Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102021108/ta1396sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102021108/ta1396Isup2.hkl |
Transparent yellow crystals of UO2(NO3)2(H2O)3 up to 1 mm in maximum dimension were synthesized from a solution containing Cu(NO3)2(H2O)3, UO2(NO3)2(H2O)6 and K2CO3, in a molar ratio of 2:5:1, in solution in water (50 ml). Following evaporation in an open vessel for 14 d at 294 K and ambient pressure, crystals were recovered from the vessel walls.
The locations of the highest peak, 2.07 e Å−3, and deepest hole, −1.31 e Å−3, in the difference Fourier map are 0.79 Å from U2 and 0.86 Å from U1, respectively. H-atom positions were not included in the refinement.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SHELXTL-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 1993); software used to prepare material for publication: Microsoft Word.
UO2(NO3)2(H2O)3 | Z = 2 |
Mr = 448.08 | F(000) = 400 |
Triclinic, P1 | Dx = 3.31 Mg m−3 |
a = 7.0359 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.1730 (15) Å | Cell parameters from 3612 reflections |
c = 10.084 (2) Å | θ = 3–34.5° |
α = 81.697 (4)° | µ = 18.10 mm−1 |
β = 82.041 (4)° | T = 298 K |
γ = 63.642 (4)° | Block-like, yellow |
V = 449.64 (16) Å3 | 0.12 × 0.11 × 0.10 mm |
Make Model CCD area-detector diffractometer | 3614 independent reflections |
Radiation source: fine-focus sealed tube | 2138 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
ω scans | θmax = 34.5°, θmin = 2.1° |
Absorption correction: empirical (using intensity measurements) (SHELXL97; Sheldrick, 1997a) | h = −10→11 |
Tmin = 0.098, Tmax = 0.164 | k = −11→11 |
9093 measured reflections | l = −15→15 |
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)] = 0.043 | H-atom parameters not refined |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.022P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3614 reflections | Δρmax = 2.08 e Å−3 |
130 parameters | Δρmin = −1.34 e Å−3 |
0 restraints |
UO2(NO3)2(H2O)3 | γ = 63.642 (4)° |
Mr = 448.08 | V = 449.64 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0359 (15) Å | Mo Kα radiation |
b = 7.1730 (15) Å | µ = 18.10 mm−1 |
c = 10.084 (2) Å | T = 298 K |
α = 81.697 (4)° | 0.12 × 0.11 × 0.10 mm |
β = 82.041 (4)° |
Make Model CCD area-detector diffractometer | 3614 independent reflections |
Absorption correction: empirical (using intensity measurements) (SHELXL97; Sheldrick, 1997a) | 2138 reflections with I > 2σ(I) |
Tmin = 0.098, Tmax = 0.164 | Rint = 0.090 |
9093 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters not refined |
S = 1.01 | Δρmax = 2.08 e Å−3 |
3614 reflections | Δρmin = −1.34 e Å−3 |
130 parameters |
Experimental. psi-scan absorption correction in XPREP |
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. |
x | y | z | Uiso*/Ueq | ||
U1 | 0.5 | 0.5 | 0.5 | 0.02672 (13) | |
U2 | 0.5 | 0.0 | 0.0 | 0.02345 (13) | |
N1 | 0.7299 (13) | 0.7396 (12) | 0.5443 (8) | 0.0317 (17) | |
N2 | 0.1821 (12) | 0.3840 (11) | 0.1100 (7) | 0.0290 (16) | |
O1 | 0.6923 (11) | 0.2816 (10) | 0.5820 (7) | 0.0379 (16) | |
O2 | 0.2872 (11) | 0.5974 (10) | 0.7145 (6) | 0.0381 (16) | |
O3 | 0.7583 (12) | 0.6536 (11) | 0.4372 (7) | 0.0425 (18) | |
O4 | 0.5901 (12) | 0.7177 (12) | 0.6281 (7) | 0.0461 (19) | |
O5 | 0.3921 (10) | 0.0888 (9) | −0.1553 (6) | 0.0323 (15) | |
O6 | 0.2587 (11) | −0.1640 (11) | 0.0681 (7) | 0.0427 (18) | |
O7 | 0.1515 (10) | 0.2201 (10) | 0.1133 (7) | 0.0355 (15) | |
O8 | 0.3585 (10) | 0.3756 (9) | 0.0545 (6) | 0.0346 (15) | |
O9 | 0.8370 (13) | 0.8224 (12) | 0.5642 (8) | 0.053 (2) | |
O10 | 0.0494 (12) | 0.5377 (10) | 0.1591 (8) | 0.0455 (19) | |
O11 | −0.0687 (10) | −0.0235 (10) | 0.2683 (7) | 0.0347 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.0220 (3) | 0.0269 (3) | 0.0279 (3) | −0.0078 (2) | 0.0013 (2) | −0.0049 (2) |
U2 | 0.0212 (3) | 0.0219 (2) | 0.0275 (3) | −0.0092 (2) | 0.0034 (2) | −0.0075 (2) |
N1 | 0.023 (4) | 0.023 (4) | 0.020 (4) | −0.011 (3) | 0.002 (3) | −0.005 (3) |
N2 | 0.021 (4) | 0.016 (3) | 0.021 (4) | −0.007 (3) | 0.007 (3) | −0.006 (3) |
O1 | 0.027 (4) | 0.030 (3) | 0.048 (4) | −0.006 (3) | −0.008 (3) | 0.001 (3) |
O2 | 0.039 (4) | 0.037 (4) | 0.034 (4) | −0.014 (3) | 0.011 (3) | −0.007 (3) |
O3 | 0.039 (4) | 0.045 (4) | 0.045 (4) | −0.019 (4) | 0.005 (4) | −0.008 (4) |
O4 | 0.041 (5) | 0.057 (5) | 0.046 (5) | −0.026 (4) | 0.014 (4) | −0.016 (4) |
O5 | 0.037 (4) | 0.028 (3) | 0.027 (3) | −0.010 (3) | −0.006 (3) | −0.006 (3) |
O6 | 0.041 (4) | 0.043 (4) | 0.052 (5) | −0.027 (4) | 0.015 (4) | −0.020 (4) |
O7 | 0.029 (4) | 0.037 (4) | 0.043 (4) | −0.018 (3) | 0.008 (3) | −0.012 (3) |
O8 | 0.031 (4) | 0.029 (3) | 0.047 (4) | −0.015 (3) | 0.007 (3) | −0.012 (3) |
O9 | 0.056 (6) | 0.051 (5) | 0.066 (6) | −0.031 (5) | −0.001 (4) | −0.015 (4) |
O10 | 0.042 (4) | 0.032 (4) | 0.054 (5) | −0.015 (3) | 0.019 (4) | −0.021 (3) |
O11 | 0.030 (4) | 0.037 (4) | 0.035 (4) | −0.013 (3) | 0.002 (3) | −0.009 (3) |
U1—O1 | 1.738 (6) | U2—O8 | 2.539 (6) |
U1—O2 | 2.453 (6) | N1—O9 | 1.198 (10) |
U1—O3 | 2.485 (7) | N1—O4 | 1.255 (10) |
U1—O4 | 2.490 (7) | N1—O3 | 1.269 (10) |
U2—O5 | 1.745 (6) | N2—O10 | 1.203 (9) |
U2—O6 | 2.440 (7) | N2—O8 | 1.269 (9) |
U2—O7 | 2.473 (7) | N2—O7 | 1.281 (9) |
O1i—U1—O1 | 180.0 | O5—U2—O7 | 89.8 (3) |
O1—U1—O2 | 90.6 (3) | O6—U2—O7 | 64.0 (2) |
O2i—U1—O2 | 180.0 | O7—U2—O7ii | 180.0 |
O1—U1—O3 | 90.4 (3) | O5—U2—O8 | 89.7 (2) |
O2—U1—O3 | 114.6 (2) | O6—U2—O8 | 115.5 (2) |
O3—U1—O3i | 180.0 | O7—U2—O8 | 51.4 (2) |
O1—U1—O4 | 87.6 (3) | O8—U2—O8ii | 180.0 |
O2—U1—O4 | 64.4 (2) | O9—N1—O4 | 124.4 (9) |
O3—U1—O4 | 50.2 (2) | O9—N1—O3 | 121.9 (9) |
O4—U1—O4i | 180.0 | O4—N1—O3 | 113.6 (8) |
O5—U2—O5ii | 180.0 | O10—N2—O8 | 121.8 (8) |
O5—U2—O6 | 89.9 (3) | O10—N2—O7 | 121.1 (8) |
O6ii—U2—O6 | 180.0 | O8—N2—O7 | 117.1 (7) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | UO2(NO3)2(H2O)3 |
Mr | 448.08 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.0359 (15), 7.1730 (15), 10.084 (2) |
α, β, γ (°) | 81.697 (4), 82.041 (4), 63.642 (4) |
V (Å3) | 449.64 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 18.10 |
Crystal size (mm) | 0.12 × 0.11 × 0.10 |
Data collection | |
Diffractometer | Make Model CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SHELXL97; Sheldrick, 1997a) |
Tmin, Tmax | 0.098, 0.164 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9093, 3614, 2138 |
Rint | 0.090 |
(sin θ/λ)max (Å−1) | 0.797 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.109, 1.01 |
No. of reflections | 3614 |
No. of parameters | 130 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 2.08, −1.34 |
Computer programs: SMART (Bruker, 1998), SMART, SHELXTL-NT (Bruker, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ATOMS (Dowty, 1993), Microsoft Word.
U1—O1 | 1.738 (6) | U2—O5 | 1.745 (6) |
U1—O2 | 2.453 (6) | U2—O6 | 2.440 (7) |
U1—O3 | 2.485 (7) | U2—O7 | 2.473 (7) |
U1—O4 | 2.490 (7) | U2—O8 | 2.539 (6) |
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UO2(NO3)2(H2O)3 was first obtained as a by-product in a synthesis experiment intended to produce uranyl carbonates by room-temperature evaporation of a solution containing uranyl nitrate with various carbonates and nitrates. Subsequently, large single crystals of UO2(NO3)2(H2O)3 were obtained from a solution of UO2(NO3)(H2O)6, K2CO3 and Cu(NO3)2(H2O)3 at room temperature and pressure. The structures are known or estimated for the chemically related compounds (UO2)(NO3)2(H2O)2 (Taylor & Mueller, 1965), (UO2)(NO3)2(H2O)6 (Dalley et al., 1971) and (UO2)(NO3)2(H2O)3 (Vdovenko et al., 1963). Each contains the [(UO2)(H2O)2(NO3)2] finite cluster. These compounds crystallize in space groups Cmc21, P21/c and P1, respectively. Whereas (UO2)(NO3)2(H2O)2 and (UO2)(NO3)2(H2O)6 differ from UO2(NO3)2(H2O)3 in their hydration state and space group, the structure published by Vdovenko et al. (1963) corresponds to that for UO2(NO3)2(H2O)3. That published structure is incomplete, as only the U and O atoms were located. The refined structure, including N-atom positions, is given herein.
There are two symmetrically distinct UVI atoms, positioned on centers of symmetry, both of which are part of linear (UO2)2+ uranyl ions and which are coordinated by six equatorial atoms of O, forming hexagonal bipyramids (Fig. 1). Two opposite equatorial edges of each hexagonal bipyramid share edges with NO3 groups, giving the [(UO2)(H2O)2(NO3)2] cluster. Two H2O groups correspond to equatorial ligands of the uranyl polyhedra. One H2O group is located between the [(UO2)(H2O)2(NO3)2] clusters (Fig. 2).
Bond-valence sums were calculated for each ion using the method of Brese & O'Keeffe (1991). The U bond-valence sums (Burns at al., 1997) are 6.18 and 6.12 for the two unique U positions. The N bond-valence sums are 5.29 and 5.07. For O-atom positions O1, O3, O4, O5, O7, O8, O9 and O10, the bond-valence sums are within the normal range (1.80–2.07). For atoms O2, O6 and O11, values consistant with H2O were obtained (0.44, 0.46 and 0.00, respectively).