Crystal structure of bis­{μ2-2,2′-[(4,10-dimethyl-1,4,7,10-tetra­aza­cyclo­dodecane-1,7-di­yl)bis(meth­yl­ene)]bis­(4-oxo-4H-pyran-3-olato)}dicobalt­calcium bis­(perchlorate) 1.36-hydrate

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

doi:10.1107/S2056989017016693

research communications

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ISSN: 2056-9890

Volume 73| Part 12| December 2017| Pages 1959-1965

https://doi.org/10.1107/S2056989017016693

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Crystal structure of bis{μ₂-2,2′-[(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene)]bis(4-oxo-4H-pyran-3-olato)}dicobaltcalcium bis(perchlorate) 1.36-hydrate

Patrizia Rossi,^a Eleonora Macedi,^a ^* Paola Paoli,^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 C. Massera, Università di Parma, Italy (Received 10 November 2017; accepted 20 November 2017; online 28 November 2017)

The title compound, [CaCo₂(C₂₂H₃₀N₄O₆)₂](ClO₄)₂·1.36H₂O or {Ca[Co(H_–2L1)]₂}·2ClO₄·1.36H₂O {where L1 is 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane}, is a trinuclear complex whose asymmetric unit comprises a quarter of the {Ca[Co(H_–2L1)]₂}²⁺ trinuclear complex, half of a perchlorate ion and 0.34-water molecules. In the neutral [Co(H_–2L1)] moiety, the cobalt ion is hexacoordinated in a trigonal–prismatic fashion by the surrounding N₄O₂ donor set. A Ca²⁺ cation holds together two neutral [Co(H_–2L1)] moieties and is octacoordinated in a distorted trigonal–dodecahedral fashion by the surrounding O atoms belonging to the deprotonated oxide and carbonyl groups of two [Co(H_–2L1)] units. The coordination of the Co^II cation preorganizes L1 and an electron-rich area forms, which is able to host hard metal ions. The comparison between the present structure and the previously published ones suggests a high versatility of this ligand; indeed, hard metal ions with different nature and dimensions lead to complexes having different stoichiometry (mono- and dinuclear monomers and trinuclear dimers) or even a polymeric structure. The heterotrinuclear Co^II–Ca^II–Co^II complexes are connected in three dimensions via weak C—H⋯O hydrogen bonds, which are also responsible for the interactions with the perchlorate anions and the lattice water molecules. The perchlorate anion is disordered about a twofold rotation axis and was refined giving the two positions a fixed occupancy factor of 0.5. The crystal studied was refined as a two-component inversion twin [BASF parameter = 0.14 (4)].

Keywords: crystal structure; macrocycle; polyamine ligands; heterotrinuclear complexes; alkaline-earth cations; maltol.

CCDC reference: 1586509

1. Chemical context

Polynuclear metal complexes have long been studied due to their versatility. They find applications in many fields, ranging from molecular recognition to transport and catalysis (Gokel & Barbour, 2017 ; Weber & Gokel, 2012 ; Ambrosi et al., 2007a ,b , 2008 , 2009a ,b ; Martell & Hancock, 1996 ; Voegtle, 1996 ; Zelewsky, 1996 ; Lehn, 1988 ), to name just a few. Moreover, they find applications in the field of bioinorganic chemistry (Fanelli et al., 2016 ; Marchetti et al., 2015 ; Patra et al., 2014 ), for instance as anticancer agents (Bruijnincx & Sadler, 2008 ) and artificial metalloproteases (Suh & Chei, 2008 ).

On the other hand, hard metal ions also find applications in the biological field. Both rare earth and alkaline earth metal ions are used in the biomedical field, in bioassays and bioimaging applications (Xiao et al., 2016 ; Yin et al., 2015 ; DaCosta et al., 2014 ; Merbach et al., 2013 ; Di Bernardo et al., 2012 ; Price et al., 2012 ). Furthermore, hard metal ions are quite difficult to bind in water because they need a high coordination number without usually showing specific coordination requirements, issues that could be overcome using preorganized receptors bearing oxygenated donor sites. It follows that systems able to bind hard metal ions, both in aqueous solution and in the solid state, are very attractive. Indeed, they have found applications in fields ranging from new materials to medicinal chemistry (Blindauer et al., 2017 ; Esteves et al., 2016 ; Lomidze et al., 2016 ; Yang et al., 2014 ; Price et al., 2012; Pasatoiu et al., 2011 ; Pasatoiu et al., 2010 ; Aime et al., 2006 ; Bernot et al., 2006 ; Gatteschi et al., 2006 ; Malandrino & Fragalà, 2006 ; Terai et al., 2006 ).

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 ) capable of forming a mononuclear Co^II species where both side-arms are forced by the transition metal ion to move and locate on the same part with respect to the macrocyclic plane (Borgogelli et al., 2013 ). Such a cobalt-driven preorganization allows the formation of an electron-rich area formed by the four converging oxygen atoms of the two maltolate functions of L1, suitable to host hard metal ions such as Ln^III (Ln = Gd, Eu; Benelli et al., 2013 ; Rossi et al., 2017 ), Na^I (Borgogelli et al., 2013) and Ba^II (Paoli et al., 2017 ). The resulting heteropolynuclear systems differ in the number of the complexes involved in the coordination, depending on the nature of the hard cation. Indeed, the coordination of the hard ion leads to Co^II–Ln^III–Co^II heterotrinuclear dimers, a Na^I–Co^II heterodinuclear monomer and a Ba^II–Co^II heterodinuclear metal coordination polymer.

Herein we present a Co^II–Ca^II–Co^II heterotrinuclear dimer of L1 and a brief comparison with the previous L1-containing structures, highlighting the high versatility of this ligand.

2. Structural commentary

The title compound is a trinuclear complex cation of formula {Ca[Co(H_–2L1)]₂}·2ClO₄·1.36H₂O and crystallizes in the tetragonal system in space group I $[\overline{4}]$ . In the {Ca[Co(H_-2L1)]₂}²⁺ trinuclear complex (Fig. 1), two neutral [Co(H_-2L1)] moieties are held together by the Ca²⁺ cation, which is coordinated by oxygen atoms provided by the maltolate groups of the two complexes. The asymmetric unit comprises a quarter of the {Ca[Co(H_–2L1)]₂}²⁺ trinuclear complex, half of a perchlorate ion and 0.34 water molecules. The two halves of each cobalt complex are related by a twofold rotation axis, the cobalt ion lying on the symmetry element. The two cobalt complexes are then related by a fourfold rotoinversion axis, the calcium ion lying on the symmetry element. The disordered perchlorate ion and the water molecule lie on a twofold axis, with the chlorine atom (for ClO₄⁻) and the oxygen atom (for H₂O) lying on the symmetry element.

Figure 1
The molecular structure of the {Ca[Co(H_–2L1)]₂}²⁺ cation, with the atom labelling and 30% probability displacement ellipsoids. H atoms have been omitted for clarity. [Symmetry codes: (i) −x, −y, z; (ii) y, −x, −z; (iii) −y, x, −z.]

In the neutral [Co(H_–2L1)] moiety, the Co²⁺ ion is hexacoordinated by four nitrogen atoms of the macrocyclic base and two deprotonated hydroxyl oxygen atoms provided by both the maltolate rings of the ligand; it exhibits a distorted trigonal–prismatic geometry (Muetterties & Guggenberger, 1974 ), with the N1,N2ⁱ,O1ⁱ/N1ⁱ,N2,O1 atoms [symmetry code: (i) −x, −y, z] defining the two triangular faces, which are parallel within 15.6 (2)° (Fig. 2, left). The cobalt ion is displaced 1.064 (1) Å above the mean plane defined by the four nitrogen atoms of the tetraazamacrocycle [maximum deviation of 0.044 (6) Å for N1]; according to the Cambridge Structural Database (CSD, Version 5.38, May 2017; Groom et al., 2016 ) such distance 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 an N₄O₂ donor set. The Co—N(Maltol) bond distances, by contrast, are beyond this range (Table 1) but are in line with those reported for other Co—L1 complexes [Co—N(Maltol): range 2.26–2.44 Å; Co—N(CH₃) range: 2.13—2.22 Å; Benelli et al., 2013; Borgogelli et al., 2013; Rossi et al., 2017; Paoli et al., 2017].

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

Co1—N1	2.192 (7)
Co1—N2	2.375 (7)
Co1—O1	2.060 (4)
Ca1—O1	2.429 (4)
Ca1—O2	2.469 (4)
N1⋯N1ⁱ	3.881 (9)
N2⋯N2ⁱ	4.206 (10)
Co1⋯Ca1	3.727 (1)
Co1⋯Co1ⁱⁱ	7.454 (2)

N1—Co1—N1ⁱ	124.5 (2)
N1—Co1—N2	78.0 (2)
N1—Co1—N2ⁱ	77.0 (3)
N2—Co1—N2ⁱ	124.6 (3)
O1—Co1—N1	121.2 (2)
O1—Co1—N1ⁱ	102.9 (2)
O1—Co1—N2	81.6 (2)
O1—Co1—N2ⁱ	152.4 (2)
O1—Co1—O1ⁱ	74.3 (2)
O1—Ca1—O1ⁱ	61.7 (2)
O1—Ca1—O1ⁱⁱ	137.5 (1)
O1—Ca1—O2	67.1 (1)
O1—Ca1—O2ⁱ	123.5 (1)
O1—Ca1—O2ⁱⁱ	73.9 (1)
O1—Ca1—O2ⁱⁱⁱ	96.6 (1)
O2—Ca1—O2ⁱ	169.1 (2)
Co1—O1—Ca1	112.0 (2)
Symmetry codes: (i) −x, −y, z; (ii) y, −x, −z; (iii) −y, x, −z.

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

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 with the N2⋯N2ⁱ distance being longer than N1⋯N1ⁱ by 0.32 Å [Table 1, symmetry code: (i) −x, −y, z], as found only in 12% of cases (88%: Δ < 0.32 Å; 12%: Δ > 0.32 Å). This is probably due to the fact that the Maltol units linked to the nitrogen atoms are involved in chelate six-membered rings, which stiffen the system and force those nitrogen atoms to move farther apart.

The mean planes of the two maltolate rings of the neutral [Co(H_–2L1)] moiety form a dihedral angle of about 55°, while the dihedral angle between the N1,N2,N1ⁱ,N2ⁱ [symmetry code: (i) −x, −y, z] and maltolate ring mean planes is about 63°. The distance between the maltolate ring centroids is 7.8463 (3) Å. The dimension of the binding area defined by the four oxygen donor atoms of the ligand is roughly estimated by the distance separating the opposite O1⋯O2ⁱ [symmetry code: (i) −x, −y, z] atoms (and the other symmetry-related oxygen atoms), which is 4.315 (6) Å. Notably, such a distance is longer than those retrieved for analogous trinuclear complexes (opposite O⋯O distances range: 3.98–4.22 Å; Benelli et al., 2013; Rossi et al., 2017), while it is shorter than those retrieved for the one-dimensional coordination polymer of L1 (opposite O⋯O distances: 4.5 Å; Paoli et al., 2017) and the mononuclear complex of L1 (opposite O⋯O distances: 4.49 Å; Borgogelli et al., 2013). As for the dinuclear complex of L1 (Borgogelli et al., 2013), the opposite O⋯O distances of the binding area are quite different from each other (4.12 and 4.42 Å), and are, respectively, shorter and longer than the corresponding distance in the title compound.

The coordination polyhedron around the Ca²⁺ ion can be described as a distorted trigonal dodecahedron (Muetterties & Guggenberger, 1974), with all eight deprotonated hydroxyl and carbonyl oxygen atoms of the two [Co(H_–2L1)] moieties of the trinuclear complex situated at the corners of the polyhedron (Fig. 2, right). The maltolate unit acts as a bidentate ligand through the hydroxyl oxygen atom, which bridges the Ca^II and Co^II cations. All the Ca—O distances are in agreement with data found in the CSD.

The Co²⁺ and Ca²⁺ cations are located 3.727 (1) Å apart from each other and, because of the symmetry of the system, the line connecting the three cations (Co^II–Ca^II–Co^II) is normal to the mean plane described by the four nitrogen atoms of the macrocycle (Fig. 1). The values for the Co⋯Ca distance and the Co—O1—Ca angle are in agreement with data ranges found in the CSD, even if they fall in non-populated regions (only ten hits – corresponding to twenty distances or angle values – are retrieved when the Co–O–Ca fragment is searched). The Co⋯Coⁱⁱ distance and the Co–Ca–Coⁱⁱ angle value [symmetry code: (ii) y, −x, −z] can only be compared with the single hit containing a cobalt-μ₂-oxygen-calcium-μ₂-oxygen-cobalt motif (Fig. 3) deposited in the CSD (refcode: DAPNOA; Li et al., 2017 ), which shows a shorter Co⋯Co distance (6.25 Å) and a smaller Co⋯Ca⋯Co angle value (132°) with respect to the title compound. When all alkaline-earth ions instead of calcium are considered in the fragment searched in the CSD (Fig. 3), both the Co⋯Co distance and Co⋯Ca⋯Co angle values fall within the expected range.

Figure 3
Fragment searched in the CSD. [AE = alkaline-earth metal ion.]

As a result of the symmetry of the system, the two [Co(H_–2L1)] complexes in the {Ca[Co(H_–2L1)]₂}²⁺ cation are rotated by 90°, as indicated by the angle between the two mean planes defined by the Co1,O1,O1ⁱ,Ca1 and Coⁱⁱ,O1ⁱⁱ,O1ⁱⁱⁱ,Ca1 atoms [symmetry codes: (i) −x, −y, z; (ii) y, −x, −z; (iii) −y, x, −z; Fig. 1]. Such an angle value falls in the most populated region for the cobalt-μ₂-oxygen-AE-μ₂-oxygen-cobalt fragment (AE = alkaline-earth ion).

Finally, the shortest Co⋯Co/Co⋯Ca/Ca⋯Ca distances between metal cations belonging to different {Ca[Co(H_–2L1)]₂}²⁺ units are 8.9799 (4)/9.7227 (5)/8.9799 (4) Å.

In the present structure and in all the Co-containing structures of L1 published up to now, the cobalt complexes are well superimposable with each other, but for that belonging to the Na^I–Co^II heterodinuclear complex (r.m.s. deviation values of 0.788 Å and within 0.301 Å for the superimposition of the title compound with the Na^I–Co^II complex and with all other structures, respectively), where the two maltolate rings show a different arrangement, both rings being tilted toward the same direction (instead of opposite directions) with respect to the cobalt-μ₂-oxygen-hard metal mean plane (M = Na^I, Ca^II, Ba^II, Gd^III, Eu^III; in the case of the mononuclear Co^II species, with respect to the cobalt–μ₂-oxygen mean plane; Fig. 4). Moreover, when considering the heterotrinuclear complexes only, the superimposition of the Co^II–Ca^II–Co^II dimer with the whole structures of the Co^II–Ln^III–Co^II dimers (Ln^III = Gd^III, Eu^III) shows high r.m.s. deviation values (1.7 Å), in agreement with a different mutual disposition of the two subunits in the dimers.

Figure 4
Comparison between the overall shapes of the present structure and the other Co-containing structures of L1. Top line, from left to right: Co^II–Ca^II–Co^II, Co^II–Eu^III–Co^II (Rossi et al., 2017

), Co^II–Gd^III–Co^II (refcode: FEZBUJ) complexes; bottom line, from left to right: Co^II species (refcode: WELGEB), Ba^II–Co^II coordination polymer (refcode: ZELBAW), Na^I–Co^II complex (refcode: WELGOL).

The electron-rich area, which forms following the cobalt-driven preorganization of L1, is able to host hard metal ions with different dimensions and coordination requirements, leading to complexes having different stoichiometry (mono- and dinuclear monomers and trinuclear dimers) or even a polymeric structure (Fig. 4). In the case of the Na^I–Co^II structure, a monomer forms, probably because of the lower ionic charge and coordination number (CN) of the Na^I cation (CN: 5, Na⁺ ionic radius: 1.00 Å; Shannon, 1976 ) with respect to the other cations. Indeed, the low ionic charge and coordination number allow the stabilization of the ion with only one [Co(H_–2L1)] moiety. In the case of the Ba^II–Co^II structure, the Ba^II cation shows the highest coordination number (CN: 9, Ba²⁺ ionic radius: 1.47 Å; Shannon, 1976) in the series of structures, and the cationic fragment shows the largest binding area, which is necessary to accommodate such large ionic dimensions. In the case of the heterotrinuclear structures, all of the Gd^III, Eu^III and Ca^II cations have the same coordination number (CN: 8) and similar ionic radii (1.053, 1.066 and 1.12 Å for Gd^III, Eu^III and Ca^II, respectively; Shannon, 1976): two [Co(H_–2L1)] units are needed to stabilize the high ionic charge and fully satisfy the coordination requirements of the cations.

3. Supramolecular features

In the crystal, the heterotrinuclear Co^II–Ca^II–Co^II complexes are connected in the three dimensions via weak C—H⋯O hydrogen bonds (Desiraju & Steiner, 1999 ).

The perchlorate anion interacts with five complexes: four out of five (magenta in Figs. 5 and 6) are connected to form a layer perpendicular to the c axis, the fifth complex also belongs to a layer (blue in Figs. 5 and 6) perpendicular to the c axis, adjacent layers being staggered relative to one other (Fig. 6). All interactions are weak C—H⋯O—Cl hydrogen bonds (Table 2) involving the methylene hydrogen atoms of the macrocycle. The perchlorate anions are located between the layers (Fig. 5).

Table 2
Hydrogen-bond geometry (Å, °)

Note that both models of the disordered perchlorate anion form the same interactions; only one value for each interaction involving oxygen atoms of the ClO₄⁻ anion is therefore reported.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1^iv—H1A^iv⋯O3C	0.99	2.64	3.56 (2)	156
C2ⁱⁱⁱ—H2Aⁱⁱⁱ⋯O4C	0.99	2.68	3.55 (2)	147
C4^iv—H4C^iv⋯O1C	0.98	2.50	3.47 (2)	167
C5^v—H5A^v⋯O2C	0.99	2.59	3.48 (2)	148
C5ⁱⁱⁱ—H5Bⁱⁱⁱ⋯O4C	0.99	2.35	3.29 (2)	157
C6—H6A⋯O1W	0.99	2.35	3.23 (9)	149
C6^vi—H6B^vi⋯O1C	0.99	2.44	3.37 (2)	158
C6^vii—H6B^vii⋯O1C	0.99	2.55	3.51 (2)	164
Symmetry codes: (iii) −y, x, −z; (iv) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (v) x − $[{1\over 2}]$ , y − $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (vi) −x − $[{1\over 2}]$ , −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (vii) x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , z + $[{1\over 2}]$ .

Figure 5
Crystal packing of the title compound viewed along the a axis. Staggered layers of complexes (in magenta and blue) perpendicular to the c axis are present, which are interconnected thanks to hydrogen bonds in the c-axis direction. The perchlorate anions are located between the layers. Interactions with water molecules are also shown. Hydrogen bonds involving ClO₄⁻ anions are depicted as light-blue dotted lines. Hydrogen bonds involving water molecules are depicted as green (along the a axis) and red (along the b axis) dotted lines. The ClO₄⁻ anions and water molecules are depicted in ball-and-stick mode.

Figure 6
Crystal packing of the title compound viewed along the c axis. Staggered layers of complexes (in magenta and blue) perpendicular to the c axis are visible. The ClO₄⁻ anions and water molecules are depicted in ball-and-stick mode.

Water molecules also interact with the complexes via weak C—H⋯O hydrogen bonds (Table 2) along the a and b axes (Fig. 5). These interactions also involve the methylene hydrogen atoms of the macrocycle.

4. Synthesis and crystallization

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

To obtain the title compound, {Ca[Co(H_–2L1)]₂}·2ClO₄·1.36H₂O, 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 CaCl₂ were added. The solution was saturated with NaClO₄. The title compound quickly precipitated as a microcrystalline pink solid. Crystals suitable for X-ray analysis were obtained by slow evaporation of a more diluted aqueous solution.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	[CaCo₂(C₂₂H₃₀N₄O₆)₂](ClO₄)₂·1.36H₂O
M_r	1271.92
Crystal system, space group	Tetragonal, I $[\overline{4}]$
Temperature (K)	100
a, c (Å)	8.9799 (4), 32.555 (3)
V (Å³)	2625.2 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.92
Crystal size (mm)	0.46 × 0.38 × 0.18

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd. Yarnton, England.]$ )
T_min, T_max	0.557, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3291, 2340, 1386
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.681

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.081, 0.86
No. of reflections	2340
No. of parameters	200
No. of restraints	30
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.25
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.14 (4)
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd. Yarnton, England.]$ ), CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd. Yarnton, England.]$ ), SIR2014 (Burla et al., 2015 ) and SHELXL2014 (Sheldrick, 2015 ).

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.

The perchlorate anion is disordered about a twofold rotation axis and was refined giving the two positions a fixed occupancy factor of 0.5. The chlorine atom is located on a twofold rotation axis.

The oxygen atom of the water molecule lies on a twofold rotation axis, the refined occupancy factor is 0.34 (2); the hydrogen atoms were not found in the difference-Fourier map and they were not introduced in the refinement.

All non-hydrogen atoms were refined anisotropically: as for the disordered perchlorate anion, the SIMU instruction was used to restrain the anisotropic displacement parameters of the disordered atoms, while the ISOR instruction was used to restrain the anisotropic displacement parameters of the isolated water oxygen atom.

The structure was refined as a two-component inversion twin [BASF parameter = 0.14 (4)].

Supporting information

CCDC reference: 1586509

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989017016693/xi2003sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017016693/xi2003Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017016693/xi2003Isup3.mol

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Bis{µ₂-2,2'-[(4,10-dimethyl-1,4,7,10-tetraazacyclododecane-1,7-diyl)bis(methylene)]bis(4-oxo-4H-pyran-3-olato)}dicobaltcalcium bis(perchlorate) 1.36-hydrate top

Crystal data top

[CaCo₂(C₂₂H₃₀N₄O₆)₂](ClO₄)₂·1.36H₂O	D_x = 1.609 Mg m⁻³
M_r = 1271.92	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 1087 reflections
a = 8.9799 (4) Å	θ = 3.7–28.8°
c = 32.555 (3) Å	µ = 0.92 mm⁻¹
V = 2625.2 (3) Å³	T = 100 K
Z = 2	Prism, pink
F(000) = 1318	0.46 × 0.38 × 0.18 mm

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2340 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1386 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 16.4547 pixels mm^-1	θ_max = 29.0°, θ_min = 3.8°
ω scans	h = −12→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −12→9
T_min = 0.557, T_max = 1.000	l = −43→30
3291 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0355P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max < 0.001
S = 0.86	Δρ_max = 0.35 e Å⁻³
2340 reflections	Δρ_min = −0.25 e Å⁻³
200 parameters	Absolute structure: Refined as an inversion twin
30 restraints	Absolute structure parameter: 0.14 (4)

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. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.0000	0.0000	−0.11449 (3)	0.0355 (3)
Ca1	0.0000	0.0000	0.0000	0.0350 (5)
O1	−0.1168 (4)	0.0747 (5)	−0.06406 (11)	0.0431 (10)
N1	0.1622 (8)	0.1428 (7)	−0.1458 (2)	0.0439 (16)
C1	0.0890 (10)	0.2753 (10)	−0.1643 (3)	0.062 (3)
H1A	0.1533	0.3164	−0.1862	0.075*
H1B	0.0761	0.3530	−0.1430	0.075*
O2	−0.2696 (5)	0.0475 (5)	0.00717 (15)	0.0510 (13)
N2	−0.1567 (7)	0.1741 (8)	−0.14838 (19)	0.0464 (16)
C2	−0.0591 (10)	0.2353 (12)	−0.1819 (2)	0.055 (2)
H2A	−0.0466	0.1599	−0.2038	0.066*
H2B	−0.1062	0.3247	−0.1941	0.066*
O3	−0.4188 (5)	0.3327 (5)	−0.07952 (15)	0.0562 (12)
C3	−0.2837 (8)	0.0927 (9)	−0.1656 (3)	0.048 (2)
H3A	−0.3229	0.1474	−0.1897	0.058*
H3B	−0.3639	0.0865	−0.1448	0.058*
C4	0.2708 (9)	0.1931 (10)	−0.1142 (3)	0.066 (2)
H4A	0.2181	0.2471	−0.0924	0.099*
H4B	0.3213	0.1063	−0.1024	0.099*
H4C	0.3446	0.2589	−0.1269	0.099*
C5	0.2389 (11)	0.0621 (10)	−0.1785 (3)	0.055 (3)
H5A	0.3289	0.1183	−0.1866	0.066*
H5B	0.1727	0.0555	−0.2027	0.066*
C6	−0.2118 (8)	0.3006 (8)	−0.1240 (2)	0.047 (2)
H6A	−0.1266	0.3648	−0.1163	0.056*
H6B	−0.2804	0.3607	−0.1411	0.056*
C7	−0.2900 (7)	0.2535 (7)	−0.0865 (2)	0.0452 (16)
C8	−0.2406 (6)	0.1491 (6)	−0.0589 (2)	0.0378 (14)
C9	−0.3217 (7)	0.1295 (7)	−0.0201 (2)	0.0445 (17)
C10	−0.4591 (7)	0.2091 (7)	−0.0171 (2)	0.0491 (18)
H10	−0.5227	0.1926	0.0057	0.059*
C11	−0.4987 (8)	0.3054 (9)	−0.0458 (2)	0.061 (2)
H11	−0.5894	0.3582	−0.0422	0.073*
Cl1	0.0000	0.0000	0.29295 (6)	0.0614 (6)
O1C	0.018 (3)	0.0426 (14)	0.3345 (2)	0.069 (3)	0.5
O2C	−0.0574 (17)	−0.1450 (14)	0.2799 (4)	0.090 (3)	0.5
O3C	0.1595 (14)	−0.0078 (17)	0.2807 (4)	0.081 (3)	0.5
O4C	−0.079 (2)	0.1014 (16)	0.2716 (4)	0.087 (3)	0.5
O1W	0.0000	0.5000	−0.0653 (3)	0.077 (5)	0.68 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0367 (9)	0.0418 (9)	0.0282 (5)	−0.0009 (10)	0.000	0.000
Ca1	0.0388 (7)	0.0388 (7)	0.0274 (10)	0.000	0.000	0.000
O1	0.040 (2)	0.059 (3)	0.030 (2)	0.011 (2)	0.000 (2)	0.002 (2)
N1	0.050 (4)	0.043 (4)	0.039 (4)	0.005 (3)	−0.002 (4)	0.003 (4)
C1	0.066 (6)	0.061 (6)	0.059 (6)	−0.003 (5)	0.023 (6)	0.007 (6)
O2	0.050 (2)	0.062 (3)	0.041 (4)	0.003 (2)	−0.003 (3)	0.001 (3)
N2	0.053 (4)	0.048 (4)	0.039 (4)	0.009 (3)	0.002 (4)	0.000 (4)
C2	0.060 (6)	0.070 (7)	0.036 (5)	0.001 (6)	0.005 (5)	0.013 (5)
O3	0.049 (3)	0.065 (3)	0.054 (3)	0.018 (3)	−0.008 (3)	−0.008 (3)
C3	0.033 (5)	0.062 (6)	0.050 (6)	0.000 (4)	−0.017 (4)	−0.012 (5)
C4	0.057 (5)	0.084 (6)	0.057 (5)	−0.029 (4)	0.000 (5)	−0.001 (6)
C5	0.050 (5)	0.073 (7)	0.041 (5)	−0.013 (6)	0.012 (5)	0.006 (5)
C6	0.053 (4)	0.044 (4)	0.043 (5)	0.005 (4)	−0.006 (4)	0.004 (4)
C7	0.039 (3)	0.051 (4)	0.046 (4)	0.011 (3)	−0.009 (4)	−0.007 (4)
C8	0.034 (3)	0.043 (3)	0.037 (3)	0.001 (3)	−0.006 (4)	−0.008 (4)
C9	0.045 (4)	0.046 (4)	0.043 (4)	−0.006 (4)	0.000 (4)	−0.017 (4)
C10	0.033 (3)	0.057 (4)	0.058 (4)	0.003 (3)	0.005 (3)	−0.010 (4)
C11	0.045 (4)	0.073 (5)	0.064 (5)	0.022 (4)	0.001 (4)	−0.020 (5)
Cl1	0.072 (2)	0.072 (2)	0.0405 (11)	0.007 (3)	0.000	0.000
O1C	0.075 (7)	0.093 (7)	0.040 (3)	0.021 (6)	−0.013 (6)	−0.016 (5)
O2C	0.087 (6)	0.085 (6)	0.098 (6)	−0.009 (6)	−0.001 (6)	−0.005 (6)
O3C	0.070 (6)	0.095 (6)	0.078 (6)	−0.003 (6)	0.004 (5)	−0.006 (6)
O4C	0.100 (7)	0.092 (7)	0.071 (6)	0.017 (6)	−0.027 (6)	0.018 (5)
O1W	0.106 (8)	0.062 (7)	0.064 (7)	−0.012 (5)	0.000	0.000

Geometric parameters (Å, º) top

Co1—O1	2.060 (4)	C3—C5ⁱ	1.506 (9)
Co1—O1ⁱ	2.061 (4)	C3—H3A	0.9900
Co1—N1	2.192 (6)	C3—H3B	0.9900
Co1—N1ⁱ	2.192 (6)	C4—H4A	0.9800
Co1—N2	2.375 (6)	C4—H4B	0.9800
Co1—N2ⁱ	2.375 (6)	C4—H4C	0.9800
Ca1—O1ⁱⁱ	2.429 (4)	C5—C3ⁱ	1.506 (9)
Ca1—O1ⁱ	2.429 (4)	C5—H5A	0.9900
Ca1—O1ⁱⁱⁱ	2.429 (4)	C5—H5B	0.9900
Ca1—O1	2.429 (4)	C6—C7	1.471 (9)
Ca1—O2ⁱⁱⁱ	2.469 (4)	C6—H6A	0.9900
Ca1—O2ⁱⁱ	2.469 (4)	C6—H6B	0.9900
Ca1—O2ⁱ	2.469 (4)	C7—C8	1.372 (8)
Ca1—O2	2.469 (4)	C8—C9	1.467 (8)
Ca1—C9ⁱⁱ	3.182 (7)	C9—C10	1.430 (9)
Ca1—C9ⁱⁱⁱ	3.182 (7)	C10—C11	1.320 (9)
Ca1—C9ⁱ	3.182 (7)	C10—H10	0.9500
Ca1—C9	3.182 (7)	C11—H11	0.9500
O1—C8	1.309 (6)	Cl1—O4C	1.345 (12)
N1—C5	1.459 (9)	Cl1—O4Cⁱ	1.345 (12)
N1—C1	1.486 (10)	Cl1—O1Cⁱ	1.413 (7)
N1—C4	1.489 (9)	Cl1—O1C	1.413 (7)
C1—C2	1.492 (10)	Cl1—O2Cⁱ	1.463 (14)
C1—H1A	0.9900	Cl1—O2C	1.463 (13)
C1—H1B	0.9900	Cl1—O3C	1.488 (13)
O2—C9	1.245 (7)	Cl1—O3Cⁱ	1.488 (13)
N2—C3	1.466 (9)	O1C—O1Cⁱ	0.83 (2)
N2—C6	1.472 (9)	O2C—O4Cⁱ	1.312 (17)
N2—C2	1.502 (9)	O2C—O3Cⁱ	1.651 (16)
C2—H2A	0.9900	O3C—O4Cⁱ	1.148 (17)
C2—H2B	0.9900	O3C—O2Cⁱ	1.651 (16)
O3—C11	1.334 (8)	O4C—O3Cⁱ	1.148 (17)
O3—C7	1.376 (7)	O4C—O2Cⁱ	1.312 (17)

O1—Co1—O1ⁱ	74.3 (2)	C3—N2—C6	109.3 (6)
O1—Co1—N1	121.2 (2)	C3—N2—C2	111.0 (6)
O1ⁱ—Co1—N1	102.9 (2)	C6—N2—C2	107.8 (7)
O1—Co1—N1ⁱ	102.9 (2)	C3—N2—Co1	108.1 (5)
O1ⁱ—Co1—N1ⁱ	121.2 (2)	C6—N2—Co1	117.2 (4)
N1—Co1—N1ⁱ	124.5 (3)	C2—N2—Co1	103.4 (5)
O1—Co1—N2	81.6 (2)	C1—C2—N2	109.3 (7)
O1ⁱ—Co1—N2	152.37 (19)	C1—C2—H2A	109.8
N1—Co1—N2	78.0 (3)	N2—C2—H2A	109.8
N1ⁱ—Co1—N2	77.0 (3)	C1—C2—H2B	109.8
O1—Co1—N2ⁱ	152.37 (19)	N2—C2—H2B	109.8
O1ⁱ—Co1—N2ⁱ	81.6 (2)	H2A—C2—H2B	108.3
N1—Co1—N2ⁱ	77.0 (3)	C11—O3—C7	119.5 (6)
N1ⁱ—Co1—N2ⁱ	78.0 (3)	N2—C3—C5ⁱ	111.0 (7)
N2—Co1—N2ⁱ	124.6 (3)	N2—C3—H3A	109.4
O1ⁱⁱ—Ca1—O1ⁱ	137.50 (11)	C5ⁱ—C3—H3A	109.4
O1ⁱⁱ—Ca1—O1ⁱⁱⁱ	61.67 (17)	N2—C3—H3B	109.4
O1ⁱ—Ca1—O1ⁱⁱⁱ	137.50 (11)	C5ⁱ—C3—H3B	109.4
O1ⁱⁱ—Ca1—O1	137.50 (11)	H3A—C3—H3B	108.0
O1ⁱ—Ca1—O1	61.67 (17)	N1—C4—H4A	109.5
O1ⁱⁱⁱ—Ca1—O1	137.50 (11)	N1—C4—H4B	109.5
O1ⁱⁱ—Ca1—O2ⁱⁱⁱ	123.52 (14)	H4A—C4—H4B	109.5
O1ⁱ—Ca1—O2ⁱⁱⁱ	73.89 (15)	N1—C4—H4C	109.5
O1ⁱⁱⁱ—Ca1—O2ⁱⁱⁱ	67.05 (14)	H4A—C4—H4C	109.5
O1—Ca1—O2ⁱⁱⁱ	96.61 (14)	H4B—C4—H4C	109.5
O1ⁱⁱ—Ca1—O2ⁱⁱ	67.05 (14)	N1—C5—C3ⁱ	112.4 (7)
O1ⁱ—Ca1—O2ⁱⁱ	96.61 (14)	N1—C5—H5A	109.1
O1ⁱⁱⁱ—Ca1—O2ⁱⁱ	123.52 (14)	C3ⁱ—C5—H5A	109.1
O1—Ca1—O2ⁱⁱ	73.89 (15)	N1—C5—H5B	109.1
O2ⁱⁱⁱ—Ca1—O2ⁱⁱ	169.1 (2)	C3ⁱ—C5—H5B	109.1
O1ⁱⁱ—Ca1—O2ⁱ	73.89 (15)	H5A—C5—H5B	107.8
O1ⁱ—Ca1—O2ⁱ	67.05 (14)	C7—C6—N2	112.8 (6)
O1ⁱⁱⁱ—Ca1—O2ⁱ	96.61 (14)	C7—C6—H6A	109.0
O1—Ca1—O2ⁱ	123.52 (14)	N2—C6—H6A	109.0
O2ⁱⁱⁱ—Ca1—O2ⁱ	90.51 (2)	C7—C6—H6B	109.0
O2ⁱⁱ—Ca1—O2ⁱ	90.51 (2)	N2—C6—H6B	109.0
O1ⁱⁱ—Ca1—O2	96.61 (14)	H6A—C6—H6B	107.8
O1ⁱ—Ca1—O2	123.52 (14)	C8—C7—O3	121.1 (6)
O1ⁱⁱⁱ—Ca1—O2	73.89 (15)	C8—C7—C6	125.9 (6)
O1—Ca1—O2	67.06 (14)	O3—C7—C6	112.9 (6)
O2ⁱⁱⁱ—Ca1—O2	90.51 (2)	O1—C8—C7	122.6 (6)
O2ⁱⁱ—Ca1—O2	90.51 (2)	O1—C8—C9	118.1 (6)
O2ⁱ—Ca1—O2	169.1 (2)	C7—C8—C9	119.0 (6)
O1ⁱⁱ—Ca1—C9ⁱⁱ	47.97 (15)	O1—C8—Ca1	44.4 (3)
O1ⁱ—Ca1—C9ⁱⁱ	105.63 (15)	C7—C8—Ca1	154.3 (4)
O1ⁱⁱⁱ—Ca1—C9ⁱⁱ	108.44 (15)	C9—C8—Ca1	76.6 (4)
O1—Ca1—C9ⁱⁱ	94.80 (16)	O2—C9—C10	124.9 (7)
O2ⁱⁱⁱ—Ca1—C9ⁱⁱ	166.55 (15)	O2—C9—C8	119.9 (6)
O2ⁱⁱ—Ca1—C9ⁱⁱ	20.98 (16)	C10—C9—C8	115.2 (6)
O2ⁱ—Ca1—C9ⁱⁱ	77.22 (14)	O2—C9—Ca1	45.3 (3)
O2—Ca1—C9ⁱⁱ	100.50 (14)	C10—C9—Ca1	162.3 (4)
O1ⁱⁱ—Ca1—C9ⁱⁱⁱ	108.44 (15)	C8—C9—Ca1	76.7 (3)
O1ⁱ—Ca1—C9ⁱⁱⁱ	94.80 (16)	C11—C10—C9	120.8 (7)
O1ⁱⁱⁱ—Ca1—C9ⁱⁱⁱ	47.97 (15)	C11—C10—H10	119.6
O1—Ca1—C9ⁱⁱⁱ	105.63 (15)	C9—C10—H10	119.6
O2ⁱⁱⁱ—Ca1—C9ⁱⁱⁱ	20.98 (16)	C10—C11—O3	123.9 (7)
O2ⁱⁱ—Ca1—C9ⁱⁱⁱ	166.55 (15)	C10—C11—H11	118.1
O2ⁱ—Ca1—C9ⁱⁱⁱ	100.50 (14)	O3—C11—H11	118.1
O2—Ca1—C9ⁱⁱⁱ	77.22 (14)	O4C—Cl1—O4Cⁱ	117.9 (12)
C9ⁱⁱ—Ca1—C9ⁱⁱⁱ	156.3 (2)	O4C—Cl1—O1Cⁱ	128.0 (12)
O1ⁱⁱ—Ca1—C9ⁱ	94.80 (16)	O4Cⁱ—Cl1—O1Cⁱ	111.7 (9)
O1ⁱ—Ca1—C9ⁱ	47.97 (15)	O4C—Cl1—O1C	111.7 (9)
O1ⁱⁱⁱ—Ca1—C9ⁱ	105.63 (15)	O4Cⁱ—Cl1—O1C	128.0 (12)
O1—Ca1—C9ⁱ	108.44 (15)	O1Cⁱ—Cl1—O1C	34.2 (8)
O2ⁱⁱⁱ—Ca1—C9ⁱ	77.22 (14)	O4C—Cl1—O2Cⁱ	55.5 (8)
O2ⁱⁱ—Ca1—C9ⁱ	100.50 (14)	O4Cⁱ—Cl1—O2Cⁱ	105.5 (7)
O2ⁱ—Ca1—C9ⁱ	20.98 (16)	O1Cⁱ—Cl1—O2Cⁱ	123.9 (7)
O2—Ca1—C9ⁱ	166.55 (15)	O1C—Cl1—O2Cⁱ	89.7 (7)
C9ⁱⁱ—Ca1—C9ⁱ	92.42 (5)	O4C—Cl1—O2C	105.5 (7)
C9ⁱⁱⁱ—Ca1—C9ⁱ	92.42 (5)	O4Cⁱ—Cl1—O2C	55.5 (8)
O1ⁱⁱ—Ca1—C9	105.63 (15)	O1Cⁱ—Cl1—O2C	89.7 (7)
O1ⁱ—Ca1—C9	108.44 (15)	O1C—Cl1—O2C	123.9 (7)
O1ⁱⁱⁱ—Ca1—C9	94.80 (16)	O2Cⁱ—Cl1—O2C	146.3 (10)
O1—Ca1—C9	47.97 (15)	O4C—Cl1—O3C	113.5 (8)
O2ⁱⁱⁱ—Ca1—C9	100.50 (14)	O4Cⁱ—Cl1—O3C	47.5 (8)
O2ⁱⁱ—Ca1—C9	77.22 (14)	O1Cⁱ—Cl1—O3C	110.7 (11)
O2ⁱ—Ca1—C9	166.55 (15)	O1C—Cl1—O3C	99.1 (10)
O2—Ca1—C9	20.99 (16)	O2Cⁱ—Cl1—O3C	68.0 (7)
C9ⁱⁱ—Ca1—C9	92.42 (5)	O2C—Cl1—O3C	102.7 (7)
C9ⁱⁱⁱ—Ca1—C9	92.42 (5)	O4C—Cl1—O3Cⁱ	47.5 (8)
C9ⁱ—Ca1—C9	156.3 (2)	O4Cⁱ—Cl1—O3Cⁱ	113.5 (8)
C8—O1—Co1	134.6 (4)	O1Cⁱ—Cl1—O3Cⁱ	99.1 (10)
C8—O1—Ca1	113.4 (4)	O1C—Cl1—O3Cⁱ	110.7 (11)
Co1—O1—Ca1	111.99 (16)	O2Cⁱ—Cl1—O3Cⁱ	102.7 (7)
C5—N1—C1	108.2 (7)	O2C—Cl1—O3Cⁱ	68.0 (7)
C5—N1—C4	110.2 (7)	O3C—Cl1—O3Cⁱ	148.9 (11)
C1—N1—C4	109.1 (7)	O1Cⁱ—O1C—Cl1	72.9 (4)
C5—N1—Co1	111.2 (5)	O4Cⁱ—O2C—Cl1	57.7 (8)
C1—N1—Co1	111.3 (5)	O4Cⁱ—O2C—O3Cⁱ	105.8 (11)
C4—N1—Co1	106.9 (5)	Cl1—O2C—O3Cⁱ	56.7 (7)
N1—C1—C2	110.9 (7)	O4Cⁱ—O3C—Cl1	59.7 (9)
N1—C1—H1A	109.5	O4Cⁱ—O3C—O2Cⁱ	104.7 (12)
C2—C1—H1A	109.5	Cl1—O3C—O2Cⁱ	55.3 (7)
N1—C1—H1B	109.5	O3Cⁱ—O4C—O2Cⁱ	139.0 (15)
C2—C1—H1B	109.5	O3Cⁱ—O4C—Cl1	72.8 (10)
H1A—C1—H1B	108.0	O2Cⁱ—O4C—Cl1	66.8 (10)
C9—O2—Ca1	113.8 (4)

Symmetry codes: (i) −x, −y, z; (ii) y, −x, −z; (iii) −y, x, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1^iv—H1A^iv···O3C	0.99	2.64	3.56 (2)	156
C2ⁱⁱⁱ—H2Aⁱⁱⁱ···O4C	0.99	2.68	3.55 (2)	147
C4^iv—H4C^iv···O1C	0.98	2.50	3.47 (2)	167
C5^v—H5A^v···O2C	0.99	2.59	3.48 (2)	148
C5ⁱⁱⁱ—H5Bⁱⁱⁱ···O4C	0.99	2.35	3.29 (2)	157
C6—H6A···O1W	0.99	2.35	3.23 (9)	149
C6^vi—H6B^vi···O1C	0.99	2.44	3.37 (2)	158
C6^vii—H6B^vii···O1C	0.99	2.55	3.51 (2)	164

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

Selected bond lengths and angles (Å, °) top

Co1—N1	2.192 (7)
Co1—N2	2.375 (7)
Co1—O1	2.060 (4)
Ca1—O1	2.429 (4)
Ca1—O2	2.469 (4)
N1···N1ⁱ	3.881 (9)
N2···N2ⁱ	4.206 (10)
Co1···Ca1	3.727 (1)
Co1···Co1ⁱⁱ	7.454 (2)

N1—Co1—N1ⁱ	124.5 (2)
N1—Co1—N2	78.0 (2)
N1—Co1—N2ⁱ	77.0 (3)
N2—Co1—N2ⁱ	124.6 (3)
O1—Co1—N1	121.2 (2)
O1—Co1—N1ⁱ	102.9 (2)
O1—Co1—N2	81.6 (2)
O1—Co1—N2ⁱ	152.4 (2)
O1—Co1—O1ⁱ	74.3 (2)
O1—Ca1—O1ⁱ	61.7 (2)
O1—Ca1—O1ⁱⁱ	137.5 (1)
O1—Ca1—O2	67.1 (1)
O1—Ca1—O2ⁱ	123.5 (1)
O1—Ca1—O2ⁱⁱ	73.9 (1)
O1—Ca1—O2ⁱⁱⁱ	96.6 (1)
O2—Ca1—O2ⁱ	169.1 (2)
Co1—O1—Ca1	112.0 (2)

Symmetry codes: (i) -x, -y, z; (ii) y, -x, -z; (iii) -y, x, -z.

Hydrogen-bond geometry (Å, °) top

Note that both models of the disordered perchlorate anion form the same interactions; only one value for each interaction involving oxygen atoms of the ClO₄^- anion is therefore reported.

D—H···A	D—H	H···A	D···A	D—H···A
C1^iv—H1A^iv···O3C	0.99	2.64	3.56 (2)	156.1
C2ⁱⁱⁱ—H2Aⁱⁱⁱ···O4C	0.99	2.68	3.55 (2)	146.8
C4^iv—H4C^iv···O1C	0.98	2.50	3.47 (2)	167.2
C5^v—H5A^v···O2C	0.99	2.59	3.48 (2)	148.4
C5ⁱⁱⁱ—H5Bⁱⁱⁱ···O4C	0.99	2.35	3.29 (2)	157.4
C6—H6A···O1W	0.99	2.35	3.23 (9)	148.6
C6^vi—H6B^vi···O1C	0.99	2.44	3.37 (2)	157.7
C6^vii—H6B^vii···O1C	0.99	2.55	3.51 (2)	164.0

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

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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