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A 3D heterometallic framework containing Co–O–Li linkages: Hydrothermal synthesis, crystal structure and magnetic property
Inorganica Chimica Acta 407 (2013) 239–242
Contents lists available at ScienceDirect
Inorganica Chimica Acta journal homepage: www.elsevier.com/locate/ica
A 3D heterometallic framework containing Co–O–Li linkages: Hydrothermal synthesis, crystal structure and magnetic property Yue Yuan, Dan Wang, Shi Xin Liu, Ying Wang ⇑, Ju Yan Liu ⇑, Bin Ding ⇑, Xiao Jun Zhao ⇑ Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic–Organic Hybrid Functional Material Chemistry, Tianjin Normal University, Ministry of Education, Tianjin 300387, People’s Republic of China
a r t i c l e
i n f o
Article history: Received 29 March 2013 Received in revised form 15 July 2013 Accepted 18 July 2013 Available online 2 August 2013 Keywords: Dioxyacetic acid Co–O–Li linkage Ligand conformations Magnetic property
a b s t r a c t Using dioxyacetic acid (H2oda), CoCl26H2O and LiOH, a three-dimensional (3D) heterometallic complex [CoLi2(oda)2]n (1) containing 1D Co–O–Li chains has been isolated under hydrothermal conditions. 1 represents a 3D hybrid magnetic rigid framework. To the best of our knowledge, such a chain with the arrangement of Co–O–Li linkages based on carboxylic acid has been first reported. Further analysis reveals that cis-conformation of dioxyacetic acid greatly favor chelate coordination of lithium(I) centers. Magnetic measurements indicate that in the low temperature, complex 1 shows weak ferromagnetic interaction, indicative of spin-canting behavior. Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction The design and syntheses of new metal–organic coordination architectures have attracted great attention not only because of their intriguing variety of architectures and topologies [1], but also their potential applicable properties in recent years [2]. Up to now, a great number of inorganic–organic hybrid coordination polymers have been reported based on the ligands containing O donors such as carboxylates [3], especially the dioxyacetic acid (H2oda). H2oda possesses the features of potential interest for corrosion inhibition [4,5], and its coordinatioin chemistry with the main-group metal ions, transition metal ions and lanthanoid(III) cations, which displayed novel supra-molecular structures [6,7]. As part of an ongoing research project dealing with the coordination chemistry of H2oda [7], herein we report the three-dimensional (3D) main group-transitional mixed-metal complex, namely, [CoLi(oda)2]n (1), which contains 1D Co–O–Li linkages under hydrothermal conditions. Magnetic measurements indicate that in the low temperature, complex 1 shows weak ferromagnetic interaction, indicative of spin-canting behavior. 2. Experimental 2.1. Materials and general methods All the solvents and reagents for synthesis were obtained commercially and used as received. Analyses for C, H, and N were ⇑ Corresponding authors. E-mail address: [email protected] (Y. Wang). 0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.ica.2013.07.030
carried out on a Perkin-Elmer 240 elemental analyzer. Powder X-ray diffraction (PXRD) measurements were recorded on a D/ Max-2500 X-ray diffractometer using Cu Ka radiation. The magnetisation data for 1 was recorded on a Quantum Design MPMS-XL7 SQUID magnetometer. Variable-temperature magnetic susceptibility measurements were performed in an applied field of 2 kOe in the temperature range of 300–1.8 K. The molar magnetic susceptibilities were corrected for the diamagnetism estimated from Pascal’s tables and for the sampleholder by a previous calibration. 2.2. Synthesis of complex 1 CoCl26H2O (0.0476 g, 0.2 mmol), H2oda (0.1341 g, 1.0 mmol), LiOH (0.0024 g, 0.1 mmol) and H2O (15 mL) were placed in a 25 mL Teflon-lined steel vessel and heated to 160 °C for 3 days, then cooled to room temperature. The resulting red block-shaped crystals for 1 were washed several times by water and diethyl ether. The yield is 65% based on CoCl26H2O. Elemental Anal. Calc. for 1 C8H8CoLi2O10 (336.95): Co, 17.49; Li, 4.12; C, 28.52; H, 2.39. Found: Co, 17.71; Li, 4.33; C, 28.56; H, 2.42%. Hydrothermal conditions are essential for the synthesis of 1, higher temperature may facilitate the formation of higher-dimensional inorganic connectivity. 2.3. Crystal structure determination X-ray single-crystal diffraction data for complex 1 was collected on an APEX II CCD at 293(2) K with a graphite-monochromated Mo Ka radiation (k = 0.71073 Å). The absorption correction was
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performed using the CRYSTAL CLEAR programs [8,9]. All non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms were located at geometrically calculated positions. Crystallographic data and structural refinements for complex 1 are summarized in Table 1. Selected bond lengths and angles are listed in Table S1. The coordination mode of H2oda is demonstrated in Scheme 1.
3. Results and discussion 3.1. Description of crystal structure of complex 1 X-ray single-crystal determination shows that 1 contains one crystallographic independent CoII ion (Co1), two crystallographic independent LiI ions (Li1 and Li2) and two oda2 ligands (Fig. 1). Co1 is in the octahedral geometry and six-coordinated by six oxygen atoms (O1, O9A, O4B, O2A, O7A, O6, and O2A) from four oda2 ligands (Fig. S1). Both Li1 and Li2 are located in the distorted square pyramid and penta-coordinated by five oxygen atoms from three oda2 ligands, as displayed in Fig. S2. Co1 Li2 and Co1C Li1 distances separated by two l2-bridged oxygen atoms are 3.151 and 3.051 Å, respectively. The carboxylic acid group of H2oda is fully de-protonated, as is illustrated in Fig. 2. The cis-ligand in complex 1 connects three cobalt(II) and three lithium(I) ions in l3- and l2-modes. The cis-conformation of oda2 may favor chelate coordination of Li1 and Li2. All the Li–O bond distances and angles are listed in the Table S1, all of which fall in the normal range [10]. As shown in Fig. 3, Co1 and Li2 are bridged by two carboxylate oxygen atoms (O6 and O7A) to form dimeric heterometallic building blocks. Further these dimeric building blocks are linked by three neighboring LiI centers and one CoII ions via five carboxylate oxygen atoms forming infinite Co–O–Li inorganic connectivity. Only a very limited number of 3D inorganic connectivity (within Table 1 Crystal data and structure refinement information for complex 1. 1 Empricial formula Fw Crystal syst. Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z F (0 0 0) Dcalc (Mg/m3) Flack parameter Absorption coefficient (mm1) Data/restraints/params Goodness of fit (GOF) on F2 R1a [I > 2r(I)] wR2a [I > 2r(I)] a
C8H8CoLi2O10 336.95 monoclinic P21 13.4400(13) 9.2798(9) 9.2817(9) 90.00 90.00 90.00 1157.62(19) 4 676 1.933 0.09(2) 1.533 2049/0/190 1.068 0.0315 0.0817
R1 ¼ R jj Fo j j Fc jj = j Fo j, ðwR2 ¼ ½RwðFo2 Fc2 Þ2=RwðFo2 Þ21=2Þ.
M
O
O O
O M
M M
O M
Scheme 1. Coordination mode of oda2 in 1.
M
Fig. 1. Perspective view of 1. Gray, C; red, O; yellow, Li; purple, Co. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. The hexa-dentate coordination mode of oda2 in 1. Gray, C; red, O; yellow, Li; purple, Co. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
organic–inorganic hybrids) are known, the 3D inorganic connectivity is desirable for properties resulting from cooperative phenomenon such as magnetism and conductivity [11]. For example, recently Bu and co-workers also use mixed-carboxylic acid ligands to obtain manganese and magnesium homo-chiral materials containing 3D inorganic connectivity [12]. It is noted that no typical strong O–H O hydrogen bonds can be observed in the 3D framework due to the rigid framework. 3.2. Magnetic properties The magnetic susceptibilities of complex 1 were measured in the temperature range from 2 to 300 K under 1000 Oe field as shown in Fig. 4. The vMT value at 300 K is 2.588 cm3 K mol1, which is greater than that expected for a high-spin CoII ion through the spin-only formula (calc. 1.88 cm3 K mol1 with g = 2.0). As the temperature decreases, the vMT value gradually reaches a minimum value of 1.564 cm3 K mol1 at 4.5 K. At a further decreasing temperature, the vMT value sharply increases to a value of 1.702 cm3 K mol1 at 2.0 K. The magnetic susceptibility above 35 K obeys the Curie–Weiss law with C = 2.8 cm3 K mol1 and a negative Weiss constant h = 21.9 K, which might be related to both antiferromagnet interaction and spin–orbit coupling effects for the CoII ion. The vMT value sharp increase at a low temperature below 4 K, a most probable reason for the unusual low-temperature rise in vMT value is a contamination of the sample with magnetic ‘nano-particles’, or another material, showing magnetic ordering [13]. In the structure of 1, the magnetic exchange interaction occurs mainly through the short carobxylate bridges. In order to get estimation of the strength of the magnetic exchange interaction, it may use the following simple phenomenological equation [14]:
vT ¼ AexpðE1 =kTÞ þ BexpðE2 =kTÞ
ð1Þ
Y. Yuan et al. / Inorganica Chimica Acta 407 (2013) 239–242
241
Fig. 3. 3D inorganic connectivity along a axis for (a) and 1D Co–O–Li chain for (b) in 1. Gray, C; red, O; yellow, Li; purple, Co. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
that in the low temperature, complex 1 shows weak ferromagnetic interaction, indicative of spin-canting behavior. Acknowledgments This work was supported financially by Tianjin Normal University (Grant No. 5RL090), the Natural Science Foundation of Tianjin (Grant No. 11JCYBJC03600), and Young Scientist Fund of China (Grant No. 21001080 and Grant No. 21301128)). Appendix A. Supplementary material X-ray crystallographic files in CIF format for 1 and some graphics. Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.ica.2013. 07.030. Fig. 4. The plot of vMT vs. T for complex 1 at 1 KOe. The red line represents the best fit of vMT according to Eq. (1). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Here A + B equals the Curie constant, and E1, E2 represent the spin–orbit coupling ‘‘activation energies’’ and the antiferromagP netic interaction one, respectively. The agreement factor R = (vm2 P 2 3 Tcalc vmTobs) / (vmTobs) is 4.27 10 . The value C = A + B = 2.84 cm3 K mol1 is in good agreement with Curie constant. The value E1/k = 57.3 K represents the effect of spin–orbit coupling, which is a little higher than the reported one [15]. The value E2 with a small exchange interaction J = 2.0 cm1 (J/ k = 2E2/k = 2.8 K) according to the Ising chain approximation [vT / exp(J/2kT)] is close to that reported by Masciocchi and coworkers [15], indicative of a weak antiferromagnetic interaction between CoII ions bridged by oxygen bridges.
4. Conclusions In summary, under hydrothermal conditions, a three-dimensional (3D) CoII and LiI heterometallic complex [CoLi2(oda)2]n (1) containing 1D Co–O–Li linkage has been isolated. 1 represents a 3D hybrid magnetic framework. Magnetic measurements indicate
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Inorganica Chimica Acta journal homepage: www.elsevier.com/locate/ica
A 3D heterometallic framework containing Co–O–Li linkages: Hydrothermal synthesis, crystal structure and magnetic property Yue Yuan, Dan Wang, Shi Xin Liu, Ying Wang ⇑, Ju Yan Liu ⇑, Bin Ding ⇑, Xiao Jun Zhao ⇑ Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Key Laboratory of Inorganic–Organic Hybrid Functional Material Chemistry, Tianjin Normal University, Ministry of Education, Tianjin 300387, People’s Republic of China
a r t i c l e
i n f o
Article history: Received 29 March 2013 Received in revised form 15 July 2013 Accepted 18 July 2013 Available online 2 August 2013 Keywords: Dioxyacetic acid Co–O–Li linkage Ligand conformations Magnetic property
a b s t r a c t Using dioxyacetic acid (H2oda), CoCl26H2O and LiOH, a three-dimensional (3D) heterometallic complex [CoLi2(oda)2]n (1) containing 1D Co–O–Li chains has been isolated under hydrothermal conditions. 1 represents a 3D hybrid magnetic rigid framework. To the best of our knowledge, such a chain with the arrangement of Co–O–Li linkages based on carboxylic acid has been first reported. Further analysis reveals that cis-conformation of dioxyacetic acid greatly favor chelate coordination of lithium(I) centers. Magnetic measurements indicate that in the low temperature, complex 1 shows weak ferromagnetic interaction, indicative of spin-canting behavior. Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction The design and syntheses of new metal–organic coordination architectures have attracted great attention not only because of their intriguing variety of architectures and topologies [1], but also their potential applicable properties in recent years [2]. Up to now, a great number of inorganic–organic hybrid coordination polymers have been reported based on the ligands containing O donors such as carboxylates [3], especially the dioxyacetic acid (H2oda). H2oda possesses the features of potential interest for corrosion inhibition [4,5], and its coordinatioin chemistry with the main-group metal ions, transition metal ions and lanthanoid(III) cations, which displayed novel supra-molecular structures [6,7]. As part of an ongoing research project dealing with the coordination chemistry of H2oda [7], herein we report the three-dimensional (3D) main group-transitional mixed-metal complex, namely, [CoLi(oda)2]n (1), which contains 1D Co–O–Li linkages under hydrothermal conditions. Magnetic measurements indicate that in the low temperature, complex 1 shows weak ferromagnetic interaction, indicative of spin-canting behavior. 2. Experimental 2.1. Materials and general methods All the solvents and reagents for synthesis were obtained commercially and used as received. Analyses for C, H, and N were ⇑ Corresponding authors. E-mail address: [email protected] (Y. Wang). 0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.ica.2013.07.030
carried out on a Perkin-Elmer 240 elemental analyzer. Powder X-ray diffraction (PXRD) measurements were recorded on a D/ Max-2500 X-ray diffractometer using Cu Ka radiation. The magnetisation data for 1 was recorded on a Quantum Design MPMS-XL7 SQUID magnetometer. Variable-temperature magnetic susceptibility measurements were performed in an applied field of 2 kOe in the temperature range of 300–1.8 K. The molar magnetic susceptibilities were corrected for the diamagnetism estimated from Pascal’s tables and for the sampleholder by a previous calibration. 2.2. Synthesis of complex 1 CoCl26H2O (0.0476 g, 0.2 mmol), H2oda (0.1341 g, 1.0 mmol), LiOH (0.0024 g, 0.1 mmol) and H2O (15 mL) were placed in a 25 mL Teflon-lined steel vessel and heated to 160 °C for 3 days, then cooled to room temperature. The resulting red block-shaped crystals for 1 were washed several times by water and diethyl ether. The yield is 65% based on CoCl26H2O. Elemental Anal. Calc. for 1 C8H8CoLi2O10 (336.95): Co, 17.49; Li, 4.12; C, 28.52; H, 2.39. Found: Co, 17.71; Li, 4.33; C, 28.56; H, 2.42%. Hydrothermal conditions are essential for the synthesis of 1, higher temperature may facilitate the formation of higher-dimensional inorganic connectivity. 2.3. Crystal structure determination X-ray single-crystal diffraction data for complex 1 was collected on an APEX II CCD at 293(2) K with a graphite-monochromated Mo Ka radiation (k = 0.71073 Å). The absorption correction was
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performed using the CRYSTAL CLEAR programs [8,9]. All non-hydrogen atoms were refined with anisotropic thermal parameters. Hydrogen atoms were located at geometrically calculated positions. Crystallographic data and structural refinements for complex 1 are summarized in Table 1. Selected bond lengths and angles are listed in Table S1. The coordination mode of H2oda is demonstrated in Scheme 1.
3. Results and discussion 3.1. Description of crystal structure of complex 1 X-ray single-crystal determination shows that 1 contains one crystallographic independent CoII ion (Co1), two crystallographic independent LiI ions (Li1 and Li2) and two oda2 ligands (Fig. 1). Co1 is in the octahedral geometry and six-coordinated by six oxygen atoms (O1, O9A, O4B, O2A, O7A, O6, and O2A) from four oda2 ligands (Fig. S1). Both Li1 and Li2 are located in the distorted square pyramid and penta-coordinated by five oxygen atoms from three oda2 ligands, as displayed in Fig. S2. Co1 Li2 and Co1C Li1 distances separated by two l2-bridged oxygen atoms are 3.151 and 3.051 Å, respectively. The carboxylic acid group of H2oda is fully de-protonated, as is illustrated in Fig. 2. The cis-ligand in complex 1 connects three cobalt(II) and three lithium(I) ions in l3- and l2-modes. The cis-conformation of oda2 may favor chelate coordination of Li1 and Li2. All the Li–O bond distances and angles are listed in the Table S1, all of which fall in the normal range [10]. As shown in Fig. 3, Co1 and Li2 are bridged by two carboxylate oxygen atoms (O6 and O7A) to form dimeric heterometallic building blocks. Further these dimeric building blocks are linked by three neighboring LiI centers and one CoII ions via five carboxylate oxygen atoms forming infinite Co–O–Li inorganic connectivity. Only a very limited number of 3D inorganic connectivity (within Table 1 Crystal data and structure refinement information for complex 1. 1 Empricial formula Fw Crystal syst. Space group a (Å) b (Å) c (Å) a (°) b (°) c (°) V (Å3) Z F (0 0 0) Dcalc (Mg/m3) Flack parameter Absorption coefficient (mm1) Data/restraints/params Goodness of fit (GOF) on F2 R1a [I > 2r(I)] wR2a [I > 2r(I)] a
C8H8CoLi2O10 336.95 monoclinic P21 13.4400(13) 9.2798(9) 9.2817(9) 90.00 90.00 90.00 1157.62(19) 4 676 1.933 0.09(2) 1.533 2049/0/190 1.068 0.0315 0.0817
R1 ¼ R jj Fo j j Fc jj = j Fo j, ðwR2 ¼ ½RwðFo2 Fc2 Þ2=RwðFo2 Þ21=2Þ.
M
O
O O
O M
M M
O M
Scheme 1. Coordination mode of oda2 in 1.
M
Fig. 1. Perspective view of 1. Gray, C; red, O; yellow, Li; purple, Co. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Fig. 2. The hexa-dentate coordination mode of oda2 in 1. Gray, C; red, O; yellow, Li; purple, Co. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
organic–inorganic hybrids) are known, the 3D inorganic connectivity is desirable for properties resulting from cooperative phenomenon such as magnetism and conductivity [11]. For example, recently Bu and co-workers also use mixed-carboxylic acid ligands to obtain manganese and magnesium homo-chiral materials containing 3D inorganic connectivity [12]. It is noted that no typical strong O–H O hydrogen bonds can be observed in the 3D framework due to the rigid framework. 3.2. Magnetic properties The magnetic susceptibilities of complex 1 were measured in the temperature range from 2 to 300 K under 1000 Oe field as shown in Fig. 4. The vMT value at 300 K is 2.588 cm3 K mol1, which is greater than that expected for a high-spin CoII ion through the spin-only formula (calc. 1.88 cm3 K mol1 with g = 2.0). As the temperature decreases, the vMT value gradually reaches a minimum value of 1.564 cm3 K mol1 at 4.5 K. At a further decreasing temperature, the vMT value sharply increases to a value of 1.702 cm3 K mol1 at 2.0 K. The magnetic susceptibility above 35 K obeys the Curie–Weiss law with C = 2.8 cm3 K mol1 and a negative Weiss constant h = 21.9 K, which might be related to both antiferromagnet interaction and spin–orbit coupling effects for the CoII ion. The vMT value sharp increase at a low temperature below 4 K, a most probable reason for the unusual low-temperature rise in vMT value is a contamination of the sample with magnetic ‘nano-particles’, or another material, showing magnetic ordering [13]. In the structure of 1, the magnetic exchange interaction occurs mainly through the short carobxylate bridges. In order to get estimation of the strength of the magnetic exchange interaction, it may use the following simple phenomenological equation [14]:
vT ¼ AexpðE1 =kTÞ þ BexpðE2 =kTÞ
ð1Þ
Y. Yuan et al. / Inorganica Chimica Acta 407 (2013) 239–242
241
Fig. 3. 3D inorganic connectivity along a axis for (a) and 1D Co–O–Li chain for (b) in 1. Gray, C; red, O; yellow, Li; purple, Co. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
that in the low temperature, complex 1 shows weak ferromagnetic interaction, indicative of spin-canting behavior. Acknowledgments This work was supported financially by Tianjin Normal University (Grant No. 5RL090), the Natural Science Foundation of Tianjin (Grant No. 11JCYBJC03600), and Young Scientist Fund of China (Grant No. 21001080 and Grant No. 21301128)). Appendix A. Supplementary material X-ray crystallographic files in CIF format for 1 and some graphics. Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.ica.2013. 07.030. Fig. 4. The plot of vMT vs. T for complex 1 at 1 KOe. The red line represents the best fit of vMT according to Eq. (1). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
Here A + B equals the Curie constant, and E1, E2 represent the spin–orbit coupling ‘‘activation energies’’ and the antiferromagP netic interaction one, respectively. The agreement factor R = (vm2 P 2 3 Tcalc vmTobs) / (vmTobs) is 4.27 10 . The value C = A + B = 2.84 cm3 K mol1 is in good agreement with Curie constant. The value E1/k = 57.3 K represents the effect of spin–orbit coupling, which is a little higher than the reported one [15]. The value E2 with a small exchange interaction J = 2.0 cm1 (J/ k = 2E2/k = 2.8 K) according to the Ising chain approximation [vT / exp(J/2kT)] is close to that reported by Masciocchi and coworkers [15], indicative of a weak antiferromagnetic interaction between CoII ions bridged by oxygen bridges.
4. Conclusions In summary, under hydrothermal conditions, a three-dimensional (3D) CoII and LiI heterometallic complex [CoLi2(oda)2]n (1) containing 1D Co–O–Li linkage has been isolated. 1 represents a 3D hybrid magnetic framework. Magnetic measurements indicate
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