Novel hepta­valent actinide compounds: tetra­sodium dihydroxidotetra­oxido­neptunate(VII) hydroxide dihydrate and its plutonium analogue

The title compounds, Na₄[NpO₄(OH)₂]OH·2H₂O and Na₄[PuO₄(OH)₂]OH·2H₂O, are isostructural and isomorphous, and contain complex [AnO₄(OH)₂]^3- anions (Ac is an actinide) in the form of distorted tetra­gonal bipyramids, Na⁺ cations, crystallization water mol­ecules and outer-sphere OH groups. The complex [AnO₄(OH)₂]^3- anions occupy general positions and the coordinated OH groups deviate significantly from a centrosymmetric relative orientation. The [AnO₄(OH)₂]^3- anions exhibit anisotropic actinide contraction; the shortening of the An-O(hydroxide) bonds on going from Np to Pu is greater than that of the AnO₄ groups.

S1. Comment

The majority of structural studies of An^VII 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 Pu^VII 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 Np^VII, (I), Na₄[NpO₄(OH)₂](OH).2H₂O, and Pu^VII, (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 An^VII 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 Np^VII and Pu^VII and permits a comparison of bond lengths in isostructural Np^VII and Pu^VII 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 Np^VII and Pu^VII compounds (Charushnikova et al., 2007; Grigoriev & Krot, 2007a).

Related literature

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).

S2. Experimental

The starting solutions for the syntheses of (I) and (II) were 0.075 M ²³⁷Np^VII in 2.5 M LiOH and 0.06 M ²³⁹Pu^VII 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 Pu^VI hydroxide compounds was found.

All attempts at the synthesis have given twinned crystals, both for Np and Pu.

S3. Refinement

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 U_iso 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).

Computing details

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).

Figures

	Fig. 1. A view of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. Dashed lines indicate hydrogen bonds.
	Fig. 2. A view of (I) showing the layer structure with interlayer hydrogen bonds. Thin lines (solid and dashed) delineate the distorted octahedra surrounding Na1 and its congeners.

(I) Tetrasodium dihydroxidotetraoxidoneptunate(VII) hydroxide dihydrate

Crystal data

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) Å^3

Data collection

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

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: difference Fourier map
wR(F^2) = 0.054	All H-atom parameters refined
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0277P)^2 + 0.1404P] where P = (Fo^2 + 2Fc^2)/3
4029 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 2.16 e Å^−3
9 restraints	Δρmin = −1.82 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
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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Np1—O1	1.891 (2)	Na2—O3^iv	2.479 (3)
Np1—O2	1.888 (2)	Na2—O6^v	2.524 (3)
Np1—O3	1.917 (2)	Na2—O6	2.529 (3)
Np1—O4	1.880 (2)	Na3—O8^vi	2.321 (3)
Np1—O5	2.315 (2)	Na3—O9	2.363 (3)
Np1—O6	2.362 (2)	Na3—O2^vii	2.413 (3)
Na1—O5^i	2.356 (3)	Na3—O6	2.472 (3)
Na1—O5	2.381 (3)	Na3—O6^vii	2.514 (3)
Na1—O1^ii	2.382 (3)	Na3—O3	2.526 (3)
Na1—O4^i	2.420 (3)	Na4—O9	2.325 (3)
Na1—O3	2.501 (3)	Na4—O7^i	2.377 (3)
Na1—O4^ii	2.550 (3)	Na4—O7^vi	2.420 (3)
Na2—O8^iii	2.327 (3)	Na4—O3	2.469 (3)
Na2—O1	2.433 (3)	Na4—O5^i	2.613 (3)
Na2—O2^iv	2.439 (3)	Na4—O4	2.864 (3)
O1—Np1—O2	91.52 (10)	O2^iv—Na2—O6^v	88.01 (9)
O1—Np1—O3	177.96 (10)	O3^iv—Na2—O6^v	91.40 (9)
O1—Np1—O4	89.53 (10)	O8^iii—Na2—O6	89.56 (9)
O1—Np1—O5	93.62 (9)	O1—Na2—O6	73.19 (8)
O1—Np1—O6	87.44 (9)	O2^iv—Na2—O6	163.23 (10)
O2—Np1—O3	88.67 (10)	O3^iv—Na2—O6	97.81 (9)
O2—Np1—O4	178.95 (9)	O6^v—Na2—O6	91.36 (8)
O2—Np1—O5	93.47 (10)	O8^vi—Na3—O9	90.37 (10)
O2—Np1—O6	87.60 (9)	O8^vi—Na3—O2^vii	99.31 (10)
O3—Np1—O4	90.28 (10)	O9—Na3—O2^vii	109.28 (11)
O3—Np1—O5	88.40 (9)	O8^vi—Na3—O6	170.16 (12)
O3—Np1—O6	90.54 (9)	O9—Na3—O6	90.16 (9)
O4—Np1—O5	86.58 (10)	O2^vii—Na3—O6	89.78 (9)
O4—Np1—O6	92.33 (9)	O8^vi—Na3—O6^vii	90.08 (10)
O5—Np1—O6	178.47 (8)	O9—Na3—O6^vii	176.70 (11)
O5^i—Na1—O5	88.77 (9)	O2^vii—Na3—O6^vii	73.86 (9)
O5^i—Na1—O1^ii	166.05 (10)	O6—Na3—O6^vii	88.84 (9)
O5—Na1—O1^ii	105.19 (10)	O8^vi—Na3—O3	94.84 (10)
O5^i—Na1—O4^i	74.58 (9)	O9—Na3—O3	86.15 (10)
O5—Na1—O4^i	93.43 (9)	O2^vii—Na3—O3	158.84 (10)
O1^ii—Na1—O4^i	104.25 (9)	O6—Na3—O3	75.39 (8)
O5^i—Na1—O3	93.78 (9)	O6^vii—Na3—O3	90.56 (9)
O5—Na1—O3	74.72 (8)	O9—Na4—O7^i	110.87 (11)
O1^ii—Na1—O3	89.78 (9)	O9—Na4—O7^vi	99.20 (10)
O4^i—Na1—O3	163.76 (9)	O7^i—Na4—O7^vi	93.10 (10)
O5^i—Na1—O4^ii	101.00 (9)	O9—Na4—O3	88.29 (10)
O5—Na1—O4^ii	170.10 (10)	O7^i—Na4—O3	160.11 (11)
O1^ii—Na1—O4^ii	65.05 (8)	O7^vi—Na4—O3	88.85 (9)
O4^i—Na1—O4^ii	90.80 (9)	O9—Na4—O5^i	160.69 (11)
O3—Na1—O4^ii	102.70 (9)	O7^i—Na4—O5^i	71.66 (9)
O8^iii—Na2—O1	100.12 (11)	O7^vi—Na4—O5^i	99.76 (10)
O8^iii—Na2—O2^iv	106.87 (10)	O3—Na4—O5^i	88.50 (9)
O1—Na2—O2^iv	106.27 (9)	O9—Na4—O4	82.73 (9)
O8^iii—Na2—O3^iv	169.56 (11)	O7^i—Na4—O4	115.40 (10)
O1—Na2—O3^iv	89.14 (9)	O7^vi—Na4—O4	148.90 (10)
O2^iv—Na2—O3^iv	65.46 (8)	O3—Na4—O4	60.09 (8)
O8^iii—Na2—O6^v	80.99 (10)	O5^i—Na4—O4	79.18 (8)
O1—Na2—O6^v	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.

Hydrogen-bond geometry (Å, º)

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···O8^viii	0.79 (2)	2.49 (3)	3.154 (4)	142 (4)
O7—H7···O4^ix	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···O1^vi	0.85 (2)	1.94 (2)	2.781 (3)	173 (5)
O9—H9B···O7^viii	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.

(II) Tetrasodium dihydroxidotetraoxidoplutonate(VII) hydroxide dihydrate

Crystal data

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) Å^3

Data collection

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

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)] = 0.028	Hydrogen site location: difference Fourier map
wR(F^2) = 0.039	All H-atom parameters refined
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0086P)^2] where P = (Fo^2 + 2Fc^2)/3
5736 reflections	(Δ/σ)max = 0.001
149 parameters	Δρmax = 2.54 e Å^−3
9 restraints	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
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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Pu1—O1	1.8824 (15)	Na2—O3^iv	2.459 (2)
Pu1—O2	1.8805 (18)	Na2—O6	2.5002 (19)
Pu1—O3	1.9109 (15)	Na2—O6^v	2.522 (2)
Pu1—O4	1.8811 (19)	Na3—O8^vi	2.310 (2)
Pu1—O5	2.2952 (19)	Na3—O9	2.349 (2)
Pu1—O6	2.339 (2)	Na3—O2^vii	2.396 (2)
Na1—O5^i	2.345 (2)	Na3—O6	2.4501 (19)
Na1—O5	2.360 (2)	Na3—O6^vii	2.477 (2)
Na1—O1^ii	2.370 (2)	Na3—O3	2.505 (2)
Na1—O4^i	2.410 (2)	Na4—O9	2.316 (2)
Na1—O3	2.484 (2)	Na4—O7^i	2.357 (2)
Na1—O4^ii	2.5247 (19)	Na4—O7^vi	2.3992 (19)
Na2—O8^iii	2.310 (2)	Na4—O3	2.453 (2)
Na2—O2^iv	2.4174 (18)	Na4—O5^i	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)	O3^iv—Na2—O6	97.86 (7)
O1—Pu1—O4	89.58 (7)	O8^iii—Na2—O6^v	81.32 (8)
O1—Pu1—O5	93.39 (7)	O2^iv—Na2—O6^v	87.78 (7)
O1—Pu1—O6	87.62 (7)	O1—Na2—O6^v	164.86 (7)
O2—Pu1—O3	88.68 (7)	O3^iv—Na2—O6^v	91.08 (7)
O2—Pu1—O4	178.79 (8)	O6—Na2—O6^v	91.60 (7)
O2—Pu1—O5	93.42 (7)	O8^vi—Na3—O9	90.06 (7)
O2—Pu1—O6	87.49 (8)	O8^vi—Na3—O2^vii	99.22 (7)
O3—Pu1—O4	90.23 (7)	O9—Na3—O2^vii	108.73 (7)
O3—Pu1—O5	88.35 (7)	O8^vi—Na3—O6	170.25 (9)
O3—Pu1—O6	90.63 (7)	O9—Na3—O6	90.17 (7)
O4—Pu1—O5	87.07 (8)	O2^vii—Na3—O6	89.94 (7)
O4—Pu1—O6	92.01 (7)	O8^vi—Na3—O6^vii	90.27 (7)
O5—Pu1—O6	178.62 (7)	O9—Na3—O6^vii	177.04 (8)
O5^i—Na1—O5	88.49 (7)	O2^vii—Na3—O6^vii	74.11 (7)
O5^i—Na1—O1^ii	166.70 (7)	O6—Na3—O6^vii	89.02 (7)
O5—Na1—O1^ii	104.81 (7)	O8^vi—Na3—O3	94.71 (7)
O5^i—Na1—O4^i	74.91 (7)	O9—Na3—O3	85.98 (7)
O5—Na1—O4^i	93.27 (7)	O2^vii—Na3—O3	159.59 (7)
O1^ii—Na1—O4^i	103.77 (7)	O6—Na3—O3	75.58 (6)
O5^i—Na1—O3	93.69 (7)	O6^vii—Na3—O3	91.07 (7)
O5—Na1—O3	74.79 (6)	O9—Na4—O7^i	110.84 (8)
O1^ii—Na1—O3	89.93 (7)	O9—Na4—O7^vi	98.80 (7)
O4^i—Na1—O3	163.89 (7)	O7^i—Na4—O7^vi	92.77 (7)
O5^i—Na1—O4^ii	101.20 (7)	O9—Na4—O3	87.94 (7)
O5—Na1—O4^ii	170.09 (8)	O7^i—Na4—O3	160.69 (8)
O1^ii—Na1—O4^ii	65.51 (6)	O7^vi—Na4—O3	88.57 (7)
O4^i—Na1—O4^ii	91.29 (7)	O9—Na4—O5^i	160.74 (7)
O3—Na1—O4^ii	102.23 (7)	O7^i—Na4—O5^i	72.19 (7)
O8^iii—Na2—O2^iv	106.36 (7)	O7^vi—Na4—O5^i	100.05 (7)
O8^iii—Na2—O1	99.93 (8)	O3—Na4—O5^i	88.61 (7)
O2^iv—Na2—O1	106.13 (7)	O9—Na4—O4	82.43 (6)
O8^iii—Na2—O3^iv	169.47 (8)	O7^i—Na4—O4	115.77 (7)
O2^iv—Na2—O3^iv	65.82 (6)	O7^vi—Na4—O4	149.16 (7)
O1—Na2—O3^iv	89.32 (7)	O3—Na4—O4	60.61 (6)
O8^iii—Na2—O6	89.68 (7)	O5^i—Na4—O4	79.37 (6)
O2^iv—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.

Hydrogen-bond geometry (Å, º)

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···O8^viii	0.76 (2)	2.59 (3)	3.152 (3)	132 (3)
O7—H7···O4^ix	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···O1^vi	0.84 (2)	1.94 (2)	2.770 (2)	174 (3)
O9—H9B···O7^viii	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.