/2,
y + 1/2, z + 1/2. 4492

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and 2 are summarized in Table 1. Selected bond distances, angles, and hydrogen bonds are listed in Tables 2
4.

’ RESULTS AND DISCUSSION Structure of [Cu2(btb)3.5(C4AS)(H2O)] 3 2.5(H2O) (1). Singlecrystal X-ray analysis reveals that 1 crystallizes in a monoclinic system with space group P21/n and an asymmetric unit contains two Cu(II) atoms, one C4AS, three and a half btb ligands, one coordinated water molecules, and two and a half lattice water molecules (Figure 1a). Cu1 is six-coordinated by four nitrogen atoms from four different btb ligands (Cu1
N17#1 = 2.005(3) Å, Cu1
N20 = 2.001(3) Å, Cu1
N15 = 2.001(3) Å, and Cu1
N1 = 2.021(3) Å) and two sulfonate oxygen atoms from two different C4AS ligands (Cu1
O7#2 = 2.338(2) Å and Cu1
O12#1 = 2.348(2) Å) in a distorted octahedral coordination geometry. Cu2 is five-coordinated by three nitrogen atoms from three different btb ligands (Cu2
N6 = 1.977(3) Å, Cu2
N7 = 1.994(2) Å, and Cu2
N11#3 = 1.985(3) Å) and two oxygen atoms from two water molecules (Cu2
O1W = 2.432(2) Å and

Table 3. Hydrogen Bonds for 1 (Å and deg)a d(D
H) d(H 3 3 3 A) d(D 3 3 3 A) — (DHA)

D
H 3 3 3 A O(1W)
H(1B0 ) 3 3 3 O(10)#2 O(2W)
H(2A0 ) 3 3 3 O(8) O(2W)
H(2B0 ) 3 3 3 O(2)#3

0.84

2.00

2.828(8)

170.0

0.84

1.90

2.715(3)

163.2

0.68

1.98

2.660(4)

170.7

Symmetry transformations used to generate equivalent atoms: (#2)
x + 1,
y + 1,
z + 2; (#3) x + 1/2,
y + 1/2, z + 1/2.

a

Cu2
O2W = 1.964(2) Å) in a square pyramidal sphere. Both the C4AS and btb ligands adopt bidentate coordination modes (Schemes 1 and 2). In this way, the two sulfonate groups of C4AS bridge the Cu(II) atoms to yield a 1D chain with the Cu 3 3 3 Cu separation of 11.726 Å. Interestingly, two neighboring 1D chains are arranged in a trans fashion with the dihedral angle of 11.603
between benzene rings A and B (Figures 1b and S2a). There are O
H 3 3 3 O hydrogen-bonding interactions between adjacent hydrophilic chains (Figure S2b and Table 3). In addition, the proper distances between O3W and sulfonate oxygen atoms (O3W
O5#2 = 2.737 and O3W
O16 = 2.664 Å; symmetry code: (#2)
x + 1,
y + 1,
z + 2) indicate the formation of a O
H 3 3 3 O hydrogen bond, which suggests intermolecular hydrogen-bonding interactions between neighboring hydrophobic chains (Figure S2c of the Supporting Information). If the C4AS ligand is ignored, the btb ligands link the Cu(II) atoms to form a 3D porous skeleton (Figures S2d and 1c). The 1D chains constructed by C4AS ligands and Cu(II) atoms are bonded to the 3D porous skeleton through the Cu
O bonds (Figure 1d). The twisted btb ligands occupied the cavities of the calixarenes. Better insight into such an intricate framework can be accessed by reducing multidimensional structures to simple node-andconnecting nets. Cu1 can be assigned to a six-connected node, while the Cu2 can be considered as a three-connected node. The C4AS and btb act as linkers. Accordingly, the complicated 3D structure of 1 can be simplified to a binodal (3,6)-connected net with the Schl€afli symbol of (42 3 6)(46 3 68 3 8). As far as we know, compound 1 represents the first (3,6)-connected framework based on C4AS.

Table 4. Selected Bond Distances (Å) and Angles (deg) for 2a Cu(1)
N(14)#1

1.984(4)

Cu(1)
N(14)

1.984(4)

Cu(1)
N(9) Cu(1)
O(3W)

2.069(4) 2.399(4)

Cu(1)
N(9)#1 Cu(1)
O(3W)#1

2.069(4) 2.399(4) 1.976(4)

Cu(2)
N(13)

1.968(4)

Cu(2)
N(3)

Cu(2)
N(7)

1.997(5)

Cu(2)
O(12)

2.043(4)

Cu(2)
O(1W)

2.273(6)

Cu(3)
N(6)#2

1.955(6)

Cu(3)
N(12)#1

2.000(6)

Cu(3)
O(2W)

1.973(5)

Cu(3)
N(15)

2.005(4)

Cu(3)
O(6)#3

2.474(5)

2.414(5)

N(14)
Cu(1)
N(14)#1

180.0(2)

N(14)
Cu(1)
N(9) N(14)
Cu(1)
N(9)

90.41(18) 89.59(18)

N(14)#1
Cu(1)
N(9)#1 N(14)#1
Cu(1)
N(9)

89.59(18) 89.59(18)

N(9)#1
Cu(1)
N(9)

180.000(1)

N(14)
Cu(1)
O(3W)

84.92(15)

N(14)#1
Cu(1)
O(3W)

95.08(15)

N(9)#1
Cu(1)-O(3W)

95.08(15)

N(9)
Cu(1)
O(3W)

85.60(15)

N(14)
Cu(1)
O(3W)#1

95.08(15)

N(14)#1
Cu(1)
O(3W)#1

84.92(15)

N(9)#1
Cu(1)
O(3W)#1

85.60(15)

N(9)
Cu(1)
O(3W)

94.40(16)

O(3W)
Cu(1)
O(3W)#1

180.000(2)

N(13)
Cu(2)
N(3)

177.99(19)

N(13)
Cu(2)
N(7)

89.41(19)

N(3)
Cu(2)
N(7) N(3)
Cu(2)
O(12)

91.80(19) 90.50(17)

N(13)
Cu(2)
O(12) N(7)
Cu(2)
O(12)

88.3(17) 177.70(17)

Cu(3)
O(2)#3 #1

#1

N(13)
Cu(2)
O(1W)

90.29(17)

N(3)
Cu(2)
O(1W)

91.31(19)

N(7)
Cu(2)
O(1W)

92.31(19)

N(6)#2
Cu(3)
O(2W)

88.4(3)

N(6)#2
Cu(3)
N(12)#1

92.8(3)

O(2W)
Cu(3)
N(12)#1

176.0(2)

N(6)#2
Cu(3)
N(15)

177.5(3)

O(2W)
Cu(3)
N(15)

90.2(2)

N(12)#1
Cu(3)
N(15)

88.7(2)

N(6)#2
Cu(3)
O(2)#3

90.2(3)

O(2W)-Cu(3)
O(2)#3

91.8(2)

N(12)#1
Cu(3)
O(2)#3

92.1(2)

#3

N(15)
Cu(3)
O(2) a

87.38(18)

Symmetry transformations used to generate equivalent atoms: (#1)
x + 2,
y,
z + 2; (#2) x,
y
1/2, z + 1/2; (#3)
x + 3,
y
1,
z + 2. 4493

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Figure 1. (a) Coordination environments of Cu(II) atoms in 1 (25% probability displacement ellipsoids). Symmetry codes: (#1)
x + 1/2, y
1/2,
z + 3/2; (#2)
x + 1,
y + 1,
z + 2; (#3) x + 1/2,
y + 1/2, z + 1/2; (#4)
x,
y + 1,
z + 2; (#5)
x + 1/2, y + 1/2,
z + 3/2; (#6) x
1/2,
y + 1/2, z
1 /2. (b) Two trans arrangement chains constructed by C4AS and Cu1 atoms. (c) Schematic representation of the 3D porous framework constructed by btb and Cu(II) atoms. (d) View of the binodal (3,6)-connected net of 1 with the Schl€afli symbol of (42 3 6)(46 3 68 3 8).

Scheme 1. Coordination Modes of C4AS in Compounds 1 (Left) and 2 (Right)

4494

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Scheme 2. Coordination Modes of btb (I), btp (II and III), and htz (IV)

Structure of [Cu2.5(btp)2(C4AS)(htz)(H2O)3] 3 4.75(H2O) (2). Single-crystal X-ray analysis reveals that 2 crystallizes in a monoclinic system with space group P21/c and an asymmetric unit contains two and a half Cu(II) atoms, one C4AS, two btp ligands, one htz ligand, three coordinated water molecules, and four and three-quarters free water molecules (Figure 2a). Although both Cu1 and Cu3 atoms adopt octahedral coordination geometries, their coordination environments are entirely different. Cu1 is coordinated by two water oxygen atoms from two water molecules (Cu1
O3W = 2.399(4) and Cu1
O3W#1 = 2.399(4) Å) and by four nitrogen atoms from two btp ligands and two htz ligands (Cu1
N9 = 2.069(4) Å, Cu1
N9#1 = 2.069(4), Cu1
N14 = 1.984(4) Å and Cu1
N14#1 = 1.984(4) Å). Cu3 is coordinated by three oxygen atoms from one water molecule and two C4AS ligands (Cu3
O2W = 1.973(5) Å, Cu3
O2#3 = 2.414(4) Å, and Cu3
O6#4 = 2.474(4) Å) and by three nitrogen atoms from two btp ligands and one htz ligand (Cu3
N6#2 = 1.955(6) Å, Cu3
N12#1 = 2.000(6) Å, and Cu3
N15 = 2.005(4) Å). However, Cu2 is five-coordinated by three nitrogen atoms from two btp ligands and one htz ligand (Cu2
N7 = 1.997(5) Å, Cu2
N3 = 1.976(6) Å, and Cu2
N13 = 1.968(4) Å) and by two oxygen atoms from one water molecule and one C4AS (Cu2
O1W = 2.273(4) Å and Cu2
O12 = 2.043(4) Å) in a distorted square-pyramidal geometry. The C4AS ligands show tridentate modes and link neighboring Cu(II) atoms to form 1D chains with the Cu 3 3 3 Cu distance of 13.267 Å (Figure 2b). Like 1, two neighboring 1D chains are also arranged in a trans fashion. However, the dihedral angle between benzene rings A and B is 39.319
(Figures 2b and S3a). There are O
H 3 3 3 O hydrogen-bonding interactions between the coordinated water molecules and sulfonate oxygen atoms of adjacent hydrophilic chains (O3W
O11 = 2.735 Å), although the hydrogen atoms of O3W could not be found in difference Fourier maps. Moreover, there exist hydrogen-bonding interactions between hydroxyl groups and sulfonate anions of neighboring hydrophobic and hydrophobic chains (O4#4
O15 = 2.870 Å; symmetry code: (#4) x,
y
1/2, z
1/2) (Figure S3b of the Supporting Information). The btp and htz link the Cu(II) atoms to generate a 2D wavelike layer along the a-axis. Notably, single-stranded helical chains of both handedness are found in the layers. Adjacent helical chains are symmetry equivalently related through inversion centers and possess the opposite chirality, indicative of an achirality feature of the layer (Figure 2c). Moreover, the 1D chains and the 2D wavelike layers

form a 3D framework via sharing the Cu(II) atoms (Figure 2d). The wavy btp ligands are filled in the cavities of the C4AS. From a topological viewpoint, tridentate C4AS can be considered as a three-connected node, Cu3 acts a 4-connected node, three adjacent trinuclear Cu(II) atoms (Cu1, Cu2, and Cu2#1) are regarded as a six-connected node (Figure S4 of the Supporting Information), htz and btp containing N1 are considered as one linker, and btp containing N7 is defined as another linker. So, the 3D framework of 2 can be simplified as a (3,4,6)-connected net with Schl€afli symbol of (62 3 8)(52 3 62 3 7 3 8)(54 3 62 3 7 3 87 3 9) (Figure 2d). In compounds 1 and 2, the C4AS ligands exhibit cone conformations, but their coordination modes and pinches are quite different (Scheme 2). The C4AS in 1 is bonded to two Cu(II) ions through its two adjacent sulfonate groups, whereas the C4AS bridges three Cu(II) ions with its three sulfonate groups in 2. Moreover, in 1, the trans S 3 3 3 S distances of C4AS are 9.739 and 11.220 Å (the distance between two oppositely oriented sulfonate groups), and the dihedral angles between the opposite aromatic rings are 75.573 and 68.516
. In 2, the corresponding S 3 3 3 S distances (9.200 and 11.899 Å) are similar to those of 1, while their dihedral angles (40.645 and 33.899
for 2) are quite different from those of 1. This difference may come from the different pinches of C4AS ligands in 1 and 2 (Scheme 1). The N positions of bis(triazolyl) also have an effect on the framework structure. In btb of 1, the three N atoms of the triazole ring are at the 1, 2, and 4 sites, whereas the ones in btp and htz of 2 are at the 1, 3, and 4 positions. Obviously, the 2-position N atom of btp will increase the steric hindrances when coordinated with the metal atoms. Therefore, the N-donor ligands show different coordination modes in 1 and 2 (Scheme 2). In 1, the btb shows a bidentate coordination mode, while the btp adopts both bidentate and tridentate coordination modes in 2 (Scheme 2). Thermal Analysis. To estimate the stability of compounds 1 and 2, their thermogravimetric analyses (TGA) were carried out. The experiments were performed on samples consisting of numerous single crystals of 1 and 2 under a N2 atmosphere with a heating rate of 10
C/min. As shown in Figure 3, compounds 1 and 2 show similar weight loss steps. The first weight losses from 39 to 255
C for 1 (obsd 3.6%, calcd 3.9%) and from 39 to 288
C for 2 (obsd 8.1%, calcd 9.2%) are attributed to the release of their water molecules. The second losses from 255 to 451
C for 1 (obsd 41.7%, calcd 42.1%) and from 288 to 411
C for 2 (obsd 4495

dx.doi.org/10.1021/cg2007167 |Cryst. Growth Des. 2011, 11, 4491–4497

Crystal Growth & Design

ARTICLE

Figure 2. (a) Coordination environments of Cu(II) atoms in 2 (25% probability displacement ellipsoids). Symmetry codes: (#1)
x + 2,
y,
z + 2; (#2) x,
y
1/2, z + 1/2; (#3)
x + 3,
y
1,
z + 2; (#4) x,
y
1/2, z
1/2. (b) Two trans arrangement chains constructed by C4AS and Cu(II) atoms in 2. (c) View of the 2D wavelike layer containing helical chains of both handedness constructed by Cu(II) ions, btp, and htz along the a axis. (d) Schematic representation of a binodal (3,4,6)-connected net with the Schl€afli symbol of (62 3 8)(52 3 62 3 7 3 8)(54 3 62 3 7 3 87 3 9).

Figure 3. TGA curves of compounds 1 and 2.

47.1%, calcd 48.4%) correspond to the departure of C4AS. The third weight losses from 451 to 540
C for 1 and from 451 to 486
C for 2 may be attributed to the departure of N-donor ligands. IR Spectra. The O
H stretching vibrations of water molecules in complexes 1 and 2 are observed at 3126
3422 and 3119
3419 cm
1, respectively. For 1 and 2, the C
H asymmetric and symmetric stretching vibrations of the methylene are observed at 2953 and 2947 cm
1, respectively. The stretching vibrations of CdN are observed in the ranges 1547
1600 and 1361
1447 cm
1 for 1 and 2, respectively.8i The skeleton vibrations of the C
C of btb and btp ligands are observed at 1289
1041 and 1175
1039 cm
1, respectively. Optical Energy Gap. The UV
vis absorption spectra of compounds 1 and 2 were carried out in the crystalline state at 4496

dx.doi.org/10.1021/cg2007167 |Cryst. Growth Des. 2011, 11, 4491–4497

Crystal Growth & Design

Figure 4. UV
vis absorption spectra of C4AS, 1, and 2.

room temperature (Figure 4). The C4AS ligand exhibits a strong absorption band in the range 259
294 nm, which can be ascribed to π* f π transitions of the ligands. Energy bands of complex 1 from 524 to 722 and of complex 2 from 482 to 688 are assigned as d
d transitions.8h

’ CONCLUSION In conclusion, two unusual coordination polymers based on a C4AS ligand and flexible N-donor ligands have been successfully synthesized under hydrothermal conditions. Compounds 1 and 2 represent the first 3D coordination polymers constructed by transition metals, C4AS, and N-donor bridging ligands. The coordination modes of C4AS and the N-donor bridging ligands have significant effects on the final structures of the compounds. This work presents a new route for the construction of highdimensional frameworks based on calixarenes and N-donor flexible ligands. ’ ASSOCIATED CONTENT

bS

Supporting Information. Some diagrams of the structures; powder XRD patterns of complexes; cif data. This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*J.-F.M.: e-mail, [email protected]; fax, +86-43185098620. J.Y.: e-mail, [email protected].

’ ACKNOWLEDGMENT We thank the National Science Foundation of China (21001023 and 21071028), the Specialized Research Fund for the Doctoral Program of Higher Education, the Science Foundation of Jilin Province (20090137 and 20100109), the Fundamental Research Funds for the Central Universities, and the Training Fund of NENU’S Scientific Innovation Project for support.

ARTICLE

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