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

The title chiral bis-aldimine, C24H26N2S, was synthesized using a solvent-free Schiff condensation. The mol-ecule displays crystallographic C 2 symmetry, with the S atom lying on the twofold axis parallel to [100]. As a consequence of the (S,S) stereochemistry, the tolyl groups are oriented towards opposite faces of the thiophene core, giving a twisted conformation for the whole mol-ecule. Mol-ecules are arranged in the crystal in a herringbone-like pattern, without any significant inter-molecular contacts.

Related literature

For the solvent-free approach in 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: Skene & Dufresne (2006 ▶); Fridman & Kaftory (2007 ▶); de Lima et al. (2010 ▶); Kudyakova et al. (2011 ▶, 2012 ▶).

Experimental

Crystal data

C24H26N2S

M = 374.53

Orthorhombic,

a = 6.278 (3) Å

b = 7.900 (3) Å

c = 21.500 (7) Å

V = 1066.4 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.16 mm−1

T = 298 K

0.50 × 0.32 × 0.10 mm

Data collection

Bruker P4 diffractometer

Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T min = 0.754, T max = 0.985

3046 measured reflections

1767 independent reflections

1352 reflections with I > 2σ(I)

R int = 0.066

3 standard reflections every 97 reflections intensity decay: 2.5%

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.155

S = 1.06

1767 reflections

125 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.26 e Å−3

Absolute structure: Flack x determined using 412 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004 ▶)

Absolute structure parameter: −0.08 (18)

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL2013.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813021685/nc2315sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021685/nc2315Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813021685/nc2315Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C24H26N2S	Dx = 1.166 Mg m−3
Mr = 374.53	Melting point: 423 K
Orthorhombic, P22121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2bc 2	Cell parameters from 71 reflections
a = 6.278 (3) Å	θ = 4.2–12.3°
b = 7.900 (3) Å	µ = 0.16 mm−1
c = 21.500 (7) Å	T = 298 K
V = 1066.4 (7) Å3	Plate, colourless
Z = 2	0.50 × 0.32 × 0.10 mm
F(000) = 400

Bruker P4 diffractometer	1352 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 25.1°, θmin = 1.9°
2θ/ω scans	h = −7→5
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −9→9
Tmin = 0.754, Tmax = 0.985	l = −25→25
3046 measured reflections	3 standard reflections every 97 reflections
1767 independent reflections	intensity decay: 2.5%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H-atom parameters constrained
wR(F2) = 0.155	w = 1/[σ2(Fo2) + (0.0559P)2 + 0.760P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1767 reflections	Δρmax = 0.22 e Å−3
125 parameters	Δρmin = −0.26 e Å−3
0 restraints	Absolute structure: Flack x determined using 412 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
0 constraints	Absolute structure parameter: −0.08 (18)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
S1	0.6440 (3)	0.5000	1.0000	0.0580 (5)
C2	0.8347 (8)	0.3700 (6)	0.9686 (2)	0.0536 (12)
C3	1.0327 (8)	0.4251 (7)	0.9825 (2)	0.0645 (15)
H3B	1.1562	0.3696	0.9701	0.077*
C4	0.7765 (9)	0.2268 (7)	0.9303 (2)	0.0579 (13)
H4A	0.8834	0.1535	0.9172	0.069*
N5	0.5897 (7)	0.1971 (6)	0.91410 (19)	0.0578 (11)
C6	0.5569 (9)	0.0468 (7)	0.8745 (2)	0.0651 (15)
H6B	0.6951	0.0064	0.8594	0.078*
C7	0.4544 (14)	−0.0898 (8)	0.9141 (3)	0.099 (2)
H7B	0.5485	−0.1196	0.9476	0.148*
H7C	0.4271	−0.1879	0.8890	0.148*
H7D	0.3226	−0.0483	0.9309	0.148*
C8	0.4176 (8)	0.0904 (6)	0.8199 (2)	0.0540 (12)
C9	0.2393 (8)	0.1892 (7)	0.8261 (2)	0.0605 (14)
H9B	0.2074	0.2369	0.8645	0.073*
C10	0.1074 (9)	0.2188 (8)	0.7765 (3)	0.0665 (14)
H10A	−0.0132	0.2855	0.7822	0.080*
C11	0.1489 (9)	0.1524 (7)	0.7186 (3)	0.0627 (13)
C12	0.3281 (10)	0.0573 (7)	0.7125 (2)	0.0697 (15)
H12D	0.3618	0.0133	0.6736	0.084*
C13	0.4616 (9)	0.0235 (8)	0.7617 (2)	0.0657 (14)
H13D	0.5812	−0.0441	0.7559	0.079*
C14	0.0019 (11)	0.1849 (9)	0.6647 (3)	0.091 (2)
H14A	0.0789	0.1720	0.6265	0.136*
H14B	−0.0533	0.2980	0.6675	0.136*
H14C	−0.1138	0.1055	0.6659	0.136*

	U11	U22	U33	U12	U13	U23
S1	0.0456 (10)	0.0627 (11)	0.0658 (10)	0.000	0.000	−0.0035 (10)
C2	0.051 (3)	0.062 (3)	0.048 (2)	0.001 (3)	0.001 (2)	−0.004 (2)
C3	0.046 (3)	0.085 (4)	0.062 (3)	0.005 (3)	0.002 (2)	−0.018 (3)
C4	0.056 (3)	0.063 (3)	0.055 (3)	0.005 (3)	0.002 (2)	−0.004 (3)
N5	0.059 (3)	0.057 (3)	0.057 (2)	0.002 (2)	−0.007 (2)	−0.006 (2)
C6	0.068 (3)	0.064 (4)	0.064 (3)	0.006 (3)	−0.017 (3)	−0.011 (3)
C7	0.151 (7)	0.063 (4)	0.082 (4)	−0.013 (4)	−0.040 (5)	0.012 (3)
C8	0.055 (3)	0.048 (3)	0.059 (3)	0.000 (2)	0.001 (2)	−0.005 (2)
C9	0.056 (3)	0.068 (3)	0.057 (3)	0.004 (3)	0.006 (2)	−0.009 (3)
C10	0.056 (3)	0.063 (3)	0.080 (3)	0.007 (3)	0.000 (3)	−0.005 (3)
C11	0.064 (3)	0.055 (3)	0.068 (3)	−0.009 (3)	−0.010 (3)	0.000 (3)
C12	0.080 (4)	0.069 (4)	0.059 (3)	0.000 (3)	−0.002 (3)	−0.009 (3)
C13	0.064 (3)	0.066 (3)	0.067 (3)	0.015 (3)	−0.003 (2)	−0.018 (3)
C14	0.098 (5)	0.087 (5)	0.088 (4)	−0.005 (4)	−0.032 (4)	0.008 (4)

S1—C2	1.716 (5)	C8—C9	1.371 (7)
S1—C2i	1.716 (5)	C8—C13	1.387 (7)
C2—C3	1.350 (7)	C9—C10	1.370 (7)
C2—C4	1.446 (7)	C9—H9B	0.9300
C3—C3i	1.403 (10)	C10—C11	1.377 (8)
C3—H3B	0.9300	C10—H10A	0.9300
C4—N5	1.246 (6)	C11—C12	1.359 (8)
C4—H4A	0.9300	C11—C14	1.502 (8)
N5—C6	1.475 (7)	C12—C13	1.374 (8)
C6—C8	1.504 (7)	C12—H12D	0.9300
C6—C7	1.518 (9)	C13—H13D	0.9300
C6—H6B	0.9800	C14—H14A	0.9600
C7—H7B	0.9600	C14—H14B	0.9600
C7—H7C	0.9600	C14—H14C	0.9600
C7—H7D	0.9600
C2—S1—C2i	91.5 (3)	C9—C8—C6	122.0 (5)
C3—C2—C4	127.6 (5)	C13—C8—C6	120.1 (5)
C3—C2—S1	111.2 (4)	C10—C9—C8	121.1 (5)
C4—C2—S1	121.1 (4)	C10—C9—H9B	119.5
C2—C3—C3i	113.0 (3)	C8—C9—H9B	119.5
C2—C3—H3B	123.5	C9—C10—C11	121.6 (5)
C3i—C3—H3B	123.5	C9—C10—H10A	119.2
N5—C4—C2	123.0 (5)	C11—C10—H10A	119.2
N5—C4—H4A	118.5	C12—C11—C10	117.0 (5)
C2—C4—H4A	118.5	C12—C11—C14	122.0 (6)
C4—N5—C6	116.4 (4)	C10—C11—C14	121.0 (6)
N5—C6—C8	110.3 (4)	C11—C12—C13	122.6 (5)
N5—C6—C7	107.9 (4)	C11—C12—H12D	118.7
C8—C6—C7	110.7 (5)	C13—C12—H12D	118.7
N5—C6—H6B	109.3	C12—C13—C8	119.9 (5)
C8—C6—H6B	109.3	C12—C13—H13D	120.0
C7—C6—H6B	109.3	C8—C13—H13D	120.0
C6—C7—H7B	109.5	C11—C14—H14A	109.5
C6—C7—H7C	109.5	C11—C14—H14B	109.5
H7B—C7—H7C	109.5	H14A—C14—H14B	109.5
C6—C7—H7D	109.5	C11—C14—H14C	109.5
H7B—C7—H7D	109.5	H14A—C14—H14C	109.5
H7C—C7—H7D	109.5	H14B—C14—H14C	109.5
C9—C8—C13	117.8 (5)
C2i—S1—C2—C3	0.5 (3)	C7—C6—C8—C13	−100.2 (6)
C2i—S1—C2—C4	−177.0 (5)	C13—C8—C9—C10	0.9 (8)
C4—C2—C3—C3i	176.0 (5)	C6—C8—C9—C10	−175.9 (5)
S1—C2—C3—C3i	−1.3 (7)	C8—C9—C10—C11	−0.6 (9)
C3—C2—C4—N5	−171.3 (5)	C9—C10—C11—C12	−0.7 (9)
S1—C2—C4—N5	5.7 (7)	C9—C10—C11—C14	179.6 (6)
C2—C4—N5—C6	179.4 (4)	C10—C11—C12—C13	1.6 (9)
C4—N5—C6—C8	−132.6 (5)	C14—C11—C12—C13	−178.6 (6)
C4—N5—C6—C7	106.3 (6)	C11—C12—C13—C8	−1.4 (9)
N5—C6—C8—C9	−42.7 (7)	C9—C8—C13—C12	0.0 (8)
C7—C6—C8—C9	76.6 (7)	C6—C8—C13—C12	176.9 (5)
N5—C6—C8—C13	140.5 (5)