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BY-NC-ND 4.0 license Open Access Published by De Gruyter (O) June 9, 2018

Crystal structure of 1-heptylpyridazin-1-ium iodide, C11H19N2I

Musa A. Said EMAIL logo , Mohamed R. Aouad , Saud M. Almutairi , David L. Hughes EMAIL logo and Mouslim Messali EMAIL logo

Abstract

C11H19N2I, triclinic, P1̄ (no. 2), a = 5.7074(3) Å, b = 8.9811(5) Å, c = 14.4312(8) Å, α = 100.989(4)°, β = 94.768(4)°, γ = 97.327(4)°, V = 715.83(7) Å3, Z = 2, Rgt(F) = 0.0386, wRref(F2) = 0.0913, T = 295(2) K.

CCDC no.: 1836644

The asymmetric unit of 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:Light yellow prism
Size:0.35 × 0.11 × 0.10 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:2.21 mm−1
Diffractometer, scan mode:Xcalibur 3/Sapphire3, Thin slice φ and ω-scans
θmax, completeness:27.5°, >99%
N(hkl)measured, N(hkl)unique, Rint:11282, 3285, 0.041
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2794
N(param)refined:127
Programs:CrysAlis [1], SHELX [2], [3], WinGX [4]
Table 2:

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

AtomxyzUiso*/Ueq
I0.90826(4)0.75400(3)0.58391(2)0.06733(12)
N10.5799(5)0.6420(3)0.34437(19)0.0579(7)
N20.7257(5)0.7389(4)0.3100(2)0.0685(8)
C30.6800(7)0.8800(4)0.3215(3)0.0741(10)
H30.78120.95040.29840.089*
C40.4921(8)0.9308(5)0.3657(3)0.0754(11)
H40.46591.03220.37180.090*
C50.3474(7)0.8281(6)0.3997(3)0.0766(11)
H50.21690.85660.42940.092*
C60.3969(6)0.6810(5)0.3895(2)0.0676(9)
H60.30260.60890.41410.081*
C110.6434(8)0.4853(5)0.3325(3)0.0798(11)
H11A0.80120.49030.36480.096*
H11B0.53280.42340.36240.096*
C120.6393(10)0.4109(6)0.2323(4)0.0920(14)
H12A0.68960.31100.22890.110*
H12B0.75200.47200.20270.110*
C130.3966(9)0.3914(6)0.1775(3)0.1012(15)
H13A0.35470.49200.17500.121*
H13B0.28120.34120.21160.121*
C140.3793(10)0.2984(8)0.0763(4)0.1124(17)
H14A0.49290.34950.04190.135*
H14B0.42390.19840.07870.135*
C150.1357(11)0.2765(9)0.0219(4)0.126(2)
H15A0.02180.22740.05700.151*
H15B0.09270.37650.01850.151*
C160.1157(14)0.1844(13)−0.0753(5)0.160(3)
H16A0.16250.0851−0.07250.192*
H16B0.22480.2350−0.11160.192*
C17−0.1308(14)0.1613(12)−0.1255(5)0.184(4)
H17A−0.13410.1008−0.18830.275*
H17B−0.23920.1092−0.09070.275*
H17C−0.17690.2591−0.12980.275*

Source of materials

The title ionic liquid was prepared according to a method reported earlier [5, 6] . To a solution of pyridazine (1 g, 12.5 mmol in 10 mL of toluene) was added dropwise 1-iodoheptane (2.825 g, 12.5 mmol) and the mixture was placed in a closed container and exposed to irradiation for 5 hours at room temperature using a sonication bath. Completion of the reaction was marked by the precipitation of a solid from the initially obtained clear and homogenous mixture in toluene. The pyridazinium-based ionic liquid is isolated by filtration and washed three times with ethyl acetate to remove any unreacted starting materials and solvent. Finally the 1-heptylpyridazin-1-ium iodide was dried at a reduced pressure to remove all volatile organic compounds to produce a yellow powder. (Yield 77%, m.p. 89–92 °C). Crystals were obtained from a mixture of dichloromethane and n-hexane (1:2). Elemental analysis: Anal. Calc. for C11H19IN2: C, 43.15%; H, 6.25%; N, 9.15%; Found: C, 43.10%; H, 6.19%; N, 9.11%. 1H NMR (DMSO, 400 MHz): δ = 0.81 (t, 3H), 1.23–1.30 (m, 8H), 1.99 (quintet, 2H), 4.83 (t, 2H), 7.65 (t, 1H), 8.77 (t, 1H), 9.66 (d, 1H), 10.02 (d, 1H); 13C NMR (DMSO, 100 MHz): δ = 14.4 (CH3), 22.6 (CH2), 25.8 (CH2), 28.8 (CH2), 29.9 (CH2), 31.7 (CH2), 65.0 (CH2), 136.5 (CH), 137.0 (CH), 150.3 (CH), 155.0 (CH).

Experimental details

The diffraction data were processed using the CrysAlisPro-CCD and -RED [1] programs. The structure was determined by the intrinsic phasing routines in the SHELXT program [2] and refined by full-matrix least-squares methods, on F2’s, in SHELXL [3]. Hydrogen atoms were included in idealized positions and their Uiso values were set to ride on the Ueq values of the parent carbon atoms.

Comment

Ionic liquids (ILs) have received increased attention in recent years due to their outstanding and unique properties, such as negligible vapor pressure, non-volatility, non-flammability, excellent thermal stability, and high electrical conductivity [7]. Based on these characteristics, a broad range of applications of ILs has been reported in a variety of different fields, including the electrodeposition of metals and the development of corrosion inhibitors [8], [9], [10]. Furthermore, a number of biological activities of pyridazine derivatives have been reported including anticancer, antituberculosis, antihypertensive and antimicrobial activities [11], [12], [13].

The asymmetric unit of the title crystal structure contains one cation and the iodide anion. Bond lengths and angles in the organic cation are in the expected ranges. The heptyl group has an all-trans arrangement and is aligned about C(11) with a cis N(2)—N(1)—C(11)—C(12) torsion angle of −61.6(5)°; the N(2)—N(1)—C(11)—H(11b) angle is trans at 177.2°.

The iodide ion lies over the pyridazinium ring at 3.686 Å from N(1). There are also five short H⋯I contacts in the range 3.04–3.15 Å, to neighboring cations, forming ‘weak’ C—H⋯I hydrogen bonds, Table 3, which link ions in planes parallel to the ab plane, at z ∼ ½. All the short inter-ion distances involve the iodide ion; the heptyl chains lie parallel but do not show any close contacts between chains. In a recent work from our group, we found a bromide anion linked to a pyridinium cation by a C—H⋯Br hydrogen bond with the H⋯Br distance 2.89 Å; there were four further short C—H⋯Br contacts, to three separate cations, at distances ranging from ca 3.07 to 3.11 Å [14].

Table 3:

‘Weak’ hydrogen bonds, in Ångstroms and degrees.

D–H⋯Ad(D–H)d(H⋯A)d(D⋯A)<(DHA)
C(3)–H(3)⋯I#10.933.113.739(4)126.8
C(4)–H(4)⋯I#20.933.083.861(4)143.2
C(5)–H(5)⋯I#30.933.153.892(4)137.8
C(11)–H(11A)⋯I#40.973.083.808(4)133.4
C(11)–H(11B)⋯I#50.973.043.985(5)164.8
  1. Symmetry transformations used to generate equivalent atoms:

  2. #1 : 2−x, 2−y, 1−z  #2 : 1−x, 2−y, 1−z  #3 : x−1, y, z

  3. #4 : 2−x, 1−y, 1−z  #5 : 1−x, 1−y, 1−z.

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Received: 2018-03-01
Accepted: 2018-04-12
Published Online: 2018-06-09
Published in Print: 2018-07-26

©2018 Musa A. Said et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

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