Diamine Substitution Reactions of Tetrahydrate Succinato Nickel

cadmium chain and polynuclear cadmium macrocycle using phenylsuccinic acid. Sheng Hu , Peng Zhang , Fang-Yong Yu , Dian-Rong Lin , Mei-Xian Chen...
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CRYSTAL GROWTH & DESIGN

Diamine Substitution Reactions of Tetrahydrate Succinato Nickel, Cobalt, and Zinc Coordination Polymers

2005 VOL. 5, NO. 5 1825-1830

Zhao-Hui Zhou,* Jin-Mei Yang, and Hui-Lin Wan Department of Chemistry, College of Chemistry and Chemical Engineering, and State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China Received April 13, 2005;

Revised Manuscript Received May 29, 2005

ABSTRACT: Investigation on the substitution reactions of tetrahydrate succinato metal coordination polymers with diamine ligands results in the isolations of four new coordination polymers, [M(suc)(bpy)(H2O)2]n‚nH2O (M ) Ni, 2; M ) Co, 2a), [Ni(suc)(phen)(H2O)]n (3), and [Zn(suc)(bpy)]n‚2nH2O (4) (H2suc ) succinic acid, bpy ) 2,2′bipyridine, and phen ) 1,10-phenanthroline). In the isomorphous compounds of 2 and 2a, the metal(II) ions are linked by a bridging succinate ligand to form 1D helix chains in bis-monodentate mode. In compounds 3 and 4, the succinate ligand connects adjacent nickel/zinc(II) atoms through three oxygen atoms from two carboxyl groups, forming an infinite zipper like chain along the a axis. The nickel compound 3 forms a double helix chain through strong hydrogen bonding. Notably, the double-stranded ribbons in compound 4 formed through moderately strong faceto-face π-π stacking segregated an unprecedented water chain constructed from dimeric water molecules. Introduction Crystal engineering of coordination polymers has attracted great attention due to their potential as functional materials, as well as their intriguing compositions and topologies.1 Considerable progress has been made on the theoretical forecast and practical approaches aiming at controlling the topology structure and geometry of the networks. However, the general and precise principles for the solid structures of the target products are still subjective because the self-assembly process is highly influenced by several factors, such as the metal/ligand nature,2 solvent,3 counteranions,4 temperature,5 and even pH value.6 Among these factors, the choice of the organic spacers is the single greatest influence in determining the type and topology of the product. The organic spacers serve to link metal sites and to propagate structural information expressed in the metal coordination preferences through the extended structure. Dicarboxylates, such as three isomeric benzene dicarboxylic acids, that is, phthalic acid, isophthalic acid, and terephthalic acid, are most widely used for designing coordination polymers. They not only can bridge metal ions but also can bind them in a variety of coordination modes. Unlike these rigid dicarboxylate spacer ligands, the saturated aliphatic dicarboxylate succinate ligand exhibits conformational and coordination versatility due to single-bonded carbon chains and are viewed as important flexible spacer ligands.7 Noteworthy examples of these polymers can result in microporous structures with novel M-O-M connectivities. [Ni7(suc)6(OH)2(H2O)2]‚2H2O,8 which contains a remarkable honeycomb nickel oxide network, [Ni7(suc)4(OH)6(H2O)3]‚7H2O,9 is built up by nickel oxide chains and can reversibly re-absorb water molecules; the 3-D network [Co5(suc)4(OH)2]10 is constructed from succinate-pillared layers. Several lower dimensional * To whom correspondence should be addressed. Tel: + 86-5922184531. Fax: + 86-592-2183047. E-mail: [email protected].

structures have been reported at present11 with the introduction of some N-donor chelate ligands. With this background and as an extension of studies on dicarboxylate networks, we have used the succinate anion as a ligand, which has longer spacer length and may be fruitful to generate an extended framework and create a wide variety of binding modes. In this paper, we have explored the reactions of polymeric tetrahydrate succinato nickel(II), cobalt(II), or zinc(II) salts and diamine chelate ligands such as 2,2′bipyridine (bpy) and 1,10-phenanthroline (phen). The substitution reactions result in the isolations of six coordination polymers, 2-5, with two different succinato coordination modes. Single-crystal X-ray diffraction analyses revealed their substitutions of 1D helical-chain structures. Especially, interesting 1D water chains exist in the bipyridine succinato zinc(II) complex 4, which are formed out of dimeric water molecules. Water chains appear to be important due their occurrence in several biological processes related to water and ion transport.12 Experimental Section All chemicals were commercially available and used without further purification. Elemental microanalyses (C, H, and N) were performed on an EA 1100 elemental analyzer. UV-vis spectra were recorded on a TU-1901 spectrometer, and infrared spectra were recorded from KBr pellets on a Nicolet FT-IR 360 spectrophotometer in the range of 400-4000 cm-1. Transformations of Tetrahydrate Succinato Complexes [M(suc)(H2O)4]n [M ) Ni, 1; Co, 1a] to [M(suc)(bpy)(H2O)2]n‚nH2O [M ) Ni, 2; Co, 2a]. Succinato metal salts [Ni(suc)(H2O)4]n (1) (green) and [Co(suc)(H2O)4]n (1a) (red) were prepared as reported.13 A solution of 2,2′-bipyridine (0.156 g, 1 mmol) in ethanol (10 mL) was added to the solution of succinato metal salts 1 or 1a (0.247 g, 1 mmol) in water (20 mL). The mixture was refluxed for 8 h. The solution was kept at room temperature. A few days later, blocklike blue crystals of 2 (0.277 g, yield 72%) and blocklike yellow crystals of 2a (0.261 g, yield 68%) were obtained. For 2, Calcd. for C14H18N2O7Ni: C, 43.7; H, 4.7; N, 7.3. Found: C, 43.2; H, 4.6; N, 7.1. IR (KBr, cm-1): ν(O-H) 3428vs, νas(CdO) 1587s, 1555vs, νs(CdO)

10.1021/cg050150r CCC: $30.25 © 2005 American Chemical Society Published on Web 06/29/2005

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Table 1. Crystal Data Summaries of Intensity Data Collections and Structure Refinements for 2/2a, 3, and 4 2 empirical formula formula weight crystal color crystal system cell constants a (Å) b (Å) c (Å) R (deg) β (deg) γ (deg) V (Å3) space group formula units Dcalc (g ‚cm-3) µ (mm-1) F000 diffractometer radiation temp (K) reflns collected/unique crystal size (mm) data/params θ range (deg) GOF on F2 R1, wR2 [I > 2σ(I)]a R1, wR2 (all data)a largest diff. peak and hole (e Å-3) a

2a

C14H18N2O7Ni 385.01 blue monoclinic

C14H18N2O7Co 385.23 yellow monoclinic

8.0456(7) 11.443(1) 16.999(2)

8.1405(3) 11.4833(5) 17.0073(7)

93.866(2) 1561.4(2) P21/c 4 1.638 1.283 800 293(2) 8625/2754 0.26 × 0.11 × 0.10 2754/235 2.15 to 25.00 1.004 0.058, 0.128 0.078, 0.136 0.644, -0.491

3 C16H14N2O5Ni 373.00 blue triclinic

7.4798(4) 10.2092(6) 10.5362(6) 97.533(1) 94.193(1) 106.675(1) 100.837(1) 1585.6(1) 742.21(7) P21/c P1 h 4 2 1.614 1.669 1.122 1.338 796 384 Smart Apex CCD Mo KR (λ ) 0.710 73 Å) 293(2) 293(2) 17754/3737 8535/3405 0.27 × 0.24 × 0.12 0.22 × 0.15 × 0.08 3737/241 3405/223 2.14 to 27.98 2.06 to 28.18 1.063 1.078 0.040, 0.096 0.046, 0.104 0.046, 0.100 0.052, 0.107 0.405, -0.378 0.749, -0.444

4 C14H16N2O6Zn 373.66 light pink triclinic 7.2520(7) 8.9863(9) 11.399(1) 77.661(2) 85.244(2) 88.405(2) 723.1(1) P1 h 2 1.716 1.733 384 173(2) 5420/3306 0.12 × 0.06 × 0.06 3306/220 1.83 to 28.45 0.993 0.055, 0.101 0.071, 0.107 0.544, -0.483

R1 ) ∑||Fo| - |Fc||/∑|Fo|; wR2 )∑[w(Fo2 - Fc2)2]/∑[w(Fo2)2]1/2.

1421s, 1403s, ν (Ni-O) 767s. UV-vis: λmax ) 490 nm,  ) 32.6. For 2a, Calcd. for C14H18N2O7Co: C, 43.7; H, 4.7; N, 7.3. Found: C, 43.1; H, 4.6; N, 7.0. IR (KBr, cm-1): ν(O-H) 3408vs, νas(CdO) 1586s, 1552vs, νs(CdO) 1423s, 1400s, ν (Co-O) 767s. UV-vis: λmax ) 470 nm,  ) 28.4. Transformations of Tetrahydrate Succinato Complexes [M(suc)(H2O)4]n [M ) Ni, 1; Co, 1a] to [M(suc)(phen)(H2O)]n [M ) Ni, 3; Co, 3a14]. The conversions of 1 and 1a to 3 and 3a were similar to the procedures mentioned above, using 1,10-phenanthroline (0.198 g, 1 mmol) instead of 2,2′-bipyridine. Blue prism single crystals of 3 (0.251 g, yield 67%) and blocklike yellow single crystals of 3a14 (0.246 g, yield 66%) were obtained after a few weeks. For 3, Calcd. for C16H14N2O5Ni: C, 51.5; H, 3.8; N, 7.5. Found: C, 50.9; H, 3.7; N, 7.3. IR (KBr, cm-1): ν(O-H) 3158m,νas(CdO) 1579s, 1543vs, νs(CdO) 1422vs, 1408vs, ν (Ni-O) 727m. UV-vis: λmax ) 485 nm,  ) 25.1. Transformations of Tetrahydrate Succinato Complexes [Zn(suc)(H2O)4]n (1b)15 to [Zn(suc)(bpy)]n‚2nH2O (4) and [Zn(suc)(phen)]n‚H2suc (5).16 Succinate zinc salt 1b was synthesized as reference.15 A solution of 2,2′-bipyridine (0.156 g, 1 mmol) in ethanol (10 mL) was added to the solution of succinato metal salts 1b (0.254 g, 1 mmol) in water (20 mL). The mixture was refluxed for 8 h. The solution was kept at room temperature. Several weeks later, needle light-pink crystals of 4 (0.198 g, yield 53%) suitable for X-ray diffraction were isolated. The conversion of 1b to 5 was the same as the procedure for 1b to 4 using 1,10-phenanthroline (0.198 g, 1 mmol) instead of 2,2′-bipyridine. Block yellowish crystals of 516 (0.244 g, yield 51%) were isolated after one week, and further proof of the identity of crystalline product was provided by X-ray unit cell determination of the isolated single crystals. For 4, Calcd. for C14H16N2O6Zn: C, 45.0; H, 4.3; N, 7.5. Found: C, 45.3; H, 3.9; N, 7.4. IR (KBr, cm-1): ν(O-H) 3434s,νas(CdO) 1609s, 1587vs, νs(CdO) 1429m, 1401s, ν (Zn-O) 676m. UV-vis: λmax ) 302 nm,  ) 2.1 × 105. X-ray Structural Determination. Crystals 2-4 were measured on a Bruker Smart Apex CCD area detector diffractometer with graphite monochromate Mo KR radiation (λ ) 0.710 73 Å) at 296 K. The data were collected for Lorentz and polarization effects. An absorption correction was applied using SADABS program. The structures were primary solved by

WinGX package17 and refined by full-matrix least-squares procedures with anisotropic thermal parameters for all the non-hydrogen atoms with SHELXL 97.18 Hydrogen atoms were located from difference Fourier map but refined isotropically. Crystal data collection and refinement parameters were summarized in Table 1. Selected bond lengths and bond angles were listed in Table 2.

Results and Discussion Synthesis. Complexes 2-4 have been synthesized by the substitutions of polymeric tetrahydrate succinato nickel, cobalt, and zinc complexes as shown in Scheme 1. That gives rise to different coordination modes of succinate anion in each case. The reactions of tetrahydrate succinato complexes with 2,2′-bipyridine resulted in the formations of isomorphous 2 and 2a at reflux condition. As indicated in the structural description of 2 and 2a given below, only two of the four carboxyl oxygen atoms in the succinate ligand coordinate to the metal(II) ion, and there are still two water molecules coordinated to the metal atom. In contrast, the isomorphous complexes 3 and 3a can be obtained from the reactions of 1 or 1a and 1,10-phenanthroline, respectively, in which one carboxyl group of the succinate ligand coordinates to the metal atom in bidentate mode, while the other carboxyl group binds to the metal atom in monodentate mode. Only one of four carboxyl oxygen atoms is free, and there is still a water molecule bound to the metal atom. Between the free carboxyl oxygen atom and the coordinated water molecule, a strong intramolecular hydrogen bond exists as reported previously.14 Here we provide a brief discussion on the packing of the crystal structure and illustrate the importance of reactions with respect to the final structure. However, the reactions of tetrahydrate succinato zinc complex with 2,2′-bipyridine and 1,10-phenanthroline ligands lead to the depositions of complexes 4 and

Diamine Substitution Reactions of [M(suc)(H2O)4]n

Crystal Growth & Design, Vol. 5, No. 5, 2005 1827

Table 2. Selected Bond Distances (Å) and Selected Bond Angles (deg) for 2, 2a, 3, and 4 Bond Distances M1-O1 M1-O3a M1-O1w M1-O2w M1-N1 M1-N2

2

2a

2.056(3) 2.071(3) 2.054(3) 2.096(3) 2.070(3) 2.076(4)

2.071(1) 2.106(2) 2.081(2) 2.142(2) 2.129(2) 2.131(2)

3 Ni1-O1 Ni1-O3a Ni1-O4a Ni1-O1w Ni1-N1 Ni1-N2

2.029(2) 2.169(2) 2.097(2) 2.049(2) 2.073(2) 2.097(2)

4 Zn1-O1 Zn1-O3a Zn1-O4a Zn1-N1 Zn1-N2

1.955(2) 1.967(3) 2.469(3) 2.040(3) 2.040(3)

Bond Angles 2 O1-M1-O1w O1-M1-O3a O1-M1-O2w O3a-M1-O2w O1w-M1-O3a O1w-M1-O2w O1-M1-N1 O1-M1-N2 O3a-M1-N1 O3a-M1-N2 O1w-M1-N1 O1w-M1-N2 N1-M1-O2w N2-M1-O2w N1-M1-N2 a

87.25(3) 88.35(3) 93.02(2) 176.94(2) 90.88(3) 91.91(3) 95.14(4) 174.16(4) 88.25(4) 90.26(4) 177.44(4) 98.44(5) 88.91(4) 88.11(3) 79.15(5)

2a 89.77(7) 90.00(6) 91.97(6) 177.50(6) 89.43(7) 92.11(7) 95.06(6) 172.00(6) 88.53(6) 91.28(7) 174.75(7) 98.13(7) 89.77(7) 86.55(7) 77.09(7)

3 O1-Ni1-O3a O1-Ni1-O4a O1-Ni1-O1w O1w-Ni1-O3a O1w-Ni1-O4a O4a-Ni1-O3a O1-Ni1-N1 O1-Ni1-N2 O1w-Ni1-N1 O1w-Ni1-N2 N1-Ni1-O3a N1-Ni1-O4a N2-Ni1-O3a N2-Ni1-O4a N1-Ni1-N2

87.91(7) 92.34(8) 95.88(8) 161.23(7) 99.63(7) 61.78(6) 91.23(8) 167.31(8) 94.64(8) 93.60(8) 103.67(7) 164.85(8) 85.79(8) 94.36(8) 79.60(8)

4 O1-Zn1-O3a O1-Zn1-O4a O3a-Zn1-O4a O1-Zn1-N1 O1-Zn1-N2 O3a-Zn1-N1 O3a-Zn1-N2 N1-Zn1-O4a N2-Zn1-O4a N1-Zn1-N2

105.3(1) 96.0(1) 57.20(9) 127.0(1) 107.9(1) 107.7(1) 130.9(1) 136.7(1) 84.1(1) 79.2(1)

Symmetric transformation: for 2, -x + 1, y + 1/2, -z + 3/2; for 2a, -x, y + 1/2, -z + 3/2; for 3, x + 1, y, z; for 4, x - 1, y, z.

Scheme 1. Syntheses and Conversions of Succinato Nickel(II), Cobalt(II), and Zinc(II) Complexes

5, respectively. In complex 4, the zinc atom is fivecoordinated, and the coordination modes of carboxyl groups in succinate ligands are similar to those in 3 and 3a. But in complex 5, the zinc atom is tetracoordinated, and the succinate ligand binds to the two metal atoms in bis-monodentate fashion. However, a one-pot reaction of metal chloride or nitrate salt MX2 (M ) Ni, Co; X ) Cl-, NO3-) with succinate and diamine ligands results in the isolation of mononuclear diamine complexes such as [Ni(bpy)3]Cl2 and [Ni(phen)3]Cl2 without the coordination of succinate. Previous formations of polymeric succinato metal complexes [M(suc)(H2O)4]n are necessary for the further substitution of diamine ligand. The diamine succinate complexes could not be obtained from the reversed substitution of mononuclear diamine complexes with succinate ligand. Description of the Crystal Structures. Compounds 2 and 2a are isomorphous, and only the structure of the nickel derivative 2 is described here. X-ray

diffraction analysis reveals bipyridine succinato nickel dihydrate 2 possesses 1D helical chains with the basic building unit [Ni(suc)(bpy)(H2O)2]. Each nickel is coordinated by two oxygen atoms from two bis-monodentate succinate ligands in cis position, two water molecules, and two nitrogen atoms from one chelating bpy in a distorted octahedral configuration (Figure 1). The best equatorial plane is defined by O1, O1w, N1, and N2, in which the mean deviation is 0.032 Å. The distances of Ni-O in the axial position are longer than those in the least-squares plane, and the distances of the two Ni-N bonds are almost equal (Table 2). Moreover, the bond distances of M-Ocarboxyl in bis-monodentate complexes 2 and 2a [2, 2.056(3), 2.071(3) Å; 2a, 2.071(1), 2.106(2) Å] are comparable to their tetrahydrate precursors [M(suc)(H2O)4] [M ) Ni, 2.056(2), 2.062(2) Å; M ) Co, 2.089(2), 2.096(2) Å]. The succinate anions bridge the nickel atoms to form 1D chains and propagate spirally along the b axis (Ni‚‚‚Ni ) 7.972 Å and Co‚‚‚Co ) 7.285

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Figure 1. ORTEP plot of the unit in [Ni(suc)(bpy)(H2O)2]n (2) at the 30% probability level. Hydrogen atoms are omitted for clarity.

Å). A similar succinate coordination mode exists in [M(suc)(dpdo)(H2O)2] (M ) Zn or Mn, dpdo ) 4,4′dipyridyl N,N′-dioxide).11 Both the terminal carboxyl groups are orientated such that two strong intramolecular hydrogen bonds are formed between the uncoordinated carboxyl oxygen atom and the coordinate water molecules with O(2)‚‚‚O(2w) ) 2.621 and O(4a)‚ ‚‚O(1w) ) 2.635 Å. Each bpy ligand has two parallel bpy neighbors from the different helical chains. These adjacent bpy ligands approach each other so that the five immediate C-C bonds between the C8 and C12 atoms of the middle bpy ligand are covered by the reverse sequential C-C bonds from above and below the bpy ligands. The spacings between the bpy planes are alternatively 3.45 and 3.71 Å, indicating substantial edge-to-edge stacking interactions extending in the [100] direction. Such interactions are different from the faceto-face stacking interactions observed in the polymeric CuII bpy/phen complexes.11 Each helix chain has stacking interactions with four chains arranged on both sides, and the interactions are reinforced by hydrogen bonds between the coordination water and the uncoordinated carboxyl oxygen atom. Similarly, 3 and 3a14 are also isomorphous, so that only the structure of nickel complex 3 is described here. Similar to 2 and 2a, the coordination polymers 3 and 3a are also comprised of 1D helix chains. A portion of the chain is shown in Figure 2a. The distorted octahedral nickel(II) sphere consists of two nitrogen donors from a chelate phen ligand, three oxygen atoms from two different succinate ligands, and one oxygen atom from a coordinated water. An intramolecular hydrogen bond exists between the uncoordinated carboxyl oxygen and coordinated water molecule [O(2)‚‚‚O(1w) ) 2.638 Å]. Unlike those in 2, the two carboxyl groups of the succinate ligand in 3 exhibit another kind of coordination mode, that is, one of the carboxyl groups adopts a bidentate chelating mode, while the other has a monodentate mode. The M-O bond distances of monodentate carboxyl groups [3, M ) Ni, 2.029(2) Å; 3a, M ) Co, 2.037(2) Å] are shorter than their tetrahydrate precursors [M(suc)-

Figure 2. (a) ORTEP plot of the unit in [Ni(suc)(phen)(H2O)]n (3) at the 30% probability level. Hydrogen atoms are omitted for clarity. (b) View of the double-helical chains in 3 along the b-axis, in which the 1,10-phenanthroline ligands are omitted for clarity.

(H2O)4] [M ) Ni, 2.056(2), 2.062(2) Å; M ) Co, 2.089(2), 2.096(2) Å], while the bond distances of bidentate carboxyl groups [3, 2.169(2), 2.097(2) Å; 3a, 2.139(2), 2.190(2) Å] are longer than their related tetrahydrate precursors. The distances of M‚‚‚M are 7.480 Å in 3 and 7.522 Å in 3a. It is worth noting that two centrosymmetrically related single-strained chains in 3 result in an unusual double-helix chain, formed by intrachain hydrogen bonds between the coordinate carboxyl oxygen atoms and coordinate water molecules with the d(Ocarboxyl‚‚‚Owater) of 2.724 Å, which is shown in Figure 2b. Complex 4 contains [Zn(suc)(bpy)]n helix chains and lattice water molecules. Figure 3a shows a fragment of the chain in the structure of 4. The Zn(II) atom possesses an N2O3 environment by virtue of three carboxyl oxygen atoms of two carboxyl groups from two different succinate ligand units, one carboxyl group donating a single oxygen atom and the other affording two oxygen atoms, and two nitrogen atoms from a chelate 2,2′bipyridine to furnish a slightly distorted squarepyramidal coordination. The best basal plane is defined by O3a, O4a, N1, and N2, in which the mean deviation is 0.063 Å, and the other oxygen, O1, is located at the apical site. The Zn-N bond distances are equal [Zn(1)N(1) ) 2.040(3) and Zn(1)-N(2) ) 2.040(3) Å], which are similar to other Zn-N bond distances in the literature.19 Among three Zn-O (carboxyl) distances, two of them compare well with the distances found in

Diamine Substitution Reactions of [M(suc)(H2O)4]n

Crystal Growth & Design, Vol. 5, No. 5, 2005 1829 Table 3. Selected Bond Lengths and Angles Associated with the Helical Water Chain and the Host Structure in 4 D-H‚‚‚A O1w-H‚‚‚O2 O1w-H‚‚‚O2w O2w-H‚‚‚O3 O2w-H‚‚‚O2wa a

Figure 3. (a) ORTEP plot of the unit in [Zn(suc)(bpy)]n (4) at the 30% probability level. Hydrogen atoms are omitted for clarity. (b) Packing diagram of [Zn(suc)(bpy)]n‚2nH2O (4) along b axis. Hydrogen atoms are omitted for clarity.

the zinc carboxylate reported [Zn(1)-O(1) ) 1.955(2) and Zn(1)-O(3a) ) 1.967(3) Å],20 and the other is longer than the common Zn-O(carboxyl) bond length [Zn(1)O(4a) ) 2.469(3) Å], indicating that the O(4a) atom coordinates to the Zn(1) atom weakly. The succinate ligands bridge each pair of adjacent Zn(II) atoms to produce a chain running along the a axis, and the approximately perpendicular orientation of 2,2′-bipyridine ligands allows pairing of two centrosymmetrically related single-stranded chains to generate a doublestranded zipper-like chain, in which aromatic π-π stacking interactions exist between bpy pairs. The faceto-face distance between the paired bpy rings is about 3.6 Å, indicating moderately strong aromatic π-π stacking interactions. The striking feature of the structure in complex 4 is the formation of unprecedented 1D water chains interconnected by series of hydrogen bonds, lying between the double-stranded chains of the metal-organic framework forming a second series of ribbons along the a-axis. The infinite water chains appear to be important in the control of proton fluxes in a variety of biomolecules and also to facilitate the selective permeation of water across membranes.21 Therefore, the knowledge of structural constraints required in the stabilization of water chains and the influence of the chain structure on the host remains incomplete. So far, the water chains that have

D-H (Å) H‚‚‚A (Å) D‚‚‚A (Å) D-H‚‚‚A (deg) 0.85(1) 0.84(1) 0.84(1) 0.85(1)

1.91(2) 2.05(4) 1.98(2) 1.89(1)

2.756(4) 2.736(5) 2.781(4) 2.731(5)

164(4) 136(3) 158(4) 173(5)

Symmetry codes: 1 - x, 1 - y, -z.

beenhighlightedareformedoutofmonomers,22 dimers,23,24 cyclic tetramers,25 and hexamers.26 Among these, there are only two dimeric chain structures, which are similar to the chain structure in the bipyridine succinato zinc(II) complex 4. In one of them, the water chain is segregated by a layer formed by bpedo [trans-bis(4pyridyl)ethylene dioxide] molecules;23 the other the water chain is self-assembled in the pores of a metalorganic host lattice.24 In the bipyridine succinato zinc(II) complex 4, the water chains are constructed from a sequence of dimeric water molecules. O(1w) and O(2w) atoms of the water molecules are connected by a hydrogen bond with a distance of 2.736(5) Å. The O(2w) atom further links another asymmetric unit O(2wa) atom by virtue of a hydrogen bond, giving a distance of 2.731 Å. These bond distances compare well with that found in bpedo [trans-bis(4-pyridyl)ethylene dioxide] water layers23 and are shorter than that found in 1D chains of water molecules anchored onto a helical host.24 The angles within these ribbons range from 136(3)° to 173(5)°. Each water ribbon is linked to the chain of zinc compounds by two hydrogen bonds, O(1w)‚‚‚O(2) ) 2.756(4) Å and O(2w)‚‚‚O(3) ) 2.781(4) Å (Table 3). Thus, the observed water structure is stabilized by further hydrogen bonding interactions with the metalorganic chains. In the above transition metal dicarboxylate systems, the substitution of a coordinated water molecule, which plays a major role in determining the coordination mode of dicarboxylate ligands, is primarily influenced by the employment of chelate amine ligands.1c,27 Comparing the structures of 2 and 2a, 3 and 3a, 4, and 5, their synthetic conditions are very similar, and the main difference among them is the employment of diamine ligands. The subtle differences in diamine ligands prove to have a significant effect on the structure of the complex formed. For six-coordinated Ni(II) and Co(II) complexes, the coordinated succinate ligands are transformed from trans configuration in the tetrahydrate metal polymers 1 and 1a to cis configuration in the bipyridine succinato complexes 2 and 2a and phenanthroline succinato complexes 3 and 3a by the introduction of cis chelation of the rigid bpy and phen ligands. Contrasted with the bpy ligand, the phen ligand possesses a bigger conjugating rigid ring and stronger donor ability, so it can take the place of the two coordinate water molecules much more easily in tetrahydrate metal polymers 1 and 1a. At the same time, it can also decrease the electron density at the central metal, which results in the further coordination of a carboxyl group with the substitution of another water molecule. The coordination number of the d10-configuration in zinc complexes changes from six-coordination number in the tetrahydrate metal polymer 1b to five in the bipyridine succinato zinc complex 4 and four in the phenanthroline

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succinato zinc complex 5 by utilization of chelate bpy and phen ligands, respectively. Unlike the almost coplanar bpy ligand in 2 and 2a (dihedral angle of the two phenyl rings is 1.2°), the heterocycle of the bpy ligand in the zinc complex 4 is not flat as its pyridyl planes are twisted by 8.8°, resulting in the weak coordination of O(4a) and zinc atom [Zn(1)-O(4a) ) 2.469(3) Å]. In summary, the low-dimensional coordination polymers 2 and 2a, 3, and 4 have been synthesized from the substitution of diamine ligands with polymeric succinato complexes. Direct reaction of the metal(II) salt with the diamine ligand will block the formation of the desired coordination polymer. The polymeric succinate skeleton is important for further substitution with the diamine ligand, which implies the polymeric substitution reaction of the diamine ligand. For the octahedral environment Ni or Co complexes with a rigid bpy ligand, two coordination water molecules are substituted by the succinate ligand, and the coordination mode of the succinate ligand is bis-monodentate. When the ligand possesses stronger coordination or donor ability like phen, three coordination water molecules are replaced and both the terminal carboxylate groups of the succinate anion function in different coordination modes. One is monodentately bonded to one metal atom, and the other chelates the metal atom in bidentate mode. The steric bulk of these two ligands is relatively similar in the region of the metal atom, and the main difference is the electronic factors such as the relative donor strength or p-acid character of the ligands, which is an important factor in determining the final coordination sphere at the metal atoms. For the different coordination surroundings of Zn complexes, the coordination number varies from six to five with bpy ligand and to four with phen ligand, with the substitution of coordination water molecules. The tortion of the phenyl rings of the bpy ligand in complex 4 results in a weak coordination, which makes the coordination mode of the succinato ligand in complex 4 different from that in complex 5. These results indicate that the formation of the polymeric skeleton, coordination ability, and steric factors of the rigid aromatic chelate ligands play important roles in coordination mode of the succinate ligand, which may help us to understand the influence of organic spacers in determining the type and topology of the product. Acknowledgment. We thank the Ministry of Science & Technology (Grant 001CB108906) and the National Science Foundation of China for the generous support of this research. Supporting Information Available: X-ray crystallographic files in CIF format, IR and UV-vis spectra of the complexes, packing diagram of 2, and ORTEP diagrams of 2a and 3a. This material is available free of charge via the Internet at http://pubs.acs.org.

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