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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2077.
Published online 2008 October 4. doi:  10.1107/S1600536808031516
PMCID: PMC2959684

8-Iodo­quinolinium triiodide tetra­hydro­furan solvate

Abstract

The title compound, C9H7IN+·I3 ·C4H8O, was synthesized from 8-amino­quinoline using the Sandmeyer reaction. The 8-iodo­quinolinium cation is essentially planar and the triiodide ion is almost linear. N—H(...)O hydrogen bonds, and inter­molecular I(...)I [3.7100 (5) Å] and I(...)H inter­actions, between the cation, anion and solvent mol­ecules result in the formation of sheets oriented parallel to the (An external file that holds a picture, illustration, etc.
Object name is e-64-o2077-efi1.jpg03) plane. Between the sheets, 8-iodo­quinolinium and triiodide ions are stacked alternately, with I(...)C distances in the range ~3.8–4.0 Å.

Related literature

For the synthesis, see: Lucas & Kennedy (1943 [triangle]); Sandmeyer (1884 [triangle]). For related structures, see: Son & Hoefelmeyer (2008 [triangle]); Svensson & Kloo (2003 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2077-scheme1.jpg

Experimental

Crystal data

  • C9H7IN+·I3 ·C4H8O
  • M r = 708.86
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2077-efi2.jpg
  • a = 7.8674 (4) Å
  • b = 17.6510 (9) Å
  • c = 13.1465 (7) Å
  • β = 90.343 (1)°
  • V = 1825.59 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.82 mm−1
  • T = 100 (2) K
  • 0.57 × 0.36 × 0.27 mm

Data collection

  • Bruker SMART APEXII diffractometer
  • Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 2008 [triangle]), T min = 0.111, T max = 0.262
  • 18253 measured reflections
  • 3363 independent reflections
  • 3291 reflections with I > 2σ(I)
  • R int = 0.079

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.111
  • S = 0.97
  • 3363 reflections
  • 172 parameters
  • H-atom parameters constrained
  • Δρmax = 0.55 e Å−3
  • Δρmin = −2.63 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031516/ci2653sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031516/ci2653Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by funding from the South Dakota 2010 Initiative, Center for Research and Development of Light-Activated Materials. Purchase of the X-ray diffractometer was made possible with funds from the National Science Foundation (EPS-0554609).

supplementary crystallographic information

Comment

8-Iodoquinoline is a starting material for the synthesis of 8-substituted quinoline derivatives. The molecule 8-iodoquinoline was synthesized starting from 8-aminoquinoline using the Sandmeyer reaction (Sandmeyer, 1884), similar to the synthesis of iodobenzene (Lucas & Kennedy, 1943). During its synthesis, two 8-iodoquinolinium salt crystals, 8-iodoquinolinium chloride dihydrate (Son & Hoefelmeyer, 2008) and 8-iodoquinolinium triiodide.THF were isolated. The synthesis, characterization and crystal structure of 8-iodoquinolinium triiodide.THF are reported here.

The 8-iodoquinolinium cation is essentially planar (Fig. 1). The C9—C8—I1 angle is 121.9 (3) °, slightly larger than the ideal value of 120°. A weak intermolecular interaction is present between atom I1 of the cation and I2 of the triiodide anion; I1···I2(1 + x, y, 1 + z) = 3.7100 (5) Å. The geometry of triiodide is almost linear, with I2—I3 = 2.9416 (8) Å, I3—I4 = 2.9014 (8) Å and I4—I3—I2 angle is 177.445 (17)°. The shape resembles symmetric, free triiodide that typically occurs in the presence of bulky cations (Svensson & Kloo, 2003).

The 8-iodoquinolinium cation, I3- and THF form an extended sheet (Fig. 2) parallel to the (1 0 3) plane through I1···I2, I3···H4 (3.15 Å) and I4···H5 (3.09 Å) interactions and N—H···O hydrogen bonds (Table 1). Between the sheets, 8-iodoquinolinium and I3- ions are stacked alternately, with the I2···C2ii, I3···C8ii and I3···C9ii distances being 3.742 (5), 3.840 (4) and 3.838 (4) Å, respectively [symmetry code: (ii) -1/2 + x, 1/2 - y, -1/2 + z].

Experimental

In a 500 ml beaker, a mixture of 8-aminoquinoline (10 g, 0.069 mol) and water (50 ml) was heated with stirring. While cooling the mixture in an ice bath, concentrated HCl (50 ml) was added to form a red solution. NaNO2 (7.8 g, 0.113 mol) was dissolved in water (50 ml) and cooled in an ice bath separately. NaNO2 solution was slowly transferred to the 8-aminoquinoline solution. Light brown precipitate formed during the addition step but eventually disappeared to form a reddish transparent solution. KI (17.9 g, 0.108 mol) was dissolved in water (25 ml) and added to the reaction mixture. Bubbles and brownish vapor evolved during addition. The solution turned to dark brown with black precipitate. The solution was refluxed with a watch glass on top of the beaker, and it became reddish brown with formation of a heavy organic layer; the black precipitate remained. After cooling and standing overnight, golden brown crystals of 8-iodoquinolinium chloride dihydrate had formed spontaneously in the solution. The mixture was neutralized upon addition of NaOH solution, which led to dissolution of the golden brown crystals and retention of the black precipitate. The liquid portion was separated from the black precipitate. 8-Iodoquinoline could be recoverd from the liquid portion upon extraction with toluene. The black precipitate was dissolved in THF and crystallized by pentane vapor diffusion to obtain the crystal of 8-iodoquinolinium triiodide.THF [yield: 7.14 g (15%), m.p. 366–368 K]. 1H NMR (acetone-d): 7.647–7.725 (dd, 1H, quin CH), 8.237–8.305 (dd, 1H, quin CH), 8.339–8.385 (dd, 1H, quin CH), 8.559–8.602 (dd, 1H, quin CH), 9.260–9.309 (dd, 1H, quin CH), 9.380–9.415 (dd, 1H, quin CH), 12.999 (br, 1H, NH). 13C NMR (acetone-d): 91.517 (quin C8), 124.089 (quin CH), 130.558 (quin C9/10), 130.817 (quin CH), 132.183 (quin CH), 138.064 (quin C9/10), 146.463 (quin CH), 147.614 (quin CH), 149.842 (quin CH). Elemental analysis result suggests that about 75% of THF depleted during storage. Analysis calculated for C13H15I4NO: C 22.03, H 2.13, N 1.98%; found: C 19.30, H 1.32, N 2.19%.

Refinement

H atoms were positioned geometrically (N—H = 0.88 Å and C—H = 0.93 Å) and allowed to ride on the parent atoms with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
Asymmetric unit of 8-iodoquinolinium triiodide.THF. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Crystal structure of 8-iodoquinolinium triiodide.THF, viewed along the c axis. Dotted lines denote hydrogen bonding and close contacts. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C9H7IN+·I3·C4H8OF(000) = 1280
Mr = 708.86Dx = 2.579 Mg m3
Monoclinic, P21/nMelting point: 367 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 7.8674 (4) ÅCell parameters from 9984 reflections
b = 17.6510 (9) Åθ = 2.8–25.4°
c = 13.1465 (7) ŵ = 6.82 mm1
β = 90.343 (1)°T = 100 K
V = 1825.59 (16) Å3Block, metallic violet
Z = 40.57 × 0.36 × 0.27 mm

Data collection

Bruker SMART APEXII diffractometer3363 independent reflections
Radiation source: fine-focus sealed tube3291 reflections with I > 2σ(I)
graphiteRint = 0.079
ω scansθmax = 25.4°, θmin = 1.9°
Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 2008) or (SADABS; Bruker, 2003)???h = −9→9
Tmin = 0.111, Tmax = 0.262k = −21→21
18253 measured reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 0.98w = 1/[σ2(Fo2) + (0.0437P)2 + 2.836P] where P = (Fo2 + 2Fc2)/3
3363 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.55 e Å3
0 restraintsΔρmin = −2.63 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
C20.2020 (7)0.3301 (2)0.9044 (4)0.0231 (10)
H20.24250.38070.90940.028*
C30.0503 (6)0.3161 (3)0.8562 (4)0.0265 (10)
H3−0.01380.35650.82750.032*
C4−0.0077 (5)0.2427 (3)0.8500 (3)0.0229 (9)
H4−0.11340.23220.81770.027*
C50.0356 (6)0.1062 (3)0.8839 (3)0.0234 (9)
H5−0.07060.09430.85310.028*
C60.1379 (6)0.0497 (3)0.9214 (3)0.0231 (9)
H60.1035−0.00170.91550.028*
C70.2952 (6)0.0678 (3)0.9690 (3)0.0221 (9)
H70.36400.02810.99540.027*
C80.3493 (5)0.1402 (3)0.9775 (3)0.0181 (8)
C90.2463 (5)0.1992 (3)0.9385 (3)0.0167 (8)
C100.0900 (6)0.1829 (3)0.8917 (3)0.0197 (9)
C110.5434 (6)0.3891 (3)0.1252 (3)0.0233 (9)
H11A0.60240.34860.16370.028*
H11B0.42970.39720.15510.028*
C120.6463 (6)0.4619 (3)0.1272 (4)0.0250 (9)
H12A0.72120.46380.18790.030*
H12B0.57080.50680.12750.030*
C130.7520 (6)0.4587 (3)0.0285 (3)0.0243 (9)
H13A0.72690.5028−0.01580.029*
H13B0.87530.45780.04390.029*
C140.6948 (5)0.3849 (3)−0.0216 (3)0.0237 (9)
H14A0.68850.3907−0.09650.028*
H14B0.77490.3433−0.00520.028*
I10.58420 (4)0.162595 (15)1.04875 (2)0.02127 (14)
I2−0.00026 (4)0.166821 (16)0.18354 (2)0.02404 (14)
I30.05172 (4)0.330240 (15)0.21544 (2)0.01836 (14)
I40.11961 (4)0.488485 (17)0.25933 (2)0.02294 (14)
N10.2941 (4)0.2734 (2)0.9445 (3)0.0182 (7)
H10.38970.28450.97620.022*
O10.5292 (4)0.36930 (18)0.0195 (2)0.0210 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C20.026 (3)0.017 (2)0.027 (2)−0.0006 (16)0.003 (2)0.0016 (16)
C30.022 (2)0.034 (3)0.023 (2)0.012 (2)0.0013 (18)0.005 (2)
C40.015 (2)0.035 (3)0.018 (2)−0.0014 (18)−0.0022 (15)−0.0022 (18)
C50.022 (2)0.029 (2)0.020 (2)−0.0101 (19)0.0027 (16)−0.0036 (18)
C60.030 (2)0.017 (2)0.022 (2)−0.0091 (18)0.0006 (17)−0.0029 (17)
C70.025 (2)0.021 (2)0.020 (2)0.0005 (17)0.0047 (17)−0.0024 (17)
C80.0144 (19)0.025 (2)0.0151 (19)0.0012 (18)0.0005 (15)−0.0010 (17)
C90.0149 (19)0.022 (2)0.0128 (17)0.0022 (17)0.0027 (14)0.0011 (16)
C100.022 (2)0.022 (2)0.014 (2)−0.0064 (17)0.0038 (16)−0.0040 (17)
C110.022 (2)0.029 (2)0.019 (2)−0.0016 (18)0.0018 (16)−0.0011 (18)
C120.022 (2)0.023 (2)0.030 (2)−0.0029 (18)−0.0053 (18)−0.0038 (19)
C130.020 (2)0.026 (2)0.027 (2)−0.0063 (19)−0.0055 (17)0.0035 (19)
C140.017 (2)0.032 (3)0.022 (2)−0.0001 (18)0.0041 (17)0.0014 (18)
I10.0187 (2)0.0219 (2)0.0232 (2)0.00115 (10)−0.00448 (14)0.00111 (10)
I20.0264 (2)0.0248 (2)0.0209 (2)−0.00137 (10)0.00150 (15)−0.00241 (10)
I30.0143 (2)0.0245 (2)0.0163 (2)0.00172 (9)−0.00029 (13)0.00112 (9)
I40.0240 (2)0.0216 (2)0.0232 (2)0.00220 (10)−0.00198 (14)0.00159 (10)
N10.0137 (17)0.024 (2)0.0172 (17)0.0021 (14)0.0010 (13)−0.0015 (14)
O10.0182 (15)0.0214 (16)0.0233 (15)−0.0030 (12)0.0010 (12)−0.0034 (13)

Geometric parameters (Å, °)

C2—N11.343 (6)C9—C101.401 (7)
C2—C31.370 (8)C11—O11.436 (5)
C2—H20.95C11—C121.519 (6)
C3—C41.375 (7)C11—H11A0.99
C3—H30.95C11—H11B0.99
C4—C101.415 (7)C12—C131.547 (6)
C4—H40.95C12—H12A0.99
C5—C61.372 (7)C12—H12B0.99
C5—C101.423 (6)C13—C141.527 (6)
C5—H50.95C13—H13A0.99
C6—C71.419 (7)C13—H13B0.99
C6—H60.95C14—O11.440 (5)
C7—C81.352 (6)C14—H14A0.99
C7—H70.95C14—H14B0.99
C8—C91.413 (6)I2—I32.9430 (4)
C8—I12.104 (4)I3—I42.9011 (4)
C9—N11.364 (6)N1—H10.88
N1—C2—C3120.9 (4)O1—C11—H11A110.7
N1—C2—H2119.5C12—C11—H11A110.7
C3—C2—H2119.5O1—C11—H11B110.7
C2—C3—C4119.0 (4)C12—C11—H11B110.7
C2—C3—H3120.5H11A—C11—H11B108.8
C4—C3—H3120.5C11—C12—C13104.1 (4)
C3—C4—C10120.0 (4)C11—C12—H12A110.9
C3—C4—H4120.0C13—C12—H12A110.9
C10—C4—H4120.0C11—C12—H12B110.9
C6—C5—C10119.4 (4)C13—C12—H12B110.9
C6—C5—H5120.3H12A—C12—H12B109.0
C10—C5—H5120.3C14—C13—C12103.6 (3)
C5—C6—C7120.1 (4)C14—C13—H13A111.0
C5—C6—H6119.9C12—C13—H13A111.0
C7—C6—H6119.9C14—C13—H13B111.0
C8—C7—C6121.6 (4)C12—C13—H13B111.0
C8—C7—H7119.2H13A—C13—H13B109.0
C6—C7—H7119.2O1—C14—C13105.4 (3)
C7—C8—C9119.1 (4)O1—C14—H14A110.7
C7—C8—I1119.3 (3)C13—C14—H14A110.7
C9—C8—I1121.6 (3)O1—C14—H14B110.7
N1—C9—C10117.6 (4)C13—C14—H14B110.7
N1—C9—C8121.9 (4)H14A—C14—H14B108.8
C10—C9—C8120.5 (4)I4—I3—I2175.753 (14)
C9—C10—C4119.4 (4)C2—N1—C9123.0 (4)
C9—C10—C5119.3 (5)C2—N1—H1118.5
C4—C10—C5121.3 (4)C9—N1—H1118.5
O1—C11—C12105.2 (3)C11—O1—C14104.5 (3)
N1—C2—C3—C40.5 (7)C8—C9—C10—C50.1 (6)
C2—C3—C4—C10−0.9 (7)C3—C4—C10—C9−0.4 (7)
C10—C5—C6—C71.1 (7)C3—C4—C10—C5−178.2 (4)
C5—C6—C7—C8−0.9 (7)C6—C5—C10—C9−0.7 (6)
C6—C7—C8—C90.3 (6)C6—C5—C10—C4177.1 (4)
C6—C7—C8—I1−179.9 (3)O1—C11—C12—C13−25.5 (4)
C7—C8—C9—N1−179.8 (4)C11—C12—C13—C141.4 (5)
I1—C8—C9—N10.4 (5)C12—C13—C14—O123.0 (4)
C7—C8—C9—C100.0 (6)C3—C2—N1—C91.4 (7)
I1—C8—C9—C10−179.8 (3)C10—C9—N1—C2−2.7 (6)
N1—C9—C10—C42.2 (6)C8—C9—N1—C2177.1 (4)
C8—C9—C10—C4−177.7 (4)C12—C11—O1—C1441.1 (4)
N1—C9—C10—C5−180.0 (4)C13—C14—O1—C11−40.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···I10.882.803.297 (4)117
N1—H1···O1i0.881.942.690 (5)142

Symmetry codes: (i) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2653).

References

  • Bruker (2006). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Lucas, H. J. & Kennedy, E. R. (1943). Org. Synth. Coll. Vol. II, pp. 351–352.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Sandmeyer, T. (1884). Ber. Dtsch. Chem. Ges.17, 1633–1635.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Son, J.-H. & Hoefelmeyer, J. D. (2008). Acta Cryst. E64, o2076. [PMC free article] [PubMed]
  • Svensson, P. H. & Kloo, L. (2003). Chem. Rev.103, 1649–1684. [PubMed]

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