Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109044394/fa3208sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109044394/fa3208Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109044394/fa3208IIsup3.hkl |
For related literature, see: Charushnikova et al. (2007); Grigor'ev, Baturin, Tananaev & Krot (1993); Grigoriev & Krot (2007a, 2007b, 2008); Tomilin et al. (1981a, 1981b, 1981c, 1983).
The starting solutions for the syntheses of (I) and (II) were 0.075 M 237NpVII in 2.5 M LiOH and 0.06 M 239PuVII in 2.5 M LiOH. The preparation of such solutions is described by Charushnikova et al. (2007).
For the synthesis of (I), 0.1 ml of the solution was put into a plastic container, then 0.2 ml of 16.7 M NaOH was added and the container was placed in a desiccator with granulated KOH (to absorb CO2 and water vapour). After 3 d of evaporation at room temperature, crystalline hydroxides had been formed with inclusions of black crystals of (I).
For the synthesis of (II), 0.05 ml of the corresponding initial solution was put into a plastic container, then 0.2 ml of 16.7 M NaOH was added and the container was placed in a desiccator with granulated KOH. After 1 d, a mixture of black, plate crystals of (II) and small grey crystals of PuVI hydroxide compounds was found.
All attempts at the synthesis have given twinned crystals, both for Np and Pu.
Both structures were solved with twinned crystals [the second domains are rotated from the first by 180° about the reciprocal axis (001)]. The refined BASF parameters for the second domains are 0.4946 (4) and 0.4908 (2) for (I) and (II), respectively.
The H atoms of the OH groups and crystallization water molecules were located in difference Fourier maps and refined with O–H distances restrained to 0.82 (2) and 0.85 (2) Å, respectively. The displacement parameters of these H atoms were constrained to 1.2 and 1.5 times the Uiso of their parent atoms.
The largest electron-density peak on the final difference Fourier synthesis for (I) is 2.158 e Å-3 (0.68 Å from Np1), the deepest hole is -1.824 e Å-3 (0.62 Å from Np1). The largest electron-density peak on the final difference Fourier synthesis for (II) is 2.543 e Å-3 (0.69 Å from Pu1), the deepest hole is -1.986 e Å-3 (0.42 Å from Pu1).
For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).
Na4[NpO4(OH)2](OH)·2H2O | Z = 2 |
Mr = 480.02 | F(000) = 432 |
Triclinic, P1 | Dx = 3.382 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9632 (2) Å | Cell parameters from 8013 reflections |
b = 8.1157 (2) Å | θ = 2.0–35.0° |
c = 10.9434 (3) Å | µ = 7.33 mm−1 |
α = 105.007 (2)° | T = 293 K |
β = 101.213 (2)° | Fragment, black |
γ = 105.935 (2)° | 0.12 × 0.06 × 0.06 mm |
V = 471.36 (2) Å3 |
Bruker Kappa APEXII area-detector diffractometer | 4029 independent reflections |
Radiation source: fine-focus sealed tube | 3812 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω– and ϕ–scans | θmax = 35.0°, θmin = 2.0° |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2002) | h = −9→9 |
Tmin = 0.451, Tmax = 0.625 | k = −13→12 |
22639 measured reflections | l = 0→17 |
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: difference Fourier map |
wR(F2) = 0.054 | All H-atom parameters refined |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0277P)2 + 0.1404P] where P = (Fo2 + 2Fc2)/3 |
4029 reflections | (Δ/σ)max = 0.001 |
149 parameters | Δρmax = 2.16 e Å−3 |
9 restraints | Δρmin = −1.82 e Å−3 |
Na4[NpO4(OH)2](OH)·2H2O | γ = 105.935 (2)° |
Mr = 480.02 | V = 471.36 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.9632 (2) Å | Mo Kα radiation |
b = 8.1157 (2) Å | µ = 7.33 mm−1 |
c = 10.9434 (3) Å | T = 293 K |
α = 105.007 (2)° | 0.12 × 0.06 × 0.06 mm |
β = 101.213 (2)° |
Bruker Kappa APEXII area-detector diffractometer | 4029 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2002) | 3812 reflections with I > 2σ(I) |
Tmin = 0.451, Tmax = 0.625 | Rint = 0.038 |
22639 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 9 restraints |
wR(F2) = 0.054 | All H-atom parameters refined |
S = 1.10 | Δρmax = 2.16 e Å−3 |
4029 reflections | Δρmin = −1.82 e Å−3 |
149 parameters |
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 | ||
Np1 | 0.63709 (2) | 0.414646 (15) | 0.247923 (11) | 0.00968 (3) | |
Na1 | 0.2127 (2) | 0.46725 (19) | 0.41560 (13) | 0.0193 (3) | |
Na2 | 1.0543 (2) | 0.3396 (2) | 0.07342 (14) | 0.0211 (3) | |
Na3 | 0.5236 (3) | 0.72145 (19) | 0.09527 (14) | 0.0211 (3) | |
Na4 | 0.6165 (3) | 0.8535 (2) | 0.42625 (15) | 0.0253 (3) | |
O1 | 0.8539 (4) | 0.2829 (3) | 0.2395 (3) | 0.0178 (4) | |
O2 | 0.3952 (4) | 0.2286 (3) | 0.1023 (2) | 0.0172 (4) | |
O3 | 0.4227 (4) | 0.5527 (3) | 0.2527 (3) | 0.0151 (4) | |
O4 | 0.8743 (4) | 0.6025 (3) | 0.3929 (2) | 0.0180 (4) | |
O5 | 0.4867 (5) | 0.3026 (3) | 0.4010 (2) | 0.0171 (4) | |
H5 | 0.421 (7) | 0.193 (3) | 0.373 (5) | 0.021* | |
O6 | 0.7915 (4) | 0.5368 (3) | 0.0952 (2) | 0.0155 (4) | |
H6 | 0.907 (5) | 0.624 (4) | 0.138 (4) | 0.019* | |
O7 | 0.2470 (5) | −0.0813 (3) | 0.3625 (3) | 0.0218 (5) | |
H7 | 0.186 (8) | −0.155 (5) | 0.392 (5) | 0.026* | |
O8 | 0.2420 (5) | −0.1323 (4) | 0.1170 (3) | 0.0249 (5) | |
H8A | 0.244 (9) | −0.113 (6) | 0.197 (2) | 0.037* | |
H8B | 0.279 (9) | −0.027 (4) | 0.110 (5) | 0.037* | |
O9 | 0.8145 (5) | 0.9542 (4) | 0.2823 (3) | 0.0251 (5) | |
H9A | 0.835 (7) | 1.059 (4) | 0.276 (5) | 0.038* | |
H9B | 0.952 (5) | 0.958 (6) | 0.320 (5) | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Np1 | 0.00930 (4) | 0.01039 (5) | 0.00943 (4) | 0.00323 (3) | 0.00268 (3) | 0.00356 (4) |
Na1 | 0.0147 (6) | 0.0262 (7) | 0.0145 (6) | 0.0062 (6) | 0.0024 (5) | 0.0049 (5) |
Na2 | 0.0151 (6) | 0.0311 (7) | 0.0173 (6) | 0.0084 (6) | 0.0048 (5) | 0.0079 (6) |
Na3 | 0.0261 (7) | 0.0240 (7) | 0.0175 (6) | 0.0136 (6) | 0.0069 (6) | 0.0084 (5) |
Na4 | 0.0293 (8) | 0.0222 (7) | 0.0203 (7) | 0.0057 (6) | 0.0078 (6) | 0.0030 (6) |
O1 | 0.0160 (10) | 0.0186 (10) | 0.0222 (11) | 0.0087 (9) | 0.0053 (9) | 0.0094 (10) |
O2 | 0.0161 (10) | 0.0154 (10) | 0.0166 (11) | 0.0026 (9) | 0.0032 (8) | 0.0036 (8) |
O3 | 0.0156 (9) | 0.0153 (9) | 0.0166 (10) | 0.0079 (8) | 0.0059 (8) | 0.0051 (8) |
O4 | 0.0152 (10) | 0.0188 (11) | 0.0144 (10) | 0.0002 (9) | 0.0015 (8) | 0.0042 (9) |
O5 | 0.0204 (11) | 0.0156 (10) | 0.0158 (11) | 0.0029 (9) | 0.0089 (9) | 0.0066 (9) |
O6 | 0.0151 (10) | 0.0164 (10) | 0.0148 (11) | 0.0038 (9) | 0.0047 (8) | 0.0063 (9) |
O7 | 0.0220 (12) | 0.0185 (11) | 0.0212 (12) | 0.0030 (10) | 0.0047 (10) | 0.0059 (9) |
O8 | 0.0270 (13) | 0.0197 (12) | 0.0236 (13) | 0.0077 (11) | 0.0038 (11) | 0.0026 (10) |
O9 | 0.0204 (12) | 0.0205 (12) | 0.0371 (16) | 0.0070 (10) | 0.0083 (11) | 0.0142 (11) |
Np1—O1 | 1.891 (2) | Na2—O3iv | 2.479 (3) |
Np1—O2 | 1.888 (2) | Na2—O6v | 2.524 (3) |
Np1—O3 | 1.917 (2) | Na2—O6 | 2.529 (3) |
Np1—O4 | 1.880 (2) | Na3—O8vi | 2.321 (3) |
Np1—O5 | 2.315 (2) | Na3—O9 | 2.363 (3) |
Np1—O6 | 2.362 (2) | Na3—O2vii | 2.413 (3) |
Na1—O5i | 2.356 (3) | Na3—O6 | 2.472 (3) |
Na1—O5 | 2.381 (3) | Na3—O6vii | 2.514 (3) |
Na1—O1ii | 2.382 (3) | Na3—O3 | 2.526 (3) |
Na1—O4i | 2.420 (3) | Na4—O9 | 2.325 (3) |
Na1—O3 | 2.501 (3) | Na4—O7i | 2.377 (3) |
Na1—O4ii | 2.550 (3) | Na4—O7vi | 2.420 (3) |
Na2—O8iii | 2.327 (3) | Na4—O3 | 2.469 (3) |
Na2—O1 | 2.433 (3) | Na4—O5i | 2.613 (3) |
Na2—O2iv | 2.439 (3) | Na4—O4 | 2.864 (3) |
O1—Np1—O2 | 91.52 (10) | O2iv—Na2—O6v | 88.01 (9) |
O1—Np1—O3 | 177.96 (10) | O3iv—Na2—O6v | 91.40 (9) |
O1—Np1—O4 | 89.53 (10) | O8iii—Na2—O6 | 89.56 (9) |
O1—Np1—O5 | 93.62 (9) | O1—Na2—O6 | 73.19 (8) |
O1—Np1—O6 | 87.44 (9) | O2iv—Na2—O6 | 163.23 (10) |
O2—Np1—O3 | 88.67 (10) | O3iv—Na2—O6 | 97.81 (9) |
O2—Np1—O4 | 178.95 (9) | O6v—Na2—O6 | 91.36 (8) |
O2—Np1—O5 | 93.47 (10) | O8vi—Na3—O9 | 90.37 (10) |
O2—Np1—O6 | 87.60 (9) | O8vi—Na3—O2vii | 99.31 (10) |
O3—Np1—O4 | 90.28 (10) | O9—Na3—O2vii | 109.28 (11) |
O3—Np1—O5 | 88.40 (9) | O8vi—Na3—O6 | 170.16 (12) |
O3—Np1—O6 | 90.54 (9) | O9—Na3—O6 | 90.16 (9) |
O4—Np1—O5 | 86.58 (10) | O2vii—Na3—O6 | 89.78 (9) |
O4—Np1—O6 | 92.33 (9) | O8vi—Na3—O6vii | 90.08 (10) |
O5—Np1—O6 | 178.47 (8) | O9—Na3—O6vii | 176.70 (11) |
O5i—Na1—O5 | 88.77 (9) | O2vii—Na3—O6vii | 73.86 (9) |
O5i—Na1—O1ii | 166.05 (10) | O6—Na3—O6vii | 88.84 (9) |
O5—Na1—O1ii | 105.19 (10) | O8vi—Na3—O3 | 94.84 (10) |
O5i—Na1—O4i | 74.58 (9) | O9—Na3—O3 | 86.15 (10) |
O5—Na1—O4i | 93.43 (9) | O2vii—Na3—O3 | 158.84 (10) |
O1ii—Na1—O4i | 104.25 (9) | O6—Na3—O3 | 75.39 (8) |
O5i—Na1—O3 | 93.78 (9) | O6vii—Na3—O3 | 90.56 (9) |
O5—Na1—O3 | 74.72 (8) | O9—Na4—O7i | 110.87 (11) |
O1ii—Na1—O3 | 89.78 (9) | O9—Na4—O7vi | 99.20 (10) |
O4i—Na1—O3 | 163.76 (9) | O7i—Na4—O7vi | 93.10 (10) |
O5i—Na1—O4ii | 101.00 (9) | O9—Na4—O3 | 88.29 (10) |
O5—Na1—O4ii | 170.10 (10) | O7i—Na4—O3 | 160.11 (11) |
O1ii—Na1—O4ii | 65.05 (8) | O7vi—Na4—O3 | 88.85 (9) |
O4i—Na1—O4ii | 90.80 (9) | O9—Na4—O5i | 160.69 (11) |
O3—Na1—O4ii | 102.70 (9) | O7i—Na4—O5i | 71.66 (9) |
O8iii—Na2—O1 | 100.12 (11) | O7vi—Na4—O5i | 99.76 (10) |
O8iii—Na2—O2iv | 106.87 (10) | O3—Na4—O5i | 88.50 (9) |
O1—Na2—O2iv | 106.27 (9) | O9—Na4—O4 | 82.73 (9) |
O8iii—Na2—O3iv | 169.56 (11) | O7i—Na4—O4 | 115.40 (10) |
O1—Na2—O3iv | 89.14 (9) | O7vi—Na4—O4 | 148.90 (10) |
O2iv—Na2—O3iv | 65.46 (8) | O3—Na4—O4 | 60.09 (8) |
O8iii—Na2—O6v | 80.99 (10) | O5i—Na4—O4 | 79.18 (8) |
O1—Na2—O6v | 164.46 (9) | ||
H5—O5—O6—H6 | −149 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+2, −y+1, −z; (vi) x, y+1, z; (vii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O7 | 0.81 (2) | 2.14 (2) | 2.927 (3) | 162 (5) |
O6—H6···O8viii | 0.79 (2) | 2.49 (3) | 3.154 (4) | 142 (4) |
O7—H7···O4ix | 0.79 (2) | 2.31 (3) | 3.039 (4) | 154 (5) |
O8—H8A···O7 | 0.85 (2) | 1.76 (2) | 2.603 (4) | 178 (4) |
O8—H8B···O2 | 0.85 (2) | 2.03 (2) | 2.876 (4) | 175 (5) |
O9—H9A···O1vi | 0.85 (2) | 1.94 (2) | 2.781 (3) | 173 (5) |
O9—H9B···O7viii | 0.83 (2) | 1.87 (2) | 2.676 (4) | 165 (5) |
Symmetry codes: (vi) x, y+1, z; (viii) x+1, y+1, z; (ix) x−1, y−1, z. |
Na4[PuO4(OH)2](OH)·2H2O | Z = 2 |
Mr = 482.02 | F(000) = 434 |
Triclinic, P1 | Dx = 3.461 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.9177 (2) Å | Cell parameters from 7446 reflections |
b = 8.0736 (2) Å | θ = 2.0–40.0° |
c = 10.8696 (3) Å | µ = 7.79 mm−1 |
α = 105.007 (2)° | T = 100 K |
β = 101.224 (2)° | Fragment, black |
γ = 105.760 (2)° | 0.16 × 0.06 × 0.04 mm |
V = 462.72 (2) Å3 |
Bruker Kappa APEXII area-detector diffractometer | 5736 independent reflections |
Radiation source: fine-focus sealed tube | 4796 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω– and ϕ–scans | θmax = 40.0°, θmin = 2.0° |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2002) | h = −10→10 |
Tmin = 0.515, Tmax = 0.758 | k = −14→14 |
31123 measured reflections | l = 0→19 |
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)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.039 | All H-atom parameters refined |
S = 0.86 | w = 1/[σ2(Fo2) + (0.0086P)2] where P = (Fo2 + 2Fc2)/3 |
5736 reflections | (Δ/σ)max = 0.001 |
149 parameters | Δρmax = 2.54 e Å−3 |
9 restraints | Δρmin = −1.99 e Å−3 |
Na4[PuO4(OH)2](OH)·2H2O | γ = 105.760 (2)° |
Mr = 482.02 | V = 462.72 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.9177 (2) Å | Mo Kα radiation |
b = 8.0736 (2) Å | µ = 7.79 mm−1 |
c = 10.8696 (3) Å | T = 100 K |
α = 105.007 (2)° | 0.16 × 0.06 × 0.04 mm |
β = 101.224 (2)° |
Bruker Kappa APEXII area-detector diffractometer | 5736 independent reflections |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2002) | 4796 reflections with I > 2σ(I) |
Tmin = 0.515, Tmax = 0.758 | Rint = 0.049 |
31123 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 9 restraints |
wR(F2) = 0.039 | All H-atom parameters refined |
S = 0.86 | Δρmax = 2.54 e Å−3 |
5736 reflections | Δρmin = −1.99 e Å−3 |
149 parameters |
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 | ||
Pu1 | 0.636080 (17) | 0.414739 (13) | 0.247926 (10) | 0.00471 (2) | |
Na1 | 0.21183 (19) | 0.46774 (15) | 0.41582 (10) | 0.0100 (2) | |
Na2 | 1.05366 (18) | 0.34046 (15) | 0.07393 (11) | 0.0099 (2) | |
Na3 | 0.52187 (18) | 0.71929 (14) | 0.09431 (10) | 0.0100 (2) | |
Na4 | 0.61628 (18) | 0.85254 (14) | 0.42687 (10) | 0.0119 (2) | |
O1 | 0.8529 (3) | 0.2821 (2) | 0.24009 (18) | 0.0091 (3) | |
O2 | 0.3938 (3) | 0.2289 (2) | 0.10200 (18) | 0.0092 (3) | |
O3 | 0.4207 (3) | 0.5534 (2) | 0.25272 (18) | 0.0086 (3) | |
O4 | 0.8756 (3) | 0.6042 (2) | 0.39297 (19) | 0.0093 (4) | |
O5 | 0.4857 (3) | 0.3035 (3) | 0.40065 (19) | 0.0093 (4) | |
H5 | 0.449 (5) | 0.200 (2) | 0.386 (3) | 0.011* | |
O6 | 0.7897 (3) | 0.5351 (3) | 0.0951 (2) | 0.0080 (4) | |
H6 | 0.891 (4) | 0.620 (3) | 0.145 (3) | 0.010* | |
O7 | 0.2480 (3) | −0.0810 (2) | 0.36329 (18) | 0.0105 (3) | |
H7 | 0.174 (5) | −0.162 (3) | 0.376 (3) | 0.013* | |
O8 | 0.2410 (4) | −0.1325 (3) | 0.1161 (2) | 0.0124 (4) | |
H8A | 0.229 (5) | −0.122 (4) | 0.193 (2) | 0.019* | |
H8B | 0.290 (5) | −0.035 (3) | 0.109 (3) | 0.019* | |
O9 | 0.8122 (3) | 0.9519 (2) | 0.28120 (18) | 0.0121 (3) | |
H9A | 0.832 (5) | 1.056 (3) | 0.275 (3) | 0.018* | |
H9B | 0.962 (3) | 0.956 (4) | 0.308 (3) | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pu1 | 0.00480 (3) | 0.00532 (3) | 0.00417 (3) | 0.00187 (2) | 0.00115 (3) | 0.00178 (3) |
Na1 | 0.0083 (5) | 0.0139 (5) | 0.0069 (5) | 0.0031 (4) | 0.0015 (4) | 0.0032 (4) |
Na2 | 0.0081 (5) | 0.0133 (5) | 0.0083 (5) | 0.0046 (4) | 0.0022 (4) | 0.0029 (4) |
Na3 | 0.0120 (5) | 0.0111 (5) | 0.0079 (5) | 0.0058 (4) | 0.0027 (4) | 0.0030 (4) |
Na4 | 0.0138 (5) | 0.0104 (5) | 0.0104 (5) | 0.0033 (4) | 0.0040 (4) | 0.0022 (4) |
O1 | 0.0090 (8) | 0.0095 (8) | 0.0098 (9) | 0.0042 (6) | 0.0024 (7) | 0.0041 (7) |
O2 | 0.0094 (8) | 0.0098 (9) | 0.0083 (9) | 0.0036 (7) | 0.0015 (7) | 0.0030 (7) |
O3 | 0.0102 (8) | 0.0086 (8) | 0.0085 (8) | 0.0042 (6) | 0.0039 (7) | 0.0033 (7) |
O4 | 0.0085 (8) | 0.0095 (9) | 0.0079 (9) | 0.0008 (7) | 0.0018 (7) | 0.0026 (7) |
O5 | 0.0118 (9) | 0.0063 (9) | 0.0086 (9) | 0.0023 (7) | 0.0029 (8) | 0.0017 (8) |
O6 | 0.0077 (8) | 0.0080 (9) | 0.0069 (9) | 0.0015 (7) | 0.0010 (7) | 0.0024 (7) |
O7 | 0.0105 (8) | 0.0093 (8) | 0.0111 (8) | 0.0018 (7) | 0.0024 (7) | 0.0046 (7) |
O8 | 0.0143 (9) | 0.0103 (9) | 0.0115 (9) | 0.0039 (8) | 0.0025 (8) | 0.0030 (8) |
O9 | 0.0109 (8) | 0.0100 (8) | 0.0165 (10) | 0.0046 (7) | 0.0034 (7) | 0.0057 (7) |
Pu1—O1 | 1.8824 (15) | Na2—O3iv | 2.459 (2) |
Pu1—O2 | 1.8805 (18) | Na2—O6 | 2.5002 (19) |
Pu1—O3 | 1.9109 (15) | Na2—O6v | 2.522 (2) |
Pu1—O4 | 1.8811 (19) | Na3—O8vi | 2.310 (2) |
Pu1—O5 | 2.2952 (19) | Na3—O9 | 2.349 (2) |
Pu1—O6 | 2.339 (2) | Na3—O2vii | 2.396 (2) |
Na1—O5i | 2.345 (2) | Na3—O6 | 2.4501 (19) |
Na1—O5 | 2.360 (2) | Na3—O6vii | 2.477 (2) |
Na1—O1ii | 2.370 (2) | Na3—O3 | 2.505 (2) |
Na1—O4i | 2.410 (2) | Na4—O9 | 2.316 (2) |
Na1—O3 | 2.484 (2) | Na4—O7i | 2.357 (2) |
Na1—O4ii | 2.5247 (19) | Na4—O7vi | 2.3992 (19) |
Na2—O8iii | 2.310 (2) | Na4—O3 | 2.453 (2) |
Na2—O2iv | 2.4174 (18) | Na4—O5i | 2.592 (2) |
Na2—O1 | 2.422 (2) | Na4—O4 | 2.8319 (19) |
O1—Pu1—O2 | 91.50 (7) | O1—Na2—O6 | 73.37 (6) |
O1—Pu1—O3 | 178.24 (8) | O3iv—Na2—O6 | 97.86 (7) |
O1—Pu1—O4 | 89.58 (7) | O8iii—Na2—O6v | 81.32 (8) |
O1—Pu1—O5 | 93.39 (7) | O2iv—Na2—O6v | 87.78 (7) |
O1—Pu1—O6 | 87.62 (7) | O1—Na2—O6v | 164.86 (7) |
O2—Pu1—O3 | 88.68 (7) | O3iv—Na2—O6v | 91.08 (7) |
O2—Pu1—O4 | 178.79 (8) | O6—Na2—O6v | 91.60 (7) |
O2—Pu1—O5 | 93.42 (7) | O8vi—Na3—O9 | 90.06 (7) |
O2—Pu1—O6 | 87.49 (8) | O8vi—Na3—O2vii | 99.22 (7) |
O3—Pu1—O4 | 90.23 (7) | O9—Na3—O2vii | 108.73 (7) |
O3—Pu1—O5 | 88.35 (7) | O8vi—Na3—O6 | 170.25 (9) |
O3—Pu1—O6 | 90.63 (7) | O9—Na3—O6 | 90.17 (7) |
O4—Pu1—O5 | 87.07 (8) | O2vii—Na3—O6 | 89.94 (7) |
O4—Pu1—O6 | 92.01 (7) | O8vi—Na3—O6vii | 90.27 (7) |
O5—Pu1—O6 | 178.62 (7) | O9—Na3—O6vii | 177.04 (8) |
O5i—Na1—O5 | 88.49 (7) | O2vii—Na3—O6vii | 74.11 (7) |
O5i—Na1—O1ii | 166.70 (7) | O6—Na3—O6vii | 89.02 (7) |
O5—Na1—O1ii | 104.81 (7) | O8vi—Na3—O3 | 94.71 (7) |
O5i—Na1—O4i | 74.91 (7) | O9—Na3—O3 | 85.98 (7) |
O5—Na1—O4i | 93.27 (7) | O2vii—Na3—O3 | 159.59 (7) |
O1ii—Na1—O4i | 103.77 (7) | O6—Na3—O3 | 75.58 (6) |
O5i—Na1—O3 | 93.69 (7) | O6vii—Na3—O3 | 91.07 (7) |
O5—Na1—O3 | 74.79 (6) | O9—Na4—O7i | 110.84 (8) |
O1ii—Na1—O3 | 89.93 (7) | O9—Na4—O7vi | 98.80 (7) |
O4i—Na1—O3 | 163.89 (7) | O7i—Na4—O7vi | 92.77 (7) |
O5i—Na1—O4ii | 101.20 (7) | O9—Na4—O3 | 87.94 (7) |
O5—Na1—O4ii | 170.09 (8) | O7i—Na4—O3 | 160.69 (8) |
O1ii—Na1—O4ii | 65.51 (6) | O7vi—Na4—O3 | 88.57 (7) |
O4i—Na1—O4ii | 91.29 (7) | O9—Na4—O5i | 160.74 (7) |
O3—Na1—O4ii | 102.23 (7) | O7i—Na4—O5i | 72.19 (7) |
O8iii—Na2—O2iv | 106.36 (7) | O7vi—Na4—O5i | 100.05 (7) |
O8iii—Na2—O1 | 99.93 (8) | O3—Na4—O5i | 88.61 (7) |
O2iv—Na2—O1 | 106.13 (7) | O9—Na4—O4 | 82.43 (6) |
O8iii—Na2—O3iv | 169.47 (8) | O7i—Na4—O4 | 115.77 (7) |
O2iv—Na2—O3iv | 65.82 (6) | O7vi—Na4—O4 | 149.16 (7) |
O1—Na2—O3iv | 89.32 (7) | O3—Na4—O4 | 60.61 (6) |
O8iii—Na2—O6 | 89.68 (7) | O5i—Na4—O4 | 79.37 (6) |
O2iv—Na2—O6 | 163.64 (8) | ||
H5—O5—O6—H6 | −139 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+2, −y+1, −z; (vi) x, y+1, z; (vii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O7 | 0.77 (2) | 2.18 (2) | 2.921 (3) | 163 (3) |
O6—H6···O8viii | 0.76 (2) | 2.59 (3) | 3.152 (3) | 132 (3) |
O7—H7···O4ix | 0.75 (2) | 2.28 (2) | 3.013 (2) | 167 (3) |
O8—H8A···O7 | 0.84 (2) | 1.77 (2) | 2.600 (3) | 172 (3) |
O8—H8B···O2 | 0.79 (2) | 2.08 (2) | 2.865 (3) | 174 (3) |
O9—H9A···O1vi | 0.84 (2) | 1.94 (2) | 2.770 (2) | 174 (3) |
O9—H9B···O7viii | 0.87 (2) | 1.81 (2) | 2.667 (2) | 169 (3) |
Symmetry codes: (vi) x, y+1, z; (viii) x+1, y+1, z; (ix) x−1, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | Na4[NpO4(OH)2](OH)·2H2O | Na4[PuO4(OH)2](OH)·2H2O |
Mr | 480.02 | 482.02 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 100 |
a, b, c (Å) | 5.9632 (2), 8.1157 (2), 10.9434 (3) | 5.9177 (2), 8.0736 (2), 10.8696 (3) |
α, β, γ (°) | 105.007 (2), 101.213 (2), 105.935 (2) | 105.007 (2), 101.224 (2), 105.760 (2) |
V (Å3) | 471.36 (2) | 462.72 (2) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 7.33 | 7.79 |
Crystal size (mm) | 0.12 × 0.06 × 0.06 | 0.16 × 0.06 × 0.04 |
Data collection | ||
Diffractometer | Bruker Kappa APEXII area-detector diffractometer | Bruker Kappa APEXII area-detector diffractometer |
Absorption correction | Multi-scan (TWINABS; Sheldrick, 2002) | Multi-scan (TWINABS; Sheldrick, 2002) |
Tmin, Tmax | 0.451, 0.625 | 0.515, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22639, 4029, 3812 | 31123, 5736, 4796 |
Rint | 0.038 | 0.049 |
(sin θ/λ)max (Å−1) | 0.807 | 0.904 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.054, 1.10 | 0.028, 0.039, 0.86 |
No. of reflections | 4029 | 5736 |
No. of parameters | 149 | 149 |
No. of restraints | 9 | 9 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 2.16, −1.82 | 2.54, −1.99 |
Computer programs: APEX2 (Bruker, 2006), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL97 (Sheldrick, 2008).
Np1—O1 | 1.891 (2) | Np1—O4 | 1.880 (2) |
Np1—O2 | 1.888 (2) | Np1—O5 | 2.315 (2) |
Np1—O3 | 1.917 (2) | Np1—O6 | 2.362 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O7 | 0.813 (19) | 2.14 (2) | 2.927 (3) | 162 (5) |
O6—H6···O8i | 0.794 (19) | 2.49 (3) | 3.154 (4) | 142 (4) |
O7—H7···O4ii | 0.788 (19) | 2.31 (3) | 3.039 (4) | 154 (5) |
O8—H8A···O7 | 0.849 (18) | 1.755 (19) | 2.603 (4) | 178 (4) |
O8—H8B···O2 | 0.847 (18) | 2.03 (2) | 2.876 (4) | 175 (5) |
O9—H9A···O1iii | 0.849 (18) | 1.937 (19) | 2.781 (3) | 173 (5) |
O9—H9B···O7i | 0.828 (18) | 1.87 (2) | 2.676 (4) | 165 (5) |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y−1, z; (iii) x, y+1, z. |
Pu1—O1 | 1.8824 (15) | Pu1—O4 | 1.8811 (19) |
Pu1—O2 | 1.8805 (18) | Pu1—O5 | 2.2952 (19) |
Pu1—O3 | 1.9109 (15) | Pu1—O6 | 2.339 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5···O7 | 0.770 (16) | 2.177 (18) | 2.921 (3) | 163 (3) |
O6—H6···O8i | 0.760 (17) | 2.59 (3) | 3.152 (3) | 132 (3) |
O7—H7···O4ii | 0.745 (17) | 2.281 (18) | 3.013 (2) | 167 (3) |
O8—H8A···O7 | 0.836 (16) | 1.770 (17) | 2.600 (3) | 172 (3) |
O8—H8B···O2 | 0.793 (16) | 2.076 (17) | 2.865 (3) | 174 (3) |
O9—H9A···O1iii | 0.836 (16) | 1.938 (16) | 2.770 (2) | 174 (3) |
O9—H9B···O7i | 0.866 (16) | 1.812 (16) | 2.667 (2) | 169 (3) |
Symmetry codes: (i) x+1, y+1, z; (ii) x−1, y−1, z; (iii) x, y+1, z. |
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The majority of structural studies of AnVII compounds have been carried out on compounds containing [NpO4(OH)2]3- anions and alkali cations (Tomilin et al., 1981a,b,c, 1983; Grigor'ev et al., 1993; Charushnikova et al., 2007; Grigoriev & Krot, 2007b, 2008). Recently, there has been two structure determinations of PuVII compounds: K3[PuO4(OH)2].2H2O (Charushnikova et al., 2007) and Cs3[PuO4(OH)2].3H2O (Grigoriev & Krot, 2007a). In all of these compounds, except for Na3[NpO4(OH)2], the [AnO4(OH)2]3- anions are centrosymmetric. In Na3[NpO4(OH)2], the [NpO4(OH)2]3- anion occupies a special position on a twofold axis (Tomilin et al., 1981b; Grigoriev & Krot, 2007b).
The title compounds of NpVII, (I), Na4[NpO4(OH)2](OH).2H2O, and PuVII, (II), Na4[PuO4(OH)2](OH).2H2O, are isostructural and isomorphous and contain the complex anions [AnO4(OH)2]3-, which are distorted tetragonal bipyramids, Na+ cations, crystallization water molecules and outer-sphere OH groups (Fig. 1). The main bond lengths and angles in the anions are given in Tables 1 and 3. In contrast to the previously mentioned AnVII compounds, the complex anions [AnO4(OH)2]3- in (I) and (II) occupy general positions. The torsion angles H5—O5···O6—H6 are 149 (4) and 139 (3)° in (I) and (II), respectively, showing that the orientation of OH groups in [AnO4(OH)2]3- anions is far from centrosymmetric.
The Na cations have different structural roles. All have coordination number 6, but differ in the nature of their oxygen environments. It is possible to find in the structures electroneutral layers {Na3[AnO4(OH)2]}n, parallel to the (010) plane and formed by [AnO4(OH)2]3- anions and Na1, Na2 and Na3 cations. The environment of Na1 is formed only by O atoms of three complex anions of the same layer. The coordination polyhedra of Na1 (distorted octahedra) share edges to form zigzag chains in the [100] direction. The interlayer space is filled by Na4 cations, crystallization water molecules and outer-sphere OH groups. The environments of Na2 and Na3 are formed by O atoms of one layer and interlayer crystallization water molecules. Na4 atoms are also coordinated by bridging OH groups. The hydrogen bonds, in which the proton donors are OH groups of [AnO4(OH)2]3- anions, crystallization water molecules and outer-sphere OH groups, link neighbouring layers (Tables 2, 4; Fig. 2).
The isomorphism of (I) and (II) once more demonstrates the chemical analogy between NpVII and PuVII and permits a comparison of bond lengths in isostructural NpVII and PuVII compounds. The average An—O distances are 1.894 and 1.889 Å in AnO4 groups and 2.338 and 2.317 Å to OH groups for Np and Pu, respectively. The shortening of the An—O(OH) bonds on changing from Np to Pu (0.021 Å) is greater than that for the AnO4 groups (0.005 Å). Taking into account that the s.u.s of individual An—O distances in these structures are not greater than 0.002 Å, we can conclude that actinide contraction in the compounds under investigation is anisotropic. A similar behaviour was found for other isomorphous pairs of NpVII and PuVII compounds (Charushnikova et al., 2007; Grigoriev & Krot, 2007a).