Crystal structures of two SmIII complexes with dipicolinate [DPA]2− ligands: comparison of luminescent properties of products obtained at different pH values

Mortensen, S.S.; Sørensen, T.J.

doi:10.1107/S2056989023004814

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 79| Part 7| July 2023| Pages 619-625

https://doi.org/10.1107/S2056989023004814

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Crystal structures of two Sm^III complexes with dipicolinate [DPA]²⁻ ligands: comparison of luminescent properties of products obtained at different pH values

Sabina Svava Mortensen ^a ^* and Thomas Just Sørensen ^a

^aDepartment of Chemistry & Nano-Science Center, University of Copenhagen, Universitetsparken 5, 2100 København Ø, Denmark
^*Correspondence e-mail: sabina.svava.mortensen@hotmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 March 2023; accepted 2 June 2023; online 9 June 2023)

The formation of the two title compounds, Na₃[Sm(DPA)₃]·14H₂O trisodium tris(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)samarate(III) tetradecahydrate, Na₃[Sm(C₇H₃NO₄)₃]·14H₂O, and catena-poly[[[diaqua(6-carboxypyridine-2-carboxylato-κ³O²,N,O⁶)samarium(III)]-μ-pyridine-2,6-dicarboxylato-κ⁴O²,N,O⁶:O²] tetrahydrate], {[Sm(C₇H₃NO₄)(C₇H₄NO₄)(H₂O)₂]·4H₂O}_n, depends on the pH value adjusted with NaOH solution. In both crystal structures, the coordination spheres of the Sm^III cations were found to be best described by a tricapped trigonal prism (TTP), with a more regular O₆N₃ donor set for Na₃[Sm(DPA)₃]·14H₂O than that of O₇N₂ for [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O. The supramolecular features of both crystal structures are dominated by O—H⋯O hydrogen bonds between water molecules and the O atoms of the dipicolinato ligands. Samples were made from solutions at pH = 2, pH = 5, pH = 7, and pH = 10, and the crystals present in each sample were ground to a powder. The powder samples were analyzed with powder X-ray diffraction and luminescence spectroscopy. The splitting of the bands in the luminescence spectra recorded on powders at 77 K was observed to vary with the pH.

Keywords: crystal structure; luminescence; samarium(III); PXRD; hydrogen bonding.

CCDC references: 2246127; 2246128

1. Chemical context

The luminescent properties of lanthanide(III) complexes involving the tridentate dipicolinato ligand, [DPA]^2–, have been studied in great detail (Aebischer et al., 2009 ; Brayshaw et al., 1995 ; Chauvin et al., 2004 ; Kim et al., 1998 ; Kofod et al., 2020 ; Mondry & Starynowicz, 1995 ; Murray et al., 1990 ; Salaam et al., 2022 ; Zhou et al., 1994 ). The luminescent characteristics can be explained by the fact that the formed lanthanide(III) complex with three [DPA]^2– ligands coordinating to the central lanthanide(III) cation exhibits an almost perfect tricapped trigonal prism (TTP) coordination environment (Albertsson, 1970 ; Brayshaw et al., 1995; Kim et al., 1998; Li et al., 2019 ; Murray et al., 1990; Salaam et al., 2022; Zhou et al., 1994). The luminescence properties have been studied in great depth; however, our knowledge of Sm^III with [DPA]^2– as the ligand is rather limited (Chuasaard et al., 2017 ; Kumar et al., 2019 ; Sharif et al., 2016 ; Viveros-Andrade et al., 2017 ).

In the present communication, we report the crystal structures of two compounds with Sm^III cations and [DPA]^2– ligands, viz. salt-like Na₃[Sm(DPA)₃]·14H₂O and polymeric [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O. Both crystallized from mixtures of Sm(CF₃SO₃)₃ and H₂DPA solutions at different pH values adjusted with NaOH solution. The amount of the two compounds crystallized in each sample was found to be controlled by the pH value. This behavior was also monitored by powder X-ray diffraction (PXRD) of the bulk products and their luminescence spectra.

2. Structural commentary

Fig. 1 shows the coordination environment of the central Sm^III cation in the crystal structure of Na₃[Sm(DPA)₃]·14H₂O (CCDC number: 2246128). The donor set consists of six oxygen atoms from three chelating [DPA^2–] ligands, forming the top and bottom plane of a trigonal prism, and of three capping nitrogen donor atoms placed in the central plane of the trigonal prism. Each of the four Na^I cations (two on general positions and two on inversion centers) coordinates by aqua ligands and carboxylate O atoms, thus linking the [Sm(DPA)₃]^3– anions into a tri-periodic structure.

Figure 1
Coordination around the Sm^III cation in Na₃[Sm(DPA)₃]·14H₂O. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, y + 1, z.]

Fig. 2 illustrates the coordination environment of the central Sm^III cation in the crystal structure of [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O(CCDC number: 2246127). Although the coordination number of 9 is the same as in Na₃[Sm(DPA)₃]·14H₂O, here the donor set consists of seven oxygen atoms and two nitrogen atoms. Both [HDPA]⁻ and [DPA]^2– ligands N,O,O′-chelate the metal cation. The coordination sphere is completed by two aqua ligands and the carboxylate O atom of another symmetry-related [DPA]^2– anion, making it a polymeric structure, with chains of molecules extending parallel to [001].

Figure 2
Coordination around the Sm^III cation in [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ .]

For both coordination environments of the Sm^III cation in the title compounds, a symmetry-deviation analysis was performed to determine the deviation from an ideal coordination environment for coordination number 9. This was achieved by calculating a symmetry-deviation value, σ_ideal, using AlignIt (Storm Thomsen et al., 2022 ). More details of this method are described in the supporting information. Na₃[Sm(DPA)₃]·14H₂O was found to be best described as having the shape of a tricapped trigonal prism (TTP), with σ_ideal = 1.16, which is in good agreement with what has been reported for other isostructural Ln^III complexes (Albertsson, 1970, 1972 ; Hojnik et al., 2015 ; Mondry & Starynowicz, 1995; Tancrez et al., 2005 ; Elahi & Rajasekharan, 2016 ). The donor set in [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O is less symmetric compared to Na₃[Sm(DPA)₃]·14H₂O, consisting of two nitrogen atoms and seven oxygen atoms. Nevertheless, the Sm^III cation in [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O was also found to have a coordination polyhedron derived from a TTP, with σ_ideal = 0.73. This is in good agreement with what was reported for the Eu^III analogue (Liu et al., 2014 ).

3. Supramolecular features

Both Na₃[Sm(DPA)₃]·14H₂O and [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O contain water molecules, either solely present as solvent molecules for the Na-containing phase (14 per formula unit), or as solvent molecules and as ligands (2 and 4, respectively) for the other phase. Hence, the packing of the structural entities is mainly consolidated by O—H⋯O hydrogen-bonding networks (Tables 1, 2; Figs. 3, 4). The shortest hydrogen bonds in the two structures are formed between the carboxylate and carboxylic acid groups in [DPA]^2– and [HDPA]⁻ to the water molecules, including, for example, O4W—H4WB⋯O5W, O8W—H8WA⋯O10^vii, and O9W—H9WB⋯O1^viii in the Na₃[Sm(DPA)₃]·14H₂O structure, and O1W—H1WB⋯O7, O4W—H4WA⋯O2^v, and O6W—H6WB⋯O6 in the [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O structure. Notably, in [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O a very strong hydrogen bond [O4⋯O4W = 2.4703 (19) Å] is established between the carboxy group of the [HDPA]⁻ ligand and a solvent water molecule.

Table 1
Hydrogen-bond geometry (Å, °) for Na₃[Sm(DPA)₃]·14H₂O

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O13Wⁱ	0.85 (1)	1.98 (1)	2.8163 (19)	167 (3)
O2W—H2WA⋯O11Wⁱⁱ	0.86 (1)	2.10 (1)	2.927 (2)	160 (3)
O2W—H2WA⋯O12Wⁱⁱⁱ	0.86 (1)	2.76 (3)	3.2317 (19)	116 (2)
O2W—H2WB⋯O1W	0.86 (1)	1.90 (1)	2.742 (2)	164 (3)
O4W—H4WA⋯O5W	0.85 (1)	1.91 (1)	2.741 (2)	167 (3)
O4W—H4WB⋯O5	0.85 (1)	2.02 (1)	2.8534 (17)	169 (3)
O6W—H6WA⋯O12^iv	0.86 (1)	2.00 (1)	2.8435 (19)	168 (3)
O6W—H6WB⋯O8^v	0.87 (1)	2.09 (2)	2.8645 (18)	149 (3)
O7W—H7WA⋯O6W	0.84 (1)	1.93 (1)	2.7611 (19)	167 (3)
O7W—H7WB⋯O3^vi	0.85 (1)	2.54 (2)	3.1551 (17)	131 (2)
O7W—H7WB⋯O5^vi	0.85 (1)	2.31 (2)	3.0267 (17)	142 (2)
O8W—H8WA⋯O10^vii	0.84 (1)	1.87 (1)	2.7065 (17)	171 (2)
O9W—H9WA⋯O6^vi	0.85 (1)	1.94 (1)	2.7871 (16)	175 (2)
O9W—H9WB⋯O1^viii	0.85 (1)	1.87 (1)	2.7160 (16)	173 (2)
O10W—H10A⋯O2W^viii	0.85 (1)	1.90 (1)	2.7419 (18)	178 (2)
O11W—H11A⋯O9	0.85 (1)	1.97 (1)	2.8128 (17)	174 (3)
O11W—H11B⋯O12W	0.85 (1)	2.13 (1)	2.973 (2)	178 (3)
O12W—H12A⋯O2ⁱⁱⁱ	0.85 (1)	2.11 (1)	2.9542 (18)	173 (3)
O12W—H12B⋯O8W^vii	0.86 (1)	2.03 (2)	2.8057 (18)	149 (3)
O13W—H13A⋯O12W^vii	0.85 (1)	1.99 (1)	2.8235 (18)	170 (2)
O13W—H13B⋯O7^viii	0.85 (1)	2.09 (1)	2.9274 (17)	171 (2)
O13W—H13B⋯O8^viii	0.85 (1)	2.57 (2)	3.1929 (17)	132 (2)
Symmetry codes: (i) ; (ii) x, y+1, z; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Table 2
Hydrogen-bond geometry (Å, °) for [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2ⁱ	0.85 (1)	1.88 (1)	2.7218 (16)	169 (2)
O1W—H1WB⋯O7	0.85 (1)	1.91 (1)	2.7103 (15)	157 (2)
O2W—H2WA⋯O3W	0.85 (1)	1.87 (1)	2.7115 (16)	170 (2)
O2W—H2WB⋯O6Wⁱⁱ	0.85 (1)	1.90 (1)	2.7193 (16)	163 (2)
O3W—H3WA⋯O5ⁱⁱⁱ	0.85 (1)	2.04 (1)	2.8679 (15)	164 (2)
O3W—H3WB⋯O6^iv	0.85 (1)	2.01 (1)	2.8568 (16)	173 (2)
O4W—H4WA⋯O2^v	0.85 (1)	1.79 (1)	2.6360 (18)	174 (3)
O4W—H4WB⋯O5W	0.85 (1)	2.05 (2)	2.773 (2)	143 (3)
O5W—H5WA⋯O1^v	0.85 (1)	2.10 (1)	2.9340 (17)	167 (2)
O5W—H5WB⋯O6W^vi	0.85 (1)	2.14 (1)	2.9579 (19)	162 (2)
O6W—H6WA⋯O3W^vii	0.85 (1)	2.10 (1)	2.8696 (16)	151 (2)
O6W—H6WB⋯O6	0.85 (1)	1.83 (1)	2.6828 (16)	177 (2)
O4—H4⋯O4W	1.01 (3)	1.47 (3)	2.4703 (19)	174 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) ; (iii) x, y, z+1; (iv) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) x, y+1, z; (vi) x, y+1, z+1; (vii) .

Figure 3
Hydrogen-bonding network in the Na₃[Sm(DPA)₃]·14H₂O unit cell. Color code: Sm = dark blue, N = light blue, C = gray, H = white, O = red and Na = orange.

Figure 4
Hydrogen-bonding network in the [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O unit cell. Color code: Sm = dark blue, N = light blue, C = gray, H = white, and O = red.

4. Phase formation at different pH values

By combining a solution of Sm(CF₃SO₃)₃ and H₂DPA solutions at different pH values, the two title compounds crystallized in each batch. However, the amounts of each compound in a batch were found to be dependent on the pH value of the H₂DPA solution, which was controlled by addition of NaOH solution. Samples were made at pH = 2, pH = 5, pH = 7, and pH = 10, and the varying amount of the two compounds could be observed from the crystal photographs of each batch (Fig. 5). [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O was the dominating compound at pH = 2 (Fig. 5a), while Na₃[Sm(DPA)₃]·14H₂O was found to dominate at pH = 5, pH = 7, and pH = 10 (Fig. 5b,c,d). This finding is supported by PXRD data recorded from crystals crushed to a powder for all samples (Fig. 6).

Figure 5
Crystal photographs from selected samples obtained at different pH values; [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O crystals are circled in red and Na₃[Sm(DPA)₃]·14H₂O in blue. (a) Crystals obtained from a solution at pH = 2, where [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O dominates. (b) Crystals obtained from a solution at pH = 5, where an almost equal distribution of [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O and Na₃[Sm(DPA)₃]·14H₂O was found. (c) Crystals obtained from a solution at pH = 7, where more Na₃[Sm(DPA)₃]·14H₂O than [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O crystallized. (d) Crystals obtained from a solution at pH = 10, where Na₃[Sm(DPA)₃]·14H₂O dominates. The images in each panel were selected from three crystallization batches performed at each pH value.

Figure 6
PXRD pattern of the bulk for samples prepared from solution at pH = 2, pH = 5, pH = 7, and pH = 10, as well as simulated PXRD pattern on basis of the current single-crystal data.

5. Analysis of luminescence spectra for samples obtained at different pH values

The crystal field splitting is sensitive to the coordination environment and the donor atoms (Eliseeva & Bünzli, 2010 ). As Sm^III is a luminescent lanthanide(III) cation, the crystal field splitting of the spin-orbit defined ^SL_J term into the individual electronic states, here double-degenerate Kramers doublets defined by ±m_J values, can be observed from the luminescence spectra (Cheisson & Schelter, 2019 ; Wybourne, 2004 ; Chen et al., 2005 ; Mortensen et al., 2022 ; Carnall et al., 1968 ). Because Sm^III is a Kramers cation, it has an uneven number of electrons (4f⁵) and all states will be double degenerate without the presence of a magnetic field (Eliseeva & Bünzli, 2010). The electronic states in Sm^III are a complicated ⁶H_5/2 ground state and a ⁴G_5/2 emitting state that both have a large multiplicity (Eliseeva & Bünzli, 2010; Chen et al., 2005). The emitting state, ⁴G_5/2, can split into maximum Kramers levels. The maximum splitting is calculated as (2J + 1)/2 (Eliseeva & Bünzli, 2010). For the states observed from the emission spectra, the maximum splitting is three, four, five, and six for ⁶H_5/2, ⁶H_7/2, ⁶H_9/2, and ⁶H_11/2, respectively. To avoid deconvolution of nine bands or more in each transition, the spectra were recorded at 77 K for the polycrystalline material. At 77 K, one of the ±m_J doublets is predominately populated in ⁴G_5/2. Thus, only three bands will be observed for the ⁴G_5/2 → ⁶H_5/2 transition (Lupei et al., 2012 ; Chen et al., 2005; Skaudzius et al., 2018 ; Sakirzanovas et al., 2011 ). The number of observed bands for a ⁴G_5/2 → ⁶H_J transition should correspond to the maximum splitting of ⁶H_J (Eliseeva & Bünzli, 2010; Lupei et al., 2012; Chen et al., 2005; Skaudzius et al., 2018; Sakirzanovas et al., 2011). Additional bands can be an indicator for transitions from the less populated higher-energy ⁴G_5/2 states or the presence of more than one emitting species (Chen et al., 2005; Sakirzanovas et al., 2011). Because both Na₃[Sm(DPA)₃]·14H₂O and [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O are present in the samples, more bands than the maximum splitting are expected (Judd, 1962 ; Ofelt, 1962 ).

The luminescent properties of the samples obtained at different pH values were investigated in order to evaluate the effect of having different compounds present in each sample. From the emission spectra it was apparent that there is a change in the luminescenct properties with the change in compound distribution at different pH values (Fig. 7).

Figure 7
Normalized emission spectra in 2-methyltetrahydrofuran glass at 77 K (excitation at 394 nm) for samples prepared at pH = 2, pH = 5, pH = 7, and pH = 10.

Five bands are observed for the ⁴G_5/2 → ⁶H_7/2 transition in the emission spectra from all samples. This indicates that more than one species is present in the solid reaction product, as this is one more band than the maximum splitting for ⁶H_7/2 would allow per Sm^III atom. Hence, Sm^III exists in more than one coordination environment in the powdered samples of the bulk material. Thermal populations of more Kramers levels in ⁴G_5/2 would result in eight bands (Lupei et al., 2012; Chen et al., 2005; Skaudzius et al., 2018, Sakirzanovas et al., 2011). As this is not the case, the five bands are ascribed as a result of the presence of both Na₃[Sm(DPA)₃]·14H₂O and [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O, which both have a significant contribution to the emission spectrum of the samples obtained at different pH.

The change in the luminescent properties is apparent in the ⁴G_5/2 → ⁶H_9/2 transition, where the splitting patterns clearly varies. Additionally, there is a change in the intensity of the ⁴G_5/2 → ⁶H_9/2 transition compared to the the ⁴G_5/2 → ⁶H_7/2 transition. At pH = 2, the ⁴G_5/2 → ⁶H_7/2 transition is the most intense, whereas at pH = 10, the ⁴G_5/2 → ⁶H_9/2 transition has a higher intensity compared to ⁴G_5/2 → ⁶H_7/2 transition. Also, the ⁴G_5/2 → ⁶H_5/2 transition increased in intensity compared to the ⁴G_5/2 → ⁶H_7/2 band with increasing pH. However, no clear spectral components could be assigned to either Na₃[Sm(DPA)₃]·14H₂O or [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O. Additional spectra are included in the supporting information.

6. Database survey

Na₃[Sm(DPA)₃]·14H₂O is isostructural with other Na₃[Ln(DPA)₃]·14H₂O compounds previously reported for La^III, Ce^III, Pr^III, Nd^III, Sm^III, Eu^III, Gd^III, Tb^III, Dy^III, Ho^III, Yb^III, and Lu^III (Albertsson, 1970; Hojnik et al., 2015; Albertsson, 1972; Albertsson et al., 1972; Mondry & Starynowicz, 1995; Tancrez et al., 2005; Elahi & Rajasekharan, 2016). Crystal data of Na₃[Sm(DPA)₃]·14H₂O have been deposited at the CCDC (CSD code SOPGOT; Hu et al., 1989 ); however, without atomic coordinates, which motivated us to reinvestigate the crystal structure.

[Sm(DPA)(HDPA)(H₂O)₂]·4H₂O is isostructural with other [Ln(DPA)(HDPA)(H₂O)₂]·4H₂O compounds previously reported for Ce^III, Pr^III, Nd^III, Sm^III, Eu^III, Gd^III, Tb^III, Dy^III, and Er^III (Brayshaw et al., 2005 ; Cheng et al., 2007 ; Chuasaard et al., 2017; Ghosh & Bharadwaj, 2003 ; Hou et al., 2011 ; Kang, 2011 ; Liu et al., 2005 ; Moghzi et al., 2020 ; Najafi et al., 2017 ; Rafizadeh et al., 2005 ; Song et al., 2005 ; Wang et al., 2012 ; Xu et al., 2009 ; Kong et al., 2022 ). The crystal structure of [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O has been reported previously several times (CSD code FONCUH; best result in terms of reliability factors: FONCUH01; Rafizadeh et al., 2005). For interpretation of the luminescence spectra and a comparison with Na₃[Sm(DPA)₃]·14H₂O, we have also reinvestigated the crystal structure of [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O.

7. Synthesis and crystallization

All chemicals were used as received without further purification. All crystallization experiments were conducted three times.

0.2 M Sm(CF₃SO₃)₃ stock solution

Sm(CF₃SO₃)₃ (2.39 g, 0.400 mmol; 98% from STREM Chemicals) was used to create a 0.20 M stock solution by dissolving the salt in water to create a solution with a volume of 20.0±0.04 ml.

0.2 M H₂DPA stock solution

H₂DPA (pyridine-2,6-dicarboxylic acid; 0.669 g, 4.01 mmol; Riedel-De Haën) was used to create a 0.2 M stock solution by dissolving the acid in water to create a solution with a volume of 20±0.04 ml.

Sm(DPA) at pH = 2 – crystallization

1.0 ml of the 0.2 M Sm(CF₃SO₃)₃ stock solution was added to a sample vial with 3.0 ml of the 0.2 M H₂DPA stock solution. The sample was heated at 353 K for 1 h. The sample vial was closed with a lid and left in a dark place. After 1 d crystals had formed.

Sm(DPA) at pH = 5 – crystallization

NaOH (1.0 M) was added to the H₂DPA stock solution to adjust the pH to 5. 0.5 ml of the 0.2 M Sm(CF₃SO₃)₃ solution were added to a sample vial with 1.5 ml of the 0.2 M H₂DPA stock solution. The sample was heated at 353 K for 1 h. The sample vial was placed in a container with acetone, placing a lid on top of the container and left for acetone diffusion. After 3 d crystals had formed.

Sm(DPA) at pH = 7 – crystallization

NaOH (1.0 M) was added to the H₂DPA stock solution to adjust the pH to 7. 0.5 ml of the 0.2 M Sm(CF₃SO₃)₃ solution were added to a sample vial with 1.5 ml of the 0.2 M H₂DPA stock solution. The sample was heated at 353 K for 1 h. The sample was then filtered through a Q-Max RR syringe filter from Frisinette and transferred to a vial. The latter was placed in a container with acetone, placing a lid on top of the container and left for an acetone diffusion. After 1 d crystals had formed.

Sm(DPA) at pH = 10 – crystallization

NaOH (1.0 M) was added to the H₂DPA stock solution to adjust the pH to 10. 0.5 ml of the 0.2 M Sm(CF₃SO₃)₃ solution were added to a sample vial with 1.5 ml of the 0.2 M H₂DPA stock solution. The sample was heated at 353 K for 1 h. The sample was then filtered through a Q-Max RR syringe filter from Frisinette and transferred to a vial. The later was placed in a container with acetone, placing a lid on top of the container and left for an acetone diffusion. After 1 d crystals had formed.

8. Other experimental procedures

For both PXRD and optical spectroscopy measurements, the crystals, which had precipitated in each sample, were collected by suction filtration with a vacuum pump. The crystals were removed from the filter, dried in air and ground to a powder.

Powder X-ray Diffraction

PXRD diffractograms were recorded for all samples prepared at different pH values. Data were collected using a Bruker D8 Advance diffractometer using a Cu Kα source (λ = 1.5406 Å). Samples were measured using a low-background silica sample holder at 293 K.

Optical Spectroscopy

Crystal powders from all samples prepared at different pH were added to a 5.0 mm diameter NMR silica cylinder (Bruker) together with 2-methyltetrahydrofuran glass. The samples were cooled using liquid nitrogen and were measured using a cold-finger setup. This setup was used for both the emission and excitation spectra and for determination of luminescent lifetimes.

Emission and excitation spectra were measured with a xenon arc lamp as the excitation source on a PTI QuantaMaster8075 from Horiba Scientific.

For emission spectroscopy, an excitation wavelength at 401 nm (24938 cm⁻¹) was used. Emission was detected from 550 nm (18182 cm⁻¹) to 760 nm (13158 cm⁻¹). The emission slits were kept at 1.0 nm for the two outermost slits and 5.0 nm or the middle slit for all samples, and the excitation slits were all kept at 8.0 nm. The voltage bias was kept at 3.2 V for the reference detector.

For excitation spectroscopy, an emission wavelength at 598 nm (16722 cm⁻¹) was used. Excitation was detected from 250 nm (40000 cm⁻¹) to 590 nm (16949 cm⁻¹). Emission slits were all kept at 8.0 nm and excitation slits were kept at 1.0 nm for the two outermost slits and 5.0 nm for the middle slit for all samples. The voltage bias was kept at 6.8 V for the reference detector.

Luminescence Lifetimes

The luminescence lifetimes were determined for all powder samples using a TCSPC FluoTime300 from PicoQuant. The excitation wavelength was 405 nm (24691 cm⁻¹), and the emission wavelength 600 nm (16667 cm⁻¹). The effective sync rate was kept at 1 kHz, with 5000 pulses, a period length of 1.0 ms, a burst length of 625 µs, and a time/channel at 80 ns. The temperature was kept at 298 K. The luminescence lifetimes were fitted using a mono-exponential decay function using the software EasyTau 2 (PicoQuant, 2018 ).

9. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms attached to aromatic carbon atoms were added automatically using a riding model with U_iso(H) = 1.2U_eq(C). All hydrogen atoms of water molecules were discernible in difference-Fourier maps. They were refined with a distance restraint of 0.85 Å, and with U_iso(H) = 1.5U_eq(C). The H atom of the carboxylate group (H4) in [Sm(DPA)(HDPA)(H₂O)₂]·4H₂O was found in difference-Fourier maps and was refined freely. The comparatively high residual positive electron density in Na₃[Sm(DPA)₃]·14H₂O is located at distances of ≃1.4 Å from atoms H6WA and H6WB. Contributions of additional atoms and/or disorder did not result in other reasonable models.

Table 3
Experimental details

	Na₃[Sm(C₇H₃NO₄)₃]·14H₂O	[Sm(C₇H₃NO₄)(C₇H₄NO₄)(H₂O)₂]·4H₂O
Crystal data
M_r	966.85	589.66
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/c
Temperature (K)	100	100
a, b, c (Å)	10.2674 (10), 10.9688 (10), 17.1570 (16)	13.9292 (8), 11.1969 (7), 12.8086 (7)
α, β, γ (°)	73.835 (3), 77.573 (3), 72.894 (3)	90, 103.049 (2), 90
V (Å³)	1754.9 (3)	1946.1 (2)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	1.81	3.10
Crystal size (mm)	0.78 × 0.58 × 0.26	0.48 × 0.40 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2019 )	Multi-scan (SADABS; Bruker, 2019)
T_min, T_max	0.615, 0.747	0.575, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	107477, 13465, 12700	74345, 7424, 6679
R_int	0.045	0.044
(sin θ/λ)_max (Å⁻¹)	0.771	0.769

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.058, 1.11	0.018, 0.042, 1.08
No. of reflections	13465	7424
No. of parameters	574	319
No. of restraints	28	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	3.32, −1.15	0.73, −1.09
Computer programs: APEX2 and SAINT (Bruker, 2019), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2246127; 2246128

Crystal structure: contains datablocks mo_d8v5334_0m_a, I, II. DOI: https://doi.org/10.1107/S2056989023004814/wm5678sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004814/wm5678Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989023004814/wm5678IIsup3.hkl

Spectra, symmetry deviation analysis, and PXRD. DOI: https://doi.org/10.1107/S2056989023004814/wm5678sup3.pdf

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Trisodium tris(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)samarate(III) tetradecahydrate (I) top

Crystal data top

Na₃[Sm(C₇H₃NO₄)₃]·14H₂O	Z = 2
M_r = 966.85	F(000) = 974
Triclinic, P1	D_x = 1.830 Mg m⁻³
a = 10.2674 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9688 (10) Å	Cell parameters from 9982 reflections
c = 17.1570 (16) Å	θ = 2.4–33.2°
α = 73.835 (3)°	µ = 1.81 mm⁻¹
β = 77.573 (3)°	T = 100 K
γ = 72.894 (3)°	Prism, colourless
V = 1754.9 (3) Å³	0.78 × 0.58 × 0.26 mm

Data collection top

Bruker APEXII CCD diffractometer	12700 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.045
Absorption correction: multi-scan (SADABS; Bruker, 2019)	θ_max = 33.2°, θ_min = 2.0°
T_min = 0.615, T_max = 0.747	h = −15→15
107477 measured reflections	k = −16→16
13465 independent reflections	l = −26→26

Refinement top

Refinement on F²	28 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.021P)² + 2.2772P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.004
13465 reflections	Δρ_max = 3.32 e Å⁻³
574 parameters	Δρ_min = −1.15 e Å⁻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.

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

	x	y	z	U_iso*/U_eq
Sm1	0.48815 (2)	0.74844 (2)	0.75088 (2)	0.00321 (2)
Na1	0.500000	0.500000	0.500000	0.00980 (16)
Na2	0.50358 (6)	0.25158 (6)	0.75459 (4)	0.00837 (11)
Na3	0.14568 (7)	1.30026 (7)	0.74024 (5)	0.01388 (13)
Na4	0.500000	0.000000	1.000000	0.00854 (16)
O1	0.32228 (11)	0.96519 (11)	0.72600 (7)	0.00735 (19)
O2	0.10717 (12)	1.09223 (11)	0.74353 (8)	0.0111 (2)
O3	0.42909 (11)	0.53805 (11)	0.78804 (7)	0.00775 (19)
O4	0.29239 (12)	0.41204 (11)	0.78682 (8)	0.0117 (2)
O5	0.47032 (11)	0.71148 (11)	0.62035 (7)	0.00748 (19)
O6	0.55858 (13)	0.70498 (12)	0.49004 (7)	0.0109 (2)
O7	0.60619 (11)	0.90222 (11)	0.77079 (7)	0.00738 (19)
O8	0.69830 (11)	1.07466 (11)	0.72233 (7)	0.00862 (19)
O9	0.39263 (11)	−0.21216 (11)	0.88660 (7)	0.00830 (19)
O10	0.43084 (12)	−0.19347 (12)	1.00559 (7)	0.0103 (2)
O11	0.70788 (11)	−0.41510 (11)	0.71542 (7)	0.00843 (19)
O12	0.89428 (11)	−0.57662 (11)	0.74960 (7)	0.0100 (2)
N1	0.23451 (12)	0.75259 (12)	0.76118 (8)	0.0053 (2)
N2	0.60933 (13)	0.87570 (12)	0.62274 (8)	0.0055 (2)
N3	0.63346 (13)	−0.37902 (12)	0.86490 (8)	0.0059 (2)
C1	0.19098 (15)	0.98546 (14)	0.73974 (9)	0.0061 (2)
C2	0.13830 (14)	0.86619 (14)	0.75074 (9)	0.0065 (2)
C3	0.00166 (16)	0.87325 (16)	0.74916 (11)	0.0123 (3)
H3	−0.063565	0.953392	0.742608	0.015*
C4	−0.03531 (17)	0.75749 (17)	0.75761 (13)	0.0169 (3)
H4	−0.125743	0.759170	0.755871	0.020*
C5	0.06437 (16)	0.63935 (16)	0.76868 (12)	0.0132 (3)
H5	0.042040	0.560674	0.774643	0.016*
C6	0.19804 (14)	0.64151 (14)	0.77064 (9)	0.0065 (2)
C7	0.31407 (15)	0.51924 (14)	0.78274 (9)	0.0066 (2)
C8	0.54421 (15)	0.74740 (14)	0.55205 (9)	0.0065 (2)
C9	0.61918 (15)	0.84837 (14)	0.55005 (9)	0.0063 (2)
C10	0.69509 (17)	0.90667 (16)	0.47973 (10)	0.0110 (3)
H10	0.702967	0.884285	0.430172	0.013*
C11	0.75889 (19)	0.99887 (18)	0.48485 (10)	0.0141 (3)
H11	0.809417	1.039876	0.438477	0.017*
C12	0.74666 (17)	1.02945 (16)	0.55983 (10)	0.0114 (3)
H12	0.787242	1.092062	0.564500	0.014*
C13	0.67220 (15)	0.96399 (14)	0.62765 (9)	0.0062 (2)
C14	0.65829 (14)	0.98425 (14)	0.71282 (9)	0.0059 (2)
C15	0.46267 (15)	−0.24388 (14)	0.94523 (9)	0.0068 (2)
C16	0.59566 (15)	−0.34874 (15)	0.93826 (9)	0.0072 (2)
C17	0.67366 (17)	−0.40708 (17)	1.00180 (10)	0.0134 (3)
H17	0.646641	−0.382103	1.051571	0.016*
C18	0.79362 (18)	−0.50416 (19)	0.98895 (11)	0.0167 (3)
H18	0.847093	−0.546644	1.030714	0.020*
C19	0.83254 (16)	−0.53684 (17)	0.91333 (10)	0.0122 (3)
H19	0.911577	−0.602159	0.903756	0.015*
C20	0.75090 (15)	−0.46988 (14)	0.85216 (9)	0.0066 (2)
C21	0.78861 (15)	−0.49090 (14)	0.76585 (9)	0.0068 (2)
O1W	0.04883 (15)	1.24786 (15)	1.03199 (9)	0.0206 (3)
H1WA	−0.008 (2)	1.201 (2)	1.0422 (18)	0.031*
H1WB	0.1197 (19)	1.203 (2)	1.0544 (16)	0.031*
O2W	0.14195 (14)	1.18981 (14)	0.88110 (9)	0.0173 (2)
H2WA	0.122 (3)	1.1150 (15)	0.8944 (17)	0.026*
H2WB	0.114 (3)	1.223 (3)	0.9238 (11)	0.026*
O3W	0.13440 (13)	1.42018 (13)	0.60105 (9)	0.0175 (3)
H3WA	0.190 (2)	1.467 (2)	0.5968 (17)	0.026*
H3WB	0.0554 (15)	1.470 (2)	0.5944 (17)	0.026*
O4W	0.28586 (13)	0.60772 (13)	0.57011 (8)	0.0153 (2)
H4WA	0.221 (2)	0.665 (2)	0.5476 (15)	0.023*
H4WB	0.331 (2)	0.644 (2)	0.5892 (15)	0.023*
O5W	0.05492 (16)	0.76417 (16)	0.50456 (10)	0.0248 (3)
H5WA	−0.011 (2)	0.728 (3)	0.5275 (18)	0.037*
H5WB	0.078 (3)	0.751 (3)	0.4552 (9)	0.037*
O6W	0.16147 (15)	0.72091 (14)	0.34836 (9)	0.0194 (3)
H6WA	0.133 (3)	0.686 (3)	0.3180 (15)	0.029*
H6WB	0.179 (3)	0.7923 (17)	0.3158 (14)	0.029*
O7W	0.42934 (13)	0.58120 (12)	0.36593 (8)	0.0119 (2)
H7WA	0.3439 (11)	0.614 (2)	0.3659 (16)	0.018*
H7WB	0.444 (3)	0.5135 (17)	0.3476 (15)	0.018*
O8W	0.62364 (12)	0.31062 (11)	0.83406 (7)	0.0097 (2)
H8WA	0.597 (2)	0.276 (2)	0.8833 (7)	0.015*
H8WB	0.569 (2)	0.3851 (13)	0.8228 (15)	0.015*
O9W	0.37670 (12)	0.20510 (11)	0.67876 (7)	0.00911 (19)
H9WA	0.391 (2)	0.233 (2)	0.6273 (6)	0.014*
H9WB	0.365 (2)	0.1282 (13)	0.6909 (15)	0.014*
O10W	0.42198 (12)	0.09077 (12)	0.86809 (7)	0.0103 (2)
H10A	0.3359 (10)	0.122 (2)	0.8710 (15)	0.016*
H10B	0.442 (3)	0.0245 (17)	0.8480 (14)	0.016*
O11W	0.12847 (13)	−0.08265 (14)	0.95098 (9)	0.0170 (2)
H11A	0.2100 (14)	−0.117 (3)	0.9312 (16)	0.025*
H11B	0.132 (3)	−0.091 (3)	1.0010 (7)	0.025*
O12W	0.13612 (13)	−0.11638 (14)	1.12813 (9)	0.0168 (2)
H12A	0.0624 (18)	−0.111 (3)	1.1623 (13)	0.025*
H12B	0.187 (2)	−0.1918 (15)	1.1490 (16)	0.025*
O13W	0.71107 (12)	−0.07398 (12)	0.91019 (7)	0.0118 (2)
H13A	0.751 (2)	−0.0124 (18)	0.8938 (15)	0.018*
H13B	0.688 (3)	−0.077 (2)	0.8664 (10)	0.018*
O14W	0.87868 (14)	−0.40551 (14)	0.56379 (8)	0.0173 (2)
H14A	0.820 (2)	−0.413 (3)	0.6072 (11)	0.026*
H14B	0.849 (3)	−0.412 (3)	0.5230 (12)	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sm1	0.00305 (3)	0.00300 (3)	0.00357 (3)	−0.00045 (2)	−0.00041 (2)	−0.00111 (2)
Na1	0.0114 (4)	0.0097 (4)	0.0094 (4)	−0.0041 (3)	−0.0013 (3)	−0.0026 (3)
Na2	0.0084 (3)	0.0083 (3)	0.0095 (3)	−0.0017 (2)	−0.0021 (2)	−0.0035 (2)
Na3	0.0141 (3)	0.0118 (3)	0.0153 (3)	−0.0031 (2)	−0.0016 (3)	−0.0031 (3)
Na4	0.0096 (4)	0.0086 (4)	0.0074 (4)	−0.0014 (3)	−0.0015 (3)	−0.0024 (3)
O1	0.0053 (4)	0.0053 (4)	0.0107 (5)	−0.0013 (3)	−0.0009 (4)	−0.0009 (4)
O2	0.0087 (5)	0.0051 (5)	0.0181 (6)	0.0005 (4)	−0.0007 (4)	−0.0038 (4)
O3	0.0057 (4)	0.0051 (4)	0.0116 (5)	−0.0010 (3)	−0.0013 (4)	−0.0008 (4)
O4	0.0104 (5)	0.0048 (5)	0.0199 (6)	−0.0029 (4)	0.0004 (4)	−0.0039 (4)
O5	0.0089 (4)	0.0099 (5)	0.0054 (4)	−0.0053 (4)	0.0004 (4)	−0.0025 (4)
O6	0.0172 (5)	0.0126 (5)	0.0061 (5)	−0.0080 (4)	0.0004 (4)	−0.0041 (4)
O7	0.0092 (5)	0.0075 (5)	0.0064 (5)	−0.0036 (4)	−0.0016 (4)	−0.0013 (4)
O8	0.0089 (5)	0.0072 (5)	0.0121 (5)	−0.0031 (4)	−0.0019 (4)	−0.0044 (4)
O9	0.0072 (4)	0.0106 (5)	0.0060 (5)	0.0009 (4)	−0.0017 (4)	−0.0031 (4)
O10	0.0138 (5)	0.0098 (5)	0.0069 (5)	−0.0004 (4)	−0.0012 (4)	−0.0043 (4)
O11	0.0069 (4)	0.0097 (5)	0.0071 (5)	0.0006 (4)	−0.0012 (4)	−0.0020 (4)
O12	0.0064 (4)	0.0098 (5)	0.0127 (5)	0.0014 (4)	−0.0005 (4)	−0.0052 (4)
N1	0.0051 (5)	0.0045 (5)	0.0060 (5)	−0.0007 (4)	−0.0003 (4)	−0.0014 (4)
N2	0.0059 (5)	0.0047 (5)	0.0061 (5)	−0.0016 (4)	−0.0009 (4)	−0.0015 (4)
N3	0.0060 (5)	0.0049 (5)	0.0064 (5)	−0.0010 (4)	−0.0007 (4)	−0.0014 (4)
C1	0.0065 (6)	0.0045 (6)	0.0070 (6)	−0.0012 (4)	−0.0011 (4)	−0.0008 (5)
C2	0.0053 (5)	0.0054 (6)	0.0085 (6)	−0.0009 (4)	−0.0007 (4)	−0.0017 (5)
C3	0.0053 (6)	0.0076 (6)	0.0239 (8)	0.0002 (5)	−0.0031 (5)	−0.0048 (6)
C4	0.0070 (6)	0.0100 (7)	0.0358 (10)	−0.0024 (5)	−0.0046 (6)	−0.0071 (7)
C5	0.0068 (6)	0.0081 (7)	0.0260 (9)	−0.0025 (5)	−0.0019 (6)	−0.0057 (6)
C6	0.0054 (5)	0.0050 (6)	0.0092 (6)	−0.0015 (4)	0.0006 (4)	−0.0028 (5)
C7	0.0059 (5)	0.0052 (6)	0.0079 (6)	−0.0008 (4)	0.0006 (4)	−0.0018 (5)
C8	0.0075 (6)	0.0065 (6)	0.0060 (6)	−0.0022 (5)	−0.0012 (4)	−0.0015 (5)
C9	0.0074 (6)	0.0062 (6)	0.0056 (6)	−0.0023 (5)	−0.0011 (4)	−0.0010 (5)
C10	0.0148 (7)	0.0134 (7)	0.0070 (6)	−0.0086 (6)	0.0001 (5)	−0.0018 (5)
C11	0.0204 (8)	0.0174 (8)	0.0077 (7)	−0.0131 (6)	0.0019 (6)	−0.0017 (6)
C12	0.0151 (7)	0.0125 (7)	0.0093 (6)	−0.0099 (6)	0.0002 (5)	−0.0016 (5)
C13	0.0067 (5)	0.0054 (6)	0.0070 (6)	−0.0022 (4)	−0.0013 (4)	−0.0011 (5)
C14	0.0037 (5)	0.0055 (6)	0.0091 (6)	−0.0001 (4)	−0.0022 (4)	−0.0026 (5)
C15	0.0079 (6)	0.0062 (6)	0.0054 (6)	−0.0018 (5)	0.0003 (4)	−0.0010 (5)
C16	0.0074 (6)	0.0071 (6)	0.0067 (6)	−0.0004 (5)	−0.0022 (5)	−0.0014 (5)
C17	0.0128 (7)	0.0162 (7)	0.0085 (7)	0.0035 (6)	−0.0050 (5)	−0.0033 (6)
C18	0.0136 (7)	0.0210 (8)	0.0108 (7)	0.0062 (6)	−0.0072 (6)	−0.0033 (6)
C19	0.0091 (6)	0.0129 (7)	0.0110 (7)	0.0038 (5)	−0.0041 (5)	−0.0023 (5)
C20	0.0061 (5)	0.0057 (6)	0.0073 (6)	−0.0007 (4)	−0.0015 (4)	−0.0011 (5)
C21	0.0051 (5)	0.0067 (6)	0.0087 (6)	−0.0016 (4)	0.0003 (5)	−0.0029 (5)
O1W	0.0154 (6)	0.0214 (7)	0.0224 (7)	0.0007 (5)	−0.0086 (5)	−0.0020 (5)
O2W	0.0145 (6)	0.0194 (6)	0.0200 (6)	−0.0046 (5)	−0.0026 (5)	−0.0076 (5)
O3W	0.0104 (5)	0.0145 (6)	0.0238 (7)	−0.0024 (4)	0.0002 (5)	−0.0012 (5)
O4W	0.0120 (5)	0.0174 (6)	0.0193 (6)	−0.0056 (5)	−0.0020 (4)	−0.0070 (5)
O5W	0.0208 (7)	0.0254 (8)	0.0269 (8)	−0.0074 (6)	−0.0052 (6)	−0.0008 (6)
O6W	0.0188 (6)	0.0178 (6)	0.0235 (7)	−0.0049 (5)	−0.0067 (5)	−0.0045 (5)
O7W	0.0143 (5)	0.0099 (5)	0.0121 (5)	−0.0025 (4)	−0.0024 (4)	−0.0040 (4)
O8W	0.0101 (5)	0.0073 (5)	0.0109 (5)	−0.0004 (4)	−0.0035 (4)	−0.0010 (4)
O9W	0.0127 (5)	0.0082 (5)	0.0078 (5)	−0.0047 (4)	−0.0021 (4)	−0.0014 (4)
O10W	0.0105 (5)	0.0090 (5)	0.0102 (5)	0.0008 (4)	−0.0025 (4)	−0.0027 (4)
O11W	0.0093 (5)	0.0195 (6)	0.0188 (6)	0.0020 (5)	−0.0015 (5)	−0.0056 (5)
O12W	0.0098 (5)	0.0183 (6)	0.0216 (7)	−0.0027 (5)	0.0017 (5)	−0.0076 (5)
O13W	0.0107 (5)	0.0146 (6)	0.0096 (5)	−0.0023 (4)	−0.0026 (4)	−0.0023 (4)
O14W	0.0132 (6)	0.0215 (6)	0.0118 (6)	−0.0012 (5)	−0.0001 (4)	−0.0002 (5)

Geometric parameters (Å, º) top

Sm1—O1	2.4700 (11)	N3—C20	1.3400 (19)
Sm1—O3	2.4367 (11)	C1—C2	1.508 (2)
Sm1—O5	2.4371 (11)	C2—C3	1.388 (2)
Sm1—O7	2.4764 (11)	C3—H3	0.9300
Sm1—O9ⁱ	2.4288 (11)	C3—C4	1.391 (2)
Sm1—O11ⁱ	2.5128 (11)	C4—H4	0.9300
Sm1—N1	2.5597 (12)	C4—C5	1.389 (2)
Sm1—N2	2.5428 (12)	C5—H5	0.9300
Sm1—N3ⁱ	2.5522 (13)	C5—C6	1.387 (2)
Na1—O6ⁱⁱ	2.4461 (12)	C6—C7	1.507 (2)
Na1—O6	2.4461 (12)	C8—C9	1.513 (2)
Na1—O4W	2.4087 (13)	C9—C10	1.389 (2)
Na1—O4Wⁱⁱ	2.4087 (13)	C10—H10	0.9300
Na1—H4WB	2.54 (3)	C10—C11	1.387 (2)
Na1—O7Wⁱⁱ	2.4100 (13)	C11—H11	0.9300
Na1—O7W	2.4100 (13)	C11—C12	1.389 (2)
Na2—Na3ⁱⁱⁱ	3.6071 (10)	C12—H12	0.9300
Na2—O4	2.4261 (13)	C12—C13	1.389 (2)
Na2—O8ⁱⁱⁱ	2.4308 (13)	C13—C14	1.509 (2)
Na2—C7	3.1086 (16)	C15—C16	1.511 (2)
Na2—C14ⁱⁱⁱ	3.0944 (16)	C16—C17	1.387 (2)
Na2—O7Wⁱⁱ	2.4764 (14)	C17—H17	0.9300
Na2—O8W	2.3415 (13)	C17—C18	1.393 (2)
Na2—H8WB	2.41 (2)	C18—H18	0.9300
Na2—O9W	2.2670 (13)	C18—C19	1.387 (2)
Na2—O10W	2.4208 (14)	C19—H19	0.9300
Na3—O2	2.4117 (14)	C19—C20	1.389 (2)
Na3—O4ⁱ	2.5614 (14)	C20—C21	1.512 (2)
Na3—O12^iv	2.5306 (13)	O1W—H1WA	0.852 (10)
Na3—O2W	2.3805 (16)	O1W—H1WB	0.850 (10)
Na3—O3W	2.3931 (16)	O2W—H2WA	0.861 (10)
Na3—H3WA	2.66 (3)	O2W—H2WB	0.862 (10)
Na3—O9Wⁱ	2.4307 (14)	O3W—H3WA	0.847 (10)
Na4—O10	2.4001 (12)	O3W—H3WB	0.846 (10)
Na4—O10^v	2.4001 (12)	O4W—H4WA	0.849 (10)
Na4—O10W^v	2.4107 (12)	O4W—H4WB	0.847 (10)
Na4—O10W	2.4107 (12)	O5W—H5WA	0.852 (10)
Na4—O13W^v	2.4400 (12)	O5W—H5WB	0.871 (10)
Na4—O13W	2.4400 (12)	O6W—H6WA	0.862 (10)
O1—C1	1.2800 (17)	O6W—H6WB	0.867 (10)
O2—C1	1.2416 (18)	O7W—H7WA	0.844 (10)
O3—C7	1.2828 (17)	O7W—H7WB	0.847 (10)
O4—C7	1.2404 (18)	O8W—H8WA	0.844 (9)
O5—C8	1.2806 (18)	O8W—H8WB	0.844 (9)
O6—C8	1.2401 (18)	O9W—H9WA	0.846 (9)
O7—C14	1.2810 (18)	O9W—H9WB	0.848 (9)
O8—C14	1.2399 (17)	O10W—H10A	0.845 (10)
O9—C15	1.2724 (18)	O10W—H10B	0.843 (10)
O10—C15	1.2458 (18)	O11W—H11A	0.848 (10)
O11—C21	1.2766 (18)	O11W—H11B	0.846 (10)
O12—C21	1.2468 (18)	O12W—H12A	0.849 (10)
N1—C2	1.3372 (19)	O12W—H12B	0.862 (10)
N1—C6	1.3354 (18)	O13W—H13A	0.845 (10)
N2—C9	1.3386 (19)	O13W—H13B	0.846 (10)
N2—C13	1.3409 (18)	O14W—H14A	0.852 (10)
N3—C16	1.3387 (19)	O14W—H14B	0.846 (10)

O1—Sm1—O7	74.91 (4)	O10—Na4—O13W^v	90.20 (4)
O1—Sm1—O11ⁱ	153.30 (4)	O10W^v—Na4—O10W	180.0
O1—Sm1—N1	62.60 (4)	O10W—Na4—O13W	79.58 (4)
O1—Sm1—N2	77.31 (4)	O10W—Na4—O13W^v	100.42 (4)
O1—Sm1—N3ⁱ	133.62 (4)	O10W^v—Na4—O13W^v	79.58 (4)
O3—Sm1—O1	125.28 (4)	O10W^v—Na4—O13W	100.42 (4)
O3—Sm1—O5	75.87 (4)	O13W^v—Na4—O13W	180.0
O3—Sm1—O7	152.08 (4)	C1—O1—Sm1	125.52 (9)
O3—Sm1—O11ⁱ	74.52 (4)	C1—O2—Na3	130.03 (10)
O3—Sm1—N1	62.70 (4)	C7—O3—Sm1	126.16 (9)
O3—Sm1—N2	134.63 (4)	Na2—O4—Na3ⁱⁱⁱ	92.60 (5)
O3—Sm1—N3ⁱ	78.41 (4)	C7—O4—Na2	111.84 (10)
O5—Sm1—O1	92.07 (4)	C7—O4—Na3ⁱⁱⁱ	144.16 (11)
O5—Sm1—O7	126.55 (4)	C8—O5—Sm1	124.80 (9)
O5—Sm1—O11ⁱ	74.58 (4)	C8—O6—Na1	120.67 (10)
O5—Sm1—N1	75.42 (4)	C14—O7—Sm1	124.81 (9)
O5—Sm1—N2	63.44 (4)	C14—O8—Na2ⁱ	110.69 (9)
O5—Sm1—N3ⁱ	134.19 (4)	C15—O9—Sm1ⁱⁱⁱ	123.86 (10)
O7—Sm1—O11ⁱ	94.32 (4)	C15—O10—Na4	120.46 (10)
O7—Sm1—N1	133.37 (4)	C21—O11—Sm1ⁱⁱⁱ	125.58 (10)
O7—Sm1—N2	63.14 (4)	C21—O12—Na3^vi	157.96 (10)
O7—Sm1—N3ⁱ	73.78 (4)	C2—N1—Sm1	120.78 (9)
O9ⁱ—Sm1—O1	75.25 (4)	C6—N1—Sm1	120.08 (9)
O9ⁱ—Sm1—O3	91.81 (4)	C6—N1—C2	118.93 (12)
O9ⁱ—Sm1—O5	152.88 (4)	C9—N2—Sm1	119.93 (9)
O9ⁱ—Sm1—O7	73.85 (4)	C9—N2—C13	119.10 (13)
O9ⁱ—Sm1—O11ⁱ	125.88 (4)	C13—N2—Sm1	120.81 (10)
O9ⁱ—Sm1—N1	77.46 (4)	C16—N3—Sm1ⁱⁱⁱ	118.99 (10)
O9ⁱ—Sm1—N2	133.52 (4)	C16—N3—C20	118.90 (13)
O9ⁱ—Sm1—N3ⁱ	63.72 (4)	C20—N3—Sm1ⁱⁱⁱ	121.98 (10)
O11ⁱ—Sm1—N1	132.31 (4)	O1—C1—C2	114.80 (13)
O11ⁱ—Sm1—N2	76.04 (4)	O2—C1—O1	125.97 (14)
O11ⁱ—Sm1—N3ⁱ	62.28 (4)	O2—C1—C2	119.22 (13)
N2—Sm1—N1	120.44 (4)	N1—C2—C1	114.50 (12)
N2—Sm1—N3ⁱ	116.16 (4)	N1—C2—C3	122.49 (14)
N3ⁱ—Sm1—N1	123.40 (4)	C3—C2—C1	123.00 (13)
O6ⁱⁱ—Na1—O6	180.00 (5)	C2—C3—H3	120.8
O6ⁱⁱ—Na1—H4WB	113.8 (4)	C2—C3—C4	118.35 (14)
O6—Na1—H4WB	66.2 (4)	C4—C3—H3	120.8
O4Wⁱⁱ—Na1—O6	97.97 (4)	C3—C4—H4	120.4
O4W—Na1—O6ⁱⁱ	97.97 (4)	C5—C4—C3	119.25 (15)
O4Wⁱⁱ—Na1—O6ⁱⁱ	82.03 (4)	C5—C4—H4	120.4
O4W—Na1—O6	82.03 (4)	C4—C5—H5	120.8
O4W—Na1—O4Wⁱⁱ	180.0	C6—C5—C4	118.42 (14)
O4W—Na1—H4WB	19.5 (3)	C6—C5—H5	120.8
O4Wⁱⁱ—Na1—H4WB	160.5 (3)	N1—C6—C5	122.55 (14)
O4Wⁱⁱ—Na1—O7W	85.01 (4)	N1—C6—C7	114.55 (12)
O4W—Na1—O7Wⁱⁱ	85.01 (4)	C5—C6—C7	122.90 (13)
O4W—Na1—O7W	94.99 (4)	O3—C7—Na2	81.93 (8)
O4Wⁱⁱ—Na1—O7Wⁱⁱ	94.99 (4)	O3—C7—C6	114.75 (12)
O7Wⁱⁱ—Na1—O6ⁱⁱ	91.13 (4)	O4—C7—Na2	46.42 (8)
O7Wⁱⁱ—Na1—O6	88.87 (4)	O4—C7—O3	125.91 (14)
O7W—Na1—O6	91.13 (4)	O4—C7—C6	119.34 (13)
O7W—Na1—O6ⁱⁱ	88.87 (4)	C6—C7—Na2	157.60 (10)
O7Wⁱⁱ—Na1—H4WB	74.3 (5)	O5—C8—C9	115.43 (13)
O7W—Na1—H4WB	105.7 (5)	O6—C8—O5	125.08 (14)
O7W—Na1—O7Wⁱⁱ	180.0	O6—C8—C9	119.48 (13)
Na3ⁱⁱⁱ—Na2—H8WB	119.8 (4)	N2—C9—C8	114.36 (12)
O4—Na2—Na3ⁱⁱⁱ	45.18 (3)	N2—C9—C10	121.99 (13)
O4—Na2—O8ⁱⁱⁱ	173.35 (5)	C10—C9—C8	123.64 (13)
O4—Na2—C7	21.74 (4)	C9—C10—H10	120.6
O4—Na2—C14ⁱⁱⁱ	151.35 (4)	C11—C10—C9	118.75 (15)
O4—Na2—O7Wⁱⁱ	89.10 (5)	C11—C10—H10	120.6
O4—Na2—H8WB	75.0 (4)	C10—C11—H11	120.3
O8ⁱⁱⁱ—Na2—Na3ⁱⁱⁱ	128.45 (4)	C10—C11—C12	119.43 (15)
O8ⁱⁱⁱ—Na2—C7	164.79 (4)	C12—C11—H11	120.3
O8ⁱⁱⁱ—Na2—C14ⁱⁱⁱ	22.02 (4)	C11—C12—H12	120.9
O8ⁱⁱⁱ—Na2—O7Wⁱⁱ	94.67 (5)	C13—C12—C11	118.19 (14)
O8ⁱⁱⁱ—Na2—H8WB	111.1 (4)	C13—C12—H12	120.9
C7—Na2—Na3ⁱⁱⁱ	65.15 (3)	N2—C13—C12	122.50 (14)
C7—Na2—H8WB	57.5 (3)	N2—C13—C14	114.75 (12)
C14ⁱⁱⁱ—Na2—Na3ⁱⁱⁱ	106.82 (3)	C12—C13—C14	122.74 (13)
C14ⁱⁱⁱ—Na2—C7	171.39 (4)	O7—C14—Na2ⁱ	103.23 (9)
C14ⁱⁱⁱ—Na2—H8WB	131.1 (3)	O7—C14—C13	115.40 (12)
O7Wⁱⁱ—Na2—Na3ⁱⁱⁱ	101.31 (4)	O8—C14—Na2ⁱ	47.30 (7)
O7Wⁱⁱ—Na2—C7	74.28 (4)	O8—C14—O7	125.03 (14)
O7Wⁱⁱ—Na2—C14ⁱⁱⁱ	105.37 (5)	O8—C14—C13	119.55 (13)
O7Wⁱⁱ—Na2—H8WB	80.2 (5)	C13—C14—Na2ⁱ	121.13 (9)
O8W—Na2—Na3ⁱⁱⁱ	135.37 (4)	O9—C15—C16	116.08 (13)
O8W—Na2—O4	92.78 (5)	O10—C15—O9	124.98 (14)
O8W—Na2—O8ⁱⁱⁱ	92.68 (5)	O10—C15—C16	118.92 (13)
O8W—Na2—C7	77.19 (4)	N3—C16—C15	114.28 (13)
O8W—Na2—C14ⁱⁱⁱ	111.41 (4)	N3—C16—C17	122.66 (14)
O8W—Na2—O7Wⁱⁱ	90.09 (5)	C17—C16—C15	123.05 (14)
O8W—Na2—H8WB	20.4 (3)	C16—C17—H17	120.9
O8W—Na2—O10W	93.71 (5)	C16—C17—C18	118.15 (15)
O9W—Na2—Na3ⁱⁱⁱ	41.54 (3)	C18—C17—H17	120.9
O9W—Na2—O4	83.79 (5)	C17—C18—H18	120.3
O9W—Na2—O8ⁱⁱⁱ	90.77 (5)	C19—C18—C17	119.40 (15)
O9W—Na2—C7	99.36 (5)	C19—C18—H18	120.3
O9W—Na2—C14ⁱⁱⁱ	72.04 (4)	C18—C19—H19	120.7
O9W—Na2—O7Wⁱⁱ	89.31 (5)	C18—C19—C20	118.56 (15)
O9W—Na2—O8W	176.53 (5)	C20—C19—H19	120.7
O9W—Na2—H8WB	156.3 (3)	N3—C20—C19	122.26 (14)
O9W—Na2—O10W	86.76 (5)	N3—C20—C21	114.72 (12)
O10W—Na2—Na3ⁱⁱⁱ	74.40 (3)	C19—C20—C21	123.01 (13)
O10W—Na2—O4	88.49 (5)	O11—C21—C20	115.27 (13)
O10W—Na2—O8ⁱⁱⁱ	87.38 (4)	O12—C21—O11	126.00 (14)
O10W—Na2—C7	104.39 (4)	O12—C21—C20	118.71 (13)
O10W—Na2—C14ⁱⁱⁱ	75.29 (4)	H1WA—O1W—H1WB	109 (3)
O10W—Na2—O7Wⁱⁱ	175.59 (5)	Na3—O2W—H2WA	116.0 (19)
O10W—Na2—H8WB	102.7 (5)	Na3—O2W—H2WB	128.6 (19)
Na2ⁱ—Na3—H3WA	86.7 (4)	H2WA—O2W—H2WB	107 (3)
O2—Na3—Na2ⁱ	108.54 (4)	Na3—O3W—H3WA	99.2 (19)
O2—Na3—O4ⁱ	144.68 (5)	Na3—O3W—H3WB	112.4 (19)
O2—Na3—O12^iv	95.66 (5)	H3WA—O3W—H3WB	109 (3)
O2—Na3—H3WA	119.8 (4)	Na1—O4W—H4WA	126.1 (18)
O2—Na3—O9Wⁱ	83.28 (4)	Na1—O4W—H4WB	88.8 (18)
O4ⁱ—Na3—Na2ⁱ	42.21 (3)	H4WA—O4W—H4WB	110 (3)
O4ⁱ—Na3—H3WA	83.5 (3)	H5WA—O5W—H5WB	107 (3)
O12^iv—Na3—Na2ⁱ	154.56 (4)	H6WA—O6W—H6WB	104 (3)
O12^iv—Na3—O4ⁱ	112.43 (5)	Na1—O7W—Na2ⁱⁱ	131.75 (5)
O12^iv—Na3—H3WA	88.0 (6)	Na1—O7W—H7WA	114.8 (18)
O2W—Na3—Na2ⁱ	81.53 (4)	Na1—O7W—H7WB	104.9 (18)
O2W—Na3—O2	76.69 (5)	Na2ⁱⁱ—O7W—H7WA	94.6 (18)
O2W—Na3—O4ⁱ	78.94 (5)	Na2ⁱⁱ—O7W—H7WB	104.5 (18)
O2W—Na3—O12^iv	97.00 (5)	H7WA—O7W—H7WB	103 (2)
O2W—Na3—O3W	176.16 (6)	Na2—O8W—H8WA	106.0 (17)
O2W—Na3—H3WA	162.4 (4)	Na2—O8W—H8WB	84.7 (17)
O2W—Na3—O9Wⁱ	103.12 (5)	H8WA—O8W—H8WB	106 (2)
O3W—Na3—Na2ⁱ	101.53 (4)	Na2—O9W—Na3ⁱⁱⁱ	100.26 (5)
O3W—Na3—O2	104.30 (5)	Na2—O9W—H9WA	117.2 (17)
O3W—Na3—O4ⁱ	101.73 (5)	Na2—O9W—H9WB	118.1 (17)
O3W—Na3—O12^iv	79.24 (5)	Na3ⁱⁱⁱ—O9W—H9WA	113.2 (17)
O3W—Na3—H3WA	18.3 (3)	Na3ⁱⁱⁱ—O9W—H9WB	94.1 (17)
O3W—Na3—O9Wⁱ	80.70 (5)	H9WA—O9W—H9WB	111 (2)
O9Wⁱ—Na3—Na2ⁱ	38.20 (3)	Na2—O10W—H10A	101.1 (17)
O9Wⁱ—Na3—O4ⁱ	77.79 (4)	Na2—O10W—H10B	102.4 (17)
O9Wⁱ—Na3—O12^iv	158.99 (5)	Na4—O10W—Na2	128.07 (5)
O9Wⁱ—Na3—H3WA	74.6 (6)	Na4—O10W—H10A	113.7 (17)
O10^v—Na4—O10	180.00 (6)	Na4—O10W—H10B	102.6 (17)
O10—Na4—O10W^v	92.22 (4)	H10A—O10W—H10B	107 (2)
O10—Na4—O10W	87.78 (4)	H11A—O11W—H11B	105 (3)
O10^v—Na4—O10W	92.22 (4)	H12A—O12W—H12B	103 (3)
O10^v—Na4—O10W^v	87.78 (4)	Na4—O13W—H13A	107.4 (17)
O10^v—Na4—O13W^v	89.80 (4)	Na4—O13W—H13B	107.5 (17)
O10—Na4—O13W	89.80 (4)	H13A—O13W—H13B	102 (2)
O10^v—Na4—O13W	90.20 (4)	H14A—O14W—H14B	112 (3)

Sm1—O1—C1—O2	164.44 (12)	O9—C15—C16—C17	−170.69 (15)
Sm1—O1—C1—C2	−16.46 (18)	O10—C15—C16—N3	−168.08 (13)
Sm1—O3—C7—Na2	149.87 (9)	O10—C15—C16—C17	10.7 (2)
Sm1—O3—C7—O4	165.65 (12)	N1—C2—C3—C4	−0.9 (3)
Sm1—O3—C7—C6	−14.47 (18)	N1—C6—C7—Na2	−130.8 (2)
Sm1—O5—C8—O6	162.94 (12)	N1—C6—C7—O3	4.68 (19)
Sm1—O5—C8—C9	−16.30 (18)	N1—C6—C7—O4	−175.43 (14)
Sm1—O7—C14—Na2ⁱ	121.58 (8)	N2—C9—C10—C11	−2.0 (2)
Sm1—O7—C14—O8	168.27 (11)	N2—C13—C14—Na2ⁱ	−115.99 (12)
Sm1—O7—C14—C13	−12.81 (17)	N2—C13—C14—O7	9.65 (19)
Sm1ⁱⁱⁱ—O9—C15—O10	157.66 (12)	N2—C13—C14—O8	−171.36 (13)
Sm1ⁱⁱⁱ—O9—C15—C16	−20.84 (17)	N3—C16—C17—C18	−2.2 (3)
Sm1ⁱⁱⁱ—O11—C21—O12	176.34 (11)	N3—C20—C21—O11	3.42 (19)
Sm1ⁱⁱⁱ—O11—C21—C20	−5.05 (17)	N3—C20—C21—O12	−177.86 (13)
Sm1—N1—C2—C1	−4.62 (17)	C1—C2—C3—C4	178.19 (16)
Sm1—N1—C2—C3	174.58 (12)	C2—N1—C6—C5	1.1 (2)
Sm1—N1—C6—C5	−173.65 (12)	C2—N1—C6—C7	−179.45 (13)
Sm1—N1—C6—C7	5.79 (17)	C2—C3—C4—C5	1.1 (3)
Sm1—N2—C9—C8	4.58 (16)	C3—C4—C5—C6	−0.2 (3)
Sm1—N2—C9—C10	−174.00 (12)	C4—C5—C6—N1	−0.9 (3)
Sm1—N2—C13—C12	175.90 (12)	C4—C5—C6—C7	179.67 (16)
Sm1—N2—C13—C14	−2.79 (16)	C5—C6—C7—Na2	48.6 (3)
Sm1ⁱⁱⁱ—N3—C16—C15	3.18 (16)	C5—C6—C7—O3	−175.88 (15)
Sm1ⁱⁱⁱ—N3—C16—C17	−175.62 (12)	C5—C6—C7—O4	4.0 (2)
Sm1ⁱⁱⁱ—N3—C20—C19	178.06 (12)	C6—N1—C2—C1	−179.35 (13)
Sm1ⁱⁱⁱ—N3—C20—C21	−0.53 (16)	C6—N1—C2—C3	−0.1 (2)
Na1—O6—C8—O5	−17.7 (2)	C8—C9—C10—C11	179.54 (15)
Na1—O6—C8—C9	161.50 (10)	C9—N2—C13—C12	0.5 (2)
Na2—O4—C7—O3	−21.8 (2)	C9—N2—C13—C14	−178.15 (13)
Na2—O4—C7—C6	158.31 (11)	C9—C10—C11—C12	0.7 (3)
Na2ⁱ—O8—C14—O7	−74.53 (16)	C10—C11—C12—C13	1.1 (3)
Na2ⁱ—O8—C14—C13	106.58 (12)	C11—C12—C13—N2	−1.8 (2)
Na3—O2—C1—O1	−6.3 (2)	C11—C12—C13—C14	176.80 (15)
Na3—O2—C1—C2	174.60 (10)	C12—C13—C14—Na2ⁱ	65.32 (17)
Na3ⁱⁱⁱ—O4—C7—Na2	−129.7 (2)	C12—C13—C14—O7	−169.04 (14)
Na3ⁱⁱⁱ—O4—C7—O3	−151.47 (13)	C12—C13—C14—O8	10.0 (2)
Na3ⁱⁱⁱ—O4—C7—C6	28.6 (3)	C13—N2—C9—C8	179.98 (13)
Na3^vi—O12—C21—O11	125.3 (3)	C13—N2—C9—C10	1.4 (2)
Na3^vi—O12—C21—C20	−53.3 (3)	C15—C16—C17—C18	179.08 (16)
Na4—O10—C15—O9	−87.53 (17)	C16—N3—C20—C19	2.1 (2)
Na4—O10—C15—C16	90.94 (14)	C16—N3—C20—C21	−176.44 (13)
O1—C1—C2—N1	12.93 (19)	C16—C17—C18—C19	1.5 (3)
O1—C1—C2—C3	−166.27 (15)	C17—C18—C19—C20	0.9 (3)
O2—C1—C2—N1	−167.90 (14)	C18—C19—C20—N3	−2.8 (2)
O2—C1—C2—C3	12.9 (2)	C18—C19—C20—C21	175.69 (15)
O5—C8—C9—N2	6.77 (19)	C19—C20—C21—O11	−175.16 (14)
O5—C8—C9—C10	−174.68 (15)	C19—C20—C21—O12	3.6 (2)
O6—C8—C9—N2	−172.51 (14)	C20—N3—C16—C15	179.22 (12)
O6—C8—C9—C10	6.0 (2)	C20—N3—C16—C17	0.4 (2)
O9—C15—C16—N3	10.52 (19)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O13W^vii	0.85 (1)	1.98 (1)	2.8163 (19)	167 (3)
O2W—H2WA···O11Wⁱ	0.86 (1)	2.10 (1)	2.927 (2)	160 (3)
O2W—H2WA···O12W^viii	0.86 (1)	2.76 (3)	3.2317 (19)	116 (2)
O2W—H2WB···O1W	0.86 (1)	1.90 (1)	2.742 (2)	164 (3)
O4W—H4WA···O5W	0.85 (1)	1.91 (1)	2.741 (2)	167 (3)
O4W—H4WB···O5	0.85 (1)	2.02 (1)	2.8534 (17)	169 (3)
O6W—H6WA···O12^ix	0.86 (1)	2.00 (1)	2.8435 (19)	168 (3)
O6W—H6WB···O8^x	0.87 (1)	2.09 (2)	2.8645 (18)	149 (3)
O7W—H7WA···O6W	0.84 (1)	1.93 (1)	2.7611 (19)	167 (3)
O7W—H7WB···O3ⁱⁱ	0.85 (1)	2.54 (2)	3.1551 (17)	131 (2)
O7W—H7WB···O5ⁱⁱ	0.85 (1)	2.31 (2)	3.0267 (17)	142 (2)
O8W—H8WA···O10^v	0.84 (1)	1.87 (1)	2.7065 (17)	171 (2)
O9W—H9WA···O6ⁱⁱ	0.85 (1)	1.94 (1)	2.7871 (16)	175 (2)
O9W—H9WB···O1ⁱⁱⁱ	0.85 (1)	1.87 (1)	2.7160 (16)	173 (2)
O10W—H10A···O2Wⁱⁱⁱ	0.85 (1)	1.90 (1)	2.7419 (18)	178 (2)
O11W—H11A···O9	0.85 (1)	1.97 (1)	2.8128 (17)	174 (3)
O11W—H11B···O12W	0.85 (1)	2.13 (1)	2.973 (2)	178 (3)
O12W—H12A···O2^viii	0.85 (1)	2.11 (1)	2.9542 (18)	173 (3)
O12W—H12B···O8W^v	0.86 (1)	2.03 (2)	2.8057 (18)	149 (3)
O13W—H13A···O12W^v	0.85 (1)	1.99 (1)	2.8235 (18)	170 (2)
O13W—H13B···O7ⁱⁱⁱ	0.85 (1)	2.09 (1)	2.9274 (17)	171 (2)
O13W—H13B···O8ⁱⁱⁱ	0.85 (1)	2.57 (2)	3.1929 (17)	132 (2)

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

catena-Poly[[[diaqua(6-carboxypyridine-2-carboxylato-κ³O²,N,O⁶)samarium(III)]-µ-pyridine-2,6-dicarboxylato-κ⁴O²,N,O⁶:O²] tetrahydrate] (II) top

Crystal data top

[Sm(C₇H₃NO₄)(C₇H₄NO₄)(H₂O)₂]·4H₂O	F(000) = 1164
M_r = 589.66	D_x = 2.013 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.9292 (8) Å	Cell parameters from 9554 reflections
b = 11.1969 (7) Å	θ = 2.4–35.1°
c = 12.8086 (7) Å	µ = 3.10 mm⁻¹
β = 103.049 (2)°	T = 100 K
V = 1946.1 (2) Å³	Plate, colourless
Z = 4	0.48 × 0.40 × 0.15 mm

Data collection top

Bruker APEXII CCD diffractometer	6679 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.044
Absorption correction: multi-scan (SADABS; Bruker, 2019)	θ_max = 33.1°, θ_min = 2.4°
T_min = 0.575, T_max = 0.747	h = −21→21
74345 measured reflections	k = −17→17
7424 independent reflections	l = −17→19

Refinement top

Refinement on F²	12 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.042	w = 1/[σ²(F_o²) + (0.012P)² + 2.2391P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.007
7424 reflections	Δρ_max = 0.73 e Å⁻³
319 parameters	Δρ_min = −1.09 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Sm1	0.73193 (2)	0.29610 (2)	0.84878 (2)	0.00303 (2)
O1	0.65850 (8)	0.10076 (9)	0.86514 (9)	0.00783 (19)
O2	0.53228 (8)	−0.01891 (10)	0.87649 (10)	0.0123 (2)
O3	0.64950 (8)	0.49371 (9)	0.85969 (9)	0.00847 (19)
O4	0.51949 (9)	0.60513 (11)	0.87239 (10)	0.0145 (2)
H4	0.5646 (18)	0.676 (2)	0.875 (2)	0.022*
O5	0.84574 (8)	0.07310 (10)	0.27878 (9)	0.00810 (19)
O6	0.92027 (9)	−0.10506 (10)	0.28114 (9)	0.0106 (2)
O7	0.72787 (8)	0.22062 (9)	0.54309 (8)	0.00693 (18)
O8	0.78295 (8)	0.16945 (10)	0.71580 (8)	0.00725 (18)
C1	0.56995 (11)	0.08151 (13)	0.86995 (12)	0.0074 (2)
C2	0.50502 (11)	0.18986 (13)	0.86725 (12)	0.0083 (2)
C3	0.40535 (12)	0.18312 (16)	0.86702 (17)	0.0177 (3)
H3	0.374223	0.108078	0.869860	0.021*
C4	0.35229 (13)	0.28896 (17)	0.8625 (2)	0.0240 (4)
H4A	0.283664	0.286989	0.860236	0.029*
C5	0.40023 (12)	0.39746 (16)	0.86144 (16)	0.0176 (3)
H5	0.365676	0.470880	0.859381	0.021*
C6	0.50027 (11)	0.39530 (14)	0.86343 (12)	0.0091 (2)
C7	0.56268 (11)	0.50434 (13)	0.86471 (12)	0.0083 (3)
C8	0.88073 (10)	−0.02353 (13)	0.32337 (11)	0.0061 (2)
C9	0.87488 (10)	−0.03865 (12)	0.43907 (11)	0.0052 (2)
C10	0.90835 (11)	−0.13997 (13)	0.49895 (12)	0.0073 (2)
H10	0.934576	−0.205672	0.467574	0.009*
C11	0.90257 (11)	−0.14290 (13)	0.60575 (12)	0.0084 (2)
H11	0.925058	−0.210990	0.648565	0.010*
C12	0.86374 (10)	−0.04573 (13)	0.64965 (11)	0.0066 (2)
H12	0.861422	−0.044590	0.723200	0.008*
C13	0.82835 (10)	0.04988 (12)	0.58257 (11)	0.0049 (2)
C14	0.77620 (10)	0.15538 (12)	0.61763 (11)	0.0049 (2)
N1	0.55123 (9)	0.29383 (11)	0.86438 (10)	0.0063 (2)
N2	0.83414 (9)	0.05330 (11)	0.47961 (9)	0.0046 (2)
O1W	0.63395 (9)	0.34532 (11)	0.67167 (9)	0.0117 (2)
H1WA	0.5864 (10)	0.3940 (15)	0.6529 (18)	0.018*
H1WB	0.6530 (15)	0.3178 (19)	0.6179 (11)	0.018*
O2W	0.87579 (8)	0.18700 (10)	0.93554 (9)	0.0091 (2)
H2WA	0.8967 (16)	0.1939 (19)	1.0029 (3)	0.014*
H2WB	0.9169 (11)	0.1431 (15)	0.9135 (16)	0.014*
O3W	0.95920 (8)	0.19105 (10)	1.14835 (9)	0.00890 (19)
H3WA	0.9230 (12)	0.1699 (19)	1.1904 (13)	0.013*
H3WB	0.9949 (13)	0.2501 (12)	1.1748 (16)	0.013*
O4W	0.63135 (11)	0.77889 (12)	0.89098 (16)	0.0307 (4)
H4WA	0.6029 (18)	0.8463 (11)	0.888 (2)	0.046*
H4WB	0.6931 (4)	0.785 (3)	0.896 (3)	0.046*
O5W	0.80409 (10)	0.90705 (12)	0.90443 (12)	0.0217 (3)
H5WA	0.7688 (15)	0.9695 (12)	0.900 (2)	0.033*
H5WB	0.8408 (15)	0.919 (2)	0.9662 (9)	0.033*
O6W	0.96769 (9)	−0.05672 (10)	0.09389 (9)	0.0116 (2)
H6WA	0.9816 (16)	0.0173 (5)	0.0980 (18)	0.017*
H6WB	0.9508 (15)	−0.072 (2)	0.1523 (9)	0.017*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sm1	0.00394 (3)	0.00300 (3)	0.00234 (3)	−0.00019 (2)	0.00113 (2)	−0.00035 (2)
O1	0.0069 (4)	0.0056 (4)	0.0115 (5)	−0.0009 (4)	0.0033 (4)	0.0000 (4)
O2	0.0093 (5)	0.0066 (5)	0.0214 (6)	−0.0034 (4)	0.0040 (4)	0.0004 (4)
O3	0.0085 (5)	0.0062 (4)	0.0105 (5)	0.0012 (4)	0.0017 (4)	−0.0005 (4)
O4	0.0147 (5)	0.0075 (5)	0.0220 (6)	0.0043 (4)	0.0055 (5)	−0.0020 (4)
O5	0.0116 (5)	0.0074 (4)	0.0064 (4)	0.0034 (4)	0.0044 (4)	0.0019 (4)
O6	0.0176 (5)	0.0080 (5)	0.0085 (5)	0.0054 (4)	0.0075 (4)	0.0001 (4)
O7	0.0088 (4)	0.0078 (5)	0.0043 (4)	0.0032 (4)	0.0018 (4)	0.0014 (3)
O8	0.0109 (5)	0.0079 (4)	0.0035 (4)	0.0020 (4)	0.0025 (4)	−0.0006 (4)
C1	0.0078 (6)	0.0066 (6)	0.0074 (6)	−0.0014 (5)	0.0010 (5)	−0.0009 (5)
C2	0.0064 (6)	0.0084 (6)	0.0109 (6)	0.0005 (5)	0.0032 (5)	0.0002 (5)
C3	0.0078 (6)	0.0134 (7)	0.0341 (10)	−0.0006 (5)	0.0090 (6)	0.0023 (7)
C4	0.0089 (7)	0.0171 (8)	0.0493 (13)	0.0024 (6)	0.0136 (8)	0.0039 (8)
C5	0.0113 (7)	0.0137 (7)	0.0301 (9)	0.0049 (6)	0.0095 (6)	0.0018 (7)
C6	0.0092 (6)	0.0083 (6)	0.0106 (6)	0.0025 (5)	0.0036 (5)	0.0005 (5)
C7	0.0112 (6)	0.0071 (6)	0.0070 (6)	0.0033 (5)	0.0025 (5)	−0.0001 (5)
C8	0.0080 (6)	0.0061 (6)	0.0053 (6)	0.0007 (4)	0.0034 (5)	−0.0003 (5)
C9	0.0060 (5)	0.0052 (5)	0.0049 (5)	0.0004 (4)	0.0022 (4)	0.0000 (4)
C10	0.0095 (6)	0.0058 (6)	0.0067 (6)	0.0021 (5)	0.0024 (5)	0.0000 (5)
C11	0.0117 (6)	0.0069 (6)	0.0066 (6)	0.0021 (5)	0.0017 (5)	0.0022 (5)
C12	0.0087 (6)	0.0064 (6)	0.0042 (6)	0.0004 (5)	0.0006 (5)	0.0002 (4)
C13	0.0060 (5)	0.0055 (5)	0.0033 (5)	−0.0003 (4)	0.0014 (4)	0.0001 (4)
C14	0.0057 (5)	0.0041 (5)	0.0051 (5)	−0.0007 (4)	0.0018 (4)	−0.0006 (4)
N1	0.0066 (5)	0.0069 (5)	0.0059 (5)	0.0008 (4)	0.0023 (4)	−0.0001 (4)
N2	0.0057 (5)	0.0044 (5)	0.0041 (5)	−0.0002 (4)	0.0023 (4)	−0.0003 (4)
O1W	0.0127 (5)	0.0169 (6)	0.0049 (5)	0.0090 (4)	0.0012 (4)	−0.0004 (4)
O2W	0.0088 (5)	0.0123 (5)	0.0055 (4)	0.0047 (4)	0.0003 (4)	−0.0017 (4)
O3W	0.0100 (5)	0.0109 (5)	0.0065 (5)	−0.0018 (4)	0.0032 (4)	−0.0005 (4)
O4W	0.0192 (7)	0.0093 (6)	0.0653 (12)	0.0012 (5)	0.0129 (7)	−0.0009 (6)
O5W	0.0188 (6)	0.0118 (6)	0.0316 (8)	0.0030 (5)	−0.0005 (5)	−0.0017 (5)
O6W	0.0169 (5)	0.0098 (5)	0.0107 (5)	0.0030 (4)	0.0087 (4)	0.0015 (4)

Geometric parameters (Å, º) top

Sm1—O2W	2.3952 (11)	C6—N1	1.3382 (19)
Sm1—O1W	2.4320 (11)	C6—C7	1.497 (2)
Sm1—O8	2.4422 (10)	C8—C9	1.512 (2)
Sm1—O1	2.4434 (11)	C9—N2	1.3360 (18)
Sm1—O5ⁱ	2.4707 (11)	C9—C10	1.3896 (19)
Sm1—O7ⁱ	2.5092 (11)	C10—C11	1.389 (2)
Sm1—O3	2.5112 (11)	C10—H10	0.9500
Sm1—N2ⁱ	2.5693 (12)	C11—C12	1.389 (2)
Sm1—N1	2.5695 (12)	C11—H11	0.9500
O1—C1	1.2673 (17)	C12—C13	1.3914 (19)
O2—C1	1.2516 (18)	C12—H12	0.9500
O3—C7	1.2313 (18)	C13—N2	1.3399 (18)
O4—C7	1.2930 (18)	C13—C14	1.507 (2)
O4—H4	1.01 (3)	O1W—H1WA	0.8499 (10)
O5—C8	1.2683 (17)	O1W—H1WB	0.8500 (10)
O6—C8	1.2505 (17)	O2W—H2WA	0.8500 (10)
O7—C14	1.2681 (17)	O2W—H2WB	0.8500 (10)
O8—C14	1.2495 (17)	O3W—H3WA	0.8499 (10)
C1—C2	1.509 (2)	O3W—H3WB	0.8499 (10)
C2—N1	1.3348 (19)	O4W—H4	1.47 (3)
C2—C3	1.390 (2)	O4W—H4WA	0.8499 (10)
C3—C4	1.391 (2)	O4W—H4WB	0.8499 (11)
C3—H3	0.9500	O5W—H5WA	0.8499 (10)
C4—C5	1.388 (3)	O5W—H5WB	0.8499 (10)
C4—H4A	0.9500	O6W—H6WA	0.8499 (10)
C5—C6	1.388 (2)	O6W—H6WB	0.8499 (10)
C5—H5	0.9500

O2W—Sm1—O1W	141.52 (4)	C5—C4—C3	119.59 (16)
O2W—Sm1—O8	71.50 (4)	C5—C4—H4A	120.2
O1W—Sm1—O8	70.81 (4)	C3—C4—H4A	120.2
O2W—Sm1—O1	79.99 (4)	C4—C5—C6	117.89 (15)
O1W—Sm1—O1	97.19 (4)	C4—C5—H5	121.1
O8—Sm1—O1	74.54 (4)	C6—C5—H5	121.1
O2W—Sm1—O5ⁱ	86.13 (4)	N1—C6—C5	122.90 (15)
O1W—Sm1—O5ⁱ	78.35 (4)	N1—C6—C7	112.76 (13)
O8—Sm1—O5ⁱ	77.26 (4)	C5—C6—C7	124.34 (14)
O1—Sm1—O5ⁱ	151.28 (4)	O3—C7—O4	124.59 (14)
O2W—Sm1—O7ⁱ	72.88 (4)	O3—C7—C6	119.70 (13)
O1W—Sm1—O7ⁱ	143.96 (4)	O4—C7—C6	115.71 (13)
O8—Sm1—O7ⁱ	136.37 (4)	O6—C8—O5	126.15 (13)
O1—Sm1—O7ⁱ	75.20 (3)	O6—C8—C9	117.94 (13)
O5ⁱ—Sm1—O7ⁱ	124.35 (3)	O5—C8—C9	115.89 (12)
O2W—Sm1—O3	140.24 (4)	N2—C9—C10	122.25 (13)
O1W—Sm1—O3	71.63 (4)	N2—C9—C8	114.60 (12)
O8—Sm1—O3	139.39 (4)	C10—C9—C8	123.15 (12)
O1—Sm1—O3	125.34 (4)	C11—C10—C9	118.44 (13)
O5ⁱ—Sm1—O3	80.61 (4)	C11—C10—H10	120.8
O7ⁱ—Sm1—O3	84.12 (4)	C9—C10—H10	120.8
O2W—Sm1—N2ⁱ	75.51 (4)	C10—C11—C12	119.64 (13)
O1W—Sm1—N2ⁱ	124.84 (4)	C10—C11—H11	120.2
O8—Sm1—N2ⁱ	129.07 (4)	C12—C11—H11	120.2
O1—Sm1—N2ⁱ	135.45 (4)	C11—C12—C13	117.95 (13)
O5ⁱ—Sm1—N2ⁱ	62.69 (4)	C11—C12—H12	121.0
O7ⁱ—Sm1—N2ⁱ	62.31 (4)	C13—C12—H12	121.0
O3—Sm1—N2ⁱ	65.06 (4)	N2—C13—C12	122.55 (13)
O2W—Sm1—N1	133.67 (4)	N2—C13—C14	114.27 (12)
O1W—Sm1—N1	73.83 (4)	C12—C13—C14	123.12 (12)
O8—Sm1—N1	119.53 (4)	O8—C14—O7	126.27 (13)
O1—Sm1—N1	63.14 (4)	O8—C14—C13	117.83 (12)
O5ⁱ—Sm1—N1	138.95 (4)	O7—C14—C13	115.90 (12)
O7ⁱ—Sm1—N1	71.36 (4)	C2—N1—C6	118.86 (13)
O3—Sm1—N1	62.37 (4)	C2—N1—Sm1	119.84 (9)
N2ⁱ—Sm1—N1	111.35 (4)	C6—N1—Sm1	121.18 (10)
C1—O1—Sm1	125.96 (9)	C9—N2—C13	119.07 (12)
C7—O3—Sm1	123.70 (10)	C9—N2—Sm1ⁱⁱ	118.28 (9)
C7—O4—H4	113.1 (14)	C13—N2—Sm1ⁱⁱ	120.87 (9)
C8—O5—Sm1ⁱⁱ	123.71 (9)	Sm1—O1W—H1WA	130.3 (16)
C14—O7—Sm1ⁱⁱ	125.23 (9)	Sm1—O1W—H1WB	117.5 (15)
C14—O8—Sm1	143.85 (10)	H1WA—O1W—H1WB	112 (2)
O2—C1—O1	125.69 (14)	Sm1—O2W—H2WA	119.0 (15)
O2—C1—C2	117.75 (13)	Sm1—O2W—H2WB	134.2 (14)
O1—C1—C2	116.56 (13)	H2WA—O2W—H2WB	107 (2)
N1—C2—C3	122.34 (14)	H3WA—O3W—H3WB	110 (2)
N1—C2—C1	114.31 (12)	H4—O4W—H4WA	115 (2)
C3—C2—C1	123.35 (14)	H4—O4W—H4WB	132 (2)
C2—C3—C4	118.37 (16)	H4WA—O4W—H4WB	113 (3)
C2—C3—H3	120.8	H5WA—O5W—H5WB	99 (2)
C4—C3—H3	120.8	H6WA—O6W—H6WB	104 (2)

Sm1—O1—C1—O2	178.70 (11)	C10—C11—C12—C13	2.4 (2)
Sm1—O1—C1—C2	−1.16 (18)	C11—C12—C13—N2	−2.8 (2)
O2—C1—C2—N1	177.56 (14)	C11—C12—C13—C14	174.28 (13)
O1—C1—C2—N1	−2.6 (2)	Sm1—O8—C14—O7	−0.5 (3)
O2—C1—C2—C3	−2.8 (2)	Sm1—O8—C14—C13	−179.20 (10)
O1—C1—C2—C3	177.02 (16)	Sm1ⁱⁱ—O7—C14—O8	172.44 (11)
N1—C2—C3—C4	0.7 (3)	Sm1ⁱⁱ—O7—C14—C13	−8.81 (17)
C1—C2—C3—C4	−178.89 (18)	N2—C13—C14—O8	−167.61 (13)
C2—C3—C4—C5	−1.8 (3)	C12—C13—C14—O8	15.1 (2)
C3—C4—C5—C6	0.9 (3)	N2—C13—C14—O7	13.53 (18)
C4—C5—C6—N1	1.3 (3)	C12—C13—C14—O7	−163.75 (13)
C4—C5—C6—C7	−178.78 (18)	C3—C2—N1—C6	1.4 (2)
Sm1—O3—C7—O4	178.63 (11)	C1—C2—N1—C6	−179.02 (13)
Sm1—O3—C7—C6	−0.58 (19)	C3—C2—N1—Sm1	−174.76 (13)
N1—C6—C7—O3	4.5 (2)	C1—C2—N1—Sm1	4.83 (17)
C5—C6—C7—O3	−175.46 (16)	C5—C6—N1—C2	−2.4 (2)
N1—C6—C7—O4	−174.77 (13)	C7—C6—N1—C2	177.65 (13)
C5—C6—C7—O4	5.3 (2)	C5—C6—N1—Sm1	173.72 (13)
Sm1ⁱⁱ—O5—C8—O6	163.39 (12)	C7—C6—N1—Sm1	−6.26 (17)
Sm1ⁱⁱ—O5—C8—C9	−17.75 (17)	C10—C9—N2—C13	2.4 (2)
O6—C8—C9—N2	178.29 (13)	C8—C9—N2—C13	−178.01 (12)
O5—C8—C9—N2	−0.67 (19)	C10—C9—N2—Sm1ⁱⁱ	−162.53 (11)
O6—C8—C9—C10	−2.1 (2)	C8—C9—N2—Sm1ⁱⁱ	17.07 (15)
O5—C8—C9—C10	178.93 (13)	C12—C13—N2—C9	0.4 (2)
N2—C9—C10—C11	−2.6 (2)	C14—C13—N2—C9	−176.91 (12)
C8—C9—C10—C11	177.79 (13)	C12—C13—N2—Sm1ⁱⁱ	164.91 (10)
C9—C10—C11—C12	0.1 (2)	C14—C13—N2—Sm1ⁱⁱ	−12.39 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2ⁱⁱⁱ	0.85 (1)	1.88 (1)	2.7218 (16)	169 (2)
O1W—H1WB···O7	0.85 (1)	1.91 (1)	2.7103 (15)	157 (2)
O2W—H2WA···O3W	0.85 (1)	1.87 (1)	2.7115 (16)	170 (2)
O2W—H2WB···O6W^iv	0.85 (1)	1.90 (1)	2.7193 (16)	163 (2)
O3W—H3WA···O5^v	0.85 (1)	2.04 (1)	2.8679 (15)	164 (2)
O3W—H3WB···O6^vi	0.85 (1)	2.01 (1)	2.8568 (16)	173 (2)
O4W—H4WA···O2^vii	0.85 (1)	1.79 (1)	2.6360 (18)	174 (3)
O4W—H4WB···O5W	0.85 (1)	2.05 (2)	2.773 (2)	143 (3)
O5W—H5WA···O1^vii	0.85 (1)	2.10 (1)	2.9340 (17)	167 (2)
O5W—H5WB···O6W^viii	0.85 (1)	2.14 (1)	2.9579 (19)	162 (2)
O6W—H6WA···O3W^ix	0.85 (1)	2.10 (1)	2.8696 (16)	151 (2)
O6W—H6WB···O6	0.85 (1)	1.83 (1)	2.6828 (16)	177 (2)
O4—H4···O4W	1.01 (3)	1.47 (3)	2.4703 (19)	174 (2)

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

Acknowledgements

The Villum Foundation, the Carlsberg Foundation, and the University of Copenhagen are thanked for generous support.

Funding information

Funding for this research was provided by: Villum Fonden; Carlsbergfondet; Københavns Universitet.

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