supplementary materials
Bis(pyridinium) trans-tetrachloridodioxidouranate(VI) dioxane solvate
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.
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.
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
bis(pyridinium) uranyl tetrachloridodioxidouranium(VI) dioxane solvate]
top
Crystal data top
| (C5H6N)2[UCl4O2]·C4H8O2 | Z = 1 |
| Mr = 660.15 | F000 = 310 |
| Triclinic, P1 | Dx = 2.148 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation
λ = 0.71073 Å |
| a = 7.766 (2) Å | Cell parameters from 2368 reflections |
| b = 8.666 (2) Å | θ = 4–25º |
| c = 9.202 (2) Å | µ = 8.50 mm−1 |
| α = 63.57 (3)º | T = 100 (1) K |
| β = 67.08 (2)º | Block, colourless |
| γ = 81.96 (2)º | 0.2 × 0.1 × 0.1 mm |
| V = 510.4 (3) Å3 | |
Data collection top
Kuma KM-4-CCD four-circle
diffractometer | 1770 independent reflections |
| Radiation source: fine-focus sealed tube | 1142 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.097 |
| T = 100(2) K | θmax = 25.0º |
| ω scans | θmin = 2.6º |
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006) | h = −9→8 |
| Tmin = 0.29, Tmax = 0.43 | k = −10→9 |
| 3821 measured reflections | l = −10→5 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.056 | H-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 reflections | Δρmax = 1.80 e Å−3 |
| 115 parameters | Δρmin = −2.38 e Å−3 |
| 54 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods | |
Crystal data top
| (C5H6N)2[UCl4O2]·C4H8O2 | γ = 81.96 (2)º |
| Mr = 660.15 | V = 510.4 (3) Å3 |
| Triclinic, P1 | Z = 1 |
| a = 7.766 (2) Å | Mo Kα |
| b = 8.666 (2) Å | µ = 8.50 mm−1 |
| c = 9.202 (2) Å | T = 100 (1) K |
| α = 63.57 (3)º | 0.2 × 0.1 × 0.1 mm |
| β = 67.08 (2)º | |
Data collection top
Kuma KM-4-CCD four-circle
diffractometer | 1770 independent reflections |
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006) | 1142 reflections with I > 2σ(I) |
| Tmin = 0.29, Tmax = 0.43 | Rint = 0.097 |
| 3821 measured reflections | |
Refinement top
| R[F2 > 2σ(F2)] = 0.056 | 54 restraints |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 0.89 | Δρmax = 1.80 e Å−3 |
| 1770 reflections | Δρmin = −2.38 e Å−3 |
| 115 parameters | |
Special details top
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) top| | x | y | z | Uiso*/Ueq | |
| U1 | 1.0000 | 1.0000 | 0.0000 | 0.0190 (3) | |
| O1 | 0.8449 (10) | 0.8196 (8) | 0.0864 (8) | 0.0147 (18) | |
| Cl1 | 1.1731 (4) | 0.8012 (3) | 0.2188 (3) | 0.0233 (9) | |
| Cl2 | 0.7746 (4) | 1.1044 (3) | 0.2426 (3) | 0.0220 (9) | |
| O1A | 0.3181 (10) | 0.5610 (8) | 0.5613 (8) | 0.013 (2) | |
| C2A | 0.4823 (16) | 0.6717 (13) | 0.4704 (13) | 0.017 (3) | |
| H2A2 | 0.4632 | 0.7624 | 0.5122 | 0.022* | |
| H2A1 | 0.5058 | 0.7287 | 0.3439 | 0.022* | |
| C3A | 0.6456 (17) | 0.5718 (14) | 0.4994 (13) | 0.018 (3) | |
| H3A2 | 0.7573 | 0.6508 | 0.4375 | 0.023* | |
| H3A1 | 0.6230 | 0.5183 | 0.6256 | 0.023* | |
| N1B | 0.9618 (13) | 0.6611 (10) | 0.6810 (10) | 0.016 (2) | |
| H1B | 1.0681 | 0.6435 | 0.6087 | 0.019* | |
| C2B | 0.9005 (17) | 0.5495 (14) | 0.8497 (13) | 0.022 (3) | |
| H2B | 0.9733 | 0.4548 | 0.8923 | 0.027* | |
| C3B | 0.7294 (17) | 0.5742 (14) | 0.9614 (13) | 0.020 (3) | |
| H3B | 0.6810 | 0.4911 | 1.0796 | 0.024* | |
| C4B | 0.6257 (18) | 0.7202 (14) | 0.9030 (13) | 0.023 (3) | |
| H4B | 0.5107 | 0.7412 | 0.9792 | 0.028* | |
| C5B | 0.7038 (17) | 0.8332 (14) | 0.7241 (12) | 0.018 (3) | |
| H5B | 0.6409 | 0.9347 | 0.6777 | 0.022* | |
| C6B | 0.8639 (17) | 0.8001 (14) | 0.6192 (14) | 0.021 (3) | |
| H6B | 0.9103 | 0.8759 | 0.4983 | 0.026* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| U1 | 0.0264 (6) | 0.0098 (4) | 0.0142 (4) | 0.0037 (4) | −0.0084 (3) | 0.0003 (3) |
| O1 | 0.015 (2) | 0.015 (2) | 0.015 (2) | 0.0000 (10) | −0.0054 (11) | −0.0072 (11) |
| Cl1 | 0.031 (2) | 0.0219 (17) | 0.0137 (15) | 0.0129 (17) | −0.0104 (16) | −0.0067 (13) |
| Cl2 | 0.026 (2) | 0.0193 (17) | 0.0173 (15) | 0.0095 (16) | −0.0073 (15) | −0.0077 (13) |
| O1A | 0.005 (5) | 0.014 (4) | 0.020 (4) | 0.001 (4) | −0.004 (4) | −0.008 (3) |
| C2A | 0.017 (3) | 0.017 (3) | 0.017 (3) | 0.0005 (10) | −0.0060 (14) | −0.0072 (15) |
| C3A | 0.018 (3) | 0.018 (3) | 0.018 (3) | 0.0004 (10) | −0.0066 (14) | −0.0075 (15) |
| N1B | 0.016 (2) | 0.016 (2) | 0.016 (2) | 0.0006 (10) | −0.0053 (13) | −0.0073 (13) |
| C2B | 0.022 (3) | 0.022 (3) | 0.022 (3) | 0.0011 (10) | −0.0083 (15) | −0.0093 (15) |
| C3B | 0.020 (3) | 0.020 (3) | 0.020 (3) | 0.0009 (10) | −0.0076 (14) | −0.0082 (15) |
| C4B | 0.023 (3) | 0.023 (3) | 0.023 (3) | 0.0006 (10) | −0.0086 (15) | −0.0100 (16) |
| C5B | 0.018 (3) | 0.018 (3) | 0.018 (3) | 0.0008 (10) | −0.0067 (14) | −0.0078 (15) |
| C6B | 0.021 (3) | 0.021 (3) | 0.021 (3) | 0.0007 (10) | −0.0081 (14) | −0.0088 (15) |
Geometric parameters (Å, °) top
| U1—O1 | 1.789 (7) | C3A—H3A1 | 0.9900 |
| U1—O1i | 1.789 (7) | N1B—C2B | 1.337 (11) |
| U1—Cl2i | 2.679 (3) | N1B—C6B | 1.350 (12) |
| U1—Cl2 | 2.679 (3) | N1B—H1B | 0.8800 |
| U1—Cl1 | 2.684 (3) | C2B—C3B | 1.386 (15) |
| U1—Cl1i | 2.684 (3) | C2B—H2B | 0.9500 |
| O1A—C2A | 1.430 (13) | C3B—C4B | 1.409 (13) |
| O1A—C3Aii | 1.440 (12) | C3B—H3B | 0.9500 |
| C2A—C3A | 1.477 (13) | C4B—C5B | 1.411 (12) |
| C2A—H2A2 | 0.9900 | C4B—H4B | 0.9500 |
| C2A—H2A1 | 0.9900 | C5B—C6B | 1.331 (14) |
| C3A—O1Aii | 1.440 (12) | C5B—H5B | 0.9500 |
| C3A—H3A2 | 0.9900 | C6B—H6B | 0.9500 |
| | | |
| O1—U1—O1i | 180.000 (1) | O1Aii—C3A—H3A2 | 109.2 |
| O1—U1—Cl2i | 88.5 (2) | C2A—C3A—H3A2 | 109.2 |
| O1i—U1—Cl2i | 91.5 (2) | O1Aii—C3A—H3A1 | 109.2 |
| O1—U1—Cl2 | 91.5 (2) | C2A—C3A—H3A1 | 109.2 |
| O1i—U1—Cl2 | 88.5 (2) | H3A2—C3A—H3A1 | 107.9 |
| Cl2i—U1—Cl2 | 180.000 (1) | C2B—N1B—C6B | 121.4 (10) |
| O1—U1—Cl1 | 88.4 (2) | C2B—N1B—H1B | 119.3 |
| O1i—U1—Cl1 | 91.6 (2) | C6B—N1B—H1B | 119.3 |
| Cl2i—U1—Cl1 | 90.57 (8) | N1B—C2B—C3B | 119.0 (10) |
| Cl2—U1—Cl1 | 89.43 (8) | N1B—C2B—H2B | 120.5 |
| O1—U1—Cl1i | 91.6 (2) | C3B—C2B—H2B | 120.5 |
| O1i—U1—Cl1i | 88.4 (2) | C2B—C3B—C4B | 121.2 (10) |
| Cl2i—U1—Cl1i | 89.43 (8) | C2B—C3B—H3B | 119.4 |
| Cl2—U1—Cl1i | 90.57 (8) | C4B—C3B—H3B | 119.4 |
| Cl1—U1—Cl1i | 180.000 (1) | C3B—C4B—C5B | 115.7 (11) |
| C2A—O1A—C3Aii | 107.7 (8) | C3B—C4B—H4B | 122.2 |
| O1A—C2A—C3A | 110.4 (8) | C5B—C4B—H4B | 122.2 |
| O1A—C2A—H2A2 | 109.6 | C6B—C5B—C4B | 121.2 (10) |
| C3A—C2A—H2A2 | 109.6 | C6B—C5B—H5B | 119.4 |
| O1A—C2A—H2A1 | 109.6 | C4B—C5B—H5B | 119.4 |
| C3A—C2A—H2A1 | 109.6 | C5B—C6B—N1B | 121.4 (10) |
| H2A2—C2A—H2A1 | 108.1 | C5B—C6B—H6B | 119.3 |
| O1Aii—C3A—C2A | 112.1 (10) | N1B—C6B—H6B | 119.3 |
| Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6B—H6B···Cl1 | 0.95 | 2.87 | 3.525 (12) | 127 |
| C2A—H2A2···Cl2iii | 0.99 | 2.88 | 3.754 (12) | 147 |
| N1B—H1B···O1Aiv | 0.88 | 1.92 | 2.725 (11) | 151 |
| C4B—H4B···Cl1v | 0.95 | 2.85 | 3.803 (13) | 177 |
| Symmetry codes: (iii) −x+1, −y+2, −z+1; (iv) x+1, y, z; (v) x−1, y, z+1. |
Table 1
Selected geometric parameters (Å, °) top| U1—O1 | 1.789 (7) | U1—Cl1 | 2.684 (3) |
| U1—Cl2 | 2.679 (3) | | |
| | | |
| O1—U1—Cl2 | 91.5 (2) | O1i—U1—Cl1 | 91.6 (2) |
| O1i—U1—Cl2 | 88.5 (2) | Cl2—U1—Cl1 | 89.43 (8) |
| Cl2i—U1—Cl2 | 180.000 (1) | Cl2—U1—Cl1i | 90.57 (8) |
| O1—U1—Cl1 | 88.4 (2) | Cl1—U1—Cl1i | 180.000 (1) |
| Symmetry codes: (i) −x+2, −y+2, −z. |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6B—H6B···Cl1 | 0.95 | 2.87 | 3.525 (12) | 127 |
| C2A—H2A2···Cl2ii | 0.99 | 2.88 | 3.754 (12) | 147 |
| N1B—H1B···O1Aiii | 0.88 | 1.92 | 2.725 (11) | 151 |
| C4B—H4B···Cl1iv | 0.95 | 2.85 | 3.803 (13) | 177 |
| Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x+1, y, z; (iv) x−1, y, z+1. |
This work was supported by the Ministry of Science and Higher Education (grant
No. N204 0317 33).
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
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 Compound, 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.
O hydrogen bonding. There are additional intermolecular C-H![[Figure 1]](./nc2081fig1thm.gif)
![[Figure 2]](./nc2081fig2thm.gif)
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).