4-Fluoro-anilinium tetra-chloridoferrate(III) 18-crown-6 clathrate.

The reaction of 4-fluoro-aniline hydro-chloride, 18-crown-6 and ferric chloride in methano-lic solution yields the title compound, (C(6)H(7)FN)[FeCl(4)]·C(12)H(24)O(6), which has an unusual supramolecular structure. N-H⋯O hydrogen-bonding inter-actions between the NH(3) (+) substituents of the 4-fluoro-anilinium cations and the O atoms of the crown ether mol-ecules result in a rotator-stator-like structure.

Related literature

For a related 18-crown-6 clathrate, see: Fender et al. (2002 ▶). For the ferroelectric properties of selected transition metal complexes, see: Fu et al. (2007 ▶); Ye et al. (2009 ▶); Zhang et al. (2009 ▶).

Experimental

Crystal data

(C6H7FN)[FeCl4]·C12H24O6

M = 574.09

Monoclinic,

a = 11.45 (1) Å

b = 24.14 (2) Å

c = 9.719 (9) Å

β = 96.82 (2)°

V = 2667 (4) Å3

Z = 4

Mo Kα radiation

μ = 1.00 mm−1

T = 293 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.818, T max = 0.818

26978 measured reflections

6039 independent reflections

3173 reflections with I > 2σ(I)

R int = 0.068

Refinement

R[F 2 > 2σ(F 2)] = 0.078

wR(F 2) = 0.271

S = 1.07

6039 reflections

281 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.35 e Å−3

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: PRPKAPPA (Ferguson, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002009X/im2203sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002009X/im2203Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C6H7FN)[FeCl4]·C12H24O6	F(000) = 1188
Mr = 574.09	Dx = 1.430 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5625 reflections
a = 11.45 (1) Å	θ = 2.3–27.5°
b = 24.14 (2) Å	µ = 1.00 mm−1
c = 9.719 (9) Å	T = 293 K
β = 96.82 (2)°	Block, pale yellow
V = 2667 (4) Å3	0.20 × 0.20 × 0.20 mm
Z = 4

Rigaku SCXmini diffractometer	6039 independent reflections
Radiation source: fine-focus sealed tube	3173 reflections with I > 2σ(I)
graphite	Rint = 0.068
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 2.3°
ω scans	h = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −31→31
Tmin = 0.818, Tmax = 0.818	l = −12→12
26978 measured 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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.271	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1312P)2 + 0.8151P] where P = (Fo2 + 2Fc2)/3
6039 reflections	(Δ/σ)max = 0.005
281 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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 > 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
O1	0.5434 (4)	0.09467 (19)	0.7021 (5)	0.0842 (13)
O2	0.7834 (4)	0.06611 (18)	0.6808 (4)	0.0816 (12)
O3	0.9463 (3)	0.14900 (18)	0.7297 (5)	0.0741 (11)
O4	0.8972 (4)	0.23864 (18)	0.8904 (5)	0.0849 (13)
O5	0.6635 (4)	0.25943 (19)	0.9254 (5)	0.0903 (14)
O6	0.4892 (4)	0.1787 (2)	0.8722 (5)	0.0895 (14)
C1	0.5820 (8)	0.0397 (3)	0.6788 (9)	0.102 (2)
H1A	0.5188	0.0190	0.6268	0.122*
H1B	0.6025	0.0212	0.7670	0.122*
C2	0.6847 (7)	0.0408 (3)	0.6013 (8)	0.093 (2)
H2A	0.7049	0.0033	0.5776	0.112*
H2B	0.6653	0.0613	0.5158	0.112*
C3	0.8831 (6)	0.0647 (3)	0.6178 (7)	0.0800 (18)
H3A	0.8688	0.0824	0.5278	0.096*
H3B	0.9053	0.0265	0.6039	0.096*
C4	0.9802 (6)	0.0937 (3)	0.7041 (7)	0.0798 (18)
H4A	0.9987	0.0743	0.7913	0.096*
H4B	1.0500	0.0939	0.6565	0.096*
C5	1.0380 (5)	0.1806 (3)	0.7950 (8)	0.086 (2)
H5A	1.1034	0.1806	0.7400	0.104*
H5B	1.0650	0.1648	0.8850	0.104*
C6	0.9964 (6)	0.2383 (3)	0.8120 (9)	0.091 (2)
H6A	1.0596	0.2603	0.8595	0.109*
H6B	0.9739	0.2546	0.7216	0.109*
C7	0.8554 (8)	0.2921 (3)	0.9050 (10)	0.104 (3)
H7A	0.8286	0.3074	0.8145	0.124*
H7B	0.9180	0.3154	0.9488	0.124*
C8	0.7560 (8)	0.2905 (3)	0.9917 (11)	0.113 (3)
H8A	0.7825	0.2743	1.0812	0.136*
H8B	0.7293	0.3280	1.0067	0.136*
C9	0.5658 (7)	0.2584 (4)	0.9976 (9)	0.100 (2)
H9A	0.5470	0.2955	1.0261	0.120*
H9B	0.5813	0.2355	1.0798	0.120*
C10	0.4667 (6)	0.2353 (3)	0.9035 (9)	0.091 (2)
H10A	0.3948	0.2377	0.9469	0.109*
H10B	0.4561	0.2567	0.8184	0.109*
C11	0.4035 (6)	0.1551 (4)	0.7758 (10)	0.101 (2)
H11A	0.3981	0.1759	0.6899	0.122*
H11B	0.3276	0.1569	0.8108	0.122*
C12	0.4324 (6)	0.0968 (3)	0.7491 (10)	0.100 (2)
H12A	0.4329	0.0753	0.8334	0.119*
H12B	0.3736	0.0813	0.6797	0.119*
F1	0.8204 (4)	0.00256 (15)	0.3199 (4)	0.0906 (12)
N1	0.7364 (3)	0.14716 (16)	−0.1213 (4)	0.0498 (9)
H1C	0.7853	0.1760	−0.1140	0.075*
H1D	0.6625	0.1592	−0.1276	0.075*
H1E	0.7467	0.1277	−0.1967	0.075*
C13	0.8711 (5)	0.0971 (3)	0.0489 (7)	0.0748 (17)
H13A	0.9340	0.1117	0.0085	0.090*
C14	0.7606 (4)	0.11179 (19)	0.0016 (5)	0.0493 (11)
C15	0.6684 (5)	0.0924 (3)	0.0657 (7)	0.0699 (16)
H15A	0.5920	0.1037	0.0355	0.084*
C16	0.6894 (6)	0.0558 (3)	0.1752 (7)	0.0758 (17)
H16A	0.6279	0.0427	0.2206	0.091*
C17	0.8011 (6)	0.0396 (2)	0.2148 (6)	0.0658 (15)
C18	0.8913 (6)	0.0598 (3)	0.1588 (7)	0.0804 (18)
H18A	0.9676	0.0493	0.1922	0.096*
Fe2	0.25883 (7)	0.12580 (3)	0.22601 (9)	0.0635 (3)
Cl1	0.44359 (16)	0.11643 (9)	0.3030 (3)	0.1179 (8)
Cl2	0.2109 (2)	0.06493 (9)	0.0642 (2)	0.1121 (7)
Cl3	0.22522 (16)	0.20828 (7)	0.13775 (19)	0.0840 (5)
Cl4	0.1561 (2)	0.11388 (10)	0.3981 (2)	0.1144 (8)

	U11	U22	U33	U12	U13	U23
O1	0.079 (3)	0.078 (3)	0.094 (3)	−0.018 (2)	0.006 (2)	−0.002 (2)
O2	0.104 (4)	0.073 (3)	0.070 (3)	0.002 (2)	0.015 (2)	−0.007 (2)
O3	0.058 (2)	0.079 (3)	0.086 (3)	0.010 (2)	0.012 (2)	0.006 (2)
O4	0.081 (3)	0.076 (3)	0.100 (3)	−0.021 (2)	0.021 (2)	−0.006 (2)
O5	0.086 (3)	0.078 (3)	0.109 (4)	0.010 (2)	0.022 (3)	−0.015 (3)
O6	0.062 (3)	0.098 (3)	0.109 (4)	0.013 (2)	0.013 (2)	0.017 (3)
C1	0.122 (7)	0.089 (5)	0.091 (5)	−0.017 (5)	0.003 (5)	−0.016 (4)
C2	0.115 (6)	0.074 (4)	0.090 (5)	−0.018 (4)	0.011 (4)	−0.024 (4)
C3	0.093 (5)	0.077 (4)	0.073 (4)	0.029 (4)	0.017 (3)	−0.005 (3)
C4	0.080 (4)	0.072 (4)	0.089 (5)	0.020 (3)	0.017 (4)	0.000 (3)
C5	0.045 (3)	0.101 (5)	0.114 (5)	−0.010 (3)	0.010 (3)	0.013 (4)
C6	0.068 (4)	0.097 (5)	0.110 (6)	−0.021 (4)	0.020 (4)	0.006 (4)
C7	0.127 (7)	0.066 (4)	0.120 (6)	−0.022 (4)	0.025 (5)	−0.029 (4)
C8	0.112 (6)	0.092 (5)	0.136 (7)	−0.022 (5)	0.017 (5)	−0.046 (5)
C9	0.091 (5)	0.109 (6)	0.108 (6)	0.024 (4)	0.044 (5)	0.002 (5)
C10	0.071 (4)	0.085 (5)	0.121 (6)	0.029 (4)	0.036 (4)	0.012 (4)
C11	0.057 (4)	0.117 (6)	0.129 (6)	−0.003 (4)	0.011 (4)	0.036 (5)
C12	0.059 (4)	0.102 (6)	0.135 (7)	−0.028 (4)	0.002 (4)	0.013 (5)
F1	0.122 (3)	0.087 (2)	0.065 (2)	0.032 (2)	0.019 (2)	0.0282 (19)
N1	0.048 (2)	0.049 (2)	0.053 (2)	0.0015 (17)	0.0086 (18)	0.0046 (18)
C13	0.053 (3)	0.096 (4)	0.075 (4)	−0.004 (3)	0.006 (3)	0.019 (3)
C14	0.054 (3)	0.048 (3)	0.047 (3)	0.002 (2)	0.011 (2)	−0.003 (2)
C15	0.053 (3)	0.078 (4)	0.081 (4)	0.012 (3)	0.018 (3)	0.022 (3)
C16	0.072 (4)	0.075 (4)	0.086 (4)	0.011 (3)	0.032 (3)	0.024 (3)
C17	0.090 (4)	0.055 (3)	0.053 (3)	0.007 (3)	0.010 (3)	0.005 (2)
C18	0.061 (4)	0.105 (5)	0.074 (4)	0.015 (3)	0.003 (3)	0.026 (4)
Fe2	0.0551 (5)	0.0653 (5)	0.0706 (5)	0.0049 (4)	0.0089 (4)	−0.0102 (4)
Cl1	0.0592 (10)	0.1006 (14)	0.187 (2)	0.0182 (9)	−0.0152 (12)	−0.0312 (14)
Cl2	0.1251 (17)	0.0938 (13)	0.1119 (15)	0.0013 (11)	−0.0090 (12)	−0.0418 (12)
Cl3	0.0859 (11)	0.0766 (10)	0.0914 (11)	0.0080 (8)	0.0180 (9)	0.0043 (9)
Cl4	0.1298 (18)	0.1178 (16)	0.1061 (15)	0.0209 (13)	0.0577 (13)	0.0211 (12)

O1—C12	1.401 (8)	C8—H8B	0.9700
O1—C1	1.425 (9)	C9—C10	1.480 (12)
O2—C3	1.357 (8)	C9—H9A	0.9700
O2—C2	1.428 (8)	C9—H9B	0.9700
O3—C5	1.388 (7)	C10—H10A	0.9700
O3—C4	1.420 (7)	C10—H10B	0.9700
O4—C7	1.388 (8)	C11—C12	1.476 (11)
O4—C6	1.441 (8)	C11—H11A	0.9700
O5—C9	1.390 (8)	C11—H11B	0.9700
O5—C8	1.391 (9)	C12—H12A	0.9700
O6—C11	1.396 (9)	C12—H12B	0.9700
O6—C10	1.428 (8)	F1—C17	1.356 (6)
C1—C2	1.471 (11)	N1—C14	1.467 (6)
C1—H1A	0.9700	N1—H1C	0.8900
C1—H1B	0.9700	N1—H1D	0.8900
C2—H2A	0.9700	N1—H1E	0.8900
C2—H2B	0.9700	C13—C14	1.341 (8)
C3—C4	1.486 (10)	C13—C18	1.396 (8)
C3—H3A	0.9700	C13—H13A	0.9300
C3—H3B	0.9700	C14—C15	1.371 (7)
C4—H4A	0.9700	C15—C16	1.381 (8)
C4—H4B	0.9700	C15—H15A	0.9300
C5—C6	1.487 (10)	C16—C17	1.349 (9)
C5—H5A	0.9700	C16—H16A	0.9300
C5—H5B	0.9700	C17—C18	1.317 (8)
C6—H6A	0.9700	C18—H18A	0.9300
C6—H6B	0.9700	Fe2—Cl1	2.170 (3)
C7—C8	1.495 (12)	Fe2—Cl2	2.175 (2)
C7—H7A	0.9700	Fe2—Cl4	2.175 (3)
C7—H7B	0.9700	Fe2—Cl3	2.184 (2)
C8—H8A	0.9700
C12—O1—C1	113.4 (6)	O5—C9—C10	107.4 (7)
C3—O2—C2	113.5 (5)	O5—C9—H9A	110.2
C5—O3—C4	112.9 (5)	C10—C9—H9A	110.2
C7—O4—C6	111.2 (5)	O5—C9—H9B	110.2
C9—O5—C8	113.0 (7)	C10—C9—H9B	110.2
C11—O6—C10	113.7 (6)	H9A—C9—H9B	108.5
O1—C1—C2	110.2 (6)	O6—C10—C9	110.3 (6)
O1—C1—H1A	109.6	O6—C10—H10A	109.6
C2—C1—H1A	109.6	C9—C10—H10A	109.6
O1—C1—H1B	109.6	O6—C10—H10B	109.6
C2—C1—H1B	109.6	C9—C10—H10B	109.6
H1A—C1—H1B	108.1	H10A—C10—H10B	108.1
O2—C2—C1	111.2 (6)	O6—C11—C12	110.7 (6)
O2—C2—H2A	109.4	O6—C11—H11A	109.5
C1—C2—H2A	109.4	C12—C11—H11A	109.5
O2—C2—H2B	109.4	O6—C11—H11B	109.5
C1—C2—H2B	109.4	C12—C11—H11B	109.5
H2A—C2—H2B	108.0	H11A—C11—H11B	108.1
O2—C3—C4	110.3 (6)	O1—C12—C11	108.9 (6)
O2—C3—H3A	109.6	O1—C12—H12A	109.9
C4—C3—H3A	109.6	C11—C12—H12A	109.9
O2—C3—H3B	109.6	O1—C12—H12B	109.9
C4—C3—H3B	109.6	C11—C12—H12B	109.9
H3A—C3—H3B	108.1	H12A—C12—H12B	108.3
O3—C4—C3	109.9 (5)	C14—N1—H1C	109.5
O3—C4—H4A	109.7	C14—N1—H1D	109.5
C3—C4—H4A	109.7	H1C—N1—H1D	109.5
O3—C4—H4B	109.7	C14—N1—H1E	109.5
C3—C4—H4B	109.7	H1C—N1—H1E	109.5
H4A—C4—H4B	108.2	H1D—N1—H1E	109.5
O3—C5—C6	109.3 (5)	C14—C13—C18	119.8 (5)
O3—C5—H5A	109.8	C14—C13—H13A	120.1
C6—C5—H5A	109.8	C18—C13—H13A	120.1
O3—C5—H5B	109.8	C13—C14—C15	120.0 (5)
C6—C5—H5B	109.8	C13—C14—N1	120.8 (5)
H5A—C5—H5B	108.3	C15—C14—N1	119.2 (5)
O4—C6—C5	110.3 (5)	C14—C15—C16	119.7 (5)
O4—C6—H6A	109.6	C14—C15—H15A	120.1
C5—C6—H6A	109.6	C16—C15—H15A	120.1
O4—C6—H6B	109.6	C17—C16—C15	118.5 (5)
C5—C6—H6B	109.6	C17—C16—H16A	120.7
H6A—C6—H6B	108.1	C15—C16—H16A	120.7
O4—C7—C8	109.2 (7)	C18—C17—C16	122.6 (6)
O4—C7—H7A	109.8	C18—C17—F1	119.3 (6)
C8—C7—H7A	109.8	C16—C17—F1	118.1 (6)
O4—C7—H7B	109.8	C17—C18—C13	119.2 (6)
C8—C7—H7B	109.8	C17—C18—H18A	120.4
H7A—C7—H7B	108.3	C13—C18—H18A	120.4
O5—C8—C7	109.9 (7)	Cl1—Fe2—Cl2	109.35 (9)
O5—C8—H8A	109.7	Cl1—Fe2—Cl4	108.36 (13)
C7—C8—H8A	109.7	Cl2—Fe2—Cl4	110.70 (12)
O5—C8—H8B	109.7	Cl1—Fe2—Cl3	110.46 (9)
C7—C8—H8B	109.7	Cl2—Fe2—Cl3	108.32 (11)
H8A—C8—H8B	108.2	Cl4—Fe2—Cl3	109.66 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O4i	0.89	1.98	2.868 (6)	176
N1—H1D···O6i	0.89	2.04	2.924 (6)	173
N1—H1E···O2i	0.89	1.98	2.840 (6)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O4i	0.89	1.98	2.868 (6)	176
N1—H1D⋯O6i	0.89	2.04	2.924 (6)	173
N1—H1E⋯O2i	0.89	1.98	2.840 (6)	162

Symmetry code: (i) .