Butan-1-aminium tetra­chlorido­ferrate(III)–18-crown-6 (1/1)

Zhang, Y.

doi:10.1107/S160053681204994X

metal-organic compounds

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Volume 69| Part 1| January 2013| Page m38

https://doi.org/10.1107/S160053681204994X

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Butan-1-aminium tetrachloridoferrate(III)–18-crown-6 (1/1)

Yuan Zhang ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: zhangshelley86@Hotmail.com

(Received 1 December 2012; accepted 6 December 2012; online 12 December 2012)

In the crystal of the title compound, (C₄H₁₂N)[FeCl₄]·C₁₂H₂₄O₆, the butan-1-aminium cation and the tetrachloridoferrate(III) anion have m symmetry: in the cation, the non-H atoms are located on the mirror plane and in the anion, the Fe^III atom and two Cl atoms are located on the mirror plane. The 18-crown-6 molecule also has m symmetry, with two O atoms located on the mirror plane. The butan-1-amine cation and the 18-crown-6 molecule are connected by N—H⋯O hydrogen bonds.

Related literature

For related co-crystals of (18-crown-6)] and anilinium salts, see: Akutagawa et al. (2009 ).

Experimental

Crystal data

(C₄H₁₂N)[FeCl₄]·C₁₂H₂₄O₆
M_r = 536.11
Orthorhombic, P n m a
a = 9.3109 (19) Å
b = 11.431 (2) Å
c = 24.718 (5) Å
V = 2630.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.665, T_max = 0.820
24682 measured reflections
3160 independent reflections
1649 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.234
S = 1.04
3160 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.90	2.07	2.963 (5)	176
N1—H1B⋯O3	0.90	2.07	2.966 (4)	175

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681204994X/xu5660sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681204994X/xu5660Isup2.hkl

checkCIF report

Comment top

Several supramolecular rotators of [(Ani)(18-crown-6)]⁺ and [(Ani)(dibenzo18-crown-6)]⁺ in [Ni(dmit)₂]^- salts (dmit₂^- = 2-thioxo-1,3,dithiole-4,5-dithiolate; Ani⁺ = anilinium) have been reported, of which some display novel ferroelectric features (Akutagawa et al., 2009). There is a class of transition metal complexes whose electronic and magnetic properties in the solid state arise from the extended π-ligands (π-electrons and π-spins). So we try to replace the amine, crown ether and [Ni(dmit)₂]^- salts. Herein, we report the [tetrachloro-iron-anion] which replace the [Ni(dmit)₂]^- salts providing high electrical conductivity.

Supramolecular rotators was assembled between protonated butan-1-amine (C₄H₉NH₃)⁺and 18-crown-6 by of hydrogen-bonding. The ammonium moieties of (–NH3+) cations were interacted with the six oxygen atoms of crown ethers through six simple N–H···O hydrogen bonding, forming 1:1 (one crown ether ring per ammonium group) supramolecular rotator-stator structures. The FeCl₄^- anions are relatively small for embedding large and structurally diverse supramolecular cations in the crystal lattice. Again, such a feature further supports the fact that the size and shape of the supramolecular assemblies between C₄H₉NH₃⁺ and crown ethers are strongly affected by the proton-transfer state.

Related literature top

For related co-crystals of (18-crown-6)] and anilinium salts, see: Akutagawa et al. (2009).

Experimental top

C₄H₉NH₂.HCl(4 mmol, 0.442 g) and 18-crown-6 (4 mmol, 1.056 g) were dissolved in methanol solution. After addition of tervalent ferric chloride (4 mmol, 1.08 g) in concentrated hydrochloric acid medium, the precipitate was filtered and washed with a small amount of methanol. Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of methanol and DMF solution at room temperature after two days.

Structure description top

For related co-crystals of (18-crown-6)] and anilinium salts, see: Akutagawa et al. (2009).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Perspective structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Butan-1-aminium tetrachloridoferrate(III)–1,4,7,10,13,16- hexaoxacyclooctadecane (1/1) top

Crystal data top

(C₄H₁₂N)[FeCl₄]·C₁₂H₂₄O₆	F(000) = 1124
M_r = 536.11	D_x = 1.354 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3160 reflections
a = 9.3109 (19) Å	θ = 2.4–27.5°
b = 11.431 (2) Å	µ = 1.01 mm⁻¹
c = 24.718 (5) Å	T = 293 K
V = 2630.8 (9) Å³	Prism, colorless
Z = 4	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	3160 independent reflections
Radiation source: fine-focus sealed tube	1649 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→14
T_min = 0.665, T_max = 0.820	l = −32→32
24682 measured reflections

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)] = 0.079	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.234	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0881P)² + 3.1745P] where P = (F_o² + 2F_c²)/3
3160 reflections	(Δ/σ)_max = 0.001
142 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

(C₄H₁₂N)[FeCl₄]·C₁₂H₂₄O₆	V = 2630.8 (9) Å³
M_r = 536.11	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 9.3109 (19) Å	µ = 1.01 mm⁻¹
b = 11.431 (2) Å	T = 293 K
c = 24.718 (5) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	3160 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1649 reflections with I > 2σ(I)
T_min = 0.665, T_max = 0.820	R_int = 0.090
24682 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.234	H-atom parameters constrained
S = 1.04	Δρ_max = 0.74 e Å⁻³
3160 reflections	Δρ_min = −0.40 e Å⁻³
142 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.

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 > 2sigma(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	0.22073 (9)	0.2500	0.88238 (3)	0.0713 (3)
Cl1	0.4469 (2)	0.2500	0.86376 (15)	0.1792 (13)
Cl2	0.0976 (2)	0.2500	0.80773 (6)	0.0961 (6)
Cl3	0.1710 (3)	0.40675 (17)	0.92687 (8)	0.1835 (8)
N1	0.3475 (4)	0.7500	0.65867 (15)	0.0562 (11)
H1A	0.3430	0.7500	0.6950	0.084*
H1B	0.3034	0.8143	0.6457	0.084*
C8	0.5254 (9)	0.7500	0.5846 (4)	0.133 (3)
H8A	0.4780	0.6824	0.5700	0.159*
C9	0.6662 (8)	0.7500	0.5629 (4)	0.129 (3)
H9A	0.7139	0.6822	0.5771	0.155*
C7	0.4966 (7)	0.7500	0.6410 (3)	0.131 (4)
H7A	0.5430	0.6822	0.6559	0.157*
C10	0.6838 (10)	0.7500	0.5070 (4)	0.175 (5)
H10A	0.7837	0.7500	0.4973	0.262*
H10B	0.6384	0.6814	0.4925	0.262*
O4	0.1585 (5)	0.7500	0.56513 (17)	0.0986 (16)
C6	0.0868 (5)	0.8539 (6)	0.54992 (19)	0.121 (2)
H6A	−0.0039	0.8575	0.5683	0.145*
H6B	0.0687	0.8537	0.5117	0.145*
O1	0.3486 (5)	0.7500	0.77856 (16)	0.0929 (15)
C1	0.4203 (6)	0.8546 (6)	0.79449 (19)	0.127 (2)
H1C	0.5134	0.8572	0.7778	0.152*
H1D	0.4331	0.8557	0.8330	0.152*
O2	0.3379 (3)	0.9612 (3)	0.71993 (14)	0.0964 (10)
O3	0.1868 (3)	0.9589 (3)	0.62119 (14)	0.0938 (10)
C4	0.2686 (6)	1.0561 (5)	0.6389 (3)	0.121 (2)
H4A	0.2304	1.1272	0.6240	0.145*
H4B	0.3662	1.0480	0.6270	0.145*
C5	0.1737 (6)	0.9561 (6)	0.5645 (2)	0.127 (2)
H5A	0.1275	1.0264	0.5524	0.153*
H5B	0.2662	0.9511	0.5475	0.153*
C3	0.2649 (6)	1.0613 (4)	0.6980 (3)	0.121 (2)
H3A	0.3112	1.1312	0.7106	0.145*
H3B	0.1668	1.0626	0.7100	0.145*
C2	0.3375 (6)	0.9578 (6)	0.7762 (2)	0.129 (2)
H2A	0.3783	1.0284	0.7906	0.154*
H2B	0.2407	0.9508	0.7891	0.154*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0715 (5)	0.0665 (5)	0.0757 (5)	0.000	−0.0136 (4)	0.000
Cl1	0.0628 (12)	0.189 (3)	0.285 (4)	0.000	−0.0184 (17)	0.000
Cl2	0.0920 (11)	0.1220 (14)	0.0744 (9)	0.000	−0.0151 (9)	0.000
Cl3	0.256 (2)	0.1460 (13)	0.1486 (13)	0.0826 (14)	−0.0819 (13)	−0.0772 (11)
N1	0.048 (2)	0.068 (3)	0.053 (2)	0.000	0.0015 (19)	0.000
C8	0.092 (5)	0.148 (8)	0.158 (8)	0.000	0.039 (5)	0.000
C9	0.096 (5)	0.128 (7)	0.163 (8)	0.000	0.046 (5)	0.000
C7	0.059 (4)	0.239 (11)	0.096 (5)	0.000	0.013 (4)	0.000
C10	0.132 (7)	0.300 (16)	0.093 (6)	0.000	0.035 (6)	0.000
O4	0.075 (3)	0.156 (4)	0.065 (2)	0.000	−0.014 (2)	0.000
C6	0.080 (3)	0.208 (6)	0.075 (3)	0.026 (4)	−0.004 (2)	0.049 (4)
O1	0.075 (3)	0.142 (4)	0.061 (2)	0.000	−0.016 (2)	0.000
C1	0.103 (4)	0.205 (6)	0.072 (3)	−0.041 (4)	−0.021 (3)	−0.037 (4)
O2	0.095 (2)	0.078 (2)	0.116 (2)	−0.0204 (17)	0.0195 (18)	−0.0302 (18)
O3	0.0780 (19)	0.082 (2)	0.121 (2)	0.0047 (16)	0.0201 (17)	0.0362 (18)
C4	0.105 (4)	0.067 (3)	0.190 (6)	0.014 (3)	0.047 (4)	0.034 (3)
C5	0.100 (4)	0.182 (5)	0.100 (3)	0.035 (4)	0.017 (3)	0.083 (4)
C3	0.094 (3)	0.051 (3)	0.217 (7)	−0.011 (3)	0.037 (4)	−0.023 (4)
C2	0.111 (4)	0.148 (5)	0.127 (4)	−0.039 (4)	−0.001 (3)	−0.072 (4)

Geometric parameters (Å, º) top

Fe1—Cl3	2.1528 (18)	C6—H6B	0.9599
Fe1—Cl3ⁱ	2.1528 (18)	O1—C1	1.425 (6)
Fe1—Cl1	2.155 (2)	O1—C1ⁱⁱ	1.425 (6)
Fe1—Cl2	2.1723 (18)	C1—C2	1.480 (9)
N1—C7	1.456 (8)	C1—H1C	0.9600
N1—H1A	0.9000	C1—H1D	0.9601
N1—H1B	0.9001	O2—C2	1.391 (6)
C8—C9	1.416 (10)	O2—C3	1.437 (6)
C8—C7	1.419 (10)	O3—C5	1.406 (6)
C8—H8A	0.9600	O3—C4	1.416 (7)
C9—C10	1.392 (12)	C4—C3	1.463 (9)
C9—H9A	0.9600	C4—H4A	0.9601
C7—H7A	0.9600	C4—H4B	0.9600
C10—H10A	0.9601	C5—H5A	0.9600
C10—H10B	0.9601	C5—H5B	0.9600
O4—C6ⁱⁱ	1.413 (6)	C3—H3A	0.9599
O4—C6	1.413 (6)	C3—H3B	0.9600
C6—C5	1.466 (9)	C2—H2A	0.9601
C6—H6A	0.9600	C2—H2B	0.9601

Cl3—Fe1—Cl3ⁱ	112.68 (13)	C2—C1—H1C	108.3
Cl3—Fe1—Cl1	108.61 (8)	O1—C1—H1D	110.1
Cl3ⁱ—Fe1—Cl1	108.61 (8)	C2—C1—H1D	110.9
Cl3—Fe1—Cl2	108.69 (6)	H1C—C1—H1D	108.3
Cl3ⁱ—Fe1—Cl2	108.69 (6)	C2—O2—C3	113.4 (5)
Cl1—Fe1—Cl2	109.52 (12)	C5—O3—C4	111.9 (4)
C7—N1—H1A	110.2	O3—C4—C3	109.1 (4)
C7—N1—H1B	109.1	O3—C4—H4A	110.3
H1A—N1—H1B	109.5	C3—C4—H4A	109.9
C9—C8—C7	123.1 (8)	O3—C4—H4B	109.8
C9—C8—H8A	106.4	C3—C4—H4B	109.4
C7—C8—H8A	106.5	H4A—C4—H4B	108.3
C10—C9—C8	119.0 (9)	O3—C5—C6	108.2 (4)
C10—C9—H9A	107.9	O3—C5—H5A	109.2
C8—C9—H9A	106.9	C6—C5—H5A	110.0
C8—C7—N1	118.4 (6)	O3—C5—H5B	111.1
C8—C7—H7A	106.9	C6—C5—H5B	109.9
N1—C7—H7A	108.3	H5A—C5—H5B	108.4
C9—C10—H10A	111.2	O2—C3—C4	109.5 (4)
C9—C10—H10B	108.6	O2—C3—H3A	109.2
H10A—C10—H10B	109.5	C4—C3—H3A	110.3
C6ⁱⁱ—O4—C6	114.4 (6)	O2—C3—H3B	110.2
O4—C6—C5	110.1 (4)	C4—C3—H3B	109.3
O4—C6—H6A	109.0	H3A—C3—H3B	108.3
C5—C6—H6A	109.6	O2—C2—C1	109.0 (5)
O4—C6—H6B	110.1	O2—C2—H2A	110.3
C5—C6—H6B	109.9	C1—C2—H2A	110.5
H6A—C6—H6B	108.2	O2—C2—H2B	109.7
C1—O1—C1ⁱⁱ	114.1 (6)	C1—C2—H2B	108.7
O1—C1—C2	109.9 (4)	H2A—C2—H2B	108.5
O1—C1—H1C	109.3

Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90	2.07	2.963 (5)	176
N1—H1B···O3	0.90	2.07	2.966 (4)	175

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N)[FeCl₄]·C₁₂H₂₄O₆
M_r	536.11
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	9.3109 (19), 11.431 (2), 24.718 (5)
V (Å³)	2630.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.01
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.665, 0.820
No. of measured, independent and observed [I > 2σ(I)] reflections	24682, 3160, 1649
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.234, 1.04
No. of reflections	3160
No. of parameters	142
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.40

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.90	2.07	2.963 (5)	176
N1—H1B···O3	0.90	2.07	2.966 (4)	175

Acknowledgements

The author is grateful to the starter fund of Nanjing College of Chemical Technology.

References

Akutagawa, T., Koshinaka, H., Sato, D., Takeda, S., Noro, S., Takahashi, H., Kumai, R., Tokura, Y. & Nakamura, T. (2009). Nat. Mater. 8, 342–347. Web of Science CrossRef PubMed CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar