Molecular Packing Variation of Crimpled 2D Layers and 3D

Jun 7, 2008 - Compound 4 forms a novel 3D framework based on uncommon “new” 65.8 topology, crystallizes in the acentric orthorhombic space group ...
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Molecular Packing Variation of Crimpled 2D Layers and 3D Uncommon 65.8 Topology: Effect of Ligand on the Construction of Metal-Quinoline-6-carboxylate Polymers Sheng Hu, Hua-Hong Zou, Ming-Hua Zeng,* Qiang-Xin Wang, and Hong Liang*

CRYSTAL GROWTH & DESIGN 2008 VOL. 8, NO. 7 2346–2351

Key Laboratory of Medicinal Chemical Resources and Molecular Engineering, Department of Chemistry and Chemical Engineering, GuangXi Normal UniVersity, Guilin 541004, P. R. China ReceiVed NoVember 23, 2007; ReVised Manuscript ReceiVed February 3, 2008

ABSTRACT: Four coordination polymers Ni(quin-6-c)2 (1), Zn2(quin-6-c)4 (2), Co2(quin-6-c)4 (3), and Zn(OH)(quin-6-c) (4) (quin6-c ) quinoline-6-carboxylate) have been synthesized by methods of hydrothermal reaction and their crystal structures determined. In the compound 1, quin-6-c ligands act as ditopic linkers bound to Ni atoms, resulting in the formation of an unusually wavelike 2D (4,4) net. The adjacent layers are stacked offset with respect to each other, in an ABAB fashion. Compounds 2 and 3 are isostructural and feature a unique 2D molecular network composed of crimpled double-line ribbons. The 2D layers stack in a rare, interesting ABCD pattern along the crystallographic c axis. Compound 4 forms a novel 3D framework based on uncommon “new” 65.8 topology, crystallizes in the acentric orthorhombic space group Pna21 and displays powder SHG intensity ca. 460 times in comparing with that of R-quartz. The [Zn(µ2-OH)]n helical chains connected to each other through unsymmetrical quin-6-c ligands in 4 have ensured its acentricity and SHG-activity. A discussion of the crystal structures, as well as the coordination properties of quin-6-c ligands upon different geometries of the central ions, is provided. Introduction The rapidly expanding field of crystal engineering of 2D and 3D coordinated polymers is of great current interest for both structural and topological novelty as well as for their potential application as functional materials.1 The design of coordination polymers is highly influenced by factors such as the coordination nature of the metal ion, the structural characteristics of the organic ligand, the metal-ligand ratio, the reaction condition, and other possible influences, which provides a possible approach to the controlled assembly of metal-organic frameworks, with systematically tunable interesting properties.2–4 Recent research has demonstrated the dramatic influence of multifunctional ligands on the framework of inorganic materials, such as how organic components modify the inorganic frameworks.5 As is well-known, the pyridinecarboxylic acid unit is widely used in the synthesis of coordination polymers, that exhibit useful properties such as porosity and magnetism.1,2 In contrast, research on metal quinoline-carboxylate systems is still limited in comparison with the above studies.6 Quinoline-6carboxylic acid (Hquin-6-c), which is the close analogue of pyridinecarboxylic acid, presents different functional groups and a large conjugated π-system, and it may allow for diversity in the coordination mode. The steric hindrance of quinoline rings may weaken the coordination abilities of quinoline nitrogen atoms, and the orientation relationship of the coordination O and N atoms in quin-6-c is such that they are not linear with each other, so that one could anticipate that it will be applied as a configurationally asymmetric bridging ligand leading to a broader palette of coordination polymers and novel topological networks that cannot be achieved with common carboxylatearomatic amine ligands.4 To the best of our knowledge, the crystal structures of metal-organic complexes with quinoline6-carboxylate ligand have not been well explored to date, in comparison with quinoline-4-carboxylate ligand,5,6 only one crystal structure of copper(I)-rhenate hybrids with quinoline6-carboxylate has been documented in 2007.6a Herein, we report * Corresponding authors. E-mail: [email protected] (M.-H.Z.).

the hydrothermal syntheses and structures of four novel metal/ quinoline-6-carboxylate coordination polymers and the investigation of the geometric effects of ligand, the differentiation of metal atom and pH value in hydrothermal system on the crystal structures of these compounds. We selected NiII, CoII and ZnII as metal nodes for assembly with quin-6-c, respectively, and obtained four coordination polymers, namely, Ni(quin-6c)2 (1), Zn2(quin-6-c)4 (2), Co2(quin-6-c)4 (3), and Zn(OH)(quin6-c) (4). Compound 1 has a (4,4) topological network, stacking as ABAB layers, while isomorphous compounds 2 and 3 exhibit novel 2D molecular networks constructed by three types of quin6-c with different coordination modes. The 2D layers stack in an interesting ABCD pattern. By adjusting the pH value and reaction temperature, we obtain the rare [Zn(µ2-OH)]n helical chains in compound 4, which support a 3D structure with uncommon “new” 65.8 topology, displaying powder SHG intensity ca. 460 times that of R-quartz. Experimental Section Materials and Methods. All reagents and solvents employed were commercially available and used as received without further purification. The C, H, and N microanalyses were carried out with Perkin-Elmer 240 elemental analyzer. The FT-IR spectra were recorded from KBr pellets in the range 4000-400 cm-1 on a Nicolet 5DX spectrometer. Solvothermal Syntheses. Ni(quin-6-c)2 (1). A mixture of Ni(NO3)2 · 6H2O (1 mmol), quin-6-c (2 mmol), and distilled water (10 mL) in a 23 mL Teflon reactor was heated at 140 °C for three days and then cooled to room temperature at a rate of 5 K h-1. Dark green block crystals were obtained in 36% yield (based on Ni) after washing with distilled water and drying in air. Anal. Calcd for C20H12N2NiO4: C, 59.60; H, 3.00; N, 6.95. Found: C, 59.16; H, 3.06; N, 6.90. IR (KBr, cm-1): 3032 (w), 1660 (s), 1553 (w), 1448 (m), 1420 (s), 1219 (w), 1140 (w), 1013 (m), 810 (m), 780 (m), 560 (w). Zn2(quin-6-c)4 (2). Compound 2 was prepared as for 1 at 140 °C by using Zn(NO3)2 · 6H2O in place of Ni(NO3)2 · 6H2O. Colorless block crystals were found (22%, based on Zn). Anal. Calcd for C40H24Zn2N4O8: C, 58.63; H, 2.95; N, 6.84. Found: C, 58.22; H, 3.01; N, 6.80. IR (KBr, cm-1): 3035 (w), 1662 (s), 1552 (w), 1449 (m), 1418 (s), 1221 (w), 1143 (w), 1015 (m), 811 (m), 779 (m), 558 (w). Co2(quin-6-c)4 (3). Compound 3 was prepared as for 1 at 140 °C by using Co(NO3)2 · 6H2O in place of Ni(NO3)2 · 6H2O. Dark pink

10.1021/cg701153z CCC: $40.75  2008 American Chemical Society Published on Web 06/07/2008

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Table 1. Crystal Data and Structure Refinement Details for 1-4

formula formula wt temp/K cryst syst space group a/Å b/Å c/Å β/deg V/Å3 Z Dc/g cm-3 µ/mm-1 F(000) no. of rflns collected no. of indep rflns Rint GOF R1a (I < 2σ(I)) wR2a (all data)

1

2

3

4

C20H12N2NiO4 403.03 293(2) monoclinic P21/c 9.4902(5) 16.5949(9) 10.4733(6) 90.372(1) 1649.4(2) 4 1.623 1.207 824 8931 3236 0.0223 1.058 0.0289 0.0806

C40H24N4O8Zn2 819.37 293(2) monoclinic P21/c 9.450(3) 14.239(4) 24.811(6) 96.082(5) 3320(2) 4 1.639 1.510 1664 18513 7202 0.0325 1.051 0.0370 0.0864

C40H24Co2N4O8 806.49 293(2) monoclinic P21/c 9.485(1) 14.158(1) 24.828(2) 94.750(1) 3322.8(4) 4 1.612 1.063 1640 11031 6357 0.0193 1.030 0.0496 0.1273

C10H7NO3Zn 254.54 293(2) orthorhombic Pna21 10.790(6) 17.59(1) 5.148(3)

crystals were found (19%, based on Co). Anal. Calcd for C40H24Co2N4O8: C, 59.57; H, 3.00; N, 6.95. Found: C, 58.92; H, 2.94; N, 6.87. IR (KBr, cm-1): 3033 (w), 1660 (s), 1551 (w), 1450 (m), 1421 (s), 1220 (w), 1141 (w), 1014 (m), 810 (m), 781 (m), 560 (w). Zn(OH)(quin-6-c) (4). A mixture of Zn(NO3)2 · 6H2O (1 mmol), quin-6-c (0.75 mmol), NaOH (0.5 mmol) and distilled water (10 mL) in a 23 mL Teflon reactor was heated at 170 °C for five days and then cooled to room temperature at a rate of 5 K h-1. Colorless block crystals were obtained in 20% yield (based on Zn) after washing with distilled water and drying in air. Anal. Calcd for C10H7NO3Zn: C, 47.18; H, 2.77; N, 5.50. Found: C, 46.90; H, 2.71; N, 5.38. IR (KBr, cm-1): 3434 (m), 3033 (w), 1660 (s), 1555 (w), 1450 (m), 1419 (s), 1220 (w), 1141 (w), 1013 (m), 809 (m), 778 (m), 561 (w). SHG Property Measurement. According to the principles proposed by Kurtz and Perry the strength of the second harmonic generation (SHG) efficiency of the compounds was estimated by measuring the powder (76-154 µm diameter) in the form of pellets (0.8 mm thickness).7 The pressure used in compacting the pellet was 300 MPa. The experimental arrangement included a high-power mode-locked Nd: YAG laser with 200 ps pulse at a repetition rate of 5 Hz at a selected wavelength of 1064 nm. The laser beam is split into two parts, one to generate the second harmonic signal in the sample and the other to generate the second harmonic signal in the reference (R-quartz pellet). X-ray Crystallography. Diffraction intensities of 1-4 were collected on a Bruker Apex CCD area-detector diffractometer (Mo KR, λ ) 0.71073 Å). Absorption corrections were applied by using the multiscan program SADABS.8 The structures were solved with direct methods and refined with a full-matrix least-squares technique with the SHELXTL program package.9 Anisotropic thermal parameters were applied to all non-hydrogen atoms. The organic hydrogen atoms were generated geometrically (C-H 0.96 Å). Crystal data as well as details of data collection and refinements for complexes 1-4 are summarized in Table 1. Selected bond distances and bond angles are listed in Table 2.

Results Structure of Ni(quin-6-c)2 (1). Single-crystal X-ray diffraction analysis revealed that there are one NiII atom and two quin6-c ligands in the asymmetric unit of complex 1. The local coordination geometry around each NiII center in 1 adopts distorted pseudooctahedral geometry, in which each NiII atom is coordinated by four O atoms from the chelating carboxyl groups of two quin-6-c ligands (Ni-O ) 2.059(1)-2.178(1) Å) and two N atoms from another two quin-6-c ligands (Ni-N ) 2.088(2)-2.089(2) Å) to complete the coordination sphere (Figure 1a). With its chelating carboxyl groups and bridging quinoline moiety, each quin-6-c is bound to two Ni atoms, resulting in the formation of a puckered 2D network based on

977(1) 4 1.731 2.496 512 4901 1727 0.0273 1.071 0.0213 0.0513

(4, 4) topology. The 2D grid lies in the ab crystallographic plane and contains rhombus openings of a minimum size 7.13 × 4.58 Å as defined by the shortest transannular distance factoring van der Waals radii (Figure 1b). The layers are noninterpenetrated despite the large cavity size. The adjacent grids are stacked offset with respect to each other in an ABAB fashion by van der Waals interactions, only a weak interlayer nonclassical C-H · · · O hydrogen bonding (C13 · · · O1 ) 3.44 Å) has been observed. A drawing of the 2D network of 1 viewed along the c direction is presented in Figure 1c. Structure of Zn2(quin-6-c)4 (2) and Co2(quin-6-c)4 (3). Compound 3 is structurally isomeric to compound 2, so that only the structure of 2 is described here. In the coordination network of 2, the zinc ions occur in pairs and are bridged by a syn-anti bidentate bridging carboxylate group from a terminal quin-6-c ligand as shown in Figure 2a. Each zinc ion is coordinated by a further three quin-6-c ligands adopting a distorted square pyramidal geometry. On the Zn1 site, two N atoms from two quin-6-c quinoline groups, two O atoms from a quin-6-c chelating carboxylate group, and one O atom from a quin-6-c bidentate bridging carboxylate group surround the Zn atom. On the Zn2 site, one N atom from a quin-6-c quinoline group, two O atoms from a quin-6-c chelating carboxylate group, one O atom from a quin-6-c monodentate coordinated carboxylate group, and an O atom from a quinone-6-c bidentate bridging carboxylate group compose the square pyramidal coordination sphere. The Zn-N and Zn-O distances are in the range of 2.067(2)-2.100(2) and 1.971(2)-2.316(2) Å, respectively. As shown in Figure 2b, there are three types of quin-6-c units, one of which bridges the Zn atoms to 1D chains using its bis-chelating carboxylate groups and quinoline moiety, one of which bridges two 1D chains to a double-line ribbon using bidentate bridging carboxylate groups, but the N atoms of quinoline rings fail to coordinate to zinc ions, and another which bridges the double-line ribbons to an overall crimpled 2D molecular network. The 2D layer lies in the ab crystallographic plane and contains openings of a minimum size 7.01 × 6.24 Å as defined by the shortest transannular distance factoring van der Waals radii (Figure 2b). The close stacking of the crimpled 2D layers minimizes the void volume in the lattice. There is a fascinating packing style between the special conformations of the 2D layers. As shown in Figure 2c, associated with the three types of quin-6-c units, the 21/c symmetry allows dense stacking of the 2D layers in an

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Table 2. Bond Lengths (Å) and Angles (deg) for 1-4a Complex 1 Ni(1)-O(2) 2.0585(13) Ni(1)-O(4a) 2.0795(13) Ni(1)-N(1b) 2.0888(15) Ni(1)-N(2) 2.0898(16) O(2)-Ni(1)-O(4a) 157.16(5) O(2)-Ni(1)-N(1b) 96.60(6) O(4a)-Ni(1)-N(1b) 101.06(6) O(2)-Ni(1)-N(2) 95.50(6) O(4a)-Ni(1)-N(2) 97.52(6) N(1b)-Ni(1)-N(2) 94.17(6) O(2)-Ni(1)-O(3a) 101.18(5) O(4a)-Ni(1)-O(3a) 63.37(5)

Ni(1)-O(3a) Ni(1)-O(1)

2.1007(14) 2.1781(14)

N(1b)-Ni(1)-O(3a) 94.20(6) N(2)-Ni(1)-O(3a) 160.32(6) O(2)-Ni(1)-O(1) 62.25(5) O(4a)-Ni(1)-O(1) 100.20(5) N(1b)-Ni(1)-O(1) 158.61(6) N(2)-Ni(1)-O(1) 85.31(6) O(3a)-Ni(1)-O(1) 93.24(6)

Complex 2 Zn(1)-O(6) Zn(1)-O(2a) Zn(1)-N(4) Zn(1)-N(1) Zn(1)-O(1a) O(6)-Zn(1)-O(2a) O(6)-Zn(1)-N(4) O(2a)-Zn(1)-N(4) O(6)-Zn(1)-N(1) O(2a)-Zn(1)-N(1) N(4)-Zn(1)-N(1) O(6)-Zn(1)-O(1a) O(2a)-Zn(1)-O(1a) N(4)-Zn(1)-O(1a) N(1)-Zn(1)-O(1a)

1.971(2) 2.011(2) 2.067(2) 2.100(2) 2.316(2) 135.89(8) 96.69(8) 117.13(9) 100.20(8) 96.10(9) 107.09(8) 93.24(8) 59.87(8) 92.50(8) 154.57(8)

Co(1)-O(6) Co(1)-O(2a) Co(1)-N(4) Co(1)-N(1) Co(1)-O(1a) Co(1)-C(10a) O(6)-Co(1)-O(2a) O(6)-Co(1)-N(4) O(2a)-Co(1)-N(4) O(6)-Co(1)-N(1) O(2a)-Co(1)-N(1) N(4)-Co(1)-N(1) O(6)-Co(1)-O(1a) O(2a)-Co(1)-O(1a) N(4)-Co(1)-O(1a) N(1)-Co(1)-O(1a)

1.966(2) 1.999(2) 2.078(3) 2.082(3) 2.318(3) 2.482(3) 133.54(11) 95.77(10) 117.61(11) 101.51(11) 98.15(10) 107.51(11) 91.51(10) 60.15(10) 88.92(10) 157.64(10)

Zn(2)-O(7b) Zn(2)-O(5) Zn(2)-O(4a) Zn(2)-N(2) Zn(2)-O(3a) O(7b)-Zn(2)-O(5) O(7b)-Zn(2)-O(4a) O(5)-Zn(2)-O(4a) O(7b)-Zn(2)-N(2) O(5)-Zn(2)-N(2) O(4a)-Zn(2)-N(2) O(7b)-Zn(2)-O(3a) O(5)-Zn(2)-O(3a) O(4a)-Zn(2)-O(3a) N(2)-Zn(2)-O(3a)

1.9861(19) 2.0224(19) 2.084(2) 2.100(2) 2.259(2) 105.94(8) 137.81(8) 107.15(8) 105.48(9) 98.22(8) 94.92(8) 94.90(8) 89.51(8) 60.21(8) 155.13(8)

Complex 3 Co(2)-O(5) Co(2)-O(7b) Co(2)-O(4a) Co(2)-N(2) Co(2)-O(3a) O(5)-Co(2)-O(7b) O(5)-Co(2)-O(4a) O(7b)-Co(2)-O(4a) O(5)-Co(2)-N(2) O(7b)-Co(2)-N(2) O(4a)-Co(2)-N(2) O(5)-Co(2)-O(3a) O(7b)-Co(2)-O(3a) O(4a)-Co(2)-O(3a) N(2)-Co(2)-O(3a)

2.017(3) 2.023(3) 2.056(2) 2.098(3) 2.274(3) 103.77(11) 104.77(11) 140.40(11) 97.51(11) 105.85(11) 97.00(10) 88.62(11) 93.66(11) 60.38(9) 157.37(10)

Complex 4 Zn(1)-O(3a) 1.902(2) Zn(1)-O(3) 1.9389(19) O(3a)-Zn(1)-O(3) 101.05(6) O(3a)-Zn(1)-O(2b) 115.36(8) O(3)-Zn(1)-O(2b) 104.97(8)

Zn(1)-O(2b) Zn(1)-N(1) O(3a)-Zn(1)-N(1) O(3)-Zn(1)-N(1) O(2b)-Zn(1)-N(1)

1.9683(18) 2.062(2) 118.77(9) 108.38(10) 107.10(8)

a Symmetry codes for 1: (a) x + 1, y, z; (b) -x + 3/2, y - 1/2, -z + /2. Symmetry codes for 2 and 3: (a) x + 1, y, z; (b) x, y + 1, z. Symmetry codes for 4: (a) -x, -y + 1, z + 1/2; (b) -x + 1/2, y + 1/2, z - 1/2.

3

up-down fashion as ABCD layers along the crystallographic c axis, by being able to adopt different binding modes and relative orientations, of the ligands and the metal center. The quinoline rings that are pointed outside the plane of layers insert deeply into the cavities of the adjacent layers and hence maximize the intermolecular interactions for complementary shape with inversion centers, therefore resulting in the cooperative self-assembly of the final structure. Weak interlayer nonclassical C-H · · · O hydrogen bonding instead of aromatic ring stacking plays a vital role in the consolidation of the solid structure. The C · · · O distances and the C-H · · · O angles are in the ranges 3.12-3.39 Å and 131.3-162.1°, respectively. It is

Figure 1. (a) The coordination environment of Ni atom in 1 (some equivalent atoms have been generated to complete the Ni coordination, H atom omitted). (b) A wavelike (4, 4) net in 1. (c) The AB molecular packing of 2D layers.

somewhat surprising that very few 2D networks stacking in ABCD fashion have been reported.10 Structure of Zn(OH)(quin-6-c) (4). A single-crystal X-ray diffraction study performed on a block colorless crystal of 4 revealed the presence of a 3D network that is constructed from 1D Zn-OH-Zn chains running along the crystallographic c

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Figure 3. (a) Perspective views of the coordination environments of Zn atoms (some equivalent atoms have been generated to complete the Zn coordination, H atoms omitted). (b) View of the 3D net along the c axis. (c) The 4-connected 65.8 topological net in the structure of 4. The green spheres represent zinc atoms, while the blue lines represent the quin-6-c ligands. The µ2-hydroxy groups are reprented by Zn · · · Zn links (red line).

Figure 2. (a) Perspective views of the coordination environments of Zn atoms (some equivalent atoms have been generated to complete the Zn coordination, H atoms omitted). (b) Perspective view of the crimpled 2D network along the c axis. (c) The molecular packing as repeating layers of type ABCD.

direction. In the asymmetric unit there is one unique Zn atom that is bridged in a monodentate fashion by carboxylate groups and N atoms of quinoline rings from two different quin-6-c ligands, with the remaining coordination sites bound to two hydroxy groups to give tetrahedral geometry. The Zn-O(H) bond lengths occur in the range 1.902(2)-1.939(2) Å. The Zn-O(H)-Zn angle is 124.2(1)°, which is presumably caused

by the gyration of the [Zn(µ2-OH)]n helical chain. Each [Zn(µ2OH)]n chain is further linked to four nearest-neighbors, with distances of 9.725(1) Å, through the bridging quin-6-c ligands along two perpendicular directions, [001] and [010], thus resulting in a unique 3D 4-connected framework (Figure 3b). To the best of our knowledge, a metal-organic framework with 1D [Zn(µ2-OH)]n chain as building block has never been documented.1,2 The medium intensity peak at 3434 cm-1 in the infrared spectrum indicates the existence of hydroxyl groups in 4, which is in reasonable range referring to the reference value and agrees with the crystallographic analysis.11 The network topology can be simplified by considering the Zn atoms (represented by tetrahedral 4-connected nodes); the bridging quin-6-c ligands and the µ2-hydroxy groups can be

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Chart 1. The Binding Modes (I, II, III) of Quin-6-c in 1-4

represented simply as links between the nodes. A topological analysis of this net was performed with OLEX.12 The long topological (O’Keeffe) vertex symbol is 6.6.6.6.62.83 for the tetrahedral Zn node, which gives the short vertex symbol 65.8. Of the important topological nets, there are other possible topologies that are based solely upon tetrahedral nodes: the 3D networks diamond (66),13 quartz (6482),14 and quartz dual (75.9),15 sodalite (42.64),16 and lonsdaleite,17 which have been widely observed. It is worth noting that the present net has the same short vertex symbol 65.8 as CdSO4, the simplest planar 4-connected net or distorted 65.8 CdSO4 topology.18,19 However, in compound 4, the uncommon 65.8 topology based upon tetrahedral node is less known.19 Powder Second Harmonic Generation Studies. We have carried out preliminary powder SHG studies using the 1064 nm fundamental wavelength from a Nd:YAG laser.7 Consistent with the single-crystal structures, compounds 4 are SHG-active. In contrast, compound 2 is SHG-inactive because of its centrosymmetric structure. 4 exhibits a powder SHG intensity of 460 relative to that of R-quartz. For comparison, technologically important lithium niobate has a powder SHG intensity of 600 relative to that of R-quartz. Because the SHG efficiency is proportional to the square root of the SHG intensity, compound 4 thus has nearly 88% of the SHG efficiency of lithium niobate.20 Given the relatively small electronic asymmetry in the quin-6-c chromophores, and big electronic asymmetry of infinite [Zn(µ2-OH)]n helical chains, the powder SHG efficiencies observed here are quite respectable. Discussion The ligand used in this work is interesting from a structural point of view and exhibits novel bridging networks different from other quinoline derivatives.5,6 From the structural descriptions above, we can conclude that the coordination mode of quin-6-c is changeable when assembling to a given metal atom, and also vital for the framework formation. In compounds 1-4, the pyridyl nitrogen is inclined to coordinate to the metal atom, and the anionic nature of the carboxylate group leads to a neutral complex. However, the carboxylate groups exhibit different binding fashions (see Chart 1). For 2D coordination polymer 1 and 3D coordination polymer 4, simple chelating and unidentate mode of the carboxylate groups are observed. For 2D isostructural polymers 2 and 3, the chelating, unidentate and syn-anti bidentate fashions of the carboxylate groups are detected all together, expanding the metal nodes to generate novel layers. Quin-6-c ligands adopt a bent riding fashion, which result in puckered 2D layers whose grooves are buckled with each other, so that the size of quinoline rings in 1-3 plays a form recognition role in the molecular packing progress. Obviously, by being able to adopt different binding modes, relative asymmetric orientations of the pyridyl nitrogen and carboxylate group and the special conformation of quin-6-c ligands, as described above, the interesting structural diversity of 1-4 was obtained. The coordination geometry of the central metal ion may also have a very significant effect on the final structure. As

demonstrated by the comparison of Ni-complex (1) with Zncomplex (2) and cocomplex (3), the change in coordination geometry of the central metal ion from pseudooctahedral to square pyramidal causes the distinctness of the linking fashion of the quin-6-c ligands and finally results in the formation of different 2D structures. It should also be noted that the other structure-influencing factors, such as pH value and reaction temperature, could affect the overall structure obtained. It was suggested that the higher pH value and reaction temperature create more opportunities to introduce hydroxide group components in coordination polymer structures in the hydrothermal synthesis.2 The introduction of hydroxide groups is a critical factor for the modification of topological connectivity of metal atoms in compound 4, which results in an unusual 65.8 topology. Conclusions In summary, we reported a set of new coordination polymers based on different 3d ions (NiII, CoII ZnII), and quinoline-6carboxylate that generate unusually puckered 2- and 3D networks. The 2D layers in the structure of 2 and 3 exhibit novel molecular packing in ABCD fashion. Our analysis based on the structural data suggests that both the relative orientations in the ligand placement and the donor group arrangement around the metal atoms are the key factors affecting the unique patterns of structural diversity and supramolecular packing mode of compound 1-4, which can be tuned by the reaction conditions. More interestingly, compound 4 exhibits structural evidence of an uncommon 65.8 topological network constructed with undocumented [Zn(µ2-OH)]n helical chains in coordination polymers. SHG-activity of compound 4 thus clearly illustrates the potential of the rational synthesis of highly NLO-active polar solids based on incorporation of [Zn(µ2-OH)]n helical chains into more efficient acentric solids. Concerning the special quinoline-6-carboxylate ligand between different metal atoms, more novel molecular networks, known or unknown, remain to be explored. Acknowledgment. This work was supported by NSFC (No. 20561001), the Program for New Century Excellent Talents in University of the Ministry of Education China (NCET-07-217), GKN (Grant 0630006-5D), and GJY (Grant 2006-26) as well as IPGGE (Grant 2006106020703M34). Supporting Information Available: Crystallographic information files (CIF) of compounds. This material is available free of charge via the Internet at http://pubs.acs.org.

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