organic compounds
2,5-Bis{[(−)-(S)-1-(4-bromophenyl)ethyl]iminomethyl}thiophene
aCentro de Química, Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Puebla, Mexico, bDEP, Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño 64570 Monterrey, NL, Mexico, and cLaboratorio de Síntesis de Complejos, Facultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, PO Box 1067, 72001 Puebla, Puebla, Mexico
*Correspondence e-mail: angel.mendoza@correo.buap.mx
The title compound, C22H20Br2N2S, was synthesized under solvent-free conditions. The molecule shows crystallographic C2 symmetry, with the S atom of the central thiophene ring lying on a twofold rotation axis. Furthermore, as a consequence of the (S,S) stereochemistry, the molecule has a twisted conformation. The dihedral angle between the thiophene and benzene rings is 72.7 (2)° and that between the two benzene rings is 55.9 (2)°. In the crystal, molecules are arranged in a chevron-like pattern, without any significant intermolecular interactions.
CCDC reference: 987496
Related literature
For the solvent-free organic synthesis, see: Tanaka & Toda (2000). For the structure of a chiral bis-aldimine compound, see: Espinosa Leija et al. (2009). For structures of thiophenes substituted in positions 2 and 5 by imine functionalities, see: Bernès et al. (2013); Kudyakova et al. (2012).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2013); cell CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2013); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 987496
10.1107/S1600536814003651/is5340sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814003651/is5340Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814003651/is5340Isup3.cml
Under solvent-free conditions, a mixture of 2,5-thiophenedicarboxaldehyde (100 mg, 0.71 mmol) and (S)-(–)-1-(4-bromophenyl)ethylamine (285 mg, 1.42 mmol) in a 1:2 molar ratio were mixed at room temperature, giving a white solid. The crude was recrystallized from CH2Cl2, affording colorless crystals of the title compound.
Yield 96%; m.p. 147–149 °C. Spectroscopic data: [a]D25 = +59.6 (c 1, CHCl3). IR (KBr): 1623 cm-1 (C=N). 1H NMR (400 MHz, CDCl3/TMS): δ = 1.51, 1.53 (d, 6H, CHCH3,), 4.44, 4.45, 4.47, 4.49(q, 2H, CH), 7.29–7.45 (m, 10 H, Ar), 8.36 (s, 2 H, HC=N). 13C NMR (100 MHz, CDCl3/TMS) δ = 25.1 (CCH3), 68.7 (CHCH3), 120.6 (Ar), 128.3 (Ar), 130.1 (Ar), 131.4 (Ar), 144.0 (Ar), 145.1 (Ar), 152. 7 (HC=N). MS—EI: m/z= 504 (M+).
The
was determined using the of the Br atom, and was that expected from the synthesis, carried-out with an amine. All H atoms were placed in calculated positions, with C—H bond lengths fixed to 0.96 Å for the methyl group and 0.93 Å for aromatic CH groups. Isotropic displacement parameters were calculated as Uiso(H) = 1.5Ueq(carrier atom) for the methyl group and Uiso(H) = 1.2Ueq(carrier atom) otherwise.Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis RED (Agilent, 2013); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).C22H20Br2N2S | F(000) = 504 |
Mr = 504.27 | Dx = 1.521 Mg m−3 |
Monoclinic, C2 | Melting point: 420 K |
Hall symbol: C 2y | Mo Kα radiation, λ = 0.71073 Å |
a = 24.5329 (15) Å | Cell parameters from 1609 reflections |
b = 5.9762 (5) Å | θ = 4.4–25.2° |
c = 7.5944 (5) Å | µ = 3.79 mm−1 |
β = 98.536 (6)° | T = 298 K |
V = 1101.11 (14) Å3 | Prism, colourless |
Z = 2 | 0.52 × 0.15 × 0.06 mm |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2107 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1630 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 10.5564 pixels mm-1 | θmax = 26.1°, θmin = 3.0° |
ω scans | h = −30→30 |
Absorption correction: numerical (CrysAlis PRO; Agilent, 2013) | k = −7→7 |
Tmin = 0.400, Tmax = 0.815 | l = −9→9 |
6101 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0288P)2 + 0.0296P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.072 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.20 e Å−3 |
2107 reflections | Δρmin = −0.35 e Å−3 |
124 parameters | Absolute structure: Flack (1983), 914 Friedel pairs |
1 restraint | Absolute structure parameter: 0.011 (8) |
0 constraints |
C22H20Br2N2S | V = 1101.11 (14) Å3 |
Mr = 504.27 | Z = 2 |
Monoclinic, C2 | Mo Kα radiation |
a = 24.5329 (15) Å | µ = 3.79 mm−1 |
b = 5.9762 (5) Å | T = 298 K |
c = 7.5944 (5) Å | 0.52 × 0.15 × 0.06 mm |
β = 98.536 (6)° |
Agilent Xcalibur (Atlas, Gemini) diffractometer | 2107 independent reflections |
Absorption correction: numerical (CrysAlis PRO; Agilent, 2013) | 1630 reflections with I > 2σ(I) |
Tmin = 0.400, Tmax = 0.815 | Rint = 0.035 |
6101 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.072 | Δρmax = 0.20 e Å−3 |
S = 1.03 | Δρmin = −0.35 e Å−3 |
2107 reflections | Absolute structure: Flack (1983), 914 Friedel pairs |
124 parameters | Absolute structure parameter: 0.011 (8) |
1 restraint |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.15628 (2) | 0.49000 (18) | 0.61658 (7) | 0.1112 (4) | |
S1 | 0.5 | 0.2196 (2) | 0.5 | 0.0472 (4) | |
C9 | 0.47486 (16) | 0.0181 (7) | 0.6292 (5) | 0.0427 (10) | |
C11 | 0.4216 (2) | 0.4840 (10) | 1.0744 (5) | 0.0657 (13) | |
H11A | 0.4194 | 0.6248 | 1.0129 | 0.099* | |
H11B | 0.4595 | 0.4499 | 1.1175 | 0.099* | |
H11C | 0.4013 | 0.4929 | 1.173 | 0.099* | |
C4 | 0.2306 (2) | 0.4327 (11) | 0.7169 (6) | 0.0639 (15) | |
C1 | 0.33894 (18) | 0.3489 (7) | 0.8651 (5) | 0.0441 (11) | |
C6 | 0.3243 (2) | 0.5418 (9) | 0.7670 (6) | 0.0569 (13) | |
H6 | 0.3514 | 0.6457 | 0.7513 | 0.068* | |
N1 | 0.43094 (15) | 0.2748 (6) | 0.8052 (5) | 0.0452 (9) | |
C5 | 0.2703 (2) | 0.5823 (9) | 0.6921 (7) | 0.0674 (16) | |
H5 | 0.2613 | 0.711 | 0.6253 | 0.081* | |
C2 | 0.2971 (2) | 0.1997 (9) | 0.8837 (6) | 0.0603 (13) | |
H2 | 0.3056 | 0.0688 | 0.9482 | 0.072* | |
C3 | 0.2431 (2) | 0.2389 (11) | 0.8092 (7) | 0.0690 (14) | |
H3 | 0.2157 | 0.135 | 0.8218 | 0.083* | |
C7 | 0.3974 (2) | 0.3024 (8) | 0.9485 (5) | 0.0501 (12) | |
H7 | 0.398 | 0.1616 | 1.0149 | 0.06* | |
C8 | 0.44434 (18) | 0.0769 (7) | 0.7709 (6) | 0.0469 (12) | |
H8 | 0.4339 | −0.038 | 0.8414 | 0.056* | |
C10 | 0.4853 (2) | −0.1907 (8) | 0.5728 (7) | 0.0540 (13) | |
H10 | 0.4743 | −0.3205 | 0.625 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0529 (4) | 0.2036 (8) | 0.0729 (4) | 0.0279 (5) | −0.0044 (3) | −0.0229 (5) |
S1 | 0.0553 (11) | 0.0347 (8) | 0.0547 (10) | 0 | 0.0179 (8) | 0 |
C9 | 0.043 (2) | 0.038 (2) | 0.047 (2) | 0.001 (2) | 0.0052 (18) | 0.005 (2) |
C11 | 0.058 (3) | 0.085 (3) | 0.053 (2) | 0.009 (3) | 0.005 (2) | −0.003 (3) |
C4 | 0.044 (3) | 0.106 (5) | 0.042 (2) | 0.005 (3) | 0.006 (2) | −0.009 (3) |
C1 | 0.044 (3) | 0.053 (3) | 0.037 (2) | 0.001 (2) | 0.012 (2) | 0.002 (2) |
C6 | 0.052 (3) | 0.062 (3) | 0.056 (3) | −0.002 (3) | 0.007 (2) | 0.016 (3) |
N1 | 0.042 (2) | 0.052 (2) | 0.0439 (19) | 0.0014 (17) | 0.0134 (17) | 0.0053 (16) |
C5 | 0.063 (4) | 0.084 (4) | 0.053 (3) | 0.010 (3) | 0.003 (3) | 0.014 (3) |
C2 | 0.064 (4) | 0.067 (3) | 0.053 (3) | −0.002 (3) | 0.017 (2) | 0.011 (3) |
C3 | 0.051 (3) | 0.094 (4) | 0.065 (3) | −0.019 (3) | 0.017 (3) | −0.005 (3) |
C7 | 0.051 (3) | 0.060 (3) | 0.043 (2) | 0.006 (2) | 0.017 (2) | 0.011 (2) |
C8 | 0.039 (3) | 0.051 (3) | 0.051 (3) | 0.000 (2) | 0.008 (2) | 0.013 (2) |
C10 | 0.057 (3) | 0.035 (2) | 0.073 (3) | −0.001 (2) | 0.017 (3) | 0.005 (2) |
Br1—C4 | 1.899 (5) | C1—C7 | 1.505 (6) |
S1—C9i | 1.724 (4) | C6—H6 | 0.93 |
S1—C9 | 1.724 (4) | C6—C5 | 1.383 (7) |
C9—C8 | 1.442 (6) | N1—C7 | 1.468 (5) |
C9—C10 | 1.356 (6) | N1—C8 | 1.265 (5) |
C11—H11A | 0.96 | C5—H5 | 0.93 |
C11—H11B | 0.96 | C2—H2 | 0.93 |
C11—H11C | 0.96 | C2—C3 | 1.382 (7) |
C11—C7 | 1.509 (7) | C3—H3 | 0.93 |
C4—C5 | 1.356 (7) | C7—H7 | 0.98 |
C4—C3 | 1.365 (7) | C8—H8 | 0.93 |
C1—C6 | 1.391 (6) | C10—C10i | 1.405 (10) |
C1—C2 | 1.383 (7) | C10—H10 | 0.93 |
C9—S1—C9i | 91.4 (3) | C4—C5—H5 | 120.3 |
C8—C9—S1 | 121.6 (3) | C6—C5—H5 | 120.3 |
C10—C9—S1 | 111.2 (3) | C1—C2—H2 | 119 |
C10—C9—C8 | 127.1 (4) | C3—C2—C1 | 122.0 (5) |
H11A—C11—H11B | 109.5 | C3—C2—H2 | 119 |
H11A—C11—H11C | 109.5 | C4—C3—C2 | 118.9 (5) |
H11B—C11—H11C | 109.5 | C4—C3—H3 | 120.6 |
C7—C11—H11A | 109.5 | C2—C3—H3 | 120.6 |
C7—C11—H11B | 109.5 | C11—C7—H7 | 108.5 |
C7—C11—H11C | 109.5 | C1—C7—C11 | 113.2 (4) |
C5—C4—Br1 | 119.5 (4) | C1—C7—H7 | 108.5 |
C5—C4—C3 | 121.3 (5) | N1—C7—C11 | 109.9 (4) |
C3—C4—Br1 | 119.2 (4) | N1—C7—C1 | 108.2 (3) |
C6—C1—C7 | 122.2 (4) | N1—C7—H7 | 108.5 |
C2—C1—C6 | 116.9 (4) | C9—C8—H8 | 117.9 |
C2—C1—C7 | 120.9 (4) | N1—C8—C9 | 124.1 (4) |
C1—C6—H6 | 119.3 | N1—C8—H8 | 117.9 |
C5—C6—C1 | 121.3 (5) | C9—C10—C10i | 113.1 (3) |
C5—C6—H6 | 119.3 | C9—C10—H10 | 123.5 |
C8—N1—C7 | 116.7 (3) | C10i—C10—H10 | 123.5 |
C4—C5—C6 | 119.5 (5) | ||
Br1—C4—C5—C6 | 179.2 (4) | C2—C1—C6—C5 | 0.2 (7) |
Br1—C4—C3—C2 | −179.2 (4) | C2—C1—C7—C11 | −122.6 (5) |
S1—C9—C8—N1 | 4.2 (6) | C2—C1—C7—N1 | 115.3 (4) |
S1—C9—C10—C10i | 1.2 (7) | C3—C4—C5—C6 | −2.3 (8) |
C9i—S1—C9—C8 | −177.3 (4) | C7—C1—C6—C5 | −179.6 (4) |
C9i—S1—C9—C10 | −0.4 (3) | C7—C1—C2—C3 | 179.7 (4) |
C1—C6—C5—C4 | 1.0 (7) | C7—N1—C8—C9 | 176.9 (4) |
C1—C2—C3—C4 | −1.0 (7) | C8—C9—C10—C10i | 177.9 (5) |
C6—C1—C2—C3 | −0.2 (7) | C8—N1—C7—C11 | 131.9 (4) |
C6—C1—C7—C11 | 57.3 (5) | C8—N1—C7—C1 | −104.0 (4) |
C6—C1—C7—N1 | −64.8 (5) | C10—C9—C8—N1 | −172.2 (5) |
C5—C4—C3—C2 | 2.3 (7) |
Symmetry code: (i) −x+1, y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C22H20Br2N2S |
Mr | 504.27 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 298 |
a, b, c (Å) | 24.5329 (15), 5.9762 (5), 7.5944 (5) |
β (°) | 98.536 (6) |
V (Å3) | 1101.11 (14) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.79 |
Crystal size (mm) | 0.52 × 0.15 × 0.06 |
Data collection | |
Diffractometer | Agilent Xcalibur (Atlas, Gemini) diffractometer |
Absorption correction | Numerical (CrysAlis PRO; Agilent, 2013) |
Tmin, Tmax | 0.400, 0.815 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6101, 2107, 1630 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.072, 1.03 |
No. of reflections | 2107 |
No. of parameters | 124 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.20, −0.35 |
Absolute structure | Flack (1983), 914 Friedel pairs |
Absolute structure parameter | 0.011 (8) |
Computer programs: CrysAlis PRO (Agilent, 2013), CrysAlis RED (Agilent, 2013), SHELXS2013 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).
Acknowledgements
Support from VIEP-UAP (GUPJ-NAT12-G-2013) is acknowledged.
References
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In continuation of our work focused on chiral bisimines (Espinosa Leija et al., 2009; Bernès et al., 2013), we have now synthesized the title compound under the solvent-free approach because of the cleaner, safer, and easier aspects to perform in the synthetic work. So, solvent-free conditions are becoming more popular and it is often claimed that the best solvent is no solvent. (Tanaka & Toda, 2000).
The bis-aldimine compound shows an E configuration over every imine bond (Fig. 1). The molecule is an (S,S) diastereoisomer as expected by synthetic procedure. The asymmetric unit contains a half-molecule. The S atom of the molecule is located on a twofold rotation axis of the space group C2. and as a consequence the Br-aldimines groups are placed opposite to the central thiophene ring. Only some previous reports of 2,5-thiophene compounds with achiral or chiral substituents have showed C2 crystallographic symmetry like title compound (Kudyakova et al., 2012, space group C2/c; Bernès et al., 2013, space group P22121). The crystal packing does not feature any particular interactions (intra or intermolecular) and the supramolecular arrangement in the solid state shows a chevron-like pattern viewed along the b axis (Fig. 2).