Crystal structure of bis­{μ-2-[bis­(2-hy­droxy­eth­yl)amino]­ethano­lato}bis­(μ-3,5-di­methyl­pyrazolato)tricopper(II) dibromide sesquihydrate

Vynohradov, O.S.; Pavlenko, V.A.; Naumova, D.D.; Partsevska, S.V.; Shova, S.; Safarmamadov, S.M.

doi:10.1107/S2056989020012323

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ISSN: 2056-9890

Volume 76| Part 10| October 2020| Pages 1641-1644

https://doi.org/10.1107/S2056989020012323

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Crystal structure of bis{μ-2-[bis(2-hydroxyethyl)amino]ethanolato}bis(μ-3,5-dimethylpyrazolato)tricopper(II) dibromide sesquihydrate

Oleksandr S. Vynohradov,^a Vadim A. Pavlenko,^a Dina D. Naumova,^a Sofiia V. Partsevska,^a Sergiu Shova ^b and Safarmamad M. Safarmamadov ^c ^*

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, ^bPoni Petru Institute of Macromolecular Chemistry, Aleea Gr. Ghica, Voda 41A, 700487 Iasi, Romania, and ^cDepartment of Chemistry, Tajik National University, 17, Rudaki Avenue, Dushanbe, 734025, Tajikistan
^*Correspondence e-mail: sash65@mail.ru

Edited by G. Diaz de Delgado, Universidad de Los Andes, Venezuela (Received 3 August 2020; accepted 7 September 2020; online 11 September 2020)

In the title bicyclic trinuclear pyrazolate aminoalcohol complex, [Cu₃(C₅H₇N₂)₂(C₆H₁₄NO₃)₂]Br₂·1.5H₂O, the central Cu atom lies on a center of symmetry and is involved in the formation of two five-membered rings. It has a coordination number of 4, is in a distorted tetrahedral environment and is connected by the bridging oxygen atoms of the deprotonated OH groups of different aminoalcohol groups, and by the N atoms of deprotonated dimethylpyrazole ligands. The peripheral Cu atom is in a trigonal–bipyramidal coordination environment formed by the nitrogen atom of the deprotonated bridging dimethylpyrazole unit, the bridging oxygen atom of the deprotonated OH group, two oxygen atoms of the protonated hydroxy groups and the nitrogen atom of triethanolamine. One of the C atoms and the Br⁻ anion were found to be disordered over two positions with occupancy factors of 0.808 (9):0.192 (9) and 0.922 (3):0.078 (3), respectively.

Keywords: copper; copper complexes; crystal structure; pyrazole; triethanolamine; X-ray crystallography; aminoalcohol ligand.

CCDC reference: 2030043

1. Chemical context

Coordination compounds of paramagnetic transition-metal complexes with polydentate and polynuclear ligands are of great interest because of their versatile magnetic properties, in particular, magnetic superexchange mediated by ligand-bridging functions (Pavlishchuk et al., 2010 , 2011 ; Strotmeyer et al., 2003 ; Gumienna-Kontecka et al., 2007 ) or spin-crossover behavior (Suleimanov et al., 2015 ; Gural'skiy et al., 2012 ). Amino alcohols can be used for the synthesis of similar complexes since they are versatile and effective polydentate ligands in coordination chemistry (Vynohradov et al., 2020 ). It is well known that polynuclear complexes of 3d metals with amino alcohols (acting both as neutral and acidic ligands) can indicate non-trivial magnetic properties and biological activity. Mono-, di-, and trinuclear complexes of copper(II) with triethanolamine are widely studied because of their interesting magnetic properties (Escovar et al., 2005 ). The magnetic properties of copper(II) complexes with triethanolamine range from ferromagnetic to antiferromagnetic, with minor changes in the structure of the complex affecting the nature of the exchange interactions that control the ultimate magnetization (Boulsourani et al., 2011 ). In addition, copper(II) complexes with triethanolamine can bind to DNA (Sama et al., 2019 ) and show catecholase activity (Sama et al., 2017 ). Amino alcohol complexes of copper(II) and zinc show catalytic activity in the reactions of conversion of alkanes or cycloalkanes to carboxylic acids, which can help to increase the yield of products (Ansari et al., 2016 ). Triethanolamine is a polyfunctional O,N-ligand that can bind metal ions in its neutral or deprotonated form leading to an alcoholate. Finally, atoms of the same or different metals can be linked by bridging oxygen atoms to form mono- and heterometallic polynuclear complexes (Dias et al., 2015 ; Kirillov et al., 2007 ). As part of our continuing interest in multifunctional transition-metal complexes with polydentate and polynuclear ligands, we report herein the synthesis and crystal structure of a new trinuclear copper(II) mixed-ligand complex with triethanolamine and 3,5-dimethylpyrazole.

2. Structural commentary

The crystal structure of the title compound (Fig. 1) comprises trinuclear Cu₃(dmpz-H)₂(H₂TEA)₂²⁺ cationic units linked via two bridging bromine anions. The central Cu2 atom lies on a center of symmetry and is involved in the formation of two five-membered rings. Each ring is formed by two copper atoms connected by the bridging oxygen atom of the monodeprotonated triethanolamine and the bridging deprotonated dimethylpyrazole. The five-membered bimetallic rings are not planar. The nitrogen atoms of the dimethylpyrazole bridging ligand are practically in the same plane as the metal atoms, while the bridging oxygen atom is out of the plane by 0.450 (3) Å. The copper(II) atoms have different coordination environments. The peripheral Cu1 atom is in a trigonal–bipyramidal coordination environment formed by two N2 nitrogen atoms of the deprotonated bridging dimethylpyrazole ligands, the bridging oxygen atom of the deprotonated OH group, two oxygen atoms of the protonated hydroxy groups and the triethanolamine nitrogen atom. The central Cu2 atom (coordination number 4) is in a distorted (flattened) tetrahedral environment and is surrounded by the bridging oxygen atoms of the deprotonated OH groups of different amino alcohol molecules, and by N3 and N3ⁱ symmetry code: (i) $[{3\over 2}]$ − x, y, 1 − z] atoms of different deprotonated molecules of dimethylpyrazole. The interatomic distances between the N3, O1 and N3ⁱ, O1ⁱ atoms are 2.726 (4) Å. The distances between the atoms O1, O1ⁱ and N3, N3ⁱ are similar at 2.915 (4) and 2.970 (5) Å, respectively. The intermetallic separations are Cu1⋯Cu2 = 3.2829 (5) and Cu1⋯Cu1ⁱ = 6.4784 (10) Å.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level [Symmetry code: (i) $[{3\over 2}]$ − x, y, 1 − z].

The triethanolamine ligand is coordinated in a tetradentate manner by all donor atoms. As a result of such a coordination of triethanolamine from both sides of the complex molecule, three similar five-membered cyclic Cu–O–C–C–N fragments are formed. Bridging oxygen atoms arise from the coordination of the amino alcohol to a metal atom with the deprotonation of only one OH group. The coordinated triethanolamine is monodeprotonated, and the other two hydroxy groups are protonated and bonded by hydrogen bonds to the adjacent molecules via bridging bromine anions. The distances between Cu1 and the oxygen atoms of the deprotonated [Cu1—O1 = 1.930 (2) Å] and protonated [Cu1—O2 = 2.308 (2), Cu1—O3 = 2.060 (3) Å] OH groups are different.

3. Supramolecular features

In the crystal, the trinuclear cationic complexes interact via O—H⋯Br hydrogen bonding (Table 1), forming one-dimensional supramolecular networks. The distances between copper atoms within the supramolecular chain are Cu1⋯Cu1(− $[{1\over 2}]$ + x, 1 − y, z) = 7.3123 (4) Å, Cu2⋯Cu2(− $[{1\over 2}]$ + x, 1 − y, z) = 7.2470 (4) Å, Cu1(− $[{1\over 2}]$ + x, 1 − y, z)⋯Cu1( $[{3\over 2}]$ − x, y, 1 − z) = 8.9185 (12) Å, and Cu1⋯Cu1(1 − x, 1 − y, 1 − z) = 10.5517 (10) Å. The crystal structure is built up from the parallel packing of discrete pillars along the a axis (Fig. 2). The co-crystallized water molecules, which are fractionally disordered over several positions, fill the voids formed in the crystal and do not contribute significantly to extending the hydrogen-bonded network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯Br1ⁱ	0.83	2.50	3.288 (3)	158
O3—H3B⋯Br1X	0.85	2.37	3.207 (8)	168
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+1, z]$ .

Figure 2
Crystal packing of the title compound viewed along the a- (left) and b-axis (right) directions.

4. Database survey

A search of the Cambridge Structural Database (CSD version 5.40, update of August 2019; Groom et al., 2016 ) for the Cu(HO-CH₂CH₂)(O-CH₂CH₂)₂N moiety revealed 171 hits. Most similar to the title compound are the trinuclear complexes with coordinated triethanolamine and other ligands [WISQOH, WISQUN (Sun et al., 2018 ); AWEQEZ, AWEQID, AWEQOJ, AWEQUP (Boulsourani et al., 2011); DEGSOX (Ferguson et al., 1985 ); FISJIB (Tudor et al., 2005 ); KUDYUF (Dias et al., 2015); MEDHUZ, MEDHUZ01, MEDJAH, MEDJEL, MEDJIP (Escovar et al., 2005); OYALEH02 (Ansari et al., 2016); ZACTIJ01, ZAGYIS (Ozarowski et al., 2015 )].

5. Synthesis and crystallization

Cu₃(dmpz-H)₂(H₂TEA)₂Br₂ (dmpz-H = deprotonated 3,5-dimethyl-1H-pyrazole and H₂TEA = monodeprotonated triethanolamine) was synthesized at room temperature by the addition of a copper powder (2.34 mmol, 0.15 g) and copper(II) bromide (2.34 mmol, 0.525 g) mixture to an acetonitrile solution of 3,5-dimethyl-1H-pyrazole (4.68 mmol, 0.45 g). Triethanolamine (2.34 mmol, 0.31 ml) was added immediately. The reaction mixture was stirred without heating for one h with free air access until dissolution of the copper powder, and a green precipitate of the product was obtained. The precipitate was filtered off, dissolved in methanol, and filtered off from the undissolved copper residues. Green crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent. The yield was 50%. The obtained dark-green crystals were studied by elemental analysis (calculated C 31.56%, H 5.05% and N 10.04%, found C 30.83%, H 5.73%, N 10.38%). The reaction scheme is shown in Fig. 3.

Figure 3
Reaction scheme to obtain the title compound.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were included in geometrically calculated positions (O—H = 0.83–0.88 Å, C—H = 0.96–0.97 Å) with U_iso = 1.2U_eqC) or U_iso = 1.5U_eq(O,C-methyl). Atom C6 and the Br⁻ anion were found to be disordered over two resolvable positions with occupancy factors of 0.808 (9):0.192 (9) and 0.922 (3):0.078 (3), respectively. Their positional parameters were refined using available tools (see the CIF in the supporting information).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₃(C₅H₇N₂)₂(C₆H₁₄NO₃)₂]Br₂·1.5H₂O
M_r	864.08
Crystal system, space group	Monoclinic, I2/a
Temperature (K)	293
a, b, c (Å)	14.4930 (7), 8.8855 (3), 26.6017 (11)
β (°)	103.998 (5)
V (Å³)	3324.0 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	4.35
Crystal size (mm)	0.25 × 0.15 × 0.15

Data collection
Diffractometer	Rigaku Oxford Diffraction Xcalibur, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.514, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10477, 3946, 3296
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.689

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.09
No. of reflections	3946
No. of parameters	199
No. of restraints	11
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.52
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2030043

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989020012323/dj2014sup1.cif

here is the mol file of structural formula of the title compound. DOI: https://doi.org/10.1107/S2056989020012323/dj2014sup3.mol

here is the IR spectrum of the title compound. DOI: https://doi.org/10.1107/S2056989020012323/dj2014sup4.txt

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020012323/dj2014Isup5.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis{µ-2-[bis(2-hydroxyethyl)amino]ethanolato}-1:2κ⁴O,O',\ O'':O;2:3κ⁴O:O,O',O''-\ bis(µ-3,5-dimethylpyrazolato)-1:2κ²N¹:N²;\ 2:3N¹:N²-tricopper(II) dibromide sesquihydrate top

Crystal data top

[Cu₃(C₅H₇N₂)₂(C₆H₁₄NO₃)₂]Br₂·1.5H₂O	F(000) = 1744
M_r = 864.08	D_x = 1.727 Mg m⁻³
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
a = 14.4930 (7) Å	Cell parameters from 4599 reflections
b = 8.8855 (3) Å	θ = 1.6–27.9°
c = 26.6017 (11) Å	µ = 4.35 mm⁻¹
β = 103.998 (5)°	T = 293 K
V = 3324.0 (2) Å³	Block, dark green
Z = 4	0.25 × 0.15 × 0.15 mm

Data collection top

Rigaku Oxford Diffraction Xcalibur, Eos diffractometer	3946 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3296 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Detector resolution: 8.0797 pixels mm^-1	θ_max = 29.3°, θ_min = 2.4°
ω scans	h = −16→18
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	k = −9→11
T_min = 0.514, T_max = 1.000	l = −35→36
10477 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.105	w = 1/[σ²(F_o²) + (0.0485P)² + 4.2091P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
3946 reflections	Δρ_max = 0.61 e Å⁻³
199 parameters	Δρ_min = −0.52 e Å⁻³
11 restraints

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)
Cu1	0.84276 (3)	0.55507 (4)	0.62368 (2)	0.03014 (12)
Cu2	0.750000	0.49500 (6)	0.500000	0.03372 (15)
O1	0.79457 (19)	0.6382 (3)	0.55533 (8)	0.0434 (6)
O2	0.75819 (19)	0.6565 (3)	0.67875 (10)	0.0492 (6)
H2	0.701401	0.678302	0.675390	0.074*
O3	0.9595 (2)	0.4666 (3)	0.67533 (11)	0.0571 (7)
H3A	0.991686	0.384510	0.679523	0.086*	0.808 (9)
H3B	0.986816	0.387400	0.668063	0.086*	0.192 (9)
N1	0.91464 (19)	0.7483 (3)	0.64151 (10)	0.0336 (6)
N2	0.77343 (19)	0.3725 (3)	0.60337 (9)	0.0316 (5)
N3	0.72982 (19)	0.3495 (3)	0.55213 (9)	0.0323 (6)
C1	0.8348 (3)	0.7810 (4)	0.54973 (13)	0.0494 (10)
H1A	0.790451	0.859727	0.553258	0.059*
H1B	0.846751	0.789021	0.515481	0.059*
C2	0.9267 (3)	0.8016 (4)	0.59024 (13)	0.0460 (8)
H2A	0.976989	0.744829	0.580605	0.055*
H2B	0.944604	0.907048	0.592508	0.055*
C3	0.8581 (3)	0.8578 (4)	0.66391 (15)	0.0480 (9)
H3C	0.809372	0.901971	0.636341	0.058*
H3D	0.899332	0.938101	0.680996	0.058*
C4	0.8128 (3)	0.7830 (5)	0.70191 (16)	0.0561 (10)
H4A	0.861466	0.750289	0.731725	0.067*
H4B	0.771818	0.854094	0.713755	0.067*
C5	1.0076 (3)	0.7209 (5)	0.67819 (16)	0.0555 (10)
H5BC	1.056188	0.726257	0.658782	0.067*	0.192 (9)
H5BD	1.019202	0.803170	0.702872	0.067*	0.192 (9)
H5AA	1.054166	0.790854	0.671037	0.067*	0.808 (9)
H5AB	1.001831	0.738938	0.713262	0.067*	0.808 (9)
C7	0.7491 (2)	0.2588 (4)	0.63086 (12)	0.0363 (7)
C8	0.6888 (3)	0.1623 (4)	0.59740 (14)	0.0406 (8)
H8	0.661023	0.074739	0.606027	0.049*
C9	0.6785 (2)	0.2229 (4)	0.54863 (13)	0.0365 (7)
C10	0.7851 (3)	0.2510 (5)	0.68850 (13)	0.0552 (10)
H10A	0.848281	0.210080	0.696948	0.083*
H10B	0.744002	0.187678	0.702649	0.083*
H10C	0.786095	0.350270	0.702877	0.083*
C11	0.6195 (3)	0.1634 (5)	0.49835 (16)	0.0575 (11)
H11A	0.559290	0.214164	0.489894	0.086*
H11B	0.609514	0.057368	0.501520	0.086*
H11C	0.652047	0.180536	0.471421	0.086*
C6	1.0402 (3)	0.5685 (5)	0.6742 (3)	0.0616 (16)	0.808 (9)
H6A	1.093912	0.546357	0.702993	0.074*	0.808 (9)
H6B	1.060015	0.555500	0.642187	0.074*	0.808 (9)
C6B	1.0213 (14)	0.5817 (9)	0.7073 (4)	0.0616 (16)	0.192 (9)
H6BA	1.004131	0.594819	0.740059	0.074*	0.192 (9)
H6BB	1.087428	0.550866	0.714297	0.074*	0.192 (9)
Br1	1.05467 (4)	0.16214 (7)	0.65764 (5)	0.0663 (3)	0.922 (3)
O1W	1.0873 (10)	0.3397 (16)	0.5606 (5)	0.070 (3)*	0.25
H1WA	1.038994	0.394250	0.558614	0.106*	0.25
H1WB	1.082024	0.278840	0.584344	0.106*	0.25
Br1X	1.0615 (5)	0.1928 (9)	0.6317 (5)	0.0663 (3)	0.078 (3)
O2W	1.0549 (11)	0.4390 (18)	0.5497 (6)	0.082 (4)*	0.25
H2WA	0.996778	0.470066	0.536178	0.123*	0.25
H2WB	1.043988	0.373266	0.571568	0.123*	0.25
O3W	0.9438 (11)	0.5317 (17)	0.5068 (6)	0.081 (4)*	0.25
H3WA	0.954628	0.626818	0.515273	0.122*	0.25
H3WB	1.002938	0.507648	0.511103	0.122*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0351 (2)	0.0281 (2)	0.02443 (19)	−0.00146 (15)	0.00192 (15)	0.00083 (14)
Cu2	0.0532 (4)	0.0248 (3)	0.0211 (2)	0.000	0.0048 (2)	0.000
O1	0.0705 (17)	0.0284 (12)	0.0251 (10)	−0.0126 (12)	−0.0006 (11)	0.0021 (9)
O2	0.0461 (15)	0.0502 (16)	0.0552 (15)	−0.0009 (12)	0.0198 (12)	−0.0090 (12)
O3	0.0548 (16)	0.0369 (14)	0.0650 (17)	0.0088 (12)	−0.0140 (14)	−0.0003 (13)
N1	0.0327 (14)	0.0316 (14)	0.0333 (13)	−0.0008 (11)	0.0017 (11)	−0.0030 (11)
N2	0.0372 (14)	0.0304 (13)	0.0255 (12)	−0.0024 (11)	0.0043 (10)	0.0038 (10)
N3	0.0405 (15)	0.0288 (13)	0.0249 (12)	−0.0033 (11)	0.0027 (11)	0.0005 (10)
C1	0.079 (3)	0.0348 (19)	0.0291 (16)	−0.0169 (19)	0.0029 (17)	0.0028 (14)
C2	0.056 (2)	0.0382 (19)	0.0451 (19)	−0.0124 (17)	0.0148 (17)	0.0001 (16)
C3	0.053 (2)	0.041 (2)	0.050 (2)	−0.0022 (17)	0.0127 (18)	−0.0158 (17)
C4	0.058 (2)	0.062 (3)	0.051 (2)	0.001 (2)	0.0181 (19)	−0.019 (2)
C5	0.038 (2)	0.056 (2)	0.061 (2)	−0.0050 (18)	−0.0104 (18)	0.007 (2)
C7	0.0411 (18)	0.0321 (17)	0.0385 (17)	0.0058 (14)	0.0150 (14)	0.0088 (14)
C8	0.044 (2)	0.0293 (17)	0.052 (2)	−0.0003 (14)	0.0186 (16)	0.0068 (15)
C9	0.0369 (17)	0.0279 (16)	0.0434 (18)	−0.0016 (14)	0.0069 (14)	−0.0009 (14)
C10	0.079 (3)	0.051 (2)	0.0374 (19)	0.001 (2)	0.0176 (19)	0.0151 (17)
C11	0.058 (3)	0.047 (2)	0.060 (2)	−0.0145 (19)	0.001 (2)	−0.0107 (19)
C6	0.042 (3)	0.054 (3)	0.078 (4)	0.004 (2)	−0.007 (3)	−0.014 (3)
C6B	0.042 (3)	0.054 (3)	0.078 (4)	0.004 (2)	−0.007 (3)	−0.014 (3)
Br1	0.0543 (3)	0.0459 (3)	0.0959 (6)	−0.0023 (2)	0.0127 (3)	−0.0174 (3)
Br1X	0.0543 (3)	0.0459 (3)	0.0959 (6)	−0.0023 (2)	0.0127 (3)	−0.0174 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.930 (2)	C4—H4A	0.9700
Cu1—O2	2.308 (2)	C4—H4B	0.9700
Cu1—O3	2.060 (3)	C5—H5BC	0.9700
Cu1—N1	2.005 (3)	C5—H5BD	0.9700
Cu1—N2	1.916 (3)	C5—H5AA	0.9700
Cu2—O1	1.935 (2)	C5—H5AB	0.9700
Cu2—O1ⁱ	1.935 (2)	C5—C6	1.447 (6)
Cu2—N3	1.969 (2)	C5—C6B	1.447 (6)
Cu2—N3ⁱ	1.969 (2)	C7—C8	1.384 (5)
O1—C1	1.420 (4)	C7—C10	1.497 (5)
O2—H2	0.8291	C8—H8	0.9300
O2—C4	1.426 (5)	C8—C9	1.379 (5)
O3—H3A	0.8581	C9—C11	1.499 (5)
O3—H3B	0.8520	C10—H10A	0.9600
O3—C6	1.485 (5)	C10—H10B	0.9600
O3—C6B	1.485 (6)	C10—H10C	0.9600
N1—C2	1.493 (4)	C11—H11A	0.9600
N1—C3	1.486 (4)	C11—H11B	0.9600
N1—C5	1.480 (4)	C11—H11C	0.9600
N2—N3	1.372 (3)	C6—H6A	0.9700
N2—C7	1.343 (4)	C6—H6B	0.9700
N3—C9	1.340 (4)	C6B—H6BA	0.9700
C1—H1A	0.9700	C6B—H6BB	0.9700
C1—H1B	0.9700	O1W—H1WA	0.8426
C1—C2	1.508 (5)	O1W—H1WB	0.8490
C2—H2A	0.9700	O2W—H2WA	0.8768
C2—H2B	0.9700	O2W—H2WB	0.8660
C3—H3C	0.9700	O3W—H3WA	0.8786
C3—H3D	0.9700	O3W—H3WB	0.8643
C3—C4	1.489 (6)	O3W—H3WBⁱⁱ	1.06 (3)

O1—Cu1—O2	108.77 (11)	C4—C3—H3C	109.5
O1—Cu1—O3	145.70 (12)	C4—C3—H3D	109.5
O1—Cu1—N1	86.79 (10)	O2—C4—C3	110.4 (3)
O3—Cu1—O2	101.67 (11)	O2—C4—H4A	109.6
N1—Cu1—O2	80.85 (10)	O2—C4—H4B	109.6
N1—Cu1—O3	82.72 (11)	C3—C4—H4A	109.6
N2—Cu1—O1	90.73 (10)	C3—C4—H4B	109.6
N2—Cu1—O2	100.76 (10)	H4A—C4—H4B	108.1
N2—Cu1—O3	98.91 (11)	N1—C5—H5BC	107.7
N2—Cu1—N1	177.38 (10)	N1—C5—H5BD	107.7
O1—Cu2—O1ⁱ	97.76 (13)	N1—C5—H5AA	109.3
O1—Cu2—N3	88.57 (10)	N1—C5—H5AB	109.3
O1—Cu2—N3ⁱ	152.70 (11)	H5BC—C5—H5BD	107.1
O1ⁱ—Cu2—N3ⁱ	88.57 (10)	H5AA—C5—H5AB	108.0
O1ⁱ—Cu2—N3	152.70 (11)	C6—C5—N1	111.6 (4)
N3—Cu2—N3ⁱ	97.91 (15)	C6—C5—H5AA	109.3
Cu1—O1—Cu2	116.31 (11)	C6—C5—H5AB	109.3
C1—O1—Cu1	112.13 (19)	C6B—C5—N1	118.6 (6)
C1—O1—Cu2	125.31 (19)	C6B—C5—H5BC	107.7
Cu1—O2—H2	133.5	C6B—C5—H5BD	107.7
C4—O2—Cu1	104.9 (2)	N2—C7—C8	108.9 (3)
C4—O2—H2	107.1	N2—C7—C10	121.4 (3)
Cu1—O3—H3A	138.1	C8—C7—C10	129.7 (3)
Cu1—O3—H3B	121.0	C7—C8—H8	127.1
C6—O3—Cu1	106.1 (3)	C9—C8—C7	105.7 (3)
C6—O3—H3A	96.6	C9—C8—H8	127.1
C6B—O3—Cu1	113.8 (5)	N3—C9—C8	109.3 (3)
C6B—O3—H3B	116.7	N3—C9—C11	123.0 (3)
C2—N1—Cu1	102.98 (19)	C8—C9—C11	127.7 (3)
C3—N1—Cu1	110.5 (2)	C7—C10—H10A	109.5
C3—N1—C2	110.9 (3)	C7—C10—H10B	109.5
C5—N1—Cu1	110.7 (2)	C7—C10—H10C	109.5
C5—N1—C2	111.4 (3)	H10A—C10—H10B	109.5
C5—N1—C3	110.2 (3)	H10A—C10—H10C	109.5
N3—N2—Cu1	119.36 (19)	H10B—C10—H10C	109.5
C7—N2—Cu1	132.2 (2)	C9—C11—H11A	109.5
C7—N2—N3	108.1 (3)	C9—C11—H11B	109.5
N2—N3—Cu2	119.40 (19)	C9—C11—H11C	109.5
C9—N3—Cu2	132.6 (2)	H11A—C11—H11B	109.5
C9—N3—N2	108.0 (2)	H11A—C11—H11C	109.5
O1—C1—H1A	109.6	H11B—C11—H11C	109.5
O1—C1—H1B	109.6	O3—C6—H6A	110.3
O1—C1—C2	110.3 (3)	O3—C6—H6B	110.3
H1A—C1—H1B	108.1	C5—C6—O3	107.2 (4)
C2—C1—H1A	109.6	C5—C6—H6A	110.3
C2—C1—H1B	109.6	C5—C6—H6B	110.3
N1—C2—C1	109.6 (3)	H6A—C6—H6B	108.5
N1—C2—H2A	109.7	O3—C6B—H6BA	110.3
N1—C2—H2B	109.7	O3—C6B—H6BB	110.3
C1—C2—H2A	109.7	C5—C6B—O3	107.3 (4)
C1—C2—H2B	109.7	C5—C6B—H6BA	110.3
H2A—C2—H2B	108.2	C5—C6B—H6BB	110.3
N1—C3—H3C	109.5	H6BA—C6B—H6BB	108.5
N1—C3—H3D	109.5	H1WA—O1W—H1WB	101.0
N1—C3—C4	110.9 (3)	H2WA—O2W—H2WB	100.0
H3C—C3—H3D	108.0	H3WA—O3W—H3WB	95.4

Cu1—O1—C1—C2	20.5 (4)	N2—N3—C9—C8	−0.4 (4)
Cu1—O2—C4—C3	35.7 (4)	N2—N3—C9—C11	178.9 (3)
Cu1—O3—C6—C5	47.4 (5)	N2—C7—C8—C9	0.3 (4)
Cu1—O3—C6B—C5	−25.7 (17)	N3—N2—C7—C8	−0.5 (4)
Cu1—N1—C2—C1	43.4 (3)	N3—N2—C7—C10	−179.8 (3)
Cu1—N1—C3—C4	43.4 (4)	C2—N1—C3—C4	156.9 (3)
Cu1—N1—C5—C6	25.0 (5)	C2—N1—C5—C6	−88.9 (4)
Cu1—N1—C5—C6B	−18.7 (10)	C2—N1—C5—C6B	−132.6 (10)
Cu1—N2—N3—Cu2	6.0 (3)	C3—N1—C2—C1	−74.8 (4)
Cu1—N2—N3—C9	−173.7 (2)	C3—N1—C5—C6	147.6 (4)
Cu1—N2—C7—C8	172.7 (2)	C3—N1—C5—C6B	103.8 (10)
Cu1—N2—C7—C10	−6.6 (5)	C5—N1—C2—C1	162.0 (3)
Cu2—O1—C1—C2	−130.5 (3)	C5—N1—C3—C4	−79.3 (4)
Cu2—N3—C9—C8	180.0 (2)	C7—N2—N3—Cu2	−179.7 (2)
Cu2—N3—C9—C11	−0.7 (5)	C7—N2—N3—C9	0.6 (3)
O1—C1—C2—N1	−43.7 (4)	C7—C8—C9—N3	0.0 (4)
N1—C3—C4—O2	−54.2 (4)	C7—C8—C9—C11	−179.2 (4)
N1—C5—C6—O3	−48.3 (6)	C10—C7—C8—C9	179.5 (4)
N1—C5—C6B—O3	29.0 (18)

Symmetry codes: (i) −x+3/2, y, −z+1; (ii) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Br1ⁱⁱⁱ	0.83	2.50	3.288 (3)	158
O3—H3B···Br1X	0.85	2.37	3.207 (8)	168

Symmetry code: (iii) x−1/2, −y+1, z.

Acknowledgements

The authors acknowledge Denys Petlovanyi and Dmytro Vyshniak for help in conducting research, financial support and for providing interesting ideas for further scientific work.

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