Crystal structure and Hirshfeld surface analysis of (1H-imidazole-κN3)[N-(2-oxido­benzyl­idene)tyrosinato-κ3O,N,O′]copper(II)

Suzuki, S.; Akiyama, Y.; Nakane, D.; Akitsu, T.

doi:10.1107/S2056989023004735

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ISSN: 2056-9890

Volume 79| Part 7| July 2023| Pages 596-599

https://doi.org/10.1107/S2056989023004735

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Crystal structure and Hirshfeld surface analysis of (1H-imidazole-κN³)[N-(2-oxidobenzylidene)tyrosinato-κ³O,N,O′]copper(II)

Soma Suzuki,^a Yukihito Akiyama,^a Daisuke Nakane ^a and Takashiro Akitsu ^a ^*

^aDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
^*Correspondence e-mail: akitsu2@rs.tus.ac.jp

Edited by J. Ellena, Universidade de Sâo Paulo, Brazil (Received 10 April 2023; accepted 30 May 2023; online 2 June 2023)

The title copper(II) complex, [Cu(C₁₆H₁₃NO₄)(C₃H₄N₂)], consists of a tridentate ligand synthesized from L-tyrosine and salicylaldehyde. One imidazole molecule is additionally coordinating to the copper(II) ion. The crystal structure features N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds. The Hirshfeld surface analysis indicates that the most important contributions to the packing are from H⋯H (37.9%), C⋯H (28.2%) and O⋯H/H⋯O (21.2%) contacts.

Keywords: Schiff base complex; copper; amino acid; Hirshfeld analysis; crystal structure.

CCDC reference: 2266335

1. Chemical context

Amino acid Schiff bases, which can be easily synthesized by mixing primary amines and carbonyl components, are organic ligands having an azomethine (C=N) group. They play an important and diverse role in coordination chemistry (Qiu et al., 2008 ; Li et al., 2010 ; Xue et al., 2009 ; Katsuumi et al., 2020 ; Akiyama et al., 2023 ). On the other hand, copper has various oxidation states, of which the divalent oxidation state is the most stable. Copper(II) ions readily form complexes and produce abundant coordination chemistry, while amino acid Schiff base–copper(II) complexes have been studied in terms of photoreaction with titanium dioxide (Takeshita et al., 2015 ), photocatalytic reduction of hexavalent chromium (Nakagame et al., 2019 ), and antibacterial activity (Otani et al., 2022 ). The ligand forms a tridentate chelate, but the introduction of a hydroxyl group is effective in increasing solubility in aqueous solvents (Miyagawa et al., 2020 ). On the other hand, many similar metal complexes with an amino acid having a hydroxyl group, L-tyrosine, have been reported (Pu et al., 2011 ; Wang et al., 2005 ; Tan et al., 2008 ).

In this report we describe the crystal structure and intermolecular interactions of the copper(II) complex coordinated by a tyrosine derivative and imidazole, which serves as a model for histidine residues in proteins and is effective for photoreactions with titanium dioxide. To obtain the product in higher yield than from conventional synthesis, microwave radiation was employed, although conventional synthesis may also give the same product.

2. Structural commentary

The molecular structure of the title compound consists of a tridentate ligand occupying the equatorial plane synthesized from L-tyrosine, salicylaldehyde and one imidazole molecule coordinating to the copper(II) center (Fig. 1). The C10—N2 distance is 1.322 (4) Å, close to a typical C=N double-bond length for an imine (Katsuumi et al., 2020). The Cu1—O1 and Cu1—O2 bond lengths are 1.892 (2) and 1.947 (2) Å, respectively, close to a typical Cu—O single-bond length (Katsuumi et al., 2020). The Cu1—N2 and Cu1—N3 bonds of 1.958 (2) and 1.932 (2) Å corresponds to the typical Cu—N single-bond length (Katsuumi et al., 2020). These four atoms coordinating to Cu1 have similar bond distances.

Figure 1
The molecular structure of the title compound with ellipsoids drawn at the 50& probability level.

3. Supramolecular features

Four intermolecular O—H⋯O, N—H⋯O, C—H⋯O hydrogen bonds (Table 1 and Fig. 2) are observed in the crystal; one hydrogen bond (O2—H11⋯N1ⁱ; symmetry code given in Table 1) forms a chain structure along the b-axis direction. The other hydrogen bonds (O4—H11⋯N1ⁱⁱ, O3—H4A⋯O4ⁱⁱⁱ and O4—H13A⋯C13^iv) link the molecules (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2ⁱ	0.75 (4)	2.40 (4)	3.050 (3)	147 (3)
N1—H11⋯O4ⁱⁱ	0.75 (4)	2.48 (3)	3.058 (3)	136 (3)
O4—H4A⋯O3ⁱⁱⁱ	0.74	1.98	2.666 (3)	154
C13—H13A⋯O4^iv	0.99	2.58	3.364 (3)	136
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A view of the O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, shown as dashed lines. [Symmetry codes: (i) x + $[{1\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1; (ii) −x + $[{3\over 2}]$ , −y + 1, z − $[{1\over 2}]$ ; (iii) −x, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (iv) −x + 1, y + $[{1\over 2}]$ , −z + $[{3\over 2}]$ .]

Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ; McKinnon et al., 2007 ) was performed to better understand the intermolecular interactions and contacts. The intermolecular O—H⋯O hydrogen bonds are indicated by bright-red spots appearing near O3 and O4 on the Hirshfeld surfaces mapped over d_norm and by two sharp spikes of almost the same length in the region 1.6 Å < (d_e + d_i) < 2.0 Å in the 2D finger plots (Fig. 3). The contributions to the packing from H⋯H, C⋯C, C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N contacts are 37.9, 0.4, 28.2, 21.2, and 5.2%, respectively. This structure is characterized by high proportions of H⋯H and C⋯H/H⋯C interactions, where H⋯H are van der Waals interactions. The force effect, C⋯H/H⋯C, is thought to arise from C—H⋯π interactions due to the presence of aromatic rings in the structure. The low value of C⋯C/C⋯C is the result of the low contribution of π–π stacking due to non-overlapping aromatic rings in the structure.

Figure 3
Hirshfeld surfaces mapped over d_norm and the two-dimensional fingerprint plots.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.41, update of March 2022; Groom et al., 2016 ) for similar structures returned three relevant entries: {2-(4-hydroxyphenyl)-2-[(3-methoxy-2-oxidobenzylidene)amino-κ²O²,N]- propanoato-κO}(1,10-phenanthroline-κ²N,N)copper(II) dihydrate (UNOSIA; Pu et al., 2011), 2,2-bipyridine N-salicylidenetyrosinatocopper(II) (QAJTAX01; Wang et al., 2005) and [(2S)-2-(3,5-dichloro-2-oxidobenzyl-ideneamino)-3-(4-hydroxyphenyl)-propionato-κ³O,N,O](dimethylformamide-κO)copper(II) (YIXKUM; Tan et al., 2008).

5. Synthesis and crystallization

L-tyrosine (181.3 mg, 1.00 mmol) reacted with salicylaldehyde (125.5 mg, 1.03 mmol) in methanol (20 mL), which was treated with microwave irradiation at 358 K for 5 min to yield a yellow ligand solution. Copper(II) acetate monohydrate (200.9 mg, 1.01 mmol) was added to the ligand solution and treated with microwave irradiation at 358 K for 5 min to yield a green solution. To this green solution, imidazole (70.0 mg, 1.02 mmol) was added and treated with microwave irradiation at 358 K for 5 min to yield a dark-green solution.

For recrystallization, the solution was placed in the air at room temperature for several days, and the title complex was obtained (80.9 mg 0.195 mmol, yield 19.5%) as black needle-shaped crystals suitable for single-crystal X-ray diffraction experiments.

Elementary analysis: found: C, 54.48; H, 4.15; N, 10.11%. Calculated: C₁₉H₁₈CuN₃O₄, C, 55.00; H, 4.13; N, 10.13%. IR (KBr): 1059 cm⁻¹ (m), 1085 cm⁻¹ (w), 1128 cm⁻¹ (w), 1149 cm⁻¹ (m), 1225 cm⁻¹ (w), 1271 cm⁻¹ (m), 1370 cm⁻¹ (w), 1372 cm⁻¹ (w), 1378 cm⁻¹ (m), 1384 cm⁻¹ (w), 1448 cm⁻¹ (s, C=C double bond), 1516 cm⁻¹ (m), 1610 cm⁻¹ (s, C=O double bond), 1625 cm⁻¹(s, C=N double bond), 3159 cm⁻¹ (br), 3214 cm⁻¹ (br), 3297 cm⁻¹ (br, O⋯H). UV–vis (MeOH): 269 nm (ɛ= 13636 L mol⁻¹ cm⁻¹, π–π^*); 368 nm (ɛ = 5636 L mol⁻¹ cm⁻¹, n–π^*); 618 nm (ɛ = 135 L mol⁻¹ cm⁻¹, d–d).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed on geometrically calculated positions (C—H = 0.93–0.98 Å) and were constrained using a riding model with U_iso(H) = 1.2U_eq(C) for R₂CH and R₃CH H atoms and 1.5U_eq(C) for the methyl H atoms. The O-bound H14 atom was located based on a difference-Fourier map and refined freely as an isotropic atom. The N-bound H atoms were located in a difference-Fourier map. Atom H11 of the imidazole ring was refined freely as an isotropic atom.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₁₆H₁₃NO₄)(C₃H₄N₂)]
M_r	414.89
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	5.5005 (2), 12.1363 (5), 26.147 (1)
V (Å³)	1745.46 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.28
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Bruker D8 QUEST
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.55, 0.78
No. of measured, independent and observed [I > 2σ(I)] reflections	19853, 3571, 3501
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.062, 1.06
No. of reflections	3571
No. of parameters	251
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21
Absolute structure	Refined as an inversion twin
Absolute structure parameter	0.017 (12)
Computer programs: APEX2 and SAINT V8.40B (Bruker, 2019 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and ShelXle (Hübschle et al., 2011 ).

Supporting information

CCDC reference: 2266335

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989023004735/ex2071sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023004735/ex2071Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989023004735/ex2071sup3.tif

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2019); cell refinement: SAINT V8.40B (Bruker, 2019); data reduction: SAINT V8.40B (Bruker, 2019); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ShelXle (Hübschle et al., 2011).

(1H-Imidazole-κN³)[N-(2-oxidobenzylidene)tyrosinato-κ³O,N,O']copper(II) top

Crystal data top

[Cu(C₁₆H₁₃NO₄)(C₃H₄N₂)]	D_x = 1.579 Mg m⁻³
M_r = 414.89	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 9965 reflections
a = 5.5005 (2) Å	θ = 2.9–26.4°
b = 12.1363 (5) Å	µ = 1.28 mm⁻¹
c = 26.147 (1) Å	T = 173 K
V = 1745.46 (12) Å³	Prism, black
Z = 4	0.50 × 0.30 × 0.20 mm
F(000) = 852

Data collection top

Bruker D8 QUEST diffractometer	3501 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm^-1	R_int = 0.047
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 26.4°, θ_min = 1.9°
T_min = 0.55, T_max = 0.78	h = −6→6
19853 measured reflections	k = −15→15
3571 independent reflections	l = −32→32

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)] = 0.025	w = 1/[σ²(F_o²) + (0.0276P)² + 0.2834P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max = 0.001
S = 1.06	Δρ_max = 0.33 e Å⁻³
3571 reflections	Δρ_min = −0.21 e Å⁻³
251 parameters	Absolute structure: Refined as an inversion twin
0 restraints	Absolute structure parameter: 0.017 (12)

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
Cu1	0.67468 (5)	0.46981 (2)	0.56047 (2)	0.02401 (11)
O1	0.8939 (3)	0.35005 (15)	0.55615 (7)	0.0334 (4)
N1	0.9329 (6)	0.6643 (2)	0.44552 (9)	0.0420 (6)
H11	0.951 (6)	0.717 (3)	0.4317 (12)	0.031 (8)*
C1	0.5421 (5)	0.3165 (2)	0.63934 (9)	0.0263 (5)
H1	0.429138	0.291841	0.664328	0.032*
O2	0.4294 (3)	0.58526 (14)	0.56409 (7)	0.0287 (4)
N2	0.8346 (4)	0.54082 (17)	0.50227 (7)	0.0288 (4)
C2	0.7397 (5)	0.2446 (2)	0.62716 (9)	0.0266 (5)
N3	0.5042 (4)	0.41212 (17)	0.61927 (8)	0.0247 (4)
O3	0.1144 (4)	0.64649 (19)	0.60736 (8)	0.0437 (5)
C3	0.7677 (6)	0.1496 (2)	0.65788 (10)	0.0327 (6)
H3	0.654313	0.13602	0.684559	0.039*
O4	0.3089 (4)	0.22066 (16)	0.85680 (7)	0.0341 (4)
H4A	0.191 (7)	0.191 (3)	0.8583 (9)	0.051*
C4	0.9544 (6)	0.0768 (2)	0.65012 (11)	0.0355 (6)
H4	0.973698	0.014587	0.671828	0.043*
C5	1.1151 (5)	0.0952 (2)	0.60999 (11)	0.0350 (6)
H5	1.244308	0.044786	0.604282	0.042*
C6	1.0904 (5)	0.1854 (2)	0.57830 (11)	0.0337 (6)
H6	1.200419	0.194846	0.550635	0.04*
C7	0.9050 (5)	0.2637 (2)	0.58620 (9)	0.0271 (5)
C8	1.0473 (5)	0.5091 (2)	0.47797 (9)	0.0317 (6)
H8	1.136848	0.443916	0.484952	0.038*
C9	1.1065 (5)	0.5856 (2)	0.44292 (10)	0.0373 (6)
H9	1.243185	0.584623	0.420719	0.045*
C10	0.7719 (6)	0.6358 (2)	0.48134 (10)	0.0372 (7)
H10	0.632492	0.677619	0.490455	0.045*
C11	0.2751 (5)	0.5780 (2)	0.60006 (9)	0.0280 (5)
C12	0.2973 (5)	0.4790 (2)	0.63643 (8)	0.0262 (5)
H12	0.145376	0.433906	0.634481	0.031*
C13	0.3284 (5)	0.5233 (2)	0.69154 (8)	0.0301 (5)
H13A	0.485063	0.563191	0.693498	0.036*
H13B	0.197503	0.577417	0.698212	0.036*
C14	0.3233 (5)	0.43791 (19)	0.73347 (8)	0.0248 (5)
C15	0.5135 (5)	0.4309 (2)	0.76836 (10)	0.0290 (6)
H15	0.651326	0.477154	0.764186	0.035*
C16	0.5065 (5)	0.3581 (2)	0.80895 (10)	0.0305 (5)
H16	0.638341	0.354933	0.832366	0.037*
C17	0.3077 (5)	0.28973 (19)	0.81552 (8)	0.0251 (5)
C18	0.1184 (5)	0.2928 (2)	0.78049 (9)	0.0276 (5)
H18	−0.016298	0.244436	0.784071	0.033*
C19	0.1271 (5)	0.3673 (2)	0.74005 (9)	0.0275 (5)
H19	−0.004041	0.36992	0.716438	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03258 (17)	0.02037 (15)	0.01908 (14)	0.00257 (12)	0.00109 (11)	0.00198 (11)
O1	0.0418 (10)	0.0297 (9)	0.0287 (9)	0.0086 (8)	0.0108 (8)	0.0089 (8)
N1	0.0750 (19)	0.0271 (12)	0.0239 (11)	−0.0099 (12)	0.0061 (12)	0.0052 (10)
C1	0.0339 (14)	0.0223 (12)	0.0227 (11)	0.0004 (11)	0.0033 (10)	−0.0008 (9)
O2	0.0396 (9)	0.0256 (8)	0.0207 (8)	0.0061 (7)	−0.0004 (8)	0.0028 (7)
N2	0.0411 (12)	0.0236 (10)	0.0217 (9)	−0.0016 (11)	−0.0006 (9)	0.0013 (8)
C2	0.0361 (14)	0.0201 (11)	0.0236 (11)	0.0016 (10)	−0.0001 (9)	−0.0002 (9)
N3	0.0295 (11)	0.0218 (10)	0.0228 (9)	0.0034 (9)	0.0013 (8)	0.0001 (8)
O3	0.0537 (14)	0.0427 (11)	0.0346 (10)	0.0245 (11)	0.0055 (9)	0.0059 (9)
C3	0.0434 (16)	0.0243 (12)	0.0304 (13)	0.0023 (12)	0.0035 (11)	0.0046 (10)
O4	0.0361 (10)	0.0364 (10)	0.0297 (9)	0.0009 (9)	0.0002 (9)	0.0098 (8)
C4	0.0489 (17)	0.0218 (12)	0.0359 (14)	0.0042 (12)	−0.0023 (13)	0.0059 (11)
C5	0.0378 (15)	0.0242 (13)	0.0429 (15)	0.0090 (12)	−0.0013 (12)	−0.0003 (11)
C6	0.0377 (15)	0.0296 (14)	0.0340 (13)	0.0036 (12)	0.0068 (11)	0.0019 (11)
C7	0.0338 (13)	0.0208 (12)	0.0268 (12)	0.0019 (10)	−0.0011 (10)	−0.0007 (10)
C8	0.0332 (14)	0.0357 (14)	0.0261 (12)	−0.0030 (11)	−0.0010 (10)	0.0016 (10)
C9	0.0435 (15)	0.0423 (15)	0.0261 (12)	−0.0105 (13)	0.0031 (12)	−0.0006 (12)
C10	0.0593 (19)	0.0252 (12)	0.0272 (12)	0.0028 (13)	0.0049 (12)	0.0005 (10)
C11	0.0359 (14)	0.0252 (12)	0.0229 (11)	0.0050 (11)	−0.0043 (10)	−0.0033 (9)
C12	0.0316 (12)	0.0231 (11)	0.0239 (11)	0.0035 (12)	0.0029 (9)	−0.0017 (9)
C13	0.0444 (14)	0.0223 (11)	0.0236 (11)	0.0016 (13)	0.0054 (11)	−0.0008 (10)
C14	0.0296 (13)	0.0230 (11)	0.0216 (10)	0.0025 (10)	0.0044 (10)	−0.0027 (8)
C15	0.0257 (13)	0.0326 (13)	0.0288 (12)	−0.0034 (11)	0.0045 (10)	−0.0022 (10)
C16	0.0259 (12)	0.0395 (14)	0.0261 (12)	0.0004 (12)	−0.0008 (10)	0.0011 (11)
C17	0.0297 (12)	0.0236 (11)	0.0220 (10)	0.0035 (11)	0.0027 (10)	0.0002 (9)
C18	0.0279 (13)	0.0255 (12)	0.0296 (12)	−0.0043 (10)	0.0016 (10)	0.0001 (10)
C19	0.0279 (14)	0.0307 (13)	0.0239 (11)	−0.0010 (11)	−0.0035 (9)	−0.0007 (10)

Geometric parameters (Å, º) top

Cu1—O1	1.8919 (18)	C3—C4	1.371 (4)
Cu1—N3	1.932 (2)	O4—C17	1.367 (3)
Cu1—O2	1.9473 (17)	C4—C5	1.390 (4)
Cu1—N2	1.958 (2)	C5—C6	1.379 (4)
O1—C7	1.311 (3)	C6—C7	1.410 (4)
N1—C10	1.335 (4)	C8—C9	1.345 (4)
N1—C9	1.352 (4)	C11—C12	1.537 (3)
C1—N3	1.290 (3)	C12—C13	1.547 (3)
C1—C2	1.430 (4)	C13—C14	1.509 (3)
O2—C11	1.270 (3)	C14—C19	1.389 (4)
N2—C10	1.322 (4)	C14—C15	1.390 (4)
N2—C8	1.386 (4)	C15—C16	1.381 (4)
C2—C3	1.413 (3)	C16—C17	1.383 (4)
C2—C7	1.424 (4)	C17—C18	1.388 (4)
N3—C12	1.468 (3)	C18—C19	1.392 (4)
O3—C11	1.228 (3)

O1—Cu1—N3	94.49 (8)	O1—C7—C6	119.0 (2)
O1—Cu1—O2	175.72 (8)	O1—C7—C2	123.5 (2)
N3—Cu1—O2	83.45 (8)	C6—C7—C2	117.5 (2)
O1—Cu1—N2	90.31 (8)	C9—C8—N2	109.0 (3)
N3—Cu1—N2	174.98 (9)	C8—C9—N1	106.4 (3)
O2—Cu1—N2	91.86 (8)	N2—C10—N1	110.1 (3)
C7—O1—Cu1	127.44 (16)	O3—C11—O2	123.3 (2)
C10—N1—C9	108.7 (2)	O3—C11—C12	119.3 (2)
N3—C1—C2	125.5 (2)	O2—C11—C12	117.3 (2)
C11—O2—Cu1	116.69 (16)	N3—C12—C11	107.73 (19)
C10—N2—C8	105.8 (2)	N3—C12—C13	113.0 (2)
C10—N2—Cu1	126.0 (2)	C11—C12—C13	108.25 (19)
C8—N2—Cu1	127.85 (18)	C14—C13—C12	115.8 (2)
C3—C2—C7	119.4 (2)	C19—C14—C15	117.7 (2)
C3—C2—C1	117.0 (2)	C19—C14—C13	121.9 (2)
C7—C2—C1	123.6 (2)	C15—C14—C13	120.3 (2)
C1—N3—C12	119.8 (2)	C16—C15—C14	121.5 (3)
C1—N3—Cu1	124.84 (18)	C15—C16—C17	120.1 (3)
C12—N3—Cu1	114.78 (15)	O4—C17—C16	117.5 (2)
C4—C3—C2	121.6 (3)	O4—C17—C18	122.8 (2)
C3—C4—C5	118.9 (2)	C16—C17—C18	119.7 (2)
C6—C5—C4	121.3 (3)	C17—C18—C19	119.6 (2)
C5—C6—C7	121.2 (2)	C14—C19—C18	121.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2ⁱ	0.75 (4)	2.40 (4)	3.050 (3)	147 (3)
N1—H11···O4ⁱⁱ	0.75 (4)	2.48 (3)	3.058 (3)	136 (3)
O4—H4A···O3ⁱⁱⁱ	0.74	1.98	2.666 (3)	154
C13—H13A···O4^iv	0.99	2.58	3.364 (3)	136

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

Funding information

This work was supported by a Grant-in-Aid for Scientific Research (A) KAKENHI (20H00336).

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