N,N′-Bis[(E)-2-thienylmethyl­ene]-4,4′-oxydianiline

Tao, X.; Cui, H.

doi:10.1107/S1600536809033285

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2251

doi:10.1107/S1600536809033285

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N,N′-Bis[(E)-2-thienylmethylene]-4,4′-oxydianiline

Xuquan Tao ^a ^* and Hui Cui ^b

^aCollege of Materials Science and Engineering, Liaocheng University, Shandong 252059, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: taoxuquan@lcu.edu.cn

(Received 22 July 2009; accepted 21 August 2009; online 26 August 2009)

In the title molecule, C₂₂H₁₆N₂OS₂, which demonstrates non-crystallographic C₂ pseudosymmetry [C—O—C angle = 121.0 (3)°], the two benzene rings make a dihedral angle of 62.09 (14)°. The crystal packing exhibits no significantly short intermolecular contacts.

Related literature

For general background, see: Nakajima et al. (1998 ); Opstal & Verpoort (2003 ); Chakraborty & Patel (1996 ). For a related structure, see Hu et al. (2008 ).

Experimental

Crystal data

C₂₂H₁₆N₂OS₂
M_r = 388.49
Monoclinic, P 2₁ /n
a = 6.0897 (7) Å
b = 41.478 (3) Å
c = 7.5300 (12) Å
β = 90.130 (1)°
V = 1902.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 K
0.40 × 0.37 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.891, T_max = 0.985
8674 measured reflections
3319 independent reflections
2079 reflections with I > 2σ(I)
R_int = 0.073

Refinement

R[F² > 2σ(F²)] = 0.090
wR(F²) = 0.218
S = 1.08
3319 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033285/cv2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033285/cv2595Isup2.hkl

checkCIF report

Comment top

In the recent years, there is a considerable interest in the chemistry of Schiff bases (Nakajima et al., 1998). This is due to the fact that Schiff bases offer opportunities for inducing substrate chirality, tuning the metal centred electronic factor, enhancing the solubility and stability of either homogeneous or heterogeneous catalysts (Opstal & Verpoort, 2003). Schiff base complexes with metals exhibit strong anticancer activity (Chakraborty & Patel, 1996). Here, we report the synthesis and crystal structure of the title compound (I)- new flexible Schiff-base ligand.

The molecule of (I) is shown in Fig. 1. Bond lengths and angles are comparable with those observed in similar compounds (Hu et al., 2008). The C13=N1 and C18=N2 bond lengths of 1.244 (6) and 1.253 (6) Å, respectively, are usual for C=N double bond. Each half of the molecule displays a trans configuration across the C=N double bond. The dihedral angles between the benzene rings C1-C6 and C7-C12 is 62.09 (14) °.

In the crystal structure, there are no significantly short intermolecular contacts.

Related literature top

For general background, see: Nakajima et al. (1998); Opstal & Verpoort (2003); Chakraborty & Patel (1996). For a related structure, see Hu et al. (2008).

Experimental top

4-(4^'-Aminophenoxy)benzenamine (10 mmol), thiophene-2-carbaldehyde (20 mmol) and 20 ml of ethanol were mixed in 50 ml flask. After stirring for 3h at 303 K, the resulting mixture was recrystallized from ethanol, affording the title compound as orange crystalline solid.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering scheme and 30% probability displacement ellipsoids.

N,N'-Bis[(E)-2-thienylmethylene]-4,4'-oxydianiline top

Crystal data top

C₂₂H₁₆N₂OS₂	F(000) = 808
M_r = 388.49	D_x = 1.357 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.0897 (7) Å	Cell parameters from 2059 reflections
b = 41.478 (3) Å	θ = 3.9–25.0°
c = 7.5300 (12) Å	µ = 0.29 mm⁻¹
β = 90.130 (1)°	T = 298 K
V = 1902.0 (4) Å³	Block, red
Z = 4	0.40 × 0.37 × 0.05 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3319 independent reflections
Radiation source: fine-focus sealed tube	2079 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→7
T_min = 0.891, T_max = 0.985	k = −49→38
8674 measured reflections	l = −8→7

Refinement top

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)] = 0.090	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.218	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0631P)² + 3.3823P] where P = (F_o² + 2F_c²)/3
3319 reflections	(Δ/σ)_max < 0.001
244 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₂₂H₁₆N₂OS₂	V = 1902.0 (4) Å³
M_r = 388.49	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.0897 (7) Å	µ = 0.29 mm⁻¹
b = 41.478 (3) Å	T = 298 K
c = 7.5300 (12) Å	0.40 × 0.37 × 0.05 mm
β = 90.130 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3319 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2079 reflections with I > 2σ(I)
T_min = 0.891, T_max = 0.985	R_int = 0.073
8674 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.090	0 restraints
wR(F²) = 0.218	H-atom parameters constrained
S = 1.08	Δρ_max = 0.26 e Å⁻³
3319 reflections	Δρ_min = −0.36 e Å⁻³
244 parameters

Special details top

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.

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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.4955 (3)	0.05770 (4)	0.6056 (3)	0.0906 (6)
S2	0.4773 (3)	0.44248 (5)	0.5080 (3)	0.0998 (7)
N1	0.6149 (7)	0.12778 (10)	0.5599 (6)	0.0552 (11)
N2	0.6082 (7)	0.37230 (10)	0.5480 (6)	0.0529 (11)
O1	0.9917 (5)	0.25041 (8)	0.5517 (5)	0.0489 (8)
C1	0.8811 (7)	0.22122 (11)	0.5554 (6)	0.0409 (11)
C2	0.9821 (7)	0.19597 (11)	0.6410 (6)	0.0443 (12)
H2	1.1137	0.1994	0.7010	0.053*
C3	0.8919 (7)	0.16597 (11)	0.6389 (6)	0.0450 (12)
H3	0.9637	0.1492	0.6969	0.054*
C4	0.6937 (8)	0.15984 (10)	0.5516 (6)	0.0419 (11)
C5	0.5935 (8)	0.18563 (11)	0.4622 (6)	0.0470 (12)
H5	0.4627	0.1822	0.4012	0.056*
C6	0.6854 (8)	0.21602 (11)	0.4629 (6)	0.0451 (12)
H6	0.6177	0.2329	0.4024	0.054*
C7	0.8781 (7)	0.27942 (10)	0.5519 (6)	0.0397 (11)
C8	0.9794 (8)	0.30454 (12)	0.4627 (6)	0.0457 (12)
H8	1.1085	0.3009	0.4001	0.055*
C9	0.8885 (8)	0.33485 (12)	0.4669 (6)	0.0475 (12)
H9	0.9595	0.3519	0.4109	0.057*
C10	0.6885 (7)	0.34028 (11)	0.5557 (6)	0.0412 (11)
C11	0.5918 (8)	0.31457 (11)	0.6446 (6)	0.0473 (12)
H11	0.4615	0.3178	0.7062	0.057*
C12	0.6863 (7)	0.28442 (11)	0.6428 (6)	0.0440 (11)
H12	0.6201	0.2675	0.7032	0.053*
C13	0.4187 (9)	0.12173 (12)	0.5275 (7)	0.0558 (14)
H13	0.3245	0.1384	0.4960	0.067*
C14	0.3329 (9)	0.08851 (12)	0.5382 (7)	0.0556 (14)
C15	0.1330 (9)	0.07893 (13)	0.4965 (8)	0.0655 (16)
H15	0.0224	0.0927	0.4570	0.079*
C16	0.1061 (11)	0.04474 (15)	0.5191 (10)	0.085 (2)
H16	−0.0240	0.0338	0.4956	0.102*
C17	0.2895 (12)	0.03046 (15)	0.5779 (10)	0.084 (2)
H17	0.3025	0.0085	0.6006	0.101*
C18	0.4106 (9)	0.37824 (12)	0.5808 (7)	0.0555 (13)
H18	0.3178	0.3613	0.6101	0.067*
C19	0.3211 (9)	0.41082 (12)	0.5748 (7)	0.0553 (13)
C20	0.1186 (9)	0.42042 (13)	0.6180 (8)	0.0623 (15)
H20	0.0087	0.4065	0.6558	0.075*
C21	0.0893 (11)	0.45432 (15)	0.6002 (9)	0.081 (2)
H21	−0.0408	0.4650	0.6270	0.097*
C22	0.2677 (13)	0.46897 (15)	0.5412 (12)	0.100 (3)
H22	0.2775	0.4910	0.5203	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0697 (11)	0.0664 (11)	0.1356 (17)	0.0015 (9)	−0.0133 (10)	0.0213 (11)
S2	0.0662 (11)	0.0620 (11)	0.171 (2)	−0.0033 (9)	0.0046 (11)	0.0270 (11)
N1	0.049 (3)	0.052 (3)	0.064 (3)	0.002 (2)	−0.002 (2)	0.004 (2)
N2	0.050 (3)	0.045 (3)	0.064 (3)	−0.001 (2)	0.001 (2)	0.001 (2)
O1	0.0408 (17)	0.0418 (18)	0.064 (2)	−0.0024 (15)	0.0016 (15)	−0.0023 (15)
C1	0.041 (3)	0.040 (3)	0.042 (3)	0.000 (2)	0.003 (2)	−0.001 (2)
C2	0.038 (3)	0.047 (3)	0.047 (3)	0.005 (2)	−0.004 (2)	−0.001 (2)
C3	0.044 (3)	0.045 (3)	0.046 (3)	0.008 (2)	−0.006 (2)	0.007 (2)
C4	0.049 (3)	0.034 (3)	0.043 (3)	0.000 (2)	0.004 (2)	0.002 (2)
C5	0.042 (3)	0.049 (3)	0.050 (3)	−0.003 (2)	−0.012 (2)	0.000 (2)
C6	0.049 (3)	0.041 (3)	0.045 (3)	0.005 (2)	−0.008 (2)	0.004 (2)
C7	0.045 (3)	0.037 (3)	0.038 (3)	0.003 (2)	−0.005 (2)	−0.003 (2)
C8	0.038 (3)	0.052 (3)	0.047 (3)	−0.008 (2)	0.002 (2)	−0.005 (2)
C9	0.048 (3)	0.047 (3)	0.048 (3)	−0.011 (2)	−0.001 (2)	0.006 (2)
C10	0.041 (3)	0.040 (3)	0.043 (3)	−0.001 (2)	−0.005 (2)	−0.002 (2)
C11	0.045 (3)	0.046 (3)	0.050 (3)	0.001 (2)	0.010 (2)	−0.001 (2)
C12	0.044 (3)	0.041 (3)	0.046 (3)	−0.004 (2)	0.008 (2)	0.001 (2)
C13	0.061 (4)	0.047 (3)	0.059 (3)	0.010 (3)	−0.001 (3)	−0.002 (2)
C14	0.062 (3)	0.047 (3)	0.058 (3)	0.001 (3)	0.006 (3)	0.000 (2)
C15	0.061 (4)	0.038 (3)	0.097 (5)	0.001 (3)	−0.022 (3)	0.002 (3)
C16	0.062 (4)	0.063 (4)	0.131 (7)	−0.015 (3)	−0.002 (4)	−0.009 (4)
C17	0.092 (5)	0.041 (4)	0.118 (6)	−0.009 (3)	0.022 (4)	0.013 (3)
C18	0.053 (3)	0.051 (3)	0.062 (3)	−0.007 (3)	−0.003 (3)	0.001 (3)
C19	0.055 (3)	0.050 (3)	0.061 (3)	−0.002 (3)	−0.006 (3)	0.001 (3)
C20	0.057 (3)	0.051 (3)	0.079 (4)	0.000 (3)	0.012 (3)	−0.005 (3)
C21	0.072 (4)	0.066 (4)	0.103 (5)	0.020 (4)	−0.018 (4)	−0.009 (4)
C22	0.089 (5)	0.041 (4)	0.170 (8)	−0.005 (4)	−0.021 (5)	0.006 (4)

Geometric parameters (Å, º) top

S1—C14	1.694 (5)	C8—H8	0.9300
S1—C17	1.701 (7)	C9—C10	1.409 (7)
S2—C19	1.698 (5)	C9—H9	0.9300
S2—C22	1.703 (8)	C10—C11	1.390 (6)
N1—C13	1.244 (6)	C11—C12	1.377 (6)
N1—C4	1.415 (6)	C11—H11	0.9300
N2—C18	1.253 (6)	C12—H12	0.9300
N2—C10	1.416 (6)	C13—C14	1.476 (7)
O1—C1	1.386 (5)	C13—H13	0.9300
O1—C7	1.388 (5)	C14—C15	1.318 (7)
C1—C2	1.374 (6)	C15—C16	1.438 (8)
C1—C6	1.396 (6)	C15—H15	0.9300
C2—C3	1.361 (6)	C16—C17	1.338 (9)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.396 (6)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.458 (7)
C4—C5	1.403 (6)	C18—H18	0.9300
C5—C6	1.379 (6)	C19—C20	1.337 (7)
C5—H5	0.9300	C20—C21	1.423 (8)
C6—H6	0.9300	C20—H20	0.9300
C7—C12	1.371 (6)	C21—C22	1.323 (9)
C7—C8	1.385 (6)	C21—H21	0.9300
C8—C9	1.374 (6)	C22—H22	0.9300

C14—S1—C17	91.9 (3)	C12—C11—H11	119.5
C19—S2—C22	92.0 (3)	C10—C11—H11	119.5
C13—N1—C4	120.4 (4)	C7—C12—C11	119.9 (4)
C18—N2—C10	120.5 (4)	C7—C12—H12	120.0
C1—O1—C7	121.0 (3)	C11—C12—H12	120.0
C2—C1—O1	117.3 (4)	N1—C13—C14	121.2 (5)
C2—C1—C6	119.8 (4)	N1—C13—H13	119.4
O1—C1—C6	122.6 (4)	C14—C13—H13	119.4
C3—C2—C1	120.8 (4)	C15—C14—C13	126.5 (5)
C3—C2—H2	119.6	C15—C14—S1	112.5 (4)
C1—C2—H2	119.6	C13—C14—S1	120.9 (4)
C2—C3—C4	121.4 (4)	C14—C15—C16	112.0 (5)
C2—C3—H3	119.3	C14—C15—H15	124.0
C4—C3—H3	119.3	C16—C15—H15	124.0
C3—C4—C5	117.5 (4)	C17—C16—C15	112.4 (6)
C3—C4—N1	116.3 (4)	C17—C16—H16	123.8
C5—C4—N1	126.2 (4)	C15—C16—H16	123.8
C6—C5—C4	121.3 (4)	C16—C17—S1	111.2 (5)
C6—C5—H5	119.4	C16—C17—H17	124.4
C4—C5—H5	119.4	S1—C17—H17	124.4
C5—C6—C1	119.3 (4)	N2—C18—C19	122.3 (5)
C5—C6—H6	120.4	N2—C18—H18	118.8
C1—C6—H6	120.4	C19—C18—H18	118.8
C12—C7—C8	120.6 (4)	C20—C19—C18	127.9 (5)
C12—C7—O1	123.8 (4)	C20—C19—S2	111.1 (4)
C8—C7—O1	115.4 (4)	C18—C19—S2	121.1 (4)
C9—C8—C7	119.8 (4)	C19—C20—C21	112.8 (5)
C9—C8—H8	120.1	C19—C20—H20	123.6
C7—C8—H8	120.1	C21—C20—H20	123.6
C8—C9—C10	120.4 (4)	C22—C21—C20	112.5 (6)
C8—C9—H9	119.8	C22—C21—H21	123.8
C10—C9—H9	119.8	C20—C21—H21	123.8
C11—C10—C9	118.2 (4)	C21—C22—S2	111.7 (5)
C11—C10—N2	126.3 (4)	C21—C22—H22	124.2
C9—C10—N2	115.4 (4)	S2—C22—H22	124.2
C12—C11—C10	121.0 (4)

C7—O1—C1—C2	−148.1 (4)	N2—C10—C11—C12	−179.8 (4)
C7—O1—C1—C6	38.0 (7)	C8—C7—C12—C11	0.5 (7)
O1—C1—C2—C3	−175.0 (4)	O1—C7—C12—C11	175.9 (4)
C6—C1—C2—C3	−1.0 (7)	C10—C11—C12—C7	−0.2 (7)
C1—C2—C3—C4	−0.5 (7)	C4—N1—C13—C14	−179.1 (4)
C2—C3—C4—C5	1.5 (7)	N1—C13—C14—C15	−175.5 (6)
C2—C3—C4—N1	−179.4 (4)	N1—C13—C14—S1	3.3 (7)
C13—N1—C4—C3	161.5 (5)	C17—S1—C14—C15	−0.1 (5)
C13—N1—C4—C5	−19.6 (8)	C17—S1—C14—C13	−179.0 (5)
C3—C4—C5—C6	−1.1 (7)	C13—C14—C15—C16	178.8 (6)
N1—C4—C5—C6	−180.0 (5)	S1—C14—C15—C16	−0.1 (7)
C4—C5—C6—C1	−0.4 (7)	C14—C15—C16—C17	0.2 (9)
C2—C1—C6—C5	1.4 (7)	C15—C16—C17—S1	−0.3 (8)
O1—C1—C6—C5	175.2 (4)	C14—S1—C17—C16	0.2 (6)
C1—O1—C7—C12	35.5 (6)	C10—N2—C18—C19	179.9 (5)
C1—O1—C7—C8	−148.9 (4)	N2—C18—C19—C20	−175.2 (6)
C12—C7—C8—C9	0.8 (7)	N2—C18—C19—S2	4.4 (8)
O1—C7—C8—C9	−175.0 (4)	C22—S2—C19—C20	0.6 (5)
C7—C8—C9—C10	−2.5 (7)	C22—S2—C19—C18	−179.1 (5)
C8—C9—C10—C11	2.8 (7)	C18—C19—C20—C21	178.5 (5)
C8—C9—C10—N2	−178.7 (4)	S2—C19—C20—C21	−1.1 (7)
C18—N2—C10—C11	−19.9 (7)	C19—C20—C21—C22	1.2 (9)
C18—N2—C10—C9	161.6 (5)	C20—C21—C22—S2	−0.8 (9)
C9—C10—C11—C12	−1.4 (7)	C19—S2—C22—C21	0.1 (6)

Experimental details

Crystal data
Chemical formula	C₂₂H₁₆N₂OS₂
M_r	388.49
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.0897 (7), 41.478 (3), 7.5300 (12)
β (°)	90.130 (1)
V (Å³)	1902.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.40 × 0.37 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.891, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	8674, 3319, 2079
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.090, 0.218, 1.08
No. of reflections	3319
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.36

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors acknowledge the financial support of Liaocheng University (grant No. X20090101).

References

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