Synthesis, mol­ecular and crystal structure of [(NH2)2CSSC(NH2)2]2[RuBr6]Br2·3H2O

Rudnitskaya, O.V.; Komarovskikh, M.R.; Pekarskaya, M.G.; Pshenichnyy, D.S.; Akkurt, M.; Khalilov, A.N.; Bhattarai, A.; Mamedov, I.G.

doi:10.1107/S2056989024006832

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ISSN: 2056-9890

Volume 80| Part 8| August 2024| Pages 886-889

https://doi.org/10.1107/S2056989024006832

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Synthesis, molecular and crystal structure of [(NH₂)₂CSSC(NH₂)₂]₂[RuBr₆]Br₂·3H₂O

Olga V. Rudnitskaya,^a Milena R. Komarovskikh,^a Maria G. Pekarskaya,^a Daniil S. Pshenichnyy,^a Mehmet Akkurt,^b Ali N. Khalilov,^c,^d Ajaya Bhattarai ^e ^* and Ibrahim G. Mamedov ^d

^aRUDN University, 115419 Moscow, Russian Federation, ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, ^c"Composite Materials" Scientific Research Center, Azerbaijan State Economic University (UNEC), Murtuza Mukhtarov str. 194, Az 1065, Baku, Azerbaijan, ^dDepartment of Chemistry, Baku State University, Z. Khalilov str. 23, Az, 1148, Baku, Azerbaijan, and ^eDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: ajaya.bhattarai@mmamc.tu.edu.np

Edited by N. Alvarez Failache, Universidad de la Repüblica, Uruguay (Received 3 June 2024; accepted 12 July 2024; online 23 July 2024)

The title compound, bis[dithiobis(formamidinium)] hexabromidoruthenium dibromide trihydrate, [(NH₂)₂CSSC(NH₂)₂]₂[RuBr₆]Br₂·3H₂O, crystallizes in the orthorhombic system, space group Cmcm, Z = 4. The [RuBr₆]²⁻ anionic complex has an octahedral structure. The Ru—Br distances fall in the range 2.4779 (4)–2.4890 (4) Å. The S—S and C—S distances are 2.0282 (12) and 1.783 (2) Å, respectively. The H₂O molecules, Br⁻ ions, and NH₂ groups of the cation are linked by hydrogen bonds. The conformation of the cation is consolidated by intramolecular O—H⋯Br, O—H⋯O, N—H⋯Br and N—H⋯O hydrogen bonds. The [(NH₂)₂CSSC(NH₂)₂]²⁺ cations form a hydrogen-bonded system involving the Br ⁻ ions and the water molecules. Two Br ⁻ anions form four hydrogen bonds, each with the NH₂ groups of two cations, thus linking the cations into a ring. The rings are connected by water molecules, forming N—H⋯O—H⋯Br hydrogen bonds.

Keywords: crystal structure; ruthenium halido complexes; anions; cations; αα′-(dithiobisformamidinium) cation.

CCDC reference: 2370115

1. Chemical context

Oxidation of thiocarbamide in an acidic medium results in the αα′-(dithiobisformamidinium) cation {[(NH₂)₂CSSC(NH₂)₂]²⁺ or [S₂C₂(NH₂)₄]²⁺ in a simplified form; Preisler & Berger, 1947 }. There are only a few examples of compounds containing [S₂C₂(NH₂)₄]²⁺ cations described in the literature. For example, direct interaction of compounds with [S₂C₂(NH₂)₄]Cl₂ in concentrated hydrochloric acid produced [S₂C₂(NH₂)₄][MCl₄], M = Cu, Co, Zn, Hg (Golovnev et al., 2013 ), [S₂C₂(NH₂)₄]₂[Hg₂Cl₈] (Vasiliev et al., 2013 ) and [S₂C₂(NH₂)₄]₂[Os^IVCl₆]Cl₂·3H₂O (Rudnitskaya et al., 2019 ), while changing the reaction medium to concentrated hydrobromic acid resulted in the formation of [S₂C₂(NH₂)₄][HgBr₄] (Golovnev et al., 2013).

From the point of view of synthetic coordination chemistry, the reactions of rhenium and osmium complexes with thiocarbamide are of interest. These reactions led to compounds with an outer sphere dithiobisformamidinium cation. Thus, the interaction of ReO₄⁻ with thiocarbamide (tu) in hydrochloric acid allows the preparation of complexes [S₂C₂(NH₂)₄][ReCl₄(H₂O)O], [S₂C₂(NH₂)₄]₂[ReCl₅(H₂O)]Cl₃·2H₂O and [S₂C₂(NH₂)₄]₂[ReCl₅(tu)]Cl (Lis, 1979 , 1980 ; Lis & Starynowicz, 1985 ). In this case, oxidation of thiourea (hereinafter, tu) occurs by rhenium(VII). When K₂[ReCl₆] reacts with tu in dilute HCl, thiocarbamide oxidation occurs under the influence of atmospheric oxygen, giving [S₂C₂(NH₂)₄]₂[ReCl₆]Cl₂·3H₂O (Lis & Starynowicz, 1985). Similar complexes [S₂C₂(NH₂)₄]₂[OsX₆]X₂·3H₂O where X = Cl, Br were obtained by the reaction of H₂[OsX₆] and tu in concentrated HCl and HBr, respectively. In the aforementioned case, thiocarbamide was oxidized by osmium(IV) (Rudnitskaya et al., 2008 , 2019). The molecular and crystal structures of the rhenium and osmium complexes discussed above were established by X-ray diffraction. The interaction of K₄[Ru₂OCl₁₀] with α,α′-(dithiobisformamidinium) chloride forms the unique ruthenium(III) compound [Ru₂(tu)₃Cl₆]·2H₂O, containing three tu bridging molecules (Rudnitskaya et al., 2017a ). The structure of [Cl₃Ru(tu)₃RuCl₃] will be published elsewhere.

This study aimed to investigate the interaction between ruthenium compounds and αα′-bis(dithiobisformamidinium) bromide in hydrobromic acid solutions.

2. Structural commentary

The title compound (Fig. 1) is isostructural to the similar osmium complex (Rudnitskaya et al., 2008, 2019). In the α,α′-(dithiobisformamidinium) cation, the S—S bond is single and has a length of 2.0282 (12) Å, while in the osmium complex the length of this bond is 2.039 (2) Å. The cation adopts the most energetically favorable gauche conformation with a C—S—S—C torsion angle of 97.15 (11)°, which is slightly smaller than the angle in the osmium analogue (102.62°). The intrinsic symmetry of the cations is C2, and the thiocarbamide fragments retain a planar structure in both complexes. The intrinsic symmetry of the [RuBr₆]^2– ion is D2h. The coordination number of ruthenium is 6, and the anion takes the form of a distorted octahedron, d(Ru—Br) = 2.4779 (4)–2.4890 (4) Å for three Br atoms are different, but within standard errors (Table 1). The conformation of the cation is aslo consolidated by intramolecular N—H⋯S hydrogen bonds (Table 2, Fig. 1). In [(NH₂)₂CSSC(NH₂)₂]₂[OsBr₆]Br₂·3H₂O, the conformation of the cation is also stabilized by intramolecular N—H⋯S hydrogen bonds (Rudnitskaya et al., 2008). The geometric parameters of the title compound are normal and consistent with those of the related compounds described in the Database survey (Section 4).

Table 1
Selected bond lengths (Å)

Ru1—Br1	2.4779 (4)	Ru1—Br3	2.4866 (3)
Ru1—Br3ⁱ	2.4866 (3)	Ru1—Br2	2.4890 (4)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.80 (4)	2.02 (4)	2.814 (3)	167 (3)
O1—H1C⋯Br3	0.84 (3)	2.52 (3)	3.293 (3)	154 (4)
O1—H1D⋯O2	0.84 (3)	2.00 (4)	2.794 (4)	157 (5)
N1—H1B⋯Br4	0.77 (3)	2.60 (4)	3.327 (2)	157 (3)
N2—H2B⋯Br1ⁱⁱ	0.81 (3)	2.96 (4)	3.496 (2)	125 (3)
N2—H2A⋯Br2ⁱⁱⁱ	0.88 (4)	2.79 (4)	3.456 (2)	134 (3)
N2—H2B⋯Br4	0.81 (3)	2.87 (4)	3.592 (3)	149 (3)
O2—H2⋯Br4^iv	0.95 (5)	2.48 (5)	3.419 (2)	167 (4)
Symmetry codes: (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iii) ; (iv) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Figure 1
The molecular structure of [S₂C₂(NH₂)₄]₂[RuBr₆]Br₂·3H₂O, showing the atom labeling and displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (A) x, y, $[{3\over 2}]$ − z; (B) 1 − x, y, $[{3\over 2}]$ − z; (C) x, 1 − y, 1 − z.

3. Supramolecular features

The [(NH₂)₂CSSC(NH₂)₂]²⁺ cations and [RuBr₆]^2– complex anion form a system of hydrogen bonds with the Br⁻ ions and water molecules (Table 2, Figs. 1 and 2). Two cations are bound in a ring by two Br⁻ ions, each forming four hydrogen bonds with the NH₂ groups of the cations. A similar system of hydrogen bonds is present in the osmium complex.

Figure 2
View of the arrangement and interactions of the [(NH₂)₂CSSC(NH₂)₂]²⁺ cations, the RuBr₆^2– and Br⁻ anions, and water molecules in the unit cell.

For two O—H⋯Br hydrogen bonds [O1—H1C⋯Br3 and O2—H2⋯Br4^v, symmetry code: (v) x − $[{1\over 2}]$ , y + $[{1\over 2}]$ , z], the average distance of H⋯Br is 3.356 (3) Å and the average value of the O—H⋯Br angle is 161 (4)°. For four N—H⋯Br hydrogen bonds [N1—H1B⋯Br4, N2—H2B⋯Br1ⁱⁱⁱ, N2—H2A⋯Br2^iv, N2—H2B⋯Br4, symmetry codes: (iii) −x + 1, −y + 1, z − $[{1\over 2}]$ ; (iv) x, −y + 1, −z + 1], the average H⋯Br distance is 3.468 (3) Å and the average N—H⋯Br angle is 141 (3)°. These values show that hydrogen bonds are quite strong.

4. Database survey

A search of the Cambridge Crystallographic Database (updated 20 March 2023; Groom et al., 2016 ) using the [RuBr₆]^2– complex ion and the αα′-bis(dithiobisformamidinium) cation as the search fragments revealed five closely related compounds, viz. bis[α,α′-dithiobis(formamidinium)] hexabromidoosmium(IV) dibromide trihydrate (CSD refcode XAJVUB; Rudnitskaya et al., 2008), bis[disulfanediylbis(aminomethaniminium)] bis(chloride) hexachloridoosmium(IV) trihydrate (NIPBIA; Rudnitskaya et al., 2019), bis[disulfanediylbis(aminomethaniminium)] bis(bromide) hexabromidoosmium(IV) trihydrate (NIPBOG; Rudnitskaya et al., 2019), bis[(diaminomethylene)sulfonium] hexachloridoosmium (PATCIZ; Rudnitskaya et al., 2017b ) and bis[(diaminomethylene)sulfonium] hexabromidoosmium (PATCOF; Rudnitskaya et al., 2017b).

XAJVUB, NIPBIA and NIPBOG crystallize in the orthorhombic Cmcm space group with Z = 4, while PATCIZ and PATCOF crystallize in the triclinic P $[\overline{1}]$ space group with Z = 1. In XAJVUB, the [OsBr₆] ^2– anionic complex has an octahedral structure. The Os—Br distances fall in the range 2.483–2.490 Å. The α,α′-dithiobisformamidinium cation is a product of the oxidation of thiocarbamide. The S—S and C—S distances are 2.016 and 1.784 Å, respectively. The water molecules, Br⁻ ions, and NH₂ groups of the cation are linked by hydrogen bonds. In NIPBIA and NIPBOG, the osmium atoms in the [OsX₆] ²⁻ (X = Cl or Br) anions adopt slightly distorted octahedral coordination. The α,α′-dithiobisformamidinium cations are paired into rings by N—H⋯Cl⁻ hydrogen bonds. The rings are further connected into a 3D framework by hydrogen bonds involving the water molecules and S⋯Cl non-covalent interactions. In the crystal structures of PATCIZ and PATCOF, the (NH₂)₂CSH⁺ cations and [OsX₆]²⁻ anions are linked into two-tier layers in the (110) plane by the N—H⋯X(Cl, Br) and S—H⋯X(Cl, Br) hydrogen bonds and S⋯X(Cl, Br) non-covalent attractive contacts. It can be seen from the similar geometric parameter values given in Table 3 that the discussed compounds are comparable with each other.

Table 3
Selected values of bond distances (Å) and angles (°) in various salts and complexes

Compound	S—S	C—S	C—S—S	C—S—S—C	Reference
Title compound	2.0282 (12)	1.783 (2)	102.90 (9)	−95.15 (11)	This study
XAJVUB	2.024 (2)	1.778 (5)	103.2 (2)	96.3	(Rudnitskaya et al., 2008)
NIPBIA	2.036 (2)	1.789 (5)	102.43 (17)	−96.4 (4)	(Rudnitskaya et al., 2019)
NIPBOG	2.039 (2)	1.796 (5)	102.62 (15)	−97.9 (3)	(Rudnitskaya et al., 2019)
PATCIZ	–	1.739 (10)	–	–	(Rudnitskaya et al., 2017b)
PATCOF	–	1.751 (9)	–	–	(Rudnitskaya et al., 2017b)

5. Synthesis and crystallization

Synthesis of [(NH₂)₂CSSC(NH₂)₂]₂[RuBr₆]Br₂·3H₂O

To 0.10 g of K₄[Ru₂OCl₁₀], 10 mL of concentrated HBr (from Riedel de Haen) were added, and the reaction mixture was heated in a water bath until the K₄[Ru₂OCl₁₀] dissolved completely. Then a solution of 0.13 g of [S₂C₂(NH₂)₄]Br₂·2H₂O (molar ratio Ru:[S₂C₂(NH₂)₄]Br₂ = 1:1.5) was added, and the resulting solution was evaporated in a water bath to 2–3 ml. Dark, large orthorhombic crystals formed after the solution was cooled. The precipitate was filtered off, and washed with 3 ml of distilled water and 4 ml of ethanol. The mass of the obtained solid was 0.10 g (yield: 67%). Found Ru = 9.6%, for [S₂C₂(NH₂)₄]₂[RuBr₆]Br₂·3H₂O: calculated Ru = 9.67%. Sulfur and bromine were determined by microanalysis, and ruthenium was determined by reducing the sample to metallic ruthenium in a stream of H₂ at 1073 K. Errors between the found and measured values are normal depending on the technique used.

The compound is highly soluble in DMSO, giving blue solutions, while in dilute and concentrated HBr it dissolves over time (red and orange solutions, respectively) and is insoluble in alcohol and acetone.

EAS [λ_max, nm (ɛ, mol⁻¹ L cm⁻¹)]: in HBr (2 mol L⁻¹) – 400 (1800), 460 (1550), 560sh (720); in HBr (9 mol L⁻¹) – 375sh (2850), 390 (2830), 440sh (2050), 455 (2450), 465sh (2400), 520sh (800); in DMSO – 390sh (6700), 480sh (2000), 505sh (2800), 555 (3930), 619 (4060), 686 (3980), 710sh (3000), 755sh (1900).

FTIR (ν, cm⁻¹): 183, 230 ν (Ru—Br); 422 ρ(SCN₂), ρ(NH₂); 497 δ(CN₂); 577 b(SCN₂), ν(CS); 815 ν(CS), ν_s(CN), δ(CN₂); 1063 ρ(NH₂), ν_as(CN); 1119, 1385 ν_s(CN), ν(CS), ρ(NH₂); 1621, 1627, 1645 δ(NH₂), δ(OH₂), ν_as(CN); 3050 ν(NH), 3260, 3400 ν_as(NH), ν(OH).

The reaction with K₄[Ru₂OCl₁₀] was carried out similarly at a ratio of Ru:[S₂C₂(NH₂)₄]²⁺ = 1:2, and reactions with ruthenium trichlorides were carried out using ratios of reactants of 1:1.5 and 1:2.

As a result of all experiments, [S₂C₂(NH₂)₄]₂[RuBr₆]Br₂·3H₂O precipitates formed, but when the ratio of the initial components was 1:2, the precipitates contained an admixture of [S₂C₂(NH₂)₄]Br₂·2H₂O.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. All hydrogen atoms were derived from the Fourier synthesis map and refined isotopically with dependent isotropic thermal parameters with U_iso(H) = 1.2U_eq(N) and U_iso(H) = 1.5U_eq(O).

Table 4
Experimental details

Crystal data
Chemical formula	(C₂H₈N₄S₂)₂[RuBr₆]Br₂·3H₂O
M_r	1098.88
Crystal system, space group	Orthorhombic, Cmcm
Temperature (K)	150
a, b, c (Å)	11.6462 (3), 13.9943 (4), 16.9225 (5)
V (Å³)	2758.04 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	12.49
Crystal size (mm)	0.30 × 0.20 × 0.02

Data collection
Diffractometer	Bruker D8 Venture
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.043, 0.100
No. of measured, independent and observed [I > 2σ(I)] reflections	22642, 2269, 2057
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.057, 1.07
No. of reflections	2269
No. of parameters	93
No. of restraints	1
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.59
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2370115

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024006832/ny2005sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024006832/ny2005Isup2.hkl

checkCIF report

Computing details top

Bis[dithiobis(formamidinium)] hexabromidoruthenium dibromide trihydrate top

Crystal data top

(C₂H₈N₄S₂)₂[RuBr₆]Br₂·3H₂O	D_x = 2.646 Mg m⁻³
M_r = 1098.88	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Cmcm	Cell parameters from 1291 reflections
a = 11.6462 (3) Å	θ = 2.3–26.6°
b = 13.9943 (4) Å	µ = 12.49 mm⁻¹
c = 16.9225 (5) Å	T = 150 K
V = 2758.04 (13) Å³	Plate, black
Z = 4	0.30 × 0.20 × 0.02 mm
F(000) = 2056

Data collection top

Bruker D8 Venture diffractometer	2057 reflections with I > 2σ(I)
Radiation source: microsource	R_int = 0.043
φ and ω scans	θ_max = 30.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −16→16
T_min = 0.043, T_max = 0.100	k = −19→20
22642 measured reflections	l = −24→24
2269 independent reflections

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.023	Hydrogen site location: difference Fourier map
wR(F²) = 0.057	Only H-atom coordinates refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0237P)² + 6.898P] where P = (F_o² + 2F_c²)/3
2269 reflections	(Δ/σ)_max = 0.001
93 parameters	Δρ_max = 1.06 e Å⁻³
1 restraint	Δρ_min = −0.59 e Å⁻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
Ru1	0.500000	0.65423 (2)	0.750000	0.01754 (8)
Br1	0.500000	0.77930 (2)	0.85365 (2)	0.02178 (8)
Br2	0.500000	0.52583 (2)	0.64822 (2)	0.02559 (8)
Br3	0.28649 (3)	0.65551 (2)	0.750000	0.02565 (9)
Br4	0.500000	0.17169 (2)	0.58416 (2)	0.02717 (9)
S1	0.18284 (5)	0.47494 (4)	0.55623 (4)	0.02521 (13)
N1	0.2957 (2)	0.33273 (17)	0.61812 (15)	0.0280 (5)
H1A	0.264 (3)	0.353 (2)	0.657 (2)	0.034*
H1B	0.330 (3)	0.285 (2)	0.616 (2)	0.034*
N2	0.3321 (2)	0.35163 (17)	0.48633 (16)	0.0329 (5)
H2A	0.331 (3)	0.386 (3)	0.443 (2)	0.039*
H2B	0.380 (3)	0.310 (2)	0.489 (2)	0.039*
C1	0.2816 (2)	0.37771 (17)	0.55165 (16)	0.0241 (5)
O1	0.2061 (2)	0.4299 (2)	0.750000	0.0305 (6)
H1C	0.249 (4)	0.478 (3)	0.750000	0.046*
H1D	0.136 (3)	0.445 (4)	0.750000	0.046*
O2	0.000000	0.5321 (3)	0.750000	0.0360 (9)
H2	0.000000	0.579 (4)	0.709 (3)	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01735 (16)	0.01668 (16)	0.01860 (17)	0.000	0.000	0.000
Br1	0.02324 (15)	0.02066 (15)	0.02144 (16)	0.000	0.000	−0.00283 (11)
Br2	0.03078 (18)	0.02150 (16)	0.02447 (17)	0.000	0.000	−0.00468 (12)
Br3	0.01777 (15)	0.02213 (16)	0.0371 (2)	−0.00096 (11)	0.000	0.000
Br4	0.02496 (16)	0.02304 (16)	0.0335 (2)	0.000	0.000	0.00104 (13)
S1	0.0280 (3)	0.0238 (3)	0.0238 (3)	0.0043 (2)	0.0033 (2)	0.0016 (2)
N1	0.0287 (11)	0.0256 (11)	0.0298 (12)	0.0040 (8)	0.0033 (9)	0.0043 (9)
N2	0.0370 (13)	0.0272 (11)	0.0345 (13)	0.0063 (10)	0.0128 (11)	0.0034 (10)
C1	0.0228 (11)	0.0199 (10)	0.0295 (13)	−0.0019 (9)	0.0023 (9)	0.0015 (9)
O1	0.0329 (14)	0.0254 (13)	0.0333 (15)	0.0003 (11)	0.000	0.000
O2	0.042 (2)	0.032 (2)	0.035 (2)	0.000	0.000	0.000

Geometric parameters (Å, º) top

Ru1—Br1	2.4779 (4)	N1—H1A	0.80 (4)
Ru1—Br1ⁱ	2.4779 (4)	N1—H1B	0.77 (3)
Ru1—Br3ⁱⁱ	2.4866 (3)	N2—C1	1.305 (3)
Ru1—Br3	2.4866 (3)	N2—H2A	0.88 (4)
Ru1—Br2ⁱ	2.4890 (4)	N2—H2B	0.81 (3)
Ru1—Br2	2.4890 (4)	O1—H1C	0.84 (3)
S1—C1	1.783 (2)	O1—H1D	0.84 (3)
S1—S1ⁱⁱⁱ	2.0282 (12)	O2—H2	0.95 (5)
N1—C1	1.299 (3)

Br1—Ru1—Br1ⁱ	90.122 (19)	Br3—Ru1—Br2	90.298 (8)
Br1—Ru1—Br3ⁱⁱ	89.708 (8)	Br2ⁱ—Ru1—Br2	87.58 (2)
Br1ⁱ—Ru1—Br3ⁱⁱ	89.708 (8)	C1—S1—S1ⁱⁱⁱ	102.90 (9)
Br1—Ru1—Br3	89.708 (8)	C1—N1—H1A	119 (2)
Br1ⁱ—Ru1—Br3	89.708 (8)	C1—N1—H1B	117 (3)
Br3ⁱⁱ—Ru1—Br3	179.17 (2)	H1A—N1—H1B	124 (4)
Br1—Ru1—Br2ⁱ	91.151 (12)	C1—N2—H2A	123 (2)
Br1ⁱ—Ru1—Br2ⁱ	178.727 (16)	C1—N2—H2B	117 (3)
Br3ⁱⁱ—Ru1—Br2ⁱ	90.298 (8)	H2A—N2—H2B	117 (3)
Br3—Ru1—Br2ⁱ	90.298 (8)	N1—C1—N2	122.7 (2)
Br1—Ru1—Br2	178.729 (16)	N1—C1—S1	114.4 (2)
Br1ⁱ—Ru1—Br2	91.150 (12)	N2—C1—S1	122.8 (2)
Br3ⁱⁱ—Ru1—Br2	90.298 (8)	H1C—O1—H1D	112 (5)

S1ⁱⁱⁱ—S1—C1—N1	−179.53 (18)	S1ⁱⁱⁱ—S1—C1—N2	−2.0 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.80 (4)	2.02 (4)	2.814 (3)	167 (3)
O1—H1C···Br3	0.84 (3)	2.52 (3)	3.293 (3)	154 (4)
O1—H1D···O2	0.84 (3)	2.00 (4)	2.794 (4)	157 (5)
N1—H1B···Br4	0.77 (3)	2.60 (4)	3.327 (2)	157 (3)
N2—H2B···Br1^iv	0.81 (3)	2.96 (4)	3.496 (2)	125 (3)
N2—H2A···Br2ⁱⁱⁱ	0.88 (4)	2.79 (4)	3.456 (2)	134 (3)
N2—H2B···Br4	0.81 (3)	2.87 (4)	3.592 (3)	149 (3)
O2—H2···Br4^v	0.95 (5)	2.48 (5)	3.419 (2)	167 (4)

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

Selected values of bond distances (Å) and angles (°) in various salts and complexes top

Compound	S—S	C—S	C—S—S	C—S—S—C	Reference
Title compound	2.0282 (12)	1.783 (2)	102.90 (9)	-95.15 (11)	This study
XAJVUB	2.024 (2)	1.778 (5)	103.2 (2)	96.3	(Rudnitskaya et al., 2008)
NIPBIA	2.036 (2)	1.789 (5)	102.43 (17)	-96.4 (4)	(Rudnitskaya et al., 2019)
NIPBOG	2.039 (2)	1.796 (5)	102.62 (15)	-97.9 (3)	(Rudnitskaya et al., 2019)
PATCIZ	–	1.739 (10)	–	–	(Rudnitskaya et al., 2017b)
PATCOF	–	1.751 (9)	–	–	(Rudnitskaya et al., 2017b)

Acknowledgements

Authors' contributions are as follows. Conceptualization, OVR, MRK and MA; methodology, DSP and MGP; investigation, DSP and MRK; writing (original draft), MA, AB and ANK, writing (review and editing of the manuscript), IGM and ANK; visualization, MA, OVR, and IGM; funding acquisition, AB and OVR; resources, AB, and MA; supervision, MA and ANK.

Funding information

Funding for this research was provided by: Baku State University and the RUDN University Strategic Academic Leadership Program.

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