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Acta Crystallogr C. Mar 15, 2010; 66(Pt 3): m69–m74.
Published online Feb 3, 2010. doi:  10.1107/S0108270109053839
PMCID: PMC2855580
Hydrogen-bonded network structures in dipyridinium, bis­(2-methyl­pyridinium), bis­(3-methyl­pyridinium) and bis­(4-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI)
Anders Lennartsona* and Mikael Håkanssonb
aDepartment of Physics and Chemistry, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark
bDepartment of Chemistry, University of Gothenburg, SE-412 96 Göteborg, Sweden
Correspondence e-mail: lennartson/at/ifk.sdu.dk
Received November 5, 2009; Accepted December 14, 2009.
Four complexes containing the [UO2(oda)2]2− anion (oda is oxy­diacetate) are reported, namely dipyridinium dioxidobis(oxydiacetato)uranate(VI), (C5H6N)2[U(C4H4O5)2O2], (I), bis(2-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI), (C8H8N)2[U(C4H4O5)2O2], (II), bis­(3-methyl­pyridinium) di­oxido­bis(oxydiacetato)uranate(VI), (C8H8N)2[U(C4H4O5)2O2], (III), and bis­(4-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI), (C8H8N)2[U(C4H4O5)2O2], (IV). The anions are achiral and are located on a mirror plane in (I) and on inversion centres in (II)–(IV). The four complexes are assembled into three-dimensional structures via N—H(...)O and C—H(...)O inter­actions. Compounds (III) and (IV) are isomorphous; the [UO2(oda)2]2− anions form a porous matrix which is nearly identical in the two structures, and the cations are located in channels formed in this matrix. Compounds (I) and (II) are very different from (III) and (IV): (I) forms a layered structure, while (II) forms ribbons.
We recently published a study of complexes featuring the nine-coordinate chiral [Ln(oda)3]3− anion (where Ln = Pr, Eu, Gd or Dy, and oda = oxydiacetate) (Lennartson & Håkansson, 2009a [triangle]). In the case of Na5[Er(oda)3](H2O)6(BF4)2, which crystallizes in the Sohncke space group (Flack, 2003 [triangle]) R32, it was possible to crystallize a whole sample as one enantio­merically pure single crystal. This represents the first example of the preparation of enantio­merically pure bulk quanti­ties of a nine-coordinate complex displaying only achiral ligands. Since all precursors [diglycolic acid, erbium(III) chloride hexa­hydrate, sodium hydroxide, sodium bicarbonate, sodium tetra­fluoro­borate and water] were achiral, the overall synthesis may be regarded as a case of absolute asymmetric synthesis (Feringa & van Delden, 1999 [triangle]; Mislow, 2003 [triangle]). Progressing from the oxydiacetate lanthanide complexes we have examined the corresponding actinide complexes, and four complexes containing the dioxidobis(oxydiacetato)­uran­ate(VI) anion, [UO2(oda)2]2−, are presented in this paper.
Only six crystal structures of uranyl complexes containing the oxydiacetate ligand are listed in the Cambridge Structural Database (CSD, Version 5.30 of May 2009; Allen, 2002 [triangle]). In the absence of coordinating ligands, uranyl oxydiacetate forms a coordination polymer (Bombieri et al., 1974 [triangle]), which undergoes spontaneous resolution (Jacques et al., 1984 [triangle]; Perez-Garcia & Amabilino, 2007 [triangle]) on crystallization. The other structures pub­lished are oxodiacetatodi(pyridine oxide)dioxo­uranium(VI) (Bombieri et al., 1973 [triangle]), di(1,3,5,7-tetra­azaadamant-1-ium)di(μ2-hydroxo)di(oxodiacetato)tetra­oxodiuranium(VI) dihydrate (Jiang et al., 2002 [triangle]) and three structures containing the [UO2(oda)2]2− anion (Bombieri et al., 1973 [triangle]; Jiang et al., 2002 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is c-66-00m69-scheme1.jpg Object name is c-66-00m69-scheme1.jpg
Dipyridinium dioxidobis(oxydiacetato)uranate(VI), (I), bis(2-methyl­pyridinium) dioxidobis(oxydiacetato)uran­ate(VI), (II), bis­(3-methyl­pyridinium) dioxidobis(oxy­di­acet­ato)uran­ate(VI), (III), and bis­(4-methyl­pyridinium) dioxidobis(oxy­diacetato)uranate(VI), (IV), all form yellow crystals from aqueous solution. None of the crystal structures includes water, neither coordinated to the U atom nor as co-crystallized water.
The uranyl moieties in compounds (I)–(IV) are linear, as expected, and are coordinated by two oxydiacetate ligands, giving rise to complex [UO2(oda)2]2− anions. The anions differ somewhat between the four compounds. In (I), the [UO2(oda)2]2− anion is located on a mirror plane bisecting both oxydiacetate ligands (Fig. 1 [triangle]). The two oxydiacetate ligands are coordinated differently to the central U atom. One is virtually planar, and atoms O3 and O5 are both coordinated to the central U atom. The other ligand deviates considerably from planarity and, since the U1—O8 distance is probably too long to be considered a U—O bond, it is best described as a bidentate ligand. The [UO2(oda)2]2− anions in (II), (III) and (IV) are very similar (Figs. 2 [triangle]–4 [triangle] [triangle]), with the central U atoms located on crystallographic inversion centres and with the oxydiacetate ligands virtually planar. Both types of coordination mode have been reported previously (Jiang et al., 2002 [triangle]). Selected geometric parameters for (I)–(IV) are compared in Table 1 [triangle]. The[UO2(oda)2]2− anions are achiral, in contrast with the propeller-shaped [Ln(oda)3]3− anions, but this does not exclude the possibility of a chiral crystal structure, since achiral mol­ecules may assemble into chiral supra­molecular structures (Matsuura & Koshima, 2005 [triangle]; Lennartson & Håkansson, 2009b [triangle]). However, compounds (I)–(IV) form centrosymmetric crystals.
Figure 1
Figure 1
The mol­ecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) x, An external file that holds a picture, illustration, etc.
Object name is c-66-00m69-efi24.jpg − y, (more ...)
Figure 2
Figure 2
The mol­ecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (ii) −x, −y, − (more ...)
Figure 3
Figure 3
The mol­ecular structure of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (ii) −x, −y, − (more ...)
Figure 4
Figure 4
The mol­ecular structure of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (ii) −x, −y, − (more ...)
Table 1
Table 1
Selected geometric parameters (Å, °) for (I)–(IV)
The ions in (I) are associated by N—H(...)O and C—H(...)O inter­actions (Table 2 [triangle]). Classical N—H(...)O inter­actions form a short contact between atoms H1 and O7 within the asymmetric unit. Due to symmetry, each [UO2(oda)2]2− anion will inter­act with two pyridinium cations. The C—H(...)O inter­actions involving H5(...)O4(1 − x, −y, 1 − z), H7(...)O4(1 − x, −y, 2 − z) and H8(...)O7(x, y, 1 + z) give rise to layers in the bc plane (Fig. 5 [triangle]). These layers are further associated into a network structure (Fig. 6 [triangle]) by two sets of C—H(...)O inter­actions, viz. H2A(...)O2(−1 + x, y, z) and H4A(...)O1(1 + x, y, z).
Table 2
Table 2
Hydrogen-bond geometry (Å, °) for (I)
Figure 5
Figure 5
The N—H(...)O and C—H(...)O bonded layer in (I). Hydrogen bonds are shown as dashed lines. All H atoms not involved in these inter­actions have been omitted for clarity.
Figure 6
Figure 6
Diagram showing how the layers in (I) are assembled into a network structure by C—H(...)O inter­actions (dashed lines). Three layers are depicted and run horizontally in the figure. All H atoms not involved in these inter­actions (more ...)
Introducing a methyl group in the 2-position on the pyridinium cation, i.e. on going from (I) to (II), dramatically alters the crystal packing (Table 3 [triangle]). The 2-picolinium cation in (II) binds two [UO2(oda)2]2− anions through N—H(...)O and C—H(...)O inter­actions. Two sets of inter­actions, viz. H1(...)O3(−x, −y, −z) and H10(...)O5, connect the 2-picolin­ium cation to one anion, and a third inter­action, H8(...)O6(1 − x, 1 − y, −z), introduces connections to a second anion. As seen in Fig. 7 [triangle], these inter­actions give rise to infinite ribbons. Sets of ribbons are partly stacked in a similar fashion to the strakes in a ship’s hull, giving rise to layers. The layers are stacked into a three-dimensional structure, where ribbons in adjacent layers are orthogonal; a schematic drawing is presented in Fig. 8 [triangle].
Table 3
Table 3
Hydrogen-bond geometry (Å, °) for (II)
Figure 7
Figure 7
Diagram showing how the N—H(...)O and C—H(...)O inter­actions in (II) (dashed lines) give rise to ribbons. All H atoms not involved in these inter­actions have been omitted for clarity.
Figure 8
Figure 8
Schematic drawing of the ribbons in the structure of (II). The ribbons form layers which are stacked into a three-dimensional structure; three such layers are depicted.
The crystal structure of the analogous 3-picolinium complex, (III), is different from both (I) and (II) (Table 4 [triangle]). N—H(...)O and C—H(...)O inter­actions in (III) give rise to a three-dimensional network structure (Fig. 9 [triangle]). The [UO2(oda)2]2− anions in (III) form a porous matrix with channels running parallel to the crystallographic a and c axes. These channels are occupied by the 3-picolinium cations. A view along the a axis is presented in Fig. 10 [triangle].
Table 4
Table 4
Hydrogen-bond geometry (Å, °) for (III)
Figure 9
Figure 9
The C—H(...)O inter­actions in (III) (dashed lines), involving the cation (top) and the anion (bottom).
Figure 10
Figure 10
Diagram showing how the cations in (III) are located in channels running through the unit cell. All H atoms have been omitted.
Compound (IV) is isomorphous with (III). The matrices formed by the anions are almost identical, forming the same type of channels. The orientations of the cations occupying these channels differ between the two structures, and the inter­molecular inter­actions in (IV) (Table 5 [triangle]) are of course different from those in (III), as depicted in Fig. 11 [triangle].
Table 5
Table 5
Hydrogen-bond geometry (Å, °) for (IV)
Figure 11
Figure 11
C—H(...)O inter­actions in (IV) (dashed lines), involving the cation (top) and the anion (bottom).
In the case of the [Ln(oda)3]3− complexes, spontaneous resolution did not occur for Na3[Ln(oda)3](H2O)6, which crystallized in the polar space group Cc. Addition of certain salts led to more complex structures, of which Na3NH4[Ln(oda)3](SCN)(H2O)4 is racemic and Na5[Ln(oda)3](H2O)6(BF4)2 undergoes spontaneous resolution. It appears that the presence of BF4 is essential for spontaneous resolution to occur in this system. Preliminary studies show that recrystallization of (I) from water in the presence of inorganic salts leads to cocrystallization in certain cases, and the formation of a chiral supra­molecular structure may be observed at a future date.
For the preparation of uranyl oxydiacetate, diglycolic acid (0.13 g, 1.0 mmol) and sodium bicarbonate (0.17 g, 2.0 mmol) were dissolved in water (5 ml). A solution of uranyl nitrate hexa­hydrate (0.50 g, 1 mmol) in water (5 ml) was added. The solution was heated to reflux and a yellow precipitate formed. The mixture was cooled to ambient temperature and the precipitate collected by filtration, washed with water (3 × 5 ml) and acetone (3 × 5 ml), and dried by suction (yield 0.35 g, 87%). For the preparation of (I), pyridine (0.3 ml) and water (1.0 ml) were added to a mixture of uranyl oxydiacetate (0.35 g, 0.82 mmol) and diglycolic acid (0.11 g, 0.82 mmol). The mixture was heated until a clear solution was obtained. Yellow crystals of (I) formed on cooling to ambient temperature (yield 0.33 g, 54%). Compounds (II)–(IV) were pre­pared in an analogous manner, substituting pyridine by 2-, 3- and 4-picoline, respectively.
Compound (I)
Crystal data
  • (C5H6N)2[U(C4H4O5)2O2]
  • M r = 694.39
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is c-66-00m69-efi1.jpg
  • a = 6.675 (2) Å
  • b = 23.025 (5) Å
  • c = 7.500 (2) Å
  • β = 110.946 (11)°
  • V = 1076.5 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 7.61 mm−1
  • T = 100 K
  • 0.2 × 0.2 × 0.1 mm
Data collection
  • Rigaku R-AXIS IIC image-plate diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 [triangle]) T min = 0.240, T max = 0.470
  • 5883 measured reflections
  • 1853 independent reflections
  • 1763 reflections with I > 2σ(I)
  • R int = 0.032
Refinement
  • R[F 2 > 2σ(F 2)] = 0.016
  • wR(F 2) = 0.038
  • S = 1.06
  • 1853 reflections
  • 161 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.81 e Å−3
  • Δρmin = −0.96 e Å−3
Compound (II)
Crystal data
  • (C6H8N)2[U(C4H4O5)2O2]
  • M r = 722.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is c-66-00m69-efi8.jpg
  • a = 9.183 (2) Å
  • b = 11.104 (3) Å
  • c = 12.826 (4) Å
  • β = 111.490 (7)°
  • V = 1217.0 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 6.73 mm−1
  • T = 295 K
  • 0.2 × 0.2 × 0.1 mm
Data collection
  • Rigaku R-AXIS IIC image-plate diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 [triangle]) T min = 0.304, T max = 0.510
  • 7415 measured reflections
  • 2106 independent reflections
  • 1694 reflections with I > 2σ(I)
  • R int = 0.027
Refinement
  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.059
  • S = 0.92
  • 2106 reflections
  • 165 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.15 e Å−3
  • Δρmin = −1.38 e Å−3
Compound (III)
Crystal data
  • (C6H8N)2[U(C4H4O5)2O2]
  • M r = 722.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is c-66-00m69-efi8.jpg
  • a = 7.415 (2) Å
  • b = 13.312 (5) Å
  • c = 11.806 (4) Å
  • β = 91.224 (15)°
  • V = 1165.1 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 7.03 mm−1
  • T = 295 K
  • 0.4 × 0.2 × 0.1 mm
Data collection
  • Rigaku R-AXIS IIC image-plate diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 [triangle]) T min = 0.088, T max = 0.500
  • 7099 measured reflections
  • 1885 independent reflections
  • 1544 reflections with I > 2σ(I)
  • R int = 0.104
Refinement
  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.130
  • S = 1.03
  • 1885 reflections
  • 165 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 2.20 e Å−3
  • Δρmin = −3.34 e Å−3
Compound (IV)
Crystal data
  • (C6H8N)2[U(C4H4O5)2O2]
  • M r = 722.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is c-66-00m69-efi8.jpg
  • a = 7.3439 (13) Å
  • b = 12.999 (2) Å
  • c = 12.194 (2) Å
  • β = 92.438 (9)°
  • V = 1163.0 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 7.05 mm−1
  • T = 295 K
  • 0.2 × 0.2 × 0.1 mm
Data collection
  • Rigaku R-AXIS IIC image-plate diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 [triangle]) T min = 0.231, T max = 0.490
  • 6992 measured reflections
  • 2002 independent reflections
  • 1752 reflections with I > 2σ(I)
  • R int = 0.061
Refinement
  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.086
  • S = 1.14
  • 2002 reflections
  • 165 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 2.28 e Å−3
  • Δρmin = −1.99 e Å−3
The N-bound H atoms were located in difference Fourier maps and refined isotropically, with the N—H distances in (I) and (IV) restrained to 0.90 (2) Å. The C-bound H atoms were included in calculated positions, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and refined using a riding model, with U iso(H) = 1.5U eq(C) for the methyl groups and 1.5U eq(C) for the remainder. A few strong low-angle reflections were excluded since these caused saturation of the image plate.
For all compounds, data collection: CrystalClear (Rigaku, 2000 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLUTON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.
Supplementary Material
Crystal structure: contains datablocks I, II, III, IV, global. DOI: 10.1107/S0108270109053839/gg3221sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S0108270109053839/gg3221Isup2.hkl
Structure factors: contains datablocks II. DOI: 10.1107/S0108270109053839/gg3221IIsup3.hkl
Structure factors: contains datablocks III. DOI: 10.1107/S0108270109053839/gg3221IIIsup4.hkl
Structure factors: contains datablocks IV. DOI: 10.1107/S0108270109053839/gg3221IVsup5.hkl
Acknowledgments
Financial support from the Swedish Research Council (VR) is gratefully acknowledged.
Footnotes
Supplementary data for this paper are available from the IUCr electronic archives (Reference: GG3221). Services for accessing these data are described at the back of the journal.
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