Hydrogen-bonded network structures in dipyridinium, bis­(2-methyl­pyridinium), bis­(3-methyl­pyridinium) and bis­(4-methyl­pyridinium) dioxidobis(oxydiacetato)uranate(VI)

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.

S1. Comment

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 = oxodiacetate) (Lennartson & Håkansson, 2009a). In the case of Na₅[Er(oda)₃](H₂O)₆(BF₄)₂, which crystallizes in the Sohncke space group (Flack, 2003) 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 hexafluoroborate and water] were achiral, the overall synthesis may be regarded as a case of absolute asymmetric synthesis (Feringa & van Delden, 1999; Mislow, 2003). From the oxodiacetate 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 oxodiacetate ligand are listed in the Cambridge Structural Database (CSD, Version 5.30 of May 2009; Allen, 2002). In the absence of coordinating ligands, uranyl oxodiacetate forms a coordination polymer (Bombieri et al., 1974), which undergoes spontaneous resolution (Jacques et al., 1984; Perez-Garcia & Amabilino, 2007) on crystallization. The other structures published are oxodiacetatodi(pyridine oxide)dioxouranium(VI) (Bombieri et al., 1973), di(1,3,5,7-tetraazaadamant-1-ium)di(µ₂-hydroxo)di(oxodiacetato)-tetraoxodiuranium(VI) dihydrate (Jiang et al., 2002) and three structures containing the [UO₂(oda)₂]^2- anion (Bombieri et al., 1973; Jiang et al., 2002).

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 oxodiacetate 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 oxodiacetate ligands (Fig. 1). The two oxodiacetate ligands are coordinated differently to the central U atom. One is virtually planar, and both atoms O3 and O5 are 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 (Fig. 2–4), with the central U atoms located on crystallographic inversion centres and with the oxodiacetate ligands virtually planar. Both types of coordination mode have been reported previously (Jiang et al., 2002). 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; Lennartson & Håkansson, 2009b). However, compounds (I)–(IV) form centrosymmetric crystals.

The ions in (I) are associated by N—H···O and C—H···O interactions. 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). These layers are further associated into a network structure (Fig. 6) by three sets of C—H···O interactions: H2A···O2(-1 + x, y, z), H2A···O6(-1 + x, y, z) and H4A···O1(1 + x, y, z).

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. 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, 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, 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. There are weak interactions between the layers: atom H5 forms a short contact (2.69 Å) to atom O5; a schematic drawing is presented in Fig. 8.

The crystal structure of the analogous 3-picolinium complex, (III), is different from both (I) and (II). N—H···O and C—H···O interactions in (III) give rise to a three-dimensional network structure (Fig. 9). 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.

Compound (IV) is isomorphous with (III). The matrices formed by the anions are close to 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) are of course different from those in (III), as depicted in Fig. 11.

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 co-crystallization in certain cases, and the formation of a chiral supramolecular structure may be observed at a future date.

S2. Experimental

Uranyl oxodiacetate was prepared as follows. 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, whereupon a yellow precipitate formed. The mixture was cooled to ambient temperature, filtered, washed with water (3 × 5 ml) and acetone (3 × 5 ml), and dried by suction (yield 0.35 g, 87%).

Dipyridinium dioxidobis(oxydiacetato)uranate(VI), (I), was prepared as follows. Pyridine (0.3 ml) and water (1.0 ml) were added to a mixture of uranyl oxodiacetate (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.

S3. Refinement

The N-bound H atoms were located in difference Fourier maps and refined, with the N—H distances in (I) and (IV) restrained to 0.90(s.u.?) Å. The C-bound H atoms were included in calculated positions, with C—H = 0.93–0.97 Å, and refined using a riding model, with U_iso(H) = 1.2–1.5U_iso(C).

Computing details

For all compounds, data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLUTON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 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, 1/2 - y, z.]
	Fig. 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, -z.]
	Fig. 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, -z.]
	Fig. 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, -z.]
	Fig. 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.
	Fig. 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 have been omitted for clarity.
	Fig. 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.
	Fig. 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.
	Fig. 9. The C—H···O interactions in (III) (dashed lines), involving the cation (top) and the anion (bottom).
	Fig. 10. Diagram showing how the cations in (III) are located in channels running through the unit cell. All H atoms have been omitted.
	Fig. 11. C—H···O interactions in (IV) (dashed lines), involving the cation (top) and the anion (bottom).

(I) dipyridinium dioxidobis(oxydiacetato)uranate(VI)

Crystal data

(C5H6N)2[U(C4H4O5)2O2]	F(000) = 660
Mr = 694.39	Dx = 2.142 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 5883 reflections
a = 6.675 (2) Å	θ = 3.0–25.0°
b = 23.025 (5) Å	µ = 7.61 mm^−1
c = 7.500 (2) Å	T = 100 K
β = 110.946 (11)°	Prism, yellow
V = 1076.5 (5) Å^3	0.2 × 0.2 × 0.1 mm
Z = 2

Data collection

Rigaku R-AXIS IIC image-plate diffractometer	1853 independent reflections
Radiation source: rotating-anode X-ray tube, Rigaku RU-H3R	1763 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 105 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ϕ scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −27→24
Tmin = 0.240, Tmax = 0.470	l = −8→8
5883 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.038	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0169P)^2 + 0.7202P] where P = (Fo^2 + 2Fc^2)/3
1853 reflections	(Δ/σ)max = 0.001
161 parameters	Δρmax = 0.81 e Å^−3
1 restraint	Δρmin = −0.96 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2005 (5)	0.14723 (12)	0.6860 (4)	0.0098 (6)
C2	0.1218 (5)	0.19806 (12)	0.7705 (4)	0.0099 (6)
H2A	−0.0305	0.1941	0.7456	0.012*
H2B	0.1969	0.1994	0.9076	0.012*
C3	0.6803 (4)	0.15744 (12)	0.2908 (4)	0.0098 (6)
C4	0.6827 (5)	0.19771 (12)	0.1312 (4)	0.0123 (6)
H4A	0.8299	0.2064	0.1458	0.015*
H4B	0.6156	0.1784	0.0092	0.015*
C5	0.7778 (5)	−0.01458 (13)	0.5828 (4)	0.0138 (6)
H5	0.8045	−0.0311	0.4803	0.017*
C6	0.7802 (5)	−0.04867 (13)	0.7335 (4)	0.0163 (6)
H6	0.8081	−0.0883	0.7343	0.020*
C7	0.7402 (5)	−0.02294 (14)	0.8853 (4)	0.0172 (7)
H7	0.7416	−0.0453	0.9891	0.021*
C8	0.6982 (5)	0.03611 (14)	0.8813 (4)	0.0153 (6)
H8	0.6709	0.0538	0.9819	0.018*
C9	0.6976 (5)	0.06821 (13)	0.7265 (4)	0.0130 (6)
H9	0.6697	0.1079	0.7215	0.016*
O1	0.2058 (5)	0.2500	0.2704 (4)	0.0135 (6)
O2	0.6224 (5)	0.2500	0.7273 (4)	0.0122 (6)
O3	0.2918 (3)	0.16052 (9)	0.5665 (3)	0.0152 (5)
O4	0.1753 (3)	0.09789 (9)	0.7362 (3)	0.0146 (4)
O5	0.1617 (5)	0.2500	0.6843 (4)	0.0108 (6)
O6	0.6254 (3)	0.17793 (9)	0.4239 (3)	0.0132 (4)
O7	0.7398 (4)	0.10647 (9)	0.2845 (3)	0.0153 (5)
O8	0.5726 (5)	0.2500	0.1329 (4)	0.0133 (6)
U1	0.41668 (2)	0.2500	0.497706 (19)	0.00626 (7)
N1	0.7374 (4)	0.04215 (11)	0.5828 (3)	0.0118 (5)
H1	0.740 (7)	0.0628 (15)	0.486 (4)	0.030 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0074 (14)	0.0112 (14)	0.0097 (13)	−0.0017 (11)	0.0018 (11)	−0.0006 (11)
C2	0.0117 (14)	0.0092 (14)	0.0100 (14)	−0.0018 (12)	0.0051 (12)	0.0020 (11)
C3	0.0058 (14)	0.0125 (14)	0.0098 (13)	−0.0041 (12)	0.0014 (11)	−0.0029 (11)
C4	0.0134 (15)	0.0105 (15)	0.0125 (14)	0.0014 (12)	0.0040 (12)	−0.0006 (11)
C5	0.0079 (14)	0.0185 (15)	0.0147 (14)	−0.0027 (12)	0.0036 (12)	−0.0065 (12)
C6	0.0134 (15)	0.0109 (15)	0.0213 (16)	0.0007 (12)	0.0021 (13)	−0.0007 (12)
C7	0.0140 (16)	0.0206 (16)	0.0138 (15)	−0.0016 (13)	0.0013 (13)	0.0064 (12)
C8	0.0129 (15)	0.0201 (16)	0.0127 (14)	−0.0010 (12)	0.0044 (12)	−0.0034 (12)
C9	0.0113 (15)	0.0110 (14)	0.0160 (15)	0.0006 (12)	0.0041 (12)	−0.0007 (12)
O1	0.0093 (15)	0.0182 (15)	0.0114 (14)	0.000	0.0018 (12)	0.000
O2	0.0149 (16)	0.0141 (14)	0.0065 (13)	0.000	0.0025 (12)	0.000
O3	0.0192 (12)	0.0090 (10)	0.0225 (11)	−0.0026 (9)	0.0137 (10)	−0.0019 (8)
O4	0.0192 (12)	0.0097 (10)	0.0163 (10)	−0.0002 (9)	0.0080 (9)	0.0025 (8)
O5	0.0159 (16)	0.0067 (13)	0.0131 (14)	0.000	0.0091 (13)	0.000
O6	0.0156 (11)	0.0142 (10)	0.0131 (10)	0.0045 (9)	0.0090 (9)	0.0006 (8)
O7	0.0237 (12)	0.0110 (10)	0.0146 (10)	0.0037 (9)	0.0109 (10)	0.0007 (8)
O8	0.0120 (15)	0.0092 (14)	0.0208 (15)	0.000	0.0085 (13)	0.000
U1	0.00693 (9)	0.00612 (9)	0.00608 (9)	0.000	0.00275 (6)	0.000
N1	0.0089 (12)	0.0160 (13)	0.0099 (12)	−0.0020 (10)	0.0026 (10)	0.0025 (10)

Geometric parameters (Å, º)

C1—O4	1.227 (4)	C7—C8	1.386 (5)
C1—O3	1.288 (4)	C7—H7	0.9300
C1—C2	1.512 (4)	C8—C9	1.375 (4)
C2—O5	1.429 (3)	C8—H8	0.9300
C2—H2A	0.9700	C9—N1	1.340 (4)
C2—H2B	0.9700	C9—H9	0.9300
C3—O7	1.245 (4)	O1—U1	1.781 (3)
C3—O6	1.271 (4)	O2—U1	1.777 (3)
C3—C4	1.519 (4)	O3—U1	2.348 (2)
C4—O8	1.413 (3)	O5—C2^i	1.429 (3)
C4—H4A	0.9700	O5—U1	2.561 (3)
C4—H4B	0.9700	O6—U1	2.357 (2)
C5—N1	1.334 (4)	O8—C4^i	1.413 (3)
C5—C6	1.372 (4)	U1—O3^i	2.348 (2)
C5—H5	0.9300	U1—O6^i	2.357 (2)
C6—C7	1.391 (4)	N1—H1	0.875 (19)
C6—H6	0.9300
O4—C1—O3	125.8 (3)	C8—C9—H9	120.1
O4—C1—C2	118.8 (2)	C1—O3—U1	130.90 (18)
O3—C1—C2	115.5 (2)	C2—O5—C2^i	113.6 (3)
O5—C2—C1	108.0 (2)	C2—O5—U1	121.01 (15)
O5—C2—H2A	110.1	C2^i—O5—U1	121.01 (15)
C1—C2—H2A	110.1	C3—O6—U1	143.76 (19)
O5—C2—H2B	110.1	C4—O8—C4^i	116.9 (3)
C1—C2—H2B	110.1	O2—U1—O1	178.59 (12)
H2A—C2—H2B	108.4	O2—U1—O3	89.95 (7)
O7—C3—O6	124.4 (3)	O1—U1—O3	89.38 (7)
O7—C3—C4	116.9 (2)	O2—U1—O3^i	89.95 (7)
O6—C3—C4	118.7 (2)	O1—U1—O3^i	89.38 (7)
O8—C4—C3	111.2 (2)	O3—U1—O3^i	122.68 (10)
O8—C4—H4A	109.4	O2—U1—O6	84.87 (9)
C3—C4—H4A	109.4	O1—U1—O6	96.12 (8)
O8—C4—H4B	109.4	O3—U1—O6	73.72 (7)
C3—C4—H4B	109.4	O3^i—U1—O6	162.87 (7)
H4A—C4—H4B	108.0	O2—U1—O6^i	84.87 (9)
N1—C5—C6	120.2 (3)	O1—U1—O6^i	96.12 (8)
N1—C5—H5	119.9	O3—U1—O6^i	162.87 (7)
C6—C5—H5	119.9	O3^i—U1—O6^i	73.72 (7)
C5—C6—C7	118.8 (3)	O6—U1—O6^i	89.54 (10)
C5—C6—H6	120.6	O2—U1—O5	84.54 (12)
C7—C6—H6	120.6	O1—U1—O5	94.06 (11)
C8—C7—C6	119.8 (3)	O3—U1—O5	61.48 (5)
C8—C7—H7	120.1	O3^i—U1—O5	61.48 (5)
C6—C7—H7	120.1	O6—U1—O5	133.84 (5)
C9—C8—C7	119.0 (3)	O6^i—U1—O5	133.84 (5)
C9—C8—H8	120.5	C5—N1—C9	122.4 (3)
C7—C8—H8	120.5	C5—N1—H1	118 (3)
N1—C9—C8	119.8 (3)	C9—N1—H1	120 (3)
N1—C9—H9	120.1

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O7	0.87 (3)	1.82 (3)	2.688 (3)	179 (6)
C2—H2A···O2^ii	0.97	2.61	3.446 (5)	144
C4—H4A···O1^iii	0.97	2.55	3.482 (5)	161
C5—H5···O4^iv	0.93	2.28	3.168 (4)	161
C7—H7···O4^v	0.93	2.28	3.195 (4)	167
C8—H8···O7^vi	0.93	2.47	3.354 (4)	159

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

(II) bis(2-methyl-pyridinium) dioxidobis(oxydiacetato)uranate(VI)

Crystal data

(C6H8N)2[U(C4H4O5)2O2]	F(000) = 692
Mr = 722.44	Dx = 1.971 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7415 reflections
a = 9.183 (2) Å	θ = 3.0–25.0°
b = 11.104 (3) Å	µ = 6.73 mm^−1
c = 12.826 (4) Å	T = 295 K
β = 111.490 (7)°	Prism, yellow
V = 1217.0 (6) Å^3	0.2 × 0.2 × 0.1 mm
Z = 2

Data collection

Rigaku R-AXIS IIC image-plate diffractometer	2106 independent reflections
Radiation source: rotating-anode X-ray tube, Rigaku RU-H3R	1694 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 105 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ϕ scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −13→13
Tmin = 0.304, Tmax = 0.510	l = −14→15
7415 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 1.7775P] where P = (Fo^2 + 2Fc^2)/3
2106 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 1.15 e Å^−3
0 restraints	Δρmin = −1.38 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2297 (5)	−0.2415 (4)	0.1298 (4)	0.0366 (10)
C2	0.3682 (5)	−0.1601 (4)	0.1499 (4)	0.0448 (12)
H2A	0.4293	−0.1539	0.2294	0.054*
H2B	0.4348	−0.1911	0.1123	0.054*
C3	0.4244 (6)	0.0439 (5)	0.1218 (6)	0.0624 (17)
H3A	0.5088	0.0130	0.1011	0.075*
H3B	0.4672	0.0692	0.1996	0.075*
C4	0.3444 (5)	0.1465 (4)	0.0478 (5)	0.0472 (12)
C5	−0.1765 (6)	0.6455 (5)	−0.2108 (5)	0.0580 (14)
H5A	−0.2099	0.6479	−0.2910	0.087*
H5B	−0.1767	0.7255	−0.1827	0.087*
H5C	−0.2467	0.5957	−0.1898	0.087*
C6	−0.0157 (6)	0.5948 (4)	−0.1628 (4)	0.0382 (10)
C7	0.1197 (6)	0.6589 (4)	−0.1471 (4)	0.0458 (12)
H7	0.1137	0.7402	−0.1658	0.055*
C8	0.2626 (6)	0.6036 (5)	−0.1042 (5)	0.0573 (14)
H8	0.3533	0.6474	−0.0933	0.069*
C9	0.2722 (7)	0.4822 (5)	−0.0770 (6)	0.0567 (15)
H9	0.3684	0.4430	−0.0496	0.068*
C10	0.1364 (6)	0.4216 (4)	−0.0916 (4)	0.0460 (11)
H10	0.1401	0.3406	−0.0724	0.055*
N1	−0.0011 (5)	0.4779 (3)	−0.1330 (3)	0.0361 (9)
O1	0.0042 (4)	0.0549 (3)	0.1298 (3)	0.0441 (8)
O2	0.0958 (3)	−0.1982 (2)	0.0778 (3)	0.0417 (7)
O3	0.2569 (4)	−0.3464 (3)	0.1655 (3)	0.0517 (9)
O4	0.3067 (4)	−0.0462 (3)	0.1057 (3)	0.0566 (10)
O5	0.1986 (3)	0.1378 (3)	−0.0026 (3)	0.0540 (9)
O6	0.4252 (4)	0.2318 (3)	0.0393 (4)	0.0861 (15)
U1	0.0000	0.0000	0.0000	0.02645 (10)
H1	−0.084 (6)	0.441 (5)	−0.137 (4)	0.050 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.036 (2)	0.028 (2)	0.044 (3)	0.0004 (18)	0.012 (2)	0.0039 (19)
C2	0.032 (2)	0.030 (2)	0.065 (3)	0.0045 (19)	0.009 (2)	0.015 (2)
C3	0.032 (3)	0.039 (3)	0.098 (5)	−0.014 (2)	0.003 (3)	0.021 (3)
C4	0.032 (2)	0.035 (3)	0.072 (3)	−0.004 (2)	0.016 (2)	0.010 (2)
C5	0.060 (3)	0.042 (3)	0.067 (4)	0.008 (2)	0.018 (3)	0.005 (3)
C6	0.054 (3)	0.029 (2)	0.032 (2)	−0.002 (2)	0.015 (2)	−0.0031 (18)
C7	0.063 (3)	0.025 (2)	0.050 (3)	−0.012 (2)	0.022 (3)	0.001 (2)
C8	0.051 (3)	0.048 (3)	0.070 (4)	−0.021 (3)	0.018 (3)	−0.002 (3)
C9	0.042 (3)	0.047 (3)	0.073 (4)	−0.001 (2)	0.011 (3)	0.010 (3)
C10	0.049 (3)	0.034 (3)	0.053 (3)	−0.005 (2)	0.016 (2)	0.007 (2)
N1	0.043 (2)	0.027 (2)	0.037 (2)	−0.0084 (17)	0.0141 (18)	0.0000 (16)
O1	0.064 (2)	0.0293 (17)	0.0412 (18)	0.0008 (15)	0.0216 (16)	0.0011 (15)
O2	0.0303 (15)	0.0281 (15)	0.0579 (19)	−0.0018 (12)	0.0059 (14)	0.0078 (15)
O3	0.0395 (18)	0.0316 (17)	0.075 (2)	0.0020 (14)	0.0108 (17)	0.0193 (17)
O4	0.0329 (18)	0.0277 (16)	0.094 (3)	−0.0072 (15)	0.0050 (18)	0.0180 (19)
O5	0.0320 (17)	0.0413 (18)	0.082 (3)	−0.0069 (14)	0.0129 (17)	0.0208 (18)
O6	0.041 (2)	0.049 (2)	0.153 (4)	−0.0139 (18)	0.018 (2)	0.041 (3)
U1	0.02845 (13)	0.01915 (13)	0.02961 (13)	−0.00378 (8)	0.00812 (9)	0.00164 (8)

Geometric parameters (Å, º)

C1—O3	1.243 (5)	C7—C8	1.368 (7)
C1—O2	1.260 (5)	C7—H7	0.9300
C1—C2	1.503 (6)	C8—C9	1.387 (7)
C2—O4	1.416 (5)	C8—H8	0.9300
C2—H2A	0.9700	C9—C10	1.368 (7)
C2—H2B	0.9700	C9—H9	0.9300
C3—O4	1.431 (6)	C10—N1	1.333 (6)
C3—C4	1.493 (7)	C10—H10	0.9300
C3—H3A	0.9700	N1—H1	0.85 (6)
C3—H3B	0.9700	O1—U1	1.760 (3)
C4—O6	1.232 (5)	O2—U1	2.443 (3)
C4—O5	1.260 (5)	O4—U1	2.690 (3)
C5—C6	1.487 (7)	O5—U1	2.391 (3)
C5—H5A	0.9600	U1—O1^i	1.760 (3)
C5—H5B	0.9600	U1—O5^i	2.390 (3)
C5—H5C	0.9600	U1—O2^i	2.443 (3)
C6—N1	1.345 (6)	U1—O4^i	2.690 (3)
C6—C7	1.382 (6)
O3—C1—O2	125.3 (4)	C9—C10—H10	119.8
O3—C1—C2	117.2 (4)	C10—N1—C6	123.2 (4)
O2—C1—C2	117.5 (4)	C10—N1—H1	120 (4)
O4—C2—C1	106.3 (3)	C6—N1—H1	117 (4)
O4—C2—H2A	110.5	C1—O2—U1	134.1 (3)
C1—C2—H2A	110.5	C2—O4—C3	113.4 (4)
O4—C2—H2B	110.5	C2—O4—U1	124.2 (2)
C1—C2—H2B	110.5	C3—O4—U1	122.4 (3)
H2A—C2—H2B	108.7	C4—O5—U1	135.6 (3)
O4—C3—C4	105.8 (4)	O1—U1—O1^i	180.0
O4—C3—H3A	110.6	O1—U1—O5^i	87.76 (14)
C4—C3—H3A	110.6	O1^i—U1—O5^i	92.24 (14)
O4—C3—H3B	110.6	O1—U1—O5	92.24 (14)
C4—C3—H3B	110.6	O1^i—U1—O5	87.76 (14)
H3A—C3—H3B	108.7	O5^i—U1—O5	180.0
O6—C4—O5	125.1 (5)	O1—U1—O2^i	87.37 (13)
O6—C4—C3	118.1 (4)	O1^i—U1—O2^i	92.63 (13)
O5—C4—C3	116.8 (4)	O5^i—U1—O2^i	114.84 (10)
C6—C5—H5A	109.5	O5—U1—O2^i	65.16 (10)
C6—C5—H5B	109.5	O1—U1—O2	92.63 (13)
H5A—C5—H5B	109.5	O1^i—U1—O2	87.37 (13)
C6—C5—H5C	109.5	O5^i—U1—O2	65.16 (10)
H5A—C5—H5C	109.5	O5—U1—O2	114.84 (10)
H5B—C5—H5C	109.5	O2^i—U1—O2	180.0
N1—C6—C7	117.7 (4)	O1—U1—O4^i	93.82 (14)
N1—C6—C5	117.6 (4)	O1^i—U1—O4^i	86.18 (14)
C7—C6—C5	124.7 (4)	O5^i—U1—O4^i	57.73 (10)
C8—C7—C6	120.4 (4)	O5—U1—O4^i	122.27 (10)
C8—C7—H7	119.8	O2^i—U1—O4^i	57.89 (10)
C6—C7—H7	119.8	O2—U1—O4^i	122.11 (10)
C7—C8—C9	120.0 (5)	O1—U1—O4	86.18 (14)
C7—C8—H8	120.0	O1^i—U1—O4	93.82 (14)
C9—C8—H8	120.0	O5^i—U1—O4	122.27 (10)
C10—C9—C8	118.2 (5)	O5—U1—O4	57.73 (10)
C10—C9—H9	120.9	O2^i—U1—O4	122.11 (10)
C8—C9—H9	120.9	O2—U1—O4	57.89 (10)
N1—C10—C9	120.4 (5)	O4^i—U1—O4	180.0
N1—C10—H10	119.8

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.90 (6)	1.77 (6)	2.666 (5)	169.5
C7—H7···O1^ii	0.93	2.63	3.409 (6)	141
C8—H8···O6^iii	0.93	2.32	3.242 (7)	171
C10—H10···O5	0.93	2.41	3.328 (6)	170

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

(III) bis(3-methylpyridinium) dioxidobis(oxydiacetato)uranate(VI)

Crystal data

(C6H8N)2[U(C4H4O5)2O2]	F(000) = 692
Mr = 722.44	Dx = 2.059 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7099 reflections
a = 7.415 (2) Å	θ = 3.2–25.0°
b = 13.312 (5) Å	µ = 7.03 mm^−1
c = 11.806 (4) Å	T = 295 K
β = 91.224 (15)°	Prism, yellow
V = 1165.1 (7) Å^3	0.4 × 0.2 × 0.1 mm
Z = 2

Data collection

Rigaku R-AXIS IIC image-plate diffractometer	1885 independent reflections
Radiation source: rotating-anode X-ray tube, Rigaku RU-H3R	1544 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.104
Detector resolution: 105 pixels mm^-1	θmax = 25.0°, θmin = 3.2°
ϕ scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −15→15
Tmin = 0.088, Tmax = 0.500	l = −14→14
7099 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0872P)^2] where P = (Fo^2 + 2Fc^2)/3
1885 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 2.20 e Å^−3
0 restraints	Δρmin = −3.34 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3040 (7)	0.1055 (4)	−0.1778 (5)	0.0350 (13)
C2	0.4052 (8)	0.1423 (5)	−0.0752 (5)	0.0382 (14)
H2A	0.5286	0.1181	−0.0753	0.046*
H2B	0.4072	0.2152	−0.0741	0.046*
C3	0.3940 (7)	0.1299 (5)	0.1269 (4)	0.0357 (13)
H3A	0.4141	0.2018	0.1316	0.043*
H3B	0.5089	0.0959	0.1369	0.043*
C4	0.2661 (7)	0.0971 (4)	0.2150 (4)	0.0313 (12)
O1	−0.1292 (6)	0.1104 (3)	−0.0077 (3)	0.0449 (10)
O2	0.1649 (6)	0.0525 (5)	−0.1586 (3)	0.0546 (14)
O3	0.3562 (6)	0.1286 (4)	−0.2724 (3)	0.0507 (12)
O4	0.3135 (6)	0.1045 (3)	0.0216 (3)	0.0474 (11)
O5	0.1239 (5)	0.0552 (4)	0.1814 (3)	0.0489 (12)
O6	0.3048 (5)	0.1155 (3)	0.3162 (3)	0.0417 (10)
U1	0.0000	0.0000	0.0000	0.0259 (2)
C5	−0.1428 (8)	0.0746 (5)	0.3917 (5)	0.0372 (13)
H5	−0.1378	0.0447	0.3207	0.045*
C6	−0.3006 (8)	0.0792 (5)	0.4459 (5)	0.0420 (14)
H6	−0.4049	0.0527	0.4125	0.050*
C7	−0.3058 (8)	0.1237 (5)	0.5515 (5)	0.0402 (14)
H7	−0.4148	0.1269	0.5889	0.048*
C8	−0.1529 (9)	0.1636 (5)	0.6025 (5)	0.0355 (13)
C9	0.0049 (11)	0.1569 (6)	0.5431 (7)	0.0424 (17)
H9	0.1115	0.1827	0.5741	0.051*
C10	−0.1552 (11)	0.2138 (5)	0.7147 (5)	0.0583 (19)
H10A	−0.0521	0.1929	0.7592	0.087*
H10B	−0.2634	0.1957	0.7530	0.087*
H10C	−0.1517	0.2853	0.7045	0.087*
N1	0.0051 (8)	0.1127 (4)	0.4394 (5)	0.0355 (13)
H1	0.121 (9)	0.101 (5)	0.410 (6)	0.047 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.034 (3)	0.032 (3)	0.040 (3)	−0.003 (2)	0.006 (3)	−0.003 (2)
C2	0.033 (3)	0.044 (4)	0.039 (3)	−0.013 (3)	0.011 (3)	0.001 (3)
C3	0.031 (3)	0.045 (4)	0.031 (3)	−0.007 (2)	0.002 (2)	−0.004 (2)
C4	0.027 (3)	0.031 (3)	0.036 (3)	−0.003 (2)	−0.004 (2)	−0.001 (2)
O1	0.046 (2)	0.041 (2)	0.048 (3)	0.011 (2)	−0.0026 (19)	−0.0037 (19)
O2	0.044 (3)	0.088 (4)	0.032 (2)	−0.038 (3)	0.0103 (19)	−0.003 (2)
O3	0.056 (3)	0.064 (3)	0.032 (2)	−0.023 (2)	0.013 (2)	−0.007 (2)
O4	0.049 (2)	0.067 (3)	0.027 (2)	−0.028 (2)	0.0057 (18)	−0.0030 (19)
O5	0.044 (2)	0.069 (4)	0.034 (2)	−0.027 (2)	0.0056 (18)	−0.013 (2)
O6	0.036 (2)	0.059 (3)	0.031 (2)	−0.010 (2)	0.0007 (18)	−0.0061 (19)
U1	0.0261 (3)	0.0278 (3)	0.0240 (3)	−0.00483 (9)	0.0025 (2)	−0.00327 (8)
C5	0.049 (3)	0.034 (3)	0.028 (3)	−0.003 (3)	−0.003 (3)	0.001 (2)
C6	0.038 (3)	0.045 (4)	0.043 (4)	−0.005 (3)	−0.002 (3)	0.001 (3)
C7	0.037 (3)	0.036 (3)	0.048 (3)	−0.001 (3)	0.013 (3)	0.006 (3)
C8	0.050 (3)	0.025 (3)	0.031 (3)	0.004 (3)	0.003 (2)	0.001 (2)
C9	0.050 (4)	0.044 (4)	0.033 (4)	−0.005 (3)	−0.006 (3)	0.005 (4)
C10	0.087 (5)	0.046 (4)	0.042 (4)	0.001 (4)	0.008 (4)	−0.006 (3)
N1	0.041 (3)	0.033 (3)	0.033 (3)	0.001 (3)	0.005 (2)	0.002 (2)

Geometric parameters (Å, º)

C1—O3	1.229 (7)	U1—O5^i	2.426 (4)
C1—O2	1.274 (7)	U1—O4^i	2.716 (4)
C1—C2	1.494 (8)	C5—N1	1.322 (8)
C2—O4	1.435 (7)	C5—C6	1.346 (8)
C2—H2A	0.9700	C5—H5	0.9300
C2—H2B	0.9700	C6—C7	1.382 (8)
C3—O4	1.408 (6)	C6—H6	0.9300
C3—C4	1.487 (7)	C7—C8	1.379 (9)
C3—H3A	0.9700	C7—H7	0.9300
C3—H3B	0.9700	C8—C9	1.380 (10)
C4—O6	1.247 (6)	C8—C10	1.484 (8)
C4—O5	1.250 (6)	C9—N1	1.359 (12)
O1—U1	1.756 (4)	C9—H9	0.9300
O2—U1	2.364 (4)	C10—H10A	0.9600
O4—U1	2.716 (4)	C10—H10B	0.9600
O5—U1	2.426 (4)	C10—H10C	0.9600
U1—O1^i	1.756 (4)	N1—H1	0.95 (7)
U1—O2^i	2.364 (4)
O3—C1—O2	124.9 (6)	O1—U1—O4^i	87.64 (17)
O3—C1—C2	119.5 (5)	O1^i—U1—O4^i	92.35 (17)
O2—C1—C2	115.6 (5)	O2—U1—O4^i	122.21 (13)
O4—C2—C1	107.0 (4)	O2^i—U1—O4^i	57.79 (13)
O4—C2—H2A	110.3	O5^i—U1—O4^i	56.95 (12)
C1—C2—H2A	110.3	O5—U1—O4^i	123.05 (12)
O4—C2—H2B	110.3	O1—U1—O4	92.36 (17)
C1—C2—H2B	110.3	O1^i—U1—O4	87.64 (17)
H2A—C2—H2B	108.6	O2—U1—O4	57.79 (13)
O4—C3—C4	106.4 (4)	O2^i—U1—O4	122.21 (13)
O4—C3—H3A	110.5	O5^i—U1—O4	123.05 (12)
C4—C3—H3A	110.5	O5—U1—O4	56.95 (12)
O4—C3—H3B	110.5	O4^i—U1—O4	180.0
C4—C3—H3B	110.5	N1—C5—C6	120.1 (6)
H3A—C3—H3B	108.6	N1—C5—H5	119.9
O6—C4—O5	124.5 (5)	C6—C5—H5	119.9
O6—C4—C3	118.4 (5)	C5—C6—C7	119.3 (6)
O5—C4—C3	117.1 (5)	C5—C6—H6	120.3
C1—O2—U1	137.7 (4)	C7—C6—H6	120.3
C3—O4—C2	114.8 (4)	C8—C7—C6	121.4 (5)
C3—O4—U1	123.5 (3)	C8—C7—H7	119.3
C2—O4—U1	121.6 (3)	C6—C7—H7	119.3
C4—O5—U1	135.7 (3)	C7—C8—C9	116.8 (6)
O1—U1—O1^i	180.0	C7—C8—C10	122.5 (6)
O1—U1—O2	90.1 (2)	C9—C8—C10	120.6 (6)
O1^i—U1—O2	89.9 (2)	N1—C9—C8	120.2 (8)
O1—U1—O2^i	89.9 (2)	N1—C9—H9	119.9
O1^i—U1—O2^i	90.1 (2)	C8—C9—H9	119.9
O2—U1—O2^i	180.0	C8—C10—H10A	109.5
O1—U1—O5^i	90.67 (18)	C8—C10—H10B	109.5
O1^i—U1—O5^i	89.33 (18)	H10A—C10—H10B	109.5
O2—U1—O5^i	65.35 (14)	C8—C10—H10C	109.5
O2^i—U1—O5^i	114.66 (14)	H10A—C10—H10C	109.5
O1—U1—O5	89.33 (18)	H10B—C10—H10C	109.5
O1^i—U1—O5	90.67 (18)	C5—N1—C9	122.2 (7)
O2—U1—O5	114.65 (14)	C5—N1—H1	122 (4)
O2^i—U1—O5	65.35 (14)	C9—N1—H1	115 (4)
O5^i—U1—O5	180.0

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6	0.94 (7)	1.79 (7)	2.682 (7)	157 (6)
C3—H3A···O3^ii	0.97	2.57	3.441 (8)	150
C5—H5···O2^i	0.93	2.32	3.233 (8)	169
C6—H6···O6^iii	0.93	2.55	3.309 (7)	139
C7—H7···O3^iv	0.93	2.38	3.291 (7)	165

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

(IV) bis(4-methylpyridinium) dioxidobis(oxydiacetato)uranate(VI)

Crystal data

(C6H8N)2[U(C4H4O5)2O2]	F(000) = 692
Mr = 722.24	Dx = 2.063 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6992 reflections
a = 7.3439 (13) Å	θ = 3.2–25.0°
b = 12.999 (2) Å	µ = 7.05 mm^−1
c = 12.194 (2) Å	T = 295 K
β = 92.438 (9)°	Prism, yellow
V = 1163.0 (3) Å^3	0.2 × 0.2 × 0.1 mm
Z = 2

Data collection

Rigaku R-AXIS IIC image-plate diffractometer	2002 independent reflections
Radiation source: rotating-anode X-ray tube, Rigaku RU-H3R	1752 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
Detector resolution: 105 pixels mm^-1	θmax = 25.0°, θmin = 3.2°
ϕ scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	k = −15→15
Tmin = 0.231, Tmax = 0.490	l = −14→14
6992 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 1.96P] where P = (Fo^2 + 2Fc^2)/3
2002 reflections	(Δ/σ)max = 0.010
165 parameters	Δρmax = 2.28 e Å^−3
1 restraint	Δρmin = −1.99 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3021 (7)	0.0894 (4)	−0.1824 (4)	0.0293 (11)
C2	0.4046 (7)	0.1337 (4)	−0.0839 (4)	0.0307 (12)
H2A	0.5260	0.1043	−0.0770	0.037*
H2B	0.4157	0.2077	−0.0914	0.037*
C3	0.3855 (8)	0.1489 (5)	0.1096 (4)	0.0364 (13)
H3A	0.3748	0.2233	0.1111	0.044*
H3B	0.5137	0.1310	0.1159	0.044*
C4	0.2866 (7)	0.1025 (4)	0.2020 (4)	0.0306 (12)
C5	0.2897 (9)	−0.0831 (4)	0.4181 (5)	0.0434 (14)
H5	0.3901	−0.0613	0.3804	0.052*
C6	0.3121 (8)	−0.1205 (4)	0.5222 (5)	0.0389 (13)
H6	0.4279	−0.1226	0.5560	0.047*
C7	0.1649 (8)	−0.1552 (4)	0.5775 (4)	0.0302 (12)
C8	−0.0063 (7)	−0.1502 (5)	0.5253 (5)	0.0350 (14)
H8	−0.1086	−0.1737	0.5600	0.042*
C9	−0.0218 (9)	−0.1093 (5)	0.4199 (5)	0.0385 (14)
H9	−0.1359	−0.1040	0.3842	0.046*
C10	0.1847 (10)	−0.1962 (5)	0.6926 (5)	0.0510 (17)
H10A	0.3115	−0.1982	0.7153	0.077*
H10B	0.1347	−0.2643	0.6950	0.077*
H10C	0.1207	−0.1521	0.7411	0.077*
N1	0.1233 (8)	−0.0780 (4)	0.3706 (4)	0.0395 (12)
O1	0.1246 (5)	−0.1151 (3)	−0.0086 (3)	0.0370 (9)
O2	0.1430 (5)	0.0555 (3)	−0.1645 (3)	0.0392 (10)
O3	0.3736 (5)	0.0920 (4)	−0.2714 (3)	0.0482 (11)
O4	0.3053 (5)	0.1093 (3)	0.0099 (3)	0.0361 (9)
O5	0.1656 (6)	0.0347 (4)	0.1743 (3)	0.0384 (9)
O6	0.3260 (6)	0.1291 (3)	0.2964 (3)	0.0423 (10)
U1	0.0000	0.0000	0.0000	0.01952 (15)
H1	0.115 (11)	−0.045 (6)	0.306 (4)	0.08 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.027 (3)	0.038 (3)	0.022 (3)	−0.004 (2)	−0.004 (2)	0.004 (2)
C2	0.024 (3)	0.041 (3)	0.027 (3)	−0.011 (2)	0.002 (2)	0.005 (2)
C3	0.039 (3)	0.048 (3)	0.022 (3)	−0.018 (3)	−0.002 (2)	−0.005 (2)
C4	0.028 (3)	0.037 (3)	0.026 (3)	−0.005 (2)	−0.003 (2)	0.001 (2)
C5	0.045 (4)	0.040 (3)	0.047 (4)	0.004 (3)	0.022 (3)	0.008 (3)
C6	0.032 (3)	0.036 (3)	0.048 (4)	0.003 (2)	−0.001 (2)	0.000 (3)
C7	0.042 (3)	0.025 (3)	0.024 (3)	0.004 (2)	0.004 (2)	−0.001 (2)
C8	0.035 (3)	0.039 (4)	0.031 (3)	−0.007 (2)	0.006 (2)	−0.001 (3)
C9	0.040 (3)	0.042 (3)	0.032 (3)	−0.001 (3)	−0.006 (3)	−0.004 (3)
C10	0.072 (5)	0.055 (4)	0.025 (3)	0.008 (3)	−0.005 (3)	0.007 (3)
N1	0.060 (3)	0.035 (3)	0.023 (2)	0.006 (2)	0.006 (2)	0.001 (2)
O1	0.042 (2)	0.0302 (19)	0.038 (2)	0.0028 (17)	−0.0008 (17)	0.0004 (17)
O2	0.030 (2)	0.067 (3)	0.0205 (18)	−0.022 (2)	−0.0006 (15)	0.005 (2)
O3	0.035 (2)	0.086 (3)	0.024 (2)	−0.011 (2)	0.0086 (17)	−0.006 (2)
O4	0.036 (2)	0.055 (2)	0.0170 (18)	−0.0227 (18)	0.0005 (15)	−0.0002 (17)
O5	0.042 (2)	0.053 (2)	0.019 (2)	−0.023 (2)	−0.0056 (16)	0.004 (2)
O6	0.051 (3)	0.057 (3)	0.019 (2)	−0.015 (2)	−0.0022 (17)	−0.0024 (18)
U1	0.0204 (2)	0.02217 (19)	0.0158 (2)	−0.00304 (8)	−0.00104 (11)	0.00298 (9)

Geometric parameters (Å, º)

C1—O3	1.226 (6)	C7—C10	1.503 (7)
C1—O2	1.276 (6)	C8—C9	1.391 (8)
C1—C2	1.505 (7)	C8—H8	0.9300
C2—O4	1.418 (6)	C9—N1	1.310 (8)
C2—H2A	0.9700	C9—H9	0.9300
C2—H2B	0.9700	C10—H10A	0.9600
C3—O4	1.425 (6)	C10—H10B	0.9600
C3—C4	1.493 (7)	C10—H10C	0.9600
C3—H3A	0.9700	N1—H1	0.90 (6)
C3—H3B	0.9700	O1—U1	1.760 (4)
C4—O6	1.226 (6)	O2—U1	2.414 (4)
C4—O5	1.287 (6)	O4—U1	2.653 (3)
C5—N1	1.332 (8)	O5—U1	2.445 (4)
C5—C6	1.362 (8)	U1—O1^i	1.760 (4)
C5—H5	0.9300	U1—O2^i	2.414 (4)
C6—C7	1.374 (8)	U1—O5^i	2.445 (4)
C6—H6	0.9300	U1—O4^i	2.653 (3)
C7—C8	1.386 (8)
O3—C1—O2	126.2 (5)	H10B—C10—H10C	109.5
O3—C1—C2	118.6 (5)	C9—N1—C5	122.3 (5)
O2—C1—C2	115.2 (5)	C9—N1—H1	122 (5)
O4—C2—C1	107.5 (4)	C5—N1—H1	116 (5)
O4—C2—H2A	110.2	C1—O2—U1	132.8 (3)
C1—C2—H2A	110.2	C2—O4—C3	113.5 (4)
O4—C2—H2B	110.2	C2—O4—U1	123.1 (3)
C1—C2—H2B	110.2	C3—O4—U1	123.4 (3)
H2A—C2—H2B	108.5	C4—O5—U1	131.8 (3)
O4—C3—C4	107.5 (4)	O1—U1—O1^i	180.0
O4—C3—H3A	110.2	O1—U1—O2^i	92.34 (17)
C4—C3—H3A	110.2	O1^i—U1—O2^i	87.66 (17)
O4—C3—H3B	110.2	O1—U1—O2	87.66 (17)
C4—C3—H3B	110.2	O1^i—U1—O2	92.34 (17)
H3A—C3—H3B	108.5	O2^i—U1—O2	180.0
O6—C4—O5	124.9 (5)	O1—U1—O5	88.15 (18)
O6—C4—C3	119.5 (5)	O1^i—U1—O5	91.85 (18)
O5—C4—C3	115.6 (4)	O2^i—U1—O5	63.31 (12)
N1—C5—C6	119.7 (5)	O2—U1—O5	116.69 (12)
N1—C5—H5	120.2	O1—U1—O5^i	91.85 (18)
C6—C5—H5	120.2	O1^i—U1—O5^i	88.15 (18)
C5—C6—C7	120.5 (5)	O2^i—U1—O5^i	116.69 (12)
C5—C6—H6	119.7	O2—U1—O5^i	63.30 (12)
C7—C6—H6	119.7	O5—U1—O5^i	180.0
C6—C7—C8	118.4 (5)	O1—U1—O4	91.02 (15)
C6—C7—C10	121.9 (5)	O1^i—U1—O4	88.98 (15)
C8—C7—C10	119.7 (5)	O2^i—U1—O4	121.28 (11)
C7—C8—C9	118.6 (6)	O2—U1—O4	58.72 (11)
C7—C8—H8	120.7	O5—U1—O4	58.24 (12)
C9—C8—H8	120.7	O5^i—U1—O4	121.76 (12)
N1—C9—C8	120.4 (5)	O1—U1—O4^i	88.98 (15)
N1—C9—H9	119.8	O1^i—U1—O4^i	91.02 (15)
C8—C9—H9	119.8	O2^i—U1—O4^i	58.72 (11)
C7—C10—H10A	109.5	O2—U1—O4^i	121.28 (11)
C7—C10—H10B	109.5	O5—U1—O4^i	121.76 (12)
H10A—C10—H10B	109.5	O5^i—U1—O4^i	58.24 (12)
C7—C10—H10C	109.5	O4—U1—O4^i	180.0
H10A—C10—H10C	109.5

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5	0.90 (6)	1.97 (6)	2.835 (6)	165 (7)
C2—H2B···O6^ii	0.97	2.59	3.451 (6)	147
C5—H5···O3^iii	0.93	2.27	3.115 (6)	152
C6—H6···O6^iv	0.93	2.50	3.387 (7)	160
C8—H8···O6^v	0.93	2.49	3.279 (7)	143
C9—H9···O3^i	0.93	2.18	3.099 (7)	169

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