Hydrogen bonding in the crystal structure of phurcalite, Ca₂[(UO₂)₃O₂(PO₄)₂]·7H₂O: single-crystal X-ray study and TORQUE calculations

The crystal structure of phurcalite, Ca₂[(UO₂)₃O₂(PO₄)₂]·7H₂O, orthorhombic, a = 17.3785 (9) Å, b = 15.9864 (8) Å, c = 13.5477 (10) Å, V = 3763.8 (4) ų, space group Pbca, Z = 8 has been refined from single-crystal XRD data to R = 0.042 for 3182 unique [I > 3σ(I)] reflections and the hydrogen-bonding scheme has been refined by theoretical calculations based on the TORQUE method. The phurcalite structure is layered, with uranyl phosphate sheets of the phosphuranylite topology which are linked by extensive hydrogen bonds across the interlayer occupied by Ca²⁺ cations and H₂O groups. In contrast to previous studies the approach here reveals five transformer H₂O groups (compared to three expected by a previous study) and two non-transformer H₂O groups. One of the transformer H₂O groups is, nevertheless, not linked to any metal cation, which is a less frequent type of H₂O bonding in solid state compounds and minerals. The structural formula of phurcalite has been therefore redefined as {Ca₂(H₂^[3]O)₅(H₂^[4]O)₂}[(UO₂)₃O₂(PO₄)₂], Z = 8.

1. Introduction

Uranyl phosphates and arsenates represent a group of environmentally important minerals formed during a hydration–oxidation weathering of primary U minerals, mostly uraninite (Finch & Murakami, 1999; Krivovichev & Plášil, 2013; Plášil, 2014). Generally, due to their low solubility products (see e.g. Ilton et al., 2010; Astilleros et al., 2013; Göb et al., 2013), they can occur both in the vadose zone of the uranium deposits (Murakami et al., 1997; Finch & Murakami, 1999; Plášil et al., 2006, 2009; Göb et al., 2013) and in mine dumps, wastes and tailings (Buck et al., 1996; Roh et al., 2000; Fuller et al., 2002; Catalano et al., 2006; Cantrell et al., 2011; Maher et al., 2013). This makes uranyl phosphate and arsenate minerals essential for controlling U mobility in the environment. Nowadays, more than 50 uranyl phosphates and arsenates are known to occur in nature, some of them being discovered in the past decade (Mills et al., 2008; Plášil et al., 2010, 2018; Pekov et al., 2012).

The vast majority of uranyl phosphate structures are based on sheets of vertex- and edge-sharing uranyl polyhedra and phosphate tetrahedra. Uranyl phosphate minerals (and arsenates as well) have historically been classified/divided in two major groups, autunite and phosphuranylite groups (Krivovichev & Plášil, 2013). They essentially differ in details of their topological arrangement of structural units, i.e. uranyl-anion topologies. The autunite topology comprises equatorial vertex-sharing between uranyl square bipyramids and phosphate tetrahedra. The phosphuranylite type of structures contains both uranyl pentagonal and hexagonal bipyramids within the sheets that share edges, forming chains that are cross-linked by sharing vertices and edges with phosphate tetrahedra (Burns, 2005; Lussier et al., 2016). Mineral phosphuranylite (s.s.) contains additionally one extra uranyl square bipyramid located between the sheets making it the 3D framework structure (Demartin et al., 1991).

Hydrogen bonds are of particular importance for stabilizing the largely hydrated structures of uranyl phosphates and arsenates, thus controlling their thermodynamic stabilities. Consequently, it is important to determine the details of hydrogen bonding in such minerals in order to understand their stability and the mechanisms by which they break down. Nevertheless, the direct determination of the H-atom positions in uranyl-based compounds is challenging, largely due to high absorption of X-rays and small or poorly developed crystals available for the structure analysis. Therefore, the combination of methods, usually comprised of XRD structure determination and density functional theory (DFT) optimization is often adopted (Colmenero et al., 2017, 2018a,b,c, 2019a,b,c).

Here, we present a complete structure determination, including hydrogen bonding, in a complex structure of uranyl phosphate mineral phurcalite, as determined by combination of X-rays and a recently developed robust, fast real space optimization method (Ghazisaeed et al., 2018, 2019).

2. Methodology

2.1. Sample

The natural specimen used for extraction of phurcalite crystals suitable for X-ray diffraction originates from the Shinkolobwe mine, Shaba province, Democratic Republic of Congo (Africa). Phurcalite forms long-prismatic, needle-like orthorhombic crystals of intense yellow color (Fig. 1), growing in cavities of quartz with disseminated small crystals of metatorbernite–metazeunerite series of minerals. The specimen has been deposited in the mineral collection of the Musée National d'Histoire Naturelle in Luxembourg (specimen registration number PV025).

Figure 1 Phurcalite in long-prismatic crystals in quartz-dominant gangue. FOV ∼6 mm across (photo by S. Wolfsried).

2.2. Single-crystal X-ray diffraction

A long-prismatic fragment (0.091 mm × 0.012 mm × 0.009 mm) of phurcalite crystal was selected under a polarized-light microscope and mounted on a glass fiber. The X-ray data collection was done at room temperature with a Rigaku SuperNova single-crystal diffractometer (Mo Kα radiation from a micro-focus X-ray tube collimated and monochromated by mirror-optics and detected by an Atlas S2 CCD detector). In line with previous structure determinations, phurcalite is found to be orthorhombic, a = 17.3785 (9) Å, b = 15.9864 (8) Å, c = 13.5477 (10) Å, V = 3763.8 (4) ų and Z = 8. Integration of the diffraction data, including corrections for background, polarization and Lorentz effects were carried out with the CrysAlis RED program (Rigaku, 2019). An empirical absorption correction was applied to the data in the Jana2006 software, using spherical harmonics (Petříček et al., 2014). Crystallographic data and experimental details are given in Table 1. The structure of phurcalite was solved by the charge-flipping algorithm using the SHELXT program (Sheldrick, 2015). Structure refinement was done using the software Jana2006 with the full-matrix least-squares refinement based on F². The structure solution revealed positions for all atoms except of hydrogens; those were ascertained from the difference Fourier maps. The H atoms were refined using a mix of soft constraints on O—H distances and with the U_eq of each H set to 1.2 times that of the donor O atom. The bond-valence sums were calculated following the procedure of Brown (2002), and using bond-valence parameters taken from Gagné & Hawthorne (2015).

Table 1
Experimental details

Crystal data
Chemical formula	Ca2(H2O)6[(UO2)3O2(PO4)2]·(H2O)
Mr	1238.3
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	17.3785 (9), 15.9864 (8), 13.5477 (10)
V (Å^3)	3763.8 (4)
Z	8
No. of reflections for cell measurement	3639
Radiation type, wavelength (Å)	Mo Kα, 0.71073
θ range (°) for cell measurement	4.0–29
μ (mm^−1)	26.58
Crystal size (mm)	0.09 × 0.01 × 0.01
Data collection
Diffractometer	SuperNova, Dual, Cu at zero, AtlasS2
Absorption correction	Empirical (using intensity measurements) (JANA2006)
Tmin, Tmax	0.982, 1
No. of measured, independent and observed [I > 3σ(I)] reflections	20 436, 4721, 3182
Rint	0.067
(sin θ/λ)max (Å^−1)	0.698
Refinement on F^2 by Jana2006
R (obs), R (all)	0.042, 0.0647
wR (obs), wR (all)	0.080, 0.074
S (all)	1.22
No. of reflections	4721
No. of parameters	198
No. of restraints	21
H-atom treatment	All H-atom parameters refined
Δρmax, Δρmin (e Å^−3)	3.58, −3.41
Computer programs: CrysAlis PRO 1.171.38.43 (Rigaku, 2015), Jana2006 (Petříček et al., 2014).

2.3. TORQUE method calculations

The orientations of the H₂O molecules were optimized with the TORQUE method, a robust and fast real-space method for determining H₂O orientations from rotational equilibrium (Ghazisaeed et al., 2018, 2019). In all test-cases (haidingerite, Ca[AsO₃(OH)]·H₂O, barium chloride monohydrate, BaCl₂·H₂O, apophyllite, KCa₄(Si₄O₁₀)₂F_1–x(HF)_x·[(H₂O)_8–x(OH)_x], grimselite, K₃Na(UO₂)(CO₃)₃·(H₂O), and kernite, Na₂B₄O₆(OH)₂·3(H₂O), the TORQUE-predicted equilibrium H₂O orientations agreed with available neutron diffraction observations (Ghazisaeed et al., 2018). In the TORQUE method, the H₂O molecules are placed such that its oxygen matches the location known from the experiment. In contrast, no prior knowledge of the location of the two hydrogens atoms (per water molecule) is needed. Their locations are obtained from the molecular H₂O geometry, as described in the TIP3P model [H—O—H angle = 104.52°, and d(O—H) = 0.9572 Å; Jorgensen et al., 1983].

We performed two sets of TORQUE computations to investigate the extent of hydrogen bonding in phurcalite. In the first set, we orient the H₂O molecules such that they match our X-ray observations as closely as possible. Slight adjustments are needed to account for deviations of d(O—H) and H—O—H angle between experiment and water model. More specifically, we place each water molecule in the corresponding experimental H₂O plane, and adjust the bond geometry, such that the bis­ectors of the H—O—H angle coincide and place the two hydrogen atoms at ±52.26^o, from the bis­ector at the prescribed molecular O—H distance. With this placement of the H₂O molecules the complete initial crystal structure of phurcalite is completely specified. Charges for ions in the structural unit are taken from bond-valence analysis (see below), and for H₂O from the TIP3P model (Jorgensen et al., 1983). With this information, the torque on the H₂O molecules is computed and the H₂O molecules are rigidly rotated about their oxygen ions by a small increment. This torque compution/rigid rotation cycle is continued until the torque is vanishingly small and rotational equilibrium is reached (Ghazisaeed et al., 2018).

The results address stable and unstable water orientations in the X-ray derived hydrogen bond network. In the second set the H₂O molecules are oriented randomly while preserving the molecular H₂O geometry and addresses the (non)uniqueness of the identified rotational equilibria. We optimized 1000 random initial H₂O orientations and statistically analyzed the similarities and differences of the obtained rotational equilibrium configurations, similar to our previous work (Ghazisaeed et al., 2018, 2019, 2020; Steciuk et al., 2019). Moreover, we performed an additional TORQUE optimization where the H₂O initial orientations are chosen as closely as possible to our X-ray refinements.

3. Results

3.1. Crystal structure obtained from X-ray diffraction

The structure of phurcalite as obtained from the current structure determination by X-ray diffraction is in line with previous study done by Atencio et al. (1991). During the current study it was possible to reveal partially some of the positions of the H atoms in the structure and refine them to obtain a reasonable bonding geometry. The structure of phurcalite is based upon uranyl phosphate sheets [Fig. 2(a)] of phosphuranylite topology (Burns, 2005; Lussier et al., 2016), with a ring symbol 6¹5²4²3² (Krivovichev & Burns, 2007); with hexagons of the topology occupied by U⁶⁺. Unlike sheets of other members of the phosphuranylite group (Piret & Declercq, 1983; Piret et al., 1988; Demartin et al., 1991; Dal Bo et al., 2017), the sheet in phurcalite does not contain H atoms either as OH or as molecular H₂O. The composition of the sheets are hydrogen free, [(UO₂)₃O₂(PO₄)₂]⁴⁻, and stacked perpendicular to the [010] direction in phurcalite [Fig. 2(b)]. Between adjacent sheets two independent Ca sites are located. The Ca1 is linked to seven ligands, including four O of the H₂O groups, two uranyl O atoms (of the U3 and U2) and one O atom of the P2 tetrahedron. The Ca2 site is surrounded by eight ligands including five O atoms from H₂O groups, two uranyl O atoms (one to the U1 and one to the U2 polyhedra) and one bond to to P2 tetrahedron. Two of the H₂O (with Wyckoff 8c = two H₂O pfu) are shared between Ca1 and Ca2 (O13 and O20) that form dimers of the composition {Ca₂(H₂O)₇O₆}. The detailed analysis of the hydrogen bonding is given below.

Figure 2 Crystal structure of phurcalite. (a) Uranyl phosphate sheet of the phosphuranylite topology containing UO2^2+ coordinated both as UO7 (U1 and U2) and UO8 bipyramids. (b) Stacking of the sheets perpendicular to b. Adjacent sheets are linked by an extensive hydrogen bonding network (bonds are omitted for clarity). Color scheme: U is yellow, P is pink, Ca is violet, O is red, H is gray; unit-cell edges are outlined as black solid lines.

3.2. Hydrogen bonding as revealed from both X-rays and TORQUE

The stereochemical details of the hydrogen bonding as revealed from X-rays and TORQUE calculations are given in Table 2. There are seven independent O atoms corresponding to H₂O groups in the structure of phurcalite: following the XRD structure determination, H₂O is expected to belong to sites O16, O17, O19, O20, O21, O22, O23. However, the detailed orientation of O17 could not be resolved due to insufficiently resolved difference Fourier maxima from the X-ray data.

Table 2
Hydrogen-bond geometry as obtained from XRD data and TORQUE calculations

Left: XRD; Right: TORQUE. For TORQUE, we list we list the highest probability joint seven-site model (17.5%). For details, see text.

XRD					Torque
D—H⋯A	D—H (Å)	H⋯A (Å)	D⋯A (Å)	D—H⋯A (°)	D—H⋯A	D—H (Å)	H⋯A (Å)	D⋯A (Å)	D—H⋯A (°)
O16—H1O16⋯O19	0.95 (8)	1.98 (9)	2.762 (14)	139 (7)	O16—H1O16⋯O12	0.957	2.286	3.126	146.1
O16—H2O16⋯O20^iii	0.94 (9)	2.39 (8)	3.248 (14)	151 (7)	O16—H1O16⋯O10	0.955	1.884	2.801	160.0
O17—H1O17⋯O23^xii	0.95 (5)	1.89 (7)	2.763 (13)	153 (7)	O17—H1O17⋯O7	0.957	2.160	2.821	125.1
O17—H2O17⋯O19^x	0.94 (7)	2.36 (9)	2.944 (13)	120 (9)	O17—H2O17⋯O10	0.956	1.846	2.782	165.3
O19—H1O19⋯O17^x	0.95 (8)	2.02 (9)	2.944 (13)	162 (8)	O19—H2O19⋯O12	0.959	2.251	3.179	162.4
O19—H2O19⋯O11^v	0.95 (7)	1.92 (8)	2.809 (10)	155 (8)	O19—H1O19⋯O11	0.957	2.043	2.809	135.7
O20—H1O20⋯O8^xi	0.94 (8)	2.34 (8)	3.123 (11)	141 (7)	O20—H1O20⋯O18	0.959	2.009	2.966	175.3
O20—H2O20⋯O22^xi	0.94 (6)	2.18 (4)	3.074 (14)	159 (8)	O20—H2O20⋯O14	0.956	1.969	2.870	156.4
O21—H1O21⋯O12^xv	0.95 (9)	2.37 (10)	3.241 (12)	153 (7)	O21—H2O21⋯O7	0.959	2.185	3.090	156.8
O21—H2O21⋯O5^ii	0.95 (9)	2.41 (11)	2.892 (12)	111 (8)	O21—H2O21⋯O4	0.959	1.981	2.921	165.8
O22—H1O22⋯O23	0.94 (5)	1.90 (8)	2.700 (13)	141 (9)	O22—H1O22⋯O23	0.952	1.769	2.698	164.5
O22—H2O22⋯O5^vii	0.95 (8)	2.11 (8)	3.033 (12)	162 (8)	O22—H1O22⋯O5	0.961	2.076	3.033	174.4
O23—H1O23⋯O17^xiv	0.95 (6)	2.13 (9)	2.763 (13)	123 (8)	O23—H1O23⋯O16	0.957	1.806	2.751	168.9
O23—H2O23⋯O7	0.94 (9)	2.38 (9)	3.268 (12)	157 (8)	O23—H2O23⋯O17	0.959	1.911	2.764	146.7
Symmetry codes: (ii) x − ½, −y + ½, −z + 1; (iii) x − ½, y, −z + ½; (v) x, −y + ½, z + ½; (vi) x + ½, y, −z + ½; (vii) −x + , y + ½, z; (x) –x + 1, −y + 1, −z + 1; (xi) −x + 2, −y + 1, −z + 1; (xii) −x + , −y + 1, z − ½; (xiv) –x + , −y + 1, z + ½; (xv) −x + 1, y + ½, −z + ½.

3.3. Discussion – hydrogen bonding

X-ray structure refinements and results from TORQUE provide strong evidence for extensive hydrogen bonding in phurcalite. In contrast to the results of our X-ray diffraction refinements, TORQUE successfully identified reasonable H₂O hydrogen bond arrays for all seven water sites, including O17 (Table 2).

Bond-valence analysis shows that calculated sums of bond-valence at the sites are within a few percent of expected oxidation states of all elements in phurcalite (Table 3). Therefore, we chose the corresponding formal charges for all non-H₂O toms for the TORQUE simulations. We obtained rotational equilibria for 1000 randomly initialized configurations. In order to compare more directly to X-ray data, we identified structures as equivalent, if the closest acceptor for all seven H₂O sites for two configurations is the same. We TORQUE-optimized 1000 randomly chosen initial H₂O orientations and found 53 geometrically distinct O—H⋯A environments (H₂O rotational equilibrium orientations), with occurrences that range from 0.1% to 17.5% (see Fig. 3). However, only six of the seven-site H₂O environments are predicted to have an occurrence probability of 6% or higher (with a joint probability of 52.3%, Fig. 3). This observation suggests that a comparatively small number of O—H⋯A environments likely capture a significant fraction of the stereochemical variability, at least in phurcalite. The stereochemical results for the average seven-site model for the highest probability O—H⋯A environment (17.5%) are shown in Table 2, the TORQUE predicted hydrogen acceptor sites are listed in Table 4, and the corresponding hydrogen positions are listed in Table 5. The reported standard deviations were obtained from the analysis of the TORQUE-predicted equilibrium orientations that belong to an equivalent set. For example, for the highest probability configuration, 175 equilibrium orientations were averaged, and the corresponding standard deviations were computed. If we analyze the probability of orientations for each site, we find that all seven water orientations appear either with the highest or second highest probability (Table 4). This observation that not every site belongs to the highest probability orientations demonstrates that local and global rotational equilibrium do not necessarily coincide, and correlated changes in the water array must be taken into account during data analysis. A comparison of the stereochemistry of the water positions determined by X-ray diffraction and the 53 equilibrium H₂O orientations shows no simultaneous match for all seven sites. Complete O20 and O22 stereochemistry matches occur in our library with probabilities of 4.2% and 38.5%, respectively (Table 4). Partial matches exist for O17, O19, O21 and O23, and no match is found for O16. This result suggests that the X-ray derived water stereochemistry does not correspond to a rotational equilibrium state. In order to explore whether this conclusion is due to sampling, we initialized TORQUE close to our X-ray-derived H₂O positions (while preserving the predefined H₂O geometry of the TIP3P water model, see method section for details on hydrogen placement); we find again significant re-bonding of hydrogen, partial matches can be found for O19, O21, O22 and O23, while complete re-bonding is predicted for O16, O17 and O20 (Table 4, optimized hydrogen positions are listed in Table 6. However, in contrast to the X-ray derived H₂O array we find a simultaneous match for all seven water sites among the 53 equilibrium orientations with a probability of 3.8%, ranked #6 among the 53 distinct rotational equilibrium orientations (Fig. 3). Therefore, it is unlikely that the X-ray hydrogen positions correspond to an accidentally unsampled rotational equilibrium state, and uncertainties can be more likely attributed to simultaneous rotations of several H₂O molecules.

Table 3
Bond-valence analysis (all values given in valence units, vu) for phurcalite

	U1	U2	U3	Ca1	Ca2	P1	P2	ΣBV
O1	0.61	0.65	0.66					1.93
O2		0.53	0.26			1.19		1.98
O3	0.61	0.58	0.70					1.89
O4			1.65	0.24				1.88
O5		1.65			0.16			1.81
O6		0.55	0.33			1.23		2.11
O7		1.66		0.18				1.84
O8	0.44		0.21				1.21	1.87
O9		0.44			0.28		1.19	1.92
O10			1.71					1.71
O11	0.53					1.33		1.85
O12	1.78							1.78
O13				0.31	0.33	1.30		1.93
O14	1.69				0.13			1.81
O15	0.37		0.42				1.19	1.97
O16					0.28			0.28
O17				0.34				0.34
O18				0.42			1.39	1.80
O19					0.29			0.29
O20				0.25	0.20			0.45
O21					0.31			0.31
O22				0.34				0.34
O23								0.00
ΣBV	6.02	6.07	5.94	2.07	1.97	5.05	4.98

+H-bonds	H1O16	H2O16	H1O17	H2O17	H1O19	H2O19	H1O20	H2O20	H1O21	H2O21	H1O22	H2O22	H1O23	H2O23	ΣBV
O1															1.93
O2															1.98
O3															1.89
O4										0.08					+1.88 = 1.96
O5												0.07			+1.81 = 1.88
O6															2.11
O7			0.05						0.05						+1.84 = 1.94
O8															1.87
O9															1.92
O10		0.10		0.11											+1.71 = 1.92
O11					0.04										+1.85 = 1.89
O12	0.04					0.07									+1.78 = 1.89
O13															1.93
O14								0.09							+1.81 = 1.90
O15															1.97
O16	0.91	0.92											0.12		+0.28 = 2.23
O17			0.91	0.91										0.10	+0.34 = 2.26
O18							0.08								+1.80 = 1.88
O19					0.91	0.91									+0.29 = 2.11
O20							0.91	0.91							+0.45 = 2.27
O21									0.91	0.91					+0.31 = 2.13
O22											0.91	0.90			+0.34 = 2.15
O23											0.14		0.91	0.91	1.96
ΣBV	0.95	1.02	0.97	1.03	0.95	0.98	0.99	1.00	0.96	0.99	1.06	0.97	1.04	1.01
The bond-valence parameters taken from Gagné & Hawthorne (2015).

Table 4
Summary of all site occurrences among the 1000 configurations

Nearest oxygen acceptor sites for the two hydrogens are shown in parenthesis. Bold and underlined are TORQUE-predicted sites that agree with our X-ray diffraction experiment. Detailed hydrogen positions for the random TORQUE seven-site model (probability 17.5%), and EXP + TORQUE model are given in Table 5 and Table 6, respectively.

N = 1000	EXP	EXP + TORQUE seven-site model	Random TORQUE seven-site model (P = 17.5%)	Probability of occurrence
O16	(19+20)	(10+23)	(10+12)	91.2% (10+12)	8.8% (10+23)
O17	(19+23)	(7+10)	(7+10)	66.4% (7+10)	33.6% (10+23)
O19	(11+17)	(11+12)	(11+12)	90.3% (11+12)	9.7% (12+17)
O20	(8+22)	(14+18)	(14+18)	82.2 (14+18)	11.2% (4+18)	4.2% (8+22)	2.4% (4+13)
O21	(5+12)	(5+7)	(4+7)	49.3% (5+7)	46.7% (4+7)	4.0% (4+5)
O22	(5+23)	(5+14)	(5+23)	55.2% (5+14)	38.5% (5+23)	4.1% (4+5)	2.0% (14+23)	0.2% (5+20)
O23	(7+17)	(17+22)	(16+17)	39.0% (16+22)	33.8% (16+17)	26.8% (17+22)	0.2% (16+16)	0.1% (11+16)	0.1% (16+21)

Table 5
TORQUE-predicted average fractional positions and standard deviations for the TORQUE-optimized X-ray hydrogen bond scheme for the highest probability seven-site model (17.5%)

A standard deviation of (0) signifies that is smaller than the last displayed digit.

TORQUE	Site	x	y	z
O16	H1O16	0.53179 (2)	0.44109 (2)	0.43288 (1)
	H2O16	0.57752 (1)	0.40415 (1)	0.35006 (3)
O17	H1O17	0.71263 (1)	0.46332 (2)	0.50366 (0)
	H2O17	0.69911 (0)	0.42675 (0)	0.40202 (1)
O19	H1O19	0.39835 (1)	0.48544 (0)	0.45829 (1)
	H2O19	0.40868 (2)	0.41112 (0)	0.52627 (1)
O20	H1O20	0.99421 (2)	0.52502 (1)	0.37683 (2)
	H2O20	0.99646 (2)	0.43307 (1)	0.35018 (2)
O21	H1O21	0.28743 (1)	0.52979 (2)	0.31847 (1)
	H2O21	0.32157 (0)	0.53923 (0)	0.21624 (0)
O22	H1O22	0.86960 (19)	0.5092 (3)	0.66145 (4)
	H2O22	0.82376 (6)	0.58223 (11)	0.62206 (1)
O23	H1O23	0.90269 (2)	0.49392 (1)	0.80610 (5)
	H2O23	0.81637 (2)	0.48353 (6)	0.81419 (11)

Table 6
TORQUE-predicted fractional positions for hydrogen, if the method is initialized close to the corresponding refined X-ray positions

TORQUE	Site	x	y	z
O16	H1O16	0.54435	0.48978	0.37795
	H2O16	0.57984	0.40381	0.36667
O17	H1O17	0.70755	0.46820	0.50272
	H2O17	0.69837	0.42671	0.40297
O19	H1O19	0.40669	0.48376	0.45977
	H2O19	0.41338	0.40528	0.52172
O20	H1O20	0.99650	0.52464	0.37201
	H2O20	0.99494	0.43179	0.35014
O21	H1O21	0.31019	0.55300	0.31527
	H2O21	0.28558	0.46597	0.28448
O22	H1O22	0.90000	0.57427	0.64744
	H2O22	0.81632	0.57138	0.61656
O23	H1O23	0.84478	0.48224	0.71565
	H2O23	0.82143	0.48288	0.82330

Figure 3 Probabilities for the 53 non-equivalent TORQUE identified H2O equilibrium orientations in phurcalite.

The X-ray O16 water site has no match among the TORQUE determined 53 equilibrium H₂O orientations, while all other sites at least show a partial match. For O16, the X-ray observations suggest (Table 2) hydrogen bonding to O19 (water) and O20 (water). In contrast, TORQUE predicts bonding to O10 (U3) and O23 (water). The driving force for re-bonding is H32 which is only 1.87 Å from Ca2 in the refined X-ray data, closer than any of its oxygen ligands. The corresponding Ca—H electrostatic repulsion provides a driving torque for water re-orientation, and in rotational equilibrium we find d(H32–Ca2) = 3.02 Å, an increase of ∼60%. Therefore, the X-ray O16 stereochemistry is predicted to be unstable, and we note that the TORQUE-optimized O16 water orientation appears in our library with a probability of 8.8% (Table 4).

X-ray diffraction was unable to identify reasonable hydrogen bonding for O17. The origin of this inability may be explained by TORQUE-predicted re-bonding, the X-ray observations suggest hydrogen bonding (Table 2) with O19 (water) and O23 (water). However, we find hydrogen atoms only ∼1.5 Å from O17H1 and O17H2, distances comparable to the intramolecular H–H distance. Therefore, H–H repulsion induces water rotation and a new stereochemistry to O7(U2) and O10(U3), which we find for the TORQUE-optimized X-ray orientations, as well as for the highest probability model in our library and corresponds to the highest probability O17 orientation (66.3%, Tables 2 and 4). Therefore, TORQUE successfully describes a rotational equilibrium state for O17, that could not be resolved from our X-ray diffraction results. The discussion of possible hydrogen-bonding arrangements in phurcalite has been used in the theoretical bond-valence studies (Schindler & Hawthorne, 2008) focused on interactions between anionic (i.e. Lewis bases) and cationic (i.e. Lewis acids) parts of the structures of hydrated oxysalts. Their conclusions, which they found on the basis of the bond-valence theory (Brown, 2002, 2009; Hawthorne, 2012, 2015), were that phurcalite contains three transformer H₂O groups (having a corresponding O atom as three-coordinated; for details check Fig. 5 in Schindler & Hawthorne, 2008), three non-transformer H₂O groups (having a corresponding O atom as four-coordinated) and one non-transformer H₂O group not bonded to any cations; the composition of the interstitial complex was expressed as {Ca₂(H₂^[3]O)₃(H₂^[4]O)3(H₂O)₁} (Schindler & Hawthorne, 2008). Our study advances the understanding of H₂O complexes and their interactions with the surrounding crystal framework in phurcalite. From the scheme given in Fig. 4 it is possible to simply read off that there are five transformer H₂O groups (with corresponding O atom being three-coordinated); one bonded to Ca1 atom (O22) three others bonded to Ca2 atom (O16, O19, O21) and an additional one, O23, which is not linked to the metal cation (see below). Furthermore, there are two non-transformer H₂O groups (with corresponding O atom being four-coordinated). First one, O17, is linked to Ca1 site, nevertheless accepts also one weak hydrogen bond from H1_O19. Second one, O20, is shared between Ca1 and Ca2 atoms. Finally, the O23 atom belongs to the transformer H₂O group, with no linkage to any metal cation; O23 receives one hydrogen bond from H1_O22 and transform it into two hydrogen bonds, via H1_O23 and H2_O23, therefore the O23 is three-coordinated. The magnitude of strength of two corresponding hydrogen-bonds (H1_O23 + H2_O23 = 0.13 vu) match the initial strength of the hydrogen-bond accepted by O23 (0.14 vu). To summarize, the interstitial complex in phurcalite can be expressed as {Ca₂(H₂^[3]O)₅(H₂^[4]O)₂}. Therefore, the structural formula of phurcalite is {Ca₂(H₂^[3]O)₅(H₂^[4]O)₂}[(UO₂)₃O₂(PO₄)₂], Z = 8.

Figure 4 Bonding scheme concerning interstitial H2O groups in phurcalite. (Ur) – uranyl apical O atom, (Ueq) – uranyl equatorial O atom, (Wa) – H2O molecule, (P) – O atom of the PO4 group, bond-strengths given in valence-units (vu).

4. Conclusions

The structure of the mineral phurcalite (calcium uranyl phosphate heptahydrate) is stabilized by an extensive network of hydrogen bonds. Phurcalite is unique among uranyl phosphates in that it shows a high Ca:U ratio (2:3) (for instance mineral autunite has 1:2) and its structure displays an unusual hydrogen bonding scheme. Structure data obtained from a XRD experiment and theoretical calculations (TORQUE) indicate that the structure of phurcalite contains a rare functional type of H₂O group in the interlayer which is not linked to any metal cation directly, as it accepts one hydrogen bond from an adjacent H₂O group. This H₂O group thus splits the incident bond-strength (represented by one incoming hydrogen bond) into two weaker hydrogen bonds. Therefore it is a transformer H₂O group with a three-coordinated O atom. Our study advances our understanding of hydrogen bonding in complex uranyl minerals and shows the synergy of experiment and theory provides new insights into the complex hydrogen bonding in uranyl phosphates and the role of H₂O groups in complex oxysalt minerals. In summary, it is likely that the rare hydrogen bonding topology in phurcalite is responsible for its low abundance in nature.

Supporting information

Computing details

(I)

Crystal data

U3P2O23Ca2H14	F(000) = 4352
Mr = 1238.3	Dx = 4.371 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P -2xab;-2ybc;-2zac	Cell parameters from 3639 reflections
a = 17.3785 (9) Å	θ = 4.0–29°
b = 15.9864 (8) Å	µ = 26.58 mm^−1
c = 13.5477 (10) Å	T = 293 K
V = 3763.8 (4) Å^3	Prismatic, yellow
Z = 8	0.09 × 0.01 × 0.01 mm

Data collection

SuperNova, Dual, Cu at zero, AtlasS2 diffractometer	4721 independent reflections
Radiation source: X-ray tube	3182 reflections with I > 3σ(I)
Mirror monochromator	Rint = 0.067
Detector resolution: 5.2027 pixels mm^-1	θmax = 29.7°, θmin = 3.2°
ω scans	h = −20→23
Absorption correction: empirical (using intensity measurements) Jana2006	k = −18→21
Tmin = 0.982, Tmax = 1	l = −14→17
20436 measured reflections

Refinement

Refinement on F^2	14 constraints
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: difference Fourier map
wR(F^2) = 0.074	All H-atom parameters refined
S = 1.22	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0000345744I^2)
4721 reflections	(Δ/σ)max = 0.041
198 parameters	Δρmax = 3.58 e Å^−3
21 restraints	Δρmin = −3.41 e Å^−3

Special details

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

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

	x	y	z	Uiso*/Ueq
U1	0.54881 (2)	0.21707 (2)	0.13101 (3)	0.00998 (12)
U2	0.76270 (2)	0.26502 (2)	0.63371 (3)	0.00977 (12)
U3	0.65666 (3)	0.21341 (2)	0.38744 (3)	0.01061 (12)
Ca1	0.85458 (15)	0.45478 (13)	0.46853 (17)	0.0148 (8)
Ca2	0.41064 (17)	0.39027 (14)	0.28930 (18)	0.0203 (8)
P1	0.34272 (17)	0.24595 (16)	0.1203 (2)	0.0103 (8)
P2	0.96925 (17)	0.30765 (16)	0.6127 (2)	0.0099 (9)
O1	0.6546 (5)	0.2324 (4)	0.5513 (5)	0.0157 (17)*
O2	0.2945 (5)	0.2029 (4)	0.2024 (5)	0.0138 (17)*
O3	0.6563 (5)	0.1982 (4)	0.2251 (5)	0.0133 (16)*
O4	0.6589 (5)	0.1015 (4)	0.4077 (5)	0.0149 (17)*
O5	0.7665 (5)	0.1565 (4)	0.6709 (5)	0.0129 (17)*
O6	0.2887 (5)	0.2340 (5)	0.0312 (5)	0.0167 (18)*
O7	0.7706 (5)	0.3730 (4)	0.5960 (5)	0.0164 (18)*
O8	1.0188 (5)	0.3314 (5)	0.7034 (6)	0.0202 (19)*
O9	0.9016 (4)	0.2492 (4)	0.6419 (5)	0.0124 (16)*
O10	0.6582 (5)	0.3242 (4)	0.3677 (6)	0.0196 (18)*
O11	0.4163 (5)	0.1970 (4)	0.1061 (5)	0.0158 (18)*
O12	0.5616 (5)	0.1146 (4)	0.0835 (6)	0.0188 (19)*
O13	0.3570 (5)	0.3380 (4)	0.1413 (5)	0.0142 (17)*
O14	0.5283 (5)	0.3182 (4)	0.1827 (5)	0.0148 (17)*
O15	1.0273 (5)	0.2600 (5)	0.5459 (6)	0.0199 (19)*
O16	0.5318 (6)	0.4328 (6)	0.3629 (8)	0.036 (2)*
O17	0.7232 (5)	0.4726 (5)	0.4352 (7)	0.025 (2)*
O18	0.9414 (5)	0.3847 (5)	0.5614 (6)	0.023 (2)*
O19	0.3926 (6)	0.4258 (5)	0.4610 (6)	0.026 (2)*
O20	0.9627 (5)	0.4802 (5)	0.3527 (6)	0.0219 (19)*
O21	0.3255 (6)	0.5064 (6)	0.2753 (6)	0.033 (2)*
O22	0.8650 (6)	0.5448 (5)	0.6054 (7)	0.033 (2)*
O23	0.8605 (6)	0.4628 (5)	0.7794 (7)	0.037 (3)*
H1o16	0.502 (5)	0.427 (7)	0.421 (5)	0.0432*
H2o16	0.498 (5)	0.455 (7)	0.315 (6)	0.0432*
H1o19	0.349 (4)	0.457 (6)	0.482 (7)	0.0308*
H2o19	0.410 (6)	0.397 (6)	0.518 (4)	0.0308*
H1o21	0.350 (6)	0.553 (5)	0.305 (7)	0.0394*
H2o21	0.284 (5)	0.493 (7)	0.318 (7)	0.0394*
H1o22	0.881 (6)	0.535 (7)	0.671 (3)	0.0396*
H2o22	0.823 (4)	0.583 (6)	0.611 (7)	0.0396*
H1o17	0.703 (5)	0.481 (6)	0.371 (3)	0.0304*
H2o17	0.680 (3)	0.462 (7)	0.475 (6)	0.0304*
H1o20	0.973 (5)	0.523 (5)	0.307 (6)	0.0263*
H2o20	1.011 (2)	0.459 (6)	0.372 (8)	0.0263*
H1o23	0.843 (7)	0.447 (6)	0.843 (3)	0.0442*
H2o23	0.839 (7)	0.423 (6)	0.736 (5)	0.0442*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
U1	0.0060 (2)	0.0132 (2)	0.0108 (2)	0.00071 (16)	−0.00070 (18)	−0.00021 (15)
U2	0.0067 (2)	0.0138 (2)	0.0088 (2)	0.00025 (16)	−0.00027 (19)	−0.00010 (15)
U3	0.0100 (2)	0.0121 (2)	0.0097 (2)	0.00039 (18)	−0.00019 (19)	0.00007 (14)
Ca1	0.0154 (15)	0.0118 (11)	0.0172 (13)	0.0016 (10)	−0.0017 (11)	−0.0023 (8)
Ca2	0.0248 (17)	0.0169 (12)	0.0193 (14)	−0.0038 (11)	−0.0057 (12)	0.0027 (9)
P1	0.0076 (15)	0.0124 (13)	0.0110 (14)	−0.0022 (13)	0.0026 (14)	0.0021 (9)
P2	0.0026 (14)	0.0151 (14)	0.0119 (16)	−0.0012 (11)	0.0000 (12)	0.0005 (10)

Geometric parameters (Å, º)

U1—O1^i	2.280 (8)	O9—O15	2.548 (11)
U1—O3	2.282 (8)	O9—O18	2.522 (10)
U1—O8^ii	2.430 (8)	O10—O15^ii	2.891 (12)
U1—O11	2.349 (9)	O10—O16	2.801 (13)
U1—O12	1.774 (7)	O10—O17	2.782 (11)
U1—O14	1.798 (7)	O10—H1o17	2.63 (10)
U1—O15^iii	2.521 (8)	O10—H2o17	2.67 (10)
U2—O1	2.247 (8)	O11—O12	2.864 (12)
U2—O2^iv	2.345 (7)	O11—O13	2.524 (10)
U2—O3^v	2.302 (8)	O11—O14	2.936 (11)
U2—O5	1.808 (6)	O11—O15^iii	2.996 (11)
U2—O6^vi	2.333 (7)	O11—O19^i	2.809 (10)
U2—O7	1.805 (6)	O11—H2o19^i	1.92 (8)
U2—O9	2.430 (7)	O11—H1o23^ii	2.72 (10)
U3—O1	2.241 (7)	O12—O15^iii	2.972 (11)
U3—O2^vi	2.692 (8)	O12—H1o16^i	2.52 (8)
U3—O3	2.213 (7)	O12—H2o19^i	2.79 (10)
U3—O4	1.810 (6)	O12—H1o21^ix	2.37 (10)
U3—O6^vi	2.567 (8)	O12—H2o17^i	2.81 (8)
U3—O8^ii	2.787 (9)	O13—O20^iii	2.924 (11)
U3—O10	1.791 (6)	O14—O20^iii	2.870 (11)
U3—O15^ii	2.460 (9)	O14—H2o16	2.88 (10)
Ca1—O4^vii	2.497 (7)	O14—H1o22^xii	2.83 (11)
Ca1—O7	2.612 (8)	O14—H2o20^iii	2.39 (10)
Ca1—O13^vi	2.388 (7)	O15—O18	2.499 (12)
Ca1—O17	2.345 (9)	O16—O19	2.762 (14)
Ca1—O18	2.262 (9)	O16—O23^xii	2.750 (14)
Ca1—O20	2.481 (9)	O16—H1o16	0.95 (8)
Ca1—O22	2.354 (9)	O16—H2o16	0.94 (9)
Ca1—H2o22	2.87 (9)	O16—H1o20^iii	2.90 (8)
Ca1—H1o17	2.98 (8)	O16—H1o23^xii	2.92 (11)
Ca2—O5^ii	2.669 (9)	O17—O19^x	2.944 (13)
Ca2—O9^ii	2.422 (7)	O17—O23^xii	2.763 (13)
Ca2—O13	2.364 (8)	O17—H1o19^x	2.02 (9)
Ca2—O14	2.756 (8)	O17—H1o17	0.95 (5)
Ca2—O16	2.427 (11)	O17—H2o17	0.94 (7)
Ca2—O19	2.415 (9)	O17—H1o23^xii	2.13 (9)
Ca2—O20^iii	2.566 (9)	O18—O20^xi	2.966 (12)
Ca2—O21	2.381 (10)	O18—O22	2.944 (12)
Ca2—H1o16	2.46 (8)	O18—H1o20^xi	2.75 (8)
Ca2—H2o16	1.87 (10)	O18—H2o20^xi	2.78 (9)
Ca2—H1o21	2.81 (8)	O19—H1o16	1.98 (9)
Ca2—H2o21	2.77 (10)	O19—H2o16	2.74 (9)
Ca2—H1o20^iii	2.72 (8)	O19—H1o19	0.95 (8)
P1—O2	1.553 (8)	O19—H2o19	0.95 (7)
P1—O6	1.541 (8)	O19—H2o21	2.91 (9)
P1—O11	1.511 (9)	O19—H2o17^x	2.36 (9)
P1—O13	1.520 (7)	O19—H1o23^xiii	2.81 (6)
P1—H2o19^i	2.92 (9)	O20—O21^vi	2.978 (13)
P2—O8	1.547 (9)	O20—H2o16^vi	2.39 (8)
P2—O9	1.554 (8)	O20—H1o22^xi	2.75 (10)
P2—O15	1.554 (9)	O20—H1o20	0.94 (8)
P2—O18	1.494 (9)	O20—H2o20	0.94 (6)
O1—O3^v	2.603 (9)	O21—H1o19	2.94 (9)
O1—O4	2.858 (9)	O21—H1o21	0.95 (9)
O1—O5	2.807 (11)	O21—H2o21	0.95 (9)
O1—O6^vi	2.585 (12)	O21—H1o17^iii	2.94 (7)
O1—O10	2.889 (10)	O21—H1o20^iii	2.81 (9)
O1—O12^v	2.964 (10)	O22—O23	2.700 (13)
O1—O14^v	2.940 (11)	O22—H2o21^x	2.85 (9)
O1—O15^ii	2.577 (12)	O22—H1o22	0.94 (5)
O1—H2o22^viii	2.55 (10)	O22—H2o22	0.95 (8)
O2—O3^iii	2.596 (12)	O22—H2o20^xi	2.18 (4)
O2—O5^ii	2.870 (9)	O22—H2o23	2.67 (9)
O2—O6	2.374 (10)	O23—H2o16^xiv	2.83 (9)
O2—O9^ii	2.915 (10)	O23—H2o21^x	2.92 (9)
O2—O11	2.488 (12)	O23—H1o22	1.90 (8)
O2—O13	2.555 (10)	O23—H1o17^xiv	1.89 (7)
O2—O23^ii	2.897 (11)	O23—H2o17^xiv	2.99 (9)
O2—H1o23^ii	2.61 (10)	O23—H1o23	0.95 (6)
O2—H2o23^ii	2.31 (10)	O23—H2o23	0.94 (9)
O3—O4	2.917 (9)	H1o16—H2o16	1.51 (11)
O3—O7^i	2.881 (11)	H1o16—H1o19	2.83 (11)
O3—O8^ii	2.621 (12)	H1o16—H2o19	2.12 (12)
O3—O10	2.791 (10)	H2o16—H1o22^xii	2.87 (12)
O3—O12	2.859 (11)	H2o16—H1o20^iii	2.03 (12)
O3—O14	2.993 (11)	H2o16—H2o20^iii	2.54 (14)
O3—H1o21^ix	2.36 (8)	H1o19—H2o19	1.51 (13)
O4—O17^viii	2.930 (11)	H1o19—H1o21	2.85 (13)
O4—O20^viii	2.963 (11)	H1o19—H2o21	2.56 (13)
O4—O21^ix	2.921 (11)	H1o19—H1o17^x	2.40 (11)
O4—O22^viii	2.858 (12)	H1o19—H2o17^x	1.51 (14)
O4—H1o21^ix	2.99 (9)	H1o19—H1o23^xiii	2.38 (10)
O4—H2o22^viii	2.79 (9)	H2o19—H2o17^x	2.75 (14)
O4—H1o20^viii	2.95 (8)	H2o19—H1o23^xiii	2.35 (11)
O5—O9	2.804 (11)	H1o21—H2o21	1.51 (14)
O5—O13^iv	2.992 (10)	H1o21—H1o20^iii	2.66 (13)
O5—O21^iv	2.892 (12)	H2o21—H1o22^x	2.91 (14)
O5—H2o21^iv	2.41 (11)	H2o21—H2o22^x	2.42 (12)
O5—H2o22^viii	2.11 (8)	H2o21—H1o17^iii	2.93 (11)
O6—O7^iii	2.830 (10)	H2o21—H2o17^x	2.96 (13)
O6—O11	2.509 (12)	H2o21—H2o23^x	2.63 (15)
O6—O13	2.529 (11)	H1o22—H2o22	1.51 (13)
O6—H2o19^i	2.98 (10)	H1o22—H1o20^xi	2.72 (14)
O7—O17	2.821 (11)	H1o22—H2o20^xi	1.97 (11)
O7—H1o21^x	2.76 (10)	H1o22—H1o23	2.80 (10)
O7—H2o21^x	2.62 (11)	H1o22—H2o23	2.12 (14)
O7—H2o17	2.68 (8)	H2o22—H2o20^xi	2.97 (8)
O7—H2o23	2.38 (9)	H1o17—H2o17	1.50 (9)
O8—O9	2.563 (11)	H1o17—H1o23^xii	1.45 (14)
O8—O14^iv	2.851 (10)	H1o17—H2o23^xii	2.50 (11)
O8—O15	2.424 (11)	H2o17—H1o23^xii	2.34 (12)
O8—O18	2.497 (12)	H1o20—H2o20	1.50 (12)
O8—H1o20^xi	2.34 (8)	H1o23—H2o23	1.50 (8)
O1^i—U1—O3	69.6 (3)	O19^x—O17—H1o19^x	6 (2)
O1^i—U1—O8^ii	136.3 (3)	O19^x—O17—H1o17	96 (5)
O1^i—U1—O11	140.4 (2)	O19^x—O17—H2o17	44 (7)
O1^i—U1—O12	93.1 (3)	O19^x—O17—H1o23^xii	65 (2)
O1^i—U1—O14	91.5 (3)	O23^xii—O17—H1o19^x	84 (3)
O1^i—U1—O15^iii	64.7 (3)	O23^xii—O17—H1o17	18 (5)
O3—U1—O8^ii	67.5 (3)	O23^xii—O17—H2o17	95 (5)
O3—U1—O11	149.8 (2)	O23^xii—O17—H1o23^xii	17 (2)
O3—U1—O12	88.7 (3)	H1o19^x—O17—H1o17	102 (6)
O3—U1—O14	93.6 (3)	H1o19^x—O17—H2o17	45 (7)
O3—U1—O15^iii	133.5 (3)	H1o19^x—O17—H1o23^xii	70 (3)
O8^ii—U1—O11	83.0 (3)	H1o17—O17—H2o17	105 (7)
O8^ii—U1—O12	93.9 (3)	H1o17—O17—H1o23^xii	35 (6)
O8^ii—U1—O14	83.4 (3)	H2o17—O17—H1o23^xii	91 (6)
O8^ii—U1—O15^iii	158.9 (3)	Ca1—O18—P2	152.0 (5)
O11—U1—O12	86.8 (3)	Ca1—O18—O8	163.1 (4)
O11—U1—O14	89.1 (3)	Ca1—O18—O9	118.9 (4)
O11—U1—O15^iii	75.8 (3)	Ca1—O18—O15	138.3 (4)
O12—U1—O14	175.3 (4)	Ca1—O18—O20^xi	103.4 (3)
O12—U1—O15^iii	85.7 (3)	Ca1—O18—O22	51.8 (3)
O14—U1—O15^iii	95.5 (3)	Ca1—O18—H1o20^xi	117.1 (17)
O1—U2—O2^iv	135.9 (3)	Ca1—O18—H2o20^xi	86.2 (17)
O1—U2—O3^v	69.8 (3)	P2—O18—O8	35.5 (3)
O1—U2—O5	86.9 (3)	P2—O18—O9	35.0 (3)
O1—U2—O6^vi	68.7 (3)	P2—O18—O15	35.7 (3)
O1—U2—O7	98.3 (3)	P2—O18—O20^xi	103.6 (4)
O1—U2—O9	146.0 (2)	P2—O18—O22	140.2 (5)
O2^iv—U2—O3^v	67.9 (3)	P2—O18—H1o20^xi	88.0 (17)
O2^iv—U2—O5	86.4 (3)	P2—O18—H2o20^xi	119.5 (19)
O2^iv—U2—O6^vi	155.2 (3)	O8—O18—O9	61.4 (3)
O2^iv—U2—O7	92.3 (3)	O8—O18—O15	58.1 (3)
O2^iv—U2—O9	75.2 (3)	O8—O18—O20^xi	69.1 (3)
O3^v—U2—O5	97.2 (3)	O8—O18—O22	112.6 (4)
O3^v—U2—O6^vi	136.5 (3)	O8—O18—H1o20^xi	52.6 (17)
O3^v—U2—O7	88.2 (3)	O8—O18—H2o20^xi	84.1 (19)
O3^v—U2—O9	143.1 (2)	O9—O18—O15	61.0 (3)
O5—U2—O6^vi	93.2 (3)	O9—O18—O20^xi	127.6 (4)
O5—U2—O7	173.5 (4)	O9—O18—O22	122.4 (4)
O5—U2—O9	81.4 (3)	O9—O18—H1o20^xi	109.2 (17)
O6^vi—U2—O7	85.3 (3)	O9—O18—H2o20^xi	135 (2)
O6^vi—U2—O9	80.2 (3)	O15—O18—O20^xi	106.2 (4)
O7—U2—O9	92.1 (3)	O15—O18—O22	168.4 (4)
O1—U3—O2^vi	118.1 (3)	O15—O18—H1o20^xi	99.2 (18)
O1—U3—O3	178.2 (3)	O15—O18—H2o20^xi	124.5 (11)
O1—U3—O4	89.1 (3)	O20^xi—O18—O22	62.7 (3)
O1—U3—O6^vi	64.6 (3)	O20^xi—O18—H1o20^xi	18.4 (17)
O1—U3—O8^ii	117.3 (3)	O20^xi—O18—H2o20^xi	18.5 (12)
O1—U3—O10	90.8 (3)	O22—O18—H1o20^xi	69.3 (18)
O1—U3—O15^ii	66.3 (3)	O22—O18—H2o20^xi	44.6 (10)
O2^vi—U3—O3	63.0 (3)	H1o20^xi—O18—H2o20^xi	32 (3)
O2^vi—U3—O4	89.3 (3)	Ca2—O19—O11^v	119.4 (3)
O2^vi—U3—O6^vi	53.6 (2)	Ca2—O19—O16	55.4 (3)
O2^vi—U3—O8^ii	123.3 (2)	Ca2—O19—O17^x	132.7 (4)
O2^vi—U3—O10	88.9 (3)	Ca2—O19—H1o16	67 (2)
O2^vi—U3—O15^ii	171.9 (2)	Ca2—O19—H2o16	42 (2)
O3—U3—O4	92.4 (3)	Ca2—O19—H1o19	121 (6)
O3—U3—O6^vi	116.3 (3)	Ca2—O19—H2o19	129 (5)
O3—U3—O8^ii	62.0 (3)	Ca2—O19—H2o21	61.9 (19)
O3—U3—O10	87.7 (3)	Ca2—O19—H2o17^x	127 (2)
O3—U3—O15^ii	112.4 (3)	Ca2—O19—H1o23^xiii	168 (2)
O4—U3—O6^vi	92.4 (3)	O11^v—O19—O16	103.7 (4)
O4—U3—O8^ii	80.3 (3)	O11^v—O19—O17^x	98.7 (3)
O4—U3—O10	177.9 (4)	O11^v—O19—H1o16	93 (3)
O4—U3—O15^ii	97.7 (3)	O11^v—O19—H2o16	122 (2)
O6^vi—U3—O8^ii	172.3 (2)	O11^v—O19—H1o19	106 (6)
O6^vi—U3—O10	85.6 (3)	O11^v—O19—H2o19	17 (6)
O6^vi—U3—O15^ii	129.6 (3)	O11^v—O19—H2o21	145 (2)
O8^ii—U3—O10	101.6 (3)	O11^v—O19—H2o17^x	111 (2)
O8^ii—U3—O15^ii	54.6 (3)	O11^v—O19—H1o23^xiii	58 (2)
O10—U3—O15^ii	84.1 (3)	O16—O19—O17^x	143.7 (4)
O4^vii—Ca1—O7	129.5 (3)	O16—O19—H1o16	13 (2)
O4^vii—Ca1—O13^vi	122.1 (2)	O16—O19—H2o16	19.8 (19)
O4^vii—Ca1—O17	74.4 (3)	O16—O19—H1o19	145 (6)
O4^vii—Ca1—O18	135.4 (3)	O16—O19—H2o19	98 (6)
O4^vii—Ca1—O20	73.1 (3)	O16—O19—H2o21	103.5 (18)
O4^vii—Ca1—O22	72.1 (3)	O16—O19—H2o17^x	128 (2)
O4^vii—Ca1—H2o22	62.2 (19)	O16—O19—H1o23^xiii	136 (2)
O4^vii—Ca1—H1o17	68.8 (18)	O17^x—O19—H1o16	142 (3)
O7—Ca1—O13^vi	91.7 (2)	O17^x—O19—H2o16	135 (2)
O7—Ca1—O17	69.1 (3)	O17^x—O19—H1o19	12 (5)
O7—Ca1—O18	75.9 (3)	O17^x—O19—H2o19	96 (5)
O7—Ca1—O20	157.4 (3)	O17^x—O19—H2o21	70.8 (19)
O7—Ca1—O22	80.1 (3)	O17^x—O19—H2o17^x	16 (2)
O7—Ca1—H2o22	78.8 (18)	O17^x—O19—H1o23^xiii	43 (2)
O7—Ca1—H1o17	82.5 (14)	H1o16—O19—H2o16	32 (3)
O13^vi—Ca1—O17	89.5 (3)	H1o16—O19—H1o19	147 (6)
O13^vi—Ca1—O18	87.0 (3)	H1o16—O19—H2o19	85 (7)
O13^vi—Ca1—O20	73.8 (3)	H1o16—O19—H2o21	116 (3)
O13^vi—Ca1—O22	165.3 (3)	H1o16—O19—H2o17^x	127 (4)
O13^vi—Ca1—H2o22	168.9 (15)	H1o16—O19—H1o23^xiii	124 (3)
O13^vi—Ca1—H1o17	81.3 (16)	H2o16—O19—H1o19	131 (6)
O17—Ca1—O18	144.8 (3)	H2o16—O19—H2o19	117 (6)
O17—Ca1—O20	126.6 (3)	H2o16—O19—H2o21	84 (3)
O17—Ca1—O22	98.8 (3)	H2o16—O19—H2o17^x	120 (3)
O17—Ca1—H2o22	81.7 (15)	H2o16—O19—H1o23^xiii	150 (3)
O17—Ca1—H1o17	15.4 (11)	H1o19—O19—H2o19	105 (8)
O18—Ca1—O20	85.9 (3)	H1o19—O19—H2o21	59 (6)
O18—Ca1—O22	79.2 (3)	H1o19—O19—H2o17^x	21 (6)
O18—Ca1—H2o22	96.2 (17)	H1o19—O19—H1o23^xiii	54 (6)
O18—Ca1—H1o17	155.1 (17)	H2o19—O19—H2o21	158 (6)
O20—Ca1—O22	109.9 (3)	H2o19—O19—H2o17^x	104 (6)
O20—Ca1—H2o22	117.0 (16)	H2o19—O19—H1o23^xiii	52 (6)
O20—Ca1—H1o17	111.5 (11)	H2o21—O19—H2o17^x	67 (3)
O22—Ca1—H2o22	17.8 (16)	H2o21—O19—H1o23^xiii	113 (3)
O22—Ca1—H1o17	109.4 (15)	H2o17^x—O19—H1o23^xiii	53 (3)
H2o22—Ca1—H1o17	92 (2)	Ca1—O20—Ca2^vi	96.6 (3)
O5^ii—Ca2—O9^ii	66.6 (2)	Ca1—O20—O4^vii	53.7 (2)
O5^ii—Ca2—O13	72.7 (3)	Ca1—O20—O13^vi	51.6 (2)
O5^ii—Ca2—O14	133.2 (2)	Ca1—O20—O14^vi	105.0 (3)
O5^ii—Ca2—O16	144.1 (3)	Ca1—O20—O18^xi	107.3 (3)
O5^ii—Ca2—O19	75.5 (3)	Ca1—O20—O21^vi	77.6 (3)
O5^ii—Ca2—O20^iii	129.8 (3)	Ca1—O20—H2o16^vi	140 (2)
O5^ii—Ca2—O21	69.6 (3)	Ca1—O20—H1o22^xi	143.9 (13)
O5^ii—Ca2—H1o16	121.8 (19)	Ca1—O20—H1o20	133 (5)
O5^ii—Ca2—H2o16	152 (3)	Ca1—O20—H2o20	116 (6)
O5^ii—Ca2—H1o21	84 (2)	Ca2^vi—O20—O4^vii	107.7 (3)
O5^ii—Ca2—H2o21	53 (2)	Ca2^vi—O20—O13^vi	50.5 (2)
O5^ii—Ca2—H1o20^iii	133.7 (18)	Ca2^vi—O20—O14^vi	60.6 (2)
O9^ii—Ca2—O13	88.6 (2)	Ca2^vi—O20—O18^xi	154.2 (4)
O9^ii—Ca2—O14	82.2 (2)	Ca2^vi—O20—O21^vi	50.2 (2)
O9^ii—Ca2—O16	99.0 (3)	Ca2^vi—O20—H2o16^vi	44 (2)
O9^ii—Ca2—O19	80.6 (3)	Ca2^vi—O20—H1o22^xi	102.2 (16)
O9^ii—Ca2—O20^iii	145.8 (3)	Ca2^vi—O20—H1o20	89 (5)
O9^ii—Ca2—O21	135.1 (3)	Ca2^vi—O20—H2o20	109 (6)
O9^ii—Ca2—H1o16	89 (2)	O4^vii—O20—O13^vi	93.1 (3)
O9^ii—Ca2—H2o16	119 (3)	O4^vii—O20—O14^vi	156.3 (4)
O9^ii—Ca2—H1o21	143 (2)	O4^vii—O20—O18^xi	80.0 (3)
O9^ii—Ca2—H2o21	116 (2)	O4^vii—O20—O21^vi	58.9 (3)
O9^ii—Ca2—H1o20^iii	158.4 (18)	O4^vii—O20—H2o16^vi	122 (2)
O13—Ca2—O14	72.5 (3)	O4^vii—O20—H1o22^xi	142 (2)
O13—Ca2—O16	142.1 (4)	O4^vii—O20—H1o20	80 (5)
O13—Ca2—O19	148.1 (4)	O4^vii—O20—H2o20	143 (6)
O13—Ca2—O20^iii	72.6 (3)	O13^vi—O20—O14^vi	63.4 (3)
O13—Ca2—O21	87.9 (3)	O13^vi—O20—O18^xi	155.3 (4)
O13—Ca2—H1o16	163 (2)	O13^vi—O20—O21^vi	67.8 (3)
O13—Ca2—H2o16	132 (3)	O13^vi—O20—H2o16^vi	93 (2)
O13—Ca2—H1o21	104 (2)	O13^vi—O20—H1o22^xi	124 (2)
O13—Ca2—H2o21	91 (2)	O13^vi—O20—H1o20	135 (5)
O13—Ca2—H1o20^iii	91.5 (17)	O13^vi—O20—H2o20	106 (5)
O14—Ca2—O16	71.8 (3)	O14^vi—O20—O18^xi	120.0 (4)
O14—Ca2—O19	134.4 (3)	O14^vi—O20—O21^vi	110.3 (4)
O14—Ca2—O20^iii	65.1 (2)	O14^vi—O20—H2o16^vi	66 (3)
O14—Ca2—O21	138.2 (3)	O14^vi—O20—H1o22^xi	61 (2)
O14—Ca2—H1o16	90 (2)	O14^vi—O20—H1o20	118 (5)
O14—Ca2—H2o16	74 (3)	O14^vi—O20—H2o20	51 (6)
O14—Ca2—H1o21	135 (2)	O18^xi—O20—O21^vi	125.2 (4)
O14—Ca2—H2o21	155 (2)	O18^xi—O20—H2o16^vi	111 (2)
O14—Ca2—H1o20^iii	77.2 (18)	O18^xi—O20—H1o22^xi	64 (2)
O16—Ca2—O19	69.6 (4)	O18^xi—O20—H1o20	68 (5)
O16—Ca2—O20^iii	81.1 (3)	O18^xi—O20—H2o20	70 (6)
O16—Ca2—O21	110.7 (3)	O21^vi—O20—H2o16^vi	71 (2)
O16—Ca2—H1o16	22.3 (19)	O21^vi—O20—H1o22^xi	137.4 (10)
O16—Ca2—H2o16	21 (3)	O21^vi—O20—H1o20	71 (5)
O16—Ca2—H1o21	92 (2)	O21^vi—O20—H2o20	158 (6)
O16—Ca2—H2o21	118 (2)	H2o16^vi—O20—H1o22^xi	68 (2)
O16—Ca2—H1o20^iii	68.4 (18)	H2o16^vi—O20—H1o20	56 (6)
O19—Ca2—O20^iii	129.5 (3)	H2o16^vi—O20—H2o20	89 (7)
O19—Ca2—O21	79.2 (3)	H1o22^xi—O20—H1o20	78 (6)
O19—Ca2—H1o16	47.8 (19)	H1o22^xi—O20—H2o20	28 (6)
O19—Ca2—H2o16	78 (3)	H1o20—O20—H2o20	106 (8)
O19—Ca2—H1o21	70.2 (19)	Ca2—O21—O4^xv	114.6 (4)
O19—Ca2—H2o21	68 (2)	Ca2—O21—O5^ii	59.9 (3)
O19—Ca2—H1o20^iii	109.3 (17)	Ca2—O21—O20^iii	55.9 (3)
O20^iii—Ca2—O21	73.9 (3)	Ca2—O21—H1o19	68.2 (17)
O20^iii—Ca2—H1o16	101 (2)	Ca2—O21—H1o21	107 (6)
O20^iii—Ca2—H2o16	63 (3)	Ca2—O21—H2o21	104 (6)
O20^iii—Ca2—H1o21	71 (2)	Ca2—O21—H1o17^iii	113.3 (18)
O20^iii—Ca2—H2o21	93 (2)	Ca2—O21—H1o20^iii	62.5 (17)
O20^iii—Ca2—H1o20^iii	20.2 (17)	O4^xv—O21—O5^ii	135.7 (4)
O21—Ca2—H1o16	106 (2)	O4^xv—O21—O20^iii	60.3 (3)
O21—Ca2—H2o16	95 (3)	O4^xv—O21—H1o19	159.4 (17)
O21—Ca2—H1o21	19 (2)	O4^xv—O21—H1o21	85 (6)
O21—Ca2—H2o21	19 (2)	O4^xv—O21—H2o21	135 (6)
O21—Ca2—H1o20^iii	66.5 (18)	O4^xv—O21—H1o17^iii	64.3 (15)
H1o16—Ca2—H2o16	38 (3)	O4^xv—O21—H1o20^iii	61.9 (17)
H1o16—Ca2—H1o21	88 (3)	O5^ii—O21—O20^iii	107.7 (4)
H1o16—Ca2—H2o21	106 (3)	O5^ii—O21—H1o19	64.3 (18)
H1o16—Ca2—H1o20^iii	85 (3)	O5^ii—O21—H1o21	139 (6)
H2o16—Ca2—H1o21	77 (4)	O5^ii—O21—H2o21	51 (7)
H2o16—Ca2—H2o21	107 (4)	O5^ii—O21—H1o17^iii	77.8 (18)
H2o16—Ca2—H1o20^iii	48 (3)	O5^ii—O21—H1o20^iii	120.6 (17)
H1o21—Ca2—H2o21	31 (3)	O20^iii—O21—H1o19	113.9 (15)
H1o21—Ca2—H1o20^iii	58 (3)	O20^iii—O21—H1o21	90 (6)
H2o21—Ca2—H1o20^iii	86 (3)	O20^iii—O21—H2o21	159 (7)
O2—P1—O6	100.3 (5)	O20^iii—O21—H1o17^iii	99.7 (14)
O2—P1—O11	108.6 (4)	O20^iii—O21—H1o20^iii	18.4 (17)
O2—P1—O13	112.5 (4)	H1o19—O21—H1o21	75 (6)
O2—P1—H2o19^i	102.1 (17)	H1o19—O21—H2o21	58 (6)
O6—P1—O11	110.6 (4)	H1o19—O21—H1o17^iii	135 (2)
O6—P1—O13	111.5 (5)	H1o19—O21—H1o20^iii	106 (2)
O6—P1—H2o19^i	77.0 (17)	H1o21—O21—H2o21	105 (9)
O11—P1—O13	112.7 (5)	H1o21—O21—H1o17^iii	136 (6)
O11—P1—H2o19^i	36.4 (19)	H1o21—O21—H1o20^iii	72 (6)
O13—P1—H2o19^i	141 (2)	H2o21—O21—H1o17^iii	80 (6)
O8—P2—O9	111.5 (4)	H2o21—O21—H1o20^iii	163 (6)
O8—P2—O15	102.8 (5)	H1o17^iii—O21—H1o20^iii	114 (2)
O8—P2—O18	110.4 (5)	Ca1—O22—O4^vii	56.2 (2)
O9—P2—O15	110.1 (4)	Ca1—O22—O18	49.0 (2)
O9—P2—O18	111.6 (5)	Ca1—O22—O23	112.9 (4)
O15—P2—O18	110.1 (5)	Ca1—O22—H2o21^x	95 (2)
U1^v—O1—U2	110.9 (3)	Ca1—O22—H1o22	132 (7)
U1^v—O1—U3	122.0 (4)	Ca1—O22—H2o22	113 (6)
U1^v—O1—O3^v	55.2 (2)	Ca1—O22—H2o20^xi	100 (3)
U1^v—O1—O4	127.1 (4)	Ca1—O22—H2o23	93.6 (18)
U1^v—O1—O5	116.0 (3)	O4^vii—O22—O18	98.7 (3)
U1^v—O1—O6^vi	158.2 (4)	O4^vii—O22—O23	165.6 (5)
U1^v—O1—O10	104.2 (3)	O4^vii—O22—H2o21^x	106.0 (19)
U1^v—O1—O12^v	36.70 (19)	O4^vii—O22—H1o22	168 (7)
U1^v—O1—O14^v	37.68 (18)	O4^vii—O22—H2o22	76 (6)
U1^v—O1—O15^ii	62.2 (3)	O4^vii—O22—H2o20^xi	107 (3)
U1^v—O1—H2o22^viii	107.7 (18)	O4^vii—O22—H2o23	146 (2)
U2—O1—U3	120.7 (4)	O18—O22—O23	76.6 (3)
U2—O1—O3^v	56.1 (2)	O18—O22—H2o21^x	107 (2)
U2—O1—O4	119.1 (4)	O18—O22—H1o22	85 (6)
U2—O1—O5	40.02 (19)	O18—O22—H2o22	156 (5)
U2—O1—O6^vi	57.2 (3)	O18—O22—H2o20^xi	64 (3)
U2—O1—O10	107.0 (3)	O18—O22—H2o23	65 (2)
U2—O1—O12^v	101.0 (3)	O23—O22—H2o21^x	63 (2)
U2—O1—O14^v	112.8 (3)	O23—O22—H1o22	27 (7)
U2—O1—O15^ii	163.9 (4)	O23—O22—H2o22	103 (6)
U2—O1—H2o22^viii	86.1 (18)	O23—O22—H2o20^xi	84 (3)
U3—O1—O3^v	162.5 (3)	O23—O22—H2o23	20.2 (19)
U3—O1—O4	39.30 (17)	H2o21^x—O22—H1o22	84 (6)
U3—O1—O5	120.1 (3)	H2o21^x—O22—H2o22	54 (6)
U3—O1—O6^vi	63.8 (3)	H2o21^x—O22—H2o20^xi	147 (3)
U3—O1—O10	38.32 (17)	H2o21^x—O22—H2o23	57 (3)
U3—O1—O12^v	105.4 (3)	H1o22—O22—H2o22	105 (8)
U3—O1—O14^v	125.1 (4)	H1o22—O22—H2o20^xi	65 (7)
U3—O1—O15^ii	60.9 (3)	H1o22—O22—H2o23	46 (7)
U3—O1—H2o22^viii	101 (2)	H2o22—O22—H2o20^xi	140 (6)
O3^v—O1—O4	158.0 (3)	H2o22—O22—H2o23	107 (6)
O3^v—O1—O5	69.8 (3)	H2o20^xi—O22—H2o23	93 (4)
O3^v—O1—O6^vi	112.1 (4)	O2^iv—O23—O16^xiv	142.1 (4)
O3^v—O1—O10	124.2 (3)	O2^iv—O23—O17^xiv	93.9 (4)
O3^v—O1—O12^v	61.4 (3)	O2^iv—O23—O22	122.0 (4)
O3^v—O1—O14^v	65.0 (3)	O2^iv—O23—H2o16^xiv	139 (2)
O3^v—O1—O15^ii	116.9 (4)	O2^iv—O23—H2o21^x	85 (2)
O3^v—O1—H2o22^viii	96 (2)	O2^iv—O23—H1o22	134 (3)
O4—O1—O5	93.3 (3)	O2^iv—O23—H1o17^xiv	99 (3)
O4—O1—O6^vi	71.9 (3)	O2^iv—O23—H2o17^xiv	101 (2)
O4—O1—O10	77.6 (3)	O2^iv—O23—H1o23	63 (6)
O4—O1—O12^v	135.9 (4)	O2^iv—O23—H2o23	44 (5)
O4—O1—O14^v	103.3 (3)	O16^xiv—O23—O17^xiv	79.5 (4)
O4—O1—O15^ii	73.1 (3)	O16^xiv—O23—O22	92.6 (4)
O4—O1—H2o22^viii	62 (2)	O16^xiv—O23—H2o16^xiv	19.4 (19)
O5—O1—O6^vi	68.2 (3)	O16^xiv—O23—H2o21^x	129 (2)
O5—O1—O10	134.6 (4)	O16^xiv—O23—H1o22	80 (3)
O5—O1—O12^v	130.5 (3)	O16^xiv—O23—H1o17^xiv	81 (3)
O5—O1—O14^v	92.8 (3)	O16^xiv—O23—H2o17^xiv	63.4 (14)
O5—O1—O15^ii	155.5 (4)	O16^xiv—O23—H1o23	90 (6)
O5—O1—H2o22^viii	46.1 (18)	O16^xiv—O23—H2o23	159 (7)
O6^vi—O1—O10	66.6 (3)	O17^xiv—O23—O22	120.1 (4)
O6^vi—O1—O12^v	123.2 (3)	O17^xiv—O23—H2o16^xiv	98.9 (18)
O6^vi—O1—O14^v	159.7 (4)	O17^xiv—O23—H2o21^x	78.6 (19)
O6^vi—O1—O15^ii	123.5 (4)	O17^xiv—O23—H1o22	117 (3)
O6^vi—O1—H2o22^viii	90.5 (17)	O17^xiv—O23—H1o17^xiv	9 (2)
O10—O1—O12^v	73.7 (3)	O17^xiv—O23—H2o17^xiv	18.2 (11)
O10—O1—O14^v	132.6 (4)	O17^xiv—O23—H1o23	40 (6)
O10—O1—O15^ii	63.6 (3)	O17^xiv—O23—H2o23	121 (7)
O10—O1—H2o22^viii	138 (2)	O22—O23—H2o16^xiv	84.1 (18)
O12^v—O1—O14^v	74.4 (3)	O22—O23—H2o21^x	60.8 (19)
O12^v—O1—O15^ii	64.4 (3)	O22—O23—H1o22	13 (3)
O12^v—O1—H2o22^viii	144.0 (19)	O22—O23—H1o17^xiv	111 (2)
O14^v—O1—O15^ii	71.4 (3)	O22—O23—H2o17^xiv	126 (2)
O14^v—O1—H2o22^viii	70.4 (18)	O22—O23—H1o23	159 (7)
O15^ii—O1—H2o22^viii	109.7 (18)	O22—O23—H2o23	78 (5)
U2^ii—O2—U3^iii	101.8 (3)	H2o16^xiv—O23—H2o21^x	135 (3)
U2^ii—O2—P1	135.1 (4)	H2o16^xiv—O23—H1o22	72 (3)
U2^ii—O2—O3^iii	55.2 (2)	H2o16^xiv—O23—H1o17^xiv	100 (3)
U2^ii—O2—O5^ii	38.95 (17)	H2o16^xiv—O23—H2o17^xiv	82 (2)
U2^ii—O2—O6	150.4 (4)	H2o16^xiv—O23—H1o23	104 (7)
U2^ii—O2—O9^ii	53.7 (2)	H2o16^xiv—O23—H2o23	140 (7)
U2^ii—O2—O11	134.9 (4)	H2o21^x—O23—H1o22	70 (4)
U2^ii—O2—O13	102.8 (3)	H2o21^x—O23—H1o17^xiv	71 (3)
U2^ii—O2—O23^ii	102.3 (3)	H2o21^x—O23—H2o17^xiv	96 (2)
U2^ii—O2—H1o23^ii	120.0 (11)	H2o21^x—O23—H1o23	101 (7)
U2^ii—O2—H2o23^ii	85.8 (19)	H2o21^x—O23—H2o23	63 (7)
U3^iii—O2—P1	97.4 (3)	H1o22—O23—H1o17^xiv	109 (4)
U3^iii—O2—O3^iii	49.4 (2)	H1o22—O23—H2o17^xiv	119 (4)
U3^iii—O2—O5^ii	94.1 (3)	H1o22—O23—H1o23	158 (7)
U3^iii—O2—O6	60.5 (3)	H1o22—O23—H2o23	90 (6)
U3^iii—O2—O9^ii	151.5 (3)	H1o17^xiv—O23—H2o17^xiv	24 (2)
U3^iii—O2—O11	121.5 (3)	H1o17^xiv—O23—H1o23	49 (7)
U3^iii—O2—O13	100.3 (3)	H1o17^xiv—O23—H2o23	120 (7)
U3^iii—O2—O23^ii	116.6 (3)	H2o17^xiv—O23—H1o23	39 (6)
U3^iii—O2—H1o23^ii	104 (2)	H2o17^xiv—O23—H2o23	137 (6)
U3^iii—O2—H2o23^ii	121 (3)	H1o23—O23—H2o23	105 (8)
P1—O2—O3^iii	141.5 (5)	Ca2—H1o16—O12^v	147 (5)
P1—O2—O5^ii	100.0 (3)	Ca2—H1o16—O16	77 (5)
P1—O2—O6	39.7 (3)	Ca2—H1o16—O19	65 (2)
P1—O2—O9^ii	93.3 (4)	Ca2—H1o16—H2o16	49 (4)
P1—O2—O11	35.1 (3)	Ca2—H1o16—H1o19	69 (3)
P1—O2—O13	33.3 (2)	Ca2—H1o16—H2o19	85 (4)
P1—O2—O23^ii	104.6 (4)	O12^v—H1o16—O16	122 (7)
P1—O2—H1o23^ii	93.6 (19)	O12^v—H1o16—O19	99 (3)
P1—O2—H2o23^ii	118 (3)	O12^v—H1o16—H2o16	158 (6)
O3^iii—O2—O5^ii	68.9 (3)	O12^v—H1o16—H1o19	100 (3)
O3^iii—O2—O6	109.7 (4)	O12^v—H1o16—H2o19	73 (3)
O3^iii—O2—O9^ii	108.9 (3)	O16—H1o16—O19	139 (7)
O3^iii—O2—O11	169.8 (4)	O16—H1o16—H2o16	37 (4)
O3^iii—O2—O13	122.7 (4)	O16—H1o16—H1o19	138 (7)
O3^iii—O2—O23^ii	107.9 (3)	O16—H1o16—H2o19	161 (8)
O3^iii—O2—H1o23^ii	111 (2)	O19—H1o16—H2o16	103 (6)
O3^iii—O2—H2o23^ii	98 (3)	O19—H1o16—H1o19	10 (2)
O5^ii—O2—O6	114.4 (3)	O19—H1o16—H2o19	26 (3)
O5^ii—O2—O9^ii	58.0 (2)	H2o16—H1o16—H1o19	101 (6)
O5^ii—O2—O11	119.2 (4)	H2o16—H1o16—H2o19	128 (6)
O5^ii—O2—O13	66.7 (3)	H1o19—H1o16—H2o19	32 (3)
O5^ii—O2—O23^ii	137.1 (3)	Ca2—H2o16—O14	67 (3)
O5^ii—O2—H1o23^ii	156.0 (12)	Ca2—H2o16—O16	115 (8)
O5^ii—O2—H2o23^ii	121.5 (18)	Ca2—H2o16—O19	60 (2)
O6—O2—O9^ii	132.8 (4)	Ca2—H2o16—O20^iii	73 (3)
O6—O2—O11	62.1 (3)	Ca2—H2o16—O23^xii	159 (4)
O6—O2—O13	61.6 (3)	Ca2—H2o16—H1o16	93 (6)
O6—O2—O23^ii	106.9 (4)	Ca2—H2o16—H1o22^xii	120 (4)
O6—O2—H1o23^ii	88.6 (10)	Ca2—H2o16—H1o20^iii	88 (4)
O6—O2—H2o23^ii	123.3 (18)	Ca2—H2o16—H2o20^iii	84 (3)
O9^ii—O2—O11	81.2 (3)	O14—H2o16—O16	92 (7)
O9^ii—O2—O13	75.0 (3)	O14—H2o16—O19	116 (4)
O9^ii—O2—O23^ii	85.8 (3)	O14—H2o16—O20^iii	65 (2)
O9^ii—O2—H1o23^ii	102 (2)	O14—H2o16—O23^xii	95 (3)
O9^ii—O2—H2o23^ii	76 (2)	O14—H2o16—H1o16	111 (7)
O11—O2—O13	60.0 (3)	O14—H2o16—H1o22^xii	59 (3)
O11—O2—O23^ii	70.9 (3)	O14—H2o16—H1o20^iii	86 (4)
O11—O2—H1o23^ii	64 (2)	O14—H2o16—H2o20^iii	52 (3)
O11—O2—H2o23^ii	83 (3)	O16—H2o16—O19	82 (5)
O13—O2—O23^ii	129.2 (4)	O16—H2o16—O20^iii	151 (7)
O13—O2—H1o23^ii	124 (2)	O16—H2o16—O23^xii	76 (5)
O13—O2—H2o23^ii	135 (3)	O16—H2o16—H1o16	37 (5)
O23^ii—O2—H1o23^ii	18.9 (12)	O16—H2o16—H1o22^xii	92 (6)
O23^ii—O2—H2o23^ii	16.5 (19)	O16—H2o16—H1o20^iii	154 (8)
H1o23^ii—O2—H2o23^ii	35 (2)	O16—H2o16—H2o20^iii	130 (7)
U1—O3—U2^i	108.9 (3)	O19—H2o16—O20^iii	123 (3)
U1—O3—U3	122.9 (4)	O19—H2o16—O23^xii	142 (3)
U1—O3—O1^i	55.2 (2)	O19—H2o16—H1o16	45 (4)
U1—O3—O2^vi	164.8 (4)	O19—H2o16—H1o22^xii	172 (5)
U1—O3—O4	123.8 (4)	O19—H2o16—H1o20^iii	123 (5)
U1—O3—O7^i	106.1 (3)	O19—H2o16—H2o20^iii	142 (4)
U1—O3—O8^ii	58.9 (3)	O20^iii—H2o16—O23^xii	89 (3)
U1—O3—O10	107.5 (3)	O20^iii—H2o16—H1o16	166 (7)
U1—O3—O12	38.34 (19)	O20^iii—H2o16—H1o22^xii	62 (2)
U1—O3—O14	36.82 (18)	O20^iii—H2o16—H1o20^iii	23 (2)
U1—O3—H1o21^ix	90 (2)	O20^iii—H2o16—H2o20^iii	21.7 (14)
U2^i—O3—U3	120.3 (4)	O23^xii—H2o16—H1o16	105 (5)
U2^i—O3—O1^i	54.1 (2)	O23^xii—H2o16—H1o22^xii	39 (2)
U2^i—O3—O2^vi	56.8 (2)	O23^xii—H2o16—H1o20^iii	78 (4)
U2^i—O3—O4	125.4 (4)	O23^xii—H2o16—H2o20^iii	75 (3)
U2^i—O3—O7^i	38.78 (18)	H1o16—H2o16—H1o22^xii	129 (6)
U2^i—O3—O8^ii	167.7 (4)	H1o16—H2o16—H1o20^iii	161 (8)
U2^i—O3—O10	100.3 (3)	H1o16—H2o16—H2o20^iii	162 (8)
U2^i—O3—O12	102.8 (3)	H1o22^xii—H2o16—H1o20^iii	65 (4)
U2^i—O3—O14	109.3 (3)	H1o22^xii—H2o16—H2o20^iii	42 (2)
U2^i—O3—H1o21^ix	101 (2)	H1o20^iii—H2o16—H2o20^iii	36 (3)
U3—O3—O1^i	148.5 (3)	O17^x—H1o19—O19	162 (8)
U3—O3—O2^vi	67.6 (3)	O17^x—H1o19—O21	107 (3)
U3—O3—O4	38.32 (17)	O17^x—H1o19—H1o16	147 (5)
U3—O3—O7^i	130.2 (4)	O17^x—H1o19—H2o19	128 (6)
U3—O3—O8^ii	69.8 (3)	O17^x—H1o19—H1o21	100 (4)
U3—O3—O10	39.89 (19)	O17^x—H1o19—H2o21	95 (4)
U3—O3—O12	136.0 (4)	O17^x—H1o19—H1o17^x	23 (2)
U3—O3—O14	97.0 (3)	O17^x—H1o19—H2o17^x	26 (3)
U3—O3—H1o21^ix	106 (2)	O17^x—H1o19—H1o23^xiii	57 (4)
O1^i—O3—O2^vi	109.9 (4)	O19—H1o19—O21	88 (6)
O1^i—O3—O4	173.2 (3)	O19—H1o19—H1o16	22 (4)
O1^i—O3—O7^i	68.1 (3)	O19—H1o19—H2o19	37 (4)
O1^i—O3—O8^ii	113.6 (4)	O19—H1o19—H1o21	91 (6)
O1^i—O3—O10	108.6 (3)	O19—H1o19—H2o21	102 (7)
O1^i—O3—O12	65.5 (3)	O19—H1o19—H1o17^x	140 (7)
O1^i—O3—O14	62.9 (3)	O19—H1o19—H2o17^x	146 (8)
O1^i—O3—H1o21^ix	105 (2)	O19—H1o19—H1o23^xiii	107 (7)
O2^vi—O3—O4	71.3 (3)	O21—H1o19—H1o16	84 (3)
O2^vi—O3—O7^i	66.6 (3)	O21—H1o19—H2o19	125 (5)
O2^vi—O3—O8^ii	135.1 (4)	O21—H1o19—H1o21	18.8 (19)
O2^vi—O3—O10	72.9 (3)	O21—H1o19—H2o21	18 (2)
O2^vi—O3—O12	143.1 (4)	O21—H1o19—H1o17^x	129 (4)
O2^vi—O3—O14	137.9 (3)	O21—H1o19—H2o17^x	95 (5)
O2^vi—O3—H1o21^ix	98 (3)	O21—H1o19—H1o23^xiii	164 (5)
O4—O3—O7^i	107.1 (3)	H1o16—H1o19—H2o19	48 (4)
O4—O3—O8^ii	66.7 (3)	H1o16—H1o19—H1o21	81 (4)
O4—O3—O10	78.2 (3)	H1o16—H1o19—H2o21	102 (4)
O4—O3—O12	109.3 (3)	H1o16—H1o19—H1o17^x	132 (4)
O4—O3—O14	120.9 (3)	H1o16—H1o19—H2o17^x	125 (5)
O4—O3—H1o21^ix	68 (2)	H1o16—H1o19—H1o23^xiii	109 (4)
O7^i—O3—O8^ii	141.4 (3)	H2o19—H1o19—H1o21	128 (6)
O7^i—O3—O10	134.2 (4)	H2o19—H1o19—H2o21	137 (6)
O7^i—O3—O12	78.7 (3)	H2o19—H1o19—H1o17^x	105 (6)
O7^i—O3—O14	130.5 (3)	H2o19—H1o19—H2o17^x	131 (7)
O7^i—O3—H1o21^ix	63 (2)	H2o19—H1o19—H1o23^xiii	71 (5)
O8^ii—O3—O10	83.4 (3)	H1o21—H1o19—H2o21	32 (3)
O8^ii—O3—O12	68.8 (3)	H1o21—H1o19—H1o17^x	119 (4)
O8^ii—O3—O14	60.6 (3)	H1o21—H1o19—H2o17^x	82 (5)
O8^ii—O3—H1o21^ix	81 (3)	H1o21—H1o19—H1o23^xiii	151 (5)
O10—O3—O12	144.0 (4)	H2o21—H1o19—H1o17^x	117 (4)
O10—O3—O14	71.3 (3)	H2o21—H1o19—H2o17^x	90 (5)
O10—O3—H1o21^ix	146 (2)	H2o21—H1o19—H1o23^xiii	149 (5)
O12—O3—O14	75.1 (3)	H1o17^x—H1o19—H2o17^x	37 (5)
O12—O3—H1o21^ix	53 (2)	H1o17^x—H1o19—H1o23^xiii	35 (3)
O14—O3—H1o21^ix	124 (3)	H2o17^x—H1o19—H1o23^xiii	70 (5)
U3—O4—Ca1^viii	167.5 (4)	P1^v—H2o19—O6^v	30.3 (10)
U3—O4—O1	51.6 (2)	P1^v—H2o19—O11^v	27.8 (15)
U3—O4—O3	49.3 (2)	P1^v—H2o19—O12^v	100 (3)
U3—O4—O17^viii	136.8 (4)	P1^v—H2o19—O19	130 (7)
U3—O4—O20^viii	126.4 (4)	P1^v—H2o19—H1o16	141 (5)
U3—O4—O21^ix	112.8 (3)	P1^v—H2o19—H1o19	112 (6)
U3—O4—O22^viii	116.9 (3)	P1^v—H2o19—H2o17^x	113 (4)
U3—O4—H1o21^ix	96.3 (16)	P1^v—H2o19—H1o23^xiii	72 (3)
U3—O4—H2o22^viii	105 (2)	O6^v—H2o19—O11^v	57 (2)
U3—O4—H1o20^viii	109.5 (16)	O6^v—H2o19—O12^v	127 (3)
Ca1^viii—O4—O1	117.4 (3)	O6^v—H2o19—O19	99 (7)
Ca1^viii—O4—O3	140.9 (3)	O6^v—H2o19—H1o16	137 (4)
Ca1^viii—O4—O17^viii	50.4 (2)	O6^v—H2o19—H1o19	88 (5)
Ca1^viii—O4—O20^viii	53.2 (2)	O6^v—H2o19—H2o17^x	100 (4)
Ca1^viii—O4—O21^ix	78.5 (3)	O6^v—H2o19—H1o23^xiii	81 (4)
Ca1^viii—O4—O22^viii	51.6 (2)	O11^v—H2o19—O12^v	72 (3)
Ca1^viii—O4—H1o21^ix	94.0 (16)	O11^v—H2o19—O19	155 (8)
Ca1^viii—O4—H2o22^viii	65 (2)	O11^v—H2o19—H1o16	121 (6)
Ca1^viii—O4—H1o20^viii	71.3 (16)	O11^v—H2o19—H1o19	137 (7)
O1—O4—O3	100.9 (3)	O11^v—H2o19—H2o17^x	131 (4)
O1—O4—O17^viii	116.5 (4)	O11^v—H2o19—H1o23^xiii	78 (3)
O1—O4—O20^viii	129.2 (4)	O12^v—H2o19—O19	126 (7)
O1—O4—O21^ix	164.0 (3)	O12^v—H2o19—H1o16	60 (3)
O1—O4—O22^viii	65.8 (3)	O12^v—H2o19—H1o19	144 (6)
O1—O4—H1o21^ix	147.7 (16)	O12^v—H2o19—H2o17^x	126 (4)
O1—O4—H2o22^viii	54 (2)	O12^v—H2o19—H1o23^xiii	104 (4)
O1—O4—H1o20^viii	127.3 (17)	O19—H2o19—H1o16	68 (5)
O3—O4—O17^viii	119.4 (4)	O19—H2o19—H1o19	37 (5)
O3—O4—O20^viii	97.0 (3)	O19—H2o19—H2o17^x	56 (5)
O3—O4—O21^ix	63.7 (3)	O19—H2o19—H1o23^xiii	109 (7)
O3—O4—O22^viii	163.8 (4)	H1o16—H2o19—H1o19	101 (6)
O3—O4—H1o21^ix	47.1 (16)	H1o16—H2o19—H2o17^x	105 (5)
O3—O4—H2o22^viii	154 (2)	H1o16—H2o19—H1o23^xiii	142 (6)
O3—O4—H1o20^viii	79.7 (16)	H1o19—H2o19—H2o17^x	24 (4)
O17^viii—O4—O20^viii	94.0 (3)	H1o19—H2o19—H1o23^xiii	72 (5)
O17^viii—O4—O21^ix	71.2 (3)	H2o17^x—H2o19—H1o23^xiii	54 (3)
O17^viii—O4—O22^viii	76.1 (3)	Ca2—H1o21—O3^xv	156 (4)
O17^viii—O4—H1o21^ix	88.6 (18)	Ca2—H1o21—O4^xv	101 (3)
O17^viii—O4—H2o22^viii	73.8 (17)	Ca2—H1o21—O7^x	136 (3)
O17^viii—O4—H1o20^viii	107.7 (16)	Ca2—H1o21—O12^xv	101 (3)
O20^viii—O4—O21^ix	60.8 (3)	Ca2—H1o21—O21	54 (5)
O20^viii—O4—O22^viii	85.7 (3)	Ca2—H1o21—H1o19	64 (3)
O20^viii—O4—H1o21^ix	63.3 (18)	Ca2—H1o21—H2o21	73 (5)
O20^viii—O4—H2o22^viii	105.0 (17)	Ca2—H1o21—H1o20^iii	59 (3)
O20^viii—O4—H1o20^viii	18.3 (16)	O3^xv—H1o21—O4^xv	65 (2)
O21^ix—O4—O22^viii	130.1 (3)	O3^xv—H1o21—O7^x	68 (2)
O21^ix—O4—H1o21^ix	18.4 (17)	O3^xv—H1o21—O12^xv	74 (3)
O21^ix—O4—H2o22^viii	141 (2)	O3^xv—H1o21—O21	133 (8)
O21^ix—O4—H1o20^viii	57.2 (16)	O3^xv—H1o21—H1o19	133 (4)
O22^viii—O4—H1o21^ix	144.5 (16)	O3^xv—H1o21—H2o21	128 (7)
O22^viii—O4—H2o22^viii	19.4 (17)	O3^xv—H1o21—H1o20^iii	97 (4)
O22^viii—O4—H1o20^viii	100.7 (16)	O4^xv—H1o21—O7^x	109 (3)
H1o21^ix—O4—H2o22^viii	159 (3)	O4^xv—H1o21—O12^xv	123 (4)
H1o21^ix—O4—H1o20^viii	53 (3)	O4^xv—H1o21—O21	77 (6)
H2o22^viii—O4—H1o20^viii	120 (2)	O4^xv—H1o21—H1o19	162 (4)
U2—O5—Ca2^iv	111.1 (4)	O4^xv—H1o21—H2o21	104 (6)
U2—O5—O1	53.1 (2)	O4^xv—H1o21—H1o20^iii	63 (3)
U2—O5—O2^iv	54.6 (2)	O7^x—H1o21—O12^xv	90 (3)
U2—O5—O9	59.0 (3)	O7^x—H1o21—O21	102 (7)
U2—O5—O13^iv	103.2 (3)	O7^x—H1o21—H1o19	79 (3)
U2—O5—O21^iv	161.3 (5)	O7^x—H1o21—H2o21	69 (5)
U2—O5—H2o21^iv	166 (2)	O7^x—H1o21—H1o20^iii	165 (4)
U2—O5—H2o22^viii	114 (3)	O12^xv—H1o21—O21	153 (7)
Ca2^iv—O5—O1	152.6 (3)	O12^xv—H1o21—H1o19	72 (3)
Ca2^iv—O5—O2^iv	86.5 (3)	O12^xv—H1o21—H2o21	133 (6)
Ca2^iv—O5—O9	52.5 (2)	O12^xv—H1o21—H1o20^iii	85 (4)
Ca2^iv—O5—O13^iv	48.9 (2)	O21—H1o21—H1o19	86 (6)
Ca2^iv—O5—O21^iv	50.5 (2)	O21—H1o21—H2o21	37 (5)
Ca2^iv—O5—H2o21^iv	66 (2)	O21—H1o21—H1o20^iii	89 (6)
Ca2^iv—O5—H2o22^viii	128 (2)	H1o19—H1o21—H2o21	63 (5)
O1—O5—O2^iv	97.1 (3)	H1o19—H1o21—H1o20^iii	113 (4)
O1—O5—O9	105.7 (3)	H2o21—H1o21—H1o20^iii	124 (6)
O1—O5—O13^iv	147.4 (3)	Ca2—H2o21—O5^ii	61 (2)
O1—O5—O21^iv	141.3 (4)	Ca2—H2o21—O7^x	147 (4)
O1—O5—H2o21^iv	123 (2)	Ca2—H2o21—O19	50.2 (16)
O1—O5—H2o22^viii	61 (3)	Ca2—H2o21—O21	56 (5)
O2^iv—O5—O9	61.8 (3)	Ca2—H2o21—O22^x	130 (4)
O2^iv—O5—O13^iv	51.6 (2)	Ca2—H2o21—O23^x	140 (4)
O2^iv—O5—O21^iv	119.6 (3)	Ca2—H2o21—H1o19	69 (3)
O2^iv—O5—H2o21^iv	136 (2)	Ca2—H2o21—H1o21	76 (5)
O2^iv—O5—H2o22^viii	142 (2)	Ca2—H2o21—H1o22^x	134 (5)
O9—O5—O13^iv	70.3 (3)	Ca2—H2o21—H2o22^x	112 (5)
O9—O5—O21^iv	102.4 (4)	Ca2—H2o21—H1o17^iii	103 (4)
O9—O5—H2o21^iv	115 (2)	Ca2—H2o21—H2o17^x	96 (3)
O9—O5—H2o22^viii	149 (3)	Ca2—H2o21—H2o23^x	155 (4)
O13^iv—O5—O21^iv	68.0 (3)	O5^ii—H2o21—O7^x	137 (4)
O13^iv—O5—H2o21^iv	85 (2)	O5^ii—H2o21—O19	71 (3)
O13^iv—O5—H2o22^viii	137 (3)	O5^ii—H2o21—O21	111 (8)
O21^iv—O5—H2o21^iv	18 (2)	O5^ii—H2o21—O22^x	70 (3)
O21^iv—O5—H2o22^viii	82 (2)	O5^ii—H2o21—O23^x	99 (3)
H2o21^iv—O5—H2o22^viii	64 (3)	O5^ii—H2o21—H1o19	77 (4)
U2^iii—O6—U3^iii	105.4 (3)	O5^ii—H2o21—H1o21	137 (7)
U2^iii—O6—P1	147.4 (5)	O5^ii—H2o21—H1o22^x	74 (3)
U2^iii—O6—O1^iii	54.1 (2)	O5^ii—H2o21—H2o22^x	52 (3)
U2^iii—O6—O2	171.3 (5)	O5^ii—H2o21—H1o17^iii	86 (4)
U2^iii—O6—O7^iii	39.49 (18)	O5^ii—H2o21—H2o17^x	102 (4)
U2^iii—O6—O11	127.5 (4)	O5^ii—H2o21—H2o23^x	115 (4)
U2^iii—O6—O13	121.1 (4)	O7^x—H2o21—O19	104 (3)
U2^iii—O6—H2o19^i	103.2 (11)	O7^x—H2o21—O21	111 (8)
U3^iii—O6—P1	102.9 (4)	O7^x—H2o21—O22^x	71 (2)
U3^iii—O6—O1^iii	51.6 (2)	O7^x—H2o21—O23^x	72 (2)
U3^iii—O6—O2	65.9 (3)	O7^x—H2o21—H1o19	88 (4)
U3^iii—O6—O7^iii	105.2 (3)	O7^x—H2o21—H1o21	79 (6)
U3^iii—O6—O11	125.9 (3)	O7^x—H2o21—H1o22^x	75 (3)
U3^iii—O6—O13	104.5 (3)	O7^x—H2o21—H2o22^x	87 (4)
U3^iii—O6—H2o19^i	124.7 (18)	O7^x—H2o21—H1o17^iii	106 (4)
P1—O6—O1^iii	152.8 (5)	O7^x—H2o21—H2o17^x	57 (3)
P1—O6—O2	40.1 (3)	O7^x—H2o21—H2o23^x	54 (3)
P1—O6—O7^iii	116.6 (4)	O19—H2o21—O21	90 (6)
P1—O6—O11	34.3 (3)	O19—H2o21—O22^x	106 (3)
P1—O6—O13	34.0 (3)	O19—H2o21—O23^x	161 (4)
P1—O6—H2o19^i	72.7 (14)	O19—H2o21—H1o19	19 (2)
O1^iii—O6—O2	117.3 (4)	O19—H2o21—H1o21	80 (5)
O1^iii—O6—O7^iii	69.2 (3)	O19—H2o21—H1o22^x	123 (4)
O1^iii—O6—O11	165.8 (4)	O19—H2o21—H2o22^x	93 (4)
O1^iii—O6—O13	133.2 (4)	O19—H2o21—H1o17^iii	150 (4)
O1^iii—O6—H2o19^i	127.3 (17)	O19—H2o21—H2o17^x	47 (2)
O2—O6—O7^iii	139.8 (4)	O19—H2o21—H2o23^x	154 (4)
O2—O6—O11	61.2 (3)	O21—H2o21—O22^x	163 (7)
O2—O6—O13	62.7 (3)	O21—H2o21—O23^x	109 (7)
O2—O6—H2o19^i	83.2 (11)	O21—H2o21—H1o19	104 (6)
O7^iii—O6—O11	122.0 (4)	O21—H2o21—H1o21	37 (5)
O7^iii—O6—O13	84.0 (3)	O21—H2o21—H1o22^x	145 (7)
O7^iii—O6—H2o19^i	126.5 (15)	O21—H2o21—H2o22^x	160 (9)
O11—O6—O13	60.1 (3)	O21—H2o21—H1o17^iii	81 (6)
O11—O6—H2o19^i	39.9 (16)	O21—H2o21—H2o17^x	111 (7)
O13—O6—H2o19^i	99.5 (17)	O21—H2o21—H2o23^x	109 (7)
U2—O7—Ca1	135.1 (4)	O22^x—H2o21—O23^x	55.7 (16)
U2—O7—O3^v	53.0 (2)	O22^x—H2o21—H1o19	92 (3)
U2—O7—O6^vi	55.2 (2)	O22^x—H2o21—H1o21	150 (7)
U2—O7—O17	137.4 (4)	O22^x—H2o21—H1o22^x	18.8 (11)
U2—O7—H1o21^x	102.4 (18)	O22^x—H2o21—H2o22^x	19 (2)
U2—O7—H2o21^x	129 (2)	O22^x—H2o21—H1o17^iii	82 (3)
U2—O7—H2o17	129 (2)	O22^x—H2o21—H2o17^x	84 (3)
U2—O7—H2o23	98 (2)	O22^x—H2o21—H2o23^x	58 (3)
Ca1—O7—O3^v	169.9 (4)	O23^x—H2o21—H1o19	146 (4)
Ca1—O7—O6^vi	85.9 (3)	O23^x—H2o21—H1o21	117 (6)
Ca1—O7—O17	51.0 (2)	O23^x—H2o21—H1o22^x	38.1 (19)
Ca1—O7—H1o21^x	122.1 (18)	O23^x—H2o21—H2o22^x	69 (3)
Ca1—O7—H2o21^x	95 (2)	O23^x—H2o21—H1o17^iii	38 (2)
Ca1—O7—H2o17	70.0 (15)	O23^x—H2o21—H2o17^x	123 (4)
Ca1—O7—H2o23	95 (2)	O23^x—H2o21—H2o23^x	19 (2)
O3^v—O7—O6^vi	97.8 (3)	H1o19—H2o21—H1o21	85 (6)
O3^v—O7—O17	119.4 (4)	H1o19—H2o21—H1o22^x	111 (4)
O3^v—O7—H1o21^x	49.4 (18)	H1o19—H2o21—H2o22^x	83 (4)
O3^v—O7—H2o21^x	79 (2)	H1o19—H2o21—H1o17^iii	163 (5)
O3^v—O7—H2o17	100.1 (15)	H1o19—H2o21—H2o17^x	31 (3)
O3^v—O7—H2o23	90 (2)	H1o19—H2o21—H2o23^x	136 (5)
O6^vi—O7—O17	90.3 (3)	H1o21—H2o21—H1o22^x	149 (7)
O6^vi—O7—H1o21^x	136 (2)	H1o21—H2o21—H2o22^x	162 (7)
O6^vi—O7—H2o21^x	163 (2)	H1o21—H2o21—H1o17^iii	108 (6)
O6^vi—O7—H2o17	96 (2)	H1o21—H2o21—H2o17^x	78 (5)
O6^vi—O7—H2o23	134 (3)	H1o21—H2o21—H2o23^x	105 (7)
O17—O7—H1o21^x	84.9 (19)	H1o22^x—H2o21—H2o22^x	31 (3)
O17—O7—H2o21^x	77 (2)	H1o22^x—H2o21—H1o17^iii	64 (3)
O17—O7—H2o17	19.5 (14)	H1o22^x—H2o21—H2o17^x	101 (3)
O17—O7—H2o23	125 (2)	H1o22^x—H2o21—H2o23^x	45 (3)
H1o21^x—O7—H2o21^x	32 (3)	H2o22^x—H2o21—H1o17^iii	87 (4)
H1o21^x—O7—H2o17	68 (3)	H2o22^x—H2o21—H2o17^x	85 (4)
H1o21^x—O7—H2o23	81 (3)	H2o22^x—H2o21—H2o23^x	75 (4)
H2o21^x—O7—H2o17	68 (3)	H1o17^iii—H2o21—H2o17^x	161 (4)
H2o21^x—O7—H2o23	63 (3)	H1o17^iii—H2o21—H2o23^x	53 (3)
H2o17—O7—H2o23	127 (3)	H2o17^x—H2o21—H2o23^x	108 (4)
U1^iv—O8—U3^iv	98.1 (3)	O14^xiv—H1o22—O20^xi	62 (2)
U1^iv—O8—P2	140.8 (5)	O14^xiv—H1o22—O22	95 (7)
U1^iv—O8—O3^iv	53.5 (2)	O14^xiv—H1o22—O23	124 (3)
U1^iv—O8—O9	107.9 (3)	O14^xiv—H1o22—H2o16^xiv	61 (3)
U1^iv—O8—O14^iv	38.78 (18)	O14^xiv—H1o22—H2o21^x	132 (5)
U1^iv—O8—O15	130.5 (4)	O14^xiv—H1o22—H2o22	89 (6)
U1^iv—O8—O18	159.3 (4)	O14^xiv—H1o22—H1o20^xi	76 (3)
U1^iv—O8—H1o20^xi	111 (2)	O14^xiv—H1o22—H2o20^xi	56 (4)
U3^iv—O8—P2	93.7 (4)	O14^xiv—H1o22—H1o23	120 (3)
U3^iv—O8—O3^iv	48.2 (2)	O14^xiv—H1o22—H2o23	150 (4)
U3^iv—O8—O9	114.1 (3)	O20^xi—H1o22—O22	101 (6)
U3^iv—O8—O14^iv	88.5 (3)	O20^xi—H1o22—O23	103 (4)
U3^iv—O8—O15	55.8 (3)	O20^xi—H1o22—H2o16^xiv	50 (2)
U3^iv—O8—O18	102.2 (3)	O20^xi—H1o22—H2o21^x	166 (5)
U3^iv—O8—H1o20^xi	100 (2)	O20^xi—H1o22—H2o22	130 (5)
P2—O8—O3^iv	139.1 (5)	O20^xi—H1o22—H1o20^xi	19.8 (19)
P2—O8—O9	34.3 (3)	O20^xi—H1o22—H2o20^xi	13 (3)
P2—O8—O14^iv	104.9 (4)	O20^xi—H1o22—H1o23	107 (4)
P2—O8—O15	38.7 (3)	O20^xi—H1o22—H2o23	108 (5)
P2—O8—O18	34.1 (3)	O22—H1o22—O23	141 (9)
P2—O8—H1o20^xi	103 (2)	O22—H1o22—H2o16^xiv	148 (8)
O3^iv—O8—O9	138.8 (4)	O22—H1o22—H2o21^x	77 (7)
O3^iv—O8—O14^iv	66.2 (3)	O22—H1o22—H2o22	38 (5)
O3^iv—O8—O15	100.6 (4)	O22—H1o22—H1o20^xi	116 (7)
O3^iv—O8—O18	146.8 (4)	O22—H1o22—H2o20^xi	90 (6)
O3^iv—O8—H1o20^xi	98 (2)	O22—H1o22—H1o23	143 (9)
O9—O8—O14^iv	78.0 (3)	O22—H1o22—H2o23	115 (8)
O9—O8—O15	61.4 (3)	O23—H1o22—H2o16^xiv	69 (3)
O9—O8—O18	59.8 (3)	O23—H1o22—H2o21^x	71 (4)
O9—O8—H1o20^xi	123 (2)	O23—H1o22—H2o22	127 (7)
O14^iv—O8—O15	94.5 (3)	O23—H1o22—H1o20^xi	83 (4)
O14^iv—O8—O18	137.3 (4)	O23—H1o22—H2o20^xi	116 (6)
O14^iv—O8—H1o20^xi	150 (2)	O23—H1o22—H1o23	7 (2)
O15—O8—O18	61.0 (3)	O23—H1o22—H2o23	26 (2)
O15—O8—H1o20^xi	114 (2)	H2o16^xiv—H1o22—H2o21^x	134 (3)
O18—O8—H1o20^xi	69 (2)	H2o16^xiv—H1o22—H2o22	146 (7)
U2—O9—Ca2^iv	100.2 (3)	H2o16^xiv—H1o22—H1o20^xi	42 (3)
U2—O9—P2	132.7 (4)	H2o16^xiv—H1o22—H2o20^xi	60 (4)
U2—O9—O2^iv	51.1 (2)	H2o16^xiv—H1o22—H1o23	69 (3)
U2—O9—O5	39.61 (18)	H2o16^xiv—H1o22—H2o23	91 (4)
U2—O9—O8	138.7 (3)	H2o21^x—H1o22—H2o22	56 (5)
U2—O9—O15	145.2 (4)	H2o21^x—H1o22—H1o20^xi	150 (5)
U2—O9—O18	99.4 (3)	H2o21^x—H1o22—H2o20^xi	165 (5)
Ca2^iv—O9—P2	127.1 (4)	H2o21^x—H1o22—H1o23	69 (4)
Ca2^iv—O9—O2^iv	90.3 (3)	H2o21^x—H1o22—H2o23	61 (5)
Ca2^iv—O9—O5	60.9 (2)	H2o22—H1o22—H1o20^xi	149 (6)
Ca2^iv—O9—O8	107.2 (3)	H2o22—H1o22—H2o20^xi	117 (6)
Ca2^iv—O9—O15	101.7 (3)	H2o22—H1o22—H1o23	123 (6)
Ca2^iv—O9—O18	160.0 (4)	H2o22—H1o22—H2o23	115 (7)
P2—O9—O2^iv	120.6 (4)	H1o20^xi—H1o22—H2o20^xi	33 (4)
P2—O9—O5	170.9 (4)	H1o20^xi—H1o22—H1o23	88 (4)
P2—O9—O8	34.2 (3)	H1o20^xi—H1o22—H2o23	89 (5)
P2—O9—O15	34.9 (3)	H2o20^xi—H1o22—H1o23	120 (5)
P2—O9—O18	33.4 (3)	H2o20^xi—H1o22—H2o23	119 (7)
O2^iv—O9—O5	60.2 (2)	H1o23—H1o22—H2o23	32 (3)
O2^iv—O9—O8	97.9 (3)	Ca1—H2o22—O1^vii	115 (3)
O2^iv—O9—O15	154.0 (4)	Ca1—H2o22—O4^vii	52.4 (17)
O2^iv—O9—O18	105.2 (3)	Ca1—H2o22—O5^vii	143 (4)
O5—O9—O8	153.0 (4)	Ca1—H2o22—O22	49 (5)
O5—O9—O15	145.6 (4)	Ca1—H2o22—H2o21^x	93 (4)
O5—O9—O18	138.1 (4)	Ca1—H2o22—H1o22	83 (5)
O8—O9—O15	56.6 (3)	Ca1—H2o22—H2o20^xi	73 (3)
O8—O9—O18	58.8 (3)	O1^vii—H2o22—O4^vii	65 (2)
O15—O9—O18	59.1 (3)	O1^vii—H2o22—O5^vii	73 (3)
U3—O10—O1	50.9 (2)	O1^vii—H2o22—O22	117 (6)
U3—O10—O3	52.4 (2)	O1^vii—H2o22—H2o21^x	135 (4)
U3—O10—O15^ii	57.8 (3)	O1^vii—H2o22—H1o22	123 (6)
U3—O10—O16	127.2 (4)	O1^vii—H2o22—H2o20^xi	95 (3)
U3—O10—O17	143.1 (5)	O4^vii—H2o22—O5^vii	114 (4)
U3—O10—H1o17	161.1 (18)	O4^vii—H2o22—O22	84 (6)
U3—O10—H2o17	138 (2)	O4^vii—H2o22—H2o21^x	122 (4)
O1—O10—O3	103.2 (3)	O4^vii—H2o22—H1o22	121 (5)
O1—O10—O15^ii	53.0 (3)	O4^vii—H2o22—H2o20^xi	89 (3)
O1—O10—O16	108.5 (4)	O5^vii—H2o22—O22	162 (8)
O1—O10—O17	99.1 (3)	O5^vii—H2o22—H2o21^x	64 (3)
O1—O10—H1o17	118.5 (10)	O5^vii—H2o22—H1o22	125 (6)
O1—O10—H2o17	87 (2)	O5^vii—H2o22—H2o20^xi	144 (4)
O3—O10—O15^ii	86.3 (3)	O22—H2o22—H2o21^x	107 (7)
O3—O10—O16	115.0 (4)	O22—H2o22—H1o22	37 (4)
O3—O10—O17	148.0 (4)	O22—H2o22—H2o20^xi	28 (4)
O3—O10—H1o17	134.8 (11)	H2o21^x—H2o22—H1o22	93 (6)
O3—O10—H2o17	167.2 (17)	H2o21^x—H2o22—H2o20^xi	127 (5)
O15^ii—O10—O16	71.4 (3)	H1o22—H2o22—H2o20^xi	36 (4)
O15^ii—O10—O17	125.7 (4)	Ca1—H1o17—O10	98 (3)
O15^ii—O10—H1o17	132.2 (17)	Ca1—H1o17—O17	41 (4)
O15^ii—O10—H2o17	106.0 (15)	Ca1—H1o17—O21^vi	71 (2)
O16—O10—O17	78.3 (3)	Ca1—H1o17—O23^xii	151 (4)
O16—O10—H1o17	69.0 (19)	Ca1—H1o17—H1o19^x	91 (2)
O16—O10—H2o17	67.2 (14)	Ca1—H1o17—H2o21^vi	88 (3)
O17—O10—H1o17	19.9 (11)	Ca1—H1o17—H2o17	78 (3)
O17—O10—H2o17	19.7 (14)	Ca1—H1o17—H1o23^xii	136 (6)
H1o17—O10—H2o17	33 (2)	Ca1—H1o17—H2o23^xii	132 (4)
U1—O11—P1	137.8 (4)	O10—H1o17—O17	89 (6)
U1—O11—O2	138.9 (3)	O10—H1o17—O21^vi	110 (3)
U1—O11—O6	153.1 (4)	O10—H1o17—O23^xii	106 (3)
U1—O11—O12	38.20 (19)	O10—H1o17—H1o19^x	107 (3)
U1—O11—O13	104.5 (3)	O10—H1o17—H2o21^vi	101 (3)
U1—O11—O14	37.75 (19)	O10—H1o17—H2o17	75 (5)
U1—O11—O15^iii	54.7 (2)	O10—H1o17—H1o23^xii	126 (6)
U1—O11—O19^i	109.9 (4)	O10—H1o17—H2o23^xii	119 (3)
U1—O11—H2o19^i	105 (3)	O17—H1o17—O21^vi	112 (6)
U1—O11—H1o23^ii	123 (2)	O17—H1o17—O23^xii	153 (7)
P1—O11—O2	36.3 (3)	O17—H1o17—H1o19^x	56 (4)
P1—O11—O6	35.1 (3)	O17—H1o17—H2o21^vi	129 (7)
P1—O11—O12	176.0 (5)	O17—H1o17—H2o17	37 (3)
P1—O11—O13	33.7 (3)	O17—H1o17—H1o23^xii	124 (7)
P1—O11—O14	100.1 (4)	O17—H1o17—H2o23^xii	150 (8)
P1—O11—O15^iii	117.3 (4)	O21^vi—H1o17—O23^xii	85 (2)
P1—O11—O19^i	109.1 (5)	O21^vi—H1o17—H1o19^x	141 (4)
P1—O11—H2o19^i	116 (3)	O21^vi—H1o17—H2o21^vi	18.6 (18)
P1—O11—H1o23^ii	91 (2)	O21^vi—H1o17—H2o17	149 (5)
O2—O11—O6	56.7 (3)	O21^vi—H1o17—H1o23^xii	96 (5)
O2—O11—O12	145.4 (3)	O21^vi—H1o17—H2o23^xii	68 (3)
O2—O11—O13	61.3 (3)	O23^xii—H1o17—H1o19^x	97 (4)
O2—O11—O14	110.7 (3)	O23^xii—H1o17—H2o21^vi	71 (2)
O2—O11—O15^iii	153.6 (4)	O23^xii—H1o17—H2o17	124 (6)
O2—O11—O19^i	105.6 (4)	O23^xii—H1o17—H1o23^xii	29 (3)
O2—O11—H2o19^i	108 (3)	O23^xii—H1o17—H2o23^xii	19 (3)
O2—O11—H1o23^ii	60 (2)	H1o19^x—H1o17—H2o21^vi	152 (5)
O6—O11—O12	147.6 (4)	H1o19^x—H1o17—H2o17	37 (5)
O6—O11—O13	60.3 (3)	H1o19^x—H1o17—H1o23^xii	71 (4)
O6—O11—O14	125.0 (3)	H1o19^x—H1o17—H2o23^xii	104 (5)
O6—O11—O15^iii	102.2 (3)	H2o21^vi—H1o17—H2o17	165 (6)
O6—O11—O19^i	75.6 (3)	H2o21^vi—H1o17—H1o23^xii	89 (4)
O6—O11—H2o19^i	83 (3)	H2o21^vi—H1o17—H2o23^xii	57 (3)
O6—O11—H1o23^ii	84 (2)	H2o17—H1o17—H1o23^xii	105 (6)
O12—O11—O13	142.3 (4)	H2o17—H1o17—H2o23^xii	137 (7)
O12—O11—O14	75.9 (3)	H1o23^xii—H1o17—H2o23^xii	33 (3)
O12—O11—O15^iii	60.9 (3)	O7—H2o17—O10	89 (3)
O12—O11—O19^i	74.5 (3)	O7—H2o17—O12^v	83 (3)
O12—O11—H2o19^i	68 (3)	O7—H2o17—O17	89 (5)
O12—O11—H1o23^ii	93 (2)	O7—H2o17—O19^x	120 (3)
O13—O11—O14	67.3 (3)	O7—H2o17—O23^xii	153 (3)
O13—O11—O15^iii	95.3 (3)	O7—H2o17—H1o19^x	115 (5)
O13—O11—O19^i	134.2 (4)	O7—H2o17—H2o19^x	139 (4)
O13—O11—H2o19^i	142 (3)	O7—H2o17—H2o21^x	55 (2)
O13—O11—H1o23^ii	121 (2)	O7—H2o17—H1o17	122 (5)
O14—O11—O15^iii	66.1 (3)	O7—H2o17—H1o23^xii	154 (4)
O14—O11—O19^i	143.7 (4)	O10—H2o17—O12^v	80 (3)
O14—O11—H2o19^i	141 (3)	O10—H2o17—O17	87 (6)
O14—O11—H1o23^ii	141.2 (15)	O10—H2o17—O19^x	139 (2)
O15^iii—O11—O19^i	81.3 (3)	O10—H2o17—O23^xii	79 (2)
O15^iii—O11—H2o19^i	83 (3)	O10—H2o17—H1o19^x	151 (4)
O15^iii—O11—H1o23^ii	139.5 (16)	O10—H2o17—H2o19^x	128 (3)
O19^i—O11—H2o19^i	8 (3)	O10—H2o17—H2o21^x	138 (4)
O19^i—O11—H1o23^ii	61.1 (11)	O10—H2o17—H1o17	72 (5)
H2o19^i—O11—H1o23^ii	58 (3)	O10—H2o17—H1o23^xii	94 (3)
U1—O12—O1^i	50.2 (2)	O12^v—H2o17—O17	165 (9)
U1—O12—O3	52.9 (3)	O12^v—H2o17—O19^x	75.4 (18)
U1—O12—O11	55.0 (3)	O12^v—H2o17—O23^xii	117.8 (19)
U1—O12—O15^iii	57.8 (2)	O12^v—H2o17—H1o19^x	86 (4)
U1—O12—H1o16^i	121 (2)	O12^v—H2o17—H2o19^x	86 (3)
U1—O12—H2o19^i	93.4 (19)	O12^v—H2o17—H2o21^x	76 (3)
U1—O12—H1o21^ix	104 (2)	O12^v—H2o17—H1o17	141 (5)
U1—O12—H2o17^i	133 (2)	O12^v—H2o17—H1o23^xii	123 (4)
O1^i—O12—O3	53.1 (2)	O17—H2o17—O19^x	120 (9)
O1^i—O12—O11	96.7 (3)	O17—H2o17—O23^xii	67 (5)
O1^i—O12—O15^iii	51.5 (2)	O17—H2o17—H1o19^x	110 (9)
O1^i—O12—H1o16^i	108 (2)	O17—H2o17—H2o19^x	109 (8)
O1^i—O12—H2o19^i	121.6 (19)	O17—H2o17—H2o21^x	109 (5)
O1^i—O12—H1o21^ix	95 (2)	O17—H2o17—H1o17	38 (5)
O1^i—O12—H2o17^i	83 (2)	O17—H2o17—H1o23^xii	66 (6)
O3—O12—O11	102.8 (3)	O19^x—H2o17—O23^xii	84 (3)
O3—O12—O15^iii	98.4 (3)	O19^x—H2o17—H1o19^x	13 (3)
O3—O12—H1o16^i	161 (2)	O19^x—H2o17—H2o19^x	19.6 (14)
O3—O12—H2o19^i	142.1 (17)	O19^x—H2o17—H2o21^x	65 (3)
O3—O12—H1o21^ix	53 (2)	O19^x—H2o17—H1o17	110 (6)
O3—O12—H2o17^i	97.7 (16)	O19^x—H2o17—H1o23^xii	74 (4)
O11—O12—O15^iii	61.7 (3)	O23^xii—H2o17—H1o19^x	85 (5)
O11—O12—H1o16^i	82 (2)	O23^xii—H2o17—H2o19^x	64 (2)
O11—O12—H2o19^i	39.7 (18)	O23^xii—H2o17—H2o21^x	142 (5)
O11—O12—H1o21^ix	134 (2)	O23^xii—H2o17—H1o17	32 (4)
O11—O12—H2o17^i	154.4 (16)	O23^xii—H2o17—H1o23^xii	15 (2)
O15^iii—O12—H1o16^i	67 (2)	H1o19^x—H2o17—H2o19^x	25 (4)
O15^iii—O12—H2o19^i	71.0 (18)	H1o19^x—H2o17—H2o21^x	60 (5)
O15^iii—O12—H1o21^ix	146 (2)	H1o19^x—H2o17—H1o17	106 (8)
O15^iii—O12—H2o17^i	100 (2)	H1o19^x—H2o17—H1o23^xii	73 (6)
H1o16^i—O12—H2o19^i	47 (2)	H2o19^x—H2o17—H2o21^x	84 (4)
H1o16^i—O12—H1o21^ix	136 (3)	H2o19^x—H2o17—H1o17	91 (6)
H1o16^i—O12—H2o17^i	74 (3)	H2o19^x—H2o17—H1o23^xii	54 (3)
H2o19^i—O12—H1o21^ix	142 (3)	H2o21^x—H2o17—H1o17	142 (6)
H2o19^i—O12—H2o17^i	120 (2)	H2o21^x—H2o17—H1o23^xii	127 (5)
H1o21^ix—O12—H2o17^i	71 (3)	H1o17—H2o17—H1o23^xii	37 (5)
Ca1^iii—O13—Ca2	105.0 (3)	Ca2^vi—H1o20—O4^vii	104 (3)
Ca1^iii—O13—P1	129.6 (4)	Ca2^vi—H1o20—O8^xi	141 (4)
Ca1^iii—O13—O2	148.8 (4)	Ca2^vi—H1o20—O16^vi	51.1 (14)
Ca1^iii—O13—O5^ii	119.8 (3)	Ca2^vi—H1o20—O18^xi	161 (3)
Ca1^iii—O13—O6	98.0 (3)	Ca2^vi—H1o20—O20	71 (5)
Ca1^iii—O13—O11	126.0 (3)	Ca2^vi—H1o20—O21^vi	51.0 (15)
Ca1^iii—O13—O20^iii	54.6 (2)	Ca2^vi—H1o20—H2o16^vi	43 (3)
Ca2—O13—P1	124.5 (4)	Ca2^vi—H1o20—H1o21^vi	63 (3)
Ca2—O13—O2	101.1 (3)	Ca2^vi—H1o20—H1o22^xi	99 (3)
Ca2—O13—O5^ii	58.4 (2)	Ca2^vi—H1o20—H2o20	86 (5)
Ca2—O13—O6	156.6 (4)	O4^vii—H1o20—O8^xi	70 (2)
Ca2—O13—O11	108.4 (3)	O4^vii—H1o20—O16^vi	148 (3)
Ca2—O13—O20^iii	56.9 (2)	O4^vii—H1o20—O18^xi	84 (2)
P1—O13—O2	34.2 (3)	O4^vii—H1o20—O20	82 (5)
P1—O13—O5^ii	95.8 (4)	O4^vii—H1o20—O21^vi	60.9 (18)
P1—O13—O6	34.5 (3)	O4^vii—H1o20—H2o16^vi	141 (5)
P1—O13—O11	33.5 (3)	O4^vii—H1o20—H1o21^vi	64 (3)
P1—O13—O20^iii	149.4 (5)	O4^vii—H1o20—H1o22^xi	145 (3)
O2—O13—O5^ii	61.7 (3)	O4^vii—H1o20—H2o20	111 (5)
O2—O13—O6	55.7 (3)	O8^xi—H1o20—O16^vi	115 (3)
O2—O13—O11	58.7 (3)	O8^xi—H1o20—O18^xi	58.1 (18)
O2—O13—O20^iii	156.2 (4)	O8^xi—H1o20—O20	141 (7)
O5^ii—O13—O6	105.9 (4)	O8^xi—H1o20—O21^vi	97 (3)
O5^ii—O13—O11	113.7 (3)	O8^xi—H1o20—H2o16^vi	118 (5)
O5^ii—O13—O20^iii	106.5 (3)	O8^xi—H1o20—H1o21^vi	81 (3)
O6—O13—O11	59.5 (3)	O8^xi—H1o20—H1o22^xi	107 (4)
O6—O13—O20^iii	145.3 (4)	O8^xi—H1o20—H2o20	133 (6)
O11—O13—O20^iii	116.3 (4)	O16^vi—H1o20—O18^xi	126 (3)
U1—O14—Ca2	136.7 (4)	O16^vi—H1o20—O20	103 (6)
U1—O14—O1^i	50.8 (2)	O16^vi—H1o20—O21^vi	88 (2)
U1—O14—O3	49.5 (2)	O16^vi—H1o20—H2o16^vi	8 (3)
U1—O14—O8^ii	57.9 (2)	O16^vi—H1o20—H1o21^vi	85 (3)
U1—O14—O11	53.1 (2)	O16^vi—H1o20—H1o22^xi	66 (2)
U1—O14—O20^iii	145.6 (4)	O16^vi—H1o20—H2o20	88 (5)
U1—O14—H2o16	164.4 (19)	O18^xi—H1o20—O20	94 (5)
U1—O14—H1o22^xii	127.8 (19)	O18^xi—H1o20—O21^vi	143 (3)
U1—O14—H2o20^iii	139 (3)	O18^xi—H1o20—H2o16^vi	134 (5)
Ca2—O14—O1^i	170.6 (3)	O18^xi—H1o20—H1o21^vi	135 (4)
Ca2—O14—O3	136.0 (3)	O18^xi—H1o20—H1o22^xi	67 (3)
Ca2—O14—O8^ii	91.4 (3)	O18^xi—H1o20—H2o20	75 (5)
Ca2—O14—O11	88.2 (3)	O20—H1o20—O21^vi	91 (6)
Ca2—O14—O20^iii	54.2 (2)	O20—H1o20—H2o16^vi	101 (6)
Ca2—O14—H2o16	38.7 (18)	O20—H1o20—H1o21^vi	111 (6)
Ca2—O14—H1o22^xii	95.5 (19)	O20—H1o20—H1o22^xi	82 (6)
Ca2—O14—H2o20^iii	71.0 (19)	O20—H1o20—H2o20	37 (4)
O1^i—O14—O3	52.0 (2)	O21^vi—H1o20—H2o16^vi	80 (4)
O1^i—O14—O8^ii	98.1 (3)	O21^vi—H1o20—H1o21^vi	20 (2)
O1^i—O14—O11	95.7 (3)	O21^vi—H1o20—H1o22^xi	150 (4)
O1^i—O14—O20^iii	116.3 (3)	O21^vi—H1o20—H2o20	125 (5)
O1^i—O14—H2o16	136.3 (18)	H2o16^vi—H1o20—H1o21^vi	79 (4)
O1^i—O14—H1o22^xii	77.2 (18)	H2o16^vi—H1o20—H1o22^xi	73 (4)
O1^i—O14—H2o20^iii	99.5 (19)	H2o16^vi—H1o20—H2o20	91 (6)
O3—O14—O8^ii	53.2 (3)	H1o21^vi—H1o20—H1o22^xi	151 (4)
O3—O14—O11	97.9 (3)	H1o21^vi—H1o20—H2o20	144 (6)
O3—O14—O20^iii	154.9 (4)	H1o22^xi—H1o20—H2o20	45 (4)
O3—O14—H2o16	120.3 (18)	O14^vi—H2o20—O18^xi	155.4 (16)
O3—O14—H1o22^xii	97 (2)	O14^vi—H2o20—O20	111 (7)
O3—O14—H2o20^iii	139.2 (10)	O14^vi—H2o20—O22^xi	84 (2)
O8^ii—O14—O11	66.4 (3)	O14^vi—H2o20—H2o16^vi	71 (4)
O8^ii—O14—O20^iii	145.5 (4)	O14^vi—H2o20—H1o22^xi	80 (4)
O8^ii—O14—H2o16	106.9 (19)	O14^vi—H2o20—H2o22^xi	72 (3)
O8^ii—O14—H1o22^xii	139.3 (16)	O14^vi—H2o20—H1o20	121 (6)
O8^ii—O14—H2o20^iii	162 (2)	O18^xi—H2o20—O20	92 (6)
O11—O14—O20^iii	105.8 (3)	O18^xi—H2o20—O22^xi	72 (2)
O11—O14—H2o16	126.9 (18)	O18^xi—H2o20—H2o16^vi	112 (4)
O11—O14—H1o22^xii	153.7 (12)	O18^xi—H2o20—H1o22^xi	77 (4)
O11—O14—H2o20^iii	115.4 (17)	O18^xi—H2o20—H2o22^xi	84 (2)
O20^iii—O14—H2o16	49.1 (18)	O18^xi—H2o20—H1o20	73 (5)
O20^iii—O14—H1o22^xii	58 (2)	O20—H2o20—O22^xi	159 (8)
O20^iii—O14—H2o20^iii	17.8 (13)	O20—H2o20—H2o16^vi	70 (7)
H2o16—O14—H1o22^xii	60 (2)	O20—H2o20—H1o22^xi	139 (9)
H2o16—O14—H2o20^iii	57 (3)	O20—H2o20—H2o22^xi	165 (8)
H1o22^xii—O14—H2o20^iii	43 (2)	O20—H2o20—H1o20	37 (5)
U1^vi—O15—U3^iv	105.1 (3)	O22^xi—H2o20—H2o16^vi	103 (4)
U1^vi—O15—P2	141.6 (5)	O22^xi—H2o20—H1o22^xi	25.7 (16)
U1^vi—O15—O1^iv	53.1 (2)	O22^xi—H2o20—H2o22^xi	12 (2)
U1^vi—O15—O8	166.9 (4)	O22^xi—H2o20—H1o20	122 (6)
U1^vi—O15—O9	126.4 (4)	H2o16^vi—H2o20—H1o22^xi	78 (4)
U1^vi—O15—O10^iv	98.1 (3)	H2o16^vi—H2o20—H2o22^xi	99 (4)
U1^vi—O15—O11^vi	49.5 (2)	H2o16^vi—H2o20—H1o20	53 (5)
U1^vi—O15—O12^vi	36.53 (18)	H1o22^xi—H2o20—H2o22^xi	27 (3)
U1^vi—O15—O18	112.7 (4)	H1o22^xi—H2o20—H1o20	102 (6)
U3^iv—O15—P2	107.1 (4)	H2o22^xi—H2o20—H1o20	129 (5)
U3^iv—O15—O1^iv	52.8 (2)	O2^iv—H1o23—O11^iv	55.6 (19)
U3^iv—O15—O8	69.6 (3)	O2^iv—H1o23—O16^xiv	150 (4)
U3^iv—O15—O9	127.4 (4)	O2^iv—H1o23—O17^xiv	121 (5)
U3^iv—O15—O10^iv	38.06 (19)	O2^iv—H1o23—O19^xvi	102 (3)
U3^iv—O15—O11^vi	154.0 (4)	O2^iv—H1o23—O23	98 (5)
U3^iv—O15—O12^vi	99.7 (3)	O2^iv—H1o23—H1o19^xvi	108 (4)
U3^iv—O15—O18	112.2 (4)	O2^iv—H1o23—H2o19^xvi	92 (4)
P2—O15—O1^iv	146.2 (5)	O2^iv—H1o23—H1o22	110 (3)
P2—O15—O8	38.5 (3)	O2^iv—H1o23—H1o17^xiv	128 (8)
P2—O15—O9	34.9 (3)	O2^iv—H1o23—H2o17^xiv	134 (4)
P2—O15—O10^iv	120.2 (5)	O2^iv—H1o23—H2o23	62 (5)
P2—O15—O11^vi	98.5 (4)	O11^iv—H1o23—O16^xiv	101 (4)
P2—O15—O12^vi	149.0 (5)	O11^iv—H1o23—O17^xiv	128 (2)
P2—O15—O18	34.2 (3)	O11^iv—H1o23—O19^xvi	61.0 (17)
O1^iv—O15—O8	118.7 (4)	O11^iv—H1o23—O23	108 (7)
O1^iv—O15—O9	178.8 (4)	O11^iv—H1o23—H1o19^xvi	78 (3)
O1^iv—O15—O10^iv	63.5 (3)	O11^iv—H1o23—H2o19^xvi	44 (3)
O1^iv—O15—O11^vi	102.6 (3)	O11^iv—H1o23—H1o22	122 (4)
O1^iv—O15—O12^vi	64.1 (3)	O11^iv—H1o23—H1o17^xiv	150 (3)
O1^iv—O15—O18	121.2 (4)	O11^iv—H1o23—H2o17^xiv	114 (3)
O8—O15—O9	62.0 (3)	O11^iv—H1o23—H2o23	93 (6)
O8—O15—O10^iv	84.9 (4)	O16^xiv—H1o23—O17^xiv	87 (3)
O8—O15—O11^vi	136.4 (4)	O16^xiv—H1o23—O19^xvi	76 (2)
O8—O15—O12^vi	154.1 (4)	O16^xiv—H1o23—O23	71 (6)
O8—O15—O18	60.9 (3)	O16^xiv—H1o23—H1o19^xvi	80 (3)
O9—O15—O10^iv	115.9 (4)	O16^xiv—H1o23—H2o19^xvi	77 (4)
O9—O15—O11^vi	77.1 (3)	O16^xiv—H1o23—H1o22	65 (3)
O9—O15—O12^vi	114.8 (4)	O16^xiv—H1o23—H1o17^xiv	82 (6)
O9—O15—O18	59.9 (3)	O16^xiv—H1o23—H2o17^xiv	69 (3)
O10^iv—O15—O11^vi	128.9 (3)	O16^xiv—H1o23—H2o23	107 (6)
O10^iv—O15—O12^vi	73.5 (3)	O17^xiv—H1o23—O19^xvi	71.6 (13)
O10^iv—O15—O18	143.8 (4)	O17^xiv—H1o23—O23	123 (8)
O11^vi—O15—O12^vi	57.4 (3)	O17^xiv—H1o23—H1o19^xvi	53 (2)
O11^vi—O15—O18	86.6 (3)	O17^xiv—H1o23—H2o19^xvi	90 (3)
O12^vi—O15—O18	142.5 (4)	O17^xiv—H1o23—H1o22	108 (4)
Ca2—O16—O10	121.1 (4)	O17^xiv—H1o23—H1o17^xiv	22 (2)
Ca2—O16—O19	55.0 (3)	O17^xiv—H1o23—H2o17^xiv	23.7 (16)
Ca2—O16—O23^xii	126.3 (5)	O17^xiv—H1o23—H2o23	134 (8)
Ca2—O16—H1o16	81 (5)	O19^xvi—H1o23—O23	142 (9)
Ca2—O16—H2o16	44 (6)	O19^xvi—H1o23—H1o19^xvi	19 (2)
Ca2—O16—H1o20^iii	60.5 (17)	O19^xvi—H1o23—H2o19^xvi	19 (2)
Ca2—O16—H1o23^xii	142.6 (15)	O19^xvi—H1o23—H1o22	141 (5)
O10—O16—O19	130.6 (4)	O19^xvi—H1o23—H1o17^xiv	91 (3)
O10—O16—O23^xii	81.5 (4)	O19^xvi—H1o23—H2o17^xiv	54 (2)
O10—O16—H1o16	110 (6)	O19^xvi—H1o23—H2o23	154 (7)
O10—O16—H2o16	137 (6)	O23—H1o23—H1o19^xvi	151 (9)
O10—O16—H1o20^iii	127.1 (17)	O23—H1o23—H2o19^xvi	131 (10)
O10—O16—H1o23^xii	80 (2)	O23—H1o23—H1o22	15 (5)
O19—O16—O23^xii	144.9 (5)	O23—H1o23—H1o17^xiv	102 (8)
O19—O16—H1o16	28 (5)	O23—H1o23—H2o17^xiv	126 (8)
O19—O16—H2o16	79 (5)	O23—H1o23—H2o23	37 (5)
O19—O16—H1o20^iii	95.4 (17)	H1o19^xvi—H1o23—H2o19^xvi	37 (3)
O19—O16—H1o23^xii	136.4 (18)	H1o19^xvi—H1o23—H1o22	142 (5)
O23^xii—O16—H1o16	141 (6)	H1o19^xvi—H1o23—H1o17^xiv	73 (3)
O23^xii—O16—H2o16	85 (6)	H1o19^xvi—H1o23—H2o17^xiv	37 (3)
O23^xii—O16—H1o20^iii	67.2 (17)	H1o19^xvi—H1o23—H2o23	169 (7)
O23^xii—O16—H1o23^xii	19.0 (8)	H2o19^xvi—H1o23—H1o22	136 (6)
H1o16—O16—H2o16	106 (7)	H2o19^xvi—H1o23—H1o17^xiv	109 (4)
H1o16—O16—H1o20^iii	121 (6)	H2o19^xvi—H1o23—H2o17^xiv	72 (3)
H1o16—O16—H1o23^xii	123 (6)	H2o19^xvi—H1o23—H2o23	135 (8)
H2o16—O16—H1o20^iii	18 (6)	H1o22—H1o23—H1o17^xiv	87 (5)
H2o16—O16—H1o23^xii	99 (6)	H1o22—H1o23—H2o17^xiv	111 (5)
H1o20^iii—O16—H1o23^xii	82 (2)	H1o22—H1o23—H2o23	48 (5)
Ca1—O17—O4^vii	55.2 (2)	H1o17^xiv—H1o23—H2o17^xiv	38 (3)
Ca1—O17—O7	59.9 (3)	H1o17^xiv—H1o23—H2o23	115 (7)
Ca1—O17—O10	110.8 (4)	H2o17^xiv—H1o23—H2o23	153 (7)
Ca1—O17—O19^x	129.8 (4)	O2^iv—H2o23—O7	80 (3)
Ca1—O17—O23^xii	134.8 (4)	O2^iv—H2o23—O22	159 (4)
Ca1—O17—H1o19^x	124 (2)	O2^iv—H2o23—O23	120 (6)
Ca1—O17—H1o17	124 (5)	O2^iv—H2o23—H2o21^x	106 (5)
Ca1—O17—H2o17	130 (5)	O2^iv—H2o23—H1o22	177 (4)
Ca1—O17—H1o23^xii	135 (3)	O2^iv—H2o23—H1o17^xiv	100 (4)
O4^vii—O17—O7	106.9 (4)	O2^iv—H2o23—H1o23	84 (5)
O4^vii—O17—O10	147.3 (4)	O7—H2o23—O22	79 (2)
O4^vii—O17—O19^x	98.7 (3)	O7—H2o23—O23	157 (8)
O4^vii—O17—O23^xii	90.5 (3)	O7—H2o23—H2o21^x	63 (3)
O4^vii—O17—H1o19^x	96 (2)	O7—H2o23—H1o22	97 (3)
O4^vii—O17—H1o17	92 (6)	O7—H2o23—H1o17^xiv	130 (5)
O4^vii—O17—H2o17	139 (6)	O7—H2o23—H1o23	152 (8)
O4^vii—O17—H1o23^xii	83 (3)	O22—H2o23—O23	82 (6)
O7—O17—O10	83.7 (3)	O22—H2o23—H2o21^x	65 (3)
O7—O17—O19^x	98.2 (4)	O22—H2o23—H1o22	18.6 (19)
O7—O17—O23^xii	162.6 (4)	O22—H2o23—H1o17^xiv	95 (4)
O7—O17—H1o19^x	94 (3)	O22—H2o23—H1o23	116 (6)
O7—O17—H1o17	154 (6)	O23—H2o23—H2o21^x	99 (8)
O7—O17—H2o17	72 (5)	O23—H2o23—H1o22	64 (5)
O7—O17—H1o23^xii	162 (3)	O23—H2o23—H1o17^xiv	41 (5)
O10—O17—O19^x	110.5 (4)	O23—H2o23—H1o23	38 (5)
O10—O17—O23^xii	81.6 (3)	H2o21^x—H2o23—H1o22	75 (5)
O10—O17—H1o19^x	114 (2)	H2o21^x—H2o23—H1o17^xiv	70 (4)
O10—O17—H1o17	71 (6)	H2o21^x—H2o23—H1o23	100 (7)
O10—O17—H2o17	73 (6)	H1o22—H2o23—H1o17^xiv	83 (4)
O10—O17—H1o23^xii	96 (3)	H1o22—H2o23—H1o23	100 (6)
O19^x—O17—O23^xii	78.4 (3)	H1o17^xiv—H2o23—H1o23	32 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O16—H1o16···O19	0.95 (8)	1.98 (9)	2.762 (14)	139 (7)
O16—H2o16···O20^iii	0.94 (9)	2.39 (8)	3.248 (14)	151 (7)
O19—H1o19···O17^x	0.95 (8)	2.02 (9)	2.944 (13)	162 (8)
O19—H2o19···O11^v	0.95 (7)	1.92 (8)	2.809 (10)	155 (8)
O21—H1o21···O12^xv	0.95 (9)	2.37 (10)	3.241 (12)	153 (7)
O21—H2o21···O5^ii	0.95 (9)	2.41 (11)	2.892 (12)	111 (8)
O22—H1o22···O23	0.94 (5)	1.90 (8)	2.700 (13)	141 (9)
O22—H2o22···O5^vii	0.95 (8)	2.11 (8)	3.033 (12)	162 (8)
O17—H1o17···O23^xii	0.95 (5)	1.89 (7)	2.763 (13)	153 (7)
O17—H2o17···O19^x	0.94 (7)	2.36 (9)	2.944 (13)	120 (9)
O20—H1o20···O8^xi	0.94 (8)	2.34 (8)	3.123 (11)	141 (7)
O20—H2o20···O14^vi	0.94 (6)	2.39 (10)	2.870 (11)	111 (7)
O20—H2o20···O22^xi	0.94 (6)	2.18 (4)	3.074 (14)	159 (8)
O23—H1o23···O17^xiv	0.95 (6)	2.13 (9)	2.763 (13)	123 (8)
O23—H2o23···O7	0.94 (9)	2.38 (9)	3.268 (12)	157 (8)

Symmetry codes: (ii) x−1/2, −y+1/2, −z+1; (iii) x−1/2, y, −z+1/2; (v) x, −y+1/2, z+1/2; (vi) x+1/2, y, −z+1/2; (vii) −x+3/2, y+1/2, z; (x) −x+1, −y+1, −z+1; (xi) −x+2, −y+1, −z+1; (xii) −x+3/2, −y+1, z−1/2; (xiv) −x+3/2, −y+1, z+1/2; (xv) −x+1, y+1/2, −z+1/2.