- Email: [email protected]
Self-assembly of one-dimensional coordination polymer from nickel(II) macrocyclic complex and 2,6-pyridinedicarboxylate ligand
Inorganic Chemistry Communications 6 (2003) 412–415 www.elsevier.com/locate/inoche
Self-assembly of one-dimensional coordination polymer from nickel(II) macrocyclic complex and 2,6-pyridinedicarboxylate ligand Ki-Young Choi
b
a,*
, Haiil Ryu a, Youn-Mook Lim a, Nack-Do Sung b, Ueon-Sang Shin c, Mancheol Suh d
a Department of Chemistry Education, Kongju National University, Kongju 314-701, South Korea Devision of Applied Biology and Chemistry, Research Center for Transgenic Cloned pigs, Chungnam National University, Taejon 305-764, South Korea c Institute for Inorganic Chemistry of RWTH Aachen, D-52056 Aachen, Germany d Department of Geoenvironmental Science, Kongju National University, Kongju 314-701, South Korea
Received 6 October 2002; accepted 11 December 2002
Abstract The reaction of ½NiðLÞðH2 OÞ2 Cl2 (L ¼ 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) with 2,6-pyridinedicarboxylate (pdc) generates one-dimensional coordination polymer ½NiðLÞðpdcÞ H2 O (1). In the polymeric framework, the nickel(II) ion has an octahedral geometry and is bridged by two pdc ligands. The magnetic susceptibility measurement for 1 exhibits a weak antiferromagnetic interaction (J ¼ 1:04ð3Þ cm1 ; H ¼ J RSi Siþ1 ) between the S ¼ 1 nickel(II) paramagnetic centers. Ó 2003 Elsevier Science B.V. All rights reserved. Keywords: Crystal structure; Nickel(II) complex; Antiferromagnetic interaction; One-dimensional polymer; 2,6-Pyridinedicarboxylate
1. Introduction Crystal engineering of metal-organic coordination polymers has been of great interest due to their importance as promising materials [1–4]. Self-assembly of metal ions and multidentate organic ligands has achieved great success in forming supramolecular materials, which exhibit novel properties such as porosity [5,6], magnetism [7,8] and non-linear optical behavior [9,10]. The multidentate polycarboxylates such as terephthalate (tp) and 1,3,5-benzenetricarboxylate (btc) have been used as bridging ligands to stabilize many structures with open or porous frameworks [11–13]. For example, an one-dimensional nickel(II) complex ½NiðdttdÞðtpÞ 2H2 O (dttd ¼ 3,14-dimethyl-2,6,13,17tetraazatricyclo½14; 4; 01:18 ; 07:12 docosane) exhibits a distorted octahedral geometry and shows a weak anti-
ferromagnetic interaction, in which the macrocycle and tp ligands have assembled around the nickel center [12]. However, the two-dimensional networks ½NiðbhhtÞ3 ½btc2 18H2 O and ½NiðbhhtÞ3 ½btc2 18H2 O 2C5 H5 N (bhht ¼ 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) [13] exhibit the brick wall and honeycomb structures, respectively. The different molecular topologies in these complexes may be due to the different coordination modes of the btc ligand. In order to better understand some aspects of nickel(II) complex of tetraaza macrocycle containing the organic ligand, we report the synthesis, properties and crystal structure of ½NiðLÞðpdcÞ H2 O (1).
*
Corresponding author. Tel.: +82-41-850-8541; fax: +82-41-8508541. E-mail address: [email protected] (K.-Y. Choi). 1387-7003/03/$ - see front matter Ó 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S1387-7003(02)00802-X
K.-Y. Choi et al. / Inorganic Chemistry Communications 6 (2003) 412–415
2. Experimental 2.1. Materials and physical measurements All commercially available products were used without further purification. The complex ½NiðLÞðH2 OÞ2 Cl2 was prepared by the literature method [14]. IR spectra were recorded on a Perkin–Elmer Paragon 1000 FT-IR spectrophotometer using KBr pellets. Solution electronic spectra were obtained on a JASCO Uvidec 610 spectrophotometer. Solid-state spectra measured by diffuse reflectance method on a Shimadzu UV2401 PC/ DRS spectrophotometer. Magnetic measurements on powder samples were carried out under 1 T using a Quantum Design MPMS-7 SQUID magnetometer. The diamagnetic corrections of 1 were estimated from PascalÕs constants. Elemental analyses for C, H and N were performed on a Perkin–Elmer CHN-2400 analyzer. 2.2. Synthesis of ½NiðLÞðpdcÞ H2 O ð1Þ To a methanol solution (20 ml) of ½NiðLÞðH2 OÞ2 Cl2 (211 mg, 0.5 mmol) was added Na2 pdc (101 mg, 1 mmol) and the mixture was stirred for 1 h at room temperature. The solution was filtered to remove insoluble material. After the solution was left to stand at room temperature over a period of several days, a quantity of pink crystals precipitated. These were filtered out and one of them was subjected to the X-ray analysis. Anal. Calc. for C21 H37 N5 NiO5 : C, 50.62; H, 7.49; N, 14.06. Found: C, 50.74; H, 7.37; N, 14.14%. IR (KBr, cm1 ): 3448(s), 3176(s), 2969(s), 2936(s), 1612(s), 1570(s), 1459(m), 1438(m), 1360(s), 1264(w), 1120(m), 1054(w), 1018(w), 993(w), 900(w), 761(m), 721(s), 546(w) and 421(w). UV/Vis in water ½kmax , nm ðe; M1 cm1 Þ: 456 (68), in acetonitrile: 530 (7.1), in DMF: 528 (7.2), in diffuse reflectance ðkmax , nm) 528. FAB mass (m/z): 498 ðMÞþ .
413
determined by least-squares fit of 25 reflections. The intensity data were collected in the x–2h scan mode and corrected for Lorentz and polarization effects. An empirical absorption correction based on u-scan was applied (Tmax ¼ 0:881, Tmin ¼ 0:780). The structure was solved by direct methods and refined using weighted full-matrix least-squares on F 2 [15,16]. All hydrogen atoms were located by difference maps and refined isotropically. All non-hydrogen atoms were refined anisotropically.
3. Results and discussion 3.1. Structural description An ORTEP drawing of 1 with the atomic numbering scheme is shown in Fig. 1. The crystal structure of 1 consists of a pdc anion, water molecule and ½NiðLÞ2þ cations, which are located on the center of inversion. These cationic units are bridged by pdc anions to give a novel one-dimensional coordination polymer in the lattice. Each nickel atom occupies a distorted octahedral environment with the four secondary amines of the macrocycle in which two trans pdc ligands have assembled around each metal center. The Ni(1) Ni(2) dis, whereas the tance in the chain structure is 11.099(2) A closest Nið1Þ Nið2Þi distance between neighboring (symmetry code: (i) x, y þ 1=2, complexes is 7.858(2) A z þ 3=2). The nickel atom and the four nitrogen atoms
2.3. Crystallographic data Crystal data for 1: C21 H37 N5 NiO5 , M ¼ 498:27, monoclinic, P 21 /c, a ¼ 15:715ð3Þ, b ¼ 9:975ð2Þ, c ¼ , b ¼ 99:63ð1Þ°, V ¼ 2318:9ð7Þ A 3 , Z ¼ 4, 15:005ð3Þ A 3 1 l(Mo Ka ) ¼ 0.879 mm , Dc ¼ 1:427 Mg m , F ð0 00Þ ¼ 1064, crystal dimensions 0:30 0:26 0:15 mm3 , 4070 unique reflections, 2277 observed data ½I > 2rðIÞ used in the refinement, final R1 ¼ 0:0627, wR2 ¼ 0:1501 (R1 ¼ 0:1287, wR2 ¼ 0:1840 for all data), GOF ¼ 0.980, largest 3 . difference peak and hole: 0.644 and )0.829 e A X-ray diffraction data: an Enraf–Nonius CAD4 diffractometer using graphite-monochromated Mo Ka ra) at 293(2) K. The accurate unit diation (k ¼ 0:71073 A cell parameters and a crystal orientation matrix were
Fig. 1. An ORTEP view of 1 with the atomic numbering scheme (30% ) and angles (°) probability ellipsoids shown). Selected bond lengths (A for 1 are: Ni(1)–N(1) 2.070(4), Ni(1)–N(2) 2.087(5), Ni(1)–O(1) 2.115(4), Ni(2)–N(4) 2.084(5), Ni(2)–N(5) 2.090(5), Ni(2)–O(4) 2.086(4), N(3)–C(9) 1.359(6), N(3)–C(13) 1.348(6), O(1)–C(8) 1.280(7), O(2)–C(8) 1.219(7), O(3)–C(14) 1.215(7), O(4)–C(14) 1.275(6), Ni(1) Ni(2) 11.099(2), N(1)–Ni(1)–N(2) 84.7(2), N(1)–Ni(1)–Nð2Þi 95.3(2), N(1)–Ni(1)–O(1) 87.6(2), N(2)–Ni(1)–O(1) 87.6(2), Nð1Þi – Ni(1)–O(1) 92.4(2), Nð2Þi –Ni(1)–O(1) 92.5(2), N(4)–Ni(2)-N(5) 85.0(2), N(4)–Ni(2)–Nð5Þii 95.0(2), N(4)–Ni(2)–O(4) 91.0(2), N(5)– Ni(2)–O(4) 88.4(2), Nð4Þii –Ni(2)–O(4) 89.0(2), Nð5Þii –Ni(2)–O(4) 91.6(2), Ni(1)–O(1)–C(8) 134.4(4), Ni(2)–O(4)–C(14) 134.4(4), C(9)– N(3)–C(13) 117.2(5), O(1)–C(8)–O(2) 125.5(5), O(3)–C(14)–O(4) 126.0(5). Symmetry codes: (i) x þ 1, y þ 1, z þ 2; (ii) x, y, z þ 1.
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of the macrocycle are exactly in a plane. The two average Nið1ÞN4 and Nið2ÞN4 distances are 2.079(3) and . The bond distances from the nickel(II) ions 2.087(4) A to the oxygen atoms of the pdc ligands are Ni(1)–O(1) and Ni(2)–O(4) 2.086(4) A , respectively. The 2.115(4) A two bond angles related to the pdc ligands have the same value (Ni(1)–O(1)–C(8) 134.4(4)° and Ni(2)–O(4)–C(14) 134.4(4)°). The average Ni–N (secondary amines) bond is similar to that observed for the distance of 2.083(2) A octahedral nickel(II) complexes with 14-membered tetraaza macrocycles [12,14,17,18]. The N–Ni–N angles of the five-membered chelate rings are larger than those of the six-membered chelate rings. Also, the axial Ni–O (carboxylate) linkages are bent slightly off the perpendicular to the NiN4 planes by 1.0–2.5°. The dihedral angles (a) between the plane of the carboxylate group and pyridine ring involving Ni(1) and Ni(2) are 4.5 and 4.0°. Furthermore, the dihedral angles (b) between the plane of the carboxylate group and NiN2 O4 plane involving Ni(1) and Ni(2) are 3.7° and 38.5°, respectively. The uncoordinated carboxylate oxygens O(2) and O(3) of the pdc ligand form hydrogen bonds with the water and O(3) Ow(1) molecule (O(2) Ow(1) 2.888(7) A 3.020(7) A). 3.2. Chemical properties The IR spectrum of 1 reveals m(N–H) of the secondary amines and m(COO) of the carboxylate at 3176 and 1612 cm1 , respectively. Visible absorption spectra of 1 in acetonitrile and DMF solution show d–d bands at 530 and 528 nm which assigned to the transition 3 A2g ! 3 T1g ðFÞ [19]. The electronic diffuse reflectance spectrum of 1 exhibits maximum absorption at 528 nm, which is characteristic chromophore for the nickel(II) ion coordinated with N4 O2 donors [20]. However, compound 1 dissolves in water and decomposes into the building block, which is identified by the UV–Vis spectrum showing the characteristic chromophore (456 nm) of the square–planar nickel(II) macrocyclic complexes [21,22]. The magnetic susceptibilities ðvm ) of 1 were measured in the range of 5.0–300 K. The vm and effective magnetic moment ðleff ) versus temperature plots are shown in Fig. 2. The magnetic moment of 1 (per one Ni) is 3.24lB at room temperature and gradually decrease with decreasing temperature, suggesting the presence of an antiferromagnetic interaction between the nickel(II) centers. The vm data are interpreted with FisherÕs model [23,24] for the classical-spin chain system (S ¼ 1 and Hchain ¼ J RSi Siþ1 ). The vm data can be expressed as vm ¼ fN b2 g2 SðS þ 1Þ=3kT gfð1 þ uÞ=ð1 uÞg with u ¼ coth½JSðS þ 1Þ=kT ½kT =JSðS þ 1Þ:
ð1Þ
Fig. 2. Plots of vm vs T (d) and leff vs T (s) for 1. The solid line represents the best fit of the experimental data to Eq. (1).
The best-fit parameters are obtained using a nonlinear regression analysis with g ¼ 2:26ð1Þ, J ¼ 1:04ð3Þ cm1 and R ¼ 4:1 103 ðR ¼ ½Rðvobs vcalc Þ2 =Rvobs 2 1=2 ). This result indicates that there exists a very weak antiferromagnetic interaction between the Ni(II) centers along the chain via the bridging pdc ligand. The value of J for compound 1 is slightly smaller than that reported through bridging carboxylato in the nickel(II) coordination polymer ½NiðdttdÞðddcÞ H2 O (ddc ¼ 2,5-pyridinedicarboxylate) (J ¼ 1:47 cm1 ) [12]. This fact may be attributed to the decrease in the intramolecular ) and the dihedral angle b Ni(1) Ni(2) distance (11.1 A (3.7° and 38.5°) compared with ½NiðdttdÞðddcÞ H2 O , b ¼ 5:7 and 11.6). (d ¼ 11:5 A
Supplementary material Crystallographic data for compound 1 have been deposited with the Cambridge Crystallographic Data Centre (CCDC), deposition number CCDC 199234.
Acknowledgements This work was supported by the grant (No. R112002-100-03002-0) from ERC program of the Korea Science & Engineering Foundation and in part by the Ministry of Science and Technology of Korea, the National Research Laboratory Program grant to NRLCP (Nondestructive Research Laboratory of Cultural Property) of Kongju National University. References [1] P.J. Stang, B. Olenyuk, Acc. Chem. Res. 30 (1997) 502. [2] S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853.
K.-Y. Choi et al. / Inorganic Chemistry Communications 6 (2003) 412–415 [3] M.J. Zaworotko, Angew. Chem., Int. Ed. 39 (2000) 3052. [4] B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629. [5] S. Noro, S. Kitazawa, M. Kondo, K. Seki, Angew. Chem., Int. Ed. 39 (2000) 2082. [6] L. Pan, E.B. Woodlock, X. Wang, Inorg. Chem. 39 (2000) 4174. [7] O. Kahn, Acc. Chem. Res. 33 (2000) 647. [8] O. Kahn, C.J. Martinez, Science 279 (1998) 44. [9] O.R. Evans, R. Xiong, Z. Wang, G.K. Wong, W. Lin, Angew. Chem., Int. Ed. 38 (1999) 536. [10] W. Lin, Z. Wang, L. Ma, J. Am. Chem. Soc. 121 (1999) 11249. [11] M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. OÕFeeffe, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319. [12] K.-Y. Choi, K.M. Chun, I.-H. Suh, Poyhedron 20 (2001) 57. [13] H.J. Choi, M.P. Suh, J. Am. Chem. Soc. 120 (1998) 10622. [14] K.-Y. Choi, S.N. Choi, I.-H. Suh, Polyhedron 17 (1998) 1415. [15] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
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[16] G.M. Sheldrick, SHELXL-97, program for the refinement of crystal structures, University of G€ ottingen, Germany, 1997. [17] K. Mochizuki, T. Kondo, Inorg. Chem. 34 (1995) 6241. [18] K.-Y. Choi, H. Ryu, I.-H. Suh, Polyhedron 17 (1998) 1241. [19] E. Konig, in: Structure and Bonding, Springer, New York, 1971, p. 175. [20] F.L. Urbach, G.A. Melson (Eds.), Coordination Chemistry of Macrocyclic Compounds, Plenum Press, New York, 1977, pp. 350–355. [21] R.W. Hay, G.A. Lawrence, J. Chem. Soc., Dalton Trans. (1975) 1466. [22] R.W. Hay, P.D. Piplani, J. Chem. Soc., Dalton Trans. (1977) 1956. [23] H. Oshio, H. Okamoto, T. Kikuchi, T. Ito, Inorg. Chem. 36 (1997) 3201. [24] M.E. Fisher, Am. J. Phys. 32 (1964) 343.
Self-assembly of one-dimensional coordination polymer from nickel(II) macrocyclic complex and 2,6-pyridinedicarboxylate ligand Ki-Young Choi
b
a,*
, Haiil Ryu a, Youn-Mook Lim a, Nack-Do Sung b, Ueon-Sang Shin c, Mancheol Suh d
a Department of Chemistry Education, Kongju National University, Kongju 314-701, South Korea Devision of Applied Biology and Chemistry, Research Center for Transgenic Cloned pigs, Chungnam National University, Taejon 305-764, South Korea c Institute for Inorganic Chemistry of RWTH Aachen, D-52056 Aachen, Germany d Department of Geoenvironmental Science, Kongju National University, Kongju 314-701, South Korea
Received 6 October 2002; accepted 11 December 2002
Abstract The reaction of ½NiðLÞðH2 OÞ2 Cl2 (L ¼ 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) with 2,6-pyridinedicarboxylate (pdc) generates one-dimensional coordination polymer ½NiðLÞðpdcÞ H2 O (1). In the polymeric framework, the nickel(II) ion has an octahedral geometry and is bridged by two pdc ligands. The magnetic susceptibility measurement for 1 exhibits a weak antiferromagnetic interaction (J ¼ 1:04ð3Þ cm1 ; H ¼ J RSi Siþ1 ) between the S ¼ 1 nickel(II) paramagnetic centers. Ó 2003 Elsevier Science B.V. All rights reserved. Keywords: Crystal structure; Nickel(II) complex; Antiferromagnetic interaction; One-dimensional polymer; 2,6-Pyridinedicarboxylate
1. Introduction Crystal engineering of metal-organic coordination polymers has been of great interest due to their importance as promising materials [1–4]. Self-assembly of metal ions and multidentate organic ligands has achieved great success in forming supramolecular materials, which exhibit novel properties such as porosity [5,6], magnetism [7,8] and non-linear optical behavior [9,10]. The multidentate polycarboxylates such as terephthalate (tp) and 1,3,5-benzenetricarboxylate (btc) have been used as bridging ligands to stabilize many structures with open or porous frameworks [11–13]. For example, an one-dimensional nickel(II) complex ½NiðdttdÞðtpÞ 2H2 O (dttd ¼ 3,14-dimethyl-2,6,13,17tetraazatricyclo½14; 4; 01:18 ; 07:12 docosane) exhibits a distorted octahedral geometry and shows a weak anti-
ferromagnetic interaction, in which the macrocycle and tp ligands have assembled around the nickel center [12]. However, the two-dimensional networks ½NiðbhhtÞ3 ½btc2 18H2 O and ½NiðbhhtÞ3 ½btc2 18H2 O 2C5 H5 N (bhht ¼ 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) [13] exhibit the brick wall and honeycomb structures, respectively. The different molecular topologies in these complexes may be due to the different coordination modes of the btc ligand. In order to better understand some aspects of nickel(II) complex of tetraaza macrocycle containing the organic ligand, we report the synthesis, properties and crystal structure of ½NiðLÞðpdcÞ H2 O (1).
*
Corresponding author. Tel.: +82-41-850-8541; fax: +82-41-8508541. E-mail address: [email protected] (K.-Y. Choi). 1387-7003/03/$ - see front matter Ó 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S1387-7003(02)00802-X
K.-Y. Choi et al. / Inorganic Chemistry Communications 6 (2003) 412–415
2. Experimental 2.1. Materials and physical measurements All commercially available products were used without further purification. The complex ½NiðLÞðH2 OÞ2 Cl2 was prepared by the literature method [14]. IR spectra were recorded on a Perkin–Elmer Paragon 1000 FT-IR spectrophotometer using KBr pellets. Solution electronic spectra were obtained on a JASCO Uvidec 610 spectrophotometer. Solid-state spectra measured by diffuse reflectance method on a Shimadzu UV2401 PC/ DRS spectrophotometer. Magnetic measurements on powder samples were carried out under 1 T using a Quantum Design MPMS-7 SQUID magnetometer. The diamagnetic corrections of 1 were estimated from PascalÕs constants. Elemental analyses for C, H and N were performed on a Perkin–Elmer CHN-2400 analyzer. 2.2. Synthesis of ½NiðLÞðpdcÞ H2 O ð1Þ To a methanol solution (20 ml) of ½NiðLÞðH2 OÞ2 Cl2 (211 mg, 0.5 mmol) was added Na2 pdc (101 mg, 1 mmol) and the mixture was stirred for 1 h at room temperature. The solution was filtered to remove insoluble material. After the solution was left to stand at room temperature over a period of several days, a quantity of pink crystals precipitated. These were filtered out and one of them was subjected to the X-ray analysis. Anal. Calc. for C21 H37 N5 NiO5 : C, 50.62; H, 7.49; N, 14.06. Found: C, 50.74; H, 7.37; N, 14.14%. IR (KBr, cm1 ): 3448(s), 3176(s), 2969(s), 2936(s), 1612(s), 1570(s), 1459(m), 1438(m), 1360(s), 1264(w), 1120(m), 1054(w), 1018(w), 993(w), 900(w), 761(m), 721(s), 546(w) and 421(w). UV/Vis in water ½kmax , nm ðe; M1 cm1 Þ: 456 (68), in acetonitrile: 530 (7.1), in DMF: 528 (7.2), in diffuse reflectance ðkmax , nm) 528. FAB mass (m/z): 498 ðMÞþ .
413
determined by least-squares fit of 25 reflections. The intensity data were collected in the x–2h scan mode and corrected for Lorentz and polarization effects. An empirical absorption correction based on u-scan was applied (Tmax ¼ 0:881, Tmin ¼ 0:780). The structure was solved by direct methods and refined using weighted full-matrix least-squares on F 2 [15,16]. All hydrogen atoms were located by difference maps and refined isotropically. All non-hydrogen atoms were refined anisotropically.
3. Results and discussion 3.1. Structural description An ORTEP drawing of 1 with the atomic numbering scheme is shown in Fig. 1. The crystal structure of 1 consists of a pdc anion, water molecule and ½NiðLÞ2þ cations, which are located on the center of inversion. These cationic units are bridged by pdc anions to give a novel one-dimensional coordination polymer in the lattice. Each nickel atom occupies a distorted octahedral environment with the four secondary amines of the macrocycle in which two trans pdc ligands have assembled around each metal center. The Ni(1) Ni(2) dis, whereas the tance in the chain structure is 11.099(2) A closest Nið1Þ Nið2Þi distance between neighboring (symmetry code: (i) x, y þ 1=2, complexes is 7.858(2) A z þ 3=2). The nickel atom and the four nitrogen atoms
2.3. Crystallographic data Crystal data for 1: C21 H37 N5 NiO5 , M ¼ 498:27, monoclinic, P 21 /c, a ¼ 15:715ð3Þ, b ¼ 9:975ð2Þ, c ¼ , b ¼ 99:63ð1Þ°, V ¼ 2318:9ð7Þ A 3 , Z ¼ 4, 15:005ð3Þ A 3 1 l(Mo Ka ) ¼ 0.879 mm , Dc ¼ 1:427 Mg m , F ð0 00Þ ¼ 1064, crystal dimensions 0:30 0:26 0:15 mm3 , 4070 unique reflections, 2277 observed data ½I > 2rðIÞ used in the refinement, final R1 ¼ 0:0627, wR2 ¼ 0:1501 (R1 ¼ 0:1287, wR2 ¼ 0:1840 for all data), GOF ¼ 0.980, largest 3 . difference peak and hole: 0.644 and )0.829 e A X-ray diffraction data: an Enraf–Nonius CAD4 diffractometer using graphite-monochromated Mo Ka ra) at 293(2) K. The accurate unit diation (k ¼ 0:71073 A cell parameters and a crystal orientation matrix were
Fig. 1. An ORTEP view of 1 with the atomic numbering scheme (30% ) and angles (°) probability ellipsoids shown). Selected bond lengths (A for 1 are: Ni(1)–N(1) 2.070(4), Ni(1)–N(2) 2.087(5), Ni(1)–O(1) 2.115(4), Ni(2)–N(4) 2.084(5), Ni(2)–N(5) 2.090(5), Ni(2)–O(4) 2.086(4), N(3)–C(9) 1.359(6), N(3)–C(13) 1.348(6), O(1)–C(8) 1.280(7), O(2)–C(8) 1.219(7), O(3)–C(14) 1.215(7), O(4)–C(14) 1.275(6), Ni(1) Ni(2) 11.099(2), N(1)–Ni(1)–N(2) 84.7(2), N(1)–Ni(1)–Nð2Þi 95.3(2), N(1)–Ni(1)–O(1) 87.6(2), N(2)–Ni(1)–O(1) 87.6(2), Nð1Þi – Ni(1)–O(1) 92.4(2), Nð2Þi –Ni(1)–O(1) 92.5(2), N(4)–Ni(2)-N(5) 85.0(2), N(4)–Ni(2)–Nð5Þii 95.0(2), N(4)–Ni(2)–O(4) 91.0(2), N(5)– Ni(2)–O(4) 88.4(2), Nð4Þii –Ni(2)–O(4) 89.0(2), Nð5Þii –Ni(2)–O(4) 91.6(2), Ni(1)–O(1)–C(8) 134.4(4), Ni(2)–O(4)–C(14) 134.4(4), C(9)– N(3)–C(13) 117.2(5), O(1)–C(8)–O(2) 125.5(5), O(3)–C(14)–O(4) 126.0(5). Symmetry codes: (i) x þ 1, y þ 1, z þ 2; (ii) x, y, z þ 1.
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of the macrocycle are exactly in a plane. The two average Nið1ÞN4 and Nið2ÞN4 distances are 2.079(3) and . The bond distances from the nickel(II) ions 2.087(4) A to the oxygen atoms of the pdc ligands are Ni(1)–O(1) and Ni(2)–O(4) 2.086(4) A , respectively. The 2.115(4) A two bond angles related to the pdc ligands have the same value (Ni(1)–O(1)–C(8) 134.4(4)° and Ni(2)–O(4)–C(14) 134.4(4)°). The average Ni–N (secondary amines) bond is similar to that observed for the distance of 2.083(2) A octahedral nickel(II) complexes with 14-membered tetraaza macrocycles [12,14,17,18]. The N–Ni–N angles of the five-membered chelate rings are larger than those of the six-membered chelate rings. Also, the axial Ni–O (carboxylate) linkages are bent slightly off the perpendicular to the NiN4 planes by 1.0–2.5°. The dihedral angles (a) between the plane of the carboxylate group and pyridine ring involving Ni(1) and Ni(2) are 4.5 and 4.0°. Furthermore, the dihedral angles (b) between the plane of the carboxylate group and NiN2 O4 plane involving Ni(1) and Ni(2) are 3.7° and 38.5°, respectively. The uncoordinated carboxylate oxygens O(2) and O(3) of the pdc ligand form hydrogen bonds with the water and O(3) Ow(1) molecule (O(2) Ow(1) 2.888(7) A 3.020(7) A). 3.2. Chemical properties The IR spectrum of 1 reveals m(N–H) of the secondary amines and m(COO) of the carboxylate at 3176 and 1612 cm1 , respectively. Visible absorption spectra of 1 in acetonitrile and DMF solution show d–d bands at 530 and 528 nm which assigned to the transition 3 A2g ! 3 T1g ðFÞ [19]. The electronic diffuse reflectance spectrum of 1 exhibits maximum absorption at 528 nm, which is characteristic chromophore for the nickel(II) ion coordinated with N4 O2 donors [20]. However, compound 1 dissolves in water and decomposes into the building block, which is identified by the UV–Vis spectrum showing the characteristic chromophore (456 nm) of the square–planar nickel(II) macrocyclic complexes [21,22]. The magnetic susceptibilities ðvm ) of 1 were measured in the range of 5.0–300 K. The vm and effective magnetic moment ðleff ) versus temperature plots are shown in Fig. 2. The magnetic moment of 1 (per one Ni) is 3.24lB at room temperature and gradually decrease with decreasing temperature, suggesting the presence of an antiferromagnetic interaction between the nickel(II) centers. The vm data are interpreted with FisherÕs model [23,24] for the classical-spin chain system (S ¼ 1 and Hchain ¼ J RSi Siþ1 ). The vm data can be expressed as vm ¼ fN b2 g2 SðS þ 1Þ=3kT gfð1 þ uÞ=ð1 uÞg with u ¼ coth½JSðS þ 1Þ=kT ½kT =JSðS þ 1Þ:
ð1Þ
Fig. 2. Plots of vm vs T (d) and leff vs T (s) for 1. The solid line represents the best fit of the experimental data to Eq. (1).
The best-fit parameters are obtained using a nonlinear regression analysis with g ¼ 2:26ð1Þ, J ¼ 1:04ð3Þ cm1 and R ¼ 4:1 103 ðR ¼ ½Rðvobs vcalc Þ2 =Rvobs 2 1=2 ). This result indicates that there exists a very weak antiferromagnetic interaction between the Ni(II) centers along the chain via the bridging pdc ligand. The value of J for compound 1 is slightly smaller than that reported through bridging carboxylato in the nickel(II) coordination polymer ½NiðdttdÞðddcÞ H2 O (ddc ¼ 2,5-pyridinedicarboxylate) (J ¼ 1:47 cm1 ) [12]. This fact may be attributed to the decrease in the intramolecular ) and the dihedral angle b Ni(1) Ni(2) distance (11.1 A (3.7° and 38.5°) compared with ½NiðdttdÞðddcÞ H2 O , b ¼ 5:7 and 11.6). (d ¼ 11:5 A
Supplementary material Crystallographic data for compound 1 have been deposited with the Cambridge Crystallographic Data Centre (CCDC), deposition number CCDC 199234.
Acknowledgements This work was supported by the grant (No. R112002-100-03002-0) from ERC program of the Korea Science & Engineering Foundation and in part by the Ministry of Science and Technology of Korea, the National Research Laboratory Program grant to NRLCP (Nondestructive Research Laboratory of Cultural Property) of Kongju National University. References [1] P.J. Stang, B. Olenyuk, Acc. Chem. Res. 30 (1997) 502. [2] S. Leininger, B. Olenyuk, P.J. Stang, Chem. Rev. 100 (2000) 853.
K.-Y. Choi et al. / Inorganic Chemistry Communications 6 (2003) 412–415 [3] M.J. Zaworotko, Angew. Chem., Int. Ed. 39 (2000) 3052. [4] B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629. [5] S. Noro, S. Kitazawa, M. Kondo, K. Seki, Angew. Chem., Int. Ed. 39 (2000) 2082. [6] L. Pan, E.B. Woodlock, X. Wang, Inorg. Chem. 39 (2000) 4174. [7] O. Kahn, Acc. Chem. Res. 33 (2000) 647. [8] O. Kahn, C.J. Martinez, Science 279 (1998) 44. [9] O.R. Evans, R. Xiong, Z. Wang, G.K. Wong, W. Lin, Angew. Chem., Int. Ed. 38 (1999) 536. [10] W. Lin, Z. Wang, L. Ma, J. Am. Chem. Soc. 121 (1999) 11249. [11] M. Eddaoudi, D.B. Moler, H. Li, B. Chen, T.M. Reineke, M. OÕFeeffe, O.M. Yaghi, Acc. Chem. Res. 34 (2001) 319. [12] K.-Y. Choi, K.M. Chun, I.-H. Suh, Poyhedron 20 (2001) 57. [13] H.J. Choi, M.P. Suh, J. Am. Chem. Soc. 120 (1998) 10622. [14] K.-Y. Choi, S.N. Choi, I.-H. Suh, Polyhedron 17 (1998) 1415. [15] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
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[16] G.M. Sheldrick, SHELXL-97, program for the refinement of crystal structures, University of G€ ottingen, Germany, 1997. [17] K. Mochizuki, T. Kondo, Inorg. Chem. 34 (1995) 6241. [18] K.-Y. Choi, H. Ryu, I.-H. Suh, Polyhedron 17 (1998) 1241. [19] E. Konig, in: Structure and Bonding, Springer, New York, 1971, p. 175. [20] F.L. Urbach, G.A. Melson (Eds.), Coordination Chemistry of Macrocyclic Compounds, Plenum Press, New York, 1977, pp. 350–355. [21] R.W. Hay, G.A. Lawrence, J. Chem. Soc., Dalton Trans. (1975) 1466. [22] R.W. Hay, P.D. Piplani, J. Chem. Soc., Dalton Trans. (1977) 1956. [23] H. Oshio, H. Okamoto, T. Kikuchi, T. Ito, Inorg. Chem. 36 (1997) 3201. [24] M.E. Fisher, Am. J. Phys. 32 (1964) 343.