Crystal structure of the BaII-based CoII-containing one-dimensional coordination polymer poly[[aqua{μ4-2,2′-[(4,10-dimethyl-1,4,7,10-tetra­aza­cyclo­dodecane-1,7-di­yl)bis(methylidene)]bis­(4-oxo-4H-pyran-3-olato)}­perchloratocobaltbarium] perchlorate]

Paoli, P.; Macedi, E.; Rossi, P.; Giorgi, L.; Formica, M.; Fusi, V.

doi:10.1107/S2056989017015638

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 73| Part 12| December 2017| Pages 1806-1811

https://doi.org/10.1107/S2056989017015638

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Crystal structure of the Ba^II-based Co^II-containing one-dimensional coordination polymer poly[[aqua{μ₄-2,2′-[(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylidene)]bis(4-oxo-4H-pyran-3-olato)}perchloratocobaltbarium] perchlorate]

Paola Paoli,^a Eleonora Macedi,^a ^* Patrizia Rossi,^a Luca Giorgi,^b Mauro Formica ^b and Vieri Fusi ^b

^aDepartment of Industrial Engineering, University of Firenze, via Santa Marta 3, I-50139 Firenze, Italy, and ^bDepartment of Pure and Applied Sciences, Lab of Supramolecular Chemistry, University of Urbino, via della Stazione, 4, I-61029 Urbino, Italy
^*Correspondence e-mail: eleonora.macedi@unifi.it

Edited by O. Büyükgüngör, Ondokuz Mayıs University, Turkey (Received 30 September 2017; accepted 26 October 2017; online 3 November 2017)

The title compound, {[Ba{Co(H_-2L1)}(ClO₄)(H₂O)]ClO₄}_n, L1 = 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane, is a one-dimensional coordination polymer. The asymmetric unit consists of a {Ba[Co(H_–2L1)](ClO₄)(H₂O)}⁺ cationic fragment and a non-coordinating ClO₄⁻ anion. In the neutral [Co(H_–2L1)] moiety, the cobalt ion is hexacoordinated in a trigonal–prismatic fashion by the surrounding N₄O₂ donor set. The Ba²⁺ ion is nine-coordinated and exhibits a distorted [BaO₉] monocapped square-antiprismatic geometry, the six oxygen atoms coming from three distinct [Co(H_–2L1)] moieties, while the remaining three vertices are occupied by the oxygen atoms of a bidentate perchlorate anion and a water molecule. A barium–μ₂-oxygen motif develops along the a axis, connecting symmetry-related dinuclear Ba^II–Co^II cationic fragments in a wave-like chain, forming a one-dimensional metal coordination polymer. Non-coordinating ClO₄⁻ anions are located in the space between the chains. Weak C—H⋯O hydrogen bonds involving both coordinating and non-coordinating perchlorate anions build the whole crystal architecture. To our knowledge, this is the first example of a macrocyclic ligand forming a Ba^II-based one-dimensional coordination polymer, containing Co^II ions surrounded by a N₄O₂ donor set.

Keywords: crystal structure; coordination polymer; barium; cobalt; macrocycle.

CCDC reference: 1582341

1. Chemical context

Metal coordination polymers (CPs) have witnessed continuous growth, owing to their fascinating structural diversity in terms of architecture and topology and also their numerous potential applications, such as gas storage (Banerjee et al., 2016 ; Fracaroli et al., 2014 ; Sumida et al., 2012 ; Suh et al., 2012 ), chemical sensing (Campbell et al., 2015 ; Hu et al., 2014 ; Wang et al., 2013 ; Kreno et al., 2012 ), catalysis (Chughtai et al., 2015 ; Mo et al., 2014 ; Yoon et al., 2012 ; Liu, Xuan et al., 2010 ) and so forth. Recently, the interest in alkaline-earth metal ion-based CPs has been growing due to their unusual advantages such as low toxicity, wide distribution and low cost, which are of benefit for applications in the field of materials science (Raja et al., 2014 ; Foo et al., 2012 , 2013 ; Xiao et al., 2012 ).

According to a Cambridge Structural Database (CSD, Version 5.38, May 2017; Groom et al., 2016 ) search, alkaline-earth metal-based CPs are less common compared to the reported transition metal and rare-earth metal CPs (Cai et al., 2017 ). Indeed, the study of alkaline-earth–metal systems is limited by challenges in the synthesis (Lian et al., 2016 ; Douvali et al., 2015 ; Mali et al., 2015 ; Chakraborty et al., 2014 ; Zhang, Huang et al., 2012 ; Liu, Tsao et al., 2010 ), the main reason being the variable coordination numbers (the most preferred coordination numbers are six for magnesium, six to eight for calcium, and six to twelve for strontium and barium), which lead to uncontrolled coordination geometries around the metal centre (Cai et al., 2016 ; Feng et al., 2015 ; Shi et al., 2015 ; Zheng et al., 2015 ; Jia et al., 2014 ; Zhang, Yuan et al., 2013 ; Smith et al., 2013 ; Zhai et al., 2013 ; Zhang, Guo et al., 2013 ; Deng et al., 2012 ; Foo et al., 2012; Xiao et al., 2012; Xie et al., 2012 ; Zhang, Luo et al., 2012 ; Jing et al., 2010 ; Zhang et al., 2010 ; Li et al., 2009 ).

Besides, the ability of a system to bind alkaline-earth metal ions in aqueous solution is highly desirable and can be achieved thanks to the presence of oxygenated ligands and the preorganization of the receptor, which satisfies the need for a high coordination number without specific coordination requirements.

Ligand L1 {4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane} is a Maltol-based macrocycle (Amatori et al., 2012 ) and is able to form discrete heteropolynuclear complexes. It has already proved to able form a Co^II species (Borgogelli et al., 2013 ) that is able to bind hard metal ions such as Ln^III (Ln = Gd, Eu) and Na(I). In the case of Ln^III ions, heterotrinuclear Co^II–Ln^III–Co^II systems form, where the Co^II cation preorganizes the system and two Co^II species are involved in the coordination of one Ln^III ion (Benelli et al., 2013 ; Rossi et al., 2017 ). In the case of the alkaline ion, a heterodinuclear complex forms, involving only one Co^II species (Borgogelli et al., 2013).

Herein we present a Ba^II–Co^II heterodinuclear metal coordination compound of L1, where a one-dimensional wave-like infinite array of barium ions bridges the [Co(H_–2L1)] moieties through a barium–μ₂-oxygen motif. This is the first time that L1 has proven able to form a coordination polymer and, to our knowledge, this is the first example of a macrocyclic ligand forming a Ba^II-based 1D-CP containing Co^II ions surrounded by an N₄O₂ donor set.

2. Structural commentary

The title compound is the Ba^II-based Co^II-containing 1D-CP of L1 of formula {{Ba[Co(H_–2L1)](ClO₄)(H₂O)}·ClO₄}_n and crystallizes in the monoclinic system in space group P2₁/n, with a {Ba[Co(H_–2L1)](ClO₄)(H₂O)}⁺ cationic fragment (Fig. 1) and a (ClO₄)⁻ anion in the asymmetric unit.

Figure 1
The molecular structure of the {Ba[Co(H_–2L1)](ClO₄)(H₂O)}⁺ cationic fragment, with the atom labelling and 30% probability displacement ellipsoids. Only one component of the disordered perchlorate anion and water molecule is shown. H atoms have been omitted for clarity. Symmetry codes: (i) −x + 1, −y, −z; (ii) −x + 2, −y, −z.

In the neutral [Co(H_-2L1)] moiety, the Co²⁺ ion is hexacoordinated and exhibits a distorted trigonal–prismatic geometry (Muetterties & Guggenberger, 1974 ), where the cobalt ion is surrounded by four nitrogen atoms of the macrocyclic base and two deprotonated hydroxyl oxygen atoms provided by both maltolate rings of the ligand. In the distorted trigonal prism, the O1,N2,N3/O4,N1,N4 atoms define the two triangular faces, which are parallel within 12.51 (11)° (Fig. 2). The cobalt ion is displaced 1.0971 (5) Å above the mean plane described by the four nitrogen atoms of the tetraazamacrocycle [maximum deviation of 0.068 (4) Å for N3] and falls, together with the Co—N(CH₃) and Co—O bond distances (Table 1), in the expected range for Co-[12]aneN₄ complexes where the cobalt ion is hexacoordinated with a N₄O₂ donor set (Fig. 3, left). The Co—N(Maltol) bond distances, instead, are longer (Table 1) than the Co—N(CH₃) ones and longer with respect to those reported for other Co–L1 complexes [Co—N(Maltol): range 2.26–2.44; Co—N(CH₃) range: 2.13–2.19; Benelli et al., 2013; Borgogelli et al., 2013; Rossi et al., 2017].

Table 1
Selected bond lengths and angles (Å, °)

Co1—N1	2.199 (3)
Co1—N2	2.414 (3)
Co1—N3	2.220 (4)
Co1—N4	2.344 (3)
Co1—O1	2.044 (3)
Co1—O4	2.075 (3)
Ba1—O1	2.688 (3)
Ba1—O2	2.861 (3)
Ba1—O4	2.690 (3)
Ba1—O5	2.814 (3)
Ba1—O1W	2.774 (14)/2.75 (2)/2.972 (15)^a
Ba1—O11	2.853 (19)/3.154 (13)^b
Ba1—O12	2.955 (18)/2.863 (12)^b
N1⋯N3	3.903 (5)
N2⋯N4	4.164 (5)
Ba1⋯Ba1ⁱ	4.9123 (4)
Ba1⋯O2ⁱ	2.860 (3)
O2⋯O2ⁱ	2.932 (4)
Ba1⋯Ba1ⁱⁱ	4.8443 (4)
Ba1⋯O5ⁱⁱ	2.900 (3)
O5⋯O5ⁱⁱ	3.033 (4)
Ba1ⁱ⋯Ba1ⁱⁱ	8.8965 (4)

Ba1—O1—Co1	113.82 (12)
Ba1—O4—Co1	112.64 (11)
Ba1—O2—Ba1ⁱ	118.34 (10)
Ba1—O5—Ba1ⁱⁱ	115.92 (10)
Symmetry codes: (i) = −x + 1, −y, −z; (ii) = −x + 2, −y, −z. Notes: (a) the values refer to O1WA/B/C atoms, respectively; (b) the values refer to the A/B oxygen atoms, respectively, of the disordered perchlorate anion (see Refinement section).

Figure 2
Coordination polyhedra around cobalt (left) and barium (right) ions. [Symmetry codes: (i) −x + 1, −y, −z; (ii) −x + 2, −y, −z.]

Figure 3
Fragments searched in the CSD.

The conformation of the [12]aneN₄ macrocycle is the usual [3333]C-corners one (Meurant, 1987 ) with the trans nitrogen distances in agreement with those reported in the CSD for this conformation type, but the N2⋯N4 distance being longer than the N1⋯N3 one by 0.26 Å (Table 1), as found only in 36% of cases. This is probably due to the fact that the Maltol units linked to atoms N2 and N4 are involved in chelate six-membered rings, which stiffen the system and force those nitrogen atoms to move farther apart.

The two maltolate rings are almost orthogonal to each other (dihedral angle between ring mean planes about 71°); both rings form similar angles (about 55°) with the mean plane N1,N2,N3,N4. The dimensions of the binding area defined by the four oxygen donor atoms of the ligand, as roughly estimated by the distances separating the opposite O1⋯O5 and O2⋯O4 atoms, are quite similar (about 4.5 Å).

Tha Ba²⁺ ion is nine-coordinated and exhibits a distorted [BaO₉] monocapped square-antiprismatic geometry (Guggenberger & Muetterties, 1976 ), Fig. 2, where the barium cation is surrounded by six oxygen atoms from three distinct [Co(H_–2L1)] moieties {four from two maltolate groups of a moiety and two from the carbonyl groups belonging to two distinct symmetry-related moieties, O2ⁱ and O5ⁱⁱ [symmetry codes: (i) −x + 1, −y, −z; (ii) −x + 2, −y, −z]}, an oxygen atom of a disordered water molecule and two oxygen atoms of a disordered perchlorate anion, the latter acting as a bidentate ligand (Fig. 1). In the distorted monocapped square antiprism, the O5 oxygen atom caps the O5ⁱⁱ, O4, O1W, O12 face (Fig. 2, right). All bond distances (Table 1) are in agreement with data found in the CSD.

The Ba²⁺ and Co²⁺ cations are located 3.9799 (7) Å apart from each other, the line connecting them being normal to the mean plane described by the four nitrogen atoms of the macrocycle [angle value: 87.59 (7)°; Fig. 1]. As for the bridged Co–O–Ba moiety (Fig. 3, right), while the Ba—O and Co—O bond distances and the Ba⋯Co distance are in agreement with those found in the CSD, the corresponding Ba—O—Co angles (Table 1) are outside the observed range (89.5–111.4°).

3. Supramolecular features

The title compound forms wave-like chains with a repeating unit comprising a dinuclear Ba^II–Co^II cationic fragment with associated coordinating water molecules and perchlorate ions (Fig. 4). Non-coordinating ClO₄⁻ anions are located in the space between the chains.

Figure 4
Wave-like one-dimensional Ba^II-based coordination polymer that develops along the a axis. The oxygen and barium atoms belonging to the barium–μ₂-oxygen motif are depicted in ball and stick mode. Only one component of the disordered perchlorate anion and water molecule is shown. H atoms and the non-coordinating ClO₄⁻ anions have been omitted for clarity. [Symmetry codes: (i) −x + 1, −y, −z; (ii) −x + 2, −y, −z.]

A barium–μ₂-oxygen motif develops along the a axis, the angle between the two mean planes formed by atoms Ba, O2, Baⁱ and O2ⁱ and atoms Ba, O5, Baⁱⁱ and O5ⁱⁱ is about 40° [symmetry codes: (i) −x + 1, −y, −z; (ii) −x + 2, −y, −z], Fig. 4. The Ba—O bond distances, the O⋯O and Ba⋯Ba distances and the Ba—O—Ba angle values within each plane and the Baⁱ⋯Baⁱⁱ distance (Table 1) are in agreement with data reported in the CSD.

Weak C—H⋯O hydrogen bonds (Desiraju & Steiner, 1999 ) involving both coordinating and non-coordinating perchlorate anions build the whole crystal architecture (Table 2). Distinct 1D-CPs are held together by weak C—H⋯O interactions between the coordinating perchlorate anions belonging to a CP and methylene hydrogen atoms belonging to the adjacent CPs (Fig. 5).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O21	0.99	2.91/2.62	3.877 (12)/3.60 (3)	165.3/172.3
C3—H3A⋯O22ⁱⁱⁱ	0.99	2.65/2.48	3.577 (11)/3.46 (3)	155.7/166.7
C8—H8B⋯O13^iv	0.99	2.49/2.59	3.46 (2)/3.524 (15)	168.5/156.6
C22—H22⋯O21^v	0.95	2.62/2.66	3.482 (11)/3.51 (3)	151.4/149.2
C22—H22⋯O23^v	0.95	2.57/2.54	3.455 (11)/3.39 (4)	155.1/149.9
Symmetry codes: (iii) −x + $[{3\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (v) x − 1, y, z. Note: the first and second values for each entry refer to the A and B oxygen atoms, respectively, of the disordered perchlorate anion (see Refinement section).

Figure 5
Adjacent CPs connected via hydrogen bonds involving the coordinating ClO₄⁻ anions as viewed along the b axis. The coordinating ClO₄⁻ anions are depicted in ball and stick mode. Hydrogen bonds are depicted as light-blue dotted lines. Only H atoms involved in the C—H⋯O interactions and only one component of the disordered perchlorate anion and water molecule are shown.

The non-coordinating perchlorate anion connects, via a net of weak hydrogen bonds, three {Ba[Co(H_-2L1)](ClO₄)(H₂O)}⁺ cationic fragments belonging to two different 1D-CPs wave-like disposed along the b axis (Fig. 6).

Figure 6
Crystal packing of the title compound as viewed along the a axis. The non-coordinating ClO₄⁻ anions are depicted in ball and stick mode. Hydrogen bonds involving the non-coordinating ClO₄⁻ anion and two {Ba[Co(H_–2L1)](ClO₄)(H₂O)}⁺ cationic fragments on the same plane are depicted in light-blue dotted lines. Hydrogen bonds involving the non-coordinating ClO₄⁻ anion and a {Ba[Co(H_–2L1)](ClO₄)(H₂O)}⁺ cationic fragment out of plane (symmetry operation x − 1, y, z) are depicted in grey dotted lines. Only H atoms involved in the C—H⋯O interactions and only one component of the disordered perchlorate anion and water molecule are shown.

4. Database survey

Five structures containing L1 were found in a search of the CSD (Version 5.38, May 2017; Groom et al., 2016), three of them containing Co^II: a hetero-trinuclear Gd^III–Co^II–Gd^III dimer, a hetero-dinuclear Na^I–Co^II complex and a Co^II complex (Benelli et al., 2013; Amatori et al., 2012; Borgogelli et al., 2013). In addition, our group recently published the corresponding hetero-trinuclear Eu–Co–Eu dimer (Rossi et al., 2017).

A general search for structures containing both Co^II and Ba^II ions revealed 61 hits, 20 of which are polymeric structures formed by organic ligands containing both oxygen and nitrogen donor atoms and only two being 1D-CPs. It is noteworthy that none of the 20 structures contains either macrocyclic ligands or an N₄O₂ donor set around the Co^II ion. In eight out of those 20 polymeric structures, the Ba^II and Co^II ions are bridged by oxygen atoms and ten out of 20 show oxygen-bridged Ba^II ions (only eight forming an infinite chain). Finally, only six out of the 20 polymeric structures contain both oxygen-bridged Ba^II ions and oxygen-bridged Ba^II and Co^II ions.

All these data suggest that structures containing both oxygen-bridged Ba^II ions and oxygen-bridged Ba^II and Co^II ions are not common and that no Ba^II-based 1D-CPs formed by macrocyclic ligands and containing Co^II ions surrounded by an N₄O₂ donor set are present in the CSD.

5. Synthesis and crystallization

Compound L1 was obtained following the synthetic procedure previously reported (Amatori et al., 2012).

To obtain the Ba^II-based Co^II-containing 1D-CP of L1, {{Ba[Co(H_–2L1)](ClO₄)(H₂O)}·ClO₄}_n, 0.1 mmol of CoCl₂· 6H₂O in water (10 mL) were added to an aqueous solution (20 mL) containing 0.1 mmol of L1·3HClO₄·H₂O. The solution was adjusted to pH 7 with 0.1 M N(CH₃)₄OH and then 0.05 mmol of BaCl₂· 2H₂O were added. The solution was saturated with NaClO₄. The Ba^II–Co^II 1D-CP of L1 quickly precipitated as a microcrystalline pink solid. Crystals suitable for X-ray analysis were instead obtained by slow evaporation of a more diluted aqueous solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All hydrogen atoms of the macrocycle were positioned geometrically and refined as riding with C—H = 0.95–0.99 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms. Both perchlorate anions are disordered, all oxygen and chlorine atoms were set in double positions [anion 1: Cl1A/B, O11A/B, O12A/B, O13A/B, O14A/B, occupancy factor: 0.40 (3) and 0.60 (3); anion 2: Cl2A/B, O21A/B, O22A/B, O23A/B, O24A/B, occupancy factor: 0.78 (3) and 0.22 (3)]. The water molecule is disordered over three positions [SUMP command was used, occupancies 0.49 (3), 0.27 (3) and 0.24 (3)], the hydrogen atoms were not found in the Fourier-difference map and they were not introduced in the refinement. All non-hydrogen atoms were anisotropically refined: as for the disordered perchlorate anions, the SIMU instruction was used to restrain the anisotropic displacement parameters of the disordered atoms, while the ISOR instruction was used to model the disordered water oxygen atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[BaCo(C₂₂H₂₈N₄O₆)(ClO₄)(H₂O)]·ClO₄
M_r	857.67
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	8.8965 (2), 18.0995 (4), 19.0103 (6)
β (°)	94.572 (2)
V (Å³)	3051.34 (14)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.08
Crystal size (mm)	0.45 × 0.38 × 0.27

Data collection
Diffractometer	Rigaku OD Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd., Abingdon, UK.]$ ). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
T_min, T_max	0.884, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15496, 6966, 5315
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.103, 1.06
No. of reflections	6966
No. of parameters	519
No. of restraints	133
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.72
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction Ltd., Abingdon, UK.]$ ), SIR2014 (Burla, 2015 ), SHELXL2014/7 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1582341

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017015638/bq2404sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015638/bq2404Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017015638/bq2404Isup3.mol

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SIR2014 (Burla, 2015); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXL2014/7 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015).

Poly[[aqua{µ₄-2,2'-[(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylidene)]bis(4-oxo-4H-pyran-3-olato)}perchloratocobaltbarium] perchlorate] top

Crystal data top

[BaCo(C₂₂H₂₈N₄O₆)(ClO₄)(H₂O)]ClO₄	F(000) = 1708
M_r = 857.67	D_x = 1.867 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.8965 (2) Å	Cell parameters from 4989 reflections
b = 18.0995 (4) Å	θ = 2.2–27.7°
c = 19.0103 (6) Å	µ = 2.08 mm⁻¹
β = 94.572 (2)°	T = 120 K
V = 3051.34 (14) Å³	Prism, pink
Z = 4	0.45 × 0.38 × 0.27 mm

Data collection top

Rigaku OD Xcalibur, Sapphire3 diffractometer	6966 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	5315 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 16.4547 pixels mm^-1	θ_max = 29.0°, θ_min = 2.2°
ω scans	h = −12→11
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −22→22
T_min = 0.884, T_max = 1.000	l = −22→24
15496 measured reflections

Refinement top

Refinement on F²	133 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.103	w = 1/[σ²(F_o²) + (0.037P)² + 2.9358P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
6966 reflections	Δρ_max = 1.00 e Å⁻³
519 parameters	Δρ_min = −0.72 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba1	0.75388 (3)	0.05421 (2)	0.01055 (2)	0.03237 (9)
Co1	0.75301 (6)	0.26481 (3)	0.07072 (3)	0.02836 (14)
O1	0.6344 (3)	0.19069 (15)	0.00703 (16)	0.0351 (7)
N1	0.9308 (4)	0.33476 (19)	0.03199 (19)	0.0336 (8)
C1	0.5130 (6)	0.3782 (3)	0.1078 (3)	0.0545 (14)
H1A	0.4189	0.3897	0.1300	0.065*
H1B	0.5870	0.4177	0.1210	0.065*
O2	0.4340 (3)	0.07423 (16)	−0.00434 (18)	0.0400 (8)
N2	0.6147 (4)	0.35215 (19)	−0.00548 (19)	0.0350 (8)
C2	0.4817 (5)	0.3772 (3)	0.0300 (3)	0.0461 (12)
H2A	0.3957	0.3438	0.0172	0.055*
H2B	0.4530	0.4275	0.0133	0.055*
O3	0.3318 (3)	0.26420 (17)	−0.11008 (16)	0.0374 (7)
N3	0.5736 (4)	0.3060 (2)	0.1354 (2)	0.0389 (9)
C3	0.7199 (5)	0.4133 (3)	−0.0140 (3)	0.0445 (11)
H3A	0.7282	0.4440	0.0292	0.053*
H3B	0.6818	0.4449	−0.0541	0.053*
O4	0.8695 (3)	0.16663 (15)	0.09010 (15)	0.0340 (7)
N4	0.8905 (4)	0.30110 (18)	0.17530 (19)	0.0324 (8)
C4	0.8729 (5)	0.3827 (3)	−0.0275 (3)	0.0434 (11)
H4A	0.8650	0.3537	−0.0718	0.052*
H4B	0.9442	0.4239	−0.0330	0.052*
O5	1.0650 (3)	0.05816 (16)	0.05118 (17)	0.0406 (8)
C5	0.9983 (5)	0.3822 (2)	0.0890 (3)	0.0422 (11)
H5A	0.9293	0.4240	0.0962	0.051*
H5B	1.0941	0.4029	0.0746	0.051*
O6	1.1536 (4)	0.16710 (18)	0.23669 (17)	0.0462 (8)
C6	1.0284 (5)	0.3412 (3)	0.1570 (3)	0.0414 (11)
H6A	1.1114	0.3055	0.1527	0.050*
H6B	1.0601	0.3764	0.1952	0.050*
C7	0.7907 (5)	0.3517 (3)	0.2110 (3)	0.0426 (11)
H7A	0.7868	0.4003	0.1870	0.051*
H7B	0.8308	0.3593	0.2606	0.051*
C8	0.6351 (5)	0.3191 (3)	0.2090 (3)	0.0442 (12)
H8A	0.6387	0.2719	0.2353	0.053*
H8B	0.5678	0.3533	0.2324	0.053*
C9	0.4532 (6)	0.2506 (3)	0.1367 (3)	0.0589 (15)
H9A	0.4106	0.2409	0.0885	0.088*
H9B	0.4947	0.2047	0.1576	0.088*
H9C	0.3738	0.2691	0.1650	0.088*
C10	1.0466 (5)	0.2848 (3)	0.0060 (3)	0.0500 (13)
H10A	1.0003	0.2536	−0.0319	0.075*
H10B	1.1274	0.3143	−0.0121	0.075*
H10C	1.0886	0.2536	0.0448	0.075*
C11	0.5658 (5)	0.3217 (2)	−0.0762 (2)	0.0395 (10)
H11A	0.5112	0.3604	−0.1049	0.047*
H11B	0.6556	0.3072	−0.1006	0.047*
C12	0.4661 (5)	0.2566 (2)	−0.0707 (2)	0.0318 (9)
C13	0.5033 (4)	0.1960 (2)	−0.0315 (2)	0.0316 (9)
C14	0.3993 (4)	0.1344 (2)	−0.0339 (2)	0.0325 (9)
C15	0.2580 (4)	0.1477 (2)	−0.0733 (2)	0.0310 (9)
H15	0.1815	0.1109	−0.0739	0.037*
C16	0.2308 (5)	0.2098 (3)	−0.1090 (2)	0.0367 (10)
H16	0.1358	0.2158	−0.1349	0.044*
C17	0.9321 (5)	0.2400 (2)	0.2241 (2)	0.0404 (11)
H17A	0.9863	0.2604	0.2673	0.048*
H17B	0.8390	0.2160	0.2380	0.048*
C18	1.0276 (5)	0.1841 (2)	0.1936 (2)	0.0354 (10)
C19	0.9936 (4)	0.1509 (2)	0.1305 (2)	0.0307 (9)
C20	1.0956 (5)	0.0936 (2)	0.1072 (2)	0.0364 (10)
C21	1.2276 (5)	0.0819 (3)	0.1537 (3)	0.0479 (12)
H21	1.3017	0.0479	0.1404	0.058*
C22	1.2496 (6)	0.1168 (3)	0.2147 (3)	0.0536 (14)
H22	1.3377	0.1056	0.2443	0.064*
Cl1A	0.800 (2)	0.1249 (9)	−0.1620 (10)	0.047 (2)	0.40 (3)
O11A	0.658 (2)	0.0849 (10)	−0.1333 (10)	0.047 (3)	0.40 (3)
O12A	0.9088 (18)	0.1007 (11)	−0.1140 (9)	0.052 (3)	0.40 (3)
O13A	0.860 (3)	0.0808 (10)	−0.2136 (12)	0.063 (4)	0.40 (3)
O14A	0.810 (3)	0.2057 (12)	−0.1686 (12)	0.074 (4)	0.40 (3)
Cl1B	0.7844 (14)	0.1280 (7)	−0.1622 (6)	0.0479 (16)	0.60 (3)
O11B	0.6498 (15)	0.1036 (8)	−0.1448 (7)	0.051 (2)	0.60 (3)
O12B	0.8977 (12)	0.1255 (8)	−0.1006 (6)	0.056 (2)	0.60 (3)
O13B	0.8144 (15)	0.0963 (8)	−0.2287 (6)	0.064 (3)	0.60 (3)
O14B	0.750 (2)	0.2000 (8)	−0.1816 (7)	0.076 (3)	0.60 (3)
Cl2A	0.6555 (9)	0.0780 (5)	0.3226 (4)	0.0424 (12)	0.78 (3)
O21A	0.5765 (11)	0.1464 (5)	0.3243 (6)	0.066 (2)	0.78 (3)
O22A	0.7030 (10)	0.0638 (6)	0.3946 (4)	0.062 (2)	0.78 (3)
O23A	0.5501 (11)	0.0220 (4)	0.2981 (6)	0.065 (2)	0.78 (3)
O24A	0.7821 (9)	0.0858 (7)	0.2801 (4)	0.081 (3)	0.78 (3)
Cl2B	0.661 (4)	0.073 (2)	0.317 (2)	0.060 (5)	0.22 (3)
O21B	0.610 (4)	0.1450 (16)	0.2989 (19)	0.053 (6)	0.22 (3)
O22B	0.733 (4)	0.0437 (17)	0.381 (2)	0.065 (5)	0.22 (3)
O23B	0.571 (4)	0.027 (2)	0.272 (2)	0.066 (5)	0.22 (3)
O24B	0.783 (3)	0.049 (2)	0.2882 (15)	0.071 (5)	0.22 (3)
O1WA	0.6542 (14)	0.0192 (9)	0.1411 (7)	0.079 (4)	0.493 (3)
O1WB	0.721 (2)	0.0144 (13)	0.1481 (12)	0.054 (5)	0.268 (3)
O1WC	0.842 (2)	−0.0011 (8)	0.1552 (8)	0.058 (4)	0.239 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.02904 (15)	0.02521 (14)	0.04255 (17)	0.00132 (10)	0.00089 (10)	−0.00540 (11)
Co1	0.0275 (3)	0.0241 (3)	0.0336 (3)	0.0011 (2)	0.0035 (2)	−0.0029 (2)
O1	0.0309 (15)	0.0251 (15)	0.0476 (19)	0.0022 (12)	−0.0083 (13)	−0.0040 (13)
N1	0.0362 (19)	0.0289 (19)	0.037 (2)	−0.0018 (15)	0.0072 (15)	−0.0018 (16)
C1	0.052 (3)	0.049 (3)	0.065 (4)	0.019 (2)	0.015 (3)	−0.007 (3)
O2	0.0332 (16)	0.0273 (16)	0.058 (2)	−0.0005 (12)	−0.0026 (14)	0.0005 (15)
N2	0.0336 (19)	0.031 (2)	0.040 (2)	0.0002 (15)	0.0013 (15)	−0.0011 (16)
C2	0.041 (3)	0.041 (3)	0.056 (3)	0.013 (2)	0.005 (2)	−0.007 (2)
O3	0.0348 (16)	0.0409 (18)	0.0354 (18)	0.0054 (13)	−0.0043 (13)	0.0019 (14)
N3	0.0327 (19)	0.045 (2)	0.040 (2)	0.0041 (17)	0.0069 (16)	−0.0030 (18)
C3	0.057 (3)	0.029 (2)	0.048 (3)	−0.001 (2)	0.000 (2)	0.008 (2)
O4	0.0332 (16)	0.0265 (15)	0.0403 (18)	0.0056 (12)	−0.0102 (12)	−0.0067 (13)
N4	0.0350 (19)	0.0272 (18)	0.035 (2)	0.0008 (15)	0.0057 (15)	−0.0068 (15)
C4	0.047 (3)	0.041 (3)	0.043 (3)	−0.011 (2)	0.008 (2)	0.007 (2)
O5	0.0372 (17)	0.0359 (18)	0.047 (2)	0.0083 (13)	−0.0064 (14)	−0.0124 (15)
C5	0.039 (3)	0.033 (2)	0.054 (3)	−0.008 (2)	0.002 (2)	−0.003 (2)
O6	0.051 (2)	0.0442 (19)	0.040 (2)	0.0051 (15)	−0.0151 (15)	−0.0055 (16)
C6	0.037 (2)	0.036 (2)	0.050 (3)	−0.005 (2)	−0.001 (2)	−0.005 (2)
C7	0.045 (3)	0.041 (3)	0.043 (3)	0.003 (2)	0.007 (2)	−0.015 (2)
C8	0.048 (3)	0.041 (3)	0.046 (3)	0.006 (2)	0.016 (2)	−0.008 (2)
C9	0.047 (3)	0.072 (4)	0.059 (4)	−0.016 (3)	0.016 (3)	−0.007 (3)
C10	0.043 (3)	0.051 (3)	0.059 (3)	0.002 (2)	0.020 (2)	−0.008 (3)
C11	0.045 (3)	0.034 (2)	0.039 (3)	0.000 (2)	0.001 (2)	0.002 (2)
C12	0.034 (2)	0.033 (2)	0.028 (2)	−0.0013 (18)	−0.0015 (17)	0.0001 (18)
C13	0.027 (2)	0.030 (2)	0.038 (2)	0.0033 (17)	−0.0002 (17)	−0.0061 (18)
C14	0.030 (2)	0.033 (2)	0.035 (2)	0.0061 (17)	0.0020 (17)	−0.0075 (19)
C15	0.025 (2)	0.037 (2)	0.029 (2)	−0.0004 (17)	−0.0038 (16)	−0.0079 (18)
C16	0.032 (2)	0.047 (3)	0.031 (2)	0.003 (2)	−0.0022 (17)	−0.003 (2)
C17	0.048 (3)	0.038 (3)	0.035 (3)	0.001 (2)	0.001 (2)	−0.003 (2)
C18	0.034 (2)	0.032 (2)	0.039 (3)	0.0022 (18)	−0.0061 (18)	0.0016 (19)
C19	0.031 (2)	0.026 (2)	0.034 (2)	−0.0013 (16)	−0.0025 (17)	−0.0028 (18)
C20	0.035 (2)	0.029 (2)	0.043 (3)	0.0009 (18)	−0.0058 (19)	−0.002 (2)
C21	0.040 (3)	0.037 (3)	0.064 (4)	0.010 (2)	−0.013 (2)	−0.011 (2)
C22	0.044 (3)	0.049 (3)	0.063 (4)	0.012 (2)	−0.024 (2)	−0.007 (3)
Cl1A	0.049 (4)	0.040 (4)	0.054 (4)	−0.001 (3)	0.010 (3)	0.013 (3)
O11A	0.047 (5)	0.039 (5)	0.055 (5)	−0.001 (4)	0.003 (4)	0.015 (4)
O12A	0.050 (5)	0.049 (5)	0.058 (5)	0.007 (4)	0.003 (4)	0.005 (4)
O13A	0.065 (7)	0.063 (6)	0.062 (7)	0.013 (5)	0.022 (5)	0.006 (5)
O14A	0.073 (8)	0.053 (7)	0.093 (8)	0.006 (7)	−0.019 (7)	0.024 (6)
Cl1B	0.049 (3)	0.057 (3)	0.037 (2)	0.0143 (18)	0.0014 (18)	0.0026 (18)
O11B	0.042 (3)	0.064 (5)	0.049 (4)	0.011 (4)	0.008 (3)	0.006 (4)
O12B	0.049 (3)	0.066 (4)	0.051 (4)	0.009 (4)	−0.006 (3)	0.001 (4)
O13B	0.058 (5)	0.100 (6)	0.035 (4)	0.024 (5)	0.006 (4)	−0.002 (4)
O14B	0.081 (7)	0.063 (5)	0.080 (6)	0.004 (6)	−0.018 (5)	0.025 (4)
Cl2A	0.0529 (19)	0.035 (2)	0.0386 (17)	−0.0050 (18)	−0.0023 (13)	0.0003 (14)
O21A	0.076 (5)	0.045 (3)	0.074 (5)	0.008 (3)	−0.011 (4)	−0.010 (4)
O22A	0.074 (4)	0.065 (5)	0.046 (4)	0.015 (3)	−0.001 (3)	0.007 (3)
O23A	0.082 (4)	0.034 (3)	0.074 (5)	−0.020 (3)	−0.022 (4)	0.006 (4)
O24A	0.097 (4)	0.070 (6)	0.083 (4)	−0.021 (4)	0.046 (3)	−0.011 (4)
Cl2B	0.075 (8)	0.034 (6)	0.069 (9)	0.014 (5)	0.002 (6)	−0.003 (5)
O21B	0.071 (10)	0.020 (8)	0.066 (12)	−0.001 (7)	−0.002 (9)	0.004 (8)
O22B	0.086 (10)	0.039 (9)	0.068 (10)	0.012 (7)	−0.003 (8)	−0.002 (7)
O23B	0.086 (9)	0.043 (9)	0.069 (11)	0.000 (7)	0.008 (8)	−0.007 (8)
O24B	0.091 (9)	0.046 (8)	0.076 (10)	0.009 (7)	0.012 (7)	−0.006 (7)
O1WA	0.100 (8)	0.095 (7)	0.042 (5)	0.000 (7)	0.005 (6)	−0.007 (5)
O1WB	0.067 (9)	0.056 (8)	0.038 (8)	−0.005 (8)	0.004 (8)	0.001 (6)
O1WC	0.077 (8)	0.045 (7)	0.052 (8)	−0.012 (6)	0.010 (6)	−0.012 (6)

Geometric parameters (Å, º) top

Ba1—O1	2.688 (3)	C5—H5B	0.9900
Ba1—O4	2.690 (3)	O6—C22	1.339 (6)
Ba1—O1WB	2.75 (2)	O6—C18	1.370 (5)
Ba1—O1WA	2.774 (14)	C6—H6A	0.9900
Ba1—O5	2.814 (3)	C6—H6B	0.9900
Ba1—O11A	2.853 (19)	C7—C8	1.503 (6)
Ba1—O2ⁱ	2.860 (3)	C7—H7A	0.9900
Ba1—O2	2.861 (3)	C7—H7B	0.9900
Ba1—O12B	2.863 (10)	C8—H8A	0.9900
Ba1—O5ⁱⁱ	2.901 (3)	C8—H8B	0.9900
Ba1—O12A	2.955 (15)	C9—H9A	0.9800
Ba1—O1WC	2.972 (17)	C9—H9B	0.9800
Co1—O1	2.044 (3)	C9—H9C	0.9800
Co1—O4	2.075 (3)	C10—H10A	0.9800
Co1—N1	2.199 (3)	C10—H10B	0.9800
Co1—N3	2.220 (3)	C10—H10C	0.9800
Co1—N4	2.344 (4)	C11—C12	1.484 (6)
Co1—N2	2.414 (4)	C11—H11A	0.9900
O1—C13	1.330 (5)	C11—H11B	0.9900
N1—C5	1.472 (6)	C12—C13	1.351 (6)
N1—C10	1.484 (5)	C13—C14	1.448 (6)
N1—C4	1.485 (6)	C14—C15	1.432 (5)
C1—C2	1.484 (7)	C15—C16	1.326 (6)
C1—N3	1.492 (6)	C15—H15	0.9500
C1—H1A	0.9900	C16—H16	0.9500
C1—H1B	0.9900	C17—C18	1.471 (6)
O2—C14	1.252 (5)	C17—H17A	0.9900
O2—Ba1ⁱ	2.860 (3)	C17—H17B	0.9900
N2—C3	1.466 (6)	C18—C19	1.353 (6)
N2—C2	1.479 (5)	C19—C20	1.469 (6)
N2—C11	1.486 (6)	C20—C21	1.429 (6)
C2—H2A	0.9900	C21—C22	1.320 (7)
C2—H2B	0.9900	C21—H21	0.9500
O3—C16	1.334 (5)	C22—H22	0.9500
O3—C12	1.366 (5)	Cl1A—O12A	1.35 (2)
N3—C9	1.470 (6)	Cl1A—O13A	1.40 (2)
N3—C8	1.481 (6)	Cl1A—O14A	1.47 (3)
C3—C4	1.511 (6)	Cl1A—O11A	1.59 (2)
C3—H3A	0.9900	Cl1B—O11B	1.342 (18)
C3—H3B	0.9900	Cl1B—O14B	1.383 (17)
O4—C19	1.325 (5)	Cl1B—O13B	1.433 (15)
N4—C17	1.471 (5)	Cl1B—O12B	1.484 (15)
N4—C7	1.477 (5)	Cl2A—O22A	1.423 (11)
N4—C6	1.490 (5)	Cl2A—O21A	1.425 (12)
C4—H4A	0.9900	Cl2A—O23A	1.434 (10)
C4—H4B	0.9900	Cl2A—O24A	1.444 (11)
O5—C20	1.254 (5)	Cl2B—O24B	1.33 (5)
O5—Ba1ⁱⁱ	2.901 (3)	Cl2B—O23B	1.40 (4)
C5—C6	1.497 (6)	Cl2B—O21B	1.42 (4)
C5—H5A	0.9900	Cl2B—O22B	1.43 (5)

O1—Ba1—O4	56.75 (8)	N1—C4—H4A	109.6
O1—Ba1—O1WB	101.1 (5)	C3—C4—H4A	109.6
O4—Ba1—O1WB	74.2 (5)	N1—C4—H4B	109.6
O1—Ba1—O1WA	94.5 (3)	C3—C4—H4B	109.6
O4—Ba1—O1WA	78.8 (3)	H4A—C4—H4B	108.1
O1—Ba1—O5	111.22 (8)	C20—O5—Ba1	112.8 (3)
O4—Ba1—O5	60.20 (8)	C20—O5—Ba1ⁱⁱ	127.8 (3)
O1WB—Ba1—O5	85.5 (4)	Ba1—O5—Ba1ⁱⁱ	115.92 (10)
O1WA—Ba1—O5	97.9 (3)	N1—C5—C6	112.4 (4)
O1—Ba1—O11A	73.1 (4)	N1—C5—H5A	109.1
O4—Ba1—O11A	117.6 (4)	C6—C5—H5A	109.1
O1WA—Ba1—O11A	144.0 (5)	N1—C5—H5B	109.1
O5—Ba1—O11A	118.1 (4)	C6—C5—H5B	109.1
O1—Ba1—O2ⁱ	121.15 (8)	H5A—C5—H5B	107.9
O4—Ba1—O2ⁱ	146.50 (9)	C22—O6—C18	118.5 (4)
O1WB—Ba1—O2ⁱ	73.8 (5)	N4—C6—C5	110.4 (4)
O1WA—Ba1—O2ⁱ	67.9 (3)	N4—C6—H6A	109.6
O5—Ba1—O2ⁱ	126.20 (8)	C5—C6—H6A	109.6
O11A—Ba1—O2ⁱ	89.4 (4)	N4—C6—H6B	109.6
O1—Ba1—O2	59.51 (8)	C5—C6—H6B	109.6
O4—Ba1—O2	107.01 (8)	H6A—C6—H6B	108.1
O1WB—Ba1—O2	87.0 (5)	N4—C7—C8	109.4 (4)
O1WA—Ba1—O2	74.4 (3)	N4—C7—H7A	109.8
O5—Ba1—O2	166.61 (9)	C8—C7—H7A	109.8
O11A—Ba1—O2	70.2 (4)	N4—C7—H7B	109.8
O2ⁱ—Ba1—O2	61.66 (10)	C8—C7—H7B	109.8
O1—Ba1—O12B	76.5 (3)	H7A—C7—H7B	108.2
O4—Ba1—O12B	84.3 (3)	N3—C8—C7	110.9 (4)
O1WB—Ba1—O12B	155.1 (5)	N3—C8—H8A	109.5
O5—Ba1—O12B	72.8 (2)	C7—C8—H8A	109.5
O2ⁱ—Ba1—O12B	129.0 (3)	N3—C8—H8B	109.5
O2—Ba1—O12B	111.7 (2)	C7—C8—H8B	109.5
O1—Ba1—O5ⁱⁱ	149.97 (9)	H8A—C8—H8B	108.1
O4—Ba1—O5ⁱⁱ	123.92 (8)	N3—C9—H9A	109.5
O1WB—Ba1—O5ⁱⁱ	107.8 (5)	N3—C9—H9B	109.5
O1WA—Ba1—O5ⁱⁱ	115.4 (3)	H9A—C9—H9B	109.5
O5—Ba1—O5ⁱⁱ	64.08 (10)	N3—C9—H9C	109.5
O11A—Ba1—O5ⁱⁱ	83.3 (4)	H9A—C9—H9C	109.5
O2ⁱ—Ba1—O5ⁱⁱ	75.82 (9)	H9B—C9—H9C	109.5
O2—Ba1—O5ⁱⁱ	128.99 (9)	N1—C10—H10A	109.5
O12B—Ba1—O5ⁱⁱ	73.8 (3)	N1—C10—H10B	109.5
O1—Ba1—O12A	85.8 (4)	H10A—C10—H10B	109.5
O4—Ba1—O12A	93.0 (4)	N1—C10—H10C	109.5
O1WA—Ba1—O12A	169.9 (4)	H10A—C10—H10C	109.5
O5—Ba1—O12A	72.6 (3)	H10B—C10—H10C	109.5
O11A—Ba1—O12A	45.6 (5)	C12—C11—N2	111.3 (4)
O2ⁱ—Ba1—O12A	120.5 (4)	C12—C11—H11A	109.4
O2—Ba1—O12A	114.1 (3)	N2—C11—H11A	109.4
O5ⁱⁱ—Ba1—O12A	64.3 (4)	C12—C11—H11B	109.4
O1—Ba1—O1WC	114.0 (3)	N2—C11—H11B	109.4
O4—Ba1—O1WC	71.0 (3)	H11A—C11—H11B	108.0
O5—Ba1—O1WC	64.8 (3)	C13—C12—O3	123.3 (4)
O2ⁱ—Ba1—O1WC	82.8 (3)	C13—C12—C11	124.2 (4)
O2—Ba1—O1WC	108.7 (3)	O3—C12—C11	112.5 (4)
O5ⁱⁱ—Ba1—O1WC	91.4 (3)	O1—C13—C12	121.8 (4)
O1—Co1—O4	76.70 (11)	O1—C13—C14	119.4 (4)
O1—Co1—N1	122.08 (13)	C12—C13—C14	118.7 (4)
O4—Co1—N1	100.96 (12)	O2—C14—C15	123.7 (4)
O1—Co1—N3	100.86 (13)	O2—C14—C13	121.5 (4)
O4—Co1—N3	124.07 (13)	C15—C14—C13	114.8 (4)
N1—Co1—N3	124.08 (13)	C16—C15—C14	121.8 (4)
O1—Co1—N4	153.71 (12)	C16—C15—H15	119.1
O4—Co1—N4	82.53 (11)	C14—C15—H15	119.1
N1—Co1—N4	77.40 (13)	C15—C16—O3	122.6 (4)
N3—Co1—N4	77.62 (12)	C15—C16—H16	118.7
O1—Co1—N2	81.95 (12)	O3—C16—H16	118.7
O4—Co1—N2	152.96 (12)	C18—C17—N4	113.1 (4)
N1—Co1—N2	76.58 (12)	C18—C17—H17A	109.0
N3—Co1—N2	75.99 (13)	N4—C17—H17A	109.0
N4—Co1—N2	122.15 (12)	C18—C17—H17B	109.0
C13—O1—Co1	131.9 (2)	N4—C17—H17B	109.0
C13—O1—Ba1	114.1 (2)	H17A—C17—H17B	107.8
Co1—O1—Ba1	113.82 (11)	C19—C18—O6	123.0 (4)
C5—N1—C10	110.3 (4)	C19—C18—C17	124.1 (4)
C5—N1—C4	108.4 (3)	O6—C18—C17	112.9 (4)
C10—N1—C4	108.1 (4)	O4—C19—C18	122.3 (4)
C5—N1—Co1	110.6 (3)	O4—C19—C20	118.9 (4)
C10—N1—Co1	107.3 (3)	C18—C19—C20	118.7 (4)
C4—N1—Co1	112.1 (3)	O5—C20—C21	124.2 (4)
C2—C1—N3	112.0 (4)	O5—C20—C19	121.3 (4)
C2—C1—H1A	109.2	C21—C20—C19	114.5 (4)
N3—C1—H1A	109.2	C22—C21—C20	122.0 (4)
C2—C1—H1B	109.2	C22—C21—H21	119.0
N3—C1—H1B	109.2	C20—C21—H21	119.0
H1A—C1—H1B	107.9	C21—C22—O6	123.1 (4)
C14—O2—Ba1ⁱ	124.5 (3)	C21—C22—H22	118.4
C14—O2—Ba1	111.2 (2)	O6—C22—H22	118.4
Ba1ⁱ—O2—Ba1	118.33 (10)	O12A—Cl1A—O13A	89.8 (18)
C3—N2—C2	111.1 (4)	O12A—Cl1A—O14A	109.8 (13)
C3—N2—C11	108.9 (4)	O13A—Cl1A—O14A	118.6 (14)
C2—N2—C11	109.8 (3)	O12A—Cl1A—O11A	99.6 (12)
C3—N2—Co1	105.2 (3)	O13A—Cl1A—O11A	109.7 (13)
C2—N2—Co1	108.4 (3)	O14A—Cl1A—O11A	122.2 (15)
C11—N2—Co1	113.5 (3)	O12A—Cl1A—Ba1	52.5 (8)
N2—C2—C1	111.4 (4)	O13A—Cl1A—Ba1	121.1 (11)
N2—C2—H2A	109.3	O14A—Cl1A—Ba1	116.5 (12)
C1—C2—H2A	109.3	O11A—Cl1A—Ba1	51.0 (8)
N2—C2—H2B	109.3	Cl1A—O11A—Ba1	103.3 (10)
C1—C2—H2B	109.3	Cl1A—O12A—Ba1	106.3 (10)
H2A—C2—H2B	108.0	O11B—Cl1B—O14B	101.1 (12)
C16—O3—C12	118.6 (3)	O11B—Cl1B—O13B	108.6 (9)
C9—N3—C8	108.0 (4)	O14B—Cl1B—O13B	101.2 (12)
C9—N3—C1	111.1 (4)	O11B—Cl1B—O12B	111.0 (10)
C8—N3—C1	106.7 (4)	O14B—Cl1B—O12B	111.2 (9)
C9—N3—Co1	109.7 (3)	O13B—Cl1B—O12B	121.5 (12)
C8—N3—Co1	110.5 (2)	O11B—Cl1B—Ba1	61.1 (7)
C1—N3—Co1	110.8 (3)	O14B—Cl1B—Ba1	124.5 (8)
N2—C3—C4	109.5 (4)	O13B—Cl1B—Ba1	134.0 (9)
N2—C3—H3A	109.8	O12B—Cl1B—Ba1	50.2 (5)
C4—C3—H3A	109.8	Cl1B—O11B—Ba1	97.0 (7)
N2—C3—H3B	109.8	Cl1B—O12B—Ba1	106.3 (6)
C4—C3—H3B	109.8	O22A—Cl2A—O21A	104.2 (9)
H3A—C3—H3B	108.2	O22A—Cl2A—O23A	108.7 (6)
C19—O4—Co1	132.0 (2)	O21A—Cl2A—O23A	108.1 (7)
C19—O4—Ba1	115.2 (2)	O22A—Cl2A—O24A	111.8 (8)
Co1—O4—Ba1	112.64 (11)	O21A—Cl2A—O24A	109.6 (6)
C17—N4—C7	107.8 (3)	O23A—Cl2A—O24A	113.9 (9)
C17—N4—C6	110.0 (3)	O24B—Cl2B—O23B	90 (3)
C7—N4—C6	109.9 (3)	O24B—Cl2B—O21B	116 (3)
C17—N4—Co1	114.3 (3)	O23B—Cl2B—O21B	104 (3)
C7—N4—Co1	105.7 (3)	O24B—Cl2B—O22B	85 (3)
C6—N4—Co1	108.8 (3)	O23B—Cl2B—O22B	120 (3)
N1—C4—C3	110.4 (4)	O21B—Cl2B—O22B	131 (3)

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

Selected bond lengths and angles (Å, °) top

Co1—N1	2.199 (3)
Co1—N2	2.414 (3)
Co1—N3	2.220 (4)
Co1—N4	2.344 (3)
Co1—O1	2.044 (3)
Co1—O4	2.075 (3)
Ba1—O1	2.688 (3)
Ba1—O2	2.861 (3)
Ba1—O4	2.690 (3)
Ba1—O5	2.814 (3)
Ba1—O1W	2.774 (14)/2.75 (2)/2.972 (15)^a
Ba1—O11	2.853 (19)/3.154 (13)^b
Ba1—O12	2.955 (18)/2.863 (12)^b
N1···N3	3.903 (5)
N2···N4	4.164 (5)
Ba1···Ba1ⁱ	4.9123 (4)
Ba1···O2ⁱ	2.860 (3)
O2···O2ⁱ	2.932 (4)
Ba1···Ba1ⁱⁱ	4.8443 (4)
Ba1···O5ⁱⁱ	2.900 (3)
O5···O5ⁱⁱ	3.033 (4)
Ba1ⁱ···Ba1ⁱⁱ	8.8965 (4)

Ba1—O1—Co1	113.82 (12)
Ba1—O4—Co1	112.64 (11)
Ba1—O2—Ba1ⁱ	118.34 (10)
Ba1—O5—Ba1ⁱⁱ	115.92 (10)

Symmetry codes: (i) = -x + 1, -y, -z; (ii) = -x + 2, -y, -z. Notes: (a) the values refer to O1WA/B/C atoms, respectively; (b) the values refer to the A/B oxygen atoms, respectively, of the disordered perchlorate anion (see Refinement section).

Hydrogen-bond geometry (Å, °) top

The first and second values for each entry refer to the A and B oxygen atoms, respectively, of the disordered perchlorate anion (see Refinement section).

D—H···	D—H	H···A	D···A	D—H···A
C8—H8A···O21	0.99	2.91/2.62	3.877 (12)/3.60 (3)	165.3/172.3
C3—H3A···O22ⁱⁱⁱ	0.99	2.65/2.48	3.577 (11)/3.46 (3)	155.7/166.7
C8—H8B···O13^iv	0.99	2.49/2.59	3.46 (2)/3.524 (15)	168.5/156.6
C22—H22···O21^v	0.95	2.62/2.66	3.482 (11)/3.51 (3)	151.4/149.2
C22—H22···O23^v	0.95	2.57/2.54	3.455 (11)/3.39 (4)	155.1/149.9

Symmetry codes: (iii) -x + 3/2, y - 1/2, -z + 1/2; (iv) x + 1/2, -y + 1/2, z - 1/2; (v) x - 1, y, z.

Acknowledgements

The authors acknowledge the CRIST (Centro di Cristallografia Strutturale, University of Firenze) where the data collection was performed.

Funding information

Funding for this research was provided by: MIUR PRIN 2015.

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