Crystal structure of 8-iodo­quinolinium tetra­chlorido­aurate(III)

Onserio, B.O.; Tamang, S.R.; Hoefelmeyer, J.D.

doi:10.1107/S2056989015022574

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m261-m262

https://doi.org/10.1107/S2056989015022574

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Crystal structure of 8-iodoquinolinium tetrachloridoaurate(III)

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

^aDepartment of Chemistry, University of South Dakota, 414 E. Clark St., Vermillion, SD 57069, USA
^*Correspondence e-mail: jhoefelm@usd.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 3 November 2015; accepted 25 November 2015; online 12 December 2015)

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.

CCDC reference: 1438910

1. 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 ).

2. Experimental

2.1. Crystal data

(C₉H₇IN)[AuCl₄]
M_r = 594.82
Triclinic, $[P \overline 1]$
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.016
wR(F²) = 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

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) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) -x+2, -y, -z+1.

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).

Supporting information

CCDC reference: 1438910

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015022574/wm5236sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015022574/wm5236Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015022574/wm5236Isup3.rtf

checkCIF report

Synthesis and crystallization top

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.

Refinement top

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.

Related literature top

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).

Structure description top

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).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).

Figures top

	Fig. 1. 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.]
	Fig. 2. The centrosymmetric unit cell of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. 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.

8-Iodoquinolinium tetrachloridoaurate(III) top

Crystal data top

(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

Data collection top

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 top

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

Crystal data top

(C₉H₇IN)[AuCl₄]	γ = 85.178 (1)°
M_r = 594.82	V = 676.52 (7) Å³
Triclinic, P1	Z = 2
a = 7.6299 (5) Å	Mo Kα radiation
b = 7.8609 (5) Å	µ = 13.92 mm⁻¹
c = 11.7125 (7) Å	T = 100 K
α = 80.160 (1)°	0.16 × 0.11 × 0.04 mm
β = 78.143 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2482 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2407 reflections with I > 2σ(I)
T_min = 0.174, T_max = 0.573	R_int = 0.024
6855 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.016	0 restraints
wR(F²) = 0.040	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.19 e Å⁻³
2482 reflections	Δρ_min = −0.94 e Å⁻³
152 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

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

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (iii) x+1, y+1, z+1; (iv) x+1, y+1, z; (v) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

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) x+1, y+1, z+1; (ii) x+1, y+1, z; (iii) −x+2, −y, −z+1.

Acknowledgements

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m261-m262

https://doi.org/10.1107/S2056989015022574

Open

access