Synthesis, crystal structure and Hirshfeld surface analysis of catena-poly[[bis­(semicarbazide-κ2N,O)copper(II)]-μ-sulfato-κ2O:O′]

Tadjieva, G.; Ibragimov, A.B.; Yakubov, Y.; Ibragimov, B.T.; Ashurov, J.M.

doi:10.1107/S2056989022010040

research communications

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ISSN: 2056-9890

Volume 78| Part 11| November 2022| Pages 1131-1134

https://doi.org/10.1107/S2056989022010040

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Synthesis, crystal structure and Hirshfeld surface analysis of catena-poly[[bis(semicarbazide-κ²N,O)copper(II)]-μ-sulfato-κ²O:O′]

Galiya Tadjieva,^a Aziz B. Ibragimov,^a Yuldash Yakubov,^a Bakhtiyar T. Ibragimov ^b and Jamshid M. Ashurov ^b ^*

^aInstitute of General and Inorganic Chemistry of the Uzbekistan Academy of Sciences, M. Ulugbek Str. 77a, Tashkent 700125, Uzbekistan, and ^bInstitute of Bioorganic Chemistry Academy of Sciences of Uzbekistan, M. Ulugbek Str. 83, Tashkent 700125, Uzbekistan
^*Correspondence e-mail: atom.uz@mail.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 21 September 2022; accepted 15 October 2022; online 20 October 2022)

The title polymer, [Cu(SO₄)(CH₅N₃O)₂]_n, has been synthesized from aqueous solutions of CuSO₄ and semicarbazide. In the crystal structure, the Cu^II atoms are chelated by two neutral semicarbazide molecules through the oxygen atom and a nitrogen atom of the amino group. The remaining two positions of the Jahn–Teller-distorted octahedral coordination sphere are occupied by oxygen atoms of two sulfate anions in the axial positions. The coordination bonds of the latter associate the polyhedra into polymeric chains running parallel to the c axis. There is a weak intramolecular hydrogen bond between the N—H group and an oxygen atom of the SO₄^2– anion. Thirteen relatively weak intermolecular hydrogen-bonding interactions link the chains into a three-dimensional network. Hirshfeld surface analysis revealed that 64.7% of the intermolecular interactions are from O⋯H/H⋯O contacts and 20.1% from H⋯H contacts. Other interactions such as N⋯H/H⋯N or C⋯H/H⋯C contribute less to the crystal packing.

Keywords: semicarbazide; copper complex; crystal structure; Hirshfeld surface analysis; intermolecular interactions.

CCDC reference: 2213165

1. Chemical context

Semicarbazide (SEC), a water-soluble white solid, is a derivative of urea with formula O=C(NH₂)(N₂H₃). It is used in the preparation of pharmaceuticals including nitrofuran antibacterials (furazolidone, nitrofurazone, nitrofurantoin) and related compounds (Vass et al., 2008 ). Originally, SEC was primarily detected as a nitrofurazone veterinary metabolite, but over time it was found that azodicarbonamide and flour stored in sealed cans could lead to the formation of SEC as well (Tian et al., 2014 ). Therefore, the toxicity of SEC as a food contaminant is of crucial interest. SEC hydrochloride has an oral LD₅₀ of 225 mg kg⁻¹ in mice and 123 mg kg⁻¹ in the rat. Some studies suggest that SEC hydrochloride is a mutagen, an animal carcinogen and a teratogen. As a result of the lack of data in humans and an overall limited evidence of carcinogenicity in animals, SEC was classified by the International Agency for Research on Cancer as a Group 3 agent, i.e. not classifiable as to its carcinogenicity to humans (Takahashi et al., 2014 ). However, SEC products (semicarbazones and thiosemicarbazones) are known to have antiviral, anti-infective and antineoplastic activities through binding to copper or iron in cells (Becalski et al., 2004 ; Tian et al., 2014). It is well known that the biopharmaceutical properties of active pharmaceutical ingredients may be improved by metal complex formation (Khudoyberganov et al., 2022 ; Ruzmetov et al., 2022a ,b ). In turn, this phenomenon may lead to a reduction in the toxicity of hazardous organic substances in coordination compounds (Egorova & Ananikov, 2017 ; Flora & Pachauri et al., 2010 ; Ahmed et al., 2020 ). Therefore, it is of great interest to study the metal complex formation of SEC. In this context, we report here the synthesis, crystal structure and Hirshfeld surface analysis of a new copper complex of SEC with sulfate anions as co-ligands, [Cu(CH₅N₃O)₂(SO₄)]_n.

2. Structural commentary

The expanded asymmetric unit of the title polymer is shown in Fig. 1. The Cu^II atom is chelated by two SEC molecules through the oxygen atoms (O1 and O2) and the nitrogen atoms (N1 and N4) of NH₂ groups, leading to a slightly distorted square-planar coordination environment with bond lengths in the range between 1.9218 (17) and 2.015 (2) Å and bond angles between 81.50 (7) and 101.89 (8)°. Two remote oxygen atoms, O6 and O3ⁱ, of two SO₄^2– anions augment the coordination sphere (Table 1). As a result of the Jahn–Teller effect, a substantial elongation of the two axial Cu—O bonds is observed and the coordination sphere around Cu^II becomes a distinctly distorted octahedron.

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9549 (17)	Cu1—N4	2.015 (2)
Cu1—O2	1.9218 (17)	Cu1—O6	2.3776 (18)
Cu1—N1	1.9769 (19)	Cu1—O3ⁱ	2.6947 (19)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The expanded asymmetric part of the title compound [Cu(SEC)₂(SO₄)]_n with the atom-numbering scheme. The intramolecular hydrogen bond is indicated by a dashed line. Displacement ellipsoids are plotted at the 50% probability level. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z - 1/2; (ii) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ].

Coordination bonds involving the SO₄^2– ligands associate individual polyhedra into polymeric chains running parallel to the c axis (Fig. 2). A weak intramolecular hydrogen bond between N4—H4 and oxygen atom O4 of the SO₄ anion (Table 2), enclosing a six-membered ring with graph-set notation S₁¹(6) (Etter, 1990 ), consolidates the conformation (Fig. 1). The lengths of the S—O bonds are very similar, showing a distribution between 1.4702 (17) and 1.4769 (17) Å, in very good agreement with the mean value of 1.473 Å for S—O bonds (Gagné & Hawthorne, 2018 ).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.89	2.06	2.928 (3)	164
N1—H1B⋯O4ⁱⁱ	0.89	2.43	3.302 (3)	167
N1—H1B⋯O5ⁱⁱ	0.89	2.24	2.871 (3)	128
N2—H2⋯O5ⁱⁱⁱ	0.86	1.97	2.751 (3)	151
N3—H3A⋯O3^iv	0.86	2.20	2.985 (3)	152
N3—H3B⋯O1^v	0.86	2.59	3.036 (3)	113
N4—H4A⋯O4	0.89	2.47	3.125 (3)	131
N4—H4A⋯O5ⁱⁱ	0.89	2.57	3.097 (3)	119
N4—H4B⋯O5ⁱ	0.89	2.49	3.309 (3)	152
N5—H5⋯O6^vi	0.86	2.59	3.228 (3)	132
N5—H5⋯O4^vii	0.86	2.39	2.954 (3)	123
N6—H6A⋯O1^viii	0.86	2.51	3.123 (3)	129
N6—H6A⋯O2^viii	0.86	2.17	2.971 (3)	154
N6—H6A⋯O6^vi	0.86	2.03	2.845 (3)	157
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) ; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) ; (vii) ; (viii) .

Figure 2
The formation of polymeric chains. Intramolecular hydrogen bonds are indicated by dotted lines.

3. Supramolecular features

For hydrogen-bonding interactions, there are six proton acceptor and ten proton donor functionalities, forming a complex system of 13 intermolecular hydrogen bonds (Table 2). Within this network, bifurcated hydrogen bonds involving hydrogen atoms H4A, H5 and H6A are noted. Each of the atoms O4 and O5 is an acceptor for four hydrogen bonds whereas atoms O1 and O6 are hydrogen-bonded to two hydrogen atoms, and O2 and O3 to one hydrogen atom each. The hydrogen bonds form numerous different associates with various dimensions, e.g. there are many rings with graph-set notations ranging from R₁¹(n) to R₆⁶(n). The hydrogen bonds indicated in Table 2 link the polymeric chains into a three-dimensional network (Fig. 3).

Figure 3
The crystal structure of the title compound. Intermolecular hydrogen bonds are indicated by dashed lines.

4. Hirshfeld surface analysis

Hirshfeld surfaces were calculated and two-dimensional fingerprints generated using CrystalExplorer2021 (Spackman et al., 2021 ). Fig. 4 shows the Hirshfeld surface of the title compound with d_norm (normalized contact distance) plotted over the range −0.5974 to 1.0842 a.u. The interactions given in Table 2 play a key role in the molecular packing of the complex, and nearly two thirds (or 64.7%) of intermolecular interactions correspond to O⋯H/H⋯O contacts The overall two-dimensional fingerprint plot and those delineated into O⋯H/H⋯O, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C and Cu⋯O/O⋯C interactions are shown in Fig. 5. The 2.5% contribution of the Cu⋯O/O⋯Cu contact is explained by the existence of the very long Cu—O3 bond, which is considered by CrystalExplorer to be an intermolecular contact.

Figure 4
View of the Hirshfeld surface plotted over d_norm.

Figure 5
The full two-dimensional fingerprint plot of [Cu(SEC)₂(SO₄)]_n showing all interactions and those delineated into O⋯H/H⋯O, H⋯H, N⋯H/H⋯N, C⋯H/H⋯C and C⋯O/O⋯C interactions. The d_i and d_e values are the closest internal and external distances (Å) from given points on the Hirshfeld surface.

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.43, update of November 2021; Groom et al., 2016 ) for semicarbazide metal complexes gave 45 hits. In all entries, neutral semicarbazide molecules coordinate in a chelating fashion enclosing five-membered rings with exception of the Pd complex NAZYES (Bergs et al., 1997 ) where a single semicarbazide molecule coordinates monodentately through an NH₂ group. In 21 mixed-ligand complexes, chloride ions serve as co-ligands except in the structure with refcode SEGWAC (Chuklanova et al., 1988 ) where all four ligand positions of the Zn^II atom are occupied by Cl⁻ ligands and protonated semicarbazide molecules present as non-coordinating molecules. Chloride anions likewise are non-coordinating in four cases, and NO₃⁻ anions in five structures. Water molecules of crystallization are encountered in 13 complexes. There is only one coordination polymer among the identified compounds, SCACCU10 (Chiesi Villa et al., 1971 ). The coordination polyhedron of most of the metal complexes is an octahedron while a tetrahedron is revealed in six cases and penta-coordination is found in three structures. Inclusion of the SO₄²⁻ anion into the coordination sphere of the central metal cation is reported only for the title compound.

6. Synthesis and crystallization

0.02 g (0.2 mol) of semicarbazide hydrochloride, 0.022 g (0.09 mol) of copper sulfate and 0.0054 g (0.09 mol) of monoethanolamine were dissolved separately in 1 ml of water at room temperature. The three solutions were mixed and left in a thermostat at 298 K. After two days, blue crystals started to precipitate. The crystals were filtered off, washed with ethanol and dried.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. N-bound hydrogen atoms were placed in calculated positions and refined in the riding-model approximation with U_iso(H) = 1.2U_eq(N), N—H = 0.89 Å for the N1 and N4 nitrogen atoms and N—H = 0.86 for the remaining nitrogen atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(SO₄)(CH₅N₃O)₂]
M_r	309.76
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.5555 (2), 6.8624 (1), 12.9061 (2)
β (°)	97.265 (2)
V (Å³)	927.36 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	5.82
Crystal size (mm)	0.18 × 0.16 × 0.14

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku, 2020 )
T_min, T_max	0.084, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8102, 1785, 1656
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.613

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.080, 1.07
No. of reflections	1785
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.42
Computer programs: CrysAlis PRO (Rigaku, 2020), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2213165

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010040/wm5662sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022010040/wm5662Isup3.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku, 2020); cell refinement: CrysAlis PRO (Rigaku, 2020); data reduction: CrysAlis PRO (Rigaku, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[bis(semicarbazide-κ²N,O)copper(II)]-µ-sulfato-κ²O:O'] top

Crystal data top

[Cu(SO₄)(CH₅N₃O)₂]	F(000) = 628
M_r = 309.76	D_x = 2.219 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
a = 10.5555 (2) Å	Cell parameters from 4840 reflections
b = 6.8624 (1) Å	θ = 3.5–70.8°
c = 12.9061 (2) Å	µ = 5.82 mm⁻¹
β = 97.265 (2)°	T = 293 K
V = 927.36 (3) Å³	Block, light blue
Z = 4	0.18 × 0.16 × 0.14 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	1785 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	1656 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.037
Detector resolution: 10.0000 pixels mm^-1	θ_max = 71.1°, θ_min = 4.2°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlisPro; Rigaku, 2020)	k = −8→6
T_min = 0.084, T_max = 1.000	l = −15→15
8102 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)] = 0.029	w = 1/[σ²(F_o²) + (0.0437P)² + 0.5652P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.080	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.32 e Å⁻³
1785 reflections	Δρ_min = −0.41 e Å⁻³
146 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0019 (3)

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
Cu1	0.25619 (3)	0.28648 (5)	0.38274 (3)	0.02624 (15)
S1	0.15524 (5)	0.43123 (8)	0.62353 (4)	0.02198 (17)
O1	0.40378 (15)	0.4485 (2)	0.36355 (13)	0.0265 (4)
O2	0.36126 (16)	0.0997 (2)	0.46464 (15)	0.0320 (4)
O4	0.06548 (18)	0.2652 (3)	0.61509 (14)	0.0327 (4)
O3	0.26979 (17)	0.3862 (3)	0.69698 (15)	0.0390 (5)
N1	0.16194 (18)	0.4839 (3)	0.29178 (15)	0.0240 (4)
H1A	0.129486	0.430444	0.231376	0.029*
H1B	0.098181	0.533034	0.322557	0.029*
N4	0.11789 (19)	0.0915 (3)	0.40077 (17)	0.0284 (4)
H4A	0.057785	0.146007	0.433787	0.034*
H4B	0.081860	0.049058	0.338815	0.034*
N5	0.1763 (2)	−0.0647 (3)	0.46025 (18)	0.0311 (5)
H5	0.132873	−0.161448	0.479156	0.037*
N2	0.2496 (2)	0.6315 (3)	0.27463 (18)	0.0333 (5)
H2	0.225589	0.736581	0.241505	0.040*
N6	0.3650 (2)	−0.2015 (3)	0.53428 (18)	0.0318 (5)
H6A	0.446089	−0.194830	0.552441	0.038*
H6B	0.323773	−0.304631	0.547814	0.038*
N3	0.4573 (2)	0.7341 (3)	0.29420 (19)	0.0369 (5)
H3A	0.536565	0.718013	0.317642	0.044*
H3B	0.433312	0.836957	0.258968	0.044*
C1	0.3723 (2)	0.6007 (3)	0.31234 (18)	0.0238 (5)
C2	0.3037 (2)	−0.0535 (3)	0.48563 (18)	0.0240 (5)
O5	0.09208 (18)	0.6011 (3)	0.66402 (17)	0.0407 (5)
O6	0.19228 (18)	0.4786 (3)	0.52040 (13)	0.0333 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0189 (2)	0.0213 (2)	0.0375 (2)	−0.00162 (12)	−0.00018 (15)	0.00774 (14)
S1	0.0190 (3)	0.0238 (3)	0.0234 (3)	−0.0045 (2)	0.0034 (2)	−0.0019 (2)
O1	0.0184 (8)	0.0231 (8)	0.0378 (9)	0.0007 (6)	0.0025 (7)	0.0065 (7)
O2	0.0225 (9)	0.0225 (8)	0.0491 (11)	−0.0053 (7)	−0.0035 (8)	0.0109 (8)
O4	0.0322 (10)	0.0292 (9)	0.0356 (10)	−0.0134 (7)	0.0001 (8)	0.0053 (7)
O3	0.0233 (9)	0.0524 (12)	0.0391 (10)	−0.0035 (8)	−0.0043 (8)	0.0060 (9)
N1	0.0187 (10)	0.0263 (10)	0.0271 (10)	0.0015 (8)	0.0036 (8)	−0.0003 (8)
N4	0.0196 (10)	0.0276 (10)	0.0374 (11)	−0.0021 (8)	0.0007 (8)	−0.0011 (9)
N5	0.0251 (11)	0.0225 (9)	0.0453 (12)	−0.0067 (8)	0.0030 (9)	0.0045 (9)
N2	0.0246 (11)	0.0277 (11)	0.0468 (13)	0.0013 (8)	0.0014 (9)	0.0164 (10)
N6	0.0282 (12)	0.0234 (10)	0.0432 (13)	−0.0014 (8)	0.0016 (9)	0.0102 (9)
N3	0.0319 (13)	0.0342 (12)	0.0446 (13)	−0.0088 (9)	0.0050 (10)	0.0145 (10)
C1	0.0240 (12)	0.0231 (11)	0.0256 (11)	0.0011 (9)	0.0086 (9)	0.0000 (9)
C2	0.0250 (12)	0.0212 (11)	0.0262 (11)	−0.0032 (9)	0.0040 (9)	−0.0011 (9)
O5	0.0284 (10)	0.0392 (10)	0.0548 (12)	−0.0009 (8)	0.0065 (9)	−0.0220 (9)
O6	0.0425 (11)	0.0316 (9)	0.0276 (9)	−0.0112 (8)	0.0115 (8)	−0.0017 (7)

Geometric parameters (Å, º) top

Cu1—O1	1.9549 (17)	N1—N2	1.408 (3)
Cu1—O2	1.9218 (17)	N4—H4A	0.8900
Cu1—N1	1.9769 (19)	N4—H4B	0.8900
Cu1—N4	2.015 (2)	N4—N5	1.414 (3)
Cu1—O6	2.3776 (18)	N5—H5	0.8600
Cu1—O3ⁱ	2.6947 (19)	N5—C2	1.345 (3)
S1—O4	1.4769 (17)	N2—H2	0.8600
S1—O3	1.4719 (18)	N2—C1	1.341 (3)
S1—O5	1.4714 (19)	N6—H6A	0.8600
S1—O6	1.4702 (17)	N6—H6B	0.8600
O1—C1	1.258 (3)	N6—C2	1.320 (3)
O2—C2	1.261 (3)	N3—H3A	0.8600
N1—H1A	0.8900	N3—H3B	0.8600
N1—H1B	0.8900	N3—C1	1.324 (3)

O1—Cu1—N1	83.36 (7)	N2—N1—H1A	110.3
O1—Cu1—N4	173.06 (8)	N2—N1—H1B	110.3
O1—Cu1—O6	94.90 (7)	Cu1—N4—H4A	110.3
O2—Cu1—O1	92.02 (7)	Cu1—N4—H4B	110.3
O2—Cu1—N1	174.70 (8)	H4A—N4—H4B	108.6
O2—Cu1—N4	82.52 (8)	N5—N4—Cu1	107.04 (14)
O2—Cu1—O6	99.05 (7)	N5—N4—H4A	110.3
N1—Cu1—N4	101.89 (8)	N5—N4—H4B	110.3
N1—Cu1—O6	83.95 (7)	N4—N5—H5	121.8
N4—Cu1—O6	90.21 (8)	C2—N5—N4	116.32 (19)
O2—Cu1—O3ⁱ	96.00 (7)	C2—N5—H5	121.8
O1—Cu1—O3ⁱ	90.24 (7)	N1—N2—H2	121.5
N1—Cu1—O3ⁱ	81.50 (7)	C1—N2—N1	116.94 (19)
N4—Cu1—O3ⁱ	86.13 (9)	C1—N2—H2	121.5
O6—Cu1—O3ⁱ	163.90 (6)	H6A—N6—H6B	120.0
O3—S1—O4	110.64 (11)	C2—N6—H6A	120.0
O5—S1—O4	108.79 (11)	C2—N6—H6B	120.0
O5—S1—O3	108.05 (12)	H3A—N3—H3B	120.0
O6—S1—O4	110.20 (10)	C1—N3—H3A	120.0
O6—S1—O3	109.80 (11)	C1—N3—H3B	120.0
O6—S1—O5	109.31 (12)	O1—C1—N2	120.0 (2)
C1—O1—Cu1	112.13 (15)	O1—C1—N3	121.8 (2)
C2—O2—Cu1	114.46 (15)	N3—C1—N2	118.2 (2)
Cu1—N1—H1A	110.3	O2—C2—N5	119.3 (2)
Cu1—N1—H1B	110.3	O2—C2—N6	121.6 (2)
H1A—N1—H1B	108.5	N6—C2—N5	119.1 (2)
N2—N1—Cu1	107.15 (14)	S1—O6—Cu1	133.39 (11)

Cu1—O1—C1—N2	−2.6 (3)	O3—S1—O6—Cu1	76.86 (17)
Cu1—O1—C1—N3	177.26 (19)	N1—N2—C1—O1	−2.4 (3)
Cu1—O2—C2—N5	−7.0 (3)	N1—N2—C1—N3	177.7 (2)
Cu1—O2—C2—N6	174.70 (19)	N4—N5—C2—O2	6.7 (3)
Cu1—N1—N2—C1	5.9 (3)	N4—N5—C2—N6	−175.0 (2)
Cu1—N4—N5—C2	−2.9 (2)	O5—S1—O6—Cu1	−164.78 (14)
O4—S1—O6—Cu1	−45.26 (18)

Symmetry code: (i) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.89	2.06	2.928 (3)	164
N1—H1B···O4ⁱⁱ	0.89	2.43	3.302 (3)	167
N1—H1B···O5ⁱⁱ	0.89	2.24	2.871 (3)	128
N2—H2···O5ⁱⁱⁱ	0.86	1.97	2.751 (3)	151
N3—H3A···O3^iv	0.86	2.20	2.985 (3)	152
N3—H3B···O1^v	0.86	2.59	3.036 (3)	113
N4—H4A···O4	0.89	2.47	3.125 (3)	131
N4—H4A···O5ⁱⁱ	0.89	2.57	3.097 (3)	119
N4—H4B···O5ⁱ	0.89	2.49	3.309 (3)	152
N5—H5···O6^vi	0.86	2.59	3.228 (3)	132
N5—H5···O4^vii	0.86	2.39	2.954 (3)	123
N6—H6A···O1^viii	0.86	2.51	3.123 (3)	129
N6—H6A···O2^viii	0.86	2.17	2.971 (3)	154
N6—H6A···O6^vi	0.86	2.03	2.845 (3)	157

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

Funding information

The authors would like to thank the Uzbekistan government for direct financial support of this research.

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