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

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

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.

Related literature

For background information on thio­phene-based Schiff base ligands, see: Hee & Soon (2007[Hee, K. L. & Soon, W. L. (2007). Bull. Korean Chem. Soc. 28, 421-426.]); Fang et al. (2001[Fang, X., Watkin, J. G., Scott, B. L. & Kubas, G. J. (2001). Organometallics, 20, 3351-3354.]). For fluorine-functionalized complexes, see Chen et al. (2012[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.]). Zhang et al. (2011[Zhang, Z.-H., Chen, S.-C., He, M.-Y., Li, C., Chen, Q. & Du, M. (2011). Cryst. Growth Des. 11, 5171-5175.]) describe the synthesis of the title compound.

[Scheme 1]

Experimental

Crystal data
  • C18H12F4N2S2

  • Mr = 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[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.921, Tmax = 0.934

  • 6136 measured reflections

  • 1541 independent reflections

  • 1427 reflections with I > 2σ(I)

  • Rint = 0.018

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.090

  • S = 1.02

  • 1541 reflections

  • 118 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 2005[Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

All H atoms bound to carbon were assigned to calculated positions, with C—H = 0.97 Å (methylene) and 0.93 Å (aromatic and imine), and refined using a riding model, with Uiso(H)=1.2Ueq (C).

Structure description 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).

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
[Figure 1] 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.
[Figure 2] 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
C18H12F4N2S2F(000) = 404
Mr = 396.42Dx = 1.497 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5195 reflections
a = 15.500 (7) Åθ = 2.6–31.7°
b = 4.865 (2) ŵ = 0.35 mm1
c = 11.713 (6) ÅT = 296 K
β = 95.371 (9)°Shape, colourless
V = 879.3 (7) Å30.24 × 0.22 × 0.20 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer
1541 independent reflections
Radiation source: fine-focus sealed tube1427 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
phi and ω scansθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1817
Tmin = 0.921, Tmax = 0.934k = 55
6136 measured reflectionsl = 1312
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0516P)2 + 0.297P]
where P = (Fo2 + 2Fc2)/3
1541 reflections(Δ/σ)max = 0.001
118 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C18H12F4N2S2V = 879.3 (7) Å3
Mr = 396.42Z = 2
Monoclinic, P21/cMo Kα radiation
a = 15.500 (7) ŵ = 0.35 mm1
b = 4.865 (2) ÅT = 296 K
c = 11.713 (6) Å0.24 × 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)
Tmin = 0.921, Tmax = 0.934Rint = 0.018
6136 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.02Δρmax = 0.18 e Å3
1541 reflectionsΔρmin = 0.28 e Å3
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
xyzUiso*/Ueq
C10.43101 (11)0.7020 (4)0.85018 (19)0.0605 (5)
H10.47500.81660.88180.073*
C20.40375 (12)0.6938 (4)0.73736 (18)0.0610 (5)
H20.42660.80360.68260.073*
C30.33673 (12)0.5000 (4)0.71153 (16)0.0531 (4)
H30.31100.46710.63780.064*
C40.31367 (10)0.3652 (3)0.80758 (13)0.0427 (4)
C50.24772 (9)0.1542 (3)0.81301 (13)0.0428 (4)
H50.22140.08380.74460.051*
C60.15903 (10)0.1584 (3)0.89660 (15)0.0464 (4)
H6A0.18310.32310.93380.056*
H6B0.14400.20050.81620.056*
C70.07804 (9)0.0748 (3)0.95097 (13)0.0376 (3)
C80.05197 (9)0.2024 (3)1.04813 (12)0.0388 (3)
C90.02329 (9)0.1316 (3)0.90476 (12)0.0388 (3)
F10.10088 (7)0.4083 (2)1.09813 (8)0.0566 (3)
F20.04382 (6)0.2659 (2)0.80981 (8)0.0549 (3)
N10.22433 (8)0.0614 (3)0.90663 (12)0.0445 (3)
S10.37524 (3)0.47708 (10)0.92848 (4)0.05398 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0407 (9)0.0496 (10)0.0913 (15)0.0038 (8)0.0063 (9)0.0024 (10)
C20.0532 (10)0.0521 (10)0.0809 (14)0.0022 (9)0.0229 (9)0.0114 (10)
C30.0513 (10)0.0576 (11)0.0517 (10)0.0049 (8)0.0108 (8)0.0013 (8)
C40.0354 (7)0.0451 (9)0.0477 (9)0.0048 (6)0.0052 (6)0.0031 (7)
C50.0349 (7)0.0481 (9)0.0453 (9)0.0027 (7)0.0031 (6)0.0075 (7)
C60.0391 (8)0.0437 (9)0.0575 (10)0.0013 (7)0.0107 (7)0.0063 (7)
C70.0327 (7)0.0371 (8)0.0427 (8)0.0012 (6)0.0024 (6)0.0045 (6)
C80.0366 (7)0.0355 (8)0.0429 (8)0.0042 (6)0.0033 (6)0.0009 (6)
C90.0409 (8)0.0389 (8)0.0365 (8)0.0034 (6)0.0030 (6)0.0009 (6)
F10.0541 (6)0.0549 (6)0.0601 (6)0.0183 (5)0.0013 (5)0.0136 (5)
F20.0608 (6)0.0565 (6)0.0492 (6)0.0035 (5)0.0144 (4)0.0145 (5)
N10.0341 (7)0.0488 (8)0.0510 (8)0.0003 (6)0.0056 (6)0.0053 (6)
S10.0457 (3)0.0584 (3)0.0562 (3)0.00403 (19)0.0039 (2)0.0020 (2)
Geometric parameters (Å, º) top
C1—C21.350 (3)C6—N11.469 (2)
C1—S11.713 (2)C6—C71.515 (2)
C1—H10.9300C6—H6A0.9700
C2—C31.414 (3)C6—H6B0.9700
C2—H20.9300C7—C81.389 (2)
C3—C41.378 (2)C7—C91.391 (2)
C3—H30.9300C8—F11.3555 (17)
C4—C51.454 (2)C8—C9i1.380 (2)
C4—S11.7202 (17)C9—F21.3531 (18)
C5—N11.270 (2)C9—C8i1.380 (2)
C5—H50.9300
C2—C1—S1112.19 (15)N1—C6—H6A109.4
C2—C1—H1123.9C7—C6—H6A109.4
S1—C1—H1123.9N1—C6—H6B109.4
C1—C2—C3112.68 (17)C7—C6—H6B109.4
C1—C2—H2123.7H6A—C6—H6B108.0
C3—C2—H2123.7C8—C7—C9115.32 (13)
C4—C3—C2112.58 (17)C8—C7—C6122.69 (14)
C4—C3—H3123.7C9—C7—C6121.97 (14)
C2—C3—H3123.7F1—C8—C9i118.11 (13)
C3—C4—C5127.50 (15)F1—C8—C7119.36 (13)
C3—C4—S1110.81 (13)C9i—C8—C7122.51 (14)
C5—C4—S1121.70 (12)F2—C9—C8i118.72 (13)
N1—C5—C4123.20 (14)F2—C9—C7119.11 (13)
N1—C5—H5118.4C8i—C9—C7122.16 (14)
C4—C5—H5118.4C5—N1—C6116.10 (14)
N1—C6—C7111.25 (13)C1—S1—C491.74 (10)
S1—C1—C2—C30.6 (2)C6—C7—C8—C9i177.86 (14)
C1—C2—C3—C40.7 (2)C8—C7—C9—F2179.81 (13)
C2—C3—C4—C5179.95 (15)C6—C7—C9—F21.4 (2)
C2—C3—C4—S10.37 (19)C8—C7—C9—C8i0.5 (2)
C3—C4—C5—N1172.30 (16)C6—C7—C9—C8i177.88 (14)
S1—C4—C5—N18.2 (2)C4—C5—N1—C6177.93 (14)
N1—C6—C7—C8113.68 (16)C7—C6—N1—C5120.34 (16)
N1—C6—C7—C968.1 (2)C2—C1—S1—C40.36 (15)
C9—C7—C8—F1179.22 (13)C3—C4—S1—C10.02 (14)
C6—C7—C8—F10.8 (2)C5—C4—S1—C1179.62 (14)
C9—C7—C8—C9i0.5 (2)
Symmetry code: (i) x, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···F10.972.442.873 (3)107
C5—H5···F1ii0.932.563.446 (2)159
C6—H6B···F1ii0.972.633.542 (2)156
Symmetry code: (ii) x, y1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···F1i0.932.563.446 (2)159
C6—H6B···F1i0.972.633.542 (2)156
Symmetry code: (i) x, y1/2, z1/2.
 

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

First citationBrandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
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First citationChen, 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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