Please read abstract in the article.The National Research Foundation of South Africa, Tshwane University of Technology and the University of Pretoria.https://www.degruyter.com/view/j/ncrsChemistr

Makhakhayi, Luleka

Malan, F.P. (Frederick)

Manicum, Amanda-Lee Ezra

Nkambule, Comfort M.

Tembu, Vuyelwa J.

UPSpace at the University of Pretoria

Luleka Makhakhayi*, Frederick P. Malan, Vuyelwa J. Tembu, Comfort M. Nkambule andAmanda-Lee E. ManicumThe crystal structure of fac-tricarbonyl(N-benzoyl-N,N-cyclohexylmethylcarbamimidothioato-κ2S,O)-(pyridine-κN)rhenium(I), C23H24N3O4ReShttps://doi.org/10.1515/ncrs-2023-0157Received April 1, 2023; accepted April 26, 2023;published online May 11, 2023AbstractC23H24N3O4ReS, orthorhombic, Pbca (no. 61), a = 15.1264(4) Å,b = 15.1167(5) Å, c = 20.1500 Å, V = 4607.5(2) Å3, Z = 8,T = 150(2) K, Rgt(F ) = 0.0416, wRref (F 2) = 0.0691.CCDC no.: 2259028The molecular structure is shown in the figure. Table 1contains crystallographic data and Table 2 contains the list ofthe atoms including atomic coordinates and displacementparameters.1 Source of materialsThe title complex was synthesized using the starting pre-cursor, fac-[NEt4]2 [Re(CO)3Br3], as explained by Albert et al.[6], Manicum et al. [7, 8]. fac-[NEt4]2 [Re (CO)3Br3], (201.1 mg,0.336 mmol) was dissolved in 5 mL of acidic water (pH = 2.2)and stirred at room temperature for 10min. AgNO3 (134.4 mg,0.7912 mmol) was added to the solution and stirred for 24 hat room temperature. The precipitate, AgBr, was separatedand weighed. N-(cyclohexyl(methyl)carbamothioyl) benza-mide (N–CyHMCB) bidentate ligand (72.11 mg, 0.336mmol)was added to the filtrate and the reactionmixture was stirredat room temperature for 24 h. The light-yellow precipitate(fac-[Re(N–CyHMCB)(CO)3(OH2)]) was filtered off and dried.fac-[Re(N–CyHMCB)(CO)3(OH2)], (74.5 mg, 0.132mmol) wasdissolved in methanol (5mL), and pyridine (0.07mL)was added. The solution was first stirred for 24 h at roomtemperature. The light-yellow solid (product) was obtained byevaporation of the solvent and the precipitate was recrystal-lized from ethylacetate:hexane (8:2). Yield = 71.52 mg, 86%, IR(KBr, cm−1): vCO 2103, 2007, 1879.2 Experimental detailsAll the hydrogen atoms were positioned geometrically andrefined using a riding model with fixed C–HAromatic = 0.97 Å;C–Hmethyl = 0.96 Å. The H atoms isotropic displacementTable : Data collection and handling.Crystal: Yellow blockSize: . × . × .mmWavelength: Mo Kα radiation (. Å)μ: .mm−Diffractometer, scan mode: XtaLAB Synergy R, ωθmax, completeness: .°, >%N(hkl)measured, N(hkl )unique, Rint: ,, , .Criterion for Iobs, N(hkl)gt: Iobs >  σ(Iobs), N(param)refined: Programs: CrysAlispRO [], Olex [], WinGX [],SHELX [, ]*Corresponding author: Luleka Makhakhayi, Department of Chemistry,Tshwane University of Technology, Pretoria 0001, South Africa,E-mail: lulumak1990@gmail.com. https://orcid.org/0009-0007-4737-1051Frederick P. Malan, Department of Chemistry, University of Pretoria,Pretoria 0001, South Africa. https://orcid.org/0000-0003-2446-2165Vuyelwa J. Tembu, Comfort M. Nkambule and Amanda-Lee E.Manicum, Department of Chemistry, Tshwane University of Technology,Pretoria 0001, South Africa. https://orcid.org/0000-0002-7421-6467(V.J. Tembu). https://orcid.org/0000-0003-4064-1307 (A.E. Manicum)Z. Kristallogr. - N. Cryst. Struct. 2023; 238(4): 697–699Open Access. © 2023 the author(s), published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0 International License.parameters were fixed; Uiso(H) = 1.2Ueq (C) for aromatic andUiso(H) = 1.5Ueq (C) for methyl, allowing them to ride on theparent atom. The graphics were obtained by using the MER-CURY program with 50 % probability ellipsoids. All thehydrogen in the structure was omitted for clarity.3 CommentOrganometallic rhenium(I) compounds have shown greatpromise for the development of new anticancer agentsin recent years [8, 9]. A variety of tricarbonyl complexescontaining mono- and bidentate ligands with nitrogen,oxygen, selenium, and phosphorus donors were discoveredto have significant cytotoxic effects on various cancer celllines [9–12]. However, the tricarbonyl precursor is particu-larly appealing not only for its potential use in biologicalapplications but also for its flexibility of M(CO)3 to accom-modate different ligands, which has led to the developmentof several strategies to saturate the coordination spherewithligands from a single ligand to a combination of two or moreligands [13–15].The molecular structure of the title complex comprisesthree facial tricarbonyl ligands, a thiourea bidentate ligand(S,O) in the equatorial plane which is trans to the two ofthe carbonyl ligands and N-coordinated pyridine ligand(monodentate) in the axial position as shown in the Figure.The complex was obtained by using the [2 + 1] mixed ligandapproach on fac-[M(CO)3(O2H)3]+ moiety. In particular,the [2 + 1] approach provides a combination strategy of abidentate and a monodentate ligand to yield a uniqueasymmetric tailoring of the complex that affects its (bio)chemical properties such as charge, lipophilicity, andstability [16, 17]. The structure of the titled complex possessesa distorted octahedral geometry around the rheniummetal center as seen with the bond angles C1—Re—O4and C3—Re—N1, reported as 175.27(14)° and 175.88(14)°,respectively. The bite angle distortion of the structurewas 85.96(7)°, which is similar to that of other rheniummetals coordinated with thiourea ligands [18–20]. The bondlength between the three carbons from the carbonylligands and rhenium metal, Re—C1, Re—C2, and Re—C3were found as 1.897(4), 1.914(4), and 1.929(4) Å, respectively.Table : Fractional atomic coordinates and isotropic or equivalentisotropic displacement parameters (Å).Atom x y z Uiso*/UeqC . () . () . () . ()C . () . () . () . ()C . () . () . () . ()C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()C . () . () . () . ()C . () . () . () . ()C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()HA . . . .*HB . . . .*HC . . . .*C . () . () . () . ()H . . . .*C . () . () . () . ()HA . . . .*HB . . . .*C . () . () . () . ()HA . . . .*HB . . . .*C . () . () . () . ()HA . . . .*HB . . . .*C . () . () . () . ()HA . . . .*HB . . . .*C . () . () . () . ()HA . . . .*HB . . . .*N . () . () . () . ()N . () . () . () . ()N . () . () . () . ()O . () . () . () . ()O . () . () . () . ()O . () . () . () . ()O . () . () . () . ()Table : (continued)Atom x y z Uiso*/UeqRe . () . () . () . ()S . () . () . () . ()698 L. Makhakhayi et al.: The crystal structure of C23H24N3O4ReSThe bond distances Re—S1, Re—N1, and Re—O4 werearranged in decreasing order 2.471(10), 2.220(3), and2.138(3) Å, respectively. The bond length obtained inthis study agrees with the other rhenium and rhodiumstructures that were reported previously [21–23]. There arethree intramolecular hydrogen bonds in the titled complexthat stabilizes the complex further from C16—H16⋯N2which has the bond length of 2.768(5) Å, C17—H17A⋯S1witha bond length of 2.992(5) Å, and C8—H8⋯O4 with a bondlength of 2.986(5) Å.Author contributions: All the authors have accepted respon-sibility for the entire content of this submitted manuscriptand approved submission.Research funding: We would like to thank the NationalResearch Foundation of South Africa (Grant No. 129468),Tshwane University of Technology, and the University ofPretoria for institutional and financial support. 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The crystal structure of fac-tricarbonyl(N-benzoylN,N-cyclohexylmethylcarbamimidothioato-k(2)S,O)(pyridine-kN)rhenium(I), C23H24N3O4ReS

https://repository.up.ac.za/bitstream/2263/92944/1/Makhakhayi_Crystal_2023.pdf

The crystal structure of fac-tricarbonyl(N-benzoylN,N-cyclohexylmethylcarbamimidothioato-k(2)S,O)(pyridine-kN)rhenium(I), C23H24N3O4ReS

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