Crystal structure of bis-(quinolin-1-ium) tetra-chlorido-ferrate(III) chloride.

The asymmetric unit of the title hybrid compound, (C9H8N)[FeCl4]Cl, comprises a tetra-hedral tetra-chlorido-ferrate(III) anion, [FeCl4](-), a Cl(-) anion and two quinolinium cations. There are N-H⋯Cl hydrogen-bonding inter-actions between the protonated N atoms of the quinolinium cations and the chloride anion, which together with π-π stacking between adjacent quinolinium rings [centroid-to-centroid distances between C6 and C5N rings in adjacent stacked quinolinium cations of 3.609 (2) and 3.802 (2) Å] serve to hold the structure together.

Related literature

For non-linear optical properties of hybrid compounds, see: Bouchouit et al. (2008 ▸, 2010 ▸, 2015 ▸); Jayalakshmi & Kumar (2006 ▸); Sankar et al. (2007 ▸). For similar structures containing the [FeCl4]− anion, see: Khadri et al. (2013 ▸); Chen & Huang (2010 ▸); Prommon et al. (2012 ▸); Kruszynski et al. (2007 ▸).

Experimental

Crystal data

(C9H8N)2[FeCl4]Cl

M = 493.43

Triclinic,

a = 8.424 (2) Å

b = 10.435 (3) Å

c = 13.022 (4) Å

α = 109.626 (18)°

β = 100.197 (19)°

γ = 90.893 (19)°

V = 1057.7 (5) Å3

Z = 2

Mo Kα radiation

μ = 1.35 mm−1

T = 295 K

0.12 × 0.05 × 0.04 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▸) T min = 0.899, T max = 0.922

9378 measured reflections

3738 independent reflections

2927 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.074

S = 1.01

3738 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2011 ▸); cell refinement: SAINT (Bruker, 2011 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg & Berndt, 2001 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015024548/cq2018sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015024548/cq2018Isup2.hkl

Click here for additional data file.

ORTEP-3 . DOI: 10.1107/S2056989015024548/cq2018fig1.tif

An ORTEP-3 (Farrugia, 2012) plot of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015024548/cq2018fig2.tif

A packing diagram of the title compound, viewed along the b axis, showing the N—H⋯Cl hydrogen bonds as dashed lines.

CCDC reference: 1443665

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

(C9H8N)2[FeCl4]Cl	Z = 2
Mr = 493.43	F(000) = 498
Triclinic, P1	Dx = 1.549 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.424 (2) Å	Cell parameters from 2434 reflections
b = 10.435 (3) Å	θ = 2.5–24.9°
c = 13.022 (4) Å	µ = 1.35 mm−1
α = 109.626 (18)°	T = 295 K
β = 100.197 (19)°	Prism, brown
γ = 90.893 (19)°	0.12 × 0.05 × 0.04 mm
V = 1057.7 (5) Å3

Bruker APEXII diffractometer	2927 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
CCD rotation images, thin slices scans	θmax = 25.1°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −10→9
Tmin = 0.899, Tmax = 0.922	k = −12→12
9378 measured reflections	l = −15→15
3738 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0268P)2 + 0.0315P] where P = (Fo2 + 2Fc2)/3
3738 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.31 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.

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.

	x	y	z	Uiso*/Ueq
Fe1	0.11617 (5)	−0.18619 (4)	0.64487 (3)	0.02192 (12)
Cl4	0.29503 (9)	−0.33664 (7)	0.60671 (6)	0.03500 (19)
Cl3	−0.12466 (8)	−0.28089 (7)	0.55023 (6)	0.02990 (18)
Cl1	0.17477 (8)	−0.00943 (7)	0.59992 (6)	0.02792 (17)
Cl5	0.40919 (9)	0.25683 (8)	1.05985 (6)	0.0361 (2)
Cl2	0.11071 (11)	−0.11756 (8)	0.82228 (6)	0.0407 (2)
N1A	0.8158 (3)	0.5396 (2)	0.83436 (18)	0.0227 (5)
H1A	0.7565	0.5992	0.8689	0.027*
N1B	0.4922 (3)	0.1123 (2)	0.83299 (18)	0.0263 (5)
H1B	0.4486	0.1429	0.8906	0.032*
C4A	0.9484 (3)	0.3350 (3)	0.8123 (2)	0.0209 (6)
C3B	0.6376 (3)	0.0137 (3)	0.6543 (2)	0.0286 (7)
H3B	0.689	−0.0202	0.5941	0.034*
C3A	1.0018 (3)	0.3528 (3)	0.7215 (2)	0.0256 (6)
H3A	1.0639	0.2886	0.6816	0.031*
C8B	0.4286 (3)	0.3164 (3)	0.7925 (2)	0.0269 (6)
H8B	0.3793	0.348	0.8539	0.032*
C9A	0.8504 (3)	0.4318 (3)	0.8695 (2)	0.0214 (6)
C2B	0.6258 (3)	−0.0606 (3)	0.7210 (2)	0.0317 (7)
H2B	0.6671	−0.1457	0.7061	0.038*
C6A	0.9269 (3)	0.2136 (3)	0.9376 (2)	0.0312 (7)
H6A	0.9539	0.1416	0.9625	0.037*
C7A	0.8267 (3)	0.3101 (3)	0.9917 (2)	0.0282 (7)
H7A	0.7859	0.2996	1.0505	0.034*
C7B	0.4349 (3)	0.3917 (3)	0.7256 (2)	0.0310 (7)
H7B	0.3901	0.4754	0.7418	0.037*
C4B	0.5727 (3)	0.1417 (3)	0.6753 (2)	0.0211 (6)
C9B	0.4972 (3)	0.1909 (3)	0.7676 (2)	0.0217 (6)
C5A	0.9848 (3)	0.2239 (3)	0.8496 (2)	0.0277 (6)
H5A	1.0486	0.1579	0.8137	0.033*
C1B	0.5514 (3)	−0.0082 (3)	0.8115 (2)	0.0319 (7)
H1B1	0.5431	−0.0585	0.8576	0.038*
C5B	0.5761 (3)	0.2235 (3)	0.6085 (2)	0.0274 (7)
H5B	0.6258	0.1942	0.5471	0.033*
C8A	0.7892 (3)	0.4185 (3)	0.9588 (2)	0.0244 (6)
H8A	0.724	0.4826	0.9951	0.029*
C1A	0.8687 (3)	0.5569 (3)	0.7502 (2)	0.0274 (7)
H1A1	0.8423	0.6326	0.7302	0.033*
C2A	0.9637 (3)	0.4630 (3)	0.6912 (2)	0.0282 (7)
H2A	1.0007	0.4752	0.6317	0.034*
C6B	0.5079 (3)	0.3445 (3)	0.6328 (2)	0.0309 (7)
H6B	0.5097	0.3965	0.5873	0.037*

	U11	U22	U33	U12	U13	U23
Fe1	0.0269 (2)	0.0194 (2)	0.0219 (2)	0.00239 (16)	0.00657 (17)	0.00933 (17)
Cl4	0.0363 (4)	0.0294 (4)	0.0470 (5)	0.0126 (3)	0.0145 (4)	0.0193 (4)
Cl3	0.0271 (4)	0.0295 (4)	0.0319 (4)	−0.0008 (3)	0.0076 (3)	0.0082 (3)
Cl1	0.0317 (4)	0.0243 (4)	0.0322 (4)	0.0010 (3)	0.0065 (3)	0.0154 (3)
Cl5	0.0490 (5)	0.0359 (4)	0.0313 (4)	0.0214 (4)	0.0196 (4)	0.0149 (3)
Cl2	0.0691 (6)	0.0341 (4)	0.0230 (4)	0.0088 (4)	0.0136 (4)	0.0126 (3)
N1A	0.0248 (12)	0.0170 (12)	0.0259 (13)	0.0046 (9)	0.0097 (10)	0.0043 (10)
N1B	0.0307 (13)	0.0301 (14)	0.0209 (12)	0.0049 (11)	0.0092 (11)	0.0101 (11)
C4A	0.0192 (13)	0.0188 (14)	0.0216 (14)	0.0011 (11)	0.0015 (11)	0.0042 (12)
C3B	0.0278 (15)	0.0293 (17)	0.0266 (16)	0.0024 (13)	0.0097 (13)	0.0046 (13)
C3A	0.0248 (15)	0.0246 (16)	0.0260 (15)	0.0023 (12)	0.0104 (12)	0.0043 (13)
C8B	0.0255 (15)	0.0257 (16)	0.0272 (16)	0.0052 (12)	0.0086 (13)	0.0041 (13)
C9A	0.0180 (13)	0.0197 (15)	0.0228 (14)	−0.0033 (11)	0.0016 (12)	0.0041 (12)
C2B	0.0358 (17)	0.0210 (16)	0.0387 (18)	0.0083 (13)	0.0113 (15)	0.0085 (14)
C6A	0.0361 (17)	0.0306 (17)	0.0308 (17)	0.0038 (14)	0.0027 (14)	0.0175 (14)
C7A	0.0302 (16)	0.0335 (17)	0.0215 (15)	−0.0024 (13)	0.0030 (13)	0.0116 (13)
C7B	0.0296 (16)	0.0240 (16)	0.0372 (18)	0.0035 (13)	0.0004 (14)	0.0108 (14)
C4B	0.0190 (14)	0.0234 (15)	0.0186 (14)	−0.0006 (11)	0.0030 (11)	0.0048 (12)
C9B	0.0186 (14)	0.0222 (15)	0.0217 (14)	−0.0022 (11)	0.0011 (12)	0.0059 (12)
C5A	0.0278 (15)	0.0238 (16)	0.0315 (16)	0.0070 (12)	0.0041 (13)	0.0101 (13)
C1B	0.0357 (17)	0.0297 (17)	0.0359 (18)	0.0046 (14)	0.0097 (14)	0.0170 (14)
C5B	0.0268 (15)	0.0330 (17)	0.0223 (15)	−0.0012 (13)	0.0042 (13)	0.0099 (13)
C8A	0.0236 (14)	0.0273 (16)	0.0197 (14)	0.0036 (12)	0.0059 (12)	0.0039 (12)
C1A	0.0300 (16)	0.0217 (15)	0.0345 (17)	−0.0011 (12)	0.0081 (14)	0.0138 (13)
C2A	0.0302 (16)	0.0298 (17)	0.0296 (16)	−0.0002 (13)	0.0135 (13)	0.0127 (14)
C6B	0.0298 (16)	0.0327 (18)	0.0319 (17)	−0.0022 (13)	−0.0007 (14)	0.0169 (14)

Fe1—Cl2	2.1862 (10)	C9A—C8A	1.399 (4)
Fe1—Cl1	2.1880 (9)	C2B—C1B	1.386 (4)
Fe1—Cl4	2.1901 (10)	C2B—H2B	0.93
Fe1—Cl3	2.2013 (10)	C6A—C5A	1.356 (4)
N1A—C1A	1.317 (3)	C6A—C7A	1.408 (4)
N1A—C9A	1.367 (3)	C6A—H6A	0.93
N1A—H1A	0.86	C7A—C8A	1.360 (4)
N1B—C1B	1.319 (4)	C7A—H7A	0.93
N1B—C9B	1.370 (3)	C7B—C6B	1.398 (4)
N1B—H1B	0.86	C7B—H7B	0.93
C4A—C3A	1.404 (4)	C4B—C9B	1.407 (4)
C4A—C9A	1.412 (4)	C4B—C5B	1.411 (4)
C4A—C5A	1.419 (4)	C5A—H5A	0.93
C3B—C2B	1.359 (4)	C1B—H1B1	0.93
C3B—C4B	1.410 (4)	C5B—C6B	1.358 (4)
C3B—H3B	0.93	C5B—H5B	0.93
C3A—C2A	1.362 (4)	C8A—H8A	0.93
C3A—H3A	0.93	C1A—C2A	1.388 (4)
C8B—C7B	1.361 (4)	C1A—H1A1	0.93
C8B—C9B	1.400 (4)	C2A—H2A	0.93
C8B—H8B	0.93	C6B—H6B	0.93
Cl2—Fe1—Cl1	108.97 (4)	C8A—C7A—C6A	120.6 (3)
Cl2—Fe1—Cl4	110.06 (4)	C8A—C7A—H7A	119.7
Cl1—Fe1—Cl4	110.70 (4)	C6A—C7A—H7A	119.7
Cl2—Fe1—Cl3	108.87 (4)	C8B—C7B—C6B	120.7 (3)
Cl1—Fe1—Cl3	109.03 (4)	C8B—C7B—H7B	119.6
Cl4—Fe1—Cl3	109.18 (4)	C6B—C7B—H7B	119.6
C1A—N1A—C9A	123.3 (2)	C9B—C4B—C3B	118.3 (2)
C1A—N1A—H1A	118.3	C9B—C4B—C5B	117.5 (2)
C9A—N1A—H1A	118.3	C3B—C4B—C5B	124.2 (2)
C1B—N1B—C9B	122.9 (2)	N1B—C9B—C8B	120.6 (2)
C1B—N1B—H1B	118.5	N1B—C9B—C4B	118.2 (2)
C9B—N1B—H1B	118.5	C8B—C9B—C4B	121.2 (2)
C3A—C4A—C9A	118.6 (2)	C6A—C5A—C4A	120.1 (3)
C3A—C4A—C5A	123.9 (3)	C6A—C5A—H5A	119.9
C9A—C4A—C5A	117.6 (2)	C4A—C5A—H5A	119.9
C2B—C3B—C4B	120.7 (3)	N1B—C1B—C2B	120.6 (3)
C2B—C3B—H3B	119.7	N1B—C1B—H1B1	119.7
C4B—C3B—H3B	119.7	C2B—C1B—H1B1	119.7
C2A—C3A—C4A	120.6 (3)	C6B—C5B—C4B	120.8 (3)
C2A—C3A—H3A	119.7	C6B—C5B—H5B	119.6
C4A—C3A—H3A	119.7	C4B—C5B—H5B	119.6
C7B—C8B—C9B	119.1 (3)	C7A—C8A—C9A	118.9 (3)
C7B—C8B—H8B	120.4	C7A—C8A—H8A	120.5
C9B—C8B—H8B	120.4	C9A—C8A—H8A	120.5
N1A—C9A—C8A	120.6 (2)	N1A—C1A—C2A	120.5 (3)
N1A—C9A—C4A	117.8 (2)	N1A—C1A—H1A1	119.7
C8A—C9A—C4A	121.6 (2)	C2A—C1A—H1A1	119.7
C3B—C2B—C1B	119.3 (3)	C3A—C2A—C1A	119.2 (3)
C3B—C2B—H2B	120.4	C3A—C2A—H2A	120.4
C1B—C2B—H2B	120.4	C1A—C2A—H2A	120.4
C5A—C6A—C7A	121.1 (3)	C5B—C6B—C7B	120.6 (3)
C5A—C6A—H6A	119.4	C5B—C6B—H6B	119.7
C7A—C6A—H6A	119.4	C7B—C6B—H6B	119.7
C9A—C4A—C3A—C2A	1.8 (4)	C5B—C4B—C9B—N1B	179.7 (2)
C5A—C4A—C3A—C2A	−179.2 (3)	C3B—C4B—C9B—C8B	−179.3 (2)
C1A—N1A—C9A—C8A	−179.4 (2)	C5B—C4B—C9B—C8B	−0.2 (4)
C1A—N1A—C9A—C4A	0.2 (4)	C7A—C6A—C5A—C4A	1.6 (4)
C3A—C4A—C9A—N1A	−1.4 (4)	C3A—C4A—C5A—C6A	−179.3 (3)
C5A—C4A—C9A—N1A	179.6 (2)	C9A—C4A—C5A—C6A	−0.3 (4)
C3A—C4A—C9A—C8A	178.2 (2)	C9B—N1B—C1B—C2B	1.3 (4)
C5A—C4A—C9A—C8A	−0.8 (4)	C3B—C2B—C1B—N1B	0.1 (4)
C4B—C3B—C2B—C1B	−1.1 (4)	C9B—C4B—C5B—C6B	−0.4 (4)
C5A—C6A—C7A—C8A	−1.8 (4)	C3B—C4B—C5B—C6B	178.6 (3)
C9B—C8B—C7B—C6B	0.4 (4)	C6A—C7A—C8A—C9A	0.7 (4)
C2B—C3B—C4B—C9B	0.7 (4)	N1A—C9A—C8A—C7A	−179.8 (2)
C2B—C3B—C4B—C5B	−178.3 (3)	C4A—C9A—C8A—C7A	0.6 (4)
C1B—N1B—C9B—C8B	178.2 (3)	C9A—N1A—C1A—C2A	0.6 (4)
C1B—N1B—C9B—C4B	−1.7 (4)	C4A—C3A—C2A—C1A	−1.0 (4)
C7B—C8B—C9B—N1B	−179.7 (2)	N1A—C1A—C2A—C3A	−0.1 (4)
C7B—C8B—C9B—C4B	0.2 (4)	C4B—C5B—C6B—C7B	1.0 (4)
C3B—C4B—C9B—N1B	0.6 (4)	C8B—C7B—C6B—C5B	−1.0 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···Cl5i	0.86	2.16	3.014 (3)	174
N1B—H1B···Cl5	0.86	2.21	3.043 (3)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯Cl5i	0.86	2.16	3.014 (3)	174
N1B—H1B⋯Cl5	0.86	2.21	3.043 (3)	163

Symmetry code: (i) .