4-(Dimethyl­amino)­pyridinium tetra­chloridoferrate(III)

Khadri, A.; Bouchene, R.; Bouacida, S.; Merazig, H.; Roisnel, T.

doi:10.1107/S160053681300603X

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page m190

doi:10.1107/S160053681300603X

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4-(Dimethylamino)pyridinium tetrachloridoferrate(III)

Amina Khadri,^a,^b Rafika Bouchene,^a,^b Sofiane Bouacida,^c,^b ^* Hocine Merazig ^c and Thierry Roisnel ^d

^aLaboratoire de Chimie Appliquée et Technologie des Matériaux LCATM, Université Oum El Bouaghi, Algeria, ^bDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria, ^cUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Faculté des Sciences Exactes, Université Mentouri Constantine 25000, Algeria, and ^dCentre de Diffractométrie X, UMR 6226 CNRS Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du Général Leclerc, 35042 Rennes, France
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 27 February 2013; accepted 3 March 2013; online 9 March 2013)

The title salt, (C₇H₁₁N₂)[FeCl₄], consists of one essentially planar (the r.m.s. deviation for all non-H atoms being 0.004 Å) 4-(dimethylamino)pyridinium cation and a tetrahedral tetrachloridoferrate(III) anion. The cations and anions are arranged in layers parallel to (010). Besides electrostatic interactions, the crystal packing features N—H⋯Cl and C—H⋯Cl hydrogen bonds between cations and anions, forming a three-dimensional network.

Related literature

For background to hybrid compounds based on protonated substituted N-heterocyclic ligands, see: Bouacida (2008 ); Bouacida et al. (2007 , 2009 ). For a related structure, see: Nenwa et al. (2010 ).

Experimental

Crystal data

(C₇H₁₁N₂)[FeCl₄]
M_r = 320.83
Monoclinic, P 2₁ /n
a = 9.0360 (2) Å
b = 14.0492 (5) Å
c = 10.2077 (3) Å
β = 98.7259 (9)°
V = 1280.85 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.98 mm⁻¹
T = 100 K
0.17 × 0.12 × 0.04 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2011 ) T_min = 0.789, T_max = 0.924
11192 measured reflections
2925 independent reflections
2146 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.081
S = 1.03
2925 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Cl2ⁱ	0.79 (3)	2.60 (3)	3.369 (3)	165 (3)
C4—H4⋯Cl1ⁱ	0.95	2.74	3.604 (3)	152
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SIR2004 (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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681300603X/wm2729sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681300603X/wm2729Isup2.hkl

checkCIF report

Comment top

In the course of previuos studies on intermolecular hydrogen-bonding interactions in transition metal hybrid complexes with N-heterocyclic ligands (Bouacida, 2008; Bouacida et al., 2007, 2009), we report here on synthesis and structural characterization of a new organic/inorganic hybrid, involving Fe(III) and 4-(dimethylamino)pyridine, (C₇H₁₁N₂)⁺^.[FeCl₄]^-, (I). The molecular geometry of the constituents and the atom-numbering scheme of (I) are shown in Fig. 1.

The asymmetric unit of (I) consists of tetrahedral [FeCl₄]^- anions and one protoned 4-(dimethylamino)pyridine cation that is essentially planar; its r.m.s. deviation for all non-H atoms is 0.0043 Å, with a maximum deviation from the mean plane of -0.0094 (2) Å for the C4 atom. The packing of the ionic entities is realized by alternating layers of cations and anions parallel to (010) whereby the dimethylaminopyridinium molecules are oriented in a zig-zag fashion parallel to the (210) and (210) planes, respectively (Fig. 2). The crystal packing is stabilized by N—H···Cl and C—H···Cl hydrogen bonds involving the chloride atoms of the anions as acceptors (Table 1, Fig. 3). All these interactions link the layers together, forming a three-dimensional network and reinforcing the cohesion of the ionic structure.

A similar complex with a 4-(dimethylamino)pyridinium cation but a different metal-based anion, viz. (C₇H₁₁N₂)⁺[Cr(C₂O₄)₂(H₂O)₂]^-, has been reported recently (Nenwa et al., 2010).

Related literature top

For background to hybrid compounds based on protonated substituted N-heterocyclic ligands, see: Bouacida (2008); Bouacida et al. (2007, 2009). For a related structure, see: Nenwa et al. (2010).

Experimental top

4-(dimethylamino)pyridine and iron(III) chloride hexahydrate were mixed in an equimolar ratio in acidified water (HCl, 37%_wt). The solution was kept at room temperature for ten days after which crystals suitable for X-ray diffraction could be isolated.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SIR2004 (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).

Figures top

	Fig. 1. The asymmetric unit of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Packing diagram viewed along [001] showing alterning layers of 4-(dimethylamino)pyridinium cations and [FeCl₄] tetrahedraparallel to (010).
	Fig. 3. Packing diagram viewed along [100] showing N—H···Cl and C—H···Cl hydrogen-bonding interactions as dashed lines.

4-(Dimethylamino)pyridinium tetrachloridoferrate(III) top

Crystal data top

(C₇H₁₁N₂)[FeCl₄]	F(000) = 644
M_r = 320.83	D_x = 1.664 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2278 reflections
a = 9.0360 (2) Å	θ = 2.9–26.5°
b = 14.0492 (5) Å	µ = 1.98 mm⁻¹
c = 10.2077 (3) Å	T = 100 K
β = 98.7259 (9)°	Plate, orange
V = 1280.85 (7) Å³	0.17 × 0.12 × 0.04 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2925 independent reflections
Radiation source: sealed tube	2146 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −8→11
T_min = 0.789, T_max = 0.924	k = −18→18
11192 measured reflections	l = −13→13

Refinement top

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0258P)² + 0.6542P] where P = (F_o² + 2F_c²)/3
2925 reflections	(Δ/σ)_max = 0.001
133 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

(C₇H₁₁N₂)[FeCl₄]	V = 1280.85 (7) Å³
M_r = 320.83	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0360 (2) Å	µ = 1.98 mm⁻¹
b = 14.0492 (5) Å	T = 100 K
c = 10.2077 (3) Å	0.17 × 0.12 × 0.04 mm
β = 98.7259 (9)°

Data collection top

Bruker APEXII CCD diffractometer	2925 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2011)	2146 reflections with I > 2σ(I)
T_min = 0.789, T_max = 0.924	R_int = 0.041
11192 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.94 e Å⁻³
2925 reflections	Δρ_min = −0.56 e Å⁻³
133 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Fe1	−0.02427 (4)	0.25669 (2)	0.72252 (3)	0.02371 (11)
Cl1	−0.16650 (8)	0.13001 (5)	0.71136 (7)	0.0449 (2)
Cl2	0.11905 (7)	0.25489 (4)	0.91821 (6)	0.03315 (17)
Cl3	0.11063 (8)	0.25245 (5)	0.56193 (7)	0.03676 (18)
Cl4	−0.15646 (8)	0.38804 (5)	0.70930 (7)	0.03842 (18)
C1	0.3730 (3)	0.42873 (17)	0.8197 (3)	0.0281 (6)
H1	0.381	0.4214	0.913	0.034*
C2	0.4618 (3)	0.37690 (19)	0.7516 (3)	0.0374 (7)
H2	0.5322	0.3338	0.7976	0.045*
N3	0.4513 (3)	0.38586 (19)	0.6189 (3)	0.0445 (7)
H3	0.506 (4)	0.355 (2)	0.582 (3)	0.059 (11)*
C4	0.3518 (3)	0.4461 (2)	0.5506 (3)	0.0417 (7)
H4	0.3453	0.4501	0.457	0.05*
C5	0.2614 (3)	0.50068 (19)	0.6130 (3)	0.0331 (6)
H5	0.1935	0.5436	0.5635	0.04*
C6	0.2677 (3)	0.49407 (17)	0.7526 (2)	0.0260 (6)
N7	0.1790 (2)	0.54643 (15)	0.8167 (2)	0.0305 (5)
C8	0.1866 (3)	0.5381 (2)	0.9603 (3)	0.0407 (7)
H8A	0.1606	0.4731	0.9829	0.061*
H8B	0.116	0.5829	0.9908	0.061*
H8C	0.2884	0.5529	1.0036	0.061*
C9	0.0706 (3)	0.6131 (2)	0.7463 (3)	0.0448 (8)
H9A	0.1236	0.6617	0.7024	0.067*
H9B	0.0143	0.6437	0.8095	0.067*
H9C	0.0013	0.5786	0.6797	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0239 (2)	0.0260 (2)	0.02024 (19)	−0.00208 (14)	0.00016 (14)	0.00140 (15)
Cl1	0.0505 (4)	0.0485 (4)	0.0315 (4)	−0.0268 (3)	−0.0077 (3)	0.0074 (3)
Cl2	0.0327 (3)	0.0370 (4)	0.0261 (3)	−0.0089 (3)	−0.0072 (3)	0.0047 (3)
Cl3	0.0380 (4)	0.0417 (4)	0.0330 (4)	−0.0003 (3)	0.0131 (3)	−0.0032 (3)
Cl4	0.0419 (4)	0.0406 (4)	0.0322 (4)	0.0157 (3)	0.0035 (3)	0.0016 (3)
C1	0.0269 (13)	0.0283 (14)	0.0287 (14)	−0.0048 (11)	0.0035 (11)	0.0028 (11)
C2	0.0331 (15)	0.0305 (15)	0.050 (2)	−0.0057 (12)	0.0092 (13)	0.0032 (13)
N3	0.0481 (16)	0.0367 (15)	0.0554 (18)	−0.0106 (12)	0.0295 (14)	−0.0140 (13)
C4	0.0578 (19)	0.0419 (17)	0.0266 (16)	−0.0218 (15)	0.0103 (14)	−0.0071 (13)
C5	0.0404 (16)	0.0321 (15)	0.0255 (14)	−0.0088 (12)	0.0002 (12)	−0.0008 (11)
C6	0.0276 (14)	0.0264 (13)	0.0235 (13)	−0.0107 (11)	0.0022 (11)	−0.0001 (10)
N7	0.0314 (12)	0.0300 (12)	0.0299 (13)	−0.0015 (9)	0.0036 (10)	−0.0003 (10)
C8	0.0467 (17)	0.0427 (17)	0.0360 (17)	−0.0037 (14)	0.0167 (14)	−0.0030 (13)
C9	0.0347 (16)	0.0370 (17)	0.061 (2)	0.0049 (13)	0.0025 (14)	0.0062 (15)

Geometric parameters (Å, º) top

Fe1—Cl3	2.1870 (7)	C4—H4	0.95
Fe1—Cl1	2.1882 (7)	C5—C6	1.420 (3)
Fe1—Cl4	2.1912 (7)	C5—H5	0.95
Fe1—Cl2	2.2097 (7)	C6—N7	1.331 (3)
C1—C2	1.351 (4)	N7—C8	1.462 (3)
C1—C6	1.421 (3)	N7—C9	1.463 (3)
C1—H1	0.95	C8—H8A	0.98
C2—N3	1.350 (4)	C8—H8B	0.98
C2—H2	0.95	C8—H8C	0.98
N3—C4	1.349 (4)	C9—H9A	0.98
N3—H3	0.79 (3)	C9—H9B	0.98
C4—C5	1.348 (4)	C9—H9C	0.98

Cl3—Fe1—Cl1	109.18 (3)	C6—C5—H5	119.9
Cl3—Fe1—Cl4	109.72 (3)	N7—C6—C5	121.4 (2)
Cl1—Fe1—Cl4	111.80 (3)	N7—C6—C1	122.0 (2)
Cl3—Fe1—Cl2	111.12 (3)	C5—C6—C1	116.6 (2)
Cl1—Fe1—Cl2	107.27 (3)	C6—N7—C8	120.6 (2)
Cl4—Fe1—Cl2	107.73 (3)	C6—N7—C9	121.4 (2)
C2—C1—C6	120.4 (3)	C8—N7—C9	118.0 (2)
C2—C1—H1	119.8	N7—C8—H8A	109.5
C6—C1—H1	119.8	N7—C8—H8B	109.5
N3—C2—C1	120.6 (3)	H8A—C8—H8B	109.5
N3—C2—H2	119.7	N7—C8—H8C	109.5
C1—C2—H2	119.7	H8A—C8—H8C	109.5
C4—N3—C2	121.1 (3)	H8B—C8—H8C	109.5
C4—N3—H3	121 (3)	N7—C9—H9A	109.5
C2—N3—H3	118 (3)	N7—C9—H9B	109.5
C5—C4—N3	121.1 (3)	H9A—C9—H9B	109.5
C5—C4—H4	119.4	N7—C9—H9C	109.5
N3—C4—H4	119.4	H9A—C9—H9C	109.5
C4—C5—C6	120.1 (3)	H9B—C9—H9C	109.5
C4—C5—H5	119.9

C6—C1—C2—N3	−0.4 (4)	C2—C1—C6—N7	−179.8 (2)
C1—C2—N3—C4	−0.4 (4)	C2—C1—C6—C5	0.4 (3)
C2—N3—C4—C5	1.3 (4)	C5—C6—N7—C8	179.6 (2)
N3—C4—C5—C6	−1.3 (4)	C1—C6—N7—C8	−0.2 (4)
C4—C5—C6—N7	−179.4 (2)	C5—C6—N7—C9	0.1 (4)
C4—C5—C6—C1	0.4 (3)	C1—C6—N7—C9	−179.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl2ⁱ	0.79 (3)	2.60 (3)	3.369 (3)	165 (3)
C4—H4···Cl1ⁱ	0.95	2.74	3.604 (3)	152

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	(C₇H₁₁N₂)[FeCl₄]
M_r	320.83
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	9.0360 (2), 14.0492 (5), 10.2077 (3)
β (°)	98.7259 (9)
V (Å³)	1280.85 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.98
Crystal size (mm)	0.17 × 0.12 × 0.04

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2011)
T_min, T_max	0.789, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	11192, 2925, 2146
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.081, 1.03
No. of reflections	2925
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.56

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Cl2ⁱ	0.79 (3)	2.60 (3)	3.369 (3)	165 (3)
C4—H4···Cl1ⁱ	0.9500	2.7400	3.604 (3)	152.00

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

We are grateful to all personel of the LCATM laboratory, Université Oum El Bouaghi, Algeria, for their assistance. Thanks are due to MESRS (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique - Algeria) for financial support via the PNR program.

References

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