Crystal structure of N,N'-[(thio-phene-2,5-di-yl)bis-(methanylyl-idene)]di-p-toluidine.

The title compound, C20H18N2S, was synthesized by the condensation reaction between p-tolu-idine and thio-phene-2,5-dicarboxaldehye in refluxing toluene with p-toluene-sulfonic acid added as catalyst. The mol-ecule lies on a twofold rotation axis and adopts an E orientation with respect to the azomethine bonds. The dihedral angle between the unqiue benzene ring and the least-squares plane [maximum deviation = 0.0145 (14) Å] containing the azomethine and thio-phene groups is 32.31 (6)°.

Related literature

For the synthesis of the title compound, see: Vaysse & Pastour (1964 ▸). For the syntheses and crystal structures of mol­ecules related to the title compound, see: Bernès et al. (2013 ▸); Mendoza et al. (2014 ▸). For applications of symmetrical diazo­methines, see: Suganya et al. (2014 ▸); Skene & Dufresne (2006 ▸). For related structures, see: Bolduc et al. (2013 ▸).

Experimental

Crystal data

C20H18N2S

M = 318.42

Monoclinic,

a = 37.166 (2) Å

b = 6.0292 (2) Å

c = 7.5814 (4) Å

β = 93.452 (7)°

V = 1695.78 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 298 K

0.32 × 0.24 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▸) T min = 0.713, T max = 1.000

9577 measured reflections

2861 independent reflections

2153 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.145

S = 1.03

2861 reflections

106 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.15 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▸); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▸); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S205698901500849X/lh5761sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500849X/lh5761Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S205698901500849X/lh5761fig1.tif

A view of the title compound (Farrugia, 1997). Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (i) −x + 2, y, −z + ].

CCDC reference: 1062484

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

C20H18N2S	Dx = 1.247 Mg m−3
Mr = 318.42	Melting point: 508 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 37.166 (2) Å	Cell parameters from 5038 reflections
b = 6.0292 (2) Å	θ = 4.3–32.6°
c = 7.5814 (4) Å	µ = 0.19 mm−1
β = 93.452 (7)°	T = 298 K
V = 1695.78 (15) Å3	Plate, yellow
Z = 4	0.32 × 0.24 × 0.07 mm
F(000) = 672

Oxford Diffraction Xcalibur Sapphire3 diffractometer	2861 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 16.1790 pixels mm-1	θmax = 32.6°, θmin = 4.3°
ω scans	h = −55→44
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→9
Tmin = 0.713, Tmax = 1.000	l = −10→10
9577 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048	H-atom parameters constrained
wR(F2) = 0.145	w = 1/[σ2(Fo2) + (0.0795P)2 + 0.2248P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2861 reflections	Δρmax = 0.27 e Å−3
106 parameters	Δρmin = −0.15 e Å−3

Experimental. mp 508 K; UV/Vis λmax(ε)=243 nm (12215 M-1cm-1), 384 nm (26116 M-1cm-1); IR (neat): 551.84 (m), 586.34 (m), 641.18 (m), 705.16 (m), 716.43 (m), 740.14 (m), 790.77 (m-s), 817.7, (versus), 838.08 (s), 863.88 (s), 937.29 (m), 955.06 (m), 966.85 (m), 1014.07 (m), 1060.05 (m), 1107.65 (m), 1166.55 (m), 1193.28 (m), 1211.1 (m), 1238.58 (m), 1274.86 (m), 1295.31(m), 1345.37 (w), 1375.47 (m), 1409.84 (m-s), 1456.61 (m), 1497.28 (s), 1508.13 (m), 1526.25 (m), 1586.19 (s-versus), 1612.45 (m), 1636.29 (w), 1807.98 (w), 1904.79 (w), 2725.8 (w), 2858.33 (w), 2914.98,(w), 3018.47 (w); 1H NMR (300 MHz, CDCl3): δ 8.60 (s, 2H), 7.49 (s, 2H), 7.12 (m, 8H), 2.40 (s, 6H); 13C NMR (300 MHz, CDCl3): δ 151.4258, 148.3818, 146.3021,136.5105, 131.4301, 129.9226, 129.8156, 121.0701, 21.0769

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
S1	1.0000	0.43225 (6)	0.7500	0.04723 (16)
C1	0.98232 (4)	0.8419 (2)	0.7119 (2)	0.0554 (3)
H1	0.9694	0.9702	0.6832	0.066*
C2	0.96895 (4)	0.63105 (19)	0.68436 (18)	0.0476 (3)
N1	0.92443 (3)	0.36610 (17)	0.59260 (16)	0.0488 (3)
C3	0.93398 (4)	0.56950 (19)	0.60827 (19)	0.0490 (3)
H3	0.9179	0.6800	0.5696	0.059*
C4	0.88949 (4)	0.31548 (19)	0.52032 (16)	0.0449 (3)
C5	0.85902 (4)	0.4422 (2)	0.5468 (2)	0.0529 (3)
H5	0.8612	0.5722	0.6126	0.063*
C6	0.82570 (4)	0.3767 (3)	0.4762 (2)	0.0582 (4)
H6	0.8057	0.4645	0.4943	0.070*
C7	0.82125 (4)	0.1822 (2)	0.37840 (19)	0.0553 (3)
C8	0.85167 (4)	0.0561 (2)	0.35382 (19)	0.0540 (3)
H8	0.8494	−0.0745	0.2889	0.065*
C9	0.88525 (4)	0.1194 (2)	0.42325 (19)	0.0498 (3)
H9	0.9052	0.0310	0.4053	0.060*
C10	0.78489 (6)	0.1105 (4)	0.3019 (3)	0.0832 (6)
H10A	0.7841	0.1239	0.1756	0.125*
H10B	0.7666	0.2030	0.3478	0.125*
H10C	0.7807	−0.0411	0.3336	0.125*

	U11	U22	U33	U12	U13	U23
S1	0.0603 (3)	0.0289 (2)	0.0533 (3)	0.000	0.0108 (2)	0.000
C1	0.0585 (8)	0.0306 (5)	0.0780 (9)	0.0020 (5)	0.0118 (7)	0.0022 (5)
C2	0.0570 (8)	0.0343 (5)	0.0527 (7)	0.0002 (5)	0.0140 (5)	0.0022 (5)
N1	0.0557 (6)	0.0379 (5)	0.0534 (6)	−0.0001 (4)	0.0082 (5)	0.0000 (4)
C3	0.0573 (8)	0.0368 (6)	0.0538 (7)	0.0016 (5)	0.0115 (6)	0.0043 (5)
C4	0.0546 (7)	0.0352 (5)	0.0457 (6)	−0.0002 (5)	0.0105 (5)	0.0030 (4)
C5	0.0613 (8)	0.0406 (6)	0.0579 (8)	0.0020 (5)	0.0134 (6)	−0.0066 (5)
C6	0.0553 (8)	0.0543 (7)	0.0663 (9)	0.0067 (6)	0.0146 (6)	−0.0026 (6)
C7	0.0586 (8)	0.0555 (8)	0.0521 (7)	−0.0049 (6)	0.0075 (6)	0.0013 (6)
C8	0.0690 (9)	0.0418 (6)	0.0519 (7)	−0.0047 (6)	0.0084 (6)	−0.0050 (5)
C9	0.0601 (8)	0.0341 (5)	0.0560 (7)	0.0033 (5)	0.0108 (6)	0.0000 (5)
C10	0.0664 (11)	0.0948 (14)	0.0874 (13)	−0.0101 (10)	−0.0035 (10)	−0.0136 (10)

S1—C2i	1.7167 (13)	C5—H5	0.9300
S1—C2	1.7168 (13)	C6—C7	1.392 (2)
C1—C2	1.3762 (17)	C6—H6	0.9300
C1—C1i	1.403 (3)	C7—C8	1.384 (2)
C1—H1	0.9300	C7—C10	1.501 (2)
C2—C3	1.439 (2)	C8—C9	1.379 (2)
N1—C3	1.2802 (16)	C8—H8	0.9300
N1—C4	1.4122 (18)	C9—H9	0.9300
C3—H3	0.9300	C10—H10A	0.9600
C4—C5	1.3907 (19)	C10—H10B	0.9600
C4—C9	1.3963 (17)	C10—H10C	0.9600
C5—C6	1.377 (2)
C2i—S1—C2	91.43 (9)	C5—C6—H6	119.2
C2—C1—C1i	112.53 (9)	C7—C6—H6	119.2
C2—C1—H1	123.7	C8—C7—C6	117.54 (14)
C1i—C1—H1	123.7	C8—C7—C10	120.90 (15)
C1—C2—C3	127.48 (12)	C6—C7—C10	121.56 (15)
C1—C2—S1	111.75 (11)	C9—C8—C7	121.63 (12)
C3—C2—S1	120.76 (9)	C9—C8—H8	119.2
C3—N1—C4	119.09 (12)	C7—C8—H8	119.2
N1—C3—C2	121.53 (12)	C8—C9—C4	120.43 (13)
N1—C3—H3	119.2	C8—C9—H9	119.8
C2—C3—H3	119.2	C4—C9—H9	119.8
C5—C4—C9	118.30 (13)	C7—C10—H10A	109.5
C5—C4—N1	124.28 (11)	C7—C10—H10B	109.5
C9—C4—N1	117.35 (12)	H10A—C10—H10B	109.5
C6—C5—C4	120.49 (12)	C7—C10—H10C	109.5
C6—C5—H5	119.8	H10A—C10—H10C	109.5
C4—C5—H5	119.8	H10B—C10—H10C	109.5
C5—C6—C7	121.62 (14)
C1i—C1—C2—C3	−179.60 (16)	N1—C4—C5—C6	−177.78 (13)
C1i—C1—C2—S1	−0.6 (2)	C4—C5—C6—C7	0.7 (2)
C2i—S1—C2—C1	0.23 (8)	C5—C6—C7—C8	−0.2 (2)
C2i—S1—C2—C3	179.28 (15)	C5—C6—C7—C10	179.82 (17)
C4—N1—C3—C2	178.67 (12)	C6—C7—C8—C9	0.1 (2)
C1—C2—C3—N1	−178.68 (14)	C10—C7—C8—C9	−179.95 (16)
S1—C2—C3—N1	2.4 (2)	C7—C8—C9—C4	−0.4 (2)
C3—N1—C4—C5	−35.2 (2)	C5—C4—C9—C8	0.9 (2)
C3—N1—C4—C9	148.02 (13)	N1—C4—C9—C8	177.88 (12)
C9—C4—C5—C6	−1.0 (2)