Home Physical Sciences Crystal structure of [O-ethyl N-(4-nitrophenyl)thiocarbamato-κS](tri-4-tolylphosphine-κP)gold(I) tetrahydrofuran solvate, C30H30AuN2O3PS, C4H8O
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Crystal structure of [O-ethyl N-(4-nitrophenyl)thiocarbamato-κS](tri-4-tolylphosphine-κP)gold(I) tetrahydrofuran solvate, C30H30AuN2O3PS, C4H8O

  • Fong Sheen Kuan and Edward R.T. Tiekink ORCID logo EMAIL logo
Published/Copyright: July 16, 2020

Abstract

C34H38AuN2O4PS, triclinic, P1̄ (no. 2), a = 10.2034(8) Å, b = 11.5755(9) Å, c = 15.7533(12) Å, α = 69.948(2)°, β = 86.496(2)°, γ = 71.370(2)°, V = 1653.8(2) Å3, Z = 2, Rgt(F) = 0.0355, wRref(F2) = 0.0858, T = 223(2) K.

CCDC no.: 2015448

The molecular structures are 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 prism
Size:0.16 × 0.15 × 0.11 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:4.60 mm−1
Diffractometer, scan mode:Bruker AXS SMART, φ and ω
θmax, completeness:30.0°, >99%
N(hkl)measured, N(hkl)unique, Rint:13916, 9419, 0.029
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 8135
N(param)refined:391
Programs:Bruker [1], SHELX [2], [3], WinGX/ORTEP [4]
Table 2:

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

AtomxyzUiso*/Ueq
Au0.22383(2)0.23082(2)0.17550(2)0.03083(5)
S10.33883(11)0.29783(9)0.04602(6)0.0376(2)
P10.11606(10)0.15422(8)0.30186(6)0.02898(18)
O10.1504(3)0.5087(2)0.05143(17)0.0343(5)
O20.6365(4)0.3526(4)−0.3702(2)0.0636(9)
O30.7886(3)0.3784(4)−0.2961(2)0.0611(9)
O40.7170(4)0.1044(4)0.8253(2)0.0624(9)
N10.2635(3)0.5386(3)−0.0790(2)0.0351(7)
N20.6709(4)0.3801(3)−0.3083(2)0.0455(8)
C10.2468(4)0.4627(3)−0.0018(2)0.0292(7)
C20.3665(4)0.4936(3)−0.1346(2)0.0316(7)
C30.3343(4)0.4576(4)−0.2032(3)0.0440(9)
H30.2433040.458986−0.2115070.053*
C40.4339(4)0.4196(4)−0.2599(3)0.0443(9)
H40.4116830.393732−0.3061300.053*
C50.5665(4)0.4198(4)−0.2481(2)0.0344(8)
C60.5998(4)0.4587(5)−0.1818(3)0.0491(10)
H60.6904010.459071−0.1745840.059*
C70.4992(4)0.4972(5)−0.1258(3)0.0474(10)
H70.5208640.526150−0.0811290.057*
C80.0699(4)0.6446(3)0.0152(3)0.0381(8)
H8A0.0104650.661132−0.0370590.046*
H8B0.1310220.698145−0.0040200.046*
C9−0.0166(5)0.6752(4)0.0905(3)0.0509(11)
H9A−0.0729270.7658490.0694540.076*
H9B−0.0763110.6212740.1088180.076*
H9C0.0436160.6580940.1416840.076*
C100.0102(4)0.2788(3)0.3442(2)0.0302(7)
C11−0.0943(4)0.2576(3)0.4019(3)0.0371(8)
H11−0.1151690.1798660.4158460.044*
C12−0.1682(4)0.3497(4)0.4393(3)0.0392(8)
H12−0.2389090.3340860.4782560.047*
C13−0.1385(4)0.4658(3)0.4196(3)0.0358(8)
C14−0.0348(4)0.4858(4)0.3617(3)0.0392(8)
H14−0.0141210.5637000.3471760.047*
C150.0392(4)0.3939(3)0.3245(3)0.0338(7)
H150.1099580.4095570.2855400.041*
C16−0.2192(5)0.5649(4)0.4613(3)0.0481(10)
H16A−0.1690480.5526620.5157480.072*
H16B−0.3092160.5542870.4765870.072*
H16C−0.2312730.6513760.4185440.072*
C170.0001(4)0.0726(3)0.2862(2)0.0299(7)
C180.0208(4)−0.0584(3)0.3287(2)0.0340(7)
H180.098098−0.1093320.3692540.041*
C19−0.0709(4)−0.1160(4)0.3125(3)0.0412(9)
H19−0.055585−0.2050890.3426320.049*
C20−0.1840(5)−0.0437(4)0.2525(3)0.0431(9)
C21−0.2054(4)0.0883(4)0.2086(3)0.0447(9)
H21−0.2821060.1384890.1675280.054*
C22−0.1144(4)0.1464(4)0.2250(2)0.0385(8)
H22−0.1297960.2355580.1949610.046*
C23−0.2851(6)−0.1067(6)0.2361(3)0.0649(14)
H23A−0.363716−0.0405220.1979500.097*
H23B−0.317002−0.1512690.2934630.097*
H23C−0.239294−0.1684990.2062650.097*
C240.2371(4)0.0392(3)0.3950(2)0.0302(7)
C250.2307(4)0.0479(4)0.4803(2)0.0395(8)
H250.1612530.1162280.4916940.047*
C260.3244(4)−0.0419(4)0.5490(3)0.0416(9)
H260.317719−0.0334850.6064800.050*
C270.4281(4)−0.1442(3)0.5358(3)0.0380(8)
C280.4340(5)−0.1525(4)0.4498(3)0.0482(10)
H280.503223−0.2213100.4387940.058*
C290.3413(4)−0.0628(4)0.3801(3)0.0414(9)
H290.348340−0.0705130.3224080.050*
C300.5273(5)−0.2437(5)0.6131(3)0.0588(12)
H30A0.560104−0.1999610.6457940.088*
H30B0.605456−0.2952210.5895470.088*
H30C0.480186−0.2998890.6537790.088*
C310.8373(5)0.0655(7)0.8817(4)0.0722(16)
H31A0.8953200.1203620.8545530.087*
H31B0.891532−0.0248610.8904910.087*
C320.7898(6)0.0796(6)0.9680(4)0.0689(15)
H32A0.7701410.1691370.9659850.083*
H32B0.8584740.0213381.0176030.083*
C330.6602(6)0.0426(6)0.9781(4)0.0663(14)
H33A0.5923920.0902991.0110000.080*
H33B0.680318−0.0506841.0101260.080*
C340.6079(5)0.0801(5)0.8818(3)0.0557(12)
H34A0.5820080.0097500.8738250.067*
H34B0.5262490.1580570.8664600.067*

Source of material

The compound was prepared as per the literature [5] and crystals were harvested from a tetrahydrofuran solution of the compound.

Experimental details

The H atoms were geometrically placed (C—H = 0.94–0.98 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). Owing to poor agreement, a number of reflections, i.e. (0 0 1), (−2 −1 6), (−1 0 6), (0 1 0), (2 8 15), (4 0 4), (−4 6 5), (−2 0 12), (8 0 6) and (−1 0 7), were omitted from the final cycles of refinement. The maximum and minimum residual electron density peaks of 1.36 and 0.84 e Å−3, respectively, were located 0.89 and 1.31 Å from the Au and S1 atoms, respectively.

Comment

Conformational flexibility about the S—C bond in phosphanegold(I) thioamide molecules of the general formula R3PAu[SC(OR′)=NR′′] means either the alkoxyl-O atom is orientated towards the gold(I) centre, forming an intramolecular Au⋯O contact, or the arene ring is disposed towards the gold(I) centre, enabling the formation of an intramolecular Au⋯π interaction. DFT calculations suggest the latter is more favourable [6]. Nevertheless, Au⋯O interactions are generally formed, possibly owing to electronic effects/steric congestion [7], [8]. Although conformational polymorphs featuring Au⋯O or Au⋯π interactions are comparatively rare [9], [10], unsolvated forms of the title solvate, (4-tolyl)3PAu[SC(OEt)=NC6H4NO2-4]. THF (I), are known to feature Au⋯O [5] or Au⋯π [11] interactions. In on-going systematic studies of R3PAu[SC(OR′)=NR′′] molecules, the crystal and molecular structures of (I) are described.

The molecular structures are shown in the figure (50% displacement ellipsoids). The gold(I) atom is in the expected linear geometry [P1—Au—S1 = 176.88(3)°] defined by phosphane-P [Au—P1 = 2.2589(9) Å] and thiolato-S [Au—S1 = 2.3115(9) Å] atoms. The thiolato-C1—S1 [1.746(3) Å] and imine-C1—N1 [1.282(6) Å] bond lengths in (I) have lengthened and shortened, respectively, compared with the equivalent thione [1.672(2) Å] and amine [1.354(3) Å] bonds in the parent acid, i.e. EtOC(=S)N(H)C6H4NO2-4 [12]. The orientation of the thiolato ligand is such as to place the ethoxy-O1 atom in close proximity to the gold(I) atom with the Au⋯O separation being 3.009(2) Å]. The Au—S1 [2.3105(8) Å], Au—P1 [2.2611(8) Å] and Au⋯O1 [2.915(2) Å] separations in the solvent-free form [5] are very close to those in (I) with the shorter Au⋯O separation correlating with a greater deviation from 180° for the P1—Au—S1 angle [175.80(3)°], i.e. by approximately 1° compared with that in (I). For the conformational polymorph featuring the intramolecular Au⋯π interaction [11], Au—S1 [2.303(3) Å] is experimentally equivalent to those above but, the Au—P1 bond length [2.271(3) Å] appears to have lengthened, perhaps owing to steric congestion due to the proximity of the arene ring.

In the crystal of (I), tolyl-C—H⋯N(imine) interactions [C22—H22⋯N1i: H22⋯N1i = 2.60 Å, C22⋯N1i = 3.469(5) Å with angle at H22 = 153° for symmetry operation (i): −x, 1 − y, −z] lead to centrosymmetric dimers. These are connected into a supramolecular chain aligned, approximately, along [−1 −2 6], sustained by tolyl-C—H⋯π(tolyl) interactions [C26—H26⋯Cg(C17–C22)ii: H26⋯Cg(C17–C22)ii = 2.93 Å with angle at H26 = 133° for (ii) −x, −y, 1 − z]. The packing of the chains define columns parallel to the a-axis direction in which reside the solvent THF molecules. The closest contact involving the THF molecule is a tolyl-C—H⋯O(THF) interaction [C29—H29⋯O4iii: H29⋯O4iii = 2.64 Å with angle at H29 = 160° for (iii) 1 − x, −y, 1 − z]. The lack of directional interactions between the host and guest molecules accounts for the instability of the crystals of (I), which lose solvent upon standing in the atmosphere.

A further investigation of the molecular packing was conducted by calculating the Hirshfeld surfaces and two-dimensional fingerprint plots with the aid of Crystal Explorer 17 [13] following literature procedures [14]. The dominant contacts about the THF molecule are H⋯H [64.1%] and H⋯C/C⋯H [15.2%], with the next most dominant being H⋯O/O⋯H at 7.5% and H⋯S/S⋯H at 5.6%. The distribution of contacts for the gold-containing molecule follow similar trends with the dominant contacts being H⋯H [52.2%] and H⋯C/C⋯H [21.0%], but reduced and increased, respectively, compared with the THF molecule. Contacts due to H⋯N/N⋯H, with a characteristic forceps-like distribution in the two-dimensional fingerprint plot account for only 2.3% of surface contacts with greater contributions from H⋯O/O⋯H [14.2%] and H⋯S/S⋯H [5.1%] but at separations exceeding 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: 2020-06-28
Accepted: 2020-07-10
Published Online: 2020-07-16
Published in Print: 2020-08-26

©2020 Fong Sheen Kuan 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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  39. Crystal structure of 4-(4′-(pyridin-4-yl)-[1,1′-biphenyl]-4-yl)pyridin-1-ium 2-carboxy-4-(3,5-dicarboxyphenoxy)benzoate hydrate, C38H28N2O10
  40. Crystal structure of 3-[(triisopropylsilanyl)-ethynyl]-6a,12a-dihydro-1H-1,4-diaza-benzo[α]anthracene-2,7,12-trione, C27H28N2O3Si
  41. Crystal structure of [(bis(1,10-phenanthroline-κ2N,N′)-(2-carboxy-4-(3-carboxy-5-carboxylatophenoxy)benzoato-κ2O:O′))nickel(II) monohydrate, (1,10-phenanthroline-κ2N:N′)-(μ2-(5-(3′,4′-dicarboxylphenoxy)-isophthalate-κ2O:O′))nickel(II)], C40H24N4O9Ni ⋅ H2O
  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
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