2,3,5,6-Tetra­fluoro-1,4-bis­({[(thio­phen-2-yl)methyl­idene]amino}­meth­yl)benzene

Gao, N.; Luo, H.-K.; Qin, R.-R.; He, M.-Y.

doi:10.1107/S1600536814012434

organic compounds

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https://doi.org/10.1107/S1600536814012434

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2,3,5,6-Tetrafluoro-1,4-bis({[(thiophen-2-yl)methylidene]amino}methyl)benzene

Ning Gao,^a Hai-Kun Luo,^a Rui-Rui Qin ^a and Ming-Yang He ^a ^*

^aSchool of Petrochemical Engineering, Changzhou University, Changzhou 213164, People's Republic of China
^*Correspondence e-mail: hemingyangjpu@yahoo.com

(Received 3 May 2014; accepted 28 May 2014; online 4 June 2014)

In the title compound, C₁₈H₁₂F₄N₂S₂, a bis-thiophenyl Schiff base ligand with a perifluorinated aromatic core, the complete molecule is generated by crystallographic inversion symmetry. The thiophene and tetrafluorinated benzene rings are oriented at a dihedral angle of 77.38 (4)°. The crystal structure exhibits C—H⋯F hydrogen bonds, resulting in supramolecular chains along the c-axis direction.

CCDC reference: 1005697

Related literature

For background information on thiophene-based Schiff base ligands, see: Hee & Soon (2007 ); Fang et al. (2001 ). For fluorine-functionalized complexes, see Chen et al. (2012 ). Zhang et al. (2011 ) describe the synthesis of the title compound.

Experimental

Crystal data

C₁₈H₁₂F₄N₂S₂
M_r = 396.42
Monoclinic, P 2₁ /c
a = 15.500 (7) Å
b = 4.865 (2) Å
c = 11.713 (6) Å
β = 95.371 (9)°
V = 879.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.921, T_max = 0.934
6136 measured reflections
1541 independent reflections
1427 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.090
S = 1.02
1541 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯F1ⁱ	0.93	2.56	3.446 (2)	159
C6—H6B⋯F1ⁱ	0.97	2.63	3.542 (2)	156
Symmetry code: (i) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1005697

Crystal structure: contains datablocks I, 1. DOI: https://doi.org/10.1107/S1600536814012434/im2454sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814012434/im2454Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536814012434/im2454Isup3.cml

checkCIF report

Comment top

In the past decade, thiophen-based bidentate Schiff base ligands have been utilized intensively to assemble various coordination compounds with intriguing structural features and potential applications (Hee & Soon, 2007; Fang et al., 2001). As part of our ongoing studies of the effect of fluorine substitution on crystal structures of coordination polymers (Chen et al., 2012), herein, we wish to report the crystal structure of the title compound, 2,3,5,6-tetrafluoro-1,4-bis(1-(1-thiophen-2-yl)methyleneaminomethyl)benzene, (I).

A perspective view of (I), including the atomic numbering scheme, is shown in Fig. 1. (I) crystallizes around a crystallographic centre with a half molecule in the asymmetric unit. Bond lengths and angles are within normal ranges. The terminal thiophenyl groups are coplanar, and they form a dihedral angle of 77.38 (4)° with the central tetrafluorinated benzene ring. Intermolecular C—H···F hydrogen-bonding interactions link the adjacent molecules to generate one-dimensional supramolecular chains along the c axis (see Fig. 2).

Related literature top

For background information on thiophene-based Schiff base ligands, see: Hee & Soon (2007); Fang et al. (2001). For fluorine-functionalized complexes, see Chen et al. (2012). Zhang et al. (2011) describe the synthesis of the title compound.

Experimental top

Compound (I) was synthesized and purified according to the method described by Zhang et al. (2011) through a condensation of 2,3,5,6-tetrafluoro-1,4-benzenedimethanamine with thiophene-2-carboxaldehyde (yied 75%). ¹H NMR (CDCl₃): δ 2.71 (s, 4H, CH₂), 7.19 (s, 2H, CH), 7.58 (s, 2H, CH), 7.84 (s, 2H, CH), 8.02 (s, 2H, CH).

Colourless needle-like single crystals (m.p. 452.3—452.6 K) suitable for X-ray analysis were obtained by dissolving (I) (20.0 mg) in dichloromethane (6 ml) solution and then slowly evaporating the solvent at room temperature for a period of about one week.

Structure description top

For background information on thiophene-based Schiff base ligands, see: Hee & Soon (2007); Fang et al. (2001). For fluorine-functionalized complexes, see Chen et al. (2012). Zhang et al. (2011) describe the synthesis of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted for clarity.
	Fig. 2. View of the one-dimensional supramolecular chain structure constructed via intermolecular C—H···F hydrogen-bonding interactions (irrelative hydrogen atoms are omitted for clarity).

2,3,5,6-Tetrafluoro-1,4-bis({[(thiophen-2-yl)methylidene]amino}methyl)benzene top

Crystal data top

C₁₈H₁₂F₄N₂S₂	F(000) = 404
M_r = 396.42	D_x = 1.497 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5195 reflections
a = 15.500 (7) Å	θ = 2.6–31.7°
b = 4.865 (2) Å	µ = 0.35 mm⁻¹
c = 11.713 (6) Å	T = 296 K
β = 95.371 (9)°	Shape, colourless
V = 879.3 (7) Å³	0.24 × 0.22 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	1541 independent reflections
Radiation source: fine-focus sealed tube	1427 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −18→17
T_min = 0.921, T_max = 0.934	k = −5→5
6136 measured reflections	l = −13→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0516P)² + 0.297P] where P = (F_o² + 2F_c²)/3
1541 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₈H₁₂F₄N₂S₂	V = 879.3 (7) Å³
M_r = 396.42	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.500 (7) Å	µ = 0.35 mm⁻¹
b = 4.865 (2) Å	T = 296 K
c = 11.713 (6) Å	0.24 × 0.22 × 0.20 mm
β = 95.371 (9)°

Data collection top

Bruker SMART APEX CCD diffractometer	1541 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1427 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.934	R_int = 0.018
6136 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.02	Δρ_max = 0.18 e Å⁻³
1541 reflections	Δρ_min = −0.28 e Å⁻³
118 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
C1	0.43101 (11)	0.7020 (4)	0.85018 (19)	0.0605 (5)
H1	0.4750	0.8166	0.8818	0.073*
C2	0.40375 (12)	0.6938 (4)	0.73736 (18)	0.0610 (5)
H2	0.4266	0.8036	0.6826	0.073*
C3	0.33673 (12)	0.5000 (4)	0.71153 (16)	0.0531 (4)
H3	0.3110	0.4671	0.6378	0.064*
C4	0.31367 (10)	0.3652 (3)	0.80758 (13)	0.0427 (4)
C5	0.24772 (9)	0.1542 (3)	0.81301 (13)	0.0428 (4)
H5	0.2214	0.0838	0.7446	0.051*
C6	0.15903 (10)	−0.1584 (3)	0.89660 (15)	0.0464 (4)
H6A	0.1831	−0.3231	0.9338	0.056*
H6B	0.1440	−0.2005	0.8162	0.056*
C7	0.07804 (9)	−0.0748 (3)	0.95097 (13)	0.0376 (3)
C8	0.05197 (9)	−0.2024 (3)	1.04813 (12)	0.0388 (3)
C9	0.02329 (9)	0.1316 (3)	0.90476 (12)	0.0388 (3)
F1	0.10088 (7)	−0.4083 (2)	1.09813 (8)	0.0566 (3)
F2	0.04382 (6)	0.2659 (2)	0.80981 (8)	0.0549 (3)
N1	0.22433 (8)	0.0614 (3)	0.90663 (12)	0.0445 (3)
S1	0.37524 (3)	0.47708 (10)	0.92848 (4)	0.05398 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0407 (9)	0.0496 (10)	0.0913 (15)	−0.0038 (8)	0.0063 (9)	−0.0024 (10)
C2	0.0532 (10)	0.0521 (10)	0.0809 (14)	0.0022 (9)	0.0229 (9)	0.0114 (10)
C3	0.0513 (10)	0.0576 (11)	0.0517 (10)	0.0049 (8)	0.0108 (8)	0.0013 (8)
C4	0.0354 (7)	0.0451 (9)	0.0477 (9)	0.0048 (6)	0.0052 (6)	−0.0031 (7)
C5	0.0349 (7)	0.0481 (9)	0.0453 (9)	0.0027 (7)	0.0031 (6)	−0.0075 (7)
C6	0.0391 (8)	0.0437 (9)	0.0575 (10)	−0.0013 (7)	0.0107 (7)	−0.0063 (7)
C7	0.0327 (7)	0.0371 (8)	0.0427 (8)	−0.0012 (6)	0.0024 (6)	−0.0045 (6)
C8	0.0366 (7)	0.0355 (8)	0.0429 (8)	0.0042 (6)	−0.0033 (6)	0.0009 (6)
C9	0.0409 (8)	0.0389 (8)	0.0365 (8)	−0.0034 (6)	0.0030 (6)	0.0009 (6)
F1	0.0541 (6)	0.0549 (6)	0.0601 (6)	0.0183 (5)	0.0013 (5)	0.0136 (5)
F2	0.0608 (6)	0.0565 (6)	0.0492 (6)	0.0035 (5)	0.0144 (4)	0.0145 (5)
N1	0.0341 (7)	0.0488 (8)	0.0510 (8)	−0.0003 (6)	0.0056 (6)	−0.0053 (6)
S1	0.0457 (3)	0.0584 (3)	0.0562 (3)	−0.00403 (19)	−0.0039 (2)	−0.0020 (2)

Geometric parameters (Å, º) top

C1—C2	1.350 (3)	C6—N1	1.469 (2)
C1—S1	1.713 (2)	C6—C7	1.515 (2)
C1—H1	0.9300	C6—H6A	0.9700
C2—C3	1.414 (3)	C6—H6B	0.9700
C2—H2	0.9300	C7—C8	1.389 (2)
C3—C4	1.378 (2)	C7—C9	1.391 (2)
C3—H3	0.9300	C8—F1	1.3555 (17)
C4—C5	1.454 (2)	C8—C9ⁱ	1.380 (2)
C4—S1	1.7202 (17)	C9—F2	1.3531 (18)
C5—N1	1.270 (2)	C9—C8ⁱ	1.380 (2)
C5—H5	0.9300

C2—C1—S1	112.19 (15)	N1—C6—H6A	109.4
C2—C1—H1	123.9	C7—C6—H6A	109.4
S1—C1—H1	123.9	N1—C6—H6B	109.4
C1—C2—C3	112.68 (17)	C7—C6—H6B	109.4
C1—C2—H2	123.7	H6A—C6—H6B	108.0
C3—C2—H2	123.7	C8—C7—C9	115.32 (13)
C4—C3—C2	112.58 (17)	C8—C7—C6	122.69 (14)
C4—C3—H3	123.7	C9—C7—C6	121.97 (14)
C2—C3—H3	123.7	F1—C8—C9ⁱ	118.11 (13)
C3—C4—C5	127.50 (15)	F1—C8—C7	119.36 (13)
C3—C4—S1	110.81 (13)	C9ⁱ—C8—C7	122.51 (14)
C5—C4—S1	121.70 (12)	F2—C9—C8ⁱ	118.72 (13)
N1—C5—C4	123.20 (14)	F2—C9—C7	119.11 (13)
N1—C5—H5	118.4	C8ⁱ—C9—C7	122.16 (14)
C4—C5—H5	118.4	C5—N1—C6	116.10 (14)
N1—C6—C7	111.25 (13)	C1—S1—C4	91.74 (10)

S1—C1—C2—C3	−0.6 (2)	C6—C7—C8—C9ⁱ	−177.86 (14)
C1—C2—C3—C4	0.7 (2)	C8—C7—C9—F2	−179.81 (13)
C2—C3—C4—C5	−179.95 (15)	C6—C7—C9—F2	−1.4 (2)
C2—C3—C4—S1	−0.37 (19)	C8—C7—C9—C8ⁱ	−0.5 (2)
C3—C4—C5—N1	−172.30 (16)	C6—C7—C9—C8ⁱ	177.88 (14)
S1—C4—C5—N1	8.2 (2)	C4—C5—N1—C6	−177.93 (14)
N1—C6—C7—C8	−113.68 (16)	C7—C6—N1—C5	−120.34 (16)
N1—C6—C7—C9	68.1 (2)	C2—C1—S1—C4	0.36 (15)
C9—C7—C8—F1	179.22 (13)	C3—C4—S1—C1	0.02 (14)
C6—C7—C8—F1	0.8 (2)	C5—C4—S1—C1	179.62 (14)
C9—C7—C8—C9ⁱ	0.5 (2)

Symmetry code: (i) −x, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···F1	0.97	2.44	2.873 (3)	107
C5—H5···F1ⁱⁱ	0.93	2.56	3.446 (2)	159
C6—H6B···F1ⁱⁱ	0.97	2.63	3.542 (2)	156

Symmetry code: (ii) x, −y−1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1ⁱ	0.93	2.56	3.446 (2)	159
C6—H6B···F1ⁱ	0.97	2.63	3.542 (2)	156

Symmetry code: (i) x, −y−1/2, z−1/2.

Acknowledgements

We gratefully acknowledge financial support from the Open Foundation of Jiangsu Province Key Laboratory of Fine Petrochemical Technology (KF1005) and the Analysis Centre of Changzhou University.

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, S.-C., Zhang, Z.-H., Xu, H., Gao, H.-B., Qin, R.-R., Chen, Q., He, M.-Y. & Du, M. (2012). Inorg. Chem. Commun. 15, 180–184. Web of Science CSD CrossRef Google Scholar
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https://doi.org/10.1107/S1600536814012434

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2,3,5,6-Tetra­fluoro-1,4-bis­­({[(thio­phen-2-yl)methyl­­idene]amino}­meth­yl)benzene

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,3,5,6-Tetrafluoro-1,4-bis({[(thiophen-2-yl)methylidene]amino}methyl)benzene