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Volume 67 
Part 5 
Pages m145-m148  
May 2011  

Received 15 March 2011
Accepted 11 April 2011
Online 15 April 2011

Poly[tetra-[mu]2-L-lactato-indium(III)sodium(I)]

aCollege of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang, Jiangxi 330022, People's Republic of China
Correspondence e-mail: qyliuchem@hotmail.com

The asymmetric unit of the title compound, [InNa(C3H5O3)4]n, consists of one InIII ion, one NaI ion and four crystallographically independent L-lactate monoanions. The coordination of the InIII ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal-bipyramidal coordination geometry. The NaI ion is six-coordinated by four carboxylate O atoms and two hydroxy O atoms from four L-lactate ligands in a distorted octahedral geometry. Each InIII ion is coordinated by four surrounding L-lactate ligands to form an [In(L-lactate)4]- unit, which is further linked by NaI ions through Na-O bonds to give a two-dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.

Comment

The construction of coordination polymers with desired properties from multifunctional ligands with metal ions is of current interest and great importance because these materials can exhibit a variety of physical properties, such as catalysis, molecular magnetism, photoluminescence, adsorption and phase separation (Janiak, 2003[Janiak, C. (2003). J. Chem. Soc. Dalton Trans. pp. 2781-2804.]; Kitagawa et al., 2004[Kitagawa, S., Kitaura, R. & Noro, S. I. (2004). Angew. Chem. Int. Ed. 43, 2334-2375.]; O'Keeffe et al., 2000[O'Keeffe, M., Eddaoudi, M., Li, H. L., Reineke, T. & Yaghi, O. M. (2000). J. Solid State Chem. 152, 3-20.]). The rational synthesis of these materials, however, remains a great challenge. Ionothermal synthesis, a new synthetic methodology developed recently involving the use of an ionic liquid as both solvent and template in the preparation of crystalline solids, offers many advantages over traditional hydrothermal and solvothermal materials synthesis methods (Parnham & Morris, 2007[Parnham, E. R. & Morris, R. E. (2007). Acc. Chem. Res. 40, 1005-1013.]; Reichert et al., 2006[Reichert, W. M., Holbrey, J. D., Vigour, K. B., Morgan, T. D., Broker, G. A. & Rogers, R. D. (2006). Chem. Commun. pp. 4767-4779.]). Compared with traditional hydrothermal and solvothermal methods, the change from molecular to ionic reaction media leads to new types of materials being accessible, with structural properties that may be traced directly to the chemistry of the ionic liquid (IL) (Chen et al., 2008[Chen, S. M., Zhang, J. & Bu, X. H. (2008). Inorg. Chem. 47, 5567-5569.]; Zhang et al., 2010[Zhang, N., Liu, Q.-Y., Wang, Y.-L., Shan, Z.-M., Yang, E.-L. & Hu, H.-C. (2010). Inorg. Chem. Commun. 13, 706-710.]). Therefore, the ionic species of ILs may control the structures of the materials formed in ionothermal synthesis. There are some examples in which ILs have been successfully applied to the syntheses of novel coordination compounds (Chen et al., 2009[Chen, W.-X., Ren, Y.-P., Long, L.-S., Huang, R.-B. & Zheng, L.-S. (2009). CrystEngComm, 11, 1522-1525.]; Xu et al., 2007[Xu, L., Choi, E.-Y. & Kwon, Y.-U. (2007). Inorg. Chem. 46, 10670-10680.]). Of particular interest is a recent study by Morris and co-workers (Lin et al., 2007[Lin, Z., Slawin, A. M. Z. & Morris, R. E. (2007). J. Am. Chem. Soc. 129, 4880-4881.]) on the use of an enantiopure anion as one component of the IL to induce homochirality in a nickel(II) structure constructed of entirely achiral building blocks, despite the fact that the anion of the IL is not occluded by the material. Nevertheless, there are still relatively few examples of coordination polymers prepared by ionothermal reaction to date.

[Scheme 1]

The InIII ion is liable to hydrolysis, which limits its use in the construction of coordination compounds under hydrothermal or solvothermal conditions. However, InIII ions can be used to construct new frameworks under ionothermal conditions because the InIII ion will not hydrolyse in IL solvents. A series of In compounds prepared under ionothermal reaction conditions has been reported recently (Zhang et al., 2008[Zhang, J., Chen, S. M. & Bu, X. H. (2008). Angew. Chem. Int. Ed. 47, 5434-5437.]). We report here the title indium compound, poly[tetra-[mu]2-L-lactato-indium(III)sodium(I)], (I)[link]. To the best of our knowledge, no indium compound based on the lactate ligand has been reported previously.

The asymmetric unit of (I)[link] consists of one InIII ion, one NaI ion and four L-lactate monoanions. As depicted in Fig. 1[link], the In1 ion is seven-coordinated by five carboxylate O atoms (O1, O4, O7, O8 and O10) and two hydroxy O atoms (O3 and O6) from four L-lactate ligands in a pentagonal-bipyramidal coordination environment, with atoms O6 and O10 occupying the apical positions. The In-O bond lengths range from 2.133 (2) to 2.356 (2) Å and the O-In-O bond angles vary from 55.29 (8) to 164.80 (9)° (Table 1[link]). The Na1 ion is six-coordinated by two carboxylate O atoms [O2 and O5ii; symmetry code: (ii) x - 1, y, z] and two hydroxy O atoms [O12i and O9iii; symmetry codes: (i) -x + 1, y + [{1\over 2}], -z + [{1\over 2}]; (iii) -x + 1, y - [{1\over 2}], -z + [{1\over 2}]] in a distorted square-planar geometry, with two carboxylate O atoms (O8iii and O11i) in the apical positions. The Na1 ion is surrounded by four L-lactate ligands, with Na1-O distances varying from 2.364 (3) to 2.476 (3) Å (Fig. 1[link] and Table 1[link]). The [NaO6] octahedron is distorted, with O-Na-O bond angles varying from 65.13 (8) to 175.47 (11)° (Table 1[link]).

Though all the L-lactate ligands bridge one InIII ion and one NaI ion, the four crystallographically independent L-lactate ligands display three different coordination modes. The first type of L-lactate ligand chelates an InIII ion through its hydroxy O atom (O3) and one carboxylate O atom (O1), and bridges an NaI ion through its second carboxylate O atom (O2) (Fig. 2[link]). The second type of L-lactate ligand coordination is similar to the first; it chelates an NaI ion through its hydroxy O atom (O12) and one carboxylate O atom (O11), and bridges an InIII ion through its second carboxylate O atom (O10). The third type of L-lactate ligand employs its carboxylate group (O7 and O8) to chelate an InIII ion, and its hydroxy O atom (O9) and one of its carboxylate O atoms (O8) to chelate an NaI ion. Therefore, there is a [mu]2-O (O8) bridge present in this type of L-lactate ligand.

Each InIII ion is coordinated by four surrounding L-lactate ligands to form an [In(L-lactate)4]- unit (Fig. 2[link]). Each of these [In(L-lactate)4]- units is linked by four neighbouring NaI ions through Na-O bonds to generate a two-dimensional layer along the ab plane (Fig. 3[link]). Within the layer, there are hydrogen bonds between the hydroxy groups and the carboxylate O atoms [O3...O2i and O6...O5iv; symmetry code: (iv) -x + 2, y + [{1\over 2}], -z + [{1\over 2}]] (Table 2[link]). The two-dimensional layers are stacked along the c direction to produce the crystal packing (Fig. 4[link]). Interlayer hydrogen bonds are observed between the hydroxy groups and the carboxylate O atoms [O9...O10v and O12...O7vi; symmetry codes: (v) x + [{1\over 2}], -y + [{3\over 2}], -z; (vi) x - [{1\over 2}], -y + [{1\over 2}], -z] (Table 2[link]).

Some coordination compounds incorporating the lactate ligand have been reported previously. Most of them are mononuclear structures, such as [Co(lactate)2(H2O)2]·H2O (Carballo et al., 2002[Carballo, R., Covelo, B., Vázquez-López, E. M., Castiñeiras, A. & Niclós, J. (2002). Z. Anorg. Allg. Chem. 628, 468-472.]), [Mn(lactate)2(H2O)2] (Lis, 1982[Lis, T. (1982). Acta Cryst. B38, 937-939.]) and [Al(lactate)3] (Bombi et al., 1990[Bombi, G. G., Corain, B., Sheikh-Osman, A. A. & Valle, G. C. (1990). Inorg. Chim. Acta, 171, 79-83.]). A few compounds with two-dimensional structures containing bridging lactate ligands have also been reported. However, all of them are homometallic compounds. For example, {[Eu(lactate)2(H2O)2]ClO4}n possesses a cationic two-dimensional laminar layer charged with the perchlorate ions (Qu et al., 2008[Qu, Z.-R., Ye, Q., Zhao, H., Fu, D.-W., Ye, H.-Y., Xiong, R.-G., Akutagawa, T. & Nakamura, T. (2008). Chem. Eur. J. 14, 3452-3456.]). In the [Cu(lactate)2]n complex (Balboa et al., 2007[Balboa, S., Castiñeiras, A., Herle, P. S. & Strähle, J. (2007). Z. Anorg. Allg. Chem. 633, 2420-2424.]), the lactate ligand chelates a CuII ion through its hydroxy O atom and one carboxylate O atom, and bridges one CuII ion through the second carboxylate O atom, to generate a neutral two-dimensional framework where the basic structural unit is the mononuclear [Cu(lactate)2] unit.

[Figure 1]
Figure 1
The structure of (I)[link], showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Methyl H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 1, y + [{1\over 2}], -z + [{1\over 2}]; (ii) x - 1, y, z; (iii) -x + 1, y - [{1\over 2}], -z + [{1\over 2}].]
[Figure 2]
Figure 2
A view of the [In(L-lactate)4]- unit surrounded by four NaI ions. [Symmetry codes: (i) -x + 1, y + [{1\over 2}], -z + [{1\over 2}]; (iii) -x + 1, y - [{1\over 2}], -z + [{1\over 2}]; (vi) x + 1, y, z.]
[Figure 3]
Figure 3
A perspective view of the two-dimensional layered structure of (I)[link]. H atoms have been omitted for clarity. Dashed lines between hydroxy O and carboxylate O atoms indicate hydrogen bonds. [Symmetry codes: (i) -x + 1, y + [{1\over 2}], -z + [{1\over 2}]; (iv) -x + 2, y + [{1\over 2}], -z + [{1\over 2}].]
[Figure 4]
Figure 4
A view of the packing of (I)[link] along the a axis. H atoms have been omitted for clarity. Dashed lines between hydroxy O and carboxylate O atoms indicate interlayer hydrogen bonds.

Experimental

In(NO3)3·4.5H2O (229.2 mg, 0.6 mmol) and the monosodium salt of 5-sulfoisophthalic acid (53.6 mg, 0.2 mmol) were mixed with 1-ethyl-3-methylimidazolium L-lactate (0.6 g) in a 25 ml Parr Teflon-lined stainless steel vessel. The vessel was sealed and heated to 413 K. The temperature was maintained for 12 d and then the mixture was allowed to cool naturally to obtain colourless crystals of (I)[link] [yield 51%, based on In(NO3)3·4.5H2O]. IR (KBr pellet, [nu], cm-1): 3465, 3391, 3105, 2950, 1638, 1598, 1564, 1473, 1417, 1254, 1124, 1073, 954, 868, 776, 666, 588, 540, 518.

Crystal data
  • [InNa(C3H5O3)4]

  • Mr = 494.09

  • Orthorhombic, P 21 21 21

  • a = 9.4744 (12) Å

  • b = 9.5803 (12) Å

  • c = 19.145 (2) Å

  • V = 1737.7 (4) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 1.45 mm-1

  • T = 296 K

  • 0.18 × 0.13 × 0.09 mm

Data collection
  • Bruker APEXII area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.781, Tmax = 0.881

  • 10916 measured reflections

  • 4259 independent reflections

  • 3680 reflections with I > 2[sigma](I)

  • Rint = 0.029

Refinement
  • R[F2 > 2[sigma](F2)] = 0.029

  • wR(F2) = 0.057

  • S = 1.02

  • 4259 reflections

  • 247 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • [Delta][rho]max = 0.45 e Å-3

  • [Delta][rho]min = -0.42 e Å-3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), with 1766 Friedel pairs

  • Flack parameter: 0.03 (2)

Table 1
Selected geometric parameters (Å, °)

In1-O10 2.133 (2)
In1-O4 2.162 (2)
In1-O1 2.183 (2)
In1-O6 2.217 (2)
In1-O3 2.255 (2)
In1-O8 2.338 (2)
In1-O7 2.356 (2)
Na1-O12i 2.364 (3)
Na1-O5ii 2.423 (3)
Na1-O2 2.435 (3)
Na1-O8iii 2.437 (2)
Na1-O11i 2.462 (2)
Na1-O9iii 2.476 (3)
O10-In1-O4 122.10 (9)
O10-In1-O1 91.88 (9)
O4-In1-O1 81.77 (10)
O10-In1-O6 164.80 (9)
O4-In1-O6 73.05 (8)
O1-In1-O6 91.77 (10)
O10-In1-O3 83.36 (9)
O1-In1-O3 72.36 (9)
O6-In1-O3 83.70 (9)
O10-In1-O8 93.10 (8)
O6-In1-O8 75.68 (8)
O3-In1-O8 74.12 (8)
O10-In1-O7 87.13 (9)
O4-In1-O7 81.37 (9)
O6-In1-O7 94.55 (9)
O8-In1-O7 55.29 (8)
O12i-Na1-O2 99.82 (12)
O5ii-Na1-O2 88.19 (8)
O12i-Na1-O8iii 110.79 (10)
O5ii-Na1-O8iii 77.75 (9)
O2-Na1-O8iii 85.24 (10)
O12i-Na1-O11i 66.95 (9)
O5ii-Na1-O11i 103.98 (11)
O2-Na1-O11i 98.95 (12)
O8iii-Na1-O11i 175.47 (11)
O12i-Na1-O9iii 84.43 (10)
O5ii-Na1-O9iii 92.82 (11)
O8iii-Na1-O9iii 65.13 (8)
O11i-Na1-O9iii 110.47 (11)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) x-1, y, z; (iii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Table 2
Hydrogen-bond geometry (Å, °)

D-H...A D-H H...A D...A D-H...A
O3-H3...O2i 0.86 (4) 1.76 (4) 2.620 (3) 177 (4)
O6-H6...O5iv 0.82 (4) 1.77 (4) 2.578 (4) 170 (4)
O9-H9...O10v 0.83 (4) 2.26 (4) 3.087 (4) 173 (4)
O12-H12...O7vi 0.87 (4) 2.05 (4) 2.916 (3) 173 (4)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) [-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (v) [x+{\script{1\over 2}}], [-y+{\script{3\over 2}}, -z]; (vi) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

H atoms bonded to C atoms were placed in calculated positions and treated using a riding-model approximation, with C-H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl groups, and C-H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for methylidyne groups. Hydroxy H atoms were located in a difference map and refined with Uiso(H) = 1.5Ueq(O).

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND. Version 3.0. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.


Supplementary data for this paper are available from the IUCr electronic archives (Reference: LG3055 ). Services for accessing these data are described at the back of the journal.


Acknowledgements

This work was support by the National Natural Science Foundation of China (grant No. 20901033), the Scientific Research Foundation for the Returned Overseas Chinese Scholars (SEM), the NSF of Jiangxi Provincial (grant No. 2009GZH0056) and the Project of Education Department of Jiangxi Province (grant Nos. GJJ10016 and GJJ11381).

References

Balboa, S., Castiñeiras, A., Herle, P. S. & Strähle, J. (2007). Z. Anorg. Allg. Chem. 633, 2420-2424.  [ChemPort]
Bombi, G. G., Corain, B., Sheikh-Osman, A. A. & Valle, G. C. (1990). Inorg. Chim. Acta, 171, 79-83.  [ChemPort]
Brandenburg, K. (2005). DIAMOND. Version 3.0. Crystal Impact GbR, Bonn, Germany.
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Carballo, R., Covelo, B., Vázquez-López, E. M., Castiñeiras, A. & Niclós, J. (2002). Z. Anorg. Allg. Chem. 628, 468-472.  [CSD] [CrossRef] [ChemPort]
Chen, W.-X., Ren, Y.-P., Long, L.-S., Huang, R.-B. & Zheng, L.-S. (2009). CrystEngComm, 11, 1522-1525.  [ChemPort]
Chen, S. M., Zhang, J. & Bu, X. H. (2008). Inorg. Chem. 47, 5567-5569.  [ISI] [PubMed] [ChemPort]
Flack, H. D. (1983). Acta Cryst. A39, 876-881.  [CrossRef] [details]
Janiak, C. (2003). J. Chem. Soc. Dalton Trans. pp. 2781-2804.
Kitagawa, S., Kitaura, R. & Noro, S. I. (2004). Angew. Chem. Int. Ed. 43, 2334-2375.  [ISI] [CrossRef] [ChemPort]
Lin, Z., Slawin, A. M. Z. & Morris, R. E. (2007). J. Am. Chem. Soc. 129, 4880-4881.  [ISI] [PubMed] [ChemPort]
Lis, T. (1982). Acta Cryst. B38, 937-939.  [CrossRef] [details]
O'Keeffe, M., Eddaoudi, M., Li, H. L., Reineke, T. & Yaghi, O. M. (2000). J. Solid State Chem. 152, 3-20.  [ISI] [CrossRef] [ChemPort]
Parnham, E. R. & Morris, R. E. (2007). Acc. Chem. Res. 40, 1005-1013.  [ISI] [PubMed] [ChemPort]
Qu, Z.-R., Ye, Q., Zhao, H., Fu, D.-W., Ye, H.-Y., Xiong, R.-G., Akutagawa, T. & Nakamura, T. (2008). Chem. Eur. J. 14, 3452-3456.  [ChemPort]
Reichert, W. M., Holbrey, J. D., Vigour, K. B., Morgan, T. D., Broker, G. A. & Rogers, R. D. (2006). Chem. Commun. pp. 4767-4779.  [CSD] [CrossRef]
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [details]
Xu, L., Choi, E.-Y. & Kwon, Y.-U. (2007). Inorg. Chem. 46, 10670-10680.  [ISI] [CSD] [CrossRef] [PubMed] [ChemPort]
Zhang, J., Chen, S. M. & Bu, X. H. (2008). Angew. Chem. Int. Ed. 47, 5434-5437.  [ChemPort]
Zhang, N., Liu, Q.-Y., Wang, Y.-L., Shan, Z.-M., Yang, E.-L. & Hu, H.-C. (2010). Inorg. Chem. Commun. 13, 706-710.  [ChemPort]


Acta Cryst (2011). C67, m145-m148   [ doi:10.1107/S0108270111013606 ]