Synthesis, spectroscopic analysis and crystal structure of (N-{2-[(2-amino­eth­yl)amino]­eth­yl}-4′-methyl-[1,1′-biphenyl]-4-sulfonamidato)tri­carb­on­ylrhenium(I)

Kaluthanthiri, D.; Perera, T.; Fronczek, F.R.

doi:10.1107/S2056989024005656

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ISSN: 2056-9890

Volume 80| Part 7| July 2024| Pages 742-745

https://doi.org/10.1107/S2056989024005656

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Synthesis, spectroscopic analysis and crystal structure of (N-{2-[(2-aminoethyl)amino]ethyl}-4′-methyl-[1,1′-biphenyl]-4-sulfonamidato)tricarbonylrhenium(I)

Dinithi Kaluthanthiri,^a,^b Theshini Perera ^a ^* and Frank R. Fronczek ^c

^aDepartment of Chemistry, University of Sri Jayewardenepura, Sri Lanka, ^bDepartment of Pharmacy and Pharmaceutical Sciences, University of Sri Jayewardenepura, Sri Lanka, and ^cDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: theshi@sjp.ac.lk

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 20 May 2024; accepted 12 June 2024; online 18 June 2024)

The title compound, [Re(C₁₇H₂₂N₃O₂S)(CO)₃] is a net neutral fac-Re(I)(CO)₃ complex of the 4-methylbiphenyl sulfonamide derivatized diethylenetriamine ligand. The NNN-donor monoanionic ligand coordinates with the Re core in tridentate fashion, establishing an inner coordination sphere resulting in a net neutral complex. The complex possesses pseudo-octahedral geometry where one face of the octahedron is occupied by three carbonyl ligands and the other faces are occupied by one sp² nitrogen atom of the sulfonamide group and two sp³ nitrogen atoms of the dien backbone. The Re—Nsp² bond distance, 2.173 (4) Å, is shorter than the Re—Nsp³ bond distances, 2.217 (5) and 2.228 (6) Å, and is similar to the range reported for typical Re—Nsp² bond lengths (2.14 to 2.18 Å).

Keywords: rhenium complexes; diethylenetriamine; biphenyl; sulfonamide; crystal structure.

CCDC reference: 2362252

1. Chemical context

Organometallic compounds have garnered significant interest due to their notable properties in cell imaging and anticancer applications. Particularly, Re complexes are noted for their kinetic inertness and large Stokes shift (Stephenson et al., 2004 ; Guo et al., 1997 ). Research has shown that tridentate ligand systems are more robust and possess better pharmacokinetics than those bearing bidentate ligands, leading to reduced side effects (Schibli et al., 2000 ). Our focus involves a sulfonamide ligand, which has a diethylenetriamine (dien) backbone and 4-methylbiphenyl (4-Mebip) as the pendant group. The N(SO₂)(4-Mebip)dienH ligand, along with its bidentate Pt^II complex have both been reported to exhibit remarkable anticancer properties against non-small lung cancer (Kaluthanthiri et al., 2023 ). Motivated by its potential as a cytotoxic drug lead, here we have focused on rhenium, in its lowest oxidation state because it exhibits less reactivity toward species in the cellular environment (Schibli & Schubiger, 2002 ). Given rhenium's soft metal center characteristics, a preference for soft donors, particularly nitrogen, is observed and tridentate metal complexes featuring nitrogen donors are commonly employed (Christoforou et al., 2007 ; Kaushalya et al., 2022 ; Darshani et al., 2020 ). In this study, the Re(CO)₃[N(SO₂)(4-Mebip)dien] complex was successfully synthesized and its molecular structure was confirmed by single-crystal X-ray diffraction analysis and ¹H NMR spectroscopy. Furthermore, comprehensive characterization was conducted using FTIR, UV–vis, and fluorescence spectroscopic techniques.

2. Structural commentary

The Re(CO)₃[N(SO₂)(4-Mebip)dien] complex is shown in Fig. 1. The Re—C distances in Re—CO bonds are in the range of 1.895 (8)–1.914 (6) Å, which is consistent with related data reported (Christoforou et al., 2007; Darshani et al., 2020). The longest Re—C distance is trans to the sp² nitrogen atom N3. The C11—C14 bond distance between the two phenyl rings of the anionic ligand in the biphenyl group in Re(CO)₃[N(SO₂)(4-Mebip)dien] is 1.484 (8) Å. The biphenyl moiety is twisted out of planarity, the dihedral angle between the two planes being 36.5 (3)°. The average Re—N bond length in our Re complex is 2.206 Å, which is consistent with the distances found in related Re(CO)₃ complexes containing a dien backbone (Christoforou et al., 2007). The Re—N3 bond (sp² nitrogen) distance [2.173 (4) Å] in the complex is significantly shorter than the other Re—N (sp³ N) bonds [2.217 (5) and 2.228 (6) Å], which explains the anionic nature of the N3 amino nitrogen. The S—N bond length for the deprotonated sulfonamido group is 1.579 (4) Å for the complex and is within the accepted range for S—N bonds available in deprotonated sulfonamides coordinated to Re, Cu and Zn metals (Christoforou et al., 2007; Goodwin et al., 2004 ; Congreve et al., 2003 ).

Figure 1
The asymmetric unit with 50% probability displacement ellipsoids and atom labels. H atoms are represented by spheres of arbitrary radius.

3. Supramolecular features

The unit cell is shown in Fig. 2. The intermolecular interactions are predominantly N—H⋯O hydrogen bonds as listed in Table 1 and shown in Fig. 3. The N1⋯O2 separations in these hydrogen bonds are in the range 2.941 (5)–3.053 (7) Å. The graph sets (Etter et al., 1990 ) are centrosymmetric R₂²(10) rings and C₁¹(6) chains, forming double-stranded chains in the [001] direction. One of the NH₂ H atoms is not involved in the hydrogen bonding. Interleaved between the double-stranded hydrogen-bonded chains are hydrophobic layers of stacked biphenyl moieties, as can be seen in Fig. 2. The closest distance [4.079 (4) Å] between centers of gravity (Cg) of these rings is between the phenyl ring C14–C19 carrying the methyl group and its centrosymmetric equivalent at 1 − x, 2 − y, 2 − z. There are no other Cg⋯Cg distances closer than 5.5 Å. The phenyl ring C8–C13 has no close intermolecular contacts to other phenyl rings, but has a close contact to carbonyl C5—O1 at x, $[{3\over 2}]$ − y, − $[{1\over 2}]$ + z, with Cg⋯O1 3.758 (7) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯O3ⁱ	0.89	2.27	3.053 (7)	146
N1—H12N⋯O2ⁱⁱ	0.89	2.59	3.028 (7)	111
N2—H2N⋯O4ⁱⁱⁱ	0.98	1.98	2.941 (5)	167
Symmetry codes: (i) ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
View of the unit cell. H atoms are not shown.

Figure 3
View of the hydrogen bonding, shown as blue dashed lines, and chain formation along the [001] direction. H atoms on C are omitted and the unit cell axes are shown.

4. Database survey

A search of the Cambridge Structural Database (CSD, version 5.45, update of March 2024; Groom et al., 2016 ) for the diethylenetriamine SO₂Re(CO)₃ fragment yielded four hits, LIMDIV and LIMDOB (Christoforou et al., 2007); SUNFUF and SUNGAM (Darshani et al., 2020). These structures have been mentioned above. A similar search for [N-(2-aminoethyl)ethane-1,2-diamine]Re(CO)₃ salts yielded seven hits: BUPXAO, BUPXES, BUPYIX, and BUPYOD (Abhayawardhana et al., 2020 ), IWENAZ (Mundwiler et al., 2004 ), TIYVIH and TIYVON (Christoforou et al., 2007). In these structures, the Re—N distances are in the range 2.203 (7)–2.244 (3) Å, with a mean value 2.219 Å for 21 individual measurements. The Re—C distances are in the range 1.878 (12)–1.956 (15) Å with a mean value 1.917 Å. There is no indication that the Re—N or Re—C distances to the central ligand atoms differ from those to the terminal atoms.

5. Synthesis, crystallization and spectroscopic data

The ligand N(SO₂)(4-Mebip)dienH was synthesized by following a reported procedure (Fig. 4; Kaluthanthiri et al., 2023). A solution of the ligand N(SO₂)(4-Mebip)dienH (0.0272 g, 0.0816 mmol) in 2 ml of methanol was added to a solution of [Re(CO)₃(H₂O)₃]Br (0.033 g, 0.0816 mmol) in 3 ml of water. The solution was then adjusted to pH 7–8 with aqueous NaOH and refluxed for 16 h (Fig. 4). The complex formed was collected by filtration as a white powder (0.025 g, 51% yield). Crystals suitable for X-ray crystallography were grown by slow evaporation of an acetonitrile/ methanol solution. UV–vis (MeOH) [λ_max (nm)]: 203, 266; FT–IR (ATR) (cm⁻¹): 969 ([(S—N)], 1342, 1128 [ν(S=O)], 2008, 1865 [ν(CO)]. ¹H NMR (400 MHz, DMSO-d₆) δ(ppm): 7.81 (m, 2H, Ha/a′), 7.74 (m, 2H, Hb/b′), 7.62 (m, 2H, Hc/c′) 7.29 (m, 2H, Hd/d′), 6.69 (b, 1H, N2H), 5.15 (m, 1H, endo N1H), 3.47 (m, 1H, exo N1H), 3.34–3.38 (m, 1H, CH), 2.64–2.90 (m, 7H, CH₂), 2.35 (s, 3H, CH₃). Although the ligand shows excellent fluorescence properties even at low concentrations, its Re complex offers quenched fluorescence properties attributed to the direct binding of sulfonamide nitrogen to Re center in the complex (Fig. 5). Furthermore, a slight blue shift (about 9 nm) was observed in the complex.

Figure 4
Synthetic route for preparation of N(SO₂)(4-Mebip)dienH and Re(CO)₃[N(SO₂)(4-Mebip)dien].

Figure 5
Fluorescence emission spectra of N(SO₂)(4-Mebip)dienH and Re(CO)₃[N(SO₂)(4-Mebip)dien] in methanol at 298 K.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were located in difference maps and treated as riding in geometrically idealized positions with C—H distances of 0.94 Å and with U_iso(H) = 1.2U_eq for the attached C atom (0.97 Å and 1.5U_eq for the methyl group). The H atoms on nitrogen had N—H distances of 0.89 Å for NH₂ and 0.98 Å for NH, and U_iso values were assigned as 1.2U_eq for the N atom.

Table 2
Experimental details

Crystal data
Chemical formula	[Re(C₁₇H₂₂N₃O₂S)(CO)₃]
M_r	602.66
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	18.5651 (9), 7.6604 (4), 15.4897 (11)
β (°)	95.472 (2)
V (Å³)	2192.8 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.67
Crystal size (mm)	0.22 × 0.13 × 0.05

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.572, 0.765
No. of measured, independent and observed [I > 2σ(I)] reflections	119413, 4849, 3513
R_int	0.102
(sin θ/λ)_max (Å⁻¹)	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.071, 1.08
No. of reflections	4849
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.00, −1.80
Computer programs: APEX3 and SAINT (Bruker, 2016 ), SHELXT2018/2 (Sheldrick, 2015 a), SHELXL2018/1 (Sheldrick, 2015b), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2362252

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989024005656/vm2303sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024005656/vm2303Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024005656/vm2303Isup3.cdx

checkCIF report

Computing details top

(N-{2-[(2-Aminoethyl)amino]ethyl}-4'-methyl-[1,1'-biphenyl]-4-sulfonamidato)tricarbonylrhenium(I) top

Crystal data top

[Re(C₁₇H₂₂N₃O₂S)(CO)₃]	F(000) = 1176
M_r = 602.66	D_x = 1.825 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.5651 (9) Å	Cell parameters from 2346 reflections
b = 7.6604 (4) Å	θ = 2.6–24.1°
c = 15.4897 (11) Å	µ = 5.67 mm⁻¹
β = 95.472 (2)°	T = 296 K
V = 2192.8 (2) Å³	Needle, colorless
Z = 4	0.22 × 0.13 × 0.05 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4849 independent reflections
Radiation source: fine-focus sealed tube	3513 reflections with I > 2σ(I)
TRIUMPH curved graphite monochromator	R_int = 0.102
φ and ω scans	θ_max = 27.2°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −23→23
T_min = 0.572, T_max = 0.765	k = −9→9
119413 measured reflections	l = −19→19

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0179P)² + 6.5423P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.071	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 2.00 e Å⁻³
4849 reflections	Δρ_min = −1.80 e Å⁻³
273 parameters	Extinction correction: SHELXL2017/1 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00017 (5)

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
Re1	0.86146 (2)	0.45261 (3)	0.61070 (2)	0.04344 (9)
S1	0.82122 (8)	0.3572 (2)	0.81148 (8)	0.0456 (4)
O1	0.7335 (3)	0.7018 (7)	0.5732 (4)	0.0875 (16)
O2	0.9354 (3)	0.7562 (8)	0.7131 (3)	0.104 (2)
O3	0.9230 (3)	0.6052 (8)	0.4508 (3)	0.0879 (17)
O4	0.8016 (2)	0.2083 (5)	0.8619 (2)	0.0563 (11)
O5	0.8906 (2)	0.4354 (6)	0.8338 (2)	0.0568 (11)
N1	0.9482 (3)	0.2530 (9)	0.6360 (3)	0.0769 (19)
H11N	0.991541	0.302049	0.634639	0.092*
H12N	0.945892	0.205082	0.688023	0.092*
N2	0.8135 (3)	0.2133 (6)	0.5486 (3)	0.0487 (12)
H2N	0.801808	0.237533	0.486680	0.058*
N3	0.8132 (2)	0.3099 (6)	0.7118 (2)	0.0440 (12)
C1	0.9364 (5)	0.1159 (12)	0.5660 (6)	0.099 (3)
H1C	0.949062	0.163356	0.511455	0.119*
H1D	0.967551	0.016551	0.580794	0.119*
C2	0.8629 (5)	0.0603 (10)	0.5568 (4)	0.080 (2)
H2A	0.852992	−0.008484	0.606844	0.096*
H2B	0.854413	−0.012739	0.505655	0.096*
C3	0.7445 (4)	0.1752 (9)	0.5872 (4)	0.0598 (18)
H3A	0.727485	0.059835	0.569374	0.072*
H3B	0.707984	0.259311	0.565914	0.072*
C4	0.7553 (4)	0.1838 (10)	0.6838 (4)	0.0655 (19)
H4A	0.710554	0.219162	0.706318	0.079*
H4B	0.768274	0.069138	0.706919	0.079*
C5	0.7818 (4)	0.6059 (8)	0.5873 (4)	0.0525 (16)
C6	0.9077 (4)	0.6386 (11)	0.6748 (4)	0.069 (2)
C7	0.9009 (3)	0.5469 (10)	0.5110 (4)	0.0607 (17)
C8	0.7558 (3)	0.5190 (8)	0.8291 (3)	0.0457 (14)
C9	0.6854 (3)	0.4687 (8)	0.8401 (4)	0.0550 (16)
H9	0.672952	0.351064	0.838917	0.066*
C10	0.6339 (3)	0.5938 (8)	0.8529 (4)	0.0561 (17)
H10	0.586941	0.558250	0.860192	0.067*
C11	0.6498 (3)	0.7698 (8)	0.8553 (3)	0.0492 (15)
C12	0.7211 (3)	0.8167 (8)	0.8449 (4)	0.0534 (16)
H12	0.733858	0.934122	0.846868	0.064*
C13	0.7730 (3)	0.6936 (8)	0.8319 (4)	0.0506 (15)
H13	0.820003	0.728879	0.824931	0.061*
C14	0.5948 (3)	0.9040 (8)	0.8704 (4)	0.0517 (16)
C15	0.5233 (4)	0.8895 (10)	0.8371 (4)	0.070 (2)
H15	0.508519	0.791583	0.804678	0.084*
C16	0.4733 (4)	1.0176 (11)	0.8511 (5)	0.075 (2)
H16	0.425596	1.003962	0.827930	0.090*
C17	0.4927 (4)	1.1647 (10)	0.8984 (5)	0.0662 (19)
C18	0.5630 (4)	1.1776 (9)	0.9336 (5)	0.0654 (18)
H18	0.577106	1.273921	0.967606	0.079*
C19	0.6130 (4)	1.0513 (9)	0.9197 (4)	0.0613 (16)
H19	0.660456	1.064908	0.944103	0.074*
C20	0.4383 (4)	1.3088 (11)	0.9120 (5)	0.092 (3)
H20A	0.461891	1.420204	0.911398	0.138*
H20B	0.419068	1.292329	0.966780	0.138*
H20C	0.399557	1.304649	0.866244	0.138*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.04118 (13)	0.06022 (16)	0.02905 (11)	−0.00246 (13)	0.00405 (8)	0.00870 (12)
S1	0.0592 (9)	0.0527 (9)	0.0250 (6)	−0.0062 (8)	0.0056 (6)	0.0006 (6)
O1	0.070 (3)	0.073 (4)	0.118 (4)	0.023 (3)	0.002 (3)	−0.001 (3)
O2	0.113 (5)	0.112 (5)	0.079 (4)	−0.062 (4)	−0.029 (3)	0.013 (3)
O3	0.071 (3)	0.134 (5)	0.062 (3)	−0.002 (3)	0.023 (2)	0.050 (3)
O4	0.090 (3)	0.052 (3)	0.0283 (19)	−0.006 (2)	0.012 (2)	0.0072 (18)
O5	0.056 (2)	0.074 (3)	0.039 (2)	−0.009 (2)	−0.0056 (18)	−0.002 (2)
N1	0.044 (3)	0.138 (6)	0.049 (3)	0.022 (3)	0.008 (3)	0.029 (4)
N2	0.071 (3)	0.047 (3)	0.028 (2)	0.012 (3)	0.006 (2)	0.004 (2)
N3	0.055 (3)	0.055 (3)	0.023 (2)	−0.009 (2)	0.0078 (19)	−0.002 (2)
C1	0.085 (6)	0.093 (7)	0.126 (8)	0.017 (5)	0.041 (6)	0.006 (6)
C2	0.112 (7)	0.076 (5)	0.052 (4)	0.042 (5)	0.008 (4)	−0.002 (4)
C3	0.080 (5)	0.056 (4)	0.044 (3)	−0.025 (4)	0.010 (3)	−0.003 (3)
C4	0.070 (4)	0.087 (5)	0.041 (3)	−0.027 (4)	0.016 (3)	−0.015 (3)
C5	0.059 (4)	0.049 (4)	0.051 (4)	−0.009 (3)	0.013 (3)	−0.004 (3)
C6	0.056 (4)	0.100 (6)	0.050 (4)	−0.017 (4)	−0.004 (3)	0.027 (4)
C7	0.053 (4)	0.084 (5)	0.045 (3)	0.005 (4)	0.006 (3)	0.016 (4)
C8	0.057 (4)	0.050 (4)	0.031 (3)	−0.012 (3)	0.010 (2)	−0.005 (2)
C9	0.070 (4)	0.043 (3)	0.053 (3)	−0.019 (4)	0.016 (3)	−0.011 (3)
C10	0.050 (4)	0.055 (4)	0.065 (4)	−0.028 (3)	0.014 (3)	−0.015 (3)
C11	0.060 (4)	0.052 (4)	0.036 (3)	−0.007 (3)	0.008 (3)	−0.001 (3)
C12	0.064 (4)	0.044 (4)	0.053 (4)	−0.012 (3)	0.011 (3)	0.001 (3)
C13	0.053 (4)	0.054 (4)	0.047 (3)	−0.015 (3)	0.012 (3)	−0.001 (3)
C14	0.053 (4)	0.062 (4)	0.040 (3)	−0.006 (3)	0.008 (3)	0.009 (3)
C15	0.065 (5)	0.087 (6)	0.057 (4)	−0.003 (4)	0.001 (3)	−0.011 (4)
C16	0.053 (4)	0.109 (7)	0.063 (4)	0.001 (4)	0.002 (3)	0.005 (4)
C17	0.069 (5)	0.069 (5)	0.065 (4)	0.011 (4)	0.025 (4)	0.016 (4)
C18	0.068 (5)	0.046 (4)	0.083 (5)	0.002 (4)	0.013 (4)	−0.002 (4)
C19	0.056 (4)	0.055 (4)	0.072 (4)	−0.001 (4)	0.002 (3)	−0.003 (4)
C20	0.075 (5)	0.100 (7)	0.106 (6)	0.019 (5)	0.030 (5)	0.012 (5)

Geometric parameters (Å, º) top

Re1—C6	1.895 (8)	C4—H4A	0.9700
Re1—C5	1.896 (7)	C4—H4B	0.9700
Re1—C7	1.914 (6)	C8—C13	1.375 (8)
Re1—N3	2.173 (4)	C8—C9	1.389 (8)
Re1—N2	2.217 (5)	C9—C10	1.381 (9)
Re1—N1	2.228 (6)	C9—H9	0.9300
S1—O5	1.433 (4)	C10—C11	1.381 (8)
S1—O4	1.448 (4)	C10—H10	0.9300
S1—N3	1.579 (4)	C11—C12	1.394 (8)
S1—C8	1.775 (6)	C11—C14	1.484 (8)
O1—C5	1.163 (7)	C12—C13	1.376 (8)
O2—C6	1.170 (9)	C12—H12	0.9300
O3—C7	1.143 (7)	C13—H13	0.9300
N1—C1	1.510 (10)	C14—C15	1.381 (9)
N1—H11N	0.8900	C14—C19	1.387 (9)
N1—H12N	0.8900	C15—C16	1.381 (10)
N2—C2	1.486 (8)	C15—H15	0.9300
N2—C3	1.493 (7)	C16—C17	1.372 (10)
N2—H2N	0.9800	C16—H16	0.9300
N3—C4	1.479 (7)	C17—C18	1.370 (9)
C1—C2	1.423 (10)	C17—C20	1.524 (9)
C1—H1C	0.9700	C18—C19	1.372 (9)
C1—H1D	0.9700	C18—H18	0.9300
C2—H2A	0.9700	C19—H19	0.9300
C2—H2B	0.9700	C20—H20A	0.9600
C3—C4	1.493 (8)	C20—H20B	0.9600
C3—H3A	0.9700	C20—H20C	0.9600
C3—H3B	0.9700

C6—Re1—C5	86.6 (3)	H3A—C3—H3B	108.1
C6—Re1—C7	87.1 (3)	N3—C4—C3	110.3 (5)
C5—Re1—C7	87.9 (3)	N3—C4—H4A	109.6
C6—Re1—N3	101.4 (2)	C3—C4—H4A	109.6
C5—Re1—N3	94.7 (2)	N3—C4—H4B	109.6
C7—Re1—N3	171.2 (2)	C3—C4—H4B	109.6
C6—Re1—N2	172.9 (2)	H4A—C4—H4B	108.1
C5—Re1—N2	99.0 (2)	O1—C5—Re1	179.1 (6)
C7—Re1—N2	97.5 (2)	O2—C6—Re1	178.4 (7)
N3—Re1—N2	73.78 (16)	O3—C7—Re1	178.4 (6)
C6—Re1—N1	98.1 (3)	C13—C8—C9	119.0 (6)
C5—Re1—N1	174.9 (3)	C13—C8—S1	121.6 (5)
C7—Re1—N1	94.3 (2)	C9—C8—S1	119.4 (5)
N3—Re1—N1	82.45 (18)	C10—C9—C8	119.9 (6)
N2—Re1—N1	76.3 (2)	C10—C9—H9	120.1
O5—S1—O4	117.7 (3)	C8—C9—H9	120.1
O5—S1—N3	109.4 (2)	C11—C10—C9	122.1 (6)
O4—S1—N3	110.0 (2)	C11—C10—H10	118.9
O5—S1—C8	106.5 (3)	C9—C10—H10	118.9
O4—S1—C8	104.8 (3)	C10—C11—C12	116.9 (6)
N3—S1—C8	108.0 (3)	C10—C11—C14	122.1 (6)
C1—N1—Re1	107.3 (4)	C12—C11—C14	121.0 (6)
C1—N1—H11N	110.2	C13—C12—C11	121.7 (6)
Re1—N1—H11N	110.2	C13—C12—H12	119.2
C1—N1—H12N	110.2	C11—C12—H12	119.2
Re1—N1—H12N	110.2	C8—C13—C12	120.5 (6)
H11N—N1—H12N	108.5	C8—C13—H13	119.8
C2—N2—C3	111.0 (5)	C12—C13—H13	119.8
C2—N2—Re1	113.3 (4)	C15—C14—C19	116.5 (6)
C3—N2—Re1	108.2 (3)	C15—C14—C11	122.5 (6)
C2—N2—H2N	108.1	C19—C14—C11	120.9 (6)
C3—N2—H2N	108.1	C14—C15—C16	121.4 (7)
Re1—N2—H2N	108.1	C14—C15—H15	119.3
C4—N3—S1	115.8 (3)	C16—C15—H15	119.3
C4—N3—Re1	117.1 (3)	C17—C16—C15	121.4 (7)
S1—N3—Re1	125.6 (3)	C17—C16—H16	119.3
C2—C1—N1	110.7 (6)	C15—C16—H16	119.3
C2—C1—H1C	109.5	C18—C17—C16	117.5 (7)
N1—C1—H1C	109.5	C18—C17—C20	120.8 (7)
C2—C1—H1D	109.5	C16—C17—C20	121.7 (7)
N1—C1—H1D	109.5	C17—C18—C19	121.4 (7)
H1C—C1—H1D	108.1	C17—C18—H18	119.3
C1—C2—N2	110.5 (7)	C19—C18—H18	119.3
C1—C2—H2A	109.5	C18—C19—C14	121.7 (6)
N2—C2—H2A	109.5	C18—C19—H19	119.1
C1—C2—H2B	109.5	C14—C19—H19	119.1
N2—C2—H2B	109.5	C17—C20—H20A	109.5
H2A—C2—H2B	108.1	C17—C20—H20B	109.5
N2—C3—C4	110.8 (5)	H20A—C20—H20B	109.5
N2—C3—H3A	109.5	C17—C20—H20C	109.5
C4—C3—H3A	109.5	H20A—C20—H20C	109.5
N2—C3—H3B	109.5	H20B—C20—H20C	109.5
C4—C3—H3B	109.5

O5—S1—N3—C4	162.7 (5)	C8—C9—C10—C11	0.0 (9)
O4—S1—N3—C4	32.0 (5)	C9—C10—C11—C12	−0.6 (9)
C8—S1—N3—C4	−81.8 (5)	C9—C10—C11—C14	−179.1 (6)
O5—S1—N3—Re1	−31.7 (4)	C10—C11—C12—C13	0.7 (9)
O4—S1—N3—Re1	−162.5 (3)	C14—C11—C12—C13	179.3 (5)
C8—S1—N3—Re1	83.7 (4)	C9—C8—C13—C12	−0.4 (8)
Re1—N1—C1—C2	−48.9 (8)	S1—C8—C13—C12	179.4 (4)
N1—C1—C2—N2	49.9 (9)	C11—C12—C13—C8	−0.3 (9)
C3—N2—C2—C1	−148.2 (6)	C10—C11—C14—C15	−37.0 (9)
Re1—N2—C2—C1	−26.3 (7)	C12—C11—C14—C15	144.5 (6)
C2—N2—C3—C4	76.7 (7)	C10—C11—C14—C19	142.6 (6)
Re1—N2—C3—C4	−48.2 (6)	C12—C11—C14—C19	−35.9 (8)
S1—N3—C4—C3	169.7 (5)	C19—C14—C15—C16	1.4 (10)
Re1—N3—C4—C3	2.9 (7)	C11—C14—C15—C16	−179.1 (6)
N2—C3—C4—N3	29.9 (8)	C14—C15—C16—C17	0.1 (11)
O5—S1—C8—C13	20.8 (5)	C15—C16—C17—C18	−1.9 (10)
O4—S1—C8—C13	146.3 (5)	C15—C16—C17—C20	178.3 (7)
N3—S1—C8—C13	−96.5 (5)	C16—C17—C18—C19	2.2 (10)
O5—S1—C8—C9	−159.4 (4)	C20—C17—C18—C19	−178.0 (6)
O4—S1—C8—C9	−33.9 (5)	C17—C18—C19—C14	−0.7 (11)
N3—S1—C8—C9	83.3 (5)	C15—C14—C19—C18	−1.1 (10)
C13—C8—C9—C10	0.5 (9)	C11—C14—C19—C18	179.3 (6)
S1—C8—C9—C10	−179.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O3ⁱ	0.89	2.27	3.053 (7)	146
N1—H12N···O2ⁱⁱ	0.89	2.59	3.028 (7)	111
N2—H2N···O4ⁱⁱⁱ	0.98	1.98	2.941 (5)	167

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

Acknowledgements

Instrumentation was supported by the Instrument Center and the Material Center of the University of Sri Jayewardenepura.

Funding information

This research was funded by grant No. ASP/01/RE/SCI/2022/25 of the University of Sri Jayewardenepura. The upgrade of the diffractometer was made possible by grant No. LEQSF (2011–12)-ENH-TR-01, administered by the Louisiana Board of Regents.

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