КООРДИНАЦИОННАЯ ХИМИЯ, 2015, том 41, № 6, с. 338-341

УДК 541.49

A THREE-DIMENSIONAL COORDINATION POLYMER BASED ON 3,5-PYRAZOLEDICARBOXYLIC ACID (H3Pdc): [Cd2(HPdc)15a(H2O)2]„ © 2015 L. Song1, L. Li1, T. Yang1, X. H. Zhou1, *, and X. J. Yin2

1Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials, National Jiangsu

Syngerstic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing, 210023 P.R. China 2School of Chemistry and Biological Engineering, Hechi University, Yizhou, 546300 P.R. China

*E-mail: iamxhzhou@njupt.edu.cn Received December 12, 2014

The title coordination polymer, [Cd2(HPdc)i.5Cl(H2O)2]n (I) (H3Pdc = 3,5-pyrazoledicarboxylic acid), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction (CIF file CCDC no. 1037505). Complex I crystallizes in orthorhombic space group Pbcn with a = 10.2631(11), b = = 17.1997(18), c = 14.3044(15) A, V = 2525.0(5) A3, C15H14Cd4Cl2N6O16, M = 1054.82, pc = 2.775 g/cm3, ^(MoKa) = 3.627 mm-1, F(000) = 2000, GOOF = 1.067, Z = 4, the final R1 = 0.0562 and wR2 = 0.1301 for I > 2ct(I). The Cd(1) ions and HPdc2- ligands connect to form a serial of the 2D corrugated 63 sheets packing parallel along the z axis. Each 63 sheet is connected with the two neighboring sheets by the Cl-and Cd(2) ions to construct the 3D framework of I. The 3D structure can also be rationalized as a 4-connected trinodal ( topological network (the long Schlafli symbol is ( by considering the Cd(1), Cd(2) ions and HPdc2- ligands as 4-connected nodes, the Cl- ions as linkers, respectively.

DOI: 10.7868/S0132344X15060079


According to the definition oflUPAC, a coordination polymer (CP) is a coordination compound with repeating coordination entities extending in 1, 2, or 3 dimensions. However, a metal-organic framework (MOF) is a coordination network with organic ligands containing potential voids [1]. Both of them have attracted much interest because of their intriguing structural topologies and their interesting applications as functional materials in guest sensing and recognition [2—5], catalysis [6—8], magnetism [9, 10], etc. The preparations of CPs and MOFs are self-assembly process of the various components under hydrothermal or solvothermal conditions, which depend strongly on the several factors, such as the coordination nature ofligand structure, the solvent systems, counterions, and so on [11, 12]. Undoubtedly, the ligand is the key factor for manipulating the topologies of CPs and MOFs.

3,5-Pyrazoledicarboxylic acid (H3Pdc) is a multifunctional ligand possessing many advantages, such as multiple coordination sites involving two pyrazole nitrogen atoms and four carboxylate oxygen atoms, three different abstractable hydrogens, sterically compact

planar heteroaromatic dicarboxylates, etc. [13—17]. In this work, based on H3Pdc, we synthesize a three dimensional coordination polymer [Cd2(HPdc)15Cl(H2O)2]B (I) and describe its structure in detail.


All chemicals were reagent grade and used as received. Elemental analyses for C, H and N were performed on a PerkinElmer 240C analyzer. Infrared spectra were recorded on a Vector22 Bruker Spectrophotometer with KBr pellets in the 400—4000 cm-1 region. The crystal structure was determined by single-crystal X-ray diffraction and using SHELXS-97, SHELXL-97 software for structure solution and refinement correspondingly.

Synthesis of complex I. A mixture of CdCl2 (0.2 mmol, 36.7 mg), H3Pdc (0.2 mmol, 34.8 mg), CH3CN (2 mL) and H2O (5 mL) was sealed in a 15 mL Teflon-lined bomb and heated at 140°C for 3 days. The reaction mixture was slowly cooled to room temperature in a rate of 10°C/30 mins. Colorless block crystals of I



suitable for X-ray diffraction analysis were isolated in 23% yield.

For C15H14N6O16Cl2Cd4

anal. calcd., %: C, 17.08; H, 1.34; N, 7.97. Found, %: C, 17.34; H, 1.17; N, 7.84.

X-ray structure determination. A colorless single crystal of I with dimensions of 0.22 x 0.24 x 0.26 mm was mounted on a Bruker Smart Apex CCD area detector diffractometer using graphite-monochromated Mo^a radiation (X = 0.71073 A ) using the 9 scan mode in the range 2.31° < 9 < 28.34° at 291(2) K. Raw irame data were integrated with the SAINT program [18]. The structure was solved by direct methods using SHELXS-97 and refined by full-matrix least-squares on F2 using SHELXS-97 [19]. An empirical absorption correction was applied with the program SADABS [20]. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed in calculated positions and refined as riding mode with C—H = 0.93 A for sp2 hy-bridizated carbon atom, N-H = 0.86 A for sp2 hybrid-izated nitrogen atom, O-H = 0.96 A for carboxylate oxygen atom, respectively, and Uiso(H) = 1.2Ueq(C, N or O). The H atoms of the water molecules were located in calculated positions and refined as riding mode with O-H = 0.96 A and Uiso(H) = 1.2Ueq(O). The final R1 = 0.0562 and wR2 = 0.1301 for 2187 observed reflections with I > 2g(I) (w = 1/[ct2(F02) + (0.06P)2 + + 1.66P], where P = (Fo2 + 2FC2 )/3). (Ap)max = 1.123 e/A3, (Ap)min = -1.191 e/A3 and (A/a)max = 0.001. Crystal-lographic details for I have been summarized in Table 1. Selected bond lengths and angles for I are given in Table 2. The full tables of atomic coordinates, bond lengths, and bond angles were deposited with the Cambridge Crystallographic Data Centre (CCDC no. 1037505; deposit@ccdc.cam.ac.uk or http:// www.ccdc.cam.ac.uk/data_request/cif) or can be obtained from the authors.

Table 1. Crystallographic data and structure refinement for complex I

Parameter Value

Fw 1054.82

Crystal system Orthorhombic

Space group Pbcn

a , A 10.2631(11)

b, A 17.1997(18)

c, A 14.3044(15)

V, A3 2525.0(5)

Z 4

Pcalcd g cm-3 2.775

p., mm-1 3.627

F(000) 2000

Reflections collected 14187

Unique reflections 3055

Rint 0.0265

GOOF (F2) 1.067

R1, wR2 (I> 2ct(I))* 0.0562, 0.1301

R1, wR2 (all data)* 0.0662, 0.1319

APmaxAPmirn e A-3 1.123/—1.191

* Rx = S||F0| - |FC||/S|F0|; wR2 = [Sw( F02 - Fc2)2/Sw(F02)]1/2.

two oxygen atoms (O(1)lu and O(2)lu) from other HPdc2- ligand, oxygen atom (O(4)lv) from the third HPdc2- ligand, one Cl- ion and one oxygen atom (O(2w)) from one H2O molecule. The Cd-O bond lengths range from 2.192(5) to 2.485(5) Â, the Cd-N bond lengths range from 2.262(6) to 2.273(6) Â and the Cd-Cl bond lengths range from 2.484(2) to 2.570(2) Â (Table 2), which are comparable to those values found in other reported Cd(II) complexes [21,


The asymmetric unit of I contains two crystallo-graphically independent Cd2+ ions, one Cl- ion, one and a half HPdc2- ligands, two coordinated H2O molecules (Fig. 1). The Cd(1) ion has the distorted octahedral coordination environment. The coordination sphere of the Cd(1) ion is completed by one oxygen atom (O(1)) and one nitrogen atom (N(1)) from a HPdc2- ligand, two oxygen atoms(O(3) and O(5)u) from two other HPdc2- ligands, one Cl- ion and one oxygen atom (O(1w)) from one H2O molecule. The Cd(2) ion has the distorted pentagonal bipyramid coordination environment. The coordination sphere of the Cd(2) ion is completed by one oxygen atom (O(5)) and one nitrogen atom (N(3)) from a HPdc2- ligand,

Fig. 1. View of the asymmetric unit of I with the thermal ellipsoids drawn at the 50% probability level. All H atoms have been omitted for clarity.

KOOP,3HHAUHOHHAH XHMH3 tom 41 № 6 2015


340 SONG et al.

Table 2. Selected bond lengths (A) and bond angles (deg) for I*

Bond d, Â Bond d, Â Bond d, Â

Cd(1)-O(1) 2.364(5) Cd(1)-O(3)i 2.216(5) Cd(1)-O(5)u 2.192(5)

Cd(1)-O(1w) 2.485(5) Cd(1)-N(1) 2.273(6) Cd(1)-Cl(1) 2.570(2)

Cd(2)-O(1)iu 2.417(5) Cd(2)-O(2)iii 2.466(6) Cd(2)-O(4)iv 2.382(5)

Cd(2)-O(5) 2.391(5) Cd(2)-O(2w) 2.406(5) Cd(2)-N(3) 2.262(6)

Cd(2)-Cl(1) 2.484(2)

Angle ro, deg Angle ro, deg Angle ro, deg

O(5)iiCd(1)O(3)i 100.89(19) O(5)uCd(1)N(1) 111.8(2) O(3)'Cd(1)N(1) 143.5(2)

O(5)uCd(1)O(1) 175.22(19) O(3)'Cd(1)O(1) 78.76(18) N(1)Cd(1)O(1) 69.9(2)

O(5)uCd(1)O(1w) 83.92(18) O(3)'Cd(1)O(1w) 86.64(19) N(1)Cd(1)O(1w) 81.36(19)

O(1)Cd(1)O(1w) 100.80(17) O(5)uCd(1)Cl(1) 86.45(14) O(3)'Cd(1)Cl(1) 107.90(15)

N(1)Cd(1)Cl(1) 90.31(15) O(1)Cd(1)Cl(1) 89.12(14) O(1w)Cd(1)Cl(1) 163.88(13)

N(3)Cd(2)O(4)iv 146.9(2) N(3)Cd(2)O(5) 69.7(2) O(4)ivCd(2)O(5) 77.63(18)

N(3)Cd(2)O(2w) 97.2(2) O(4)ivCd(2)O(2w) 72.61(18) O(5)Cd(2)O(2w) 81.75(18)

N(3)Cd(2)O(1)ui 85.9(2) O(4)ivCd(2)O(1)iu 118.69(19) O(5)Cd(2)O(1)iu 141.79(18)

O(2w)Cd(2)O(1)iu 72.33(18) N(3)Cd(2)O(2)iii 129.0(2) O(4)ivCd(2)O(2)iii 84.01(18)

O(5)Cd(2)O(2)iii 160.72(17) O(2w)Cd(2)O(2)iu 98.45(18) O(1)iiiCd(2)O(2)iii 54.05(18)

N(3)Cd(2)Cl(1) 105.46(17) O(4)ivCd(2)Cl(1) 81.40(13) O(5)Cd(2)Cl(1) 94.10(13)

O(2w)Cd(2)Cl(1) 153.97(14) O(1)iuCd(2)Cl(1) 121.24(13) O(2)iiiCd(2)Cl(1) 77.20(14)

Cd(2)Cl(1)Cd(1) 114.40(8)

* Symmetry codes: ' -x + 1/2, y + 1/2, z; u x - 1/2, -y + 1/2, -z + 1; iU -x + 1, y, -z + 3/2; iv -x + 1, -y, -z + 1.

22]. The Cl ion in I acts as ^-bridging ligand to bridge Cd(1) and Cd(2) ions. The HPdc2- ligands in I adopt two coordination modes (a and b) as depicted below:









O''' -M


\/t r \

ON N' M mm


networks by the Cl- and Cd(2) ions to construct the 3D framework of I (Fig. 2c). The 3D structure can also be rationalized as a 4- connected trinodal ( topological network (the long Schlâfli symbol is ( by considering the Cd(1) ions, Cd(2) ions and HPdc2-ligands as 4-connected nodes, the Cl- ions as linkers, respectively.

In coordination mode a, the HPdc2- ligand acts in a ^4-n2N,O,n1O,n2N',O',n1O' fashion, chelating two Cd(2) ions and bridging two Cd(1) ions, respectively. In coordination mod

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