Crystal structure of a heterotrimetallic 12-metallacrown-4 with 2-propyl­valerate anion bridges

Aziz, O.A.; Zeller, M.; Zaleski, C.M.

doi:10.1107/S2056989022010489

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ISSN: 2056-9890

Volume 78| Part 12| December 2022| Pages 1178-1183

https://doi.org/10.1107/S2056989022010489

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Crystal structure of a heterotrimetallic 12-metallacrown-4 with 2-propylvalerate anion bridges

Ozha A. Aziz,^a Matthias Zeller ^b and Curtis M. Zaleski ^a ^*

^aDepartment of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA, and ^bDepartment of Chemistry, Purdue University, West Lafayette, IN 47907, USA
^*Correspondence e-mail: cmzaleski@ship.edu

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 13 October 2022; accepted 31 October 2022; online 8 November 2022)

The synthesis and single-crystal X-ray structure for tetraaquatetrakis(μ-2-propylvalerato)tetrakis(μ₄-salicylhydroximato)dysprosiumtetramanganesesodium dimethylformamide tetrasolvate, [DyMn₄Na(C₇H4NO₃)₄(C₈H₁₅O₂)₄(H₂O)₄]·4C₃H₇NO or DyNa(2-PV)₄[12-MC_Mn^III_Nshi-4](H₂O)₄·4DMF, 1, where MC is metallacrown, shi³⁻ is salicylhydroximate, 2-PV is 2-propylvalerate, and DMF is N,N-dimethylformamide, is reported. The slightly domed metallamacrocycle contains four ring Mn^III ions and four shi³⁻ ligands that generate an [Mn^III—N—O] repeat unit that recurs four times. The ring Mn^III ions are five-coordinate with a square-pyramidal shape. Furthermore, the metallacrown binds both a Dy^III ion and a Na⁺ ion in the central cavity. The central ions are located on opposite faces of the cavity with the Dy^III ion located on the convex side of the MC and the Na⁺ ion located on the concave side. Each central ion is eight-coordinate although they possess different geometries. The Dy^III ion has a square-antiprismatic shape, while the Na⁺ ion has an extremely distorted biaugmented trigonal–prismatic shape. The four 2-propylvalerate anions help to tether the Dy^III to the MC cavity by forming bridges between the Dy^III ion and each ring Mn^III ion. Moreover, the interstitial DMF molecules are hydrogen bonded to the water molecules that complete the coordination environment of the Na⁺ ion. The metallacrown framework (excluding the Dy^III and Na⁺ ions), the bridging 2-propylvalerate, and the interstitial DMF molecule experience whole-molecule disorder due to the rotational orientation of the metallamacrocycle. Additionally, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional orientations, and the main moiety interstitial DMF molecule is disordered over one additional orientation. The main moiety of the metallacrown framework refined to 0.9030 (14), while the minor B-moiety refined to 0.0971 (14). The main moiety alkyl chain of the 2-propylvalerate refined to 0.287 (3): 0.309 (3): 0.307 (3), and the minor B-moiety alkyl chain refined to 0.0971 (14). Lastly, the main moiety interstitial DMF refined to 0.549 (3): 0.354 (3), and the minor B-moiety DMF refined to 0.0971 (14).

Keywords: metallacrown; dysprosium; manganese; crystal structure.

CCDC reference: 2216645

1. Chemical context

Materials that combine both 3d and 4f metal ions have potentially interesting magnetic properties as a result of the interaction between the paramagnetic centers. In particular, 3d–4f materials have applications in the areas of single-molecule magnetism (Liu et al., 2015 ), single-chain magnetism (Wang et al., 2014 ), and magnetorefrigeration (Lun et al., 2021 ). The systematic synthesis of these heterometallic compounds is of interest to chemists and material scientists, and metallacrowns (MC) are a class of molecules particularly suited for the investigation of such materials because of their ability to interchange components of the molecule while maintaining the overall structural features (Mezei et al., 2007 ; Lutter et al., 2018 ).

Metallacrowns are metallamacrocyclic compounds with a metal–nitrogen–oxygen repeat unit about the inner ring. Several 3d–4f metallacrown systems have proven to be single-molecule magnets (SMM) (Boron, 2022 ) and magnetorefrigerates (Lutter et al., 2021 ; Salerno et al., 2021 ; Saha et al., 2022 ). Indeed, we have been particularity focused on a lanthanide–manganese 12-metallacrown-4 system, LnNaY₄[12-MC_Mn^III_Nshi-4], where Y is a carboxylate anion and shi³⁻ is salicylhydroximate (Azar et al., 2014 ). These metallacrowns are based on a 12-membered MC ring with four oxygen atoms comprising the MC cavity. In addition, four Mn^III are part of the MC ring and the central cavity captures two cations in the central cavity: an Ln^III ion and a Na⁺ ion. The two cations bind to opposite sides of the MC cavity. Furthermore, four carboxylate anions bridge between each ring Mn^III ions and the central Ln^III ion. We first reported these heterotrimetallic compounds with acetate bridges in 2014 (Azar et al., 2014) and demonstrated that the MCs could bind a range of Ln^III ions in the central cavity, Pr to Yb (except Pm). Subsequently, we investigated the single-molecule magnet behavior of a series of DyNaY₄[12-MC_Mn^III_Nshi-4] compounds, where Y is acetate, trimethylacetate, benzoate, or 2-hydroxybenzoate (i.e. salicylate) (Boron et al., 2016 ). In this series, only the MCs with bridging 2-hydroxybenzoate anions displayed single-molecule magnet properties. We hypothesized that the Lewis basicity of the bridging ligand may affect the magnetic coupling between the metal centers, thus switching on or off the SMM behavior. The pK_a of the parent carboxylic acid was used as a proxy for the Lewis basicity of the carboxylate, with lower pK_a values indicating greater electron-withdrawing ability for the subsequent carboxylate anion. For the investigated carboxylate anions, 2-hydroxybenzoic acid has the lowest pK_a (2.98) while the other acids are of comparable pK_a values, 4.20 for benzoic acid, 4.76 for acetic acid, and 5.03 for trimethylacetic acid (Haynes, 2010 ). Therefore, 2-hydroxybenzoate is the most electron-withdrawing in the series, and this may affect the magnetic coupling between the Dy^III and Mn^III ions. We have also extended the types of DyNaY₄[12-MC_Mn^III_Nshi-4] structures by synthesizing complexes with 3-hydroxy- and 4-hydroxybenzoate (Manickas et al., 2020 ) and with halogenated benzoate anions (2-fluoro-, 3-fluoro-, 4-fluoro-, 2-chloro-, 3-chloro-, 3-bromo-, and 2-iodobenzoate; (Michael et al., 2021 ). These carboxylates have a range of pK_a values that spans from 2.86 to 4.57 (Haynes, 2010), although at this time we have not investigated the SMM properties of these compounds.

Seeking to expand the types of DyNaY₄[12-MC_Mn^III_Nshi-4] structures beyond benzoate anions, we decided to determine if 2-propylvalerate, which has two propyl chains off the carboxylate carbon atom, could lead to MC formation. Herein we report the synthesis and crystal structure DyNa(2-PV)₄[12-MC_Mn^III_Nshi-4](H₂O)₄·4DMF, 1, where 2-PV is 2-propylvalerate and DMF is N,N-dimethylformamide. Although the pK_a of the parent 2-propylvaleric acid is 4.6 (Haynes, 2010) and the MC is not expected to possess SMM based on previous results, the 3d–4f compound will allow further investigation into the molecular characteristics that lead to single-molecule magnetism.

2. Structural commentary

DyNa(2-PV)₄[12-MC_Mn^III_Nshi-4](H₂O)₄·4DMF, 1, is centered about a crystallographic C₄ axis along the Dy^III and Na⁺ ions located in the central cavity of the metallamacrocycle. The fourfold rotational axis generates a metallacrown with four ring Mn^III ions and four shi³⁻ ligands that yield the Mn^III–N–O repeat unit. In addition, four 2-propylvalerate anions form bridges between each ring Mn^III ion and the central Dy^III ion, and four interstitial DMF molecules are hydrogen bonded to the sodium-coordinated water molecules of the metallacrown. The metallacrown framework (excluding the Dy^III and Na⁺ ions), the bridging 2-propylvalerate, and the interstitial DMF molecule experience whole molecule disorder as a result of the rotational orientation of the macrocycle. The main moiety of the molecule has an Mn^III–N–O counterclockwise rotation about the C₄ axis, while the minor B-moiety has an Mn^III–N–O clockwise rotation about the C₄ axis. Furthermore, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional orientations, and the main moiety interstitial DMF molecule is disordered over one additional orientation. The main moiety of the metallacrown framework occupancy refined to 0.9030 (14), while the minor B-moiety refined to 0.0971 (14). The main moiety alkyl chain of the 2-propylvalerate occupancies refined to 0.287 (3):0.309 (3):0.307 (3), and the minor B-moiety alkyl chain occupancy refined to 0.0971 (14). Lastly, the main moiety interstitial DMF refined to 0.549 (3):0.354 (3), and the minor B-moiety DMF refined to 0.0971 (14). In the following sections, all numbers refer to the major component, unless stated otherwise. The Refinement section contains complete details of the treatment of the disorder.

The oxidation states of the metal ions were determined based on overall molecular charge considerations, structure features of the manganese ion, and bond-valence sum (BVS) values. The four triply deprotonated shi³⁻ ligands and four 2-propylvalerate anions provide an overall 16- charge, which is counterbalanced by one Dy^III ion, one Na⁺ ion, and four Mn^III ions (16+ total charge). In addition, the Mn^III ion possesses an elongated bond along the z-axis [2.126 (5) Å] and compressed bonds in the xy lane [1.840 (4) to 1.946 (5) Å], which are typical of high spin 3d⁴ ions. Lastly, the BVS values (Liu & Thorp, 1993 ; Trzesowska et al., 2004 ) indicate that the Dy^III and Mn^III ions have a 3+ charge (Table 1).

Table 1
Average bond length (Å) and bond-valence-sum (BVS) values (v.u.) used to support assigned oxidation states of the dysprosium and manganese ions of 1

	Avg. Bond length	BVS value	Assigned oxidation state
Dy1	2.361	3.14	3+
Mn1	1.953	3.02	3+

Both central ions, Dy^III and Na⁺, are eight-coordinate although with different coordination geometries (Fig. 1; Table 2). The metallacrown framework of 1 is slightly domed with the Dy^III ion located on the convex side of the metallamacrocycle and the Na⁺ ion located on the concave side. The Dy^III ion is bound to the four oxime oxygen atoms of the MC cavity, which are provided by four different shi³⁻ ligands, and four carboxylate oxygen atoms of four different 2-propylvalerate anions. The carboxylate groups of the 2-propylvalerate anions form three atom bridges to each ring Mn^III ion. An analysis of the geometry with the program SHAPE 2.1 (Llunell et al., 2013 ; Pinsky & Avnir, 1998 ) best describes the shape as a square antiprism (Casanova et al., 2005 ). The Continuous Shape Measure (CShM) value is 0.747, indicating that the geometry approaches that of an ideal square antiprism. The Na⁺ ion is also bound to the four oxime oxygen atoms of the MC cavity, and the coordination environment is completed by four water molecules. Each water molecule also hydrogen bonds (Fig. 2) to two interstitial DMF molecules. The geometry of the Na⁺ ion cannot be clearly defined based on CShM values as the two lowest values are 3.667 for a biaugmented trigonal prism and 3.803 for a square antiprism. Typically values above 3.0 indicate significant distortions from ideal geometry; thus, for the Na⁺ ion the geometry cannot be unambiguously specified (Cirera et al., 2005 ).

Table 2
Continuous Shape Measure (CShM) values for the geometry about the eight-coordinate central Dy^III and Na⁺ ions of 1

Shape	Dy^III	Na⁺
Octagon (D_8h)	32.056	32.142
Heptagonal pyramid (C_7v)	23.666	26.075
Hexagonal bipyramid (D_6h)	16.870	13.023
Cube (O_h)	9.253	5.054
Square antiprism (D_4d)	0.747	3.803
Triangular dodecahedron (D_2d)	2.730	4.048
Johnson gyrobifastigium (J26; D_2s)	17.553	16.887
Johnson elongated triangular bipyramid (J14; D_3h)	30.395	28.728
Johnson biaugmented trigonal prism (J50; C_2v)	3.036	5.420
Biaugmented trigonal prism (C_2v)	1.991	3.667
Johnson snub diphenoid (J84; D_2d)	5.971	8.256
Triakis tetrahedron (T_d)	10.118	5.959
Elongated trigonal bipyramid (D_3h)	25.708	25.581

Figure 1
The single-crystal X-ray structure of DyNa(O₂C₈H₁₅)₄[12-MC_Mn^III_N(shi)-4](H₂O)₄·4DMF, 1. A side view with only the metal atoms labeled for clarity. The displacement ellipsoids are at the 50% probability level. For clarity, hydrogen atoms, solvent molecules, and disorder have been omitted. Color scheme: aqua – Dy^III, green – Mn^III, yellow – Na⁺, red – oxygen, blue – nitrogen, and gray – carbon. All figures were generated with the program Mercury (Macrae et al., 2020

). [Symmetry codes: (i) +x, −y + $[{1\over 2}]$ , z; (ii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z; (iii) −x + $[{1\over 2}]$ , y, z.]

Figure 2
The single-crystal X-ray structure of DyNa(O₂C₈H₁₅)₄[12-MC_Mn^III_N(shi)-4](H₂O)₄·4DMF, 1. A top view with the four bridging 2-propylvalerate anions removed for clarity. See Fig. 1

for additional display details. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z; (ii) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z; (iii) −x + $[{1\over 2}]$ , y, z.]

The ring Mn^III ion is five-coordinate with a square-pyramidal shape (Table 3). The basal region of the ligand environment consists of two trans chelate rings from two different shi³⁻ ligands. One shi³⁻ ligand forms a five-membered chelate ring by binding with the oxime and carbonyl oxygen atoms of the ligand, and the other shi³⁻ ligand forms a six-membered chelate ring by binding with the oxime nitrogen and phenolate oxygen atom of the ligand. The apical position is occupied by the carboxylate oxygen atom of the bridging 2-propylvalerate anion. Lastly, the water molecule that is coordinated to the Na⁺ ion forms a long interaction [2.527 (5) Å] with the Mn^III ion.

Table 3
Continuous Shape Measure (CShM) values for the geometry about the five-coordinate ring Mn^III ion of 1

Shape	Pentagon (D_5h)	Vacant octahedron (C_4v)	Trigonal bipyramid (D_3h)	Spherical square pyramid (C_4v)	Johnson trigonal bipyramid (J12; D_3h)
Mn1	30.515	0.832	5.422	0.739	7.504

3. Supramolecular features

For 1, the main metallacrown molecule forms hydrogen bonds to the interstitial DMF molecules via the water molecules bound to the central sodium ion. Each water molecule is hydrogen bonded to the carbonyl oxygen atom of two adjacent DMF molecules (Table 4, Fig. 3). This generates a small hydrogen-bonding network on the concave side of the metallacrown between the four sodium-bound water molecules and the four interstitial DMF molecules. A similar hydrogen-bonding connectivity is also observed for the minor B-moiety of the compound. These hydrogen bonds and pure van der Waals forces contribute to the overall packing of the molecules.

Table 4
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O7	0.86 (2)	2.02 (2)	2.860 (15)	165 (5)
O6—H6E⋯O7ⁱ	0.83 (2)	1.99 (2)	2.809 (19)	167 (5)
O6B—H6C⋯O7Bⁱ	0.84 (2)	2.00 (2)	2.80 (3)	159 (10)
O6B—H6D⋯O7B	0.85 (2)	2.01 (2)	2.859 (19)	177 (10)
Symmetry code: (i) $[-y+{\script{1\over 2}}, x, z]$ .

Figure 3
Intermolecular hydrogen bonding between the water molecules coordinated to the Na⁺ ion of 1 and the interstitial DMF molecules. Each coordinated water molecule forms hydrogen bonds with two neighboring DMF molecules. For clarity, only the hydrogen atoms (white) of the water molecules and only two of the four DMF molecules are displayed. See Fig. 1

for additional display details. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z; (iii) −x + $[{1\over 2}]$ , y, z.]

4. Database survey

A survey of the Cambridge Structural Database (CSD version 5.43, update September 2022, Groom et al., 2016 ) reveals forty LnXY₄[12-MC_Mn^III_N(shi)-4] structures, where X is a counter-cation with a 1+ charge and Y is a carboxylate anion (Azar et al., 2014; Travis et al., 2015 , 2016 ; Boron et al., 2016; Cao et al., 2016 ; Qin et al., 2017 ; Anthanasopoulou et al., 2018 ; Manickas et al., 2020; Michael et al., 2021). The central Ln^III metal ions include the lanthanide ions from Pr to Yb (except Pm) and yttrium. The counter-cation X is usually an Na⁺ or K⁺ ion that is also bound to the central cavity, but other unbound counter-cations such as tetrabutylammonium, tetraethylammonium, and triethylammonium have been employed. A range of bridging carboxylate anions (Y) have been used including acetate (OAc), trimethylacetate (TMA), benzoate (ben), 2-hydroxybenzoate (2-OHben), 3-hydroxybenzoate (3-OHben), 4-hydroxylbenzoate (4-OHben), 2-fluorobenzoate (2-Fben), 3-fluorobenzoate (3-Fben), 4-fluorobenzoate (4-Fben), 2-chlorobenzoate (2-Clben), 4-chlorobenzoate (4-Clben), 3-bromobenzoate (3-Brben), and 2-iodobenzoate (2-Iben). Of the forty structures, thirteen contain both Dy^III and Na⁺ as in 1 (Azar et al., 2014; Boron et al., 2016; Manickas et al., 2020; Michael et al., 2021). The structural comparison of 1 will be limited to the MCs that contain Dy^III and Na⁺ ions captured in the central MC cavity (Table 5). Analysis of the parameters that define the MC cavity and framework such as the cavity radius, the cross cavity Mn^III—Mn^III distance, the distance between adjacent Mn^III ions, the cross cavity oxime oxygen–oxime oxygen distance, and the distance of the Dy^III ion from the oxime oxygen mean plane reveals that the identity of the bridging carboxylate has little impact on the overall metallacrown structure. [These parameters were determined as previously defined (Azar et al., 2014)]. Indeed, this is a hallmark of metallacrown chemistry, the ability to switch components of the molecular systems without significantly affecting the overall structure. This asset allows the systematic investigation of chemical and physical properties such as magnetism or luminescence across a range of structures (Boron et al., 2016; Chow et al., 2016 ).

Table 5
Structural feature comparison of 1 and other DyNa(carboxylate)₄[12-MC_Mn^III_N(shi)-4] compounds (Å)

Compound	MC cavity radius^a	Avg. cross-cavity Mn^III—Mn^III distance^a	Avg. adjacent Mn^III—Mn^III distance^a	Avg. cross-cavity O_oxime—O_oxime distance^a	Dy^III–oxime oxygen mean plane distance^b
DyNa(2-PV)₄[12-MC-4], 1	0.54	6.51	4.60	3.68	1.6069 (37)
DyNa(OAc)₄[12-MC-4]	0.55	6.52	4.61	3.71	1.5918 (7)
DyNa(TMA)₄[12-MC-4]	0.56	6.51	4.60	3.73	1.5790 (19)
DyNa(ben)₄[12-MC-4]	0.54	6.51	4.60	3.69	1.5811 (18)
DyNa(2-OHben)₄[12-MC-4]	0.54	6.47	4.57	3.68	1.5094 (46)
DyNa(3-OHben)₄[12-MC-4]	0.56	6.53	4.62	3.72	1.5463 (25)
DyNa(4-OHben)₄[12-MC-4]	0.54	6.49	4.59	3.69	1.5925 (66)
DyNa(2-Fben)₄[12-MC-4]	0.55	6.51	4.60	3.71	1.5424 (52)
DyNa(3-Fben)₄[12-MC-4]	0.56	6.51	4.60	3.72	1.5567 (34)
DyNa(4-Fben)₄[12-MC-4]	0.54	6.52	4.61	3.68	1.5589 (45)
DyNa(2-Clben)₄[12-MC-4]	0.53	6.50	4.60	3.67	1.5883 (79)
DyNa(4-Clben)₄[12-MC-4]	0.55	6.54	4.62	3.71	1.5593 (13)
DyNa(3-Brben)₄[12-MC-4]	0.56	6.51	4.60	3.71	1.5685 (13)
DyNa(2-Iben)₄[12-MC-4]	0.54	6.50	4.59	3.68	1.5764 (117)
Notes: (a) Measured with Mercury (Macrae et al., 2020 ); (b) measured with SHELXL (Sheldrick, 2015b ).

5. Synthesis and crystallization

Materials

Dysprosium(III) nitrate pentahydrate (99.99%) and manganese(II) nitrate tetrahydrate (98%) were purchased from Alfa Aesar. Salicylhydroxamic acid (H₃shi, >98%) and sodium 2-propylvalerate (>98.0%) were purchased from TCI America. DMF (ACS grade) was purchased from VWR Chemicals BDH. All reagents were used as received and without further purification.

Synthesis

DyNa(2-PV)₄[12-MC_Mn^III_N(shi)-4](H₂O)₄·4DMF, 1. Manganese(II) nitrate tetrahydrate (2 mmol, 0.5020 g) was dissolved in 10 mL of DMF to produce a clear and colorless solution. Dysprosium(III) nitrate pentahydrate (0.125 mmol, 0.0548 g), salicylhydroxamic acid (2 mmol, 0.3063 g), and sodium 2-propylvalerate (4 mmol, 0.4648 g) were then dissolved in 10 mL of DMF, resulting in a clear, slightly tan solution. Next the manganese(II) nitrate solution was added to the latter solution resulting in a clear yellow solution. Then the solution slowly darkened, eventually producing a dark-brown/black color. The solution was stirred overnight and then gravity filtered the next day. No precipitate was recovered, and the dark-brown/black filtrate was allowed to slowly evaporate to aid crystal growth. After 11 days, dark-brown/black X-ray-quality crystals formed. The crystals were isolated and washed with cold DMF. The percentage yield was 64% (0.1562 g) based on dysprosium(III) nitrate pentahydrate. FT–IR (ATR, cm⁻¹): 1656, 1600, 1571, 1551, 1514, 1465, 1435, 1390, 1319, 1258, 1249, 1155, 1100, 1060, 1030, 932, 866, 820, 769, 754, 679, 665, 649, 606.

6. Refinement

Minor whole molecule disorder was detected for the metallacrown molecule (excluding the dysprosium and sodium ions) and all organic fragments, and the disorder was refined. The metallacrown is disordered by clockwise versus counterclockwise rotation orientation of the metallamacrocycle, as are the 2-propylvalerate anion and the interstitial DMF molecule (major and minor components). In addition, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional sites, and the main moiety interstitial DMF molecule is disordered over one additional site. The U_ij components of ADPs for disordered atoms closer to each other than 2.7 Å were restrained to be similar (SIMU command of SHELXL). Occupancies were constrained to sum to unity for all sites using SUMP commands. The major and minor (B-moiety) metallacrown units were restrained to have similar geometries. For the B-moiety benzene ring of the salicylhydroximate, the C atoms were restrained to be close to planar (FLAT command of SHELXL). For the 2-propylvalerate anion, the major (including the additional alkyl-chain disorder) and B-moieties were restrained to have similar geometries. The C-atom positions of the 2-propylvalerate were further restrained based on typical carbon–carbon bond distances and angles. The B-moiety carboxylate carbon atom (C8B) was restrained to planarity (CHIV 0 command of SHELXL).

For the interstitial DMF molecule, the N atom was restrained to be equidistant from both carbon atoms of the methyl groups. In addition, the major (including the additional disorder) and B-moieties were restrained to have similar geometries. Hydrogen-atom positions of the water molecule coordinated to the sodium ion were refined and O—H and H⋯H distances were restrained to 0.84 (2) and 1.36 (2) Å, respectively. The water-O and H-atom positions were further restrained based on hydrogen-bonding considerations to the interstitial DMF molecule, and distances of all water H atoms to the sodium ion were restrained to be similar.

All other hydrogen atoms were placed in calculated positions and refined as riding on their carrier atoms with C—H distances of 0.95 Å for sp² carbon atoms and to 1.00, 0.99 and 0.98 Å for aliphatic C—H, CH₂ and CH₃ moieties, respectively. The U_iso values for hydrogen atoms were set to a multiple of the U_eq value of the carrying carbon or oxygen atom (1.2 times for C—H and CH₂ groups and 1.5 for water molecules and methyl groups).

Subject to these conditions, the occupancy ratios refined as follows: main moiety metallacrown unit, 0.9030 (14); B-moiety metallacrown unit: 0.0971 (14); main alkyl chain of 2-propylvalerate, 0.287 (3):0.309 (3):0.307 (3); B-moiety alkyl chain, 0.0971 (14); main moiety interstitial DMF, 0.549 (3):0.354 (3); and B-moiety DMF, 0.0971 (14). Additional crystal data, data collection, and structure refinement details are summarized in Table 6.

Table 6
Experimental details

Crystal data
Chemical formula	[DyMn₄Na(C₇H₄NO₃)₄(C₈H₁₅O₂)₄(H₂O)₄]·4C₃H₇NO
M_r	1942.94
Crystal system, space group	Tetragonal, P4/n
Temperature (K)	150
a, c (Å)	18.2654 (9), 13.4219 (9)
V (Å³)	4477.9 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.45
Crystal size (mm)	0.45 × 0.43 × 0.15

Data collection
Diffractometer	Bruker AXS D8 Quest
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.020, 0.060
No. of measured, independent and observed [I > 2σ(I)] reflections	87812, 7801, 5435
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.747

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.257, 1.07
No. of reflections	7801
No. of parameters	708
No. of restraints	2628
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.36, −1.96
Computer programs: APEX4 and SAINT (Bruker, 2022 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b), ShelXle (Hübschle et al., 2011 ), Mercury (Macrae et al., 2020), and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2216645

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989022010489/ex2062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010489/ex2062Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX4 (Bruker, 2022); cell refinement: SAINT (Bruker, 2022); data reduction: SAINT (Bruker, 2022); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b), ShelXle (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

Tetraaquatetrakis(µ-2-propylvalerato)tetrakis(µ₄-salicylhydroximato)dysprosiumtetramanganesesodium dimethylformamide tetrasolvate, top

Crystal data top

[DyMn₄Na(C₇H₄NO₃)₄(C₈H₁₅O₂)₄(H₂O)₄]·4C₃H₇NO	D_x = 1.441 Mg m⁻³
M_r = 1942.94	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/n	Cell parameters from 9870 reflections
a = 18.2654 (9) Å	θ = 2.5–32.0°
c = 13.4219 (9) Å	µ = 1.45 mm⁻¹
V = 4477.9 (5) Å³	T = 150 K
Z = 2	Plate, brown
F(000) = 2002.2	0.45 × 0.43 × 0.15 mm

Data collection top

Bruker AXS D8 Quest diffractometer	7801 independent reflections
Radiation source: fine focus sealed tube X-ray source	5435 reflections with I > 2σ(I)
Triumph curved graphite crystal monochromator	R_int = 0.070
Detector resolution: 7.4074 pixels mm^-1	θ_max = 32.1°, θ_min = 2.2°
ω and phi scans	h = −27→24
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −27→27
T_min = 0.020, T_max = 0.060	l = −19→19
87812 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.072	Hydrogen site location: mixed
wR(F²) = 0.257	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.1326P)² + 7.8338P] where P = (F_o² + 2F_c²)/3
7801 reflections	(Δ/σ)_max = 0.013
708 parameters	Δρ_max = 1.36 e Å⁻³
2628 restraints	Δρ_min = −1.96 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.

Refinement. Minor whole molecule disorder was detected for the metallacrown molecule and all organic fragments (excluding the dysprosium and sodium ions), and the disorder was refined. The metallacrown is disordered by clockwise vs counterclockwise rotation orientation of the metallacycle, as are the 2-propylvalerate anion and the interstitial DMF molecule (main moiety and B-moiety). In addition, the alkyl chain of the 2-propylvalerate of the main moiety is disordered over two additional sites, and the interstitial DMF molecule of the main moiety is disordered over one additional site. The Uij components of ADPs for disordered atoms closer to each other than 2.7 Angstrom were restrained to be similar (SIMU command of Shelxl). Occupancies were constrained to sum up to unity for all sites using SUMP commands.

The major and minor (B-moiety) metallacrown units were restrained to have similar geometries. For the B-moiety benzene ring of the salicylhydroximate, the C atoms were restrained to be close to planar (FLAT command of Shelxl).

For the 2-propylvalerate anion, the major (including the additional alkyl chain disorder) and B moieties were restrained to have similar geometries. The C atoms positions 2-propylvalerate were further restrained based on typical carbon-carbon bond distances and angles. The B-moiety carboxylate carbon atom (C8B) was restrained to planarity (CHIV command of Shelxl).

H atom positions of the water molecule coordinated to the sodium ion were refined and O-H and H···H distances were restrained to 0.84 (2) and 1.36 (2) Angstrom, respectively. The water O and H atom positions were further restrained based on hydrogen bonding considerations to the interstitial DMF molecule and distances of all water H atoms to the sodium ion were restrained to be similar.

All other hydrogen atoms were placed in calculated positions and refined as riding on their carrier atoms with C-H distances of 0.95 Angstrom for sp2 carbon atoms. The Uiso values for hydrogen atoms were set to a multiple of the Ueq value of the carrying carbon atom (1.2 times for sp2 hybridized carbon atoms, 1.5 for water molecules and methyl groups).

Subject to these conditions the occupancy ratios were refined as follows:

main metallacrown unit: 0.9030 (14) B-moiety metallacrown unit: 0.0971 (14)

main alkyl chain of 2-propylvalerate: 0.287 (3): 0.309 (3): 0.307 (3) B-moiety alkyl chain: 0.0971 (14)

main interstitial DMF: 0.549 (3): 0.354 (3) B-moiety DMF: 0.0971 (14)

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Dy1	0.250000	0.250000	0.78820 (3)	0.05635 (17)
Na1	0.250000	0.250000	0.5233 (3)	0.0524 (8)
Mn1	0.14036 (4)	0.39036 (4)	0.64460 (7)	0.0514 (2)	0.9030 (14)
O1	0.23534 (18)	0.34977 (18)	0.6685 (3)	0.0490 (7)	0.9030 (14)
O2	0.19756 (19)	0.4788 (2)	0.6261 (3)	0.0563 (8)	0.9030 (14)
O3	0.4255 (2)	0.4468 (2)	0.5953 (4)	0.0683 (11)	0.9030 (14)
N1	0.2918 (3)	0.4000 (2)	0.6508 (9)	0.0499 (9)	0.9030 (14)
C1	0.2672 (3)	0.4663 (3)	0.6306 (4)	0.0504 (9)	0.9030 (14)
C2	0.3191 (3)	0.5252 (3)	0.6105 (5)	0.0563 (11)	0.9030 (14)
C3	0.2920 (3)	0.5972 (3)	0.6059 (6)	0.0631 (12)	0.9030 (14)
H3	0.241645	0.605935	0.618711	0.076*	0.9030 (14)
C4	0.3373 (4)	0.6556 (3)	0.5831 (7)	0.0696 (15)	0.9030 (14)
H4	0.318007	0.703811	0.579281	0.084*	0.9030 (14)
C5	0.4104 (4)	0.6431 (3)	0.5662 (7)	0.0706 (16)	0.9030 (14)
H5	0.441614	0.683117	0.550566	0.085*	0.9030 (14)
C6	0.4391 (3)	0.5732 (3)	0.5714 (5)	0.0664 (14)	0.9030 (14)
H6	0.489816	0.565843	0.559009	0.080*	0.9030 (14)
C7	0.3947 (3)	0.5131 (3)	0.5948 (5)	0.0581 (11)	0.9030 (14)
O4	0.1581 (3)	0.3123 (3)	0.8654 (4)	0.0740 (12)	0.9030 (14)
O5	0.1146 (3)	0.4144 (3)	0.7956 (4)	0.0773 (12)	0.9030 (14)
C8	0.1192 (5)	0.3701 (5)	0.8633 (6)	0.0876 (18)	0.9030 (14)
C9	0.0809 (12)	0.3783 (19)	0.9652 (13)	0.104 (3)	0.287 (3)
H9	0.083089	0.327758	0.993659	0.125*	0.287 (3)
C10	0.0002 (12)	0.3888 (18)	0.943 (2)	0.107 (4)	0.287 (3)
H10A	−0.026153	0.392395	1.007540	0.128*	0.287 (3)
H10B	−0.005916	0.436207	0.908509	0.128*	0.287 (3)
C11	−0.0354 (14)	0.3317 (19)	0.883 (3)	0.112 (4)	0.287 (3)
H11A	−0.024496	0.283824	0.914116	0.135*	0.287 (3)
H11B	−0.012164	0.331805	0.816430	0.135*	0.287 (3)
C12	−0.1184 (14)	0.336 (2)	0.868 (3)	0.134 (8)	0.287 (3)
H12A	−0.134736	0.295366	0.826735	0.201*	0.287 (3)
H12B	−0.142903	0.334483	0.932844	0.201*	0.287 (3)
H12C	−0.130515	0.382683	0.834713	0.201*	0.287 (3)
C13	0.1196 (14)	0.4221 (16)	1.0385 (17)	0.110 (3)	0.287 (3)
H13A	0.102073	0.473193	1.032217	0.132*	0.287 (3)
H13B	0.172113	0.422004	1.020370	0.132*	0.287 (3)
C14	0.1138 (17)	0.401 (2)	1.1475 (15)	0.118 (4)	0.287 (3)
H14A	0.065666	0.377546	1.159867	0.142*	0.287 (3)
H14B	0.117293	0.445042	1.189532	0.142*	0.287 (3)
C15	0.177 (2)	0.345 (2)	1.177 (2)	0.126 (7)	0.287 (3)
H15A	0.155796	0.298178	1.197504	0.188*	0.287 (3)
H15B	0.205757	0.365358	1.232659	0.188*	0.287 (3)
H15C	0.209632	0.337212	1.119868	0.188*	0.287 (3)
O6	0.1794 (2)	0.3562 (3)	0.4701 (3)	0.0613 (9)	0.9030 (14)
H6A	0.207 (2)	0.383 (3)	0.433 (5)	0.092*	0.9030 (14)
H6E	0.144 (3)	0.343 (3)	0.435 (5)	0.092*	0.9030 (14)
C9C	0.0715 (15)	0.3936 (16)	0.9511 (19)	0.101 (3)	0.309 (3)
H9C	0.106691	0.370299	0.998520	0.122*	0.309 (3)
C10C	0.0167 (16)	0.3347 (15)	0.9718 (19)	0.109 (4)	0.309 (3)
H10C	0.039180	0.302612	1.022895	0.131*	0.309 (3)
H10D	−0.025323	0.359039	1.004438	0.131*	0.309 (3)
C11C	−0.0138 (15)	0.2868 (18)	0.898 (2)	0.111 (4)	0.309 (3)
H11C	0.009971	0.238535	0.907550	0.133*	0.309 (3)
H11D	0.002898	0.305348	0.832615	0.133*	0.309 (3)
C12C	−0.0956 (15)	0.272 (2)	0.888 (3)	0.122 (7)	0.309 (3)
H12D	−0.103422	0.228717	0.846672	0.183*	0.309 (3)
H12E	−0.119444	0.314501	0.857290	0.183*	0.309 (3)
H12F	−0.116690	0.263779	0.954439	0.183*	0.309 (3)
C13C	0.0880 (15)	0.4648 (13)	0.992 (2)	0.109 (3)	0.309 (3)
H13C	0.047967	0.481026	1.036652	0.131*	0.309 (3)
H13D	0.093563	0.501176	0.937993	0.131*	0.309 (3)
C14C	0.1596 (16)	0.4577 (15)	1.051 (2)	0.115 (4)	0.309 (3)
H14C	0.157564	0.485240	1.114240	0.138*	0.309 (3)
H14D	0.202082	0.474735	1.011202	0.138*	0.309 (3)
C15C	0.162 (2)	0.3702 (17)	1.070 (3)	0.120 (6)	0.309 (3)
H15D	0.212086	0.352187	1.056624	0.180*	0.309 (3)
H15E	0.127934	0.345735	1.024615	0.180*	0.309 (3)
H15F	0.149029	0.359666	1.138777	0.180*	0.309 (3)
C9D	0.0619 (11)	0.375 (2)	0.9491 (15)	0.103 (3)	0.307 (3)
H9D	0.064660	0.428430	0.964243	0.124*	0.307 (3)
C10D	−0.0186 (13)	0.3685 (16)	0.922 (2)	0.105 (4)	0.307 (3)
H10E	−0.046788	0.388208	0.979130	0.126*	0.307 (3)
H10F	−0.027281	0.401942	0.865313	0.126*	0.307 (3)
C11D	−0.0511 (17)	0.2995 (18)	0.896 (3)	0.118 (5)	0.307 (3)
H11E	−0.034898	0.263808	0.947376	0.142*	0.307 (3)
H11F	−0.028719	0.284003	0.832606	0.142*	0.307 (3)
C12D	−0.1338 (17)	0.290 (2)	0.885 (4)	0.132 (8)	0.307 (3)
H12G	−0.153174	0.264001	0.943212	0.198*	0.307 (3)
H12H	−0.144137	0.261731	0.824655	0.198*	0.307 (3)
H12I	−0.157015	0.338228	0.880081	0.198*	0.307 (3)
C13D	0.0917 (15)	0.3450 (15)	1.0424 (18)	0.108 (3)	0.307 (3)
H13E	0.114151	0.296643	1.029356	0.130*	0.307 (3)
H13F	0.051448	0.338078	1.090934	0.130*	0.307 (3)
C14D	0.1487 (15)	0.3961 (19)	1.086 (2)	0.113 (4)	0.307 (3)
H14E	0.174549	0.423623	1.033458	0.136*	0.307 (3)
H14F	0.184933	0.368783	1.126639	0.136*	0.307 (3)
C15D	0.100 (2)	0.4496 (19)	1.155 (3)	0.130 (7)	0.307 (3)
H15G	0.095446	0.497242	1.121771	0.194*	0.307 (3)
H15H	0.124177	0.455943	1.219388	0.194*	0.307 (3)
H15I	0.051571	0.428170	1.164385	0.194*	0.307 (3)
Mn1B	0.4210 (3)	0.3002 (3)	0.6438 (6)	0.0469 (15)	0.0971 (14)
O1B	0.3183 (10)	0.3217 (11)	0.655 (3)	0.050 (4)	0.0971 (14)
O2B	0.4248 (12)	0.4055 (10)	0.618 (3)	0.052 (3)	0.0971 (14)
O3B	0.2210 (14)	0.5183 (15)	0.620 (3)	0.058 (4)	0.0971 (14)
N1B	0.304 (2)	0.3966 (16)	0.648 (11)	0.054 (4)	0.0971 (14)
C1B	0.3622 (14)	0.4357 (11)	0.627 (4)	0.054 (3)	0.0971 (14)
C2B	0.3539 (14)	0.5138 (11)	0.608 (2)	0.056 (3)	0.0971 (14)
C3B	0.4195 (17)	0.5499 (18)	0.584 (4)	0.060 (3)	0.0971 (14)
H3B	0.463964	0.522861	0.582859	0.073*	0.0971 (14)
C4B	0.421 (2)	0.6238 (19)	0.563 (5)	0.062 (4)	0.0971 (14)
H4B	0.465052	0.648291	0.546111	0.074*	0.0971 (14)
C5B	0.355 (2)	0.660 (2)	0.567 (5)	0.063 (4)	0.0971 (14)
H5B	0.355061	0.711149	0.552398	0.076*	0.0971 (14)
C6B	0.290 (2)	0.6277 (15)	0.591 (4)	0.060 (4)	0.0971 (14)
H6B	0.246663	0.656543	0.595648	0.072*	0.0971 (14)
C7B	0.2863 (14)	0.5516 (15)	0.609 (4)	0.058 (3)	0.0971 (14)
O4B	0.249 (3)	0.352 (2)	0.881 (3)	0.090 (5)	0.0971 (14)
O5B	0.190 (3)	0.437 (3)	0.793 (3)	0.075 (6)	0.0971 (14)
C8B	0.215 (2)	0.414 (2)	0.872 (2)	0.091 (5)	0.0971 (14)
C9B	0.212 (3)	0.450 (3)	0.976 (3)	0.105 (4)	0.0971 (14)
H9B	0.244392	0.493722	0.971060	0.126*	0.0971 (14)
C10B	0.135 (3)	0.480 (4)	0.988 (4)	0.106 (4)	0.0971 (14)
H10G	0.102155	0.436896	0.990354	0.127*	0.0971 (14)
H10H	0.133232	0.502994	1.054169	0.127*	0.0971 (14)
C11B	0.102 (3)	0.531 (4)	0.920 (6)	0.107 (5)	0.0971 (14)
H11G	0.126655	0.524595	0.854898	0.128*	0.0971 (14)
H11H	0.114377	0.580442	0.944008	0.128*	0.0971 (14)
C12B	0.020 (3)	0.531 (5)	0.899 (6)	0.109 (11)	0.0971 (14)
H12J	0.007978	0.569567	0.850948	0.163*	0.0971 (14)
H12K	0.005171	0.483275	0.871238	0.163*	0.0971 (14)
H12L	−0.007204	0.539560	0.961048	0.163*	0.0971 (14)
C13B	0.245 (3)	0.404 (4)	1.054 (4)	0.107 (5)	0.0971 (14)
H13G	0.275633	0.434715	1.097827	0.128*	0.0971 (14)
H13H	0.277073	0.366752	1.022537	0.128*	0.0971 (14)
C14B	0.187 (4)	0.365 (5)	1.116 (7)	0.112 (5)	0.0971 (14)
H14G	0.146656	0.347873	1.073754	0.135*	0.0971 (14)
H14H	0.167172	0.398959	1.167225	0.135*	0.0971 (14)
C15B	0.227 (6)	0.297 (4)	1.169 (6)	0.115 (10)	0.0971 (14)
H15J	0.191748	0.270452	1.210549	0.173*	0.0971 (14)
H15K	0.246830	0.264050	1.118237	0.173*	0.0971 (14)
H15L	0.267251	0.314898	1.211273	0.173*	0.0971 (14)
O6B	0.2072 (19)	0.383 (3)	0.472 (3)	0.065 (6)	0.0971 (14)
H6C	0.178 (4)	0.368 (3)	0.428 (7)	0.097*	0.0971 (14)
H6D	0.247 (3)	0.393 (4)	0.443 (7)	0.097*	0.0971 (14)
O7	0.2905 (12)	0.4390 (12)	0.371 (2)	0.071 (4)	0.549 (3)
C16	0.3400 (8)	0.4850 (8)	0.3568 (10)	0.086 (3)	0.549 (3)
H16	0.381901	0.482146	0.398582	0.104*	0.549 (3)
N2	0.3391 (8)	0.5377 (9)	0.2882 (13)	0.082 (3)	0.549 (3)
C17	0.4050 (11)	0.5828 (11)	0.2738 (15)	0.120 (5)	0.549 (3)
H17A	0.446742	0.551047	0.258363	0.179*	0.549 (3)
H17B	0.415204	0.610433	0.334803	0.179*	0.549 (3)
H17C	0.396990	0.616954	0.218513	0.179*	0.549 (3)
C18	0.2743 (11)	0.5436 (12)	0.2230 (15)	0.122 (5)	0.549 (3)
H18A	0.272351	0.592718	0.193768	0.183*	0.549 (3)
H18B	0.229911	0.534844	0.262163	0.183*	0.549 (3)
H18C	0.277733	0.507079	0.169677	0.183*	0.549 (3)
O7B	0.338 (2)	0.417 (2)	0.366 (4)	0.086 (7)	0.0971 (14)
C16B	0.293 (3)	0.467 (3)	0.352 (7)	0.088 (5)	0.0971 (14)
H16B	0.242889	0.459512	0.370384	0.105*	0.0971 (14)
N2B	0.313 (3)	0.532 (2)	0.311 (5)	0.089 (5)	0.0971 (14)
C17B	0.255 (4)	0.588 (3)	0.313 (7)	0.097 (8)	0.0971 (14)
H17D	0.273533	0.633174	0.283004	0.145*	0.0971 (14)
H17E	0.212737	0.570271	0.276391	0.145*	0.0971 (14)
H17F	0.241486	0.597465	0.382769	0.145*	0.0971 (14)
C18B	0.392 (3)	0.546 (4)	0.323 (7)	0.095 (7)	0.0971 (14)
H18D	0.404240	0.593394	0.291920	0.142*	0.0971 (14)
H18E	0.404357	0.547736	0.393683	0.142*	0.0971 (14)
H18F	0.420059	0.507229	0.290140	0.142*	0.0971 (14)
O7C	0.296 (2)	0.441 (2)	0.386 (4)	0.077 (6)	0.354 (3)
C16C	0.2949 (12)	0.4984 (12)	0.3350 (17)	0.087 (4)	0.354 (3)
H16C	0.250026	0.522809	0.321376	0.104*	0.354 (3)
N2C	0.3591 (11)	0.5251 (12)	0.299 (2)	0.080 (4)	0.354 (3)
C17C	0.3557 (17)	0.5992 (13)	0.257 (2)	0.112 (6)	0.354 (3)
H17G	0.404347	0.613588	0.233349	0.168*	0.354 (3)
H17H	0.321143	0.599778	0.201064	0.168*	0.354 (3)
H17I	0.339192	0.633706	0.308216	0.168*	0.354 (3)
C18C	0.4231 (14)	0.4784 (15)	0.303 (2)	0.118 (6)	0.354 (3)
H18G	0.465149	0.504563	0.274964	0.176*	0.354 (3)
H18H	0.433399	0.465172	0.372309	0.176*	0.354 (3)
H18I	0.413916	0.433936	0.264112	0.176*	0.354 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Dy1	0.0591 (2)	0.0591 (2)	0.0508 (3)	0.000	0.000	0.000
Na1	0.0498 (10)	0.0498 (10)	0.058 (2)	0.000	0.000	0.000
Mn1	0.0453 (4)	0.0447 (4)	0.0641 (5)	0.0015 (2)	0.0072 (3)	0.0063 (3)
O1	0.0445 (15)	0.0446 (15)	0.0580 (19)	0.0001 (12)	0.0063 (13)	0.0018 (13)
O2	0.0482 (16)	0.0458 (17)	0.075 (2)	0.0004 (13)	0.0103 (16)	0.0038 (16)
O3	0.0549 (19)	0.0484 (18)	0.102 (3)	−0.0038 (15)	0.022 (2)	−0.0030 (19)
N1	0.049 (2)	0.0442 (18)	0.057 (2)	−0.0025 (15)	0.009 (3)	−0.0048 (17)
C1	0.051 (2)	0.0420 (19)	0.058 (2)	−0.0031 (16)	0.0111 (18)	−0.0014 (17)
C2	0.055 (2)	0.046 (2)	0.068 (3)	−0.0066 (18)	0.005 (2)	−0.006 (2)
C3	0.057 (2)	0.048 (2)	0.085 (3)	−0.003 (2)	0.007 (2)	0.001 (2)
C4	0.062 (3)	0.045 (2)	0.101 (4)	−0.004 (2)	0.011 (3)	0.001 (3)
C5	0.066 (3)	0.051 (3)	0.095 (4)	−0.011 (2)	0.010 (3)	0.000 (3)
C6	0.059 (3)	0.050 (2)	0.090 (4)	−0.011 (2)	0.018 (3)	−0.004 (3)
C7	0.056 (2)	0.044 (2)	0.074 (3)	−0.0055 (18)	0.016 (2)	−0.005 (2)
O4	0.086 (3)	0.076 (3)	0.060 (2)	0.006 (2)	0.019 (2)	−0.006 (2)
O5	0.087 (3)	0.076 (3)	0.069 (3)	0.003 (2)	0.021 (2)	−0.002 (2)
C8	0.100 (4)	0.095 (4)	0.067 (3)	0.010 (4)	0.026 (3)	−0.015 (3)
C9	0.117 (6)	0.113 (6)	0.083 (5)	0.015 (6)	0.024 (5)	−0.012 (5)
C10	0.115 (7)	0.121 (7)	0.084 (6)	0.015 (6)	0.029 (6)	−0.011 (6)
C11	0.121 (8)	0.123 (8)	0.093 (7)	0.006 (8)	0.026 (7)	−0.010 (8)
C12	0.140 (15)	0.155 (16)	0.107 (14)	0.016 (15)	0.038 (13)	−0.003 (14)
C13	0.121 (6)	0.121 (6)	0.087 (6)	0.011 (6)	0.019 (6)	−0.013 (6)
C14	0.132 (8)	0.128 (8)	0.095 (7)	0.008 (8)	0.023 (7)	−0.015 (7)
C15	0.143 (13)	0.146 (13)	0.088 (11)	−0.007 (12)	0.018 (12)	−0.011 (12)
O6	0.057 (2)	0.064 (2)	0.063 (2)	−0.0103 (17)	−0.0029 (18)	0.0144 (19)
C9C	0.114 (6)	0.110 (6)	0.080 (5)	0.017 (5)	0.025 (5)	−0.013 (5)
C10C	0.119 (7)	0.122 (7)	0.086 (6)	0.013 (7)	0.026 (6)	−0.011 (6)
C11C	0.109 (8)	0.125 (8)	0.098 (7)	0.019 (7)	0.027 (7)	−0.013 (7)
C12C	0.111 (14)	0.145 (15)	0.110 (13)	−0.013 (14)	0.036 (13)	−0.011 (13)
C13C	0.123 (7)	0.118 (7)	0.086 (6)	0.013 (6)	0.024 (6)	−0.021 (6)
C14C	0.127 (7)	0.121 (7)	0.096 (7)	0.007 (7)	0.022 (6)	−0.014 (6)
C15C	0.137 (11)	0.126 (11)	0.098 (10)	0.021 (10)	0.023 (10)	−0.014 (10)
C9D	0.114 (6)	0.113 (6)	0.082 (5)	0.019 (6)	0.025 (5)	−0.009 (5)
C10D	0.115 (7)	0.118 (7)	0.083 (7)	0.012 (7)	0.031 (6)	−0.013 (7)
C11D	0.127 (9)	0.131 (9)	0.096 (8)	0.010 (9)	0.025 (9)	−0.004 (8)
C12D	0.136 (16)	0.130 (16)	0.130 (15)	0.016 (15)	0.020 (15)	−0.022 (15)
C13D	0.120 (6)	0.123 (7)	0.082 (6)	0.011 (6)	0.025 (6)	−0.011 (6)
C14D	0.127 (7)	0.121 (7)	0.091 (7)	0.014 (7)	0.022 (6)	−0.012 (6)
C15D	0.140 (13)	0.131 (13)	0.118 (12)	0.018 (12)	0.035 (11)	−0.004 (12)
Mn1B	0.036 (3)	0.038 (3)	0.066 (4)	0.001 (2)	−0.001 (2)	−0.002 (2)
O1B	0.042 (7)	0.032 (7)	0.075 (8)	0.003 (6)	0.009 (7)	0.007 (7)
O2B	0.048 (6)	0.035 (6)	0.073 (7)	−0.002 (6)	0.006 (6)	0.001 (6)
O3B	0.054 (7)	0.047 (7)	0.074 (7)	−0.004 (7)	0.009 (7)	−0.005 (7)
N1B	0.052 (7)	0.040 (7)	0.070 (7)	−0.006 (6)	0.010 (7)	0.000 (7)
C1B	0.055 (6)	0.037 (6)	0.072 (6)	−0.004 (6)	0.012 (6)	0.000 (6)
C2B	0.052 (5)	0.040 (5)	0.076 (5)	−0.006 (5)	0.012 (5)	−0.001 (5)
C3B	0.056 (6)	0.043 (6)	0.083 (6)	−0.004 (6)	0.012 (6)	−0.002 (6)
C4B	0.057 (7)	0.045 (7)	0.084 (7)	−0.007 (7)	0.011 (7)	−0.002 (7)
C5B	0.058 (7)	0.046 (7)	0.085 (7)	−0.012 (7)	0.015 (7)	0.002 (7)
C6B	0.055 (7)	0.043 (7)	0.081 (7)	−0.007 (7)	0.013 (7)	−0.001 (7)
C7B	0.055 (6)	0.042 (6)	0.078 (6)	−0.007 (6)	0.010 (6)	−0.003 (6)
O4B	0.104 (10)	0.094 (9)	0.071 (9)	0.012 (9)	0.012 (9)	−0.019 (9)
O5B	0.076 (12)	0.081 (12)	0.068 (12)	0.001 (11)	−0.006 (11)	−0.009 (11)
C8B	0.103 (8)	0.097 (8)	0.072 (8)	0.011 (8)	0.019 (8)	−0.015 (8)
C9B	0.118 (7)	0.112 (7)	0.083 (7)	0.012 (7)	0.020 (7)	−0.016 (7)
C10B	0.118 (7)	0.115 (7)	0.084 (6)	0.014 (6)	0.023 (6)	−0.015 (6)
C11B	0.120 (9)	0.115 (10)	0.086 (9)	0.013 (9)	0.023 (9)	−0.015 (9)
C12B	0.12 (2)	0.12 (2)	0.084 (19)	0.02 (2)	0.038 (19)	−0.017 (19)
C13B	0.120 (8)	0.116 (8)	0.085 (8)	0.011 (8)	0.019 (8)	−0.014 (8)
C14B	0.126 (9)	0.122 (9)	0.088 (8)	0.011 (8)	0.023 (8)	−0.015 (8)
C15B	0.132 (19)	0.131 (19)	0.082 (18)	−0.005 (19)	0.019 (18)	−0.010 (18)
O6B	0.058 (11)	0.070 (12)	0.066 (12)	−0.008 (11)	0.004 (11)	0.012 (11)
O7	0.071 (6)	0.071 (6)	0.070 (9)	−0.005 (5)	−0.001 (5)	0.021 (6)
C16	0.098 (7)	0.089 (6)	0.072 (5)	−0.030 (6)	−0.022 (5)	0.010 (5)
N2	0.114 (7)	0.071 (5)	0.062 (6)	−0.032 (5)	−0.007 (6)	0.012 (4)
C17	0.133 (11)	0.110 (9)	0.116 (10)	−0.054 (9)	−0.015 (9)	0.025 (8)
C18	0.139 (11)	0.117 (10)	0.111 (10)	0.006 (9)	0.001 (9)	0.014 (8)
O7B	0.100 (13)	0.080 (12)	0.077 (12)	−0.026 (12)	0.005 (12)	0.019 (12)
C16B	0.106 (9)	0.083 (9)	0.074 (9)	−0.026 (9)	−0.002 (9)	0.013 (9)
N2B	0.108 (9)	0.083 (8)	0.076 (9)	−0.026 (8)	−0.003 (8)	0.012 (8)
C17B	0.118 (15)	0.094 (14)	0.078 (14)	−0.025 (14)	−0.003 (14)	0.007 (13)
C18B	0.113 (13)	0.089 (12)	0.082 (12)	−0.027 (12)	0.008 (12)	0.018 (12)
O7C	0.082 (10)	0.075 (9)	0.075 (12)	−0.007 (8)	0.001 (9)	0.018 (8)
C16C	0.110 (8)	0.075 (7)	0.076 (7)	−0.016 (7)	0.012 (7)	0.017 (6)
N2C	0.102 (8)	0.076 (7)	0.062 (7)	−0.033 (7)	−0.004 (7)	0.004 (6)
C17C	0.136 (12)	0.095 (11)	0.105 (11)	−0.018 (11)	0.012 (11)	0.014 (10)
C18C	0.126 (11)	0.116 (11)	0.110 (11)	−0.026 (10)	−0.001 (10)	0.017 (10)

Geometric parameters (Å, º) top

Dy1—O4B	2.24 (4)	C10D—C11D	1.43 (2)
Dy1—O4ⁱ	2.277 (5)	C10D—H10E	0.9900
Dy1—O4ⁱⁱ	2.277 (5)	C10D—H10F	0.9900
Dy1—O4ⁱⁱⁱ	2.277 (5)	C11D—C12D	1.53 (2)
Dy1—O4	2.277 (5)	C11D—H11E	0.9900
Dy1—O1	2.444 (3)	C11D—H11F	0.9900
Dy1—O1ⁱⁱ	2.444 (3)	C12D—H12G	0.9800
Dy1—O1ⁱⁱⁱ	2.444 (3)	C12D—H12H	0.9800
Dy1—O1ⁱ	2.444 (3)	C12D—H12I	0.9800
Dy1—O1Bⁱⁱⁱ	2.54 (3)	C13D—C14D	1.52 (2)
Dy1—O1Bⁱⁱ	2.54 (3)	C13D—H13E	0.9900
Dy1—O1Bⁱ	2.54 (3)	C13D—H13F	0.9900
Na1—O6	2.436 (5)	C14D—C15D	1.61 (2)
Na1—O6ⁱⁱ	2.436 (5)	C14D—H14E	0.9900
Na1—O6ⁱ	2.436 (5)	C14D—H14F	0.9900
Na1—O6ⁱⁱⁱ	2.436 (5)	C15D—H15G	0.9800
Na1—O1Bⁱ	2.53 (3)	C15D—H15H	0.9800
Na1—O1Bⁱⁱ	2.53 (3)	C15D—H15I	0.9800
Na1—O1Bⁱⁱⁱ	2.53 (3)	Mn1B—O3Bⁱ	1.85 (3)
Na1—O1B	2.53 (3)	Mn1B—O1B	1.923 (17)
Na1—O6Bⁱⁱ	2.64 (5)	Mn1B—N1Bⁱ	1.95 (4)
Na1—O6Bⁱ	2.64 (5)	Mn1B—O2B	1.955 (17)
Na1—O6Bⁱⁱⁱ	2.64 (5)	Mn1B—O6Bⁱ	2.41 (4)
Na1—O6B	2.64 (5)	O1B—N1B	1.397 (18)
Mn1—O3ⁱⁱ	1.840 (4)	O2B—C1B	1.275 (18)
Mn1—O1	1.914 (3)	O3B—C7B	1.349 (19)
Mn1—O2	1.939 (4)	N1B—C1B	1.317 (19)
Mn1—N1ⁱⁱ	1.946 (5)	C1B—C2B	1.459 (17)
Mn1—O5	2.126 (5)	C2B—C3B	1.404 (19)
Mn1—O6	2.527 (5)	C2B—C7B	1.414 (19)
O1—N1	1.401 (5)	C3B—C4B	1.38 (2)
O2—C1	1.294 (6)	C3B—H3B	0.9500
O3—C7	1.335 (7)	C4B—C5B	1.37 (2)
N1—C1	1.319 (7)	C4B—H4B	0.9500
C1—C2	1.459 (7)	C5B—C6B	1.37 (2)
C2—C3	1.406 (8)	C5B—H5B	0.9500
C2—C7	1.415 (8)	C6B—C7B	1.412 (19)
C3—C4	1.384 (8)	C6B—H6B	0.9500
C3—H3	0.9500	O4B—C8B	1.29 (2)
C4—C5	1.373 (9)	O5B—C8B	1.23 (2)
C4—H4	0.9500	C8B—C9B	1.54 (2)
C5—C6	1.383 (9)	C9B—C13B	1.47 (2)
C5—H5	0.9500	C9B—C10B	1.52 (2)
C6—C7	1.402 (7)	C9B—H9B	1.0000
C6—H6	0.9500	C10B—C11B	1.44 (2)
O4—C8	1.274 (10)	C10B—H10G	0.9900
O5—C8	1.220 (10)	C10B—H10H	0.9900
C8—C9C	1.526 (16)	C11B—C12B	1.53 (2)
C8—C9	1.543 (16)	C11B—H11G	0.9900
C8—C9D	1.558 (16)	C11B—H11H	0.9900
C9—C13	1.452 (16)	C12B—H12J	0.9800
C9—C10	1.515 (15)	C12B—H12K	0.9800
C9—H9	1.0000	C12B—H12L	0.9800
C10—C11	1.470 (16)	C13B—C14B	1.52 (2)
C10—H10A	0.9900	C13B—H13G	0.9900
C10—H10B	0.9900	C13B—H13H	0.9900
C11—C12	1.530 (16)	C14B—C15B	1.61 (2)
C11—H11A	0.9900	C14B—H14G	0.9900
C11—H11B	0.9900	C14B—H14H	0.9900
C12—H12A	0.9800	C15B—H15J	0.9800
C12—H12B	0.9800	C15B—H15K	0.9800
C12—H12C	0.9800	C15B—H15L	0.9800
C13—C14	1.517 (17)	O6B—H6C	0.84 (2)
C13—H13A	0.9900	O6B—H6D	0.850 (18)
C13—H13B	0.9900	O7—C16	1.248 (18)
C14—C15	1.594 (17)	C16—N2	1.333 (15)
C14—H14A	0.9900	C16—H16	0.9500
C14—H14B	0.9900	N2—C17	1.472 (14)
C15—H15A	0.9800	N2—C18	1.475 (16)
C15—H15B	0.9800	C17—H17A	0.9800
C15—H15C	0.9800	C17—H17B	0.9800
O6—H6A	0.857 (17)	C17—H17C	0.9800
O6—H6E	0.832 (18)	C18—H18A	0.9800
C9C—C13C	1.44 (2)	C18—H18B	0.9800
C9C—C10C	1.50 (2)	C18—H18C	0.9800
C9C—H9C	1.0000	O7B—C16B	1.25 (2)
C10C—C11C	1.43 (2)	C16B—N2B	1.36 (2)
C10C—H10C	0.9900	C16B—H16B	0.9500
C10C—H10D	0.9900	N2B—C18B	1.47 (2)
C11C—C12C	1.53 (2)	N2B—C17B	1.47 (2)
C11C—H11C	0.9900	C17B—H17D	0.9800
C11C—H11D	0.9900	C17B—H17E	0.9800
C12C—H12D	0.9800	C17B—H17F	0.9800
C12C—H12E	0.9800	C18B—H18D	0.9800
C12C—H12F	0.9800	C18B—H18E	0.9800
C13C—C14C	1.53 (2)	C18B—H18F	0.9800
C13C—H13C	0.9900	O7C—C16C	1.25 (2)
C13C—H13D	0.9900	C16C—N2C	1.358 (18)
C14C—C15C	1.62 (2)	C16C—H16C	0.9500
C14C—H14C	0.9900	N2C—C18C	1.448 (18)
C14C—H14D	0.9900	N2C—C17C	1.469 (17)
C15C—H15D	0.9800	C17C—H17G	0.9800
C15C—H15E	0.9800	C17C—H17H	0.9800
C15C—H15F	0.9800	C17C—H17I	0.9800
C9D—C13D	1.47 (2)	C18C—H18G	0.9800
C9D—C10D	1.52 (2)	C18C—H18H	0.9800
C9D—H9D	1.0000	C18C—H18I	0.9800

O4B—Dy1—O4ⁱⁱ	111.0 (14)	C10C—C9C—C8	108.9 (16)
O4ⁱ—Dy1—O4ⁱⁱ	125.9 (3)	C13C—C9C—H9C	90.3
O4B—Dy1—O4ⁱⁱⁱ	99.8 (12)	C10C—C9C—H9C	90.3
O4ⁱ—Dy1—O4ⁱⁱⁱ	78.06 (11)	C8—C9C—H9C	90.3
O4ⁱⁱ—Dy1—O4ⁱⁱⁱ	78.06 (11)	C11C—C10C—C9C	125 (2)
O4ⁱ—Dy1—O4	78.06 (11)	C11C—C10C—H10C	106.1
O4ⁱⁱ—Dy1—O4	78.06 (11)	C9C—C10C—H10C	106.1
O4ⁱⁱⁱ—Dy1—O4	125.9 (3)	C11C—C10C—H10D	106.1
O4ⁱ—Dy1—O1	78.69 (16)	C9C—C10C—H10D	106.1
O4ⁱⁱ—Dy1—O1	142.57 (15)	H10C—C10C—H10D	106.3
O4ⁱⁱⁱ—Dy1—O1	138.77 (16)	C10C—C11C—C12C	123 (2)
O4—Dy1—O1	81.14 (15)	C10C—C11C—H11C	106.5
O4B—Dy1—O1ⁱⁱ	116.6 (12)	C12C—C11C—H11C	106.5
O4ⁱ—Dy1—O1ⁱⁱ	138.77 (16)	C10C—C11C—H11D	106.5
O4ⁱⁱ—Dy1—O1ⁱⁱ	81.14 (15)	C12C—C11C—H11D	106.5
O4ⁱⁱⁱ—Dy1—O1ⁱⁱ	142.57 (15)	H11C—C11C—H11D	106.5
O4—Dy1—O1ⁱⁱ	78.69 (16)	C11C—C12C—H12D	109.5
O1—Dy1—O1ⁱⁱ	64.39 (9)	C11C—C12C—H12E	109.5
O4B—Dy1—O1ⁱⁱⁱ	170.3 (14)	H12D—C12C—H12E	109.5
O4ⁱ—Dy1—O1ⁱⁱⁱ	142.57 (15)	C11C—C12C—H12F	109.5
O4ⁱⁱ—Dy1—O1ⁱⁱⁱ	78.69 (16)	H12D—C12C—H12F	109.5
O4ⁱⁱⁱ—Dy1—O1ⁱⁱⁱ	81.14 (15)	H12E—C12C—H12F	109.5
O4—Dy1—O1ⁱⁱⁱ	138.77 (16)	C9C—C13C—C14C	107.4 (19)
O1—Dy1—O1ⁱⁱⁱ	97.80 (17)	C9C—C13C—H13C	110.2
O1ⁱⁱ—Dy1—O1ⁱⁱⁱ	64.40 (9)	C14C—C13C—H13C	110.2
O4B—Dy1—O1ⁱ	106.2 (15)	C9C—C13C—H13D	110.2
O4ⁱ—Dy1—O1ⁱ	81.14 (15)	C14C—C13C—H13D	110.2
O4ⁱⁱ—Dy1—O1ⁱ	138.77 (16)	H13C—C13C—H13D	108.5
O4ⁱⁱⁱ—Dy1—O1ⁱ	78.69 (16)	C13C—C14C—C15C	101.0 (19)
O4—Dy1—O1ⁱ	142.57 (15)	C13C—C14C—H14C	111.6
O1—Dy1—O1ⁱ	64.40 (9)	C15C—C14C—H14C	111.6
O1ⁱⁱ—Dy1—O1ⁱ	97.80 (17)	C13C—C14C—H14D	111.6
O1ⁱⁱⁱ—Dy1—O1ⁱ	64.40 (9)	C15C—C14C—H14D	111.6
O4B—Dy1—O1Bⁱⁱⁱ	144.4 (13)	H14C—C14C—H14D	109.4
O4ⁱ—Dy1—O1Bⁱⁱⁱ	160.8 (7)	C14C—C15C—H15D	109.5
O4ⁱⁱ—Dy1—O1Bⁱⁱⁱ	72.2 (7)	C14C—C15C—H15E	109.5
O4ⁱⁱⁱ—Dy1—O1Bⁱⁱⁱ	115.1 (5)	H15D—C15C—H15E	109.5
O4—Dy1—O1Bⁱⁱⁱ	102.4 (5)	C14C—C15C—H15F	109.5
O1—Dy1—O1Bⁱⁱⁱ	82.4 (7)	H15D—C15C—H15F	109.5
O1ⁱⁱ—Dy1—O1Bⁱⁱⁱ	27.9 (4)	H15E—C15C—H15F	109.5
O1ⁱⁱⁱ—Dy1—O1Bⁱⁱⁱ	37.6 (4)	C13D—C9D—C10D	122 (2)
O1ⁱ—Dy1—O1Bⁱⁱⁱ	87.7 (7)	C13D—C9D—C8	111.2 (19)
O4B—Dy1—O1Bⁱⁱ	88.6 (13)	C10D—C9D—C8	118.0 (18)
O4ⁱ—Dy1—O1Bⁱⁱ	102.4 (5)	C13D—C9D—H9D	99.9
O4ⁱⁱ—Dy1—O1Bⁱⁱ	115.1 (5)	C10D—C9D—H9D	99.9
O4ⁱⁱⁱ—Dy1—O1Bⁱⁱ	160.8 (7)	C8—C9D—H9D	99.9
O4—Dy1—O1Bⁱⁱ	72.2 (7)	C11D—C10D—C9D	122 (2)
O1—Dy1—O1Bⁱⁱ	27.9 (4)	C11D—C10D—H10E	106.9
O1ⁱⁱ—Dy1—O1Bⁱⁱ	37.6 (4)	C9D—C10D—H10E	106.9
O1ⁱⁱⁱ—Dy1—O1Bⁱⁱ	87.7 (7)	C11D—C10D—H10F	106.9
O1ⁱ—Dy1—O1Bⁱⁱ	82.4 (7)	C9D—C10D—H10F	106.9
O1Bⁱⁱⁱ—Dy1—O1Bⁱⁱ	60.4 (9)	H10E—C10D—H10F	106.7
O4B—Dy1—O1Bⁱ	143.3 (15)	C10D—C11D—C12D	122 (2)
O4ⁱ—Dy1—O1Bⁱ	115.1 (5)	C10D—C11D—H11E	106.8
O4ⁱⁱ—Dy1—O1Bⁱ	102.4 (5)	C12D—C11D—H11E	106.8
O4ⁱⁱⁱ—Dy1—O1Bⁱ	72.2 (7)	C10D—C11D—H11F	106.8
O4—Dy1—O1Bⁱ	160.8 (7)	C12D—C11D—H11F	106.8
O1—Dy1—O1Bⁱ	87.7 (7)	H11E—C11D—H11F	106.6
O1ⁱⁱ—Dy1—O1Bⁱ	82.4 (7)	C11D—C12D—H12G	109.5
O1ⁱⁱⁱ—Dy1—O1Bⁱ	27.9 (4)	C11D—C12D—H12H	109.5
O1ⁱ—Dy1—O1Bⁱ	37.6 (4)	H12G—C12D—H12H	109.5
O1Bⁱⁱⁱ—Dy1—O1Bⁱ	60.4 (9)	C11D—C12D—H12I	109.5
O1Bⁱⁱ—Dy1—O1Bⁱ	90.7 (15)	H12G—C12D—H12I	109.5
O6—Na1—O6ⁱⁱ	85.06 (8)	H12H—C12D—H12I	109.5
O6—Na1—O6ⁱ	85.06 (8)	C9D—C13D—C14D	111 (2)
O6ⁱⁱ—Na1—O6ⁱ	145.9 (3)	C9D—C13D—H13E	109.5
O6—Na1—O6ⁱⁱⁱ	145.9 (3)	C14D—C13D—H13E	109.5
O6ⁱⁱ—Na1—O6ⁱⁱⁱ	85.06 (8)	C9D—C13D—H13F	109.5
O6ⁱ—Na1—O6ⁱⁱⁱ	85.06 (8)	C14D—C13D—H13F	109.5
O6—Na1—O1Bⁱ	150.7 (6)	H13E—C13D—H13F	108.1
O6ⁱⁱ—Na1—O1Bⁱ	110.9 (4)	C13D—C14D—C15D	103 (2)
O6ⁱ—Na1—O1Bⁱ	93.1 (5)	C13D—C14D—H14E	111.2
O6ⁱⁱⁱ—Na1—O1Bⁱ	62.5 (6)	C15D—C14D—H14E	111.2
O6—Na1—O1Bⁱⁱ	62.5 (6)	C13D—C14D—H14F	111.2
O6ⁱⁱ—Na1—O1Bⁱⁱ	93.1 (5)	C15D—C14D—H14F	111.2
O6ⁱ—Na1—O1Bⁱⁱ	110.9 (4)	H14E—C14D—H14F	109.2
O6ⁱⁱⁱ—Na1—O1Bⁱⁱ	150.7 (6)	C14D—C15D—H15G	109.5
O1Bⁱ—Na1—O1Bⁱⁱ	91.4 (12)	C14D—C15D—H15H	109.5
O6—Na1—O1Bⁱⁱⁱ	110.9 (4)	H15G—C15D—H15H	109.5
O6ⁱⁱ—Na1—O1Bⁱⁱⁱ	62.5 (6)	C14D—C15D—H15I	109.5
O6ⁱ—Na1—O1Bⁱⁱⁱ	150.7 (6)	H15G—C15D—H15I	109.5
O6ⁱⁱⁱ—Na1—O1Bⁱⁱⁱ	93.1 (5)	H15H—C15D—H15I	109.5
O1Bⁱ—Na1—O1Bⁱⁱⁱ	60.8 (7)	O3Bⁱ—Mn1B—O1B	174.4 (18)
O1Bⁱⁱ—Na1—O1Bⁱⁱⁱ	60.8 (7)	O3Bⁱ—Mn1B—O2B	98.1 (10)
O1Bⁱ—Na1—O1B	60.8 (7)	O1B—Mn1B—O2B	81.2 (8)
O1Bⁱⁱ—Na1—O1B	60.8 (7)	N1Bⁱ—Mn1B—O2B	166 (3)
O1Bⁱⁱⁱ—Na1—O1B	91.4 (12)	O3Bⁱ—Mn1B—O6Bⁱ	95.9 (17)
O6—Na1—O6Bⁱⁱ	71.0 (7)	O1B—Mn1B—O6Bⁱ	78.5 (16)
O6ⁱⁱ—Na1—O6Bⁱⁱ	15.2 (7)	N1Bⁱ—Mn1B—O6Bⁱ	85 (4)
O6ⁱ—Na1—O6Bⁱⁱ	144.3 (8)	O2B—Mn1B—O6Bⁱ	84.1 (14)
O6ⁱⁱⁱ—Na1—O6Bⁱⁱ	100.0 (8)	O3Bⁱ—Mn1B—Na1	134.2 (11)
O1Bⁱ—Na1—O6Bⁱⁱ	120.7 (9)	O1B—Mn1B—Na1	41.2 (10)
O1Bⁱⁱ—Na1—O6Bⁱⁱ	81.5 (10)	N1Bⁱ—Mn1B—Na1	65 (3)
O1Bⁱⁱⁱ—Na1—O6Bⁱⁱ	64.8 (10)	O2B—Mn1B—Na1	101.6 (9)
O1B—Na1—O6Bⁱⁱ	142.0 (10)	O6Bⁱ—Mn1B—Na1	46.4 (12)
O6—Na1—O6Bⁱ	100.0 (8)	N1B—O1B—Mn1B	112.6 (15)
O6ⁱⁱ—Na1—O6Bⁱ	144.3 (8)	N1B—O1B—Na1	112 (6)
O6ⁱ—Na1—O6Bⁱ	15.2 (7)	Mn1B—O1B—Na1	108.7 (13)
O6ⁱⁱⁱ—Na1—O6Bⁱ	71.0 (7)	N1B—O1B—Dy1	117 (4)
O1Bⁱ—Na1—O6Bⁱ	81.5 (10)	Mn1B—O1B—Dy1	115.3 (12)
O1Bⁱⁱ—Na1—O6Bⁱ	120.7 (9)	Na1—O1B—Dy1	89.0 (6)
O1Bⁱⁱⁱ—Na1—O6Bⁱ	142.0 (10)	C1B—O2B—Mn1B	112.2 (14)
O1B—Na1—O6Bⁱ	64.8 (10)	C7B—O3B—Mn1Bⁱⁱ	130 (2)
O6Bⁱⁱ—Na1—O6Bⁱ	149.9 (18)	C1B—N1B—O1B	113 (2)
O6—Na1—O6Bⁱⁱⁱ	144.3 (8)	C1B—N1B—Mn1Bⁱⁱ	131 (3)
O6ⁱⁱ—Na1—O6Bⁱⁱⁱ	71.0 (7)	O1B—N1B—Mn1Bⁱⁱ	114 (2)
O6ⁱ—Na1—O6Bⁱⁱⁱ	100.0 (8)	O2B—C1B—N1B	121.0 (18)
O6ⁱⁱⁱ—Na1—O6Bⁱⁱⁱ	15.2 (7)	O2B—C1B—C2B	119.9 (18)
O1Bⁱ—Na1—O6Bⁱⁱⁱ	64.8 (10)	N1B—C1B—C2B	118.9 (19)
O1Bⁱⁱ—Na1—O6Bⁱⁱⁱ	142.0 (10)	C3B—C2B—C7B	121.2 (19)
O1Bⁱⁱⁱ—Na1—O6Bⁱⁱⁱ	81.5 (10)	C3B—C2B—C1B	114.3 (19)
O1B—Na1—O6Bⁱⁱⁱ	120.7 (9)	C7B—C2B—C1B	124.5 (19)
O6Bⁱⁱ—Na1—O6Bⁱⁱⁱ	86.1 (4)	C4B—C3B—C2B	121 (2)
O6Bⁱ—Na1—O6Bⁱⁱⁱ	86.1 (4)	C4B—C3B—H3B	119.3
O1Bⁱ—Na1—O6B	142.0 (10)	C2B—C3B—H3B	119.3
O1Bⁱⁱ—Na1—O6B	64.8 (10)	C5B—C4B—C3B	117 (3)
O1Bⁱⁱⁱ—Na1—O6B	120.7 (9)	C5B—C4B—H4B	121.6
O1B—Na1—O6B	81.5 (10)	C3B—C4B—H4B	121.6
O6Bⁱⁱ—Na1—O6B	86.1 (4)	C4B—C5B—C6B	124 (3)
O6Bⁱ—Na1—O6B	86.1 (4)	C4B—C5B—H5B	118.0
O6Bⁱⁱⁱ—Na1—O6B	149.9 (18)	C6B—C5B—H5B	118.0
O3ⁱⁱ—Mn1—O1	168.5 (2)	C5B—C6B—C7B	120 (2)
O3ⁱⁱ—Mn1—O2	97.45 (17)	C5B—C6B—H6B	119.8
O1—Mn1—O2	81.70 (15)	C7B—C6B—H6B	119.8
O3ⁱⁱ—Mn1—N1ⁱⁱ	90.57 (19)	O3B—C7B—C6B	120 (2)
O1—Mn1—N1ⁱⁱ	88.75 (16)	O3B—C7B—C2B	124 (2)
O2—Mn1—N1ⁱⁱ	168.3 (3)	C6B—C7B—C2B	116.1 (19)
O3ⁱⁱ—Mn1—O5	94.6 (2)	C8B—O4B—Dy1	133 (3)
O1—Mn1—O5	96.9 (2)	O5B—C8B—O4B	124 (3)
O2—Mn1—O5	94.0 (2)	O5B—C8B—C9B	128 (3)
N1ⁱⁱ—Mn1—O5	93.8 (4)	O4B—C8B—C9B	108 (2)
O3ⁱⁱ—Mn1—O6	89.8 (2)	C13B—C9B—C10B	121 (3)
O1—Mn1—O6	78.68 (15)	C13B—C9B—C8B	113 (3)
O2—Mn1—O6	86.28 (16)	C10B—C9B—C8B	106 (3)
N1ⁱⁱ—Mn1—O6	85.3 (4)	C13B—C9B—H9B	105.3
O5—Mn1—O6	175.52 (19)	C10B—C9B—H9B	105.3
O3ⁱⁱ—Mn1—Na1	124.15 (18)	C8B—C9B—H9B	105.3
O1—Mn1—Na1	45.80 (12)	C11B—C10B—C9B	124 (3)
O2—Mn1—Na1	103.48 (11)	C11B—C10B—H10G	106.3
N1ⁱⁱ—Mn1—Na1	64.9 (3)	C9B—C10B—H10G	106.3
O5—Mn1—Na1	133.91 (17)	C11B—C10B—H10H	106.2
O6—Mn1—Na1	41.91 (11)	C9B—C10B—H10H	106.2
N1—O1—Mn1	112.7 (3)	H10G—C10B—H10H	106.4
N1—O1—Dy1	121.3 (4)	C10B—C11B—C12B	122 (3)
Mn1—O1—Dy1	119.88 (15)	C10B—C11B—H11G	106.8
N1—O1—Na1	104.4 (4)	C12B—C11B—H11G	106.8
Mn1—O1—Na1	103.43 (15)	C10B—C11B—H11H	106.8
Dy1—O1—Na1	87.70 (12)	C12B—C11B—H11H	106.8
C1—O2—Mn1	112.1 (3)	H11G—C11B—H11H	106.6
C7—O3—Mn1ⁱ	129.8 (3)	C11B—C12B—H12J	109.5
C1—N1—O1	112.6 (5)	C11B—C12B—H12K	109.5
C1—N1—Mn1ⁱ	130.9 (4)	H12J—C12B—H12K	109.5
O1—N1—Mn1ⁱ	116.1 (3)	C11B—C12B—H12L	109.5
O2—C1—N1	120.4 (4)	H12J—C12B—H12L	109.5
O2—C1—C2	120.0 (4)	H12K—C12B—H12L	109.5
N1—C1—C2	119.6 (5)	C9B—C13B—C14B	112 (3)
C3—C2—C7	118.8 (5)	C9B—C13B—H13G	109.2
C3—C2—C1	118.0 (5)	C14B—C13B—H13G	109.2
C7—C2—C1	123.1 (5)	C9B—C13B—H13H	109.2
C4—C3—C2	121.4 (6)	C14B—C13B—H13H	109.2
C4—C3—H3	119.3	H13G—C13B—H13H	107.9
C2—C3—H3	119.3	C13B—C14B—C15B	107 (3)
C5—C4—C3	119.3 (6)	C13B—C14B—H14G	110.4
C5—C4—H4	120.3	C15B—C14B—H14G	110.4
C3—C4—H4	120.3	C13B—C14B—H14H	110.4
C4—C5—C6	120.9 (6)	C15B—C14B—H14H	110.4
C4—C5—H5	119.5	H14G—C14B—H14H	108.6
C6—C5—H5	119.5	C14B—C15B—H15J	109.5
C5—C6—C7	121.0 (6)	C14B—C15B—H15K	109.5
C5—C6—H6	119.5	H15J—C15B—H15K	109.5
C7—C6—H6	119.5	C14B—C15B—H15L	109.5
O3—C7—C6	117.9 (5)	H15J—C15B—H15L	109.5
O3—C7—C2	123.5 (5)	H15K—C15B—H15L	109.5
C6—C7—C2	118.5 (5)	Mn1Bⁱⁱ—O6B—Na1	92.1 (13)
C8—O4—Dy1	144.7 (5)	Mn1Bⁱⁱ—O6B—H6C	137 (7)
C8—O5—Mn1	124.0 (5)	Na1—O6B—H6C	95 (6)
O5—C8—O4	127.1 (7)	Mn1Bⁱⁱ—O6B—H6D	115 (7)
O5—C8—C9C	110.5 (16)	Na1—O6B—H6D	95 (6)
O4—C8—C9C	122.3 (16)	H6C—O6B—H6D	107 (3)
O5—C8—C9	124.4 (14)	O7—C16—N2	125.5 (16)
O4—C8—C9	108.3 (14)	O7—C16—H16	117.2
O5—C8—C9D	117.9 (15)	N2—C16—H16	117.2
O4—C8—C9D	113.9 (16)	C16—N2—C17	119.0 (13)
C13—C9—C10	122.4 (16)	C16—N2—C18	118.2 (12)
C13—C9—C8	115.7 (17)	C17—N2—C18	122.5 (13)
C10—C9—C8	106.3 (18)	N2—C17—H17A	109.5
C13—C9—H9	103.3	N2—C17—H17B	109.5
C10—C9—H9	103.3	H17A—C17—H17B	109.5
C8—C9—H9	103.3	N2—C17—H17C	109.5
C11—C10—C9	116.6 (15)	H17A—C17—H17C	109.5
C11—C10—H10A	108.1	H17B—C17—H17C	109.5
C9—C10—H10A	108.1	N2—C18—H18A	109.5
C11—C10—H10B	108.1	N2—C18—H18B	109.5
C9—C10—H10B	108.1	H18A—C18—H18B	109.5
H10A—C10—H10B	107.3	N2—C18—H18C	109.5
C10—C11—C12	118.1 (17)	H18A—C18—H18C	109.5
C10—C11—H11A	107.8	H18B—C18—H18C	109.5
C12—C11—H11A	107.8	O7B—C16B—N2B	120 (3)
C10—C11—H11B	107.8	O7B—C16B—H16B	119.8
C12—C11—H11B	107.8	N2B—C16B—H16B	119.8
H11A—C11—H11B	107.1	C16B—N2B—C18B	113 (3)
C11—C12—H12A	109.5	C16B—N2B—C17B	113 (3)
C11—C12—H12B	109.5	C18B—N2B—C17B	125 (3)
H12A—C12—H12B	109.5	N2B—C17B—H17D	109.5
C11—C12—H12C	109.5	N2B—C17B—H17E	109.5
H12A—C12—H12C	109.5	H17D—C17B—H17E	109.5
H12B—C12—H12C	109.5	N2B—C17B—H17F	109.5
C9—C13—C14	118.5 (17)	H17D—C17B—H17F	109.5
C9—C13—H13A	107.7	H17E—C17B—H17F	109.5
C14—C13—H13A	107.7	N2B—C18B—H18D	109.5
C9—C13—H13B	107.7	N2B—C18B—H18E	109.5
C14—C13—H13B	107.7	H18D—C18B—H18E	109.5
H13A—C13—H13B	107.1	N2B—C18B—H18F	109.5
C13—C14—C15	110.9 (15)	H18D—C18B—H18F	109.5
C13—C14—H14A	109.5	H18E—C18B—H18F	109.5
C15—C14—H14A	109.5	O7C—C16C—N2C	119 (2)
C13—C14—H14B	109.5	O7C—C16C—H16C	120.5
C15—C14—H14B	109.5	N2C—C16C—H16C	120.5
H14A—C14—H14B	108.1	C16C—N2C—C18C	118.3 (16)
C14—C15—H15A	109.5	C16C—N2C—C17C	115.5 (18)
C14—C15—H15B	109.5	C18C—N2C—C17C	126.2 (19)
H15A—C15—H15B	109.5	N2C—C17C—H17G	109.5
C14—C15—H15C	109.5	N2C—C17C—H17H	109.5
H15A—C15—H15C	109.5	H17G—C17C—H17H	109.5
H15B—C15—H15C	109.5	N2C—C17C—H17I	109.5
Na1—O6—Mn1	94.24 (17)	H17G—C17C—H17I	109.5
Na1—O6—H6A	109 (4)	H17H—C17C—H17I	109.5
Mn1—O6—H6A	124 (6)	N2C—C18C—H18G	109.5
Na1—O6—H6E	110 (4)	N2C—C18C—H18H	109.5
Mn1—O6—H6E	112 (5)	H18G—C18C—H18H	109.5
H6A—O6—H6E	107 (3)	N2C—C18C—H18I	109.5
C13C—C9C—C10C	135.8 (18)	H18G—C18C—H18I	109.5
C13C—C9C—C8	115.4 (18)	H18H—C18C—H18I	109.5

Mn1—O1—N1—C1	6.0 (10)	O5—C8—C9D—C13D	−153.5 (19)
Dy1—O1—N1—C1	−146.3 (6)	O4—C8—C9D—C13D	37 (3)
Na1—O1—N1—C1	117.5 (7)	O5—C8—C9D—C10D	58 (3)
Mn1—O1—N1—Mn1ⁱ	−167.2 (5)	O4—C8—C9D—C10D	−111 (2)
Dy1—O1—N1—Mn1ⁱ	40.4 (9)	C13D—C9D—C10D—C11D	−70 (4)
Na1—O1—N1—Mn1ⁱ	−55.7 (8)	C8—C9D—C10D—C11D	75 (4)
Mn1—O2—C1—N1	−3.1 (9)	C9D—C10D—C11D—C12D	170 (3)
Mn1—O2—C1—C2	175.1 (4)	C10D—C9D—C13D—C14D	−141 (3)
O1—N1—C1—O2	−1.9 (12)	C8—C9D—C13D—C14D	72 (3)
Mn1ⁱ—N1—C1—O2	170.1 (7)	C9D—C13D—C14D—C15D	89 (3)
O1—N1—C1—C2	179.9 (6)	Mn1B—O1B—N1B—C1B	5 (12)
Mn1ⁱ—N1—C1—C2	−8.2 (14)	Na1—O1B—N1B—C1B	−117 (9)
O2—C1—C2—C3	12.2 (9)	Dy1—O1B—N1B—C1B	143 (7)
N1—C1—C2—C3	−169.5 (8)	Mn1B—O1B—N1B—Mn1Bⁱⁱ	173 (5)
O2—C1—C2—C7	−167.2 (6)	Na1—O1B—N1B—Mn1Bⁱⁱ	51 (9)
N1—C1—C2—C7	11.0 (11)	Dy1—O1B—N1B—Mn1Bⁱⁱ	−50 (10)
C7—C2—C3—C4	2.2 (11)	Mn1B—O2B—C1B—N1B	−2 (9)
C1—C2—C3—C4	−177.3 (7)	Mn1B—O2B—C1B—C2B	−178 (2)
C2—C3—C4—C5	−1.0 (12)	O1B—N1B—C1B—O2B	−2 (14)
C3—C4—C5—C6	0.1 (13)	Mn1Bⁱⁱ—N1B—C1B—O2B	−167 (8)
C4—C5—C6—C7	−0.4 (12)	O1B—N1B—C1B—C2B	173 (6)
Mn1ⁱ—O3—C7—C6	166.9 (5)	Mn1Bⁱⁱ—N1B—C1B—C2B	8 (15)
Mn1ⁱ—O3—C7—C2	−17.1 (10)	O2B—C1B—C2B—C3B	−3 (4)
C5—C6—C7—O3	177.8 (7)	N1B—C1B—C2B—C3B	−179 (8)
C5—C6—C7—C2	1.5 (11)	O2B—C1B—C2B—C7B	175 (5)
C3—C2—C7—O3	−178.4 (6)	N1B—C1B—C2B—C7B	0 (8)
C1—C2—C7—O3	1.0 (10)	C7B—C2B—C3B—C4B	1 (3)
C3—C2—C7—C6	−2.4 (10)	C1B—C2B—C3B—C4B	180 (3)
C1—C2—C7—C6	177.0 (6)	C2B—C3B—C4B—C5B	1 (5)
Mn1—O5—C8—O4	22.3 (14)	C3B—C4B—C5B—C6B	0 (7)
Mn1—O5—C8—C9C	−158.7 (11)	C4B—C5B—C6B—C7B	−3 (7)
Mn1—O5—C8—C9	−161.6 (12)	Mn1Bⁱⁱ—O3B—C7B—C6B	−180 (3)
Mn1—O5—C8—C9D	−145.4 (13)	Mn1Bⁱⁱ—O3B—C7B—C2B	4 (7)
Dy1—O4—C8—O5	12.0 (18)	C5B—C6B—C7B—O3B	−172 (5)
Dy1—O4—C8—C9C	−166.8 (12)	C5B—C6B—C7B—C2B	5 (6)
Dy1—O4—C8—C9	−164.6 (11)	C3B—C2B—C7B—O3B	172 (5)
Dy1—O4—C8—C9D	−179.9 (12)	C1B—C2B—C7B—O3B	−6 (5)
O5—C8—C9—C13	−84 (2)	C3B—C2B—C7B—C6B	−4 (4)
O4—C8—C9—C13	92 (2)	C1B—C2B—C7B—C6B	178 (3)
O5—C8—C9—C10	55 (2)	Dy1—O4B—C8B—O5B	−22 (5)
O4—C8—C9—C10	−128.2 (18)	Dy1—O4B—C8B—C9B	158 (4)
C13—C9—C10—C11	−168 (3)	O5B—C8B—C9B—C13B	178 (4)
C8—C9—C10—C11	56 (4)	O4B—C8B—C9B—C13B	−3 (4)
C9—C10—C11—C12	174 (3)	O5B—C8B—C9B—C10B	43 (5)
C10—C9—C13—C14	82 (3)	O4B—C8B—C9B—C10B	−137 (4)
C8—C9—C13—C14	−146 (2)	C13B—C9B—C10B—C11B	174 (7)
C9—C13—C14—C15	90 (3)	C8B—C9B—C10B—C11B	−57 (8)
O5—C8—C9C—C13C	−58 (3)	C9B—C10B—C11B—C12B	148 (7)
O4—C8—C9C—C13C	121 (2)	C10B—C9B—C13B—C14B	25 (8)
O5—C8—C9C—C10C	121 (2)	C8B—C9B—C13B—C14B	−102 (6)
O4—C8—C9C—C10C	−60 (3)	C9B—C13B—C14B—C15B	160 (6)
C13C—C9C—C10C—C11C	148 (4)	O7—C16—N2—C17	−173 (3)
C8—C9C—C10C—C11C	−31 (4)	O7—C16—N2—C18	0 (4)
C9C—C10C—C11C—C12C	−131 (4)	O7B—C16B—N2B—C18B	−22 (11)
C10C—C9C—C13C—C14C	108 (4)	O7B—C16B—N2B—C17B	−172 (9)
C8—C9C—C13C—C14C	−74 (3)	O7C—C16C—N2C—C18C	13 (5)
C9C—C13C—C14C—C15C	−20 (3)	O7C—C16C—N2C—C17C	−169 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O7	0.86 (2)	2.02 (2)	2.860 (15)	165 (5)
O6—H6E···O7ⁱⁱ	0.83 (2)	1.99 (2)	2.809 (19)	167 (5)
O6B—H6C···O7Bⁱⁱ	0.84 (2)	2.00 (2)	2.80 (3)	159 (10)
O6B—H6D···O7B	0.85 (2)	2.01 (2)	2.859 (19)	177 (10)

Symmetry code: (ii) −y+1/2, x, z.

Average bond length (Å) and bond-valence-sum (BVS) values (v.u.) used to support assigned oxidation states of the dysprosium and manganese ions of 1 top

	Avg. Bond length	BVS value	Assigned oxidation state
Dy1	2.361	3.14	3+
Mn1	1.953	3.02	3+

Continuous Shape Measure (CShM) values for the geometry about the eight-coordinate central Dy^III and Na⁺ ions of 1 top

Shape	Dy^III	Na⁺
Octagon (D_8h)	32.056	32.142
Heptagonal pyramid (C_7v)	23.666	26.075
Hexagonal bipyramid (D_6h)	16.870	13.023
Cube (O_h)	9.253	5.054
Square antiprism (D_4d)	0.747	3.803
Triangular dodecahedron (D_2d)	2.730	4.048
Johnson gyrobifastigium (J26; D_2s)	17.553	16.887
Johnson elongated triangular bipyramid (J14; D_3h)	30.395	28.728
Johnson biaugmented trigonal prism (J50; C_2v)	3.036	5.420
Biaugmented trigonal prism (C_2v)	1.991	3.667
Johnson snub diphenoid (J84; D_2d)	5.971	8.256
Triakis tetrahedron (T_d)	10.118	5.959
Elongated trigonal bipyramid (D_3h)	25.708	25.581

Continuous Shape Measure (CShM) values for the geometry about the five-coordinate ring Mn^III ion of 1 top

Shape	Pentagon (D_5h)	Vacant octahedron (C_4v)	Trigonal bipyramid (D_3h)	Spherical square pyramid (C_4v)	Johnson trigonal bipyramid (J12; D_3h)
Mn1	30.515	0.832	5.422	0.739	7.504

Structural Feature Comparison of 1 and other DyNa(carboxylate)₄[12-MC_Mn^IIIN(shi)-4] compounds (Å, °) top

Compound	MC cavity radius^a	Avg. cross cavity Mn^III—Mn^III distance^a	Avg. adjacent Mn^III—Mn^III Distance^a	Avg. cross-cavity O_oxime—O_oxime distance^a	Dy^III–oxime oxygen mean plane distance^b
DyNa(2-PV)₄[12-MC-4], 1	0.54	6.51	4.60	3.68	1.6069 (37)
DyNa(OAc)₄[12-MC-4]	0.55	6.52	4.61	3.71	1.5918 (7)
DyNa(TMA)₄[12-MC-4]	0.56	6.51	4.60	3.73	1.5790 (19)
DyNa(ben)₄[12-MC-4]	0.54	6.51	4.60	3.69	1.5811 (18)
DyNa(2-OHben)₄[12-MC-4]	0.54	6.47	4.57	3.68	1.5094 (46)
DyNa(3-OHben)₄[12-MC-4]	0.56	6.53	4.62	3.72	1.5463 (25)
DyNa(4-OHben)₄[12-MC-4]	0.54	6.49	4.59	3.69	1.5925 (66)
DyNa(2-Fben)₄[12-MC-4]	0.55	6.51	4.60	3.71	1.5424 (52)
DyNa(3-Fben)₄[12-MC-4]	0.56	6.51	4.60	3.72	1.5567 (34)
DyNa(4-Fben)₄[12-MC-4]	0.54	6.52	4.61	3.68	1.5589 (45)
DyNa(2-Clben)₄[12-MC-4]	0.53	6.50	4.60	3.67	1.5883 (79)
DyNa(4-Clben)₄[12-MC-4]	0.55	6.54	4.62	3.71	1.5593 (13)
DyNa(3-Brben)₄[12-MC-4]	0.56	6.51	4.60	3.71	1.5685 (13)
DyNa(2-Iben)₄[12-MC-4]	0.54	6.50	4.59	3.68	1.5764 (117)

Notes: (a) Measured with Mercury (Macrae et al., 2020); (b) measured with SHELXL (Sheldrick, 2015b).

Acknowledgements

CMZ thanks the Department of Chemistry and Biochemistry at Shippensburg University for continued support.

Funding information

Funding for this research was provided by: National Science Foundation, Major Research Instrumentation Program (award No. CHE 1625543 to M. Zeller); Shippensburg University Student Faculty Research Engagement (SFRE) Program (grant to O. A. Aziz, C. M. Zaleski).

References

Anthanasopoulou, A. A., Carrella, L. M. & Rentschler, E. (2018). Inorganics 6, 66. Google Scholar
Azar, M. R., Boron, T. T. III, Lutter, J. C., Daly, C. I., Zegalia, K. A., Nimthong, R., Ferrence, G. M., Zeller, M., Kampf, J. W., Pecoraro, V. L. & Zaleski, C. M. (2014). Inorg. Chem. 53, 1729–1742. Web of Science CSD CrossRef CAS PubMed Google Scholar
Boron, T. T. III (2022). Advances in Metallacrown Chemistry, edited by C. M. Zaleski, pp. 157–219. Cham: Springer Nature. Google Scholar
Boron, T. T. III, Lutter, J. C., Daly, C. I., Chow, C. Y., Davis, A. H., Nimthong-Roldán, A., Zeller, M., Kampf, J. W., Zaleski, C. M. & Pecoraro, V. L. (2016). Inorg. Chem. 55, 10597–10607. Web of Science CSD CrossRef CAS PubMed Google Scholar
Bruker (2022). APEX4 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, F., Wei, R.-M., Li, J., Yang, L., Han, Y., Song, Y. & Dou, J.-M. (2016). Inorg. Chem. 55, 5914–5923. Web of Science CSD CrossRef CAS PubMed Google Scholar
Casanova, D., Llunell, M., Alemany, P. & Alvarez, S. (2005). Chem. Eur. J. 11, 1479–1494. Web of Science CrossRef PubMed CAS Google Scholar
Chow, C. Y., Eliseeva, S. V., Trivedi, E. R., Nguyen, T. N., Kampf, J. W., Petoud, S. & Pecoraro, V. L. (2016). J. Am. Chem. Soc. 138, 5100–5109. Web of Science CSD CrossRef CAS PubMed Google Scholar
Cirera, J., Ruiz, E. & Alvarez, S. (2005). Organometallics, 24, 1556–1562. Web of Science CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Haynes, W. M. (2010). CRC Handbook of Chemistry and Physics, 91st ed., pp. 8-42–8-51. Boca Raton, FL: CRC Press. Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Liu, K., Shi, W. & Cheng, P. (2015). Coord. Chem. Rev. 289–290, 74–122. Web of Science CrossRef CAS Google Scholar
Liu, W. & Thorp, H. H. (1993). Inorg. Chem. 32, 4102–4105. CrossRef CAS Web of Science Google Scholar
Llunell, M., Casanova, D., Cirera, J., Alemany, P. & Alvarez, S. (2013). SHAPE. Shape Software, Barcelona, Spain. Google Scholar
Lun, H. J., Xu, L., Kong, X. J., Long, L. S. & Zheng, L. S. (2021). Inorg. Chem. 60, 10079–10083. Web of Science CSD CrossRef CAS PubMed Google Scholar
Lutter, J. C., Boron, T. T. III, Chadwick, K. E., Davis, A. H., Kleinhaus, S., Kampf, J. W., Zaleski, C. M. & Pecoraro, V. L. (2021). Polyhedron, 202, 115190. Web of Science CSD CrossRef Google Scholar
Lutter, J. C., Zaleski, C. M. & Pecoraro, V. L. (2018). Advances in Inorganic Chemistry, edited by R. van Eldik & R. Puchta, pp. 177–246. Amsterdam: Elsevier. Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Manickas, E. C., Zeller, M. & Zaleski, C. M. (2020). Acta Cryst. E76, 1213–1221. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mezei, G., Zaleski, C. M. & Pecoraro, V. L. (2007). Chem. Rev. 107, 4933–5003. Web of Science CrossRef PubMed CAS Google Scholar
Michael, C. H., Zeller, M. & Zaleski, C. M. (2021). J. Chem. Crystallogr. 51, 562–574. Web of Science CSD CrossRef CAS Google Scholar
Pinsky, M. & Avnir, D. (1998). Inorg. Chem. 37, 5575–5582. Web of Science CrossRef PubMed CAS Google Scholar
Qin, Y., Gao, Q., Chen, Y., Liu, W., Lin, F., Zhang, X., Dong, Y. & Li, Y. (2017). J. Clust Sci. 28, 891–903. Web of Science CSD CrossRef CAS Google Scholar
Saha, S., Das, K. S., Sharma, T., Bala, S., Adhikary, A., Huang, G. Z., Tong, M. L., Ghosh, A., Das, B., Rajaraman, G. & Mondal, R. (2022). Inorg. Chem. 61, 2141–2153. CSD CrossRef CAS PubMed Google Scholar
Salerno, E. V., Kampf, J. W., Pecoraro, V. L. & Mallah, T. (2021). Inorg. Chem. Front. 8, 2611–2623. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Travis, J. R., Zeller, M. & Zaleski, C. M. (2015). Acta Cryst. E71, 1300–1306. Web of Science CSD CrossRef IUCr Journals Google Scholar
Travis, J. R., Zeller, M. & Zaleski, C. M. (2016). Polyhedron, 114, 29–36. Web of Science CSD CrossRef CAS Google Scholar
Trzesowska, A., Kruszynski, R. & Bartczak, T. J. (2004). Acta Cryst. B60, 174–178. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Z. X., Zhang, X., Zhang, Y. Z., Li, M. X., Zhao, H., Andruh, M. & Dunbar, K. R. (2014). Angew. Chem. Int. Ed. 53, 11567–11570. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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