Crystal structures of three uranyl–acetate–bi­py­ri­dine com­plexes crystallized from hydraulic fracking fluid

Hydraulic fracking exposes shale plays to acidic hydraulic fracking fluid (HFF), releasing toxic uranium (U) along with the desired oil and gas. With no existing methods to ensure U remains sequestered in the shale, this study sought to add organic ligands to HFF to explore potential U retention in shale plays. To test this possibility, incubations were set up in which uranyl acetate and one organic bi­py­ri­dine ligand (either 2,2′-, 2,3′-, 2,4′-, or 4,4′-bi­py­ri­dine) were added to pristine HFF as the crystallization medium. After several months and com­plete evaporation of all volatiles, bulk yellow crystalline material was obtained from the incubations, three of which yielded crystals suitable for single-crystal analysis, resulting in two novel structures and a high-quality structure of a previously described com­pound. The UO₂^VI acetate com­plexes bis­(acetato-κ²O,O′)(2,2′-bi­py­ri­dine-κ²N,N′)dioxidouranium(VI), [U(C₂H₃O₂)₂O₂(C₁₀H₈N₂)₂] or [2,2′-bi­py­ri­dine]U^VIO₂(CH₃CO₂)₂, (I), and bis­(acetato-κ²O,O′)(2,4′-bi­py­ri­dine-κN^1′)dioxidouranium(VI), [U(C₂H₃O₂)₂O₂(C₁₀H₈N₂)₂] or [2,4′-bi­py­ri­dine]₂U^VIO₂(CH₃CO₂)₂, (III), contain eight-coordinate U^VI in a pseudo-hexa­gonal bipyramidal coordination geometry and are mol­ecular, packing via weak C—H...O/N inter­actions, whereas catena-poly[bis­(2,3′-bipyridinium) [di-μ-acetato-μ₃-hydroxido-μ-hydroxido-di-μ₃-oxido-hexa­oxidotriuranium(VI)]–2,3′-bi­py­ri­dine–water (1/1/1)], (C₁₀H₉N₂)₂[U₃(C₂H₃O₂)₂O₈(OH)₂]·C₁₀H₈N₂·H₂O or {[2,3′-bipyridinium]₂[2,3′-bi­py­ri­dine][(U^VIO₂)₃(O)₂(OH)₂(CH₃CO₂)₂·H₂O]}_n, (II), forms an ionic one-dimensional polymer with seven-coordinate penta­gonal bipyramidal U^VI centers and hydrogen-bonding inter­actions within each chain. The formation of these crystals could indicate the potential for bi­py­ri­dine to bind with U in shale during fracking, which will be explored in a future study via ICP-MS (inductively coupled plasma mass spectrometry) analyses of U concentration in HFF/bi­py­ri­dine/shale incubations. The variation seen here between the mol­ecular structures may indicate variance in the ability of bi­py­ri­dine isomers to form com­plexes with U, which could impact their ability to retain U within shale in the context of fracking.

Computing details

Bis(acetato-κ²O,O')(2,2'-bipyridine-κ²N,N')dioxidouranium(VI) (I_AW2829U)

Crystal data

[U(C2H3O2)2O2(C10H8N2)]	F(000) = 1008
Mr = 544.30	Dx = 2.330 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.7340 (8) Å	Cell parameters from 9880 reflections
b = 19.010 (2) Å	θ = 2.2–30.5°
c = 10.6154 (11) Å	µ = 10.49 mm^−1
β = 96.106 (2)°	T = 125 K
V = 1551.9 (3) Å^3	Block, yellow
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer	4720 independent reflections
Radiation source: sealed X-ray tube, Bruker APEXII CCD	4280 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 8.3333 pixels mm^-1	θmax = 30.5°, θmin = 2.1°
φ and ω scans	h = −10→11
Absorption correction: multi-scan (SADABS: Bruker, 2013)	k = −26→26
Tmin = 0.28, Tmax = 0.42	l = −15→15
37906 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.016	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.035	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0136P)^2 + 1.5912P] where P = (Fo^2 + 2Fc^2)/3
4720 reflections	(Δ/σ)max = 0.001
210 parameters	Δρmax = 1.06 e Å^−3
0 restraints	Δρmin = −0.56 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. CheckCIF reported "PLAT977 Type_2 Test for negative density on H-atom positions" for the three AFIX 137 hydrogens on C12. For the disordered C12 methyl group with two orientations rotated by 60 deg., HFIX 123 was used, subsequently with refinement of the site occupation, where the free variable refined to 0.505 (3).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
U	0.72204 (2)	0.33122 (2)	0.34035 (2)	0.01312 (3)
O1	0.4915 (2)	0.33481 (8)	0.33062 (15)	0.0189 (3)
O2	0.9520 (2)	0.32775 (8)	0.34741 (16)	0.0198 (3)
O3	0.6938 (2)	0.27455 (8)	0.54552 (14)	0.0194 (3)
O4	0.7284 (2)	0.20501 (8)	0.38640 (15)	0.0224 (3)
O5	0.7356 (2)	0.37058 (8)	0.11979 (15)	0.0190 (3)
O6	0.6966 (2)	0.25809 (8)	0.15022 (15)	0.0238 (4)
N1	0.8201 (2)	0.41311 (9)	0.53314 (17)	0.0150 (3)
N2	0.6570 (2)	0.46772 (9)	0.32062 (17)	0.0156 (3)
C1	0.9224 (3)	0.38536 (12)	0.6306 (2)	0.0181 (4)
H1A	0.951625	0.336899	0.627365	0.022*
C2	0.9874 (3)	0.42408 (12)	0.7356 (2)	0.0188 (4)
H2A	1.060631	0.402727	0.802378	0.023*
C3	0.9436 (3)	0.49444 (12)	0.7413 (2)	0.0206 (4)
H3A	0.983732	0.521905	0.813299	0.025*
C4	0.8401 (3)	0.52449 (12)	0.6405 (2)	0.0186 (4)
H4A	0.808733	0.572768	0.642401	0.022*
C5	0.7829 (3)	0.48257 (11)	0.5363 (2)	0.0144 (4)
C6	0.6850 (3)	0.51214 (11)	0.4207 (2)	0.0145 (4)
C7	0.6296 (3)	0.58192 (11)	0.4135 (2)	0.0187 (4)
H7A	0.650676	0.611892	0.485057	0.022*
C8	0.5437 (3)	0.60747 (12)	0.3018 (2)	0.0213 (5)
H8A	0.506159	0.655037	0.295151	0.026*
C9	0.5138 (3)	0.56184 (12)	0.1997 (2)	0.0219 (5)
H9A	0.454847	0.577536	0.121638	0.026*
C10	0.5716 (3)	0.49289 (12)	0.2137 (2)	0.0196 (4)
H10A	0.549433	0.461869	0.143631	0.024*
C11	0.7050 (3)	0.21294 (11)	0.5014 (2)	0.0169 (4)
C12	0.6914 (3)	0.14993 (12)	0.5854 (2)	0.0220 (5)
H12A	0.673526	0.16561	0.670976	0.033*	0.51 (3)
H12B	0.592892	0.120736	0.551336	0.033*	0.51 (3)
H12C	0.798875	0.122381	0.588556	0.033*	0.51 (3)
H12D	0.703336	0.106874	0.536269	0.033*	0.49 (3)
H12E	0.78397	0.151749	0.655909	0.033*	0.49 (3)
H12F	0.577987	0.150104	0.618689	0.033*	0.49 (3)
C13	0.7238 (3)	0.30785 (12)	0.0762 (2)	0.0165 (4)
C14	0.7426 (3)	0.29360 (12)	−0.0602 (2)	0.0195 (4)
H14A	0.78596	0.335912	−0.099174	0.029*
H14B	0.629206	0.280683	−0.10423	0.029*
H14C	0.824834	0.254881	−0.066527	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U	0.01680 (4)	0.00834 (4)	0.01466 (4)	−0.00089 (3)	0.00377 (3)	−0.00027 (3)
O1	0.0174 (8)	0.0175 (8)	0.0218 (8)	−0.0030 (6)	0.0027 (6)	0.0015 (6)
O2	0.0176 (8)	0.0189 (8)	0.0236 (8)	0.0015 (6)	0.0050 (6)	−0.0001 (6)
O3	0.0275 (9)	0.0137 (7)	0.0177 (7)	−0.0030 (6)	0.0051 (6)	0.0008 (6)
O4	0.0380 (10)	0.0114 (7)	0.0189 (7)	−0.0007 (7)	0.0079 (7)	0.0008 (6)
O5	0.0281 (9)	0.0122 (7)	0.0173 (7)	0.0013 (6)	0.0055 (6)	−0.0003 (6)
O6	0.0419 (11)	0.0125 (7)	0.0178 (8)	−0.0050 (7)	0.0064 (7)	−0.0007 (6)
N1	0.0158 (9)	0.0105 (8)	0.0190 (8)	−0.0011 (7)	0.0034 (7)	−0.0007 (6)
N2	0.0169 (9)	0.0112 (8)	0.0188 (8)	0.0001 (7)	0.0029 (7)	0.0001 (6)
C1	0.0185 (11)	0.0140 (10)	0.0218 (10)	0.0009 (8)	0.0023 (8)	0.0016 (8)
C2	0.0162 (11)	0.0212 (11)	0.0191 (10)	−0.0026 (8)	0.0023 (8)	0.0002 (8)
C3	0.0213 (11)	0.0218 (11)	0.0189 (10)	−0.0039 (9)	0.0037 (8)	−0.0057 (8)
C4	0.0200 (11)	0.0135 (10)	0.0230 (10)	−0.0010 (8)	0.0051 (8)	−0.0043 (8)
C5	0.0133 (9)	0.0123 (9)	0.0187 (9)	−0.0018 (7)	0.0065 (7)	−0.0014 (7)
C6	0.0129 (9)	0.0121 (9)	0.0195 (9)	−0.0020 (7)	0.0064 (7)	−0.0008 (7)
C7	0.0226 (11)	0.0121 (10)	0.0227 (10)	0.0010 (8)	0.0078 (9)	−0.0014 (8)
C8	0.0264 (12)	0.0114 (10)	0.0270 (11)	0.0043 (9)	0.0078 (9)	0.0018 (8)
C9	0.0246 (12)	0.0186 (11)	0.0224 (11)	0.0049 (9)	0.0021 (9)	0.0029 (8)
C10	0.0218 (11)	0.0160 (10)	0.0206 (10)	0.0012 (8)	0.0010 (8)	−0.0006 (8)
C11	0.0162 (10)	0.0139 (10)	0.0203 (10)	−0.0022 (8)	0.0009 (8)	0.0021 (8)
C12	0.0281 (13)	0.0166 (10)	0.0211 (11)	−0.0030 (9)	0.0010 (9)	0.0058 (8)
C13	0.0163 (10)	0.0157 (10)	0.0177 (10)	0.0015 (8)	0.0022 (8)	0.0006 (8)
C14	0.0250 (12)	0.0161 (10)	0.0179 (10)	0.0024 (9)	0.0045 (9)	−0.0008 (8)

Geometric parameters (Å, º)

U—O2	1.7733 (16)	C3—H3A	0.95
U—O1	1.7761 (16)	C4—C5	1.396 (3)
U—O6	2.4415 (16)	C4—H4A	0.95
U—O4	2.4479 (16)	C5—C6	1.482 (3)
U—O3	2.4602 (15)	C6—C7	1.394 (3)
U—O5	2.4709 (15)	C7—C8	1.384 (3)
U—N1	2.6185 (18)	C7—H7A	0.95
U—N2	2.6473 (18)	C8—C9	1.388 (3)
U—C11	2.836 (2)	C8—H8A	0.95
U—C13	2.840 (2)	C9—C10	1.388 (3)
O3—C11	1.268 (3)	C9—H9A	0.95
O4—C11	1.262 (3)	C10—H10A	0.95
O5—C13	1.279 (3)	C11—C12	1.504 (3)
O6—C13	1.262 (3)	C12—H12A	0.98
N1—C1	1.342 (3)	C12—H12B	0.98
N1—C5	1.352 (3)	C12—H12C	0.98
N2—C10	1.340 (3)	C12—H12D	0.98
N2—C6	1.357 (3)	C12—H12E	0.98
C1—C2	1.385 (3)	C12—H12F	0.98
C1—H1A	0.95	C13—C14	1.495 (3)
C2—C3	1.383 (3)	C14—H14A	0.98
C2—H2A	0.95	C14—H14B	0.98
C3—C4	1.389 (3)	C14—H14C	0.98
O2—U—O1	179.09 (7)	N1—C1—H1A	118.5
O2—U—O6	90.34 (7)	C2—C1—H1A	118.5
O1—U—O6	88.96 (7)	C3—C2—C1	118.7 (2)
O2—U—O4	87.50 (7)	C3—C2—H2A	120.7
O1—U—O4	92.75 (6)	C1—C2—H2A	120.7
O6—U—O4	66.74 (5)	C2—C3—C4	119.2 (2)
O2—U—O3	97.43 (7)	C2—C3—H3A	120.4
O1—U—O3	83.41 (6)	C4—C3—H3A	120.4
O6—U—O3	118.40 (5)	C3—C4—C5	118.9 (2)
O4—U—O3	52.83 (5)	C3—C4—H4A	120.5
O2—U—O5	84.70 (7)	C5—C4—H4A	120.5
O1—U—O5	94.41 (7)	N1—C5—C4	121.8 (2)
O6—U—O5	52.91 (5)	N1—C5—C6	116.16 (18)
O4—U—O5	118.95 (5)	C4—C5—C6	122.00 (19)
O3—U—O5	171.18 (5)	N2—C6—C7	121.8 (2)
O2—U—N1	77.49 (7)	N2—C6—C5	115.93 (18)
O1—U—N1	103.18 (6)	C7—C6—C5	122.27 (19)
O6—U—N1	167.37 (6)	C8—C7—C6	119.9 (2)
O4—U—N1	115.38 (6)	C8—C7—H7A	120.1
O3—U—N1	67.30 (5)	C6—C7—H7A	120.1
O5—U—N1	121.51 (5)	C7—C8—C9	118.3 (2)
O2—U—N2	102.77 (6)	C7—C8—H8A	120.8
O1—U—N2	77.09 (6)	C9—C8—H8A	120.8
O6—U—N2	119.66 (5)	C10—C9—C8	118.8 (2)
O4—U—N2	167.45 (6)	C10—C9—H9A	120.6
O3—U—N2	117.72 (5)	C8—C9—H9A	120.6
O5—U—N2	69.82 (5)	N2—C10—C9	123.5 (2)
N1—U—N2	61.04 (6)	N2—C10—H10A	118.2
O2—U—C11	93.19 (7)	C9—C10—H10A	118.2
O1—U—C11	87.42 (7)	O4—C11—O3	119.36 (19)
O6—U—C11	92.41 (6)	O4—C11—C12	120.3 (2)
O4—U—C11	26.34 (6)	O3—C11—C12	120.3 (2)
O3—U—C11	26.50 (6)	O4—C11—U	59.41 (11)
O5—U—C11	145.15 (6)	O3—C11—U	59.98 (11)
N1—U—C11	91.63 (6)	C12—C11—U	178.56 (16)
N2—U—C11	143.54 (6)	C11—C12—H12A	109.5
O2—U—C13	85.75 (7)	C11—C12—H12B	109.5
O1—U—C13	93.37 (7)	H12A—C12—H12B	109.5
O6—U—C13	26.27 (6)	C11—C12—H12C	109.5
O4—U—C13	92.39 (6)	H12A—C12—H12C	109.5
O3—U—C13	144.65 (6)	H12B—C12—H12C	109.5
O5—U—C13	26.72 (6)	H12D—C12—H12E	109.5
N1—U—C13	146.42 (6)	H12D—C12—H12F	109.5
N2—U—C13	95.51 (6)	H12E—C12—H12F	109.5
C11—U—C13	118.45 (6)	O6—C13—O5	118.96 (19)
C11—O3—U	93.51 (13)	O6—C13—C14	120.5 (2)
C11—O4—U	94.26 (13)	O5—C13—C14	120.57 (19)
C13—O5—U	92.97 (12)	O6—C13—U	58.93 (11)
C13—O6—U	94.81 (13)	O5—C13—U	60.31 (11)
C1—N1—C5	118.31 (19)	C14—C13—U	174.52 (16)
C1—N1—U	117.82 (14)	C13—C14—H14A	109.5
C5—N1—U	123.72 (14)	C13—C14—H14B	109.5
C10—N2—C6	117.71 (19)	H14A—C14—H14B	109.5
C10—N2—U	119.31 (14)	C13—C14—H14C	109.5
C6—N2—U	122.34 (14)	H14A—C14—H14C	109.5
N1—C1—C2	123.1 (2)	H14B—C14—H14C	109.5
C5—N1—C1—C2	1.9 (3)	N1—C5—C6—C7	176.32 (19)
U—N1—C1—C2	177.67 (17)	C4—C5—C6—C7	−6.3 (3)
N1—C1—C2—C3	0.7 (3)	N2—C6—C7—C8	−0.1 (3)
C1—C2—C3—C4	−1.7 (3)	C5—C6—C7—C8	177.8 (2)
C2—C3—C4—C5	0.2 (3)	C6—C7—C8—C9	0.6 (3)
C1—N1—C5—C4	−3.6 (3)	C7—C8—C9—C10	−0.2 (3)
U—N1—C5—C4	−179.05 (15)	C6—N2—C10—C9	1.2 (3)
C1—N1—C5—C6	173.81 (18)	U—N2—C10—C9	172.24 (18)
U—N1—C5—C6	−1.7 (2)	C8—C9—C10—N2	−0.7 (4)
C3—C4—C5—N1	2.6 (3)	U—O4—C11—O3	−1.9 (2)
C3—C4—C5—C6	−174.7 (2)	U—O4—C11—C12	178.36 (19)
C10—N2—C6—C7	−0.8 (3)	U—O3—C11—O4	1.9 (2)
U—N2—C6—C7	−171.52 (15)	U—O3—C11—C12	−178.37 (19)
C10—N2—C6—C5	−178.84 (19)	U—O6—C13—O5	−6.1 (2)
U—N2—C6—C5	10.4 (2)	U—O6—C13—C14	173.66 (19)
N1—C5—C6—N2	−5.6 (3)	U—O5—C13—O6	6.0 (2)
C4—C5—C6—N2	171.74 (19)	U—O5—C13—C14	−173.75 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O4^i	0.95	2.54	3.380 (3)	148
C7—H7A···O1^ii	0.95	2.55	3.362 (3)	143
C10—H10A···O5	0.95	2.29	2.877 (3)	120
C12—H12E···O1^i	0.98	2.33	3.311 (3)	175
C14—H14B···O2^iii	0.98	2.50	3.296 (3)	138
C14—H14C···O1^iv	0.98	2.46	3.389 (3)	158

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

catena-Poly[bis(2,3'-bipyridinium) [di-µ-acetato-µ₃-hydroxido-µ-hydroxido-di-µ₃-oxido-hexaoxidotriuranium(VI)]–2,3'-bipyridine–water (1/1/1)] (II_AW2903U)

Crystal data

(C10H9N2)2[U3(C2H3O2)2O8(OH)2]·C10H8N2·H2O	F(000) = 2712
Mr = 1482.78	Dx = 2.449 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.8090 (13) Å	Cell parameters from 9794 reflections
b = 12.6324 (12) Å	θ = 2.4–30.5°
c = 23.699 (2) Å	µ = 12.13 mm^−1
β = 103.412 (1)°	T = 125 K
V = 4021.3 (6) Å^3	Needle, yellow
Z = 4	0.20 × 0.04 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer	12285 independent reflections
Radiation source: sealed X-ray tube, Bruker APEXII CCD	8925 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.107
Detector resolution: 8.3333 pixels mm^-1	θmax = 30.6°, θmin = 1.8°
φ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS: Bruker, 2013)	k = −18→18
Tmin = 0.51, Tmax = 0.79	l = −33→33
98670 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: mixed
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0238P)^2] where P = (Fo^2 + 2Fc^2)/3
12285 reflections	(Δ/σ)max = 0.003
547 parameters	Δρmax = 1.58 e Å^−3
22 restraints	Δρmin = −1.54 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
U1	0.70187 (2)	0.48978 (2)	0.81887 (2)	0.00964 (5)
U2	0.82854 (2)	0.63580 (2)	0.71320 (2)	0.00788 (5)
U3	0.75860 (2)	0.34264 (2)	0.68621 (2)	0.00804 (5)
O1	0.5873 (3)	0.5440 (3)	0.77836 (17)	0.0179 (9)
O2	0.8119 (3)	0.4348 (3)	0.86252 (16)	0.0178 (9)
O3	0.7069 (3)	0.6695 (3)	0.67373 (17)	0.0171 (9)
O4	0.9540 (3)	0.6069 (3)	0.74897 (15)	0.0144 (8)
O5	0.6435 (3)	0.3794 (3)	0.63880 (15)	0.0125 (8)
O6	0.8754 (3)	0.3030 (3)	0.72926 (15)	0.0134 (8)
O7	0.7673 (3)	0.4873 (3)	0.74153 (15)	0.0128 (8)
O8	0.8288 (3)	0.4935 (3)	0.64359 (15)	0.0108 (8)
H8	0.886 (2)	0.481 (5)	0.639 (3)	0.04 (2)*
O9	0.7083 (3)	0.1588 (3)	0.68989 (14)	0.0094 (8)
O10	0.8417 (3)	0.8209 (3)	0.73945 (16)	0.0104 (8)
H10	0.893 (3)	0.838 (6)	0.764 (2)	0.05 (3)*
O11	0.8082 (3)	0.2696 (3)	0.60472 (15)	0.0174 (9)
O12	0.8128 (3)	0.0942 (3)	0.60014 (17)	0.0237 (10)
O13	0.6068 (3)	0.3836 (3)	0.86954 (17)	0.0224 (10)
O14	0.6102 (3)	0.2084 (3)	0.86533 (16)	0.0228 (10)
O1W	0.4636 (4)	0.3861 (4)	0.7048 (2)	0.0255 (11)
H1WA	0.474 (5)	0.443 (6)	0.720 (3)	0.04 (3)*
H1WB	0.419 (6)	0.364 (6)	0.719 (3)	0.05 (3)*
N1	0.6704 (4)	0.2690 (4)	0.4444 (2)	0.0218 (12)
N2	0.7096 (4)	0.5328 (4)	0.54663 (19)	0.0153 (10)
H2	0.750 (4)	0.520 (4)	0.5807 (14)	0.018*
N3	0.1877 (4)	0.0726 (4)	0.5649 (2)	0.0263 (13)
N4	0.5377 (4)	0.1477 (4)	0.6000 (2)	0.0169 (11)
H4	0.589 (3)	0.153 (4)	0.6302 (17)	0.02*
N5	1.3058 (4)	0.2815 (4)	0.7419 (2)	0.0229 (12)
N6	1.0150 (4)	0.4441 (4)	0.6281 (2)	0.0217 (12)
C1	0.8318 (4)	0.1851 (4)	0.5837 (2)	0.0134 (12)
C2	0.8839 (5)	0.1950 (5)	0.5349 (2)	0.0202 (13)
H2A	0.885176	0.12583	0.516306	0.03*
H2B	0.952259	0.219623	0.550167	0.03*
H2C	0.848273	0.245914	0.506283	0.03*
C3	0.5939 (4)	0.2931 (4)	0.8887 (2)	0.0133 (11)
C4	0.5524 (5)	0.2868 (5)	0.9421 (2)	0.0259 (15)
H4A	0.593093	0.330254	0.972928	0.039*
H4B	0.553431	0.213117	0.955074	0.039*
H4C	0.483766	0.313072	0.932926	0.039*
C11	0.6549 (5)	0.1768 (5)	0.4164 (3)	0.0283 (16)
H11A	0.705477	0.124419	0.425566	0.034*
C12	0.5692 (5)	0.1526 (5)	0.3744 (3)	0.0218 (14)
H12A	0.560977	0.085103	0.356206	0.026*
C13	0.4959 (5)	0.2300 (5)	0.3599 (3)	0.0214 (14)
H13A	0.436383	0.217028	0.331311	0.026*
C14	0.5124 (4)	0.3266 (4)	0.3884 (2)	0.0155 (12)
H14A	0.464085	0.381412	0.379524	0.019*
C15	0.6000 (4)	0.3423 (4)	0.4298 (2)	0.0150 (12)
C16	0.6211 (4)	0.4448 (4)	0.4621 (2)	0.0136 (12)
C17	0.5758 (4)	0.5399 (5)	0.4410 (2)	0.0188 (13)
H17A	0.529046	0.542551	0.4046	0.023*
C18	0.6003 (5)	0.6307 (5)	0.4742 (3)	0.0231 (14)
H18A	0.57109	0.696499	0.460163	0.028*
C19	0.6670 (5)	0.6259 (5)	0.5274 (2)	0.0184 (13)
H19A	0.682743	0.687964	0.550394	0.022*
C21	0.1091 (5)	0.0416 (5)	0.5834 (3)	0.0349 (18)
H21A	0.046714	0.038286	0.556176	0.042*
C22	0.1125 (6)	0.0133 (5)	0.6410 (3)	0.0371 (18)
H22A	0.054151	−0.009227	0.652332	0.044*
C23	0.2027 (5)	0.0191 (5)	0.6807 (3)	0.0287 (16)
H23A	0.208328	0.00035	0.720161	0.034*
C24	0.2850 (5)	0.0531 (5)	0.6616 (3)	0.0229 (14)
H24A	0.347908	0.058871	0.688192	0.027*
C25	0.2754 (4)	0.0785 (5)	0.6040 (3)	0.0187 (13)
C26	0.3636 (5)	0.1054 (4)	0.5804 (2)	0.0165 (13)
C27	0.3620 (5)	0.0938 (4)	0.5215 (2)	0.0190 (13)
H27A	0.302356	0.074472	0.494523	0.023*
C28	0.4482 (5)	0.1110 (4)	0.5033 (3)	0.0217 (14)
H28A	0.4483	0.105865	0.463343	0.026*
C29	0.5356 (5)	0.1360 (4)	0.5441 (2)	0.0170 (12)
H29A	0.595475	0.144836	0.531422	0.02*
C31	1.3528 (5)	0.2249 (6)	0.7879 (3)	0.0331 (18)
H31A	1.423528	0.225516	0.798172	0.04*
C32	1.3025 (6)	0.1652 (6)	0.8212 (3)	0.0367 (19)
H32A	1.338144	0.126861	0.853964	0.044*
C33	1.2002 (6)	0.1625 (6)	0.8060 (3)	0.0366 (19)
H33A	1.163941	0.120622	0.827284	0.044*
C34	1.1518 (5)	0.2216 (5)	0.7594 (3)	0.0290 (16)
H34A	1.081107	0.222591	0.748739	0.035*
C35	1.2060 (4)	0.2798 (5)	0.7281 (3)	0.0193 (13)
C36	1.1567 (5)	0.3425 (5)	0.6763 (3)	0.0177 (13)
C37	1.2002 (5)	0.3575 (5)	0.6297 (3)	0.0231 (14)
H37A	1.263866	0.328347	0.630504	0.028*
C38	1.1506 (5)	0.4149 (5)	0.5823 (3)	0.0278 (16)
H38A	1.179645	0.426037	0.550193	0.033*
C39	1.0572 (5)	0.4561 (5)	0.5824 (3)	0.0245 (15)
H39A	1.021907	0.493781	0.549301	0.029*
C110	0.6873 (4)	0.4449 (4)	0.5154 (2)	0.0158 (12)
H11B	0.717912	0.380176	0.530318	0.019*
C210	0.4529 (5)	0.1340 (4)	0.6172 (3)	0.0185 (13)
H21B	0.454124	0.144568	0.656995	0.022*
C310	1.0649 (5)	0.3887 (5)	0.6734 (3)	0.0212 (14)
H31B	1.035696	0.380299	0.70572	0.025*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.01372 (11)	0.00664 (10)	0.01017 (9)	0.00001 (8)	0.00606 (8)	−0.00024 (7)
U2	0.00957 (11)	0.00640 (10)	0.00797 (9)	−0.00040 (8)	0.00266 (8)	−0.00023 (7)
U3	0.01095 (11)	0.00617 (10)	0.00722 (9)	−0.00004 (8)	0.00254 (8)	−0.00002 (7)
O1	0.014 (2)	0.013 (2)	0.025 (2)	0.0031 (17)	0.0036 (18)	0.0007 (17)
O2	0.027 (3)	0.010 (2)	0.0160 (19)	0.0011 (18)	0.0027 (18)	0.0003 (16)
O3	0.013 (2)	0.015 (2)	0.021 (2)	0.0048 (17)	0.0003 (17)	−0.0007 (17)
O4	0.013 (2)	0.018 (2)	0.0111 (18)	0.0025 (17)	0.0014 (16)	−0.0026 (15)
O5	0.012 (2)	0.0098 (19)	0.0147 (19)	0.0036 (16)	0.0014 (16)	0.0012 (15)
O6	0.016 (2)	0.0092 (19)	0.0149 (18)	0.0022 (17)	0.0034 (16)	−0.0007 (15)
O7	0.020 (2)	0.0081 (19)	0.0131 (18)	−0.0050 (16)	0.0088 (16)	−0.0002 (15)
O8	0.014 (2)	0.0084 (19)	0.0098 (17)	0.0023 (17)	0.0026 (16)	0.0000 (14)
O9	0.017 (2)	0.0030 (17)	0.0091 (17)	−0.0014 (15)	0.0045 (15)	−0.0004 (14)
O10	0.013 (2)	0.0067 (19)	0.0115 (18)	0.0026 (16)	0.0023 (16)	−0.0012 (14)
O11	0.033 (3)	0.007 (2)	0.0142 (19)	0.0023 (18)	0.0114 (18)	−0.0020 (15)
O12	0.050 (3)	0.0035 (19)	0.024 (2)	0.006 (2)	0.022 (2)	0.0031 (16)
O13	0.038 (3)	0.010 (2)	0.026 (2)	−0.0071 (19)	0.023 (2)	−0.0035 (17)
O14	0.042 (3)	0.013 (2)	0.020 (2)	0.005 (2)	0.019 (2)	0.0001 (17)
O1W	0.017 (3)	0.030 (3)	0.028 (3)	0.000 (2)	0.002 (2)	−0.005 (2)
N1	0.020 (3)	0.019 (3)	0.021 (3)	0.006 (2)	−0.007 (2)	−0.002 (2)
N2	0.015 (3)	0.018 (3)	0.011 (2)	0.004 (2)	−0.001 (2)	0.0039 (19)
N3	0.018 (3)	0.020 (3)	0.039 (3)	−0.002 (2)	0.003 (3)	0.003 (2)
N4	0.017 (3)	0.010 (2)	0.018 (2)	0.001 (2)	−0.007 (2)	−0.0012 (19)
N5	0.015 (3)	0.028 (3)	0.023 (3)	0.006 (2)	−0.001 (2)	−0.005 (2)
N6	0.022 (3)	0.018 (3)	0.025 (3)	0.001 (2)	0.005 (2)	−0.001 (2)
C1	0.022 (3)	0.012 (3)	0.009 (2)	0.001 (2)	0.009 (2)	0.002 (2)
C2	0.021 (4)	0.026 (3)	0.016 (3)	0.004 (3)	0.010 (3)	0.002 (2)
C3	0.013 (3)	0.013 (3)	0.015 (3)	0.000 (2)	0.006 (2)	−0.001 (2)
C4	0.046 (5)	0.017 (3)	0.021 (3)	0.000 (3)	0.021 (3)	0.000 (3)
C11	0.027 (4)	0.025 (4)	0.027 (3)	0.006 (3)	−0.006 (3)	0.000 (3)
C12	0.028 (4)	0.015 (3)	0.020 (3)	0.000 (3)	0.000 (3)	−0.005 (2)
C13	0.023 (4)	0.023 (3)	0.019 (3)	−0.005 (3)	0.005 (3)	−0.003 (2)
C14	0.012 (3)	0.015 (3)	0.017 (3)	0.000 (2)	0.001 (2)	−0.002 (2)
C15	0.015 (3)	0.018 (3)	0.010 (2)	−0.004 (2)	−0.001 (2)	0.001 (2)
C16	0.012 (3)	0.017 (3)	0.013 (3)	0.003 (2)	0.005 (2)	−0.001 (2)
C17	0.015 (3)	0.020 (3)	0.018 (3)	−0.001 (3)	−0.001 (2)	0.001 (2)
C18	0.029 (4)	0.012 (3)	0.025 (3)	0.008 (3)	−0.001 (3)	0.004 (2)
C19	0.022 (3)	0.011 (3)	0.019 (3)	−0.002 (3)	−0.001 (3)	0.002 (2)
C21	0.019 (4)	0.026 (4)	0.057 (5)	0.004 (3)	0.001 (3)	−0.002 (3)
C22	0.029 (4)	0.028 (4)	0.059 (5)	−0.002 (3)	0.021 (4)	−0.004 (4)
C23	0.037 (4)	0.020 (4)	0.034 (4)	0.000 (3)	0.018 (3)	−0.009 (3)
C24	0.027 (4)	0.016 (3)	0.028 (3)	−0.001 (3)	0.011 (3)	−0.006 (3)
C25	0.013 (3)	0.016 (3)	0.026 (3)	0.000 (2)	0.004 (3)	−0.003 (2)
C26	0.019 (3)	0.011 (3)	0.018 (3)	0.006 (2)	−0.001 (2)	0.003 (2)
C27	0.020 (3)	0.013 (3)	0.021 (3)	0.004 (3)	−0.002 (3)	−0.003 (2)
C28	0.034 (4)	0.012 (3)	0.017 (3)	0.005 (3)	0.001 (3)	0.001 (2)
C29	0.020 (3)	0.010 (3)	0.022 (3)	0.002 (2)	0.008 (3)	−0.002 (2)
C31	0.021 (4)	0.049 (5)	0.028 (4)	0.017 (3)	0.002 (3)	−0.009 (3)
C32	0.043 (5)	0.044 (5)	0.023 (3)	0.024 (4)	0.009 (3)	0.006 (3)
C33	0.040 (5)	0.046 (5)	0.029 (4)	0.015 (4)	0.019 (4)	0.012 (3)
C34	0.025 (4)	0.038 (4)	0.027 (3)	0.009 (3)	0.012 (3)	0.004 (3)
C35	0.007 (3)	0.023 (3)	0.027 (3)	0.008 (2)	0.002 (3)	−0.006 (3)
C36	0.015 (3)	0.017 (3)	0.022 (3)	−0.004 (2)	0.005 (3)	−0.004 (2)
C37	0.010 (3)	0.035 (4)	0.026 (3)	−0.001 (3)	0.008 (3)	−0.003 (3)
C38	0.031 (4)	0.037 (4)	0.020 (3)	0.003 (3)	0.016 (3)	0.000 (3)
C39	0.024 (4)	0.032 (4)	0.017 (3)	0.001 (3)	0.005 (3)	−0.005 (3)
C110	0.016 (3)	0.013 (3)	0.017 (3)	0.004 (2)	0.000 (2)	0.002 (2)
C210	0.023 (4)	0.013 (3)	0.018 (3)	0.001 (3)	0.001 (3)	0.004 (2)
C310	0.015 (3)	0.028 (4)	0.021 (3)	0.002 (3)	0.005 (3)	0.000 (3)

Geometric parameters (Å, º)

U1—O2	1.770 (4)	C4—H4B	0.98
U1—O1	1.786 (4)	C4—H4C	0.98
U1—O7	2.223 (3)	C11—C12	1.391 (9)
U1—O12^i	2.376 (4)	C11—H11A	0.95
U1—O13	2.386 (4)	C12—C13	1.392 (8)
U1—O9^i	2.502 (3)	C12—H12A	0.95
U1—O10^ii	2.538 (4)	C13—C14	1.388 (8)
U1—U2	3.8425 (3)	C13—H13A	0.95
U1—U3	3.8853 (4)	C14—C15	1.385 (8)
U2—O3	1.774 (4)	C14—H14A	0.95
U2—O4	1.782 (4)	C15—C16	1.498 (8)
U2—O7	2.224 (3)	C16—C110	1.376 (7)
U2—O14^i	2.398 (4)	C16—C17	1.393 (8)
U2—O10	2.415 (4)	C17—C18	1.388 (8)
U2—O8	2.441 (4)	C17—H17A	0.95
U2—O9^i	2.482 (3)	C18—C19	1.380 (8)
U2—U3	3.8431 (4)	C18—H18A	0.95
U2—U3^i	3.9102 (4)	C19—H19A	0.95
U3—O6	1.769 (4)	C21—C22	1.400 (10)
U3—O5	1.782 (4)	C21—H21A	0.95
U3—O7	2.236 (4)	C22—C23	1.379 (9)
U3—O11	2.380 (4)	C22—H22A	0.95
U3—O9	2.431 (3)	C23—C24	1.385 (9)
U3—O8	2.459 (4)	C23—H23A	0.95
U3—O10^ii	2.496 (4)	C24—C25	1.380 (8)
O8—H8	0.84 (2)	C24—H24A	0.95
O10—H10	0.84 (2)	C25—C26	1.492 (8)
O11—C1	1.252 (6)	C26—C210	1.383 (8)
O12—C1	1.260 (6)	C26—C27	1.399 (8)
O13—C3	1.259 (6)	C27—C28	1.373 (9)
O14—C3	1.249 (6)	C27—H27A	0.95
O1W—H1WA	0.80 (8)	C28—C29	1.397 (8)
O1W—H1WB	0.82 (8)	C28—H28A	0.95
N1—C15	1.328 (7)	C29—H29A	0.95
N1—C11	1.334 (7)	C31—C32	1.389 (10)
N2—C110	1.331 (7)	C31—H31A	0.95
N2—C19	1.346 (7)	C32—C33	1.374 (10)
N2—H2	0.884 (19)	C32—H32A	0.95
N3—C21	1.323 (8)	C33—C34	1.371 (9)
N3—C25	1.345 (7)	C33—H33A	0.95
N4—C29	1.325 (7)	C34—C35	1.382 (9)
N4—C210	1.337 (8)	C34—H34A	0.95
N4—H4	0.88 (2)	C35—C36	1.487 (8)
N5—C31	1.338 (8)	C36—C310	1.382 (8)
N5—C35	1.341 (7)	C36—C37	1.386 (8)
N6—C310	1.332 (7)	C37—C38	1.378 (8)
N6—C39	1.353 (7)	C37—H37A	0.95
C1—C2	1.503 (7)	C38—C39	1.392 (9)
C2—H2A	0.98	C38—H38A	0.95
C2—H2B	0.98	C39—H39A	0.95
C2—H2C	0.98	C110—H11B	0.95
C3—C4	1.507 (7)	C210—H21B	0.95
C4—H4A	0.98	C310—H31B	0.95
O2—U1—O1	176.55 (18)	U3—O9—U2^ii	105.47 (12)
O2—U1—O7	91.07 (16)	U3—O9—U1^ii	131.40 (16)
O1—U1—O7	92.33 (16)	U2^ii—O9—U1^ii	100.88 (12)
O2—U1—O12^i	88.17 (16)	U2—O10—U3^i	105.52 (14)
O1—U1—O12^i	89.45 (17)	U2—O10—U1^i	132.80 (16)
O7—U1—O12^i	143.20 (13)	U3^i—O10—U1^i	101.05 (13)
O2—U1—O13	89.03 (17)	U2—O10—H10	116 (5)
O1—U1—O13	87.94 (17)	U3^i—O10—H10	90 (5)
O7—U1—O13	141.54 (13)	U1^i—O10—H10	103 (5)
O12^i—U1—O13	75.25 (13)	C1—O11—U3	143.5 (3)
O2—U1—O9^i	90.50 (15)	C1—O12—U1^ii	145.0 (4)
O1—U1—O9^i	91.26 (15)	C3—O13—U1	146.4 (4)
O7—U1—O9^i	68.88 (12)	C3—O14—U2^ii	143.6 (4)
O12^i—U1—O9^i	74.34 (12)	H1WA—O1W—H1WB	101 (7)
O13—U1—O9^i	149.58 (12)	C15—N1—C11	117.1 (5)
O2—U1—O10^ii	92.94 (15)	C110—N2—C19	121.0 (5)
O1—U1—O10^ii	87.78 (15)	C110—N2—H2	112 (4)
O7—U1—O10^ii	68.26 (12)	C19—N2—H2	127 (4)
O12^i—U1—O10^ii	148.53 (13)	C21—N3—C25	117.7 (6)
O13—U1—O10^ii	73.33 (12)	C29—N4—C210	118.1 (5)
O9^i—U1—O10^ii	137.05 (11)	C29—N4—H4	130 (4)
O2—U1—U2	96.34 (13)	C210—N4—H4	111 (4)
O1—U1—U2	86.89 (13)	C31—N5—C35	117.8 (6)
O7—U1—U2	30.24 (9)	C310—N6—C39	117.7 (5)
O12^i—U1—U2	113.40 (9)	O11—C1—O12	124.2 (5)
O13—U1—U2	169.86 (10)	O11—C1—C2	116.8 (5)
O9^i—U1—U2	39.38 (8)	O12—C1—C2	119.0 (5)
O10^ii—U1—U2	97.75 (8)	C1—C2—H2A	109.5
O2—U1—U3	88.76 (12)	C1—C2—H2B	109.5
O1—U1—U3	93.91 (12)	H2A—C2—H2B	109.5
O7—U1—U3	29.50 (9)	C1—C2—H2C	109.5
O12^i—U1—U3	172.00 (10)	H2A—C2—H2C	109.5
O13—U1—U3	112.09 (9)	H2B—C2—H2C	109.5
O9^i—U1—U3	98.30 (8)	O14—C3—O13	124.2 (5)
O10^ii—U1—U3	39.08 (8)	O14—C3—C4	118.1 (5)
U2—U1—U3	59.641 (7)	O13—C3—C4	117.6 (5)
O3—U2—O4	175.88 (18)	C3—C4—H4A	109.5
O3—U2—O7	88.95 (16)	C3—C4—H4B	109.5
O4—U2—O7	94.57 (16)	H4A—C4—H4B	109.5
O3—U2—O14^i	87.71 (17)	C3—C4—H4C	109.5
O4—U2—O14^i	88.20 (16)	H4A—C4—H4C	109.5
O7—U2—O14^i	141.65 (13)	H4B—C4—H4C	109.5
O3—U2—O10	84.77 (15)	N1—C11—C12	124.0 (6)
O4—U2—O10	93.97 (16)	N1—C11—H11A	118.0
O7—U2—O10	138.55 (12)	C12—C11—H11A	118.0
O14^i—U2—O10	79.08 (13)	C11—C12—C13	118.1 (6)
O3—U2—O8	88.29 (15)	C11—C12—H12A	120.9
O4—U2—O8	90.96 (15)	C13—C12—H12A	120.9
O7—U2—O8	69.10 (13)	C14—C13—C12	118.0 (6)
O14^i—U2—O8	72.61 (13)	C14—C13—H13A	121.0
O10—U2—O8	151.08 (12)	C12—C13—H13A	121.0
O3—U2—O9^i	95.01 (15)	C15—C14—C13	119.2 (6)
O4—U2—O9^i	88.26 (14)	C15—C14—H14A	120.4
O7—U2—O9^i	69.24 (12)	C13—C14—H14A	120.4
O14^i—U2—O9^i	149.11 (12)	N1—C15—C14	123.5 (5)
O10—U2—O9^i	70.58 (12)	N1—C15—C16	115.2 (5)
O8—U2—O9^i	138.13 (12)	C14—C15—C16	121.3 (5)
O3—U2—U1	86.59 (13)	C110—C16—C17	118.4 (5)
O4—U2—U1	97.53 (12)	C110—C16—C15	118.6 (5)
O7—U2—U1	30.23 (9)	C17—C16—C15	123.0 (5)
O14^i—U2—U1	170.14 (10)	C18—C17—C16	118.6 (5)
O10—U2—U1	108.37 (9)	C18—C17—H17A	120.7
O8—U2—U1	99.16 (9)	C16—C17—H17A	120.7
O9^i—U2—U1	39.75 (8)	C19—C18—C17	120.4 (5)
O3—U2—U3	88.45 (12)	C19—C18—H18A	119.8
O4—U2—U3	93.49 (12)	C17—C18—H18A	119.8
O7—U2—U3	30.60 (9)	N2—C19—C18	119.6 (5)
O14^i—U2—U3	111.09 (9)	N2—C19—H19A	120.2
O10—U2—U3	167.58 (9)	C18—C19—H19A	120.2
O8—U2—U3	38.50 (9)	N3—C21—C22	123.7 (7)
O9^i—U2—U3	99.75 (8)	N3—C21—H21A	118.1
U1—U2—U3	60.733 (6)	C22—C21—H21A	118.1
O3—U2—U3^i	76.91 (12)	C23—C22—C21	118.2 (7)
O4—U2—U3^i	104.47 (12)	C23—C22—H22A	120.9
O7—U2—U3^i	100.78 (9)	C21—C22—H22A	120.9
O14^i—U2—U3^i	115.54 (10)	C22—C23—C24	118.3 (6)
O10—U2—U3^i	37.95 (9)	C22—C23—H23A	120.9
O8—U2—U3^i	162.42 (9)	C24—C23—H23A	120.9
O9^i—U2—U3^i	36.81 (8)	C25—C24—C23	119.9 (6)
U1—U2—U3^i	70.880 (8)	C25—C24—H24A	120.1
U3—U2—U3^i	130.122 (7)	C23—C24—H24A	120.1
O6—U3—O5	176.24 (16)	N3—C25—C24	122.3 (6)
O6—U3—O7	88.60 (15)	N3—C25—C26	115.9 (5)
O5—U3—O7	94.32 (15)	C24—C25—C26	121.6 (6)
O6—U3—O11	87.86 (15)	C210—C26—C27	117.5 (6)
O5—U3—O11	88.39 (15)	C210—C26—C25	120.7 (5)
O7—U3—O11	143.74 (13)	C27—C26—C25	121.6 (5)
O6—U3—O9	86.48 (15)	C28—C27—C26	118.8 (6)
O5—U3—O9	92.94 (15)	C28—C27—H27A	120.6
O7—U3—O9	137.44 (12)	C26—C27—H27A	120.6
O11—U3—O9	78.29 (12)	C27—C28—C29	119.4 (6)
O6—U3—O8	93.59 (15)	C27—C28—H28A	120.3
O5—U3—O8	85.29 (15)	C29—C28—H28A	120.3
O7—U3—O8	68.58 (12)	N4—C29—C28	122.2 (6)
O11—U3—O8	75.64 (12)	N4—C29—H29A	118.9
O9—U3—O8	153.91 (12)	C28—C29—H29A	118.9
O6—U3—O10^ii	98.20 (15)	N5—C31—C32	122.7 (7)
O5—U3—O10^ii	85.08 (15)	N5—C31—H31A	118.6
O7—U3—O10^ii	68.85 (12)	C32—C31—H31A	118.6
O11—U3—O10^ii	147.28 (13)	C33—C32—C31	118.9 (7)
O9—U3—O10^ii	70.10 (12)	C33—C32—H32A	120.5
O8—U3—O10^ii	135.36 (12)	C31—C32—H32A	120.5
O6—U3—U2	90.94 (12)	C34—C33—C32	118.5 (7)
O5—U3—U2	90.39 (12)	C34—C33—H33A	120.8
O7—U3—U2	30.42 (9)	C32—C33—H33A	120.8
O11—U3—U2	113.59 (9)	C33—C34—C35	119.8 (7)
O9—U3—U2	167.77 (8)	C33—C34—H34A	120.1
O8—U3—U2	38.17 (8)	C35—C34—H34A	120.1
O10^ii—U3—U2	98.50 (8)	N5—C35—C34	122.2 (6)
O6—U3—U1	89.81 (12)	N5—C35—C36	116.1 (6)
O5—U3—U1	93.89 (12)	C34—C35—C36	121.7 (6)
O7—U3—U1	29.31 (9)	C310—C36—C37	117.7 (6)
O11—U3—U1	172.81 (10)	C310—C36—C35	120.3 (5)
O9—U3—U1	108.37 (8)	C37—C36—C35	122.0 (6)
O8—U3—U1	97.72 (8)	C38—C37—C36	119.8 (6)
O10^ii—U3—U1	39.87 (8)	C38—C37—H37A	120.1
U2—U3—U1	59.626 (6)	C36—C37—H37A	120.1
O6—U3—U2^ii	80.07 (12)	C37—C38—C39	118.7 (6)
O5—U3—U2^ii	101.72 (12)	C37—C38—H38A	120.6
O7—U3—U2^ii	99.84 (9)	C39—C38—H38A	120.6
O11—U3—U2^ii	115.01 (9)	N6—C39—C38	122.1 (6)
O9—U3—U2^ii	37.72 (8)	N6—C39—H39A	119.0
O8—U3—U2^ii	167.10 (8)	C38—C39—H39A	119.0
O10^ii—U3—U2^ii	36.53 (8)	N2—C110—C16	122.0 (5)
U2—U3—U2^ii	130.049 (7)	N2—C110—H11B	119.0
U1—U3—U2^ii	71.218 (8)	C16—C110—H11B	119.0
U1—O7—U2	119.53 (16)	N4—C210—C26	123.9 (5)
U1—O7—U3	121.19 (15)	N4—C210—H21B	118.0
U2—O7—U3	118.98 (15)	C26—C210—H21B	118.0
U2—O8—U3	103.33 (13)	N6—C310—C36	124.0 (6)
U2—O8—H8	113 (5)	N6—C310—H31B	118.0
U3—O8—H8	113 (5)	C36—C310—H31B	118.0
U3—O11—C1—O12	17.9 (11)	C24—C25—C26—C210	−17.8 (9)
U3—O11—C1—C2	−163.6 (4)	N3—C25—C26—C27	−18.6 (8)
U1^ii—O12—C1—O11	−35.4 (11)	C24—C25—C26—C27	156.5 (6)
U1^ii—O12—C1—C2	146.1 (5)	C210—C26—C27—C28	0.2 (8)
U2^ii—O14—C3—O13	3.3 (11)	C25—C26—C27—C28	−174.3 (5)
U2^ii—O14—C3—C4	−179.1 (5)	C26—C27—C28—C29	2.1 (8)
U1—O13—C3—O14	−32.1 (11)	C210—N4—C29—C28	0.6 (8)
U1—O13—C3—C4	150.3 (5)	C27—C28—C29—N4	−2.6 (9)
C15—N1—C11—C12	−1.8 (10)	C35—N5—C31—C32	0.1 (9)
N1—C11—C12—C13	1.4 (10)	N5—C31—C32—C33	1.1 (11)
C11—C12—C13—C14	−0.4 (9)	C31—C32—C33—C34	−1.9 (11)
C12—C13—C14—C15	−0.1 (8)	C32—C33—C34—C35	1.7 (11)
C11—N1—C15—C14	1.2 (9)	C31—N5—C35—C34	−0.3 (9)
C11—N1—C15—C16	−179.5 (5)	C31—N5—C35—C36	−179.2 (5)
C13—C14—C15—N1	−0.3 (9)	C33—C34—C35—N5	−0.6 (10)
C13—C14—C15—C16	−179.5 (5)	C33—C34—C35—C36	178.2 (6)
N1—C15—C16—C110	−22.9 (8)	N5—C35—C36—C310	−148.6 (6)
C14—C15—C16—C110	156.4 (6)	C34—C35—C36—C310	32.5 (9)
N1—C15—C16—C17	157.9 (6)	N5—C35—C36—C37	31.1 (8)
C14—C15—C16—C17	−22.8 (8)	C34—C35—C36—C37	−147.8 (6)
C110—C16—C17—C18	0.8 (9)	C310—C36—C37—C38	−1.4 (9)
C15—C16—C17—C18	−180.0 (6)	C35—C36—C37—C38	178.9 (6)
C16—C17—C18—C19	−1.1 (9)	C36—C37—C38—C39	−0.3 (10)
C110—N2—C19—C18	−1.0 (9)	C310—N6—C39—C38	−1.6 (9)
C17—C18—C19—N2	1.2 (10)	C37—C38—C39—N6	1.9 (10)
C25—N3—C21—C22	−0.9 (10)	C19—N2—C110—C16	0.8 (9)
N3—C21—C22—C23	0.7 (11)	C17—C16—C110—N2	−0.7 (9)
C21—C22—C23—C24	0.3 (10)	C15—C16—C110—N2	−179.9 (5)
C22—C23—C24—C25	−1.0 (9)	C29—N4—C210—C26	1.9 (8)
C21—N3—C25—C24	0.3 (9)	C27—C26—C210—N4	−2.2 (9)
C21—N3—C25—C26	175.3 (6)	C25—C26—C210—N4	172.2 (5)
C23—C24—C25—N3	0.7 (9)	C39—N6—C310—C36	−0.2 (9)
C23—C24—C25—C26	−174.1 (5)	C37—C36—C310—N6	1.7 (9)
N3—C25—C26—C210	167.1 (5)	C35—C36—C310—N6	−178.5 (6)

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···N6	0.84 (2)	1.92 (2)	2.751 (6)	176 (7)
O10—H10···O1W^i	0.84 (2)	2.04 (3)	2.829 (6)	158 (7)
O1W—H1WA···O1	0.80 (8)	2.24 (8)	2.924 (7)	144 (7)
O1W—H1WB···N5^iii	0.82 (8)	2.05 (8)	2.856 (8)	167 (8)
N2—H2···O8	0.88 (2)	1.66 (2)	2.546 (6)	178 (6)
N4—H4···O9	0.88 (2)	1.91 (2)	2.790 (6)	173 (6)
C2—H2C···N1	0.98	2.57	3.351 (8)	137
C14—H14A···O3^iv	0.95	2.49	3.045 (7)	117
C22—H22A···O13^v	0.95	2.55	3.401 (9)	149
C110—H11B···O11	0.95	2.37	3.246 (7)	154
C210—H21B···O4^ii	0.95	2.34	3.153 (7)	143
C310—H31B···O6	0.95	2.6	3.373 (7)	139

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) −x+3/2, y−1/2, −z+3/2; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x+1/2, y−1/2, −z+3/2.

Bis(acetato-κ²O,O')(2,4'-bipyridine-\ κN^1')dioxidouranium(VI) (III_AW2913U)

Crystal data

[U(C2H3O2)2O2(C10H8N2)2]	Z = 1
Mr = 700.48	F(000) = 334
Triclinic, P1	Dx = 1.983 Mg m^−3
a = 8.006 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.786 (3) Å	Cell parameters from 4878 reflections
c = 8.833 (3) Å	θ = 2.4–30.4°
α = 78.274 (5)°	µ = 6.97 mm^−1
β = 84.648 (5)°	T = 125 K
γ = 74.814 (5)°	Block, yellow
V = 586.6 (3) Å^3	0.24 × 0.14 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer	2260 independent reflections
Radiation source: sealed X-ray tube, Bruker APEXII CCD	2260 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 8.3333 pixels mm^-1	θmax = 26.0°, θmin = 2.4°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS: Bruker, 2013)	k = −10→10
Tmin = 0.35, Tmax = 0.72	l = −10→10
5760 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0285P)^2 + 1.9118P] where P = (Fo^2 + 2Fc^2)/3
2260 reflections	(Δ/σ)max < 0.001
161 parameters	Δρmax = 2.26 e Å^−3
0 restraints	Δρmin = −2.63 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
U	0.5	1.0	1.0	0.01498 (9)
O1	0.4374 (4)	0.8416 (4)	1.1328 (4)	0.0198 (7)
O2	0.2843 (4)	1.0027 (4)	0.8178 (4)	0.0227 (7)
O3	0.1923 (4)	1.1542 (4)	0.9917 (4)	0.0221 (7)
N1	0.6000 (5)	0.8068 (5)	0.8079 (4)	0.0187 (8)
N2	0.8256 (6)	0.5594 (5)	0.3423 (5)	0.0290 (10)
C1	0.6095 (7)	0.6487 (6)	0.8490 (6)	0.0236 (10)
H1B	0.583062	0.607259	0.953926	0.028*
C2	0.6562 (6)	0.5428 (6)	0.7457 (5)	0.0224 (10)
H2B	0.659233	0.432421	0.779693	0.027*
C3	0.6984 (6)	0.6006 (6)	0.5916 (5)	0.0200 (10)
C4	0.6895 (7)	0.7641 (6)	0.5494 (5)	0.0241 (10)
H4A	0.717602	0.808646	0.445814	0.029*
C5	0.6392 (7)	0.8616 (6)	0.6595 (6)	0.0248 (11)
H5A	0.63225	0.973022	0.627986	0.03*
C6	0.7506 (6)	0.4952 (6)	0.4732 (5)	0.0206 (10)
C7	0.7236 (6)	0.3413 (6)	0.4985 (5)	0.0217 (10)
H7A	0.668701	0.299732	0.592049	0.026*
C8	0.7791 (7)	0.2502 (6)	0.3832 (6)	0.0270 (11)
H8A	0.762534	0.144998	0.396903	0.032*
C9	0.8583 (7)	0.3141 (7)	0.2489 (6)	0.0289 (12)
H9A	0.898205	0.253572	0.169094	0.035*
C10	0.8782 (8)	0.4680 (7)	0.2330 (6)	0.0328 (13)
H10A	0.931921	0.511925	0.139886	0.039*
C11	0.1621 (6)	1.0998 (6)	0.8776 (5)	0.0204 (10)
C12	−0.0147 (6)	1.1491 (6)	0.8128 (6)	0.0251 (11)
H12A	−0.039326	1.0575	0.779774	0.038*
H12B	−0.019017	1.237007	0.723752	0.038*
H12C	−0.101419	1.185014	0.892399	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U	0.01675 (14)	0.01482 (13)	0.01439 (13)	−0.00319 (9)	0.00165 (8)	−0.00708 (9)
O1	0.0232 (17)	0.0156 (16)	0.0225 (16)	−0.0071 (14)	0.0003 (13)	−0.0054 (14)
O2	0.0210 (17)	0.0253 (18)	0.0235 (17)	−0.0023 (14)	−0.0008 (13)	−0.0131 (15)
O3	0.0218 (18)	0.0241 (18)	0.0202 (16)	−0.0015 (14)	−0.0009 (13)	−0.0095 (14)
N1	0.022 (2)	0.019 (2)	0.0161 (18)	−0.0036 (16)	−0.0005 (15)	−0.0079 (16)
N2	0.039 (3)	0.026 (2)	0.024 (2)	−0.009 (2)	0.0061 (19)	−0.0126 (19)
C1	0.028 (3)	0.022 (3)	0.020 (2)	−0.002 (2)	−0.0004 (19)	−0.009 (2)
C2	0.026 (3)	0.017 (2)	0.023 (2)	0.000 (2)	−0.0009 (19)	−0.009 (2)
C3	0.019 (2)	0.021 (2)	0.022 (2)	−0.0038 (19)	−0.0003 (18)	−0.010 (2)
C4	0.034 (3)	0.023 (3)	0.018 (2)	−0.010 (2)	0.004 (2)	−0.007 (2)
C5	0.031 (3)	0.020 (3)	0.025 (2)	−0.006 (2)	0.001 (2)	−0.008 (2)
C6	0.020 (2)	0.022 (2)	0.020 (2)	−0.0031 (19)	−0.0006 (18)	−0.009 (2)
C7	0.026 (3)	0.024 (3)	0.018 (2)	−0.008 (2)	−0.0012 (18)	−0.006 (2)
C8	0.032 (3)	0.022 (3)	0.029 (3)	−0.004 (2)	−0.002 (2)	−0.013 (2)
C9	0.032 (3)	0.030 (3)	0.027 (3)	−0.004 (2)	0.003 (2)	−0.019 (2)
C10	0.042 (3)	0.034 (3)	0.024 (3)	−0.008 (3)	0.008 (2)	−0.016 (2)
C11	0.021 (2)	0.020 (2)	0.021 (2)	−0.008 (2)	−0.0013 (18)	−0.004 (2)
C12	0.021 (3)	0.025 (3)	0.029 (3)	−0.002 (2)	−0.006 (2)	−0.006 (2)

Geometric parameters (Å, º)

U—O1^i	1.777 (3)	C2—H2B	0.95
U—O1	1.777 (3)	C3—C4	1.394 (7)
U—O2	2.461 (3)	C3—C6	1.495 (6)
U—O2^i	2.461 (3)	C4—C5	1.388 (6)
U—O3^i	2.481 (3)	C4—H4A	0.95
U—O3	2.481 (3)	C5—H5A	0.95
U—N1	2.571 (4)	C6—C7	1.396 (7)
U—N1^i	2.571 (4)	C7—C8	1.391 (6)
U—C11^i	2.859 (5)	C7—H7A	0.95
U—C11	2.859 (5)	C8—C9	1.378 (8)
O2—C11	1.270 (6)	C8—H8A	0.95
O3—C11	1.267 (5)	C9—C10	1.381 (8)
N1—C5	1.339 (6)	C9—H9A	0.95
N1—C1	1.347 (6)	C10—H10A	0.95
N2—C6	1.341 (7)	C11—C12	1.500 (7)
N2—C10	1.348 (6)	C12—H12A	0.98
C1—C2	1.392 (6)	C12—H12B	0.98
C1—H1B	0.95	C12—H12C	0.98
C2—C3	1.396 (7)
O1^i—U—O1	180.0	C5—N1—C1	117.0 (4)
O1^i—U—O2	88.92 (13)	C5—N1—U	120.7 (3)
O1—U—O2	91.08 (13)	C1—N1—U	122.2 (3)
O1^i—U—O2^i	91.08 (13)	C6—N2—C10	117.4 (5)
O1—U—O2^i	88.92 (13)	N1—C1—C2	123.3 (5)
O2—U—O2^i	180.0	N1—C1—H1B	118.3
O1^i—U—O3^i	89.22 (14)	C2—C1—H1B	118.3
O1—U—O3^i	90.78 (14)	C1—C2—C3	119.3 (5)
O2—U—O3^i	127.48 (10)	C1—C2—H2B	120.3
O2^i—U—O3^i	52.52 (10)	C3—C2—H2B	120.3
O1^i—U—O3	90.78 (14)	C4—C3—C2	117.3 (4)
O1—U—O3	89.22 (14)	C4—C3—C6	119.9 (4)
O2—U—O3	52.52 (10)	C2—C3—C6	122.8 (4)
O2^i—U—O3	127.48 (10)	C5—C4—C3	119.6 (5)
O3^i—U—O3	180.0	C5—C4—H4A	120.2
O1^i—U—N1	91.78 (13)	C3—C4—H4A	120.2
O1—U—N1	88.22 (13)	N1—C5—C4	123.5 (5)
O2—U—N1	63.91 (11)	N1—C5—H5A	118.3
O2^i—U—N1	116.09 (11)	C4—C5—H5A	118.3
O3^i—U—N1	63.70 (11)	N2—C6—C7	122.9 (4)
O3—U—N1	116.30 (11)	N2—C6—C3	115.0 (4)
O1^i—U—N1^i	88.22 (13)	C7—C6—C3	122.1 (4)
O1—U—N1^i	91.78 (13)	C8—C7—C6	118.3 (5)
O2—U—N1^i	116.10 (11)	C8—C7—H7A	120.9
O2^i—U—N1^i	63.90 (11)	C6—C7—H7A	120.9
O3^i—U—N1^i	116.30 (11)	C9—C8—C7	119.4 (5)
O3—U—N1^i	63.70 (11)	C9—C8—H8A	120.3
N1—U—N1^i	180.0	C7—C8—H8A	120.3
O1^i—U—C11^i	89.91 (15)	C8—C9—C10	118.4 (4)
O1—U—C11^i	90.09 (14)	C8—C9—H9A	120.8
O2—U—C11^i	153.71 (12)	C10—C9—H9A	120.8
O2^i—U—C11^i	26.29 (12)	N2—C10—C9	123.6 (5)
O3^i—U—C11^i	26.23 (12)	N2—C10—H10A	118.2
O3—U—C11^i	153.77 (12)	C9—C10—H10A	118.2
N1—U—C11^i	89.89 (13)	O3—C11—O2	119.1 (4)
N1^i—U—C11^i	90.11 (13)	O3—C11—C12	120.9 (4)
O1^i—U—C11	90.09 (14)	O2—C11—C12	120.0 (4)
O1—U—C11	89.91 (15)	O3—C11—U	60.0 (2)
O2—U—C11	26.29 (12)	O2—C11—U	59.1 (2)
O2^i—U—C11	153.71 (12)	C12—C11—U	179.0 (3)
O3^i—U—C11	153.77 (12)	C11—C12—H12A	109.5
O3—U—C11	26.23 (12)	C11—C12—H12B	109.5
N1—U—C11	90.11 (13)	H12A—C12—H12B	109.5
N1^i—U—C11	89.89 (13)	C11—C12—H12C	109.5
C11^i—U—C11	180.0 (3)	H12A—C12—H12C	109.5
C11—O2—U	94.6 (3)	H12B—C12—H12C	109.5
C11—O3—U	93.8 (3)
C5—N1—C1—C2	−0.5 (7)	C2—C3—C6—N2	−164.8 (5)
U—N1—C1—C2	177.2 (4)	C4—C3—C6—C7	−164.8 (5)
N1—C1—C2—C3	1.1 (8)	C2—C3—C6—C7	14.8 (7)
C1—C2—C3—C4	−0.6 (7)	N2—C6—C7—C8	0.8 (7)
C1—C2—C3—C6	179.7 (4)	C3—C6—C7—C8	−178.8 (4)
C2—C3—C4—C5	−0.3 (7)	C6—C7—C8—C9	0.0 (7)
C6—C3—C4—C5	179.4 (5)	C7—C8—C9—C10	−0.6 (8)
C1—N1—C5—C4	−0.6 (7)	C6—N2—C10—C9	0.2 (8)
U—N1—C5—C4	−178.2 (4)	C8—C9—C10—N2	0.5 (9)
C3—C4—C5—N1	0.9 (8)	U—O3—C11—O2	−1.0 (5)
C10—N2—C6—C7	−0.9 (8)	U—O3—C11—C12	179.3 (4)
C10—N2—C6—C3	178.7 (5)	U—O2—C11—O3	1.0 (5)
C4—C3—C6—N2	15.5 (7)	U—O2—C11—C12	−179.3 (4)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O2^ii	0.95	2.57	3.487 (6)	163
C12—H12B···N2^ii	0.98	2.61	3.309 (7)	129

Symmetry code: (ii) −x+1, −y+2, −z+1.