2,5-Bis{[(-)-(S)-1-(4-bromo-phen-yl)eth-yl]imino-meth-yl}thio-phene.

The title compound, C22H20Br2N2S, was synthesized under solvent-free conditions. The mol-ecule shows crystallographic C 2 symmetry, with the S atom of the central thio-phene ring lying on a twofold rotation axis. Furthermore, as a consequence of the (S,S) stereochemistry, the mol-ecule has a twisted conformation. The dihedral angle between the thio-phene and benzene rings is 72.7 (2)° and that between the two benzene rings is 55.9 (2)°. In the crystal, mol-ecules are arranged in a chevron-like pattern, without any significant inter-molecular inter-actions.

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

C22H20Br2N2S

M = 504.27

Monoclinic,

a = 24.5329 (15) Å

b = 5.9762 (5) Å

c = 7.5944 (5) Å

β = 98.536 (6)°

V = 1101.11 (14) Å3

Z = 2

Mo Kα radiation

μ = 3.79 mm−1

T = 298 K

0.52 × 0.15 × 0.06 mm

Data collection

Agilent Xcalibur (Atlas, Gemini) diffractometer

Absorption correction: numerical (CrysAlis PRO; Agilent, 2013 ▶) T min = 0.400, T max = 0.815

6101 measured reflections

2107 independent reflections

1630 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.072

S = 1.03

2107 reflections

124 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.35 e Å−3

Absolute structure: Flack (1983 ▶), 914 Friedel pairs

Absolute structure parameter: 0.011 (8)

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814003651/is5340sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003651/is5340Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814003651/is5340Isup3.cml

CCDC reference: 987496

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

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)