Home Crystal structure of 1,1′-methylenebis(3-ethyl-1H-imidazol-3-ium) bis(hexafluorophosphate(V)), C11H18F12N4P2
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Crystal structure of 1,1′-methylenebis(3-ethyl-1H-imidazol-3-ium) bis(hexafluorophosphate(V)), C11H18F12N4P2

  • Wan-Ming Xiong , Jing Chen , Wen Zhao , Yao-Hong Zhou , Chen Jing and Xu-Liang Nie EMAIL logo
Published/Copyright: September 21, 2019

Abstract

C11H18F12N4P2, monoclinic, P21/c (no. 14), a = 14.975(3) Å, b = 9.897(2) Å, c = 13.525(3) Å, β = 105.507(3)°, V = 1931.5(7) Å3, Z = 4, Rgt(F) = 0.0590, wRref(F2) = 0.1843, T = 296(2) K.

CCDC no.: 1940049

The crystal 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:Colorless block
Size:0.20 × 0.12 × 0.12 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.34 mm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω-scans
θmax, completeness:25.5°, >99%
N(hkl)measured, N(hkl)unique, Rint:14106, 3570, 0.043
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2259
N(param)refined:304
Programs:Bruker programs [1], SHELX [2]
Table 2:

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

AtomxyzUiso*/Ueq
N10.64354(18)0.8500(3)0.8126(2)0.0442(7)
N20.64395(17)0.6342(3)0.81526(19)0.0394(6)
N30.74785(18)0.4503(3)0.8840(2)0.0427(7)
N40.87592(19)0.3683(3)0.9774(2)0.0518(8)
P10.85268(7)0.76085(10)0.64287(7)0.0526(3)
P20.41790(7)0.75019(8)0.92372(7)0.0456(3)
F10.94425(19)0.6755(3)0.6774(2)0.1064(10)
F20.76110(15)0.8502(2)0.60531(17)0.0731(7)
F30.86801(19)0.7786(3)0.53140(19)0.0956(9)
F40.83498(18)0.7465(2)0.75284(17)0.0730(7)
F50.91078(18)0.8945(3)0.6781(2)0.0978(9)
F60.7923(2)0.6315(3)0.60493(19)0.0911(8)
F7 a0.3756(11)0.6036(8)0.9142(8)0.093(5)
F8 b0.5149(6)0.679(2)0.9702(8)0.109(7)
F9 c0.4634(16)0.8877(10)0.9366(10)0.137(9)
F10 d0.3219(9)0.810(2)0.8831(8)0.131(8)
F110.4338(2)0.7508(3)0.81344(19)0.0959(10)
F120.4025(2)0.7486(2)1.03569(18)0.0793(8)
F7B e0.4669(18)0.6173(13)0.9337(10)0.153(10)
F8B f0.5103(7)0.823(2)0.9716(8)0.112(8)
F9B g0.3686(14)0.8930(12)0.9073(8)0.107(7)
F10B f0.3234(10)0.682(2)0.8733(7)0.131(11)
C10.6645(2)0.7443(3)0.8722(3)0.0434(8)
H10.68960.74620.94290.052*
C20.6085(2)0.8067(4)0.7140(3)0.0511(9)
H20.58850.86140.65640.061*
C30.6080(2)0.6723(4)0.7151(2)0.0489(9)
H30.58730.61540.65890.059*
C40.6519(2)0.4975(3)0.8549(3)0.0506(9)
H4A0.61500.43750.80310.061*
H4B0.62730.49390.91440.061*
C50.7932(2)0.4091(3)0.9783(3)0.0497(9)
H50.76960.40941.03530.060*
C60.8055(3)0.4347(4)0.8225(3)0.0573(10)
H60.79190.45560.75300.069*
C70.8845(3)0.3840(4)0.8796(3)0.0618(10)
H70.93640.36290.85730.074*
C80.6570(3)0.9904(4)0.8483(4)0.0737(12)
H8A0.64720.99660.91620.088*
H8B0.61141.04740.80260.088*
C90.7503(3)1.0400(4)0.8521(4)0.0947(17)
H9A0.79560.98530.89880.142*
H9B0.75621.13210.87520.142*
H9C0.76011.03490.78490.142*
C100.9460(3)0.3124(4)1.0663(3)0.0715(12)
H10A1.00710.34181.06350.086*
H10B0.93510.34751.12900.086*
C110.9437(4)0.1650(5)1.0687(5)0.128(3)
H11A0.88890.13581.08660.192*
H11B0.99760.13231.11880.192*
H11C0.94320.13011.00230.192*
  1. aOccupancies: a = 0.54(2), b = 0.52(2), c = 0.51(2), d = 0.51(3), e = 0.46(2), f = 0.48(2), g = 0.49(2), h = 0.49(3).

Source of materials

1-Ethylimidazole (9.61 g, 0.1 mol) was dissolved in methylbenzene (20 mL), 1,2-dibromomethane (8.70 g, 0.05 mol) was quickly added under stirring. The mixture first reacted at 60 °C for 10 min, and then heated to 110 °C for 8 h. After the reaction completed (monitored by TLC), a white solid was produced after cooled slowly. The resulting suspension was filtered, crushed and washed with ethyl acetate and diethyl ether 3 times respectively. The white powder intermediates (C1EM—Br) dryed in vacuo (15.56 g, yield 85%). Then the intermediates (C1EM—Br) (1.10 g, 0.003 mol), potassium hexafluoro phosphate (1.10 g, 0.006 mol) was dissolved in water (20 mL). The mixture stirred well for 12 h at 85 °C and then cooled slowly. Then crystals suitable for X-ray analysis were obtained.

Experimental details

All H atoms were included in calculated positions and refined as riding atoms, with C—H = 0.90–0.97 Å with Uiso(H) = 1.5 Ueq(C) for methyl H atoms and 1.2 Ueq(C) for all other H atoms. One of the two hexafluorophosphate anions schows a disorder (cf. the figure; Table 2)

Comment

Ionic liquid, as a new type of environmentally friendly solvent and liquid acid base catalyst, owing to the advantages of adjustable structure, high catalytic efficiency, mild conditions, and can be recycled, etc., has been widely used in catalytic science, electrochemistry, environmental science, extraction and separation, biomass energy, resource conversion and other fields [3], [4], [5]. Because of the unique physical and chemical properties of ionic liquids, ionic liquids have the unique potential advantages of biodiesel preparation. In recent years, various functional ionic liquids have been synthesized, and have been used to prepare biodiesel highly efficiently and environmental friendly [6], [7]. It was found that dinuclear alkaline ionic liquid bis-(3-methyl-1-imidazolium-)ethylene dihydroxide([MC2]OH) shows excellent catalytic efficiency, the highest conversion rate of cotton seed oil was up to 98.5%, and the stability and separation effect of the catalyst was very ideal [8].

Recently, our group still focused on biodiesel catalysis in ionic liquids [9], [10] and reported four related crystal structures [11], [12], [13], [14]. In order to find an ionic liquid catalyst with better catalytic efficiency, we were engaged in synthesizing the ionic liquid catalyst with imidazole.

Bond lengths and angles within the imidazole ring are very similar to those given in the literature for diimidazole ionic liquid [14]. The title structure consists of one C1EM2+ 1,1′-methylenebis(3-ethyl-1H-imidazol-3-ium) cation and two PF6 anions (cf. the figure). Two cationic 1-ethylimidazolium rings were bound to the both sides of methylene group. The dihedral angle of two imidazole rings is 74.67(1)°. The torsion angles of C4—N2—C2—C3 and C4—N3—C6—C7 are 176.0(3)° and 177.3(4)°, respectively.

Acknowledgement

X-ray data were collected at Instrumental Analysis Center Nanchang Hangkong University, Nanchang, 330063, People’s Republic of China.

This work was supported by the National Natural Science Foundation of China (No. 31760193, 31760068) and the Research Foundation of Educational Department of Jiangxi Province [GJJ160382, 160379].

References

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Received: 2019-06-24
Accepted: 2019-07-24
Published Online: 2019-09-21
Published in Print: 2019-12-18

©2019 Wan-Ming Xiong et al., published by De Gruyter, Berlin/Boston

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

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  71. Crystal structure of 3-acetyl-6-bromo-4-hydroxy-2H-chromen-2-one, C11H7BrO4
  72. Crystal structure of N′2,N′6-bis((E)-1-(pyrazin-2-yl)ethylidene)pyridine-2,6-dicarbohydrazide — methanol (1/2), C21H25N9O4
  73. The crystal structure of 3-nitro-4-(p-tolylamino)-2H-chromen-2-one, C16H12N2O4
  74. The crystal structure of 1,2-bis((4-methoxyphenyl)ethynyl)benzene, C24H18O2
  75. Crystal structure of a low-temperature (100 K) polymorph of catena-poly[(μ2-4,4′-bipyridine-κ2N,N′)-bis(O,O′-diethyldithiophosphato-κ1S)zinc(II)], C18H28N2O4P2S4Zn
  76. The pseudosymmetric low temperature polymorph of catena-poly[(μ2-4,4′-bipyridyl-κN,N′)-bis(O,O′-diethyldithiophosphato-κS)-cadmium(II)], {C18H28CdN2O4P2S4}n
  77. Crystal structure of 3-iodophthalic acid, C8H5IO4
  78. The crystal structure of tert-butyl (tert-butoxy(oxo)methyl)(5-bromo-2-fluorophenyl)carbamate, C16H21BrFNO4
  79. The crystal structure of bis(μ2-5,7-dichloroquinolin-8-olato-κ3N,O:O)-tetrakis(5,7-dichloroquinolin-8-olato-κ2N,O)bis(methanol-κ1O)dieuropium(III) — toluene (1/1), C63H39Cl12Eu2N6O8
  80. Crystal structure of dichlorido-(N′-(1-(3-ethylpyrazin-2-yl)ethylidene)-4-methoxybenzohydrazide-κ3N,N′,O)cadmium(II), C16H18N4O2Cl2Cd
  81. A redetermination of the crystal structure of catena-poly[(bis(O,O′-isopropyl dithiophosphato-κ2S,S′)-(μ2-1,2-bis(3-pyridylmethylene)hydrazine-κ2N,N′)cadmium(II)], {C24H38CdN4O4P2S4}n
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