organic compounds
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
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 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
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Data collection: APEX2 (Bruker, 2007); cell 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
https://doi.org/10.1107/S1600536814012434/im2454sup1.cif
contains datablocks I, 1. DOI: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
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.
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).
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
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
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.
Data collection: APEX2 (Bruker, 2007); cell
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).C18H12F4N2S2 | F(000) = 404 |
Mr = 396.42 | Dx = 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 |
Bruker SMART APEX CCD diffractometer | 1541 independent reflections |
Radiation source: fine-focus sealed tube | 1427 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
phi and ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −18→17 |
Tmin = 0.921, Tmax = 0.934 | k = −5→5 |
6136 measured reflections | l = −13→12 |
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(Fo2) + (0.0516P)2 + 0.297P] where P = (Fo2 + 2Fc2)/3 |
1541 reflections | (Δ/σ)max = 0.001 |
118 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C18H12F4N2S2 | V = 879.3 (7) Å3 |
Mr = 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)° |
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 = 0.934 | Rint = 0.018 |
6136 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.18 e Å−3 |
1541 reflections | Δρmin = −0.28 e Å−3 |
118 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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. |
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. |
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
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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).