Buy article online - an online subscription or single-article purchase is required to access this article.
Four complexes containing the [UO
2(oda)
2]
2− anion (oda is oxydiacetate) are reported, namely dipyridinium dioxidobis(oxydiacetato)uranate(VI), (C
5H
6N)
2[U(C
4H
4O
5)
2O
2], (I), bis(2-methylpyridinium) dioxidobis(oxydiacetato)uranate(VI), (C
8H
8N)
2[U(C
4H
4O
5)
2O
2], (II), bis(3-methylpyridinium) dioxidobis(oxydiacetato)uranate(VI), (C
8H
8N)
2[U(C
4H
4O
5)
2O
2], (III), and bis(4-methylpyridinium) dioxidobis(oxydiacetato)uranate(VI), (C
8H
8N)
2[U(C
4H
4O
5)
2O
2], (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 [UO
2(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.
Supporting information
CCDC references: 774065; 774066; 774067; 774068
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.
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 Uiso(H) =
1.2–1.5Uiso(C).
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).
(I) dipyridinium dioxidobis(oxydiacetato)uranate(VI)
top
Crystal data top
(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) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 2 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.016 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0169P)2 + 0.7202P] where P = (Fo2 + 2Fc2)/3 |
1853 reflections | (Δ/σ)max = 0.001 |
161 parameters | Δρmax = 0.81 e Å−3 |
1 restraint | Δρmin = −0.96 e Å−3 |
Crystal data top
(C5H6N)2[U(C4H4O5)2O2] | V = 1076.5 (5) Å3 |
Mr = 694.39 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 6.675 (2) Å | µ = 7.61 mm−1 |
b = 23.025 (5) Å | T = 100 K |
c = 7.500 (2) Å | 0.2 × 0.2 × 0.1 mm |
β = 110.946 (11)° | |
Data collection top
Rigaku R-AXIS IIC image-plate diffractometer | 1853 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1763 reflections with I > 2σ(I) |
Tmin = 0.240, Tmax = 0.470 | Rint = 0.032 |
5883 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.016 | 1 restraint |
wR(F2) = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.81 e Å−3 |
1853 reflections | Δρmin = −0.96 e Å−3 |
161 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 | |
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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—C2i | 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—C4i | 1.413 (3) |
C5—C6 | 1.372 (4) | U1—O3i | 2.348 (2) |
C5—H5 | 0.9300 | U1—O6i | 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—C2i | 113.6 (3) |
O5—C2—C1 | 108.0 (2) | C2—O5—U1 | 121.01 (15) |
O5—C2—H2A | 110.1 | C2i—O5—U1 | 121.01 (15) |
C1—C2—H2A | 110.1 | C3—O6—U1 | 143.76 (19) |
O5—C2—H2B | 110.1 | C4—O8—C4i | 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—O3i | 89.95 (7) |
O6—C3—C4 | 118.7 (2) | O1—U1—O3i | 89.38 (7) |
O8—C4—C3 | 111.2 (2) | O3—U1—O3i | 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 | O3i—U1—O6 | 162.87 (7) |
H4A—C4—H4B | 108.0 | O2—U1—O6i | 84.87 (9) |
N1—C5—C6 | 120.2 (3) | O1—U1—O6i | 96.12 (8) |
N1—C5—H5 | 119.9 | O3—U1—O6i | 162.87 (7) |
C6—C5—H5 | 119.9 | O3i—U1—O6i | 73.72 (7) |
C5—C6—C7 | 118.8 (3) | O6—U1—O6i | 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 | O3i—U1—O5 | 61.48 (5) |
C6—C7—H7 | 120.1 | O6—U1—O5 | 133.84 (5) |
C9—C8—C7 | 119.0 (3) | O6i—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) top
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···O2ii | 0.97 | 2.61 | 3.446 (5) | 144 |
C4—H4A···O1iii | 0.97 | 2.55 | 3.482 (5) | 161 |
C5—H5···O4iv | 0.93 | 2.28 | 3.168 (4) | 161 |
C7—H7···O4v | 0.93 | 2.28 | 3.195 (4) | 167 |
C8—H8···O7vi | 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)
top
Crystal data top
(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) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 2 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0396P)2 + 1.7775P] where P = (Fo2 + 2Fc2)/3 |
2106 reflections | (Δ/σ)max = 0.001 |
165 parameters | Δρmax = 1.15 e Å−3 |
0 restraints | Δρmin = −1.38 e Å−3 |
Crystal data top
(C6H8N)2[U(C4H4O5)2O2] | V = 1217.0 (6) Å3 |
Mr = 722.44 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.183 (2) Å | µ = 6.73 mm−1 |
b = 11.104 (3) Å | T = 295 K |
c = 12.826 (4) Å | 0.2 × 0.2 × 0.1 mm |
β = 111.490 (7)° | |
Data collection top
Rigaku R-AXIS IIC image-plate diffractometer | 2106 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1694 reflections with I > 2σ(I) |
Tmin = 0.304, Tmax = 0.510 | Rint = 0.027 |
7415 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.92 | Δρmax = 1.15 e Å−3 |
2106 reflections | Δρmin = −1.38 e Å−3 |
165 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 | |
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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—O1i | 1.760 (3) |
C5—H5B | 0.9600 | U1—O5i | 2.390 (3) |
C5—H5C | 0.9600 | U1—O2i | 2.443 (3) |
C6—N1 | 1.345 (6) | U1—O4i | 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—O1i | 180.0 |
O4—C3—H3A | 110.6 | O1—U1—O5i | 87.76 (14) |
C4—C3—H3A | 110.6 | O1i—U1—O5i | 92.24 (14) |
O4—C3—H3B | 110.6 | O1—U1—O5 | 92.24 (14) |
C4—C3—H3B | 110.6 | O1i—U1—O5 | 87.76 (14) |
H3A—C3—H3B | 108.7 | O5i—U1—O5 | 180.0 |
O6—C4—O5 | 125.1 (5) | O1—U1—O2i | 87.37 (13) |
O6—C4—C3 | 118.1 (4) | O1i—U1—O2i | 92.63 (13) |
O5—C4—C3 | 116.8 (4) | O5i—U1—O2i | 114.84 (10) |
C6—C5—H5A | 109.5 | O5—U1—O2i | 65.16 (10) |
C6—C5—H5B | 109.5 | O1—U1—O2 | 92.63 (13) |
H5A—C5—H5B | 109.5 | O1i—U1—O2 | 87.37 (13) |
C6—C5—H5C | 109.5 | O5i—U1—O2 | 65.16 (10) |
H5A—C5—H5C | 109.5 | O5—U1—O2 | 114.84 (10) |
H5B—C5—H5C | 109.5 | O2i—U1—O2 | 180.0 |
N1—C6—C7 | 117.7 (4) | O1—U1—O4i | 93.82 (14) |
N1—C6—C5 | 117.6 (4) | O1i—U1—O4i | 86.18 (14) |
C7—C6—C5 | 124.7 (4) | O5i—U1—O4i | 57.73 (10) |
C8—C7—C6 | 120.4 (4) | O5—U1—O4i | 122.27 (10) |
C8—C7—H7 | 119.8 | O2i—U1—O4i | 57.89 (10) |
C6—C7—H7 | 119.8 | O2—U1—O4i | 122.11 (10) |
C7—C8—C9 | 120.0 (5) | O1—U1—O4 | 86.18 (14) |
C7—C8—H8 | 120.0 | O1i—U1—O4 | 93.82 (14) |
C9—C8—H8 | 120.0 | O5i—U1—O4 | 122.27 (10) |
C10—C9—C8 | 118.2 (5) | O5—U1—O4 | 57.73 (10) |
C10—C9—H9 | 120.9 | O2i—U1—O4 | 122.11 (10) |
C8—C9—H9 | 120.9 | O2—U1—O4 | 57.89 (10) |
N1—C10—C9 | 120.4 (5) | O4i—U1—O4 | 180.0 |
N1—C10—H10 | 119.8 | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.90 (6) | 1.77 (6) | 2.666 (5) | 169.5 |
C7—H7···O1ii | 0.93 | 2.63 | 3.409 (6) | 141 |
C8—H8···O6iii | 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)
top
Crystal data top
(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) Å3 | 0.4 × 0.2 × 0.1 mm |
Z = 2 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0872P)2] where P = (Fo2 + 2Fc2)/3 |
1885 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 2.20 e Å−3 |
0 restraints | Δρmin = −3.34 e Å−3 |
Crystal data top
(C6H8N)2[U(C4H4O5)2O2] | V = 1165.1 (7) Å3 |
Mr = 722.44 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.415 (2) Å | µ = 7.03 mm−1 |
b = 13.312 (5) Å | T = 295 K |
c = 11.806 (4) Å | 0.4 × 0.2 × 0.1 mm |
β = 91.224 (15)° | |
Data collection top
Rigaku R-AXIS IIC image-plate diffractometer | 1885 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1544 reflections with I > 2σ(I) |
Tmin = 0.088, Tmax = 0.500 | Rint = 0.104 |
7099 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 2.20 e Å−3 |
1885 reflections | Δρmin = −3.34 e Å−3 |
165 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 | |
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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
C1—O3 | 1.229 (7) | U1—O5i | 2.426 (4) |
C1—O2 | 1.274 (7) | U1—O4i | 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—O1i | 1.756 (4) | N1—H1 | 0.95 (7) |
U1—O2i | 2.364 (4) | | |
| | | |
O3—C1—O2 | 124.9 (6) | O1—U1—O4i | 87.64 (17) |
O3—C1—C2 | 119.5 (5) | O1i—U1—O4i | 92.35 (17) |
O2—C1—C2 | 115.6 (5) | O2—U1—O4i | 122.21 (13) |
O4—C2—C1 | 107.0 (4) | O2i—U1—O4i | 57.79 (13) |
O4—C2—H2A | 110.3 | O5i—U1—O4i | 56.95 (12) |
C1—C2—H2A | 110.3 | O5—U1—O4i | 123.05 (12) |
O4—C2—H2B | 110.3 | O1—U1—O4 | 92.36 (17) |
C1—C2—H2B | 110.3 | O1i—U1—O4 | 87.64 (17) |
H2A—C2—H2B | 108.6 | O2—U1—O4 | 57.79 (13) |
O4—C3—C4 | 106.4 (4) | O2i—U1—O4 | 122.21 (13) |
O4—C3—H3A | 110.5 | O5i—U1—O4 | 123.05 (12) |
C4—C3—H3A | 110.5 | O5—U1—O4 | 56.95 (12) |
O4—C3—H3B | 110.5 | O4i—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—O1i | 180.0 | C7—C8—C10 | 122.5 (6) |
O1—U1—O2 | 90.1 (2) | C9—C8—C10 | 120.6 (6) |
O1i—U1—O2 | 89.9 (2) | N1—C9—C8 | 120.2 (8) |
O1—U1—O2i | 89.9 (2) | N1—C9—H9 | 119.9 |
O1i—U1—O2i | 90.1 (2) | C8—C9—H9 | 119.9 |
O2—U1—O2i | 180.0 | C8—C10—H10A | 109.5 |
O1—U1—O5i | 90.67 (18) | C8—C10—H10B | 109.5 |
O1i—U1—O5i | 89.33 (18) | H10A—C10—H10B | 109.5 |
O2—U1—O5i | 65.35 (14) | C8—C10—H10C | 109.5 |
O2i—U1—O5i | 114.66 (14) | H10A—C10—H10C | 109.5 |
O1—U1—O5 | 89.33 (18) | H10B—C10—H10C | 109.5 |
O1i—U1—O5 | 90.67 (18) | C5—N1—C9 | 122.2 (7) |
O2—U1—O5 | 114.65 (14) | C5—N1—H1 | 122 (4) |
O2i—U1—O5 | 65.35 (14) | C9—N1—H1 | 115 (4) |
O5i—U1—O5 | 180.0 | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
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···O3ii | 0.97 | 2.57 | 3.441 (8) | 150 |
C5—H5···O2i | 0.93 | 2.32 | 3.233 (8) | 169 |
C6—H6···O6iii | 0.93 | 2.55 | 3.309 (7) | 139 |
C7—H7···O3iv | 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)
top
Crystal data top
(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) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 2 | |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0435P)2 + 1.96P] where P = (Fo2 + 2Fc2)/3 |
2002 reflections | (Δ/σ)max = 0.010 |
165 parameters | Δρmax = 2.28 e Å−3 |
1 restraint | Δρmin = −1.99 e Å−3 |
Crystal data top
(C6H8N)2[U(C4H4O5)2O2] | V = 1163.0 (3) Å3 |
Mr = 722.24 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3439 (13) Å | µ = 7.05 mm−1 |
b = 12.999 (2) Å | T = 295 K |
c = 12.194 (2) Å | 0.2 × 0.2 × 0.1 mm |
β = 92.438 (9)° | |
Data collection top
Rigaku R-AXIS IIC image-plate diffractometer | 2002 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 1752 reflections with I > 2σ(I) |
Tmin = 0.231, Tmax = 0.490 | Rint = 0.061 |
6992 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 1 restraint |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 2.28 e Å−3 |
2002 reflections | Δρmin = −1.99 e Å−3 |
165 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 | |
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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—O1i | 1.760 (4) |
C5—H5 | 0.9300 | U1—O2i | 2.414 (4) |
C6—C7 | 1.374 (8) | U1—O5i | 2.445 (4) |
C6—H6 | 0.9300 | U1—O4i | 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—O1i | 180.0 |
O4—C3—H3A | 110.2 | O1—U1—O2i | 92.34 (17) |
C4—C3—H3A | 110.2 | O1i—U1—O2i | 87.66 (17) |
O4—C3—H3B | 110.2 | O1—U1—O2 | 87.66 (17) |
C4—C3—H3B | 110.2 | O1i—U1—O2 | 92.34 (17) |
H3A—C3—H3B | 108.5 | O2i—U1—O2 | 180.0 |
O6—C4—O5 | 124.9 (5) | O1—U1—O5 | 88.15 (18) |
O6—C4—C3 | 119.5 (5) | O1i—U1—O5 | 91.85 (18) |
O5—C4—C3 | 115.6 (4) | O2i—U1—O5 | 63.31 (12) |
N1—C5—C6 | 119.7 (5) | O2—U1—O5 | 116.69 (12) |
N1—C5—H5 | 120.2 | O1—U1—O5i | 91.85 (18) |
C6—C5—H5 | 120.2 | O1i—U1—O5i | 88.15 (18) |
C5—C6—C7 | 120.5 (5) | O2i—U1—O5i | 116.69 (12) |
C5—C6—H6 | 119.7 | O2—U1—O5i | 63.30 (12) |
C7—C6—H6 | 119.7 | O5—U1—O5i | 180.0 |
C6—C7—C8 | 118.4 (5) | O1—U1—O4 | 91.02 (15) |
C6—C7—C10 | 121.9 (5) | O1i—U1—O4 | 88.98 (15) |
C8—C7—C10 | 119.7 (5) | O2i—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 | O5i—U1—O4 | 121.76 (12) |
N1—C9—C8 | 120.4 (5) | O1—U1—O4i | 88.98 (15) |
N1—C9—H9 | 119.8 | O1i—U1—O4i | 91.02 (15) |
C8—C9—H9 | 119.8 | O2i—U1—O4i | 58.72 (11) |
C7—C10—H10A | 109.5 | O2—U1—O4i | 121.28 (11) |
C7—C10—H10B | 109.5 | O5—U1—O4i | 121.76 (12) |
H10A—C10—H10B | 109.5 | O5i—U1—O4i | 58.24 (12) |
C7—C10—H10C | 109.5 | O4—U1—O4i | 180.0 |
H10A—C10—H10C | 109.5 | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
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···O6ii | 0.97 | 2.59 | 3.451 (6) | 147 |
C5—H5···O3iii | 0.93 | 2.27 | 3.115 (6) | 152 |
C6—H6···O6iv | 0.93 | 2.50 | 3.387 (7) | 160 |
C8—H8···O6v | 0.93 | 2.49 | 3.279 (7) | 143 |
C9—H9···O3i | 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. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | (C5H6N)2[U(C4H4O5)2O2] | (C6H8N)2[U(C4H4O5)2O2] | (C6H8N)2[U(C4H4O5)2O2] | (C6H8N)2[U(C4H4O5)2O2] |
Mr | 694.39 | 722.44 | 722.44 | 722.24 |
Crystal system, space group | Monoclinic, P21/m | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 295 | 295 | 295 |
a, b, c (Å) | 6.675 (2), 23.025 (5), 7.500 (2) | 9.183 (2), 11.104 (3), 12.826 (4) | 7.415 (2), 13.312 (5), 11.806 (4) | 7.3439 (13), 12.999 (2), 12.194 (2) |
β (°) | 110.946 (11) | 111.490 (7) | 91.224 (15) | 92.438 (9) |
V (Å3) | 1076.5 (5) | 1217.0 (6) | 1165.1 (7) | 1163.0 (3) |
Z | 2 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 7.61 | 6.73 | 7.03 | 7.05 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 | 0.2 × 0.2 × 0.1 | 0.4 × 0.2 × 0.1 | 0.2 × 0.2 × 0.1 |
|
Data collection |
Diffractometer | Rigaku R-AXIS IIC image-plate diffractometer | Rigaku R-AXIS IIC image-plate diffractometer | Rigaku R-AXIS IIC image-plate diffractometer | Rigaku R-AXIS IIC image-plate diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2000) | Multi-scan (CrystalClear; Rigaku, 2000) | Multi-scan (CrystalClear; Rigaku, 2000) | Multi-scan (CrystalClear; Rigaku, 2000) |
Tmin, Tmax | 0.240, 0.470 | 0.304, 0.510 | 0.088, 0.500 | 0.231, 0.490 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5883, 1853, 1763 | 7415, 2106, 1694 | 7099, 1885, 1544 | 6992, 2002, 1752 |
Rint | 0.032 | 0.027 | 0.104 | 0.061 |
(sin θ/λ)max (Å−1) | 0.594 | 0.595 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.016, 0.038, 1.06 | 0.022, 0.059, 0.92 | 0.050, 0.130, 1.03 | 0.033, 0.086, 1.14 |
No. of reflections | 1853 | 2106 | 1885 | 2002 |
No. of parameters | 161 | 165 | 165 | 165 |
No. of restraints | 1 | 0 | 0 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.81, −0.96 | 1.15, −1.38 | 2.20, −3.34 | 2.28, −1.99 |
Hydrogen-bond geometry (Å, º) for (I) top
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···O2i | 0.97 | 2.61 | 3.446 (5) | 144 |
C4—H4A···O1ii | 0.97 | 2.55 | 3.482 (5) | 161 |
C5—H5···O4iii | 0.93 | 2.28 | 3.168 (4) | 161 |
C7—H7···O4iv | 0.93 | 2.28 | 3.195 (4) | 167 |
C8—H8···O7v | 0.93 | 2.47 | 3.354 (4) | 159 |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, −y, −z+1; (iv) −x+1, −y, −z+2; (v) x, y, z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.90 (6) | 1.77 (6) | 2.666 (5) | 169.5 |
C7—H7···O1ii | 0.93 | 2.63 | 3.409 (6) | 141.2 |
C8—H8···O6iii | 0.93 | 2.32 | 3.242 (7) | 170.8 |
C10—H10···O5 | 0.93 | 2.41 | 3.328 (6) | 169.6 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −y+1, −z; (iii) −x+1, −y+1, −z. |
Hydrogen-bond geometry (Å, º) for (III) top
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···O3i | 0.97 | 2.57 | 3.441 (8) | 150.0 |
C5—H5···O2ii | 0.93 | 2.32 | 3.233 (8) | 168.7 |
C6—H6···O6iii | 0.93 | 2.55 | 3.309 (7) | 138.6 |
C7—H7···O3iv | 0.93 | 2.38 | 3.291 (7) | 164.9 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x, −y, −z; (iii) x−1, y, z; (iv) x−1, y, z+1. |
Hydrogen-bond geometry (Å, º) for (IV) top
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···O6i | 0.97 | 2.59 | 3.451 (6) | 147.1 |
C5—H5···O3ii | 0.93 | 2.27 | 3.115 (6) | 151.6 |
C6—H6···O6iii | 0.93 | 2.50 | 3.387 (7) | 160.2 |
C8—H8···O6iv | 0.93 | 2.49 | 3.279 (7) | 143.1 |
C9—H9···O3v | 0.93 | 2.18 | 3.099 (7) | 168.9 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y, −z; (iii) −x+1, −y, −z+1; (iv) −x, −y, −z+1; (v) −x, −y, −z. |
Selected geometric parameters (Å, °) for (I) to (IV) topCompound | (I) | (II) | (III) | (IV) |
U1—O1 | 1.781 (3) | 1.760 (3) | 1.756 (4) | 1.760 (4) |
U1—O2 | 1.777 (3) | 2.443 (3) | 2.364 (4) | 2.414 (4) |
U1—O4 | 2.348 (2) | 2.690 (3) | 2.716 (4) | 2.653 (3) |
U1—O5 | 2.561 (3) | 2.391 (3) | 2.426 (4) | 2.445 (4) |
U1—O6 | 2.357 (2) | | | |
O1—U1—O2 | 178.59 (12) | 92.63 (13) | 90.1 (2) | 87.66 (17) |
O1—U1—O3 | 89.38 (7) | | | |
O1—U1—O5 | 94.06 (11) | 92.24 (14) | 89.33 (18) | 88.15 (18) |
O1—U1—O6 | 96.12 (8) | | | |
O2—U1—O4 | | 57.89 (10) | 57.79 (13) | 58.72 (11) |
O2—U1—O5 | | 114.84 (10) | 114.65 (14) | 116.69 (12) |
O3—U1—O5 | 61.48 (5) | | | |
O3—U1—O6 | 73.72 (7) | | | |
O4—U1—O5 | | 57.73 (10) | 56.95 (12) | 58.24 (12) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
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.