Startseite Naturwissenschaften Crystal structure of [(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-κS]-(triphenylphosphine-κP)-gold(I), C28H26AuN2O3PS
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Crystal structure of [(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-κS]-(triphenylphosphine-κP)-gold(I), C28H26AuN2O3PS

  • Chien Ing Yeo und Edward R.T. Tiekink ORCID logo EMAIL logo
Veröffentlicht/Copyright: 14. Juli 2020

Abstract

C28H26AuN2O3PS, triclinic, P1̄ (no. 2), a = 8.6339(3) Å, b = 11.0503(3) Å, c = 14.5091(5) Å, α = 95.615(2)°, β = 105.606(3)°, γ = 94.009(2)°, V = 1320.14(8) Å3, Z = 2, Rgt(F) = 0.0332, wRref(F2) = 0.0886, T = 100 K.

CCDC no.: 2014870

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Yellow slab
Size:0.30 × 0.27 × 0.16 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:5.74 mm−1
Diffractometer, scan mode:SuperNova, ω
θmax, completeness:27.5°, >99%
N(hkl)measured, N(hkl)unique, Rint:30503, 6068, 0.067
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 5608
N(param)refined:327
Programs:CrysAlisPRO [1], SHELX [2], [3], WinGX/ORTEP [4]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Au0.90609(2)0.14301(2)0.37306(2)0.01835(7)
S10.86000(13)0.22266(11)0.51492(8)0.0251(2)
P10.94848(12)0.07667(9)0.23047(8)0.0154(2)
O11.1696(3)0.2830(3)0.5424(2)0.0226(6)
O20.5538(4)0.6587(3)0.8053(3)0.0328(8)
O30.5482(4)0.4944(3)0.8745(2)0.0321(7)
N11.0654(4)0.3865(3)0.6516(3)0.0210(7)
N20.5967(4)0.5576(3)0.8199(3)0.0232(7)
C11.0436(5)0.3071(4)0.5776(3)0.0186(8)
C20.9391(5)0.4218(4)0.6885(3)0.0188(8)
C30.8639(5)0.3472(4)0.7399(3)0.0209(8)
H30.8910980.2657940.7451560.025*
C40.7516(5)0.3901(4)0.7829(3)0.0197(8)
H40.7020130.3396500.8184970.024*
C50.7117(5)0.5092(3)0.7732(3)0.0178(8)
C60.7810(5)0.5843(4)0.7209(3)0.0215(8)
H60.7503360.6644600.7134830.026*
C70.8964(5)0.5396(4)0.6795(3)0.0210(8)
H70.9467610.5904280.6445600.025*
C81.3295(5)0.3504(4)0.5922(3)0.0246(9)
H81.3528340.3473430.6632160.029*
C91.3336(6)0.4813(4)0.5720(4)0.0326(10)
H9A1.3131210.4841200.5025240.049*
H9B1.4400910.5240600.6058030.049*
H9C1.2502930.5209770.5946450.049*
C101.4476(5)0.2804(5)0.5538(4)0.0341(11)
H10A1.4353840.1947460.5652440.051*
H10B1.5580760.3161600.5867580.051*
H10C1.4258680.2847830.4843840.051*
C110.8160(5)−0.0541(3)0.1596(3)0.0171(8)
C120.8076(5)−0.1605(3)0.2035(3)0.0187(8)
H120.866172−0.1614920.2689780.022*
C130.7135(5)−0.2646(4)0.1513(3)0.0232(9)
H130.710985−0.3378800.1803050.028*
C140.6235(5)−0.2618(4)0.0573(3)0.0213(8)
H140.557566−0.3328520.0223340.026*
C150.6286(5)−0.1565(4)0.0135(3)0.0231(9)
H150.566404−0.155499−0.0512300.028*
C160.7255(5)−0.0513(4)0.0646(3)0.0205(8)
H160.7295670.0212170.0347670.025*
C211.1512(5)0.0318(4)0.2450(3)0.0192(8)
C221.2685(5)0.0749(4)0.3304(3)0.0265(9)
H221.2408240.1224300.3807360.032*
C231.4286(5)0.0475(5)0.3416(4)0.0338(11)
H231.5098930.0781890.3992220.041*
C241.4681(5)−0.0226(4)0.2703(4)0.0336(11)
H241.576592−0.0409310.2790640.040*
C251.3512(5)−0.0678(4)0.1848(4)0.0272(10)
H251.379645−0.1165190.1353510.033*
C261.1917(5)−0.0407(4)0.1723(3)0.0225(9)
H261.110931−0.0715350.1144720.027*
C310.9253(5)0.1958(3)0.1508(3)0.0180(8)
C321.0193(5)0.2090(4)0.0875(3)0.0222(8)
H321.0995970.1552910.0848390.027*
C330.9950(5)0.3019(4)0.0280(3)0.0244(9)
H331.0578360.310981−0.0159890.029*
C340.8779(5)0.3813(4)0.0333(3)0.0247(9)
H340.8623740.445337−0.0064080.030*
C350.7843(5)0.3670(4)0.0963(3)0.0233(9)
H350.7035890.4204330.0988990.028*
C360.8082(5)0.2753(4)0.1554(3)0.0206(8)
H360.7449040.2663150.1991580.025*

Source of material

NaOH (Merck; 0.020 g, 0.50 mmol) in water (5 mL) was added to a suspension of Ph3PAuCl (0.247 g, 0.50 mmol) in acetonitrile (20 mL), followed by addition of iPrOC(=S)N(H)C6H4NO2-4 (0.120 g, 0.50 mmol) in chloroform (20 mL). After stirring for 2 h, the solution was left for slow evaporation at room temperature, yielding yellow crystals after 2 weeks. Yield: 0.314 g (90%). M. pt. (Biobase automatic melting point apparatus MP450): 439–440 K. Elemental Analysis for C28H26AuN2O3PS (Leco TruSpec Micro CHN Elemental Analyser: C, 48.14; H, 3.75; N, 4.01%. Found: C, 47.78; H, 3.47; N, 3.76%. IR (Bruker Vertex 70v FTIR Spectrophotometer; cm−1): 1435 (s) ν(C=N), 1149 (s) ν(C—O), 1097 (s) ν(C—S). 1H NMR (Bruker Ascend 400 MHz NMR spectrometer with chemical shifts relative to tetramethylsilane in CDCl3 solution at 298 K; ppm): δ 7.93 (dt, 2H, m-aryl-H, 3JHH = 8.92 Hz, 4JHH = 2.42 Hz), 7.56–7.39 (m, br, 15H, Ph3P), 6.89 (dt, 2H, o-aryl-H, 3JHH = 8.92 Hz, 4JHH = 2.42 Hz), 5.25 (sept, 1H, OCH, JHH = 6.20 Hz), 1.33 (d, 6H, CH3, JHH = 6.20 Hz). 13C{1H} NMR (as for 1H NMR): δ 164.7 (Cq), 157.6 (aryl, Cipso), 142.6 (aryl, Cpara), 134.1 (d, m-Ph3P, 3JCP = 13.79 Hz), 131.9 (d, p-Ph3P, 4JCP = 2.36 Hz), 129.2 (d, o-Ph3P, 2JCP = 11.55 Hz), 129.1 (d, i-Ph3P, 1JCP = 57.52 Hz), 124.9 (aryl, Cmeta), 122.5 (aryl, Cortho), 71.5 (OCH), 22.0 (CH3). 31P{1H} NMR (as for 1H NMR but with chemical shift referenced to 85% aqueous H3PO4 as the external reference): δ 37.9.

Experimental details

The C-bound H atoms were geometrically placed (C—H = 0.95–1.00 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The maximum and minimum residual electron density peaks of 3.05 and 2.13 eÅ−3, respectively, were each located 0.86 Å from the Au atom.

Comment

Phosphanegold(I) thioamide molecules of the general formula R3PAu[SC(OR′)=NR′′] are known to adopt two distinct molecular conformations. The basic, linear P—Au—S fragment is common to all structures with the difference arising in the relative orientations of the OR′ and NR′′ groups with respect to the gold atom which lead to an intramolecular Au⋯O or Au⋯π interaction, respectively. This variation in structure is nicely exemplified by the series of structures where R′′ = 4-nitrophenyl. Thus, when R′ = Me, and R = Ph [5], R = o-tolyl, as CHCl3 and H2O solvates, and R = m-tolyl [6], the conformation featuring the Au⋯O contact is observed. This conformation is also seen in the crystals of the R′ = Et compounds with R = Ph (as the CH2Cl2 solvate) [7] and p-tolyl [8]. More recently, for R′ = Et and R = p-tolyl, the conformation where a Au⋯π interaction forms instead of a Au⋯O contact was reported, i.e. a conformational polymorph [9]. Studies suggest the Au⋯O/Au⋯π phenomenon correlates with kinetic factors associated with crystallisation as DFT calculations indicate the Au⋯π interactions are more stable than Au⋯O contacts [10], [11]. In continuing systematic studies in this area, the title compound, i.e. Ph3PAu[SC(O-iPr)=NC6H4NO2-4], (I), was investigated crystallographically.

The molecular structure of (I) is shown in the figure (70% displacement ellipsoids) and features a linear coordination of the gold atom [P1—Au—S1 = 176.31(3)°] defined by phosphane-P [Au—P1 = 2.2582(10) Å] and thiolate-S [Au—S1 = 2.3032(11) Å] atoms. The C1—S1 [1.750(4) Å] and C1—N1 [1.282(6) Å] bond lengths in (I) have lengthened and shortened, respectively, compared with the equivalent bonds in the neutral ligand, i.e. iPrOC(=S)N(H)C6H4NO2-4, of 1.678(3) and 1.352(3) Å, respectively [12]. As is usually found in R3PAu[SC(OR′)=NC6H4NO2-4] structures, an intramolecular Au⋯O interaction [3.060(3) Å] is observed in (I).

The molecular packing for (I) features phenyl-C—H⋯O(nitro) interactions [C35—H35⋯O3i: H35⋯O3i = 2.54 Å, C35⋯O3i = 3.451(6) Å with an angle at H35 = 162° for symmetry operation (i) 1 − x, 1 − y, 1 − z] which link molecules into centrosymmetric dimers. The dimers are linked into a supramolecular tube along the a-axis via methyl-C—H⋯π(nitrophenyl) [C10—H10b⋯Cg(C2—C7) = 2.93 Å with angle at H10b = 159 Å for (ii) 1 + x, y, z] and π(nitrophenyl)⋯π(P-phenyl) inter-centroid Cg(C2—C7)⋯Cg(C31–C36) distance = 3.753(2) Å with angle of inclination = 18.7(2)° for (iii) 2 − x, 1 − y, 1 − z].

As the tubes exhibit no directional interactions between them in the crystal, the supramolecular association was also probed by an analysis of the calculated Hirshfeld surfaces and two-dimensional fingerprint plots using Crystal Explorer 17 [13] and literature procedures [14]. As anticipated, H⋯H contacts dominate the Hirshfeld surface, contributing 43.3% of all contacts. Distinctive features are noted in the fingerprint plots for the H⋯C/C⋯H [24.2%] and H⋯O/O⋯H [14.6%] contacts reflecting the specified intermolecular contacts. Similarly, a characteristic arrow distribution is noted for the C⋯C contacts but, the contribution to the surface is small at 2.9%. Other contacts, such as H⋯S/S⋯H [7.2%] and H⋯N/N⋯H [3.0%] along with a number of other minor contributions occur at distances beyond the sums of the respective van der Waals radii.

Acknowledgements

Sunway University Sdn Bhd is thanked for financial support of this work through Grant No. STR-RCTR-RCCM-001–2019.

References

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Received: 2020-06-22
Accepted: 2020-07-08
Published Online: 2020-07-14
Published in Print: 2020-08-26

©2020 Chien Ing Yeo et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  42. Crystal structure of 4-(3-(pyridin-3-yl)ureido)benzoic acid — adipic acid (2/1), C16H16N3O5
  43. Crystal structure of poly[bis{μ2-5-carboxy-4′-methyl-[1,1′-biphenyl]-3-carboxylato-κ2O:O′}-{μ2-4,4′-bipyridine-κ2N:N′}]cobalt(II), C40H30N2O8Co
  44. Crystal structure of aqua-(2,2′-bipyridine-κ2N,N′)(((3-nitrophenyl)sulfonyl)glycine-κ2N,O)copper(II) dihydrate, C18H20CuN4O9S
  45. Crystal structure of bis{2-bromo-6-(((4-(1-(methoxyimino)ethyl)phenyl)imino)methyl)phenolato-κ2N,O}copper(II), C32H28Br2CuN4O4
  46. Crystal structure of bis(2-(2-((2,6-dichlorophenyl)amino)phenyl)acetato-κ2O,O′)-(1,10-phenanthroline-κ2N,N′)zinc(II), C40H28Cl4N4O4Zn
  47. Crystal structure of 2-(3,6-dimethyl-2,3-dihydro-4H-benzo[b][1,4]oxazin-4-yl)-2-oxoethyl acetate, C14H17NO4
  48. Crystal structure of poly[dibromido-bis(μ2-1,6-di(1H-imidazol-1-yl)hexane-κ2N:N′)cadmium(II)], C24H36Br2N8Cd
  49. Synthesis and crystal structure of ((6R,7S)-3-ethyl-6-phenyl-6,7-dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-7-yl)(phenyl)methanone hemihydrate, 2(C19H18N4OS) ⋅ H2O
  50. Crystal structure of 2-(5-(pyridin-3-yl)-4-(pyridin-4-yl)-4H-1,2,4-triazol-3-yl)pyridine, C17H12N6
  51. The crystal structure of N-((1E,2E)-1,3-bis(4-fluorophenyl)but-2-en-1-ylidene)-4-methylbenzenesulfonamide, C23H19F2NO2S
  52. Crystal structure of diacetato-κ1O-diethanol-κ1O-bis(μ2-2-(((2-hydroxyethyl)imino)methyl)-5-methoxyphenolato-κ4O,N,O′:O′′)dinickel(II), C28H42Ni2N2O12
  53. The crystal structure of catena-poly[chlorido-(μ2-1,4-bis(pyridin-3-yl-methoxy)benzene-κ2N:N′)copper(II)], C18H16ClN2O2Cu
  54. N′,N′′′-(((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(methaneylylidene))bis(2-hydroxybenzohydrazide)nickel(II), C30H24N4NiO6
  55. Crystal structure of (E)-3′,6′-bis(ethylamino)-2′,7′-dimethyl-2-(2-((quinolin-2-ylmethylene)amino)ethyl)spiro[isoindoline-1,9′-xanthen]-3-one, C38H37N5O2
  56. Crystal structure of 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl-1-ium 5,3′,5′-tricarboxy-[1,10-biphenyl]-2-carboxylate, C25H17N2O8
  57. The crystal structure of 1-carboxy-2-(1H-indol-3-yl)-N,N,N-trimethylethan-1-ammonium chloride, C14H19N2O2Cl
  58. The crystal structure of 5-bromo-2-fluoronicotinic acid monohydrate, C6H5BrFNO3
  59. Crystal structure of ethyl 3-(trifluoromethyl)-1H-pyrazole-4-carboxylate, C7H7F3N2O2
  60. Crystal structure of tetrakis(1H-benzo[d]imidazol-3-ium) bis(μ5-phenylphosphonato)-pentakis(μ2-oxido)-decaoxo-penta-molybdenum dihydrate, C40H42Mo5N8O23P2
  61. Structure of 7-(3,3,4,4,5,5-hexafluoro-2-(2-methylbenzo[b]thiophen-3-yl)cyclopent-1-en-1-yl)-8-methylquinoline, C24H15F6NS
  62. Crystal structure of monocarbonyl[2-((cyclopentylmethylene)amino)-5-methylphenolato-κ2N,O] (tricyclohexylphosphine)rhodium(I), C32H48NO2PRh
  63. The crystal structure of fac-tricarbonyl(1,10-phenanthroline-κ2N,N′)-(pyrazole-κN)rhenium(I)nitrate, C18H12O3N4Re
  64. Crystal structure of poly[diaqua-bis(μ2-4-(3-(pyridin-3-yl)-1H-1,2,4-triazol-5-yl)benzoato-κ2N:O)nickel(II)], C28H22O6N8Ni
  65. Crystal structure of 4,4′-bis(pyridin-1-ium-4-yl)biphenyl poly[bis(μ2-4,4′-bis(pyrid-4-yl)biphenyl-K2N:N′)-tetrakis(μ4-4′-methyl-[1,1′-biphenyl]-3,5-dicarboxylato-K4O,O′:O′′:O′′′)-bis[[μ2-1,1′-biphenyl]-3-carboxyl-5-carboxylato-K2O:O′]tetracobalt(II)]— [1,1′-biphenyl]-3,5-dicarboxylic acid (1/2), C93H68N3O16Co2
  66. The crystal structure of 4a-formyl-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,12b,13,14b-icosahydro-1-2-6a,6b,9,9,12a-heptamethylpicen-10-yl acetate, C32H50O3
  67. Crystal structure of 3,3′-(1,2-phenylenebis(methylene))bis(1-methyl-1H-imidazol-3-ium) bis(hexafluoridophosphate), C16H20F12N4P2
  68. Crystal structure of catena-poly[diaqua-(μ2-tartrato-κ4O,O′:O′′,O′′′)zinc(II)], C4H8O8Zn
  69. The crystal structure of (6aR,6bS,8aS,8bR,9S,11aS,12aS,12bS)-10-(4-acetoxy-3-methylbutyl)-6a,8a,9-trimethyl-3,4,5,6,6a,6b,7,8,8a,8b,9,10,11a,12,12a,12b-hexadecahydro-1H-naphtho[2′,1′:4,5]indeno[2,1-b]furan-4-yl acetate, C31H48O5
  70. Crystal structure of 4,4′-(oxybis(methylene))bis(bromobenzene), C14H12Br2O
  71. Crystal structure of (N,N-dimethylsulphoxide)-[N-(3-ethoxy-2-(oxide)benzylidene)-3-methoxybenzenecarbohydrazonato-κ3N,O,O′]-dioxo-molybdenum(VI), C19H22MoN2O7S
  72. Crystal structure of dichlorido-bis(dimethyl sulphoxide-κO)-bis(4-methylbenzyl-κC1)tin(IV), C20H30Cl2O2S2Sn
  73. Crystal structure of (E)-2-amino-N′-(2-hydroxy-4-(2-(piperidin-1-yl)ethoxy)benzylidene)benzohydrazide monohydrate, C21H26N4O3 ⋅ H2O
  74. Crystal structure of chloridotris(4-chlorophenyl)(dimethyl sulfoxide-κO)tin(IV), C20H18Cl4OSSn
  75. Crystal structure of catena{di-aqua-sodium-[N-(hydroxyethyl), N-isopropyl-dithiocarbamato]}n, [C6H16NNaO2S2]n
  76. Crystal structure of 2,2,4,4,6,6-hexakis(4-chlorophenyl)-1,3,5,2,4,6-trithiatristanninane, C36H24Cl6S3Sn3
  77. Crystal structure of 6-methoxy-3-(5-(3-methoxyphenyl)-1,3,4-oxadiazol-2-yl)-4H-chromen-4-one-methanol (1/1), C20H18N2O6
  78. Crystal structure of hexanedihydrazide, C6H14N4O2
  79. Crystal structure of tert-butyl 2-(hydroxymethyl)-5-{4-[(methoxycarbonyl)amino]phenyl}-2,5-dihydro-1H-pyrrole-1-carboxylate, C18H24N2O5
  80. Crystal structure of [(Z)-O-isopropyl N-(4-nitrophenyl)thiocarbamato-κS]-(triphenylphosphine-κP)-gold(I), C28H26AuN2O3PS
  81. Crystal structure of [O-ethyl N-(4-nitrophenyl)thiocarbamato-κS](tri-4-tolylphosphine-κP)gold(I) tetrahydrofuran solvate, C30H30AuN2O3PS, C4H8O
Heruntergeladen am 20.12.2025 von https://www.degruyterbrill.com/document/doi/10.1515/ncrs-2020-0306/html
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