Synthesis, crystal structure and Hirshfeld surface analysis of di­aqua­bis­(o-phenyl­enedi­amine-κ2N,N′)nickel(II) naphthalene-1,5-di­sulfonate

Suyunov, J.R.; Turaev, K.K.; Alimnazarov, B.K.; Nazarov, Y.E.; Mengnorov, I.J.; Ibragimov, B.T.; Ashurov, J.M.

doi:10.1107/S2056989023009350

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 11| November 2023| Pages 1083-1087

https://doi.org/10.1107/S2056989023009350

Open

access

Synthesis, crystal structure and Hirshfeld surface analysis of diaquabis(o-phenylenediamine-κ²N,N′)nickel(II) naphthalene-1,5-disulfonate

Jabbor R Suyunov,^a Khayit Kh. Turaev,^a Bekmurod Kh. Alimnazarov,^a Yusuf E. Nazarov,^a Islombek J. Mengnorov,^b Bakhtiyar T. Ibragimov ^b and Jamshid M. Ashurov ^b ^*

^aTermez State University, "Barkamol avlod", at street, 43., Termez city, Uzbekistan, and ^bInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, 100125, M. Ulugbek Str 83, Tashkent, Uzbekistan
^*Correspondence e-mail: ashurovjamshid1@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 17 October 2023; accepted 25 October 2023; online 26 October 2023)

The reaction of o-phenylenediamine (OPD), sodium naphthalene1,5-disulfonate (Na₂NDS) and nickel sulfate in an ethanol–water mixture yielded the title compound, [Ni(OPD)₂(H₂O)₂]·NDS or [Ni(C₆H₈N₂)₂(H₂O)₂](C₁₀H₆O₆S₂). This salt consists of a complex [Ni(OPD)₂(H₂O)₂]²⁺ cation with two bidentate OPD ligands and trans aqua ligands, and a non-coordinating NDS^2– anion, which is the double-deprotonated form of H₂NDS. The Ni^II atom is situated at a center of inversion and exhibits a slightly tetragonally distorted {O₂N₄} octahedral coordination environment, with four shorter equatorial Ni—N bonds [2.0775 (17) and 2.0924 (18) Å] and a longer axial Ni—O bond [2.1381 (17) Å]. The OPD ligand is located about an inversion center and is nearly coplanar with the NiN₄ plane [dihedral angle 0.95 (9)°]. In the crystal, the cations and anions are connected by charge-assisted intermolecular N—H⋯O and O—H⋯O hydrogen-bonding interactions into the tri-periodic network structure. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (44.1%), O⋯H/H⋯O (34.3%), C⋯H/H⋯C (14.8%) C⋯C (6.5%) (involving the cations) and O⋯H/H⋯O (50%), H⋯H (25%), C⋯H/H⋯C (15.3%), C⋯C (8.2%) (involving the anions) interactions.

Keywords: o-Phenylenediamine; 1,5-naphthalenedisulfonic acid; crystal structure; intermolecular interactions; hydrogen bonding; Hirshfeld surface.

CCDC reference: 2303464

1. Chemical context

o-Phenylenediamine (OPD) condenses with ketones and aldehydes to a variety of useful products. Its reactions with carboxylic acids and their derivatives produce the important class of benzimidazoles (Vishvanath & Ketan, 2014 ; Aniket et al., 2015 ; Pardeshi & Thore, 2015 ). Hence, OPD is commonly used in various industrial processes, including the production of dyes, polymers and the synthesis of fungicides, corrosion inhibitors, pigments, and pharmaceuticals (Abdullah et al., 2019 ; Sagasser et al., 2019 ; Pisarevskaya et al., 2020 ; Jadoun et al., 2021 ). It also exhibits electrical conductivity and is used in the production of conductive materials, such as sensors and batteries (Sayyah et al., 2009 ; Bottari et al., 2020 ). OPD is also a versatile ligand in coordination chemistry. It forms complexes with different metal ions, such as lanthanides (Koroteev et al., 2020 ), zinc (González Guillen et al., 2018 ; Zick & Geiger, 2016 ), cobalt (Ngopoh et al., 2015 ; Konieczny et al., 2019 ), copper (Djebli et al., 2012 ; Chakraborty et al., 2014 ), cadmium (González Guillen et al., 2018) or nickel (Sabbani & Das, 2009 ; Lu et al., 2009 ; Willett et al., 2012 ; Adhikari et al., 2021 ).

Compounds comprising 1,5-naphthalenedisulfonic acid (H₂NDS) or its deprotonated form (sulfonates) are of interest in supramolecular chemistry (Shi et al., 2014 ; Xu et al., 2019 ; Chen et al., 2020 ), because the sulfonate group can accept up to six hydrogen bonds (Chen et al., 2020; Oh et al., 2020 ; Chen et al., 2022 ). H₂NDS can react with organic compounds under formation of organic cations and the NDS^2– anion, or with metal compounds either under formation of non-coordinating NDS^2– anions, or with NDS^2– as a ligand (Huo et al., 2005 ; Kokunov et al., 2015 ). As a ligand, NDS^2– can bind in a bridging mode (Lian & Qu, 2013 ; Das et al., 2015 ; Tai et al., 2015 ).

In this work, we focus on the synthesis, crystal structure, and Hirshfeld surface analysis of a nickel(II) complex, [Ni(OPD)₂(H₂O)₂]·NDS, where the NDS^2– anion is not part of the metal coordination sphere.

2. Structural commentary

The structures of the molecular entities of the title compound are shown in Fig. 1. This salt consists of an Ni^II-centered complex cation with two bidentate OPD ligands and trans-aligned aqua ligands, as well as of a non-coordinating NDS^2– anion, which is the double-deprotonated form of H₂NDS. The Ni^II atom is situated at a crystallographic inversion center (Wyckoff letter d of space group P2₁/n) and exhibits a slightly tetragonally distorted {O₂N₄} octahedral coordination environment, with two pairs of shorter equatorial Ni—N bonds [2.0775 (17) and 2.0924 (18) Å] and a pair of longer axial Ni—O bonds [2.1381 (17) Å]. The OPD ligand, likewise located over a crystallographic inversion center at the middle of the central C11—C11(−x + 1, −y + 2, −z + 1) bond, is almost coplanar with the NiN₄ plane, with a dihedral angle of 0.95 (9)°. The deviation of the ideal octahedral coordination sphere around nickel might be explained as follows: The inflexible nature of the OPDA ring system with an N⋯N distance between the amino groups of 2.770 (2) Å determines the N2—Ni1—N1 and N2—Ni1—N1(−x + 2, −y + 1, −z + 1) bite angles of 83.26 (7) and 96.74 (7) °, respectively.

Figure 1
The structures of the molecular entities in the title salt, showing the atom-labeling scheme and displacement ellipsoids drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius and hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) 1 − x, 2 − y, 1 − z.]

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, the complex Ni(OPD)₂(H₂O)₂]²⁺ cation and the NDS^2– anion are associated via charge-assisted intermolecular O—H⋯O and N—H⋯O hydrogen bonds (Table 1). Each [Ni(OPD)₂(H₂O)₂]²⁺ cation forms N—H⋯O and O—H⋯O hydrogen bonds with six neighboring organic anions whereby the two aqua and two OPD ligands act solely as hydrogen-bonding donor groups (Fig. 2). All six acceptor oxygen atoms of the SO₃⁻ groups of the NDS²⁻ anions participate as double acceptor atoms (Fig. 3). Hydrogen bonds N1—H1B⋯O2ⁱⁱⁱ, N2—H2A⋯O1 and O1W–H1WB⋯O1 lead to the formation of supramolecular zigzag chains parallel to [100]. These chains are further connected by N1—H1A⋯O2ⁱⁱ and N1—H1B⋯O2ⁱⁱⁱ hydrogen bonds, resulting in sheets parallel to (110). Additionally, cations and neighboring dianions are linked through O1W—H1WA⋯O3^iv and N2—H2B⋯O3ⁱ hydrogen bonds. The molecules stack along [001], thereby forming a consolidated tri-periodic supramolecular network (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89 (1)	2.48 (2)	3.268 (3)	148 (3)
N1—H1B⋯O2ⁱⁱ	0.89 (1)	2.18 (1)	3.066 (3)	175 (3)
N2—H2A⋯O1	0.88 (1)	2.10 (1)	2.941 (2)	160 (3)
N2—H2B⋯O3ⁱⁱⁱ	0.89 (1)	2.06 (1)	2.908 (3)	158 (2)
O1W—H1WA⋯O3^iv	0.85 (1)	2.12 (2)	2.876 (3)	148 (3)
O1W—H1WB⋯O1	0.85 (1)	2.04 (2)	2.803 (2)	150 (3)
Symmetry codes: (i) ; (ii) ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Formation of hydrogen bonds (dashed lines) between the [Ni(OPD)₂(H₂O)₂]²⁺ cation with six neighboring anions. Symmetry codes refer to Table 1

Figure 3
Formation of hydrogen bonds (dashed lines) between the NDS^2– anion with six neighboring cations. Symmetry codes refer to Table 1

Figure 4
The crystal packing of the title salt in a view along [010] based on the formation of O—H⋯O and N—H⋯O hydrogen bonds (dashed blue lines). The coordination sphere around Ni^II is given in the polyhedral representation.

The supramolecular interactions discussed above were quantitatively investigated and visualized using Hirshfeld surface analysis performed with CrystalExplorer (Spackman et al., 2021 ), with a standard resolution of the three-dimensional d_norm surfaces plotted over a fixed color scale of −0.5408 (red) to 1.4249 (blue) a.u.. Visualizations were performed using a red–white–blue color scheme, where red highlights contacts shorter than the sum of the van der Waals (vdW) radii, white contacts around vdW separations, and blue contacts longer than the sum of the vdW radii. It should be noted that the Hirshfeld surfaces and fingerprint plots were calculated separately for the [Ni(OPD)₂(H₂O)₂]²⁺ cation and the NDS^2– dianion. The d_norm surface has twelve bright-red spots on the Hirshfeld surface for the cation and anion each (Fig. 5), resulting from the two O—H⋯O and four N—H⋯O intermolecular hydrogen bonds, as discussed above (Fig. 5; the number is doubled due to inversion symmetry for both entities). The classical O—H⋯O and N—H⋯O hydrogen bonds correspond to H⋯H and H⋯O contacts in the two-dimensional fingerprint plots (with contributions of 44.1 and 50% to the Hirshfeld surface for the [Ni(OPD)₂(H₂O)₂]²⁺ cation and NDS^2– anion, respectively; Fig. 6b and 6f). O⋯H/H⋯O and C⋯H/H⋯C, interactions in the cation, and H⋯H and C⋯H/H⋯C interactions in the dianion follow with contributions of 34.3, 14.8, 25 and 15.3%, respectively (Fig. 6c,d,g,h). Other minor contributions are from C⋯C (6.5%) and C⋯O (0.3%) contacts in the cation, and from C⋯C (8.2%), C⋯O (0.3%), O⋯O (0.1%) and S⋯H (0.1%) contacts in the dianion. The O⋯H/H⋯O contacts are visible as a spike with a sharp tip on the side of the corresponding two-dimensional fingerprint plot, which is indicative of strong intermolecular interactions between atoms. On the other hand, the C⋯H/H⋯C contacts form less pronounced spikes, suggesting that these interactions are much weaker.

Figure 5
View of the three-dimensional Hirshfeld surface for the [Ni(OPD)₂(H₂O)₂]²⁺ cation and the NDS^2– dianion plotted over d_norm. Parts (a) and (b) show the front and back sides, respectively, of the [Ni(OPD)₂(H₂O)₂]²⁺ dication. Parts (c) and (d) show the front and back sides, respectively, of the NDS^2– dianion.

Figure 6
Two-dimensional fingerprint plots for the [Ni(OPD)₂(H₂O)₂]²⁺ cation [parts (a), (b), (c) and (d)] and the NDS²⁻dianion [parts (e), (f), (g) and (h)]. The d_i and d_e values are the closest internal and external distances (in Å) from a given point on the Hirshfeld surface.

4. Database survey

In a search of the Cambridge Structural Database (CSD, version 2022.3.0; Groom et al., 2016 ), a total of 207 compounds containing the o-phenylenediamine moiety were identified. Out of these, 129 compounds were metal complexes, while 78 compounds were organic salts. One organic salt comprising protonated o-phenylenediamine and 1,5-naphthalenedisulfonate has been studied (CSD refcode PEFYOQ; Deng et al., 2012 ). When searching with 1,5-naphthalenedisulfonic acid as the search criterion, 90 metal complexes and 170 organic salt compounds were found. In the majority of metal complexes, 1,5-naphthalenedisulfonic acid was found in its dianionic form and was not part of the coordination sphere. However, in ten cases a bridging mode for the 1,5-naphthalenedisulfonate anion was found. Only one compound was identified where the 1,5-naphthalenedisulfonate anion coordinates to a transition-metal cation (copper) in a monodentate manner (XABPEW; Chen et al., 2002 ).

5. Synthesis and crystallization

The starting materials are commercially available and were used without further purification. The ligand OPDA (0.216 g, 2 mmol) was dissolved in 10 ml of a 1:1 v/v ethanol/water mixture. This solution was then added to a solution containing nickel(II) sulfate heptahydrate (0.281 g, 1 mmol) and disodium naphthalene-1,5-disulfonate (0.332 g, 1 mmol) in 10 ml of the same mixed ethanol/water solvent. The resulting mixture was heated under reflux and stirred for 40 min. After 5 d of slow solvent evaporation at room temperature, a light-green crystalline product was obtained with a yield of 65% (based on Ni). Elemental analysis calculated (%) for C₂₂H₂₆N₄NiO₈S₂: C 44.24, H 4.39, N 9.38; found: C 44.18, H 4.34, N 9.31.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were placed in calculated positions and refined using a riding-model approximation, with U_iso(H) = 1.2U_eq(C) and C—H = 0.93 Å for aromatic H atoms. Hydrogen atoms of the amino groups and of the water molecule were located using a difference-Fourier map and refined with bond-length restraints of 0.89 (1) and 0.85 (1) Å, respectively.

Table 2
Experimental details

Crystal data
Chemical formula	[Ni(C₆H₈N₂)₂(H₂O)₂](C₁₀H₆O₆S₂)
M_r	597.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	563
a, b, c (Å)	12.7613 (3), 7.7054 (1), 13.4641 (3)
β (°)	111.554 (2)
V (Å³)	1231.36 (5)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	3.22
Crystal size (mm)	0.22 × 0.18 × 0.14

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.573, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11384, 2380, 2152
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.04
No. of reflections	2380
No. of parameters	194
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.49
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2303464

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023009350/wm5701sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023009350/wm5701Isup2.hkl

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2023); cell refinement: CrysAlis PRO (Rigaku OD, 2023); data reduction: CrysAlis PRO (Rigaku OD, 2023); 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).

Diaquabis(o-phenylenediamine-κ²N,N')nickel(II) naphthalene-1,5-disulfonate top

Crystal data top

[Ni(C₆H₈N₂)₂(H₂O)₂](C₁₀H₆O₆S₂)	F(000) = 620
M_r = 597.30	D_x = 1.611 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
a = 12.7613 (3) Å	Cell parameters from 6737 reflections
b = 7.7054 (1) Å	θ = 4.1–71.0°
c = 13.4641 (3) Å	µ = 3.22 mm⁻¹
β = 111.554 (2)°	T = 563 K
V = 1231.36 (5) Å³	Block, light green
Z = 2	0.22 × 0.18 × 0.14 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	2380 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2152 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.038
Detector resolution: 10.0000 pixels mm^-1	θ_max = 71.3°, θ_min = 4.1°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −9→9
T_min = 0.573, T_max = 1.000	l = −14→16
11384 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)] = 0.036	w = 1/[σ²(F_o²) + (0.048P)² + 0.8302P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.50 e Å⁻³
2380 reflections	Δρ_min = −0.49 e Å⁻³
194 parameters	Extinction correction: SHELXL (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.0006 (2)
Primary atom site location: iterative

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
Ni1	1.000000	0.500000	0.500000	0.02713 (17)
S1	0.69836 (5)	0.87424 (8)	0.39745 (4)	0.03779 (18)
O1W	0.83329 (14)	0.4677 (2)	0.38469 (14)	0.0412 (4)
O1	0.73435 (15)	0.7254 (2)	0.46852 (14)	0.0488 (5)
N1	0.99045 (16)	0.2387 (2)	0.53808 (16)	0.0330 (4)
O3	0.62288 (17)	0.8217 (3)	0.29283 (14)	0.0574 (5)
N2	0.93181 (15)	0.5408 (2)	0.61643 (14)	0.0298 (4)
O2	0.79217 (17)	0.9758 (3)	0.39332 (19)	0.0636 (6)
C11	0.47191 (16)	1.0579 (3)	0.52339 (16)	0.0276 (4)
C6	0.91414 (17)	0.3765 (3)	0.66003 (16)	0.0297 (4)
C1	0.94563 (18)	0.2253 (3)	0.62287 (17)	0.0319 (5)
C7	0.62041 (18)	1.0098 (3)	0.45202 (17)	0.0313 (5)
C10	0.50918 (19)	1.2316 (3)	0.54324 (18)	0.0350 (5)
H10	0.473811	1.306841	0.575033	0.042*
C5	0.86718 (19)	0.3671 (3)	0.73833 (18)	0.0381 (5)
H5	0.846130	0.468202	0.763862	0.046*
C8	0.65220 (18)	1.1796 (3)	0.47028 (19)	0.0385 (5)
H8	0.711068	1.221455	0.451995	0.046*
C9	0.5960 (2)	1.2909 (3)	0.5166 (2)	0.0405 (5)
H9	0.618250	1.406318	0.529312	0.049*
C2	0.9316 (2)	0.0661 (3)	0.6643 (2)	0.0446 (6)
H2	0.953980	−0.035050	0.639981	0.054*
C4	0.8518 (2)	0.2078 (4)	0.7781 (2)	0.0474 (6)
H4	0.819333	0.201834	0.829604	0.057*
C3	0.8845 (2)	0.0572 (4)	0.7417 (2)	0.0510 (6)
H3	0.874888	−0.049782	0.769179	0.061*
H2A	0.8674 (14)	0.596 (3)	0.585 (2)	0.049 (8)*
H2B	0.9775 (17)	0.607 (3)	0.6689 (15)	0.038 (7)*
H1A	0.946 (2)	0.188 (4)	0.4786 (15)	0.062 (9)*
H1B	1.0556 (14)	0.182 (3)	0.561 (2)	0.052 (8)*
H1WA	0.822 (3)	0.447 (5)	0.3199 (11)	0.072 (11)*
H1WB	0.787 (2)	0.546 (4)	0.386 (3)	0.085 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0287 (3)	0.0260 (3)	0.0306 (3)	0.00340 (18)	0.0155 (2)	0.00141 (19)
S1	0.0365 (3)	0.0456 (3)	0.0367 (3)	0.0168 (2)	0.0198 (2)	0.0050 (2)
O1W	0.0343 (9)	0.0495 (10)	0.0395 (9)	0.0062 (7)	0.0133 (7)	−0.0073 (8)
O1	0.0481 (10)	0.0549 (11)	0.0464 (10)	0.0299 (8)	0.0208 (8)	0.0131 (8)
N1	0.0353 (10)	0.0280 (9)	0.0418 (11)	0.0046 (8)	0.0212 (9)	0.0015 (8)
O3	0.0633 (12)	0.0736 (14)	0.0348 (9)	0.0262 (10)	0.0175 (9)	−0.0035 (9)
N2	0.0291 (9)	0.0302 (9)	0.0316 (9)	0.0041 (7)	0.0131 (8)	−0.0002 (7)
O2	0.0550 (12)	0.0644 (13)	0.0938 (17)	0.0090 (10)	0.0538 (12)	0.0030 (11)
C11	0.0259 (9)	0.0302 (10)	0.0258 (9)	0.0070 (8)	0.0085 (8)	0.0004 (8)
C6	0.0246 (10)	0.0356 (11)	0.0280 (10)	0.0001 (8)	0.0088 (8)	0.0024 (8)
C1	0.0294 (10)	0.0331 (11)	0.0347 (11)	0.0014 (8)	0.0135 (9)	0.0040 (9)
C7	0.0279 (10)	0.0368 (11)	0.0300 (10)	0.0089 (8)	0.0117 (9)	0.0014 (8)
C10	0.0348 (11)	0.0331 (11)	0.0374 (11)	0.0067 (9)	0.0137 (9)	−0.0044 (9)
C5	0.0349 (11)	0.0492 (14)	0.0331 (11)	−0.0016 (10)	0.0158 (9)	−0.0019 (10)
C8	0.0286 (11)	0.0411 (12)	0.0475 (13)	0.0015 (9)	0.0160 (10)	0.0034 (10)
C9	0.0386 (12)	0.0301 (11)	0.0516 (14)	−0.0005 (9)	0.0153 (11)	−0.0049 (10)
C2	0.0493 (14)	0.0354 (12)	0.0517 (15)	0.0012 (11)	0.0217 (12)	0.0085 (11)
C4	0.0461 (14)	0.0645 (17)	0.0366 (12)	−0.0081 (12)	0.0209 (11)	0.0059 (12)
C3	0.0573 (16)	0.0501 (15)	0.0487 (15)	−0.0050 (13)	0.0231 (13)	0.0153 (12)

Geometric parameters (Å, º) top

Ni1—O1Wⁱ	2.1381 (17)	C11—C7ⁱⁱ	1.434 (3)
Ni1—O1W	2.1381 (17)	C11—C10	1.413 (3)
Ni1—N1	2.0924 (18)	C6—C1	1.385 (3)
Ni1—N1ⁱ	2.0924 (18)	C6—C5	1.393 (3)
Ni1—N2ⁱ	2.0776 (17)	C1—C2	1.386 (3)
Ni1—N2	2.0775 (17)	C7—C8	1.365 (3)
S1—O1	1.4558 (18)	C10—H10	0.9300
S1—O3	1.4419 (19)	C10—C9	1.363 (3)
S1—O2	1.448 (2)	C5—H5	0.9300
S1—C7	1.777 (2)	C5—C4	1.382 (4)
O1W—H1WA	0.846 (10)	C8—H8	0.9300
O1W—H1WB	0.850 (10)	C8—C9	1.403 (3)
N1—C1	1.456 (3)	C9—H9	0.9300
N1—H1A	0.886 (10)	C2—H2	0.9300
N1—H1B	0.889 (10)	C2—C3	1.383 (4)
N2—C6	1.447 (3)	C4—H4	0.9300
N2—H2A	0.882 (10)	C4—C3	1.383 (4)
N2—H2B	0.891 (10)	C3—H3	0.9300
C11—C11ⁱⁱ	1.427 (4)

O1W—Ni1—O1Wⁱ	180.0	H2A—N2—H2B	109 (3)
N1ⁱ—Ni1—O1Wⁱ	86.20 (8)	C11ⁱⁱ—C11—C7ⁱⁱ	117.6 (2)
N1ⁱ—Ni1—O1W	93.80 (8)	C10—C11—C11ⁱⁱ	119.1 (2)
N1—Ni1—O1Wⁱ	93.80 (8)	C10—C11—C7ⁱⁱ	123.28 (19)
N1—Ni1—O1W	86.20 (8)	C1—C6—N2	118.72 (18)
N1—Ni1—N1ⁱ	180.0	C1—C6—C5	119.5 (2)
N2ⁱ—Ni1—O1W	90.88 (7)	C5—C6—N2	121.8 (2)
N2ⁱ—Ni1—O1Wⁱ	89.12 (7)	C6—C1—N1	118.23 (19)
N2—Ni1—O1W	89.12 (7)	C6—C1—C2	120.1 (2)
N2—Ni1—O1Wⁱ	90.88 (7)	C2—C1—N1	121.6 (2)
N2ⁱ—Ni1—N1ⁱ	83.26 (7)	C11ⁱⁱ—C7—S1	120.95 (16)
N2—Ni1—N1ⁱ	96.74 (7)	C8—C7—S1	117.60 (17)
N2—Ni1—N1	83.26 (7)	C8—C7—C11ⁱⁱ	121.45 (19)
N2ⁱ—Ni1—N1	96.74 (7)	C11—C10—H10	119.4
N2—Ni1—N2ⁱ	180.00 (10)	C9—C10—C11	121.2 (2)
O1—S1—C7	106.30 (10)	C9—C10—H10	119.4
O3—S1—O1	110.91 (13)	C6—C5—H5	119.9
O3—S1—O2	112.29 (13)	C4—C5—C6	120.1 (2)
O3—S1—C7	107.13 (10)	C4—C5—H5	119.9
O2—S1—O1	112.67 (12)	C7—C8—H8	120.0
O2—S1—C7	107.12 (11)	C7—C8—C9	120.0 (2)
Ni1—O1W—H1WA	121 (2)	C9—C8—H8	120.0
Ni1—O1W—H1WB	115 (3)	C10—C9—C8	120.7 (2)
H1WA—O1W—H1WB	107 (3)	C10—C9—H9	119.7
Ni1—N1—H1A	106 (2)	C8—C9—H9	119.7
Ni1—N1—H1B	115 (2)	C1—C2—H2	119.9
C1—N1—Ni1	109.60 (13)	C3—C2—C1	120.2 (2)
C1—N1—H1A	112 (2)	C3—C2—H2	119.9
C1—N1—H1B	106.1 (19)	C5—C4—H4	119.9
H1A—N1—H1B	108 (3)	C5—C4—C3	120.2 (2)
Ni1—N2—H2A	107.0 (18)	C3—C4—H4	119.9
Ni1—N2—H2B	110.6 (16)	C2—C3—H3	120.1
C6—N2—Ni1	110.14 (13)	C4—C3—C2	119.8 (2)
C6—N2—H2A	110.8 (19)	C4—C3—H3	120.1
C6—N2—H2B	109.3 (17)

Ni1—N1—C1—C6	2.3 (2)	O2—S1—C7—C8	5.8 (2)
Ni1—N1—C1—C2	−179.29 (18)	C11ⁱⁱ—C11—C10—C9	1.3 (4)
Ni1—N2—C6—C1	1.6 (2)	C11ⁱⁱ—C7—C8—C9	1.7 (3)
Ni1—N2—C6—C5	−178.80 (17)	C11—C10—C9—C8	−1.1 (4)
S1—C7—C8—C9	−177.84 (18)	C6—C1—C2—C3	1.0 (4)
O1—S1—C7—C11ⁱⁱ	−53.0 (2)	C6—C5—C4—C3	1.0 (4)
O1—S1—C7—C8	126.48 (19)	C1—C6—C5—C4	−0.3 (3)
N1—C1—C2—C3	−177.3 (2)	C1—C2—C3—C4	−0.3 (4)
O3—S1—C7—C11ⁱⁱ	65.6 (2)	C7ⁱⁱ—C11—C10—C9	−178.7 (2)
O3—S1—C7—C8	−114.9 (2)	C7—C8—C9—C10	−0.4 (4)
N2—C6—C1—N1	−2.7 (3)	C5—C6—C1—N1	177.67 (19)
N2—C6—C1—C2	178.9 (2)	C5—C6—C1—C2	−0.8 (3)
N2—C6—C5—C4	−179.9 (2)	C5—C4—C3—C2	−0.7 (4)
O2—S1—C7—C11ⁱⁱ	−173.73 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱⁱ	0.89 (1)	2.48 (2)	3.268 (3)	148 (3)
N1—H1B···O2ⁱ	0.89 (1)	2.18 (1)	3.066 (3)	175 (3)
N2—H2A···O1	0.88 (1)	2.10 (1)	2.941 (2)	160 (3)
N2—H2B···O3^iv	0.89 (1)	2.06 (1)	2.908 (3)	158 (2)
O1W—H1WA···O3^v	0.85 (1)	2.12 (2)	2.876 (3)	148 (3)
O1W—H1WB···O1	0.85 (1)	2.04 (2)	2.803 (2)	150 (3)

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

Funding information

The authors thank the Uzbekistan government for direct financial support of this research. A Grant for Fundamental Research from the Center of Science and Technology of Uzbekistan is gratefully acknowledged.

References

Abdullah, Kh., Hussien, N., Salam, A., Kareem, A., Rahman, A. & Mourad, S. (2019). Biochem. Cell. Arch. 19, 1705–1711. Google Scholar
Adhikari, S., Bhattacharjee, T., Bhattacharjee, S., Daniliuc, C. G., Frontera, A., Lopato, E. M. & Bernhard, S. (2021). Dalton Trans. 50, 5632–5643. CSD CrossRef CAS PubMed Google Scholar
Aniket, P., Shantanu, D. S., Anagha, O. B. & Ajinkya, P. S. (2015). Int. J. ChemTech Res. 8, 496–500. Google Scholar
Bottari, F., Moro, G., Sleegers, N., Florea, A., Cowen, T., Piletsky, S., van Nuijs, A. L. N. & De Wael, K. (2020). Electroanalysis, 32, 135–141. CrossRef CAS Google Scholar
Chakraborty, P., Jana, A. & Mohanta, S. (2014). Polyhedron, 77, 39–46. CSD CrossRef CAS Google Scholar
Chen, B., Ye, W., Li, Z., Jin, S., Wang, J., Guo, M. & Wang, D. (2022). J. Mol. Struct. 1249, 131602. CSD CrossRef Google Scholar
Chen, C. H., Cai, J. W., Feng, X. L. & Chen, X. M. (2002). Chin. J. Inorg. Chem. 18, 659–664. CAS Google Scholar
Chen, J., Li, J., Fu, X., Xie, Q., Zeng, T., Jin, S., Xu, W. & Wang, D. (2020). J. Mol. Struct. 1204, 127491. CSD CrossRef Google Scholar
Das, D., Mahata, G., Adhikary, A., Konar, S. & Biradha, K. (2015). Cryst. Growth Des. 15, 4132–4141. CSD CrossRef CAS Google Scholar
Deng, Z.-P., Huo, L.-H., Zhao, H. & Gao, S. (2012). Cryst. Growth Des. 12, 3342–3355. Web of Science CSD CrossRef CAS Google Scholar
Djebli, Y., Boufas, S., Bencharif, L., Roisnel, T. & Bencharif, M. (2012). Acta Cryst. E68, m1411–m1412. CSD CrossRef IUCr Journals 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
González Guillén, A., Oszajca, M., Luberda-Durnaś, K., Gryl, M., Bartkiewicz, S., Miniewicz, A. & Lasocha, W. (2018). Cryst. Growth Des. 18, 5029–5037. 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, L.-H., Gao, S., Xu, S.-X. & Zhao, H. (2005). Acta Cryst. E61, m449–m450. Web of Science CSD CrossRef IUCr Journals Google Scholar
Jadoun, S., Riaz, U., Yáñez, J. & Pal Singh Chauhan, N. (2021). Eur. Polym. J. 156, 110600. CrossRef Google Scholar
Kokunov, Yu. V., Kovalev, V. V., Gorbunova, Yu. E. & Kozyukhin, S. A. (2015). Russ. J. Inorg. Chem. 60, 151–156. CrossRef CAS Google Scholar
Konieczny, P., González-Guillén, A. B., Luberda-Durnaś, K., Čižmár, E., Pełka, R., Oszajca, M. & Łasocha, W. (2019). Dalton Trans. 48, 7560–7570. CSD CrossRef CAS PubMed Google Scholar
Koroteev, P. S., Ilyukhin, A. B., Babeshkin, K. A. & Efimov, N. N. (2020). J. Mol. Struct. 1207, 127800. CSD CrossRef Google Scholar
Lian, Z. & Qu, J. (2013). Z. Kristallogr. New Cryst. Struct. 228, 482–484. CSD CrossRef CAS Google Scholar
Lu, X., Wang, Z. & Liu, M. (2009). Chin. J. Chem. 27, 221–226. CSD CrossRef CAS Google Scholar
Ngopoh, F. A. I., Lachkar, M., Đorđević, T., Lengauer, C. L. & El Bali, B. (2015). J. Chem. Crystallogr. 45, 369–375. CSD CrossRef CAS Google Scholar
Oh, H., Kim, D., Kim, D., Park, I.-H. & Jung, O.-S. (2020). Cryst. Growth Des. 20, 7027–7033. CSD CrossRef CAS Google Scholar
Pardeshi, S. D. & Thore, S. N. (2015). Int. J. Chem. Phys. 4, 300–307. CAS Google Scholar
Pisarevskaya, E. Y., Kolesnichenko, I. I., Averin, A. A., Gorbunov, A. M. & Efimov, O. N. (2020). Synth. Met. 270, 116596. CrossRef Google Scholar
Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Sabbani, S. & Das, S. K. (2009). Inorg. Chem. Commun. 12, 364–367. CSD CrossRef CAS Google Scholar
Sagasser, J., Ma, B. N., Baecker, D., Salcher, S., Hermann, M., Lamprecht, J., Angerer, S., Obexer, P., Kircher, B. & Gust, R. (2019). J. Med. Chem. 62, 8053–8061. CrossRef CAS PubMed Google Scholar
Sayyah, S. M., El–Deeb, M. M., Kamal, S. M. & Azooz, R. (2009). J. Appl. Polym. Sci. 112, 3695–3706. CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shi, Ch., Wei, B. & Zhang, W. (2014). Cryst. Growth Des. 14, 6570–6580. CSD CrossRef CAS Google Scholar
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tai, X.-S., Zhang, Y.-P. & Zhao, W.-H. (2015). Res. Chem. Intermed. 41, 4339–4347. CSD CrossRef CAS Google Scholar
Vishvanath, D. P. & Ketan, P. P. (2014). Int. J. ChemTech Res. 8, 457–465. Google Scholar
Willett, R. D., Gómez-García, C. J., Twamley, B., Gómez-Coca, S. & Ruiz, E. (2012). Inorg. Chem. 51, 5487–5493. CSD CrossRef CAS PubMed Google Scholar
Xu, W., Lu, Y., Xia, Y. Y., Liu, B., Jin, S., Zhong, B., Wang, D. & Guo, M. (2019). J. Mol. Struct. 1189, 81–93. CSD CrossRef CAS Google Scholar
Zick, P. L. & Geiger, D. K. (2016). Acta Cryst. E72, 1037–1042. 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.