Crystal structure of 8-iodo­quinolinium tetra­chlorido­aurate(III)

Benard O Onserio; Sem Raj Tamang; James D Hoefelmeyer

doi:10.1107/S2056989015022574

. 2015 Dec 12;71(Pt 12):m261–m262. doi: 10.1107/S2056989015022574

Crystal structure of 8-iodoquinolinium tetrachloridoaurate(III)

Benard O Onserio ^a, Sem Raj Tamang ^a, James D Hoefelmeyer ^a,^*

PMCID: PMC4719864 PMID: 26870455

Abstract

The structure of the title salt, (C₉H₇IN)[AuCl₄], is comprised of planar 8-iodoquinolinium cations (r.m.s. deviation = 0.05 Å) and square-planar tetrachloridoaurate(III) anions. The asymmetric unit contains one 8-iodoquinolinium cation and two halfs of [AuCl₄]⁻ anions, in each case with the central Au^III atom located on an inversion center. Intermolecular halogen–halogen contacts were found between centrosymmetric pairs of I [3.6178 (4) Å] and Cl atoms [3.1484 (11), 3.3762 (13), and 3.4935 (12) Å]. Intermolecular N—H⋯Cl and C—H⋯Cl hydrogen bonding is also found in the structure. These interactions lead to the formation of a three-dimensional network. Additionally, there is an intramolecular N—H⋯I hydrogen bond between the aromatic iminium and iodine. There are no aurophilic interactions or short contacts between I and Au atoms, and there are no notable π-stacking interactions between the aromatic cations.

Keywords: crystal structure, 8-iodoquinolinium cation, tetrachloridoaurate anion, salt structure

Related literature

There are only two reported structures containing the 8-iodoquinolinium cation, viz. 8-iodoquinolinium chloride dihydrate (Son & Hoefelmeyer, 2008a ▸) and 8-iodoquinolinium triiodide tetrahydrofuran solvate (Son & Hoefelmeyer, 2008b ▸). Recently, the zwitterionic 8-iodoquinoline N-oxide was also reported (Hwang et al., 2014 ▸). graphic file with name e-71-0m261-scheme1.jpg

Experimental

Crystal data

(C₉H₇IN)[AuCl₄]
M _r = 594.82
Triclinic,
a = 7.6299 (5) Å
b = 7.8609 (5) Å
c = 11.7125 (7) Å
α = 80.160 (1)°
β = 78.143 (1)°
γ = 85.178 (1)°
V = 676.52 (7) Å³
Z = 2
Mo Kα radiation
μ = 13.92 mm⁻¹
T = 100 K
0.16 × 0.11 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.174, T _max = 0.573
6855 measured reflections
2482 independent reflections
2407 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.040
S = 1.04
2482 reflections
152 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT (Bruker, 2009 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: Mercury (Macrea et al., 2006 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015022574/wm5236sup1.cif

e-71-0m261-sup1.cif^{(212.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022574/wm5236Isup2.hkl

e-71-0m261-Isup2.hkl^{(198.7KB, hkl)}

Click here for additional data file.^{(1.4KB, rtf)}

Supporting information file. DOI: 10.1107/S2056989015022574/wm5236Isup3.rtf

Click here for additional data file.^{(1.8MB, tif)}

x y z x y z x y z x y z x z x y z x y z . DOI: 10.1107/S2056989015022574/wm5236fig1.tif

The expanded asymmetric unit of the crystal shown with intermolecular halogen⋯halogen contacts and hydrogen bonds as dashed lines. [Symmetry codes: (i) 1 − x, 2 − y, 2 − z; (ii) 2 − x, −y, 1 − z; (iii) 1 − x, −1 − y, 1 − z; (iv) −x, −y − 1, −z; (v) x + 1, y + 1, z + 1; (vi) x + 1, y + 1, z; (vii) −x + 2, −y, −z + 1.]

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S2056989015022574/wm5236fig2.tif

The centrosymmetric unit cell of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S2056989015022574/wm5236fig3.tif

Examination of the nearest distances (Å) between iodine and Au—Cl bond centroids. These distances are beyond the sum of the van der Waals radii of the atoms.

CCDC reference: 1438910

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H99⋯Cl3ⁱ	0.80 (5)	2.62 (5)	3.287 (3)	142 (4)
N1—H99⋯I1	0.80 (5)	2.81 (5)	3.264 (3)	118 (4)
C2—H2⋯Cl1ⁱⁱ	0.93	2.79	3.493 (4)	133
C3—H3⋯Cl1ⁱⁱⁱ	0.93	2.81	3.722 (4)	168

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

Purchase of the X-ray diffractometer was made possible by funding from the National Science Foundation (grant No. EPS-0554609).

supplementary crystallographic information

S1. Synthesis and crystallization

In a 4 ml vial, HAuCl₄·3H₂O (0.12 g, 0.33 mmol), 8-iodoquinoline (0.10 g, 0.39 mmol) and acetonitrile (2 ml) were combined and sonicated for 30 minutes. The 4 ml vial was placed in a 20 ml vial with 5 ml diethylether. Diffusion of the ether vapor into the solution within the smaller vial gave yellow-green crystals, mostly with a cuboid-like form.

S2. Refinement

C-bound H atoms were placed in ideal positions and refined as riding atoms (C—H = 0.93 Å; U_iso(H) = 1.2U_eq(H)). The H atom bound to the N atom was located from a difference map and refined freely. The highest remaining electron density peak was located 0.20 Å from H6. A transmission factor of 0.62 was calculated using the ratio of T_min (0.4593) to T_max (0.7452) taken from the absorption correction output file, whereas experimental T_min (0.174) and T_max (0.573) give a transmission factor of 0.30.