- Email: [email protected]
Synthesis and structure analysis of three new lanthanide complexes, [Ce(NO3)6]·[(H-phen)6·(NO3)3], [Pr(NO3)6]·[(H-phen)6·(NO3)3] and [Sm(NO3)3·(phen)·(H2O)2]·[(H-phen)·(NO3)·H2O]
Accepted Manuscript Research paper Synthesis and structure analysis of three new lanthanide complexes, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(H-phen)6.(NO3)3] and [Sm(NO3)3].(phen).(H2O)2].[(H- phen).(NO3).H2O] Lopamudra Giri, V.R. Pedireddi PII: DOI: Reference:
S0020-1693(17)31780-2 https://doi.org/10.1016/j.ica.2018.03.021 ICA 18166
To appear in:
Inorganica Chimica Acta
Received Date: Revised Date: Accepted Date:
18 November 2017 6 January 2018 9 March 2018
Please cite this article as: L. Giri, V.R. Pedireddi, Synthesis and structure analysis of three new lanthanide complexes, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(H-phen)6.(NO3)3] and [Sm(NO3)3].(phen).(H2O)2].[(H- phen). (NO3).H2O], Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.03.021
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Synthesis and structure analysis of three new lanthanide complexes, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(H-phen)6.(NO3)3] and [Sm(NO3)3].(phen).(H2O)2].[(Hphen).(NO3).H2O] Lopamudra Giri* and V. R. Pedireddi Solid State & Supramolecular Structural Chemistry Laboratory, School of Basic Sciences, Indian Institute of Technology Bhubaneswar, Argul, Bhubaneswar 752 050, India. Email: [email protected] Abstract Three coordination assemblies, 1 – 3, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(Hphen)6.(NO3)3,] and [Sm(NO3)3(phen)(H2O)2].[(H-phen).(NO3).H2O], respectively, wherein (H-phen = 1,10-phenanthroline), have been reported. In the complexes of 1 and 2, secondary coordination spheres yield a host-network, into which primary coordination sphere is encapsulated. In the complex, 3, however, both primary and secondary coordination spheres direct the formation of crossed ribbon structure, with voids being filled by water molecules. Nevertheless, acid molecules did not present in any of the complexes 1 – 3. Threedimensional structures are determined by single crystal X-ray diffraction method and the analysis of packing of the molecules within the crystal lattices has been discussed in detail. Keywords: Host-guest Assembly; X-ray Diffraction; Lanthanides
Introduction Metal-organic Framework (MOF) structures are well known for their various potential applications in the areas of gas storage, catalysis, selectivity etc., thus, led to the synthesis of a myriad of such network structures as reported in the recent literature.1-6 Amongst notable examples, carboxylate mediated complexes are of great significance, especially to tune the porosity in the complexes.7-11 But, it is noteworthy to mention that transition metal based complexes of aryl carboxylates are thoroughly explored than lanthanides, as reported in the recent literature.12-15 However, since lanthanides are well-known for various divergent properties starting from spectroscopy to magnetism, a systematic study of lanthanide series of metal complexes through carboxylates and also possibly along with other auxiliary ligands would be of great immense value addition for the development of novel tailor-made ensembles.16-21 Thus, our endeavours begin with the programming of synthesis of different assemblies, as specified in Chart 1, considering the ability of -COOH and 1,10phenanthroline to coordinate with lanthanide ions. However, unlike in the case of with transition metal ions mediated complexes, carboxylic acids did not take part at all in either of the complexes, either as a coordinated species to metal or as a free entity. The structural features and systematic packing analysis of these complexes have been elucidated using the data obtained from single crystal X-ray diffraction experiments, as discussed below. Chart I Ce(NO3)3.6H2O
Pr(NO3)3.6H2O
rac-1,3-cyclohexanedicarboxylic acid
1,10-phenanthroline (phen)
Sm(NO3)3.6H2O
1
2
3
Experimental The complexes studied herein were synthesized by following conventional crystallization methods, for example, slow-evaporation of the solutions.
In a typical
experiment, 108 mg of cerium nitrate dissolved in 5 mL of CH3OH, was added to a 25 mL solution of a mixture of rac-1,3-cyclohexanedicarboxylic acid (43 mg, 0.25 mmol) and 1,10phenanthroline (45 mg, 0.25 mmol) at ambient conditions and kept for slow evaporation. Good quality single crystals were obtained within 72 h. Crystal Structure determination Good quality single crystals of all the complexes 1 - 3 were chosen after being viewed under Leica microscope and glued to glass fiber by using an adhesive and mounted on the goniometer of Bruker single-crystal X-ray diffractometer (D8 VENTURE) equipped with a PHOTON 100 CMOS detector. In all the cases data collection was smooth without any complications, and all the crystals were stable throughout the data collection period. Data collection was performed using and scans. The structures were determined using intrinsic phasing method followed by full-matrix least-squares refinement against F2 using SHELXTL. All non-hydrogen atoms were refined by anisotropic method and hydrogen atoms were either refined or placed in calculated positions. All the structural refinements converged to good R-factors, as listed in Table 1, and the intermolecular interactions were computed by using PLATON software (Table 2). The packing diagrams were generated by using Diamond (version 3.2.6.0) and Mercury (version 3.9).
Results and discussion Structures of co-ordination assemblies of [Ce(NO3)6].[(H-phen)6.(NO3)3], (1) and [Pr(NO3)6].
[(H-phen)6.(NO3)3], (2): Crystals obtained from the respective CH3OH
solutions as detailed in the experimental section, gave identical unit cell dimensions, upon structure determination by X-ray diffraction methods. parameters are listed in Table 1.
The pertinent crystallographic
The data reveals that assemblies of 1 and 2 show
isostructural relation with the crystals adopting a R c space group in trigonal crystal system. The molecular contents in the crystal lattices are given in Figures 1(a) and (b) for 1 and 2, respectively, in the form of ORTEP.
(b)
(a)
(c)
(d)
(e)
(f)
Figure 1. (a) and (b) ORTEP of molecular units present in the crystal structures of 1 and 2, respectively. (c) Host-guest arrangement observed in the crystal structures of 1 and 2 (shown only for 1) with two types of voids, being occupied by primary coordination spheres and nitrate ions. (d) and (e) Interaction between the host and guest species. (f) Projection of arrangement along the stacking direction with layers of H-phen sandwiching primary coordination sphere and nitrate ions. Table 1. Crystallographic parameters of crystal structures of complexes 1, 2 and 3. Parameters
1
2
3
Formula
[Ce(NO3)6] [(C12H9N2)6.(NO3)3] 1785.48 Block Colourless Trigonal R c 293(2) 0.71073 17.533(1) 17.533(1) 40.030(1) 90 90 120 10657.1(1) 6 1.669 0.746 56.67 -22 ≤ h ≤ 22 -23 ≤ k ≤23 -53 ≤ l ≤ 53 5442 40673 2963 2321 184 0.032 0.079 1.063 1580436
[Pr(NO3)6] [(C12H9N2))6.(NO3)3] 1786.27 Block Colourless Trigonal R c 293(2) 0.71073 17.565(1) 17.565(1) 40.173(1) 90 90 120 10724.1(1) 6 1.660 0.786 52.89 -22 ≤ h ≤22 -21 ≤ k ≤ 21 -50 ≤ l ≤ 50 5448 42865 2455 2070 184 0.033 0.082 1.134 1580437
[Sm(NO3)3(C12H8N2)( H2O)2] [(C12H9N2).(NO3).H2O] 813.86 Block Colourless Triclinic P 293(2) 0.71073 8.033(1) 9.728(1) 19.546(3) 93.65(1) 92.01(1) 101.62(1) 1491.4(1) 2 1.813 2.056 57.28 -10≤ h ≤ 10 -13 ≤ k ≤ 13 -26 ≤ l ≤ 26 810 52451 7535 6496 517 0.027 0.059 1.031 1580438
Mr crystal shape crystal colour crystal system space group T, K λ(Mo-Kα)/Å a/Å b/Å c/Å α/0 β/0 γ/0 V/Å3 Z Dc / g cm-3 µ, mm-1 2θ range [0] limiting indices
F(000) total reflections unique reflections reflection at I ˃ 2σ (I) No. of parameters R1, I ˃ 2σ (I) wR2 I ˃ 2σ (I) GoF on F2
CCDC No.
In each of the structures, the metal species (Ce(III) or Pr(III)) are surrounded by six nitrate groups through a total of twelve Ce-O and Pr-O coordination bonds, as listed in Table 2. The observed distances in the range 2.62 - 2.66, Å, in the structures of 1 and 2, indeed are well in agreement with such distances observed in the related structures. It is pertinent to note that literature search reveals that, in fact, such hexanitrate coordinated lanthanide ions were reported earlier also,22 but not for the Ce(III) and Pr(III). In further structure analysis, it is noted that such coordination networks, thus, created anionic primary coordination spheres (see Figures 1(a) and (b)), with twelve coordination environment around each metal species. Apart from it, in the lattices, uncoordinated three nitrate molecules and six protonated Hphen are also present balancing the charge appropriately. In fact, this is very much similar composition as reported for Eu(III) species in the literature. 22 Table 2. Selective bond distances in the coordination assemblies 1 – 3. Ce(1) – O(3) Ce(1) – O(4)
1 2.658(1) 2.624(2)
Pr(1) – O(1) Pr(1) – O(2)
2 2.614(2) 2.649(3)
Sm(1) – O(1) Sm(1) – O(2) Sm(1) – O(3) Sm(1) – O(4) Sm(1) – O(6) Sm(1) – O(7) Sm(1) – O(9) Sm(1) – O(10) Sm(1) – N(4) Sm(1) – N(5)
3 2.430(2) 2.444(1) 2.490(1) 2.646(2) 2.542(3) 2.530(1) 2.535(2) 2.517(1) 2.613(1) 2.617(4)
In the packing analysis of the molecules, further, it was noted that a host-guest network is realized with the creation of voids of two types, into which primary coordination spheres or uncoordinated nitrate ions are embedded, as shown in Figure 1(c). Within each void, the primary coordination sphere is connected to six host molecules through C-H…O hydrogen bonds with H…O distance of 2.50 Å. However, nitrate ions are connected to three host molecules through N+-H…O- hydrogen bonds with H…O- distance of 2.16 Å. Such interactions are shown in Figure 1(d) and (e). In three-dimensional arrangement, along the
stacking direction, the molecules are oriented in such a way that the primary coordination spheres and nitrates are being sandwiched between the layers of H-phen molecules, as represented in Figure 1(f). Extending the study to further metal ions to evaluate recurrence of isostructurality, Sm(III) salt is employed in the co-crystallization process, keeping other reactants intact and the obtained crystals are analyzed by single crystal x-ray diffraction methods.
Table 3. Hydrogen bond distances (Å) and angles ( ) for 1 and molecular complexes 1- 3. D–H…A C–H…O N+–H…OO–H…OO–H…O
2.50 2.16
1 3.51 2.90
165 140
2.48 2.12
2 3.51 2.91
3 166 139
2.20 2.72 2.75 2.20
2.81 2.96 3.28 2.91
156 164 140 171
Three columns for each structure represent H…A, D…A distances and D-H…A angles, respectively, for a typical hydrogen bond, being represented as D-H…A. #
Structure of [Sm(NO3)3].(phen).(H2O)2].[(H-phen).(NO3).H2O], (3): In the crystals of 3, unlike in 1 and 2, the metal ion is coordinated to only three nitrate ions, two water molecules and a H-phen through Sm-O and Sm-N bonds, yielding a neutral ten coordination sphere of Sm(III), in a triclinic space group P . The complete structure determination and refinement parameters are listed in Table 1. The contents present in the crystal lattice are shown in Figure 2(a).
(a)
(b)
(c)
Figure 2. (a) Structural units in the crystal lattice of 3. (b) Packing of molecules in the crystal structure of 3, in the form of crossed ribbons. (c) The 2D supramolecular network extended by hydrogen bonding interactions.
The observed Sm-O and Sm-N bonds, in the range 2.43 - 2.62 Å (see Table 2), , in are in agreement with the distances noted in the related structures reported in the literature. Further, uncoordinated but protonated H-phen molecule is also present along with a nitrate ion and a H2O molecule (see Figure 2(a)). Such variations in the asymmetric unit is also well reflected in the different packing arrangement of molecules in 3 than in 1 and 2.
In the
crystal packing of complex 3 each nitrate anion is hydrogen bonded to the coordination sphere as well as H-phen molecule (via N+–H…O-, O–H…O-), while the guest water molecules establish only an interaction with coordination sphere through O-H…O hydrogen bond with H…O distance of 2.20 Å to form 2D sheets (Figure 2(b)), which are extended further in 3D, resulting a crossed ribbons structure as depicted in Figure 2(c).
Conclusions: In this report, preparation and structure characterization by single crystal X-ray diffraction methods of three new coordination assemblies of 1,10-phenanthroline with Ce(III), Pr(III) and Sm(III) have been illustrated.
In all these structures, the three-
dimensional assemblies are realized through the effective role played by the second coordination spheres.
Acknowledgments: We gratefully acknowledge IIT Bhubaneswar for the financial support.
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Three new coordination polymer of 1,10-phenanthroline with Ce(III), Pr(III) and Sm(III). Role of secondary coordination spheres for complex formation. Formation of exotic host-guest networks by lanthanides. Utilization of noncovalent interactions for structure stabilization.
S0020-1693(17)31780-2 https://doi.org/10.1016/j.ica.2018.03.021 ICA 18166
To appear in:
Inorganica Chimica Acta
Received Date: Revised Date: Accepted Date:
18 November 2017 6 January 2018 9 March 2018
Please cite this article as: L. Giri, V.R. Pedireddi, Synthesis and structure analysis of three new lanthanide complexes, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(H-phen)6.(NO3)3] and [Sm(NO3)3].(phen).(H2O)2].[(H- phen). (NO3).H2O], Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.03.021
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Synthesis and structure analysis of three new lanthanide complexes, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(H-phen)6.(NO3)3] and [Sm(NO3)3].(phen).(H2O)2].[(Hphen).(NO3).H2O] Lopamudra Giri* and V. R. Pedireddi Solid State & Supramolecular Structural Chemistry Laboratory, School of Basic Sciences, Indian Institute of Technology Bhubaneswar, Argul, Bhubaneswar 752 050, India. Email: [email protected] Abstract Three coordination assemblies, 1 – 3, [Ce(NO3)6].[(H-phen)6.(NO3)3], [Pr(NO3)6].[(Hphen)6.(NO3)3,] and [Sm(NO3)3(phen)(H2O)2].[(H-phen).(NO3).H2O], respectively, wherein (H-phen = 1,10-phenanthroline), have been reported. In the complexes of 1 and 2, secondary coordination spheres yield a host-network, into which primary coordination sphere is encapsulated. In the complex, 3, however, both primary and secondary coordination spheres direct the formation of crossed ribbon structure, with voids being filled by water molecules. Nevertheless, acid molecules did not present in any of the complexes 1 – 3. Threedimensional structures are determined by single crystal X-ray diffraction method and the analysis of packing of the molecules within the crystal lattices has been discussed in detail. Keywords: Host-guest Assembly; X-ray Diffraction; Lanthanides
Introduction Metal-organic Framework (MOF) structures are well known for their various potential applications in the areas of gas storage, catalysis, selectivity etc., thus, led to the synthesis of a myriad of such network structures as reported in the recent literature.1-6 Amongst notable examples, carboxylate mediated complexes are of great significance, especially to tune the porosity in the complexes.7-11 But, it is noteworthy to mention that transition metal based complexes of aryl carboxylates are thoroughly explored than lanthanides, as reported in the recent literature.12-15 However, since lanthanides are well-known for various divergent properties starting from spectroscopy to magnetism, a systematic study of lanthanide series of metal complexes through carboxylates and also possibly along with other auxiliary ligands would be of great immense value addition for the development of novel tailor-made ensembles.16-21 Thus, our endeavours begin with the programming of synthesis of different assemblies, as specified in Chart 1, considering the ability of -COOH and 1,10phenanthroline to coordinate with lanthanide ions. However, unlike in the case of with transition metal ions mediated complexes, carboxylic acids did not take part at all in either of the complexes, either as a coordinated species to metal or as a free entity. The structural features and systematic packing analysis of these complexes have been elucidated using the data obtained from single crystal X-ray diffraction experiments, as discussed below. Chart I Ce(NO3)3.6H2O
Pr(NO3)3.6H2O
rac-1,3-cyclohexanedicarboxylic acid
1,10-phenanthroline (phen)
Sm(NO3)3.6H2O
1
2
3
Experimental The complexes studied herein were synthesized by following conventional crystallization methods, for example, slow-evaporation of the solutions.
In a typical
experiment, 108 mg of cerium nitrate dissolved in 5 mL of CH3OH, was added to a 25 mL solution of a mixture of rac-1,3-cyclohexanedicarboxylic acid (43 mg, 0.25 mmol) and 1,10phenanthroline (45 mg, 0.25 mmol) at ambient conditions and kept for slow evaporation. Good quality single crystals were obtained within 72 h. Crystal Structure determination Good quality single crystals of all the complexes 1 - 3 were chosen after being viewed under Leica microscope and glued to glass fiber by using an adhesive and mounted on the goniometer of Bruker single-crystal X-ray diffractometer (D8 VENTURE) equipped with a PHOTON 100 CMOS detector. In all the cases data collection was smooth without any complications, and all the crystals were stable throughout the data collection period. Data collection was performed using and scans. The structures were determined using intrinsic phasing method followed by full-matrix least-squares refinement against F2 using SHELXTL. All non-hydrogen atoms were refined by anisotropic method and hydrogen atoms were either refined or placed in calculated positions. All the structural refinements converged to good R-factors, as listed in Table 1, and the intermolecular interactions were computed by using PLATON software (Table 2). The packing diagrams were generated by using Diamond (version 3.2.6.0) and Mercury (version 3.9).
Results and discussion Structures of co-ordination assemblies of [Ce(NO3)6].[(H-phen)6.(NO3)3], (1) and [Pr(NO3)6].
[(H-phen)6.(NO3)3], (2): Crystals obtained from the respective CH3OH
solutions as detailed in the experimental section, gave identical unit cell dimensions, upon structure determination by X-ray diffraction methods. parameters are listed in Table 1.
The pertinent crystallographic
The data reveals that assemblies of 1 and 2 show
isostructural relation with the crystals adopting a R c space group in trigonal crystal system. The molecular contents in the crystal lattices are given in Figures 1(a) and (b) for 1 and 2, respectively, in the form of ORTEP.
(b)
(a)
(c)
(d)
(e)
(f)
Figure 1. (a) and (b) ORTEP of molecular units present in the crystal structures of 1 and 2, respectively. (c) Host-guest arrangement observed in the crystal structures of 1 and 2 (shown only for 1) with two types of voids, being occupied by primary coordination spheres and nitrate ions. (d) and (e) Interaction between the host and guest species. (f) Projection of arrangement along the stacking direction with layers of H-phen sandwiching primary coordination sphere and nitrate ions. Table 1. Crystallographic parameters of crystal structures of complexes 1, 2 and 3. Parameters
1
2
3
Formula
[Ce(NO3)6] [(C12H9N2)6.(NO3)3] 1785.48 Block Colourless Trigonal R c 293(2) 0.71073 17.533(1) 17.533(1) 40.030(1) 90 90 120 10657.1(1) 6 1.669 0.746 56.67 -22 ≤ h ≤ 22 -23 ≤ k ≤23 -53 ≤ l ≤ 53 5442 40673 2963 2321 184 0.032 0.079 1.063 1580436
[Pr(NO3)6] [(C12H9N2))6.(NO3)3] 1786.27 Block Colourless Trigonal R c 293(2) 0.71073 17.565(1) 17.565(1) 40.173(1) 90 90 120 10724.1(1) 6 1.660 0.786 52.89 -22 ≤ h ≤22 -21 ≤ k ≤ 21 -50 ≤ l ≤ 50 5448 42865 2455 2070 184 0.033 0.082 1.134 1580437
[Sm(NO3)3(C12H8N2)( H2O)2] [(C12H9N2).(NO3).H2O] 813.86 Block Colourless Triclinic P 293(2) 0.71073 8.033(1) 9.728(1) 19.546(3) 93.65(1) 92.01(1) 101.62(1) 1491.4(1) 2 1.813 2.056 57.28 -10≤ h ≤ 10 -13 ≤ k ≤ 13 -26 ≤ l ≤ 26 810 52451 7535 6496 517 0.027 0.059 1.031 1580438
Mr crystal shape crystal colour crystal system space group T, K λ(Mo-Kα)/Å a/Å b/Å c/Å α/0 β/0 γ/0 V/Å3 Z Dc / g cm-3 µ, mm-1 2θ range [0] limiting indices
F(000) total reflections unique reflections reflection at I ˃ 2σ (I) No. of parameters R1, I ˃ 2σ (I) wR2 I ˃ 2σ (I) GoF on F2
CCDC No.
In each of the structures, the metal species (Ce(III) or Pr(III)) are surrounded by six nitrate groups through a total of twelve Ce-O and Pr-O coordination bonds, as listed in Table 2. The observed distances in the range 2.62 - 2.66, Å, in the structures of 1 and 2, indeed are well in agreement with such distances observed in the related structures. It is pertinent to note that literature search reveals that, in fact, such hexanitrate coordinated lanthanide ions were reported earlier also,22 but not for the Ce(III) and Pr(III). In further structure analysis, it is noted that such coordination networks, thus, created anionic primary coordination spheres (see Figures 1(a) and (b)), with twelve coordination environment around each metal species. Apart from it, in the lattices, uncoordinated three nitrate molecules and six protonated Hphen are also present balancing the charge appropriately. In fact, this is very much similar composition as reported for Eu(III) species in the literature. 22 Table 2. Selective bond distances in the coordination assemblies 1 – 3. Ce(1) – O(3) Ce(1) – O(4)
1 2.658(1) 2.624(2)
Pr(1) – O(1) Pr(1) – O(2)
2 2.614(2) 2.649(3)
Sm(1) – O(1) Sm(1) – O(2) Sm(1) – O(3) Sm(1) – O(4) Sm(1) – O(6) Sm(1) – O(7) Sm(1) – O(9) Sm(1) – O(10) Sm(1) – N(4) Sm(1) – N(5)
3 2.430(2) 2.444(1) 2.490(1) 2.646(2) 2.542(3) 2.530(1) 2.535(2) 2.517(1) 2.613(1) 2.617(4)
In the packing analysis of the molecules, further, it was noted that a host-guest network is realized with the creation of voids of two types, into which primary coordination spheres or uncoordinated nitrate ions are embedded, as shown in Figure 1(c). Within each void, the primary coordination sphere is connected to six host molecules through C-H…O hydrogen bonds with H…O distance of 2.50 Å. However, nitrate ions are connected to three host molecules through N+-H…O- hydrogen bonds with H…O- distance of 2.16 Å. Such interactions are shown in Figure 1(d) and (e). In three-dimensional arrangement, along the
stacking direction, the molecules are oriented in such a way that the primary coordination spheres and nitrates are being sandwiched between the layers of H-phen molecules, as represented in Figure 1(f). Extending the study to further metal ions to evaluate recurrence of isostructurality, Sm(III) salt is employed in the co-crystallization process, keeping other reactants intact and the obtained crystals are analyzed by single crystal x-ray diffraction methods.
Table 3. Hydrogen bond distances (Å) and angles ( ) for 1 and molecular complexes 1- 3. D–H…A C–H…O N+–H…OO–H…OO–H…O
2.50 2.16
1 3.51 2.90
165 140
2.48 2.12
2 3.51 2.91
3 166 139
2.20 2.72 2.75 2.20
2.81 2.96 3.28 2.91
156 164 140 171
Three columns for each structure represent H…A, D…A distances and D-H…A angles, respectively, for a typical hydrogen bond, being represented as D-H…A. #
Structure of [Sm(NO3)3].(phen).(H2O)2].[(H-phen).(NO3).H2O], (3): In the crystals of 3, unlike in 1 and 2, the metal ion is coordinated to only three nitrate ions, two water molecules and a H-phen through Sm-O and Sm-N bonds, yielding a neutral ten coordination sphere of Sm(III), in a triclinic space group P . The complete structure determination and refinement parameters are listed in Table 1. The contents present in the crystal lattice are shown in Figure 2(a).
(a)
(b)
(c)
Figure 2. (a) Structural units in the crystal lattice of 3. (b) Packing of molecules in the crystal structure of 3, in the form of crossed ribbons. (c) The 2D supramolecular network extended by hydrogen bonding interactions.
The observed Sm-O and Sm-N bonds, in the range 2.43 - 2.62 Å (see Table 2), , in are in agreement with the distances noted in the related structures reported in the literature. Further, uncoordinated but protonated H-phen molecule is also present along with a nitrate ion and a H2O molecule (see Figure 2(a)). Such variations in the asymmetric unit is also well reflected in the different packing arrangement of molecules in 3 than in 1 and 2.
In the
crystal packing of complex 3 each nitrate anion is hydrogen bonded to the coordination sphere as well as H-phen molecule (via N+–H…O-, O–H…O-), while the guest water molecules establish only an interaction with coordination sphere through O-H…O hydrogen bond with H…O distance of 2.20 Å to form 2D sheets (Figure 2(b)), which are extended further in 3D, resulting a crossed ribbons structure as depicted in Figure 2(c).
Conclusions: In this report, preparation and structure characterization by single crystal X-ray diffraction methods of three new coordination assemblies of 1,10-phenanthroline with Ce(III), Pr(III) and Sm(III) have been illustrated.
In all these structures, the three-
dimensional assemblies are realized through the effective role played by the second coordination spheres.
Acknowledgments: We gratefully acknowledge IIT Bhubaneswar for the financial support.
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Three new coordination polymer of 1,10-phenanthroline with Ce(III), Pr(III) and Sm(III). Role of secondary coordination spheres for complex formation. Formation of exotic host-guest networks by lanthanides. Utilization of noncovalent interactions for structure stabilization.