A bis-chelate o-vanillin-2-ethano­lamine copper(II) complex bearing both imine and amine forms of the ligand

Plyuta, N.; Kokozay, V.N.; Rusanova, J.A.; Buvailo, H.; Goreshnik, E.; Petrusenko, S.

doi:10.1107/S205698902101166X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 77| Part 12| December 2021| Pages 1272-1275

https://doi.org/10.1107/S205698902101166X

Open

access

A bis-chelate o-vanillin-2-ethanolamine copper(II) complex bearing both imine and amine forms of the ligand

Nataliya Plyuta,^a ^* Vladimir N. Kokozay,^a Julia A. Rusanova,^a Halyna Buvailo,^a Evgeny Goreshnik ^b and Svitlana Petrusenko ^a

^aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64/13, 01601 Kyiv, Ukraine, and ^bDepartment of Inorganic Chemistry and Technology, Jožef Stefan Institute, Jamova, cesta 39, SI-1000 Ljubljana, Slovenia
^*Correspondence e-mail: plyutanataliya@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 12 October 2021; accepted 4 November 2021; online 9 November 2021)

The molecular bis-chelate complex (2-{[(2-hydroxyethyl-κO)amino-κN]methyl}-6-methoxyphenolato-κO)(2-{[(2-hydroxyethyl)imino-κN]methyl}-6-methoxyphenolato-κO)copper(II), [Cu(C₁₀H₁₄NO₃)(C₁₀H₁₂NO₃)] or [Cu(HL^im)(HL^am); HL^im = C₁₀H₁₄NO₃; HL^am = C₁₀H₁₂NO₃, represents the first compound containing a salicylidene-2-ethanolamine type ligand in both imino HL^im (Schiff base) and amino HL^am (reduced Schiff base) forms that has been structurally characterized on the basis of X-ray data. Two molecules of the monodeprotonated ligands coordinate the Cu^II ion in an (N,O_phen)-bidentate and an (N,O_phen,O_alc)-tridentate fashion in the case of the imino and amino forms, respectively. The shape of the CuN₂O₃ coordination polyhedron is a distorted square-pyramid (geometry index τ₅ = 0.26). Intermolecular N—H⋯O and O—H⋯O hydrogen bonds, involving H atoms of the amino and hydroxyethyl groups, create a two-dimensional supramolecular array extending parallel to (010).

Keywords: crystal structure; copper; geometry index; hydrogen bonding.

CCDC reference: 2120197

1. Chemical context

Over the last decade, research on transition-metal complexes with salicylidene-type Schiff bases (SB) gained a new impetus after a number of highly effective and simple M-(SB) catalysts were obtained, where M = Cu, Co, Al, etc (Payne et al., 2020 ; Mitra et al., 2015 ; Fei et al., 2014 ; Saha et al., 2013 ). It has been shown that incorporation of partially or fully reduced Schiff bases (RSB) into the coordination spheres of metal cations can significantly increase their catalytic activities (Liu et al., 2020 ; Huo et al., 2021 ; Adão et al., 2014 ; Sreenivasulu et al., 2005 ). Despite the fact that complexes with RSB ligands are supposed to be very promising objects for the creation of new catalysts, information about their syntheses and structures is rather limited. Continuing our work on the elaboration of alternative methods for the synthesis of coordination compounds (Kokozay et al., 2018 ), we have investigated the following system: zinc (powder) – copper (powder) – H₂L – ammonium thiocyanate – methanol, to prepare heterometallic Cu/Zn complexes with the Schiff base H₂L^im, which is formed in situ upon condensation of o-vanillin and 2-aminoethanol. The complex [Cu(HL^im)(HL^am)] (where H₂L^im = 2-[(2-hydroxyethyl)iminomethyl]-6-methoxyphenol; H₂L^am = 2-[(2-hydroxyethyl)aminomethyl]-6-methoxyphenol) was formed in the reaction mixture as an unintended by-product for which only a few crystals suitable for X-ray analysis were isolated.

Herein, we report the crystal structure of the title compound, [Cu(HL^im)(HL^am)] (I), which represents the first example of a mixed (SB/RSB) complex derived from salicylidene-2-aminoethanol type ligands.

2. Structural commentary

The asymmetric unit of (I) comprises one neutral molecular complex [Cu(HL^im)(HL^am)] (Fig. 1). The copper(II) ion has an O₃N₂ coordination set defined by two monodeprotonated molecules of the organic ligands realizing their bidentate (N,O) and tridentate (O,N,O) functions for the SB and RSB forms, respectively. This difference in coordination behavior of the ligands can be explained by a higher flexibility of the amine ligand, and is observed in similar bis-chelate copper(II) complexes with salicylidene-2-aminoethanol type ligands. Usually, [Cu(SB)₂] complexes are square-planar and [Cu(RSB)₂] complexes are octahedral. For the corresponding imine complexes, see: Li et al. (2005 ); Zabierowski et al. (2013 , 2014 ); Xin et al. (2019 ); for amine complexes, see: Xie et al. (2000 ). It is worth noting that such a dependence was not found for similar Ni^II complexes, which have an octahedral shape via both tridentate imino and amino ligands. For [Ni(SB)₂], see: Floyd et al. (2005 ); Wang et al. (2011a ,b ); for [Ni(RSB)₂], see: Zhang et al. (2007 ). The shape of the coordination polyhedron of the Cu^II ion in (I) can be described as distorted [4 + 1] square-pyramidal. The equatorial Cu—O(N) bond lengths vary from 1.923 (2) to 2.030 (3) Å and are in accordance with those found in related complexes (Stetsiuk et al., 2018 ; Xie et al., 2000; Zabierowski et al., 2013). The length of the long apical Cu—O bond of 2.432 (3) Å lies within the range of Cu^II—O bond lengths extending up to ca 2.70 Å (Alvarez, 2013 ). The deviations in cis and trans [O—Cu—O(N)] angles [80.08 (10)–108.36 (10)° and 157.96 (12)–173.44 (11)°, respectively] are caused by the steric hindrances that are typical for chelate rings. According to the τ criterion for five-coordinate complexes (Addison et al., 1984 ; O'Sullivan et al., 1999 ), the distortion of the CuN₂O₃ coordination polyhedron is about 26% along the pathway from regular square-pyramidal to regular trigonal–bipyramidal. The bond-valence sums calculated for Cu^II with CN = 4 (1.86 valence units) and CN = 5 (1.99 valence units) (Allmann, 1975 ; Shields et al., 2000 ) can serve as an additional argument in favor of the coordination number of 5 for Cu^II in (I).

Figure 1
Molecular structure of (I)

, with the numbering scheme and displacement ellipsoids drawn at the 50% probability level (carbon-bound H atoms are omitted for clarity).

3. Supramolecular features

Each molecule of (I) forms six intermolecular hydrogen bonds with four adjacent molecules whereby the following groups take part: non-coordinating hydroxyethyl and amino groups (as H-atom donors), half of the phenolato and methoxy groups (as H-atom acceptors) and the coordinating hydroxyethyl groups (both as H-atom donors and acceptors). Chains based on two hydrogen bonds O6—H6⋯O1ⁱⁱ and ⁱⁱⁱO6⋯H2—N2 (Table 1, Fig. 2) are formed along [001]. These chains are linked by O3—H3⋯O5ⁱ bonds (Table 1) into supramolecular sheets extending parallel to (010) (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5ⁱ	0.82	1.98	2.766 (3)	161
O6—H6⋯O1ⁱⁱ	0.75 (5)	2.19 (5)	2.916 (4)	163 (5)
N2—H2⋯O6ⁱⁱⁱ	0.98	2.27	3.107 (4)	142
Symmetry codes: (i) $[-x+2, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ .

Figure 2
Fragment of the crystal packing of (I), showing intermolecular O6—H6⋯O1 (green) and N2—H2⋯O6 (yellow) hydrogen bonds forming chains along [001]. [Symmetry codes: (′) 1 − x, 1 − y, $[{1\over 2}]$ + z; (′′) 1 − x, 1 − y, − $[{1\over 2}]$ + z].

Figure 3
The hydrogen-bonded sheet extending parallel to (010) in the crystal structure of (I)

. N—H⋯O (yellow) and O—H⋯O hydrogen bonds through participation of coordinating (green) and free (black) hydroxyethyl groups are shown.

4. Database survey

Among the 33 deposited crystal structures of bis-complexes with a salicylidene-2-aminoethanol-type ligand (CSD, version 5.42, last update February 2021; Groom et al., 2016 ), there are 30 hits for complexes with SBs and three hits for complexes with RSBs (Xie et al., 2000, 2003 ; Zhang et al., 2007). M(SB)(RSB) complexes including both forms of a ligand are not known up to now.

5. Synthesis and crystallization

o-Vanillin (0.3 g, 0.002 mol) and 2-aminoethanol (0.12 ml, 0.002 mol) were dissolved in methanol and then stirred magnetically at 323–333 K for 20 mins. Copper powder (0.06 g, 0.001 mol), zinc powder (0.07 g, 0.001 mol) and NH₄SCN (0.15 g, 0.002 mol) were added to the hot yellow solution with further stirring until total dissolution of powder was observed (about 4 h). The resulting brown solution was filtered and left for 1 d. A green powdery precipitate with a few green crystals available for X-ray crystallographic analysis was collected by filtration.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Carbon-bound H atoms were placed in idealized positions and refined using a riding model. H atoms of the NH and OH groups were located in a difference-Fourier map. For the final model they were also treated as riding on their parent atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₁₀H₁₄NO₃)(C₁₀H₁₂NO₃)]
M_r	453.97
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	8.3068 (9), 24.3280 (19), 10.1370 (9)
V (Å³)	2048.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.11
Crystal size (mm)	0.31 × 0.15 × 0.05

Data collection
Diffractometer	New Gemini, Dual, Cu at zero, Atlas
Absorption correction	Analytical (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.509, 0.855
No. of measured, independent and observed [I > 2σ(I)] reflections	10546, 3777, 3539
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.079, 1.06
No. of reflections	3777
No. of parameters	268
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.38
Absolute structure	Classical Flack method preferred over Parsons because s.u. lower
Absolute structure parameter	−0.011 (15)
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2120197

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902101166X/wm5622sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902101166X/wm5622Isup2.hkl

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: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(2-{[(2-Hydroxyethyl-κO)amino-κN]methyl}-6-methoxyphenolato-κO)(2-{[(2-hydroxyethyl)imino-κN]methyl}-6-methoxyphenolato-κO)copper(II) top

Crystal data top

[Cu(C₁₀H₁₄NO₃)(C₁₀H₁₂NO₃)]	D_x = 1.472 Mg m⁻³
M_r = 453.97	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 4616 reflections
a = 8.3068 (9) Å	θ = 4.1–28.6°
b = 24.3280 (19) Å	µ = 1.11 mm⁻¹
c = 10.1370 (9) Å	T = 150 K
V = 2048.6 (3) Å³	Plate, green
Z = 4	0.31 × 0.15 × 0.05 mm
F(000) = 948

Data collection top

New Gemini, Dual, Cu at zero, Atlas diffractometer	3777 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3539 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 10.6426 pixels mm^-1	θ_max = 28.8°, θ_min = 3.5°
ω scans	h = −10→9
Absorption correction: analytical (CrysAlisPro; Rigaku OD, 2015)	k = −31→31
T_min = 0.509, T_max = 0.855	l = −13→12
10546 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0466P)² + 0.2171P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.079	(Δ/σ)_max = 0.002
S = 1.06	Δρ_max = 0.31 e Å⁻³
3777 reflections	Δρ_min = −0.38 e Å⁻³
268 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower
1 restraint	Absolute structure parameter: −0.011 (15)

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. 1. Fixed Uiso At 1.2 times of: All C(H) groups, All C(H,H) groups, All N(H) groups At 1.5 times of: All C(H,H,H) groups, All O(H) groups 2.a Ternary CH refined with riding coordinates: N2(H2) 2.b Secondary CH2 refined with riding coordinates: C9(H9A,H9B), C10(H10A,H10B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B) 2.c Aromatic/amide H refined with riding coordinates: C3(H3A), C4(H4), C5(H5), C8(H8), C13(H13), C14(H14), C15(H15) 2.d Idealised Me refined as rotating group: C1(H1A,H1B,H1C), C11(H11A,H11B,H11C) 2.e Idealised tetrahedral OH refined as rotating group: O3(H3)

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

	x	y	z	U_iso*/U_eq
Cu1	0.71596 (4)	0.50706 (2)	0.41167 (6)	0.01347 (11)
O1	0.3846 (3)	0.37604 (10)	0.2532 (3)	0.0268 (6)
O2	0.5898 (3)	0.44465 (9)	0.3556 (2)	0.0194 (5)
O3	0.8418 (3)	0.47888 (13)	0.8013 (3)	0.0303 (6)
H3	0.910708	0.461250	0.840828	0.045*
O4	1.0725 (3)	0.63655 (10)	0.5057 (3)	0.0219 (5)
O5	0.8755 (2)	0.56419 (8)	0.4016 (3)	0.0176 (5)
O6	0.5411 (3)	0.52613 (11)	0.5985 (3)	0.0187 (5)
H6	0.567 (5)	0.5466 (18)	0.649 (5)	0.028*
N1	0.8651 (3)	0.46065 (12)	0.5178 (3)	0.0154 (6)
N2	0.5490 (3)	0.55538 (11)	0.3227 (3)	0.0155 (6)
H2	0.475620	0.530360	0.276506	0.019*
C1	0.2700 (6)	0.33956 (19)	0.1958 (5)	0.0428 (12)
H1A	0.200504	0.359757	0.137664	0.064*
H1B	0.206937	0.322833	0.264295	0.064*
H1C	0.325208	0.311543	0.146868	0.064*
C2	0.4986 (4)	0.35356 (15)	0.3365 (3)	0.0196 (7)
C3	0.5087 (5)	0.29840 (15)	0.3675 (3)	0.0245 (8)
H3A	0.434851	0.273654	0.332428	0.029*
C4	0.6303 (5)	0.27994 (15)	0.4515 (4)	0.0303 (9)
H4	0.636593	0.242899	0.473592	0.036*
C5	0.7397 (5)	0.31605 (16)	0.5012 (4)	0.0255 (8)
H5	0.821347	0.303071	0.555711	0.031*
C6	0.7321 (4)	0.37315 (15)	0.4720 (3)	0.0187 (7)
C7	0.6087 (4)	0.39289 (12)	0.3878 (3)	0.0155 (7)
C8	0.8504 (4)	0.40836 (15)	0.5316 (3)	0.0184 (7)
H8	0.924904	0.391349	0.586611	0.022*
C9	0.9906 (5)	0.48739 (15)	0.5970 (4)	0.0208 (8)
H9A	1.048384	0.513686	0.542842	0.025*
H9B	1.066860	0.460018	0.627594	0.025*
C10	0.9173 (5)	0.51648 (16)	0.7138 (4)	0.0246 (8)
H10A	1.000746	0.536379	0.760726	0.029*
H10B	0.838544	0.542958	0.682967	0.029*
C11	1.1634 (5)	0.67643 (17)	0.5768 (4)	0.0309 (9)
H11A	1.234707	0.695184	0.517408	0.046*
H11B	1.225148	0.658469	0.644258	0.046*
H11C	1.091562	0.702508	0.616645	0.046*
C12	0.9635 (3)	0.65617 (12)	0.4146 (4)	0.0180 (6)
C13	0.9540 (4)	0.71095 (14)	0.3758 (4)	0.0247 (8)
H13	1.025083	0.736751	0.410207	0.030*
C14	0.8373 (5)	0.72677 (16)	0.2852 (4)	0.0294 (9)
H14	0.832475	0.763044	0.256536	0.035*
C15	0.7285 (5)	0.68872 (16)	0.2376 (4)	0.0249 (8)
H15	0.648537	0.699987	0.179372	0.030*
C16	0.7364 (4)	0.63357 (14)	0.2756 (3)	0.0172 (7)
C17	0.8560 (4)	0.61619 (13)	0.3639 (3)	0.0156 (7)
C18	0.6167 (4)	0.59254 (15)	0.2197 (3)	0.0191 (7)
H18A	0.529395	0.612378	0.177709	0.023*
H18B	0.669693	0.570550	0.152753	0.023*
C19	0.4499 (4)	0.58501 (13)	0.4204 (4)	0.0201 (7)
H19A	0.354505	0.599835	0.378298	0.024*
H19B	0.510825	0.615315	0.457572	0.024*
C20	0.4019 (4)	0.54520 (15)	0.5289 (4)	0.0220 (8)
H20A	0.329361	0.563357	0.589924	0.026*
H20B	0.345529	0.514124	0.490604	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01244 (19)	0.01677 (18)	0.01119 (17)	0.00087 (13)	−0.0031 (2)	0.0002 (3)
O1	0.0330 (15)	0.0203 (12)	0.0270 (14)	−0.0059 (11)	−0.0155 (11)	0.0038 (11)
O2	0.0223 (13)	0.0170 (11)	0.0191 (11)	0.0016 (10)	−0.0084 (10)	0.0035 (10)
O3	0.0191 (13)	0.0563 (18)	0.0155 (12)	0.0059 (14)	−0.0001 (11)	0.0035 (13)
O4	0.0167 (12)	0.0237 (12)	0.0254 (12)	−0.0012 (10)	−0.0079 (11)	−0.0016 (11)
O5	0.0133 (10)	0.0172 (9)	0.0224 (11)	0.0013 (8)	−0.0023 (12)	0.0018 (13)
O6	0.0148 (13)	0.0261 (13)	0.0152 (11)	0.0016 (10)	−0.0013 (10)	−0.0025 (11)
N1	0.0091 (13)	0.0265 (15)	0.0107 (12)	0.0014 (11)	−0.0009 (10)	0.0005 (12)
N2	0.0123 (13)	0.0199 (14)	0.0143 (12)	−0.0019 (11)	−0.0028 (11)	−0.0014 (12)
C1	0.047 (3)	0.032 (2)	0.049 (3)	−0.017 (2)	−0.029 (2)	0.006 (2)
C2	0.0239 (19)	0.0221 (17)	0.0126 (15)	0.0020 (14)	−0.0013 (14)	0.0024 (14)
C3	0.030 (2)	0.0193 (16)	0.0239 (17)	−0.0026 (15)	−0.0004 (15)	−0.0018 (15)
C4	0.037 (2)	0.0180 (17)	0.036 (2)	0.0062 (16)	−0.0021 (17)	0.0066 (16)
C5	0.028 (2)	0.0234 (19)	0.0253 (18)	0.0093 (15)	−0.0033 (16)	0.0062 (17)
C6	0.0193 (18)	0.0226 (18)	0.0143 (17)	0.0049 (14)	0.0016 (13)	0.0019 (15)
C7	0.0187 (16)	0.0168 (13)	0.0109 (17)	0.0015 (12)	0.0027 (12)	0.0024 (13)
C8	0.0133 (17)	0.0290 (19)	0.0131 (15)	0.0095 (14)	0.0000 (13)	0.0046 (15)
C9	0.0138 (18)	0.033 (2)	0.0157 (16)	−0.0009 (15)	−0.0048 (15)	0.0074 (16)
C10	0.024 (2)	0.0272 (19)	0.0228 (18)	0.0012 (17)	−0.0099 (17)	−0.0019 (16)
C11	0.029 (2)	0.029 (2)	0.035 (2)	−0.0051 (17)	−0.0109 (18)	−0.0042 (18)
C12	0.0134 (14)	0.0215 (14)	0.0191 (14)	0.0022 (11)	0.0007 (17)	0.000 (2)
C13	0.0205 (18)	0.0205 (15)	0.033 (2)	−0.0040 (13)	0.0023 (15)	0.0013 (15)
C14	0.027 (2)	0.0220 (18)	0.039 (2)	0.0011 (16)	0.0012 (18)	0.0126 (17)
C15	0.0217 (19)	0.027 (2)	0.025 (2)	0.0035 (15)	−0.0027 (15)	0.0091 (17)
C16	0.0152 (17)	0.0231 (17)	0.0132 (16)	0.0018 (13)	0.0022 (13)	0.0021 (15)
C17	0.0144 (16)	0.0184 (15)	0.0139 (14)	0.0030 (13)	0.0054 (12)	0.0038 (13)
C18	0.0179 (18)	0.0265 (18)	0.0129 (15)	0.0031 (14)	−0.0018 (13)	0.0026 (15)
C19	0.0137 (15)	0.0221 (14)	0.0245 (17)	0.0014 (11)	0.0019 (16)	−0.0019 (19)
C20	0.0126 (18)	0.0302 (19)	0.0232 (18)	0.0016 (14)	0.0009 (14)	0.0037 (16)

Geometric parameters (Å, º) top

Cu1—O2	1.930 (2)	C5—C6	1.422 (5)
Cu1—O5	1.923 (2)	C6—C7	1.417 (5)
Cu1—O6	2.432 (3)	C6—C8	1.437 (5)
Cu1—N1	1.992 (3)	C8—H8	0.9300
Cu1—N2	2.030 (3)	C9—H9A	0.9700
O1—C1	1.426 (5)	C9—H9B	0.9700
O1—C2	1.382 (4)	C9—C10	1.508 (5)
O2—C7	1.310 (4)	C10—H10A	0.9700
O3—H3	0.8200	C10—H10B	0.9700
O3—C10	1.420 (5)	C11—H11A	0.9600
O4—C11	1.425 (4)	C11—H11B	0.9600
O4—C12	1.379 (4)	C11—H11C	0.9600
O5—C17	1.332 (4)	C12—C13	1.392 (5)
O6—H6	0.75 (5)	C12—C17	1.417 (5)
O6—C20	1.432 (4)	C13—H13	0.9300
N1—C8	1.286 (5)	C13—C14	1.390 (5)
N1—C9	1.467 (5)	C14—H14	0.9300
N2—H2	0.9800	C14—C15	1.381 (6)
N2—C18	1.491 (4)	C15—H15	0.9300
N2—C19	1.476 (4)	C15—C16	1.397 (5)
C1—H1A	0.9600	C16—C17	1.402 (5)
C1—H1B	0.9600	C16—C18	1.518 (5)
C1—H1C	0.9600	C18—H18A	0.9700
C2—C3	1.381 (5)	C18—H18B	0.9700
C2—C7	1.422 (5)	C19—H19A	0.9700
C3—H3A	0.9300	C19—H19B	0.9700
C3—C4	1.396 (5)	C19—C20	1.519 (5)
C4—H4	0.9300	C20—H20A	0.9700
C4—C5	1.360 (6)	C20—H20B	0.9700
C5—H5	0.9300

O2—Cu1—O6	93.16 (10)	N1—C9—H9A	109.5
O2—Cu1—N1	92.92 (11)	N1—C9—H9B	109.5
O2—Cu1—N2	87.35 (11)	N1—C9—C10	110.5 (3)
O5—Cu1—O2	157.96 (12)	H9A—C9—H9B	108.1
O5—Cu1—O6	108.36 (10)	C10—C9—H9A	109.5
O5—Cu1—N1	90.55 (10)	C10—C9—H9B	109.5
O5—Cu1—N2	91.65 (10)	O3—C10—C9	111.5 (3)
N1—Cu1—O6	93.37 (10)	O3—C10—H10A	109.3
N1—Cu1—N2	173.44 (11)	O3—C10—H10B	109.3
N2—Cu1—O6	80.08 (10)	C9—C10—H10A	109.3
C2—O1—C1	117.4 (3)	C9—C10—H10B	109.3
C7—O2—Cu1	128.1 (2)	H10A—C10—H10B	108.0
C10—O3—H3	109.5	O4—C11—H11A	109.5
C12—O4—C11	116.8 (3)	O4—C11—H11B	109.5
C17—O5—Cu1	128.2 (2)	O4—C11—H11C	109.5
Cu1—O6—H6	119 (3)	H11A—C11—H11B	109.5
C20—O6—Cu1	99.2 (2)	H11A—C11—H11C	109.5
C20—O6—H6	111 (3)	H11B—C11—H11C	109.5
C8—N1—Cu1	124.1 (2)	O4—C12—C13	123.9 (3)
C8—N1—C9	116.5 (3)	O4—C12—C17	114.8 (3)
C9—N1—Cu1	119.1 (2)	C13—C12—C17	121.2 (3)
Cu1—N2—H2	106.1	C12—C13—H13	120.3
C18—N2—Cu1	113.8 (2)	C14—C13—C12	119.5 (3)
C18—N2—H2	106.1	C14—C13—H13	120.3
C19—N2—Cu1	111.4 (2)	C13—C14—H14	119.9
C19—N2—H2	106.1	C15—C14—C13	120.1 (3)
C19—N2—C18	112.6 (3)	C15—C14—H14	119.9
O1—C1—H1A	109.5	C14—C15—H15	119.4
O1—C1—H1B	109.5	C14—C15—C16	121.1 (3)
O1—C1—H1C	109.5	C16—C15—H15	119.4
H1A—C1—H1B	109.5	C15—C16—C17	119.9 (3)
H1A—C1—H1C	109.5	C15—C16—C18	119.8 (3)
H1B—C1—H1C	109.5	C17—C16—C18	120.2 (3)
O1—C2—C7	113.5 (3)	O5—C17—C12	118.1 (3)
C3—C2—O1	124.4 (3)	O5—C17—C16	123.8 (3)
C3—C2—C7	122.1 (3)	C16—C17—C12	118.1 (3)
C2—C3—H3A	120.2	N2—C18—C16	112.7 (3)
C2—C3—C4	119.7 (3)	N2—C18—H18A	109.1
C4—C3—H3A	120.2	N2—C18—H18B	109.1
C3—C4—H4	119.9	C16—C18—H18A	109.1
C5—C4—C3	120.1 (3)	C16—C18—H18B	109.1
C5—C4—H4	119.9	H18A—C18—H18B	107.8
C4—C5—H5	119.2	N2—C19—H19A	109.9
C4—C5—C6	121.6 (4)	N2—C19—H19B	109.9
C6—C5—H5	119.2	N2—C19—C20	108.7 (3)
C5—C6—C8	117.7 (3)	H19A—C19—H19B	108.3
C7—C6—C5	119.2 (3)	C20—C19—H19A	109.9
C7—C6—C8	123.1 (3)	C20—C19—H19B	109.9
O2—C7—C2	118.6 (3)	O6—C20—C19	110.6 (3)
O2—C7—C6	124.2 (3)	O6—C20—H20A	109.5
C6—C7—C2	117.2 (3)	O6—C20—H20B	109.5
N1—C8—C6	127.5 (3)	C19—C20—H20A	109.5
N1—C8—H8	116.2	C19—C20—H20B	109.5
C6—C8—H8	116.2	H20A—C20—H20B	108.1

Cu1—O2—C7—C2	178.7 (2)	C5—C6—C7—C2	−0.3 (5)
Cu1—O2—C7—C6	−0.9 (5)	C5—C6—C8—N1	179.7 (3)
Cu1—O5—C17—C12	153.4 (3)	C7—C2—C3—C4	−0.1 (5)
Cu1—O5—C17—C16	−27.4 (5)	C7—C6—C8—N1	−1.2 (6)
Cu1—O6—C20—C19	−44.8 (3)	C8—N1—C9—C10	−102.7 (3)
Cu1—N1—C8—C6	2.6 (5)	C8—C6—C7—O2	0.2 (5)
Cu1—N1—C9—C10	71.2 (3)	C8—C6—C7—C2	−179.4 (3)
Cu1—N2—C18—C16	−62.6 (3)	C9—N1—C8—C6	176.1 (3)
Cu1—N2—C19—C20	−44.5 (3)	C11—O4—C12—C13	9.3 (5)
O1—C2—C3—C4	179.1 (3)	C11—O4—C12—C17	−169.1 (3)
O1—C2—C7—O2	1.8 (4)	C12—C13—C14—C15	2.2 (6)
O1—C2—C7—C6	−178.6 (3)	C13—C12—C17—O5	177.7 (3)
O4—C12—C13—C14	−178.6 (3)	C13—C12—C17—C16	−1.6 (5)
O4—C12—C17—O5	−3.9 (5)	C13—C14—C15—C16	−2.2 (6)
O4—C12—C17—C16	176.9 (3)	C14—C15—C16—C17	0.3 (6)
N1—C9—C10—O3	63.7 (4)	C14—C15—C16—C18	−179.0 (3)
N2—C19—C20—O6	63.9 (4)	C15—C16—C17—O5	−177.6 (3)
C1—O1—C2—C3	0.1 (5)	C15—C16—C17—C12	1.5 (5)
C1—O1—C2—C7	179.4 (4)	C15—C16—C18—N2	−134.9 (3)
C2—C3—C4—C5	−0.9 (6)	C17—C12—C13—C14	−0.3 (6)
C3—C2—C7—O2	−178.9 (3)	C17—C16—C18—N2	45.8 (4)
C3—C2—C7—C6	0.7 (5)	C18—N2—C19—C20	−173.8 (3)
C3—C4—C5—C6	1.3 (6)	C18—C16—C17—O5	1.6 (5)
C4—C5—C6—C7	−0.7 (6)	C18—C16—C17—C12	−179.2 (3)
C4—C5—C6—C8	178.5 (4)	C19—N2—C18—C16	65.4 (3)
C5—C6—C7—O2	179.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.82	1.98	2.766 (3)	161
O6—H6···O1ⁱⁱ	0.75 (5)	2.19 (5)	2.916 (4)	163 (5)
N2—H2···O6ⁱⁱⁱ	0.98	2.27	3.107 (4)	142

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

Acknowledgements

EG gratefully acknowledges the Slovenian Research Agency (ARRS) for financial support of the present study.

Funding information

This work was been supported by the Ministry of Education and Science of Ukraine: Grant of the Ministry of Education and Science of Ukraine for perspective development of the scientific direction `Mathematical sciences and natural sciences' at Taras Shevchenko National University of Kyiv. The work was also supported by the Slovenian Research Agency (ARRS) within the research program P1-0045, Inorganic Chemistry and Technology.

References

Adão, P., Barroso, S., Avecilla, F., Oliveira, M. C. & Pessoa, J. C. (2014). J. Organomet. Chem. 760, 212–223. Google Scholar
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Allmann, R. (1975). Monatsh. Chem. 106, 779–793. CrossRef CAS Web of Science Google Scholar
Alvarez, S. (2013). Dalton Trans. 42, 8617–8636. Web of Science CrossRef CAS PubMed Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fei, B.-L., Wang, J.-H., Yan, Q.-L., Liu, Q.-B., Long, J.-Y., Li, Y.-G., Shao, K.-Z., Su, Z.-M. & Sun, W.-Y. (2014). Chem. Lett. 43, 1158–1160. Web of Science CSD CrossRef CAS Google Scholar
Floyd, J. M., Gray, G. M., VanEngen Spivey, A. G., Lawson, C. M., Pritchett, T. M., Ferry, M. J., Hoffman, R. C. & Mott, A. G. (2005). Inorg. Chim. Acta, 358, 3773–3785. Web of Science CSD CrossRef CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Huo, S., Chen, H. & Zuo, W. (2021). Eur. J. Inorg. Chem. pp. 37–42. Web of Science CSD CrossRef Google Scholar
Kokozay, V. N., Vassilyeva, O. Y. & Makhankova, V. G. (2018). Direct Synthesis of Metal Complexes, edited by B. Kharisov, pp. 183–237. Amsterdam: Elsevier. Google Scholar
Li, L.-Z., Zhao, C., Xu, T., Ji, H.-W., Yu, Y.-H., Guo, G.-Q. & Chao, H. (2005). J. Inorg. Biochem. 99, 1076–1082. Web of Science CSD CrossRef PubMed CAS Google Scholar
Liu, K., Zhang, J., Huo, S., Dong, Q., Hao, Z., Han, Z., Lu, G.-L. & Lin, J. (2020). Inorg. Chim. Acta, 500, 119224. Web of Science CSD CrossRef Google Scholar
Mitra, M., Raghavaiah, P. & Ghosh, R. (2015). New J. Chem. 39, 200–205. Web of Science CSD CrossRef CAS Google Scholar
O'Sullivan, C., Murphy, G., Murphy, B. & Hathaway, B. (1999). J. Chem. Soc. Dalton Trans. pp. 1835–1844. Web of Science CSD CrossRef Google Scholar
Payne, J., McKeown, P., Kociok-Köhn, G. & Jones, M. D. (2020). Chem. Commun. 56, 7163–7166. Web of Science CSD CrossRef CAS Google Scholar
Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Saha, D., Maity, T., Bera, R. & Koner, S. (2013). Polyhedron, 56, 230–236. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shields, G. P., Raithby, P. R., Allen, F. H. & Motherwell, W. D. S. (2000). Acta Cryst. B56, 455–465. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sreenivasulu, B., Vetrichelvan, M., Zhao, F., Gao, S. & Vittal, J. J. (2005). Eur. J. Inorg. Chem. pp. 4635–4645. Web of Science CSD CrossRef Google Scholar
Stetsiuk, O., El-Ghayoury, A., Kokozay, V. N., Avarvari, N. & Petrusenko, S. R. (2018). J. Coord. Chem. 71, 68–77. Web of Science CSD CrossRef CAS Google Scholar
Wang, C.-Y., Li, J.-F., Wang, P. & Yuan, C.-J. (2011a). Acta Cryst. E67, m1227–m1228. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, C.-Y., Ye, J.-Y., Wu, X. & Han, Z.-P. (2011b). Acta Cryst. E67, m1229. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xie, Y., Bu, W., Chan, A. S.-C., Xu, X., Liu, Q., Zhang, Z., Yu, J. & Fan, Y. (2000). Inorg. Chim. Acta, 310, 257–260. Web of Science CSD CrossRef CAS Google Scholar
Xie, Y., Ni, J., Liu, X., Liu, Q., Xu, X., Du, C. & Zhu, Y. (2003). Trans. Met. Chem. 28, 367–370. Web of Science CSD CrossRef CAS Google Scholar
Xin, W., Jinglan, K., Yonghui, Z., Liguo, Y. & Linna, G. (2019). Z. Kristallogr. New Cryst. Struct. 234, 315–316. Web of Science CSD CrossRef CAS Google Scholar
Zabierowski, P., Szklarzewicz, J., Kurpiewska, K., Lewiński, K. & Nitek, W. (2013). Polyhedron, 49, 74–83. Web of Science CSD CrossRef CAS Google Scholar
Zabierowski, P., Szklarzewicz, J. & Nitek, W. (2014). Acta Cryst. C70, 659–661. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, S.-H., Zou, H.-H., Zeng, M.-H. & Liang, H. (2007). Acta Cryst. E63, m2564. Web of Science CSD CrossRef IUCr Journals Google Scholar

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