Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113014832/fa3320sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113014832/fa3320Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113014832/fa3320Isup4.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113014832/fa3320IIsup3.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113014832/fa3320IIsup5.mol |
CCDC references: 956984; 956985
UO2(NO3)2.6H2O (0.2 mmol), valeric acid (0.6 mmol) and NaOH (0.6 mmol) were dissolved in water (6 ml). Yellow prismatic crystals of (I) formed upon isothermal evaporation of the reaction mixture. The same procedure with KOH instead of NaOH afforded plate-like crystals of (II). It is noteworthy that, under the conditions described, Na+, in contrast with K+, did not enter into the structure. Absorption bands in the FT–IR spectra of (I) and (II) correspond to vibrations of the UO22+ and C4H9COO- ions, and for (I) to H2O molecules. Full assignment of absorption bands was made according to Moita et al. (1994) and is provided as Supplementary materials.
Refinement of (I) using the space group C2 gave large correlations and an absolute structure parameter of 0.38 (8) (Flack, 1983), and moreover gave the same disordered structural model as was found when the space group C2/m was used. The final refinement used C2/m, which did not produce a correlation problem. The uranyl O atoms and the valerate unit are disordered over two sites across the mirror plane. In (II), three of the seven independent carboxylate anions are disordered, each over two sites with equal occupancies. One of these was refined isotropically (C1–C5A,B). The lengths of 24 C—C bonds and nine 1,3-distances in (II) were restrained. A common set of anisotropic displacement parameters was refined for the last four C atoms of each valerate ligand. In addition, restraints to isotropic behaviour were applied to the anisotropic displacement parameters of two O and four C atoms. H atoms were placed in calculated positions and refined as riding, with C—H = 0.96, 0.98 or 0.99 Å and O—H = 0.85 Å [Please check added text], and with Uiso(H) = 1.5Ueq(C,O) for methyl groups and water molecules or 1.2Ueq(C) for other C atoms. Calculations of coordination sequences and noncovalent interactions were carried out with the program package TOPOS (Blatov, 2012).
For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[U(C5H9O2)2O2(H2O)2] | F(000) = 476 |
Mr = 508.31 | Dx = 2.185 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 125 reflections |
a = 7.782 (4) Å | θ = 2.5–26.8° |
b = 10.802 (5) Å | µ = 10.53 mm−1 |
c = 9.512 (5) Å | T = 100 K |
β = 104.885 (9)° | Prism, yellow |
V = 772.7 (7) Å3 | 0.21 × 0.11 × 0.08 mm |
Z = 2 |
Bruker APEXII CCD area-detector diffractometer | 1187 independent reflections |
Radiation source: fine-focus sealed tube | 1187 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
ω scans | θmax = 30.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −10→10 |
Tmin = 0.261, Tmax = 0.430 | k = −15→15 |
4876 measured reflections | l = −13→13 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.025P)2] where P = (Fo2 + 2Fc2)/3 |
1187 reflections | (Δ/σ)max < 0.001 |
85 parameters | Δρmax = 2.06 e Å−3 |
0 restraints | Δρmin = −2.05 e Å−3 |
[U(C5H9O2)2O2(H2O)2] | V = 772.7 (7) Å3 |
Mr = 508.31 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 7.782 (4) Å | µ = 10.53 mm−1 |
b = 10.802 (5) Å | T = 100 K |
c = 9.512 (5) Å | 0.21 × 0.11 × 0.08 mm |
β = 104.885 (9)° |
Bruker APEXII CCD area-detector diffractometer | 1187 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 1187 reflections with I > 2σ(I) |
Tmin = 0.261, Tmax = 0.430 | Rint = 0.068 |
4876 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.059 | H-atom parameters constrained |
S = 1.00 | Δρmax = 2.06 e Å−3 |
1187 reflections | Δρmin = −2.05 e Å−3 |
85 parameters |
Experimental. FT–IR spectra were measured using a Perkin–Elmer Spectrum 100 FT–IR spectrometer, using pressed KBr pellets. |
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 | Occ. (<1) | |
U1 | 1.0000 | 0.0000 | 1.0000 | 0.00883 (9) | |
O1 | 1.0000 | 0.2248 (5) | 1.0000 | 0.0481 (18) | |
H1 | 1.0628 | 0.2782 | 0.9704 | 0.072* | |
O2 | 1.0290 (12) | 0.0000 | 0.8233 (10) | 0.026 (2) | 0.5 |
O3 | 1.1439 (13) | 0.0000 | 1.1743 (11) | 0.042 (3) | 0.5 |
O4 | 0.7057 (7) | −0.1000 (6) | 0.9038 (7) | 0.0189 (12) | 0.5 |
O5 | 1.2305 (8) | 0.0995 (6) | 0.8998 (8) | 0.0209 (13) | 0.5 |
C1 | 0.6208 (15) | 0.0000 | 0.8634 (12) | 0.013 (2) | 0.5 |
C2 | 0.4305 (8) | 0.0000 | 0.7720 (7) | 0.0239 (13) | |
H2 | 0.3507 | 0.0095 | 0.8333 | 0.029* | 0.5 |
H3 | 0.4048 | −0.0775 | 0.7215 | 0.029* | 0.5 |
C3 | 0.4012 (14) | 0.1116 (9) | 0.6565 (10) | 0.0246 (19) | 0.5 |
H4 | 0.4099 | 0.1916 | 0.7087 | 0.029* | 0.5 |
H5 | 0.4960 | 0.1095 | 0.6043 | 0.029* | 0.5 |
C4 | 0.2191 (14) | 0.1023 (10) | 0.5463 (11) | 0.028 (2) | 0.5 |
H6 | 0.2084 | 0.0203 | 0.4985 | 0.033* | 0.5 |
H7 | 0.1247 | 0.1086 | 0.5986 | 0.033* | 0.5 |
C5 | 0.1909 (16) | 0.2019 (11) | 0.4314 (12) | 0.033 (2) | 0.5 |
H8 | 0.0756 | 0.1920 | 0.3654 | 0.050* | 0.5 |
H9 | 0.1985 | 0.2817 | 0.4769 | 0.050* | 0.5 |
H10 | 0.2806 | 0.1952 | 0.3788 | 0.050* | 0.5 |
C6 | 1.2869 (14) | 0.0000 | 0.8611 (13) | 0.014 (2) | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.00675 (13) | 0.00607 (13) | 0.01403 (15) | 0.000 | 0.00333 (10) | 0.000 |
O1 | 0.033 (3) | 0.009 (2) | 0.115 (6) | 0.000 | 0.043 (3) | 0.000 |
O2 | 0.020 (4) | 0.043 (6) | 0.016 (4) | 0.000 | 0.009 (4) | 0.000 |
O3 | 0.016 (5) | 0.097 (11) | 0.018 (5) | 0.000 | 0.010 (4) | 0.000 |
O4 | 0.009 (3) | 0.011 (3) | 0.035 (4) | −0.001 (2) | 0.003 (2) | −0.001 (2) |
O5 | 0.017 (3) | 0.009 (3) | 0.039 (4) | 0.003 (2) | 0.013 (3) | 0.004 (2) |
C1 | 0.017 (5) | 0.011 (5) | 0.014 (5) | 0.000 | 0.011 (4) | 0.000 |
C2 | 0.014 (3) | 0.034 (4) | 0.023 (3) | 0.000 | 0.002 (2) | 0.000 |
C3 | 0.032 (5) | 0.022 (4) | 0.020 (4) | −0.006 (4) | 0.006 (4) | 0.002 (4) |
C4 | 0.027 (5) | 0.030 (5) | 0.024 (5) | 0.004 (4) | 0.003 (4) | 0.006 (4) |
C5 | 0.040 (6) | 0.031 (6) | 0.030 (5) | 0.005 (4) | 0.011 (5) | 0.009 (4) |
C6 | 0.007 (4) | 0.021 (6) | 0.015 (5) | 0.000 | 0.005 (4) | 0.000 |
U1—O3 | 1.746 (11) | C1—O4ii | 1.273 (9) |
U1—O3i | 1.746 (11) | C1—C2 | 1.512 (13) |
U1—O2i | 1.752 (9) | C2—C6iv | 1.567 (12) |
U1—O2 | 1.752 (9) | C2—C3ii | 1.608 (10) |
U1—O1i | 2.428 (5) | C2—C3 | 1.608 (10) |
U1—O1 | 2.428 (5) | C2—H2 | 0.9599 |
U1—O5i | 2.482 (6) | C2—H3 | 0.9600 |
U1—O5ii | 2.482 (6) | C3—C4 | 1.534 (14) |
U1—O5iii | 2.482 (6) | C3—H4 | 0.9900 |
U1—O5 | 2.482 (6) | C3—H5 | 0.9900 |
U1—O4 | 2.485 (6) | C4—C5 | 1.508 (14) |
U1—O4i | 2.485 (6) | C4—H6 | 0.9900 |
O1—H1 | 0.8500 | C4—H7 | 0.9900 |
O2—O3i | 1.351 (13) | C5—H8 | 0.9600 |
O3—O2i | 1.351 (13) | C5—H9 | 0.9599 |
O4—C1 | 1.273 (9) | C5—H10 | 0.9601 |
O4—O5i | 1.806 (10) | C6—O5ii | 1.251 (8) |
O5—C6 | 1.251 (8) | C6—C2v | 1.567 (12) |
O5—O4i | 1.806 (10) | ||
O3—U1—O3i | 180 | O5i—U1—O4i | 137.4 (2) |
O3—U1—O2i | 45.4 (4) | O5ii—U1—O4i | 68.9 (2) |
O3i—U1—O2i | 134.6 (4) | O5iii—U1—O4i | 111.1 (2) |
O3—U1—O2 | 134.5 (4) | O5—U1—O4i | 42.6 (2) |
O3i—U1—O2 | 45.4 (4) | O4—U1—O4i | 180 |
O2i—U1—O2 | 180 | U1—O1—H1 | 132.8 |
O3—U1—O1i | 90 | O3i—O2—U1 | 67.0 (6) |
O3i—U1—O1i | 90 | O2i—O3—U1 | 67.5 (6) |
O2i—U1—O1i | 90 | C1—O4—O5i | 107.1 (7) |
O2—U1—O1i | 90 | C1—O4—U1 | 95.8 (5) |
O3—U1—O1 | 90 | O5i—O4—U1 | 68.6 (3) |
O3i—U1—O1 | 90 | C6—O5—O4i | 106.4 (7) |
O2i—U1—O1 | 90 | C6—O5—U1 | 94.8 (5) |
O2—U1—O1 | 90 | O4i—O5—U1 | 68.8 (3) |
O1i—U1—O1 | 180 | O4ii—C1—O4 | 116.1 (11) |
O3—U1—O5i | 89.2 (3) | O4ii—C1—C2 | 122.0 (5) |
O3i—U1—O5i | 90.8 (3) | O4—C1—C2 | 122.0 (5) |
O2i—U1—O5i | 49.3 (3) | O4ii—C1—U1 | 58.4 (5) |
O2—U1—O5i | 130.7 (3) | O4—C1—U1 | 58.4 (5) |
O1i—U1—O5i | 64.34 (14) | C2—C1—U1 | 171.9 (7) |
O1—U1—O5i | 115.66 (14) | C1—C2—C6iv | 114.8 (7) |
O3—U1—O5ii | 90.8 (3) | C1—C2—C3ii | 109.8 (5) |
O3i—U1—O5ii | 89.2 (3) | C6iv—C2—C3ii | 111.9 (5) |
O2i—U1—O5ii | 130.7 (3) | C1—C2—C3 | 109.8 (5) |
O2—U1—O5ii | 49.3 (3) | C6iv—C2—C3 | 111.9 (5) |
O1i—U1—O5ii | 64.34 (14) | C3ii—C2—C3 | 97.2 (8) |
O1—U1—O5ii | 115.66 (14) | C1—C2—H2 | 110.0 |
O5i—U1—O5ii | 128.7 (3) | C3ii—C2—H2 | 119.6 |
O3—U1—O5iii | 89.2 (3) | C3—C2—H2 | 109.5 |
O3i—U1—O5iii | 90.8 (3) | C1—C2—H3 | 109.6 |
O2i—U1—O5iii | 49.3 (3) | C6iv—C2—H3 | 100.6 |
O2—U1—O5iii | 130.7 (3) | C3—C2—H3 | 109.7 |
O1i—U1—O5iii | 115.66 (14) | H2—C2—H3 | 108.2 |
O1—U1—O5iii | 64.34 (14) | C4—C3—C2 | 111.2 (7) |
O5i—U1—O5iii | 51.3 (3) | C4—C3—H4 | 109.4 |
O5ii—U1—O5iii | 180 | C2—C3—H4 | 109.4 |
O3—U1—O5 | 90.8 (3) | C4—C3—H5 | 109.4 |
O3i—U1—O5 | 89.2 (3) | C2—C3—H5 | 109.4 |
O2i—U1—O5 | 130.7 (3) | H4—C3—H5 | 108.0 |
O2—U1—O5 | 49.3 (3) | C5—C4—C3 | 112.7 (9) |
O1i—U1—O5 | 115.66 (14) | C5—C4—H6 | 109.1 |
O1—U1—O5 | 64.34 (14) | C3—C4—H6 | 109.1 |
O5i—U1—O5 | 180 | C5—C4—H7 | 109.1 |
O5ii—U1—O5 | 51.3 (3) | C3—C4—H7 | 109.1 |
O5iii—U1—O5 | 128.7 (3) | H6—C4—H7 | 107.8 |
O3—U1—O4 | 131.0 (3) | C4—C5—C5vi | 86.1 (9) |
O3i—U1—O4 | 49.0 (3) | C4—C5—H8 | 109.5 |
O2i—U1—O4 | 91.1 (3) | C5vi—C5—H8 | 141.6 |
O2—U1—O4 | 88.9 (3) | C4—C5—H9 | 109.5 |
O1i—U1—O4 | 64.24 (14) | H8—C5—H9 | 109.5 |
O1—U1—O4 | 115.76 (14) | C4—C5—H10 | 109.5 |
O5i—U1—O4 | 42.6 (2) | C5vi—C5—H10 | 96.9 |
O5ii—U1—O4 | 111.1 (2) | H8—C5—H10 | 109.5 |
O5iii—U1—O4 | 68.9 (2) | H9—C5—H10 | 109.5 |
O5—U1—O4 | 137.3 (2) | O5—C6—O5ii | 118.4 (10) |
O3—U1—O4i | 49.0 (3) | O5—C6—C2v | 120.8 (5) |
O3i—U1—O4i | 131.0 (3) | O5ii—C6—C2v | 120.8 (5) |
O2i—U1—O4i | 88.9 (3) | O5—C6—U1 | 59.5 (5) |
O2—U1—O4i | 91.1 (3) | O5ii—C6—U1 | 59.5 (5) |
O1i—U1—O4i | 115.76 (14) | C2v—C6—U1 | 174.9 (7) |
O1—U1—O4i | 64.24 (14) |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) x, −y, z; (iii) −x+2, y, −z+2; (iv) x−1, y, z; (v) x+1, y, z; (vi) −x+1/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4vii | 0.85 | 1.93 | 2.781 (7) | 180 |
O1—H1···O5viii | 0.85 | 2.20 | 2.808 (8) | 128 |
Symmetry codes: (vii) x+1/2, y+1/2, z; (viii) −x+5/2, −y+1/2, −z+2. |
K[U(C5H9O2)3O2] | F(000) = 4672 |
Mr = 612.50 | Dx = 1.927 Mg m−3 |
Orthorhombic, C2221 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2c 2 | Cell parameters from 1355 reflections |
a = 17.294 (3) Å | θ = 2.6–22.2° |
b = 23.405 (4) Å | µ = 7.92 mm−1 |
c = 20.862 (3) Å | T = 100 K |
V = 8444 (2) Å3 | Plate, yellow |
Z = 16 | 0.24 × 0.15 × 0.03 mm |
Bruker APEXII CCD area-detector diffractometer | 10209 independent reflections |
Radiation source: fine-focus sealed tube | 8322 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.072 |
ω scans | θmax = 28.0°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | h = −18→22 |
Tmin = 0.252, Tmax = 0.797 | k = −30→30 |
37788 measured reflections | l = −27→27 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.193 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.25 | (Δ/σ)max = 0.008 |
10209 reflections | Δρmax = 2.77 e Å−3 |
366 parameters | Δρmin = −1.85 e Å−3 |
63 restraints | Absolute structure: Flack (1983), with 4677 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.061 (16) |
K[U(C5H9O2)3O2] | V = 8444 (2) Å3 |
Mr = 612.50 | Z = 16 |
Orthorhombic, C2221 | Mo Kα radiation |
a = 17.294 (3) Å | µ = 7.92 mm−1 |
b = 23.405 (4) Å | T = 100 K |
c = 20.862 (3) Å | 0.24 × 0.15 × 0.03 mm |
Bruker APEXII CCD area-detector diffractometer | 10209 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1998) | 8322 reflections with I > 2σ(I) |
Tmin = 0.252, Tmax = 0.797 | Rint = 0.072 |
37788 measured reflections |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.193 | Δρmax = 2.77 e Å−3 |
S = 1.25 | Δρmin = −1.85 e Å−3 |
10209 reflections | Absolute structure: Flack (1983), with 4677 Friedel pairs |
366 parameters | Absolute structure parameter: 0.061 (16) |
63 restraints |
Experimental. FT–IR spectra were measured using a Perkin–Elmer Spectrum 100 FT–IR spectrometer, using pressed KBr pellets. |
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 | Occ. (<1) | |
U1 | 0.0000 | 0.10330 (3) | 0.7500 | 0.03262 (18) | |
U2 | 0.32439 (4) | 0.0000 | 1.0000 | 0.0370 (2) | |
U3 | 0.34413 (3) | −0.08589 (3) | 0.67491 (3) | 0.03730 (16) | |
K1 | 0.4201 (3) | 0.0000 | 0.5000 | 0.0403 (10) | |
K2 | 0.0000 | 0.29034 (19) | 0.7500 | 0.0474 (12) | |
K3 | 0.20505 (19) | 0.01060 (15) | 0.81415 (15) | 0.0379 (7) | |
O1 | −0.0331 (9) | 0.1027 (7) | 0.8305 (6) | 0.069 (4) | |
O2 | 0.0726 (9) | 0.1921 (7) | 0.7716 (8) | 0.072 (4) | |
O3 | 0.1384 (8) | 0.1109 (6) | 0.7845 (7) | 0.060 (3) | |
O4 | 0.0563 (8) | 0.0102 (5) | 0.7711 (9) | 0.075 (5) | |
O5 | 0.3244 (7) | 0.0717 (5) | 1.0172 (5) | 0.046 (3) | |
O6 | 0.4421 (6) | 0.0165 (6) | 0.9372 (5) | 0.052 (3) | |
O7 | 0.3337 (7) | 0.0246 (6) | 0.8848 (5) | 0.053 (3) | |
O8 | 0.1958 (6) | 0.0060 (7) | 0.9489 (6) | 0.054 (3) | |
O9 | 0.2687 (7) | −0.1247 (6) | 0.6436 (6) | 0.053 (3) | |
O10 | 0.4212 (7) | −0.0468 (5) | 0.7079 (6) | 0.048 (3) | |
O11 | 0.4406 (10) | −0.1623 (6) | 0.6445 (6) | 0.070 (4) | |
O12 | 0.4146 (6) | −0.0952 (5) | 0.5728 (5) | 0.042 (2) | |
O13 | 0.3180 (7) | −0.0077 (5) | 0.5969 (6) | 0.050 (3) | |
O14 | 0.2630 (7) | −0.0011 (6) | 0.6940 (5) | 0.054 (3) | |
O15 | 0.2761 (7) | −0.0914 (5) | 0.7815 (5) | 0.044 (3) | |
O16 | 0.3585 (7) | −0.1560 (5) | 0.7607 (5) | 0.046 (3) | |
C1 | 0.1340 (17) | 0.1637 (14) | 0.7807 (15) | 0.103 (9)* | |
C2A | 0.170 (3) | 0.2166 (18) | 0.809 (3) | 0.152 (12)* | 0.50 |
H2AA | 0.1439 | 0.2258 | 0.8498 | 0.183* | 0.50 |
H2AB | 0.1616 | 0.2490 | 0.7792 | 0.183* | 0.50 |
C3A | 0.255 (3) | 0.210 (3) | 0.821 (3) | 0.152 (12)* | 0.50 |
H3AA | 0.2808 | 0.2470 | 0.8156 | 0.183* | 0.50 |
H3AB | 0.2767 | 0.1832 | 0.7882 | 0.183* | 0.50 |
C4A | 0.272 (5) | 0.186 (3) | 0.887 (3) | 0.152 (12)* | 0.50 |
H4AA | 0.2477 | 0.1482 | 0.8909 | 0.183* | 0.50 |
H4AB | 0.3283 | 0.1818 | 0.8916 | 0.183* | 0.50 |
C5A | 0.242 (6) | 0.225 (3) | 0.939 (3) | 0.152 (12)* | 0.50 |
H5AA | 0.2482 | 0.2060 | 0.9802 | 0.228* | 0.50 |
H5AB | 0.1868 | 0.2326 | 0.9312 | 0.228* | 0.50 |
H5AC | 0.2707 | 0.2608 | 0.9383 | 0.228* | 0.50 |
C2B | 0.207 (3) | 0.195 (3) | 0.762 (3) | 0.152 (12)* | 0.50 |
H2BA | 0.2171 | 0.2009 | 0.7174 | 0.228* | 0.50 |
H2BC | 0.1870 | 0.2298 | 0.7804 | 0.228* | 0.50 |
C3B | 0.2763 (18) | 0.173 (3) | 0.797 (3) | 0.152 (12)* | 0.50 |
H3BA | 0.3212 | 0.1977 | 0.7879 | 0.183* | 0.50 |
H3BB | 0.2885 | 0.1340 | 0.7813 | 0.183* | 0.50 |
C4B | 0.264 (3) | 0.170 (4) | 0.869 (3) | 0.152 (12)* | 0.50 |
H4BA | 0.2134 | 0.1872 | 0.8791 | 0.183* | 0.50 |
H4BB | 0.2636 | 0.1299 | 0.8824 | 0.183* | 0.50 |
C5B | 0.326 (5) | 0.202 (4) | 0.905 (3) | 0.152 (12)* | 0.50 |
H5BA | 0.3193 | 0.1957 | 0.9507 | 0.228* | 0.50 |
H5BB | 0.3230 | 0.2426 | 0.8950 | 0.228* | 0.50 |
H5BC | 0.3772 | 0.1873 | 0.8916 | 0.228* | 0.50 |
C6 | 0.000 (4) | −0.0145 (13) | 0.7371 (17) | 0.062 (10) | 0.50 |
C7 | 0.010 (7) | −0.0762 (17) | 0.755 (4) | 0.141 (14) | 0.50 |
H7A | 0.0625 | −0.0896 | 0.7536 | 0.170* | 0.50 |
H7B | −0.0155 | −0.0896 | 0.7169 | 0.170* | 0.50 |
C8 | −0.035 (5) | −0.093 (2) | 0.813 (3) | 0.141 (14) | 0.50 |
H8A | −0.0293 | −0.1330 | 0.8052 | 0.170* | 0.50 |
H8B | −0.0886 | −0.0853 | 0.8033 | 0.170* | 0.50 |
C9 | −0.034 (5) | −0.097 (2) | 0.885 (2) | 0.141 (14) | 0.50 |
H9A | −0.0716 | −0.0692 | 0.9029 | 0.170* | 0.50 |
H9B | 0.0180 | −0.0857 | 0.9005 | 0.170* | 0.50 |
C10 | −0.053 (5) | −0.155 (3) | 0.910 (3) | 0.141 (14) | 0.50 |
H10A | −0.0545 | −0.1546 | 0.9566 | 0.170* | 0.50 |
H10B | −0.0130 | −0.1823 | 0.8955 | 0.170* | 0.50 |
H10C | −0.1032 | −0.1673 | 0.8930 | 0.170* | 0.50 |
C11 | 0.4070 (11) | 0.0303 (11) | 0.8873 (8) | 0.061 (6) | |
C12 | 0.4497 (19) | 0.0480 (13) | 0.8273 (15) | 0.104 (5) | |
H12A | 0.4132 | 0.0674 | 0.7980 | 0.125* | |
H12B | 0.4689 | 0.0133 | 0.8053 | 0.125* | |
C13 | 0.5187 (19) | 0.0882 (10) | 0.8408 (14) | 0.104 (5) | |
H13A | 0.5514 | 0.0889 | 0.8019 | 0.125* | |
H13B | 0.5499 | 0.0707 | 0.8754 | 0.125* | |
C14 | 0.5028 (16) | 0.1494 (10) | 0.8598 (14) | 0.104 (5) | |
H14A | 0.4727 | 0.1684 | 0.8255 | 0.125* | |
H14B | 0.4715 | 0.1501 | 0.8995 | 0.125* | |
C15 | 0.5772 (16) | 0.1816 (13) | 0.8707 (15) | 0.104 (5) | |
H15A | 0.5657 | 0.2221 | 0.8782 | 0.125* | |
H15B | 0.6103 | 0.1779 | 0.8328 | 0.125* | |
H15C | 0.6039 | 0.1658 | 0.9081 | 0.125* | |
C16 | 0.1622 (10) | 0.0000 | 1.0000 | 0.048 (5) | |
C17 | 0.0757 (10) | 0.0000 | 1.0000 | 0.069 (5) | |
H17A | 0.0598 | −0.0350 | 0.9895 | 0.082* | 0.50 |
H17B | 0.0598 | 0.0264 | 0.9632 | 0.082* | 0.50 |
C18 | 0.0330 (16) | 0.0213 (19) | 1.057 (3) | 0.069 (5) | 0.50 |
H18A | 0.0539 | 0.0573 | 1.0700 | 0.082* | 0.50 |
H18B | 0.0429 | −0.0054 | 1.0906 | 0.082* | 0.50 |
C19 | −0.0542 (16) | 0.0226 (18) | 1.053 (2) | 0.069 (5) | 0.50 |
H19A | −0.0692 | 0.0431 | 1.0136 | 0.082* | 0.50 |
H19B | −0.0729 | −0.0172 | 1.0490 | 0.082* | 0.50 |
C20 | −0.096 (2) | 0.0498 (17) | 1.108 (2) | 0.069 (5) | 0.50 |
H20A | −0.1510 | 0.0519 | 1.0990 | 0.082* | 0.50 |
H20B | −0.0753 | 0.0884 | 1.1153 | 0.082* | 0.50 |
H20C | −0.0874 | 0.0269 | 1.1472 | 0.082* | 0.50 |
C21 | 0.4524 (12) | −0.1406 (10) | 0.5877 (10) | 0.066 (6) | |
C22 | 0.5108 (19) | −0.1678 (11) | 0.5443 (15) | 0.122 (6) | |
H22A | 0.5630 | −0.1540 | 0.5563 | 0.146* | |
H22B | 0.5006 | −0.1554 | 0.4997 | 0.146* | |
C23 | 0.510 (2) | −0.2323 (12) | 0.5468 (18) | 0.122 (6) | |
H23A | 0.5313 | −0.2441 | 0.5889 | 0.146* | |
H23B | 0.5463 | −0.2465 | 0.5137 | 0.146* | |
C24 | 0.4340 (19) | −0.2626 (15) | 0.5376 (18) | 0.122 (6) | |
H24A | 0.4077 | −0.2500 | 0.4979 | 0.146* | |
H24B | 0.3991 | −0.2567 | 0.5746 | 0.146* | |
C25 | 0.460 (2) | −0.3233 (15) | 0.5330 (16) | 0.122 (6) | |
H25A | 0.4149 | −0.3481 | 0.5262 | 0.146* | |
H25B | 0.4860 | −0.3343 | 0.5728 | 0.146* | |
H25C | 0.4957 | −0.3275 | 0.4969 | 0.146* | |
C26 | 0.2732 (13) | 0.0181 (8) | 0.6360 (10) | 0.061 (6) | |
C27 | 0.231 (3) | 0.0714 (13) | 0.6171 (16) | 0.137 (7) | |
H27A | 0.1756 | 0.0661 | 0.6286 | 0.164* | |
H27B | 0.2507 | 0.1032 | 0.6436 | 0.164* | |
C28 | 0.234 (3) | 0.0898 (9) | 0.5486 (14) | 0.137 (7) | |
H28A | 0.2126 | 0.0584 | 0.5221 | 0.164* | |
H28B | 0.2889 | 0.0943 | 0.5367 | 0.164* | |
C29 | 0.192 (2) | 0.1441 (10) | 0.5305 (13) | 0.137 (7) | |
H29A | 0.2049 | 0.1540 | 0.4856 | 0.164* | |
H29B | 0.1357 | 0.1375 | 0.5330 | 0.164* | |
C30 | 0.213 (3) | 0.1931 (8) | 0.5730 (15) | 0.137 (7) | |
H30A | 0.1797 | 0.2258 | 0.5633 | 0.164* | |
H30B | 0.2672 | 0.2037 | 0.5657 | 0.164* | |
H30C | 0.2061 | 0.1820 | 0.6179 | 0.164* | |
C31 | 0.3111 (11) | −0.1346 (6) | 0.7976 (8) | 0.041 (4) | |
C32 | 0.2879 (17) | −0.1604 (15) | 0.8567 (15) | 0.102 (5) | |
H32A | 0.3194 | −0.1430 | 0.8912 | 0.122* | |
H32B | 0.3024 | −0.2013 | 0.8546 | 0.122* | |
C33 | 0.2067 (16) | −0.1577 (13) | 0.8771 (13) | 0.102 (5) | |
H33A | 0.1900 | −0.1173 | 0.8804 | 0.122* | |
H33B | 0.2008 | −0.1757 | 0.9198 | 0.122* | |
C34 | 0.1576 (13) | −0.1884 (12) | 0.8291 (12) | 0.102 (5) | |
H34A | 0.1546 | −0.2300 | 0.8372 | 0.122* | |
H34B | 0.1741 | −0.1812 | 0.7843 | 0.122* | |
C35 | 0.0841 (15) | −0.1576 (13) | 0.8462 (14) | 0.102 (5) | |
H35A | 0.0419 | −0.1715 | 0.8190 | 0.122* | |
H35B | 0.0910 | −0.1165 | 0.8395 | 0.122* | |
H35C | 0.0715 | −0.1648 | 0.8913 | 0.122* |
U11 | U22 | U33 | U12 | U13 | U23 | |
U1 | 0.0222 (4) | 0.0287 (3) | 0.0469 (4) | 0.000 | −0.0068 (3) | 0.000 |
U2 | 0.0215 (4) | 0.0604 (5) | 0.0291 (3) | 0.000 | 0.000 | −0.0013 (3) |
U3 | 0.0305 (3) | 0.0432 (3) | 0.0382 (3) | 0.0000 (2) | −0.0049 (2) | 0.0012 (2) |
K1 | 0.031 (2) | 0.063 (3) | 0.0266 (19) | 0.000 | 0.000 | 0.000 (2) |
K2 | 0.050 (3) | 0.025 (2) | 0.067 (3) | 0.000 | −0.010 (3) | 0.000 |
K3 | 0.0304 (16) | 0.0468 (19) | 0.0364 (15) | 0.0076 (14) | −0.0041 (12) | 0.0042 (13) |
O1 | 0.081 (10) | 0.091 (10) | 0.034 (6) | −0.009 (8) | 0.008 (6) | −0.018 (6) |
O2 | 0.065 (6) | 0.066 (5) | 0.085 (6) | −0.005 (4) | −0.003 (4) | 0.002 (4) |
O3 | 0.048 (5) | 0.059 (5) | 0.072 (5) | 0.002 (4) | −0.008 (4) | 0.003 (4) |
O4 | 0.044 (8) | 0.033 (6) | 0.147 (15) | 0.004 (6) | −0.040 (9) | 0.009 (7) |
O5 | 0.043 (7) | 0.046 (6) | 0.048 (6) | −0.006 (5) | 0.000 (5) | −0.005 (5) |
O6 | 0.017 (5) | 0.107 (11) | 0.033 (5) | −0.007 (6) | −0.001 (4) | −0.001 (6) |
O7 | 0.032 (7) | 0.095 (10) | 0.032 (5) | 0.003 (6) | 0.001 (5) | 0.011 (5) |
O8 | 0.022 (5) | 0.092 (10) | 0.050 (6) | 0.013 (6) | −0.006 (5) | 0.020 (6) |
O9 | 0.037 (7) | 0.067 (8) | 0.055 (7) | −0.012 (6) | 0.000 (5) | −0.013 (6) |
O10 | 0.035 (7) | 0.057 (8) | 0.050 (6) | −0.010 (5) | −0.003 (5) | −0.009 (5) |
O11 | 0.109 (13) | 0.053 (8) | 0.047 (7) | 0.041 (8) | −0.014 (7) | −0.011 (6) |
O12 | 0.034 (6) | 0.048 (7) | 0.044 (5) | 0.003 (5) | −0.002 (4) | −0.001 (5) |
O13 | 0.049 (7) | 0.046 (7) | 0.055 (7) | 0.017 (6) | 0.014 (5) | 0.023 (5) |
O14 | 0.034 (6) | 0.073 (8) | 0.054 (7) | 0.027 (6) | 0.017 (5) | 0.034 (6) |
O15 | 0.045 (7) | 0.048 (7) | 0.040 (5) | 0.002 (5) | 0.007 (5) | 0.004 (5) |
O16 | 0.053 (8) | 0.046 (6) | 0.039 (6) | 0.006 (5) | −0.005 (5) | 0.001 (5) |
C6 | 0.061 (11) | 0.062 (11) | 0.062 (12) | 0.002 (5) | 0.000 (5) | −0.003 (5) |
C7 | 0.139 (15) | 0.140 (15) | 0.145 (15) | −0.001 (5) | −0.001 (5) | 0.002 (5) |
C8 | 0.139 (15) | 0.140 (15) | 0.145 (15) | −0.001 (5) | −0.001 (5) | 0.002 (5) |
C9 | 0.139 (15) | 0.140 (15) | 0.145 (15) | −0.001 (5) | −0.001 (5) | 0.002 (5) |
C10 | 0.139 (15) | 0.140 (15) | 0.145 (15) | −0.001 (5) | −0.001 (5) | 0.002 (5) |
C11 | 0.041 (11) | 0.110 (17) | 0.034 (8) | 0.021 (11) | 0.008 (7) | 0.005 (9) |
C12 | 0.112 (13) | 0.098 (11) | 0.103 (10) | 0.014 (9) | 0.045 (10) | −0.003 (8) |
C13 | 0.112 (13) | 0.098 (11) | 0.103 (10) | 0.014 (9) | 0.045 (10) | −0.003 (8) |
C14 | 0.112 (13) | 0.098 (11) | 0.103 (10) | 0.014 (9) | 0.045 (10) | −0.003 (8) |
C15 | 0.112 (13) | 0.098 (11) | 0.103 (10) | 0.014 (9) | 0.045 (10) | −0.003 (8) |
C16 | 0.026 (11) | 0.070 (15) | 0.048 (12) | 0.000 | 0.000 | 0.011 (11) |
C17 | 0.024 (9) | 0.057 (11) | 0.125 (17) | 0.000 | 0.000 | 0.016 (10) |
C18 | 0.024 (9) | 0.057 (11) | 0.125 (17) | 0.000 | 0.000 | 0.016 (10) |
C19 | 0.024 (9) | 0.057 (11) | 0.125 (17) | 0.000 | 0.000 | 0.016 (10) |
C20 | 0.024 (9) | 0.057 (11) | 0.125 (17) | 0.000 | 0.000 | 0.016 (10) |
C21 | 0.051 (12) | 0.078 (14) | 0.069 (13) | 0.028 (11) | −0.017 (10) | −0.024 (11) |
C22 | 0.128 (7) | 0.119 (7) | 0.118 (7) | 0.009 (5) | 0.001 (5) | −0.002 (5) |
C23 | 0.128 (7) | 0.119 (7) | 0.118 (7) | 0.009 (5) | 0.001 (5) | −0.002 (5) |
C24 | 0.128 (7) | 0.119 (7) | 0.118 (7) | 0.009 (5) | 0.001 (5) | −0.002 (5) |
C25 | 0.128 (7) | 0.119 (7) | 0.118 (7) | 0.009 (5) | 0.001 (5) | −0.002 (5) |
C26 | 0.073 (14) | 0.041 (10) | 0.070 (12) | 0.026 (9) | 0.031 (10) | 0.014 (8) |
C27 | 0.23 (2) | 0.064 (9) | 0.116 (12) | 0.035 (12) | 0.027 (14) | 0.027 (8) |
C28 | 0.23 (2) | 0.064 (9) | 0.116 (12) | 0.035 (12) | 0.027 (14) | 0.027 (8) |
C29 | 0.23 (2) | 0.064 (9) | 0.116 (12) | 0.035 (12) | 0.027 (14) | 0.027 (8) |
C30 | 0.23 (2) | 0.064 (9) | 0.116 (12) | 0.035 (12) | 0.027 (14) | 0.027 (8) |
C31 | 0.055 (11) | 0.024 (7) | 0.044 (8) | −0.007 (7) | −0.020 (8) | 0.005 (6) |
C32 | 0.077 (10) | 0.123 (12) | 0.104 (10) | 0.034 (9) | 0.013 (7) | 0.035 (9) |
C33 | 0.077 (10) | 0.123 (12) | 0.104 (10) | 0.034 (9) | 0.013 (7) | 0.035 (9) |
C34 | 0.077 (10) | 0.123 (12) | 0.104 (10) | 0.034 (9) | 0.013 (7) | 0.035 (9) |
C35 | 0.077 (10) | 0.123 (12) | 0.104 (10) | 0.034 (9) | 0.013 (7) | 0.035 (9) |
U1—O1 | 1.775 (12) | C5B—H5BC | 0.9800 |
U1—O1i | 1.775 (12) | C6—O4i | 1.14 (6) |
U1—O4i | 2.426 (12) | C6—C7 | 1.502 (11) |
U1—O4 | 2.426 (12) | C7—C8 | 1.502 (10) |
U1—O2 | 2.470 (15) | C7—H7A | 0.9601 |
U1—O2i | 2.470 (15) | C7—H7B | 0.9600 |
U1—O3 | 2.505 (13) | C8—C9 | 1.500 (11) |
U1—O3i | 2.505 (13) | C8—H8A | 0.9600 |
U2—O5 | 1.716 (11) | C8—H8B | 0.9700 |
U2—O5ii | 1.716 (11) | C9—C10 | 1.498 (10) |
U2—O6ii | 2.451 (10) | C9—H9A | 0.9900 |
U2—O6 | 2.451 (10) | C9—H9B | 0.9900 |
U2—O8 | 2.470 (10) | C10—H10A | 0.9800 |
U2—O8ii | 2.470 (10) | C10—H10B | 0.9800 |
U2—O7 | 2.476 (10) | C10—H10C | 0.9800 |
U2—O7ii | 2.476 (10) | C11—C12 | 1.51 (3) |
U3—O9 | 1.719 (12) | C12—C13 | 1.55 (4) |
U3—O10 | 1.757 (12) | C12—H12A | 0.9900 |
U3—O16 | 2.441 (11) | C12—H12B | 0.9900 |
U3—O14 | 2.462 (12) | C13—C14 | 1.512 (10) |
U3—O12 | 2.464 (11) | C13—H13A | 0.9900 |
U3—O13 | 2.491 (10) | C13—H13B | 0.9900 |
U3—O15 | 2.520 (10) | C14—C15 | 1.508 (10) |
U3—O11 | 2.526 (13) | C14—H14A | 0.9900 |
K1—O13iii | 2.690 (11) | C14—H14B | 0.9900 |
K1—O13 | 2.690 (11) | C15—H15A | 0.9800 |
K1—O12 | 2.698 (11) | C15—H15B | 0.9800 |
K1—O12iii | 2.698 (11) | C15—H15C | 0.9800 |
K1—O6iv | 2.747 (11) | C16—O8ii | 1.223 (15) |
K1—O6v | 2.747 (11) | C16—C17 | 1.496 (10) |
K2—O2i | 2.657 (17) | C17—C18 | 1.48 (5) |
K2—O2 | 2.657 (16) | C17—C18ii | 1.48 (5) |
K2—O11vi | 2.670 (13) | C17—H17A | 0.8924 |
K2—O11vii | 2.670 (13) | C17—H17B | 1.0234 |
K2—O16vi | 2.759 (13) | C18—C19 | 1.510 (10) |
K2—O16vii | 2.759 (13) | C18—H18A | 0.9603 |
K3—O3 | 2.688 (14) | C18—H18B | 0.9599 |
K3—O7 | 2.688 (12) | C19—C20 | 1.498 (10) |
K3—O14 | 2.713 (11) | C19—H19A | 0.9900 |
K3—O4 | 2.724 (13) | C19—H19B | 0.9900 |
K3—O15 | 2.769 (12) | C20—H20A | 0.9800 |
K3—O8 | 2.817 (12) | C20—H20B | 0.9800 |
O2—C1 | 1.27 (3) | C20—H20C | 0.9800 |
O3—C1 | 1.24 (3) | C21—C22 | 1.498 (10) |
O4—C6i | 1.14 (6) | C22—C23 | 1.511 (10) |
O4—C6 | 1.34 (5) | C22—H22A | 0.9900 |
O6—C11 | 1.25 (2) | C22—H22B | 0.9900 |
O6—K1viii | 2.747 (11) | C23—C24 | 1.509 (10) |
O7—C11 | 1.28 (2) | C23—H23A | 0.9900 |
O8—C16 | 1.223 (15) | C23—H23B | 0.9900 |
O11—C21 | 1.31 (3) | C24—C25 | 1.49 (4) |
O11—K2ix | 2.670 (13) | C24—H24A | 0.9900 |
O12—C21 | 1.29 (2) | C24—H24B | 0.9900 |
O13—C26 | 1.28 (2) | C25—H25A | 0.9800 |
O14—C26 | 1.30 (2) | C25—H25B | 0.9800 |
O15—C31 | 1.227 (19) | C25—H25C | 0.9800 |
O16—C31 | 1.23 (2) | C26—C27 | 1.50 (4) |
O16—K2ix | 2.759 (12) | C27—C28 | 1.49 (4) |
C1—C2A | 1.504 (10) | C27—H27A | 0.9900 |
C2A—C3A | 1.501 (10) | C27—H27B | 0.9900 |
C2A—H2AA | 0.9900 | C28—C29 | 1.509 (10) |
C2A—H2AB | 0.9900 | C28—H28A | 0.9900 |
C2A—H2BC | 0.7316 | C28—H28B | 0.9900 |
C3A—C4A | 1.505 (10) | C29—C30 | 1.495 (10) |
C3A—H3AA | 0.9900 | C29—H29A | 0.9900 |
C3A—H3AB | 0.9900 | C29—H29B | 0.9900 |
C4A—C5A | 1.502 (10) | C30—H30A | 0.9800 |
C4A—H4AA | 0.9900 | C30—H30B | 0.9800 |
C4A—H4AB | 0.9900 | C30—H30C | 0.9800 |
C5A—H5AA | 0.9800 | C31—C32 | 1.43 (3) |
C5A—H5AB | 0.9800 | C32—C33 | 1.47 (4) |
C5A—H5AC | 0.9800 | C32—H32A | 0.9900 |
C2B—C3B | 1.500 (10) | C32—H32B | 0.9900 |
C2B—H2BA | 0.9600 | C33—C34 | 1.497 (10) |
C2B—H2BC | 0.9600 | C33—H33A | 0.9900 |
C3B—C4B | 1.502 (10) | C33—H33B | 0.9900 |
C3B—H3BA | 0.9900 | C34—C35 | 1.504 (10) |
C3B—H3BB | 0.9900 | C34—H34A | 0.9900 |
C4B—C5B | 1.503 (10) | C34—H34B | 0.9900 |
C4B—H4BA | 0.9900 | C35—H35A | 0.9800 |
C4B—H4BB | 0.9900 | C35—H35B | 0.9800 |
C5B—H5BA | 0.9800 | C35—H35C | 0.9800 |
C5B—H5BB | 0.9800 | ||
O1—U1—O1i | 179.1 (10) | O3—K3—U3 | 122.1 (3) |
O1—U1—O4i | 92.0 (7) | O7—K3—U3 | 88.4 (3) |
O1i—U1—O4i | 87.1 (7) | O14—K3—U3 | 30.2 (2) |
O1—U1—O4 | 87.1 (7) | O4—K3—U3 | 107.3 (4) |
O1i—U1—O4 | 92.0 (7) | O15—K3—U3 | 32.0 (2) |
O4i—U1—O4 | 52.3 (6) | O8—K3—U3 | 132.1 (3) |
O1—U1—O2 | 89.9 (6) | U1—K3—U3 | 119.80 (7) |
O1i—U1—O2 | 90.9 (6) | O3—K3—U2 | 117.0 (3) |
O4i—U1—O2 | 173.1 (5) | O7—K3—U2 | 30.2 (2) |
O4—U1—O2 | 121.2 (5) | O14—K3—U2 | 129.4 (3) |
O1—U1—O2i | 90.9 (6) | O4—K3—U2 | 137.1 (4) |
O1i—U1—O2i | 89.9 (6) | O15—K3—U2 | 87.7 (2) |
O4i—U1—O2i | 121.2 (5) | O8—K3—U2 | 31.3 (2) |
O4—U1—O2i | 173.1 (5) | U1—K3—U2 | 132.77 (8) |
O2—U1—O2i | 65.4 (8) | U3—K3—U2 | 107.26 (7) |
O1—U1—O3 | 92.1 (6) | C1—O2—U1 | 90.6 (16) |
O1i—U1—O3 | 87.9 (6) | C1—O2—K2 | 151.1 (18) |
O4i—U1—O3 | 120.0 (4) | U1—O2—K2 | 117.2 (6) |
O4—U1—O3 | 68.2 (4) | C1—O3—U1 | 89.7 (16) |
O2—U1—O3 | 53.3 (5) | C1—O3—K3 | 155.6 (17) |
O2i—U1—O3 | 118.6 (5) | U1—O3—K3 | 114.4 (5) |
O1—U1—O3i | 87.9 (6) | C6i—O4—U1 | 95 (2) |
O1i—U1—O3i | 92.1 (6) | C6—O4—U1 | 89.9 (18) |
O4i—U1—O3i | 68.2 (4) | C6i—O4—K3 | 149 (2) |
O4—U1—O3i | 120.0 (4) | C6—O4—K3 | 150 (2) |
O2—U1—O3i | 118.6 (5) | U1—O4—K3 | 115.9 (5) |
O2i—U1—O3i | 53.3 (5) | C11—O6—U2 | 94.8 (10) |
O3—U1—O3i | 171.8 (6) | C11—O6—K1viii | 148.9 (11) |
O1—U1—C6 | 94.8 (9) | U2—O6—K1viii | 116.3 (4) |
O1i—U1—C6 | 84.3 (9) | C11—O7—U2 | 92.9 (10) |
O4i—U1—C6 | 24.3 (13) | C11—O7—K3 | 149.0 (10) |
O4—U1—C6 | 28.9 (12) | U2—O7—K3 | 116.8 (5) |
O2—U1—C6 | 148.8 (13) | C16—O8—U2 | 92.6 (9) |
O2i—U1—C6 | 145.1 (13) | C16—O8—K3 | 154.3 (11) |
O3—U1—C6 | 95.7 (13) | U2—O8—K3 | 112.5 (4) |
O3i—U1—C6 | 92.4 (13) | C21—O11—U3 | 93.2 (10) |
O1—U1—C6i | 84.3 (9) | C21—O11—K2ix | 148.1 (14) |
O1i—U1—C6i | 94.8 (9) | U3—O11—K2ix | 110.0 (5) |
O4i—U1—C6i | 28.9 (12) | C21—O12—U3 | 96.6 (12) |
O4—U1—C6i | 24.3 (13) | C21—O12—K1 | 143.2 (13) |
O2—U1—C6i | 145.1 (13) | U3—O12—K1 | 115.5 (4) |
O2i—U1—C6i | 148.8 (13) | C26—O13—U3 | 92.3 (10) |
O3—U1—C6i | 92.4 (13) | C26—O13—K1 | 147.8 (11) |
O3i—U1—C6i | 95.7 (13) | U3—O13—K1 | 114.9 (4) |
C6—U1—C6i | 11.1 (15) | C26—O14—U3 | 93.0 (10) |
O1—U1—C1 | 93.2 (8) | C26—O14—K3 | 150.7 (11) |
O1i—U1—C1 | 87.3 (9) | U3—O14—K3 | 116.2 (4) |
O4i—U1—C1 | 146.1 (8) | C31—O15—U3 | 93.0 (10) |
O4—U1—C1 | 94.6 (8) | C31—O15—K3 | 149.7 (10) |
O2—U1—C1 | 27.0 (7) | U3—O15—K3 | 112.4 (4) |
O2i—U1—C1 | 92.2 (9) | C31—O16—U3 | 96.7 (9) |
O3—U1—C1 | 26.4 (7) | C31—O16—K2ix | 145.7 (10) |
O3i—U1—C1 | 145.5 (8) | U3—O16—K2ix | 109.7 (4) |
C6—U1—C1 | 121.8 (15) | O3—C1—O2 | 126 (3) |
C6i—U1—C1 | 118.8 (14) | O3—C1—C2A | 140 (3) |
O1—U1—C1i | 87.3 (9) | O2—C1—C2A | 88 (3) |
O1i—U1—C1i | 93.2 (8) | O3—C1—U1 | 63.9 (14) |
O4i—U1—C1i | 94.6 (8) | O2—C1—U1 | 62.3 (14) |
O4—U1—C1i | 146.1 (8) | C2A—C1—U1 | 148 (3) |
O2—U1—C1i | 92.2 (9) | C1—C2A—C3A | 112.2 (11) |
O2i—U1—C1i | 27.0 (7) | C1—C2A—H2AA | 108.8 |
O3—U1—C1i | 145.5 (8) | C3A—C2A—H2AA | 109.1 |
O3i—U1—C1i | 26.4 (7) | C1—C2A—H2AB | 109.6 |
C6—U1—C1i | 118.8 (14) | C3A—C2A—H2AB | 109.1 |
C6i—U1—C1i | 121.8 (15) | H2AA—C2A—H2AB | 107.9 |
C1—U1—C1i | 119.1 (14) | C1—C2A—H2BC | 101.4 |
O5—U2—O5ii | 180.0 (8) | C3A—C2A—H2BC | 77.5 |
O5—U2—O6ii | 92.4 (5) | H2AA—C2A—H2BC | 142.9 |
O5ii—U2—O6ii | 87.6 (5) | C2A—C3A—C4A | 112.2 (11) |
O5—U2—O6 | 87.6 (5) | C2A—C3A—H3AA | 109.1 |
O5ii—U2—O6 | 92.4 (5) | C4A—C3A—H3AA | 109.4 |
O6ii—U2—O6 | 67.7 (5) | C2A—C3A—H3AB | 109.1 |
O5—U2—O8 | 92.0 (5) | C4A—C3A—H3AB | 109.0 |
O5ii—U2—O8 | 88.0 (5) | H3AA—C3A—H3AB | 107.9 |
O6ii—U2—O8 | 170.9 (4) | C5A—C4A—C3A | 112.3 (11) |
O6—U2—O8 | 120.5 (4) | C5A—C4A—H4AA | 109.4 |
O5—U2—O8ii | 88.0 (5) | C3A—C4A—H4AA | 109.4 |
O5ii—U2—O8ii | 92.0 (5) | C5A—C4A—H4AB | 108.8 |
O6ii—U2—O8ii | 120.5 (4) | C3A—C4A—H4AB | 109.0 |
O6—U2—O8ii | 170.9 (4) | H4AA—C4A—H4AB | 109.0 |
O8—U2—O8ii | 51.6 (5) | C4A—C5A—H5AA | 109.5 |
O5—U2—O7 | 88.6 (5) | C4A—C5A—H5AB | 109.1 |
O5ii—U2—O7 | 91.4 (5) | H5AA—C5A—H5AB | 109.5 |
O6ii—U2—O7 | 120.1 (4) | C4A—C5A—H5AC | 109.8 |
O6—U2—O7 | 52.5 (4) | H5AA—C5A—H5AC | 109.5 |
O8—U2—O7 | 68.0 (4) | H5AB—C5A—H5AC | 109.5 |
O8ii—U2—O7 | 119.4 (4) | C3B—C2B—H2BA | 112.0 |
O5—U2—O7ii | 91.4 (5) | C3B—C2B—H2BC | 112.8 |
O5ii—U2—O7ii | 88.6 (5) | H2BA—C2B—H2BC | 109.5 |
O6ii—U2—O7ii | 52.5 (4) | C2B—C3B—C4B | 112.6 (11) |
O6—U2—O7ii | 120.1 (4) | C2B—C3B—H3BA | 110.0 |
O8—U2—O7ii | 119.4 (4) | C4B—C3B—H3BA | 108.7 |
O8ii—U2—O7ii | 68.0 (4) | C2B—C3B—H3BB | 109.2 |
O7—U2—O7ii | 172.6 (6) | C4B—C3B—H3BB | 108.0 |
O5—U2—C16 | 90.0 (4) | H3BA—C3B—H3BB | 107.8 |
O5ii—U2—C16 | 90.0 (4) | C5B—C4B—C3B | 112.2 (11) |
O6ii—U2—C16 | 146.2 (2) | C5B—C4B—H4BA | 109.5 |
O6—U2—C16 | 146.2 (2) | C3B—C4B—H4BA | 108.0 |
O8—U2—C16 | 25.8 (3) | C5B—C4B—H4BB | 109.2 |
O8ii—U2—C16 | 25.8 (3) | C3B—C4B—H4BB | 108.7 |
O7—U2—C16 | 93.7 (3) | H4BA—C4B—H4BB | 109.0 |
O7ii—U2—C16 | 93.7 (3) | C4B—C5B—H5BA | 109.1 |
O5—U2—C11ii | 94.1 (6) | C4B—C5B—H5BB | 109.5 |
O5ii—U2—C11ii | 85.9 (6) | H5BA—C5B—H5BB | 111.0 |
O6ii—U2—C11ii | 26.0 (5) | C4B—C5B—H5BC | 109.8 |
O6—U2—C11ii | 93.7 (5) | H5BA—C5B—H5BC | 109.5 |
O8—U2—C11ii | 145.5 (5) | H5BB—C5B—H5BC | 109.5 |
O8ii—U2—C11ii | 94.6 (5) | O4i—C6—O4 | 119 (3) |
O7—U2—C11ii | 146.0 (5) | O4i—C6—C7 | 128 (6) |
O7ii—U2—C11ii | 26.6 (5) | O4—C6—C7 | 102 (6) |
C16—U2—C11ii | 120.2 (4) | O4i—C6—U1 | 60.8 (15) |
O5—U2—C11 | 85.9 (6) | O4—C6—U1 | 61.2 (13) |
O5ii—U2—C11 | 94.1 (6) | C7—C6—U1 | 159 (5) |
O6ii—U2—C11 | 93.7 (5) | C6—C7—C8 | 112.9 (11) |
O6—U2—C11 | 26.0 (5) | C6—C7—H7A | 114.6 |
O8—U2—C11 | 94.6 (5) | C8—C7—H7A | 115.7 |
O8ii—U2—C11 | 145.5 (5) | C6—C7—H7B | 93.2 |
O7—U2—C11 | 26.6 (5) | C8—C7—H7B | 110.1 |
O7ii—U2—C11 | 146.0 (5) | H7A—C7—H7B | 107.8 |
C16—U2—C11 | 120.2 (4) | C9—C8—C7 | 145 (9) |
C11ii—U2—C11 | 119.6 (8) | C9—C8—H8A | 96.6 |
O5—U2—K3 | 97.4 (4) | C7—C8—H8A | 93.0 |
O5ii—U2—K3 | 82.6 (4) | C9—C8—H8B | 103.0 |
O6ii—U2—K3 | 150.4 (2) | C7—C8—H8B | 106.1 |
O6—U2—K3 | 84.8 (2) | H8A—C8—H8B | 104.4 |
O8—U2—K3 | 36.3 (3) | C8—C9—C10 | 113.2 (11) |
O8ii—U2—K3 | 87.8 (3) | C8—C9—H9A | 108.0 |
O7—U2—K3 | 33.1 (3) | C10—C9—H9A | 108.1 |
O7ii—U2—K3 | 154.0 (3) | C8—C9—H9B | 109.9 |
C16—U2—K3 | 62.02 (4) | C10—C9—H9B | 109.7 |
C11ii—U2—K3 | 168.3 (5) | H9A—C9—H9B | 107.7 |
C11—U2—K3 | 59.5 (4) | C9—C10—H10A | 109.6 |
O9—U3—O10 | 179.2 (6) | C9—C10—H10B | 108.6 |
O9—U3—O16 | 90.0 (5) | H10A—C10—H10B | 109.5 |
O10—U3—O16 | 89.2 (5) | C9—C10—H10C | 110.3 |
O9—U3—O14 | 93.2 (6) | H10A—C10—H10C | 109.5 |
O10—U3—O14 | 87.1 (5) | H10B—C10—H10C | 109.5 |
O16—U3—O14 | 118.8 (4) | O6—C11—O7 | 119.3 (16) |
O9—U3—O12 | 90.0 (5) | O6—C11—C12 | 122 (2) |
O10—U3—O12 | 90.5 (5) | O7—C11—C12 | 119 (2) |
O16—U3—O12 | 121.6 (4) | O6—C11—U2 | 59.3 (9) |
O14—U3—O12 | 119.5 (4) | O7—C11—U2 | 60.5 (8) |
O9—U3—O13 | 90.2 (6) | C12—C11—U2 | 178.4 (18) |
O10—U3—O13 | 90.6 (5) | C11—C12—C13 | 113 (3) |
O16—U3—O13 | 172.6 (4) | C11—C12—H12A | 109.0 |
O14—U3—O13 | 53.9 (4) | C13—C12—H12A | 109.2 |
O12—U3—O13 | 65.8 (4) | C11—C12—H12B | 109.0 |
O9—U3—O15 | 87.4 (5) | C13—C12—H12B | 108.7 |
O10—U3—O15 | 92.0 (5) | H12A—C12—H12B | 107.7 |
O16—U3—O15 | 50.7 (4) | C12—C13—C14 | 119 (2) |
O14—U3—O15 | 68.4 (4) | C12—C13—H13A | 107.5 |
O12—U3—O15 | 171.8 (4) | C14—C13—H13A | 107.7 |
O13—U3—O15 | 122.0 (4) | C12—C13—H13B | 107.8 |
O9—U3—O11 | 91.8 (6) | C14—C13—H13B | 107.2 |
O10—U3—O11 | 88.0 (6) | H13A—C13—H13B | 107.0 |
O16—U3—O11 | 68.9 (4) | C15—C14—C13 | 111 (2) |
O14—U3—O11 | 170.8 (5) | C15—C14—H14A | 109.6 |
O12—U3—O11 | 52.7 (4) | C13—C14—H14A | 109.2 |
O13—U3—O11 | 118.4 (4) | C15—C14—H14B | 109.3 |
O15—U3—O11 | 119.6 (4) | C13—C14—H14B | 109.7 |
O9—U3—C26 | 91.0 (7) | H14A—C14—H14B | 108.1 |
O10—U3—C26 | 89.6 (7) | C14—C15—H15A | 109.6 |
O16—U3—C26 | 146.0 (5) | C14—C15—H15B | 109.2 |
O14—U3—C26 | 27.2 (4) | H15A—C15—H15B | 109.5 |
O12—U3—C26 | 92.4 (5) | C14—C15—H15C | 109.6 |
O13—U3—C26 | 26.6 (5) | H15A—C15—H15C | 109.5 |
O15—U3—C26 | 95.4 (5) | H15B—C15—H15C | 109.5 |
O11—U3—C26 | 145.0 (5) | O8ii—C16—O8 | 123.2 (18) |
O9—U3—C31 | 88.7 (5) | O8ii—C16—C17 | 118.4 (9) |
O10—U3—C31 | 90.5 (5) | O8—C16—C17 | 118.4 (9) |
O16—U3—C31 | 25.3 (4) | O8ii—C16—U2 | 61.6 (9) |
O14—U3—C31 | 93.6 (4) | O8—C16—U2 | 61.6 (9) |
O12—U3—C31 | 146.9 (4) | C17—C16—U2 | 180.000 (3) |
O13—U3—C31 | 147.3 (4) | C18—C17—C18ii | 120 (3) |
O15—U3—C31 | 25.4 (4) | C18—C17—C16 | 120.0 (15) |
O11—U3—C31 | 94.2 (5) | C18ii—C17—C16 | 120.0 (15) |
C26—U3—C31 | 120.7 (5) | C18—C17—H17A | 110.5 |
O9—U3—C21 | 91.0 (6) | C18ii—C17—H17A | 48.7 |
O10—U3—C21 | 89.2 (6) | C16—C17—H17A | 108.0 |
O16—U3—C21 | 95.5 (6) | C18—C17—H17B | 105.1 |
O14—U3—C21 | 145.4 (5) | C18ii—C17—H17B | 58.0 |
O12—U3—C21 | 26.1 (5) | C16—C17—H17B | 105.7 |
O13—U3—C21 | 91.8 (5) | H17A—C17—H17B | 106.8 |
O15—U3—C21 | 146.2 (5) | C17—C18—C19 | 118 (4) |
O11—U3—C21 | 26.6 (6) | C17—C18—H18A | 109.9 |
C26—U3—C21 | 118.4 (6) | C19—C18—H18A | 111.8 |
C31—U3—C21 | 120.8 (6) | C17—C18—H18B | 106.4 |
O9—U3—K2ix | 105.1 (5) | C19—C18—H18B | 103.0 |
O10—U3—K2ix | 74.3 (4) | C20—C19—C18 | 117 (3) |
O16—U3—K2ix | 37.6 (3) | C20—C19—H19A | 108.1 |
O14—U3—K2ix | 148.2 (3) | C18—C19—H19A | 108.1 |
O12—U3—K2ix | 86.8 (3) | C20—C19—H19B | 108.1 |
O13—U3—K2ix | 148.8 (3) | C18—C19—H19B | 108.3 |
O15—U3—K2ix | 86.3 (3) | H19A—C19—H19B | 107.3 |
O11—U3—K2ix | 36.1 (3) | C19—C20—H20A | 109.6 |
C26—U3—K2ix | 163.9 (5) | C19—C20—H20B | 109.4 |
C31—U3—K2ix | 61.7 (4) | H20A—C20—H20B | 109.5 |
C21—U3—K2ix | 61.5 (4) | C19—C20—H20C | 109.4 |
O13iii—K1—O13 | 98.0 (6) | H20A—C20—H20C | 109.5 |
O13iii—K1—O12 | 117.1 (3) | H20B—C20—H20C | 108.0 |
O13—K1—O12 | 59.9 (3) | O11—C21—O12 | 117.5 (16) |
O13iii—K1—O12iii | 59.9 (3) | O11—C21—C22 | 119 (2) |
O13—K1—O12iii | 117.1 (3) | O12—C21—C22 | 123 (2) |
O12—K1—O12iii | 176.0 (5) | O11—C21—U3 | 60.1 (9) |
O13iii—K1—O6iv | 156.7 (4) | O12—C21—U3 | 57.3 (9) |
O13—K1—O6iv | 102.7 (4) | C22—C21—U3 | 177.7 (19) |
O12—K1—O6iv | 83.0 (4) | C21—C22—C23 | 113 (3) |
O12iii—K1—O6iv | 100.5 (4) | C21—C22—H22A | 108.7 |
O13iii—K1—O6v | 102.7 (4) | C23—C22—H22A | 108.9 |
O13—K1—O6v | 156.7 (4) | C21—C22—H22B | 109.0 |
O12—K1—O6v | 100.5 (4) | C23—C22—H22B | 108.9 |
O12iii—K1—O6v | 83.0 (4) | H22A—C22—H22B | 107.7 |
O6iv—K1—O6v | 59.6 (4) | C22—C23—C24 | 118 (3) |
O13iii—K1—U3 | 117.5 (3) | C22—C23—H23A | 107.7 |
O13—K1—U3 | 31.1 (2) | C24—C23—H23A | 108.1 |
O12—K1—U3 | 30.6 (2) | C22—C23—H23B | 107.7 |
O12iii—K1—U3 | 147.1 (2) | C24—C23—H23B | 107.6 |
O6iv—K1—U3 | 85.8 (2) | H23A—C23—H23B | 107.1 |
O6v—K1—U3 | 126.5 (3) | C23—C24—C25 | 101 (3) |
O13iii—K1—U3iii | 31.1 (2) | C23—C24—H24A | 111.9 |
O13—K1—U3iii | 117.5 (3) | C25—C24—H24A | 111.6 |
O12—K1—U3iii | 147.1 (2) | C23—C24—H24B | 111.3 |
O12iii—K1—U3iii | 30.6 (2) | C25—C24—H24B | 111.5 |
O6iv—K1—U3iii | 126.5 (3) | H24A—C24—H24B | 109.3 |
O6v—K1—U3iii | 85.8 (2) | C24—C25—H25A | 109.4 |
U3—K1—U3iii | 145.01 (12) | C24—C25—H25B | 109.6 |
O13iii—K1—U2v | 131.0 (3) | H25A—C25—H25B | 109.5 |
O13—K1—U2v | 131.0 (3) | C24—C25—H25C | 109.4 |
O12—K1—U2v | 92.0 (3) | H25A—C25—H25C | 109.5 |
O12iii—K1—U2v | 92.0 (3) | H25B—C25—H25C | 109.5 |
O6iv—K1—U2v | 29.8 (2) | O13—C26—O14 | 120.7 (16) |
O6v—K1—U2v | 29.8 (2) | O13—C26—C27 | 122 (2) |
U3—K1—U2v | 107.49 (6) | O14—C26—C27 | 117.8 (19) |
U3iii—K1—U2v | 107.49 (6) | O13—C26—U3 | 61.0 (8) |
O2i—K2—O2 | 60.3 (7) | O14—C26—U3 | 59.8 (9) |
O2i—K2—O11vi | 132.9 (4) | C27—C26—U3 | 176 (2) |
O2—K2—O11vi | 92.2 (5) | C28—C27—C26 | 118 (3) |
O2i—K2—O11vii | 92.2 (5) | C28—C27—H27A | 108.0 |
O2—K2—O11vii | 132.9 (4) | C26—C27—H27A | 108.0 |
O11vi—K2—O11vii | 130.9 (6) | C28—C27—H27B | 107.5 |
O2i—K2—O16vi | 143.0 (4) | C26—C27—H27B | 107.5 |
O2—K2—O16vi | 89.3 (4) | H27A—C27—H27B | 107.2 |
O11vi—K2—O16vi | 62.4 (4) | C27—C28—C29 | 118 (3) |
O11vii—K2—O16vi | 94.9 (5) | C27—C28—H28A | 107.6 |
O2i—K2—O16vii | 89.3 (4) | C29—C28—H28A | 108.1 |
O2—K2—O16vii | 143.0 (4) | C27—C28—H28B | 108.1 |
O11vi—K2—O16vii | 94.9 (5) | C29—C28—H28B | 107.8 |
O11vii—K2—O16vii | 62.4 (4) | H28A—C28—H28B | 107.2 |
O16vi—K2—O16vii | 125.9 (5) | C30—C29—C28 | 112.5 (10) |
O2i—K2—U3vi | 161.9 (3) | C30—C29—H29A | 109.5 |
O2—K2—U3vi | 103.1 (3) | C28—C29—H29A | 109.1 |
O11vi—K2—U3vi | 33.9 (3) | C30—C29—H29B | 108.9 |
O11vii—K2—U3vi | 105.3 (4) | C28—C29—H29B | 108.9 |
O16vi—K2—U3vi | 32.7 (2) | H29A—C29—H29B | 107.8 |
O16vii—K2—U3vi | 102.8 (3) | C29—C30—H30A | 109.3 |
O2i—K2—U3vii | 103.1 (3) | C29—C30—H30B | 109.2 |
O2—K2—U3vii | 161.9 (3) | H30A—C30—H30B | 109.5 |
O11vi—K2—U3vii | 105.3 (4) | C29—C30—H30C | 109.9 |
O11vii—K2—U3vii | 33.9 (3) | H30A—C30—H30C | 109.5 |
O16vi—K2—U3vii | 102.8 (3) | H30B—C30—H30C | 109.5 |
O16vii—K2—U3vii | 32.7 (2) | O15—C31—O16 | 119.6 (15) |
U3vi—K2—U3vii | 94.21 (9) | O15—C31—C32 | 116 (2) |
O2i—K2—U1 | 30.1 (3) | O16—C31—C32 | 123.7 (18) |
O2—K2—U1 | 30.1 (3) | O15—C31—U3 | 61.6 (8) |
O11vi—K2—U1 | 114.5 (3) | O16—C31—U3 | 57.9 (8) |
O11vii—K2—U1 | 114.5 (3) | C32—C31—U3 | 174.8 (17) |
O16vi—K2—U1 | 117.1 (3) | C31—C32—C33 | 120 (2) |
O16vii—K2—U1 | 117.1 (3) | C31—C32—H32A | 107.5 |
U3vi—K2—U1 | 132.90 (4) | C33—C32—H32A | 107.6 |
U3vii—K2—U1 | 132.90 (4) | C31—C32—H32B | 107.3 |
O3—K3—O7 | 112.0 (4) | C33—C32—H32B | 107.0 |
O3—K3—O14 | 92.0 (4) | H32A—C32—H32B | 106.9 |
O7—K3—O14 | 102.3 (4) | C32—C33—C34 | 109 (3) |
O3—K3—O4 | 61.4 (4) | C32—C33—H33A | 109.4 |
O7—K3—O4 | 164.2 (5) | C34—C33—H33A | 109.7 |
O14—K3—O4 | 92.5 (5) | C32—C33—H33B | 109.9 |
O3—K3—O15 | 152.4 (4) | C34—C33—H33B | 110.4 |
O7—K3—O15 | 82.7 (4) | H33A—C33—H33B | 108.3 |
O14—K3—O15 | 61.4 (3) | C33—C34—C35 | 95 (2) |
O4—K3—O15 | 109.6 (4) | C33—C34—H34A | 112.1 |
O3—K3—O8 | 103.8 (4) | C35—C34—H34A | 113.4 |
O7—K3—O8 | 60.3 (3) | C33—C34—H34B | 113.1 |
O14—K3—O8 | 159.8 (3) | C35—C34—H34B | 112.3 |
O4—K3—O8 | 106.0 (5) | H34A—C34—H34B | 110.0 |
O15—K3—O8 | 103.7 (4) | C34—C35—H35A | 108.8 |
O3—K3—U1 | 31.5 (3) | C34—C35—H35B | 110.3 |
O7—K3—U1 | 141.2 (3) | H35A—C35—H35B | 109.5 |
O14—K3—U1 | 93.9 (2) | C34—C35—H35C | 109.3 |
O4—K3—U1 | 30.0 (3) | H35A—C35—H35C | 109.5 |
O15—K3—U1 | 135.5 (3) | H35B—C35—H35C | 109.5 |
O8—K3—U1 | 106.2 (2) |
Symmetry codes: (i) −x, y, −z+3/2; (ii) x, −y, −z+2; (iii) x, −y, −z+1; (iv) −x+1, y, −z+3/2; (v) −x+1, −y, z−1/2; (vi) −x+1/2, y+1/2, −z+3/2; (vii) x−1/2, y+1/2, z; (viii) −x+1, −y, z+1/2; (ix) x+1/2, y−1/2, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [U(C5H9O2)2O2(H2O)2] | K[U(C5H9O2)3O2] |
Mr | 508.31 | 612.50 |
Crystal system, space group | Monoclinic, C2/m | Orthorhombic, C2221 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 7.782 (4), 10.802 (5), 9.512 (5) | 17.294 (3), 23.405 (4), 20.862 (3) |
α, β, γ (°) | 90, 104.885 (9), 90 | 90, 90, 90 |
V (Å3) | 772.7 (7) | 8444 (2) |
Z | 2 | 16 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 10.53 | 7.92 |
Crystal size (mm) | 0.21 × 0.11 × 0.08 | 0.24 × 0.15 × 0.03 |
Data collection | ||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1998) | Multi-scan (SADABS; Sheldrick, 1998) |
Tmin, Tmax | 0.261, 0.430 | 0.252, 0.797 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4876, 1187, 1187 | 37788, 10209, 8322 |
Rint | 0.068 | 0.072 |
(sin θ/λ)max (Å−1) | 0.703 | 0.661 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.059, 1.00 | 0.066, 0.193, 1.25 |
No. of reflections | 1187 | 10209 |
No. of parameters | 85 | 366 |
No. of restraints | 0 | 63 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.06, −2.05 | 2.77, −1.85 |
Absolute structure | ? | Flack (1983), with 4677 Friedel pairs |
Absolute structure parameter | ? | 0.061 (16) |
Computer programs: APEX2 (Bruker, 2005), SHELXTL (Sheldrick, 2008).
(I) | (II) | Assignment |
3374 (s, br) | νs(H2O), νas(H2O) | |
2960 (s) | 2960 s | νas(CH3) |
2933 (s) | 2935 s | νs(CH3) |
2873 (m) | 2873 m | νs(CH3) |
1634 (m) | δ(H2O) | |
1530 (sh) | 1534 vs | νas(COO) |
1501 (vs) | 1464 vs | δas(CH3) |
1468 (vs) | δas(CH3) | |
1426 (sh) | 1429 s | νs(COO) |
1412 (sh) | 1413 s | δ(CαH2) |
1381 (w) | 1379 w | δs(CH3) |
1364 (w) | 1361 w | ω(CαH2) |
1323 (m) | 1319 m | ω(CβH2) |
1300 (w) | 1297 w | ω(CβH2) |
1246 (w) | 1241 w | tw(CαH2) |
1204 (w) | 1199 w | tw(CβH2) |
1106 (m) | 1099 w | ν(CβCα) |
951 (vs) | 927 vs | νas(UO2) |
942 (sh) | νas(UO2) | |
868 (w) | 867 w | ν(CαC) |
761 (w) | 762 w | γ(CβH2) |
731 (w) | 720 w | γ(CβH2) |
685 (w) | 669 w | δ(COO) |
648 (w) | 649 w | δ(COO) |
Notes: vs = very strong, s = strong, m = medium, w = weak, br = broad and sh = shoulder. |
Uranyl carboxylates are used in the nuclear industry for decontamination of uranium (Haas & Northup, 2004). They occur in nature (Lenhart et al., 2000; Rosberg et al., 2000) and affect biological systems (Miller, 2009). In addition, uranyl complexes with organic ions can be used for the construction of uranyl–organic frameworks (Wang & Chen, 2011). To date, the structures of about 70 uranyl complexes with short monocarboxylates (formate, acetate, propionate, isobutyrate and crotonate) have been reported. Uranyl carboxylates with longer hydrocarbon chains are less well studied (Leciejewicz et al., 1995). In particular, the structures of valerate-containing uranyl complexes have not previously been analysed. However, the existence of several uranium(VI) compounds with n-valerate anions (n-C4H9COO) has been reported. Courtois (1914) described needle-like crystals formulated as [UO2(n-C4H9COO)2(H2O)2], which can release water molecules in dry air under heating. Rimbach (1904) synthesized K[UO2(n-C4H9COO)3(H2O)2] by the reaction of potassium diuranate and valeric acid in water. Here, we report the structures of two uranyl complexes with n-valerate anions, viz. [UO2(n-C4H9COO)2(H2O)2], (I), and K[UO2(n-C4H9COO)3], (II).
FT–IR spectroscopy reveals the presence of uranyl, bidentate–chelating carboxylate and alkyl groups in both compounds, as well as terminally coordinated water molecules in (I). The X-ray structure analyses show that (I) and (II) have one and three crystallographically independent UVI cations, respectively. In both complexes, the UVI cations adopt hexagonal–bipyramidal geometry, with the O atoms of the uranyl cations situated in the axial positions.
In (I), a number of atoms lie on symmetry elements: atom U1 is on a site of 2/m symmetry, water atom O1 lies on a twofold axis, and uranyl atoms O2 and O3, as well as atoms C1, C2 and C6, are on mirror planes. Most of the atoms in (I) are disordered, as shown in Fig. 1. We interpret the disorder assembly as consisting of two disorder groups, with atom O2 and its centrosymmetrically related congener belonging to one disorder group, and atom O3 and its symmetry relative to the other. The uranyl fragment UO2 in (I) is symmetrical [U1—O2 = 1.752 (9) Å and U1—O3 = 1.746 (11) Å] and linear. The equatorial plane consists of four O atoms from two chelating valerate anions and two aqua ligands, which are trans to each other. The discrete [UO2(C4H9COO)2(H2O)2] molecules in (I) form two-dimensional hydrogen-bonded motifs. Each of the two disordered congeners forms one hydrogen bond, O1—H1···O4(x + 1/2, y + 1/2, z) (H···O = 1.93 Å and O—H···O = 180°) and O1—H1···O5(-x + 5/2, -y + 1/2, -z + 2) (H···O = 2.20 Å and O—H···O = 129°). According to the criteria of Steiner (2002), these hydrogen bonds are of average strength.
In (II), only two of the three independent uranyl cations, U1O22+ and U2O22+ (Figs. 2a and 2b), which lie on twofold axes, are symmetrical [U1—O1 = 1.775 (12) Å, U2—O5 = 1.716 (11) Å, and O—U—O = 179.1 (10) and 180.0 (8)°, respectively]. Atom U3 occupies a general position (Fig. 2c), with a less symmetric U3O22+ cation [U3—O9 = 1.719 (12) Å, U3—O10 = 1.757 (12) Å and O9—U3—O10 = 179.2 (6)°]. In the equatorial plane of the uranyl cations in (II), there are six O atoms from three chelating valerate anions. The main structural unit of (II) is the anionic mononuclear complex [UO2(C4H9COO)3]-, which forms a three-dimensional framework by means of electrostatic interactions with the K+ cations (Fig. 3).
The Cambridge Structural Database (CSD, Version?; Allen, 2002) includes three anionic uranyl complexes K[UO2L3] which, like (II), possess alkyl monocarboxylate ligands L-. These are orthorhombic K[UO2(C3H7COO)3] [(III); Pushkin et al., 2012], cubic K[UO2(C2H5COO)3] [(IV); Serezhkina et al., 2013] and tetragonal K[UO2(CH3COO)3] [(V); Serezhkina et al., 2010]. Compounds (III)–(V) have bidentate–chelating n-butyrate, propionate and acetate ligands, respectively. The structure of (III) contains four independent U atoms (and K+ cations), whereas (IV) and (V) contain one independent U atom (and K+ cation) each. All K+ cations in (II)–(V) adopt distorted octahedral coordinations, except for one trigonal prismatic K+ cation in (III) (Pushkin et al., 2012). The three-dimensional frameworks in (II)–(V), which consist of K, U and O atoms, can be examined in a simple fashion by omitting from consideration the terminal groups (the hydrocarbon chains and the O atoms of the uranyl cations). The four frameworks in (II)–(V), of composition KUO6, have each U (K) atom connected to three K (U) atoms by double –O– bridges (Fig. 4). The bulky carboxylate anions fill the voids in these frameworks (Fig. 5). The peculiarities of the three-dimensional frameworks are then differentiated only by the steric characteristics and dispositions of the hydrocarbon residues and the manner in which the frameworks accommodate them.
It might be reasonable to expect that the minimum distance between U atoms in one of these structures, dUU, would become greater as the alkyl side chain progresses from shorter to longer. The minimum dUU does at first increase, from 6.53 to 7.38 Å, on going from acetate (V) to propionate (IV), but it then decreases to 6.41 Å in the butyrate compound (III) and further to 6.24 Å for valerate (II). We can understand this with reference to the concept of coordination spheres (CS) and coordination sequences. The CS's are successive neighbourhoods of topologically relevant atoms (U and K) around a central atom, here U. For example, in Fig. 4, R0 is the central atom, and the atoms labelled R1 are those of its first CS. The O atoms are bridges and, for the present purposes, are not counted as a CS. The CS's are compared using the further concept of coordination sequences CPN (O'Keeffe, 1995), which gives the number of atoms in the Nth CS around the central atom. We take U as the central atom for (II)–(V), so odd CS's consist only of K and even CS's are all U. Thus, CP shows the number of R atoms (R = K or U) of the Nth coordination shell which are connected to the central U atom through the R—(O—R—)N chains. If each R atom were connected to three other R atoms through O-atom bridges (Fig. 4), the number of atoms would double in successive CS's. The theoretical population of CS's for (II)–(V) would then be 3, 6, 12, 24, 48, 96, 192 etc. However, this avalanche-like increase of CPN is obviated by a steric factor. What actually occurs is that at some point two adjacent R—(O—R—)N chains share a common R atom (Fig. 6) to form a cyclic pattern. As a result, as linkages appear, the CPN values for (II)–(V) become smaller than the theoretically possible values. For acetate (V), this decrease starts from the fourth CS (Fig. 7, curve a) and eight-membered rings are formed; these would be 16-membered rings if O atoms were counted. From a topological point of view, the KUO6 framework in (V) represents a three-coordinated uninodal net of a rare 3/8/t7 type (Alexandrov et al., 2011). In cubic (IV) (propionate), the linkage of adjacent chains starts only in the fifth CS (Fig. 7, curve b). Accordingly, the cycles in the structure of (IV) contain at least ten atoms. The KUO6 framework in (IV) also represents a three-coordinated uninodal net, but of one of the most common topological types, srs (Hyde et al., 2008). In contrast with the uninodal nets in (IV) and (V), the KUO6 frameworks for valerate (II) and butyrate (III) represent more complicated three-coordinated 6-nodal nets. For the U1 atoms in (II) and (III), the linkage of chains starts from the fourth CS (Fig. 7, curve c), as in (V). But for atoms U2, U3 and U4 in (II) and (III), chain linkage begins in the third CS (Fig. 7, curves d and e), so that six-membered rings can also be found in the structures of these complexes. Evidently, the KUO6 frameworks in (II)–(V) are similar in the first CS, but rearrange and distort in subsequent CS's.
These differences in successive CS's allow the KUO6 frameworks to accommodate more or less voluminous groups. Since the voids in these structures are continuous and unbounded, it is not possible to determine their volumes. Instead, one can estimate the size of the largest sphere that can fit in the largest cavity in the KUO6 framework. For (II)–(V), the volumes of these spheres are 1062, 873, 312 and 349 Å3, respectively. Thus, the KUO6 frameworks in (II) and (III) provide more space for the voluminous valerate and butyrate anions through the formation of smaller six-membered rings in earlier CS's.
It is noteworthy that the propionate complex, (IV), which has the largest minimum rings (ten-membered) of all compounds (II)–(V), has the highest possible symmetry, cubic. It could be that, even in the absence of hydrocarbon chains, the KUO6 framework can not be constructed with larger minimum rings because it reaches the steric hindrance limit. Potassium uranyl propionate, (IV), may be an example of a system in which the hydrocarbon chains (–C3H5) fit well in the voids of such a highly symmetric three-dimensional framework. Smaller hydrocarbon chains [–C2H3 in (V)] require adjacent R—(O—R—)N chains to link earlier in order to approach one another. This could cause the lowering of the symmetry to tetragonal. Longer hydrocarbon chains [–C4H7 and –C5H9 in (III) and (II), respectively] do not fit the voids of such a symmetric framework, and it distorts to accommodate them. The distortion is manifested in the alternating interatomic U···U distances, an increase in the number of independent U atoms and K+ cations and even a change in coordination geometry around some of the K+ centres. The symmetry of (II) and (III) is lowered to orthorhombic. The variation of the KUO6 frameworks in these four compounds provides a new example of three-dimensional topological isomerism in coordination compounds of UVI.
The effect of alkyl group length in the K[UO2L3] homologous series on the characteristics of noncovalent interactions was analysed by means of a stereoatomic model of crystal structure (Serezhkin, 2007), based on Voronoi–Dirichlet polyhedra (VDP) descriptors (Blatov et al., 1995). This approach allows one to describe all types of interatomic interactions from a single point of view without using any system of crystal–chemical radii (Serezhkin et al., 2012). The VDP of a point – an atom in the present context – is a convex polyhedron of minimum volume, containing this atom and bounded by planes which are perpendicular bisectors of the line segments connecting this atom to all other atoms. Thus, each face of a VDP in a crystal structure belongs to two atoms A and B, and can be characterized by its `rank of interatomic contact' (RC) (Shevchenko & Serezhkin, 2004), which is the number of chemical bonds in the shortest chain connecting A and B. Thus, RC = 1 for all covalent bonds, and RC = 2 for A and B atoms in the chain A–D–B. If a face of the VDP of atom A is generated with atom B from another molecule (or chain or layer), the rank of the A···B contact is set to zero, because there is no bonding chain connecting A and B. According to this approach, all faces with RC ≥ 2 correspond to different types of non-covalent intramolecular interactions, and the partial contributions of each type can be unambiguously estimated by calculating the relative surface areas of the corresponding faces of the VDP. Our calculations on (II)–(V) showed that the partial contribution of the H···H dispersion interactions increases significantly through the series from the acetate to the valerate derivatives (Fig. 8). Thus, in acetate (V), only 28.5% of noncovalent interactions correspond to H···H contacts, whereas for (IV), (III) and (II) these valuee are 42.6, 57.6 and 60.5%, respectively. On the other hand, the surface areas corresponding to H···O hydrogen bonds and O···O dispersion interactions decrease in this sequence. The respective partial contributions for H···O and O···O contacts are 41.3 and 15.8% in (V), 35.2 and 9.8% in (IV), 22.0 and 9.1% in (III), and 19.6 and 7.7% in (II). The partial contributions of noncovalent H···C interactions in (II)–(V) are almost the same (8.7% on average) and those of the remaining types of contacts (C···C, C···O etc.) do not exceed 4%.