Literature DB >> 26870455

Crystal structure of 8-iodo-quinolinium tetra-chlorido-aurate(III).

Benard O Onserio¹, Sem Raj Tamang¹, James D Hoefelmeyer¹.

Abstract

The structure of the title salt, (C9H7IN)[AuCl4], is comprised of planar 8-iodo-quinolinium cations (r.m.s. deviation = 0.05 Å) and square-planar tetra-chlorido-aurate(III) anions. The asymmetric unit contains one 8-iodo-quinolinium cation and two halfs of [AuCl4](-) anions, in each case with the central Au(III) atom located on an inversion center. Inter-molecular 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]. Inter-molecular N-H⋯Cl and C-H⋯Cl hydrogen bonding is also found in the structure. These inter-actions lead to the formation of a three-dimensional network. Additionally, there is an intra-molecular N-H⋯I hydrogen bond between the aromatic iminium and iodine. There are no aurophilic inter-actions or short contacts between I and Au atoms, and there are no notable π-stacking inter-actions between the aromatic cations.

Entities: Chemical Disease Gene Species

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

Year: 2015 PMID： 26870455 PMCID： PMC4719864 DOI： 10.1107/S2056989015022574

Source DB: PubMed Journal: Acta Crystallogr E Crystallogr Commun

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 ▸).

Experimental

Crystal data

(C9H7IN)[AuCl4] M = 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 Δρmax = 1.19 e Å−3 Δρmin = −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 ▸). Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015022574/wm5236sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022574/wm5236Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S2056989015022574/wm5236Isup3.rtf Click here for additional data file. 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. . 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. . 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

(C₉H₇IN)[AuCl₄]	Z = 2
M_r = 594.82	F(000) = 536
Triclinic, P1	D_x = 2.920 Mg m⁻³
a = 7.6299 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8609 (5) Å	Cell parameters from 5508 reflections
c = 11.7125 (7) Å	θ = 2.6–25.6°
α = 80.160 (1)°	µ = 13.92 mm⁻¹
β = 78.143 (1)°	T = 100 K
γ = 85.178 (1)°	Plate, light green
V = 676.52 (7) Å³	0.16 × 0.11 × 0.04 mm

Bruker APEXII CCD diffractometer	2407 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.024
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 25.4°, θ_min = 1.8°
T_min = 0.174, T_max = 0.573	h = −9→9
6855 measured reflections	k = −9→9
2482 independent reflections	l = −14→14

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.040	w = 1/[σ²(F_o²) + (0.019P)² + 0.5573P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2482 reflections	Δρ_max = 1.19 e Å⁻³
152 parameters	Δρ_min = −0.94 e Å⁻³

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.

	x	y	z	U_iso*/U_eq
I1	0.54637 (3)	0.86196 (3)	0.88748 (2)	0.01671 (7)
Au2	0.0000	0.0000	0.0000	0.01009 (6)
Au1	0.5000	0.0000	0.5000	0.00870 (6)
Cl3	0.07524 (11)	0.00792 (10)	−0.20000 (7)	0.01714 (17)
Cl2	0.20893 (10)	0.01686 (10)	0.47699 (7)	0.01590 (17)
Cl4	0.00376 (12)	−0.29552 (11)	0.02554 (8)	0.01672 (18)
C8	0.5841 (5)	0.6220 (4)	0.8290 (3)	0.0137 (7)
C7	0.4426 (5)	0.5185 (5)	0.8453 (3)	0.0167 (8)
H7	0.3321	0.5507	0.8887	0.020*
C6	0.4621 (5)	0.3624 (5)	0.7968 (3)	0.0201 (8)
H6	0.3655	0.2923	0.8092	0.024*
C5	0.6244 (5)	0.3160 (5)	0.7317 (3)	0.0173 (8)
H5	0.6359	0.2155	0.6982	0.021*
C10	0.7737 (5)	0.4170 (4)	0.7144 (3)	0.0136 (7)
C4	0.9432 (5)	0.3733 (5)	0.6493 (3)	0.0163 (7)
H4	0.9589	0.2741	0.6142	0.020*
N1	0.9009 (4)	0.6662 (4)	0.7494 (3)	0.0146 (6)
C9	0.7541 (5)	0.5716 (5)	0.7656 (3)	0.0134 (7)
Cl1	0.49806 (11)	−0.29443 (10)	0.53814 (8)	0.01473 (17)
C3	1.0864 (5)	0.4757 (5)	0.6369 (3)	0.0172 (8)
H3	1.1983	0.4458	0.5942	0.021*
C2	1.0612 (5)	0.6228 (5)	0.6887 (3)	0.0166 (8)
H2	1.1569	0.6925	0.6812	0.020*
H99	0.890 (6)	0.755 (6)	0.776 (4)	0.026 (12)*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01797 (12)	0.01529 (12)	0.01717 (12)	0.00269 (9)	−0.00223 (9)	−0.00651 (9)
Au2	0.01106 (10)	0.00938 (10)	0.01044 (10)	−0.00048 (7)	−0.00355 (7)	−0.00150 (7)
Au1	0.00681 (9)	0.01063 (10)	0.00881 (10)	0.00010 (7)	−0.00208 (7)	−0.00155 (7)
Cl3	0.0245 (4)	0.0160 (4)	0.0109 (4)	−0.0024 (3)	−0.0030 (3)	−0.0017 (3)
Cl2	0.0086 (4)	0.0191 (4)	0.0211 (4)	0.0000 (3)	−0.0055 (3)	−0.0036 (3)
Cl4	0.0233 (4)	0.0104 (4)	0.0166 (4)	−0.0010 (3)	−0.0040 (4)	−0.0020 (3)
C8	0.0163 (17)	0.0134 (17)	0.0117 (17)	0.0026 (14)	−0.0041 (14)	−0.0028 (13)
C7	0.0180 (18)	0.0184 (18)	0.0124 (17)	−0.0002 (14)	−0.0022 (14)	−0.0001 (14)
C6	0.025 (2)	0.0210 (19)	0.0133 (18)	0.0035 (16)	−0.0067 (15)	0.0009 (15)
C5	0.027 (2)	0.0131 (17)	0.0139 (18)	−0.0024 (15)	−0.0092 (15)	−0.0016 (14)
C10	0.0198 (18)	0.0127 (17)	0.0077 (16)	0.0013 (14)	−0.0048 (14)	0.0014 (13)
C4	0.0235 (19)	0.0133 (17)	0.0130 (17)	0.0058 (14)	−0.0080 (15)	−0.0021 (14)
N1	0.0164 (15)	0.0125 (15)	0.0153 (15)	0.0006 (12)	−0.0041 (12)	−0.0024 (12)
C9	0.0177 (17)	0.0125 (17)	0.0098 (16)	0.0008 (13)	−0.0067 (14)	0.0027 (13)
Cl1	0.0150 (4)	0.0115 (4)	0.0176 (4)	−0.0005 (3)	−0.0037 (3)	−0.0014 (3)
C3	0.0138 (17)	0.0234 (19)	0.0117 (17)	0.0055 (15)	−0.0005 (14)	−0.0007 (14)
C2	0.0159 (18)	0.0173 (18)	0.0159 (18)	−0.0029 (14)	−0.0053 (14)	0.0026 (14)

I1—C8	2.093 (3)	C6—H6	0.9300
Au2—Cl3	2.2857 (8)	C5—C10	1.404 (5)
Au2—Cl3ⁱ	2.2857 (8)	C5—H5	0.9300
Au2—Cl4ⁱ	2.2894 (8)	C10—C4	1.407 (5)
Au2—Cl4	2.2895 (8)	C10—C9	1.429 (5)
Au1—Cl1ⁱⁱ	2.2817 (8)	C4—C3	1.381 (5)
Au1—Cl1	2.2817 (8)	C4—H4	0.9300
Au1—Cl2ⁱⁱ	2.2818 (8)	N1—C2	1.331 (5)
Au1—Cl2	2.2818 (8)	N1—C9	1.360 (5)
C8—C7	1.369 (5)	N1—H99	0.80 (4)
C8—C9	1.418 (5)	C3—C2	1.377 (5)
C7—C6	1.422 (5)	C3—H3	0.9300
C7—H7	0.9300	C2—H2	0.9300
C6—C5	1.371 (5)

Cl3—Au2—Cl3ⁱ	180.0	C6—C5—C10	121.4 (3)
Cl3—Au2—Cl4ⁱ	90.15 (3)	C6—C5—H5	119.3
Cl3ⁱ—Au2—Cl4ⁱ	89.85 (3)	C10—C5—H5	119.3
Cl3—Au2—Cl4	89.85 (3)	C5—C10—C4	123.3 (3)
Cl3ⁱ—Au2—Cl4	90.15 (3)	C5—C10—C9	118.8 (3)
Cl4ⁱ—Au2—Cl4	180.0	C4—C10—C9	117.9 (4)
Cl1ⁱⁱ—Au1—Cl1	180.0	C3—C4—C10	120.9 (3)
Cl1ⁱⁱ—Au1—Cl2ⁱⁱ	90.54 (3)	C3—C4—H4	119.6
Cl1—Au1—Cl2ⁱⁱ	89.46 (3)	C10—C4—H4	119.6
Cl1ⁱⁱ—Au1—Cl2	89.46 (3)	C2—N1—C9	123.7 (3)
Cl1—Au1—Cl2	90.54 (3)	C2—N1—H99	118 (3)
Cl2ⁱⁱ—Au1—Cl2	180.0	C9—N1—H99	118 (3)
C7—C8—C9	119.9 (3)	N1—C9—C8	122.7 (3)
C7—C8—I1	120.2 (3)	N1—C9—C10	117.9 (3)
C9—C8—I1	119.8 (3)	C8—C9—C10	119.4 (3)
C8—C7—C6	121.0 (3)	C2—C3—C4	119.0 (3)
C8—C7—H7	119.5	C2—C3—H3	120.5
C6—C7—H7	119.5	C4—C3—H3	120.5
C5—C6—C7	119.5 (4)	N1—C2—C3	120.6 (3)
C5—C6—H6	120.3	N1—C2—H2	119.7
C7—C6—H6	120.3	C3—C2—H2	119.7

D—H···A	D—H	H···A	D···A	D—H···A
N1—H99···Cl3ⁱⁱⁱ	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···Cl1^iv	0.93	2.79	3.493 (4)	133
C3—H3···Cl1^v	0.93	2.81	3.722 (4)	168

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

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

5 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Regioselective introduction of heteroatoms at the C-8 position of quinoline N-oxides: remote C-H activation using N-oxide as a stepping stone.

Authors: Heejun Hwang; Jinwoo Kim; Jisu Jeong; Sukbok Chang
Journal: J Am Chem Soc Date: 2014-07-16 Impact factor: 15.419