Crystal structure of trans-bis­[2-(1H-benzotriazol-1-yl)acetato-κO]bis­(ethano­lamine-κ2N,O)copper(II)

Alieva, G.K.; Ashurov, J.M.; Kadirova, S.A.; Ibragimov, B.T.; Zakhidov, K.A.

doi:10.1107/S2056989019000744

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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 233-236

https://doi.org/10.1107/S2056989019000744

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Crystal structure of trans-bis[2-(1H-benzotriazol-1-yl)acetato-κO]bis(ethanolamine-κ²N,O)copper(II)

Guloy K. Alieva,^a ^* Jamshid M. Ashurov,^b Shahnoza A. Kadirova,^c Bakhtiyar T. Ibragimov ^b and Kasim A. Zakhidov ^d

^aInstitute of General and Inorganic Chemistry of Uzbekistan Academy of Sciences, M.Ulugbek Str, 77a, Tashkent, ^bInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek Str 83, Tashkent, ^cChemistry Department, National University of Uzbekistan, Tashkent, and ^dSamarkand State University 140104, University blv. 15, Samarkand, Samarkand region, Uzbekistan
^*Correspondence e-mail: x-ray.uz@mail.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 24 December 2018; accepted 16 January 2019; online 18 January 2019)

The reaction of 2-(1H-benzotriazol-1-yl)acetic acid (HBTA; C₈H₇N₃O₂) and monoethanolamine (MEA; C₂H₇NO) with CuCl₂·2H₂O resulted in the formation of the title complex, [Cu(C₈H₆N₃O₂)₂(C₂H₇NO)₂] or [Cu(BTA)₂(MEA)₂]. Its asymmetric unit comprises one BTA anion coordinating to the Cu²⁺ cation (site symmetry $[\overline{1}]$ ) through the carboxyl O atom, and one MEA ligand chelating the metal cation by two heteroatoms (O and N). The equatorial Cu—O and Cu—N bond lengths are similar at 2.029 (1) and 1.980 (2) Å, respectively, while the length of the axial Cu—O bond is considerably greater [2.492 (2) Å], as is typical for Jahn–Teller-distorted systems. An intramolecular hydrogen bond is present between the hydroxy group of the MEA ligand and the non-coordinating O atom of the carboxylate group. Intermolecular hydrogen bonding involving the amino function of the MEA ligand and the carboxylate group results in eight-membered rings with an R₂²(8) graph-set motif. The molecules are further linked by C—H⋯π interactions involving the triazole rings and methylene groups of MEA, thus generating an overall three-dimensional supramolecular framework.

Keywords: copper(II); crystal structure; benzotriazol; monoethanolamine; hydrogen bonding.

CCDC reference: 1891272

1. Chemical context

Recently, systematic studies of the structures and metal complex formation features of benzoic acid (Ibragimov et al., 2016a ,b ) and benzotriazole derivatives have been carried out by our group. Benzotriazoles consist of nitrogen-containing bicyclic ring systems and demonstrate many types of biological activities, such as antibacterial (Wan et al., 2010 ; Suma et al., 2012 ), antimicrobial (Nanjunda Swamy et al., 2006 ; Singh et al., 2009 ; Patel et al., 2012 ; Ramachandran et al., 2011 ), antifungal (Khabnadideh et al., 2012 ; Rezaei et al., 2009 ; Gaikwad et al., 2012 ; Rakesh et al., 2010 ), anticancer, anti-inflammatory, analgesic, antimalarial and antitubercular (Kopańska (née Zastąpiło) et al., 2004 ; Jamkhandi et al., 2015 ). Functional groups such as carboxylate, hydroxyl and pyridyl can be introduced to benzotriazole, increasing the coordination possibilities (Stoumpos et al., 2008 ; Wang et al., 2008a ,b ). The interaction of metal ions with HBTA results in the formation of complexes in which it demonstrates monodentate (Ma et al., 2015 ; Zeng et al., 2012 ; Wang et al., 2014a ) coordination. HBTA also can show bridging (Li et al., 2016 ; Wang et al., 2014b ) and catena-type (Wang et al., 2011 , 2014b; Liu et al., 2012 ) coordination modes. The interaction of metal cations with MEA results in the formation of complexes in which MEA demonstrates monodentate (Hajji & Guerfel, 2016 ; Luo et al., 2012 ; Ren et al., 2014 ; Heinrich et al., 2012 ; Guzei et al., 2010a ) and bidentate (Ibragimov et al., 2017 ; Seppälä et al., 2013 ; Yeşilel et al., 2012 ; Xue et al., 2016 ; Ashurov et al., 2015 ) coordination modes. In some complexes, MEA has bridging properties (Shahid et al., 2015 ; Tudor et al., 2013 ; Schwarz et al., 2010 ; Maclaren et al., 2012 ; Seppälä et al., 2012 ). In addition, there are metal complexes in which MEA molecules show non-coordinating behaviour (Wang et al., 2013 ; Lemmerer & Billing, 2010 ; Calderone et al., 2011 ; Yadav et al., 2015 ; Sutradhar et al., 2012 ; Liu et al., 2011 ).

We have reported the synthesis of mixed-ligand complexes of Cu and Zn with MEA and α-naphthylacetic acid (NAA) and determined the structures of [Cu (NAA)₂(MEA)₂] and [Zn(NAA)₂(MEA)₂] (Ashurov et al., 2015). A search in the Cambridge Structural Database (CSD Version 5.39, last update August 2018; Groom et al., 2016 ) revealed that crystal structures have been reported for complexes of HBTA and MEA with many metal ions. However, no mixed-ligand metal complex including HBTA and MEA is documented in the CSD. Here, the synthesis and structure of the title compound, [Cu(BTA)₂(MEA)₂], (I), is described.

2. Structural commentary

The molecular structure of trans-bis(ethanolamine-κ²N,O)bis[2-(1H-benzotriazol-1-yl)acetato-κO]copper(II), (I), is shown in Fig. 1 and consists of isolated [Cu(MEA)₂(BTA)₂] units. The Cu²⁺ cation is located on a center of inversion. Its coordination polyhedron is a distorted N₂O₄ octahedron formed by two oxygen atoms (O2) of the carboxy groups of symmetry-related BTA anions, by two nitrogen atoms (N4) of two symmetry-related MEA ligands in the equatorial plane and by two O atoms (O3) of the same set of MEA ligands in the axial positions. The Cu—O2 and Cu—N4 bond lengths are 2.029 (1) and 1.980 (2) Å, respectively, whereas the length of the axial Cu—O3 bond is 2.492 (2) Å, typical for Jahn–Teller distortions. The MEA ligand is neutral and acts as a bidentate N- and O-donor ligand and forms CuNC₂O five-membered chelate rings which have a twist conformation; the O3—C10—C9—N4 torsion angle is −60.3 (3)°. The planar benzotriazole ring system (N1–N3/C1–C6: r.m.s. deviation = 0.0064 Å) is co-planar with the methyl carbon atom C7 [deviation from the plane of 0.158 (2) Å], whereas the carboxylate group is nearly normal to this plane [88.0 (2)°]. The difference of the C8—O(1,2) distances of the carboxylate group (Δ = 0.036 Å) is due to the monodentate coordination, with the longer C—O distance involving the coordinating O2 atom.

Figure 1
The molecular structure of [Cu(MEA)₂(BTA)₂] with the atom-numbering scheme. Displacement ellipsoids are drawn at the 25% probability level.

The molecular structure is stabilized by an intramolecular O3—H3⋯O1 hydrogen bond between the OH group of the MEA ligand and the non-coordinating carboxylate O atom (Fig. 1, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1ⁱ	0.80 (1)	1.86 (1)	2.634 (2)	163 (3)
N4—H4A⋯O2ⁱⁱ	0.89 (1)	2.41 (2)	3.046 (2)	129 (2)
N4—H4B⋯O3ⁱⁱ	0.89 (1)	2.12 (1)	2.973 (2)	161 (2)
C7—H7A⋯O1ⁱⁱⁱ	0.97	2.53	3.449 (3)	158
C9—H9A⋯N3^iv	0.97	2.58	3.345 (3)	136
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y+1, z; (iii) x, y-1, z; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

3. Supramolecular features

In the crystal structure of (I), molecules are linked by C7—H7A⋯O1ⁱⁱⁱ, N4—H4A⋯O2ⁱⁱ and N4—H4B⋯O3ⁱⁱ hydrogen bonds between the amino function and carboxylate/hydroxy O-atom acceptors (Table 1, Fig. 2), forming chains propagating parallel to [010]. Adjacent chains are linked by C9—H9A⋯N3^iv hydrogen bonds into a layered arrangement parallel to (10 $[\overline{1}]$ ) (Fig. 3). Additional C—H⋯π interactions between the triazole rings and methylene groups of MEA (H⋯Cg = 2.88, C—H⋯Cg = 140°, $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z) generate a three-dimensional supramolecular framework.

Figure 2
Chain structures formed by hydrogen bonds in the structure of (I)

. Hydrogen bonds are shown as dashed lines.

Figure 3
A partial view along the b axis of the crystal packing of compound (I)

. Intermolecular hydrogen bonds are shown as dashed lines.

4. Database survey

There are thirty-one structures of coordination compounds that are derived from 2-(1H-benzotriazol-1-yl)acetic acid and different metal cations in the CSD (Version 5.39, last update August 2018; Groom et al., 2016). The interaction of metal ions with BTA results in the formation of complexes in which metals demonstrate monodentate [CUYGAG (Ma et al., 2015), DUWQES (Zheng et al., 2010 ), LAMYUV (Zeng et al., 2012), TIVWOM (Wang et al., 2014b), TOBDUK (Hang & Ye, 2008 )] and bridging [COHFOW (Ren et al., 2013 ), DEZHIB (Zeng, 2013 ), GADVEP (Li et al., 2016), TIVXAZ (Wang et al., 2014b)] coordination modes. BTA also can show catena-type structures [DEZHOH (Zeng, 2013), DUWQAO (Zheng et al., 2010), DUWQIW (Zheng et al., 2010), GUTZAX (Wang et al., 2009 ), IPAGIQ (Wang et al., 2011), TIVXED (Wang et al., 2014b), TIVXON (Wang et al., 2014b), UFETEF (Hu et al., 2008 ), YATPAM (Liu, 2012), ZIPLOB (Chen et al., 2010 ) etc]. In most cases, MEA behaves as a chelating ligand; however, there are metal complexes in which non-coordinating MEA molecules are situated in the outer coordination sphere [AXUQAN (Ibragimov et al., 2016c ), FAFTOV (Spitsin et al., 1986 ), TIRQEQ (Halvorson et al., 1995 ), WUZZOH (Guzei et al., 2010b ) etc]. Mixed-ligand metal complexes including BTA and MEA have not been reported in the CSD up to date.

5. Synthesis and crystallization

To an aqueous solution (2.5 ml) of CuCl₂·2H₂O (0.048 g, 0.282 mmol) was slowly added an ethanol solution (5 ml) containing MEA (0.034 g, 0.565 mmol) and HBTA (0.1 g, 0.565 mmol) under constant stirring. Blue crystals of the product were obtained by solvent evaporation at room temperature after one week. Yield: 70%. Elemental analysis: Calc. for C₂₀H₂₆CuN₈O₆ (538.04): C, 44.65; H, 4.87 N, 20.83%. Found: C, 44.73; H, 4.93; N, 20.88%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound hydrogen atoms were placed in calculated positions and refined as riding atoms with C—H = 0.93 and 0.97 Å for aromatic and methylene hydrogen atoms, respectively, and with U_iso(H) = 1.2U_eq(C). The positions of the O- and N bound H atoms were located from a difference-Fourier map and were refined with soft distance restraints, 0.82 Å for the hydroxyl group and 0.95 Å for the primary amine group.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₈H₆N₃O₂)₂(C₂H₇NO)₂]
M_r	538.03
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	12.4283 (4), 4.84866 (9), 20.6944 (5)
β (°)	105.823 (3)
V (Å³)	1199.80 (5)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	1.75
Crystal size (mm)	0.36 × 0.22 × 0.12

Data collection
Diffractometer	Rigaku Xcalibur Ruby
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2015 )
T_min, T_max	0.558, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8833, 2444, 2152
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.096, 1.06
No. of reflections	2444
No. of parameters	173
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.31
Computer programs: CrysAlis PRO (Rigaku OD, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), Mercury (Macrae et al., 2006 and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1891272

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989019000744/wm5481sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019000744/wm5481Isup2.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: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2006; software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Bis[2-(1H-benzotriazol-1-yl)acetato-κO]bis(ethanolamine-κ²N,O)copper(II) top

Crystal data top

[Cu(C₈H₆N₃O₂)₂(C₂H₇NO)₂]	F(000) = 558
M_r = 538.03	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 12.4283 (4) Å	Cell parameters from 3723 reflections
b = 4.84866 (9) Å	θ = 3.7–75.7°
c = 20.6944 (5) Å	µ = 1.75 mm⁻¹
β = 105.823 (3)°	T = 293 K
V = 1199.80 (5) Å³	Block, blue
Z = 2	0.36 × 0.22 × 0.12 mm

Data collection top

Rigaku Xcalibur Ruby diffractometer	2444 independent reflections
Radiation source: fine-focus sealed X-ray tube	2152 reflections with I > 2σ(I)
Detector resolution: 10.2576 pixels mm^-1	R_int = 0.031
ω scans	θ_max = 75.9°, θ_min = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −15→15
T_min = 0.558, T_max = 1.000	k = −5→5
8833 measured reflections	l = −20→25

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)] = 0.033	w = 1/[σ²(F_o²) + (0.048P)² + 0.364P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.24 e Å⁻³
2444 reflections	Δρ_min = −0.31 e Å⁻³
173 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0009 (2)

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
Cu	0.5000	0.5000	0.5000	0.03515 (14)
O2	0.53163 (12)	0.2852 (3)	0.58733 (6)	0.0434 (3)
O3	0.66203 (12)	0.2720 (3)	0.47288 (7)	0.0449 (3)
O1	0.46322 (14)	0.5886 (3)	0.64711 (7)	0.0535 (4)
N1	0.56782 (14)	0.3490 (4)	0.76528 (8)	0.0420 (4)
N4	0.62260 (16)	0.7586 (3)	0.54159 (8)	0.0432 (4)
N3	0.60695 (19)	0.6560 (5)	0.84410 (10)	0.0659 (6)
C7	0.57879 (18)	0.2195 (5)	0.70430 (9)	0.0458 (5)
H7A	0.5484	0.0342	0.7013	0.055*
H7B	0.6574	0.2054	0.7061	0.055*
N2	0.64071 (17)	0.5465 (5)	0.79544 (10)	0.0582 (5)
C8	0.51797 (16)	0.3819 (4)	0.64159 (9)	0.0383 (4)
C3	0.50966 (19)	0.5287 (5)	0.84514 (11)	0.0494 (5)
C2	0.48288 (17)	0.3334 (4)	0.79457 (10)	0.0430 (4)
C10	0.74518 (19)	0.4794 (5)	0.49439 (13)	0.0568 (6)
H10A	0.7391	0.6123	0.4585	0.068*
H10B	0.8187	0.3956	0.5041	0.068*
C9	0.73262 (19)	0.6246 (5)	0.55560 (12)	0.0557 (5)
H9A	0.7405	0.4930	0.5919	0.067*
H9B	0.7910	0.7621	0.5696	0.067*
C1	0.3878 (2)	0.1733 (5)	0.78222 (14)	0.0628 (6)
H1	0.3704	0.0434	0.7479	0.075*
C4	0.4385 (3)	0.5704 (7)	0.88710 (14)	0.0763 (8)
H4	0.4549	0.7005	0.9214	0.092*
C6	0.3200 (3)	0.2185 (7)	0.82423 (19)	0.0817 (9)
H6	0.2551	0.1146	0.8180	0.098*
C5	0.3452 (3)	0.4120 (7)	0.87504 (19)	0.0849 (10)
H5	0.2967	0.4345	0.9018	0.102*
H4A	0.609 (2)	0.836 (6)	0.5773 (10)	0.078 (9)*
H4B	0.623 (2)	0.895 (4)	0.5130 (11)	0.063 (7)*
H3	0.6329 (19)	0.295 (5)	0.4336 (6)	0.055 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0477 (2)	0.0285 (2)	0.0312 (2)	0.00425 (15)	0.01401 (15)	0.00123 (13)
O2	0.0614 (9)	0.0372 (7)	0.0338 (6)	0.0079 (6)	0.0165 (6)	0.0036 (5)
O3	0.0546 (8)	0.0376 (7)	0.0420 (7)	0.0017 (6)	0.0123 (6)	0.0019 (6)
O1	0.0741 (10)	0.0485 (8)	0.0375 (7)	0.0204 (8)	0.0144 (7)	0.0023 (6)
N1	0.0441 (9)	0.0473 (10)	0.0336 (8)	−0.0002 (7)	0.0088 (6)	0.0049 (7)
N4	0.0584 (10)	0.0309 (9)	0.0406 (9)	0.0015 (7)	0.0143 (8)	−0.0008 (7)
N3	0.0681 (13)	0.0681 (14)	0.0559 (11)	−0.0137 (11)	0.0077 (10)	−0.0147 (10)
C7	0.0558 (12)	0.0469 (11)	0.0350 (9)	0.0103 (9)	0.0130 (8)	0.0053 (8)
N2	0.0507 (11)	0.0671 (13)	0.0535 (11)	−0.0122 (9)	0.0085 (8)	−0.0018 (9)
C8	0.0472 (10)	0.0361 (10)	0.0322 (8)	0.0001 (8)	0.0119 (7)	0.0025 (7)
C3	0.0562 (12)	0.0505 (13)	0.0401 (10)	0.0043 (10)	0.0109 (9)	0.0045 (9)
C2	0.0446 (10)	0.0441 (11)	0.0385 (9)	0.0040 (8)	0.0082 (8)	0.0103 (8)
C10	0.0449 (11)	0.0573 (14)	0.0721 (15)	−0.0031 (10)	0.0227 (11)	−0.0066 (11)
C9	0.0502 (12)	0.0472 (13)	0.0611 (13)	−0.0009 (10)	0.0009 (10)	−0.0049 (10)
C1	0.0580 (14)	0.0556 (15)	0.0722 (15)	−0.0095 (11)	0.0133 (12)	0.0092 (12)
C4	0.105 (2)	0.0715 (18)	0.0614 (15)	0.0215 (17)	0.0369 (16)	0.0050 (13)
C6	0.0641 (16)	0.0718 (19)	0.121 (3)	0.0015 (14)	0.0447 (17)	0.0307 (19)
C5	0.087 (2)	0.082 (2)	0.105 (2)	0.0210 (18)	0.060 (2)	0.0341 (19)

Geometric parameters (Å, º) top

Cu—N4ⁱ	1.9798 (18)	C7—H7A	0.9700
Cu—N4	1.9798 (18)	C7—H7B	0.9700
Cu—O2	2.0292 (12)	C3—C2	1.383 (3)
Cu—O2ⁱ	2.0293 (12)	C3—C4	1.413 (4)
Cu—O3ⁱ	2.4917 (15)	C2—C1	1.378 (3)
O2—C8	1.270 (2)	C10—C9	1.494 (3)
O3—C10	1.424 (3)	C10—H10A	0.9700
O3—H3	0.802 (10)	C10—H10B	0.9700
O1—C8	1.234 (2)	C9—H9A	0.9700
N1—N2	1.349 (3)	C9—H9B	0.9700
N1—C2	1.355 (3)	C1—C6	1.383 (4)
N1—C7	1.449 (2)	C1—H1	0.9300
N4—C9	1.470 (3)	C4—C5	1.356 (5)
N4—H4A	0.885 (10)	C4—H4	0.9300
N4—H4B	0.887 (10)	C6—C5	1.380 (5)
N3—N2	1.305 (3)	C6—H6	0.9300
N3—C3	1.363 (3)	C5—H5	0.9300
C7—C8	1.530 (3)

N4ⁱ—Cu—N4	180.0	N3—C3—C4	130.7 (3)
N4ⁱ—Cu—O2	90.08 (6)	C2—C3—C4	120.1 (2)
N4—Cu—O2	89.92 (6)	N1—C2—C3	104.13 (18)
N4ⁱ—Cu—O2ⁱ	89.92 (6)	N1—C2—C1	132.9 (2)
N4—Cu—O2ⁱ	90.08 (6)	C3—C2—C1	122.9 (2)
O2—Cu—O2ⁱ	180.0	O3—C10—C9	111.30 (18)
C8—O2—Cu	123.91 (12)	O3—C10—H10A	109.4
C10—O3—H3	107.8 (19)	C9—C10—H10A	109.4
N2—N1—C2	109.84 (17)	O3—C10—H10B	109.4
N2—N1—C7	120.00 (17)	C9—C10—H10B	109.4
C2—N1—C7	129.44 (18)	H10A—C10—H10B	108.0
C9—N4—Cu	111.72 (13)	N4—C9—C10	110.35 (18)
C9—N4—H4A	113.6 (19)	N4—C9—H9A	109.6
Cu—N4—H4A	110 (2)	C10—C9—H9A	109.6
C9—N4—H4B	106.4 (17)	N4—C9—H9B	109.6
Cu—N4—H4B	109.1 (18)	C10—C9—H9B	109.6
H4A—N4—H4B	106 (3)	H9A—C9—H9B	108.1
N2—N3—C3	107.5 (2)	C2—C1—C6	115.6 (3)
N1—C7—C8	111.94 (16)	C2—C1—H1	122.2
N1—C7—H7A	109.2	C6—C1—H1	122.2
C8—C7—H7A	109.2	C5—C4—C3	116.9 (3)
N1—C7—H7B	109.2	C5—C4—H4	121.5
C8—C7—H7B	109.2	C3—C4—H4	121.5
H7A—C7—H7B	107.9	C5—C6—C1	122.4 (3)
N3—N2—N1	109.23 (18)	C5—C6—H6	118.8
O1—C8—O2	126.26 (17)	C1—C6—H6	118.8
O1—C8—C7	119.79 (16)	C4—C5—C6	122.0 (3)
O2—C8—C7	113.94 (17)	C4—C5—H5	119.0
N3—C3—C2	109.3 (2)	C6—C5—H5	119.0

N2—N1—C7—C8	−86.8 (2)	C7—N1—C2—C1	8.5 (4)
C2—N1—C7—C8	82.4 (3)	N3—C3—C2—N1	0.9 (2)
C3—N3—N2—N1	−0.6 (3)	C4—C3—C2—N1	−179.9 (2)
C2—N1—N2—N3	1.2 (2)	N3—C3—C2—C1	−178.9 (2)
C7—N1—N2—N3	172.31 (19)	C4—C3—C2—C1	0.3 (3)
Cu—O2—C8—O1	16.3 (3)	Cu—N4—C9—C10	50.9 (2)
Cu—O2—C8—C7	−162.68 (14)	O3—C10—C9—N4	−60.3 (3)
N1—C7—C8—O1	−3.5 (3)	N1—C2—C1—C6	179.8 (2)
N1—C7—C8—O2	175.61 (17)	C3—C2—C1—C6	−0.4 (3)
N2—N3—C3—C2	−0.2 (3)	N3—C3—C4—C5	179.0 (3)
N2—N3—C3—C4	−179.3 (3)	C2—C3—C4—C5	−0.1 (4)
N2—N1—C2—C3	−1.2 (2)	C2—C1—C6—C5	0.4 (4)
C7—N1—C2—C3	−171.29 (19)	C3—C4—C5—C6	0.0 (5)
N2—N1—C2—C1	178.6 (2)	C1—C6—C5—C4	−0.1 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1ⁱ	0.80 (1)	1.86 (1)	2.634 (2)	163 (3)
N4—H4A···O2ⁱⁱ	0.89 (1)	2.41 (2)	3.046 (2)	129 (2)
N4—H4B···O3ⁱⁱ	0.89 (1)	2.12 (1)	2.973 (2)	161 (2)
C7—H7A···O1ⁱⁱⁱ	0.97	2.53	3.449 (3)	158
C9—H9A···N3^iv	0.97	2.58	3.345 (3)	136

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

Funding information

This work was supported by a Grant for Fundamental Research of the Center of Science and Technology, Uzbekistan (No. BA-FA– F7–004).

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