Startseite Crystal structure of chlorido-(η6–1-isopropyl-4-methyl benzene)-(1-(pyridin-2-yl)-N-(p-tolyl)methanimine-κ2N,N′)ruthenium(II) hexafluorophosphate(V), C23H26ClF6N2PRu
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Crystal structure of chlorido-(η6–1-isopropyl-4-methyl benzene)-(1-(pyridin-2-yl)-N-(p-tolyl)methanimine-κ2N,N′)ruthenium(II) hexafluorophosphate(V), C23H26ClF6N2PRu

  • Joel M. Gichumbi , Holger B. Friedrich und Bernard Omondi EMAIL logo
Veröffentlicht/Copyright: 10. Februar 2017

Abstract

C23H26ClF6N2PRu, triclinic, P1̅ (no. 2), a = 8.9950(6) Å, b = 11.1669(8) Å, c = 12.4128(9) Å, α = 80.520(2)°, β = 87.5360(10)°, γ = 86.3200(10)°, V = 1226.59(15) Å3, Z = 2, Rgt(F) = 0.0267, wRref(F2) = 0.0622, T = 173(2) K.

CCDC no.:: 1528297

The title crystal structure is shown in the figure. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Yellow block
Size:0.18 × 0.13 × 0.12 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:8.7 cm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω
2θmax, completeness:56.8°, >99%
N(hkl)measured, N(hkl)unique, Rint:31876, 6121, 0.042
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 5409
N(param)refined:314
Programs:Bruker programs [11], SHELX [12]
Table 2

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

AtomxyzUiso*/Ueq
C10.6025(2)0.52363(19)0.65711(18)0.0284(4)
H10.70340.5430.64190.034*
C20.5595(2)0.41164(19)0.64094(18)0.0304(5)
H20.62960.35580.61350.036*
C30.4138(2)0.38115(19)0.66484(18)0.0296(5)
H30.38290.30390.65540.036*
C40.3141(2)0.46535(19)0.70286(17)0.0266(4)
H40.21360.44640.72080.032*
C50.3625(2)0.57688(17)0.71424(16)0.0211(4)
C60.2654(2)0.67694(18)0.74080(16)0.0231(4)
H60.16210.66750.75670.028*
C70.2267(2)0.88000(18)0.76569(16)0.0226(4)
C80.1139(2)0.8632(2)0.84537(18)0.0285(4)
H80.10310.78560.88870.034*
C90.0165(2)0.9612(2)0.86144(19)0.0328(5)
H9−0.06090.94950.9160.039*
C100.0300(2)1.0759(2)0.79935(19)0.0319(5)
C110.1461(2)1.0908(2)0.72200(18)0.0304(5)
H110.1581.16880.67960.036*
C120.2453(2)0.99492(18)0.70497(17)0.0255(4)
H120.32511.00750.65240.031*
C13−0.0788(3)1.1806(2)0.8156(2)0.0492(7)
H13A−0.10611.22660.74430.074*
H13B−0.03241.23410.85790.074*
H13C−0.16841.14910.85520.074*
C140.7773(2)0.8593(2)0.67413(17)0.0293(5)
C150.7926(2)0.7466(2)0.74044(17)0.0268(4)
H150.86130.68590.71920.032*
C160.7067(2)0.72056(19)0.83990(16)0.0235(4)
H160.71660.64190.88280.028*
C170.6073(2)0.80976(18)0.87537(16)0.0236(4)
C180.5902(2)0.92438(18)0.80519(17)0.0257(4)
H180.52220.98560.82640.031*
C190.6709(2)0.94879(19)0.70600(18)0.0300(5)
H190.65511.02490.65970.036*
C200.8668(3)0.8864(3)0.5692(2)0.0466(7)
H20A0.96170.91840.58350.07*
H20B0.81110.9470.51760.07*
H20C0.88620.81170.53790.07*
C210.5222(2)0.7893(2)0.98378(17)0.0291(4)
H210.42930.84380.97780.035*
C220.4784(3)0.6589(2)1.01948(19)0.0391(6)
H22A0.42440.63320.96110.059*
H22B0.41430.65421.08570.059*
H22C0.56830.60541.03460.059*
C230.6200(3)0.8277(2)1.06876(19)0.0379(5)
H23A0.71190.77531.07560.057*
H23B0.56580.81991.13950.057*
H23C0.64480.91251.04550.057*
N10.50673(17)0.60562(14)0.69351(13)0.0209(3)
N20.32296(16)0.77905(14)0.74233(13)0.0205(3)
F10.12870(16)0.59118(16)0.49576(15)0.0605(5)
F20.12009(16)0.38912(15)0.53006(13)0.0527(4)
F30.02962(16)0.49340(18)0.37312(12)0.0594(5)
F40.02056(16)0.47202(14)0.12879(11)0.0455(4)
F50.16799(14)0.53898(14)−0.01701(13)0.0496(4)
F60.05565(16)0.36324(12)−0.00774(12)0.0446(3)
P100.50.50.03507(19)
P200.500.02441(16)
Cl10.49348(6)0.82821(5)0.52082(4)0.02720(11)
Ru10.55275(2)0.78196(2)0.70978(2)0.01841(5)

Source of material

To a suspension of [(η6-p-cymene)Ru(μ-Cl)Cl]2 (0.2 mmol) in methanol (20 mL) was added (1-(pyridin-2-yl)-N-(p-tolyl)methanimine (0.42 mmol). The mixture was stirred at room temperature for 3 hours followed by the reduction in the volume of the solvent in vacuo to about 10 mL before adding NH4PF6 (0.42 mmol). The mixture was then cooled in an ice bath while stirring for 2 hours leading to a precipitate which was collected by filtration. The filtrate was washed with diethyl ether and dried in vacuo. Crystals of the title compound were obtained by the liquid diffusion method, in which the solutions of the compounds in acetone were layered with hexane and left undisturbed for two days.

Orange powder. Yield 80%. m.p. 188 °C (decomp). 1H-NMR (400 MHz, DMSO-d6). δ = 9.56 (d, JHH = 5.44 Hz, 1H, Py), 8.88 (s, 1H, CH = N), 8.30 (t, JHHH = 7.56 Hz, 2H, Py), 7.87 (s, 1H, Py), 7.71 (d, JHH = 8.16 Hz, 2H, Ar), 7.44 (d, JHH = 8.16 Hz, 2H, Ar), 6.09 (d, JHH = 6.20 Hz, 1H, p-cymene), 5.75 (d, JHH = 6.21 Hz, 1H, Ar, p-cymene), 5.62 (q, 2H, Ar, p-cymene), 2.67 (sep, 1H, CH(Me)2), 2.44 (s, 3H, CH3), 2.16 (s, 3H, CH3), 0.98 (d, JHH = 6.84 Hz, 6H, CH-Me2 (p-cymene)). 13C-NMR (400 MHz, DMSO-d6). δ 167.02 (CH = N), 155.91 (Py), 154.56 (Py), 149.42 (Py), 139.88 (Py), 139.62 (Py), 129.87 (Ar), 128.74 (Ar), 122.40 (Ar), 104.93 (Ar), 103.56 (Ar), 86.50 (Ar, p-cymene), 86.24; (Ar, p-cymene), 85.07 (Ar, p-cymene), 84.75 (Ar, p-cymene), 30.45 (CH), 21.68 (CH3), 21.54 (CH3), 20.78 (CH3), 18.26 (CH3); IR (solid state): (−CH = N) 1608 cm−1, (P-F) 833 cm−1. MS (ESI, m/z): 467.08 [M+].

Experimental details

All hydrogen atoms were placed in idealised positions and refined in riding models with Uiso assigned the values of 1.2Ueq those of their parent atoms. The distances of C-H were constrained to 0.95 Å for all aromatic hydrogens.

Discussion

Half-sandwich ruthenium(II) arene complexes have found application as catalyst precursors for a wide range of chemical transformations, and are used in biological applications [1], [2]. Among the half-sandwich complexes, arene ruthenium complexes represent one of the most sought after organometallic compounds due to their potential applications in catalytic and biological applications [3]. The coordinated arene moieties are relatively inert towards substitution and act as spectator ligand [4]. These stabilize and protect the metal centre and thereby prevent rapid oxidation of the Ru(II) to Ru(III) [4]. The title compound is part of our continuing studies of half-sandwich ruthenium(II) complexes [5], [6], [7], [8].

The asymmetric unit of the title structure contains one cationic ruthenium complex in general position and two half [PF6] anions located at two inversion centers of the triclinic space group P1̅. The cationic ruthenium(II) complex possess a piano stool geometry where the chelating ligand and the chloride occupy the positions of the three legs of a piano-stool and the arene ring occupies the remaining coordination sites as the seat of the stool [3]. The Ru-N bond lengths of the complex are 2.0606(12) and 2.0804(13) Å. These distances are comparable to those reported for other arene ruthenium complexes with N,N′-donor ligands [5], [6], [7]. The N-Ru-N bond angles was derived to be 76.52(6)°. The N-Ru-Cl bond angles are 84.04(4) and 84.05(5)°. These values are close to those reported for related compounds [5], [6], [7], [8], [9], [10]. All C—C, C—N and P—F bond lengths and angles are in the expected ranges.

Acknowledgement

We wish to extend our sincere thanks to the NRF, THRIP (Grant No. Tp 1208035643) and UKZN (URF) for financial support. Gichumbi, M. Joel thanks Prof. E.N. Njoka for his support.

References

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Received: 2016-8-5
Accepted: 2017-1-18
Published Online: 2017-2-10
Published in Print: 2017-3-1

©2017 Joel M. Gichumbi et al., published by De Gruyter.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Artikel in diesem Heft

  1. Cover and Frontmatter
  2. The crystal structure of triphenylphosphineoxide – 2,5-dichloro-3,6-dihydroxycyclohexa-2,5-diene-1,4-dione (2/1), C42H32Cl2O6P2
  3. Crystal structure of poly-[diaqua-[bis(μ2-hydroxy)-bis(μ4-3,4,5,6-tetrachlorophthalato-κ3O,O′:O′; κ2O′′:O′′′)dilanthanum(III)], C8H3Cl4LaO6
  4. Crystal structure of 1,1′-(3,4-diphenylthieno[2,3-b]thiophene-2,5-diyl)bis[1-phenyl-methanone], C32H20O2S2
  5. Crystal structure of 4a-hydroxy-9-(3,5-dibromo-phenyl)-3,4,4a,5,6,7,9,9a-octahydro-2H-xanthene-1,8-dione, C19H18Br2O4
  6. Crystal structure of 5-hydroxy-4,6,9,10-tetramethyl-1-oxo-6-vinyldecahydro-3a,9-propanocyclopenta[8]annulen-8-yl 2-((2-methyl-1-(3-methylbenzamido)propan-2-yl)thio)acetate, C34H49NO5S
  7. Crystal structure of pyridinium bis(naphthalane-2,3-diolato-κ2O,O′)borate monohydrate, C25H20BNO5
  8. Crystal structure of 1,1′-((1E,1′E)-(((ethane-1,2-diylbis(oxy))bis(2,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(naphthalen-2-olato)nickel(II), C72H52N4O8Ni2
  9. The crystal structure of 3-(2-acetyl-4-butyramido-phenoxy)-2-hydroxy-N-isopropylpropan-1-aminium tetraphenylborate, C42H49BN2O4
  10. Crystal structure of 4-bromobenzyl (Z)-N′-(adamantan-1-yl)-4-phenylpiperazine-1-carbothioimidate, C28H34BrN3S
  11. Crystal structure of poly-[(μ6-benzene-1,2,4,5-tetracarboxylato)-(μ2-1,2-bis(imidazol-1-ylmethyl)benzene)dicobalt(II)], Co2C24H16N4O8
  12. Crystal structure of catena-(bis(μ2-1, 2-bis(imidazole-1-ylmethyl)benzene-κN:N′)-dichlororido-nickel(II)), C28H28Cl2N8Ni
  13. Crystal structure of (Z)-1-(1,5-dimethyl-1H-pyrazol-3-yl)-3-hydroxy-3-(4-methoxyphenyl)prop-2-en-1-one, C15H16N2O3
  14. Crystal structure of (Z)-1-(1,5-dimethyl-1H-pyrazol-3-yl)-3-hydroxy-3-phenylprop-2-en-1-one, C14H14N2O2
  15. Crystal structure of (E)-2-(4-hydroxy-3-methoxybenzylidene)-6-methoxy-3,4-dihydronaphthalen-1(2H)-one, C19H18O4
  16. Crystal structure of (Z)-1-(1,5-dimethyl-1H-pyrazol-3-yl)-3-(4-ethoxyphenyl)-3-hydroxyprop-2-en-1-one, C16H18N2O3
  17. Crystal structure of (Z)-1-(1,5-dimethyl-1H-pyrazol-3-yl)-3-hydroxy-3-(p-toly)prop-2-en-1-one, C15H16N2O2
  18. Crystal structure of 1-acetyl-3-(3-chlorophenyl)-5-(4-isopropylphenyl)-4,5-dihydro-(1H)-pyrazole, C20H21ClN2O
  19. The crystal structure of 1-methyl-2,4-dinitro-5-iodoimidazole, C4H3IN4O4
  20. The crystal structure of 4-chloro-3,5-dinitroaniline, C6H4ClN3O4
  21. Crystal structure of N,N-dimethyl-N′-(2-methyl-4-oxo-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-3(4H)-yl)formimidamide, C14H18N4OS
  22. Crystal structure of tetrakis(μ2-acetato-κ2O:O′)-bis[μ3-4-chloro-2,6-bis((methylimino)methyl)phenolato-κ2N,O:O,N′]-(μ4-oxido)tetracopper(II), C28H32Cl2Cu4N4O11
  23. Crystal structure of catena-poly[diaqua-bis(μ2-ethane-1,2-diyl-bis(pyridine-3-carboxylate-κ2N:N′))copper(II)] dinitrate, C28H28CuN6O16
  24. Synthesis and crystal structure of catena-poly[(μ2-nicotinato-κ2O,O′: κ1N)-(nitrato-κ1O)-(bis(2-benzimidazol-ylmethyl)amine-κ3N,N′,N′′)lead(II)], C22H18N7O5Pb
  25. The twinned crystal structure of (4SR)-7-benzyl-2,4,8,8-tetramethyl-7,8-dihydroimidazo[5,1-c][1,2,4]triazine-3,6(2H,4H)-dione, C16H20N4O2
  26. Crystal structure of (Z)-3-hydroxy-3-(4-methoxyphenyl)-1-(pyridin-2-yl)prop-2-en-1-one, C15H13NO3
  27. Crystal structure of 2-amino-4-(2,3-dichlorophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile, C16H12Cl2N2O2
  28. Crystal structure of catena-poly[(μ2-butane-1,4-diyl-bis(pyridine-3-carboxylato-κN))silver(I)] tetrafluoroborate, C16H16AgN2O4BF4
  29. Crystal structure of poly[diaqua-(1,10-phenanthroline-κ2N,N′)-(μ2-2,5-dihydroxytere-phthalato)-bis(μ4-2,5-dihydroxyterephthalato)dicerium(III)], C24H16CeN2O10
  30. Crystal structure of 5,7,4′-trihydroxy-3,8,3′-trymethoxyflavone, C18H16O8
  31. Crystal structure of N-(3,4-dichlorobenzylidene)-4-methylaniline, C14H11Cl2N
  32. Crystal structure of 4-(3-Methoxy-phenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydro-quinoline-3-carboxylic acid ethyl ester, C22H27NO4
  33. Crystal structure of 2-amino-4-(3-fluorophenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile, C16H13FN2O2
  34. Crystal structure of 1,1,(3,4-dihydroxythieno[2,3-b] thiophene-2,5-diyl)bis(2-bromoethanone), C10H6Br2O4S2
  35. The crystal structure of N,N′-(4,4′-oxydibenzyl)-bisisonicotinamide 3.5 hydrate, C24H24N4O6
  36. Crystal structure of catena-poly[hexakis(μ2-chlorido)-hexakis(4-(1H-pyrazol-5-yl)pyridine-κN)tricadmium(II)], Cd3C48H42Cl6N18
  37. Crystal structure of 2-(4-(dimethylamino)phenyl)-1,3-dimethyl-1H-perimidin-3-ium iodide, C21H22I1N3
  38. Crystal structure of 4-(1,3-dimethyl-2,3-dihydro-1H-perimidin-2-yl)benzonitrile, C20H17N3
  39. Crystal structure of tetrakis(μ2-acetato-κ2O:O′)-bis(2,2′-sulfonyldipyrazine-κ1N)dicopper(II), C24H24Cu2N8O12S2
  40. Crystal structure of 1-(4-chlorophenyl)-6,8-diphenyl-1H-pyrazolo[4,3-c]quinoline, C28H18ClN3
  41. Crystal structure of methyl 3-((1-(2-(methoxycarbonyl)benzyl)-1H-1,2,3-triazol-4-yl)methoxy)-2-naphthoate, C24H21N3O5
  42. Crystal structure of (tris(2-pyridylmethyl)amine-κ4N,N′,N′′,N′′′′)-chloranilato-κO,O′-zinc(II) – methanol (1/1), C25H22Cl2N4O5Zn
  43. Crystal structure of 1,1-dimethyl-3-(4-methoxyphenyl)urea, C10H14N2O2
  44. Crystal structure of 4a-Hydroxy-9-(2-nitro-phenyl)-3,4,4a,5,6,7,9,9a-octahydro-2H-xanthene-1,8-dione, C19H19NO6
  45. Crystal structure of chlorido-(η6–1-isopropyl-4-methyl benzene)-(1-(pyridin-2-yl)-N-(p-tolyl)methanimine-κ2N,N′)ruthenium(II) hexafluorophosphate(V), C23H26ClF6N2PRu
  46. Crystal structure of phenyl(2-phenyl-2,3-dihydro-1H-perimidin-2-yl)methanone, C24H18N2O
  47. Crystal structure of (E)-3-methyl-4-((3-(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)-1-phenyl-1H-pyrazol-4-yl)methylene)-1-phenyl-1H-pyrazol-5(4H)-one, C29H23N7O
  48. Crystal structure of 2-(4-(2-butyl-1,3-dioxo-2,3-dihydro-1H-benzo[de]isoquinolin-6-yl)piperazin-1-yl)-2-oxoethyldiethylcarbamodithioate, C27H34N4O3S2
  49. Crystal structure of poly-[diaqua-bis(μ-4,4′-bipyridine-κ2N:N′)cobalt(II)] bis(4-chlorobenzenesulfonate) – 4,4′-bipyridine – water (1/1/2), C42H40Cl2CoN6O10S2
  50. Crystal structure of (η6-benzene)-(N-(2,6-dimethylphenyl)-1-(pyridin-2-yl)methanimine-κ2N,N′)ruthenium(II) perchlorate monohydrate, C20H20Cl2N2O5Ru
  51. Crystal structure of 4,10,16,22-tetrahydroxy-6,12,18,24-tetramethoxy-2,8,14,20-tetraethylphenylresorcin[4]arene – ethyl acetate (1/1), C68H72O10
  52. Crystal structure of chlorido-(N-(2,5-dichlorophenyl)-1-(pyridin-2-yl)methanimine-κ2N,N′)(η6-1-isopropyl-4-methyl benzene) ruthenium (II) tetrafluoroborate, C22H22Cl3N2BF4Ru
  53. Crystal structure of 3-(5-methyl-1-p-tolyl-1H-1,2,3-triazol-4-yl)-1-phenyl-1H-pyrazole-4-carbaldehyde, a rare Z′ = 3 structure, C20H17N5O
  54. Crystal structure of 5-(5-(4-chlorophenyl)-1-phenyl-1H-pyrazol-3-yl)-N-phenyl-1,3,4-thiadiazol-2-amine, C23H16ClN5S
  55. Crystal structure of 7-hydroxy-3-(4-hydroxyphenyl)-4H-1-benzopyran-4-one-N,N-dimethylformamide (1/1), C18H17NO5
  56. Crystal structure of halogen-bonded 2-chloro-1,10-phenanthroline—1,4-diiodotetrafluorobenzene (2/1), C30H14Cl2F4I2N4
  57. Crystal structure of 1-(4,4-dimethyl-2,6-dithioxo-1,3,5-triazinan-1-yl)-3-(diethylaminocarbonyl)thiourea, C11H20N6OS3
  58. Crystal structure of methyl 1-(4-fluorobenzyl)-3-phenyl-1H-pyrazole-5-carboxylate, C18H15FN2O2
  59. Crystal structure of 1,1-dimethyl-3-(4-methylphenyl)urea, C10H14N2O
  60. Crystal structure of yttrium gallium antimonide, Y5Ga1.24Sb2.77
  61. Crystal structure of 2-(bis(4-methoxyphenyl)amino)-2-oxoacetic acid, C16H15NO5
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