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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m239.
Published online 2007 December 21. doi:  10.1107/S1600536807066949
PMCID: PMC2915159

Bis(pyridinium) trans-tetrachlorido­dioxidouranate(VI) dioxane solvate

Abstract

In the crystal structure of the title compound, (C5H6N)2[UCl4O2]·C4H8O2, the pyridinium cations occupy general positions and the anions and the solvent dioxane mol­ecule are located on centres of inversion. The dioxane mol­ecules are connected to two symmetry-related pyridinium cations via O—H(...)O hydrogen bonding. There are additional inter­molecular C—H(...)Cl contacts, which are indicative of weak C—H(...)Cl inter­actions.

Related literature

For related literature, see Kaczmarek et al. (2004 [triangle]); Pospieszna-Markiewicz & Radecka-Paryzek (2004 [triangle]); Sessler et al. (2006 [triangle]); Allen (2002 [triangle]).

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Object name is e-64-0m239-scheme1.jpg

Experimental

Crystal data

  • (C5H6N)2[UCl4O2]·C4H8O2
  • M r = 660.15
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m239-efi1.jpg
  • a = 7.766 (2) Å
  • b = 8.666 (2) Å
  • c = 9.202 (2) Å
  • α = 63.57 (3)°
  • β = 67.08 (2)°
  • γ = 81.96 (2)°
  • V = 510.4 (3) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 8.49 mm−1
  • T = 100 (1) K
  • 0.2 × 0.1 × 0.1 mm

Data collection

  • Kuma KM-4-CCD four-circle diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 [triangle]) T min = 0.29, T max = 0.43
  • 3821 measured reflections
  • 1770 independent reflections
  • 1142 reflections with I > 2σ(I)
  • R int = 0.097

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.090
  • S = 0.89
  • 1770 reflections
  • 115 parameters
  • 54 restraints
  • H-atom parameters constrained
  • Δρmax = 1.80 e Å−3
  • Δρmin = −2.38 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: XP (Siemens, 1989 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807066949/nc2081sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066949/nc2081Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Ministry of Science and Higher Education (grant No. N204 0317 33).

supplementary crystallographic information

Comment

The use of uranium as a source of energy has caused increasing attention which is focused on the problem of fuel reprocessing and waste storage. Much effort has been devoted, in recent years, to the preparation and characterization of specific complexing agents for the uranyl ion (UO22+), so-called "uranophiles" with the objective of a possible application for the separation of uranium species in waste liquids from the nuclear fuel cycle and for the recovery and utilization of uranium from the sea water (Sessler et al. 2006). The title compound was isolated during our study on the synthesis and characterization of uranyl complexes containing macrocyclic and acyclic polyaza and polyoxaaza Schiff bases derived from biogenic amines and their analogs to evaluate their potential as uranyl sequestering agents (Pospieszna-Markiewicz & Radecka-Paryzek, 2004; Kaczmarek et al., 2004).

The asymmetric unit of the title compound (I) consists of one uranyl tetrachloride dianion and one dioxane molecule which are located on centres of inversion and one pyridinium cation which occupy a general position. This is quite common for similar complexes. In the Cambridge Structural Database (Allen, 2002; Version August 2007) there are 34 structures containing tetrachloro-uranyl dianions and a total of 144 structures which contain tetra-coordinated uranyl cations. Of those, 25 tetrachloro (79 for all) crystallizes with Z'<1, of which 22 (71 for all) have Z'=1/2.

In the crystal structure of the title compound the uranium atoms are coordinated by two oxygen and four chlorine atoms within slightly distorted octahedra (Fig. 1 and Tab.1). The U—O bond lengths of 1.789 (7)Å and the U—Cl bond lengths of 2.679 (3)Å and 2,684 (3)Å are close to the average CSD values (U—O = 1.77 (2)Å and U—Cl = 2.6791) Å, respectively).

Each two symmetry related pyridinium cations are connected by strong N—H···O hydrogen bonding to the dioxane molecule, forming hydrogen-bonded (pyridine···dioxane···pyridine)2+ cations (Tab. 2). These building units are connected by weak C—H···Cl interactions to the dications into a three-dimensional network (Tab. 2 and Fig. 2).

Experimental

The title compound was isolated during the slow diffusion of dioxane into pyridine hydrochloride solution of the uranyl(VI) Schiff base complex prepared through one-step template reaction of 2,6-diacetylpyridine with spermidine in the presence of uranyl(VI) acetateunder following conditions: to a mixture of uranyl acetate (42.5 mg, 0.1 mmol) in methanol (10 cm3) and 2,6-diacetylpyridine (16,3 mg, 0.1 mmol) in methanol (10 cm3), spermidine (0.016 cm3, 0.1 mmol) in methanol (10 cm3) was added dropwise with stirring; the reaction wascarried out for 4 h, the solution volume was then reduced to 10 cm3 by roto-evaporation and a yellow precipitate formed on addition of a small amount of diethyl ether was filtered off, washed with ether, and dried in vacuo.

Refinement

The H atoms were positioned with idealized geometry and were refined isotropic using a riding model with Uiso(H) = 1.2. Ueq(C,N) of the parent atom. Weak restraints (ISOR) were applied to the displacement parameters of C, N and O atoms.

Figures

Fig. 1.
Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% propability level, H atoms are drawn as spheres with arbitrary radii. Symmetry codes: (i) 2 - x,2 - y,-z, (ii) 1 - x,1 - y,1 - z.
Fig. 2.
Crystal structure of (I) with view along the a axis. O—H···O hydrogen bonding and C—H···Cl interactions are shown as dashed lines.

Crystal data

(C5H6N)2[UCl4O2]·C4H8O2Z = 1
Mr = 660.15F000 = 310
Triclinic, P1Dx = 2.148 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.766 (2) ÅCell parameters from 2368 reflections
b = 8.666 (2) Åθ = 4–25º
c = 9.202 (2) ŵ = 8.50 mm1
α = 63.57 (3)ºT = 100 (1) K
β = 67.08 (2)ºBlock, colourless
γ = 81.96 (2)º0.2 × 0.1 × 0.1 mm
V = 510.4 (3) Å3

Data collection

Kuma KM-4-CCD four-circle diffractometer1770 independent reflections
Radiation source: fine-focus sealed tube1142 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.097
T = 100(2) Kθmax = 25.0º
ω scansθmin = 2.6º
Absorption correction: multi-scan(CrysAlis RED; Oxford Diffraction, 2006)h = −9→8
Tmin = 0.29, Tmax = 0.43k = −10→9
3821 measured reflectionsl = −10→5

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.02P)2] where P = (Fo2 + 2Fc2)/3
S = 0.89(Δ/σ)max < 0.001
1770 reflectionsΔρmax = 1.80 e Å3
115 parametersΔρmin = −2.38 e Å3
54 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
U11.00001.00000.00000.0190 (3)
O10.8449 (10)0.8196 (8)0.0864 (8)0.0147 (18)
Cl11.1731 (4)0.8012 (3)0.2188 (3)0.0233 (9)
Cl20.7746 (4)1.1044 (3)0.2426 (3)0.0220 (9)
O1A0.3181 (10)0.5610 (8)0.5613 (8)0.013 (2)
C2A0.4823 (16)0.6717 (13)0.4704 (13)0.017 (3)
H2A20.46320.76240.51220.022*
H2A10.50580.72870.34390.022*
C3A0.6456 (17)0.5718 (14)0.4994 (13)0.018 (3)
H3A20.75730.65080.43750.023*
H3A10.62300.51830.62560.023*
N1B0.9618 (13)0.6611 (10)0.6810 (10)0.016 (2)
H1B1.06810.64350.60870.019*
C2B0.9005 (17)0.5495 (14)0.8497 (13)0.022 (3)
H2B0.97330.45480.89230.027*
C3B0.7294 (17)0.5742 (14)0.9614 (13)0.020 (3)
H3B0.68100.49111.07960.024*
C4B0.6257 (18)0.7202 (14)0.9030 (13)0.023 (3)
H4B0.51070.74120.97920.028*
C5B0.7038 (17)0.8332 (14)0.7241 (12)0.018 (3)
H5B0.64090.93470.67770.022*
C6B0.8639 (17)0.8001 (14)0.6192 (14)0.021 (3)
H6B0.91030.87590.49830.026*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
U10.0264 (6)0.0098 (4)0.0142 (4)0.0037 (4)−0.0084 (3)0.0003 (3)
O10.015 (2)0.015 (2)0.015 (2)0.0000 (10)−0.0054 (11)−0.0072 (11)
Cl10.031 (2)0.0219 (17)0.0137 (15)0.0129 (17)−0.0104 (16)−0.0067 (13)
Cl20.026 (2)0.0193 (17)0.0173 (15)0.0095 (16)−0.0073 (15)−0.0077 (13)
O1A0.005 (5)0.014 (4)0.020 (4)0.001 (4)−0.004 (4)−0.008 (3)
C2A0.017 (3)0.017 (3)0.017 (3)0.0005 (10)−0.0060 (14)−0.0072 (15)
C3A0.018 (3)0.018 (3)0.018 (3)0.0004 (10)−0.0066 (14)−0.0075 (15)
N1B0.016 (2)0.016 (2)0.016 (2)0.0006 (10)−0.0053 (13)−0.0073 (13)
C2B0.022 (3)0.022 (3)0.022 (3)0.0011 (10)−0.0083 (15)−0.0093 (15)
C3B0.020 (3)0.020 (3)0.020 (3)0.0009 (10)−0.0076 (14)−0.0082 (15)
C4B0.023 (3)0.023 (3)0.023 (3)0.0006 (10)−0.0086 (15)−0.0100 (16)
C5B0.018 (3)0.018 (3)0.018 (3)0.0008 (10)−0.0067 (14)−0.0078 (15)
C6B0.021 (3)0.021 (3)0.021 (3)0.0007 (10)−0.0081 (14)−0.0088 (15)

Geometric parameters (Å, °)

U1—O11.789 (7)C3A—H3A10.9900
U1—O1i1.789 (7)N1B—C2B1.337 (11)
U1—Cl2i2.679 (3)N1B—C6B1.350 (12)
U1—Cl22.679 (3)N1B—H1B0.8800
U1—Cl12.684 (3)C2B—C3B1.386 (15)
U1—Cl1i2.684 (3)C2B—H2B0.9500
O1A—C2A1.430 (13)C3B—C4B1.409 (13)
O1A—C3Aii1.440 (12)C3B—H3B0.9500
C2A—C3A1.477 (13)C4B—C5B1.411 (12)
C2A—H2A20.9900C4B—H4B0.9500
C2A—H2A10.9900C5B—C6B1.331 (14)
C3A—O1Aii1.440 (12)C5B—H5B0.9500
C3A—H3A20.9900C6B—H6B0.9500
O1—U1—O1i180.000 (1)O1Aii—C3A—H3A2109.2
O1—U1—Cl2i88.5 (2)C2A—C3A—H3A2109.2
O1i—U1—Cl2i91.5 (2)O1Aii—C3A—H3A1109.2
O1—U1—Cl291.5 (2)C2A—C3A—H3A1109.2
O1i—U1—Cl288.5 (2)H3A2—C3A—H3A1107.9
Cl2i—U1—Cl2180.000 (1)C2B—N1B—C6B121.4 (10)
O1—U1—Cl188.4 (2)C2B—N1B—H1B119.3
O1i—U1—Cl191.6 (2)C6B—N1B—H1B119.3
Cl2i—U1—Cl190.57 (8)N1B—C2B—C3B119.0 (10)
Cl2—U1—Cl189.43 (8)N1B—C2B—H2B120.5
O1—U1—Cl1i91.6 (2)C3B—C2B—H2B120.5
O1i—U1—Cl1i88.4 (2)C2B—C3B—C4B121.2 (10)
Cl2i—U1—Cl1i89.43 (8)C2B—C3B—H3B119.4
Cl2—U1—Cl1i90.57 (8)C4B—C3B—H3B119.4
Cl1—U1—Cl1i180.000 (1)C3B—C4B—C5B115.7 (11)
C2A—O1A—C3Aii107.7 (8)C3B—C4B—H4B122.2
O1A—C2A—C3A110.4 (8)C5B—C4B—H4B122.2
O1A—C2A—H2A2109.6C6B—C5B—C4B121.2 (10)
C3A—C2A—H2A2109.6C6B—C5B—H5B119.4
O1A—C2A—H2A1109.6C4B—C5B—H5B119.4
C3A—C2A—H2A1109.6C5B—C6B—N1B121.4 (10)
H2A2—C2A—H2A1108.1C5B—C6B—H6B119.3
O1Aii—C3A—C2A112.1 (10)N1B—C6B—H6B119.3

Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6B—H6B···Cl10.952.873.525 (12)127
C2A—H2A2···Cl2iii0.992.883.754 (12)147
N1B—H1B···O1Aiv0.881.922.725 (11)151
C4B—H4B···Cl1v0.952.853.803 (13)177

Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) x+1, y, z; (v) x−1, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NC2081).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Kaczmarek, M. T., Pospieszna-Markiewicz, I. & Radecka-Paryzek, W. (2004). J. Inclus. Phenom. Macrocyclic Chem.49, 115–119.
  • Oxford Diffraction (2006). CrysAlis CCD (Version 1.171.29.9) and CrysAlis RED (Version 1.171.29.9). Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Pospieszna-Markiewicz, I. & Radecka-Paryzek, W. (2004). J. Alloys Compd, 374, 253–257.
  • Sessler, J., Melfi, P. J. & Pantos, G. D. (2006). Coord. Chem. Rev.250, 816–843.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Siemens (1989). XP Release 3.4. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography