Crystal structure of a TbIII–CuII glycine­hydroxamate 15-metallacrown-5 sulfate complex

Pavlishchuk, A.V.; Vasylenko, I.V.; Zeller, M.; Addison, A.W.

doi:10.1107/S2056989021011907

Jerry P. Jasinski tribute

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1197-1202

https://doi.org/10.1107/S2056989021011907

Open

access

Crystal structure of a Tb^III–Cu^II glycinehydroxamate 15-metallacrown-5 sulfate complex

Anna V. Pavlishchuk,^a,^b ^* Inna V. Vasylenko,^b Matthias Zeller ^c and Anthony W. Addison ^d

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 62, Kyiv, 01601, Ukraine, ^bL.V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospect Nauki 31, Kiev 03028, Ukraine, ^cDepartment of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, IA 47907-2084, USA, and ^dDepartment of Chemistry, Drexel University, Philadelphia, PA 19104-2816, USA
^*Correspondence e-mail: annpavlis@ukr.net

(Received 1 August 2021; accepted 9 November 2021; online 18 November 2021)

The core of the title complex, bis[hexaaquahemiaquapentakis(μ₃-glycinehydroxamato)sulfatopentacopper(II)terbium(III)] sulfate hexahydrate, [TbCu₅(SO₄)(GlyHA)₅(H₂O)_6.5]₂(SO₄)·6H₂O (1), which belongs to the 15-metallacrown-5 family, consists of five glycinehydroxamate dianions (GlyHA²⁻; C₂H₄N₂O₂) and five copper(II) ions linked together forming a metallamacrocyclic moiety. The terbium(III) ion is connected to the centre of the metallamacrocycle through five hydroxamate oxygen atoms. The coordination environment of the Tb³⁺ ion is completed to an octacoordination level by oxygen atoms of a bidentate sulfate and an apically coordinated water molecule, while the copper(II) atoms are square-planar, penta- or hexacoordinate due to the apical coordination of water molecules. Continuous shape calculations indicate that the coordination polyhedron of the Tb³⁺ ion in 1 is best described as square antiprismatic. The positive charge of each pair of [TbCu₅(GlyHA)₅(H₂O)_6.5(SO₄)]₂²⁺ fragments is compensated by a non-coordinated sulfate anion, which is located on an inversion center with 1:1 disordered oxygen atoms. Complex 1 is isomorphous with the previously reported compounds [LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]₂(SO₄), where Ln^III = Pr, Nd, Sm, Eu, Gd, Dy and Ho.

Keywords: crystal structure; terbium(III); copper(II); metallamacrocycle; 15-metallacrown-5.

CCDC reference: 2121203

1. Chemical context

Numerous research studies devoted to polynuclear 3d–4f assemblies have been stimulated by their non-trivial luminescence properties (Jankolovits et al., 2011 ; Maity et al., 2015 ), single-molecule magnet (SMM) behaviour (Dhers et al., 2016 ; Zangana et al., 2014 ) and their significant magnetocaloric effect (Pavlishchuk & Pavlishchuk, 2020 ; Zheng et al., 2014 ). The 15-metallacrown-5 complexes are 3d–4f metallamacrocyclic assemblies, which can be easily obtained from one-step reactions between an α-substituted hydroxamic acid and the corresponding salts of transition metals and lanthanides (Stemmler et al., 1999 ; Pavlishchuk et al., 2011 , 2019 ). Compounds bearing 15-metallacrown-5 {LnCu₅}³⁺ units have demonstrated the ability to serve as sensors (Zabrodina et al., 2018 ), can absorb and adsorb various small molecules (Lim et al., 2010 ; Pavlishchuk et al., 2014 ; Ostrowska et al., 2016 ) and display SMM behaviour (Wang et al., 2019 , 2021 ; Zaleski et al., 2006 ; Wu et al., 2021 ). Taking into account the fact that 15-metallacrowns-5 are also suitable building blocks for the generation of porous coordination polymers and discrete assemblies (Pavlishchuk et al., 2017a ,b , 2018 ), the synthesis of new examples of this class of metallamacrocyclic assemblies and studies of their structural features are of particular interest. Herein we report the crystal structure of the new 15-metallacrown-5 complex [TbCu₅(GlyHA)₅(H₂O)_6.5(SO₄)]₂ (SO₄)·13(H₂O) (1), which complements the previously reported series of isomorphous metallamacrocycles with Pr, Nd, Sm, Eu, Gd, Dy and Ho ions at their centres.

2. Structural commentary

Complex 1 crystallizes in the space group P $[\overline{1}]$ and is isostructural with the previously reported complexes [LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]₂(SO₄), where GlyHA²⁻ is the dianion of glycinehydroxamic acid and Ln^III = Pr, Nd, Sm, Eu, Gd, Dy and Ho (Pavlishchuk et al., 2011). Each unit cell in 1 contains two [TbCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]⁺ 15-metallacrown-5 cations related by an inversion center, one non-coordinated sulfate anion for charge-balance and non-coordinated water molecules (Figs. 1 and 2).

Figure 1
The unit cell of complex 1 containing two [TbCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]⁺ metallacrown cations and non-coordinated sulfate anions (located on a inversion center with O atoms 1:1 disordered). Non-coordinated water molecules are omitted for clarity of presentation.

Figure 2
Structure of the [TbCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]⁺ metallacrown cations in 1. The dashed lines indicate the disorder of the non-coordinated sulfate anion. Displacement ellipsoids are shown at the 50% probability level. [Symmetry code: (i) x, y, z + 1.]

The core of the [TbCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]⁺ complex cation in 1 is constructed from five copper(II) ions linked by five bridging glycinehydroxamate dianions (GlyHA²⁻) and a terbium(III) ion bound at the centre of the metallocycle (Fig. 1). The copper(II) equatorial coordination environment in 1 is formed by two oxygen atoms (from a carboxylate and a deprotonated hydroxamate group) and two nitrogen atoms (from an amine and a deprotonated hydroxamate). The equatorial Cu—O_eq and Cu—N_eq distances range from 1.928 (3) to 1.969 (3) Å and 1.890 (4) to 2.018 (4) Å (Table 1), respectively, which is typical of aminohydroxamate 15-metallacrown-5 complexes (Stemmler et al., 1999; Pavlishchuk et al., 2011; Katkova et al., 2015a ; Meng et al., 2016 ). As a result of the apical coordination of water molecules to copper(II) ions, Cu1 has distorted square-bipyramidal coordination [Cu1—O20 = 2.601 (4) Å and Cu1—O21 = 2.736 (4) Å], while Cu3, Cu4 and Cu5 are in square-pyramidal environments [Cu3—O16 = 2.508 (4) Å, Cu4—O17 = 2.481 (4) Å and Cu5—O18 = 2.379 (4) with τ-values (Addison et al., 1984 ) ranging from 0.07 to 0.13]. As a result of the disorder of the O19 water molecule between two symmetry-equivalent positions with occupancy factors of 0.5, 50% of the Cu2 atoms in 1 have square-planar coordination environments, while the other 50% possess a square-pyramidal coordination [Cu2—O19 = 2.409 (10), τ = 0.022 (Addison et al., 1984)]. The terbium(III) ions at the centres of the [Cu₅(GlyHA)₅] metallamacrocyclic cores in 1 are bound by five hydroxamate oxygen atoms. The Tb—O_eq bond lengths are typical for 15-metallacrown-5 complexes and range from 2.370 (3) to 2.430 (3) Å (Stemmler et al., 1999; Pavlishchuk et al., 2011; Katkova et al., 2015a; Meng et al., 2016).

Table 1
Selected bond lengths (Å)

Cu1—N3	1.915 (4)	Cu4—O8	1.940 (3)
Cu1—O1	1.928 (3)	Cu4—O7	1.947 (3)
Cu1—O2	1.969 (3)	Cu4—N10	2.012 (4)
Cu1—N4	1.991 (4)	Cu4—O17	2.481 (4)
Cu1—O20	2.601 (4)	Cu5—N1	1.890 (4)
Cu1—O21	2.736 (4)	Cu5—O9	1.943 (3)
Cu2—N5	1.900 (4)	Cu5—O10	1.946 (3)
Cu2—O3	1.928 (3)	Cu5—N2	2.003 (4)
Cu2—O4	1.936 (3)	Cu5—O18	2.379 (4)
Cu2—N6	2.018 (4)	Tb1—O9	2.370 (3)
Cu2—O19	2.409 (10)	Tb1—O1	2.372 (3)
Cu3—N7	1.904 (4)	Tb1—O15	2.383 (3)
Cu3—O6	1.944 (3)	Tb1—O3	2.386 (3)
Cu3—O5	1.949 (3)	Tb1—O7	2.411 (3)
Cu3—N8	2.014 (4)	Tb1—O5	2.430 (3)
Cu3—O16	2.508 (4)	Tb1—O12	2.436 (3)
Cu4—N9	1.894 (4)	Tb1—O11	2.451 (3)

The coordination environment of the Tb³⁺ ion is completed to an octacoordination level via the two oxygen atoms O11 [Tb1—O11 = 2.451 (3) Å] and O12 [Tb1—O12 = 2.436 (3) Å] from the bidentate sulfate anions and O15 [Tb1—O15 = 2.383 (3) Å] from a water molecule coordinated in the trans-position opposite to the SO₄²⁻ ion. An analysis of selected structural parameters for complex 1 and those of isomorphous compounds with other Ln^III ions (Table 2) reveals the influence of the lanthanide contraction. Similar behaviour was found in other series of lanthanide(III) containing metallamacrocycles (Pavlishchuk et al., 2011; Zaleski et al., 2011 ). According to Shape 2.1 (Casanova et al., 2005 ) calculations (Fig. 3, Table 3), the coordination geometry of the Tb^III ion in 1 is a square antiprism (D_4d), which is of particular interest with respect to potential generation of lanthanide(III)-containing SMMs (Liu et al., 2018 ). The deviations from an idealized square-antiprismatic geometry in the [LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]₂(SO₄) complexes decrease with reduction of the deviation of the Ln^III ion from the mean plane of the metallacrown core, which parallels the ionic radii of the Ln^III ions (Table 3). It may be noted that, in the case of a series of related 15-metallacrown-5 complexes with octacoordinate Ln^III ions containing bidentate carbonates or acetates instead of sulfates, the coordination of the lanthanide ions is triangular dodecahedral (D_2d) (Table 3).

Table 2
Comparison of the structural characteristics (Å, °) of {LnCu₅}³⁺ 15-metallacrown-5 complexes with octacoordinate Ln^III ions and various bidentate anions

Complex^a	Cu—O/N_eq	Ln—O_eq	Ln—O_aq	Ln⋯Cu	Cu⋯Cu	Deviation of Ln^III from Cu₅ plane	LnO₈ geometry^b
Pr—SO₄	1.898 (2)–2.013 (2)	2.4247 (18)–2.4716 (18)	2.495 (2)–2.528 (2)	3.862 (3)–3.923 (2)	4.530 (2)–4.604 (2)	0.459	SAPR-8
Nd—SO₄	1.898 (2)–2.0156 (19)	2.4145 (16)–2.4642 (16)	2.4787 (18)–2.5108 (17)	3.862 (3)–3.915 (4)	4.524 (4)–4.598 (5)	0.452	SAPR-8
Sm—SO₄	1.900 (4)–2.015 (4)	2.398 (3) −2.450 (3)	2.441 (4)–2.484 (4)	3.8539 (9)–3.9083 (8)	4.518 (1)–4.592 (1)	0.439	SAPR-8
Eu—SO₄	1.896 (3)–2.013 (3)	2.389 (3)–2.437 (3)	2.431 (3)–2.467 (3)	3.844 (7)–3.899 (8)	4.504 (8)–4.585 (9)	0.439	SAPR-8
Eu—CO₃	1.886 (14)–2.022 (13)	2.406 (11)–2.493 (11)	2.369 (13)–2.392 (15)	3.890 (2)–3.911 (3)	4.575 (3)–4.589 (3)	0.351	TDD-8
Eu-OAc	1.902 (3)–2.041 (2)	2.440 (4)–2.515 (2)	2.4057 (18)–2.443 (2)	3.8517 (4)–3.9049 (4)	4.5664 (5)–4.6074 (4)	0.469	TDD-8
Gd—SO₄	1.892 (3)–2.014 (3)	2.378 (3)–2.434 (3)	2.398 (3)–2.452 (3)	3.838 (7)–3.897 (9)	4.501 (8)–4.578 (11)	0.430	SAPR-8
Gd—CO₃	1.898 (2)–2.022 (2)	2.381 (2)–2.484 (2)	2.288 (17)–2.396 (10)	3.8699 (5)–3.9097 (5)	4.5677 (7)–4.5846 (7)	0.337	TDD-8
Gd-OAc	1.890 (12)–2.041 (11)	2.393 (3)–2.438 (9)	2.426 (10)–2.512 (10)	3.845 (2)–3.897 (2)	4.562 (2)–4.602 (2)	0.458	TDD-8
Tb—SO₄	1.890 (4)–2.018 (4)	2.370 (3)–2.430 (3)	2.383 (3)–2.451 (3)	3.8398 (8)–3.8944 (8)	4.501 (1)–4.577 (1)	0.427	SAPR-8
Tb-OAc	1.889 (11)–2.036 (11)	2.383 (9)–2.431 (9)	2.409 (10)–2.488 (10)	3.840 (2)–3.896 (2)	4.562 (2)–4.598 (2)	0.445	TDD-8
Dy—SO₄	1.8908 (18)–2.0206 (19)	2.3640 (15) −2.4234 (15)	2.3665 (17)–2.4334 (17)	3.834 (2)–3.889 (2)	4.493 (2)–4.573 (2)	0.424	SAPR-8
Dy—CO₃	1.898 (3)–2.022 (3)	2.382 (3)–2.469 (3)	2.27 (2)–2.380 (8)	3.8715 (5)–3.9016 (6)	4.5645 (7)–4.5797 (8)	0.354	TDD-8
Ho—SO₄	1.887 (3)–2.016 (3)	2.356 (2)–2.416 (2)	2.357 (2)–2.417 (2)	3.827 (2)–3.884 (2)	4.485 (2)–4.565 (2)	0.422	SAPR-8
Ho—CO₃	1.898 (2)–2.022 (2)	2.374 (2)–2.475 (2)	2.30 (3)–2.374 (12)	3.8670 (5)–3.9021 (5)	4.5583 (7)–4.5808 (7)	0.330	TDD-8
Notes: (a) Complex Tb—SO₄ is 1; Ln-SO₄ correspond to the [LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]₂(SO₄) series with Ln = Pr, Nd, Sm, Eu, Gd, Dy and Ho described in (Pavlishchuk et al., 2011); Ln-CO₃ are [LnCu₅(GlyHA)₅(CO₃)(NO₃)(H₂O)₅] with Ln = Eu, Gd, Dy and Ho described in Pavlishchuk et al. (2019) and Stemmler et al. (1999); Ln-OAc are [LnCu₅(GlyHA)₅(OAc)(H₂O)₅](NO₃)₂ Ln = Eu, Gd and Tb described in Katkova et al. (2015a) and Meng et al. (2016). (b) LnO₈ geometries: SAPR-8 = square antiprism (D4d) and TDD-8 = triangular dodecahedron (D_2d).

Table 3
Continuous shape calculations for octacoordinated Ln³⁺ ions in 1 obtained with Shape 2.1 software (Casanova et al., 2005)

	OP-8	HPY-8	HBPY-8	CU-8	SAPR-8	TDD-8	JGBF-8	JETBPY-8
Pr–SO₄	30.846	22.755	15.952	11.561	2.215	2.397	13.029	25.482
Nd–SO₄	30.677	22.888	15.968	11.587	2.141	2.364	13.033	25.516
Sm–SO₄	30.387	22.903	15.951	11.562	2.020	2.311	13.013	25.752
Eu–SO₄	30.516	23.164	16.270	11.783	1.952	2.363	13.190	25.864
Gd–SO₄	30.465	23.110	16.032	11.570	1.907	2.269	13.151	26.121
Tb–SO₄	30.381	23.117	16.159	11.666	1.854	2.322	13.140	26.276
Dy–SO₄	30.357	23.195	16.112	11.603	1.799	2.254	13.168	26.433
Ho–SO₄	30.272	23.212	16.095	11.588	1.761	2.247	13.186	26.496
Octacoordinated ions: OP-8 = octagon (D_8h); HPY-8 = heptagonal pyramid (C_7v); HBPY-8 = hexagonal bipyramid (D_6h); CU-8 = cube (O_h); SAPR-8 = square antiprism (D_4d); TDD-8 = triangular dodecahedron (D_2d); JGBF-8 = Johnson gyrobifastigium J26 (D_2d); JETBPY-8 = Johnson elongated triangular bipyramid J14 (D_3h).

Figure 3
The Tb^III coordination sphere geometry in 1.

The Cu⋯Cu and Ln⋯Cu separations for complex 1 range from 4.501 (1) to 4.577 (1) Å and 3.8398 (8) to 3.8944 (8) Å, respectively, and are typical for {LnCu₅}³⁺ metallacrowns (Stemmler et al., 1999; Pavlishchuk et al., 2011; Katkova et al., 2015a; Meng et al., 2016). The Cu—O, Cu—N and Cu⋯Cu distances do not vary significantly amongst metallamacrocycles with different bidentate counter-anions (Table 2). The metallacrown moiety in 1 is close to planar, the deviation of Tb^III ions from the mean plane Cu1–Cu5 being 0.4270 (4) Å. The Ln—O distances, Ln—Cu separations and deviations of the Ln^III ions from the Cu₅ planes of the metallamacrocycles trend with the lanthanide contraction in all members of the isomorphous [LnCu₅(GlyHA)₅]³⁺ series. However, there are some minor differences in the observed values for a given Ln^III ion, depending on the coordinated bidentate counter-anion, which is likely associated with the different planarities of the {LnCu₅}³⁺ cores (Table 2).

3. Supramolecular features

The [LnCu₅(GlyHA)₅]³⁺ cations in complex 1 are non-oligomerized, which is typical for 15-metallacrown-5 complexes. The water apical to Tb^III in 1 (O15) is involved in the formation of intramolecular hydrogen bonds (O15—H15A⋯O21 and O15—H15B⋯O16) with apically coordinated water molecules O16 and O21 on copper(II) ions Cu3 and Cu1, respectively. Intramolecular hydrogen bonds in 1 are also formed between the bidentate sulfate and apically coordinated water molecules O17, O18 and O20 (O17—H17A⋯O12, O18—H18B⋯O14 and O20—H20B⋯O11) on copper(II) ions Cu4, Cu5 and Cu1. An extended system of intermolecular hydrogen bonds [N2—H2A⋯O15ⁱⁱⁱ, N8—H8B⋯O12^vi (SO₄), N10—H10A⋯O20ⁱ, O10ⁱⁱⁱⁱ⋯H21B—O21, O6^vi⋯H17B—O17, O21—H21A⋯O18^iv, O16—H16A⋯O17^iv] links adjacent [TbCu₅(GlyHA)₅(H₂O)_6.5(SO₄)]⁺ cations and non-coordinated sulfate anions [N4—H4A⋯O27^iv(SO₄), O18—H18A⋯O27(SO₄), N4—H4A⋯O25^x(SO₄) and O20—H20A⋯O25(SO₄)]. Non-coordinated water molecules in 1 are linked by hydrogen bonds with carbonyl oxygen and amine nitrogen atoms in the glycinehydroxamate unit from the metallacrown core (O4ⁱ⋯H23A—O23, O8⋯H24B—O24, N6—H6B⋯O24^vi, N8—H8A⋯O23, N10—H10B⋯O22^viii), apically coordinated water molecules (O16—H16B⋯O22, O19—H19A⋯O24^vii, O19–-H19B⋯O24^vi) or bidentate sulfate (O11ⁱ⋯H24A-–O24 and O13ⁱⁱ⋯H23B—O23). Hydrogen-bond parameters and symmetry codes are given in Table 4.

Table 4
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O24—H24B⋯O8	0.84 (2)	2.01 (3)	2.807 (5)	159 (7)
O24—H24A⋯O11ⁱ	0.84 (2)	2.21 (3)	3.015 (5)	162 (7)
O23—H23B⋯O13ⁱⁱ	0.85 (2)	2.02 (3)	2.853 (5)	166 (6)
O23—H23A⋯O4ⁱ	0.84 (2)	1.89 (2)	2.734 (5)	176 (7)
O22—H22B⋯O23	0.84 (2)	1.89 (3)	2.701 (6)	162 (8)
O22—H22A⋯O26ⁱⁱⁱ	0.84 (2)	2.18 (4)	2.968 (9)	155 (8)
O22—H22A⋯O28ⁱⁱ	0.84 (2)	1.92 (3)	2.733 (9)	161 (8)
O21—H21B⋯O10ⁱⁱⁱ	0.83 (2)	1.91 (3)	2.728 (5)	165 (8)
O21—H21A⋯O18^iv	0.84 (2)	1.94 (3)	2.765 (5)	167 (7)
O20—H20B⋯O11	0.83 (2)	2.14 (3)	2.960 (5)	168 (7)
O20—H20A⋯O26^v	0.83 (2)	2.09 (3)	2.916 (9)	170 (7)
O20—H20A⋯O25	0.83 (2)	2.02 (5)	2.719 (9)	142 (7)
O19—H19B⋯O24^vi	0.84 (2)	2.07 (9)	2.866 (11)	157 (22)
O19—H19A⋯O24^vii	0.84 (2)	1.72 (7)	2.535 (12)	162 (21)
O18—H18B⋯O14	0.83 (2)	1.90 (2)	2.732 (5)	173 (7)
O18—H18A⋯O26^v	0.84 (2)	2.04 (3)	2.857 (9)	163 (7)
O18—H18A⋯O27	0.84 (2)	1.91 (4)	2.648 (9)	146 (6)
O17—H17B⋯O6^vi	0.83 (2)	1.90 (2)	2.730 (5)	176 (7)
O17—H17A⋯O12	0.83 (2)	2.10 (3)	2.905 (5)	163 (6)
O16—H16B⋯O22	0.84 (2)	1.89 (2)	2.721 (6)	173 (7)
O16—H16A⋯O17^iv	0.84 (2)	1.95 (2)	2.784 (5)	172 (7)
O15—H15B⋯O16	0.84 (2)	1.86 (2)	2.692 (5)	170 (6)
O15—H15A⋯O21	0.84 (2)	1.85 (3)	2.668 (5)	166 (6)
N10—H10B⋯O22^viii	0.91	2.13	2.920 (6)	145
N10—H10A⋯O20ⁱ	0.91	2.24	2.987 (5)	139
N8—H8B⋯O12^vi	0.91	2.04	2.937 (5)	168
N8—H8A⋯O23	0.91	2.20	3.031 (5)	152
N6—H6B⋯O13^ix	0.91	2.64	3.363 (5)	137
N6—H6B⋯O24^vi	0.91	2.24	2.984 (6)	139
N6—H6A⋯O13^iv	0.91	2.25	3.158 (5)	175
N4—H4B⋯O2^x	0.91	2.33	3.182 (5)	156
N4—H4A⋯O27^iv	0.91	2.18	3.037 (9)	156
N4—H4A⋯O25^x	0.91	2.01	2.789 (9)	143
N2—H2B⋯O27	0.91	2.55	3.418 (9)	159
N2—H2B⋯O28^v	0.91	2.08	2.868 (9)	144
N2—H2A⋯O15ⁱⁱⁱ	0.91	2.07	2.946 (5)	162
Symmetry codes: (i) x, y+1, z; (ii) x+1, y+1, z; (iii) ; (iv) x+1, y, z; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .

4. Database survey

Compounds most closely related to 1 are its isomorphous counterparts [LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]₂(SO₄), where GlyHA²⁻ is the dianion of glycinehydroxamic acid and Ln^III = Pr, Nd, Sm, Eu, Gd, Dy and Ho (Pavlishchuk et al., 2011). A search of the Cambridge Structural Database (Version 5.41, 2021; Groom et al., 2016 ) reveals other compounds that also feature an LnCu₅(GlyHA)₅ core, with counter-anions such as nitrate, acetate, chloride, lactate, carbonate, sulfate, isophthalate, terephthalate and all lanthanide ions other than radioactive Pm (Katkova et al., 2015a,b ; Pavlishchuk et al., 2011, 2017a, Pavlishchuk et al., 2018, 2019; Stemmler et al., 1999; Muravyeva et al., 2016 ; Kremlev et al., 2016 ). Most of these complexes feature, similar to 1, individual molecular complex cations (Katkova et al., 2015a,b; Pavlishchuk et al., 2011, 2017a, 2018, 2019; Stemmler et al., 1999; Muravyeva et al., 2016; Kremlev et al., 2016), but a small number of oligomerized examples have also been reported (Pavlishchuk et al., 2017a, 2018).

5. Synthesis and crystallization

Complex 1 was synthesized and crystallized according a general procedure described previously (Pavlishchuk et al., 2011). Single crystals were obtained by slow evaporation from an aqueous solution of 1.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The structure is isomorphous with its Dy, Eu, Gd, Ho, Nd, Pr analogues (Pavlishchuk et al., 2011) and was solved by isomorphous replacement. The O19 water molecule is disordered over two mutually exclusive positions across an inversion center and was refined as half occupied. The non-coordinated sulfate ion is located on an inversion center and the oxygen atoms are disordered over two sets of positions with half occupancy.

Table 5
Experimental details

Crystal data
Chemical formula	[TbCu₅(C₂H₄N₂O₂)₅(SO₄)(H₂O)_6.5]₂(SO₄)·6H₂O
M_r	2464.44
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	9.6370 (4), 11.5888 (5), 16.2367 (6)
α, β, γ (°)	99.6716 (13), 91.3031 (12), 105.3123 (12)
V (Å³)	1719.80 (12)
Z	1
Radiation type	Cu Kα
μ (mm⁻¹)	15.11
Crystal size (mm)	0.20 × 0.20 × 0.08

Data collection
Diffractometer	Bruker AXS D8 Quest CMOS diffractometer with PhotonII charge-integrating pixel array detector (CPAD)
Absorption correction	Multi-scan (SADABS; Krause et al., 2015
T_min, T_max	0.454, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	16278, 7029, 6786
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.10
No. of reflections	7029
No. of parameters	562
No. of restraints	22
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.59, −1.34
Computer programs: APEX3 and SAINT (Bruker, 2018 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), shelXle (Hübschle et al., 2011 ) and publCIF (Westrip, 2010 ).

C—H bond distances were constrained to 0.99 for aliphatic CH₂ moieties. N—H bond distances were constrained to 0.91 Å for pyramidal (sp³-hybridized) ammonium NH₂⁺ groups. Water H-atom positions were refined, and O—H distances were restrained to 0.84 (2) Å. The H⋯H distances within the O23 and O24 water molecules were further restrained to 1.35 (2) Å. U_iso(H) values were set to kU_eq(C/N/O) with k =1.5 for OH, and 1.2 for CH₂ and NH₂⁺ units, respectively.

Supporting information

CCDC reference: 2121203

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989021011907/yy2004sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021011907/yy2004Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015), shelXle (Hübschle et al., 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis[hexaaquahemiaquapentakis(µ₃-glycinehydroxamato)sulfatopentacopper(II)terbium(III)] sulfate hexahydrate top

Crystal data top

[TbCu₅(C₂H₄N₂O₂)₅(SO₄)(H₂O)_6.5]₂(SO₄)·6H₂O	Z = 1
M_r = 2464.44	F(000) = 1214
Triclinic, P1	D_x = 2.380 Mg m⁻³
a = 9.6370 (4) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.5888 (5) Å	Cell parameters from 9965 reflections
c = 16.2367 (6) Å	θ = 4.0–79.9°
α = 99.6716 (13)°	µ = 15.11 mm⁻¹
β = 91.3031 (12)°	T = 150 K
γ = 105.3123 (12)°	Plate, blue
V = 1719.80 (12) Å³	0.20 × 0.20 × 0.08 mm

Data collection top

Bruker AXS D8 Quest CMOS diffractometer with PhotonII charge-integrating pixel array detector (CPAD)	7029 independent reflections
Radiation source: I-mu-S microsource X-ray tube	6786 reflections with I > 2σ(I)
Laterally graded multilayer (Goebel) mirror monochromator	R_int = 0.050
Detector resolution: 7.4074 pixels mm^-1	θ_max = 80.3°, θ_min = 2.8°
ω and phi scans	h = −12→12
Absorption correction: multi-scan (SADABS; Krause et al., 2015	k = −14→14
T_min = 0.454, T_max = 0.754	l = −19→15
16278 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: mixed
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0656P)² + 1.8351P] where P = (F_o² + 2F_c²)/3
7029 reflections	(Δ/σ)_max < 0.001
562 parameters	Δρ_max = 1.59 e Å⁻³
22 restraints	Δρ_min = −1.34 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. The structure is ismorphous with its Dy, Eu, Gd, Ho, Nd, Pr analogues (AVP85_10mz121, AVP355_10mz172, AVP621_09mz411 and AVP629_10mz194, AVP65_10mz125 and AVP651_10mz191, AVP70_10mz147, AVP75_10mz148 and AVP754_10mz650), and was solved by isomorphous replacement.

The water molecule of O19 is disordered over two mutually exclusive positions across an inversion center and was refined as half occupied. The non-coordinated sulfate ion is located on an inversion center and the oxygen atoms are disordered over two sets of positions with half occupancy.

Water H atom positions were refined and O-H distances were restrained to 0.84 (2) Angstrom, respectively. Some H···H distances were further restrained to 1.35 (2) Angstrom.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.4433 (5)	0.2625 (4)	0.5042 (3)	0.0167 (8)
C2	0.3610 (5)	0.2938 (4)	0.5788 (3)	0.0195 (9)
H2C	0.320220	0.220082	0.602893	0.023*
H2D	0.427084	0.354919	0.622292	0.023*
C3	0.6783 (5)	0.0423 (4)	0.2493 (3)	0.0158 (8)
C4	0.6931 (6)	−0.0360 (5)	0.3110 (3)	0.0235 (10)
H4C	0.794720	−0.038433	0.316648	0.028*
H4D	0.632740	−0.119964	0.290399	0.028*
C5	0.7890 (5)	0.3483 (4)	0.0317 (3)	0.0175 (9)
C6	0.8858 (5)	0.2707 (4)	−0.0019 (3)	0.0221 (10)
H6C	0.874472	0.253424	−0.063895	0.027*
H6D	0.987712	0.315424	0.015213	0.027*
C7	0.5254 (5)	0.6985 (4)	0.1304 (3)	0.0159 (8)
C8	0.6022 (5)	0.7507 (4)	0.0594 (3)	0.0179 (9)
H8C	0.532673	0.736705	0.010561	0.022*
H8D	0.643978	0.839491	0.076935	0.022*
C9	0.2149 (5)	0.5808 (4)	0.3895 (3)	0.0163 (9)
C10	0.1644 (5)	0.6898 (4)	0.3802 (3)	0.0222 (10)
H10C	0.058903	0.664428	0.366493	0.027*
H10D	0.184336	0.748022	0.434014	0.027*
Cu1	0.57451 (7)	0.15475 (6)	0.38923 (4)	0.01792 (16)
Cu2	0.71639 (7)	0.16393 (6)	0.12404 (4)	0.01884 (16)
Cu3	0.68477 (7)	0.53540 (6)	0.08031 (4)	0.01553 (15)
Cu4	0.34975 (7)	0.64627 (6)	0.24858 (4)	0.01548 (15)
Cu5	0.28203 (7)	0.39948 (6)	0.44370 (4)	0.01615 (15)
Tb1	0.48345 (2)	0.35681 (2)	0.24306 (2)	0.01322 (9)
N1	0.4245 (4)	0.3141 (3)	0.4416 (2)	0.0171 (7)
N2	0.2431 (4)	0.3430 (4)	0.5530 (2)	0.0195 (8)
H2A	0.236548	0.406266	0.592889	0.023*
H2B	0.157731	0.284301	0.547628	0.023*
N3	0.6105 (4)	0.1242 (3)	0.2732 (2)	0.0178 (7)
N4	0.6482 (5)	0.0108 (4)	0.3943 (3)	0.0215 (8)
H4A	0.724750	0.031948	0.432837	0.026*
H4B	0.577960	−0.048780	0.410697	0.026*
N5	0.7027 (4)	0.3075 (3)	0.0865 (2)	0.0166 (7)
N6	0.8492 (4)	0.1541 (3)	0.0304 (2)	0.0171 (7)
H6A	0.931299	0.139490	0.049586	0.021*
H6B	0.805401	0.091646	−0.011692	0.021*
N7	0.5575 (4)	0.6039 (3)	0.1480 (2)	0.0172 (7)
N8	0.7190 (4)	0.6918 (3)	0.0356 (2)	0.0159 (7)
H8A	0.805912	0.742721	0.057077	0.019*
H8B	0.720395	0.676114	−0.021109	0.019*
N9	0.2929 (4)	0.5471 (3)	0.3302 (2)	0.0173 (7)
N10	0.2378 (4)	0.7509 (4)	0.3133 (3)	0.0226 (8)
H10A	0.298699	0.824200	0.336523	0.027*
H10B	0.171092	0.763954	0.278010	0.027*
O1	0.5000 (3)	0.2882 (3)	0.37163 (19)	0.0166 (6)
O2	0.5244 (4)	0.1896 (3)	0.5060 (2)	0.0196 (6)
O3	0.6029 (4)	0.1998 (3)	0.2163 (2)	0.0199 (7)
O4	0.7336 (4)	0.0300 (3)	0.1769 (2)	0.0196 (7)
O5	0.6158 (3)	0.3809 (3)	0.11866 (19)	0.0157 (6)
O6	0.7979 (4)	0.4510 (3)	0.0074 (2)	0.0189 (6)
O7	0.4861 (3)	0.5537 (3)	0.2123 (2)	0.0166 (6)
O8	0.4330 (3)	0.7478 (3)	0.1689 (2)	0.0193 (6)
O9	0.3463 (3)	0.4493 (3)	0.3393 (2)	0.0170 (6)
O10	0.1827 (4)	0.5265 (3)	0.4519 (2)	0.0195 (7)
O11	0.2853 (4)	0.1696 (3)	0.2229 (2)	0.0238 (7)
O12	0.2734 (4)	0.3216 (3)	0.1464 (2)	0.0205 (7)
O13	0.1448 (4)	0.1123 (3)	0.0876 (2)	0.0253 (7)
O14	0.0575 (4)	0.2189 (4)	0.2058 (2)	0.0311 (8)
O15	0.7222 (3)	0.4609 (3)	0.3006 (2)	0.0184 (6)
H15A	0.767 (6)	0.430 (5)	0.331 (3)	0.028*
H15B	0.782 (5)	0.495 (5)	0.269 (3)	0.028*
O16	0.8851 (4)	0.5789 (3)	0.1920 (2)	0.0254 (7)
H16A	0.960 (5)	0.557 (6)	0.184 (4)	0.038*
H16B	0.917 (7)	0.653 (2)	0.213 (4)	0.038*
O17	0.1408 (4)	0.5205 (3)	0.1525 (2)	0.0220 (7)
H17A	0.163 (7)	0.457 (4)	0.156 (4)	0.033*
H17B	0.155 (7)	0.528 (6)	0.1031 (18)	0.033*
O18	0.0716 (4)	0.2521 (3)	0.3767 (2)	0.0241 (7)
H18A	0.043 (7)	0.185 (3)	0.393 (4)	0.036*
H18B	0.070 (7)	0.236 (6)	0.3246 (13)	0.036*
O19	0.5200 (11)	0.0381 (11)	0.0275 (6)	0.047 (2)	0.5
H19A	0.472 (19)	−0.003 (15)	0.060 (9)	0.071*	0.5
H19B	0.55 (2)	0.02 (2)	−0.021 (6)	0.071*	0.5
O20	0.3102 (4)	0.0221 (3)	0.3519 (3)	0.0283 (8)
H20A	0.236 (5)	0.022 (7)	0.377 (4)	0.043*
H20B	0.291 (8)	0.063 (6)	0.318 (4)	0.043*
O21	0.8274 (4)	0.3337 (4)	0.3966 (2)	0.0308 (8)
H21A	0.909 (4)	0.320 (7)	0.392 (5)	0.046*
H21B	0.841 (8)	0.380 (6)	0.443 (3)	0.046*
O22	0.9749 (5)	0.8150 (4)	0.2711 (3)	0.0361 (9)
H22A	0.972 (9)	0.855 (7)	0.319 (2)	0.054*
H22B	0.980 (9)	0.857 (6)	0.234 (4)	0.054*
O23	0.9394 (4)	0.9116 (3)	0.1345 (2)	0.0243 (7)
H23A	0.876 (4)	0.947 (5)	0.150 (4)	0.036*
H23B	1.011 (4)	0.968 (4)	0.126 (4)	0.036*
O24	0.3431 (7)	0.9430 (4)	0.1264 (3)	0.0523 (14)
H24A	0.328 (11)	0.998 (6)	0.163 (4)	0.079*
H24B	0.368 (10)	0.893 (6)	0.152 (4)	0.079*
O25	0.1618 (8)	0.0365 (9)	0.4920 (5)	0.0357 (19)	0.5
O26	−0.0300 (9)	−0.0158 (7)	0.5820 (5)	0.0339 (17)	0.5
O27	−0.0484 (9)	0.1032 (7)	0.4781 (5)	0.0333 (17)	0.5
O28	−0.0592 (9)	−0.1078 (7)	0.4360 (5)	0.0346 (17)	0.5
S1	0.18461 (12)	0.20240 (10)	0.16476 (7)	0.0195 (2)
S2	0.000000	0.000000	0.500000	0.0199 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0163 (19)	0.0162 (19)	0.019 (2)	0.0070 (16)	0.0042 (17)	0.0016 (17)
C2	0.024 (2)	0.025 (2)	0.016 (2)	0.0143 (18)	0.0049 (17)	0.0080 (18)
C3	0.0152 (19)	0.0150 (19)	0.019 (2)	0.0092 (16)	0.0030 (16)	0.0011 (17)
C4	0.034 (3)	0.024 (2)	0.019 (2)	0.020 (2)	0.0063 (19)	0.0025 (19)
C5	0.018 (2)	0.019 (2)	0.016 (2)	0.0074 (17)	0.0045 (17)	0.0023 (17)
C6	0.025 (2)	0.018 (2)	0.025 (2)	0.0068 (18)	0.0113 (19)	0.0018 (18)
C7	0.0150 (19)	0.0126 (19)	0.019 (2)	0.0023 (15)	0.0009 (16)	0.0027 (17)
C8	0.018 (2)	0.017 (2)	0.021 (2)	0.0078 (16)	0.0038 (17)	0.0055 (17)
C9	0.018 (2)	0.0165 (19)	0.017 (2)	0.0114 (16)	0.0011 (16)	−0.0027 (17)
C10	0.029 (2)	0.024 (2)	0.022 (2)	0.0194 (19)	0.0081 (19)	0.0066 (19)
Cu1	0.0252 (3)	0.0179 (3)	0.0165 (3)	0.0146 (3)	0.0054 (3)	0.0048 (3)
Cu2	0.0252 (3)	0.0152 (3)	0.0212 (4)	0.0122 (3)	0.0111 (3)	0.0051 (3)
Cu3	0.0188 (3)	0.0136 (3)	0.0167 (3)	0.0074 (2)	0.0067 (2)	0.0039 (2)
Cu4	0.0173 (3)	0.0138 (3)	0.0189 (3)	0.0090 (2)	0.0052 (2)	0.0045 (2)
Cu5	0.0188 (3)	0.0174 (3)	0.0169 (3)	0.0111 (3)	0.0069 (2)	0.0053 (3)
Tb1	0.01436 (14)	0.01192 (14)	0.01535 (15)	0.00683 (10)	0.00396 (10)	0.00235 (10)
N1	0.0233 (18)	0.0181 (17)	0.0138 (18)	0.0112 (15)	0.0065 (14)	0.0044 (14)
N2	0.0220 (19)	0.0194 (18)	0.020 (2)	0.0106 (15)	0.0073 (15)	0.0036 (15)
N3	0.0234 (19)	0.0150 (17)	0.0201 (19)	0.0111 (15)	0.0070 (15)	0.0071 (15)
N4	0.029 (2)	0.0223 (19)	0.020 (2)	0.0157 (16)	0.0087 (16)	0.0072 (16)
N5	0.0159 (17)	0.0179 (17)	0.0169 (18)	0.0087 (14)	0.0056 (14)	−0.0016 (15)
N6	0.0171 (17)	0.0183 (18)	0.0193 (19)	0.0092 (14)	0.0060 (14)	0.0053 (15)
N7	0.0192 (18)	0.0170 (17)	0.0174 (18)	0.0075 (14)	0.0036 (15)	0.0043 (15)
N8	0.0212 (18)	0.0104 (15)	0.0183 (18)	0.0060 (14)	0.0061 (14)	0.0057 (14)
N9	0.0202 (18)	0.0166 (17)	0.0185 (19)	0.0108 (14)	0.0029 (15)	0.0032 (15)
N10	0.0212 (19)	0.0169 (18)	0.034 (2)	0.0125 (15)	0.0102 (17)	0.0039 (17)
O1	0.0207 (15)	0.0205 (15)	0.0148 (15)	0.0141 (12)	0.0090 (12)	0.0057 (12)
O2	0.0277 (17)	0.0195 (15)	0.0172 (16)	0.0146 (13)	0.0065 (13)	0.0050 (13)
O3	0.0307 (17)	0.0187 (15)	0.0182 (16)	0.0155 (13)	0.0121 (13)	0.0095 (13)
O4	0.0251 (16)	0.0183 (15)	0.0197 (16)	0.0123 (13)	0.0084 (13)	0.0041 (13)
O5	0.0193 (14)	0.0119 (13)	0.0197 (16)	0.0103 (11)	0.0064 (12)	0.0031 (12)
O6	0.0271 (17)	0.0166 (14)	0.0172 (16)	0.0107 (13)	0.0104 (13)	0.0053 (12)
O7	0.0180 (14)	0.0154 (14)	0.0205 (16)	0.0086 (12)	0.0114 (12)	0.0067 (12)
O8	0.0201 (15)	0.0193 (15)	0.0238 (17)	0.0120 (12)	0.0072 (13)	0.0070 (13)
O9	0.0204 (15)	0.0178 (15)	0.0210 (16)	0.0168 (12)	0.0109 (12)	0.0065 (13)
O10	0.0280 (17)	0.0209 (15)	0.0172 (16)	0.0160 (13)	0.0094 (13)	0.0081 (13)
O11	0.0247 (17)	0.0219 (16)	0.0246 (18)	0.0061 (13)	−0.0008 (14)	0.0042 (14)
O12	0.0253 (16)	0.0174 (15)	0.0180 (16)	0.0028 (13)	0.0002 (13)	0.0058 (13)
O13	0.0280 (17)	0.0206 (16)	0.0241 (18)	0.0028 (14)	0.0013 (14)	0.0010 (14)
O14	0.0210 (17)	0.043 (2)	0.0267 (19)	0.0086 (16)	0.0047 (14)	−0.0019 (16)
O15	0.0178 (15)	0.0222 (16)	0.0167 (16)	0.0076 (12)	0.0016 (12)	0.0041 (13)
O16	0.0190 (16)	0.0268 (17)	0.0287 (19)	0.0047 (14)	0.0044 (14)	0.0029 (15)
O17	0.0281 (17)	0.0224 (16)	0.0183 (16)	0.0111 (14)	0.0040 (14)	0.0043 (14)
O18	0.0261 (17)	0.0227 (17)	0.0236 (18)	0.0066 (14)	0.0045 (14)	0.0040 (14)
O19	0.038 (5)	0.064 (6)	0.026 (4)	−0.007 (4)	−0.001 (4)	0.005 (4)
O20	0.0309 (19)	0.0200 (17)	0.035 (2)	0.0066 (15)	0.0100 (16)	0.0063 (15)
O21	0.0287 (19)	0.044 (2)	0.0241 (19)	0.0232 (17)	0.0003 (15)	−0.0036 (16)
O22	0.047 (2)	0.036 (2)	0.032 (2)	0.0236 (19)	−0.0020 (19)	0.0038 (17)
O23	0.0215 (16)	0.0173 (15)	0.035 (2)	0.0072 (13)	0.0068 (15)	0.0026 (14)
O24	0.090 (4)	0.039 (2)	0.037 (2)	0.043 (3)	−0.015 (2)	−0.008 (2)
O25	0.023 (4)	0.058 (5)	0.034 (4)	0.014 (4)	0.007 (3)	0.022 (4)
O26	0.042 (4)	0.034 (4)	0.025 (4)	0.011 (3)	0.007 (3)	0.002 (3)
O27	0.038 (4)	0.030 (4)	0.041 (5)	0.018 (3)	0.007 (3)	0.018 (3)
O28	0.044 (5)	0.026 (4)	0.033 (4)	0.009 (3)	0.004 (3)	0.003 (3)
S1	0.0186 (5)	0.0195 (5)	0.0200 (5)	0.0044 (4)	0.0019 (4)	0.0037 (4)
S2	0.0189 (7)	0.0180 (7)	0.0235 (8)	0.0071 (6)	−0.0005 (6)	0.0026 (6)

Geometric parameters (Å, º) top

C1—N1	1.294 (6)	Cu5—N2	2.003 (4)
C1—O2	1.298 (5)	Cu5—O18	2.379 (4)
C1—C2	1.509 (6)	Tb1—O9	2.370 (3)
C2—N2	1.480 (6)	Tb1—O1	2.372 (3)
C2—H2C	0.9900	Tb1—O15	2.383 (3)
C2—H2D	0.9900	Tb1—O3	2.386 (3)
C3—N3	1.301 (5)	Tb1—O7	2.411 (3)
C3—O4	1.304 (6)	Tb1—O5	2.430 (3)
C3—C4	1.488 (7)	Tb1—O12	2.436 (3)
C4—N4	1.488 (6)	Tb1—O11	2.451 (3)
C4—H4C	0.9900	Tb1—S1	3.0756 (11)
C4—H4D	0.9900	N1—O1	1.396 (5)
C5—N5	1.295 (6)	N2—H2A	0.9100
C5—O6	1.298 (6)	N2—H2B	0.9100
C5—C6	1.509 (6)	N3—O3	1.389 (5)
C6—N6	1.491 (6)	N4—H4A	0.9100
C6—H6C	0.9900	N4—H4B	0.9100
C6—H6D	0.9900	N5—O5	1.395 (4)
C7—N7	1.288 (6)	N6—H6A	0.9100
C7—O8	1.298 (5)	N6—H6B	0.9100
C7—C8	1.509 (6)	N7—O7	1.388 (5)
C8—N8	1.489 (5)	N8—H8A	0.9100
C8—H8C	0.9900	N8—H8B	0.9100
C8—H8D	0.9900	N9—O9	1.391 (5)
C9—O10	1.282 (6)	N10—H10A	0.9100
C9—N9	1.306 (6)	N10—H10B	0.9100
C9—C10	1.498 (6)	O11—S1	1.500 (4)
C10—N10	1.487 (7)	O12—S1	1.502 (3)
C10—H10C	0.9900	O13—S1	1.461 (3)
C10—H10D	0.9900	O14—S1	1.448 (4)
Cu1—N3	1.915 (4)	O15—H15A	0.84 (2)
Cu1—O1	1.928 (3)	O15—H15B	0.84 (2)
Cu1—O2	1.969 (3)	O16—H16A	0.84 (2)
Cu1—N4	1.991 (4)	O16—H16B	0.84 (2)
Cu1—O20	2.601 (4)	O17—H17A	0.83 (2)
Cu1—O21	2.736 (4)	O17—H17B	0.83 (2)
Cu2—N5	1.900 (4)	O18—H18A	0.84 (2)
Cu2—O3	1.928 (3)	O18—H18B	0.83 (2)
Cu2—O4	1.936 (3)	O19—H19A	0.84 (2)
Cu2—N6	2.018 (4)	O19—H19B	0.84 (2)
Cu2—O19	2.409 (10)	O20—H20A	0.83 (2)
Cu3—N7	1.904 (4)	O20—H20B	0.83 (2)
Cu3—O6	1.944 (3)	O21—H21A	0.84 (2)
Cu3—O5	1.949 (3)	O21—H21B	0.83 (2)
Cu3—N8	2.014 (4)	O22—H22A	0.84 (2)
Cu3—O16	2.508 (4)	O22—H22B	0.84 (2)
Cu4—N9	1.894 (4)	O23—H23A	0.84 (2)
Cu4—O8	1.940 (3)	O23—H23B	0.85 (2)
Cu4—O7	1.947 (3)	O24—H24A	0.84 (2)
Cu4—N10	2.012 (4)	O24—H24B	0.84 (2)
Cu4—O17	2.481 (4)	O25—S2	1.519 (7)
Cu5—N1	1.890 (4)	O26—S2	1.401 (8)
Cu5—O9	1.943 (3)	O27—S2	1.485 (7)
Cu5—O10	1.946 (3)	O28—S2	1.458 (8)

N1—C1—O2	125.3 (4)	O5—Tb1—O11	112.83 (11)
N1—C1—C2	114.2 (4)	O12—Tb1—O11	57.34 (11)
O2—C1—C2	120.5 (4)	O9—Tb1—S1	83.26 (8)
N2—C2—C1	110.0 (4)	O1—Tb1—S1	102.84 (8)
N2—C2—H2C	109.7	O15—Tb1—S1	174.96 (8)
C1—C2—H2C	109.7	O3—Tb1—S1	96.74 (9)
N2—C2—H2D	109.7	O7—Tb1—S1	101.43 (8)
C1—C2—H2D	109.7	O5—Tb1—S1	101.06 (8)
H2C—C2—H2D	108.2	O12—Tb1—S1	28.74 (8)
N3—C3—O4	123.0 (4)	O11—Tb1—S1	28.77 (8)
N3—C3—C4	115.9 (4)	C1—N1—O1	115.9 (3)
O4—C3—C4	121.1 (4)	C1—N1—Cu5	119.5 (3)
C3—C4—N4	111.1 (4)	O1—N1—Cu5	124.1 (3)
C3—C4—H4C	109.4	C2—N2—Cu5	109.8 (3)
N4—C4—H4C	109.4	C2—N2—H2A	109.7
C3—C4—H4D	109.4	Cu5—N2—H2A	109.7
N4—C4—H4D	109.4	C2—N2—H2B	109.7
H4C—C4—H4D	108.0	Cu5—N2—H2B	109.7
N5—C5—O6	123.7 (4)	H2A—N2—H2B	108.2
N5—C5—C6	116.0 (4)	C3—N3—O3	115.1 (4)
O6—C5—C6	120.3 (4)	C3—N3—Cu1	117.5 (3)
N6—C6—C5	110.5 (4)	O3—N3—Cu1	125.5 (3)
N6—C6—H6C	109.5	C4—N4—Cu1	110.6 (3)
C5—C6—H6C	109.5	C4—N4—H4A	109.5
N6—C6—H6D	109.5	Cu1—N4—H4A	109.5
C5—C6—H6D	109.5	C4—N4—H4B	109.5
H6C—C6—H6D	108.1	Cu1—N4—H4B	109.5
N7—C7—O8	124.1 (4)	H4A—N4—H4B	108.1
N7—C7—C8	115.5 (4)	C5—N5—O5	115.7 (4)
O8—C7—C8	120.4 (4)	C5—N5—Cu2	118.6 (3)
N8—C8—C7	109.8 (4)	O5—N5—Cu2	125.5 (3)
N8—C8—H8C	109.7	C6—N6—Cu2	109.6 (3)
C7—C8—H8C	109.7	C6—N6—H6A	109.7
N8—C8—H8D	109.7	Cu2—N6—H6A	109.7
C7—C8—H8D	109.7	C6—N6—H6B	109.7
H8C—C8—H8D	108.2	Cu2—N6—H6B	109.7
O10—C9—N9	123.8 (4)	H6A—N6—H6B	108.2
O10—C9—C10	121.2 (4)	C7—N7—O7	116.2 (4)
N9—C9—C10	115.0 (4)	C7—N7—Cu3	119.0 (3)
N10—C10—C9	111.3 (4)	O7—N7—Cu3	124.6 (3)
N10—C10—H10C	109.4	C8—N8—Cu3	109.7 (3)
C9—C10—H10C	109.4	C8—N8—H8A	109.7
N10—C10—H10D	109.4	Cu3—N8—H8A	109.7
C9—C10—H10D	109.4	C8—N8—H8B	109.7
H10C—C10—H10D	108.0	Cu3—N8—H8B	109.7
N3—Cu1—O1	90.36 (14)	H8A—N8—H8B	108.2
N3—Cu1—O2	175.68 (15)	C9—N9—O9	116.1 (4)
O1—Cu1—O2	86.12 (13)	C9—N9—Cu4	119.1 (3)
N3—Cu1—N4	83.85 (16)	O9—N9—Cu4	124.1 (3)
O1—Cu1—N4	173.91 (15)	C10—N10—Cu4	109.9 (3)
O2—Cu1—N4	99.57 (15)	C10—N10—H10A	109.7
N3—Cu1—O20	89.10 (15)	Cu4—N10—H10A	109.7
O1—Cu1—O20	85.07 (13)	C10—N10—H10B	109.7
O2—Cu1—O20	88.10 (14)	Cu4—N10—H10B	109.7
N4—Cu1—O20	92.89 (15)	H10A—N10—H10B	108.2
N3—Cu1—O21	82.42 (14)	N1—O1—Cu1	106.2 (2)
O1—Cu1—O21	80.09 (13)	N1—O1—Tb1	125.6 (2)
O2—Cu1—O21	99.41 (13)	Cu1—O1—Tb1	126.24 (14)
N4—Cu1—O21	100.98 (15)	C1—O2—Cu1	104.0 (3)
O20—Cu1—O21	162.82 (12)	N3—O3—Cu2	108.6 (2)
N5—Cu2—O3	89.51 (15)	N3—O3—Tb1	122.4 (2)
N5—Cu2—O4	172.53 (15)	Cu2—O3—Tb1	128.77 (15)
O3—Cu2—O4	84.79 (13)	C3—O4—Cu2	107.7 (3)
N5—Cu2—N6	83.61 (16)	N5—O5—Cu3	107.1 (2)
O3—Cu2—N6	171.24 (15)	N5—O5—Tb1	124.1 (2)
O4—Cu2—N6	101.58 (15)	Cu3—O5—Tb1	123.88 (13)
N5—Cu2—O19	92.3 (3)	C5—O6—Cu3	107.0 (3)
O3—Cu2—O19	97.4 (3)	N7—O7—Cu4	107.2 (2)
O4—Cu2—O19	93.2 (3)	N7—O7—Tb1	124.7 (2)
N6—Cu2—O19	88.3 (3)	Cu4—O7—Tb1	125.89 (14)
N7—Cu3—O6	174.11 (15)	C7—O8—Cu4	106.9 (3)
N7—Cu3—O5	91.24 (15)	N9—O9—Cu5	107.2 (2)
O6—Cu3—O5	84.79 (13)	N9—O9—Tb1	126.2 (2)
N7—Cu3—N8	82.67 (16)	Cu5—O9—Tb1	126.55 (14)
O6—Cu3—N8	100.63 (14)	C9—O10—Cu5	107.4 (3)
O5—Cu3—N8	169.87 (14)	S1—O11—Tb1	99.41 (17)
N7—Cu3—O16	96.61 (14)	S1—O12—Tb1	100.02 (16)
O6—Cu3—O16	87.37 (13)	Tb1—O15—H15A	121 (4)
O5—Cu3—O16	84.87 (13)	Tb1—O15—H15B	118 (4)
N8—Cu3—O16	103.81 (14)	H15A—O15—H15B	107 (6)
N9—Cu4—O8	172.67 (15)	Cu3—O16—H16A	122 (5)
N9—Cu4—O7	89.19 (15)	Cu3—O16—H16B	114 (5)
O8—Cu4—O7	85.34 (13)	H16A—O16—H16B	102 (7)
N9—Cu4—N10	83.73 (17)	Cu4—O17—H17A	92 (5)
O8—Cu4—N10	100.54 (16)	Cu4—O17—H17B	111 (5)
O7—Cu4—N10	165.82 (17)	H17A—O17—H17B	103 (6)
N9—Cu4—O17	90.56 (14)	Cu5—O18—H18A	120 (5)
O8—Cu4—O17	94.98 (13)	Cu5—O18—H18B	115 (5)
O7—Cu4—O17	97.53 (13)	H18A—O18—H18B	107 (7)
N10—Cu4—O17	94.81 (15)	Cu2—O19—H19A	99 (10)
N1—Cu5—O9	88.98 (14)	Cu2—O19—H19B	113 (10)
N1—Cu5—O10	163.89 (16)	H19A—O19—H19B	135 (10)
O9—Cu5—O10	85.41 (13)	Cu1—O20—H20A	131 (5)
N1—Cu5—N2	83.21 (16)	Cu1—O20—H20B	95 (5)
O9—Cu5—N2	171.78 (14)	H20A—O20—H20B	93 (7)
O10—Cu5—N2	101.44 (14)	Cu1—O21—H21A	124 (5)
N1—Cu5—O18	104.51 (15)	Cu1—O21—H21B	110 (5)
O9—Cu5—O18	93.14 (13)	H21A—O21—H21B	101 (7)
O10—Cu5—O18	90.88 (14)	H22A—O22—H22B	113 (8)
N2—Cu5—O18	91.31 (15)	H23A—O23—H23B	105 (3)
O9—Tb1—O1	71.67 (10)	H24A—O24—H24B	108 (3)
O9—Tb1—O15	100.80 (11)	O14—S1—O13	110.9 (2)
O1—Tb1—O15	75.87 (11)	O14—S1—O11	111.0 (2)
O9—Tb1—O3	144.63 (11)	O13—S1—O11	111.6 (2)
O1—Tb1—O3	73.91 (10)	O14—S1—O12	110.1 (2)
O15—Tb1—O3	78.22 (11)	O13—S1—O12	110.3 (2)
O9—Tb1—O7	70.65 (10)	O11—S1—O12	102.68 (19)
O1—Tb1—O7	131.81 (10)	O14—S1—Tb1	118.92 (16)
O15—Tb1—O7	82.82 (11)	O13—S1—Tb1	130.15 (15)
O3—Tb1—O7	142.47 (10)	O11—S1—Tb1	51.82 (13)
O9—Tb1—O5	143.39 (10)	O12—S1—Tb1	51.24 (13)
O1—Tb1—O5	139.79 (10)	O26ⁱ—S2—O26	180.0
O15—Tb1—O5	77.50 (11)	O26ⁱ—S2—O28ⁱ	114.8 (5)
O3—Tb1—O5	71.55 (10)	O26—S2—O28ⁱ	65.2 (5)
O7—Tb1—O5	72.88 (10)	O26ⁱ—S2—O28	65.2 (5)
O9—Tb1—O12	83.74 (11)	O26—S2—O28	114.8 (5)
O1—Tb1—O12	129.16 (11)	O28ⁱ—S2—O28	180.0 (5)
O15—Tb1—O12	153.99 (11)	O26ⁱ—S2—O27	68.7 (5)
O3—Tb1—O12	112.70 (11)	O26—S2—O27	111.3 (5)
O7—Tb1—O12	74.50 (11)	O28ⁱ—S2—O27	70.8 (5)
O5—Tb1—O12	83.70 (11)	O28—S2—O27	109.2 (5)
O9—Tb1—O11	88.43 (11)	O26ⁱ—S2—O25	69.6 (5)
O1—Tb1—O11	77.71 (11)	O26—S2—O25	110.4 (5)
O15—Tb1—O11	147.49 (12)	O28ⁱ—S2—O25	73.6 (5)
O3—Tb1—O11	76.51 (12)	O28—S2—O25	106.4 (5)
O7—Tb1—O11	129.39 (11)	O27—S2—O25	104.2 (5)

N1—C1—C2—N2	18.5 (6)	O10—C9—N9—Cu4	−173.1 (3)
O2—C1—C2—N2	−161.5 (4)	C10—C9—N9—Cu4	6.7 (5)
N3—C3—C4—N4	−9.9 (6)	O7—Cu4—N9—C9	167.0 (4)
O4—C3—C4—N4	168.5 (4)	N10—Cu4—N9—C9	−0.7 (4)
N5—C5—C6—N6	5.8 (6)	O17—Cu4—N9—C9	−95.5 (3)
O6—C5—C6—N6	−176.2 (4)	O7—Cu4—N9—O9	−2.8 (3)
N7—C7—C8—N8	−10.1 (5)	N10—Cu4—N9—O9	−170.5 (3)
O8—C7—C8—N8	170.5 (4)	O17—Cu4—N9—O9	94.8 (3)
O10—C9—C10—N10	168.9 (4)	C9—C10—N10—Cu4	9.8 (5)
N9—C9—C10—N10	−10.9 (6)	C1—N1—O1—Cu1	11.7 (4)
O2—C1—N1—O1	−0.6 (6)	Cu5—N1—O1—Cu1	−159.6 (2)
C2—C1—N1—O1	179.4 (4)	C1—N1—O1—Tb1	176.5 (3)
O2—C1—N1—Cu5	171.2 (3)	Cu5—N1—O1—Tb1	5.2 (5)
C2—C1—N1—Cu5	−8.8 (5)	N1—C1—O2—Cu1	−10.6 (5)
O9—Cu5—N1—C1	175.3 (4)	C2—C1—O2—Cu1	169.4 (3)
O10—Cu5—N1—C1	105.8 (6)	C3—N3—O3—Cu2	−5.7 (4)
N2—Cu5—N1—C1	−2.1 (4)	Cu1—N3—O3—Cu2	158.1 (2)
O18—Cu5—N1—C1	−91.7 (4)	C3—N3—O3—Tb1	179.5 (3)
O9—Cu5—N1—O1	−13.6 (3)	Cu1—N3—O3—Tb1	−16.7 (5)
O10—Cu5—N1—O1	−83.1 (6)	N3—C3—O4—Cu2	7.1 (5)
N2—Cu5—N1—O1	169.0 (3)	C4—C3—O4—Cu2	−171.2 (4)
O18—Cu5—N1—O1	79.4 (3)	C5—N5—O5—Cu3	−9.7 (4)
C1—C2—N2—Cu5	−19.1 (5)	Cu2—N5—O5—Cu3	164.1 (2)
O4—C3—N3—O3	−1.0 (6)	C5—N5—O5—Tb1	−165.6 (3)
C4—C3—N3—O3	177.4 (4)	Cu2—N5—O5—Tb1	8.2 (4)
O4—C3—N3—Cu1	−166.2 (3)	N5—C5—O6—Cu3	8.8 (5)
C4—C3—N3—Cu1	12.2 (5)	C6—C5—O6—Cu3	−169.1 (3)
C3—C4—N4—Cu1	3.3 (5)	C7—N7—O7—Cu4	3.2 (4)
O6—C5—N5—O5	0.7 (6)	Cu3—N7—O7—Cu4	−171.6 (2)
C6—C5—N5—O5	178.6 (4)	C7—N7—O7—Tb1	167.2 (3)
O6—C5—N5—Cu2	−173.6 (3)	Cu3—N7—O7—Tb1	−7.7 (5)
C6—C5—N5—Cu2	4.4 (5)	N7—C7—O8—Cu4	−3.7 (5)
O3—Cu2—N5—C5	165.2 (4)	C8—C7—O8—Cu4	175.7 (3)
N6—Cu2—N5—C5	−9.4 (3)	C9—N9—O9—Cu5	−0.7 (4)
O19—Cu2—N5—C5	−97.4 (4)	Cu4—N9—O9—Cu5	169.3 (2)
O3—Cu2—N5—O5	−8.4 (3)	C9—N9—O9—Tb1	177.4 (3)
N6—Cu2—N5—O5	177.0 (3)	Cu4—N9—O9—Tb1	−12.5 (5)
O19—Cu2—N5—O5	88.9 (4)	N9—C9—O10—Cu5	4.2 (5)
C5—C6—N6—Cu2	−12.1 (5)	C10—C9—O10—Cu5	−175.6 (4)
O8—C7—N7—O7	0.3 (6)	Tb1—O11—S1—O14	−110.9 (2)
C8—C7—N7—O7	−179.1 (4)	Tb1—O11—S1—O13	124.81 (18)
O8—C7—N7—Cu3	175.5 (3)	Tb1—O11—S1—O12	6.7 (2)
C8—C7—N7—Cu3	−3.9 (5)	Tb1—O12—S1—O14	111.5 (2)
C7—C8—N8—Cu3	18.0 (4)	Tb1—O12—S1—O13	−125.78 (18)
O10—C9—N9—O9	−2.5 (6)	Tb1—O12—S1—O11	−6.7 (2)
C10—C9—N9—O9	177.3 (4)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O24—H24B···O8	0.84 (2)	2.01 (3)	2.807 (5)	159 (7)
O24—H24A···O11ⁱⁱ	0.84 (2)	2.21 (3)	3.015 (5)	162 (7)
O23—H23B···O13ⁱⁱⁱ	0.85 (2)	2.02 (3)	2.853 (5)	166 (6)
O23—H23A···O4ⁱⁱ	0.84 (2)	1.89 (2)	2.734 (5)	176 (7)
O22—H22B···O23	0.84 (2)	1.89 (3)	2.701 (6)	162 (8)
O22—H22A···O26^iv	0.84 (2)	2.18 (4)	2.968 (9)	155 (8)
O22—H22A···O28ⁱⁱⁱ	0.84 (2)	1.92 (3)	2.733 (9)	161 (8)
O21—H21B···O10^iv	0.83 (2)	1.91 (3)	2.728 (5)	165 (8)
O21—H21A···O18^v	0.84 (2)	1.94 (3)	2.765 (5)	167 (7)
O20—H20B···O11	0.83 (2)	2.14 (3)	2.960 (5)	168 (7)
O20—H20A···O26ⁱ	0.83 (2)	2.09 (3)	2.916 (9)	170 (7)
O20—H20A···O25	0.83 (2)	2.02 (5)	2.719 (9)	142 (7)
O19—H19B···O24^vi	0.84 (2)	2.07 (9)	2.866 (11)	157 (22)
O19—H19A···O24^vii	0.84 (2)	1.72 (7)	2.535 (12)	162 (21)
O18—H18B···O14	0.83 (2)	1.90 (2)	2.732 (5)	173 (7)
O18—H18A···O26ⁱ	0.84 (2)	2.04 (3)	2.857 (9)	163 (7)
O18—H18A···O27	0.84 (2)	1.91 (4)	2.648 (9)	146 (6)
O17—H17B···O6^vi	0.83 (2)	1.90 (2)	2.730 (5)	176 (7)
O17—H17A···O12	0.83 (2)	2.10 (3)	2.905 (5)	163 (6)
O16—H16B···O22	0.84 (2)	1.89 (2)	2.721 (6)	173 (7)
O16—H16A···O17^v	0.84 (2)	1.95 (2)	2.784 (5)	172 (7)
O15—H15B···O16	0.84 (2)	1.86 (2)	2.692 (5)	170 (6)
O15—H15A···O21	0.84 (2)	1.85 (3)	2.668 (5)	166 (6)
N10—H10B···O22^viii	0.91	2.13	2.920 (6)	145
N10—H10A···O20ⁱⁱ	0.91	2.24	2.987 (5)	139
N8—H8B···O12^vi	0.91	2.04	2.937 (5)	168
N8—H8A···O23	0.91	2.20	3.031 (5)	152
N6—H6B···O13^ix	0.91	2.64	3.363 (5)	137
N6—H6B···O24^vi	0.91	2.24	2.984 (6)	139
N6—H6A···O13^v	0.91	2.25	3.158 (5)	175
N4—H4B···O2^x	0.91	2.33	3.182 (5)	156
N4—H4A···O27^v	0.91	2.18	3.037 (9)	156
N4—H4A···O25^x	0.91	2.01	2.789 (9)	143
N2—H2B···O27	0.91	2.55	3.418 (9)	159
N2—H2B···O28ⁱ	0.91	2.08	2.868 (9)	144
N2—H2A···O15^iv	0.91	2.07	2.946 (5)	162

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

Comparison of the structural characteristics (Å, °) of {LnCu₅}³⁺ 15-metallacrown-5 complexes with octacoordinate Ln^III ions and various bidentate anions top

Complex^a	Cu—O/N_eq	Ln—O_eq	Ln—O_aq	Ln···Cu	Cu···Cu	Deviation of Ln^III from Cu₅ plane	LnO₈ geometry^b
Pr-SO₄	1.898 (2)–2.013 (2)	2.4247 (18) -2.4716 (18)	2.495 (2)–2.528 (2)	3.862 (3)–3.923 (2)	4.530 (2)–4.604 (2)	0.459	SAPR-8
Nd-SO₄	1.898 (2)–2.0156 (19)	2.4145 (16)–2.4642 (16)	2.4787 (18)–2.5108 (17)	3.862 (3)–3.915 (4)	4.524 (4)–4.598 (5)	0.452	SAPR-8
Sm-SO₄	1.900 (4)–2.015 (4)	2.398 (3) -2.450 (3)	2.441 (4)–2.484 (4)	3.8539 (9)–3.9083 (8)	4.518 (1)–4.592 (1)	0.439	SAPR-8
Eu-SO₄	1.896 (3)–2.013 (3)	2.389 (3)–2.437 (3)	2.431 (3)–2.467 (3)	3.844 (7)–3.899 (8)	4.504 (8)–4.585 (9)	0.439	SAPR-8
Eu-CO₃	1.886 (14)–2.022 (13)	2.406 (11)–2.493 (11)	2.369 (13)–2.392 (15)	3.890 (2)–3.911 (3)	4.575 (3)–4.589 (3)	0.351	TDD-8
Eu-OAc	1.902 (3)–2.041 (2)	2.440 (4)–2.515 (2)	2.4057 (18)–2.443 (2)	3.8517 (4)–3.9049 (4)	4.5664 (5)–4.6074 (4)	0.469	TDD-8
Gd-SO₄	1.892 (3)–2.014 (3)	2.378 (3)–2.434 (3)	2.398 (3)–2.452 (3)	3.838 (7)–3.897 (9)	4.501 (8)–4.578 (11)	0.430	SAPR-8
Gd-CO₃	1.898 (2)–2.022 (2)	2.381 (2)–2.484 (2)	2.288 (17)–2.396 (10)	3.8699 (5)–3.9097 (5)	4.5677 (7)–4.5846 (7)	0.337	TDD-8
Gd-OAc	1.890 (12)–2.041 (11)	2.393 (3)–2.438 (9)	2.426 (10)–2.512 (10)	3.845 (2)–3.897 (2)	4.562 (2)–4.602 (2)	0.458	TDD-8
Tb-SO₄	1.890 (4)–2.018 (4)	2.370 (3)–2.430 (3)	2.383 (3)–2.451 (3)	3.8398 (8)–3.8944 (8)	4.501 (1)–4.577 (1)	0.427	SAPR-8
Tb-OAc	1.889 (11)–2.036 (11)	2.383 (9)–2.431 (9)	2.409 (10)–2.488 (10)	3.840 (2)–3.896 (2)	4.562 (2)–4.598 (2)	0.445	TDD-8
Dy-SO₄	1.8908 (18)–2.0206 (19)	2.3640 (15) -2.4234 (15)	2.3665 (17)–2.4334 (17)	3.834 (2)–3.889 (2)	4.493 (2)–4.573 (2)	0.424	SAPR-8
Dy-CO₃	1.898 (3)–2.022 (3)	2.382 (3)–2.469 (3)	2.27 (2)–2.380 (8)	3.8715 (5)–3.9016 (6)	4.5645 (7)–4.5797 (8)	0.354	TDD-8
Ho-SO₄	1.887 (3)–2.016 (3)	2.356 (2)–2.416 (2)	2.357 (2)–2.417 (2)	3.827 (2)–3.884 (2)	4.485 (2)–4.565 (2)	0.422	SAPR-8
Ho-CO₃	1.898 (2)–2.022 (2)	2.374 (2)–2.475 (2)	2.30 (3)–2.374 (12)	3.8670 (5)–3.9021 (5)	4.5583 (7)–4.5808 (7)	0.330	TDD-8

Notes: (a) Complex Tb-SO₄ is 1; Ln-SO₄ correspond to the [LnCu₅(GlyHA)₅(SO₄)(H₂O)_6.5]₂(SO₄) series with Ln = Pr, Nd, Sm, Eu, Gd, Dy and Ho described in (Pavlishchuk et al., 2011); Ln-CO₃ are [LnCu₅(GlyHA)₅(CO₃)(NO₃)(H₂O)₅] with Ln = Eu, Gd, Dy and Ho described in Pavlishchuk et al. (2019) and Stemmler et al. (1999); Ln-OAc are [LnCu₅(GlyHA)₅(OAc)(H₂O)₅](NO₃)₂ Ln = Eu, Gd and Tb described in Katkova et al. (2015a) and Meng et al. (2016). (b) LnO₈ geometries: SAPR-8 = square antiprism (D4d) and TDD-8 = triangular dodecahedron (D₂_d).

Continuous shape calculations for octacoordinated Ln³⁺ ions in 1 obtained with Shape 2.1 software (Casanova et al., 2005) top

	OP-8	HPY-8	HBPY-8	CU-8	SAPR-8	TDD-8	JGBF-8	JETBPY-8
Pr–SO₄	30.846	22.755	15.952	11.561	2.215	2.397	13.029	25.482
Nd–SO₄	30.677	22.888	15.968	11.587	2.141	2.364	13.033	25.516
Sm–SO₄	30.387	22.903	15.951	11.562	2.020	2.311	13.013	25.752
Eu–SO₄	30.516	23.164	16.270	11.783	1.952	2.363	13.190	25.864
Gd–SO₄	30.465	23.110	16.032	11.570	1.907	2.269	13.151	26.121
Tb–SO₄	30.381	23.117	16.159	11.666	1.854	2.322	13.140	26.276
Dy–SO₄	30.357	23.195	16.112	11.603	1.799	2.254	13.168	26.433
Ho–SO₄	30.272	23.212	16.095	11.588	1.761	2.247	13.186	26.496

Octacoordinated ions: OP-8 = octagon (D₈_h); HPY-8 = heptagonal pyramid (C₇_v); HBPY-8 = hexagonal bipyramid (D₆_h); CU-8 = cube (O_h); SAPR-8 = square antiprism (D₄_d); TDD-8 = triangular dodecahedron (D₂_d); JGBF-8 = Johnson gyrobifastigium J26 (D₂_d); JETBPY-8 = Johnson elongated triangular bipyramid J14 (D₃_h).

Acknowledgements

This work was supported partly by the Ministry of Education and Science of Ukraine: Grant of the Ministry of Education and Science of Ukraine for perspective development of a scientific direction `Mathematical sciences and natural sciences' at Taras Shevchenko National University of Kyiv. This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under Grant No. CHE 1625543 (funding for the single-crystal X-ray diffractometer). AWA thanks Drexel University for support.

Funding information

Funding for this research was provided by: National Science Foundation, Division of Materials Research (grant No. CHE 1625543 to M. Zeller); National Research Foundation of Ukraine (grant No. 2020.02/0202 to A. V. Pavlishchuk).

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Bruker (2018). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. 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
Dhers, S., Feltham, H. L. C., Rouzières, M., Clérac, R. & Brooker, S. (2016). Dalton Trans. 45, 18089–18093. Web of Science CSD CrossRef CAS PubMed 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
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Jankolovits, J., Andolina, C. M., Kampf, J. W., Raymond, K. N. & Pecoraro, V. L. (2011). Angew. Chem. 123, 9834–9838. CrossRef Google Scholar
Katkova, M. A., Zabrodina, G. S., Muravyeva, M. S., Khrapichev, A. A., Samsonov, M. A., Fukin, G. K. & Ketkov, S. Yu. (2015a). Inorg. Chem. Commun. 52, 31–33. Web of Science CSD CrossRef CAS Google Scholar
Katkova, M. A., Zabrodina, G. S., Muravyeva, M. S., Shavyrin, A. S., Baranov, E. V., Khrapichev, A. A. & Ketkov, S. Y. (2015b). Eur. J. Inorg. Chem. pp. 5202–5208. Web of Science CSD CrossRef 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
Kremlev, K. V., Samsonov, M. A., Zabrodina, G. S., Arapova, A. V., Yunin, P. A., Tatarsky, D. A., Plyusnin, P. E., Katkova, M. A. & Ketkov, S. Y. (2016). Polyhedron, 114, 96–100. CSD CrossRef CAS Google Scholar
Lim, C., Jankolovits, J., Kampf, J. & Pecoraro, V. (2010). Chem. Asian J. 5, 46–49. Web of Science CSD CrossRef PubMed CAS Google Scholar
Liu, J.-L., Chen, Y.-C. & Tong, M.-L. (2018). Chem. Soc. Rev. 47, 2431–2453. CrossRef CAS PubMed Google Scholar
Maity, M., Majee, M. C., Kundu, S., Samanta, S. K., Sañudo, E. C., Ghosh, S. & Chaudhury, M. (2015). Inorg. Chem. 54, 9715–9726. CrossRef CAS PubMed Google Scholar
Meng, Y., Yang, H., Li, D., Zeng, S., Chen, G., Li, S. & Dou, J. (2016). RSC Adv. 6, 47196–47202. CSD CrossRef CAS Google Scholar
Muravyeva, M. S., Zabrodina, G. S., Samsonov, M. A., Kluev, E. A., Khrapichev, A. A., Katkova, M. A. & Mukhina, I. V. (2016). Polyhedron, 114, 165–171. CSD CrossRef CAS Google Scholar
Ostrowska, M., Fritsky, I. O., Gumienna-Kontecka, E. & Pavlishchuk, A. V. (2016). Coord. Chem. Rev. 327–328, 304–332. Web of Science CrossRef CAS Google Scholar
Pavlishchuk, A., Naumova, D., Zeller, M., Calderon Cazorla, S. & Addison, A. W. (2019). Acta Cryst. E75, 1215–1223. CSD CrossRef IUCr Journals Google Scholar
Pavlishchuk, A. V., Kolotilov, S. V., Fritsky, I. O., Zeller, M., Addison, A. W. & Hunter, A. D. (2011). Acta Cryst. C67, m255–m265. Web of Science CSD CrossRef IUCr Journals Google Scholar
Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Lofland, S. E. & Addison, A. W. (2018). Eur. J. Inorg. Chem. pp. 3504–3511. Web of Science CSD CrossRef Google Scholar
Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Lofland, S. E., Kiskin, M. A., Efimov, N. N., Ugolkova, E. A., Minin, V. V., Novotortsev, V. M. & Addison, A. W. (2017b). Eur. J. Inorg. Chem. pp. 4866–4878. Web of Science CrossRef Google Scholar
Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Lofland, S. E., Thompson, L. K., Addison, A. W. & Hunter, A. D. (2017a). Inorg. Chem. 56, 13152–13165. Web of Science CSD CrossRef CAS PubMed Google Scholar
Pavlishchuk, A. V., Kolotilov, S. V., Zeller, M., Thompson, L. K. & Addison, A. W. (2014). Inorg. Chem. 53, 1320–1330. Web of Science CSD CrossRef CAS PubMed Google Scholar
Pavlishchuk, A. V. & Pavlishchuk, V. V. (2020). Theor. Exp. Chem. 56, 1–25. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stemmler, A. J., Kampf, J. W., Kirk, M. L., Atasi, B. H. & Pecoraro, V. L. (1999). Inorg. Chem. 38, 2807–2817. Web of Science CSD CrossRef PubMed CAS Google Scholar
Wang, J., Li, Q.-W., Wu, S.-G., Chen, Y.-C., Wan, R.-C., Huang, G.-Z., Liu, Y., Liu, J.-L., Reta, D., Giansiracusa, M. J., Wang, Z.-X., Chilton, N. F. & Tong, M.-L. (2021). Angew. Chem. Int. Ed. 60, 5299–5306. CSD CrossRef CAS Google Scholar
Wang, J., Ruan, Z.-Y., Li, Q.-W., Chen, Y.-C., Huang, G.-Z., Liu, J.-L., Reta, D., Chilton, N. F., Wang, Z.-X. & Tong, M.-L. (2019). Dalton Trans. 48, 1686–1692. Web of Science CSD CrossRef CAS PubMed Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, S.-G., Ruan, Z.-Y., Huang, G.-Z., Zheng, J.-Y., Vieru, V., Taran, G., Wang, J., Chen, Y.-C., Liu, J.-L., Ho, L. T. A., Chibotaru, L. F., Wernsdorfer, W., Chen, X.-M. & Tong, M.-L. (2021). Chem, 7, 982–992. CSD CrossRef CAS Google Scholar
Zabrodina, G. S., Katkova, M. A., Samsonov, M. A. & Ketkov, S. Y. (2018). Z. Anorg. Allg. Chem. 644, 907–911. CSD CrossRef CAS Google Scholar
Zaleski, C. M., Depperman, E. C., Kampf, J. W., Kirk, M. L. & Pecoraro, V. L. (2006). Inorg. Chem. 45, 10022–10024. CSD CrossRef PubMed CAS Google Scholar
Zaleski, C. M., Lim, C.-S., Cutland-Van Noord, A. D., Kampf, J. W. & Pecoraro, V. L. (2011). Inorg. Chem. 50, 7707–7717. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zangana, K. H., Pineda, E. M., Vitorica-Yrezabal, I. J., McInnes, E. J. L. & Winpenny, R. E. P. (2014). Dalton Trans. 43, 13242–13249. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zheng, Y.-Z., Zhou, G.-J., Zheng Z., & Winpenny, R. E. P. (2014). Chem. Soc. Rev. 43, 1462–1475. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.