Revisiting a natural wine salt: calcium (2R,3R)-tar­trate tetra­hydrate

Polo, A.; Soriano, A.; Rodríguez, R.; Macías, R.; García-Orduña, P.; Sanz Miguel, P.J.

doi:10.1107/S2053229624008015

research papers

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 80| Part 10| October 2024|

https://doi.org/10.1107/S2053229624008015

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Revisiting a natural wine salt: calcium (2R,3R)-tartrate tetrahydrate

Alvaro Polo,^a Alejandro Soriano,^a Ricardo Rodríguez,^a Ramón Macías,^a Pilar García-Orduña ^a ^* and Pablo J. Sanz Miguel ^a ^*

^aDepartamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza–CSIC, 50009 Zaragoza, Spain
^*Correspondence e-mail: mpgaror@unizar.es, pablo.sanz@unizar.es

Edited by R. Diniz, Universidade Federal de Minas Gerais, Brazil (Received 27 June 2024; accepted 14 August 2024; online 4 September 2024)

The crystal structure of the salt calcium (2R,3R)-tartrate tetrahydrate {systematic name: poly[[diaqua[μ₄-(2R,3R)-2,3-dihydroxybutanedioato]calcium(II)] dihydrate]}, {[Ca(C₄H₈O₈)(H₂O)₂]·2H₂O}_n, is reported. The absolute configuration of the crystal was established unambiguously using anomalous dispersion effects in the diffraction patterns. High-quality data also allowed the location and free refinement of all the H atoms, and therefore to a careful analysis of the hydrogen-bond interactions.

Keywords: crystal structure; wine crystal; calcium tartrate; hydrogen bonding; chirality; hydration.

CCDC reference: 2377585

1. Introduction

The opening of a bottle of wine is a process that can elicit a variety of expectations, either in terms of the wine's taste, colour, smell, sensations or even in the occasional discovery of brilliant crystals, typically found on the surface of the cork in contact with the wine. The so-called Weinsteine or wine diamonds (Derewenda, 2008 ) are regarded by winemakers as a sign of quality, as their presence indicates that wine has been handled with natural methods and proper timing. It is known that such diamonds are actually crystalline tartrate salts.

Tartaric acid (Astbury, 1923 ), also known as 2,3-dihydroxybutanedioic acid, is a naturally occurring substance that is typically found on grapes and other plants. Although two enantiomers (2R,3R/2S,3S) and a meso form (2S,3R/2R,3S) are possible, only the 2R,3R enantiomer, namely L-(+)-tartaric acid, is biologically produced by vining plants. Deprotonation to its tartrate form (Fig. 1) during the fermentation and aging steps of wine production in the presence of alkali earth metal cations, usually K⁺ and Ca²⁺, may result in the slow crystallization of 2R,3R salts. This process can extend over a prolonged period, frequently becoming noticeable after commercial release.

Figure 1
The enantiomeric and meso forms of tartrate.

Pioneering studies on the unit-cell parameters of the title compound, Ca[(2R,3R)-C₄H₄O₆]·4H₂O (1), were reported by Evans (1935 ), yielding a P2₁2₁2₁ space group crystal structure, with unit-cell parameters a = 9.20 (2), b = 10.54 (2) and c = 9.62 (2) Å. Several studies since then have confirmed the crystal structure of this salt, corroborating the space group and unit-cell dimensions (Ambady, 1968 ; Hawthorne et al., 1982 ; Boese & Heinemann, 1993 ; Kaduk, 2007 ). In all the studies, aqueous solutions of tartaric acid were employed, from which crystals were grown. Although tartaric acid and its derivatives, especially its sodium ammonium salt, have long been central to the analysis of stereochemistry and chirality (Gal, 2008 ), since the pioneering works of Pasteur and Biott (see Flack, 2009 , and references therein), it is important to note that in none of these structural reports about Ca(C₄H₄O₆)·4H₂O was it possible to identify which of the enantiomers was being measured through anomalous dispersion effects.

Interestingly, triclinic polymorphs of racemic 1 (i.e. with both enantiomers in the unit cell) have also been reported (Le Bail et al., 2009 ; Appelhans et al., 2009 ; Fukami et al., 2016 ). Furthermore, not only polymorphs, but also hydrates and solvates of Ca and tartrate have been reported. In this context, calcium tartrate has been found to also crystallize as its anhydrous (Appelhans et al., 2009; Aljafree et al., 2024 ), trihydrate (de Vries & Kroon, 1984 ) and hexahydrate forms (Ventruti et al., 2015 ), and has been observed to cocrystallize with other species (Wartchow, 1996 ). The absolute configuration of these hydrates and solvates has been established experimentally, except in the case of the trihydrate form, which was found to contain the meso-tartaric form. Obviously, different hydration is related to dissimilar connectivity and crystal packing.

Here, we report the crystal structure of the calcium (2R,3R)-tartrate tetrahydrate salt (1), obtained from a crystal which was found and picked up from the cork of a Crianza red wine bottle from D.O. Campo de Borja (2016). This tetrahydrated salt crystallizes in the orthorhombic space group P2₁2₁2₁, with the unit-cell dimensions [a = 9.1587 (4), b = 9.5551 (4) and c = 10.5041 (5) Å], which are close to those reported by Evans (1935). High-quality experimental diffraction data allowed us to establish unambiguously the absolute structure and therefore the absolute configuration of the salt, and to analyze intermolecular interactions in the crystal packing.

2. Experimental

2.1. Single-crystal selection

Single crystals were found in the cork of a wine bottle, removed and selected under a microscope.

2.2. Single-crystal X-ray diffraction

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were located in difference Fourier maps and freely refined. High-quality and complete diffraction data, with 99.2% of the reflections measured until a maximal resolution of (sin θ/λ)_max = 0.667 Å⁻¹ (with almost all the Friedel pairs: number of Friedel pairs measured out to the maximal resolution divided by the number of theoretically possible is 0.981, very close to unity), a mean redundancy higher than 20 and a good agreement factor (R_int = 0.030) of this Ca-containing crystal allowed us to establish the absolute structure in the solid state and therefore the absolute configuration of the molecule. For that purpose, the Flack parameter (Flack & Bernardinelli, 1999 , 2000 ) has been refined. The obtained values are 0.028 (19) by classical fit to all intensities and 0.023 (3) using 937 quotients (Parsons et al., 2013 ). The obtained values of the parameter and its standard uncertainty (s.u.) value provide evidence for a strong inversion-distinguishing power and a correct estimation of the absolute structure for this structural model.

Table 1
Experimental details

Crystal data
Chemical formula	[Ca(C₄H₄O₆)(H₂O)₂]·2H₂O
M_r	260.22
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	9.1587 (4), 9.5551 (4), 10.5041 (5)
V (Å³)	919.24 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.73
Crystal size (mm)	0.15 × 0.13 × 0.09

Data collection
Diffractometer	Bruker D8 VENTURE
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.889, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	47365, 2275, 2268
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.035, 1.09
No. of reflections	2275
No. of parameters	184
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.25
Absolute structure	Flack x determined using 937 quotients [(I⁺) − (I⁻)]/[(I⁺) + (I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.023 (3)
Computer programs: SAINT in APEX3 (Bruker, 2016), SHELXS2013 (Sheldrick, 2008 ), SHELXL2018 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ) and XCIF in PLATON (Spek, 2020 ).

3. Results and discussion

The asymmetric unit of Ca[(2R,3R)-C₄H₄O₆]·4H₂O (1) is formed by a Ca²⁺ ion, a tartrate ligand and four water molecules. In the crystal structure, the tartrate ion exhibits typical bonding connections (Ambady, 1968). Salient bond distances and angles are listed in Tables S1 and S2 of the supporting information. The two C—O bonds of each carboxylate group, which, along with the hydroxy substituents, chelate two Ca²⁺ cations, are significantly longer than the other two carboxylate C—O bonds, where the O atoms bind to additional adjacent Ca atoms [C1—O11 = 1.2659 (14) Å and C4—O41 = 1.2681 (14) Å versus C1—O12 = 1.2483 (15) Å and C4—O42 = 1.2472 (14) Å]. All the C atoms of the tartrate skeleton exhibit similar C—C separations, and are positioned in an almost coplanar manner, with maximal deviations from the best plane of 0.0020 (6) Å. It is noteworthy that the folding of this dicarboxylate entity is asymmetrical. Specifically, the O21 atom of the alcohol group lies nearly in the plane defined by the C1 atom and the atoms coordinated to its sp² hybridization, namely, C1, C2, O11 and O12 [0.069 (2) Å], whereas the alcohol O31 atom is placed significantly out of the analogous plane [atoms C3, C4, O41 and O42, 0.575 (2) Å].

3.1. Ca environment

In the crystal packing, each tartrate anion acts as a tetratopic ligand, serving as a chelate for two Ca²⁺ cations and as a terminal ligand for two additional Ca²⁺ cations (Fig. 2), whereas the Ca²⁺ cations (Ca1) are coordinated to four symmetry-related tartrate anions and two water molecules in a distorted pseudo-octahedral coordination environment (Fig. 3).

Figure 2
Ca²⁺ cations bonded to a tartrate anion in 1. [Symmetry codes: (i) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (ii) −x + $[{1\over 2}]$ , −y + 1, z + $[{1\over 2}]$ ; (iii) −x + 1, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

Figure 3
Coordination sphere of the Ca²⁺ cation in 1. [Symmetry codes: (iv) −x, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (v) −x + 1, y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vi) −x + $[{1\over 2}]$ , −y + 1, z − $[{1\over 2}]$ .

Among the eight coordination sites of Ca, two are occupied by monodentate O atoms from carboxylate groups [O12—Ca1—O42 = 137.72 (3)°], with another two sites hosting water molecules [O1W—Ca1—O2W = 97.34 (3)°]. The coordination sphere of Ca1 is completed by two chelating tartrate ligands bonded by different edges, namely, O11—C1—C2—O21 and O31—C3—C4—O41. In both chelates, separation from the deprotonated O atoms to the Ca²⁺ cation [Ca1—O11 = 2.3733 (8) Å and Ca1—O41 = 2.4137 (9) Å] are significantly shorter compared to those of the alcohol groups [Ca1—O21 = 2.4544 (9) Å and Ca1—O31 = 2.5102 (9) Å]. These Ca—O distances range from 2.3733 (8) (Ca1—O11) to 2.5102 (9) Å (Ca—O31), which are consistent with the expected values (Ambady, 1968). It is noteworthy that this coordination of the Ca²⁺ ion in 1 notably differs from that of the triclinic polymorph, where the eight-coordinated Ca²⁺ ion is bound to two bis-chelated tartrate ligands and four water molecules.

3.2. Hydrogen bonding

The two additional water molecules fulfilling the unit cell of 1, and which are not coordinated to Ca, are involved in hydrogen-bonding interactions. The crystal lattice is mainly stabilized by electrostatics and hydrogen bonding. The tartrate anions are connected via short hydrogen bonds [O31—H31⋯O41 = 2.5529 (12) Å] in a zigzag fashion along the a axis (Fig. 4). Finally, water molecules participate in eight additional hydrogen bonds involving tartrate anions and other water molecules (Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O31—H31⋯O41^vii	0.84 (3)	1.71 (3)	2.5529 (12)	174 (2)
O21—H21⋯O4W	0.83 (2)	1.88 (2)	2.7023 (13)	174 (2)
O1W—H2W⋯O31	0.82 (3)	2.11 (3)	2.9236 (13)	170 (2)
O2W—H3W⋯O3W	0.82 (2)	1.95 (2)	2.7483 (13)	164 (2)
O2W—H4W⋯O11^viii	0.87 (2)	2.12 (2)	2.8658 (13)	144 (2)
O3W—H5W⋯O42^ix	0.90 (3)	2.26 (3)	3.0318 (13)	144 (2)
O3W—H6W⋯O11^x	0.80 (2)	2.09 (2)	2.8809 (13)	168 (2)
O4W—H7W⋯O2W^x	0.77 (3)	2.16 (3)	2.9199 (14)	170 (2)
O4W—H8W⋯O1W^xi	0.83 (3)	2.31 (3)	3.1263 (15)	171 (2)
Symmetry codes: (vii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (viii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ix) ; (x) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (xi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 4
Hydrogen bonding involving tartrate anions in 1. Calcium cations and water molecules have been omitted for clarity.

4. Summary

The title calcium (2R,3R)-tartrate tetrahydrate salt (1) crystallized in the orthorhombic space group P2₁2₁2₁, as anticipated by Evans (1935). In this work, anomalous dispersion effects in the crystal diffraction patterns led to the determination of the absolute configuration of the L-(+)-tartrate salt 1. The absolute configuration has been resolved on the basis of anomalous dispersion effects in the crystal diffraction patterns and matches the enantiomer expected from a natural wine-making process. The good crystal quality allowed for precise determination of the geometrical arrangement, particularly enabling the localization of H atoms, and therefore the observation and accurate characterization of the hydrogen-bonding network.

Supporting information

CCDC reference: 2377585

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2053229624008015/dg3060sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2053229624008015/dg3060Isup2.hkl

Additional tables. DOI: https://doi.org/10.1107/S2053229624008015/dg3060sup3.pdf

Computing details top

Poly[[diaqua[µ₄-(2R,3R)-2,3-dihydroxybutanedioato]calcium(II)] dihydrate] top

Crystal data top

[Ca(C₄H₄O₆)(H₂O)₂]·2H₂O	D_x = 1.880 Mg m⁻³
M_r = 260.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9609 reflections
a = 9.1587 (4) Å	θ = 4.8–28.3°
b = 9.5551 (4) Å	µ = 0.73 mm⁻¹
c = 10.5041 (5) Å	T = 100 K
V = 919.24 (7) Å³	Prism, colorless
Z = 4	0.15 × 0.13 × 0.09 mm
F(000) = 544

Data collection top

Bruker D8 VENTURE diffractometer	2268 reflections with I > 2σ(I)
Radiation source: Mo microsource	R_int = 0.030
φ and ω scans	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −12→12
T_min = 0.889, T_max = 0.937	k = −12→12
47365 measured reflections	l = −14→14
2275 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.014	All H-atom parameters refined
wR(F²) = 0.035	w = 1/[σ²(F_o²) + (0.0154P)² + 0.187P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2275 reflections	Δρ_max = 0.28 e Å⁻³
184 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 937 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.023 (3)

Special details top

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.

Refinement. Hydrogen atoms were included in the model in observed positions and freely refined.

Crystal data, data collection and structure refinement details are summarized in Table 1. The crystal was selected and mounted on a MiTeGen MicroMount, protected with Fomblin oil. X-ray diffraction data were collected at 100 K on a D8 VENTURE Bruker diffractometer with Mo Kα radiation from IµS- DIAMOND microfocus source. Images were collected through ω and φ scans with a narrow step strategy. The raw data collection and processing, including absorption corrections, were done using APEX3 software package (Bruker, 2010). Structure was solved with direct methods and refined with Shelxls and Shelxl programs (Sheldrick, 2008, 2015), respectively. All non-hydrogen atoms were anisotropically refined.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.10736 (12)	0.64913 (12)	0.20067 (11)	0.0077 (2)
O11	0.05541 (9)	0.53123 (9)	0.16952 (9)	0.01010 (16)
O12	0.03571 (9)	0.75923 (9)	0.21440 (8)	0.00979 (16)
C2	0.27205 (12)	0.65990 (11)	0.22480 (11)	0.0072 (2)
H2	0.314 (2)	0.7252 (18)	0.1660 (17)	0.013 (4)*
O21	0.33762 (9)	0.52561 (9)	0.21224 (8)	0.00901 (16)
H21	0.414 (2)	0.540 (2)	0.171 (2)	0.024 (5)*
C3	0.29749 (13)	0.72088 (11)	0.35680 (10)	0.0071 (2)
H3	0.256 (2)	0.815 (2)	0.3574 (17)	0.016 (4)*
O31	0.22707 (9)	0.63913 (9)	0.45305 (8)	0.00848 (16)
H31	0.145 (3)	0.677 (2)	0.463 (2)	0.035 (6)*
C4	0.45907 (12)	0.73722 (12)	0.39115 (11)	0.0074 (2)
O41	0.48713 (9)	0.73136 (10)	0.50925 (9)	0.01108 (17)
O42	0.54987 (9)	0.76187 (9)	0.30555 (8)	0.00938 (16)
Ca1	0.18656 (2)	0.31714 (2)	0.17634 (2)	0.00667 (6)
O1W	0.22625 (10)	0.33681 (10)	0.41016 (9)	0.01211 (17)
H1W	0.141 (3)	0.312 (3)	0.435 (2)	0.039 (6)*
H2W	0.234 (3)	0.420 (3)	0.429 (2)	0.033 (6)*
O2W	0.18996 (10)	0.06249 (9)	0.16357 (9)	0.01289 (17)
H3W	0.266 (3)	0.018 (2)	0.153 (2)	0.032 (6)*
H4W	0.139 (3)	0.021 (2)	0.223 (2)	0.029 (5)*
O3W	0.42815 (10)	−0.08403 (10)	0.07665 (9)	0.01504 (18)
H5W	0.500 (3)	−0.113 (3)	0.129 (3)	0.042 (6)*
H6W	0.465 (2)	−0.058 (2)	0.012 (2)	0.022 (5)*
O4W	0.57266 (12)	0.57406 (12)	0.06310 (11)	0.0228 (2)
H7W	0.594 (3)	0.533 (3)	0.003 (3)	0.039 (6)*
H8W	0.621 (3)	0.647 (3)	0.063 (2)	0.034 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0078 (5)	0.0107 (5)	0.0046 (5)	−0.0001 (4)	−0.0001 (3)	0.0010 (4)
O11	0.0083 (4)	0.0089 (3)	0.0131 (4)	−0.0008 (3)	−0.0017 (3)	−0.0009 (3)
O12	0.0089 (4)	0.0098 (3)	0.0107 (4)	0.0019 (3)	0.0001 (3)	−0.0001 (3)
C2	0.0066 (5)	0.0074 (5)	0.0076 (5)	0.0006 (4)	−0.0003 (4)	−0.0005 (4)
O21	0.0069 (4)	0.0081 (4)	0.0121 (4)	0.0009 (3)	0.0016 (3)	−0.0020 (3)
C3	0.0068 (5)	0.0074 (5)	0.0070 (4)	0.0000 (4)	0.0001 (4)	0.0002 (3)
O31	0.0063 (4)	0.0119 (4)	0.0073 (4)	−0.0005 (3)	0.0016 (3)	0.0013 (3)
C4	0.0068 (5)	0.0058 (4)	0.0095 (5)	−0.0004 (4)	−0.0005 (4)	−0.0008 (4)
O41	0.0082 (4)	0.0171 (4)	0.0080 (4)	−0.0028 (3)	−0.0007 (3)	0.0007 (3)
O42	0.0076 (4)	0.0114 (3)	0.0092 (4)	−0.0010 (3)	0.0013 (3)	0.0000 (3)
Ca1	0.00612 (10)	0.00727 (10)	0.00663 (10)	0.00011 (8)	−0.00011 (7)	−0.00023 (8)
O1W	0.0110 (4)	0.0151 (5)	0.0102 (4)	−0.0030 (3)	0.0008 (3)	−0.0006 (3)
O2W	0.0103 (4)	0.0106 (4)	0.0178 (4)	0.0010 (3)	0.0025 (4)	0.0010 (3)
O3W	0.0116 (4)	0.0179 (4)	0.0157 (5)	0.0014 (4)	0.0022 (4)	0.0057 (4)
O4W	0.0236 (5)	0.0228 (5)	0.0220 (5)	−0.0094 (4)	0.0124 (4)	−0.0101 (4)

Geometric parameters (Å, º) top

C1—O12	1.2483 (15)	O41—Ca1ⁱⁱ	2.4137 (9)
C1—O11	1.2659 (14)	O42—Ca1ⁱⁱⁱ	2.4784 (9)
C1—C2	1.5330 (15)	Ca1—O12^iv	2.4016 (9)
O11—Ca1	2.3733 (8)	Ca1—O41^v	2.4136 (9)
O12—Ca1ⁱ	2.4015 (9)	Ca1—O2W	2.4371 (9)
C2—O21	1.4229 (13)	Ca1—O42^vi	2.4784 (9)
C2—C3	1.5220 (15)	Ca1—O1W	2.4900 (9)
C2—H2	0.959 (18)	Ca1—O31^v	2.5102 (9)
O21—Ca1	2.4544 (9)	Ca1—H1W	2.75 (2)
O21—H21	0.83 (2)	O1W—H1W	0.86 (3)
C3—O31	1.4312 (13)	O1W—H2W	0.82 (3)
C3—C4	1.5313 (16)	O2W—H3W	0.82 (2)
C3—H3	0.974 (19)	O2W—H4W	0.87 (2)
O31—Ca1ⁱⁱ	2.5102 (9)	O3W—H5W	0.90 (3)
O31—H31	0.84 (3)	O3W—H6W	0.80 (2)
C4—O42	1.2472 (14)	O4W—H7W	0.77 (3)
C4—O41	1.2681 (14)	O4W—H8W	0.83 (3)

O12—C1—O11	125.61 (10)	O41^v—Ca1—O21	129.72 (3)
O12—C1—C2	116.20 (10)	O2W—Ca1—O21	144.25 (3)
O11—C1—C2	118.18 (10)	O11—Ca1—O42^vi	132.76 (3)
C1—O11—Ca1	124.68 (7)	O12^iv—Ca1—O42^vi	137.72 (3)
C1—O12—Ca1ⁱ	134.03 (8)	O41^v—Ca1—O42^vi	131.06 (3)
O21—C2—C3	111.42 (9)	O2W—Ca1—O42^vi	77.23 (3)
O21—C2—C1	109.84 (9)	O21—Ca1—O42^vi	67.18 (3)
C3—C2—C1	109.08 (9)	O11—Ca1—O1W	92.21 (3)
O21—C2—H2	110.9 (11)	O12^iv—Ca1—O1W	70.71 (3)
C3—C2—H2	106.0 (10)	O41^v—Ca1—O1W	145.89 (3)
C1—C2—H2	109.6 (11)	O2W—Ca1—O1W	97.34 (3)
C2—O21—Ca1	120.55 (6)	O21—Ca1—O1W	72.84 (3)
C2—O21—H21	104.9 (14)	O42^vi—Ca1—O1W	78.36 (3)
Ca1—O21—H21	121.7 (15)	O11—Ca1—O31^v	89.30 (3)
O31—C3—C2	111.45 (9)	O12^iv—Ca1—O31^v	138.76 (3)
O31—C3—C4	108.95 (9)	O41^v—Ca1—O31^v	63.91 (3)
C2—C3—C4	113.68 (9)	O2W—Ca1—O31^v	96.36 (3)
O31—C3—H3	108.8 (11)	O21—Ca1—O31^v	80.26 (3)
C2—C3—H3	107.4 (11)	O42^vi—Ca1—O31^v	78.48 (3)
C4—C3—H3	106.3 (11)	O1W—Ca1—O31^v	149.66 (3)
C3—O31—Ca1ⁱⁱ	115.29 (6)	O11—Ca1—H1W	88.3 (5)
C3—O31—H31	104.6 (16)	O12^iv—Ca1—H1W	52.8 (5)
Ca1ⁱⁱ—O31—H31	95.5 (16)	O41^v—Ca1—H1W	128.0 (5)
O42—C4—O41	125.35 (11)	O2W—Ca1—H1W	92.2 (5)
O42—C4—C3	119.59 (10)	O21—Ca1—H1W	87.0 (5)
O41—C4—C3	114.95 (10)	O42^vi—Ca1—H1W	93.8 (5)
C4—O41—Ca1ⁱⁱ	125.89 (7)	O1W—Ca1—H1W	17.9 (5)
C4—O42—Ca1ⁱⁱⁱ	129.37 (8)	O31^v—Ca1—H1W	166.9 (5)
O11—Ca1—O12^iv	77.52 (3)	Ca1—O1W—H1W	98.7 (16)
O11—Ca1—O41^v	79.05 (3)	Ca1—O1W—H2W	108.8 (16)
O12^iv—Ca1—O41^v	75.20 (3)	H1W—O1W—H2W	106 (2)
O11—Ca1—O2W	149.92 (3)	Ca1—O2W—H3W	122.1 (16)
O12^iv—Ca1—O2W	78.88 (3)	Ca1—O2W—H4W	114.1 (15)
O41^v—Ca1—O2W	77.10 (3)	H3W—O2W—H4W	109 (2)
O11—Ca1—O21	65.82 (3)	H5W—O3W—H6W	108 (2)
O12^iv—Ca1—O21	126.25 (3)	H7W—O4W—H8W	107 (2)

O12—C1—O11—Ca1	−169.66 (9)	O21—C2—C3—C4	58.87 (11)
C2—C1—O11—Ca1	9.98 (14)	C1—C2—C3—C4	−179.70 (9)
O11—C1—O12—Ca1ⁱ	47.52 (17)	C2—C3—O31—Ca1ⁱⁱ	163.52 (7)
C2—C1—O12—Ca1ⁱ	−132.12 (9)	C4—C3—O31—Ca1ⁱⁱ	37.29 (10)
O12—C1—C2—O21	176.93 (10)	O31—C3—C4—O42	156.19 (10)
O11—C1—C2—O21	−2.74 (14)	C2—C3—C4—O42	31.26 (14)
O12—C1—C2—C3	54.54 (13)	O31—C3—C4—O41	−27.48 (13)
O11—C1—C2—C3	−125.12 (10)	C2—C3—C4—O41	−152.41 (10)
C3—C2—O21—Ca1	115.99 (8)	O42—C4—O41—Ca1ⁱⁱ	−179.72 (8)
C1—C2—O21—Ca1	−5.00 (11)	C3—C4—O41—Ca1ⁱⁱ	4.20 (14)
O21—C2—C3—O31	−64.72 (11)	O41—C4—O42—Ca1ⁱⁱⁱ	−2.40 (18)
C1—C2—C3—O31	56.71 (11)	C3—C4—O42—Ca1ⁱⁱⁱ	173.52 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O31—H31···O41^vii	0.84 (3)	1.71 (3)	2.5529 (12)	174 (2)
O21—H21···O4W	0.83 (2)	1.88 (2)	2.7023 (13)	174 (2)
O1W—H2W···O31	0.82 (3)	2.11 (3)	2.9236 (13)	170 (2)
O2W—H3W···O3W	0.82 (2)	1.95 (2)	2.7483 (13)	164 (2)
O2W—H4W···O11^iv	0.87 (2)	2.12 (2)	2.8658 (13)	144 (2)
O3W—H5W···O42^viii	0.90 (3)	2.26 (3)	3.0318 (13)	144 (2)
O3W—H6W···O11^ix	0.80 (2)	2.09 (2)	2.8809 (13)	168 (2)
O4W—H7W···O2W^ix	0.77 (3)	2.16 (3)	2.9199 (14)	170 (2)
O4W—H8W···O1Wⁱⁱⁱ	0.83 (3)	2.31 (3)	3.1263 (15)	171 (2)

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

Acknowledgements

Financial support from the University of Zaragoza, the Aragón Government and the MCIU/AEI/FEDER is kindly acknowledged.

Funding information

Funding for this research was provided by: Gobierno de Aragon (AP predoctoral fellow; award Nos. E42_23R and E05_23R); MCIU/AEI/FEDER (award Nos. PID2021-122406NB-I00 and PID2022-137208NB-I00); Universidad de Zaragoza.

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