Synthesis, crystal structure and Hirshfeld surface analysis of a cadmium complex of naphthalene-1,5-di­sulfonate and o-phenyl­enedi­amine

Suyunov, J.; Torambetov, B.; Turaev, K.; Kadirova, S.; Alimnazarov, B.; Ashurov, J.

doi:10.1107/S2056989023010125

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 12| December 2023| Pages 1190-1193

https://doi.org/10.1107/S2056989023010125

Open

access

Synthesis, crystal structure and Hirshfeld surface analysis of a cadmium complex of naphthalene-1,5-disulfonate and o-phenylenediamine

Jabbor Suyunov,^a Batirbay Torambetov,^b ^* Khayit Turaev,^a Shakhnoza Kadirova,^b Bekmurod Alimnazarov ^a and Jamshid Ashurov ^c

^aTermez State University, Barkamol Avlod St. 43, Termez, 190111, Uzbekistan, ^bNational University of Uzbekistan named after Mirzo Ulugbek, 4 University St, Tashkent, 100174, Uzbekistan, and ^cInstitute of Bioorganic Chemistry, Academy of Sciences of Uzbekistan, M. Ulugbek St. 83, Tashkent, 100125, Uzbekistan
^*Correspondence e-mail: torambetov_b@mail.ru

Edited by G. Diaz de Delgado, Universidad de Los Andes Mérida, Venezuela (Received 6 June 2023; accepted 22 November 2023; online 30 November 2023)

A novel o-phenylenediamine (opda)-based cadmium complex, bis(benzene-1,2-diamine-κ²N,N′)bis(benzene-1,2-diamine-κN)cadmium(II) naphthalene-1,5-disulfonate, [Cd(C₆H₈N₂)₄](C₁₀H₆O₆S₂), was synthesized. The complex salt crystallizes in the monoclinic space group C2/c. The Cd atom occupies a special position and coordinates six nitrogen atoms from four o-phenylenediamine molecules, two as chelating ligands and two as monodentate ligands. The amino H atoms of opda interact with two O atoms of the naphthalene-1,5-disulfonate anions. The anions act as bridges between [Cd(opda)₄]²⁺ cations, forming a two-dimensional network in the [010] and [001] directions. The Hirshfeld surface analysis shows that the primary factors contributing to the supramolecular interactions are short contacts, particularly van der Waals forces of the type H⋯H, O⋯H and C⋯H.

Keywords: crystal structure; cadmium complex; o-phenylenediamine; naphthalene-1,5-disulfonate; Hirshfeld surface analysis.

CCDC reference: 2257108

1. Chemical context

Cadmium is widely used in the fabrication of rechargeable batteries, in alloys, coatings (electroplating), solar cells, plastic stabilizers, phosphate fertilizers, and pigments (Omar et al., 2014 ; Morrow, 2010 ; Indumathi et al., 2011 ; Kapadnis et al., 2020 ; Wakkaf et al., 2020 ; Roberts, 2014 ; Cesaratto et al., 2014 ). Given its common use, cadmium is now spreading widely in the environment (Kumar et al., 2019 ; Wang et al., 2023 ) and, due to its toxicity, it is necessary to prevent the technogenic spread of cadmium and its harmful consequences.

When it comes to complex formation, organic ligands with multiple donor centers that form chelates play a crucial role. Stable complexes are obtained by the formation of a ring consisting of five or six members, including a metal atom in the ring. Additionally, when the bidentate ligand is involved in coordination with the central atom by forming a five-membered ring, it further increases the stability of the complex (Lawrance, 2010 ). The conformational change of five- and six-membered diamine chelate rings in metal complexes has been thoroughly documented (Corey et al., 1959 ; Gollogly et al., 1967 ; Ma et al., 2005 , 2012 ). In this regard, the o-phenylenediamine (opda) ligand has been extensively studied as a linking agent that effectively forms a chelating ring with a variety of metal cations. Developing metal ion sorbents utilizing these organic ligands is both economically and practically efficient. We present a report on the crystal structure and Hirshfeld surface analysis of a newly synthesized Cd complex salt of naphthalene-1,5-disulfonate with o-phenylenediamine (opda) as its base.

2. Structural commentary

The complex salt [Cd(opda)₄](C₁₀H₆O₆S₂) crystallizes in the monoclinic system, space group C2/c. The Cd atom occupies a special position with twofold symmetry (Wyckoff position 4e). The midpoint of the naphthalene-1,5-disulfonate anion lies on a center of inversion (Wyckoff position 4b). Therefore, the asymmetric unit consists of one half of the complex cation and anion.

Fig. 1 shows the coordination environment of the Cd atom and the hydrogen bonds between the amine hydrogens and the oxygen atoms of the anion. The Cd atom coordinates six nitrogen atoms which come from two o-phenylenediamine molecules and their two symmetry-related counterparts [symmetry operation: (i) 1 − x, y, $[{3\over 2}]$ − z]. The naphthalene-1,5-disulfonate anion is completed by atoms related by 1 − x, 2 − y, 1 − z [symmetry operation: (ii)]. Two of the o-phenylenediamine ligands are coordinated in a chelating fashion while the other two form monodentate bonds. The chelating and monodentate ligands are located in cis positions. The complex exhibits a distorted octahedral coordination sphere for the metal atom due to the reduction of the N1—Cd1—N2 angle [70.41 (6)°]. This value is similar to those found in other cadmium complexes reported by several authors (Gonzalez Guillen et al., 2018 ; Malinina et al., 2007 ; Rahman et al., 2017 ; Supriya, 2009 ) where a chelate ring is observed. The largest bond angle between atoms in the basal plane in this polyhedron is 101.57 (6)° for N1ⁱ—Cd1—N3. Distortions are also observed in the angles between opposite vertex atoms. A value of 162.11 (10)° is observed for N1ⁱ—Cd1—N1 and 170.30 (6)° for N2—Cd1—N3ⁱ and N2ⁱ—Cd1—N3. All Cd1—N bonds have very close values with the maximum difference of only 0.0842 Å. The chelating coordination mode slightly affects the positions of the N and C atoms in the opda ligands. The opda ligands are approximately planar, with a maximum deviation from the least-squares plane of 0.003 Å for atom C12 in the monodentate one (r.m.s. deviation 0.002 Å) and 0.005 Å for atom C1 in the bidentate one (0.002 Å r.m.s. deviation). The dihedral angle between the main planes of the phenyl ring (C1–C6 or C7–C12) and the N—C—C—N fragment is 4.16 (12)° in the bidentate ligand and 1.73 (13)° in the monodentate ligand.

Figure 1
Molecular structure of the title compound. The hydrogen bond is indicated by a dashed line. Displacement ellipsoids are plotted at the 30% probability level. [Symmetry codes: (i) 1 − x, 2 − y, 1 − z; (ii) 1 − x, y, 3/2 - z.]

3. Supramolecular features

In the crystal, the [Cd(opda)₄]²⁺ cation and the naphthalene-1,5-disulfonate dianion interact via N1—H1B⋯O1, N3—H3A⋯O2, N3—H3B⋯O2ⁱⁱ, N4—H4A⋯O1ⁱⁱ and N2—H2A⋯O2ⁱ hydrogen bonds (Fig. 1, Table 1). Here the O1 atom participates in a bifurcated hydrogen bond with N1 and N4ⁱⁱ and the O2 atom does the same with atoms N3 and N3ⁱⁱ. These hydrogen bonds form infinite two-dimensional networks along the [010] and [001] directions in which the naphthalene-1,5-disulfonate dianions serve as bridges between [Cd(opda)₄]²⁺ cations as hydrogen bond acceptors in both directions (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2	0.86 (3)	2.36 (3)	3.185 (2)	160 (2)
N2—H2A⋯O2ⁱ	0.81 (3)	2.30 (3)	3.046 (3)	154 (3)
N1—H1B⋯O1	0.83 (3)	2.18 (3)	2.955 (2)	156 (3)
N3—H3B⋯O2ⁱⁱ	0.81 (3)	2.37 (3)	3.097 (2)	150 (2)
N4—H4A⋯O1ⁱⁱ	0.91 (3)	2.11 (3)	3.021 (3)	176 (3)
Symmetry codes: (i) ; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Figure 2
Crystal packing of the corrugated layers parallel to the (200) plane showing hydrogen bonds in cyan lines. Projection along the perpendicular to the (200) plane.

Each [Cd(opda)₄]²⁺ cation is surrounded by naphthalene-1,5-disulfonate²⁻ anions from four positions, and their oxygen atoms (symmetry codes x, y, z; 1 - x, y, $[{3\over 2}]$ − z; 1 − x, −1 + y, $[{3\over 2}]$ − z; x, −1 + y, z) are hydrogen-bonded to the NH groups of the cation. These hydrogen bonds serve to grow the network along the [010] direction (Fig. 2). At the same time, the naphthalene-1,5-disulfonate anions are attached to neighboring [Cd(opda)₄]²⁺ cations, through hydrogen bonds that ensure the growth of the crystal network in the [001] direction (Figs. 2 and 3).

Figure 3
View of the molecular packing showing the hydrogen-bonding interactions that extend along the c-axis direction.

4. Hirshfeld surface analysis

To further investigate the intermolecular interactions present in the title compound, a Hirshfeld surface analysis (Spackman & Byrom, 1997 ) was performed and the two-dimensional fingerprint plots were generated with CrystalExplorer17 (Spackman et al., 2021 ). The Hirshfeld surfaces mapped over d_norm for both moieties (representing various interactions with the default colors) are shown in Fig. 4. The default scaling was used {−0.4573, 1.2430 Å for the [Cd(opda)₄] cation and −0.4579, 1.0829 Å for the naphthalene-1,5-disulfone anion}.

Figure 4
Hirshfeld surfaces of the [Cd(opda)₄]²⁺ cation and the [naphthalene-1,5-disulfonate]²⁻ anion mapped with d_norm.

The two-dimensional (2D) fingerprint plots (McKinnon et al., 2007 ) are shown in Fig. 5. The most significant interactions, whose contribution to the Hirshfeld surface area exceed 20.0% at least for one of the ions in the structure, are H⋯H {54% and 28% for the [Cd(opda)₄] cation and naphthalene-1,5-disulfone anion moieties, respectively}, H⋯O/O⋯H (22.1% and 43.5%) and C⋯H/H⋯C (22.5% and 26.4%). These interactions play a crucial role in the overall consolidation of the crystal structure.

Figure 5
Contributions of the various contacts to the two-dimensional fingerprint plots built using the Hirshfeld surfaces of the [Cd(opda)₄]²⁺ cation (at the top) and the [naphthalene-1,5-disulfonate]²⁻ anion (at the bottom).

5. Database survey

A survey of the Cambridge Structural Database (CSD, version 5.43, update of November 2021; Groom et al., 2016) revealed that 74 crystal structures have been reported for chelate complexes of o-phenylenediamine with several metal atoms. The CSD includes structures of complexes of Ni^II and Cr^II based on o-phenylenediamine with ratios of 1:4 and six-coordination numbers (OPDANI, Elder et al., 1974 ; FENVOK, Ariyananda et al., 2005 ; SOFXIU, Jubb et al., 1991 ). However, no co-crystal complexes and metal complexes containing o-phenylenediamine and the naphthalene-1,5-disulfonate anion together in the crystal have been reported.

6. Synthesis and crystallization

Ethanol/water 1:1 (10 mL) solutions of Cd(CH₃COO)₂·2H₂O (0.266 g, 0.001 mol) and sodium naphthalene-1,5-disulfonate (0.332 g, 0.001 mol) were combined. To the obtained solution, a 10 ml ethanol solution of o-phenylenediamine (opda) (0.432 g, 0.004 mol) was added dropwise and then stirred at 323 K for 30 minutes. The final solution was left to crystallize and X-ray quality single crystals were produced after 15 days by slow evaporation of the solvent.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All the hydrogen atoms were located in difference-Fourier maps and refined isotropically.

Table 2
Experimental details

Crystal data
Chemical formula	[Cd(C₆H₈N₂)₄](C₁₀H₆O₆S₂)
M_r	831.24
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	23.5743 (2), 7.7286 (1), 19.7260 (2)
β (°)	103.858 (1)
V (Å³)	3489.39 (7)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	6.62
Crystal size (mm)	0.3 × 0.26 × 0.2

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023)
T_min, T_max	0.698, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16542, 3390, 3298
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.061, 1.04
No. of reflections	3390
No. of parameters	264
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.51
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015 a), SHELXL2018/3 (Sheldrick, 2015b) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2257108

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989023010125/dj2067sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023010125/dj2067Isup2.hkl

checkCIF report

Computing details top

Bis(benzene-1,2-diamine-κ²N,N')bis(benzene-1,2-diamine-κN)cadmium(II) naphthalene-1,5-disulfonate top

Crystal data top

[Cd(C₆H₈N₂)₄](C₁₀H₆O₆S₂)	F(000) = 1704
M_r = 831.24	D_x = 1.582 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54184 Å
a = 23.5743 (2) Å	Cell parameters from 13387 reflections
b = 7.7286 (1) Å	θ = 3.9–71.3°
c = 19.7260 (2) Å	µ = 6.62 mm⁻¹
β = 103.858 (1)°	T = 293 K
V = 3489.39 (7) Å³	Block, colourless
Z = 4	0.3 × 0.26 × 0.2 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	3390 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3298 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.030
Detector resolution: 10.0000 pixels mm^-1	θ_max = 71.4°, θ_min = 3.9°
ω scans	h = −23→28
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −9→9
T_min = 0.698, T_max = 1.000	l = −24→24
16542 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)] = 0.023	w = 1/[σ²(F_o²) + (0.0374P)² + 1.6331P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.061	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.29 e Å⁻³
3390 reflections	Δρ_min = −0.51 e Å⁻³
264 parameters	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00060 (3)
Primary atom site location: dual

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
Cd1	0.500000	0.30368 (2)	0.750000	0.03390 (8)
S1	0.57283 (2)	0.75940 (6)	0.64093 (2)	0.03278 (11)
O3	0.63434 (6)	0.7592 (2)	0.67223 (8)	0.0538 (4)
O2	0.53752 (7)	0.82032 (19)	0.68767 (7)	0.0461 (4)
O1	0.55070 (7)	0.59515 (18)	0.60921 (8)	0.0471 (3)
N3	0.55688 (7)	0.5428 (2)	0.81048 (8)	0.0324 (3)
N1	0.56647 (7)	0.2566 (2)	0.68088 (9)	0.0359 (3)
N2	0.57034 (7)	0.0874 (2)	0.80405 (10)	0.0412 (4)
C17	0.50295 (7)	0.9405 (2)	0.52814 (8)	0.0264 (3)
C7	0.61049 (7)	0.5314 (2)	0.86432 (8)	0.0320 (4)
N4	0.55812 (9)	0.3778 (3)	0.93793 (11)	0.0553 (5)
C15	0.60837 (7)	0.9911 (2)	0.55757 (9)	0.0334 (4)
H15	0.645358	0.968869	0.585633	0.040*
C16	0.56084 (7)	0.9092 (2)	0.57062 (8)	0.0277 (3)
C13	0.54760 (8)	1.1410 (3)	0.46009 (9)	0.0341 (4)
H13	0.543889	1.218105	0.423086	0.041*
C14	0.60174 (8)	1.1089 (3)	0.50191 (10)	0.0382 (4)
H14	0.634285	1.165022	0.493536	0.046*
C12	0.60984 (8)	0.4504 (3)	0.92721 (9)	0.0391 (4)
C6	0.62457 (8)	0.1375 (2)	0.78897 (10)	0.0361 (4)
C1	0.62273 (8)	0.2241 (2)	0.72671 (10)	0.0348 (4)
C2	0.67355 (10)	0.2866 (3)	0.71257 (13)	0.0493 (5)
H2	0.672048	0.345609	0.671084	0.059*
C8	0.66153 (9)	0.5986 (3)	0.85278 (11)	0.0468 (5)
H8	0.661275	0.653233	0.810709	0.056*
C5	0.67805 (9)	0.1121 (3)	0.83592 (12)	0.0506 (5)
H5	0.679763	0.052972	0.877417	0.061*
C11	0.66247 (10)	0.4376 (3)	0.97790 (12)	0.0572 (6)
H11	0.663070	0.383961	1.020270	0.069*
C3	0.72678 (10)	0.2621 (4)	0.75990 (16)	0.0609 (6)
H3	0.760948	0.304468	0.750326	0.073*
C4	0.72872 (10)	0.1742 (3)	0.82129 (15)	0.0619 (7)
H4	0.764382	0.156738	0.853024	0.074*
C9	0.71343 (10)	0.5848 (4)	0.90398 (14)	0.0677 (7)
H9	0.747926	0.630189	0.896406	0.081*
C10	0.71319 (11)	0.5032 (4)	0.96591 (14)	0.0718 (8)
H10	0.747871	0.492453	1.000044	0.086*
H3A	0.5610 (10)	0.613 (4)	0.7782 (13)	0.049 (7)*
H2A	0.5562 (12)	0.003 (4)	0.7824 (14)	0.063 (8)*
H1A	0.5530 (11)	0.162 (4)	0.6578 (13)	0.051 (7)*
H1B	0.5681 (12)	0.337 (4)	0.6538 (15)	0.064 (9)*
H3B	0.5317 (11)	0.593 (3)	0.8244 (13)	0.054 (7)*
H4A	0.5264 (13)	0.448 (4)	0.9240 (14)	0.064 (8)*
H2B	0.5746 (12)	0.072 (4)	0.8486 (16)	0.071 (9)*
H4B	0.5614 (16)	0.361 (5)	0.980 (2)	0.102 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02348 (11)	0.03120 (12)	0.04631 (12)	0.000	0.00697 (7)	0.000
S1	0.0289 (2)	0.0389 (2)	0.0286 (2)	0.00213 (17)	0.00313 (16)	0.00811 (16)
O3	0.0305 (7)	0.0741 (10)	0.0503 (9)	0.0027 (7)	−0.0035 (6)	0.0233 (8)
O2	0.0478 (8)	0.0612 (10)	0.0323 (7)	0.0017 (6)	0.0153 (6)	0.0050 (6)
O1	0.0549 (9)	0.0323 (7)	0.0501 (8)	0.0017 (6)	0.0044 (6)	0.0089 (6)
N3	0.0312 (8)	0.0332 (8)	0.0283 (7)	0.0007 (6)	−0.0019 (6)	0.0012 (6)
N1	0.0329 (8)	0.0379 (9)	0.0361 (8)	0.0067 (7)	0.0064 (6)	−0.0009 (7)
N2	0.0349 (8)	0.0400 (10)	0.0458 (10)	0.0000 (7)	0.0041 (7)	0.0097 (8)
C17	0.0245 (8)	0.0272 (8)	0.0277 (7)	0.0021 (6)	0.0070 (6)	0.0004 (6)
C7	0.0308 (9)	0.0319 (9)	0.0299 (8)	0.0015 (7)	0.0003 (6)	−0.0013 (7)
N4	0.0487 (11)	0.0661 (13)	0.0476 (11)	−0.0084 (10)	0.0048 (8)	0.0217 (10)
C15	0.0237 (8)	0.0391 (10)	0.0359 (9)	0.0002 (7)	0.0039 (6)	0.0026 (7)
C16	0.0265 (8)	0.0303 (8)	0.0259 (7)	0.0031 (6)	0.0059 (6)	0.0006 (6)
C13	0.0298 (8)	0.0371 (9)	0.0359 (9)	−0.0002 (7)	0.0091 (7)	0.0108 (7)
C14	0.0251 (8)	0.0428 (11)	0.0475 (10)	−0.0044 (7)	0.0103 (7)	0.0090 (8)
C12	0.0384 (10)	0.0393 (10)	0.0351 (9)	0.0002 (8)	0.0001 (7)	0.0038 (8)
C6	0.0292 (9)	0.0315 (9)	0.0449 (10)	0.0043 (7)	0.0035 (7)	0.0007 (8)
C1	0.0274 (9)	0.0344 (9)	0.0421 (10)	0.0066 (7)	0.0072 (7)	−0.0038 (7)
C2	0.0404 (11)	0.0536 (13)	0.0580 (13)	0.0055 (9)	0.0196 (10)	0.0023 (10)
C8	0.0370 (10)	0.0579 (13)	0.0454 (11)	−0.0042 (9)	0.0096 (8)	0.0041 (9)
C5	0.0380 (11)	0.0556 (14)	0.0517 (12)	0.0084 (9)	−0.0022 (9)	0.0069 (10)
C11	0.0511 (13)	0.0697 (15)	0.0404 (11)	0.0033 (11)	−0.0091 (9)	0.0125 (10)
C3	0.0315 (11)	0.0721 (16)	0.0802 (18)	−0.0003 (11)	0.0158 (11)	−0.0033 (14)
C4	0.0299 (11)	0.0720 (17)	0.0753 (17)	0.0078 (10)	−0.0039 (10)	−0.0017 (13)
C9	0.0311 (11)	0.093 (2)	0.0735 (16)	−0.0103 (12)	0.0026 (10)	0.0021 (15)
C10	0.0386 (12)	0.098 (2)	0.0636 (16)	0.0009 (13)	−0.0183 (11)	0.0066 (14)

Geometric parameters (Å, º) top

Cd1—N3ⁱ	2.4230 (15)	N4—H4B	0.82 (4)
Cd1—N3	2.4230 (15)	C15—H15	0.9300
Cd1—N1ⁱ	2.3388 (16)	C15—C16	1.364 (2)
Cd1—N1	2.3388 (16)	C15—C14	1.406 (3)
Cd1—N2	2.4153 (17)	C13—H13	0.9300
Cd1—N2ⁱ	2.4153 (17)	C13—C14	1.366 (2)
S1—O3	1.4335 (15)	C14—H14	0.9300
S1—O2	1.4601 (15)	C12—C11	1.398 (3)
S1—O1	1.4556 (15)	C6—C1	1.390 (3)
S1—C16	1.7765 (16)	C6—C5	1.388 (3)
N3—C7	1.446 (2)	C1—C2	1.381 (3)
N3—H3A	0.86 (3)	C2—H2	0.9300
N3—H3B	0.81 (3)	C2—C3	1.386 (3)
N1—C1	1.437 (2)	C8—H8	0.9300
N1—H1A	0.88 (3)	C8—C9	1.392 (3)
N1—H1B	0.83 (3)	C5—H5	0.9300
N2—C6	1.434 (2)	C5—C4	1.380 (4)
N2—H2A	0.81 (3)	C11—H11	0.9300
N2—H2B	0.87 (3)	C11—C10	1.370 (4)
C17—C17ⁱⁱ	1.423 (3)	C3—H3	0.9300
C17—C16	1.440 (2)	C3—C4	1.380 (4)
C17—C13ⁱⁱ	1.415 (2)	C4—H4	0.9300
C7—C12	1.393 (3)	C9—H9	0.9300
C7—C8	1.379 (3)	C9—C10	1.376 (4)
N4—C12	1.403 (3)	C10—H10	0.9300
N4—H4A	0.91 (3)

N3ⁱ—Cd1—N3	80.58 (7)	H4A—N4—H4B	106 (3)
N1ⁱ—Cd1—N3	101.57 (6)	C16—C15—H15	119.8
N1ⁱ—Cd1—N3ⁱ	92.10 (6)	C16—C15—C14	120.34 (15)
N1—Cd1—N3ⁱ	101.57 (6)	C14—C15—H15	119.8
N1—Cd1—N3	92.10 (6)	C17—C16—S1	121.00 (12)
N1ⁱ—Cd1—N1	162.11 (10)	C15—C16—S1	117.74 (12)
N1—Cd1—N2	70.41 (6)	C15—C16—C17	121.26 (15)
N1—Cd1—N2ⁱ	96.90 (6)	C17ⁱⁱ—C13—H13	119.3
N1ⁱ—Cd1—N2	96.89 (6)	C14—C13—C17ⁱⁱ	121.44 (16)
N1ⁱ—Cd1—N2ⁱ	70.41 (6)	C14—C13—H13	119.3
N2—Cd1—N3	94.02 (6)	C15—C14—H14	119.9
N2—Cd1—N3ⁱ	170.30 (6)	C13—C14—C15	120.15 (16)
N2ⁱ—Cd1—N3ⁱ	94.02 (6)	C13—C14—H14	119.9
N2ⁱ—Cd1—N3	170.30 (6)	C7—C12—N4	120.60 (17)
N2—Cd1—N2ⁱ	92.41 (9)	C7—C12—C11	118.13 (19)
O3—S1—O2	113.53 (10)	C11—C12—N4	121.22 (19)
O3—S1—O1	113.92 (10)	C1—C6—N2	118.20 (16)
O3—S1—C16	107.01 (9)	C5—C6—N2	122.42 (19)
O2—S1—C16	105.95 (8)	C5—C6—C1	119.26 (18)
O1—S1—O2	110.66 (9)	C6—C1—N1	117.96 (17)
O1—S1—C16	105.00 (8)	C2—C1—N1	121.76 (19)
Cd1—N3—H3A	105.4 (16)	C2—C1—C6	120.12 (19)
Cd1—N3—H3B	99.6 (19)	C1—C2—H2	119.8
C7—N3—Cd1	126.76 (11)	C1—C2—C3	120.4 (2)
C7—N3—H3A	110.4 (16)	C3—C2—H2	119.8
C7—N3—H3B	111.3 (18)	C7—C8—H8	119.9
H3A—N3—H3B	100 (2)	C7—C8—C9	120.1 (2)
Cd1—N1—H1A	102.8 (16)	C9—C8—H8	119.9
Cd1—N1—H1B	114 (2)	C6—C5—H5	119.8
C1—N1—Cd1	107.87 (12)	C4—C5—C6	120.3 (2)
C1—N1—H1A	110.1 (17)	C4—C5—H5	119.8
C1—N1—H1B	111 (2)	C12—C11—H11	119.6
H1A—N1—H1B	111 (3)	C10—C11—C12	120.8 (2)
Cd1—N2—H2A	100 (2)	C10—C11—H11	119.6
Cd1—N2—H2B	116.2 (19)	C2—C3—H3	120.2
C6—N2—Cd1	105.88 (12)	C4—C3—C2	119.5 (2)
C6—N2—H2A	113 (2)	C4—C3—H3	120.2
C6—N2—H2B	110.7 (19)	C5—C4—H4	119.8
H2A—N2—H2B	111 (3)	C3—C4—C5	120.4 (2)
C17ⁱⁱ—C17—C16	117.68 (18)	C3—C4—H4	119.8
C13ⁱⁱ—C17—C17ⁱⁱ	119.12 (18)	C8—C9—H9	120.3
C13ⁱⁱ—C17—C16	123.20 (15)	C10—C9—C8	119.3 (2)
C12—C7—N3	119.18 (16)	C10—C9—H9	120.3
C8—C7—N3	119.98 (17)	C11—C10—C9	120.8 (2)
C8—C7—C12	120.84 (17)	C11—C10—H10	119.6
C12—N4—H4A	113.3 (18)	C9—C10—H10	119.6
C12—N4—H4B	110 (3)

Cd1—N3—C7—C12	−62.9 (2)	C17ⁱⁱ—C13—C14—C15	0.8 (3)
Cd1—N3—C7—C8	116.43 (18)	C7—C12—C11—C10	0.0 (4)
Cd1—N1—C1—C6	33.6 (2)	C7—C8—C9—C10	0.2 (4)
Cd1—N1—C1—C2	−141.87 (17)	N4—C12—C11—C10	177.5 (3)
Cd1—N2—C6—C1	−31.2 (2)	C16—C15—C14—C13	−0.6 (3)
Cd1—N2—C6—C5	144.82 (18)	C13ⁱⁱ—C17—C16—S1	1.4 (2)
O3—S1—C16—C17	−179.81 (14)	C13ⁱⁱ—C17—C16—C15	−179.75 (17)
O3—S1—C16—C15	1.27 (17)	C14—C15—C16—S1	178.96 (14)
O2—S1—C16—C17	−58.37 (15)	C14—C15—C16—C17	0.0 (3)
O2—S1—C16—C15	122.71 (15)	C12—C7—C8—C9	0.6 (3)
O1—S1—C16—C17	58.79 (15)	C12—C11—C10—C9	0.7 (5)
O1—S1—C16—C15	−120.12 (15)	C6—C1—C2—C3	0.7 (3)
N3—C7—C12—N4	1.2 (3)	C6—C5—C4—C3	0.0 (4)
N3—C7—C12—C11	178.65 (19)	C1—C6—C5—C4	0.9 (3)
N3—C7—C8—C9	−178.7 (2)	C1—C2—C3—C4	0.1 (4)
N1—C1—C2—C3	176.0 (2)	C2—C3—C4—C5	−0.5 (4)
N2—C6—C1—N1	−0.6 (3)	C8—C7—C12—N4	−178.1 (2)
N2—C6—C1—C2	174.92 (19)	C8—C7—C12—C11	−0.7 (3)
N2—C6—C5—C4	−175.1 (2)	C8—C9—C10—C11	−0.8 (5)
C17ⁱⁱ—C17—C16—S1	−178.68 (15)	C5—C6—C1—N1	−176.70 (19)
C17ⁱⁱ—C17—C16—C15	0.2 (3)	C5—C6—C1—C2	−1.2 (3)

Symmetry codes: (i) −x+1, y, −z+3/2; (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
N3—H3A···O2	0.86 (3)	2.36 (3)	3.185 (2)	160 (2)
N2—H2A···O2ⁱⁱⁱ	0.81 (3)	2.30 (3)	3.046 (3)	154 (3)
N1—H1B···O1	0.83 (3)	2.18 (3)	2.955 (2)	156 (3)
N3—H3B···O2ⁱ	0.81 (3)	2.37 (3)	3.097 (2)	150 (2)
N4—H4A···O1ⁱ	0.91 (3)	2.11 (3)	3.021 (3)	176 (3)

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

Funding information

This work was supported by Uzbekistan Ministry of higher education, science and innovation.

References

Ariyananda, W. G. P. & Norman, R. E. (2005). Acta Cryst. E61, m187–m189. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cesaratto, A., D'Andrea, C., Nevin, A., Valentini, G., Tassone, F., Alberti, R. & Comelli, D. (2014). Anal. Methods 6, 130–138. CrossRef CAS Google Scholar
Corey, E. J. & Bailar, J. C. (1959). J. Am. Chem. Soc. 81, 2620–2629. CrossRef CAS Web of Science 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
Elder, R. C., Koran, D. & Mark, H. B. (1974). Inorg. Chem. 13, 1644–1649. CrossRef CAS Google Scholar
Gollogly, J. & Hawkins, C. (1967). Aust. J. Chem. 20, 2395–2402. CrossRef CAS Google Scholar
Gonzalez Guillen, A., Oszajca, M., Luberda-Durnaś, K., Gryl, M., Bartkiewicz, S., Miniewicz, A. & Lasocha, W. (2018). Cryst. Growth Des. 18, 9, 5029–5037. Google Scholar
Indumathi, S. N., Vasudevan, T., Sundarrajan, S., Subba Rao, B. V., Murthy, C. V. S. & Yadav, D. R. (2011). Metal Finishing, 109, 15–21. CAS Google Scholar
Jubb, J., Larkworthy, L. F., Oliver, L. F., Povey, D. C. & Smith, G. W. (1991). J. Chem. Soc. Dalton Trans. pp. 2045–2050. CSD CrossRef Web of Science Google Scholar
Kapadnis, R. S., Bansode, S. B., Supekar, A. T., Bhujbal, P. K., Kale, S. S., Jadkar, S. R. & Pathan, H. M. (2020). ES Energy & Environment, 10, 3-12. CAS Google Scholar
Kumar, S. & Sharma, A. (2019). Rev. Environ. Health, 34, 327–338. CrossRef CAS PubMed Google Scholar
Lawrance, G. A. (2010). Introduction to Coordination Chemistry. John Wiley & Sons Ltd. Google Scholar
Ma, G., Fischer, A., Nieuwendaal, R., Ramaswamy, K. & Hayes, S. E. (2005). Inorg. Chim. Acta, 358, 3165–3173. CrossRef CAS Google Scholar
Ma, K.-R., Shi, J., Zhang, D.-J. & Xu, J.-N. (2012). J. Mol. Struct. 1013, 138–142. CrossRef CAS Google Scholar
Malinina, E. A., Drozdova, V. V., Goeva, L. V., Polyakova, I. N. & Kuznetsov, N. T. (2007). Russ. J. Inorg. Chem. 52, 854–858. CrossRef Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. 3814–3816. Google Scholar
Morrow, H. (2010). Kirk-Othmer Encyclopedia of Chemical Technology. Cadmium and Cadmium Alloys. 4, 1–36. https://doi. org/10.1002/0471238961.0301041303011818.a01.pub3. Google Scholar
Omar, N., Firouz, Y., Monem, M. A., Samba, A., Gualous, H., Coosemans, T., Van den Bossche, P. & Van Mierlo, J. (2014). Reference Module in Chemistry: Molecular Sciences and Chemical Engineering, https://doi. org/10.1016/B978-0-12-409547-2.10740-1 Google Scholar
Rahman, W. S. K. A., Ahmad, J., Halim, S. N. A., Jotani, M. M. & Tiekink, E. R. T. (2017). Acta Cryst. E73, 1363–1367. CrossRef IUCr Journals Google Scholar
Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Roberts, T. L. (2014). Cadmium and Phosphorous Fertilizers: The Issues and the Science. Procedia Engineering, 83, 52–59. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spackman, M. A. & Byrom, P. G. (1997). Chem. Phys. Lett. 267, 215–220. CrossRef CAS Web of Science 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
Supriya, S. (2009). J. Chem. Sci. 121, 137–143. CrossRef CAS Google Scholar
Wakkaf, T., Allouche, M., Harrath, A. H., Mansour, L., Alwasel, S., Ansari, K. G. M. T., Beyrem, H., Sellami, B. & Boufahja, F. (2020). Environ. Pollut. 266, 115263. https://doi.org/10.1016/j.envpol.2020.115263 Google Scholar
Wang, H., Sun, Sh., Ren, Y., Yang, R., Guo, J., Zong, Yu., Zhang, Q., Zhao, J., Zhang, W., Xu, W., Guan, Sh. & Xu, J. (2023). Biol. Trace Elem. Res. 201, 139–148. CrossRef CAS PubMed 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.