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research papers
Revisiting a natural wine salt: calcium (2R,3R)-tartrate tetrahydrate
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
The R,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 of the crystal was established unambiguously using effects in the diffraction patterns. High-quality data also allowed the location and free of all the H atoms, and therefore to a careful analysis of the hydrogen-bond interactions.
of the salt calcium (2Keywords: 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 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 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 of this salt, corroborating the 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 (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 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 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 R,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 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 and therefore the 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 . 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 (Rint = 0.030) of this Ca-containing crystal allowed us to establish the in the solid state and therefore the of the molecule. For that purpose, the (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 (s.u.) value provide evidence for a strong inversion-distinguishing power and a correct estimation of the for this structural model.
|
3. Results and discussion
The R,3R)-C4H4O6]·4H2O (1) is formed by a Ca2+ ion, a tartrate ligand and four water molecules. In the 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 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 + |
![]() | Figure 3 Coordination sphere of the Ca2+ cation in 1. [Symmetry codes: (iv) −x, y − |
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 1, and which are not coordinated to Ca, are involved in hydrogen-bonding interactions. The 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
).
|
![]() | 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 P212121, as anticipated by Evans (1935). In this work, effects in the crystal diffraction patterns led to the determination of the of the L-(+)-tartrate salt 1. The has been resolved on the basis of 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
https://doi.org/10.1107/S2053229624008015/dg3060sup1.cif
contains datablocks I, global. DOI: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
[Ca(C4H4O6)(H2O)2]·2H2O | Dx = 1.880 Mg m−3 |
Mr = 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 |
Bruker D8 VENTURE diffractometer | 2268 reflections with I > 2σ(I) |
Radiation source: Mo microsource | Rint = 0.030 |
φ and ω scans | θmax = 28.3°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −12→12 |
Tmin = 0.889, Tmax = 0.937 | k = −12→12 |
47365 measured reflections | l = −14→14 |
2275 independent reflections |
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(Fo2) + (0.0154P)2 + 0.187P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2275 reflections | Δρmax = 0.28 e Å−3 |
184 parameters | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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—O12iv | 2.4016 (9) |
O11—Ca1 | 2.3733 (8) | Ca1—O41v | 2.4136 (9) |
O12—Ca1i | 2.4015 (9) | Ca1—O2W | 2.4371 (9) |
C2—O21 | 1.4229 (13) | Ca1—O42vi | 2.4784 (9) |
C2—C3 | 1.5220 (15) | Ca1—O1W | 2.4900 (9) |
C2—H2 | 0.959 (18) | Ca1—O31v | 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) | O41v—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—O42vi | 132.76 (3) |
C1—O11—Ca1 | 124.68 (7) | O12iv—Ca1—O42vi | 137.72 (3) |
C1—O12—Ca1i | 134.03 (8) | O41v—Ca1—O42vi | 131.06 (3) |
O21—C2—C3 | 111.42 (9) | O2W—Ca1—O42vi | 77.23 (3) |
O21—C2—C1 | 109.84 (9) | O21—Ca1—O42vi | 67.18 (3) |
C3—C2—C1 | 109.08 (9) | O11—Ca1—O1W | 92.21 (3) |
O21—C2—H2 | 110.9 (11) | O12iv—Ca1—O1W | 70.71 (3) |
C3—C2—H2 | 106.0 (10) | O41v—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) | O42vi—Ca1—O1W | 78.36 (3) |
Ca1—O21—H21 | 121.7 (15) | O11—Ca1—O31v | 89.30 (3) |
O31—C3—C2 | 111.45 (9) | O12iv—Ca1—O31v | 138.76 (3) |
O31—C3—C4 | 108.95 (9) | O41v—Ca1—O31v | 63.91 (3) |
C2—C3—C4 | 113.68 (9) | O2W—Ca1—O31v | 96.36 (3) |
O31—C3—H3 | 108.8 (11) | O21—Ca1—O31v | 80.26 (3) |
C2—C3—H3 | 107.4 (11) | O42vi—Ca1—O31v | 78.48 (3) |
C4—C3—H3 | 106.3 (11) | O1W—Ca1—O31v | 149.66 (3) |
C3—O31—Ca1ii | 115.29 (6) | O11—Ca1—H1W | 88.3 (5) |
C3—O31—H31 | 104.6 (16) | O12iv—Ca1—H1W | 52.8 (5) |
Ca1ii—O31—H31 | 95.5 (16) | O41v—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) | O42vi—Ca1—H1W | 93.8 (5) |
C4—O41—Ca1ii | 125.89 (7) | O1W—Ca1—H1W | 17.9 (5) |
C4—O42—Ca1iii | 129.37 (8) | O31v—Ca1—H1W | 166.9 (5) |
O11—Ca1—O12iv | 77.52 (3) | Ca1—O1W—H1W | 98.7 (16) |
O11—Ca1—O41v | 79.05 (3) | Ca1—O1W—H2W | 108.8 (16) |
O12iv—Ca1—O41v | 75.20 (3) | H1W—O1W—H2W | 106 (2) |
O11—Ca1—O2W | 149.92 (3) | Ca1—O2W—H3W | 122.1 (16) |
O12iv—Ca1—O2W | 78.88 (3) | Ca1—O2W—H4W | 114.1 (15) |
O41v—Ca1—O2W | 77.10 (3) | H3W—O2W—H4W | 109 (2) |
O11—Ca1—O21 | 65.82 (3) | H5W—O3W—H6W | 108 (2) |
O12iv—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
O31—H31···O41vii | 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···O11iv | 0.87 (2) | 2.12 (2) | 2.8658 (13) | 144 (2) |
O3W—H5W···O42viii | 0.90 (3) | 2.26 (3) | 3.0318 (13) | 144 (2) |
O3W—H6W···O11ix | 0.80 (2) | 2.09 (2) | 2.8809 (13) | 168 (2) |
O4W—H7W···O2Wix | 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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