Two calcium pyrene phospho­nate frameworks with contrasting dimensionality and porosity

This article is part of the special issue Metal–organic frameworks – frontiers and perspectives.

Two new calcium phospho­nate metal–organic frameworks (P-MOFs), IEF-33 and IEF-34, have been solvothermally synthesized from a pyrene tetra­phospho­nate ligand and structurally characterized by single-crystal X-ray diffraction. The two compounds arise from different degrees of ligand hydrolysis and exhibit distinct architectures: IEF-33 forms a 2D layered framework interacting through hydrogen bonds with interlayer water-filled channels, whereas IEF-34 adopts a 3D porous network with 1D channels. Gas sorption measurements demonstrate the permanent porosity of IEF-34, which exhibits a BET surface area of 491 m² g⁻¹ and a CO₂ uptake of 1.6 mmol g⁻¹ at 273 K. Both materials show good chemical stability in aqueous and organic media, and moderate thermal stability. In addition, IEF-33 and IEF-34 show strong visible-light absorption with optical band gaps of 2.51 and 2.62 eV, respectively.

1. Introduction

Metal–organic frameworks (MOFs) have emerged over the last few decades as one of the most interesting and versatile classes of crystalline porous materials. Built from inorganic nodes interconnected by organic linkers, these materials present an extraordinary structural and functional diversity combined with high modularity, resulting in an exponential growth of the number of reported structures of MOFs [there are now >110 000 entries in the Cambridge Structural Database (CSD); see https://support.ccdc.cam.ac.uk/support/solutions/articles/103000306242-how-many-mofs-are-there-in-the-csd-] as well as of their potential applications in diverse fields such as fluid storage and separation, catalysis, sensing, medicine and energy (Furukawa et al., 2013; Li et al., 2009; Kumar et al., 2015; Horcajada et al., 2012; Xia et al., 2015).

Despite this remarkable structural diversity, the vast majority of reported MOFs rely on carboxyl­ate-based linkers. While these materials often exhibit excellent porosity and functionality, their chemical and hydro­thermal stability remain significant challenges (An et al., 2024). In this context, phospho­nate-based MOFs (P-MOFs) have attracted researchers' attention because of the stronger metal–oxygen bonds associated with the phospho­nate group, which generally confer superior thermal, chemical and hydrolytic robustness than their carboxyl­ate counterparts (Gagnon et al., 2012; Shearan et al., 2019; Mysore Ramesha & Meynen, 2020). However, because of this coordination versatility and the high charge of the phospho­nate groups, these types of ligands frequently promote the formation of dense inorganic sublattices with complex connectivity and low crystallinity, complicating their structural elucidation. As a result, despite their attractive stability, the number of structurally resolved and permanently porous P-MOFs remains relatively limited (Zheng et al., 2024).

In parallel, the growing dependence on critical raw materials and the increasing geopolitical uncertainties affecting their availability have stimulated the search for MOFs based on earth-abundant sustainable elements (see https://single-market-economy.ec.europa.eu/sectors/raw-materials/areas-specific-interest/critical-raw-materials_en). In this con­text, calcium appears particularly attractive owing to its abundant nature (it is the fifth most abundant element in the Earth's crust, at 3.6–4.1%), low toxicity, low cost and excellent environmental compatibility. Nevertheless, calcium-based MOFs remain severely under-represented compared with their transition-metal counterparts. This scarcity can be largely attributed to the large ionic radius and high coordination versatility of Ca²⁺, which typically favor dense crystal packing and structural instability upon activation, thereby hindering the development of permanently porous materials (Fromm, 2008; Xian et al., 2021).

Such structural challenges are further exacerbated in calcium phospho­nate frameworks, where the strong metal–oxygen interactions and multitopic nature of phospho­nate ligands often favor the crystallization of compact, non-porous architectures rather than the intended open-framework materials. To date, fewer than 160 calcium phospho­nate structures have been reported in the CSD, and fewer than 60 correspond to coordination polymers exclusively constructed from Ca²⁺ cations and phospho­nate ligands (i.e. without additional coordinating functionalities). Among these, only around 20 structures satisfy the IUPAC definition of a MOF (i.e. structures containing potential voids) (Batten et al., 2013). From these structures, only two studies have explored their adsorption properties through H₂O and NH₃ sorption measurements (Colodrero et al., 2009) or by N₂ and CO₂ uptake (Glavinović et al., 2022). This scarcity of adsorption studies highlights a significant knowledge gap regarding the true porous potential of this family of materials.

Within this context, the use of rigid, multitopic phospho­nate ligands emerges as a promising strategy for obtaining porous structures (Taddei et al., 2016; Firmino et al., 2018). Pyrene-based tetra­phospho­nates are particularly interesting because of their aromatic core, high rigidity and intrinsic optoelectronic properties, which have already demonstrated good performance when incorporated into hybrid materials (Salcedo-Abraira, Serrano-Nieto et al., 2023; Serrano-Nieto et al., 2025; Firmino et al., 2020; Salcedo-Abraira, Biglione et al., 2023). Nevertheless, only one calcium pyrene tetra­phospho­nate structure has been reported so far. This material corresponds to a non-porous coordination network (Serrano-Nieto et al., 2025), leaving the exploration of porosity and adsorption behavior in this system essentially unexplored.

In this work, we report the synthesis and full structural characterization of two novel calcium-based P-MOFs (labeled IEF-33 and IEF-34 from IMDEA Energy Framework) containing the pyrene tetra­phospho­nate ligand. The thermal and structural stability, and textural and optoelectronic properties of both materials were also investigated. IEF-33 is built from the fully hydrolyzed and partially deprotonated version of the ligand [Py(PO₃Et₂)₄], i.e. [Py(PO₃H)₄]⁴⁻, resulting in a two-dimensional coordination network connectivity in which Ca²⁺ centers are coordinated by both phospho­nate groups and water molecules, with adjacent layers interconnected through hydrogen bonds. In contrast, IEF-34 contains the partially hydrolyzed and deprotonated ligand [Py(PO₃Et)₂(PO₃HEt)₂]²⁻ with the Ca atoms totally surrounded by the phospho­nate groups, leading to a three-dimensional network with void channels (with a specific surface BET area of 490 m² g⁻¹) that are accessible to both N₂ and CO₂ gases. Both materials combined a good structural stability in organic media, relative stability in aqueous media and enhanced light absorption compared with the pristine ligand.

2. Materials and methods

All the chemicals were used as received without further pur­ification: Ca(NO₃)₂·4H₂O (99%, Alfa Aesar, 236.15 g mol⁻¹), pyrene (98%, Sigma Aldrich, 202.25 g mol⁻¹), bromine (≥95.5%, Sigma Aldrich, 159.81 g mol⁻¹), nitro­benzene (99%, Thermo Scientific), P(OEt)₃ (98%, Sigma Aldrich, 166.16 g mol⁻¹), [Pd(PPh₃)₄] (99%, Sigma Aldrich, 1155.56 g mol⁻¹), EtOH (≥99.8%, ACS reagent), MeOH (≥99.8%, ACS reagent), n-hexane (technical grade, VWR Chemicals) and HCl (37%, ACS reagent). Py(PO₃Et₂)₄ was synthesized using a previously reported procedure (see the supporting information for further information) (Salcedo-Abraira, Serrano-Nieto et al., 2023).

2.1. Synthesis

2.1.1. Single-crystal synthesis of IEF-33, {[Ca₂(C₁₆H₁₀P₄O₁₂)­(H₂O)₄]·3H₂O}_n (molecular weight 724.39 g mol⁻¹)

In a 2.5 ml Teflon-lined reactor, 10.63 mg (0.045 mmol) of Ca(NO₃)₂·4H₂O and 16.79 mg (0.0225 mmol) of Py(PO₃Et₂)₄ were dissolved in 0.5 ml of MeOH and 1 ml of distilled water, then the reactor was closed. The reactor was heated in an oven to 120 °C over 6 h, maintained at this temperature for 48 h and finally cooled down to 30 °C over 6 h. The resulting brown crystals were recovered by filtration and washed with distilled water and methanol, and were dried at room temperature (RT).

2.1.2. Scaled-up synthesis of IEF-33

In a 25 ml Teflon-lined reactor, 106.3 mg (0.45 mmol) of Ca(NO₃)₂·4H₂O and 167.9 mg (0.225 mmol) of Py(PO₃Et₂)₄ were dissolved in 5 ml of MeOH and 10 ml of distilled water, then the reactor was closed. The reactor was heated in an oven at 120 °C for 87 h. The resulting brown crystals were recovered by filtration and washed with distilled water and methanol, and were dried at RT. Solid recovered: 90 mg (70 ± 5% yield based on the linker).

2.1.3. Single-crystal synthesis of IEF-34, [Ca(C₂₀H₂₀P₄O₁₂)]_n (molecular weight 616.32 g mol⁻¹)

In a 2.5 ml Teflon-lined reactor, 10.63 mg (0.045 mmol) of Ca(NO₃)₂·4H₂O and 16.79 mg (0.0225 mmol) of Py(PO₃Et₂)₄ were dissolved in 1 ml of EtOH and 0.5 ml of distilled water. Then 10 µl of 5 M HCl were added and the reactor was closed. The reactor was heated in an oven to 120 °C over 8 h, maintained at this temperature for 48 h and finally cooled down to 30 °C over 8 h. The resulting yellow crystals were recovered by filtration and washed with distilled water and ethanol, and were dried at 100 °C for 12 h.

2.1.4. Scaled-up synthesis of IEF-34

In a 25 ml Teflon-lined reactor, 98.52 mg (0.42 mmol) of Ca(NO₃)₂·4H₂O and 155.84 mg (0.21 mmol) of Py(PO₃Et₂)₄ were dissolved in 9.2 ml of EtOH and 4.6 ml of distilled water. Then 100 µl of 5 M HCl were added and the reactor was closed. The reactor was heated in an oven to 130 °C over 8 h, maintained at this temperature for 48 h and finally cooled down to 30 °C over 8 h. The resulting yellow crystals were recovered by filtration and washed with distilled water and ethanol, and were dried at 100 °C for 12 h. Solid recovered: 77 ± 4 mg (60 ± 3% yield based on the linker).

2.2. Crystallographic studies

Suitable single crystals of Py(PO₃Et₂)₄, IEF-33 and IEF-34 were mounted on a MiTeGen polymer loop and covered with oil. Data were collected at room temperature using a Bruker Venture and a Rigaku XtaLAB Synergy diffractometer with Mo Kα radiation (λ = 0.71073 Å) for Py(PO₃Et₂)₄ and IEF-34, respectively. Data for IEF-33 were collected at the ALBA synchrotron (Spain) on the XALOC beamline at 100 K using a single φ-scan data acquisition strategy (Juanhuix et al., 2014). The data for Py(PO₃Et₂)₄ were reduced using APEX3 and an absorption correction was applied using SADABS. For IEF-33, data indexing, integration and scaling were performed with the XDS program (Kabsch, 2010) and an absorption correction was not applied. Data reduction for IEF-34 was performed with the CrysAlisPro suite and a semi-empirical absorption correction (ABSPACK) was applied. The structures were solved using SHELXT (Sheldrick, 2015b) and refined with SHELXL (Sheldrick, 2015a) integrated within the Olex2 graphical interface (Dolomanov et al., 2009). The volumes of the solvent-accessible voids were calculated using a 1.2 Å probe. All non-H atoms were refined anisotropically. Hydrogen atoms were placed in calculated positions and refined with idealized geometries.

Powder X-ray diffraction (PXRD) data used for crystallographic studies were collected on a BRUKER D8 DISCOVER equipped with a microfocus Cu Kα radiation source (λ = 1.54059 Å) over a 2θ range of 4–50° with a 0.02° step size and 40 s of acquisition time per step.

2.3. Instrumentation

Routine PXRD data were collected using an Empyrean Panalytical diffractometer (Cu Kα, λ = 1.5406 Å) equipped with a PIXcel3D detector, operating at 45 kV and 40 mA from 3 to 35° 2θ with a step size of 0.013° and a scan rate of 0.1° s⁻¹. Scanning electron microscopy (SEM) micrographs were collected on a Hitachi TM-1000 microscope operating at 15 kV. Fourier-transform infrared (FTIR) spectra were collected in the 4000 to 400 cm⁻¹ range using a Thermo Nicolet 6700 FTIR spectrometer with an ATR accessory instrument (Thermo Scientific, USA). Elemental analyses were carried out in a Flash 2000 analyzer from Thermo Scientific. Inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses were carried out using a 2300 DV spectrometer from Perkin Elmer. TGA was performed using an SDT650 thermobalance (TA instruments) over the 25–1000 °C range at 5 °C min⁻¹ and under an air flow of 100 ml min⁻¹. Variable-temperature (VT) PXRD data were acquired on a D8 Advance Bruker AXS θ–2θ diffractometer (Cu Kα radiation, λ = 1.54060 Å) equipped with a LYNXEYE XE detector, operating at 40 kV and 40 mA, and an Anton Paar XRK 900 high-temperature chamber. Both nitro­gen (at 77 K) and CO₂ (at both 273 K and 293 K) sorption isotherms were collected using a 3Flex instrument from Micromeritics. Prior to the gas sorption experiments, samples were degassed at 120 °C for 6 h under secondary vacuum. Diffuse reflectance UV–Vis measurements were recorded using a Perkin Elmer spectrometer (Lambda 19) equipped with an integrating sphere and a praying mantis accessory.

3. Results and discussion

3.1. Synthesis and structural elucidation

The reactivity of Ca²⁺ cations with the lab-made pyrene octa­ethyl tetra­phospho­nate ligand was investigated using the solvothermal high-throughput method (Stock, 2010). Upon synthetic optimization, two novel calcium phospho­nate phases were isolated, labeled as IEF-33 and IEF-34. The generation of one or the other phase was mostly determined by the mixture of solvents employed: IEF-33 required the use of an MeOH/H₂O mixture in a 1:2 (v/v) ratio, while IEF-34 was obtained using an EtOH/H₂O 2:1 (v/v) mixture with the addition of 1 equivalent of HCl per metal. Interestingly, the IEF-33 structure contained the totally hydrolyzed ligand, whereas in IEF-34 half of the phospho­nate groups in the ligand were in their esterified version (where HCl is used during the synthesis). Compared with the synthetic conditions previously reported for the dense calcium pyrene tetra­phospho­nate framework IEF-22(Ca) (Serrano-Nieto et al., 2025), the preparation of the more open and porous IEF-33 and IEF-34 relies on significantly milder reaction conditions and a more straightforward synthetic approach. Specifically, both MOFs were obtained at lower temperatures (120–130 versus 150 °C), using a lower metal concentration (0.03 versus 0.1 M) and employing the esterified version of the ligand (Table 1, Tables S1 and S2, and Fig. S1) instead of its acidic counterpart. The latter was employed for IEF-22, requiring an additional synthetic step during ligand preparation.

Table 1
Crystal data and structure refinement for Py(PO₃Et₂)₄, IEF-33 and IEF-34

	Py(PO3Et2)4	IEF-33	IEF-34
CCDC number	2548440	2548343	2248686
Empirical formula	C32H46O12P4	Ca2C16H24O19P4	CaC20H20O12P4
Formula weight	746.57	724.39	616.32
Temperature (K)	296.15	100.00	295.7 (4)
Crystal system	triclinic	triclinic	monoclinic
Space group	P1	P1	C2/c
a (Å)	10.0133 (4)	8.4993 (3)	21.6124 (1)
b (Å)	10.1039 (4)	12.5656 (9)	18.4191 (8)
c (Å)	10.9607 (4)	12.5832 (1)	8.3124 (4)
α (°)	66.7250 (1)	103.252 (7)	90
β (°)	74.4070 (1)	98.700 (5)	108.823 (4)
γ (°)	89.869 (2)	97.446 (4)	90
Volume (Å^3)	974.40 (7)	1274.05 (2)	3132.0 (3)
Z	1	2	4
ρcalc (g cm^−3)	1.272	1.888	1.307
μ (mm^−1)	0.249	1.212	0.455
F(000)	394.0	744.0	1264.0
Crystal size (mm)	0.1 × 0.003 × 0.003	0.1 × 0.01 × 0.01	0.1 × 0.05 × 0.02
Radiation	Mo Kα (λ = 0.71073)	Synchrotron (λ = 0.82656)	Mo Kα (λ = 0.71073)
2θ range for data collection (°)	4.23 to 56.664	3.93 to 52.762	6.372 to 50.052
Index ranges	−13 ≤ h ≤ 13, −13 ≤ k ≤ 13, −14 ≤ l ≤ 14	−9 ≤ h ≤ 9, −12 ≤ k ≤ 12, 0 ≤ l ≤ 13	−25 ≤ h ≤ 25, −21 ≤ k ≤ 21, −9 ≤ l ≤ 9
Reflections collected	49829	10741	36413
Independent reflections	4852 (Rint = 0.0729, Rsigma = 0.0392)	3082 (Rint = 0.2687, Rsigma = 0.2076)	2761 (Rint = 0.0882, Rsigma = 0.0434)
Data/restraints/parameters	4852/179/241	3082/1/377	2761/179/216
Goodness-of-fit on F^2	1.042	1.040	1.102
Final R factors [I ≥ 2σ(I)]	R1 = 0.0711, wR2 = 0.2121	R1 = 0.1205, wR2 = 0.3061	R1 = 0.0615, wR2 = 0.1560
Final R factors (all data)	R1 = 0.0907, wR2 = 0.2414	R1 = 0.1757, wR2 = 0.3234	R1 = 0.0945, wR2 = 0.1726
Largest difference peak/hole (e Å^−3)	0.46/−0.35	1.67/−0.70	0.40/−0.29

IEF-33 was obtained as small brown needle-shaped crystals (∼75 µm long, Fig. S2), hindering structural determination by conventional SCXRD. Therefore, synchrotron SCXRD was employed, revealing that IEF-33, formulated as {[Ca₂(C₁₆H₁₀P₄O₁₂)(H₂O)₄]·3H₂O}_n or {[Ca₂(Py(PO₃)₄)­(H₂O)₄]·3H₂O}_n, crystallizes in the triclinic space group P1 (No. 2) with unit-cell parameters a = 8.4993 (3) Å, b = 12.5656 (9) Å, c = 12.5832 (1) Å, α = 103.252 (7)°, β = 98.700 (5)°, γ = 97.446 (4)°, V = 1274.05 (2) ų and Z = 2 (Table 1). The IEF-33 structure is built from [Ca₂(Py(PO₃)₄)­(H₂O)₄]_n layers along the (001) plane, interacting through hydrogen bonds [Fig. 1(a)]. The asymmetric unit contains one fully hydrolyzed pyrene tetra­phospho­nate ligand coordinating two crystallographically independent Ca²⁺ cations (Ca1 and Ca2), each one with two coordinated water molecules, and three crystallization water molecules. The secondary building unit (SBU) consists of [Ca₂(PO₃H)₄­(H₂O)₄]_n chains running along the [100] direction [Fig. 1(b)]. These chains contain the Ca1 and Ca2 cations alternating in two different coordination spheres. Ca1 is found in a highly distorted [CaO₇] pentagonal bipyramid environment with d(Ca1—O) distances between 2.362 (1) and 2.761 (1) Å [Tables S4 and S5, and Fig. S3(a)] and in a distorted [CaO₆] octahedral environment with d(Ca2—O) distances between 2.279 (1) and 2.415 (1) Å [Tables S4 and S5, and Fig. S3(b)]. The Ca1 coordination sphere contains the P2 phospho­nate group of one ligand, which is acting as a chelating ligand (through O5 and O6), the P3 and P4 phospho­nate groups from different ligands acting as monodentate ligands (by O1, O8 and O11, respectively) and two coordinated water molecules [O1W and O2W, Fig. S3(a)]. On the other hand, Ca2 contains four phospho­nate groups (P1, P2, P3 and P4, each one from a different ligand) acting as monodentate ligands in the octahedra basal positions (by O2, O5, O7 and O11, respectively) with the O3W and O4W from two water molecules occupying the apical positions [Fig. S3(b)]. These pentagonal bipyramids and octahedra share two vertices (O11 and O5), generating chains in the [100] direction [Figs. 1(b) and S4]. Bonds between these chains are formed by the ligands, creating layers in the (001) plane in which the pyrene cores are π stacked [d(Py–Py) ≃ 4 Å, Fig. S5]. Each ligand is bonded to eight different Ca atoms. The P1 and P3 groups act as bidentate ligands through O1 and O2 (from P1) and through O8 and O7 (from P3), bonding to one Ca1 and one Ca2, respectively; the P2 group acts as a chelating ligand (through O5 and O6) to one Ca1, and also a bidentate ligand, bridging Ca1 and Ca2 by O5; and finally the P4 group acts as a monodentate ligand (O11), bridging one Ca1 and one Ca2 (Fig. S6). It is worth noting that during the synthesis all the eth­oxy groups were hydrolyzed, remaining as four OH groups in the coordinated ligand. This resulted in the connection of four chains, one per phospho­nate group of the ligand, where the octahedra and the pentagonal bipyramids alternate between the chains, establishing intra-layer hydrogen bonds through the coordinated water molecules (Fig. S7). Finally, the stacking of the layers generates elongated channels of ca 7.5 × 3.5 Å (considering van der Waals radii). These voids are occupied by free water molecules that participate in an extended hydrogen-bonding network with adjacent layers (Fig. S8). These channels account for approximately 12.8% of the unit-cell volume (according to PLATON calculations).

Figure 1 IEF-33 crystal structure viewed along the [100] direction (a) and the IEF-33 SBU viewed along the [001] direction (b). Calcium, phospho­rus, oxygen, carbon and hydrogen atoms are represented in green, orange, red, black and white, respectively.

IEF-34 was obtained as small rhombohedral pale yellow crystals (100 µm in length, Fig. S9), allowing its structure to be determined using conventional SCXRD (Table 1). IEF-34, with the formula [Ca(C₂₀H₂₀P₄O₁₂)]_n (or [Ca(Py(PO₃H_0.5Et_0.5)₂(PO₃H_1.5Et_0.5)₂)]_n), crystallizes in the monoclinic space group C2/c (No. 15) with unit-cell parameters a = 21.6124 (1) Å, b = 18.4191 (8) Å, c = 8.3124 (4) Å, β = 108.823 (4)°, V = 3132.0 (3) ų and Z = 4. The asymmetric unit contains half a pyrene tetra­ethyl tetra­phospho­nate ligand coordinated to one Ca²⁺ cation. Unlike IEF-33, where complete hydrolysis of the phospho­nate ester groups occurs, IEF-34 retains one ethyl substituent dis­ordered between the two phospho­nate moieties of the asymmetric unit, yielding the partially hydrolyzed ligand [Py(PO₃H_0.5Et_0.5)₂(PO₃H_1.5Et_0.5)₂]²⁻. The three-dimensional structure of IEF-34 is built up from distorted [CaO₆] octahedra [Figs. 2 and S10(a), and Tables 1, S6 and S7] acting as SBUs bonded by [Py(PO₃H_0.5Et_0.5)₂(PO₃H_1.5Et_0.5)₂]²⁻ with d(Ca1—O) distances ranging from 2.304 (4) to 2.412 (4) Å. These octahedra are interconnected by the different phos­pho­nate groups, creating a zigzag chain along the [001] direction. Each calcium center is bound to six different phospho­nate groups from neighboring ligands. Specifically, the coordination sphere is composed of four P1 and two P2 phospho­nate groups from different ligands: two O1 and two O2 from the P1 groups, and two O5 atoms from the P2 groups, where the O1 and O5 pairs of atoms are in the cis position and the O2 pair is in the trans position [Fig. S10(a)]. On the other hand, each ligand, where each phospho­nate group presents half a non-hydrolyzed ethyl group, is connected to six different Ca atoms: two per P1 group (O1 and O2) and one per P2 group (O5), as illustrated in Fig. S10(b). A notable feature of IEF-34 is the presence of one-dimensional channels running parallel to the [001] direction. Two types of apertures can be identified: narrower channels (7.5 × 2 Å) in between disordered ethyl groups and larger cavities of ca 10 × 10 Å delimited by the pyrene cores along the [001] direction with the ethyl groups located inside (considering the van der Waals radii). These channels represent 13.2% of the unit-cell volume according to solvent-accessible volume calculations in PLATON, being the permanent porosity further confirmed by N₂ and CO₂ gas sorption experiments (see below).

Figure 2 Crystal structure of IEF-34 viewed along the [001] direction (a) and [CaO6] octahedra chains in the [001] direction (b). Calcium, phospho­rus, oxygen, carbon and hydrogen atoms are represented in green, orange, red, black and white, respectively.

3.2. Physicochemical characterization

The purity of the polycrystalline samples of both IEF-33 and IEF-34 was confirmed by powder X-ray diffraction (PXRD) combined with chemical analysis. (IEF-33: theoretical (%) Ca 11.06, P 17.10, C 26.52, H 3.34, O 41.96; experimental (%) Ca 11.2 ± 0.6, P 18.8 ± 0.9, C 27.26 ± 0.08, H 2.96 ± 0.08. IEF-34: theoretical (%) Ca 6.50, P 20.10, C 38.97, H 3.27, O 31.15; experimental (%) Ca 6.8 ± 0.3, P 19.0 ± 0.9, C 39.4 ± 0.1, H 3.66 ± 0.01; see the supporting information for further details). Comparison of the position and intensity of the main reflections in the experimental PXRD patterns with the simulated ones confirmed the successful formation of the phases (Fig. S11), while a Pawley profile fitting (Fig. S12 and Table S7) showed the absence of other crystalline impurities. The ligand connectivity was confirmed by Fourier-transform infrared spectroscopy (FTIR, Fig. S13), where the elimination of the νC_aliphatic—H, δC_aliphatic—H and νP—O—C bands (at 2900–2982, 1370–1478 and 798 cm⁻¹, respectively) (Pretsch et al., 2009) was observed in IEF-33 due to the hydrolysis of the eth­oxy groups of the phospho­nate (while those signals are still present in IEF-34), combined with a shift in the main νP—O and νP=O bands with respect to the Py(PO₃Et₂)₄ ligand (from 1247 and 1217 cm⁻¹ to 1127 cm⁻¹ for IEF-33 and to 1216 and 1175 cm⁻¹ for IEF-34; and from 1012 and 957 to 1017 and 913 for IEF-33 and to 1027 and 944 cm⁻¹ for IEF-34).

The potential permanent porosity of both IEF-33 and IEF-34 was evaluated by N₂ and CO₂ sorption isotherms. IEF-33 showed almost no N₂ or CO₂ uptake (Fig. S14) despite the a priori accessible porosity according to the crystallographic data (pore dimensions: 7.5 × 3.5 Å versus the kinetic diameters of N₂ and CO₂ of 3.6 and 3.3 Å, respectively). This behavior can be rationalized by considering the phase transition occurring upon activation (see Thermal and chemical stability below). On the other hand, IEF-34 presented permanent porosity accessible to N₂ and CO₂ (Fig. 3), with an S_BET surface area of 491.3 ± 0.5 m² g⁻¹ and a total pore volume (V_p) of 0.19 cm³ g⁻¹ according to the N₂ isotherm [Fig. 3(a)]. The Horvath–Kawazoe pore size distribution [inset to Fig. 3(a)] showed a broad pore size distribution between 6–7.5 Å, in good agreement with the crystallographic data considering the free rotation inside the pore and the disordered nature of the eth­oxy groups and their partial occupancy. Finally, IEF-34 showed a CO₂ uptake of 1.6 and 1.1 mmol g⁻¹ at 1 bar [at 273 and 293 K, respectively; Fig. 3(b)], in line with previously reported P-MOFs (Salcedo-Abraira et al., 2021; Taddei et al., 2014; Serrano-Nieto et al., 2026; Glavinović et al., 2022) but still far from the benchmarked Mg carboxyl­ate MOF-74, which has the record for CO₂ uptake in the field of MOFs (8 mmol g⁻¹ at 296 K and 1 bar; Li et al., 2020).

Figure 3 (a) N2 sorption isotherm at 77 K and Horvath–Kawazoe pore size distribution (inset), and (b) CO2 sorption isotherms at 273 K (blue) and 293 K (red) of IEF-34. Adsorption and desorption points are represented by solid and open symbols, respectively.

3.3. Thermal and chemical stability

In order to assess the thermal stability of the two MOFs, thermogravimetric analyses coupled with differential scanning calorimetry (TGA–DSC) and variable-temperature PXRD (VTPXRD) experiments were carried out. TGA of IEF-33 showed three consecutive weight losses associated with the removal of water molecules (Fig. S15). The first weight loss (from RT to 80 °C) of 7.7% corresponds to the departure of three free water molecules located between the layers (theoretical loss 7.45%). A second weight loss of 6.1% from 80 to 100 °C is attributed to the removal of three of the four coordinated water molecules (theoretical loss 7.45%). The remaining coordinated water molecule seems to be released more gradually from 100 to 200 °C, resulting in an additional weight loss of 2.5% (theoretical loss 2.48%). After complete dehydration, a plateau is observed up to 400 °C where IEF-33 is oxidized prior to decomposition (Fig. S15). This oxidation may be attributed to the formation of phosphates from the phospho­nate groups (Howell, 2022). VTPXRD (Fig. S16) revealed an initial phase transition as a consequence of water departure starting at 30 °C and finishing at 150 °C, in line with the TGA. This transition was found to be irreversible, as the original structure was not recovered after cooling back to room temperature or following subsequent exposure to water, indicating a permanent structural rearrangement upon dehydration (Fig. S17). This phase remained stable up to 360 °C, where it evolved due to oxidation prior to the decomposition. Note that it was not possible to identify the nature of the final residue because of its amorphous nature, hindering complete compositional characterization. These observations are consistent with the absence of N₂ and CO₂ uptake from IEF-33 despite its a priori structural porosity.

On the other hand, and consistent with its rigid 3D network and permanent porosity, IEF-34 showed a progressive initial weight loss (∼5%) from room temperature to ca 120 °C that might correspond to some residual solvent molecules trapped within the pores during the synthesis. Then a plateau is observed up to 300 °C, where IEF-34 started to decompose (Fig. S18; note that the final residue was not identified). VTPXRD showed no significant structural evolution up to 270 °C, where the structure collapsed due to decomposition (Fig. S19), in agreement with the TGA data.

The chemical stability of IEF-33 and IEF-34 was evaluated by suspending the materials (5 mg ml⁻¹) under stirring for 24 h in a series of organic solvents (methanol, MeOH; ethanol, EtOH; aceto­nitrile, ACN; tetra­hydro­furan, THF; N,N′-di­methyl­formamide, DMF; di­methyl­sulfoxide, DMSO; CH₂Cl₂; hexane; octane; and toluene). In addition, their hydrolytic stability was evaluated over a broad range of pH. After treatment, the solids were recovered and their structural integrity was evaluated by PXRD. IEF-33 retained its crystallinity over the 2 > pH > 10 range, losing its crystallinity at pH 13 (Fig. S20). Upon exposure to different organic solvents, IEF-33 preserved its crystalline structure with only minor changes in peak positions and relative intensities in most cases. The only exception was for DMSO, where the appearance of additional diffraction peaks suggested the formation of a secondary phase. This behavior is probably associated with the replacement of the interlayer water molecules by DMSO, leading to a partial structural reorganization of the layered framework (Fig. S21).

On the other hand, IEF-34 exhibited remarkable hydrolytic structural stability, maintaining its crystallinity across almost the entire pH range (pH 1–12). Under strongly basic conditions (pH 14), the material was transformed into Ca(OH)₂ (JCPDS Card No. 87-s0315, Fig. S22). IEF-34 presented negligible changes in PXRD patterns when exposed to the various organic solvents (Fig. S23), showing superior stability in organic media to IEF-33. We hypothesize that the enhanced chemical stability of IEF-34 relative to IEF-33 originates from the different coordination environment of the Ca²⁺ centers; specifically, while IEF-33 features labile coordinated water molecules, the calcium atoms in IEF-34 are exclusively coordinated by phospho­nate groups, resulting in a more robust inorganic framework that effectively resists chemical degradation.

Complementary gravimetric measurements after solvent treatment revealed solvent-dependent mass variations (Fig. S24). The largest mass loss was observed after exposure to deionized water (>40 wt%), whereas hydro­carbon solvents led to more moderate values (<30 wt%). Intermediate mass changes were measured for THF and toluene (<20 wt%), while ethanol, aceto­nitrile, DMF and DMSO exhibited the lowest variations (<10 wt%). Interestingly, despite these differences in mass variation, PXRD patterns confirmed that the crystalline framework was preserved after treatment in all cases (except for the partial structural reorganization observed in DMSO).

3.4. Optoelectronic properties

Given the promising photoactive properties previously reported for pyrene-tetra­phospho­nate-based materials (Serrano-Nieto et al., 2025; Salcedo-Abraira, Serrano-Nieto et al., 2023), the optoelectronic properties of IEF-33 and IEF-34 were investigated by solid-state diffuse reflectance UV–Vis spectroscopy. Identifying their light-absorption behavior is particularly relevant for assessing their potential in applications such as photocatalysis, optoelectronics and solar energy conversion. These MOFs showed light absorption across almost all the visible range (Fig. 4), with a broad absorption maximum ranging from 250 to 400 nm due to the aromatic pyrene core, and in line with the optoelectronic properties of the ligand. Between 400 and 800 nm, IEF-33 presented stronger absorption than IEF-34, absorbing within the whole range (while IEF-34 started to absorb at ca 650 nm). These differences in terms of optical properties are probably related to the pyrene core π–π stacking present in the IEF-33 structure, which is also responsible for the different colors of the two materials (brown for IEF-33 and pale yellow for IEF-34), and are also reflected in the estimated optical band gap: 2.51 versus 2.62 eV for IEF-33 and IEF-34, respectively (Fig. S25), which both correspond to indirect transitions.

Figure 4 Solid-state UV–Vis diffuse reflectance (a) and absorption (b) spectra of the Py(PO3Et2)4 ligand (black), IEF-33 (red) and IEF-34 (blue).

The combination of permanent porosity (in IEF-34), broad visible light absorption and high chemical stability across a wide pH range suggests that these calcium-based frameworks could be of interest for several applications. For instance, while the CO₂ uptake at low pressures remains modest and further selectivity studies are required, the robust 3D structure and high stability of IEF-34 provide a baseline for exploring gas sorption in chemically demanding environments (Xian et al., 2021). Furthermore, the photoactive pyrene core, coupled with the observed narrow band gaps, indicates that these materials may serve as platforms for the (photo)catalytic degradation of organic pollutants or solar-to-chemical energy conversion (Serrano-Nieto et al., 2025; Lustig & Li, 2018). Finally, the inherent biocompatibility of the calcium-phospho­nate backbone opens up potential avenues for future exploration in biomedical fields, such as drug delivery or biosensing (Alvarez et al., 2013; Liu et al., 2012).

4. Conclusions

Two novel calcium-based P-MOFs were solvothermally synthesized using a photoactive pyrene tetra­phospho­nate ligand. Single-crystal X-ray diffraction revealed that differences in ligand hydrolysis led to markedly different architectures: hydrogen-bonded 2D coordination layers in IEF-33 and a 3D porous network with 1D channels in IEF-34. These MOFs have open structures with free water molecules (IEF-33) or voids (IEF-34), showing their potential porosity. Furthermore, IEF-34 had a CO₂ adsorption of ca 1.6 mmol g⁻¹ at 273 K, which is in the range of the highest values reported for P-MOFs. Additionally, both materials showed moderate thermal stability (up to 350 and 270 °C for IEF-33 and IEF-34, respectively) and good chemical stability in aqueous and organic solvents, which when combined with their optoelectronic properties (band gaps of 2.51 and 2.62 eV) make IEF-33 and IEF-34 potential candidates for several applications [e.g. molecule adsorption, sensing, (photo)catalysis]. Specifically, the permanent porosity of IEF-34 opens up potential avenues for energy-efficient gas separation in harsh environments and future biomedical exploration. More broadly, this work expands the still-limited family of porous calcium P-MOFs and provides new insights into the crystal engineering of sustainable MOFs.

5. Related literature

The following reference is cited in the supporting information: Bernhardt et al. (2006).

Supporting information

Computing details

(Py(PO3Et2)4)

Crystal data

C32H46O12P4	Z = 1
Mr = 746.57	F(000) = 394
Triclinic, P1	Dx = 1.272 Mg m^−3
a = 10.0133 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1039 (4) Å	Cell parameters from 9650 reflections
c = 10.9607 (4) Å	θ = 2.2–26.6°
α = 66.725 (1)°	µ = 0.25 mm^−1
β = 74.407 (1)°	T = 296 K
γ = 89.869 (2)°	Needle, yellow
V = 974.40 (7) Å^3	0.1 × 0.003 × 0.003 mm

Data collection

Bruker SMART APEX2 area detector diffractometer	4852 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	3437 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.073
Detector resolution: 7.9 pixels mm^-1	θmax = 28.3°, θmin = 2.1°
ω and φ scans	h = −13→13
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1474 before and 0.0820 after correction. The Ratio of minimum to maximum transmission is 0.7089. The λ/2 correction factor is Not present.	k = −13→13
Tmin = 0.529, Tmax = 0.746	l = −14→14
49829 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H-atom parameters constrained
wR(F^2) = 0.242	w = 1/[σ^2(Fo^2) + (0.1433P)^2 + 0.2979P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
4852 reflections	Δρmax = 0.46 e Å^−3
241 parameters	Δρmin = −0.35 e Å^−3
179 restraints

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.43806 (7)	0.68662 (8)	0.29357 (8)	0.0625 (3)
P2	0.93545 (7)	0.86643 (11)	0.32008 (11)	0.0826 (3)
O3	0.5524 (2)	0.6130 (2)	0.2211 (2)	0.0710 (5)
O2	0.3996 (3)	0.8024 (2)	0.1676 (3)	0.0839 (6)
O5	0.9768 (2)	0.8080 (3)	0.4584 (3)	0.0894 (7)
O1	0.3224 (2)	0.5849 (3)	0.4043 (2)	0.0847 (7)
O4	0.9751 (3)	0.7839 (4)	0.2351 (4)	0.1151 (11)
C5	0.5357 (2)	0.9587 (2)	0.4634 (2)	0.0475 (5)
C4	0.4590 (2)	0.8804 (2)	0.4157 (2)	0.0501 (5)
C7	0.3123 (2)	0.8895 (3)	0.4401 (3)	0.0592 (6)
H7	0.261579	0.840299	0.407986	0.071*
C3	0.5297 (3)	0.7983 (3)	0.3468 (3)	0.0538 (5)
C6	0.6823 (2)	0.9546 (3)	0.4395 (3)	0.0524 (5)
O6	1.0057 (3)	1.0270 (4)	0.2548 (4)	0.1122 (10)
C8	0.2454 (2)	0.9675 (3)	0.5083 (3)	0.0604 (6)
H8	0.149904	0.970719	0.521736	0.072*
C1	0.7503 (2)	0.8754 (3)	0.3653 (3)	0.0594 (6)
C2	0.6730 (3)	0.7976 (3)	0.3212 (3)	0.0606 (6)
H2	0.718693	0.744148	0.273685	0.073*
C9	0.3218 (5)	0.7580 (5)	0.0942 (4)	0.1026 (12)
H9A	0.347365	0.665621	0.093359	0.123*
H9B	0.222618	0.745969	0.140888	0.123*
C11	0.5747 (6)	0.4639 (4)	0.2945 (5)	0.1100 (14)
H11A	0.629576	0.460616	0.356097	0.132*
H11B	0.485204	0.406861	0.351054	0.132*
C13	0.9424 (7)	0.6577 (6)	0.5468 (8)	0.153 (2)
H13A	0.842208	0.634222	0.570954	0.184*
H13B	0.986393	0.603032	0.494508	0.184*
C10	0.3504 (10)	0.8618 (8)	−0.0404 (6)	0.192 (4)
H10A	0.446087	0.864289	−0.089811	0.288*
H10B	0.334734	0.955015	−0.039080	0.288*
H10C	0.290412	0.838065	−0.085772	0.288*
C14	0.9798 (11)	0.6104 (8)	0.6682 (8)	0.207 (4)
H14A	1.071080	0.656498	0.649862	0.311*
H14B	0.980900	0.507099	0.703788	0.311*
H14C	0.913590	0.634622	0.735386	0.311*
C12	0.6408 (12)	0.4043 (8)	0.2078 (8)	0.256 (6)
H12A	0.704453	0.477739	0.126832	0.384*
H12B	0.573426	0.363318	0.180694	0.384*
H12C	0.691643	0.329560	0.254072	0.384*
C15A	1.024 (2)	1.1071 (17)	0.1218 (16)	0.179 (5)	0.613 (17)
H15A	0.937678	1.147926	0.111771	0.215*	0.613 (17)
H15B	1.039539	1.043772	0.073293	0.215*	0.613 (17)
C16A	1.134 (2)	1.222 (2)	0.0542 (16)	0.223 (8)	0.613 (17)
H16A	1.184382	1.220554	0.117966	0.335*	0.613 (17)
H16B	1.096374	1.313031	0.022813	0.335*	0.613 (17)
H16C	1.196202	1.211130	−0.023860	0.335*	0.613 (17)
C15B	1.114 (2)	1.099 (2)	0.133 (2)	0.160 (6)	0.387 (17)
H15C	1.142952	1.027981	0.095194	0.191*	0.387 (17)
H15D	1.073087	1.170314	0.068754	0.191*	0.387 (17)
C16B	1.235 (3)	1.169 (4)	0.129 (4)	0.266 (15)	0.387 (17)
H16D	1.250538	1.127820	0.218751	0.399*	0.387 (17)
H16E	1.225492	1.270555	0.104094	0.399*	0.387 (17)
H16F	1.312861	1.158572	0.061454	0.399*	0.387 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0599 (4)	0.0669 (4)	0.0772 (5)	0.0029 (3)	−0.0231 (3)	−0.0442 (4)
P2	0.0424 (4)	0.1023 (7)	0.1273 (8)	0.0059 (4)	−0.0131 (4)	−0.0792 (6)
O3	0.0784 (13)	0.0691 (11)	0.0785 (12)	0.0099 (9)	−0.0226 (10)	−0.0434 (10)
O2	0.1007 (16)	0.0806 (13)	0.1008 (15)	0.0179 (12)	−0.0553 (13)	−0.0510 (12)
O5	0.0586 (12)	0.0879 (15)	0.157 (2)	0.0176 (10)	−0.0486 (13)	−0.0756 (16)
O1	0.0720 (13)	0.0905 (15)	0.0983 (15)	−0.0206 (11)	−0.0093 (11)	−0.0552 (13)
O4	0.0576 (13)	0.163 (3)	0.178 (3)	0.0204 (15)	−0.0188 (15)	−0.134 (2)
C5	0.0430 (10)	0.0481 (11)	0.0565 (12)	0.0012 (8)	−0.0166 (9)	−0.0254 (9)
C4	0.0430 (11)	0.0531 (11)	0.0602 (12)	0.0006 (9)	−0.0167 (9)	−0.0280 (10)
C7	0.0460 (12)	0.0668 (14)	0.0833 (16)	0.0032 (10)	−0.0251 (11)	−0.0455 (13)
C3	0.0505 (12)	0.0578 (12)	0.0639 (13)	0.0022 (9)	−0.0192 (10)	−0.0340 (11)
C6	0.0404 (11)	0.0569 (12)	0.0671 (13)	0.0030 (9)	−0.0164 (10)	−0.0321 (11)
O6	0.0738 (15)	0.120 (2)	0.135 (2)	−0.0275 (15)	0.0135 (16)	−0.0734 (19)
C8	0.0399 (11)	0.0707 (15)	0.0862 (17)	0.0050 (10)	−0.0229 (11)	−0.0451 (13)
C1	0.0436 (11)	0.0675 (14)	0.0788 (16)	0.0040 (10)	−0.0160 (11)	−0.0431 (13)
C2	0.0483 (12)	0.0693 (15)	0.0752 (15)	0.0041 (11)	−0.0146 (11)	−0.0429 (13)
C9	0.113 (3)	0.116 (3)	0.112 (3)	0.016 (2)	−0.063 (2)	−0.061 (2)
C11	0.141 (4)	0.080 (2)	0.112 (3)	0.039 (2)	−0.037 (3)	−0.043 (2)
C13	0.166 (5)	0.101 (3)	0.219 (6)	−0.009 (3)	−0.114 (5)	−0.054 (4)
C10	0.309 (11)	0.156 (5)	0.114 (4)	−0.029 (6)	−0.096 (5)	−0.035 (4)
C14	0.310 (11)	0.135 (5)	0.162 (6)	−0.061 (6)	−0.074 (7)	−0.042 (5)
C12	0.440 (17)	0.120 (5)	0.177 (7)	0.112 (8)	−0.034 (8)	−0.066 (5)
C15A	0.152 (10)	0.189 (9)	0.166 (8)	−0.040 (9)	0.012 (9)	−0.080 (7)
C16A	0.246 (16)	0.218 (13)	0.144 (10)	−0.128 (12)	0.045 (9)	−0.077 (9)
C15B	0.113 (9)	0.141 (9)	0.173 (9)	−0.058 (8)	0.058 (9)	−0.077 (8)
C16B	0.22 (2)	0.23 (2)	0.23 (2)	−0.04 (2)	0.063 (19)	−0.054 (19)

Geometric parameters (Å, º)

P1—O3	1.571 (2)	C9—C10	1.382 (7)
P1—O2	1.559 (2)	C11—H11A	0.9700
P1—O1	1.461 (2)	C11—H11B	0.9700
P1—C3	1.808 (2)	C11—C12	1.347 (7)
P2—O5	1.564 (3)	C13—H13A	0.9700
P2—O4	1.461 (3)	C13—H13B	0.9700
P2—O6	1.567 (3)	C13—C14	1.380 (8)
P2—C1	1.797 (3)	C10—H10A	0.9600
O3—C11	1.451 (4)	C10—H10B	0.9600
O2—C9	1.442 (4)	C10—H10C	0.9600
O5—C13	1.423 (6)	C14—H14A	0.9600
C5—C5^i	1.439 (4)	C14—H14B	0.9600
C5—C4	1.426 (3)	C14—H14C	0.9600
C5—C6	1.424 (3)	C12—H12A	0.9600
C4—C7	1.430 (3)	C12—H12B	0.9600
C4—C3	1.401 (3)	C12—H12C	0.9600
C7—H7	0.9300	C15A—H15A	0.9700
C7—C8	1.350 (4)	C15A—H15B	0.9700
C3—C2	1.387 (3)	C15A—C16A	1.416 (14)
C6—C8^i	1.432 (3)	C16A—H16A	0.9600
C6—C1	1.407 (3)	C16A—H16B	0.9600
O6—C15A	1.319 (16)	C16A—H16C	0.9600
O6—C15B	1.391 (15)	C15B—H15C	0.9700
C8—H8	0.9300	C15B—H15D	0.9700
C1—C2	1.398 (3)	C15B—C16B	1.390 (18)
C2—H2	0.9300	C16B—H16D	0.9600
C9—H9A	0.9700	C16B—H16E	0.9600
C9—H9B	0.9700	C16B—H16F	0.9600
O3—P1—C3	106.19 (12)	C12—C11—H11A	109.1
O2—P1—O3	102.14 (13)	C12—C11—H11B	109.1
O2—P1—C3	101.95 (12)	O5—C13—H13A	108.1
O1—P1—O3	114.16 (13)	O5—C13—H13B	108.1
O1—P1—O2	116.28 (15)	H13A—C13—H13B	107.3
O1—P1—C3	114.55 (12)	C14—C13—O5	116.6 (5)
O5—P2—O6	99.53 (17)	C14—C13—H13A	108.1
O5—P2—C1	107.14 (13)	C14—C13—H13B	108.1
O4—P2—O5	115.42 (18)	C9—C10—H10A	109.5
O4—P2—O6	116.45 (18)	C9—C10—H10B	109.5
O4—P2—C1	111.17 (14)	C9—C10—H10C	109.5
O6—P2—C1	106.01 (15)	H10A—C10—H10B	109.5
C11—O3—P1	120.9 (2)	H10A—C10—H10C	109.5
C9—O2—P1	120.1 (2)	H10B—C10—H10C	109.5
C13—O5—P2	118.3 (3)	C13—C14—H14A	109.5
C4—C5—C5^i	119.8 (2)	C13—C14—H14B	109.5
C6—C5—C5^i	120.0 (2)	C13—C14—H14C	109.5
C6—C5—C4	120.2 (2)	H14A—C14—H14B	109.5
C5—C4—C7	118.3 (2)	H14A—C14—H14C	109.5
C3—C4—C5	119.1 (2)	H14B—C14—H14C	109.5
C3—C4—C7	122.6 (2)	C11—C12—H12A	109.5
C4—C7—H7	119.0	C11—C12—H12B	109.5
C8—C7—C4	121.9 (2)	C11—C12—H12C	109.5
C8—C7—H7	119.0	H12A—C12—H12B	109.5
C4—C3—P1	121.67 (18)	H12A—C12—H12C	109.5
C2—C3—P1	118.03 (19)	H12B—C12—H12C	109.5
C2—C3—C4	120.3 (2)	O6—C15A—H15A	108.0
C5—C6—C8^i	118.3 (2)	O6—C15A—H15B	108.0
C1—C6—C5	119.0 (2)	O6—C15A—C16A	117.1 (14)
C1—C6—C8^i	122.7 (2)	H15A—C15A—H15B	107.3
C15A—O6—P2	119.4 (7)	C16A—C15A—H15A	108.0
C15B—O6—P2	129.2 (8)	C16A—C15A—H15B	108.0
C7—C8—C6^i	121.7 (2)	C15A—C16A—H16A	109.5
C7—C8—H8	119.2	C15A—C16A—H16B	109.5
C6^i—C8—H8	119.2	C15A—C16A—H16C	109.5
C6—C1—P2	124.26 (18)	H16A—C16A—H16B	109.5
C2—C1—P2	115.81 (19)	H16A—C16A—H16C	109.5
C2—C1—C6	119.9 (2)	H16B—C16A—H16C	109.5
C3—C2—C1	121.5 (2)	O6—C15B—H15C	106.5
C3—C2—H2	119.3	O6—C15B—H15D	106.5
C1—C2—H2	119.3	H15C—C15B—H15D	106.5
O2—C9—H9A	109.8	C16B—C15B—O6	123 (2)
O2—C9—H9B	109.8	C16B—C15B—H15C	106.5
H9A—C9—H9B	108.2	C16B—C15B—H15D	106.5
C10—C9—O2	109.5 (4)	C15B—C16B—H16D	109.5
C10—C9—H9A	109.8	C15B—C16B—H16E	109.5
C10—C9—H9B	109.8	C15B—C16B—H16F	109.5
O3—C11—H11A	109.1	H16D—C16B—H16E	109.5
O3—C11—H11B	109.1	H16D—C16B—H16F	109.5
H11A—C11—H11B	107.8	H16E—C16B—H16F	109.5
C12—C11—O3	112.5 (4)
P1—O3—C11—C12	159.9 (7)	C5^i—C5—C6—C8^i	0.9 (4)
P1—O2—C9—C10	−154.4 (5)	C5^i—C5—C6—C1	−178.7 (3)
P1—C3—C2—C1	−176.8 (2)	C5—C4—C7—C8	−1.1 (4)
P2—O5—C13—C14	−179.6 (6)	C5—C4—C3—P1	175.79 (17)
P2—O6—C15A—C16A	−154.0 (13)	C5—C4—C3—C2	−2.2 (4)
P2—O6—C15B—C16B	−126 (2)	C5—C6—C1—P2	177.1 (2)
P2—C1—C2—C3	−178.5 (2)	C5—C6—C1—C2	−2.5 (4)
O3—P1—O2—C9	71.2 (3)	C4—C5—C6—C8^i	−178.8 (2)
O3—P1—C3—C4	−179.9 (2)	C4—C5—C6—C1	1.6 (4)
O3—P1—C3—C2	−1.8 (2)	C4—C7—C8—C6^i	−0.1 (4)
O2—P1—O3—C11	−152.7 (3)	C4—C3—C2—C1	1.3 (4)
O2—P1—C3—C4	73.5 (2)	C7—C4—C3—P1	−4.4 (4)
O2—P1—C3—C2	−108.4 (2)	C7—C4—C3—C2	177.5 (3)
O5—P2—O6—C15A	164.4 (11)	C3—P1—O3—C11	100.9 (3)
O5—P2—O6—C15B	116.1 (17)	C3—P1—O2—C9	−179.1 (3)
O5—P2—C1—C6	57.0 (3)	C3—C4—C7—C8	179.1 (3)
O5—P2—C1—C2	−123.4 (2)	C6—C5—C4—C7	−179.0 (2)
O1—P1—O3—C11	−26.3 (3)	C6—C5—C4—C3	0.8 (3)
O1—P1—O2—C9	−53.7 (3)	C6—C1—C2—C3	1.2 (4)
O1—P1—C3—C4	−52.9 (3)	O6—P2—O5—C13	−174.8 (4)
O1—P1—C3—C2	125.1 (2)	O6—P2—C1—C6	−48.6 (3)
O4—P2—O5—C13	−49.3 (5)	O6—P2—C1—C2	131.1 (3)
O4—P2—O6—C15A	39.7 (11)	C8^i—C6—C1—P2	−2.5 (4)
O4—P2—O6—C15B	−8.6 (17)	C8^i—C6—C1—C2	177.8 (3)
O4—P2—C1—C6	−176.1 (3)	C1—P2—O5—C13	75.1 (4)
O4—P2—C1—C2	3.6 (3)	C1—P2—O6—C15A	−84.6 (11)
C5^i—C5—C4—C7	1.3 (4)	C1—P2—O6—C15B	−132.8 (17)
C5^i—C5—C4—C3	−178.9 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

(IEF-33)

Crystal data

C16H18Ca2O16P4·3(H2O)	Z = 2
Mr = 724.39	F(000) = 744
Triclinic, P1	Dx = 1.888 Mg m^−3
a = 8.4993 (3) Å	Synchrotron radiation, λ = 0.82656 Å
b = 12.5656 (9) Å	Cell parameters from 973 reflections
c = 12.5832 (13) Å	θ = 2.4–25.9°
α = 103.252 (7)°	µ = 1.21 mm^−1
β = 98.700 (5)°	T = 100 K
γ = 97.446 (4)°	Needle, white
V = 1274.05 (17) Å^3	0.1 × 0.01 × 0.01 mm

Data collection

Pilatus DECTRIS 6M diffractometer	Rint = 0.269
Radiation source: synchrotron	θmax = 26.4°, θmin = 2.0°
phi scan	h = −9→9
10741 measured reflections	k = −12→12
3082 independent reflections	l = 0→13
1564 reflections with I > 2σ(I)

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.121	H-atom parameters constrained
wR(F^2) = 0.323	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3082 reflections	Δρmax = 1.67 e Å^−3
377 parameters	Δρmin = −0.71 e Å^−3

Special details

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

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

	x	y	z	Uiso*/Ueq
Ca2	0.2964 (3)	0.0567 (3)	0.7165 (3)	0.0599 (12)
Ca1	0.8233 (3)	1.0756 (3)	0.7818 (3)	0.0597 (12)
P1	0.5173 (3)	0.8398 (3)	0.6831 (4)	0.0552 (14)
P3	0.0725 (3)	0.2579 (3)	0.6782 (4)	0.0541 (14)
P2	0.3759 (3)	0.7283 (3)	0.2330 (4)	0.0571 (15)
P4	−0.0079 (3)	0.1387 (3)	0.2284 (4)	0.0539 (14)
O9	0.0300 (9)	0.3590 (8)	0.7594 (11)	0.067 (4)
H9	0.091231	0.370593	0.821416	0.101*
O4W	0.2481 (10)	0.0073 (9)	0.5233 (12)	0.080 (4)
H4WA	0.201500	−0.047526	0.466706	0.120*
H4WB	0.285142	0.059295	0.493822	0.120*
O3	0.5962 (8)	0.7846 (8)	0.7718 (10)	0.058 (3)
H3	0.694346	0.785566	0.768745	0.087*
O10	−0.1636 (8)	0.1693 (7)	0.1667 (9)	0.050 (3)
H10	−0.244001	0.146819	0.192011	0.075*
O3W	0.3743 (9)	0.1010 (8)	0.9164 (10)	0.069 (4)
H3WA	0.431452	0.160839	0.968420	0.103*
H3WB	0.347088	0.052986	0.956733	0.103*
O1	0.6450 (8)	0.9186 (7)	0.6583 (10)	0.054 (3)
O11	−0.0474 (8)	0.0327 (7)	0.2644 (10)	0.056 (3)
O12	0.1098 (8)	0.1300 (8)	0.1505 (10)	0.057 (3)
O5	0.4381 (9)	0.8495 (9)	0.2676 (10)	0.064 (3)
O4	0.4860 (9)	0.6601 (9)	0.1659 (10)	0.060 (3)
H4	0.549311	0.636172	0.209173	0.090*
O8	−0.0640 (9)	0.1592 (8)	0.6513 (10)	0.059 (3)
O6	0.2114 (9)	0.7042 (8)	0.1603 (10)	0.060 (3)
O2	0.3819 (8)	0.8920 (8)	0.7256 (10)	0.057 (3)
O7	0.2312 (9)	0.2285 (8)	0.7258 (11)	0.067 (4)
O2W	1.0256 (9)	1.1649 (8)	0.9389 (11)	0.070 (4)
H2WA	1.119316	1.132345	0.941861	0.106*
H2WB	0.994064	1.156997	1.005183	0.106*
C8	0.1577 (13)	0.3901 (13)	0.2526 (15)	0.050 (4)
H8	0.115999	0.338301	0.182883	0.060*
O1W	0.6922 (8)	1.0535 (8)	0.9378 (11)	0.063 (4)
H1WA	0.597412	1.077647	0.932616	0.095*
H1WB	0.749063	1.096636	1.002679	0.095*
C13	0.1394 (12)	0.3586 (13)	0.3538 (15)	0.047 (4)
C12	0.1981 (12)	0.4330 (13)	0.4529 (15)	0.044 (4)
C2	0.4356 (13)	0.7579 (13)	0.4572 (17)	0.054 (5)
H2	0.483633	0.830705	0.457793	0.065*
C7	0.2301 (13)	0.4880 (14)	0.2557 (16)	0.057 (5)
H7	0.240952	0.505285	0.187205	0.069*
C15	0.0468 (12)	0.2262 (14)	0.4522 (18)	0.061 (6)
H15	0.000002	0.152801	0.450387	0.073*
C5	0.2828 (13)	0.5439 (14)	0.4586 (16)	0.054 (5)
C4	0.2949 (13)	0.5717 (12)	0.3564 (17)	0.054 (5)
C11	0.1834 (12)	0.4086 (14)	0.5549 (17)	0.058 (5)
C1	0.4298 (12)	0.7264 (12)	0.5562 (18)	0.063 (6)
C6	0.3465 (14)	0.6250 (13)	0.5601 (17)	0.055 (5)
C9	0.3225 (14)	0.5948 (13)	0.6596 (16)	0.060 (5)
H9A	0.361303	0.648326	0.728530	0.072*
C14	0.0612 (12)	0.2507 (12)	0.3540 (14)	0.046 (4)
C10	0.2461 (13)	0.4922 (12)	0.6608 (16)	0.057 (5)
H10A	0.233760	0.475288	0.729231	0.069*
C16	0.0974 (12)	0.3039 (13)	0.5570 (16)	0.052 (5)
C3	0.3685 (13)	0.6790 (13)	0.3569 (16)	0.053 (5)
O7W	0.5298 (14)	0.6815 (11)	0.9421 (12)	0.098 (5)
H7WA	0.623272	0.670671	0.972626	0.147*
H7WB	0.549874	0.709092	0.887128	0.147*
O6W	0.2059 (12)	0.5951 (13)	0.9408 (14)	0.116 (6)
H6WA	0.204294	0.623071	1.010512	0.173*
H6WB	0.305437	0.614177	0.934433	0.173*
O5W	0.1852 (15)	0.3815 (12)	0.9979 (15)	0.114 (6)
H5WA	0.224428	0.445405	0.988365	0.171*
H5WB	0.086065	0.386653	1.005046	0.171*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca2	0.0297 (12)	0.053 (2)	0.096 (3)	−0.0050 (12)	0.0097 (14)	0.023 (2)
Ca1	0.0293 (12)	0.061 (2)	0.088 (3)	0.0016 (12)	0.0115 (14)	0.021 (2)
P1	0.0233 (15)	0.055 (3)	0.086 (4)	−0.0018 (14)	0.0098 (18)	0.021 (3)
P3	0.0273 (15)	0.047 (3)	0.090 (4)	0.0015 (14)	0.0135 (18)	0.023 (3)
P2	0.0259 (15)	0.053 (3)	0.097 (5)	−0.0004 (15)	0.0137 (18)	0.030 (3)
P4	0.0227 (14)	0.049 (2)	0.091 (4)	0.0014 (14)	0.0147 (18)	0.019 (2)
O9	0.030 (4)	0.060 (7)	0.110 (12)	−0.013 (4)	0.019 (5)	0.025 (7)
O4W	0.040 (5)	0.065 (8)	0.136 (14)	−0.007 (5)	0.023 (6)	0.030 (8)
O3	0.020 (4)	0.062 (7)	0.090 (10)	−0.002 (4)	0.009 (4)	0.020 (6)
O10	0.029 (4)	0.050 (6)	0.076 (10)	0.007 (4)	0.014 (4)	0.023 (6)
O3W	0.044 (5)	0.063 (7)	0.111 (12)	0.014 (4)	0.021 (5)	0.040 (7)
O1	0.031 (4)	0.042 (6)	0.089 (10)	0.007 (4)	0.011 (5)	0.019 (6)
O11	0.025 (4)	0.048 (6)	0.098 (10)	−0.008 (4)	0.010 (4)	0.030 (6)
O12	0.031 (4)	0.057 (7)	0.076 (10)	0.005 (4)	0.004 (5)	0.009 (6)
O5	0.033 (4)	0.067 (7)	0.092 (11)	−0.006 (4)	0.016 (5)	0.025 (7)
O4	0.037 (4)	0.056 (7)	0.091 (11)	0.005 (4)	0.013 (5)	0.027 (7)
O8	0.036 (4)	0.057 (7)	0.085 (10)	0.000 (4)	0.008 (5)	0.023 (6)
O6	0.036 (4)	0.063 (7)	0.088 (11)	0.003 (4)	0.019 (5)	0.034 (7)
O2	0.030 (4)	0.046 (6)	0.106 (11)	0.005 (4)	0.014 (5)	0.038 (6)
O7	0.031 (4)	0.057 (7)	0.113 (12)	0.001 (4)	0.016 (5)	0.026 (7)
O2W	0.032 (4)	0.061 (7)	0.118 (12)	0.004 (4)	0.022 (5)	0.021 (7)
C8	0.028 (6)	0.060 (11)	0.066 (15)	0.011 (6)	0.001 (6)	0.030 (9)
O1W	0.027 (4)	0.055 (7)	0.110 (12)	0.007 (4)	0.017 (5)	0.023 (7)
C13	0.019 (5)	0.074 (11)	0.047 (13)	0.018 (6)	0.007 (6)	0.009 (10)
C12	0.019 (5)	0.065 (10)	0.049 (14)	0.008 (6)	0.003 (6)	0.020 (10)
C2	0.026 (6)	0.045 (10)	0.106 (18)	0.008 (6)	0.026 (8)	0.036 (11)
C7	0.028 (6)	0.079 (13)	0.074 (16)	0.011 (7)	0.023 (7)	0.026 (11)
C15	0.012 (5)	0.072 (12)	0.112 (19)	0.008 (6)	0.011 (7)	0.050 (13)
C5	0.024 (5)	0.074 (12)	0.063 (14)	−0.009 (6)	0.012 (7)	0.025 (11)
C4	0.033 (6)	0.035 (9)	0.086 (17)	0.002 (6)	−0.004 (7)	0.012 (10)
C11	0.014 (5)	0.077 (12)	0.081 (16)	0.017 (6)	0.002 (7)	0.017 (12)
C1	0.018 (5)	0.045 (10)	0.14 (2)	0.009 (6)	0.026 (8)	0.049 (11)
C6	0.034 (6)	0.049 (10)	0.083 (17)	0.010 (6)	0.014 (8)	0.015 (11)
C9	0.033 (6)	0.058 (10)	0.075 (16)	−0.012 (6)	0.011 (7)	0.001 (10)
C14	0.027 (6)	0.052 (10)	0.068 (14)	0.006 (6)	0.016 (7)	0.032 (9)
C10	0.030 (6)	0.057 (10)	0.089 (17)	−0.011 (6)	0.015 (7)	0.036 (11)
C16	0.019 (5)	0.062 (10)	0.067 (14)	−0.001 (6)	0.001 (6)	0.010 (10)
C3	0.028 (6)	0.052 (10)	0.076 (15)	0.002 (6)	0.007 (7)	0.015 (10)
O7W	0.100 (8)	0.109 (12)	0.094 (14)	0.009 (7)	0.022 (8)	0.043 (10)
O6W	0.056 (6)	0.161 (15)	0.123 (16)	0.028 (7)	0.015 (7)	0.019 (12)
O5W	0.104 (9)	0.097 (11)	0.134 (18)	−0.015 (8)	0.021 (9)	0.032 (11)

Geometric parameters (Å, º)

Ca2—Ca1^i	4.250 (3)	O3W—H3WA	0.9023
Ca2—Ca1^ii	4.394 (3)	O3W—H3WB	0.9027
Ca2—O4W	2.325 (15)	O4—H4	0.8400
Ca2—O3W	2.415 (13)	O2W—H2WA	0.9412
Ca2—O11^iii	2.336 (7)	O2W—H2WB	0.9356
Ca2—O5^iv	2.364 (7)	C8—H8	0.9500
Ca2—O2^ii	2.301 (9)	C8—C13	1.44 (2)
Ca2—O7	2.279 (11)	C8—C7	1.29 (2)
Ca1—P3^v	3.518 (5)	O1W—H1WA	0.8957
Ca1—O1	2.390 (10)	O1W—H1WB	0.8963
Ca1—O11^iv	2.543 (9)	C13—C12	1.35 (2)
Ca1—O12^iv	2.995 (10)	C13—C14	1.43 (2)
Ca1—O5^vi	2.569 (10)	C12—C5	1.46 (2)
Ca1—O8^v	2.392 (11)	C12—C11	1.41 (2)
Ca1—O6^vi	2.761 (11)	C2—H2	0.9500
Ca1—O2W	2.362 (12)	C2—C1	1.40 (2)
Ca1—O1W	2.449 (11)	C2—C3	1.40 (2)
P1—O3	1.557 (11)	C7—H7	0.9500
P1—O1	1.490 (9)	C7—C4	1.43 (2)
P1—O2	1.503 (10)	C15—H15	0.9500
P1—C1	1.86 (2)	C15—C14	1.36 (2)
P3—O9	1.556 (12)	C15—C16	1.42 (2)
P3—O8	1.521 (9)	C5—C4	1.42 (2)
P3—O7	1.517 (10)	C5—C6	1.42 (2)
P3—C16	1.782 (18)	C4—C3	1.41 (2)
P2—O5	1.486 (11)	C11—C10	1.47 (3)
P2—O4	1.562 (11)	C11—C16	1.43 (2)
P2—O6	1.503 (10)	C1—C6	1.39 (2)
P2—C3	1.812 (18)	C6—C9	1.42 (2)
P4—O10	1.569 (9)	C9—H9A	0.9500
P4—O11	1.516 (10)	C9—C10	1.37 (2)
P4—O12	1.499 (11)	C10—H10A	0.9500
P4—C14	1.819 (17)	O7W—H7WA	0.8700
O9—H9	0.8400	O7W—H7WB	0.8700
O4W—H4WA	0.8700	O6W—H6WA	0.8700
O4W—H4WB	0.8700	O6W—H6WB	0.8700
O3—H3	0.8400	O5W—H5WA	0.8700
O10—H10	0.8400	O5W—H5WB	0.8700
Ca1^i—Ca2—Ca1^ii	159.01 (15)	O4—P2—C3	106.9 (6)
O4W—Ca2—Ca1^ii	99.4 (2)	O6—P2—Ca2^iv	132.8 (4)
O4W—Ca2—Ca1^i	101.6 (2)	O6—P2—Ca1^vi	59.9 (4)
O4W—Ca2—O3W	173.8 (3)	O6—P2—O4	106.9 (7)
O4W—Ca2—O11^iii	96.4 (4)	O6—P2—C3	110.8 (6)
O4W—Ca2—O5^iv	93.9 (4)	C3—P2—Ca2^iv	109.7 (5)
O3W—Ca2—Ca1^i	84.3 (2)	C3—P2—Ca1^vi	113.9 (5)
O3W—Ca2—Ca1^ii	74.7 (2)	Ca1^iv—P4—Ca2^iii	77.61 (10)
O11^iii—Ca2—Ca1^i	30.8 (2)	O10—P4—Ca2^iii	81.5 (3)
O11^iii—Ca2—Ca1^ii	146.2 (3)	O10—P4—Ca1^iv	138.7 (4)
O11^iii—Ca2—O3W	87.7 (4)	O10—P4—C14	105.3 (6)
O11^iii—Ca2—O5^iv	169.5 (5)	O11—P4—Ca2^iii	31.0 (3)
O5^iv—Ca2—Ca1^i	147.5 (3)	O11—P4—Ca1^iv	48.6 (3)
O5^iv—Ca2—Ca1^ii	28.3 (3)	O11—P4—O10	111.1 (4)
O5^iv—Ca2—O3W	81.9 (4)	O11—P4—C14	107.3 (7)
O2^ii—Ca2—Ca1^ii	65.14 (18)	O12—P4—Ca2^iii	133.1 (4)
O2^ii—Ca2—Ca1^i	114.5 (2)	O12—P4—Ca1^iv	65.9 (4)
O2^ii—Ca2—O4W	92.2 (4)	O12—P4—O10	106.9 (6)
O2^ii—Ca2—O3W	83.5 (4)	O12—P4—O11	112.6 (6)
O2^ii—Ca2—O11^iii	84.6 (3)	O12—P4—C14	113.4 (5)
O2^ii—Ca2—O5^iv	92.9 (3)	C14—P4—Ca2^iii	108.1 (4)
O7—Ca2—Ca1^ii	110.6 (2)	C14—P4—Ca1^iv	114.8 (5)
O7—Ca2—Ca1^i	67.5 (2)	P3—O9—H9	108.6
O7—Ca2—O4W	93.3 (5)	Ca2—O4W—H4WA	141.2
O7—Ca2—O3W	90.8 (4)	Ca2—O4W—H4WB	114.2
O7—Ca2—O11^iii	98.0 (3)	H4WA—O4W—H4WB	104.5
O7—Ca2—O5^iv	83.4 (3)	P1—O3—H3	109.5
O7—Ca2—O2^ii	173.6 (5)	P4—O10—H10	109.4
P3^v—Ca1—Ca2^v	51.38 (8)	Ca2—O3W—H3WA	134.3
O1—Ca1—Ca2^v	107.6 (2)	Ca2—O3W—H3WB	122.7
O1—Ca1—P3^v	120.6 (3)	H3WA—O3W—H3WB	103.1
O1—Ca1—O11^iv	85.4 (3)	P1—O1—Ca1	129.1 (7)
O1—Ca1—O12^iv	70.9 (3)	Ca2^iii—O11—Ca1^iv	121.1 (4)
O1—Ca1—O5^vi	76.0 (3)	P4—O11—Ca2^iii	129.4 (5)
O1—Ca1—O8^v	100.5 (4)	P4—O11—Ca1^iv	104.8 (4)
O1—Ca1—O6^vi	130.2 (3)	P4—O12—Ca1^iv	86.9 (5)
O1—Ca1—O1W	91.7 (3)	Ca2^iv—O5—Ca1^vi	125.9 (4)
O11^iv—Ca1—Ca2^v	28.07 (17)	P2—O5—Ca2^iv	128.7 (5)
O11^iv—Ca1—P3^v	77.4 (2)	P2—O5—Ca1^vi	100.3 (4)
O11^iv—Ca1—O12^iv	53.1 (3)	P2—O4—H4	109.5
O11^iv—Ca1—O5^vi	153.8 (4)	P3—O8—Ca1^i	126.6 (7)
O11^iv—Ca1—O6^vi	136.9 (2)	P2—O6—Ca1^vi	92.0 (5)
O12^iv—Ca1—Ca2^v	77.83 (16)	P1—O2—Ca2^vii	131.8 (5)
O12^iv—Ca1—P3^v	129.21 (17)	P3—O7—Ca2	128.2 (6)
O5^vi—Ca1—Ca2^v	145.1 (3)	Ca1—O2W—H2WA	113.5
O5^vi—Ca1—P3^v	96.2 (2)	Ca1—O2W—H2WB	112.1
O5^vi—Ca1—O12^iv	133.0 (3)	H2WA—O2W—H2WB	100.9
O5^vi—Ca1—O6^vi	54.8 (3)	C13—C8—H8	119.7
O8^v—Ca1—Ca2^v	56.2 (2)	C7—C8—H8	119.7
O8^v—Ca1—P3^v	20.3 (3)	C7—C8—C13	120.7 (17)
O8^v—Ca1—O11^iv	76.3 (3)	Ca1—O1W—H1WA	111.0
O8^v—Ca1—O12^iv	128.7 (3)	Ca1—O1W—H1WB	111.7
O8^v—Ca1—O5^vi	89.0 (3)	H1WA—O1W—H1WB	103.3
O8^v—Ca1—O6^vi	74.1 (3)	C12—C13—C8	119.4 (15)
O8^v—Ca1—O1W	160.8 (4)	C12—C13—C14	118.1 (16)
O6^vi—Ca1—Ca2^v	108.96 (17)	C14—C13—C8	122.4 (16)
O6^vi—Ca1—P3^v	64.1 (2)	C13—C12—C5	120.9 (16)
O6^vi—Ca1—O12^iv	149.6 (4)	C13—C12—C11	122.6 (16)
O2W—Ca1—Ca2^v	67.6 (2)	C11—C12—C5	116.5 (16)
O2W—Ca1—P3^v	77.3 (3)	C1—C2—H2	121.0
O2W—Ca1—O1	154.2 (4)	C1—C2—C3	118.0 (14)
O2W—Ca1—O11^iv	80.7 (3)	C3—C2—H2	121.0
O2W—Ca1—O12^iv	83.4 (3)	C8—C7—H7	118.2
O2W—Ca1—O5^vi	123.2 (4)	C8—C7—C4	123.6 (17)
O2W—Ca1—O8^v	97.2 (4)	C4—C7—H7	118.2
O2W—Ca1—O6^vi	72.9 (3)	C14—C15—H15	118.1
O2W—Ca1—O1W	76.8 (4)	C14—C15—C16	123.8 (15)
O1W—Ca1—Ca2^v	133.7 (2)	C16—C15—H15	118.1
O1W—Ca1—P3^v	145.6 (3)	C4—C5—C12	117.5 (16)
O1W—Ca1—O11^iv	119.9 (3)	C6—C5—C12	123.2 (17)
O1W—Ca1—O12^iv	69.3 (3)	C6—C5—C4	119.3 (15)
O1W—Ca1—O5^vi	79.6 (3)	C5—C4—C7	117.9 (14)
O1W—Ca1—O6^vi	86.7 (3)	C3—C4—C7	122.3 (18)
O3—P1—Ca2^vii	129.3 (5)	C3—C4—C5	119.8 (17)
O3—P1—C1	106.8 (7)	C12—C11—C10	121.0 (15)
O1—P1—Ca2^vii	86.4 (4)	C12—C11—C16	120.2 (17)
O1—P1—O3	108.9 (5)	C16—C11—C10	118.6 (17)
O1—P1—O2	114.4 (5)	C2—C1—P1	113.7 (11)
O1—P1—C1	109.8 (7)	C6—C1—P1	122.7 (16)
O2—P1—Ca2^vii	29.5 (4)	C6—C1—C2	123.0 (18)
O2—P1—O3	108.3 (6)	C5—C6—C9	116.8 (15)
O2—P1—C1	108.4 (5)	C1—C6—C5	118.5 (19)
C1—P1—Ca2^vii	112.8 (4)	C1—C6—C9	124.7 (18)
O9—P3—Ca1^i	90.2 (4)	C6—C9—H9A	118.4
O9—P3—C16	104.9 (7)	C10—C9—C6	123.3 (17)
O8—P3—Ca1^i	33.1 (5)	C10—C9—H9A	118.4
O8—P3—O9	110.3 (5)	C13—C14—P4	123.1 (13)
O8—P3—C16	111.0 (7)	C15—C14—P4	117.1 (12)
O7—P3—Ca1^i	96.3 (4)	C15—C14—C13	119.7 (16)
O7—P3—O9	111.0 (7)	C11—C10—H10A	120.4
O7—P3—O8	111.2 (6)	C9—C10—C11	119.2 (17)
O7—P3—C16	108.3 (6)	C9—C10—H10A	120.4
C16—P3—Ca1^i	143.6 (5)	C15—C16—P3	118.2 (12)
Ca1^vi—P2—Ca2^iv	82.13 (11)	C15—C16—C11	115.2 (16)
O5—P2—Ca2^iv	31.9 (3)	C11—C16—P3	126.1 (14)
O5—P2—Ca1^vi	52.4 (4)	C2—C3—P2	115.0 (12)
O5—P2—O4	113.3 (5)	C2—C3—C4	120.8 (17)
O5—P2—O6	110.6 (6)	C4—C3—P2	124.1 (14)
O5—P2—C3	108.3 (8)	H7WA—O7W—H7WB	104.5
O4—P2—Ca2^iv	83.1 (4)	H6WA—O6W—H6WB	104.5
O4—P2—Ca1^vi	139.3 (5)	H5WA—O5W—H5WB	104.5
Ca2^vii—P1—O1—Ca1	72.2 (5)	O7—P3—C16—C15	96.7 (10)
Ca2^vii—P1—C1—C2	65.8 (9)	O7—P3—C16—C11	−74.5 (12)
Ca2^vii—P1—C1—C6	−105.7 (10)	C8—C13—C12—C5	−1.3 (18)
Ca2^iv—P2—O5—Ca1^vi	155.4 (11)	C8—C13—C12—C11	179.4 (10)
Ca2^iv—P2—O6—Ca1^vi	−41.3 (7)	C8—C13—C14—P4	5.3 (16)
Ca2^iv—P2—C3—C2	27.5 (10)	C8—C13—C14—C15	−179.6 (10)
Ca2^iv—P2—C3—C4	−155.5 (9)	C8—C7—C4—C5	2.0 (19)
Ca2^iii—P4—O11—Ca1^iv	155.3 (11)	C8—C7—C4—C3	−177.8 (12)
Ca2^iii—P4—O12—Ca1^iv	−42.3 (6)	C13—C8—C7—C4	−0.8 (19)
Ca2^iii—P4—C14—C13	−160.3 (8)	C13—C12—C5—C4	2.4 (18)
Ca2^iii—P4—C14—C15	24.5 (10)	C13—C12—C5—C6	179.9 (12)
Ca1^i—P3—O7—Ca2	48.3 (8)	C13—C12—C11—C10	−178.8 (11)
Ca1^i—P3—C16—C15	−33.1 (15)	C13—C12—C11—C16	−2.9 (18)
Ca1^i—P3—C16—C11	155.7 (7)	C12—C13—C14—P4	−174.5 (9)
Ca1^vi—P2—O5—Ca2^iv	−155.4 (11)	C12—C13—C14—C15	0.6 (17)
Ca1^vi—P2—C3—C2	−62.5 (9)	C12—C5—C4—C7	−2.7 (18)
Ca1^vi—P2—C3—C4	114.5 (10)	C12—C5—C4—C3	177.1 (11)
Ca1^iv—P4—O11—Ca2^iii	−155.3 (11)	C12—C5—C6—C1	177.7 (11)
Ca1^iv—P4—C14—C13	115.4 (9)	C12—C5—C6—C9	−1 (2)
Ca1^iv—P4—C14—C15	−59.9 (9)	C12—C11—C10—C9	−1.1 (19)
P1—C1—C6—C5	179.4 (9)	C12—C11—C16—P3	177.9 (9)
P1—C1—C6—C9	−1.9 (18)	C12—C11—C16—C15	6.5 (17)
O9—P3—O8—Ca1^i	−55.9 (9)	C2—C1—C6—C5	8.7 (19)
O9—P3—O7—Ca2	140.9 (7)	C2—C1—C6—C9	−172.6 (12)
O9—P3—C16—C15	−144.6 (9)	C7—C8—C13—C12	0.4 (18)
O9—P3—C16—C11	44.2 (11)	C7—C8—C13—C14	−179.4 (11)
O3—P1—O1—Ca1	−58.3 (8)	C7—C4—C3—P2	5.3 (17)
O3—P1—O2—Ca2^vii	140.6 (8)	C7—C4—C3—C2	−177.8 (12)
O3—P1—C1—C2	−146.5 (8)	C5—C12—C11—C10	1.7 (17)
O3—P1—C1—C6	42.0 (11)	C5—C12—C11—C16	177.6 (11)
O10—P4—O11—Ca2^iii	−18.1 (11)	C5—C4—C3—P2	−174.4 (10)
O10—P4—O11—Ca1^iv	137.2 (5)	C5—C4—C3—C2	2.4 (18)
O10—P4—O12—Ca1^iv	−136.4 (4)	C5—C6—C9—C10	2 (2)
O10—P4—C14—C13	−74.4 (10)	C4—C5—C6—C1	−4.8 (19)
O10—P4—C14—C15	110.3 (10)	C4—C5—C6—C9	176.4 (11)
O1—P1—O2—Ca2^vii	19.0 (12)	C11—C12—C5—C4	−178.1 (11)
O1—P1—C1—C2	−28.7 (10)	C11—C12—C5—C6	−0.6 (19)
O1—P1—C1—C6	159.9 (10)	C1—P1—O1—Ca1	−174.9 (6)
O11—P4—O12—Ca1^iv	−14.1 (6)	C1—P1—O2—Ca2^vii	−103.9 (9)
O11—P4—C14—C13	167.1 (9)	C1—C2—C3—P2	178.2 (8)
O11—P4—C14—C15	−8.1 (10)	C1—C2—C3—C4	1.1 (18)
O12—P4—O11—Ca2^iii	−138.0 (7)	C1—C6—C9—C10	−176.9 (12)
O12—P4—O11—Ca1^iv	17.3 (7)	C6—C5—C4—C7	179.7 (11)
O12—P4—C14—C13	42.2 (12)	C6—C5—C4—C3	−0.5 (19)
O12—P4—C14—C15	−133.1 (9)	C6—C9—C10—C11	−1 (2)
O5—P2—O6—Ca1^vi	−13.9 (7)	C14—P4—O11—Ca2^iii	96.5 (8)
O5—P2—C3—C2	−6.2 (11)	C14—P4—O11—Ca1^iv	−108.2 (5)
O5—P2—C3—C4	170.8 (10)	C14—P4—O12—Ca1^iv	107.9 (6)
O4—P2—O5—Ca2^iv	−20.2 (12)	C14—C13—C12—C5	178.6 (10)
O4—P2—O5—Ca1^vi	135.2 (6)	C14—C13—C12—C11	−0.8 (18)
O4—P2—O6—Ca1^vi	−137.7 (5)	C14—C15—C16—P3	−179.1 (9)
O4—P2—C3—C2	116.2 (10)	C14—C15—C16—C11	−7.0 (18)
O4—P2—C3—C4	−66.9 (11)	C10—C11—C16—P3	−6.1 (17)
O8—P3—O7—Ca2	17.8 (11)	C10—C11—C16—C15	−177.5 (11)
O8—P3—C16—C15	−25.5 (11)	C16—P3—O8—Ca1^i	−171.8 (6)
O8—P3—C16—C11	163.3 (10)	C16—P3—O7—Ca2	−104.4 (9)
O6—P2—O5—Ca2^iv	−140.2 (8)	C16—C15—C14—P4	179.0 (9)
O6—P2—O5—Ca1^vi	15.2 (7)	C16—C15—C14—C13	3.5 (18)
O6—P2—C3—C2	−127.7 (10)	C16—C11—C10—C9	−177.1 (11)
O6—P2—C3—C4	49.2 (12)	C3—P2—O5—Ca2^iv	98.1 (9)
O2—P1—O1—Ca1	62.9 (9)	C3—P2—O5—Ca1^vi	−106.4 (5)
O2—P1—C1—C2	97.0 (9)	C3—P2—O6—Ca1^vi	106.3 (6)
O2—P1—C1—C6	−74.5 (12)	C3—C2—C1—P1	−178.3 (9)
O7—P3—O8—Ca1^i	67.7 (9)	C3—C2—C1—C6	−6.8 (18)

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

(IEF-34)

Crystal data

2(C20H20CaO12P4)	F(000) = 1264
Mr = 616.32	Dx = 1.307 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.6124 (10) Å	Cell parameters from 10348 reflections
b = 18.4191 (8) Å	θ = 3.2–29.8°
c = 8.3124 (4) Å	µ = 0.46 mm^−1
β = 108.823 (4)°	T = 296 K
V = 3132.0 (3) Å^3	Rhombohedral, clear colourless
Z = 4	0.1 × 0.05 × 0.02 mm

Data collection

XtaLAB Synergy, Single source at home/near, HyPix diffractometer	2761 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	1911 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.088
Detector resolution: 10.0000 pixels mm^-1	θmax = 25.0°, θmin = 3.2°
ω scans	h = −25→25
Absorption correction: multi-scan CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −21→21
Tmin = 0.790, Tmax = 1.000	l = −9→9
36413 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.173	w = 1/[σ^2(Fo^2) + (0.0781P)^2 + 6.7439P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2761 reflections	Δρmax = 0.40 e Å^−3
216 parameters	Δρmin = −0.29 e Å^−3
179 restraints

Special details

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	−0.500000	0.55883 (7)	−0.250000	0.0470 (4)
P1	−0.61779 (6)	0.44226 (7)	−0.57048 (17)	0.0529 (4)
P2	−0.57772 (7)	0.28918 (8)	0.00841 (17)	0.0625 (4)
O5	−0.52735 (16)	0.34560 (19)	0.0541 (4)	0.0644 (9)
O2	−0.60578 (16)	0.41324 (19)	−0.7262 (4)	0.0645 (9)
O1	−0.56080 (16)	0.47723 (19)	−0.4482 (5)	0.0687 (10)
O4	−0.62252 (19)	0.2888 (2)	0.1234 (4)	0.0797 (11)
H4	−0.620922	0.328650	0.168648	0.119*
O6	−0.5519 (2)	0.2107 (2)	0.0267 (6)	0.1038 (15)
H6	−0.530960	0.202327	0.126337	0.156*	0.5
O3	−0.6815 (4)	0.4901 (5)	−0.6770 (9)	0.047 (2)	0.5
C5	−0.7215 (2)	0.2712 (2)	−0.4591 (5)	0.0491 (11)
C6	−0.7027 (2)	0.3278 (3)	−0.5480 (6)	0.0510 (11)
C10	−0.7750 (6)	0.5637 (8)	−0.6911 (17)	0.103 (5)	0.5
H10A	−0.765407	0.607464	−0.741248	0.155*	0.5
H10B	−0.804488	0.574442	−0.629243	0.155*	0.5
H10C	−0.794797	0.529079	−0.778895	0.155*	0.5
C2	−0.6113 (2)	0.3548 (3)	−0.2991 (6)	0.0521 (12)
H2	−0.574747	0.382916	−0.245208	0.062*
C8	−0.7577 (2)	0.1592 (3)	−0.2784 (6)	0.0677 (15)
H8	−0.769204	0.121902	−0.218133	0.081*
C1	−0.6465 (2)	0.3695 (3)	−0.4661 (6)	0.0506 (11)
C4	−0.6840 (2)	0.2571 (3)	−0.2878 (6)	0.0537 (11)
C3	−0.6284 (2)	0.3000 (3)	−0.2094 (6)	0.0533 (12)
C7	−0.7047 (2)	0.1995 (3)	−0.2014 (6)	0.0674 (15)
H7	−0.680720	0.189727	−0.088771	0.081*
C9	−0.7144 (4)	0.5335 (6)	−0.5750 (12)	0.056 (2)	0.5
H9A	−0.723989	0.502640	−0.491532	0.067*	0.5
H9B	−0.685845	0.572364	−0.515518	0.067*	0.5
C11	−0.4926 (14)	0.1936 (17)	0.000 (5)	0.107 (7)	0.25
H11A	−0.457882	0.222393	0.076351	0.129*	0.25
H11B	−0.495730	0.206440	−0.115546	0.129*	0.25
O3A	−0.6726 (5)	0.5035 (6)	−0.5971 (15)	0.081 (3)	0.5
H3A	−0.663679	0.527684	−0.509751	0.122*	0.5
C12	−0.4396 (12)	0.179 (2)	0.052 (4)	0.127 (9)	0.25
H12A	−0.418079	0.146122	−0.001882	0.191*	0.25
H12B	−0.440223	0.158757	0.157908	0.191*	0.25
H12C	−0.416371	0.224433	0.073303	0.191*	0.25
C12A	−0.4755 (18)	0.1150 (16)	0.028 (5)	0.140 (10)	0.25
H12D	−0.506616	0.086531	−0.056997	0.210*	0.25
H12E	−0.476295	0.100826	0.138723	0.210*	0.25
H12F	−0.432528	0.107038	0.021241	0.210*	0.25
C11A	−0.5093 (11)	0.192 (2)	−0.063 (3)	0.100 (7)	0.25
H11C	−0.509288	0.230490	−0.142595	0.120*	0.25
H11D	−0.525232	0.148194	−0.128415	0.120*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.0300 (6)	0.0374 (7)	0.0618 (8)	0.000	−0.0016 (5)	0.000
P1	0.0431 (7)	0.0528 (8)	0.0676 (8)	−0.0144 (6)	0.0246 (6)	−0.0062 (6)
P2	0.0600 (8)	0.0646 (9)	0.0534 (8)	−0.0226 (7)	0.0052 (6)	−0.0045 (6)
O5	0.059 (2)	0.072 (2)	0.0549 (19)	−0.0234 (17)	0.0077 (16)	−0.0140 (16)
O2	0.067 (2)	0.073 (2)	0.060 (2)	−0.0243 (18)	0.0282 (17)	−0.0069 (17)
O1	0.063 (2)	0.069 (2)	0.081 (2)	−0.0298 (18)	0.0327 (18)	−0.0247 (19)
O4	0.089 (3)	0.088 (3)	0.064 (2)	−0.037 (2)	0.028 (2)	−0.014 (2)
O6	0.095 (3)	0.074 (3)	0.112 (3)	−0.007 (2)	−0.009 (3)	−0.003 (2)
O3	0.042 (4)	0.063 (5)	0.038 (4)	−0.009 (3)	0.015 (3)	−0.018 (4)
C5	0.043 (2)	0.056 (3)	0.049 (2)	−0.020 (2)	0.0164 (19)	−0.008 (2)
C6	0.041 (2)	0.061 (3)	0.051 (3)	−0.018 (2)	0.015 (2)	−0.008 (2)
C10	0.071 (8)	0.133 (12)	0.093 (9)	0.033 (8)	0.008 (7)	−0.015 (8)
C2	0.044 (2)	0.060 (3)	0.053 (3)	−0.018 (2)	0.017 (2)	−0.013 (2)
C8	0.059 (3)	0.076 (4)	0.062 (3)	−0.031 (3)	0.012 (2)	0.007 (3)
C1	0.044 (2)	0.058 (3)	0.054 (3)	−0.016 (2)	0.022 (2)	−0.009 (2)
C4	0.047 (2)	0.063 (3)	0.048 (3)	−0.017 (2)	0.012 (2)	−0.003 (2)
C3	0.045 (2)	0.062 (3)	0.051 (3)	−0.020 (2)	0.013 (2)	−0.015 (2)
C7	0.060 (3)	0.081 (4)	0.053 (3)	−0.027 (3)	0.006 (2)	0.004 (3)
C9	0.039 (5)	0.078 (6)	0.050 (5)	0.021 (5)	0.014 (4)	−0.017 (5)
C11	0.103 (13)	0.097 (11)	0.117 (13)	0.025 (11)	0.028 (12)	−0.030 (12)
O3A	0.075 (7)	0.071 (7)	0.110 (9)	−0.010 (5)	0.046 (7)	0.006 (7)
C12	0.114 (18)	0.124 (18)	0.138 (18)	0.061 (16)	0.032 (16)	−0.030 (17)
C12A	0.15 (2)	0.094 (17)	0.16 (2)	0.060 (16)	0.033 (17)	−0.017 (17)
C11A	0.094 (12)	0.097 (11)	0.111 (13)	0.025 (11)	0.035 (11)	−0.027 (11)

Geometric parameters (Å, º)

Ca1—O5^i	2.341 (3)	C10—H10B	0.9600
Ca1—O5^ii	2.341 (3)	C10—H10C	0.9600
Ca1—O2^iii	2.413 (3)	C10—C9	1.463 (14)
Ca1—O2^iv	2.413 (3)	C2—H2	0.9300
Ca1—O1	2.303 (3)	C2—C1	1.377 (6)
Ca1—O1^v	2.303 (3)	C2—C3	1.376 (6)
P1—O2	1.498 (4)	C8—H8	0.9300
P1—O1	1.469 (3)	C8—C7	1.342 (6)
P1—O3	1.633 (8)	C4—C3	1.409 (6)
P1—C1	1.810 (5)	C4—C7	1.432 (7)
P1—O3A	1.599 (10)	C7—H7	0.9300
P2—O5	1.464 (3)	C9—H9A	0.9700
P2—O4	1.565 (4)	C9—H9B	0.9700
P2—O6	1.539 (5)	C11—H11A	0.9700
P2—C3	1.799 (5)	C11—H11B	0.9700
O4—H4	0.8200	C11—C12A	1.494 (19)
O6—H6	0.8200	O3A—H3A	0.8200
O6—C11	1.41 (2)	C12—H12A	0.9600
O6—C11A	1.405 (19)	C12—H12B	0.9600
O3—C9	1.501 (12)	C12—H12C	0.9600
C5—C5^vi	1.432 (8)	C12—C11A	1.520 (18)
C5—C6	1.412 (6)	C12A—H12D	0.9600
C5—C4	1.416 (6)	C12A—H12E	0.9600
C6—C8^vi	1.440 (7)	C12A—H12F	0.9600
C6—C1	1.413 (6)	C11A—H11C	0.9700
C10—H10A	0.9600	C11A—H11D	0.9700
O5^i—Ca1—O5^ii	82.46 (17)	C1—C2—H2	118.9
O5^ii—Ca1—O2^iv	82.15 (12)	C3—C2—H2	118.9
O5^ii—Ca1—O2^iii	79.39 (12)	C3—C2—C1	122.3 (4)
O5^i—Ca1—O2^iv	79.39 (12)	C6^vi—C8—H8	119.1
O5^i—Ca1—O2^iii	82.15 (12)	C7—C8—C6^vi	121.7 (5)
O2^iii—Ca1—O2^iv	155.38 (18)	C7—C8—H8	119.1
O1^v—Ca1—O5^ii	161.14 (12)	C6—C1—P1	123.1 (3)
O1—Ca1—O5^i	161.14 (12)	C2—C1—P1	117.8 (3)
O1—Ca1—O5^ii	92.02 (13)	C2—C1—C6	119.2 (4)
O1^v—Ca1—O5^i	92.02 (13)	C5—C4—C7	118.0 (4)
O1—Ca1—O2^iii	114.67 (12)	C3—C4—C5	119.2 (4)
O1—Ca1—O2^iv	82.00 (12)	C3—C4—C7	122.7 (4)
O1^v—Ca1—O2^iii	82.00 (12)	C2—C3—P2	116.3 (3)
O1^v—Ca1—O2^iv	114.67 (12)	C2—C3—C4	119.9 (4)
O1—Ca1—O1^v	98.5 (2)	C4—C3—P2	123.7 (4)
O2—P1—O3	94.3 (3)	C8—C7—C4	121.9 (5)
O2—P1—C1	109.3 (2)	C8—C7—H7	119.1
O2—P1—O3A	117.3 (5)	C4—C7—H7	119.1
O1—P1—O2	114.44 (19)	O3—C9—H9A	110.0
O1—P1—O3	120.7 (4)	O3—C9—H9B	110.0
O1—P1—C1	109.5 (2)	C10—C9—O3	108.5 (8)
O1—P1—O3A	101.8 (5)	C10—C9—H9A	110.0
O3—P1—C1	107.5 (4)	C10—C9—H9B	110.0
O3A—P1—C1	103.6 (5)	H9A—C9—H9B	108.4
O5—P2—O4	113.5 (2)	O6—C11—H11A	109.1
O5—P2—O6	115.2 (2)	O6—C11—H11B	109.1
O5—P2—C3	110.1 (2)	O6—C11—C12A	113 (2)
O4—P2—C3	108.6 (2)	H11A—C11—H11B	107.8
O6—P2—O4	102.2 (3)	C12A—C11—H11A	109.1
O6—P2—C3	106.7 (2)	C12A—C11—H11B	109.1
P2—O5—Ca1^i	135.6 (2)	P1—O3A—H3A	108.0
P1—O2—Ca1^ii	115.31 (17)	H12A—C12—H12B	109.5
P1—O1—Ca1	159.9 (2)	H12A—C12—H12C	109.5
P2—O4—H4	109.5	H12B—C12—H12C	109.5
P2—O6—H6	109.9	C11A—C12—H12A	109.5
C11—O6—P2	120.9 (14)	C11A—C12—H12B	109.5
C11A—O6—P2	117.2 (17)	C11A—C12—H12C	109.5
C9—O3—P1	116.8 (6)	C11—C12A—H12D	109.5
C6—C5—C5^vi	120.2 (5)	C11—C12A—H12E	109.5
C6—C5—C4	119.6 (4)	C11—C12A—H12F	109.5
C4—C5—C5^vi	120.2 (5)	H12D—C12A—H12E	109.5
C5—C6—C8^vi	117.9 (4)	H12D—C12A—H12F	109.5
C5—C6—C1	119.8 (4)	H12E—C12A—H12F	109.5
C1—C6—C8^vi	122.2 (4)	O6—C11A—C12	113 (2)
H10A—C10—H10B	109.5	O6—C11A—H11C	109.0
H10A—C10—H10C	109.5	O6—C11A—H11D	109.0
H10B—C10—H10C	109.5	C12—C11A—H11C	109.0
C9—C10—H10A	109.5	C12—C11A—H11D	109.0
C9—C10—H10B	109.5	H11C—C11A—H11D	107.8
C9—C10—H10C	109.5
P1—O3—C9—C10	−172.0 (9)	C5^vi—C5—C4—C7	0.4 (8)
P2—O6—C11—C12A	179 (2)	C5—C6—C1—P1	179.1 (4)
P2—O6—C11A—C12	110 (3)	C5—C6—C1—C2	−1.0 (7)
O5—P2—O6—C11	−31.9 (19)	C5—C4—C3—P2	178.6 (4)
O5—P2—O6—C11A	−56.6 (13)	C5—C4—C3—C2	0.2 (7)
O5—P2—C3—C2	2.9 (5)	C5—C4—C7—C8	0.3 (8)
O5—P2—C3—C4	−175.5 (4)	C6—C5—C4—C3	−0.1 (7)
O2—P1—O1—Ca1	141.3 (6)	C6—C5—C4—C7	179.8 (5)
O2—P1—O3—C9	−179.5 (8)	C6^vi—C8—C7—C4	−0.7 (9)
O2—P1—C1—C6	−57.1 (4)	C8^vi—C6—C1—P1	−0.8 (7)
O2—P1—C1—C2	122.9 (4)	C8^vi—C6—C1—C2	179.1 (5)
O1—P1—O2—Ca1^ii	−5.7 (3)	C1—P1—O2—Ca1^ii	−128.9 (2)
O1—P1—O3—C9	−57.7 (10)	C1—P1—O1—Ca1	−95.6 (7)
O1—P1—C1—C6	176.8 (4)	C1—P1—O3—C9	68.7 (9)
O1—P1—C1—C2	−3.2 (4)	C1—C2—C3—P2	−179.2 (4)
O4—P2—O5—Ca1^i	−4.2 (4)	C1—C2—C3—C4	−0.6 (7)
O4—P2—O6—C11	−155.5 (18)	C4—C5—C6—C8^vi	−179.6 (5)
O4—P2—O6—C11A	179.8 (13)	C4—C5—C6—C1	0.5 (7)
O4—P2—C3—C2	127.8 (4)	C3—P2—O5—Ca1^i	117.8 (3)
O4—P2—C3—C4	−50.6 (5)	C3—P2—O6—C11	90.6 (18)
O6—P2—O5—Ca1^i	−121.5 (3)	C3—P2—O6—C11A	65.9 (13)
O6—P2—C3—C2	−122.7 (4)	C3—C2—C1—P1	−179.0 (4)
O6—P2—C3—C4	58.8 (5)	C3—C2—C1—C6	1.0 (7)
O3—P1—O2—Ca1^ii	120.9 (4)	C3—C4—C7—C8	−179.9 (5)
O3—P1—O1—Ca1	29.9 (8)	C7—C4—C3—P2	−1.3 (7)
O3—P1—C1—C6	44.0 (5)	C7—C4—C3—C2	−179.7 (5)
O3—P1—C1—C2	−136.0 (4)	O3A—P1—O2—Ca1^ii	113.6 (5)
C5^vi—C5—C6—C8^vi	−0.2 (8)	O3A—P1—O1—Ca1	13.7 (8)
C5^vi—C5—C6—C1	179.9 (5)	O3A—P1—C1—C6	68.7 (6)
C5^vi—C5—C4—C3	−179.5 (5)	O3A—P1—C1—C2	−111.2 (6)

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