Di­aqua­tris­(pentane-2,4-dionato-O,O')­holmium(III) mono­hydrate and di­aqua­tris­(pentane-2,4-dionato-O,O')holmium(III) 4-hydroxy­pentan-2-one solvate dihydrate

The structures of the title compounds, [Ho(C₅H₇O₂)₃(H₂O)₂]·H₂O and [Ho(C₅H₇O₂)₃(H₂O)₂]·C₅H₈O₂·2H₂O, both show an eight-coordinate holmium(III) ion in a square antiprismatic configuration. The packing of these structures consists of an infinite two-dimensional network of hydrogen-bonded mol­ecules. In both structures, the same hydrogen-bonded chain of Ho^III complexes is found.

S1. Comment

Holmium in the trivalent state, like other rare earths, reacts with acetylacetonate (pentane-2,4-dione) to form a complex coordinated with three acetylacetonate ligands and one or two water molecules (Stites et al., 1948; Brown et al., 1960). The crystal structure of diaquatris(pentane-2,4-dionato-O,O')holmium(III) monohydrate was reported by Aslanov (1971) with R = 0.13, but no further data are available from the Cambridge Structural Database (Version? Ref?). The pentanedione–Ho complex is essential for the development of a new intra-arterial radionuclide therapy for the treatment of liver metastases (Nijsen et al., 1999). For the preparation of microspheres embedded with holmium we needed a stable hydrophobic holmium complex which can be incorporated easily and in high concentration into poly(L-lactic acid) (PLA) microspheres. This study reports structural data on the holmium acetylacetonate complex, which was chosen for further investigation because it has the above mentioned properties.

The holmium acetylacetonate complex showed a high chemical stability in PLA microspheres before and after irradiation in a nuclear reactor. Release of neutron-activated holmium from the microspheres is < 1.6% after 192 h incubation in liver homogenate. As the incorporation of holmium in PLA microspheres can be as high as 17% w/w, holmium-loaded microspheres are therefore suitable for selective internal radionuclide therapy. Neutron-activated ¹⁶⁶Ho is a β emitter which can be used for treatment of liver metastases. It also emits γ photons that can be used for imaging the distribution of activity in the patient. Owing to the high selectivity of the technique by which it is administered, the radiation is mainly restricted to the tumour.

Crystals of diaquatris(pentane-2,4-dionato-O,O')holmium(III) were obtained under different experimental conditions, such as pH (see Experimental). The crystal structures were determined to identify unambiguously the composition of the materials obtained. Two of these structures are presented here, namely, diaquatris(pentane-2,4-dionato-O,O')holmium(III) monohydrate, (I), and diaquatris(pentane-2,4-dionato-O,O')holmium(III) 4-hydroxypentan-2-one solvate dihydrate, (II), obtained at pH 8.5 and 9.0, respectively.

In both structures, the Ho^III displays square antiprismatic coordination by eight O atoms. There are no significant differences between the geometric parameters of these complexes.

In structure (II), hydrogen bonds between the complexes join them into a chain running in the [010] direction. A link between two Ho atoms is formed either by a hydrogen-bonded motif with graph set R₂²(8) or by two symmetry-related motifs, each with graph set R₂²(6) (Bernstein et al., 1995). Two non-coordinating water molecules and a free 4-hydroxypentan-2-one molecule also form a hydrogen-bonded chain in the [010] direction. This solvent chain donates three hydrogen bonds to the oxygen atoms coordinated to Ho and accepts one hydrogen bond from a coordinated water molecule, thus forming a two-dimensional network in the (010) plane (see Fig. 3). The hydroxyl atom of the 4-hydroxypentan-2-one is disordered over two positions. The minor position forms a bifurcated intra/intermolecular hydrogen bond, whereas the major component forms only an intermolecular hydrogen bond.

In structure (I), the complexes are joined by hydrogen bonds into an infinite one-dimensional chain running in the [101] direction. This chain is identical to that found in structure (II). The non-coordinating water molecule links these chains in a two-dimensional network in the (010) plane. One of the H atoms of this water molecule is disordered over two positions, in both of which it forms hydrogen bonds.

S2. Experimental

Pentane-2,4-dione (180 g, 1.80 mol) was dissolved in water (1080 g, 59.34 mol), followed by addition of ammonium hydroxide (28% w/w) until a solution of pH 8.5 was reached. Holmium chloride hexahydrate (10 g, 26.4 mmol) in water (30 g, 1.64 mol) was then added to the solution, yielding yellow crystals (pink under fluorescent lighting) of (I) after 24 h at room temperature. Satisfactory spectroscopic data (¹H NMR, ¹³C NMR and IR) were obtained. At pH 9.0 crystals of (II) were obtained, which were also yellow in daylight and pink under fluorescent lighting.

S3. Refinement

For both structures, H atoms bonded to O were located on difference Fourier maps and their coordinates were included as parameters in the refinement. Distance restraints were applied to ensure reasonable intramolecular geometries. Methyl-H atoms were located from difference Fourier syntheses and refined as part of a rigid group allowed to rotate around the C—C bond but not tip or distort. All other H atoms were introduced at calculated positions, riding on their carrier atoms. The high uncertainties shown by some of the data given in Tables 2 and 4 are due to H95 and H96 being disordered components. The occupation ratio of the disordered H atom of (I) was fixed; the occupation ratio of the disordered H atom of (II) was refined. Displacement parameters of all H atoms were related to their carrier atom by a fixed constant. The highest peak of 1.66 Å⁻³ in the difference Fourier synthesis was located 1.07 Å from Ho1; the deepest trough of −1.96 Å⁻³ was 0.92 Å from the same position.

Computing details

Data collection: COLLECT (Nonius, 1997) for (I); locally modified CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) for (I); SET4 (de Boer & Duisenberg, 1984) for (II). Data reduction: DENZO-SMN for (I); HELENA (Spek, 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: PLATON.

Figures

	Fig. 1. Displacement ellipsoid plot (Spek, 1990) of (I), showing the atomic labelling scheme and 50% probability displacement ellipsoids. H atoms and the non-coordinating water molecule have been omitted for clarity.
	Fig. 2. Displacement ellipsoid plot (Spek, 1990) of (II), showing the atomic labelling scheme and 50% probability displacement ellipsoids. H atoms and the non-coordinating water molecule have been omitted for clarity.
	Fig. 3. Crystal packing diagram for (II). The hydrogen-bonded chain of solvent molecules has been accentuated by using solid bonds. Methyl groups and H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) Diaquatris(pentane-2,4-dionato-O,O')holmium(III) monohydrate

Crystal data

[Ho(C5H7O2)3(H2O)2]·H2O	F(000) = 1024
Mr = 516.30	Dx = 1.744 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 447 reflections
a = 8.242 (2) Å	θ = 2.0–25.0°
b = 21.782 (6) Å	µ = 4.07 mm^−1
c = 12.557 (3) Å	T = 150 K
β = 119.292 (14)°	Needle, yellow-pink
V = 1966.1 (9) Å^3	0.35 × 0.08 × 0.03 mm
Z = 4

Data collection

Nonius Kappa-CCD diffractometer	3548 independent reflections
Radiation source: rotating anode	2947 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
Detector resolution: 18.4 pixels mm^-1	θmax = 25.2°, θmin = 1.9°
area detector ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (Spek, 1990)	k = −25→26
Tmin = 0.614, Tmax = 0.855	l = −15→13
15088 measured reflections

Refinement

Refinement on F^2	11 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.027P)^2 + 9.5P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.099	(Δ/σ)max = 0.002
S = 1.15	Δρmax = 1.19 e Å^−3
3548 reflections	Δρmin = −1.51 e Å^−3
254 parameters

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ho1	0.15075 (4)	0.02902 (1)	0.77056 (3)	0.0205 (1)
O1	0.2537 (6)	−0.0663 (2)	0.8708 (4)	0.0276 (17)
O2	−0.0779 (6)	−0.0425 (2)	0.6565 (4)	0.0290 (16)
O3	0.2452 (6)	0.0527 (2)	0.9773 (4)	0.0285 (16)
O4	−0.0995 (6)	0.0718 (2)	0.7813 (4)	0.0282 (14)
O5	0.2563 (6)	0.1284 (2)	0.7856 (4)	0.0272 (14)
O6	−0.0497 (6)	0.0789 (2)	0.5801 (4)	0.0244 (16)
O7	0.4873 (6)	0.0317 (2)	0.8751 (4)	0.0252 (14)
O8	0.2527 (6)	−0.0093 (2)	0.6371 (4)	0.0273 (14)
C1	0.3454 (11)	−0.1699 (3)	0.9180 (7)	0.037 (2)
C2	0.2168 (9)	−0.1211 (3)	0.8345 (6)	0.0240 (19)
C3	0.0613 (9)	−0.1393 (3)	0.7243 (6)	0.0226 (17)
C4	−0.0776 (9)	−0.0999 (3)	0.6421 (6)	0.0249 (19)
C5	−0.2402 (10)	−0.1268 (3)	0.5296 (6)	0.031 (2)
C6	0.3113 (11)	0.1010 (4)	1.1620 (7)	0.042 (3)
C7	0.1931 (10)	0.0928 (3)	1.0264 (6)	0.029 (2)
C8	0.0320 (10)	0.1279 (3)	0.9644 (6)	0.032 (2)
C9	−0.1096 (9)	0.1149 (3)	0.8461 (6)	0.030 (2)
C10	−0.2882 (10)	0.1514 (4)	0.7905 (7)	0.036 (3)
C11	0.2831 (11)	0.2361 (4)	0.7963 (8)	0.043 (3)
C12	0.1763 (10)	0.1789 (3)	0.7374 (7)	0.029 (2)
C13	−0.0005 (9)	0.1839 (3)	0.6349 (6)	0.027 (2)
C14	−0.1036 (9)	0.1340 (3)	0.5633 (6)	0.0245 (19)
C15	−0.2921 (9)	0.1476 (4)	0.4550 (6)	0.031 (2)
O9	0.5699 (7)	0.0149 (3)	0.6226 (5)	0.0415 (19)
H11	0.47440	−0.15570	0.95380	0.0550*
H12	0.32990	−0.20760	0.87120	0.0550*
H13	0.31550	−0.17820	0.98310	0.0550*
H31	0.04970	−0.18170	0.70410	0.0270*
H51	−0.35530	−0.11920	0.53240	0.0470*
H52	−0.22200	−0.17110	0.52710	0.0470*
H53	−0.24880	−0.10750	0.45660	0.0470*
H61	0.29480	0.14270	1.18460	0.0630*
H62	0.44230	0.09460	1.18560	0.0630*
H63	0.27400	0.07110	1.20440	0.0630*
H74	0.558 (9)	0.005 (2)	0.908 (6)	0.0380*
H75	0.530 (9)	0.057 (2)	0.927 (5)	0.0380*
H81	0.01780	0.16270	1.00480	0.0390*
H84	0.341 (7)	−0.003 (4)	0.631 (6)	0.0410*
H85	0.190 (9)	−0.028 (3)	0.577 (5)	0.0410*
H101	−0.26670	0.19080	0.83300	0.0540*
H102	−0.38380	0.12840	0.79840	0.0540*
H103	−0.33000	0.15880	0.70390	0.0540*
H111	0.20490	0.27200	0.75700	0.0650*
H112	0.39450	0.23780	0.78720	0.0650*
H113	0.31980	0.23590	0.88320	0.0650*
H131	−0.05410	0.22370	0.61240	0.0320*
H151	−0.33380	0.18820	0.46500	0.0470*
H152	−0.38150	0.11650	0.44990	0.0470*
H153	−0.28310	0.14680	0.38010	0.0470*
H94	0.647 (10)	0.038 (4)	0.668 (8)	0.0620*
H95	0.620 (16)	0.000 (8)	0.589 (14)	0.0620*	0.500
H96	0.626 (15)	−0.016 (3)	0.640 (16)	0.0620*	0.500

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ho1	0.0172 (2)	0.0263 (2)	0.0146 (2)	0.0005 (1)	0.0052 (1)	−0.0004 (1)
O1	0.026 (3)	0.030 (3)	0.024 (3)	−0.003 (2)	0.010 (2)	−0.003 (2)
O2	0.020 (2)	0.033 (3)	0.025 (3)	−0.002 (2)	0.004 (2)	−0.004 (2)
O3	0.023 (3)	0.042 (3)	0.017 (2)	0.005 (2)	0.007 (2)	−0.004 (2)
O4	0.021 (2)	0.041 (3)	0.019 (2)	0.001 (2)	0.007 (2)	−0.001 (2)
O5	0.020 (2)	0.034 (3)	0.022 (2)	0.004 (2)	0.006 (2)	0.002 (2)
O6	0.026 (3)	0.027 (3)	0.018 (2)	0.003 (2)	0.009 (2)	0.002 (2)
O7	0.018 (2)	0.032 (3)	0.018 (2)	0.005 (2)	0.003 (2)	0.002 (2)
O8	0.017 (2)	0.045 (3)	0.016 (2)	−0.002 (2)	0.005 (2)	−0.003 (2)
C1	0.034 (4)	0.036 (4)	0.034 (4)	−0.001 (3)	0.011 (4)	0.003 (3)
C2	0.021 (3)	0.035 (4)	0.016 (3)	0.001 (3)	0.009 (3)	0.002 (3)
C3	0.018 (3)	0.023 (3)	0.020 (3)	−0.006 (3)	0.004 (3)	−0.004 (3)
C4	0.020 (3)	0.039 (4)	0.015 (3)	−0.005 (3)	0.008 (3)	−0.004 (3)
C5	0.030 (4)	0.038 (4)	0.022 (4)	−0.005 (3)	0.010 (3)	−0.001 (3)
C6	0.037 (4)	0.060 (6)	0.026 (4)	0.007 (4)	0.013 (4)	−0.013 (4)
C7	0.027 (4)	0.037 (4)	0.024 (4)	−0.002 (3)	0.013 (3)	0.000 (3)
C8	0.033 (4)	0.039 (4)	0.024 (4)	0.007 (3)	0.013 (3)	−0.006 (3)
C9	0.022 (4)	0.040 (4)	0.026 (4)	0.007 (3)	0.011 (3)	0.009 (3)
C10	0.025 (4)	0.058 (5)	0.028 (4)	0.012 (4)	0.016 (3)	0.003 (4)
C11	0.033 (4)	0.033 (4)	0.048 (5)	0.003 (3)	0.008 (4)	−0.002 (4)
C12	0.027 (4)	0.033 (4)	0.029 (4)	0.000 (3)	0.016 (3)	−0.004 (3)
C13	0.025 (4)	0.029 (4)	0.026 (4)	0.007 (3)	0.012 (3)	0.003 (3)
C14	0.020 (3)	0.039 (4)	0.017 (3)	0.003 (3)	0.011 (3)	0.004 (3)
C15	0.021 (4)	0.043 (4)	0.021 (4)	0.005 (3)	0.003 (3)	0.004 (3)
O9	0.020 (3)	0.068 (4)	0.027 (3)	−0.005 (3)	0.004 (2)	−0.009 (3)

Geometric parameters (Å, º)

Ho1—O1	2.360 (4)	C8—C9	1.397 (10)
Ho1—O2	2.321 (5)	C9—C10	1.510 (12)
Ho1—O3	2.374 (5)	C11—C12	1.496 (11)
Ho1—O4	2.327 (5)	C12—C13	1.399 (11)
Ho1—O5	2.306 (5)	C13—C14	1.402 (10)
Ho1—O6	2.401 (4)	C14—C15	1.511 (10)
Ho1—O7	2.420 (5)	C1—H13	0.9792
Ho1—O8	2.364 (5)	C1—H11	0.9800
O1—C2	1.261 (8)	C1—H12	0.9811
O2—C4	1.263 (8)	C3—H31	0.9501
O3—C7	1.260 (9)	C5—H51	0.9804
O4—C9	1.271 (8)	C5—H52	0.9794
O5—C12	1.273 (8)	C5—H53	0.9790
O6—C14	1.261 (8)	C6—H63	0.9810
O7—H75	0.79 (5)	C6—H62	0.9798
O7—H74	0.78 (6)	C6—H61	0.9807
O8—H84	0.78 (7)	C8—H81	0.9506
O8—H85	0.79 (6)	C10—H101	0.9799
O9—H96	0.78 (10)	C10—H102	0.9789
O9—H95	0.79 (16)	C10—H103	0.9801
O9—H94	0.79 (9)	C11—H113	0.9794
C1—C2	1.505 (10)	C11—H111	0.9794
C2—C3	1.407 (10)	C11—H112	0.9799
C3—C4	1.399 (10)	C13—H131	0.9510
C4—C5	1.511 (10)	C15—H151	0.9789
C6—C7	1.502 (10)	C15—H152	0.9797
C7—C8	1.394 (11)	C15—H153	0.9791
Ho1···O9^i	4.214 (7)	H11···H62^ii	2.5461
Ho1···O7^ii	4.178 (5)	H12···H31	2.3049
Ho1···H95^i	3.87 (16)	H13···H101^vii	2.5453
Ho1···H96^i	3.93 (16)	H13···C10^vii	3.0165
Ho1···H94^i	3.70 (10)	H31···H111^vi	2.5811
Ho1···H53^iii	3.7373	H31···H12	2.3049
Ho1···H74^ii	3.62 (7)	H31···H52	2.2666
Ho1···H75^ii	3.88 (5)	H51···C15^ix	3.0501
Ho1···H85^iii	3.87 (6)	H51···H152^ix	2.2870
O1···O7^ii	2.940 (6)	H52···H31	2.2666
O2···O9^i	2.994 (8)	H53···O6^iii	2.7862
O3···O7^ii	2.771 (7)	H53···Ho1^iii	3.7373
O4···C13	3.388 (9)	H53···O8^iii	2.7966
O4···O9^i	2.760 (8)	H53···C14^iii	3.0890
O6···O8^iii	2.841 (6)	H61···H81	2.3357
O7···O1^ii	2.940 (6)	H61···H111^x	2.3424
O7···Ho1^ii	4.178 (5)	H61···C11^x	3.0130
O7···O3^ii	2.771 (7)	H62···C2^ii	2.9975
O8···O6^iii	2.841 (6)	H62···H11^ii	2.5461
O8···O9	2.759 (9)	H62···H74^ii	2.4668
O8···C15^iii	3.299 (10)	H63···O9^ii	2.6737
O9···O8	2.759 (9)	H63···H96^ii	2.0884
O9···O9^iv	2.785 (8)	H74···O3^ii	2.00 (6)
O9···O4^v	2.760 (8)	H74···C6^ii	2.86 (6)
O9···Ho1^v	4.214 (6)	H74···C7^ii	2.79 (6)
O9···O2^v	2.994 (8)	H74···H62^ii	2.4668
O1···H74^ii	2.77 (6)	H74···O1^ii	2.77 (6)
O1···H75^ii	2.29 (6)	H74···Ho1^ii	3.62 (7)
O2···H96^i	2.42 (15)	H75···Ho1^ii	3.88 (5)
O2···H95^i	2.39 (16)	H75···H102^v	2.5795
O3···H74^ii	2.00 (6)	H75···O1^ii	2.29 (6)
O3···H75^ii	2.90 (5)	H75···O3^ii	2.90 (5)
O4···H95^i	2.86 (16)	H75···C1^ii	2.99 (5)
O4···H94^i	2.01 (9)	H75···C2^ii	3.03 (5)
O4···H96^i	2.83 (13)	H81···H61	2.3357
O5···H102^v	2.8911	H81···H101	2.3616
O6···H53^iii	2.7862	H84···O9	1.98 (7)
O6···H85^iii	2.06 (6)	H84···H96	2.31 (17)
O7···H102^v	2.7375	H84···H95	2.60 (17)
O8···H53^iii	2.7966	H84···H94	2.50 (12)
O9···H63^ii	2.6737	H85···O6^iii	2.06 (6)
O9···H84	1.98 (7)	H85···C14^iii	2.78 (6)
O9···H95^iv	2.35 (15)	H85···Ho1^iii	3.87 (6)
O9···H96^iv	2.88 (18)	H85···C15^iii	2.83 (7)
C3···C15^iii	3.593 (11)	H94···Ho1^v	3.70 (10)
C5···C14^iii	3.557 (12)	H94···H84	2.50 (12)
C9···C12	3.536 (12)	H94···C10^v	2.82 (9)
C9···C14	3.600 (10)	H94···O4^v	2.01 (9)
C9···C13	3.526 (10)	H94···C9^v	2.73 (9)
C12···C9	3.536 (12)	H95···O2^v	2.39 (16)
C13···C9	3.526 (10)	H95···Ho1^v	3.87 (16)
C13···O4	3.388 (9)	H95···O9^iv	2.35 (15)
C14···C9	3.600 (10)	H95···O4^v	2.86 (16)
C14···C5^iii	3.557 (12)	H95···H84	2.60 (17)
C15···C3^iii	3.593 (11)	H96···C4^v	3.04 (13)
C15···O8^iii	3.299 (10)	H96···Ho1^v	3.93 (16)
C1···H113^ii	3.0286	H96···O2^v	2.42 (15)
C1···H75^ii	2.99 (5)	H96···O4^v	2.83 (13)
C2···H75^ii	3.03 (5)	H96···C6^ii	2.94 (14)
C2···H62^ii	2.9975	H96···H84	2.31 (17)
C2···H153^iii	3.0520	H96···O9^iv	2.88 (18)
C3···H111^vi	3.0176	H96···H63^ii	2.0884
C3···H153^iii	2.7262	H101···H81	2.3616
C4···H96^i	3.04 (13)	H101···H13^vii	2.5453
C6···H74^ii	2.86 (6)	H102···H75^i	2.5795
C6···H11^ii	3.0277	H102···O5^i	2.8911
C6···H96^ii	2.94 (14)	H102···O7^i	2.7375
C7···H74^ii	2.79 (6)	H111···H131	2.2733
C7···H11^ii	2.9635	H111···C3^xi	3.0176
C9···H94^i	2.73 (9)	H111···H31^xi	2.5811
C10···H94^i	2.82 (9)	H111···H61^viii	2.3424
C10···H13^vii	3.0165	H113···H11^ii	2.5925
C11···H61^viii	3.0130	H113···C1^ii	3.0286
C14···H85^iii	2.78 (6)	H131···H151	2.2722
C14···H53^iii	3.0890	H131···H111	2.2733
C15···H51^ix	3.0501	H151···H131	2.2722
C15···H85^iii	2.83 (7)	H152···H51^ix	2.2870
H11···C6^ii	3.0277	H153···C3^iii	2.7262
H11···H113^ii	2.5925	H153···C2^iii	3.0520
H11···C7^ii	2.9635
O1—Ho1—O2	73.15 (16)	C7—C8—C9	123.7 (6)
O1—Ho1—O3	76.58 (15)	C8—C9—C10	120.2 (6)
O1—Ho1—O4	114.77 (17)	O4—C9—C8	123.2 (7)
O1—Ho1—O5	139.41 (17)	O4—C9—C10	116.6 (6)
O1—Ho1—O6	145.29 (15)	C11—C12—C13	119.1 (6)
O1—Ho1—O7	73.40 (17)	O5—C12—C11	116.2 (7)
O1—Ho1—O8	84.71 (16)	O5—C12—C13	124.7 (6)
O2—Ho1—O3	123.61 (17)	C12—C13—C14	124.2 (6)
O2—Ho1—O4	80.18 (17)	C13—C14—C15	117.3 (6)
O2—Ho1—O5	147.18 (16)	O6—C14—C15	117.4 (6)
O2—Ho1—O6	74.56 (16)	O6—C14—C13	125.3 (7)
O2—Ho1—O7	136.04 (16)	C2—C1—H11	109.44
O2—Ho1—O8	77.79 (18)	C2—C1—H12	109.45
O3—Ho1—O4	71.05 (17)	C2—C1—H13	109.44
O3—Ho1—O5	78.33 (16)	H11—C1—H12	109.45
O3—Ho1—O6	133.54 (16)	H11—C1—H13	109.57
O3—Ho1—O7	74.10 (17)	H12—C1—H13	109.47
O3—Ho1—O8	144.28 (18)	C4—C3—H31	117.41
O4—Ho1—O5	85.92 (18)	C2—C3—H31	117.44
O4—Ho1—O6	71.28 (17)	C4—C5—H51	109.40
O4—Ho1—O7	140.55 (16)	C4—C5—H52	109.41
O4—Ho1—O8	144.60 (16)	C4—C5—H53	109.49
O5—Ho1—O6	72.84 (16)	H52—C5—H53	109.58
O5—Ho1—O7	69.31 (17)	H51—C5—H53	109.45
O5—Ho1—O8	97.98 (17)	H51—C5—H52	109.49
O6—Ho1—O7	125.23 (17)	C7—C6—H63	109.55
O6—Ho1—O8	76.33 (17)	C7—C6—H62	109.48
O7—Ho1—O8	71.49 (16)	H62—C6—H63	109.45
Ho1—O1—C2	132.8 (4)	H61—C6—H62	109.42
Ho1—O2—C4	134.0 (5)	H61—C6—H63	109.46
Ho1—O3—C7	132.7 (4)	C7—C6—H61	109.47
Ho1—O4—C9	132.1 (5)	C7—C8—H81	118.15
Ho1—O5—C12	133.3 (5)	C9—C8—H81	118.17
Ho1—O6—C14	127.7 (4)	C9—C10—H102	109.55
Ho1—O7—H75	113 (6)	H101—C10—H103	109.39
H74—O7—H75	100 (6)	C9—C10—H103	109.48
Ho1—O7—H74	129 (5)	H101—C10—H102	109.46
Ho1—O8—H84	133 (6)	C9—C10—H101	109.49
H84—O8—H85	102 (8)	H102—C10—H103	109.46
Ho1—O8—H85	125 (6)	C12—C11—H113	109.48
H94—O9—H96	101 (13)	H111—C11—H112	109.53
H94—O9—H95	102 (14)	H112—C11—H113	109.50
H95—O9—H96	54 (17)	C12—C11—H112	109.40
O1—C2—C1	117.0 (6)	H111—C11—H113	109.47
C1—C2—C3	118.6 (6)	C12—C11—H111	109.45
O1—C2—C3	124.4 (6)	C12—C13—H131	117.89
C2—C3—C4	125.2 (6)	C14—C13—H131	117.95
O2—C4—C5	117.0 (6)	C14—C15—H153	109.47
O2—C4—C3	124.0 (6)	H151—C15—H153	109.61
C3—C4—C5	118.9 (6)	H152—C15—H153	109.45
O3—C7—C8	124.5 (6)	H151—C15—H152	109.45
O3—C7—C6	116.7 (7)	C14—C15—H151	109.43
C6—C7—C8	118.7 (7)	C14—C15—H152	109.42
O2—Ho1—O1—C2	24.1 (7)	O7—Ho1—O5—C12	169.0 (7)
O3—Ho1—O1—C2	155.9 (7)	O8—Ho1—O5—C12	102.3 (7)
O4—Ho1—O1—C2	94.4 (7)	O1—Ho1—O6—C14	162.2 (6)
O5—Ho1—O1—C2	−150.9 (6)	O2—Ho1—O6—C14	140.1 (7)
O6—Ho1—O1—C2	1.8 (9)	O3—Ho1—O6—C14	18.1 (7)
O7—Ho1—O1—C2	−127.0 (7)	O4—Ho1—O6—C14	55.5 (6)
O8—Ho1—O1—C2	−54.8 (7)	O5—Ho1—O6—C14	−36.0 (6)
O1—Ho1—O2—C4	−26.1 (6)	O7—Ho1—O6—C14	−83.9 (7)
O3—Ho1—O2—C4	−86.6 (7)	O8—Ho1—O6—C14	−139.0 (7)
O4—Ho1—O2—C4	−145.9 (6)	Ho1—O1—C2—C1	165.0 (5)
O5—Ho1—O2—C4	147.8 (6)	Ho1—O1—C2—C3	−17.3 (12)
O6—Ho1—O2—C4	141.0 (7)	Ho1—O2—C4—C3	21.0 (11)
O7—Ho1—O2—C4	15.8 (7)	Ho1—O2—C4—C5	−160.1 (5)
O8—Ho1—O2—C4	62.0 (6)	Ho1—O3—C7—C6	−168.9 (5)
O1—Ho1—O3—C7	−151.1 (7)	Ho1—O3—C7—C8	13.3 (12)
O2—Ho1—O3—C7	−92.2 (7)	Ho1—O4—C9—C10	150.1 (5)
O4—Ho1—O3—C7	−28.6 (7)	Ho1—O4—C9—C8	−31.8 (10)
O5—Ho1—O3—C7	61.0 (7)	Ho1—O5—C12—C11	163.6 (6)
O6—Ho1—O3—C7	8.8 (8)	Ho1—O5—C12—C13	−16.8 (12)
O7—Ho1—O3—C7	132.6 (7)	Ho1—O6—C14—C13	32.1 (11)
O8—Ho1—O3—C7	148.5 (6)	Ho1—O6—C14—C15	−149.8 (5)
O1—Ho1—O4—C9	102.5 (6)	C1—C2—C3—C4	175.0 (8)
O2—Ho1—O4—C9	168.7 (6)	O1—C2—C3—C4	−2.7 (13)
O3—Ho1—O4—C9	37.9 (5)	C2—C3—C4—C5	−177.7 (8)
O5—Ho1—O4—C9	−41.1 (6)	C2—C3—C4—O2	1.2 (13)
O6—Ho1—O4—C9	−114.4 (6)	C6—C7—C8—C9	−164.6 (8)
O7—Ho1—O4—C9	8.8 (7)	O3—C7—C8—C9	13.0 (13)
O8—Ho1—O4—C9	−139.2 (5)	C7—C8—C9—C10	173.7 (8)
O1—Ho1—O5—C12	−166.5 (6)	C7—C8—C9—O4	−4.2 (12)
O2—Ho1—O5—C12	22.5 (8)	O5—C12—C13—C14	−7.8 (14)
O3—Ho1—O5—C12	−113.8 (7)	C11—C12—C13—C14	171.8 (8)
O4—Ho1—O5—C12	−42.3 (7)	C12—C13—C14—C15	−179.6 (7)
O6—Ho1—O5—C12	29.4 (7)	C12—C13—C14—O6	−1.5 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H74···O3^ii	0.78 (6)	2.00 (6)	2.771 (7)	168 (6)
O7—H75···O1^ii	0.79 (5)	2.29 (6)	2.940 (6)	140 (5)
O8—H84···O9	0.78 (7)	1.98 (7)	2.759 (9)	177 (7)
O8—H85···O6^iii	0.79 (6)	2.06 (6)	2.841 (6)	174 (8)
O9—H94···O4^v	0.79 (9)	2.01 (9)	2.760 (8)	159 (9)
O9—H95···O2^v	0.79 (16)	2.39 (16)	2.994 (8)	134 (14)
O9—H95···O9^iv	0.79 (16)	2.35 (15)	2.785 (8)	115 (13)
O9—H96···O2^v	0.78 (10)	2.42 (15)	2.994 (8)	131 (12)

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

(II) diaquatris(pentane-2,4-dionato-O,O')holmium(III) 4-hydroxypentan-2-one solvate dihydrate

Crystal data

[Ho(C5H7O2)3(H2O)2]·C5H8O2·H2O	F(000) = 1280
Mr = 634.43	Dx = 1.622 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.4903 (11) Å	θ = 11.5–18.4°
b = 11.0242 (6) Å	µ = 3.10 mm^−1
c = 20.5442 (15) Å	T = 293 K
β = 93.440 (7)°	Needle, yellow-pink
V = 2597.7 (3) Å^3	0.70 × 0.20 × 0.05 mm
Z = 4

Data collection

Enraf-Nonius CAD-4T diffractometer	3764 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.041
Graphite monochromator	θmax = 25.3°, θmin = 1.8°
ω scan	h = −13→13
Absorption correction: gaussian (Spek, 1990)	k = 0→13
Tmin = 0.517, Tmax = 0.857	l = −24→24
9388 measured reflections	3 standard reflections every 60 min
4697 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	10 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.032	w = 1/[σ^2(Fo2) + (0.02P)^2 + 5P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.069	(Δ/σ)max = 0.002
S = 1.17	Δρmax = 1.66 e Å^−3
4697 reflections	Δρmin = −1.96 e Å^−3
338 parameters

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ho1	0.09895 (1)	0.25600 (2)	0.01737 (1)	0.0133 (1)
O1	0.1774 (3)	0.0628 (3)	−0.00892 (15)	0.0178 (9)
O2	0.2035 (2)	0.2780 (3)	−0.07590 (14)	0.0186 (9)
O3	0.0480 (3)	0.1236 (3)	0.09768 (15)	0.0205 (10)
O4	−0.0277 (3)	0.3622 (3)	0.08201 (15)	0.0192 (9)
O5	0.2687 (2)	0.2352 (3)	0.08184 (14)	0.0208 (9)
O6	0.1888 (3)	0.4502 (3)	0.02913 (15)	0.0176 (9)
O7	−0.0631 (3)	0.1521 (3)	−0.03122 (16)	0.0202 (10)
O8	−0.0093 (3)	0.3934 (3)	−0.05510 (15)	0.0170 (9)
C1	0.3268 (4)	−0.0835 (5)	−0.0139 (3)	0.0274 (17)
C2	0.2772 (4)	0.0399 (4)	−0.0288 (2)	0.0178 (12)
C3	0.3420 (4)	0.1201 (5)	−0.0651 (2)	0.0228 (14)
C4	0.3009 (4)	0.2307 (4)	−0.0894 (2)	0.0196 (14)
C5	0.3713 (4)	0.3001 (5)	−0.1365 (3)	0.0289 (17)
C6	−0.0520 (4)	−0.0030 (5)	0.1689 (2)	0.0265 (17)
C7	−0.0355 (4)	0.1160 (4)	0.1353 (2)	0.0187 (14)
C8	−0.1103 (4)	0.2125 (5)	0.1479 (2)	0.0216 (14)
C9	−0.1014 (4)	0.3282 (4)	0.1233 (2)	0.0192 (14)
C10	−0.1795 (4)	0.4264 (5)	0.1470 (2)	0.0271 (17)
C11	0.4608 (4)	0.2267 (5)	0.1270 (3)	0.0319 (16)
C12	0.3650 (4)	0.2911 (4)	0.0881 (2)	0.0202 (14)
C13	0.3838 (4)	0.4076 (5)	0.0644 (2)	0.0219 (14)
C14	0.2942 (4)	0.4832 (4)	0.0399 (2)	0.0179 (12)
C15	0.3210 (4)	0.6141 (5)	0.0269 (3)	0.0262 (17)
O9	0.2122 (4)	0.5464 (5)	0.1861 (2)	0.0412 (14)
O10	0.1587 (3)	0.7770 (3)	0.14954 (16)	0.0248 (10)
C16	0.3925 (5)	0.5171 (6)	0.2492 (3)	0.0369 (17)
C17	0.3068 (4)	0.5993 (5)	0.2134 (2)	0.0217 (14)
C18	0.3288 (4)	0.7230 (5)	0.2102 (2)	0.0241 (14)
C19	0.2549 (4)	0.8074 (5)	0.1781 (2)	0.0226 (14)
C20	0.2897 (5)	0.9381 (5)	0.1758 (3)	0.0337 (17)
O11	0.0619 (3)	0.1936 (4)	0.30302 (17)	0.0281 (11)
O12	0.2021 (3)	0.2892 (4)	0.21159 (17)	0.0337 (11)
H11	0.40850	−0.08370	−0.02120	0.0420*
H12	0.28760	−0.14240	−0.04180	0.0420*
H13	0.31590	−0.10340	0.03080	0.0420*
H31	0.41770	0.09790	−0.07350	0.0270*
H51	0.38270	0.38180	−0.12110	0.0430*
H52	0.33050	0.30130	−0.17860	0.0430*
H53	0.44570	0.26160	−0.13970	0.0430*
H61	−0.07370	−0.06390	0.13710	0.0390*
H62	−0.11230	0.00480	0.19900	0.0390*
H63	0.01960	−0.02610	0.19210	0.0390*
H74	−0.085 (4)	0.163 (5)	−0.0695 (17)	0.0300*
H75	−0.080 (5)	0.083 (3)	−0.023 (3)	0.0300*
H81	−0.17070	0.19730	0.17490	0.0260*
H84	0.021 (4)	0.460 (3)	−0.065 (3)	0.0260*
H85	−0.073 (3)	0.422 (5)	−0.047 (3)	0.0260*
H101	−0.13680	0.47510	0.17890	0.0410*
H102	−0.24530	0.39020	0.16620	0.0410*
H103	−0.20620	0.47650	0.11090	0.0410*
H111	0.53330	0.26810	0.12220	0.0480*
H112	0.46670	0.14490	0.11160	0.0480*
H113	0.44370	0.22590	0.17220	0.0480*
H131	0.46000	0.43630	0.06500	0.0260*
H151	0.40350	0.62380	0.02360	0.0400*
H152	0.29570	0.66330	0.06190	0.0400*
H153	0.28090	0.63880	−0.01330	0.0400*
H94	0.205 (11)	0.467 (4)	0.191 (6)	0.0620*	0.56 (9)
H161	0.37750	0.51610	0.29470	0.0550*
H162	0.47020	0.54600	0.24410	0.0550*
H163	0.38470	0.43650	0.23190	0.0550*
H181	0.39750	0.75170	0.23080	0.0290*
H201	0.37140	0.94380	0.16870	0.0500*
H202	0.27450	0.97640	0.21640	0.0500*
H203	0.24570	0.97790	0.14080	0.0500*
H95	0.158 (10)	0.594 (13)	0.168 (7)	0.0620*	0.44 (9)
H114	0.104 (4)	0.193 (6)	0.338 (2)	0.0420*
H115	−0.005 (3)	0.221 (5)	0.306 (3)	0.0420*
H124	0.199 (6)	0.241 (5)	0.180 (2)	0.0500*
H125	0.156 (5)	0.254 (5)	0.236 (3)	0.0500*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ho1	0.0146 (1)	0.0147 (1)	0.0108 (1)	0.0001 (1)	0.0023 (1)	0.0006 (1)
O1	0.0183 (16)	0.0194 (17)	0.0163 (16)	0.0011 (13)	0.0055 (13)	−0.0007 (13)
O2	0.0189 (15)	0.0226 (18)	0.0152 (14)	0.0034 (13)	0.0074 (12)	0.0036 (13)
O3	0.0206 (16)	0.0241 (18)	0.0175 (16)	0.0022 (14)	0.0060 (13)	0.0030 (14)
O4	0.0246 (16)	0.0190 (17)	0.0150 (16)	0.0010 (13)	0.0092 (13)	0.0005 (13)
O5	0.0191 (15)	0.0244 (19)	0.0183 (15)	0.0006 (14)	−0.0033 (12)	0.0051 (15)
O6	0.0178 (15)	0.0166 (17)	0.0182 (16)	−0.0012 (13)	−0.0005 (13)	−0.0011 (13)
O7	0.0242 (17)	0.0191 (18)	0.0169 (16)	−0.0033 (14)	−0.0014 (14)	0.0076 (14)
O8	0.0165 (16)	0.0174 (17)	0.0176 (16)	0.0001 (13)	0.0047 (13)	0.0012 (14)
C1	0.024 (3)	0.025 (3)	0.034 (3)	0.005 (2)	0.009 (2)	0.002 (2)
C2	0.021 (2)	0.019 (2)	0.013 (2)	0.0014 (19)	−0.0030 (18)	−0.0018 (19)
C3	0.017 (2)	0.030 (3)	0.022 (2)	0.002 (2)	0.0066 (19)	−0.002 (2)
C4	0.020 (2)	0.024 (3)	0.015 (2)	−0.0059 (19)	0.0031 (17)	−0.004 (2)
C5	0.026 (3)	0.033 (3)	0.029 (3)	0.000 (2)	0.012 (2)	0.005 (2)
C6	0.036 (3)	0.021 (3)	0.024 (3)	0.002 (2)	0.014 (2)	0.003 (2)
C7	0.021 (2)	0.021 (3)	0.014 (2)	−0.0051 (19)	−0.0004 (18)	0.0008 (19)
C8	0.022 (2)	0.027 (3)	0.017 (2)	−0.0017 (19)	0.0112 (19)	0.002 (2)
C9	0.021 (2)	0.025 (3)	0.012 (2)	0.000 (2)	0.0031 (18)	0.000 (2)
C10	0.033 (3)	0.024 (3)	0.026 (3)	0.002 (2)	0.015 (2)	−0.001 (2)
C11	0.023 (2)	0.037 (3)	0.035 (3)	0.003 (2)	−0.005 (2)	0.003 (3)
C12	0.019 (2)	0.024 (3)	0.018 (2)	0.0043 (19)	0.0032 (18)	−0.0042 (19)
C13	0.015 (2)	0.028 (3)	0.023 (2)	−0.0025 (19)	0.0028 (19)	−0.001 (2)
C14	0.020 (2)	0.022 (2)	0.012 (2)	−0.0025 (19)	0.0038 (18)	−0.0028 (18)
C15	0.027 (3)	0.020 (3)	0.032 (3)	−0.005 (2)	0.004 (2)	−0.001 (2)
O9	0.045 (2)	0.046 (3)	0.033 (2)	−0.002 (2)	0.0045 (19)	0.001 (2)
O10	0.0228 (16)	0.029 (2)	0.0218 (16)	−0.0011 (14)	−0.0044 (13)	0.0035 (15)
C16	0.041 (3)	0.036 (3)	0.032 (3)	0.006 (3)	−0.011 (2)	−0.002 (3)
C17	0.020 (2)	0.035 (3)	0.010 (2)	0.002 (2)	0.0001 (18)	0.001 (2)
C18	0.018 (2)	0.035 (3)	0.019 (2)	−0.003 (2)	−0.0009 (18)	−0.004 (2)
C19	0.024 (2)	0.031 (3)	0.013 (2)	−0.004 (2)	0.0034 (19)	0.000 (2)
C20	0.035 (3)	0.036 (3)	0.029 (3)	−0.007 (2)	−0.006 (2)	0.001 (2)
O11	0.0284 (19)	0.035 (2)	0.0210 (18)	0.0017 (16)	0.0032 (15)	0.0016 (16)
O12	0.046 (2)	0.038 (2)	0.0180 (18)	−0.0097 (18)	0.0083 (17)	0.0002 (16)

Geometric parameters (Å, º)

Ho1—O1	2.387 (3)	C12—C13	1.395 (7)
Ho1—O2	2.334 (3)	C13—C14	1.395 (7)
Ho1—O3	2.305 (3)	C14—C15	1.503 (7)
Ho1—O4	2.342 (3)	C1—H13	0.9597
Ho1—O5	2.302 (3)	C1—H12	0.9602
Ho1—O6	2.383 (3)	C1—H11	0.9595
Ho1—O7	2.356 (3)	C3—H31	0.9297
Ho1—O8	2.416 (3)	C5—H51	0.9610
O1—C2	1.266 (6)	C5—H52	0.9588
O2—C4	1.280 (5)	C5—H53	0.9602
O3—C7	1.270 (6)	C6—H61	0.9593
O4—C9	1.290 (5)	C6—H62	0.9598
O5—C12	1.266 (5)	C6—H63	0.9601
O6—C14	1.271 (6)	C8—H81	0.9293
O7—H75	0.81 (4)	C10—H103	0.9602
O7—H74	0.82 (4)	C10—H101	0.9591
O8—H84	0.84 (4)	C10—H102	0.9603
O8—H85	0.82 (4)	C11—H113	0.9607
O9—C17	1.328 (7)	C11—H111	0.9601
O10—C19	1.265 (6)	C11—H112	0.9594
O9—H94	0.89 (5)	C13—H131	0.9304
O9—H95	0.88 (13)	C15—H152	0.9596
O11—H115	0.83 (4)	C15—H151	0.9604
O11—H114	0.84 (4)	C15—H153	0.9607
O12—H124	0.84 (5)	C16—C17	1.498 (8)
O12—H125	0.85 (6)	C17—C18	1.389 (8)
C1—C2	1.499 (7)	C18—C19	1.398 (7)
C2—C3	1.400 (7)	C19—C20	1.497 (8)
C3—C4	1.389 (7)	C16—H161	0.9607
C4—C5	1.507 (7)	C16—H162	0.9596
C6—C7	1.500 (7)	C16—H163	0.9592
C7—C8	1.401 (7)	C18—H181	0.9286
C8—C9	1.378 (7)	C20—H202	0.9602
C9—C10	1.506 (7)	C20—H203	0.9600
C11—C12	1.500 (7)	C20—H201	0.9607
Ho1···O12	4.110 (4)	H12···H153^vii	2.4844
Ho1···O8^i	4.086 (3)	H12···C15^vii	3.0464
Ho1···H124	3.47 (4)	H12···C8^ii	2.9943
Ho1···H61^ii	3.8117	H13···C20^vii	3.0465
Ho1···H75^ii	3.75 (3)	H31···H53	2.2940
Ho1···H84^i	3.58 (4)	H31···H11	2.2776
Ho1···H85^i	3.62 (6)	H51···H103^i	2.5784
Ho1···H114^iii	3.73 (4)	H52···O12^iii	2.8039
O1···O7^ii	2.854 (5)	H53···H31	2.2940
O2···O11^iii	2.906 (4)	H53···C18^ix	3.0480
O4···O8^i	2.788 (5)	H61···H74^ii	2.5983
O5···O12	2.879 (5)	H61···Ho1^ii	3.8117
O6···O8^i	2.765 (5)	H61···O1^ii	2.8245
O7···O10^i	2.721 (5)	H62···H81	2.2714
O7···O1^ii	2.854 (5)	H62···O9^vi	2.7249
O7···C1^ii	3.309 (6)	H62···H94^vi	2.5892
O8···O10^i	3.137 (5)	H63···O10^vii	2.8633
O8···O6^i	2.765 (5)	H74···C19^i	2.89 (4)
O8···O11^iii	3.220 (5)	H74···O10^i	1.92 (4)
O8···O4^i	2.788 (5)	H74···H61^ii	2.5983
O8···Ho1^i	4.086 (3)	H75···O3^ii	2.78 (4)
O9···O10	2.711 (6)	H75···O1^ii	2.09 (5)
O9···O12	2.887 (7)	H75···Ho1^ii	3.75 (3)
O9···C14	3.276 (6)	H75···C1^ii	2.98 (6)
O10···O7^i	2.721 (5)	H75···C2^ii	2.90 (5)
O10···O11^iv	2.918 (5)	H81···H62	2.2714
O10···O9	2.711 (6)	H81···C17^vi	3.0511
O10···O8^i	3.137 (5)	H81···C18^vi	3.0769
O11···O2^v	2.906 (4)	H81···H102	2.2958
O11···O8^v	3.220 (5)	H84···Ho1^i	3.58 (4)
O11···O10^vi	2.918 (5)	H84···O4^i	1.99 (3)
O11···O12	2.756 (5)	H84···O6^i	2.75 (5)
O11···C6^iv	3.397 (7)	H84···H103^i	2.4796
O11···C10^vi	3.375 (7)	H84···C10^i	2.84 (5)
O12···Ho1	4.110 (4)	H84···C9^i	2.81 (4)
O12···O9	2.887 (7)	H85···O4^i	2.76 (5)
O12···O11	2.756 (5)	H85···C14^i	2.76 (4)
O12···O5	2.879 (5)	H85···Ho1^i	3.62 (6)
O12···C12	3.242 (6)	H85···C15^i	2.93 (4)
O12···C16	3.390 (7)	H85···O6^i	1.99 (5)
O1···H61^ii	2.8245	H94···H124	2.50 (7)
O1···H75^ii	2.09 (5)	H94···H125	2.60 (9)
O2···H103^i	2.8010	H94···H62^iv	2.5892
O2···H114^iii	2.07 (4)	H94···O12	2.01 (5)
O3···H75^ii	2.78 (4)	H94···H163	2.2078
O3···H203^vii	2.8781	H95···O11^iv	2.85 (12)
O3···H124	2.68 (6)	H95···O8^i	2.80 (14)
O4···H85^i	2.76 (5)	H95···C19	2.61 (14)
O4···H84^i	1.99 (3)	H95···O10	2.05 (14)
O5···H124	2.21 (5)	H95···H115^iv	2.33 (14)
O6···H85^i	1.99 (5)	H101···O11^iv	2.5773
O6···H84^i	2.75 (5)	H101···H114^iv	2.4594
O8···H114^iii	2.79 (5)	H102···H81	2.2958
O8···H95^i	2.80 (13)	H103···H51^i	2.5784
O9···H62^iv	2.7249	H103···H84^i	2.4796
O10···H95	2.05 (14)	H103···H153^i	2.4832
O10···H63^viii	2.8633	H103···O2^i	2.8010
O10···H152	2.7624	H111···H131	2.3259
O10···H115^iv	2.13 (4)	H112···H11^x	2.5061
O10···H74^i	1.92 (4)	H114···C5^v	3.09 (5)
O11···H125	1.92 (6)	H114···O2^v	2.07 (4)
O11···H101^vi	2.5773	H114···H125	2.31 (8)
O11···H95^vi	2.85 (12)	H114···C10^vi	3.07 (6)
O12···H52^v	2.8039	H114···Ho1^v	3.73 (4)
O12···H94	2.01 (5)	H114···O8^v	2.79 (5)
O12···H163	2.6661	H114···C4^v	2.77 (5)
C1···O7^ii	3.309 (6)	H114···H101^vi	2.4594
C1···C15^vii	3.439 (8)	H115···H95^vi	2.33 (13)
C6···O11^vi	3.397 (7)	H115···O10^vi	2.13 (4)
C10···O11^iv	3.375 (7)	H115···H125	2.44 (7)
C12···O12	3.242 (6)	H115···C19^vi	3.06 (4)
C14···O9	3.276 (6)	H124···H94	2.50 (7)
C15···C1^viii	3.439 (8)	H124···C12	2.82 (6)
C16···O12	3.390 (7)	H124···O5	2.21 (5)
C1···H75^ii	2.98 (6)	H124···Ho1	3.47 (4)
C2···H75^ii	2.90 (5)	H124···O3	2.68 (6)
C4···H114^iii	2.77 (5)	H125···H114	2.31 (8)
C5···H114^iii	3.09 (5)	H125···O11	1.92 (6)
C8···H12^ii	2.9943	H125···H94	2.60 (9)
C9···H84^i	2.81 (4)	H125···H115	2.44 (7)
C9···H153^i	2.9890	H131···H111	2.3259
C10···H153^i	3.0058	H131···H151^ix	2.5602
C10···H84^i	2.84 (5)	H131···H151	2.3133
C10···H114^iv	3.07 (7)	H151···H131^ix	2.5602
C12···H124	2.82 (6)	H151···H131	2.3133
C14···H85^i	2.76 (4)	H152···C19	2.9286
C15···H85^i	2.93 (4)	H152···O10	2.7624
C15···H12^viii	3.0464	H153···C10^i	3.0058
C17···H81^iv	3.0511	H153···H103^i	2.4832
C18···H81^iv	3.0769	H153···C9^i	2.9890
C18···H53^ix	3.0480	H153···H12^viii	2.4844
C19···H95	2.61 (14)	H162···H181	2.4264
C19···H152	2.9286	H163···O12	2.6661
C19···H74^i	2.89 (4)	H163···H94	2.2078
C19···H115^iv	3.06 (4)	H181···H201	2.4812
C20···H13^viii	3.0465	H181···H162	2.4264
H11···H31	2.2776	H201···H181	2.4812
H11···H112^x	2.5061	H203···O3^viii	2.8781
O1—Ho1—O2	71.77 (11)	O6—C14—C15	116.6 (4)
O1—Ho1—O3	73.29 (11)	C2—C1—H11	109.49
O1—Ho1—O4	146.13 (11)	C2—C1—H12	109.43
O1—Ho1—O5	73.92 (11)	H11—C1—H12	109.48
O1—Ho1—O6	131.10 (12)	C2—C1—H13	109.45
O1—Ho1—O7	76.70 (12)	H12—C1—H13	109.46
O1—Ho1—O8	127.41 (11)	H11—C1—H13	109.52
O2—Ho1—O3	144.96 (12)	C4—C3—H31	117.77
O2—Ho1—O4	141.39 (11)	C2—C3—H31	117.79
O2—Ho1—O5	91.30 (9)	C4—C5—H52	109.51
O2—Ho1—O6	75.45 (11)	C4—C5—H53	109.51
O2—Ho1—O7	97.77 (11)	C4—C5—H51	109.41
O2—Ho1—O8	72.56 (10)	H51—C5—H52	109.49
O3—Ho1—O4	73.59 (11)	H51—C5—H53	109.42
O3—Ho1—O5	76.58 (11)	H52—C5—H53	109.48
O3—Ho1—O6	128.58 (11)	C7—C6—H61	109.49
O3—Ho1—O7	76.54 (11)	C7—C6—H63	109.41
O3—Ho1—O8	134.01 (12)	H61—C6—H62	109.47
O4—Ho1—O5	104.91 (11)	C7—C6—H62	109.53
O4—Ho1—O6	76.91 (11)	H61—C6—H63	109.42
O4—Ho1—O7	88.92 (12)	H62—C6—H63	109.52
O4—Ho1—O8	73.83 (11)	C9—C8—H81	117.41
O5—Ho1—O6	71.59 (11)	C7—C8—H81	117.49
O5—Ho1—O7	144.68 (12)	C9—C10—H102	109.47
O5—Ho1—O8	143.52 (11)	C9—C10—H103	109.44
O6—Ho1—O7	143.73 (11)	H101—C10—H102	109.57
O6—Ho1—O8	72.73 (11)	H101—C10—H103	109.42
O7—Ho1—O8	71.29 (11)	H102—C10—H103	109.47
Ho1—O1—C2	127.8 (3)	C9—C10—H101	109.46
Ho1—O2—C4	129.4 (3)	C12—C11—H113	109.47
Ho1—O3—C7	135.3 (3)	H112—C11—H113	109.43
Ho1—O4—C9	133.0 (3)	H111—C11—H112	109.51
Ho1—O5—C12	135.6 (3)	H111—C11—H113	109.43
Ho1—O6—C14	132.6 (3)	C12—C11—H112	109.47
Ho1—O7—H75	124 (4)	C12—C11—H111	109.50
H74—O7—H75	106 (6)	C12—C13—H131	118.28
Ho1—O7—H74	122 (4)	C14—C13—H131	118.37
Ho1—O8—H84	119 (3)	C14—C15—H153	109.40
H84—O8—H85	96 (5)	H152—C15—H153	109.44
Ho1—O8—H85	123 (4)	H151—C15—H152	109.55
C17—O9—H95	117 (9)	H151—C15—H153	109.41
C17—O9—H94	118 (8)	C14—C15—H152	109.58
H114—O11—H115	115 (5)	C14—C15—H151	109.46
H124—O12—H125	100 (6)	O9—C17—C16	116.0 (5)
C1—C2—C3	118.3 (4)	O9—C17—C18	123.9 (5)
O1—C2—C3	124.6 (4)	C16—C17—C18	120.1 (4)
O1—C2—C1	117.1 (4)	C17—C18—C19	124.6 (4)
C2—C3—C4	124.4 (4)	O10—C19—C20	117.9 (4)
O2—C4—C5	116.3 (4)	C18—C19—C20	120.0 (4)
O2—C4—C3	124.2 (4)	O10—C19—C18	122.1 (5)
C3—C4—C5	119.5 (4)	C17—C16—H163	109.53
C6—C7—C8	118.9 (4)	H161—C16—H162	109.42
O3—C7—C8	123.8 (4)	C17—C16—H162	109.51
O3—C7—C6	117.3 (4)	H162—C16—H163	109.51
C7—C8—C9	125.1 (4)	H161—C16—H163	109.37
O4—C9—C10	115.6 (4)	C17—C16—H161	109.49
O4—C9—C8	125.2 (4)	C17—C18—H181	117.71
C8—C9—C10	119.2 (4)	C19—C18—H181	117.64
O5—C12—C11	115.6 (4)	C19—C20—H202	109.45
O5—C12—C13	124.4 (4)	C19—C20—H203	109.51
C11—C12—C13	119.9 (4)	H201—C20—H203	109.38
C12—C13—C14	123.3 (4)	H202—C20—H203	109.55
O6—C14—C13	124.5 (4)	H201—C20—H202	109.48
C13—C14—C15	118.9 (4)	C19—C20—H201	109.46
O2—Ho1—O1—C2	40.2 (3)	O1—Ho1—O6—C14	−20.5 (4)
O3—Ho1—O1—C2	−137.1 (4)	O2—Ho1—O6—C14	−69.6 (4)
O4—Ho1—O1—C2	−149.6 (3)	O3—Ho1—O6—C14	81.5 (4)
O5—Ho1—O1—C2	−56.7 (3)	O4—Ho1—O6—C14	137.6 (4)
O6—Ho1—O1—C2	−10.1 (4)	O5—Ho1—O6—C14	26.8 (4)
O7—Ho1—O1—C2	143.2 (4)	O7—Ho1—O6—C14	−152.8 (3)
O8—Ho1—O1—C2	89.7 (4)	O8—Ho1—O6—C14	−145.5 (4)
O1—Ho1—O2—C4	−40.2 (3)	Ho1—O1—C2—C1	153.2 (3)
O3—Ho1—O2—C4	−35.7 (4)	Ho1—O1—C2—C3	−28.8 (6)
O4—Ho1—O2—C4	148.6 (3)	Ho1—O2—C4—C3	28.2 (6)
O5—Ho1—O2—C4	32.4 (4)	Ho1—O2—C4—C5	−153.8 (3)
O6—Ho1—O2—C4	103.0 (4)	Ho1—O3—C7—C6	164.4 (3)
O7—Ho1—O2—C4	−113.3 (4)	Ho1—O3—C7—C8	−17.0 (7)
O8—Ho1—O2—C4	179.1 (4)	Ho1—O4—C9—C10	−171.0 (3)
O1—Ho1—O3—C7	−151.6 (4)	Ho1—O4—C9—C8	11.2 (7)
O2—Ho1—O3—C7	−156.0 (4)	Ho1—O5—C12—C11	−166.8 (3)
O4—Ho1—O3—C7	21.2 (4)	Ho1—O5—C12—C13	16.5 (7)
O5—Ho1—O3—C7	131.5 (4)	Ho1—O6—C14—C13	−17.5 (6)
O6—Ho1—O3—C7	78.7 (4)	Ho1—O6—C14—C15	164.5 (3)
O7—Ho1—O3—C7	−71.7 (4)	O1—C2—C3—C4	−6.4 (7)
O8—Ho1—O3—C7	−25.3 (5)	C1—C2—C3—C4	171.5 (4)
O1—Ho1—O4—C9	−5.5 (5)	C2—C3—C4—C5	−170.4 (4)
O2—Ho1—O4—C9	159.5 (3)	C2—C3—C4—O2	7.5 (7)
O3—Ho1—O4—C9	−17.9 (4)	O3—C7—C8—C9	−2.2 (7)
O5—Ho1—O4—C9	−88.7 (4)	C6—C7—C8—C9	176.4 (4)
O6—Ho1—O4—C9	−155.3 (4)	C7—C8—C9—C10	−173.1 (4)
O7—Ho1—O4—C9	58.4 (4)	C7—C8—C9—O4	4.6 (7)
O8—Ho1—O4—C9	129.2 (4)	C11—C12—C13—C14	−166.3 (4)
O1—Ho1—O5—C12	118.0 (4)	O5—C12—C13—C14	10.3 (7)
O2—Ho1—O5—C12	47.4 (4)	C12—C13—C14—C15	169.1 (4)
O3—Ho1—O5—C12	−165.8 (4)	C12—C13—C14—O6	−8.9 (7)
O4—Ho1—O5—C12	−97.1 (4)	O9—C17—C18—C19	0.0 (7)
O6—Ho1—O5—C12	−26.8 (4)	C16—C17—C18—C19	179.9 (9)
O7—Ho1—O5—C12	152.9 (4)	C17—C18—C19—C20	−177.8 (4)
O8—Ho1—O5—C12	−14.3 (5)	C17—C18—C19—O10	1.2 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H74···O10^i	0.82 (4)	1.92 (4)	2.721 (5)	165 (5)
O7—H75···O1^ii	0.81 (4)	2.09 (5)	2.854 (5)	159 (5)
O8—H84···O4^i	0.84 (4)	1.99 (3)	2.788 (5)	157 (4)
O8—H85···O6^i	0.82 (4)	1.99 (5)	2.765 (5)	157 (5)
O9—H94···O12	0.89 (5)	2.01 (5)	2.887 (7)	173 (12)
O11—H114···O2^v	0.84 (4)	2.07 (4)	2.906 (4)	171 (6)
O11—H115···O10^vi	0.83 (4)	2.13 (4)	2.918 (5)	159 (6)
O12—H124···O5	0.84 (5)	2.21 (5)	2.879 (5)	136 (5)
O12—H125···O11	0.85 (6)	1.92 (6)	2.756 (5)	170 (6)
C10—H101···O11^iv	0.96	2.58	3.375 (7)	141

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