Crystal engineering of ionic cocrystals comprising Na/K salts of hesperetin with hesperetin molecules and solubility modulation

Hesperetin (HES) is a weakly acidic flavonoid of topical interest owing to its antiviral properties. Despite the presence of HES in many dietary supplements, its bioavailability is hindered by poor aqueous solubility (1.35 µg ml⁻¹) and rapid first-pass metabolism. Cocrystallization has evolved as a promising approach to generate novel crystal forms of biologically active compounds and enhance the physicochemical properties without covalent modification. In this work, crystal engineering principles were employed to prepare and characterize various crystal forms of HES. Specifically, two salts and six new ionic cocrystals (ICCs) of HES involving sodium or potassium salts of HES were studied using single-crystal X-ray diffraction (SCXRD) or powder X-ray diffraction and thermal measurements. Structures of seven of the new crystalline forms were elucidated by SCXRD, which revealed two families of isostructural ICCs in terms of their crystal packing and confirmed the presence of phenol⋯phenolate (PhOH⋯PhO⁻) supramolecular heterosynthons. Diverse HES conformations were observed amongst these structures, including unfolded and folded (previously unreported) conformations. One ICC, HES with the sodium salt of HES (NESNAH), was scalable to the gram scale and found to be stable after accelerated stability testing (exposure to elevated heat and humidity). HESNAH reached C_max after 10 min in PBS buffer 6.8 compared with 240 min in pure HES. In addition, relative solubility was observed to be 5.5 times greater, offering the possibility of improved HES bioavailability.

1. Introduction

Flavonoids feature a polyphenolic backbone and are widely distributed in plants, fruits and vegetables (Panche et al., 2016). They are widely studied for their beneficial health effects as highlighted in epidemiological studies (Hertog, 1996; Arts, 2008). Hesperetin (HES, Fig. 1), a bioactive flavonoid, is naturally available in citrus fruits and has been formulated into dietary supplements as it possesses potent antioxidant and anti-inflammatory properties (Parhiz et al., 2015). HES can also play an important protective role in the prevention of various diseases associated with inflammation and oxidative stress, including cancer [e.g. carcinoid tumours (Zarebczan et al., 2011; Sohel et al., 2022)], neurodegenerative diseases [e.g. Alzheimer's disease (Ikram et al., 2019; kheradmand et al., 2018)] and cardiovascular diseases (Roohbakhsh et al., 2015; Wang et al., 2017). Most recently, arising from the COVID-19 pandemic, HES has attracted attention because of its ability to bind to multiple regions of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), suppressing entry into host cells and subsequent replication of viral particles (Khezri et al., 2022; Agrawal et al., 2021). Unfortunately, HES suffers from poor aqueous solubility (1.35 µg ml⁻¹, 25°C) (Liu & Chen, 2008) and undergoes rapid first-pass metabolism (Kanaze et al., 2007), two factors that can severely limit bioavailability and efficacy. Therefore, improving the solubility and bioavailability of HES is a practical concern for potential pharmacological utility.

Figure 1 Graphical representation of the salts and ICCs of HES obtained in the study.

In pharmaceutical science, solid-state screening of active pharmaceutical ingredients (APIs), including salts (Berge et al., 1977; Gould, 1986; Morris et al., 1994; Stahl & Wermuth, 2002), polymorphs (Haleblian & Mccrone, 1969; Miller et al., 2005), hydrates/solvates (Healy et al., 2017; Khankari & Grant, 1995) and cocrystals (Aitipamula et al., 2012) is employed to counter undesirable physicochemical properties, enabling the development of bioactive molecules as drug products. Generally, salt formation is the most common and effective way to enhance the solubility of ionizable molecules, with approximately 50% of marketed drug products being in salt form (Byrn et al., 2017). For weakly ionizable or non-ionizable molecules, where polymorphs and hydrates/solvates tend to not have a significant impact on solubility (Pudipeddi & Serajuddin, 2005), crystal engineering of pharmaceutical cocrystals has become widely used over the last two decades. Pharmaceutical cocrystals offer an opportunity to control the physicochemical properties of drug molecules (Bolla et al., 2022), including solubility (Thakuria et al., 2013; Babu & Nangia, 2011), hydrolytic stability (Duggirala et al., 2014) and bioavailability (Nangia & Desiraju, 2022; Shan et al., 2014), without changing the molecular structure of an API and thereby compromising its intrinsic biological activities. Indeed, the US Food and Drug Administration (2018) and European Medicines Agency (2015) have released regulatory guidelines for industrial use of pharmaceutical cocrystals, i.e. cocrystals in which at least one of the coformers is a drug molecule (Almarsson & Zaworotko, 2004). To date, at least ten drug products whereby pharmaceutical cocrystals serve as drug substances have been approved and brought to market (Kavanagh et al., 2019; Almansa et al., 2017).

Cocrystals can be classified as molecular cocrystals (MCCs) comprising two or more molecular compounds (A and B), or ionic cocrystals (ICCs) (Braga et al., 2010) comprising at least one salt (A⁺B⁻C, where A⁺ = cation, B⁻ = anion and C = neutral molecule or another salt). Since ICCs include no fewer than three components, at least two components can be changed if one of the coformers is an API or an ionic form of an API, thereby providing more opportunities to modulate the physicochemical properties compared with MCCs, which typically offer only one variable component in addition to the API. Additionally, ICCs comprising the API with its conjugate salt would offer the possibility to increase the drug loading mass, potentially reducing the drug dosage. Cocrystals are typically sustained by hydrogen bonds (Aakeröy & Seddon, 1993; Bhattacharya & Zaworotko, 2018) and halogen bonds (Mukherjee et al., 2014). In the case of ICCs containing metal ions, coordination bonds are likely to be established between organic moieties and metals (Braga et al., 2018; Grepioni et al., 2022). Given that coordination bonds are typically stronger than hydrogen bonds, these organic–inorganic assemblies can potentially enhance the relevant properties. Indeed, a particularly relevant example is the marketed drug product Depakote. It is an ICC-containing valproic acid and sodium valproate, which exhibits non-hygroscopicity compared with its parent salt (Petruševski et al., 2008; Kavanagh et al., 2019). Likewise, our group demonstrated how ICCs of lithium salicylate with L-proline and lithium halides (Cl⁻, Br⁻) with glucose improve hygroscopicity and can also modulate the pharmacokinetics of parent lithium salts (Duggirala et al., 2014; Smith et al., 2013). These `organic–inorganic' ICCs can also be used for solid-state chiral resolution, whereby the lithium cation or zinc cation that favour tetrahedral coordination exhibit homochiral preference when LiX (X = Cl, Br, I) or ZnCl₂ are cocrystallized with racemic coformers (Shemchuk et al., 2021, 2020, 2018).

Cocrystals can be rationally designed by crystal engineering based on the exploitation of supramolecular synthons (Desiraju, 1995). Supramolecular heterosynthons (Walsh et al., 2003) between two different but complementary functional groups are particularly valuable to facilitate cocrystal design once the relevant hierarchies are established, e.g. if a supramolecular heterosynthon is favoured over a competing supramolecular homosynthon between two identical self-complementary functional groups or versus other heterosynthons that might form between coformers (Jin, Sanii et al., 2022; Haskins et al., 2022; Duggirala et al., 2015; Kavuru et al., 2010; Shattock et al., 2008; Bis et al., 2007). In our previous work, we demonstrated that the phenol–phenolate supramolecular heterosynthon (PhOH⋯PhO⁻) is reliable and robust enough to be exploited for the design of ICCs of phenolic compounds (Jin, Sanii et al., 2022). In this contribution, we report a crystal engineering approach to address the solubility issue of HES through cocrystallization. HES would be expected to form both salts and cocrystals owing to its weakly acidic nature (pK_a = 6.67) and hydrogen-bonding capabilities, respectively. To date, molecular cocrystals and an ICC of HES with palmatine chloride have been reported (Wang et al., 2021; Zhang, Yang et al., 2021; Liu et al., 2022; Zhang, Zhu et al., 2021; Zhang et al., 2022; Chadha et al., 2017; Kavuru et al., 2010). A survey of the Cambridge Structural Database using ConQuest (version 2020.3.0 with June 2022 update) revealed no salt forms of HES. By introducing pharmaceutically acceptable metal cations, i.e. potassium (K⁺) and sodium (Na⁺), here we report the synthesis and characterization of K⁺ and Na⁺ salts of HES as well as ICCs comprising HES and these conjugate salts. We also report the dissolution profiles of scalable ICCs in PBS buffer solution.

2. Experimental

2.1. Reagents and materials

HES (>97%) and sodium methoxide (ca 5 mol l⁻¹ in MeOH) were purchased from Tokyo Chemical Industry Co. Ltd. Potassium hydroxide (>85%) was purchased from Sigma–Aldrich. All solvents were purchased from Sigma–Aldrich or Alfa Aesar and used without further purification.

2.2. Synthesis

All cocrystallization experiments to isolate single crystals were conducted via slow evaporation, heating–cooling or liquid/vapour diffusion, either at room temperature or in a refrigerator at 5.4°C. Scale-up experiments were conducted by slurrying. Experimental details are as follows.

2.2.1. Hydrated sodium salt of HES, HESNA·H₂O

Single crystals: HES (30 mg, 0.1 mmol) and 1 M sodium methoxide in MeOH (50 µl, 0.05 mmol) were dissolved in 2.3 ml of MeOH in a test tube; 2.5 ml of n-hexane was layered on top. The tube was sealed using parafilm and allowed to stand at room temperature. Colourless block crystals of HESNA·H₂O were isolated after 7 days.

2.2.2. 1:1 ICC of HES and HESNA, HESNAH

Single crystals: HES (30 mg, 0.1 mmol) and 1 M sodium methoxide in MeOH (50 µl, 0.05 mmol) were dissolved in 2.3 ml of EtOH in a test tube; 2.5 ml of n-hexane was layered on top. The tube was sealed using parafilm and allowed to stand at room temperature. Colourless block crystals of HESNAH were harvested after 2 days.

Scale-up: bulk powder of HESNAH was obtained by slurrying HES (2.0 g, 6.6 mmol) and 5 M sodium methoxide in MeOH (700 µl, 3.5 mmol) in 6 ml MeOH (or H₂O, or EtOH) under ambient conditions for 48 h. The resulting powder was filtered and dried in an oven at 50°C overnight.

2.2.3. Ethanol solvate of HESNAH, HESNAH·2EtOH

Single crystals: HES (30 mg, 0.1 mmol) and 1 M sodium methoxide in MeOH (50 µl, 0.05 mmol) were dissolved in 2.5 ml of EtOH in a vial. The vial was uncapped and put in a beaker containing 2.5 ml of n-hexane. The beaker was sealed and left at room temperature. After about 6 h, yellowish block crystals of HESNAH·2EtOH were harvested.

2.2.4. Hydrated potassium salt of HES, HESK·3H₂O

Single crystals: HES (15 mg, 0.05 mmol) and 1 M KOH in H₂O (100 µl, 0.1 mmol) were dissolved in 0.5 ml H₂O and heated to 120°C for ca 15 min in a capped vial on a hot plate. The hot plate was turned off and the vial was allowed to cool on the hot plate. Colourless block crystals of HESK·3H₂O were harvested after 12 h.

2.2.5. Hydrated 1:1 ICC of HES and HESK, HESKHE·2H₂O

Single crystals: HES (30 mg, 0.1 mmol) and 1 M KOH in H₂O (100 µl, 0.1 mmol) were dissolved in a vial containing 2.3 ml of an EtOH/H₂O mixture with a volume ratio of 1:1. The vial was sealed with pierced parafilm to allow the solvent to slowly evaporate at room temperature. Colourless block crystals of HESKHE·2H₂O were harvested after 3 days.

2.2.6. HESKHE anhydrate

Powder: the powder of HESKHE·2H₂O was placed in an oven at 160°C for 30 min.

2.2.7. Ethanol solvate of HESKHE, HESKHE·xEtOH

Single crystals: HES (30 mg, 0.1 mmol) and 1 M KOH in H₂O (50 µl, 0.05 mmol) were dissolved in 2 ml EtOH in a vial. The vial was sealed with pierced parafilm and left in the fridge at 5.4°C. Colourless block crystals of HESKHE·xEtOH were harvested after 3 days.

Scale-up: a bulk sample of HESKHE·xEtOH was obtained by slurrying HES (1.5 g, 5 mmol) and solid KOH (151.1 mg, 2.7 mmol) in 6.5 ml EtOH under ambient conditions for 48 h. The resulting powder was filtered and dried in an oven at 50°C overnight.

2.2.8. Methanol solvate of HESKHE, HESKHE·xMeOH

HES (30 mg, 0.1 mmol) and 1 M KOH in H₂O (50 µl, 0.05 mmol) were dissolved in 2 ml of MeOH in a test tube; 2.5 ml of n-hexane was layered on top. The tube was sealed using parafilm and allowed to stand at room temperature. After 2 days, colourless block crystals of HESKHE·xMeOH were harvested.

2.3. Thermogravimetric analysis

Thermogravimetric analysis (TGA) was performed on a TA Instruments Q50 TG from room temperature to 350°C at a 10°C min⁻¹ heating rate under an N₂ purge of 60 ml min⁻¹.

2.4. Differential scanning calorimetry

Thermal analysis was carried out by employing a TA Instruments DSC Q20. Samples were heated in a differential scanning calorimetry (DSC) pan with a pierced lid at a 10°C min⁻¹ heating rate under an N₂ atmosphere.

2.5. Powder X-ray diffraction

All powder X-ray diffraction (PXRD) patterns were collected on an Empyrean diffractometer (PANalytical) with the following experimental parameters: Cu Kα radiation (λ = 1.54056 Å), 40 kV and 40 mA, scan speed 8° min⁻¹, step size 0.05°, angle range 5–40° 2θ.

2.6. Variable-temperature powder X-ray diffraction

Variable-temperature powder X-ray diffraction (vt-PXRD) was carried out and diffraction patterns were collected using a PANalytical X'Pert Pro-MPD diffractometer equipped with a PIXcel3D detector operating in scanning line detector mode. The diffractometer is outfitted with an Empyrean Cu LFF (long fine-focus) HR (9430 033 7300x) tube operated at 40 kV and 40 mA, and Cu Kα radiation (λ_α = 1.54056 Å). An Anton Paar TTK 450 stage coupled with the Anton Paar TCU 110 Temperature Control Unit was used. Measurements were in continuous scanning mode with the goniometer in the theta–theta orientation. HESNAH and HESKHE·xEtOH powders were loaded on a zero-background sample holder made for the Anton Paar TTK 450 chamber. The data were collected in the range 5–40° (2θ) at designated temperature points with a step size of 0.0334225 and a scan time of 50.165 s per step under an N₂ atmosphere.

2.7. Single-crystal X-ray diffraction and structure determination

Single-crystal structures of HESNA·H₂O, HESNAH, HESK·3H₂O, HESKHE·2H₂O and HESKHE·xMeOH were determined using either Mo Kα (λ = 0.71073 Å) or Cu Kα (λ = 1.5418 Å) radiation on a Bruker D8 Quest fixed-chi diffractometer equipped with a Bruker APEX-II CCD detector and a nitro­gen-flow Oxford Cryosystem attachment. Data were indexed, integrated and scaled in APEX3 (Bruker, 2016). Absorption corrections were performed by the multi-scan method using SADABS (Sheldrick, 1996). Space groups were determined using XPREP as implemented in APEX3. Single-crystal structures of HESNAH·2EtOH and HESKHE·xEtOH were collected using Mo Kα radiation (λ = 0.71073 Å) on a Rigaku mm007 Oxford diffractrometer equipped with an R-axis IV++ image plate detector and an Oxford cryosystem 800. All crystal structures were solved using the intrinsic phasing method in SHELXT (Sheldrick, 2015a) and refined with SHELXL (Sheldrick, 2015b) using the least-squares method implemented in Olex2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically. Hydrogen atoms of alkyl groups were placed in geometrically calculated positions and included in the refinement process using a riding model (AFIX 137, AFIX 23 or AFIX 13) with isotropic thermal parameters: U_iso (H) = −1.5U_eq (–CH₃), U_iso (H) = −1.2U_eq (–CH₂) and U_iso (H) = −1.2U_eq (–CH). Hydrogen atoms on benzene rings were placed in geometric positions via AFIX 43 restriction with the isotropic thermal parameter U_iso (H) = −1.2U_eq (–CH) and refined in a riding model. Hydrogen atoms on the hydroxyl groups of phenolic moieties were found via difference Fourier map inspection and refined with the distance restraint (DFIX O—H 0.84 Å) and with the thermal parameters U_iso (H) = −1.2U_eq (–OH). Hydrogen atoms on H₂O molecules were located via AFIX 7 and refined in a riding model with the isotropic thermal parameters U_iso (H) = −1.5U_eq (–OH). Hydrogen atoms on the hydroxyl groups of EtOH and MeOH molecules were located via AFIX 147 and refined in a riding model with the isotropic thermal parameters U_iso (H) = −1.2U_eq (–OH). H6 in HESNAH and HESKHE·2H₂O were refined without any restraint or constraint. A distance restraint DFIX is applied on H1WB and H5, and H1WA and H9A in HESKHE·2H₂O.

Chiral carbon atoms and neighbouring carbon atoms of HES moieties were modelled for disorder in HESNA·H₂O without any restraints and constraints applied to C9; in HESNAH·2EtOH with RIGU restraint applied to C8 and C9; in HESK·3H₂O with distance (SADI) and ADP (ISOR and DELU) restraints applied to C8 and C9; in HESKHE·xEtOH with ADP restraints (SIMU, DELU and ISOR) applied to C9, C24 and C25, and with the distance restraint SADI applied on related covalent bonds. One phenolic ring (C26–C31) was modelled for disorder in HESKHE·xMeOH. Due to the disordered solvent molecules, HESKHE·xMeOH and HESKHE·xEtOH were treated by SQUEEZE in PLATON (Spek, 2020), leaving 10.4 and 7.9% void volumes, respectively.

Crystal data have been deposited with the Cambridge Crystallographic Data Centre (CCDC codes 2208281–2208287). Selected crystallographic data and refinement parameters for the crystal structures are given in Table 1.

Table 1
Crystallographic data and structure refinement parameters

Hydrogen atoms were treated by a mixture of independent and constrained refinement.

	HESNA·H2O	HESNAH	HESNAH·2EtOH	HESK·3H2O	HESKHE·2H2O	HESKHE·xMeOH	HESKHE·xEtOH
Crystal data
Chemical formula	C16H13O6Na·H2O	C32H27O12Na	C32H27O12Na·2C2H6O	C16H13O6K·3H2O	C32H27O12K·2H2O	C32H27O12K·xCH4O	C32H27O12K·xC2H6O
Mr	342.27	313.26	718.66	394.41	678.67	674.68	688.70
Crystal system	Monoclinic	Monoclinic	Triclinic	Orthorhombic	Monoclinic	Monoclinic	Monoclinic
Space group	P21/c	P2/n	P1	Pbca	P2/n	C2/c	C2/c
T (K)	150	150	150	113	116	113	113
a (Å)	11.0666 (4)	10.7741 (6)	10.8865 (5)	19.9343 (3)	11.2185 (2)	19.6211 (3)	19.4072 (8)
b (Å)	13.2714 (4)	9.6357 (6)	10.9884 (6)	7.8657 (2)	10.2204 (2)	20.3628 (3)	20.4384 (8)
c (Å)	10.0412 (3)	13.8452 (9)	16.1451 (8)	31.4425 (7)	13.5244 (2)	17.2684 (3)	17.3645 (11)
α (°)	90	90	81.871 (4)	90	90	90	90
β (°)	94.430 (1)	107.103 (2)	74.681 (5)	90	106.427 (1)	104.282 (1)	104.006 (5)
γ (°)	90	90	68.049 (5)	90	90	90	90
V (Å^3)	1470.34 (8)	1373.79 (15)	1725.73 (17)	3446.19 (14)	1487.38 (5)	6686.19 (19)	6682.9 (6)
Z, Z′	4, 1	2, 0.5	2, 1	8, 1	2, 0.5	8, 1	8, 1
Radiation type	Mo Kα	Mo Kα	Mo Kα	Cu Kα	Cu Kα	Cu Kα	Mo Kα
μ (mm^−1)	0.15	0.13	0.12	3.15	2.23	1.96	0.23
Diffractometer	Bruker APEX-II CCD	Bruker APEX-II CCD	Rigaku mm007 Oxford	Bruker APEX-II CCD	Bruker APEX-II CCD	Bruker APEX-II CCD	Rigaku mm007 Oxford
Tmin, Tmax	0.710, 0.746	0.715, 0.746	0.904, 1.000	0.542, 0.753	0.509, 0.753	0.594, 0.753	0.373, 1.000
Measured [I > 2σ(I)] reflections	14984	13484	18542	29419	14054	39471	26486
Independent [I > 2σ(I)] reflections	3368	3173	7061	3040	2610	5880	6841
Observed [I > 2σ(I)] reflections	2734	2484	5100	2903	2414	5781	5112
Rint	0.024	0.045	0.047	0.071	0.049	0.040	0.062
Refinement
R[F^2 > 2σ(F^2)]	0.048	0.043	0.061	0.045	0.054	0.055	0.080
wR(F^2)	0.124	0.117	0.165	0.117	0.161	0.147	0.205
S	1.04	1.07	1.05	1.08	1.07	1.13	1.02
Reflections	3368	3173	7061	3040	2610	5880	6841
Parameters	234	212	501	267	222	541	485
Restraints	2	2	11	19	4	405	52

2.8. Cambridge Structural Database analysis

A Cambridge Structural Database (CSD) survey using ConQuest was conducted to search for the distribution of Na/K—O bond lengths with the following constraints: R₁ ≤ 0.05; only organics with 3D coordinates determined from SCXRD; without errors and disorder; Na⁺ or K⁺ cations coordinated to oxygen atoms only; excluding F, Cl, Br, I, S, As, N, P, C, Si and H atoms; coordination number unspecified; bond type between sodium or potassium and oxygen atoms set to `any'.

2.9. Accelerated stability test

Two scalable ICCs of HES (HESNAH and HESKHE·xEtOH) were subjected to an accelerated stability test in a humidity chamber at 40°C and 75% relative humidity (RH) (Huynh-Ba, 2008). Samples were removed after 14 days and PXRD and TGA data were then collected.

2.10. Powder dissolution tests

The dissolution experiments for pure HES and HESNAH were performed in 500 ml of pH 6.8 phosphate buffer solution (PBS) at 37°C under non-sink conditions. A mass of 60 mg equivalent of HES was sieved to 80–106 µm using a standard-mesh sieve and added to 500 ml PBS solution with stirring at 100 rpm. 1 ml aliquots were taken at 2, 4, 6, 8, 10, 15, 30, 40, 60, 90, 120, 150, 180, 210, 240, 270 and 300 min. Each aliquot was filtered through a 0.45 µm Corning syringe filter. 500 µl of filtered aliquot and 500 µl MeOH were added to a vial and injected into the high-performance liquid chromatography (HPLC) instrument. The remaining undissolved solid was analysed by PXRD and TGA. All dissolution experiments were carried out in triplicate.

2.11. High-performance liquid chromatography

The dissolution aliquots were analysed using a Shimadzu (LC-20A) HPLC instrument with the Gemini C18 (250 × 4.6 × 5 µm) column. The wavelength was set to 235 nm, the injection volume was set to 5 µl with a flow rate of 1 ml min⁻¹ and the oven was set at 40°C. The mobile phase started with a composition of 25%:75% of 0.1% orthophospho­ric acid in aceto­nitrile and 0.1% orthophospho­ric acid in H₂O with a gradient increase to 100% of 0.1% orthophospho­ric acid in aceto­nitrile from 0 to 13 min, and was then held at 100% for 2 min and afterwards reduced back to 25%:75% over a 2 min gradient. This composition was held constant for a further 3 min.

3. Results and discussion

3.1. Solid form screening of HES

Fig. 1 illustrates the crystalline forms of HES reported here. With respect to reactions of HES with sodium methoxide, one salt (HESNA·H₂O) and two ICCs (HESNAH and HESNAH·2EtOH) were isolated as single crystals suitable for characterization by SCXRD. Attempts were made to scale up all three solid forms. HESNA·H₂O was isolated from MeOH/n-hexane liquid diffusion while attempting to synthesize ICCs. Subsequent attempts to repeat the experiment or to prepare the bulk powder were unsuccessful, affording HESNAH according to PXRD and SCXRD characterization. The same issue was also encountered for scale-up of HESNAH·2EtOH. HESNAH was the only form that could be readily scaled up. This was achieved via slurrying using H₂O, MeOH or EtOH. In addition, no phase transformation was observed when HESNAH was exposed to accelerated stability testing conditions (75% RH, 40°C) for 14 days as advised by PXRD and TGA (Fig. S1 of the supporting information). Vt-PXRD suggested HESNAH retained its structure up to 280°C (Fig. S2). Therefore, only HESNAH was deemed suitable for dissolution studies.

With respect to reactions of HES with potassium hydroxide, one salt (HESK·3H₂O) and three ICCs (HESKHE·2H₂O, HESKHE·xMeOH and HESKHE·xEtOH) were isolated as single crystals suitable for characterization by SCXRD. One ICC (HESKHE) was obtained as a microcrystalline powder by dehydration of HESKHE·2H₂O at 160°C (dehydration evidenced by TGA and DSC data; Fig. S3). PXRD patterns [Fig. S4(a)] of HESKHE and HESKHE·2H₂O are different. HESKHE was observed to transform back to HESKHE·2H₂O after exposure to humidity for one day as supported by TGA [Fig. S4(b)], which revealed that transformations between HESKHE and HESKHE·2H₂O are reversible. Attempts were made to scale up the salt and ICCs. Single crystals of HESK·3H₂O were isolated in H₂O using a heating–cooling method but this could not be reproduced. For the ICCs, only bulk preparation of HESKHE·xEtOH was successful via EtOH slurry. Unfortunately, HESKHE·xEtOH exhibited different TGA features after exposure to humidity for 14 days, likely due to water absorption on the sample surface and EtOH removal from the structure (Fig. S1). In addition, multiple phase changes were observed in vt-PXRD (Fig. S2) after heating to 160°C, which could be attributed to desolvation and/or dissociation of HESKHE·xEtOH. Therefore, HESKHE·xEtOH was deemed to be unsuitable for dissolution studies.

3.2. Crystal structure description

HESNA·H₂O (C₁₆H₁₃O₆⁻·Na⁺·H₂O) is a hydrated salt that crystallizes in the space group P2₁/c with one Na⁺ cation, one HES⁻ anion and one H₂O molecule in the asymmetric unit. Each Na⁺ cation is five coordinated to —OH, —OCH₃, —O— and PhO⁻ groups from three HES⁻ anions and by one H₂O molecule which acts as terminal aqua ligand (for Na—O bond lengths see Table S1 of the supporting information). Na⁺ cations cross-link HES⁻ anions into a 2D coordination network along the bc crystallographic plane [Fig. 2(a)], which comprises side-by-side enclosed `squares' when viewed down the c axis, as illustrated in Fig. 2(b), revealing a bilayer 2D coordination network. Along the a axis, adjacent 2D polymeric sheets are stacked and interact via hydrogen bonds between H<sub>2</sub>O molecules and HES<sup>−</sup> anions [Fig. 2(b)]. Hydrogen bonds between HES<sup>−</sup> anions sustain the 2D coordination networks. HES<sup>−</sup> anions were found to organize in cyclic dimers through pairs of charge-assisted PhOH⋯PhO<sup>−</sup> hydrogen bonds (O2⋯O6<sup>−</sup>: 2.526 (2) Å) [Fig. 2(c)], termed `motif I' herein. Further discussion about the interactions between HES⁻ anions is presented below.

Figure 2 Crystal structure of HESNA·H2O. (a) and (b) Bilayered 2D coordination networks propagate along the crystallographic bc plane and are cross-linked by hydrogen bonds between H2O molecules and HES^− anions along the a axis. (c) Cyclic dimers of HES^− form through pairs of PhOH⋯PhO^− hydrogen bonds (motif I) which exist throughout the 2D coordination networks. HES^− anions are shown in red.

HESNAH (C₁₆H₁₄O₆·C₁₆H₁₃O₆⁻·Na⁺) is an anhydrous ICC that crystallizes in the space group P2/n. The asymmetric unit contains half the chemical formula (Z′ = 0.5) since Na⁺ cations and the protons between HES moieties are located on a crystallographic twofold axis. A symmetric or close-to-symmetric charge-assisted [PhO⋯H⋯PhO]⁻ hydrogen bond is formed with a short O6⋯O6′ distance of 2.4618 (18) Å, the proton was located via difference Fourier map inspection (Kreevoy et al., 1998). Each Na⁺ cation is six-coordinate through two —OH, two —OCH₃ and two —C=O groups from four HES moieties (for Na—O bond lengths see Table S1), forming coordination polymer chains that propagate along the b axis and stack along the a and c axes [Figs. 3(a) and 3(b)]. The resulting 3D network is sustained by hydrogen bonds. Like HESNA·H₂O, motif I cyclic dimers form through pairs of hydrogen bonds between phenolate groups (partly deprotonated in HESNAH) and phenolic groups of HES moieties (O2⋯O6 2.636 (2) Å). A chain of cyclic dimers connected by [PhO⋯H⋯PhO]⁻ hydrogen bonds [Fig. 3(c)] is thereby generated. Fig. 3(c) reveals that HES moieties in HESNAH are folded into a `V' shape with a dihedral angle between the benzopyrone rings and phenolic rings of 89.89°. A conformational comparison of HES is addressed below.

Figure 3 Crystal structure of HESNAH. (a) Coordination polymer chains propagate along the b axis, giving rise to a 2D network through [PhO⋯H⋯PhO]^− hydrogen bonds along the crystallographic bc plane. (b) Packing of 2D hydrogen-bonding networks in a way that (c) HES moieties self-assemble into cyclic dimers through pairs of PhOH⋯PhO^− hydrogen bonds (motif I).

HESNAH·2EtOH (C₁₆H₁₄O₆·C₁₆H₁₃O₆⁻·Na⁺·2EtOH) crystallizes in the space group P1, with HES⁻ anions, Na⁺ cations and HES molecules in a 1:1:1 ratio and two EtOH solvate molecules. Na⁺ cations are seven-coordinate through bonding to HES and HES⁻ via two —OH, two —OCH₃, two —C=O groups and an EtOH molecule (EtOH1) which acts as a terminal ligand (for Na—O bond lengths see Table S1), resulting in infinite polymer chains propagating along the b axis [Fig. 4(a)]. HES molecules and HES⁻ anions arrange on each side of the polymer chains. PhOH⋯PhOH hydrogen bonds (O5⋯O2: 2.945 (3) Å) between HES molecules are present in the polymer chains. Along the c axis, adjacent chains are related to each other by PhOH⋯PhO⁻ hydrogen bonds (O6⋯O7⁻: 2.566 (3) Å) between HES molecules and HES⁻ anions [Fig. 4(a)]. Along the a axis, free EtOH molecules (EtOH2) lie between adjacent chains through EtOH⋯PhO⁻ and EtOH⋯PhOH hydrogen bonds [Fig. 4(b)]. Cyclic dimers formed through pairs of PhOH⋯PhOH hydrogen bonds (O11⋯O8: 2.853 (3) Å) between HES⁻ anions (termed `motif II' herein) from adjacent chains [Fig. 4(b) and 4(c)] were observed. Further discussion concerning the interactions between HES⁻ anions is presented below.

Figure 4 Crystal structure of HESNAH·2EtOH. (a) Coordination polymer chains propagate along the b axis with HES and HES^− arranged on each side and linked to neighbouring chains along the c axis via PhOH⋯PhO^− hydrogen bonds. (b) Adjacent chains along the a axis are connected by EtOH molecules and by (c) cyclic dimers of HES^− anions through pairs of PhOH⋯PhOH hydrogen bonds (motif II). HES molecules and HES^− anions are show in green and red, respectively.

HESK·3H₂O (C₁₆H₁₃O₆⁻·K⁺·3H₂O) is a salt hydrate that crystallizes in the space group Pbca with one HES⁻ anion, one K⁺ cation and three H₂O molecules in the asymmetric unit. Each K⁺ cation is coordinated to six neighbouring oxygen atoms from three HES⁻ anions, including —OH and —OCH₃ groups on the phenolic rings of one HES⁻, the —OH group on the benzopyrone ring of the second HES⁻, —O— moieties of the third HES⁻ and two H₂O molecules [H₂O(1), H₂O(2)] (for K—O bond lengths see Table S1). K⁺ cations cross-link HES⁻ anions into a 2D coordination network along the ac crystallographic plane. When viewed down the b axis, all phenolate and phenolic groups of HES⁻ and coordinated H₂O molecules are positioned on the same side, the A_side, whereas the B_side is occupied by alkyl and —C=O groups, indicating that the A_side is rich in hydrogen-bond acceptors and donors whereas the B_side is deficient [Fig. 5(a)]. Adjacent coordinated polymer layers stack alternately in an `A<sub>side</sub>-to-A<sub>side</sub>' and `B_side-to-B_side' fashion along the c axis [Fig. 5(b)]. It is not surprising that only weak hydrogen bonds (e.g. C1—H⋯O4) were observed between `B<sub>side</sub>-to-B<sub>side</sub>' layers given the deficiency of hydrogen-bonding points of the B<sub>side</sub>. On the contrary, the `A_side-to-A_side' stacking and the presence of free H₂O molecules between layers facilitate a complex hydrogen-bonding network comprised of two kinds of charge-assisted hydrogen-bonded ring motifs, R₅⁵(12) and R₄⁴(12) (Fig. 6). PhOH⋯PhO⁻ hydrogen bonds were not observed in HESK·3H₂O. Rather, phenolate groups interact with three H₂O molecules simultaneously.

Figure 5 Crystal structure of HESK·3H2O. (a) 2D coordination network with different functional groups located on two sides, i.e. the Aside and Bside. (b) Packing of the coordination polymer layers alternating in an `Aside-to-Aside' and `Bside-to-Bside' fashion; non-coordinated H2O molecules (space-filling mode, oxygen atoms are orange) lie between layers in the `Aside-to-Aside' region. HES^− anions are shown in red.

Figure 6 A portion of the hydrogen-bonding network comprised of R5^5(12) and R4^4(12) hydrogen-bonded motifs in HESK·3H2O. Red and green indicate different layers; non-coordinated H2O molecules are shown in black.

HESKHE·2H₂O (C₁₆H₁₄O₆·C₁₆H₁₃O₆⁻·K⁺·2H₂O) is a hydrated ICC that crystallizes in the space group P2/n with half of the formula unit (Z′ = 0.5) in the asymmetric unit. Like HESNAH, as a consequence of K⁺ and the proton sitting on a twofold axis, symmetric or close-to-symmetric charge-assisted [PhO⋯H⋯PhO]⁻ hydrogen bonds [O6⋯O6′: 2.451 (2) Å] were observed between HES moieties. Eight coordination is observed around the K⁺ cation, involving oxygen atoms of four HES moieties and two H₂O molecules which act as terminal aqua ligands (for K—O bond lengths see Table S1). The HES moieties fold perpendicularly between the phenolic ring and benzopyrone ring with a dihedral angle of 86.58°, which is slightly smaller than the 89.89° value found in HESNAH. Therefore, similar coordination polymer chains to those observed in HESNAH propagate along the b axis and give rise to a 3D network through hydrogen bonds [Figs. S5(a) and S5(b)]. The crystal packing is sustained via [PhO⋯H⋯PhO]⁻ and PhOH⋯PhO⁻ hydrogen bonds [O2⋯O6: 2.660 (3) Å] that form cyclic dimers between HES moieties like in HESNAH, and hydrogen bonds between H₂O molecules and phenolic groups of HES moieties that form R₂²(8) hydrogen-bonded motifs [Figs. S5(c) and S5(d)]. The similar packing patterns in HESKHE·2H₂O and HESNAH mean that they can be classified as isostructural (Kálmán et al., 1993; Wood et al., 2012) despite the incorporation of H₂O molecules in HESKHE·2H₂O and cation substitution. The presence of H₂O molecules contributes to the larger unit-cell volume [1487.38 (5) ų HESKHE·2H₂O; 1373.79 (15) ų HESNAH]. Despite structural similarities, HESKHE·2H₂O and HESNAH have distinct PXRD patterns (Fig. S6).

HESKHE·xEtOH (C₁₆H₁₄O₆·C₁₆H₁₃O₆⁻·K⁺·xEtOH) crystallizes in the space group C2/c. The asymmetric unit contains two half K⁺ cations, one HES molecule, one HES anion and a non-stoichiometric quantity of EtOH molecules. One K⁺ cation (K1⁺) is coordinated to four —OH and two —OCH₃ groups of four HES⁻ anions. The second K⁺ cation (K2⁺) is coordinated to four neutral and two anionic HES moieties via four —OH, two —OCH₃ and two —C=O groups (for K—O bond lengths see Table S1). Their coordination numbers are 6 and 8, respectively. The resulting structure is a `double-wall' square grid propagating in the ab crystallographic plane. The square grid is sustained by PhOH⋯PhO⁻ [O6⋯O7⁻: 2.482 (4) Å] and PhOH⋯PhOH hydrogen bonds [O6⋯O11: 2.947 (7) Å] and its cavities are filled with EtOH molecules (Fig. 7). EtOH molecules interact with HES⁻ through EtOH⋯PhO⁻ hydrogen bonds and with HES though EtOH⋯PhOH hydrogen bonds.

Figure 7 `Double-wall' square grid filled with EtOH molecules in the crystal structure of HESKHE·xEtOH. HES molecules and HES^− anions are shown in green and red, respectively.

HESKHE·xMeOH (C₁₆H₁₄O₆·C₁₆H₁₃O₆⁻·K⁺·xMeOH) and HESKHE·xEtOH are isostructural with the same unit-cell parameters and space group except for the replacement of EtOH with MeOH (Fig. S7). The two crystals have PXRD patterns that are substantially the same (Fig. S6).

3.3. CSD survey for distribution of Na/K—O bond lengths

A CSD survey resulted in a sample size of 5145 Na—O bond lengths in 666 coordination structures containing sodium. The distribution of Na—O bond distances is presented in Fig. 8(a). Most bond lengths fall in the range 2.1–3.1 Å with a mean value of 2.431 ± 0.127 Å. The CSD survey of K—O bonds resulted in 3692 bond lengths in 462 structures of potassium complexes. The K—O bond length distribution is shown in Fig. 8(b). The majority of K—O bonds exhibit lengths from 2.4 to 3.4 Å, averaging at 2.835 ± 0.137 Å. Na—O and K—O bond lengths extracted from the structures of HES reported here were in the ranges 2.2610 (16) to 2.6371 (15) Å and 2.6450 (19) to 2.8714 (24) Å, respectively (Table S1 and orange bars in Fig. 8). The bond lengths observed in the structures reported here are therefore in good accordance with the literature values, with Na—O bonds consistently shorter than K—O bonds.

Figure 8 Histograms of (a) Na—O and (b) K—O bond length distributions. Purple and blue bars represent the bond distances retrieved from the CSD. Orange bars represent the bond distances observed in structures reported here.

3.4. Hydrogen-bonding analysis

In the crystal structures reported here, there are two hydrogen-bond acceptors, i.e. C=O and PhOH, that compete with PhO⁻ to form a supramolecular synthon with the hydrogen-bond donor PhOH. According to our CSD analysis, the PhOH⋯PhO⁻ supramolecular synthon occurs in 58.8% of crystal structures that contain PhOH, C=O and PhO⁻ in the absence of COOH or COO⁻ moieties, whereas PhOH⋯PhOH and PhOH⋯O=C synthons occur in 11.8 and 23.5% of related structures, respectively (CSD survey parameters are presented in Table S2). These results indicate that PhOH⋯PhO⁻ supramolecular synthons are generally preferred versus the relevant competing supramolecular synthons. The CSD data are consistent with the results obtained. We note that the structure of HES inherently favours this situation as six-membered-ring intramolecular hydrogen bonds persist between –OH and C=O moieties on the benzopyrone rings of HES, meaning that C=O is less likely to form intermolecular hydrogen bonds with additional PhOH moieties from neighbouring molecules. PhOH⋯PhOH synthons were observed in only three structures: HESNAH·2EtOH, HESKHE·xEtOH, HESKHE·xMeOH. In contrast, six of the seven crystal structures (except for HESK·3H₂O) are sustained by PhOH⋯PhO⁻ synthons which exhibit shorter distances [2.451 (2) Å to 2.660 (3) Å] than PhOH⋯PhOH [2.853 (3) Å to 2.947 (7) Å] hydrogen bonds. Table 2 details the geometric parameters of PhOH⋯PhO⁻ and PhOH⋯PhOH hydrogen bonds observed in the structures reported. PhOH⋯PhO⁻ hydrogen bonds are expected to be stronger as they are charge-assisted as explained through energy decomposition analysis in our previous work (Jin, Sanii et al., 2022). It has been suggested that symmetric [PhO⋯H⋯PhO]⁻ hydrogen bonds can be classified as quasi-covalent bonds in nature due to incomplete proton transfer (Steiner, 2002). The [PhO⋯H⋯PhO]⁻ hydrogen bonds observed in HESNAH [2.4618 (18) Å] and HESKHE·2H₂O [2.451 (2) Å], reported here, HESTEA-γ [2.4256 (19) Å] reported by us recently (Jin, Haskins et al., 2022), and bis­(4-Nitro­phenoxide) dihydrate [2.434 (6) Å] reported by Kreevoy et al. (1998), are shorter than other PhOH⋯PhO⁻ hydrogen bonds [2.479 (3) Å to 2.660 (3) Å] observed in this work.

Table 2
PhOH⋯PhO⁻ and PhOH⋯PhOH hydrogen-bond parameters observed in the salt and ICC structures of HES reported here

Solid forms	d (D—H) (Å)	d (H⋯A) (Å)	D (D⋯A) (Å)	θ (°)
PhOH⋯PhO^− hydrogen bonds
HESNA·H2O	0.852 (19)	1.674 (19)	2.526 (2)	180 (3)
HESNAH	0.86 (2)	1.79 (2)	2.636 (2)	165 (2)
	1.2312 (13)	1.2312 (13)	2.4618 (18)	178 (2)
HESNAH·2EtOH	0.87 (2)	1.70 (2)	2.566 (3)	173 (3)
HESKHE·2H2O	0.82 (2)	1.84 (2)	2.660 (3)	174 (3)
	1.225 (2)	1.225 (2)	2.451 (2)	180 (5)
HESKHE·xMeOH	0.84	1.65	2.479 (3)	169
HESKHE·xEtOH	0.84 (4)	1.66 (4)	2.482 (4)	164 (5)
PhOH⋯PhOH hydrogen bonds
HESNAH·2EtOH	0.85 (2)	2.47 (3)	2.945 (3)	116 (3)
	0.83 (3)	2.04 (3)	2.853 (3)	165 (3)
HESKHE·xMeOH	0.85 (6)	2.02 (6)	2.872 (4)	178 (10)
HESKHE·xEtOH	0.87 (6)	2.21 (6)	2.947 (7)	143 (4)

HES features multiple phenolic moieties that can participate in hydrogen bonding. Twelve HES entries in the CSD contain HES molecules that form infinite chains via supramolecular homosynthons (PhOH⋯PhOH, five structures) or other supramolecular heterosynthons (PhOH⋯O=C, four structures). The refcodes are summarized in Table S3. No cyclic dimers were found between HES molecules. When HES is deprotonated, the results reported here and in our previous study on polymorphic ICCs of HES with its tetra­ethyl­ammonium salt (Jin, Haskins et al., 2022) reveal that HES⁻ anions may form infinite chains with (in HESTEA-β) or without (in HESTEA-α, HESTEA-γ) HES molecules. They may also self-assemble into cyclic dimers which were found in four out of the seven structures reported in this work. Motif I cyclic dimers formed by pairs of PhOH⋯PhO⁻ hydrogen bonds exist in HESNA·H₂O, HESNAH and HESKHE·2H₂O. Motif II cyclic dimers generated by pairs of PhOH⋯PhOH hydrogen bonds between HES⁻ anions are present in HESNAH·2EtOH. No dimers comprising HES and HES⁻ were observed. It is therefore possible that HES⁻ anions and HES molecules are prone to form infinite chains, while HES⁻ anions can self-assemble into cyclic dimers.

3.5. HES conformation analysis

HES can exhibit flexibility around its chiral carbon atom, which is evident when the conformations of HES moieties extracted from the structures of HES reported here are overlaid by aligning the phenolic rings (Fig. 9). Since the torsional angles cannot be determined due to the disorder of the chiral carbon atoms, in general, the conformational variability of HES moieties can be readily assessed through the analysis of dihedral angles between the benzopyrone rings (chiral carbons excluded) and phenolic rings. In HESNA·H₂O, HESNAH·2EtOH, HESK·3H₂O, HESKHE·xMeOH and HESKHE·xEtOH, HES moieties were found to exist in various conformations in such a manner that the benzopyrone rings and phenolic rings are unfolded [Fig. 9(a)]. The dihedral angles in these five structures are given in Table S4 and range from 55.83 to 89.13°. Interestingly, in HESNAH and HESKHE·2H₂O, HES moieties exhibit conformations in which the benzopyrone and phenolic rings are folded with dihedral angles of 89.89 and 86.58°, respectively [Fig. 9(b)]. By inspection of HES conformations in all structures deposited in the CSD, we found that all HES moieties in the CSD are unfolded as shown in Fig. 9(a); the folded conformation has not been previously reported.

Figure 9 Overlay of (a) unfolded conformations of HES moieties found in HESNA·H2O (cyan), HESNAH·2EtOH (green for HES^−, blue for HES), HESK·3H2O (orange), HESKHE·xMeOH (magenta for HES), HESKHE·xEtOH (purple for HES^−, yellow for HES); and (b) folded conformations found in HESNAH (red) and HESKHE·2H2O (olive). HES^− in HESKHE·xMeOH is not included due to phenolic ring disorder. Hydrogen atoms have been omitted for clarity.

3.6. Powder dissolution analysis

Powder dissolution tests were performed for pure HES and HESNAH. The dissolution profiles are presented in Fig. 10. Pure HES produced a dissolution profile typical of a poorly soluble molecular compound, demonstrating a slower rate of dissolution before reaching a maximum concentration (C_max) of 27.71 ± 0.30 µg ml⁻¹ after 240 min. The residue after dissolution was identified as the anhydrous form of HES (Fig. S8). For HESNAH, an improvement in the HES C_max was achieved, known as a `spring' effect (Babu & Nangia, 2011), reaching 44.43 ± 4.74 µg ml⁻¹ within 10 min, i.e. 5.5 times more than pure HES at 10 min. Subsequently, the concentration dropped to 23.8 ± 0.65 µg ml⁻¹, lower than HES bulk solubility, which we attribute to transformation of HESNAH to the hydrated form of HES as indicated by PXRD and TGA (Fig. S8). The fact that HESNAH dissolved at a faster rate compared with pure HES could be beneficial for absorption in the body (Hörter & Dressman, 1997).

Figure 10 Dissolution profiles of HES and HESNAH in pH 6.8 PBS buffer.

4. Conclusions

The present study demonstrates that crystal engineering based on PhOH⋯PhO⁻ supramolecular heterosynthons can be utilized to isolate two new sodium/potassium salts of HES and six ICCs of HES with its conjugate salts. From the structural analysis, we found, as expected, that charge-assisted PhOH⋯PhO⁻ hydrogen bonds are shorter and more linear than the neutral PhOH⋯PhOH hydrogen bonds. Notably, symmetric or close-to-symmetric [PhO⋯H⋯PhO]⁻ hydrogen bonds were observed with short distances. HES moieties were found to exhibit various conformations: unfolded conformations in most structures and folded conformations, we believe for the first time in HES structures, in HESNAH and HESKHE·2H₂O. Issues relating to scale-up and stability were encountered for both salts and five of the ICCs. HESNAH, however, was found to be scalable and showed a modest improvement in dissolution with respect to pure HES. The improved in vitro performance of HESNAH offers the possibility to enhance the pharmacokinetics of HES but requires further study. Overall, the results indicate that, for weakly ionizable compounds such as HES, salt formation may be not an effective route for modulation of physicochemical properties, especially solubility, which is supported by the difficulties we encountered in reproducing the formation of HESNA·H₂O and HESK·3H₂O. In addition, the results further support the robustness and reliability of PhOH⋯PhO⁻ supramolecular heterosynthons for crystal engineering of ICCs of phenolic compounds. This is potentially relevant to a broad range of biologically active compounds such as flavonoids and polyphenols.

Supporting information

Computing details

Data collection: CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for HESKHE_xEtOH, HESNAH_2EtOH. Cell refinement: SAINT V8.40B (?, 2016) for HESKHE_2H2O, HESKHE_xMeOH, HESK_3H2O; CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for HESKHE_xEtOH, HESNAH_2EtOH; SAINT V8.38A (Bruker, 2018) for HESNAH, HESNA_H2O. Data reduction: SAINT V8.40B (?, 2016) for HESKHE_2H2O, HESKHE_xMeOH, HESK_3H2O; CrysAlis PRO 1.171.39.46 (Rigaku OD, 2018) for HESKHE_xEtOH, HESNAH_2EtOH; SAINT V8.38A (Bruker, 2018) for HESNAH, HESNA_H2O. Program(s) used to solve structure: SHELXT 2018/2 (Sheldrick, 2018) for HESKHE_2H2O, HESKHE_xEtOH, HESKHE_xMeOH, HESK_3H2O; XT (Sheldrick, 2015) for HESNAH; SHELXT 2014/5 (Sheldrick, 2014) for HESNAH_2EtOH, HESNA_H2O. For all structures, program(s) used to refine structure: SHELXL 2018/3 (Sheldrick, 2015); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

(HESKHE_2H2O)

Crystal data

C32H31KO14	F(000) = 708
Mr = 678.67	Dx = 1.515 Mg m^−3
Monoclinic, P2/n	Cu Kα radiation, λ = 1.54178 Å
a = 11.2185 (2) Å	Cell parameters from 8622 reflections
b = 10.2204 (2) Å	θ = 4.3–66.7°
c = 13.5244 (2) Å	µ = 2.23 mm^−1
β = 106.427 (1)°	T = 116 K
V = 1487.38 (5) Å^3	Block, clear light colourless
Z = 2	0.02 × 0.02 × 0.02 mm

Data collection

Bruker APEX-II CCD diffractometer	2414 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.049
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1000 before and 0.0781 after correction. The Ratio of minimum to maximum transmission is 0.6764. The λ/2 correction factor is Not present.	θmax = 66.7°, θmin = 4.3°
Tmin = 0.509, Tmax = 0.753	h = −12→13
14054 measured reflections	k = −11→9
2610 independent reflections	l = −13→16

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.161	w = 1/[σ^2(Fo^2) + (0.0982P)^2 + 1.649P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
2610 reflections	Δρmax = 0.33 e Å^−3
222 parameters	Δρmin = −0.89 e Å^−3
4 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
K1	0.250000	0.75764 (7)	0.750000	0.0239 (3)
O6	0.34801 (16)	0.12888 (17)	0.31911 (12)	0.0222 (4)
O5	0.17356 (17)	0.47456 (18)	0.46430 (14)	0.0261 (4)
O1	0.33577 (18)	−0.04043 (18)	0.89289 (14)	0.0277 (4)
O3	0.58768 (16)	0.31726 (17)	0.62889 (13)	0.0238 (4)
O2	0.46977 (18)	−0.09896 (18)	0.76907 (15)	0.0284 (4)
H5	0.209 (2)	0.524 (3)	0.510 (2)	0.034*
H2	0.526 (2)	−0.114 (3)	0.743 (2)	0.034*
H6	0.250000	0.129 (5)	0.250000	0.034*
O4	0.31528 (19)	0.58194 (19)	0.63047 (15)	0.0341 (5)
C12	0.4788 (2)	0.3143 (2)	0.55095 (18)	0.0209 (5)
C13	0.4682 (2)	0.2247 (2)	0.47334 (19)	0.0208 (5)
H13	0.535580	0.167917	0.474198	0.025*
C15	0.2580 (2)	0.3018 (2)	0.39118 (18)	0.0209 (5)
H15	0.182365	0.295844	0.337504	0.025*
C5	0.5012 (2)	0.2599 (2)	0.76954 (19)	0.0218 (5)
C2	0.3854 (2)	0.0636 (3)	0.85365 (19)	0.0225 (5)
C14	0.3576 (2)	0.2172 (2)	0.39267 (18)	0.0195 (5)
C16	0.2714 (2)	0.3935 (2)	0.46839 (18)	0.0205 (5)
C3	0.4590 (2)	0.0312 (2)	0.78894 (18)	0.0210 (5)
C10	0.3965 (3)	0.4995 (3)	0.6301 (2)	0.0266 (6)
C4	0.5166 (2)	0.1286 (3)	0.74894 (18)	0.0215 (5)
H4	0.567800	0.105647	0.706440	0.026*
O1W	0.0569 (2)	0.6674 (3)	0.5811 (2)	0.0555 (7)
H1WA	−0.014651	0.665385	0.597458	0.083*
H1WB	0.069570	0.584098	0.567477	0.083*
C11	0.3812 (2)	0.4027 (2)	0.55030 (18)	0.0207 (5)
C8	0.5730 (2)	0.3620 (3)	0.72751 (19)	0.0247 (6)
H8	0.657908	0.368818	0.777070	0.030*
C9	0.5174 (3)	0.4982 (3)	0.7132 (2)	0.0283 (6)
H9A	0.503873	0.528346	0.778708	0.034*
H9B	0.576223	0.559381	0.694818	0.034*
C6	0.4252 (3)	0.2920 (3)	0.8306 (2)	0.0299 (6)
H6A	0.412000	0.381358	0.843874	0.036*
C7	0.3676 (3)	0.1943 (3)	0.8729 (2)	0.0302 (6)
H7	0.316128	0.217550	0.915144	0.036*
C1	0.2768 (3)	−0.0130 (3)	0.9714 (2)	0.0303 (6)
H1A	0.200814	0.037647	0.941968	0.045*
H1B	0.333402	0.037618	1.026674	0.045*
H1C	0.255630	−0.095332	0.999560	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0326 (5)	0.0194 (4)	0.0237 (4)	0.000	0.0143 (3)	0.000
O6	0.0287 (9)	0.0202 (9)	0.0195 (8)	0.0039 (7)	0.0100 (7)	−0.0026 (7)
O5	0.0319 (10)	0.0224 (9)	0.0246 (9)	0.0087 (7)	0.0091 (8)	−0.0042 (7)
O1	0.0376 (10)	0.0245 (10)	0.0294 (10)	−0.0039 (8)	0.0231 (8)	−0.0036 (7)
O3	0.0232 (9)	0.0281 (10)	0.0217 (9)	−0.0038 (7)	0.0087 (7)	−0.0007 (7)
O2	0.0365 (10)	0.0201 (9)	0.0380 (11)	0.0023 (8)	0.0259 (9)	−0.0027 (8)
O4	0.0470 (12)	0.0251 (10)	0.0310 (10)	0.0053 (9)	0.0125 (9)	−0.0067 (8)
C12	0.0254 (12)	0.0199 (12)	0.0202 (12)	−0.0036 (9)	0.0112 (10)	0.0034 (9)
C13	0.0243 (13)	0.0199 (12)	0.0223 (12)	0.0028 (9)	0.0133 (10)	0.0020 (9)
C15	0.0278 (13)	0.0187 (12)	0.0175 (11)	0.0028 (10)	0.0085 (10)	0.0018 (9)
C5	0.0239 (12)	0.0234 (13)	0.0177 (12)	−0.0010 (9)	0.0052 (10)	−0.0007 (9)
C2	0.0262 (12)	0.0226 (13)	0.0207 (12)	−0.0014 (10)	0.0102 (10)	−0.0023 (9)
C14	0.0280 (13)	0.0172 (11)	0.0177 (11)	0.0001 (9)	0.0137 (10)	0.0036 (9)
C16	0.0289 (13)	0.0156 (12)	0.0208 (12)	0.0035 (9)	0.0132 (10)	0.0025 (9)
C3	0.0227 (12)	0.0211 (12)	0.0205 (11)	0.0020 (9)	0.0081 (10)	−0.0015 (9)
C10	0.0407 (15)	0.0173 (12)	0.0252 (13)	−0.0023 (11)	0.0149 (11)	−0.0005 (10)
C4	0.0214 (12)	0.0256 (13)	0.0192 (11)	0.0015 (9)	0.0087 (9)	−0.0008 (9)
O1W	0.0519 (15)	0.0586 (16)	0.0559 (15)	0.0063 (12)	0.0149 (12)	−0.0019 (12)
C11	0.0298 (13)	0.0166 (12)	0.0196 (12)	−0.0019 (10)	0.0130 (10)	0.0007 (9)
C8	0.0272 (13)	0.0273 (14)	0.0195 (12)	−0.0067 (10)	0.0063 (10)	−0.0046 (10)
C9	0.0375 (15)	0.0216 (13)	0.0268 (13)	−0.0099 (11)	0.0106 (11)	−0.0033 (10)
C6	0.0401 (16)	0.0237 (13)	0.0316 (14)	−0.0017 (11)	0.0193 (12)	−0.0062 (11)
C7	0.0404 (16)	0.0263 (15)	0.0316 (14)	−0.0009 (11)	0.0228 (12)	−0.0049 (11)
C1	0.0354 (15)	0.0353 (15)	0.0277 (14)	−0.0038 (12)	0.0210 (12)	−0.0032 (11)

Geometric parameters (Å, º)

K1—O1^i	2.8050 (19)	C15—C14	1.409 (3)
K1—O1^ii	2.8050 (19)	C15—C16	1.379 (3)
K1—O2^i	2.817 (2)	C5—C4	1.391 (4)
K1—O2^ii	2.817 (2)	C5—C8	1.524 (3)
K1—O4^iii	2.6540 (19)	C5—C6	1.384 (4)
K1—O4	2.6540 (19)	C2—C3	1.402 (3)
K1—O1W^iii	2.821 (3)	C2—C7	1.386 (4)
K1—O1W	2.821 (3)	C16—C11	1.407 (4)
O6—H6	1.2253 (17)	C3—C4	1.378 (4)
O6—C14	1.325 (3)	C10—C11	1.438 (3)
O5—H5	0.810 (18)	C10—C9	1.497 (4)
O5—C16	1.364 (3)	C4—H4	0.9500
O1—C2	1.375 (3)	O1W—H1WA	0.8913
O1—C1	1.430 (3)	O1W—H1WB	0.8913
O3—C12	1.369 (3)	C8—H8	1.0000
O3—C8	1.463 (3)	C8—C9	1.515 (4)
O2—H2	0.819 (18)	C9—H9A	0.9900
O2—C3	1.369 (3)	C9—H9B	0.9900
O4—C10	1.242 (3)	C6—H6A	0.9500
C12—C13	1.373 (4)	C6—C7	1.396 (4)
C12—C11	1.418 (4)	C7—H7	0.9500
C13—H13	0.9500	C1—H1A	0.9800
C13—C14	1.404 (4)	C1—H1B	0.9800
C15—H15	0.9500	C1—H1C	0.9800
O1^i—K1—O1^ii	85.26 (8)	C6—C5—C8	122.7 (2)
O1^ii—K1—O2^i	78.53 (6)	O1—C2—C3	115.6 (2)
O1^ii—K1—O2^ii	55.47 (5)	O1—C2—C7	125.3 (2)
O1^i—K1—O2^i	55.47 (5)	C7—C2—C3	119.1 (2)
O1^i—K1—O2^ii	78.53 (6)	O6—C14—C13	119.1 (2)
O1^i—K1—O1W^iii	69.36 (7)	O6—C14—C15	120.8 (2)
O1^i—K1—O1W	146.45 (7)	C13—C14—C15	120.1 (2)
O1^ii—K1—O1W^iii	146.45 (7)	O5—C16—C15	117.9 (2)
O1^ii—K1—O1W	69.36 (7)	O5—C16—C11	120.4 (2)
O2^i—K1—O2^ii	117.29 (8)	C15—C16—C11	121.7 (2)
O2^ii—K1—O1W^iii	134.10 (7)	O2—C3—C2	116.9 (2)
O2^i—K1—O1W^iii	69.15 (7)	O2—C3—C4	123.2 (2)
O2^i—K1—O1W	134.10 (7)	C4—C3—C2	119.9 (2)
O2^ii—K1—O1W	69.15 (7)	O4—C10—C11	122.6 (3)
O4^iii—K1—O1^ii	144.83 (6)	O4—C10—C9	120.8 (2)
O4—K1—O1^ii	100.26 (6)	C11—C10—C9	116.6 (2)
O4—K1—O1^i	144.83 (6)	C5—C4—H4	119.3
O4^iii—K1—O1^i	100.26 (6)	C3—C4—C5	121.3 (2)
O4—K1—O2^i	91.30 (6)	C3—C4—H4	119.3
O4—K1—O2^ii	132.96 (6)	K1—O1W—H1WA	110.3
O4^iii—K1—O2^ii	91.30 (6)	K1—O1W—H1WB	110.4
O4^iii—K1—O2^i	132.96 (6)	H1WA—O1W—H1WB	103.7
O4^iii—K1—O4	94.84 (9)	C12—C11—C10	120.4 (2)
O4^iii—K1—O1W	89.49 (7)	C16—C11—C12	117.7 (2)
O4—K1—O1W	64.33 (7)	C16—C11—C10	121.9 (2)
O4^iii—K1—O1W^iii	64.33 (7)	O3—C8—C5	109.49 (19)
O4—K1—O1W^iii	89.49 (7)	O3—C8—H8	107.5
O1W^iii—K1—O1W	141.86 (12)	O3—C8—C9	108.6 (2)
C14—O6—H6	116.1 (17)	C5—C8—H8	107.5
C16—O5—H5	97.7 (18)	C9—C8—C5	115.8 (2)
C2—O1—K1^iv	113.62 (14)	C9—C8—H8	107.5
C2—O1—C1	117.3 (2)	C10—C9—C8	110.9 (2)
C1—O1—K1^iv	121.05 (15)	C10—C9—H9A	109.5
C12—O3—C8	113.77 (18)	C10—C9—H9B	109.5
K1^iv—O2—H2	129 (2)	C8—C9—H9A	109.5
C3—O2—K1^iv	113.60 (14)	C8—C9—H9B	109.5
C3—O2—H2	113 (2)	H9A—C9—H9B	108.0
C10—O4—K1	142.26 (18)	C5—C6—H6A	119.7
O3—C12—C13	118.0 (2)	C5—C6—C7	120.6 (3)
O3—C12—C11	120.6 (2)	C7—C6—H6A	119.7
C13—C12—C11	121.4 (2)	C2—C7—C6	120.3 (2)
C12—C13—H13	120.1	C2—C7—H7	119.9
C12—C13—C14	119.8 (2)	C6—C7—H7	119.9
C14—C13—H13	120.1	O1—C1—H1A	109.5
C14—C15—H15	120.3	O1—C1—H1B	109.5
C16—C15—H15	120.3	O1—C1—H1C	109.5
C16—C15—C14	119.4 (2)	H1A—C1—H1B	109.5
C4—C5—C8	118.5 (2)	H1A—C1—H1C	109.5
C6—C5—C4	118.7 (2)	H1B—C1—H1C	109.5
K1^iv—O1—C2—C3	−40.4 (3)	C5—C8—C9—C10	−66.7 (3)
K1^iv—O1—C2—C7	139.4 (2)	C5—C6—C7—C2	−0.4 (4)
K1^iv—O2—C3—C2	36.7 (3)	C2—C3—C4—C5	−1.4 (4)
K1^iv—O2—C3—C4	−143.5 (2)	C14—C15—C16—O5	179.5 (2)
K1—O4—C10—C11	166.72 (19)	C14—C15—C16—C11	−1.6 (4)
K1—O4—C10—C9	−14.4 (4)	C16—C15—C14—O6	−179.4 (2)
O5—C16—C11—C12	179.1 (2)	C16—C15—C14—C13	1.3 (3)
O5—C16—C11—C10	−2.2 (4)	C3—C2—C7—C6	−1.7 (4)
O1—C2—C3—O2	2.3 (3)	C4—C5—C8—O3	32.8 (3)
O1—C2—C3—C4	−177.6 (2)	C4—C5—C8—C9	156.0 (2)
O1—C2—C7—C6	178.5 (3)	C4—C5—C6—C7	1.7 (4)
O3—C12—C13—C14	179.2 (2)	C11—C12—C13—C14	−1.7 (4)
O3—C12—C11—C16	−179.4 (2)	C11—C10—C9—C8	−27.9 (3)
O3—C12—C11—C10	1.8 (3)	C8—O3—C12—C13	−151.3 (2)
O3—C8—C9—C10	56.9 (3)	C8—O3—C12—C11	29.5 (3)
O2—C3—C4—C5	178.7 (2)	C8—C5—C4—C3	176.8 (2)
O4—C10—C11—C12	177.2 (2)	C8—C5—C6—C7	−175.7 (3)
O4—C10—C11—C16	−1.5 (4)	C9—C10—C11—C12	−1.7 (3)
O4—C10—C9—C8	153.2 (2)	C9—C10—C11—C16	179.6 (2)
C12—O3—C8—C5	68.7 (3)	C6—C5—C4—C3	−0.7 (4)
C12—O3—C8—C9	−58.6 (3)	C6—C5—C8—O3	−149.8 (2)
C12—C13—C14—O6	−179.0 (2)	C6—C5—C8—C9	−26.6 (3)
C12—C13—C14—C15	0.3 (3)	C7—C2—C3—O2	−177.5 (2)
C13—C12—C11—C16	1.5 (3)	C7—C2—C3—C4	2.6 (4)
C13—C12—C11—C10	−177.3 (2)	C1—O1—C2—C3	170.4 (2)
C15—C16—C11—C12	0.2 (3)	C1—O1—C2—C7	−9.8 (4)
C15—C16—C11—C10	178.9 (2)

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

(HESKHE_xEtOH)

Crystal data

C32H27KO12·C2H6O	F(000) = 2880
Mr = 688.70	Dx = 1.369 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.4072 (8) Å	Cell parameters from 11675 reflections
b = 20.4384 (8) Å	θ = 2.0–33.6°
c = 17.3645 (11) Å	µ = 0.23 mm^−1
β = 104.006 (5)°	T = 113 K
V = 6682.9 (6) Å^3	Prism, clear light colourless
Z = 8	0.16 × 0.14 × 0.13 mm

Data collection

Dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images diffractometer	6841 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5112 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
ω scans	θmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −24→24
Tmin = 0.373, Tmax = 1.000	k = −25→25
26486 measured reflections	l = −16→21

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.080	w = 1/[σ^2(Fo^2) + (0.0733P)^2 + 29.3626P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.205	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 1.05 e Å^−3
6841 reflections	Δρmin = −0.99 e Å^−3
485 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
52 restraints	Extinction coefficient: 0.0018 (3)
Primary atom site location: dual

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)
K1	0.500000	0.15403 (8)	0.750000	0.0693 (5)
K2	0.500000	0.46138 (5)	0.750000	0.0332 (3)
O8	0.58381 (13)	0.23949 (13)	0.8501 (3)	0.0684 (11)
O7	0.79833 (12)	0.12037 (11)	0.91463 (16)	0.0381 (6)
O10	0.80946 (11)	0.34955 (10)	0.90355 (15)	0.0326 (6)
O9	0.59176 (12)	0.36479 (12)	0.8379 (2)	0.0555 (9)
O11	0.8964 (4)	0.5615 (3)	0.7650 (3)	0.161 (3)
O12	0.97181 (15)	0.61359 (13)	0.8975 (2)	0.0539 (8)
O5	0.56619 (13)	0.40942 (12)	0.6470 (2)	0.0481 (7)
O6	0.77600 (14)	0.52304 (12)	0.6339 (2)	0.0506 (8)
O3	0.78010 (12)	0.29340 (11)	0.64322 (18)	0.0426 (7)
O4	0.57229 (15)	0.28430 (14)	0.6578 (3)	0.0834 (14)
O2	0.92370 (14)	0.06740 (12)	0.76338 (17)	0.0424 (6)
O1	0.92256 (11)	0.02309 (10)	0.62261 (15)	0.0337 (6)
O1E	0.93408 (14)	0.11566 (13)	0.90669 (18)	0.0469 (7)
H1E	0.894107	0.123368	0.915327	0.070*
C19	0.65568 (18)	0.23849 (17)	0.8695 (3)	0.0435 (10)
C18	0.68961 (17)	0.17944 (16)	0.8828 (3)	0.0402 (9)
H18	0.662767	0.140172	0.878606	0.048*
C17	0.76421 (17)	0.17684 (15)	0.9028 (2)	0.0305 (7)
C22	0.80315 (16)	0.23571 (15)	0.9107 (2)	0.0312 (7)
H22	0.853579	0.234667	0.925642	0.037*
C21	0.76817 (16)	0.29466 (15)	0.8968 (2)	0.0290 (7)
C20	0.69368 (17)	0.29842 (15)	0.8758 (2)	0.0350 (8)
C25	0.65758 (18)	0.35938 (17)	0.8575 (3)	0.0415 (9)
C24	0.70529 (19)	0.41792 (17)	0.8601 (3)	0.0515 (12)
H24A	0.712423	0.425654	0.806267	0.062*	0.657 (14)
H24B	0.681382	0.456944	0.875266	0.062*	0.657 (14)
H24C	0.684845	0.445465	0.813227	0.062*	0.343 (14)
H24D	0.703583	0.443852	0.907741	0.062*	0.343 (14)
C23B	0.7740 (3)	0.4105 (2)	0.9152 (5)	0.0302 (16)	0.657 (14)
H23B	0.767901	0.412042	0.970738	0.036*	0.657 (14)
C26	0.8273 (2)	0.46430 (18)	0.9048 (4)	0.0607 (14)
C31	0.8611 (3)	0.4936 (3)	0.9738 (4)	0.0818 (17)
H31	0.851887	0.479810	1.022623	0.098*
C30	0.9095 (3)	0.5441 (3)	0.9727 (3)	0.0769 (16)
H30	0.932703	0.564660	1.021133	0.092*
C29	0.92419 (19)	0.56453 (17)	0.9033 (3)	0.0429 (9)
C28	0.8876 (4)	0.5369 (2)	0.8348 (3)	0.0782 (17)
C27	0.8393 (3)	0.4865 (2)	0.8378 (4)	0.0844 (19)
H27	0.814037	0.467370	0.789346	0.101*
C32	1.0073 (3)	0.6441 (3)	0.9698 (4)	0.0860 (19)
H32A	1.045533	0.672028	0.960371	0.129*
H32B	1.027425	0.610541	1.009049	0.129*
H32C	0.973445	0.670883	0.989666	0.129*
C16	0.63568 (17)	0.40894 (16)	0.6463 (2)	0.0366 (8)
C15	0.66960 (18)	0.46724 (16)	0.6418 (2)	0.0376 (8)
H15	0.644657	0.507311	0.641114	0.045*
C14	0.74092 (18)	0.46777 (16)	0.6382 (2)	0.0390 (9)
C13	0.77758 (18)	0.40802 (17)	0.6399 (3)	0.0411 (9)
H13	0.826052	0.407781	0.637814	0.049*
C12	0.74278 (17)	0.35014 (16)	0.6446 (2)	0.0361 (8)
C11	0.67096 (17)	0.34810 (16)	0.6487 (2)	0.0371 (8)
C10	0.6351 (2)	0.28742 (19)	0.6536 (4)	0.0639 (15)
C9B	0.6755 (3)	0.2285 (4)	0.6322 (8)	0.035 (2)	0.54 (2)
H9BA	0.658232	0.187786	0.652108	0.042*	0.54 (2)
H9BB	0.667418	0.225084	0.573864	0.042*	0.54 (2)
C8B	0.7502 (3)	0.2369 (3)	0.6678 (7)	0.0359 (19)	0.661 (19)
H8B	0.757814	0.237832	0.726824	0.043*	0.661 (19)
C5	0.7925 (2)	0.17909 (18)	0.6447 (3)	0.0539 (12)
C4	0.83720 (19)	0.15049 (16)	0.7106 (3)	0.0435 (10)
H4	0.838581	0.167024	0.762065	0.052*
C3	0.87984 (18)	0.09800 (15)	0.7019 (2)	0.0355 (8)
C2	0.87766 (16)	0.07443 (15)	0.6258 (2)	0.0330 (8)
C7	0.8329 (2)	0.10241 (19)	0.5607 (3)	0.0464 (10)
H7	0.830883	0.085790	0.509101	0.056*
C6	0.7904 (2)	0.1552 (2)	0.5703 (3)	0.0610 (13)
H6A	0.759706	0.174721	0.525176	0.073*
C1	0.92094 (19)	−0.00422 (18)	0.5466 (2)	0.0398 (9)
H1A	0.952353	−0.042410	0.552936	0.060*
H1B	0.937049	0.028589	0.513655	0.060*
H1C	0.872320	−0.017595	0.520881	0.060*
C2E	1.0038 (3)	0.2104 (2)	0.8935 (4)	0.0787 (17)
H2EA	1.019985	0.187317	0.851594	0.118*
H2EB	1.041953	0.238638	0.922937	0.118*
H2EC	0.962198	0.237126	0.869574	0.118*
C1E	0.9844 (2)	0.1620 (2)	0.9485 (3)	0.0551 (11)
H1EA	1.027705	0.138674	0.977458	0.066*
H1EB	0.964157	0.185147	0.987992	0.066*
H2	0.927 (3)	0.085 (2)	0.8086 (14)	0.066*
H5	0.553 (2)	0.3703 (9)	0.651 (3)	0.066*
H8	0.569 (2)	0.2785 (12)	0.844 (3)	0.066*
H6	0.752 (2)	0.5540 (18)	0.609 (3)	0.066*
C23A	0.7776 (4)	0.4066 (4)	0.8615 (10)	0.039 (4)	0.343 (14)
H23A	0.782289	0.403663	0.805563	0.046*	0.343 (14)
C9A	0.6847 (6)	0.2260 (4)	0.6777 (12)	0.042 (4)	0.46 (2)
H9AA	0.708909	0.226737	0.734851	0.051*	0.46 (2)
H9AB	0.657656	0.184665	0.665293	0.051*	0.46 (2)
C8A	0.7365 (6)	0.2342 (4)	0.6270 (10)	0.025 (3)	0.339 (19)
H8A	0.710771	0.233044	0.569693	0.030*	0.339 (19)
H11	0.878 (2)	0.548 (8)	0.717 (3)	0.33 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0848 (11)	0.0557 (9)	0.0748 (11)	0.000	0.0337 (9)	0.000
K2	0.0217 (5)	0.0164 (5)	0.0597 (7)	0.000	0.0062 (4)	0.000
O8	0.0229 (13)	0.0230 (14)	0.153 (3)	0.0007 (10)	0.0085 (16)	0.0206 (17)
O7	0.0324 (12)	0.0145 (11)	0.0661 (18)	0.0061 (9)	0.0096 (11)	0.0047 (11)
O10	0.0239 (11)	0.0152 (11)	0.0578 (16)	0.0005 (8)	0.0080 (10)	0.0019 (10)
O9	0.0233 (12)	0.0198 (12)	0.118 (3)	0.0037 (9)	0.0074 (14)	0.0138 (14)
O11	0.308 (9)	0.104 (4)	0.077 (3)	−0.115 (5)	0.061 (4)	−0.013 (3)
O12	0.0511 (16)	0.0306 (14)	0.082 (2)	−0.0176 (12)	0.0208 (15)	−0.0067 (14)
O5	0.0275 (12)	0.0245 (13)	0.093 (2)	0.0055 (10)	0.0159 (13)	−0.0119 (14)
O6	0.0382 (15)	0.0243 (14)	0.091 (2)	0.0040 (10)	0.0192 (14)	0.0111 (14)
O3	0.0264 (12)	0.0226 (12)	0.079 (2)	0.0096 (9)	0.0138 (12)	−0.0028 (12)
O4	0.0322 (15)	0.0258 (14)	0.199 (4)	−0.0035 (11)	0.041 (2)	−0.029 (2)
O2	0.0452 (15)	0.0278 (13)	0.0548 (17)	0.0092 (11)	0.0134 (13)	−0.0064 (12)
O1	0.0271 (11)	0.0185 (11)	0.0545 (16)	0.0091 (9)	0.0079 (10)	−0.0035 (10)
O1E	0.0388 (14)	0.0340 (14)	0.071 (2)	−0.0004 (11)	0.0199 (13)	−0.0112 (13)
C19	0.0263 (17)	0.0222 (17)	0.081 (3)	0.0013 (13)	0.0107 (17)	0.0122 (18)
C18	0.0280 (17)	0.0158 (15)	0.076 (3)	−0.0026 (12)	0.0109 (17)	0.0093 (16)
C17	0.0284 (16)	0.0163 (15)	0.047 (2)	0.0029 (12)	0.0085 (14)	0.0051 (14)
C22	0.0230 (15)	0.0178 (15)	0.052 (2)	0.0027 (12)	0.0073 (14)	0.0015 (14)
C21	0.0252 (15)	0.0166 (15)	0.046 (2)	−0.0005 (11)	0.0100 (14)	0.0029 (13)
C20	0.0255 (16)	0.0182 (16)	0.060 (2)	0.0021 (12)	0.0082 (15)	0.0078 (15)
C25	0.0292 (17)	0.0213 (17)	0.074 (3)	0.0035 (13)	0.0118 (17)	0.0088 (17)
C24	0.0293 (18)	0.0177 (17)	0.105 (4)	0.0037 (13)	0.012 (2)	0.0130 (19)
C23B	0.029 (2)	0.018 (2)	0.044 (4)	0.0027 (17)	0.010 (2)	0.003 (2)
C26	0.0307 (19)	0.0189 (18)	0.122 (4)	0.0001 (15)	−0.002 (2)	0.018 (2)
C31	0.079 (4)	0.061 (3)	0.118 (5)	−0.031 (3)	0.048 (4)	−0.005 (3)
C30	0.090 (4)	0.066 (3)	0.079 (4)	−0.044 (3)	0.028 (3)	−0.018 (3)
C29	0.0378 (19)	0.0217 (17)	0.069 (3)	−0.0074 (14)	0.0132 (18)	−0.0013 (17)
C28	0.133 (5)	0.037 (3)	0.062 (3)	−0.030 (3)	0.019 (3)	0.002 (2)
C27	0.107 (5)	0.040 (3)	0.084 (4)	−0.031 (3)	−0.020 (3)	−0.008 (3)
C32	0.083 (4)	0.065 (3)	0.100 (4)	−0.049 (3)	0.003 (3)	−0.012 (3)
C16	0.0239 (16)	0.0245 (17)	0.060 (2)	0.0061 (13)	0.0077 (15)	−0.0065 (16)
C15	0.0326 (17)	0.0207 (16)	0.058 (2)	0.0074 (13)	0.0089 (16)	−0.0055 (15)
C14	0.0314 (17)	0.0224 (17)	0.062 (2)	0.0021 (13)	0.0087 (16)	−0.0020 (16)
C13	0.0261 (16)	0.0263 (18)	0.071 (3)	0.0056 (13)	0.0125 (17)	0.0008 (17)
C12	0.0276 (16)	0.0218 (16)	0.058 (2)	0.0094 (13)	0.0084 (15)	−0.0030 (15)
C11	0.0268 (16)	0.0218 (17)	0.062 (2)	0.0036 (13)	0.0082 (16)	−0.0082 (16)
C10	0.034 (2)	0.0254 (19)	0.136 (5)	0.0021 (16)	0.028 (2)	−0.021 (2)
C9B	0.039 (3)	0.025 (3)	0.045 (4)	0.008 (2)	0.014 (3)	−0.002 (3)
C8B	0.038 (3)	0.024 (3)	0.046 (4)	0.012 (2)	0.011 (3)	0.003 (3)
C5	0.045 (2)	0.0218 (18)	0.106 (4)	0.0128 (16)	0.039 (2)	0.009 (2)
C4	0.040 (2)	0.0172 (16)	0.083 (3)	0.0015 (14)	0.034 (2)	−0.0046 (17)
C3	0.0315 (17)	0.0158 (15)	0.064 (2)	−0.0001 (12)	0.0206 (16)	−0.0022 (15)
C2	0.0253 (15)	0.0130 (14)	0.063 (2)	0.0054 (11)	0.0162 (15)	0.0027 (15)
C7	0.038 (2)	0.036 (2)	0.068 (3)	0.0140 (16)	0.0177 (19)	0.0105 (19)
C6	0.048 (2)	0.044 (2)	0.094 (4)	0.0271 (19)	0.023 (2)	0.027 (2)
C1	0.0358 (18)	0.0300 (18)	0.053 (2)	0.0106 (14)	0.0098 (16)	−0.0067 (16)
C2E	0.078 (4)	0.042 (3)	0.130 (5)	0.002 (2)	0.052 (4)	−0.004 (3)
C1E	0.042 (2)	0.037 (2)	0.087 (3)	0.0054 (17)	0.016 (2)	−0.010 (2)
C23A	0.027 (5)	0.017 (5)	0.069 (11)	−0.002 (4)	0.005 (5)	0.014 (5)
C9A	0.048 (5)	0.016 (4)	0.075 (10)	0.006 (3)	0.038 (6)	−0.007 (5)
C8A	0.033 (6)	0.020 (5)	0.024 (7)	0.010 (4)	0.010 (5)	0.000 (5)

Geometric parameters (Å, º)

K1—O8^i	2.711 (3)	C23B—H23B	1.0000
K1—O8	2.711 (4)	C23B—C26	1.550 (6)
K1—O11^ii	2.817 (5)	C26—C31	1.358 (8)
K1—O11^iii	2.817 (5)	C26—C27	1.320 (8)
K1—O12^iii	2.867 (3)	C26—C23A	1.592 (11)
K1—O12^ii	2.867 (3)	C31—H31	0.9500
K2—O9	2.843 (3)	C31—C30	1.400 (6)
K2—O9^i	2.843 (3)	C30—H30	0.9500
K2—O5	2.663 (3)	C30—C29	1.369 (7)
K2—O5^i	2.663 (3)	C29—C28	1.352 (6)
K2—O2^iv	2.666 (2)	C28—C27	1.401 (7)
K2—O2^v	2.666 (2)	C27—H27	0.9500
K2—O1^iv	2.671 (2)	C32—H32A	0.9800
K2—O1^v	2.671 (2)	C32—H32B	0.9800
K2—H5	2.89 (4)	C32—H32C	0.9800
O8—C19	1.353 (4)	C16—C15	1.373 (5)
O8—H8	0.844 (19)	C16—C11	1.415 (4)
O7—C17	1.322 (4)	C15—H15	0.9500
O10—C21	1.367 (4)	C15—C14	1.401 (5)
O10—C23B	1.462 (5)	C14—C13	1.410 (5)
O10—C23A	1.434 (9)	C13—H13	0.9500
O9—C25	1.245 (4)	C13—C12	1.374 (5)
O11—C28	1.361 (7)	C12—C11	1.414 (5)
O11—H11	0.87 (2)	C11—C10	1.434 (5)
O12—C29	1.384 (4)	C10—C9B	1.530 (8)
O12—C32	1.422 (6)	C10—C9A	1.576 (10)
O5—C16	1.351 (4)	C9B—H9BA	0.9900
O5—H5	0.848 (9)	C9B—H9BB	0.9900
O6—C14	1.330 (4)	C9B—C8B	1.441 (5)
O6—H6	0.845 (19)	C8B—H8B	1.0000
O3—C12	1.370 (4)	C8B—C5	1.546 (7)
O3—C8B	1.405 (7)	C5—C4	1.387 (6)
O3—C8A	1.464 (10)	C5—C6	1.371 (7)
O4—C10	1.241 (5)	C5—C8A	1.544 (10)
O2—C3	1.348 (5)	C4—H4	0.9500
O2—H2	0.848 (9)	C4—C3	1.385 (4)
O1—C2	1.374 (3)	C3—C2	1.397 (5)
O1—C1	1.427 (4)	C2—C7	1.373 (5)
O1E—H1E	0.8400	C7—H7	0.9500
O1E—C1E	1.426 (5)	C7—C6	1.392 (5)
C19—C18	1.368 (5)	C6—H6A	0.9500
C19—C20	1.420 (5)	C1—H1A	0.9800
C18—H18	0.9500	C1—H1B	0.9800
C18—C17	1.406 (4)	C1—H1C	0.9800
C17—C22	1.410 (4)	C2E—H2EA	0.9800
C22—H22	0.9500	C2E—H2EB	0.9800
C22—C21	1.375 (4)	C2E—H2EC	0.9800
C21—C20	1.405 (4)	C2E—C1E	1.486 (7)
C20—C25	1.427 (4)	C1E—H1EA	0.9900
C25—C24	1.507 (5)	C1E—H1EB	0.9900
C24—H24A	0.9900	C23A—H23A	1.0000
C24—H24B	0.9900	C9A—H9AA	0.9900
C24—H24C	0.9900	C9A—H9AB	0.9900
C24—H24D	0.9900	C9A—C8A	1.497 (12)
C24—C23B	1.449 (7)	C8A—H8A	1.0000
C24—C23A	1.416 (10)
O8^i—K1—O8	99.78 (13)	C31—C26—C23A	148.2 (7)
O8—K1—O11^ii	134.73 (13)	C27—C26—C23B	127.7 (5)
O8—K1—O11^iii	99.27 (18)	C27—C26—C31	118.4 (4)
O8^i—K1—O11^ii	99.27 (18)	C27—C26—C23A	93.2 (7)
O8^i—K1—O11^iii	134.73 (13)	C26—C31—H31	120.2
O8^i—K1—O12^iii	80.07 (10)	C26—C31—C30	119.7 (5)
O8—K1—O12^ii	80.07 (10)	C30—C31—H31	120.2
O8—K1—O12^iii	122.95 (10)	C31—C30—H30	119.3
O8^i—K1—O12^ii	122.95 (10)	C29—C30—C31	121.3 (5)
O11^ii—K1—O11^iii	95.7 (3)	C29—C30—H30	119.3
O11^ii—K1—O12^iii	100.60 (13)	C30—C29—O12	124.7 (4)
O11^iii—K1—O12^iii	55.18 (12)	C28—C29—O12	117.2 (4)
O11^iii—K1—O12^ii	100.60 (13)	C28—C29—C30	118.0 (4)
O11^ii—K1—O12^ii	55.18 (12)	O11—C28—C27	122.3 (5)
O12^iii—K1—O12^ii	146.48 (13)	C29—C28—O11	118.4 (5)
O9^i—K2—O9	92.05 (11)	C29—C28—C27	119.2 (5)
O9^i—K2—H5	60.0 (7)	C26—C27—C28	123.2 (5)
O9—K2—H5	66.7 (9)	C26—C27—H27	118.4
O5^i—K2—O9^i	75.09 (10)	C28—C27—H27	118.4
O5^i—K2—O9	72.75 (8)	O12—C32—H32A	109.5
O5—K2—O9	75.09 (10)	O12—C32—H32B	109.5
O5—K2—O9^i	72.75 (8)	O12—C32—H32C	109.5
O5—K2—O5^i	132.99 (12)	H32A—C32—H32B	109.5
O5—K2—O2^v	138.68 (9)	H32A—C32—H32C	109.5
O5^i—K2—O2^v	84.10 (8)	H32B—C32—H32C	109.5
O5—K2—O2^iv	84.10 (8)	O5—C16—C15	119.2 (3)
O5^i—K2—O2^iv	138.68 (9)	O5—C16—C11	118.9 (3)
O5—K2—O1^v	84.15 (8)	C15—C16—C11	121.9 (3)
O5—K2—O1^iv	118.59 (8)	C16—C15—H15	119.9
O5^i—K2—O1^iv	84.15 (8)	C16—C15—C14	120.1 (3)
O5^i—K2—O1^v	118.59 (8)	C14—C15—H15	119.9
O5—K2—H5	17.0 (4)	O6—C14—C15	122.3 (3)
O5^i—K2—H5	116.2 (5)	O6—C14—C13	118.3 (3)
O2^v—K2—O9	143.74 (9)	C15—C14—C13	119.4 (3)
O2^iv—K2—O9	108.80 (8)	C14—C13—H13	120.2
O2^v—K2—O9^i	108.80 (8)	C12—C13—C14	119.6 (3)
O2^iv—K2—O9^i	143.74 (9)	C12—C13—H13	120.2
O2^iv—K2—O2^v	71.28 (12)	O3—C12—C13	117.3 (3)
O2^iv—K2—O1^v	75.95 (8)	O3—C12—C11	120.5 (3)
O2^v—K2—O1^v	58.36 (8)	C13—C12—C11	122.2 (3)
O2^v—K2—O1^iv	75.95 (8)	C16—C11—C10	121.6 (3)
O2^iv—K2—O1^iv	58.36 (8)	C12—C11—C16	116.7 (3)
O2^v—K2—H5	149.5 (9)	C12—C11—C10	121.8 (3)
O2^iv—K2—H5	100.8 (5)	O4—C10—C11	123.0 (3)
O1^iv—K2—O9^i	157.89 (9)	O4—C10—C9B	122.8 (4)
O1^v—K2—O9	157.89 (9)	O4—C10—C9A	119.3 (5)
O1^iv—K2—O9	74.29 (8)	C11—C10—C9B	112.5 (4)
O1^v—K2—O9^i	74.29 (8)	C11—C10—C9A	115.5 (4)
O1^iv—K2—O1^v	123.65 (10)	C10—C9B—H9BA	109.9
O1^iv—K2—H5	126.0 (9)	C10—C9B—H9BB	109.9
O1^v—K2—H5	91.2 (9)	H9BA—C9B—H9BB	108.3
K1—O8—H8	113 (3)	C8B—C9B—C10	108.9 (5)
C19—O8—K1	124.9 (3)	C8B—C9B—H9BA	109.9
C19—O8—H8	110 (3)	C8B—C9B—H9BB	109.9
C21—O10—C23B	115.2 (3)	O3—C8B—C9B	114.5 (6)
C21—O10—C23A	116.9 (4)	O3—C8B—H8B	109.0
C25—O9—K2	132.5 (2)	O3—C8B—C5	105.4 (5)
K1^vi—O11—H11	105 (8)	C9B—C8B—H8B	109.0
C28—O11—K1^vi	125.3 (4)	C9B—C8B—C5	109.9 (6)
C28—O11—H11	129 (9)	C5—C8B—H8B	109.0
C29—O12—K1^vi	123.3 (3)	C4—C5—C8B	111.9 (5)
C29—O12—C32	116.3 (4)	C4—C5—C8A	137.8 (7)
C32—O12—K1^vi	120.4 (3)	C6—C5—C8B	128.3 (5)
K2—O5—H5	97 (3)	C6—C5—C4	119.8 (3)
C16—O5—K2	130.8 (2)	C6—C5—C8A	102.4 (7)
C16—O5—H5	108 (3)	C5—C4—H4	119.8
C14—O6—H6	116 (3)	C3—C4—C5	120.5 (4)
C12—O3—C8B	115.6 (3)	C3—C4—H4	119.8
C12—O3—C8A	114.8 (4)	O2—C3—C4	123.5 (4)
K2^vii—O2—H2	120 (3)	O2—C3—C2	117.3 (3)
C3—O2—K2^vii	124.5 (2)	C4—C3—C2	119.2 (4)
C3—O2—H2	116 (3)	O1—C2—C3	115.3 (3)
C2—O1—K2^vii	124.2 (2)	C7—C2—O1	124.5 (3)
C2—O1—C1	117.6 (3)	C7—C2—C3	120.2 (3)
C1—O1—K2^vii	117.62 (18)	C2—C7—H7	120.0
C1E—O1E—H1E	109.5	C2—C7—C6	119.9 (4)
O8—C19—C18	118.7 (3)	C6—C7—H7	120.0
O8—C19—C20	119.4 (3)	C5—C6—C7	120.4 (4)
C18—C19—C20	121.9 (3)	C5—C6—H6A	119.8
C19—C18—H18	120.0	C7—C6—H6A	119.8
C19—C18—C17	120.0 (3)	O1—C1—H1A	109.5
C17—C18—H18	120.0	O1—C1—H1B	109.5
O7—C17—C18	121.2 (3)	O1—C1—H1C	109.5
O7—C17—C22	119.6 (3)	H1A—C1—H1B	109.5
C18—C17—C22	119.2 (3)	H1A—C1—H1C	109.5
C17—C22—H22	120.0	H1B—C1—H1C	109.5
C21—C22—C17	120.0 (3)	H2EA—C2E—H2EB	109.5
C21—C22—H22	120.0	H2EA—C2E—H2EC	109.5
O10—C21—C22	116.7 (3)	H2EB—C2E—H2EC	109.5
O10—C21—C20	121.5 (3)	C1E—C2E—H2EA	109.5
C22—C21—C20	121.8 (3)	C1E—C2E—H2EB	109.5
C19—C20—C25	121.2 (3)	C1E—C2E—H2EC	109.5
C21—C20—C19	117.1 (3)	O1E—C1E—C2E	111.3 (4)
C21—C20—C25	121.6 (3)	O1E—C1E—H1EA	109.4
O9—C25—C20	123.7 (3)	O1E—C1E—H1EB	109.4
O9—C25—C24	121.3 (3)	C2E—C1E—H1EA	109.4
C20—C25—C24	114.9 (3)	C2E—C1E—H1EB	109.4
C25—C24—H24A	108.9	H1EA—C1E—H1EB	108.0
C25—C24—H24B	108.9	O10—C23A—C26	103.0 (7)
C25—C24—H24C	107.8	O10—C23A—H23A	108.4
C25—C24—H24D	107.8	C24—C23A—O10	116.4 (8)
H24A—C24—H24B	107.7	C24—C23A—C26	111.9 (8)
H24C—C24—H24D	107.1	C24—C23A—H23A	108.4
C23B—C24—C25	113.4 (3)	C26—C23A—H23A	108.4
C23B—C24—H24A	108.9	C10—C9A—H9AA	111.4
C23B—C24—H24B	108.9	C10—C9A—H9AB	111.4
C23A—C24—C25	118.0 (4)	H9AA—C9A—H9AB	109.2
C23A—C24—H24C	107.8	C8A—C9A—C10	102.0 (8)
C23A—C24—H24D	107.8	C8A—C9A—H9AA	111.4
O10—C23B—H23B	109.2	C8A—C9A—H9AB	111.4
O10—C23B—C26	103.8 (4)	O3—C8A—C5	102.6 (7)
C24—C23B—O10	112.7 (4)	O3—C8A—C9A	114.8 (9)
C24—C23B—H23B	109.2	O3—C8A—H8A	109.7
C24—C23B—C26	112.5 (4)	C5—C8A—H8A	109.7
C26—C23B—H23B	109.2	C9A—C8A—C5	110.0 (8)
C31—C26—C23B	113.7 (5)	C9A—C8A—H8A	109.7
K1—O8—C19—C18	−40.8 (6)	C23B—C26—C27—C28	178.1 (5)
K1—O8—C19—C20	139.6 (3)	C26—C31—C30—C29	−0.5 (9)
K1^vi—O11—C28—C29	9.5 (10)	C31—C26—C27—C28	2.9 (9)
K1^vi—O11—C28—C27	−173.9 (5)	C31—C26—C23A—O10	−48.7 (14)
K1^vi—O12—C29—C30	−180.0 (4)	C31—C26—C23A—C24	77.1 (12)
K1^vi—O12—C29—C28	−2.8 (5)	C31—C30—C29—O12	−179.3 (5)
K2—O9—C25—C20	−156.2 (3)	C31—C30—C29—C28	3.5 (8)
K2—O9—C25—C24	21.3 (6)	C30—C29—C28—O11	173.3 (6)
K2—O5—C16—C15	−62.1 (5)	C30—C29—C28—C27	−3.4 (8)
K2—O5—C16—C11	119.2 (3)	C29—C28—C27—C26	0.2 (10)
K2^vii—O2—C3—C4	175.7 (2)	C27—C26—C31—C30	−2.7 (8)
K2^vii—O2—C3—C2	−3.8 (4)	C27—C26—C23A—O10	125.8 (8)
K2^vii—O1—C2—C3	6.4 (4)	C27—C26—C23A—C24	−108.4 (9)
K2^vii—O1—C2—C7	−173.7 (3)	C32—O12—C29—C30	0.0 (7)
O8—C19—C18—C17	179.8 (4)	C32—O12—C29—C28	177.2 (5)
O8—C19—C20—C21	179.4 (4)	C16—C15—C14—O6	−179.9 (4)
O8—C19—C20—C25	−3.9 (7)	C16—C15—C14—C13	−0.5 (6)
O7—C17—C22—C21	178.6 (3)	C16—C11—C10—O4	−1.6 (8)
O10—C21—C20—C19	179.2 (4)	C16—C11—C10—C9B	163.9 (6)
O10—C21—C20—C25	2.5 (6)	C16—C11—C10—C9A	−164.9 (8)
O10—C23B—C26—C31	−106.9 (5)	C15—C16—C11—C12	−1.3 (6)
O10—C23B—C26—C27	77.7 (6)	C15—C16—C11—C10	179.9 (4)
O9—C25—C24—C23B	153.6 (5)	C15—C14—C13—C12	0.4 (6)
O9—C25—C24—C23A	−163.3 (8)	C14—C13—C12—O3	177.8 (4)
O11—C28—C27—C26	−176.4 (7)	C14—C13—C12—C11	−0.8 (6)
O12—C29—C28—O11	−4.0 (8)	C13—C12—C11—C16	1.2 (6)
O12—C29—C28—C27	179.3 (5)	C13—C12—C11—C10	−180.0 (4)
O5—C16—C15—C14	−177.7 (4)	C12—O3—C8B—C9B	47.7 (9)
O5—C16—C11—C12	177.4 (4)	C12—O3—C8B—C5	168.6 (4)
O5—C16—C11—C10	−1.5 (6)	C12—O3—C8A—C5	−169.9 (5)
O6—C14—C13—C12	179.8 (4)	C12—O3—C8A—C9A	−50.6 (12)
O3—C12—C11—C16	−177.3 (4)	C12—C11—C10—O4	179.6 (5)
O3—C12—C11—C10	1.5 (6)	C12—C11—C10—C9B	−14.9 (8)
O3—C8B—C5—C4	108.0 (6)	C12—C11—C10—C9A	16.3 (10)
O3—C8B—C5—C6	−71.8 (7)	C11—C16—C15—C14	1.0 (6)
O4—C10—C9B—C8B	−152.7 (8)	C11—C10—C9B—C8B	41.8 (10)
O4—C10—C9A—C8A	151.2 (8)	C11—C10—C9A—C8A	−44.8 (12)
O2—C3—C2—O1	−1.6 (4)	C10—C9B—C8B—O3	−59.7 (11)
O2—C3—C2—C7	178.5 (3)	C10—C9B—C8B—C5	−178.1 (7)
O1—C2—C7—C6	−178.8 (3)	C10—C9A—C8A—O3	62.7 (13)
C19—C18—C17—O7	−178.8 (4)	C10—C9A—C8A—C5	177.8 (9)
C19—C18—C17—C22	1.5 (6)	C9B—C8B—C5—C4	−128.2 (7)
C19—C20—C25—O9	2.8 (7)	C9B—C8B—C5—C6	52.0 (9)
C19—C20—C25—C24	−174.8 (4)	C8B—O3—C12—C13	164.6 (6)
C18—C19—C20—C21	−0.2 (6)	C8B—O3—C12—C11	−16.8 (7)
C18—C19—C20—C25	176.5 (4)	C8B—C5—C4—C3	−179.7 (4)
C18—C17—C22—C21	−1.7 (5)	C8B—C5—C6—C7	179.7 (4)
C17—C22—C21—O10	−178.3 (3)	C5—C4—C3—O2	−179.1 (3)
C17—C22—C21—C20	1.0 (6)	C5—C4—C3—C2	0.4 (5)
C22—C21—C20—C19	0.0 (6)	C4—C5—C6—C7	−0.1 (6)
C22—C21—C20—C25	−176.7 (4)	C4—C5—C8A—O3	73.2 (10)
C21—O10—C23B—C24	−47.7 (6)	C4—C5—C8A—C9A	−49.4 (13)
C21—O10—C23B—C26	−169.7 (4)	C4—C3—C2—O1	178.9 (3)
C21—O10—C23A—C24	38.3 (13)	C4—C3—C2—C7	−1.0 (5)
C21—O10—C23A—C26	161.1 (5)	C3—C2—C7—C6	1.1 (6)
C21—C20—C25—O9	179.4 (4)	C2—C7—C6—C5	−0.5 (6)
C21—C20—C25—C24	1.7 (6)	C6—C5—C4—C3	0.1 (6)
C20—C19—C18—C17	−0.6 (7)	C6—C5—C8A—O3	−109.2 (8)
C20—C25—C24—C23B	−28.7 (6)	C6—C5—C8A—C9A	128.2 (10)
C20—C25—C24—C23A	14.4 (10)	C1—O1—C2—C3	178.1 (3)
C25—C24—C23B—O10	51.3 (6)	C1—O1—C2—C7	−1.9 (5)
C25—C24—C23B—C26	168.3 (4)	C23A—O10—C21—C22	156.8 (8)
C25—C24—C23A—O10	−34.2 (14)	C23A—O10—C21—C20	−22.4 (9)
C25—C24—C23A—C26	−152.3 (6)	C23A—C26—C31—C30	171.0 (8)
C24—C23B—C26—C31	130.9 (5)	C23A—C26—C27—C28	−173.8 (7)
C24—C23B—C26—C27	−44.5 (7)	C8A—O3—C12—C13	−164.4 (8)
C23B—O10—C21—C22	−160.2 (4)	C8A—O3—C12—C11	14.2 (8)
C23B—O10—C21—C20	20.5 (5)	C8A—C5—C4—C3	177.5 (6)
C23B—C26—C31—C30	−178.5 (5)	C8A—C5—C6—C7	−178.2 (5)

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

(HESKHE_xMeOH)

Crystal data

C32H27KO12·CH4O	F(000) = 2816
Mr = 674.68	Dx = 1.340 Mg m^−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
a = 19.6211 (3) Å	Cell parameters from 9446 reflections
b = 20.3628 (3) Å	θ = 4.3–66.6°
c = 17.2684 (3) Å	µ = 1.96 mm^−1
β = 104.282 (1)°	T = 113 K
V = 6686.19 (19) Å^3	Block, clear light colourless
Z = 8	0.24 × 0.13 × 0.13 mm

Data collection

Bruker APEX-II CCD diffractometer	5781 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.040
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1062 before and 0.0742 after correction. The Ratio of minimum to maximum transmission is 0.7893. The λ/2 correction factor is Not present.	θmax = 66.6°, θmin = 3.2°
Tmin = 0.594, Tmax = 0.753	h = −23→23
39471 measured reflections	k = −24→24
5880 independent reflections	l = −20→18

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0587P)^2 + 17.3819P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.001
5880 reflections	Δρmax = 0.47 e Å^−3
541 parameters	Δρmin = −0.50 e Å^−3
405 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)
O1	1.42442 (8)	0.47142 (8)	0.62350 (10)	0.0246 (4)
O10	0.69240 (8)	0.14689 (8)	0.59480 (11)	0.0265 (4)
O3	1.27722 (9)	0.20547 (8)	0.64512 (12)	0.0338 (4)
O7	0.70178 (9)	0.37713 (8)	0.58598 (11)	0.0271 (4)
O5	1.06624 (9)	0.08771 (9)	0.64779 (12)	0.0326 (4)
O6	1.27497 (10)	−0.02504 (9)	0.63484 (13)	0.0374 (5)
H6	1.246394	−0.054755	0.614662	0.056*
O2	1.42580 (10)	0.42775 (9)	0.76558 (12)	0.0353 (4)
O9	0.90812 (9)	0.13203 (9)	0.66018 (13)	0.0383 (5)
O12	0.52976 (11)	−0.11595 (9)	0.60134 (12)	0.0400 (5)
O1M	0.56731 (10)	0.37986 (10)	0.59010 (13)	0.0399 (5)
H1M	0.608077	0.374937	0.583714	0.060*
O8	0.91560 (9)	0.25886 (10)	0.64986 (15)	0.0420 (5)
O4	1.07156 (11)	0.21337 (10)	0.65880 (18)	0.0562 (7)
C22	0.69791 (12)	0.26133 (11)	0.58905 (15)	0.0240 (5)
C21	0.73284 (12)	0.20190 (11)	0.60201 (14)	0.0221 (5)
C2	1.37831 (12)	0.42160 (11)	0.62669 (16)	0.0263 (5)
C20	0.80714 (12)	0.19892 (11)	0.62340 (15)	0.0242 (5)
C16	1.13538 (13)	0.08834 (12)	0.64758 (15)	0.0262 (5)
C18	0.81021 (13)	0.31884 (12)	0.61718 (16)	0.0268 (5)
C3	1.37987 (14)	0.39830 (12)	0.70372 (17)	0.0297 (5)
C15	1.16916 (13)	0.02995 (12)	0.64302 (15)	0.0269 (5)
H15	1.144864	−0.010484	0.642298	0.032*
C19	0.84449 (13)	0.25927 (12)	0.62973 (16)	0.0279 (5)
C12	1.24092 (13)	0.14854 (12)	0.64645 (16)	0.0283 (5)
C1	1.42343 (14)	0.49823 (13)	0.54639 (15)	0.0311 (6)
H1A	1.376469	0.515572	0.521913	0.047*
H1B	1.435091	0.463698	0.512267	0.047*
H1C	1.458070	0.533722	0.552325	0.047*
C14	1.23995 (13)	0.03042 (12)	0.63942 (16)	0.0292 (5)
C25	0.84279 (13)	0.13730 (12)	0.64089 (16)	0.0292 (5)
C29A	0.5788 (3)	−0.0682 (2)	0.5912 (3)	0.0298 (10)	0.702 (4)
C11	1.16978 (13)	0.14985 (12)	0.65045 (16)	0.0280 (5)
C13	1.27552 (13)	0.09058 (13)	0.64125 (17)	0.0323 (6)
H13	1.323378	0.091187	0.638892	0.039*
C7	1.33188 (15)	0.39512 (14)	0.56097 (19)	0.0394 (7)
H7	1.329759	0.411665	0.508990	0.047*
C4	1.33603 (16)	0.34748 (13)	0.7133 (2)	0.0410 (7)
O11A	0.61667 (17)	−0.07199 (16)	0.73298 (18)	0.0461 (8)	0.702 (4)
C5	1.29001 (16)	0.31962 (14)	0.6472 (2)	0.0484 (8)
C24	0.79637 (15)	0.07845 (13)	0.6386 (2)	0.0413 (7)
H24A	0.820221	0.039506	0.623178	0.050*	0.702 (4)
H24B	0.789948	0.070567	0.692916	0.050*	0.702 (4)
H24C	0.797270	0.052460	0.590401	0.050*	0.298 (4)
H24D	0.816843	0.050753	0.685703	0.050*	0.298 (4)
C6	1.28791 (17)	0.34364 (15)	0.5716 (2)	0.0531 (9)
H6A	1.256184	0.324898	0.526413	0.064*
C26A	0.6756 (2)	0.0308 (2)	0.5847 (3)	0.0276 (9)	0.702 (4)
C10	1.13376 (15)	0.21052 (14)	0.6547 (2)	0.0448 (7)
C32	0.4924 (2)	−0.14647 (18)	0.5292 (2)	0.0580 (10)
H32A	0.458811	−0.178233	0.541061	0.087*
H32B	0.525629	−0.169206	0.504456	0.087*
H32C	0.466949	−0.112993	0.492452	0.087*
C1M	0.52138 (16)	0.33525 (16)	0.5411 (2)	0.0537 (9)
H1MA	0.529279	0.291127	0.564200	0.080*
H1MB	0.530235	0.335064	0.487636	0.080*
H1MC	0.472631	0.348477	0.537177	0.080*
C23A	0.72675 (18)	0.08530 (15)	0.5826 (2)	0.0245 (8)	0.702 (4)
H23A	0.734247	0.086517	0.527422	0.029*	0.702 (4)
C28A	0.6228 (2)	−0.04504 (19)	0.6621 (2)	0.0333 (9)	0.702 (4)
C30A	0.5852 (3)	−0.0430 (2)	0.5186 (3)	0.0366 (10)	0.702 (4)
H30A	0.555711	−0.059136	0.470233	0.044*	0.702 (4)
C31A	0.6343 (2)	0.0058 (2)	0.5160 (3)	0.0353 (9)	0.702 (4)
H31A	0.639019	0.021767	0.465889	0.042*	0.702 (4)
C8B	1.2480 (2)	0.2624 (2)	0.6706 (4)	0.0375 (10)	0.702 (4)
H8B	1.257823	0.261147	0.730214	0.045*	0.702 (4)
C27A	0.6704 (2)	0.0045 (2)	0.6583 (3)	0.0356 (9)	0.702 (4)
H27A	0.700070	0.021038	0.706342	0.043*	0.702 (4)
C9B	1.1717 (2)	0.2709 (2)	0.6383 (4)	0.0413 (10)	0.702 (4)
H9BA	1.161345	0.278780	0.580022	0.050*	0.702 (4)
H9BB	1.155274	0.309474	0.663595	0.050*	0.702 (4)
C23B	0.7241 (5)	0.0916 (4)	0.6378 (7)	0.0327 (17)	0.298 (4)
H23B	0.725210	0.102040	0.694652	0.039*	0.298 (4)
C8A	1.2344 (5)	0.2650 (4)	0.6242 (7)	0.0244 (17)	0.298 (4)
H8A	1.207846	0.266489	0.566820	0.029*	0.298 (4)
C9A	1.1859 (5)	0.2734 (4)	0.6844 (6)	0.0222 (16)	0.298 (4)
H9AA	1.160101	0.315611	0.676739	0.027*	0.298 (4)
H9AB	1.212683	0.269052	0.740790	0.027*	0.298 (4)
O11B	0.5509 (6)	−0.0353 (5)	0.7266 (6)	0.066 (3)	0.298 (4)
C30B	0.6085 (5)	−0.0573 (4)	0.5430 (5)	0.042 (2)	0.298 (4)
H30B	0.599377	−0.085388	0.497662	0.050*	0.298 (4)
C31B	0.6575 (4)	−0.0069 (4)	0.5498 (5)	0.0439 (19)	0.298 (4)
H31B	0.681811	−0.000633	0.509168	0.053*	0.298 (4)
C26B	0.6708 (4)	0.0342 (4)	0.6161 (5)	0.0308 (19)	0.298 (4)
C27B	0.6352 (4)	0.0249 (3)	0.6756 (4)	0.0451 (19)	0.298 (4)
H27B	0.644340	0.053023	0.720882	0.054*	0.298 (4)
C28B	0.5862 (5)	−0.0254 (4)	0.6687 (5)	0.0421 (19)	0.298 (4)
C29B	0.5729 (5)	−0.0665 (4)	0.6024 (6)	0.034 (3)	0.298 (4)
H2	1.4273 (18)	0.4075 (17)	0.808 (2)	0.045 (9)*
H8	0.926 (2)	0.222 (2)	0.658 (3)	0.070 (13)*
H4	1.3356 (16)	0.3299 (16)	0.767 (2)	0.039 (8)*
K1	1.000000	0.03538 (3)	0.750000	0.02226 (18)
K2	1.000000	0.34682 (5)	0.750000	0.0462 (2)
C17	0.73600 (12)	0.32064 (11)	0.59701 (14)	0.0227 (5)
H18	0.8364 (14)	0.3618 (14)	0.6230 (16)	0.024 (7)*
H22	0.6474 (16)	0.2626 (14)	0.5733 (17)	0.029 (7)*
H5	1.0576 (19)	0.127 (2)	0.659 (2)	0.052 (10)*
H11A	0.648 (3)	−0.057 (3)	0.773 (3)	0.09 (2)*	0.7053
H11B	0.546 (9)	0.002 (4)	0.747 (9)	0.09 (6)*	0.2947

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0235 (8)	0.0195 (8)	0.0311 (9)	−0.0082 (6)	0.0074 (7)	0.0010 (6)
O10	0.0209 (8)	0.0151 (8)	0.0423 (10)	−0.0012 (6)	0.0052 (7)	0.0006 (7)
O3	0.0252 (9)	0.0214 (9)	0.0562 (12)	−0.0096 (7)	0.0130 (8)	−0.0005 (8)
O7	0.0239 (8)	0.0145 (8)	0.0423 (10)	0.0022 (6)	0.0069 (7)	0.0014 (7)
O5	0.0225 (9)	0.0223 (9)	0.0548 (12)	−0.0046 (7)	0.0132 (8)	0.0059 (8)
O6	0.0278 (9)	0.0254 (9)	0.0591 (13)	−0.0043 (7)	0.0108 (9)	−0.0123 (9)
O2	0.0415 (11)	0.0310 (10)	0.0363 (11)	−0.0096 (8)	0.0152 (9)	0.0057 (8)
O9	0.0215 (9)	0.0221 (9)	0.0678 (14)	0.0040 (7)	0.0045 (9)	0.0084 (9)
O12	0.0430 (11)	0.0276 (10)	0.0489 (12)	−0.0167 (8)	0.0102 (9)	−0.0030 (8)
O1M	0.0330 (10)	0.0396 (11)	0.0503 (12)	−0.0025 (9)	0.0162 (9)	−0.0141 (9)
O8	0.0180 (9)	0.0202 (9)	0.0845 (16)	0.0001 (7)	0.0063 (9)	0.0097 (10)
O4	0.0304 (11)	0.0256 (10)	0.119 (2)	0.0016 (8)	0.0318 (12)	0.0173 (12)
C22	0.0181 (12)	0.0192 (11)	0.0338 (13)	0.0006 (9)	0.0047 (9)	0.0006 (9)
C21	0.0216 (11)	0.0168 (11)	0.0273 (12)	−0.0021 (9)	0.0051 (9)	0.0007 (9)
C2	0.0218 (11)	0.0148 (11)	0.0458 (14)	−0.0045 (9)	0.0147 (10)	−0.0044 (10)
C20	0.0219 (12)	0.0168 (11)	0.0336 (13)	0.0005 (9)	0.0061 (10)	0.0031 (9)
C16	0.0224 (12)	0.0236 (12)	0.0318 (13)	−0.0060 (9)	0.0048 (10)	0.0039 (10)
C18	0.0238 (12)	0.0172 (11)	0.0384 (14)	−0.0028 (9)	0.0058 (10)	0.0051 (10)
C3	0.0290 (13)	0.0191 (11)	0.0464 (15)	−0.0024 (10)	0.0198 (11)	0.0003 (10)
C15	0.0264 (12)	0.0209 (12)	0.0331 (13)	−0.0071 (9)	0.0068 (10)	0.0010 (9)
C19	0.0205 (12)	0.0211 (12)	0.0410 (14)	−0.0018 (9)	0.0055 (10)	0.0051 (10)
C12	0.0244 (12)	0.0219 (12)	0.0376 (14)	−0.0090 (9)	0.0057 (10)	−0.0006 (10)
C1	0.0325 (13)	0.0315 (13)	0.0303 (13)	−0.0088 (11)	0.0095 (11)	0.0035 (10)
C14	0.0275 (13)	0.0228 (12)	0.0365 (14)	−0.0026 (10)	0.0062 (10)	−0.0032 (10)
C25	0.0254 (13)	0.0191 (12)	0.0424 (14)	0.0017 (10)	0.0070 (11)	0.0041 (10)
C29A	0.028 (2)	0.0168 (19)	0.045 (2)	−0.0066 (16)	0.0111 (18)	−0.0014 (17)
C11	0.0243 (12)	0.0222 (12)	0.0372 (13)	−0.0049 (9)	0.0073 (10)	0.0044 (10)
C13	0.0218 (12)	0.0270 (13)	0.0481 (15)	−0.0052 (10)	0.0086 (11)	−0.0027 (11)
C7	0.0334 (14)	0.0323 (14)	0.0533 (17)	−0.0114 (12)	0.0127 (13)	−0.0139 (13)
C4	0.0395 (15)	0.0215 (13)	0.071 (2)	−0.0050 (11)	0.0315 (15)	0.0035 (13)
O11A	0.0488 (19)	0.0454 (18)	0.0402 (17)	−0.0186 (14)	0.0035 (14)	0.0062 (14)
C5	0.0385 (16)	0.0229 (13)	0.092 (2)	−0.0099 (12)	0.0324 (16)	−0.0046 (14)
C24	0.0295 (14)	0.0175 (12)	0.075 (2)	0.0013 (10)	0.0083 (13)	0.0082 (12)
C6	0.0366 (16)	0.0350 (16)	0.088 (2)	−0.0183 (13)	0.0159 (16)	−0.0263 (16)
C26A	0.0318 (18)	0.0195 (17)	0.033 (2)	0.0001 (14)	0.0107 (16)	0.0046 (17)
C10	0.0318 (15)	0.0232 (13)	0.083 (2)	−0.0039 (11)	0.0211 (14)	0.0101 (14)
C32	0.063 (2)	0.058 (2)	0.053 (2)	−0.0366 (18)	0.0151 (17)	−0.0145 (16)
C1M	0.0326 (16)	0.0380 (17)	0.083 (2)	0.0034 (13)	−0.0004 (16)	−0.0148 (16)
C23A	0.0258 (17)	0.0131 (15)	0.034 (2)	0.0001 (12)	0.0066 (14)	0.0038 (13)
C28A	0.035 (2)	0.0228 (18)	0.0408 (19)	−0.0029 (15)	0.0080 (17)	0.0057 (15)
C30A	0.032 (2)	0.039 (2)	0.035 (2)	−0.0081 (17)	0.0010 (17)	0.0011 (17)
C31A	0.035 (2)	0.038 (2)	0.031 (2)	−0.0062 (17)	0.0037 (16)	0.0087 (17)
C8B	0.037 (2)	0.0208 (18)	0.058 (3)	−0.0111 (16)	0.018 (2)	−0.005 (2)
C27A	0.039 (2)	0.0250 (18)	0.039 (2)	−0.0079 (16)	0.0032 (17)	−0.0044 (16)
C9B	0.038 (2)	0.0221 (19)	0.067 (3)	−0.0052 (16)	0.019 (2)	0.003 (2)
C23B	0.030 (3)	0.020 (3)	0.047 (4)	−0.002 (3)	0.006 (3)	0.004 (3)
C8A	0.028 (4)	0.017 (3)	0.033 (4)	−0.005 (3)	0.017 (3)	−0.002 (3)
C9A	0.025 (3)	0.013 (3)	0.033 (4)	−0.006 (3)	0.015 (3)	−0.001 (3)
O11B	0.083 (7)	0.057 (6)	0.064 (6)	−0.028 (5)	0.029 (5)	−0.015 (4)
C30B	0.037 (4)	0.037 (4)	0.052 (4)	−0.006 (4)	0.014 (4)	−0.005 (4)
C31B	0.040 (4)	0.040 (4)	0.054 (4)	−0.008 (3)	0.017 (3)	0.004 (4)
C26B	0.030 (3)	0.015 (3)	0.046 (4)	−0.005 (3)	0.005 (3)	0.008 (3)
C27B	0.039 (4)	0.032 (4)	0.059 (4)	−0.011 (3)	0.003 (4)	0.000 (3)
C28B	0.037 (4)	0.029 (4)	0.057 (4)	−0.010 (3)	0.006 (3)	0.001 (3)
C29B	0.030 (4)	0.025 (4)	0.049 (4)	−0.003 (4)	0.013 (4)	0.004 (4)
K1	0.0177 (3)	0.0167 (3)	0.0319 (4)	0.000	0.0052 (3)	0.000
K2	0.0560 (6)	0.0426 (5)	0.0388 (5)	0.000	0.0093 (4)	0.000
C17	0.0243 (12)	0.0179 (11)	0.0265 (12)	0.0015 (9)	0.0070 (9)	0.0025 (9)

Geometric parameters (Å, º)

O1—C2	1.369 (3)	C7—H7	0.9500
O1—C1	1.435 (3)	C7—C6	1.398 (4)
O1—K1^i	2.6587 (16)	C4—C5	1.390 (5)
O10—C21	1.361 (3)	C4—H4	1.00 (3)
O10—C23A	1.463 (4)	O11A—C28A	1.374 (5)
O10—C23B	1.406 (9)	O11A—K2^ii	2.897 (3)
O3—C12	1.364 (3)	O11A—H11A	0.85 (2)
O3—C8B	1.410 (5)	C5—C6	1.385 (5)
O3—C8A	1.467 (10)	C5—C8B	1.537 (5)
O7—C17	1.322 (3)	C5—C8A	1.540 (9)
O5—C16	1.357 (3)	C24—H24A	0.9900
O5—K1	2.6594 (18)	C24—H24B	0.9900
O5—H5	0.85 (4)	C24—H24C	0.9900
O6—H6	0.8400	C24—H24D	0.9900
O6—C14	1.334 (3)	C24—C23A	1.473 (5)
O2—C3	1.356 (3)	C24—C23B	1.440 (10)
O2—H2	0.83 (4)	C6—H6A	0.9500
O2—K1^i	2.6810 (19)	C26A—C23A	1.502 (5)
O9—C25	1.247 (3)	C26A—C31A	1.359 (6)
O9—K1	2.8548 (18)	C26A—C27A	1.406 (6)
O12—C29A	1.410 (5)	C10—C9B	1.499 (5)
O12—C32	1.423 (4)	C10—C9A	1.640 (9)
O12—C29B	1.312 (6)	C32—H32A	0.9800
O12—K2^ii	2.871 (2)	C32—H32B	0.9800
O1M—H1M	0.8400	C32—H32C	0.9800
O1M—C1M	1.406 (4)	C1M—H1MA	0.9800
O8—C19	1.352 (3)	C1M—H1MB	0.9800
O8—H8	0.79 (4)	C1M—H1MC	0.9800
O8—K2	2.744 (2)	C23A—H23A	1.0000
O4—C10	1.241 (4)	C28A—C27A	1.388 (6)
C22—C21	1.382 (3)	C30A—H30A	0.9500
C22—C17	1.409 (3)	C30A—C31A	1.393 (6)
C22—H22	0.96 (3)	C31A—H31A	0.9500
C21—C20	1.414 (3)	C8B—H8B	1.0000
C2—C3	1.405 (4)	C8B—C9B	1.474 (7)
C2—C7	1.378 (4)	C27A—H27A	0.9500
C20—C19	1.421 (3)	C9B—H9BA	0.9900
C20—C25	1.432 (3)	C9B—H9BB	0.9900
C16—C15	1.373 (4)	C23B—H23B	1.0000
C16—C11	1.418 (3)	C23B—C26B	1.551 (10)
C18—C19	1.378 (3)	C8A—H8A	1.0000
C18—C17	1.412 (3)	C8A—C9A	1.582 (13)
C18—H18	1.01 (3)	C9A—H9AA	0.9900
C3—C4	1.381 (4)	C9A—H9AB	0.9900
C15—H15	0.9500	O11B—C28B	1.364 (11)
C15—C14	1.405 (4)	O11B—K2^ii	2.669 (9)
C12—C11	1.415 (4)	O11B—H11B	0.85 (2)
C12—C13	1.376 (4)	C30B—H30B	0.9500
C1—H1A	0.9800	C30B—C31B	1.3900
C1—H1B	0.9800	C30B—C29B	1.3900
C1—H1C	0.9800	C31B—H31B	0.9500
C14—C13	1.406 (3)	C31B—C26B	1.3900
C25—C24	1.500 (4)	C26B—C27B	1.3900
C29A—C28A	1.395 (6)	C27B—H27B	0.9500
C29A—C30A	1.387 (7)	C27B—C28B	1.3900
C11—C10	1.434 (4)	C28B—C29B	1.3900
C13—H13	0.9500	K1—H5	2.85 (4)
C2—O1—C1	117.48 (19)	O10—C23A—C26A	107.2 (3)
C2—O1—K1^i	124.75 (15)	O10—C23A—H23A	107.3
C1—O1—K1^i	116.95 (13)	C24—C23A—C26A	115.6 (3)
C21—O10—C23A	116.1 (2)	C24—C23A—H23A	107.3
C21—O10—C23B	116.0 (4)	C26A—C23A—H23A	107.3
C12—O3—C8B	116.1 (2)	O11A—C28A—C29A	118.5 (4)
C12—O3—C8A	115.9 (4)	O11A—C28A—C27A	122.7 (4)
C16—O5—K1	131.14 (15)	C27A—C28A—C29A	118.8 (4)
C16—O5—H5	104 (2)	C29A—C30A—H30A	119.7
K1—O5—H5	94 (2)	C29A—C30A—C31A	120.7 (4)
C14—O6—H6	109.5	C31A—C30A—H30A	119.7
C3—O2—H2	110 (2)	C26A—C31A—C30A	120.5 (4)
C3—O2—K1^i	123.67 (15)	C26A—C31A—H31A	119.7
K1^i—O2—H2	126 (2)	C30A—C31A—H31A	119.7
C25—O9—K1	132.39 (16)	O3—C8B—C5	104.8 (3)
C29A—O12—C32	114.4 (3)	O3—C8B—H8B	108.1
C29A—O12—K2^ii	126.1 (3)	O3—C8B—C9B	115.6 (4)
C32—O12—K2^ii	119.52 (17)	C5—C8B—H8B	108.1
C29B—O12—C32	122.6 (5)	C9B—C8B—C5	111.8 (4)
C29B—O12—K2^ii	117.5 (4)	C9B—C8B—H8B	108.1
C1M—O1M—H1M	109.5	C26A—C27A—H27A	119.3
C19—O8—H8	105 (3)	C28A—C27A—C26A	121.3 (4)
C19—O8—K2	125.60 (17)	C28A—C27A—H27A	119.3
K2—O8—H8	115 (3)	C10—C9B—H9BA	109.7
C21—C22—C17	120.3 (2)	C10—C9B—H9BB	109.7
C21—C22—H22	120.4 (17)	C8B—C9B—C10	109.7 (4)
C17—C22—H22	119.3 (17)	C8B—C9B—H9BA	109.7
O10—C21—C22	116.8 (2)	C8B—C9B—H9BB	109.7
O10—C21—C20	121.9 (2)	H9BA—C9B—H9BB	108.2
C22—C21—C20	121.2 (2)	O10—C23B—C24	117.4 (7)
O1—C2—C3	115.3 (2)	O10—C23B—H23B	104.3
O1—C2—C7	124.5 (2)	O10—C23B—C26B	107.0 (7)
C7—C2—C3	120.2 (2)	C24—C23B—H23B	104.3
C21—C20—C19	117.5 (2)	C24—C23B—C26B	117.8 (7)
C21—C20—C25	120.7 (2)	C26B—C23B—H23B	104.3
C19—C20—C25	121.7 (2)	O3—C8A—C5	102.0 (6)
O5—C16—C15	119.3 (2)	O3—C8A—H8A	113.3
O5—C16—C11	118.4 (2)	O3—C8A—C9A	109.2 (7)
C15—C16—C11	122.3 (2)	C5—C8A—H8A	113.3
C19—C18—C17	119.7 (2)	C5—C8A—C9A	104.8 (7)
C19—C18—H18	122.1 (15)	C9A—C8A—H8A	113.3
C17—C18—H18	118.2 (15)	C10—C9A—H9AA	112.2
O2—C3—C2	116.8 (2)	C10—C9A—H9AB	112.2
O2—C3—C4	123.4 (3)	C8A—C9A—C10	98.0 (6)
C4—C3—C2	119.8 (3)	C8A—C9A—H9AA	112.2
C16—C15—H15	120.2	C8A—C9A—H9AB	112.2
C16—C15—C14	119.5 (2)	H9AA—C9A—H9AB	109.8
C14—C15—H15	120.2	C28B—O11B—K2^ii	121.4 (6)
O8—C19—C20	119.6 (2)	C28B—O11B—H11B	107 (10)
O8—C19—C18	118.6 (2)	K2^ii—O11B—H11B	131 (10)
C18—C19—C20	121.8 (2)	C31B—C30B—H30B	120.0
O3—C12—C11	120.7 (2)	C31B—C30B—C29B	120.0
O3—C12—C13	117.4 (2)	C29B—C30B—H30B	120.0
C13—C12—C11	121.9 (2)	C30B—C31B—H31B	120.0
O1—C1—H1A	109.5	C30B—C31B—C26B	120.0
O1—C1—H1B	109.5	C26B—C31B—H31B	120.0
O1—C1—H1C	109.5	C31B—C26B—C23B	129.2 (6)
H1A—C1—H1B	109.5	C27B—C26B—C23B	110.8 (6)
H1A—C1—H1C	109.5	C27B—C26B—C31B	120.0
H1B—C1—H1C	109.5	C26B—C27B—H27B	120.0
O6—C14—C15	121.7 (2)	C26B—C27B—C28B	120.0
O6—C14—C13	118.6 (2)	C28B—C27B—H27B	120.0
C15—C14—C13	119.7 (2)	O11B—C28B—C27B	120.8 (6)
O9—C25—C20	123.2 (2)	O11B—C28B—C29B	119.2 (6)
O9—C25—C24	121.1 (2)	C29B—C28B—C27B	120.0
C20—C25—C24	115.6 (2)	O12—C29B—C30B	122.2 (6)
C28A—C29A—O12	114.6 (4)	O12—C29B—C28B	117.6 (6)
C30A—C29A—O12	125.7 (4)	C28B—C29B—C30B	120.0
C30A—C29A—C28A	119.6 (4)	O1^ii—K1—O1^iii	121.34 (7)
C16—C11—C10	121.8 (2)	O1^iii—K1—O5^iv	85.17 (5)
C12—C11—C16	116.6 (2)	O1^iii—K1—O5	118.47 (5)
C12—C11—C10	121.5 (2)	O1^ii—K1—O5	85.17 (5)
C12—C13—C14	119.9 (2)	O1^ii—K1—O5^iv	118.47 (5)
C12—C13—H13	120.0	O1^iii—K1—O2^ii	73.97 (6)
C14—C13—H13	120.0	O1^ii—K1—O2^iii	73.97 (6)
C2—C7—H7	120.4	O1^iii—K1—O2^iii	58.36 (6)
C2—C7—C6	119.3 (3)	O1^ii—K1—O2^ii	58.36 (6)
C6—C7—H7	120.4	O1^iii—K1—O9	159.00 (6)
C3—C4—C5	120.4 (3)	O1^iii—K1—O9^iv	75.04 (5)
C3—C4—H4	121.9 (19)	O1^ii—K1—O9	75.04 (5)
C5—C4—H4	117.7 (19)	O1^ii—K1—O9^iv	159.00 (6)
C28A—O11A—K2^ii	124.3 (2)	O1^ii—K1—H5	94.8 (7)
C28A—O11A—H11A	112 (5)	O1^iii—K1—H5	124.0 (7)
K2^ii—O11A—H11A	123 (5)	O5^iv—K1—O5	132.76 (9)
C4—C5—C8B	112.0 (4)	O5^iv—K1—O2^iii	139.51 (6)
C4—C5—C8A	141.4 (5)	O5—K1—O2^ii	139.51 (6)
C6—C5—C4	119.5 (3)	O5—K1—O2^iii	83.95 (6)
C6—C5—C8B	128.5 (4)	O5^iv—K1—O2^ii	83.95 (6)
C6—C5—C8A	99.1 (5)	O5^iv—K1—O9	74.80 (6)
C25—C24—H24A	108.8	O5—K1—O9^iv	74.80 (6)
C25—C24—H24B	108.8	O5^iv—K1—O9^iv	73.12 (6)
C25—C24—H24C	108.2	O5—K1—O9	73.12 (6)
C25—C24—H24D	108.2	O5^iv—K1—H5	115.5 (8)
H24A—C24—H24B	107.7	O5—K1—H5	17.3 (8)
H24C—C24—H24D	107.4	O2^ii—K1—O2^iii	70.34 (9)
C23A—C24—C25	113.6 (2)	O2^ii—K1—O9^iv	142.64 (6)
C23A—C24—H24A	108.8	O2^ii—K1—O9	109.41 (6)
C23A—C24—H24B	108.8	O2^iii—K1—O9^iv	109.41 (6)
C23B—C24—C25	116.2 (4)	O2^iii—K1—O9	142.64 (6)
C23B—C24—H24C	108.2	O2^ii—K1—H5	152.8 (8)
C23B—C24—H24D	108.2	O2^iii—K1—H5	100.4 (8)
C7—C6—H6A	119.6	O9^iv—K1—O9	92.83 (8)
C5—C6—C7	120.8 (3)	O9^iv—K1—H5	64.3 (7)
C5—C6—H6A	119.6	O9—K1—H5	62.1 (8)
C31A—C26A—C23A	120.9 (4)	O12^v—K2—O12^i	149.39 (8)
C31A—C26A—C27A	119.0 (4)	O12^i—K2—O11A^v	106.27 (8)
C27A—C26A—C23A	120.0 (4)	O12^i—K2—O11A^i	54.45 (7)
O4—C10—C11	123.2 (2)	O12^v—K2—O11A^v	54.45 (7)
O4—C10—C9B	120.9 (3)	O12^v—K2—O11A^i	106.27 (8)
O4—C10—C9A	119.5 (4)	O8^iv—K2—O12^i	120.77 (6)
C11—C10—C9B	115.1 (3)	O8—K2—O12^i	80.39 (6)
C11—C10—C9A	114.3 (4)	O8^iv—K2—O12^v	80.39 (6)
O12—C32—H32A	109.5	O8—K2—O12^v	120.77 (6)
O12—C32—H32B	109.5	O8—K2—O8^iv	98.49 (9)
O12—C32—H32C	109.5	O8^iv—K2—O11A^v	132.67 (8)
H32A—C32—H32B	109.5	O8—K2—O11A^v	93.86 (8)
H32A—C32—H32C	109.5	O8—K2—O11A^i	132.67 (8)
H32B—C32—H32C	109.5	O8^iv—K2—O11A^i	93.86 (8)
O1M—C1M—H1MA	109.5	O11A^i—K2—O11A^v	110.41 (14)
O1M—C1M—H1MB	109.5	O11B^v—K2—O8	119.5 (2)
O1M—C1M—H1MC	109.5	O11B^i—K2—O8	133.0 (2)
H1MA—C1M—H1MB	109.5	O7—C17—C22	119.6 (2)
H1MA—C1M—H1MC	109.5	O7—C17—C18	121.0 (2)
H1MB—C1M—H1MC	109.5	C22—C17—C18	119.5 (2)
O10—C23A—C24	111.9 (3)
O1—C2—C3—O2	0.6 (3)	C13—C12—C11—C10	−179.0 (3)
O1—C2—C3—C4	−179.1 (2)	C7—C2—C3—O2	−178.5 (2)
O1—C2—C7—C6	179.1 (2)	C7—C2—C3—C4	1.8 (4)
O10—C21—C20—C19	−179.7 (2)	C4—C5—C6—C7	0.5 (5)
O10—C21—C20—C25	−2.0 (4)	C4—C5—C8B—O3	−107.1 (4)
O10—C23B—C26B—C31B	81.8 (9)	C4—C5—C8B—C9B	126.9 (4)
O10—C23B—C26B—C27B	−100.1 (8)	C4—C5—C8A—O3	−66.5 (8)
O3—C12—C11—C16	177.0 (2)	C4—C5—C8A—C9A	47.3 (10)
O3—C12—C11—C10	−1.1 (4)	O11A—C28A—C27A—C26A	179.7 (4)
O3—C12—C13—C14	−177.7 (2)	C5—C8B—C9B—C10	173.5 (4)
O3—C8B—C9B—C10	53.7 (6)	C5—C8A—C9A—C10	−177.4 (6)
O3—C8A—C9A—C10	−68.8 (8)	C24—C23B—C26B—C31B	−53.0 (11)
O5—C16—C15—C14	177.4 (2)	C24—C23B—C26B—C27B	125.1 (8)
O5—C16—C11—C12	−177.2 (2)	C6—C5—C8B—O3	71.3 (5)
O5—C16—C11—C10	0.9 (4)	C6—C5—C8B—C9B	−54.7 (6)
O6—C14—C13—C12	−179.6 (2)	C6—C5—C8A—O3	112.7 (5)
O2—C3—C4—C5	179.8 (3)	C6—C5—C8A—C9A	−133.5 (7)
O9—C25—C24—C23A	−153.6 (3)	C32—O12—C29A—C28A	−171.0 (4)
O9—C25—C24—C23B	163.2 (6)	C32—O12—C29A—C30A	10.1 (7)
O12—C29A—C28A—O11A	2.7 (7)	C32—O12—C29B—C30B	−27.8 (9)
O12—C29A—C28A—C27A	−176.7 (4)	C32—O12—C29B—C28B	156.8 (5)
O12—C29A—C30A—C31A	177.9 (4)	C23A—O10—C21—C22	160.7 (2)
O4—C10—C9B—C8B	155.0 (4)	C23A—O10—C21—C20	−20.6 (3)
O4—C10—C9A—C8A	−148.3 (6)	C23A—C26A—C31A—C30A	−177.6 (4)
C22—C21—C20—C19	−1.0 (4)	C23A—C26A—C27A—C28A	178.9 (4)
C22—C21—C20—C25	176.6 (2)	C28A—C29A—C30A—C31A	−0.9 (9)
C21—O10—C23A—C24	46.7 (4)	C30A—C29A—C28A—O11A	−178.4 (5)
C21—O10—C23A—C26A	174.4 (3)	C30A—C29A—C28A—C27A	2.2 (8)
C21—O10—C23B—C24	−41.1 (9)	C31A—C26A—C23A—O10	96.9 (5)
C21—O10—C23B—C26B	−176.1 (5)	C31A—C26A—C23A—C24	−137.7 (4)
C21—C22—C17—O7	−178.6 (2)	C31A—C26A—C27A—C28A	−1.7 (7)
C21—C22—C17—C18	1.0 (4)	C8B—O3—C12—C11	17.6 (4)
C21—C20—C19—O8	−179.9 (2)	C8B—O3—C12—C13	−164.4 (3)
C21—C20—C19—C18	1.2 (4)	C8B—C5—C6—C7	−177.8 (3)
C21—C20—C25—O9	−179.8 (3)	C27A—C26A—C23A—O10	−83.7 (5)
C21—C20—C25—C24	−2.7 (4)	C27A—C26A—C23A—C24	41.7 (6)
C2—C3—C4—C5	−0.5 (4)	C27A—C26A—C31A—C30A	3.0 (7)
C2—C7—C6—C5	0.7 (5)	C23B—O10—C21—C22	−154.9 (6)
C20—C25—C24—C23A	29.3 (4)	C23B—O10—C21—C20	23.8 (6)
C20—C25—C24—C23B	−14.0 (6)	C23B—C26B—C27B—C28B	−178.3 (8)
C16—C15—C14—O6	−179.9 (2)	C8A—O3—C12—C11	−17.5 (6)
C16—C15—C14—C13	0.6 (4)	C8A—O3—C12—C13	160.5 (5)
C16—C11—C10—O4	2.5 (5)	C8A—C5—C6—C7	−178.9 (4)
C16—C11—C10—C9B	−166.5 (4)	O11B—C28B—C29B—O12	−4.3 (9)
C16—C11—C10—C9A	162.4 (4)	O11B—C28B—C29B—C30B	−179.8 (10)
C3—C2—C7—C6	−1.9 (4)	C30B—C31B—C26B—C23B	178.0 (10)
C3—C4—C5—C6	−0.6 (4)	C30B—C31B—C26B—C27B	0.0
C3—C4—C5—C8B	177.9 (3)	C31B—C30B—C29B—O12	−175.3 (10)
C3—C4—C5—C8A	178.4 (6)	C31B—C30B—C29B—C28B	0.0
C15—C16—C11—C12	1.5 (4)	C31B—C26B—C27B—C28B	0.0
C15—C16—C11—C10	179.6 (3)	C26B—C27B—C28B—O11B	179.8 (10)
C15—C14—C13—C12	−0.1 (4)	C26B—C27B—C28B—C29B	0.0
C19—C20—C25—O9	−2.3 (4)	C27B—C28B—C29B—O12	175.5 (10)
C19—C20—C25—C24	174.8 (3)	C27B—C28B—C29B—C30B	0.0
C19—C18—C17—O7	178.8 (2)	C29B—C30B—C31B—C26B	0.0
C19—C18—C17—C22	−0.8 (4)	K1^i—O1—C2—C3	−9.0 (3)
C12—O3—C8B—C5	−168.9 (3)	K1^i—O1—C2—C7	170.07 (19)
C12—O3—C8B—C9B	−45.3 (6)	K1—O5—C16—C15	62.0 (3)
C12—O3—C8A—C5	167.4 (4)	K1—O5—C16—C11	−119.3 (2)
C12—O3—C8A—C9A	56.9 (8)	K1^i—O2—C3—C2	7.9 (3)
C12—C11—C10—O4	−179.5 (3)	K1^i—O2—C3—C4	−172.43 (19)
C12—C11—C10—C9B	11.5 (5)	K1—O9—C25—C20	154.88 (19)
C12—C11—C10—C9A	−19.6 (6)	K1—O9—C25—C24	−22.1 (4)
C1—O1—C2—C3	−178.2 (2)	K2^ii—O12—C29A—C28A	9.8 (7)
C1—O1—C2—C7	0.8 (3)	K2^ii—O12—C29A—C30A	−169.1 (4)
C25—C20—C19—O8	2.5 (4)	K2^ii—O12—C29B—C30B	158.9 (4)
C25—C20—C19—C18	−176.4 (3)	K2^ii—O12—C29B—C28B	−16.5 (8)
C25—C24—C23A—O10	−50.6 (4)	K2—O8—C19—C20	−140.4 (2)
C25—C24—C23A—C26A	−173.6 (3)	K2—O8—C19—C18	38.5 (3)
C25—C24—C23B—O10	36.2 (10)	K2^ii—O11A—C28A—C29A	−13.8 (6)
C25—C24—C23B—C26B	166.4 (6)	K2^ii—O11A—C28A—C27A	165.6 (3)
C29A—C28A—C27A—C26A	−0.9 (7)	K2^ii—O11B—C28B—C27B	−154.3 (5)
C29A—C30A—C31A—C26A	−1.8 (8)	K2^ii—O11B—C28B—C29B	25.6 (10)
C11—C16—C15—C14	−1.3 (4)	C17—C22—C21—O10	178.7 (2)
C11—C12—C13—C14	0.3 (4)	C17—C22—C21—C20	0.0 (4)
C11—C10—C9B—C8B	−35.7 (6)	C17—C18—C19—O8	−179.3 (2)
C11—C10—C9A—C8A	51.0 (8)	C17—C18—C19—C20	−0.4 (4)
C13—C12—C11—C16	−1.0 (4)

Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y−1/2, z; (iii) −x+5/2, y−1/2, −z+3/2; (iv) −x+2, y, −z+3/2; (v) −x+3/2, y+1/2, −z+3/2.

(HESK_3H2O)

Crystal data

C16H17KO8·H2O	Dx = 1.520 Mg m^−3
Mr = 394.41	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 9265 reflections
a = 13.9343 (3) Å	θ = 4.2–66.5°
b = 7.8657 (2) Å	µ = 3.15 mm^−1
c = 31.4425 (7) Å	T = 113 K
V = 3446.19 (14) Å^3	Plate, clear light colourless
Z = 8	0.02 × 0.02 × 0.02 mm
F(000) = 1648

Data collection

Bruker APEX-II CCD diffractometer	2903 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.071
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0900 before and 0.0719 after correction. The Ratio of minimum to maximum transmission is 0.7197. The λ/2 correction factor is Not present.	θmax = 66.6°, θmin = 2.8°
Tmin = 0.542, Tmax = 0.753	h = −14→16
29419 measured reflections	k = −9→9
3040 independent reflections	l = −37→37

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0493P)^2 + 5.4499P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
3040 reflections	Δρmax = 0.48 e Å^−3
267 parameters	Δρmin = −0.35 e Å^−3
19 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)
K1	0.93794 (3)	0.42338 (7)	0.34963 (2)	0.02174 (17)
O3	0.41452 (11)	0.7079 (2)	0.37317 (5)	0.0192 (4)
O1	0.83514 (11)	0.5921 (2)	0.42278 (5)	0.0238 (4)
O2W	0.92288 (12)	0.1826 (2)	0.28438 (5)	0.0242 (4)
H2WA	0.883694	0.220025	0.264940	0.036*
H2WB	0.895321	0.091328	0.294168	0.036*
O6	0.19745 (11)	0.8684 (2)	0.26554 (5)	0.0214 (4)
O1W	0.93277 (12)	0.5825 (2)	0.27032 (5)	0.0234 (4)
H1WA	0.897981	0.522620	0.252877	0.035*
H1WB	0.989935	0.581369	0.259147	0.035*
O5	0.07517 (12)	0.6221 (2)	0.39138 (5)	0.0247 (4)
O3W	0.66364 (12)	0.3677 (2)	0.28966 (5)	0.0243 (4)
H3WA	0.707535	0.373923	0.270053	0.036*
H3WB	0.633367	0.273406	0.284295	0.036*
O2	0.74982 (13)	0.4384 (2)	0.36021 (5)	0.0265 (4)
O4	0.19469 (14)	0.5509 (3)	0.45062 (6)	0.0407 (5)
C12	0.32182 (16)	0.7183 (3)	0.35877 (7)	0.0170 (5)
C13	0.30729 (16)	0.7879 (3)	0.31957 (7)	0.0181 (5)
H13	0.360510	0.825192	0.303151	0.022*
C14	0.21237 (16)	0.8047 (3)	0.30317 (7)	0.0184 (5)
C16	0.15099 (16)	0.6770 (3)	0.36762 (7)	0.0190 (5)
C11	0.24496 (16)	0.6618 (3)	0.38489 (7)	0.0180 (5)
C2	0.73726 (17)	0.5971 (3)	0.42350 (7)	0.0210 (5)
C3	0.69204 (17)	0.5147 (3)	0.38907 (7)	0.0218 (5)
C15	0.13460 (16)	0.7472 (3)	0.32850 (7)	0.0197 (5)
H15	0.070758	0.757541	0.318226	0.024*
C4	0.59346 (18)	0.5147 (4)	0.38606 (8)	0.0294 (6)
H4	0.563562	0.457614	0.362974	0.035*
C10	0.26110 (19)	0.5975 (4)	0.42632 (8)	0.0288 (6)
C7	0.68115 (19)	0.6758 (3)	0.45401 (8)	0.0284 (6)
H7	0.710478	0.730136	0.477657	0.034*
C1	0.88317 (19)	0.6626 (4)	0.45878 (8)	0.0308 (6)
H1A	0.952594	0.647345	0.455558	0.046*
H1B	0.861479	0.604768	0.484654	0.046*
H1C	0.868432	0.784164	0.460842	0.046*
C5	0.53695 (19)	0.5965 (5)	0.41605 (9)	0.0392 (8)
C6	0.5809 (2)	0.6751 (4)	0.44997 (9)	0.0384 (7)
H6	0.542725	0.729780	0.470954	0.046*
C9A	0.3609 (3)	0.6124 (10)	0.44287 (14)	0.0195 (13)	0.675 (18)
H9AA	0.371969	0.527746	0.465650	0.023*	0.675 (18)
H9AB	0.371738	0.727353	0.454729	0.023*	0.675 (18)
C8A	0.4285 (2)	0.5802 (5)	0.40576 (10)	0.0189 (11)	0.724 (10)
H8A	0.415408	0.465062	0.393561	0.023*	0.724 (10)
C9B	0.3708 (6)	0.539 (2)	0.4357 (4)	0.018 (3)	0.325 (18)
H9BA	0.381406	0.526169	0.466647	0.021*	0.325 (18)
H9BB	0.384212	0.428405	0.421774	0.021*	0.325 (18)
C8B	0.4367 (6)	0.6770 (14)	0.4176 (3)	0.016 (2)	0.276 (10)
H8B	0.435254	0.783559	0.434988	0.019*	0.276 (10)
H5	0.0997 (19)	0.580 (3)	0.4141 (7)	0.019*
H2	0.7176 (18)	0.409 (3)	0.3383 (7)	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0159 (3)	0.0274 (3)	0.0220 (3)	0.00165 (19)	−0.00217 (18)	−0.0022 (2)
O3	0.0148 (7)	0.0265 (9)	0.0164 (7)	−0.0031 (7)	−0.0019 (6)	0.0046 (6)
O1	0.0162 (8)	0.0347 (10)	0.0206 (8)	−0.0030 (7)	−0.0005 (6)	−0.0025 (7)
O2W	0.0234 (8)	0.0247 (9)	0.0245 (9)	0.0002 (7)	−0.0038 (7)	0.0021 (7)
O6	0.0180 (8)	0.0263 (9)	0.0200 (8)	0.0028 (7)	−0.0027 (6)	0.0016 (7)
O1W	0.0204 (8)	0.0263 (9)	0.0237 (8)	−0.0024 (7)	−0.0029 (7)	−0.0025 (7)
O5	0.0159 (8)	0.0330 (10)	0.0251 (9)	−0.0036 (7)	0.0055 (7)	0.0004 (8)
O3W	0.0223 (9)	0.0271 (9)	0.0234 (9)	−0.0009 (7)	−0.0004 (7)	−0.0034 (7)
O2	0.0182 (8)	0.0379 (10)	0.0234 (8)	0.0014 (8)	−0.0043 (7)	−0.0047 (8)
O4	0.0262 (10)	0.0728 (15)	0.0232 (9)	−0.0178 (10)	0.0010 (7)	0.0124 (10)
C12	0.0137 (10)	0.0184 (11)	0.0189 (11)	−0.0002 (9)	0.0000 (8)	−0.0039 (9)
C13	0.0148 (10)	0.0216 (12)	0.0179 (11)	−0.0015 (9)	0.0015 (8)	−0.0009 (9)
C14	0.0187 (11)	0.0175 (11)	0.0191 (11)	0.0009 (9)	−0.0008 (9)	−0.0040 (9)
C16	0.0160 (11)	0.0179 (11)	0.0231 (11)	−0.0027 (9)	0.0053 (9)	−0.0060 (9)
C11	0.0173 (11)	0.0189 (11)	0.0179 (10)	−0.0016 (9)	0.0030 (9)	−0.0037 (9)
C2	0.0170 (11)	0.0238 (12)	0.0222 (12)	0.0015 (10)	0.0019 (9)	0.0068 (9)
C3	0.0170 (11)	0.0264 (13)	0.0220 (11)	0.0005 (10)	0.0009 (9)	0.0065 (10)
C15	0.0129 (10)	0.0206 (12)	0.0257 (12)	0.0020 (9)	−0.0003 (9)	−0.0037 (9)
C4	0.0186 (12)	0.0444 (16)	0.0251 (12)	−0.0017 (11)	−0.0032 (10)	0.0148 (12)
C10	0.0216 (13)	0.0436 (16)	0.0211 (12)	−0.0111 (11)	0.0011 (10)	0.0028 (11)
C7	0.0317 (14)	0.0309 (14)	0.0226 (12)	0.0056 (11)	0.0058 (10)	0.0056 (11)
C1	0.0267 (13)	0.0459 (17)	0.0198 (12)	−0.0103 (12)	−0.0016 (10)	−0.0001 (11)
C5	0.0181 (13)	0.075 (2)	0.0246 (13)	0.0125 (14)	0.0053 (10)	0.0278 (14)
C6	0.0321 (14)	0.0544 (19)	0.0287 (14)	0.0229 (14)	0.0153 (12)	0.0181 (13)
C9A	0.022 (2)	0.020 (3)	0.017 (2)	0.0011 (19)	0.0011 (14)	0.0009 (18)
C8A	0.0169 (17)	0.022 (2)	0.0178 (17)	−0.0003 (13)	0.0004 (12)	0.0052 (14)
C9B	0.015 (3)	0.022 (4)	0.016 (4)	−0.007 (3)	−0.007 (3)	0.001 (3)
C8B	0.016 (3)	0.016 (3)	0.016 (3)	0.0000 (10)	−0.0001 (10)	−0.0004 (10)

Geometric parameters (Å, º)

K1—O3^i	2.7653 (16)	C14—C15	1.419 (3)
K1—O1	3.0170 (17)	C16—C11	1.422 (3)
K1—O2W	2.7999 (18)	C16—C15	1.367 (3)
K1—O1W	2.7911 (18)	C11—C10	1.415 (3)
K1—O5^ii	2.7970 (18)	C2—C3	1.410 (4)
K1—O2	2.6451 (18)	C2—C7	1.384 (4)
K1—C4^i	3.440 (3)	C3—C4	1.377 (3)
K1—C5^i	3.331 (3)	C15—H15	0.9500
K1—C8B^i	3.373 (8)	C4—H4	0.9500
O3—C12	1.371 (3)	C4—C5	1.387 (4)
O3—C8A	1.448 (3)	C10—C9A	1.489 (5)
O3—C8B	1.452 (8)	C10—C9B	1.624 (10)
O1—C2	1.365 (3)	C7—H7	0.9500
O1—C1	1.427 (3)	C7—C6	1.403 (4)
O2W—H2WA	0.8709	C1—H1A	0.9800
O2W—H2WB	0.8705	C1—H1B	0.9800
O6—C14	1.302 (3)	C1—H1C	0.9800
O1W—H1WA	0.8702	C5—C6	1.376 (5)
O1W—H1WB	0.8706	C5—C8A	1.551 (4)
O5—C16	1.364 (3)	C5—C8B	1.535 (9)
O5—H5	0.859 (17)	C6—H6	0.9500
O3W—H3WA	0.8699	C9A—H9AA	0.9900
O3W—H3WB	0.8698	C9A—H9AB	0.9900
O2—C3	1.353 (3)	C9A—C8A	1.521 (6)
O2—H2	0.854 (17)	C8A—H8A	1.0000
O4—C10	1.255 (3)	C9B—H9BA	0.9900
C12—C13	1.364 (3)	C9B—H9BB	0.9900
C12—C11	1.421 (3)	C9B—C8B	1.531 (11)
C13—H13	0.9500	C8B—H8B	1.0000
C13—C14	1.426 (3)
O3^i—K1—O1	114.75 (5)	C12—C11—C16	116.5 (2)
O3^i—K1—O2W	80.64 (5)	C10—C11—C12	121.6 (2)
O3^i—K1—O1W	122.22 (5)	C10—C11—C16	121.9 (2)
O3^i—K1—O5^ii	73.07 (5)	O1—C2—C3	114.9 (2)
O3^i—K1—C4^i	55.44 (5)	O1—C2—C7	126.1 (2)
O3^i—K1—C5^i	44.03 (6)	C7—C2—C3	119.0 (2)
O3^i—K1—C8B^i	24.93 (15)	O2—C3—C2	116.9 (2)
O1—K1—C4^i	95.55 (6)	O2—C3—C4	123.2 (2)
O1—K1—C5^i	84.92 (7)	C4—C3—C2	119.9 (2)
O1—K1—C8B^i	90.88 (17)	C14—C15—H15	119.8
O2W—K1—O1	145.13 (5)	C16—C15—C14	120.4 (2)
O2W—K1—C4^i	66.58 (6)	C16—C15—H15	119.8
O2W—K1—C5^i	86.86 (7)	K1^iii—C4—H4	97.6
O2W—K1—C8B^i	96.59 (19)	C3—C4—K1^iii	98.63 (17)
O1W—K1—O1	118.14 (5)	C3—C4—H4	119.3
O1W—K1—O2W	69.30 (5)	C3—C4—C5	121.3 (3)
O1W—K1—O5^ii	100.74 (5)	C5—C4—K1^iii	73.79 (17)
O1W—K1—C4^i	135.49 (6)	C5—C4—H4	119.3
O1W—K1—C5^i	155.37 (7)	O4—C10—C11	123.2 (2)
O1W—K1—C8B^i	146.85 (15)	O4—C10—C9A	119.9 (3)
O5^ii—K1—O1	73.80 (5)	O4—C10—C9B	120.1 (4)
O5^ii—K1—O2W	140.64 (5)	C11—C10—C9A	116.2 (3)
O5^ii—K1—C4^i	116.93 (6)	C11—C10—C9B	114.7 (4)
O5^ii—K1—C5^i	93.75 (7)	C2—C7—H7	120.1
O5^ii—K1—C8B^i	70.70 (18)	C2—C7—C6	119.9 (3)
O2—K1—O3^i	136.93 (6)	C6—C7—H7	120.1
O2—K1—O1	54.12 (5)	O1—C1—H1A	109.5
O2—K1—O2W	92.76 (5)	O1—C1—H1B	109.5
O2—K1—O1W	93.83 (5)	O1—C1—H1C	109.5
O2—K1—O5^ii	126.41 (6)	H1A—C1—H1B	109.5
O2—K1—C4^i	82.75 (6)	H1A—C1—H1C	109.5
O2—K1—C5^i	93.43 (6)	H1B—C1—H1C	109.5
O2—K1—C8B^i	117.34 (14)	C4—C5—K1^iii	82.64 (16)
C5^i—K1—C4^i	23.56 (7)	C4—C5—C8A	111.9 (3)
C5^i—K1—C8B^i	26.46 (15)	C4—C5—C8B	136.9 (4)
C12—O3—K1^iii	125.12 (13)	C6—C5—K1^iii	95.3 (2)
C12—O3—C8A	113.68 (19)	C6—C5—C4	118.9 (2)
C12—O3—C8B	121.9 (3)	C6—C5—C8A	129.2 (3)
C8A—O3—K1^iii	120.99 (15)	C6—C5—C8B	101.2 (4)
C2—O1—K1	119.99 (14)	C8A—C5—K1^iii	92.03 (16)
C2—O1—C1	116.39 (19)	C7—C6—H6	119.5
C1—O1—K1	123.56 (14)	C5—C6—C7	121.0 (3)
K1—O2W—H2WA	109.4	C5—C6—H6	119.5
K1—O2W—H2WB	109.4	C10—C9A—H9AA	110.3
H2WA—O2W—H2WB	104.5	C10—C9A—H9AB	110.3
K1—O1W—H1WA	109.6	C10—C9A—C8A	107.3 (3)
K1—O1W—H1WB	109.4	H9AA—C9A—H9AB	108.5
H1WA—O1W—H1WB	104.5	C8A—C9A—H9AA	110.3
K1^iv—O5—H5	116.5 (19)	C8A—C9A—H9AB	110.3
C16—O5—K1^iv	116.70 (13)	O3—C8A—C5	102.8 (2)
C16—O5—H5	105.7 (19)	O3—C8A—C9A	110.1 (3)
H3WA—O3W—H3WB	104.6	O3—C8A—H8A	109.4
K1—O2—H2	114.1 (18)	C5—C8A—H8A	109.4
C3—O2—K1	133.92 (15)	C9A—C8A—C5	115.5 (3)
C3—O2—H2	110.3 (18)	C9A—C8A—H8A	109.4
O3—C12—C11	120.0 (2)	C10—C9B—H9BA	110.3
C13—C12—O3	117.5 (2)	C10—C9B—H9BB	110.3
C13—C12—C11	122.4 (2)	H9BA—C9B—H9BB	108.5
C12—C13—H13	119.9	C8B—C9B—C10	107.2 (8)
C12—C13—C14	120.1 (2)	C8B—C9B—H9BA	110.3
C14—C13—H13	119.9	C8B—C9B—H9BB	110.3
O6—C14—C13	120.8 (2)	O3—C8B—C5	103.4 (5)
O6—C14—C15	120.7 (2)	O3—C8B—C9B	110.4 (7)
C15—C14—C13	118.4 (2)	O3—C8B—H8B	112.4
O5—C16—C11	118.5 (2)	C5—C8B—H8B	112.4
O5—C16—C15	119.4 (2)	C9B—C8B—C5	105.3 (7)
C15—C16—C11	122.1 (2)	C9B—C8B—H8B	112.4
K1^iii—O3—C12—C13	27.5 (3)	C13—C12—C11—C16	1.6 (3)
K1^iii—O3—C12—C11	−150.93 (16)	C13—C12—C11—C10	−176.9 (2)
K1^iii—O3—C8A—C5	−4.8 (3)	C13—C14—C15—C16	−0.2 (3)
K1^iii—O3—C8A—C9A	118.7 (3)	C16—C11—C10—O4	−0.4 (4)
K1^iii—O3—C8B—C5	−59.8 (6)	C16—C11—C10—C9A	−171.2 (4)
K1^iii—O3—C8B—C9B	−172.0 (8)	C16—C11—C10—C9B	163.3 (6)
K1—O1—C2—C3	1.9 (3)	C11—C12—C13—C14	−0.6 (3)
K1—O1—C2—C7	−177.24 (19)	C11—C16—C15—C14	1.3 (4)
K1^iv—O5—C16—C11	−134.15 (17)	C11—C10—C9A—C8A	−37.5 (6)
K1^iv—O5—C16—C15	47.0 (3)	C11—C10—C9B—C8B	44.2 (11)
K1—O2—C3—C2	−5.1 (3)	C2—C3—C4—K1^iii	77.1 (2)
K1—O2—C3—C4	174.84 (18)	C2—C3—C4—C5	0.9 (4)
K1^iii—C4—C5—C6	−92.0 (3)	C2—C7—C6—C5	0.3 (4)
K1^iii—C4—C5—C8A	89.2 (2)	C3—C2—C7—C6	−1.1 (4)
K1^iii—C4—C5—C8B	64.1 (6)	C3—C4—C5—K1^iii	90.3 (2)
K1^iii—C5—C6—C7	−83.4 (3)	C3—C4—C5—C6	−1.7 (4)
K1^iii—C5—C8A—O3	3.4 (2)	C3—C4—C5—C8A	179.6 (3)
K1^iii—C5—C8A—C9A	−116.5 (4)	C3—C4—C5—C8B	154.4 (6)
K1^iii—C5—C8B—O3	45.9 (5)	C15—C16—C11—C12	−2.0 (3)
K1^iii—C5—C8B—C9B	161.7 (7)	C15—C16—C11—C10	176.5 (2)
O3—C12—C13—C14	−179.0 (2)	C4—C5—C6—C7	1.1 (4)
O3—C12—C11—C16	180.0 (2)	C4—C5—C8A—O3	−79.4 (3)
O3—C12—C11—C10	1.5 (3)	C4—C5—C8A—C9A	160.6 (4)
O1—C2—C3—O2	1.3 (3)	C4—C5—C8B—O3	−19.8 (10)
O1—C2—C3—C4	−178.7 (2)	C4—C5—C8B—C9B	96.1 (8)
O1—C2—C7—C6	178.0 (2)	C10—C9A—C8A—O3	62.0 (5)
O6—C14—C15—C16	178.6 (2)	C10—C9A—C8A—C5	177.8 (4)
O5—C16—C11—C12	179.1 (2)	C10—C9B—C8B—O3	−54.2 (11)
O5—C16—C11—C10	−2.4 (3)	C10—C9B—C8B—C5	−165.1 (7)
O5—C16—C15—C14	−179.8 (2)	C7—C2—C3—O2	−179.5 (2)
O2—C3—C4—K1^iii	−102.9 (2)	C7—C2—C3—C4	0.5 (4)
O2—C3—C4—C5	−179.1 (2)	C1—O1—C2—C3	−175.3 (2)
O4—C10—C9A—C8A	151.4 (4)	C1—O1—C2—C7	5.6 (4)
O4—C10—C9B—C8B	−151.5 (6)	C6—C5—C8A—O3	102.0 (3)
C12—O3—C8A—C5	−179.7 (2)	C6—C5—C8A—C9A	−18.0 (6)
C12—O3—C8A—C9A	−56.2 (4)	C6—C5—C8B—O3	139.0 (5)
C12—O3—C8B—C5	155.1 (3)	C6—C5—C8B—C9B	−105.1 (7)
C12—O3—C8B—C9B	42.9 (10)	C8A—O3—C12—C13	−157.9 (2)
C12—C13—C14—O6	−178.9 (2)	C8A—O3—C12—C11	23.7 (3)
C12—C13—C14—C15	−0.2 (3)	C8A—C5—C6—C7	179.6 (3)
C12—C11—C10—O4	178.0 (3)	C8B—O3—C12—C13	164.2 (5)
C12—C11—C10—C9A	7.3 (5)	C8B—O3—C12—C11	−14.2 (6)
C12—C11—C10—C9B	−18.3 (7)	C8B—C5—C6—C7	−162.5 (4)

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

(HESNAH)

Crystal data

C16H13.5Na0.5O6	F(000) = 652
Mr = 313.26	Dx = 1.515 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.7741 (6) Å	Cell parameters from 5911 reflections
b = 9.6357 (6) Å	θ = 2.8–27.6°
c = 13.8452 (9) Å	µ = 0.13 mm^−1
β = 107.103 (2)°	T = 150 K
V = 1373.79 (15) Å^3	Block, clear colourless
Z = 4	0.02 × 0.02 × 0.02 mm

Data collection

Bruker APEX-II CCD diffractometer	3173 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	2484 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.045
Detector resolution: 7.9 pixels mm^-1	θmax = 27.7°, θmin = 2.6°
φ and ω scans	h = −13→13
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0810 before and 0.0699 after correction. The Ratio of minimum to maximum transmission is 0.9583. The λ/2 correction factor is Not present.	k = −12→12
Tmin = 0.715, Tmax = 0.746	l = −16→18
13484 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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0442P)^2 + 0.593P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3173 reflections	Δρmax = 0.33 e Å^−3
212 parameters	Δρmin = −0.29 e Å^−3
2 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
Na1	0.250000	0.75989 (9)	0.750000	0.0247 (2)
O1	0.33446 (12)	−0.08033 (12)	0.88695 (9)	0.0258 (3)
O2	0.45167 (13)	−0.12475 (12)	0.75021 (10)	0.0264 (3)
O3	0.57590 (12)	0.33155 (13)	0.63723 (9)	0.0261 (3)
O6	0.34877 (12)	0.14363 (13)	0.32268 (9)	0.0260 (3)
H6	0.250000	0.141 (3)	0.250000	0.031*
O4	0.27316 (14)	0.58852 (13)	0.63720 (10)	0.0309 (3)
O5	0.14106 (14)	0.48226 (14)	0.46522 (10)	0.0327 (3)
H5	0.169 (2)	0.537 (2)	0.5173 (14)	0.039*
H2	0.507 (2)	−0.135 (2)	0.7167 (16)	0.039*
C12	0.46482 (17)	0.32694 (17)	0.55863 (13)	0.0226 (4)
C3	0.44804 (16)	0.00986 (17)	0.78075 (12)	0.0202 (3)
C11	0.35754 (17)	0.41238 (17)	0.55670 (13)	0.0222 (4)
C2	0.38462 (16)	0.03521 (17)	0.85353 (13)	0.0214 (3)
C16	0.24605 (17)	0.40247 (17)	0.47150 (13)	0.0235 (4)
C10	0.36363 (19)	0.50769 (17)	0.63716 (13)	0.0253 (4)
C4	0.50247 (16)	0.11853 (17)	0.74204 (13)	0.0214 (3)
H4	0.547080	0.100507	0.693507	0.026*
C14	0.34982 (17)	0.23002 (17)	0.39756 (12)	0.0220 (4)
C13	0.46217 (17)	0.23847 (18)	0.48064 (13)	0.0241 (4)
H13	0.535853	0.183102	0.482682	0.029*
C5	0.49240 (16)	0.25427 (17)	0.77366 (13)	0.0219 (4)
C15	0.24167 (18)	0.31135 (18)	0.39458 (13)	0.0243 (4)
H15	0.165016	0.303589	0.339245	0.029*
C7	0.37540 (18)	0.16898 (19)	0.88575 (14)	0.0272 (4)
H7	0.332452	0.186805	0.935370	0.033*
C8	0.55832 (18)	0.37140 (18)	0.73314 (13)	0.0254 (4)
H8	0.646499	0.385114	0.782025	0.030*
C6	0.42901 (18)	0.27799 (19)	0.84560 (14)	0.0280 (4)
H6A	0.421952	0.370070	0.867936	0.034*
C9	0.48818 (19)	0.50961 (18)	0.72127 (14)	0.0279 (4)
H9A	0.469608	0.532988	0.785260	0.034*
H9B	0.545414	0.582830	0.707830	0.034*
C1	0.28267 (19)	−0.0624 (2)	0.96956 (14)	0.0307 (4)
H1A	0.204570	−0.004481	0.948341	0.046*
H1B	0.347492	−0.017199	1.025572	0.046*
H1C	0.260265	−0.153183	0.991651	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0342 (6)	0.0165 (4)	0.0261 (5)	0.000	0.0129 (4)	0.000
O1	0.0298 (7)	0.0250 (6)	0.0265 (6)	−0.0033 (5)	0.0144 (5)	−0.0005 (5)
O2	0.0325 (7)	0.0193 (6)	0.0328 (7)	0.0013 (5)	0.0180 (6)	−0.0028 (5)
O3	0.0233 (6)	0.0297 (6)	0.0264 (6)	−0.0033 (5)	0.0090 (5)	0.0008 (5)
O6	0.0302 (7)	0.0265 (6)	0.0245 (6)	0.0040 (5)	0.0128 (5)	−0.0042 (5)
O4	0.0439 (8)	0.0203 (6)	0.0300 (7)	0.0059 (6)	0.0133 (6)	−0.0033 (5)
O5	0.0368 (8)	0.0324 (7)	0.0276 (7)	0.0150 (6)	0.0074 (6)	−0.0053 (6)
C12	0.0244 (9)	0.0216 (8)	0.0236 (8)	−0.0034 (7)	0.0097 (7)	0.0041 (7)
C3	0.0187 (8)	0.0199 (8)	0.0213 (8)	0.0031 (6)	0.0048 (7)	−0.0006 (6)
C11	0.0282 (9)	0.0174 (7)	0.0231 (8)	−0.0009 (7)	0.0108 (7)	0.0009 (6)
C2	0.0192 (8)	0.0230 (8)	0.0219 (8)	−0.0006 (6)	0.0061 (7)	0.0003 (7)
C16	0.0283 (9)	0.0201 (8)	0.0245 (8)	0.0049 (7)	0.0114 (7)	0.0035 (7)
C10	0.0367 (10)	0.0163 (7)	0.0251 (9)	−0.0034 (7)	0.0129 (8)	0.0018 (6)
C4	0.0201 (8)	0.0233 (8)	0.0213 (8)	0.0018 (7)	0.0068 (7)	−0.0001 (7)
C14	0.0294 (9)	0.0194 (8)	0.0208 (8)	0.0008 (7)	0.0130 (7)	0.0017 (6)
C13	0.0239 (9)	0.0249 (8)	0.0274 (9)	0.0031 (7)	0.0134 (7)	0.0031 (7)
C5	0.0199 (8)	0.0225 (8)	0.0219 (8)	−0.0019 (7)	0.0039 (7)	−0.0009 (7)
C15	0.0278 (9)	0.0237 (8)	0.0217 (8)	0.0031 (7)	0.0077 (7)	0.0009 (7)
C7	0.0287 (9)	0.0286 (9)	0.0283 (9)	−0.0024 (7)	0.0144 (8)	−0.0074 (7)
C8	0.0268 (9)	0.0252 (9)	0.0238 (8)	−0.0057 (7)	0.0068 (7)	−0.0026 (7)
C6	0.0315 (10)	0.0220 (8)	0.0326 (9)	−0.0030 (7)	0.0125 (8)	−0.0069 (7)
C9	0.0369 (11)	0.0203 (8)	0.0263 (9)	−0.0074 (7)	0.0090 (8)	−0.0034 (7)
C1	0.0307 (10)	0.0387 (10)	0.0269 (9)	−0.0023 (8)	0.0151 (8)	0.0009 (8)

Geometric parameters (Å, º)

Na1—O1^i	2.4038 (14)	C11—C10	1.430 (2)
Na1—O1^ii	2.4038 (14)	C2—C7	1.377 (2)
Na1—O2^ii	2.4399 (13)	C16—C15	1.370 (2)
Na1—O2^i	2.4399 (14)	C10—C9	1.496 (3)
Na1—O4	2.3361 (14)	C4—H4	0.9500
Na1—O4^iii	2.3362 (14)	C4—C5	1.394 (2)
O1—C2	1.376 (2)	C14—C13	1.406 (3)
O1—C1	1.423 (2)	C14—C15	1.395 (2)
O2—H2	0.860 (16)	C13—H13	0.9500
O2—C3	1.368 (2)	C5—C8	1.526 (2)
O3—C12	1.361 (2)	C5—C6	1.382 (2)
O3—C8	1.447 (2)	C15—H15	0.9500
O6—H6	1.2312 (14)	C7—H7	0.9500
O6—C14	1.327 (2)	C7—C6	1.391 (3)
O4—C10	1.248 (2)	C8—H8	1.0000
O5—H5	0.873 (16)	C8—C9	1.516 (3)
O5—C16	1.349 (2)	C6—H6A	0.9500
C12—C11	1.413 (2)	C9—H9A	0.9900
C12—C13	1.369 (2)	C9—H9B	0.9900
C3—C2	1.395 (2)	C1—H1A	0.9800
C3—C4	1.383 (2)	C1—H1B	0.9800
C11—C16	1.418 (2)	C1—H1C	0.9800
O1^i—Na1—O1^ii	100.35 (7)	O4—C10—C9	120.93 (16)
O1^i—Na1—O2^i	64.97 (4)	C11—C10—C9	116.06 (16)
O1^i—Na1—O2^ii	80.77 (5)	C3—C4—H4	119.7
O1^ii—Na1—O2^ii	64.97 (4)	C3—C4—C5	120.51 (16)
O1^ii—Na1—O2^i	80.77 (5)	C5—C4—H4	119.7
O2^i—Na1—O2^ii	125.80 (7)	O6—C14—C13	118.89 (15)
O4^iii—Na1—O1^ii	152.87 (5)	O6—C14—C15	120.94 (16)
O4—Na1—O1^ii	90.89 (4)	C15—C14—C13	120.17 (15)
O4—Na1—O1^i	152.87 (5)	C12—C13—C14	119.64 (16)
O4^iii—Na1—O1^i	90.89 (4)	C12—C13—H13	120.2
O4—Na1—O2^ii	126.26 (5)	C14—C13—H13	120.2
O4^iii—Na1—O2^ii	93.02 (4)	C4—C5—C8	119.41 (15)
O4—Na1—O2^i	93.02 (4)	C6—C5—C4	118.83 (16)
O4^iii—Na1—O2^i	126.26 (5)	C6—C5—C8	121.65 (15)
O4—Na1—O4^iii	90.04 (7)	C16—C15—C14	119.96 (16)
C2—O1—Na1^iv	110.37 (10)	C16—C15—H15	120.0
C2—O1—C1	117.24 (14)	C14—C15—H15	120.0
C1—O1—Na1^iv	124.39 (11)	C2—C7—H7	120.0
Na1^iv—O2—H2	134.4 (15)	C2—C7—C6	119.96 (16)
C3—O2—Na1^iv	109.01 (10)	C6—C7—H7	120.0
C3—O2—H2	111.5 (16)	O3—C8—C5	109.99 (14)
C12—O3—C8	114.87 (13)	O3—C8—H8	107.5
C14—O6—H6	117.2 (10)	O3—C8—C9	109.21 (14)
C10—O4—Na1	132.72 (12)	C5—C8—H8	107.5
C16—O5—H5	102.1 (15)	C9—C8—C5	114.75 (15)
O3—C12—C11	121.21 (15)	C9—C8—H8	107.5
O3—C12—C13	117.40 (16)	C5—C6—C7	120.95 (16)
C13—C12—C11	121.38 (16)	C5—C6—H6A	119.5
O2—C3—C2	116.98 (15)	C7—C6—H6A	119.5
O2—C3—C4	122.95 (15)	C10—C9—C8	112.21 (14)
C4—C3—C2	120.06 (15)	C10—C9—H9A	109.2
C12—C11—C16	117.69 (15)	C10—C9—H9B	109.2
C12—C11—C10	120.63 (16)	C8—C9—H9A	109.2
C16—C11—C10	121.66 (16)	C8—C9—H9B	109.2
O1—C2—C3	115.18 (14)	H9A—C9—H9B	107.9
O1—C2—C7	125.14 (15)	O1—C1—H1A	109.5
C7—C2—C3	119.68 (16)	O1—C1—H1B	109.5
O5—C16—C11	120.29 (15)	O1—C1—H1C	109.5
O5—C16—C15	118.58 (16)	H1A—C1—H1B	109.5
C15—C16—C11	121.13 (16)	H1A—C1—H1C	109.5
O4—C10—C11	122.97 (17)	H1B—C1—H1C	109.5
Na1^iv—O1—C2—C3	−36.99 (17)	C11—C12—C13—C14	−1.2 (3)
Na1^iv—O1—C2—C7	142.48 (16)	C11—C16—C15—C14	−2.3 (3)
Na1^iv—O2—C3—C2	34.75 (17)	C11—C10—C9—C8	−27.4 (2)
Na1^iv—O2—C3—C4	−144.55 (14)	C2—C3—C4—C5	−1.3 (3)
Na1—O4—C10—C11	−177.89 (12)	C2—C7—C6—C5	−0.3 (3)
Na1—O4—C10—C9	−0.2 (2)	C16—C11—C10—O4	−0.9 (3)
O1—C2—C7—C6	−179.34 (17)	C16—C11—C10—C9	−178.65 (15)
O2—C3—C2—O1	0.9 (2)	C10—C11—C16—O5	−1.1 (3)
O2—C3—C2—C7	−178.65 (16)	C10—C11—C16—C15	179.59 (16)
O2—C3—C4—C5	178.00 (16)	C4—C3—C2—O1	−179.83 (15)
O3—C12—C11—C16	179.25 (15)	C4—C3—C2—C7	0.7 (3)
O3—C12—C11—C10	0.8 (2)	C4—C5—C8—O3	23.9 (2)
O3—C12—C13—C14	−179.87 (14)	C4—C5—C8—C9	147.49 (16)
O3—C8—C9—C10	54.13 (19)	C4—C5—C6—C7	−0.3 (3)
O6—C14—C13—C12	−179.91 (15)	C13—C12—C11—C16	0.6 (2)
O6—C14—C15—C16	−178.33 (16)	C13—C12—C11—C10	−177.81 (16)
O4—C10—C9—C8	154.78 (16)	C13—C14—C15—C16	1.7 (3)
O5—C16—C15—C14	178.34 (15)	C5—C8—C9—C10	−69.9 (2)
C12—O3—C8—C5	71.61 (18)	C15—C14—C13—C12	0.0 (2)
C12—O3—C8—C9	−55.16 (18)	C8—O3—C12—C11	28.4 (2)
C12—C11—C16—O5	−179.53 (15)	C8—O3—C12—C13	−152.89 (15)
C12—C11—C16—C15	1.2 (2)	C8—C5—C6—C7	−176.52 (17)
C12—C11—C10—O4	177.50 (16)	C6—C5—C8—O3	−159.91 (16)
C12—C11—C10—C9	−0.3 (2)	C6—C5—C8—C9	−36.3 (2)
C3—C2—C7—C6	0.1 (3)	C1—O1—C2—C3	172.69 (15)
C3—C4—C5—C8	177.39 (15)	C1—O1—C2—C7	−7.8 (3)
C3—C4—C5—C6	1.1 (3)

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

(HESNAH_2EtOH)

Crystal data

C34H33NaO13·C2H6O	Z = 2
Mr = 718.66	F(000) = 756
Triclinic, P1	Dx = 1.383 Mg m^−3
a = 10.8865 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9884 (6) Å	Cell parameters from 8177 reflections
c = 16.1451 (8) Å	θ = 2.0–31.9°
α = 81.871 (4)°	µ = 0.12 mm^−1
β = 74.681 (5)°	T = 150 K
γ = 68.049 (5)°	Block, dull colourless
V = 1725.73 (17) Å^3	0.02 × 0.02 × 0.02 mm

Data collection

Dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images diffractometer	7061 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −13→13
Tmin = 0.904, Tmax = 1.000	k = −13→13
18542 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.165	w = 1/[σ^2(Fo^2) + (0.0697P)^2 + 1.0094P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
7061 reflections	Δρmax = 0.71 e Å^−3
501 parameters	Δρmin = −0.45 e Å^−3
11 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)
O7	0.04258 (17)	0.26213 (17)	0.74313 (10)	0.0247 (4)
O3	0.75675 (17)	0.76579 (16)	0.02451 (10)	0.0257 (4)
O1	0.52567 (18)	1.31872 (16)	0.17003 (11)	0.0265 (4)
O8	0.32193 (18)	0.41001 (17)	0.50684 (11)	0.0264 (4)
H8	0.372 (3)	0.382 (3)	0.4591 (13)	0.032*
O10	0.25517 (18)	0.00032 (17)	0.50246 (10)	0.0267 (4)
O12	0.36238 (17)	−0.49372 (16)	0.31498 (11)	0.0254 (4)
O11	0.53428 (18)	−0.47891 (17)	0.39399 (11)	0.0255 (4)
O2	0.74320 (17)	1.14463 (17)	0.21207 (11)	0.0257 (4)
O9	0.46429 (19)	0.24371 (17)	0.38522 (11)	0.0299 (4)
O6	0.98875 (18)	0.49207 (18)	−0.20727 (11)	0.0284 (4)
H6	1.006 (3)	0.4119 (19)	−0.2200 (18)	0.034*
O5	0.8307 (2)	0.30159 (18)	0.06049 (11)	0.0311 (4)
H5	0.794 (3)	0.321 (3)	0.1127 (12)	0.037*
O2E	0.99635 (18)	0.96881 (18)	0.19390 (11)	0.0319 (4)
H2E	0.996281	0.892670	0.209828	0.048*
O4	0.7094 (2)	0.45887 (18)	0.19025 (11)	0.0335 (5)
O1E	0.7667 (2)	0.2411 (2)	0.38340 (13)	0.0413 (5)
H1E	0.766068	0.177697	0.419142	0.062*
C20	0.2965 (2)	0.2028 (2)	0.49924 (14)	0.0203 (5)
C21	0.2318 (2)	0.1131 (2)	0.54138 (15)	0.0205 (5)
C29	0.3429 (2)	−0.3697 (2)	0.33503 (15)	0.0222 (5)
C17	0.1209 (2)	0.2448 (2)	0.66573 (14)	0.0218 (5)
C14	0.9241 (2)	0.5038 (2)	−0.12412 (14)	0.0210 (5)
C19	0.2646 (2)	0.3179 (2)	0.54371 (15)	0.0207 (5)
C28	0.4358 (2)	−0.3627 (2)	0.37810 (14)	0.0210 (5)
C11	0.7869 (2)	0.5346 (2)	0.04949 (15)	0.0207 (5)
C2	0.5531 (2)	1.1908 (2)	0.15394 (15)	0.0227 (5)
C16	0.8418 (2)	0.4095 (2)	0.01326 (15)	0.0212 (5)
C15	0.9070 (2)	0.3947 (2)	−0.07246 (15)	0.0233 (5)
H15	0.940172	0.311062	−0.096370	0.028*
C12	0.8054 (2)	0.6422 (2)	−0.00538 (15)	0.0204 (5)
C13	0.8736 (2)	0.6279 (2)	−0.09042 (15)	0.0223 (5)
H13	0.886180	0.701295	−0.125572	0.027*
C22	0.1484 (2)	0.1315 (2)	0.62190 (15)	0.0228 (5)
H22	0.108698	0.067875	0.648523	0.027*
C25	0.3970 (3)	0.1728 (2)	0.41962 (15)	0.0253 (5)
C3	0.6700 (2)	1.0987 (2)	0.17623 (14)	0.0214 (5)
C18	0.1806 (2)	0.3383 (2)	0.62381 (15)	0.0233 (5)
H18	0.162031	0.415865	0.651710	0.028*
C27	0.4236 (3)	−0.2417 (3)	0.40091 (15)	0.0268 (6)
H27	0.486307	−0.235903	0.430031	0.032*
C30	0.2406 (3)	−0.2568 (3)	0.31622 (17)	0.0302 (6)
H30	0.177283	−0.262161	0.287407	0.036*
C10	0.7227 (3)	0.5512 (3)	0.13938 (16)	0.0285 (6)
C26	0.3203 (3)	−0.1274 (3)	0.38189 (16)	0.0290 (6)
C4	0.7042 (3)	0.9673 (2)	0.16161 (16)	0.0298 (6)
H4	0.783528	0.903624	0.176484	0.036*
C31	0.2301 (3)	−0.1358 (3)	0.33929 (17)	0.0322 (6)
H31	0.160295	−0.058454	0.325574	0.039*
C7	0.4712 (3)	1.1510 (3)	0.12012 (16)	0.0319 (6)
H7	0.390391	1.213957	0.106755	0.038*
C32	0.2484 (3)	−0.5110 (3)	0.2961 (2)	0.0360 (7)
H32A	0.169358	−0.482968	0.344503	0.054*
H32B	0.270911	−0.603856	0.286855	0.054*
H32C	0.227201	−0.458002	0.244154	0.054*
C23	0.3035 (3)	0.0035 (3)	0.41005 (17)	0.0337 (7)
H23	0.228297	0.070745	0.386079	0.040*
C24	0.4225 (3)	0.0459 (3)	0.38120 (17)	0.0338 (7)
H24A	0.443771	0.057445	0.317719	0.041*
H24B	0.502390	−0.023367	0.398014	0.041*
C1	0.4758 (3)	1.4149 (3)	0.10571 (19)	0.0380 (7)
H1A	0.537148	1.390459	0.049339	0.057*
H1B	0.471476	1.500953	0.118958	0.057*
H1C	0.384616	1.419195	0.104793	0.057*
C6	0.5059 (3)	1.0207 (3)	0.10563 (18)	0.0394 (7)
H6A	0.449111	0.994224	0.082034	0.047*
C5	0.6228 (3)	0.9281 (3)	0.12513 (16)	0.0397 (8)
C4E	1.0678 (3)	0.9704 (3)	0.10491 (18)	0.0407 (7)
H4EA	1.056924	1.062197	0.084149	0.049*
H4EB	1.026906	0.935553	0.070126	0.049*
C3E	1.2162 (3)	0.8902 (4)	0.0924 (2)	0.0530 (9)
H3EA	1.261540	0.896449	0.031654	0.080*
H3EB	1.227530	0.798215	0.109805	0.080*
H3EC	1.256737	0.923391	0.127517	0.080*
C8A	0.6480 (8)	0.7922 (4)	0.1014 (3)	0.0201 (13)	0.693 (17)
H8A	0.564009	0.790569	0.088006	0.024*	0.693 (17)
C2E	0.9006 (4)	0.2526 (4)	0.3622 (3)	0.0563 (9)
H2EA	0.901026	0.326905	0.319761	0.068*
H2EB	0.969148	0.171427	0.335470	0.068*
C1E	0.9382 (4)	0.2737 (4)	0.4382 (3)	0.0710 (11)
H1EA	1.022120	0.293819	0.420256	0.107*
H1EB	0.952709	0.194199	0.476074	0.107*
H1EC	0.864896	0.347396	0.468968	0.107*
Na1	0.60941 (10)	0.33906 (9)	0.29742 (6)	0.0230 (2)
C9A	0.6871 (10)	0.6882 (5)	0.1723 (4)	0.0229 (14)	0.68 (2)
H9AA	0.610410	0.704040	0.223610	0.028*	0.68 (2)
H9AB	0.766448	0.692865	0.188947	0.028*	0.68 (2)
C8B	0.718 (2)	0.7708 (11)	0.1141 (6)	0.026 (3)	0.307 (17)
H8B	0.799682	0.750128	0.137848	0.031*	0.307 (17)
C9B	0.635 (2)	0.6898 (11)	0.1620 (10)	0.029 (3)	0.32 (2)
H9BA	0.548601	0.716236	0.143845	0.035*	0.32 (2)
H9BB	0.615040	0.699539	0.224711	0.035*	0.32 (2)
H11	0.577 (3)	−0.472 (3)	0.4278 (16)	0.035*
H2	0.820 (2)	1.089 (2)	0.2100 (19)	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O7	0.0264 (9)	0.0260 (9)	0.0163 (8)	−0.0069 (7)	0.0026 (7)	−0.0047 (7)
O3	0.0301 (10)	0.0195 (9)	0.0210 (8)	−0.0064 (7)	0.0028 (7)	−0.0039 (7)
O1	0.0329 (10)	0.0165 (9)	0.0265 (9)	−0.0019 (7)	−0.0104 (8)	−0.0025 (7)
O8	0.0356 (10)	0.0229 (9)	0.0218 (9)	−0.0159 (8)	0.0020 (7)	−0.0057 (7)
O10	0.0415 (11)	0.0240 (10)	0.0170 (8)	−0.0186 (8)	0.0027 (7)	−0.0073 (7)
O12	0.0273 (10)	0.0213 (9)	0.0324 (9)	−0.0088 (7)	−0.0100 (8)	−0.0098 (7)
O11	0.0268 (10)	0.0259 (10)	0.0264 (9)	−0.0091 (8)	−0.0081 (7)	−0.0061 (7)
O2	0.0213 (9)	0.0225 (10)	0.0299 (9)	−0.0021 (7)	−0.0060 (7)	−0.0059 (7)
O9	0.0397 (11)	0.0242 (10)	0.0250 (9)	−0.0184 (8)	0.0061 (8)	−0.0044 (7)
O6	0.0329 (10)	0.0307 (10)	0.0196 (8)	−0.0136 (8)	0.0050 (7)	−0.0093 (7)
O5	0.0449 (12)	0.0244 (10)	0.0221 (9)	−0.0154 (9)	0.0014 (8)	−0.0033 (7)
O2E	0.0275 (10)	0.0282 (10)	0.0290 (9)	−0.0044 (8)	0.0012 (8)	0.0030 (8)
O4	0.0492 (12)	0.0265 (10)	0.0225 (9)	−0.0181 (9)	0.0027 (8)	−0.0010 (7)
O1E	0.0395 (12)	0.0476 (14)	0.0413 (12)	−0.0193 (10)	−0.0152 (9)	0.0057 (10)
C20	0.0237 (13)	0.0211 (13)	0.0163 (11)	−0.0095 (10)	−0.0009 (9)	−0.0043 (9)
C21	0.0248 (13)	0.0184 (12)	0.0196 (11)	−0.0088 (10)	−0.0042 (9)	−0.0034 (9)
C29	0.0279 (13)	0.0174 (12)	0.0209 (11)	−0.0092 (10)	−0.0003 (10)	−0.0065 (9)
C17	0.0217 (12)	0.0225 (13)	0.0175 (11)	−0.0041 (10)	−0.0035 (9)	−0.0020 (9)
C14	0.0188 (12)	0.0260 (13)	0.0183 (11)	−0.0084 (10)	−0.0016 (9)	−0.0052 (9)
C19	0.0225 (12)	0.0191 (12)	0.0214 (12)	−0.0091 (10)	−0.0032 (9)	−0.0021 (9)
C28	0.0234 (13)	0.0222 (13)	0.0171 (11)	−0.0098 (10)	0.0013 (9)	−0.0071 (9)
C11	0.0203 (12)	0.0204 (12)	0.0212 (12)	−0.0070 (10)	−0.0039 (9)	−0.0026 (9)
C2	0.0266 (13)	0.0205 (13)	0.0190 (11)	−0.0079 (10)	−0.0002 (10)	−0.0053 (9)
C16	0.0216 (12)	0.0222 (13)	0.0222 (12)	−0.0112 (10)	−0.0043 (9)	−0.0006 (9)
C15	0.0250 (13)	0.0230 (13)	0.0224 (12)	−0.0088 (10)	−0.0021 (10)	−0.0079 (10)
C12	0.0186 (12)	0.0194 (12)	0.0229 (12)	−0.0055 (9)	−0.0032 (9)	−0.0059 (9)
C13	0.0216 (12)	0.0234 (13)	0.0208 (12)	−0.0081 (10)	−0.0018 (9)	−0.0032 (10)
C22	0.0254 (13)	0.0239 (13)	0.0204 (12)	−0.0129 (10)	0.0001 (10)	−0.0036 (10)
C25	0.0320 (14)	0.0220 (13)	0.0230 (12)	−0.0126 (11)	−0.0024 (10)	−0.0031 (10)
C3	0.0245 (13)	0.0199 (12)	0.0169 (11)	−0.0071 (10)	0.0004 (9)	−0.0040 (9)
C18	0.0286 (13)	0.0199 (13)	0.0208 (12)	−0.0082 (10)	−0.0026 (10)	−0.0058 (9)
C27	0.0296 (14)	0.0330 (15)	0.0219 (12)	−0.0178 (12)	0.0020 (10)	−0.0102 (10)
C30	0.0329 (15)	0.0240 (14)	0.0323 (14)	−0.0068 (11)	−0.0076 (11)	−0.0059 (11)
C10	0.0320 (14)	0.0243 (13)	0.0249 (13)	−0.0101 (11)	0.0020 (11)	−0.0034 (10)
C26	0.0333 (15)	0.0230 (14)	0.0254 (13)	−0.0120 (11)	0.0092 (11)	−0.0094 (10)
C4	0.0351 (15)	0.0201 (13)	0.0230 (12)	−0.0048 (11)	0.0060 (11)	−0.0032 (10)
C31	0.0346 (15)	0.0216 (14)	0.0349 (14)	−0.0063 (11)	−0.0017 (12)	−0.0067 (11)
C7	0.0336 (15)	0.0425 (17)	0.0241 (13)	−0.0181 (13)	−0.0045 (11)	−0.0071 (12)
C32	0.0282 (15)	0.0310 (16)	0.0557 (18)	−0.0106 (12)	−0.0139 (13)	−0.0148 (13)
C23	0.0434 (17)	0.0292 (15)	0.0266 (13)	−0.0181 (13)	0.0077 (12)	−0.0105 (11)
C24	0.0464 (17)	0.0313 (15)	0.0233 (13)	−0.0214 (13)	0.0083 (12)	−0.0095 (11)
C1	0.0452 (18)	0.0298 (16)	0.0384 (16)	−0.0100 (13)	−0.0182 (13)	0.0078 (12)
C6	0.057 (2)	0.0471 (19)	0.0276 (14)	−0.0359 (16)	−0.0028 (13)	−0.0078 (13)
C5	0.070 (2)	0.0307 (16)	0.0197 (13)	−0.0307 (16)	0.0124 (13)	−0.0129 (11)
C4E	0.0477 (18)	0.0415 (18)	0.0267 (14)	−0.0153 (14)	−0.0030 (13)	0.0065 (12)
C3E	0.0381 (18)	0.080 (3)	0.0385 (17)	−0.0291 (18)	0.0119 (14)	−0.0098 (17)
C8A	0.016 (3)	0.025 (2)	0.0182 (19)	−0.0079 (19)	0.0010 (17)	−0.0063 (15)
C2E	0.051 (2)	0.042 (2)	0.078 (3)	−0.0082 (16)	−0.0214 (19)	−0.0163 (18)
C1E	0.054 (2)	0.070 (3)	0.086 (3)	−0.010 (2)	−0.025 (2)	−0.010 (2)
Na1	0.0273 (5)	0.0225 (5)	0.0187 (5)	−0.0112 (4)	−0.0003 (4)	−0.0027 (4)
C9A	0.022 (3)	0.0248 (18)	0.020 (2)	−0.009 (2)	0.001 (2)	−0.0044 (14)
C8B	0.034 (9)	0.026 (5)	0.024 (5)	−0.016 (5)	−0.006 (5)	−0.002 (4)
C9B	0.028 (7)	0.025 (2)	0.031 (6)	−0.011 (3)	0.005 (5)	−0.006 (3)

Geometric parameters (Å, º)

O7—C17	1.307 (3)	C13—H13	0.9500
O3—C12	1.368 (3)	C22—H22	0.9500
O3—C8A	1.448 (4)	C25—C24	1.507 (3)
O3—C8B	1.399 (9)	C3—C4	1.388 (3)
O1—C2	1.372 (3)	C18—H18	0.9500
O1—C1	1.431 (3)	C27—H27	0.9500
O1—Na1^i	2.5267 (19)	C27—C26	1.397 (4)
O8—H8	0.838 (17)	C30—H30	0.9500
O8—C19	1.369 (3)	C30—C31	1.387 (4)
O10—C21	1.376 (3)	C10—C9A	1.543 (6)
O10—C23	1.445 (3)	C10—C9B	1.500 (11)
O12—C29	1.371 (3)	C26—C31	1.374 (4)
O12—C32	1.435 (3)	C26—C23	1.501 (4)
O12—Na1^ii	2.5960 (19)	C4—H4	0.9500
O11—C28	1.369 (3)	C4—C5	1.397 (4)
O11—Na1^ii	2.4669 (19)	C31—H31	0.9500
O11—H11	0.830 (17)	C7—H7	0.9500
O2—C3	1.361 (3)	C7—C6	1.376 (4)
O2—Na1^i	2.4557 (19)	C32—H32A	0.9800
O2—H2	0.829 (17)	C32—H32B	0.9800
O9—C25	1.242 (3)	C32—H32C	0.9800
O9—Na1	2.2885 (18)	C23—H23	1.0000
O6—H6	0.871 (17)	C23—C24	1.477 (4)
O6—C14	1.340 (3)	C24—H24A	0.9900
O5—H5	0.850 (17)	C24—H24B	0.9900
O5—C16	1.343 (3)	C1—H1A	0.9800
O2E—H2E	0.8400	C1—H1B	0.9800
O2E—C4E	1.443 (3)	C1—H1C	0.9800
O4—C10	1.240 (3)	C6—H6A	0.9500
O4—Na1	2.3117 (19)	C6—C5	1.381 (5)
O1E—H1E	0.8400	C5—C8A	1.500 (5)
O1E—C2E	1.456 (4)	C5—C8B	1.655 (13)
O1E—Na1	2.339 (2)	C4E—H4EA	0.9900
C20—C21	1.416 (3)	C4E—H4EB	0.9900
C20—C19	1.426 (3)	C4E—C3E	1.497 (4)
C20—C25	1.437 (3)	C3E—H3EA	0.9800
C21—C22	1.367 (3)	C3E—H3EB	0.9800
C29—C28	1.399 (3)	C3E—H3EC	0.9800
C29—C30	1.382 (4)	C8A—H8A	1.0000
C17—C22	1.414 (3)	C8A—C9A	1.524 (9)
C17—C18	1.416 (3)	C2E—H2EA	0.9900
C14—C15	1.403 (3)	C2E—H2EB	0.9900
C14—C13	1.397 (3)	C2E—C1E	1.463 (5)
C19—C18	1.365 (3)	C1E—H1EA	0.9800
C28—C27	1.379 (3)	C1E—H1EB	0.9800
C11—C16	1.420 (3)	C1E—H1EC	0.9800
C11—C12	1.418 (3)	C9A—H9AA	0.9900
C11—C10	1.439 (3)	C9A—H9AB	0.9900
C2—C3	1.396 (3)	C8B—H8B	1.0000
C2—C7	1.379 (4)	C8B—C9B	1.49 (2)
C16—C15	1.380 (3)	C9B—H9BA	0.9900
C15—H15	0.9500	C9B—H9BB	0.9900
C12—C13	1.377 (3)
C12—O3—C8A	116.9 (2)	O12—C32—H32C	109.5
C12—O3—C8B	114.6 (4)	H32A—C32—H32B	109.5
C2—O1—C1	115.7 (2)	H32A—C32—H32C	109.5
C2—O1—Na1^i	112.87 (14)	H32B—C32—H32C	109.5
C1—O1—Na1^i	130.53 (16)	O10—C23—C26	106.3 (2)
C19—O8—H8	106 (2)	O10—C23—H23	106.8
C21—O10—C23	115.54 (18)	O10—C23—C24	112.8 (2)
C29—O12—C32	116.16 (19)	C26—C23—H23	106.8
C29—O12—Na1^ii	115.71 (14)	C24—C23—C26	116.8 (2)
C32—O12—Na1^ii	127.66 (14)	C24—C23—H23	106.8
C28—O11—Na1^ii	119.48 (14)	C25—C24—H24A	109.3
C28—O11—H11	112 (2)	C25—C24—H24B	109.3
Na1^ii—O11—H11	126 (2)	C23—C24—C25	111.7 (2)
C3—O2—Na1^i	115.11 (14)	C23—C24—H24A	109.3
C3—O2—H2	110 (2)	C23—C24—H24B	109.3
Na1^i—O2—H2	133 (2)	H24A—C24—H24B	107.9
C25—O9—Na1	166.55 (17)	O1—C1—H1A	109.5
C14—O6—H6	107.3 (19)	O1—C1—H1B	109.5
C16—O5—H5	110 (2)	O1—C1—H1C	109.5
C4E—O2E—H2E	109.5	H1A—C1—H1B	109.5
C10—O4—Na1	160.17 (18)	H1A—C1—H1C	109.5
C2E—O1E—H1E	109.5	H1B—C1—H1C	109.5
C2E—O1E—Na1	122.6 (2)	C7—C6—H6A	119.8
Na1—O1E—H1E	125.1	C7—C6—C5	120.5 (3)
C21—C20—C19	116.3 (2)	C5—C6—H6A	119.8
C21—C20—C25	121.1 (2)	C4—C5—C8A	127.3 (4)
C19—C20—C25	122.4 (2)	C4—C5—C8B	99.3 (7)
O10—C21—C20	120.1 (2)	C6—C5—C4	119.5 (3)
C22—C21—O10	117.4 (2)	C6—C5—C8A	113.2 (4)
C22—C21—C20	122.4 (2)	C6—C5—C8B	141.0 (7)
O12—C29—C28	115.0 (2)	O2E—C4E—H4EA	109.2
O12—C29—C30	124.8 (2)	O2E—C4E—H4EB	109.2
C30—C29—C28	120.2 (2)	O2E—C4E—C3E	112.0 (2)
O7—C17—C22	120.5 (2)	H4EA—C4E—H4EB	107.9
O7—C17—C18	121.1 (2)	C3E—C4E—H4EA	109.2
C22—C17—C18	118.4 (2)	C3E—C4E—H4EB	109.2
O6—C14—C15	121.1 (2)	C4E—C3E—H3EA	109.5
O6—C14—C13	118.0 (2)	C4E—C3E—H3EB	109.5
C13—C14—C15	120.9 (2)	C4E—C3E—H3EC	109.5
O8—C19—C20	119.8 (2)	H3EA—C3E—H3EB	109.5
C18—C19—O8	118.3 (2)	H3EA—C3E—H3EC	109.5
C18—C19—C20	121.9 (2)	H3EB—C3E—H3EC	109.5
O11—C28—C29	116.5 (2)	O3—C8A—C5	106.3 (3)
O11—C28—C27	124.7 (2)	O3—C8A—H8A	109.1
C27—C28—C29	118.8 (2)	O3—C8A—C9A	110.3 (5)
C16—C11—C10	121.8 (2)	C5—C8A—H8A	109.1
C12—C11—C16	117.3 (2)	C5—C8A—C9A	112.9 (5)
C12—C11—C10	120.8 (2)	C9A—C8A—H8A	109.1
O1—C2—C3	115.9 (2)	O1E—C2E—H2EA	109.2
O1—C2—C7	123.8 (2)	O1E—C2E—H2EB	109.2
C7—C2—C3	120.3 (2)	O1E—C2E—C1E	112.0 (3)
O5—C16—C11	121.5 (2)	H2EA—C2E—H2EB	107.9
O5—C16—C15	117.4 (2)	C1E—C2E—H2EA	109.2
C15—C16—C11	121.0 (2)	C1E—C2E—H2EB	109.2
C14—C15—H15	120.2	C2E—C1E—H1EA	109.5
C16—C15—C14	119.7 (2)	C2E—C1E—H1EB	109.5
C16—C15—H15	120.2	C2E—C1E—H1EC	109.5
O3—C12—C11	121.0 (2)	H1EA—C1E—H1EB	109.5
O3—C12—C13	116.8 (2)	H1EA—C1E—H1EC	109.5
C13—C12—C11	122.2 (2)	H1EB—C1E—H1EC	109.5
C14—C13—H13	120.6	O1^ii—Na1—O12^i	73.11 (6)
C12—C13—C14	118.9 (2)	O11^i—Na1—O1^ii	130.93 (7)
C12—C13—H13	120.6	O11^i—Na1—O12^i	61.45 (6)
C21—C22—C17	120.3 (2)	O2^ii—Na1—O1^ii	63.22 (6)
C21—C22—H22	119.9	O2^ii—Na1—O12^i	134.15 (7)
C17—C22—H22	119.9	O2^ii—Na1—O11^i	164.37 (7)
O9—C25—C20	122.6 (2)	O9—Na1—O1^ii	89.75 (7)
O9—C25—C24	120.8 (2)	O9—Na1—O12^i	71.40 (7)
C20—C25—C24	116.5 (2)	O9—Na1—O11^i	92.45 (7)
O2—C3—C2	117.0 (2)	O9—Na1—O2^ii	94.37 (7)
O2—C3—C4	124.0 (2)	O9—Na1—O4	164.81 (8)
C4—C3—C2	119.0 (2)	O9—Na1—O1E	90.03 (8)
C17—C18—H18	119.7	O4—Na1—O1^ii	77.84 (7)
C19—C18—C17	120.6 (2)	O4—Na1—O12^i	96.32 (7)
C19—C18—H18	119.7	O4—Na1—O11^i	89.20 (7)
C28—C27—H27	119.5	O4—Na1—O2^ii	87.89 (7)
C28—C27—C26	121.1 (2)	O4—Na1—O1E	105.15 (8)
C26—C27—H27	119.5	O1E—Na1—O1^ii	146.81 (8)
C29—C30—H30	119.9	O1E—Na1—O12^i	137.42 (7)
C29—C30—C31	120.2 (3)	O1E—Na1—O11^i	82.24 (7)
C31—C30—H30	119.9	O1E—Na1—O2^ii	83.71 (7)
O4—C10—C11	122.9 (2)	C10—C9A—H9AA	109.9
O4—C10—C9A	120.6 (3)	C10—C9A—H9AB	109.9
O4—C10—C9B	119.9 (5)	C8A—C9A—C10	109.1 (5)
C11—C10—C9A	116.0 (3)	C8A—C9A—H9AA	109.9
C11—C10—C9B	114.6 (6)	C8A—C9A—H9AB	109.9
C27—C26—C23	121.0 (3)	H9AA—C9A—H9AB	108.3
C31—C26—C27	119.4 (2)	O3—C8B—C5	100.9 (8)
C31—C26—C23	119.6 (3)	O3—C8B—H8B	109.7
C3—C4—H4	119.8	O3—C8B—C9B	117.6 (12)
C3—C4—C5	120.4 (3)	C5—C8B—H8B	109.7
C5—C4—H4	119.8	C9B—C8B—C5	108.8 (12)
C30—C31—H31	119.9	C9B—C8B—H8B	109.7
C26—C31—C30	120.3 (3)	C10—C9B—H9BA	110.8
C26—C31—H31	119.9	C10—C9B—H9BB	110.8
C2—C7—H7	119.8	C8B—C9B—C10	104.9 (11)
C6—C7—C2	120.3 (3)	C8B—C9B—H9BA	110.8
C6—C7—H7	119.8	C8B—C9B—H9BB	110.8
O12—C32—H32A	109.5	H9BA—C9B—H9BB	108.8
O12—C32—H32B	109.5
O7—C17—C22—C21	−179.1 (2)	C22—C17—C18—C19	−1.2 (4)
O7—C17—C18—C19	178.6 (2)	C25—C20—C21—O10	−6.1 (4)
O3—C12—C13—C14	−179.4 (2)	C25—C20—C21—C22	171.9 (2)
O3—C8A—C9A—C10	−56.4 (8)	C25—C20—C19—O8	5.8 (4)
O3—C8B—C9B—C10	59 (2)	C25—C20—C19—C18	−172.4 (2)
O1—C2—C3—O2	0.6 (3)	C3—C2—C7—C6	−1.9 (4)
O1—C2—C3—C4	−179.9 (2)	C3—C4—C5—C6	−1.6 (4)
O1—C2—C7—C6	179.8 (2)	C3—C4—C5—C8A	177.0 (3)
O8—C19—C18—C17	−178.7 (2)	C3—C4—C5—C8B	174.6 (4)
O10—C21—C22—C17	179.6 (2)	C18—C17—C22—C21	0.6 (4)
O10—C23—C24—C25	−51.6 (3)	C27—C26—C31—C30	0.7 (4)
O12—C29—C28—O11	0.6 (3)	C27—C26—C23—O10	−70.0 (3)
O12—C29—C28—C27	−179.9 (2)	C27—C26—C23—C24	56.8 (3)
O12—C29—C30—C31	−179.9 (2)	C30—C29—C28—O11	−179.8 (2)
O11—C28—C27—C26	179.7 (2)	C30—C29—C28—C27	−0.2 (3)
O2—C3—C4—C5	179.4 (2)	C10—C11—C16—O5	3.1 (4)
O9—C25—C24—C23	−158.3 (3)	C10—C11—C16—C15	−177.8 (2)
O6—C14—C15—C16	179.0 (2)	C10—C11—C12—O3	−3.4 (4)
O6—C14—C13—C12	179.2 (2)	C10—C11—C12—C13	176.0 (2)
O5—C16—C15—C14	−178.5 (2)	C26—C23—C24—C25	−175.2 (2)
O4—C10—C9A—C8A	−153.5 (5)	C4—C5—C8A—O3	−73.9 (5)
O4—C10—C9B—C8B	153.0 (10)	C4—C5—C8A—C9A	47.1 (7)
C20—C21—C22—C17	1.5 (4)	C4—C5—C8B—O3	−113.5 (9)
C20—C19—C18—C17	−0.4 (4)	C4—C5—C8B—C9B	122.2 (13)
C20—C25—C24—C23	24.6 (4)	C31—C26—C23—O10	107.8 (3)
C21—O10—C23—C26	−179.4 (2)	C31—C26—C23—C24	−125.4 (3)
C21—O10—C23—C24	51.4 (3)	C7—C2—C3—O2	−177.7 (2)
C21—C20—C19—O8	−179.4 (2)	C7—C2—C3—C4	1.8 (3)
C21—C20—C19—C18	2.4 (4)	C7—C6—C5—C4	1.4 (4)
C21—C20—C25—O9	−173.2 (2)	C7—C6—C5—C8A	−177.3 (3)
C21—C20—C25—C24	3.8 (4)	C7—C6—C5—C8B	−172.5 (6)
C29—C28—C27—C26	0.2 (3)	C32—O12—C29—C28	161.1 (2)
C29—C30—C31—C26	−0.8 (4)	C32—O12—C29—C30	−18.5 (3)
C19—C20—C21—O10	179.0 (2)	C23—O10—C21—C20	−21.8 (3)
C19—C20—C21—C22	−3.0 (4)	C23—O10—C21—C22	160.1 (2)
C19—C20—C25—O9	1.4 (4)	C23—C26—C31—C30	−177.1 (2)
C19—C20—C25—C24	178.4 (2)	C1—O1—C2—C3	140.3 (2)
C28—C29—C30—C31	0.5 (4)	C1—O1—C2—C7	−41.4 (3)
C28—C27—C26—C31	−0.4 (4)	C6—C5—C8A—O3	104.7 (5)
C28—C27—C26—C23	177.4 (2)	C6—C5—C8A—C9A	−134.2 (6)
C11—C16—C15—C14	2.4 (4)	C6—C5—C8B—O3	61.2 (13)
C11—C12—C13—C14	1.2 (4)	C6—C5—C8B—C9B	−63.1 (14)
C11—C10—C9A—C8A	33.9 (8)	C5—C8A—C9A—C10	−175.2 (5)
C11—C10—C9B—C8B	−44.9 (18)	C5—C8B—C9B—C10	173.1 (11)
C2—C3—C4—C5	0.0 (3)	C8A—O3—C12—C11	−21.3 (5)
C2—C7—C6—C5	0.3 (4)	C8A—O3—C12—C13	159.2 (4)
C16—C11—C12—O3	−179.5 (2)	Na1^i—O1—C2—C3	−30.2 (2)
C16—C11—C12—C13	0.0 (4)	Na1^i—O1—C2—C7	148.1 (2)
C16—C11—C10—O4	−1.2 (4)	Na1^ii—O12—C29—C28	−26.1 (2)
C16—C11—C10—C9A	171.2 (5)	Na1^ii—O12—C29—C30	154.3 (2)
C16—C11—C10—C9B	−162.7 (11)	Na1^ii—O11—C28—C29	27.7 (3)
C15—C14—C13—C12	−0.5 (4)	Na1^ii—O11—C28—C27	−151.84 (18)
C12—O3—C8A—C5	174.7 (3)	Na1^i—O2—C3—C2	30.8 (2)
C12—O3—C8A—C9A	52.0 (7)	Na1^i—O2—C3—C4	−148.70 (19)
C12—O3—C8B—C5	−162.8 (5)	Na1—O9—C25—C20	−178.1 (6)
C12—O3—C8B—C9B	−44.7 (19)	Na1—O9—C25—C24	5.0 (10)
C12—C11—C16—O5	179.2 (2)	Na1—O4—C10—C11	−132.4 (4)
C12—C11—C16—C15	−1.8 (3)	Na1—O4—C10—C9A	55.6 (8)
C12—C11—C10—O4	−177.0 (2)	Na1—O4—C10—C9B	28.3 (14)
C12—C11—C10—C9A	−4.6 (6)	Na1—O1E—C2E—C1E	138.7 (3)
C12—C11—C10—C9B	21.4 (11)	C8B—O3—C12—C11	13.9 (10)
C13—C14—C15—C16	−1.2 (4)	C8B—O3—C12—C13	−165.5 (10)

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

(HESNA_H2O)

Crystal data

C16H15NaO7	F(000) = 712
Mr = 342.27	Dx = 1.546 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.0666 (4) Å	Cell parameters from 5942 reflections
b = 13.2714 (4) Å	θ = 3.1–27.5°
c = 10.0412 (3) Å	µ = 0.15 mm^−1
β = 94.430 (1)°	T = 150 K
V = 1470.34 (8) Å^3	Block, clear colourless
Z = 4	0.02 × 0.02 × 0.02 mm

Data collection

Bruker APEX-II CCD diffractometer	3368 independent reflections
Radiation source: microfocus sealed X-ray tube, Incoatec Iµs	2734 reflections with I > 2σ(I)
Mirror optics monochromator	Rint = 0.024
Detector resolution: 7.9 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
φ and ω scans	h = −10→14
Absorption correction: multi-scan SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0429 before and 0.0383 after correction. The Ratio of minimum to maximum transmission is 0.9516. The λ/2 correction factor is Not present.	k = −17→17
Tmin = 0.710, Tmax = 0.746	l = −13→12
14984 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)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.124	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 1.526P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3368 reflections	Δρmax = 0.55 e Å^−3
234 parameters	Δρmin = −0.59 e Å^−3
2 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)
Na1	0.27927 (7)	0.12994 (6)	1.14130 (8)	0.0246 (2)
O2	0.62761 (13)	0.66225 (11)	0.55484 (14)	0.0261 (3)
O6	0.27002 (14)	0.28888 (10)	1.22094 (13)	0.0255 (3)
O3	0.26690 (13)	0.49816 (10)	0.84055 (13)	0.0226 (3)
O1	0.50551 (12)	0.62392 (11)	0.32801 (13)	0.0241 (3)
O1W	0.07959 (13)	0.11781 (11)	1.05300 (15)	0.0289 (3)
H1WA	0.034697	0.093099	1.113045	0.043*
H1WB	0.050175	0.178115	1.037007	0.043*
O5	0.03894 (14)	0.58715 (12)	1.21296 (15)	0.0288 (3)
O4	0.04464 (15)	0.70155 (12)	1.01009 (15)	0.0335 (4)
C12	0.22684 (17)	0.47787 (14)	0.96503 (18)	0.0196 (4)
C15	0.15060 (18)	0.43622 (15)	1.21765 (19)	0.0231 (4)
H15	0.124561	0.421896	1.303609	0.028*
C11	0.15097 (17)	0.54853 (15)	1.02503 (19)	0.0200 (4)
C3	0.50881 (18)	0.64095 (14)	0.56105 (19)	0.0221 (4)
C16	0.11308 (17)	0.52264 (15)	1.15251 (19)	0.0220 (4)
C13	0.26303 (18)	0.39009 (15)	1.02639 (19)	0.0218 (4)
H13	0.311444	0.343578	0.982114	0.026*
C2	0.44081 (18)	0.62097 (14)	0.43955 (19)	0.0215 (4)
C14	0.22819 (18)	0.36815 (15)	1.15700 (19)	0.0216 (4)
C4	0.4528 (2)	0.63647 (15)	0.6794 (2)	0.0265 (4)
H4	0.498796	0.649061	0.761594	0.032*
C7	0.31936 (19)	0.59961 (16)	0.4393 (2)	0.0286 (5)
H7	0.273095	0.587015	0.357372	0.034*
C1	0.4402 (2)	0.60257 (17)	0.2027 (2)	0.0288 (5)
H1A	0.496057	0.603636	0.131650	0.043*
H1B	0.377081	0.653600	0.184360	0.043*
H1C	0.402629	0.535853	0.206375	0.043*
C10	0.11332 (19)	0.63971 (16)	0.9599 (2)	0.0258 (4)
C6	0.2636 (2)	0.59636 (17)	0.5600 (2)	0.0328 (5)
H6	0.179391	0.582099	0.559462	0.039*
C5	0.3304 (2)	0.61379 (16)	0.6797 (2)	0.0306 (5)
C9	0.1592 (2)	0.65784 (18)	0.8252 (2)	0.0346 (5)
H9A	0.088960	0.678982	0.764544	0.042*
H9B	0.215086	0.716086	0.834139	0.042*
C8A	0.2778 (2)	0.60574 (17)	0.8144 (2)	0.0213 (5)	0.85
H8A	0.337874	0.634747	0.883498	0.026*	0.85
H2	0.662 (2)	0.6789 (18)	0.6305 (18)	0.026*
H5	0.024 (2)	0.6361 (15)	1.159 (2)	0.026*
C8B	0.2178 (13)	0.5825 (11)	0.7615 (14)	0.027 (3)	0.15
H8B	0.156087	0.553073	0.694510	0.032*	0.15

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0224 (4)	0.0259 (4)	0.0255 (4)	0.0010 (3)	0.0017 (3)	−0.0017 (3)
O2	0.0255 (7)	0.0341 (8)	0.0182 (7)	−0.0041 (6)	−0.0017 (6)	−0.0005 (6)
O6	0.0348 (8)	0.0223 (7)	0.0189 (6)	−0.0005 (6)	−0.0015 (6)	0.0009 (6)
O3	0.0281 (7)	0.0198 (7)	0.0205 (7)	0.0015 (5)	0.0069 (5)	0.0009 (5)
O1	0.0226 (7)	0.0323 (8)	0.0173 (6)	−0.0052 (6)	0.0008 (5)	−0.0013 (6)
O1W	0.0263 (8)	0.0301 (8)	0.0312 (8)	0.0036 (6)	0.0069 (6)	0.0033 (6)
O5	0.0304 (8)	0.0323 (8)	0.0244 (7)	0.0069 (6)	0.0077 (6)	−0.0027 (6)
O4	0.0388 (9)	0.0301 (8)	0.0324 (8)	0.0124 (7)	0.0088 (7)	−0.0005 (6)
C12	0.0187 (9)	0.0233 (9)	0.0167 (8)	−0.0023 (7)	0.0004 (7)	−0.0010 (7)
C15	0.0234 (9)	0.0293 (10)	0.0168 (9)	−0.0036 (8)	0.0022 (7)	−0.0019 (8)
C11	0.0177 (9)	0.0224 (9)	0.0200 (9)	−0.0016 (7)	0.0015 (7)	−0.0020 (7)
C3	0.0272 (10)	0.0173 (9)	0.0220 (9)	0.0019 (7)	0.0033 (8)	0.0022 (7)
C16	0.0182 (9)	0.0266 (10)	0.0212 (9)	−0.0016 (7)	0.0018 (7)	−0.0061 (8)
C13	0.0225 (9)	0.0219 (9)	0.0209 (9)	0.0006 (7)	0.0020 (7)	−0.0028 (7)
C2	0.0243 (10)	0.0182 (9)	0.0226 (9)	−0.0017 (7)	0.0054 (7)	0.0022 (7)
C14	0.0231 (9)	0.0210 (9)	0.0203 (9)	−0.0044 (7)	−0.0012 (7)	−0.0015 (7)
C4	0.0347 (11)	0.0224 (10)	0.0229 (10)	0.0040 (8)	0.0062 (8)	0.0040 (8)
C7	0.0252 (10)	0.0282 (10)	0.0324 (11)	−0.0038 (8)	0.0012 (8)	0.0004 (9)
C1	0.0297 (11)	0.0344 (11)	0.0215 (10)	−0.0047 (9)	−0.0036 (8)	−0.0014 (8)
C10	0.0273 (10)	0.0256 (10)	0.0245 (10)	0.0027 (8)	0.0028 (8)	−0.0014 (8)
C6	0.0233 (10)	0.0304 (11)	0.0463 (13)	−0.0012 (9)	0.0128 (9)	0.0060 (10)
C5	0.0363 (12)	0.0245 (10)	0.0329 (11)	0.0070 (9)	0.0143 (9)	0.0076 (9)
C9	0.0419 (13)	0.0307 (11)	0.0325 (12)	0.0106 (10)	0.0109 (10)	0.0088 (9)
C8A	0.0223 (12)	0.0199 (11)	0.0222 (11)	−0.0010 (9)	0.0045 (10)	0.0009 (9)
C8B	0.021 (7)	0.036 (8)	0.021 (6)	−0.006 (6)	−0.005 (6)	0.002 (6)

Geometric parameters (Å, º)

Na1—O2^i	2.3320 (16)	C11—C10	1.423 (3)
Na1—O6	2.2610 (16)	C3—C2	1.408 (3)
Na1—O3^ii	2.6370 (16)	C3—C4	1.383 (3)
Na1—O1^i	2.3791 (16)	C13—H13	0.9500
Na1—O1W	2.3222 (17)	C13—C14	1.425 (3)
Na1—C6^ii	3.113 (2)	C2—C7	1.373 (3)
O2—C3	1.351 (2)	C4—H4	0.9500
O2—H2	0.851 (16)	C4—C5	1.388 (3)
O6—C14	1.299 (2)	C7—H7	0.9500
O3—C12	1.385 (2)	C7—C6	1.403 (3)
O3—C8A	1.458 (3)	C1—H1A	0.9800
O3—C8B	1.453 (14)	C1—H1B	0.9800
O1—C2	1.376 (2)	C1—H1C	0.9800
O1—C1	1.430 (2)	C10—C9	1.500 (3)
O1W—H1WA	0.8742	C6—H6	0.9500
O1W—H1WB	0.8741	C6—C5	1.381 (3)
O5—C16	1.361 (2)	C5—C8A	1.517 (3)
O5—H5	0.853 (16)	C5—C8B	1.600 (14)
O4—C10	1.251 (3)	C9—H9A	0.9900
C12—C11	1.423 (3)	C9—H9B	0.9900
C12—C13	1.364 (3)	C9—C8A	1.496 (3)
C15—H15	0.9500	C9—C8B	1.376 (15)
C15—C16	1.369 (3)	C8A—H8A	1.0000
C15—C14	1.416 (3)	C8B—H8B	1.0000
C11—C16	1.420 (3)
O2^i—Na1—O3^ii	144.24 (6)	C7—C2—C3	119.84 (19)
O2^i—Na1—O1^i	67.19 (5)	O6—C14—C15	120.59 (18)
O2^i—Na1—C6^ii	88.59 (6)	O6—C14—C13	120.59 (18)
O6—Na1—O2^i	99.33 (6)	C15—C14—C13	118.79 (18)
O6—Na1—O3^ii	109.07 (5)	C3—C4—H4	119.6
O6—Na1—O1^i	93.31 (6)	C3—C4—C5	120.8 (2)
O6—Na1—O1W	97.58 (6)	C5—C4—H4	119.6
O6—Na1—C6^ii	171.68 (7)	C2—C7—H7	120.0
O3^ii—Na1—C6^ii	64.65 (6)	C2—C7—C6	120.1 (2)
O1^i—Na1—O3^ii	89.44 (5)	C6—C7—H7	120.0
O1^i—Na1—C6^ii	92.10 (6)	O1—C1—H1A	109.5
O1W—Na1—O2^i	99.20 (6)	O1—C1—H1B	109.5
O1W—Na1—O3^ii	98.13 (6)	O1—C1—H1C	109.5
O1W—Na1—O1^i	163.88 (6)	H1A—C1—H1B	109.5
O1W—Na1—C6^ii	78.51 (6)	H1A—C1—H1C	109.5
Na1^iii—O2—H2	127.3 (16)	H1B—C1—H1C	109.5
C3—O2—Na1^iii	119.71 (12)	O4—C10—C11	122.56 (19)
C3—O2—H2	112.4 (16)	O4—C10—C9	121.11 (19)
C14—O6—Na1	127.22 (12)	C11—C10—C9	116.33 (18)
C12—O3—Na1^iv	126.77 (11)	Na1^iv—C6—H6	81.0
C12—O3—C8A	112.94 (15)	C7—C6—Na1^iv	103.69 (14)
C12—O3—C8B	120.7 (6)	C7—C6—H6	119.9
C8B—O3—Na1^iv	97.0 (6)	C5—C6—Na1^iv	85.31 (13)
C2—O1—Na1^iii	118.32 (12)	C5—C6—C7	120.3 (2)
C2—O1—C1	116.80 (16)	C5—C6—H6	119.9
C1—O1—Na1^iii	123.62 (12)	C4—C5—C8A	117.3 (2)
Na1—O1W—H1WA	109.7	C4—C5—C8B	148.9 (6)
Na1—O1W—H1WB	109.7	C6—C5—C4	119.5 (2)
H1WA—O1W—H1WB	104.3	C6—C5—C8A	123.2 (2)
C16—O5—H5	106.8 (16)	C6—C5—C8B	91.0 (6)
O3—C12—C11	119.64 (17)	C10—C9—H9A	107.2
C13—C12—O3	118.08 (17)	C10—C9—H9B	107.2
C13—C12—C11	122.28 (18)	H9A—C9—H9B	106.8
C16—C15—H15	120.0	C8A—C9—C10	110.57 (19)
C16—C15—C14	120.04 (18)	C8B—C9—C10	120.4 (6)
C14—C15—H15	120.0	C8B—C9—H9A	107.2
C16—C11—C12	116.57 (17)	C8B—C9—H9B	107.2
C16—C11—C10	121.61 (18)	O3—C8A—C5	105.81 (17)
C10—C11—C12	121.82 (17)	O3—C8A—C9	110.73 (19)
O2—C3—C2	117.15 (17)	O3—C8A—H8A	108.2
O2—C3—C4	123.40 (18)	C5—C8A—H8A	108.2
C4—C3—C2	119.44 (19)	C9—C8A—C5	115.6 (2)
O5—C16—C15	119.02 (18)	C9—C8A—H8A	108.2
O5—C16—C11	118.70 (18)	O3—C8B—C5	102.0 (9)
C15—C16—C11	122.26 (18)	O3—C8B—H8B	105.9
C12—C13—H13	120.0	C5—C8B—H8B	105.9
C12—C13—C14	119.96 (18)	C9—C8B—O3	118.4 (10)
C14—C13—H13	120.0	C9—C8B—C5	117.6 (10)
O1—C2—C3	115.02 (17)	C9—C8B—H8B	105.9
C7—C2—O1	125.14 (18)
Na1^iii—O2—C3—C2	−13.7 (2)	C3—C4—C5—C8A	177.25 (19)
Na1^iii—O2—C3—C4	165.28 (15)	C3—C4—C5—C8B	166.9 (11)
Na1—O6—C14—C15	135.04 (16)	C16—C15—C14—O6	175.99 (18)
Na1—O6—C14—C13	−47.2 (2)	C16—C15—C14—C13	−1.8 (3)
Na1^iv—O3—C12—C11	−137.93 (14)	C16—C11—C10—O4	−0.5 (3)
Na1^iv—O3—C12—C13	42.6 (2)	C16—C11—C10—C9	−179.67 (19)
Na1^iv—O3—C8A—C5	−16.0 (2)	C13—C12—C11—C16	−0.7 (3)
Na1^iv—O3—C8A—C9	109.93 (17)	C13—C12—C11—C10	−179.73 (19)
Na1^iv—O3—C8B—C5	−69.8 (7)	C2—C3—C4—C5	−0.8 (3)
Na1^iv—O3—C8B—C9	159.4 (10)	C2—C7—C6—Na1^iv	−93.1 (2)
Na1^iii—O1—C2—C3	11.5 (2)	C2—C7—C6—C5	−0.5 (3)
Na1^iii—O1—C2—C7	−167.87 (16)	C14—C15—C16—O5	−179.73 (17)
Na1^iv—C6—C5—C4	104.35 (19)	C14—C15—C16—C11	−1.1 (3)
Na1^iv—C6—C5—C8A	−73.3 (2)	C4—C3—C2—O1	−177.86 (17)
Na1^iv—C6—C5—C8B	−69.2 (5)	C4—C3—C2—C7	1.5 (3)
O2—C3—C2—O1	1.1 (2)	C4—C5—C8A—O3	−102.3 (2)
O2—C3—C2—C7	−179.49 (18)	C4—C5—C8A—C9	134.8 (2)
O2—C3—C4—C5	−179.73 (19)	C4—C5—C8B—O3	−48.6 (16)
O3—C12—C11—C16	179.82 (16)	C4—C5—C8B—C9	82.6 (14)
O3—C12—C11—C10	0.8 (3)	C7—C6—C5—C4	1.2 (3)
O3—C12—C13—C14	177.33 (17)	C7—C6—C5—C8A	−176.4 (2)
O1—C2—C7—C6	178.45 (19)	C7—C6—C5—C8B	−172.3 (6)
O4—C10—C9—C8A	153.2 (2)	C1—O1—C2—C3	179.11 (17)
O4—C10—C9—C8B	−169.3 (8)	C1—O1—C2—C7	−0.2 (3)
C12—O3—C8A—C5	176.19 (17)	C10—C11—C16—O5	0.0 (3)
C12—O3—C8A—C9	−57.9 (2)	C10—C11—C16—C15	−178.60 (19)
C12—O3—C8B—C5	149.5 (4)	C10—C9—C8A—O3	56.6 (3)
C12—O3—C8B—C9	18.7 (14)	C10—C9—C8A—C5	176.8 (2)
C12—C11—C16—O5	−179.02 (16)	C10—C9—C8B—O3	−18.6 (14)
C12—C11—C16—C15	2.4 (3)	C10—C9—C8B—C5	−141.9 (7)
C12—C11—C10—O4	178.48 (19)	C6—C5—C8A—O3	75.4 (3)
C12—C11—C10—C9	−0.7 (3)	C6—C5—C8A—C9	−47.5 (3)
C12—C13—C14—O6	−174.38 (18)	C6—C5—C8B—O3	120.4 (8)
C12—C13—C14—C15	3.4 (3)	C6—C5—C8B—C9	−108.3 (10)
C11—C12—C13—C14	−2.1 (3)	C8A—O3—C12—C11	28.8 (2)
C11—C10—C9—C8A	−27.6 (3)	C8A—O3—C12—C13	−150.73 (19)
C11—C10—C9—C8B	9.9 (8)	C8B—O3—C12—C11	−9.6 (8)
C3—C2—C7—C6	−0.9 (3)	C8B—O3—C12—C13	170.9 (7)
C3—C4—C5—C6	−0.6 (3)

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